Dimethylformamide → 3-[5-Isopropenyl-2,6-bis-(2-trimethylsilanyl-ethoxy)-pyrimidine-4-carbonyl]-5-methyl-benzonitrile

HRID 426275Notes

Reaction equation

HRID 426275 reaction equation
Cl[C:2]1[C:7]([C:8]([CH3:10])=[CH2:9])=[C:6]([O:11][CH2:12][CH2:13][Si:14]([CH3:17])([CH3:16])[CH3:15])[N:5]=[C:4]([O:18][CH2:19][CH2:20][Si:21]([CH3:24])([CH3:23])[CH3:22])[N:3]=1.C([CH2:27][C:28]1[CH:29]=[C:30]([CH:33]=[C:34]([CH3:36])[CH:35]=1)[C:31]#[N:32])#N.[H-].[Na+].CN(C=[O:43])C>>[C:8]([C:7]1[C:2]([C:27]([C:28]2[CH:29]=[C:30]([CH:33]=[C:34]([CH3:36])[CH:35]=2)[C:31]#[N:32])=[O:43])=[N:3][C:4]([O:18][CH2:19][CH2:20][Si:21]([CH3:24])([CH3:23])[CH3:22])=[N:5][C:6]=1[O:11][CH2:12][CH2:13][Si:14]([CH3:17])([CH3:16])[CH3:15])([CH3:10])=[CH2:9]

Participants

5

Reactant 4

HCID 6228DimethylformamideHCID 24758Sodium hydrideHCID 591847764-Chloro-5-isopropenyl-2,6-bis-(2-trimethylsilanyl-ethoxy)-pyrimidineHCID 667054463-(Cyanomethyl)-5-methylbenzonitrile

Product 1

HCID 591846973-[5-Isopropenyl-2,6-bis-(2-trimethylsilanyl-ethoxy)-pyrimidine-4-carbonyl]-5-methyl-benzonitrileYield 58%

Conditions

Temperature
0 °C

Procedure

4-Chloro-5-isopropenyl-2,6-bis-(2-trimethylsilanyl-ethoxy)-pyrimidine (2.12 g, 5.49 mmol, prepared according to Pews et al. J. Fluorine. Chem. 1989, 42, 179-186) and 3-cyanomethyl-5-methyl-benzonitrile (0.8166 g, 5.23 mmol) was dissolved in DMF (10 mL) and cooled to 0° C. 60% Sodium hydride (0.157 g, 3.92 mmol, 2.0 eq.) was added portionwise and the reaction was stirred at 0° C. for 6 h, then rt for 1 h. Oxygen was bubbled into reaction mixture overnight. The reaction was quenched with 1N HCl and saturated ammonium chloride solution was added. The mixture was extracted with ethyl acetate, the organic layer was dried (MgSO4), concentrated and purified by flash column chromatography (silica gel, 0 to 5% ethyl acetate/hexane) to give a yellow solid (1.568 g, 58%). 1H NMR (300 MHz, CDCl3): δ 7.87 (s, 1H), 7.84 (s, 1H), 7.60 (s, 1H), 4.96 (s, 1H), 4.96 (s, 1H), 4.66 (s, 1H), 4.6-4.4 (m, 2H), 4.4-4.3 (m, 1H) 2.39 (s, 3H), 1.91 (s, 1H), 1.20-1.00 (m, 4H), 0.03 (br s, 9H), 0.027 (br s, 9H). Mass spectrum: 495.9 (M+H)+.

Workup

  1. waitrt for 1 h
  2. customOxygen was bubbled into reaction mixture overnight
  3. customThe reaction was quenched with 1N HCl and saturated ammonium chloride solution
  4. additionwas added
  5. extractionThe mixture was extracted with ethyl acetate
  6. dry with materialthe organic layer was dried (MgSO4)
  7. concentrationconcentrated
  8. custompurified by flash column chromatography (silica gel, 0 to 5% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-e8285a34a4544b22a517433323b831f4
Source dataset
uspto-grants-2012_01
Patent number
US08106064B2

Reaction notes

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