The syn isomer of the oxime of 2-amino-5-methylbenzophenone (1) was prepared according to our
previous procedure [5].
4-Chlorobutyryloximine of 2-(4-Chlorobutyryl)amino-5-methylbenzophenone (anti isomer) (2) and
2-(3-Chloropropyl)-6-methyl-4-phenylquinazoline 3-Oxide (3). A solution of 4-chlorobutyryl chloride (10 ml,
0.089 mol) in 1,4-dioxane (10 ml) was added dropwise to a stirred solution of compound 1 (10 g, 0.044 mol) in
1,4-dioxane (70 ml) cooled to <10°C, stirred for 3 h, poured into water, and extracted with chloroform. The
chloroform extract was evaporated. The orange oily residue was crystallized from benzene to give 2.29 g (33%)
quinazoline 3-oxide 3, mp 140-144°C. UV spectrum (EtOH), λmax, nm (log ε): 232 (4.08), 261 (4.27), 312
(3.64), 355 (3.57). Mass spectrum, m/z: 312 [M]+. IR spectrum, ν, cm-1: 2985 (CH), 1600 (C=N), 1300 (N–O).
1H NMR spectrum, δ, ppm (J, Hz): 7.86-7.09 (8H, m, Ar–H); 3.82 (2H, t, J = 6.7, СH2Cl); 3.25 (2H, t, J = 7.2,
N=C–СH2); 2.40 (3H, s, CH3); 2.36 (2H, q, J = 7.0, СH2–CH2–CH2). Mother liquor chromatograhed on the silica
gel column using benzene as the eluent. Yield of the compound 2 2.84 g (30%) (oil). UV spectrum (EtOH), λmax
,
nm (log ε): 239 (4.38), 323 (3.52). Mass spectrum (FAB), m/z: 434 [М]+. IR spectrum ν, cm-1: 3265 (NH), 2945
1
(СH), 1745 (O–C=O), 1675 (NH–C=O), 1595 (С=N). Н NMR spectrum, δ, ppm (J, Hz): 10.19 (1H, s, NH);
7.85-6.94 (8H, m, Ar–H); 3.58 (2H, t, J = 6.5, NHCO–CH2–CH2–CH2Cl); 3.55 (2H, t, J = 6.5, OCO–CH2–CH2–
CH2Cl); 2.53 (2H, t, J = 7.2, NHCO–CH2); 2.30 (2H, t, J = 7.2, OCO-CH2); 2.25 (3H, s, CH3); 1.99 (2H, q,
J = 6.9, NHCO–CH2–CH2–CH3); 1.91 (2H, q, J = 6.9, OCO–CH2–CH2-CH3).
X-Ray Diffraction Structural Analysis. Unit cell parameters of triclinic crystals of 3 grown in benzene
at 100(2) K: a = 7.5514(3), b = 9.5772(4), c = 10.5746(5) Å, V = 752.19(6) Å3, dcalc = 1.381 g/cm3, space group
P-1, Mr = 312.79, Z = 2, wavelength 0.71073 Å, F(000) 328, α = 81.0500(10), β = 84.6750(10),
γ = 88.9510(10)º, GOOF 1.000. θmax = 30º. Index range: -10 ≤ h ≤ 10, -13 ≤ k ≤ 13, -14 ≤ l ≤ 14; 9804 measured
reflections, 4353 independent reflections (Rint = 0.0214). R-factor (I>2σ(I)): R1 = 0.0355, wR2 = 0.0889. R-factor
(over total set): R1 = 0.0430, wR2 = 0.0941; ∆ρmax 0.388, ∆ρmin –0.279 eÅ-3.
The unit cell parameters and experimental data for the compound studied were obtained on a
Bruker SMART APEX2 CCD diffractometer using MoKα radiation and a graphite monochromator. The
structure was solved by the directly method and refined anisotropically relative to F2 by the method of least
squares for the non-hydrogen atoms using the SHELXTL-98 program package [14]. The hydrogen atom
positions were calculated geometrically.
The coordinates of the non-hydrogen atoms and their equivalent isotropic temperature parameters for 3
may be obtained from the authors (e-mail: wizard@homei.net.ua).
The authors thank Z. A. Starikova (X-Ray Structural Centre, Institute of Organoelement Compounds of
the Russian Academy of Sciences, Moscow, Russia) for the X-ray diffraction structural analysis of 3.
REFERENCES
1.
2.
O. V. Kulikov, S. A. Andronati, V. I. Pavlovskii, O. V. Mazepa, and T. A. Kabanova, Visnyk ONU, 5,
No. 2, 68 (2000).
V. I. Pavlovsky and O. V. Kulikov, in: V. G. Kartsev (editor), Selected Methods for Synthesis and
Modification of Heterocycles, Vol. 1, IBS Press, Moscow (2002), p. 542.
S. A. Andronati, Yu. A. Simonov, V. I. Pavlovsky, O. V. Kulikov, M. Gdanets, and A. V. Mazepa, Zh.
Obshch. Khim., 75, 969 (2005).
3.
4.
5.
L. H. Sternbach, E. Reeder, O. Keller, and W. Metlesics, J. Org. Chem., 26, 4488 (1961).
V. I. Pavlovsky, O. V. Kulikov, T. L. Karaseva, T. A. Kabanova, A. V. Mazepa, and S. I. Andronati,
Ukr. Khim. Zh., 64, 123 (1998).
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