Methyl chloroformate → 4-Bromo-2-methylphenyl methyl carbonate

HRID 471943Notes

Reaction equation

HRID 471943 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([CH3:9])[CH:3]=1.C(N(CC)CC)C.Cl[C:18]([O:20][CH3:21])=[O:19]>ClCCl>[C:18](=[O:19])([O:20][CH3:21])[O:8][C:5]1[CH:6]=[CH:7][C:2]([Br:1])=[CH:3][C:4]=1[CH3:9]

Participants

5

Reactant 3

HCID 6586Methyl chloroformateHCID 8471TriethylamineHCID 168964-Bromo-2-methylphenol

Product 1

HCID 593949854-Bromo-2-methylphenyl methyl carbonateYield 86.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

4-Bromo-2-methyl-phenol (3.63 g, 19.41 mmol) was dissolved in dichloromethane (18 mL) and triethylamine (5.41 mL, 38.80 mmol), cooled to 0° C., then treated with methyl chloroformate (2.25 mL, 29.12 mmol) and allowed to warm to room temperature over 2 h. The reaction was quenched with water and the layers separated. The aqueous layer was extracted with dichloromethane and the combined organic extracts was dried over Na2SO4, filtered, and concentrated in vacuo to yield an oil that was purified by silica gel chromatography (10% ethyl acetate/hexane) to yield 4-bromo-2-methylphenyl methyl carbonate (4.1 g, 86% yield) as a white solid. 1H NMR (400.0 MHz, DMSO-d6) δ 7.56 (d, J=2.1 Hz, 1H), 7.44 (dd, J=2.3, 8.6 Hz, 1H), 7.18 (d, J=8.6 Hz, 1H), 3.84 (s, 3H), 2.15 (s, 3H).

Workup

  1. customThe reaction was quenched with water
  2. customthe layers separated
  3. extractionThe aqueous layer was extracted with dichloromethane
  4. dry with materialthe combined organic extracts was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto yield an oil that
  8. customwas purified by silica gel chromatography (10% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-a52d71c9749f44a9b98f90e354c75742
Source dataset
uspto-grants-2014_01
Patent number
US08633189B2

Reaction notes

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