Shimadzu RF-540 spectrofluorometer using hexane. Mass spectra were taken on an MX-1303 instrument with
an ionization energy of 70 eV. Monitoring of the reaction course and the homogeneity of the obtained
compounds was performed using TLC on Silufol UV-254 plates in the solvent system hexane–ethyl acetate
(3:1).
X-ray Analysis of Compound 3. Crystals of compound 3 (C56H40Cl4Cu2N2O2·2C2H5OH, M = 1144.00)
are rhombic with space group Pbca, at T = 163 K: a = 15.763(3), b = 13.718(3), c = 23.921(5) Å;
V = 5172.7(18) Å3; Z = 4; dcalc = 1.469 mg/cm3; F(000) = 2376; µ = 1.08 mm-1. Unit cell parameters and the
intensities of 4551 reflections were measured on a Syntex P21 four circle, automatic diffractometer (T = 163 K,
λMoKα radiation, graphite monochromator, θ/2θ scanning, θmax = 28°). The structure was solved by a direct
method and refined in a full matrix least squares analysis in the anisotropic approximation for non-hydrogen
atoms. The ethanol solvate molecule was revealed in difference Fourier synthesis. The hydrogen atoms of the
hydroxyl groups were localized directly by difference Fourier synthesis and refined in the isotropic
approximation. The positions of the remaining hydrogen atoms were calculated geometrically and refined in the
isotropic approximation with fixed positions (the "riding" model) and thermal parameters [Uiso(H) = 1.5 Ueq(C)
for CH3 groups and Uiso(H) = 1.2 Ueq(C) for all of the remaining groups]. The final difference factors were
R1 = 0.074 for 3292 independent reflections with I > 2σ(I) and wR2 = 0.1592 for all 4551 independent
reflections. All of the calculations were carried out using the SHELXTL PLUS (version 5.10) computer package
[8]. Tables 1-3 show the data for the atomic coordinates, bond lengths, valence and torsional angles, and
anisotropic thermal parameters for compound 3.
α-Pyridyl([2.2]paracyclophan-4-yl)phenylmethanol (2). A. A solution of 2-benzoylpyridine (2.56 g,
14 mmol) in benzene (5 ml) was added to a benzene solution of 4-([2.2]paracyclophanyl)lithium prepared from
butyllithium (17 mmol) and 4-bromoparacyclophane (1a) (4 g, 14 mmol) and the mixture was heated with
stirring for 6 h. After cooling, the reaction mixture was treated with a saturated solution of ammonium chloride.
The organic layer was separated and the aqueous layer was extracted with ether (3 × 50 ml). The combined
extracts were dried over MgSO4. Ether was evaporated and compound 2 was separated chromatographically on
an alumina column using hexane–ethyl acetate eluent (30:1). Yield 0.44 g (8%).
B. 4-Benzoyl[2.2]paracyclophane (1b) (4 g, 13 mmol) was added to a solution of 2-pyridyllithium in
absolute ether (50 ml) prepared from butyllithium (26 mmol) and 2-bromopyridine (1.3 ml, 13 mmol) at -80°C
and the mixture was stirred at -40 to -30°C for 1 h. The alcohol 2 was separated similarly to method A to give a
yield of 3.19 g (62%) as colorless crystals with mp 123°C (ethyl acetate) and Rf 0.63. Mass spectrum, m/z (I, %):
M+ 391 (37), [M-C5H5N]+· = Φ1 312 (48), [Φ1-OH]+· 295 (42), [M-104]+· 287 (51). IR spectrum, ν, cm-1: 3335
(OH). UV spectrum, λmax, nm (log ε): 207 (4.77); 216 (4.7), 228 sh (4.57), 230 sh (4.29); 300 (3.4); 310 (3.36).
1H NMR spectrum, δ, ppm (1:1 mixture of diastereomers): 8.7 and 8.5 (0.5H each, both br. d, J = 4.9 Hz,
H-α Py); 7.60-7.05 (8H, m, 5H Ph and 3H Py); 6.85-6.20 (6H, m, Harom, paracycl); 6.2 (1H, s, H-5 arom.
paracycl); 5.98 and 5.5 (0.5H each, both s, OH); 3.4-2.5 (8H, m, Haliph.). Fluorescence spectrum, λmax, nm: 358.
Found, %: C 85.7; H 6.42; N 3.61. C28H25NO. Calculated, %: C 85.9; H 6.39; N 3.58. M 391.
α-Pyridyl([2.2]paracyclophan-4-yl)phenylmethanol Cu(II) Chloride (3). A solution of CuCl2·2H2O
(0.2 g, 1.17 mmol) in ethanol (10 ml) was added to a solution of the alcohol 2 (2.3 g, 0.53 mmol) and the
mixture was refluxed with stirring for 3 h. The product was cooled and left for 1 day. The precipitate formed was
filtered off and dried in air to give the complex 3 (1.32 g, 93%) as emerald colored prismatic crystals with
mp 169-170°C (decomp.) (see X-ray data for compound 3).
Cyclocondensation of Triarylmethanol 2. Compound 2 (0.4 g, 1 mmol) was refluxed in formic acid as
described in the study [1] and the product was separated chromatographically on an alumina column using
hexane as eluent. The first product was 1-phenyl-6-aza[3.2.2][1,2,5]-1,1α-dehydro-6H-cyclophano[1,2-a]-
pyridine (5) (0.13 g, 35%) as bright-yellow crystals with mp 218-221°C (hexane) and Rf 0.65. Mass spectrum,
m/z (I, %): M+· 373 (100), [M-104]+· 269 (65), 104 (7), 43 (23). UV spectrum, λmax, nm (log ε): 208 (4.26); 230
1
sh (4.15), 260 sh (4.12), 278 sh (4.06), 330 sh (3.16), 350 sh (3.02), 420 (2.88). H NMR spectrum, δ, ppm
752
Kryvenko
