G. Ishii et al. / Tetrahedron 69 (2013) 1462e1469
1467
(
(
1
d, J¼8.0 Hz, 1H), 7.10 (s, 1H), 7.05 (d, J¼8.0 Hz, 1H), 2.47 (s, 3H), 2.36
2H), 7.49 (t, J¼7.3 Hz, 2H), 7.44 (t, J¼7.3 Hz, 1H); 13C NMR (CDCl
3
,
s, 3H); 13C NMR (CDCl
, 125 MHz):
d
¼143.4, 141.6, 132.2, 130.9,
125 MHz):
110.8.
d
¼145.6, 139.0, 132.5, 129.0, 128.6, 127.6, 127.1, 118.9,
3
26.9, 118.3, 109.5, 21.6, 20.2.
ꢀ
4
6
d
.3.5. 3,4-Dimethyl-1-benzonitrile. Mp 63e64 C (commercial, mp
4.3.16. 4-Fluoro-1-benzonitrile. Colorless oil (commercial); IR
ꢀ
ꢁ1
1
ꢁ1
1
4e67 C); IR (N u€ jol): 2224 cm
;
H NMR (CDCl
, 500 MHz):
(neat): 2232 cm
;
H NMR (CDCl
, 400 MHz):
d
¼7.70 (dd,
3
3
¼7.41 (s, 1H), 7.39 (d, J¼7.8 Hz, 1H), 7.21 (d, J¼7.8 Hz, 1H), 2.32 (s,
J
HeF¼5.2 Hz, JHeH¼9.0 Hz, 2H), 7.20 (tt, JHeF¼8.6 Hz, JHeH¼9.0 Hz,
H), 2.29 (s, 3H); 13C NMR (CDCl
, 125 MHz):
d¼142.4, 137.8, 132.8,
2H); C NMR (CDCl
13
, 125 MHz):
d¼165.0 (JCeF¼130 Hz), 134.7
3
3
3
130.2, 129.6, 119.3, 109.4, 20.1, 19.5.
(JCeF¼10.0 Hz), 118.0, 116.8 (JCeF¼2.2 Hz), 108.6.
ꢀ
4
.3.6. 2,5-Dimethyl-1-benzonitrile. Colorless oil (commercial); IR
4.3.17. 4-Chloro-1-benzonitrile. Mp 92e95 C (commercial, mp
ꢁ1
1
ꢀ
ꢁ1
1
(
neat): 2227 cm ; H NMR (CDCl
3
, 500 MHz):
d
¼7.36 (s, 1H), 7.27
90e93 C); IR (N u€ jol): 2226 cm
d
;
H NMR (CDCl
3
, 400 MHz):
13
13
(
d, J¼7.9 Hz, 1H), 7.18 (d, J¼7.9 Hz, 1H), 2.48 (s, 3H), 2.33 (s, 3H);
C
¼7.61 (d, J¼8.8 Hz, 2H), 7.48 (d, J¼8.8 Hz, 2H); C NMR (CDCl
3
,
NMR (CDCl
3
, 125 MHz):
d¼138.4, 135.8, 133.3, 132.3, 129.8, 118.0,
125 MHz):
d¼139.5, 133.3, 129.6, 117.9, 110.7.
112.2, 20.3, 19.6.
ꢀ
.3.18. 4-Bromo-1-benzonitrile. Mp 106e107 C (commercial, mp
4
ꢀ
ꢀ
ꢁ1 1
4
.3.7. 2,4,6-Trimethyl-1-benzonitrile. Mp 50e51 C (commercial,
113 C); IR (N u€ jol): 2224 cm ; H NMR (CDCl
(dt, J¼8.6, 2.1 Hz, 2H), 7.53 (dt, J¼8.9, 2.0 Hz); C NMR (CDCl
125 MHz):
¼133.4, 132.6, 128.0, 118.0, 111.2.
3
, 400 MHz):
d
¼7.64
ꢀ
ꢁ1
1
13
mp 54e55 C); IR (N u€ jol): 2218 cm ; H NMR (CDCl
, 500 MHz):
, 125 MHz):
3
,
3
13
d
¼6.93 (s, 2H), 2.48 (s, 6H), 2.32 (s, 3H); C NMR (CDCl
3
d
d¼142.7, 141.9, 128.1, 117.6, 110.2, 21.5, 20.6.
ꢀ
.3.19. 2,5-Dichloro-1-benzonitrile. Mp 122e125 C (commercial,
4
ꢀ
ꢀ
mp 128e132 C); IR (N u€ jol): 2230 cm ; H NMR (CDCl
, 500 MHz):
3
ꢁ1 1
4
.3.8. 4-Methoxy-1-benzonitrile. Mp 54e55 C (commercial, mp
ꢀ
ꢁ1
1H NMR (CDCl
5
7e59 C); IR (N u€ jol): 2216 cm
;
3
, 500 MHz):
d
¼7.66 (d, J¼2.6 Hz, 1H), 7.52 (dd, J¼10.0, 2.6 Hz, 1H), 7.46 (d,
13
13
d
¼7.59 (d, J¼8.9 Hz, 2H), 6.95 (d, J¼8.9 Hz, 2H), 3.86 (s, 3H);
C
J¼10.0 Hz, 1H); C NMR (CDCl
3
, 100 MHz):
d
¼135.3, 134.1, 133.5,
NMR (CDCl
3
, 125 MHz):
d
¼55.5, 103.8, 114.7, 119.2, 133.9, 162.8.
133.3, 131.2, 114.7 (2C).
ꢀ
ꢀ
4
.3.9. 2,4-Dimethoxy-1-benzonitrile. Mp 93e94 C (commercial,
4.3.20. 2,6-Dichloro-1-benzonitrile. Mp 142e145 C (commercial,
ꢀ
ꢁ1
1
ꢀ
ꢁ1 1
mp 93e94 C); IR (N u€ jol): 2219 cm ; H NMR (CDCl
3
, 500 MHz):
mp 143e146 C); IR (N u€ jol): 2231 cm ; H NMR (CDCl
, 400 MHz):
¼138.5, 133.8,
3
13
d
¼7.48 (d, J¼8.5 Hz, 1H), 6.51 (d, J¼8.5 Hz, 1H), 6.46 (s, 1H), 3.90 (s,
d
¼7.50e7.42 (m, 3H); C NMR (CDCl
3
, 125 MHz): d
3
H), 3.86 (s, 3H); 13C NMR (CDCl
3
, 125 MHz):
d
¼164.6, 162.8, 134.8,
128.1, 114.5, 113.3.
116.9, 105.7, 98.4, 93.8, 55.9, 55.6.
4
.3.21. 2-Cyanothiophene. Colorless oil (commercial); IR (neat):
ꢀ
ꢁ1 1
;
4
.3.10. 2,4,6-Trimethoxy-1-benzonitrile. Mp 139e140 C (commer-
2222 cm
H NMR (CDCl
3
, 400 MHz):
d
¼7.65 (d, J¼3.8 Hz, 1H),
ꢀ
ꢁ1
1
13
cial, mp 143e145 C); IR (N u€ jol): 2212 cm
5
;
H NMR (CDCl
,
,
7.62 (d, J¼5.0 Hz, 1H), 7.75 (dd, J¼5.0, 3.8 Hz, 1H); C NMR (CDCl
3
,
3
13
00 MHz):
d
¼6.09 (s, 2H), 3.88 (s, 6H), 3.86 (s, 3H); C NMR (CDCl
3
125 MHz):
d¼137.3, 132.5, 127.6, 114.2, 109.8.
125 MHz):
d
¼165.3, 163.8, 114.6, 90.3, 84.0, 56.0, 55.6.
ꢀ
(lit.,16 mp
43e44 C); IR (N u€ jol): 2214 cm ; 1H NMR (CDCl
ꢀ
3
, 400 MHz);
4
.3.22. 4-Allyloxy-1-benzonitrile. Mp 42e44
C
ꢀ
ꢁ1
4
.3.11. 4-(N,N-Dimethylamino)-1-benzonitrile. Mp 74e75 C (com-
ꢀ
ꢁ1
1
mercial, mp 75 C); IR (N u€ jol): 2210 cm
;
H NMR (CDCl
,
d
¼7.58 (dt, J¼9.0, 2.4 Hz, 2H), 6.96 (dt, J¼8.8, 2.4 Hz, 2H), 6.00e6.10
3
5
6
3
00 MHz):
H); C NMR (CDCl
9.9.
d
¼7.47 (d, J¼9.1 Hz, 2H), 6.64 (d, J¼9.1 Hz, 2H), 3.04 (s,
(m, 1H), 5.42 (dq, J¼17.2, 1.5 Hz, 1H), 5.34 (dq, J¼10.4, 1.3 Hz, 1H),
13
13
3
, 125 MHz):
d
¼152.4, 133.3, 120.7, 111.3, 97.2,
4.59 (dt, J¼5.5, 1.4 Hz, 2H); C NMR (CDCl
3
, 125 MHz):
d
¼161.8,
113.9, 132.0, 119.7, 118.5, 115.4, 104.0, 69.0; HRMS (APCI) Calcd for
C
10
H
10NO (M þ H) 169.0762. Found 169.0757.
1
5
4
2
7
1
.3.12. 2-Isopropyl-1-benzonitrile. Colorless oil (lit. ); IR (neat):
ꢁ1
1
ꢀ
222 cm ; H NMR (CDCl
3
, 400 MHz):
d
¼7.60 (dd, J¼7.6,1.2 Hz,1H),
4.3.23. Piperonylonitrile. Mp 89e92
93e95 C); IR (N u€ jol): 2222 cm
C
(commercial, mp
, 500 MHz):
ꢀ
ꢁ1
1
.54 (td, J¼7.6,1.2 Hz,1H), 7.39 (d, J¼7.5 Hz,1H), 7.27 (td, J¼7.6,1.2 Hz,
;
H NMR (CDCl
3
1
3
H), 3.39 (sep, J¼6.9 Hz, 1H), 1.32 (d, J¼9.3 Hz, 6H); C NMR (CDCl
25 MHz):
HRMS (APCI) Calcd for C10
3
,
d
¼7.21 (dd, J¼8.0, 1.7 Hz, 1H), 7.04 (d, J¼1.7 Hz, 1H), 6.87 (d, J¼8.0,
13
1
d
¼152.4, 133.0, 132.8, 126.7, 125.9, 118.1, 111.6, 32.4, 23.2;
1H), 6.07 (s, 2H): C NMR (CDCl
188.8, 111.4, 109.1, 104.9, 102.2.
3
, 125 MHz);
d
¼151.5, 148.0, 128.2,
H
12N 146.0970. Found 146.0967.
ꢀ
17
4
3
d
.3.13. 1-Naphthonitrile. Mp 35e36
C
(commercial, mp
, 500 MHz):
4.3.24. 4-(Methoxymethoxy)-1-benzonitrile. Colorless oil (lit. ); IR
ꢀ
ꢁ1
1
ꢁ1 1
6e38 C); IR (N u€ jol): 2219 cm
;
H NMR (CDCl
(neat): 2225 cm
2.0 Hz, 2H), 7.10 (dt, J¼8.4, 2.3 Hz, 2H), 5.22 (s, 2H), 3.47 (s, 3H);
NMR (CDCl ,125 MHz):
;
H NMR (CDCl
, 500 MHz):
d
¼7.59 (dt, J¼8.4,
3
3
13
¼8.22 (d, J¼8.2 Hz, 1H), 8.05 (d, J¼8.2 Hz, 1H), 7.91 (d, J¼7.9 Hz,
C
1
1
1
H), 7.89 (d, J¼7.9 Hz, 1H), 7.67 (t, J¼8.2 Hz, 1H), 7.59 (t, J¼8.2 Hz,
3
d
¼160.5,133.9,119.0,116.7,105.0, 94.1, 56.3;
13
H), 7.49 (t, J¼7.9 Hz, 1H); C NMR (CDCl
3
, 125 MHz):
d¼133.2,
9 2
HRMS (APCI) Calcd for C H10NO
(M þ H) 164.0712. Found 164.0706.
32.8, 132.5, 132.2, 128.5, 128.4, 127.4, 124.9, 124.8, 117.7, 110.0.
0
4
.3.25. 4-Cyano-4 -pentylbiphenyl. Colorless oil (commercial, mp
ꢀ
ꢀ
ꢁ1 1
4.3.14. 2-Naphthonitrile. Mp 68e70
C
(commercial, mp
23 C); IR (neat): 2226 cm ; H NMR (CDCl
3
, 400 MHz):
d
¼7.69 (q,
ꢀ
ꢁ1
1
6
d
6e70 C); IR (N u€ jol): 2225 cm
;
H NMR (CDCl , 500 MHz):
3
J¼8.0 Hz, 4H) 7.51 (d, J¼8.4 Hz, 2H) 7.29 (d, J¼8.4 Hz, 2H), 2.68 (t,
J¼7.7 Hz, 2H), 1.65 (quint, J¼7.5 Hz, 2H), 1.40e1.31 (m, 4H), 0.90 (t,
13
¼8.24 (s, 1H), 7.93e7.88 (m, 3H), 7.68e7.58 (m, 3H); C NMR
13
(
CDCl , 125 MHz):
3
d
¼134.6, 134.1, 132.2, 129.2, 129.0, 128.4, 128.0,
J¼7.2 Hz, 3H); C NMR (CDCl
3
, 100 MHz):
d
¼145.6, 143.8, 136.4,
127.6, 126.3, 119.2, 109.3.
132.5, 129.2, 127.4, 127.0, 119.0, 110.5, 35.6, 31.5, 31.1, 22.5, 14.0.
ꢀ
4
8
d
.3.15. 4-Cyanobiphenyl. Mp 85e88
C
(commercial, mp
4.3.26. Nonanecarbonitrile. Colorless oil (commercial); IR (neat):
ꢀ
ꢁ1
1
ꢁ1 1
5e87 C); IR (N u€ jol): 2225 cm
;
H NMR (CDCl , 500 MHz):
¼7.73 (d, J¼8.8 Hz, 2H), 7.69 (d, J¼8.8 Hz, 2H), 7.59 (d, J¼7.3 Hz,
2247 cm ; H NMR (CDCl
3
, 500 MHz):
d
¼2.40 (t, J¼7.3 Hz, 2H),1.60
3
(quint, J¼7.3 Hz, 2H),1.50 (quint, J¼7.3 Hz, 2H),1.2e1.4 (m, 8H), 0.90