1806 Bull. Chem. Soc. Jpn., 77, No. 10 (2004)
HEADLINE ARTICLES
0.4
0.4
0.3
0.2
0.1
0.0
-0.1
0.3
0.2
0.1
0.0
-0.1
1a
2a
3a
1a
2a
3a
-2 -1
0
1
2
3
4
5
-2 -1
0
1
2
3
4
log(η
/Pa s)
log(η
/Pa s)
Fig. 6. Pressure effects plotted against viscosity ꢀ for the
three reactants at 15 C in MPD.
Fig. 5. Pressure effects plotted against viscosity ꢀ for the
three reactants at 35 C in GTA.
ꢂ
ꢂ
carbon atoms to the naphthalenone group did not cause a shift
of ꢀmax to an even lower value. On the contrary, the structural
change moved the ꢀmax to a slightly higher value, probably be-
cause the reaction was slower in 3a. A higher viscosity was
required to break the equilibrium between the initial and the
transition state in 3a. This structural dependence of the viscos-
ity effect may be considered as an indication of the absence of
major solvent reorganizations in the vicinity of the naphthale-
none moiety in 2a.
earlier reviews cited therein.
3
4
For examples see Ref. 2.
T. Asano, H. Furuta, and H. Sumi, J. Am. Chem. Soc., 116,
5545 (1994).
5 N. Agmon and J. J. Hopfield, J. Chem. Phys., 78, 6947
(1983).
6
(1983).
7
(1986).
N. Agmon and J. J. Hopfield, J. Chem. Phys., 79, 2042
H. Sumi and R. A. Marcus, J. Chem. Phys., 84, 4894
8
9
H. Sumi, J. Phys. Chem., 95, 3334 (1991).
A. M. Berezhkovskii and V. Yu. Zitserman, Chem. Phys.
Conclusion
From the present results, it would be reasonable to conclude
that solvent reorganizations took place mainly around the
ethenyl moiety in the cyclization shown in Scheme 1. Since
all of the movements are relative to each other, this conclusion
can be rephrased as follows. During the cyclization, the substi-
tuted ethenyl group changed its position in the solvation sphere
while the naphthalenone group stayed in the same position. To
the best of our knowledge, this is the first successful attempt to
demonstrate the existence of spatial selectivity in the solvent
reorganizations in a homogenous solution reaction. The asyn-
chornism between the solvent reorganizations and the chemi-
cal structural changes and the spatial selectivity in the solvent
reorganizations may be considered as two fundamental fea-
tures of solution reactions.
Lett., 158, 369 (1989).
10 A. M. Berezhkovskii, Yu. A. D’yakov, and V. Yu.
Zitserman, J. Chem. Phys., 109, 4182 (1998).
11 A. M. Berezhkovskii, V. Yu. Zitserman, D.-Y. Yang,
J. Kuo, and S. H. Lin, Physica A, 251, 399 (1998).
12 M. V. Basilevsky, V. M. Ryaboy, and N. N. Weinberg,
J. Phys. Chem., 94, 8734 (1990).
13 M. V. Basilevsky, V. M. Ryaboy, and N. N. Weinberg,
J. Phys. Chem., 95, 5533 (1991).
14 T. Asano, K. Cosstick, H. Furuta, K. Matsuo, and H. Sumi,
Bull. Chem. Soc. Jpn., 69, 551 (1996).
15 T. Asano, K. Matsuo, and H. Sumi, Bull. Chem. Soc. Jpn.,
70, 239 (1997).
16 J. C. Kim, Y. Ohga, T. Asano, N. N. Weinberg, and A. V.
George, Bull. Chem. Soc. Jpn., 74, 103 (2001).
17 Y. Goto, T. Takahashi, Y. Ohga, T. Asano, M. Hildebrand,
and N. N. Weinberg, Phys. Chem. Chem. Phys., 5, 1825 (2003).
18 H. Kono, H. Osako, M. Sasaki, T. Takahashi, Y. Ohga,
T. Asano, M. Hildebrand, and N. N. Weinberg, Phys. Chem.
Chem. Phys., 6, 2260 (2004).
Further experiments with different chromenes are under
way and the results will be reported when they are completed.
This work was partially supported by a Grant-in-Aid of
the Japan Society for Promotion of Science and Culture
(13440191).
19 J.-L. Pozzo, A. Samat, R. Guglielmetti, R. Dubest, and
J. Aubard, Helv. Chim. Acta, 80, 725 (1997).
References
20 T. Asano, Pure Appl. Chem., 71, 1691 (1999).
21 T. Asano and T. Okada, J. Phys. Chem., 88, 238 (1984).
22 The dipole moments calculated by PM3 using MacSpartan
Pro programs23 of the reactants were, 2.71 D (1a), 0.76 D (1b),
2.66 D (2a), 0.65 D (2b), 2.24 D (3a), and 0.40 D (3b).
23 ‘‘MacSpartan Pro,’’ Wavefunction, Inc., 18401 Von
Karman Avenue, Suit 370 Irvine, CA 92612, USA (2000).
#
Preliminary results were reported in Y. Goto, K. Sugita, T.
Takahashi, Y. Ohga, and T. Asano, Chem. Lett., 32, 618 (2003).
C. Reichardt, ‘‘Solvents and Solvents Effects in Organic
Chemistry, 3rd ed,’’ Wiley-VCH, Weinheim (2003).
A. Drljaca, C. D. Hubbard, R. van Eldik, T. Asano, M. V.
Basilevsky, and W. J. le Noble, Chem. Rev., 98, 2167 (1998), and
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