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

HRID 707808Notes

Reaction equation

HRID 707808 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

5

Reactant 3

HCID 176Acetic AcidHCID 67184N-bromobutanimideHCID 58203803HCID 58203803, compound

Product 1

HCID 582040089-Bromo-2-chloro-6,7-dihydrothieno[2',3':4,5]oxepino[3,2-b]pyridine

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

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

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

Sources & evidence

ORD record
ord-70d72ab9bf134ae48fa50f6bf48fc19c
Source dataset
uspto-grants-2015_11
Patent number
US09175009B2

Reaction notes

Loading…