Sodium Nitrite → 1-(3,4-Dihydro-6-methoxy-7-nitro-1(2H)-quinolinyl)ethanone

HRID 1014373Notes

Reaction equation

HRID 1014373 reaction equation
[C:1]([N:4]1[C:13]2[C:8](=[CH:9][C:10]([O:14][CH3:15])=[CH:11][CH:12]=2)[CH2:7][CH2:6][CH2:5]1)(=[O:3])[CH3:2].[N:16]([O-:18])=[O:17].[Na+]>FC(F)(F)C(O)=O>[C:1]([N:4]1[C:13]2[C:8](=[CH:9][C:10]([O:14][CH3:15])=[C:11]([N+:16]([O-:18])=[O:17])[CH:12]=2)[CH2:7][CH2:6][CH2:5]1)(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 23668193Sodium NitriteHCID 40082022HCID 40082022, compound

Product 1

HCID 594421241-(3,4-Dihydro-6-methoxy-7-nitro-1(2H)-quinolinyl)ethanoneYield 59%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

A solution of 1-acetyl-6-(methyloxy)-1,2,3,4-tetrahydroquinoline (500 mg, 2.44 mmol, Aldrich) in trifluoroacetic acid (4 mL, Aldrich) was treated with sodium nitrite (169 mg, 2.45 mmol, added slowly in about 4 portions, Aldrich). The dark brown reaction was stirred for 2 h and then poured over ice. The mixture was extracted with ethyl acetate and the organic layer was separated, dried over magnesium sulfate, filtered, concentrated, and purified by chromatography on SiO2 (0 to 100% ethyl acetate/hexanes) to give 1-acetyl-6-(methyloxy)-7-nitro-1,2,3,4-tetrahydroquinoline (357 mg, 59%). 1H NMR (400 MHz, DMSO-d6) is complicated due to amide rotomers δ ppm 1.83-1.94 (m, 2 H), 2.14-2.25 (m, 3 H), 2.76-2.85 (m, 2 H), 3.64-3.73 (m, 2 H), 3.86-3.92 (m, 3 H), 7.14-7.25 (m, 1 H), 8.38 (very broad singlet, 1H).

Workup

  1. additionadded slowly in about 4 portions, Aldrich)
  2. customThe dark brown reaction
  3. additionpoured over ice
  4. extractionThe mixture was extracted with ethyl acetate
  5. customthe organic layer was separated
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. custompurified by chromatography on SiO2 (0 to 100% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-71aba4e7df374dfcb88bd85b6971438c
Source dataset
uspto-grants-2011_07
Patent number
US07981903B2

Reaction notes

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