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

HRID 80015

반응식

HRID 80015 반응식
[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

참가 물질

6

반응물 3

HCID 7835EpichlorohydrinHCID 87683,4-DihydroxybenzaldehydeHCID 24758Sodium hydride

생성물 1

HCID 156593722-Hydroxymethyl-1,4-benzodioxan-6-carbaldehyde수율 11.8%

시약·촉매·용매 2

HCID 6228Dimethylformamide용매2회HCID 14798Sodium Hydroxide용매

실험 절차

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 it 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).

후처리

  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

출처 및 근거

ORD 기록
ord-54157112bb0a4b87ac0b67c91dfeb55d
출처 데이터셋
uspto-grants-2014_09
특허 번호
USRE045174E1

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