The Journal of Organic Chemistry
Note
1-Benzyl-4-phenyl-1H-1,2,3-triazole17 (3ai). Yellowish green
needles (97%): mp = 42 °C; H NMR (300 MHz, CDCl3) δ 7.35−
(d, J = 10.2 Hz, 2H), 7.63 (s, 1H), 7.26 (t, J = 6.9 Hz, 2H), 7.19−7.14
(m, 1H), 5.95−5.82 (m, 1H), 5.20 (d, J = 9.0 Hz, 2H), 5.14 (s, 1H),
4.84 (d, J = 6.0 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 147.6, 131.0,
130.3, 128.5, 128.4, 127.8, 126.9, 125.4, 119.8, 119.4, 52.6.
1
7.31 (m, 3H), 7.25−7.21 (m, 2H), 7.17 (s, 1H), 5.47 (s, 2H), 2.67 (t, J
= 7.5 Hz, 2H), 1.63−1.57 (m, 2H), 1.33−1.28 (m, 4H), 0.87 (t, J = 6.9
Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 148.6, 134.7, 128.6, 128.2,
127.5, 120.4, 53.7, 31.2, 28.9, 25.5, 22.2, 13.9.
1,5-Diallyl-4-phenyl-1H-1,2,3-triazole23 (5h′a). Yellow liquid
1
(12%): H NMR (300 MHz, CDCl3) 7.61−7.56 (m, 2H), 7.37−7.32
1-Benzyl-4-hexyl-1H-1,2,3-triazole17 (3aj). Yellowish green
(m, 2H), 7.29−7.26 (m, 1H), 5.98−5.81 (m, 1H), 5.23−5.03 (m, 3H),
4.92−4.86 (m, 2H), 3.52−3.49 (m, 2H); 13C NMR (75 MHz, CDCl3)
δ 145.6, 132.4, 131.6, 131.2, 130.1, 128.6, 127.7, 127.0, 118.6, 117.7,
50.7, 27.0.
1
needles (99%): mp = 55−56 °C; H NMR (300 MHz, CDCl3) δ
7.33−7.24 (m, 3H), 7.21−7.17 (m, 3H), 5.44 (s, 2H), 2.65 (t, J = 7.8
Hz, 2H), 1.63−1.56 (m, 2H), 1.33−1.26 (m, 6H), 0.84 (t, J = 6.6 Hz,
3H); 13C NMR (75 MHz, CDCl3) δ 148.8, 134.8, 128.5, 128.3, 127.7,
120.4, 53.8, 31.5, 29.3, 28.8, 25.7, 22.5, 14.0.
ASSOCIATED CONTENT
■
1-Phenethyl-4-phenyl-1H-1,2,3-triazole18 (4ba). White amor-
phous solid (98%): mp = 140 °C; 1H NMR (300 MHz, CDCl3) δ 7.74
(d, J = 7.2 Hz, 2H), 7.44 (s, 1H), 7.40−7.35 (m, 2H), 7.31−7.23 (m,
4H), 7.11 (d, J = 6.2 Hz, 2H), 4.61 (t, J = 7.5 Hz, 2H), 3.23 (t, J = 7.2
Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 147.3, 136. 9, 130.5, 128.7,
128.7, 128.6, 127.9, 127.0, 125.5, 119.8, 51.7, 36.8.
S
* Supporting Information
1H and 13C spectra for all compounds. This material is available
AUTHOR INFORMATION
Corresponding Author
■
1-(1-Phenethyl-1H-1,2,3-triazol-4-yl)cyclohexanol (4bf).
1
Ivory needles (95%): mp = 109 °C; H NMR (300 MHz, CDCl3) δ
7.29−7.04 (m, 6H), 4.55 (t, J = 7.2 Hz, 2H), 3.19 (t, J = 7.2 Hz, 2H),
2.46 (brs, OH), 1.93−1.70 (m, 6H), 1.59−1.32 (m, 4H) ; 13C NMR
(75 MHz, CDCl3) δ 144.6, 136.9, 128.6, 128.6, 126.9, 120.0, 69.5,
51.7, 38.2, 36.9, 25.4, 22.1; IR (KBr, cm−1) 3315, 3138, 3038, 2950,
2929, 2855, 1500, 1456, 1405, 1336, 1263, 1211, 1182, 1164, 1152,
1132, 1079, 1065, 1049, 1032, 995, 975, 907, 850, 816, 755, 735, 701,
670; HRMS calcd for C16H21N3O 271.1685, found 271.1643.
Notes
The authors declare no competing financial interest.
REFERENCES
■
(1) (a) Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B.
Angew. Chem., Int. Ed. 2002, 41, 2596−2599. (b) Tornøe, C. W.;
Christensen, C.; Meldal, M. J. Org. Chem. 2002, 67, 3057−3064.
(c) Speer, A. E.; Adam, G. C.; Cravatt, B. F. J. Am. Chem. Soc. 2003,
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12809−12818.
4-Hexyl-1-phenethyl-1H-1,2,3-triazole19 (4bj). White amor-
1
phous solid (92%): mp = 40 °C; H NMR (300 M Hz, CDCl3) δ
7.21−7.12 (m, 3H), 6.984 (d, J = 6.6 Hz, 2H), 6.90 (s, 1H), 4.44 (t, J
= 6.9 Hz, 2H), 3.09 (t, J = 6.9 Hz, 2H), 2.57 (t, J = 7.8 Hz, 2H), 1.53−
1.49 (m, 2H), 1.20−1.19 (m, 6H), 0.81−0.77 (m, 3H) ; 13C NMR (75
MHz, CDCl3) δ 147.9, 137.0, 128.5, 128.5, 126.8, 120.8, 51.4, 36.8,
31.5, 29.4, 28.8, 25.6, 22.6, 14.1.
(2) (a) Wu, P.; Feldman, A. K.; Nugent, A. K.; Hawker, C. J.; Scheel,
4-Phenyl-1-(3-phenylpropyl)-1H-1,2,3-triazole20 (4ca). Ivory
A.; Voit, B.; Pyun, J.; Frec
Angew. Chem., Int. Ed. 2004, 43, 3928−3932. (b) Helms, B.; Mynar, J.;
Hawker, C. J.; Frec
́
het, J. M. J.; Sharpless, K. B.; Fokin, V. V.
1
needles (93%): mp = 81−82 °C; H NMR (300 MHz, CDCl3), 7.81
́
het, J. M. J. J. Am. Chem. Soc. 2004, 126, 15020−
(d, J = 7.8 Hz, 2H), 7.69 (s, 1H), 7.41 (t, J = 7.2 Hz, 2H), 7.31−7.26
(m, 3H), 7.22−7.16 (m, 3H), 4.39 (t, J = 6.9 Hz, 2H), 2.69 (t, J = 7.8
Hz, 2H), 2.30 (quintet, J = 7.2 Hz, 2H); 13C NMR (75 MHz, CDCl3)
δ 147.5, 139.9, 130.4, 128.7, 128.4, 128.3, 128.0, 126.2, 125.5, 119.4,
49.5, 32.5, 31.7.
15021. (c) Rodionov, V.; Fokin, V. V.; Finn, M. G. Angew. Chem., Int.
Ed. 2005, 44, 2210−2215.
̈
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(3) (a) Ozcubukcu, S.; Ozkal, E.; Jimeno, C.; Pericas, M. A. Org. Lett.
2009, 11 (20), 4680−4683. (b) Shao, C.; Cheng, G.; Su, D.; Xu, J.;
Wang, X.; Hu, Y. Adv. Synth. Catal. 2010, 352, 1587−1592. (c) Liu,
M.; Reiser, O. Org. Lett. 2011, 13 (5), 1102−1105. (d) Buckley, B. R.;
Dann, S. E.; Heaney, H.; Stubbs, E. C. Eur. J. Org. Chem. 2011, 770−
776. (e) Liu, Q.; Ji, Y. Green Chem. 2011, 13, 562−565.
1-(Naphthalene-6-yl)-2-(4-phenyl-1H-1,2,3-triazol-1-yl)-
ethanone21 (4da). Ivory needles (95%): mp = 183−185 °C; H
1
NMR (300 MHz, CDCl3), 8.56 (s, 1H), 8.02−7.85 (m, 7H), 7.66−
7.60 (m, 2H), 7.43 (t, J = 7.2 Hz, 2H), 7.33 (t, J = 7.2 Hz, 1H), 6.03
(s, 2H); 13C NMR (75 MHz, CDCl3) δ 190.0, 148.1, 136.0, 132.2,
131.1, 130.4, 130.2, 129.7, 129.3, 129.2, 128.7, 128.1, 127.9, 127.3,
125.7, 123.2, 121.4, 55.5.
(4) (a) Loftsson, T.; Brewester, M. E. J. Pharm. Sci. 1996, 85, 1017−
1025. (b) Loftsson, T.; Jarho, P.; Masson, Mar; Jarvinen, Tomi Expert
́ ́
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Opin. Drug Delivery 2005, 2 (2), 1−17. (c) Challa, R.; Ahuja, A.; Ali, J.;
Khar, R. K. AAPS PharmSciTech 2005, 6 (2), E329−E357.
(5) Rajewski, R. A.; Stella, V. J. J. Pharm. Sci. 1996, 85 (11), 1142−
1169.
(6) (a) Takahashi, K. Chem. Rev. 1998, 98, 2013−2033. (b) Kalck, P.;
Miquel, L.; Dessoudeix, M. Catal. Today 1998, 42, 431−440.
(c) Bhosale, S. V.; Bhosale, S. V. Mini-Rev. Org. Chem. 2007, 4,
231−242.
(7) To know the role of cyclodextrin as a ligand of catalyst, we added
cyclodextrin to the aq solution (D2O, pH ∼5) of Cu(I) catalytic
system and then monitored the protons of cyclodextrin by NMR. We
could not find any conspicuous change of protons of cyclodextrin in
this system. When reacted in the presence of cyclodextrin without
Cu(I) catalyst, no reaction occurred at room temperature. So
cyclodextrin seems to work only as a phase transfer catalyst. But, at
this time, because click reaction takes place in the cavity of
cyclodextrin, the interaction between cyclodextrin and copper catalyst
in click reaction cannot be excluded completely.
2-(4-Hexyl-1H-1,2,3-triazol-1-yl)-1-(naphthalene-6-yl)-
ethanone (4dj). Pale yellow needles (96%): mp = 110 °C; 1H NMR
(300 MHz, CDCl3), 8.51 (s, 1H), 7.99−7.87 (m, 2H), 7.82−7.78 (m,
2H), 7.68−7.53 (m, 2H), 7.47 (s, 1H), 5.93 (s, 2H), 2.77 (t, J = 7.5
Hz, 2H), 1.71 (quintet, J = 6.9 Hz, 2H), 1.35−1.29 (m, 6H), 0.88 (t, J
= 6.3 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 190.3, 148.7, 135.9,
132.2, 131.2, 130.1, 129.6, 129.2, 129.0, 127.8, 127.2, 123.1, 122.3,
55.4, 31.6, 29.4, 29.0, 25.8, 22.6, 14.2; IR (KBr, cm−1) 3120, 3061,
2951, 2932, 2858, 1695, 1625, 1595, 1470, 1436, 1363, 1340, 1271,
1261, 1217, 1178, 1128, 1067, 1030, 861, 819, 759, 746; HRMS calcd
for C20H23N3O 321.1841, found 321.1873.
Methyl-4-((4-phenyl-1H-1,2,3-triazol-1-yl)methyl)benzoate
(5ga). White needles (92%): mp = 167−169 °C; 1H NMR (300 MHz,
CDCl3) 8.02 (d, J = 9.0 Hz, 2H), 7.78 (d, J = 6.6 Hz, 2H), 7.67 (s,
1H), 7.41−7.31 (m, 5H), 5.63 (s, 2H), 3.91 (s, 3H); 13C NMR (75
MHz, CDCl3) δ 160.9, 148.4, 139.4, 130.5, 130.3, 130.0, 128.7, 128.2,
127.8, 127.7, 125.6, 119.5, 53.8, 52.3; IR (KBr, cm−1) 3109, 3083,
3058, 2953, 1714, 1614, 1485, 1465, 1442, 1418, 1357, 1317, 1281,
1224, 1195, 1114, 1078, 1049, 1021, 839, 801, 771, 746, 713, 696;
HRMS calcd for C17H15N3O2 293.1164, found 293.1173.
(8) The cost of 25 g of β-cyclodextrin is $56.2 from Sigma-Aldrich,
whereas 1 g of α-cyclodextrin costs $24.5, and 1 g of γ-cyclodextrin
costs $257.
(9) (a) Uekama, K.; Fujinaga, T.; Hirayama, F.; Otagiri, M.; Yamasali,
M.; Seo, H.; Hasimoto, T.; Tsuruoka, M. J. Pharm. Sci. 1983, 72 (11),
1-Allyl-4-phenyl-1H-1,2,3-triazole22 (5ha). White needles
1
(79%): mp = 56−58 °C; H NMR (300 MHz, CDCl3) 7.69−7.65
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dx.doi.org/10.1021/jo3000095 | J. Org. Chem. 2012, 77, 4117−4122