Rhone-Poulenc Chimie

Rhodia Chimie

Centre National De La Recherche Scientifique

Societe Nationale Des Poudres Et Explosifs

Atofina

Rhodia Fiber & Resin Intermediates

Institut National De Recherche Chimique Appliquee Ircha

Francois Mathey

Michel Spagnol

Francois Mercier

Frederic Robin

Virginie Mouries

Philippe Savignac

Fr&eacute;d&eacute;ric Robin

Jean Malinge

Paolo Burattin

Anne Breque

Hubert Bonnard

Eliane Deschamps

Francois Nief

Bernard Deschamps

Frederic Eymery

Francois-Xavier Buzin

Guillaume De Lauzon

Georges Muller

The invention relates to novel bridged biphosphole ligands according to the general formula:where R, R, Rare chosen from hydrogen, alkyl, aryl or silyl, Ris chosen from hydrogen, alkyl, aryl or halogen, Rpossibly being replaced with a direct bond between the two phosphorus atoms and T is a divalent group. The invention also relates to metallocenes obtained from these ligands. These metallocenes are useful as catalytic components for the polymerization of olefins.

Bridged biphospholes and metallocenes prepared therefrom

New optically active bis&lsqb;1-phospha-2,3-diphenyl-4,5-dimethylnorbornadiene&rsqb; diphosphines and new optically active transition metal complexes with said phosphines are described. The complexes are useful as catalysts to promote hydrogenation of substrates.

Optically active diphosphines, preparation thereof according to a process for the resolution of the racemic mixture and use thereof

A process for separating the (d/l) and (meso) diastereoisomers of bis-&lsqb;1-phospha-2,3-diphenyl-4,5-dimethylnorbornadiene&rsqb; comprising converting the mixture of diastereoisomers of bis-&lsqb;1-phospha-2,3-diphenyl-4,5-dimethylnorbornadiene&rsqb; to a mixture of the corresponding diastereoisomers of diphosphine disulphide or dioxide, then in separating the two diastereoisomers in dioxide or disulphide form.

Method for separating a diphosphine diastereoisomers

6,6&prime;-bis-(1-phosphanorbornadiene) diphosphines, their preparation and their uses

Furylphosphines and organometallic complexes containing them

The present invention relates to optically active diphosphines. It is also targeted at their preparation according to a process for the resolution of the racemic mixture of the said phosphines to optically active isomers. The subject of the invention is new optically active bis&lsqb;1-phospha-2,3-diphenyl-4,5-dimethylnorbornadiene&rsqb; diphosphines and a process for resolving the racemic bis&lsqb;1-phospha-2,3-diphenyl-4,5-dimethylnorbornadiene&rsqb; mixture which comprises reacting it with a palladium or platinum complex as chiral auxiliary in an organic solvent, thus forming diastereoisomer complexes, and then resolving the said optically pure complexes. The invention also relates to new optically active metal complexes comprising the said phosphines and to their use in a process for the preparation of optically active carboxylic acids and/or derivatives according to a process for the hydrogenation of &agr;,&bgr;-unsaturated carboxylic acids and/or derivatives.

6&prime;,6-bis-(1-phosphanorbornadiene) diphosphines

Asymmetric hydrogenation method of a ketonic compound and derivative

The present invention relates to optically active diphosphines. It is also targeted at their preparation according to a process for the resolution of the racemic mixture of the said phosphines to optically active isomers. The subject of the invention is new optically active bis[1-phospha-2,3-diphenyl-4,5-dimethylnorbornadiene] diphosphines and a process for resolving the racemic bis[1-phospha-2,3-diphenyl-4,5-dimethylnorbornadiene] mixture which comprises reacting it with a palladium or platinum complex as chiral auxiliary in an organic solvent, thus forming diastereoisomer complexes, and then resolving the said optically pure complexes. The invention also relates to new optically active metal complexes comprising the said phosphines and to their use in a process for the preparation of optically active carboxylic acids and/or derivatives according to a process for the hydrogenation of .alpha.,.beta.-unsaturated carboxylic acids and/or derivatives.

Optically active diphosphines, preparation thereof according to a

The phospholes and P-functional phospholes correspond to the general formula: ##STR1## in which: R.sub.1 and R.sub.2 are identical or different and represent hydrogen or a lower alkyl group of C.sub.1 to C.sub.4 such as a methyl group, and R.sub.3 represents an aryl group (such as --C.sub.6 H.sub.5) or a substituted aryl group (such as --CH.sub.2 C.sub.6 H.sub.5) or an alkyl group (such as --CH.sub.3, --C.sub.2 H.sub.5, --C.sub.3 H.sub.7 to C.sub.12 H.sub.25) or a --(CH.sub.2).sub.n Z group where Z denotes a function of the --COO-alkyl type (such as --COOC.sub.2 H.sub.5), --CH, --CO-aryl (such as --COC.sub.6 H.sub.5), --CO-alkyl (such as --COCH.sub.3) or --OH and n.gtoreq.1. At least one alkyl- or arylhalogeno phosphine is reacted with a butadiene whose carbons in the 2 and/ or 3 positions carry possibly a lower alkyl substituent, the cyclic adduct resulting from this reaction is then subjected to the action of a tertiary amine selected from among those having a pKa comprised between 5 and 11, then the product obtained is functionalized if the corresponding P-functional product is desired. Some of the phospholes thus produced are novel, particularly those of the above formula wherein R.sub.3 =--(CH.sub.2).sub.n Z such as above defined with n.noteq.2 for Z=CN.

Phospholes with functional substituents on the phosphorus and process

The invention relates to the manufacture of 1,1'-diphosphaferrocenes. The process consists of reacting a mixture of an alkali metal phenyl and an alkali metal phospholyl in the presence of a Lewis acid, in a basic ether, preferably at between -20.degree. and +20.degree. C., and then reacting the product obtained with ferrous chloride. The process according to the invention is useful for lowering the production cost of 1,1'-diphosphaferrocenes.

Process for the synthesis of 1,1-diphosphaferrocenes

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Paris, France

Francois Mathey