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

HRID 218250

反応式

HRID 218250 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])=[C:53]([CH3:63])[CH:52]=[CH:51][C:48]=1[CH:49]=O)([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40]>O1CCCC1.CCCCCC.[Cl-].[Na+].O>[CH3:63][C:53]1[C:54]([O:55][Si:56]([C:59]([CH3:62])([CH3:61])[CH3:60])([CH3:58])[CH3:57])=[C:47]([O:46][Si:39]([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:40])[CH3:41])[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)=[CH:51][CH:52]=1

参加物

7

反応物 3

HCID 370917Triphenyl(3,4,5-trimethoxybenzyl)phosphonium bromideHCID 877685842,3-Bis-tert-butyldimethylsilyloxy-4-methylbenzaldehydeHCID 178418339Butyllithium

生成物 1

HCID 601306753-Methyl-6-[(z)-2-(3,4,5-trimethoxyphenyl)vinyl]-1,2-di(tert-butyldimethylsilyloxy)benzene収率 48.7%

試薬・触媒・溶媒 3

HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒HCID 57417360Sodium chloride; water溶媒

反応条件

温度
0 °C

実験手順

A suspension of 3,4,5-trimethoxybenzyltriphenylphosphonium bromide (1.77 g, 3.4 mmol) in tetrahydrofuran (40 mL) was cooled to 0° C. and butyllithium (2.1 mL of a 1.6 N solution in hexane, 3.39 mmol) was added dropwise. The brick red solution was stirred at 0° C. for 20 min, then cooled to −78° C. and a solution of 16 (0.86 g, 2.26 mmol) in tetrahydrofuran (15 mL) was added dropwise. The temperature was allowed to rise to room temperature overnight, than the reaction was poured into brine (100 mL, containing 5 mL of 1 n HCl) and extracted twice with tert-butylmethyl ether (ca 100+50 mL). The combined organic extracts were washed with brine, dried over sodium sulphate and the solvent removed under reduced pressure to give a crude which was purified by column (cyclohexane:AcOEt 9:1) to give 0.6 g of 17:

後処理

  1. temperaturecooled to −78° C.
  2. waitto rise to room temperature overnight, than the reaction
  3. extractionextracted twice with tert-butylmethyl ether (ca 100+50 mL)
  4. washThe combined organic extracts were washed with brine
  5. dry with materialdried over sodium sulphate
  6. customthe solvent removed under reduced pressure
  7. customto give a crude which
  8. customwas purified by column (cyclohexane:AcOEt 9:1)

出典と根拠

ORDレコード
ord-18e381c1bb114dd0aeaf98be7402d914
出典データセット
uspto-grants-2012_06
特許番号
US08198302B2

関連ノート

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