[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]3[C:20]([CH3:21])=[C:19]([CH3:22])[S:18][C:10]=3[NH:11][C:12](=S)[C:13]([CH3:16])([CH3:15])[N:14]=2)=[CH:4][CH:3]=1.O.[NH2:24][NH2:25].C(N(CC)CC)C.[C:33](Cl)(=[O:35])[CH3:34]>ClCCl.O1CCCC1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]3[C:20]([CH3:21])=[C:19]([CH3:22])[S:18][C:10]=3[NH:11]/[C:12](=[N:24]\[NH:25][C:33](=[O:35])[CH3:34])/[C:13]([CH3:16])([CH3:15])[N:14]=2)=[CH:4][CH:3]=1A round bottomed flask was charged with 5-(4-chlorophenyl)-3,3,6,7-tetramethyl-1H-thieno[2,3-e][1,4]diazepine-2(3H)-thione (123 mg, 0.353 mmol) and a stir bar. Tetrahydrofuran (10 mL, 0.05 M) was added, and the solution was cooled to 0° C. for the addition of hydrazine hydrate (132 μl, 1.763 mmol). Stirred at room temperature 30 min, at which point both TLC and LC/MS analysis indicated essentially complete consumption of the starting material. Triethylamine (295 μl, 2.115 mmol, 6 equiv) was added, followed by acetic acid chloride (150 μl, 2.115 mmol, 6 equiv) (careful! exothermic!), and the solution stirred at rt 1 h. The solution was diluted with dichloromethane and concentrated for purification by column chromatography (eluting with dichloromethane/methanol/ammonium hydroxide), which yielded (Z)—N′-(5-(4-chlorophenyl)-3,3,6,7-tetramethyl-1H-thieno[2,3-e][1,4]diazepin-2(3H)-ylidene)acetohydrazide as a dark red oil (m/z=389) that was used in the subsequent reaction.
読み込み中…
