Patent GB-935099-A (GB)
Title: New werner complexes and process for the manufacture thereof
Inventor: PIERRE MARIE JOSEPH GHISLAIN D
IPC: C07C7/152
Filed: 1960-07-19
Abstract: A mixture of xylenes may be resolved into its components by clathration using as clathrating agent a compound of the formula MA2Xn which is insoluble or sparingly soluble in water, wherein M is a bivalent metal of atomic number greater than 12, A is a monovalent polyatomic anion, and X is a primary, phenyl-substituted alkylamine of which the alkylamine contains from 1 to 12 carbon atoms, said substituent group being itself further substituted by a polarizable non-hydrocarbon radical, and n is either 2 or 4.  In an example [Ni(SCN)2{a -(p-bromophenyl)-ethylamine}4] is prepared and used as the clathrating agent in the following manner: a solution of a -(p-bromophenyl)-ethylamine in a mixture of the three xylenes is mixed with an aqueous solution of NiCl2.6H2O and KSCN and the resulting precipitate is decomposed by 6NHCl to obtain a product enriched in p-xylene.ALSO:The invention comprises Werner complexes of the general formula MA2Xn wherein M is a bivalent metal of atomic number greater than 12, A is a monovalent polyatomic anion, and X is a primary, phenyl substituted alkylamine of which the alkyl group contains from 1 to 12 carbon atoms, said substituent phenyl group being itself further substituted by a polarisable nonhydrocarbon radical, and n is either 2 or 4.  The bivalent metal preferably has an atomic number in the range of from 25 to 29, this range comprising nickel, cobalt, iron, manganese and copper. Preferably A is a monovalent triatomic anion which includes one carbon atom only, the carbon atom being either doubly or triply bonded to a nitrogen atom, e.g. the cyanate, thiocyanate and selenocyanate anions, or their -iso forms.  The alkyl group preferably has 1 to 5 carbon atoms, and the amine radical is advantageously in the alpha-position with respect to the phenyl group.  Polarisable non-hydrocarbon radicals mentioned are halogen, trifluoromethyl-, hydroxy-, alkoxy-, nitro-, cyano-, NN dialkylamino-, carbamyl-, sulphamyl- and carboalkoxy.  An extensive list of suitable amines is given, the following being typical:- o-chlorobenzylamine, a -(o-chlorophenyl)ethylamine, a -(p-bromophenyl) ethylamine, p-dimethylaminobenzylamine, a -(p-fluorophenyl)ethylamine, a -(p-iodophenyl) ethylamine, a -(p-bromophenyl)nonylamine, a -(p-methoxyphenyl)ethylamine, a -(p-butoxyphenyl)ethylamine and a -(m-nitrophenyl) ethylamine. In the examples [Ni(SCN)2\sTa -(p-bromophenyl)-butylamine\sV4], [Ni(SCN)2\sTa -(p-methoxyphenyl)-ethylamine\sV4], [Ni(SCN)2 \sTa (p-chlorophenyl)-hexylamine\sV4], [Ni(SCN)2 \sTa -(p-chlorophenyl)-dodecylamine\sV4] and [Ni (SCN)2\sTa -(p-bromophenyl)-ethylamine\sV2] are prepared by reacting the appropriate amine with Ni(SCN)2 prepared in situ from NiCl2.  6H2O and KSCN.  The preparation of the complexes containing only two molecules of the amine is identical with the preparation of amines containing four such molecules except that half the quantity of amine is used. The complexes may be used in solution as oxidation or polymerisation catalysts (e.g. in drying oils) or for impregnating catalytic masses.  In solid form, they can be used in heterogeneous catalysis or as clathrating agents, e.g. for separating pure isomers of xylene.