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

HRID 218250노트

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HRID 218250 반응식
[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

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 8028Tetrahydrofuran용매2회HCID 8058Hexane용매HCID 57417360Sodium chloride; water용매

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온도
0 °C

실험 절차

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:

후처리

  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)

출처 및 근거

ORD 기록
ord-18e381c1bb114dd0aeaf98be7402d914
출처 데이터셋
uspto-grants-2012_06
특허 번호
US08198302B2

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