WO2009077590A1 - Procédé de fabrication d'esters de l'acide 2,2-dichlorocyclopropanecarboxylique - Google Patents

Procédé de fabrication d'esters de l'acide 2,2-dichlorocyclopropanecarboxylique Download PDF

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Publication number
WO2009077590A1
WO2009077590A1 PCT/EP2008/067894 EP2008067894W WO2009077590A1 WO 2009077590 A1 WO2009077590 A1 WO 2009077590A1 EP 2008067894 W EP2008067894 W EP 2008067894W WO 2009077590 A1 WO2009077590 A1 WO 2009077590A1
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formula
alkyl
cycloalkyl
compound
compounds
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PCT/EP2008/067894
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German (de)
English (en)
Inventor
Martin Sukopp
Michael Keil
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention relates to a process for the preparation of 2,2-Dichlorcyclopropancarbonklaestern.
  • a large number of salts, esters and other derivatives of 2,2-dichlorocyclopropane carboxylic acids are of interest as fungicidal or insecticidal agents or as starting compounds for the preparation of such active compounds.
  • haloform compounds trihalomethanes
  • chloroform trichloromethane
  • dihalocarbenes which are capable of addition to olefinic double bonds to form a gem-dihalocyclopropane group.
  • DE 2 324 390 describes a process for the preparation of derivatives of cyclobutane, in which an aqueous alkali metal hydroxide solution having an organic phase containing a haloformate and a compound capable of reacting with dihalomethyls, in the presence of an onium compound as phase transferka -
  • the catalyst is brought into contact with each other.
  • the reaction of tert.-alkyl esters of .alpha.,. Beta.-unsaturated carboxylic acids with chloroform and aqueous alkali in the presence of quaternary ammonium compounds is described.
  • the object of the present invention is to provide a process by means of which 2,2-dichlorocyclopropanecarboxylic acid esters can be prepared in high yields without the need of using sulfonium and phosphonium compounds.
  • the process should minimize the undesirable side reactions that normally occur.
  • the reaction time should be reduced, whereby the reaction and any side reactions should remain controllable despite exotherm.
  • the present invention relates to a process for the preparation of compounds of formula (I),
  • R 1 is d-Ce-alkyl, C 3 -C 8 -cycloalkyl, C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl, C 3 -C 8 -cycloalkyl-C 1 -C 4 -alkyl or benzyl,
  • R 2 represents hydrogen, Ci-C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-Ci-C 4 -alkyl or benzyl, and
  • R 3 and R 4 independently of one another represent hydrogen, C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl,
  • R 1 , R 2 , R 3 and R 4 have the previously given meaning
  • R 5 (CH 3) 3 NI, wherein R 5 is C 2 -C 0 -alkyl, Cs-Cs-cycloalkyl, C 3 -C 8 - Cycloalkyl-Ci-C4-alkyl, phenyl, ToIyI or benzyl, is reacted.
  • the compounds of formula (I) are obtained in high yield.
  • Side reactions such as hydrolysis of the ester group or addition of CCI 3 "to the ⁇ -carbon atom, occur to a much lesser extent, premature hydrolysis of the ester group in the compounds of formula (II) under the conditions of reaction with chloroform especially because of that problematic because the carboxylic acid corresponding to the ester of the formula (II) is no longer cyclopropanated.
  • the iodide instead of the corresponding chloride or bromide as a catalyst, the selectivity to undesirable side reactions is significantly increased. It is believed that this is due to partial deactivation of the catalyst by the iodide.
  • variables for organic groups are, for example, the term "d-C ⁇ -Alky!, Collective terms that stand for the individual members of these groups of organic entities.
  • the prefix C x -Cy denotes the number of possible carbon atoms in each case.
  • C 1 -C 6 -alkyl as used herein and in the alkyl moieties of C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl or C 3 -C 6 -cycloalkyl-C 1 -C 4 -alkyl denotes a saturated, straight-chain or branched hydrocarbon group comprising 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1 Methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpent
  • C 1 -C 4 -alkyl includes, for example, methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl.
  • C 2 -C 10 -alkyl denotes a saturated, straight-chain or branched hydrocarbon group comprising 2 to 10 carbon atoms, such as the aforementioned C 1 -C 6 -alkyl and 1-heptyl, 2-heptyl, 3-heptyl, 1, 1 Dimethylpentyl, 1-octyl, 2-octyl, 3-octyl, 1, 1-dimethylhexyl, 2,2,4-trimethylpenyl, 2-ethylhexyl, 1-nonyl, 2-nonyl, 2,4-dimethylheptyl, 1-decyl , 2-decyl, 2-propylheptyl etc.
  • C 1 -C 6 -alkoxy as used herein and in the alkoxy groups of C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl describes straight-chain or branched alkyl groups comprising 1 to 6, in particular 1 to 4, carbon atoms which are bonded via a Oxygen atom, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, 1, 1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3 Methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,
  • Cs-Cs-cycloalkyl as used herein and in the cycloalkyl groups of C3-C8-cycloalkyl-Ci-C4-alkyl describes mono- or bicyclic hydrocarbon groups comprising 3 to 8 carbon atoms.
  • monocyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • bicyclic groups include bicyclo [2.2.1] heptyl,
  • C 3 -C 6 -cycloalkyl include in particular cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • the expression describes straight-chain or branched alkyl groups having 1 to 4 carbon atoms, one of the hydrogen atoms of these groups being replaced by a C 1 -C 6 -alkoxy group as defined above.
  • these are methoxymethyl, ethoxymethyl, n-propoxymethyl, 1-methylethoxymethyl, n-butoxymethyl, 1-methylpropoxymethyl, 2-methylpropoxymethyl, 1, 1-dimethylethoxymethyl, n-pentoxymethyl, 1-methylbutoxymethyl, 2-methylbutoxymethyl, 3-methyl - Butoxymethyl, 1, 1-dimethylpropoxymethyl, 1, 2-dimethylpropoxymethyl, 2,2-dimethylpropoxymethyl, 1-ethylpropoxymethyl, n-hexoxymethyl, 1-methylpentoxymethyl, 2-methylpentoxymethyl, 3-methylpentoxymethyl, 4-methylpentoxymethyl, 1, 1 Dimethylbutoxymethyl, 1, 2-dimethylbutoxymethyl, 1, 3-dimethylbutoxymethyl, 2,2-dimethylbutoxymethyl, 2,3-dimethylbut
  • C 1 -C 4 -alkoxy-C 1 -C 2 -alkyl are in particular methoxymethyl, ethoxymethyl, n-propoxymethyl, 1-methylethoxymethyl, n-butoxymethyl, 1-methylpropoxymethyl, 2-methylpropoxymethyl, 1, 1-dimethylethoxymethyl, 2 -Methoxyethyl, 2-ethoxy. ethyl, 2-n-propoxyethyl, 2- (1-methylethoxy) ethyl, 2- (n-butoxy) ethyl, 2- (1-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl and 2- (1 , 1-dimethylethoxy) ethyl.
  • C 3 -C 8 -cycloalkyl-C 1 -C 4 -alkyl describes straight-chain or branched alkyl groups having 1 to 4 carbon atoms, one of the hydrogen atoms of these groups being replaced by a C 5 -C 8 -cycloalkyl group as defined above.
  • Examples of these are cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, 1-cyclopropylethyl, 1-cyclobutylethyl, 1-cyclopentylethyl, 1-cyclohexylethyl, 1-cycloheptylethyl, 1-cyclooctylethyl, 2-cyclopropylethyl, 2- Cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 1-cyclopropylpropyl, 1-cyclobutylpropyl, 1-cyclopentylpropyl, 1-cyclohexylpropyl, 1-cycloheptylpropyl, 1-cyclooctylpropyl, 2-cyclopropyl
  • C 3 -C 6 -cycloalkyl-C 1 -C 2 -alkyl are in particular cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, 2-cyclopropylethyl, 2-cyclobutylethyl, 2-cyclopentylethyl or 2-cyclohexylethyl.
  • the reaction according to the invention is carried out by bringing into contact, in particular mixing, the abovementioned constituents of the reaction mixture in reaction vessels customary for such reactions, it being possible to design the reaction reaction both continuously and discontinuously.
  • the reaction is carried out without pressure.
  • the reaction can also be carried out under pressure.
  • under reaction conditions in connection with the addition of chloroform and the compound of formula (II) denotes that these are a reaction vessel containing a mixture of the compounds other than chloroform and the compound of formula (II); H. a portion or the total amount of the aqueous alkali metal hydroxide solution and the ammonium iodide and optionally an inert solvent, are fed at reaction temperature and reaction pressure.
  • chloroform and the compound of the formula (II) may be added separately or in admixture with the reaction.
  • the addition of chloroform and the compound of formula (II) can be carried out over the reaction time distributed in aliquots or continuously.
  • Chloroform and the compound of the formula (II) are usually added in a ratio to one another, corresponding to the ratio of the respective total amounts, to the reaction.
  • chloroform and the compound of the formula (II) is preferably carried out at a rate which corresponds essentially to the reaction rate or the consumption of the two starting compounds in the reaction with one another.
  • the reaction mixture may contain, in addition to the aforementioned ingredients, an inert solvent other than water and chloroform.
  • Suitable solvents are the solvents known from the prior art, such as alkanes, cycloalkanes, acyclic ethers or cyclic ethers.
  • the reaction in the process according to the invention is preferably carried out essentially without addition of a solvent which is different from water and chloroform, ie. H.
  • the content of a solvent other than water and of chloroform is usually less than 20% by volume, in particular less than 5% by volume and especially less than 1% by volume, in each case based on the total volume of the reaction mixture.
  • ammonium iodide of the formula R 5 (CH 3) 3 NI denotes an application rate of this compound which lower than that of the compound of the formula (II) and the rate of reaction of the reaction of the compound of the formula (II) to a compound of the formula (I), in particular compared to the reaction rates of the side reactions occurring, significantly increased.
  • the ammonium iodide of the formula R 5 (CH 3 ) 3NI is customarily used in an amount of from 0.01 to 10 mol%, preferably from 0.02 to 5 mol% and particularly preferably from 0.5 to 2 mol%, in each case based on 1 mol (100 mol%) of the compound of formula (II), use.
  • Ammonium iodide of the formula R 5 (CH3) 3l ⁇ ll is preferably selected fertilize under connects, wherein R 5 is C2-C6 alkyl, Cs-C ⁇ cycloalkyl, phenyl or benzyl. R 5 is particularly preferably C 2 -C 6 -alkyl and very particularly preferably ethyl.
  • ammonium iodide of the formula R 5 (CH 3) 3 NI can be isolated, for example, by extraction and used again in the process according to the invention.
  • ammonium iodide of the formula R 5 (CH 3) 3 NI is generally readily water-soluble and can be separated by extraction from the reaction product of the formula (I). This results in a significantly better phase separation and a more complete separation of ammonium iodide of the formula R 5 (CH 3) 3 NI and reaction product of the formula (I) than in the use of the corresponding ammonium chlorides or bromides.
  • inorganic iodide includes the salts of hydroiodic acid.
  • examples of inorganic iodides are alkali metal iodides, such as lithium iodide, sodium iodide or potassium iodide, alkaline earth metal iodides, such as calcium iodide, transition metal iodides, such as iron iodide, copper iodide or zinc iodide, metal iodides, such as aluminum iodide, or iodides of non-metal-containing onium ions, such as ammonium iodide.
  • Preferred inorganic iodides are alkali metal or alkaline earth metal iodides, especially alkaline earth metal iodides such as sodium iodide or potassium iodide.
  • the inorganic iodide and the compound of the formula R 5 (CH 3) 3 NX will usually be used in approximately equimolar amounts, ie for example in a molar ratio of 0.8: 1 to 1: 0.8, based on each other , However, preference is given to using the inorganic iodide in slight excess, based on the compound of the formula R 5 (CH 3) 3 NX.
  • the used amount of the compound of the formula R 5 (CH3) 3l ⁇ IX connects to the fertil of formula (II) applies the previously to the amount of compound of the formula R 5 (CH 3) 3 NI said.
  • the chloroform is used in an amount of from 1 to 10 mol, preferably from 1.2 to 5 mol and more preferably from 1.5 to 2.5 mol, in each case based on 1 mol of the compound of the formula (II ).
  • the aqueous alkali metal hydroxide solution is customarily used in an amount of from 1 to 15 mol, preferably from 2 to 8 mol and more preferably from 4 to 6 mol, in each case based on 1 mol of the compound of the formula (II) , calculated as alkali metal hydroxide use.
  • the aqueous alkali metal hydroxide solution used according to the invention preferably has an alkali metal hydroxide content of at least 30% by weight and more preferably of at least 40% by weight.
  • the maximum content of the solution of alkali metal hydroxide is determined by the solubility of the alkali metal hydroxide at the reaction temperature. Usually, however, the content of the alkali metal hydroxide solution will not exceed 80% by weight and more preferably 60% by weight
  • alkali metal hydroxides are lithium hydroxide, sodium hydroxide and potassium hydroxide.
  • the aqueous alkali metal hydroxide solution is preferably selected from sodium hydroxide solution and potassium hydroxide solution, the aqueous alkali metal hydroxide solution is particularly preferably sodium hydroxide solution and very particularly preferably sodium hydroxide solution having a sodium hydroxide content of from 40 to 60% by weight.
  • the reaction is therefore preferably carried out at a temperature in the range from 15 to 65 ° C. and more preferably from 30 to 50 ° C.
  • the reaction time depends on the respective starting compounds and the selected reaction parameters. Usually, however, the reaction time is in the range of 2 to 24 hours. Preferably, one will choose the reaction parameters so that the reaction time is in the range of 4 to 16 hours.
  • reaction mixtures in particular the aqueous reaction mixtures, with an acrylate stabilizer and / or reacting the compound of the formula (II) with chloroform to carry out an oxygen depleted atmosphere, d. H. at an oxygen content of the reaction atmosphere of less than 20% and in particular less than 10% or under a protective gas atmosphere, for. B. under nitrogen or argon.
  • Suitable acrylate stabilizers are, for example, compounds which act as antioxidant and / or radical scavenger. These compounds include, for example, hydroxyphenols, alkyl-substituted hydroxyphenols and their alkyl ethers, such as methylhydroquinone, di-tert-butoxytoluene, hydroquinone monomethyl ether, hydroquinone monobenzyl ether or 4-tert-butylcatechol, compounds having nitroxyl groups, such as 2,2,6,6- Tetramethylpiperidine-N-oxyl (TEMPO) or 4-hydroxy-TEMPO, aminophenols such as 2-aminophenol, phenothiazines and substituted phenothiazines or bisulfites. Such compounds are preferably used in an amount of 1 to 1000 ppm, preferably 10 to 100 ppm and in particular 30 to 70 ppm (ppm by weight), based on the weight fraction of the compounds of formula (II).
  • hydroxyphenols alkyl-sub
  • R 1 in the compounds of the formula (I) and (II) is preferably C 1 -C 4 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy-C 1 -C 2 -alkyl or benzyl.
  • R 1 is particularly preferably C 1 -C 4 -alkyl or benzyl.
  • R 1 is C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, 1-methylethyl or n-butyl.
  • R 2 in the compounds of the formula (I) and (II) is preferably hydrogen or C 1 -C 4 -alkyl.
  • R 2 particularly preferably represents hydrogen, methyl or ethyl.
  • R 3 and R 4 in the compounds of the formula (I) and (II) independently of one another are preferably hydrogen or C 1 -C 4 -alkyl. Particularly preferably, R 3 and R 4 independently of one another are hydrogen, methyl or ethyl. In particular, we at least one of the two radicals R 3 or R 4 and in particular both radicals R 3 and R 4 is hydrogen.
  • esters of the formula (I) can be obtained from the reaction mixture in a manner known per se, for. B. by extractive means and / or by distillation measures. In general, one will first remove the aqueous phase and then neutralize any basic constituents in the organic phase. In general, then a distillative workup of the organic phase, but other measures, such as chromatography and / or crystallization, conceivable.
  • the ester of the general formula (I) obtained in the process is saponified after its preparation, for. B. by hydrolysis with aqueous alkali metal hydroxide solution.
  • Another object of the invention relates to the preparation of a carboxylic acid of general formula Ia
  • the ester of general formula (I) may be isolated prior to saponification or recovered as a crude product.
  • the saponification can also be carried out in the resulting reaction mixture without prior recovery of the ester.
  • the hydrolysis is carried out by aqueous alkali metal hydroxide, in particular by sodium hydroxide solution or potassium hydroxide solution.
  • the aqueous alkali metal hydroxide used for the saponification is unused alkali metal hydroxide from step (i). But you can also add additional alkali metal hydroxide.
  • the saponification is carried out in the presence of organic solvents that are miscible with water, especially in the presence of alcohols, in order to increase the saponification rate.
  • the reaction temperature required for the saponification is typically in the range from 30 to 120 ° C., in particular in the range from 35 to 100 ° C. and in particular in the range from 40 to 80 ° C.
  • the resulting acid can then be isolated from the reaction mixture in the usual way.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'esters de l'acide 2,2-dichlorocyclopropanecarboxylique, selon lequel un ester d'acide carboxylique α,β-insaturé est mis en réaction avec du chloroforme en présence d'une solution aqueuse d'hydroxyde de métal alcalin et de quantités catalytiquement actives d'un iodure d'aluminium de formule R5 (CH3)3NI, R5 représentant un alkyle en C2-C10, un cycloalkyle en C3-C8, un C3-C8-cycloalkyl-C1-C4-alkyle, un phényle, un tolyle ou un benzyle.
PCT/EP2008/067894 2007-12-19 2008-12-18 Procédé de fabrication d'esters de l'acide 2,2-dichlorocyclopropanecarboxylique WO2009077590A1 (fr)

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EP07150159 2007-12-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8288563B2 (en) 2009-03-16 2012-10-16 Basf Se Process for the preparation of pyrazole derivatives

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2201514A1 (de) * 1971-01-14 1972-08-17 Bdh Pharmaceuticals Ltd Verfahren zur Herstellung von Dihalogencyclopropancarbonsaeuren und/oder deren Estern
DE2324390A1 (de) * 1972-05-16 1973-11-29 Shell Int Research Verfahren zur herstellung von derivaten des cyclopropans

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2201514A1 (de) * 1971-01-14 1972-08-17 Bdh Pharmaceuticals Ltd Verfahren zur Herstellung von Dihalogencyclopropancarbonsaeuren und/oder deren Estern
DE2324390A1 (de) * 1972-05-16 1973-11-29 Shell Int Research Verfahren zur herstellung von derivaten des cyclopropans

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8288563B2 (en) 2009-03-16 2012-10-16 Basf Se Process for the preparation of pyrazole derivatives

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