| 摘要 |
Mono- or di-nitriles of aromatic or heterocyclic compounds are prepared by treating an alkyl-substituted (but otherwise unsubstituted) aromatic or heterocyclic compound with ammonia in the presence of a catalyst comprising a semiporous refractory solid having a heavy-metal ion capable of forming a Werner ammine complex ionically combined therewith, the reaction being effected at 850-1200 DEG F. at atmospheric, raised or reduced pressure with a contact time between 0.01 sec. and 20 minutes and with the use of at least 2 mols., preferably 10-100 mols., of ammonia per mol. of aromatic or heterocyclic compound. Aromatic or heterocyclic compounds specified as suitable for treatment are toluene, ethylbenzene, diethylbenzenes, xylenes, trimethylbenzenes, methylnaphthalenes, methylanthracenes, methylpyridines, 2, 4- and 2, 5-butidines, methylthiophene, methylfuran, methyloxazole and 2-methylpyrimidine. The catalyst may be (1) a mineral containing an appropriate heavy metal in its lattice, e.g. cahnite, almandite, siderite or certain spinels, or (2) a mineral into which an appropriate heavy-metal ion has been introduced by base-exchange, a number of minerals being specified in this connection, or (3) a synthetic zeolite or molecular sieve into which the desired heavy metal ion has been incorporated by base-exchange. A heavy metal is defined as a metal having an atomic number of 23-30, 43-48 or 75-80, all inclusive. Specified heavy metals are chromium, cobalt, nickel, copper, zinc, palladium, silver and platinum. Examples are given in which (1) toluene and ammonia yield benzonitrile in the presence of an artificial zeolite into which various heavy-metal ions have been introduced by base-exchange and (2) similarly, p-xylene yields p-tolunitrile and a small proportion of terephthalonitrile.ALSO:Catalysts for making di-nitriles comprise a semi-porous refractory solid having a heavy-metal ion capable of forming a Werner ammine complex ionically combined therewith. The catalyst may be (1) a mineral containing an appropriate heavy metal in its lattice, e.g. cahnite, almandite, siderite or certain spinels, or (2) a mineral into which an appropriate heavy-metal ion has been introduced by base-exchange, a number of minerals being specified in this connection, or (3) a synthetic zeolite or molecular sieve into which the desired heavy metal ion has been incorporated by base-exchange. A heavy metal is defined as a metal having an atomic number of 23-30, 43-48, or 75-80, all inclusive. Specified heavy metals are chromium, cobalt, nickel, copper, zinc, palladium, silver, and platinum. The catalyst may be used alone or on a support and may be activated by heating at a temperature up to 700 DEG C. in vacuo or in a gas. After use, the catalyst may be regenerated by heating at 1000 DEG F. in an oxygen-containing gas. Examples are given. |
