2-methyl-1,2,3,5-tetrahydro-1,5-benzodiazepine-4-thione

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A disposable tube was charged with 4-methyl-4,5-dihydro-1H-benzo[b][1,4]diazepine-2(3H)-thione (163 mg, 0.848 mmol) and a stirbar. nBuOH (5 mL) was added, followed by acetohydrazide (126 mg, 1.695 mmol), and the solution was stirred at 130° C. overnight. The solution was concentrated and purified by silica gel chromatography (eluting with methylene chloride/methanol/1% ammonium hydroxide) to yield 1,5-dimethyl-5,6-dihydro-4H-benzo[b][1,2,4]triazolo[4,3-d][1,4]diazepine as an off-white amorphous solid (0.126 g, 0.588 mmol, 69%). The solution was concentrated purified by silica gel chromatography (eluting with methylene chloride/methanol/1% ammonium hydroxide)

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

Procedure: A disposable tube was charged with 4-methyl-4,5-dihydro-1H-benzo[b][1,4]diazepin-2(3H)-one (220 mg, 1.248 mmol) in THF (12 mL). Lawesson's Reagent (278 mg, 0.687 mmol) was added, and the solution was stirred at 80° C. 1 h. The solution was concentrated with celite and purified by silica gel chromatography to yield 4-methyl-4,5-dihydro-1H-benzo[b][1,4]diazepine-2(3H)-thione as a yellow foam (0.163 g, 0.848 mmol, 68%). 1 h The solution was concentrated with celite purified by silica gel chromatography

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

Procedure: A solution of 4-methyl-4,5-dihydro-1H-benzo[b][1,4]diazepine-2(3H)-thione (200 mg, 1.04 mmol) and acetohydrazide (150 mg, 2.07 mmol) in n-BuOH (10 mL) was heated at 130° C. overnight. The reaction mixture was evaporated, and then water (10 mL) was added, extracted with ethyl acetate (10 mL), dried with Na2SO4, and concentrated to give the crude product, which was purified by prep-TLC to give 1,5-dimethyl-5,6-dihydro-4H-benzo[b][1,2,4]triazolo[4,3-d][1,4]diazepine (100 mg, 45%). The reaction mixture was evaporated water (10 mL) was added extracted with ethyl acetate (10 mL) dried with Na2SO4 concentrated to give the crude product, which was purified by prep-TLC

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

Procedure: A solution of 4-methyl-4,5-dihydro-1H-benzo[b][1,4]diazepin-2(3H)-one (220 mg, 1.25 mmol) and P2S5 (444 mg, 2.0 mmol) in pyridine (10 mL) was heated at 120° C. for 30 min. To the mixture, water (10 mL) was added, and then extracted with ethyl acetate (20 mL), dried with Na2SO4, concentrated and purified by CombiFlash (PE:EA=10:1) to give 4-methyl-4,5-dihydro-1H-benzo[b][1,4]diazepine-2(3H)-thione (200 mg, 83%). LRMS (M+H)+: 192 m/z. extracted with ethyl acetate (20 mL) dried with Na2SO4 concentrated purified by CombiFlash (PE:EA=10:1)