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    • 1. 发明授权
    • Oxo alcohols using catalysts comprising ditertiary phosphines
    • 使用包含文献磷酸酯的催化剂的OXO酒精
    • US3527818A
    • 1970-09-08
    • US3527818D
    • 1968-06-05
    • SHELL OIL CO
    • MASON RONALD FWINKLE JOHN L VAN
    • B01J31/16B01J31/20B01J31/24C07C29/16C07F9/6568C07F15/06
    • C07F9/65683B01J31/20B01J31/2414B01J2531/845C07C29/16C07C31/125
    • 1,127,965. Hydrocarbylene-his (monophosphabicyclo hydrocarbons); cobalt-containing complexes. SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ N.V. 24 Nov., 1966 [26 Nov., 1965], No. 52662/66. Heading C2C. [Also in Division B1] Novel hydrocarbylene - bis (monophosphabicyclo hydrocarbons) where the hydrocarbylene group may contain one or more functional groups as substituents and in which, in each bicyclic structure, the phosphorus atom, being linked to the hydrocarbylene group, is a member of a ring without being a bridge-head atom and the smallest phosphorus-containing ring consists of at least 5 atoms, are prepared by reacting a secondary phosphine, preferably a bicyclic heterocyclic secondary phosphine, with a polyolefinic compound containing at least two isolated ethylenic bonds in the presence of a free-radical-generating catalyst and in the absence of substantial amounts of oxygen. Specified catalysts are azonitriles, a dialkyl or diacyl peroxide, actinic radiation and high energy or ionizing radiation. Typical products may be represented by the formula where Q is hydrocarbylene, y, z, y 1 and z 1 each represent integers of 1 or more and y + z = 3 and y 1 + z 1 = 3, R is hydrogen or C 1-4 alkyl. Specified functional substituents are carbonyl, carboxyl, nitro, amino, hydroxy, cyano, sulphonyl and sulphoxyl. The compounds may also be prepared by reacting a diprimary hydrocarbylene phosphine with a cyclo-octadiene in the presence of a free radical-generating catalyst and in the substantial absence of oxygen. The novel compounds are used as phosphine ligands in complexes containing cobalt, e.g. cobalt carbonyl. Such complexes are used as catalysts for the production of alcohols and/or aldehydes by the reaction of olefins with CO and H 2 , and the catalysts may be prepared in situ, e.g. from cobalt octanoate. The hydroformylation of 1-dodecene is described.