1,3-diaminothiourea

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 2.65 g (25 mmol) of thiocarbohydrazide and 9.77 g (25 mmol) of 2-(3-pentadecylphenoxy)butanoic acid in 30 mL of toluene was added 0.42 g (2.5 mmol) of 3-nitrobenzene boronic acid was heated at reflux for 24 hr. The reaction was cooled and the reaction was allowed to settle. The supernatant liquid was decanted. To the residual solid was added 20 mL of acetonitrile. The mixture was stirred for 15 minutes. The solid was collected, rinsed with 5 mL of cold acetonitrile and dried in vacuo to afford 7.20 g (60.4%) of the desired product as a white solid. Analytical data are consistent with the assigned structure. was heated at reflux for 24 hr The reaction was cooled The supernatant liquid was decanted To the residual solid was added 20 mL of acetonitrile The solid was collected rinsed with 5 mL of cold acetonitrile dried in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 4.9 g (47 mmol) of thiocarbohydrazide and 9.8 g (47 mmol) of 4-nitrophenylbutanoic acid in 30 mL of toluene was added 0.8 g (4.7 mmol) of 3-nitrobenzeneboronic acid. The mixture was heated at reflux for 24 hr. The reaction was cooled and the reaction mixture was allowed to settle. The supernatant liquid was decanted. To the residual solid was added 50 mL of acetonitrile. The mixture was stirred for 30 minutes. The solid was collected, rinsed with 10 mL of acetonitrile and dried in vacuo to yield 8.5 g (65.4%) of the desired product as a white sandy material. All the analytical data confirmed the assigned structure. The mixture was heated at reflux for 24 hr The reaction was cooled The supernatant liquid was decanted To the residual solid was added 50 mL of acetonitrile The solid was collected rinsed with 10 mL of acetonitrile dried in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 4.9 g (47 mmol) of thiocarbohydrazide and 15 g (47 mmol) of 4-(dodecylsulfonyl)butanoic acid in 30 ml of toluene was added 0.8 g (4.7 mmol) of 3-nitrobenzeneboronic acid. The mixture was heated at reflux for 24 hr. Upon cooling, the thick precipitate was collected, rinsed with a small amount of acetonitrile (10 ml), dried in vacuo to yield 16 g (87.4%) of the desired product as a white solid. All of the analytical data confirmed the assigned structure. The mixture was heated at reflux for 24 hr Upon cooling the thick precipitate was collected rinsed with a small amount of acetonitrile (10 ml) dried in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Methyl dithiocarbazinate (24.4 gm., 0.2 mole) was dissolved in 200 ml. of absolute ethanol and 18 ml. (0.3 mole of hydrazine) of 85% hydrazine hydrate was added. The resulting solution was refluxed until no more solid thiocarbohydrazide precipitated (about 45 minutes). A small amount of 3-hydrazino-4-amino-5-mercapto-1,2,4-triazole that had formed was removed as follows. The reaction mixture was chilled, and the resulting solid product was collected and recrystallized from water acidified with a few drops of hydrochloric acid. Methyl dithiocarbazinate (24.4 gm., 0.2 mole) was dissolved in 200 ml precipitated (about 45 minutes)

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 882 g (4.14 mols) of 4-(cyclopropyl-methyl-methylene)-N-methylrhodanine (as an E/Z mixture) are introduced into a solution of 712 g (17.8 mols) of sodium hydroxide in 4.4 l of water. After the addition of 7 ml of alkylaryl polyglycol ether, the mixture is stirred at 70° C. until complete dissolution occurs (about 16 hours). 438 g (4.14 mols) of thiocarbohydrazide and 115 ml of 1-decanol are then added, the mixture is stirred for one hour at 70° C., and 1525 ml of acetic acid are rapidly added dropwise, causing the reaction product to precipitate. The mixture is stirred at 80° C. for a further 2 hours, allowed to cool to room temperature and the precipitate is filtered off with suction, washed several times with water and also with petroleum ether and dried at 70° C. 725 g (82.6% of theory) of the above compound of melting point 142°-143° C. are obtained. (about 16 hours) the mixture is stirred for one hour at 70° C. to precipitate The mixture is stirred at 80° C. for a further 2 hours to cool to room temperature the precipitate is filtered off with suction washed several times with water also with petroleum ether and dried at 70° C 725 g (82.6% of theory) of the above compound of melting point 142°-143° C. are obtained

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 200 ml of concentrated sulphuric acid and then 72 g of water were added dropwise to 111 g (1 mol) of pivaloyl cyanide at 20° to 25° C. The reaction mixture was subsequently stirred at 20° to 25° C. for 20 hours and was added to a solution of 106 g (1 mol) of thiocarbohydrazide in 500 ml of water and 150 ml of concentrated hydrochloric acid at the above temperature. The mixture was subsequently stirred at 80° to 90° C. for 2 hours, cooled to 5° to 10° C. and filtered. The solid residue was recrystallized from methanol. 130 g (65% of theory) of 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5(4H)-one (VII) of melting point 216° C. were obtained. The mixture was subsequently stirred at 80° to 90° C. for 2 hours cooled to 5° to 10° C. filtered The solid residue was recrystallized from methanol

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 200 ml of concentrated sulphuric acid and then 72 g of water were added dropwise to 111 g (1 mol) of pivaloyl cyanide at 20° to 25° C. The reaction mixture was subsequently stirred at 20° to 25° C. for 20 hours and was added to a solution of 106 g (1 mol) of thiocarbohydrazide in 500 ml of water and 150 ml of concentrated hydrochloric acid at the above temperature. The mixture was subsequently stirred at 80° to 90° C. for 2 hours, cooled to 5° to 10° C. and filtered. The solid residue was recrystallized from methanol. 130 g (65% of theory) of 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5(4H)-one (VII) of melting point 216° C. were obtained. The mixture was subsequently stirred at 80° to 90° C. for 2 hours cooled to 5° to 10° C. filtered The solid residue was recrystallized from methanol

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hydrogen chloride gas was passed into a mixture of 222 g (2 mol) of pivaloyl cyanide and 120 g (2 mol) of glacial acetic acid under 8 bars and at 20° to 25° C. for four hours. Thereafter, the mixture was let down and excess glacial acetic acid was stripped off in vacuo. The product was then added to a mixture of 212 g (2 mol) of thiocarbohydrazide, 840 g of water and 280 g of concentrated hydrochloric acid. When the addition had ended, the reaction mixture was warmed to 90° C. for 1.5 hours and then subsequently stirred at room temperature overnight. The mixture was then cooled to 0° C. and the solid obtained was filtered off, washed with 400 ml of cold water and dried at 40° C. in vacuo. 314.4 g (78.6% of theory) of 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5(4H)-one (VII) of melting point 205°-209° C. were obtained. When the addition The mixture was then cooled to 0° C. the solid obtained was filtered off washed with 400 ml of cold water dried at 40° C. in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Trimethylpyruvic acid of formula (VI) can be subjected to a condensation reaction with 1 to 1.5 moles of thiocarbohydrazide (NH2 --NH--CS--NH--NH2) in aqueous solution containing a hydrogen halide acid, at a temperature between 20° and 100° C., to give 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5(4H)-one of formula (VII).

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: which is formed in step (1) and which was hitherto unknown, is reacted, in a second stage, either directly in the solution obtained or after intermediate isolation and if appropriate after prior saponification to give free trimethylpyruvic acid (VI), with thiocarbohydrazide (H2N--NH--CS--NH--NH2) in an aqueous solution containing a hydrogen halide acid, at a temperature from about 20° to 100° C. in a manner which is in itself known to give 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5(4H)-one (VII), and this compound is alkylated in alkaline solution, in a third stage, by means of methyl iodide or methyl bromide or other alkylating agents (especially ethyl iodide or ethyl bromide) in a known manner. which is formed in step (1) and which is reacted, in a second stage directly in the solution obtained from about 20° to 100° C.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Thiocarbohydrazide, 212.2 grams, is added to 500 ml. of propionic acid and heated to its reflux temperature for approximately 90 minutes. The reaction mixture is cooled to room temperature and diluted with anhydrous ether. After standing overnight in the refrigerator, the desired 4-amino-5-ethyl-4H-1,2,4-triazole-3 -thiol is filtered, washed with anhydrous ether and air dried to yield a product having a m.p. of 143°-6° C. reflux temperature for approximately 90 minutes the desired 4-amino-5-ethyl-4H-1,2,4-triazole-3 -thiol is filtered washed with anhydrous ether and air dried to yield a product

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Thiocarbohydrazide, 212.2 grams, is added to 500 ml. of propionic acid and heated to its reflux temperature for approximately 90 minutes. The reaction mixture is cooled to room temperature and diluted with anhydrous ether. After standing overnight in the refrigerator, the desired 4-amino-5-ethyl-4H-1,2,4-triazole-3 -thiol is filtered, washed with anhydrous ether and air dried to yield a product having a m.p. of 143°-6° C. reflux temperature for approximately 90 minutes the desired 4-amino-5-ethyl-4H-1,2,4-triazole-3 -thiol is filtered washed with anhydrous ether and air dried to yield a product