, The residue was purified by flash chromatography (cyclohexane/ethylacetate 1:1) affording 17 mg (41%) of 5-I and 2 mg (4%) of 5-II. IR (NaCl, cm ?1 ) 3207, 3117, CD 3 ) 2 SO) ? 10.82 (s, 1H, 1-H), 7.89 (d, J = 7.8 Hz, 1H, 3? -H), 7.71 (dd, J = 8.7 Hz, J = 2.3 Hz, 1H, 8-H), 7.52 (dt' , J = 7.4 Hz, J = 0.8 Hz, 1H, 5? -H), vol.7, 1011.

. Hr-ms,

, OAc) 2 (2.4 mg, 0.010 mmol) and N-iodosuccinimide (47 mg, 0.210 mmol). The mixture was stirred at 100 °C under microwave irradiation for 15 minutes. The crude mixture was evaporated, diluted in ethyl acetate (10 mL), and washed with a 2 M aqueous solution of NaOH (5 mL). The residue was purified by flash chromatography (cyclohexane/ethylacetate 1:1) affording 26 mg (60%) of 6-I and 2 mg (3%) of 6-II. IR (NaCl, cm ?1 ) 3060, 2?-iodo-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one (6-I). To a solution of 7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one 6 (30 mg, 0.105 mmol, vol.1, 1016.

=. O), C-4? ), 131.8 (C-5? or C-6? ), 131.5 (C-5a), 118.3 (C-9a), 96.8 (C-2? ), vol.144

. Hr-ms, To a solution of 7-bromo-1,3-dihydro-1-benzyl-5-phenyl-2H-1,4-benzodiazepin-2-one (30 mg, 0.074 mmol) in CH 3 CN (740 ? L), were added Pd(OAc) 2 (1.6 mg, 0.0074 mmol) and N-iodosuccinimide (33.5 mg, 0.148 mmol). The mixture stirred at 100 °C under microwave irradiation for 15 minutes under microwave irradiation. The crude mixture was evaporated, diluted in ethyl acetate (10 mL), and washed with a 2M aqueous solution of NaOH (5 mL). The residue was purified by flash chromatography (cyclohexane/ethylacetate 1:1) affording 27 mg (69%) of 7-I and 3 mg (6%) of 7-II. IR (KBr, cm ?1 ) 3061, 3029, ESI+ ) m/z Calcd for C 16 H 13 ClIN 2 O [M+ H + ] 410.9761, Found 410.9766. Synthesis of 7-bromo-2?-iodo-1,3-dihydro-1-benzyl-5-phenyl-2H-1,4-benzodiazepin-2-one (7-I), vol.938, 1015.

. Hr-ms, ESI+ ) m/z Calcd for C 22 H 19 BrIN 2 O

, The mixture was stirred at 100 °C under microwave irradiation for 15 minutes. The crude mixture was evaporated, diluted in ethyl acetate (10 mL), and washed with a 2 M aqueous solution of NaOH (5 mL). The residue was purified by flash chromatography (cyclohexane/ethylacetate 1:1) affording 27 mg (61%) of 8-I and 2 mg (3%) of 8-II. IR (NaCl, cm ?1 ) 3057, 2?-iodo-4?-methyl-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one (8-I). To a solution of 4? -methyl-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one 8 (30 mg, 0.11 mmol, 0984.

. Hr-ms,

, To a solution of 1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one 1 (10 mg, 0.04 mmol) in DMF (400 ? L), were added Pd(OAc) 2 (0.9 mg, 0.004 mmol) and N-bromosuccinimide (36 mg, 0.2 mmol). The mixture References 1. Fahey, D. R. The coordination-catalyzed ortho-halogenation of azobenzene, 2?-bromo-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one (1-Br), vol.27, pp.283-292, 1971.

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