Methyl chloroformate → Methyl (4-fluoro-3-nitrophenyl)carbamate

HRID 472931Notes

Reaction equation

HRID 472931 reaction equation
Cl[C:2]([O:4][CH3:5])=[O:3].[F:6][C:7]1[CH:13]=[CH:12][C:10]([NH2:11])=[CH:9][C:8]=1[N+:14]([O-:16])=[O:15].CCN(C(C)C)C(C)C>ClCCl>[F:6][C:7]1[CH:13]=[CH:12][C:10]([NH:11][C:2](=[O:3])[O:4][CH3:5])=[CH:9][C:8]=1[N+:14]([O-:16])=[O:15]

Participants

5

Reactant 3

HCID 6586Methyl chloroformateHCID 677684-Fluoro-3-nitroanilineHCID 81531Diisopropylethylamine

Product 1

HCID 3636899Methyl (4-fluoro-3-nitrophenyl)carbamate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Methyl chloroformate (13.2 mL, 170.2 mmol) was added dropwise to a cold (0° C.) dichloromethane (200 mL) solution of 4-fluoro-3-nitro aniline (24.15 g, 154.7 mmol) and DIPEA (35 mL, 201 mmol). The reaction mixture was stirred at rt overnight. The solution was then diluted with 200 mL of dichloromethane and washed with 2M HCl, brine and dried over anhydrous MgSO4. The solvent was concentrated and the product was directly used for next step without further purification. Yield: 35.5 g (99%); 1H NMR (400 MHz, CHLOROFORM-D) δ 3.81 (s, 3H), 7.02 (s, 1H), 7.23 (m, 1H), 7.72 (d, J=8.59 Hz, 1H), 8.17 (dd, J=6.35, 2.64 Hz, 1H).

Workup

  1. washwashed with 2M HCl, brine
  2. dry with materialdried over anhydrous MgSO4
  3. concentrationThe solvent was concentrated
  4. customthe product was directly used for next step without further purification

Sources & evidence

ORD record
ord-eb15137ad0d148ad996a892b305c3c62
Source dataset
uspto-grants-2014_01
Patent number
US08633235B2

Reaction notes

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