July 2014
Synthesis of Tetrahydroquinolines Mediated by Redox of SnCl2/FeCl3
1105
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EXPERIMENTAL
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Unless noted otherwise, all starting materials were obtained from
commercial supplies and used without further purification. The
reaction was monitored by GC analysis. Mass spectra were
determined on an Apex IV FT-ICR mass spectrometer (Bruker
Company, Madison, WI). 1H-NMR spectra were recorded at JEOL
JNM-ECA 600 in CDCl3 using TMS as internal standard. 13C-NMR
spectra were recorded at 150 MHz using CDCl3 as an internal standard.
Column chromatography was performed on silica gel (300–400 mesh);
gradients of petroleum ether and Et2O were used as eluent.
General procedure: synthesis of 4-methyl-4-neopentyl-2-p-
ropyltetrahydroquinoline (1). SnCl2 (0.3694 g, 1.9483 mmol)
was added to a dried Schlenk tube with a Teflon-coated magnetic
stir bar under N2 atmosphere, and then CH2ClCH2Cl (12.7 mL)
was added as a solvent. FeCl3 (0.6320g, 2.0×1.9483 mmol) was
added with stirring. This reaction was stirred at 0°C for 1 h. The
color of this solution turned to aqua. Then, n-butyraldehyde
(0.176 mL, 1.9483 mmol), aniline (0.178 mL, 1.9483mmol), and
diisobutylene (0.304 mL, 1.9483 mmol) were added sequentially to
the solution at room temperature. The color turned to white from
deep red during this process. Dodecane was added as an internal
standard. The reaction was stirred at room temperature and
monitored by GC analysis until the reaction was finished, and then
it was quenched with 3 M ammonia aqueous solution and
extracted with Et2O (30 mL × 3). The combined organic layers
were washed with H2O and brine in sequential order, then dried
over anhydrous Na2SO4, filtered, and concentrated in vacuo. The
residue was purified by silica gel chromatography using (Et2O:
petroleum ether = 1:20) as eluent to give the product as a mixture
of cis and trans isomers of 4-methyl-4-neopentyl-2-propyl
tetrahydroquinoline 1.
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The other compounds were prepared similarly.
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet