Nitric Acid → HCID 10631124, compound

HRID 1861745Notes

Reaction equation

HRID 1861745 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) δ6.81 (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. concentrationconcentrated under reduced pressure
  6. customto yield a dark red oil
  7. customThe vessel was evacuated
  8. customflushed with nitrogen three times
  9. stirringstirred under an atmosphere of hydrogen for 16 h
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customto yield a yellow oil, which
  13. customwas purified by flash chromatography (silica gel, CH2Cl2/methanol, 9:1)

Sources & evidence

ORD record
ord-63db38c210584f11b3b8e640ffc3df4d
Source dataset
uspto-grants-2003_03
Patent number
US06534516B1

Reaction notes

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