5ꢀ(3,5ꢀBut2ꢀ4ꢀHydroxyphenyl)ꢀ1,2,3,5ꢀtetrahydrophenazine Russ.Chem.Bull., Int.Ed., Vol. 58, No. 5, May, 2009
943
should be accompanied by the exothermic effect of
~8 kcal mol–1 per hydrogen bond, resulting in the high
total exothermic effect of this polymerization reaction.
References
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Compd. (Engl. Transl.), 1987, 824].
Experimental
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[Chem. Heterocycl. Compd. (Engl. Transl.), 1990, 414].
6. F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G.
Orpen, R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1987, S1.
7. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr. T.
Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S.
Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi,
G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji,
M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai,
M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross,
C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann,
O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski,
P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J.
Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels,
M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck,
K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G.
Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu,
A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J.
Fox, T. Keith, M. A. AlꢀLaham, C. Y. Peng, A. Nanayakkara,
M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen,
M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03, Reviꢀ
sion B.03, Pittsburgh PA, Gaussian Inc., 2003.
The IR spectra were recorded on a Varian Excalibur 3100
FTꢀIR instrument using attenuated total internal reflectance.
The H NMR spectra were measured on a Varian UNITYꢀ300
1
spectrometer.
5ꢀ(3,5ꢀDiꢀtertꢀbutylꢀ4ꢀhydroxyphenyl)ꢀ1,2,3,5ꢀtetrahydroꢀ
phenazine (5). A mixture of quinoneimine 1 (0.31 g, 1 mmol)
and cyclohexanone 2 (0.3 mL, 2.8 mmol) was refluxed for
2 min. Then CH3CN (2 mL) was added, and the reaction mixꢀ
ture was cooled with ice and ground with a rod. The resulting
greenishꢀyellow crystalline precipitate was filtered off, washed
with cold CH3CN, and dried; m.p. 210—215 °C (from CH3CN).
The yield was 0.13 g (33.7%). To prepare the analytically pure
compound, the substance was chromatographed on alumina
using CHCl3 as the eluent. The solvent was distilled off, and the
residue was recrystallized from CH3CN and dried in vacuo at
100 °C. Found (%): C, 80.27; H, 8.43; N, 7.14. C26H32N2O.
Calculated (%): C, 80.38; H, 8.30; N, 7.21. IR, ν/cm–1: 3633
(OH), 1614, 1581 (arom.), 1234 (But). 1H NMR (CDCl3), δ:
1.42 (s, 18 H, But); 1.80 (m, 2 H, C(2)H2); 2.14 (m, 2 H,
C(3)H2); 2.62 (t, 2 H, C(1)H2, J = 6.4 Hz); 4.21 (t, 1 H, C(4)H,
J = 4.8 Hz); 5.33 (s, 1 H, OH); 5.92 (dd, 1 H, С(6)H, 3J = 8.1 Hz,
4J = 1.1 Hz); 6.68 (m, 1 H, С(7)H); 6.83 (m, 1 H, C(8)H); 6.90
(s, 2 H, C(2´)H, C(6´)H); 7.22 (dd, 1 H, C(9)H, 3J = 7.7 Hz,
4J = 1.5 Hz).
Xꢀray diffraction study. Crystals suitable for Xꢀray diffracꢀ
tion study were grown by slow evaporation of a solution of
compound 5 in CH3CN at room temperature. The resulting
crystals contained one CH3CN solvent molecule per molecule
5. The solvated crystals of compound 5 (C26H32N2O•CH3CN)
at 110 K are orthorhombic, a = 18.024(2) Å, b = 14.727(2) Å,
c = 18.462(3) Å, V = 4900.5(11) Å3, Z = 8, space group Pbca,
μ = 0.071 mm–1, dcalc = 1.165 g cm–3. The intensities of 31557
reflections were measured on a SMART 1000 CCD diffractoꢀ
meter (λ(MoꢀKα) = 0.71073 Å, graphite monochromator,
ωꢀscanning technique, the scan step was 0.3°, the exposure time
per frame was 10 s, 2θ < 54°). The Xꢀray diffraction data were
processed using the SAINT Plus9 and SADABS programs.10
The structure was solved by direct methods and refined by the
fullꢀmatrix leastꢀsquares method with anisotropic displacement
parameters for all nonhydrogen atoms based on F2hkl. The
hydrogen atoms were positioned geometrically, except for
the hydrogen atom of the OH group, whose position was located
in difference electron density maps and then normalized to the
distance of 0.85 Å. All hydrogen atoms were refined using a
riding model (Uiso(H) = nUeq(C,O), where n = 1.5 for the
carbon atoms of the methyl groups and the oxygen atom, n = 1.2
for the other C atoms). The refinement was performed using
5328 independent reflections. The refinement based on all indeꢀ
pendent reflections converged to wR2 = 0.0857 (R1 = 0.0549
based on 1584 reflections with I > 2σ(I)). All calculations were
carried out on an IBM PC AT using the SHELXTL program
package.11
8. J. B. Foresman, E. Frisch, Exploring Chemistry with
Electronic Structure Methods (2nd ed.), Gaussian Inc.,
Pittsburg, 1996.
9. SMART and SAINT, Release 5.0, Area Detector Control and
Integration Software, Bruker AXS, Analytical XꢀRay Instruꢀ
ments, Madison, Wisconsin, USA, 1998.
10. G. M. Sheldrick, SADABS, Program for Exploiting the
Redundancy of Areaꢀdetector XꢀRay Data, Göttingen
University, Göttingen (Germany), 1999.
11. G. M. Sheldrick, SHELXTL, Program for Solution and
Refinement of Crystal Structure, Version 5.10, Bruker AXS
Inc., Madison, Wisconsin, USA, 1998.
Received April 28, 2008;
in revised form November 18, 2008