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

Reaktionsgleichung

Reaktionsgleichung von HRID 218250
[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

Komponenten

7

Edukt 3

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

Produkt 1

HCID 601306753-Methyl-6-[(z)-2-(3,4,5-trimethoxyphenyl)vinyl]-1,2-di(tert-butyldimethylsilyloxy)benzeneAusbeute 48,7 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittelHCID 57417360Sodium chloride; waterLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

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:

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-18e381c1bb114dd0aeaf98be7402d914
Quelldatensatz
uspto-grants-2012_06
Patentnummer
US08198302B2

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