Dichloromethane → HCID 21831347, compound

HRID 977629Notes

Reaction equation

HRID 977629 reaction equation
[F:1][CH2:2][C:3]1([CH2:22][F:23])[CH:8]=[C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][N:10]=2)[C:6]2[CH:15]=[C:16]([N+:19]([O-:21])=[O:20])[CH:17]=[CH:18][C:5]=2[O:4]1.C(Cl)Cl.[C:27]1([CH3:40])[CH:32]=[C:31]([CH3:33])[CH:30]=[C:29]([CH3:34])[C:28]=1[S:35]([O:38][NH2:39])(=[O:37])=[O:36]>CCOCC>[C:27]1([CH3:40])[CH:32]=[C:31]([CH3:33])[CH:30]=[C:29]([CH3:34])[C:28]=1[S:35]([O-:38])(=[O:37])=[O:36].[NH2:39][N+:10]1[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=1[C:7]1[C:6]2[CH:15]=[C:16]([N+:19]([O-:21])=[O:20])[CH:17]=[CH:18][C:5]=2[O:4][C:3]([CH2:2][F:1])([CH2:22][F:23])[CH:8]=1

Participants

5

Reactant 3

HCID 6344Dichloromethane2×HCID 11830845O-(2,4,6-Trimethylbenzenesulfonyl)hydroxylamineHCID 218313462,2-bisfluoromethyl-6-nitro-4-(2-pyridyl)-2H-1-benzopyran

Product 1

HCID 21831347HCID 21831347, compoundYield 71.7%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a mixture of 200 mg of 2,2-bisfluoromethyl-6-nitro-4-(2-pyridyl)-2H-1-benzopyran and 2 ml of methylene chloride was added dropwise a mixture of 135 mg of (O-mesitylenesulfonyl)hydroxylamine and 3 ml of methylene chloride at room temperature with stirring. The mixture was stirred for 1 hour and ether was added thereto. The separated crystal was collected by filtration to obtain 240 mg of N-amino-2-(2,2-bisfluoromethyl-6-nitro-2H-1-benzopyran-4-yl)pyridinium mesitylenesulfonate. To a mixture of 60 mg of the above-obtained N-amino-2-(2,2-bisfluoromethyl-6-nitro-2H-1-benzopyran-4-yl)pyridinium mesitylenesulfonate and 1 ml of dimethylformamide was added 5 mg of sodium hydride and 36 mg of cyano bromide under ice-cooling with stirring. The mixture was stirred under ice-cooling for 1 hour. Water was added thereto and the mixture was extracted with ether. The organic layer was washed with water and dried. The solvent was distilled off and the resultant residue was purified using silica gel column chromatography (developing solution, MeOH:CH2Cl2 =5:95) to obtain 11 mg of 2-(2,2-bisfluoromethyl-6-nitro-2H-1-benzopyran-4-yl)pyridine N-cyanoimine represented by the following formula having a melting point of 212°-214° C.

Workup

  1. additionwas added dropwise
  2. stirringThe mixture was stirred for 1 hour
  3. filtrationThe separated crystal was collected by filtration

Sources & evidence

ORD record
ord-6e5ee78aadde4d588c2474f4ff22dc35
Source dataset
uspto-grants-1997_03
Patent number
US05614633

Reaction notes

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