Acetic Acid → benzyl 4-[3,4-dihydro-1(2H)-quinolinylimino]-1-azepanecarboxylate

HRID 1813903Notes

Reaction equation

HRID 1813903 reaction equation
[N:1]1([NH2:11])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH2:4][CH2:3][CH2:2]1.O=[C:13]1[CH2:19][CH2:18][CH2:17][N:16]([C:20]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)=[O:21])[CH2:15][CH2:14]1.C(O)(=O)C>C(O)C>[N:1]1([N:11]=[C:13]2[CH2:19][CH2:18][CH2:17][N:16]([C:20]([O:22][CH2:23][C:24]3[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=3)=[O:21])[CH2:15][CH2:14]2)[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH2:4][CH2:3][CH2:2]1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 1512681Benzyl 4-oxoazepane-1-carboxylateHCID 64233141,2,3,4-Tetrahydroquinolin-1-amine

Product 1

HCID 72777072benzyl 4-[3,4-dihydro-1(2H)-quinolinylimino]-1-azepanecarboxylateYield 99.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution of 3,4-dihydro-1(2H)-quinolinylamine (2.97 g, 20.1 mmol), benzyl 4-oxo-1-azepanecarboxylate (4.96 g, 20.1 mmol), and glacial acetic acid (0.2 ml) in ethanol (200 ml) was allowed to reflux for 2.5 hours. The reaction was then cooled and evaporated in vacuo. The hydrazone product was purified by flash chromatography (90 g SiO2, 1% MeOH/CH2Cl2) providing benzyl 4-[3,4-dihydro-1(2H)-quinolinylimino]-1-azepanecarboxylate (7.55 g) as an oil. To a solution of benzyl 4-[3,4-dihydro-1(2H)-quinolinylimino]-1-azepanecarboxylate (6.79 g, 17.99 mmol) in ethanol (200 ml) was added trifluoroacetic acid (6.22 g, 53.96 mmol). The reaction was heated and allowed to stir at reflux for 2.5 hours, at which time it was cooled to rt., evaporated, and extracted into dichloromethane. This extract was washed with water, brine, dried with anhydrous sodium sulfate, and evaporated under reduced pressure. Crystallization from ethyl acetate/hexanes provided 2.93 g of the title compound (mp 131-133° C.). 1H NMR (CDCl3) δ 7.38, 7.29, 7.00, 6.86, 5.19, 3.98, 3.78, 2.97, 2.24; IR (drift) 2947, 1699, 1473, 1420, 1358, 1260, 1250, 1235, 1216, 1101, 997, 764, 757, 746, 703 cm−1.

Workup

  1. temperatureto reflux for 2.5 hours
  2. temperatureThe reaction was then cooled
  3. customevaporated in vacuo
  4. customThe hydrazone product was purified by flash chromatography (90 g SiO2, 1% MeOH/CH2Cl2)

Sources & evidence

ORD record
ord-2090db9c14be4c9b841f6dff6d7eb7fa
Source dataset
uspto-grants-2005_04
Patent number
US06875762B2

Reaction notes

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