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Russ.Chem.Bull., Int.Ed., Vol. 56, No. 11, November, 2007
Kolos et al.
and diamine 4d (0.15 g, 1 mmol) in mꢀxylene (30 mL) was
refluxed for 6 h. The solution was concentrated to 2/3 of the
initial volume on a rotary evaporator. The precipitate that formed
was purified by reprecipitation from an ethanolic NaOH soluꢀ
tion. The yield of diazepinone 5d was obtained in a yield of
0.22 g (75%), m.p. 241—242 °C.
Salt of 4ꢀbromobenzoyl[bis(4ꢀhydroxyꢀ2ꢀoxoꢀ2Hꢀchromenꢀ
3ꢀyl)]methane with 4ꢀmethylꢀoꢀphenylenediamine (7c). The yield
was 59%, m.p. 212—214 °C. Found (%): C, 60.07; H, 4.17;
+
N, 4.30. C26H14BrO7–C7H11N2 •H2O. Calculated (%):
C, 60.10; H, 4.13; N, 4.25. 1H NMR, δ: 2.18 (s, 3 H, Me); 6.27
(s, 1 H, CH); 6.45 (d, 1 H, oꢀPDA, J = 8.0 Hz); 6.67 (s, 1 H,
oꢀPDA); 6.88 (d, 1 H, oꢀPDA, J = 8.0 Hz); 7.20—7.24 (m, 4 H,
H(6), H(8)); 7.46 (t, 2 H, H(7), J = 7.3 Hz); 7.55 and 7.65
(both d, 2 H each, Ar, J = 8.8 Hz); 7.75 (d, 2 H, H(5),
J = 8.1 Hz).
2ꢀPhenylquinoxaline (8a). A mixture of adduct 3a (0.44 g,
1 mmol) and diamine 4a (0.11 g, 1 mmol) in DMF (10 mL) was
refluxed for 20 min. Then the reaction mixture was cooled and
benzene (5 mL) was added. Product 8a was obtained in a yield of
0.14 g (68%), m.p. 76 °C (from EtOH) (cf. lit. data14: m.p.
77—78 °C).
2ꢀ(4ꢀBromophenyl)ꢀ6ꢀbromoquinoxaline (8b) was synthesized
analogously. The yield was 65%, m.p. 148 °C (from EtOH)
(cf. lit. data14: m.p. 148—149 °C). 1H NMR, δ: 7.82 (d, 2 H,
oꢀH arom., J = 8.6 Hz); 7.95—8.05 (m, 2 H, H(7), H(8)); 8.30
(d, 2 H, mꢀH arom., J = 8.6 Hz); 8.38 (s, 1 H, H(5)); 9.63
(s, 1 H, H(3)).
B. Enamine 6 (0.15 g, 0.5 mmol) in mꢀxylene (15 mL) was
refluxed for 3.5 h. Then the solution was concentrated to 1/2 of
the initial volume on a rotary evaporator. The precipitate that
formed was purified by reprecipitation from an ethanolic NaOH
solution. The yield was 64%. Diazepine 5d synthesized by the
method A and the product prepared by the method B showed no
melting point depression. Found (%): C, 70.38; H, 4.70;
N, 11.20. C15H11N3O4. Calculated (%): C, 70.18; H, 4.77;
1
N, 11.69. H NMR, δ: 3.74 (s, 2 H, CH2); 6.97—7.02 (m, 2 H,
oꢀH arom., pꢀH arom.); 7.38—7.49 (m, 2 H, mꢀH arom.); 7.70
(d, 1 H, H(9), J = 8.0 Hz); 7.93 (d, 1 H, H(8), J = 8.0 Hz); 8.32
(d, 1 H, H(6), J = 8.0 Hz); 11.12 (s, 1 H, NH); 13.35
(s, 1 H, OH).
Earlier,9 compound 5d was characterized as the 8ꢀnitro isoꢀ
mer, m.p. 199—200 °C.
Salt of [bis(4ꢀhydroxyꢀ2ꢀoxoꢀ2Hꢀchromenꢀ3ꢀyl)]ꢀ4ꢀnitroꢀ
benzoylmethane with oꢀphenylenediamine (7d). A mixture of adꢀ
duct 3c (0.485 g, 1 mmol) and diamine 4a (0.11 g, 1 mmol) in
MeOH (10—12 mL) was refluxed for 1.25 h. After cooling,
yellow crystals of salt 7d were isolated in a yield of 0.38 g
(63%); no additional purification was required, m.p.
161—162 °C. Found (%): C, 62.85; H, 3.76; N, 6.87.
Xꢀray diffraction study. Triclinic crystals of 7d were preꢀ
+
pared by crystallization from EtOH, C26H14NO9–C6H9N2
•
•C2H5OH•H2O, at 20 °C a = 10.515(6) Å, b = 11.264(3) Å, c =
15.508(5) Å, α = 93.04(2)°, β = 104.90(4)°, γ = 116.18(4)°, V =
1563(1) Å3, Mr = 657.62, Z = 2, space group P–1, dcalc
=
1.397 g cm–3, µ(MoꢀKα) = 0.106 mm–1, F(000) = 688. The unit
cell parameters and the intensities of 8656 reflections (5154 inꢀ
dependent reflections, Rint = 0.032) were measured on a
Xcaliburꢀ3 diffractometer (MoꢀKα radiation, CCD detector,
+
C26H15O7–C6H8O2N3 •H2O. Calculated (%): C, 62.64;
H, 3.52; N, 6.98. 1H NMR, δ: 6.35 (s, 1 H, CH); 6.80—6.85 and
6.90—6.96 (both m, 2 H each, oꢀPDA); 7.16—7.22 (m, 4 H,
H(6), H(8)); 7.40—7.47 (t, 2 H, H(7), J = 7.0 Hz); 7.73 (d, 2 H,
H(5), J = 7.6 Hz); 7.90 and 8.17 (both d, 2 H each, Ar, J =
8.9 Hz). 13C NMR, δ: 49.06 (C(1″), C(sp3)); 61.52 (C(3), C(3´),
coumarin); 105.68 (C(3), C(6), oꢀPDA); 120.98 (C(4), C(5),
oꢀPDA); 124.55 (C(5), C(5´), coumarin); 125.58 (C(9), C(9´),
coumarin); 128.18 (C(7), C(7´), coumarin); 128.45 (C(6), C(6´),
coumarin); 128.55 (C(8), C(8´), coumarin); 129.40 (C(2), C(2´),
4ꢀNO2C6H4); 133.70 (C(3), C(3´), 4ꢀNO2C6H4); 136.62 (C(1),
C(2), oꢀPDA); 148.03 (C(4), 4ꢀNO2C6H4); 154.37 (C(10),
C(10´), coumarin); 157.72 (C(1), 4ꢀNO2C6H4); 168.95 (C(4),
C(4´), coumarin); 173.36 (C(2), C(2´), coumarin); 202.58
(C(2″), C=O).
graphite monochromator, ω scanning technique, 2θ
= 50°).
max
The hydrogen atoms were located in difference electron density
maps and refined using a riding model with Uiso = nUeq of the
parent nonhydrogen atoms (n = 1.5 for the hydroxy groups and
n = 1.2 for the other hydrogen atoms). The hydrogen atoms of
the protonated amino group and the hydroxy group O(3)H were
refined isotropically. The structure was refined by the fullꢀmaꢀ
trixꢀleastꢀsquares method based on F 2 with anisotropic displaceꢀ
ment parameters for nonhydrogen atoms to wR2 = 0.101 based
on 5062 reflections (R1 = 0.046 based on 2190 reflections with
F > 4σ(F ), S = 0.766). The atomic coordinates and complete
tables of the bond lengths and bond angles were deposited with
the Cambridge Structural Database.
Compounds 7a—c were synthesized analogously.
Salt of benzoyl[bis(4ꢀhydroxyꢀ2ꢀoxoꢀ2Hꢀchromenꢀ3ꢀ
yl)]methane with oꢀphenylenediamine (7a). The yield was 57%,
m.p. 155—156 °C. Found (%): C, 67.80; H, 4.60; N, 5.00.
References
+
C26H15O7–C6H9N2 •H2O. Calculated (%): C, 67.84; H, 4.63;
N, 4.94. 1H NMR, δ: 6.33 (s, 1 H, CH); 6.78—6.86 and
6.90—6.98 (both m, 2 H each, oꢀPDA); 7.18—7.24 (m, 4 H,
H(6), H(8)); 7.26—7.32 (m, 3 H, Ar); 7.46 (t, 2 H, H(7), J =
7.3 Hz); 7.70—7.75 (m, 4 H, H(5), 2 HAr).
1. I. Manolov, C. MaichleꢀMoessmer, and N. Danchev, Eur.
J. Med. Chem., 2006, 41, 882.
2. I. Manolov, C. MaichleꢀMoessmer, I. Nicolova, and
N. Danchev, Arch. Pharm., 2006, 336, 319.
Salt of 4ꢀbromobenzoyl[bis(4ꢀhydroxyꢀ2ꢀoxoꢀ2Hꢀchromenꢀ
3ꢀyl)]methane with oꢀphenylenediamine (7b). The yield was 60%,
m.p. 176—177 °C. Found (%): C, 59.50; H, 3.86; N, 4.40.
3. G. Cravotto, S. Tagliapietra, R. Cappelo, G. Palmisano,
M. Curini, and M. Boccalini, Arch. Pharm., 2006, 336, 129.
4. A. Sandeep, B. Devanand, and R. Shinde, Bioorg. Med. Chem.
Lett., 2006, 16, 6181.
+
C26H14BrO7–C6H9N2 •H2O. Calculated (%): C, 59.55; H, 3.90;
N, 4.34. 1H NMR, δ: 6.28 (s, 1 H, CH); 6.80—6.86 and
6.90—6.95 (both m, 2 H each, oꢀPDA); 7.20—7.28 (m, 4 H,
H(6), H(8)); 7.48 (t, 2 H, H(7), J = 7.0 Hz); 7.53 and 7.65
(both d, 2 H each, Ar, J = 8.8 Hz); 7.72 (d, 2 H, H(5),
J = 7.7 Hz).
5. M. Choudhary, N. Fatima, K. Khan, S. Jalil, S. Iqbal, and
A. Rahman, Bioorg. Med. Chem., 2006, 14, 8066.
6. V. G. Belikov, Farmatsevticheskaya khimiya [Pharmaceutical
Chemistry], Vysshaya shkola, Moscow, 1993, 768 (in
Russian).