Potassium Carbonate → Methyl 8-bromo-4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-2-carboxylate

HRID 1949669Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[CH:4][C:5]2=[C:6]([CH:15]=1)[O:7][CH2:8][CH2:9][C:10]([CH:13]=O)=[C:11]2Cl.C(=O)([O-])[O-].[K+].[K+].[C:22]([O:26][CH3:27])(=[O:25])[CH2:23][SH:24]>CN(C=O)C.O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11]3[S:24][C:23]([C:22]([O:26][CH3:27])=[O:25])=[CH:13][C:10]=3[CH2:9][CH2:8][O:7][C:6]=2[CH:15]=1

Participants

Conditions

Temperature: 50 °C

Procedure

(Z)-8-Bromo-5-chloro-2,3-dihydrobenzo[b]oxepine-4-carbaldehyde 9 was dissolved in 10 mL DMF and treated sequentially with potassium carbonate (2.20 g, 16.6 mmol) and methyl thioglycolate (0.83 mL). The whole was heated at 50° C. overnight, cooled to room temperature, diluted with water and extracted with ethylacetate. The combined organics were washed with brine, dried over sodium sulfate and concentrated. The crude residue was purified by flash column chromatography (20-50% ethylacetate in hexanes) to give 2.20 g (78% yield) 10 as a colorless solid. 1H NMR (DMSO-d6, 500 MHz) 7.70 (s, 1H), 7.67 (d, J=8.5 Hz, 1H), 7.31-7.28 (m, 2H), 4.32 (t, J=5.0 Hz, 2H), 3.84 (s, 3H), 3.21 (t, J=5.0 Hz, 2H).

Workup

temperaturecooled to room temperature
extractionextracted with ethylacetate
washThe combined organics were washed with brine
dry with materialdried over sodium sulfate
concentrationconcentrated
customThe crude residue was purified by flash column chromatography (20-50% ethylacetate in hexanes)

Sources & evidence

ORD record: ord-b938f82361bc4d28a6c3c4dd80e5db31
Source dataset: uspto-grants-2013_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08399690B2

Reaction notes

Loading…