4-(Allyloxy)benzonitrile.28 (2g). Colorless solid; Yield – 83%;
mp: 43–46 °C (lit.3 43–44 °C); Rf (25% EtOAc–hexane) 0.5;
Prepared as given in the general experimental procedure. IR
7.21 (d, J = 8.04 Hz, 1H), 7.03 (s, 1H), 6.86 (d, J = 8.08 Hz,
1H), 6.07 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 151.5, 147.9,
128.2, 118.9, 111.3, 109.1, 104.9, 102.2; HRESI-MS (m/z): Cal-
culated for C8H5NO2 (M + H): 148.0399, found (M + H):
148.0394.
1
(Neat, cm−1): 2223.73; H NMR (400 MHz, CDCl3): δ 7.57 (d,
J = 8.76 Hz, 2H), 6.96 (d, J = 8.72 Hz, 2H), 6.08–5.98 (m, 1H),
5.42 (d, J = 17.24 Hz, 1H), 5.33 (d, J = 10.52 Hz, 1H), 4.59 (dd,
J1 = 0.92 Hz, J2 = 5.36 Hz, 2H); 13C NMR (100 MHz, CDCl3):
δ 161.8, 133.9, 132.0, 119.1, 118.4, 115.3, 104.0, 69.0;
HRESI-MS (m/z): Calculated for C10H9NO (M + Na): 182.0582,
found (M + Na): 182.0597.
Pyridine-2-carbonitrile.31 (2n). Colorless solid; Yield – 80%;
mp: 46–49 °C (lit.3 45–48 °C); Rf (25% EtOAc–hexane) 0.4;
Prepared as given in the general experimental procedure. IR
1
(Neat, cm−1); 2221.5; H NMR (400 MHz, CDCl3): δ 8.74 (d, J
= 4.48 Hz, 1H), 7.87 (t, J = 7.76 Hz, 1H), 7.72 (d, J = 7.72 Hz,
1H), 7.55 (t, J = 5.48 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ
151.1, 137.0, 134.0, 128.5, 126.9, 117.1069; HRESI-MS (m/z):
Calculated for C6H4N2 (M + H): 105.0453, found (M + H):
105.0461.
Cinnamonitrile.6a (2h). Colorless liquid; Yield – 85%; Rf
(25% EtOAc–hexane) 0.50; Prepared as shown in general exper-
1
imental procedure. IR (Neat): 2218 cm−1, H NMR (400 MHz,
CDCl3): δ 7.46–7.37 (m, 6H), 5.87 (d, J = 16.68 Hz, 1H); 13C
NMR (100 MHz, CDCl3): δ 150.5, 133.5, 131.2, 129.1, 127.3,
118.1, 96.3; HRESI-MS (m/z): Calculated for C9H7N (M + H):
130.0657, found (M + H): 130.0644.
4-((6-Azidohexyl)oxy)-3,5-dimethoxybenzonitrile (2p). Color-
less Liquid; Yield – 77%; Rf (25% EtOAc–hexane) 0.6; Prepared
as given in the general experimental procedure. IR (Neat, cm−1);
1
4-(Prop-2-yn-1-yloxy)benzonitrile (2i). Colorless solid; Yield
– 81%; mp: 111–113 °C; Rf (25% EtOAc–hexane) 0.5; Prepared
as shown in general experimental procedure. IR (Neat, cm−1):
2226.9, 2094.4; H NMR (400 MHz, CDCl3): δ 6.85 (s, 2H),
4.02 (t, J = 6.56 Hz, 2H), 3.86 (s, 6H), 3.28 (t, J = 6.88 Hz, 2H),
1.79–1.72 (m, 2H), 1.67–1.60 (m, 2H), 1.53–1.41 (m, 4H); 13C
NMR (100 MHz, CDCl3): δ 153.8, 141.7, 119.0, 109.5, 106.5,
73.4, 56.3, 51.4, 29.9, 28.8, 26.4, 25.3; HRESI-MS (m/z): Calcu-
lated for C15H20N4O3 (M + Na): 327.1433, found (M + H):
327.1432.
1
2223; H NMR (400 MHz, CDCl3): δ 7.61 (d, J = 8.8 Hz, 2H),
7.04 (d, J = 8.76 Hz, 2H), 4.76 (d, J = 2.12 Hz, 2H), 2.57 (t, J =
2 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 160.6, 133.9, 118.9,
115.6, 104.9, 76.7, 76.5, 55.9; HRESI-MS (m/z): Calculated for
C10H7NO (M + H): 158.0606, found (M + H): 158.0602.
1-Naphthonitrile.6a (2j). Colorless solid; Yield – 79%; mp:
55–57 °C (lit.3 56–58 °C); Rf (25% EtOAc–hexane) 0.5; Pre-
pared as given in the general experimental procedure. IR (Neat,
Acknowledgements
This work is funded by Indian Institute of Science, CSIR, New-
Delhi (No. 01(2415)/10/EMR-II) and RL Fine Chem. Thanks
are due to Dr A. R. Ramesha and Prof. S. Chandrasekhar for
encouragement and useful discussions. M. L. thanks CSIR,
New-Delhi for a senior research fellowship.
1
cm−1); 2222; H NMR (400 MHz, CDCl3): δ 8.24 (d, J = 8.28
Hz, 1H), 8.08 (d, J = 8.28 Hz, 1H), 7.93–7.90 (m, 2H), 7.70 (t,
J = 7.68 Hz, 1H), 7.62 (t, J = 7.28 Hz, 1H), 7.53 (t, J = 7.72 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ 133.3, 132.9, 132.6,
132.3, 128.6, 128.5, 127.5, 125.1, 124.9, 117.8, 110.1;
HRESI-MS (m/z): Calculated for C11H7N (M + H): 154.0657,
found (M+): 154.0648.
References
1 (a) A. J. Fatiadi, in Preparation and Synthetic Applications of Cyano
Compounds, ed. S. Patai and Z. Rappaport, Wiley, New York, 1983;
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W. G. Dauben, Wiley, New York, vol. 31, 1984, pp. 1–374; (c) R.
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2001, 34, 563; (f) M. B. Smith and J. March, March’s Advanced Organic
Chemistry: Reactions, Mechanisms, and Structure, Wiley, Hoboken, NJ,
6th edn, 2007.
4-Nitrobenzonitrile.6a (2k). Colorless solid; Yield – 91%; mp:
147–149 °C (lit.3 148–149 °C); Rf (25% EtOAc–hexane) 0.5;
Prepared as given in the general experimental procedure. IR
(Neat, cm−1); 2222; 1H NMR (400 MHz, CDCl3): δ 8.37 (d, J =
8.96 Hz, 2H), 7.90 (d, J = 8.92 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 150.0, 133.4, 124.2, 118.3, 116.8; Anal. Calcd for
C7H4N2O2 C, 56.76; H, 2.72; N, 18.91; Found: C, 56.67; H,
3.26; N, 19.14.
2 (a) F. Hagedorn, H. P. Gelbke, in Ullmanns Enzyklopadie der Tech-
nischen Chemie, ed. E. Bartholome, E. Biekert, H. Hellmann, H. Ley,
W. M. Weigert and E. Weise, Verlag Chemie, Weinheim, 4th edn, 1979,
vol. 17, p. 333; (b) G. P. Ellis and T. M. Romney-Alexander, Chem. Rev.,
1987, 87, 779; (c) V. V. Grushin and H. Alper, Chem. Rev., 1994, 94,
1047; (d) L. R. Subramanian, Science of Synthesis, Georg Thieme, Stutt-
gart, 2004, vol. 19, p. 163.
3 (a) K. W. Rosenmund and E. Struck, Ber. Dtsch. Chem. Ges., 1919, 2,
1749; (b) D. F. Mowry, Chem. Rev., 1948, 42, 189; (c) K. Friedrich, and
K. Wallenfels, in The Chemistry of the Cyano Group, ed. Z. Rappoport,
Interscience, London, 1970, p. 67; (d) J. Lindley, Tetrahedron, 1984, 40,
1433; (e) P. Kurtz in Houben-Weyl, Methoden der Organischen Chemie,
ed. E. Muller, Georg Thieme, Stuttgart, 4th edn, 1952, Part III, vol. 8,
p. 302.
Methyl 2-cyanobenzoate.29 (2l). Colorless solid; Yield – 83%;
mp: 50–53 °C (lit.3 50–52 °C); Rf (25% EtOAc–hexane) 0.4;
Prepared as given in the general experimental procedure. IR
1
(Neat, cm−1); 2229; H NMR (400 MHz, CDCl3): δ 8.16–8.14
(m, 1H), 7.83–7.81 (m, 1H), 7.71–7.65 (m, 2H), 4.01 (s, 3H);
13C NMR (100 MHz, CDCl3): δ 164.5, 134.8, 132.7, 132.5,
132.4, 131.2, 117.5, 112.9, 52.8; HRESI-MS (m/z): Calculated
for C9H7NO2 (M + Na): 184.0374, found (M + Na): 184.0382.
Benzo[d][1,3]dioxole-5-carbonitrile.30 (2m). Colorless solid;
Yield – 82%; mp: 89–92 °C (lit.3 90–93 °C); Rf (25% EtOAc–
hexane) 0.5; Prepared as given in the general experimental pro-
4 (a) M. Sundermeier, A. Zapf and M. Beller, Chem. Commun., 2004,
1388; (b) D. Wang, L. Kuang, Z. Li and K. Ding, Synlett, 2008, 69;
(c) H.-J. Cristau, A. Ouali, J.-F. Spindler and M. Taillefer, Chem.–Eur. J.,
1
cedure. IR (Neat, cm−1); 2226; H NMR (400 MHz, CDCl3): δ
2758 | Org. Biomol. Chem., 2012, 10, 2753–2759
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