Carbon tetrabromide → Ethyl 3-(bromomethyl)phenoxyacetate

HRID 979544Notes

Reaction equation

HRID 979544 reaction equation
O[CH2:2][C:3]1[CH:4]=[C:5]([CH:13]=[CH:14][CH:15]=1)[O:6][CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9].C(Br)(Br)(Br)[Br:17].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C=O)C>[Br:17][CH2:2][C:3]1[CH:4]=[C:5]([CH:13]=[CH:14][CH:15]=1)[O:6][CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

5

Reactant 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 18367402Ethyl [3-(hydroxymethyl)phenoxy]acetate

Product 1

HCID 11459982Ethyl 3-(bromomethyl)phenoxyacetateYield 71.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution containing ethyl 3-(hydroxymethyl)phenoxyacetate (2.6 g.) and carbon tetrabromide (8.3 g.) in DMF (30 ml.) was treated with a solution of triphenylphosphine (6.55 g.) in DMF (20 ml.) with stirring. The temperature was maintained below 15° C. during the addition using an ice bath. After 1 hour the mixture was poured into ice-water (300 ml.) and the aqueous mixture was extracted with ether (3×100 ml.). The combined extracts were washed with water (3×100 ml.) and saturated brine (100 ml.), dried (MgSO4) and concentrated. The resultant oil was purified by flash column chromatography, eluting with petrol (60°-80° )/ether (80:20 v/v) to give ethyl 3 (bromomethyl)phenoxyacetate (2.4 g.) as a colourless oil, NMR: 1.3 (3H,t), 4.25 (2H,q), 4.4 (2H,s), 4.6 (2H,s) and 6.7-7.4 (4H,m)ppm.

Workup

  1. temperatureThe temperature was maintained below 15° C. during the addition
  2. extractionthe aqueous mixture was extracted with ether (3×100 ml.)
  3. washThe combined extracts were washed with water (3×100 ml.) and saturated brine (100 ml.)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customThe resultant oil was purified by flash column chromatography
  7. washeluting with petrol (60°-80° )/ether (80:20 v/v)

Sources & evidence

ORD record
ord-60963bfaf7744b7c97012ab8691c7041
Source dataset
uspto-grants-1987_05
Patent number
US04668698

Reaction notes

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