260
X. Fan et al. / Tetrahedron 70 (2014) 256e261
4.6. Characterization data
2H), 7.84 (dd, J¼13.2, 8.1 Hz, 4H), 7.57e7.47 (m, 6H), 7.46e7.40 (m,
2H), 5.07 (s, 4H), 4.29 (s, 4H); 13C NMR (100 MHz, CDCl3):
133.6,
d
4.6.1. 1,4-Diphenylbuta-1,3-diyne (3a). White solid: 53 mg, 95%;
132.3, 131.7, 129.0, 128.4, 127.1, 126.3, 125.8, 125.0, 123.9, 75.4, 70.7,
70.1, 57.4; HRMS (EI, m/z) calcd for C28H22O2 [M]þ, 390.1620, found
390.1619.
mp 86.8e87 ꢀC; 1H NMR (400 MHz, CDCl3):
d
7.48 (dd, J¼8.0, 1.4 Hz,
4H), 7.39e7.28 (m, 6H). This compound was known.21a
4.6.2. 1,4-Dip-tolylbuta-1,3-diyne (3b). White solid: 59 mg, 93%;
4.6.14. 1,6-Bis(1-(naphthalen-1-yl)but-3-enyloxy)hexa-2,4-diyne
mp 179e183 ꢀC; 1H NMR (400 MHz, CDCl3):
d
7.42 (d, J¼7.9 Hz, 4H),
(3n). Yellow oil: 127 mg, 98%; 1H NMR (400 MHz, CDCl3):
d
¼8.19
7.14 (d, J¼7.8 Hz, 4H), 2.37 (s, 6H). This compound was known.21a
(d, J¼8.0 Hz, 2H), 7.88 (d, J¼7.5 Hz, 2H), 7.80 (d, J¼8.0 Hz, 2H), 7.50
(dt, J¼15.4, 7.4 Hz, 8H), 5.87 (dd, J¼17.1, 10.1 Hz, 2H), 5.30 (t,
J¼5.5 Hz, 2H), 5.08 (dd, J¼17.8, 14.3 Hz, 4H), 4.27 (d, J¼16.4 Hz,
4.6.3. 1,4-Bis(4-pentylphenyl)buta-1,3-diyne (3c). White solid:
93 mg, 99%; mp 87e88 ꢀC; 1H NMR (400 MHz, CDCl3):
d
7.43 (d,
2H), 4.00 (d, J¼16.4 Hz, 2H), 2.71 (dtd, J¼20.6, 14.3, 6.6 Hz, 4H); 13
C
J¼8.1 Hz, 4H), 7.14 (d, J¼8.0 Hz, 4H), 2.62e2.58 (m, 4H), 1.64e1.55
(m, 4H), 1.36e1.25 (m, 8H), 0.89 (t, J¼6.8 Hz, 6H). This compound
was known.11b
NMR (100 MHz, CDCl3): d 135.9, 134.6, 133.9, 130.9, 128.9, 128.3,
126.1, 125.5, 125.3, 124.6, 123.2, 116.9, 78.5, 75.4, 70.3, 56.3, 41.5;
HRMS (EI, m/z) calcd for
C
34H30O2 [M]þ, 470.2246, found
470.2230.
4.6.4. 1,4-Bis(4-methoxyphenyl)buta-1,3-diyne (3d). White solid:
47 mg, 65% or 68 mg, 94% (using DBU as base); mp 138e139 ꢀC; 1H
4.6.15. 1,6-Bis(benzyloxy)hexa-2,4-diyne (3o). Yellow oil: 78 mg,
NMR (400 MHz, CDCl3):
d
7.46 (d, J¼8.8 Hz, 4H), 6.85 (d, J¼8.4 Hz,
98%; 1H NMR (400 MHz, CDCl3):
d 7.45e7.26 (m, 10H), 4.61 (s, 4H),
4H), 3.82 (s, 6H). This compound was known.21a
4.25 (s, 4H). This compound was known.24a
4.6.5. 1,4-Bis(4-fluorophenyl)buta-1,3-diyne
(3e). White solid:
4.6.16. 1,6-Bis(4-methoxybenzyloxy)hexa-2,4-diyne
(3p). Yellow
7.28
(d, J¼8.4 Hz, 4H), 6.88 (d, J¼8.5 Hz, 4H), 4.53 (s, 4H), 4.21 (s, 4H),
57 mg, 87%; mp 188e193 ꢀC; 1H NMR (400 MHz, CDCl3):
solid: 88 mg, 91%; mp 63e64 ꢀC; 1H NMR (400 MHz, CDCl3):
d
d
7.58e7.47 (m, 4H), 7.04 (t, J¼8.6 Hz, 4H). This compound was
known.11a
3.79 (s, 6H); 13C NMR (100 MHz, CDCl3):
d 159.4, 129.8, 129.1, 113.8,
75.4, 71.4, 70.5, 57.1, 55.2; HRMS (EI, m/z) calcd for C22H22O4 [M]þ,
4.6.6. Hexadeca-7,9-diyne (3f). Yellow oil: 53 mg, 88%; 1H NMR
350.1518, found 350.1526.
(400 MHz, CDCl3):
d
2.24 (t, J¼7.0 Hz, 4H), 1.56e1.47 (m, 4H),
1.42e1.34 (m, 4H), 1.29 (ddd, J¼10.2, 8.7, 2.5 Hz, 8H), 0.89 (t,
4.6.17. 1,6-Bis(benzo[d][1,3]dioxol-5-ylmethoxy)hexa-2,4-diyne
J¼6.9 Hz, 6H). This compound was known.8b
(3q). Yellow solid: 71 mg, 68% or 79 mg, 76% (using DBU as base);
mp 58e63 ꢀC; 1H NMR (400 MHz, CDCl3):
d
6.93e6.73 (m, 6H),
4.6.7. 2,2,7,7-Tetramethylocta-3,5-diyne (3g). White solid: 44 mg,
5.95 (s, 4H), 4.50 (s, 4H), 4.22 (s, 4H); 13C NMR (100 MHz, CDCl3):
99%; mp 86e88 ꢀC; 1H NMR (400 MHz, CDCl3):
d
1.24 (s, 18H). This
d 147.8, 147.4, 130.8, 121.9, 108.8, 108.1, 101.0, 75.3, 71.6, 70.5,
compound was known.21a
57.1; HRMS (EI, m/z) calcd for C22H18O6 [M]þ, 378.1103, found
378.1102.
4.6.8. 1,4-Dicyclopropylbuta-1,3-diyne (3h). Yellow oil: 30 mg, 85%;
1H NMR (400 MHz, CDCl3):
1.31e1.25 (m, 2H), 1.08e0.49 (m, 8H).
This compound was known.11a
d
4.6.18. 1,6-Bis(cinnamyloxy)hexa-2,4-diyne
(3r). White
solid:
7.39 (d,
74 mg, 79%; mp 64e66 ꢀC; 1H NMR (400 MHz, CDCl3):
d
J¼7.6 Hz, 4H), 7.31 (t, J¼7.5 Hz, 4H), 7.24 (t, J¼7.1 Hz, 2H), 6.64 (d,
4.6.9. 2,7-Dimethylocta-3,5-diyne-2,7-diol (3i). White solid: 45 mg,
J¼15.9 Hz, 2H), 6.25 (dt, J¼15.9, 6.2 Hz, 2H), 4.27 (s, 4H), 4.23 (d,
98%; mp 133e134 ꢀC; 1H NMR (400 MHz, CDCl3):
d
5.55 (s, 2H), 1.35
J¼6.2 Hz, 4H); 13C NMR (100 MHz, CDCl3):
d 136.4, 133.6, 128.5,
127.8, 126.5, 124.7, 75.4, 70.4, 57.4; HRMS (EI, m/z) calcd for
(s, 12H). This compound was known.8b
C
24H22O2 [M]þ, 342.1620, found 342.1609.
4.6.10. 1,4-Bis(trimethylsilyl)buta-1,3-diyne
(3j). White
solid:
0.19 (s,
46 mg, 86%; mp 80e81 ꢀC; 1H NMR (400 MHz, CDCl3):
d
4.6.19. 1,4-Di(pyridin-3-yl)buta-1,3-diyne (3s). White solid: 49 mg,
88%; mp 156e159 ꢀC; 1H NMR (400 MHz, CDCl3):
8.78 (s, 2H), 8.61
18H). This compound was known.31
d
(d, J¼4.8 Hz, 2H), 7.88e7.79 (m, 2H), 7.31 (dd, J¼7.9, 5.0 Hz, 2H). This
4.6.11. 1,6-Bis(1-phenylbut-3-enyloxy)hexa-2,4-diyne (3k). Yellow
oil: 92 mg, 90%; 1H NMR (400 MHz, CDCl3):
7.39e7.26 (m, 10H),
compound was known.11b
d
5.76 (ddt, J¼14.0, 10.1, 6.9 Hz, 2H), 5.05 (t, J¼13.0 Hz, 4H), 4.53 (t,
J¼6.7 Hz, 2H), 4.19 (d, J¼16.3 Hz, 2H), 3.93 (d, J¼16.3 Hz, 2H), 2.62
(dt, J¼14.3, 7.1 Hz, 2H), 2.52e2.38 (m, 2H). This compound was
known.14a
4.6.20. 1,4-Di(thiophen-2-yl)buta-1,3-diyne
(3t). White
solid:
7.34 (dd,
49 mg, 83%; mp 85e88 ꢀC; 1H NMR (400 MHz, CDCl3):
d
J¼7.5, 4.4 Hz, 2H), 7.04e6.96 (m,1H). This compound was known.11a
4.6.21. 2-Methyl-6-phenylhexa-3,5-diyn-2-ol (4ai). White solid:
4.6.12. 1,6-Bis(1,2,3,4-tetrahydronaphthalen-1-yloxy)hexa-2,4-diyne
48 mg, 42%; mp 68e69 ꢀC; 1H NMR (400 MHz, CDCl3):
d 7.48 (dd,
(3l). Yellow oil: 101 mg, 99%; 1H NMR (400 MHz, CDCl3):
J¼8.0, 1.4 Hz, 2H), 7.38e7.27 (m, 3H), 1.57 (d, J¼5.5 Hz, 6H). This
d
¼7.41e7.33 (m, 2H), 7.25e7.14 (m, 4H), 7.13e7.06 (m, 2H), 4.67 (t,
compound was known.24a
J¼4.3 Hz, 2H), 4.33 (s, 4H), 2.84 (dt, J¼16.8, 5.3 Hz, 2H), 2.76e2.66
(m, 2H), 2.08e1.97 (m, 4H), 1.92 (ddd, J¼15.2, 5.9, 3.2 Hz, 2H),
4.6.22. 2-Methyldodeca-3,5-diyn-2-ol (4fi). Colorless oil: 47 mg,
1.79e1.70 (m, 2H); 13C NMR (100 MHz, CDCl3):
d
137.7,
40%; 1H NMR (400 MHz, CDCl3):
d
2.28 (t, J¼7.0 Hz, 2H), 1.59e1.46
135.5, 129.6, 129.0, 127.8, 125.7, 76.0, 74.0, 70.2, 55.8, 28.9, 27.7,
18.5; HRMS (EI, m/z) calcd for C26H26O2 [M]þ, 370.1933, found
370.1939.
(m, 8H), 1.43e1.25 (m, 6H), 0.89 (t, J¼6.9 Hz, 3H). This compound
was known.32
4.6.23. 3-(Phenylbuta-1,3-diynyl)pyridine
(4as). White
solid:
8.76 (s,
4.6.13. 1,6-Bis(naphthalen-1-ylmethoxy)hexa-2,4-diyne (3m). Yello
56 mg, 48%; mp 102e106 ꢀC; 1H NMR (400 MHz, CDCl3)
d
w oil: 87 mg, 81%; 1H NMR (400 MHz, CDCl3):
d
8.14 (d, J¼8.3 Hz,
1H), 8.63e8.55 (m, 1H), 7.85e7.78 (m, 1H), 7.58e7.52 (m, 2H),