Shell Oil Comapny

Shell Internationale Research Maatschappij, B.v.

Pieter A Verbrugge

Petrus A Kramer

Jannetje De Waal

Elisabeth W Uurbanus

Albertus J Mulder

David W Sopher

Roger A Sheldon

Johannes Van Berkel

Hendrik C Kelderman

Johannes W Van Der Meer

Antony G Brinnand

Martin Anderson

Willy Brunmayer-Schilt

The invention provides a process for the preparation of N-benzoylcarbamates of general formula ##STR1## wherein R.sup.1 represents a hydrogen atom, a halogen atom, a C.sub.1-4 alkyl group, a C.sub.1-4 alkoxy group or a trifluoromethyl group, R.sup.2 represents a halogen atom, a C.sub.1-4 alkyl group, a C.sub.1-4 alkoxy group or a trifluoromethyl group, R.sup.3 represents a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, and R represents a C.sub.1-8 alkyl group optionally substituted by one or more halogen atoms or a phenyl group optionally substituted by one or more substituents selected from halogen atoms and methyl groups, characterized by reacting an alkali metal salt of a benzamide of general formula ##STR2## wherein R.sup.1, R.sup.2 and R.sup.3 are as defined above, with a carbonate of formula

Process for preparing carbamates, and intermediates therein

This invention provides benzamide compounds of general formula ##STR1## wherein each of A and B independently represents a hydrogen or halogen atom, X represents an oxygen or a sulphur atom, n is 0, 1, 2, 3 or 4, each Z moiety independently represents a halogen atom or a C.sub.1-6 alkyl group, and Y represents a C.sub.1-6 haloalkyl group, a C.sub.1-6 haloalkoxy group, a group of formula ##STR2## wherein P is 0, 1 or 2, each Z' moiety independently represents a halogen atom or a C.sub.1-6 alkyl group, Y' represents a C.sub.1-6 haloalkyl, C.sub.1-6 haloalkoxy, nitro or cyano group and Q represents N or C-H, or, when n is 2 or 3, Y may also be a halogen atom; processes for their preparation; and their use as pesticides.

Benzamide compounds, their preparation and their use as pesticides

Process for the preparation of a compound of formula or a salt thereof ##STR1## wherein R.sub.1 represents a hydrogen atom or a group of formula R.sub.2 SO.sub.2 or phenyl--CH(R.sub.3)-- wherein R.sub.2 represents a phenyl, tolyl or C.sub.1-4 alkyl group and R.sub.3 represents a hydrogen atom or a phenyl or C.sub.1-4 alkyl group, which process comprises contacting nickel in an oxidation state of at least 3 with a 3-hydroxymethyl azetidine derivative of formula ##STR2## wherein R.sub.4 represents a group of formula R.sub.2 SO.sub.2 or phenyl--CH(R.sub.3)-- and R.sub.5 represents a hydrogen atom or a hydroxymethyl group or a group of formula COOH or a salt thereof, followed, where R.sub.5 is not a hydrogen atom, by the decarboxylation of the compound of the 3,3-dicarboxylic intermediate product or a salt thereof and, if desired to produce a compound in which R.sub.1 represents a hydrogen atom, by deprotection of the N-atom. Also, novel N-substituted azetidine carboxylate derivatives of the formula ##STR3## wherein X represents a group CH.sub.2 OH or COOY where Y represents a hydrogen or an alkali or alkaline earth metal atom.

N-substituted azetidine carboxylate derivatives

Preparation of azetidine-3-carboxylic acid or a salt thereof from N-benzylazetidine-3-carboxylic acid or a salt thereof by catalytically hydrogenating the N-benzylazetidine-3-carboxylic compound in the presence of water, formate ions, and ammonium and/or alkylammonium ions. Novel ammonium and alkylammonium salts are claimed.

Catalytic hydrogenolysis

Process for the preparation of a compound of formula or a salt thereof ##STR1## wherein R.sub.1 represents a hydrogen atom or a group of formula R.sub.2 SO.sub.2 or phenyl--CH(R.sub.3)--wherein R.sub.2 represents a phenyl, tolyl or C.sub.1-4 alkyl group and R.sub.3 represents a hydrogen atom or a phenyl of C.sub.1-4 alkyl group, which process comprises contacting nickel in an oxidation state of at least 3 with a 3-hydroxymethyl azetidine derivative of formula ##STR2## wherein R.sub.4 represents a group of formula R.sub.2 SO.sub.2 or phenyl--CH(R.sub.3)--and R.sub.5 represents a hydrogen atom or a hydroxymethyl group or a group of formula COOH or a salt thereof, followed, where R.sub.5 is not a hydrogen atom, by the decarboxylation of the compound of the 3,3-dicarboxylic intermediate product or a salt thereof and, if desired to produce a compound in which R.sub.1 represents a hydrogen atom, by deprotection of the N-atom. Also, novel N-substituted azetidine carboxylate derivatives of the formula ##STR3## wherein X represents a group CH.sub.2 OH or COOY where Y represents a hydrogen or an alkali or alkaline earth metal atom.

Process for preparing azetidine derivatives; and intermediates therein

Process for the preparation of esters of 1,5-dimethyl bicyclo [3.2.1] octan-8-ol and/or derivatives thereof by reacting 1,5-dimethyl-1,5-cyclooctadiene with an inorganic polybasic acid.

Esters of 1,5-dimethyl bicyclo [3.2.1] octan-8-ol

Process for the preparation of Diels-Alder type adducts by reacting a compound with formula ##STR1## or the corresponding hydrated derivative, wherein R.sup.1, R.sup.2, and R.sup.4 are H or lower alkyl, R.sup.3 is lower alkyl, X is O,S, (O--CR.sup.5 R.sup.6 R.sup.7).sub.2 or ##STR2## wherein R.sup.5, R.sup.6 and R.sup.7 an H or lower alkyl, n is 2-5 and Y is H, alkyl or alkenyl or Y and R.sup.2 together form an alkylene group which may contain one or more substituents, with a cyclopentadiene and/or an oligomer thereof in the presence of an aqueous solution of a strong proton donor having a conjugate with a low nucleophilicity.

Process for the preparation of bicyclo [2.2.] heptene derivatives

When the reaction of aldehydes with alkali metal trihaloacetates is carried out in the presence of a highly polar aprotic solvent (DMF, DMSO), novel organic alkali metal carbonates, which are precursors of pyrethroid insecticides, are formed in high yields and at a high rate. Novel sulfonates and dihalophosphites, derived from these carbonates have also been claimed.

Trihalomethylation of aldehydes

Conversion of esters (R.sup.1)(R.sup.2)C(C Hal.sub.3)OX, X being-P Hal.sub.2, --C(O)OR.sup.3 or ##STR1## R.sup.1, R.sup.3 and R.sup.4 being optionally substituted hydrocarbyl groups and R.sup.2 methyl or hydrogen, with zinc in acetic acid gives a very high yield of a dihalovinyl compound (R.sup.1)(R.sup.2)C.dbd.C Hal.sub.2, e.g., of the ethyl ester of the parent acid of pyrethroid insecticides.

Process of preparing dihalovinyl compounds

Cyclopropyl dihalo phosphites

Preparation of novel alkyl 2,2-dihalovinylcyclopropylacetates (intermediates in the preparation of insecticides) by reaction of a phosphine with a compound generating a dihalocarbene and reaction of the product resulting therefrom with an alkyl formylcyclopropylacetate, both reactions being carried out in a solvent.

1R, Cis 2,2-dihalovinyl-3,3-dimethylcyclopropylmethanol and ester

Isolation of cis acids of the formula ##STR1## wherein each of the groups X.sup.1 and X.sup.2 represents a fluorine, chlorine or bromine atom or a hydrocarbyl group, from a mixture of cis and trans acids of this formula, by idolactonization, forming novel cis-lactones of the formula ##STR2## isolation of these cis-lactones and reduction thereof to the said cis acids. The process may be used for the isolation of cis precursors to insecticides from mixtures with their trans isomers.

Cis-lactone pyrethroid intermediates

Trihalocyclopropyl carbonates

2-Formyl-3,3-dimethylcyclopropylacetic acid is prepared by ozonolysis of 3-acetyl-6,6-dimethylbicyclo[3.1.0]-2-hexene followed by reductive cleavage of the ozonolysis product thus formed. The 3-acetyl-6,6-dimethylbicyclo[3.1.0]-2-hexene is prepared by contacting 2-(2-acetyl-3-oxobutyl)-3,3-dimethylcyclopropanecarbaldehyde with a base in the presence of a solvent.

Preparation of 2-formyl-3,3-dimethylcyclopropaneacetic acid

The invention relates to 2-(2,2-dihalovinyl)-3,3-dimethylcyclopropylacetones which are intermediates for the preparation of pyrethroids which have good insecticidal properties.

Growing community of inventors

Amsterdam, Netherlands

Pieter A Verbrugge