p-Toluenesulfonic acid → HCID 23173000, compound

HRID 1088731Notes

Reaction equation

HRID 1088731 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].[CH2:26]([CH2:30][C:31](=O)[CH3:32])[C:27]([CH3:29])=O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1.ClCCl>[C:19]([C:4]1[C:3]([S:21][C:22]([F:25])([F:24])[F:23])=[C:2]([N:1]2[C:31]([CH3:32])=[CH:30][CH:26]=[C:27]2[CH3:29])[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]=1)#[N:20]

Participants

6

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 80352,5-HexanedioneHCID 9953940Fipronil sulfide

Product 1

HCID 23173000HCID 23173000, compoundYield 62.2%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole (8.0 g) and acetonylacetone (4.34 g) in toluene (250 ml) containing p-toluenesulphonic acid (0.5 g) was heated under reflux with a Dean and Stark take-off head fitted to the flask. After 311/2 hours evaporation in vacuo gave a dark solid, which was dissolved in dichloromethane (100 ml) and washed in turn with water (100 ml) and saturated sodium carbonate solution (50 ml). The organic layer was dried over anhydrous magnesium sulphate, and evaporated in vacuo to give a dark semisolid. Purification by dry column chromatography (Kieselgel 60G) eluting with dichloromethane/hexane (1:3) gave 3-cyano-1-(2,6-dichloro-4-trifluoromethyl- phenyl)-5-(2,5-dimethylpyrrol-1-yl)-4-trifluoromethylthiopyrazole as a white solid (5.9 g), m.p. 142.3°-144° C.

Workup

  1. temperaturewas heated
  2. temperatureunder reflux with a Dean and Stark take-off head
  3. customfitted to the flask
  4. customAfter 311/2 hours evaporation in vacuo
  5. customgave a dark solid, which
  6. washwashed in turn with water (100 ml) and saturated sodium carbonate solution (50 ml)
  7. dry with materialThe organic layer was dried over anhydrous magnesium sulphate
  8. customevaporated in vacuo
  9. customto give a dark semisolid
  10. customPurification
  11. dry with materialby dry column chromatography (Kieselgel 60G)
  12. washeluting with dichloromethane/hexane (1:3)

Sources & evidence

ORD record
ord-056e99c424c4487aacaff7d3b8614b63
Source dataset
uspto-grants-1990_10
Patent number
US04963575

Reaction notes

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