2,2-Dimethoxypropane → HCID 23116333, compound

HRID 499881Notes

Reaction equation

HRID 499881 reaction equation
[CH3:1][O:2][CH2:3][O:4][C:5]1[C:6]([Br:25])=[C:7]([CH2:17][CH2:18][O:19][CH2:20][CH:21]([OH:24])[CH2:22][OH:23])[C:8]([CH2:15][CH3:16])=[C:9]([O:11][CH2:12][O:13][CH3:14])[CH:10]=1.CO[C:28](OC)([CH3:30])[CH3:29].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>CN(C)C=O>[CH3:1][O:2][CH2:3][O:4][C:5]1[CH:10]=[C:9]([O:11][CH2:12][O:13][CH3:14])[C:8]([CH2:15][CH3:16])=[C:7]([CH2:17][CH2:18][O:19][CH2:20][CH:21]2[CH2:22][O:23][C:28]([CH3:30])([CH3:29])[O:24]2)[C:6]=1[Br:25]

Participants

5

Reactant 3

HCID 64952,2-DimethoxypropaneHCID 521998p-Toluenesulfonic acid monohydrateHCID 23116351HCID 23116351, compound

Product 1

HCID 23116333HCID 23116333, compoundYield 93%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

3-(2-Allyloxyethyl)-1,5-bis(methoxymethoxy)-2-bromo-4-ethylbenzene (5.0 g, 13 mmol) obtained in Example 33, Step 2 was dissolved in a mixed solvent of tetrahydrofuran (50 mL) and water (10 mL). To the solution were added 4-methylmorpholine N-oxide (1.9 g, 16 mmol) and a 2.5% solution of osmium tetroxide in 2-methyl-2-propanol (1.0 mL) at room temperature with stirring, and the mixture was stirred overnight. After addition of a saturated aqueous solution of sodium thiosulfate, the reaction mixture was further stirred for 2 hours and then extracted twice with ethyl acetate. The organic layers were combined, washed with a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 3-{2-[3,5-bis(methoxymethoxy)-2-bromo-6-ethylphenyl]ethoxy}propane-1,2-diol. The obtained 3-{2-[3,5-bis(methoxymethoxy)-2-bromo-6-ethylphenyl]ethoxy}propane-1,2-diol was dissolved in N,N-dimethylformamide (50 mL), and 2,2-dimethoxypropane (6.4 mL, 52 mmol) and p-toluenesulfonic acid monohydrate (0.12 g, 0.63 mmol) were added thereto at room temperature with stirring, followed by stirring for 30 minutes. After neutralization with a saturated aqueous solution of sodium hydrogencarbonate, the reaction mixture was extracted twice with ethyl acetate. The organic layers were combined, washed with a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/9-1/4) to obtain 1,5-bis(methoxymethoxy)-3-{2-[(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy]ethyl}-2-bromo-4-ethylbenzene (5.6 g, 93%) as a colorless oil.

Workup

  1. stirringby stirring for 30 minutes
  2. extractionAfter neutralization with a saturated aqueous solution of sodium hydrogencarbonate, the reaction mixture was extracted twice with ethyl acetate
  3. washwashed with a saturated aqueous solution of sodium chloride
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/9-1/4)

Sources & evidence

ORD record
ord-381a21911904439691cdc71f08d01d20
Source dataset
uspto-grants-2010_08
Patent number
US07767693B2

Reaction notes

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