| 摘要 |
Addition reactions between a compound containing an active hydrogen atom and a compound containing an unsaturated linkage both as defined below are effected in the presence as catalyst of a mixture of at least two alkali metals from non-successive periods of the Periodic Table. The compound with an active hydrogen may be:-(1) A carbocyclic or heterocyclic compound having attached to a nuclear unsaturated carbon atom, a hydrogen-bearing carbon atom of a hydrocarbon group. The ring may be aromatic or non-aromatic or may have both, fused or unfused, and suitable heterocyclic rings are pyridine, furan, thiophene, pyrrole, pyrazole, indole or carbazole. The hydrocarbon substitutent may be unsaturated but is preferably saturated, straight or branched chain or cyclic and may be substituted by an aryl group. The nucleus may be substituted by chlorine, methoxy, ethoxy or nitro-groups; hydroaromatic compounds preferably contain non-geminately arranged substituents. The unsaturated compound attaches itself to the hydrogen-bearing nuclearly-bound carbon atoms. Many are specified; (2) Unsubstituted aromatic mono- or poly-cyclic carbocyclic or heterocyclic compounds, e.g. benzene, naphthalene, anthracene, pyridine, furan, or thiophene; (3) Acyclic or cyclic compounds with an olefinic double bond, many monoolefines and cyclo-olefines being specified; (4) Ammonia and primary or secondary aliphatic amines of the formula R1R2NH where R1 and R2 are hydrogen or aliphatic radicals; (5) The corresponding phosphines, R1R2PH each of which attach the unsaturated compound to the nitrogen or phosphorus atom to form a primary, secondary or tertiary amine or phosphine. The unsaturated compound may be:-(1) A compound having a non-conjugated non-aromatic carbon-to-carbon double bond, many mono- and poly-olefines, both cyclic and acyclic being specified; (2) A compound containing a non-conjugated carbon-to-oxygen double bond in which the oxygen-bonded carbon carries no hydrogen, e.g. mono- and di-ketones either acyclic or cyclic; (3) An unsubstituted carbocyclic aromatic or heterocyclic compound or an alkyl-substituted derivative having at least one nuclear hydrogen atom; the active hydrogen compound adds on to the nucleus of such compounds. It is preferred to use at least an equimolar amount of the active hydrogen containing compound as compared to the unsaturated compound. Preferred conditions are 100 DEG - 350 DEG C. and 5-100 atmospheres using batch or continuous operation in glass or steel lined apparatus. An inert solvent may be added. The total alkali metal added may be 0,01-0,20 mole per mole of the active hydrogen containing compound, of which 1-99 mole per cent. may be of one metal the remainder being the other. Preferred combinations are lithium and potassium, lithium and caesium and potassium and caesium. Promoters may be added, e.g. fused ring polycyclic aromatic hydrocarbons, acetylenic hydrocarbons, heterocyclic compounds containing four or five carbons atoms and nitrogen in the ring, alcohols, carboxylic acids, ethers, organic nitrates and cyanides, hydrocarbon halides, and organic peroxy and compounds. The following reactions are exemplified:-(1) the addition of ethylene to toluene to give npropyl benzene and 3-phenyl pentane; (2) the addition of ethylene to alpha-methyl styrene; (4) the addition of propylene to toluene or 1-methyl-1-cyclohexane the latter giving 1-isobutyl-1-cyclohexene; (5) the addition of ethylene to cyclohexene to give ethylcyclohexenes; (6) the dimerisation of propylene to 4-methyl-1-pentene; (7) the codimerisation of ethylene and propylene giving pentene-1 and -2; (8) the polymerisation of ethylene to a light hydrocarbon oil. Specification 740,978 is referred to. |
