Ethyl Corporation

Albemarle Corporation

Ethyl Corportation

Charles R Everly

Joe D Sauer

Jerry M Roper

Ronny W Lin

Steven P Diefenbach

John Y Lee

John M Power

Niomi L Krzystowczyk

Gunner E Nelson

Chi Hung Cheng

Won S Park

David W Owens

K Pushpananda Senaratne

Gene C Robinson

Arcelio J Malcolm

Stephen E Belmont

Yunqi Liu

Andrew O Wikman

Fluoroaryl Grignard reagents are produced from a hydrocarbyl Grignard reagent and fluoroaromatic compounds via separate additions of different fluoroaromatic compounds, such that the conversion of hydrocarbyl Grignard reagent to the desired fluoroaryl Grignard reagent is essentially complete, and thus the reaction product is free or essentially free of agents that may negatively affect subsequent reactions. The fluoroaryl Grignard reagents may be further reacted with boron trihalides in order to obtain tris(fluoroaryl)boranes or tetrakis(fluoroaryl)borates.

Clean generation of a fluoroaryl grignard reagent

Tri- or tetrafluorophthalimides are produced in a halogen-exchange reaction utilizing a metal fluoride salt and a dihydrocarbyl sulfoxide as the solvent. No phase-transfer catalyst is employed. The process has been found capable of producing the fully fluorinated phthalimide in yields of over 90% GC in reactions performed at 135-155 &deg; C. in reaction periods of as little as one hour even though no phase-transfer catalyst is employed.

Process for making fluorophthalimides

Perfluoroaryl Grignard reagents are produced from a hydrocarbyl Grignard reagent and polyhaloaromatic compounds via separate additions of different polyhaloaromatic compounds, such that the conversion of hydrocarbyl Grignard reagent to the desired perfluoroaryl Grignard reagent is essentially complete, and thus the reaction product is free or essentially free of agents that may negatively affect subsequent reactions. The perfluoroaryl Grignard reagents may be further reacted with boron trihalides in order to obtain tris(perfluoroaryl)boranes or tetrakis(perfluoroaryl)borates.

Clean generation of a perfluoroaryl grignard reagent

A mixture formed from one or more alkyl disulfides, benzene, and at least about 1.5 equivalents of Lewis acid catalyst is heated to form alkanethiobenzene. Reaction in a mixture formed from excess benzene, dimethyldisulfide (DMDS) and AlCl.sub.3 in which the mole ratio of AlCl.sub.3 to DMDS was 2:1 was complete in 2 hours and afforded 98% conversion and 93% yield of thioanisole. In contrast, the same reaction when attempted using a 1:1 mole ratio of AlCl.sub.3 to DMDS after 6 hours achieved only 66% conversion and a thioanisole yield of only 35%. So far as is known, this is the first example of a highly efficient electrophilic aromatic substitution of the inactivated benzene ring by an alkanethio group.

Alkanethiolation process

Improved process for separating ethylsilane from silane by selective adsorption onto an effectively treated carbon bed and method of treatment of such carbon bed to enhance the selective adsorption of ethylsilane.

Silane compositions and process

Silane and monoalkylsilanes can be alkylated using an alkali metal aluminate, MAlR.sub.4, wherein M is Li, Na, or K and each R is a straight chain, alkyl radical solely composed of carbon and hydrogen containing from about 4 to about 18 carbon atoms. The aluminate can be used as a reactant, optionally in the presence of a straight chain alpha-olefin corresponding to the alkyl group in the aluminate. Alternatively, the aluminate can be used as a catalyst for the reaction of the olefin and the silane reactant, in which case from about 5 to about 10 mole percent of the aluminate (based on the silane reactant) is employed. The catalytic reaction is promoted by a smaller amount of a lithium salt such as lithium chloride. Both embodiments are conducted at somewhat elevated temperatures, approximately 160.degree.-210.degree. C., and at autogenous pressures, using reaction times of 8-20 hours. The products are useful as functional fluids or as intermediates.

Formation of alkylsilanes

Novel 4-(.alpha.,.alpha.-dihydrocarbyl-.alpha.-cyano-methyl)-2,6-mono or dihydrocarbyl substituted phenols are prepared by reacting a 2,6-mono or dihydrocarbyl substituted phenol with a ketone and an alkali metal cyanide or an alkaline earth metal cyanide in an inert reaction solvent.

Preparation of

Novel bis(3',5'-mono or dihydrocarbyl-4'-hydroxybenzyl)-1,3-diketones are prepared by reacting a (3',5'-mono or dihydrocarbyl-4'-hydroxybenzyl)-1,3-diketone with an N,N-dihydrocarbyl-2,6-mono or dihydrocarbyl-4-aminomethylphenol and an alkyl halide in the presence of an alkaline earth metal halide. The products are useful as antioxidants.

Chemical process

4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)2,6-di-hydrocarbyl-substituted phenols having the formula ##STR1## wherein R.sub.1 and R.sub.2 are the same or different monovalent substituents selected from the group consisting of alkyl, aralkyl and cyclic alkyl radicals and R.sub.3 is selected from hydrogen, hydrocarbyl radicals, substituted hydrocarbyl radicals and hydrocarbyloxy radicals are prepared by reacting an N,N-di-hydrocarbyl-4-(.alpha.-hydrocarbyl-.alpha.-aminomethyl)2,6-di-hydro carbyl-substituted phenol having the formula ##STR2## wherein R.sub.1, R.sub.2 and R.sub.3 are as defined above and R.sub.4 and R.sub.5 are the same or different and are selected from hydrogen, hydrocarbyl radicals and substituted hydrocarbyl radicals with an alkali metal cyanide or an alkaline earth metal cyanide in a suitable solvent. The 4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)2,6-di-substituted phenol thus formed can readily be converted to the corresponding 4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)phenol by dealkylating the substituent groups ortho to the hydroxyl group from the 4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)2,6-di-substituted phenol which then can be converted on hydrolysis to the corresponding .alpha.-hydrocarbyl-4-hydroxyphenylacetic acid. These acids have utility as insecticidal and acaricidal intermediates and are deemed to have utility as insecticides themselves as are the 4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)2,6-di-substituted phenols of the present invention.

Method of preparing

4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)2,6-di-substituted phenols having the formula ##STR1## wherein R.sub.1 and R.sub.2 are the same or different monovalent substituents selected from the group consisting of alkyl, aralkyl and cyclic alkyl radicals and R.sub.3 is selected from hydrogen, hydrocarbyl radicals, substituted hydrocarbyl radicals and hydrocarbyloxy radicals are prepared by reacting a 4-(.alpha.-hydrocarbyl-.alpha.-hydrocarbyloxymethyl)2,6-di-substituted phenol having the formula ##STR2## wherein R.sub.1, R.sub.2 and R.sub.3 are as defined above and R.sub.4 is selected from hydrocarbyl radicals or substituted hydrocarbyl radicals with an alkali metal cyanide or an alkaline earth metal cyanide in a suitable solvent. The 4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)2,6-di-substituted phenol thus formed can readily be converted to the corresponding 4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)phenol by dealkylating the substituent groups ortho to the hydroxyl group from the 4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)2,6-di-substituted phenol which then can be converted on hydrolysis to the corresponding .alpha.-hydrocarbyl-4-hydroxyphenylacetic acid. These acids have utility as insecticidal and acaricidal intermediates and are deemed to have utility as insecticides themselves as are the 4-(.alpha.-hydrocarbyl-.alpha.-cyanomethyl)2,6-di-substituted phenols of the present invention.

4-(.alpha.-hydrocarbyl-.alpha.-cyano-methyl)2,6-di-substituted phenols having the formula ##STR1## wherein R is selected from hydrogen, hydrocarbyl radicals, substituted hydrocarbyl radicals and hydrocarbyloxy radicals and R.sub.1 and R.sub.2 are the same or different monovalent substituent selected from the group consisting of alkyl, aralkyl and cyclic alkyl radicals and are prepared by reacting a di-substituted phenol having the formula ##STR2## when R.sub.1 and R.sub.2 are as defined above with an aldehyde having at least one aldehyde radical and containing an R group as defined above and an alkali metal cyanide or an alkaline earth metal cyanide in a suitable solvent. The 4-(.alpha.-hydrocarbyl-.alpha.-cyano-methyl)2,6-di-substituted phenol thus formed can readily be converted to the corresponding 4-(.alpha.-hydrocarbyl-.alpha.-cyano-methyl)-phenol by dealkylating the substituent groups ortho to the hydroxyl group from the 4-(.alpha.-hydrocarbyl-.alpha.-cyano-methyl)-2,6-di-substituted phenol which then can be converted on hydrolysis to the corresponding .alpha.-hydrocarbyl-4-hydroxyphenylacetic acid. These acids are insecticidal and acaricidal intermediates and are deemed to have utility as insecticides themselves as are the 4-(.alpha.-hydrocarbyl-.alpha.-cyano-methyl)2,6-di-substituted phenols of the present invention.

Preparation of 4-(.alpha.-alkyl-.alpha.-cyano-methyl)-2,6-di-substituted

Esters of 3,5-dihydrocarbyl-4-hydroxybenzylmalonic acid are prepared by reacting a 2,6-dihydrocarbyl-4-hydroxymethylphenol with an ester of a 1,3-dicarboxylic acid in the presence of an alkali or an alkaline earth metal hydride. The products are useful as antioxidants.

Process for the preparation of 3,5-dihydrocarbyl-4-hydroxybenzylmalonic

Esters of 3,5-dihydrocarbyl-4-hydroxybenzylmalonic acid are prepared by reacting a 2,6-dihydrocarbyl-4-halomethylphenol with an ester of a 1,3-dicarboxylic acid in the presence of an alkali or an alkaline earth metal hydride. The products are useful as antioxidants.

Novel (3',5'-dihydrocarbyl-4'-hydroxybenzyl)-1,3-diketones are prepared by reacting an N,N-dihydrocarbyl-2,6-dihydrocarbyl-4-aminomethylphenol with a 1,3-diketone in the presence of a basic substance. The products are useful as antioxidants.

Chemical process for preparing 1,3 diketones

Novel (3',5'-dihydrocarbyl-4'-hydroxybenzyl)-1,3-diketones are prepared by reacting an N,N-dihydrocarbyl-2,6-dihydrocarbyl-4-aminomethylphenol with a 1,3-diketone and an alkyl halide in the presence of an alkali or an alkaline earth metal hydride. The products are useful as antioxidants.

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Baton Rouge, LA, United States of America

Charles R Everly