4-[(4-aminophenyl)methyl]aniline

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The synthesis of 2-amino-5-{[4-(4-amino-benzyl)-phenylamino]-methyl}-3,7-dihydro-pyrrolo[2,3-d]pyrimidin-4-one 24 follows the same steps as the synthesis of 4-[(2-amino-4-oxo-4,7-dihydro-3H-pyrrolo[2,3-d]pyrimidin-5-ylmethyl)-amino]-benzoic acid 21, except that octanoic acid{5-[(dibenzylamino)-methyl]-4-oxo-4,7-dihydro-3H-pyrrolo[2,3-d]pyrimidin-2-yl}-amide 18 is reacted with 4,4′-methylene dianiline 22 to form octanoic acid (5-{[4-(4-amino-benzyl)-phenylamino]-methyl}-4-oxo-4,7-dihydro-3H-pyrrolo[2,3-d]pyrimidin-2-yl)-amide 23. Octanoic acid (5-{[4-(4-amino-benzyl)-phenylamino]-methyl}-4-oxo-4,7-dihydro-3H-pyrrolo[2,3-d]pyrimidin-2-yl)-amide 23 is then reacted with 5M KOH to form 2-amino-5-{[4-(4-amino-benzyl)-phenylamino]-methyl}-3,7-dihydro-pyrrolo[2,3-d]pyrimidin-4-one 24.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4,4'-methylene dianiline (198 g; 1 mole), acetophenone (240 g; 2 moles) and a catalytic amount of stannous chloride was refluxed in toluene (3L) for 30 hours using a Dean-Stark trap. The theoretical amount of water was removed from the system. The toluene was then removed under vacuum. The theoretical amount of water was removed from the system The toluene was then removed under vacuum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4,4'-methylene dianiline (198 g; 1 mole), acetophenone (240 g; 2 moles) and a catalytic amount of stannous chloride was refluxed in toluene (3L) for 30 hours using a Dean-Stark trap. The theoretical amount of water was removed from the system. The toluene was then removed under vacuum. The theoretical amount of water was removed from the system The toluene was then removed under vacuum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 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

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An 2-anilinecarboxylic acid derivative (e.g. sodium 2-anilinecarboxylate) or an 3-anilinecarboxylic acid derivative (e.g. sodium 3-anilinecarboxylate) and aniline are treated with formalin under acidic conditions to give the corresponding 4,4′-diaminodiphenylmethane derivative. This is diazotized using sodium nitrite under acidic conditions in the presence of hydrochloric acid, followed by reaction with sodium azide, to give the desired product.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An 2-anilinesulfonic acid derivative (e.g. sodium 2-anilinesulfonate) or an 3-anilinesulfonic acid derivative (e.g. sodium 3-anilinesulfonate) and aniline are treated with formalin under acidic conditions, to give the corresponding 4,4′-diaminodiphenylmethane derivative. This is diazotized using sodium nitrite under acidic conditions in the presence of hydrochloric acid, followed by reaction with sodium azide, to give the desired product.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An 2-anilinesulfonic acid derivative (e.g. sodium 2-anilinesulfonate) or an 3-anilinesulfonic acid derivative (e.g. sodium 3-anilinesulfonate) and aniline are treated with formalin under acidic conditions, to give the corresponding 4,4′-diaminodiphenylmethane derivative. This is diazotized using sodium nitrite under acidic conditions in the presence of hydrochloric acid, followed by reaction with sodium azide, to give the desired product.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An 2-anilinesulfonic acid derivative (e.g. sodium 2-anilinesulfonate) or an 3-anilinesulfonic acid derivative (e.g. sodium 3-anilinesulfonate) is treated with formalin under acidic conditions to give the corresponding 4,4′-diaminodiphenylmethane derivative. This is diazotized using sodium nitrite under acidic conditions in the presence of hydrochloric acid, followed by reaction with sodium azide, to give the desired product.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4,4′-methylenedianiline (19.8 g), potassium carbonate (20 g) in ethyl acetate (300 mL) and water (200 mL) was stirred in an ice bath. Benzyl chloroformate (15 mL) was slowly added to the mixture. The resulting mixture was stirred for 1 hour, then the organic layer was separated, and the aqueous layer extracted with additional ethyl acetate. The combined organic extracts were washed with water and brine, dried (Na2SO4), and the solvent removed in vacuo. The crude mixture was isolated by column chromatography on silica gel, eluting with 30% ethyl acetate/hexanes, to give 4-(4-aminobenzyl)phenyl-carbamic acid benzyl ester as solid. The resulting mixture was stirred for 1 hour the organic layer was separated the aqueous layer extracted with additional ethyl acetate The combined organic extracts were washed with water and brine dried (Na2SO4) the solvent removed in vacuo The crude mixture was isolated by column chromatography on silica gel eluting with 30% ethyl acetate/hexanes

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A novel process for making 4,4'-methylene diphenyl diisocyanate and corresponding oligomer in improved selectivity and yield comprises condensing formaldehyde and aniline under neutral or basic conditions to yield an anil condensate, followed by reacting the anil condensate with additional aniline and a protonic salt of aniline to yield 4,4'-methylene dianiline and corresponding oligomer, then followed by conventional phosgenation. yield to yield an anil condensate

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4.8 g of isophthalic acid and 33.6 g of trimellitic acid are added at room temperature to 419 g of a solution of N,N'-bis-[methoxy carbonyl propyl-(2)-]-4,4'-diaminodiphenyl methane in a mixture of 36% by weight of γ-butyrolactone and 64% by weight of toluene (29.2% N), followed by the addition at 50° C. of 204 g of 4,4'-diisocyanatodiphenylmethane. After stirring for 2 hours at 50° C., another 87.4 g of 4,4'-diisocyanatodiphenyl methane and 0.6 g of endoethylene piperazine are added at 50° C., followed by homogenisation for 1 hour at 50° C. Then another 201.2 g of trimellitic acid anhydride and 120 g of terephthalic acid dimethyl ester are added to this solution in portions at 50° C., followed by homogenisation for 30 minutes at 50° C. The suspension obtained is left standing overnight at room temperature and, on the following day, is heated to 205° C. with elimination of carbon dioxide, methanol and toluene, maintained for 3 hours at 205° C. and, then, for 1 hour at 215° C. 218.8 g of terephthalic acid dimethyl ester are then added at from 170° to 180° C., followed by the addition at from 150° to 160° C. of 318 g of N,N',N"-tris-hydroxyethyl triazolidine-3,5-dione, 1.8 g of lead acetate and 0.6 g of titanium tetrabutylate. The mixture is then heated for 2 hours to 170° C. Then 30 g of xylene and 160 g of a polyester produced from 4 moles of terephthalic acid, 1.5 moles of glycerol and 3 moles of glycol (OH-content 4.53%, acid number 4.8 mg KOH) are added at from 160° to 170° C., after which the mixture is again subjected to condensation for 3 hours at from 200° to 220° C. first directly and, finally, in vacuo until a sample diluted to 50% by weight with γ-butyrolactone has a viscosity of approximately 10,000 mPa.s at 25° C. 1501 g of a brittle, approximately 80% by weight resin are obtained, of which a 15% by weight solution in γ-butyrolactone has a viscosity of 156 mPa.s at 25° C. followed by homogenisation for 1 hour at 50° C followed by homogenisation for 30 minutes at 50° C The suspension obtained is left standing overnight at room temperature and, on the following day maintained for 3 hours at 205° C. for 1 hour at 215° C The mixture is then heated for 2 hours to 170° C

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4.8 g of isophthalic acid and 33.6 g of trimellitic acid are added at room temperature to 419 g of a solution of N,N'-bis-[methoxy carbonyl propyl-(2)-]-4,4'-diaminodiphenyl methane in a mixture of 36% by weight of γ-butyrolactone and 64% by weight of toluene (29.2% N), followed by the addition at 50° C. of 204 g of 4,4'-diisocyanatodiphenylmethane. After stirring for 2 hours at 50° C., another 87.4 g of 4,4'-diisocyanatodiphenyl methane and 0.6 g of endoethylene piperazine are added at 50° C., followed by homogenisation for 1 hour at 50° C. Then another 201.2 g of trimellitic acid anhydride and 120 g of terephthalic acid dimethyl ester are added to this solution in portions at 50° C., followed by homogenisation for 30 minutes at 50° C. The suspension obtained is left standing overnight at room temperature and, on the following day, is heated to 205° C. with elimination of carbon dioxide, methanol and toluene, maintained for 3 hours at 205° C. and, then, for 1 hour at 215° C. 218.8 g of terephthalic acid dimethyl ester are then added at from 170° to 180° C., followed by the addition at from 150° to 160° C. of 318 g of N,N',N"-tris-hydroxyethyl triazolidine-3,5-dione, 1.8 g of lead acetate and 0.6 g of titanium tetrabutylate. The mixture is then heated for 2 hours to 170° C. Then 30 g of xylene and 160 g of a polyester produced from 4 moles of terephthalic acid, 1.5 moles of glycerol and 3 moles of glycol (OH-content 4.53%, acid number 4.8 mg KOH) are added at from 160° to 170° C., after which the mixture is again subjected to condensation for 3 hours at from 200° to 220° C. first directly and, finally, in vacuo until a sample diluted to 50% by weight with γ-butyrolactone has a viscosity of approximately 10,000 mPa.s at 25° C. 1501 g of a brittle, approximately 80% by weight resin are obtained, of which a 15% by weight solution in γ-butyrolactone has a viscosity of 156 mPa.s at 25° C. followed by homogenisation for 1 hour at 50° C followed by homogenisation for 30 minutes at 50° C The suspension obtained is left standing overnight at room temperature and, on the following day maintained for 3 hours at 205° C. for 1 hour at 215° C The mixture is then heated for 2 hours to 170° C