2674
P. Supsana et al.
LETTER
Shoar, R. H.; Hossein, O. A. J. Chem. Res., Synop. 2005,
formate intermediate was detected by mass spectrometry
in one experiment which lends substantial support to the
proposed mechanism. In comparison with others, this
method is preferable since the use of several reagents that
are more toxic or expensive is avoided.
590. (d) Sarvari, M. H. Synthesis 2005, 787. (e) Niknam,
K.; Karami, B.; Kiasar, A. R. Bull. Korean Chem. Soc. 2005,
26, 975. (f) Khan, T. A.; Peruncheralathan, S.; Ila, H.;
Junjappa, H. Synlett 2004, 2019. (g) Sharghi, H.; Sarvari,
M. H. Synthesis 2003, 243. (h) Yang, S. H.; Chang, S. Org.
Lett. 2001, 3, 4209. (i) Lai, G.; Bhamare, N. K.; Anderson,
W. K. Synlett 2001, 230. (j) Tamami, B.; Kiasat, A. R.
Synth. Commun. 2000, 30, 235. (k) Paraskar, A. S.; Jagtap,
H. S.; Sudalai, A. J. Chem. Res., Synop. 2000, 30.
(l) Iranpoor, N.; Zeynizadeh, B. Synth. Commun. 1999, 29,
2747. (m) Chaudhari, S. S.; Akamanchi, K. G. Synth.
Commun. 1999, 29, 1741. (n) Kumar, H. M. S.; Reddy, B.
V. S.; Reddy, P. T.; Yadav, J. S. Synthesis 1999, 586.
(o) Kato, Y.; Ooi, R.; Asano, Y. Mol. Cat. B. Enzym. 1999,
6, 249. (p) Ortiz-Marciales, M.; Pinero, L.; Algarin, W.;
Morales, J. Synth. Commun. 1998, 28, 2807. (q) Thomas,
H. G.; Greyn, H. D. Synthesis 1990, 129. (r) Saednya, A.
Synthesis 1983, 748.
Acknowledgment
We thank Dr. A. Troganis for NMR spectra and Dr. F. Sakellaridis
and Dr. A. Badeka for mass spectra on machines funded by the
Horizontal Laboratory and Unit Centres of the University of
Ioannina. We are particularly grateful to A. Cakebread and R. Tye
for low- and high-resolution mass spectra obtained on a JEOL JMS-
AX 505W machine funded by the University of London Inter-
collegiate Research Services Scheme.
References and Notes
(9) Maeyama, K.; Kobayashi, M.; Kato, H.; Yonezawa, N.
Synth. Commun. 2002, 32, 2525.
(10) Narashimhan, N. S.; Mali, R. S.; Barve, M. V. Synthesis
1979, 906.
(11) Liebscher, J.; Hartman, H. Z. Chem. 1975, 15, 302.
(12) De Luca, L.; Giacomelli, G.; Riu, A. J. Org. Chem. 2001, 66,
6823.
(13) Quast, H.; Hergenroether, T. Liebigs Ann. Chem. 1992, 581.
(14) Vowinkel, E.; Bartel, J. Chem. Ber. 1974, 107, 1221.
(15) Loader, C. E.; Anderson, H. J. Can. J. Chem. 1981, 59, 2673.
(16) Dictionary of Organic Compounds, 4th ed., Vol. 5; Pollock,
J. R. A.; Stevens, R., Eds.; Oxford University Press: New
York, 1965.
(17) Conversion of Aldoximes into Nitriles (Table 1); General
Procedure: The appropriate aldoxime (3 mmol) in anhyd
DMF (10 mL) was heated at 135 °C for 48 h. After cooling,
the reaction mixture was diluted with H2O (50 mL) and
extracted with EtOAc (3 × 20 mL). The combined organic
extracts were washed with brine (25 mL) and then dried
(Na2SO4). The solvent was removed under vacuo and the
crude product was purified by column chromatography
(EtOAc–hexane, 1:4) to give the corresponding nitrile. The
structure of the products was confirmed by comparison of
their mp or bp, TLC, IR or 1H NMR data with authentic
samples obtained commercially or prepared by literature
methods.
(1) (a) Smith, M.; March, J. Advanced Organic Chemistry:
Reactions, Mechanisms and Structure, 6th ed.; Wiley
Interscience: Chichester, 2007. (b) Larock, R. C.
Comprehensive Organic Transformations, 2nd ed.; Wiley:
New York, 1999. (c) Trost, B.; Flemming, I. Comprehensive
Organic Synthesis; Pergamon Press: Oxford, 1991.
(d) Katritzky, A. R.; Meth-Cohn, O.; Rees, C. W.
Comprehensive Organic Functional Group
Transformations; Oxford: Pergamon, 1995.
(2) (a) Romero, M.; Renard, P.; Caignard, D. H.; Atassi, G.;
Solans, X.; Constans, P.; Bailly, C.; Pujol, M. D. J. Med.
Chem. 2007, 50, 294. (b) Pei, Z. H.; Li, X. F.; Longenecker,
K.; von Geldern, T. W.; Wiedemann, P. E.; Lubben, T. H.;
Zinker, B. A.; Stewart, K.; Ballaron, S. J.; Stashko, M. A.;
Mika, A. K.; Beno, D. W. A.; Long, M.; Wells, H.; Kempf-
Grote, A. J.; Madar, D. J.; McDermott, T. S.; Bhagavatula,
L.; Fickes, M. G.; Pireh, D.; Solomon, L. R.; Lake, M. R.;
Edalji, R.; Fry, E. H.; Sham, H. L.; Trevillyan, J. M. J. Med.
Chem. 2006, 49, 3520. (c) Sakya, S. M.; Hou, X. J.; Minich,
M. L.; Rast, B.; Shavnya, A.; DeMello, K. M. L.; Cheng, H.;
Li, J.; Jaynes, B. H.; Mann, D. W.; Petras, C. F.; Seibel, S.
B.; Haven, M. L. Bioorg. Med. Chem. Lett. 2007, 17, 1076.
(d) Iyengar, B. S.; Dorr, R. T.; Remers, W. A. J. Med. Chem.
2004, 47, 218. (e) Kamath, S.; Buolamwini, J. K. J. Med.
Chem. 2003, 46, 4657.
(3) (a) Jin, F.; Confalone, P. N. Tetrahedron Lett. 2000, 41,
3271. (b) Connor, J. A.; Gibson, D.; Price, R. J. Chem. Soc.,
Perkin Trans. 1 1987, 619. (c) Tagaki, K.; Sakakibara, Y.
Chem. Lett. 1989, 1957. (d) Kubota, H.; Rice, K. C.
Tetrahedron Lett. 1998, 39, 2907. (e) Adachi, M.;
Sugasawa, T. Synth. Commun. 1990, 20, 71. (f)Jackson, W.
R.; Perlmuter, P. Chem. Ber. 1986, 338.
Preparation of 6-Bromo-2-hydroxynaphthalene-1-
carbonitrile (Table 1, entry 13):
Obtained as yellow microcrystals (EtOAc–hexane); yield:
0.48 g (68%); mp 202–203 °C. IR (Nujol): 3200, 2220 cm–1.
1H NMR (400 MHz, DMSO-d6): d = 7.32 (d, J = 9.2 Hz, 1
H, H-3), 7.77–781 (m, 2 H, H-7, H-8), 8.08 (d, J = 9.2 Hz, 1
H, H-4), 8.24 (s, 1 H, H-5), 11.85 (br s, 1 H, OH). MS (EI,
70 eV): m/z (%) = 246 (96) [M+], 221 (7), 192 (7), 140 (29),
113 (30), 87 (11), 70 (7), 63 (15), 50 (5). HRMS–EI: m/z
[M+] calcd for C11H6BrNO: 246.9633; found: 246.9628.
Preparation of 4-Chloro-1-hydroxynaphthalene-2-
carbonitrile (Table 1, entry 14):
Obtained as yellow microcrystals (EtOAc–hexane); yield:
0.31 g (50%); mp 187–190 °C. IR (Nujol): 3200, 2200 cm–1.
1H NMR (400 MHz, DMSO-d6): d = 7.62–7.86 (m, 3 H, H-
3, H-6, H-7), 8.11 (d, J = 7.0 Hz, 1 H, H-5), 8.40 (d, J = 8.4
Hz, 1 H, H-8), 8.62 (br s, 1 H, OH). 13C NMR (100 MHz,
DMSO-d6): d = 93.78, 116.62, 121.38, 123.17, 123.71,
125.62, 126.23, 127.38, 130.66, 132.51, 158.07. MS (EI, 70
eV): m/z (%) = 203 (100) [M+], 174 (9), 148 (21), 140 (50),
113 (32), 88 (15), 74 (17), 63 (21), 50 (17). HRMS–EI: m/z
[M+] calcd for C11H6ClNO: 203.0138; found: 203.0145.
(4) Yamaguchi, K.; Mizuno, N. Angew. Chem. Int. Ed. 2003, 42,
1480.
(5) (a) Mlochowski, J.; Kloc, K.; Kubicz, E. J. Prakt. Chem.
1994, 336, 467. (b) Carmeli, M.; Shefer, N.; Rozen, S.
Tetrahedron Lett. 2006, 47, 8969. (c) Stanković, S.;
Espenson, J. H. Chem. Commun. 1998, 1579.
(d) Ramalingam, T.; Reddy, B. V. S.; Srinivas, R.; Yadav, J.
S. Synth. Commun. 2000, 30, 4507.
(6) (a) Ruck, R. T.; Bergman, R. G. Angew. Chem. Int. Ed. 2004,
43, 5375. (b) Boruah, M.; Konwar, D. J. Org. Chem. 2002,
67, 7138; and references cited therein.
(7) Yan, M.; Xu, Q.-Y.; Chan, A. S. C. Tetrahedron: Asymmetry
2000, 11, 845.
(8) (a) Dewan, S. K.; Singh, R.; Kumar, A. ARKIVOC 2006, (ii),
41. (b) Narsaiah, A. V.; Sreenu, D.; Nagaiah, K. Synth.
Commun. 2006, 36, 137. (c) Heravi, M.; Khadijeh, B.;
Synlett 2007, No. 17, 2671–2674 © Thieme Stuttgart · New York