Shell Oil Comapny

Roger A Sheldon

Peter Been

Derek A Wood

Arend Reinink

Pieter A Verbrugge

Ronald F Mason

Albertus J Mulder

Robert Van Helden

Johannes W Van Der Meer

Hendricus J Heijmen

Herbert P Rosinger

Marinus J Van Den Brink

An alpha-pivaloyl-substituted acetic acid ester of the formula (H.sub.3 C).sub.3 CCOCH.sub.2 COOR, wherein R is an optionally-substituted alkyl, aryl, alkaryl, or aralkyl group, is prepared by (a) reacting an alpha-pivaloyl-substituted malonic acid ester with a base selected from the class consisting of alkali metal alkoxides and compounds of the formula MXY, wherein M is an alkaline earth metal, X is an alkoxy group, and Y is either an alkoxy group or a halogen atom, and (b) acidifying the resulting reaction mixture.

Preparation of alpha-pivaloyl-substituted acetic acid esters

4-Acetyl-2-alkoxy-7,7-dimethyl-3-oxabicyclo[4.1.0]heptanes are new chemical compounds useful as intermediates for certain pyrethroid esters. They are prepared by ozonolysis of 4-hydroxy-2-carene and reduction of the product formed.

4-Acetyl-2-alkoxy-7,7-dimethyl-3-oxabicyclo[4.1.0]heptane

In the preparation of .alpha.-cyano esters from an acid halide and an aromatic aldehyde in the presence of water, a water-soluble cyanide, a substantially water-immiscible aprotic solvent and optionally a phase transfer catalyst, a stalled reaction is restarted by addition of an alkaline compound capable of generating cyanide ions.

Preparation of .alpha.-cyano esters

Esters of the formula ##STR1## wherein R is an optionally substituted hydrocarbyl group and Ar is an optionally substituted aromatic group are prepared from the corresponding aromatic aldehyde, the corresponding hydrocarbyl acid anhydride in the presence of water, and a water-soluble cyanide.

Preparation of esters

3-Phenoxytoluene is selectively chlorinated at the methyl moiety by treating it with sulfuryl chloride in the presence of a free-radical initiator in a specified manner under specified conditions.

Chlorination of 3-phenoxytoluene

Certain carboxylic acid esters also containing a cyano group are prepared by reacting an acid halide, an aldehyde and a water-soluble cyanide in the presence of one or more water-immiscible (cyclo)alkane solvents.

Certain carboxylic acid esters also containing a cyano group are prepared by reacting an acid halide, an aldehyde and a water-soluble cyanide in the presence of a water immiscible aprotic solvent and preferably a phase-transfer catalyst.

Certain carboxylic acid esters also containing a cyano group are prepared by reacting an acid halide, an aldehyde and a water-soluble cyanide in the presence of a water-immiscible aprotic solvent and surface-active agent as catalyst.

Certain carboxylic acid esters also containing a cyano group are prepared by reacting an acid halide, an aldehyde and a water-soluble cyanide in the presence of a water-immiscible aprotic solvent and an onium catalyst.

Certain carboxylic acid esters also containing a cyano group are prepared by reacting an acid halide, an aldehyde and a water soluble cyanide in the presence of a water-immiscible aprotic solvent and a macrocylic polyether catalyst.

Certain cyclopropanecarboxylic acid esters also containing a cyano group are prepared by reacting an aldehyde, a salt of hydrocyanic acid and a 2-halocyclobutanone in an aprotic solvent.

Meta-aryloxybenzaldehydes are prepared by treating a mixture of meta-aryloxybenzyl- and benzal halides with hexamethylenetetramine (or equivalent amounts of ammonia and formaldehyde) and hydrolyzing the resulting product under acid conditions.

Preparation of meta-aryloxy-benzaldehydes

3-Bromobenzaldehyde is prepared by treating benzaldehyde with bromine chloride in the presence of aluminum chloride and a solvent, under specified conditions.

Growing community of inventors

Amsterdam, Netherlands

Roger A Sheldon