Sodium hydride → 3',4'-Dibenzyloxy-3,4,5-trimethoxy-(Z)-stilbene

HRID 866048

반응식

HRID 866048 반응식
[H-].[Na+].[Br-].[CH3:4][O:5][C:6]1[CH:7]=[C:8]([CH:11]=[C:12]([O:16][CH3:17])[C:13]=1[O:14][CH3:15])[CH2:9][PH3+].[CH2:18]([O:25][C:26]1[CH:27]=[C:28]([CH:31]=[CH:32][C:33]=1[O:34][CH2:35][C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)[CH:29]=O)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>O>[CH2:18]([O:25][C:26]1[CH:27]=[C:28]([CH:31]=[CH:32][C:33]=1[O:34][CH2:35][C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)/[CH:29]=[CH:9]\[C:8]1[CH:7]=[C:6]([O:5][CH3:4])[C:13]([O:14][CH3:15])=[C:12]([O:16][CH3:17])[CH:11]=1)[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

참가 물질

5

반응물 3

HCID 24758Sodium hydrideHCID 795263,4-Bis(benzyloxy)benzaldehydeHCID 233739753,4,5-Trimethoxybenzylphosphonium bromide

생성물 1

HCID 53865423',4'-Dibenzyloxy-3,4,5-trimethoxy-(Z)-stilbene수율 61%

시약·촉매·용매 1

HCID 962Water용매

실험 절차

To a stirred suspension of sodium hydride (0.75, 31.4 mmol) in N,N-dimethylimidazolidinone (10 ml) was added 3,4,5-trimethoxy-benzyl-phosphonium bromide (8.26 g 15.71 mmol) under argon. The aldehyde (4.0 g, 1258 mmol) from Example 40 was added to the deep red solution followed by 2 ml of N,N-dimethylimidazolidinone. Before adding ice (10 g)-water (75 ml) the mixture was stirred overnight. Upon extraction with ethyl acetate (3×100 ml), the organic phase was washed with water (3×75 ml), dried and evaporated to a dark colored mass (9.0 g). The crude product in hexane-ethyl acetate (9:1) was chromatographed on a column of SILICA GEL (200 g) to afford a mixture of E- and Z-isomers (3.70 g, 61% yield). A 1.1 g sample of the mixture was rechromatographed on a column of SILICA GEL and eluted with hexane-ethyl acetate (19:1) to furnish Z-isomer (0.25 g) and E-isomer (0.32 g). The Z-isomer was further purified by preparative TLC (hexane-ethyl acetate, 7:3) to yield 3', 4'-Dibenzyloxy-3,4,5-trimethoxy-(Z)-stilbene as a chromatographically homogeneous and viscous oil: IR νmax 1581, 1509, 1462, 1454, 1412, 1265, 1237, 1128, 1007 cm-1 ; 1H-NMR (400 MHz) 3.731 (6H, s, 2×OCH3), 3.856 (3H, s, OCH3), 4.856 (2H, s, ArCH2), 5.121 (2H, s, ARCH2), 6.589 (2H, s, ArH), 6.600 (3H, m, ArH), 6.747 (1H, d, J=8.6 Hz, ArH), 6.758 (1H, brs, ArH), 7,273-7,407 (10H, ArH).

후처리

  1. extractionUpon extraction with ethyl acetate (3×100 ml)
  2. washthe organic phase was washed with water (3×75 ml)
  3. customdried
  4. customevaporated to a dark colored mass (9.0 g)
  5. customThe crude product in hexane-ethyl acetate (9:1) was chromatographed on a column of SILICA GEL (200 g)
  6. customto afford
  7. additiona mixture of E- and Z-isomers (3.70 g, 61% yield)
  8. customA 1.1 g sample of the mixture was rechromatographed on a column of SILICA GEL
  9. washeluted with hexane-ethyl acetate (19:1)
  10. customto furnish Z-isomer (0.25 g) and E-isomer (0.32 g)
  11. customThe Z-isomer was further purified by preparative TLC (hexane-ethyl acetate, 7:3)

출처 및 근거

ORD 기록
ord-8409b7739dd84d27bd17a4b7f95c5a62
출처 데이터셋
uspto-grants-1996_10
특허 번호
US05569786

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