Water → 1-(((S)-2-(Bromomethyl)-3-methylbutoxy)methyl)benzene

HRID 1522952Notes

Reaction equation

HRID 1522952 reaction equation
[CH2:1]([O:8][CH2:9][C@H:10]([CH:13]([CH3:15])[CH3:14])[CH2:11]O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CN(C)C=O.P(Br)(Br)([Br:23])=O.O>CC1C=CC=CC=1>[CH2:1]([O:8][CH2:9][C@H:10]([CH:13]([CH3:15])[CH3:14])[CH2:11][Br:23])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 6228DimethylformamideHCID 24613Phosphorus oxybromideHCID 68782329(R)-2-(benzyloxymethyl)-3-methylbutan-1-ol

Product 1

HCID 117159911-(((S)-2-(Bromomethyl)-3-methylbutoxy)methyl)benzeneYield 79.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Dissolve (R)-2-(benzyloxy-methyl)-3-methyl butanol (15.6 g, 75 mmol) and N,N-dimethyl formamide (0.6 g, 8.25 mmol) in methyl benzene (351 ml), add phosphorus oxybromide (25.8 g, 90 mmol) in droplets slowly, and control the temperature below 60° C. in that process; then, let them to react at 80° C. for 2 hours; cool down to room temperature, add water (702 ml), stir for 20 minutes, and separate the layers; extract the aqueous layer with petroleum ether for three cycles, combine the organic layers and wash twice with saturated sodium bicarbonate and saturated sodium chloride respectively; dry the organic layer with anhydrous sodium sulfate, filter, and condense the filtrate so as to obtain 17.5 g of oily matter; treat the oil matter by reduced pressure distillation to obtain 16.1 g of colorless transparent liquid; the yield is 79.2%, and the chiral purity is ≧99.9%.

Workup

  1. customthe temperature below 60° C.
  2. customto react at 80° C. for 2 hours
  3. customseparate the layers
  4. extractionextract the aqueous layer with petroleum ether for three cycles
  5. washwash twice with saturated sodium bicarbonate and saturated sodium chloride respectively
  6. dry with materialdry the organic layer with anhydrous sodium sulfate
  7. filtrationfilter
  8. customcondense the filtrate so as
  9. customto obtain 17.5 g of oily matter
  10. additiontreat the oil matter
  11. distillationby reduced pressure distillation

Sources & evidence

ORD record
ord-a0be147b62344f169ef28d9e5979b9e5
Source dataset
uspto-grants-2015_07
Patent number
US09079839B2

Reaction notes

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