Water → HCID 12044969, compound

HRID 1609875Notes

Reaction equation

[N+:1]([C:4]1[CH:5]=[C:6]([C:22]#[N:23])[NH:7][C:8]=1[C:9]1[CH:10]=[CH:11][C:12]2[NH:17][C:16](=[O:18])[O:15][C:14]([CH3:20])([CH3:19])[C:13]=2[CH:21]=1)([O-])=O.[Cl-].[NH4+].O>C(O)C.O.[Zn]>[NH2:1][C:4]1[CH:5]=[C:6]([C:22]#[N:23])[NH:7][C:8]=1[C:9]1[CH:10]=[CH:11][C:12]2[NH:17][C:16](=[O:18])[O:15][C:14]([CH3:19])([CH3:20])[C:13]=2[CH:21]=1

Participants

Conditions

Temperature: 80 °C

Procedure

A solution of 4-nitro-5-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)-1H-pyrrole-2-carbonitrile (0.4 g, 1.28 mmol) in ethanol/water (5:1, 20 mL) was treated sequentially with zinc powder (2.5 wt, 1.0 g) and ammonium chloride (5 wt, 2.0 g). The suspension was heated at 80° C. or 30 min, cooled to room temperature, poured into water (30 mL) and extracted with ethyl acetate (3×15 mL). The combined organic layer was washed with brine, dried over MgSO4 and purified by flash column chromatography on silica gel eluting with ethyl acetate to give 4-amino-5-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-3,1-benzoxazin-6-yl)-1H-pyrrole-2-carbonitrile (0.29 g, 80%) as a yellow solid. 1H NMR (500 MHz, d6-DMSO) δ1.63 (s, 6H), 4.29 (s, 2H); 6.39 (s, 1H), 6.89 (d, 1H, J=8.1 Hz), 7.49 (s, 1H), 7.52 (dd, 1H, J=8.1 and 2.3 Hz), 10.25 (s, 1H), 11.76 (s, 1H). MS (ESI (−)) m/z 281 (M−H)−. Anal. calcd for C15H14N4O2, C, 63.8, H, 5.00, N, 19.9. Found, C, 63.7, H, 5.10, N, 19.82

Workup

temperaturecooled to room temperature
extractionextracted with ethyl acetate (3×15 mL)
washThe combined organic layer was washed with brine
dry with materialdried over MgSO4
custompurified by flash column chromatography on silica gel eluting with ethyl acetate

Sources & evidence

ORD record: ord-d4630f4124134cb1bd1cd566eeb671e6
Source dataset: uspto-grants-2006_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06982261B2

Reaction notes

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