T. Li et al. / Tetrahedron 68 (2012) 6413e6419
6417
þ
þ
þ
1
30.0 (CH), 124.6 (C),123.4 (C), 91.9 (C), 89.9 (C); HRMS (ESI ): calcd
2 2 3
(CH ), 19.7 (CH ), 14.3 (CH ); HRMS (ESI ): calcd for [C13H15Br]
requires m/z 250.0357, found 250.0357.
þ
for [C14
9
H Cl] requires m/z 212.0393, found 212.0396.
4
.2.5. 1-Methoxy-3-(2-phenylethynyl)benzene. 1H NMR (400 MHz,
4.2.14. 1-(Hept-1-ynyl)-4-methoxybenzene. 1
H
NMR (400 MHz,
CDCl : 7.55e7.52 (m, 2H, ArH), 7.37e7.34 (m, 3H, ArH), 7.27e7.23
3
)
d
3
CDCl ) d: 7.33e7.35 (m, 2H), 6.81e6.83 (m, 2H), 3.80 (s, 3H), 2.39 (t,
(
(
(
m, 1H, ArH), 7.13 (d, J¼7.6 Hz, 2H, ArH), 7.06 (s, 1H, ArH), 6.91e9.88
J¼7.2 Hz, 2H), 1.57e1.64 (m, 2H), 1.43e1.46 (m, 2H), 1.34e1.40 (m,
13
13
m, 1H, ArH), 2.82 (s, 3H, OCH
C),133.3 (CH),131.1 (CH),130.0 (CH),130.0 (CH),125.9 (CH),125.8 (C),
24.8 (CH),117.9 (C),116.6 (CH), 90.9 (C), 90.8 (C), 56.9 (OCH ); HRMS
12O] requires m/z 208.0888, found 208.0884.
3
); C NMR (100 MHz, CDCl
3
)
d
: 161.0
2H), 0.93 (t, J¼7.2 Hz, 3H); C NMR (100 MHz, CDCl
3
) d: 137.7 (CH),
134.4 (CH), 117.9 (CH), 115.4 (CH), 90.4 (C), 81.8 (C), 56.8 (CH
3
), 32.8
þ
1
3
(CH
2
), 30.2 (CH
2
), 23.9 (CH
2
), 21.0 (CH
2
), 15.7 (CH
3
); HRMS (ESI ):
þ
þ
þ
(
ESI ): calcd for [C15
H
calcd for [C14
H18O] requires m/z 202.1358, found 202.1360.
4
.2.6. 1-Fluoro-4-(2-phenylethynyl)benzene. 1
H
NMR (400 MHz,
.2.15. 1-(Hept-1-ynyl)-4-methylbenzene. 1
4
H
NMR
(400 MHz,
CDCl : 7.53e7.50 (m, 4H, ArH), 7.36e7.34 (m, 3H, ArH), 7.05 (t,
3
) d
CDCl
3
)
d
: 7.28 (d, J¼8.0 Hz, 2H), 7.07 (d, J¼8.0 Hz, 2H), 2.38 (t,
13
J¼8.6 Hz, 2H, ArH);
3
C NMR (100 MHz, CDCl ) d: 165.4 (d,
J¼7.2 Hz, 2H), 2.32 (s, 3H), 1.56e1.63 (m, 2H), 1.32e1.46 (m, 4H),
J¼249.5 Hz, C), 135.2 (d, J¼8.3 Hz, CH), 133.2 (CH), 130.0 (d,
13
0
.92 (t, J¼7.2 Hz, 3H); C NMR (100 MHz, CDCl
3
) d: 137.6 (C), 131.6
J¼3.7 Hz, CH), 124.7 (C), 121.0 (d, J¼3.4 Hz, CH), 117.4 (C), 117.2 (C),
(
C), 129.2 (CH), 121.2 (CH), 89.9 (C), 80.8 (C), 31.4 (CH
2
), 28.8 (CH
2
),
þ
þ
9
0.7 (C), 89.2 (C); HRMS (ESI ): calcd for [C14
H
9
F] requires m/z
þ
2
C
2.5 (CH
2
), 21.7 (CH
2
), 19.7 (CH
þ
18
] requires m/z 186.1409, found 186.1409.
3
), 14.3 (CH
3
); HRMS (ESI ): calcd for
1
96.0688, found 196.0690.
.2.7. 1-(2-Phenylethynyl)naphthalene. 1H NMR (400 MHz, CDCl
)
3
[
14
H
4
4
.2.16. 1-(Hept-1-ynyl)benzene. 1
H NMR (400 MHz, CDCl ) d:
3
d
: 8.45 (d, J¼8.0 Hz, 1H, ArH), 7.88e7.76 (m, 3H, ArH), 7.67e7.59 (m,
13
7.41e7.43 (m, 2H), 7.29e7.30 (m, 3H), 2.43 (t, J¼7.2 Hz, 2H),1.60e1.67
3
H, ArH), 7.56e7.54 (m, 2H, ArH), 7.48e7.39 (m, 3H, ArH); C NMR
: 134.9 (C), 134.8 (C), 133.3 (C), 132.0 (CH), 130.4
13
(
m, 2H),1.37e1.48 (m, 4H), 0.95 (t, J¼7.2 Hz, 3H); C NMR (100 MHz,
CDCl : 133.2 (CH), 129.8 (CH), 129.1 (CH), 125.7 (CH), 92.1 (C), 82.2
C), 32.8 (CH ), 30.1 (CH ), 23.9 (CH ), 21.0 (CH ), 15.7 (CH ); HRMS
requires m/z 172.1252, found 172.1250.
(
(
(
(
100 MHz, CDCl
3
)
d
3
) d
CH), 130.1 (CH), 130.1 (CH), 130.0 (CH), 128.5 (CH), 128.1 (CH), 127.9
CH), 127.0 (CH), 125.0 (CH), 122.5 (C), 95.9 (C), 89.2 (C); HRMS
ESI ): calcd for [C18
(
2
2
2
2
3
þ þ
16
(ESI ): calcd for [C13H ]
þ
þ
H
12
]
requires m/z 228.0939, found 228.0938.
4.2.17. 1-(Trifluoromethyl)-3-(2-phenylethynyl)benzene. 1
(400 MHz, CDCl
: 7.80 (s, 1H, ArH), 7.70 (d, J¼7.6 Hz, 2H, ArH),
7.59e7.54 (m, 3H, ArH), 7.48 (t, J¼8.0 Hz, 1H, ArH), 7.37 (t, J¼3.2 Hz,
H
NMR
4
.2.8. 1-Bromo-4-(2-phenylethynyl)benzene. 1
H
NMR (400 MHz,
13
CDCl : 7.52e7.47 (m, 4H, ArH), 7.40e7.35 (m, 5H, ArH); C NMR
100 MHz, CDCl : 137.7 (C), 134.6 (CH), 133.2 (CH), 130.1 (CH),
30.0 (CH), 124.5 (CH), 124.1 (C), 123.8 (C), 92.1 (C), 89.9 (C); HRMS
3
)
d
3
) d
(
3
) d
13
1
(
3H, ArH); C NMR (100 MHz, CDCl
(CH), 130.4 (q, J¼186 Hz), 130.1 (C), 130.0 (C), 129.9 (CH), 126.7 (CH),
26.4 (q, J¼44 Hz), 125.9 (CH), 124.2 (CH), 92.5 (C), 89.4 (C); HRMS
3
) d: 136.2 (C), 134.1 (CH), 133.3
þ þ
9
ESI ): calcd for [C14H Br] requires m/z 255.9888, found 255.9886.
1
(
4
.2.9. 1-(2-(2-Methoxyphenyl)ethynyl)benzene. 1H NMR (400 MHz,
: 7.67e7.64 (m, 2H, ArH), 7.59 (d, J¼7.6 Hz, 1H, ArH),
.42e7.39 (m, 4H, ArH), 7.04e6.97 (m, 2H, ArH), 3.99 (s, 3H, OCH );
: 161.5 (C), 135.2 (CH), 133.3 (CH), 131.4
CH), 129.9 (CH), 129.8 (CH), 125.2 (CH), 122.1 (C), 114.0 (C), 112.3
þ þ
9
ESI ): calcd for [C15H F] requires m/z 246.0656, found 246.0653.
3
CDCl ) d
4
.2.18. 2-(2-Phenylethynyl)pyridine. 1H NMR (400 MHz, CDCl
3
) d:
7
3
1
3
C NMR (100 MHz, CDCl
3
)
d
8.78 (s, 1H), 8.55 (d, J¼4.8 Hz, 1H, ArH), 7.83e7.81 (m, 1H, ArH),
7
.58e7.54 (m, 2H, ArH), 7.38e7.37 (m, 3H, ArH), 7.31e7.28 (m, 1H,
(
(
[
13
þ
CH), 95.1 (C), 87.4 (C), 57.5 (OCH
C
3
); HRMS (ESI ): calcd for
12O] requires m/z 208.1000, found 208.1000.
ArH); C NMR (100 MHz, CDCl
3
) d: 151.4 (CH), 144.8 (C), 138.0 (CH),
þ
1
33.7 (CH), 130.7 (CH), 130.0 (CH), 128.8 (CH), 124.4 (CH), 123.8 (C),
15
H
þ
þ
91.2 (C), 90.0 (C); HRMS (ESI ): calcd for [C13
9
H N] requires m/z
4
d
.2.10. 1,3-Bis(2-phenylethynyl)benzene. 1H NMR (400 MHz, CDCl
: 7.39e7.32 (m, 7H, ArH), 7.49 (d, J¼7.6 Hz, 2H, ArH), 7.54 (t,
3
)
179.0735, found 179.0731.
13
4.2.19. 3-(2-Phenylethynyl)pyridine. 1H NMR (400 MHz, CDCl3)
.78 (s, 1H), 8.55 (d, J¼4.0 Hz, 1H, ArH), 7.83e7.80 (m, 1H, ArH),
7.57e7.55 (m, 2H, ArH), 7.38e7.37 (m, 3H, ArH), 7.30e7.28 (m, 1H,
d:
J¼3.6 Hz, 4H, ArH), 7.72 (s, 1H, ArH); C NMR (100 MHz, CDCl
3
)
d:
136.2 (CH), 133.3 (CH), 132.9 (CH), 130.1 (CH), 130.1 (CH), 130.1 (CH),
8
þ
125.2 (C), 124.6 (C), 91.6 (C), 90.2 (C); HRMS (ESI ): calcd for
þ
13
[C
22
H
14
]
requires m/z 278.1096, found 278.1096.
3
ArH); C NMR (100 MHz, CDCl ) d: 152.4 (CH), 148.7 (C),138.7 (CH),
1
32.0 (CH), 129.0 (CH), 128.7 (CH), 123.3 (CH), 122.7 (CH), 120.7 (C),
4
.2.11. 1-Nitro-4-(2-phenylethynyl)benzene. 1
CDCl
: 8.24 (d, J¼8.8 Hz, 2H, ArH), 7.69 (d, J¼7.6 Hz, 2H, ArH),
.60e7.57 (m, 2H, ArH), 7.42e7.41 (m, 3H, ArH); C NMR (100 MHz,
H
NMR (400 MHz,
þ
þ
9
92.9 (C), 86.1 (C); HRMS (ESI ): calcd for [C13H N] requires m/z
3
) d
179.0735, found 179.0735.
1
3
7
CDCl
3
)
d
: 148.6 (C), 133.9 (CH), 133.5 (CH), 131.9 (CH), 130.9 (CH),
.2.20. 2-Methyl-5-(2-phenylethynyl)pyridine. 1H NMR (400 MHz,
4
þ
1
30.2 (CH), 125.3 (C), 123.7 (C), 96.3 (C), 89.2 (C); HRMS (ESI ):
CDCl
3
)
d
: 8.66 (s, 1H), 7.70 (m, J¼8.0 Hz, 1H, ArH), 7.55e7.53 (m, 2H,
þ
9 2
calcd for [C14H NO ] requires m/z 223.0633, found 223.0635.
ArH), 7.37e7.35 (m, 3H, ArH), 7.16e7.14 (m, 1H, ArH), 2.58 (s, 3H,
1
3
.2.12. 1-Chloro-4-(hept-1-ynyl)benzene. 1
CH ); C NMR (100 MHz, CDCl3)
d: 157.9 (CH), 151.8 (C), 138.9 (CH),
3
4
H
NMR
(400 MHz,
1
31.8 (CH), 128.8 (CH), 128.6 (CH), 123.0 (CH),117.6 (C), 92.1 (C), 86.4
CDCl
3
)
d
: 7.39 (d, J¼8.4 Hz, 2H, ArH), 7.32 (d, J¼8.4 Hz, 2H, ArH),
þ þ
3 9
); HRMS (ESI ): calcd for [C13H N] requires m/z
(
C), 24.7 (CH
2
.47e2.44 (m, 2H), 1.71e1.63 (m, 2H), 1.51e1.40 (m, 4H), 1.00e0.97
m, 3H); 1 C NMR (100 MHz, CDCl
3
193.0891, found 193.0891.
(
(
3
) d: 134.4 (C), 131.5 (CH), 130.1
CH), 121.7 (C), 93.2 (C), 81.1 (C), 32.8 (CH
2
), 30.0 (CH
2
), 23.9 (CH
2
),
4.2.21. 4-(2-Phenylethynyl)benzonitrile. 1H NMR (400 MHz, CDCl )
þ
þ
3
21.0 (CH
2
), 15.6 (CH
3
); HRMS (ESI ): calcd for [C13H15Cl] requires
13
d
: 7.55e7.53 (m, 4H, ArH), 7.39e7.33 (m, 5H, ArH); C NMR
100 MHz, CDCl : 133.7 (C), 133.6 (CH), 130.8 (CH), 130.1 (CH),
129.8 (CH), 123.8 (CH), 120.2 (C), 113.1 (C), 95.4 (C), 89.4 (C); HRMS
m/z 206.0862, found 206.0864.
(
3
) d
4
.2.13. 1-Bromo-4-(hept-1-ynyl)benzene. 1
CDCl
: 7.41 (d, J¼8.0 Hz, 2H, ArH), 7.26 (d, J¼7.6 Hz, 2H, ArH), 2.39
t, J¼7.2 Hz, 2H), 1.58e1.65 (m, 2H), 1.33e1.47 (m, 4H), 0.94 (t,
H
NMR
(400 MHz,
þ
þ
3
)
d
9
(ESI ): calcd for [C15H N] requires m/z 203.0735, found 203.0738.
(
13
4.2.22. 1-(3-(2-Phenylethynyl)phenyl)ethanone. 1H NMR (400 MHz,
CDCl
: 8.17 (s, 1H, ArH), 7.97 (d, J¼8.0 Hz, 1H, ArH), 7.77 (d, 4H,
J¼7.2 Hz, 3H); C NMR (75 MHz, CDCl
3
)
d: 133.3 (C), 131.6 (CH),
123.3 (CH), 121.8 (C), 92.0 (C), 79.8 (C), 31.4 (CH
2
), 28.6 (CH ), 22.5
2
3
) d