Methyl iodide → HCID 19037074, compound

HRID 264846Notes

Reaction equation

HRID 264846 reaction equation
[CH3:1][NH:2][C:3]([C:5]1[C:15]2[CH:16]=[C:17]([N+:20]([O-:22])=[O:21])[CH:18]=[CH:19][C:14]=2[O:13][C:7]2([CH2:12][CH2:11][O:10][CH2:9][CH2:8]2)[CH:6]=1)=[O:4].[CH3:23]I.[H-].[Na+]>CN(C)C=O>[CH3:1][N:2]([CH3:23])[C:3]([C:5]1[C:15]2[CH:16]=[C:17]([N+:20]([O-:22])=[O:21])[CH:18]=[CH:19][C:14]=2[O:13][C:7]2([CH2:12][CH2:11][O:10][CH2:9][CH2:8]2)[CH:6]=1)=[O:4]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 19037053HCID 19037053, compound

Product 1

HCID 19037074HCID 19037074, compoundYield 97.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a mixture of 0.64 g of N-methyl-6-nitrospiro[2H-1-benzopyran-2,4'-tetrahydropyran]-4-carboxamide, 1.05 g of methyl iodide and 40 ml of dried N,N-dimethylformamide was added 0.13 g of sodium hydride (60%) with stirring under ice-cooling and the mixture was stirred at room temperature for 17 hours. Ice water was added therein and the resultant mixture was extracted with ether. An organic layer was washed with water and dried. The solvent was distilled to obtain 0.65 g of N,N-dimethyl-6-nitrospiro[2H-1-benzopyran-2,4'-tetrahydropyran]-4-carboxamide. Subsequently, 0.63 g of a Lawesson's reagent and 30 ml of benzene were added therein, and the mixture was refluxed with heating for 1.5 hours. After the reaction solution was vacuum-condensed, the residue was purified according to silica gel column chromatography (developing solution, MeOH:CH2Cl2 =1:99) to obtain 0.43 g of N,N-dimethyl-6-nitrospiro[2H-1-benzopyran-2,4'-tetrahydropyran]-4-carbothioamide. Subsequently, 1.80 g of methyl iodide, 0.28 g of cyanamide and 20 ml of tetrahydrofuran were added therein. 0.29 g of sodium hydride (60%) was added therein with stirring under ice-cooling and the mixture was stirred at room temperature for 17 hours. Ice water was added therein and the resultant mixture was extracted with methylene chloride. After an organic layer was washed with water and dried, the solvent was distilled. The resultant residue was purified according to silica gel column chromatography (developing solution, MeOH:CH2Cl2 =1:99) to obtain 0.28 g of N-cyano-N',N'-dimethyl-6-nitrospiro[2H-1-benzopyran-2,4'-tetrahydro-pyran]-4-amidine with a melting point of 202°-203° C.

Workup

  1. temperaturecooling
  2. stirringthe mixture was stirred at room temperature for 17 hours
  3. extractionthe resultant mixture was extracted with ether
  4. washAn organic layer was washed with water
  5. customdried
  6. distillationThe solvent was distilled

Sources & evidence

ORD record
ord-0bf6dc1385134455a98feaf4083727cd
Source dataset
uspto-grants-1997_07
Patent number
US05646308

Reaction notes

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