Methyl iodide → HCID 19037073, compound

HRID 264832Notes

Reaction equation

HRID 264832 reaction equation
[CH3:1][O:2][CH2:3][C:4]1([CH3:21])[CH:9]=[C:8]([C:10]([NH:12][CH3:13])=[O:11])[C:7]2[CH:14]=[C:15]([N+:18]([O-:20])=[O:19])[CH:16]=[CH:17][C:6]=2[O:5]1.[CH3:22]I.[H-].[Na+]>CN(C)C=O>[CH3:1][O:2][CH2:3][C:4]1([CH3:21])[CH:9]=[C:8]([C:10]([N:12]([CH3:22])[CH3:13])=[O:11])[C:7]2[CH:14]=[C:15]([N+:18]([O-:20])=[O:19])[CH:16]=[CH:17][C:6]=2[O:5]1

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 19037037HCID 19037037, compound

Product 1

HCID 19037073HCID 19037073, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a mixture of 130 mg of 2-methoxymethyl-N,2-dimethyl-6-nitro-2H-1-benzopyran-4-carboxamide, 83 μl of methyl iodide and 5 ml of dried N,N-dimethylformamide was added 21 mg of sodium hydride (60%) with stirring under ice-cooling and stirred at room temperature for 15 hours. Ice water was added to the reaction solution and it was extracted with ether. An organic layer was washed with water and dried, and the solvent was distilled. The resultant residue was purified according to silica gel column chromatography (developing solution, MeOH:CH2Cl2 =1:99) to obtain 130 mg of 2-methoxymethyl-N,N,2-trimethyl-6-nitro-2H-1-benzopyran-4-carboxamide. Subsequently, 103 mg of a Lawesson's reagent and 8 ml of benzene were added therein and the resultant mixture was refluxed with heating for 1 hour. After the reaction solution was vacuum-condensed, the residue was purified according to silica gel column chromatography (developing solution, hexane:AcOEt=3:1) to obtain 140 mg of 2-methoxymethyl-N,N,2-trimethyl-6-nitro-2H-1-benzopyran-4-carbothioamide. Subsequently, 290 μl of iodomethane, 104 mg of cyanamide and 8 ml of dried tetrahydrofuran were added therein and 96 mg of sodium hydride (60%) was added therein with stirring under ice-cooling, and the resultant mixture was stirred at room temperature for 15 hours. Ice water was added to the reaction product and it was extracted with ethyl acetate. an organic layer was washed with water and dried, and the solvent was distilled. The resultant residue was purified according to silica gel column chromatography (developing solution, hexane:AcOEt=2:3) to obtain 125 mg of N-cyano-2-methoxymethyl-N',N',2-trimethyl-6-nitro-2H-1-benzopyran-4-amidine with a melting point of 143°-146° C.

Workup

  1. temperaturecooling
  2. stirringstirred at room temperature for 15 hours
  3. extractionwas extracted with ether
  4. washAn organic layer was washed with water
  5. customdried
  6. distillationthe solvent was distilled
  7. customThe resultant residue was purified

Sources & evidence

ORD record
ord-fc6b378eb55a4a85a52353c768e5b0cd
Source dataset
uspto-grants-1997_07
Patent number
US05646308

Reaction notes

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