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

HRID 2223093Notes

Reaction equation

HRID 2223093 reaction equation
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]

Participants

5

Reactant 4

HCID 176Acetic AcidHCID 3717072,4,6-Triisopropylbenzenesulfonyl azideHCID 3251421Potassium bis(trimethylsilyl)amideHCID 59713649HCID 59713649, compound

Product 1

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

Procedure

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.

Workup

  1. customAfter workup, purification of the crude product by silica gel column chromatography (49:1 CH2Cl2:EtOAc)

Sources & evidence

ORD record
ord-f47a274b78d34fb8bcb6c543b4e1f757
Source dataset
uspto-grants-2008_05
Patent number
US07375101B2

Reaction notes

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