| 摘要 |
1,254,063. Hydroformylation process; cobaltsecondary phosphine - carbon monoxide - complexes. SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ N.V. 26 Feb., 1969 [28 Feb., 1968], No. 10188/69. Headings C2C and C2P. Aldehydes and/or alcohols are obtained by a hydroformylation process comprising reacting olefines with CO and H 2 in the presence of a novel complex catalyst comprising cobalt, CO and a bicyclic heterocyclic secondary phosphine in which a phosphorus-containing heterocyclic ring with at least five carbon atoms is present. The catalyst is suitably one of the formula [L m Co(CO) n ] x wherein L is the defined heterocyclic secondary phosphine, m and n are positive integers, m + n is 4, and x is an integer from 1 to 3. The bicyclic secondary phosphines are generically monophosphabicycloalkanes having 8 or 9 ring atoms in which the smallest phosphorus-containing ring contains at least 5 atoms and the phosphorus atom is a member of a bridge linkage and in which the ring carbon atoms are unsubstituted or substituted, e.g. by C 1 -C 4 alkyl groups. The preferred secondary phosphine is monophosphabicyclononane and a particularly preferred catalyst is cobalt-tricarbonyl - 9 - phosphabicyclo 3,3,1 - nonane believed to be dimeric and to have the formula The process may be applied to the hydroformylation of C 2 -C 19 mono-olefines and may be carried out at 28 to 85 atmospheres pressure and at 125‹ to 210‹ C. Examples are given for the hydroformylation of 1-dodecene and propylene, respectively, to form mainly the corresponding primary alcohol in each case. The complexes used as catalyst may be prepared by combining an inorganic or organic cobalt salt with the appropriate phosphine ligand in liquid phase and then heating the solution in an atmosphere of hydrogen and carbon monoxide, the latter step, if desired, being carried out in situ in the hydroformylation process. The catalysts may also be prepared from a carbon monoxide complex of cobalt, e.g. by heating di-cobalt octacarbonyl with a suitable phosphine ligand, e.g. in a hydrocarbon solvent, to replace one or more of the carbon monoxide molecules. The bicyclic heterocyclic secondary phosphines may be obtained by reacting phosphine with an appropriate cyclic hydrocarbon containing two ring non-conjugated and non-homoconjugated double bonds and an example is given for the production of a mixture of 9- phosphabicyclo[4.2.1]nonane and 9-phosphabicyclo[3.3.1]nonane by reacting 1,5-cyclooctadiene with phosphine in deaerated pentane in the presence of azobisisobutyronitrile and in an oxygen-freed pressure vessel. Exposure of the phosphine product to air yields the secondary phosphine oxide and phosphinic acid. Specification 1,109,787 is referred to. |
