Trichloroacetyl chloride → HCID 9911260, compound

HRID 1421497Notes

Reaction equation

HRID 1421497 reaction equation
[C:1]([C:3]1[C:7]([CH:8]=[CH2:9])=[CH:6][N:5]([CH:10]2[CH:15]=[CH:14][C:13]([C:16]([F:19])([F:18])[F:17])=[CH:12][C:11]2(Cl)[Cl:20])[N:4]=1)#[N:2].[Cl:22][C:23](Cl)([Cl:27])[C:24](Cl)=[O:25].P(Cl)(Cl)([Cl:31])=O>C(OCC)C.[Zn]>[C:1]([C:3]1[C:7]([CH:8]2[CH2:9][C:24](=[O:25])[C:23]2([Cl:27])[Cl:22])=[CH:6][N:5]([C:10]2[C:15]([Cl:31])=[CH:14][C:13]([C:16]([F:18])([F:19])[F:17])=[CH:12][C:11]=2[Cl:20])[N:4]=1)#[N:2]

Participants

6

Reactant 3

HCID 6420Trichloroacetyl chlorideHCID 24813Phosphorus oxychlorideHCID 18779840HCID 18779840, compound

Product 1

HCID 9911260HCID 9911260, compoundYield 57%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 3283Diethyl EtherSolvent2×

Procedure

3-Cyano-1-(2,2-dichloro-4-trifluoromethylphenyl)-4-vinylpyrazole (5.00 g, 15.06 mmol, WO97/07102-A1) was dissolved in anhydrous diethyl ether (50 ml) in a dry, nitrogen-flushed flask. Activated zinc (2.97 g, 45.8 mmol) was added and the suspension was vigorously stirred. A mixture of trichloroacetyl chloride (3.57 ml, 37.65 mmol) and phosphorus oxychloride (4.1 ml, 37.65 mmol) in diethyl ether (20 ml) was added dropwise at room temperature via a pressure-equalising dropping funnel over a period of 30 minutes--the resulting exotherm being controlled by the rate of addition. On completion of addition, the mixture was heated to reflux for 4 hr then cooled to room temperature. The mixture was filtered and poured onto 200 ml of crushed ice before extracting with diethyl ether (3×100 ml). The combined organics were washed successively with saturated aqueous NaHCO3 solution and brine before drying over MgSO4, filtering, and evaporating the ether in vacuo to leave a black oil. This was purified by silica chromatography (eluting with 10% diethyl ether/hexane) to give 3.80 g of the title compound as a white solid.

Workup

  1. customflushed flask
  2. additionwas added dropwise at room temperature via
  3. customof 30 minutes
  4. additionthe resulting exotherm being controlled by the rate of addition
  5. additionOn completion of addition
  6. temperaturethe mixture was heated
  7. temperatureto reflux for 4 hr
  8. filtrationThe mixture was filtered
  9. additionpoured onto 200 ml of crushed ice
  10. extractionbefore extracting with diethyl ether (3×100 ml)
  11. washThe combined organics were washed successively with saturated aqueous NaHCO3 solution and brine
  12. dry with materialbefore drying over MgSO4
  13. filtrationfiltering
  14. customevaporating the ether in vacuo
  15. customto leave a black oil
  16. customThis was purified by silica chromatography (eluting with 10% diethyl ether/hexane)

Sources & evidence

ORD record
ord-bebbb5728165415cb370914065aff0aa
Source dataset
uspto-grants-2000_06
Patent number
US06077859

Reaction notes

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