Trifluoroacetic anhydride → 6-Bromo-2-methoxycarbonylmethyl-8-nitro-N-ethoxalyltetrahydroquinoline

HRID 52483

Reaction equation

HRID 52483 reaction equation
[Br:1][C:2]1[CH2:3][CH:4]2[C:9](=[CH:10][CH:11]=1)[N:8]([C:12]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[O:13])[CH:7]([CH2:19][C:20]([O:22][CH3:23])=[O:21])[CH2:6][CH2:5]2.[N+:24]([O-])([O-:26])=[O:25].[NH4+].FC(F)(F)C(OC(=O)C(F)(F)F)=O>C(Cl)(Cl)Cl>[Br:1][C:2]1[CH2:3][CH:4]2[C:9](=[C:10]([N+:24]([O-:26])=[O:25])[CH:11]=1)[N:8]([C:12]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[O:13])[CH:7]([CH2:19][C:20]([O:22][CH3:23])=[O:21])[CH2:6][CH2:5]2

Participants

5

Reactant 3

HCID 9845Trifluoroacetic anhydrideHCID 22985Ammonium nitrateHCID 676514876-bromo-2-methoxycarbonylmethyl-N-ethoxalyltetrahydroquinoline

Product 1

HCID 676513916-Bromo-2-methoxycarbonylmethyl-8-nitro-N-ethoxalyltetrahydroquinolineYield 106.7%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a refluxed solution of 6-bromo-2-methoxycarbonylmethyl-N-ethoxalyltetrahydroquinoline (40 g) and ammonium nitrate (8 g, 0.1 mol) in chloroform (100 mL) was added dropwise trifluoroacetic anhydride (56.5 mL, 0.4 mol) over 40 min. The reflux was continued for 90 min and crashed ice was added. The organic layer was separated, washed with saturated aqueous sodium bicarbonate and brine, dried over magnesium sulfate, and concentrated to give 46 g of the title compound (quant): 1H NMR (270 MHz, CDCl3) δ8.11 and 7.99 (d and d, 1H, J=2 Hz), 7.66 and 7.61 (d and d, 1H, J=2 Hz), 5.03~5.16 and 4.74~4.85 (m and m, 1H), 4.37~4.49 and 4.13 (m and q, 2H, J=7.2 Hz), 3.72 and 3.62 (s and s, 3H), 2.44~3.02 (m, 5H), 1.65~1.80 and 1.50~1.60 (m and m, 1H), 1.42 and 1.23 (t and t, 3H, J=7.2 and 7.2 Hz).

Workup

  1. additionwas added
  2. customThe organic layer was separated
  3. washwashed with saturated aqueous sodium bicarbonate and brine
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-880ae8be6c3c480a916014a0acbec60d
Source dataset
uspto-grants-1997_04
Patent number
US05616586

Linked notes

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