Water → Methyl 4-(4-formyl-2-methoxyphenoxy)butanoate

HRID 33986

反応式

HRID 33986 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.[CH3:12][O:13][C:14](=[O:19])[CH2:15][CH2:16][CH2:17]Br.C(=O)([O-])[O-].[K+].[K+].O>CN(C=O)C>[CH3:12][O:13][C:14](=[O:19])[CH2:15][CH2:16][CH2:17][O:9][C:8]1[CH:10]=[CH:11][C:3]([CH:2]=[O:1])=[CH:4][C:5]=1[O:6][CH3:7]

参加物

6

反応物 4

HCID 962WaterHCID 1183VanillinHCID 11430Potassium CarbonateHCID 107604Methyl 4-bromobutyrate

生成物 1

HCID 10753291Methyl 4-(4-formyl-2-methoxyphenoxy)butanoate収率 66%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

A solution of vanillin (47)(40.00 g, 262.89 mmol) and methyl-4-bromobutyrate (50.00 g, 276.18 mmol) in DMF (200 mL) was allowed to stir over potassium carbonate (51.53 g, 372.40 mmol) for 16 hours. Water was added to the reaction mixture at which time the product crystallised. The resulting mixture was filtered and dried in vacuo for 16 hours to afford the keto-ester (48) as a white solid (41.3 g, 66%). MP=57-59° C. 1H NMR (250 MHz, CDCl3) δ 9.80 (s, 1H), 7.46-7.40 (m, 2H), 6.97 (d, J=8.1 Hz, 1H), 4.16 (t, J=6.3 Hz, 2H), 3.92 (s, 3H), 3.70 (s, 3H), 2.57 (t, J=7.2 Hz, 2H), 2.20 (pent, J=6.7 Hz, 2H). 13C NMR (67.8 MHz, CDCl3) 188.2 (Cl), 173.7 (C12), 153.8 (Cquat.), 152.0 (Cquat.), 144.1 (Cquat.), 125.8 (Cmethine), 110.3 (C3), 108.5 (C6), 69.0 (C9), 57.0 (C8), 52.2 (C13), 30.6 (C11), 24.5 (C10). It was decided to adopt the numbering system shown in the figure below for the molecule for ease of peak assignment in 13C NMR.

後処理

  1. customcrystallised
  2. filtrationThe resulting mixture was filtered
  3. customdried in vacuo for 16 hours

出典と根拠

ORDレコード
ord-44a5e748fd264f4bbf8f4ac6744d97fd
出典データセット
uspto-grants-2008_09
特許番号
US07429658B2

関連ノート

読み込み中…