8-Chloro-3-methylquinoline
(c) V. V. Kouznetsov, L. Y. V. Me´ndez and C. M. M. Go´mez, Curr. Org.
Chem., 2005, 9, 141–161.
9 (a) J. Barluenga, F. Rodr´ıguez and F. J. Fan˜ana´s, Chem.–Asian J., 2009,
4, 1036–1048; (b) S. Madapa, Z. Tusi and S. Batra, Curr. Org. Chem.,
2008, 12, 1116–1183.
◦
1
Rf 0.80 (toluene–EtOAc, 1 : 1). bp 134–137 C/1.5 mmHg. H
NMR (300 MHz, CDCl3): d 8.81 (d, J = 2.2 Hz, 1H), 7.85 (dd,
J = 1.0, 2.1 Hz, 1H), 7.69 (dd, J = 1.3, 7.5 Hz, 1H), 7.59 (dd,
J = 1.3, 8.2 Hz, 1H), 7.35 (dd, J = 7.5, 8.1 Hz, 1H), 2.47 (d, J =
0.8 Hz, 3H). 13C NMR (75 MHz, CDCl3): d 152.9, 142.7, 135.1,
133.2, 131.6, 129.5, 128.6, 126.5, 126.4, 18.6. HRMS: calcd for
C10H9ClN: 178.0418 [M+H]+, found: 178.0425.
10 For recent reviews on transition metal-catalysed dehydrogenation
reactions with alcohols and amines, see: (a) R. Yamaguchi, K.-i. Fujita
and M. Zhu, Heterocycles, 2010, 81, 1093–1140; (b) G. E. Dobereiner
and R. H. Crabtree, Chem. Rev., 2010, 110, 681–703; (c) T. D. Nixon,
M. K. Whittlesey and J. M. J. Williams, Dalton Trans., 2009, 753–762.
11 (a) C. S. Cho, W. X. Ren and N. S. Yoon, J. Mol. Catal. A: Chem., 2009,
299, 117–120; (b) H. V. Mierde, P. Van, Der Voort, D. De, Vos and F.
Verpoort, Eur. J. Org. Chem., 2008, 1625–1631; (c) C. S. Cho and W. X.
Ren, J. Organomet. Chem., 2007, 692, 4182–4186; (d) R. Mart´ınez, D. J.
Ramo´n and M. Yus, Eur. J. Org. Chem., 2007, 1599–1605; (e) C. S. Cho,
H. J. Seok and S. C. Shim, J. Heterocycl. Chem., 2005, 42, 1219–1222;
(f) K. Taguchi, S. Sakaguchi and Y. Ishii, Tetrahedron Lett., 2005, 46,
4539–4542; (g) K. Motokura, T. Mizugaki, K. Ebitani and K. Kaneda,
Tetrahedron Lett., 2004, 45, 6029–6032; (h) C. S. Cho, B. T. Kim, H.-J.
Choi, T.-J. Kim and S. C. Shim, Tetrahedron, 2003, 59, 7997–8002.
12 (a) C. S. Cho, D. T. Kim, T.-J. Kim and S. C. Shim, Bull. Korean Chem.
Soc., 2003, 24, 1026–1028; (b) C. S. Cho, B. H. Oh and S. C. Shim, J.
Heterocycl. Chem., 1999, 36, 1175–1178.
7,8-Benzo-3-methylquinoline
Rf 0.67 (toluene–EtOAc, 85 : 15). mp 87–88 ◦C. bp 155–165 ◦C/4
mmHg. 1H NMR (300 MHz, CDCl3): d 9.25 (dd, J = 1.4, 8.0 Hz,
1H), 8.85 (d, J = 2.1 Hz, 1H), 7.96 (dd, J = 0.9, 2.0 Hz, 1H), 7.92–
7.88 (m, 1H), 7.79 (d, J = 8.8 Hz, 1H), 7.76–7.66 (m, 2H), 7.63 (d,
J = 8.9 Hz, 1H), 2.57 (s, 3H). 13C NMR (75 MHz, CDCl3): d 150.4,
144.6, 135.3, 133.3, 131.6, 131.4, 127.9, 127.8, 127.8, 127.1, 126.3,
125.2, 124.2, 18.8. HRMS: calcd for C14H12N: 194.0965 [M+H]+,
found: 194.0958.
13 For a similar reaction between aniline and trialkylamines, see: C. S.
Cho, B. H. Oh, J. S. Kim, T.-J. Kim and S. C. Shim, Chem. Commun.,
2000, 1885–1886.
14 Y. Tsuji, K.-T. Huh and Y. Watanabe, J. Org. Chem., 1987, 52, 1673–
5,6-Benzo-3-methylquinoline
1680.
Rf 0.56 (toluene–EtOAc, 1 : 1). mp 81–82 C (lit.39 81.5–82 ◦C
◦
15 H. Aramoto, Y. Obora and Y. Ishii, J. Org. Chem., 2009, 74, 628–633.
16 L. U. Nordstrøm and R. Madsen, Chem. Commun., 2007, 5034–5036.
17 T. Jensen and R. Madsen, J. Org. Chem., 2009, 74, 3990–3992.
18 M. Tursky, L. L. R. Lorentz-Petersen, L. B. Olsen and R. Madsen, Org.
Biomol. Chem., 2010, 8, 5575–5581.
19 Y. Shvo, D. Crarkie, Y. Rahamim and D. F. Chodosh, J. Am. Chem.
Soc., 1986, 108, 7400–7402.
20 K. N. Campbell and I. J. Schaffner, J. Am. Chem. Soc., 1945, 67, 86–89.
21 In addition, 4-hydroxy-3-methylbutan-2-one reacts with aniline and
sulfuric acid to produce 3,4-dimethylquinoline, see: R. H. F. Manske,
L. Marion and F. Leger, Can. J. Res., 1942, 20B, 133–152.
22 S. Ba¨hn, A. Tillack, S. Imm, K. Mevius, D. Michalik, D. Hollmann, L.
Neubert and M. Beller, ChemSusChem, 2009, 2, 551–557.
23 A special 3-hydroxyaldehyde (2-deoxyribose) was recently reacted with
aniline under acidic conditions to afford the quinoline skeleton after
elimination of water and Michael addition, see: J. S. Yadav, B. V. S.
Reddy, S. Meraj, P. Vishnumurthy, K. Narsimulu and A. C. Kunwar,
Synthesis, 2006, 2923–2926.
(heptane)). bp 152–158 ◦C/5 mmHg. 1H NMR (300 MHz,
CDCl3): d 8.82 (d, J = 2.1 Hz, 1H), 8.78–8.75 (m, 1H), 8.63 (d, J =
8.0 Hz, 1H), 8.03–7.89 (m, 3H), 7.74–7.60 (m, 2H), 2.63 (s, 3H).
13C NMR (75 MHz, CDCl3): d 151.3, 146.3, 132.0, 131.0, 130.4,
130.0, 129.6, 128.8, 128.1, 127.3, 127.0, 125.3, 122.7, 19.2. MS:
m/z 193 [M].
4-(Phenylamino)-2-butanone
Rf 0.32 (toluene–EtOAc, 85 : 15). 1H NMR (300 MHz, CDCl3): d
7.22–7.14 (m, 2H), 6.71 (dt, J = 1.1, 7.3 Hz, 1H), 6.64–6.58 (m,
2H), 3.42 (t, J = 6.1 Hz, 2H), 2.75 (t, J = 6.1 Hz, 2H), 2.16 (s, 3H).
13C NMR (75 MHz, CDCl3): d 208.2, 147.8, 129.4, 117.8, 113.2,
42.7, 38.5, 30.5. MS: m/z 163 [M]. NMR data are in accordance
with literature values.40
24 (a) S. E. Denmark and S. Venkatraman, J. Org. Chem., 2006, 71, 1668–
1676; (b) J. J. Eisch and T. Dluzniewski, J. Org. Chem., 1989, 54, 1269–
1274.
25 T. Nagamine, A. Januszko, P. Kaszynski, K. Ohta and Y. Endo, J.
Mater. Chem., 2006, 16, 3836–3843.
Notes and references
26 C. von Rechenberg, Einfache und fraktionierte Destillation in Theorie
und Praxis, Staackmann, Leipzig, 2nd edn, 1923, p. 299.
27 J. C. Lewis, R. G. Bergman and J. A. Ellman, J. Am. Chem. Soc., 2007,
129, 5332–5333.
1 (a) J. P. Michael, Nat. Prod. Rep., 2008, 25, 166–187; (b) J. P. Michael,
Nat. Prod. Rep., 2007, 24, 223–246.
2 K. Kaur, M. Jain, R. P. Reddy and R. Jain, Eur. J. Med. Chem., 2010,
45, 3245–3264.
3 (a) A. Lilienkampf, J. Mao, B. Wan, Y. Wang, S. G. Franzblau and A.
P. Kozikowski, J. Med. Chem., 2009, 52, 2109–2118; (b) M. V. N. de
Souza, K. C. Pais, C. R. Kaiser, M. A. Peralta, M. de L. Ferreira and
M. C. S. Lourenco, Bioorg. Med. Chem., 2009, 17, 1474–1480.
4 (a) V. J. Venditto and E. E. Simanek, Mol. Pharmaceutics, 2010, 7,
307–349; (b) J. Datta, K. Ghoshal, W. A. Denny, S. A. Gamage, D. G.
Brooke, P. Phiasivongsa, S. Redkar and S. T. Jacob, Cancer Res., 2009,
69, 4277–4285; (c) G. Gakhar, T. Ohira, A. Shi, D. H. Hua and T. A.
Nguyen, Drug Dev. Res., 2008, 69, 526–534.
5 S. Chen, R. Chen, M. He, R. Pang, Z. Tan and M. Yang, Bioorg. Med.
Chem., 2009, 17, 1948–1956.
6 K. Grossmann, Pest Manag. Sci., 2010, 66, 113–120.
7 (a) M. Malathi, P. S. Mohan, R. J. Butcher and C. K. Venil, Can. J.
Chem., 2009, 87, 1692–1703; (b) E. Kos´cien´, E. Gondek, M. Pokladko,
B. Jarosz, R. O. Vlokh and A. V. Kityk, Mater. Chem. Phys., 2009, 114,
860–867.
8 (a) J. Marco-Contelles, E. Pe´rez-Mayoral, A. Samadi, M. C. Carreiras
and E. Soriano, Chem. Rev., 2009, 109, 2652–2671; (b) S. A. Yamashkin
and E. A. Oreshkina, Chem. Heterocycl. Compd., 2006, 42, 701–718;
28 J.-A. Su, E. Siew, E. V. Brown and S. L. Smith, Org. Magn. Reson.,
1977, 10, 122–125.
29 I. Kondolff, H. Doucet and M. Santelli, Tetrahedron, 2004, 60, 3813–
3818.
30 J. v. Braun, A. Petzold and J. Seemann, Chem. Ber., 1922, 55, 3779–
3792.
31 F. Mongin, L. Mojovic, B. Guillamet, F. Tre´court and G. Que´guiner,
J. Org. Chem., 2002, 67, 8991–8994.
32 F. H. Case, S. Catino and F. Scholnick, J. Org. Chem., 1954, 19, 31–36.
33 W. P. Utermohlen, J. Org. Chem., 1943, 8, 544–549.
34 E. Maschmann, Chem. Ber., 1926, 59, 2825–2826.
35 K. N. Campbell, C. H. Helbing and J. F. Kerwin, J. Am. Chem. Soc.,
1946, 68, 1840–1843.
36 H. Y. Choi, E. S. Srisook, K. S. Jang and D. Y. Chi, J. Org. Chem., 2005,
70, 1222–1226.
37 C. Jutz and R. M. Wagner, Angew. Chem., 1972, 84, 299–302.
38 P. M. Draper and D. B. MacLean, Can. J. Chem., 1968, 46, 1487–1497.
39 N. S. Prostakov, V. G. Pleshakov, T. Kholdarova, V. P. Zvolinskii and
L. N. Plaksii, Chem. Heterocycl. Compd., 1972, 8, 1264–1267.
40 T. C. Wabnitz and J. B. Spencer, Org. Lett., 2003, 5, 2141–2144.
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