Acetic Acid → HCID 178455438, compound

HRID 2264478Notes

Reaction equation

HRID 2264478 reaction equation
[C:1]([Si:5]([CH3:24])([CH3:23])[O:6][C:7]1[CH:12]=[C:11]([C:13]([CH3:21])([CH3:20])[O:14][SiH2:15][C:16]([CH3:19])([CH3:18])[CH3:17])[CH:10]=[CH:9][C:8]=1[F:22])([CH3:4])([CH3:3])[CH3:2].[Li]C(CC)C.B(OC)(OC)[O:31]C.C(O)(=O)C.OO.O>C1COCC1>[C:1]([Si:5]([CH3:24])([CH3:23])[O:6][C:7]1[C:8]([F:22])=[C:9]([OH:31])[CH:10]=[C:11]([C:13]([CH3:21])([CH3:20])[O:14][SiH2:15][C:16]([CH3:19])([CH3:18])[CH3:17])[CH:12]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 6

HCID 176Acetic AcidHCID 784Hydrogen PeroxideHCID 962WaterHCID 8470Trimethyl borateHCID 131727842HCID 131727842, compoundHCID 178418400CID 53628100

Product 1

HCID 178455438HCID 178455438, compoundYield 64%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 2-(tert-butyl-dimethyl-silanyloxy)-4-(tert-butyl-dimethyl-silanyloxymethyl)-1-fluoro-benzene (23.70 g, 63.9 mmol, 1.0 equiv) in anhydrous THF (130 mL) was added at −78° C. under Ar a solution of sec-BuLi (54.5 mL, 71.6 mmol, 1.1 equiv, 1.3 M solution in hexane) within 30 min. Then a solution of trimethyl borate (7.13 mL, 6.64 g, 63.9 mmol, 1.0 equiv) in anhydrous THF (30 mL) was added slowly within 30 min and the cooling bath removed. A solution of conc. acetic acid (5.49 mL, 5.76 g, 95.9 mmol, 1.5 equiv) was slowly added followed by addition of a solution of 35% hydrogen peroxide in water (6.2 mL, 6.83 g, 70.3 mmol, 1.1 equiv) and the reaction mixture kept at 0° C. for 30 min. After stirring at rt for an additional 4 h, the reaction was extracted with diethyl ether (2×100 mL) and the combined organic phases washed with a solution of 10% NaOH (2×100 mL) and a sat. solution of sodium chloride (2×100 mL). The organic phase was dried over Na2SO4, concentrated by evaporation under reduced pressure and the crude material purified with column chromatography on silica eluting with hexane/ethyl acetate (19:1) providing 15.80 g (64%) of the title compound. 1H NMR (400 MHz, CDCl3): δ 0.00 (s, 6H), 0.10 (s, 6H), 0.85 (s, 9H), 0.91 (s, 9H), 4.50 (s, 2H), 4.93 (br s, 1H), 6.37 (d, J=5.6 Hz, 1H), 6.47 (d, J=5.6 Hz, 1H). MS (EI): 329.2 [M-tert-Bu]+.

Workup

  1. customthe cooling bath removed
  2. extractionthe reaction was extracted with diethyl ether (2×100 mL)
  3. washthe combined organic phases washed with a solution of 10% NaOH (2×100 mL)
  4. dry with materialThe organic phase was dried over Na2SO4
  5. concentrationconcentrated by evaporation under reduced pressure
  6. customthe crude material purified with column chromatography on silica eluting with hexane/ethyl acetate (19:1)

Sources & evidence

ORD record
ord-08cf88733941436d9c3d344f30574fa9
Source dataset
uspto-grants-2010_12
Patent number
US07855194B2

Reaction notes

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