8-Bromo-4,5-dihydro-6-oxa-1-thia-benzo[e]azulene → 4,5-Dihydrobenzo[b]thieno[2,3-d]oxepine-8-carbonitrile

HRID 1849036Notes

Reaction equation

HRID 1849036 reaction equation
Br[C:2]1[CH:15]=[CH:14][C:5]2[C:6]3[S:7][CH:8]=[CH:9][C:10]=3[CH2:11][CH2:12][O:13][C:4]=2[CH:3]=1.[Cu](C#N)[C:17]#[N:18]>CN(C=O)C.CCOC(C)=O>[S:7]1[C:6]2[C:5]3[CH:14]=[CH:15][C:2]([C:17]#[N:18])=[CH:3][C:4]=3[O:13][CH2:12][CH2:11][C:10]=2[CH:9]=[CH:8]1

Participants

5

Reactant 2

HCID 670505438-Bromo-4,5-dihydro-6-oxa-1-thia-benzo[e]azuleneHCID 178418260HCID 178418260, compound

Product 1

HCID 582037704,5-Dihydrobenzo[b]thieno[2,3-d]oxepine-8-carbonitrileYield 124.3%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 8-bromo-4,5-dihydro-6-oxa-1-thia-benzo[e]azulene (0.500 grams, 1.77 mmol) and copper cyanide (0.48 grams, 5.30 mmol) in 10 ml of DMF was flash heated on Biotage microwave. The reaction mixture was diluted with a large volume of EtOAc and this solution was filtered through celite by vacuum filtration. The filtrate was plated onto a 1/1 mixture on silica/celite and dry load purified by MPLC on a 14 gram silica column eluting with 10 to 80% EtOAc/heptanes to give 500 mg (123%) of 4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-8-carbonitrile as determined by LC/MS.

Workup

  1. temperatureheated on Biotage microwave
  2. filtrationthis solution was filtered through celite by vacuum filtration
  3. customdry load
  4. custompurified by MPLC on a 14 gram silica column
  5. washeluting with 10 to 80% EtOAc/heptanes

Sources & evidence

ORD record
ord-ab23f86fed304336b36fd03bb9de1e6e
Source dataset
uspto-grants-2015_02
Patent number
US08952043B2

Reaction notes

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