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Formation of 4-tert-Butyl-1,2,3,4-tetrahydroquinoline from One-pot Reactions of Quinoline/organoaluminum Complex with tert-Butyllithium
Formation of 4-tert-Butyl-1,2,3,4-tetrahydroquinoline from One-pot Reactions of Quinoline/organoaluminum Complex with tert-Butyllithium
Journal of the Korean Chemical Society. 2015. Dec, 59(6): 533-536
Copyright © 2015, Korean Chemical Society
  • Received : September 03, 2015
  • Accepted : September 24, 2015
  • Published : December 20, 2015
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Hye Jin Jeong
Sung Keon Namgoong

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EXPERIMENTAL
- Materials
All the organometallic and organoaluminum reagents used in this work, except Al( t -Bu) 3 , were purchased from Aldrich. THF solvent was freshly distilled and used.
- General Procedure
The solution of AlX 3 (1.0 mmol) was added to the solution of quinoline (1.0 mmol) in THF (2 mL) at 0 ºC under nitrogen atmosphere. The reaction mixture was stirred for 1 h at room temperature. The resulting mixture was then cooled to -78 ºC and the organometallic reagent (1.1 mmol) was added dropwise to the reaction mixture. After THF solution was stirred for another 12 h at -78 ºC, the reaction was then quenched with water (2 mL) at -78 ºC. The resulting mixture was stirred for additional 4 h at room temperature. THF was evaporated under reduced pressure and CH 2 Cl 2 (2 mL) was added to the resulting mixture. The organic layer was separated and dried over MgSO 4 . The dichloromethane solution was filtered and evaporated. The crude reaction mixture was purified column chromatography (ethyl acetate:hexane, 1:20) to give the homologated product as a either colorless oil or white solid.
- 2-t-Butylquinoline 110
Colorless oil; 1 H NMR (300 MHz, CDCl 3 ): δ 1.5 (s, 9H, (CH 3 ) 3 ),7.5 (m, 2H, Ar-H), 7.7 (m, 1H, Ar-H), 7.8 (d, J = 8.4 Hz, 1H, Ar-H), 8.1 (m, 2H, Ar-H); 13 C NMR (75 MHz, CDCl 3 ): δ 30.1, 38.1, 118.2, 125.6, 126.4, 127.2, 129.0, 129.4, 135.9, 147.4, 169.2 ppm.
- 4-t-Butyl-1,2,3,4-tetrahydroquinoline 213
Colorless oil; 1 H NMR (300 MHz, CDCl 3 ): δ 0.98 (s, 9H (CH 3 ) 3 ), 1.8 (m, 1H, H-3), 2.2 (m, 1H, H-3′), 2.5 (dd, J = 2.4 and 5.4 Hz, 1H, H-4), 3.4 (m, 2H, H-2), 3.8 (s, 1H, NH), 6.5 (d, J = 7.8 Hz, 1H, Ar-H), 6.6, (m, 1H, Ar-H), 7.0 (m, 2H, Ar-H); 13 C NMR (75 MHz, CDCl 3 ): δ 23.6, 29.1, 35.0, 39.4, 45.3, 113.4, 115.1, 122.4, 127.0, 131.2, 144.8 ppm; m/z (EI): 189 (M + , 20%), 132 ((M- t -Bu) + , 100%).
- 2-(4-Methoxyphenyl)quinoline 315
White solid; mp: 122-123 °C (lit 15 : 122-124 °C); 1 H NMR (300 MHz, CDCl 3 ): δ 3.9 (s, 3H, OMe), 7.1 (m, 2H, Ar-H), 7.5 (m, 1H, Ar-H), 7.7 (m, 1H, Ar-H), 7.8 (m, 2H, Ar-H), 8.2 (m, 4H, Ar-H); 13 C NMR (75 MHz, CDCl 3 ): δ 55.4, 114.2, 118.6, 125.9, 126.9, 127.4, 128.9, 129.5, 132.3, 136.6, 148.3, 156.9, 160.8 ppm.
Acknowledgements
This work was supported by a research grant from Institute of Natural Science of Seoul Women’s University (2014).
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