Nitric Acid → HCID 10631124, compound

HRID 850359Notes

Reaction equation

HRID 850359 reaction equation
[CH2:1]([CH:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[NH:6][CH2:5][CH2:4]1)[CH3:2].OS(O)(=O)=O.[N:18]1C2C(=CC=CC=2)C=CC=1.[N+]([O-])(O)=O.C([O-])(O)=O.[Na+].[OH-].[Na+]>O.[Pd].CCOC(C)=O.CCO>[NH2:18][C:9]1[CH:8]=[C:7]2[C:12]([CH:3]([CH2:1][CH3:2])[CH2:4][CH2:5][NH:6]2)=[CH:11][CH:10]=1

Participants

10

Reactant 6

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 7047QuinolineHCID 14798Sodium HydroxideHCID 516892Sodium BicarbonateHCID 1086663722494-02-6

Product 1

HCID 10631124HCID 10631124, compoundYield 57%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 962WaterSolventHCID 21584252Ethanol ethylacetateSolvent

Conditions

Temperature
-10 °C

Procedure

A 25-mL rb flask containing (R/S)-4-ethyl-1,2,3,4-tetrahydroquinoline (340 mg, 2.1 mmol) was cooled to -10° C., and conc. H2SO4 (5 mL) was added slowly. The resulting solution was warmed to rt to effect complete dissolution of the quinoline, then cooled again to -10° C. and stirred vigorously. Fuming HNO3 (85 μL) was added dropwise, slowly, and the reaction mixture turned dark red. After 10 min, the reaction mixture was poured onto cracked ice and diluted with water (5 mL). Sat'd NaHCO3 (80 mL) was added, and the pH was adjusted to pH 9 with 3.0 M NaOH. This aqueous phase was extracted with EtOAc (3×75 mL), and the combined extracts were dried (Na2SO4), and concentrated under reduced pressure to yield a dark red oil. This crude material was placed into a 250-mL rb flask with 1:1 EtOAc/EtOH (40 mL) and 10% Pd on C (approx. 1 mol %). The vessel was evacuated and flushed with nitrogen three times, then stirred under an atmosphere of hydrogen for 16 h, filtered, and concentrated under reduced pressure to yield a yellow oil, which was purified by flash chromatography (silica gel, CH2Cl2 /methanol, 9:1), affording 210 mg (57%) of the desired product as a dark yellow oil (Rf 0.50, CH2Cl2 /MeOH, 9:1). Data for (R/S)-7-amino-4-ethyl-1,2,3,4-tetrahydroquinoline: 1H NMR (400 MHz, CDCl3) δ 6.81 (d, 1H, J=8.1, 5-H), 6.02 (dd, 1H, J=8.0, 2.2, 6-H), 5.84 (d, 1H, J=2.3, 8-H), 3.48 (s, 2H, NH2), 3.27 (ddd, 1H, J=11.1, 11.1, 3.5, 2-H), 3.20 (ddd, 1H, J=9.8, 5.3, 4.5, 2-H), 2.55 (dddd, 1H, J=10.2, 5.2, 5.2, 5.2, 4H), 1.90 (dddd, 1H, J=9.6, 9.6, 9.6, 4.7, 3-H), 1.72 (m, 2H, 3-H, CH2CH3), 1.48 (m, 1H, CH2CH3), 0.96 (t, 3H, J=7.4, CH3).

Workup

  1. temperatureThe resulting solution was warmed to rt
  2. temperaturecooled again to -10° C.
  3. additionthe reaction mixture was poured
  4. extractionThis aqueous phase was extracted with EtOAc (3×75 mL)
  5. dry with materialthe combined extracts were dried (Na2SO4)
  6. concentrationconcentrated under reduced pressure
  7. customto yield a dark red oil
  8. customThe vessel was evacuated
  9. customflushed with nitrogen three times
  10. stirringstirred under an atmosphere of hydrogen for 16 h
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure
  13. customto yield a yellow oil, which
  14. customwas purified by flash chromatography (silica gel, CH2Cl2 /methanol, 9:1)

Sources & evidence

ORD record
ord-f411e11c775046ab8f623bb0692fa393
Source dataset
uspto-grants-2000_01
Patent number
US06017924

Reaction notes

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