The Journal of Organic Chemistry
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previously reported. The products which are not reported earlier were
2-Methoxy-6-(4-p-tolylbuta-1,3-diynyl)naphthalene (3hc,
Table 2): White solid (231 mg, 78%); mp 92−95 °C; IR (KBr)
3062, 3006, 2968, 1917, 1618, 1595, 1481, 1382, 1265, 1222, 1164,
1031, 896 cm−1; 1H NMR (CDCl3, 500 MHz) δ 2.37 (s, 3H), 3.93 (s,
3H), 7.10 (s, 1H), 7.14−7.18 (m, 3H), 7.44 (d, J = 8.0 Hz, 2H), 7.50
(d, J = 8.5 Hz, 1H), 7.66−7.71 (m, 2H), 7.98 (s, 1H); 13C NMR
(CDCl3, 125 MHz) δ 21.8, 55.5, 74.1, 74.2, 81.9, 82.0, 106.1, 117.1,
117.4, 118.7, 119.8, 127.1, 129.3 (2C), 129.4, 129.6, 132.6 (2C), 132.9,
134.8, 140.2, 158.9; HRMS calcd for C22H16O [M + H]+ 297.1271,
found 297.1279.
1
characterized by their IR, H NMR, and 13C NMR spectroscopic data
and elemental analysis or HRMS data. All these data are provided
below.
1-(Deca-1,3-diynyl)benzene (3aa, Table 2):20a Colorless
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viscous liquid (136 mg, 81%); H NMR (CDCl3, 300 MHz) δ 0.88
(t, J = 5.4 Hz, 3H), 1.25−1.43 (m, 6H), 1.52−1.62 (m, 2H), 2.35 (t, J
= 7.0 Hz, 2H), 7.26−7.33 (m, 3H), 7.45−7.48 (m, 2H); 13C NMR
(CDCl3, 75 MHz) δ 14.2, 19.7, 22.6, 28.4, 28.7, 31.4, 65.2, 74.6, 74.8,
85.0, 122.3, 128.3 (2C), 128.7, 132.5 (2C).
(E)-Tridec-4-en-6-yne (5aa, Table 2):20c Yellowish viscous liquid
1-(4-Cyclohexylbuta-1,3-diynyl)benzene (3ba, Table 2):10d
1
1
(156 mg, 88%); H NMR (CDCl3, 500 MHz) δ 0.91 (t, J = 7.5 Hz,
White solid (162 mg, 78%); mp 95−98 °C; H NMR (CDCl3, 500
6H), 1.24−1.35 (m, 4H), 1.36−1.43 (m, 4H), 1.48−1.58 (m, 2H),
2.03−2.07 (m, 2H), 2.26−2.30 (m, 2H), 5.45 (d, J = 16.0 Hz, 1H),
6.00−6.06 (m, 1H); 13C NMR (CDCl3, 125 MHz) δ 13.6, 14.0, 19.3,
22.0, 22.5, 28.6, 28.8, 31.4, 35.0, 79.2, 88.7, 110.0, 143.0.
MHz) δ 1.33 (t, J = 9.0 Hz, 2H), 1.50−1.57 (m, 4H), 1.72−1.76 (m,
2H), 1.83−1.85 (m, 2H), 2.53−2.56 (m, 1H), 7.28−7.38 (m, 3H),
7.47 (d, J = 7.0 Hz, 2H); 13C NMR (CDCl3, 125 MHz) δ 24.9, 25.8,
29.9, 32.3, 61.1, 74.5, 75.5, 88.7, 122.3, 128.5 (2C), 128.9 (2C), 132.6
(2C).
1-((E)-Hept-3-en-1-ynyl)benzene (5ja, Table 3):20d Yellow
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liquid (151 mg, 89%); H NMR (CDCl3, 500 MHz) δ 0.84−0.87
1-(4-Cyclohexylbuta-1,3-diynyl)-4-methoxybenzene (3bb,
Table 2): Dirty white solid (195 mg, 82%); mp 92−94 °C; IR
(KBr) 2929, 2854, 2138, 1602, 1566, 1508, 1442, 1282, 1249, 1172,
(m, 3H), 1.35−1.42 (m, 2H), 2.04−2.08 (m, 2H), 5.62 (d, J = 16.0
Hz, 1H), 6.14−6.20 (m, 1H), 7.20−7.23 (m, 3H), 7.33−7.35 (m, 2H);
13C NMR (CDCl3, 125 MHz) δ 13.8, 22.1, 35.4, 88.0, 88.5, 109.8,
123.8, 128.4, 127.9 (2C), 131.5 (2C), 145.1.
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1031, 831 cm−1; H NMR (CDCl3, 300 MHz) δ 1.32−1.34 (m, 2H),
1.49−1.56 (m, 4H), 1.70−1.75 (m, 2H), 1.79−1.85 (m, 2H), 2.49−
2.57 (m,1H), 3.80 (s, 3H), 6.81 (d, J = 7.5 Hz, 2H), 7.40 (d, J = 8.0
Hz, 2H); 13C NMR (CDCl3, 75 MHz) δ 24.8 (2C), 25.9, 29.9, 32.3
(2C), 55.4, 65.3, 73.2, 75.6, 88.0, 114.2 (2C), 114.3, 134.1(2C), 160.0.
Anal. Calcd for C17H18O: C, 85.67; H, 7.61. Found: C, 85.63; H, 7.59.
3-(4-Phenylbuta-1,3-diynyl)thiophene (3da, Table 2):20b
(E)-Ethyl-5-p-tolylpent-4-en-2-ynoate (5mb, Table 3): Yellow
liquid (184 mg, 86%); IR (neat) 3444, 2981, 2923, 2204, 1728, 1705,
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1604, 1514, 1367, 1276, 1253, 1097, 1020 cm−1; H NMR (CDCl3,
500 MHz) δ 1.34 (t, J = 7.5 Hz, 3H), 2.36 (s, 3H), 4.25−4.29 (q, J =
7.5 Hz, 2H), 6.14 (d, J = 16.0 Hz, 1H), 7.16 (d, J = 7.5 Hz, 2H), 7.22
(d, J = 16.0 Hz, 1H), 7.31 (d, J = 7.5 Hz, 2H); 13C NMR (CDCl3, 125
MHz) δ 14.2, 21.5, 62.0, 82.3. 86.4, 103.6, 127.0 (2C), 129.7 (2C),
132.5, 140.5, 147.8, 154.2; HRMS calcd for C14H14O2 [M + H]+
215.1069, found 215.1072.
1-((E)-Hept-3-en-1-ynyl)-4-methylbenzene (5fa, Table 3):
Yellow liquid (167 mg, 91%); IR (neat) 3448, 3028, 2960, 2929,
2871, 2187, 1716, 1660, 1604, 1508, 1458, 1178 cm−1; 1H NMR
(CDCl3, 500 MHz) δ 0.94 (t, J = 7.5 Hz, 3H), 1.44−1.50 (m, 2H),
2.12−2.17 (m, 2H), 2.34 (s, 3H), 5.70 (d, J = 16.0 Hz, 1H), 6.20−6.26
(m, 2H), 7.11 (t, J = 8.0 Hz, 2H), 7.32 (t, J = 8.0 Hz, 2H); 13C NMR
(CDCl3, 125 MHz) δ 13.7, 21.5, 22.1, 35.4, 87.8, 88.1, 109.9, 120.7,
129.1 (2C), 131.4 (2C), 138.0, 144.6. Anal. Calcd for C14H16: C,
91.25; H, 8.75. Found: C, 91.27; H, 8.72.
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White solid (174 mg, 84%); mp 86−87 °C; H NMR (CDCl3, 500
MHz) δ 7.19 (d, J = 6.0 Hz, 1H), 7.29−7.40 (m, 4H), 7.53 (d, J = 8.5
Hz, 2H), 7.60 (s, 1H); 13C NMR (CDCl3, 125 MHz) δ 73.7, 74.1,
81.5, 81.7, 121.1, 122.0, 125.7, 128.6 (2C), 129.3, 130.3 (2C), 131.4,
132.6.
1-(4-(4-tert-Butylphenyl)buta-1,3-diynyl)-4-methoxy-
benzene (3gb, Table 2):10b White solid (236 mg, 82%); mp 81−84
°C; 1H NMR (CDCl3, 500 MHz) δ 1.32 (s, 9H), 3.82 (s, 3H), 6.86 (d,
J = 8.5 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H), 7.46−7.48 (m, 4H); 13C
NMR (CDCl3, 125 MHz) δ 31.2 (3C), 35.0, 55.4, 73.1, 73.7, 81.5,
81.6, 114.0, 114.3 (2C), 119.0, 125.6 (2C), 132.3 (2C), 134.2 (2C),
152.6, 160.4.
1-(4-p-Tolylbuta-1,3-diynyl)benzene (3jc, Table 2):10d White
solid (173 mg, 80%); mp 117−118 °C; 1H NMR (400 MHz, CDCl3)
δ 2.38 (s, 3H), 7.15 (d, J = 8.0 Hz, 2H), 7.33−7.38 (m, 3H), 7.42−
7.45 (m, 2H), 7.53−7.55 (m, 2H); 13C NMR (CDCl3, 100 MHz) δ
21.7, 73.5, 74.2, 81.4, 82.0, 118.9, 122.0, 128.5 (2C), 129.2 (2C), 129.4
(2C), 132.5 (2C), 132.6 (2C).
3-((E)-Hept-3-en-1-ynyl)thiophene (5da, Table 3): Dark gray
liquid (153 mg, 87%); IR (neat) 3107, 2958, 2930, 2871, 2198, 1654,
1
1519, 1456, 1355, 1184, 954 cm−1; H NMR (CDCl3, 500 MHz) δ
0.94 (t, J = 7.0 Hz, 3H), 1.42−1.50 (m, 2H), 2.12−2.16 (m, 2H), 5.68
(d, J = 16.0 Hz, 1H), 6.20−6.26 (m, 1H), 7.11 (d, J = 5.0 Hz, 1H),
7.24−7.26 (m, 1H), 7.40 (d, J = 3.5 Hz, 1H); 13C NMR (CDCl3, 125
MHz) δ 13.7, 22.1, 35.4, 83.0, 88.0, 109.7, 122.7, 125.3, 128.1, 129.9,
144.9; HRMS calcd for C11H12S [M + H]+ 177.0731, found 177.0738.
1-(Trifluoromethyl)-2-((E)-4-p-tolylbut-3-en-1-ynyl)benzene
(5eb, Table 3): Colorless liquid (229 mg, 80%); IR (neat) 3028,
2956, 2198, 1598, 1569, 1488, 1448, 1317, 1263, 1182, 1164, 1118,
1-(4-(2-(Trifluoromethyl)phenyl)buta-1,3-diynyl)benzene
(3ea,Table 2): Dirty white solid (218 mg, 81%); mp 84−85 °C; IR
(KBr) 3029, 2210, 1598, 1569, 1487, 1448, 1317, 1261, 1163, 1110,
1
1031, 812 cm−1; H NMR (CDCl3, 300 MHz) δ 7.33−7.37 (m, 4H),
7.51−7.56 (m, 3H), 7.67 (d, J = 8.1 Hz, 2H); 13C NMR (CDCl3, 75
MHz) δ 73.7, 74.0, 81.7, 83.6, 121.6, 121.7, 123.2 (q, JC−F = 273.4 Hz,
1C), 126.2 (q, JC−F = 9.8 Hz, 1C), 128.6 (2C), 128.9, 129.3, 129.6,
131.6, 132.4 (2C), 132.7, 135.1. Anal. Calcd for C17H9F3: C, 75.55; H,
3.36. Found: C, 75.50; H, 3.31.
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952 cm−1; H NMR (CDCl3, 500 MHz) δ 2.38 (s, 3H), 6.38 (d, J =
16.0 Hz, 1H), 7.09 (d, J = 16.0 Hz, 1H), 7.18 (d, J = 8.0 Hz, 2H),
7.35−7.41 (m, 3H), 7.50 (t, J = 7.5 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H),
7.68 (d, J = 7.5 Hz, 1H); 13C NMR (CDCl3, 125 MHz) δ 21.4, 87.3,
94.9, 106.7, 122.0, 123.4 (q, JC−F = 271.2 Hz, 1C), 125.9 (q, JC−F = 5.0
Hz, 1C), 126.0, 126.6 (2C), 127.8, 129.6 (2C), 131.5, 133.5, 133.8,
139.2, 142.7. Anal. Calcd for C18H13F3: C, 75.51; H, 4.58. Found: C,
75.47; H, 4.61.
2-Methoxy-6-(4-phenylbuta-1,3-diynyl)naphthalene (3ha,
Table 2): White solid (239 mg, 85%); mp 89−91 °C; IR (KBr)
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3026, 2918, 2130, 1923, 1587, 1512, 1446, 1102, 1074, 812 cm−1; H
NMR (CDCl3, 500 MHz) δ 3.95 (s, 3H), 7.11 (s, 1H), 7.15−7.19 (m,
1H), 7.34−7.36 (m, 3H), 7.49−7.56 (m, 3H), 7.66−7.72 (m, 2H),
7.99 (s, 1H); 13C NMR (CDCl3, 125 MHz) δ 56.4, 73.7, 74.3, 81.6,
82.1, 106.3, 116.9, 117.8, 119.4, 126.8, 129.3 (2C), 129.4, 129.6, 131.5,
132.6 (2C), 132.9, 134.8, 140.5, 158.4; HRMS calcd for C21H14O [M
+ H]+ 283.1116, found 283.1123.
1-(4-(4-Bromophenyl)buta-1,3-diynyl)benzene (3ia, Table
2):10d White solid (233 mg, 83%); mp 91−93 °C; 1H NMR
(CDCl3, 500 MHz) δ 7.37−7.42 (m, 5H), 7.50 (d, J = 7.5 Hz, 2H),
7.56 (d, J = 7.0 Hz, 2H); 13C NMR (CDCl3, 125 MHz) δ 73.8, 74.0,
75.2, 81.7, 121.9, 128.5 (2C), 128.7, 129.3 (2C), 131.7, 131.9, 132.6
(2C), 133.9 (2C).
3-((E)-4-Cyclohexylbut-3-en-1-ynyl)thiophene (5dc, Table 3):
Light gray liquid (175 mg, 81%); IR (neat) 3107, 3016, 2923, 2850,
1
2198, 1660, 1519, 1448, 1353, 1184 cm−1; H NMR (CDCl3, 500
MHz) δ 1.09−1.22 (m, 3H), 1.25−1.33 (m, 2H), 1.66 (d, J = 12.5 Hz,
1H), 1.75 (d, J = 11.0 Hz, 4H), 2.05−2.11 (m, 1H), 5.63 (d, J = 16.0
Hz, 1H), 6.17−6.22 (dd, J1 = 16.0 Hz, J2 = 16.0 Hz, 1H), 7.10 (d, J =
5.0 Hz, 1H), 7.24−7.26 (m, 1H), 7.39 (d, J = 2.0 Hz, 1H); 13C NMR
(CDCl3, 125 MHz) δ 25.9, 26.1 (2C), 32.4 (2C), 41.5, 83.3, 88.1,
107.2, 122.8, 125.3, 128.0, 129.9, 150.5. Anal. Calcd for C14H16S: C,
77.72; H, 7.45. Found: C, 77.74; H, 7.41.
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dx.doi.org/10.1021/jo5011069 | J. Org. Chem. 2014, 79, 7391−7398