Hexamethylphosphoramide → 7-bromo-3-phenyl-3,4-dihydrobenzo[b]oxepin-5(2H)-one

HRID 2096606Notes

Reaction equation

[Br:1][C:2]1[CH:13]=[CH:12][C:5]2[O:6][CH2:7][CH:8]=[CH:9][C:10](=[O:11])[C:4]=2[CH:3]=1.CN(P(N(C)C)(N(C)C)=O)C.[C:25]1([Mg]Br)[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1>C1COCC1>[Br:1][C:2]1[CH:13]=[CH:12][C:5]2[O:6][CH2:7][CH:8]([C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[CH2:9][C:10](=[O:11])[C:4]=2[CH:3]=1

Participants

Conditions

Temperature: -78 °C

Procedure

To a solution of 7-bromobenzo[b]oxepin-5(2H)-one (1.33 g, 5.6 mmol), CuBr—SMe2(60 mg, 0.3 mmol) and HMPA (2.058 g, 11.5 mmol) in THF (30 mL) was added phenylmagnesium bromide (3.0 M, 3.7 mL) at −78° C., the mixture was stirred at −78° C. for 1 hour. The mixture was quenched by HCl (10%, 5 mL), extracted with ethoxyethane, and then washed with NaHCO3, brine, dried over Na2SO4, concentrated and purified by column chromatography to give 7-bromo-3-phenyl-3,4-dihydrobenzo[b]oxepin-5(2H)-one (300 mg, 17%). 1H-NMR(CH2D2): 3.11 (m, 2H), 3.49 (m, 1H), 4.28 (m, 2H), 6.93 (m, 1H), 7.17 (m, 1H), 7.23 (m, 4H), 7.45 (m, 1H), 7.83 (m, 1H)

Workup

customThe mixture was quenched by HCl (10%, 5 mL)
extractionextracted with ethoxyethane
washwashed with NaHCO3, brine
dry with materialdried over Na2SO4
concentrationconcentrated
custompurified by column chromatography

Sources & evidence

ORD record: ord-7471d846756446ca8724664c8e774c83
Source dataset: uspto-grants-2013_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08450308B2

Reaction notes

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