Triphenylphosphine → Methyl [3-(3-bromopropoxy)phenyl]acetate

HRID 881654Notes

Reaction equation

HRID 881654 reaction equation
[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([OH:11])[CH:6]=1.[Br:13][CH2:14][CH2:15][CH2:16]O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C(Cl)Cl>[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([O:11][CH2:16][CH2:15][CH2:14][Br:13])[CH:6]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 123083-Bromo-1-propanolHCID 39129Methyl 3-HydroxyphenylacetateHCID 75555Diisopropyl diazene-1,2-dicarboxylate

Product 1

HCID 10565189Methyl [3-(3-bromopropoxy)phenyl]acetateYield 86%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 3-hydroxyphenyl acetic acid methyl ester (1) (5.28 g, 0.032 mol), 3-bromo-1-propanol (6.95 g, 0.05 mol), and Ph3P in CH2Cl2 (100 mL) was treated with diisopropyl azodicarboxylate (6.67 g, 0.033 mol) dropwise. The reaction mixture stirred at room temperature for 12 hours and was concentrated to an oil, which was purified by flash chromatography (gradient elution, 9:1 to 7:3 Hexanes/EtOAc to give the desired product as oil 7.90 g in 86% yield. 1H NMR (CDCl3) δ 7.25 (t, 1H), 6.88 (d, 1H), 6.84 (m, 2H), 4.11 (t, 2H), 3.70 (s, 3H), 3.61 (m, 4H), 2.34 (m, 2H). 13C NMR (CDCl3) δ 169.0, 155.9, 132.5, 126.7, 119.0, 112.7, 110.3, 62.3, 49.2, 38.3, 29.5, 27.1.

Workup

  1. concentrationwas concentrated to an oil, which
  2. customwas purified by flash chromatography (
  3. washgradient elution, 9:1 to 7:3 Hexanes/EtOAc

Sources & evidence

ORD record
ord-17c0dcd5b9d846a7960f727aacd88138
Source dataset
uspto-grants-2015_03
Patent number
US08993628B2

Reaction notes

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