1,2-Dibromoethane → Methyl 2-[(2-bromoethyl)oxy]-3-[(phenylcarbonyl)oxy]benzoate

HRID 253291Notes

Reaction equation

HRID 253291 reaction equation
[OH:1][C:2]1[C:11]([O:12][C:13]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[O:14])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[Br:21][CH2:22][CH2:23]Br.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C)C=O>[Br:21][CH2:22][CH2:23][O:1][C:2]1[C:11]([O:12][C:13]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[O:14])=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

5

Reactant 3

HCID 78391,2-DibromoethaneHCID 10796Cesium carbonateHCID 66891613Methyl 3-(benzoyloxy)-2-hydroxybenzoate

Product 1

HCID 66891818Methyl 2-[(2-bromoethyl)oxy]-3-[(phenylcarbonyl)oxy]benzoateYield 52.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of methyl 2-hydroxy-3-[(phenylcarbonyl)oxy]benzoate (42.1 g, 155 mmol) in N,N-dimethylformamide (300 mL) was added 1,2-dibromoethane (135 mL, 1550 mmol) and cesium carbonate (76 g, 232 mmol), and the reaction mixture was stirred at room temperature under nitrogen for 6.5 h. The volume of the reaction mixture was reduced by half in vacuo, and then partitioned between water (500 mL) and ethyl acetate (500 mL). The layers were separated, and the organic layer was washed with brine (200 mL), dried over anhydrous magnesium sulfate and concentrated. The crude precipitate was triturated with 50% diethyl ether/hexanes (200 mL). The solid was washed with 50% diethyl ether/hexanes (2×200 mL) and isolated to give 30.6 g (52% over 2 steps) of methyl 2-[(2-bromoethyl)oxy]-3-[(phenylcarbonyl)oxy]benzoate as an off-white powder: 1H NMR (400 MHz, CDCl3): 8.23-8.21 (m, 2H), 7.77 (dd, J=1.6, 7.6 Hz, 1H), 7.68-7.64 (m, 1H), 7.53 (t, J=6.0 Hz, 2H), 7.39 (dd, J=1.8, 8.0 Hz, 1H), 7.25 (t, J=6.4 Hz, 1H), 4.31 (t, J=6.4 Hz, 2H), 3.93 (s, 3H), 3.52 (t, J=6.4 Hz, 2H).

Workup

  1. custompartitioned between water (500 mL) and ethyl acetate (500 mL)
  2. customThe layers were separated
  3. washthe organic layer was washed with brine (200 mL)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated
  6. customThe crude precipitate was triturated with 50% diethyl ether/hexanes (200 mL)
  7. washThe solid was washed with 50% diethyl ether/hexanes (2×200 mL)
  8. customisolated

Sources & evidence

ORD record
ord-7c4f5c16c9804fd8a6ad5bc32052e9d3
Source dataset
uspto-grants-2011_01
Patent number
US07872014B2

Reaction notes

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