Acetic Acid → 9-Bromo-2-chloro-6,7-dihydrothieno[2',3':4,5]oxepino[3,2-b]pyridine

HRID 1848988Notes

Reaction equation

[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[O:14][CH2:13][CH2:12][C:11]3[CH:10]=[CH:9][S:8][C:7]=3[C:6]=2[N:15]=1.C(O)(=O)C.[Br:20]N1C(=O)CCC1=O>C(Cl)Cl>[Br:20][C:9]1[S:8][C:7]2[C:6]3[N:15]=[C:2]([Cl:1])[CH:3]=[CH:4][C:5]=3[O:14][CH2:13][CH2:12][C:11]=2[CH:10]=1

Participants

Conditions

Temperature: 2.5 °C

Procedure

9-Chloro-4,5-dihydro-6-oxa-1-thia-10-aza-benzo[e]azulene (4.33 g, 18.2 mmol) was dissolved in methylene chloride (40 mL, 600 mmol)/acetic acid (40 mL, 700 mmol). The solution was cooled down to 0-5° C. and added a solution of N-Bromosuccinimide (3.57 g, 20.0 mmol) in 10 mL of DCM slowly. The reaction mixture was stirred for 18 hours. After removal of the solvents, the residue was partitioned between ethyl acetate and saturated sodium carbonate aqueous solution. The organic layer was washed with water, brine and dried over sodium sulfate. After filtration, the filtrate was concentrated to give 2-Bromo-9-chloro-4,5-dihydro-6-oxa-1-thia-10-aza-benzo[e]azulene. 1HNMR (DMSO, 400 MHz): δ 7.48 (d, J=8.4 Hz, 1H, ArH), 7.28 (d, J=8.4 Hz, 1H, ArH), 7.18 (s, 1H, ═CH), 4.32 (t, J=4.4 Hz, 2H, CH2), 3.17 (t, J=4.4 Hz, 2H, CH2).

Workup

customAfter removal of the solvents
customthe residue was partitioned between ethyl acetate and saturated sodium carbonate aqueous solution
washThe organic layer was washed with water, brine
dry with materialdried over sodium sulfate
filtrationAfter filtration
concentrationthe filtrate was concentrated

Sources & evidence

ORD record: ord-716e5ce13e384b62bdfd6e1d9c5aeec3
Source dataset: uspto-grants-2015_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08952043B2

Reaction notes

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