Y. Suzuki et al. / Tetrahedron 67 (2011) 3809e3814
3813
4.2. Typical experimental procedure for the conversion of
N,N-dialkyl amides (1) into nitriles (2)
d
d
¼6.87 (s, 2H), 3.90 (s, 3H), 3.88 (s, 6H); 13C NMR (125 MHz, CDCl3)
¼153.5, 142.3, 118.9, 109.4, 106.7, 61.0, 56.3.
To a solution of N,N-dimethyl benzamide (298 mg, 2 mmol) in
dry THF (4 mL) was added DIBAL-H (1.04 M in hexane, 2.3 mL,
1.2 equiv) at ꢁ78 ꢀC. The mixture was stirred for 1.5 h under an
argon atmosphere at from ꢁ70 ꢀC to ꢁ40 ꢀC slowly. Then, aq NH3
(concentration: 28.0e30.0%, 4 mL) and I2 (762 mg, 3.0 equiv) were
added at 0 ꢀC, and the reaction mixture was stirred for 2 h at room
temperature. Reaction mixture was poured into saturated aq
Na2SO3 solution (10 mL) and extracted with ethyl acetate
(15 mLꢂ3). The organic layer was dried over Na2SO4. After removal
of the solvent under reduced pressure, the residue was purified by
short column chromatography on silica gel (eluent: hexane/ethyl
acetate¼4:1) to afford benzonitrile in 67% yield (138 mg).
4.2.11. 1-Naphthonitrile. Mp 35e36 ꢀC (commercial, mp 36e38 ꢀC);
IR (neat): 2222 cmꢁ1 1H NMR (500 MHz, CDCl3)
;
d¼8.22 (d, 1H,
J¼8.38 Hz), 8.06 (d, 1H, J¼8.38 Hz), 7.93e7.88 (m, 2H), 7.68 (t, 1H,
J¼8.38 Hz), 7.61 (t, 1H, J¼8.38 Hz), 7.51 (dd, 1H, J¼7.25 Hz, 8.38 Hz);
13C NMR (125 MHz, CDCl3)
127.5, 125.1, 124.8, 117.8, 110.1.
d
¼133.2, 132.8, 132.6, 132.3, 128.6, 128.5,
4.2.12. 2-Naphthonitrile. Mp
6ꢁ81e70 ꢀC
(commercial,
mp
66e67 ꢀC); IR (Nujol): 2225 cm
;
1H NMR (500 MHz, CDCl3)
d
¼8.24 (s, 1H), 7.95e7.87 (m, 3H), 7.68e7.58 (m, 3H); 13C NMR
(125 MHz, CDCl3):
d
¼133.2, 132.8, 132.6, 132.3, 128.6, 128.5, 127.5,
125.1, 124.8, 117.8, 110.1.
Most of the present prepared nitriles are commercially available
and they are identified with authentic nitrile compounds.
4.2.13. 2-Cyanothiophene. Colorless oil (commercial); IR (neat):
2222 cmꢁ1
;
1H NMR (500 MHz, CDCl3)
d
¼7.64 (dd, 1H, J¼3.85,
1.13 Hz), 7.62 (dd, 1H, J¼4.98, 1.13 Hz), 7.14 (dd, 1H, J¼4.98 Hz,
3.85 Hz);13C NMR (125 MHz, CDCl3)
¼137.3, 132.5, 127.6, 114.1, 109.8.
4.2.1. Benzonitrile. Colorless oil (commercial); IR (neat):
2230 cmꢁ1
;
1H NMR (500 MHz, CDCl3)
d
¼7.67 (d, 2H, J¼7.70 Hz),
d
7.61 (t, 1H, J¼7.70 Hz), 7.48 (t, 2H, J¼7.70 Hz); 13C NMR (125 MHz,
CDCl3):
d
¼132.7, 132.1, 129.1, 118.8, 112.4.
4.2.14. 3-Cyanopyridine. mp 49e51 ꢀC (commercial, mp 50 ꢀC); IR
(Nujol): 2229 cmꢁ1 1H NMR (500 MHz, CDCl3)
;
d
¼8.91 (sd, 1H,
4.2.2. p-Chlorobenzonitrile. Mp 92e94 ꢀC (commercial, mp 92 ꢀC);
J¼2.00 Hz), 8.83 (dd, 1H, J¼4.87, 2.00 Hz), 7.99 (dt, 1H, J¼7.95,
IR (Nujol): 2225 cmꢁ1
;
1H NMR (500 MHz, CDCl3)
d
¼7.61 (d, 2H,
2.00 Hz), 7.46 (ddd, 1H, J¼7.95, 4.87, 0.86 Hz); 13C NMR (125 MHz,
J¼8.61 Hz), 7.47 (d, 2H, J¼8.61 Hz); 13C NMR (125 MHz, CDCl3)
CDCl3)
d
¼153.0, 152.5, 139.2, 123.6, 116.5, 110.1.
d¼139.5, 133.4, 129.7, 117.9, 110.8.
4.2.15. Cinnamnitrile. Colorless oil (commercial); IR (neat):
4.2.3. p-Bromobenzonitrile. Mp 114e115 ꢀC (commercial, mp
2217 cmꢁ1; 1H NMR (500 MHz, CDCl3)
d
¼7.39e7.47 (m, 6H), 5.88 (d,
113 ꢀC); IR (Nujol): 2223 cmꢁ1
;
1H NMR (500 MHz, CDCl3)
d¼7.64
1H, J¼16.90 Hz); 13C NMR (125 MHz, CDCl3)
¼150.6, 133.6, 131.2,
d
(d, 2H, J¼8.59 Hz), 7.53 (d, 2H, J¼8.59 Hz); 13C NMR (125 MHz,
129.1, 127.3, 118.1, 96.3.
CDCl3)
d
¼133.4, 132.6, 128.0, 118.0, 111.2.
4.2.16. 3-Phenylpropanenitrile. Colorless oil (commercial); IR
(neat): 2247 cmꢁ1 1H NMR (500 MHz, CDCl3)
4.2.4. p-Nitrobenzonitrile. Mp 145e147 ꢀC (commercial, mp
;
d
¼7.33 (t, 2H,
147 ꢀC); IR (Nujol): 2232 cmꢁ1
;
1H NMR (500 MHz, CDCl3)
d¼8.37
J¼8.30 Hz), 7.26 (t, 1H, J¼8.30 Hz), 7.22 (d, 2H, J¼8.30 Hz), 2.93 (t,
(d, 2H, J¼8.90 Hz), 7.90 (d, 2H, J¼8.90 Hz); 13C NMR (125 MHz,
2H, J¼7.45 Hz), 2.59 (t, 2H, J¼7.45 Hz); 13C NMR (125 MHz, CDCl3):
CDCl3)
d
¼150.0, 133.5, 124.3, 118.2, 116.8.
d
¼138.0, 128.7, 128.2, 127.1, 119.0, 31.4, 19.2.
4.2.5. 4-Methylbenzonitrile. Colorless oil (commercial); IR (neat):
4.3. Typical procedure for the conversion of isopropyl esters
(3) into nitriles (4)
2228 cmꢁ1
;
1H NMR (500 MHz, CDCl3)
d
¼7.53 (d, 2H, J¼8.60 Hz),
7.27 (d, 2H, J¼8.60 Hz), 2.42 (s, 3H); 13C NMR (125 MHz, CDCl3)
d
¼143.6, 132.0, 129.8, 119.1, 109.2, 21.7.
To a solution of isopropyl tetradecanoate (555 mg, 2.05 mmol)
in CH2Cl2 (2 mL) was added DIBAL-H (1.04 M in hexane, 3 mL,
1.5 equiv) at ꢁ78 ꢀC. The mixture was stirred for 3 h at ꢁ78 ꢀC
under argon atmosphere. Then, aq NH3 (6 mL), THF (3 mL), and I2
(1.85 mg, 7.30 mmol) were added. The resulting solution was
warmed to room temperature and stirred for 3 h. Reaction mixture
was poured into saturated aq Na2SO3 solution (10 mL) and extrac-
ted with chloroform (15 mLꢂ3). The organic layer was dried over
Na2SO4. After removal of the solvent under reduced pressure, the
residue was purified by short column chromatography on silica gel
to give tetradecanenitrile in 90% (386 mg).
4.2.6. 4-Methoxybenzonitrile. Mp 60e62 ꢀC (commercial, 60 ꢀC); IR
(Nujol): 2217 cmꢁ1
;
1H NMR (500 MHz, CDCl3)
d
¼7.59 (d, 2H,
J¼8.38 Hz), 6.95 (d, 2H, J¼8.38 Hz), 3.86 (s, 3H); 13C NMR (125 MHz,
CDCl3)
d
¼162.8, 133.9, 119.2, 114.7, 103.9, 55.1.
4.2.7. p-(N,N-Dimethylamino)benzonitrile. Mp 75e77 ꢀC (commer-
cial, mp 75 ꢀC); IR (neat): 2210 cmꢁ1 1H NMR (500 MHz, CDCl3)
;
d
¼7.46 (d, 2H, J¼7.00 Hz), 6.64 (d, 2H, J¼7.00 Hz), 3.04 (s, 6H); 13C
NMR (125 MHz, CDCl3)
d
¼152.4, 133.3, 120.7, 111.4, 97.4, 39.9.
4.2.8. 3-Methylbenzonitrile. Colorless oil (commercial); IR (neat):
4.3.1. Octanenitrile. Colorless oil (commercial); IR¼2247 cmꢁ1
;
1H
2229 cmꢁ1; 1H NMR (500 MHz, CDCl3)
d
¼7.43e7.47 (m, 2H), 7.40 (d,
NMR (400 MHz, CDCl3)
d
¼0.89 (t, J¼6.8 Hz, 3H), 1.27e1.38 (m, 6H),
1H, J¼8.05 Hz), 7.33e7.37 (m, 1H), 2.39 (s, 3H); 13C NMR (125 MHz,
1.41e1.48 (m, 2H),1.62e1.70 (m, 2H), 2.34 (t, J¼7.1 Hz, 2H); 13C NMR
CDCl3)
d¼139.1, 133.5, 132.3, 129.1, 128.9, 118.9, 112.1, 21.0.
(100 MHz, CDCl3)
d¼14.0, 17.1, 22.5, 25.3, 28.4, 28.6, 31.5, 119.9.
4.2.9. 2-Methylbenzonitrile. Colorless oil (commercial); IR (neat):
2225 cmꢁ1 1H NMR (500 MHz, CDCl3)
7.48 (t,1H, J¼7.73 Hz), 7.32 (d,1H, J¼7.73 Hz), 7.27 (t,1H, J¼7.73 Hz);
13C NMR (125 MHz, CDCl3), 132.6, 132.5, 130.2, 126.2, 118.1, 112.7,
20.4.
4.3.2. Decanenitrile. Colorless oil (commercial); IR¼2247 cmꢁ1; 1H
;
d
¼7.59 (d, 1H, J¼7.73 Hz),
NMR (400 MHz, CDCl3)
d
¼0.88 (t, J¼6.9 Hz, 3H), 1.22e1.29 (m, 10H),
1.41e1.48 (m, 2H),1.62e1.69 (m, 2H), 2.34 (t, J¼7.1 Hz, 2H); 13C NMR
(100 MHz, CDCl3)
119.9.
d¼14.1, 17.1, 22.6, 25.3, 28.6, 28.7, 29.1, 29.2, 31.8,
4.2.10. 3,4,5-Trimethoxybenzonitirlꢁe1. Mp 92e93 ꢀC (lit.9 mp
4.3.3. Dodecanenitrile. Colorless oil (commercial); IR¼2246 cmꢁ1
;
92e94 ꢀC); IR (Nujol): 2224 cm
;
1H NMR (500 MHz, CDCl3)
1H NMR (400 MHz, CDCl3)
d
¼0.88 (t, J¼6.9 Hz, 3H), 1.21e1.30 (m,