| 摘要 |
1,191,815. Cobalt-containing phosphine complexes; oxo synthesis. SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ N.V. 26 Feb., 1969 [28 Feb., 1968], No. 10189/69. Heading C2C. A complex suitable for use as a catalyst in the oxo process and comprising cobalt, carbon monoxide and a secondary phosphine in which the phosphorus atom is linked to a non-acetylenic hydrocarbyl group, preferably having from 10 to 36 carbon atoms, and to a perhydropentalenyl group is obtained by combining an organic or inorganic cobalt salt with the said phosphine, e.g. in liquid phase, followed by reduction and carbonylation, e.g. by heating in an atmosphere of H 2 and CO. The cobalt salt may suitably be a carboxylate, e.g. acetate or octanoate or a chloride, fluoride, or sulphate or mixture of such salts. The reduction and carbonylation may be carried out prior to the use of the complex as catalyst or they may be effected in situ in the hydroformylation process. In another method the complex is obtained by heating dicobalt octacarbonyl with the phosphine ligand to replace one or more of the CO molecules. In an example a catalyst complex is prepared in situ from cobalt octanoate and eicosyl (octahydropentalenyl-1-) phosphine in a reactor which is charged with 1-dodecene and KOH and then closed and pressured with H 2 -CO gas. The reaction is conducted at 183-184‹ C. at 85 atmospheres to yield primary alkanols comprising mainly straight-chain n-tridecanol and some branched chain alkanols. The catalyst may be represented by the empirical formula [L m CO(CO) n ] x wherein L is a secondary phosphine of the defined type, m and n are integers whose sum is 4, and x is an integer from 1 to 3. The catalyst formed from eicosyl (octahydropentalenyl-1-)- phosphine may be in the form of a dimer of the formula or of the corresponding monomer. The oxo process is preferably carried out at a pressure of from 21 to 105 atmospheres and at between 100‹ C. and 300‹ C. and generally yields primary alcohols as main products, the alcohols when normal alkenes are used being predominantly normal straight-chain alcohols. The olefins used may be mono- or polyolefins, e.g. dienes, and may be straight- or branched-chain. Other olefinic compounds may also be used, e.g. unsaturated alcohols, aldehydes and acids which yield the corresponding compounds containing an aldehyde or OH group on one of the C atoms of the original olefinic bond, unsaturated aldehydes yielding principally diols. The secondary phosphines may be obtained by reacting a primary phosphine QPH 2 , wherein Q is a non-acetylenic hydrocarbyl group with 1,5-cyclooctadiene in the presence of a freeradical generating catalyst, e.g. a dialkyl peroxide which decomposes at 110‹ C. or higher, and in the absence of substantial amounts of oxygen. When the QPH 2 reactant is eicosyl phosphine a product consisting of approximately 84% of 9-eicosyl-9-phospha-bicyclononanes and about 16% of eicosyl-(octahydropentalenyl-1-) phosphine is obtained from which the latter is separated by a fractional precipitation method which also yields the tertiary phosphines-9-eicosyl-9-phospha-bicyclo[3,3,1]- nonane and 9-eicosyl-9-phospha-bicyclo[4,2,1]- nonane. They may also be obtained by reacting diethyl phosphite with, 1,5-cyclooctadiene to form diethyl-(octahydropentalenyl-1) phosphonate which upon treatment with a reducing agent, e.g. lithium aluminium hydride, a silane or a siloxane is reduced to the novel (octahydropentalenyl-1-) phosphine which is then reacted with an olefin in the presence of a free radical to yield the desired secondary phosphine. |
