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A. R. Katritzky et al.
PAPER
13C NMR: = 3.7, 54.4, 55.5, 74.0, 83.8, 126.9, 127.2, 127.9, 128.2,
128.2, 128.8, 139.7.
References
(1) (a) For a review on recent methods of allylic amination, see:
Johannsen, M.; Jorgensen, K. A. Chem. Rev. 1998, 98,
1689. (b) Olofsson, K.; Larhed, M.; Hallberg, A. J. Org.
Chem. 2000, 65, 7235. (c) Olofsson, K.; Sahlin, H.; Larhed,
M.; Hallberg, A. J. Org. Chem. 2001, 66, 544.
(2) (a) Kondo, T.; Nakai, H.; Goto, T. Tetrahedron 1973, 29,
1801. (b) Kobayashi, K.; Miyazawa, S.; Terahara, A.;
Mishima, H.; Kurihara, H. Tetrahedron Lett. 1976, 537.
(c) Teng, C.-Y. P.; Ganem, B. Tetrahedron Lett. 1982, 23,
313. (d) Comins, D. L.; Green, G. M. Tetrahedron Lett.
1999, 40, 217.
(3) (a) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura,
H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301.
(b) Burgess, K.; Liu, L. T.; Pal, B. J. Org. Chem. 1993, 58,
4758.
(4) Trost, B. M.; Van Vranken, D. L. J. Am. Chem. Soc. 1993,
115, 444.
Anal. Calcd for C24H23N: C, 88.57; H, 7.12; N, 4.30. Found: C,
88.40; H, 7.60; N, 4.33.
4-(1-Phenyl-2-butynyl)morpholine (7b)
Obtained as a colorless liquid (3 h) (88%).
1H NMR: = 1.95 (d, J = 2.1 Hz, 3 H), 2.48 2.58 (m, 4 H), 3.66
3.76 (m, 4 H), 4.47 4.48 (br d, 1 H), 7.21 7.40 (m, 3 H), 7.50 7.60
(m, 2 H).
13C NMR: = 3.34, 49.6, 61.5, 66.9, 74.6, 83.5, 127.3, 127.8, 128.3,
138.2.
Anal. Calcd for C14H17NO: C, 78.10; H, 7.96; N, 6.51. Found: C,
78.37; H, 8.35; N, 6.53.
4-[1-(2-Naphthyl)-2-butynyl]morpholine (7c)
Obtained as a pale yellow liquid (30 min) (83%).
1H NMR: = 2.02 (d, J = 2.4 Hz, 3 H), 2.54 2.66 (m, 4 H), 3.66
3.78 (m, 4 H), 4.64 4.65 (br d, 1 H), 7.45 7.52 (m, 2 H), 7.70 (dd,
J = 8.4, 1.8 Hz, 1 H), 7.82 7.89 (m, 3 H), 8.02 (bs, 1 H).
13C NMR: = 3.6, 49.8, 61.7, 66.9, 74.6, 84.0, 125.8, 125.8, 126.4,
127.2, 127.4, 127.7, 127.9, 132.8, 132.9, 135.7.
(5) (a) Ahlbrecht, H.; Eichler, J. Synthesis 1974, 672. (b) Julia,
M.; Schouteeten, A.; Baillarge, M. Tetrahedron Lett. 1974,
3433. (c) Martin, S. F.; Dupriest, M. T. Tetrahedron Lett.
1977, 3925. (d) Werstiuk, N. H. Tetrahedron 1983, 39, 205.
(6) (a) Ahlbrecht, H. Chimia 1977, 31, 391. (b) Ahlbrecht, H.;
Dollinger, H. Synthesis 1985, 743.
Anal. Calcd for C18H19NO: C, 81.47; H, 7.22; N, 5.28. Found: C,
81.06; H, 7.37; N, 5.27.
(7) Trost, B. M.; Spagnol, M. D. J. Chem. Soc. Perkin. Trans. 1
1995, 2083.
(8) Cheikh, R. B.; Chaabouni, R.; Laurent, A.; Mison, P.; Nafti,
A. Synthesis 1983, 685.
4-[1-(4-Methylphenyl)-3-phenyl-2-propynyl]morpholine (7d)
Obtained as a colorless liquid (2 h) (87%).
(9) Torregrosa, J. L.; Baboulene, M.; Speziale, V.; Lattes, A.
Tetrahedron 1982, 38, 2355.
1H NMR: = 2.35 (s, 3 H), 2.61 2.65 (m, 4 H), 3.72 3.73 (m, 4 H),
4.74 (s, 1 H), 7.17(br d, J = 8.4 Hz, 2 H), 7.30 7.33 (m, 3 H), 7.50
7.52 (m, 4 H).
13C NMR: = 21.1, 9.8, 61.7, 65.8, 67.1, 85.2, 88.2, 122.9, 128.1,
128.2, 128.4, 128.5, 128.8, 131.7, 134.7, 137.4.
(10) Granitzer, W.; Stutz, A. Tetrahedron Lett. 1979, 3145.
(11) (a) Schweizer, E. E.; Smucker, L. D.; Votral, R. J. J. Org.
Chem. 1966, 31, 467. (b) Cavalla, D.; Warren, S.
Tetrahedron Lett. 1982, 23, 4505. (c) De Castro Dantas, T.
N.; Laval, J. P.; Lattes, A. Tetrahedron 1983, 39, 3337.
(12) (a) Germon, C.; Alexakis, A.; Normant, J. F. Tetrahedron
Lett. 1980, 21, 3763. (b) Germon, C.; Alexakis, A.;
Normant, J. F. Synthesis 1984, 40.
Anal. Calcd for C20H21NO: C, 82.44; H, 7.26; N, 4.81. Found: C,
82.29; H, 7.50; N, 4.81.
(13) (a) Bruylants, P. Bull. Soc. Chim. Belg. 1924, 33, 467.
(b) Bruylants, P. Bull. Soc. Chim. Belg. 1926, 35, 139.
(14) Agami, C.; Couty, F.; Evano, G. Org. Lett. 2000, 2, 2085.
(15) Katritzky, A. R.; Yao, J.; Denisko, O. V. J. Org. Chem.
2000, 65, 8063.
(16) (a) Katritzky, A. R. J. Heterocycl. Chem. 1999, 36, 1501.
(b) Katritzky, A. R.; Lan, X.; Yang, J. Z.; Denisko, O. V.
Chem. Rev. 1998, 98, 409.
4-(1-Isopropyl-3-phenyl-2-propynyl)piperidine (7e)
Obtained as a colorless liquid (2 h) (90%).
1H NMR: = 1.01 (d, J = 6.6 Hz, 3 H), 1.097 (d, J = 6.6 Hz, 3 H),
1.43 1.64 (m, 6 H), 1.87 1.95 (m, 1 H), 2.40 2.42 (m, 2 H), 2.61
2.65 (m, 2 H), 2.98 (d, J = 9.9 Hz, 1 H), 7.25 7.7.30 (m, 3 H),
7.42 7.46 (m, 2 H).
13C NMR: = 19.8, 20.6, 24.7, 26.2, 30.4, 50.8, 65.6, 85.9, 87.9,
123.8, 127.6, 128.2, 131.7.
(17) (a) Katritzky, A. R.; Yannakopoulou, K. Heterocycles 1989,
28, 1121. (b) Katritzky, A. R.; Gallos, J. K.;
HRMS–FAB): m/z [M+H]+ calcd for C17H24N, 242.1908; found,
Yannakopoulou, K. Synthesis 1989, 31. (c)Katritzky, A. R.;
Pilarski, B.; Urogdi, L. Org. Prep. Proced. Intl. 1989, 21,
135. (d) Katritzky, A. R.; Yang, Z.; Lam, J. N. Tetrahedron
1992, 48, 4971. (e) Katritzky, A. R.; Rachwal, S.; Rachwal,
B. J. Org. Chem. 1994, 59, 5206. (f) Katritzky, A. R.;
Abdel-Fattah, A. A. A.; Tymoshenko, D. O.; Belyakov, S.
A.; Griviriga, I.; Steel, P. J. J. Org. Chem. 1999, 64, 6071.
(18) (a) Katritzky, A. R.; Strah, S.; Belyakov, S. A. Tetrahedron
1998, 54, 7167. (b) Katritzky, A. R.; Rachwal, S.; Rachwal,
B. J. Chem. Soc., Perkin Trans. 1 1987, 805.
(19) Katritzky, A. R.; Yannakopoulou, K.; Lue, P.; Rasala, D.;
Urogdi, L. J. Chem. Soc., Perkin Trans. I 1989, 225.
(20) Katritzky, A. R.; Long, Q.-H.; Lue, P.; Jozwiak, A.
Tetrahedron 1990, 46, 8153.
(21) (a) Hu, N. X.; Aso, Y.; Otsubo, T.; Ogura, F. Tetrahedron
Lett. 1988, 29, 4949. (b) Rische, T.; Barfacker, L.;
Eilbracht, P. Eur. J. Org. Chem. 1999, 1653.
242.1895.
[1-(4-Morpholino)-1-(2-naphthyl)]methyl-1H-1,2,3-
benzotriazole (1c)
Benzotriazole (5g, 42 mmol) was taken together with morpholine
(3.66 mL, 42 mmol) in absolute EtOH (50 mL). The mixture was
stirred for 10 min at r.t. followed by the addition of 2-naphthalde-
hyde (6.5 g, 42 mmol). The reaction mixture was stirred at r.t. for an
additional 15 h and then it was concentrated under reduced pressure
to yield the benzotriazolylarylamine 1c in quantitative yield. The
product was sufficiently pure for the subsequent reaction with Grig-
nard reagent.
1H NMR: = 2.66 2.69 (m, 4 H), 3.78 3.81 (m, 4 H), 6.84 (s, 1 H),
7.36 7.58 (m, 6 H), 7.73 7.97 (m, 5 H).
13C NMR: = 50.1, 66.8, 83.1, 111.5, 120.0, 124.0, 124.7, 126.5,
126.7, 127.4, 127.6, 128.2, 128.7, 132.3, 133.0, 133.3, 146.1.
(22) Katritzky, A. R.; Rachwal, S. Pol. J. Chem. 1992, 66, 1653.
Synthesis 2002, No. 2, 199–202 ISSN 0039-7881 © Thieme Stuttgart · New York