1,3-diaminourea

Conditions: temp:125.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Analogously to Example 3, a solution of carbodihydrazide in phenol is prepared from 3,200 g (64 mol) of hydrazine hydrate and 6,848 g (32 mol) of diphenyl carbonate and the water of hydration and also 1,500 ml of phenol are then distilled off. After addition of 3 g of dimethyltin oxide and 1,848 g (33.6 mol) of propionitrile, the mixture is heated to a weak reflux (125° C.). The temperature can be increased to 180° C. in the course of 11 hours under a continuous reflux. Thereafter, the evolution of NH3 has ended. Phenol is now distilled off at a bottom temperature of 160° C. under reduced pressure (decreasing to 15 mbar), the residue remaining liquid. Residual phenol is therefore removed under 1 mbar using an oil pump. After cooling, the residue is dissolved in 3 L of hot water. 80 ml of diethylamine and 10 g of tartaric acid (to remove a slight turbidity caused by the catalyst) are added to the solution. A diethylamine excess and traces of phenol are removed by incipient distillation. After cooling to 10° C., the product is filtered off with suction, washed with 500 ml of cold 50% strength ethanol and dried at 100° C. in vacuo. 3,478 g (85% of theory) of 3-ethyl-4-amino-1,2,4-triazol-5-one of melting point 171° C. are obtained. the water of hydration and also 1,500 ml of phenol are then distilled off the mixture is heated to The temperature can be increased to 180° C. in the course of 11 hours under a continuous reflux Phenol is now distilled off at a bottom temperature of 160° C. under reduced pressure (decreasing to 15 mbar) Residual phenol is therefore removed under 1 mbar After cooling the residue is dissolved in 3 L of hot water 80 ml of diethylamine and 10 g of tartaric acid (to remove a slight turbidity are added to the solution are removed by incipient distillation After cooling to 10° C. the product is filtered off with suction washed with 500 ml of cold 50% strength ethanol dried at 100° C. in vacuo

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

Procedure: Following the general procedure of Example 1, condensation of 2-hydroxy-1-naphthaldehyde and carbohydrazide gave a white solid (97%): mp>285° C. (dec); 1H NMR d 11.90 (br s, 2 H); 11.05 (s, 2 H), 9.23 (s, 2 H), 8.33 (d, 2 H, J=8.4 Hz), 7.88 (d, 2 H, J=9.0 Hz), 7.87 (d, 2 H, J=7.8 Hz), 7.59 (t, 2 H, J=7.6 Hz), 7.38 (t, 2 H, J=7.5 Hz), 7.22 (d, 2 H, J=9.0 Hz); 13C NMR d 156.71, 151.56, 143.24, 131.88, 131.50, 128.72, 127.87, 127.56, 123.35, 121.58, 118.61, 109.40; MS (CI) m/e 399.0 (M +H)+; Anal. (C23H18N4O3 0.3 H2O) C, H, N.

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

Procedure: Following the general procedure of Example 1, condensation of 2-hydroxy-1-naphthaldehyde and carbohydrazide gave a white solid (97%): mp>285° C. (dec); 1H NMR d 11.90 (br s, 2 H); 11.05 (s, 2 H), 9.23 (s, 2 H), 8.33 (d, 2 H, J=8.4 Hz), 7.88 (d, 2 H, J=9.0 Hz), 7.87 (d, 2 H, J=7.8 Hz), 7.59 (t, 2 H, J=7.6 Hz), 7.38 (t, 2 H, J=7.5 Hz), 7.22 (d, 2 H, J=9.0 Hz); 13C NMR d 156.71, 151.56, 143.24, 131.88, 131.50, 128.72, 127.87, 127.56, 123.35, 121.58, 118.61, 109.40; MS (CI) m/e 399.0 (M +H)+; Anal. (C23H18N4O3 0.3 H2O) C, H, N.

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

Procedure: A mixture of 11.25 g (0.125 mole) carbohydrazide, 25 g sodium bicarbonate, 200 ml methanol and 37 g (0.25 mole) 1-butanesulfonyl chloride was heated to 60° C until evolution of CO2 ceased. The mix was cooled and water was added to precipitate the product. The initial precipitate weighed 12 g (dry). This melted with decomposition at 195°-197° C. The mix was cooled to precipitate the product 12 g (dry) This melted with decomposition at 195°-197° C.

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

Procedure: A mixture of 11.25 g (0.125 mole) carbohydrazide, 25 g sodium bicarbonate, 200 ml methanol and 37 g (0.25 mole) 1-butanesulfonyl chloride was heated to 60° C until evolution of CO2 ceased. The mix was cooled and water was added to precipitate the product. The initial precipitate weighed 12 g (dry). This melted with decomposition at 195°-197° C. The mix was cooled to precipitate the product 12 g (dry) This melted with decomposition at 195°-197° C.

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 1-liter reaction flask was charged 29.5 g (0.2 mole) n-propane sulfonyl chloride, 200 ml ethanol, 9 g (0.1 mole) carbohydrazide and 16.8 g (0.2 mole) sodium bicarbonate. The mix was stirred and heated gradually to 80° C over a one hour period and was then allowed to reflux for four hours. The separated sodium chloride was filtered off (hot). The filtrate was cooled whereupon the crystalline product separated (17 g) m.p. 191°-194° C. Into a 1-liter reaction flask to reflux for four hours The separated sodium chloride was filtered off (hot) The filtrate was cooled whereupon the crystalline product separated (17 g) m.p. 191°-194° C.

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

Procedure: A mixture of 45 g (0.5 mole) carbohydrazide, 85 g NaHCO3 (1.0 mole) and 250 ml methanol was stirred and 128.5 g (1.0 mole) ethane sulfonyl chloride was dropped in. The temperature rose from 25° to 45° C during the reaction which took 1 hour. Stirring was continued for two hours. The product was filtered, washed and dried. Yield: 145.9 g m.p. 195° C. The temperature rose from 25° to 45° C during the reaction which Stirring was continued for two hours The product was filtered washed dried

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 45 g (0.5 mole) carbohydrazide, 84 g NaHCO3 (1.0 mole) and 50 ml methanol was stirred as 114.5 g (1.0 mole) methane sulfonyl chloride was added over 30 minutes. The temperature rose from 25° to 40° C. The stirring was continued for 15 minutes (temp. 44° C). The mixture was then heated to 65° C for two hours, and was then cooled to 25° C and the solid product (including sodium chloride was filtered and washed with methanol and dried. Yield: 146 g. The material was first suspended in water to remove sodium chloride and then filtered, washed with water and dried. Yield: 81 g, m.p. = 207° C dec. was added over 30 minutes rose from 25° to 40° C (temp. 44° C) was then cooled to 25° C was filtered washed with methanol dried to remove sodium chloride filtered washed with water dried

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 45 g (0.5 mole) carbohydrazide, 84 g NaHCO3 (1.0 mole) and 50 ml methanol was stirred as 114.5 g (1.0 mole) methane sulfonyl chloride was added over 30 minutes. The temperature rose from 25° to 40° C. The stirring was continued for 15 minutes (temp. 44° C). The mixture was then heated to 65° C for two hours, and was then cooled to 25° C and the solid product (including sodium chloride was filtered and washed with methanol and dried. Yield: 146 g. The material was first suspended in water to remove sodium chloride and then filtered, washed with water and dried. Yield: 81 g, m.p. = 207° C dec. was added over 30 minutes rose from 25° to 40° C (temp. 44° C) was then cooled to 25° C was filtered washed with methanol dried to remove sodium chloride filtered washed with water dried

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 211 g (1.0 mole) p-chlorobenzenesulfonyl chloride was added to a suspension of 45 g (0.5 mole) carbohydrazide and 100 g sodium bicarbonate in 1000 ml ethanol in a 3 liter reaction flask. The mixture was stirred and heated gradually to gentle reflux (80° C) as carbon dioxide was evolved. Heating was continued until CO2 no longer evolved (3 hours). The mix was cooled to 20° C and filtered. The mixture of product and sodium chloride was dried at 60° C. Yield = 227 g. The solid mixture was suspended in 2000 ml water, stirred to dissolve the sodium chloride, and then the insoluble product was filtered, washed and dried. Yield = 129 g, m.p. 239°-240° C (dec.) heated gradually Heating (3 hours) filtered The mixture of product and sodium chloride was dried at 60° C stirred to dissolve the sodium chloride the insoluble product was filtered washed dried

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 190.5 g (1.0 mole) p-toluene sulfonyl chloride, 45 g (0.5 mole) carbohydrazide, 84 g (1.0 mole) sodium bicarbonate and 1000 ml methanol were placed in a 2 liter flask. The mixture was stirred and heated to reflux (65° C) for 90 minutes. Carbon dioxide evolution was complete at this point. The solid product and sodium chloride were filtered off. The material was suspended in water to dissolve the sodium chloride and the residual solid product was filtered off, washed well with water, and dried at 60° C. Yield: 139 g -- Dec. temp. 232° C. heated The solid product and sodium chloride were filtered off to dissolve the sodium chloride the residual solid product was filtered off washed well with water dried at 60° C

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 190.5 g (1.0 mole) p-toluene sulfonyl chloride, 45 g (0.5 mole) carbohydrazide, 84 g (1.0 mole) sodium bicarbonate and 1000 ml methanol were placed in a 2 liter flask. The mixture was stirred and heated to reflux (65° C) for 90 minutes. Carbon dioxide evolution was complete at this point. The solid product and sodium chloride were filtered off. The material was suspended in water to dissolve the sodium chloride and the residual solid product was filtered off, washed well with water, and dried at 60° C. Yield: 139 g -- Dec. temp. 232° C. heated The solid product and sodium chloride were filtered off to dissolve the sodium chloride the residual solid product was filtered off washed well with water dried at 60° C