Phenyl chloroformate → phenyl 2-(8-fluoro-6-nitro-3,4-dihydroquinolin-1(2H)-yl)ethyl(methyl)carbamate

HRID 1922463Notes

Reaction equation

HRID 1922463 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N+:17]([O-:19])=[O:18])[CH:5]=[C:6]2[C:11]=1[N:10]([CH2:12][CH2:13][N:14](C)[CH3:15])[CH2:9][CH2:8][CH2:7]2.Cl[C:21]([O:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)=[O:22]>ClCCl.O.C(=O)([O-])[O-].[K+].[K+]>[F:1][C:2]1[CH:3]=[C:4]([N+:17]([O-:19])=[O:18])[CH:5]=[C:6]2[C:11]=1[N:10]([CH2:12][CH2:13][N:14]([CH3:15])[C:21](=[O:22])[O:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[CH2:9][CH2:8][CH2:7]2

Participants

6

Reactant 2

HCID 15891Phenyl chloroformateHCID 533922632-(8-Fluoro-6-nitro-3,4-dihydroquinolin-1(2H)-yl)-N,N-dimethylethanamine

Product 1

HCID 59807154phenyl 2-(8-fluoro-6-nitro-3,4-dihydroquinolin-1(2H)-yl)ethyl(methyl)carbamateYield 82.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 11430Potassium CarbonateSolvent

Procedure

To a stirred solution of 2-(8-fluoro-6-nitro-3,4-dihydroquinolin-1(2H)-yl)-N,N-dimethylethanamine (500 mg, 1.871 mmol) in Dichloromethane (8 ml) at room temperature was added phenyl chloroformate (0.352 ml, 2.81 mmol) via a syringe dropwise, slowly. The resulting solution was stirred overnight at room temperature. The reaction mixture was then diluted with water and potassium carbonate (dilute) and extracted with dichloromethane (3×). The combined organics were dried, filtered and concentrated, then chromatographed in 0-50% ethyl acetate in hexanes, giving the desired phenyl 2-(8-fluoro-6-nitro-3,4-dihydroquinolin-1(2H)-yl)ethyl(methyl)carbamate (576 mg, 1.543 mmol, 82% yield). 1H NMR (DMSO-d6) δ 7.85-7.76 (m, 1H); 7.75-7.70 (m, 1H); 7.34 (t, J=7 Hz, 1H); 7.22-7.16 (m, 1H); 6.99-6.95 (m, 2H); 3.77-3.65 (m, 3H); 3.60-3.54 (m, 1H); 3.43 (t, J=5.5 Hz, 2H); 3.02, 2.93 (2s, 3H); 2.75 (t, J=5.8, 2H); 1.90-1.81 (m, 2H). ESI-MS (m/z, %): 374 (MH+, 100).

Workup

  1. extractionextracted with dichloromethane (3×)
  2. customThe combined organics were dried
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customchromatographed in 0-50% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-a1bfad1f03d148d3900a8d0385ee216b
Source dataset
uspto-grants-2012_05
Patent number
US08173813B2

Reaction notes

Loading…