Pivaloyl chloride → Cyenopyrafen

HRID 1096680Notes

Reaction equation

HRID 1096680 reaction equation
[O:1]=[C:2]([C:16]1[N:20]([CH3:21])[N:19]=[C:18]([CH3:22])[C:17]=1[CH3:23])[CH:3]([C:6]1[CH:11]=[CH:10][C:9]([C:12]([CH3:15])([CH3:14])[CH3:13])=[CH:8][CH:7]=1)[C:4]#[N:5].[C:24](Cl)(=[O:29])[C:25]([CH3:28])([CH3:27])[CH3:26]>C1(C)C(C)=CC=CC=1>[CH3:26][C:25]([CH3:28])([CH3:27])[C:24]([O:1]/[C:2](/[C:16]1[N:20]([CH3:21])[N:19]=[C:18]([CH3:22])[C:17]=1[CH3:23])=[C:3](\[C:6]1[CH:7]=[CH:8][C:9]([C:12]([CH3:15])([CH3:14])[CH3:13])=[CH:10][CH:11]=1)/[C:4]#[N:5])=[O:29]

Participants

4

Reactant 2

HCID 62493Pivaloyl chlorideHCID 119839523-Oxo-2-(4-tert-butylphenyl)-3-(1,3,4-trimethylpyrazol-5-yl)propionitrile

Product 1

HCID 18772482CyenopyrafenYield 95.9%

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent2×

Conditions

Temperature
70 °C

Procedure

In a 10 L-reaction flask, 456 g (1.47 mol) of 3-oxo-2-(4-tert-butylphenyl)-3-(1,3,4-trimethylpyrazol-5-yl) propionitrile and 2738 g of xylene were added, the temperature was raised to 70° C., and 534 g (4.43 mol) of pivaloyl chloride was added dropwise under reflux over 10 hours while removing hydrogen chloride under a reduced pressure at 68 to 71° C./10 to 13 kPa. After reacting as such for 3 hours, 2181 g of a mixture of pivaloyl chloride and xylene was distilled off at 70° C. under a reduced pressure in order to remove excess pivaloyl chloride. After adding 456 g of warm water of 70° C., 228 g of 2.7% sodium hydrogen carbonate aqueous solution was added dropwise. After separating the resulting aqueous phase, the resulting organic phase was washed with 456 g of warm water of 70° C., the resulting aqueous phase was separated to obtain a xylene solution. A quantitative analysis with liquid chromatography showed that the xylene solution contained 555 g (yield 95.6%) of (2E)-3-(2,2-dimethylpropanoyloxy)-2-(4-tert-butylphenyl)-3-(1,3,4-trimethylpyrazol-5-yl) acrylonitrile. After distilling off xylene at 90° C., 1141 g of heptane was added, and crystallization was carried out by gradually cooling from 70° C. After aging at 0° C. for 1 hour, the resulting crystal was filtered, and dried to obtain 533 g (yield 91.9%) of (2E)-3-(2,2-dimethylpropanoyloxy)-2-(4-tert-butylphenyl)-3-(1,3,4-trimethylpyrazol-5-yl) acrylonitrile (melting point: 110° C.).

Workup

  1. additionwere added
  2. temperatureunder reflux over 10 hours
  3. customwhile removing hydrogen chloride under a reduced pressure at 68 to 71° C./10 to 13 kPa
  4. customsuch for 3 hours
  5. distillation2181 g of a mixture of pivaloyl chloride and xylene was distilled off at 70° C. under a reduced pressure in order
  6. customto remove excess pivaloyl chloride
  7. additionAfter adding 456 g of warm water of 70° C., 228 g of 2.7% sodium hydrogen carbonate aqueous solution
  8. additionwas added dropwise
  9. customAfter separating the resulting aqueous phase
  10. washthe resulting organic phase was washed with 456 g of warm water of 70° C.
  11. customthe resulting aqueous phase was separated
  12. customto obtain a xylene solution

Sources & evidence

ORD record
ord-054c52c0f41e459b80bd16e9c5e0f543
Source dataset
uspto-grants-2012_03
Patent number
US08138368B2

Reaction notes

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