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

HRID 903637Notes

Reaction equation

HRID 903637 reaction equation
Cl[C:2]1[C:7]2[CH2:8][C:9](=[O:17])[C:10]3[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=3[S:12][C:6]=2[CH:5]=[CH:4][CH:3]=1.[Cu](C#N)[C:19]#[N:20].CN1CCCC1=O.N>S([O-])([O-])(=O)=O.[Cu+2].O>[C:19]([C:2]1[C:7]2[CH2:8][C:9](=[O:17])[C:10]3[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=3[S:12][C:6]=2[CH:5]=[CH:4][CH:3]=1)#[N:20]

Participants

7

Reactant 4

HCID 222AmmoniaHCID 13387N-methyl-2-pyrrolidoneHCID 8270451-chlorodibenzo[b,f]thiepin-10(11H)-oneHCID 178418260HCID 178418260, compound

Product 1

HCID 126870859-Cyano 10,11-dihydro-11-oxo-dibenzo[b,f]thiepinYield 27.9%

Reagents, catalysts & solvents 2

HCID 24462Copper SulfateCatalystHCID 962WaterSolvent

Conditions

Temperature
200 °C

Procedure

The mixture of 2.6 g of 9-chloro-10,11-dihydro-11-oxo-dibenzo[b,f]thiepin, 2.0 g of copper cyanide, 0.1 g of anhydrous copper sulfate and 50 ml of N-methyl pyrrolidone was heated with stirring at 200° C. overnight in a flask equipped with a tube packed with silica gel. After cooling, to the reaction mixture were added 100 ml of conc. aqueous ammonia and 200 ml of water, and the resulting mixture was extracted with benzene. The extract was washed with water, diluted hydrochloric acid and then water, which was dried over potassium sulfate and the solvent was evaporated therefrom. The residue thus obtained was chromatographed on 200 g of silica gel, and eluted with chloroform/methanol (50/1). 0.6 g of the starting material was recovered from a first eluate. Recrystallization of the residue of a second eluate from benzene gave 0.7 g of 9-cyano-10,11-dihydro-11-oxo-dibenzo[b,f]thiepin as pale yellow prismatic crystals having a melting point of 165°-167° C.

Workup

  1. temperaturewas heated
  2. customequipped with a tube
  3. temperatureAfter cooling, to the reaction mixture
  4. extractionthe resulting mixture was extracted with benzene
  5. washThe extract was washed with water, diluted hydrochloric acid
  6. dry with materialwater, which was dried over potassium sulfate
  7. customthe solvent was evaporated
  8. customThe residue thus obtained
  9. customwas chromatographed on 200 g of silica gel
  10. washeluted with chloroform/methanol (50/1)
  11. custom0.6 g of the starting material was recovered from a first eluate
  12. customRecrystallization of the residue of a second eluate from benzene

Sources & evidence

ORD record
ord-5ef292a43ca14534ade51fe749e6e0f7
Source dataset
uspto-grants-1980_10
Patent number
US04228284

Reaction notes

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