Sodium Carbonate → alpha-(4-tert-Butylphenyl)-beta-[(methylthio)carbonyloxy]-beta-(2-trifluoromethylphenyl)acrylonitrile

HRID 1168411Notes

Reaction equation

HRID 1168411 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11](=[C:14]([OH:25])[C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[C:21]([F:24])([F:23])[F:22])[C:12]#[N:13])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[C:26](=[O:29])([O-])[O-].[Na+].[Na+].ClC1C=C[S:35][C:34]=1C(OC)=O>C(C(C)=O)C>[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11](=[C:14]([O:25][C:26]([S:35][CH3:34])=[O:29])[C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[C:21]([F:23])([F:24])[F:22])[C:12]#[N:13])=[CH:7][CH:6]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 10340Sodium CarbonateHCID 2777566Methyl 3-chlorothiophene-2-carboxylateHCID 70026415alpha-(4-Tert-butylphenyl)-beta-hydroxy-beta-(2-trifluoromethylphenyl)acrylonitrile

Product 1

HCID 86759172alpha-(4-tert-Butylphenyl)-beta-[(methylthio)carbonyloxy]-beta-(2-trifluoromethylphenyl)acrylonitrileYield 98.2%

Reagents, catalysts & solvents 1

HCID 6569Methyl Ethyl KetoneSolvent2×

Conditions

Temperature
70 °C

Procedure

A mixture comprising 5.0 g of α-(4-tert-butylphenyl)-β-hydroxy-β-(2-trifluoromethylphenyl)acrylonitrile, 1.5 g of sodium carbonate and 30 ml of methyl ethyl ketone, was heated to 70° C., and a mixture comprising 2.1 g of methyl chlorothiolformate and 10 ml of methyl ethyl ketone, was dropwise added over a period of 10 minutes. After completion of the dropwise addition, the reaction was carried out for 30 minutes at a temperature of from 70 to 75° C. The reaction mixture was cooled, and then an inorganic salt was filtered off. The cake was washed with 20 ml of methyl ethyl ketone. Methyl ethyl ketone in the filtrate was distilled off, and to the residue, 50 ml of an isoparaffin type hydrocarbon (tradename: ISOPAR G, manufactured by EXXON CHEMICAL) was added, followed by heating for dissolution, and the solution was left to cool to room temperature. Precipitated crystals were collected by filtration, and the cake was washed with 10 ml of ISOPAR G (tradename) and then dried at 65° C. for 12 hours to obtain 4.9 g of the desired product (isomer ratio 2:98). The HPLC conditions for the analysis of this product were as follows. Further, the NMR spectrum data of this product were the same as in Preparation Example 4.

Workup

  1. additionAfter completion of the dropwise addition
  2. temperatureThe reaction mixture was cooled
  3. filtrationan inorganic salt was filtered off
  4. washThe cake was washed with 20 ml of methyl ethyl ketone
  5. distillationMethyl ethyl ketone in the filtrate was distilled off
  6. additionto the residue, 50 ml of an isoparaffin type hydrocarbon (tradename: ISOPAR G, manufactured by EXXON CHEMICAL) was added
  7. temperatureby heating for dissolution
  8. waitthe solution was left
  9. temperatureto cool to room temperature
  10. customPrecipitated crystals
  11. filtrationwere collected by filtration
  12. washthe cake was washed with 10 ml of ISOPAR G (tradename)
  13. customdried at 65° C. for 12 hours

Sources & evidence

ORD record
ord-8caf893b6c134ee3b8af7c0b74bc5a2d
Source dataset
uspto-grants-2003_09
Patent number
US06624179B1

Reaction notes

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