C[Al](C)C.[C:5]1([NH2:12])[C:6]([NH2:11])=[CH:7][CH:8]=[CH:9][CH:10]=1.C.C(OC([N:21]1[CH2:27][CH2:26][CH2:25][N:24]([C:28]2[CH:33]=[CH:32][C:31]([Cl:34])=[C:30]([C:35](OCC)=O)[CH:29]=2)[CH2:23][CH2:22]1)=O)(C)(C)C>C1(C)C=CC=CC=1.CO.O>[Cl:34][C:31]1[CH:32]=[CH:33][C:28]([N:24]2[CH2:25][CH2:26][CH2:27][NH:21][CH2:22][CH2:23]2)=[CH:29][C:30]=1[C:35]1[NH:12][C:5]2[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=2[N:11]=1
To a solution of trimethylaluminium (2.0 M solution in toluene) (90 mL, 180 mmol) in toluene (300 mL) cooled to 0° C. under nitrogen was added benzene-1,2-diamine (6.5 g, 60 mmol) portionwise. The solution was stirred for 30 minutes at 0° C. then at 15-20° C. until evolution of methane ceased. 4-(4-chloro-3-ethoxycarbonyl-phenyl)-[1,4]diazepane-1-carboxylic acid tert-butyl ester (15.2 g, 40 mmol) was added in one portion to the resulting solution. The reaction was heated to reflux for 24 h then cooled to 0° C. Water (70 mL) was added carefully followed by MeOH (700 mL) The solid precipitated was filtered and the filtrate was concentrated under reduced pressure. The precipitate was washed with hot DCM:MeOH 1:1 (400 mL) followed by AcOEt (200 mL) The solution was concentrated under reduced pressure. Two extracts were combined and purified by flash chromatography (eluent: AcOEt:MeOH:NH3 gradient from 100% AcOEt to AcOEt:MeOH:NH3 73:25:2) to afford 9.3 g of a mixture of 2-(2-Chloro-5-[1,4]diazepan-1-yl-phenyl)-1H-benzoimidazole and N-(2-amino-phenyl)-2-chlorodiazepan-1-yl-benzamide.
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