4,4'-二氨基二环己基甲烷

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Molten 4,4'-methylenebis(cyclohexylamine) (224.0 g, 1.065 moles) was placed in a 1 liter round bottom flask and 85% lactic acid (225.5 g, 2.13 moles) added slowly through an addition funnel with stirring and cooling. The resultant liquid was then heated in an oil bath to 190° C. whereupon distillation of water occurred. Heating was continued at 190° C. for 4 hours after which time distillation of water subsided and the liquid was poured into a Pyrex baking dish. Upon cooling the product solidified into a clear, amber colored glass. The solid was broken up and recrystallized twice from tetrahydrofuran containing 10% methanol to give lustrous, white flakes; m.p. 195°-199° C.; infrared (Nujol), 1640 cm-1, 3300 cm-1 ; proton nuclear magnetic resonance (DMSO-d6 /TMS, 100 MHz), δ0.6-1.5 (complex multiplet with doublet superimposed at δ1.15, 18 protons), δ1.5-1.8 (doublet, 8 protons), δ3.50 (broad singlet, 2 protons), δ3.7-4.1 (multiplet, 2 protons), δ5.35 (doublet, 2 protons), δ7.30 (doublet, 2 protons). cooling Heating after which time distillation of water the liquid was poured into a Pyrex baking dish Upon cooling the product recrystallized twice from tetrahydrofuran containing 10% methanol to give lustrous

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 4,4'-Methylenebis(cyclohexylamine) (25 g, 0.12 mole) and glycolic acid (18.2 g, 0.24 mole) were combined in a 250 ml round bottom flask heated in an oil bath. The solids were melted together with mixing and heated to 175° C. whereupon distillation of water occurred. After heating for 3 hours the evolution of water subsided and crystallization commenced. The solid was removed and recrystallized from methanol to yield 34 g (87%) of lustrous white needles; m.p. 208°-212° C. heated in an oil bath with mixing crystallization The solid was removed recrystallized from methanol

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 4,4'-Methylenebis(cyclohexylamine) (56.5 g, 0.27 mole) was dissolved in hot isopropanol (500 ml) and glycolic acid (40.9 g, 0.54 mole) added portion-wise with stirring. Upon cooling, a white gummy solid separated which was isolated by decantation and redissolved in a small volume of ethanol. Crystallization produced a white crystalline, deliquescent solid; m.p. 96°-102° C. Thorough drying under vacuum increased the melting point (m.p. 149°-151° C.) and reduced the deliquescence. Upon cooling a white gummy solid separated which was isolated by decantation Crystallization produced a white crystalline, deliquescent solid Thorough drying under vacuum increased the melting point (m.p. 149°-151° C.)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Due to these disadvantages and others, the utilization of catalysts containing metallic ruthenium has become preferred in the art in such hydrogenation processes as described in U.S. Pat. Nos. 2,606,924; 2,606,925; 2,494,563; 3,347,917; 3,676,495; and others. U.S. Pat. No. 2,606,924 to Whitman (1952) and U.S. Pat. No. 2,494,563 to Kirk, et al. (1950) describe processes for the preparation of certain stereoisomeric bis (4-aminocyclohexyl)methanes by the hydrogenation of bis(4-aminophenyl)methane with a ruthenium metal catalyst in the presence or absence of volatile organic solvent. More particularly, Whitman (2,606,924) discloses that steroisomeric bis(4-aminocyclohexyl)methane mixtures liquid at normal temperatures can be produced by the hydrogenation of bis(4-aminophenyl)methane at a temperature of 75°-125°C. and a pressure of between 100-15,000 psi in the presence of a ruthenium catalyst. Kirk, et al. (2,494,563) teach that the hydrogenation of bis(4-aminophenyl)methane in the presence of a ruthenium catalyst at temperatures between 140°-250°C. and pressures above 500 psi, e.g., 1,500-3,500 psi, results in a reaction product which, upon distillation and redistillation in vacuo, provides stereoisomeric bis (4-aminocyclohexyl)methane mixtures having a freezing point above 40°C. pressures above 500 psi, e.g., 1,500-3,500 psi, results in a reaction product which, upon distillation and redistillation in vacuo

反应条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Agitated in a reaction vessel are 210 parts of 4,4'-diaminodicyclohexylmethane with 360 parts of O-octyl carbamate and 150 parts of n-octanol-(1) at a reflux temperature of 185° C.-205° C. for 2 hours while the ammonia is removed by means of distillation. At this point, an additional 650 parts of n-octanol are allowed to flow into the reaction mixture and the reaction is continued at reflux temperature for 10 hours. The reaction mixture, which has been cooled to 100° C., is filtered, and the product is allowed to crystallize by cooling the filtrate. By filtration, washing with octanol and drying, 468 parts of bis(4-octoxycarbonylaminocyclohexyl)methane, C31H58N2O4 (molecular weight 522) are obtained corresponding with 89.6 percent theory relative to 4,4'-bisaminodicyclohexylmethane. The melting point is 129° C.-130° C. at a reflux temperature of 185° C.-205° C. for 2 hours is removed by means of distillation at reflux temperature for 10 hours is filtered to crystallize by cooling the filtrate By filtration washing with octanol drying

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 1,3-bis(aminomethyl)cyclohexane; compounds represented by the formulae (35) to (69); 2,6-diaminopyridine; 3,4-diaminopyridine; 2,4-diaminopyrimidine; 3,6-diaminoacridine; 3,6-diaminocarbazole;

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Molten 4,4'-methylenebis(cyclohexylamine) (224.0 g, 1.065 moles) was placed in a 1 liter round bottom flask and 85% lactic acid (225.5 g, 2.13 moles) added slowly through an addition funnel with stirring and cooling. The resultant liquid was then heated in an oil bath to 190° C. whereupon distillation of water occurred. Heating was continued at 190° C. for 4 hours after which time distillation of water subsided and the liquid was poured into a Pyrex baking dish. Upon cooling the product solidified into a clear, amber colored glass. The solid was broken up and recrystallized twice from tetrahydrofuran containing 10% methanol to give lustrous, white flakes; m.p. 195°-199° C.; infrared (Nujol), 1640 cm-1, 3300 cm-1 ; proton nuclear magnetic resonance (DMSO-d6 /TMS, 100 MHz), δ0.6-1.5 (complex multiplet with doublet superimposed at δ1.15, 18 protons), δ1.5-1.8 (doublet, 8 protons), δ3.50 (broad singlet, 2 protons), δ3.7-4.1 (multiplet, 2 protons), δ5.35 (doublet, 2 protons), δ7.30 (doublet, 2 protons). cooling Heating after which time distillation of water the liquid was poured into a Pyrex baking dish Upon cooling the product recrystallized twice from tetrahydrofuran containing 10% methanol to give lustrous

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 4,4'-Methylenebis(cyclohexylamine) (25 g, 0.12 mole) and glycolic acid (18.2 g, 0.24 mole) were combined in a 250 ml round bottom flask heated in an oil bath. The solids were melted together with mixing and heated to 175° C. whereupon distillation of water occurred. After heating for 3 hours the evolution of water subsided and crystallization commenced. The solid was removed and recrystallized from methanol to yield 34 g (87%) of lustrous white needles; m.p. 208°-212° C. heated in an oil bath with mixing crystallization The solid was removed recrystallized from methanol

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 4,4'-Methylenebis(cyclohexylamine) (56.5 g, 0.27 mole) was dissolved in hot isopropanol (500 ml) and glycolic acid (40.9 g, 0.54 mole) added portion-wise with stirring. Upon cooling, a white gummy solid separated which was isolated by decantation and redissolved in a small volume of ethanol. Crystallization produced a white crystalline, deliquescent solid; m.p. 96°-102° C. Thorough drying under vacuum increased the melting point (m.p. 149°-151° C.) and reduced the deliquescence. Upon cooling a white gummy solid separated which was isolated by decantation Crystallization produced a white crystalline, deliquescent solid Thorough drying under vacuum increased the melting point (m.p. 149°-151° C.)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Instead of the pure 4,4'-diaminodicyclohexylmethane, mixtures of the diaminodicyclohexylmethane position isomers which are composed of 70 to 99 mol % of the 4,4'-diamino isomer, 1-30 mol % of the 2,4'-diamino isomer, 0-2 mol % of the 2,2'-diamino isomer and, if appropriate, diamines with a correspondingly higher degree of condensation and which are obtained by hydrogenation of diaminodiphenylmethane of technical quality can also be used. Up to 30% of the isophthalic acid can be replaced by terephthalic acid.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Instead of the pure 4,4'-diaminodicyclohexylmethane, mixtures of the diaminodicyclohexylmethane position isomers which are composed of 70 to 99 mol % of the 4,4'-diamino isomer, 1-30 mol % of the 2,4'-diamino isomer, 0-2 mol % of the 2,2'-diamino isomer and, if appropriate, diamines with a correspondingly higher degree of condensation and which are obtained by hydrogenation of diaminodiphenylmethane of technical quality can also be used. Up to 30% of the isophthalic acid can be replaced by terephthalic acid.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Bis(p-aminocyclohexyl)methane phthalamide was prepared by the aqueous reaction of bis(p-aminocyclohexyl)methane with phthalimide, according to a procedure similar to that published by Spring and Woods noted hereinabove. Thus, an emulsion of the amine in water was made using vigorous stirring. Phthalimide (1.0 mole per 2.4 moles of amine) was finely grounded and added to the emulsion at room temperature within a 10-minute period. The mixture was stirred for an additional 40 minutes and poured into a separatory funnel and extracted with chloroform. The chloroform solution was dried over magnesium sulfate, filtered and stripped. The product was washed with hexane and with anhydrous ethyl ether and then stripped in a vacuum oven. added to the emulsion at room temperature within a 10-minute period poured into a separatory funnel extracted with chloroform The chloroform solution was dried over magnesium sulfate filtered The product was washed with hexane and with anhydrous ethyl ether