Methylamine → 2,2-bis(fluoromethyl)-N-methyl-6-nitro-2H-1-benzopyran-4-carboxamide

HRID 264838Notes

Reaction equation

HRID 264838 reaction equation
[F:1][CH2:2][C:3]1([CH2:19][F:20])[CH:8]=[C:7]([C:9](O)=[O:10])[C:6]2[CH:12]=[C:13]([N+:16]([O-:18])=[O:17])[CH:14]=[CH:15][C:5]=2[O:4]1.[C:21](N1C=CN=C1)([N:23]1C=CN=C1)=O.CN.C(=O)([O-])[O-].[K+].[K+]>O1CCCC1>[F:1][CH2:2][C:3]1([CH2:19][F:20])[CH:8]=[C:7]([C:9]([NH:23][CH3:21])=[O:10])[C:6]2[CH:12]=[C:13]([N+:16]([O-:18])=[O:17])[CH:14]=[CH:15][C:5]=2[O:4]1

Participants

6

Reactant 4

HCID 6329MethylamineHCID 11430Potassium CarbonateHCID 682631,1'-CarbonyldiimidazoleHCID 211949872,2-bisfluoromethyl-6-nitro-2H-1-benzopyran-4-carboxylic acid

Product 1

HCID 190370412,2-bis(fluoromethyl)-N-methyl-6-nitro-2H-1-benzopyran-4-carboxamideYield 15.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of 0.78 g of 2,2-bis(fluoromethyl)-6-nitro-2H-1-benzopyran-4-carboxylic acid and 5 ml of tetrahydrofuran was added 0.67 g of 1,1'-carbonyldiimidazole with stirring under ice-cooling and the mixture was stirred for 1 hour. Then, 6.3 ml of 40% methylamine (methanol solution) was added therein. The resultant mixture was stirred under ice-cooling for 1 hour and then at room temperature for 14 hours. An aqueous potassium carbonate solution was added therein and the mixture was extracted with ether. An organic layer was washed with water and dried, and the solvent was distilled. The obtained residue was purified according to silica gel column chromatography (developing solution, MeOH:CH2Cl2 =1:99) to obtain 0.13 g of 2,2-bis(fluoromethyl)-N-methyl-6-nitro-2H-1-benzopyran-4-carboxamide with a melting point of 178°-179° C.

Workup

  1. temperaturecooling
  2. stirringthe mixture was stirred for 1 hour
  3. temperaturecooling for 1 hour
  4. extractionthe mixture was extracted with ether
  5. washAn organic layer was washed with water
  6. customdried
  7. distillationthe solvent was distilled
  8. customThe obtained residue was purified

Sources & evidence

ORD record
ord-c5d156e79f4c4534b588cc877d04b46f
Source dataset
uspto-grants-1997_07
Patent number
US05646308

Reaction notes

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