Nitric Acid → HCID 10631124, 화합물

HRID 850359노트

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HRID 850359 반응식
[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

참가 물질

10

반응물 6

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

생성물 1

HCID 10631124HCID 10631124, 화합물수율 57%

시약·촉매·용매 3

HCID 23938Palladium촉매HCID 962Water용매HCID 21584252Ethanol ethylacetate용매

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온도
-10 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-f411e11c775046ab8f623bb0692fa393
출처 데이터셋
uspto-grants-2000_01
특허 번호
US06017924

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