CH620192A5 - Process for the preparation of esters of substituted cyclopropanecarboxylic acids - Google Patents

Description

The subject of the present invention is a process for the synthesis of substituted cyclopropanecarboxylic esters of the following general formula:

V

01 /

.CH = C

I '

V 5

R COOR

in which R1, R2, R3 and R4, identical or different, each represent a hydrogen atom or a hydrocarbon group, R1 and R2 or R1 and R3 can be linked to together form a nucleus with the carbon atoms to which they are attached , R5 is an alcohol residue and Y and Z, identical or different, each represent a hydrogen atom, or a halogen atom.

The substituted cyclopropanecarboxylic esters represented by the general formula I are useful as insecticides or as intermediates for the synthesis of insecticides. In particular, allethronyl-, pyrethronyl-, 3-phenoxybenzyl- and 5-benzyl-3-furylmethylesters, 2,2-dimethyl-3- (2 ', 2'-dihalogenovinyl) cyclopropanecarboxylic acids have insecticidal activity at least several times as high as that of the corresponding esters of chrysanthemic acid and they have much better photostability and these esters are included in pyrethrin analogs which have recently attracted attention in the art as insecticides [see "European Chemical News", November, 23, 39 (1973); M. Elliot et al., "Nature", 244, 456 (1973); D.G. Brawn et al., “J. Agr.

Food Chem. ”, 21, No. 5, 767 (1973)].

It is known in the art that the above esters can be prepared by decomposing a lower alkyl ester of chrysanthemic acid with ozone, then subjecting the lower alkyl ester of 3-formyl-2,2-dimethylcyclo- acid propanecarboxylic obtained at the Wittig reaction (see Japanese patent N "47531/74).

However, this known method is not advantageous industrially because the lower alkyl ester starting from chrysanthemic acid is expensive and an expensive phosphorus compound should be used as the reactant.

Following the present research to develop a process for the preparation of the above esters, 2,2-dimethyl-3- (2 ', 2'-dihalogenovinyl) cyclopropane-carboxylic acids at low cost with industrial advantages, has now found methods in which the Wittig reaction is not used.

5

10

15

20

25

30

35

40

45

50

55

60

65

620192

4

The essential reaction of the present methods is represented by the following diagram:

R

\

C - C - CH

R

2 / |

CH X / \

basic substance V

4 N c

R COOR

R CH

\ r /

CC

s / \ / \ r3

vs

- <

R

R

\ 5

COOR

Among the basic substances to be used for this reaction, there may be mentioned for example: 1) alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, 2) alkaline earth metal hydroxides such as hydroxide calcium and barium hydroxide, 3) alkali metal alcoholates such as sodium methylate, sodium ethylate, potassium methylate, potassium ethylate, sodium n-propylate, n-butylate sodium, sodium isoamylate, potassium t-butoxide and potassium isoamylate, 4) organic bases containing nitrogen such as 1,5-diaza-bicyclo- [3,4,0] -nonene-5 (abbreviated as DBN), 1,5-diaza-bicyclo- [5,4,0] -undecene-5 (abbreviated as DBU), 1,4-diaza-bicyclo- [2,2, 2] -octane (abbreviated as DABCO), 2-dimethylamino-1-pyrroline and 5-methyl-1-azabicyclo- [3,3,0] -octane, 5) organolithic compounds such as n-butyllithium, sec-butyllithium, diisopropylaminolithium and dicyclohexylaminolithium, 6) alkali metal hydrides such as sodium hydride and potassium hydride, 7) alkali metal amides such as sodium amide and potassium amide, and 8) alkali metals such as sodium metallic and metallic potassium.

The treatment can be carried out with a basic substance such as one of those indicated above at a temperature between approximately -80 ° C. and approximately 100 ° C. It is preferred, when using an alkali metal alcoholate, an alkali metal hydroxide or an organic base containing nitrogen, to carry out the treatment at a temperature of about 10 to about 100 ° C and, when using sodium hydride, sodium amide, etc., carry out the treatment at - 70 ° C up to + 25 ° C.

The use of a solvent is not particularly critical in this reaction but, if desired, solvents which do not take part in the reaction can be used such as ethyl ether, tetrahydrofuran, benzene, toluene, methanol, n-propanol, isopropanol, n-butanol, t-butanol, n-hexane, n-octane, chlorobenzene, dichloromethane, ethyl acetate, tetrachloride carbon and acetonitrile.

When an alcohol is used as the solvent as illustrated in the examples below, it often happens that all or part of the substituted cyclopropanecarboxylic ester obtained is converted into a form of an ester of cyclopropanecarboxylic acid substituted with l alcohol used as solvent; that is to say that there is an ester exchange between the ester of substituted cyclopropanecarboxylic acid obtained and the alcohol used as solvent.

A substituted cyclopropanecarboxylic ester of the general formula above is thus prepared. If desired, as illustrated in the examples below, the substituted cyclopropanecarboxylic ester of formula l is not isolated, but converted to a corresponding substituted cyclopropanecarboxylic acid by adding water to the reaction mixture containing the ester of formula I to effect the hydrolysis of the latter. In this case, a water-soluble solvent such as methyl alcohol, ethyl alcohol or tetrahydrofuran is used as the solvent.

The basic substance is generally used in an amount of 0.3 to 7.0 mol / mol of the y-halo-6-unsaturated carboxylic ester of formula V. However, in the case of an organic base containing nitrogen, it is possible to use a large excess of the organic base so that it also acts as a solvent. When the substituted cyclopropane-15 carboxylic ester formed by the reaction is hydrolyzed and a corresponding carboxylic acid is directly prepared, this can be achieved effectively by adding an excess of the basic substance in an amount necessary for the hydrolysis , then neutralizing the aqueous layer when the reaction is complete.

The starting compound of formula V is obtained by the reaction of an allyl alcohol of the following general formula:

1

25

30

II

CXYZ

in which R1, R2, R3, Y and Z have the above meaning and X is a halogen atom chosen from F, Cl, Br and I, with an orthocarboxylic ester of general formula:

R4-CH2-C (OR5) 3

III

wherein R4 and R5 have the above meaning and three of the R5 groups may be the same or different in the presence or absence of an acid catalyst.

The synthesis takes place as follows:

40 C See head of next page)

During this reaction, various by-products are formed but, from various physical values described below, it is explained that the main reaction product, i.e., the intermediate compound of the present invention, is a compound with the following general formula V:

1

R R ^

R - C - C - CH = C

i

Z

CH X

^ \ c

55 R COOR

wherein R1, R2, R3, R4, R5, X, Y and Z have the above meaning.

In the 1-halo-3-alkene-2-ol of general formula II m above, R1, R2 and R3, which may be the same or different, each represent a hydrogen atom or an alkyl group having up to 15 carbon atoms, a cycloalkyl group having up to 8 carbon atoms, an alkenyl group having up to 15 carbon atoms, a cycloalkenyl group 65 having up to 8 carbon atoms, an alkynyl group having up to 15 carbon atoms, an aryl group having up to 10 carbon atoms and R1 and R2 or R1 or R3 may be linked to form a ring together with the

5

620 192

-f- R4 - CH2C (OR5) 3 [III]

R1 OH I I C CH

27 ^ / \

R C CXYZ

> 3

R-

[II]

OR5 f-

4 1 / "0R

R4 - Cll0 - C <

1 0

R

>>

-R5OH C CH -R5OH

27 \ / \

R C CXYZ

13 Rp

OR5 R1 R5

R - CH = C \ oli

X0 R - C - C = CH - CXYZ

I

I CH> CH

2 '% / \ / \ 5

R C CXYZ R COOR5

1 3

R

R1 R5

2 1 1 A

-> R - C - C - CH "= C \ Il XZ

^ CH X

R4 \ oOR5

carbon atoms to which they are attached. X is a halogen atom chosen from F, Cl, Br and I and Y, Z are a hydrogen or halogen atom.

As a typical example of l-halo-3-alkene-2-ol represented by formula II, mention may be made of l, l, l-trichloro-4-methyl-3-penten-2-ol, l, l, l-tribromo-4-methyl-3-penten-2-ol, l-chloro-l, l-dibromo-4-methyl-3-penten-2-ol, l-bromo-1,1-dichloro- 4-methyl-3-penten-2-ol, l, l-dichloro-4-methyl-3-penten-2-ol, l, l-dibromo-4-methyl-3-penten-2-ol, 1,1,1-trichloro-4-methyl-3-hepten-2-ol, l, l, l-tribromo-4-methyl-3-hepten-2-ol, l, l-dichloro-4 -methyl-3-hepten-2-ol, 1,1-dibromo-4-methyl-3-hepten-2-ol, l, l, l-trichloro-4,6,6-tri-methyl-3 -hepten-2-ol, l, l, l-tribromo-4,6,6-trimethyl-3-hepten-2-ol, l, l, l-trichloro-4-ethyl-3-hexen-2 -ol, l, l, l-tribromo-4-ethyl-3-hexen-2-ol, l, l, l-trichloro-4-methyl-3-hexen-2-ol, l, l, l-tribromo-4-methyl-3-hexen-2-ol, l, l, l-trichloro-3-hepten-2-ol and l, l, l-tribromo-3-heptén-2-ol.

Among the preceding l-halo-3-alkene-2-ols, the 1,1,1-trichloro-4-methyl-3-penten-2-ol is a known compound and so this compound can be synthesized for example according to a process represented by the following reaction: [see “J. Chem. Soc. ", (C) 1966,

670]: OH

MgX

CC1-CH0 3

CCI.

where X represents Cl or Br and represents a group ch3 ch3

I l ch2 = c-ch2 or ch3-c = ch-,

Other 1-halo-3-alkene-2-ol are new compounds and in general they can be prepared according to a process represented by the following reaction:

620192

6

CXYZ * CHO

CXYZ

In the above formula, R1, R2, R3, Y and Z have the meaning indicated above for the formula I and X and X 'represent a halogen atom.

The above process for the synthesis of 1-halo-3-alkene-2-ol using Grignard reagents as starting material involves industrial difficulties and it is preferred to prepare l-halo-3 alcene-2-ol by the following process developed by Kuraray Co Ltd:

+ CXYZ-CHO

LIVES

Prins reaction,

VI

catalyst: acid

R

11

OH

v

C-CH-CH-CXYZ

^ A5

isomerization

II

CXYZ

where R1, R2, R3, X, Y and Z have the above meaning.

In the unsaturated hydrocarbon of formula VI to be used for this reaction synthesis, at least one of R1 and R2 has at least one active hydrogen atom linked to the carbon atom in position a- (the carbon atom attached directly to the double bond).

In the compound of the following formula:

R

11

f

• H

R

\ 2.y

^ C-CH-CH-CXYZ

I 3

R

Rn is a group which has lost an active hydrogen atom linked to the carbon atom in position a of R1 when R12 is the same group as R2 of formula VI, and R11 is the same group as R1 when R12 is a group which has lost an active hydrogen atom linked to the carbon atom in position a of R12.

As illustrated above, the 1-halo-3-alkene-2-ol of formula II is prepared by subjecting an unsaturated hydrocarbon of formula VI and a haloacetaldehyde of formula VII to the Prins reaction and, as required, to the isomerization of the double bond in the reaction product obtained.

Among the unsaturated hydrocarbons of formula VI, there may be mentioned for example propene, isobutene, 2-methyl-1-butene, diisobutene, 1-pentene, 2-ethyl-1-butene and 2- 1-methyl-pentene.

Among the haloacetaldehydes of formula VII, mention may be made, for example, of trichloroacetaldehyde (chloral), tribromoacetaldehyde (bromal), dichloroacetaldehyde, dibromoacetaldehyde, monochloroacetaldehyde, mono-bromoacetaldehyde and dichlorochloride, dichlorochloride and dichlorochloride.

Among the acid catalysts to be used for the reaction (the Prins reaction) between the unsaturated hydrocarbon of formula VI and the haloacetaldehyde of formula VII, mention may be made, for example, of Lewis acids such as alu-20 chloride. minium, aluminum bromide, boron trifluoride / diethyl ether, zinc chloride, ferric chloride, tin tetrachloride, tin dichloride, tin tetrabromide, titanium tetrachloride, thallium trichloride, bismuth trichloride, tellurium tetrachloride, tellurium dichloride, antimony pentachloride and phosphorus pentoxide; inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, sulfonic acids such as benzenesulfonic acid, o-toluenesulfonic acid,

m-toluenesulfonic acid and p-toluenesulfonic acid and ion exchange resins containing a sulfonyl or carbonyl group. Among these acid catalysts, aluminum chloride, aluminum bromide, zinc chloride, tin tetrachloride, boron trifluoride / diethyl ether, are preferred.

sulfuric acid and phosphoric acid.

The amount of acid catalyst used varies depending on the type of catalyst used, but generally an amount of acid catalyst is used from about 0.5 to about 30 mol% and preferably from about 3 to about 15 mol % calculated relative to the haloacetaldehyde of formula VII. 40 The amount of unsaturated hydrocarbon of formula VI used can be varied within a relatively wide range of about 0.5 to about 6 mol / mol of haloacetaldehyde of formula VII but, in order to effectively consume the haloacetaldehyde of formula VII for the reaction, it is preferred to use the unsaturated hydrocarbon of formula VI in an amount of 1.0 to 4 mol / mol of the haloacetaldehyde of formula VII.

The reaction is generally carried out at a temperature ranging from −20 ° C. to ordinary temperature at atmospheric pressure, but, if desired, the reaction can be carried out under pressure at a temperature higher than ordinary temperature.

The use of a solvent is not particularly critical for this reaction, but it is possible to use a solvent which does not participate in the reaction, for example petroleum ether 55, n-pentane, n -hexane or nitromethane.

In many cases, this Prins reaction gives 1-halo-4-alkene-2-ol as the main reaction product. In these cases, it is necessary to convert this unsaturated alcohol into a l-halo-3-alkene-2-ol by the isomerization of the double co bond. This isomerization can be carried out by heat treatment in the presence or in the absence of a catalyst.

As the isomerization catalyst, at least one substance chosen from transition metals, groups VI-B, VIIB and VIII of the periodic table and 65 compounds of these transition metals is used.

Preferred isomerization catalysts include chromium acetylacetonate [III], molybdenum disulfide, tungsten trioxide, manganese acetylacetonate [III],

7

620192

ruthenium trichloride, cobalt acetylacetonate [II], hexaminecobalt chloride, rhodium acetylacetonate [III], rhodium trichloride, iridium trichloride, Raney nickel, nickel acetylacetonate ], palladium chloride, palladium black, 5% palladium carbon, etc.

The isomerization can be carried out at a temperature between 60 and 250 ° C., although the reaction temperature is varied to a certain extent depending on the type of starting 1-halo-4-alkene-2-ol. When the isomerization catalyst is used, the isomerization temperature can be lowered, and the isomerization rate can be increased by the presence of an isomerization catalyst, then it is compared based on the same temperature isomerization.

The catalyst is used in an amount of 0.001 to 30%

by weight and preferably 0.1 to 10% by weight calculated relative to 1-halo-4-alkene-2-ol.

This isomerization reaction can be carried out continuously or batchwise. In order to advance the isomerization with good selectivity, it is preferable to increase the purity of the starting 1-halo-4-alkene-2-ol and to conduct the reaction in an atmosphere of nitrogen or another inert gas.

Reaction between l-halo-3-alkene-2-ol and orthocarboxylic ester.

The orthocarboxylic ester of formula III above comprises a large number of compounds. In view of the ease of preparation, the availability, the ease of handling and the usefulness of the intermediate compound of formula V above prepared by reaction 1), it is advantageous to use an orthocarboxylic ester of formula III above. above having the following structure:

R4 is selected from a hydrogen atom, alkyl groups having up to 15 carbon atoms, cycloalkyl groups having up to 8 carbon atoms, alkenyl groups having up to 15 carbon atoms, cycloalkenyl groups having up to 8 carbon atoms,

alkynyl groups having up to 15 carbon atoms, aryl groups having up to 8 carbon atoms and aralkyl groups having up to 10 carbon atoms. It is particularly preferred that R4 is a hydrogen atom, a methyl, ethyl, propyl, butyl, cyclohexyl, phenyl or benzyl group.

The three alcohol residues R5 (residues formed when a hydroxyl group is removed from an alcohol) may be the same or different. Among the residues R5, there may be mentioned, for example, alkyl groups having up to 15 carbon atoms, cycloalkyl groups having up to 8 carbon atoms, alkenyl groups having up to 15 carbon atoms, groups cycloalkenyl having up to 8 carbon atoms and hydrocarbon groups containing an atom other than carbon such as nitrogen, phosphorus, sulfur or oxygen or a halogen atom.

Among these hydrocarbon groups, mention may be made, for example, of hydrocarbon groups of the following formulas:

, 7 -CH

10

9

-ch2a0u —ch2 — ch = ç — ch2 — RU

where R6 represents a hydrogen atom or a methyl group, R7 is an alkenyl, alkadienyl or alkynyl group having up to

6 carbon atoms or a benzyl group, R8 is a hydrogen atom, an ethynyl group or a cyano group, R9 is a hydrogen atom, a halogen atom or an alkyl group having up to 5 carbon atoms , R10 is a halogen atom, an alkyl, alkenyl or alkynyl group having up to 6 carbon atoms or a benzyl, thienyl, furylmethyl, phenoxy or phenylthio group, R9 and R10 can be attached to each other at their ends to form a polymethylene chain in which an oxygen or sulfur atom can be found, Q is an oxygen or sulfur atom or a group - CH = CH -, n is an integer having the value 1 or 2, A is an o-, m- or p-phenoxyphenyl group, a phthalimido group, a thiophthalimido group, a di- or tetrahydrophthalimido group or a dialkylmaleimido group, R11 is a phenyl, thienyl or furyl group and W is an atom hydrogen, methyl, alkoxy, cyano or a halogen atom.

Among the preferred examples of the group R5 of the orthocarboxylic ester of formula III above, mention may be made of methyl, ethyl, propyl, butyl, octyl, cyclohexyl, benzyl, prenyl, geranyl, allethronyl, pyrethronyl, 3-phenoxy groups. benzyl, 5-benzyl-3-furylmethyl, tetrahydrophthalimidomethyl and 3-benzylpropargyl.

Among the preferred examples of the orthocarboxylic ester of formula III, mention may be made of 1,1,1-trimethoxyethane (methyl orthoacetate), 1,1,1-triethoxyethane (ethyl orthoacetate), 1,1,1 -tricyclohexyloxyethane, 1,1,1-tri-n-butyloxy-ethane, 1,1,1-triethoxypropane (ethyl orthopropionate), 1,1,1-triethoxybutane, 1,1,1-triethoxypentane , 3-methyl-1,1,1-triethoxybutane, 3,7-dimethyl-1,1,1-triethoxy-octane, 2-phenyl-1,1,1-triethoxyethane, 2- (o- methylphenyl) -1,1,1-triethoxyethane, 2- (m-methylphenyl) -1,1,1-triethoxyethane, 2-cyclohexyl-l, l, l-trimethoxyethane, 1,1-dimethoxy-l- cyclohexyloxyethane, 1,1-dimethoxy-l-pentoxyethane, 3-methyl-l, l, l-triethoxybutene, 1,1-triethoxy-5-heptine, l-benzyloxy-l, l-diethoxyethane, 1 , 1-diethoxy-1-geranyloxyethane, 1,1,1-tribenzyloxyethane, 1,1,1-trioctyloxyethane, 1,1-diethoxy-1-octyloxyethane, 1,1-diethoxy-1-prenyloxyethane, 1,1-diethoxyoctyloxyethane, 1,1-diethoxy-1-prenyloxyethane, 1,1-diethoxy-1-allethronyloxyethane, 1,1-diethoxy-1-pyrethroxyoxyhane, 1,1-diethoxy-1- (3-phenoxybenzyloxy) ethane, 1,1-diethoxy-1- benzyl-3-furylmethyloxy) ethane, l, l-diethoxy-l- (tetra-hydrophthalimidomethyloxy) ethane, l, l-diethoxy-l- (tetra-hydrophthalimidomethyloxy) ethane and l, l-diethoxy-l- ( 3-benzylpropargyloxy) ethane.

In the reaction between the orthocarboxylic ester of formula III and the 1-halo-3-alkene-2-ol of formula II, the presence of an acid catalyst is not particularly critical, but the use of a catalyst acid can promote the speed of reaction a).

Among the acid catalysts to be used for reaction a), there may be mentioned, for example, lower fatty acids such as acetic acid, propionic acid, butyric acid,

isobutyric acid, cyclohexylcarboxylic acid, valeric acid, malonic acid, succinic acid and adipic acid; aromatic carboxylic acids such as benzoic acid and m-chlorobenzoic acid, phenols such as phenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, o-cresol, m- cresol, p-cresol, o-xylenol, p-xylenol, 2,6-dimethylphenol, 2,6-di-t-butylphenol, 2,4,6-tri-sec-butylphenol, 2,4,6-tri-t-butylphenol, 4-methyl-2,6-di-t-butylphenol, 4-methyl-3,5-di-t-butylphenol, hydroquinone, 2,5 -di-t-butylhydroquinone, a-naphthol and ß-naphthol; sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid and boric acid and Lewis acids such as chloride aluminum, zinc chloride, ferric chloride and

5

10

15

20

25

30

35

40

45

50

55

60

65

620192

VS"

O

boron trifluoride. It is preferred to use a fatty acid having from 2 to 6 carbon atoms, a phenol or an aromatic carboxylic acid. The acid catalyst is used in an amount of 0.001 to 20% by weight and preferably 0.01 to 15% by weight calculated relative to the starting 1-halo-3-alkene-2-ol of formula II.

The use of a solvent is not particularly critical for reaction a), but, if desired, solvents which do not take part in the reaction can be used such as n-octane, toluene, l 'o-xylene, m-xylene, p-xylene, di-n-butyl ether and tetralin. When the orthocarboxylic ester of formula III above is used in an amount which represents an excess with respect to the 1-halo-3-alkene-2-ol of formula II, the ester of formula III can also act as solvent . It often happens that the orthocarboxylic ester is broken down to some extent during the reaction.

Thus, even if it is not desired that the orthocarboxylic ester act as a solvent, it is preferred to use the orthocarboxylic ester in an amount of 1.3 to 3 mol / mol of 1-halo-3-alkene-2-ol.

The reaction is carried out with heating, generally at 100-200 ° C and preferably at 120-160 ° C. When the temperature is below 100 ° C, the reaction rate is too low and, when the temperature is above 200 ° C, the formation of by-products is increased. In order to avoid side reactions, it is preferred to remove an alcohol formed as a by-product from the reaction system continuously and rapidly.

According to the boiling point, the NMR spectrum, the IR spectrum and the elemental analysis of the intermediate compound formed according to the above reaction, the intermediate compound is a y-halo-5-unsaturated-carboxylic ester having the formula V above.

The y-halo-8-unsaturated-carboxylic ester of formula V comprises, for example, the compounds illustrated below,

each of these compounds being considered as a new compound not introduced in the literature.

1) Ethyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate

2) methyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate

3) Ethyl 3,3-dimethyl-4,6,6-tribromo-5-hexenoate

4) 3,3-dimethyl-4,6,6-tribromo-5-t-butyl hexenoate

5) Ethyl 2,2,3-trimethyl-4,6,6-trichloro-5-hexenoate

6) 2,3,3-trimethyl-4,6,6-trichloro-5-hexenoate hexenoate

7) Ethyl 2,3,3-trimethyl-4,6,6-tribromo-5-hexenoate

8) 2,3,3-trimethyl-4,6,6-tribromo-5-n-octyl hexenoate

9) ethyl 3-methyl-4,6,6-trichloro-5-hexenoate

10) Benzyl 3-methyl-4,6,6-trichloro-5-hexenoate

11) ethyl 3-methyl-4,6,6-tribromo-5-hexenoate

12) Ethyl 3-methyl-3-ethyl-4,6,6-tribromo-5-hexenoate

13) Cyclohexyl 3-methyl-3-ethyl-4,6,6-tribromo-5-hexenoate

14) Ethyl 3-methyl-3-phenyI-4,6,6-trichloro-5-hexenoate

15) methyl 3-methyl-3-phenyl-4,6,6-trichloro-5-hexenoate

16) Ethyl 3-methyl-3-benzyl-4,6,6-trichloro-5-hexenoate

17) Ethyl 2-cyclohexyl-3,3-dimethyl-4,6,6-trichloro-5-hexenoate

18) Ethyl 3,3-dimethyl-4,6-dichloro-5-hexenoate

19) methyl 3,3-dimethyl-4-chloro-5-hexenoate

20) Benzyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate

21) n-Octyl 3,3-dimethyl-4,6,6-tribromo-5-hexenoate

22) m-phenoxy-benzyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate

23) m-Phenoxybenzyl 3,3-dimethyl-4,6,6-tribromo-5-hexenoate

24) Pyrethronyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate

25) Allethronyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate

26) 5-Benzyl-3-furylmethyl 3,3-dimethyl-4,6,6-tribromo-5-hexenoate

27) 5-Benzyl-3-furylmethyl 3,3-dimethyl-4,6,6-tribromo-5-hexenoate

28) 3,4,5,6-tetrahydrophthalimidomethyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate

29) 5-Phenoxyfurfuryl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate

30) 5-Propargyl-furfuryl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate.

Conversion of a substituted cyclopropanecarboxylic ester

of formula / 'into a substituted cyclopropanecarboxylic ester

of formula I.

If the substituted cyclopropanecarboxylic ester of formula Y prepared as described above has no insecticidal activity or only a very weak insecticidal activity, it is advantageous to convert the ester into an ester having a different alcoholic residue and having this makes a higher insecticidal activity.

This goal can be achieved by reacting the substituted cyclopropanecarboxylic ester of formula with an alcohol of formula:

R130H VIII

in which R13 is an alcohol residue other than R5 as defined above, or a reactive derivative of said alcohol such as a halide (R13X, X = a halogen atom), an arylsulfonate or an alkali metal alcoholate in presence of an appropriate auxiliary product.

Among the alcohol residues R13 of the alcohol of formula VIII above, mention may be made of the same groups as those indicated above with regard to the alcohol residue R5. Among the alcohols of formula VIII which are particularly preferred, are those having an alcohol residue represented by the following general formula:

-CH

10

-ch2a0u -CH2-CH = Ç-CH2R11

w where R6, R7, R8, R9, R10, RH, Q, A, W and n have the meaning indicated above with respect to the alcohol residue R5 of the orthocarboxylic ester.

Among the alcohols of formula VIII, the following may be mentioned, for example: allethrolone, pyrethrolone, o-, m- or p-phenoxybenzyl alcohol, a-cyano-m-phenoxybenzyl alcohol, alcohol 3 -benzylbenzyl, 5-phenoxyfurfuiyl alcohol, 5-propargylfurfuryl alcohol, 5-benzyl-3-fuiyl-methyl alcohol, a-cyano-5-benzyl-3-furylmethyl alcohol, 4-benzyl- 2-butyn-1-ol, 3-phenyl-2-propyn-1-ol and 3,4,5,6-tetrahydrophthalimidomethyl alcohol.

Examples of this reaction are as follows:

1) an ester exchange reaction;

2) a reaction between an acid halide of the substituted cyclopropanecarboxylic acid and the alcohol;

3) a reaction between the substituted cyclopropanecarboxylic acid and the alcohol;

4) a reaction between a salt of the substituted cyclopropanecarboxylic acid and an arylsulfonate (for example a tosylate) of the alcohol.

This step can be applied to the preparation of a substituted cyclopropanecarboxylic ester having an alcohol residue R13 from a cyclopropanecarboxylic ester of formula Y

5

10

15

20

25

30

35

40

45

50

55

60

65

9

620 192

in which the alcohol residue R5 is a lower alkyl group such as a methyl, ethyl, propyl or butyl group.

Substituted cyclopropanecarboxylic esters having an alcohol residue R13 are compounds having excellent insecticidal activity and can be used effectively as insecticides or other agricultural chemical compounds.

Examples of such substituted cyclopropanecarboxylic esters are as follows:

1) 2 ', 2'-dimethyl-3' - (2 ", 2" -dichlorovinyl) 3-phenoxybenzyl cyclopropane-carboxylate

2) 2 ', 2'-dimethyl-3' - (2 ", 2" -dichlorovinyl) 3,4,5,6-tetrahydrophthalimidomethyl cyclopropane-carboxylate

3) 2 ', 2'-dimethyl-3' - (2 ", 2, '- dichlorovinyl) 5-benzyl-3-furylmethyl cyclopropane-carboxylate

4) 2 ', 2'-dimethyl-3' - (2 ", 2" -dichlorovinyl) 3-benzylbenzyl cyclopropane-carboxylate

5) 2 ', 2'-dimethyl-3' - (2 ", 2" -dichlorovinyl) 5-phenoxyfurfuryl cyclopropane-carboxylate

6) 2 ', 2'-dimethyl-3' - (2 ", 2" -dichlorovinyl) 2-allyl-3-methyl-2-cyclopenten-l-on-4-yl cyclopropane-carboxylate

7) 2 ', 2'-dimethyl-3' - (2 ", 2" -dichlorovinyl) 5-propargylfurfuryle cyclopropane-carboxylate

8) 2 ', 2'-dimethyl-3' - (2 ", 2" -dichlorovinyl) a-ethynyl-3-phenoxybenzyl cyclopropane-carboxylate

9) 2 ', 2'-dimethyl-3' - (2 ", 2" -dibromovinyl) 3-phenoxybenzyl cyclopropane-carboxylate

10) 3,4,5,6-tetrahydrophthalimidomethyl 2 ', 2'-dimethyl-3' - (2 ", 2" -dibromovinyl) cyclopropane-carboxylate

11) 2 ', 2'-dimethyl-3' - (2 ", 2" -dibromovinyl) 5-benzyl-3-furylmethyl cyclopropane-carboxylate

12) 2 ', 2'-dimethyl-3' - (2 "-monochlorovinyl) cyclopropane-carboxylate of 3-phenoxybenzyl

13) 1 ', 2', 2'-trimethyl-3 '- (2 ", 2" -dichlorovinyl) 3-phenoxybenzyl cyclopropane-carboxylate

14) 3-phenoxybenzyl 2'-methyl-2'-phenyl-3 '- (2 ", 2" -dichlorovinyl) cyclopropane-carboxylate

15) 2 ', 2'-dimethyl-3'-vinylcyclopropanecarboxylate of 5-benzyl-3-furylmethyl.

The ester exchange reaction between the cyclopropanecarboxylic ester of formula I 'and the alcohol of formula VIII can be carried out using a basic substance such as that used in the process according to claim 1, for example an alcoholate of alkali metal, and removing from the reaction mixture a lower alcohol formed by the reaction.

When an inert solvent such as benzene, toluene, n-octane, n-hexane, etc. is used for this ester exchange reaction, the reaction can be carried out with great regularity.

The cyclopropanecarboxylic acid ester of formula Ia to be used for the reaction is an ester in which the group R5 is a methyl, ethyl, n-propyl, isopropyl, n-butyl or t-butyl group.

When a cyclopropanecarboxylic acid is used as the reactive derivative of the cyclopropanecarboxylic ester of formula l and reacted with an alcohol of formula VIII, the reaction is carried out under anhydrous conditions.

In order to establish anhydrous conditions, the reaction is carried out with heating in the presence of an acid catalyst such as hydrochloric acid or sulfuric acid, and a solvent capable of forming an azeotropic mixture with water such as benzene. or toluene, to remove water from the reaction mixture.

A dehydrating agent such as dicyclohexylcarbodiimide can also be used.

When a cyclopropanecarboxylic acid halide is used as the reactive derivative of the cyclopropanecarboxylic ester of formula I and reacted with an alcohol of formula VIII, if a tertiary amine such as pyridine or triethylamine is used as dehydrohalogena- agent

tion, the desired ester can be obtained under mild reaction conditions.

When a silver, lead or alkali metal salt of a cyclopropanecarboxylic acid is used as the reactive derivative of the cyclopropanecarboxylic ester of formula I and it is reacted with an aryl sulfonate of an alcohol of formula VIII as reactive derivative of the alcohol of formula VIII, the reaction can be efficiently carried out in the presence of an inert solvent such as benzene, acetone, chloroform, ligroin or ether by heating to the boiling point of the solvent or at a lower temperature.

The following examples illustrate the invention without limiting it. In these examples, all parts are by weight.

Example 1:

0.1 part of isobutyric acid was added to a mixture of 10.2 parts of 1,1,1 -trichloro-4-methyl-3-penten-2-ol and 16.2 parts of ethyl orthoacetate , and, in a nitrogen atmosphere, the mixture was stirred for 2 h at 130-145 ° C and then for another 2 h at 145-155 ° C. The alcohol formed as a by-product during the reaction was removed continuously by distillation from the reaction system. When the reaction was complete, the liquid reaction mixture was subjected directly to distillation under reduced pressure to obtain 11.1 parts of an oily fraction boiling at 83-84 ° C / 0.28 mm Hg. The yield was 81% calculated compared to 1,1,1-trichloro-

Starting 4-methyl-3-penten-2-ol. The properties of the product thus obtained were as follows:

IR spectrum (liquid film method):

1610cm-1 (C = C), 1730cm- '(CO).

NMR spectrum (100 MHz) S ^ 's4:

1.08 (s) 6 H, 1.20 (t, J = 7 Hz) 3 H, 2.14 (d, J = 14 Hz) 1 H, 2.42 (d, J = 14 Hz) 1 H , 4.01 (q, J = 7 Hz) 2 H, 4.83 (d, J = 11 Hz) 1 H, 5.95 (d, J = 11 Hz) 1 H.

Elementary analysis:

Calculated: C 43.90 H 5.53%

Found: C 43.77 H 5.47%

From the above properties, the compound thus obtained was identified as being 3,3-dimethyl-4,6,6-trichloro-

Ethyl 5-hexenoate.

2.7 parts of the compound thus obtained were dissolved in 25 parts of dry benzene, 1.9 parts of sodium t-butoxide were added to the solution and the mixture was stirred at room temperature for 1 h. The liquid reaction mixture was poured into ice water and extracted with ether. Ether and benzene were removed from the organic layer by distillation and the residue was distilled under reduced pressure to obtain 2.1 parts of 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl ) -cyclopropanecarboxylate ethyl desired (the yield was 89%).

The properties of the compound thus obtained were as follows:

M.p .: 102-103 ° C / 2.0 mm Hg.

IR spectrum (liquid film method):

1620 cm-1 (C = C), 1730 cm "1 (CO).

NMR spectrum (100 MHz) ô ^ 's4:

1.15 (s), 1.20 (t, J = 7 Hz), 1.22 (s) 9H; 1.47 (d, J = 5 Hz) 1H; 2.10 (dd, J = 5.8 Hz) 1H, 4.03 (q, J = 7 Hz) 2H; 5.52 (d, J = 8 Hz) 1H.

Elementary analysis:

Calculated: C 50.65 H 5.95%

Found: C 50.51 H 6.24%

Mass spectrum, m / e (M + •): 236, 238, 240.

5

10

15

20

25

30

35

40

45

50

55

60

65

620192

10

Example 2:

The procedure was as in Example 1 using 0.4 parts of phenol in place of isobutyric acid to obtain 9.7 parts of an oily fraction boiling at 83-84 ° C / 0.28 mm of Hg .

0.5 part of the oily substance thus obtained was dissolved (which was considered to be ethyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate) in 10 parts of dry tetrahydrofuran and 0.4 part powdered potassium hydroxide was added to the solution and the mixture was stirred at 45-50 ° C for 1.5 h.

The liquid reaction mixture was filtered directly using celite to remove the solids. The tetrahydrofuran was removed from the filtrate by distillation. When the oily substance obtained was analyzed by gas chromatography, it was found that the desired ethyl 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) -cyclopropanecarboxylate had formed with a yield of around 20%.

Example 3:

0.5 parts of ethyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate was added to 5 parts of 1,5-diazabicyclo- [5,4,0] -undecene-5 ( DBU) and the mixture was stirred at 45-50 ° C for 1 h. The liquid reaction mixture was sufficiently stirred with about 50 parts of water and the lower organic layer was analyzed by gas chromatography. It was found that the desired 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) cyclopropane-carboxylate was formed with a yield of about 15%.

When these crystals were recrystallized fractionally from n-hexane, they could be divided into the cis-isomer which melted at 88-89 ° C and the trans-isomer which melted at 94-96 ° C. The results of the NMR spectrum analysis (60 MHz) of the transparent isomer were as follows:

5TMS4:! '18 (s) 3H '1> 3 ° 3H' 1.53 (from J == 5> 5 Hz) 1H>

2.20 (dd, J = 8 Hz & 5.5 Hz) 1 H, 5.58 (d, J = 8 Hz) 1 H.

Example 4:

1.1 parts of potassium hydroxide were dissolved in 30 parts of anhydrous methanol and 2.7 parts of ethyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate were added to the solution. prepared as described in Example 2. The mixture was stirred for 2 h under reflux of methanol. The liquid reaction mixture was diluted with about 100 parts of diethyl ether and washed with about 25 parts of water. The aqueous layer was extracted three times with diethyl ether. The diethyl ether extract obtained was subjected to distillation to separate therefrom substances with a low boiling point and to isolate 1.0 part (the yield was 45%) of 2,2-dimethyl-3- (2 ' , 2'-dichloro-vinyl) methyl cyclopropanecarboxylate having the properties described below.

The eis: trans ratio of the product determined by gas chromatography was 35: 65.

M.p. 67-68 ° C / 0.2 mm Hg.

NMR spectrum (60 MHz) 5 ^ 4:

1.12-1.25 (m) 6H; 1.42-2.25 (m) 2H; 3.60 (s) 3H; 5.57 (d, J = 8.5 Hz), 6.23 (d, J = 8.5 Hz) 1H.

When the above aqueous layer was neutralized with hydrochloric acid and extracted with diethyl ether, 0.8 parts of 2,2-dimethyl-3- (2 ', 2'-dichloro-vinyl) cyclopropanecarboxylic. The yield was 38%. When the product was analyzed as in Example 4, it was found that the eis: trans ratio was 21: 79.

Example 5:

0.4 parts of metallic sodium were dissolved in 30 parts of anhydrous methanol and 2.7 parts of ethyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate were added to the solution.

The mixture was stirred for 2 h under reflux of methanol. The liquid reaction mixture was cooled with ice water and neutralized with methanol saturated with HCl. The precipitated solids were filtered off and the filtrate was concentrated until the volume was reduced to one tenth. The concentrate was diluted with diethyl ether, washed with water and then dried. The solvent was then distilled off and the residue was subjected to distillation under reduced pressure to obtain 2.0 parts of methyl 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) cyclopropanecarboxylate which boiled at 68-70 ° C / 0.2 mm Hg. The yield was 90%. The eis: trans ratio of the product determined by gas chromatography was 22: 78.

Example 6:

0.4 parts of metallic sodium were dissolved in 20 parts of anhydrous ethanol and 2.7 parts of ethyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate were added to the solution. The mixture was stirred for 2 h under reflux of ethanol. The liquid reaction mixture was diluted with about 50 parts of diethyl ether and neutralized with dried HCl gas. The precipitated sodium chloride crystals were filtered off and the low boiling substances were distilled from the filtrate. The residue was then subjected to distillation under reduced pressure to obtain 2.1 parts of ethyl 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) cyclopropanecarboxylate boiling at 72-73 ° C / 0, 3 mm Hg. The yield was 87%. The properties of the product were consistent with those of the ethyl 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) cyclopropanecarboxylate described in Example 1.

Example 7:

0.03 part of isobutyric acid was added to a mixture of 4.1 parts of 1,1,1-trichloro-4-methyl-3-penten-2-ol and 7.0 parts of ethyl orthopropionate and the mixture was stirred at 130-145 ° C for 4 h in a nitrogen atmosphere. The ethyl alcohol formed during the reaction was removed by continuous distillation from the reaction mixture. When the reaction was complete, the liquid reaction mixture was subjected directly to distillation under reduced pressure to obtain 4.9 parts of a fraction of an oily substance which boiled at 92-99 ° C / 0.25 mm Hg From gas chromatography of the product, it was found to be composed of two bodies.

Therefore, the product was subjected to column chromatography on Silicagel using benzene as the developing liquid and 1.6 parts of a compound having the following properties were obtained:

M.p. 104-106 ° C / 0.4 mm Hg.

IR spectrum (liquid film method):

1610 cm- '(C = C), 1730 cm "' (CO).

NMR spectrum (100 MHz) 8 ^ 4;

1.20 (t, J = 7 Hz), 0.9-1.3, 12H; 2.4-2.7 (m) 1H; 4.01 (q, J = 7 Hz), 4.03 (q, J = 7 Hz) 2H; 4.63 (d, J = 11 Hz), 4.78 (d, J = 11 Hz) 1H; 5.96 (d, J = 11 Hz), 5.97 (d, J = 11 Hz) 1H.

Elementary analysis:

Calculated: C 45.94 H 5.96%

Found: C 46.20 H 6.02%

Given the above properties, it was concluded that the above product was ethyl 2,3,3-trimethyl-4,6,6-trichloro-5-hexenoate.

1.0 part of this compound was dissolved in 5 parts of dry benzene and 0.67 part of sodium t-butoxide was added to the solution and the mixture was stirred under reflux of benzene for 30 min. The liquid reaction mixture was poured into ice water and extracted with diethyl ether and then

5

10

15

20

25

30

35

40

45

50

55

60

65

11

620 192

distilled ether and benzene from the organic layer to obtain 0.72 part of 1,2,2-trimethyl-3- (2 ', 2'-dichlorovinyl) -cyclopropanecarboxylate in the form of a product oily. The yield was 82%. The results of the NMR spectrum analysis (60 MHz) were as follows:

ôtms4: i'04 (s) 'U3 (s)' >> 18 (s). !> 23 (t. J = 7 Hz) 12H;

2.25 (d, J = 8 Hz) 1H; 4.08 (q, J = 7 Hz) 2H; 5.57 (d, J = 8 Hz) 1H.

Example 8:

By the ester exchange of the intermediate compound prepared in Example 1 (ethyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate), the 5-benzyl- ester was obtained. 3-furylmethyl IX,

the m-phenoxybenzyl ester X and the allethronyl ester XI of 3,3-dimethyl-4,6,6-trichloro-5-hexenoic acid. The ester thus obtained was dissolved in an amount which is shown in Table I in 30 parts of dry benzene and the indicated amount of sodium t-butoxide or potassium t-butoxide was added to the solution and stirred the mixture for 20 min under a reflux of benzene. The liquid reaction mixture was poured into ice water and quickly extracted with diethyl ether. The ether and benzene were distilled off from the organic layer and the residue was subjected to column chromatography to obtain the corresponding 2,2-dimethyl-3- (2 ', 2'-) acid ester. dichlorovinyl) cyclopropanecarboxylic, that is to say the 5-benzyl-3-furylmethyl ester IX ', the m-phenoxybenzyl ester X' or the allethronyl ester XI '.

Table I

Starting compound Basic substance Product

[IX] 3.8 parts t-BuONa, 1.9 parts [IX '] m.p. = 55 ° C

[X] 3.9 parts t-BuOK, 2.2 parts [X '] no = 1.5615

[XI] 3.4 parts t-BuOK, 2.2 parts [XI '] n ^ ° = 1,5142

Example 9:

0.3 parts of isobutyric acid was added to a mixture of 33.7 parts of 1,1,1-tribromo-4-methyl-3-penten-2-ol and 48.7 parts of ethyl orthoacetate ; in a nitrogen atmosphere, the mixture was stirred for 2 h at 130-145 ° C, then for another 2 h at 145-155 ° C. The ethyl alcohol formed as a by-product was removed by continuous distillation of the reaction of the reaction mixture during the reaction. The liquid reaction mixture was subjected directly to distillation under reduced pressure to obtain a fraction of an oily substance having a boiling point of 125-127 ° C / 0.25 mm Hg. Thus, 28, 3 parts of ethyl 3,3-dimethyl-4,6,6-tribromo-5-hexenoate, The yield was 70% calculated with respect to 1.1, l-tribromo-4-methyl-3-penten- 2-ol. The physical properties of the product were as follows:

IR spectrum (liquid film method):

1600cm- '(C = C), 1730cm-' (CO).

NMR spectrum (60 MHz) 8 ^ 4:

1.12 (s) 6H, 1.22 (t, J = 7 Hz) 3H, 2.17 (d, J = 15 Hz) 1H, 2.49 (d, J = 15 Hz) 1H, 4.08 (q, J = 7 Hz) 2H, 4.93 (d, J = 11 Hz) 1H, 6.66 (d, J = 11 Hz) 1H.

4.1 parts of the ethyl 3,3-dimethyl-4,6,6-tribromo-5-hexenoate thus obtained were dissolved in 35 parts of dry benzene, and 1.9 parts of t- were added to the solution. sodium butylate,

and the mixture was stirred for 1 h under reflux of benzene. The liquid reaction mixture was poured into ice water and extracted with diethyl ether, then the ether and benzene were distilled from the organic layer. The residue was subjected to distillation under reduced pressure to obtain 3.2 parts of ethyl 2,2-dimethyl-3- (2 ', 2'-dibromovinyl) cyclopropane-carboxylate boiling at 92-94 ° C / 0 , 5 mm Hg. The yield was 98%.

The physical properties of the compound thus obtained were as follows:

IR spectrum (liquid film method):

1600cm- '(C = C), 1730 cm-' (CO).

NMR spectrum (100 MHz) 8 ^ 4:

1.19 (s), 1.23 (t, J = 7 Hz), 1.26 (s) 9H; 1.53 (d, J = 5 Hz) 1H; 2.08 (dd, J = 5 Hz & 8 Hz) 1 H, 4.03 (q, J = 7 Hz) 2H; 6.04 (d, J = 8 Hz) 1H.

Example 10:

The procedure was as in Example 1 using 1,1-dichloro-4-methyl-3-penten-2-ol in place of 1,1,1-trichloro-4-methyl-3-penten-2 -ol to prepare ethyl 3,3-dimethyl-4,6-dichloro-5-hexenoate. The ester thus obtained was then treated with sodium t-butoxide under a reflux of benzene to prepare ethyl 2,2-dimethyl-3- (2'-chlorovinyl) cyclopropane-carboxylate. The structure of the ester was confirmed by analysis of the IR spectrum and the NMR spectrum.

Example 11:

The 1,1,1-tribromo-4-methyl-3-hepten-2-ol was used instead of the 1,1,1-tribromo-4-methyl-3-penten-2-ol and the Ethyl 3-methyl-3-propyl-4,6,6-tribromo-5-hexenoate as described in Example 9. The ester was treated with sodium t-butoxide under benzene reflux to prepare ethyl 2-methyl-2-propyl-3- (2 ', 2'-dibromovinyl) cyclopropane-carboxylate. The structure of the ester was confirmed by NMR spectrum analysis.

The preparation of allyl type alcohols of general formula II above to be used for the implementation of the present process is now illustrated by the following reference examples in which all the parts are by weight.

Reference example 1:

33 parts of 1,1,1-trichloro-4-methyl-4-penten-2-ol (having a purity greater than 98%) were stirred at 140-150 ° C in a nitrogen atmosphere for a period of determined time and, when the product obtained by gas chromatography was analyzed, the product obtained by gas chromatography was found, it was found that the 1,1,1-trichloro-4-methyl-3-penten-2-ol had formed with the conversion and selectivity indicated in Table II below.

Table II

Reaction time

Conversion

Selectivity

(h)

(%)

(%)

19

76

95

24

82

94

30

86

94

34

86

94

The product obtained was distilled under reduced pressure while carrying out the treatment for 34 h to obtain a fraction of a solid substance boiling at 105-120 ° C / 18 mm Hg,

and the solid substance thus isolated was recrystallized from n-hexane to isolate the pure l, l, l-trichloro-4-methyl-3-penten-2-ol, the properties of which were as follows:

P.f. 83 ° C.

IR spectrum (KBr disk):

1670 cm -1 (C = O), 3270 cm ~ • (OH).

NMR spectrum (60 MHz) 8 ^ 4:

1.78 (s) 6H, 2.63 (bs) 1H, 4.60 (d, J = 9 Hz) 1H, 5.29 (bd, J = 9 Hz) 1H.

5

10

15

20

25

30

35

40

45

50

55

60

65

620192

12

Elementary analysis:

Calculated: C 35.41 H 4.46%

Found: C 35.56 H 4.47%

Reference example 2:

1 part of palladium black was added to 100 parts of 1,1,1-trichloro-4-methyl-4-penten-2-ol (having a purity greater than 98%) and the mixture was stirred for 18 h at 140-150 ° C in a nitrogen atmosphere. After analysis by gas chromatography of the product, it was found that the isomerization to the desired 1,1,1-trichloro-4-methyl-3-penten-2-ol had taken place with a conversion of 83% and a 94% selectivity. The reaction mixture obtained was diluted with ether, washed with water and filtered to remove the catalyst. The etheric layer was dried with magnesium sulphate and subjected to distillation under reduced pressure to isolate 90 parts of a fraction of a solid substance boiling at 110-115 ° C / 20 mm Hg. recrystallized the solid

from a hexane to isolate pure 1,1,1-trichloro-4-methyl-3-penten-2-ol.

5 Reference examples 3 to 18 and comparative example 1:

At 2 parts of 1,1,1-trichloro-4-methyl-4-penten-2-ol, at least one substance selected from the transition metals of groups VIB, VIIB and VIIIB of the periodic table and compounds was added. of these transition metals in an amount of 10% by weight calculated relative to the starting l, l, l-trichloro-4-methyl-4-penten-2-ol, and the mixture was stirred at 140-150 ° C for 4 h. The reaction product was analyzed by gas chromatography to examine the conversion and selectivity of the desired 1,1,1-trichloro-4-methyl-3-penten-2-ol. The results are shown in Table III. By way of comparison, the isomerization of the 1,1,1-trichloro-4-methyl-4-penten-2-ol was conducted under the same conditions, but without using a catalyst (Comparative Example 1).

Table III

Selectivity of l, l, l-trichloro-4-

Catalyst

Conversion (%)

methyl-3-penten-2-ol example not added

about 30

about 90

comparison 1

example of acetylacetonate

75

85

reference 3

chromium (III)

example of disulfide

75

80

reference 4

molybdenum

example of trioxide

45

95

reference 5

tungsten

example of acetylacetonate

60

90

reference 6

manganese (III)

example of trichloride

75

60

reference 7

ruthenium

example of acetylacetonate

80

85

reference 8

cobalt (II)

chloride example

80

95

reference 9

hexaminecobalt

example of acetylacetonate

80

90

reference 10

rhodium (III)

example of trichloride

45

90

reference 11

rhodium

example of trichloride

70

95

reference 12

iridium

Raney nickel example

65

85

reference 13

example of acetylacetonate

80

80

reference 14

nickel (II)

example of palladium chloride

80

85

reference 15

example of palladium black

80

95

reference 16

example of palladium oxide

80

95

reference 17

example of a 1: 1 mixture of acetyl-

80

80

reference 18

cobalt (II) acetonate and nickel (II) acetylacetonate

Reference example 19:

A mixture of 281 parts of tribromoacetaldehyde, 168 parts of isobutene and 150 parts of ether was cooled.

65 petroleum to -20 to -5 ° C, and 13 parts of anhydrous aluminum chloride were added to the mixture in portions, in batches. The mixture was stirred at the above temperature for 5 h. As the reaction continued, crystals

13

620192

were precipitated from the reaction mixture. When the reaction was complete, diethyl ether was added to the reaction mixture to form a homogeneous solution. The solution was then stirred at room temperature for 30 min and 200 parts of water was added to the reaction mixture. The organic layer was isolated, low boiling substances were distilled off and the residue was subjected to distillation under reduced pressure to obtain 287 parts of 1,1,1-tribromo-4-methyl-4 -pentén-2-ol.

The yield was 85%.

IR spectrum (KBr disk):

1645 cm "1 (C = C), 3500 cm" 1 (OH).

NMR spectrum (60 MHz) 8 ^ 4:

1.82 (s) 3H; 2.03-3.05 (m) 2H; 3.87-4.10 (m) 1H; 4.88 (s) 2H.

50 parts of the 1,1,1-tribromo-4-methyl-4-penten-2-ol thus obtained (having a purity greater than 98%) were stirred

at 130-135 ° C for 5 h in a nitrogen atmosphere.

When the product was analyzed by gas chromatography, it was found that 1,1,1-tribromo-4-methyl-3-penten-2-ol had formed at a conversion of 88% and a selectivity of 97 %. The reaction product was dissolved in diethyl ether and the solution was treated with active carbon to discolor it. The diethyl ether was then distilled off and the residual solid was recrystallized from petroleum ether to obtain 38 parts of l, l, l-tribromo-4-methyl-3-penten-2-ol which melted at 81.5-82 ° C.

M.p. 120-122 ° C / 1 mm Hg.

IR spectrum (KBr disk):

1670 cm - '(C = C), 3310 cm-1 (OH).

NMR spectrum (60 MHz) 5 ^ 4:

1.80 (s) 6H, 2.71 (d, J = 6 Hz) 1H, 4.38-4.68 (m) 1H, 5.30 (bd, J = 8 Hz) 1H.

R

Claims (15)

620 192 1-bromo-1,1-dichloro-4-methyl-3-penten-2-ol, 1,1 -dichloro-4-methyl-3-penten-2-ol, 1,1 -dibromo-4-methyl- 3-penten-2-ol, 1,1,1 -trichloro-4-methyl-3-hepten-2-ol, 1,1,1 -tribromo-4-methyl-3-hepten-2-ol, 1, 1-dichloro-4-methyl-3-hepten-2-ol, 1,1 -dibromo-4-methyl-3-hepten-2-ol, 1,1,1 -trichloro-4,6,6-trimethyl- 3-hepten-2-ol, 1,1,1-tribromo-4,6,6-trimethyl-3-hepten-2-ol, 1,1,1 -trichloro-4-ethyl-3-hexen-2- ol, 1,1,1-tribromo-4-ethyl-3-hexen-2-ol, 1,1,1 -trichloro-4-methyl-3-hexen-2-ol, 1,1,1 -tribromo- 4-methyl-3-hexen-2-ol, 1,1,1-trichloro-3-hepten-2-ol, and 1,1,1-tribromo-3-hepten-2-ol. 1-chloro-1,1 -dibromo-4-methyl-3-penten-2-ol, 1,1,1-trichloro-4-methyl-3-penten-2-ol, 1,1,1-tribromo-4-methyl-3-penten-2-ol, "1) a 1-halo-3-alkene-2-ol is reacted with the following general formula: R1 OH l- l y K / \ VS II not CXYZ 50 in which R1, R2, R3, Y and Z have the above meaning and X is a halogen atom chosen from F, Cl, Br and I, with an orthocarboxylic ester of the following general formula: R4-CH2-C (OR5) 3 III R ' 55 in which R4 and R5 have the above meaning and the three of the groups R5 are identical or different to produce an ester of γ-halo-6-unsaturated carboxylic acid of the following general formula: 60 R1 R3 He / v - C - C - CH - C CH X ^ \ 5 n cooR3 in which R1, R2, R3, R4, R5, X, Y and Z have the above meaning, and 1. Process for the preparation of substituted cyclopropanecarboxylic esters of general formula Y as follows: R \ I y R ' .CC V 'H = R- 2) treating said ester thus obtained with a basic substance. 2. Method according to claim 1, characterized in that the y-halo-S-unsaturated-carboxylic esters of general formula V are chosen from the following: 2 I I R - C - C I I CH X v CH VS R4 COOR- in which R1, R2, R3, R4, R5, Y and Z have the above meaning and X means halogen, with a basic substance. 2 3 620192 3. Method according to claim 1, characterized in that the product obtained is subjected to a trans-esterification reaction with an alcohol of formula R13OH in which R13 represents an alcohol residue different from R5, or with a reactive derivative of said alcohol, in order to replace the remainder of alcohol R5 with the remainder of alcohol R13. Ethyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate, methyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate, 3,3-dimethyl-4,6 , Ethyl 6-tribromo-5-hexenoate, t-butyl 3,3-dimethyl-4,6,6-tribromo-5-hexenoate, 2,3,3-trimethyl-4,6,6-trichloro- Ethyl 5-hexenoate, 2,3,3-trimethyl-4,6,6-trichloro-5-n-propyl hexenoate, 2,3,3-trimethyl-4,6,6-tribomo-5-hexenoate ethyl, 2,3,3-trimethyl-4,6,6-tribromo-5-n-octyl hexenoate, 3-methyl-4,6,6-trichloro-5-hexenoate, 3-methyl Benzyl-4,6,6-trichloro-5-hexenoate, ethyl 3-methyl-4,6,6-tribromo-5-hexenoate, 3-methyl-3-ethyl-4,6,6-tribromo- Ethyl 5-hexenoate, 3-methyl-3-ethyl-4,6,6-tribromo-5-cyclohexyl hexenoate, 3-methyl-3-phenyl-4,6,6-trichloro-5-hexenoate ethyl, 3-methyl-3-phenyl-4,6,6-trichloro-5-hexenoate, ethyl 3-methyl-3-benzyl-4,6,6-trichloro-5-hexenoate, 2-cyclohexyl -3,3-dimethyl-4,6,6-trichloro-5-ethyl hexenoate, 3,3-dimethyl-4,6-dichloro-5-ethyl hexenoate, 3,3-dimethyl-4-chloro -5-hexenoate d e methyl, benzyl 3,3-dimethyl-4,6,6-trichloro-5-hexenoate, and n-octyl 3,3-dimethyl-4,6,6-tribromo-5-hexenoate, 3,3- dimethyl-4,6,6-trichloro-5-hexenoate of m-phenoxybenzyl, 3,3-dimethyl-4,6,6-tribromo-5-hexenoate of m-phenoxybenzyl, 3-3-dimethyl-4,6, Pyrethronyl 6-trichloro-5-hexenoate, allethronile 3,3-dimethyl-4,6,6-trichloro-5-hexenoate, 5-3,3-dimethyl-4,6,6-trichloro-5-hexenoate -benzyl-3-furylmethyl, 3,3-dimethyl-4,6,6-trichloro-5-hexenoate of 5-benzyl-3-furylmethyl, 3,3-dimethyl-4,6,6-trichloro-5-hexenoate of 3,4,5,6-tetrahydrophthalimidomethyl, 3,3-dimethyl-4,6,6-trichloro-5-hexenoate of 5-phenoxyfurfuryl and 3,3-dimethyl-4,6,6-trichloro-5-hexenoate of 5-propargylfurfuryle. 4. Method according to claim 3, characterized in that R13 is a group represented by one of the following formulas: R 5. Method according to claim 3, characterized in that The reactive alcohol derivative of formula R13OH is a halide, an arylsulfonate or an alkali metal alcoholate of said alcohol. \ 5 COOR in which R1, R2, R3 and R4, identical or different, each represent a hydrogen atom or a hydrocarbon group, R1 and R2 or R1 and R3 can be linked to form a nucleus together with the carbon atoms to which they are attached , R5 is an alcohol residue and Y and Z, identical or different, each represent a hydrogen atom or a halogen atom, characterized in that an γ-halo-5-unsaturated-carboxylic ester is treated with the following general formula V: R R- 6. Process for the preparation of substituted cyclopropanecarboxylic esters of general formula above, characterized in that 7. Method according to claim 6, characterized in that in the l-halo-3-alkene-2-ol of formula II, R1, R2 and R3, identical or different, each represent a hydrogen atom, an alkyl group having up to 15 carbon atoms, a cycloalkyl group having up to 8 carbon atoms, an alkenyl group having up to 15 carbon atoms, a cycloalkenyl group having up to 8 carbon atoms, an alkynyl group having up to 15 carbon atoms, a group aryl having up to 8 carbon atoms or an aralkyl group having up to 10 carbon atoms, R1 and R2 or R1 and R3 may be attached together to form a ring together with the carbon atom to which they are attached, X is a halogen atom chosen from F, Cl, Br and I and Y and Z represent a hydrogen atom or a halogen atom chosen from F, Cl, Br and I. 7 -CH2A or -CH2-CH = C-CH2-w ■ Ri i Where R6 is a hydrogen atom or a methyl group, R7 is an alkenyl, alkadienyl or alkynyl group having up to 6 carbon atoms or a benzyl group, R8 is a hydrogen atom, an ethynyl group or a group cyano, R9 is a hydrogen atom, a halogen atom or an alkyl group having up to 5 carbon atoms, R10 is a halogen atom, an alkyl, alkenyl or alkynyl group having up to 6 atoms carbon or a benzyl, thienyl, furylmethyl, phenoxy or phenylthio group, R9 and R1 "can be linked together at their terminal ends to form a polymethylene chain in which an oxygen or sulfur atom can be contained, Q is a oxygen or sulfur atom or a group - CH = CH—, n is an integer having the value 1 or 2, A is an o-, m- or p-phenoxyphenyl group, a phthalimido, thiophthalimido, di- or tetrahydrophthalimido or dialkylmaleimido, R11 is a phenyl group, a thienyl or furyl group and W is an hydrogen tome, methyl group, alkoxy group, cyano group or halogen atom. 8. Method according to claim 6, characterized in that the l-halo-3-alkene-2-ol of general formula II is chosen from the following: 9. Method according to claim 6, characterized in that the l-halo-3-alkene-2-ol of general formula II is 1,1,1-trichloro-4-methyl-3-penten-2-ol. 10. Method according to claim 6, characterized in that the l-halo-3-alkene-2-ol of general formula II is 1,1,1-tri-bromo-4-methyl-3-penten-2- ol. 11. Method according to claim 6, characterized in that the orthocarboxylic ester of general formula III is an ester of orthocarboxylic acid where R4 is a hydrogen atom, an alkyl group having up to 15 carbon atoms, a cycloalkyl group having up to 8 carbon atoms, an alkenyl group having up to 15 carbon atoms, a cycloalkenyl group having up to 8 carbon atoms, a group alkynyl having up to 15 carbon atoms, an aryl group having up to 8 carbon atoms or an aralkyl group having up to 10 carbon atoms, and R5 is an alkyl group having up to 15 carbon atoms, a cycloalkyl group having up to 8 carbon atoms, an alkenyl group having up to 15 carbon atoms, a cycloalkenyl group having up to 8 carbon atoms, an aralkyl group having up to 10 carbon atoms, or a group hydrocarbon containing an atom other than carbon chosen from nitrogen, phosphorus, sulfur and oxygen or a halogen atom, two or three of the R5 groups being identical or different. 12. Method according to claim 6, characterized in that the reaction of l-halo-3-alkene-2-ol with the orthocarboxylic ester is carried out in the presence of an acid catalyst. 13. Method according to claim 6, characterized in that one conducts the reaction of l-halo-3-alkene-2-ol with the orthocarboxylic ester in the presence of an acid catalyst, said acid catalyst being chosen from acids lower fats, aromatic carboxylic acids, phenols, sulfonic acids, mineral acids and Lewis acids. 14. Method according to claim 6, characterized in that the reaction is carried out between the l-halo-3-alkene-2-ol and the orthocarboxylic acid ester in step 1) at a temperature of 100 to 200 ° C. 15. The method of claim 6, characterized in that the basic substance used in step 2) is chosen from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, organic bases containing nitrogen, organolithic compounds, alkali metal hydrides, alkali metal amides and alkali metals.