Acetic Acid → Tert-butyl{4-[4-(4-methoxyphenyl)-3-methylbut-3-en-1-yl]phenoxy}-dimethylsilane

HRID 718560

Reaction equation

HRID 718560 reaction equation
[Si:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([CH2:15][CH2:16][C:17](=O)[CH3:18])=[CH:11][CH:10]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[Br-].[C:21]1([CH3:47])[CH:26]=[CH:25][CH:24]=[C:23](C[P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[CH:22]=1.C[C:49](O)=[O:50]>C1COCC1>[C:4]([Si:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([CH2:15][CH2:16][C:17]([CH3:18])=[CH:47][C:21]2[CH:26]=[CH:25][C:24]([O:50][CH3:49])=[CH:23][CH:22]=2)=[CH:11][CH:10]=1)([CH3:3])[CH3:2])([CH3:7])([CH3:6])[CH3:5]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 187986664-(4-tert-Butyldimethylsilyloxy-phenyl)-2-butanoneHCID 22004950(m-Tolyl)methyltriphenylphosphonium bromide

Product 1

HCID 86702792Tert-butyl{4-[4-(4-methoxyphenyl)-3-methylbut-3-en-1-yl]phenoxy}-dimethylsilane

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
70 °C

Procedure

Potassium f-butylat (45 mL, 45 mmol, 1.0 equiv., 1M in THF) and 4-[4-(tert-butyldimethylsilyloxy)phenyl]butan-2-one (12.5 g, 45 mmol, 1.0 equiv.) in THF (23 mL) were added simultaneously to a solution of (m-tolyl)methyltriphenylphosphonium bromide (20.1 g, 45 mmol, 1.0 equiv.) in THF (45 mL) at 70° C. The mixture was stirred at 70° C. for 16 h. After addition of 20% aq. AcOH-solution at 25° C., the aqueous layer was extracted with hexane. The combined organic phases were washed with MeOH/H2O (4:1; 2-3×), dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 99:1) to yield tert-butyl{4-[4-(4-methoxyphenyl)-3-methylbut-3-en-1-yl]phenoxy}-dimethylsilane as a light yellow oil. This compound was dissolved in THF (32 mL), n-Bu4NF (35 mL, 35 mmol, 0.8 equiv., 1.0 M in THF) was added, and the mixture was stirred at 25° C. for 1 h. After addition of H2O, the aqueous layer was extracted with MTBE (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (hexane/EtOAc 9:1→4:1) to yield 7.40 g (65% over 2 steps) of the title compound as a light yellow oil.

Workup

  1. extractionthe aqueous layer was extracted with hexane
  2. washThe combined organic phases were washed with MeOH/H2O (4:1; 2-3×)
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated
  6. customThe residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 99:1)

Sources & evidence

ORD record
ord-ade6e4f9ef244671883da1bd0f6679ee
Source dataset
uspto-grants-2015_11
Patent number
US09193935B2

Linked notes

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