LETTER
Environmentally Benign Cyanation
2497
Acknowledgment
(20) Oakwood, T. S.; Weisgerber, C. A. Org. Synth., Coll. Vol. 3;
Wiley: New York, 1955, 112.
The authors thank the ‘Chunhui Project’ of the Ministry of
Education of China (Z2004-1-62034), and Key Laboratory of Eco-
Environment-Related Polymer Materials (Northwest Normal
University), Ministry of Education of China for the financial
support of this work.
(
21) (a) Tanaka, M.; Koyanagi, M. Synthesis 1981, 973. (b)Cao,
Y. Q.; Du, Y. F.; Chen, B. H.; Li, J. T. Synth. Commun. 2004,
34, 2951. (c) Ando, T.; Kawate, T.; Yamawaki, J.;
Hanafusa, T. Synthesis 1983, 637.
(
(
22) Tanaka, M. Tetrahedron Lett. 1980, 21, 2959.
23) (a) Olah, G. A.; Arvanaghi, M.; Prakash, G. K. S. Synthesis
1
983, 636. (b) Harle, H.; Jochims, J. C. Chem. Ber. 1986,
References and Notes
119, 1400.
(
(
24) Choudary, B. M.; Reddy, P. N. J. Mol. Catal. A: Chem.
996, 112, 385.
25) (a) Schareina, T.; Zapf, A.; Beller, M. Tetrahedron Lett.
005, 46, 2585. (b) Schareina, T.; Zapf, A.; Beller, M. J.
(
1) (a) Saikia, P.; Laskar, D. D.; Prajapati, D.; Sandhu, J. S.
Tetrahedron Lett. 2002, 43, 7525. (b) Baek, H. S.; Lee, S. J.;
Yoo, B. W.; Ko, J. J.; Kim, S. H.; Kim, J. H. Tetrahedron
Lett. 2000, 41, 8097. (c) Yoo, B. W.; Kim, D. Y.; Choi, J.
W.; Hwang, S. K.; Choi, K. I.; Kim, J. H. Bull. Korean
Chem. Soc. 2003, 24, 263.
1
2
Organomet. Chem. 2004, 689, 4576. (c) Schareina, T.;
Zapf, A.; Beller, M. Chem. Commun. 2004, 1388.
(
d) Weissman, S. A.; Zewge, D.; Chen, C. J. Org. Chem.
(
(
(
(
(
(
2) Gohain, M.; Gogoi, B. J.; Prajapati, D.; Sandhu, J. S. New J.
Chem. 2003, 27, 1038.
2
2
005, 70, 1508. (e) Grossman, O.; Gelman, D. Org. Lett.
006, 8, 1189.
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J.; Choi, K. I.; Kim, J. H. Tetrahedron Lett. 2002, 43, 4813.
4) Duplais, C.; Bures, F.; Sapountzis, I.; Korn, T. J.; Cahiez, G.;
Knochel, P. Angew. Chem. Int. Ed. 2004, 43, 2968.
5) Yoo, B. W.; Lee, S. J.; Choi, K. H.; Keum, S. R.; Ko, J. J.;
Choi, K. I.; Kim, J. H. Tetrahedron Lett. 2001, 42, 7287.
6) Veronese, A. C.; Callegari, R.; Basato, M.; Valle, G. J.
Chem. Soc., Perkin Trans. 1 1994, 1779.
(
26) General Procedure: A mixture of AgI (0.1 g, 0.45 mmol),
PEG400 (0.24 g, 0.6 mmol), KI (0.08 g, 0.45 mmol), and
K [Fe(CN) ] (1.15 g, 3 mmol) (dried at 80 °C under vacuum
4
6
for 24 h and finely powdered prior to use) in anhyd DMF
(
(
10 mL) was first stirred for 10 min, then aroyl chloride
15 mmol) was added. The mixture was stirred for the
appropriate time indicated in Table 2 at r.t. The progress of
the reaction was monitored by TLC (PE–EtOAc, 5:1). Then
7) Park, Y. S.; Han, J. H.; Yoo, B.; Choi, K. I.; Kim, J. H.;
Yoon, C. M.; Yoo, B. W. Bull. Korean Chem. Soc. 2005, 26,
CH Cl (20 mL) was added. The suspension was filtered to
2
2
remove the solid, the filtrate was washed with cold H O (3 ×
878.
2
3
0 mL), and dried over anhyd MgSO . Then the solvent was
(
(
8) Okimoto, M.; Chiba, T. Synthesis 1996, 1188.
9) Zhang, W.; Shi, M. Org. Biomol. Chem. 2006, 4, 1671.
4
removedby distillation andtheresidue was crystallized from
hexane to give the product. 2-Chlorobenzoyl cyanide: IR
(
(
10) Watahiki, T.; Ohba, S.; Oriyama, T. Org. Lett. 2003, 5, 2679.
11) Nemoto, H.; Ibaragi, T.; Bando, M.; Kido, M.; Shibuya, M.
Tetrahedron Lett. 1999, 40, 1319.
12) Zhou, S.; Yan, B.; Liu, Y. J. Org. Chem. 2005, 70, 4006.
13) Liu, Y. H.; Yan, B. Organometallics 2006, 25, 544.
14) Demko, Z. P.; Sharpless, K. B. Angew. Chem. Int. Ed. 2002,
–
1
1
(
4
KBr): 2089 (C≡N), 1776 cm (C=O). H NMR (CDCl ,
3
00 MHz): d = 7.29–7.81 (m, 4 H, Ph). Anal. Calcd for
C H ClNO: C, 58.03; H, 2.44; N, 8.46. Found: C, 57.91; H,
(
(
(
8
4
2
.50; N, 8.39. 3-Chlorobenzoyl cyanide: IR (KBr): 1964
–
1
1
(
C≡N), 1793 cm (C=O). H NMR (CDCl , 400 MHz): d =
3
7.22–7.78 (m, 4 H, Ph). Anal. Calcd for C H ClNO: C,
41, 2113.
8 4
5
8.03; H, 2.44; N, 8.46. Found: C, 58.11; H, 2.49; N, 8.53.
(
(
(
15) Zhuo, J. C.; Wyler, H. Helv. Chim. Acta 1993, 76, 1916.
16) Connors, R.; Tran, E.; Durst, T. Can. J. Chem. 1996, 74, 221.
17) Kuwabara, H.; Ushigoe, Y.; Nojima, M. J. Chem. Soc.,
Perkin Trans. 1 1996, 871.
–
1
2
-Furoyl cyanide: IR (KBr): 2067 (C≡N), 1758 cm (C=O).
1
H NMR (CDCl , 400 MHz): d = 6.70–7.69 (m, 3 H, Furan).
3
Anal. Calcd. for C H NO : C, 59.51; H, 2.50; N, 11.57.
6
3
2
Found: C, 59.70; H, 2.43; N, 11.49. 2-Thiophenecarbonyl
(
18) Hunig, S.; Schaller, R. Angew. Chem., Int. Ed. Engl. 1982,
1
cyanide: IR (KBr): 2052 (C≡N), 1766 (C=O). H NMR
21, 36.
(
CDCl , 400 MHz): d = 7.10–7.71 (m, 3 H, Thiophene).
(
19) Koenig, K. E.; Weber, W. P. Tetrahedron Lett. 1974, 2275.
3
Anal. Calcd for C H NOS: C, 52.54; H, 2.20; N, 11.66.
6
3
Found: C, 52.42; H, 2.30; N, 11.72.
Synlett 2006, No. 15, 2495–2497 © Thieme Stuttgart · New York