Patent GB-937791-A (GB)
Title: Process for clathration of organic aromatic compounds by means of werner complexes
Inventor: PIERRE MARIE JOSEPH GHIS LAIN
IPC: C07F15/04
Filed: 1960-10-11
Abstract: A mixture of aromatic compounds containing at least one compound clathratable by a Werner complex of formula Ni(SCN)2X4, X being a primary phenyl-substituted alkylamine, the phenyl group itself being substituted or unsubstituted and the alkyl chain containing from 1 to 30 carbon atoms, may be resolved by contacting the mixture with a Werner complex of formula Ni(SCN)2X4, said complex having been formed from a Werner complex of formula Ni(SCN)2X2 in the presence of the clathratable compound(s), to form a clathrate and dissociating the clathrate. The clathrate may be formed in any of the following ways: (1) by contacting the mixture with a Werner complex of formula Ni(SCN)2X2, and adding to the contacted mixture further primary phenylsubstituted alkylamine (2) by adding a Werner complex of formula Ni(SCN)2X2 to the mixture containing further primary phenyl-substituted alkylamine (3) by heating a Werner complex of formula Ni(SCN)2X4 in the presence of the mixture to a temperature sufficient to bring about complete dissociation of the Werner complex into Ni(SCN)2X2 and 2X, and then cooling to effect recombination of the dissociated components to form of clathrate consisting of Ni(SCN)2X4 and the clathratable compound(s).  The dissociation may be effected by heating the clathrate, or by treatment with a mineral acid which does not react with the clathrated compound(s), or by treatment with heated water vapour, or by elution with an inert solvent, e.g. pentane, hexane or cyclohexane.  Many of the Werner complexes which may be used in the process of the invention are described and claimed in Specifications 931,775 and 935,099.  At least one of the four molecules of combined primary phenyl-substituted alkylamine may be different from the others.  In examples the following mixtures are clathrated using a large number of Werner complexes, one or more of the components being selectively clathrated: (1) to (3) o- and p-xylenes (4) the xylenes (5) the xylenes and ethylbenzene (7) the cymenes (8) a - and b -methylnaphthalenes (9) 2,3- and 2,6-dimethylnaphthalenes (10) n- and isopropylbenzenes; n-, iso-, sec-, and tert.- butylbenzenes, styrene and ethylbenzene; the diethylbenzenes; the ethyltoluenes; the ethylisopropylbenzenes; the cycohexyltoluenes; the trimethylbenzenes; o-ethyltoluene and mesitylene; the dimethylethylbenzenes; naphthalene, tetralin and decalin; naphthalene and diphenyl; and a - and b -ethylnaphthalenes.  Specification 811,137 also is referred to.ALSO:The invention comprises a clathrate consisting of a Werner complex of formula Ni(SCN)2X4, X being a primary phenylsubstituted alkylamine, the phenyl group being itself either substituted or unsubstituted and the alkyl chain containing from 1 to 30 carbon atoms, and one or more aromatic compounds; a process for preparing the same by contacting with a Werner complex of formula Ni(SCN)2X4 at least one aromatic compound clathratable by said Werner complex, said Werner complex having been formed from a Werner complex of formula Ni(SCN)2X2 in the presence of said clathratable compound or compounds; and a method of resolving mixtures of aromatic compounds by clathration.  The clathrate may be formed in any of the following ways (1) by contacting a mixture including at least one clathratable compound with a Werner complex of formula Ni(SCN)2X2, and adding to the contacted mixture further primary phenyl-substituted alkylamine, (2) by adding a Werner complex of formula Ni(SCN)2X2 to a mixture including at least one clathratable compound and further primary phenyl-substituted alkylamine, (3) by heating a Werner complex of formula Ni(SCN)2X4 with at least one clathratable compound to a temperature sufficient to bring about complete dissociation of the Werner complex into Ni(SCN)2X2 and 2X, and then cooling to effect recombination of the dissociated components to form a clathrate consisting of Ni(SCN)2X4 and said clathratable compound or compounds. A mixture of aromatic organic compounds which contains at least one compound clathratable by Ni(SCN)2X4 may be resolved by forming a clathrate with the clathratable compound or compounds and dissociating the clathrate in order to obtain the clathratable aromatic organic compound or compounds.  The dissociation may be effected by heating the clathrate, or by treatment with a mineral acid which does not react with the clathrated compound or compounds, or by treatment with heated water vapour, or by elution with an inert solvent, e.g. pentane, hexane or cyclohexane.  Many of the Werner complexes which may be used in the process of the invention are described and claimed in Specifications 931,775, and 935,099.  At least one of the four molecules of combined primary phenyl-substituted alkylamine in the Werner complex, Ni(SCN)2X4, may be different from the others.  In the examples the following mixtures are clathrated using a large number of Werner complexes, one or more of the components of the mixtures being selectively clathrated: (1) to (3) o- and p-xylenes, (4) the xylenes, (5) the xylenes and ethylbenzene, (6) the chlorotoluenes, (7) the cymenes, (8) a -and b -methylnaphthalenes, (9) 2,3- and 2,6-dimethylnaphthalenes, (10) n- and isopropylbenzenes; n-, iso-, sec, and ter-butylbenzenes; styrene and ethylbenzene; the diethylbenzenes; the ethyltoluenes; the ethylisopropylbenzenes; the cyclohexyltoluenes, the chlorotoluenes; the bromotoluenes; o-, and p-dichlorotoluenes; the trimethylbenzenes; o-ethyltoluene and mesitiylene; dimethyl ethylbenzenes; naphthalene, tetralin and decalin; naphthalene and disphenyl; and a - and b -ethylnaphthalenes.  Specification 811,137 also is referred to.