Triphenylphosphine → Ethyl 2-bromomethyl-2,3-dihydrobenzofuran-5-carboxylate

HRID 256403Notes

Reaction equation

HRID 256403 reaction equation
O[CH2:2][CH:3]1[CH2:7][C:6]2[CH:8]=[C:9]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:10]=[CH:11][C:5]=2[O:4]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:36]N1C(=O)CCC1=O>C(Cl)Cl>[Br:36][CH2:2][CH:3]1[CH2:7][C:6]2[CH:8]=[C:9]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:10]=[CH:11][C:5]=2[O:4]1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 67184N-bromobutanimideHCID 13728720Ethyl 2-hydroxymethyl-2,3-dihydrobenzofuran-5-carboxylate

Product 1

HCID 20163653Ethyl 2-bromomethyl-2,3-dihydrobenzofuran-5-carboxylateYield 82.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 5.0 g (22.5 mmole) ethyl 2-hydroxymethyl-2,3-dihydrobenzofuran-5-carboxylate in 80 ml methylene chloride under nitrogen was added in one portion 6.5 (24.7 mmole) triphenylphosphine and the resulting solution was stirred for ten minutes. To this was added, in portions over twenty minutes, 4.39 g (24.7 mmole) N-bromosuccinimide and the resulting mixture was stirred overnight at room temperature. The mixture was diluted with methylene chloride, extracted with water, brine and dried (MgSO4). Evaporation in vacuo afforded an oil which was triturated with ethyl ether and filtered to remove insoluble triphenylphosphine oxide. Evaporation of the filtrate yielded 8.4 g of crude product which was charged to a column containing 200 g silica gel and eluted with methylene chloride to provide 5.29 g of purified product, TLC Rf 0.85. Mass spectrum (m/e) 286 (M+). 1H-NMR(CDCl3) ppm(delta): 3.2 (CH2Br), 3.6 (benzyl CH2).

Workup

  1. additionTo this was added, in portions over twenty minutes
  2. extractionextracted with water, brine
  3. dry with materialdried (MgSO4)
  4. customEvaporation in vacuo
  5. customafforded an oil which
  6. customwas triturated with ethyl ether
  7. filtrationfiltered
  8. customto remove insoluble triphenylphosphine oxide
  9. customEvaporation of the filtrate
  10. customyielded 8.4 g of crude product which
  11. additionwas charged to a column
  12. additioncontaining 200 g silica gel
  13. washeluted with methylene chloride

Sources & evidence

ORD record
ord-8aae5879fd0a4b39bf308ee91db20a20
Source dataset
uspto-grants-1987_10
Patent number
US04703052

Reaction notes

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