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

HRID 1465109Notes

Reaction equation

HRID 1465109 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-3b2e476db7304e6f83f6c2ebf0e9d946
Source dataset
uspto-grants-2015_04
Patent number
US08999976B2

Reaction notes

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