PAPER
Copper(II) Bromide Catalyzed Novel Preparation of Propargylic Ethers and Sulfides
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Anal. Calcd for C16H20O: C, 84.16; H, 8.83. Found: C, 84.21; H,
8.97.
13C NMR (75 MHz, CDCl3): d = 25.5, 25.6, 26.1, 26.3, 35.7, 39.9,
42.8, 44.8, 84.2, 92.4, 123.6, 127.8, 128.2, 131.5.
EI-MS: m/z = 298 [M+], 230, 215, 183, 155, 141, 128, 115, 91, 77.
1-[1-(2-Chloroethoxy)cyclohexyl]-2-phenylethyne (3q)
Pale yellow oil; yield: 82%.
Anal. Calcd for C20H26S: C, 80.48; H, 8.78. Found: C, 80.56; H,
8.69.
IR (KBr): 3080, 3058, 3028, 2936, 2858, 2741, 2669, 2221, 1590,
1449 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.58–2.04 (m, 10 H), 3.68 (t,
J = 6.2 Hz, 2 H), 3.92 (t, J = 6.2 Hz, 2 H), 7.28–7.46 (m, 5 H).
13C NMR (75 MHz, CDCl3): d = 22.8, 25.4, 37.2, 43.4, 63.8, 74.4,
86.2, 90.1, 122.8, 128.2, 128.2, 131.6.
Acknowledgment
The authors thank State Key Laboratory of Applied Organic Che-
mistry for financed support.
EI-MS: m/z = 262 [M+], 219, 182, 157, 141, 129, 115, 102, 91, 77.
References
Anal. Calcd for C16H19ClO: C, 73.13; H, 7.29. Found: C, 73.21; H,
7.46.
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1-[1-(Benzyloxy)cyclohexyl]-2-phenylethyne (3r)
Brown oil; yield: 75%.
IR (KBr): 3084, 3062, 3031, 2935, 2857, 2736, 2668, 2607, 2220,
1722, 1599, 1491, 1448 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.54–2.07 (m, 10 H), 4.73 (s, 2 H),
7.22–7.45 (m, 10 H).
13C NMR (75 MHz, CDCl3): d = 22.9, 25.5, 37.4, 65.6, 74.5, 86.2,
90.8, 123.0, 127.2, 127.7, 128.1, 128.2, 128.2, 131.7, 139.4.
EI-MS: m/z = 290 [M+], 247, 233, 205, 192, 141, 129, 91, 77.
Anal. Calcd for C21H22O: C, 86.85; H, 7.64. Found: C, 86.97; H,
7.55.
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Tetrahedron 2002, 58, 9847. (g) Kondo, T.; Kanda, Y.;
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Uemura, S. J. Am. Chem. Soc. 2002, 124, 11846.
1-(1-Isopropoxycyclohexyl)-2-phenylethyne (3s)
Pale yellow oil; yield: 53%.
IR (KBr): 3080, 3059, 3028, 2970, 2934, 2857, 2711, 2668, 2615,
2203, 1727, 1598, 1490, 1446 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.23 (d, J = 6.6 Hz, 6 H), 1.55–
2.03 (m, 10 H), 4.19 (m, 1 H), 7.28–7.44 (m, 5 H).
13C NMR (75 MHz, CDCl3): d = 23.2, 24.6, 25.5, 38.4, 66.3, 74.1,
85.2, 91.7, 123.3, 127.9, 128.2, 131.5.
EI-MS: m/z = 242 [M+], 227, 199, 184, 171, 157, 129, 115, 102, 91,
77.
Anal. Calcd for C17H22O: C, 84.25; H, 9.15. Found: C, 84.47; H,
9.23.
1-[1-(Ethylsulfanyl)cyclohexyl)-2-phenylethyne (3t)
(d) Nishibayashi, Y.; Yoshikawa, M.; Inada, Y.; Milton, M.
D.; Hidai, M.; Uemura, S. Angew. Chem. Int. Ed. 2003, 42,
2681. (e) Milton, M. D.; Inada, Y.; Nishibayashi, Y.;
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Pale yellow oil; yield: 86%.
IR (KBr): 3078, 3056, 3027, 2931, 2854, 2666, 2219, 1597, 1490,
1445 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.31 (t, J = 7.5 Hz, 3 H), 1.60–2.13
(m, 10 H), 2.81 (q, J = 7.5 Hz, 2 H), 2.27–7.44 (m, 5 H).
13C NMR (75 MHz, CDCl3): d = 15.9, 23.0, 25.5, 37.4, 58.4, 73.8,
85.7, 91.0, 123.1, 128.0, 128.2, 131.6.
EI-MS: m/z = 245 [M+ + 1], 244 [M+], 215, 183, 155, 141, 115, 105,
91, 77.
Anal. Calcd for C16H20S: C, 78.63; H, 8.25. Found: C, 78.76; H,
8.19.
1-[1-(Cyclohexylsulfanyl)cyclohexyl]-2-phenylethyne (3u)
Pale yellow oil; yield: 38%.
IR (KBr): 3459, 2930, 2852, 2224, 1637, 1490, 1445, 912 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.25–2.16 (m, 20 H), 3.05–3.12
(m, 1 H), 7.25–7.43 (m, 5 H).
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Synthesis 2008, No. 2, 191–196 © Thieme Stuttgart · New York