Process for the hydrogenation of ethylenically unsaturated organ

Details Process for the hydrogenation of ethylenically unsaturated organ Process for the hydrogenation of ethylenically unsaturated organ

1993-08-12

1995-06-20

Henley, III, Raymond

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acids and salts thereof

556 21, 556136, 502162, C07C22900, C07F 900, B01J 3100

Patent

active

054262160

DESCRIPTION:

BRIEF SUMMARY
This is a national-phase application filed under 35 USC 371 of PCT application FR 91/01077, filed Dec. 27, 1991.


FIELD OF THE INVENTION

The invention relates to the hydrogenation of ethylenically unsaturated organic compounds having at least one aliphatic C.dbd.C double bond. It comprises a process which makes it possible advantageously to carry out such an operation in a homogeneous medium, in the presence of a catalyst formed by a ruthenium complex. It further relates to a catalyst system of Ru with a phosphorus ligand which is capable of effecting asymmetric hydrogenation with an excellent yield and an enantiomeric excess.


PRIOR ART

Neutral ruthenium complexes of the structure bis(2-methylallyl)bis(phosphite)ruthenium are known to have been described in the article by M. COOKE et al., J. Chem. Soc. (A), pages 16-20 (1971). More precisely, these are complexes of the formula ##STR1## where compound (C1): L=(MeO).sub.3 P
It so happens that said article by M. COOKE et al. neither describes nor suggests the use of these five compounds in the field of the catalytic hydrogenation of ethylenically unsaturated compounds.
Furthermore, it is known that ionic ruthenium complexes have been recommended in the past for the catalytic hydrogenation of olefins. In this connection, see on the one hand EP-A-0 366 390, which recommends for this purpose the use of complexes of the formula or CH.sub.3 in the 4-position of each phenyl ring of the bis(diphenylphosphino) fragment, n=2, complexes of the formula
Furthermore, the article by T. OHTA et al., J. Org. Chem., 52, pages 3174-3176 (1987), has disclosed neutral ruthenium catalysts for the hydrogenation of carboxylic acids ethylenically unsaturated in the alpha,beta or beta,gamma-positions. These catalysts, which have the S or R configuration, are represented by the formulae ##STR2##


OBJECT OF THE INVENTION

There is a need for a novel technical solution for the catalytic hydrogenation of ethylenically unsaturated organic compounds which is different from the technical solutions recommended by the documents EP-A-0 366 390 and EP-A-0 272 787 and the article by T. OHTA et al. cited above.
The novel technical solution which has been researched is based on the use of neutral ruthenium complexes which are structurally analogous to the compound C5 according to the article by M. COOKE et al.


SUBJECT OF THE INVENTION

According to a first feature of the invention, a novel technical solution is recommended for the catalytic hydrogenation of ethylenically unsaturated organic compounds containing at least one aliphatic C.dbd.C double bond. In fact, it has so far never been contemplated to use a compound carrying allylic ligands as a catalyst. The references indicated above, and many others, refer to various complexes of Ru with phosphines which are used for the hydrogenation of C.dbd.C bonds in a homogeneous medium, but none of the catalysts contains an allylic ligand.
In contrast to this state of affairs, the present invention results from the surprising finding that phosphine complexes of Ru in which Ru carries two allylic ligands can catalyze the asymmetric hydrogenation of C.dbd.C bonds very effectively.
Thus the present invention comprises a process for the hydrogenation of ethylenically unsaturated organic compounds in a homogeneous medium with a (diphosphino)ruthenium complex as a catalyst, wherein, in this catalyst, a ruthenium atom carries two ligands formed by allylic groups.
According to a second feature of the invention, the compounds of formula (1) below, in which Q is other than CH.sub.2 CH.sub.2 when R.sup.1 .dbd.R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.methyl, are recommended as novel industrial products useful in the field of the catalytic hydrogenation of olefins and of ethylenically unsaturated organic compounds in general.


DETAILED DESCRIPTION OF THE INVENTION

The catalyst used according to the invention for the catalytic hydrogenation of ethylenically unsaturated compounds, and belonging to the group consisting of diallylic compounds of (diphosphino)rut

REFERENCES:
patent: 5004823 (1991-04-01), Devon et al.
patent: 5177231 (1993-01-01), Manimaran et al.
patent: 5190905 (1993-03-01), Kolich et al.
patent: 5198562 (1993-03-01), Noyuri et al.
patent: 5200539 (1993-04-01), Stanley et al.
patent: 5223648 (1993-06-01), Hermann et al.
Journal of Organic Chemistry, vol. 52, No. 14, 10 Jul. 1987, Easton U.S. pp. 3174-3176; T. Ohta, et al. "Asymmetric Hydrogenation of Unsaturated Carboxylic Acids Catalyzed by Binap-Ruthenium (II) Complexes".
Journal of the Chemical Society, Section A 1971, London, pp. 16-20; M. Cooke, et al. "Pi-Allylic Complexes of Ruthemium".

Affiliated with

Also associated with

Rating

Process for the hydrogenation of ethylenically unsaturated organ does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Process for the hydrogenation of ethylenically unsaturated organ, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for the hydrogenation of ethylenically unsaturated organ will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-1845214