Ciba-geigy Corporation

Hans Greuter

Pierre Martin

Daniel Bellus

Laurenz Gsell

Peter Ackermann

Eginhard Steiner

Hans H Bosshard

John G Dingwall

Jozef Drabek

Willy Meyer

Marcus Baumann

The reaction of 2-mercapto-benzothiazole or -benzimidazole with .alpha.,.beta.-unsaturated carboxylic acid derivatives in a strongly acid reaction medium gives compounds of the formula I ##STR1## in which X is sulfur or NH, each radical R independently of one another is H, alkyl, halogenalkyl, alkoxy, alkylthio, alkylsulfonyl, phenyl, alkylphenyl, phenylalkyl, cycloalkyl, halogen, NO.sub.2, CN, COOH, COOalkyl or a tertiary amino or carbamoyl group and R.sup.1, R.sup.2 and R.sup.3 independently of one another are H, alkyl, halogenalkyl, hydroxyalkyl, alkoxyalkyl unesterified or esterified carboxyl or carboxylalkyl, carbamyol, carbamyolalkyl or unsubstituted or substituted aryl or aralkyl, or R.sup.1 and R.sup.2 together are straight-chain or branched alkylene, which can be substituted by 1 or 2 carboxyl groups, R.sup.4 is unsubstituted or substituted amino, alkoxy, cycloalkoxy, aryloxy or aralkyloxy, or R.sup.2 and R.sup.4 together are CH.sub.2 --CO--O-- or --CH.sub.2 CO--NR.sup.5 -- or R.sup.3 and R.sup.4 together are --CO--O-- or --CO--NR.sup.5 --, forming an anhydride or imide ring, wherein R.sup.5 is unsubstituted or substituted alkyl, cycloalkyl, aryl, aralkyl or hydrogen.

Process for the preparation of .beta.-(benzothiazolylthio)- and

The reaction of 2-mercapto-benzothiazole or -benzimidazole with .alpha.,.beta.-unsaturated carboxylic acids in a strongly acid reaction medium gives compounds of the formula I ##STR1## in which X is sulfur or NH, each radical R independently of one another is H, alkyl, halogenoalkyl, alkoxy, alkylthio, alkylsulfonyl, phenyl, alkylphenyl, phenylalkyl, cycloalkyl, halogen, NO.sub.2, CN, COOH, COOalkyl, OH or an amino or carbamyl group and R.sup.1, R.sup.2 and R.sup.3 independently of one another are H, alkyl, halogenoalkyl, hydroxyalkyl, alkoxyalkyl, carboxyalkyl, carboxyl or unsubstituted or substituted aryl or aralkyl, or R.sup.1 and R.sup.2 together are straight-chain or branched alkylene, which can be substituted by 1 or 2 carboxyl groups.

There is described a new process for the preparation of optically active 2-(2',2'-dihalogenovinyl)-cyclopropane-1-carboxylic acids substituted in the 3 position, and derivatives thereof. A racemate of certain cyclobutanones is reacted with a sulfurous acid salt of an optically active base to obtain a mixture of diastereomeric 4-(2',2',2'-trihalogenoethyl)-cyclobutane-2-sulfonic acid salts; this mixture is then separated into the pure diastereomeric sulfonic acid salts. Either the pure diastereomeric sulfonic acid salts are converted directly to the desired optically active products, or the optically active cyclobutanones obtained from the pure diastereomeric sulfonic acids salts by decomposition are converted, in the presence of a base, to the desired product. Optionally, the product, optically active 2-(2',2'-dihalogenovinyl)-cyclopropane-2-carboxylic acids can be converted to their 1',2'-dibromo derivatives.

4-(2',2,2'-Trihalogenoethyl)-cyclobutane-1-sulfonic acid salts with

The preparation and use as an intermediate for making insecticides has been disclosed for a compound of the formula: ##STR1## in which X and Y are each chlorine or bromine.

2,4,4,4-Tetrahalobutanoic acid halide

There is described a new process for the preparation of optically active 2-(2',2'-dihalogenovinyl)-cyclopropane-1-carboxylic acids substituted in the 3 position, and derivatives thereof. A racemate of certain cyclobutanones is reacted with a sulfurous acid salt of an optically active base to obtain a mixture of diastereomeric 4-2-(2',2',2'-trihalogenoethyl)-cyclobutane-1-sulfonic acid salts; this mixture is then separated into the pure diastereomeric sulfonic acid salts. Either the pure diastereomeric sulfonic acid salts are converted directly to the desired optically active products, or the optically active cyclobutanones obtained from the pure diastereomeric sulfonic acids salts by decomposition is converted, in the presence of a base to the desired product. Optionally, the product, optically active 2-(2',2'-dihalogenovinyl)-cyclopropane-1-carboxylic acids can be converted to their 1',2'-dibromo derivatives. SU

Process for producing optically active

Compounds of the formulae Ia, Ib, IIa and IIb ##STR1## are described, wherein R represents alkyl, haloalkyl, benzyl, naphthyl or substituted or unsubstituted phenyl and one of R.sub.1 and R.sub.2 represents methyl and the other represents hydrogen or methyl, or R.sub.1 and R.sub.2 together represent alkylene of 2 or 3 carbon atoms. The compound of the formulae Ia, Ib, IIa and IIb are valuable intermediates for the manufacture of pyrethroid pesticides or precursors thereof.

Sulfonic acid esters of 2,2,2-trichloroethylhydroxycyclobutanones

A process for the preparation of 2-(2',2',2',-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the formula ##STR1## in which one of the radicals R.sub.1 and R.sub.2 is methyl and the other is hydrogen or methyl, or R.sub.1 and R.sub.2 together are an alkylene group having 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, comprising reacting a 2,4,4,4-tetrahalogenobutyric acid chloride in the presence of an organic base with an ethylene compound which is disubstituted in 1-position by the radicals R.sub.1 and R.sub.2, as defined above, to form a 2-(2',2',2'-trihalogenoethyl)-2-halogenocyclobutan-1-one and then rearranging the latter, in the presence of a catalyst, into a 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-one of the above formula; said 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones being valuable intermediates for the preparation of 2-(2',2'-dihalogenovinyl)-cyclopropanecarboxylic acid and its insecticidally active esters; as well as the 2-(2',2',2'-trihalogenoethyl)-4-halogenocyclobutan-1-ones of the above formula and the intermediates utilized for their preparation.

Process for the preparation of

Novel 2-(2',2'-dihalovinyl)-cyclobutan-1-ones and 2-(2',240 ,2'-trihaloethyl)-cyclobutan-1-ones of the formula ##STR1## are disclosed, wherein R.sub.1 represents --CH.dbd.CX.sub.2 or --CH.sub.2 --CX.sub.3, and X in each case represents chlorine or bromine, one of R.sub.2 and R.sub.3 represents methyl and the other represents hydrogen or methyl, or R.sub.2 and R.sub.3 together represent an alkylene group having 2 to 4 carbon atoms. The invention relates also to the production and the use of the said cyclobutanones.

2-(2',2'-Dihalovinyl)-cyclobutanones and

Cyclopropanecarboxylic acid esters of the formula ##STR1## wherein X.sub.1 represents chlorine or bromine, R.sub.1 represents hydrogen, methyl, vinyl, ethynyl or cyano, Y.sub.1 represents hydrogen, fluorine, chlorine or bromine, and n is 2, processes for their manufacture and their use in pest control.

Pesticidal spiropentanecarboxylates

Cyclobutane-1-carboxylates of the formula ##STR1## wherein R.sub.1 and R.sub.2 each represent hydrogen, fluorine, chlorine, bromine or methyl and

Pesticidal 1-(phenyl)-cyclobutane-1-carboxylates

Process for the production of 2-amino-3-hydroxypyridines of the formula ##STR1## wherein R.sub.1 and R.sub.2 independently of one another represent hydrogen or an alkyl group having 1 to 4 carbon atoms, wherein a furan-2-carboxylic acid of formula ##STR2## wherein R.sub.1 and R.sub.2 have the meaning given above, or a derivative thereof, for example a quaternary ammonium salt, an ester, an amide, a halogenide, an amidine salt, an iminoether salt or the nitrile, is reacted at a temperature of between 100.degree. and 300.degree. C in a solvent containing amide groups, in the presence of an acid catalyst, with ammonia.

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Eiken, Switzerland

Hans Greuter