Sodium hydride → methyl (E)-[3-(4-ethyl-3,5-dimethoxy-phenyl)-1-methyl-piperidin-4-ylidene]acetate

HRID 382807ノート

反応式

HRID 382807 の反応式
[CH3:1][O:2][C:3]([CH2:5]P(OC)(OC)=O)=[O:4].[H-].[Na+].[CH2:14]([C:16]1[C:21]([O:22][CH3:23])=[CH:20][C:19]([CH:24]2[C:29](=O)[CH2:28][CH2:27][N:26]([CH3:31])[CH2:25]2)=[CH:18][C:17]=1[O:32][CH3:33])[CH3:15]>O1CCCC1>[CH2:14]([C:16]1[C:17]([O:32][CH3:33])=[CH:18][C:19]([CH:24]2[CH2:25][N:26]([CH3:31])[CH2:27][CH2:28]/[C:29]/2=[CH:5]\[C:3]([O:2][CH3:1])=[O:4])=[CH:20][C:21]=1[O:22][CH3:23])[CH3:15]

参加物

5

反応物 3

HCID 24758Sodium hydrideHCID 80029Trimethyl phosphonoacetateHCID 183619573-(4-Ethyl-3,5-dimethoxy-phenyl)-1-methyl-piperidin-4-one

生成物 1

HCID 86757543methyl (E)-[3-(4-ethyl-3,5-dimethoxy-phenyl)-1-methyl-piperidin-4-ylidene]acetate収率 91.2%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

A solution of 39 ml (262.4 mmol) of trimethyl phosphonoacetate in 450 ml of tetrahydrofuran was added dropwise at 0° to a suspension of 9.54 g (238.5 mmol) of sodium hydride (55% in mineral oil) in 450 ml of tetrahydrofuran and the mixture was stirred for 30 minutes. Subsequently, the white suspension was treated with a solution of 33.15 g (119.5 mmol) of 3-(4-ethyl-3,5-dimethoxy-phenyl)-1-methyl-piperidin-4-one in 450 ml of tetrahydrofuran and the mixture was stirred at 50° for 2 hours. After cooling to room temperature the mixture was poured on to 500 ml of ice-water and extracted three times with 400 ml of diethyl ether. The organic phases were washed with 400 ml of water and 400 ml of saturated sodium chloride solution, dried (Na2SO4), filtered and evaporated. Chromatography (silica gel, methylene chloride/methanol 19:1) and recrystalization from hexane yielded 36.33 g (91%) of methyl (E)-[3-(4-ethyl-3,5-dimethoxy-phenyl)-1-methyl-piperidin-4-ylidene]acetate as pale yellow crystals of m.p. 110-112°.

後処理

  1. stirringthe mixture was stirred at 50° for 2 hours
  2. extractionextracted three times with 400 ml of diethyl ether
  3. washThe organic phases were washed with 400 ml of water and 400 ml of saturated sodium chloride solution
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. customevaporated
  7. customChromatography (silica gel, methylene chloride/methanol 19:1) and recrystalization from hexane

出典と根拠

ORDレコード
ord-87c16e7dc7ff4b7b86bfcc7e258a59bf
出典データセット
uspto-grants-2001_10
特許番号
US06310208B1

反応ノート

読み込み中…