Ethanol → HCID 17173442, compound

HRID 1514870Notes

Reaction equation

HRID 1514870 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:5](C(O)=O)=[CH:4][C:3]=1[CH3:11].C([N:14]([CH2:17]C)CC)C.[N-]=[N+]=[N-].[CH3:22][CH2:23][OH:24].[O:25]1CCOCC1>C([O-])(O)=O.[Na+]>[CH2:23]([O:24][C:17](=[O:25])[NH:14][C:5]1[CH:9]=[CH:10][C:2]([Br:1])=[C:3]([CH3:11])[CH:4]=1)[CH3:22]

Participants

7

Reactant 5

HCID 702EthanolHCID 8471TriethylamineHCID 312751,4-DioxaneHCID 33558AzideHCID 821314-Bromo-3-methylbenzoic acid

Product 1

HCID 17173442HCID 17173442, compound

Reagents, catalysts & solvents 1

HCID 516892Sodium BicarbonateSolvent

Procedure

To a solution of 4-bromo-3-methyl-benzoic acid (300 mg) in 1,4-dioxane (5 mL) were added triethylamine (0.245 mL) and diphenylphosphory azide (0.316 mL). The mixture was stirred at room temperature for 16 h and then after adding EtOH (0.8 mL), the mixture was heated at 80° C. for 7 h. The reaction mixture was diluted with saturated NaHCO3 aqueous solution. The aqueous layer was extracted with EtOAc, and the organic extracts were washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The crude product was purified by column chromatography (SiO2, EtOAc:Hexane=5:95 to 40:60) to give (4-bromo-3-methyl-phenyl)-carbamic acid ethyl ester as colorless oil: MS (m/z) 258 (M−1); 1H NMR (CDCl3, 400 MHz) δ 7.42 (d, 1H), 7.30 (s, 1H), 7.08 (dd, 1H), 6.53 (s, 1H), 4.22 (q, 2H), 2.36 (s, 3H), 1.30 (t, 3H).

Workup

  1. temperaturethe mixture was heated at 80° C. for 7 h
  2. extractionThe aqueous layer was extracted with EtOAc
  3. washthe organic extracts were washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified by column chromatography (SiO2, EtOAc:Hexane=5:95 to 40:60)

Sources & evidence

ORD record
ord-da6c8e5c0bcc48c6a85d542ac84239de
Source dataset
uspto-grants-2012_07
Patent number
US08222248B2

Reaction notes

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