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

A process for the preparation of a substituted cyclopropane-carboxylic ester of the formula ##STR21## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.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.sup.1 and R.sup.2 or R.sup.1 and R.sup.3 together with the carbon atoms to which they are attached form a ring;

• R.sup.13 is a group of the formula ##STR22## wherein R.sup.6 is a hydrogen atom or a methyl group;
• R.sup.7 is an alkenyl, alkadienyl or alkynyl group having up to 6 carbon atoms or a benzyl group;
• R.sup.8 is a hydrogen atom, an ethynyl group or a cyano group;
• R.sup.9 is a hydrogen atom, a halogen atom or an alkyl group having up to 5 carbon atoms;
• R.sup.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.sup.9 and R.sup.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.dbd.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.sup.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.degree. C to 200.degree. C, a 1-halogeno-3-alkene-2-ol of the formula ##STR23## wherein R.sup.1, R.sup.2, R.sup.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.sup.4 is as defined above and R.sup.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.sup.5 being the same or different, to produce a .gamma.-halogeno-.delta.-unsaturated-carboxylic acid ester of the formula ##STR24## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, X, Y and Z are as defined above, (ii) reacting said .gamma.-halogeno-.delta.-unsaturated-carboxylic acid ester of formula V with a basic substance at a temperature of from about -80.degree. C to about 100.degree. C to produce a substituted cyclopropanecarboxylic ester of the formula ##STR25## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.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.sup.13 is as defined above, to produce said compound of formula I by ester exchange.