Acetonitrile → N-Cyano-N'-methyl-6-nitro-2,2-dimethyl-2H-1-benzopyran-4-carboxamidine

HRID 36074Notes

Reaction equation

HRID 36074 reaction equation
[CH3:1][NH:2][C:3]([C:5]1[C:10]2[CH:11]=[C:12]([N+:15]([O-:17])=[O:16])[CH:13]=[CH:14][C:9]=2[O:8][C:7]([CH3:19])([CH3:18])[CH:6]=1)=S.C1(C)C=CC(S(Cl)(=O)=O)=CC=1.C([N:33]([CH2:36]C)CC)C.C(#[N:40])C>>[C:1]([NH:2][C:3]([C:5]1[C:10]2[CH:11]=[C:12]([N+:15]([O-:17])=[O:16])[CH:13]=[CH:14][C:9]=2[O:8][C:7]([CH3:19])([CH3:18])[CH:6]=1)=[N:33][CH3:36])#[N:40]

Participants

5

Reactant 4

HCID 6342AcetonitrileHCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 10423672N,2,2-trimethyl-6-nitro-2H-1-benzopyran-4-carbothioamide

Product 1

HCID 15234743N-Cyano-N'-methyl-6-nitro-2,2-dimethyl-2H-1-benzopyran-4-carboxamidine

Procedure

A mixture of 0.56 g of N-methyl-6-nitro-2,2-dimethyl-2H-1-benzopyran-4-carbothioamide, 0.39 g of p-toluenesulfonyl chloride, 0.21 g of triethylamine, and 3 ml of acetonitrile was heated at reflux for 30 minutes. The solvent was removed by distillation, and to the residue were added 0.27 g of cyanamide, 0.17 g of sodium hydride, and 4 ml of ethanol, followed by heating under reflux for 30 minutes. Concentrated hydrochloric acid and water were added to the reaction mixture, and the mixture was extracted with methylene chloride. The organic layer was washed successively with a 2N potassium carbonate aqueous solution and a saturated sodium chloride aqueous solution and dried over magnesium sulfate. The solvent was removed by distillation, and the residue was subjected to silica gel column chromatography (developing solution: n-hexane:ethyl acetate=1:1) and then recrystallized from a mixture of ethyl acetate and diethyl ether to obtain 50 mg of the titled compound.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 30 minutes
  3. customThe solvent was removed by distillation
  4. additionto the residue were added 0.27 g of cyanamide, 0.17 g of sodium hydride, and 4 ml of ethanol
  5. temperatureby heating
  6. temperatureunder reflux for 30 minutes
  7. additionConcentrated hydrochloric acid and water were added to the reaction mixture
  8. extractionthe mixture was extracted with methylene chloride
  9. washThe organic layer was washed successively with a 2N potassium carbonate aqueous solution
  10. dry with materiala saturated sodium chloride aqueous solution and dried over magnesium sulfate
  11. customThe solvent was removed by distillation
  12. customrecrystallized from a mixture of ethyl acetate and diethyl ether

Sources & evidence

ORD record
ord-4217d1255689450c83b6b2cb67e2bd9d
Source dataset
uspto-grants-1995_05
Patent number
US05412117

Reaction notes

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