Benzoylhydrazine → 8,9-difluoro-1-phenyl-4H,6H-2,3,6,10b-tetraaza-benzo[e]azulen-5-one

HRID 914705Notes

Reaction equation

C(O[C:4]1[CH2:10][C:9](=[O:11])[NH:8][C:7]2[CH:12]=[C:13]([F:17])[C:14]([F:16])=[CH:15][C:6]=2[N:5]=1)C.[C:18]([NH:26][NH2:27])(=O)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C(O)(=O)C>[F:17][C:13]1[C:14]([F:16])=[CH:15][C:6]2[N:5]3[C:4]([CH2:10][C:9](=[O:11])[NH:8][C:7]=2[CH:12]=1)=[N:27][N:26]=[C:18]3[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

Conditions

Temperature: 120 °C

Procedure

To a solution of 4-ethoxy-7,8-difluoro-1,3-dihydro-benzo[b][1,4]diazepin-2-one (Preparation 3(B) (5.38 g, 22.4 mmol) in acetic acid (100 mL) was added benzoic hydrazide (3.11 g, 22.85 mmol). The reaction was heated to 120° C. for 18 hours and the volatiles were concentrated in vacuo. The residue was dissolved in CH2Cl2 and the organic solution was washed with aqueous NaHCO3 (1×), dried (Na2SO4), filtered and concentrated. The solid residue was triturated with a warm mixture of EtOAc and hexanes and was filtered. The solids were triturated in 50% hexanes in Et2O and filtered to provide 3.97 g of 8,9-difluoro-1-phenyl-4H,6H-2,3,6,10b-tetraaza-benzo[e]azulen-5-one. 1H NMR (DMSO-d6) δ 7.52-7.36 (m, 6H), 7.06 (m, 1H), 3.91 (d, 1H), 3.76 (d, 1H); MS 313.1 (M+1), 311.1 (M−1).

Workup

concentrationthe volatiles were concentrated in vacuo
dissolutionThe residue was dissolved in CH2Cl2
washthe organic solution was washed with aqueous NaHCO3 (1×)
dry with materialdried (Na2SO4)
filtrationfiltered
concentrationconcentrated
customThe solid residue was triturated with a warm mixture of EtOAc and hexanes
filtrationwas filtered
customThe solids were triturated in 50% hexanes in Et2O
filtrationfiltered

Sources & evidence

ORD record: ord-a2da400dc23c44d99b0e4e612794c387
Source dataset: uspto-grants-2007_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07265104B2

Reaction notes

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