Hydrazine hydrate (1:1) → 6-Amino-7-fluoro-4-methyl-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one

HRID 518976Notes

Reaction equation

C(O[C:4](=[O:20])[CH:5]([N:7]1[C:12]2[CH:13]=[C:14]([NH2:18])[C:15]([F:17])=[CH:16][C:11]=2[O:10][CH2:9][C:8]1=S)[CH3:6])C.O.[NH2:22][NH2:23]>CCO>[NH2:18][C:14]1[CH:13]=[C:12]2[C:11](=[CH:16][C:15]=1[F:17])[O:10][CH2:9][C:8]1[N:7]2[CH:5]([CH3:6])[C:4](=[O:20])[NH:22][N:23]=1

Participants

Conditions

Temperature: 90 °C

Procedure

To a solution of 2-(6-amino-7-fluoro-3-thioxo-2,3-dihydro-benzo[1,4]oxazin-4-yl)-propionic acid ethyl ester (0.400 g, 1.34 mmol) in EtOH (15 mL) was added hydrazine hydrate (98%, 0.430 g, 13.4 mmol) and the reaction mixture was stirred at 90° C. for 2 h. The reaction mixture was cooled to ambient temperature then concentrated in vacuo and the residue was purified by column on silica gel (basified by treatment with triethyl amine, eluting with 10-20% MeOH in DCM) to give 6-amino-7-fluoro-4-methyl-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one as a light yellow solid (0.316 g, 94%). 1H NMR (DMSO-d6, 400 MHz): δ 10.73 (s, 1H), 6.78 (d, J=11.6 Hz, 1H), 6.62 (d, J=8.8 Hz 1H), 4.84 (brs, 2H), 4.44-4.53 (m, 3H), 1.29 (d, J=6.8 Hz, 3H).

Workup

temperatureThe reaction mixture was cooled to ambient temperature
concentrationthen concentrated in vacuo
customthe residue was purified by column on silica gel (basified by treatment with triethyl amine, eluting with 10-20% MeOH in DCM)

Sources & evidence

ORD record: ord-f33928c5252f4dec83bac3b0e869e177
Source dataset: uspto-grants-2015_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09115151B2

Reaction notes

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