Potassium Carbonate → (2z)-3-(2,2-Dimethylpropanoyloxy)-2-(5-ethyl-2-phenyl-1,2,3-triazol-4-yl)-3-(1,3,4-trimethylpyrazol-5-yl)acrylonitrile

HRID 1992762Notes

Reaction equation

HRID 1992762 reaction equation
O=C(C1N(C)N=C(C)C=1C)C(C1C=CC(C(C)(C)C)=CC=1)C#N.C(=O)([O-])[O-].[K+].[K+].C(Cl)(=O)C(C)(C)C.[CH3:37][C:38]([CH3:68])([CH3:67])[C:39]([O:41]/[C:42](/[C:59]1[N:63]([CH3:64])[N:62]=[C:61]([CH3:65])[C:60]=1[CH3:66])=[C:43](\[C:46]1[C:50]([CH2:51][CH3:52])=[N:49][N:48]([C:53]2[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=2)[N:47]=1)/[C:44]#[N:45])=[O:40]>>[CH3:67][C:38]([CH3:37])([CH3:68])[C:39]([O:41]/[C:42](/[C:59]1[N:63]([CH3:64])[N:62]=[C:61]([CH3:65])[C:60]=1[CH3:66])=[C:43](/[C:46]1[C:50]([CH2:51][CH3:52])=[N:49][N:48]([C:53]2[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=2)[N:47]=1)\[C:44]#[N:45])=[O:40]

Participants

5

Reactant 4

HCID 11430Potassium CarbonateHCID 62493Pivaloyl chlorideHCID 119839523-Oxo-2-(4-tert-butylphenyl)-3-(1,3,4-trimethylpyrazol-5-yl)propionitrileHCID 66781252(2E)-3-(2,2-dimethylpropanoyloxy)-2-(2-phenyl-5-ethyl-1,2,3-triazol-4-yl)-3-(1,3,4-trim ethylpyrazol-5-yl) acrylonitrile

Product 1

HCID 66781253(2z)-3-(2,2-Dimethylpropanoyloxy)-2-(5-ethyl-2-phenyl-1,2,3-triazol-4-yl)-3-(1,3,4-trimethylpyrazol-5-yl)acrylonitrileYield 78.6%

Conditions

Temperature
60 °C

Procedure

In a 10 L-reaction flask, 223 g (0.639 mol) of 3-oxo-2-(4-tert-butylphenyl)-3-(1,3,4-trimethylpyrazol-5-yl)propionitrile and 4456 g of 1,4-doxane were added, 97.2 g (0.351 mol) of potassium carbonate was added thereto, then the temperature was raised to 60° C., and the resulting mixture was stirred for 3 hours. In order to remove water formed as a by-product, 486 g of the solvent was distilled off under a reduced pressure, then 92.5 g (0.767 mol) of pivaloyl chloride was dropwise at 60° C. over 1 hour. After reacting for 2 hours, 1,4-dioxane being a solvent was distilled off, then 456 g of toluene was added and dissolved. The resulting solution was washed two times with 446 g of water to obtain a toluene solution containing 217 g (yield 78.6%) of (2Z)-3-(2,2-dimethylpropanoyloxy)-2-(5-ethyl-2-phenyl-1,2,3-triazol-4-yl)-3-(1,3,4-trimethylpyrazol-5-yl)acrylonitrile and 43 9 (yield 15.5%) of (2E)-3-(2,2-dimethylpropanoyloxy)-2-(5-ethyl-2-phenyl-1,2,3-triazol-4-yl)-3-(1,3,4-trimethylpyrazol-5-yl)acrylonitrile. After distilling off toluene under a reduced pressure, the residue was dissolved in 780 g of acetonitrile, and crystallization was carried out by gradually cooling to 0° C. After filtering, the resulting crystal was washed with 260 g of acetonitrile, then dried to obtain 166 g (yield 63.1%) of (2Z)-3-(2,2-dimethylpropanoyloxy)-2-(5-ethyl-2-phenyl-1,2,3-triazol-4-yl)-3-(1,3,4-trimethylpyrazol-5-yl)acrylonitrile.

Workup

  1. additionwere added
  2. customIn order to remove water
  3. customformed as a by-product
  4. distillation486 g of the solvent was distilled off under a reduced pressure
  5. waitAfter reacting for 2 hours
  6. distillation1,4-dioxane being a solvent was distilled off
  7. addition456 g of toluene was added
  8. dissolutiondissolved
  9. washThe resulting solution was washed two times with 446 g of water
  10. customto obtain a toluene solution

Sources & evidence

ORD record
ord-40e29690a9704e348975aba146c48385
Source dataset
uspto-grants-2010_01
Patent number
US07649104B2

Reaction notes

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