Cyanamide → N-cyano-2,2-bis(fluoromethyl)-N'-methyl-6-nitro-2H-1-benzopyran-4-amidine

HRID 264840Notes

Reaction equation

HRID 264840 reaction equation
[F:1][CH2:2][C:3]1([CH2:20][F:21])[CH:8]=[C:7]([C:9](=S)[NH:10][CH3:11])[C:6]2[CH:13]=[C:14]([N+:17]([O-:19])=[O:18])[CH:15]=[CH:16][C:5]=2[O:4]1.[I-].ClC1C=CC=C[N+]=1C.[N:31]#[C:32][NH2:33].[H-].[Na+]>O1CCCC1.C(N(CC)CC)C>[C:32]([NH:33][C:9]([C:7]1[C:6]2[CH:13]=[C:14]([N+:17]([O-:19])=[O:18])[CH:15]=[CH:16][C:5]=2[O:4][C:3]([CH2:20][F:21])([CH2:2][F:1])[CH:8]=1)=[N:10][CH3:11])#[N:31]

Participants

7

Reactant 4

HCID 9864CyanamideHCID 24758Sodium hydrideHCID 1670692-Chloro-1-methylpyridinium iodideHCID 104033502,2-bis(fluoromethyl)-N-methyl-6-nitro-2H-1-benzopyran-4-carbothioamide

Product 1

HCID 19037066N-cyano-2,2-bis(fluoromethyl)-N'-methyl-6-nitro-2H-1-benzopyran-4-amidineYield 25%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

A mixture of 84 mg of 2,2-bis(fluoromethyl)-N-methyl-6-nitro-2H-1-benzopyran-4-carbothioamide, 140 mg of 2-chloro-1-methylpyridinium iodide, 0.06 ml of triethylamine and 2 ml of dried tetrahydrofuran was refluxed with heating for 2 hours. After the reaction solution was cooled to room temperature, 42 mg of cyanamide and 38 mg of sodium hydride (60%) were added therein and the resultant mixture was refluxed with heating for 4 hours. Ice water was added therein and the mixture was extracted with methylene chloride. 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). The resultant product was recrystallized by a mixed solvent of ethyl acetate and hexane to obtain 21.5 mg of N-cyano-2,2-bis(fluoromethyl)-N'-methyl-6-nitro-2H-1-benzopyran-4-amidine with a melting point of 259°-261° C.

Workup

  1. temperaturewas refluxed
  2. temperaturewith heating for 2 hours
  3. temperaturewith heating for 4 hours
  4. extractionthe mixture was extracted with methylene chloride
  5. washAn organic layer was washed with water
  6. customdried
  7. distillationthe solvent was distilled
  8. customThe obtained residue was purified
  9. customThe resultant product was recrystallized by a mixed solvent of ethyl acetate and hexane

Sources & evidence

ORD record
ord-338aa32e1da14c8a85f2881eec108f73
Source dataset
uspto-grants-1997_07
Patent number
US05646308

Reaction notes

Loading…