KR820000211B1 - Process for preparation of 2,2-dimethyl-3-vinyl-cycloproprpane carboxylic acid esters of halogenated benzyl alchols - Google Patents

Abstract

Dihalovinylcyclopropanecarboxylates (I; R = F, Cl, Br or CH3; m,n = 0-5; m+n < 5; R1 = hydroxy, C1-4 alkoxy or halogen) were prepd. by reaction of II and III in 10-120≰C. Thus, 0.1 mol 2,2-dimethyl-3-dichlorovinyl-cyclopropane carboxylic chloride reacted with 0.1 mol pentafluorobenzyl alcohol in 120≰C to give 2,2-dimethyl-3-dichlorovinyl-cyclopropanecarboxylicpentafluorobenzylester.

Description

Method for producing 2,2-dimethyl, 3-vinylcyclopropane carboxylic acid ester of halogenated benzyl alcohol

The present invention relates to a process for preparing 2,2-dimethyl, 3-vinylcyclopropane carboxylic acid ester of benzyl alcohol of the general formula (I) as effective insecticide and acaricide.

Wherein R is independently F, Cl, Br or CH ₃ and m and n are 0, 1, 2, 3, 4 or 5 and the sum of m + n is 5 or less.

Under these conditions, (i) m and n cannot both be zero when each R is F or Br, and (ii) when each R is Cl, m is 0, 1, 2, 3 or 4 and n is 1, 2 , 3, 4 or 5 and (iii) when each R is methyl, m is 0 and n is 5.

The esters according to the invention surprisingly show strong and fast action of insecticidal and acaricide. The compound thus implies advances in the art.

Preferably for the same or different R, F or Cl or Br (especially Cl or Br), m is an integer from 2 to 5 or n is an integer from 3 to 5, and R is methyl, m is 0 and n are 5.

It was announced earlier that the 2,2-dimethyl-3 (2-methylbuten-1-yl) -cyclopropanecarboxylic acid ester of polychlorinated benzyl alcohol exhibited pesticidal properties (French Patent No. 2,271,196 and Japanese Patent Specification No. 75 / 003,037). However, these materials have not always had a satisfactory effect on pesticidal rate, strength and duration.

According to the preparation method according to the present invention, the following general formula (II) compound is reacted with the following general formula (III) compound at 20 ° to 120 ° C, optionally in the presence of an inert diluent (including solvent), Get ester.

Wherein R, m and n are as defined above and R ¹ is halogen, hydroxy or alkoxy having 1 to 4 carbon atoms.

Formula (I) compounds exist in several stereoisomers. Substituents of a cyclopropane ring may be present in the cis or trans position with each other. The carbon atoms C ₁ and C ₃ may in each case be in R- or S-configuration to be optionally derived into active or racemic cis- and / or trans-isomers.

Examples of the active compounds according to the invention are mentioned next.

2, 2-dimethyl-3- (2-methylbuten-1-yl) -cyclochloropropane-carboxylic acid pentafluorobenzyl ester,

2,2-dimethyl-3-difluorovinylcyclopropane carboxylic acid pentafluorobenzyl ester,

2, 2-dimethyl-3-dibromovinyl-cyclopropane carboxylic acid pentafluorobenzyl ester,

2,2-dimethyl-2-dibromovinyl-cyclopropane carboxylic acid pentaclobenzyl ester,

2, 2-dimethyl-3-dichlorovinyl-cyclopropane carboxylic acid pentafluorobenzyl ester,

2, 2-dimethyl- 3-dichlorovinyl-cyclopropane carboxylic acid 2, 3, 5, 6- tetrafluorobenzyl ester,

2, 2-dimethyl- 3-dichlorovinyl-cyclopropane carboxylic acid 2, 4, 6- trifluorobenzyl ester,

2, 2-dimethyl-3-dichlorovinyl cyclopropane carboxylic acid 2, 3, 5-trifluorobenzyl ester,

2, 2-dimethyl- 3-dichlorovinyl-cyclopropane carboxylic acid 2, 4-difluorobenzyl ester,

2, 2-dimethyl- 3-dichlorovinyl-cyclopropane carboxylic acid 2,6-difluorobenzyl ester,

2, 2-dimethyl- 3-dichlorovinyl-cyclopropane carboxylic acid tetrafluoro- 3-chlorobenzyl ester,

2, 2-dimethyl- 3-dichlorovinyl cyclopropane carboxylic acid 2, 3, 6- trifluorobenzyl ester,

2, 2-dimethyl- 3-dichlorovinyl-cyclopropane carboxylic acid trifluoro-3,5-dichlorobenzyl ester,

2, 2- dimethyl- 3-dichlorovinyl cyclopropane carboxylic acid 2, 6- difluoro-3, 5-dichlorobenzyl ester,

2, 2-dimethyl-3-dichlorovinyl-cyclopropane carboxylic acid 2, 3-difluoro-5- chlorobenzyl ester,

2, 2-dimethyl- 3-dichlorovinyl-cyclopropane carboxylic acid 2-fluoro 3, 5-dichlorobenzyl ester and the corresponding 3-dibromovinyl compound.

The esters listed above include both racemic and optional active isomers as well as cis- and or trans-isomers.

In the case of using 2,2-dimethyl-3-dichlorovinylcyclopropane carboxylic acid chlorolide as the general formula (II) compound and pentafluorobenzyl alcohol as the benzyl alcohol of the general formula (III), the reaction route is represented by the following scheme. Can be represented.

General formula (II) compound is a known compound. (German Federal Republic Open Statement No. 2, 439,177)

The alcohol of general formula (III) is known in most cases.

See, J. Chem. Soc. C. 1967, 293; J. Chem. Soc. 1962, 3227; J. Chem. Soc. 1961, 808; J. Chem. Soc. 1959, 166; J. Chem. Soc. 11,814 (1968)]

Alcohols of general formula (III) (whether new or known) can be prepared by known methods such as the reduction of the corresponding carbonyl compounds of general formula (IV) with complex metal hydrides.

Wherein m and n are as defined above and Y is hydroxyl, alkoxy, chlorine, bolso or hydrogen.

If excess LiA | H ₄ is used, one or two BSOs can be reductively removed simultaneously from the nucleus during this manufacturing process.

Carbonyl compounds of formula (IV) required for activating are in most cases known compounds and novel compounds can be prepared by known methods (Synthesis 1976, p.652).

In the case of using 2,4,6-trifluorobenwmaldehyde, the reduction of the aldehyde or acid halide of the general formula (IV) can be represented by the following scheme.

Scheme (1) shows the reduction of carbonyl functional groups carried out using metal hydrides such as NaBH ₄ or LiAlH ₄ . This reduction is carried out in the presence of an inert organic diluent at a temperature of 0 ° C to 100 ° C.

In addition to inert organic diluents such as mixtures of ethers (eg diethyl ether, dioxane or THF) with alcohols (eg ethyl alcohol or methyl alcohol) or water, NaBH ₄ is a suitable diluent for causing reduction.

The compound of formula (IV) to be reduced is generally dissolved in one of the diluents mentioned above and a reducing agent is added.

However, a reducing agent may be added to the compound to be reduced at low temperature (−30 ° C. to −50 ° C.) in the solvent, and allowed to stand so that the temperature gradually rises (up to 50 to 60 ° C. in some cases).

This reaction is usually carried out at atmospheric pressure.

If desired, an amount of water corresponding to the reducing agent used in the reaction mixture is added followed by distillation of the organic layer.

In the case of using LiAlH ₄ , it is possible to use the theoretical amount of LiAlH ₄ necessary for this purpose if the carbonyl functional group is to be reduced. When a metal hydride having a milder reducing action is used as the reducing agent, an excessive use of metal hydride does not affect the reaction route.

Scheme (2) shows the reduction of a carbonyl functional group in which the B-substituent at the P-position of the nucleus is simultaneously reductively removed. In this reaction, it is necessary to use as a reducing agent a -hydrogen-donating agent which is much more powerful than LiAlH ₄ or NaBH ₄ . In addition to the amount necessary for the reduction of the carbonyl functional group, one reduction equivalent of LiAlH ₄ is required to remove each fluorine substituent.

In ether, in particular THF has proved to be particularly suitable as a diluent.

Reduction with LiAlH ₄ is carried out at a temperature between 20 ° and 100 ° C., preferably between 50 ° and 70 ° C. The reaction is carried out and the product is processed as described above.

Examples of the general formula (III) compound include the following compounds.

Pentafluorobenzyl alcohol, 2, 3, 5, 6-tetrafluorobenzyl alcohol, 2, 4, 6-trifluorobenzyl alcohol, 2, 3, 5-trifluorobenzyl alcohol, 1, 4-difluoro Lobenzyl alcohol, 3,5-difluorobenzyl alcohol, 2,6-difluorobenzyl alcohol, tetrafluoro-3-chlorobenzyl alcohol, 2, 4,6-trifluoro-3, 5-dichlorobenzyl Alcohols, 2,6-difluoro-3,5-dichlorobenzyl alcohol, 2,3-difluoro-5-chlorobenzyl alcohol and 2-fluoro-3,5-dichlorobenzyl alcohol

When R is fluorine or bromine, preferred benzyl alcohols are as follows.

Pentachlorobenzyl alcohol, 2, 3, 5, 6-tetrachlorobenzyl alcohol, 2, 3, 5-tetrachlorobenzyl alcohol, 2, 3, 4-tetrachlorobenzyl alcohol, 2, 3, 5-trichlorobenzyl alcohol , 2,4,5-trifluorobenzyl alcohol, 3,5-dichlorobenzyl alcohol, 2,4-dichlorobenzyl alcohol and 2,6-dichlorobenzyl alcohol.

As already mentioned, most benzyl alcohols of the general formula (III) are new.

This novel compound can be defined by the following general formula (III).

Wherein m is 0, 1 or 2, n is 1, 2, 3 or 4, and m is 0 and n is 2, the 6-position of the phenyl ring should be unsubstituted.

2, 3, 5, 6-tetrafluorobenzyl alcohol, 2, 4, 6-trifluorobenzyl alcohol, 2 3, 5-trifluorobenzyl alcohol, 2, 4-difluorobenzyl alcohol, 3, 5 -Difluorobenzyl alcohol, tetrafluoro-3-chlorobenzyl alcohol, 2, 4, 6-trifluoro-3, 5-dichlorobenzyl alcohol, 2, 6-difluoro-3, 5-dichlorobenzyl alcohol Particular preference is given to novel benzyl alcohols in the 2,3-difluoro-5-chlorobenzyl alcohol and the 2-fluoro-3,5-dichlorobenzyl alcohol groups.

As mentioned above, the compounds according to the invention exhibit excellent pesticidal and acaricide activity. This compound is effective against plant pests, pests that harm health, and pests of stored foods, and has excellent effects on insects, insects and mites.

The compounds according to the invention can thus be used successfully as insecticides for the protection of plants and for hygiene and for the protection of stored foods.

Compounds that are tolerant to plants are less toxic to warm-blooded animals and can be used for the removal of ticks parasitic, especially in insects and cropland forests, and for the protection and hygiene aspects of stored food or stored products.

This compound is typically effective against all or several growth stage species with sensitivity and resistance.

The pests described above are as follows.

Isopoda: eg, Oniscus asellus; Armadillidium vulgare, and Porcellio scaber.

Diplpooda; Yes, Braniulus guttula tus.

Chilopoda; Eg, Geophilus carpophagu s and Scutigera Symphyla; Scu tigerella immaculata, Thysanura; Eg, Lepisma saccharina.

Collembola; Yes, Onychiurus armatus.

Lothoptera; For example, Wingspan (Blattaor-entalis), Peri planeta americana, Leucophea maderae (Leucophea maderae), Wheels (Blattella germanica), Acheta domesticus, and ground puppy Gryllotalpa spp.), Flemish (Locusta migratoria migratorioides)

Melanoplus differentialis and Meloplus differentialis (Schistocerca gregaria).

Dermaptera; Yes, Porficula auricula ria.

Termite (Isoptera); Eg, Reticulitermes spp.

Anoplura; Yes, Phylloxera vastatrix.

Pemphigus spp., Pediculus h umanus corporis, Haematopinus spp., And Li nognathus spp.,

Mallophaga; Eg, Trichodectes spp., And Damarinea spp.

Thysanoptera; Eg, Hercinothrip s femoralis and Thrips tabaci.

Felling (Heteroptera); Eg, Eurygaster spp, Dysdercus intermdius,

Pisma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.

Homoptera; Examples: Areurodes brassicae, Bemisiatabaci, Triareurodes vap orariorum, Aphids gossypii, Brevicoryne bricaca assicae, Cryptomyzus ribis, Doralis fab ae, Doralis pomi, Eriosoma lanigerum, H yalopterusa rundinis, Bearded aphid (Macrosiphum avenae) ), Black aphid subspecies (Myzus spp.), Phorodon humuli, Rhodalosiphum padi, Empoasca spp., Euscelis bilobatus, Endus cicada (Nephotettix cincticeps), Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Apidion Aspid to Tuschedera iotus hederae), Pseudoc-occus spp., and Psylla spp.

Lepidoptera; Pectinophora gossypiella. Bupaluspiniarius, Cheimatobia brum ata, Litocolletis blanc-ardella, Hypo nomeuta padella, Plutella maculipennis , Marcosomaneust ria, Euproctis chrysorrhoea, Lymantria spp. (Agrotis spp.), Euxoa spp., Feltia spp., Earias insulana, Helios this spp., Laphygma exigua , Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Ka Carpocapsa pomonella, blood Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana , Capua reticulana, Capristoneura fumiferana, Clysia ambiguella, Homona magnanima, and Tortrix viridana coleoptera (Coleoptera); Examples: Anobium punctatum, Rhizop-ertha dominica, Bruchidius obtectus, Acanthosc-elides obtectus, Hyro-rupes Bacillus (Hylotrupes bajulus), Agelastica alni, Leptinotarsa decemineata, Phaedon cochleariae, Diabrotica subspecies, Psilio Psylliodes chry socephala, Epirachna varivestis, Atomaria spp., Oryzaephilus surinamensis, A nthonomus spp. Sitophilus spp., Otio rrhy-nchus sulcatus, Cosmopolites sordidus, Cethorthorus-hynchus assimilis, Hyperaphos Hypera pos tica, Dermestes spp., Trogoderma spp., Anthrenus spp., Atentaus spp., Rickus subspecies (Lyctus spp.), Marygethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Trivorium subspecies (Tribolium spp.), Tenebrio molitor, Agriotes spp., Conoderus spp., Melontaron lonlontha, Amphimalon soltitiaris (Amphimallon solstitialis), and Costelytra zealandica.

Hymenoptera: Yes; Diprion spp., H oplocampa spp., Lasius spp., Monomorium ph araonis, and Vespa spp.

Diptera: yes; Aedes spp., Anop heles spp., Curex spp., Drosophila melanogaster, Musca spp., Fannia spp. , Calliphora erythrocephala, Lucilia spp., Chrysomyia sp p., Cuterebra spp., Gastrophilus spp. ), Hypobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp. , Tania subspecies, Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis Capitata (Ceraitis capitata), Dacus oleae and Tipula paludosa.

Siphonaptera: yes; Xenopsylla cheopis, and Ceratophyllus spp.

Arachnida: Yes; Scorpio maurus and Latrodectus mactans.

Acarina: e.g., Acarus siro, Argas spp., Ornit-hodoros spp., Dermanyssus gallinae, Eriopies levis Eriophyes ribis, Ph yllocoptruta oleivora, Boophilus spp., Rip ipicephalus spp., Amblyomma spp., Hyaloma subspecies (Hyalomma spp.), Mites (Ixodes spp.), Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus subspecies (Ta rsonemus) spp.), Bryobia praetiosa, Panonicus spp., and Tetranychus spp.

The active compounds are conventional formulations such as solutions, emulsions, wetting agents, suspensions, powders, powders, foaming agents, pasting agents, soluble powders, granules, aerosols, suspension-emulsifying concentrates, seed treatment powders, natural and It can be converted into formulations for use with combustion instruments such as combustion cartridges, combustion cans and combustion coils, as well as synthetic capsules, fine capsules of polymers for seed and fine capsules coated with the composition, ULV (ultra low volume) cold mists and warming agents. Can be.

This formulation may be prepared by mixing known methods, for example, active compounds with weights such as liquid or solid or liquefied gas diluents or carriers, optionally with surfactants such as emulsifiers and / or dispersants and / or foaming agents. When water is used as the weighting agent, the organic solvent can be used, for example, as a cosolvent.

Liquid diluents or carriers, in particular solvents, are mainly aromatic hydrocarbon groups such as xylene, toluene, benzene or alkyl-naphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexine or paraffins for example light fraction Aliphatic or substituted hydrocarbons such as butanol or glycols as well as alcohols such as ethers or esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, such as dimethylformamide and dimethyl sulfoxide Polar stone solvents are also suitable.

By liquid gas diluent or carrier is meant an aerosol jetting agent such as liquid, for example dichloro difluoromethane or trichloro fluoromethane, gaseous at room temperature and atmospheric pressure.

As a solid carrier, it is preferable to use crushed natural minerals such as kaolin, clay, talc, choke, salt, attacgit, montmorillonite or diatomaceous earth and crushed synthetic minerals such as highly dispersed silicic acid, alumina and silicate. Do.

Preferred examples of emulsifiers and foaming agents include polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers such as alkyllauryl polyglycol ethers, alkylsulfonates, alkylsulfates and arylsulfonates as well as albumin hydrolysis products. The same nonionic and anionic emulsifiers are mentioned, and examples of preferred dispersants are lignin sulfite waste liquor and methylcellulose.

Additives such as carboxymethylcellulose and powders, granular lattice natural and synthetic polymers, gum arabic, polyvinyl alcohol and polyvinylacetate can be used in the formulation.

Inorganic pigments such as colorants such as iron oxides, titanium oxides and prussian browns and organic dyes such as alizarin dyes, azo dyes or metalphthalocyanine dyes, iron, manganese, boron, copper, cobalt, molybdenum and zinc salts Micronutrients such as these can be used.

The formulations generally contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90% by weight.

The active compounds according to the invention can be used in the form of commercially available formulations or in forms which are convenient for use made from these formulations.

The content of the active compound in the form of use prepared from commercially available formulations can vary widely. The concentration of the active compound in the form of use is 0.0000001 to 100% by weight, preferably 0.01 to 10% by weight of the active compound.

This compound may be prepared in a formulation suitable for a particular use form and used in a conventional manner.

When used for pests that are harmful to health and pests, the active compounds have excellent residual effects on the material and clay, and also have good safety against calcareous alkalinity.

The present invention also provides an insecticidal composition wherein the compound of the invention is contained as an active ingredient in a mixture with a solid or liquefied gas diluent or carrier or in a mixture with a liquid diluent or carrier containing a surfactant.

The present invention provides a method for controlling arthropods, especially insects and ticks, or habitats of these pests, in the form of the active compounds alone or in admixture with diluents or carriers.

In addition, the present invention can protect the crop from damage of arthropods by using the compound of the present invention alone or in a mixture with a diluent or a carrier during or immediately before the crop is grown.

It will be appreciated that the present invention can be improved with conventional methods of obtaining crops.

The pesticidal effect according to the compound of the present invention was explained as the following biological example.

In these embodiments, the compounds according to the invention correspond to the numbers of the corresponding preparation examples (indicated in parentheses) described below.

Example A

Aerosol test

Test pest: straw flies (phosphate ester resistance)

Solvent: Acetone

This compound is dissolved in the desired amount of acetone to obtain a suitable formulation of the active compound.

25 pests used in the test are placed in barbed wire and placed in the center of a 1m3 glass box. 2 ml of the active compound preparation is sprayed into this box, the box is sealed and the condition of the pest is continuously examined through the glass wall and the time required for 100% of this pest to die is measured.

The active compound, the amount and time of active compound used for obtaining 100% killing are described in the following table.

TABLE A

Example B

Laphygma test

Solvent: 3 parts by weight of dimethyl formamide

Emulsifier: To obtain a suitable formulation of 1 part by weight of alkylaryl polyglycol ether active compound, 1 part by weight of the active compound is mixed with the above amount of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

Cotton leaf (Gossypium hirsutum) is sprayed with active compound preparation until dew forms and infected with Laphyg-ma exigua mother layer.

The mortality rate was measured after a certain period of time. 100% means that all caterpillars have been killed, and% means that no caterpillars have been killed.

The active compound, the concentration of the active compound, the measurement time and the results are shown in the following table.

TABLE B

Example 1

2,2-dimethyl-3-dichlorovinylcyclopropane carboxylic acid pentafluorobenzyl ester

0.1 mole of pentafluorobenzyl alcohol is added dropwise at 70 ° C to 0.1 mole of 2,2-dimethyl-3-dichlorovinylcyclopropanecarboxylic acid chloride (cis / trans). The mixture is heated to 120 ° C. for several minutes until the generated gas stops. The oil purified by thin layer chromatography was obtained quantitatively. Boiling Point _0.1 120 to 130 ° C. Spectroscopic Analysis:

IR (cm- ¹ ): 2900, 1740, 1660, 1510, 1460, 1415, 1385, 1355, 1310, 1220, 1161, 1130, 1080, 1050, 995, 970, 940, 810, 780

Mass spectrum (m / e) 181, 163, 165, 91, 127, 109, 191, 207, 353, 388 (M).

NMR (ppm): 6.6 and 5.6d (1), 5.2s (2), 0.8-2.4m (8)

The product is left to stand for several days to precipitate a colorless crystalline material (melting point 74 ° C.). The other esters having spectroscopic analysis as described below as cis-isomers can be prepared in the same manner as above.

Example 2

IR (cm- ¹ ): 1730, 1630

Mes Spectrum (m / e): 763, 91, 127, 207, 335, 370 (M)

NMR (ppm): 7 (1); 6.2, 56d (1); 5.2 s (2); 0.9-2.5 m (8)

Example 3

Mes Spectrum (m / e): 145, 163, 165, 129, 191, 317, 352 (M)

NMR (ppm): 7 m (2); 6.2; 5.6d (1); 5.1 s (2), 0.9-2.5 m (8)

Example 4

IR (cm- ¹ ): 2950, 1740, 1650, 1630, 1500, 1420, 1390, 1350, 1280, 1230, 1160, 1135, 1100, 1020, 940, 870, 820, 780

Example 5

IR (cm- ¹ ): 1735, 1630

Mes Spectrum (m / e): 195, 163, 165, 127, 91, 191, 207, 367, 402 (M)

Example 6

IR (cm- ¹ ): 2950, 1735, 1620, 1515, 1460, 1350, 1280, 1230, 1160, 1140, 1100, 1090, 1055, 990, 965, 920, 885, 850, 820

Mes Spectrum (m / e): 127, 109, 163, 165, 91, 191, 207, 251, 299, (M-Cl)

Example 7

IR (cm- ¹ ): 2950, 1735, 1635, 1600, 1485, 1280, 1230, 1170, 1140, 1120, 1055, 920

Mes Spectrum (m / e): 127, 109, 163, 165, 91, 191, 207, 251, 299, 334 (M)

NMR (ppm): 6.7-7.6 m (3), 6.2 and 5.6 d (1); 5.2 s (2), 0.7-2.4 m (8)

Example 8

IR (cm- ¹ ): 1730, 1620,

Mes Spectrum (m / e): 163, 165, 179, 127, 91, 191, 207, 351, 386 (M)

Example 9

IR (cm- ¹ ): 1730, 1620,

Mes Spectrum (m / e): 161,163,165, 91, 191, 207, 333, 386 (M)

The following compounds are obtained in a similar way.

Example No

Claims (1)

The following general formula (II) compound is reacted with the following general formula (III) compound at a temperature of 20 to 120 ° C, characterized in that the halogenated benzyl alcohol of the following general formula (I) Process for producing propane carboxylic acid ester.

Wherein R is independently F, Cl, Br or CH ₃ and m and n are each 0, 1, 2, 3, 4 or 5 and the sum of m + n is 5 or less. Under the above conditions, i) when each R is F or Br, m and n cannot both be 0 and ii) when each R is Cl, m is 0, 1, 2, 3, or 5 and n is 1, 2, 3, 4 or 5 and iii) when each R is CH ₃ m is 0 and n is 5 and R ¹ is hydroxy, alkoxy or halogen having 1 to 4 carbon atoms.