Isoamyl Nitrite → 4,6-Bis(1,1-dimethylethyl)-5-[(2-methoxyethoxy)methoxy]-2-pyrimidinecarboxaldehyde oxime

HRID 1742609

反応式

HRID 1742609 の反応式
[Na].[CH3:2][C:3]([C:6]1[C:11]([O:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH3:18])=[C:10]([C:19]([CH3:22])([CH3:21])[CH3:20])[N:9]=[C:8]([CH3:23])[N:7]=1)([CH3:5])[CH3:4].[N:24](OCCC(C)C)=[O:25].[Cl-].[NH4+]>N.O1CCCC1>[CH3:5][C:3]([C:6]1[C:11]([O:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH3:18])=[C:10]([C:19]([CH3:22])([CH3:21])[CH3:20])[N:9]=[C:8]([CH:23]=[N:24][OH:25])[N:7]=1)([CH3:2])[CH3:4]

参加物

7

反応物 4

HCID 8053Isoamyl NitriteHCID 25517Ammonium ChlorideHCID 5360545SodiumHCID 199229904,6-Ditert-butyl-5-[(2-methoxyethoxy)methoxy]-2-methylpyrimidine

生成物 1

HCID 1363784124,6-Bis(1,1-dimethylethyl)-5-[(2-methoxyethoxy)methoxy]-2-pyrimidinecarboxaldehyde oxime収率 21.3%

試薬・触媒・溶媒 2

HCID 222Ammonia溶媒2 回HCID 8028Tetrahydrofuran溶媒

実験手順

Sodium metal (0.28 g, 12.6 mmoles) is dissolved in 50 mL of freshly distilled ammonia at reflux under argon. The reaction mixture is stirred at reflux until the solution turns light gray. 4,6-Bis(1,1-dimethylethyl)-5-[(2-methoxyethoxy)methoxy]-2-methylpyrimidine (3.0 g, 9.7 mmoles) is dissolved in 20 mL of tetrahydrofuran and added to the reaction. After 10 minutes, isoamyl nitrite (2.3 g, 19.3 mmoles) is added, and the reaction mixture is stirred at reflux for 2 hours. It is quenched by the addition of ammonium chloride (1.0 g, 18.7 mmoles) and the ammonia is allowed to evaporate at room temperature. The remaining oil is partitioned between 50 mL of ethyl acetate and 50 mL of water. The organic layer is washed with water (3×50 mL) and brine (50 mL), dried over magnesium sulfate, and the solvent is evaporated. The crude product is adsorbed onto a silica gel plug which is eluted with 300 mL of 5% ether in chloroform, followed by 300 mL of ether. Evaporation of the ether eluant gives 4,6-bis(1,1-dimethylethyl)-5-[(2-methoxyethoxy)methoxy]-2-pyrimidinecarboxaldehyde oxime (0.7 g, 21%), mp 90°-97° C. H1 -NMR (CDCl3) δ 10.40 (s, 1H=NOH), 8.17 (s, 1H, HON=CH<bs>--- -),5.00 (s, 2H, O--CH2 --O) , 3.97 (m, 2H) , 3.64 (m, 2H), 3.42 (s, 1H, OCH3), 1.45 (s, 18H, C. (CH3)3). C13 -NMR (CDCl3) δ 170, 155, 148, 147, 102, 72, 70, 60, 39, 30.

後処理

  1. temperatureat reflux under argon
  2. temperatureat reflux until the solution
  3. additionadded to the reaction
  4. stirringthe reaction mixture is stirred
  5. temperatureat reflux for 2 hours
  6. customto evaporate at room temperature
  7. customThe remaining oil is partitioned between 50 mL of ethyl acetate and 50 mL of water
  8. washThe organic layer is washed with water (3×50 mL) and brine (50 mL)
  9. dry with materialdried over magnesium sulfate
  10. customthe solvent is evaporated
  11. washis eluted with 300 mL of 5% ether in chloroform
  12. customEvaporation of the ether eluant

出典と根拠

ORDレコード
ord-43d3b08462eb469dbd80d84a0c4fb174
出典データセット
uspto-grants-1994_08
特許番号
US05340815

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