PAPER
One-Pot Cyanation
3237
IR (neat): 2247 cm–1 (CN).
1H NMR (500 MHz, CDCl3): δ = 2.62 (t, J = 7.5 Hz, 2 H), 2.94 (t,
J = 7.5 Hz, 2 H), 7.16–7.20 (m, 2 H), 7.30–7.34 (m, 2 H).
Phenylthioethyl Cyanide (3m)20
Yield: 33.3 mg (34%); yellow oil.
IR (neat): 2251 cm–1 (CN).
1H NMR (500 MHz, CDCl3): δ = 2.59 (t, J = 7.5 Hz, 2 H), 3.13 (t,
J = 7.5 Hz, 2 H), 7.26–7.42 (m, 3 H), 7.42–7.44 (m, 2 H).
13C NMR (125 MHz, CDCl3): δ = 19.3, 30.9, 118.7, 129.0, 129.6,
133.2, 136.4.
13C NMR (125 MHz, CDCl3): δ = 18.2, 30.2, 117.9, 127.7, 129.3,
131.4, 133.1.
MS (EI): m/z (%) = 165 (M+, 100), 166 (M+ + 1, 10), 167 (M+ + 2,
30), 168 (M+ + 3, 5).
MS (EI): m/z (%) = 163 (M+, 70), 123 (M+ – 40, 100).
4-Bromophenethyl Cyanide (3g)
Yield: 104.6 mg (83%); yellow oil.
2-Phenylethyl Cyanide (3n)21
Yield: 55.9 mg (71%); yellow oil.
IR (neat): 2247 cm–1 (CN).
IR (neat): 2248 cm–1 (CN).
1H NMR (300 MHz, CDCl3): δ = 2.62 (t, J = 7.5 Hz, 2 H), 2.96 (t,
J = 7.5 Hz, 2 H), 7.22–7.37 (m, 5 H).
1H NMR (500 MHz, CDCl3): δ = 2.61 (t, J = 7.5 Hz, 2 H), 2.9 (t,
J = 7.5 Hz, 2 H), 7.10–7.13 (m, 2 H), 7.45–7.48 (m, 2 H).
13C NMR (125 MHz, CDCl3): δ = 19.2, 30.9, 118.7, 121.2, 130.0,
13C NMR (75 MHz, CDCl3): δ = 19.3, 31.5, 119.1, 127.2, 128.2,
128.9, 138.0.
132.0, 136.9.
MS (EI): m/z (%) = 209 (M+, 70), 211 (M+ + 2, 70), 169 (M+ – 40,
MS (EI): m/z (%) = 131 (M+, 90), 91 (M+ – 40, 100).
100).
HRMS (EI): m/z calcd for C9H8BrN: 208.9840; found: 208.9830.
Acknowledgment
2-Iodophenethyl Cyanide (3h)
Yield: 111.1 mg (72%); yellow oil.
This work was partially supported by a Grant-in-Aid for Scientific
Research (C) (No. 25410120) supported by MEXT, and by a grant
from the CCIS program supported by MEXT. The authors thank
Shin-Etsu Chemical Co., Ltd., for a gift of the hydrosilanes.
IR (neat): 2247 cm–1 (CN).
1H NMR (500 MHz, CDCl3): δ = 2.63–2.68 (m, 2 H), 3.05–3.09 (m,
2 H), 6.96–6.99 (m, 1 H), 7.30–7.36 (m, 2 H), 7.83–7.85 (m, 1 H).
13C NMR (125 MHz, CDCl3): δ = 17.8, 36.5, 99.7, 118.6, 128.9,
129.2, 129.9, 139.8, 140.4.
MS (EI): m/z = 257 (M+, 100%).
Supporting Information for this article is available online at
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HRMS (EI): m/z calcd for C9H8IN: 256.9701; found: 256.9717.
4-Hydroxyphenethyl Cyanide (3i)18
Yield: 80.4 mg (91%); yellow oil.
References
(1) The Chemistry of the Cyano Group; Rappoport, Z., Ed.;
Wiley-Interscience: London, 1970.
IR (neat): 2253 cm–1 (CN).
1H NMR (300 MHz, CDCl3): δ = 2.59 (t, J = 7.5 Hz, 2 H), 2.89 (t,
J = 7.5 Hz, 2 H), 5.17 (s, 1 H), 6.77–6.81 (m, 2 H), 7.07–7.12 (m, 2
H).
13C NMR (75 MHz, CDCl3): δ = 19.7, 30.7, 115.7, 119.2, 129.5,
130.1, 154.8.
MS (EI): m/z (%) = 147 (M+, 20), 107 (M+ – 40, 100).
(2) For some recent examples of functional transformations of
cyanides, see: (a) Addis, D.; Enthaler, S.; Junge, K.; Wendt,
B.; Beller, M. Tetrahedron Lett. 2009, 50, 3654.
(b) Enthaler, S.; Addis, D.; Junge, K.; Erre, G.; Beller, M.
Chem. Eur. J. 2008, 14, 9491. (c) Saavedra, J. Z.; Resemdez,
A.; Rovira, A.; Eagon, S.; Haddenham, D.; Singaram, B. J.
J. Org. Chem. 2012, 77, 221. (d) Lee, W.-C.; Sears, J. M.;
Enow, R. A.; Eads, K.; Krogstad, D. A.; Frost, B. J. Inorg.
Chem. 2013, 52, 1737.
(3) Furukawa, N.; Kishimoto, K.; Ogawa, S.; Kawai, T.;
Fujihara, H.; Oae, S. Tetrahedron Lett. 1981, 22, 4409.
(4) For recent examples on the reactions using Me3SiCN, see:
Soleimani, E. Synlett 2007, 1625; and references cited
therein.
4-(Trifluoromethyl)benzyl Cyanide (3k)19
Yield: 87.8 mg (79%); yellow oil.
IR (neat): 2254 cm–1 (CN).
1H NMR (500 MHz, CDCl3): δ = 3.83 (s, 2 H), 7.47 (d, J = 8.0 Hz,
2 H), 7.65 (d, J = 8.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 23.6, 117.0, 123.9 (q, JC,F = 271.9
Hz), 126.2 (q, JC,F = 3.9 Hz), 128.4, 130.6 (q, JC,F = 32.6 Hz), 134.0.
MS (EI): m/z (%) = 185 (M+, 70), 116 (M+ – 69, 100).
(5) Chen, G.; Wang, Z.; Wu, J.; Ding, K. Org. Lett. 2008, 10,
4573.
(6) Bandini, M.; Cozzi, G. P.; Giacomini, M.; Melchiorre, P.;
Selva, S.; Umani-Ronchi, A. J. J. Org. Chem. 2002, 67,
3700.
1,2-Bis(2-cyanoethyl)benzene (3l)
Yield: 73.0 mg (66%); yellow oil.
(7) (a) Sakai, N.; Moriya, T.; Konakahara, T. J. Org. Chem.
2007, 72, 5920. (b) Sakai, N.; Fujii, K.; Konakahara, T.
Tetrahedron Lett. 2008, 49, 6873. (c) Sakai, N.; Moriya, T.;
Fujii, K.; Konakahara, T. Synthesis 2008, 3533. (d) Sakai,
N.; Nagasawa, K.; Ikeda, R.; Nakaike, Y.; Konakahara, T.
Tetrahedron Lett. 2011, 52, 3133. (e) Sakai, N.; Usui, Y.;
Ikeda, R.; Konakahara, T. Adv. Synth. Catal. 2011, 353,
3397. (f) Sakai, N.; Kawana, K.; Ikeda, R.; Nakaike, Y.;
Konakahara, T. Eur. J. Org. Chem. 2011, 3178. (g) Sakai,
N.; Usui, Y.; Moriya, T.; Ikeda, R.; Konakahara, T. Eur. J.
Org. Chem. 2012, 4603.
IR (neat): 2256 cm–1 (CN).
1H NMR (300 MHz, CDCl3): δ = 2.64 (t, J = 7.5 Hz, 4 H), 3.02 (t,
J = 7.5 Hz, 4 H), 7.21–7.31 (m, 4 H).
13C NMR (75 MHz, CDCl3): δ = 18.9, 27.9, 118.8, 128.0, 129.4,
135.8.
MS (EI): m/z (%) = 184 (M+, 40), 144 (M+ – 40, 100).
HRMS (EI): m/z [M]+ calcd for C12H12N2: 184.1000; found:
184.1022.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 3233–3238