Nitric Acid → Chlorofluoronitroacetic Acid

HRID 2253552Notes

Reaction equation

HRID 2253552 reaction equation
[Cl:1][C:2]([F:9])([N+:6]([O-:8])=[O:7])[C:3]([OH:5])=[O:4].OS(O)(=O)=O.O=S(=O)=O.[N+:19]([O-:22])(O)=[O:20].[F:23][C:24]([F:29])([F:28])[C:25]([OH:27])=[O:26].[Cl:30][C:31]([F:35])=[C:32]([F:34])[Cl:33]>>[Cl:1][C:2]([F:9])([N+:6]([O-:8])=[O:7])[C:3]([OH:5])=[O:4].[F:23][C:24]([F:29])([F:28])[C:25]([O:27][C:31]([Cl:30])([F:35])[C:32]([Cl:33])([F:34])[N+:19]([O-:22])=[O:20])=[O:26]

Participants

7

Reactant 5

HCID 944Nitric AcidHCID 6422Trifluoroacetic acidHCID 11736DichlorodifluoroetheneHCID 24681Fuming sulfuric acid2×HCID 13452256Chlorofluoronitroacetic Acid

Product 2

HCID 13452256Chlorofluoronitroacetic AcidHCID 538811491,2-Dichloro-1,2-difluoro-1-nitroethyl trifluoroacetate

Procedure

The yield of chlorofluoronitroacetic acid in the nitration reaction was increased to 44% by replacing sulfuric acid with oleum. When a mixture of oleum, nitric acid and trifluoracetic acid was reacted with 1,2-dichlorodifluoroethylene, chlorofluoronitroacetic acid was obtained in 63% yield along with 14% of the 1,2-addition product, 1,2-dichloro-1,2-difluoro-2-nitroethyl trifluoroacetate, bringing the total yield of the nitration reaction to 77%. Apparently the 1,2-addition product was formed first and then was hydrolyzed in situ, to give the acetic acid derivative. The lower boiling point and diminished water sensitivity of the 1,2-addition product makes it a potentially attractive alternative to chlorofluoronitroacetic acid in subsequent nitration reactions.

Workup

  1. temperaturewas increased to 44%

Sources & evidence

ORD record
ord-17f6765859934b99bfa0ce534671ffb2
Source dataset
uspto-grants-1993_08
Patent number
USH0001223

Reaction notes

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