Sumitomo Chemical Company, Limited

Yoji Sakito

Gohfu Suzukamo

Yukio Yoneyoshi

Masami Fukao

Koji Hagiya

Toshio Nishioka

Hiroko Sakane

Naoto Konya

Shinji Nishii

Gohfu Suzukmo

The present invention relates to a method for producing optically active alcohol derivatives, which are useful as fungicides, herbicides or plant growth regulators, represented by the formula, ##STR1## by carrying out the asymmetric reduction of a ketone compound represented by the formula, ##STR2## with a boron hydride-reducing agent modified with an optically active amino alcohol represented by the formula, ##STR3## and also relates to the boron hydride type compound obtained by reacting the above optically active amino alcohol with a boron hydride compound and its production method.

Method for producing an optically active azolyl-.alpha.,

The optically active benzylamine derivatives of the present invention are very useful for use as the asymmetric ligand of an asymmetric reducing agent. By using the optically active amine-boron complex prepared from the compound of the present invention, optically active products can be obtained in a specifically high optical yield. Moreover, the separation and recovery of the reaction products and asymmetric ligand can be easily achieved.

Optically active hydroxybenzylamine derivative and process for producing

Disclosed is a process for producing an optically active amine represented by the formula (IV) ##STR1## wherein R.sub.7 and R.sub.8 each denote an alkyl group, aryl group or aralkyl group, providing that they do not denote the same group at the same time, and * indicates an asymmetric carbon atom, which comprises reacting an asymmetric reducing agent obtained from (1) an optically active amine derivative represented by the formula (I) ##STR2## wherein R.sub.1 denotes an alkyl group, aryl group or aralkyl group; R.sub.2 denotes a hydrogen atom, alkyl group or aralkyl group; R.sub.3 denotes an aryl group or a substituent represented by the formula (II) ##STR3## wherein R.sub.4 and R.sub.5 each denote a hydrogen atom, aryl group or aralkyl group, and * is as defined above, (2) a metal borohydride and (3) sulfuric acid, with either the syn-isomer or the anti-isomer of an oxime derivative represented by the formula (III) or with a mixture rich in either one of the two isomers ##STR4## wherein R.sub.6 denotes an alkyl group, aralkyl group or alkyl-substituted silyl group, and R.sub.7 and R.sub.8 are as defined above. The optically active amine obtained can be used as a resolving agent for preparing medicinal agents, agricultural chemicals, or intermediates thereof.

Process for producing optically active amines

A method for producing an optically active amine which is an important compound as a resolving agent for medicines, agricultural chemicals, intermediates thereof, etc is disclosed.

Method for producing optically active amines

Alkenecarboxylic esters of the formula I ##STR1## where R.sup.1 is alkyl of 1 to 6 carbon atoms, R.sub.2 is hydrogen or alkyl or 1 to 4 carbon atoms, the substituents being identical or different, and n is 1, 2 or 3 are prepared by reacting lactones of the formula II ##STR2## where R.sup.2 has the same meanings as in the formula I, R.sub.3 is hydrogen or methyl and m is 0, 1 or 2, with the proviso that n and m differ by 1 when R.sub.3 is hydrogen and by 2 when R.sub.3 is methyl, with alkanols having 1 to 6 carbon atoms at from 50.degree. to 450.degree. C. in the presence of zeolites and/or phosphates as catalysts.

Method for producing an optically active

Process for producing optically active compounds

Optically active hydroxybenzylamine

Trans-2,2-dimethyl-3-(2,2-dihalovinyl)-cyclopropane carboxylic acid halides which are an intermediate for insecticides are prepared by allowing arylphosphines to react with cis- or cis-/trans-mixed 2,2-dimethyl-3-(2,2-dihalovinyl)-cyclopropane carboxylic acid halides of the formula ##STR1## wherein both X and Y are halogen atoms, respectively, at a temperature of -10.degree. to 100.degree. C., in the presence of absence of halogen compounds.

Process for preparing

Trans-2,2-dimethyl-3-(2,2-dihalovinyl)-cyclopropane carboxylic acid esters which are intermediate of insecticides are prepared by allowing (1) alkali metal alkoxides and titanium alkoxides or (2) silicon iodides to react with cis- or cis-/trans-mixed 2,2-dimethyl-3-(2,2-dihalovinyl)-cyclopropane carboxylic acid esters of the formula ##STR1## wherein X is a halogen atom and R is an alkyl, cycloalkyl or aralkyl group having 1-10 carbon atoms.

Process for preparing trans-2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropane

Method for producing an optically active azolyl-.alpha.

Optically active chrysanthemic acid or its derivatives of the formula ##STR1## (wherein X represents a hydroxyl group, a halogen atom, a C.sub.1-20 alkoxy group or a 2,2-dimethyl-3-isobutenyl-cyclopropane carboxyl group and * mark shows asymmetric carbon atom) is racemized by allowing it to react with a bromine compound or a SH compound, in the presence of light.

Method for racemization of optically active chrysanthemic acid or its

Racemization of an optically active chrysanthemic acid or its ester of the formula: ##STR1## wherein R represents a hydrogen atom, an alkyl group of 1-20 carbon atoms, a cycloalkyl group of 3-20 carbon atoms or an aralkyl group of 7-20 carbon atoms and * mark indicates asymmetric carbon atom, is effected by contacting the acid or its ester with at least one compound selected from the group consisting of a carboxylic acid bromide, a silicon bromide, an S-bromine compound, and N-bromine compound, a halo-bromine compound and an SH compound in the presence of a peroxide or an azo compound.

Racemization of an optically active chrysanthemic acid derivatives of the formula: ##STR1## wherein X represents a chlorine atom, bromine atom or 2,2-dimethyl-3-isobutenyl-cyclopropane carboxyl group and * mark represents asymmetric carbon atom, is effected by contacting the acid derivatives with at least one compound selected from the group consisting of hydrogen bromide, a carboxylic acid bromide, an N-bromine compound, an S-bromine compound, a halobromine compound, a silicon-bromide compound, a phosphorus-bromide compound and an SH compound in the presence of a peroxide or an azo compound.

Method for racemization of optically active chrysanthemic acid

Racemization of optically active chrysanthemic acid or its ester of the formula: ##STR1## wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aralkyl group of 1-20 carbon atoms and * indicates an asymmetric carbon atom, is effected by contacting it with hydrogen bromide or a phosphorus bromide compound. This method may also be effected in the presence of a peroxide or an azo compound. This method is industrially very useful.

Tetrahydronaphthalene derivatives of the formula: ##STR1## wherein either one of R.sup.1 and R.sup.2 is hydrogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy and the other is acetyl and R.sup.3 is hydrogen or methyl in a racemic or optically active form, which are useful as perfumes or intermediates for production of perfumes, are prepared from an R.sup.4 -benzene and pyrocine through the intermediary compounds of the formula: ##STR2## wherein R.sup.4 is hydrogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy present at either one of 6- and 7-positions and A is hydrogen, carboxyl, C.sub.2 -C.sub.5 alkoxycarbonyl, halogen, methyl, hydroxymethyl or halomethyl.

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Montreal, Canada

Yoji Sakito