Patent GB-619706-A (GB)
Title: Manufacture of new cycloaliphatic diamines
Filed: 1946-12-16
Abstract: Catalysts comprise ruthenium compounds supported on a carrier, e.g. charcoal, silica gel, kieselguhr or alumina.  One method of preparation given involves fusing finely divided ruthenium oxide with sodium peroxide in a nickel crucible, pouring the aqueous solution of the resulting melt over activated charcoal, and drying and powdering the resulting charcoal containing ruthenium oxide. The catalysts may also be prepared by methods involving reduction of a compound of ruthenium in the presence of a carrier substance. A number of ruthenium compounds are specified.ALSO:Dialicyclic diamines are prepared by reacting with hydrogen in the presence of a hydrogenation catalyst at a temperature of at least 20 DEG  C., e.g. within the range 75 DEG  C. to 100 DEG  C., on aromatic compound of the general formula <FORM:0619706/IV(b)/1> wherein R6 and R7 represent nitro, nitroso, amino or monoalkyl substituted amino groups, R3 and R4 represent hydrogen atoms or alkyl or alkoxy groups attached to a carbon atom in the aromatic ring, and R3 represents a saturated or unsaturated divalent alicyclic hydrocarbon radical, preferably a saturated radical containing not more than 6 carbon atoms.  The reaction may be effected at a pressure within the range of from 100 lbs./sq. ins. to 15,000 lbs./sq. ins., and the quantity of catalyst employed may be within the range of from 0.001 per cent to 5 per cent of the weight of the aromatic compound being reduced.  The hydrogenation catalyst may be cobalt on alumina, platinum, nickel, iron or a ruthenium catalyst, e.g. a ruthenium oxide, such as ruthenium sesquioxide, dioxide and tetroxide, perruthenites such as barium perrutherites, ruthenates such as potassium, sodium, silver, barium, strontium, calcium and magnesium ruthenates, perruthenates such as potassium and sodium perruthenates, ruthenium halides such as ruthenium pentafluoride, dichloride, trichloride and tetrachloride, ruthenium chloro salts such as potassium chloro perruthenate, ruthenium sulphides such as ruthenium disulphide and trisulphide, and ruthenium sulphate.  The catalysts are preferably supported on a carrier, e.g., charcoal, silica gel, kieselguhr or alumina.  Suitable compounds which may be hydrogenated are bis-(p-aminophenyl)-methane, 1 : 2-bis-(p-aminophenyl)-ethane, 1 : 10-di-(p-aminotolyl) - decones, 1 : 10 - di - (p - nitrophenyl)-decone, 1 : 4-di-(p-aminophenyl)-2 : 2 : 3 : 3-tetramethylbutane, p : p1 - diamonoditolylmethanes, p : p1 - diaminodiphenetylmethanes, p : p1 - diaminodianisylmethanes, p : p - dinitrodianisylmethanes, p : p1 - dinitroditolylmethanes, 2 : 2 - di - (o - methyl - p - nitrophenyl) - propane, bis - (4 - nitroso - 2 - methylphenyl) - methane, 1 : 2 - di - (4 - nitroso - 3-methoxyphenyl) - ethane, 2 : 2 - di - (4 - nitroso-2 - methylphenyl) - propane, N : N1 - dimethyl-(p : p1 - diaminodiphenyl) - methane, N : N1-dimethyl - (p : p1 - diaminodiphenyl) - 1 : 2-ethane, N : N1 - diethyl - (p : p1 - diaminodiphenyl) - methane, p : p1 - diaminodiphenylmethane, p : p1 - diaminodiphenylmethylmethane, p : p1 - diaminodiphenyl - dimethylmethane, p : p1 - dinitrodiphenyl - 1 : 2-ethane, p : p1 - dinitrodiphenyl - 1 : 3 - propane, p : p1 - dinitrodiphenylmethylmethane, p : p1 - dinitrosodiphenylmethane, p : p1-dinitrosodiphenyl - 1 : 2 - ethane, p : p1-dinitrosodiphenyl - 1 - 3 - propane, p : p1-dinitrostilbene, p : p1 - diaminostilbene and N : N1 - dimethyldiaminostilbene.  In examples the following compounds are prepared: bis-(4-aminocyclohexyl)-methane and 1 : 2-bis-(4-aminocyclohexyl)-ethane.