chloromethyl thiocyanate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: To a stirred solution of 3.81 grams(g)(0.05 mole) of sodium sulfide in 100 mL of dimethylformamide was added 8 g (0.041 mole) of 4-Phenyl-3-chloro-1,2,5-thiadiazole. The mixture was stirred 18 hours and to this mixture was added 6.68 g (1.5 molar equivalents) of chloromethyithiocyanate. This mixture was stirred for ~14 hours and then diluted with 100 mL of water and extracted with 200 mL of methylene chloride. The organic layer was separated and washed with water (2×100 mL), dried and concentrated under reduced pressure. The thus recovered crude material was chromatographed on silica gel with a 10% EtoAc:90% hexane mixture to yield 8.99 g (83 percent of theoretical) as an oil. Upon crystallization, a light yellow solid melting at 58°-60° C. was recovered in a yield of 69 percent of theoretical; 1H NMR (300 MHz, CDCl3)δ 4.77 (s, 2H), 7.49 (m, 3H), 7.82 (m, 2H); 13C NMR (75 MHz, CDCl3) δ 38.28, 111.46, 127.97, 128.78, 130.06, 151.77, 157.93; MS (EI) m/e 265(M+), 207, 148, 116. This mixture was stirred for ~14 hours extracted with 200 mL of methylene chloride The organic layer was separated washed with water (2×100 mL) dried concentrated under reduced pressure The thus recovered crude material was chromatographed on silica gel with a 10% EtoAc 90% hexane mixture to yield 8.99 g (83 percent of theoretical) as an oil Upon crystallization a light yellow solid melting at 58°-60° C. was recovered in a yield of 69 percent of theoretical

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

Procedure: To a mixture of 5.8 g (0.03 mole) 2-mercapto-3-allyl-4(3H)-quinazolinone (the product of Example 5) in 200 ml dimethoxyethane, 5.4 g (0.05 mole) chloromethyl thiocyanate and 2.4 g (0.05 mole) 50% sodium hydride were added. The resulting mixture was stirred overnight at ambient temperature, refluxed at 50° C. for 8 hours, stirred overnight, refluxed at 50° C. for 8 hours and stirred overnight. The reaction mixture was washed with water, extracted with methylene chloride, dried over magnesium sulfate and stripped. The oily residue was triturated with ether, to give the above-identified product, as a solid, melting point 73°-76° C. refluxed at 50° C. for 8 hours stirred overnight refluxed at 50° C. for 8 hours stirred overnight The reaction mixture was washed with water extracted with methylene chloride dried over magnesium sulfate The oily residue was triturated with ether to give the above-identified product

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:62.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirring mixture a 1.5 grams (0.0047 mole) of 3,4,5-trichloro-N,N-dimethyl-2-(mercapto)benzenesulfonamide in 80 milliliters of methanol at 25° C, was added 0.39 grams of sodium methoxide. The mixture was stirred for 15 minutes and thereafter 1.0 gram (0.009 mole) of chloromethylthiocyanate was added thereto and the mixture stirred at room temperature for 3 hours. At the end of this time period, the reaction mixture was filtered to remove the solids which had precipitated. The filtrate further heated at 62° C for 2 hours and after cooling, the solvent was reduced in volume by evaporation under reduced pressure. The solids were thereafter removed by filtration. Additional filtrations gave additional solids. The recovered solids were combined and dissolved in chloroform and filtered. The solvent was removed by evaporation under reduced pressure and the solid product which remained was air dried. The 3,4,5-trichloro-N,N-dimethyl-2-((thiocyanomethyl)thio)benzenesulfonamide product was recovered in a yield of 0.7 grams (40 percent of theoretical) and melted at 155°-156° C. the mixture stirred at room temperature for 3 hours At the end of this time period, the reaction mixture was filtered to remove the solids which had precipitated after cooling the solvent was reduced in volume by evaporation under reduced pressure The solids were thereafter removed by filtration Additional filtrations gave additional solids filtered The solvent was removed by evaporation under reduced pressure dried The 3,4,5-trichloro-N,N-dimethyl-2-((thiocyanomethyl)thio)benzenesulfonamide product was recovered in a yield of 0.7 grams (40 percent of theoretical) and melted at 155°-156° C.

Conditions: temp:62.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirring mixture a 1.5 grams (0.0047 mole) of 3,4,5-trichloro-N,N-dimethyl-2-(mercapto)benzenesulfonamide in 80 milliliters of methanol at 25° C, was added 0.39 grams of sodium methoxide. The mixture was stirred for 15 minutes and thereafter 1.0 gram (0.009 mole) of chloromethylthiocyanate was added thereto and the mixture stirred at room temperature for 3 hours. At the end of this time period, the reaction mixture was filtered to remove the solids which had precipitated. The filtrate further heated at 62° C for 2 hours and after cooling, the solvent was reduced in volume by evaporation under reduced pressure. The solids were thereafter removed by filtration. Additional filtrations gave additional solids. The recovered solids were combined and dissolved in chloroform and filtered. The solvent was removed by evaporation under reduced pressure and the solid product which remained was air dried. The 3,4,5-trichloro-N,N-dimethyl-2-((thiocyanomethyl)thio)benzenesulfonamide product was recovered in a yield of 0.7 grams (40 percent of theoretical) and melted at 155°-156° C. the mixture stirred at room temperature for 3 hours At the end of this time period, the reaction mixture was filtered to remove the solids which had precipitated after cooling the solvent was reduced in volume by evaporation under reduced pressure The solids were thereafter removed by filtration Additional filtrations gave additional solids filtered The solvent was removed by evaporation under reduced pressure dried The 3,4,5-trichloro-N,N-dimethyl-2-((thiocyanomethyl)thio)benzenesulfonamide product was recovered in a yield of 0.7 grams (40 percent of theoretical) and melted at 155°-156° C.

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

Procedure: To a vigorously stirred solution of 9.6 grams (0.04 mole) of sodium sulfide nonahydrate in 100 milliliters of dimethylformamide was gradually added 6.6 grams (0.04 mole) of 2,6-dichloropyrazine-1-oxide in 50 milliliters of dimethylformamide. The reaction mixture was stirred overnight at ~40° C. Thereafter, 4.3 grams (0.04 mole) of chloromethylthiocyanate were gradually added and the mixture stirred for 4 hours. At the completion of the reaction, the dimethylformamide was removed by evaporation under reduced pressure and the residue was dissolved in a mixture of water and chloroform. Two phases formed and the aqueous phase was acidified with hydrochloric acid and extracted with chloroform. The organic portions were combined and washed with both a saturated sodium bicarbonate solution and a saturated sodium chloride solution and dried over magnesium sulfate. The chloroform was thereafter removed by evaporation leaving the 6-chloro-2-(thiocyanatomethylthio)pyrazine-1-oxide as a residue. The product was recrystallized from methanol and was recovered in a yield of 3.0 grams (32 percent of theoretical). The product melted at 95°-98° C and upon analysis was found to have carbon, hydrogen, chlorine, nitrogen and sulfur contents of 31.00, 1.82, 15.20, 18.04 and 27.20 percent, respectively, as compared with the theoretical contents of 30.84, 1.71, 15.20, 17.99 and 27.41 percent, respectively, as calculated for the above-named compound. the mixture stirred for 4 hours At the completion of the reaction the dimethylformamide was removed by evaporation under reduced pressure the residue was dissolved in a mixture of water and chloroform Two phases formed extracted with chloroform washed with both a saturated sodium bicarbonate solution a saturated sodium chloride solution and dried over magnesium sulfate The chloroform was thereafter removed by evaporation

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

Procedure: To a vigorously stirred solution of 9.6 grams (0.04 mole) of sodium sulfide nonahydrate in 100 milliliters of dimethylformamide was gradually added 5.2 grams (0.04 mole) of 3-chloropyrazine-1-oxide in 50 milliliters of dimethylformamide. The reaction mixture was stirred overnight at 45°-50° C. Thereafter, 4.3 grams (0.04 mole) of chloromethylthiocyanate were gradually added and the mixture stirred for 4 hours. At the completion of the reaction, the dimethylformamide was removed by evaporation under reduced pressure and the residue was dissolved in a mixture of water and chloroform. Two phases formed and the aqueous phase was acidified with hydrochloric acid and extracted with chloroform. The organic portions were combined and washed with both a saturated sodium bicarbonate solution and a saturated sodium chloride solution and dried over magnesium sulfate. The chloroform was thereafter removed by evaporation leaving the 3-(thiocyanatomethylthio)pyrazine-1-oxide as a residue. The product was recrystallized from methanol and was recovered in a yield of 4.75 grams (60 percent of theoretical). The product melted at 104°-106° C and upon analysis was found to have carbon, hydrogen, nitrogen and sulfur contents of 36.40, 2.66, 20.59 and 32.20 percent, respectively, as compared with the theoretical contents of 36.18, 2.51, 21.11 and 32.16 percent, respectively, as calculated for the above-named compound. the mixture stirred for 4 hours At the completion of the reaction the dimethylformamide was removed by evaporation under reduced pressure the residue was dissolved in a mixture of water and chloroform Two phases formed extracted with chloroform washed with both a saturated sodium bicarbonate solution a saturated sodium chloride solution and dried over magnesium sulfate The chloroform was thereafter removed by evaporation