Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.
SUPERACTIVITY AND DUAL REACTIVITY OF THE SYSTEM
Scheme 2.
1281
NIS
+
+
H2SO4
+
HOSO2OI
ΔH = 19.7, ΔG = 19.6 kcal/mol
O
O
N
H
NIS–H+
H2SO4
+ HOSO2OI
ΔH = 37.2, ΔG = 36.4 kcal/mol
O
OH
N
H
5. Carreno, M.C., Carcia Ruano, J.L., Sanz, G., Tole-
do, M.A., and Urbano, A., Tetrahedron Lett., 1996,
vol. 37, p. 4081.
90%), 30 ml, was cooled to 0–5°C and added to 2.25 g
(10 mmol) of N-iodosuccinimide, and the mixture was
stirred for 20–30 min until it became homogeneous. To
effect monoiodination, 5 mmol of the corresponding
arene was added at 0 or 20°C (Table 1) to the resulting
dark brown solution, and the mixture was vigorously
stirred for 20–180 min. To introduce two iodine atoms
into the substrate molecule, its amount was reduced by
half. When the reaction was complete, the mixture was
poured into 100 ml of an ice–water mixture and treated
with a solution of Na2SO3. Compounds Ib, Xb, and
XIb were extracted into methylene chloride, the
extract was dried over CaCl2, the solvent was distilled
off, and the residue was recrystallized if necessary.
Compounds IIb, IIIb, VIb–VIIIb, IXb, and IXc were
filtered off, dried, and recrystallized from appropriate
solvent (Table 1). Compounds IVb and Vb were dis-
solved in benzene, the solution was filtered through
a layer of silica gel, and the solvent was distilled off
from the filtrate.
6. Olah, G.A., Wang, Q., Sandford, G., and Pra-
kash, G.K.S., J. Org. Chem., 1993, vol. 58, p. 3194.
7. Prakash, G.K.S., Mathew, T., Hoole, D., Esteves, P.M.,
Wang, Q., Rasul, G., and Olah, G.A., J. Am. Chem. Soc.,
2004, vol. 126, p. 15770.
8. Chaikovskii, V.K., Filimonov, V.D., and Skorokho-
dov, V.I., Russ. J. Org. Chem., 2001, vol. 37, p. 1503.
9. Katayama, S., Nobuyuki, A., and Nagata, R., J. Org.
Chem., 2001, vol. 66, p. 3474.
10. Chaikovskii, V.K., Filimonov, V.D., Kulupanova, O.A.
and Chernova, T.N., Russ. J. Org. Chem., 1998, vol. 34,
p. 997.
11. Becke, A.D., J. Chem. Phys., 1993, vol. 98, p. 5648.
12. Glukhovtsev, M.N., Pross, A., McGrath, M.P., and
Radom, L., J. Chem. Phys., 1995, vol. 103, p. 1878.
13. GAUSSIAN 98W. User’s Reference, Fritsch, E. and
Fritsch, M.J., Eds., Pittsburgh: Gaussian, 1998, p. 280.
14. Sintezy iodistykh organicheskikh soedinenii (Syntheses
of Iodine-Containing Organic Compounds), Yagupol’-
skii, L.M., Novikov, A.N., and Merkushev, E.B., Eds.,
Tomsk: Tomsk. Gos. Univ., 1976, p. 90.
15. Dictionary of Organic Compounds, Heilbron, J. and
Bunbury, H.M., Eds., London: Eyre and Spottswoode,
1953, vol. 3.
16. Novikov, A.N. and Grigor’ev, M.G., Izv. Vyssh. Uchebn.
Zaved., Ser. Khim. Khim. Tekhnol., 1977, vol. 20, p. 1716.
17. Lulinski, P. and Skulski, L., Bull. Chem. Soc. Jpn.,
REFERENCES
1. Chaikovski, V.K., Kharlova, T.S., Filimonov, V.D., and
Saryucheva, T.A., Synthesis, 1999, p. 748.
2. Chaikovskii, V.K., Kharlova, T.S., and Filimonov, V.D.,
Izv. Ross. Akad. Nauk, Ser. Khim., 1999, p. 1303.
3. Chaikovski, V.K., Filimonov, V.D., Yagovkin, A.Y., and
Kharlova, T.S., Tetrahedron Lett., 2000, vol. 41, p. 9101.
4. Merkushev, E.B., Synthesis, 1988, p. 923.
1997, vol. 70, p. 1665.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007