Process for preparation of substituted cyclopropane carboxylic acids and esters thereof and intermediates of said acids and esters

Claim 2

A process for the preparation of a substituted cyclopropane-carboxylic ester of the formula ##STR17## wherein R 1 , R 2 , R 3 and R 4 , which may be the same or different, each represents 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, an aryl group having up to 8 carbon atoms or am aralkyl group having up to 10 carbon atoms or R 1 and R 2 or R 1 and R 3 together with the carbon atoms to which they are attached form a ring; R 5 represents 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 hydrocarbon group containing a hetero atom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen; and Y and Z, which may be the same or different, each represents a hydrogen atom or a halogen atom selected from the group consisting of F, Cl, Br and I, which process comprises (i) reacting at a temperature of from 100° C to 200° C, a 1-halogen-3-alkene-2-ol of the formula ##STR18## wherein R 1 , R 2 , R 3 , Y and Z are as defined above, and X is a halogen atom selected from the group consisting of F, Cl, Br and I, with an ortho-carboxylic ester of the formula R.sup.4 --CH.sub.2 --C(OR.sup.5).sub.3 III wherein R 4 and R 5 are as defined above, the three groups R 5 being the same or different, to produce a γ-halogeno-δ-unsaturated-carboxylic acid ester of the formula ##STR19## wherein R 1 , R 2 , R 3 , R 4 , R 5 , X, Y and Z are as defined above, and (ii) treating said compound of formula V with a basic substance at a temperature of from about -80° C to about 100° C to produce said compound of formula I'.

Claim 3

A process according to claim 1 wherein the 1-halogeno-3-alkene-2-ol of formula [II] is selected from the group consisting of 1,1,1-trichloro-4-methyl-3-penten-2-ol, 1,1,1-tribromo-4-methyl-3-penten-2-ol, 1-chloro-1,1-dibromo-4-methyl-3-penten-2-ol, 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,

Claim 4

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.

Claim 5

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.

Claim 6

A process according to claim 1 wherein the 1-halogeno-3-alkene-2-ol of formula [II] is 1,1,1-trichloro-4-methyl-3-penten-2-ol.

Claim 7

A process according to claim 1 wherein the 1-halogeno-3-alkene-2-ol of general [II] is 1,1,1-tribromo-4-methyl-3-penten-2-ol.

Claim 8

A process according to claim 1 wherein the 1-halogeno-3-alkene-2-ol of formula II is prepared by reacting an unsaturated compound of the formula ##STR20## wherein R 1 , R 2 and R 3 are as defined in claim 1 with a halogenoacetaldehyde of the formula CXYZ.CHO Vii wherein X, Y and Z are as defined in claim 34, in the presence of an acid catalyst to produce a 1-halogeno-4-alkene-2-ol, and heating said last-mentioned compound at a temperature of from 60° C to 250° C to produce the isomeric compound of formula II.

Claim 9

A process according to claim 5 wherein the unsaturated compound of formula VI is selected from the group consisting of propene, isobutene, 2-methyl-1-butene diisobutene, 1-pentene, 2-ethyl-1-butene and 2-methyl-1-pentene and the halogenoacetaldehyde of formula VII is selected from the group consisting of trichloroacetaldehyde, tribromoacetaldehyde, dichloroacetaldehyde, dibromoacetaldehyde, monochloroacetaldehyde dichlorobromoacetaldehyde, dibromochloroacetaldehyde and monobromoacetaldehyde.

Claim 10

A process according to claim 5 wherein the 1-halogeno-3-alkene-2ol of formula II is 1,1,1-trichloro-4-methyl-3-penten-2-ol, the unsaturated compound of formula VI is isobutene, the halogenoacetaldehyde of formula VII is trichloroacetaldehyde and the 1-halogeno-4-alkene-2-ol is 1,1,1-trichloro-4-methyl-4-penten-2-ol.

Claim 11

A process according to claim 5 wherein the 1-halogeno-3-alkene-2-ol of formula II is 1,1,1-tribromo-4-methyl-3-penten-2-ol, the unsaturated compound of formula VI is isobutene, the halogeno acetaldehyde of formula VII is tribromoacetaldehyde and the 1-halogeno-4-alkene-2-ol is 1,1,1-tribromo-4-methyl-4-penten-2-ol.

Claim 12

A process according to claim 1, wherein the reaction of the 1-halogeno-3-alkene-2-ol with the orthocarboxylic ester is carried out in the presence of an acid catalyst.

Claim 13

A process according to claim 9, wherein said acid catalyst is selected from the group consisting of a lower fatty acid, an aromatic carboxylic acid, a phenol, a sulfonic acid, a mineral acid and a Lewis acid.

Claim 14

A process according to claim 1 wherein said basic substance is selected from the group consisting of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal alcoholate, a nitrogen-containing organic base, an organic lithium compound, an alkali metal hydride, an alkali metal amide and an alkali metal.

Claim 15

A process for the preparation of a substituted cyclopropane-carboxylic ester of the formula ##STR21## wherein R 1 , R 2 , R 3 and R 4 , which may be the same or different, each represents 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, an aryl group having up to 8 carbon atoms or an aralkyl group having up to 10 carbon atoms or R 1 and R 2 or R 1 and R 3 together with the carbon atoms to which they are attached form a ring; R 13 is a group of the formula ##STR22## wherein R 6 is a hydrogen atom or a methyl group; R 7 is an alkenyl, alkadienyl or alkynyl group having up to 6 carbon atoms or a benzyl group; R 8 is a hydrogen atom, an ethynyl group or a cyano group; R 9 is a hydrogen atom, a halogen atom or an alkyl group having up to 5 carbon atoms; R 10 is a halogen atom, an alkyl, alkenyl or alkynyl group having up to 6 carbon atoms, or a benzyl, thenyl, furylmethyl, phenoxy or phenylthio group, or R 9 and R 10 together form a polymethylene chain or such a chain interrupted by an oxygen or sulfur atom; Q is an oxygen or sulfur atom or a group --CH═CH--; n is an integer of 1 or 2; A is an o-, m- or p-phenoxyphenyl group, a phthalimido group, a thiophthalimido group, a di- or tetra-hydrophthalimido group or a dialkylmaleimido group; R 11 is a phenyl group, a thienyl group or a furyl group; and W is a hydrogen atom, a methyl group, an alkoxy group, a cyano group or a halogen atom; and Y and Z, which may be the same or different, each represents a hydrogen atom or a halogen atom selected from the group consisting of F, Cl, Br and I, which process comprises (i) reacting at a temperature of from 100° C to 200° C, a 1-halogeno-3-alkene-2-ol of the formula ##STR23## wherein R 1 , R 2 , R 3 , Y and Z are as defined above, and X is a halogen atom selected from the group consisting of F, Cl, Br and I, with an ortho-carboxylic ester represented by the formula R.sup.4 --CH.sub.2 --C(OR.sup.5).sub.3 III wherein R 4 is as defined above and R 5 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 hydrocarbon group containing a hetero atom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen, the three groups R 5 being the same or different, to produce a γ-halogeno-δ-unsaturated-carboxylic acid ester of the formula ##STR24## wherein R 1 , R 2 , R 3 , R 4 , R 5 , X, Y and Z are as defined above, (ii) reacting said γ-halogeno-δ-unsaturated-carboxylic acid ester of formula V with a basic substance at a temperature of from about -80° C to about 100° C to produce a substituted cyclopropanecarboxylic ester of the formula ##STR25## wherein R 1 , R 2 , R 3 , R 4 , R 5 , Y and Z are as defined above, and (iii) contacting said ester of the formula I' with an alcohol of the formula R.sup.13 OH VIII wherein R 13 is as defined above, to produce said compound of formula I by ester exchange.

Claim 16

A process for the preparation of a substituted cyclopropane-carboxylic ester of the formula ##STR21## wherein R 1 , R 2 , R 3 and R 4 , which may be the same or different, each represents 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, an aryl group having up to 8 carbon atoms or an aralkyl group having up to 10 carbon atoms or R 1 and R 2 or R 1 and R 3 together with the carbon atoms to which they are attached form a ring; R 13 is a group of the formula ##STR22## wherein R 6 is a hydrogen atom or a methyl group; R 7 is an alkenyl, alkadienyl or alkynyl group having up to 6 carbon atoms or a benzyl group; R 8 is a hydrogen atom, an ethynyl group or a cyano group; R 9 is a hydrogen atom, a halogen atom or an alkyl group having up to 5 carbon atoms; R 10 is a halogen atom, an alkyl, alkenyl or alkynyl group having up to 6 carbon atoms, or a benzyl, thenyl, furylmethyl, phenoxy or phenylthio group, or R 9 and R 10 together form a polymethylene chain or such a chain interrupted by an oxygen or sulfur atom; Q is an oxygen or sulfur atom or a group --CH═CH--; n is an integer of 1 or 2; A is an o-, m- or p-phenoxyphenyl group, a phthalimido group, a thiophthalimido group, a di- or tetra-hydrophthalimido group or a dialkylmaleimido group; R 11 is a phenyl group, a thienyl group or a furyl group; and W is a hydrogen atom, a methyl group, an alkoxy group, a cyano group or a halogen atom; and Y and Z, which may be the same or different, each represents a hydrogen atom or a halogen atom selected from the group consisting of F, Cl, Br and I, which process comprises (i) reacting at a temperature of from 100° C to 200° C, a 1-halogeno-3-alkene-2-ol of the formula ##STR23## wherein R 1 , R 2 , R 3 , Y and Z are as defined above, and X is a halogen atom selected from the group consisting of F, Cl, Br and I, with an ortho-carboxylic ester represented by the formula R.sup.4 --CH.sub.2 --C(OR.sup.5).sub.3 III wherein R 4 is as defined above and R 5 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 hydrocarbon group containing a hetero atom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen, the three groups R 5 being the same or different, to produce a γ-halogeno-δ-unsaturated-carboxylic acid ester of the formula ##STR24## wherein R 1 , R 2 , R 3 , R 4 , R 5 , X, Y and Z are as defined above, (ii) reacting said γ-halogeno-δ-unsaturated-carboxylic acid ester of formula V with a basic substance at a temperature of from about -80° C to about 100° C to produce a substituted cyclopropanecarboxylic ester of the formula ##STR25## wherein R 1 , R 2 , R 3 , R 4 , R 5 , Y and Z are as defined above, and (iii) contacting said ester of the formula I' with an alcohol of the formula R.sup.13 OH VIII wherein R 13 is as defined above, to produce said compound of formula I by ester exchange.

Claim 17

A process according to claim 1, wherein the 1-halogeno-3-alkene-2-ol of general formula [II] is prepared by isomerizing a 1-halogeno-4-alkene-2-ol.

Claim 18

A process according to claim 13, wherein the 1-halogeno-3-alkene-2-ol of formula II is 1,1,1-trichloro-3-methyl-3-pentene-2-ol and the 1-halogeno-4-alkene-2-ol is 1,1,1-trichloro-3-methyl-4-pentene-2-ol.

Claim 19

A process according to claim 13, wherein the 1-halogeno-3-alkene-2-ol of formula II is 1,1,1-tribromo-3-methyl-3-pentene-2-ol and the 1-halogeno-4-alkene-2-ol, is 1,1,1-tribromo-3-methyl-4-pentene-2-ol.