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WO2000075112A1 - Nouveaux derives de n-(2,2,2-trifluoroethyl)-4-methoxy-6-[(substitue ou non substitue) m-cyanophenoxy]-2-pyridinecaroxamide, leur procede de production et herbicides afferents - Google Patents

Nouveaux derives de n-(2,2,2-trifluoroethyl)-4-methoxy-6-[(substitue ou non substitue) m-cyanophenoxy]-2-pyridinecaroxamide, leur procede de production et herbicides afferents Download PDF

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WO2000075112A1
WO2000075112A1 PCT/JP2000/003666 JP0003666W WO0075112A1 WO 2000075112 A1 WO2000075112 A1 WO 2000075112A1 JP 0003666 W JP0003666 W JP 0003666W WO 0075112 A1 WO0075112 A1 WO 0075112A1
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compound
methoxy
reaction
formula
substituted
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Japanese (ja)
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Hisashi Kanno
Tsutomu Sato
Masato Arahira
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Kureha Corp
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Kureha Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • the present invention relates to an N- (2,2,2-tritrifluoroethyl) 14-methoxy-16-[(substituted or unsubstituted) metacyanophenoxy] —2-pyridinepyridinecarboxamide derivative,
  • the present invention relates to a production method and a herbicide. Background art
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel compound exhibiting an excellent herbicidal effect, a method for producing the same, and a novel herbicide containing the compound as an active ingredient. It is in.
  • the present inventors have conducted various studies to find a novel pyridine derivative which is industrially useful.
  • the present inventors have found that a novel compound N- (2,2,2-trifur (4-ethyloxy) 14-methoxy-16-[(substituted or unsubstituted) metacyanophenoxy] -12-pyridinecarboxamide derivative is included in the compound described in the above document, and The present inventors have found that they exhibit higher herbicidal activity than compounds having a close relationship with pyridinecarboxamide derivatives, and have completed the present invention.
  • N- (2,2,2-trifluoroethyl) _4-methoxy-16- (metacyanophenoxy) -1-pyridine lipoxamide (compound I_1) is compared with the following four compounds.
  • the combination of the pyridine group at the ⁇ ! ⁇ 4 position, the methano group on the phenyl ring, and the 2,2,2-trifluoroethyl group in the amide part was excellent. It was found to be a factor indicating herbicidal activity.
  • X represents a 4- alkyl group and a halogen atom.
  • N represents an integer of 0 to 4.
  • the second gist of the present invention is that, as represented by the following reaction formula (A), N- (2,2,2-trifluoroethyl) -14-methoxy represented by the general formula (II)
  • a 6-halogeno 2-pyridinecarboxamide derivative is reacted with a (substituted or unsubstituted) metacyanophenol represented by the formula (III), wherein the N— (2, 2, 2—Trifluoroethyl) 1 4—Methoxy
  • x is c, to c 4 alkyl group,.
  • Tau 1 of a halogen atom is a halogen atom.
  • N is an integer of 0-4.
  • the third gist of the present invention is to provide 4-methoxy 6-[(substituted or unsubstituted) methacyanophenoxy represented by the general formula (IV) as represented by the following reaction formula (B). ] — Reacting a 2,2-pyridinecarboxylic acid derivative with a 2,2,2-trifluoroethylamine represented by the formula (V); 2, 4-trifluoromethyl) 6-[(substituted or unsubstituted) metacyanophenoxy] 1-2-pyridine-based method for producing a ruboxamide derivative. Reaction formula (B)
  • X represents a C i -C 4 alkyl group and a halogen atom.
  • R represents a leaving group (halogen atom, lower alkoxy group, hydroxyl group).
  • N represents an integer of 0 to 4.
  • a fourth gist of the invention is that N— (2,2,2-trifluoroethyl) -14-methoxy-16 — [(substituted or unsubstituted) metacyanphenoxy] -12-pyridine represented by the formula (I)
  • a herbicide characterized by containing a carboxamide derivative as an active ingredient.
  • the 2-pyridinecarboxamide derivative hereinafter, abbreviated as the present compound (I)
  • Examples of the C! C ⁇ alkyl group in X include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • preferred X is a methyl group or a chlorine atom.
  • Examples of the compound (I) having the combination of the above substituents and integers include the compounds shown in Table 1 below.
  • Aliphatic hydrocarbons such as xane, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and benzene, dimethylformamide, dimethylacetamide, N-methyl-1-pyrrolidinone, etc.
  • examples include amides, ethers such as dimethyl ether, dimethyloxetane, diisopropyl ether, tetrahydrofuran, diglyme, and dioxane; and alcohols such as methanol and ethanol.
  • water, carbon disulfide, acetonitril, ethyl acetate, pyridine, dimethyl sulfoxide, hexamethylphosphoric amide, or the like may be used as a solvent.
  • solvents may be used as a mixture of two or more kinds. All individual reaction steps of the process of the invention are performed in a solvent or solvent mixture. Further, a solvent composition composed of solvents that do not form a uniform layer may be used. In this case, it is preferable to add a phase transfer catalyst, for example, a conventional quaternary ammonium salt or crown ether to the reaction system.
  • a phase transfer catalyst for example, a conventional quaternary ammonium salt or crown ether
  • the base used in the reaction step or the separation step of the present invention is usually an alkali metal such as lithium, sodium and potassium, an alkaline earth metal such as magnesium, sodium methoxide, and sodium ethoxide.
  • Alkoxides of alkali metals such as potassium t-butoxide; metal hydride compounds such as sodium hydride and potassium hydride; metal carbonates such as sodium carbonate and sodium carbonate; calcium carbonate and carbonic acid
  • Alkaline earth metal carbonates such as barium, alkaline earth metal hydrogen compounds such as calcium hydride, sodium hydroxide
  • Alkali metal hydroxides such as aluminum and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, magnesium oxide, oxidizing power Alkaline earth metal hydroxides such as lysium, methyl Alkali metal organometallic compounds such as lithium, ethyllithium, n-butyllithium, and phenyllithium; and organics such as methylmag
  • the acid used in the reaction step or the separation step of the present invention is usually an inorganic acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid or sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid or the like.
  • Organic acids may be mentioned. These acids may be used as a mixture of two or more.
  • the present compound (I) is a compound represented by the following general formula (II): N— (2,2,2-triethylroethyl) _4-methyl
  • the halogen atom at the 6-position on the pyridine ring of the ethoxy-6-halogeno-2-pyridinepyridine compound (hereinafter abbreviated as compound (II)) is represented by the general formula (III) (substituted or unsubstituted). Substitution) It is obtained by substituting an oxygen atom in a hydroxyl group of a metacyanophenol compound (hereinafter abbreviated as compound (III)) to form a carbon-oxygen bond.
  • the funinoxylation reaction of the compound (II) is generally performed by mixing the compound (II) and the compound (III) in a solvent under basic conditions.
  • the amount of compound (III) to be used is generally 0.8 to 10-fold mol, preferably 1 to 2-fold mol, relative to compound (II).
  • the amount of the base used is the same as or less than the amount of the compound (III), and is usually 0.8 to: L0 mol, preferably 1 to 2 mol. .
  • a monovalent copper salt such as cuprous chloride as a catalyst.
  • the amount of the monovalent copper salt to be added to compound (III) is usually 0.01 to 10-fold mol, preferably 0.1 to 2-fold mol.
  • the reaction temperature is usually in the range of 20 ° (: to 200 t :, preferably 60T: to 180 C.)
  • the reaction time is usually several minutes to several days.
  • amino compound examples include 3-amino-6-methylbenzonitrile, 3-amino-6-chlorobenzonitrile, 3-amino-6-bromobenzonitrile,
  • Examples thereof include 3-amino-6-fluorobenzonitryl and 3-amino-2,6-difluorobenzonitrile, and these compounds are commercially available.
  • nitrated ⁇ examples include, for example, 2-methyl-5-nitrobenzonitrile, 2-chloro-5-nitrobenzonitrile, 2-bromo-5-nitrobenzonitrile, 2-fluoro-5-nitrobenzonitrile Benzonitrile, 4-methyl-5-nitrobenzonitrile, 4-funoleo-5-nitrobenzonitrile, 4-octorolo-5-nitrobenzonitrile, 2,6-difluoro-3-2- Benzonitrile and the like, and these compounds are commercially available.
  • a compound obtained by dehydrating a compound of the formula (III) having a rubamoyl group at a site corresponding to a cyano group can be used.
  • This carboxylic acid amide compound can be produced by amidating the corresponding carboxylic acid.
  • the above compound (II) can be produced as follows.
  • the leaving group (R) in a 2-substituted carbonyl-4-methoxy-16-halogenopyridine derivative (VI) is usually replaced with a 2,2,2,3 represented by the formula (V) in an organic solvent.
  • 2-trifluoroethylamine 4-methoxy-6-halogeno-2-pyridinecarboxamide derivative (II) can be produced.
  • R represents a leaving group (halogen atom, lower alkoxy group, hydroxyl group), and T 1 is the same as described above.)
  • reaction conditions are as follows: 4-Methoxy-6-[(substituted or unsubstituted) metacyanopoxy-12-pyridinepyridine represented by the general formula (IV) described below. ) Is replaced by the amino group nitrogen of 2,2,2-trifluoroethylamine represented by the formula (V), and the conditions for forming a carbon-nitrogen bond can be used.
  • the compound (VI-a) in which R is a halogen atom in the compound (VI) can be produced by halogenating the corresponding carboxylic acid compound (VI-b) (the compound in which R is a hydroxyl group in the compound (VI)).
  • the reaction temperature is usually from 0 to 250 ° C, preferably from 30 to 150 ° C.
  • the amount of the halogenating reagent is usually 0.3 to 10 moles, preferably 1 to 5 moles. It is more preferable to use a reaction such as dimethylformamide.
  • the reaction time is usually several minutes to several days.
  • R represents a halogen atom or a hydroxyl group
  • T 1 is the same as described above.
  • the leaving group (R 1 ) is a lower alkanol (BOH (B is a lower alkyl group. )) Is a group that is substituted by the hydroxyl oxygen of the above, and is a substituent that is bonded to the carbonyl group in compound (VI-d).
  • the leaving group (R 1 ) is usually a halogen atom, for example, a chlorine atom, a bromine atom or a hydroxyl group, preferably a halogen atom, particularly preferably a chlorine atom.
  • the reaction of substituting a halogen atom using lower alcohol (BOH) is a force that proceeds without the presence of a base.
  • Hydrogen halide generated in the course of the reaction A base such as triethylamine may be coexistent in the reaction solution in order to remove the acid.
  • a lower class alkanol for compound (VI-d) The amount of the compound used is usually 1.0 to 1000 times mol, preferably 1.0 to 100 times mol.
  • the reaction temperature is usually in the range of 0 to 2001, preferably in the range of 0 to 100.
  • the reaction time is usually several minutes to several days.
  • a commercial product can be used for the lower alcohol.
  • the compound (VI-c) can be usually produced by reacting an excess of lower alcohol with the compound (VI-d) in a solvent or without solvent.
  • the amount of the lower alkynol used for the compound (VI-d) is usually 1.0 to: L000-fold mol, preferably 1.0 to 100-fold mol.
  • the reaction temperature is usually 0 to 250T, preferably 0 to 801C. When the reaction temperature exceeds the boiling point of the lower alcohol used, the reaction vessel is preferably sealed. Further, the reaction can be promoted by using an acid catalyst such as hydrochloric acid or sulfuric acid, or by using a dehydrating agent such as molecular sieves.
  • the reaction time is usually several minutes to several days.
  • the above compound (VI-b) can be produced as follows. First, as a first method, a compound represented by the general formula (VII) is produced by substituting a metal for the halogen atom (T 2 ) of the compound represented by the general formula (VIII). Between the metallized carbon atom of the hydrogenated compound and the carbon atom of carbon dioxide
  • a method of producing a compound (VI-b) by forming a carbon bond A method of producing a compound (VI-b) by forming a carbon bond.
  • the compound (VI-b) is obtained by converting a 2,6-dihalogeno-4-methoxypyridine derivative represented by the general formula (VIII) (hereinafter abbreviated as compound (VIII)) to a metal.
  • a 2- (metal-substituted) -6-halogeno-4-methoxypyridine derivative (hereinafter abbreviated as compound (VII)) represented by the general formula (VII) is produced. It can be produced by reacting VII) with carbon dioxide, followed by substitution with proton. The power of these is shown in the reaction formula below.
  • Reaction formula (F) Reaction formula (F)
  • T 2 represents a halogen atom
  • M represents a metal (for example, an alkali metal, an alkaline earth metal 'Q (Q represents a halogen atom.)
  • Q represents a halogen atom.
  • 1/2 Cu ⁇ alkali metal
  • T 1 is the same as above, and T 1 and T 2 may be the same or different.
  • the above compound (VII) is obtained by treating compound (VIII) with the following metallating agent.
  • the metallizing agent usually include organometallic compounds of alkali metals such as butyllithium, methyllithium and phenyllithium, alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as magnesium.
  • organic metal compounds of alkali metals prepared with the above-mentioned reagents, organic copper compounds prepared from Grignard reagents and monovalent copper salts, and the like can also be used.
  • the amount of the metalating reagent to be used is not preferably large because the halogen atom to be further substituted is present in the molecule, and is usually 0.5 to 2 moles, preferably 0.8 to 1.5 moles to the compound (VIII). It is twice the mole.
  • For the amount of carbon dioxide use a large excess of equivalent or more to make it react sufficiently.
  • the temperature of the treatment with the metallating agent and the reaction with carbon dioxide is usually from -100 to 1001: 100, preferably from -80 to 80.
  • the reaction time is several minutes to several hours, respectively.
  • Compound (VI-b) can be produced by reacting the obtained compound (VII) with carbon dioxide and then substituting with proton.
  • the proton substitution is performed by treating the reaction solution with an acidic aqueous solution.
  • the acid generally include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, and sulfuric acid, and organic acids such as formic acid, acetic acid, and p-toluenesulfonic acid. These acids may be used as a mixture of two or more.
  • a solvent inert to the organometallic compound can be used.
  • aliphatic hydrocarbons such as petroleum ether, pentane, hexane, heptane, and methylcyclohexane
  • ethers such as dimethyl ether, dimethyloxetane, diisopropyl ether, tetrahydrofuran, diglyme, and dioxane
  • benzene, toluene And aromatic hydrocarbons such as xylene and methylnaphthalene.
  • solvents may be used as a mixture of two or more kinds.
  • a second method for producing the compound (VI-b) includes a method of hydrolyzing a 2-cyano-16-halogeno-4-methoxypyridine derivative represented by the general formula (IX). These are shown by the following reaction formulas. Reaction formula (G)
  • the above hydrolysis may be performed under any of acidic and basic conditions.
  • catalysts such as hydrochloric acid, hydrobromic acid and sulfuric acid are usually used.
  • Use of the inorganic acid As a solvent, an aqueous solution of an organic acid such as acetic acid is usually used in addition to water.
  • an alkali metal base such as sodium hydroxide or potassium hydroxide is usually used as the base.
  • water or an aqueous alcohol solution is usually used as the hydrolysis temperature is usually from 20 to the reflux point, preferably from 50 to the reflux point.
  • the reaction time is several minutes to several hours.
  • Compound (D is prepared as follows.
  • 2-Cyanopyridine 4,6-dichropyridine is prepared by chlorinating 2-cyanopyridine according to the method described in British Patent No. 1301724.
  • 2-cyano 6-chloro-14-methoxypyridine [compound [IX, T ⁇ Cl]] is produced.
  • a third method for producing the compound (VI-b) includes a method of hydrolyzing a lower alkyl ester of 6-halogeno-14-methoxypicolinic acid represented by the general formula (X). These are shown in the following reaction formulas.
  • the above hydrolysis may be performed under any of acidic and basic conditions.
  • an inorganic acid such as hydrochloric acid, hydrobromic acid or sulfuric acid is usually used as a catalyst.
  • an aqueous solution of an organic acid such as acetic acid is usually used in addition to water.
  • an alkali metal base such as sodium hydroxide and potassium hydroxide is usually used as the base.
  • an aqueous alcohol solution is usually used in addition to water.
  • the hydrolysis temperature is usually in the range of 20 to the reflux point, preferably in the range of 50 to the reflux point.
  • the reaction time is several minutes to several hours.
  • Compound (X) is produced as follows. First, N-methylpyridonic acid and thionyl chloride are reacted to synthesize 4,6-dichloropicolinic acid chloride, and then the obtained 4,6-dichloropicolinic acid chloride and a lower salt are synthesized. 4,6-Dichroic picolinic acid as a raw material for the synthesis of compound (X) Production of alkyl esters (J. Org. Chem., 23, 1030 (1958)). The 4,6-dichloropicolinic acid obtained by oxidizing 4,6-dichloromethyl-2-methylpyridine is converted to an acid halide, and then reacted with lower alkanols to form 4,6-dichloropicolinic acid.
  • 2-picoline N-hydroxy is more effective than a method of directly converting a 2-methyl group of a pyridine ring into a carboxyl group by oxidation.
  • Preferred is a method of synthesizing 2-pyridinemethanol from amides and oxidizing to a carboxyl group via a hydroxymethyl group to generate substituted picolinic acid.
  • the leaving group (R) in the 4-methoxyethoxy 6-[(substituted or unsubstituted) methacyano-pentoxy-2-pyridinecarboxylic acid derivative represented by the following general formula (IV) is represented by the formula (V)
  • the amino group nitrogen of 2,2,2— trifluoroethylamine represented by the formula (1) forms a carbon-nitrogen bond, and the N— (2,2,2— Trifluoroethyl) —4—Methoxy 6 — [(substituted or unsubstituted) methacyanophenoxy] — Produces 2-pyridinecarboxamide derivatives. These are shown by the following reaction formulas.
  • the leaving group (R) is a group substituted by a nitrogen of the amino group of the compound (V) during the reaction, and means a substituent bonded to the carbonyl group in the compound (IV).
  • the leaving group (R) is usually a halogen atom such as a chlorine atom or a bromine atom, a lower alkoxy group such as a methoxy group or an ethoxy group, or a hydroxyl group, preferably a halogen atom, and particularly preferably a chlorine atom. .
  • a halogen atom substitution reaction when a compound in which R in compound (IV) is a halogen atom is used, a halogen atom substitution reaction [when a compound in which the amino portion of compound (V) is in a salt form such as a hydrochloride is used. An equivalent amount or more of a base such as triethylamine is added to form a free amine and used. In this case, since hydrogen halide is generated during the reaction, it is preferable to add the compound (V) in excess of one equivalent or more for the purpose of capturing the hydrogen halide. Specifically, the amount of compound (V) to be used is generally 2.0 to 10.0 times, preferably 2.0 to 5.0
  • a base such as triethylamine may be co-present in the reaction solution instead of adding compound (V) in excess to capture hydrogen halide.
  • the compound The amount of the compound (V) to be used is generally 1.0 to 5.0 times, preferably 1.0 to 3.0 times, the mole of the compound (IV).
  • the reaction temperature is usually 0 to 150 t, preferably 0 to 80.
  • Commercially available 2,2,2-trifluoroethylamine (compound (V)) can be used.
  • compound (IV) When a compound in which R in compound (IV) is a lower alkoxy group is used and a base is not used, it is preferable to add compound (IV) in excess of compound (V).
  • the amount of use is usually 1.0 to 1000 times, preferably 1.0 to 100 times.
  • the reaction 3 ⁇ 4S is usually 0 to 250, preferably 0 to 180. When the reaction temperature exceeds 38 (boiling point of compound (V)), it is desirable to seal the reaction vessel.
  • reaction for converting an amine to an alkali amide proceeds even under a high temperature condition as described above.
  • the reaction temperature is usually 0 to 150 t :, preferably 0 to 100 t.
  • the amount of compound (IV) to be used is generally 1.0 to 5.0 moles, preferably 1.0 to 3.0 moles, relative to compound (V).
  • the amount of the base used is usually 1.0 to 3.0 times, and preferably 1.0 to 2.0 times.
  • the reaction time is in each case several minutes to several days.
  • the reaction is usually carried out using an excess of compound (V) in a solvent or without solvent.
  • the amount of compound (IV) to be used is generally 1.0 to 100-fold mol, preferably 1.0 to 10-fold mol, relative to compound (V).
  • the reaction temperature is generally 0-250, preferably 0-180. In addition, when dehydration such as carposimid is used, the above high temperature is not required.
  • the reaction temperature is usually 0 to 120, preferably 0 to 80, in the presence of a solvent.
  • the amount of compound (IV) to be used is generally 1.0 to 20 moles, preferably 1.0 to 20 moles, relative to compound (V). In any case, if the reaction temperature exceeds 381: (boiling point of compound (V)), it is desirable to seal the reaction vessel.
  • the reaction time is several minutes to several days even in the case of misalignment.
  • reaction conditions are the same as in the above-mentioned method for producing the compound (IV-a) by halogenation of the corresponding carboxylic acid compound (IV-b).
  • reaction formula (J) the compound (IV-b) used in the above-mentioned production step can be produced by hydrolysis of the compound (XI). These are shown in the following reaction formulas. Reaction formula (J)
  • Y represents a cyano group or a lower alkoxycarbonyl group, and X and ⁇ are the same as described above.
  • the above hydrolysis can be performed under any of acidic and basic conditions.
  • an inorganic acid such as hydrochloric acid, hydrobromic acid, or sulfuric acid is usually used as a catalyst.
  • an organic solution such as acetic acid is usually used in addition to water.
  • an alkali metal base such as sodium hydroxide or potassium hydroxide is usually used as the base.
  • an aqueous alcohol solution is usually used in addition to water.
  • the hydrolysis temperature is usually in the range from 20 to the reflux point, preferably in the range from 50 ° C to the reflux point.
  • the reaction time is several minutes to several hours.
  • Compound (XI) which is the starting material for this reaction, can be produced by subjecting compound (XII) to a phenoxylation reaction with compound (III).
  • the reaction conditions are the same as in the method for producing compound (I) by funinoxylation of compound (II) in the second aspect of the present invention. It is. These are represented by the following reaction formulas.
  • the reaction formula (K) is represented by the following reaction formulas.
  • Compound (XII) means compound (IX) and compound (X).
  • the reaction temperature and reaction time described in each of the above-described reaction steps are all within the range that does not adversely affect the yield because of the necessity of the reaction operation. The time can be long.
  • This compound (I) can be used as it is as a herbicide. Generally, it is used in the form of powders, wettable powders, granules, emulsions, etc. together with formulation auxiliaries. In this case, one or more of the present compounds (I) are usually contained in the drug product. 0.1 to 95 wt%, preferably from 0.5 to 90 wt%, more preferably 2 to 70 weight 0/0 containing organic.
  • Carriers used as formulation aids, diluents, and surfactants for example, solid carriers usually include talc, kaolin, bentonite, diatomaceous earth, white carbon, clay, and the like.
  • the liquid diluent include water, xylene, toluene, benzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, and alcohol.
  • Surfactants can be used depending on their effects.
  • the emulsifier usually include polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan monolaurate and the like.
  • Examples of the dispersant usually include lignin sulfonate and dibutyl naphthalene sulfonate.
  • Examples of the wetting agent generally include an alkyl sulfonate and an alkylphenyl sulfonate.
  • the concentration of this compound (I) is usually in the range of 0.001 to 1.0%.
  • the amount of the present compound (I) to be used is usually 0.001 to 10 kg, preferably 0.01 to 5 kg per lha.
  • the concentration and amount used of these may vary depending on the dosage form, the timing of use, the method of use, the place of use, the target crop, and the like, and it is, of course, possible to increase or decrease without being limited to the above range.
  • the present compound (I) can be used in combination with other active ingredients such as fungicides, insecticides, acaricides, herbicides and the like.
  • N- (2,2,2-Trifluoroethyl) 1-4-Methoxy-6-Chloro-l-Pyridine-Irboxamide (0.40g, 0.00149mol) and 4-Chloro-l-cyanophenol (0.25 g, 0.00149 X l.lmol) and cuprous chloride (0.022 g, 0.00149 X0.15 mol) were dissolved in dimethylformamide (about 5 ml), and sodium hydride (0.062 g, 60% in mine-ral oil, 0.00149 X 1.04 mol) was added. Then, the mixture was stirred for about 3 hours at about 110 to 20 L; the reaction solution was partitioned between ethyl acetate and saturated aqueous sodium bicarbonate.
  • the mixture was stirred at about 110 to 120 for about 4 hours, the reaction solution was partitioned with ethyl acetate-water, and the organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated. After purification by silica gel column chromatography (eluent: ethyl acetate Zn-hexane), the product was reprecipitated with diethyl ether Z hexane to obtain the desired product.
  • 3-Amino-6-chlorobenzoic acid (4.6 g, 0.027 mol) is suspended in a mixed solvent of 30 ml of concentrated sulfuric acid and 20 ml of acetic acid, and sodium nitrite (2.07 g, 0.027 X l. Lmol) is added. The mixture was stirred at room temperature. Thereafter, about 200 ml of water was added, and the mixture was stirred for about 2 hours at about 100 t. After partitioning with ethyl acetate / water, the mixture was washed with saturated saline. After drying over anhydrous sodium sulfate, concentrating and silica gel column chromatography
  • a pot filled with horticultural soil (Kureha Chemical Co., Ltd .; same hereafter) is seeded with yamgra, Frasavaso ⁇ , Hakobe, and violet. It was cultivated in ⁇ 10).
  • test compound is dissolved or suspended in acetone, and then Tween20 (manufactured by Wako Pure Chemical Industries, Ltd.) and water are added.
  • concentrations of acetone and Tween20 are 10% (v / v) and 0.5% (v / v, respectively).
  • concentration of the test compound was adjusted so as to have a predetermined amount when sprayed at a ratio of the spraying liquid strength ⁇ OOLZlha. This was evenly sprayed on the plant prepared in (1) with a sprayer.
  • Plants sprayed with the test solution were cultivated again in an artificial weather vessel (at 5 to 10), and after 34 days, the herbicidal rate of the sprayed plots relative to the non-sprayed plots was evaluated by optimism. This was classified according to the following criteria, and shown in Table 2 as the herbicidal activity of the test compound.
  • Survey criteria 1 Herbicidal rate is less than 30%
  • Herbicidal rate is 30% or more and less than 60%
  • Herbicidal rate is 60% or more and less than 80%
  • Herbicidal rate is 80% or more and less than 90%
  • Herbicidal rate is 90% or more
  • Compound (I-11), compound (I-12) and compound (I_10) correspond to the compounds described in Table 1, respectively, and the controls (A) to (D) correspond to the description 2 3 means compounds (A) to (D).
  • .N (2,2,2-trifluoroethyl) 1-4-methoxy 6 — [(substituted or unsubstituted) metacyanophenoxy] —2 monopyridinecarboxamide is Since it is a new compound and exhibits high herbicidal properties, it is useful as an active ingredient of a herbicide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pyridine Compounds (AREA)

Abstract

L'invention concerne des dérivés de N-(2,2,2-Trifluoroéthyl)-4-méthoxy-6-[(substitué ou non substitué) m-cyanophénoxy]-2-pyridinecaroxamide, s'utilisant comme ingrédient actif d'herbicides possédant d'excellentes propriétés ; un procédé de préparation de ces dérivés ; et des herbicides les contenant.
PCT/JP2000/003666 1999-06-09 2000-06-06 Nouveaux derives de n-(2,2,2-trifluoroethyl)-4-methoxy-6-[(substitue ou non substitue) m-cyanophenoxy]-2-pyridinecaroxamide, leur procede de production et herbicides afferents Ceased WO2000075112A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2000249545A AU2000249545A1 (en) 1999-06-09 2000-06-06 Novel n-(2,2,2-trifluoroethyl)-4-methoxy-6-((substituted or unsubstituted) m-cyanophenoxy)-2-pyridinecarboxamide derivatives, process for the preparation thereof and herbicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/162221 1999-06-09
JP16222199 1999-06-09

Publications (1)

Publication Number Publication Date
WO2000075112A1 true WO2000075112A1 (fr) 2000-12-14

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AU (1) AU2000249545A1 (fr)
WO (1) WO2000075112A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003000679A3 (fr) * 2001-06-23 2003-04-24 Bayer Cropscience Gmbh Pyridine substituee herbicide, son procede de fabrication et son utilisation comme herbicide et regulateur de croissance des plantes
WO2003051119A1 (fr) * 2001-12-15 2003-06-26 Bayer Cropscience Limited Nouveaux composes herbicides et procede
WO2005007627A1 (fr) * 2003-07-18 2005-01-27 Nihon Nohyaku Co., Ltd. Derive de phenylpyridine, produit intermediaire correspondant, et herbicide contenant ledit derive de phenylpyridine en tant qu'ingredient actif
WO2006006569A1 (fr) * 2004-07-12 2006-01-19 Nihon Nohyaku Co., Ltd. Dérivé de phénylpyridine ou sel de celui-ci, herbicide contenant celui-ci comme ingrédient actif et procédé d'utilisation de celui-ci

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5384305A (en) * 1990-11-28 1995-01-24 Shell Research Limited Herbicidal carboxamide compounds
EP0881217A1 (fr) * 1995-12-28 1998-12-02 Kureha Kagaku Kogyo Kabushiki Kaisha Procede de production de pyridinecarboxamides ou de thiocarboxamides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5384305A (en) * 1990-11-28 1995-01-24 Shell Research Limited Herbicidal carboxamide compounds
EP0881217A1 (fr) * 1995-12-28 1998-12-02 Kureha Kagaku Kogyo Kabushiki Kaisha Procede de production de pyridinecarboxamides ou de thiocarboxamides

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003000679A3 (fr) * 2001-06-23 2003-04-24 Bayer Cropscience Gmbh Pyridine substituee herbicide, son procede de fabrication et son utilisation comme herbicide et regulateur de croissance des plantes
US6794336B2 (en) 2001-06-23 2004-09-21 Aventis Crop Science Gmbh Herbicidal substituted pyridines, their preparation, and their use as herbicides and plant growth regulators
RU2304141C2 (ru) * 2001-06-23 2007-08-10 Байер Кропсайенс Гмбх Производные пиридина и гербицидное средство на их основе
WO2003051119A1 (fr) * 2001-12-15 2003-06-26 Bayer Cropscience Limited Nouveaux composes herbicides et procede
WO2005007627A1 (fr) * 2003-07-18 2005-01-27 Nihon Nohyaku Co., Ltd. Derive de phenylpyridine, produit intermediaire correspondant, et herbicide contenant ledit derive de phenylpyridine en tant qu'ingredient actif
WO2006006569A1 (fr) * 2004-07-12 2006-01-19 Nihon Nohyaku Co., Ltd. Dérivé de phénylpyridine ou sel de celui-ci, herbicide contenant celui-ci comme ingrédient actif et procédé d'utilisation de celui-ci

Also Published As

Publication number Publication date
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