Title of Invention	A PROCESS FOR PRODUCING CYCLOPROPANECARBOXYLATES
Abstract	A Process for producing a cyclopropanecarboxylate of Formula (1) : which process comprises reacting cyclopropanecarboxylic acid of formula (2) : with a monohydroxy compound of formula (3): R6OH (3), in the presence of around 0.001 to 200 mole % of a catalyst compound comprising an element of Group 4 of the Periodic Table of Elements, per mol of cyclopropanecarboxylic acid of formula (2), and within a range of around 20 to around 200° C, wherein R', R2, R3, R4, and R5 independently represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, or an aryl group which may be substituted; and R6 represents an alkyl group which may be substituted, or an aryl group which may be substituted. ABSTRACT 58/MAS/2002 A process for producing cyclopropanecarboxylates A Process for producing a cyclopropanecarboxylate of Formula (1): which process comprises reacting cyclopropanecarboxylic acid of formula (2) : with a monohydroxy compound of formula (3): R6OH (3), in the presence of around 0.001 to 200 mole % of a catalyst compound comprising an element of Group 4 of the Periodic Table of Elements, per mol of cyclopropanecarboxylic acid of formula (2), and within a range of around 20 to around 200 C, wherein R1, R2, R3, R4, and R5 independently represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, or an aryl group which may be substituted; and R6 represents an alkyl group which may be substituted, or an aryl group which may be substituted.

Title of Invention

A PROCESS FOR PRODUCING CYCLOPROPANECARBOXYLATES

Abstract

A Process for producing a cyclopropanecarboxylate of Formula (1) : which process comprises reacting cyclopropanecarboxylic acid of formula (2) : with a monohydroxy compound of formula (3): R6OH (3), in the presence of around 0.001 to 200 mole % of a catalyst compound comprising an element of Group 4 of the Periodic Table of Elements, per mol of cyclopropanecarboxylic acid of formula (2), and within a range of around 20 to around 200° C, wherein R', R2, R3, R4, and R5 independently represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, or an aryl group which may be substituted; and R6 represents an alkyl group which may be substituted, or an aryl group which may be substituted. ABSTRACT 58/MAS/2002 A process for producing cyclopropanecarboxylates A Process for producing a cyclopropanecarboxylate of Formula (1): which process comprises reacting cyclopropanecarboxylic acid of formula (2) : with a monohydroxy compound of formula (3): R6OH (3), in the presence of around 0.001 to 200 mole % of a catalyst compound comprising an element of Group 4 of the Periodic Table of Elements, per mol of cyclopropanecarboxylic acid of formula (2), and within a range of around 20 to around 200 C, wherein R1, R2, R3, R4, and R5 independently represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, or an aryl group which may be substituted; and R6 represents an alkyl group which may be substituted, or an aryl group which may be substituted.

Full Text	Field of the Invention: The present invention relates to a process for producing cyclopropanecarboxylates. Background of the invention There have been known a production method of carboxylic acid ester from a carboxylic acid and an alcohol using a protonic acid catalyst. A production method using sulfuric acid as a catalyst is disclosed (Japanese Patent Laid-Open Publication No. 9-188649), and also disclosed is a method of using p-toluenesulfonic acid as a catalyst (Japanese Patent Laid-Open Publication No. 11-228491). However, the methods using mineral acid or organic acid having strong acidity cause significant coloring due to a side reaction, which has made these methods not necessarily efficient as industrial production methods. Summary of the Invention According to the present invention, a cyclopropanecarboxylate can be conveniently produced, through dehydration reaction, from a cyclopropanecarboxylic acid and an alcohol in the presence of the catalyst as defined below. The present invention provides a process for producing a cyclopropanecarboxylate of formula (1): jhich process comprises reacting a cyclopropanecarboxylic acid of formula (2): fith a monohydroxy compound of formula (3): RGQH (3), in the presence of a compound comprising an element of Group 4 of the Periodic Table of Elements, 'herein in formula (1) and (2), R\ R^, R^, R^, and R^ independently represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, an aryl group which may be substituted; and in formula (3), R^ represents an alkyl group which may be substituted, or an aryl group which may be substituted. Detailed Description of the Invention The halogen atom or the term "halo" in the present specification means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom in R-"- through R^. The alkyl group which may be substituted and the alkenyl group whichmay be substitutedmay be linear, branched, or cyclic. Thetermalkenylor alkynyl inR^ through R^ and substituents that may be present therein means the same group as specified for R^ to R^ below. The aryl group represented by R^ through R^ and the "aryl" including those present as the substituent group as in aryloxy, or haloaryloxy includes a (C6-C14)aryl group such as phenyl, biphenyl, naphthyl, anthracenyl or the like. R^, R^, R', R, and R^ in the cyclopropanecarboxylic acid (2} and the cyclopropanecarboxylate (1) will be explained below. Examples of the alkyl group which may be substituted represented by R^, R^, R"', R^, or R^ include, for example, a (Cl-10)alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, menthyl and the like. Examples of the alkenyl group which may be substituted represented by RS R^, ^^, R\ or R^ include, for example, a (C2-C5)alkenyl group such as vinyl, 1-methylvinyl, 1-propenyl, 2-methyl-l-propenyl, 1-butenyl, 3-methyl-2-butenyl or the like. The alkyl group, alkenyl and alkynyl groups represented by R^, R^, R^, R', or R^ may be independently substituted with at least one member selected from a halogen atom, an alkoxy group, an alkoxycarbonyl group, a haloalkoxycarbonyl group, an aryl group, a halocycloalkylidene group, an alkoxyimino group, an alkylsulfonyl group, an alkylsulfonyloxy group, and a hydroxysulfinyl group. Examples of the alkenyl group substituted with halogen include, a halo (C2-C5) alkenyl group such as 2, 2-dichlorovinyl, 2,2-dibromovinyl, 2-chloro-2-fluorovinyl, 2-chloro-2-trifluoroinethyl vinyl, 2-bromo-2-tribromon:iethylvinyl, or the like. Examples of the alkynyl group which may be substituted includes a propargyl group and the like. Examples of the alkoxy group include, for example, a {C1-C4)alkoxy group such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy^ sec-butoxy, or tert-butoxy group or the like. Examples of the alkoxycarbonyl group include, for example, a {C1-C4)alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, see-butoxycarbonyl, tert-butoxycarbonyl or the like. Examples of the haloalkoxycarbonyl group include, for example, a halo(C1-C4)alkoxy-carbonyl group such as a 2,2,2-trifluoro-l-(triflucromethyl)ethoxycarbonyl group or the like. Preferred aryl group are phenyl, 1-naphthyl, and 2-naphthyl groups and the like. Examples of the halocycloalkylidene group include, for example, a halo{C3-C5)cycloalkylidene group such as difluorocyclopropylidene group or the like. Examples of the alkoxyimino group include, for example, a (C1-C3} alkoxy-imino group such as methoxyimino, ethoxyimino, an n-propoxyimino or the like. Examples of the alkylsulfonyl group include, for example, a (C1-C4)alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsulfonyl, tert-butylsulfonyl or the like. Examples of the alkylsulfonyloxy group include, for example, a (C1-C4 ) alkylsulfonyl group such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, i-propylsulfonyloxy, tert-butylsulfonyloxy or the like. The cyclopropanecarboxyic acid (1) includes any optical isomer or mixture thereof. Specific examples of the cyclopropanecarboxylic acid (2) include, for example, cyclopropanecarboxylic acid, 2-fluorocyclopropanecarboxylic acid, 2,2-dichlorocyclopropanecarboxylic acid, 2,2-dimethyl-3-(dimethoxymethyl)cyclopropanecarboxylic acid, 2,2,3,3-tetramethylcyclopropanecarboxylic acid, 2,2-dimethyl-3-(l-propenyl)cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid, 2,2-dimethyl-3-C3-methyl-2-butenyl)cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2, 2,2-trichloroethyl)cyclopropanecarboxylic 2,2-dimethyl-3-[2-{2,2,2-trifluoro-l-Ctri.fluoroinethyl)-ethoxycarbonyl}vinyl]cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2-aza-2-methoxyvinyl)cyclopropanecarboxylic acid, 2,2-dimethyl-3-{4-aza-4-methoxy-3-methylbut-l,3-dienyl)-cyclopropanecarboxylic acid, 2,2-diraethyl-3-[2-{(tert-butyl)sulfonyl}-2-(tert-butoxy-carbonyl)vinyl]cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2,2,2-tribroino-l-(methylsulfonyloxy)ethyl}-cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2,2-dibromo-2-{hydroxysulfinyl)-1-(methoxy) -ethyl}cyclopropanecarboxylic acid, 2,2-dimethyl-3-{2,2,2-tribromo-l- {methylsulfonyloxy)ethyl}-cyclopropanecarboxylic acid, 2-methyl-2-ethyl-3-(1-propenyl)cyclopropanecarboxylic acid, 2,2-diethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid, and 2-inethyl-2-phenyl-3-{2-inethyl-l-propenyl) cyclopropanecarboxylic acid. Preferred are 2,2-dxraethyl-3- (2,2-dichlorovinyl}cyclopropanecarboxylic acid, and 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid. Next a description will be made to the monohydroxy compound of formula (3). Examples of the alkyl group, which may be substituted, represented by R^, include, for example, a (Cl-ClO)alkyl group which may be substituted with a member selected from a halogen atom, a cyano group, a nitro group, an alkenyl group, a haloalkenyl group, an alkynyl group, or an aryl or heterocyclic group which may be substituted with at lest one member selected from an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkoxyalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aryoxy group, a haloaryloxy group, an aralkyl group(e.g. (C7-C8}aralkyl such as benzyl, phenethyl), an acyl group[e.g. (Cl-C2)acyl such as formyl, acetyl), a haloacyloxyalkyl group(e.g. trifluoroacetyloxyalkyl), an amino group, and a halogen atom; or R^ represents: a 1-, or 2-indanyl group which may be substituted with an alkynyl group or an aryl or heteroaryl group(e.g. 5- or 6-membered heteroaryl group such as thienyl); or a cycloalkenyl group (e.g., cyclopentenyl )substituted with at least one member selected from an oxo group, an alkyl group, an alkenyl and an alkynyl group (e.g. 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-one, 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentene-l-one). The term "alkyl" used in the alkyl, haloalkyl, and alkoxyalkyl groups as recited in the definition of R^ and substituents thereof includes a C1-C14 alkyl group. Examples of the (C1-C14 ) alkyl group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl group and the like. Examples of the haloalkyl group include fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl and the like. The term "alkoxy" used in the alkoxy, haloalkoxy, and alkoxyalkyl groups includes a C1-C4 alkoxy group as defined above in this specification. Examples of the alkenyl groups as recited above include a (C2-C5)alkenyl group (e.g. vinyl, 1-propenyl, l-methyl-2-propenyl, 1-butenyl, 2-penten-2-yl group or the like). The haloalkenyl group that may be present on the alkyl group represented by R^ means the same haloalkenyl group as described for the haloalkenyl group represented by R^ to R^. Examples of the alkynyl groups that may be present on the alkyl group represented by R^ include a (C2-C5)alkynyl group (e.g, ethinyl, propynyl, butynyl, pentynyl or the like). Examples of the heterocyclic group which may be substituted, include, for example, a furyl group, an isoxazolyl group, a pyrrolyl group, a thiazolyl group, an imidazolidine~2,4-dione group, a 4,5,6,7-tetrahydroisoindole group, an indole group, a pyridyl group, and further specific examples thereof include aphenoxyfurylgroup, abenzylfuryl group, apropargylfuryl group, a methylisoxazolyl group,a trifluoromethylthiazolyl group, a trifluoromethoxythiazolyl group, a propynylpyrrolyl group, a propynyldioxoimidazolidinyl group, a dioxotetrahydroisoindolyl group, an oxothiazolyl group, a halopyridyl group and the like. Examples of the aryl group which may be substituted, representedby R^, include an aryl group, whichmay be substituted with a phenyl, an alkynyl group, an acyl group, an alkyl group, an alkoxy group, or a halogen atom. The monohydroxy compound of formula (3} includes, for example, following alkyl alcohol, aralkyl alcohol, aryl alcohol and the like. Specific examples of the alkyl alcohol include, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, neopentyl alcohol, n-hexyl alcohol, n-octyl alcohol, n-decyl alcohol, and the like. Specific examples of the alcohol compound of formula (3) , wherein R^ represents the alkyl substituted with a halogen atom include, fluoroethyl alcohol, difluoroethyl alcohol, trifluoroethyl alcohol, and tetrafluoroethyl alcohol. Specific examples of the alcohol compound of formula (3) , wherein R^ represents a methyl group substituted with a member selectedfromthealkenyl, haloalkenyl, or alkynyl group include, 4-methylhept-4-en-l-yn-3-Dl, 4-fluorohept-4-en-l-yn-3-ol and the like. Specific examples of the alcohol compound of formula (3) , wherein R represents a methyl or ethyl group substituted with the heterocyclic group which maybe substituted as defined above, include, for example, 2-furylmethyl alcohol, 3-furylmethyl alcohol, {5-phenoxy-3-furyl)methyl alcohol, (5-benzyl-3-furyl)methane-l-ol, {5-(difluoromethyl)-3-furyl}raethan6-l-ol, 5-propargylfurfuryl alcohol, (5-methylisoxazole-3-yl)methane-l-ol, l-{2-{trifluoromethyl)-l,3-thiazole-4-yl}prop-2-yn-l-ol, l-{2-(trifluoromethoxy)-1,3~thiazole-4-yl}prop-2-yn-l-ol, l-{l-prop-2-ynyl-5-(trifluoromethyl}pyrrole-3-yllprop-2-yn-l-ol, (l-prop-2-ynylpyrrole-3-yl)methane-l-ol, 3- (hydroxymethyl) -l-propynyl-in:iida2olidine-2, 4-dione, 2-{hydroxymethyl)-4,5,6,7-tetrahydroisoindole~l, 3-dione, {1-{2-propynyl)pyrrole-3-yl}methane-l-ol, 5-(hydroxymethyl)-4-methyl-(2-propynyl)-1, 3-thiazoline-2- one, (l-prop-2-yny1-2-methylindole-3-yl)methane-l-ol, {l-prop-2-ynyl-2-(trifluoromethyl)indole-3-yl}methane-l-ol, (2,3, 6-trifluoro-4-pyridyl)methane-l-ol, and the like. Specific examples of the alcohol compound of formula (3) , wherein R^ represents a methyl or ethyl group substituted with at least one member selected from the aryl group which may be substitutedas defined above, acyano group, or the alkynyl group, include, for example, aralkyl alcohols such as: benzyl alcohol, 2-m6thyl-3-phenylbenzyl alcohol, 2,3,5,6-tetrafluorobenzyl alcohol, 2,3,5,6-tetrafluoro-4-methylbenzyl alcohol, 2,3,5,6-tetrafluoro~4-methoxybenzyl alcohol, 2,3,5, 6-tetraf luoro--4- (methoxymethyl) benzyl alcohol, 2,3,5,5-tetrafluoro-4-propargylbenzyl alcohol, (2,3,5,6-tetramethylphenyl)methyl alcohol, (pentamethylphenyl)methyl alcohol, (ethylphenyl) methyl alcohol, (n-propylphenyl) methyl alcohol, (isopropylphenyl)methyl alcohol, (n-butylphenyl)methyl alcohol, (sec-butylphenyl)methyl alcohol, (tert-butylphenyl)methyl alcohol, (n-pentylphenyl)methyl alcohol, (neopentylphenyl)methyl alcohol, (n-hexylphenyl}methyl alcohol, (n-octylphenyl)methyl alcohol, (n-decylphenyl)methyl alcohol, (n-dodecylphenyl)methyl alcohol, (n-tetradecylphenyl)methyl alcohol, naphthylmethyl alcohol, anthracenylmethyl alcohol, 1-phenylethyl alcohol, l-{l-naphthyl)ethyl alcohol, 1-(2-naphthyl)ethyl alcohol, 4-prop-2-ynylphenyl)methane-l-ol, 3~prop-2-ynylphenyl)methane-l-ol, and the like. Examples of the alcohol compound of formula (3} , wherein R^ represents 1-, or 2-indanyl group which may be substituted with analkynyl grouper an aryl or heteroaryl group (e.g. thienyl) include^ for example, 4-prop-2-enylindan-l-ol, 4-phenylindan-2-ol, 4-(2-thienyl)indan~2-ol, and the like. Examples of the aryl alcohol includes, phenol, 1-naphthol, 2-naphthol, 4-prop-2-ynylphenol, 3-prop-2-ynylphenol, 4-hydroxyacetophenone, 4-hydroxybenzaldehyde, and the above-described compounds having aromatic rings substituted with an alkyl group, an alkoxy group, a halogen atom, or the like. Preferred monohydroxy compound (3) are primary alcohols, such as benzyl alcohol, pentafluoroethyl alcohol, 3,3-dibromo-2-propene-l-ol, perfluoropropyl alcohol, hexafluoroisopropyl alcohol, perfluorobutyl alcohol, perfluoropentyl alcohol, perfluorohexyl alcohol, perfluorooctyl alcohol, perfluorodecyl alcohol, {1-(2-propynyl)~5-(trifluoromethyl)-4-pyrazolyl}methane-l-ol, l-{1-(2-propynyl)-5-(trifluoromethyl)pyrrole-3-yl}prop-2-yn-l-ol, l-{2-(trifluoromethyl)-1,3-thiazole-4-yl}prop-2-yn-l-ol, l-(2-(trifluoromethoxy)-1, 3-thiazole-4-yl}prop-2-yn-l-ol, and 4-fluorohept-4-en-l-yn-3-ol. Preferred are aralkyl alcohols and hydroxycyclopentenones, and more preferred are: 3-phenoxybenzyl alcohol; 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-one; and 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclQpentene-l-one. An asymmetric center (s) may be present in the monohydroxy compound (3) , and any optical isomer or a mixture thereof may be used in the present process to produce an optically active desiredester (s) (1) withretentionof configurationwith respect to the asymmetric center(s) in the alcohol moiety. The monohydroxy compound (2) may be used in excess. Preferably, the monohydroxy compound (2) is used 1 mol or less per mol of the cyclopropanecarboxylic acids (1) . After completion of the reaction, unreacted materials may generally be recovered by such operation as distillation, extraction, or the like. Next, a description will be made to the catalyst compound comprisinganelement of Group 4 of the Periodic Table of Elements . Examples of the catalyst compound include a zirconiuin compound, a titanium compound, a hafnium compound and the like. Preferred catalyst compounds are zirconium, titanium, and hafnium compounds having Lewis acidity, and can be represented by formula (4): M(0)„,{X}„(Y)4-2m-n (4) wherein M represents an element of Group 4 of the Periodic Table of Elements; X and Y independently represent a halogen atom, an alkoxy group, an acetylacetonate group, an acyloxy group, an amino group which may be substituted with up to two alkyl groups, or a cyclopentadienyl group; and m is equal to 0 or 1, and n is equal to 0, 1, or 2. Specific examples of the titanium and hafnium compounds include, for example, titanium halide such as titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide; titanium acetate, titanium acetylacetonate, titanium ethoxide, titanium i-propoxide, titanium n-butoxide, titanium t-butoxide; titanium oxychloride; titanium amide such as tetrakis(dimethylamino)titanium, tetrakis(diethylamino)titanium or the like; titanocene dichloride, titanocene dimethoxide, decamethyltitanocene dichloride; hafnium halide such as hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, hafnium tetraiodide or the like; hafnium acetate, hafnium acetylacetonate, hafnium alkoxide such as hafnium ethoxide. hafnium i-propoxide, hafnium n-butoxide, hafnium t-butoxide or the like; hafnium oxychloride; amide compound of hafnium such 33 tetrakis(dimethylamino)hafnium, tetrakis(diethylamino)hafnium or the like; hafnocene dichloride, hafnocene dimethoxide, and decamethylhafnocene dichloride. Among the specific compounds, preferred are titanium tetrachloride, titanium i-propoxide, titanocene dichloride, hafnium tetrachloride, hafnium t-butoxide, and hafnocene dichloride. Specific examples of the zirconium compound includes, for example, zirconium halide such as zirconium tetrafluoride, zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide or th§ like; zirconium acetate, zirconium acetylacetonate; zirconium alkoxide such as zirconiumethoxide, zirconium i-propoxide, zirconium n-butoxide, zirconium t-butoxide or the like; zirconium oxychloride; amide compound of zirconium such as tetrakis{dimethylamino)zirconium, tetrakis(diethylamino)zirconium or the like; zirconocene compound such as zirconocene dichloride, zirconocene dimethoxide, and decamethylzirconocene dichloride. Preferably are zirconium tetrachloride, zirconium t-butoxide, and zirconocene dichloride. The compound comprising an element of Group 4 of the Periodic Table of Elements may be used as commercially available anhydride or hydrate without any processing. A complex comprising a compound comprising an element of Group 4 of the Periodic Table of Elements and a compound having a ligating property such as tetrahydrofuran and tetramethylethylenediamine may also be usea. Although any amount of the compound comprising an element of Group 4 of the Periodic Table of Elements may be used, it is normally catalytic and preferably around 0.001 to 200 mole % per mol of the cyclopropanecarboxylic acid (1), more preferably within the range of around 0.1 to 20 mole %, and still more preferably within the range of around 0.1 to 10 mole %. The reaction of the cyclopropanecarboxylic acids (1) with the monohydroxy compound (2) in the presence of the catalyst of the present invention is usually conducted in an inert gas atmosphere such as argon and nitrogen. The reaction may be performed under a normal pressure, a pressurized pressure, or a reduced pressure. Preferably, the reaction is performed under a normal pressure or a reduced pressure. In addition, it is preferable to perform reaction while continuously removing water, which is formed as a byproduct of dehydration reaction, from the reaction system by such a method as distillation or the like. The reaction may be performed in the absence of a solvent or in a solvent. The solvent that may be used includes: halogenated hydrocarbons such as dichloromethane, chloroform, and 1, 2-dichloroethane, aliphatic hydrocarbons such as hexane, heptane, octane, nonane or the like; aromatichydrocarbons such as benzene, toluene, xylene, chlorobenzene or the like; and ether solvents such as diethyl ether, tetrahydrofuran or the like. By-produced water may be removed from the reaction system by using a solvent that forms an azeotrope with the byproduct water. Although a reaction temperature is not particularly defined, it is preferably within a range of around 20 to around 200 'C. The catalyst may be removed by washing the reaction mixture withwater or acidic water makes, and the cyciopropanecarboxy late esters (1) can be isolated by performing normal operation such as distillation, recrystallization, and column chromatography, if necessary, from the reaction mixtures. Examples The present invention will be described in detail with the following examples, but it is not to be construed that the present invention is limited to the examples. Example 1 In a 10 ml test tube-type reactor, 0.4 3 g of 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid (E/Z=80/20), 0.50 g of 3-phenoxybenzyl alcohol, 5.8 mg of zirconium tetrachloride, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145 'C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2, 2-dimethyl-3- (2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in ayieldof 98% (E/Z=84/16, selectivity: 99%) based on the material alcohol. Example 2 The reaction was performed in a similar manner as in Example 1 except that 9.4 mg of a complex of zirconium tetrachloride with 2 • tetrahydrof uran was charged instead of 5. 8 rag of zirconium tetrachloride in Example 1. A reaction mixture thereof was analyzed with gas chromatography to find that {3-phenoxyphenyl)methyl 2,2~dimethyl-3-(2-methyi-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 95% (E/Z=85/15, selectivity: 98%) based on the material alcohol. Example 3 The reaction was performed in a similar manner as in Example 1 except that 7 . 3mgof zirconocene dichloride was charged instead of 5.8 mg of zirconium tetrachloride in Example 1. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was obtained in a yield of 97% (selectivity: 98%) based on the material alcohol. Example 4 The reaction was performed in a similar manner as in Example 1 except that 9. 6 mg of zirconium t~butoxide was charged instead of 5.8 mg of zirconium tetrachloride in Example 1. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl) methyl 2,2-dimethyl-3-(2-raethyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 911 (selectivity: 92%) based on the material alcohol. Example 5 The reaction was performed in a similar manner as in Example 1 except that 6.6 mg of zirconium acetate was charged instead of 5.8 mg of zirconium tetrachloride in Example 1. A reaction mixture thereof was analyzed with gas chromatography to find that {3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 95% (selectivity: 96%) based on the material alcohol. Example 6 The reaction was performed in a similar manner as in Example 1 except that 0.47 g of (5-benzyl-3-furyl)methane~l-ol was charged instead of 0.50 g of 3-phenoxybenzyl alcohol in Example 1. A reaction mixture thereof was analyzed with gas chromatography to find that (5-benzyl-S-furyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 92% (selectivity: 99%) based on the material alcohol. Comparative Example 1 The reaction was performed in a similar manner as in Example 1 except that 12. 5 mg of concentrated sulfuric acid was charged instead of 5.8 mg of zirconium tetrachloride in Example 1. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 81% (selectivity: 87%) based on the material alcohol. Comparative Example 2 The reaction was performed in a similar manner as in Example 1 except that 23.7 mg of p-toluenesulfonic acid was charged instead of 5.8 mg of zirconium tetrachloride in Example 1. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-{2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 61% (selectivity: 93%) based on the material alcohol. Example 7 In a 10 ml test tube-type reactor, 0.43 g of 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid, 0.38 g of 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-on, 48.0 mg of zirconium t-butoxide, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145'C while water generated as a by-product during reaction was being separatedandcollectedin the trap. A react ion mixture thereof was analyzed with gas chromatography to find that 3- (2-propenyl)-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- {2-methyl-l-propenyl}cyclopropanecarboxylate was obtained in a yield of 62% ( selectivity: 97%) based on the material alcohol. Example 8 In a 10 ml test tube-type reactor, 0.85 g of 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid, 0.75 g of 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-on, 58 mg of zirconium tetrachloride, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 16 hours at 145'C while water generated as a by-product during reaction was being separated and collected in the trap. A react ion mixture thereof was analyzed with gas chromatography to find that 3-(2-propenyl}-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- (2-methyl-l-propenyl)cyclopropanecarboxyl-ate was obtained in a yield Qf 85% ( selectivity: 90%) based on the material alcohol. Examples 9 to 11 Experiments were conducted in a similar manner as in Example 3 except that the following alcohol compounds and the zirconium compounds were used in place of the alcohol and zirconium compounds used in Example 8. A: 4-hydroxy-3-methyl- Example 12 In a 10 ml test tube-type reactor, 0.16 g of 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylic acid, 0.22 g of 2,3,5, 5-tetraf luoro-4- (methoxymethyl) benzyl alcohol, 3.3 mg of zirconium tetraisopropoxide, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145 'C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate was obtained in a yield of 8 3% ( selectivity: 98%) based on the material alcohol. Example 13 In a 10 ml test tube-type reactor, 0.34 g of 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid, 0.45 g of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol, 4.7 mg of zirconium tetrachloride, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145°C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that 2,3,5,6-tetrafluoro-4- (methoxymethyl)benzyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 68% ( selectivity: 98%) based on the material alcohol. Examples 14 to 18 Experiments were conducted in a similar manner as in Example 13 except that following zirconium compounds and amounts. Example 19 In a 10ml test tube-type reactor, 0.43 g of 2,2-dimethyl-3-(2-methyl-1-propenyl}cyclopropanecarboxylic acid, 0.50 g of 3-phenoxybenzyl alcohol, 8.0 mg of hafnium tetrachloride, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145 'C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl) cyclopropanecarboxylate was obtained in a yield of 86% (selectivity: 94%) based on the material alcohol. Example 20 The reaction was performed in a similar manner as in Example 19 except that 11.6 mg of a hafnium tetrachloride-2 tetrahydrofuran complex was charged instead of 8 . 0 mg of hafnium tetrachloride in Example 19. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenaxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 97% (selectivity: 98%) based on the material alcohol. Example 21 The reaction was performed in a similar manner as in Example 19 except that 12.0 mg of a hafnium tetrachloride-2pyridine complex was charged instead of 8.0 mg of hafnium tetrachloride in Example 19. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl~l-propenyl)cyclopropanecarboxylate was obtained in a yield of 96% (selectivity: 98%) based on the material alcohol. Example 22 The reaction was performed in a similarmanner as in Example 19 except that 12.5 mg of a hafnium tetrabromide complex was charged instead of 8.0 mg of hafnium tetrachloride in Example 19. A reaction mixture thereof was analyzed with gas chromatography to find that {3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 87% (selectivity: 93%) based on the material alcohol. Example 23 The reaction was performed in a similar manner as in Example 19 except that 10.5 mg of pentamethylcyclopentadienylhafnium trichloride was charged instead of 8.0 mg of hafnium tetrachloride in Example 19. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 90% (selectivity: 94%) based on the material alcohol. Example 2 4 The reaction was performed in a similar manner as in Example 19 except that S.9 mg of tetrakis(diethylamino) hafnium was charged instead of 8.0 mg of hafnium tetrachloride in Example 19. A reaction mixture thereof was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl}methyl 2,2-dimethyl-3-(2-methyl-l-propenyl) cyclopropanecarboxylate was obtained in a yield of 93% (selectivity: 99%) based on the material alcohol. Comparative Example 3 The reaction was performed in a similar manner as in Example 19 except that 12 . 5 mg of concentrated sulfuric acid was prepared instead of 8.0 mg of hafnium tetrachloride in Example 19. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2, 2-din:iethyl-3- (2-methyl-l-propenyl) cyclopropanecarboxylate ivas obtained in a yield of 81% (selectivity: 87%) based on the naterial alcohol. Comparative Example 4 The reaction was performed in a similar manner as in Example 19 except that 23.7 mg of p-toluenesulfonic acid was charged instead of 8.0 mg of hafnium tetrachloride in Example 19. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl) methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 61% (selectivity: 93%} based on the material alcohol. Example 25 In a 10 ml test tube-type reactor were charged 0.43 g of 2,2-dimethyl-3-(2-methyl-l-propenyl)- cyclopropanecarboxylic acid, 0.38 g of 4-hydroxy-3-methyl-2- {2-propenyl-}-2-cyclopentene-l-one, 58.1 mg of a hafnium tetrachloride-2tetrahydrofuran, and 5 ml of xylene. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145 "C while water generated as a by-product during reaction was being separated and collected in the trap. The resulting reaction mixture was analyzed with gas chromatography to find that 3-(2-propenyl)-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-{2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 65% (selectivity: 84%) based on the material alcohol Example 26 The reaction was performed in a similar manner as in Example 25 except that 62.1 mg of a hafnium tetrachloride■ 2dioxane was charged instead of 58.1 mg of a hafnium tetrachloride-2 tetrahydrofuran in Example 25. A reaction mixture thereof was analyzed with gas chromatography to find that 3-(2-propenyl)-2-raethyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-{2-methyl-l-propenyl}cyclopropanecarboxylate was obtained in a yield of 59% (selectivity: 80%} based on the material alcohol. Comparative Example 5 The reaction was performed in a similar manner as in Example 25 except that 12 . 5 mg of concentrated sulfuric acid was charged instead of 58.1 mg of a hafnium tetrachloride- 2 tetrahydrofuran in Example 25. A reaction mixture thereof was analyzed with gas chromatography to find that 3-(2-propenyl)-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-(2-methyl-l-propenyl}cyclopropanecarboxylate was obtained in a yield of 30% (selectivity: 31%) based on the material alcohol. Comparative Example 6 Reaction was performed in a similar manner as in Example 25 except that 23.7 mg of p-toluenesulfonic acid was charged insteadof 58. 1 mg of a hafnium tetrachloride- 2 tetrahydtof uran in Example 25. A reaction mixture thereof was analyzed with gas chromatography to find that 3-(2-propenyl)-2~methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-{2-methyl-1-propenyl)cyclopropanecarboxylate was obtained in a yield of 6.4% (selectivity: 8%) based on the material alcohol. Example 27 In a 10ml test tube-type reactor, there were prepared 0 . 43 g of 2,2-dimethyl-3-(2-methyl-l-propenyl} cyclopropanecarboxylic acid, 0.38 g of 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-one, 58.1 mg of a complex made of hafnium tetrachloride and 2- tetrahydrofuran, and 5ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 14 5 'C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that 3-(2-propenyl)-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 61% (selectivity: 79%) based on the material alcohol. Example 2 8 The reaction was performed in a similar manner as in Example 2 7 except that 62.1 mg of a hafnium tetrachloride2dioxane complex was charged instead of 58.1 mg of a hafnium tetrachloride-2tetrahydrofuran complex in Example 27. A reaction mixture thereof was analyzed with gas chromatography to find that 3-(2-propenyl) -2-raethyl-4-oxo-2-cyclopentenyl 2,2-diniethyl-3- (2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 58% (selectivity: 79%} based on the material alcohol. Comparative Example 7 The reaction was performed in a similar manner as in Example 27 except that 12 . 5 mg of concentrated sulfuric acid was charged instead of 58.1 mg of a hafnium tetrachloride- 2tetrahydrofuran complex in Example 27. A reaction mixture thereof was analyzed with gas chromatography to find that 3-(2-propynyl) -2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- (2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 9.3% (selectivity: 12%) based on the material alcohol. Comparative Example 8 The reaction was performed in a similarmanner as in Example 27 except that 23.7 mg of p-toluenesulfonic acid was charged instead of58.1mgofa hafnium tetrachloride ■2tetrahydrofur an complex in Example 27. A reaction mixture thereof was analyzed with gas chromatography to find that 3-(2-propynyl) -2-raethyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- (2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 0.8% (selectivity: 4.4%) based on the material alcohol. Example 2 9 In a 10 ml test tube-type reactor, 0.16 g of 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylic acid, 0.22 g of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol, 4 . 6 mg of a hafnium tetrachloride•2tetrahydrofuranzirconium complex, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145 'C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate was obtainedinayieldof 80% ( selectivity: 99%) basedonthematerial alcohol. Example 30 The reaction was conducted in a similar manner as in Example 2 9 except that 5.0 mg of hafnium tetrabromide was used in place of 4 . 6 mg of a hafnium tetrachloride • 2tetrahydrifuran complex. Analysis of the reaction mixture showed that the yield of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate was 95% (selectivity: 97%) based on the alcohol. Example 31 In a 10 ml test tube-type reactor, 0.34 g of 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid, 0.45 g of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol, 18.6 mg of a hafnium tetrachloride2tetrahydrofuranzirconium complex, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that 2, 3, 5, 6-tetrafluoro-4- (methoxymethyl)benzyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 70% ( selectivity: 99%) based on the material alcohol. Example 32 The reaction was conducted in a similarmanner as in Example 31 except that 19.9 mg of hafnium tetrabromide was used in place of 18. 6 mg of a hafnium tetrachloride- 2tetrahydrofuran complex. Analysis of the reaction mixture showed that the yield of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate was 81% (selectivity: 87%) based on the alcohol. DECLARATION I, Hideo KOSAKA, a national of Japan, c/o Sumitomo Chemical Intellectual Property Service, Limited, 5-33, Kitahama 4-chome, Chuo-ku, Osaka-shi, Osaka 541-8550, Japan, declare that to the best of my knowledge and belief the attached is a full, true and faithful translation into English made by me of the certified copy of Japanese Patent Application No.2001-016106 attached thereto. JAPAN PATENT OFFICE This is to certify that the annexed is a true copy of the following application as filed with this Office. Date of Application: January 24, 2001 Application Number: 2001-016106 Applicant(s): Sumitomo Chemical Company, Limited November 9, 2001 Commissioner, Patent Office OIKAWA, Kozo 2001-3099311 [Name of Document] Patent Application [Reference No.] P152448 [Application Date] January 24, 2001 [Destination] Commissioner, Patent Office [International Patent Classification] C07C 69/747 [Inventor] [Address] c/o Sumitomo Chemical Co., Ltd. 2-10-1 Tsukahara Takatsuki-shi, Osaka Pref., Japan [Name] SOUDA, Hiroshi [Inventor] [Address] c/o Sumitomo Chemical Co., Ltd. 2-10-1 Tsukahara Takatsuki-shi, Osaka Pref., Japan [Name] IWAKURA, Kazunori [Applicant for Patent] [Identification No.] 000002093 [Name] Sumitomo Chemical Co., Ltd. [Attorney] [Identification Number] 100093285 [Patent Attorney] [Name] KUBOYAMA, Takashi [Telephone No.] 06-6220-3405 [Selected Attorney] [Identification Number] 100094477 [Patent Attorney] [Name] JINNO, Naoyoshi [Telephone Number] 06-6220-3405 [Selected Attorney] [Identification Ho.] 100113000 [Patent Attorney] [Name] NAKAYAMA, Tohru [Telephone No.] 06-6220-3405 [Designation of Charge] [Ledger No. for Prepayment]01023 8 [Amount of Payment] 21,000 yen [List of Filed Document] [Object Name] Specification 1 [Object Name] Abstract 1 [No. of Comprehensive Power of Attorney] 9903380 [Necessity of Confirmation] Yes Document Name: SPECIFICATION Title of the Invention: Production Method of Cyclopropanecarboxylate Esters Claims: 1. A production method of a cyclopropanecarboxylate ester represented by a general formula (3) (3) (in which RS R^, R^, R\ R^, and R^ represent the same as defined below}, which method is characterized by reacting a cyclopropanecarboxylic acid represented by a general formula (1) : (1), (in which R^, R^, R"^, R', and R^ independently represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which maybe substituted, andanaralkyl group which may be substituted, or an aryl group which may be substituted), with a monohydroxy compound represented by a general formula (2): R^OH (2) (in which R^ expresses: an alkyl group which may be substituted with a halogen atom, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, or a heterocyclic group; an aralkyl group which may be substituted with a phenoxy group, a nitro group, a cyano group, a halogen atom or an alkoxy group; or an aryl group which may be substituted with an alkyl group, an alkoxy group or a halogen atom) , in the presence of a compound of an element of Group 4 in the Periodic Table of Element. 2. The production method according to Claim 1, wherein the compound of an element of Group 4 in the Periodic Table of Element is a compound of Lewis acid 3 . The production method according to Claim 1, wherein the compound of an element of Group 4 in the Periodic Table of Element is a compound represented by a general formula (4): M(0)„(X)n(Y)4-2m-n (4) (in which X and Y independently represent a halogen atom, an alkoxy group, an acyloxy group, a cyclopentadienyl group, an amino group, or NO3, and M represents an element of Group 4 in the Periodic Table of Element; and m is equal to 0 or 1, and n is equal to 0, 1, or 2}. 4. The production method according to Claim 1, wherein the compound of an element of Group 4 in the Periodic Table of Element is a hafnium compound or a titani.um compound. 5. The production method according to Claim 1, wherein the compound of an element of Group 4 in the Periodic Table of Element is a hafnium or titanium halide, a hafnium or titanium alkoxide, or a hafnium or titanium amide compound. 6. The production method according to any one of Claims 1 to 5, wherein the cyclopropanecarboxylic acid represented by the general formula {1) is 2, 2-diniethyl-3- (2, 2-dichlorovinyl) cyclopropanecarboxylic acid. 7 . The production method according to any one of Claims 1 to 5, wherein the cyclopropanecarboxylic acid represented by the general formula (1) is 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid. 8 . The production method according toany one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is a primary alcohol. 9. The production method according to any one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is a benzyl alcohol. 10 . The production method according to any one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is a 3-phenoxybenzyl alcohol. 11. The production method according to any one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is a hydroxycyclopentenone. 12 . The production method according to any one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is 4-hydroxy-3-methyl-2-(2-propynyl)- 2-cyclopentene-l-one. 13 . The production method according to any one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentene-l-one. Detailed Description of the Invention: [0001] Field of the Invention: The present invention relates to a production method of cyclopropanecarboxylate esters. [0002] Prior Art: As a general synthetic method of ester compounds f romcyclopropanecarboxylic acids and various kinds of alcohols, there has been a wellknown method for providing a desired ester compound, which comprises converting corresponding cyclopropanecarboxylic acid to its acid chloride, and then reacting the same with a respective monohydroxy compound. This method, however, was not necessarily efficient as an industrial production method because it required a lengthy steps. [0003] Another method for producing the ester that has been proposed involves only one step, in which cyclopropanecarboxylic acid and a respective monohydroxy compound ate dehydrated. In general, dehydration is performed in the presence of an acid catalyst. A production method using sulfuric acid as a catalyst is reported in Japanese Patent Laid-open Publication HEX No. 9-188649, and also reported is another method of using p-toluenesulfonic acid as a catalyst in the Japanese Patent Laid-open Publication HEI No. 11-228491. However, since such methods of using mineral acid or organic acid having strong acidity cause significant coloring due to a side reaction, and also take a long reaction time, these methods were not necessarily efficient as industrial production methods. In the Japanese Patent Laid-open Publication SHO No. 60-64945, there is reported a production method of useing dicyclohexylcarbodiimide or diisopropylcarbodiimide as a dehydrating agent. However, the dehydrating agent used in the production method is expensive, and a necessary amount thereof is more than the equivalent amount of cyclopropanecarboxylic acid, which has made the method not necessarily efficient as an industrial production method. [0004] Problems to be Solved by the Invention: The present invention is to provide a production method of desired cyclopropanecarboxylate esters in excellent yieldby performing dehydration of cyclopropanecarboxylic acids and a monohydroxy compound in the presence of a compound of an element of Group 4 of the Periodic Table of Elements. [0005] Means for Solving the Problems: In order to accomplish the above object, inventors of the present invention have extensively studied and finally achieved the present invention. Thus, the present invention provides a production method of a cyclopropanecarboxylate ester represented by a general formula (3) (3) (in which R1, R2, R3, R4 R5, and R6 represent the same as defined below), which method is characterized by reacting a cyclopropanecarboxylic acid represented by a general formula (1): (1} (in which R\ R^, R^, R\ and R^ independently represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, andanaralkyl group which may be substituted, or an aryl group which may be substituted), with a raonohydroxy compound represented by a general formula (2); R6OH (2) (in which R6 represents an alkyl group which may be substituted with a halogen atom, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, or a heterocyclic group; an aralkyi group which may be substituted with a phenoxy group, a nitro group, a cyano group, a halogen atom, or an alkoxy group; or an aryl group which may be substituted with an alkyl group, an alkoxy group, or a halogen atom) , in the presence of an element of Group 4 of the Periodic Table of Elements. [0006] Mode for Carrying out the Invention: Herein below, the present Invention will be described in detail. In the present invention, a cyclopropanecarboxylic acid (1) and a monohydroxy compound (2) are reacted in the presence of an element of Group 4 of the Periodic Table of Elements for producing cyclopropanecarboxylate esters (3). [0007] The cyclopropanecarboxylic acids to be used as raw materials in the present invention are represented by the general formula (1) , in which R"-, R^, R-', R% andR^ independently represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, and an aralkyl group which may be substituted, or an aryl group which may be substituted. [0008] As the alkyl group which may be substituted, there are given an alkyl group with carbon number of 1 to 10 which may be linear, branched, or cyclic, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, menthyl and the like. As the substituents substituting for the alkyl group, there are given: a halogen atom such as fluorine, chlorine, bromine, iodine or the like; an alkoxy group such as methoxy, ethoxy, n-propoxy, i-propoxy. n-butoxy, sec-butoxy, tert-butoxy or the like; an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, see-butoxycarbonyl, tert-butoxycarbonyl or the like; an alkoxyimino group such as methoxyimino, ethoxylmino, n-propoxyimino or the like; an alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsuifonyl, tert-butylsulfonyl or the like; an alkylsulfonyloxy group such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, i-propylsulfonyloxy, tert-butylsulfonyloxy or the like; and a hydroxysulfinyl group or the like. [0009] As the alkenyl group which may be substituted, there are given: vinyl; 1-methylvinyl; 1-propenyl; 2-methyl-l-propenyl; 1-butenyl; 3-methyl-2-butenyl; 2,2-dichlorovinyl; 2,2-dibromovinyl; 2-chloro-2-fluorovinyl; 2-chloro-2-trifluoromethylvinyl; 2-bromo-2-tribrori:iomethylvinyl and the like. As the alkynyl group which may be substituted, there are given a propargyl group and the like. As the substituents substituting for these alkenyl group and alkynyl group, there are given: a halogen atom such as fluorine, chlorine, bromine, or iodine; an aryl group such as phenyl, 1-naphthyl, 2-naphthyl or the like; an alkoxy group such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, tert-butoxy or the like; an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl or the like; an alkoxyimino group such as methoxyimino, ethoxyimino, n-propoxyimino or the like; an alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsulfonyl, tert-butylsulfonyl or the like; and an alkylsulfonyloxy group such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, i-propylsulfonyloxy, tert-butylsulfonyloxy or the like. [0010] As the aralkyl group which may be substituted, there are given: benzyl; biphenylmethyl; phenylethyl; naphthylmethyl; and naphthylethyl. [0011] As the substituents substituting for the aralkyl group, there are given: a halogen atom such as fluorine, chlorine, bromine, and iodine; an alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl or the like; an alkoxy group such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, tert-butoxy or the like; an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl ot the like; an alkoxyimino group such as methoxyimino, ethoxyimino, n-propoxyimino or the like; an alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-ptopylsulfonyl, tert-butylsulfonyl or the like; and an alkylsulfonyloxy group such as methylsulfonyloxy. ethylsulfonyloxy, n-propylsulfonyloxy, i-propylsulfonyloxy, tert~butylsulfonyloxy or the like. [0012] As the aryl group which may be substituted^, there are given: phenyl; 1-naphthyl; 2-naphthyl and the like. [0013] As the substituents substituting for the aryl group, there are given: a halogen atom such as fluorine, chlorine, bromine, oriodine; analkyl group suchasmethyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl or the like; an alkoxy group such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-batoxy, tert-butoxy or the like; an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl/ tert-butoxycarbonyl or the like; an alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsul£onyl, tert-butylsulfonyl or the like; and an alkylsulfonyloxy group such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, i-propylsulfonyloxy, tert-butylsulfonyloxy or the like. [0014] As the specific compounds of cyclopropanecarboxylic acids (1) that serve as materials, there are given, for example: cyclopropanecarboxylic acid; 2-fluorocyclopropanecarboxylic acid; 1, 2-dichlorocyclopropanecarboxylic acid; 2,2-dimethyl-3-(dimethoxymethyl)cyclopropanecarboxylic acid; 2,2,3,3-tetramethylcyclopropanecaEboxylic acid; 2,2-dimethyl-3-[1-propenyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(3-methyl-2-butenyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-{2-chloro-2-fluorovinyl)-cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2-bromovinyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2, 2-dibromovinyl)cyclopropanecarboxylic acid; 2,2~dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(l,2-dibromo-2,2-dichloroethyl)-cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-cyclopropanecarboxylic acid; 2,2-dimethyl-3-{3, 3,3-trifluoro-2-(trifluoromethyl)-1-propenyl}cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2-phenyl-l-propenyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2-phenylvinyl}cyclopropanecarboxylic acid; 2-methyl-2-phenyl-3-{2-methyl-l-propenyl)cyclopropane-carboxylic acid and the like. Preferred are 2,2-dimethyl-3-(2, 2-dichlorovinyl)-cyclopropanecarboxylic acid, 2, 2-dimethyl-3-(2-methyl-l-propenyl) cyclopropanecarboxylic acid and the like. [0015] The cyclopropanecarboxylic acids (1) to be used in the present invention have an asymmetric carbon. There are two or more stereoisomers, all of which are included in the present invention. In the present invention, the stereochemistry of the cyclopropanecarboxylic acids (1) is retained, so as to produce cyclopropanecarboxylate esters (3) having the same stereochemistry in the portion derived from the carboxylic acid. [0016] As the monohydroxy compound to be used in the present invention representedby the general formula (2), there are given alkyl, aralkyl, and aryl alcohols, which may be substituted. [0017] As the alkyl group of the alkyl alcohol which may be substituted, there are given an alkyl group with carbon number of 1 to 10 which may be linear, branched, or cyclic, and may have a double bond or a triple bonded. As the substituents substituting therefore, there are given: a halogen atom such as fluorine, chlorine, bromine, and iodine; a furyl group; a phenoxyfuryl group; abenzylfuryl group; adifluoromethyl group; a propargylfuryl group; a methylisoxazolyl group; a trifluoromethylthiazolyl group; a trifluoromethoxythiazolyl group; apropynylpyrrolyl group; apropynyldioxoimidazolidinyl group; an oxo group; a propenyl group; a propynyl group; a dioxotetrahydroisoindolyl group; an oxothiazolyl group and the like. [0018] As the specific compounds of the alkyl alcoholcompound which may be substituted, there are given: methyl alcohol; ethyl alcohol; n-propyl alcohol; isopropyl alcohol; n-butyl alcohol; sec-butyl alcohol; tert-butyl alcohol; n-pentyl alcohol; neopentyl alcohol; amyl alcohol; n-hexyl alcohol; n~octyl alcohol; n-decyl alcohol; 2-furylmethyl alcohol; 3-furylmethyl alcohol; (5-phenoxy-3-furyl)methyl alcohol; (5-benzyl-3-furyl)methane-l-ol; {5-(difluoromethyl)-3-furyl}methane-l-ol; 5-propargylfurfuryl alcohol; (5-methyli30xazole-3-yl)methane-l-ol; l-{2-(trifluoromethyl)-1,3-thiazole-4-yl}prop-2-yn-l-ol; l-(2-(trifluoromethoxy)-1,3-thiazole-4-yl}prop-2-yn-l-ol; l-{l-prop-2-ynyl-5-(trifluoromethyl)pyrrole-3-yl}prop-2-yn-l-ol; (l-prop-2-ynylpyrrole-3-yl}methane-l-ol; 3-(hydroxymethyl)-l-propynyl-imidazolldine~2,4-dione; 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-one; 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentene-l-one; 2-(hydroxymethyl)-4,5,6,7-tetrahydrQisQindole-l,3-dione; {1-(2-propynyl)pyrrole-3-yl}methane-l-ol; 5-(hydroxymethyl)-4-methyl-(2-propynyl)-1,3-thia2oline-2- one; 4-methylhept-4-en-l-yn-3-ol; chloromethyl alcohol; dichloromethyl alcohol; trichloromethyl alcohol; bromomethyl alcohol; dibromomethyl alcohol; tribromomethyl alcohol; fluoromethyl alcohol; difluoromethyl alcohol; trifluoromethyl alcohol; fluoroethyl alcohol; difluoroethyl alcohol; trifluoroethyl alcohol; and tetrafluoroethyl alcohol; pentafluoroethyl alcohol; 3,3-dibronio-2-propene-l-ol; perf luoropropyl alcohol; hexafluoroisopropyl alcohol; perfiuorobutyl alcohol; perfluoropentyl alcohol; perfluorohexyl alcohol; perfluorooctyl alcohol; perfluorodecyl alcohol; {1-(2-propynyl)-5-(trifluoromethyl)-4-pyrazolyl}methane-1- ol; 1-{1-(2-propynyl)-5-trifluoromethyl}pyrrole-3-yl}prop-2-yn- l-ol; l-{2-(trifluoromethyl)-1,3-thiazole-4-yl}prop-2-yn-l-ol, l-{2-(trifluoromethoxy)-1,3-thiazole-4-yl}prop-2-yn-l-ol, and 4-fluorohept-4-en-l-yn-3-ol. [0019] As the aralkyl of the aralkyl alcohol which may be substituted, there are given, for example: benzyl; phenylethyl; phenylpropyl; naphthylmethyl; naphthylethyl; anthracenylmethyl; and indolylmethyl. Substituents thereof include: an allcyl group; a halogen atom; an alkoxyalkyl group; a haloalkyl group; an alkenyl group; an alkynyl group; a haloalkoxy group; a haloalkylacetyloxy group; a phenoxy group; a phenyl group; a cyano group; a halophenoxy group; an amino group; a pyridyl group; a thienyl group and the like. [0020] As the specific examples of the aralkyl alcohol which maybe substituted, there are given, for example: benzyl alcohol; 2-methyl-3-phenylbenzyl alcohol; 2,3,5,6-tetrafluorobenzyl alcohol; 2,3,5,6-tetrafluoro-4-methylbenzyl alcohol; 2,3,5,6-tetrafluoro-4-methoxybenzyl alcohol; 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol; 2,3,5,6-tetrafluoro-4-propargylbenzyl alcohol; 2,3,5,6-tetrafluoro-4-(difluoromethyl)benzyl alcohol; 2,3,5,6-tetrafluoro-4-(difluoromethoxy)benzyl alcohol; 2,3,5,6-tetrafluoro-4-(2,2,2-trifluoroacetyloxy)methyl-benzyl alcohol; 4-(trifluoromethyl)benzyl alcohol; 2,3,4, 5-tetrafluoro-6-niethylbenzyl alcohol; 3-phenylbenzyl alcohol, 2,6-dichlorobenzyl alcohol; 3-phenoxybenzyl alcohol; 2-hydroxy-2-(3-phenoxyph6nyl)ethanenitrile; 2-hydroxy-2-{4-(methoxymethyl)phenyl}ethanenitrile; 2-{3-(4-chlorophenoxy)phenyl}-2-hydrQxyethanenitrile; 2- (4-amino-2,3,5,6-tetrafluorophenyl)-2-hydroxyethane-nitrile; 2- {4-fluoro-3-phenoxyphenyl)-2-hydroxyethanenitrile; (2-methylphenyl)methyl alcohol, (3-methylphenyl)methyl alcohol; 4-prop-2-ynylphenyl)methane-l-ol,■ 3-prop-2-ynylphenyl)methane-l-ol,■ (l-prop-2-yny1-2-methylindole-3-yl)methane-l-ol; (l-prop-2-ynyl-2-(trifluoromethyl)indole-3-yl}methane-l-ol,■ 4-prop-2-enylindan-l-ol; 4-phenylindan-2-oI; 4- (2-thienyl)indan-2-ol; (2,3,6-trifluoro-4-pyridyl}methane-l-ol; alkoxyaralkyl alcohols generated from the haloaralkyl alcohol whose halogen atom is optionally replaced with methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-fautoxy, or tert-butoxy; cyanoaralkyl alcohol; nitroaralkyl alcohol and the like. [0021] As the aryl alcohol which may be substituted, there are given; phenol; 1-naphthol; 2-naphthol; 4-prop-2-ynylphenol; 3-prop-2-ynylphenol; 4-hydroxyacetophenone; 4-hydroxybenzaldehyde; and the above-mentioned compounds whose aromatic rings are substituted with an alkyl group, an alkoxy group, a halogen atom, or the like. [0022] As the preferable monohydroxy compound (2) there are given, for example: primary alcohols; benzyl alcohols; and hydroxycyclopentenones, and more preferably there are given: 3-phenoxybenzyl alcohol; 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-one; and 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentene-l-one. [0023] The monohydroxy compound (2)to be used in the present invention may have a asymmetric carbon. There may be two or more stereoisomers, all of which are included in the present invention. In the present invention, the stereochemistry of the monohydroxy compound {2) is retained, so as to produce cyclopropanecarboxylate esters (3) having the same stereochemistry in the portion derived from the alcohol. [0024] An amount of the monohydroxy compound (2) is one equivalent or more to the cyclopropanecarboxylic acids (1), and may be used in excess if necessary. In view of recovery and cost of the raw materials, an amount of the monohydroxy compound (2) may be one equivalent or less to the cyclopropanecarboxylic acids (1). Upon completion of reaction, unreacted materials may generally be recovered by such operation as distillation, extraction, and/or phase-separation. [0025] As the compound of an element of Group 4 of the Periodic Table of Elements to be used as a catalyst in the present invention, there are given a Lewis acid compound, and more preferably, a compound represented by a general formula (4): M(0)™(X)n(Y) ,.2m-n (4), (in which X and Y independently represent a halogen atom, an alkoxy group, an acyloxy group, a cyclopentadienyl group, an amino group, or NO3, and M represents an element of Group 4 of the Periodic Table of Elements; and m is equal to 0 or 1, and n is equal to 0, 1, or 2). As the specific examples of the compound of an element of Group 4 of the Periodic Table of Elements, there are given: titanium tetrafluoride; titanium tetrachloride; titanium tetrabromide; titanium tetraiodide; titanium acetate; titanium acetylacetonato; titanium ethoxide; titanium i-propoxide; titanium n-butoxide; titanium t-butoxide; titanium nitrate; titanium oxynitrate; titanium oxychloride; tetrakis- (dimethylamino) titanium; tetrakis(diethylamino) titanium; titanocene dichloride; titanocene dimethoxide; decamethyltitanocene dichloride; hafnium tetrafluoride; hafnium tetrachloride; hafnium tetrabromide; hafnium tetraiodide; hafnium acetate; hafnium acetylacetonato; hafnium ethoxide; hafnium i-propoxide; hafnium n-butoxide; hafnium t-butoxide; hafnium nitrate; hafnium oxynitrate; hafnium oxychloride; tetrakis (dimethylamino) hafnium; tetrakis (diethylamino) hafnium; hafnocene dichloride; hafnocene dimethoxide; decamethylhafnocene dichloride and the like. Preferably, there are given: titanium tetrachloride; titanium i-propoxide; titanocene dichloride; hafnium tetrachloride; hafnium t-butoxide; hafnocene dichloride and the like. [0026] As for the compound of an element of Group 4 of the Periodic Table of Elements, commercially available anhydride or hydrate may be used without any processing. It is also possible to use a complex made with a compound having a ligating property such as tetrahydrofuran and tetramathyl-ethylenediamine. [0027] Although an amount of an element of Group 4 of the Periodic Table of Elements is not particularly limited, it is normally around 0.001 to 200 mole % to the cyclopropanecarboxylic acids (1), preferably within the range of around 0.1 to 2 0 mole %, and more preferably within the range of around 0.1 to 10 mole %. [0028] In the reaction of the cyclopropanecarboxylic acids (1) and the monohydroxy compound (2) in the presence of the compound of an element of Group 4 of the Periodic Table of Elements, it is usually performed in an inert gas atmosphere such as argon, nitrogen or the like. The reaction may be performed under a normal pressure, a pressurized pressure, or a reduced pressure . Preferably, the reaction is performed under a normal pressure or a reduced pressure. In addition, it is preferable to perform reaction while continuously removing water, which is a byproduct of dehydration, from a reaction system by such a method as distillation. [0029] The reaction may be performed in the absence of a solvent or in a solvent. As the solvent to be used, there are given: halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane or the like; aliphatic hydrocarbons such as hexane, heptane, octane, nonane or the like; aromatic hydrocarbons such as benzene, toluene, xylene. chlorobenzene or the like; and ether solvents such as diethyl ether, tetrahydrofuran or the like. Byproduced water can be selectively continuously removed, by adding a solvent which forms azeotrope with water. [0030] Although a reaction temperature is not particularly limited, it is preferably within around 20 to 200 °C. [0031] The cyclopropanecarboxylate esters {3} produced in the reaction can be separated readily from reaction mixture by removing the catalyst by washing with water or acidic water and performing normal operation such as distillation, recrystallization, column chromatography or the lik^, if necessary. [0032] Effects of the Invention: According to the present invention, the carboxylic acids (1) is reacted with a monohydroxy compound (2) in the presence of a compound of an element of Group 4 of the Periodic Table of Elements to yield the desired cyclopropanecarboxylate esters (3) in excellent yield and selectivity, therefore it is advantageous as an industrial production method. [0033] Example: Although the present invention will be described in detail with the following examples, it should be understood that the present invention is not limited to the Examples. [0034] Example 1: In a 10ml test tube-type reactor, 0.43 g of 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid, 0.50 g of 3-phenoxybenEyl alcohol, 8.0 mg of hafnium tetrachloride, and 5 ml of xylene were charged. The reactor was eguipped with a Dean-Stark trap with a cooling tube, and under stirring and reflux the reaction was carried out for 8 hours at 145 'C while water generated as a by-product during reaction was being separated and removed into the trap. The reaction mixture was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl) methyl 2, 2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 86% (selectivity of 94%) based on the raw material alcohol. [0035] Example 2 The reaction was performed in a similar manner as in Example 1 except that 11.6 mg of hafnium tetrachloride 2•tetrahydrofuran complex was charged instead of 8.0 mg of hafnium tetrachloride in Example 1. A reaction mixture thereof was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl) met hy"" 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 97% (selectivity of 98%) based on the raw material alcohol, [0036] Example 3 Reaction was performed in a similar manner as in Example 1 except that 12. Omg of hafnium tetrachloride 2-pyridine complex was charged instead of 8.Omg of hafnium tetrachloride in Example 1 A reaction mixture thereof was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-{2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 96% (selectivity of 98%) based on the raw material alcohol. [0037] Example 4 The reaction was performed in a similar manner as in Example 1 except that 12.5 mg of hafnium tetrabromide was charged instead of 8.0 mg of hafnium tetrachloride in Example 1. The reaction mixture was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was obtained in a yield of 87% (selectivity of 93%} based on the raw material alcohol. [0038] Example 5 The reaction was performed in a similar manner as in Example 1 except that 10.5 mg of pentamethylcyclopentadienyl hafnium trichloride was charged instead of 8.0 mg of hafnium tetrachloride in Example 1. The reaction mixture was analyzed with gas chromatography, and the result indicated that {3-phenoxyphenyl) methyl 2, 2-dimethyl-3-(2-methyl-l-propenyl}cyclopropanecarboxylate was obtained in a yield of 90% (selectivity of 94%} based on the raw material alcohol. [0039] Example 6 The reaction was performed in a similar manner as in Example 1 except that 8.9 mg of tetrakis (diethylamino) hafnium was charged instead of 8. 0 mg of hafnium tetrachloride in Example 1. The reaction mixture was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl) cyclopropanecarboxylate was obtained in a yield of 93% (selectivity of 99%) based on the raw material alcohol. [0040] Comparative Example 1 The reaction was performed in a similar manner as in Example 1 except that 12.5 mg of concentrated sulfuric acid was charged instead of 8 . 0 mg of hafnium tetrachloride in Example 1. The reaction mixture was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl)- methyl 2, 2-diinethyl-3- (2-methyl-l-propenyl) cyclopropanecarboxylate was obtained in a yield of 81% {selectivity of 37%) based on the raw material alcohol, [0041] Comparative Example 2 The reaction was performed in a similar manner as in Example 1 except that 23.7 mg of p-toluenesulfonic acid was charged instead of 3.0 mg of hafnium tetrachloride in Example 1. The reaction mixture was analyzed with gas chromatography, and the result indicated that {3-phenoxyphenyl)- methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 61% (selectivity of 93%) based on the raw material alcohol. [0042] Example 7 In a 10ml test tube-type reactor, there were charged 0.4 3 g of 2,2-dimethyl-3-(2-methyl-l-propenyl)-cyclopropanecarboxylic acid, 0.38 g of 4-hydroxy-3-methyl-2- (2-propenyl)-2-cyclopentene-l-one, 58.1 mg of hafnium tetrachloride 2■tetrahydrofuran complex, and 5 ml of xylene. The reactor was equipped with a Dean-Stark trap with a cooling tube, and under stirring and reflux the reaction was carried out for 8 hours at 145 °C while water generated as a by-product during reaction was being separated and removed into the trap. The reaction mixture was analyzed with gas chromatography, and the result indicated that 3-(2-propenyl] -2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- (2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 65% (selectivity of 84%) based on the raw material alcohol [0043] Example 8 The reaction was performed according to Example 6 except that 62 .1 mg of hafnium tetrachloride 2 • dioxane complex was charged instead of 58.1 mg of of hafnium tetrachloride 2■tetrahydrofuran complex in Example 7. The teaction mixture was analyzed with gas chromatography, and the result indicated that 3-(2-propenyl) -2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- (2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 59% (selectivity of 80%) baaed on the raw material alcohol. [0044] Example 9 In a 10ml test tube-type reactor, there were charged 0.43 g of 2,2-dimethyl-3-(2-methyl-l-propenyl}-cyclopropanecarboxylic acid, 0.38 g of 4-hydroxy-3-methyl-2-(2-pi:opynyl) -2-cyclopentene-l-one, 58.1 mg of hafnium tetrachloride 2-tetrahydrofuran complex, and 5 ml of xylene. The teactor was equipped with a Dean-Stark trap with a cooling tube, and under stirring and reflux the reaction was carried out for 8 hours at 145 °C while water generated as a by-product during reaction was being separated and removed into the trap. The reaction mixture was analyzed with gas chromatography, and the result indicated that 3-{2-propynyl) -2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- (2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 61% (selectivity of 79%) based on the raw material alcohol. [0045] Example 10 The reaction was performed in a similar manner as in Example 6 except that 62.1 mg of hafnium tetrachloride 2'dioxane complex was charged instead of 58.1 mg of hafnium tetrachloride 2-tetrahydrofuran in Example 9. The reaction mixture was analyzed with gas chromatography, and the result indicated that 3-(2-propynyl) -2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- (2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 58% (selectivity of 79%) based on the raw material alcohol. Document Name: Abstract Summary: (Object) To provide a production method of cyclopropanecarboxylate esters (Solution) A production method of cyclopropanecarboxylate esters characterized by reacting cyclopropanecarboxylic acids represented by a general formula (1) with a monohydroxy compound represented by a general formula (2): R^OH (2) . in the presence of a compound of an element of Group 4 of the Periodic Table of Elements. (Selected Figure) None Patent Application No.2001-016106 [Name of Document] Correction Data [Document Corrected] Patent Application [Acknowledged Data • Additional Data] [Applicant] [Applicant's ID Number] 000002093 [Address] 5-33 Kitahama 4-chome Chuo-ku Osaka-shi, Osaka [Name] SUMITOMO CHEMICAL COMPAHY, LIMITED [Agent] Requestor [Agent's ID Number] 100093285 [Address] c/o SUMITOMO CHEMICAL COMPANY, LIMITED, 5-33 Kitahama 4-chome Chuo-ku Osaka-shi, Osaka [Name] Takashi KCJBOYAMA [Agent] [Agent's ID Number] 100094477 [Address] c/o SUMITOMO CHEMICAL COMPANY, LIMITED, 5-33 Kitahama 4-chome Chuo-ku Osaka-shi, Osaka [Name] Naoyoshi JINNO [Agent] [Agent's ID Number] 100113000 [Address] c/o SUMITOMO CHEMICAL COMPANY, LIMITED, 5-33 Kitahama 4-chome Chuo-ku Osaka-shi, Osaka [Name] Toru NAKAYAMA Patent Application No.2001-016106 Applicant's Past Record Applicant's ID Number [000002093] 1. Date of Alteration 28 August, 1990 [Reason for Alteration] New Registration Address 5-33, Kitahama 4-chome, Chuo-ku, Osaka-shi, Osaka, JAPAN Name SUMITOMO CHEMICAL COMPANY, LIMITED

Full Text

Field of the Invention:
The present invention relates to a process for producing cyclopropanecarboxylates.
Background of the invention
There have been known a production method of carboxylic acid ester from a carboxylic acid and an alcohol using a protonic acid catalyst. A production method using sulfuric acid as a catalyst is disclosed (Japanese Patent Laid-Open Publication No. 9-188649), and also disclosed is a method of using p-toluenesulfonic acid as a catalyst (Japanese Patent Laid-Open Publication No. 11-228491).
However, the methods using mineral acid or organic acid having strong acidity cause significant coloring due to a side reaction, which has made these methods not necessarily efficient as industrial production methods.
Summary of the Invention
According to the present invention, a cyclopropanecarboxylate can be conveniently produced, through dehydration reaction, from a cyclopropanecarboxylic acid and an alcohol in the presence of the catalyst as defined below.
The present invention provides a process for producing a cyclopropanecarboxylate of formula (1):

jhich process comprises reacting
a cyclopropanecarboxylic acid of formula (2):

fith a monohydroxy compound of formula (3):
RGQH (3),
in the presence of
a compound comprising an element of Group 4 of the Periodic Table of Elements, 'herein in formula (1) and (2),
R\ R^, R^, R^, and R^ independently represent
a hydrogen atom, a halogen atom,
an alkyl group which may be substituted,
an alkenyl group which may be substituted,
an alkynyl group which may be substituted,
an aryl group which may be substituted; and
in formula (3),
R^ represents
an alkyl group which may be substituted, or
an aryl group which may be substituted.

Detailed Description of the Invention
The halogen atom or the term "halo" in the present specification means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom in R-"- through R^.
The alkyl group which may be substituted and the alkenyl group whichmay be substitutedmay be linear, branched, or cyclic.
Thetermalkenylor alkynyl inR^ through R^ and substituents that may be present therein means the same group as specified for R^ to R^ below.
The aryl group represented by R^ through R^ and the "aryl" including those present as the substituent group as in aryloxy, or haloaryloxy includes a (C6-C14)aryl group such as phenyl, biphenyl, naphthyl, anthracenyl or the like.
R^, R^, R', R*, and R^ in the cyclopropanecarboxylic acid (2} and the cyclopropanecarboxylate (1) will be explained below.
Examples of the alkyl group which may be substituted represented by R^, R^, R"', R^, or R^ include, for example, a (Cl-10)alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, menthyl and the like.
Examples of the alkenyl group which may be substituted represented by RS R^, ^^, R\ or R^ include, for example, a (C2-C5)alkenyl group such as vinyl, 1-methylvinyl, 1-propenyl, 2-methyl-l-propenyl, 1-butenyl, 3-methyl-2-butenyl or the like.
The alkyl group, alkenyl and alkynyl groups represented by R^, R^, R^, R', or R^ may be independently substituted with at least one member selected from

a halogen atom, an alkoxy group, an alkoxycarbonyl group,
a haloalkoxycarbonyl group, an aryl group,
a halocycloalkylidene group, an alkoxyimino group,
an alkylsulfonyl group, an alkylsulfonyloxy group, and
a hydroxysulfinyl group.
Examples of the alkenyl group substituted with halogen
include, a halo (C2-C5) alkenyl group such as 2, 2-dichlorovinyl,
2,2-dibromovinyl, 2-chloro-2-fluorovinyl,
2-chloro-2-trifluoroinethyl vinyl, 2-bromo-2-tribromon:iethylvinyl, or the like.
Examples of the alkynyl group which may be substituted includes a propargyl group and the like.
Examples of the alkoxy group include, for example, a {C1-C4)alkoxy group such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy^ sec-butoxy, or tert-butoxy group or the like.
Examples of the alkoxycarbonyl group include, for example, a {C1-C4)alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, see-butoxycarbonyl, tert-butoxycarbonyl or the like.
Examples of the haloalkoxycarbonyl group include, for example, a halo(C1-C4)alkoxy-carbonyl group such as a 2,2,2-trifluoro-l-(triflucromethyl)ethoxycarbonyl group or the like.
Preferred aryl group are phenyl, 1-naphthyl, and 2-naphthyl groups and the like.
Examples of the halocycloalkylidene group include, for example, a halo{C3-C5)cycloalkylidene group such as

difluorocyclopropylidene group or the like.
Examples of the alkoxyimino group include, for example, a (C1-C3} alkoxy-imino group such as methoxyimino, ethoxyimino, an n-propoxyimino or the like.
Examples of the alkylsulfonyl group include, for example, a (C1-C4)alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsulfonyl, tert-butylsulfonyl or the like.
Examples of the alkylsulfonyloxy group include, for example, a (C1-C4 ) alkylsulfonyl group such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, i-propylsulfonyloxy, tert-butylsulfonyloxy or the like.
The cyclopropanecarboxyic acid (1) includes any optical isomer or mixture thereof.
Specific examples of the cyclopropanecarboxylic acid (2) include, for example, cyclopropanecarboxylic acid, 2-fluorocyclopropanecarboxylic acid, 2,2-dichlorocyclopropanecarboxylic acid, 2,2-dimethyl-3-(dimethoxymethyl)cyclopropanecarboxylic acid,
2,2,3,3-tetramethylcyclopropanecarboxylic acid, 2,2-dimethyl-3-(l-propenyl)cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid,
2,2-dimethyl-3-C3-methyl-2-butenyl)cyclopropanecarboxylic acid,
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2, 2,2-trichloroethyl)cyclopropanecarboxylic

2,2-dimethyl-3-[2-{2,2,2-trifluoro-l-Ctri.fluoroinethyl)-ethoxycarbonyl}vinyl]cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2-aza-2-methoxyvinyl)cyclopropanecarboxylic acid,
2,2-dimethyl-3-{4-aza-4-methoxy-3-methylbut-l,3-dienyl)-cyclopropanecarboxylic acid,
2,2-diraethyl-3-[2-{(tert-butyl)sulfonyl}-2-(tert-butoxy-carbonyl)vinyl]cyclopropanecarboxylic acid,
2,2-dimethyl-3-(2,2,2-tribroino-l-(methylsulfonyloxy)ethyl}-cyclopropanecarboxylic acid,
2,2-dimethyl-3-(2,2-dibromo-2-{hydroxysulfinyl)-1-(methoxy) -ethyl}cyclopropanecarboxylic acid,
2,2-dimethyl-3-{2,2,2-tribromo-l- {methylsulfonyloxy)ethyl}-cyclopropanecarboxylic acid,
2-methyl-2-ethyl-3-(1-propenyl)cyclopropanecarboxylic acid, 2,2-diethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid, and
2-inethyl-2-phenyl-3-{2-inethyl-l-propenyl) cyclopropanecarboxylic acid.
Preferred are 2,2-dxraethyl-3-
(2,2-dichlorovinyl}cyclopropanecarboxylic acid, and 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid.
Next a description will be made to the monohydroxy compound of formula (3).
Examples of the alkyl group, which may be substituted, represented by R^, include, for example,
a (Cl-ClO)alkyl group which may be substituted with a member selected from

a halogen atom, a cyano group, a nitro group,
an alkenyl group, a haloalkenyl group, an alkynyl group,
or
an aryl or heterocyclic group which may be substituted
with at lest one member selected from
an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkoxyalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aryoxy group,
a haloaryloxy group, an aralkyl group(e.g. (C7-C8}aralkyl such as benzyl, phenethyl), an acyl group[e.g. (Cl-C2)acyl such as formyl, acetyl),
a haloacyloxyalkyl group(e.g.
trifluoroacetyloxyalkyl), an amino group, and a halogen atom; or R^ represents:
a 1-, or 2-indanyl group which may be substituted with an alkynyl group or an aryl or heteroaryl group(e.g. 5- or 6-membered heteroaryl group such as thienyl); or
a cycloalkenyl group (e.g., cyclopentenyl )substituted with at least one member selected from an oxo group, an alkyl group, an alkenyl and an alkynyl group (e.g. 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-one, 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentene-l-one).
The term "alkyl" used in the alkyl, haloalkyl, and alkoxyalkyl groups as recited in the definition of R^ and substituents thereof includes a C1-C14 alkyl group.

Examples of the (C1-C14 ) alkyl group include, for example,
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl group and the like.
Examples of the haloalkyl group include fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl and the like.
The term "alkoxy" used in the alkoxy, haloalkoxy, and alkoxyalkyl groups includes a C1-C4 alkoxy group as defined above in this specification.
Examples of the alkenyl groups as recited above include a (C2-C5)alkenyl group (e.g. vinyl, 1-propenyl, l-methyl-2-propenyl, 1-butenyl, 2-penten-2-yl group or the like). The haloalkenyl group that may be present on the alkyl group represented by R^ means the same haloalkenyl group as described for the haloalkenyl group represented by R^ to R^.
Examples of the alkynyl groups that may be present on the alkyl group represented by R^ include a (C2-C5)alkynyl group (e.g, ethinyl, propynyl, butynyl, pentynyl or the like).
Examples of the heterocyclic group which may be substituted, include, for example, a furyl group, an isoxazolyl group, a pyrrolyl group, a thiazolyl group, an imidazolidine~2,4-dione group, a 4,5,6,7-tetrahydroisoindole group, an indole group, a pyridyl group, and further specific examples thereof include aphenoxyfurylgroup, abenzylfuryl group, apropargylfuryl group, a methylisoxazolyl group,a trifluoromethylthiazolyl group, a trifluoromethoxythiazolyl group, a propynylpyrrolyl group, a propynyldioxoimidazolidinyl group, a dioxotetrahydroisoindolyl group, an oxothiazolyl group,

a halopyridyl group and the like.
Examples of the aryl group which may be substituted, representedby R^, include an aryl group, whichmay be substituted with a phenyl, an alkynyl group, an acyl group, an alkyl group, an alkoxy group, or a halogen atom.
The monohydroxy compound of formula (3} includes, for example, following alkyl alcohol, aralkyl alcohol, aryl alcohol and the like.
Specific examples of the alkyl alcohol include, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, neopentyl alcohol, n-hexyl alcohol, n-octyl alcohol, n-decyl alcohol, and the like.
Specific examples of the alcohol compound of formula (3) , wherein R^ represents the alkyl substituted with a halogen atom include,
fluoroethyl alcohol, difluoroethyl alcohol, trifluoroethyl alcohol, and tetrafluoroethyl alcohol.
Specific examples of the alcohol compound of formula (3) , wherein R^ represents a methyl group substituted with a member selectedfromthealkenyl, haloalkenyl, or alkynyl group include, 4-methylhept-4-en-l-yn-3-Dl, 4-fluorohept-4-en-l-yn-3-ol and the like.
Specific examples of the alcohol compound of formula (3) , wherein R* represents a methyl or ethyl group substituted with the heterocyclic group which maybe substituted as defined above, include, for example,
2-furylmethyl alcohol, 3-furylmethyl alcohol, {5-phenoxy-3-furyl)methyl alcohol,

(5-benzyl-3-furyl)methane-l-ol, {5-(difluoromethyl)-3-furyl}raethan6-l-ol, 5-propargylfurfuryl alcohol, (5-methylisoxazole-3-yl)methane-l-ol,
l-{2-{trifluoromethyl)-l,3-thiazole-4-yl}prop-2-yn-l-ol, l-{2-(trifluoromethoxy)-1,3~thiazole-4-yl}prop-2-yn-l-ol, l-{l-prop-2-ynyl-5-(trifluoromethyl}pyrrole-3-yllprop-2-yn-l-ol,
(l-prop-2-ynylpyrrole-3-yl)methane-l-ol,
3- (hydroxymethyl) -l-propynyl-in:iida2olidine-2, 4-dione,
2-{hydroxymethyl)-4,5,6,7-tetrahydroisoindole~l, 3-dione,
{1-{2-propynyl)pyrrole-3-yl}methane-l-ol,
5-(hydroxymethyl)-4-methyl-(2-propynyl)-1, 3-thiazoline-2-
one,
(l-prop-2-yny1-2-methylindole-3-yl)methane-l-ol,
{l-prop-2-ynyl-2-(trifluoromethyl)indole-3-yl}methane-l-ol,
(2,3, 6-trifluoro-4-pyridyl)methane-l-ol,
and the like.
Specific examples of the alcohol compound of formula (3) , wherein R^ represents a methyl or ethyl group substituted with at least one member selected from the aryl group which may be substitutedas defined above, acyano group, or the alkynyl group, include, for example, aralkyl alcohols such as: benzyl alcohol, 2-m6thyl-3-phenylbenzyl alcohol, 2,3,5,6-tetrafluorobenzyl alcohol, 2,3,5,6-tetrafluoro-4-methylbenzyl alcohol, 2,3,5,6-tetrafluoro~4-methoxybenzyl alcohol, 2,3,5, 6-tetraf luoro--4- (methoxymethyl) benzyl alcohol, 2,3,5,5-tetrafluoro-4-propargylbenzyl alcohol,

(2,3,5,6-tetramethylphenyl)methyl alcohol,
(pentamethylphenyl)methyl alcohol,
(ethylphenyl) methyl alcohol, (n-propylphenyl) methyl alcohol,
(isopropylphenyl)methyl alcohol,
(n-butylphenyl)methyl alcohol,
(sec-butylphenyl)methyl alcohol,
(tert-butylphenyl)methyl alcohol,
(n-pentylphenyl)methyl alcohol,
(neopentylphenyl)methyl alcohol,
(n-hexylphenyl}methyl alcohol,
(n-octylphenyl)methyl alcohol, (n-decylphenyl)methyl alcohol,
(n-dodecylphenyl)methyl alcohol,
(n-tetradecylphenyl)methyl alcohol, naphthylmethyl alcohol,
anthracenylmethyl alcohol, 1-phenylethyl alcohol,
l-{l-naphthyl)ethyl alcohol, 1-(2-naphthyl)ethyl alcohol,
4-prop-2-ynylphenyl)methane-l-ol,
3~prop-2-ynylphenyl)methane-l-ol, and the like.
Examples of the alcohol compound of formula (3} , wherein R^ represents 1-, or 2-indanyl group which may be substituted with analkynyl grouper an aryl or heteroaryl group (e.g. thienyl) include^ for example,
4-prop-2-enylindan-l-ol, 4-phenylindan-2-ol,
4-(2-thienyl)indan~2-ol, and the like.
Examples of the aryl alcohol includes, phenol, 1-naphthol, 2-naphthol, 4-prop-2-ynylphenol, 3-prop-2-ynylphenol, 4-hydroxyacetophenone, 4-hydroxybenzaldehyde, and the above-described compounds having aromatic rings substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

Preferred monohydroxy compound (3) are primary alcohols, such as benzyl alcohol, pentafluoroethyl alcohol, 3,3-dibromo-2-propene-l-ol, perfluoropropyl alcohol, hexafluoroisopropyl alcohol, perfluorobutyl alcohol, perfluoropentyl alcohol, perfluorohexyl alcohol, perfluorooctyl alcohol, perfluorodecyl alcohol, {1-(2-propynyl)~5-(trifluoromethyl)-4-pyrazolyl}methane-l-ol,
l-{1-(2-propynyl)-5-(trifluoromethyl)pyrrole-3-yl}prop-2-yn-l-ol,
l-{2-(trifluoromethyl)-1,3-thiazole-4-yl}prop-2-yn-l-ol, l-(2-(trifluoromethoxy)-1, 3-thiazole-4-yl}prop-2-yn-l-ol, and 4-fluorohept-4-en-l-yn-3-ol.
Preferred are aralkyl alcohols and hydroxycyclopentenones, and more preferred are: 3-phenoxybenzyl alcohol;
4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-one; and 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclQpentene-l-one.
An asymmetric center (s) may be present in the monohydroxy compound (3) , and any optical isomer or a mixture thereof may be used in the present process to produce an optically active desiredester (s) (1) withretentionof configurationwith respect to the asymmetric center(s) in the alcohol moiety.
The monohydroxy compound (2) may be used in excess. Preferably, the monohydroxy compound (2) is used 1 mol or less per mol of the cyclopropanecarboxylic acids (1) . After completion of the reaction, unreacted materials may generally be recovered by such operation as distillation, extraction, or the like.

Next, a description will be made to the catalyst compound comprisinganelement of Group 4 of the Periodic Table of Elements .
Examples of the catalyst compound include a zirconiuin compound, a titanium compound, a hafnium compound and the like.
Preferred catalyst compounds are zirconium, titanium, and hafnium compounds having Lewis acidity, and can be represented by formula (4):
M(0)„,{X}„(Y)4-2m-n (4)
wherein M represents an element of Group 4 of the Periodic Table of Elements; X and Y independently represent a halogen atom, an alkoxy group, an acetylacetonate group, an acyloxy group, an amino group which may be substituted with up to two alkyl groups, or a cyclopentadienyl group; and m is equal to 0 or 1, and n is equal to 0, 1, or 2.
Specific examples of the titanium and hafnium compounds include, for example, titanium halide such as titanium tetrafluoride, titanium tetrachloride,
titanium tetrabromide, titanium tetraiodide; titanium acetate, titanium acetylacetonate, titanium ethoxide, titanium i-propoxide, titanium n-butoxide, titanium t-butoxide; titanium oxychloride; titanium amide such as tetrakis(dimethylamino)titanium,
tetrakis(diethylamino)titanium or the like; titanocene dichloride, titanocene dimethoxide, decamethyltitanocene dichloride; hafnium halide such as hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, hafnium tetraiodide or the like; hafnium acetate, hafnium acetylacetonate, hafnium alkoxide such as hafnium ethoxide.

hafnium i-propoxide, hafnium n-butoxide, hafnium t-butoxide or
the like; hafnium oxychloride; amide compound of hafnium such
33 tetrakis(dimethylamino)hafnium,
tetrakis(diethylamino)hafnium or the like; hafnocene dichloride, hafnocene dimethoxide, and decamethylhafnocene dichloride.
Among the specific compounds, preferred are titanium tetrachloride, titanium i-propoxide, titanocene dichloride, hafnium tetrachloride, hafnium t-butoxide, and hafnocene dichloride.
Specific examples of the zirconium compound includes, for example, zirconium halide such as zirconium tetrafluoride, zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide or th§ like; zirconium acetate, zirconium acetylacetonate; zirconium alkoxide such as zirconiumethoxide, zirconium i-propoxide, zirconium n-butoxide, zirconium t-butoxide or the like; zirconium oxychloride; amide compound of zirconium such as tetrakis{dimethylamino)zirconium, tetrakis(diethylamino)zirconium or the like; zirconocene compound such as zirconocene dichloride, zirconocene dimethoxide, and decamethylzirconocene dichloride. Preferably are zirconium tetrachloride, zirconium t-butoxide, and zirconocene dichloride.
The compound comprising an element of Group 4 of the Periodic Table of Elements may be used as commercially available anhydride or hydrate without any processing. A complex comprising a compound comprising an element of Group 4 of the Periodic Table of Elements and a compound having a ligating property such as tetrahydrofuran and tetramethylethylenediamine may also be

usea.
Although any amount of the compound comprising an element of Group 4 of the Periodic Table of Elements may be used, it is normally catalytic and preferably around 0.001 to 200 mole % per mol of the cyclopropanecarboxylic acid (1), more preferably within the range of around 0.1 to 20 mole %, and still more preferably within the range of around 0.1 to 10 mole %.
The reaction of the cyclopropanecarboxylic acids (1) with the monohydroxy compound (2) in the presence of the catalyst of the present invention is usually conducted in an inert gas atmosphere such as argon and nitrogen. The reaction may be performed under a normal pressure, a pressurized pressure, or a reduced pressure. Preferably, the reaction is performed under a normal pressure or a reduced pressure. In addition, it is preferable to perform reaction while continuously removing water, which is formed as a byproduct of dehydration reaction, from the reaction system by such a method as distillation or the like.
The reaction may be performed in the absence of a solvent or in a solvent. The solvent that may be used includes: halogenated hydrocarbons such as dichloromethane, chloroform, and 1, 2-dichloroethane, aliphatic hydrocarbons such as hexane, heptane, octane, nonane or the like; aromatichydrocarbons such as benzene, toluene, xylene, chlorobenzene or the like; and ether solvents such as diethyl ether, tetrahydrofuran or the like. By-produced water may be removed from the reaction system by using a solvent that forms an azeotrope with the byproduct water.
Although a reaction temperature is not particularly defined, it is preferably within a range of around 20 to around 200 'C.

The catalyst may be removed by washing the reaction mixture withwater or acidic water makes, and the cyciopropanecarboxy late esters (1) can be isolated by performing normal operation such as distillation, recrystallization, and column chromatography, if necessary, from the reaction mixtures.
Examples
The present invention will be described in detail with the following examples, but it is not to be construed that the present invention is limited to the examples.
Example 1
In a 10 ml test tube-type reactor, 0.4 3 g of
2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic
acid (E/Z=80/20), 0.50 g of 3-phenoxybenzyl alcohol, 5.8 mg
of zirconium tetrachloride, and 5 ml of xylene were charged.
The reactor was equipped with a Dean-Stark trap and a condenser,
and the reaction mixture was stirred under reflux for 8 hours
at 145 'C while water generated as a by-product during reaction
was being separated and collected in the trap. A reaction mixture
thereof was analyzed with gas chromatography to find that
(3-phenoxyphenyl)methyl 2, 2-dimethyl-3-
(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in ayieldof 98% (E/Z=84/16, selectivity: 99%) based on the material alcohol.
Example 2
The reaction was performed in a similar manner as in Example 1 except that 9.4 mg of a complex of zirconium tetrachloride

with 2 • tetrahydrof uran was charged instead of 5. 8 rag of zirconium tetrachloride in Example 1.
A reaction mixture thereof was analyzed with gas chromatography to find that {3-phenoxyphenyl)methyl 2,2~dimethyl-3-(2-methyi-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 95% (E/Z=85/15, selectivity: 98%) based on the material alcohol.
Example 3
The reaction was performed in a similar manner as in Example 1 except that 7 . 3mgof zirconocene dichloride was charged instead of 5.8 mg of zirconium tetrachloride in Example 1.
A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was obtained in a yield of 97% (selectivity: 98%) based on the material alcohol.
Example 4
The reaction was performed in a similar manner as in Example 1 except that 9. 6 mg of zirconium t~butoxide was charged instead of 5.8 mg of zirconium tetrachloride in Example 1.
A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl) methyl 2,2-dimethyl-3-(2-raethyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 911 (selectivity: 92%) based on the material alcohol.
Example 5

The reaction was performed in a similar manner as in Example 1 except that 6.6 mg of zirconium acetate was charged instead of 5.8 mg of zirconium tetrachloride in Example 1.
A reaction mixture thereof was analyzed with gas chromatography to find that {3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 95% (selectivity: 96%) based on the material alcohol.
Example 6
The reaction was performed in a similar manner as in Example 1 except that 0.47 g of (5-benzyl-3-furyl)methane~l-ol was charged instead of 0.50 g of 3-phenoxybenzyl alcohol in Example 1.
A reaction mixture thereof was analyzed with gas chromatography to find that (5-benzyl-S-furyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 92% (selectivity: 99%) based on the material alcohol.
Comparative Example 1
The reaction was performed in a similar manner as in Example 1 except that 12. 5 mg of concentrated sulfuric acid was charged instead of 5.8 mg of zirconium tetrachloride in Example 1.
A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 81% (selectivity: 87%) based on the material alcohol.

Comparative Example 2
The reaction was performed in a similar manner as in Example 1 except that 23.7 mg of p-toluenesulfonic acid was charged instead of 5.8 mg of zirconium tetrachloride in Example 1.
A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-{2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 61% (selectivity: 93%) based on the material alcohol.
Example 7
In a 10 ml test tube-type reactor, 0.43 g of
2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic
acid, 0.38 g of
4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-on, 48.0 mg of zirconium t-butoxide, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145'C while water generated as a by-product during reaction was being separatedandcollectedin the trap. A react ion mixture thereof was analyzed with gas chromatography to find that 3- (2-propenyl)-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- {2-methyl-l-propenyl}cyclopropanecarboxylate was obtained in a yield of 62% ( selectivity: 97%) based on the material alcohol.
Example 8

In a 10 ml test tube-type reactor, 0.85 g of
2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic
acid, 0.75 g of
4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-on, 58 mg of zirconium tetrachloride, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 16 hours at 145'C while water generated as a by-product during reaction was being separated and collected in the trap. A react ion mixture thereof was analyzed with gas chromatography to find that 3-(2-propenyl}-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- (2-methyl-l-propenyl)cyclopropanecarboxyl-ate was obtained in a yield Qf 85% ( selectivity: 90%) based on the material alcohol.
Examples 9 to 11
Experiments were conducted in a similar manner as in Example 3 except that the following alcohol compounds and the zirconium compounds were used in place of the alcohol and zirconium compounds used in Example 8.
A: 4-hydroxy-3-methyl- Example 12

In a 10 ml test tube-type reactor, 0.16 g of 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylic acid, 0.22 g of 2,3,5, 5-tetraf luoro-4- (methoxymethyl) benzyl alcohol, 3.3 mg of zirconium tetraisopropoxide, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145 'C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate was obtained in a yield of 8 3% ( selectivity: 98%) based on the material alcohol.
Example 13
In a 10 ml test tube-type reactor, 0.34 g of 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid, 0.45 g of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol, 4.7 mg of zirconium tetrachloride, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145°C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that 2,3,5,6-tetrafluoro-4- (methoxymethyl)benzyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 68% ( selectivity: 98%) based on the material alcohol.

Examples 14 to 18
Experiments were conducted in a similar manner as in Example 13 except that following zirconium compounds and amounts.

Example 19
In a 10ml test tube-type reactor, 0.43 g of 2,2-dimethyl-3-(2-methyl-1-propenyl}cyclopropanecarboxylic acid, 0.50 g of 3-phenoxybenzyl alcohol, 8.0 mg of hafnium tetrachloride, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145 'C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl) cyclopropanecarboxylate was obtained in a yield of 86% (selectivity: 94%) based on the material alcohol.
Example 20
The reaction was performed in a similar manner as in Example

19 except that 11.6 mg of a hafnium tetrachloride-2 tetrahydrofuran complex was charged instead of 8 . 0 mg of hafnium tetrachloride in Example 19.
A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenaxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 97% (selectivity: 98%) based on the material alcohol.
Example 21
The reaction was performed in a similar manner as in Example 19 except that 12.0 mg of a hafnium tetrachloride-2pyridine complex was charged instead of 8.0 mg of hafnium tetrachloride in Example 19.
A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl~l-propenyl)cyclopropanecarboxylate was obtained in a yield of 96% (selectivity: 98%) based on the material alcohol.
Example 22
The reaction was performed in a similarmanner as in Example 19 except that 12.5 mg of a hafnium tetrabromide complex was charged instead of 8.0 mg of hafnium tetrachloride in Example 19.
A reaction mixture thereof was analyzed with gas chromatography to find that {3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 87% (selectivity: 93%) based on the

material alcohol.
Example 23
The reaction was performed in a similar manner as in Example 19 except that 10.5 mg of pentamethylcyclopentadienylhafnium trichloride was charged instead of 8.0 mg of hafnium tetrachloride in Example 19.
A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 90% (selectivity: 94%) based on the material alcohol.
Example 2 4
The reaction was performed in a similar manner as in Example 19 except that S.9 mg of tetrakis(diethylamino) hafnium was charged instead of 8.0 mg of hafnium tetrachloride in Example 19. A reaction mixture thereof was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl}methyl
2,2-dimethyl-3-(2-methyl-l-propenyl) cyclopropanecarboxylate was obtained in a yield of 93% (selectivity: 99%) based on the material alcohol.
Comparative Example 3
The reaction was performed in a similar manner as in Example 19 except that 12 . 5 mg of concentrated sulfuric acid was prepared instead of 8.0 mg of hafnium tetrachloride in Example 19. A reaction mixture thereof was analyzed with gas chromatography

to find that (3-phenoxyphenyl)methyl 2, 2-din:iethyl-3- (2-methyl-l-propenyl) cyclopropanecarboxylate ivas obtained in a yield of 81% (selectivity: 87%) based on the naterial alcohol.
Comparative Example 4
The reaction was performed in a similar manner as in Example 19 except that 23.7 mg of p-toluenesulfonic acid was charged instead of 8.0 mg of hafnium tetrachloride in Example 19. A reaction mixture thereof was analyzed with gas chromatography to find that (3-phenoxyphenyl) methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 61% (selectivity: 93%} based on the material alcohol.
Example 25
In a 10 ml test tube-type reactor were charged 0.43 g of 2,2-dimethyl-3-(2-methyl-l-propenyl)-
cyclopropanecarboxylic acid, 0.38 g of 4-hydroxy-3-methyl-2-
{2-propenyl-}-2-cyclopentene-l-one, 58.1 mg of a hafnium
tetrachloride-2tetrahydrofuran, and 5 ml of xylene. The
reactor was equipped with a Dean-Stark trap and a condenser,
and the reaction mixture was stirred under reflux for 8 hours
at 145 "C while water generated as a by-product during reaction
was being separated and collected in the trap. The resulting
reaction mixture was analyzed with gas chromatography to find
that 3-(2-propenyl)-2-methyl-4-oxo-2-cyclopentenyl
2,2-dimethyl-3-{2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 65% (selectivity: 84%) based on the

material alcohol
Example 26
The reaction was performed in a similar manner as in Example 25 except that 62.1 mg of a hafnium tetrachloride■ 2dioxane was charged instead of 58.1 mg of a hafnium tetrachloride-2 tetrahydrofuran in Example 25. A reaction mixture thereof was analyzed with gas chromatography to find that 3-(2-propenyl)-2-raethyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-{2-methyl-l-propenyl}cyclopropanecarboxylate was obtained in a yield of 59% (selectivity: 80%} based on the material alcohol.
Comparative Example 5
The reaction was performed in a similar manner as in Example
25 except that 12 . 5 mg of concentrated sulfuric acid was charged
instead of 58.1 mg of a hafnium tetrachloride- 2 tetrahydrofuran
in Example 25. A reaction mixture thereof was analyzed with gas
chromatography to find that
3-(2-propenyl)-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-(2-methyl-l-propenyl}cyclopropanecarboxylate was obtained in a yield of 30% (selectivity: 31%) based on the material alcohol.
Comparative Example 6
Reaction was performed in a similar manner as in Example 25 except that 23.7 mg of p-toluenesulfonic acid was charged insteadof 58. 1 mg of a hafnium tetrachloride- 2 tetrahydtof uran in Example 25. A reaction mixture thereof was analyzed with gas

chromatography to find that
3-(2-propenyl)-2~methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-{2-methyl-1-propenyl)cyclopropanecarboxylate was obtained in a yield of 6.4% (selectivity: 8%) based on the material alcohol.
Example 27
In a 10ml test tube-type reactor, there were prepared 0 . 43
g of 2,2-dimethyl-3-(2-methyl-l-propenyl}
cyclopropanecarboxylic acid, 0.38 g of 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-one, 58.1 mg of a complex made of hafnium tetrachloride and 2- tetrahydrofuran, and 5ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 14 5 'C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that 3-(2-propenyl)-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 61% (selectivity: 79%) based on the material alcohol.
Example 2 8
The reaction was performed in a similar manner as in Example 2 7 except that 62.1 mg of a hafnium tetrachloride*2dioxane complex was charged instead of 58.1 mg of a hafnium tetrachloride-2tetrahydrofuran complex in Example 27.
A reaction mixture thereof was analyzed with gas chromatography to find that 3-(2-propenyl)

-2-raethyl-4-oxo-2-cyclopentenyl 2,2-diniethyl-3-
(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 58% (selectivity: 79%} based on the material alcohol.
Comparative Example 7
The reaction was performed in a similar manner as in Example 27 except that 12 . 5 mg of concentrated sulfuric acid was charged instead of 58.1 mg of a hafnium tetrachloride- 2tetrahydrofuran complex in Example 27.
A reaction mixture thereof was analyzed with gas
chromatography to find that 3-(2-propynyl)
-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-
(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 9.3% (selectivity: 12%) based on the material alcohol.
Comparative Example 8
The reaction was performed in a similarmanner as in Example 27 except that 23.7 mg of p-toluenesulfonic acid was charged instead of58.1mgofa hafnium tetrachloride ■2tetrahydrofur an complex in Example 27.
A reaction mixture thereof was analyzed with gas
chromatography to find that 3-(2-propynyl)
-2-raethyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-
(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 0.8% (selectivity: 4.4%) based on the material alcohol.
Example 2 9
In a 10 ml test tube-type reactor, 0.16 g of 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylic acid, 0.22

g of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol, 4 . 6 mg of a hafnium tetrachloride•2tetrahydrofuranzirconium complex, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145 'C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl
2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate was obtainedinayieldof 80% ( selectivity: 99%) basedonthematerial alcohol.
Example 30
The reaction was conducted in a similar manner as in Example 2 9 except that 5.0 mg of hafnium tetrabromide was used in place of 4 . 6 mg of a hafnium tetrachloride • 2tetrahydrifuran complex. Analysis of the reaction mixture showed that the yield of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl
2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate was 95% (selectivity: 97%) based on the alcohol.
Example 31
In a 10 ml test tube-type reactor, 0.34 g of 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid, 0.45 g of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol, 18.6 mg of a hafnium tetrachloride*2tetrahydrofuranzirconium complex, and 5 ml of xylene were charged. The reactor was equipped with a Dean-Stark

trap and a condenser, and the reaction mixture was stirred under reflux for 8 hours at 145C while water generated as a by-product during reaction was being separated and collected in the trap. A reaction mixture thereof was analyzed with gas chromatography to find that 2, 3, 5, 6-tetrafluoro-4- (methoxymethyl)benzyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 70% ( selectivity: 99%) based on the material alcohol.
Example 32
The reaction was conducted in a similarmanner as in Example 31 except that 19.9 mg of hafnium tetrabromide was used in place of 18. 6 mg of a hafnium tetrachloride- 2tetrahydrofuran complex. Analysis of the reaction mixture showed that the yield of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl
2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate was 81% (selectivity: 87%) based on the alcohol.

DECLARATION
I, Hideo KOSAKA, a national of Japan, c/o Sumitomo Chemical Intellectual Property Service, Limited, 5-33, Kitahama 4-chome, Chuo-ku, Osaka-shi, Osaka 541-8550, Japan, declare that to the best of my knowledge and belief the attached is a full, true and faithful translation into English made by me of the certified copy of Japanese Patent Application No.2001-016106 attached thereto.

JAPAN PATENT OFFICE
This is to certify that the annexed is a true copy of the following application as filed with this Office.
Date of Application: January 24, 2001
Application Number: 2001-016106
Applicant(s): Sumitomo Chemical Company, Limited
November 9, 2001 Commissioner, Patent Office OIKAWA, Kozo
2001-3099311

[Name of Document] Patent Application
[Reference No.] P152448
[Application Date] January 24, 2001
[Destination] Commissioner, Patent Office
[International Patent Classification]
C07C 69/747 [Inventor]
[Address] c/o Sumitomo Chemical Co., Ltd.
2-10-1 Tsukahara Takatsuki-shi, Osaka Pref., Japan
[Name] SOUDA, Hiroshi
[Inventor]
[Address] c/o Sumitomo Chemical Co., Ltd.
2-10-1 Tsukahara Takatsuki-shi, Osaka Pref., Japan
[Name] IWAKURA, Kazunori
[Applicant for Patent]
[Identification No.] 000002093
[Name] Sumitomo Chemical Co., Ltd.
[Attorney]
[Identification Number] 100093285
[Patent Attorney]
[Name] KUBOYAMA, Takashi
[Telephone No.] 06-6220-3405
[Selected Attorney]
[Identification Number] 100094477
[Patent Attorney]
[Name] JINNO, Naoyoshi

[Telephone Number] 06-6220-3405
[Selected Attorney] [Identification Ho.] 100113000 [Patent Attorney]
[Name] NAKAYAMA, Tohru
[Telephone No.] 06-6220-3405
[Designation of Charge] [Ledger No. for Prepayment]01023 8 [Amount of Payment] 21,000 yen
[List of Filed Document]
[Object Name] Specification 1
[Object Name] Abstract 1
[No. of Comprehensive Power of Attorney]
9903380
[Necessity of Confirmation] Yes

Document Name: SPECIFICATION Title of the Invention:
Production Method of Cyclopropanecarboxylate Esters Claims:
1. A production method of a cyclopropanecarboxylate
ester represented by a general formula (3)
(3) (in which RS R^, R^, R\ R^, and R^ represent the same as defined
below}, which method is characterized by reacting a
cyclopropanecarboxylic acid represented by a general formula
(1) :
(1), (in which R^, R^, R"^, R', and R^ independently represent a hydrogen
atom, a halogen atom, an alkyl group which may be substituted,
an alkenyl group which may be substituted, an alkynyl group which
maybe substituted, andanaralkyl group which may be substituted,
or an aryl group which may be substituted), with
a monohydroxy compound represented by a general formula (2):
R^OH (2) (in which R^ expresses: an alkyl group which may be substituted with a halogen atom, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, or a heterocyclic group; an aralkyl group which may be substituted with a phenoxy group, a nitro group, a cyano group, a halogen atom or an alkoxy group;

or an aryl group which may be substituted with an alkyl group, an alkoxy group or a halogen atom) , in the presence of a compound of an element of Group 4 in the Periodic Table of Element.
2. The production method according to Claim 1, wherein
the compound of an element of Group 4 in the Periodic Table of Element is a compound of Lewis acid
3 . The production method according to Claim 1, wherein
the compound of an element of Group 4 in the Periodic Table of Element is a compound represented by a general formula (4):
M(0)„(X)n(Y)4-2m-n (4)
(in which X and Y independently represent a halogen atom, an alkoxy group, an acyloxy group, a cyclopentadienyl group, an amino group, or NO3, and M represents an element of Group 4 in the Periodic Table of Element; and m is equal to 0 or 1, and n is equal to 0, 1, or 2}.
4. The production method according to Claim 1, wherein the compound of an element of Group 4 in the Periodic Table of Element is a hafnium compound or a titani.um compound.
5. The production method according to Claim 1, wherein the compound of an element of Group 4 in the Periodic Table of Element is a hafnium or titanium halide, a hafnium or titanium alkoxide, or a hafnium or titanium amide compound.
6. The production method according to any one of Claims

1 to 5, wherein the cyclopropanecarboxylic acid represented by the general formula {1) is 2, 2-diniethyl-3- (2, 2-dichlorovinyl) cyclopropanecarboxylic acid.
7 . The production method according to any one of Claims 1 to 5, wherein the cyclopropanecarboxylic acid represented by the general formula (1) is 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid.
8 . The production method according toany one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is a primary alcohol.
9. The production method according to any one of Claims
1 to 7, wherein the monohydroxy compound represented by the general formula (2) is a benzyl alcohol.
10 . The production method according to any one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is a 3-phenoxybenzyl alcohol.
11. The production method according to any one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is a hydroxycyclopentenone.
12 . The production method according to any one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is 4-hydroxy-3-methyl-2-(2-propynyl)-

2-cyclopentene-l-one.
13 . The production method according to any one of Claims 1 to 7, wherein the monohydroxy compound represented by the general formula (2) is 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentene-l-one.
Detailed Description of the Invention:
[0001]
Field of the Invention:
The present invention relates to a production method of cyclopropanecarboxylate esters. [0002] Prior Art:
As a general synthetic method of ester compounds f romcyclopropanecarboxylic acids and various kinds of alcohols, there has been a wellknown method for providing a desired ester compound, which comprises converting corresponding cyclopropanecarboxylic acid to its acid chloride, and then reacting the same with a respective monohydroxy compound.
This method, however, was not necessarily efficient as an industrial production method because it required a lengthy steps. [0003]
Another method for producing the ester that has been proposed involves only one step, in which cyclopropanecarboxylic acid and a respective monohydroxy compound ate dehydrated. In general, dehydration is performed in the presence of an acid catalyst. A production method using

sulfuric acid as a catalyst is reported in Japanese Patent Laid-open Publication HEX No. 9-188649, and also reported is another method of using p-toluenesulfonic acid as a catalyst in the Japanese Patent Laid-open Publication HEI No. 11-228491.
However, since such methods of using mineral acid or organic acid having strong acidity cause significant coloring due to a side reaction, and also take a long reaction time, these methods were not necessarily efficient as industrial production methods.
In the Japanese Patent Laid-open Publication SHO No. 60-64945, there is reported a production method of useing dicyclohexylcarbodiimide or diisopropylcarbodiimide as a dehydrating agent.
However, the dehydrating agent used in the production method is expensive, and a necessary amount thereof is more than the equivalent amount of cyclopropanecarboxylic acid, which has made the method not necessarily efficient as an industrial production method.
[0004]
Problems to be Solved by the Invention:
The present invention is to provide a production method of desired cyclopropanecarboxylate esters in excellent yieldby performing dehydration of cyclopropanecarboxylic acids and a monohydroxy compound in the presence of a compound of an element of Group 4 of the Periodic Table of Elements. [0005] Means for Solving the Problems:
In order to accomplish the above object, inventors

of the present invention have extensively studied and finally achieved the present invention. Thus, the present invention provides a production method of a cyclopropanecarboxylate ester represented by a general formula (3)
(3) (in which R1, R2, R3, R4 R5, and R6 represent the same as defined
below), which method is characterized by reacting a
cyclopropanecarboxylic acid represented by a general formula
(1):
(1} (in which R\ R^, R^, R\ and R^ independently represent a hydrogen
atom, a halogen atom, an alkyl group which may be substituted,
an alkenyl group which may be substituted, an alkynyl group which
may be substituted, andanaralkyl group which may be substituted,
or an aryl group which may be substituted), with
a raonohydroxy compound represented by a general formula (2);
R6OH (2)
(in which R6 represents an alkyl group which may be substituted
with a halogen atom, an alkenyl group, an alkynyl group, a
cycloalkyl group, a cycloalkenyl group, or a heterocyclic group;
an aralkyi group which may be substituted with a phenoxy group,
a nitro group, a cyano group, a halogen atom, or an alkoxy group;
or an aryl group which may be substituted with an alkyl group,
an alkoxy group, or a halogen atom) , in the presence of an element
of Group 4 of the Periodic Table of Elements.

[0006]
Mode for Carrying out the Invention:
Herein below, the present Invention will be described in detail.
In the present invention, a cyclopropanecarboxylic acid (1) and a monohydroxy compound (2) are reacted in the presence of an element of Group 4 of the Periodic Table of Elements for producing cyclopropanecarboxylate esters (3).
[0007]
The cyclopropanecarboxylic acids to be used as raw materials in the present invention are represented by the general formula (1) , in which R"-, R^, R-', R% andR^ independently represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, and an aralkyl group which may be substituted, or an aryl group which may be substituted.
[0008]
As the alkyl group which may be substituted, there are given an alkyl group with carbon number of 1 to 10 which may be linear, branched, or cyclic, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, menthyl and the like. As the substituents substituting for the alkyl group, there are given: a halogen atom such as fluorine, chlorine, bromine, iodine or the like; an alkoxy group such as methoxy, ethoxy, n-propoxy, i-propoxy.

n-butoxy, sec-butoxy, tert-butoxy or the like; an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, see-butoxycarbonyl, tert-butoxycarbonyl or the like; an alkoxyimino group such as methoxyimino, ethoxylmino, n-propoxyimino or the like; an alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsuifonyl, tert-butylsulfonyl or the like; an alkylsulfonyloxy group such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, i-propylsulfonyloxy, tert-butylsulfonyloxy or the like; and a hydroxysulfinyl group or the like.
[0009]
As the alkenyl group which may be substituted, there are given: vinyl; 1-methylvinyl; 1-propenyl; 2-methyl-l-propenyl; 1-butenyl; 3-methyl-2-butenyl; 2,2-dichlorovinyl; 2,2-dibromovinyl; 2-chloro-2-fluorovinyl; 2-chloro-2-trifluoromethylvinyl;
2-bromo-2-tribrori:iomethylvinyl and the like. As the alkynyl group which may be substituted, there are given a propargyl group and the like.
As the substituents substituting for these alkenyl group and alkynyl group, there are given: a halogen atom such as fluorine, chlorine, bromine, or iodine; an aryl group such as phenyl, 1-naphthyl, 2-naphthyl or the like; an alkoxy group such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, tert-butoxy or the like; an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl,

i-propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl or the like; an alkoxyimino group such as methoxyimino, ethoxyimino, n-propoxyimino or the like; an alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsulfonyl, tert-butylsulfonyl or the like; and an alkylsulfonyloxy group such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, i-propylsulfonyloxy, tert-butylsulfonyloxy or the like.
[0010]
As the aralkyl group which may be substituted, there are given: benzyl; biphenylmethyl; phenylethyl; naphthylmethyl; and naphthylethyl.
[0011]
As the substituents substituting for the aralkyl group, there are given: a halogen atom such as fluorine, chlorine, bromine, and iodine; an alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl or the like; an alkoxy group such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, tert-butoxy or the like; an alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl ot the like; an alkoxyimino group such as methoxyimino, ethoxyimino, n-propoxyimino or the like; an alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-ptopylsulfonyl, tert-butylsulfonyl or the like; and an alkylsulfonyloxy group such as methylsulfonyloxy.

ethylsulfonyloxy, n-propylsulfonyloxy, i-propylsulfonyloxy, tert~butylsulfonyloxy or the like.
[0012]
As the aryl group which may be substituted^, there are given: phenyl; 1-naphthyl; 2-naphthyl and the like.
[0013]
As the substituents substituting for the aryl group,
there are given: a halogen atom such as fluorine, chlorine,
bromine, oriodine; analkyl group suchasmethyl, ethyl, n-propyl,
i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl,
cyclohexyl or the like; an alkoxy group such as methoxy, ethoxy,
n-propoxy, i-propoxy, n-butoxy, sec-batoxy, tert-butoxy or the
like; an alkoxycarbonyl group such as methoxycarbonyl,
ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl,
n-butoxycarbonyl, sec-butoxycarbonyl/ tert-butoxycarbonyl or
the like; an alkylsulfonyl group such as methylsulfonyl,
ethylsulfonyl, n-propylsulfonyl, i-propylsul£onyl,
tert-butylsulfonyl or the like; and an alkylsulfonyloxy group
such as methylsulfonyloxy, ethylsulfonyloxy,
n-propylsulfonyloxy, i-propylsulfonyloxy,
tert-butylsulfonyloxy or the like. [0014]
As the specific compounds of
cyclopropanecarboxylic acids (1) that serve as materials,
there are given, for example:
cyclopropanecarboxylic acid;
2-fluorocyclopropanecarboxylic acid;

1, 2-dichlorocyclopropanecarboxylic acid; 2,2-dimethyl-3-(dimethoxymethyl)cyclopropanecarboxylic acid;
2,2,3,3-tetramethylcyclopropanecaEboxylic acid;
2,2-dimethyl-3-[1-propenyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid;
2,2-dimethyl-3-(3-methyl-2-butenyl)cyclopropanecarboxylic acid;
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid;
2,2-dimethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylic acid;
2,2-dimethyl-3-{2-chloro-2-fluorovinyl)-cyclopropanecarboxylic acid;
2,2-dimethyl-3-(2-bromovinyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2, 2-dibromovinyl)cyclopropanecarboxylic acid;
2,2~dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylic acid;
2,2-dimethyl-3-(l,2-dibromo-2,2-dichloroethyl)-cyclopropanecarboxylic acid;
2,2-dimethyl-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-cyclopropanecarboxylic acid;
2,2-dimethyl-3-{3, 3,3-trifluoro-2-(trifluoromethyl)-1-propenyl}cyclopropanecarboxylic acid;
2,2-dimethyl-3-(2-phenyl-l-propenyl)cyclopropanecarboxylic acid; 2,2-dimethyl-3-(2-phenylvinyl}cyclopropanecarboxylic acid;

2-methyl-2-phenyl-3-{2-methyl-l-propenyl)cyclopropane-carboxylic acid and the like.
Preferred are 2,2-dimethyl-3-(2, 2-dichlorovinyl)-cyclopropanecarboxylic acid, 2, 2-dimethyl-3-(2-methyl-l-propenyl) cyclopropanecarboxylic acid and the like.
[0015]
The cyclopropanecarboxylic acids (1) to be used in the present invention have an asymmetric carbon. There are two or more stereoisomers, all of which are included in the present invention. In the present invention, the stereochemistry of the cyclopropanecarboxylic acids (1) is retained, so as to produce cyclopropanecarboxylate esters (3) having the same stereochemistry in the portion derived from the carboxylic acid.
[0016]
As the monohydroxy compound to be used in the present invention representedby the general formula (2), there are given alkyl, aralkyl, and aryl alcohols, which may be substituted.
[0017]
As the alkyl group of the alkyl alcohol which may be substituted, there are given an alkyl group with carbon number of 1 to 10 which may be linear, branched, or cyclic, and may have a double bond or a triple bonded. As the substituents substituting therefore, there are given: a halogen atom such as fluorine, chlorine, bromine, and iodine; a furyl group; a phenoxyfuryl group; abenzylfuryl group; adifluoromethyl group; a propargylfuryl group; a methylisoxazolyl group; a

trifluoromethylthiazolyl group; a trifluoromethoxythiazolyl group; apropynylpyrrolyl group; apropynyldioxoimidazolidinyl group; an oxo group; a propenyl group; a propynyl group; a dioxotetrahydroisoindolyl group; an oxothiazolyl group and the like.
[0018]
As the specific compounds of the alkyl alcoholcompound which may be substituted, there are given: methyl alcohol; ethyl alcohol; n-propyl alcohol; isopropyl alcohol; n-butyl alcohol; sec-butyl alcohol; tert-butyl alcohol; n-pentyl alcohol; neopentyl alcohol; amyl alcohol; n-hexyl alcohol; n~octyl alcohol; n-decyl alcohol; 2-furylmethyl alcohol; 3-furylmethyl alcohol; (5-phenoxy-3-furyl)methyl alcohol;
(5-benzyl-3-furyl)methane-l-ol; {5-(difluoromethyl)-3-furyl}methane-l-ol; 5-propargylfurfuryl alcohol; (5-methyli30xazole-3-yl)methane-l-ol;
l-{2-(trifluoromethyl)-1,3-thiazole-4-yl}prop-2-yn-l-ol; l-(2-(trifluoromethoxy)-1,3-thiazole-4-yl}prop-2-yn-l-ol; l-{l-prop-2-ynyl-5-(trifluoromethyl)pyrrole-3-yl}prop-2-yn-l-ol; (l-prop-2-ynylpyrrole-3-yl}methane-l-ol; 3-(hydroxymethyl)-l-propynyl-imidazolldine~2,4-dione; 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-one; 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentene-l-one; 2-(hydroxymethyl)-4,5,6,7-tetrahydrQisQindole-l,3-dione; {1-(2-propynyl)pyrrole-3-yl}methane-l-ol;

5-(hydroxymethyl)-4-methyl-(2-propynyl)-1,3-thia2oline-2-
one; 4-methylhept-4-en-l-yn-3-ol;
chloromethyl alcohol; dichloromethyl alcohol;
trichloromethyl alcohol; bromomethyl alcohol;
dibromomethyl alcohol; tribromomethyl alcohol;
fluoromethyl alcohol; difluoromethyl alcohol;
trifluoromethyl alcohol; fluoroethyl alcohol;
difluoroethyl alcohol; trifluoroethyl alcohol; and
tetrafluoroethyl alcohol; pentafluoroethyl alcohol;
3,3-dibronio-2-propene-l-ol; perf luoropropyl alcohol;
hexafluoroisopropyl alcohol; perfiuorobutyl alcohol;
perfluoropentyl alcohol; perfluorohexyl alcohol;
perfluorooctyl alcohol; perfluorodecyl alcohol;
{1-(2-propynyl)-5-(trifluoromethyl)-4-pyrazolyl}methane-1-
ol;
1-{1-(2-propynyl)-5-trifluoromethyl}pyrrole-3-yl}prop-2-yn-
l-ol;
l-{2-(trifluoromethyl)-1,3-thiazole-4-yl}prop-2-yn-l-ol,
l-{2-(trifluoromethoxy)-1,3-thiazole-4-yl}prop-2-yn-l-ol,
and 4-fluorohept-4-en-l-yn-3-ol.
[0019]
As the aralkyl of the aralkyl alcohol which may be substituted, there are given, for example: benzyl; phenylethyl; phenylpropyl; naphthylmethyl; naphthylethyl; anthracenylmethyl; and indolylmethyl.
Substituents thereof include: an allcyl group; a halogen atom; an alkoxyalkyl group; a haloalkyl group; an alkenyl group; an alkynyl group; a haloalkoxy group; a haloalkylacetyloxy group;

a phenoxy group; a phenyl group; a cyano group; a halophenoxy group; an amino group; a pyridyl group; a thienyl group and the like.
[0020]
As the specific examples of the aralkyl alcohol which maybe substituted, there are given, for example: benzyl alcohol; 2-methyl-3-phenylbenzyl alcohol;
2,3,5,6-tetrafluorobenzyl alcohol;
2,3,5,6-tetrafluoro-4-methylbenzyl alcohol;
2,3,5,6-tetrafluoro-4-methoxybenzyl alcohol;
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol;
2,3,5,6-tetrafluoro-4-propargylbenzyl alcohol;
2,3,5,6-tetrafluoro-4-(difluoromethyl)benzyl alcohol; 2,3,5,6-tetrafluoro-4-(difluoromethoxy)benzyl alcohol; 2,3,5,6-tetrafluoro-4-(2,2,2-trifluoroacetyloxy)methyl-benzyl alcohol;
4-(trifluoromethyl)benzyl alcohol;
2,3,4, 5-tetrafluoro-6-niethylbenzyl alcohol;
3-phenylbenzyl alcohol, 2,6-dichlorobenzyl alcohol; 3-phenoxybenzyl alcohol;
2-hydroxy-2-(3-phenoxyph6nyl)ethanenitrile; 2-hydroxy-2-{4-(methoxymethyl)phenyl}ethanenitrile; 2-{3-(4-chlorophenoxy)phenyl}-2-hydrQxyethanenitrile; 2- (4-amino-2,3,5,6-tetrafluorophenyl)-2-hydroxyethane-nitrile;
2- {4-fluoro-3-phenoxyphenyl)-2-hydroxyethanenitrile; (2-methylphenyl)methyl alcohol, (3-methylphenyl)methyl alcohol;

4-prop-2-ynylphenyl)methane-l-ol,■
3-prop-2-ynylphenyl)methane-l-ol,■
(l-prop-2-yny1-2-methylindole-3-yl)methane-l-ol;
(l-prop-2-ynyl-2-(trifluoromethyl)indole-3-yl}methane-l-ol,■
4-prop-2-enylindan-l-ol; 4-phenylindan-2-oI;
4- (2-thienyl)indan-2-ol;
(2,3,6-trifluoro-4-pyridyl}methane-l-ol;
alkoxyaralkyl alcohols generated from the haloaralkyl alcohol
whose halogen atom is optionally replaced with methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, sec-fautoxy, or tert-butoxy;
cyanoaralkyl alcohol; nitroaralkyl alcohol and the like.
[0021]
As the aryl alcohol which may be substituted, there
are given; phenol; 1-naphthol; 2-naphthol;
4-prop-2-ynylphenol; 3-prop-2-ynylphenol;
4-hydroxyacetophenone; 4-hydroxybenzaldehyde; and the above-mentioned compounds whose aromatic rings are substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.
[0022]
As the preferable monohydroxy compound (2) there are given, for example: primary alcohols; benzyl alcohols; and hydroxycyclopentenones, and more preferably there are given: 3-phenoxybenzyl alcohol; 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopentene-l-one; and 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopentene-l-one.

[0023]
The monohydroxy compound (2)to be used in the present invention may have a asymmetric carbon. There may be two or more stereoisomers, all of which are included in the present invention. In the present invention, the stereochemistry of the monohydroxy compound {2) is retained, so as to produce cyclopropanecarboxylate esters (3) having the same stereochemistry in the portion derived from the alcohol.
[0024]
An amount of the monohydroxy compound (2) is one equivalent or more to the cyclopropanecarboxylic acids (1), and may be used in excess if necessary. In view of recovery and cost of the raw materials, an amount of the monohydroxy compound (2) may be one equivalent or less to the cyclopropanecarboxylic acids (1). Upon completion of reaction, unreacted materials may generally be recovered by such operation as distillation, extraction, and/or phase-separation.
[0025]
As the compound of an element of Group 4 of the Periodic Table of Elements to be used as a catalyst in the present invention, there are given a Lewis acid compound, and more preferably, a compound represented by a general formula (4):
M(0)™(X)n(Y) ,.2m-n (4),
(in which X and Y independently represent a halogen atom, an alkoxy group, an acyloxy group, a cyclopentadienyl group, an amino group, or NO3, and M represents an element of Group 4 of the Periodic Table of Elements; and m is equal to 0 or 1, and

n is equal to 0, 1, or 2).
As the specific examples of the compound of an element of Group 4 of the Periodic Table of Elements, there are given: titanium tetrafluoride; titanium tetrachloride; titanium tetrabromide; titanium tetraiodide; titanium acetate; titanium acetylacetonato; titanium ethoxide; titanium i-propoxide; titanium n-butoxide; titanium t-butoxide; titanium nitrate; titanium oxynitrate; titanium oxychloride; tetrakis- (dimethylamino) titanium; tetrakis(diethylamino) titanium; titanocene dichloride; titanocene dimethoxide; decamethyltitanocene dichloride; hafnium tetrafluoride; hafnium tetrachloride; hafnium tetrabromide; hafnium tetraiodide; hafnium acetate; hafnium acetylacetonato; hafnium ethoxide; hafnium i-propoxide; hafnium n-butoxide; hafnium t-butoxide; hafnium nitrate; hafnium oxynitrate; hafnium oxychloride; tetrakis (dimethylamino) hafnium; tetrakis (diethylamino) hafnium; hafnocene dichloride; hafnocene dimethoxide; decamethylhafnocene dichloride and the like. Preferably, there are given: titanium tetrachloride; titanium i-propoxide; titanocene dichloride; hafnium tetrachloride; hafnium t-butoxide; hafnocene dichloride and the like.
[0026]
As for the compound of an element of Group 4 of the Periodic Table of Elements, commercially available anhydride or hydrate may be used without any processing. It is also possible to use a complex made with a compound having a ligating property such as tetrahydrofuran and tetramathyl-ethylenediamine.

[0027]
Although an amount of an element of Group 4 of the Periodic Table of Elements is not particularly limited, it is normally around 0.001 to 200 mole % to the cyclopropanecarboxylic acids (1), preferably within the range of around 0.1 to 2 0 mole %, and more preferably within the range of around 0.1 to 10 mole %.
[0028]
In the reaction of the cyclopropanecarboxylic acids (1) and the monohydroxy compound (2) in the presence of the compound of an element of Group 4 of the Periodic Table of Elements, it is usually performed in an inert gas atmosphere such as argon, nitrogen or the like. The reaction may be performed under a normal pressure, a pressurized pressure, or a reduced pressure . Preferably, the reaction is performed under a normal pressure or a reduced pressure. In addition, it is preferable to perform reaction while continuously removing water, which is a byproduct of dehydration, from a reaction system by such a method as distillation.
[0029]
The reaction may be performed in the absence of a solvent or in a solvent. As the solvent to be used, there are given: halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane or the like; aliphatic hydrocarbons such as hexane, heptane, octane, nonane or the like; aromatic hydrocarbons such as benzene, toluene, xylene.

chlorobenzene or the like; and ether solvents such as diethyl ether, tetrahydrofuran or the like. Byproduced water can be selectively continuously removed, by adding a solvent which forms azeotrope with water.
[0030]
Although a reaction temperature is not particularly limited, it is preferably within around 20 to 200 °C.
[0031]
The cyclopropanecarboxylate esters {3} produced in the reaction can be separated readily from reaction mixture by removing the catalyst by washing with water or acidic water and performing normal operation such as distillation, recrystallization, column chromatography or the lik^, if necessary.
[0032]
Effects of the Invention:
According to the present invention, the carboxylic acids (1) is reacted with a monohydroxy compound (2) in the presence of a compound of an element of Group 4 of the Periodic Table of Elements to yield the desired cyclopropanecarboxylate esters (3) in excellent yield and selectivity, therefore it is advantageous as an industrial production method.
[0033] Example:

Although the present invention will be described in detail with the following examples, it should be understood that the present invention is not limited to the Examples.
[0034] Example 1:
In a 10ml test tube-type reactor, 0.43 g of 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylic acid, 0.50 g of 3-phenoxybenEyl alcohol, 8.0 mg of hafnium tetrachloride, and 5 ml of xylene were charged. The reactor was eguipped with a Dean-Stark trap with a cooling tube, and under stirring and reflux the reaction was carried out for 8 hours at 145 'C while water generated as a by-product during reaction was being separated and removed into the trap. The reaction mixture was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl) methyl 2, 2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 86% (selectivity of 94%) based on the raw material alcohol.
[0035] Example 2
The reaction was performed in a similar manner as in Example 1 except that 11.6 mg of hafnium tetrachloride 2•tetrahydrofuran complex was charged instead of 8.0 mg of hafnium tetrachloride in Example 1.
A reaction mixture thereof was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl) met hy""

2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 97% (selectivity of 98%) based on the raw material alcohol,
[0036] Example 3
Reaction was performed in a similar manner as in Example 1 except that 12. Omg of hafnium tetrachloride 2-pyridine complex was charged instead of 8.Omg of hafnium tetrachloride in Example 1
A reaction mixture thereof was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-{2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 96% (selectivity of 98%) based on the raw material alcohol.
[0037]
Example 4
The reaction was performed in a similar manner as in Example 1 except that 12.5 mg of hafnium tetrabromide was charged instead of 8.0 mg of hafnium tetrachloride in Example 1. The reaction mixture was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was obtained in a yield of 87% (selectivity of 93%} based on the raw material alcohol.
[0038]

Example 5
The reaction was performed in a similar manner as in Example 1 except that 10.5 mg of pentamethylcyclopentadienyl hafnium trichloride was charged instead of 8.0 mg of hafnium tetrachloride in Example 1. The reaction mixture was analyzed with gas chromatography, and the result indicated that {3-phenoxyphenyl) methyl 2, 2-dimethyl-3-(2-methyl-l-propenyl}cyclopropanecarboxylate was obtained in a yield of 90% (selectivity of 94%} based on the raw material alcohol.
[0039] Example 6
The reaction was performed in a similar manner as in Example 1 except that 8.9 mg of tetrakis (diethylamino) hafnium was charged instead of 8. 0 mg of hafnium tetrachloride in Example 1. The reaction mixture was analyzed with gas chromatography, and the result indicated that
(3-phenoxyphenyl)methyl 2,2-dimethyl-3-(2-methyl-l-propenyl) cyclopropanecarboxylate was obtained in a yield of 93%
(selectivity of 99%) based on the raw material alcohol.
[0040]
Comparative Example 1
The reaction was performed in a similar manner as in Example 1 except that 12.5 mg of concentrated sulfuric acid was charged instead of 8 . 0 mg of hafnium tetrachloride in Example 1. The reaction mixture was analyzed with gas chromatography, and the result indicated that (3-phenoxyphenyl)- methyl

2, 2-diinethyl-3- (2-methyl-l-propenyl) cyclopropanecarboxylate was obtained in a yield of 81% {selectivity of 37%) based on the raw material alcohol,
[0041]
Comparative Example 2
The reaction was performed in a similar manner as in Example 1 except that 23.7 mg of p-toluenesulfonic acid was charged instead of 3.0 mg of hafnium tetrachloride in Example 1. The reaction mixture was analyzed with gas chromatography, and the result indicated that {3-phenoxyphenyl)- methyl 2,2-dimethyl-3-(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 61% (selectivity of 93%) based on the raw material alcohol.
[0042] Example 7
In a 10ml test tube-type reactor, there were charged 0.4 3 g of 2,2-dimethyl-3-(2-methyl-l-propenyl)-cyclopropanecarboxylic acid, 0.38 g of 4-hydroxy-3-methyl-2-
(2-propenyl)-2-cyclopentene-l-one, 58.1 mg of hafnium
tetrachloride 2■tetrahydrofuran complex, and 5 ml of xylene.
The reactor was equipped with a Dean-Stark trap with a cooling
tube, and under stirring and reflux the reaction was carried
out for 8 hours at 145 °C while water generated as a by-product
during reaction was being separated and removed into the trap.
The reaction mixture was analyzed with gas chromatography, and
the result indicated that 3-(2-propenyl]
-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-

(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 65% (selectivity of 84%) based on the raw material alcohol
[0043] Example 8
The reaction was performed according to Example 6 except that 62 .1 mg of hafnium tetrachloride 2 • dioxane complex was charged instead of 58.1 mg of of hafnium tetrachloride 2■tetrahydrofuran complex in Example 7.
The teaction mixture was analyzed with gas chromatography, and
the result indicated that 3-(2-propenyl)
-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-
(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 59% (selectivity of 80%) baaed on the raw material alcohol.
[0044] Example 9
In a 10ml test tube-type reactor, there were charged 0.43 g of 2,2-dimethyl-3-(2-methyl-l-propenyl}-cyclopropanecarboxylic acid, 0.38 g of 4-hydroxy-3-methyl-2-(2-pi:opynyl) -2-cyclopentene-l-one, 58.1 mg of hafnium tetrachloride 2-tetrahydrofuran complex, and 5 ml of xylene. The teactor was equipped with a Dean-Stark trap with a cooling tube, and under stirring and reflux the reaction was carried out for 8 hours at 145 °C while water generated as a by-product during reaction was being separated and removed into the trap. The reaction mixture was analyzed with gas chromatography, and

the result indicated that 3-{2-propynyl)
-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-
(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 61% (selectivity of 79%) based on the raw material alcohol.
[0045] Example 10
The reaction was performed in a similar manner as in Example 6 except that 62.1 mg of hafnium tetrachloride 2'dioxane complex was charged instead of 58.1 mg of hafnium tetrachloride 2-tetrahydrofuran in Example 9.
The reaction mixture was analyzed with gas
chromatography, and the result indicated that 3-(2-propynyl)
-2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3-
(2-methyl-l-propenyl)cyclopropanecarboxylate was obtained in a yield of 58% (selectivity of 79%) based on the raw material alcohol.

Document Name: Abstract Summary:
(Object) To provide a production method of cyclopropanecarboxylate esters
(Solution) A production method of
cyclopropanecarboxylate esters characterized by reacting cyclopropanecarboxylic acids represented by a general formula (1)

with a monohydroxy compound represented by a general formula (2):
R^OH (2) .
in the presence of a compound of an element of Group 4 of the
Periodic Table of Elements.
(Selected Figure) None

Patent Application No.2001-016106
[Name of Document] Correction Data [Document Corrected] Patent Application [Acknowledged Data • Additional Data] [Applicant]
[Applicant's ID Number] 000002093
[Address] 5-33 Kitahama 4-chome Chuo-ku Osaka-shi, Osaka [Name] SUMITOMO CHEMICAL COMPAHY, LIMITED [Agent] Requestor
[Agent's ID Number] 100093285
[Address] c/o SUMITOMO CHEMICAL COMPANY, LIMITED,
5-33 Kitahama 4-chome Chuo-ku Osaka-shi, Osaka [Name] Takashi KCJBOYAMA [Agent]
[Agent's ID Number] 100094477
[Address] c/o SUMITOMO CHEMICAL COMPANY, LIMITED,
5-33 Kitahama 4-chome Chuo-ku Osaka-shi, Osaka [Name] Naoyoshi JINNO [Agent]
[Agent's ID Number] 100113000
[Address] c/o SUMITOMO CHEMICAL COMPANY, LIMITED,
5-33 Kitahama 4-chome Chuo-ku Osaka-shi, Osaka [Name] Toru NAKAYAMA

Patent Application No.2001-016106
Applicant's Past Record
Applicant's ID Number [000002093]
1. Date of Alteration 28 August, 1990 [Reason for Alteration] New Registration
Address 5-33, Kitahama 4-chome, Chuo-ku, Osaka-shi,
Osaka, JAPAN Name SUMITOMO CHEMICAL COMPANY, LIMITED

Documents:

0058-mas-2002 abstract-duplicate.pdf

0058-mas-2002 abstract.pdf

0058-mas-2002 claims-duplicate.pdf

0058-mas-2002 claims.pdf

0058-mas-2002 correspondence-others.pdf

0058-mas-2002 correspondence-po.pdf

0058-mas-2002 description (complete)-duplicate.pdf

0058-mas-2002 description (complete).pdf

0058-mas-2002 form-1.pdf

0058-mas-2002 form-18.pdf

0058-mas-2002 form-26.pdf

0058-mas-2002 form-3.pdf

0058-mas-2002 form-5.pdf

0058-mas-2002 petition.pdf

58-mas-2002 claims granted.pdf

58-mas-2002 description (complete) granted.pdf

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Patent Number

219739

Indian Patent Application Number

58/MAS/2002

PG Journal Number

27/2008

Publication Date

04-Jul-2008

Grant Date

13-May-2008

Date of Filing

24-Jan-2002

Name of Patentee

SUMITOMO CHEMICAL COMPANY, LIMITED

Applicant Address

Inventors:

#	Inventor's Name	Inventor's Address
1	KAZUNORI IW AKURA
2	HIROSHI SOUDA

PCT International Classification Number

C07C121/75

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2001-016106	2001-01-24	Japan
2	2001-016107	2001-01-24	Japan