Methallyl alcohol → HCID 10707028, compound

HRID 2066640Notes

Reaction equation

HRID 2066640 reaction equation
[CH3:1][C:2](=[CH2:5])[CH2:3][OH:4].[H-].[Na+].[CH2:8]([O:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20]Cl)=[CH:18][CH:17]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>CN(C=O)C>[CH2:8]([O:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20][O:4][CH2:3][C:2]([CH3:5])=[CH2:1])=[CH:18][CH:17]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

5

Reactant 3

HCID 10557Methallyl alcoholHCID 24758Sodium hydrideHCID 700424-Benzyloxybenzyl chloride

Product 1

HCID 10707028HCID 10707028, compoundYield 93.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Conditions

Temperature
0 °C

Procedure

A solution of 2-methyl-2-propen-1-ol (120) (1.17 mL, 13.9 mmol) in anhydrous DMF (5 mL, then 2×1 mL to rinse) was added to a suspension of 60% NaH (674 mg, 16.9 mmol) in anhydrous DMF (5 mL) under N2 at 0° C. and the mixture was stirred at 0° C. for 30 min. A solution of 4-(benzyloxy)benzyl chloride (3.87 g, 16.6 mmol) in anhydrous DMF (6 mL, then 2×2 mL to rinse) was added and the mixture was stirred at room temperature for 16 h. The resulting mixture was added to ice/aqueous NaHCO3 (100 mL) and extracted with EtOAc (4×100 mL). The extracts were washed with water (100 mL), the EtOAc was removed, and the residual oil was chromatographed on silica gel. Elution with petroleum ether firstly gave foreruns, then further elution with 0-25% CH2Cl2/petroleum ether gave 1-(benzyloxy)-4-{[(2-methyl-2-propenyl)oxy]methyl}benzene (122) (reported by Wennerberg et al., 1999 via alkylation of 4-(benzyloxy)benzyl alcohol) (3.48 g, 93%) as an oil that was used directly in the next step; 1H NMR (CDCl3) δ 7.45-7.28 (m, 5H), 7.27 (dt, J=8.5, 2.4 Hz, 2H), 6.95 (dt, J=8.7, 2.4 Hz, 2H), 5.07 (s, 2H), 4.99 (m, 1H), 4.91 (m, 1H), 4.42 (s, 2H), 3.91 (s, 2H), 1.76 (s, 3H).

Workup

  1. additionwas added
  2. stirringthe mixture was stirred at room temperature for 16 h
  3. extractionextracted with EtOAc (4×100 mL)
  4. washThe extracts were washed with water (100 mL)
  5. customthe EtOAc was removed
  6. customthe residual oil was chromatographed on silica gel
  7. washElution with petroleum ether firstly gave foreruns
  8. washfurther elution with 0-25% CH2Cl2/petroleum ether

Sources & evidence

ORD record
ord-9e2cd52be19b4d20b4c478d368b966a1
Source dataset
uspto-grants-2012_10
Patent number
US08293734B2

Reaction notes

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