Nitric Acid → HCID 10631124、化合物

温度

-10 °C

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).

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)

ORDレコード

ord-f411e11c775046ab8f623bb0692fa393

出典データセット

uspto-grants-2000_01

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US06017924