Ammonium Chloride → 3-Ethyl-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-1,2-di(tert-butyldimethylsilyloxy)benzene

HRID 218246

Reaction equation

HRID 218246 reaction equation
[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]([CH2:63][CH3:64])[CH:52]=[CH:51][C:48]=1[CH:49]=O)([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40].[NH4+].[Cl-]>O1CCCC1.CCCCCC.C(OCC)(=O)C>[CH2:63]([C:53]1[C:54]([O:55][Si:56]([C:59]([CH3:60])([CH3:62])[CH3:61])([CH3:57])[CH3:58])=[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)[CH3:64]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 370917Triphenyl(3,4,5-trimethoxybenzyl)phosphonium bromideHCID 859965242,3-Di(tert-butyldimethylsilyloxy)-4-ethyl benzaldehydeHCID 178418339Butyllithium

Product 1

HCID 601306903-Ethyl-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-1,2-di(tert-butyldimethylsilyloxy)benzeneYield 21.5%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of 3,4,5-trimethoxybenzyltriphenylphosphonium bromide (3.9 g, 7.5 mmol) in tetrahydrofuran (40 mL) was cooled to 0° C. and butyllithium (4.7 mL of a 1.6 N solution in hexane, 7.5 mmol) was added dropwise. The brick red solution was stirred at 0° C. for 20 min, then a solution of 12 (2 g, ca 5 mmol) in tetrahydrofuran (15 mL) was added dropwise. The temperature was allowed to rise to room temperature over 4 hours, than the reaction was poured into ethyl acetate (ca 150 mL) and NH4Cl sat (ca 100 mL) the phases separated and the organic layer re-extracted with AcOEt. 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 13:

Workup

  1. waitto rise to room temperature over 4 hours, than the reaction
  2. customseparated
  3. extractionthe organic layer re-extracted with AcOEt
  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)

Sources & evidence

ORD record
ord-1ad46038f5d04092a37b9eae33895dff
Source dataset
uspto-grants-2012_06
Patent number
US08198302B2

Linked notes

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