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WO1993020035A1 - Procede de production d'un derive de cyclopropane - Google Patents

Procede de production d'un derive de cyclopropane Download PDF

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Publication number
WO1993020035A1
WO1993020035A1 PCT/JP1993/000414 JP9300414W WO9320035A1 WO 1993020035 A1 WO1993020035 A1 WO 1993020035A1 JP 9300414 W JP9300414 W JP 9300414W WO 9320035 A1 WO9320035 A1 WO 9320035A1
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Prior art keywords
formula
compound represented
same meaning
reaction
compound
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Ceased
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PCT/JP1993/000414
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English (en)
Japanese (ja)
Inventor
Tsutomu Inoue
Mitsumasa Takata
Tatsumi Suzuki
Kenji Saito
Keiichi Ishimitsu
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.)
Nippon Soda Co Ltd
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Nippon Soda Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP11065892A external-priority patent/JP3171277B2/ja
Priority claimed from JP4118334A external-priority patent/JPH05286888A/ja
Priority claimed from JP2363693A external-priority patent/JPH06211780A/ja
Application filed by Nippon Soda Co Ltd filed Critical Nippon Soda Co Ltd
Publication of WO1993020035A1 publication Critical patent/WO1993020035A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/24—Sulfones; Sulfoxides having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C07C317/46—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
    • C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
    • C07C49/427—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
    • C07C49/433—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings the condensed ring system containing seven carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/792—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/18—Saturated compounds containing keto groups
    • C07C62/24—Saturated compounds containing keto groups the keto group being part of a ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety

Definitions

  • the present invention relates to a method for producing a cyclopropane derivative useful as a herbicide.
  • JP-A-5-70426 describes that the following cyclopropane derivatives are useful as herbicides.
  • G 1 represents a lower alkyl, an optionally substituted phenyl, an optionally substituted aralkyl, or an optionally substituted heterocycle.
  • G 2 is the same or different and represents a halogen, an alkoxy, an alkylthio, an alkylsulfonyl, an alkyl, an alkoxyalkyl, an alkoxycarbonyl, and n is 0-4.
  • G 3 and are the same or different and represent hydrogen or lower alkyl.
  • a stereoisomer exists between the substituent at the 5-position and the cyclic propane ring in the bicycling portion of the synthetic propane derivative.
  • C1CH 2 CH CHC0CH 3 was an unstable substance, and had problems in the control of the reaction and the yield fluctuation.
  • COCHaCHClCHiiCl is unstable and difficult to isolate.
  • references describing reactions related to the reactions D and E include WO91 / 02026, WO92 / 13821, and JP-A-4-24. 7053 and JP-A-5-704426.
  • WO91 / 02026, WO92 / 13821, and JP-A-4-24. 7053 and JP-A-5-704426 are cis.
  • the present invention provides a method for producing a desired cyclopropane derivative in high yield and high purity.
  • the present invention comprises the steps of the following reactions A to G;
  • R 1 represents an alkyl group
  • R 2 represents an optionally substituted phenyl group, an optionally substituted aralkyl group or an optionally substituted heterocyclic ring.
  • X ⁇ and X 2 are the same or different and represent a halogen atom
  • R 1 , R 3 R 4 and R 5 represent the same or different and represent hydrogen or alkyl.
  • a solvent using methylene chloride, black hole Holm, Jikuroroetan, an inert solvent such as nitrobenzene, as a catalyst, A l C l 3, A l B r 3, S nC l 4, TIC 1
  • the reaction is carried out at a temperature of from 120 ° C to the boiling point of the solvent, preferably from 0 ° C to room temperature.
  • an inert solvent such as methylene chloride, ether, or BTX is used as a solvent
  • an organic base such as DBU, a base such as potassium carbonate, sodium carbonate, sodium ethylate, and potassium ethylate are used as bases.
  • the reaction is carried out at a temperature of from 120 ° C. to the boiling point of the solvent, preferably from 0 ° C. to room temperature, using an inorganic base such as a metal alcohol such as a metal alcoholate. It can also be obtained by a two-phase reaction using a catalyst such as BTEC and a hydroxylation power, sodium hydroxide or the like as a base.
  • R 1 , R 3 and R 4 have the same meanings as described above (The reaction is carried out using a cyclopropane derivative represented by the formula [V] in the presence of a base in a suitable solvent.
  • alcohols such as methanol and ethanol, DMF or a mixed solvent thereof, and as a base, a sodium alcohol or a potassium alcohol is used.
  • the reaction is carried out at room temperature to 150 ° C., preferably at the boiling point of the alcohol used.
  • the amount of the base is 1 to 5 moles, preferably 1 to 2 moles, per mole of the cyclopropane derivative.
  • R 1 , R 2 , and R 3 have the same meanings as described above, and L ′ represents a leaving group such as halogen, alkylcarbonyloxy, alkoxycarbonyloxy, and benzoyloxy.
  • the compound [V [-1] or [VI-2] and the compound IW] are reacted in a solvent in the presence of an equimolar or excess base.
  • Bases et al used KOH, N a 0 an alkali metal hydroxide such as H, an alkaline earth metal hydroxide, tri (C, one C 6 alkyl) ⁇ Mi emissions, pyridinium Jin, carbonate sodium phosphate Sodium, methylene chloride, methylene chloride, chloroform, toluene, ethyl acetate, dimethylformamide, THF, dimethoxetane, acetonitrile and the like.
  • the reaction mixture is stirred at 0 ° C to 50 ° C until the reaction is completed. It can also be obtained by reacting in a two-phase system using a phase transfer catalyst such as BTEAC.
  • the latter rearrangement is carried out in the presence of a cyano compound and a mild base.
  • the above compound [XI-1] or compound [XI-2] can be prepared by, for example, converting 1 mol of the compound [X1 ⁇ 1] or compound [XI-2] to 1 to 4 mol of a base, preferably 1 to 2 mol.
  • the reaction is carried out with 0.1 mol of the base and 0.1 mol to 0.5 mol or more, preferably 0.1 mol.
  • the base used here any of the above bases can be used.
  • the cyano compound a polymer holding lithium cyanide, acetate cyanohydrin, hydrogen cyanide, or potassium cyanide is used.
  • the reaction is completed in a shorter time by adding a small amount of a phase transfer catalyst such as a crown ether.
  • a phase transfer catalyst such as a crown ether.
  • the reaction is carried out at a temperature lower than 80 ° C, preferably at 20 ° C to 40 ° C.
  • Solvents used are 1,2-dichloroethane, toluene, acetonitril, methylene chloride, ethyl acetate, Examples include dimethylformamide, methylisobutyl ketone, THF, and dimethoxyethane.
  • the reaction in the first half can be obtained by reacting compound [VI-1] or ["VI-2"] with compound [''! "] In a solvent with an equimolar or excess of dicyclohexylcarpoimide (DCC).
  • DCC dicyclohexylcarpoimide
  • reaction mixture is stirred at 0 ° C to 50 ° C until the reaction is completed.
  • R 2 has the same meaning as described above, and X represents a halogen atom.
  • the compound of formula [XI] is reacted with cyanide in an inert solvent in the presence of a catalyst.
  • the inert solvent include BTX solvents such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride and chloroform.
  • BTX solvents such as benzene and toluene
  • halogenated hydrocarbons such as methylene chloride and chloroform.
  • cyanide for example, trialkylsilyl cyanide can be cited (Reference: Synthesis, 1979,
  • the compound represented by the formula [ ⁇ ] is reacted with a cyanide under an inert gas atmosphere at 140 to 200 ° C., preferably at I 50 to 170.
  • cyanide include copper (I) cyanide, mercury cyanide, silicon
  • inert gas include nitrogen gas (reference: Angew. Chem., 68, 425 (1956)).
  • phase transfer catalyst examples include sodium cyanide and potassium cyanide, and examples of the inert solvent include solvents such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride and chloroform.
  • phase transfer catalyst examples include ammonium salts, phosphonium salts, and crown ethers, which are known as phase transfer catalysts (Reference: Tetrahedron Lett., 1979, 22775).
  • the compound represented by the formula [XI] is reacted with a cyanide in an inert solvent in the presence of a phase transfer catalyst at 50 to 100 ° C, preferably 70 to 90 ° C.
  • a phase transfer catalyst at 50 to 100 ° C, preferably 70 to 90 ° C.
  • the cyanide include copper cyanide (1), sodium cyanide, and potassium cyanide.
  • the inert solvent include DMF, DMSO, and acetonitrile, and preferably acetonitrile.
  • the phase transfer catalyst include ammonium salts, phosphonium salts, and crown ethers, which are known as phase transfer catalysts.
  • the compound represented by the formula [W ′ ′′] reacts with the compound represented by the formula [XIII] by the following reaction to produce the compound represented by the formula [XIV] in high yield.
  • R 2 has the same meaning as described above, and A represents an optionally substituted 5- to 7-membered carbocyclic ring or an optionally substituted 5- to 7-membered heterocyclic ring containing N, 0 or S.
  • the reaction is carried out by heating an equimolar mixed solution of ['] and [XIE] and a base.
  • the base include pyridine, triethylamine, DB ⁇ ⁇ ⁇ and the like.
  • the solvent methylene chloride, chloroform, acetonitrile, toluene and the like are used, and the reaction is carried out from room temperature to the boiling point of these solvents.
  • the compound represented by the formula (xm) is, for example,
  • R e , R 7 , R 8 , R 0, R 10 v R 11 are the same or different and are each independently a halogen atom, an optionally substituted alkyl group, an alkoxycarbonyl group, or an optionally substituted It represents a good alkenyl group or a phenyl group which may be substituted, and may form a 3- to 7-membered carbon ring which may be substituted by R 7 and R 8 .
  • R I2, R I3, R 14 , R 15 taken same or different from and represent hydrogen or lower alkyl.
  • R 16 represents hydrogen.
  • R 17 represents OR 18 , R 18 represents hydrogen, lower alkyl, aralkyl, lower acetyl-alkylsulfonyl, arylsulfonyl, or R 16 and R 17 may together represent a single bond.
  • Z represents oxygen, sulfur or N—R 19 , where R 18 is hydrogen, lower alkyl, optionally substituted aralkyl, optionally substituted cycloalkyl, optionally substituted phenyl, Or a heterocyclic ring which may be substituted.
  • Oxidation reaction When an alkylthio group is present in the compound [xw], it can be converted into an alkylsulfonyl group in high yield by oxidation.
  • the reaction is performed by a usual oxidation reaction.
  • the reaction is carried out by heating at least twice the molar amount of hydrogen peroxide and the compound [XIV] using sodium tungstate as a catalyst.
  • the solvent water, alcohols, or a mixed solvent thereof is used, and the reaction is carried out at a temperature other than 100 or the boiling point of these solvents.
  • R 1 , R 2 and R 3 have the same meanings as described above, and M represents a metal atom.
  • Metal atoms are alkali metals and alkaline earth metals.
  • As the solvent hydrolyzed using alcohol, water, and preferably from room temperature a mixture thereof is used to the boiling point of the solvent at room temperature N a 0 H, KOH, alkali etc. Na 2 C0 3. K 2 C 03 . Reaction ::
  • R 1 and R 2 have the same meaning as described above.
  • the reaction is carried out in a solvent in the presence of an organic acid.
  • organic acid acetic acid-formic acid, propionic acid, citric acid and the like are used, and water, alcohols and the like are used as solvents, and the reaction temperature is preferably around room temperature.
  • R 1 , R 2 and ⁇ have the same meanings as described above.
  • reaction G is carried out by adjusting the solution to an acidic or neutral condition with an acid (usually, the reaction solution of the reaction D is used as it is.
  • the acid is an inorganic acid such as hydrochloric acid, sulfuric acid or the like. Is fine.
  • R 1 and R 2 have the same meaning as described above.
  • the reaction is performed in a solvent in the presence of a base.
  • a base an organic salt group such as ammonia, (C, -C) alkylamine, di (C, -C) alkylamine, tri (C, -C) alkylamine, pyridine, or DBU is used.
  • the reaction is carried out in an organic solvent such as alcohols, ethers and THF under cooling to the boiling point of the solvent, preferably at room temperature.
  • the synthesized compound was identified by NMR, IR, MS and the like.
  • the compounds according to the present invention include a number of tautomeric forms, for example,
  • the filtrate was further separated by silica gel chromatography to obtain 8.1 g of the E-form and 27.8 g of the Z-form [cis-ethoxycarbonyl trans-methyl-form Z-cyclopropane pan; the same applies hereinafter).
  • 0.2 ml of tin tetrachloride was added to 50 ml of a methylene chloride solution of 2.6 g of 2-methyl-4-methylsulfonyl-3-cyclomethoxybenzoic acid chloride and 1.1 g of trimethylsilyl cyanide. It was added at room temperature under a nitrogen atmosphere. After stirring for 20 hours, the reaction solution was poured into water. The aqueous layer was separated, and the organic layer was washed twice with 50 ml of water, and then dried and concentrated to obtain a crude product of 3-methoxy-2-methyl-4-mesylbenzoyl cyanide.
  • Triethylamine was added to a solution of this crude product and 1.2 g of t.rans-5-ethoxycarboxyl cis-5-methyl-12-bicyclo [4.1.0] heptene-12,4-dione in 20 ml methylene chloride. 0.9 ml was added. After stirring the reaction mixture at room temperature for 5 hours, it was poured into 1N hydrochloric acid. The aqueous layer was separated, and the organic layer was washed with saturated saline. After drying and concentration, the residue was purified by silica gel column chromatography (eluent: hexane monoacetate) to obtain 1.2 g of the target compound (E-form).
  • Triethylamine ⁇ .8 was added to 2.49 g and 0.83 g of methylene chloride solution, respectively, and then 2-methyl-14-methylsulfonyl-3-methoxybenzoic acid chloride 4.2 g of methylene chloride solution 1 was added to this solution. 0 ml was added dropwise at 10 ° C for 0.1 hour. After stirring at room temperature for 2 hours, the mixture was poured into 1N hydrochloric acid and the organic layer was separated. After washing sequentially with water and a saturated aqueous sodium chloride solution, the mixture was dried over magnesium sulfate and concentrated to obtain 6.9 g of a mixture of E-form and Z-form of 0-acyl form.
  • the herbicide represented by the formula (I) can be obtained in high yield and high purity irrespective of the configuration of the compound obtained in the course of the process.
  • Compounds obtained on the way can be intermediates for agricultural chemicals, etc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de production d'un composé répondant à la formule générale [1], selon le schéma (A), où R1 représente alkyle; R2 représente alkyle, phényle éventuellement substitué, aralkyle éventuellement substitué ou bien un hétérocycle éventuellement substitué; R3 et R4 représentent chacun alkyle; X1 et X2 représentent chacun halogène; L représente un groupe labile; et M représente un atome de métal.
PCT/JP1993/000414 1992-04-03 1993-04-01 Procede de production d'un derive de cyclopropane Ceased WO1993020035A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP4/110658 1992-04-03
JP11065892A JP3171277B2 (ja) 1992-04-03 1992-04-03 （２−アシルシクロプロピル）アルキルマロン酸ジエステルの製造法
JP4/118333 1992-04-10
JP4/118334 1992-04-10
JP11833392 1992-04-10
JP4118334A JPH05286888A (ja) 1992-04-10 1992-04-10 ビシクロ〔４，１，０〕ヘプタン−２，４−ジオン誘導体の新規な製法
JP5/23636 1993-01-19
JP2363693A JPH06211780A (ja) 1993-01-19 1993-01-19 ベンゾイルシアナイド誘導体、その製法及びそれを用いた反応

Publications (1)

Publication Number Publication Date
WO1993020035A1 true WO1993020035A1 (fr) 1993-10-14

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PCT/JP1993/000414 Ceased WO1993020035A1 (fr) 1992-04-03 1993-04-01 Procede de production d'un derive de cyclopropane

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WO (1) WO1993020035A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3171277B2 (ja) 1992-04-03 2001-05-28 日本曹達株式会社 （２−アシルシクロプロピル）アルキルマロン酸ジエステルの製造法
CN114794105A (zh) * 2022-06-13 2022-07-29 广西民族大学 蒈烷-3,4-二醇在作为或制备除草剂方面的应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6087238A (ja) * 1983-09-16 1985-05-16 ストウフアー・ケミカル・カンパニー ２‐（２‐置換ベンゾイル）‐１，３‐シクロヘキサンジオン
JPH03255047A (ja) * 1989-07-04 1991-11-13 Nippon Soda Co Ltd 置換ビシクロヘプタジオン誘導体、その製造方法及び除草剤
JPH04247052A (ja) * 1991-01-31 1992-09-03 Nippon Soda Co Ltd ビシクロ〔４，１，０〕ヘプタン−２，４−ジオン誘導体、その製造法
JPH04247053A (ja) * 1991-01-31 1992-09-03 Nippon Soda Co Ltd ビシクロ〔４，１，０〕ヘプタン−２，４−ジオン誘導体の製造方法
JPH0570426A (ja) * 1991-06-04 1993-03-23 Nippon Soda Co Ltd ３−置換ベンゾイル−ビシクロ〔４、１、０〕ヘプタン−２，４−ジオン誘導体、その除草剤及び除草用組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6087238A (ja) * 1983-09-16 1985-05-16 ストウフアー・ケミカル・カンパニー ２‐（２‐置換ベンゾイル）‐１，３‐シクロヘキサンジオン
JPH03255047A (ja) * 1989-07-04 1991-11-13 Nippon Soda Co Ltd 置換ビシクロヘプタジオン誘導体、その製造方法及び除草剤
JPH04247052A (ja) * 1991-01-31 1992-09-03 Nippon Soda Co Ltd ビシクロ〔４，１，０〕ヘプタン−２，４−ジオン誘導体、その製造法
JPH04247053A (ja) * 1991-01-31 1992-09-03 Nippon Soda Co Ltd ビシクロ〔４，１，０〕ヘプタン−２，４−ジオン誘導体の製造方法
JPH0570426A (ja) * 1991-06-04 1993-03-23 Nippon Soda Co Ltd ３−置換ベンゾイル−ビシクロ〔４、１、０〕ヘプタン−２，４−ジオン誘導体、その除草剤及び除草用組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3171277B2 (ja) 1992-04-03 2001-05-28 日本曹達株式会社 （２−アシルシクロプロピル）アルキルマロン酸ジエステルの製造法
CN114794105A (zh) * 2022-06-13 2022-07-29 广西民族大学 蒈烷-3,4-二醇在作为或制备除草剂方面的应用
CN114794105B (zh) * 2022-06-13 2024-03-15 广西民族大学 蒈烷-3,4-二醇在作为或制备除草剂方面的应用

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