Methyl Acrylate → Methyl 2-((4-bromophenyl)(hydroxy)methyl)acrylate

HRID 2423392Notes

Reaction equation

HRID 2423392 reaction equation
[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.[C:10]([O:14][CH3:15])(=[O:13])[CH:11]=[CH2:12].C1N2CCN(CC2)C1>CO>[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]([OH:7])[C:11](=[CH2:12])[C:10]([O:14][CH3:15])=[O:13])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 7294Methyl AcrylateHCID 9237DabcoHCID 707414-Bromobenzaldehyde

Product 1

HCID 603917Methyl 2-((4-bromophenyl)(hydroxy)methyl)acrylateYield 47.2%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of 2.46 g (13.3 mmol) of 4-bromobenzaldehyde, 1.0 mL (11.1 mmol) of methyl acrylate and 125 mg (1.11 mmol) of 1,4-diazobicyclo[2.2.2]octane in 5 mL MeOH was stirred at ambient temperature for 46 hr. The solvent was evaporated and the residue taken up in EtOAc. The organics were washed with 0.5 N HCl (aq), then with brine, and concentrated. The residue was purified by silica gel chromatography (120 g of silica gel eluting with 0-30% EtOAc in hexanes over 45 minutes) to give 1.42 g (40%) of methyl 2-[(4-bromophenyl)(hydroxy)methyl]-2-propenoate as a clear oil. 1H NMR (400 MHz, CDCl3): δ 7.47 (d, J=2 Hz, 2H), 7.27 (d, J=2 Hz, 2H), 6.33 (s, 1H), 5.82 (s, 1H), 5.51 (d, J=5 Hz, 1H), 3.72 (s, 3H), 3.07 (d, J=5 Hz, 1H). ESI-LCMS m/z 293 (M+Na)+.

Workup

  1. customThe solvent was evaporated
  2. washThe organics were washed with 0.5 N HCl (aq)
  3. concentrationwith brine, and concentrated
  4. customThe residue was purified by silica gel chromatography (120 g of silica gel eluting with 0-30% EtOAc in hexanes over 45 minutes)

Sources & evidence

ORD record
ord-88da0cabead04eb08fae84f298dbe64b
Source dataset
uspto-grants-2011_06
Patent number
US07960552B2

Reaction notes

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