Cesium carbonate → 4-(2-Methoxy-6-nitrophenyl)-[1,4]diazepane-1-carboxylic acid tert-butyl ester

HRID 532822Notes

Reaction equation

[C:1]([N:8]1[CH2:14][CH2:13][CH2:12][NH:11][CH2:10][CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].Br[C:16]1[C:21]([N+:22]([O-:24])=[O:23])=[CH:20][CH:19]=[CH:18][C:17]=1[O:25][CH3:26].C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C.CCCCCC.C(OCC)(=O)C.O>[C:4]([O:3][C:1]([N:8]1[CH2:14][CH2:13][CH2:12][N:11]([C:16]2[C:21]([N+:22]([O-:24])=[O:23])=[CH:20][CH:19]=[CH:18][C:17]=2[O:25][CH3:26])[CH2:10][CH2:9]1)=[O:2])([CH3:7])([CH3:6])[CH3:5]

Participants

Conditions

Temperature: 60 °C

Procedure

A mixture of BOC-homopiperazine (1.0 g, 5 mmol, 1 equiv), 2-bromo-1-methoxy-3-nitrobenzene (1.16 g, 1 equiv), cesium carbonate (1.7 g, 1 equiv) in 10 mL of DMF was heated at 60° C. over 72 hrs. After cooling down to room temperature, ethyl acetate (100 mL) and water (50 mL) were added. The organic layer was subjected to flash chromatography (5 to 40% ethyl acetate in hexane) to give 4-(2-methoxy-6-nitrophenyl)-[1,4]diazepane-1-carboxylic acid tert-butyl ester (0.50 g, 25%), which was then treated with 50 mL of 4N HCl in dioxane at 60° C. for 2 hrs. The mixture was then evaporated to dryness and used in the next step directly. MS (ES) m/z 252.1 (M+H+).

Workup

temperatureAfter cooling down to room temperature

Sources & evidence

ORD record: ord-f31543b863f943d1886a0b222267a7e9
Source dataset: uspto-grants-2014_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08853202B2

Reaction notes

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