m-Chloroperbenzoic acid → Fipronil

HRID 861227Notes

Reaction equation

HRID 861227 reaction equation
[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:16])[F:15])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]#[N:20])[C:3]=1[S:21][C:22]([F:25])([F:24])[F:23].ClC1C=CC=C(C(OO)=[O:34])C=1>ClCCl.C(OCC)(=O)C>[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:15])([F:16])[F:17])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]#[N:20])[C:3]=1[S:21]([C:22]([F:25])([F:24])[F:23])=[O:34]

Participants

5

Reactant 2

HCID 70297m-Chloroperbenzoic acid2×HCID 9953940Fipronil sulfide

Product 1

HCID 3352FipronilYield 57.8%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A stirred solution of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole (10.0 g) in dichloromethane (100 ml) was treated with m-chloroperbenzoic acid (4.5 g). After stirring overnight additional m-chloroperbenzoic acid (1.6 g) was added in 2 portions, and left for 2 days. The reaction product was diluted with ethyl acetate (30 ml) and then washed in turn with sodium sulphite solution (50 ml), sodium carbonate solution (50 ml) and with water (50 ml). After drying over magnesium sulphate, this was filtered and evaporated in vacuo. Purification by chromatography on silica eluting with dichloromethane gave 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole as a white solid (6.0 g), m.p. 200.5°-201° C.

Workup

  1. additionwas added in 2 portions
  2. washwashed in turn with sodium sulphite solution (50 ml), sodium carbonate solution (50 ml) and with water (50 ml)
  3. dry with materialAfter drying over magnesium sulphate
  4. filtrationthis was filtered
  5. customevaporated in vacuo
  6. customPurification by chromatography on silica eluting with dichloromethane

Sources & evidence

ORD record
ord-c2bb231aa9b94114846c815d43048248
Source dataset
uspto-grants-1998_02
Patent number
US05714191

Reaction notes

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