Acrylonitrile → 2-(1,1-Dimethylethyl)-5-hydroxy-4-pyridinecarbonitrile

HRID 1112719Notes

Reaction equation

HRID 1112719 reaction equation
[CH3:1][C:2]([C:5]1O[C:7]([O:10]CC)=[CH:8][N:9]=1)([CH3:4])[CH3:3].[C:13](#[N:16])[CH:14]=[CH2:15]>>[C:13]([C:14]1[CH:15]=[C:5]([C:2]([CH3:1])([CH3:3])[CH3:4])[N:9]=[CH:8][C:7]=1[OH:10])#[N:16]

Participants

3

Reactant 2

HCID 7855AcrylonitrileHCID 12634259HCID 12634259, compound

Product 1

HCID 126342602-(1,1-Dimethylethyl)-5-hydroxy-4-pyridinecarbonitrileYield 37%

Conditions

Temperature
20 °C

Procedure

A neat mixture of 2-(1,1-dimethylethyl)-5-ethoxyoxazole (17 g., 0.1 mole) and acrylonitrile (6.1 g., 0.11 mole) is stirred and heated at 70°-75° C. for 16 hours. The resulting dark reaction mixture is cooled to 20° C. and chromatographed on silica gel (600 g.). Elution with 1% methanol in chloroform (4.35 l.) yields recovered 2-(1,1-dimethylethyl)-5-ethoxyoxazole (10.7 g., 63% recovery). Continued elution with the same eluant (300 ml.) affords impure product (3.2 g.). Further elution with the same eluant (2.5 l.) gives the desired product as a solid (6.5 g., 37%), m.p. 185°-195° C. Two recrystallizations of the latter from methanol-water (1:1; v:v) provides an analytical sample of 4-cyano-6-(1,1-dimethylethyl)-3-pyridinol as colorless crystals (4.5 g., 26%), m.p. 201°-202° C.

Workup

  1. temperatureheated at 70°-75° C. for 16 hours
  2. customThe resulting dark reaction mixture
  3. customchromatographed on silica gel (600 g.)
  4. washElution with 1% methanol in chloroform (4.35 l.)
  5. customyields
  6. customrecovered 2-(1,1-dimethylethyl)-5-ethoxyoxazole (10.7 g., 63% recovery)
  7. washContinued elution with the same eluant (300 ml.)
  8. customaffords impure product (3.2 g.)
  9. washFurther elution with the same eluant (2.5 l.)

Sources & evidence

ORD record
ord-03b2409184b44b688c22ac73be750a34
Source dataset
uspto-grants-1978_10
Patent number
US04123537

Reaction notes

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