Heptane → 2-(2-Phenyl-5-ethyl-1,2,3-triazol-4-yl)-3-(1,3,4-trimethyl-5-pyrazolyl)-3-oxopropionitrile

HRID 1096689Notes

Reaction equation

HRID 1096689 reaction equation
[C:1]1([N:7]2[N:11]=[C:10]([CH2:12][C:13]#[N:14])[C:9]([CH2:15][CH3:16])=[N:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([O:19][C:20]([C:22]1[N:26]([CH3:27])[N:25]=[C:24]([CH3:28])[C:23]=1[CH3:29])=O)C.CCCCCCC.CC(C)([O-])C.[K+]>COCCOCCOC>[C:1]1([N:7]2[N:11]=[C:10]([CH:12]([C:20]([C:22]3[N:26]([CH3:27])[N:25]=[C:24]([CH3:28])[C:23]=3[CH3:29])=[O:19])[C:13]#[N:14])[C:9]([CH2:15][CH3:16])=[N:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 4

HCID 8900HeptaneHCID 9855653Ethyl 1,3,4-trimethyl-1H-pyrazole-5-carboxylateHCID 18002320(5-Ethyl-2-phenyl-2H-1,2,3-triazol-4-yl)acetonitrileHCID 23665647Potassium tert-butoxide

Product 1

HCID 667812552-(2-Phenyl-5-ethyl-1,2,3-triazol-4-yl)-3-(1,3,4-trimethyl-5-pyrazolyl)-3-oxopropionitrileYield 68%

Reagents, catalysts & solvents 1

HCID 8150DiglymeSolvent

Conditions

Temperature
92.5 °C

Procedure

In a 2 L-reaction flask equipped with a rectification column, 106 g (0.5 mol) of 2-phenyl-4-cyanomethyl-5-ethyl-1,2,3-triazole, 91 g (0.5 mol) of 1,3,4-trimethylpyrazol-5-carboxylic acid ethyl ester, 530 g of heptane, and 106 g of diethylene glycol dimethyl ether were added, then azeotropic dehydration was carried out by heating at 90 to 95° C. Thereafter 61.7 g (0.55 mol) of potassium-tert-butoxide was carefully added under nitrogen atmosphere, then the resulting solution was heated at 95° C. and reacted for 15 hours while removing the eluent from the rectification column. After cooling to 30° C. or less, 3000 g of water was added to separate out heptane phase, and the resulting aqueous phase was further washed with 600 g of heptane to separate into phases. A quantitative analysis of the obtained aqueous phase with liquid chromatography showed that the aqueous phase contained 118.5 g (yield 68%) of 2-(2-phenyl-5-ethyl-1,2,3-triazol-4-yl)-3-(1,3,4-trimethyl-5-pyrazolyl)-3-oxopropionitrile. The aqueous solution was warmed at 40° C., pH was adjusted to 1 by adding 35% hydrochloric acid with stirring. The crystal obtained by cooling to 15° C. over 2 hours was filtered. The crystal cake was washed three times with 200 ml of water and then dried to obtain 116 g (yield 66.5%) of 2-(2-phenyl-5-ethyl-1,2,3-triazol-4-yl)-3-(1,3,4-trimethyl-5-pyrazolyl)-3-oxopropionitrile (melting point 119° C.).

Workup

  1. customIn a 2 L-reaction flask
  2. additionwere added
  3. temperaturethe resulting solution was heated at 95° C.
  4. customreacted for 15 hours
  5. customwhile removing the eluent from the rectification column
  6. temperatureAfter cooling to 30° C. or less
  7. addition3000 g of water was added
  8. customto separate out heptane phase
  9. washthe resulting aqueous phase was further washed with 600 g of heptane
  10. customto separate into phases

Sources & evidence

ORD record
ord-4c470c7ae28a4af5b7fcfb741f3ae216
Source dataset
uspto-grants-2012_03
Patent number
US08138368B2

Reaction notes

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