Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus esters
Patent
1995-08-07
1998-02-10
Ambrose, Michael G.
Organic compounds -- part of the class 532-570 series
Organic compounds
Phosphorus esters
558 77, 568454, C07F 96574, C07C 4549
Patent
active
057171262
DESCRIPTION:
BRIEF SUMMARY
This application was filed under 35 U.S.C. 371 and was based upon PCT International Application No. PCT/EP94/01999, which was filed on Jun. 20, 1994.
The present invention relates to phosphorus-containing calixarenes.
Carbonylation reactions are understood as meaning the production of oxygen-containing products by reacting an organic compound with carbon monoxide and preferably a further reactant, especially hydrogen, in the presence of a catalyst. An industrially particularly important reaction is the hydroformylation of olefins by reaction with carbon monoxide and hydrogen with formation of aldehydes which contain one carbon atom more than the starting materials. The catalysts used are group VIII transition metal complexes which contain phosporus-containing ligands, for example phosphites (cf. J. Falbe, New Synthesis with Carbon Monoxide, Springer Verlag, New York 1980).
In addition to cobalt catalysts rhodium catalysts have in recent years become increasingly important for the hydroformylation of lower .alpha.-olefins, since they permit reaction at a lower pressure. As a rule, triphenylphosphine is used in excess as the phosphorus ligand, a high ligand/rhodium ratio being required in order to increase the selectivity of the reaction to give the commercially desired n-aldehyde product.
In recent years, attempts have been made to obtain more effective phosphorus ligands for the hydroformylation. In addition to phosphites having different substituents, phosphites too were tested for their suitability as catalysts. When these form a coordinate bond with a transition metal center, phosphites give catalysts having higher activity, but the life of these catalyst systems is unsatisfactory owing to the considerable sensitivity of the phosphite ligands to hydrolysis. Bisaryldiol-substituted chelating polyphosphites, as described in EP-A 21 46 22, are said to have dramatically reduced sensitivity to hydrolysis. The rhodium complexes of these ligands are said to form extremely active hydroformylation catalysts. EP-A 213 639 describes chelate bisphosphites which have diorganophosphite functionality at one phosphorus atom and triorganophosphite functionality at the second phosphorus atom. EP-A 155 508 furthermore discloses the use of bis-aryldiol-substituted monophosphites in the rhodium-catalyzed hydroformylation of sterically hindered olefins, eg. isobutene. EP-A 472 071 discloses chelate bisphosphite ligands in which bis-aryldiols are linked via bisphosphite ester bridges to alkane-diols or o-aryldiols. Finally, diol- and triol-substituted mono-phosphites and their use in hydroformylation are described in EP-A 149 894, EP-A 96 988 and EP-A 96 986.
In the hydroformylation of olefins, depending on the double bond position at which the carbon monoxide undergoes addition, straight-chain aldehydes, which are referred to as n-aldehydes, or branched aldehydes, ie. isoaldehydes, are formed. This is shown schematically in equation (1): ##STR2## However, it is generally desirable for the fraction of n-aldehyde, referred to below as n-fraction, to be as large as possible compared with that of the isoaldehyde in the hydroformylation product, since the n-aldehydes lead to products having particularly advantageous plasticizer properties in the further processing of the aldehydes to plasticizer alcohols and plasticizers (cf. for example U.S. Pat. No. 4,426,542).
When the chelate bisphosphite ligands of the abovementioned prior art are used, hydroformylation products having a very high n-fraction of up 96% are obtained in the rhodium-catalyzed hydroformylation of olefins.
It is an object of the present invention to provide ligands for the rhodium- or ruthenium-catalyzed hydroformylation of olefins, with the aid of which the n-fraction in the hydroformylation product can be even further increased.
We have found that this object is achieved by phosphorus-containing calixarenes of the general formula I ##STR3## where n is an integer from 2 to 4, sulfonate or carboxylate, -C.sub.20 -alkyl and phenyl or phenoxy group which is unsubsti
REFERENCES:
patent: 4416829 (1983-11-01), Lee et al.
Khasnis, D.V. et al. Chemistry in Molecular Baskets: Variable Coordination 75, 253-256.
Kneuper Heinz-Josef
Langguth Ernst
Lorz Peter Michael
Paciello Rocco
Roper Michael
Ambrose Michael G.
BASF - Aktiengesellschaft
Shurtleff John H.
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