Reactions of 5-diazoimidazoles with steroid hydrazones

Article abstract of DOI:10.1007/s10593-005-0070-2

The reaction of 5-diazoimidazoles with steroid hydrazones was studied. The structure of the steroid derivative was found to have a significant effect on the direction of the nitrogen transfer in the unstable intermediate tetrazene. The presence of a labile proton in the reaction mixture permits stabilization of one of the tetrazene forms such that only direction was found for the nitrogen transfer in all the reactions studied, leading to imidazole azides and iminosteroid derivatives.

Full text of DOI:10.1007/s10593-005-0070-2

Chemistry of Heterocyclic Compounds, Vol. 40, No. 10, 2004
RECYCLIZATION OF 2-IMINOCOUMARINS
USING NUCLEOPHILIC REAGENTS. 6*. REACTION
OF 2-IMINOCOUMARIN-3-CARBOXAMIDES
WITH 2-AMINOBENZOPHENONES
S. V. Rusanova, I. A. Zhuravel', S. N. Kovalenko, V. P. Chernykh, and V. N. Baumer
It has been shown that the reaction of 2-iminocoumarin-3-carboxamides with substituted
2
3
-aminobenzophenones occurs in accordance with recyclization mechanism to form substituted
-(4-phenylquinazolin-2-yl)coumarins. The structure of the compounds obtained was confirmed by
spectroscopic data and by X-ray analysis.
Keywords: 2-aminobenzophenones, 3-(4-arylquinazolin-2-yl)coumarins, 2-iminocoumarins, X-ray
analysis, recyclization.
In previous reports we have shown that, depending on the conditions, the reaction of 2-imino-2H-1-
benzopyran-3-carboxamides with N-nucleophilic reagents can take place both via formation of 2-N-substituted
iminocoumarins (acid medium, 20°C) [2-7] and by recyclization mechanism to give 3-substituted coumarins
(
neutral medium, 120-200°C) [2, 7]. In certain examples the use of binucleophilic reagents (o-substituted
anilines, arenecarboxylic acid hydrazides, thiosemicarbazides, anthranilic acid derivatives) gives
-heterylcoumarins which are the products of their subsequent cyclization [1, 6-8]. In this study we continue to
3
investigate the reaction of 2-imino-2H-1-benzopyran-3-carboxamides with nucleophilic reagents and to study the
behavior of these compounds when reacting with substituted 2-aminobenzophenones.
1
The starting R -substituted 2-iminocoumarin-3-carboxamides 1 were prepared by known methods and
introduced into the reaction with substituted 2-aminobenzophenones 2. As shown by us, the recyclization
1
2
3
products R -substituted 3-[6-R -4-(R -phenyl)quinazolin-2-yl]coumarins 7a-u (see Scheme 1 and Table 1) rather
than the expected 2-substituted coumarins 3 are formed in glacial acetic acid, even in the cold.
1
Analysis of the H NMR spectra of the reaction products shows that the signals for the protons of the
imino group (12-13 ppm) and the protons of the amide group (9.0-9.2, 7.7-7.9 ppm), which are characteristic of
the spectra of the starting 2-iminocoumarin-3-carboxamides 1 [9], are lost in the course of the reaction. The
1
presence in the H NMR spectra of the overlapping signals for the aromatic protons of the coumarin and
quinazoline fragments in the region of 6.54-8.70 ppm and the singlet signal for the H-4 proton of the coumarin
ring (8.65-9.49 ppm) agree fully with the proposed structure (Table 2).
_
*
_
______
For Communication 5 see [1].
_________________________________________________________________________________________
National Pharmaceutical University, Kharkov, 61002, Ukraine; e-mail: ulk@ukrfa.kharkov.ua.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1533-1542, October, 2004. Original
article submitted April 24, 2003.
0
009-3122/04/4010-1323©2004 Springer Science+Business Media, Inc.
1323

Scheme 1
R3
O
NH2 O
NH2
R1
+
–
NH3
O
NH
1
R2
2
O
N
NH2
R1
NH3
R3
O
O
R2
3
O
O
N
NH2
N
NH2
R1
R1
R3
HN
O
HO NH2
OH
HO
R3
R2
R2
5
4
R3
R3
R2
R2
N
N
–
NH3
N
R1
N
R1
CONH2
OH
O
O
6
7
a-u
1
3
1
3
1
3
1
3
1
3
7
a R = R = H; b R = H, R = Cl; c R = 7-OH, R = H; d R = 6-Br, R = H; e R = 6-Br, R = Cl;
1
3
1
3
1
3
1
3
f R = 6-Br, R = H; g R = 6-Cl, R = H; h R = 6-Cl, R = Cl; i R = 6-OMe, R = H;
1
3
1
3
1
3
1
3
j R = 6-OMe, R = H; k R = 7-OMe, R = H; l R = 7-OMe, R = Cl; m R = 7-OEt, R = H;
n R = 7-NEt
1
3
1
3
1
3
1
3
2
, R = H; o R = 8-OMe, R = H; p R = 8-OMe, R = Cl; q R = 8-OEt, R = H;
1
3
1
3
1
3
r R = 8-OEt, R = Cl; s R = 8-CH CH = CH , R = H; t R = 5,6-benzo, R = H;
2
2
1
3
2
2
6
u R = 6-n-C H13-7-OH, R = H; a-e,g-u R = Cl, f R = Br
The IR spectra of the compounds prepared show the absence of the N–H stretching vibrations of the
-
1
-1
imine and amide fragments (3400-3300 cm ) and those of the amide carbonyl group (1670-1690 cm ) seen in
the starting 2-iminocoumarin-3-carboxamides 1 [9] but the appearance of a strong stretching vibration band for
-
1
-1
the lactone C=O (1713-1763 cm ) and a weak band for the C=N stretching vibrations (1632-1694 cm ) which,
1
324

in some examples, may be overlapped by the more intense aromatic C=C stretching vibration bands (Table 1).
The existence of an intense molecular ion peak (m/z 414, I = 100%) and characteristic coumarin fragmentation
+
+
+
ions (m/z: 414.9999 [M] , 379.3037 [M-Cl] . 190.1656, 177.2742 [M-C H ClN ] , 127.1440) in the case of the
1
4
8
2
molecule of 3-(6-chloro-4-phenylquinazolin-2-yl)-8-methoxycoumarin (7o) also confirms the correctness of the
proposed structure.
These facts have allowed us to propose that the given reaction occurs according to the recyclization
mechanism [5] which includes the stage of forming intermediate 2-[(2-aroylaryl)imino]-2H-1-benzopyran-3-
carboxamides 3 which could not be isolated. The instability of these structures is evidently connected with the
activation of the carbonyl group of the benzophenone fragment under the action of ammonium ion liberated in
the first stage and this leads to the formation of the novel intermediates – amino alcohols 4. Further, as a result of
the attack of the amino group on the carbon atom of the C=N bond of iminocoumarin the iminolactone ring is
opened followed by a cis-trans isomerization of the intermediate 5 to 6 and then its cyclization to give
1
2
3
R -substituted 3-[6-R -4-(R -phenyl)quinazolin-2-yl)coumarins 7a-u.
1
2
3
TABLE 1. R -Substituted 3-[6-R -4-(R -Phenyl)quinazolin-2-yl]coumarins
-
1
Com-
pound
Empirical
formula
Found N, %
Calculated N, %
IR spectrum, ν, cm
Yield,
%
—
—————
mp, °С
C=O
C=N
C=C
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
a
b
c
d
e
f
С
С
С
С
С
С
С
С
С
С
С
С
С
С
С
С
С
С
С
С
С
23
23
23
23
23
23
23
23
24
24
24
24
25
27
24
24
25
25
26
27
29
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
13ClN
12Cl
13ClN
12BrClN
11BrCl
12Br
2
O
2
7.30
240-242
194-196
301-303
223-225
204-206
242-244
235-237
237-239
238-240
230-232
207-209
218-220
193-195
197-199
224-226
235-237
206-208
218-220
178-180
>300
1751
1736
1713
1751
1739
1753
1763
1747
1743
1719
1727
1743
1739
1715
1738
1739
1741
1724
1746
1759
1720
1604
1603
1613
1612
1605
1596
1600
1600
1604
1570
1615
1612
1616
1615
1605
1603
1602
1616
1596
1600
1616
71
68
52
84
87
85
78
71
73
70
66
59
73
51
75
77
78
74
80
63
55
7
.28
2
N
2
O
2
6.67
.68
6
2
O
3
6.96
.99
1694
1632
1650
1640
1651
6
2
O
2
6.07
.04
6
2
N
2
O
2
5.60
.62
5
2
N
2
O
2
5.50
.51
5
g
h
i
12Cl
2
3
N
2
2
O
2
2
6.68
.68
6
11Cl
N
O
6.20
.17
6
15ClN
14Cl
15ClN
14Cl
2
O
3
6.77
.75
1680
1687
1671
6
j
2
N
2
O
3
6.20
.23
6
k
l
2
O
3
6.77
.75
6
2
N
2
O
3
6.21
.23
6
m
n
o
p
q
r
s
17ClN
22ClN
15ClN
2
3
2
O
O
O
3
2
3
6.55
.53
6
9.21
.22
9
6.77
.75
6
14Cl
17ClN
16Cl
2
N
2
O
3
6.20
.23
6
2
O
3
6.55
.53
6
2
N
2
O
3
6.03
.05
6
17ClN
15ClN
25ClN
2
2
2
O
O
O
2
2
3
6.60
.59
6
t
6.41
.44
1671
6
u
5.77
.78
253-255
5
1
325

1
1
2
3
TABLE 2. H NMR Spectral Characteristics of R -Substituted 3-[6-R -4-(R -Phenyl)quinazolin-2-yl]coumarins
Chemical shifts, δ, ppm (SSCC, J, Hz)
Aromatic protons
Com-
pound
Other protons
5
Coumarin ring
2
Quinazoline ring
3
Benzene ring
4
1
7
7
7
7
7
7
7
7
7
a
7.32-7.38 (2H, m, H-6, Н-8); 7.76 (1H, d, J = 8, H-5); 7.91 (1H, dd, J
1
= 8, J
2
= 1, H-7);
7.62 (3H, m); 7.84 (2H, m)
7.52-7.90 (4H, m)
8
.80 (1H, s, H-4)
6.80 (2H, m, H-6, H-8); 7.64 (1H, m, H-7);
.90 (1H, m, H-5); 8.78 (1H, s, H-4)
6.80 (2H, m, H-6, H-8); 8.03 (1H, m, H-5);
.71 (1H, s, H-4)
7.40 (1H, d, J = 10, H-8); 7.54 (1H, m, H-7);
.73 (1H, d, J = 8, H-5); 8.76 (1H, s, H-4)
7.43 (1H, d, J = 9, H-8); 7.57 (1H, m, H-7);
.86 (1H, dd, J = 10, J = 1, H-5); 8.77 (1H, s, H-4)
7.38 (1H, d, J = 10, H-8); 7.43 (1H, m, H-7);
.74 (1H, dd, J = 8, J = 1, H-5); 8.73 (1H, s, H-4)
7.47 (1H, d, J = 9, H-8); 7.65 (1H, m, H-7);
.58 (1H, m, H-5); 8.75 (1H, s, H-4)
7.47 (1H, d, J = 9, H-8); 7.58 (1H, m, H-7);
.70 (1H, m, H-5); 8.77 (1H, s, H-4)
8.15 (1H, d, H-8); 8.18 (1H, s, H-5)
b
c
d
e
f
8.11 (3H, m)
7
8.02 (3H, m)
7.62-7.97 (5H, m)
10.80 (1H, s, OH)
8
7.96 (1H, m, H-7); 8.09 (1H, m, H-5);
8.18 (1H, m, H-8)
8.09 (1H, dd, J
8.20 (2H, m, H-7, H-8)
8.08 (2H, m, H-5, H-7); 8.24 (1H, s, H-8)
7.54 (3H, m); 7.90 (2H, m)
7.62-7.70 (4H. m)
7
1 2
= 9, J = 1, H-5);
7
1
2
7.43-8.08 (5H, m)
7
1
2
g
h
i
7.65 (1H, dd, J
8.09 (1H, m, H-5); 8.14 (1H, d, J = 7, H-8)
8.08 (2H, dd, J = 10, J = 1, H-5, H-7);
1
= 7, J
2
= 1, H-7);
7.65-8.05 (5H, m)
7
1
2
7.58-7.70 (4H, m)
7
8.20 (1H, d, J = 10, H-8),
7.28 (1H, dd, J
1
= 10, J
2
= 1, H-8);
8.06-8.12 (3H, m, H-5, H-7, H-8)
7.43-7.52 (4H, m);
7.87 (1H, m)
3.81 (3H, s, OCH
3
)
)
7
8
.62 (1H, m, H-7); 7.87 (1H, m, H-5);
.80 (1H, s, H-4)
7
j
7.26 (1H, dd, J
H-7); 7.50 (1H, d, J = 5, H-5); 8.77 (1H, s, H-4)
1
= 10, J
2
= 1, H-8); 7.40 (1H, d, J = 9, 7.70 (1H, m, H-7); 8.17 (1H, dd, J
H-5); 8.40 (1H, d, J = 9, H-8)
1
= 9, J
2
= 1,
7.50-7.70 (4H, m)
3.77 (3H, s, OCH
3

TABLE 2 (continued)
1
2
3
4
5
7
7
7
7
7
7
7
7
7
k
l
7.00 (1H, dd, J
1
= 9, J
2
= 1, H-6); 7.07 (1H, d, J = 5,
8.04-8.14 (3H, m, H-5, H-7, H-8)
7.66 (3H, m); 7.87 (2H, m)
3.90 (3H, s, ОCH
3
)
)
H-8); 7.87 (1H, m, H-5); 8.80 (1H, s, H-4)
6.96 (1H, dd, J = 9, J = 1, H-6); 7.02 (1H, d, J = 5,
H-8); 7.80 (1H, d, J = 9, H-5); 8.72 (1H, s, H-4)
6.92 (1H, dd, J = 9, J = 1, H-6); 7.00 (1H, d, J = 5,
H-8); 7.64 (1H, m, H-5); 8.74 (1H, s, H-4)
6.54 (1H, d, J = 5, H-8); 6.71 (1H, dd, J = 8, J
H-6); 7.58 (1H, m, H-5); 8.65 (1H, s, H-4)
7.26 (1H, t, J = 7, H-6); 7.81 (2H, m, H-5, H-7);
.70 (1H, s, H-4)
7.32 (1H, t, J = 8, H-6); 7.65 (2H, m, H-5, H-7);
.75 (1H, s, H-4)
7.28 (1H, t, J = 8, H-6); 7.46 (1H, dd, J
H-5); 7.65 (1H, m, H-7); 8.80 (1H, s, H-4)
7.34 (1H, d, J = 6, H-6); 7.58 (1H, d, J = 6, H-7);
.64 (1H, m, H-5); 8.78 (1H, s, H-4)
7.31 (1H, t, J = 8, H-6); 7.62 (1H, m, H-7);
.74 (1H, d, J = 8, H-5); 8.71 (1H, s, H-4)
1
2
7.61 (1H, m, H-7); 8.02 (1H, dd, J
H-5); 8.14 (1H, d, J = 9, H-8)
8.00-8.12 (3H, m, H-5, H-7, H-8)
1
= 9, J
2
= 1,
7.52-7.70 (4H, m)
7.64-7.85 (5H, m)
3.86 (3H, s, ОCH
3
m
n
o
p
q
r
1
2
1.34 (6H, t, J = 7, 2СH
4.11 (2H, q, J = 7, 2СH
2
CH
CH
CH
CH
3
);
2
3
)
1
2
= 1,
7.94 (1H, d, J = 8, H-7); 7.98 (1H, d, J = 9, H-5); 7.58-7.86 (5H, m)
8.06 (1H, dd, J = 9, J = 1, H-8)
1.15 (6H, t, J = 7, 2СH
3.45 (4H, q, J = 7, 2СH
2
3
);
1
2
2
3
)
7.92 (1H, d, J = 9, H-7); 8.10 (1H, s, H-5);
8.25 (1H, d, J = 9, H-8)
8.03 (1H, d, J = 6, H-5); 8.18 (1H, d, J = 5, H-8) 7.55-7.74 (4H, m)
7.36 (2H, m); 7.65 (2H, m);
7.81 (1H, m)
4.02 (3H, s, ОCH
3
)
8
3.91 (3H, s, ОCH
3
)
8
1
= 8, J
2
= 1,
8.06-8.17 (3H, m, H-5, H-7, H-8)
7.30 (1H, m); 7.65 (2H, m);
7.88 (2H, m)
1.42 (3H, t, J = 7, СH
4.20 (2H, q, J = 7, СH
2 3
CH );
2
3
CH )
7.72 (1H, d, J = 5, H-7), 8.10 (1H, dd, J
1
= 7,
7.32 (2H, m);
7.64-7.72 (2H, m)
1.42 (3H, t, J = 7, СH
4.20 (2H, q, J = 7, СH
2
3
CH );
7
J
2
= 1, H-5); 8.24 (1H, d, J = 5, H-8)
2
3
CH )
3
.57 (2H, d, J = 9,
СH СH=CH ); 5.07 (2H, dd,
= 18, J = 7, СH СH=CH );
.02 (1H, m, СH СH=CH
s
8.00-8.12 (3H, m, H-5, H-7, H-8)
7.50 (1H, d);
7.64 (2H, m); 7.86 (2H, m)
7
2
2
J
1
2
2
2
6
2
2
)
7
7
t
7.65-8.06 (6H, m); 9.49 (1H, s, H-4)
7.55 (1H, s, H-8); 7.77 (1H, m, H-5);
8.20 (1H, m, H-7); 8.26 (1H, m, H-5);
7.63-7.90 (5H, m)
8
.56 (1H, d, J = 8, H-8)
u
8.00-8.10 (3H, m, H-5, H-7, H-8)
7.62 (3H, m); 7.85 (2H, m)
0.88 (3H, m); 1.29 (6H, s,
(CH (СH CH ); 1.53 (2H, s,
(СH CH ); 2.50 (2H, s,
CH (СH CH );
8
.70 (1H, s, H-4)
)
2 2
2
)
3
3
CH
CH
2
)
2 4
3
3
2
2
2
)
3
3
.20 (1H, s, OH)

With the object of confirming the structure of the final products we have carried out an X-ray
investigation of 3-(6-chloro-4-phenylquinazolin-2-yl)-7-hydroxycoumarin 7c. The assignment of crystal of this
compound to hexagonal syngony proved quite unexpected, but as the verification of the presence of twinning in
the polarizing microscope proved negative, the refinement was carried out in the hexagonal cell by a direct
method with subsequent electron density synthesis. It was found that the structure of compound 7c was made up
of triads of the molecules formed through O–H···O hydrogen bonding. The atomic coordinates can be obtained
from the authors; the bond lengths and bond angles in the structure are given in Tables 3 and 4. Figure 1 shows
the numbering scheme for the atoms in the basic molecular structures.
Three molecules of the compound make up the independent cell unit. In each molecule the coumarin and
benzimidazole fragments lie in virtually one plane. Differences are observed in torsional angles between the
planes of the phenyl substituent and the quinazoline fragment. As a result of the geometrical requirements in the
least-squares refinement and the existence of pseudosymmetry it can be proposed that the standard deviations of
the obtained geometrical parameters of the molecules (Tables 3 and 4) are reduced when compared with the
actually observed scatter in the bond lengths and bond angles.
TABLE 3. Bond Lengths (d) in the Triad of Basic Molecules of Compound 7c
d, Å
Bond
С
А
В
Cl(1)–C(19)
O(1)–C(10)
O(1)–C(2)
1.784(4)
1.401(4)
1.415(4)
1.198(5)
1.377(5)
1.331(5)
1.467(2)
1.501(4)
1.367(4)
1.375(4)
1.378(4)
1.381(3)
1.382(3)
1.426(4)
1.381(3)
1.321(2)
1.350(2)
1.313(2)
1.344(2)
1.496(5)
1.527(4)
1.373(3)
1.390(3)
1.374(4)
1.379(4)
1.377(3)
1.378(4)
1.3953(19)
1.3967(19)
1.3973(19)
1.397(2)
1.3962(19)
1.3953(19)
1.787(4)
1.414(4)
1.414(5)
1.194(5)
1.382(5)
1.329(5)
1.471(2)
1.521(4)
1.384(4)
1.382(4)
1.375(4)
1.378(4)
1.380(3)
1.431(4)
1.381(3)
1.322(2)
1.352(2)
1.310(2)
1.347(2)
1.507(5)
1.532(4)
1.380(3)
1.383(3)
1.378(4)
1.382(4)
1.378(3)
1.378(4)
1.3956(15)
1.3946(18)
1.3957(18)
1.3977(19)
1.3946(19)
1.3949(15)
1.784(4)
1.403(4)
1.408(5)
1.192(5)
1.375(5)
1.333(5)
1.471(2)
1.511(4)
1.374(4)
1.378(4)
1.376(4)
1.385(4)
1.381(3)
1.434(4)
1.384(3)
1.321(2)
1.350(2)
1.310(2)
1.345(2)
1.497(5)
1.524(4)
1.382(3)
1.390(3)
1.381(4)
1.379(4)
1.378(3)
1.381(3)
1.3941(19)
1.3959(19)
1.3948(19)
1.3955(15)
1.3954(19)
1.3960(19)
C(2)–O(11)
C(2)–C(3)
C(3)–C(4)
C(3)–C(14)
C(4)–C(5)
C(5)–C(6)
C(5)–C(10)
C(6)–C(7)
C(7)–C(8)
C(8)–C(9)
C(8)–O(12)
C(9)–C(10)
N(13)–C(22)
N(13)–C(14)
C(14)–N(15)
N(15)–C(16)
C(16)–C(17)
C(16)–C(23)
C(17)–C(18)
C(17)–C(22)
C(18)–C(19)
C(19)–C(20)
C(20)–C(21)
C(21)–C(22)
C(23)–C(24)
C(23)–C(28)
C(24)–C(25)
C(25)–C(26)
C(26)–C(27)
C(27)–C(28)
1
328

TABLE 4. Bond Angles (ω) in The Triad of Basic Molecules of Compound 7c
ω, deg
А
Angle
С
B
C(10)–O(1)–C(2)
O(11)–C(2)–C(3)
O(11)–C(2)–O(1)
C(3)–C(2)–O(1)
120.7(4)
132.4(3)
106.1(3)
121.4(4)
118.8(3)
118.0(3)
123.2(3)
122.3(4)
117.0(3)
125.4(4)
117.3(3)
123.4(4)
116.5(3)
122.8(3)
111.6(3)
124.3(3)
116.3(3)
123.2(3)
119.3(3)
117.4(3)
116.2(3)
130.2(3)
109.8(3)
120.0(3)
112.9(3)
123.4(3)
116.2(3)
119.8(3)
121.1(3)
125.6(3)
113.1(2)
113.9(4)
128.6(4)
115.7(3)
114.8(3)
114.0(4)
121.0(3)
115.3(3)
123.6(3)
120.9(3)
119.94(12)
120.7(4)
119.2(4)
119.84(13)
119.41(15)
119.56(15)
119.90(13)
119.93(12)
122.7(4)
133.5(4)
107.1(3)
119.4(4)
119.2(3)
118.2(3)
122.7(3)
124.0(4)
115.5(4)
128.6(4)
115.0(3)
124.3(4)
115.9(4)
123.7(4)
111.7(3)
124.5(3)
116.4(4)
123.5(4)
119.1(3)
117.0(3)
116.6(3)
129.8(3)
110.9(3)
119.4(3)
113.0(3)
122.3(3)
116.0(4)
117.7(3)
121.9(3)
124.1(3)
113.1(2)
113.3(4)
129.3(4)
115.1(3)
115.1(3)
113.1(4)
122.2(3)
116.6(3)
123.4(3)
120.0(3)
120.01(11)
127.1(4)
112.7(4)
119.86(12)
119.68(13)
119.82(12)
120.05(12)
119.91(12)
124.3(4)
133.8(4)
107.2(3)
118.5(4)
118.9(3)
117.7(3)
123.0(3)
124.6(4)
113.5(3)
131.1(4)
115.0(3)
126.4(4)
113.9(4)
125.7(3)
110.8(3)
123.4(3)
113.7(4)
126.1(3)
118.6(3)
115.1(3)
116.0(3)
130.5(3)
109.5(3)
119.6(3)
113.0(3)
123.8(3)
116.3(4)
119.8(3)
122.3(3)
124.9(3)
112.7(2)
113.3(4)
128.9(4)
115.3(3)
115.7(3)
113.0(4)
122.8(4)
116.9(3)
123.8(3)
119.0(3)
120.01(12)
122.2(4)
117.8(4)
120.01(12)
119.99(12)
119.85(13)
119.85(13)
119.90(12)
C(4)–C(3)–C(2)
C(4)–C(3)–C(14)
C(2)–C(3)–C(14)
C(3)–C(4)–C(5)
C(6)–C(5)–C(10)
C(6)–C(5)–C(4)
C(10)–C(5)–C(4)
C(5)–C(6)–C(7)
C(6)–C(7)–C(8)
C(7)–C(8)–C(9)
C(7)–C(8)–O(12)
C(9)–C(8)–O(12)
C(10)–C(9)–C(8)
C(5)–C(10)–C(9)
C(5)–C(10)–O(1)
C(9)–C(10)–O(1)
C(22)–N(13)–C(14)
N(15)–C(14)–N(13)
N(15)–C(14)–C(3)
N(13)–C(14)–C(3)
C(14)–N(15)–C(16)
N(15)–C(16)–C(17)
N(15)–C(16)–C(23)
C(17)–C(16)–C(23)
C(18)–C(17)–C(22)
C(18)–C(17)–C(16)
C(22)–C(17)–C(16)
C(17)–C(18)–C(19)
C(18)–C(19)–C(20)
C(18)–C(19)–Cl(1)
C(20)–C(19)–Cl(1)
C(21)–C(20)–C(19)
C(20)–C(21)–C(22)
N(13)–C(22)–C(21)
N(13)–C(22)–C(17)
C(21)–C(22)–C(17)
C(24)–C(23)–C(28)
C(24)–C(23)–C(16)
C(28)–C(23)–C(16)
C(23)–C(24)–C(25)
C(24)–C(25)–C(26)
C(27)–C(26)–C(25)
C(28)–C(27)–C(26)
C(27)–C(28)–C(23)
1
329

Fig. 1. Atom numbering in the triad of the basic molecules of 3-(6-chloro-4-phenylquinazolin-2-yl)-
-hydroxycoumarin (7c).
7
Hence the reaction of 2-iminocoumarin-3-carboxamides with substituted 2-aminobenzophenones in
glacial acetic acid in the cold occurs in accordance with recyclization mechanism to give substituted
3
3
-(4-arylquinazolin-2-yl)coumarins and is a convenient method for the synthesis of this series of
-heterylcoumarins.
EXPERIMENTAL
IR spectra for the synthesized compounds were recorded on a Specord M-80 spectrophotometer for KBr
1
tablets. H NMR spectra were recorded on a Varian WXR-400 (200 MHz) instrument using DMSO-d and TMS
6
as internal standard. Electron impact mass spectra were obtained on a Finnigan MAT 4615B instrument with
ionization energy of 70 eV and with ballistic heating of the sample. X-ray analysis was carried out on a Siemens
P3/PC four-circle, automatic diffractometer.
1
R -Substituted 2-Iminocoumarin-3-carboxamides 1 were prepared by the method in [9].
3
-(4-Arylquinazolin-2-yl)coumarins 7a-u (General Method). The corresponding 2-amino-
benzophenone 2 (2 mmol) was dissolved with heating in glacial acetic acid (10 ml). 2-Iminocoumarin-3-
carboxamide 1 (2 mmol) was added to the warm solution (30-40°C) and it was refluxed using a reflux condenser
for 20-30 min. A heavy precipitate was formed upon cooling the reaction mixture. This was filtered off, washed
with water and with ethanol, and recrystallized from mixture of ethanol–water (compounds 7c,d,g,s-u) or from
ethanol–DMF (compounds 7a,b,e,f,t).
1
330

X-ray Analysis of 3-(6-Chloro-4-phenylquinazolin-2-yl)-7-hydroxycoumarin (7c). Measurement of
the intensities was carried out by the 2θ/θ scanning method in the range of angles 4<2θ<50° at a rate of from
2
to 30 deg./min to give 2724 nonzero, nonequivalent reflections, of which 1954 were observed with I > 2σ(I).
The crystals are hexagonal with space group P6 ; M = 400.80; T = 293(2) K; C H ClN O ; a = 20.520(6),
1
r
23 13
2
3
3
3
-1
c = 22.915 (10) Å; V = 8356(5) Å ; Z = 18; d = 1.434 g/cm ; F = 3708; µ(MoKα) = 0.234 mm . The
calc
000
structure was refined by full-matrix, least-squares analysis using the SHELX-97 computer program. Due to the
presence of pseudosymmetry in the molecular packing (the presence of a third order pseudoaxis led to a strong
correlation of the refined parameters) in the refinement of the structure there are additional geometrical
requirements superimposed, e.g. all of the aromatic rings are constrained to be given as planar, identical bonds in
the different molecules equal to one another, etc. The overall number of such geometrical restraints was 945. The
hydrogen atoms were brought into the refinement on geometrical grounds and specifically attached to the
corresponding non-hydrogen atom. The final confidence coefficients were R = 0.0430, wR = 0.1098 for those
1
2
observed and R = 0.0471, wR = 0.1114 for all reflections S = 0.975.
1
2
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1
331