Nitric Acid → HCID 10631124, 화합물

HRID 1938431노트

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HRID 1938431 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 cone. 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 3.0M 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, CH2 Cl2 /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) 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. 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, CH2 Cl2 /methanol, 9:1)

출처 및 근거

ORD 기록
ord-25244e0de0944209872c7ee5e3578c0a
출처 데이터셋
uspto-grants-1997_12
특허 번호
US05693646

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