Patent GB-1109787-A (GB)
Title: New phosphine derivatives and their use in the hydroformylation of olefinic compounds
IPC: C07C45/49
Filed: 1966-03-28
Abstract: Aldehydes and/or alcohols are prepared by reacting an olefin, CO and H2 in the presence of a novel complex catalyst comprising Co, CO and a heterocyclic phosphine in which a heterocyclic group with at least 5 carbon atoms is present.  The phosphines may be tertiary 6-membered heterocyclic phosphines where the bridge is composed solely of carbon and hydrogen atoms and may be substituted by a wide range of aliphatic, cycloaliphatic or aromatic hydrocarbons, each containing no more than 10 carbon atoms, and all such substituents combined containing less than 40 carbon atoms. The phosphines may contain functional groups such as carbonyl, carboxyl, nitro, amino, hydroxy, cyano, sulphonyl and sulphoxyl. The phosphorus atom may be linked to a hydrocarbyl radical which preferably contains 4-36 carbon atoms. Tertiary 7-membered heterocyclic phosphines, substituted as above, can also be used, preferably with the bridge and its substituents containing 6-34 carbon atoms; the total number of carbon atoms in the ligand being less than 48.  Bicyclic heterocyclic tertiary phosphines having 8-9 ring atoms, including phosphorus, in which the smallest ring contains at least 5 atoms and the phosphorus atom is not a bridgehead atom are especially preferred.  Bicyclic tertiary phosphines that are unsaturated in the bicylic portion of the ligand are very suitable and usually contain 8-44 carbon atoms.  In the bicyclic phosphines the substituents may be selected from the same range as for the monocyclic phosphines and the hydrocarbyl group linked to the phosphorus atom preferably has 1-36 carbon atoms.  The novel catalysts may be monomeric or polymeric, e.g. cobalt-tricarbonyl - 9 - phenyl - 9 - phosphabicyclo[4,2,1]-nonane which is believed to be dimeric.  The catalysts can be prepared by combining organic or inorganic cobalt salts, e.g. carboxylates, octanoates, chlorides and sulphates or a mixture of salts containing a cobalt alkanoate of 6-12 carbon atoms, with the desired phosphine ligand in the liquid phase.  An atmosphere of H2 and CO is then used to reduce the valence state of the cobalt.  The reduction can be performed prior to, or simultaneously with, the hydroformylation process and the catalyst may thus be formed in situ.  The catalysts can also be prepared by heating a carbon monoxide complex of cobalt with a suitable phosphine ligand; in a hydrocarbon solvent if desired.  Temperatures of 100-300 DEG  C. at 1-340 atm. can be used. The process is generally applicable to the hydroformylation of aliphatic or cycloaliphatic compounds having at least one aliphatic double bond such as mono-olefins, cyclopentene and dihydronaphthalene.  Non-hydrocarbons such as olefinically unsaturated alcohols, aldehydes and acids may be converted to the corresponding alcohols, aldehydes and acids having an aldehyde or hydroxy group on one of the carbon atoms previously involved in the double bond.  Examples given include: vinyl chloride, allyl acetate, and diethyl maleate.  The 6- and 7-membered tertiary heterocyclic phosphines can be prepared by reacting divinyl substituted hydrocarbons, e.g. dienes, containing 2 non-conjugated double bonds with primary phosphines in the presence of a free radical generating catalyst and in the absence of substantial amounts of oxygen.  The free radical generating catalysts can include actinic radiation but are preferably dialkyl peroxides.  The bicyclic heterocyclic phosphines are prepared by reacting a cyclic hydrocarbon containing 2-ring non-conjugative and non-homoconjugative double bonds with phosphine or a primary phosphine in the presence of a free radical generating catalyst in the absence of substantial amounts of oxygen and are included in the invention per se.  An alternative method comprises the above described reaction of a cyclic diene with PH3 followed by reaction with a cyclic or non-cyclic compound, having at least one ethylenic double bond, in the presence of a free radical generating catalyst to produce a tertiary bicyclic phosphine.