Water → 1,2-Di(t-butyldimethylsilyloxy)-3-ethoxy-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-benzene

HRID 218261ノート

反応式

HRID 218261 の反応式
C([Li])CCC.[Br-].[CH3:7][O:8][C:9]1[CH:10]=[C:11]([CH:14]=[C:15]([O:19][CH3:20])[C:16]=1[O:17][CH3:18])[CH2:12][PH3+].[CH2:21]([O:23][C:24]1[CH:31]=[CH:30][C:27]([CH:28]=O)=[C:26]([O:32][Si:33]([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34])[C:25]=1[O:40][Si:41]([C:44]([CH3:47])([CH3:46])[CH3:45])([CH3:43])[CH3:42])[CH3:22].O>C1COCC1>[Si:33]([O:32][C:26]1[C:27](/[CH:28]=[CH:12]\[C:11]2[CH:10]=[C:9]([O:8][CH3:7])[C:16]([O:17][CH3:18])=[C:15]([O:19][CH3:20])[CH:14]=2)=[CH:30][CH:31]=[C:24]([O:23][CH2:21][CH3:22])[C:25]=1[O:40][Si:41]([C:44]([CH3:45])([CH3:47])[CH3:46])([CH3:42])[CH3:43])([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34]

参加物

6

反応物 4

HCID 962WaterHCID 233739753,4,5-Trimethoxybenzylphosphonium bromideHCID 859964854-Ethoxy-2,3-di(t-butyldimethylsilyloxy)benzaldehydeHCID 178418339Butyllithium

生成物 1

HCID 601306911,2-Di(t-butyldimethylsilyloxy)-3-ethoxy-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-benzene収率 34%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

n-Butyl lithium (0.85 mL, 1.36 mmol, 1.6 M in hexanes) was added dropwise over 10 min to a solution of 3,4,5-trimethoxybenzylphosphonium bromide (0.58 g, 1.12 mmol) in THF (7 mL) at −10° C. The reaction mixture was stirred at this temperature for 15 min then cooled to −70 C and a solution of 35 (0.47 g, 1.14 mmol) in THF (3 mL) was added and the reaction mixture was allowed to warm to room temperature with stirring overnight. The reaction mixture was cooled to 0° C. and water was added. The reaction mixture was extracted with TBME (3×) and the organic phase was washed successively with water and brine, dried (Na2SO4) and concentrated in vacuo to give crude product (0.67 g). Purification by column chromatography (SiO2 2:98 EtOAc:cyclohexane+1% Et3N) gave 36 (0.21 g, 34%) as an 89:11 mixture of Z:E isomers.

後処理

  1. temperaturethen cooled to −70 C
  2. stirringwith stirring overnight
  3. temperatureThe reaction mixture was cooled to 0° C.
  4. extractionThe reaction mixture was extracted with TBME (3×)
  5. washthe organic phase was washed successively with water and brine
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. customto give crude product (0.67 g)
  9. customPurification by column chromatography (SiO2 2:98 EtOAc:cyclohexane+1% Et3N)

出典と根拠

ORDレコード
ord-bc7cbebff0c643d29402b9c53bd0a05c
出典データセット
uspto-grants-2012_06
特許番号
US08198302B2

反応ノート

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