H. M. Meshram et al. / Tetrahedron Letters 53 (2012) 1780–1785
1785
Enugala, R.; Adapa, S. R. ARKIVOC 2006, xiii, 171; (g) Dhakshinamoorthy, A.;
Kanagaraj, K.; Pitchumani, K. Tetrahedron Lett. 2011, 52, 69.
References and notes
25. (a) Meshram, H. M. Tetrahedron Lett. 1993, 34, 252; (b) Varma, R. S.; Meshram,
H. M. Tetrahedron Lett. 1997, 38, 5427; (c) Varma, R. S.; Saini, R. K.; Meshram, H.
M. Tetrahedron Lett. 1997, 38, 6525; (d) Varma, R. S.; Meshram, H. M.
Tetrahedron Lett. 1997, 38, 7973; (e) Meshram, H. M.; Srinivas, D.; Yadav, J. S.
Tetrahedron Lett. 1997, 38, 8743; (f) Meshram, H. M.; Reddy, G. S.; Yadav, J. S.
Tetrahedron Lett. 1997, 38, 8891; (g) Meshram, H. M.; Sumithra, G.; Reddy, G. S.;
Ganesh, Y. S. S.; Yadav, J. S. Synth. Commun. 1999, 29, 2807; (h) Meshram, H. M.;
Ganesh, Y. S. S.; Yadav, J. S. Synth. Commun. 2003, 33, 2497; (i) Meshram, H. M.;
Reddy, P. N.; Murthy, P. V.; Yadav, J. S. Synth. Commun. 2007, 37, 4117.
26. Laszlo, P.; Pennetreau, P.; Krief, A. Tetrahedron Lett. 1986, 27, 3153.
27. (a) Jazzaa, A. A.; Clark, J. H.; Robertson, M. Chem. Lett. 1982, 405; (b) Clark, J. H.;
Cork, D. G.; Robertson, M. S. Chem. Lett. 1983, 1145; (c) Clark, J. H.; Cork, D. G.;
Gibbs, H. W. J. Chem. Soc., Perkin Trans. 1 1983, 2253.
28. General procedure for the preparation of K10-montmorillonite clay supported
ammonium thiocyanate: In a round bottomed 500 ml flask equipped with stir
bar and containing 100 ml acetone, was added 7.6 g of ammonium thiocyanate
salt and stirred at room temperature until the complete dissolution of salt. To
this clear solution, 10 g of montmorillonite K10 clay was added in portions
over 10 min with stirring. After complete addition, the formation of reddish
suspension was observed which was vigorously stirred for another 30 min at
1. (a) Prakash, O.; Kaur, H.; Batra, H.; Rani, N.; Singh, S. P.; Moriarty, R. M. J. Org.
Chem. 2001, 66, 2019; (b) Rudolph, J.; Theis, H.; Hanke, R.; Endermann, R.;
Johannsen, L.; Geschke, F.-U. J. Med. Chem. 2001, 44, 619; (c) Kamal, A.;
Choudan, G. Tetrahedron Lett. 2005, 46, 1489; (d) Mohanazadeh, F.; Aghvami, M.
Tetrahedron Lett. 2007, 48, 7240.
2. (a) Shahidi, F. In Sulphur Compounds in Foods; Mussinan, C. J., Keelan, M. E., Eds.;
American Chemical Society: Washington, DC, 1994; p 106. Chapter 9; (b)
Mehta, R. G.; Liu, J.; Constantinou, A.; Thomas, C. F.; Hawthorne, M.; You, M.;
Gerhaeusers, C.; Pezzuto, J. M.; Moon, R. C.; Moriarty, R. M. Carcinogenesis 1995,
16, 399; (c) Garson, M. J.; Simpson, J. S.; Flowers, A. E.; Dumdei, E. J. In Studies in
Natural Products Chemistry; Atta-ur-Rahman, Ed.; Elsevier, 2000; Vol. 21, p 329;
(d) Capon, R. J.; Skene, C.; Liu, E. H.-T.; Lacey, E.; Gill, J. H.; Heiland, K.; Friedel, T.
J. Org. Chem. 2001, 66, 7765; (e) Yasman, Y.; Edrada, R. A.; Wray, V.; Proksch, P.
J. Nat. Prod. 2003, 66, 1512.
3. (a) Wood, J. L. Org. React. 1946, 3, 240; (b) Metzer, J. B. In Comprehensive
Heterocyclic Chemistry; Katritzky, A., Ed.; Pergamon: Oxford, 1984; Vol. 6, p
235; (c) Kelly, T. R.; Kim, M. H.; Curtis, A. D. M. J. Org. Chem. 1993, 58, 5855; (d)
Kodomari, M.; Aoyama, T.; Suzuki, Y. Tetrahedron Lett. 2002, 43, 1717; (e)
Aoyama, T.; Murata, S.; Arai, I.; Araki, N.; Takido, T.; Suzuki, Y.; Kodomari, M.
Tetrahedron 2006, 62, 3201; (f) Aoyama, T.; Murata, S.; Takido, T.; Kodomari, M.
Tetrahedron 2007, 63, 11933; (g) Falck, J. R.; Gao, S.; Prasad, R. N.; Reddy, K. S.
Bioorg. Med. Chem. Lett. 2008, 18, 1768; (h) Li, L.; Ganesh, M.; Seidel, D. J. Am.
Chem. Soc. 2009, 131, 11648.
room temperature. Then the suspension is placed in
a rotary vacuum
evaporator and the solvent was removed under reduced pressure. The dry
solid crust adhering to the walls of the flask was flaked off with a spatula, and
solvent evaporation was resumed. After complete drying, yielded, about 17.6 g
of clay supported ammonium thiocyanate as a light red free flowing powder
which shows no loss of reactivity after standing in an open powder box for one
week.
4. (a) Newman, A. A. Chemistry and Biochemistry of Thiocyanic Acid and its
Derivatives, 1st ed.; Academic Press, 1975; (b) Leblanc, B. L.; Jursic, B. C. Synth.
Commun. 1998, 28, 3591.
5. Baig, R. B. N.; Sudhir, V. S.; Chandrasekaran, S. Tetrahedron: Asymmetry 2008, 19,
1425.
General procedure for the synthesis of
a-oxo thiocyanates by using K10-
montmorillonite clay supported ammonium thiocyanate under catalyst and
solvent free conditions: Phenacyl bromide (1 mmol) and K10-montmorillonite
clay supported ammonium thiocyanate (3 mmol) were taken in mortar, mixed
with spatula, and ground with pestle for stipulated time (see Table 3). After
complete conversion as indicated by TLC, the solid reaction mixture was
directly loaded on silica gel column by avoiding aqueous work up-extraction
step. Later elution with ethyl acetate–hexane (9:1–3:1) solvent system and
evaporation of solvents in rotary vacuum evaporator afforded pure phenacyl
thiocyanate (99%). Same procedure as discussed above was followed to prepare
all thiocyanate compounds shown in this work. All compounds prepared were
characterized by IR, Mass, and NMR spectroscopy. Spectral data for the
representative compounds are given as below:
6. Renard, P.-Y.; Schwebel, H.; Vayron, P.; Leclerc, E.; Dias, S.; Mioskowski, C.
Tetrahedron Lett. 2001, 42, 8479.
7. Yadav, J. S.; Reddy, B. V. S.; Reddy, U. V. S.; Krishna, A. D. Tetrahedron Lett. 2007,
48, 5243.
8. Yadav, J. S.; Reddy, B. V. S.; Reddy, U. V. S.; Chary, D. N. Synthesis 2008, 8, 1283.
9. Bhalerao, D. S.; Akamanchi, K. G. Synth. Commun. 2010, 40(6), 799.
10. Reddy, B. V. S.; Reddy, S. M. S.; Madan, C. Tetrahedron Lett. 2011, 52, 1432.
11. Sayyahi, S.; Saghanezhad, J. Chin. Chem. Lett. 2011, 22, 300.
12. Li, J.; Cao, J.-j.; Wei, J.-f.; Shi, X.-y.; Zhang, L.-h.; Feng, J.-j.; Chen, Z.-g. Eur. J. Org.
Chem. 2011, 2, 229.
13. Kiasat, A. R.; Sayyahi, S. Mol. Divers. 2010, 14, 155.
14. Iranpoor, N.; Firouzabadi, H.; Shaterian, H. R. Tetrahedron Lett. 2002, 43, 3439.
15. Nair, V.; Nair, L. G.; George, T. G.; Augustine, A. Tetrahedron 2000, 56, 7607.
16. Palsuledesai, C. C.; Murru, S.; Sahoo, S. K.; Patel, B. K. Org. Lett. 2009, 11, 3382.
17. Bisogno, F. R.; Cuetos, A.; Lavandera, I.; Gotor, V. Green Chem. 2009, 11, 452.
18. Smith, P. A. S.; Emerson, D. W. J. Am. Chem. Soc. 1960, 82, 3076.
19. Sheldon, R. A. Green Chem. 2007, 9, 1273.
29. Spectral data for representative compounds: 1-(Anthracen-10-yl)-2-
thiocyanatoethanone (13b, Table 2, entry 15): Yellow solid. mp 122–124 °C;
1H NMR (300 MHz, D6 DMSO) d: 8.67 (s 1H), 8.11 (d, 2H, J = 8.1 Hz) 7.79 (d, 2H
J = 8.3 Hz), 7.61–7.52 (m, 4H), 4.81 (s, 2H) ppm. 13C NMR (75 MHz, D6 DMSO) d:
195.2, 136.6, 130.4, 128.6, 127.8, 126.8, 125.8, 125.4, 123.9, 111.9, 42.4 ppm.
IR(KBR): mmax = 2972, 2144, 1713, 1672, 1613, 1556, 1475, 1321, 1242, 1160,
20. Trost, B. M. Science 1991, 254, 1471.
21. Corma, A.; Garcia, H. Chem. Rev. 2003, 103, 4307.
915, 860, 714 cmÀ1. MS-ESI: m/z = 300 [M+Na]+. Anal. Calcd for C17H11NOS: C,
73.62; H, 4.00; N, 5.05. Found: C, 73.49; H, 3.91; N, 5.14. Ethyl 2-methyl-3-oxo-
3-phenyl-2-thiocyanatopropanoate (28b, Table 2, entry 30): Yellow viscous oil.
1H NMR (300 MHz, CDCl3) d: 7.95–7.34 (m, 5H), 4.24 (q, 2H, J = 7.2 Hz); 3.74 (s,
3H) 1.29 (t, 3H, J = 7.2) ppm. 13C NMR (75 MHz, CDCl3) d: 199.4, 169.7, 137.2,
22. (a) Kodomari, M.; Kuzuoka, T.; Yoshitomi, S. Synthesis 1983, 141; (b) Ando, T.;
Clark, J. H.; Cork, D. G.; Fujita, M.; Kimura, T. J. Org. Chem. 1987, 52, 681; (c)
Kodomari, M.; Nawa, S.; Miyoshi, T. Chem. Commun. 1995, 1895; (d) Suzuki, Y.;
Kodomari, M. Chem. Lett. 1998, 1091; (e) Aoyama, T.; Murata, S.; Nagata, Y.;
Takido, T.; Kodomari, M. Tetrahedron Lett. 2005, 46, 4875; (f) Aoyama, T.;
Takido, T.; Kodomari, M. Synlett 2005, 2739; (g) Aoyama, T.; Aria, I.;
Matsumoto, T.; Takido, T.; Kodomari, M. . Synthesis 2009, 24, 4113.
23. Varma, R. S. Green Chem. 1999, 1, 43.
24. (a) Balogh, M.; Cornelis, A.; Laszlo, P. Tetrahedron Lett. 1984, 25, 3313; (b)
Laszlo, P.; Pcnnetreau, P. J. Org. Chem. 1987, 52, 2407; (c) Barlow, S. J.; Bastock,
T. W.; Clark, J. H.; Cullen, S. R. J. Chem. Soc., Perkin Trans. 2 1994, 411; (d)
Lancaster, N. L.; Moodie, R. B.; Sandall, J. P. B. J. Chem. Soc., Perkin Trans. 2 1997,
847; (e) Varma, R. S.; Dahiya, R. Tetrahedron Lett. 1998, 39, 1307; (f) Varala, R.;
134.1, 129.1, 128.7, 111.2, 74.9, 63.1, 15.9, 14.3 ppm. IR(KBR):
mmax = 2939,
2151, 1689, 1651, 1597, 1457, 1223, 959 cmÀ1. MS-ESI: m/z = 286 [M+Na]+.
Anal. Calcd for C13H13NO3S: C, 59.30; H, 4.98; N, 5.32. Found: C, 59.19; H, 5.11;
N, 5.21. 4-(Thiocyanatomethyl) benzonitrile (31b, Table 3, entry 4): White
solid. mp 76–78 °C; 1H NMR (300 MHz, CDCl3): d 7.70 (d, 2H, J = 7.9 Hz), 7.49
(d, 2H, J = 7.9 Hz), 4.14 (s, 2H) ppm. 13C NMR (75 MHz, CDCl3): d 134.4, 129.8,
126.7, 119.5, 115.7, 111.7, 38.7 ppm. IR(KBR): mmax = 3094, 2987, 2923, 2849,
2222, 2154, 1499, 1408, 1247, 1104, 847, 640, 554 cmÀ1. EI-MS: m/z = 175
[M+1]+. Anal. Calcd for C9H6N2S: C, 62.05; H, 3.47; N, 16.08. Found: C, 61.96; H,
3.61; N, 15.97.