| 摘要 |
1,182,353. Phosphorus-containing cobalt hydrocarbonyls. MONTECATINI EDISON S.p.A. 1 Feb., 1967 [7 Feb., 1966], No. 4965/67. Heading C2C. [Also in Division C5] The invention comprises cobalt hydrocarbonyls having the formula HCo(CO) 2 (PR 3 ) 2 , wherein R is a C 1 -C 10 alkyl group. They may be obtained either (a) by reacting a cobalt carbonyl [Co(CO) 3 (PR 3 )] 2 in hydrocarbon solution at 50-200‹ C. under hydrogen pressure (generally 20-30 atm.) with a trialkyl phosphine (PR 3 ) in the presence of an aliphatic alphaolefin, (b) by heating at 140-180‹ C. under hydrogen pressure a hydrocarbon solution of the said carbonyl of the formula [Co(CO) 3 (PR 3 )] 2 with a stoichiometric excess of a trialkyl phosphine (PR 3 ), or (c) by direct synthesis from a cobalt (Co++) hydrocarbon-soluble salt of an organic acid (e.g. cobalt 2-ethyl hexanoate), a trialkyl phosphine (PR 3 ) and carbon monoxide in a molar ratio Co: CO: PR 3 =1 2 : 2 in hydrocarbon solution at 100-180‹ C. under hydrogen pressure. The products are useful as hydrogenation catalysts, e.g. for the hydrogenation of saturated and unsaturated aldehydes, ketones, alkenes or alkynes and examples are given for the preparation of the hydrocarbonyls and for the hydrogenation of acetone to isopropyl alcohol using HCo(CO) 2 [P(C 2 H 5 ) 3 ] 2 and HCo(CO) 2 [P(C 4 H 9 ) 3 ] 2 respectively as catalysts, of n-butyraldehyde to n-butyl alcohol using HCo(CO) 2 [P(nC 6 H 3 ) 3 ] 2 as catalyst and of 2-ethyl hexenol to 2-ethyl hexanol using HCo(CO) 2 [P(C 2 H 5 ) 3 ] 2 as catalyst. The compound [Co(CO) 3 P(C 2 H 5 ) 3 ] 2 is obtained by reacting Co 2 (CO) 8 with P(C 2 H 5 ) 3 in n-heptane at room temperature in an autoclave which has been swept out with nitrogen, removing the carbon monoxide released and then heating at 70‹ C. Reference has been directed by the Comptroller to Specification 942,435. |
