Acetic Acid → 3-azido-7-chloro-1,3-dihydro-5-(6-methoxy-2-pyridinyl)-1-methyl-2H-1,4-benzodiazepin-2-one

反応式

C[Si]([N-][Si](C)(C)C)(C)C.[K+].[Cl:11][C:12]1[CH:13]=[CH:14][C:15]2[N:21]([CH3:22])[C:20](=[O:23])[CH2:19][N:18]=[C:17]([C:24]3[CH:29]=[CH:28][CH:27]=[C:26]([O:30][CH3:31])[N:25]=3)[C:16]=2[CH:32]=1.CC(C1C=C(C(C)C)C(S([N:48]=[N+:49]=[N-:50])(=O)=O)=C(C(C)C)C=1)C.C(O)(=O)C>>[N:48]([CH:19]1[N:18]=[C:17]([C:24]2[CH:29]=[CH:28][CH:27]=[C:26]([O:30][CH3:31])[N:25]=2)[C:16]2[CH:32]=[C:12]([Cl:11])[CH:13]=[CH:14][C:15]=2[N:21]([CH3:22])[C:20]1=[O:23])=[N+:49]=[N-:50]

参加物

反応物 4

HCID 176Acetic Acid

HCID 3717072,4,6-Triisopropylbenzenesulfonyl azide

HCID 3251421Potassium bis(trimethylsilyl)amide

HCID 59713649HCID 59713649、化合物

生成物 1

HCID 597141213-azido-7-chloro-1,3-dihydro-5-(6-methoxy-2-pyridinyl)-1-methyl-2H-1,4-benzodiazepin-2-one収率 62.3%

実験手順

As illustrated in the scheme above and following General Procedure 6, KHMDS (0.19 mL of 0.5 M in toluene, 0.095 mmol), 7-chloro-1,3-dihydro-5-(6-methoxy-2-pyridinyl)-1-methyl-2H-1,4-benzodiazepin-2-one (0.0290 g, 0.0918 mmol), trisyl azide (0.0710 g, 0.229 mmol) and acetic acid (0.023 mL, 0.40 mmol) were combined. After workup, purification of the crude product by silica gel column chromatography (49:1 CH2Cl2:EtOAc) provided the title compound (0.0204 g, 62%). 1H-NMR (CDCl3): δ 7.95 (d, J=7.2 Hz, 1H), 7.78-7.70 (m, 2H), 7.54 (dd, J=2.4 Hz, J=8.8 Hz, 1H), 7.31 (d, J=8.8 Hz, 1H), 6.87 (d, J=8.4 Hz, 1H), 4.64 (s, 1H), 3.80 (s, 3H), 3.44 (s, 3H). MS (ESI) (M+H)+=357.