Ammonia → 9-Cyano-2-methoxy-10,11-dihydro-11-oxo-dibenzo[b,f]thiepin

HRID 903631Notes

Reaction equation

HRID 903631 reaction equation
[CH3:1][N:2]1CCCC1=O.F[C:9]1[C:14]2[CH2:15][C:16](=[O:26])[C:17]3[CH:23]=[C:22]([O:24][CH3:25])[CH:21]=[CH:20][C:18]=3[S:19][C:13]=2[CH:12]=[CH:11][CH:10]=1.[Cu](C#N)C#N.N>S([O-])([O-])(=O)=O.[Cu+2].O>[C:1]([C:9]1[C:14]2[CH2:15][C:16](=[O:26])[C:17]3[CH:23]=[C:22]([O:24][CH3:25])[CH:21]=[CH:20][C:18]=3[S:19][C:13]=2[CH:12]=[CH:11][CH:10]=1)#[N:2]

Participants

7

Reactant 4

HCID 222AmmoniaHCID 13387N-methyl-2-pyrrolidoneHCID 233370699-Fluoro-2-methoxy-10,11-dihydro-11-oxo-dibenzo[b,f]-thiepinHCID 178418260HCID 178418260, compound

Product 1

HCID 126871079-Cyano-2-methoxy-10,11-dihydro-11-oxo-dibenzo[b,f]thiepin

Reagents, catalysts & solvents 2

HCID 24462Copper SulfateCatalystHCID 962WaterSolvent

Procedure

To 50 ml of N-methylpyrrolidone were added 5.8 g of 9-fluoro-2-methoxy-10,11-dihydro-11-oxo-dibenzo[b,f]-thiepin, 5.4 g of copper cyanide and 0.2 g anhydrous copper sulfate, and the resulting mixture was heated with stirring at 230°-240° C. for 14 hours. After cooling, to the reaction mixture were added 200 ml of 28% aqueous ammonia and 320 ml of water, and the resulting mixture was extracted with benzene. The aqueous and benzene layers were filtered through celite. The collected benzene layer was washed with water several times, diluted hydrochloric acid and then water, which was dried over anhydrous sodium sulfate. The solvent was evaporated to obtain about 6 g of residue which was chromatographed on silica gel. 1.0 g of the starting material was recovered from benzene/chloroform (1/1) eluate and there was obtained from chloroform eluate 9-cyano-2-methoxy-10,11-dihydro-11-oxo-dibenzo[b,f]-thiepin, which was washed with ethanol to give 2.1 g of pale yellow needles having a melting point of 188°-189° C.

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureAfter cooling, to the reaction mixture
  3. extractionthe resulting mixture was extracted with benzene
  4. filtrationThe aqueous and benzene layers were filtered through celite
  5. washThe collected benzene layer was washed with water several times, diluted hydrochloric acid
  6. dry with materialwater, which was dried over anhydrous sodium sulfate
  7. customThe solvent was evaporated

Sources & evidence

ORD record
ord-03fe1077ac67468a865823af6ef48dea
Source dataset
uspto-grants-1980_10
Patent number
US04228284

Reaction notes

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