Y. Suzuki et al. / Tetrahedron 67 (2011) 7956e7962
7961
7.61 (t, 1H, J¼7.70 Hz), 7.67 (d, 2H, J¼7.70 Hz); 13C NMR (125 MHz,
(d, 1H, J¼7.73 Hz); 13C NMR (125 MHz, CDCl3):
d
¼20.43, 112.74,
CDCl3):
d
¼112.43, 118.81, 129.09, 132.13, 132.73.
118.10, 126.17, 130.19, 132.47, 132.59, 141.90.
4.3.2. 4-Fluorobenzonitrile (ꢁ21b). Mp 34e35 ꢀC (commercial, mp
4.3.14. 2-Iodobenzonitrile (2n). Mp 53e55 ꢀC (commercial, mp
35 C); IR (Nujol): 2233 cm
;
1H NMR (400 MHz, CDCl3):
d
¼7.18
55 C); IR (Nujol): 2224 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d¼7.28 (t,
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(dd, JHeH¼9.1 Hz, JHeF¼8.4 Hz, 2H), 7.69 (dd, JHeH¼9.1 Hz,
1H, J¼7.70 Hz), 7.44 (t, 1H, J¼7.70 Hz), 7.60 (d, 1H, J¼7.70 Hz), 7.91
JHeF¼5.2 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d
¼108.54 (d,
(d, 1H, J¼7.70 Hz); 13C NMR (100 MHz, CDCl3):
¼98.34, 119.26,
d
JCeF¼3.81 Hz), 116.83 (d, JCeF¼22.89 Hz), 118.00, 134.66 (d,
JCeF¼8.58 Hz), 165.01 (d, JCeF¼257.49 Hz).
120.58, 128.24, 133.64, 134.20, 139.49.
4.3.15. 1-Cyanonaphthalene (2o). Mp 35e36 ꢀC (commercial, mp
36e38 ꢀC); IR (neat): 2222 cmꢁ1; 1H NMR (500 MHz, CDCl3):
4.3.3. 4-Chlorobenzonitrile (2c). Mp 92e94 ꢀC (commercial, mp
d¼7.51
92 C); IR (Nujol): 2225 cmꢁ1; 1H NMR (500 MHz, CDCl3):
d
¼7.47 (d,
(dd, 1H, J¼7.25, 8.38 Hz), 7.61 (t, 1H, J¼8.38 Hz), 7.68 (t, 1H,
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2H, J¼8.61 Hz), 7.61 (d, 2H, J¼8.61 Hz); 13C NMR (125 MHz, CDCl3):
J¼8.38 Hz), 7.88e7.93 (m, 2H), 8.06 (d, 1H, J¼8.38 Hz), 8.22 (d, 1H,
d
¼110.77, 117.94, 129.67, 133.35, 139.54.
J¼8.38 Hz); 13C NMR (125 MHz, CDCl3):
¼110.09, 117.75, 124.84,
d
125.05, 127.47, 128.52, 128.59, 132.26, 132.55, 132.83, 133.21.
4.3.4. 4-Bromobenzonitrile (2d). Mp 114e115 ꢀC (commercial, mp
113 C); IR (Nujol): 2223 cmꢁ1; 1H NMR (500 MHz, CDCl3):
d
¼7.53
4.3.16. 2-Cyanonaphthalene (2pꢁ).1 Mp 66e67 ꢀC (commercial, mp
ꢀ
€
(d, 2H, J¼8.59 Hz), 7.64 (d, 2H, J¼8.59 Hz); 13C NMR (125 MHz,
67 C). IR (Nujol): 2225 cm
d
;
1H NMR (500 MHz, CDCl3):
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CDCl3):
d
¼111.23, 118.03, 128.00, 132.63, 133.39.
¼7.58e7.68 (m, 3H), 7.87e7.95 (m, 3H), 8.24 (s, 1H); 13C NMR
(125 MHz, CDCl3):
d
¼110.09, 117.75, 124.84, 125.05, 127.47, 128.52,
4.3.5. 4-Nitrobenzonitrile (2e). Mp 145e147 ꢀC (commercial, mp
128.59, 132.26, 132.55, 132.83, 133.21.
147 C); IR (Nujol): 2232 cmꢁ1; 1H NMR (500 MHz, CDCl3):
d
¼7.90
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(d, 2H, J¼8.90 Hz), 8.37(d, 2H, J¼8.90 Hz); 13C NMR (125 MHz,
4.3.17. 4-Cyanobiphenyl (2q). Mp 84e86 ꢀC (commercial, mp
87 C). IR (Nujol): 2226 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d
¼7.42 (t,
1H, J¼7.25 Hz), 7.48 (t, 2H, J¼7.25 Hz), 7.59 (d, 2H, J¼7.25 Hz), 7.70
(m, 4H); 13C NMR (100 MHz, CDCl3):
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CDCl3):
d
¼116.77, 118.32, 124.27, 133.45, 150.02.
4.3.6. 4-Methylbenzonitrile (2f). Colorless oil (commercial); IR
d
¼110.90, 118.91, 127.20,
(neat): 2228 cmꢁ1
;
1H NMR (500 MHz, CDCl3):
d
¼2.42(s, 3H), 7.27
127.71, 128.63, 129.09, 132.57, 139.16, 145.65.
(d, 2H, J¼8.60 Hz), 7.53 (d, 2H, J¼8.60 Hz); 13C NMR (125 MHz,
CDCl3):
d
¼21.74, 109.21, 119.07, 129.76, 131.95, 143.63.
4.3.ꢀ18. 3-Cyanopyridine (2r). Mp 49e51 ꢀC (commercial, mp
50 C); IR (Nujol): 2229 cmꢁ1; 1H NMR (500 MHz, CDCl3):
d
¼7.46
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4.3.7. 4-Methoxybenzonitrile (2g). Mp 60e62 ꢀC (commercial, mp
(ddd, 1H, J¼7.95, 4.87, 0.86 Hz), 7.99 (dt, 1H, J¼7.95, 2.00 Hz),
60 C); IR (Nujol): 2217 cmꢁ1; 1H NMR (500 MHz, CDCl3):
d
¼3.86(s,
8.83(dd, 1H, J¼4.87, 2.00 Hz), 8.91 (sd, 1H, J¼2.00 Hz); 13C NMR
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3H), 6.95 (d, 2H, J¼8.38 Hz), 7.59 (d, 2H, J¼8.38 Hz); 13C NMR
(125 MHz, CDCl3):
152.98.
d
¼110.13, 116.46, 123.59, 139.20, 152.47,
(125 MHz, CDCl3):
d¼55.51, 103.94, 114.71, 119.19, 133.94, 162.81.
4.3.8. 3,4,5-Trimethoxybenzonitrileꢁ1(2h). Mp 92e94 ꢀC (lit.12 Mp
4.3.19. 2-Cyanothiophene (2s). Colorless oil (commercial); IR (neat):
2222 cmꢁ1 1H NMR (500 MHz, CDCl3):
¼7.14 (dd, 1H, J¼4.98,
1H NMR (500 MHz, CDCl3):
;
d
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92e94 C); IR (Nujol): 2224 cm
;
d
¼3.88 (s, 6H), 3.90 (s, 3H), 6.87 (s, 2H); 13C NMR (125 MHz, CDCl3):
3.85 Hz), 7.62 (dd, 1H, J¼4.98, 1.13 Hz), 7.64 (dd, 1H, J¼3.85, 1.13 Hz);
d¼56.33, 60.99, 106.65, 109.39, 118.90, 142.29, 153.51.
13C NMR (125 MHz, CDCl3):
d¼109.80, 114.14, 127.56, 132.51, 137.34.
4.3.9. Pꢀiperonylonitrile (2i). Mp ꢁ190e92 ꢀC (commercial, mp
4.3.20. Decanenitrile (2u). Colorless oil (commercial); IR (Nujol):
€
1H NMR (400 MHz, CDCl3):
2247 cmꢁ1
;
1H NMR (400 MHz, CDCl3):
d
¼0.88 (t, 3H, J¼6.90 Hz),
€
91e93 C). IR (Nujol): 2222 cm
;
d
¼6.07 (s, 2H), 6.87 (d, 1H, J¼8.15 Hz), 7.04 (d, 1H, J¼1.59 Hz), 7.22
1.22e1.29 (m, 10H), 1.41e1.48 (m, 2H), 1.62e1.69 (m, 2H), 2.34 (t,
(dd, 1H, J¼8.15, 1.59 Hz); 13C NMR (100 MHz, CDCl3):
d¼102.18,
2H, J¼7.10 Hz): 13C NMR (100 MHz, CDCl3):
d
¼14.1, 17.1, 22.6, 25.3,
104.96, 109.11, 111.40, 118.87, 128.21, 148.02, 151.51.
28.6, 28.7, 29.1, 29.2, 31.8, 119.9.
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4.3.10. 4-(tert-Butyl)benzonitrile (2j). Colorless oil (commercial); IR
4.3.21. Dodecanenitrile (2v). Colorless oil (commercial); IR (Nujol):
(neat): 2227 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d
¼1.31 (s, 9H), 7.46
2246 cmꢁ1
;
1H NMR (500 MHz, CDCl3):
d
¼0.88 (t, 3H, J¼6.90 Hz),
(d, 2H, J¼8.60 Hz), 7.57 (d, 2H, J¼8.60 Hz); 13C NMR (100 MHz,
1.24e1.40 (m, 14H), 1.40e1.48 (m, 2H), 1.66 (quintet, 2H, J¼7.16 Hz),
CDCl3):
d
¼30.88, 35.20, 109.24, 119.11, 126.11, 131.90, 156.58.
2.33 (t, 2H, J¼7.16 Hz); 13C NMR (125 MHz, CDCl3):
¼14.09, 17.11,
d
22.65, 25.36, 28.65, 28.75, 29.28(d), 29.48, 29.53, 31.86, 119.86.
4.3.11. 4-(Dimethyl)aminobenzonitrile (2k). Mp 75e77 ꢀC (com-
ꢁ1
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mercial, mp 75 C). IR (Nujol): 2210 cm
;
1H NMR (500 MHz,
4.3.22. Tetradecanꢁe1nitrile (2w). Colorless oil (commercial); IR
1H NMR (500 MHz, CDCl3):
d
¼0.88 (t, 3H,
€
(Nujol): 2247 cm
CDCl3):
d
¼3.04 (s, 6H), 6.64 (d, 2H, J¼7.00 Hz), 7.46 (d, 2H,
;
J¼7.00 Hz); 13C NMR (125 MHz, CDCl3):
d
¼39.91, 97.35, 111.36,
J¼6.70 Hz), 1.24e1.34 (m, 18H), 1.41e1.48 (m, 2H), 1.62e1.69 (m, 2H),
120.71, 133.27, 152.43.
2.33(t,2H,J¼7.20 Hz); 13CNMR(125MHz,CDCl3):
¼14.08,17.08,22.65,
d
25.34, 28.63, 28.72, 29.26, 29.31, 29.46, 29.55, 29.60(d), 31.88,119.82.
4.3.12. 3-Methylbenzonitrile (2l). Colorless oil (commercial); IR
(neat): 2229 cmꢁ1
;
1H NMR (500 MHz, CDCl3):
d
¼2.39 (s, 3H),
4.3.23. Hexadecanenitrile (2x). Oil. IR (neat): 2247 cmꢁ1 1H NMR
;
7.33e7.37 (m, 1H), 7.40 (d, 1H, J¼8.05 Hz), 7.43e7.47 (m, 2H); 13C
(400 MHz, CDCl3):
d
¼0.88 (t, 3H, J¼6.78 Hz), 1.24e1.34 (m, 22H),
NMR (125 MHz, CDCl3):
132.33, 133.53, 139.11.
d¼21.01, 112.11, 118.90, 128.88, 129.13,
1.40e1.49 (m, 2H), 1.57e1.70 (m, 2H), 2.33 (t, 2H, J¼7.13 Hz); 13C
NMR (125 MHz, CDCl3):
d
¼14.08, 17.08, 22.65, 25.34, 28.63, 28.73,
29.27, 29.32, 29.46, 29.56, 29.61(q), 31.89, 119.82.
4.3.13. 2-Methylbenzonitrile (2m). Colorless oil (commercial); IR
(neat): 2225 cmꢁ1; 1H NMR (500 MHz, CDCl3):
¼2.55 (s, 3H), 7.27
(t, 1H, J¼7.73 Hz), 7.32 (d, 1H, J¼7.73 Hz), 7.48 (t, 1H, J¼7.73 Hz), 7.59
d
4.3.24. 3-Phenylpropanenitrile (2y). Colorless oil (commercial); IR
(neat): 2247 cmꢁ1
;
1H NMR (500 MHz, CDCl3):
d
¼2.59 (t, 2H,