GB827350A - Radio-oxonation of olefins - Google Patents

Abstract

Olefinic compounds are reacted with hydrogen and carbon monoxide in the presence of a salt, oxide or carbonyl of a catalytically active heavy metal in the presence of at least 0.001 kilowatt hours per hour of high energy ionising radiation per pound of olefin feed. The "high energy ionizing radiation" is defined as radiation from terrestrial sources consisting of photons having a wavelength less than 50 , such as gamma and X-rays, rapidly moving charged or uncharged particles of an atomic or subatomic nature having an energy above 30 EV., such as alpha particles and beta rays, and neutrons. The radiation can be obtained from any convenient source such as charged particle accelerators, e.g. Van de Graaf generators; linear accelerators; betatrons; and nuclear reactors, e.g. atomic piles. Materials from nuclear reactors, e.g. spent fuel elements; and materials made radioactive by insertion in a nuclear reactor, e.g. cobalt 60, can also be used. If the radiation is obtained from a nuclear reactor it is preferred to shield the reactor so that substantially only gamma radiation is received by the reactants. When using a radio isotope the oxo reactants may be flowed in, around or through the source. For example, to obtain gamma irradiation rods of cobalt 60 suitably clad in a protective coating such as stainless steel or aluminium can be disposed in the reactor with the reactors flowing about. In the examples a cobalt 60 pipe source of radiation is used.ALSO:Oxonated compounds are obtained by a process comprising reacting an olefinic compound with carbon monoxide and hydrogen in the presence of a salt, oxide or carbonyl of a catalytically-active heavy metal in the presence of at least 0.001 kilowatt hours per hour of high energy ionizing radiation per pound of olefinic feed. The "heavy metal" referred to is one having a specific gravity greater than 4, e.g. iron, cobalt, molybdenum and rhodium and suitable salts are those of stearic, palmitic, oleic, linoleic and naphthenic acids. The "high energy ionizing radiation" is defined as radiation from terrestial sources consisting of photons having a wavelength less than 50 , such as gamma and X-rays, rapidly moving charged or uncharged particles of an atomic or subatomic nature having an energy above 30 ev., such as alpha particles and beta rays, and neutrons. The radiation may be obtained from any convenient source such as charged particle accelerators, linear accelerators, betatrons and nuclear reactors. Materials from nuclear reactors and materials made radioactive by insertion in a nuclear reactor, e.g. cobalt 60, may also be used. In the examples: (a) propylene is oxonated in the presence of a carbonyl catalyst in the presence of a cobalt 60 pipe source of gamma radiation at 135 DEG C. and 3100 p.s.i.g.; the product is hydrogenated in the presence of a copper chromite catalyst at 145 DEG C. and under 3300 p.s.i. of hydrogen; and (b) heptene-1 is similarly oxonated.