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WO2016195384A1 - Benzoyl cyclohexanedione compound, and herbicide containing same - Google Patents

Benzoyl cyclohexanedione compound, and herbicide containing same Download PDF

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Publication number
WO2016195384A1
WO2016195384A1 PCT/KR2016/005820 KR2016005820W WO2016195384A1 WO 2016195384 A1 WO2016195384 A1 WO 2016195384A1 KR 2016005820 W KR2016005820 W KR 2016005820W WO 2016195384 A1 WO2016195384 A1 WO 2016195384A1
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WIPO (PCT)
Prior art keywords
compound
ethoxy
triazol
methylsulfonyl
benzoyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/KR2016/005820
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French (fr)
Korean (ko)
Inventor
고영관
김은애
이일영
연규환
구동완
류재욱
염현석
곽미영
조숙희
김경애
김낙정
최정섭
서지희
이규양
오승애
김재덕
오태현
최준혁
박성준
홍미숙
정봉진
명을재
김태준
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Korea Research Institute of Chemical Technology KRICT
FarmHannong Co Ltd
Original Assignee
Korea Research Institute of Chemical Technology KRICT
FarmHannong Co Ltd
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Filing date
Publication date
Application filed by Korea Research Institute of Chemical Technology KRICT, FarmHannong Co Ltd filed Critical Korea Research Institute of Chemical Technology KRICT
Priority claimed from KR1020160067840A external-priority patent/KR101866271B1/en
Publication of WO2016195384A1 publication Critical patent/WO2016195384A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N29/00—Biocides, pest repellants or attractants, or plant growth regulators containing halogenated hydrocarbons
    • A01N29/10—Halogen attached to an aliphatic side chain of an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/06—Oxygen or sulfur directly attached to a cycloaliphatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system

Definitions

  • the present invention relates to a novel benzoylcyclohexanedione compound, a preparation method thereof, and a herbicide comprising the compound.
  • herbicides are one of the agricultural materials that play a very important role in improving the productivity of crops, various kinds of herbicides have been developed and used for this purpose.
  • sulfonylurea herbicides such as pyrazosulfuron ethyl or flucetosulfuron, or aryloxyphenoxypropionate herbicides such as metamipop have been used.
  • phenoxaprop ethyl or Iodosulfuron has been used.
  • triketone herbicides such as mesotrione and sulfonylureage herbicides such as nicosulfuron have been developed and used.
  • non-selective herbicides herbicides such as glyphosate or glufosinate have been used.
  • R 1 represents a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkyl group, or the like; m represents 0, 1, 2 or 3; n represents 0 or 1; A represents alkylene; T or Represents; R 2 represents a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group or a phenyl group, etc.,
  • Q is , , , R 3 represents a hydroxy group, a halogen atom, an alkylcarbonyloxy group, or a 5 or 6 heteroarylthio group;
  • R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 independently represent a halogen atom or an alkyl group,
  • R 10 represents an alkyl group, and
  • R 11 represents an alkyl group or a cycloalkyl group.
  • Patent Document 1 International Publication No. WO2003-066607, "Novel tetrazole derivative useful as a herbicide"
  • An object of the present invention is to provide a benzoylcyclohexanedione compound having a novel structure.
  • the present invention is characterized by a benzoylcyclohexanedione compound represented by the following formula (1), or an agriculturally acceptable salt thereof:
  • R 1 represents a halogen atom, a hydroxyl group, or -OC (O)-(C 1 -C 6 alkyl);
  • R 2 and R 3 each independently represent a hydrogen atom or a C 1 to C 6 alkyl group
  • R 4 is -C 1 -C 6 alkylene-, -C 2 -C 6 alkenylene-, -C 2 -C 6 alkynylene-, C 1 -C 6 haloalkylene group,-(C 1 -C 6 alkyl Lene) -O- (C 1 -C 6 alkylene)-or-(C 1 -C 6 alkylene) -S- (C 1 -C 6 alkylene)-;
  • X represents a halogen atom or a C 1 to C 6 alkyl group
  • Y represents -NO 2 , or -S (O) 2- (C 1 -C 2 alkyl);
  • Z is , or Is selected from,
  • R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl group, or a C 1 -C 6 haloalkyl group;
  • n the integer of 0, 1, or 2.
  • the present invention is 0.1 to 99.9% by weight of at least one active compound selected from the group consisting of benzoylcyclohexanedione compound represented by the formula (1) and agrochemically acceptable salts thereof; And from 0.1 wt% to 99.9 wt% of at least one additive selected from the group consisting of surfactants and solid or liquid diluents.
  • the present invention is characterized by a method for controlling weeds by sleeping or foliage treatment of the herbicide composition.
  • the present invention reacts the 3-oxo-1-cycloalkenyl-3-alkoxy benzoate represented by the following formula (2) with the acetone cyanohydrin reagent represented by the following formula (3), R
  • the manufacturing method of the benzoyl cyclohexanedione compound represented by following General formula (1a) whose 1 is a hydroxyl group is characterized by the above-mentioned.
  • R 2 , R 3 , R 4 , X, Y, Z and n are as defined in Formula 1, respectively.
  • the present invention is a benzoylcyclohexane represented by the following general formula (1b) in which R 1 is a halogen group by reacting a compound represented by the formula (1a) in which R 1 is a hydroxyl group with a halogenation reagent It is characterized by the method for producing a dion compound.
  • R 2 , R 3 , R 4 , X, Y, Z and n are the same as defined in Chemical Formula 1 above, and Hal. Represents the halogen atom.
  • the present invention is a compound represented by the formula (1a) wherein R 1 is a hydroxyl group by reacting with an alkylcarbonyl chloride represented by R 6 -C (O) -Cl, R 1 is alkyl It is characterized by a method for producing a benzoylcyclohexanedione compound represented by the following formula (1c) which is a carbonyloxy group.
  • R 2 , R 3 , R 4 , X, Y, Z and n are as defined in the formula (1), respectively, R 6 represents a C 1 to C 4 alkyl group.
  • novel compounds according to the invention exhibit excellent crop selectivity and herbicidal activity.
  • it is useful as a selective herbicide because of its excellent safety against rice and excellent effect of removing grass and weeds, weeds, and broadleaf weeds in sleep treatment or foliage treatment.
  • the present invention relates to a compound selected from the group consisting of a benzoylcyclohexanedione compound represented by the following formula (1) and an agriculturally acceptable salt.
  • R 1 represents a halogen atom, a hydroxyl group, or -OC (O)-(C 1 -C 6 alkyl);
  • R 2 and R 3 each independently represent a hydrogen atom or a C 1 to C 6 alkyl group
  • R 4 is -C 1 -C 6 alkylene-, -C 2 -C 6 alkenylene-, -C 2 -C 6 alkynylene-, C 1 -C 6 haloalkylene group,-(C 1 -C 6 alkyl Lene) -O- (C 1 -C 6 alkylene)-or-(C 1 -C 6 alkylene) -S- (C 1 -C 6 alkylene)-;
  • X represents a halogen atom or a C 1 to C 6 alkyl group
  • Y represents -NO 2 , or -S (O) 2- (C 1 -C 2 alkyl);
  • Z is , or Is selected from,
  • R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl group, or a C 1 -C 6 haloalkyl group;
  • n the integer of 0, 1, or 2.
  • Group R 1 represents a halogen atom, a hydroxy group, or -OC (O)-(C 1 -C 4 alkyl);
  • R 2 and R 3 each independently represent a hydrogen atom, a methyl group, an ethyl group, a normal propyl group, or an isopropyl group;
  • R 4 is -C 1 -C 4 alkylene-, -C 2 -C 4 alkenylene-, -C 2 -C 4 alkynylene-, -C 1 -C 4 haloalkylene-,-(C 1- C 4 alkylene) -O-CH 2 -,-(C 1 -C 4 alkylene) -O-CH 2 CH 2 -,-(C 1 -C 4 alkylene) -S-CH 2- , or- (C 1 -C 4 alkylene) -S-CH 2 CH 2- ;
  • X represents a halogen atom or a C 1 to C 4 alkyl group
  • Y is -NO 2 , Or -S (O) 2 -CH 3 ;
  • Z is , or Is selected from,
  • R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, or a C 1 -C 4 haloalkyl group;
  • N is the case of the compound which shows the integer of 0, 1, or 2.
  • R 1 represents a chloro atom, a hydroxyl group, or -OC (O)-(C 1 -C 4 alkyl);
  • R 2 and R 3 each independently represent a hydrogen atom or a methyl group
  • R 4 is -C 1 -C 4 alkylene-, -C 2 -C 4 alkenylene-, -C 2 -C 4 alkynylene-, -C 1 -C 2 haloalkylene-,-(C 1- C 2 alkylene) -O-CH 2 -,-(C 1 -C 2 alkylene) -O-CH 2 CH 2 -,-(C 1 -C 2 alkylene) -S-CH 2- , or- (C 1 -C 2 alkylene) -S-CH 2 CH 2- ;
  • X represents a chloro atom or a methyl group
  • Y is -NO 2 , Or -S (O) 2 -CH 3 ;
  • Z is , , , , or Represents
  • N is the case of the compound which shows the integer of 0 or 2.
  • R 1 represents a chloro atom, a hydroxyl group, or -OC (O)-(C 1 -C 4 alkyl);
  • R 2 and R 3 each independently represent a hydrogen atom or a methyl group
  • X represents a chloro atom or a methyl group
  • Y is -NO 2 , Or -S (O) 2 -CH 3 ;
  • Z is , or Represents
  • N is the case of the compound which shows the integer of 0 or 2.
  • benzoylcyclohexanedione compound represented by Chemical Formula 1 are as follows:
  • a compound selected from the group consisting of agrochemically acceptable salts thereof is selected from the group consisting of agrochemically acceptable salts thereof.
  • benzoylcyclohexanedione compound represented by Chemical Formula 1 according to the present invention may be used in the form of an agriculturally acceptable salt.
  • Agrochemically acceptable salts may include, for example, metal salts, salts with organic bases, salts with inorganic acids, salts with organic acids, salts with basic or acidic amino acids, and the like.
  • Suitable metal salts include, for example, alkali metal salts such as sodium salts, potassium salts and the like; Alkaline earth metal salts such as calcium salts, magnesium salts, barium salts, and the like; Aluminum salts and the like.
  • Salts with organic bases are, for example, trimethylamine, triethylamine, diisopropylethylamine, pyridine, picoline, 2,6-lutidine, ethanolamine, diethanolamine, triethanolamine, cyclohexylamine, It may include a salt of a base, and selected from ethylene-diamine-dibenzylamino, etc.-dicyclohexyl amine, N, N.
  • Salts with inorganic acids may include, for example, salts with inorganic acids selected from hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, and the like.
  • Salts with organic acids are, for example, salts with organic acids selected from formic acid, acetic acid, trifluoroacetic acid, phthalic acid, fumaric acid, oxalic acid, tartaric acid, maleic acid, citric acid, succinic acid, methanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid, and the like. This may be included.
  • Salts with basic amino acids may include, for example, salts with basic amino acids selected from arginine, lysine, ornithine and the like.
  • Salts with acidic amino acids may include, for example, salts with acidic amino acids selected from aspartic acid, glutamic acid and the like.
  • some of the compounds represented by Formula 1 according to the present invention may be crystallized or recrystallized from solvents such as aqueous and organic solvents. In this case, the compound represented by Formula 1 may form a solvate.
  • solvents such as aqueous and organic solvents.
  • the compound represented by Formula 1 may form a solvate.
  • water-containing compounds that can be prepared by methods such as lyophilization, stoichiometric solvates, including hydrates, are also within the scope of the present invention.
  • the compound represented by Chemical Formula 1 according to the present invention may have one or more asymmetric centers, and in the case of such compounds, enantiomers or diastereomers may be present.
  • the present invention therefore encompasses each isomer or a mixture of these isomers.
  • the compound represented by Chemical Formula 1 according to the present invention may exist in tautomer form, and the present invention also includes each tautomer or a mixture thereof.
  • halo or halogen in the present invention may be used interchangeably. Specifically, radicals derived from chlorine, fluorine, iodine and bromine may be included.
  • 'Alkyl' in the present invention means a straight chain, branched, or cyclic saturated hydrocarbon radical containing 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms). Specifically methyl, ethyl, normal propyl, isopropyl, cyclopropyl, normal butyl, sec -butyl, tert -butyl, normalpentyl, isopentyl, cyclopentyl, normalhexyl, 2- (methyl) pentyl, cyclohexyl, and the like.
  • 'Haloalkyl' in the present invention means an alkyl radical having 1 to 10 halogen atoms substituted. Specifically, trichloromethyl, dichloroethyl, and the like may be included.
  • 'alkoxy' may include, for example, methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, sec -butoxy, t -butoxy and the like.
  • the present invention includes a method for producing a benzoylcyclohexadione compound represented by the formula (1).
  • the preparation method according to Scheme 1 may be performed under a cyanide compound and basic conditions.
  • the cyanide compound at least one selected from sodium cyanide, potassium cyanide, acetone cyanide, hydrogenated cyanide, and the like may be used.
  • the base may be an organic base including triethylamine, aliphatic amines of diisopropylethylamine, aromatic amines such as dimethylaniline, pyridine, or the like, or an alkali metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, or the like.
  • Inorganic bases can be used.
  • the said base can also be used 1 type or in mixture of 2 or more types.
  • the amount of the cyanide compound and the base may be used in the range of 1 to 4 molar ratios, and preferably in the range of 1 to 2 molar ratios, based on 1 mole of the compound represented by Chemical Formula 2.
  • the reaction temperature is possible in the range of -10 ° C to 80 ° C, preferably maintaining a temperature of 5 ° C to 40 ° C.
  • the reaction solvent any conventional organic solvent which has been used in the art may be used, and there is no particular limitation on the selection thereof. Specific examples of the reaction solvent include toluene, dichloromethane, chloroform, 1,2-dichloroethane, diethyl ether, dimethoxyethane, tetrahydrofuran, acetone, acetonitrile, ethyl acetate, dimethylformamide, and the like. This may be included.
  • the organic layer may be diluted with an organic solvent, washed with acid, and the obtained organic layer may be dried, concentrated and purified by column chromatography.
  • R 2 , R 3 , R 4 , X, Y, Z and n are as defined in Formula 1, respectively, and Hal. Represents a halogen atom.
  • the preparation method according to Scheme 2 includes a) obtaining a compound represented by Chemical Formula 1a as a preparation method according to Scheme 1 and b-1) halogenating the compound represented by Chemical Formula 1a.
  • the halogenation process may be performed using a halogenation reagent under conventional organic solvent conditions.
  • the halogenation reagent may be used at least one selected from oxalyl chloride, oxalyl bromide, diethylaminosulfur trifluoride, and the like.
  • the amount of the halogenating reagent may be used in the range of 1 to 3 molar ratios, based on 1 mole of the compound represented by Formula 1a, and preferably in the range of 1 to 1.5 molar ratios.
  • the halogenation reaction temperature is possible in the range of 0 °C to 40 °C, it is more preferable to maintain the room temperature.
  • the reaction solvent any conventional organic solvent which has been used in the art may be used, and there is no particular limitation on the selection thereof. Specific examples of the reaction solvent may include dichloromethane, chloroform, 1,2-dichloroethane and the like. After the reaction is completed, the organic layer may be diluted with an organic solvent, washed with water, and the obtained organic layer may be dried, concentrated and purified by column chromatography.
  • R 2 , R 3 , R 4 , X, Y, Z and n are as defined in Formula 1, respectively, and R 6 represents a C 1 to C 4 alkyl group.
  • the preparation method according to Scheme 3 includes a) obtaining a compound represented by Chemical Formula 1a as a preparation method according to Scheme 1, and b-2) alkylcarbonylating the compound represented by Chemical Formula 1a.
  • the alkylcarbonylation process can be carried out under basic conditions with alkylcarbonyl chloride.
  • the alkylcarbonyl chloride may specifically include acetyl chloride, propionyl chloride, butyryl chloride, and the like.
  • the base may be an organic base including triethylamine, aliphatic amines of diisopropylethylamine, aromatic amines such as dimethylaniline, pyridine, or the like, or an alkali metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, or the like.
  • Inorganic bases can be used.
  • the said base can also be used 1 type or in mixture of 2 or more types.
  • the amount of the alkylcarbonyl chloride and the base may be used in the range of 1 to 4 molar ratios, based on 1 mole of the compound represented by Chemical Formula 1a, and preferably in the range of 1 to 2 molar ratios.
  • the alkylcarbonylation reaction temperature is possible in the range of 0 ° C to 40 ° C, more preferably at room temperature.
  • the reaction solvent any conventional organic solvent which has been used in the art may be used, and there is no particular limitation on the selection thereof. Specific examples of the reaction solvent may include dichloromethane, chloroform, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, ethyl acetate and the like.
  • the organic layer may be diluted with an organic solvent, washed with water, and the obtained organic layer may be dried, concentrated and purified by column chromatography.
  • Step 1) reacting the substituted methyl hydroxybenzoate represented by Formula 5 with a dibromoalkane reagent represented by Br-R 4 -Br to prepare a substituted methyl bromoalkoxy benzoate represented by Formula 6 Process of doing;
  • Step 2 reacting the compound represented by Chemical Formula 6 with an azole reagent represented by Z-H to prepare a compound represented by Chemical Formula 7;
  • Step 3) hydrolyzing the compound represented by Chemical Formula 7 to prepare a benzoic acid compound represented by Chemical Formula 8;
  • Step 1) proceeds using a dibromoalkane reagent represented by Br-R 4 -Br, and may be performed using a conventional organic solvent in the presence of a base.
  • the reaction temperature ranges from room temperature to the reflux temperature of the organic solvent used, specifically 20 ° C. to 120 ° C., preferably 50 ° C. to 80 ° C.
  • the step process is carried out using an azole reagent represented by Z-H, and may be performed using a conventional organic solvent in the presence of a base and tetrabutylammonium bromide (TBAB) catalyst.
  • the reaction temperature is in the range of reflux temperature of the organic solvent used, specifically, 20 °C to 120 °C, preferably to maintain the temperature range of 70 °C to 90 °C.
  • the step 3) converts the ester group to a carboxylic acid group by hydrolysis.
  • the hydrolysis can be carried out using an acid or a base. In the embodiment of the present invention, it proceeded under alkaline hydrolysis conditions using an alkali metal hydroxide mainly containing sodium hydroxide.
  • the step process can be performed under conditions using a base and a conventional organic solvent using a cycloalkane dione reagent.
  • the reaction temperature ranges from room temperature to the reflux temperature of the organic solvent used, specifically 20 ° C. to 80 ° C., and preferably maintains a temperature around room temperature.
  • Conventional bases used in the preparation method of the present invention may include an organic base or an inorganic base.
  • the organic base one or more selected from the group consisting of tri (C 1 -C 6 alkyl) amine, pyridine, dimethyl aniline, and the like can be used.
  • the organic base may specifically include trimethylamine, triethylamine, diethylisopropylamine, diisopropylethylamine, and the like.
  • As the inorganic base at least one selected from the group consisting of hydroxides, hydrides, carbonates, and C 1 to C 6 alkoxides of alkali metals or alkaline earth metals may be used.
  • the inorganic base may specifically include lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium hydride, potassium hydride, sodium methoxide, potassium methoxide and the like.
  • the base may be used in the range of 1 to 3 molar ratios, preferably 1 to 2 molar ratios, based on 1 mole of the reactant.
  • any solvent that does not participate in the reaction can be used.
  • solvents include, for example, ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane; Halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; Aromatic hydrocarbons such as benzene, toluene and xylene; Aliphatic hydrocarbons such as normal hexane, cyclohexane and heptane; Nitrites such as acetonitrile and propionitrile; Ketones such as acetone; Acetates such as ethyl acetate; Amides such as dimethylformamide (DMF); One or two isomers selected from the group consisting of and the like can be appropriately selected and used.
  • ethers such as diethyl ether, tetrahydrofuran (TH
  • Methyl 2,4-dichloro-3-hydroxybenzoate (90.48 mmol) was dissolved in 300 mL of acetone, followed by addition of 1,2-dibromoethane (452.4 mmol) and potassium carbonate (180.96 mmol). The reaction mixture was stirred at 60 ° C. for at least 6 hours, and when the reaction was complete the solvent was concentrated under reduced pressure. The organic layer was extracted with ethyl acetate and water, dried over anhydrous magnesium sulfate, and the solvent was removed. Column chromatography can be used to yield 26 g (88% yield) of the desired compound.
  • the reaction mixture was diluted with ethyl acetate, washed twice with aqueous ammonium chloride solution, washed once with 1N aqueous hydrogen chloride solution, dried over anhydrous magnesium sulfate, and the solvent was removed.
  • Column chromatography can be used to obtain 0.38 g (yield 61%) of the desired compound.
  • Methyl 3-hydroxy-2-methylbenzoate (50 g, 0.301 mole) is dissolved in 50 mL of ethyl acetate and 200 mL of acetic acid, nitric acid (24.4 mL, 0.331 mmol) is slowly added dropwise over 10 minutes, and at room temperature, 1 Stir for hours.
  • the reaction solution was diluted with 1 L of water and washed twice with water, extracted with ethyl acetate.
  • the extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure.
  • the extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure.
  • the extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 157 mg (83% yield) of the target compound.
  • the extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 31 mg (52% yield) of the title compound in the solid state.
  • reaction solution was diluted with water and extracted with ethyl acetate (50 mL) and washed with water and brine.
  • the extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure.
  • the extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure.
  • the extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 100 mg (68% yield) of the title compound.
  • the extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 100 mg (60% yield) of the title compound.
  • the benzoylcyclohexanedione compound represented by Chemical Formula 1 of the present invention may be usefully used as a herbicide, and when used as a herbicide, carriers, surfactants, dispersants, adjuvants, and the like, which are commonly used in formulating pesticides, may be used. It can be used by formulating in various forms, such as a hydrating agent, an emulsion, a powder suspension, and a liquid, in combination with the compound. These formulations can be used directly and can be processed by dilution in appropriate media.
  • Spray volumes can be used from several hundred liters to several thousand liters per hectare (ha).
  • the herbicide composition of the present invention comprises 0.1 wt% to 99.9 wt% of at least one active ingredient selected from the group consisting of a benzoylcyclohexanedione compound represented by Formula 1 and agrochemically acceptable salts thereof; And 0.1% to 99.9% by weight of one or two or more additives selected from surfactants and solid or liquid diluents; It includes.
  • the herbicide composition may include the active ingredient in the range of 0.1% by weight to 99.9% by weight, and the content of the active ingredient may vary depending on the form of the preparation. In addition, the herbicide composition may be included in the range of 0.1% to 99.9% by weight.
  • the additive may be a surfactant, a solid diluent or a liquid diluent, the surfactant may be contained in the range of about 0.1% to 20% by weight, and the solid or liquid diluent may be contained in the range of 0% to 99.9% by weight. You can also
  • Table 3 summarizes the contents of the active ingredients, surfactants and diluents by the type of preparation.
  • Formulation Content ratio (unit: weight%) Active ingredient Surfactants diluent Hydrating agent 10 to 90 1 to 10 0 to 80 Suspension 3 to 50 0 to 15 40 to 95 Emulsion / Liquid 3 to 50 0 to 15 40 to 95 Granulation 0.1 to 95 1 to 15 5 to 99.5
  • the surfactant is a material having a high surfactant, and may be an amphiphilic material having hydrophilic and lipophilic molecular groups in a molecule. These surfactants are excellent in detergency, dispersibility, emulsifying power, solubilizing power, wetting power, bactericidal power, foaming power, and penetration power, so that they are wetted, collapsed, dispersed, or emulsified to effectively express medicinal effects. .
  • surfactant examples include (C 8 -C 12 alkyl) benzenesulfonate, (C 3 -C 6 alkyl) naphthalenesulfonate, di (C 3 -C 6 alkyl) naphthalenesulfonate, di (C 8 -C 12 alkyl ) Sulfosuccinate, lignin sulfonate, naphthalene sulfosuccinate formalin condensate, (C 8 -C 12 alkyl) naphthalenesulfonate formalin condensate, polyoxyethylene (C 8 -C 12 alkyl) phenylsulfonate Sodium or calcium salts of sulfonates; Sodium or calcium salts of sulfates such as (C 8 -C 12 alkyl) sulfate, polyoxyethylene (C 8 -C 12 alkyl) sulfate, polyoxyethylene (C 8 -C 12 al
  • the surfactant may be nonionic such as polyoxyethylene (C 8 -C 12 alkyl) ether, polyoxyethylene (C 8 -C 12 alkyl) phenyl ether, polyoxyethylene (C 8 -C 12 alkyl) phenyl polymer.
  • Surfactants may be included. The above surfactants may be used alone or in combination of two or more thereof, and the surfactants that may be used in the present invention are not limited to the compounds exemplified above.
  • the content of the active ingredient can be adjusted according to the use, it is sometimes necessary to use a higher content of the surfactant than the active ingredient and may be added in the formulation or used in tank mixing.
  • Diluents included in the herbicide composition of the present invention may be classified into solid diluents and liquid diluents depending on their properties. Highly absorbent diluents as solid diluents are particularly good when making hydrates.
  • the liquid diluent and the solvent are preferably stable without phase separation even at 0 ° C.
  • Liquid diluents include water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butyrate carbonate, Chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p -diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene Glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N, N -dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol
  • Solid diluents include talc, titanium dioxide, feldspar clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husk, wholemeal, soybean flour, pumice, wood flour, walnut husk, Lignin and the like can be used.
  • a small amount of other additives may be added to prevent foaming, cake formation, corrosion, microbial propagation, and the like.
  • the method for making the herbicide composition of the present invention is carried out by conventional methods.
  • the components only need to be mixed, and the fine solid composition may be mixed and ground in a hammer or a flour mill.
  • Suspensions may be prepared by admixing in a wet mill and granulating by spraying an active substance on the granular carrier.
  • the following components were thoroughly mixed and the liquid surfactant was mixed while spraying onto the solid components. Grinding in a hammer mill brought the particle size to 100 ⁇ m or less.
  • the formulation of the present invention was sprayed by diluting to an appropriate concentration in actual use.
  • the benzoylcyclohexanedione compound according to the present invention is excellent in the effect of controlling various weeds by treating the soil. Specifically, the benzoylcyclohexanedione compound according to the present invention was excellent in controlling the weeds, which is undesirable in the sleep treatment or foliage treatment. The benzoylcyclohexanedione compound according to the present invention exhibits high safety against rice when subjected to sleep treatment or foliage treatment. The benzoylcyclohexanedione compound according to the present invention has an excellent effect of controlling flowering plants, weeds, weeds, or broadleaf weeds.
  • the herbicide containing the benzoylcyclohexanedione compound as an active ingredient is suitable for paddy farming and field farming.
  • the herbicide of the present invention can be used up to 10 g to 1 kg per hectare (ha) as an active ingredient, preferably 10 g to 400 g.
  • the choice of dosage is determined by factors such as weed generation, growth level, and preparation.
  • the compounds of the present invention can be used alone, acetyl-CoA carboxylase inhibitors (ACC), acetolactate synthase inhibitors (ALS), amides, auxin herbicides, auxin transport inhibitors, carotenoid biosynthesis inhibitors, enolpyrubil Sikimate 3-phosphate synthase inhibitors (ESPS), glutamine synthetase inhibitors, lipid biosynthesis inhibitors, mitosis inhibitors, protoporpyrogenogen IX oxidase inhibitors, photosynthesis inhibitors, synergists, growth substances, cell wall biosynthesis inhibitors and other herbicides It is also useful to use in admixture with one or more herbicidally active compounds selected from the group consisting of:
  • acetyl-CoA carboxylase inhibitors include alkoxydim, cletodim, cloproxidim, cyclooxydim, cetoxydim, tralcoxydim, butoxyroxim, clepoxydim or as cyclohexenone oxime ethers.
  • Tefraloxydim, phenoxyphenoxypropionic acid esters include metamipop, sihalofop-butyl, diclopop-methyl, phenoxaprop-ethyl, phenoxaprop-P-ethyl, pentiaprop- Ethyl, Fluazifop-Butyl, Fluazifop-P-Butyl, Haloxifop-Ethoxyethyl, Haloxifop-Methyl, Haloxifop-P-Methyl, Isoxapyrifop, Propacquisapop, Quiz Allopop-ethyl, quizallofo-P-ethyl or quizallofo-tefuryl can be used.
  • acetolactate synthase inhibitor is imidazolinone as imazapyr, imazaquin, imazamethabenz-methyl, imaco, imazapic, imazetapyr or imazametapyr, pyrimidyl ether Thiobac-acid, pyrithiobac-sodium, bispyribac-sodium or pyribenzoxime, florasullam as sulfonamide, flumetsulam or metosullam, amidosulfuron as a sulfonylurea, azimsulfuron, bensulfuron-methyl , Chlorimuron-ethyl, chlorsulfuron, cynosulfuron, cyclosulfuron, etamethsulfuron-methyl, ethoxysulfuron, plazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, Nicosulfur
  • auxin herbicide clopyralide or picloram, 2,4-D or benazolin may be used as the pyridine carboxylic acid.
  • Naphthalam or diflufenzopyr may be used as the auxin transport inhibitor, and the carotenoid biosynthesis inhibitor may be benzophenaf, clomazone, diflufenican, fluorochloridone, flulidone, pyrazolinate, or pyra. You may use oxypsifen, isoxaplutol, isoxachlortol, mesotrione, sulcotrione (chlormethulon), ketospiradox, flutamone, norflurazon or amitrol.
  • Glyphosate or sulfosate may be used as the enolpyruvyl mate 3-phosphate synthase inhibitor (ESPS), and villanafos (non-alpafoss) or glufosinate-ammonium may be used as the glutamine synthetase inhibitor.
  • EPS enolpyruvyl mate 3-phosphate synthase inhibitor
  • villanafos non-alpafoss
  • glufosinate-ammonium may be used as the glutamine synthetase inhibitor.
  • the lipid biosynthesis inhibitors include anilophos or mefenacet as anilide, dimethenamid, S-dimethenamid, acetochlor, alachlor, butachlor, buteneaclor, dietathyl-ethyl, dimethalide as chloroacetanilide Chlor, metazachlor, methol achlor, S-methol achlor, pretyl achlor, propacchlor, priaclor, terbuchlor, tenylchlor or xylaclor, butyrate as thiourea, cycloate, di- Alate, dimepiperate, EPTC, esprocarb, molinate, pebulate, prosulfocarb, thiobencarb (benthiocarb), tri-acrylate or benolate, benfuresate or perfluidone Can be used.
  • mitosis inhibitors include asulam as carbamate, carbetamid, chlorprofam, orbencarb, prolonamide (propizamide), propam or thiocarbazil, benipine as dinitroaniline, butraline , Dinitramine, etafluralin, fluchlorine, oryzaline, pendimethalin, prodiamine or trifluralin, dithiopyr or thiazopyr as pyridine, butamiphosph, chlortal-dimethyl (DCPA) or male Acid hydrazide can be used.
  • asulam as carbamate, carbetamid, chlorprofam, orbencarb
  • prolonamide propam
  • thiocarbazil benipine as dinitroaniline, butraline , Dinitramine, etafluralin, fluchlorine, oryzaline
  • pendimethalin prodiamine or trifluralin
  • the protoporpynogen IX oxidase inhibitors are diphenyl ethers such as asifluorfen, asifluorophene-sodium, acloniphene, biphenox, chlornitropen (CNP), ethoxyphene, fluorodiphene, fluoroglycopene Ethyl, pomesafen, furyloxyphene, lactofen, nitrophene, nitrofluorophene or oxyfluorene, oxadiargyl or oxadione as oxadiazole, azaphenidine, butafenacyl as cyclic imide, Carpentrazone-ethyl, cinidon-ethyl, flumichlorac-pentyl, flumioxazine, flumipropine, flupropacyl, fluthiacet-methyl, sulfentrazone or thidiazimine, pyrazole as pyrazole Phen
  • the photosynthesis inhibitors are propanyl, pyridate pyridafol, benzothiadiazinone as benzozone, bromophenoxime as dinitrophenol, dinocept, dinocept-acetate, dinoterb or DNOC, ciperquat as dipyridylene- Chloride, dipenzoquat-methylsulfate, diquat or paraquat-dichloride, as urea chlorbromuron, chlorotoluron, diphenoxuron, dimefuron, diuron, etidimuron, phenuron, fluoromethuron, iso Proturon, isouron, linuron, metabenzthiazuron, metazole, methopenzuron, methoxuron, monolinuron, neburon, siduron or tebutiuuron, bromocinyl or ethynyl as phenol, chlor Lidazone, triazine,
  • Tridiphan may be used as the oxirane as the synergist, and 2,4-DB, clomeprop, dichlorprop, dichlorprop-P (2,4) as aryloxyalkanoic acid as the growth material.
  • -DP-P fluorooxypyr
  • MCPA mecoprop
  • mecoprop-P or triclopyr chloramben or dicamba as benzoic acid
  • quinclolac or quinmerak as quinolinecarboxylic acid
  • the cell wall synthesis inhibitor isoxaben or diclobenyl can be used.
  • Examples of the other herbicides include: dalapon as dichloropropionic acid, etofumesate as dihydrobenzofuran, chlorfenac (phenac) as phenylacetic acid, or aziprotrin, barban, bensulfide, benzthiazurone, benzofluorine, Minaphos, Butidazole, Buturon, Carpenstrol, Chlorbufam, Chlorfenprop-methyl, Chloroxolone, Cynmethylene, Cumyluron, Cyclolone, Ciprazine, Ciprazole, Dibenzyluron, Dipro Petrin, Dimron, Eglinazine-Ethyl, Endotal, Ethiozin, Flucarbazone, Fluorbentranil, Flupoxam, Isocarbamide, Isopropelin, Carbutylate, Mefluidide, Monuron, Napro Pamide, napropanilide, nitraline,
  • the compounds according to the invention have herbicidal activity against harmful plants.
  • the 'harmful plants' are unwanted plants that grow on cropland, and refer to plants that need to be controlled.
  • the number of weeds is very large and the classification methods are very diverse.
  • the flowers and weeds include sorghum, dolpi, wheat, American dog breeze, barbarian, minbari, king blue, pup grass, pulp grass, fall puppy grass, dredges, vines, large binori, rhythm birds, poa grass or wangpo grass.
  • the herbaceous weeds include a swell, tadpoles, hyangbuja, beetle dongsae, shackles, snares, barberry.
  • the broad-leaved weeds include water wolves, crows, lizards and the like.
  • Monocotyledonous weed species may include flower beds and weeds or weeds.
  • the dicotyledonous weed species include nasturtium, hairy scallop, creeper grass, wormwood, wormwood, american fern, western dandelion, gazelweed, forget-me-not, hairy starfish, locust, barley grass, cedar, wormwood needle, jindukchal, maple leaf pig grass, Chrysanthemum weeds such as bittersweet, alder, persimmon, american mugwort, squirrel, dandelion, ragweed, fat, red sprout; Nectar and weeds such as scented oil, persimmon grass, perilla grass and motherwort; Antidote and weeds, such as sesame seeds, big slug, and baby slug; Hyunsam and weeds, such as wrinkled leaves and turf
  • the soil kept in a sieve was placed in a stirrer and mixed while supplying water, and mixed with water to give 1 g of water fertilizer (N-P-K: 21-17-17) per 2 kg of soil.
  • steam sterilization was used in a soil sterilizer at 120 ° C. for 30 minutes.
  • Sowing was evenly spread over the surface of the paddy soil, so that the appropriate amount of seeds were placed in the proper position and pressed to be buried in the soil.
  • Swallowtail M. vaginalis
  • tadpoles S. juncoides
  • the drug treatment was prepared about 15 days after rice transplantation so that the final amount of preparation was 0.2% Tween 20, 50% acetone, and 50% water.
  • the amount of active compound was chosen to be the specific amount desired.
  • Foliage was filled with horticultural soil in a 350 cm 2 square plastic pot.
  • seed (10-15 grains), underground diameters (2 objects), and rice of three varieties of barley, sorghum and dolphins, weeds and crows, two broad-leaved weeds, were stored in low temperature (6 ° C).
  • diluent 50% acetone, Tween-20 0.1%) to the final throughput of the test compound 75 g ai / ha Dilution) to prepare a test compound solution.
  • the prepared experimental compound solution was foliage treated using a hand spray in a fume hood at an amount of 14 mL per pot.
  • Patent Document 1 International Patent Publication No. WO2003-066607
  • the chemical structures of the control compounds 1 and 2 are as follows.
  • the compound represented by the formula (1) according to the present invention was excellent in the effect of controlling the weed paddy field weeds, such as water squirrel, tadpole.
  • the results of experiments on crop weakening with respect to the compounds of the compounds Nos. 9, 27 and 35 and the control compounds 1 and 2 which are confirmed to be excellent herbicidal activity are shown in Table 4 above. According to Table 4, it can be seen that the compound represented by Formula 1 according to the present invention exhibits high safety against rice.
  • the compound represented by the formula (1) according to the present invention was excellent in controlling the weeds, such as sorghum, dolpi, barium, crow, lizard.
  • the results of the crop weakness test on the compounds of Compound Nos. 44, 48, 61, 62, 67, 68, 70, 91, and 104 and Control Compounds 1 and 2, which were confirmed to have excellent herbicidal activity, are shown in Table 5 above. It is described. According to Table 5, it can be seen that the compound represented by the formula (1) according to the present invention shows a high safety for rice.

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Abstract

The present invention relates to a novel benzoyl cyclohexanedione compound, a preparation method therefor, and a herbicide containing the compound. The compound of the present invention is very safe in rice crops and has excellent herbicidal activity against Poaceae weeds, Cyperaceae weeds or broad-leaved weeds, thereby being useful as a herbicide for water treatment or foliar treatment.

Description

벤조일사이클로헥산다이온 화합물 및 이 화합물을 포함하는 제초제Benzoylcyclohexanedione compound and herbicides containing the compound

본 발명은 신규의 벤조일사이클로헥산다이온 화합물과 이의 제조방법, 그리고 이 화합물을 포함하는 제초제에 관한 것이다.The present invention relates to a novel benzoylcyclohexanedione compound, a preparation method thereof, and a herbicide comprising the compound.

일반적으로 제초제는 농작물의 생산성 향상에 매우 중요한 역할을 하는 농자재 중의 하나이며, 이러한 목적으로 그 동안 여러 종류의 제초제들이 개발되어 사용되어 왔다. In general, herbicides are one of the agricultural materials that play a very important role in improving the productivity of crops, various kinds of herbicides have been developed and used for this purpose.

벼 재배용 제초제로서 피라조설퓨론 에틸 (Pyrazosulfuron ethyl)이나 플루세토설퓨론 (Flucetosulfuron) 같은 설포닐우레아계 제초제, 또는 메타미포프 (Metamifop)와 같은 아릴옥시페녹시프로피오네이트계 제초제들이 사용되어 왔다. 밀 재배용 제초제로서 페녹시프롭 에틸 (Phenoxaprop ethyl) 또는 아이오도설퓨런 (Iodosulfuron) 등이 사용되어 왔다. 옥수수 재배용 제초제로서 메조트리온 (Mesotrione)과 같은 트리케톤계 제초제와 니코설퓨런 (Nicosulfuron) 등의 설포닐우레아게 제초제가 개발되어 사용되고 있다. 한편 비선택성 제초제로서는 글라이포세이트 (Glyphosate) 또는 글루포시네이트 (Glufosinate) 등의 제초제들이 사용되어 왔다.As herbicides for rice cultivation, sulfonylurea herbicides such as pyrazosulfuron ethyl or flucetosulfuron, or aryloxyphenoxypropionate herbicides such as metamipop have been used. As a herbicide for wheat cultivation, phenoxaprop ethyl or Iodosulfuron has been used. As corn herbicides, triketone herbicides such as mesotrione and sulfonylureage herbicides such as nicosulfuron have been developed and used. Meanwhile, as non-selective herbicides, herbicides such as glyphosate or glufosinate have been used.

그러나 아직도 농업에 손실을 초래하는 많은 잡초들이 발생하고 있으며, 특히 최근에는 기존 제초제의 장기간 반복사용에 의한 저항성 잡초발생이 문제가 되고 있어, 새로운 제초제의 연구 개발이 계속 요구되고 있다.However, a lot of weeds are still occurring, which cause a loss in agriculture. In particular, in recent years, resistance to weeds caused by long-term repeated use of existing herbicides has become a problem, and research and development of new herbicides is continuously required.

국제공개특허공보 WO2003-066607호에는 하기 화학식 A로 표시되는 벤조일사이클로헥산다이온 화합물이 개시되어 있다.International Publication No. WO2003-066607 discloses a benzoylcyclohexanedione compound represented by the following formula (A).

[화학식 A][Formula A]

Figure PCTKR2016005820-appb-I000001
Figure PCTKR2016005820-appb-I000001

상기 화학식 A에서, R1은 할로젠원자, 알킬기, 할로알킬기, 알콕시기, 알콕시알킬기 등을 나타내고; m은 0, 1, 2 또는 3을 나타내고; n은 0 또는 1을 나타내고; A는 알킬렌을 나타내고; T는

Figure PCTKR2016005820-appb-I000002
또는
Figure PCTKR2016005820-appb-I000003
를 나타내고; R2는 할로젠원자, 알킬기, 알케닐기, 알키닐기, 할로알킬기 또는 페닐기 등을 나타내며, In formula (A), R 1 represents a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkoxyalkyl group, or the like; m represents 0, 1, 2 or 3; n represents 0 or 1; A represents alkylene; T
Figure PCTKR2016005820-appb-I000002
or
Figure PCTKR2016005820-appb-I000003
Represents; R 2 represents a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group or a phenyl group, etc.,

Q는

Figure PCTKR2016005820-appb-I000004
,
Figure PCTKR2016005820-appb-I000005
,
Figure PCTKR2016005820-appb-I000006
,
Figure PCTKR2016005820-appb-I000007
를 나타내고, R3은 하이드록시기, 할로젠원자, 알킬카보닐옥시기, 또는 5 또는 6각의 헤테로아릴싸이오기 등을 나타내고; R4, R5, R6, R7, R8, 및 R9는 서로 독립적으로 할로젠원자 또는 알킬기를 나타내며, R10은 알킬기를 나타내며, R11은 알킬기 또는 사이클로 알킬기를 나타낸다.Q is
Figure PCTKR2016005820-appb-I000004
,
Figure PCTKR2016005820-appb-I000005
,
Figure PCTKR2016005820-appb-I000006
,
Figure PCTKR2016005820-appb-I000007
R 3 represents a hydroxy group, a halogen atom, an alkylcarbonyloxy group, or a 5 or 6 heteroarylthio group; R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 independently represent a halogen atom or an alkyl group, R 10 represents an alkyl group, and R 11 represents an alkyl group or a cycloalkyl group.

그러나 상기 화학식 A의 화합물은 재배작물에 대한 선택성과 문제 잡초에 대한 방제력 면에서 충분하지 않으므로, 이러한 문제점을 해결할 수 있는 신규 고성능 제초제의 개발이 요구되는 실정이다.However, since the compound of Formula A is not sufficient in terms of selectivity for cultivating crops and control of weeds, there is a need to develop a new high-performance herbicide that can solve these problems.

(선행기술문헌)(Prior art document)

(특허문헌)(Patent literature)

(특허문헌 1) 국제공개특허공보 WO2003-066607호, "제초제로 유용한 신규 테트라졸 유도체"(Patent Document 1) International Publication No. WO2003-066607, "Novel tetrazole derivative useful as a herbicide"

본 발명은 신규 구조의 벤조일사이클로헥산다이온 화합물을 제공하는 것을 목적한다.An object of the present invention is to provide a benzoylcyclohexanedione compound having a novel structure.

또한, 본 발명은 벤조일사이클로헥산다이온 화합물의 제조방법을 제공하는 것을 다른 목적한다.It is another object of the present invention to provide a method for producing a benzoylcyclohexanedione compound.

또한, 본 발명은 벤조일사이클로헥산다이온 화합물 및 이의 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 화합물이 활성성분으로 포함된 제초제를 제공하는 것을 또 다른 목적한다.It is another object of the present invention to provide a herbicide in which a compound selected from the group consisting of a benzoylcyclohexanedione compound and agrochemically acceptable salts thereof is included as an active ingredient.

상기한 과제 해결을 위한 일 양태에 의하면, 본 발명은 하기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물, 또는 이의 농약학적으로 허용 가능한 염을 그 특징으로 한다 : According to one aspect for solving the above problems, the present invention is characterized by a benzoylcyclohexanedione compound represented by the following formula (1), or an agriculturally acceptable salt thereof:

[화학식 1][Formula 1]

Figure PCTKR2016005820-appb-I000008
Figure PCTKR2016005820-appb-I000008

상기 화학식 1에서, In Chemical Formula 1,

R1은 할로젠원자, 하이드록시기, 또는 -O-C(O)-(C1～C6알킬) 를 나타내고;R 1 represents a halogen atom, a hydroxyl group, or -OC (O)-(C 1 -C 6 alkyl);

R2 및 R3은 각각 독립적으로 수소원자, 또는 C1～C6알킬기를 나타내고;R 2 and R 3 each independently represent a hydrogen atom or a C 1 to C 6 alkyl group;

R4는 -C1～C6알킬렌-, -C2～C6알케닐렌-, -C2～C6알키닐렌-, C1～C6할로알킬렌기, -(C1～C6알킬렌)-O-(C1～C6알킬렌)-, 또는 -(C1～C6알킬렌)-S-(C1～C6알킬렌)-를 나타내고;R 4 is -C 1 -C 6 alkylene-, -C 2 -C 6 alkenylene-, -C 2 -C 6 alkynylene-, C 1 -C 6 haloalkylene group,-(C 1 -C 6 alkyl Lene) -O- (C 1 -C 6 alkylene)-or-(C 1 -C 6 alkylene) -S- (C 1 -C 6 alkylene)-;

X는 할로젠원자, 또는 C1～C6알킬기를 나타내고;X represents a halogen atom or a C 1 to C 6 alkyl group;

Y는 -NO2, 또는 -S(O)2-(C1～C2알킬)를 나타내고;Y represents -NO 2 , or -S (O) 2- (C 1 -C 2 alkyl);

Z는

Figure PCTKR2016005820-appb-I000009
,
Figure PCTKR2016005820-appb-I000010
또는
Figure PCTKR2016005820-appb-I000011
로부터 선택되고,Z is
Figure PCTKR2016005820-appb-I000009
,
Figure PCTKR2016005820-appb-I000010
or
Figure PCTKR2016005820-appb-I000011
Is selected from,

R5는 수소원자, 할로젠원자, C1～C6알킬기, 또는 C1～C6할로알킬기를 나타내고;R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl group, or a C 1 -C 6 haloalkyl group;

n은 0, 1, 또는 2의 정수를 나타낸다.n represents the integer of 0, 1, or 2.

본 발명의 다른 양태에 따르면, 본 발명은 상기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물 및 이의 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 1종 이상의 활성화합물 0.1 중량% 내지 99.9 중량%; 및 계면활성제와 고체 또는 액체 희석제로 이루어진 군으로부터 선택된 1종 이상의 첨가제 0.1 중량% 내지 99.9 중량%;포함된 제초제 조성물을 그 특징으로 한다.According to another aspect of the invention, the present invention is 0.1 to 99.9% by weight of at least one active compound selected from the group consisting of benzoylcyclohexanedione compound represented by the formula (1) and agrochemically acceptable salts thereof; And from 0.1 wt% to 99.9 wt% of at least one additive selected from the group consisting of surfactants and solid or liquid diluents.

본 발명의 다른 양태에 따르면, 본 발명은 상기 제초제 조성물을 수면처리 또는 경엽처리하여 잡초를 방제하는 방법을 그 특징으로 한다.According to another aspect of the present invention, the present invention is characterized by a method for controlling weeds by sleeping or foliage treatment of the herbicide composition.

본 발명의 또 다른 양태에 따르면, 본 발명은 하기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시 벤조에이트와 하기 화학식 3으로 표시되는 아세톤 시아노하이드린 시약을 반응시켜, R1이 하이드록시기인 하기 화학식 1a로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법을 그 특징으로 한다.According to another embodiment of the present invention, the present invention reacts the 3-oxo-1-cycloalkenyl-3-alkoxy benzoate represented by the following formula (2) with the acetone cyanohydrin reagent represented by the following formula (3), R The manufacturing method of the benzoyl cyclohexanedione compound represented by following General formula (1a) whose 1 is a hydroxyl group is characterized by the above-mentioned.

Figure PCTKR2016005820-appb-I000012
Figure PCTKR2016005820-appb-I000012

(상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같다)(In the above scheme, R 2 , R 3 , R 4 , X, Y, Z and n are as defined in Formula 1, respectively)

본 발명의 또 다른 양태에 따르면, 본 발명은 R1이 하이드록시기인 상기 화학식 1a로 표시되는 화합물을 할로젠화 시약과 반응시켜, R1이 할로젠원자인 하기 화학식 1b로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법을 그 특징으로 한다.According to another embodiment of the present invention, the present invention is a benzoylcyclohexane represented by the following general formula (1b) in which R 1 is a halogen group by reacting a compound represented by the formula (1a) in which R 1 is a hydroxyl group with a halogenation reagent It is characterized by the method for producing a dion compound.

Figure PCTKR2016005820-appb-I000013
Figure PCTKR2016005820-appb-I000013

(상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같고, Hal.은 할로젠원자를 나타낸다)(In the above scheme, R 2 , R 3 , R 4 , X, Y, Z and n are the same as defined in Chemical Formula 1 above, and Hal. Represents the halogen atom.)

본 발명의 또 다른 양태에 따르면, 본 발명은 R1이 하이드록시기인 상기 화학식 1a로 표시되는 화합물을 R6-C(O)-Cl로 표시되는 알킬카르보닐 클로라이드와 반응시켜, R1이 알킬카르보닐옥시기인 하기 화학식 1c로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법을 그 특징으로 한다. According to another embodiment of the present invention, the present invention is a compound represented by the formula (1a) wherein R 1 is a hydroxyl group by reacting with an alkylcarbonyl chloride represented by R 6 -C (O) -Cl, R 1 is alkyl It is characterized by a method for producing a benzoylcyclohexanedione compound represented by the following formula (1c) which is a carbonyloxy group.

Figure PCTKR2016005820-appb-I000014
Figure PCTKR2016005820-appb-I000014

(상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같고, R6는 C1～C4알킬기를 나타낸다.)(In the above scheme, R 2 , R 3 , R 4 , X, Y, Z and n are as defined in the formula (1), respectively, R 6 represents a C 1 to C 4 alkyl group.)

본 발명에 따른 신규 화합물은 우수한 작물선택성과 제초활성을 나타낸다. 특히 벼에 대한 안전성이 우수하면서 수면처리 또는 경엽처리에서 화본과 잡초, 사초과 잡초, 또는 광엽 잡초의 제거 효과가 뛰어나므로 선택성 제초제로 유용하다.The novel compounds according to the invention exhibit excellent crop selectivity and herbicidal activity. In particular, it is useful as a selective herbicide because of its excellent safety against rice and excellent effect of removing grass and weeds, weeds, and broadleaf weeds in sleep treatment or foliage treatment.

이와 같은 본 발명을 보다 구체적으로 설명하면 하기와 같다.The present invention will be described in more detail as follows.

본 발명은 하기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물 및 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 화합물에 관한 것이다.The present invention relates to a compound selected from the group consisting of a benzoylcyclohexanedione compound represented by the following formula (1) and an agriculturally acceptable salt.

[화학식 1][Formula 1]

Figure PCTKR2016005820-appb-I000015
Figure PCTKR2016005820-appb-I000015

상기 화학식 1에서, In Chemical Formula 1,

R1은 할로젠원자, 하이드록시기, 또는 -O-C(O)-(C1～C6알킬) 를 나타내고;R 1 represents a halogen atom, a hydroxyl group, or -OC (O)-(C 1 -C 6 alkyl);

R2 및 R3은 각각 독립적으로 수소원자, 또는 C1～C6알킬기를 나타내고;R 2 and R 3 each independently represent a hydrogen atom or a C 1 to C 6 alkyl group;

R4는 -C1～C6알킬렌-, -C2～C6알케닐렌-, -C2～C6알키닐렌-, C1～C6할로알킬렌기, -(C1～C6알킬렌)-O-(C1～C6알킬렌)-, 또는 -(C1～C6알킬렌)-S-(C1～C6알킬렌)-를 나타내고;R 4 is -C 1 -C 6 alkylene-, -C 2 -C 6 alkenylene-, -C 2 -C 6 alkynylene-, C 1 -C 6 haloalkylene group,-(C 1 -C 6 alkyl Lene) -O- (C 1 -C 6 alkylene)-or-(C 1 -C 6 alkylene) -S- (C 1 -C 6 alkylene)-;

X는 할로젠원자, 또는 C1～C6알킬기를 나타내고;X represents a halogen atom or a C 1 to C 6 alkyl group;

Y는 -NO2, 또는 -S(O)2-(C1～C2알킬)를 나타내고;Y represents -NO 2 , or -S (O) 2- (C 1 -C 2 alkyl);

Z는

Figure PCTKR2016005820-appb-I000016
,
Figure PCTKR2016005820-appb-I000017
또는
Figure PCTKR2016005820-appb-I000018
로부터 선택되고,Z is
Figure PCTKR2016005820-appb-I000016
,
Figure PCTKR2016005820-appb-I000017
or
Figure PCTKR2016005820-appb-I000018
Is selected from,

R5는 수소원자, 할로젠원자, C1～C6알킬기, 또는 C1～C6할로알킬기를 나타내고;R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl group, or a C 1 -C 6 haloalkyl group;

n은 0, 1, 또는 2의 정수를 나타낸다.n represents the integer of 0, 1, or 2.

상기 화학식 1로 표시되는 화합물에 있어, 바람직하게는 In the compound represented by Formula 1, preferably

기 R1은 할로젠원자, 하이드록시기, 또는 -O-C(O)-(C1～C4알킬)를 나타내고;Group R 1 represents a halogen atom, a hydroxy group, or -OC (O)-(C 1 -C 4 alkyl);

상기 R2 및 R3은 각각 독립적으로 수소원자, 메틸기, 에틸기, 노말프로필기, 또는 이소프로필기를 나타내고;R 2 and R 3 each independently represent a hydrogen atom, a methyl group, an ethyl group, a normal propyl group, or an isopropyl group;

상기 R4는 -C1～C4알킬렌-, -C2～C4알케닐렌-, -C2～C4알키닐렌-, -C1～C4할로알킬렌-, -(C1～C4알킬렌)-O-CH2-, -(C1～C4알킬렌)-O-CH2CH2-, -(C1～C4알킬렌)-S-CH2-, 또는 -(C1～C4알킬렌)-S-CH2CH2- 를 나타내고; R 4 is -C 1 -C 4 alkylene-, -C 2 -C 4 alkenylene-, -C 2 -C 4 alkynylene-, -C 1 -C 4 haloalkylene-,-(C 1- C 4 alkylene) -O-CH 2 -,-(C 1 -C 4 alkylene) -O-CH 2 CH 2 -,-(C 1 -C 4 alkylene) -S-CH 2- , or- (C 1 -C 4 alkylene) -S-CH 2 CH 2- ;

상기 X는 할로젠원자, 또는 C1～C4알킬기를 나타내고;X represents a halogen atom or a C 1 to C 4 alkyl group;

상기 Y는 -NO2, 또는 -S(O)2-CH3 를 나타내고;Y is -NO 2 , Or -S (O) 2 -CH 3 ;

상기 Z는

Figure PCTKR2016005820-appb-I000019
,
Figure PCTKR2016005820-appb-I000020
또는
Figure PCTKR2016005820-appb-I000021
로부터 선택되고,Z is
Figure PCTKR2016005820-appb-I000019
,
Figure PCTKR2016005820-appb-I000020
or
Figure PCTKR2016005820-appb-I000021
Is selected from,

상기 R5는 수소원자, 할로젠원자, C1～C4알킬기, 또는 C1～C4할로알킬기를 나타내고;R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, or a C 1 -C 4 haloalkyl group;

상기 n은 0, 1, 또는 2의 정수를 나타내는 화합물의 경우이다. N is the case of the compound which shows the integer of 0, 1, or 2.

상기 화학식 1로 표시되는 화합물에 있어, 보다 바람직하게는In the compound represented by the formula (1), more preferably

상기 R1은 클로로원자, 하이드록시기, 또는 -O-C(O)-(C1～C4알킬)를 나타내고;R 1 represents a chloro atom, a hydroxyl group, or -OC (O)-(C 1 -C 4 alkyl);

상기 R2 및 R3은 각각 독립적으로 수소원자, 또는 메틸기를 나타내고;R 2 and R 3 each independently represent a hydrogen atom or a methyl group;

상기 R4는 -C1～C4알킬렌-, -C2～C4알케닐렌-, -C2～C4알키닐렌-, -C1～C2할로알킬렌-, -(C1～C2알킬렌)-O-CH2-, -(C1～C2알킬렌)-O-CH2CH2-, -(C1～C2알킬렌)-S-CH2-, 또는 -(C1～C2알킬렌)-S-CH2CH2- 를 나타내고;R 4 is -C 1 -C 4 alkylene-, -C 2 -C 4 alkenylene-, -C 2 -C 4 alkynylene-, -C 1 -C 2 haloalkylene-,-(C 1- C 2 alkylene) -O-CH 2 -,-(C 1 -C 2 alkylene) -O-CH 2 CH 2 -,-(C 1 -C 2 alkylene) -S-CH 2- , or- (C 1 -C 2 alkylene) -S-CH 2 CH 2- ;

상기 X는 클로로원자, 또는 메틸기를 나타내고;X represents a chloro atom or a methyl group;

상기 Y는 -NO2, 또는 -S(O)2-CH3를 나타내고;Y is -NO 2 , Or -S (O) 2 -CH 3 ;

상기 Z는

Figure PCTKR2016005820-appb-I000022
,
Figure PCTKR2016005820-appb-I000023
,
Figure PCTKR2016005820-appb-I000024
,
Figure PCTKR2016005820-appb-I000025
,
Figure PCTKR2016005820-appb-I000026
또는
Figure PCTKR2016005820-appb-I000027
를 나타내고;Z is
Figure PCTKR2016005820-appb-I000022
,
Figure PCTKR2016005820-appb-I000023
,
Figure PCTKR2016005820-appb-I000024
,
Figure PCTKR2016005820-appb-I000025
,
Figure PCTKR2016005820-appb-I000026
or
Figure PCTKR2016005820-appb-I000027
Represents;

상기 n은 0, 또는 2의 정수를 나타내는 화합물의 경우이다.N is the case of the compound which shows the integer of 0 or 2.

상기 화학식 1로 표시되는 화합물에 있어, 보다 더 바람직하게는 In the compound represented by the formula (1), even more preferably

상기 R1은 클로로원자, 하이드록시기, 또는 -O-C(O)-(C1～C4알킬)를 나타내고;R 1 represents a chloro atom, a hydroxyl group, or -OC (O)-(C 1 -C 4 alkyl);

상기 R2 및 R3은 각각 독립적으로 수소원자, 또는 메틸기를 나타내고;R 2 and R 3 each independently represent a hydrogen atom or a methyl group;

상기 R4는 -CH2-, -(CH2)2-, -(CH2)3-, -CH2CH(CH3)-, -(CH2)4-, -CH2CH(CH3)CH2-, -(CH2)5-, -CH2C(CH3)2CH2-, cis -CH2CH=CHCH2-, trans -CH2CH=CHCH2-, -CH2C≡CCH2-, -CH2CHF-, -CH2-O-CH2-, -(CH2)2-O-CH2-, -CH2-O-(CH2)2-, -(CH2)2-O-(CH2)2-, -CH2-S-CH2-, -(CH2)2-S-CH2-, -CH2-S-(CH2)2-, 또는 -(CH2)2-S-(CH2)2-를 나타내고;R 4 is -CH 2 - , -(CH 2 ) 2 -,-(CH 2 ) 3- , -CH 2 CH (CH 3 )-,-(CH 2 ) 4- , -CH 2 CH (CH 3 ) CH 2 -,-(CH 2 ) 5- , -CH 2 C (CH 3 ) 2 CH 2- , cis -CH 2 CH = CHCH 2- , trans -CH 2 CH = CHCH 2- , -CH 2 C CCH 2- , -CH 2 CHF-, -CH 2 -O-CH 2 -,-(CH 2 ) 2 -O-CH 2- , -CH 2 -O- (CH 2 ) 2 -,-(CH 2 ) 2 -O- (CH 2 ) 2- , -CH 2 -S-CH 2 -,-(CH 2 ) 2 -S-CH 2- , -CH 2 -S- (CH 2 ) 2- , or -(CH 2 ) 2 -S- (CH 2 ) 2- ;

상기 X는 클로로원자, 또는 메틸기를 나타내고;X represents a chloro atom or a methyl group;

상기 Y는 -NO2, 또는 -S(O)2-CH3를 나타내고;Y is -NO 2 , Or -S (O) 2 -CH 3 ;

상기 Z는

Figure PCTKR2016005820-appb-I000028
,
Figure PCTKR2016005820-appb-I000029
또는
Figure PCTKR2016005820-appb-I000030
를 나타내고;Z is
Figure PCTKR2016005820-appb-I000028
,
Figure PCTKR2016005820-appb-I000029
or
Figure PCTKR2016005820-appb-I000030
Represents;

상기 n은 0 또는 2의 정수를 나타내는 화합물의 경우이다.N is the case of the compound which shows the integer of 0 or 2.

상기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물을 구체적으로 예시하면 하기와 같다 : Specific examples of the benzoylcyclohexanedione compound represented by Chemical Formula 1 are as follows:

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 2); 2- (3- (2- (2H - 1, 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 2);

2-(3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 4);2- (3- (4- (2H - 1, 1,2,3-triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 4);

2-(3-(2-(1H-1,2,3-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 7);2- (3- (2- (1H-1, 1,2,3-triazol - 1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 7);

2-(3-(4-(1H-1,2,3-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 9);2- (3- (4- (1H-1, 1,2,3-triazol - 1-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 9);

2-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 12);2- (3- (2- (1H-1, 1,2,4 - triazol-1 - yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 12);

3-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 27); 3- (3- (2- (1H-1, 1,2,4 - triazol-1 - yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4-hydroxybicyclo [ 3.2.1] oc-3-ten-2-one (Compound No. 27);

2-(3-(2-(3-브로모-1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 32);2- (3- (2- (3-bromo-1 H -1,2,4-triazol-1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3- Hydroxycyclohex-2-sen-1-one (Compound No. 32);

2-(3-(2-((1H-1,2,3-트리아졸-1-일)메톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 35);2- (3- (2-((1H-1, 1,2,3-triazol - 1-yl) methoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydro Oxycyclohex-2-sen-1-one (Compound No. 35);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 41);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 41);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 44);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4-nitrobenzoyl) -3-hydroxycyclohex-2-ene -1-one (Compound No. 44);

2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 48);2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-tin-1-yl) oxy) -2-chloro-4- (methylsulfonyl) Benzoyl) -3-hydroxycyclohex-2-sen-1-one (Compound No. 48);

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 61);3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4 -Hydroxybicyclo [3.2.1] octa-3-ten-2-one (Compound No. 61);

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 아세테이트 (화합물번호 62);3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4 Oxobicyclo [3.2.1] oc-2-ten-2-yl acetate (Compound No. 62);

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 사이클로프로판카르복실레이트 (화합물번호 63);3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4 Oxobicyclo [3.2.1] oc-2-ten-2-yl cyclopropanecarboxylate (Compound No. 63);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 67);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxocyclo Hex-1-sen-1-yl acetate (Compound No. 67);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 사이클로프로판카르복실레이트 (화합물번호 68);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxocyclo Hex-1-sen-1-yl cyclopropanecarboxylate (Compound No. 68);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아이소부티레이트 (화합물번호 69);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxocyclo Hex-1-sen-1-yl isobutyrate (Compound No. 69);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 피발레이트 (화합물번호 70);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxocyclo Hex-1-sen-1-yl pivalate (Compound No. 70);

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 71);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-oxocyclohex-1 -Sen-1-yl acetate (Compound No. 71);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온 (화합물번호 91);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3 -Chlorocyclohex-2-sen-1-one (Compound No. 91);

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-클로로바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 94);3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4 -Chlorobicyclo [3.2.1] octa-3-ten-2-one (Compound No. 94);

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-4-클로로바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 96);3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -4-chlorobi Cyclo [3.2.1] octa-3-ten-2-one (Compound No. 96);

2-(3-(2-(1H-1,2,3-트리아졸-1-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 101);2- (3- (2- ( 1H -1,2,3-triazol-1-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxocyclo Hex-1-sen-1-yl acetate (Compound No. 101);

2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아이소부티레이트 (화합물번호 104);2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-tin-1-yl) oxy) -2-chloro-4- (methylsulfonyl) Benzoyl) -3-oxocyclohex-1-sen-1-yl isobutyrate (Compound No. 104);

2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-플루오로사이클로헥-2-센-1-온 (화합물번호 118); 2- (3- (3- ( 2H -1,2,3-triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-fluorocyclohex- 2-sen-1-one (Compound No. 118);

2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-브로모사이클로헥-2-센-1-온 (화합물번호 119);2- (3- (3- ( 2H -1,2,3-triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-bromocyclohex- 2-sen-1-one (Compound No. 119);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 120);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4-nitrobenzoyl) -3-hydroxy Cyclohex-2-sen-1-one (Compound No. 120);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 121);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4-nitrobenzoyl) -3-oxocyclo Hex-1-sen-1-yl acetate (Compound No. 121);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 123);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 Hydroxycyclohex-2-sen-1-one (Compound No. 123);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 124);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 Oxocyclohex-1-sen-1-yl acetate (Compound No. 124);

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온(화합물번호 125);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 -Chlorocyclohex-2-sen-1-one (Compound No. 125);

3-클로로-2-(3-(2-플루오로-2-(1H-1,2,3-트리아졸-1-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)사이클로헥-2-센-1-온 (화합물번호 133);3-chloro-2- (3- (2-fluoro-2- ( 1H -1,2,3-triazol-1-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoyl) Cyclohex-2-sen-1-one (Compound No. 133);

3-클로로-2-(3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)사이클로헥-2-센-1-온 (화합물번호 135);3-chloro-2- (3- (2-fluoro-2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoyl) Cyclohex-2-sen-1-one (Compound No. 135);

2-(3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 136); 및2- (3- (2-fluoro-2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoyl) -3-oxo Cyclohex-1-sen-1-yl acetate (Compound No. 136); and

농약학적으로 허용 가능한 이들의 염으로 이루어진 군으로부터 선택된 화합물.A compound selected from the group consisting of agrochemically acceptable salts thereof.

또한, 본 발명에 따른 상기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물은 농약학적으로 허용 가능한 염의 형태로 사용될 수 있다. 농약학적으로 허용 가능한 염이라 함은, 예를 들어, 금속염, 유기 염기와의 염, 무기산과의 염, 유기산과의 염, 염기성, 또는 산성 아미노산과의 염 등이 포함될 수 있다. 적합한 금속염은, 예를 들어, 나트륨염, 칼륨염 등과 같은 알칼리 금속염; 칼슘염, 마그네슘염, 바륨염 등과 같은 알칼리 토금속염; 알루미늄염 등이 포함될 수 있다. 유기 염기와의 염은, 예를 들어, 트리메틸아민, 트리에틸아민, 다이이소프로필에틸아민, 피리딘, 피콜린, 2,6-루티딘, 에탄올아민, 다이에탄올아민, 트리에탄올아민, 사이클로헥실아민, 다이사이클로헥실아민, N,N -다이벤질에틸렌다이아민 등으로부터 선택된 염기와의 염이 포함될 수 있다. 무기산과의 염은, 예를 들어, 염산, 브롬화수소산, 질산, 황산, 인산 등으로부터 선택된 무기산과의 염이 포함될 수 있다. 유기산과의 염은, 예를 들어, 포름산, 아세트산, 트리플루오로아세트산, 프탈산, 푸마르산, 옥살산, 타르타르산, 말레인산, 시트르산, 숙신산, 메탄술폰산, 벤젠술폰산, p-톨루엔술폰산 등으로부터 선택된 유기산과의 염이 포함될 수 있다. 염기성 아미노산과의 염은, 예를 들어, 알기닌, 라이신, 오르니틴 등으로부터 선택된 염기성 아미노산과의 염이 포함될 수 있다. 산성 아미노산과의 염은, 예를 들어, 아스파르트산, 글루탐산 등으로부터 선택된 산성 아미노산과의 염이 포함될 수 있다.In addition, the benzoylcyclohexanedione compound represented by Chemical Formula 1 according to the present invention may be used in the form of an agriculturally acceptable salt. Agrochemically acceptable salts may include, for example, metal salts, salts with organic bases, salts with inorganic acids, salts with organic acids, salts with basic or acidic amino acids, and the like. Suitable metal salts include, for example, alkali metal salts such as sodium salts, potassium salts and the like; Alkaline earth metal salts such as calcium salts, magnesium salts, barium salts, and the like; Aluminum salts and the like. Salts with organic bases are, for example, trimethylamine, triethylamine, diisopropylethylamine, pyridine, picoline, 2,6-lutidine, ethanolamine, diethanolamine, triethanolamine, cyclohexylamine, It may include a salt of a base, and selected from ethylene-diamine-dibenzylamino, etc.-dicyclohexyl amine, N, N. Salts with inorganic acids may include, for example, salts with inorganic acids selected from hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, and the like. Salts with organic acids are, for example, salts with organic acids selected from formic acid, acetic acid, trifluoroacetic acid, phthalic acid, fumaric acid, oxalic acid, tartaric acid, maleic acid, citric acid, succinic acid, methanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid, and the like. This may be included. Salts with basic amino acids may include, for example, salts with basic amino acids selected from arginine, lysine, ornithine and the like. Salts with acidic amino acids may include, for example, salts with acidic amino acids selected from aspartic acid, glutamic acid and the like.

또한, 본 발명에 따른 상기 화학식 1로 표시되는 화합물 중 일부는 수성 및 유기 용매와 같은 용매로부터 결정화되거나 또는 재결정화될 수 있다. 이러한 경우, 상기 화학식 1로 표시되는 화합물은 용매화물을 형성할 수 있다. 동결건조와 같은 방법으로 제조 가능한 다양한 양의 물 함유 화합물 이외에 수화물을 비롯한 화학 양론적 용매화물도 본 발명의 범위에 속한다.In addition, some of the compounds represented by Formula 1 according to the present invention may be crystallized or recrystallized from solvents such as aqueous and organic solvents. In this case, the compound represented by Formula 1 may form a solvate. In addition to various amounts of water-containing compounds that can be prepared by methods such as lyophilization, stoichiometric solvates, including hydrates, are also within the scope of the present invention.

또한, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 하나 또는 그 이상의 비대칭 중심을 가질 수 있고, 이러한 화합물의 경우 거울상 이성체 또는 부분입체이성체가 존재할 수 있다. 따라서 본 발명은 각 이성체 또는 이들 이성체 혼합물을 포함한다.In addition, the compound represented by Chemical Formula 1 according to the present invention may have one or more asymmetric centers, and in the case of such compounds, enantiomers or diastereomers may be present. The present invention therefore encompasses each isomer or a mixture of these isomers.

또한, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 토토머 형태로도 존재가 가능한 바, 본 발명은 각 토토머 또는 이들의 혼합물 역시 포함한다. In addition, the compound represented by Chemical Formula 1 according to the present invention may exist in tautomer form, and the present invention also includes each tautomer or a mixture thereof.

또한, 본 발명에 따른 화합물을 나타내기 위해 사용된 치환기에 대한 구체적으로 설명하면 하기와 같다. In addition, the substituents used to represent the compounds according to the present invention will be described in detail below.

본 발명에서의 '할로' 또는 '할로젠'이란 용어는 서로 교환 가능하게 사용될 수 있다. 구체적으로는 염소, 불소, 요오드 및 브롬으로부터 유도된 라디칼 등이 포함될 수 있다.The terms "halo" or "halogen" in the present invention may be used interchangeably. Specifically, radicals derived from chlorine, fluorine, iodine and bromine may be included.

본 발명에서의 '알킬'은 탄소원자가 1개 내지 6개(바람직하기로는 1개 내지 4개) 포함된 직쇄, 분지쇄, 또는 고리쇄를 이루는 포화탄화수소 라디칼을 의미한다. 구체적으로는 메틸, 에틸, 노말프로필, 이소프로필, 사이클로프로필, 노말부틸, sec-부틸, tert-부틸, 노말펜틸, 이소펜틸, 사이클로펜틸, 노말헥실, 2-(메틸)펜틸, 사이클로헥실 등이 포함될 수 있다.'Alkyl' in the present invention means a straight chain, branched, or cyclic saturated hydrocarbon radical containing 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms). Specifically methyl, ethyl, normal propyl, isopropyl, cyclopropyl, normal butyl, sec -butyl, tert -butyl, normalpentyl, isopentyl, cyclopentyl, normalhexyl, 2- (methyl) pentyl, cyclohexyl, and the like.

본 발명에서의 '할로알킬'은 할로젠원자가 1개 내지 10개 치환된 알킬 라디칼을 의미한다. 구체적으로는 트리플로로메틸, 다이클로로에틸 등이 포함될 수 있다.'Haloalkyl' in the present invention means an alkyl radical having 1 to 10 halogen atoms substituted. Specifically, trichloromethyl, dichloroethyl, and the like may be included.

본 발명에서의 '알콕시'는 O-알킬으로서, 예를 들면 메톡시, 에톡시, 노말프로폭시, 이소프로폭시, 노말부톡시, sec-부톡시, t-부톡시 등이 포함될 수 있다.In the present invention, 'alkoxy' may include, for example, methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, sec -butoxy, t -butoxy and the like.

한편, 본 발명은 상기 화학식 1로 표시되는 벤조일사이클로헥사다이온 화합물의 제조방법을 포함한다.On the other hand, the present invention includes a method for producing a benzoylcyclohexadione compound represented by the formula (1).

본 발명에 따른 제조방법에 의하면, 하기 반응식 1에 나타난 바와 같이, According to the preparation method according to the present invention, as shown in Scheme 1 below,

하기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시벤조에이트를 하기 화학식 3으로 표시되는 아세톤 시아노하이드린 시약과 반응시켜, R1이 하이드록시기인 하기 화학식 1a로 표시되는 벤조일사이클로헥사다이온 화합물을 제조하는 과정; 을 수행하여 벤조일사이클로헥사다이온 화합물을 제조할 수 있다.Reaction of 3-oxo-1-cycloalkenyl-3-alkoxybenzoate represented by the following formula (2) with an acetone cyanohydrin reagent represented by the following formula (3), wherein benzoyl represented by the following formula (1a) wherein R 1 is a hydroxy group Preparing a cyclohexadione compound; It is possible to prepare a benzoylcyclohexadione compound.

[반응식 1]Scheme 1

Figure PCTKR2016005820-appb-I000031
Figure PCTKR2016005820-appb-I000031

(상기 반응식 1에서 R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같다)(In Reaction Scheme 1, R 2 , R 3 , R 4 , X, Y, Z and n are as defined in Formula 1, respectively.)

상기 반응식 1에 따른 제조방법은 시안화 화합물과 염기 조건 하에서 수행될 수 있다. 상기 시안화 화합물로는 구체적으로 시안화 나트륨, 시안화 칼륨, 아세톤 시아나이드, 수소화 시아나이드 등으로부터 선택된 1종 이상이 사용될 수 있다. 그리고 염기는 트리에틸아민, 다이이소프로필에틸아민의 지방족 아민류, 다이메틸아닐린 등의 방향족 아민류, 피리딘 등이 포함되는 유기 염기일 수 있고, 또는 탄산리튬, 탄산나트륨, 탄산칼륨 등의 알칼리금속 카보네이트와 같은 무기 염기를 사용할 수 있다. 상기 염기는 1종 또는 2종 이상을 혼합 사용할 수도 있다. 시안화 화합물과 염기의 사용량에 있어서는, 상기 화학식 2로 표시되는 화합물 1 몰을 기준으로 각각 1 ～ 4 몰비 범위로 사용될 수 있고, 바람직하기로는 1 ～ 2 몰비 범위로 사용될 수 있다. The preparation method according to Scheme 1 may be performed under a cyanide compound and basic conditions. Specifically, as the cyanide compound, at least one selected from sodium cyanide, potassium cyanide, acetone cyanide, hydrogenated cyanide, and the like may be used. The base may be an organic base including triethylamine, aliphatic amines of diisopropylethylamine, aromatic amines such as dimethylaniline, pyridine, or the like, or an alkali metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, or the like. Inorganic bases can be used. The said base can also be used 1 type or in mixture of 2 or more types. The amount of the cyanide compound and the base may be used in the range of 1 to 4 molar ratios, and preferably in the range of 1 to 2 molar ratios, based on 1 mole of the compound represented by Chemical Formula 2.

반응온도는 -10℃ 내지 80℃ 범위에서 가능하며, 바람직하게는 5℃ 내지 40℃의 온도를 유지한다. 반응용매로는 당 분야에서 사용되어 온 통상의 유기용매는 모두 사용될 수 있으며 이의 선택에 특별한 제한을 두지 않는다. 반응용매를 구체적으로 예시하면 톨루엔, 다이클로로메탄, 클로로포름, 1,2-다이클로로에탄, 다이에틸 에테르, 다이메톡시에탄, 테트라하이드로퓨란, 아세톤, 아세토나이트릴, 에틸 아세테이트, 다이메틸포름아마이드 등이 포함될 수 있다. 반응이 종료된 후에는 유기용매로 희석하여 산으로 세척하고 얻어진 유기층을 건조, 농축하고 칼럼크로마토그래피로 정제할 수 있다.The reaction temperature is possible in the range of -10 ° C to 80 ° C, preferably maintaining a temperature of 5 ° C to 40 ° C. As the reaction solvent, any conventional organic solvent which has been used in the art may be used, and there is no particular limitation on the selection thereof. Specific examples of the reaction solvent include toluene, dichloromethane, chloroform, 1,2-dichloroethane, diethyl ether, dimethoxyethane, tetrahydrofuran, acetone, acetonitrile, ethyl acetate, dimethylformamide, and the like. This may be included. After the reaction is completed, the organic layer may be diluted with an organic solvent, washed with acid, and the obtained organic layer may be dried, concentrated and purified by column chromatography.

또한 본 발명에 따른 제조방법에 의하면, 하기 반응식 2에 나타난 바와 같이, In addition, according to the production method according to the invention, as shown in Scheme 2 below,

a)하기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시벤조에이트를 하기 화학식 3으로 표시되는 아세톤 시아노하이드린 시약과 반응시켜, R1이 하이드록시기인 하기 화학식 1a로 표시되는 화합물을 제조하는 과정; 및 a) Reacting 3-oxo-1-cycloalkenyl-3-alkoxybenzoate represented by the following formula (2) with an acetone cyanohydrin reagent represented by the following formula (3), wherein R 1 is a hydroxy group represented by the following formula (1a) Preparing a compound to be obtained; And

b-1)하기 화학식 1a로 표시되는 화합물을 할로젠화 시약과 반응시켜, R1이 할로젠원자인 하기 화학식 1b로 표시되는 벤조일사이클로헥사다이온 화합물을 제조하는 과정; 을 수행하여 벤조일사이클로헥사다이온 화합물을 제조할 수 있다.b-1) reacting a compound represented by Formula 1a with a halogenation reagent to prepare a benzoylcyclohexadione compound represented by Formula 1b wherein R 1 is a halogen atom; It is possible to prepare a benzoylcyclohexadione compound.

[반응식 2]Scheme 2

Figure PCTKR2016005820-appb-I000032
Figure PCTKR2016005820-appb-I000032

(상기 반응식 1에서 R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같고, Hal.은 할로젠원자를 나타낸다)(In Reaction Scheme 1, R 2 , R 3 , R 4 , X, Y, Z and n are as defined in Formula 1, respectively, and Hal. Represents a halogen atom.)

상기 반응식 2에 따른 제조방법은 a)상기 반응식 1에 따른 제조방법으로 상기 화학식 1a로 표시되는 화합물을 얻는 과정 및 b-1)상기 화학식 1a로 표시되는 화합물을 할로젠화 하는 과정으로 이루어진다.The preparation method according to Scheme 2 includes a) obtaining a compound represented by Chemical Formula 1a as a preparation method according to Scheme 1 and b-1) halogenating the compound represented by Chemical Formula 1a.

상기 할로젠화 과정은 통상의 유기용매 조건 하에서 할로젠화 시약을 사용하여 수행할 수 있다. 상기 할로젠화 시약으로는 구체적으로 옥살릴클로라이드, 옥살릴브로마이드, 다이에틸아미노설퍼 트라이플루오라이드 등으로부터 선택된 1종 이상이 사용될 수 있다. 할로젠화 시약의 사용량에 있어서는 상기 화학식 1a로 표시되는 화합물 1 몰을 기준으로 1 ～ 3 몰비 범위로 사용될 수 있고, 바람직하기로는 1 ～ 1.5 몰비 범위로 사용될 수 있다.  The halogenation process may be performed using a halogenation reagent under conventional organic solvent conditions. Specifically, the halogenation reagent may be used at least one selected from oxalyl chloride, oxalyl bromide, diethylaminosulfur trifluoride, and the like. The amount of the halogenating reagent may be used in the range of 1 to 3 molar ratios, based on 1 mole of the compound represented by Formula 1a, and preferably in the range of 1 to 1.5 molar ratios.

상기 할로젠화 반응온도는 0℃ 내지 40℃ 범위에서 가능하며, 상온을 유지하는 것이 보다 바람직하다. 반응용매로는 당 분야에서 사용되어 온 통상의 유기용매는 모두 사용될 수 있으며 이의 선택에 특별한 제한을 두지 않는다. 반응용매를 구체적으로 예시하면 다이클로로메탄, 클로로포름, 1,2-다이클로로에탄 등이 사포함될 수 있다. 반응이 종료된 후에는 유기용매로 희석하여 물로 세척하고 얻어진 유기층을 건조, 농축하고 칼럼크로마토그래피로 정제할 수 있다.The halogenation reaction temperature is possible in the range of 0 ℃ to 40 ℃, it is more preferable to maintain the room temperature. As the reaction solvent, any conventional organic solvent which has been used in the art may be used, and there is no particular limitation on the selection thereof. Specific examples of the reaction solvent may include dichloromethane, chloroform, 1,2-dichloroethane and the like. After the reaction is completed, the organic layer may be diluted with an organic solvent, washed with water, and the obtained organic layer may be dried, concentrated and purified by column chromatography.

또한 본 발명에 따른 제조방법에 의하면, 하기 반응식 3에 나타난 바와 같이, In addition, according to the production method according to the invention, as shown in Scheme 3 below,

a)하기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시벤조에이트를 하기 화학식 3으로 표시되는 아세톤 시아노하이드린 시약과 반응시켜, R1이 하이드록시기인 하기 화학식 1a로 표시되는 화합물을 제조하는 과정; 및 a) Reacting 3-oxo-1-cycloalkenyl-3-alkoxybenzoate represented by the following formula (2) with an acetone cyanohydrin reagent represented by the following formula (3), wherein R 1 is a hydroxy group represented by the following formula (1a) Preparing a compound to be obtained; And

b-2)하기 화학식 1a로 표시되는 화합물을 하기 화학식 4로 표시되는 알킬카르보닐 클로라이드 시약과 반응시켜, R1이 알킬카르보닐옥시기인 하기 화학식 1c로 표시되는 벤조일사이클로헥사다이온 화합물을 제조하는 과정; 을 수행하여 벤조일사이클로헥사다이온 화합물을 제조할 수 있다.b-2) reacting a compound represented by the following Chemical Formula 1a with an alkylcarbonyl chloride reagent represented by the following Chemical Formula 4 to prepare a benzoylcyclohexadione compound represented by the following Chemical Formula 1c wherein R 1 is an alkylcarbonyloxy group. process; It is possible to prepare a benzoylcyclohexadione compound.

[반응식 3]Scheme 3

Figure PCTKR2016005820-appb-I000033
Figure PCTKR2016005820-appb-I000033

(상기 반응식 3에서 R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같고, R6은 C1～C4알킬기를 나타낸다.)(In Reaction Scheme 3, R 2 , R 3 , R 4 , X, Y, Z and n are as defined in Formula 1, respectively, and R 6 represents a C 1 to C 4 alkyl group.)

상기 반응식 3에 따른 제조방법은 a)상기 반응식 1에 따른 제조방법으로 상기 화학식 1a로 표시되는 화합물을 얻는 과정 및 b-2)상기 화학식 1a로 표시되는 화합물을 알킬카르보닐화 하는 과정으로 이루어진다.The preparation method according to Scheme 3 includes a) obtaining a compound represented by Chemical Formula 1a as a preparation method according to Scheme 1, and b-2) alkylcarbonylating the compound represented by Chemical Formula 1a.

상기 알킬카르보닐화 과정은 알킬카르보닐 클로라이드와 염기 조건 하에서 수행될 수 있다. 상기 알킬카르보닐 클로라이드는 구체적으로 아세틸 클로라이드, 프로피오닐 클로라이드, 부티릴 클로라이드 등이 포함될 수 있다. 상기 염기는 트리에틸아민, 다이이소프로필에틸아민의 지방족 아민류, 다이메틸아닐린 등의 방향족 아민류, 피리딘 등이 포함되는 유기 염기일 수 있고, 또는 탄산리튬, 탄산나트륨, 탄산칼륨 등의 알칼리금속 카보네이트와 같은 무기 염기를 사용할 수 있다. 상기 염기는 1종 또는 2종 이상을 혼합 사용할 수도 있다. 알킬카르보닐 클로라이드와 염기의 사용량에 있어서는, 상기 화학식 1a로 표시되는 화합물 1 몰을 기준으로 각각 1 ～ 4 몰비 범위로 사용될 수 있고, 바람직하기로는 1 ～ 2 몰비 범위로 사용될 수 있다.  The alkylcarbonylation process can be carried out under basic conditions with alkylcarbonyl chloride. The alkylcarbonyl chloride may specifically include acetyl chloride, propionyl chloride, butyryl chloride, and the like. The base may be an organic base including triethylamine, aliphatic amines of diisopropylethylamine, aromatic amines such as dimethylaniline, pyridine, or the like, or an alkali metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, or the like. Inorganic bases can be used. The said base can also be used 1 type or in mixture of 2 or more types. The amount of the alkylcarbonyl chloride and the base may be used in the range of 1 to 4 molar ratios, based on 1 mole of the compound represented by Chemical Formula 1a, and preferably in the range of 1 to 2 molar ratios.

상기 알킬카르보닐화 반응온도는 0℃ 내지 40℃ 범위에서 가능하며, 상온을 유지하는 것이 보다 바람직하다. 반응용매로는 당 분야에서 사용되어 온 통상의 유기용매는 모두 사용될 수 있으며 이의 선택에 특별한 제한을 두지 않는다. 반응용매를 구체적으로 예시하면 다이클로로메탄, 클로로포름, 1,2-다이클로로에탄, 다이에틸 에테르, 테트라하이드로퓨란, 에틸 아세테이트 등이 포함될 수 있다. 반응이 종료된 후에는 유기용매로 희석하여 물로 세척하고 얻어진 유기층을 건조, 농축하고 칼럼크로마토그래피로 정제할 수 있다.The alkylcarbonylation reaction temperature is possible in the range of 0 ° C to 40 ° C, more preferably at room temperature. As the reaction solvent, any conventional organic solvent which has been used in the art may be used, and there is no particular limitation on the selection thereof. Specific examples of the reaction solvent may include dichloromethane, chloroform, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, ethyl acetate and the like. After the reaction is completed, the organic layer may be diluted with an organic solvent, washed with water, and the obtained organic layer may be dried, concentrated and purified by column chromatography.

한편, 상기 반응식 1 내지 3에 따른 제조방법에서 출발물질로 사용된 상기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시벤조에이트 화합물은 하기 반응식 4에 나타난 바와 같이 4 단계 제조과정을 걸쳐 합성될 수 있다.Meanwhile, the 3-oxo-1-cycloalkenyl-3-alkoxybenzoate compound represented by Formula 2 used as a starting material in the preparation method according to Schemes 1 to 3 was prepared in step 4 as shown in Scheme 4 below. Can be synthesized throughout the process.

1단계) 하기 화학식 5로 표시되는 치환된 메틸 하이드록시벤조에이트를 Br-R4-Br로 표시되는 다이브로모알칸 시약과 반응시켜, 하기 화학식 6으로 표시되는 치환된 메틸 브로모알콕시 벤조에이트를 제조하는 과정;Step 1) reacting the substituted methyl hydroxybenzoate represented by Formula 5 with a dibromoalkane reagent represented by Br-R 4 -Br to prepare a substituted methyl bromoalkoxy benzoate represented by Formula 6 Process of doing;

2단계) 하기 화학식 6으로 표시되는 화합물을 Z-H로 표시되는 아졸시약과 반응시켜, 하기 화학식 7로 표시되는 화합물을 제조하는 과정;Step 2) reacting the compound represented by Chemical Formula 6 with an azole reagent represented by Z-H to prepare a compound represented by Chemical Formula 7;

3단계) 하기 화학식 7로 표시되는 화합물을 가수분해 반응시켜, 하기 화학식 8로 표시되는 벤조산 화합물을 제조하는 과정; 및Step 3) hydrolyzing the compound represented by Chemical Formula 7 to prepare a benzoic acid compound represented by Chemical Formula 8; And

4 단계) 하기 화학식 8로 표시되는 화합물을 하기 화학식 9로 표시되는 사이클로알칸 다이온 시약과 반응시켜, 하기 화학식 2로 표시되는 화합물을 제조하는 과정.4) a process of preparing a compound represented by the following Chemical Formula 2 by reacting the compound represented by the following Chemical Formula 8 with a cycloalkane dione reagent represented by the following Chemical Formula 9.

[반응식 4]Scheme 4

Figure PCTKR2016005820-appb-I000034
Figure PCTKR2016005820-appb-I000034

(상기 반응식 4에서 R2, R3, R4, X, Y, Z 및 n은 각각 상기 화학식 1에서 정의한 바와 같다)(In Reaction Scheme 4, R 2 , R 3 , R 4 , X, Y, Z and n are as defined in Formula 1, respectively.)

상기 반응식 4에 따른 제조방법을 보다 구체적으로 설명하면 하기와 같다.Hereinafter, the preparation method according to Scheme 4 will be described in more detail.

1) 단계 과정은 Br-R4-Br로 표시되는 다이브로모알칸 시약을 사용하여 진행되며, 염기 존재 하에서 통상의 유기용매를 사용하여 진행될 수 있다. 반응온도는 상온 내지 사용된 유기용매의 환류온도 범위이며, 구체적으로는 20℃ 내지 120℃이고, 바람직하기로는 50℃ 내지 80℃ 온도 범위를 유지하는 것이다.Step 1) proceeds using a dibromoalkane reagent represented by Br-R 4 -Br, and may be performed using a conventional organic solvent in the presence of a base. The reaction temperature ranges from room temperature to the reflux temperature of the organic solvent used, specifically 20 ° C. to 120 ° C., preferably 50 ° C. to 80 ° C.

2) 단계 과정은 Z-H로 표시되는 아졸시약을 사용하여 진행되며, 염기 및 테트라부틸암모늄 브로마이드(TBAB) 촉매 존재 하에서 통상의 유기용매를 사용하여 진행될 수 있다. 반응온도는 상온 내지 사용된 유기용매의 환류온도 범위이며, 구체적으로는 20℃ 내지 120℃이고, 바람직하기로는 70℃ 내지 90℃ 온도 범위를 유지하는 것이다.2) The step process is carried out using an azole reagent represented by Z-H, and may be performed using a conventional organic solvent in the presence of a base and tetrabutylammonium bromide (TBAB) catalyst. The reaction temperature is in the range of reflux temperature of the organic solvent used, specifically, 20 ℃ to 120 ℃, preferably to maintain the temperature range of 70 ℃ to 90 ℃.

3) 단계 과정은 에스터 그룹을 가수분해하여 카르복시산 그룹으로 전환한다. 상기 가수분해는 산 또는 염기를 사용하여 진행될 수 있다. 본 발명의 실시예에서는 주로 수산화나트륨을 포함하는 알칼리금속 수산화물을 사용한 알칼리 가수분해 조건에서 진행하였다.The step 3) converts the ester group to a carboxylic acid group by hydrolysis. The hydrolysis can be carried out using an acid or a base. In the embodiment of the present invention, it proceeded under alkaline hydrolysis conditions using an alkali metal hydroxide mainly containing sodium hydroxide.

4) 단계 과정은 사이클로알칸 다이온 시약을 사용하여, 염기 및 통상의 유기용매를 사용하는 조건에서 진행될 수 있다. 반응온도는 상온 내지 사용된 유기용매의 환류온도 범위이며, 구체적으로는 20℃ 내지 80℃이고, 바람직하기로는 상온 주변의 온도를 유지하는 것이다.4) The step process can be performed under conditions using a base and a conventional organic solvent using a cycloalkane dione reagent. The reaction temperature ranges from room temperature to the reflux temperature of the organic solvent used, specifically 20 ° C. to 80 ° C., and preferably maintains a temperature around room temperature.

본 발명의 제조방법에서 사용되는 통상의 염기는 유기염기 또는 무기염기가 포함될 수 있다. 상기 유기염기로는 트리(C1～C6알킬)아민, 피리딘, 및 다이메틸 아닐린 등으로 이루어진 군으로부터 선택된 1종 이상이 사용될 수 있다. 상기 유기염기는 구체적으로 트리메틸아민, 트리에틸아민, 다이에틸이소프로필아민, 다이이소프로필에틸아민 등이 포함될 수 있다. 상기 무기염기로는 알칼리금속 또는 알칼리토금속의 수산화물, 수소화물, 카보네이트, 및 C1～C6알콕사이드 등으로 이루어진 군으로부터 선택된 1종 이상이 사용될 수 있다. 상기 무기염기는 구체적으로 수산화리튬, 수산화나트륨, 수산화칼슘, 수소화나트륨, 수소화칼륨, 나트륨 메톡사이드, 칼륨 메톡사이드 등이 포함될 수 있다. 상기한 염기는 반응물질 1 몰을 기준으로 1 내지 3 몰비, 바람직하기로는 1 내지 2 몰비 범위로 사용할 수 있다.Conventional bases used in the preparation method of the present invention may include an organic base or an inorganic base. As the organic base, one or more selected from the group consisting of tri (C 1 -C 6 alkyl) amine, pyridine, dimethyl aniline, and the like can be used. The organic base may specifically include trimethylamine, triethylamine, diethylisopropylamine, diisopropylethylamine, and the like. As the inorganic base, at least one selected from the group consisting of hydroxides, hydrides, carbonates, and C 1 to C 6 alkoxides of alkali metals or alkaline earth metals may be used. The inorganic base may specifically include lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium hydride, potassium hydride, sodium methoxide, potassium methoxide and the like. The base may be used in the range of 1 to 3 molar ratios, preferably 1 to 2 molar ratios, based on 1 mole of the reactant.

또한, 본 발명의 제조방법에서 사용되는 통상의 유기용매로는 반응에 참여하지 않는 용매라면 모두 사용이 가능하다. 이러한 용매로는 예를 들면 다이에틸 에테르, 테트라히드로푸란(THF), 다이옥산, 다이메톡시에탄과 같은 에테르류; 다이클로로메탄, 1,2-다이클로로에탄, 클로로포름, 사염화탄소, 클로로벤젠과 같은 할로겐화 탄화수소류; 벤젠, 톨루엔, 크실렌과 같은 방향족 탄화수소류; 노말헥산, 사이클로헥산, 헵탄 등의 지방족 탄화수소류; 아세토나이트릴, 프로피오나이트릴과 같은 나이트류; 아세톤과 같은 케톤류; 에틸 아세테이트와 같은 아세테이트류; 다이메틸포름아마이드(DMF)와 같은 아마이드류; 등으로 이루어진 군으로부터 선택된 1종 또는 2종 이성을 적절하게 선택하여 사용할 수 있다.In addition, as a general organic solvent used in the production method of the present invention, any solvent that does not participate in the reaction can be used. Such solvents include, for example, ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, dimethoxyethane; Halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; Aromatic hydrocarbons such as benzene, toluene and xylene; Aliphatic hydrocarbons such as normal hexane, cyclohexane and heptane; Nitrites such as acetonitrile and propionitrile; Ketones such as acetone; Acetates such as ethyl acetate; Amides such as dimethylformamide (DMF); One or two isomers selected from the group consisting of and the like can be appropriately selected and used.

이상에서 설명한 바와 같은 본 발명은 하기의 실시예에 의거하여 더욱 상세히 설명하겠으나, 본 발명이 이에 한정된 것은 아니다.The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited thereto.

[실시예] EXAMPLE

본 실시예를 통해 합성된 상기 화학식 1로 표시되는 화합물을 구체적으로 예시하면 하기 표 1과 같다. 통상의 당업자라면 하기 표 1에 예시된 화합물은 본 실시예로 구체화되어 있는 합성법을 이용하거나 응용하여 쉽게 합성할 수 있다.Specific examples of the compound represented by Formula 1 synthesized through the present Example are as shown in Table 1 below. Those skilled in the art can be easily synthesized using the compounds described in Table 1 below or using the synthesis method specified in the Examples.

Figure PCTKR2016005820-appb-I000035
Figure PCTKR2016005820-appb-I000035
Com. NoCom. No R1 R 1 R2 R 2 R3 R 3 R4 R 4 nn XX YY ZZ 1One OHOH HH HH CH2 CH 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 22 OHOH HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 33 OHOH HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-1Z-1 44 OHOH HH HH (CH2)4 (CH 2 ) 4 00 ClCl SO2MeSO 2 Me Z-1Z-1 55 OHOH HH HH (CH2)5 (CH 2 ) 5 00 ClCl SO2MeSO 2 Me Z-1Z-1 66 OHOH HH HH CH2 CH 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 77 OHOH HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 88 OHOH HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-2Z-2 99 OHOH HH HH (CH2)4 (CH 2 ) 4 00 ClCl SO2MeSO 2 Me Z-2Z-2 1010 OHOH HH HH (CH2)5 (CH 2 ) 5 00 ClCl SO2MeSO 2 Me Z-2Z-2 1111 OHOH HH HH CH2 CH 2 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 1212 OHOH HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 1313 OHOH HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 1414 OHOH HH HH (CH2)4 (CH 2 ) 4 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 1515 OHOH HH HH (CH2)5 (CH 2 ) 5 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 1616 OHOH HH HH CH2 CH 2 00 ClCl SO2MeSO 2 Me Z-3-2Z-3-2 1717 OHOH HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-3-2Z-3-2 1818 OHOH MeMe HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 1919 OHOH MeMe HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 2020 OHOH MeMe HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 2121 OHOH HH HH CH2 CH 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 2222 OHOH HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 2323 OHOH HH HH (CH2)3 (CH 2 ) 3 22 ClCl SO2MeSO 2 Me Z-1Z-1 2424 OHOH HH HH CH2 CH 2 22 ClCl SO2MeSO 2 Me Z-2Z-2 2525 OHOH HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-2Z-2 2626 OHOH HH HH (CH2)3 (CH 2 ) 3 22 ClCl SO2MeSO 2 Me Z-2Z-2 2727 OHOH HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 2828 OHOH HH HH (CH2)3 (CH 2 ) 3 22 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 2929 OHOH HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-3-2Z-3-2 3030 OHOH HH HH CH2 CH 2 22 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 3131 OHOH HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-4Z-4 3232 OHOH HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-3-3Z-3-3 3333 OHOH HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-3-4Z-3-4 3434 OHOH HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-3-3Z-3-3 3535 OHOH HH HH (CH2)2OCH2 (CH 2 ) 2 OCH 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 3636 OHOH HH HH (CH2)4 (CH 2 ) 4 22 ClCl SO2MeSO 2 Me Z-1Z-1 3737 OHOH HH HH (CH2)4 (CH 2 ) 4 22 ClCl SO2MeSO 2 Me Z-2Z-2 3838 OHOH HH HH (CH2)2OCH2 (CH 2 ) 2 OCH 2 00 ClCl SO2MeSO 2 Me Z-3-1Z-3-1 3939 OHOH HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 4040 OHOH HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 4141 OHOH HH HH (CH2)2 (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 4242 OHOH HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 ClCl SO2MeSO 2 Me Z-1Z-1 4343 OHOH HH HH (CH2)2 (CH 2 ) 2 22 MeMe SO2MeSO 2 Me Z-1Z-1 4444 OHOH HH HH (CH2)2 (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 4545 OHOH HH HH CH2CH=CHCH2(cis)CH 2 CH = CHCH 2 (cis) 00 ClCl SO2MeSO 2 Me Z-1Z-1 4646 OHOH HH HH (CH2)2 (CH 2 ) 2 22 MeMe NO2 NO 2 Z-1Z-1 4747 OHOH HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 MeMe SO2MeSO 2 Me Z-1Z-1 4848 OHOH HH HH CH2CCCH2 CH 2 CCCH 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 4949 OHOH HH HH CH2OCH2 CH 2 OCH 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 5050 OHOH HH HH CH2OCH2 CH 2 OCH 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 5151 OHOH HH HH CH2CHFCH 2 CHF 22 ClCl SO2MeSO 2 Me Z-1Z-1 5252 OC(O)i-PrOC (O) i -Pr HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 5353 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 5454 OC(O)c-PrOC (O) c -Pr HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 5555 OC(O)t-BuOC (O) t -Bu HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 5656 OC(O)i-PrOC (O) i -Pr HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 5757 OC(O)c-PrOC (O) c -Pr HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 5858 OC(O)i-PrOC (O) i -Pr HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 5959 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6060 OC(O)t-BuOC (O) t -Bu HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6161 OHOH HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6262 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6363 OC(O)c-PrOC (O) c -Pr HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6464 OC(O)i-PrOC (O) i -Pr HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6565 OC(O)t-BuOC (O) t -Bu HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6666 OC(O)EtOC (O) Et HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 6767 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 6868 OC(O)c-PrOC (O) c -Pr HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 6969 OC(O)i-PrOC (O) i -Pr HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 7070 OC(O)t-BuOC (O) t -Bu HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 7171 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 7272 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 ClCl SO2MeSO 2 Me Z-1Z-1 7373 OC(O)c-PrOC (O) c -Pr HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 ClCl SO2MeSO 2 Me Z-1Z-1 7474 OC(O)t-BuOC (O) t -Bu HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 ClCl SO2MeSO 2 Me Z-1Z-1 7575 OC(O)i-PrOC (O) i -Pr HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 ClCl SO2MeSO 2 Me Z-1Z-1 7676 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2 ) 2 22 MeMe SO2MeSO 2 Me Z-1Z-1 7777 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 7878 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2(cis)CH 2 CH = CHCH 2 (cis) 00 ClCl SO2MeSO 2 Me Z-1Z-1 7979 OC(O)i-PrOC (O) i -Pr HH HH CH2CH=CHCH2 (cis)CH 2 CH = CHCH 2 (cis) 00 ClCl SO2MeSO 2 Me Z-1Z-1 8080 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 MeMe SO2MeSO 2 Me Z-1Z-1 8181 OC(O)MeOC (O) Me HH HH CH2CCCH2 CH 2 CCCH 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 8282 OC(O)MeOC (O) Me HH HH (CH2)2 (CH 2 ) 2 22 MeMe NO2 NO 2 Z-1Z-1 8383 OC(O)MeOC (O) Me HH HH CH2CHFCH 2 CHF 22 ClCl SO2MeSO 2 Me Z-1Z-1 8484 OC(O)t-BuOC (O) t -Bu HH HH CH2CHFCH 2 CHF 22 ClCl SO2MeSO 2 Me Z-1Z-1 8585 ClCl HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 8686 ClCl HH HH (CH2)4 (CH 2 ) 4 00 ClCl SO2MeSO 2 Me Z-1Z-1 8787 ClCl HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-3-4Z-3-4 8888 ClCl HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-3-3Z-3-3 8989 ClCl HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-3-2Z-3-2 9090 ClCl HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 9191 ClCl HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 9292 ClCl HH HH (CH2)2 (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 9393 ClCl HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-1Z-1 9494 ClCl HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 22 ClCl SO2MeSO 2 Me Z-1Z-1 9595 ClCl HH HH (CH2)2 (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 9696 ClCl HH HH (CH2)2 (CH 2 ) 2 22 MeMe SO2MeSO 2 Me Z-1Z-1 9797 ClCl HH HH (CH2)2 (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 9898 ClCl HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 MeMe SO2MeSO 2 Me Z-1Z-1 9999 ClCl HH HH CH2CHFCH 2 CHF 22 ClCl SO2MeSO 2 Me Z-1Z-1 100100 OC(O)t-BuOC (O) t -Bu HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 101101 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 102102 OC(O)c-PrOC (O) c -Pr HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 103103 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 0　0 ClCl SO2MeSO 2 Me Z-2Z-2 104104 OC(O)i-PrOC (O) i -Pr HH HH CH2CCCH2 CH 2 CCCH 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 105105 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2(cis)CH 2 CH = CHCH 2 (cis) 00 MeMe NO2 NO 2 Z-1Z-1 106106 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 MeMe NO2 NO 2 Z-1Z-1 107107 OC(O)MeOC (O) Me HH HH CH2CH=CHCH2(cis)CH 2 CH = CHCH 2 (cis) 00 MeMe SO2MeSO 2 Me Z-1Z-1 108108 OHOH HH HH CH2CH=CHCH2(cis)CH 2 CH = CHCH 2 (cis) 00 MeMe NO2 NO 2 Z-1Z-1 109109 ClCl HH HH CH2CH=CHCH2(cis)CH 2 CH = CHCH 2 (cis) 00 MeMe NO2 NO 2 Z-1Z-1 110110 OHOH HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 MeMe NO2 NO 2 Z-1Z-1 111111 ClCl HH HH CH2CH=CHCH2(trans)CH 2 CH = CHCH 2 (trans) 00 MeMe NO2 NO 2 Z-1Z-1 112112 OHOH HH HH CH2OCH2 CH 2 OCH 2 00 ClCl NO2 NO 2 Z-1Z-1 113113 OHOH HH HH CH2OCH2 CH 2 OCH 2 00 MeMe NO2 NO 2 Z-1Z-1 114114 OHOH HH HH CH2CH=CHCH2(cis)CH 2 CH = CHCH 2 (cis) 00 MeMe SO2MeSO 2 Me Z-1Z-1 115115 ClCl HH HH CH2CH=CHCH2(cis)CH 2 CH = CHCH 2 (cis) 00 MeMe SO2MeSO 2 Me Z-1Z-1 116116 FF HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-2Z-2 117117 FF HH HH (CH2)2 (CH 2 ) 2 00 ClCl SO2MeSO 2 Me Z-1Z-1 118118 FF HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-1Z-1 119119 BrBr HH HH (CH2)3 (CH 2 ) 3 00 ClCl SO2MeSO 2 Me Z-1Z-1 120120 OHOH HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 121121 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 122122 ClCl HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 123123 OHOH HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 124124 OC(O)MeOC (O) Me HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 125125 ClCl HH HH (CH2)2O(CH2)2 (CH 2 ) 2 O (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 126126 OHOH HH HH CH2O(CH2)2 CH 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 127127 OC(O)MeOC (O) Me HH HH CH2O(CH2)2 CH 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 128128 ClCl HH HH CH2O(CH2)2 CH 2 O (CH 2 ) 2 00 MeMe NO2 NO 2 Z-1Z-1 129129 OHOH HH HH CH2O(CH2)2 CH 2 O (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 130130 OC(O)MeOC (O) Me HH HH CH2O(CH2)2 CH 2 O (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 131131 OHOH HH HH CH2SCH2 CH 2 SCH 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 132132 OHOH HH HH (CH2)2S(CH2)2 (CH 2 ) 2 S (CH 2 ) 2 00 MeMe SO2MeSO 2 Me Z-1Z-1 133133 ClCl HH HH CH2CHFCH 2 CHF 00 MeMe SO2MeSO 2 Me Z-2Z-2 134134 OHOH HH HH CH2CHFCH 2 CHF 00 MeMe SO2MeSO 2 Me Z-1Z-1 135135 ClCl HH HH CH2CHFCH 2 CHF 00 MeMe SO2MeSO 2 Me Z-1Z-1 136136 OC(O)MeOC (O) Me HH HH CH2CHFCH 2 CHF 00 MeMe SO2MeSO 2 Me Z-1Z-1

상기 표 1에서 구체화된 화합물들의 구조분석 결과는 하기 표 2와 같다The structural analysis results of the compounds specified in Table 1 are shown in Table 2 below.

Com.No.Com.No. NMRNMR 1One 1H NMR (300 MHz, CDCl3) δ 8.03 (d, J = 8.2 Hz, 1H), 7.74 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 6.39 (s, 2H), 3.26 (s, 3H), 3.01 (t, J = 7.0 Hz, 2H), 2.42-2.34 (m, 2H), 2.04-2.00 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.03 (d, J = 8.2 Hz, 1H), 7.74 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 6.39 (s, 2H), 3.26 (s, 3H), 3.01 (t, J = 7.0 Hz, 2H), 2.42-2.34 (m, 2H), 2.04-2.00 (m, 2H) 22 1H NMR (500 MHz, CDCl3) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz, 2H), 4.68 (t, J = 4.8 Hz, 2H), 3.25 (s, 3H), 2.81- 2.79 (m, 2H), 2.42-2.40 (m, 2H), 2.07 (quin, J = 6.5 Hz, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz , 2H), 4.68 (t, J = 4.8 Hz, 2H), 3.25 (s, 3H), 2.81-2.79 (m, 2H), 2.42-2.40 (m, 2H), 2.07 (quin, J = 6.5 Hz, 2H) 33 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.70 (s, 2H), 7.64 (d, J = 8.2 Hz, 1H), 4.76 (t, J = 7.0 Hz, 2H),4.33 (t, J = 6.0 Hz, 2H), 3.65-3.63 (m, 2H), 3.37 (s, 3H), 2.64-2.56 (m, 2H), 2.43- 2.40 (m, 2H), 2.06-1.85 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.95 (d, J = 8.2 Hz, 1H), 7.70 (s, 2H), 7.64 (d, J = 8.2 Hz, 1H), 4.76 (t, J = 7.0 Hz , 2H), 4.33 (t, J = 6.0 Hz, 2H), 3.65-3.63 (m, 2H), 3.37 (s, 3H), 2.64-2.56 (m, 2H), 2.43- 2.40 (m, 2H), 2.06-1.85 (m, 2H) 44 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 7.5 Hz, 1H), 7.63 (s, 2H), 7.09 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 6.8 Hz, 2H), 4.30 (t, J = 6.2 Hz, 2H), 3.27 (s, 3H), 2.83 (t, 2H), 2.47 (t, 2H), 2.24 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 7.5 Hz, 2H), 1.94-1.90 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.95 (d, J = 7.5 Hz, 1H), 7.63 (s, 2H), 7.09 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 6.8 Hz , 2H), 4.30 (t, J = 6.2 Hz, 2H), 3.27 (s, 3H), 2.83 (t, 2H), 2.47 (t, 2H), 2.24 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 7.5 Hz, 2H), 1.94-1.90 (m, 2H) 55 1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.58 (s, 2H), 7.05 (d, J = 8.1 Hz, 1H), 4.49 (t, J = 6.9 Hz, 2H), 4.22 (t, J = 6.4 Hz, 2H), 3.24 (s, 3H), 2.81 (t, J = 6.0 Hz, 2H), 2.44 (t, J = 6.0 Hz, 2H), 2.11-2.02 (m, 4H), 1.94- 1.89 (m, 2H), 1.59-1.49 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.91 (d, J = 8.1 Hz, 1H), 7.58 (s, 2H), 7.05 (d, J = 8.1 Hz, 1H), 4.49 (t, J = 6.9 Hz , 2H), 4.22 (t, J = 6.4 Hz, 2H), 3.24 (s, 3H), 2.81 (t, J = 6.0 Hz, 2H), 2.44 (t, J = 6.0 Hz, 2H), 2.11-2.02 (m, 4H), 1.94-1.89 (m, 2H), 1.59-1.49 (m, 2H) 66 1H NMR (300 MHz, CDCl3) δ 8.13 (s, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.88 (d, J = 8.2 Hz, 1H), 7.82 (s, 1H), 6.37 (s, 2H), 3.19 (s, 3H), 2.43-2.34 (m, 4H), 1.96-1.89 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.13 (s, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.88 (d, J = 8.2 Hz, 1H), 7.82 (s, 1H), 6.37 (s, 2H), 3.19 (s, 3H), 2.43-2.34 (m, 4H), 1.96-1.89 (m, 2H) 77 1H NMR (500 MHz, CDCl3) δ 8.17 (s, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.72 (s, 1H), 7.19 (d, J = 8.0 Hz, 1H), 5.00 (t, J = 4.7 Hz, 2H), 4.64 (t, J = 4.7 Hz, 2H), 3.20 (s, 3H), 2.62-2.60 (m, 2H), 2.55-2.53 (m, 2H), 2.07 (quin, J = 6.5 Hz, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 8.17 (s, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.72 (s, 1H), 7.19 (d, J = 8.0 Hz, 1H), 5.00 (t, J = 4.7 Hz, 2H), 4.64 (t, J = 4.7 Hz, 2H), 3.20 (s, 3H), 2.62-2.60 (m, 2H), 2.55-2.53 (m, 2H), 2.07 ( quin, J = 6.5 Hz, 2H) 88 1H NMR (300 MHz, Acetone-d 6) δ 7.99 (s, 1H), 7.81 (d, J = 8.2 Hz, 1H), 7.65 (d, J = 8.2 Hz, 1H), 7.60 (s, 1H), 4.66 (t, J = 7.2 Hz, 2H), 4.22 (t, J = 6.0 Hz, 2H), 3.51-3.49 (m, 2H), 3.22 (s, 3H), 2.45 (t, J = 6.7 Hz, 2H), 2.23 (t, J = 6.7 Hz, 2H), 1.81-1.71 (m, 2H) 1 H NMR (300 MHz, Acetone- d 6 ) δ 7.99 (s, 1H), 7.81 (d, J = 8.2 Hz, 1H), 7.65 (d, J = 8.2 Hz, 1H), 7.60 (s, 1H) , 4.66 (t, J = 7.2 Hz, 2H), 4.22 (t, J = 6.0 Hz, 2H), 3.51-3.49 (m, 2H), 3.22 (s, 3H), 2.45 (t, J = 6.7 Hz, 2H), 2.23 (t, J = 6.7 Hz, 2H), 1.81-1.71 (m, 2H) 99 1H NMR (500 MHz, CDCl3) δ 7.96 (d, J = 8.1 Hz, 1H), 7.76 (s, 1H), 7.64 (s, 1H), 7.11 (d, J = 8.1 Hz, 1H), 4.54 (t, J = 7.5 Hz, 2H), 4.30 (t, J = 6.0 Hz, 2H), 3.25 (s, 3H), 2.85 (t, J = 6.0 Hz, 2H), 2.47 (t, J = 7.5 Hz, 2H), 2.22 (t, J = 6.5 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.97-1.93 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.96 (d, J = 8.1 Hz, 1H), 7.76 (s, 1H), 7.64 (s, 1H), 7.11 (d, J = 8.1 Hz, 1H), 4.54 (t, J = 7.5 Hz, 2H), 4.30 (t, J = 6.0 Hz, 2H), 3.25 (s, 3H), 2.85 (t, J = 6.0 Hz, 2H), 2.47 (t, J = 7.5 Hz , 2H), 2.22 (t, J = 6.5 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.97-1.93 (m, 2H) 1010 1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.50-4.42 (m, 2H), 4.22 (t, J = 6.0 Hz, 2H), 3.23 (s, 3H), 2.60 (t, J = 6.6 Hz, 2H), 2.36 (t, J = 6.3 Hz, 2H), 2.11-1.87 (m, 6H), 1.57-1.49 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.50 -4.42 (m, 2H), 4.22 (t, J = 6.0 Hz, 2H), 3.23 (s, 3H), 2.60 (t, J = 6.6 Hz, 2H), 2.36 (t, J = 6.3 Hz, 2H) , 2.11-1.87 (m, 6H), 1.57-1.49 (m, 2H) 1111 1H NMR (300 MHz, CDCl3) δ 8.38 (s, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.96 (s, 1H), 7.88 (d, J = 8.2 Hz, 1H), 6.37 (s, 2H), 3.19 (s, 3H), 2.43-2.34 (m, 4H), 1.96 -1.89 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.38 (s, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.96 (s, 1H), 7.88 (d, J = 8.2 Hz, 1H), 6.37 (s, 2H), 3.19 (s, 3H), 2.43-2.34 (m, 4H), 1.96 -1.89 (m, 2H) 1212 1H NMR (300 MHz, CDCl3) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 (m, 2H), 2.04 (t, J = 6.5 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 (m, 2H), 2.04 ( t, J = 6.5 Hz, 2H) 1313 1H NMR (300 MHz, CDCl3) δ 8.27 (s, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.98 (s, 1H), 7.32 (d, J = 8.1 Hz, 1H), 4.51 (t, J = 6.6 Hz, 2H), 4.33 (t, J = 5.5 Hz, 2H), 3.72- 3.70 (m, 2H), 3.26 (s, 3H), 2.98- 2.40 (m, 4H), 2.06- 1.93 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.27 (s, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.98 (s, 1H), 7.32 (d, J = 8.1 Hz, 1H), 4.51 (t, J = 6.6 Hz, 2H), 4.33 (t, J = 5.5 Hz, 2H), 3.72-3.70 (m, 2H), 3.26 (s, 3H), 2.98-2.40 (m, 4H), 2.06- 1.93 (m, 2 H) 1414 1H NMR (500 MHz, CDCl3) δ 8.18 (s, 1H), 8.00 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H), 4.34-4.29 (m, 4H), 3.26 (s, 3H), 2.85 (t, J = 6.0 Hz, 2H), 2.47 (t, J = 6.0 Hz, 2H), 2.19 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.95-1.91 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 8.18 (s, 1H), 8.00 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H), 4.34 -4.29 (m, 4H), 3.26 (s, 3H), 2.85 (t, J = 6.0 Hz, 2H), 2.47 (t, J = 6.0 Hz, 2H), 2.19 (t, J = 7.0 Hz, 2H) , 2.10 (t, J = 6.5 Hz, 2H), 1.95-1.91 (m, 2H) 1515 1H NMR (300 MHz, CDCl3) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.28 (t, J = 6.9 Hz, 2H), 3.58-3.53 (m, 2H), 3.24 (s, 3H), 2.64 (t, J = 6.6 Hz, 2H), 2.32 (t, J = 6.6 Hz, 2H), 2.10-1.93 (m, 6H), 1.60-1.45 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.28 (t, J = 6.9 Hz, 2H), 3.58-3.53 (m, 2H), 3.24 (s, 3H), 2.64 (t, J = 6.6 Hz, 2H), 2.32 (t, J = 6.6 Hz, 2H) , 2.10-1.93 (m, 6H), 1.60-1.45 (m, 2H) 1616 1H NMR (300 MHz, CDCl3) δ 8.59 (s, 1H), 8.02 (d, J = 8.1 Hz, 1H), 7.23 (d, J = 8.1 Hz, 1H), 6.17 (s, 2H), 3.19 (s, 3H), 2.85 (t, J = 6.3 Hz, 2H), 2.46 (t, J = 6.3 Hz, 2H), 2.10 (quin, J = 6.5 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.59 (s, 1H), 8.02 (d, J = 8.1 Hz, 1H), 7.23 (d, J = 8.1 Hz, 1H), 6.17 (s, 2H), 3.19 (s, 3H), 2.85 (t, J = 6.3 Hz, 2H), 2.46 (t, J = 6.3 Hz, 2H), 2.10 (quin, J = 6.5 Hz, 2H) 1717 1H NMR (500 MHz, CDCl3) δ 8.40 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.14 (d, J = 8.0 Hz, 1H), 4.74 (t, J = 4.8 Hz, 2H), 4.67 (t, J = 4.8 Hz, 2H), 3.15 (s, 3H), 2.86-2.84 (m, 2H), 2.47-2.45 (m, 2H), 2.10 (quin, J = 6.5 Hz, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 8.40 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.14 (d, J = 8.0 Hz, 1H), 4.74 (t, J = 4.8 Hz , 2H), 4.67 (t, J = 4.8 Hz, 2H), 3.15 (s, 3H), 2.86-2.84 (m, 2H), 2.47-2.45 (m, 2H), 2.10 (quin, J = 6.5 Hz, 2H) 1818 1H NMR (500 MHz, CDCl3) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz, 2H), 4.68 (t, J = 4.8 Hz, 2H), 3.25 (s, 3H), 2.81- 2.79 (m, 2H), 2.42-2.40 (m, 2H), 2.07-1.98 (m, 1H), 1.95 (d, J = 8.0 Hz, 3H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz , 2H), 4.68 (t, J = 4.8 Hz, 2H), 3.25 (s, 3H), 2.81-2.79 (m, 2H), 2.42-2.40 (m, 2H), 2.07-1.98 (m, 1H), 1.95 (d, J = 8.0 Hz, 3H) 1919 1H NMR (500 MHz, CDCl3) δ 8.17 (s, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.72 (s, 1H), 7.19 (d, J = 8.0 Hz, 1H), 5.00 (t, J = 4.7 Hz, 2H), 4.64 (t, J = 4.7 Hz, 2H), 3.20 (s, 3H), 2.62-2.60 (m, 2H), 2.55-2.53 (m, 2H), 2.07-2.01 (m, 1H), 1.99 (d, J = 8.0 Hz, 3H) 1 H NMR (500 MHz, CDCl 3 ) δ 8.17 (s, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.72 (s, 1H), 7.19 (d, J = 8.0 Hz, 1H), 5.00 (t, J = 4.7 Hz, 2H), 4.64 (t, J = 4.7 Hz, 2H), 3.20 (s, 3H), 2.62-2.60 (m, 2H), 2.55-2.53 (m, 2H), 2.07- 2.01 (m, 1H), 1.99 (d, J = 8.0 Hz, 3H) 2020 1H NMR (300 MHz, CDCl3) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 (m, 2H), 2.04-2.01 (m, 1H), 2.00 (d, J = 8.0 Hz, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 (m, 2H), 2.04- 2.01 (m, 1H), 2.00 (d, J = 8.0 Hz, 3H) 2121 1H NMR (500 MHz, CDCl3) δ 8.05 (d, J = 7.9 Hz, 1H), 7.75 (s, 2H), 7.79 (d, J = 8.2 Hz, 1H), 6.42 (s, 2H), 3.38-3.25 (m, 2H), 3.21 (s, 3H), 2.35-2.17 (m, 4H), 1.69-1.64 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 8.05 (d, J = 7.9 Hz, 1H), 7.75 (s, 2H), 7.79 (d, J = 8.2 Hz, 1H), 6.42 (s, 2H), 3.38 -3.25 (m, 2H), 3.21 (s, 3H), 2.35-2.17 (m, 4H), 1.69-1.64 (m, 2H) 2222 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.67 (d, J = 8.5 Hz, 1H), 7.63 (s, 2H), 4.78 (t, J = 7.1 Hz, 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42-3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.95 (d, J = 8.2 Hz, 1H), 7.67 (d, J = 8.5 Hz, 1H), 7.63 (s, 2H), 4.78 (t, J = 7.1 Hz , 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42-3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H) 2323 1H NMR (300 MHz, CDCl3) δ 7.97 (d, J = 8.2 Hz, 1H), 7.64 (d, J = 8.8 Hz, 1H), 7.63 (s, 2H), 4.75 (t, J = 7.1 Hz, 2H), 4.34 (t, J = 6.0 Hz, 2H), 3.43 (t, J = 4.2 Hz, 1H), 3.31-3.28 (m, 2H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64- 2.55 (m, 3H), 1.99-1.84 (m, 1H), 1.67-1.62 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.97 (d, J = 8.2 Hz, 1H), 7.64 (d, J = 8.8 Hz, 1H), 7.63 (s, 2H), 4.75 (t, J = 7.1 Hz , 2H), 4.34 (t, J = 6.0 Hz, 2H), 3.43 (t, J = 4.2 Hz, 1H), 3.31-3.28 (m, 2H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64- 2.55 (m, 3H), 1.99-1.84 (m, 1H), 1.67-1.62 (m, 2H) 2424 1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.77 (t, J = 7.1 Hz, 2H), 4.30 (t, J = 6.5 Hz, 2H), 3.45-3.28 (m, 3H), 3.28 (s, 3H), 3.10 (t, J = 6.0 Hz, 1H), 2.64-2.50 (m, 1H), 1.92-1.82 (m, 1H), 1.69-1.63 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.77 (t, J = 7.1 Hz, 2H), 4.30 (t, J = 6.5 Hz, 2H), 3.45-3.28 (m, 3H), 3.28 (s, 3H), 3.10 (t, J = 6.0 Hz, 1H) , 2.64-2.50 (m, 1H), 1.92-1.82 (m, 1H), 1.69-1.63 (m, 2H) 2525 1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.77 (t, J = 7.1 Hz, 2H), 4.30 (t, J = 6.5 Hz, 2H), 3.45- 3.28 (m, 3H), 3.28 (s, 3H), 3.10 (t, J = 6.0 Hz, 1H), 2.64-2.50 (m, 1H), 1.92-1.82 (m, 1H), 1.69-1.63 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.91 (d, J = 8.1 Hz, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 7.05 (d, J = 8.1 Hz, 1H), 4.77 (t, J = 7.1 Hz, 2H), 4.30 (t, J = 6.5 Hz, 2H), 3.45- 3.28 (m, 3H), 3.28 (s, 3H), 3.10 (t, J = 6.0 Hz, 1H) , 2.64-2.50 (m, 1H), 1.92-1.82 (m, 1H), 1.69-1.63 (m, 2H) 2626 1H NMR (300 MHz, CDCl3) δ 7.98 (d, J = 8.2 Hz, 1H), 7.76 (s, 1H), 7.72 (d, J = 9.8 Hz, 1H), 7.72 (s, 1H), 4.71 (t, J = 7.0 Hz, 2H), 4.34 (t, J = 5.8 Hz, 2H), 3.32- 3.31 (m, 1H), 3.25 (s, 3H), 2.95- 2.78 (m, 2H), 2.59-2.48 (m, 2H), 2.30-2.12 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.98 (d, J = 8.2 Hz, 1H), 7.76 (s, 1H), 7.72 (d, J = 9.8 Hz, 1H), 7.72 (s, 1H), 4.71 (t, J = 7.0 Hz, 2H), 4.34 (t, J = 5.8 Hz, 2H), 3.32- 3.31 (m, 1H), 3.25 (s, 3H), 2.95-2.78 (m, 2H), 2.59- 2.48 (m, 2H), 2.30-2.12 (m, 2H) 2727 1H NMR (300 MHz, CDCl3) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.78 (t, J = 7.1 Hz, 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42- 3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.78 (t, J = 7.1 Hz, 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42- 3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H) , 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H) 2828 1H NMR (300 MHz, CDCl3) δ 8.34 (s, 1H), 8.02 (s, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.68 (d, J = 8.2 Hz, 1H), 4.52 (t, J = 7.0 Hz, 2H), 4.39-4.29 (m, 2H), 3.43-3.41 (m, 1H), 3.24 (s, 3H), 2.90-2.81 (m, 2H), 2.58-2.48 (m, 3H), 2.13-1.84 (m, 4H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.34 (s, 1H), 8.02 (s, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.68 (d, J = 8.2 Hz, 1H), 4.52 (t, J = 7.0 Hz, 2H), 4.39-4.29 (m, 2H), 3.43-3.41 (m, 1H), 3.24 (s, 3H), 2.90-2.81 (m, 2H), 2.58-2.48 (m , 3H), 2.13-1.84 (m, 4H) 2929 1H NMR (500 MHz, CDCl3) δ 8.40 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.17 (d, J = 8.0 Hz, 1H), 4.74 (t, J = 4.6 Hz, 2H), 4.67 (t, J = 4.6 Hz, 2H), 3.20 (t, J = 4.6 Hz, 1H), 3.14 (s, 3H), 2.92 (t, J = 5.5 Hz, 1H), 2.30-2.14 (m, 3H), 2.08-2.03 (m, 1H), 1.82-1.78 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 8.40 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.17 (d, J = 8.0 Hz, 1H), 4.74 (t, J = 4.6 Hz , 2H), 4.67 (t, J = 4.6 Hz, 2H), 3.20 (t, J = 4.6 Hz, 1H), 3.14 (s, 3H), 2.92 (t, J = 5.5 Hz, 1H), 2.30-2.14 (m, 3H), 2.08-2.03 (m, 1H), 1.82-1.78 (m, 2H) 3131 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.1 Hz, 1H), 7.59 (d, J = 6.4 Hz, 2H), 7.10 (d, J = 8.1 Hz, 1H), 6.31 (s, 1H), 4.64 (s, 4H), 3.13 (s, 3H), 2.83 (t, J = 6.0 Hz, 2H), 2.45 (t, J = 6.0 Hz, 2H), 2.10- 2.06 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.1 Hz, 1H), 7.59 (d, J = 6.4 Hz, 2H), 7.10 (d, J = 8.1 Hz, 1H), 6.31 (s , 1H), 4.64 (s, 4H), 3.13 (s, 3H), 2.83 (t, J = 6.0 Hz, 2H), 2.45 (t, J = 6.0 Hz, 2H), 2.10-2.06 (m, 2H) 3232 1H NMR (500 MHz, CDCl3) δ 8.02 (s, 1H), 7.96 (d, J = 8.1Hz, 1H), 7.14 (d, J = 8.1Hz, 1H), 4.67-4.55 (m, 4H), 3.17 (s, 3H), 2.85 (t, J = 6.1Hz, 2H), 2.47 (t, J = 6.0Hz, 2H), 2.10 (t, J = 6.3Hz, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 8.02 (s, 1H), 7.96 (d, J = 8.1 Hz, 1H), 7.14 (d, J = 8.1 Hz, 1H), 4.67-4.55 (m, 4H) , 3.17 (s, 3H), 2.85 (t, J = 6.1 Hz, 2H), 2.47 (t, J = 6.0 Hz, 2H), 2.10 (t, J = 6.3 Hz, 2H) 3535 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 9.6 Hz, 2H), 7.09 (d, J = 8.2 Hz, 1H), 5.85 (s, 2H), 4.38 (t, J = 4.2 Hz, 2H), 3.95 (t, J = 4.2 Hz, 2H), 3.25 (s, 3H), 2.82 (t, J = 6.2 Hz, 2H), 2.44 (t, J = 6.6 Hz, 2H), 2.07 (quin, J = 6.5 Hz, 2H). 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 9.6 Hz, 2H), 7.09 (d, J = 8.2 Hz, 1H), 5.85 (s , 2H), 4.38 (t, J = 4.2 Hz, 2H), 3.95 (t, J = 4.2 Hz, 2H), 3.25 (s, 3H), 2.82 (t, J = 6.2 Hz, 2H), 2.44 (t , J = 6.6 Hz, 2H), 2.07 (quin, J = 6.5 Hz, 2H). 3636 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.1 Hz, 1H), 7.75 (s, 2H), 7.11 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 7.2 Hz, 2H), 4.29 (t, J = 7.1 Hz, 2H), 3.27 (s, 3H), 3.19-3.17 (m 1H), 3.08-3.05 (m, 1H), 2.29-2.11 (m, 4H), 1.93-1.89 (m, 4H), 1.82-1.77 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.95 (d, J = 8.1 Hz, 1H), 7.75 (s, 2H), 7.11 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 7.2 Hz , 2H), 4.29 (t, J = 7.1 Hz, 2H), 3.27 (s, 3H), 3.19-3.17 (m 1H), 3.08-3.05 (m, 1H), 2.29-2.11 (m, 4H), 1.93 -1.89 (m, 4H), 1.82-1.77 (m, 2H) 3838 1H NMR (300 MHz, CDCl3) δ 8.25 (s, 1H), 7.92 (s, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.02 (d, J = 8.0 Hz, 1H), 5.58 (s, 2H), 4.34 (t, J = 4.1 Hz, 2H), 3.94 (t, J = 4.3 Hz, 2H), 3.18 (s, 3H), 2.75-2.73 (m, 2H), 2.37-2.35 (m, 2H), 2.00-1.98 (m, 2H). 1 H NMR (300 MHz, CDCl 3 ) δ 8.25 (s, 1H), 7.92 (s, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.02 (d, J = 8.0 Hz, 1H), 5.58 (s, 2H), 4.34 (t, J = 4.1 Hz, 2H), 3.94 (t, J = 4.3 Hz, 2H), 3.18 (s, 3H), 2.75-2.73 (m, 2H), 2.37-2.35 ( m, 2H), 2.00-1.98 (m, 2H). 3939 1H NMR (500 MHz, CDCl3) δ 7.94 (d, J = 7.9 Hz, 1H), 7.61 (s, 2H), 7.07 (d, J = 7.9 Hz, 1H), 4.67 (t, J = 4.9 Hz, 2H), 4.36 (t, J = 4.0 Hz, 2H), 4.12 (t, J = 4.9 Hz, 2H), 3.87 (t, J = 4.0 Hz, 2H), 3.26 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.44 (t, J = 6.3 Hz,, 2H), 2.09-1.98 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.94 (d, J = 7.9 Hz, 1H), 7.61 (s, 2H), 7.07 (d, J = 7.9 Hz, 1H), 4.67 (t, J = 4.9 Hz , 2H), 4.36 (t, J = 4.0 Hz, 2H), 4.12 (t, J = 4.9 Hz, 2H), 3.87 (t, J = 4.0 Hz, 2H), 3.26 (s, 3H), 2.82 (t , J = 6.3 Hz, 2H), 2.44 (t, J = 6.3 Hz, 2H), 2.09-1.98 (m, 2H) 4040 1H NMR (500 MHz, CDCl3) δ 7.97 (d, J = 8.1 Hz, 1H), 7.83 (s, 1H), 7.71 (s, 1H), 7.12 (d, J = 8.1 Hz, 1H), 4.65 (t, J = 4.9 Hz, 2H), 4.42 (t, J = 4.0 Hz, 2H), 3.97 (t, J = 4.9 Hz, 2H), 3.91 (t, J = 4.0 Hz, 2H), 3.25 (s, 3H), 2.85 (t, J = 6.3 Hz, 2H), 2.47 (t, J = 6.4 Hz,, 2H), 2.12-2.09 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.97 (d, J = 8.1 Hz, 1H), 7.83 (s, 1H), 7.71 (s, 1H), 7.12 (d, J = 8.1 Hz, 1H), 4.65 (t, J = 4.9 Hz, 2H), 4.42 (t, J = 4.0 Hz, 2H), 3.97 (t, J = 4.9 Hz, 2H), 3.91 (t, J = 4.0 Hz, 2H), 3.25 (s , 3H), 2.85 (t, J = 6.3 Hz, 2H), 2.47 (t, J = 6.4 Hz, 2H), 2.12-2.09 (m, 2H) 4141 1H NMR (300 MHz, CDCl3) δ 7.83 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.97 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.80 (t, 2H), 2.43 (t, 2H), 2.06 (m, 2H), 2.06 (s, 3H) ; Mass : 419 1 H NMR (300 MHz, CDCl 3 ) δ 7.83 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.97 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.80 (t, 2H), 2.43 (t, 2H), 2.06 (m, 2H), 2.06 (s, 3H); Mass: 419 4242 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.60-7.68 (m, 2H), 7.08 (d, J = 8.2 Hz, 1H), 6.13-6.2 (m, 1H), 5.98-6.11 (m, 1H), 5.14 (d, J = 5.6 Hz, 2H), 4.77 (d, J = 5.3 Hz, 1H), 3.25 (s, 3H), 2.75-2.88 (m, 2H), 2.38-2.52 (m, 2H), 2.00-2.14 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.2 Hz, 1H), 7.60-7.68 (m, 2H), 7.08 (d, J = 8.2 Hz, 1H), 6.13-6.2 (m, 1H), 5.98-6.11 (m, 1H), 5.14 (d, J = 5.6 Hz, 2H), 4.77 (d, J = 5.3 Hz, 1H), 3.25 (s, 3H), 2.75-2.88 (m, 2H ), 2.38-2.52 (m, 2H), 2.00-2.14 (m, 2H) 4343 1H NMR (300 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.2 Hz), 7.68 (s, 2H), 7.02 (d, 1H, J = 8.2 Hz), 4.93 (t, 2H), 4.57 (t, 2H), 3.26 (s, 3H), 3.18 (t, 1H), 2.90 (t, 1H), 2.11-2.29 (m, 3H), 2.03 (m, 1H), 1.94 (s, 3H), 1.76 (m, 2H) ; Mass : 445 1 H NMR (300 MHz, CDCl 3 ) δ 7.86 (d, 1H, J = 8.2 Hz), 7.68 (s, 2H), 7.02 (d, 1H, J = 8.2 Hz), 4.93 (t, 2H), 4.57 (t, 2H), 3.26 (s, 3H), 3.18 (t, 1H), 2.90 (t, 1H), 2.11-2.29 (m, 3H), 2.03 (m, 1H), 1.94 (s, 3H), 1.76 (m, 2 H); Mass: 445 4444 1H NMR (300 MHz, CDCl3) δ 7.73 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.92 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.56 (t, 2H), 2.82 (t, 2H), 2.44 (t, 2H), 2.08 (m, 2H), 1.92 (s, 3H) ; Mass : 386 1 H NMR (300 MHz, CDCl 3 ) δ 7.73 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.92 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.56 (t, 2H), 2.82 (t, 2H), 2.44 (t, 2H), 2.08 (m, 2H), 1.92 (s, 3H); Mass: 386 4545 1H NMR (300 MHz, CDCl3) δ 7.97 (d, J = 8.1 Hz, 1H), 7.59-7.66 (m, 2H), 7.13 (d, J = 8.1 Hz, 1H), 6.14-6.25 (m, 1H), 6.00-6.11 (m, 1H), 5.29 (d, J = 6.7 Hz, 2H), 4.96 (d, J = 6.7 Hz, 2H), 3.30 (s, 3H), 2.84 (t, J = 6.2 Hz, 2H), 2.47 (t, J = 6.2 Hz, 2H), 2.04-2.15 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.97 (d, J = 8.1 Hz, 1H), 7.59-7.66 (m, 2H), 7.13 (d, J = 8.1 Hz, 1H), 6.14-6.25 (m, 1H), 6.00-6.11 (m, 1H), 5.29 (d, J = 6.7 Hz, 2H), 4.96 (d, J = 6.7 Hz, 2H), 3.30 (s, 3H), 2.84 (t, J = 6.2 Hz, 2H), 2.47 (t, J = 6.2 Hz, 2H), 2.04-2.15 (m, 2H) 4646 1H NMR (500 MHz, CDCl3) δ 7.73 (d, 1H, J = 8.4 Hz), 7.67 (s, 2H), 6.95 (d, 1H, J = 8.4 Hz), 4.90 (t, 2H), 4.56 (t, 2H), 3.17 (t, 1H), 2.91 (t, 1H), 2.14-2.28 (m, 3H), 2.03 (m, 1H), 1.91 (s, 3H), 1.76 (m, 2H) ; Mass : 412 1 H NMR (500 MHz, CDCl 3 ) δ 7.73 (d, 1H, J = 8.4 Hz), 7.67 (s, 2H), 6.95 (d, 1H, J = 8.4 Hz), 4.90 (t, 2H), 4.56 (t, 2H), 3.17 (t, 1H), 2.91 (t, 1H), 2.14-2.28 (m, 3H), 2.03 (m, 1H), 1.91 (s, 3H), 1.76 (m, 2H); Mass: 412 4747 1H NMR (500 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.3 Hz), 7.66 (s, 2H), 6.99 (d, 1H, J = 8.3 Hz), 6.21 (m, 1H), 6.04 (m, 1H), 5.16 (d, 2H), 4.64 (d, 2H), 3.26 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.19 (s, 3H), 2.09 (m, 2H) ; Mass : 445 1 H NMR (500 MHz, CDCl 3 ) δ 7.86 (d, 1H, J = 8.3 Hz), 7.66 (s, 2H), 6.99 (d, 1H, J = 8.3 Hz), 6.21 (m, 1H), 6.04 (m, 1H), 5.16 (d, 2H), 4.64 (d, 2H), 3.26 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.19 (s, 3H), 2.09 ( m, 2H); Mass: 445 4848 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.0 Hz, 1H), 7.63-7.70 (m, 2H), 7.12 (d, J = 8.0 Hz, 1H), 5.35 (s, 2H), 4.94 (s, 2H), 3.29 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.45 (t, J = 6.3 Hz, 2H), 2.08 (q, J = 6.1 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.0 Hz, 1H), 7.63-7.70 (m, 2H), 7.12 (d, J = 8.0 Hz, 1H), 5.35 (s, 2H) , 4.94 (s, 2H), 3.29 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.45 (t, J = 6.3 Hz, 2H), 2.08 (q, J = 6.1 Hz, 2H) 4949 1H NMR (300 MHz, CDCl3) δ 7.88 (d, 1H, J = 8.3 Hz), 7.73 (s, 2H), 7.02 (d, 1H, J = 8.3 Hz), 6.04 (s, 2H), 5.38 (s, 2H), 3.28 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.25 (s, 3H), 2.09 (m, 2H) ; Mass : 434 1 H NMR (300 MHz, CDCl 3 ) δ 7.88 (d, 1H, J = 8.3 Hz), 7.73 (s, 2H), 7.02 (d, 1H, J = 8.3 Hz), 6.04 (s, 2H), 5.38 (s, 2H), 3.28 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.25 (s, 3H), 2.09 (m, 2H); Mass: 434 5151 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.3 Hz, 1H), 7.80 (s, 2H), 7.15 (d, J = 8.3 Hz, 1H), 7.01 (dt, J = 50.6, 6.0 Hz, 1H), 5.09-4.92 (m, 2H), 3.19 (s, 3H), 3.04-3.03 (m, 1H), 2.91-2.89 (m, 1H), 1.99-1.91 (m, 4H), 1.79-1.66 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.95 (d, J = 8.3 Hz, 1H), 7.80 (s, 2H), 7.15 (d, J = 8.3 Hz, 1H), 7.01 (dt, J = 50.6, 6.0 Hz, 1H), 5.09-4.92 (m, 2H), 3.19 (s, 3H), 3.04-3.03 (m, 1H), 2.91-2.89 (m, 1H), 1.99-1.91 (m, 4H), 1.79 -1.66 (m, 2H) 5252 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.68 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.2 Hz, 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.21 (s, 3H), 2.75 (t, J = 6.2 Hz, 2H), 2.62 (t, J = 6.9 Hz, 1H), 2.52 (t, J = 7.0 Hz, 2H), 2.14 (quin, J = 6.5 Hz, 2H), 1.19 (d, J = 7.0 Hz, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.91 (d, J = 8.1 Hz, 1H), 7.68 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.2 Hz , 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.21 (s, 3H), 2.75 (t, J = 6.2 Hz, 2H), 2.62 (t, J = 6.9 Hz, 1H), 2.52 (t , J = 7.0 Hz, 2H), 2.14 (quin, J = 6.5 Hz, 2H), 1.19 (d, J = 7.0 Hz, 6H) 5353 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.5 Hz, 1H), 7.68 (s, 2H), 7.45 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz, 2H), 4.70 (t, J = 5.0 Hz, 2H), 3.21 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.15 (s, 3H), 2.14-2.12 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.91 (d, J = 8.5 Hz, 1H), 7.68 (s, 2H), 7.45 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz , 2H), 4.70 (t, J = 5.0 Hz, 2H), 3.21 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.15 (s , 3H), 2.14-2.12 (m, 2H) 5454 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.1 Hz, 1H), 7.67 (s, 2H), 7.46 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.1 Hz, 2H), 4.70 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.75 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.14 (quin, J = 6.3 Hz, 2H), 1.58-1.57 (m, 1H), 0.99 (s, 4H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.90 (d, J = 8.1 Hz, 1H), 7.67 (s, 2H), 7.46 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.1 Hz , 2H), 4.70 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.75 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.14 (quin , J = 6.3 Hz, 2H), 1.58-1.57 (m, 1H), 0.99 (s, 4H) 5555 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.95 (t, J = 5.0 Hz, 2H), 4.70 (t, J = 4.8 Hz, 2H), 3.19 (s, 3H), 2.73 (t, J = 6.1 Hz, 2H), 2.50 (t, J = 6.4 Hz, 2H), 2.13 (quin, J = 6.7 Hz, 2H), 1.20 (s, 9H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.95 (t, J = 5.0 Hz , 2H), 4.70 (t, J = 4.8 Hz, 2H), 3.19 (s, 3H), 2.73 (t, J = 6.1 Hz, 2H), 2.50 (t, J = 6.4 Hz, 2H), 2.13 (quin , J = 6.7 Hz, 2H), 1.20 (s, 9H) 5656 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 15.8 Hz, 2H), 7.50 (d, J = 8.2 Hz, 1H), 4.91 (t, J = 5.0 Hz, 2H), 4.65 (t, J = 5.0 Hz, 2H), 3.08 (s, 3H), 2.75 (t, J = 5.2 Hz, 2H), 2.63 (sep, J = 6.9 Hz, 1H), 2.52 (t, J = 4.6 Hz, 2H), 2.14 (quin, J = 6.7 Hz, 2H), 1.19 (d, J = 7.1 Hz, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.91 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 15.8 Hz, 2H), 7.50 (d, J = 8.2 Hz, 1H), 4.91 (t , J = 5.0 Hz, 2H), 4.65 (t, J = 5.0 Hz, 2H), 3.08 (s, 3H), 2.75 (t, J = 5.2 Hz, 2H), 2.63 (sep, J = 6.9 Hz, 1H ), 2.52 (t, J = 4.6 Hz, 2H), 2.14 (quin, J = 6.7 Hz, 2H), 1.19 (d, J = 7.1 Hz, 6H) 5757 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.69 (s, 2H), 7.38 (d, J = 8.2 Hz, 1H), 4.97 (t, J = 5.1 Hz, 2H), 4.70 (t, J = 5.2 Hz, 2H), 3.21 (s, 3H), 3.07-3.05 (m, 2H), 2.32-2.17 (m, 4H), 1.76-1.75 (m, 3H), 1.08-1.04 (m, 4H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.90 (d, J = 8.2 Hz, 1H), 7.69 (s, 2H), 7.38 (d, J = 8.2 Hz, 1H), 4.97 (t, J = 5.1 Hz , 2H), 4.70 (t, J = 5.2 Hz, 2H), 3.21 (s, 3H), 3.07-3.05 (m, 2H), 2.32-2.17 (m, 4H), 1.76-1.75 (m, 3H), 1.08-1.04 (m, 4H) 5858 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.1 Hz, 1H), 7.68 (s, 2H), 7.37 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz, 2H), 4.69 (t, J = 5.3 Hz, 2H), 3.20 (s, 3H), 3.04-3.03 (m, 2H), 2.66 (quin, J = 6.9 Hz, 1H), 2.21-2.20 (m, 4H), 1.76-1.73 (m, 2H), 1.27-1.22 (m, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.90 (d, J = 8.1 Hz, 1H), 7.68 (s, 2H), 7.37 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz , 2H), 4.69 (t, J = 5.3 Hz, 2H), 3.20 (s, 3H), 3.04-3.03 (m, 2H), 2.66 (quin, J = 6.9 Hz, 1H), 2.21-2.20 (m, 4H), 1.76-1.73 (m, 2H), 1.27-1.22 (m, 6H) 5959 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.34 (d, J = 8.1 Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.69 (t, J = 5.2 Hz, 2H), 3.20 (s, 3H), 3.06-3.00 (m, 2H), 2.19 (s, 3H), 2.15-1.73 (m, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.34 (d, J = 8.1 Hz, 1H), 4.96 (t, J = 4.9 Hz , 2H), 4.69 (t, J = 5.2 Hz, 2H), 3.20 (s, 3H), 3.06-3.00 (m, 2H), 2.19 (s, 3H), 2.15-1.73 (m, 6H) 6060 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.68 (s, 2H), 7.39 (d, J = 8.1 Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.70 (t, J = 5.1 Hz, 2H), 3.23 (s, 3H), 3.01 (q, J = 6.6 Hz, 2H), 2.33-2.19 (m, 4H), 1.76-1.73 (m, 2H), 1.24 (s, 9H). 1 H NMR (500 MHz, CDCl 3 ) δ 7.90 (d, J = 8.2 Hz, 1H), 7.68 (s, 2H), 7.39 (d, J = 8.1 Hz, 1H), 4.96 (t, J = 4.9 Hz , 2H), 4.70 (t, J = 5.1 Hz, 2H), 3.23 (s, 3H), 3.01 (q, J = 6.6 Hz, 2H), 2.33-2.19 (m, 4H), 1.76-1.73 (m, 2H), 1.24 (s, 9H). 6161 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.1 Hz, 1H), 7.63 (s, 2H), 7.11 (d, J = 8.0 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.37 (t, J = 4.4 Hz, 2H), 4.14-1.12 (m, 2H), 3.89 (t, J = 4.5 Hz, 2H), 3.28 (s, 3H), 3.19 (t, J = 5.4 Hz, 1H), 2.92 (t, J = 6.4 Hz, 1H), 2.26-1.76 (m, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.95 (d, J = 8.1 Hz, 1H), 7.63 (s, 2H), 7.11 (d, J = 8.0 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.37 (t, J = 4.4 Hz, 2H), 4.14-1.12 (m, 2H), 3.89 (t, J = 4.5 Hz, 2H), 3.28 (s, 3H), 3.19 (t, J = 5.4 Hz, 1H), 2.92 (t, J = 6.4 Hz, 1H), 2.26-1.76 (m, 6H) 6262 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.33 (d, J = 8.1 Hz, 1H), 4.68 (t, J = 5.7 Hz, 2H), 4.34 (t, J = 4.5 Hz, 2H), 4.13-4.11 (m, 2H), 3.88-3.87 (t, J = 4.4 Hz, 2H), 3.25 (s, 3H), 3.07-3.01 (m, 2H), 2.18 (s, 3H), 2.15-1.73 (m, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.91 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.33 (d, J = 8.1 Hz, 1H), 4.68 (t, J = 5.7 Hz , 2H), 4.34 (t, J = 4.5 Hz, 2H), 4.13-4.11 (m, 2H), 3.88-3.87 (t, J = 4.4 Hz, 2H), 3.25 (s, 3H), 3.07-3.01 ( m, 2H), 2.18 (s, 3H), 2.15-1.73 (m, 6H) 6363 1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.61 (s, 2H), 7.30 (d, J = 8.2 Hz, 1H), 4.67 (t, J = 5.6 Hz, 2H), 4.33 (t, J = 4.1 Hz, 2H), 4.10 (t, J = 5.5 Hz, 2H), 3.86 (t, J = 4.3 Hz, 2H), 3.24 (s, 3H), 3.05-3.04 (m, 2H), 2.16- 2.07 (m, 4H), 1.75-1.59 (m, 3H), 1.04-1.01 (m, 4H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.91 (d, J = 8.2 Hz, 1H), 7.61 (s, 2H), 7.30 (d, J = 8.2 Hz, 1H), 4.67 (t, J = 5.6 Hz , 2H), 4.33 (t, J = 4.1 Hz, 2H), 4.10 (t, J = 5.5 Hz, 2H), 3.86 (t, J = 4.3 Hz, 2H), 3.24 (s, 3H), 3.05-3.04 (m, 2H), 2.16- 2.07 (m, 4H), 1.75-1.59 (m, 3H), 1.04-1.01 (m, 4H) 6464 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.37 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.35 (t, J = 4.2 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.5 Hz, 2H), 3.26 (s, 3H), 3.05-3.04 (m, 2H), 2.34-2.32 (m, 1H), 2.16-2.13 (m, 4H), 1.77-1.75 (m, 2H), 1.27-1.21 (m, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.91 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.37 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.35 (t, J = 4.2 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.5 Hz, 2H), 3.26 (s, 3H), 3.05-3.04 (m, 2H), 2.34-2.32 (m, 1H), 2.16-2.13 (m, 4H), 1.77-1.75 (m, 2H), 1.27-1.21 (m, 6H) 6565 1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.38 (d, J = 8.1 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.35 (t, J = 4.1 Hz, 2H), 4.13 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 2.7 Hz, 2H), 3.25 (s, 3H), 3.01-3.00 (m, 2H), 2.33-2.13 (m, 4H), 1.80-1.74 (m, 2H), 1.24 (s, 9H). 1 H NMR (500 MHz, CDCl 3 ) δ 7.91 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.38 (d, J = 8.1 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.35 (t, J = 4.1 Hz, 2H), 4.13 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 2.7 Hz, 2H), 3.25 (s, 3H), 3.01-3.00 (m, 2H), 2.33-2.13 (m, 4H), 1.80-1.74 (m, 2H), 1.24 (s, 9H). 6666 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.1 Hz, 1H), 7.67 (s, 2H), 7.35 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.69-4.67 (m, 2H), 3.20 (s, 3H), 3.05 (t, J = 5.0 Hz, 1H), 3.01 (t, J = 4.8 Hz, 1H), 2.44-2.43 (m, 2H), 2.29-2.05 (m, 4H), 1.76-1.72 (m, 2H), 1.15 (t, J = 4.2 Hz, 3H). 1 H NMR (500 MHz, CDCl 3 ) δ 7.90 (d, J = 8.1 Hz, 1H), 7.67 (s, 2H), 7.35 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz , 2H), 4.69-4.67 (m, 2H), 3.20 (s, 3H), 3.05 (t, J = 5.0 Hz, 1H), 3.01 (t, J = 4.8 Hz, 1H), 2.44-2.43 (m, 2H), 2.29-2.05 (m, 4H), 1.76-1.72 (m, 2H), 1.15 (t, J = 4.2 Hz, 3H). 6767 1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.44 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.7 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.6 Hz, 2H), 3.26 (s, 3H), 2.77 (t, J = 6.2 Hz, 2H), 2.54 (t, J = 6.5 Hz, 2H), 2.17 (s, 3H), 2.15-2.14 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.44 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.7 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.6 Hz, 2H), 3.26 (s, 3H), 2.77 (t , J = 6.2 Hz, 2H), 2.54 (t, J = 6.5 Hz, 2H), 2.17 (s, 3H), 2.15-2.14 (m, 2H) 6868 1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.1 Hz, 1H), 4.70 (t, J = 5.6 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.13 (t, J = 5.7 Hz, 2H), 3.89 (t, J = 4.6 Hz, 2H), 3.27 (s, 3H), 2.75 (t, J = 6.2 Hz, 2H), 2.53 (t, J = 6.5 Hz, 2H), 2.14-2.13 (m, 2H) 1.27-1.26 (m, 1H), 0.99-0.97 (m, 4H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.1 Hz, 1H), 4.70 (t, J = 5.6 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.13 (t, J = 5.7 Hz, 2H), 3.89 (t, J = 4.6 Hz, 2H), 3.27 (s, 3H), 2.75 (t , J = 6.2 Hz, 2H), 2.53 (t, J = 6.5 Hz, 2H), 2.14-2.13 (m, 2H) 1.27-1.26 (m, 1H), 0.99-0.97 (m, 4H) 6969 1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.1 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.1 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.89 (t, J = 4.4 Hz, 2H), 3.26 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.61 (t, J = 6.9 Hz, 1H), 2.53 (t, J = 7.0 Hz, 2H), 2.15 (quin, J = 6.4 Hz, 2H), 1.18 (d, J = 7.1 Hz, 6H). 1 H NMR (500 MHz, CDCl 3 ) δ 7.93 (d, J = 8.1 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.1 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.89 (t, J = 4.4 Hz, 2H), 3.26 (s, 3H), 2.76 (t , J = 6.2 Hz, 2H), 2.61 (t, J = 6.9 Hz, 1H), 2.53 (t, J = 7.0 Hz, 2H), 2.15 (quin, J = 6.4 Hz, 2H), 1.18 (d, J = 7.1 Hz, 6H). 7070 1H NMR (500 MHz, CDCl3) δ 7.92 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.48 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.7 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.26 (s, 3H), 2.75 (t, J = 6.1 Hz, 2H), 2.53 (t, J = 6.1 Hz, 2H), 2.15 (quin, J = 6.5 Hz, 2H), 1.20-2.06 (m, 9H). 1 H NMR (500 MHz, CDCl 3 ) δ 7.92 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.48 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.7 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.26 (s, 3H), 2.75 (t , J = 6.1 Hz, 2H), 2.53 (t, J = 6.1 Hz, 2H), 2.15 (quin, J = 6.5 Hz, 2H), 1.20-2.06 (m, 9H). 7171 1H NMR (300 MHz, CDCl3) δ 7.82 (d, 1H, J = 8.3 Hz), 7.68 (s, 2H), 7.36 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.53 (t, 2H), 3.23 (s, 3H), 2.75 (t, 2H), 2.50 (t, 2H), 2.18 (s, 3H), 2.14 (m, 2H), 2.08 (s, 3H) ; Mass : 461 1 H NMR (300 MHz, CDCl 3 ) δ 7.82 (d, 1H, J = 8.3 Hz), 7.68 (s, 2H), 7.36 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.53 (t, 2H), 3.23 (s, 3H), 2.75 (t, 2H), 2.50 (t, 2H), 2.18 (s, 3H), 2.14 (m, 2H), 2.08 (s, 3H); Mass: 461 7272 1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.1 Hz, 1H), 7.59-7.67 (m, 2H), 7.44 (d, J = 8.1 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.12 (m, 1H), 5.14 (d, J = 5.4 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.76 (t, J = 5.8 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 3H), 2.14 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.92 (d, J = 8.1 Hz, 1H), 7.59-7.67 (m, 2H), 7.44 (d, J = 8.1 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.12 (m, 1H), 5.14 (d, J = 5.4 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.76 (t, J = 5.8 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 3H), 2.14 (s, 3H) 7373 1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.3 Hz, 1H), 7.61-7.67 (m, 2H), 7.46 (d, J = 8.2 Hz, 1H), 6.15-6.25 (m, 1H), 5.99-6.12 (m, 1H), 5.14 (d, J = 5.3 Hz, 2H), 4.74 (d, J = 5.3 Hz, 2H), 3.24 (s, 3H), 2.75 (t, J = 6.0 Hz, 2H), 2.52 (t, J = 6.5 Hz, 2H), 2.07-2.18 (m, 2H), 1.53-1.60 (m, 1H), 0.94-1.03 (m, 4H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.92 (d, J = 8.3 Hz, 1H), 7.61-7.67 (m, 2H), 7.46 (d, J = 8.2 Hz, 1H), 6.15-6.25 (m, 1H), 5.99-6.12 (m, 1H), 5.14 (d, J = 5.3 Hz, 2H), 4.74 (d, J = 5.3 Hz, 2H), 3.24 (s, 3H), 2.75 (t, J = 6.0 Hz, 2H), 2.52 (t, J = 6.5 Hz, 2H), 2.07-2.18 (m, 2H), 1.53-1.60 (m, 1H), 0.94-1.03 (m, 4H) 7474 1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.2 Hz, 1H), 7.60-7.65 (m, 2H), 7.47 (d, J = 8.3 Hz, 1H), 6.15-6.26 (m, 1H), 5.99-6.10 (m, 1H), 5.14 (d, J = 6.0 Hz, 2H), 4.75 (d, J = 6.0 Hz, 2H), 3.23 (s, 3H), 2.73 (t, J = 6.0 Hz, 2H), 2.51 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 2H), 1.19 (s, 9H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.92 (d, J = 8.2 Hz, 1H), 7.60-7.65 (m, 2H), 7.47 (d, J = 8.3 Hz, 1H), 6.15-6.26 (m, 1H), 5.99-6.10 (m, 1H), 5.14 (d, J = 6.0 Hz, 2H), 4.75 (d, J = 6.0 Hz, 2H), 3.23 (s, 3H), 2.73 (t, J = 6.0 Hz, 2H), 2.51 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 2H), 1.19 (s, 9H) 7575 1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.2 Hz, 1H), 7.62-7.66 (m, 2H), 7.46 (d, J = 8.2 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.11 (m, 1H), 5.14 (d, J = 5.6 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.74 (t, J = 6.1 Hz, 2H), 2.55-2.65 (m, 1H), 2.52 (t, J = 6.3 Hz, 2H), 2.08-2.19 (m, 2H), 1.16 (d, J = 7.0 Hz, 6H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.92 (d, J = 8.2 Hz, 1H), 7.62-7.66 (m, 2H), 7.46 (d, J = 8.2 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.11 (m, 1H), 5.14 (d, J = 5.6 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.74 (t, J = 6.1 Hz, 2H), 2.55-2.65 (m, 1H), 2.52 (t, J = 6.3 Hz, 2H), 2.08-2.19 (m, 2H), 1.16 (d, J = 7.0 Hz, 6H) 7676 1H NMR (300 MHz, CDCl3) δ 7.80 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 7.26 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.52 (t, 2H), 3.21 (s, 3H), 3.03 (t, 1H), 2.99 (t, 1H), 2.30 (m, 1H), 2.19 (m, 2H), 2.13 (s, 3H), 2.11 (s, 3H), 2.10 (m, 1H), 1.74 (m, 2H) ; Mass : 487 1 H NMR (300 MHz, CDCl 3 ) δ 7.80 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 7.26 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.52 (t, 2H), 3.21 (s, 3H), 3.03 (t, 1H), 2.99 (t, 1H), 2.30 (m, 1H), 2.19 (m, 2H), 2.13 (s, 3H), 2.11 ( s, 3H), 2.10 (m, 1 H), 1.74 (m, 2H); Mass: 487 7777 1H NMR (300 MHz, CDCl3) δ 7.69 (s, 2H), 7.62 (d, 1H, J = 8.5 Hz), 7.31 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.53 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.17 (s, 3H), 2.15 (m, 2H), 2.08 (s, 3H) ; Mass : 428 1 H NMR (300 MHz, CDCl 3 ) δ 7.69 (s, 2H), 7.62 (d, 1H, J = 8.5 Hz), 7.31 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.53 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.17 (s, 3H), 2.15 (m, 2H), 2.08 (s, 3H); Mass: 428 7878 1H NMR (300 MHz, CDCl3) δ 7.97 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.13-6.25 (m, 1H), 6.01-6.13 (m, 1H), 5.30 (d, J = 6.2 Hz, 2H), 4.95 (d, J = 6.7 Hz, 2H), 3.29 (s, 3H), 2.79 (t, J = 6.0 Hz, 2H), 2.55 (t, J = 6.2 Hz, 2H), 2.09-2.23 (m, 5H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.97 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.13-6.25 (m, 1H), 6.01-6.13 (m, 1H), 5.30 (d, J = 6.2 Hz, 2H), 4.95 (d, J = 6.7 Hz, 2H), 3.29 (s, 3H), 2.79 (t, J = 6.0 Hz, 2H), 2.55 (t, J = 6.2 Hz, 2H), 2.09-2.23 (m, 5H) 7979 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.12-6.23 (m, 1H), 6.00-6.11 (m, 1H), 5.28 (d, J = 6.7 Hz, 2H), 4.93 (d, J = 6.9 Hz, 2H), 3.27 (s, 3H), 2.76 (t, J = 6.0 Hz, 2H), 2.56-2.67 (m, 1H), 2.53 (t, J = 6.2 Hz, 2H), 2.09-2.20 (m, 2H), 1.18 (d, J = 6.9 Hz, 6H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.12-6.23 (m, 1H), 6.00-6.11 (m, 1H), 5.28 (d, J = 6.7 Hz, 2H), 4.93 (d, J = 6.9 Hz, 2H), 3.27 (s, 3H), 2.76 (t, J = 6.0 Hz, 2H), 2.56-2.67 (m, 1H), 2.53 (t, J = 6.2 Hz, 2H), 2.09-2.20 (m, 2H), 1.18 (d, J = 6.9 Hz, 6H) 8080 1H NMR (300 MHz, CDCl3) δ 7.83 (d, 1H, J = 8.2 Hz), 7.64 (s, 2H), 7.35 (d, 1H, J = 8.2 Hz), 6.19 (m, 1H), 6.03 (m, 1H), 5.14 (d, 2H), 4.58 (d, 2H), 3.22 (s, 3H), 2.75 (t, 2H), 2.50 (t, 2H), 2.41 (s, 3H), 2.15 (m, 2H), 2.07 (s, 3H) ; Mass : 487 1 H NMR (300 MHz, CDCl 3 ) δ 7.83 (d, 1H, J = 8.2 Hz), 7.64 (s, 2H), 7.35 (d, 1H, J = 8.2 Hz), 6.19 (m, 1H), 6.03 (m, 1H), 5.14 (d, 2H), 4.58 (d, 2H), 3.22 (s, 3H), 2.75 (t, 2H), 2.50 (t, 2H), 2.41 (s, 3H), 2.15 ( m, 2H), 2.07 (s, 3H); Mass: 487 8181 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.0 Hz, 1H), 7.65-7.70 (m, 2H), 7.49 (d, J = 8.0 Hz, 1H), 5.36 (s, 2H), 4.95 (s, 2H), 3.29 (s, 3H), 2.78 (t, J = 6.3 Hz, 1H), 2.54 (d, J = 6.7 Hz, 1H), 2.17 (s, 3H), 2.13-2.18 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 8.0 Hz, 1H), 7.65-7.70 (m, 2H), 7.49 (d, J = 8.0 Hz, 1H), 5.36 (s, 2H) , 4.95 (s, 2H), 3.29 (s, 3H), 2.78 (t, J = 6.3 Hz, 1H), 2.54 (d, J = 6.7 Hz, 1H), 2.17 (s, 3H), 2.13-2.18 ( m, 2H) 8282 1H NMR (500 MHz, CDCl3) δ 7.66 (s, 2H), 7.60 (d, 1H, J = 8.4 Hz), 7.20 (d, 1H, J = 8.4 Hz), 4.87 (t, 2H), 4.50 (t, 2H), 3.03 (t, 1H), 3.01 (t, 1H), 2.10-2.31 (m, 4H), 2.11 (s, 3H), 2.10 (s, 3H), 1.75 (m, 2H) ; Mass : 454 1 H NMR (500 MHz, CDCl 3 ) δ 7.66 (s, 2H), 7.60 (d, 1H, J = 8.4 Hz), 7.20 (d, 1H, J = 8.4 Hz), 4.87 (t, 2H), 4.50 (t, 2H), 3.03 (t, 1H), 3.01 (t, 1H), 2.10-2.31 (m, 4H), 2.11 (s, 3H), 2.10 (s, 3H), 1.75 (m, 2H); Mass: 454 8383 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.40 (d, J = 8.2 Hz, 1H), 7.01 (dt, J = 50.9, 5.8 Hz, 1H), 5.07-4.95 (m, 2H), 3.20 (s, 3H), 3.10-3.01 (m, 2H), 2.23 (s, 3H), 2.21-2.13 (m, 4H), 1.84-1.72 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.40 (d, J = 8.2 Hz, 1H), 7.01 (dt, J = 50.9, 5.8 Hz, 1H), 5.07-4.95 (m, 2H), 3.20 (s, 3H), 3.10-3.01 (m, 2H), 2.23 (s, 3H), 2.21-2.13 (m, 4H), 1.84-1.72 (m, 2H) 8484 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.44 (d, J = 8.2 Hz, 1H), 7.02 (dt, J = 50.8, 5.9 Hz, 1H), 5.07-4.98 (m, 2H), 3.06-3.00 (m, 2H), 2.21-2.16 (m, 4H), 1.80-1.74 (m, 2H), 1.27 (s, 9H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.44 (d, J = 8.2 Hz, 1H), 7.02 (dt, J = 50.8, 5.9 Hz, 1H), 5.07-4.98 (m, 2H), 3.06-3.00 (m, 2H), 2.21-2.16 (m, 4H), 1.80-1.74 (m, 2H), 1.27 (s, 9H) 8585 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.86 (t, J = 6.5 Hz, 2H), 2.52 (t, J = 6.3 Hz, 2H), 2.15 (quin, J = 6.8 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz , 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.86 (t, J = 6.5 Hz, 2H), 2.52 (t, J = 6.3 Hz, 2H), 2.15 (quin , J = 6.8 Hz, 2H) 8686 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.3 Hz, 1H), 7.61 (s, 2H), 7.56 (d, J = 8.3 Hz, 1H), 4.58 (t, J = 7.0 Hz, 2H), 4.26 (t, J = 6.2 Hz, 2H), 3.24 (s, 3H), 2.89 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.26-2.16 (m, 4H), 1.93-1.88 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.3 Hz, 1H), 7.61 (s, 2H), 7.56 (d, J = 8.3 Hz, 1H), 4.58 (t, J = 7.0 Hz , 2H), 4.26 (t, J = 6.2 Hz, 2H), 3.24 (s, 3H), 2.89 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.26-2.16 (m, 4H), 1.93-1.88 (m, 2H) 8787 1H NMR (300 MHz, CDCl3) δ 8.20 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 4.60-4.66 (m, 4H), 3.16 (s, 3H), 2.92 (t, J = 6.1 Hz, 2H), 2.56 (t, J = 6.1 Hz, 2H), 2.16-2.33 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.20 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 4.60-4.66 (m, 4H) , 3.16 (s, 3H), 2.92 (t, J = 6.1 Hz, 2H), 2.56 (t, J = 6.1 Hz, 2H), 2.16-2.33 (m, 2H) 8888 1H NMR (500 MHz, CDCl3) δ 8.19 (s, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.61 (d, J = 8.2 Hz, 1H), 4.66 (t, J = 4.8 Hz, 2H), 4.62 (t, J = 4.5 Hz, 2H), 3.15 (s, 3H), 2.91 (t, J = 6.1 Hz, 2H), 2.56 (t, J = 7.0 Hz, 2H), 2.19 (quin, J = 6.4 Hz, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 8.19 (s, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.61 (d, J = 8.2 Hz, 1H), 4.66 (t, J = 4.8 Hz , 2H), 4.62 (t, J = 4.5 Hz, 2H), 3.15 (s, 3H), 2.91 (t, J = 6.1 Hz, 2H), 2.56 (t, J = 7.0 Hz, 2H), 2.19 (quin , J = 6.4 Hz, 2H) 8989 1H NMR (500 MHz, CDCl3) δ 8.39 (s, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.62 (d, J = 8.2 Hz, 1H), 4.75 (t, J = 4.8 Hz, 2H), 4.65 (t, J = 4.6 Hz, 2H), 3.12 (s, 3H), 2.90 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.18 (quin, J = 6.7 Hz, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 8.39 (s, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.62 (d, J = 8.2 Hz, 1H), 4.75 (t, J = 4.8 Hz , 2H), 4.65 (t, J = 4.6 Hz, 2H), 3.12 (s, 3H), 2.90 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.18 (quin , J = 6.7 Hz, 2H) 9090 1H NMR (300 MHz, CDCl3) δ 7.96 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 3.6 Hz, 2H), 7.60 (d, J = 8.2 Hz, 1H), 4.92 (t, J = 4.9 Hz, 2H), 4.66 (t, J = 4.9 Hz, 2H)), 3.10 (s, 3H), 2.89 (t, J = 6.0 Hz, 2H), 2.54 (t, J = 6.4 Hz, 2H), 2.18 (quin, J = 6.4 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.96 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 3.6 Hz, 2H), 7.60 (d, J = 8.2 Hz, 1H), 4.92 (t , J = 4.9 Hz, 2H), 4.66 (t, J = 4.9 Hz, 2H)), 3.10 (s, 3H), 2.89 (t, J = 6.0 Hz, 2H), 2.54 (t, J = 6.4 Hz, 2H), 2.18 (quin, J = 6.4 Hz, 2H) 9191 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.3 Hz, 1H), 7.62 (s, 2H), 7.57 (d, J = 8.3 Hz, 1H), 4.69 (t, J = 5.7 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.26 (S, 3H), 2.89 (t, J = 6.2 Hz, 2H), 2.55 (t, J = 6.5 Hz, 2H), 2.20-2.17 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.95 (d, J = 8.3 Hz, 1H), 7.62 (s, 2H), 7.57 (d, J = 8.3 Hz, 1H), 4.69 (t, J = 5.7 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.26 (S, 3H), 2.89 (t , J = 6.2 Hz, 2H), 2.55 (t, J = 6.5 Hz, 2H), 2.20-2.17 (m, 2H) 9292 1H NMR (500 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.68 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz, 2H), 4.70 (t, J = 4.9 Hz, 2H), 3.23-3.22 (m, 1H), 3.21 (s, 3H), 3.06-3.05 (m, 1H), 2.31-2.23 (m, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.94 (d, J = 8.2 Hz, 1H), 7.68 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz , 2H), 4.70 (t, J = 4.9 Hz, 2H), 3.23-3.22 (m, 1H), 3.21 (s, 3H), 3.06-3.05 (m, 1H), 2.31-2.23 (m, 6H) 9393 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.57 (d, J = 8.2 Hz, 1H), 4.75 (t, J = 7.1 Hz, 2H), 4.31 (t, J = 5.9 Hz, 2H), 3.27 (s, 3H), 2.89 (t, J = 6.0 Hz, 2H), 2.52 (m, 4H), 2.18 (quin, J = 6.4 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.95 (d, J = 8.2 Hz, 1H), 7.62 (s, 2H), 7.57 (d, J = 8.2 Hz, 1H), 4.75 (t, J = 7.1 Hz , 2H), 4.31 (t, J = 5.9 Hz, 2H), 3.27 (s, 3H), 2.89 (t, J = 6.0 Hz, 2H), 2.52 (m, 4H), 2.18 (quin, J = 6.4 Hz , 2H) 9494 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.35 (t, J = 4.6 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.27 (S, 3H), 3.24 (t, J = 4.8 Hz, 1H), 3.07 (t, J = 6.5 Hz, 1H), 2.34-1.95 (m, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.95 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.35 (t, J = 4.6 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.27 (S, 3H), 3.24 (t , J = 4.8 Hz, 1H), 3.07 (t, J = 6.5 Hz, 1H), 2.34-1.95 (m, 6H) 9595 1H NMR (300 MHz, CDCl3) δ 7.87 (d, 1H, J = 8.3 Hz), 7.71 (s, 2H), 7.39 (d, 1H, J = 8.3 Hz), 4.95 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.90 (t, 2H), 2.54 (t, 2H), 2.30 (s, 3H), 2.22 (m, 2H) ; Mass : 437.5 1 H NMR (300 MHz, CDCl 3 ) δ 7.87 (d, 1H, J = 8.3 Hz), 7.71 (s, 2H), 7.39 (d, 1H, J = 8.3 Hz), 4.95 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.90 (t, 2H), 2.54 (t, 2H), 2.30 (s, 3H), 2.22 (m, 2H); Mass: 437.5 9696 1H NMR (300 MHz, CDCl3) δ 7.84 (d, 1H, J = 8.3 Hz), 7.69 (s, 2H), 7.26 (d, 1H, J = 8.3 Hz), 4.93 (t, 2H), 4.54 (t, 2H), 3.24 (s, 3H), 3.21 (t, 1H), 3.06 (t, 1H), 2.32 (m, 1H), 2.25 (s, 3H), 2.23 (m, 1H), 2.06-2.17 (m, 2H), 1.77 (m, 2H) ; Mass : 463.5 1 H NMR (300 MHz, CDCl 3 ) δ 7.84 (d, 1H, J = 8.3 Hz), 7.69 (s, 2H), 7.26 (d, 1H, J = 8.3 Hz), 4.93 (t, 2H), 4.54 (t, 2H), 3.24 (s, 3H), 3.21 (t, 1H), 3.06 (t, 1H), 2.32 (m, 1H), 2.25 (s, 3H), 2.23 (m, 1H), 2.06- 2.17 (m, 2 H), 1.77 (m, 2 H); Mass: 463.5 9797 1H NMR (300 MHz, CDCl3) δ 7.69 (s, 2H), 7.63 (d, 1H, J = 8.5 Hz), 7.32 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.54 (t, 2H), 2.88 (t, 2H), 2.55 (t, 2H), 2.25 (s, 3H), 2.20 (m, 2H) ; Mass : 404.5 1 H NMR (300 MHz, CDCl 3 ) δ 7.69 (s, 2H), 7.63 (d, 1H, J = 8.5 Hz), 7.32 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.54 (t, 2H), 2.88 (t, 2H), 2.55 (t, 2H), 2.25 (s, 3H), 2.20 (m, 2H); Mass: 404.5 9898 1H NMR (300 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.2 Hz), 7.64 (s, 2H), 7.37 (d, 1H, J = 8.2 Hz), 6.21 (m, 1H), 6.03 (m, 1H), 5.15 (d, 2H), 4.59 (d, 2H), 3.23 (s, 3H), 2.88 (t, 2H), 2.54 (t, 2H), 2.52 (s, 3H), 2.19 (m, 2H) ; Mass : 463.5 1 H NMR (300 MHz, CDCl 3 ) δ 7.86 (d, 1H, J = 8.2 Hz), 7.64 (s, 2H), 7.37 (d, 1H, J = 8.2 Hz), 6.21 (m, 1H), 6.03 (m, 1H), 5.15 (d, 2H), 4.59 (d, 2H), 3.23 (s, 3H), 2.88 (t, 2H), 2.54 (t, 2H), 2.52 (s, 3H), 2.19 ( m, 2H); Mass: 463.5 9999 1H NMR (300 MHz, CDCl3) δ 7.99 (d, J = 8.3 Hz, 1H), 7.82 (s, 2H), 7.53 (d, J = 8.3 Hz, 1H), 7.11 (dt, J = 50.9, 5.9 Hz, 1H), 5.07-4.96 (m, 2H), 3.28-3.24 (m, 1H), 3.21 (s, 3H), 3.09-3.05 (m, 1H), 2.29-2.09 (m, 4H), 1.86-1.75 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.99 (d, J = 8.3 Hz, 1H), 7.82 (s, 2H), 7.53 (d, J = 8.3 Hz, 1H), 7.11 (dt, J = 50.9, 5.9 Hz, 1H), 5.07-4.96 (m, 2H), 3.28-3.24 (m, 1H), 3.21 (s, 3H), 3.09-3.05 (m, 1H), 2.29-2.09 (m, 4H), 1.86 -1.75 (m, 2H) 100100 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 7.9 Hz, 1H), 7.81 (d, J = 11.8 Hz, 2H), 7.52 (d, J = 7.9 Hz, 1H), 4.93 (d, J = 4.8 Hz, 2H), 4.67 (t, J = 4.8 Hz, 2H), 3.09 (s, 3H), 2.75 (t, J = 6.1 Hz, 2H), 2.53 (t, J = 6.6 Hz, 2H), 2.12-2.19 (m, 2H), 1.23 (s, 9H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 7.9 Hz, 1H), 7.81 (d, J = 11.8 Hz, 2H), 7.52 (d, J = 7.9 Hz, 1H), 4.93 (d , J = 4.8 Hz, 2H), 4.67 (t, J = 4.8 Hz, 2H), 3.09 (s, 3H), 2.75 (t, J = 6.1 Hz, 2H), 2.53 (t, J = 6.6 Hz, 2H ), 2.12-2.19 (m, 2H), 1.23 (s, 9H) 101101 1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 7.8 Hz, 1H), 7.79-7.87 (m, 1H), 7.67-7.76 (m, 1H), 7.47 (d, J = 7.8 Hz, 1H), 4.65 (t, J = 4.6 Hz, 2H), 4.39 (t, J = 3.7 Hz, 2H), 3.98 (t, J = 4.6 Hz, 2H), 3.90 (t, J = 3.7 Hz, 2H), 3.23 (s, 3H), 2.79 (t, J = 5.9 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.12-2.22 (m, 5H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.95 (d, J = 7.8 Hz, 1H), 7.79-7.87 (m, 1H), 7.67-7.76 (m, 1H), 7.47 (d, J = 7.8 Hz, 1H), 4.65 (t, J = 4.6 Hz, 2H), 4.39 (t, J = 3.7 Hz, 2H), 3.98 (t, J = 4.6 Hz, 2H), 3.90 (t, J = 3.7 Hz, 2H) , 3.23 (s, 3H), 2.79 (t, J = 5.9 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.12-2.22 (m, 5H) 102102 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.80-7.85 (m, 1H), 7.69-7.74 (m, 1H), 7.49 (d, J = 8.2 Hz, 1H), 4.66 (t, J = 4.9 Hz, 2H), 4.39 (t, J = 4.1 Hz, 2H), 3.98 (t, J = 4.9 Hz, 2H), 3.90 (t, J = 4.1 Hz, 2H), 3.23 (s, 3H), 2.78 (t, J = 6.2 Hz, 2H), 2.55 (t, J = 6.6 Hz, 2H), 2.12-2.19 (m, 2h), 1.59-1.67 (m, 1H), 0.98-1.05 (m, 4H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 8.2 Hz, 1H), 7.80-7.85 (m, 1H), 7.69-7.74 (m, 1H), 7.49 (d, J = 8.2 Hz, 1H), 4.66 (t, J = 4.9 Hz, 2H), 4.39 (t, J = 4.1 Hz, 2H), 3.98 (t, J = 4.9 Hz, 2H), 3.90 (t, J = 4.1 Hz, 2H) , 3.23 (s, 3H), 2.78 (t, J = 6.2 Hz, 2H), 2.55 (t, J = 6.6 Hz, 2H), 2.12-2.19 (m, 2h), 1.59-1.67 (m, 1H), 0.98-1.05 (m, 4H) 103103 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.5 Hz, 1H), 7.82-7.85 (m, 1H). 7.71-7.73 (m, 1H), 7.37 (d, J = 8.5 Hz, 1H), 4.65 (t, J = 4.7 Hz, 2H), 4.39 (t, J = 4.7 Hz, 2H), 3.98 (t, J = 4.7 Hz, 2H), 3.90 (t, J = 4.7 Hz, 2H), 3.23 (s, 3H), 3.07-3.11 (m, 1H), 3.02-3.06 (m, 1H), 2.31-2.36 (m, 1H), 2.14-2.26 (m, 6H), 1.74-1.85 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 8.5 Hz, 1H), 7.82-7.85 (m, 1H). 7.71-7.73 (m, 1H), 7.37 (d, J = 8.5 Hz, 1H), 4.65 (t, J = 4.7 Hz, 2H), 4.39 (t, J = 4.7 Hz, 2H), 3.98 (t, J = 4.7 Hz, 2H), 3.90 (t, J = 4.7 Hz, 2H), 3.23 (s, 3H), 3.07-3.11 (m, 1H), 3.02-3.06 (m, 1H), 2.31-2.36 (m, 1H), 2.14-2.26 (m, 6H), 1.74-1.85 (m, 2H) 104104 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.66-7.70 (m, 2H), 7.51 (d, J = 8.2 Hz, 1H), 5.36 (s, 2H), 4.94 (s, 2H), 2.76 (t, J = 6.1 Hz, 2H), 2.57-2.69 (m, 1H), 2.53 (t, J = 6.4 Hz, 2H), 2.10-2.20 (m, 2H), 1.19 (d, J = 6.9 Hz, 6H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.2 Hz, 1H), 7.66-7.70 (m, 2H), 7.51 (d, J = 8.2 Hz, 1H), 5.36 (s, 2H) , 4.94 (s, 2H), 2.76 (t, J = 6.1 Hz, 2H), 2.57-2.69 (m, 1H), 2.53 (t, J = 6.4 Hz, 2H), 2.10-2.20 (m, 2H), 1.19 (d, J = 6.9 Hz, 6H) 105105 1H NMR (300 MHz, CDCl3) δ 7.61 (d, 1H, J = 8.4 Hz), 7.60 (s, 2H), 7.32 (d, 1H, J = 8.4 Hz), 5.97-6.11 (m, 2H), 5.17 (d, 2H), 4.73 (d, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.49 (s, 3H), 2.15 (m, 2H), 2.09 (s, 3H) ; Mass : 454 1 H NMR (300 MHz, CDCl 3 ) δ 7.61 (d, 1H, J = 8.4 Hz), 7.60 (s, 2H), 7.32 (d, 1H, J = 8.4 Hz), 5.97-6.11 (m, 2H) , 5.17 (d, 2H), 4.73 (d, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.49 (s, 3H), 2.15 (m, 2H), 2.09 (s, 3H); Mass: 454 106106 1H NMR (300 MHz, CDCl3) δ 7.68 (s, 2H), 7.62 (d, 1H, J = 8.4 Hz), 7.32 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 (m, 1H), 5.13 (d, 2H), 4.54 (d, 2H), 2.77 (t, 2H), 2.53 (t, 2H), 2.45 (s, 3H), 2.14 (m, 2H), 2.09 (s, 3H) ; Mass : 454 1 H NMR (300 MHz, CDCl 3 ) δ 7.68 (s, 2H), 7.62 (d, 1H, J = 8.4 Hz), 7.32 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 (m, 1H), 5.13 (d, 2H), 4.54 (d, 2H), 2.77 (t, 2H), 2.53 (t, 2H), 2.45 (s, 3H), 2.14 (m, 2H), 2.09 ( s, 3H); Mass: 454 107107 1H NMR (300 MHz, CDCl3) δ 7.87 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.41 (d, 1H, J = 8.2 Hz), 6.18 (m, 1H), 6.06 (m, 1H), 5.27 (d, 2H), 4.79 (d, 2H), 3.28 (s, 3H), 2.79 (t, 2H), 2.54 (t, 2H), 2.48 (s, 3H), 2.18 (m, 2H), 2.11 (s, 3H) ; Mass : 487 1 H NMR (300 MHz, CDCl 3 ) δ 7.87 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.41 (d, 1H, J = 8.2 Hz), 6.18 (m, 1H), 6.06 (m, 1H), 5.27 (d, 2H), 4.79 (d, 2H), 3.28 (s, 3H), 2.79 (t, 2H), 2.54 (t, 2H), 2.48 (s, 3H), 2.18 ( m, 2H), 2.11 (s, 3H); Mass: 487 108108 1H NMR (300 MHz, CDCl3) δ 7.71 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 6.93 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 (m, 1H), 5.13 (d, 2H), 4.56 (d, 2H), 2.83 (t, 2H), 2.46 (t, 2H), 2.20 (s, 3H), 2.08 (m, 2H) ; Mass : 412 1 H NMR (300 MHz, CDCl 3 ) δ 7.71 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 6.93 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 (m, 1H), 5.13 (d, 2H), 4.56 (d, 2H), 2.83 (t, 2H), 2.46 (t, 2H), 2.20 (s, 3H), 2.08 (m, 2H); Mass: 412 109109 1H NMR (300 MHz, CDCl3) δ 7.90 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.43 (d, 1H, J = 8.2 Hz), 6.20 (m, 1H), 6.06 (m, 1H), 5.27 (d, 2H), 4.80 (d, 2H), 3.29 (s, 3H), 2.92 (t, 2H), 2.58 (s, 3H), 2.56 (t, 2H), 2.24 (m, 2H) ; Mass : 463.5 1 H NMR (300 MHz, CDCl 3 ) δ 7.90 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.43 (d, 1H, J = 8.2 Hz), 6.20 (m, 1H), 6.06 (m, 1H), 5.27 (d, 2H), 4.80 (d, 2H), 3.29 (s, 3H), 2.92 (t, 2H), 2.58 (s, 3H), 2.56 (t, 2H), 2.24 ( m, 2H); Mass: 463.5 110110 1H NMR (300 MHz, CDCl3) δ 7.71 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 6.93 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 (m, 1H), 5.13 (d, 2H), 4.56 (d, 2H), 2.83 (t, 2H), 2.46 (t, 2H), 2.20 (s, 3H), 2.08 (m, 2H) ; Mass : 412 1 H NMR (300 MHz, CDCl 3 ) δ 7.71 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 6.93 (d, 1H, J = 8.4 Hz), 6.15 (m, 1H), 5.95 (m, 1H), 5.13 (d, 2H), 4.56 (d, 2H), 2.83 (t, 2H), 2.46 (t, 2H), 2.20 (s, 3H), 2.08 (m, 2H); Mass: 412 111111 1H NMR (300 MHz, CDCl3) δ 7.65 (s, 2H), 7.61 (d, 1H, J = 8.4 Hz), 7.33 (d, 1H, J = 8.4 Hz), 6.14 (m, 1H), 5.95 (m, 1H), 5.14 (d, 2H), 4.55 (d, 2H), 2.90 (t, 2H), 2.56 (t, 2H), 2.54 (s, 3H), 2.21 (m, 2H) ; Mass : 430.5 1 H NMR (300 MHz, CDCl 3 ) δ 7.65 (s, 2H), 7.61 (d, 1H, J = 8.4 Hz), 7.33 (d, 1H, J = 8.4 Hz), 6.14 (m, 1H), 5.95 (m, 1H), 5.14 (d, 2H), 4.55 (d, 2H), 2.90 (t, 2H), 2.56 (t, 2H), 2.54 (s, 3H), 2.21 (m, 2H); Mass: 430.5 113113 1H NMR (300 MHz, CDCl3) δ 7.73 (d, 1H, J = 8.4 Hz), 7.72 (s, 2H), 6.97 (d, 1H, J = 8.4 Hz), 5.92 (s, 2H), 5.29 (s, 2H), 2.83 (t, 2H), 2.45 (t, 2H), 2.23 (s, 3H), 2.08 (m, 2H) ; Mass : 402 1 H NMR (300 MHz, CDCl 3 ) δ 7.73 (d, 1H, J = 8.4 Hz), 7.72 (s, 2H), 6.97 (d, 1H, J = 8.4 Hz), 5.92 (s, 2H), 5.29 (s, 2H), 2.83 (t, 2H), 2.45 (t, 2H), 2.23 (s, 3H), 2.08 (m, 2H); Mass: 402 114114 1H NMR (300 MHz, CDCl3) δ 7.88 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 7.02 (d, 1H, J = 8.4 Hz), 6.16 (m, 1H), 6.04 (m, 1H), 5.27 (d, 2H), 4.82 (d, 2H), 3.28 (s, 3H), 2.84 (t, 2H), 2.47 (t, 2H), 2.27 (s, 3H), 2.09 (m, 2H) ; Mass : 445 1 H NMR (300 MHz, CDCl 3 ) δ 7.88 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 7.02 (d, 1H, J = 8.4 Hz), 6.16 (m, 1H), 6.04 (m, 1H), 5.27 (d, 2H), 4.82 (d, 2H), 3.28 (s, 3H), 2.84 (t, 2H), 2.47 (t, 2H), 2.27 (s, 3H), 2.09 ( m, 2H); Mass: 445 115115 1H NMR (300 MHz, CDCl3) δ 7.90 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.43 (d, 1H, J = 8.2 Hz), 6.20 (m, 1H), 6.06 (m, 1H), 5.27 (d, 2H), 4.80 (d, 2H), 3.29 (s, 3H), 2.92 (t, 2H), 2.58 (s, 3H), 2.56 (t, 2H), 2.24 (m, 2H) ; Mass : 463.5 1 H NMR (300 MHz, CDCl 3 ) δ 7.90 (d, 1H, J = 8.3 Hz), 7.63 (s, 2H), 7.43 (d, 1H, J = 8.2 Hz), 6.20 (m, 1H), 6.06 (m, 1H), 5.27 (d, 2H), 4.80 (d, 2H), 3.29 (s, 3H), 2.92 (t, 2H), 2.58 (s, 3H), 2.56 (t, 2H), 2.24 ( m, 2H); Mass: 463.5 116116 1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 7.7 Hz, 1H), 7.78 (d, J = 7.7 Hz, 2H), 7.32 (d, J = 7.8 Hz, 1H), 4.91 (t, 2H), 4.66 (t, 2H), 3.09 (s, 3H), 2.52-1.99 (m, 6H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 7.7 Hz, 1H), 7.78 (d, J = 7.7 Hz, 2H), 7.32 (d, J = 7.8 Hz, 1H), 4.91 (t , 2H), 4.66 (t, 2H), 3.09 (s, 3H), 2.52-1.99 (m, 6H) 117117 1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.0 Hz, 1H), 7.68 (S, 2H), 7.31 (d, J = 8.4 Hz, 1H), 4.96 (t, 2H), 4.66 (t, 2H), 3.21 (s, 3H), 2.50-1.98 (m, 6H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.92 (d, J = 8.0 Hz, 1H), 7.68 (S, 2H), 7.31 (d, J = 8.4 Hz, 1H), 4.96 (t, 2H), 4.66 (t, 2H), 3.21 (s, 3H), 2.50-1.98 (m, 6H) 118118 1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.30 (d, J = 8.1 Hz, 1H), 4.74 (t, J = 7.1 Hz, 2H), 4.31 (t, J = 6.0 Hz, 2H), 3.26 (s, 3H), 2.61-1.95 (m, 8H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.30 (d, J = 8.1 Hz, 1H), 4.74 (t, J = 7.1 Hz , 2H), 4.31 (t, J = 6.0 Hz, 2H), 3.26 (s, 3H), 2.61-1.95 (m, 8H) 119119 1H NMR (500 MHz, CDCl3) δ 7.96 (d, J = 8.2 Hz, 1H), 7.63-7.60 (m, 3H), 4.76 (t, 2H), 4.32 (t, 2H), 3.28 (s, 3H), 2.59-2.56 (m, 8H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.96 (d, J = 8.2 Hz, 1H), 7.63-7.60 (m, 3H), 4.76 (t, 2H), 4.32 (t, 2H), 3.28 (s, 3H), 2.59-2.56 (m, 8H) 120120 1H NMR (300 MHz, CDCl3) δ 7.70 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 6.92 (d, 1H, J = 8.4 Hz), 4.66 (t, 2H), 4.13 (t, 2H), 4.08 (t, 2H), 3.79 (t, 2H), 2.84 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H) ; Mass : 430 1 H NMR (300 MHz, CDCl 3 ) δ 7.70 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 6.92 (d, 1H, J = 8.4 Hz), 4.66 (t, 2H), 4.13 (t, 2H), 4.08 (t, 2H), 3.79 (t, 2H), 2.84 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H); Mass: 430 121121 1H NMR (300 MHz, CDCl3) δ 7.60 (s, 2H), 7.57 (d, 1H, J = 8.3 Hz), 7.28 (d, 1H, J = 8.2 Hz), 4.64 (t, 2H), 4.07 (t, 2H), 4.06 (t, 2H), 3.76 (t, 2H), 2.74 (t, 2H), 2.51 (t, 2H), 2.40 (s, 3H), 2.15 (m, 2H), 2.06 (s, 3H) ; Mass : 472 1 H NMR (300 MHz, CDCl 3 ) δ 7.60 (s, 2H), 7.57 (d, 1H, J = 8.3 Hz), 7.28 (d, 1H, J = 8.2 Hz), 4.64 (t, 2H), 4.07 (t, 2H), 4.06 (t, 2H), 3.76 (t, 2H), 2.74 (t, 2H), 2.51 (t, 2H), 2.40 (s, 3H), 2.15 (m, 2H), 2.06 ( s, 3H); Mass: 472 122122 1H NMR (300 MHz, CDCl3) δ 7.61 (s, 2H), 7.58 (d, 1H, J = 8.3 Hz), 7.30 (d, 1H, J = 8.2 Hz), 4.64 (t, 2H), 4.09 (t, 2H), 4.06 (t, 2H), 3.76 (t, 2H), 2.87 (t, 2H), 2.55 (t, 2H), 2.49 (s, 3H), 2.20 (m, 2H) ; Mass : 448.5 1 H NMR (300 MHz, CDCl 3 ) δ 7.61 (s, 2H), 7.58 (d, 1H, J = 8.3 Hz), 7.30 (d, 1H, J = 8.2 Hz), 4.64 (t, 2H), 4.09 (t, 2H), 4.06 (t, 2H), 3.76 (t, 2H), 2.87 (t, 2H), 2.55 (t, 2H), 2.49 (s, 3H), 2.20 (m, 2H); Mass: 448.5 123123 1H NMR (300 MHz, CDCl3) δ 7.84 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.98 (d, 1H, J = 8.4 Hz), 4.69 (t, 2H), 4.20 (t, 2H), 4.12 (t, 2H), 3.84 (t, 2H), 3.26 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H) ; Mass : 463 1 H NMR (300 MHz, CDCl 3 ) δ 7.84 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.98 (d, 1H, J = 8.4 Hz), 4.69 (t, 2H), 4.20 (t, 2H), 4.12 (t, 2H), 3.84 (t, 2H), 3.26 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 ( m, 2H); Mass: 463 124124 1H NMR (300 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 7.38 (d, 1H, J = 8.4 Hz), 4.70 (t, 2H), 4.17 (t, 2H), 4.12 (t, 2H), 3.86 (t, 2H), 3.26 (s, 3H), 2.90 (t, 2H), 2.55 (t, 2H), 2.50 (s, 3H), 2.21 (m, 2H) ; Mass : 481.5 1 H NMR (300 MHz, CDCl 3 ) δ 7.86 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 7.38 (d, 1H, J = 8.4 Hz), 4.70 (t, 2H), 4.17 (t, 2H), 4.12 (t, 2H), 3.86 (t, 2H), 3.26 (s, 3H), 2.90 (t, 2H), 2.55 (t, 2H), 2.50 (s, 3H), 2.21 ( m, 2H); Mass: 481.5 125125 1H NMR (300 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 7.38 (d, 1H, J = 8.4 Hz), 4.70 (t, 2H), 4.17 (t, 2H), 4.12 (t, 2H), 3.86 (t, 2H), 3.26 (s, 3H), 2.90 (t, 2H), 2.55 (t, 2H), 2.50 (s, 3H), 2.21 (m, 2H) ; Mass : 481.5 1 H NMR (300 MHz, CDCl 3 ) δ 7.86 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 7.38 (d, 1H, J = 8.4 Hz), 4.70 (t, 2H), 4.17 (t, 2H), 4.12 (t, 2H), 3.86 (t, 2H), 3.26 (s, 3H), 2.90 (t, 2H), 2.55 (t, 2H), 2.50 (s, 3H), 2.21 ( m, 2H); Mass: 481.5 126126 1H NMR (300 MHz, CDCl3) δ 7.69 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.94 (d, 1H, J = 8.4 Hz), 5.08 (s, 2H), 4.69 (t, 2H), 4.28 (t, 2H), 2.83 (t, 2H), 2.45 (t, 2H), 2.17 (s, 3H), 2.08 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.69 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.94 (d, 1H, J = 8.4 Hz), 5.08 (s, 2H), 4.69 (t, 2H), 4.28 (t, 2H), 2.83 (t, 2H), 2.45 (t, 2H), 2.17 (s, 3H), 2.08 (m, 2H) 127127 1H NMR (300 MHz, CDCl3) δ 7.62 (s, 2H), 7.58 (d, 1H, J = 8.4 Hz), 7.32 (d, 1H, J = 8.4 Hz), 5.02 (s, 2H), 4.66 (t, 2H), 4.25 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.40 (s, 3H), 2.15 (m, 2H), 2.09 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.62 (s, 2H), 7.58 (d, 1H, J = 8.4 Hz), 7.32 (d, 1H, J = 8.4 Hz), 5.02 (s, 2H), 4.66 (t, 2H), 4.25 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.40 (s, 3H), 2.15 (m, 2H), 2.09 (s, 3H) 128128 1H NMR (300 MHz, CDCl3) δ 7.62 (s, 2H), 7.59 (d, 1H, J = 8.4 Hz), 7.33 (d, 1H, J = 8.4 Hz), 5.03 (s, 2H), 4.67 (t, 2H), 4.25 (t, 2H), 2.88 (t, 2H), 2.54 (t, 2H), 2.48 (s, 3H), 2.19 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.62 (s, 2H), 7.59 (d, 1H, J = 8.4 Hz), 7.33 (d, 1H, J = 8.4 Hz), 5.03 (s, 2H), 4.67 (t, 2H), 4.25 (t, 2H), 2.88 (t, 2H), 2.54 (t, 2H), 2.48 (s, 3H), 2.19 (m, 2H) 129129 1H NMR (300 MHz, CDCl3) δ 7.86 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 7.00 (d, 1H, J = 8.4 Hz), 5.19 (s, 2H), 4.74 (t, 2H), 4.38 (t, 2H), 3.24 (s, 3H), 2.83 (t, 2H), 2.45 (t, 2H), 2.17 (s, 3H), 2.09 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.86 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 7.00 (d, 1H, J = 8.4 Hz), 5.19 (s, 2H), 4.74 (t, 2H), 4.38 (t, 2H), 3.24 (s, 3H), 2.83 (t, 2H), 2.45 (t, 2H), 2.17 (s, 3H), 2.09 (m, 2H) 130130 1H NMR (300 MHz, CDCl3) δ 7.84 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 7.35 (d, 1H, J = 8.4 Hz), 5.15 (s, 2H), 4.74 (t, 2H), 4.40 (t, 2H), 3.22 (s, 3H), 2.76 (t, 2H), 2.52 (t, 2H), 2.39 (s, 3H), 2.17 (m, 2H), 2.09 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.84 (d, 1H, J = 8.4 Hz), 7.64 (s, 2H), 7.35 (d, 1H, J = 8.4 Hz), 5.15 (s, 2H), 4.74 (t, 2H), 4.40 (t, 2H), 3.22 (s, 3H), 2.76 (t, 2H), 2.52 (t, 2H), 2.39 (s, 3H), 2.17 (m, 2H), 2.09 ( s, 3 H) 131131 1H NMR (500 MHz, CDCl3) δ 7.88 (d, J = 8.0 Hz, 1H), 7.65-7.69 (m, 2H), 7.03 (d, J = 8.0 Hz, 1H), 5.80 (s, 3H), 5.36 (s, 3H), 3.34 (s, 3H), 2.84 (t, J = 6.4 Hz, 2H), 2.46 (t, J = 6.4 Hz, 2H), 2.32 (s, 3H), 2.06-2.13 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.88 (d, J = 8.0 Hz, 1H), 7.65-7.69 (m, 2H), 7.03 (d, J = 8.0 Hz, 1H), 5.80 (s, 3H) , 5.36 (s, 3H), 3.34 (s, 3H), 2.84 (t, J = 6.4 Hz, 2H), 2.46 (t, J = 6.4 Hz, 2H), 2.32 (s, 3H), 2.06-2.13 ( m, 2H) 132132 1H NMR (500 MHz, CDCl3) δ 7.87 (d, J = 8.3 Hz, 1H), 7.62-7.69 (m, 2H), 7.00 (d, J = 8.3 Hz, 1H), 4.72 (t, J = 6.7 Hz, 2H), 4.22 (t, J = 6.7 Hz, 2H), 3.29 (s, 3H), 3.22 (t, J = 6.7 Hz, 2H), 2.97 (t, J = 6.7 Hz, 2H), 2.84 (t, J = 6.3 Hz, 2H), 2.47 (t, J = 6.7 Hz, 2H), 2.24 (s, 3H), 2.06-2.13 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.87 (d, J = 8.3 Hz, 1H), 7.62-7.69 (m, 2H), 7.00 (d, J = 8.3 Hz, 1H), 4.72 (t, J = 6.7 Hz, 2H), 4.22 (t, J = 6.7 Hz, 2H), 3.29 (s, 3H), 3.22 (t, J = 6.7 Hz, 2H), 2.97 (t, J = 6.7 Hz, 2H), 2.84 (t, J = 6.3 Hz, 2H), 2.47 (t, J = 6.7 Hz, 2H), 2.24 (s, 3H), 2.06-2.13 (m, 2H) 133133 1H NMR (300 MHz, CDCl3) δ 8.02 (s, 1H), 7.86 (d, J = 8.1 Hz, 1H), 7.84 (s, 1H), 7.43 (d, J = 8.1 Hz, 1 Hz), 7.05 (dt, J = 5.7, 48.6 Hz, 1H), 4.81-4.74 (m, 2H), 3.07 (s, 3H), 2.90 (t, J = 6.2 Hz, 2H), 2.56 (s, 3H), 2.54 (t, J = 7.0 Hz, 2H), 2.24- 2.16 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.02 (s, 1H), 7.86 (d, J = 8.1 Hz, 1H), 7.84 (s, 1H), 7.43 (d, J = 8.1 Hz, 1 Hz), 7.05 (dt, J = 5.7, 48.6 Hz, 1H), 4.81-4.74 (m, 2H), 3.07 (s, 3H), 2.90 (t, J = 6.2 Hz, 2H), 2.56 (s, 3H), 2.54 (t, J = 7.0 Hz, 2H), 2.24- 2.16 (m, 2H) 134134 1H NMR (500 MHz, CDCl3) δ 7.84 (d, J = 8.0 Hz, 1H), 7.80 (s, 2H), 7.02 (d J = 7.9, 1H), 6.98 (dt, J = 5.6, 69.0 Hz, 1H), 4.86-4.82 (m, 2H), 3.19 (s, 3H), 3.16-3.11 (m, 2H), 2.24 (s, 3H), 2.09-2.05 (m, 2H), 1.38 (t, J = 7.0 Hz, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.84 (d, J = 8.0 Hz, 1H), 7.80 (s, 2H), 7.02 (d J = 7.9, 1H), 6.98 (dt, J = 5.6, 69.0 Hz , 1H), 4.86-4.82 (m, 2H), 3.19 (s, 3H), 3.16-3.11 (m, 2H), 2.24 (s, 3H), 2.09-2.05 (m, 2H), 1.38 (t, J = 7.0 Hz, 2H) 135135 1H NMR (500 MHz, CDCl3) δ 7.85 (d, J = 8.0 Hz, 1H), 7.80 (s, 2H), 7.02 (d, J = 7.5 Hz, 1H), 6.96 (dt, J = 6.4, 51 Hz, 1H), 4.86-4.82 (m, 2H), 3.19 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.44 (t, J = 6.7 Hz, 2H), 2.25 (s, 3H), 2.10-2.05 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.85 (d, J = 8.0 Hz, 1H), 7.80 (s, 2H), 7.02 (d, J = 7.5 Hz, 1H), 6.96 (dt, J = 6.4, 51 Hz, 1H), 4.86-4.82 (m, 2H), 3.19 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.44 (t, J = 6.7 Hz, 2H), 2.25 (s, 3H), 2.10-2.05 (m, 2H) 136136 1H NMR (500 MHz, CDCl3) δ 7.84 (d, J = 7.9 Hz, 1H), 7.81 (s, 2H), 7.40 (d, J = 7.9 Hz, 1H), 6.96 (dt, J = 6.1, 50.4 Hz, 1H), 4.85-4.81 (m, 2H), 3.19 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.51 (t, J = 6.4 Hz, 2H), 2.49 (s, 3H), 2.18-2.13 (m, 2H), 2.10 (s, 3H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.84 (d, J = 7.9 Hz, 1H), 7.81 (s, 2H), 7.40 (d, J = 7.9 Hz, 1H), 6.96 (dt, J = 6.1, 50.4 Hz, 1H), 4.85-4.81 (m, 2H), 3.19 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.51 (t, J = 6.4 Hz, 2H), 2.49 (s, 3H), 2.18-2.13 (m, 2H), 2.10 (s, 3H)

상기 표 1에서 구체화된 화합물들의 대표적인 합성방법을 예시하면 하기와 같다.Representative synthesis method of the compounds specified in Table 1 is as follows.

실시예 1. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 2)의 합성Example 1. 2- (3- (2- (2 H- 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydr Synthesis of Roxycyclohex-2-sen-1-one (Compound No. 2)

1)단계. 메틸 3-(2-브로모에톡시)-2,4-다이클로로벤조에이트Stage 1. Methyl 3- (2-bromoethoxy) -2,4-dichlorobenzoate

메틸 2,4-다이클로로-3-하이드록시벤조에이트 (90.48 mmol)를 아세톤 300 mL에 녹인 후, 1,2-다이브로모에탄 (452.4 mmol)과 탄산칼륨 (180.96 mmol)을 첨가하였다. 반응 혼합물을 60℃에서 6시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 에틸아세테이트, 물을 이용하여 추출하고 얻어진 유기층은 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 26 g (수율 88%)의 원하는 화합물을 얻을 수 있다. Methyl 2,4-dichloro-3-hydroxybenzoate (90.48 mmol) was dissolved in 300 mL of acetone, followed by addition of 1,2-dibromoethane (452.4 mmol) and potassium carbonate (180.96 mmol). The reaction mixture was stirred at 60 ° C. for at least 6 hours, and when the reaction was complete the solvent was concentrated under reduced pressure. The organic layer was extracted with ethyl acetate and water, dried over anhydrous magnesium sulfate, and the solvent was removed. Column chromatography can be used to yield 26 g (88% yield) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.55 (d, J = 8.5 Hz, 1H), 7.36 (d, J = 8.5 Hz, 1H), 4.33 (t, J = 6.8 Hz, 2H), 3.93 (s, 3H), 3.72 (t, J = 6.8 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.55 (d, J = 8.5 Hz, 1H), 7.36 (d, J = 8.5 Hz, 1H), 4.33 (t, J = 6.8 Hz, 2H), 3.93 (s , 3H), 3.72 (t, J = 6.8 Hz, 2H)

2)단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2,4-다이클로로벤조에이트Step 2). Methyl 3- (2- (2 H- 1, 1,2,3-triazol-2-yl) ethoxy) -2,4-dichlorobenzoate

상기에서 얻어진 메틸 3-(2-브로모에톡시)-2,4-다이클로로벤조에이트 (18 mmol)를 아세토나이트릴 90 mL에 녹인 후, 1H-1,2,3-트리아졸 (26 mmol), 탄산칼륨 (37 mmol), 테트라부틸암모늄 브롬화물 촉매량을 첨가하였다. 반응 혼합물을 85℃에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 에틸아세테이트, 물을 이용하여 추출하고 얻어진 유기층은 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 2.34 g (수율 42%)의 원하는 화합물을 얻을 수 있다. Methyl 3- (2-bromoethoxy) -2,4-dichlorobenzoate (18 mmol) obtained above was dissolved in 90 mL of acetonitrile, followed by 1 H -1, 1,2,3-triazole (26 mmol). ), Potassium carbonate (37 mmol) and tetrabutylammonium bromide catalyst amounts were added. The reaction mixture was stirred at 85 ° C. for at least 12 hours and the solvent was concentrated under reduced pressure at the end of the reaction. The organic layer was extracted with ethyl acetate and water, dried over anhydrous magnesium sulfate, and the solvent was removed. Column chromatography can be used to yield 2.34 g (yield 42%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.66 (s, 2H), 7.35 (d, J = 8.5 Hz, 1H), 7.32 (d, J = 8.5 Hz, 1H), 4.92 (t, J = 6.0 Hz, 2H), 4.51 (t, J = 6.0 Hz, 2H), 3.92 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.66 (s, 2H), 7.35 (d, J = 8.5 Hz, 1H), 7.32 (d, J = 8.5 Hz, 1H), 4.92 (t, J = 6.0 Hz , 2H), 4.51 (t, J = 6.0 Hz, 2H), 3.92 (s, 3H)

3)단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸싸이오)벤조에이트Step 3). Methyl 3- (2- (2 H- 1, 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylthio) benzoate

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2,4-다이클로로벤조에이트 (100 mmol)를 N,N-다이메틸포름아마이드 300 mL에 녹인 후, 나트륨싸이오메톡사이드 (130 mmol)를 첨가하였다. 반응 혼합물을 50℃에서 6시간 동안 교반시키고, 반응이 종결되면, 에틸아세테이트로 희석하였다. 유기층은 포화 소금물로 3번 세척한 후에 1N 염화수소 수용액으로 1번 세척하고, 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 22.6 g (수율 69%)의 원하는 화합물을 얻을 수 있다.Methyl 3- (2- (2H - 1, 1,2,3-triazol-2-yl) ethoxy) -2,4-dichlorobenzoate (100 mmol) obtained above was diluted with N, N -dimethylform. After dissolving in 300 mL of amide, sodium thiomethoxide (130 mmol) was added. The reaction mixture was stirred at 50 ° C. for 6 hours, and upon completion of the reaction, diluted with ethyl acetate. The organic layer was washed three times with saturated brine, and then washed once with 1N aqueous hydrogen chloride solution, dried over anhydrous magnesium sulfate, and the solvent was removed. Column chromatography can be used to yield 22.6 g (69% yield) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.66 (s, 2H), 7.60 (d, J = 8.5 Hz, 1H), 6.99(d, J = 8.5 Hz, 1H), 4.90 (t, J = 5.7 Hz, 2H), 4.49 (t, J = 5.7 Hz, 2H), 3.90 (s, 3H), 2.39 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.66 (s, 2H), 7.60 (d, J = 8.5 Hz, 1H), 6.99 (d, J = 8.5 Hz, 1H), 4.90 (t, J = 5.7 Hz , 2H), 4.49 (t, J = 5.7 Hz, 2H), 3.90 (s, 3H), 2.39 (s, 3H)

4)단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트Step 4). Methyl 3- (2- (2 H- 1, 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoate

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸싸이오)벤조에이트 (30 mmol)를 테트라하이드로퓨란 90 mL, 메탄올 90 mL, 물 180 mL에 녹인 후, 옥손 (66 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면, 감압 하에서 용매를 농축시켰다. 반응 혼합물을 에틸아세테이트로 희석하고, 염화나트륨 수용액으로 세척한 다음, 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 7.0 g (수율 65%)의 원하는 화합물을 얻을 수 있다.Obtained in the above-mentioned methyl 3- (2- (2 H- 1,2,3- triazol-2-yl) ethoxy) -2-chloro-4- (methylthio) benzoate (30 mmol) of tetrahydro- After dissolving in 90 mL of furan, 90 mL of methanol and 180 mL of water, oxone (66 mmol) was added. The reaction mixture was stirred at room temperature for at least 12 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. The reaction mixture was diluted with ethyl acetate, washed with aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and the solvent was removed. Column chromatography can be used to afford 7.0 g (65% yield) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (d, J = 8.2 Hz, 1H), 4.99 (t, J = 5.0 Hz, 2H), 4.74 (t, J = 5.0 Hz, 2H), 3.97 (s, 3H), 3.22 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (d, J = 8.2 Hz, 1H), 4.99 (t, J = 5.0 Hz, 2H), 4.74 (t , J = 5.0 Hz, 2H), 3.97 (s, 3H), 3.22 (s, 3H)

5)단계. 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조산 Step 5). 3- (2- (2H - 1, 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoic acid

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (10 mmol)를 테트라하이드로퓨란 30 mL, 물 30 mL에 녹인 후, 수산화나트륨 (15 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면, 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 얻어진 화합물 3.0 g (수율 95%)은 추가적인 정제 과정을 거치지 않고 다음 단계에 이용할 수 있다. Obtained in the above-mentioned methyl 3- (2- (2 H- 1,2,3- triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoate (10 mmol) of tetrahydro- After dissolving in 30 mL of furan and 30 mL of water, sodium hydroxide (15 mmol) was added. The reaction mixture was stirred at room temperature for at least 12 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. 1N aqueous hydrogen chloride solution was added and acid treated, followed by extraction three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. 3.0 g (95% yield) of the obtained compound can be used for the next step without further purification.

1H NMR (300 MHz, CDCl3) δ 7.84 (d, J = 8.1 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 4.95 (t, J = 5.0 Hz, 2H), 4.58 (t, J = 5.0 Hz, 2H), 3.26 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.84 (d, J = 8.1 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 4.95 (t, J = 5.0 Hz, 2H), 4.58 (t , J = 5.0 Hz, 2H), 3.26 (s, 3H)

6)단계. 3-옥소사이클로헥-1-센-1-일 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트 Step 6). 3-oxocyclohex-1-sen-1-yl 3- (2- (2 H- 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) Benzoate

상기에서 얻어진 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조산 (1.53 mmol)을 테트라하이드로퓨란 8 mL에 녹인 후, 2-클로로-1-메틸피리디움 요오드화물 (1.99 mmol), 1,3-사이클로헥사다이온 (1.84 mmol), 트리에틸아민 (4.13 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 반응 혼합물을 에틸아세테이트로 희석하고, 염화암모늄 수용액으로 2번 세척한 후에 1N 염화수소 수용액으로 1번 세척한 다음, 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.38 g (수율 61%)의 원하는 화합물을 얻을 수 있다.3- (2- (2H - 1, 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoic acid (1.53 mmol) obtained above was substituted with tetrahydrofuran 8 After dissolving in mL, 2-chloro-1-methylpyridium iodide (1.99 mmol), 1,3-cyclohexadione (1.84 mmol) and triethylamine (4.13 mmol) were added. The reaction mixture was stirred at room temperature for at least 12 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. The reaction mixture was diluted with ethyl acetate, washed twice with aqueous ammonium chloride solution, washed once with 1N aqueous hydrogen chloride solution, dried over anhydrous magnesium sulfate, and the solvent was removed. Column chromatography can be used to obtain 0.38 g (yield 61%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.96 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 6.04 (s, 1H), 4.97 (t, J = 4.8 Hz, 2H), 4.72 (t, J = 4.9 Hz, 2H), 3.21 (s, 3H), 2.66 (t, J = 6.2 Hz, 2H), 2.46 (t, J = 6.2 Hz, 2H), 2.13 (quin, J = 6.4 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.96 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 6.04 (s, 1H), 4.97 (t, J = 4.8 Hz, 2H), 4.72 (t, J = 4.9 Hz, 2H), 3.21 (s, 3H), 2.66 (t, J = 6.2 Hz, 2H), 2.46 (t, J = 6.2 Hz , 2H), 2.13 (quin, J = 6.4 Hz, 2H)

7)단계. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 Step 7). 2- (3- (2- (2H - 1, 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one

상기에서 얻어진 3-옥소사이클로헥-1-센-1-일 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (1.47 mmol)를 아세토나이트릴 7 mL에 녹인 후, 아세톤 시아노하이드린 3방울, 트리에틸아민 (2.50 mmol), 시안화칼륨 (2.21 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.50 g (수율 84%)의 원하는 화합물을 얻을 수 있다.3-oxo-cyclopenten-1-hexyl obtained in the metallocene-1-yl (ethoxy-2- (2 H- 1,2,3- triazol-2-yl)) 3 2-chloro-4- (methyl Sulfonyl) benzoate (1.47 mmol) was dissolved in 7 mL of acetonitrile, and then 3 drops of acetone cyanohydrin, triethylamine (2.50 mmol) and potassium cyanide (2.21 mmol) were added. The reaction mixture was stirred at room temperature for at least 12 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. 1N aqueous hydrogen chloride solution was added for acid treatment and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can be used to yield 0.50 g (84% yield) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz, 2H), 4.68 (t, J = 4.8 Hz, 2H), 3.25 (s, 3H), 2.81-2.79 (m, 2H), 2.42-2.40 (m, 2H), 2.07 (quin, J = 6.5 Hz, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.80 (d, J = 8.0 Hz, 1H), 7.68 (s, 2H), 7.07 (d, J = 8.0 Hz, 1H), 4.98 (t, J = 4.8 Hz , 2H), 4.68 (t, J = 4.8 Hz, 2H), 3.25 (s, 3H), 2.81-2.79 (m, 2H), 2.42-2.40 (m, 2H), 2.07 (quin, J = 6.5 Hz, 2H)

실시예 2. 2-(3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 4)의 합성Example 2. 2- (3- (4- (2H - 1, 1,2,3-triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydro Synthesis of Roxycyclohex-2-sen-1-one (Compound No. 4)

3-옥소사이클로헥-1-센-1-일 3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (0.58 mmol)를 아세토나이트릴 3 mL에 녹인 후, 아세톤 시아노하이드린 2 방울, 트리에틸아민 (0.99 mmol), 시안화칼륨 (0.87 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.20 g (수율 73%)의 원하는 화합물을 얻을 수 있다.3-oxocyclohex-1-sen-1-yl 3- (4- (2 H- 1,2,3-triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) Benzoate (0.58 mmol) was dissolved in 3 mL of acetonitrile, and then 2 drops of acetone cyanohydrin, triethylamine (0.99 mmol) and potassium cyanide (0.87 mmol) were added. The reaction mixture was stirred at room temperature for at least 12 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. 1N aqueous hydrogen chloride solution was added for acid treatment and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can be used to yield 0.20 g (73% yield) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 7.5 Hz, 1H), 7.63 (s, 2H), 7.09 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 6.8 Hz, 2H), 4.30 (t, J = 6.2 Hz, 2H), 3.27 (s, 3H), 2.83 (t, 2H), 2.47 (t, 2H), 2.24 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 7.5 Hz, 2H), 1.94-1.90 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.95 (d, J = 7.5 Hz, 1H), 7.63 (s, 2H), 7.09 (d, J = 8.1 Hz, 1H), 4.60 (t, J = 6.8 Hz , 2H), 4.30 (t, J = 6.2 Hz, 2H), 3.27 (s, 3H), 2.83 (t, 2H), 2.47 (t, 2H), 2.24 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 7.5 Hz, 2H), 1.94-1.90 (m, 2H)

실시예 3. 2-(3-(4-(1H-1,2,3-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 9)의 합성Example 3. 2- (3- (4- (1 H -1, 1,2,3-triazol - 1-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydro Synthesis of Roxycyclohex-2-sen-1-one (Compound No. 9)

3-옥소사이클로헥-1-센-1-일 3-(4-(1H-1,2,3-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (0.63 mmol)를 아세토나이트릴 3 mL에 녹인 후, 아세톤 시아노하이드린 2방울, 트리에틸아민 (1.07 mmol), 시안화칼륨 (0.95 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.22 g (수율 73%)의 원하는 화합물을 얻을 수 있다.3-oxocyclohex-1-sen-1-yl 3- (4- (1 H- 1,2,3-triazol - 1-yl) butoxy) -2-chloro-4- (methylsulfonyl) Benzoate (0.63 mmol) was dissolved in 3 mL of acetonitrile, and then 2 drops of acetone cyanohydrin, triethylamine (1.07 mmol) and potassium cyanide (0.95 mmol) were added. The reaction mixture was stirred at room temperature for at least 12 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. 1N aqueous hydrogen chloride solution was added for acid treatment and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can be used to yield 0.22 g (73% yield) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.96 (d, J = 8.1 Hz, 1H), 7.76 (s, 1H), 7.64 (s, 1H), 7.11 (d, J = 8.1 Hz, 1H), 4.54 (t, J = 7.5 Hz, 2H), 4.30 (t, J = 6.0 Hz, 2H), 3.25 (s, 3H), 2.85 (t, J = 6.0 HZ, 2H), 2.47 (t, J = 7.5 Hz, 2H), 2.22 (t, J = 6.5 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.97-1.93 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.96 (d, J = 8.1 Hz, 1H), 7.76 (s, 1H), 7.64 (s, 1H), 7.11 (d, J = 8.1 Hz, 1H), 4.54 (t, J = 7.5 Hz, 2H), 4.30 (t, J = 6.0 Hz, 2H), 3.25 (s, 3H), 2.85 (t, J = 6.0 HZ, 2H), 2.47 (t, J = 7.5 Hz , 2H), 2.22 (t, J = 6.5 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.97-1.93 (m, 2H)

실시예 4. 2-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온(화합물번호 12)의 합성Example 4. 2- (3- (2- (1 H -1, 1,2,4 - triazol-1 - yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydro Synthesis of Roxycyclohex-2-sen-1-one (Compound No. 12)

3-옥소사이클로헥-1-센-1-일 3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (0.52 mmol)를 아세토나이트릴 3 mL에 녹인 후, 아세톤 시아노하이드린 2방울, 트리에틸아민 (0.88 mmol), 시안화칼륨 (0.78 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.17 g (수율 80%)의 원하는 화합물을 얻을 수 있다. 3-oxocyclohex-1-sen-1-yl 3- (2- (1H-1, 1,2,4 - triazol-1 - yl) ethoxy) -2-chloro-4- (methylsulfonyl) Benzoate (0.52 mmol) was dissolved in 3 mL of acetonitrile, and then 2 drops of acetone cyanohydrin, triethylamine (0.88 mmol) and potassium cyanide (0.78 mmol) were added. The reaction mixture was stirred at room temperature for at least 12 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. 1N aqueous hydrogen chloride solution was added for acid treatment and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can be used to yield 0.17 g (yield 80%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 (m, 2H), 2.04 (t, J = 6.5 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.36 (s, 1H), 7.98 (s, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 4.61 (t, J = 4.7 Hz, 2H), 4.36 (t, J = 4.9 Hz, 2H), 3.26 (s, 3H), 2.83-2.69 (m, 2H), 2.58-2.35 (m, 2H), 2.04 ( t, J = 6.5 Hz, 2H)

실시예 5. 2-(3-(4-(1H-1,2,4-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 14)의 합성Example 5. 2- (3- (4- (1H-1, 1,2,4 - triazol-1 - yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydro Synthesis of Roxycyclohex-2-sen-1-one (Compound No. 14)

3-옥소사이클로헥-1-센-1-일 3-(4-(1H-1,2,4-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (0.33 mmol)를 아세토나이트릴 2 mL에 녹인 후, 아세톤 시아노하이드린 1방울, 트리에틸아민 (0.57 mmol), 시안화칼륨 (0.50 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.11 g (수율 70%)의 원하는 화합물을 얻을 수 있다. 3-oxocyclohex-1-sen-1-yl 3- (4- (1H-1, 1,2,4 - triazol-1 - yl) butoxy) -2-chloro-4- (methylsulfonyl) Benzoate (0.33 mmol) was dissolved in 2 mL of acetonitrile, and then 1 drop of acetone cyanohydrin, triethylamine (0.57 mmol) and potassium cyanide (0.50 mmol) were added. The reaction mixture was stirred at room temperature for at least 12 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. 1N aqueous hydrogen chloride solution was added for acid treatment and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can be used to obtain 0.11 g (yield 70%) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 8.18 (s, 1H), 8.00 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H), 4.34-4.29 (m, 4H), 3.26 (s, 3H), 2.85 (t, J = 6.0 Hz, 2H), 2.47 (t, J = 6.0 Hz, 2H), 2.19 (t, J = 7.0 Hz, 2H), 2.10 (t, J = 6.5 Hz, 2H), 1.95-1.91 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 8.18 (s, 1H), 8.00 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H), 4.34 -4.29 (m, 4H), 3.26 (s, 3H), 2.85 (t, J = 6.0 Hz, 2H), 2.47 (t, J = 6.0 Hz, 2H), 2.19 (t, J = 7.0 Hz, 2H) , 2.10 (t, J = 6.5 Hz, 2H), 1.95-1.91 (m, 2H)

실시예 6. 3-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 27)의 합성Example 6. 3- (3- (2- (1 H -1, 1,2,4 - triazol-1 - yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4-hydro Synthesis of Roxybicyclo [3.2.1] octa-3-ten-2-one (Compound No. 27)

4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트 (1.60 mmol)를 아세토나이트릴 8 mL에 녹인 후, 아세톤 시아노하이드린 5방울, 트리에틸아민 (2.72 mmol), 시안화칼륨 (2.4 mmol)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/디클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 0.66 g (수율 92%)의 원하는 화합물을 얻을 수 있다.4-oxobicyclo [3.2.1] oc-2-ten-2-yl 3- (2- (1H-1, 1,2,4 - triazol-1 - yl) ethoxy) -2-chloro-4 -(Methylsulfonyl) benzoate (1.60 mmol) was dissolved in 8 mL of acetonitrile, and then 5 drops of acetone cyanohydrin, triethylamine (2.72 mmol) and potassium cyanide (2.4 mmol) were added. The reaction mixture was stirred at room temperature for at least 12 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. 1N aqueous hydrogen chloride solution was added for acid treatment and then extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can give 0.66 g (92% yield) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.78 (t, J = 7.1 Hz, 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42-3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H), 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 8.27 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.0 Hz, 1H), 4.78 (t, J = 7.1 Hz, 2H), 4.35 (t, J = 6.5 Hz, 2H), 3.42-3.28 (m, 3H), 3.28 (s, 3H), 3.16 (t, J = 6.0 Hz, 1H) , 2.64-2.55 (m, 1H), 1.92-1.80 (m, 1H), 1.67-1.60 (m, 2H)

실시예 7. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 41)의 합성Example 7. 2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-hydro Synthesis of Roxycyclohex-2-sen-1-one (Compound No. 41)

1) 단계. 메틸-3-하이드록시-2-메틸-4-나이트로벤조에이트Stage 1. Methyl-3-hydroxy-2-methyl-4-nitrobenzoate

메틸 3-하이드록시-2-메틸벤조에이트 (50 g, 0.301 mole)을 에틸아세테이트 50 mL과 아세트산 200 mL에 녹이고, 질산 (24.4 mL, 0.331 mmol)을 10분에 걸쳐서 천천히 적가하고, 상온에서 1시간 동안 교반하였다. 반응용액을 물 1 L에 희석하고 에틸 아세테이트로 추출하면서 물로 2회 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (다이클로로메탄/n-헥산 = 1/1) 로 정제하여 노란색 고체상태의 목적화합물 31 g (48% 수율)을 얻었다.Methyl 3-hydroxy-2-methylbenzoate (50 g, 0.301 mole) is dissolved in 50 mL of ethyl acetate and 200 mL of acetic acid, nitric acid (24.4 mL, 0.331 mmol) is slowly added dropwise over 10 minutes, and at room temperature, 1 Stir for hours. The reaction solution was diluted with 1 L of water and washed twice with water, extracted with ethyl acetate. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography (dichloromethane / n -hexane = 1/1) to obtain 31 g (48% yield) of the title compound as a yellow solid.

1H NMR (300 MHz, CDCl3) δ 11.08 (s, OH), 8.02 (d, 1H, J = 8.8 Hz), 7.36 (d, 1H, J = 8.8 Hz), 3.97 (s, 3H), 2.54 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 11.08 (s, OH), 8.02 (d, 1H, J = 8.8 Hz), 7.36 (d, 1H, J = 8.8 Hz), 3.97 (s, 3H), 2.54 (s, 3H)

2)단계. 메틸 3-(2-브로모에톡시)-2-메틸벤조에이트Step 2). Methyl 3- (2-bromoethoxy) -2-methylbenzoate

상기에서 얻어진 메틸-3-하이드록시-2-메틸-4-나이트로벤조에이트 (3.0 g, 14.21 mmol)을 다이메틸포름아마이드 30 mL에 녹이고 탄산칼륨 (5.9 g, 42.6 mmol) 과 다이브로모에탄 (3.7 mL, 42.6 mmol)을 첨가한 후 60 ℃에서 3시간동안 교반하였다. 반응용액을 물로 희석시키고 에틸 아세테이트 150 mL로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 5/1)로 정제하여 무색 오일상태의 목적화합물 3.67 g (81% 수율)을 얻었다.Methyl-3-hydroxy-2-methyl-4-nitrobenzoate (3.0 g, 14.21 mmol) obtained above was dissolved in 30 mL of dimethylformamide, potassium carbonate (5.9 g, 42.6 mmol) and dibromoethane ( 3.7 mL, 42.6 mmol) was added and stirred at 60 ° C. for 3 hours. The reaction solution was diluted with water and extracted with 150 mL of ethyl acetate and washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography ( n -hexane / ethyl acetate = 5/1) to obtain 3.67 g (81% yield) of the title compound as a colorless oil.

1H NMR (300 MHz, CDCl3) : δ 7.72 (d, 1H, J = 8.8 Hz), 7.65 (d, 1H, J = 8.8 Hz), 4.31 (t, 2H), 3.95 (s, 3H), 3.70 (t, 2H), 2.60 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) : δ 7.72 (d, 1H, J = 8.8 Hz), 7.65 (d, 1H, J = 8.8 Hz), 4.31 (t, 2H), 3.95 (s, 3H), 3.70 (t, 2H), 2.60 (s, 3H)

3)단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-나이트로벤조에이트Step 3). Methyl 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4-nitrobenzoate

상기에서 얻어진 메틸 3-(2-브로모에톡시)-2-메틸벤조에이트 3.0 g (9.43 mmol)을 N,N-다이메틸포름아마이드 30 mL에 녹이고 1H-1,2,3-트리아졸 (0.98 g, 14.14 mmol), 탄산칼륨 (3.91 g, 28.29 mmol) 그리고 테트라부틸암모늄 브롬화물 (0.3 g, 0.94 mmol)을 차례로 첨가한 후 60 ℃에서 3시간동안 교반하였다. 반응용액을 물로 희석시키고 에틸 아세테이트 150 mL로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 3/1) 로 정제하여 N-2 위치가 치환된 고체상태의 목적화합물 1.8 g (62% 수율)과 N-1 위치가 치환된 고체상태의 화합물 1.15 g (39% 수율)을 얻었다.3.0 g (9.43 mmol) of methyl 3- (2-bromoethoxy) -2-methylbenzoate obtained above were dissolved in 30 mL of N, N -dimethylformamide, and 1 H -1,2,3-triazole ( 0.98 g, 14.14 mmol), potassium carbonate (3.91 g, 28.29 mmol) and tetrabutylammonium bromide (0.3 g, 0.94 mmol) were added sequentially and stirred at 60 ° C. for 3 hours. The reaction solution was diluted with water and extracted with 150 mL of ethyl acetate and washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography ( n -hexane / ethyl acetate = 3/1) to obtain 1.8 g (62% yield) of the target compound in the solid state of which the N-2 position was substituted and the solid of which the N-1 position was substituted. Obtained 1.15 g (39% yield) of the compound in the state.

N-2 위치가 치환된 화합물 : 1H NMR (300 MHz, CDCl3) δ 7.69 (d, 1H, J = 8.8 Hz), 7.68 (s, 2H), 7.63 (d, 1H, J = 8.8 Hz), 4.89 (t, 2H), 4.51 (s, 2H), 3.92 (s, 3H), 2.25 (s, 3H)Compound substituted with N-2 position: 1 H NMR (300 MHz, CDCl 3 ) δ 7.69 (d, 1H, J = 8.8 Hz), 7.68 (s, 2H), 7.63 (d, 1H, J = 8.8 Hz) , 4.89 (t, 2H), 4.51 (s, 2H), 3.92 (s, 3H), 2.25 (s, 3H)

N-1 위치가 치환된 화합물 : 1H NMR (300 MHz, CDCl3) δ 7.76 (m, 2H), 7.71 (d, 1H, J = 8.8 Hz), 7.64 (d, 1H, J = 8.8 Hz), 4.84 (t, 2H), 4.42 (s, 2H), 3.92 (s, 3H), 2.22 (s, 3H) Compound substituted with N-1 position: 1 H NMR (300 MHz, CDCl 3 ) δ 7.76 (m, 2H), 7.71 (d, 1H, J = 8.8 Hz), 7.64 (d, 1H, J = 8.8 Hz) , 4.84 (t, 2H), 4.42 (s, 2H), 3.92 (s, 3H), 2.22 (s, 3H)

4)단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸싸이오)벤조에이트Step 4). Methyl 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylthio) benzoate

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-나이트로벤조에이트 1.65 g (5.39 mmol)을 N,N-다이메틸포름아마이드 25 mL에 녹이고 나트륨 싸이오메톡사이드 (0.76 g, 10.78 mmol)을 5분에 걸쳐 천천히 가해주고 상온에서 3시간동안 교반하였다. 반응용액을 물로 희석시키고 에틸 아세테이트 150 mL로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 3/1) 로 정제하여 고체상태의 목적화합물 1.36 g (82% 수율)을 얻었다.1.65 g (5.39 mmol) of methyl 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4-nitrobenzoate obtained above was added to N, N- Dissolve in 25 mL of dimethylformamide and add sodium thiomethoxide (0.76 g, 10.78 mmol) slowly over 5 minutes and stir for 3 hours at room temperature The reaction solution was diluted with water and extracted with 150 mL of ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by evaporation under reduced pressure.The obtained residue was purified by silica gel column chromatography ( n -hexane / ethyl acetate = 3/1) to obtain a solid state. 1.36 g (82% yield) of the target compound were obtained.

1H NMR (300 MHz, CDCl3) δ 7.67 (d, 1H, J = 8.4 Hz), 7.66 (s, 2H), 6.95 (d, 1H, J = 8.4 Hz), 4.88 (t, 2H), 4.33 (t, 2H), 3.84 (s, 3H), 2.39 (s, 3H), 2.30 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.67 (d, 1H, J = 8.4 Hz), 7.66 (s, 2H), 6.95 (d, 1H, J = 8.4 Hz), 4.88 (t, 2H), 4.33 (t, 2H), 3.84 (s, 3H), 2.39 (s, 3H), 2.30 (s, 3H)

5) 단계. 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조에이트5) step. Methyl 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoate

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸싸이오)벤조에이트 (1.36 g, 4.43 mmol)를 메탄올/테트라하이드로퓨란/물 (1/1/1)로 희석된 혼합용매 60 mL에 녹이고 옥손 10.8 g (17.72 mmol)을 가한 후 상온에서 16시간동안 교반하였다. 녹지 않는 고체는 에틸아세테이트로 세척하면서 여과하여 제거하고, 여액은 물로 희석시키고 에틸 아세테이트 150 mL로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 2/1) 로 정제하여 고체상태의 목적화합물 1.50 g (98% 수율)을 얻었다.Methyl 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylthio) benzoate (1.36 g, 4.43 mmol) obtained above was added to Dissolve in 60 mL of a mixed solvent diluted with methanol / tetrahydrofuran / water (1/1/1), add 10.8 g (17.72 mmol) of oxone, and stir for 16 hours at room temperature. The resulting filtrate was diluted with water, washed with water and brine, extracted with 150 mL of ethyl acetate, and the extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. Purification by chromatography ( n -hexane / ethyl acetate = 2/1) gave 1.50 g (98% yield) of the title compound in the solid state.

1H NMR (300 MHz, CDCl3) δ 7.85 (d, 1H, J = 8.8 Hz), 7.73 (d, 1H, J = 8.8 Hz), 7.68 (s, 2H), 4.92 (t, 2H), 4.52 (t, 2H), 3.91 (s, 3H), 3.22 (s, 3H), 2.26 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.85 (d, 1H, J = 8.8 Hz), 7.73 (d, 1H, J = 8.8 Hz), 7.68 (s, 2H), 4.92 (t, 2H), 4.52 (t, 2H), 3.91 (s, 3H), 3.22 (s, 3H), 2.26 (s, 3H)

6)단계. 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조산Step 6). 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoic acid

상기에서 얻어진 메틸 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조에이트 1.52 g (4.48 mmol)을 메탄올 20 mL과 테트라하이드로퓨란 10 mL에 녹이고 2N-NaOH (6.7 mL, 13.5 mmol)을 첨가한 후 상온에서 3시간동안 교반하였다. 반응이 완결되면 물로 희석하고 1N-HCl을 가하여 pH 3~4 정도의 산성용액이 되게 한 다음 에틸 아세테이트로 추출(100 mL x 2)하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 감압 하에 건조시켜 고체상태의 목적화합물 1.37 g (94% 수율)을 얻었다.1.52 g (4.48 mmol) of methyl 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoate obtained above was methanol Dissolve in 20 mL and 10 mL tetrahydrofuran, add 2N-NaOH (6.7 mL, 13.5 mmol), and stir at room temperature for 3 hours.When the reaction is complete, dilute with water and add 1N-HCl to pH 3-4. After acidic solution was extracted with ethyl acetate (100 mL x 2) and washed with water and brine The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. 1.37 g (94% yield) of the target compound in the solid state was obtained.

1H NMR (300 MHz, CDCl3) δ 7.90 (m, 2H), 7.70 (s, 2H), 4.95 (t, 2H), 4.55 (t, 2H), 3.25 (s, 3H), 2.32 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.90 (m, 2H), 7.70 (s, 2H), 4.95 (t, 2H), 4.55 (t, 2H), 3.25 (s, 3H), 2.32 (s, 3H)

7)단계. 3-옥소사이클로헥-1-센-1-일 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조에이트 Step 7). 3-oxocyclohex-1-sen-1-yl 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzo Eight

상기에서 얻어진 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조산 300 mg(0.92 mmol)을 다이클로로메탄 10 mL에 녹이고 옥살릴 클로라이드 (0.23 mL, 2.77 mmol) 을 첨가하고 DMF 2 방울을 가한 후 상온에서 1시간 동안 교반하였다. 이어서 반응용액을 감압 하에 농축시켜 용매를 제거하고 건조시켰다. 또 다른 반응용기에 사이클로헥사다이온 155 mg (1.38 mmol)을 취하여 다이클로로메탄 20 mL에 녹이고 트리에틸아민 (0.38 mL, 2.77 mmol)을 첨가하고 얼음물 수조를 이용하여 냉각 시켰다. 이어서 앞에서 얻은 acid chloride 화합물을 다이클로로메탄 10 mL에 녹여서 천천히 적가하고 상온에서 1시간 동안 교반하였다. 반응이 완결되면 반응용액을 물로 희석시키고 에틸 아세테이트 (100 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 1/1)로 정제하여 오일상태의 목적화합물 370 mg (95% 수율)을 얻었다.300 mg (0.92 mmol) of 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoic acid obtained above was diluted with dichloromethane. Dissolve in 10 mL, add oxalyl chloride (0.23 mL, 2.77 mmol), add 2 drops of DMF, and stir at room temperature for 1 hour, then concentrate the reaction solution under reduced pressure to remove the solvent and dry. Take 155 mg (1.38 mmol) of cyclohexadione, dissolve in 20 mL of dichloromethane, add triethylamine (0.38 mL, 2.77 mmol), and cool using an ice-water bath. It was dissolved in 10 mL of methane and slowly added dropwise and stirred at room temperature for 1 hour.When the reaction was completed, the reaction solution was diluted with water and extracted with ethyl acetate (100 mL) and washed with water and brine. After drying, filtering and the solvent was removed by evaporation under reduced pressure and the resulting residue was purified by silica gel column chromatography. (N - hexane / ethyl acetate = 1/1) to give to give an oil (95% yield), 370 mg of the desired compound condition.

1H NMR (300 MHz, CDCl3) δ 7.92 (d, 1H, J = 8.4 Hz), 7.86 (d, 1H, J = 8.4 Hz), 7.70 (s, 2H), 6.03 (s, 1H), 4.94 (t, 2H), 4.55 (t, 2H), 3.25 (s, 3H), 2.66 (t, 2H), 2.48 (t, 2H), 2.30 (s, 3H), 2.14 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.92 (d, 1H, J = 8.4 Hz), 7.86 (d, 1H, J = 8.4 Hz), 7.70 (s, 2H), 6.03 (s, 1H), 4.94 (t, 2H), 4.55 (t, 2H), 3.25 (s, 3H), 2.66 (t, 2H), 2.48 (t, 2H), 2.30 (s, 3H), 2.14 (m, 2H)

8)단계. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온Step 8). 2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one

상기에서 얻어진 3-옥소사이클로헥-1-센-1-일 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조에이트 370 mg (0.883 mmol)을 아세토니트릴 20 mL에 녹이고 트리에틸아민 (0.18 mL, 1.32 mmol), 시안화칼륨 (57 mg, 0.88 mmol) 그리고 아세톤 시아노하이드린을 촉매량 (2 방울) 만큼 가한 후 상온에서 8시간동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 1N-HCl을 가하여 pH 3 정도의 산성용액이 되게 하고 에틸 아세테이트 (100 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (3% MeOH/DCM) 로 정제하여 오일상태의 목적화합물 279 mg (75% 수율)을 얻었다.3-oxocyclohex-1-sen-1-yl 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfur) obtained above 370 mg (0.883 mmol) of polyvinyl) benzoate was dissolved in 20 mL of acetonitrile and triethylamine (0.18 mL, 1.32 mmol), potassium cyanide (57 mg, 0.88 mmol) and acetone cyanohydrin were added in the amount of catalyst (2 drops). After stirring for 8 hours at room temperature, the reaction was completed by TLC, and the reaction solution was diluted with water, 1N-HCl was added to give an acidic solution of pH 3 and extracted with ethyl acetate (100 mL). The organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by evaporation under reduced pressure.The obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain the title compound as an oil in 279 mg ( 75% yield).

1H NMR (300 MHz, CDCl3) δ 7.83 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.97 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.80 (t, 2H), 2.43 (t, 2H), 2.06 (m, 2H), 2.06 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.83 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.97 (d, 1H, J = 8.3 Hz), 4.92 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.80 (t, 2H), 2.43 (t, 2H), 2.06 (m, 2H), 2.06 (s, 3H)

실시예 8. (E)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 42)의 합성Example 8. ( E ) -2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-ten-1-yl) oxy) -2-chloro Synthesis of -4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex-2-sen-1-one (Compound No. 42)

3-옥소사이클로헥-1-센-1-일 (E)-3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조에이트 (735 mg)를 아세토나이트릴에 녹인 후, 아세톤 시아노하이드린 (0.03 mL), 트리에틸아민 (0.44 mmol), 시안화칼륨 (154 mg)을 첨가하였다. 반응 혼합물을 상온에서 15시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 511 mg의 원하는 화합물을 얻을 수 있다. 3-oxocyclohex-1-sen-1-yl ( E ) -3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-ten-1-yl) Oxy) -2-chloro-4- (methylsulfonyl) benzoate (735 mg) was dissolved in acetonitrile and then acetone cyanohydrin (0.03 mL), triethylamine (0.44 mmol), potassium cyanide (154 mg ) Was added. The reaction mixture was stirred at room temperature for at least 15 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. 1N aqueous hydrogen chloride solution was added and acid treated, followed by extraction three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can be used to yield 511 mg of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.60-7.68 (m, 2H), 7.08 (d, J = 8.2 Hz, 1H), 6.13-6.2 (m, 1H), 5.98-6.11 (m, 1H), 5.14 (d, J = 5.6 Hz, 2H), 4.77 (d, J = 5.3 Hz, 1H), 3.25 (s, 3H), 2.75-2.88 (m, 2H), 2.38-2.52 (m, 2H), 2.00-2.14 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.2 Hz, 1H), 7.60-7.68 (m, 2H), 7.08 (d, J = 8.2 Hz, 1H), 6.13-6.2 (m, 1H), 5.98-6.11 (m, 1H), 5.14 (d, J = 5.6 Hz, 2H), 4.77 (d, J = 5.3 Hz, 1H), 3.25 (s, 3H), 2.75-2.88 (m, 2H ), 2.38-2.52 (m, 2H), 2.00-2.14 (m, 2H)

실시예 9. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 44)의 합성Example 9. 2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4-nitrobenzoyl) -3-hydroxycyclohex Synthesis of 2-sen-1-one (Compound No. 44)

3-옥소사이클로헥-1-센-1-일 3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-나이트로벤조에이트 190 mg (0.49 mmol)을 아세토니트릴 10 mL에 녹이고 트리에틸아민 (0.09 mL), 시안화칼륨 (28 mg) 그리고 아세톤 시아노하이드린 (ACH)을 촉매량 (1 방울) 만큼 가한 후 상온에서 8시간동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 1N-HCl을 가하여 pH = 3 정도의 산성용액이 되게 하고 에틸 아세테이트 (100 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (3% MeOH/DCM) 로 정제하여 목적화합물 157 mg (83% 수율)을 얻었다.3-oxocyclohex-1-sen-1-yl 3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4-nitrobenzoate 190 Mg (0.49 mmol) was dissolved in 10 mL of acetonitrile, triethylamine (0.09 mL), potassium cyanide (28 mg) and acetone cyanohydrin (ACH) were added in the amount of catalyst (1 drop), followed by stirring at room temperature for 8 hours. . After confirming the completion of the reaction by TLC, the reaction solution was diluted with water, 1N-HCl was added to make an acidic solution of pH = 3 and extracted with ethyl acetate (100 mL) and washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 157 mg (83% yield) of the target compound.

1H NMR (300 MHz, CDCl3) δ 7.73 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.92 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.56 (t, 2H), 2.82 (t, 2H), 2.44 (t, 2H), 2.08 (m, 2H), 1.92 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.73 (d, 1H, J = 8.3 Hz), 7.67 (s, 2H), 6.92 (d, 1H, J = 8.3 Hz), 4.91 (t, 2H), 4.56 (t, 2H), 2.82 (t, 2H), 2.44 (t, 2H), 2.08 (m, 2H), 1.92 (s, 3H)

실시예 10. (Z)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 45)의 합성Example 10. ( Z ) -2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-ten-1-yl) oxy) -2-chloro Synthesis of 4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex-2-sen-1-one (Compound No. 45)

3-옥소사이클로헥-1-센-1-일 (Z)-3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조에이트 (508 mg)를 아세토나이트릴에 녹인 후, 아세톤 시아노하이드린 (0.02 mL), 트리에틸아민 (0.30 mmol), 시안화칼륨 (107 mg)을 첨가하였다. 반응 혼합물을 상온에서 15시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 345 mg의 원하는 화합물을 얻을 수 있다. 3-oxocyclohex-1-sen-1-yl ( Z ) -3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-ten-1-yl) Oxy) -2-chloro-4- (methylsulfonyl) benzoate (508 mg) was dissolved in acetonitrile and then acetone cyanohydrin (0.02 mL), triethylamine (0.30 mmol), potassium cyanide (107 mg) ) Was added. The reaction mixture was stirred at room temperature for at least 15 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. 1N aqueous hydrogen chloride solution was added and acid treated, followed by extraction three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can be used to yield 345 mg of the desired compound.

1H NMR (300 MHz, CDCl3)δ 7.97 (d, J = 8.1 Hz, 1H), 7.59-7.66 (m, 2H), 7.13 (d, J = 8.1 Hz, 1H), 6.14-6.25 (m, 1H), 6.00-6.11 (m, 1H), 5.29 (d, J = 6.7 Hz, 2H), 4.96 (d, J = 6.7 Hz, 2H), 3.30 (s, 3H), 2.84 (t, J = 6.2 Hz, 2H), 2.47 (t, J = 6.2Hz, 2H), 2.04-2.15 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.97 (d, J = 8.1 Hz, 1H), 7.59-7.66 (m, 2H), 7.13 (d, J = 8.1 Hz, 1H), 6.14-6.25 (m, 1H), 6.00-6.11 (m, 1H), 5.29 (d, J = 6.7 Hz, 2H), 4.96 (d, J = 6.7 Hz, 2H), 3.30 (s, 3H), 2.84 (t, J = 6.2 Hz, 2H), 2.47 (t, J = 6.2 Hz, 2H), 2.04-2.15 (m, 2H)

실시예 11. 2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 48)의 합성Example 11. 2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-tin-1-yl) oxy) -2-chloro-4- ( Synthesis of Methylsulfonyl) benzoyl) -3-hydroxycyclohex-2-sen-1-one (Compound No. 48)

3-옥소사이클로헥-1-센-1-일 3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조에이트 (135 mg)를 아세토나이트릴에 녹인 후, 아세톤 시아노하이드린 (3 방울), 트리에틸아민 (0.08 mmol), 시안화칼륨 (29 mg)을 첨가하였다. 반응 혼합물을 상온에서 18시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 71 mg의 원하는 화합물을 얻을 수 있다.3-oxocyclohex-1-sen-1-yl 3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-tin-1-yl) oxy) -2 -Chloro-4- (methylsulfonyl) benzoate (135 mg) was dissolved in acetonitrile, followed by addition of acetone cyanohydrin (3 drops), triethylamine (0.08 mmol) and potassium cyanide (29 mg). . The reaction mixture was stirred at room temperature for 18 hours or more and the solvent was concentrated under reduced pressure at the end of the reaction. 1N aqueous hydrogen chloride solution was added and acid treated, followed by extraction three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can be used to yield 71 mg of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.0 Hz, 1H), 7.63-7.70 (m, 2H), 7.12 (d, J = 8.0 Hz, 1H), 5.35 (s, 2H), 4.94 (s, 2H), 3.29 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.45 (t, J = 6.3 Hz, 2H), 2.08 (q, J = 6.1 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.0 Hz, 1H), 7.63-7.70 (m, 2H), 7.12 (d, J = 8.0 Hz, 1H), 5.35 (s, 2H) , 4.94 (s, 2H), 3.29 (s, 3H), 2.82 (t, J = 6.3 Hz, 2H), 2.45 (t, J = 6.3 Hz, 2H), 2.08 (q, J = 6.1 Hz, 2H)

실시예 12. 2-(3-(((2H-1,2,3-트리아졸-2-일)메톡시)메톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 49)의 합성Example 12. 2- (3-((( 2H -1,2,3-triazol-2-yl) methoxy) methoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 -Hydroxycyclohex-2-sen-1-one (Compound No. 49)

3-옥소사이클로헥-1-센-1-일 3-(((2H-1,2,3-트리아졸-2-일)메톡시)메톡시)-2-메틸-4-(메틸설포닐)벤조에이트 60 mg (0.138 mmol)을 아세토니트릴 6 mL에 녹이고 트리에틸아민 (0.028 mL, 0.21 mmol), 시안화칼륨 (9.0 mg, 0.138 mmol) 그리고 아세톤 시아노하이드린을 촉매량 (1 방울) 만큼 가한 후 상온에서 8시간동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물 (30 mL)로 희석시키고 1N-HCl을 가하여 pH = 3 정도의 산성용액이 되게 하고 에틸 아세테이트 (50 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (3% MeOH/DCM) 로 정제하여 고체상태의 목적화합물 31 mg (52% 수율)을 얻었다.3-oxocyclohex-1-sen-1-yl 3-((( 2H -1,2,3-triazol-2-yl) methoxy) methoxy) -2-methyl-4- (methylsul 60 mg (0.138 mmol) of ponyl) benzoate was dissolved in 6 mL of acetonitrile and triethylamine (0.028 mL, 0.21 mmol), potassium cyanide (9.0 mg, 0.138 mmol) and acetone cyanohydrin were added in the amount of catalyst (1 drop). After stirring at room temperature for 8 hours. After completion of the reaction by TLC, the reaction solution was diluted with water (30 mL), 1N-HCl was added to give an acidic solution of pH = 3, and extracted with ethyl acetate (50 mL), washed with water and brine. I did it. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 31 mg (52% yield) of the title compound in the solid state.

1H NMR (300 MHz, CDCl3) δ 7.88 (d, 1H, J = 8.3 Hz), 7.73 (s, 2H), 7.02 (d, 1H, J = 8.3 Hz), 6.04 (s, 2H), 5.38 (s, 2H), 3.28 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.25 (s, 3H), 2.09 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.88 (d, 1H, J = 8.3 Hz), 7.73 (s, 2H), 7.02 (d, 1H, J = 8.3 Hz), 6.04 (s, 2H), 5.38 (s, 2H), 3.28 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.25 (s, 3H), 2.09 (m, 2H)

실시예 13. 3-(2-클로로-3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시)-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 51)의 합성Example 13. 3- (2-Chloro-3- (2-fluoro-2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -4- (methylsulfonyl) benzoyl Synthesis of -4--4-hydroxybicyclo [3.2.1] octa-3-ten-2-one (Compound No. 51)

4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 2-클로로-3-(2-플루오로-2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-4-(메틸설포닐)벤조에이트 (255 mg)를 아세토나이트릴 3 mL에 녹인 후, 아세톤 시아노하이드린 1 방울, 트리에틸아민 (0.15 mL), 시안화칼륨 (52 mg)을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산 처리한 다음, 10% 메탄올/다이클로로메탄으로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 223 mg (수율 87%)의 원하는 화합물을 얻을 수 있다.4-oxobicyclo [3.2.1] oc-2-ten-2-yl 2-chloro-3- (2-fluoro-2- (2- ( 2H -1,2,3-triazole-2 -Yl) ethoxy) -4- (methylsulfonyl) benzoate (255 mg) was dissolved in 3 mL of acetonitrile, then 1 drop of acetone cyanohydrin, triethylamine (0.15 mL), potassium cyanide (52 mg The reaction mixture was stirred at room temperature for at least 12 hours, and at the end of the reaction, the solvent was concentrated under reduced pressure, acid treated with 1N aqueous hydrogen chloride solution and extracted three times with 10% methanol / dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed, and 223 mg (yield 87%) of the desired compound could be obtained using column chromatography.

1H NMR (300 MHz, CDCl3) δ 7.95 (d, J = 8.3 Hz, 1H), 7.80 (s, 2H), 7.15 (d, J = 8.3 Hz, 1H), 7.01 (dt, J = 50.6, 6.0 Hz, 1H), 5.09-4.92 (m, 2H), 3.19 (s, 3H), 3.04-3.03 (m, 1H), 2.91-2.89 (m, 1H), 1.99-1.91 (m, 4H), 1.79-1.66 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.95 (d, J = 8.3 Hz, 1H), 7.80 (s, 2H), 7.15 (d, J = 8.3 Hz, 1H), 7.01 (dt, J = 50.6, 6.0 Hz, 1H), 5.09-4.92 (m, 2H), 3.19 (s, 3H), 3.04-3.03 (m, 1H), 2.91-2.89 (m, 1H), 1.99-1.91 (m, 4H), 1.79 -1.66 (m, 2H)

실시예 14. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 53)의 합성Example 14. 2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxo Synthesis of Cyclohex-1-sen-1-yl Acetate (Compound No. 53)

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (55 mg)을 테트라하이드로퓨란에 녹인 후, 아세틸클로라이드 (0.01 mL)와 N,N-다이이소프로필에틸아민 (0.02 mL)을 첨가한 후 상온에서 20분간 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 28.3 mg(47%)의 원하는 화합물을 얻을 수 있다. 2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-Sen-1-one (55 mg) was dissolved in tetrahydrofuran, and acetyl chloride (0.01 mL) and N, N -diisopropylethylamine (0.02 mL) were added, followed by stirring at room temperature for 20 minutes. When the reaction was terminated and extracted with water and ethyl acetate. The obtained organic layer can be obtained by removing the solvent and then using column chromatography to obtain 28.3 mg (47%) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.5 Hz, 1H), 7.68 (s, 2H), 7.45 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz, 2H), 4.70 (t, J = 5.0 Hz, 2H), 3.21 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.15 (s, 3H), 2.14-2.12 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.91 (d, J = 8.5 Hz, 1H), 7.68 (s, 2H), 7.45 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 5.0 Hz , 2H), 4.70 (t, J = 5.0 Hz, 2H), 3.21 (s, 3H), 2.76 (t, J = 6.2 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.15 (s , 3H), 2.14-2.12 (m, 2H)

실시예 15. 3-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 아세테이트 (화합물번호 59)의 합성Example 15. 3- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4-oxo Synthesis of Bicyclo [3.2.1] oc-2-ten-2-yl acetate (Compound No. 59)

3-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)4-하이드록시바이사이클로[3.2.1]옥-3-엔-2-온사이클로헥-2-센-1-온 (58 mg)을 테트라하이드로퓨란에 녹인 후, 아세틸클로라이드 (0.01 mL)와 N,N-다이이소프로필에틸아민 (0.02 mL)을 첨가한 후 상온에서 20분간 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 23.5 mg(37%)의 원하는 화합물을 얻을 수 있다. 3- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) 4-hydroxybicyclo [3.2 .1] Oc-3-en-2-onecyclohex-2-sen-1-one (58 mg) was dissolved in tetrahydrofuran, followed by acetyl chloride (0.01 mL) and N, N -diisopropylethylamine. (0.02 mL) was added, followed by stirring at room temperature for 20 minutes. When the reaction was terminated and extracted with water and ethyl acetate. The organic layer obtained may be freed from solvent and then subjected to column chromatography to obtain 23.5 mg (37%) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.34 (d, J = 8.1Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.69 (t, J = 5.2 Hz, 2H), 3.20 (s, 3H), 3.06-3.00 (m, 2H), 2.19 (s, 3H), 2.15-1.73 (m, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.90 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.34 (d, J = 8.1 Hz, 1H), 4.96 (t, J = 4.9 Hz , 2H), 4.69 (t, J = 5.2 Hz, 2H), 3.20 (s, 3H), 3.06-3.00 (m, 2H), 2.19 (s, 3H), 2.15-1.73 (m, 6H)

실시예 16. 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 61)의 합성Example 16. 3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) Synthesis of Benzoyl) -4-hydroxybicyclo [3.2.1] octa-3-ten-2-one (Compound No. 61)

4-옥소바이사이클로[3.2.1]옥트-2-엔-2-일 3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조에이트(3.53 mmol)를 아세토나이트릴 9 mL에 녹인 후, 트리에틸아민 (7.06 mmol), 시안화칼륨 (5.29 mmol), 아세톤 시아노하이드린 3방울을 첨가하였다. 반응 혼합물을 상온에서 12시간 이상 교반 시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 1N 염화수소 수용액을 첨가하여 산처리한 다음, 에틸아세테이트로 추출하였다. 유기층은 무수황산마그네슘을 이용하여 건조하고 용매를 제거한 후, 컬럼크로마토그래피를 이용하여 0.90g(50%)의 원하는 화합물을 얻을 수 있다.4-oxobicyclo [3.2.1] oct-2-en-2-yl 3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) Dissolve 2-chloro-4- (methylsulfonyl) benzoate (3.53 mmol) in 9 mL of acetonitrile, and then add 3 drops of triethylamine (7.06 mmol), potassium cyanide (5.29 mmol), and acetone cyanohydrin. Added. The reaction mixture was stirred at room temperature for at least 12 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. 1N aqueous hydrogen chloride solution was added and acid treated, followed by extraction with ethyl acetate. The organic layer was dried using anhydrous magnesium sulfate, and the solvent was removed, and then 0.90 g (50%) of the desired compound could be obtained using column chromatography.

1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.1Hz, 1H), 7.63 (s, 2H), 7.11 (d, J = 8.0Hz, 1H), 4.69 (t, J = 5.6Hz, 2H), 4.37 (t, J = 4.4Hz, 2H), 4.14-1.12 (m, 2H), 3.89 (t, J = 4.5Hz, 2H), 3.28 (s, 3H), 3.19 (t, J = 5.4Hz, 1H), 2.92 (t, J = 6.4Hz, 1H), 2.26-1.76 (m, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.95 (d, J = 8.1 Hz, 1H), 7.63 (s, 2H), 7.11 (d, J = 8.0 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.37 (t, J = 4.4 Hz, 2H), 4.14-1.12 (m, 2H), 3.89 (t, J = 4.5 Hz, 2H), 3.28 (s, 3H), 3.19 (t, J = 5.4 Hz, 1H), 2.92 (t, J = 6.4 Hz, 1H), 2.26-1.76 (m, 6H)

실시예 17. 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 사이클로프로판카르복실레이트 (화합물번호 63)의 합성Example 17. 3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) Synthesis of Benzoyl) -4-oxobicyclo [3.2.1] oc-2-ten-2-yl cyclopropanecarboxylate (Compound No. 63)

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (64 mg)을 테트라하이드로퓨란에 녹인 후, 아세틸클로라이드 (0.01 mL)와 N,N-다이이소프로필에틸아민 (0.02 mL)을 첨가한 후 상온에서 20분간 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 36.6 mg (53%)의 원하는 화합물을 얻을 수 있다. 3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4 -Hydroxybicyclo [3.2.1] octa-3-ten-2-one (64 mg) was dissolved in tetrahydrofuran, followed by acetyl chloride (0.01 mL) and N, N -diisopropylethylamine (0.02 mL). ) Was added and stirred at room temperature for 20 minutes. When the reaction was terminated and extracted with water and ethyl acetate. The obtained organic layer can be freed from the solvent and then subjected to column chromatography to obtain 36.6 mg (53%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H), 7.61 (s, 2H), 7.30 (d, J = 8.2Hz, 1H), 4.67 (t, J = 5.6 Hz, 2H), 4.33 (t, J = 4.1 Hz, 2H), 4.10 (t, J = 5.5 Hz, 2H), 3.86 (t, J = 4.3 Hz, 2H), 3.24 (s, 3H), 3.05-3.04 (m, 2H), 2.16-2.07 (m, 4H), 1.75-1.59 (m, 3H), 1.04-1.01 (m, 4H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.91 (d, J = 8.2 Hz, 1H), 7.61 (s, 2H), 7.30 (d, J = 8.2 Hz, 1H), 4.67 (t, J = 5.6 Hz , 2H), 4.33 (t, J = 4.1 Hz, 2H), 4.10 (t, J = 5.5 Hz, 2H), 3.86 (t, J = 4.3 Hz, 2H), 3.24 (s, 3H), 3.05-3.04 (m, 2H), 2.16-2.07 (m, 4H), 1.75-1.59 (m, 3H), 1.04-1.01 (m, 4H)

실시예 18. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 67)의 합성Example 18. 2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl)- Synthesis of 3-oxocyclohex-1-sen-1-yl acetate (Compound No. 67)

2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (0.21 mmol)을 테트라하이드로퓨란 3 mL에 녹인 후, 다이이소프로필에틸아민 (0.23 mmol)를 첨가하였다. 0℃에서 아세틸클로라이드 (0.23 mmol)를 넣은 후 상온에서 20분간 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 39.6 mg(36%)의 원하는 화합물을 얻을 수 있다. 2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3 -Hydroxycyclohex-2-sen-1-one (0.21 mmol) was dissolved in 3 mL of tetrahydrofuran and then diisopropylethylamine (0.23 mmol) was added. After adding acetyl chloride (0.23 mmol) at 0 ° C., the mixture was stirred at room temperature for 20 minutes. When the reaction was terminated and extracted with water and ethyl acetate. The organic layer obtained may be 39.6 mg (36%) of the desired compound by removing the solvent and then using column chromatography.

1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.44 (d, J = 8.2Hz, 1H), 4.69 (t, J = 5.7 Hz, 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.6 Hz, 2H), 3.26 (s, 3H), 2.77 (t, J = 6.2 Hz, 2H), 2.54 (t, J = 6.5 Hz, 2H), 2.17 (s, 3H), 2.15-2.14 (m, 2H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.93 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.44 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.7 Hz , 2H), 4.36 (t, J = 4.4 Hz, 2H), 4.12 (t, J = 5.7 Hz, 2H), 3.88 (t, J = 4.6 Hz, 2H), 3.26 (s, 3H), 2.77 (t , J = 6.2 Hz, 2H), 2.54 (t, J = 6.5 Hz, 2H), 2.17 (s, 3H), 2.15-2.14 (m, 2H)

실시예 19. (E)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 72)의 합성Example 19. ( E ) -2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-ten-1-yl) oxy) -2-chloro Synthesis of 4- (methylsulfonyl) benzoyl) -3-oxocyclohex-1-sen-1-yl acetate (Compound No. 72)

(E)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (100 mg)을 테트라하이드로퓨란에 녹인 후, 아세틸 클로라이드 (0.02 mL), N,N-다이이소프로필에틸아민 (0.04 mL)을 첨가하였다. 반응 혼합물을 상온에서 5분간 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시킨 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 80 mg의 원하는 화합물을 얻을 수 있다. ( E ) -2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-ten-1-yl) oxy) -2-chloro-4- ( Methylsulfonyl) benzoyl) -3-hydroxycyclohex-2-sen-1-one (100 mg) was dissolved in tetrahydrofuran, followed by acetyl chloride (0.02 mL), N, N -diisopropylethylamine ( 0.04 mL) was added. The reaction mixture was stirred at room temperature for 5 minutes, and when the reaction was completed, the solvent was concentrated under reduced pressure, and then extracted three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can be used to obtain 80 mg of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.92 (d, J = 8.1 Hz, 1H), 7.59-7.67 (m, 2H), 7.44 (d, J = 8.1 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.12 (m, 1H), 5.14 (d, J = 5.4 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.76 (t, J = 5.8 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 3H), 2.14 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.92 (d, J = 8.1 Hz, 1H), 7.59-7.67 (m, 2H), 7.44 (d, J = 8.1 Hz, 1H), 6.15-6.27 (m, 1H), 5.99-6.12 (m, 1H), 5.14 (d, J = 5.4 Hz, 2H), 4.74 (d, J = 5.6 Hz, 2H), 3.23 (s, 3H), 2.76 (t, J = 5.8 Hz, 2H), 2.52 (t, J = 6.4 Hz, 2H), 2.08-2.20 (m, 3H), 2.14 (s, 3H)

실시예 20. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-나이트로벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 77)의 합성Example 20. 2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4-nitrobenzoyl) -3-oxocyclohex- Synthesis of 1-sen-1-yl acetate (Compound No. 77)

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(나이트로벤조일)벤조일)-3-하이드록시사이클로헥-2-센-1-온 60 mg (0.155 mmol)을 5 mL의 테트라하이드로퓨란에 녹이고 얼음 중탕을 이용하여 냉각시킨 다음, N,N-다이이소프로필에틸아민 0.08 mL (0.43 mmol)을 첨가하고 계속해서 아세틸 클로라이드 (0.02 mL, 0.28 mmol)을 가한 후 1시간 동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 에틸 아세테이트 (50 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 1/1.5) 로 정제하여 거품상태의 목적화합물 60 mg (90% 수율)을 얻었다.2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (nitrobenzoyl) benzoyl) -3-hydroxycyclohex- 60 mg (0.155 mmol) of 2-sen-1-one are dissolved in 5 mL of tetrahydrofuran and cooled using an ice bath, then 0.08 mL (0.43 mmol) of N, N -diisopropylethylamine are added and continue. Acetyl chloride (0.02 mL, 0.28 mmol) was added thereto, followed by stirring for 1 hour. After confirming the completion of the reaction by TLC, the reaction solution was diluted with water and extracted with ethyl acetate (50 mL) and washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography ( n -hexane / ethyl acetate = 1 / 1.5) to obtain 60 mg (90% yield) of the desired compound in the form of a foam.

1H NMR (300 MHz, CDCl3) δ 7.69 (s, 2H), 7.62 (d, 1H, J = 8.5 Hz), 7.31 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.53 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.17 (s, 3H), 2.15 (m, 2H), 2.08 (s, 3H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.69 (s, 2H), 7.62 (d, 1H, J = 8.5 Hz), 7.31 (d, 1H, J = 8.5 Hz), 4.90 (t, 2H), 4.53 (t, 2H), 2.75 (t, 2H), 2.51 (t, 2H), 2.17 (s, 3H), 2.15 (m, 2H), 2.08 (s, 3H)

실시예 21. (Z)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 78)의 합성Example 21. (Z) -2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-ten-1-yl) oxy) -2-chloro Synthesis of 4- (methylsulfonyl) benzoyl) -3-oxocyclohex-1-sen-1-yl acetate (Compound No. 78)

(Z)-2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-텐-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (72 mg)을 테트라하이드로퓨란에 녹인 후, 아세틸 클로라이드 (0.01 mL), N,N-다이이소프로필에틸아민 (0.03 mL)을 첨가하였다. 반응 혼합물을 상온에서 5분간 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시킨 다음, 에틸아세테이트로 3번 추출하였다. 유기층을 무수황산마그네슘을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 33 mg의 원하는 화합물을 얻을 수 있다.( Z ) -2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-ten-1-yl) oxy) -2-chloro-4- ( Methylsulfonyl) benzoyl) -3-hydroxycyclohex-2-sen-1-one (72 mg) was dissolved in tetrahydrofuran, followed by acetyl chloride (0.01 mL), N, N -diisopropylethylamine ( 0.03 mL) was added. The reaction mixture was stirred at room temperature for 5 minutes, and when the reaction was completed, the solvent was concentrated under reduced pressure, and then extracted three times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography can be used to yield 33 mg of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.97 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.13-6.25 (m, 1H), 6.01-6.13 (m, 1H), 5.30 (d, J = 6.2 Hz, 2H), 4.95 (d, J = 6.7 Hz, 2H), 3.29 (s, 3H), 2.79 (t, J = 6.0 Hz, 2H), 2.55 (t, J = 6.2 Hz, 2H), 2.09-2.23 (m, 5H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.97 (d, J = 8.2 Hz, 1H), 7.58-7.66 (m, 2H), 7.49 (d, J = 8.2 Hz, 1H), 6.13-6.25 (m, 1H), 6.01-6.13 (m, 1H), 5.30 (d, J = 6.2 Hz, 2H), 4.95 (d, J = 6.7 Hz, 2H), 3.29 (s, 3H), 2.79 (t, J = 6.0 Hz, 2H), 2.55 (t, J = 6.2 Hz, 2H), 2.09-2.23 (m, 5H)

실시예 22. 3-(2-클로로-3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시)-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 아세테이트 (화합물번호 83)의 합성Example 22. 3- (2-Chloro-3- (2-fluoro-2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -4- (methylsulfonyl) benzoyl Synthesis of 4-oxobicyclo [3.2.1] oc-2-ten-2-yl acetate (Compound No. 83)

3-(2-클로로-3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시)-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (73 mg)을 테트라하이드로퓨란 1 mL에 녹인 후, 다이이소프로필에틸아민 (0.028 mL)를 첨가하였다. 0℃에서 아세틸클로라이드 (0.012 mL)를 넣은 후 상온에서 10분간 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 41.8 mg (53%)의 원하는 화합물을 얻을 수 있다. 3- (2-chloro-3- (2-fluoro-2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -4- (methylsulfonyl) benzoyl) -4- Hydroxybicyclo [3.2.1] octa-3-ten-2-one (73 mg) was dissolved in 1 mL of tetrahydrofuran and then diisopropylethylamine (0.028 mL) was added. Acetyl chloride (0.012 mL) was added at 0 ° C. and stirred at room temperature for 10 minutes. When the reaction was terminated and extracted with water and ethyl acetate. The obtained organic layer can be obtained by removing the solvent and then using column chromatography to obtain 41.8 mg (53%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.40 (d, J = 8.2 Hz, 1H), 7.01 (dt, J = 50.9, 5.8 Hz, 1H), 5.07-4.95 (m, 2H), 3.20 (s, 3H), 3.10-3.01 (m, 2H), 2.23 (s, 3H), 2.21-2.13 (m, 4H), 1.84-1.72 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 8.2 Hz, 1H), 7.82 (s, 2H), 7.40 (d, J = 8.2 Hz, 1H), 7.01 (dt, J = 50.9, 5.8 Hz, 1H), 5.07-4.95 (m, 2H), 3.20 (s, 3H), 3.10-3.01 (m, 2H), 2.23 (s, 3H), 2.21-2.13 (m, 4H), 1.84-1.72 (m, 2H)

실시예 23. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온 (화합물번호 85)의 합성 Example 23. 2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-chloro Synthesis of Cyclohex-2-sen-1-one (Compound No. 85)

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온을 다이클로로메탄에 녹인 후 온도를 0℃로 낮추었다. 0℃ 온도를 유지시키면서 옥살릴클로라이드, N,N-다이메틸포름아마이드 1 방울을 첨가하였다. 반응 혼합물을 상온에서 3시간 이상 교반시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 반응 혼합물을 물과 에틸아세테이트로 추출한 다음, 얻어진 유기층을 무수황산나트륨을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 원하는 화합물 100 mg (56%)의 원하는 화합물을 얻을 수 있다.2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-Cen-1-one was dissolved in dichloromethane and the temperature was lowered to 0 ° C. One drop of oxalylchloride, N, N -dimethylformamide was added while maintaining the temperature at 0 ° C. The reaction mixture was stirred at room temperature for at least 3 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. The reaction mixture was extracted with water and ethyl acetate, and the obtained organic layer was dried using anhydrous sodium sulfate and the solvent was removed. Column chromatography can be used to obtain 100 mg (56%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz, 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.86 (t, J = 6.5 Hz, 2H), 2.52 (t, J = 6.3 Hz, 2H), 2.15 (quin, J = 6.8 Hz, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.2 Hz, 1H), 7.67 (s, 2H), 7.56 (d, J = 8.2 Hz, 1H), 4.96 (t, J = 4.9 Hz , 2H), 4.71 (t, J = 4.9 Hz, 2H), 3.20 (s, 3H), 2.86 (t, J = 6.5 Hz, 2H), 2.52 (t, J = 6.3 Hz, 2H), 2.15 (quin , J = 6.8 Hz, 2H)

실시예 24. 2-(3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온 (화합물번호 86)의 합성Example 24. 2- (3- (4- ( 2H -1,2,3-triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-chloro Synthesis of Cyclohex-2-sen-1-one (Compound No. 86)

2-(3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (100 mg)을 다이클로로메탄에 녹인 후 온도를 0℃로 낮추었다. 온도를 유지시키면서 옥살릴클로라이드, N,N-다이메틸포름아마이드 1 방울을 첨가하였다. 반응 혼합물을 상온에서 3시간 이상 교반 시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 반응 혼합물을 물과 에틸아세테이트로 추출한 다음, 얻어진 유기층을 무수황산나트륨을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 원하는 화합물 18 mg(18%)의 원하는 화합물을 얻을 수 있다.2- (3- (4- ( 2H -1,2,3-triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-Sen-1-one (100 mg) was dissolved in dichloromethane and the temperature was lowered to 0 ° C. One drop of oxalylchloride, N, N -dimethylformamide was added while maintaining the temperature. The reaction mixture was stirred at room temperature for at least 3 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. The reaction mixture was extracted with water and ethyl acetate, and the obtained organic layer was dried using anhydrous sodium sulfate and the solvent was removed. Column chromatography can be used to obtain 18 mg (18%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.93 (d, J = 8.3 Hz, 1H), 7.61 (s, 2H), 7.56 (d, J = 8.3 Hz, 1H), 4.58 (t, J = 7.0 Hz, 2H), 4.26 (t, J = 6.2 Hz, 2H), 3.24 (s, 3H), 2.89 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.26-2.16 (m, 4H), 1.93-1.88 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.93 (d, J = 8.3 Hz, 1H), 7.61 (s, 2H), 7.56 (d, J = 8.3 Hz, 1H), 4.58 (t, J = 7.0 Hz , 2H), 4.26 (t, J = 6.2 Hz, 2H), 3.24 (s, 3H), 2.89 (t, J = 6.1 Hz, 2H), 2.55 (t, J = 6.4 Hz, 2H), 2.26-2.16 (m, 4H), 1.93-1.88 (m, 2H)

실시예 25. 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-클로로바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 94)의 합성Example 25. 3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) Synthesis of Benzoyl) -4-chlorobicyclo [3.2.1] octa-3-ten-2-one (Compound No. 94)

3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)바이사이클로[3.2.1]옥탄-2,4-다이온 (0.2 mmol)을 다이클로로메탄에 녹인 후 온도를 0℃로 낮추었다. 온도를 유지시키면서 옥살릴 클로라이드 (0.3 mmol), N,N-다이메틸포름아마이드 1 방울을 첨가하였다. 반응 혼합물을 상온에서 3시간 이상 교반 시키고, 반응이 종결되면 감압 하에서 용매를 농축시켰다. 반응 혼합물을 물과 에틸아세테이트로 추출한 다음, 얻어진 유기층을 무수황산나트륨을 이용하여 건조하고 용매를 제거하였다. 컬럼크로마토그래피를 이용하여 원하는 화합물 34.1 mg(32%)의 원하는 화합물을 얻을 수 있다.3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) bicyclo [3.2.1] octane-2,4-dione (0.2 mmol) was dissolved in dichloromethane and the temperature was reduced to 0 ° C. Oxalyl chloride (0.3 mmol) and 1 drop of N, N -dimethylformamide were added while maintaining the temperature. The reaction mixture was stirred at room temperature for at least 3 hours, and when the reaction was completed, the solvent was concentrated under reduced pressure. The reaction mixture was extracted with water and ethyl acetate, and the obtained organic layer was dried using anhydrous sodium sulfate and the solvent was removed. Column chromatography can be used to obtain 34.1 mg (32%) of the desired compound.

1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz, 2H), 4.35 (t, J = 4.6 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.27 (S, 3H), 3.24 (t, J = 4.8 Hz, 1H), 3.07 (t, J = 6.5 Hz, 1H), 2.34-1.95 (m, 6H) 1 H NMR (500 MHz, CDCl 3 ) δ 7.95 (d, J = 8.2 Hz, 1H), 7.63 (s, 2H), 7.47 (d, J = 8.2 Hz, 1H), 4.69 (t, J = 5.6 Hz , 2H), 4.35 (t, J = 4.6 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.88 (t, J = 4.4 Hz, 2H), 3.27 (S, 3H), 3.24 (t , J = 4.8 Hz, 1H), 3.07 (t, J = 6.5 Hz, 1H), 2.34-1.95 (m, 6H)

실시예 26. 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온 (화합물번호 95)의 합성 Example 26. 2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-chloro Synthesis of Cyclohex-2-sen-1-one (Compound No. 95)

2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 60 mg (0.143 mmol)을 5 mL의 다이클로로메탄에 녹이고 옥살일 클로라이드 (0.06 mL, 0.71 mmol)을 첨가하고 다이메틸포름아마이드 1 방울을 가한 후 상온에서 2시간 동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 에틸 아세테이트 (50 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (n-헥산/에틸 아세테이트 = 1/1)로 정제하여 거품상태의 목적화합물 55 mg (88% 수율)을 얻었다.2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- Dissolve 60 mg (0.143 mmol) of 2-sen-1-one in 5 mL of dichloromethane, add oxalyl chloride (0.06 mL, 0.71 mmol), add 1 drop of dimethylformamide, and stir at room temperature for 2 hours. It was. After confirming the completion of the reaction by TLC, the reaction solution was diluted with water and extracted with ethyl acetate (50 mL) and washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography ( n -hexane / ethyl acetate = 1/1) to obtain 55 mg (88% yield) of the target compound in a foam state.

1H NMR (300 MHz, CDCl3) δ 7.87 (d, 1H, J = 8.3 Hz), 7.71 (s, 2H), 7.39 (d, 1H, J = 8.3 Hz), 4.95 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.90 (t, 2H), 2.54 (t, 2H), 2.30 (s, 3H), 2.22 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.87 (d, 1H, J = 8.3 Hz), 7.71 (s, 2H), 7.39 (d, 1H, J = 8.3 Hz), 4.95 (t, 2H), 4.56 (t, 2H), 3.25 (s, 3H), 2.90 (t, 2H), 2.54 (t, 2H), 2.30 (s, 3H), 2.22 (m, 2H)

실시예 27. 2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-플루오로사이클로헥-2-센-1-온 (화합물번호 118)의 합성Example 27. 2- (3- (3- ( 2H -1,2,3-triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-fluoro Synthesis of Locyclohex-2-sen-1-one (Compound No. 118)

2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥스-2-에논 (0.13 mmol)을 다이클로로메탄 3 mL에 녹인 후, 0℃에서 다이에틸아미노설퍼 트라이플로라이드 (0.39 mmol)를 첨가하였다. 상온에서 18시간 이상 교반시켰다. 반응이 종결되면 물과 에틸아세테이트를 이용하여 추출하였다. 얻어진 유기층은 용매를 제거한 다음 컬럼크로마토그래피를 이용하여 13.1 mg (22%)의 원하는 화합물을 얻을 수 있다. 2- (3- (3- ( 2H -1,2,3-triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-enone (0.13 mmol) was dissolved in 3 mL of dichloromethane and then diethylaminosulfur trifluoride (0.39 mmol) was added at 0 ° C. Stir at room temperature for at least 18 hours. When the reaction was terminated and extracted with water and ethyl acetate. The organic layer obtained can be freed from solvent and then subjected to column chromatography to obtain 13.1 mg (22%) of the desired compound.

1H NMR (300 MHz, CDCl3) δ 7.94 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.30 (d, J = 8.1 Hz, 1H), 4.74 (t, J = 7.1 Hz, 2H), 4.31 (t, J = 6.0 Hz, 2H), 3.26 (s, 3H), 2.61-1.95 (m, 8H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J = 8.1 Hz, 1H), 7.62 (s, 2H), 7.30 (d, J = 8.1 Hz, 1H), 4.74 (t, J = 7.1 Hz , 2H), 4.31 (t, J = 6.0 Hz, 2H), 3.26 (s, 3H), 2.61-1.95 (m, 8H)

실시예 28. 2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 120)의 합성Example 28. 2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4-nitrobenzoyl)- Synthesis of 3-hydroxycyclohex-2-sen-1-one (Compound No. 120)

3-옥소사이클로헥-1-센-1-일 3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조에이트 125 mg (0.29 mmol)을 아세토니트릴 7 mL에 녹이고 트리에틸아민 (0.06 mL), 시안화칼륨 (19 mg) 그리고 아세톤 시아노하이드린을 촉매량 (1 방울) 만큼 가한 후 상온에서 8시간동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 1N-HCl을 가하여 pH = 3 정도의 산성용액이 되게 하고 에틸 아세테이트 (100 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (3% MeOH/DCM)로 정제하여 목적화합물 100 mg (68% 수율)을 얻었다.3-oxocyclohex-1-sen-1-yl 3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4 -125 mg (0.29 mmol) of nitrobenzoate are dissolved in 7 mL of acetonitrile, triethylamine (0.06 mL), potassium cyanide (19 mg) and acetone cyanohydrin are added in the amount of catalyst (1 drop), followed by 8 hours at room temperature. Was stirred. After confirming the completion of the reaction by TLC, the reaction solution was diluted with water, 1N-HCl was added to make an acidic solution of pH = 3 and extracted with ethyl acetate (100 mL) and washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 100 mg (68% yield) of the title compound.

1H NMR (300 MHz, CDCl3) δ 7.70 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 6.92 (d, 1H, J = 8.4 Hz), 4.66 (t, 2H), 4.13 (t, 2H), 4.08 (t, 2H), 3.79 (t, 2H), 2.84 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.70 (d, 1H, J = 8.4 Hz), 7.62 (s, 2H), 6.92 (d, 1H, J = 8.4 Hz), 4.66 (t, 2H), 4.13 (t, 2H), 4.08 (t, 2H), 3.79 (t, 2H), 2.84 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H)

실시예 29. 2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 123)의 합성 Example 29. 2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) Synthesis of Benzoyl) -3-hydroxycyclohex-2-sen-1-one (Compound No. 123)

3-옥소사이클로헥-1-센-1-일 3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조에이트 165 mg (0.356 mmol)을 아세토니트릴 10 mL에 녹이고 트리에틸아민 (0.09 mL), 시안화칼륨 (28 mg) 그리고 아세톤 시아노하이드린을 촉매량 (1 방울) 만큼 가한 후 상온에서 8시간동안 교반하였다. TLC로 반응의 완결을 확인 한 다음, 반응용액을 물로 희석시키고 1N-HCl을 가하여 pH = 3 정도의 산성용액이 되게 하고 에틸 아세테이트 (100 mL)로 추출하면서 물과 소금물로 세척 해 주었다. 추출한 유기층을 무수 황산나트륨으로 건조, 여과 후 용매는 감압 하에 증발시켜 제거하였다. 얻어진 잔유물을 실리카겔 컬럼크로마토그래피 (3% MeOH/DCM) 로 정제하여 목적화합물 100 mg (60% 수율)을 얻었다.3-oxocyclohex-1-sen-1-yl 3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4 Dissolve 165 mg (0.356 mmol) of-(methylsulfonyl) benzoate in 10 mL of acetonitrile, add triethylamine (0.09 mL), potassium cyanide (28 mg) and acetone cyanohydrin in a catalytic amount (1 drop), and then room temperature. Stirred for 8 h. After confirming the completion of the reaction by TLC, the reaction solution was diluted with water, 1N-HCl was added to make an acidic solution of pH = 3 and extracted with ethyl acetate (100 mL) and washed with water and brine. The extracted organic layer was dried over anhydrous sodium sulfate, filtered and the solvent was removed by evaporation under reduced pressure. The obtained residue was purified by silica gel column chromatography (3% MeOH / DCM) to obtain 100 mg (60% yield) of the title compound.

1H NMR (300 MHz, CDCl3) δ 7.84 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.98 (d, 1H, J = 8.4 Hz), 4.69 (t, 2H), 4.20 (t, 2H), 4.12 (t, 2H), 3.84 (t, 2H), 3.26 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 (m, 2H) 1 H NMR (300 MHz, CDCl 3 ) δ 7.84 (d, 1H, J = 8.4 Hz), 7.63 (s, 2H), 6.98 (d, 1H, J = 8.4 Hz), 4.69 (t, 2H), 4.20 (t, 2H), 4.12 (t, 2H), 3.84 (t, 2H), 3.26 (s, 3H), 2.83 (t, 2H), 2.46 (t, 2H), 2.18 (s, 3H), 2.09 ( m, 2H)

통상의 당업자라면 상기 실시예에서 예시된 합성법을 이용하거나 응용하여 상기 표 1에 예시한 화합물들을 쉽게 합성할 수 있다.Those skilled in the art can easily synthesize the compounds illustrated in Table 1 by using or applying the synthesis methods exemplified in the above examples.

[제제][Suggestions]

본 발명의 상기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물은 제초제로서 유용하게 사용할 수 있으며, 제초제로 사용하는 경우 농약의 제제화에 통상적으로 사용하는 담체, 계면활성제, 분산제, 보조제 등을 상기 화학식 1의 화합물과 배합하여 수화제, 유제, 분제 현탁제, 액제 등의 각종 형태로 제제화하여 사용할 수 있다. 이들 제제들은 직접 사용될 수 있고 적절한 매체에 희석하여 처리할 수 있다. The benzoylcyclohexanedione compound represented by Chemical Formula 1 of the present invention may be usefully used as a herbicide, and when used as a herbicide, carriers, surfactants, dispersants, adjuvants, and the like, which are commonly used in formulating pesticides, may be used. It can be used by formulating in various forms, such as a hydrating agent, an emulsion, a powder suspension, and a liquid, in combination with the compound. These formulations can be used directly and can be processed by dilution in appropriate media.

분무 부피량은 헥타아르(ha)당 수 백 리터 내지 몇 천 리터까지 사용할 수 있다.Spray volumes can be used from several hundred liters to several thousand liters per hectare (ha).

본 발명의 제초제 조성물은 상기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물 및 이의 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 1종 이상의 활성성분 0.1 중량% 내지 99.9 중량%; 및 계면활성제, 및 고체 또는 액체 희석제로부터 선택된 1종 또는 2종 이상의 첨가제 0.1 중량% 내지 99.9 중량%; 를 포함한다.The herbicide composition of the present invention comprises 0.1 wt% to 99.9 wt% of at least one active ingredient selected from the group consisting of a benzoylcyclohexanedione compound represented by Formula 1 and agrochemically acceptable salts thereof; And 0.1% to 99.9% by weight of one or two or more additives selected from surfactants and solid or liquid diluents; It includes.

상기 제초제 조성물은 활성성분을 0.1 중량% 내지 99.9 중량% 범위로 포함할 수 있고, 제제 형태에 따라 활성성분의 함량을 차이가 있을 수 있다. 또한, 상기 제초제 조성물에는 0.1 중량% 내지 99.9 중량% 범위로 포함할 수 있다. 상기 첨가제는 계면활성제, 고체 희석제 또는 액체 희석제일 수 있으며, 계면활성제는 약 0.1 중량% 내지 20 중량% 범위로 함유될 수 있고, 고체 또는 액체 희석제는 0 중량% 내지 99. 9중량% 범위로 함유시킬 수도 있다. The herbicide composition may include the active ingredient in the range of 0.1% by weight to 99.9% by weight, and the content of the active ingredient may vary depending on the form of the preparation. In addition, the herbicide composition may be included in the range of 0.1% to 99.9% by weight. The additive may be a surfactant, a solid diluent or a liquid diluent, the surfactant may be contained in the range of about 0.1% to 20% by weight, and the solid or liquid diluent may be contained in the range of 0% to 99.9% by weight. You can also

하기 표 3에는 제제의 형태별로 활성성분, 계면활성제 및 희석제의 함량을 대략적으로 요약하여 나타내었다.Table 3 below summarizes the contents of the active ingredients, surfactants and diluents by the type of preparation.

제형Formulation 함량비 (단위: 중량%)Content ratio (unit: weight%) 활성성분Active ingredient 계면활성제Surfactants 희석제diluent 수화제Hydrating agent 10 ～ 9010 to 90 1 ～ 101 to 10 0 ～ 800 to 80 현탁제Suspension 3 ～ 503 to 50 0 ～ 150 to 15 40 ～ 9540 to 95 유제/액제Emulsion / Liquid 3 ～ 503 to 50 0 ～ 150 to 15 40 ～ 9540 to 95 입제Granulation 0.1 ～ 950.1 to 95 1 ～ 151 to 15 5 ～ 99.55 to 99.5

상기 계면활성제는 계면활성이 큰 물질이며, 분자 중에 친수성 및 친유성 분자단을 가진 양친매성 물질일 수 있다. 이러한 계면활성제는 세정력, 분산력, 유화력, 가용화력, 습윤력, 살균력, 기포력 및 침투력 등이 우수하므로, 제조체 조성물에 포함되어 효과적으로 약효를 발현하도록 습윤, 붕괴, 분산, 또는 유화시키는 작용을 한다. 상기 계면활성제로는 (C8～C12알킬)벤젠설포네이트, (C3～C6알킬)나프탈렌설포네이트, 다이(C3～C6알킬)나프탈렌설포네이트, 다이(C8～C12알킬)설포석시네이트, 리그닌설포네이트, 나프탈렌설포석시네이트포르말린축합물, (C8～C12알킬)나프탈렌설포네이트포르말린축합물, 폴리옥시에틸렌(C8～C12알킬)페닐설포네이트와 같은 설포네이트의 나트륨염 또는 칼슘염; (C8～C12알킬)설페이트, 폴리옥시에틸렌(C8～C12알킬)설페이트, 폴리옥시에틸렌(C8～C12알킬)페닐설페이트와 같은 설페이트의 나트륨염 또는 칼슘염; 폴리옥시알킬렌숙시네이트와 같은 숙시네이트의 나트륨염 또는 칼슘염; 등이 포함되는 음이온성 계면활성제알 수 있다. 또한 상기 계면활성제로는 폴리옥시에틸렌(C8～C12알킬)에테르, 폴리옥시에틸렌(C8～C12알킬)페닐에테르, 폴리옥시에틸렌(C8～C12알킬)페닐폴리머와 같은 비이온성 계면활성제가 포함될 수 있다. 상기한 계면활성제는 단독 또는 2종 이상을 혼합되어 사용될 수 있으며, 본 발명에서 사용될 수 있는 계면활성제가 상기 예시적으로 열거된 화합물에 한정되지 아니한다.The surfactant is a material having a high surfactant, and may be an amphiphilic material having hydrophilic and lipophilic molecular groups in a molecule. These surfactants are excellent in detergency, dispersibility, emulsifying power, solubilizing power, wetting power, bactericidal power, foaming power, and penetration power, so that they are wetted, collapsed, dispersed, or emulsified to effectively express medicinal effects. . Examples of the surfactant include (C 8 -C 12 alkyl) benzenesulfonate, (C 3 -C 6 alkyl) naphthalenesulfonate, di (C 3 -C 6 alkyl) naphthalenesulfonate, di (C 8 -C 12 alkyl ) Sulfosuccinate, lignin sulfonate, naphthalene sulfosuccinate formalin condensate, (C 8 -C 12 alkyl) naphthalenesulfonate formalin condensate, polyoxyethylene (C 8 -C 12 alkyl) phenylsulfonate Sodium or calcium salts of sulfonates; Sodium or calcium salts of sulfates such as (C 8 -C 12 alkyl) sulfate, polyoxyethylene (C 8 -C 12 alkyl) sulfate, polyoxyethylene (C 8 -C 12 alkyl) phenylsulfate; Sodium or calcium salts of succinate, such as polyoxyalkylene succinate; Anionic surfactants, etc. are contained. Further, the surfactant may be nonionic such as polyoxyethylene (C 8 -C 12 alkyl) ether, polyoxyethylene (C 8 -C 12 alkyl) phenyl ether, polyoxyethylene (C 8 -C 12 alkyl) phenyl polymer. Surfactants may be included. The above surfactants may be used alone or in combination of two or more thereof, and the surfactants that may be used in the present invention are not limited to the compounds exemplified above.

상기 활성성분의 함량은 용도에 따라 조절될 수 있으며, 활성성분에 비하여 계면활성제를 더 많은 함량으로 사용하는 것이 필요할 때도 있으며 제제 시에 첨가하거나 탱크 혼합으로 사용할 수도 있다.The content of the active ingredient can be adjusted according to the use, it is sometimes necessary to use a higher content of the surfactant than the active ingredient and may be added in the formulation or used in tank mixing.

본 발명의 제초제 조성물에 포함되는 희석제는 성상에 따라 고체 희석제와 액체 희석제로 분류할 수 있다. 고체 희석제로서 흡수력이 높은 희석제는 수화제를 만들 때 특히 좋다. 액체 희석제와 용제는 0℃에서도 상분리가 일어나지 않고 안정한 것이 좋다. 액체 희석제로는, 물, 톨루엔, 자일렌, 석유 에테르, 식물성 오일, 아세톤, 메틸 에틸 케톤, 사이클로헥사논, 산 무수물, 아세토나이트릴, 아세토페논, 아밀 아세테이트, 2-부타논, 부틸린 카보네이트, 클로로벤젠, 사이클로헥산, 사이클로헥산올, 아세트산의 알킬 에스테르, 다이아세톤 알콜, 1,2-다이클로로프로판, 다이에탄올아민, p-다이에틸벤젠, 다이에틸렌 글리콜, 다이에틸렌 글리콜 아비에테이트, 다이에틸렌 글리콜 부틸 에테르, 다이에틸렌 글리콜 에틸 에테르, 다이에틸렌 글리콜 메틸 에테르, N,N-다이메틸포름아마이드, 다이메틸 설폭사이드, 1,4-다이옥산, 다이프로필렌 글리콜, 다이프로필렌 글리콜 메틸 에테르, 다이프로필렌 글리콜 다이벤조에이트, 디프록시톨, 알킬피롤리돈, 에틸 아세테이트, 2-에틸 헥산올, 에틸렌 카보네이트, 1,1,1-트리클로로에탄, 2-헵타논, 알파-피넨, d-리모넨, 에틸 락테이트, 에틸렌 글리콜, 에틸렌 글리콜 부틸 에테르, 에틸렌 글리콜 메틸 에테르, 감마-부티로락톤, 글리세롤, 글리세롤 아세테이트, 글리세롤 다이아세테이트, 글리세롤 트리아세테이트, 헥사데칸, 헥실렌 글리콜, 이소아밀 아세테이트, 이소보르닐 아세테이트, 이소옥탄, 이소포론, 이소프로필벤젠, 이소프로필 미리스테이트, 락트산, 라우릴아민, 메시틸 옥사이드, 메톡시프로판올, 메틸 이소아밀 케톤, 메틸 이소부틸 케톤, 메틸 라우레이트, 메틸 옥타노에이트, 메틸 올레에이트, 메틸렌 클로라이드, m-자일렌, n-헥산, n-옥틸아민, 옥타데칸산, 옥틸아민 아세테이트, 올레산, 올레일아민, o-자일렌, 페놀, 폴리에틸렌 글리콜(PEG 400), 프로피온산, 프로필 락테이트, 프로필렌 카보네이트, 프로필렌 글리콜, 프로필렌 글리콜 메틸 에테르, p-자일렌, 톨루엔, 트리에틸 포스페이트, 트리에틸렌 글리콜, 자일렌설폰산, 파라핀, 광유, 트리클로로에틸렌, 퍼클로로에틸렌, 에틸 아세테이트, 아밀 아세테이트, 부틸 아세테이트, 프로필렌 글리콜 메틸 에테르, 다이에틸렌 글리콜 메틸 에테르, 메탄올, 에탄올, 이소프로판올, 및 고분자량 알콜, 예를 들어, 아밀 알콜, 테트라하이드로푸르푸릴 알콜, 헥산올, 옥탄올, 에틸렌 글리콜, 프로필렌 글리콜, 글리세롤, N-메틸-2-피롤리돈 등이 사용될 수 있다. 고체 희석제로는 활석, 이산화티탄, 납석 점토, 실리카, 아타펄자이트 점토, 규조토, 석회암, 탄산칼슘, 벤토나이트, 칼슘 몬모릴로나이트, 목화씨 껍질, 통밀가루(wheatmeal), 콩고물, 속돌, 목분, 호두 껍질, 리그닌 등이 사용될 수 있다.Diluents included in the herbicide composition of the present invention may be classified into solid diluents and liquid diluents depending on their properties. Highly absorbent diluents as solid diluents are particularly good when making hydrates. The liquid diluent and the solvent are preferably stable without phase separation even at 0 ° C. Liquid diluents include water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butyrate carbonate, Chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p -diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene Glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N, N -dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol di Benzoate, diproxytol, alkylpyrrolidone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1,1,1-tri Loloethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol tree Acetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone Methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m -xylene, n -hexane, n -octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o -xylene, phenol, polyethylene glycol (PEG 400), propionic acid, propyl lactate, propylene carbonate, propylene glycol , Propylene glycol methyl ether, p -xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether , Diethylene glycol methyl ether, methanol, ethanol, isopropanol, and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N -methyl-2 Pyrrolidone and the like can be used. Solid diluents include talc, titanium dioxide, feldspar clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husk, wholemeal, soybean flour, pumice, wood flour, walnut husk, Lignin and the like can be used.

또한, 본 발명의 제초제 조성물을 제제화할 때는 거품생성, 케이크화, 부식발생, 미생물 번식 등을 방지하기 위하여 소량의 기타 첨가제를 가할 수도 있다.In addition, when formulating the herbicide composition of the present invention, a small amount of other additives may be added to prevent foaming, cake formation, corrosion, microbial propagation, and the like.

본 발명의 제초제 조성물을 만드는 방법은 통상의 방법에 의해 수행한다. 액제의 경우는 구성성분들을 단지 혼합하기만 하면 되고, 미세 고상 조성물은 햄머 또는 유동 제분기에서 혼합 분쇄하면 된다. 현탁제의 경우는 습식 제분기에 혼화처리하여 만들고 입제는 활성물질을 입제 담체위에 분무하여 제조할 수 있다.The method for making the herbicide composition of the present invention is carried out by conventional methods. In the case of liquids, the components only need to be mixed, and the fine solid composition may be mixed and ground in a hammer or a flour mill. Suspensions may be prepared by admixing in a wet mill and granulating by spraying an active substance on the granular carrier.

본 발명에 따른 화합물을 이용한 대표적 제제 제조예는 다음과 같다.Representative examples of preparation using the compounds according to the invention are as follows.

제제 1: 수화제Formulation 1: Hydration

하기의 성분들을 완전히 혼합하고 액체 계면활성제를 고체성분들 위에 분무하면서 혼합하였다. 햄머 밀에서 분쇄하여 입자크기가 100 ㎛ 이하가 되게 하였다.The following components were thoroughly mixed and the liquid surfactant was mixed while spraying onto the solid components. Grinding in a hammer mill brought the particle size to 100 μm or less.

유효 화합물 20 중량%20% by weight of active compound

도데실페놀 폴리에틸렌 글리콜 에테르 2 중량%Dodecylphenol polyethylene glycol ether 2% by weight

나트륨 리그린 설포네이트 4 중량%Sodium Lignin Sulfonate 4 wt%

나트륨 실리콘 알루미네이트 6 중량%Sodium silicon aluminate 6% by weight

몬트모릴로나이트 68 중량%Montmorillonite 68% by weight

제제 2: 수화제Formulation 2: Hydration

하기의 성분들을 혼합하고 입자크기가 25 ㎛ 이하가 될 때까지 햄머 밀에서 분쇄한 후 포장하였다.The following ingredients were mixed and ground in a hammer mill until the particle size was 25 μm or less and packaged.

유효 화합물 80 중량%80% by weight of active compound

나트륨 알킬 나프탈렌 설포네이트 2 중량%Sodium Alkyl Naphthalene Sulfonate 2 wt%

나트륨 리그린 설포네이트 2 중량%Sodium Lignin Sulfonate 2 wt%

합성 무정형 실리카 3 중량%3% by weight of synthetic amorphous silica

카오리나이트 13 중량%13% by weight kaolinite

제제 3: 유제Formulation 3: Emulsion

하기의 성분들을 섞고 균일하게 용해하여 유제로 하였다.The following components were mixed and uniformly dissolved to give an emulsion.

유효 화합물 30 중량%30% by weight of active compound

싸이클로헤사논 20 중량%20% by weight of cyclohesanone

폴리옥시에틸렌 알킬아릴에테르 11 중량%11% by weight of polyoxyethylene alkylaryl ether

알킬벤젠설폰산 칼슘 4 중량%Alkylbenzenesulfonate calcium 4% by weight

메틸나프탈렌 35 중량%Methylnaphthalene 35 wt%

제제 4: 입제Formulation 4: Granulation

하기의 성분들을 균일하게 혼합 분쇄한 후, 이 혼합물 100 중량부에 물 20 중량부를 가하고 혼합하여 압출식 조입기를 사용 14~32 메쉬의 입제로 가공한 후 건조하여 입제를 제조하였다.The following components were uniformly mixed and ground, 20 parts by weight of water was added to 100 parts by weight of the mixture, mixed, and processed into granules of 14-32 mesh using an extruder, followed by drying to prepare granules.

유효 화합물 5 중량%5% by weight of active compound

나트륨 라우릴 알콜 황산 에스테르 염 2 중량%Sodium lauryl alcohol sulfate ester salt 2% by weight

나트륨 리그린 설포네이트 5 중량%Sodium Lignin Sulfonate 5 wt%

카르복시메틸 셀룰로오스 2 중량%2% by weight of carboxymethyl cellulose

황산칼륨 16 중량%Potassium Sulfate 16% by weight

석고 70 중량%Gypsum 70% by weight

본 발명의 제제는 실제 사용에 있어서는 적당한 농도로 희석하여 살포하였다.The formulation of the present invention was sprayed by diluting to an appropriate concentration in actual use.

[용도][Usage]

본 발명에 따른 벤조일사이클로헥산다이온 화합물은 토양에 처리되어 여러 가지 잡초를 방제하는 효과가 탁월하다. 구체적으로, 본 발명에 따른 벤조일사이클로헥산다이온 화합물은 수면처리 또는 경엽처리 되어서는 바람직하지 못한 잡초의 방제효과가 탁월하였다. 본 발명에 따른 벤조일사이클로헥산다이온 화합물은 수면처리 또는 경엽처리 되어서는 벼에 대하여 높은 안전성을 나타내며, 화본과 잡초, 사초과 잡초, 또는 광엽 잡초를 방제하는 효과가 탁월하였다. 특히, 화본과 잡초로서 수수, 돌피, 바랭이; 사초과 잡초로서 올챙이고랭이; 광엽 잡초로서 물달개비, 까마중, 도꼬마리; 에 대한 방제 효능이 우수하다. 따라서 벤조일사이클로헥산다이온 화합물이 활성성분으로 포함된 제초제는 논 농사 및 밭 농사에 적합하다.The benzoylcyclohexanedione compound according to the present invention is excellent in the effect of controlling various weeds by treating the soil. Specifically, the benzoylcyclohexanedione compound according to the present invention was excellent in controlling the weeds, which is undesirable in the sleep treatment or foliage treatment. The benzoylcyclohexanedione compound according to the present invention exhibits high safety against rice when subjected to sleep treatment or foliage treatment. The benzoylcyclohexanedione compound according to the present invention has an excellent effect of controlling flowering plants, weeds, weeds, or broadleaf weeds. In particular, sorghum, stony, and barley as flower and weeds; Tadpoles as weeds; Broad-leaved weeds, including stilt, crow, dokmari; The effectiveness of the control against is excellent. Therefore, the herbicide containing the benzoylcyclohexanedione compound as an active ingredient is suitable for paddy farming and field farming.

본 발명의 제초제는 유효성분으로 헥타아르(ha)당 10 g 내지 1 kg까지 사용할 수 있는데, 바람직하기로는 10 g 내지 400 g 정도를 사용하는 것이 좋다. 약량의 선택은 잡초 발생량이나 생육정도, 제제 등의 요소에 의해 결정한다. The herbicide of the present invention can be used up to 10 g to 1 kg per hectare (ha) as an active ingredient, preferably 10 g to 400 g. The choice of dosage is determined by factors such as weed generation, growth level, and preparation.

또, 본 발명의 화합물은 단독으로 사용할 수 있고, 아세틸-CoA 카르복실라제 억제제(ACC), 아세토락테이트 신타제 억제제(ALS), 아마이드, 옥신 제초제, 옥신 수송 억제제, 카로테노이드 생합성 억제제, 에놀피루빌시키메이트 3-포스페이트 신타제 억제제(ESPS), 글루타민 신테타제 억제제, 지질 생합성 억제제, 유사분열 억제제, 프로토포르피리노겐 IX 옥시다제 억제제, 광합성 억제제, 상승작용제, 성장 물질, 세포벽 생합성 억제제 및 기타 제초제로 이루어지는 군으로부터 선택되는 하나 또는 그 이상의 제초 활성 화합물과 혼합하여 사용하는 것도 유용하다. In addition, the compounds of the present invention can be used alone, acetyl-CoA carboxylase inhibitors (ACC), acetolactate synthase inhibitors (ALS), amides, auxin herbicides, auxin transport inhibitors, carotenoid biosynthesis inhibitors, enolpyrubil Sikimate 3-phosphate synthase inhibitors (ESPS), glutamine synthetase inhibitors, lipid biosynthesis inhibitors, mitosis inhibitors, protoporpyrogenogen IX oxidase inhibitors, photosynthesis inhibitors, synergists, growth substances, cell wall biosynthesis inhibitors and other herbicides It is also useful to use in admixture with one or more herbicidally active compounds selected from the group consisting of:

상기 아세틸-CoA 카르복실라제 억제제(ACC)로는 사이클로헥세논 옥심 에테르로서 알록시딤, 클레토딤, 클로프록시딤, 사이클록시딤, 세톡시딤, 트랄콕시딤, 부트록시딤, 클레폭시딤 또는 테프랄옥시딤, 페녹시페녹시프로피온산 에스테르로서 들어 메타미포프, 시할로포프-부틸, 다이클로포프-메틸, 페녹사프로프-에틸, 페녹사프로프-P-에틸, 펜티아프로프-에틸, 플루아지포프-부틸, 플루아지포프-P-부틸, 할록시포프-에톡시에틸, 할록시포프-메틸, 할록시포프-P-메틸, 이속사피리포프, 프로파퀴즈아포프, 퀴즈알로포프-에틸, 퀴즈알로포프-P-에틸 또는 퀴즈알로포프-테푸릴을 사용할 수 있다. The acetyl-CoA carboxylase inhibitors (ACCs) include alkoxydim, cletodim, cloproxidim, cyclooxydim, cetoxydim, tralcoxydim, butoxyroxim, clepoxydim or as cyclohexenone oxime ethers. Tefraloxydim, phenoxyphenoxypropionic acid esters include metamipop, sihalofop-butyl, diclopop-methyl, phenoxaprop-ethyl, phenoxaprop-P-ethyl, pentiaprop- Ethyl, Fluazifop-Butyl, Fluazifop-P-Butyl, Haloxifop-Ethoxyethyl, Haloxifop-Methyl, Haloxifop-P-Methyl, Isoxapyrifop, Propacquisapop, Quiz Allopop-ethyl, quizallofo-P-ethyl or quizallofo-tefuryl can be used.

상기 아세토락테이트 신타제 억제제(ALS)로는 이미다졸리논로서 이마자피르, 이마자퀸, 이마자메타벤즈-메틸 , 이마자목, 이마자픽, 이마제타피르 또는 이마자메타피르, 피리미딜 에테르로서 피리티오박-산, 피리티오박-나트륨, 비스피리박-나트륨 또는 피리벤즈옥심, 술폰아마이드로서 플로라술람, 플루메트술람 또는 메토술람, 술포닐우레아로서 아미도설퓨론, 아짐설퓨론, 벤설퓨론-메틸, 클로리무론-에틸, 클로르설퓨론, 시노설퓨론, 사이클로설파무론, 에타메트설퓨론-메틸, 에톡시설퓨론, 플라자설퓨론, 할로설퓨론-메틸, 이마조설푸론, 메트설퓨론-메틸, 니코설퓨론, 프리미설퓨론-메틸, 프로설퓨론, 피라조설퓨론-에틸, 림설퓨론, 설퓨메투론-메틸, 티오펜설퓨론-메틸, 트리아설퓨론, 트리베누론-메틸, 트리플루설퓨론-메틸, 술포설퓨론, 플루세토설퓨론 또는 아이오도설퓨론를 사용할 수 있다. The acetolactate synthase inhibitor (ALS) is imidazolinone as imazapyr, imazaquin, imazamethabenz-methyl, imaco, imazapic, imazetapyr or imazametapyr, pyrimidyl ether Thiobac-acid, pyrithiobac-sodium, bispyribac-sodium or pyribenzoxime, florasullam as sulfonamide, flumetsulam or metosullam, amidosulfuron as a sulfonylurea, azimsulfuron, bensulfuron-methyl , Chlorimuron-ethyl, chlorsulfuron, cynosulfuron, cyclosulfuron, etamethsulfuron-methyl, ethoxysulfuron, plazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, Nicosulfuron, prisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfumeuron-methyl, thiophensulfuron-methyl, triasulfuron, tribenuron-methyl, triplelusulfuron- Methyl, sulfosulfuron, fluceto Sulfuron or iodosulfuron can be used.

상기 옥신 제초제로는 피리딘 카르복실산으로서 클로피랄리드 또는 피클로람, 2,4-D 또는 베나졸린을 사용할 수 있다.As the auxin herbicide, clopyralide or picloram, 2,4-D or benazolin may be used as the pyridine carboxylic acid.

상기 옥신 수송 억제제로는 나프탈람 또는 다이플루펜조피르를 사용할 수 있고 상기 카로테노이드 생합성 억제제로는 벤조페나프, 클로마존, 디플루페니칸, 플루오로클로리돈, 플루리돈, 피라졸리네이트, 피라족시펜, 이속사플루톨, 이속사클로르톨, 메소트리온, 술코트리온 (클로르메술론), 케토스피라독스, 플루르타몬, 노르플루라존 또는 아미트롤을 사용할 수 있다.Naphthalam or diflufenzopyr may be used as the auxin transport inhibitor, and the carotenoid biosynthesis inhibitor may be benzophenaf, clomazone, diflufenican, fluorochloridone, flulidone, pyrazolinate, or pyra. You may use oxypsifen, isoxaplutol, isoxachlortol, mesotrione, sulcotrione (chlormethulon), ketospiradox, flutamone, norflurazon or amitrol.

상기 에놀피루빌시키메이트 3-포스페이트 신타제 억제제(ESPS)로는 글리포세이트 또는 술포세이트를 사용할 수 있고, 상기 글루타민 신테타제 억제제로는 빌라나포스(비알라포스) 또는 글루포시네이트-암모늄을 사용할 수 있다.Glyphosate or sulfosate may be used as the enolpyruvyl mate 3-phosphate synthase inhibitor (ESPS), and villanafos (non-alpafoss) or glufosinate-ammonium may be used as the glutamine synthetase inhibitor. Can be.

상기 지질 생합성 억제제로는 아닐리드로서 아닐로포스 또는 메페나세트, 클로로아세트아닐리드로서 디메텐아미드, S-디메텐아미드, 아세토클로르, 알라클로르, 부타클로르, 부텐아클로르, 디에타틸-에틸, 디메타클로르, 메타자클로르, 메톨아클로르, S-메톨아클로르, 프레틸아클로르, 프로프아클로르, 프린아클로르, 테르부클로르, 테닐클로르 또는 크실아클로르, 티오우레아로서 부틸레이트, 사이클로에이트, 디-알레이트, 디메피페레이트, EPTC, 에스프로카르브, 몰리네이트, 페불레이트, 프로술포카르브, 티오벤카브 (벤티오카브), 트리-알레이트 또는 베르놀레이트, 벤푸레세이트 또는 퍼플루이돈을 사용할 수 있다.The lipid biosynthesis inhibitors include anilophos or mefenacet as anilide, dimethenamid, S-dimethenamid, acetochlor, alachlor, butachlor, buteneaclor, dietathyl-ethyl, dimethalide as chloroacetanilide Chlor, metazachlor, methol achlor, S-methol achlor, pretyl achlor, propacchlor, priaclor, terbuchlor, tenylchlor or xylaclor, butyrate as thiourea, cycloate, di- Alate, dimepiperate, EPTC, esprocarb, molinate, pebulate, prosulfocarb, thiobencarb (benthiocarb), tri-acrylate or benolate, benfuresate or perfluidone Can be used.

상기 유사분열 억제제로는 카르바메이트로서 아술람, 카르베타미드, 클로르프로팜, 오르벤카르브, 프론아미드 (프로피자미드), 프로팜 또는 티오카르바질, 디니트로아닐린로서 베네핀, 부트랄린, 디니트라민, 에탈플루랄린, 플루클로랄린, 오리잘린, 펜디메탈린, 프로디아민 또는 트리플루랄린, 피리딘으로서 디티오피르 또는 티아조피르, 부타미포스, 클로르탈-디메틸 (DCPA) 또는 말레산 히드라지드를 사용할 수 있다.Such mitosis inhibitors include asulam as carbamate, carbetamid, chlorprofam, orbencarb, prolonamide (propizamide), propam or thiocarbazil, benipine as dinitroaniline, butraline , Dinitramine, etafluralin, fluchlorine, oryzaline, pendimethalin, prodiamine or trifluralin, dithiopyr or thiazopyr as pyridine, butamiphosph, chlortal-dimethyl (DCPA) or male Acid hydrazide can be used.

상기 프로토포르피리노겐 IX 옥시다제 억제제는 다이페닐 에테르로서 아시플루오르펜, 아시플루오르펜-나트륨, 아클로니펜, 비페녹스, 클로르니트로펜 (CNP), 에톡시펜, 플루오로디펜, 플루오로글리코펜-에틸, 포메사펜, 푸릴옥시펜, 락토펜, 니트로펜, 니트로플루오르펜 또는 옥시플루오르펜, 옥사다이아졸로서 옥사디아르길 또는 옥사디아존, 사이클릭 이미드로서 아자페니딘, 부타펜아실, 카르펜트라존-에틸, 시니돈-에틸, 플루미클로락-펜틸, 플루미옥사진, 플루미프로핀, 플루프로파실, 플루티아세트-메틸, 술펜트라존 또는 티디아지민, 피라졸로서 피라플루펜-에틸을 사용할 수 있다.  The protoporpynogen IX oxidase inhibitors are diphenyl ethers such as asifluorfen, asifluorophene-sodium, acloniphene, biphenox, chlornitropen (CNP), ethoxyphene, fluorodiphene, fluoroglycopene Ethyl, pomesafen, furyloxyphene, lactofen, nitrophene, nitrofluorophene or oxyfluorene, oxadiargyl or oxadione as oxadiazole, azaphenidine, butafenacyl as cyclic imide, Carpentrazone-ethyl, cinidon-ethyl, flumichlorac-pentyl, flumioxazine, flumipropine, flupropacyl, fluthiacet-methyl, sulfentrazone or thidiazimine, pyrazole as pyrazole Phen-ethyl can be used.

상기 광합성 억제제는 프로파닐, 피리데이트 피리다폴, 벤조티아디아지논으로서 벤타존, 디니트로페놀으로서 브로모페녹심, 디노셉, 디노셉-아세테이트, 디노테르브 또는 DNOC, 디피리딜렌으로서 시페르쿼트-클로라이드, 디펜조쿼트-메틸술페이트, 디쿼트 또는 파라쿼트-디클로라이드, 우레아로서 클로르브로무론, 클로로톨루론, 디페녹수론, 디메푸론, 디우론, 에티디무론, 페누론, 플루오메투론, 이소프로투론, 이소우론, 리누론, 메타벤즈티아주론, 메타졸, 메토벤주론, 메톡수론, 모노리누론, 네부론, 시두론 또는 테부티우론, 페놀로서 브로목시닐 또는 이옥시닐, 클로리다존, 트리아진으로서 아메트린, 아트라진, 시아나진, 데스메트린, 디메타메트린, 헥사지논, 프로메톤, 프로메트린, 프로파진, 시마진, 시메트린, 테르부메톤, 테르부트린, 테르부틸아진 또는 트리에타진, 트리아지논으로서 메타미트론 또는 메트리부진, 우라실으로서 브로마실, 레나실 또는 테르바실, 비스카르바메이트로서 데스메디팜 또는 펜메디팜을 사용할 수 있다.The photosynthesis inhibitors are propanyl, pyridate pyridafol, benzothiadiazinone as benzozone, bromophenoxime as dinitrophenol, dinocept, dinocept-acetate, dinoterb or DNOC, ciperquat as dipyridylene- Chloride, dipenzoquat-methylsulfate, diquat or paraquat-dichloride, as urea chlorbromuron, chlorotoluron, diphenoxuron, dimefuron, diuron, etidimuron, phenuron, fluoromethuron, iso Proturon, isouron, linuron, metabenzthiazuron, metazole, methopenzuron, methoxuron, monolinuron, neburon, siduron or tebutiuuron, bromocinyl or ethynyl as phenol, chlor Lidazone, triazine, amethrin, atrazine, cyanazine, desmethrin, dimethamethrin, hexazinone, promethone, promethrin, propazine, simazine, cymetrine, terbumetone, terbutrin Terbutyl It is possible to use either azine or triethazine, metamitrone or metrizin as triazinone, bromasil, lenacil or terbasil as uracil, desmediparm or phenmedipham as biscarbamate.

상기 상승작용제로는 옥시란으로서 트리디판을 사용할 수 있고, 상기 성장 물질로는 아릴옥시알칸산으로서 2,4-DB, 클로메프로프, 디클로르프로프, 디클로르프로프-P(2,4-DP-P), 플루오르옥시피르, MCPA, MCPB, 메코프로프, 메코프로프-P 또는 트리클로피르, 벤조산으로서 클로르암벤 또는 디캄바, 퀴놀린카르복실산으로서 퀸클로락 또는 퀸메락을 사용할 수 있으며 상기 세포벽 합성 억제제 이속사벤 또는 디클로베닐을 사용할 수 있다. Tridiphan may be used as the oxirane as the synergist, and 2,4-DB, clomeprop, dichlorprop, dichlorprop-P (2,4) as aryloxyalkanoic acid as the growth material. -DP-P), fluorooxypyr, MCPA, MCPB, mecoprop, mecoprop-P or triclopyr, chloramben or dicamba as benzoic acid, quinclolac or quinmerak as quinolinecarboxylic acid, and The cell wall synthesis inhibitor isoxaben or diclobenyl can be used.

상기 기타 제초제로는 다이클로로프로피온산으로서 달라폰, 다이히드로벤조푸란으로서 에토푸메세이트, 페닐아세트산으로서 클로르페낙(페낙), 또는 아지프로트린, 바르반, 벤술리드, 벤즈티아주론, 벤조플루오르, 부미나포스, 부티다졸, 부투론, 카펜스트롤, 클로르부팜, 클로르펜프로프-메틸, 클로르옥수론, 신메틸린, 쿠밀루론, 사이클루론, 시프라진, 시프라졸, 디벤질루론, 디프로페트린, 딤론, 에글리나진-에틸, 엔도탈, 에티오진, 플루카바존, 플루오르벤트라닐, 플루폭삼, 이소카르바미드, 이소프로팔린, 카르부틸레이트, 메플루이디드, 모누론, 나프로파미드, 나프로파닐리드, 니트랄린, 옥사사이클로메폰, 페니소팜, 피페로포스, 프로시아진, 프로플루랄린, 피리부티카르브, 섹부메톤, 술팔레이트(CDEC), 테르부카르브, 트리아지플람, 트리아펜아미드 또는 트리메투론 및 이들의 환경친화적 염을 사용할 수 있다.Examples of the other herbicides include: dalapon as dichloropropionic acid, etofumesate as dihydrobenzofuran, chlorfenac (phenac) as phenylacetic acid, or aziprotrin, barban, bensulfide, benzthiazurone, benzofluorine, Minaphos, Butidazole, Buturon, Carpenstrol, Chlorbufam, Chlorfenprop-methyl, Chloroxolone, Cynmethylene, Cumyluron, Cyclolone, Ciprazine, Ciprazole, Dibenzyluron, Dipro Petrin, Dimron, Eglinazine-Ethyl, Endotal, Ethiozin, Flucarbazone, Fluorbentranil, Flupoxam, Isocarbamide, Isopropelin, Carbutylate, Mefluidide, Monuron, Napro Pamide, napropanilide, nitraline, oxacyclomepon, phenisopam, piperophos, prosazine, propluraline, pyributycarb, sesbumethone, sulfalate (CDEC), terbucarb, tri Aziplam, Triapena Or a de-trimethoxy Turone and their salts may be environmental friendly.

본 발명에 따른 화합물은 유해 식물에 대해 제초 활성을 갖는다. 상기 '유해 식물'은 농작물 경작지에서 자라는 원하지 않는 식물로, 방제가 필요한 식물을 일컫는다. 잡초는 그 수가 매우 많고, 분류방법도 매우 다양하다. The compounds according to the invention have herbicidal activity against harmful plants. The 'harmful plants' are unwanted plants that grow on cropland, and refer to plants that need to be controlled. The number of weeds is very large and the classification methods are very diverse.

통상적인 잡초 분류방법으로서 형태에 따라 화본과 잡초, 사초과 잡초, 광엽 잡초로 분류하기도 한다. 상기 화본과 잡초는 수수, 돌피, 개밀, 미국개기장, 바랭이, 민바랭이, 왕바랭이, 강아지풀, 수강아지풀, 가을강아지풀, 드렁새, 비노리, 큰비노리, 가락지조, 포아풀 또는 왕포아풀 등이 포함된다. 상기 사초과 잡초는 금방동사니, 올챙이고랭이, 향부자, 너도방동사니, 쇠털골, 올방개, 매자기 등이 포함된다. 상기 광엽 잡초는 물달개비, 까마중, 도꼬마리 등이 포함된다.As a common weed classification method, it may be classified into flower weed, weed, weed and broadleaf weed depending on the shape. The flowers and weeds include sorghum, dolpi, wheat, American dog breeze, barbarian, minbari, king blue, pup grass, pulp grass, fall puppy grass, dredges, vines, large binori, rhythm birds, poa grass or wangpo grass. The herbaceous weeds include a swell, tadpoles, hyangbuja, beetle dongsae, shackles, snares, barberry. The broad-leaved weeds include water wolves, crows, lizards and the like.

또한, 잡초의 엽수에 따라 단자엽 또는 쌍자엽 잡초로 분류하기도 한다. 단자엽 잡초 종으로는 화본과 잡초 또는 사초과 잡초가 포함될 수 있다. 쌍자엽 잡초 종으로는 한련초, 털진득찰, 중대가리풀, 개쑥갓, 쑥, 미국가막사리, 서양민들레, 개망초, 망초, 털별꽃아재비, 지칭개, 보리뺑이, 사철쑥, 도깨비바늘, 진득찰, 단풍잎돼지풀, 씀바귀, 고들빼기, 왕고들빼기, 미국쑥부쟁이, 조뱅이, 민들레, 돼지풀, 뚱딴지, 붉은서나물 등의 국화과 잡초; 향유, 석잠풀, 들깨풀, 익모초 등의 꿀풀과 잡초; 깨풀, 큰땅빈대, 애기땅빈대 등의 대극과 잡초; 주름잎, 밭뚝외풀 등의 현삼과 잡초; 까마중, 미국까마중 등의 가지과 잡초; 개비름, 가는털비름 등의 비름과 잡초; 괭이밥, 선괭이밥 등의 괭이밥과 잡초; 유럽쥐손이풀, 이질풀 등의 쥐손이풀과 잡초; 수박풀, 어저귀 등의 아욱과 잡초; 환삼덩굴, 삼 등의 삼과 잡초; 여뀌바늘, 겹달맞이꽃 등의 바늘꽃과 잡초; 쇠비름 등의 쇠비름과 잡초; 쇠뜨기 등의 속새과 잡초; 반하 등의 천남성과 잡초; 사상자 등의 산형과 잡초; 석류풀 등의 석류풀과 잡초; 닭의장풀 등의 닭의장풀과 잡초; 돌나물 등의 돌나물과 잡초; 애기똥풀 등의 양귀비과 잡초; 박주가리 등의 박주가리과 잡초; 제비꽃 등의 제비꽃과 잡초; 쇠별꽃 등의 석죽과 잡초; 모시물통이 등의 쐐기풀과 잡초; 꽃마리 등의 지치과 잡초; 질경이 등의 질경이과 잡초; 개소시랑개비 등의 장미과 잡초; 물달개비 등의 물옥잠과 잡초 등이 포함될 수 있다.It is also classified as monocotyledonous or dicotyledonous weeds depending on the number of weeds. Monocotyledonous weed species may include flower beds and weeds or weeds. The dicotyledonous weed species include nasturtium, hairy scallop, creeper grass, wormwood, wormwood, american fern, western dandelion, gazelweed, forget-me-not, hairy starfish, locust, barley grass, cedar, wormwood needle, jindukchal, maple leaf pig grass, Chrysanthemum weeds such as bittersweet, alder, persimmon, american mugwort, squirrel, dandelion, ragweed, fat, red sprout; Nectar and weeds such as scented oil, persimmon grass, perilla grass and motherwort; Antidote and weeds, such as sesame seeds, big slug, and baby slug; Hyunsam and weeds, such as wrinkled leaves and turfgrass; Eggplant and weeds such as crows and American crows; Amaranth and weeds, such as forage and fine hair; Hoe rice and weeds such as hoe rice and sun hoe rice; Mouse grasses and weeds, such as European mouse grasses and dysentery; Mallow and weeds, such as watermelon grass and estuary; Ginseng weeds such as hwansam vine and ginseng; Needle flowers and weeds such as needles and evening primroses; Purslane and weeds such as purslane; Genus and weeds such as horsetail; Tiannan and weeds such as barn; Mountain and weeds, such as casualties; Pomegranate grass and weeds such as pomegranate grass; Chickweed grass and weeds such as chickweed grass; Sedum and weeds such as sedum; Poppy and weeds such as celandine; Weeds, such as weeds; Violets and weeds, such as violets; Sukju and weeds, such as a stellar flower; Nettles and weeds such as ramie; Branch weeds, such as a flower; Plantain and weed, such as plantain; Rosaceae weeds such as croquettes; It may include squirts and weeds, such as water webs.

[실험예]Experimental Example

다음은 본 발명의 화합물들이 나타내는 잡초방제 효과를 실험한 예이다.The following is an example of testing the weed control effect exhibited by the compounds of the present invention.

실험예 1. 수면처리 실험 Experimental Example 1. Sleep Treatment

체(sieve)로 쳐서 보관된 논흙을 교반기에 넣어 물을 공급하면서 섞어 곤죽이 되도록 하였고, 토양 2 kg당 수도용 복합비료(N-P-K : 21-17-17)가 1 g씩 들어가도록 섞어주었다. 토양 중에 혼입된 종자와 토양 미생물에 의한 실험상의 오차를 방지하기 위해 120℃에서 30분간 토양 멸균기에서 증기 멸균하여 사용하였다. The soil kept in a sieve was placed in a stirrer and mixed while supplying water, and mixed with water to give 1 g of water fertilizer (N-P-K: 21-17-17) per 2 kg of soil. In order to prevent experimental errors caused by seeds and soil microorganisms mixed in the soil, steam sterilization was used in a soil sterilizer at 120 ° C. for 30 minutes.

파종은, 논 흙 표면을 고르게 편 후 적당량의 종자를 적절한 위치에 뿌려주고, 흙 속으로 묻힐 수 있도록 눌러 주었다. 물달개비 (M. vaginalis), 올챙이고랭이 (S. juncoides)는 2 mm 이내 정도에 묻히게 하였고, 피는 1 cm 이상 묻어 주어 발아시 물에 뜨지 않도록 하였다. 파종후 2~3일 내에 2 엽기의 벼를 포트당 2개씩 이앙하였다.Sowing was evenly spread over the surface of the paddy soil, so that the appropriate amount of seeds were placed in the proper position and pressed to be buried in the soil. Swallowtail ( M. vaginalis ) and tadpoles ( S. juncoides ) were buried within 2 mm, and blood was buried more than 1 cm so that they did not float in water. Within two to three days after sowing, two blades of rice were transferred to each pot.

약제처리는 벼 이앙 후 15일경에, 소요 원제량에 최종 조제액이 트윈 (Tween) 20 0.2%, 아세톤 50%, 물 50%가 되도록 조제하였다. 활성화합물의 양은 원하는 특정 량이 되도록 선택하였다.The drug treatment was prepared about 15 days after rice transplantation so that the final amount of preparation was 0.2% Tween 20, 50% acetone, and 50% water. The amount of active compound was chosen to be the specific amount desired.

약제처리 후 온실조건(주간온도 25～35℃/야간온도 20～25℃, 14시간 광주기)에서 2주 동안 생육시킨 다음, 각 식물에 대한 제초활성을 잡초에 대해서는 0(무방제) ～ 100(완전방제), 작물에는 0(무해) ～ 10(완전고사) 등급표에 준하여 달관 조사하여 무 처리구에 대한 방제가로 평가하였다.After the treatment, they were grown for 2 weeks in greenhouse conditions (day temperature 25 ~ 35 ℃ / night temperature 20 ~ 25 ℃, 14 hours photoperiod), and then weeding activity for each plant was 0 (uncontrolled) to 100 for weeds. (Complete control) and crops were evaluated according to the 0 (harmless) to 10 (completely tested) grade table and evaluated as the control price for the untreated areas.

실험예 2 : 경엽처리 실험Experimental Example 2 Foliage Treatment Experiment

경엽처리는 표면적 350 cm2 사각플라스틱 포트에 원예용 상토를 충진하였다. 그리고, 저온고 (6 ℃)에 보관중인 바랭이, 수수, 돌피 3종의 화본과 잡초 및 까마중, 도꼬마리 2종의 광엽 잡초의 종자 (10~15립), 지하경 (2개체) 및 벼를 파종하였다. 온실조건 (평균 온도 30ㅁ5℃, 광/암=14/10시간)에서 일정기간 생육시킨 후, 실험화합물 최종 처리량을 75 g a.i./ha양이 되도록 희석제 (50% 아세톤, Tween-20 0.1% 포함)로 희석하여 실험화합물 용액을 조제하였다. 조제된 실험화합물 용액을 포트 당 14 mL 량으로 흄 후드 내에서 핸드 스프레이를 이용하여 경엽처리하였다. 상기와 동일한 온실조건에서 관리하였고, 7일 및 14일 후(필요 시 21일 후)에 외형적인 증상 및 약효/약해를 잡초에 대해서는 0(무방제) ～ 100(완전방제), 작물에는 0(무해) ～ 10(완전고사) 등급표에 준하여 달관 조사하여 무 처리구에 대한 방제가로 평가하였다. Foliage was filled with horticultural soil in a 350 cm 2 square plastic pot. In addition, seed (10-15 grains), underground diameters (2 objects), and rice of three varieties of barley, sorghum and dolphins, weeds and crows, two broad-leaved weeds, were stored in low temperature (6 ° C). After a certain period of time in the greenhouse conditions (average temperature 30 ㅁ 5 ℃, light / dark = 14/10 hours), diluent (50% acetone, Tween-20 0.1%) to the final throughput of the test compound 75 g ai / ha Dilution) to prepare a test compound solution. The prepared experimental compound solution was foliage treated using a hand spray in a fume hood at an amount of 14 mL per pot. In the same greenhouse conditions as above, after 7 and 14 days (21 days if necessary), external symptoms and effects / weakness were 0 (uncontrolled) to 100 (complete control) for weeds and 0 (for crops). Harmless) ~ 10 (Complete Examination) according to the rating table was evaluated by the control price for the non-treated area.

또한, 본 실험에서는 대조화합물로서 특허문헌 1(국제공개특허공보 WO2003-066607호)에 개시된 화합물을 사용하였으며, 대조화합물 1과 2의 화학구조는 하기와 같다.In this experiment, the compound disclosed in Patent Document 1 (International Patent Publication No. WO2003-066607) was used as a control compound, and the chemical structures of the control compounds 1 and 2 are as follows.

[대조화합물 1][Control Compound 1]

Figure PCTKR2016005820-appb-I000036
Figure PCTKR2016005820-appb-I000036

[대조화합물 2][Control Compound 2]

Figure PCTKR2016005820-appb-I000037
Figure PCTKR2016005820-appb-I000037

본 발명의 화합물에 대해 수면처리 실험한 결과는 하기 표 4에 나타내었고 경엽처리 실험한 결과는 하기 표 5에 나타내었다. The results of the sleep treatment experiments for the compounds of the present invention are shown in Table 4 and the results of the foliage treatment experiments are shown in Table 5 below.

수면처리 제초 활성시험 (200g a.i./ha)Sleeping Herbicide Activity Test (200g a.i./ha) 실험화합물Experimental Compound 잡초weed 작물crops 물달개비Water pinnacle 올챙이고랭이Tadpole 벼rice plant 화합물번호 2Compound number 2 9999 8888 -- 화합물번호 4Compound number 4 9797 7575 -- 화합물번호 7Compound number 7 100100 9595 -- 화합물번호 9Compound number 9 100100 9090 0.00.0 화합물번호 12Compound no.12 9797 8080 -- 화합물번호 27Compound number 27 9797 7575 0.00.0 화합물번호 32Compound number 32 100100 7575 -- 화합물번호 35Compound number 35 9797 8585 0.00.0 대조화합물 1Control Compound 1 9797 6565 3.03.0 대조화합물 2Control Compound 2 100100 9090 3.03.0

상기 표 4의 수면처리 제초활성 시험결과에 의하면, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 물달개비, 올챙이고랭이와 같은 난방제 논 잡초를 방제하는 효과가 탁월하였다. 또한, 제초활성이 우수한 것으로 확인되고 있는 화합물번호 9, 27 및 35의 화합물과 대조화합물 1 및 2에 대하여 작물 약해실험을 실시한 결과가 상기 표 4에 기재되어 있다. 상기 표 4에 의하면, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 벼에 대한 높은 안전성을 나타냄을 확인할 수 있다.According to the sleep treatment herbicidal activity test results of Table 4, the compound represented by the formula (1) according to the present invention was excellent in the effect of controlling the weed paddy field weeds, such as water squirrel, tadpole. In addition, the results of experiments on crop weakening with respect to the compounds of the compounds Nos. 9, 27 and 35 and the control compounds 1 and 2 which are confirmed to be excellent herbicidal activity are shown in Table 4 above. According to Table 4, it can be seen that the compound represented by Formula 1 according to the present invention exhibits high safety against rice.

경엽처리 제초 활성시험 (75g a.i./ha)Foliar treatment herbicidal activity test (75g a.i./ha) 실험화합물Experimental Compound 잡초weed 작물crops 수수Sorghum 돌피Dolphin 바랭이wire grass 까마중Under the hood 도꼬마리Macaw 벼rice plant 화합물번호 41Compound number 41 9595 9898 9898 100100 100100 -- 화합물번호 44Compound number 44 7070 9595 7070 100100 9898 0.00.0 화합물번호 48Compound number 48 7070 9898 8080 100100 9898 0.00.0 화합물번호 61Compound number 61 8080 9595 9090 100100 9898 0.00.0 화합물번호 62Compound number 62 9898 9898 100100 100100 9898 0.00.0 화합물번호 63Compound number 63 100100 9898 9898 100100 9898 -- 화합물번호 67Compound number 67 9898 9595 9595 100100 9898 0.00.0 화합물번호 68Compound number 68 9898 9898 9898 100100 9898 0.00.0 화합물번호 69Compound number 69 9090 9595 9595 100100 9898 -- 화합물번호 70Compound number 70 9898 9898 9898 100100 100100 0.00.0 화합물번호 71Compound number 71 8080 9595 9595 100100 9090 -- 화합물번호 91Compound number 91 9898 9595 9898 100100 9898 0.00.0 화합물번호 94Compound number 94 9898 9595 9898 100100 9898 -- 화합물번호 96Compound number 96 9898 9898 100100 100100 9898 -- 화합물번호 101Compound number 101 9898 100100 100100 100100 9898 -- 화합물번호 104Compound number 104 7070 9898 8080 100100 9898 0.00.0 화합물번호 118Compound 118 9898 9898 9595 100100 9898 -- 화합물번호 119Compound 119 9898 9595 9898 100100 9898 -- 화합물번호 120Compound number 120 8080 9595 9090 100100 9595 -- 화합물번호 121Compound number 121 9595 9898 7070 100100 9090 -- 화합물번호 123Compound number 123 9595 9898 100100 100100 9898 -- 화합물번호 124Compound 124 100100 9898 9898 100100 9898 -- 화합물번호 125Compound number 125 100100 9898 9898 9898 9595 -- 화합물번호 133Compound number 133 100100 9898 9898 100100 9898 -- 화합물번호 135Compound number 135 100100 9595 9898 100100 9090 -- 화합물번호 136Compound number 136 100100 9898 9898 100100 8080 -- 대조화합물 1Control Compound 1 4040 9595 6060 9898 9595 3.03.0 대조화합물 2Control Compound 2 9595 9898 9595 9595 8080 5.05.0

상기 표 5의 경엽처리 제초활성 시험결과에 의하면, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 수수, 돌피, 바랭이, 까마중, 도꼬마리와 같은 잡초를 방제하는 효과가 탁월하였다. 또한, 제초활성이 우수한 것으로 확인되고 있는 화합물번호 44, 48, 61, 62, 67, 68, 70, 91, 104의 화합물과 대조화합물 1 및 2에 대하여 작물 약해실험을 실시한 결과가 상기 표 5에 기재되어 있다. 상기 표 5에 의하면, 본 발명에 따른 상기 화학식 1로 표시되는 화합물은 벼에 대한 높은 안전성을 나타냄을 확인할 수 있다.According to the test results of the foliage treatment herbicidal activity of Table 5, the compound represented by the formula (1) according to the present invention was excellent in controlling the weeds, such as sorghum, dolpi, barium, crow, lizard. In addition, the results of the crop weakness test on the compounds of Compound Nos. 44, 48, 61, 62, 67, 68, 70, 91, and 104 and Control Compounds 1 and 2, which were confirmed to have excellent herbicidal activity, are shown in Table 5 above. It is described. According to Table 5, it can be seen that the compound represented by the formula (1) according to the present invention shows a high safety for rice.

Claims (17)

하기 화학식 1로 표시되는 벤조일사이클로헥사다이온 화합물 및 이의 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 화합물 : A compound selected from the group consisting of a benzoylcyclohexadione compound represented by Formula 1 and an agriculturally acceptable salt thereof: [화학식 1][Formula 1]
Figure PCTKR2016005820-appb-I000038
Figure PCTKR2016005820-appb-I000038
 상기 화학식 1에서, In Chemical Formula 1, R1은 할로젠원자, 하이드록시기, 또는 -O-C(O)-(C1～C6알킬) 를 나타내고;R 1 represents a halogen atom, a hydroxyl group, or -OC (O)-(C 1 -C 6 alkyl); R2 및 R3은 각각 독립적으로 수소원자, 또는 C1～C6알킬기를 나타내고;R 2 and R 3 each independently represent a hydrogen atom or a C 1 to C 6 alkyl group; R4는 -C1～C6알킬렌-, -C2～C6알케닐렌-, -C2～C6알키닐렌-, C1～C6할로알킬렌기, -(C1～C6알킬렌)-O-(C1～C6알킬렌)-, 또는 -(C1～C6알킬렌)-S-(C1～C6알킬렌)-를 나타내고;R 4 is -C 1 -C 6 alkylene-, -C 2 -C 6 alkenylene-, -C 2 -C 6 alkynylene-, C 1 -C 6 haloalkylene group,-(C 1 -C 6 alkyl Lene) -O- (C 1 -C 6 alkylene)-or-(C 1 -C 6 alkylene) -S- (C 1 -C 6 alkylene)-; X는 할로젠원자, 또는 C1～C6알킬기를 나타내고;X represents a halogen atom or a C 1 to C 6 alkyl group; Y는 -NO2, 또는 -S(O)2-(C1～C2알킬)를 나타내고;Y represents -NO 2 , or -S (O) 2- (C 1 -C 2 alkyl); Z는
Figure PCTKR2016005820-appb-I000039
,
Figure PCTKR2016005820-appb-I000040
또는
Figure PCTKR2016005820-appb-I000041
로부터 선택되고,Z is
Figure PCTKR2016005820-appb-I000039
,
Figure PCTKR2016005820-appb-I000040
or
Figure PCTKR2016005820-appb-I000041
Is selected from, R5는 수소원자, 할로젠원자, C1～C6알킬기, 또는 C1～C6할로알킬기를 나타내고;R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 6 alkyl group, or a C 1 -C 6 haloalkyl group; n은 0, 1, 또는 2의 정수를 나타낸다.n represents the integer of 0, 1, or 2. 제 1 항에 있어서,The method of claim 1, 상기 R1은 할로젠원자, 하이드록시기, 또는 -O-C(O)-(C1～C4알킬)를 나타내고;R 1 represents a halogen atom, a hydroxyl group, or -OC (O)-(C 1 -C 4 alkyl); 상기 R2 및 R3은 각각 독립적으로 수소원자, 메틸기, 에틸기, 노말프로필기, 또는 이소프로필기를 나타내고;R 2 and R 3 each independently represent a hydrogen atom, a methyl group, an ethyl group, a normal propyl group, or an isopropyl group; 상기 R4는 -C1～C4알킬렌-, -C2～C4알케닐렌-, -C2～C4알키닐렌-, -C1～C4할로알킬렌-, -(C1～C4알킬렌)-O-CH2-, -(C1～C4알킬렌)-O-CH2CH2-, -(C1～C4알킬렌)-S-CH2-, 또는 -(C1～C4알킬렌)-S-CH2CH2- 를 나타내고; R 4 is -C 1 -C 4 alkylene-, -C 2 -C 4 alkenylene-, -C 2 -C 4 alkynylene-, -C 1 -C 4 haloalkylene-,-(C 1- C 4 alkylene) -O-CH 2 -,-(C 1 -C 4 alkylene) -O-CH 2 CH 2 -,-(C 1 -C 4 alkylene) -S-CH 2- , or- (C 1 -C 4 alkylene) -S-CH 2 CH 2- ; 상기 X는 할로젠원자, 또는 C1～C4알킬기를 나타내고;X represents a halogen atom or a C 1 to C 4 alkyl group; 상기 Y는 -NO2, 또는 -S(O)2-CH3 를 나타내고;Y is -NO 2 , Or -S (O) 2 -CH 3 ; 상기 Z는
Figure PCTKR2016005820-appb-I000042
,
Figure PCTKR2016005820-appb-I000043
또는
Figure PCTKR2016005820-appb-I000044
로부터 선택되고,Z is
Figure PCTKR2016005820-appb-I000042
,
Figure PCTKR2016005820-appb-I000043
or
Figure PCTKR2016005820-appb-I000044
Is selected from, 상기 R5는 수소원자, 할로젠원자, C1～C4알킬기, 또는 C1～C4할로알킬기를 나타내고;R 5 represents a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, or a C 1 -C 4 haloalkyl group; 상기 n은 0, 1, 또는 2의 정수를 나타내는 것을 특징으로 하는 화합물.N is an integer of 0, 1, or 2, characterized in that the compound. 제 1 항에 있어서,The method of claim 1, 상기 R1은 클로로원자, 하이드록시기, 또는 -O-C(O)-(C1～C4알킬)를 나타내고;R 1 represents a chloro atom, a hydroxyl group, or -OC (O)-(C 1 -C 4 alkyl); 상기 R2 및 R3은 각각 독립적으로 수소원자, 또는 메틸기를 나타내고;R 2 and R 3 each independently represent a hydrogen atom or a methyl group; 상기 R4는 -C1～C4알킬렌-, -C2～C4알케닐렌-, -C2～C4알키닐렌-, -C1～C2할로알킬렌-, -(C1～C2알킬렌)-O-CH2-, -(C1～C2알킬렌)-O-CH2CH2-, -(C1～C2알킬렌)-S-CH2-, 또는 -(C1～C2알킬렌)-S-CH2CH2- 를 나타내고;R 4 is -C 1 -C 4 alkylene-, -C 2 -C 4 alkenylene-, -C 2 -C 4 alkynylene-, -C 1 -C 2 haloalkylene-,-(C 1- C 2 alkylene) -O-CH 2 -,-(C 1 -C 2 alkylene) -O-CH 2 CH 2 -,-(C 1 -C 2 alkylene) -S-CH 2- , or- (C 1 -C 2 alkylene) -S-CH 2 CH 2- ; 상기 X는 클로로원자, 또는 메틸기를 나타내고;X represents a chloro atom or a methyl group; 상기 Y는 -NO2, 또는 -S(O)2-CH3를 나타내고;Y is -NO 2 , Or -S (O) 2 -CH 3 ; 상기 Z는
Figure PCTKR2016005820-appb-I000045
,
Figure PCTKR2016005820-appb-I000046
,
Figure PCTKR2016005820-appb-I000047
,
Figure PCTKR2016005820-appb-I000048
,
Figure PCTKR2016005820-appb-I000049
또는
Figure PCTKR2016005820-appb-I000050
를 나타내고;Z is
Figure PCTKR2016005820-appb-I000045
,
Figure PCTKR2016005820-appb-I000046
,
Figure PCTKR2016005820-appb-I000047
,
Figure PCTKR2016005820-appb-I000048
,
Figure PCTKR2016005820-appb-I000049
or
Figure PCTKR2016005820-appb-I000050
Represents; 상기 n은 0, 또는 2의 정수를 나타내는 것을 특징으로 하는 화합물.N is an integer of 0 or 2, characterized in that the compound. 제 1 항에 있어서,The method of claim 1, 상기 R1은 클로로원자, 하이드록시기, 또는 -O-C(O)-(C1～C4알킬)를 나타내고;R 1 represents a chloro atom, a hydroxyl group, or -OC (O)-(C 1 -C 4 alkyl); 상기 R2 및 R3은 각각 독립적으로 수소원자, 또는 메틸기를 나타내고;R 2 and R 3 each independently represent a hydrogen atom or a methyl group; 상기 R4는 -CH2-, -(CH2)2-, -(CH2)3-, -CH2CH(CH3)-, -(CH2)4-, -CH2CH(CH3)CH2-, -(CH2)5-, -CH2C(CH3)2CH2-, cis -CH2CH=CHCH2-, trans -CH2CH=CHCH2-, -CH2C≡CCH2-, -CH2CHF-, -CH2-O-CH2-, -(CH2)2-O-CH2-, -CH2-O-(CH2)2-, -(CH2)2-O-(CH2)2-, -CH2-S-CH2-, -(CH2)2-S-CH2-, -CH2-S-(CH2)2-, 또는 -(CH2)2-S-(CH2)2-를 나타내고;R 4 is -CH 2 - , -(CH 2 ) 2 -,-(CH 2 ) 3- , -CH 2 CH (CH 3 )-,-(CH 2 ) 4- , -CH 2 CH (CH 3 ) CH 2 -,-(CH 2 ) 5- , -CH 2 C (CH 3 ) 2 CH 2- , cis -CH 2 CH = CHCH 2- , trans -CH 2 CH = CHCH 2- , -CH 2 C CCH 2- , -CH 2 CHF-, -CH 2 -O-CH 2 -,-(CH 2 ) 2 -O-CH 2- , -CH 2 -O- (CH 2 ) 2 -,-(CH 2 ) 2 -O- (CH 2 ) 2- , -CH 2 -S-CH 2 -,-(CH 2 ) 2 -S-CH 2- , -CH 2 -S- (CH 2 ) 2- , or -(CH 2 ) 2 -S- (CH 2 ) 2- ; 상기 X는 클로로원자, 또는 메틸기를 나타내고;X represents a chloro atom or a methyl group; 상기 Y는 -NO2, 또는 -S(O)2-CH3를 나타내고;Y is -NO 2 , Or -S (O) 2 -CH 3 ; 상기 Z는
Figure PCTKR2016005820-appb-I000051
,
Figure PCTKR2016005820-appb-I000052
또는
Figure PCTKR2016005820-appb-I000053
를 나타내고;Z is
Figure PCTKR2016005820-appb-I000051
,
Figure PCTKR2016005820-appb-I000052
or
Figure PCTKR2016005820-appb-I000053
Represents; 상기 n은 0, 또는 2의 정수를 나타내는 것을 특징으로 하는 화합물.N is an integer of 0 or 2, characterized in that the compound. 제 1 항에 있어서, The method of claim 1, 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 2); 2- (3- (2- (2H - 1, 1,2,3-triazol-2-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 2); 2-(3-(4-(2H-1,2,3-트리아졸-2-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 4);2- (3- (4- (2H - 1, 1,2,3-triazol-2-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 4); 2-(3-(2-(1H-1,2,3-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 7);2- (3- (2- (1H-1, 1,2,3-triazol - 1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 7); 2-(3-(4-(1H-1,2,3-트리아졸-1-일)부톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 9);2- (3- (4- (1H-1, 1,2,3-triazol - 1-yl) butoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 9); 2-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 12);2- (3- (2- (1H-1, 1,2,4 - triazol-1 - yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 12); 3-(3-(2-(1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 27); 3- (3- (2- (1H-1, 1,2,4 - triazol-1 - yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4-hydroxybicyclo [ 3.2.1] oc-3-ten-2-one (Compound No. 27); 2-(3-(2-(3-브로모-1H-1,2,4-트리아졸-1-일)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 32);2- (3- (2- (3-bromo-1 H -1,2,4-triazol-1-yl) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3- Hydroxycyclohex-2-sen-1-one (Compound No. 32); 2-(3-(2-((1H-1,2,3-트리아졸-1-일)메톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 35);2- (3- (2-((1H-1, 1,2,3-triazol - 1-yl) methoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-hydro Oxycyclohex-2-sen-1-one (Compound No. 35); 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 41);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-hydroxycyclohex- 2-sen-1-one (Compound No. 41); 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 44);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4-nitrobenzoyl) -3-hydroxycyclohex-2-ene -1-one (Compound No. 44); 2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 48);2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-tin-1-yl) oxy) -2-chloro-4- (methylsulfonyl) Benzoyl) -3-hydroxycyclohex-2-sen-1-one (Compound No. 48); 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-하이드록시바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 61);3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4 -Hydroxybicyclo [3.2.1] octa-3-ten-2-one (Compound No. 61); 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 아세테이트 (화합물번호 62);3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4 Oxobicyclo [3.2.1] oc-2-ten-2-yl acetate (Compound No. 62); 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-옥소바이사이클로[3.2.1]옥-2-텐-2-일 사이클로프로판카르복실레이트 (화합물번호 63);3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4 Oxobicyclo [3.2.1] oc-2-ten-2-yl cyclopropanecarboxylate (Compound No. 63); 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 67);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxocyclo Hex-1-sen-1-yl acetate (Compound No. 67); 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 사이클로프로판카르복실레이트 (화합물번호 68);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxocyclo Hex-1-sen-1-yl cyclopropanecarboxylate (Compound No. 68); 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아이소부티레이트 (화합물번호 69);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxocyclo Hex-1-sen-1-yl isobutyrate (Compound No. 69); 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 피발레이트 (화합물번호 70);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxocyclo Hex-1-sen-1-yl pivalate (Compound No. 70); 2-(3-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 71);2- (3- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3-oxocyclohex-1 -Sen-1-yl acetate (Compound No. 71); 2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온 (화합물번호 91);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3 -Chlorocyclohex-2-sen-1-one (Compound No. 91); 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-4-클로로바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 94);3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -4 -Chlorobicyclo [3.2.1] octa-3-ten-2-one (Compound No. 94); 3-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-4-클로로바이사이클로[3.2.1]옥-3-텐-2-온 (화합물번호 96);3- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -4-chlorobi Cyclo [3.2.1] octa-3-ten-2-one (Compound No. 96); 2-(3-(2-(1H-1,2,3-트리아졸-1-일)에톡시)에톡시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 101);2- (3- (2- ( 1H -1,2,3-triazol-1-yl) ethoxy) ethoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-oxocyclo Hex-1-sen-1-yl acetate (Compound No. 101); 2-(3-((4-(2H-1,2,3-트리아졸-2-일)부-2-틴-1-일)옥시)-2-클로로-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아이소부티레이트 (화합물번호 104);2- (3-((4- ( 2H -1,2,3-triazol-2-yl) but-2-tin-1-yl) oxy) -2-chloro-4- (methylsulfonyl) Benzoyl) -3-oxocyclohex-1-sen-1-yl isobutyrate (Compound No. 104); 2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-플루오로사이클로헥-2-센-1-온 (화합물번호 118); 2- (3- (3- ( 2H -1,2,3-triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-fluorocyclohex- 2-sen-1-one (Compound No. 118); 2-(3-(3-(2H-1,2,3-트리아졸-2-일)프로폭시)-2-클로로-4-(메틸설포닐)벤조일)-3-브로모사이클로헥-2-센-1-온 (화합물번호 119);2- (3- (3- ( 2H -1,2,3-triazol-2-yl) propoxy) -2-chloro-4- (methylsulfonyl) benzoyl) -3-bromocyclohex- 2-sen-1-one (Compound No. 119); 2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 120);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4-nitrobenzoyl) -3-hydroxy Cyclohex-2-sen-1-one (Compound No. 120); 2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-나이트로벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 121);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4-nitrobenzoyl) -3-oxocyclo Hex-1-sen-1-yl acetate (Compound No. 121); 2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-하이드록시사이클로헥-2-센-1-온 (화합물번호 123);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 Hydroxycyclohex-2-sen-1-one (Compound No. 123); 2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 124);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 Oxocyclohex-1-sen-1-yl acetate (Compound No. 124); 2-(3-(2-(2-(2H-1,2,3-트리아졸-2-일)에톡시)에톡시)-2-메틸-4-(메틸설포닐)벤조일)-3-클로로사이클로헥-2-센-1-온(화합물번호 125);2- (3- (2- (2- ( 2H -1,2,3-triazol-2-yl) ethoxy) ethoxy) -2-methyl-4- (methylsulfonyl) benzoyl) -3 -Chlorocyclohex-2-sen-1-one (Compound No. 125); 3-클로로-2-(3-(2-플루오로-2-(1H-1,2,3-트리아졸-1-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)사이클로헥-2-센-1-온 (화합물번호 133);3-chloro-2- (3- (2-fluoro-2- ( 1H -1,2,3-triazol-1-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoyl) Cyclohex-2-sen-1-one (Compound No. 133); 3-클로로-2-(3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)사이클로헥-2-센-1-온 (화합물번호 135);3-chloro-2- (3- (2-fluoro-2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoyl) Cyclohex-2-sen-1-one (Compound No. 135); 2-(3-(2-플루오로-2-(2H-1,2,3-트리아졸-2-일)에톡시-2-메틸-4-(메틸설포닐)벤조일)-3-옥소사이클로헥-1-센-1-일 아세테이트 (화합물번호 136); 및2- (3- (2-fluoro-2- ( 2H -1,2,3-triazol-2-yl) ethoxy-2-methyl-4- (methylsulfonyl) benzoyl) -3-oxo Cyclohex-1-sen-1-yl acetate (Compound No. 136); And 농약학적으로 허용 가능한 이들의 염으로 이루어진 군으로부터 선택된 화합물.A compound selected from the group consisting of agrochemically acceptable salts thereof. 하기 화학식 1로 표시되는 벤조일사이클로헥산다이온 화합물 및 이의 농약학적으로 허용 가능한 염으로 이루어진 군으로부터 선택된 1종 이상의 활성성분 0.1 중량% 내지 99.9 중량%; 및0.1 wt% to 99.9 wt% of at least one active ingredient selected from the group consisting of a benzoylcyclohexanedione compound represented by Formula 1 and agrochemically acceptable salts thereof; And 계면활성제와 고체 또는 액체 희석제로 이루어진 군으로부터 선택된 1종 이상의 첨가제 0.1 중량% 내지 99.9 중량%; 를 포함하는 제초제 조성물.0.1% to 99.9% by weight of one or more additives selected from the group consisting of surfactants and solid or liquid diluents; Herbicide composition comprising a. [화학식 1][Formula 1]
Figure PCTKR2016005820-appb-I000054
Figure PCTKR2016005820-appb-I000054
 (상기 화학식 1에서, R1, R2, R3, R4, X, Y, Z 및 n은 각각 상기 청구항 1에서 정의한 바와 같다)(In Formula 1, R 1 , R 2 , R 3 , R 4 , X, Y, Z and n are as defined in claim 1, respectively) 제 6 항에 있어서,The method of claim 6, 상기 조성물이 수화제, 현탁제, 유제, 유탁제, 미탁제, 액제, 분산성 액제, 입상수화제, 입제, 분제, 액상수화제, 입상수화제, 수면부상성입제, 또는 정제로 제제화된 것을 특징으로 하는 제초제 조성물.Herbicide composition characterized in that the composition is formulated into a hydrating agent, suspending agent, emulsion, emulsion, suspending agent, liquid, dispersible liquid, granular watering agent, granule, powder, liquid watering agent, granular watering agent, waterborne granules, or tablets . 제 6 항에 있어서,The method of claim 6, 상기 활성성분은 추가로 아세틸-CoA 카르복실라제 억제제(ACC), 아세토락테이트 신타제 억제제(ALS), 아미드, 옥신 제초제, 옥신 수송 억제제, 카로테노이드 생합성 억제제, 에놀피루빌시키메이트 3-포스페이트 신타제 억제제(ESPS), 글루타민 신테타제 억제제, 지질 생합성 억제제, 유사분열 억제제, 프로토포르피리노겐 IX 옥시다제 억제제, 광합성 억제제, 상승작용제, 성장 물질, 세포벽 생합성 억제제, 및 공지 제초제로 이루어지는 군으로부터 선택되는 하나 또는 그 이상의 성분을 더 포함하는 것을 특징으로 하는 제초제 조성물.The active ingredient further comprises acetyl-CoA carboxylase inhibitors (ACC), acetolactate synthase inhibitors (ALS), amides, auxin herbicides, auxin transport inhibitors, carotenoid biosynthesis inhibitors, enolpyrubilishmate 3-phosphate synthase One selected from the group consisting of inhibitors (ESPS), glutamine synthetase inhibitors, lipid biosynthesis inhibitors, mitosis inhibitors, protoporpyrogenogen IX oxidase inhibitors, photosynthesis inhibitors, synergists, growth agents, cell wall biosynthesis inhibitors, and known herbicides Or herbicide composition further comprises more components. 제 6 항 내지 제 8 항으로 이루어진 군으로부터 선택된 제초제 조성물을 처리하여 잡초를 방제하는 방법.A method of controlling weeds by treating a herbicide composition selected from the group consisting of claims 6 to 8. 제 9항에 있어서, 수면처리 또는 경엽처리하여 잡초를 방제하는 방법.10. The method of claim 9, wherein the weeds are controlled by sleeping or foliage treatment. 제 9 항에 있어서,The method of claim 9, 벼에는 안전하면서, 화본과 잡초, 사초과 잡초, 광엽 잡초, 또는 이들의 조합을 방제하는 방법.A method of controlling rice plants, weeds, weeds, broadleaf weeds, or a combination thereof while safe for rice. 제 9 항에 있어서,The method of claim 9, 바랭이, 수수, 돌피, 올챙이고랭이, 물달개비, 까마중 또는 도꼬마리로 이루어진 군으로부터 선택된 잡초를 방제하는 방법.A method for controlling weeds selected from the group consisting of barley, sorghum, dolpi, tadpole, sea squirrels, crows or lizards. 하기 화학식 2로 표시되는 3-옥소-1-사이클로알케닐-3-알콕시 벤조에이트와 하기 화학식 3으로 표시되는 아세톤 시아노하이드린 시약을 반응시켜 제조하는, 하기 화학식 1a로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법 :The benzoylcyclohexanedione represented by the following formula (1a) prepared by reacting the 3-oxo-1-cycloalkenyl-3-alkoxy benzoate represented by the following formula (2) with the acetone cyanohydrin reagent represented by the following formula (3) Preparation of Compounds:
Figure PCTKR2016005820-appb-I000055
Figure PCTKR2016005820-appb-I000055
 (상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 청구항 1에서 정의한 바와 같다)(In the above scheme, R 2 , R 3 , R 4 , X, Y, Z and n are as defined in claim 1, respectively.) 제 13 항에 있어서,The method of claim 13, 상기 반응은 시안화 화합물과 염기 존재 하에서 수행하는 것을 특징으로 하는 벤조일사이클로헥사다이온 화합물의 제조방법.The reaction is a method for producing a benzoylcyclohexadione compound, characterized in that carried out in the presence of a cyanide compound and a base. 하기 화학식 1a로 표시되는 화합물을 할로젠화 시약과 반응시켜 제조하는, 하기 화학식 1b로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법 :A method for preparing a benzoylcyclohexanedione compound represented by Chemical Formula 1b, which is prepared by reacting a compound represented by Chemical Formula 1a with a halogenation reagent:
Figure PCTKR2016005820-appb-I000056
Figure PCTKR2016005820-appb-I000056
 (상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 청구항 1에서 정의한 바와 같고, Hal.은 할로젠원자를 나타낸다)(In the above scheme, R 2 , R 3 , R 4 , X, Y, Z and n are as defined in claim 1, respectively, and Hal. Represents a halogen atom.) 하기 화학식 1a로 표시되는 화합물을 R6-C(O)-Cl로 표시되는 알킬카르보닐 클로라이드와 반응시켜 제조하는, 하기 화학식 1c로 표시되는 벤조일사이클로헥산다이온 화합물의 제조방법 :A method for preparing a benzoylcyclohexanedione compound represented by Chemical Formula 1c prepared by reacting a compound represented by Chemical Formula 1a with an alkylcarbonyl chloride represented by R 6 -C (O) -Cl:
Figure PCTKR2016005820-appb-I000057
Figure PCTKR2016005820-appb-I000057
 (상기 반응식에서, R2, R3, R4, X, Y, Z 및 n은 각각 상기 청구항 1에서 정의한 바와 같고, R6는 C1～C4알킬기를 나타낸다.)(In the above scheme, R 2 , R 3 , R 4 , X, Y, Z and n are as defined in claim 1, respectively, and R 6 represents a C 1 to C 4 alkyl group.) 제 13 항에 있어서,The method of claim 13, 상기 화학식 2로 표시되는 화합물은 하기 4단계의 과정을 수행하여 제조된 것을 특징으로 하는 벤조일사이클로헥사다이온 화합물의 제조방법 :Compound represented by the formula (2) is a method for producing a benzoylcyclohexadione compound, characterized in that prepared by performing the following four steps: 1단계) 하기 화학식 5로 표시되는 치환된 메틸 하이드록시벤조에이트를 다이브로모알칸 시약과 반응시켜, 하기 화학식 6으로 표시되는 치환된 메틸 브로모알콕시 벤조에이트를 제조하는 과정;Step 1) reacting the substituted methyl hydroxybenzoate represented by Formula 5 with a dibromoalkane reagent to prepare a substituted methyl bromoalkoxy benzoate represented by Formula 6;
Figure PCTKR2016005820-appb-I000058
Figure PCTKR2016005820-appb-I000058
 (상기 반응식에서, R4, X 및 Y는 각각 상기 청구항 1에서 정의한 바와 같다) (Wherein R 4 , X and Y are each as defined in claim 1 above) 2단계) 하기 화학식 6으로 표시되는 화합물을 Z-H로 표시되는 아졸시약과 반응시켜, 하기 화학식 7로 표시되는 화합물을 제조하는 과정;Step 2) reacting the compound represented by Chemical Formula 6 with an azole reagent represented by Z-H to prepare a compound represented by Chemical Formula 7;
Figure PCTKR2016005820-appb-I000059
Figure PCTKR2016005820-appb-I000059
 (상기 반응식에서, R4, X, Y 및 Z는 각각 상기 청구항 1에서 정의한 바와 같다) (Wherein R 4 , X, Y and Z are each as defined in claim 1 above) 3단계) 하기 화학식 7로 표시되는 화합물을 가수분해 반응시켜, 하기 화학식 8로 표시되는 벤조산 화합물을 제조하는 과정; 및Step 3) hydrolyzing the compound represented by Chemical Formula 7 to prepare a benzoic acid compound represented by Chemical Formula 8; And
Figure PCTKR2016005820-appb-I000060
Figure PCTKR2016005820-appb-I000060
 (상기 반응식에서, R4, X, Y 및 Z는 각각 상기 청구항 1에서 정의한 바와 같다) (Wherein R 4 , X, Y and Z are each as defined in claim 1 above) 4단계) 하기 화학식 8로 표시되는 화합물을 하기 화학식 9로 표시되는 사이클로알칸 다이온 시약과 반응시켜, 하기 화학식 2로 표시되는 화합물을 제조하는 과정.4) a process of preparing a compound represented by the following Chemical Formula 2 by reacting the compound represented by the following Chemical Formula 8 with a cycloalkane dione reagent represented by the following Chemical Formula 9.
Figure PCTKR2016005820-appb-I000061
Figure PCTKR2016005820-appb-I000061
 (상기 반응식에서, R4, X, Y 및 Z는 각각 상기 청구항 1에서 정의한 바와 같다) (Wherein R 4 , X, Y and Z are each as defined in claim 1 above)
PCT/KR2016/005820 2015-06-01 2016-06-01 Benzoyl cyclohexanedione compound, and herbicide containing same Ceased WO2016195384A1 (en)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
US5536703A (en) * 1995-01-13 1996-07-16 Sandoz Ltd. Herbicidal substituted benzoyl bicycloalkanediones
WO2000000029A1 (en) * 1998-06-26 2000-01-06 Novartis Pharma Ag. Herbicidal composition
WO2003022051A1 (en) * 2001-09-06 2003-03-20 Syngenta Participations Ag Herbicidal n-alkylsulfonamino derivatives
KR20040081193A (en) * 2002-02-08 2004-09-20 바이엘 크롭사이언스 아게 Novel tetrazole derivative useful as herbicides
WO2005123667A1 (en) * 2004-06-22 2005-12-29 Syngenta Participations Ag Substituted bicyclooctenes and their use as herbicides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5536703A (en) * 1995-01-13 1996-07-16 Sandoz Ltd. Herbicidal substituted benzoyl bicycloalkanediones
WO2000000029A1 (en) * 1998-06-26 2000-01-06 Novartis Pharma Ag. Herbicidal composition
WO2003022051A1 (en) * 2001-09-06 2003-03-20 Syngenta Participations Ag Herbicidal n-alkylsulfonamino derivatives
KR20040081193A (en) * 2002-02-08 2004-09-20 바이엘 크롭사이언스 아게 Novel tetrazole derivative useful as herbicides
WO2005123667A1 (en) * 2004-06-22 2005-12-29 Syngenta Participations Ag Substituted bicyclooctenes and their use as herbicides

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