Sodium Hydroxide → 2-Hydroxy-4-[2-({[1-phenylethylidene]amino}oxy)ethoxy]benzoic acid

HRID 29648

反応式

HRID 29648 の反応式
[C:1]1([C:7](=[N:9][OH:10])[CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C[O:12][C:13](=[O:25])[C:14]1[CH:19]=[CH:18][C:17]([O:20][CH2:21][CH2:22]Br)=[CH:16][C:15]=1[OH:24].[OH-].[Na+]>O1CCCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[OH:24][C:15]1[CH:16]=[C:17]([O:20][CH2:21][CH2:22][O:10][N:9]=[C:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH3:8])[CH:18]=[CH:19][C:14]=1[C:13]([OH:25])=[O:12]

参加物

6

反応物 3

HCID 14798Sodium HydroxideHCID 69185AcetophenonoximeHCID 574195214-(2-Bromo-ethoxy)-2-hydroxy-benzoic acid methyl ester

生成物 1

HCID 860393012-Hydroxy-4-[2-({[1-phenylethylidene]amino}oxy)ethoxy]benzoic acid収率 27%

試薬・触媒・溶媒 2

HCID 67553Tetrabutylammonium Iodide触媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of 1-phenyl-ethanone oxime (1.156 g, 8.55 mmol) in tetrahydrofuran (75 mL) was added 4-(2-bromo-ethoxy)-2-hydroxy-benzoic acid methyl ester (2.346 g, 8.52 mmol), tetrabutylammonium iodide (0.968 g, 2.62 mmol) and 15% sodium hydroxide solution (30 mL). The reaction was heated at reflux overnight, cooled to room temperature and the layers were separated. The aqueous layer was neutralized to pH 7 by the addition of concentrated hydrochloric acid and extracted with ethyl acetate. The combined organics were washed with brine, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue was purified by flash chromatography using ethyl acetate/hexanes (25/75)+1% formic acid to afford 2-hydroxy-4-[2-(1-phenyl-ethylideneaminooxy)-ethoxy]-benzoic acid (0.712 g, 27%) as a white solid. mp=149.1-150.4° C.; mass spectrum (+APCI, M+H) m/z 316. 1H NMR (400 MHz, DMSO-d6); δ 13.60 (bs, 1H), 11.50 (bs, 1H), 7.66 (m, 3H), 7.39 (m, 3H), 6.53 (m, 2H), 4.44 (t, 2H), 4.31 (t, 2H), 2.17 (s, 3H). Elemental analysis: Calcd. for C17H17NO5: C, 67.7; H, 5.43; N, 4.44, Found: C, 64.45; H, 5.32; N, 4.42.

後処理

  1. temperatureThe reaction was heated
  2. temperatureat reflux overnight
  3. customthe layers were separated
  4. additionThe aqueous layer was neutralized to pH 7 by the addition of concentrated hydrochloric acid
  5. extractionextracted with ethyl acetate
  6. washThe combined organics were washed with brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash chromatography

出典と根拠

ORDレコード
ord-6fdbcbd94e574cbe9609207ad1def98e
出典データセット
uspto-grants-2008_09
特許番号
US07420083B2

関連ノート

読み込み中…