Triphenyl(3,4,5-trimethoxybenzyl)phosphonium bromide → 4-Bromo-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-1,2-di(tert-butyldimethylsilyloxy)benzene

HRID 218251ノート

反応式

HRID 218251 の反応式
[Br-].[CH3:2][O:3][C:4]1[CH:5]=[C:6]([CH:27]=[C:28]([O:32][CH3:33])[C:29]=1[O:30][CH3:31])[CH2:7][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C([Li])CCC.[Si:39]([O:46][C:47]1[C:54]([O:55][Si:56]([C:59]([CH3:62])([CH3:61])[CH3:60])([CH3:58])[CH3:57])=[CH:53][C:52]([Br:63])=[CH:51][C:48]=1[CH:49]=O)([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40]>O1CCCC1.CCCCCC.C(OC)(C)(C)C>[Br:63][C:52]1[CH:51]=[C:48](/[CH:49]=[CH:7]\[C:6]2[CH:27]=[C:28]([O:32][CH3:33])[C:29]([O:30][CH3:31])=[C:4]([O:3][CH3:2])[CH:5]=2)[C:47]([O:46][Si:39]([C:42]([CH3:45])([CH3:43])[CH3:44])([CH3:41])[CH3:40])=[C:54]([O:55][Si:56]([C:59]([CH3:62])([CH3:61])[CH3:60])([CH3:57])[CH3:58])[CH:53]=1

参加物

7

反応物 3

HCID 370917Triphenyl(3,4,5-trimethoxybenzyl)phosphonium bromideHCID 60130680HCID 60130680、化合物HCID 178418339Butyllithium

生成物 1

HCID 601306724-Bromo-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-1,2-di(tert-butyldimethylsilyloxy)benzene収率 55.9%

試薬・触媒・溶媒 3

HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒HCID 15413tert-Butyl methyl ether溶媒

反応条件

温度
0 °C

実験手順

A suspension of 3,4,5-trimethoxybenzyltriphenylphosphonium bromide (1.69 g, 3.23 mmol) in tetrahydrofuran (30 mL) was cooled to 0° C. and butyllithium (2 mL of a 1.6 N solution in hexane, 3.23 mmol) was added dropwise. The brick red solution was stirred at 0° C. for 20 min, then a solution of 19 (0.96 g, ca 2.2 mmol) in tetrahydrofuran (12 mL) was added dropwise. The temperature was allowed to rise to room temperature overnight, than the reaction was diluted with tert-butylmethyl ether (ca 100 mL) and washed with water (ca 50 mL, containing 1 mL 2N HCl) then brine (30 mL). The organic layer was dried over sodium sulphate and the solvent removed under reduced pressure to give a crude which was purified by column (elution with cyclohexane:AcOEt 10:1) to give 0.75 g of 20 still impure with 20% of the E isomer.

後処理

  1. waitto rise to room temperature overnight, than the reaction
  2. washwashed with water (ca 50 mL, containing 1 mL 2N HCl)
  3. dry with materialThe organic layer was dried over sodium sulphate
  4. customthe solvent removed under reduced pressure
  5. customto give a crude which
  6. customwas purified by column (elution with cyclohexane:AcOEt 10:1)

出典と根拠

ORDレコード
ord-ae5a82024ead43189050401038470273
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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