Sumitomo Chemical Company, Limited

Nobuo Ohno

Takashi Matsuo

Nobushige Itaya

Toshio Mizutani

Masachika Hirano

Yoshitoshi Okuno

Isao Ohno

Hisami Takeda

Keimei Fujimoto

Shigeyoshi Kitamura

Toshio Nishioka

Kiyoshi Kasamatsu

Yositosi Okuno

Takashi Kato

Osamu Magara

Yoshitaka Ume

Hajime Hirai

Tadashi Ohsumi

Masato Mizutani

Yukio Suzuki

Akihiko Mine

Takeaki Umemura

Kohichi Aketa

Akio Higo

Tetsuhiko Watanabe

Norbushige Itaya

Masakazu Miyakado

Isamu Nakayama

Takenori Kusumi

Hiroshi Kakisawa

An algicidal composition which is effective against red tide comprises, a higher fatty acid or its salt as an active ingredient, such as 6, 9, 12, 15-octadecatetraenic acid.

Algicidal composition

Substituted acetate compounds represented by the formula ##STR1## which are useful as pesticides and pesticidal composition containing the substituted acetate compounds as active ingredients, as well as processes for preparing the compounds and the compositions are disclosed.

Optically active phenyl acetates

An insecticidal composition comprising, as an active ingredient, an optically active .alpha.-cyano-3-phenoxybenzyl 2-(4-chlorophenyl)isovalerate and an inert carrier having a strong insecticidal activity without any appreciable toxicity to plants as well as to mammals.

Insecticidal composition containing optically active

A compound of the formula, ##STR1## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are respectively hydrogen atom or methyl, R.sub.5 is a member of ##STR2## wherein R.sub.6 is hydrogen atom or methyl, R.sub.7 is alkenyl, alkadienyl, alkynyl or benzyl, R.sub.8 is hydrogen atom, ethynyl or cyano, R.sub.9 is hydrogen atom, a halogen atom or alkyl, R.sub.10 is a halogen atom, alkyl, alkenyl, alkynyl, benzyl, thenyl, furylmethyl, phenoxy, substituted phenoxy of phenylthio, or R.sub.9 and R.sub.10 are bonded at the ends to form polymethylene chain containing or not containing oxygen or sulfur atom, Y is oxygen atom, sulfur atom or --CH.dbd.CH--, n is 1 or 2, Z is phthalimido, thiophthalimido, di- or tetra-hydrophthalimido or dialkylmaleimido, R.sub.11 is phenyl, thienyl or furyl and X is a halogen atom, which is useful as an active ingredient of insecticides.

Novel alkadienylcyclopropanecarboxylates

A process for isomerizing optically active .alpha.-cyano-3-phenoxybenzyl 2-(4-chlorophenyl)isovalerate at the asymmetric carbon atom of the 3-phenoxybenzyl moiety, and a process for obtaining (S)-.alpha.-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)isovalerate from (R, S)-.alpha.-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)isovalerate.

Process for preparing optically active .alpha.-cyano-3-phenoxybenzyl

A novel substituted-arylacetic acid ester of the formula, ##STR1## wherein R.sub.1 and R.sub.2 are each hydrogen or a halogen atom, a C.sub.1 -C.sub.4 alkyl, C.sub.2 -C.sub.4 alkenyl, C.sub.1 -C.sub.4 alkoxy, cyano, nitro, methylthio, C.sub.1 -C.sub.4 alkanoyl, C.sub.1 -C.sub.4 alkanoyloxy, or C.sub.1 -C.sub.4 alkoxycarbonyl group, or R.sub.1 and R.sub.2, taken together, may form methylenedioxy, a C.sub.3 -C.sub.5 alkylene or butadienylene (--CH.dbd.CH--CH.dbd.CH--) ring; R.sub.3 is a C.sub.2 -C.sub.4 alkyl, C.sub.2 -C.sub.4 alkenyl, propargyl, C.sub.3 -C.sub.6 cycloalkyl or cyclopropylmethyl group; R.sub.4 is hydrogen or a halogen atom, methyl or ethyl group; R.sub.5 is allyl, propargyl, 3-butenyl, 3-butynyl, phenyl or benzyl group; and A is oxygen or sulfur atom or --CH.dbd.CH-- group, which possesses various useful insecticidal and acaricidal activities and can be prepared by reacting a substituted-arylacetic acid of the formula: ##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and A are each as defined above, or a reactive derivative thereof with an alcohol, or halide or sulfonate thereof of the formula, ##STR3## wherein R.sub.4 and R.sub.5 are each as defined above and X is hydroxy group, a halogen atom, alkylsulfonyloxy or arylsulfonyloxy group.

Substituted-acetic acid ester

m-(p-Bromophenoxy)-.alpha.-cyanobenzyl trans- or trans-rich-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate of the formula (I), ##STR1## and their preparation and use as a low fish toxic insecticide and/or acaricide.

Low mammalian toxic and/or low fish toxic insecticides and/or acaricides

Novel insecticidal composition

Novel alkynylcyclopropanecarboxylic acid esters represented by the formula, ##STR1## wherein R.sub.1 represents hydrogen, halogen, lower alkyl having up to 5 carbon atoms, lower alkenyl having up to 5 carbon atoms, lower alkynyl having up to 5 carbon atoms, C.sub.1 -C.sub.4 alkoxy C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkylthio C.sub.1 -C.sub.4 alkyl, aryl, aryl C.sub.1 -C.sub.4 alkyl, furyl, substituted furyl, thienyl, substituted thienyl, furfuryl, substituted furfuryl, thenyl, substituted thenyl, cyclo C.sub.3 -C.sub.6 alkyl, substituted cyclo C.sub.3 -C.sub.6 alkyl, cyclo C.sub.3 -C.sub.6 alkenyl or substituted cyclo C.sub.3 -C.sub.6 alkenyl; R.sub.2 and R.sub.3 individually represent hydrogen, halogen, lower alkyl having up to 5 carbon atoms, lower alkenyl having up to 5 carbon atoms, lower alkynyl having up to 5 carbon atoms, aryl, aryl C.sub.1 -C.sub.4 alkyl or may form a carbon-carbon bond; or R.sub.1 and R.sub.3 are bonded to each other at the ends to form a polymethylene chain containing or not containing an oxygen or a sulfur atom, or R.sub. 1 and R.sub.2 are bonded to each other at the ends to form a polymethylene chain containing or not containing an oxygen or a sulfur atom; R.sub.4 represents hydrogen or methyl; R.sub.5 represents hydrogen, methyl, vinyl, 1-propenyl, 2-methyl-1-propenyl, 2-methoxymethyl-1-propenyl, 2-methoxycarbonyl-1-propenyl, 2,2-dichlorovinyl or cyclopentylidenemethyl when R.sub.4 is hydrogen, and R.sub.5 represents methyl when R.sub.4 is methyl; and R.sub.6 and R.sub.7 represent hydrogen or methyl. These novel esters are produced by reacting an alcohol or its halide or arylsulfonate of the formula, ##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.6 are as defined above, and A is hydroxy, halogen or arylsulfoxy, with a cyclopropanecarboxylic acid of the formula, ##STR3## wherein R.sub.4, R.sub.5 and R.sub.7 are as defined above, or its reactive derivative. These esters are useful as an insecticide harmless to mammals.

Acetylenic secondary alcohols

A method for racemization of optically active 2-(4-chlorophenyl)-3-methylbutyric acid which comprises the steps of (a) reacting optically active 2-(4-chlorophenyl)-3-methylbutyric acid with a hydroxide or carbonate of an alkali metal or alkaline earth metal at a temperature of more than 110.degree. C. to produce a racemate of the alkali metal or alkaline earth metal salt of the above acid, and (b) converting the resulting racemate of the salt to the acid.

Racemization of optically active 2-(4-chlorophenyl)-3-methylbutyric acid

A compound of the formula, ##STR1## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are respectively hydrogen atom or methyl, R.sub.5 is a member of ##STR2## wherein R.sub.6 is hydrogen atom or methyl, R.sub.7 is alkenyl, alkadienyl, alkynyl or benzyl, R.sub.8 is hydrogen atom, ethynyl or cyano, R.sub.9 is hydrogen atom, a halogen atom or alkyl, R.sub.10 is a halogen atom, alkyl, alkenyl, alkynyl, benzyl, thenyl, furylmethyl, phenoxy, substituted phenoxy or phenylthio, or R.sub.9 and R.sub.10 are bonded at the ends to form polymethylene chain containing or not containing oxygen or sulfur atom, Y is oxygen atom, sulfur atom or --CH.dbd.CH--, n is 1 or 2, Z is phthalimido, thiophthalimido, di- or tetra-hydrophthalimido or dialkylmaleimido, R.sub.11 is phenyl, thienyl or furyl and X is a halogen atom, which is useful as an active ingredient of insecticides.

Insecticidal alkadienylcyclopropanecarboxylates

A purification process for 3-phenoxybenzaldehyde, which comprises reacting crude 3-phenoxybenzaldehyde with an alkali metal or ammonium bisulfite, or metabisulfite in the presence of an organic quaternary ammonium salt, an inorganic acid salt of organic tertiary amines, or a macrocyclic polyether used as a catalyst, isolating the resulting 3-phenoxybenzaldehyde alkali metal or ammonium bisulfite adduct, and decomposing it by using an acid or a base, or by heating.

Purification process for 3-phenoxybenzaldehyde

Novel alkynyl esters of cyclopropanecarboxylic acid represented by the formula, ##STR1## wherein R.sub.1 represents hydrogen, lower alkyl having 1-4 carbon atoms, lower alkenyl having 2-4 carbon atoms, lower alkynyl having 2-4 carbon atoms, C.sub.1 -C.sub.2 alkoxy-C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.2 alkylthio-C.sub.1 -C.sub.4 alkyl, furyl, thienyl, furfuryl, thenyl, cyclo-C.sub.3 -C.sub.6 alkyl, oxygen atom-containing cyclo-C.sub.3 -C.sub.6 alkyl, cyclo-C.sub.5 -C.sub.6 alkenyl, oxygen atom-containing cyclo-C.sub.4 -C.sub.6 alkenyl, halo-C.sub.2 -C.sub.4 alkenyl, phenyloxymethyl, phenylthiomethyl, cyclo-C.sub.5 -C.sub.6 alkenylmethyl, oxygen atom-containing cyclo-C.sub.4 -C.sub.6 alkenylmethyl, cyclo-C.sub.5 -C.sub.6 alkylmethyl, oxygen atom-containing cyclo-C.sub.4 -C.sub.6 alkylmethyl or ##STR2## IN WHICH X is halogen, nitro, cyano, methylenedioxy, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.2 alkoxy, dimethylamino, m is 0, 1, 2 or 3, n is 0, 1, 2 or 3 and each X may be different when n is 2 or 3; R.sub.2 and R.sub.3 individually represent hydrogen, halogen (except R.sub.2), phenyl, benzyl, lower alkyl having 1 - 3 carbon atoms, lower alkenyl having 2 - 3 carbon atoms, lower alkynyl having 2 - 3 carbon atoms or may form a carbon-carbon bond or are bonded to each other at the ends to form C.sub.3 -C.sub.4 polymethylene chain, or R.sub.1 and R.sub.2 are bonded to each other at the ends to form C.sub.5 polymethylene chain; R.sub.4 represents hydrogen or methyl; R.sub.5 represents hydrogen, methyl, vinyl, 1-propenyl, 2-methyl-1-propenyl, 2-methoxy-methyl-1-propenyl, 2-methoxycarbonyl-1-propenyl, 1,3-butadienyl, 2-methyl-1,3-butadienyl, 2,2-dichlorovinyl or cyclopentylidenemethyl when R.sub.4 is hydrogen, and R.sub.5 represents methyl when R.sub.4 is methyl; and R.sub.6 and R.sub.7 represent hydrogen or methyl. These novel esters are produced by reacting an alcohol or its halide or arylsulfonate of the formula, ##STR3## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.6 are as defined above, and A is hydroxy, halogen or arylsulfoxy, with a cyclopropanecarboxylic acid of the formula, ##STR4## wherein R.sub.4, R.sub.5 and R.sub.7 are as defined above, or its reactive derivative. These esters are useful as an insecticide harmless to mammals.

Novel cyclopropanecarboxylates

A novel substituted-arylacetic acid ester of the formula, ##STR1## wherein R.sub.1 and R.sub.2 are each hydrogen or a halogen atom, a C.sub.1 -C.sub.4 alkyl, C.sub.2 -C.sub.4 alkenyl, C.sub.1 -C.sub.4 alkoxy, cyano, nitro, methylthio, C.sub.1 -C.sub.4 alkanoyl, C.sub.1 -C.sub.4 alkanoyloxy, or C.sub.1 -C.sub.4 alkoxycarbonyl group, or R.sub.1 and R.sub.2, taken together, may form methylenedioxy, a C.sub.3 -C.sub.5 alkylene or butadienylene (--CH.dbd.CH--CH.dbd.CH--) ring; R.sub.3 is a C.sub.2 -C.sub.4 alkyl, C.sub.2 -C.sub.4 alkenyl, propargyl, C.sub.3 -C.sub.6 cycloalkyl or cyclopropylmethyl group; R.sub.4 is hydrogen or a halogen atom, methyl or ethyl group; R.sub.5 is allyl, propargyl, 3-butenyl, 3-butynyl, phenyl or benzyl group; and A is oxygen or sulfur atom or --CH.dbd.CH-- group, which possesses various useful insecticidal and acaricidal activities and can be prepared by reacting a substituted-arylacetic acid of the formula; ##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and A are each as defined above, or a reactive derivative thereof with an alcohol, or halide or sulfonate thereof of the formula, ##STR3## wherein R.sub.4 and R.sub.5 are each as defined above and X is hydroxy group, a halogen atom, alkylsulfonyloxy or arylsulfonyloxy group.

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Toyonaka, Japan

Nobuo Ohno