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

HRID 426275ノート

反応式

HRID 426275 の反応式
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]

参加物

5

反応物 4

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

生成物 1

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

反応条件

温度
0 °C

実験手順

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)+.

後処理

  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)

出典と根拠

ORDレコード
ord-e8285a34a4544b22a517433323b831f4
出典データセット
uspto-grants-2012_01
特許番号
US08106064B2

反応ノート

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