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

HRID 426275Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 426275
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]

Komponenten

5

Edukt 4

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

Produkt 1

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

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

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)+.

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-e8285a34a4544b22a517433323b831f4
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08106064B2

Notizen zur Reaktion

Wird geladen…