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

HRID 518955Notes

Reaction equation

HRID 518955 reaction equation
[Br:1][C:2]1[C:19]([C:20]([F:23])([F:22])[F:21])=[CH:18][C:5]2[O:6][CH2:7][C:8](=O)[N:9]([CH:10]([CH3:16])[C:11](OCC)=[O:12])[C:4]=2[CH:3]=1.COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=S)=CC=1.O.[NH2:47][NH2:48]>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[C:4]2[C:5](=[CH:18][C:19]=1[C:20]([F:23])([F:22])[F:21])[O:6][CH2:7][C:8]1[N:9]2[CH:10]([CH3:16])[C:11](=[O:12])[NH:47][N:48]=1

Participants

5

Reactant 3

HCID 24654Hydrazine hydrate (1:1)HCID 87949Lawesson's reagentHCID 86727302ethyl 2-(6-bromo-3-oxo-7-(trifluoromethyl)-2H-benzo[b][1,4]oxazin-4(3H)-yl)propanoate

Product 1

HCID 867273016-Bromo-4-methyl-7-trifluoromethyl-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-oneYield 18.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of ethyl 2-(6-bromo-3-oxo-7-(trifluoromethyl)-2H-benzo[b][1,4]oxazin-4(3H)-yl)propanoate (7.7 g, 19.44 mmol) and Lawesson reagent (8.65 g, 21.38 mmol) in toluene (20 mL) was heated at reflux for 1 h. The reaction mixture was cooled to ambient temperature, hydrazine hydrate (4.98 g, 155 mmol) was added and the reaction mixture was heated at 80° C. for 1 h. The reaction mixture was cooled to ambient temperature and the solvent was evaporated in vacuo. The residue was purified by column chromatography on silica gel (eluting with 16-33% EtOAc in petroleum ether) to give 6-bromo-4-methyl-7-trifluoromethyl-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one as white solid (1.30 g, 18%). 1H NMR (DMSO-d6, 400 MHz): δ 10.92 (s, 1H), 7.66 (s, 1H), 7.34 (s, 1H), 4.88 (q, J=6.8 Hz, 1H), 4.72 (d, J=13.2 Hz, 1H), 4.64 (d, J=13.2 Hz, 1H), 1.30 (d, J=6.8 Hz, 3H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 1 h
  3. temperaturethe reaction mixture was heated at 80° C. for 1 h
  4. temperatureThe reaction mixture was cooled to ambient temperature
  5. customthe solvent was evaporated in vacuo
  6. customThe residue was purified by column chromatography on silica gel (eluting with 16-33% EtOAc in petroleum ether)

Sources & evidence

ORD record
ord-1184692527be4a798dd435229b0a663c
Source dataset
uspto-grants-2015_08
Patent number
US09115151B2

Reaction notes

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