Epichlorohydrin → 2-Hydroxymethyl-1,4-benzodioxan-6-carbaldehyde

HRID 38721

反応式

HRID 38721 の反応式
[OH:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[OH:10])[CH:5]=[O:6].[H-].[Na+].Cl[CH2:14][CH:15]1[CH2:17][O:16]1>CN(C=O)C.[OH-].[Na+]>[OH:16][CH2:17][CH:15]1[O:10][C:9]2[CH:8]=[CH:7][C:4]([CH:5]=[O:6])=[CH:3][C:2]=2[O:1][CH2:14]1

参加物

6

反応物 3

HCID 7835EpichlorohydrinHCID 87683,4-DihydroxybenzaldehydeHCID 24758Sodium hydride

生成物 1

HCID 156593722-Hydroxymethyl-1,4-benzodioxan-6-carbaldehyde収率 11.8%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒2 回HCID 14798Sodium Hydroxide溶媒

実験手順

To a cold (5° C.) solution of 3,4-dihydroxybenzaldehyde (3.20 g, 23.2 mmol) in DMF (70 mL) is carefully added NaH (1.96 g 55% in mineral oil, 48.5 mmol) in portions. The temperature rises to 12° C. Upon completion of the addition, the cooling is removed and a solution of 2-chloromethyl-oxirane (2.57 g, 27.7 mmol) in DMF (3 mL) is added. The reaction mixture is stirred at rt overnight. The mixture is diluted with 1N aq. NaOH (150 mL) and extracted with EA (2×200 mL). The organic extracts are washed with 1 M aq. NaOH (2×200 mL) and water (200 mL), combined, dried over MgSO4, filtered and concentrated. The remaining residue is purified by column chromatography on silica gel eluting with heptene/EA 5:1 to 1:1 to afford the title aldehyde (0.53 g) as a solid. LC: tR=0.69 min. 1H NMR (D6-DMSO): δ 9.77 (s, 1H), 7.41 (dd, J=2.3, 8.2 Hz, 1H), 7.36 (d, J=2.3 Hz, 1H), 7.04 (d, J=8.2 Hz, 1H), 5.10 (t, J=5.9 Hz, 1H, D2O exchangeable), 4.37 (dd, J=2.3, 11.1 Hz, 1H), 4.30-4.23 (m, 1H), 4.05 (dd, J=7.6, 11.1 Hz, 1H), 3.67-3.60 (m, 2H).

後処理

  1. customrises to 12° C
  2. additionUpon completion of the addition
  3. customthe cooling is removed
  4. extractionextracted with EA (2×200 mL)
  5. washThe organic extracts are washed with 1 M aq. NaOH (2×200 mL) and water (200 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe remaining residue is purified by column chromatography on silica gel eluting with heptene/EA 5:1 to 1:1

出典と根拠

ORDレコード
ord-78a4346f1bc04600882e4c1a665dd16d
出典データセット
uspto-grants-2013_09
特許番号
US08524752B2

関連ノート

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