4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline

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

Procedure: o-tolidine sulfone; 4,4′-methylene-bis-(2,6-diethyl aniline);

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A two-liter three neck round bottom flask was equipped with a magnetic stirrer, a heating mantle, a thermocouple, a glass stopper and a Dean Stark trap fitted with a condenser. 4,4′-Methylenebis(2,6-diethylbenzeneamine) (310.5 g, 1.00 mol) and methyl ethyl ketone (450 mL, 350 g, 4.85 mol) were added to the flask. This mixture was stirred at 40° C. to dissolve the 4,4′-methylenebis(2,6-diethylbenzeneamine). Hexanes (300 mL) and Amberlyst-15 (15.54 g) were added to the flask. The mixture was heated to reflux, and water was removed as an azeotrope in the Dean Stark trap. Samples were periodically taken and analyzed by gas chromatography (GC). N,N′-di-sec-butylidene-4,4′-methylenebis(2,6-diethylbenzeneamine) was formed in 94.7% yield. GC results are summarized in Table 1; units for the diamine, monoimine, and diimine are GC area percent. A two-liter three neck round bottom flask was equipped with a magnetic stirrer a heating mantle, a thermocouple, a glass stopper and a Dean Stark trap fitted with a condenser The mixture was heated to reflux water was removed as an azeotrope in the Dean Stark trap

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A two-liter three neck round bottom flask was equipped with a magnetic stirrer, a heating mantle, a thermocouple, a glass stopper and a Dean Stark trap fitted with a condenser. 4,4′-Methylenebis(2,6-diethylbenzeneamine) (310.5 g, 1.00 mol) and methyl ethyl ketone (450 mL, 350 g, 4.85 mol) were added to the flask. This mixture was stirred at 40° C. to dissolve the 4,4′-methylenebis(2,6-diethylbenzeneamine). Hexanes (300 mL) and Amberlyst-15 (15.54 g) were added to the flask. The mixture was heated to reflux, and water was removed as an azeotrope in the Dean Stark trap. Samples were periodically taken and analyzed by gas chromatography (GC). N,N′-di-sec-butylidene-4,4′-methylenebis(2,6-diethylbenzeneamine) was formed in 94.7% yield. GC results are summarized in Table 1; units for the diamine, monoimine, and diimine are GC area percent. A two-liter three neck round bottom flask was equipped with a magnetic stirrer a heating mantle, a thermocouple, a glass stopper and a Dean Stark trap fitted with a condenser The mixture was heated to reflux water was removed as an azeotrope in the Dean Stark trap

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4,4′-Methylenebis(2,6-diethylbenzeneamine) (3 g), Pt(S)/C (0.3 g), Amberlyst-15 (0.3 g), methyl ethyl ketone (25 g), and tetrahydrofuran (THF; 25 g) were charged into a 100 mL metal autoclave at 22° C. The closed autoclave was purged 3 times with 90 psig (7.22×105 Pa) of H2 at 22° C. The reaction mixture was then heated at 100-120° C. under 125 psig (9.63×105 Pa) of H2 for 5 hrs (until no further H2 uptake was observed). The product mixture was cooled to 22° C. and degassed. A diluted product sample was analyzed by GC (180° C. for 5 minutes at 10° C. per minute rate; final temperature, 270° C.). The GC data (normalization method) showed 100% conversion of 4,4′-methylenebis(2,6-diethylbenzeneamine), and an 86% yield of N,N′-di-sec-butyl-4,4′-methylenebis(2,6-diethylbenzeneamine). The closed autoclave was purged 3 times with 90 psig (7.22×105 Pa) of H2 at 22° C The product mixture was cooled to 22° C. degassed 180° C. for 5 minutes temperature, 270° C.

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4,4′-Methylenebis(2,6-diethylbenzeneamine) (4.0 g), Pt(S)/C (0.2 g), sulfonated divinylbenzene/styrene copolymer (0.2 g; H ion form, sold as Amberlyst-15 by Rohm and Haas Company, Philadelphia, Pa.), and methyl ethyl ketone (50 g) were charged into a 100 mL metal autoclave at 22° C. The closed autoclave was purged 3 times with 125 psig (9.63×105 Pa) of H2 at 22° C. to remove traces of air. The reaction mixture was then heated at 95° C. under 125 psig (9.63×105 Pa) of H2 for 3 hours (until no further H2 uptake was observed). The product mixture was cooled to 22° C. and degassed. A diluted product sample was analyzed by gas chromatography (GC; 180° C. for 5 minutes at 10° C. per minute rate; final temperature, 270° C.). The GC data (normalization method) showed 100% conversion of 4,4′-methylenebis(2,6-diethylbenzeneamine) and a 94% yield of N,N′-di-sec-butyl-4,4′-methylenebis(2,6-diethylbenzeneamine). NMR analysis (with internal standard) of a neat product sample showed a purity of 94.75%. The closed autoclave was purged 3 times with 125 psig (9.63×105 Pa) of H2 at 22° C. to remove traces of air The product mixture was cooled to 22° C. degassed temperature, 270° C.

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4,4′-Methylenebis(2,6-diethylbenzeneamine) (4.0 g), Pt(S)/C (0.2 g), sulfonated divinylbenzene/styrene copolymer (0.2 g; H ion form, sold as Amberlyst-15 by Rohm and Haas Company, Philadelphia, Pa.), and methyl ethyl ketone (50 g) were charged into a 100 mL metal autoclave at 22° C. The closed autoclave was purged 3 times with 125 psig (9.63×105 Pa) of H2 at 22° C. to remove traces of air. The reaction mixture was then heated at 95° C. under 125 psig (9.63×105 Pa) of H2 for 3 hours (until no further H2 uptake was observed). The product mixture was cooled to 22° C. and degassed. A diluted product sample was analyzed by gas chromatography (GC; 180° C. for 5 minutes at 10° C. per minute rate; final temperature, 270° C.). The GC data (normalization method) showed 100% conversion of 4,4′-methylenebis(2,6-diethylbenzeneamine) and a 94% yield of N,N′-di-sec-butyl-4,4′-methylenebis(2,6-diethylbenzeneamine). NMR analysis (with internal standard) of a neat product sample showed a purity of 94.75%. The closed autoclave was purged 3 times with 125 psig (9.63×105 Pa) of H2 at 22° C. to remove traces of air The product mixture was cooled to 22° C. degassed temperature, 270° C.

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

Procedure: in N-methylpyrrolidone (350 ml) was added 5,5'[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]-bis-1,3-isobenzofurandione (67.27 g, 0.1515 mol) under an inert atmosphere at room temperature. The resulting viscous orange solution was stirred overnight at room temperature. A solution of acetic anhydride (61.25 ml, 0.60 mol) and triethylamine (60.71 ml, 0.60 mol) was added with rapid stirring at room temperature. After stirring for 3 hours, the solution was diluted with additional N-methylpyrrolidone and precipitated in water. The resulting solid was collected and washed twice with water, washed twice with methanol, and allowed to air dry. The solid was further dried in a vacuum oven at 20 inches (0.51 m) mercury and 100° C. for 15 hours and at 245° C. for 4 hours to yield 99.4 g product. with rapid stirring at room temperature After stirring for 3 hours precipitated in water The resulting solid was collected washed twice with water washed twice with methanol to air dry The solid was further dried in a vacuum oven at 20 inches (0.51 m) mercury and 100° C. for 15 hours and at 245° C. for 4 hours

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A two-liter three neck round bottom flask was equipped with a magnetic stirrer, a heating mantle, a thermocouple, a glass stopper and a Dean Stark trap fitted with a condenser. 4,4′-Methylenebis(2,6-diethylbenzeneamine) (310.5 g, 1.00 mol) and methyl ethyl ketone (450 mL, 350 g, 4.85 mol) were added to the flask. This mixture was stirred at 40° C. to dissolve the 4,4′-methylenebis(2,6-diethylbenzeneamine). Hexanes (300 mL) and Amberlyst-15 (15.54 g) were added to the flask. The mixture was heated to reflux, and water was removed as an azeotrope in the Dean Stark trap. Samples were periodically taken and analyzed by gas chromatography (GC). N,N′-di-sec-butylidene-4,4′-methylenebis(2,6-diethylbenzeneamine) was formed in 94.7% yield. GC results are summarized in Table 1; units for the diamine, monoimine, and diimine are GC area percent. A two-liter three neck round bottom flask was equipped with a magnetic stirrer a heating mantle, a thermocouple, a glass stopper and a Dean Stark trap fitted with a condenser The mixture was heated to reflux water was removed as an azeotrope in the Dean Stark trap

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4,4′-Methylenebis(2,6-diethylbenzeneamine) (3 g), Pt(S)/C (0.3 g), Amberlyst-15 (0.3 g), methyl ethyl ketone (25 g), and tetrahydrofuran (THF; 25 g) were charged into a 100 mL metal autoclave at 22° C. The closed autoclave was purged 3 times with 90 psig (7.22×105 Pa) of H2 at 22° C. The reaction mixture was then heated at 100-120° C. under 125 psig (9.63×105 Pa) of H2 for 5 hrs (until no further H2 uptake was observed). The product mixture was cooled to 22° C. and degassed. A diluted product sample was analyzed by GC (180° C. for 5 minutes at 10° C. per minute rate; final temperature, 270° C.). The GC data (normalization method) showed 100% conversion of 4,4′-methylenebis(2,6-diethylbenzeneamine), and an 86% yield of N,N′-di-sec-butyl-4,4′-methylenebis(2,6-diethylbenzeneamine). The closed autoclave was purged 3 times with 90 psig (7.22×105 Pa) of H2 at 22° C The product mixture was cooled to 22° C. degassed 180° C. for 5 minutes temperature, 270° C.

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4,4′-Methylenebis(2,6-diethylbenzeneamine) (4.0 g), Pt(S)/C (0.2 g), sulfonated divinylbenzene/styrene copolymer (0.2 g; H ion form, sold as Amberlyst-15 by Rohm and Haas Company, Philadelphia, Pa.), and methyl ethyl ketone (50 g) were charged into a 100 mL metal autoclave at 22° C. The closed autoclave was purged 3 times with 125 psig (9.63×105 Pa) of H2 at 22° C. to remove traces of air. The reaction mixture was then heated at 95° C. under 125 psig (9.63×105 Pa) of H2 for 3 hours (until no further H2 uptake was observed). The product mixture was cooled to 22° C. and degassed. A diluted product sample was analyzed by gas chromatography (GC; 180° C. for 5 minutes at 10° C. per minute rate; final temperature, 270° C.). The GC data (normalization method) showed 100% conversion of 4,4′-methylenebis(2,6-diethylbenzeneamine) and a 94% yield of N,N′-di-sec-butyl-4,4′-methylenebis(2,6-diethylbenzeneamine). NMR analysis (with internal standard) of a neat product sample showed a purity of 94.75%. The closed autoclave was purged 3 times with 125 psig (9.63×105 Pa) of H2 at 22° C. to remove traces of air The product mixture was cooled to 22° C. degassed temperature, 270° C.

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A two-liter three neck round bottom flask was equipped with a magnetic stirrer, a heating mantle, a thermocouple, a glass stopper and a Dean Stark trap fitted with a condenser. 4,4′-Methylenebis(2,6-diethylbenzeneamine) (310.5 g, 1.00 mol) and methyl ethyl ketone (450 mL, 350 g, 4.85 mol) were added to the flask. This mixture was stirred at 40° C. to dissolve the 4,4′-methylenebis(2,6-diethylbenzeneamine). Hexanes (300 mL) and Amberlyst-15 (15.54 g) were added to the flask. The mixture was heated to reflux, and water was removed as an azeotrope in the Dean Stark trap. Samples were periodically taken and analyzed by gas chromatography (GC). N,N′-di-sec-butylidene-4,4′-methylenebis(2,6-diethylbenzeneamine) was formed in 94.7% yield. GC results are summarized in Table 1; units for the diamine, monoimine, and diimine are GC area percent. A two-liter three neck round bottom flask was equipped with a magnetic stirrer a heating mantle, a thermocouple, a glass stopper and a Dean Stark trap fitted with a condenser The mixture was heated to reflux water was removed as an azeotrope in the Dean Stark trap

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4,4′-Methylenebis(2,6-diethylbenzeneamine) (3 g), Pt(S)/C (0.3 g), Amberlyst-15 (0.3 g), methyl ethyl ketone (25 g), and tetrahydrofuran (THF; 25 g) were charged into a 100 mL metal autoclave at 22° C. The closed autoclave was purged 3 times with 90 psig (7.22×105 Pa) of H2 at 22° C. The reaction mixture was then heated at 100-120° C. under 125 psig (9.63×105 Pa) of H2 for 5 hrs (until no further H2 uptake was observed). The product mixture was cooled to 22° C. and degassed. A diluted product sample was analyzed by GC (180° C. for 5 minutes at 10° C. per minute rate; final temperature, 270° C.). The GC data (normalization method) showed 100% conversion of 4,4′-methylenebis(2,6-diethylbenzeneamine), and an 86% yield of N,N′-di-sec-butyl-4,4′-methylenebis(2,6-diethylbenzeneamine). The closed autoclave was purged 3 times with 90 psig (7.22×105 Pa) of H2 at 22° C The product mixture was cooled to 22° C. degassed 180° C. for 5 minutes temperature, 270° C.