Vanillin → Ethyl 3-methyl-4-(4-formyl-2-methoxyphenoxy)-2-butenoate

HRID 543340

反応式

HRID 543340 の反応式
[O:1]=[CH:2][C:3]1[CH:11]=[CH:10][C:8]([OH:9])=[C:5]([O:6][CH3:7])[CH:4]=1.[H-].[Na+].Br[CH2:15][C:16]([CH3:23])=[CH:17][C:18]([O:20][CH2:21][CH3:22])=[O:19].[OH-].[Na+]>CN(C=O)C.CCOCC>[CH3:15][C:16]([CH2:23][O:9][C:8]1[CH:10]=[CH:11][C:3]([CH:2]=[O:1])=[CH:4][C:5]=1[O:6][CH3:7])=[CH:17][C:18]([O:20][CH2:21][CH3:22])=[O:19]

参加物

7

反応物 4

HCID 1183VanillinHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 53411540Ethyl-4-bromo-3-methyl-but-2-enoate (E/Z; 55/45)

生成物 1

HCID 54099897Ethyl 3-methyl-4-(4-formyl-2-methoxyphenoxy)-2-butenoate

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 6228Dimethylformamide溶媒3 回

実験手順

Vanillin (3.43 g, 22.5 mmol) in 10 ml of DMF is added portionwise, at 0°, to sodium hydride (21.5 g, 23.6 mmol) in ml of DMF. The mixture is stirred for 10 min. and then ethyl 4-bromo-3-methyl-2-butenoate (4.87 g, 23.5 mmol) in 3 ml of DMF is added. After 3 hours, the reaction mixture is poured into ether and 5% sodium hydroxide solution. The aqueous layer is extracted with ether, and the organic layers are combined and washed with 5% sodium hydroxide, with water and with brine and dried. Solvent is removed in vacuo and the crude product is chromatographed to give ethyl 3-methyl-4-(4-formyl-2-methoxyphenoxy)-2-butenoate. To isopropyltriphenylphosphonium iodide (2.26 g, 5.23 mmol) in 15 ml of tetrahydrofuran (THF) is added n-butyllithium (1.6 M; 3.10 ml, 5.0 mmol) at -5°. The mixture is cooled to -60°, and ethyl 3-methyl-4-(4-formyl-2-methoxyphenoxy)-2-butenoate (0.70 g, 2.51 mmol) in 10 ml of THF is added. After 45 min. the reaction mixture is poured into ether and water, and the aqueous phase is extracted with ether. The combined ether layers are washed with water and with brine and dried. Solvent is removed in vacuo, and the crude product is triturated with hexane and the hexane-soluble fraction is purified by prep. TLC to give ethyl 3-methyl-4-[2-methoxy-4-(2-methyl-1-propenyl)phenoxy]-2-butenoate, MS m/e 304 (M+).

後処理

  1. waitAfter 3 hours
  2. extractionThe aqueous layer is extracted with ether
  3. washwashed with 5% sodium hydroxide, with water and with brine
  4. customdried
  5. customSolvent is removed in vacuo
  6. customthe crude product is chromatographed

出典と根拠

ORDレコード
ord-f89dbe30299a48088a96a06045b70f3b
出典データセット
uspto-grants-1987_04
特許番号
US04661617

関連ノート

読み込み中…