Pyrano[4,3-d]pyrimidinium salts: 111. Reactions with N-nucleophiles

Article abstract of DOI:10.1007/s11172-007-0368-6

5-Aroyl-1,3,6-trimethyluracils were converted to pyrano[4,3-d]pyrimidinium salts. Reactions of the salts obtained with ammonia, primary amines, and hydrazine were studied.

Full text of DOI:10.1007/s11172-007-0368-6

Russian Chemical Bulletin, International Edition, Vol. 56, No. 11, pp. 2330—2336, November, 2007
2330
Pyrano[4,3ꢀd]pyrimidinium salts
1. Reactions with Nꢀnucleophiles

E. B. Tsupak, M. A. Shevchenko, V. V. Kostrub, and Yu. N. Tkachenko
South Federal University, Department of Chemistry,
7 ul. Zorge, 344090 RostovꢀonꢀDon, Russian Federation.
Eꢀmail: dastr@yandex.ru
5ꢀAroylꢀ1,3,6ꢀtrimethyluracils were converted to pyrano[4,3ꢀd]pyrimidinium salts. Reacꢀ
tions of the salts obtained with ammonia, primary amines, and hydrazine were studied.
Key words: 5ꢀaroylꢀ1,3,6ꢀtrimethyluracils, 5ꢀaroylꢀ6ꢀ[2ꢀ(4ꢀmethylphenyl)ꢀ2ꢀoxoethyl]pyriꢀ
midineꢀ2,4(1H,3H )ꢀdiones, 5ꢀaroylꢀ6ꢀ(2ꢀmorpholinoethenyl)pyrimidineꢀ2,4(1H,3H )ꢀdiones,
5ꢀaroylꢀ6ꢀ(2ꢀarylethenyl)pyrimidineꢀ2,4(1H,3H )ꢀdiones, pyrano[4,3ꢀd]pyrimidinium salts,
recyclization, pyrido[4,3ꢀd]pyrimidineꢀ2,4(1H,3H )ꢀdiones, pyrido[4,3ꢀd]pyrimidinium salts,
1Hꢀpyrimidо[5,4ꢀd][1,2]diazepineꢀ2,4(3H,9H )ꢀdiones.
Pyrylium and benzopyrylium salts are important
СНꢀactivity14—16 and can be converted to phenacyl or
enamine group,17 as well as to styryl one, the presence of
which can also serve as the basis for the pyran ring
closure.18
5ꢀAroylꢀ1,3,6ꢀtrimethyluracils 1 have been converted
to 5ꢀaroylꢀ1,3ꢀdimethylꢀ6ꢀ[2ꢀ(4ꢀmethylphenyl)ꢀ2ꢀoxoꢀ
ethyl]pyrimidineꢀ2,4(1Н,3H )ꢀdiones 2а,b by the reacꢀ
tion with aromatic acyl chlorides in the presence of aluꢀ
minum chloride (Scheme 1). The condensation of keꢀ
heterocyclic compounds. 2ꢀBenzopyrylium salts, in conꢀ
trast to isomeric 1ꢀbenzopyrylium ones, are capable of
recyclization and substitution of oxygen atom, which alꢀ
lows one to use them for the preparation of various heteroꢀ
and carbocyclic systems. They are widely used in the synꢀ
thesis of naphthalenes,1 benz[a]anthracenes,2 indenes,3
chrysenes,4 benzo[b]furans,5 isoquinolines,6 and isoꢀ
quinolinium salts.7 At the same time, uracil and many of
its derivatives are widely spread in the nature and have
versatile biological activity. Thus, it can be supposed
that the fused heterocyclic cations, including uracil
and pyrylium rings, are very interesting subjects to be
studied. In particular, in the reactions with Nꢀnucleoꢀ
philes they might serve as the synthetic precursors of
pyrido[4,3ꢀd]pyrimidinium system, which lately is under
the intensive research by medical chemistry.8—11 Neverꢀ
theless, there is no information on pyrano[4,3ꢀd]pyrimiꢀ
dinium salts and their properties in the available periodic
literature.
Scheme 1
In the present work, we report our results on the reꢀ
search of convenient ways for the synthesis of pyraꢀ
no[4,3ꢀd]pyrimidinium salt derivatives starting from
5ꢀaroylꢀ1,3,6ꢀtrimethyluracils. We also studied the reacꢀ
tivity of the salts obtained toward Nꢀnucleophiles: amꢀ
monia, primary amines, and hydrazine.
One of the methods often used for the synthesis of
pyrylium and benzo[c]pyrylium cations is the cyclization
of 1,5ꢀdicarbonyl compounds in the presence of acids.12
From this point of view, 5ꢀaroylꢀ1,3,6ꢀtrimethyluracils13
seem to be very prospective starting compounds for the
preparation of pyrano[4,3ꢀd]pyrimidinium salts. The
6ꢀmethyl group in these compounds has a noticeable
1: R1 = 4ꢀMeC6H4 (a), Ph (b), 4ꢀBrC6H4 (c), 2,4ꢀCl2C6H3 (d)
2: R1 = R2 = 4ꢀMeC6H4 (a); R1 = Ph, R2 = 4ꢀMeC6H4 (b)
3: R1 = 4ꢀBrC6H4 (a), 2,4ꢀCl2C6H3 (b)
4: R1 = Ph, R2 = 4ꢀMeC6H4 (a); R1 = R2 = 4ꢀBrC6H4 (b)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2251—2257, November, 2007.
1066ꢀ5285/07/5611ꢀ2330 © 2007 Springer Science+Business Media, Inc.

Reactions of pyrano[4,3ꢀd]pyrimidinium salts
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 11, November, 2007 2331
Scheme 3
tones 1 with triethyl orthoformate and morpholine leads
to 5ꢀaroylꢀ1,3ꢀdimethylꢀ6ꢀ(2ꢀmorpholinoethenyl)pyriꢀ
midineꢀ2,4(1H,3H )ꢀdiones 3a,b, whereas with aromatic
aldehydes in the presence of piperidine, to 5ꢀaroylꢀ6ꢀ
(2ꢀarylethenyl)ꢀ1,3ꢀdimethylpyrimidineꢀ2,4(1H,3H )ꢀ
diones 4a,b.
The formation of the target 1,5ꢀdiketones 2, enamiꢀ
nes 3, and styryls 4 was confirmed by 1Н and IR spectroꢀ
scopy and mass spectrometry data.
We have shown that diketones 2a,b and enamines 3a,b
upon treatment with HClO4 in triethyl orthoformate and
styryls 4a,b upon treatment with bromine in СHCl3 were
converted to 1,3ꢀdimethylꢀ2,4ꢀdioxoꢀ1,2,3,4ꢀtetrahydroꢀ
pyrano[4,3ꢀd]pyrimidinium perchlorates and broꢀ
mides 5a—f, respectively (Scheme 2).
R1 = R2 = 4ꢀMeC6H4 (a); R1 = Ph, R2 = 4ꢀMeC6H4 (b);
R
1 = 4ꢀBrC6H4, R2 = H (c); R1 = 2,4ꢀCl2C6H3, R2 = H (d)
Scheme 4
Scheme 2
acid afforded 1,3ꢀdimethylꢀ2,4ꢀdioxoꢀ1,2,3,4ꢀtetrahydroꢀ
pyrido[4,3ꢀd]pyrimidinium salts 7a—f (Scheme 5).
5
R1
R2
X
Scheme 5
a
b
c
d
e
f
4ꢀMeC6H4
Ph
4ꢀBrC6H4
2,4ꢀCl2C6H3
Ph
4ꢀMeC6H4
4ꢀMeC6H4
H
ClO4
ClO4
ClO4
ClO4
Br
H
4ꢀMeC6H4
4ꢀBrC6H4
4ꢀBrC6H4
Br
The structure of pyrano[4,3ꢀd]pyrimidinium cations
was ascribed to salts 5 as a result of the comparative analysis
1
of the Н NMR spectra, in which, due to the cationic
charge, a downfield shift of the signals of protons of the
Nꢀmethyl groups, in comparison with the neutral starting
compounds is observed. This difference in the chemical
shift values of the N(1)Me groups is 0.4—0.6 ppm; the
N(3)Me groups are more remote from the positively
charged center and the downfield shift here is considerꢀ
ably smaller in value.
7
R1
R2
R3
X
a
b
c
d
e
f
4ꢀMeC6H4
Ph
4ꢀBrC6H4
2,4ꢀCl2C6H3
Ph
4ꢀMeC6H4
4ꢀMeC6H4
H
Ph
ClO4
ClO4
ClO4
ClO4
Br
4ꢀBrC6H4
3,5ꢀMe2C6H3
4ꢀBrC6H4
4ꢀMeOC6H4
H
4ꢀMeC6H4
4ꢀBrC6H4 3,4ꢀ(MeO)2C6H3(CH2)2
4ꢀBrC6H4
Br
When the reactions of pyrano[4,3ꢀd]pyrimidinium perꢀ
chlorates 5а—d with aforeꢀmentioned Nꢀnucleophiles
were studied, we found that they undergo the recyclization
to 1,3ꢀdimethylpyrido[4,3ꢀd]pyrimidineꢀ2,4(1H,3H )ꢀ
diones 6a—d upon treatment with ammonia (Scheme 3).
The structures of pyrido[4,3ꢀd]pyrimidines 6c,d were
In the 1Н NMR spectra of pyrido[4,3ꢀd]pyrimidinium
cations 7, chemical shifts of protons of the methyl groups
in the uracil ring are downfield shifted relatively to those
in the spectra of neutral pyridouracils 6 (by ~0.2 ppm).
The reaction of pyranopyrimidinium perchlorates
5a—d with hydrazine proceeds readily, but is not straightꢀ
forward as it is in the reaction with ammonia and arylꢀ
amines: the structures of the reaction product depend on
the presence or absence of a substituent at the С(7) atom.
Perchlorates 5a,b, containing aryl substituents in poꢀ
sitions 5 and 7, react with the ring expansion and,
after treatment with diluted alkaline solution, give the
1
confirmed not only by Н NMR and IR spectroscopy
data, but also by the synthesis of the authentic samples
from enamines 3a,b by the method described earlier19
(Scheme 4).
The heating of pyrano[4,3ꢀd]pyrimidinium perchlorꢀ
ates and bromides 5a—f with primary amines in acetic

2332
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 11, November, 2007
Tsupak et al.
neutral 1,3ꢀdimethylꢀ1Hꢀpyrimidо[5,4ꢀd][1,2]diazepineꢀ
2,4(3H,9H )ꢀdiones 8a,b (Scheme 6), the structures of
which were confirmed by spectroscopy methods. Thus, in
the 1Н NMR spectra, the methylene group resonates as a
pair of doublets in the interval δ 2.97—3.00 and 4.38—4.42
(J = 13.27—13.33 Hz). The nonequivalency of the
methylene protons, obviously, is caused by the nonplanar
structure of the sevenꢀmembered ring of diazepines 8a,b
and by the high energy barrier for its conformation to be
changed. In the mass spectrum, there is a peak pointing
out the [M – N2]+ fragmentation.
respectively. A singlet of two protons of the amino group
in the region δ 7.19—7.42 is also observed. In the mass
spectrum, there is a peak pointing out the [M – NH2]+
fragmentation.
The nature of such an interesting behavior of pyraꢀ
no[4,3ꢀd]pyrimidinium salts 5 in the reactions with hydrꢀ
azine requires further study.
In conclusion, the methods for the synthesis of
pyrano[4,3ꢀd]pyrimidinium salts, starting from 5ꢀaroylꢀ
1,3,6ꢀtrimethyluracils, were elaborated. The reactions
of the salts obtained with ammonia, primary amines,
and hydrazine, which lead to the formation of pyriꢀ
do[4,3ꢀd]pyrimidine, pyrido[4,3ꢀd]pyrimidinium, and
pyrimidо[5,4ꢀd][1,2]diazepine systems, were studied.
Scheme 6
Experimental
IR spectra of compounds obtained were recorded on a
Specord IRꢀ71 spectrometer in Nujol. 1H NMR spectra were
recorded on a Bruker Avance DPXꢀ250 and Varian Unityꢀ300
spectrometers in CDCl3, DMSOꢀd6, and CDCl3—CF3COOH
mixture; HMDS was used as the internal standard. Mass spectra
were recorded on a Kratos instrument with direct inlet of the
sample into the source of ions (EI, energy of ionization: 70 eV,
operating voltage: 1.75 kV). Compounds 1a—d were obtained
according to the procedure described earlier.13
1,3ꢀDimethylꢀ5ꢀ(4ꢀmethylbenzoyl)ꢀ6ꢀ[2ꢀ(4ꢀmethylphenyl)ꢀ
2ꢀoxoethyl]pyrimidineꢀ2,4(1Н,3H )ꢀdione (2a). A mixture of
AlCl3 (1 g, 7.49 mmol), 4ꢀtoluoyl chloride (1 mL, 1.17 g,
7.56 mmol), and 5ꢀ(4ꢀmethylbenzoyl)ꢀ1,3,6ꢀtrimethylpyrimiꢀ
dineꢀ2,4(1Н,3H )ꢀdione (1a) (2 g, 7.35 mmol) was melted and
heated for 1 h at 190—200 °C. The tarꢀlike mixture obtained was
refluxed with water (20 mL) for 15 min 3 times, water was
decanted. The residue was recrystallized from EtOH and dried
at 100 °C to obtain 0.94 g (33%) of compound 2a as colorless
crystals, m.p. 250—255 °C (EtOH). Found (%): C, 70.56;
H, 5.61. C23H22N2O4. Calculated (%): C, 70.75; H, 5.68.
1H NMR (CDCl3), δ: 2.33—2.39 (2 s, 6 Н, ArМе, Ar´Ме);
3.36—3.37 (2 s, 6 Н, N(3)Ме, N(1)Ме); 4.38 (s, 2 Н, C(6)СН2);
7.15—7.27 (m, 4 Н, H(3)Ar, H(5)Ar, H(3)Ar´, H(5)Ar´); 7.67—7.78
(m, 4 H, H(2)Ar, H(6)Ar, H(2)Ar´, H(6)Ar´). MS, m/z: 390 [М]+,
375 [М – СН3]+, 360 [М – 2 СН3]+, 271 [М – СОС7Н7]+,
119 [СОС7Н7]+, 91 [С7Н7]+. IR, ν/cm–1: 1635, 1660, 1675,
1705 (С=О).
R1 = Ph, R2 = 4ꢀMeC6H4 (a); R1 = R2 = 4ꢀMeC6H4 (b)
7ꢀUnsubstituted salts 5с,d upon treatment with hyꢀ
drazine do not undergo the ring expansion, rather they
undergo recyclization to 6ꢀaminoꢀ1,3ꢀdimethylꢀ2,4ꢀ
dioxoꢀ1,2,3,4ꢀtetrahydropyrido[4,3ꢀd]pyrimidinium perꢀ
chlorates 9a,b (Scheme 7).
Scheme 7
5ꢀBenzoylꢀ1,3ꢀdimethylꢀ6ꢀ[2ꢀ(4ꢀmethylphenyl)ꢀ2ꢀoxoꢀ
ethyl]pyrimidineꢀ2,4(1Н,3H )ꢀdione (2b) was obtained similarly
to compound 2a from AlCl3 (1 g, 7.49 mmol), 4ꢀtoluoyl chloꢀ
ride (1 mL, 1.17 g, 7.56 mmol), and ketone 1b (1.88 g,
7.29 mmol). The yield was 1.18 g (43%), colorless crystals,
m.p. 235—237 °C (EtOH). Found (%): C, 70.39; H, 5.43.
R1 = 4ꢀBrC6H4 (a), 2,4ꢀCl2C6H3 (b)
C
22H20N2O4. Calculated (%): C, 70.20; H, 5.36. 1H NMR
(CDCl3), δ: 2.39 (s, 3 Н, Ar´Ме); 3.36—3.38 (2 s, 6 Н, N(3)Ме,
N(1)Ме); 4.40 (s, 2 Н, C(6)СН2); 7.24 (d, 2 Н, H(3)Ar´, H(5)Ar´
J = 8.1 Hz); 7.38 (t, 1 H, H(3)Ar, J = 7.32 Hz); 7.50 (br.t, 1 H,
In the 1Н NMR spectra of 6ꢀaminopyrido[4,3ꢀd]pyriꢀ
midinium salts 9a,b, signals of the methylene groups, charꢀ
acteristic of diazepines 8a,b, are absent, however two
doublets are contained in the intervals δ 8.03—8.08 and
8.94—8.99 (J = 7.4—7.5 Hz), which are assigned by us to
the С(8)Н and С(7)Н protons of the pyridinium ring,
,
H(4)Ar, J = 7.32 Hz); 7.72—7.83 (m, 4 H, H(2)Ar, H(6)Ar
,
H(2)Ar´, H(6)Ar´). MS, m/z: 376 [М]+, 257 [М – СОС7Н7]+,
119 [СОС7Н7]+, 91 [С7Н7]+. IR, ν/cm–1: 1650, 1655, 1670,
1700 (С=О).

Reactions of pyrano[4,3ꢀd]pyrimidinium salts
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 11, November, 2007 2333
5ꢀ(4ꢀBromobenzoyl)ꢀ1,3ꢀdimethylꢀ6ꢀ(2ꢀmorpholinoethenyl)ꢀ
pyrimidineꢀ2,4(1H,3H )ꢀdione (3a). A mixture of pyrimidinedione
1с (3 g, 8.9 mmol), triethyl orthoformate (3.95 g, 4.44 mL,
26.7 mmol), and morpholine (2.32 g, 2.32 mL, 26.7 mmol) was
refluxed for 2 h. The mixture was cooled to 80 °C and EtOH
(10 mL) was added to it. The suspension obtained was refluxed
for 3—5 min and cooled to ~20 °C. The precipitate was filtered
off, washed with EtOH, and dried at 80—100 °C to obtain 3.47 g
(90%) of compound 3a as yellow crystals, m.p. 236—238 °C
(from EtOH). Found (%): C, 52.19; H, 4.77; Br, 18.01.
C19H20BrN3O4. Calculated (%): C, 52.55; H, 4.64; Br, 18.40.
1H NMR (CDCl3), δ: 2.96 (t, 4 Н, N(CH2)2, J = 4.8 Hz); 3.34
(s, 3 Н, N(3)Ме); 3.41 (s, 3 Н, N(1)Ме); 3.51 (t, 4 Н, O(CH2)2,
J = 4.8 Hz); 4.54 (d, 1 Н, C(6)СH, J = 13.11 Hz); 6.44 (d, 1 Н,
C(6)СHCH, J = 13.11 Hz); 7.51 (d, 2 H, H(2)Ar, H(6)Ar, J =
8.48 Hz); 7.67 (d, 2 H, H(3)Ar, H(5)Ar, J = 8.48 Hz). IR,
ν/cm–1: 1620, 1670, 1705 (С=О).
5ꢀ(2,4ꢀDichlorobenzoyl)ꢀ1,3ꢀdimethylꢀ6ꢀ(2ꢀmorpholinoꢀ
ethenyl)pyrimidineꢀ2,4(1H,3H )ꢀdione (3b) was obtained simiꢀ
larly to compound 3a from ketone 1d (2.91 g, 8.89 mmol),
triethyl orthoformate (3.95 g, 4.44 mL, 26.7 mmol), and
morpholine (2.32 g, 2.32 mL, 26.7 mmol). The yield was 2.42 g
(64%), yellow crystals, m.p. 182—186 °C (EtOH). Found (%):
C, 54.04; H, 4.40; Cl, 16.57. C19H19Cl2N3O4. Calculated (%):
C, 53.79; H, 4.51; Cl, 16.71. 1H NMR (CDCl3), δ: 3.09 (t, 4 Н,
N(CH2)2, J = 4.8 Hz); 3.33 (s, 3 Н, N(3)Ме); 3.41 (s, 3 Н,
N(1)Ме); 3.62 (t, 4 Н, O(CH2)2, J = 4.8 Hz); 4.67 (d, 1 Н,
C(6)СH, J = 12.34 Hz); 6.68 (d, 1 Н, C(6)СHCH, J = 12.34 Hz);
7.21 (dd, 1 H, H(5)Ar, Jo = 8.3 Hz, Jm = 1.93 Hz); 7.33 (d, 1 H,
H(3)Ar, J = 1.93 Hz); 7.44 (d, 2 H, H(6)Ar, J = 8.48 Hz). IR,
ν/cm–1: 1615, 1665, 1700 (С=О).
1,3ꢀDimethylꢀ5,7ꢀbis(4ꢀmethylphenyl)ꢀ2,4ꢀdioxoꢀ1,2,3,4ꢀ
tetrahydropyrano[4,3ꢀd]pyrimidinium perchlorate (5a). Perchloꢀ
ric acid (1 mL of 70% aq. solution, 1.675 g, 11.7 mmol) in
HC(OEt)3 (20 mL) was added to diketone 2a (2.07 g, 5.30 mmol).
The solution formed was diluted with AcOEt (20 mL). The
precipitate formed was filtered off, washed with AcOEt, and
dried at 100 °C to obtain 1.38 g (55%) of perchlorate 5a as
colorless crystals, m.p. 295 °C (AcOEt). Found (%): C, 58.35;
H, 4.31; Cl, 7.18. C23H21ClN2O7. Calculated (%): C, 58.42;
H, 4.48; Cl, 7.50. 1H NMR (CDCl3—CF3COOH), δ: 2.47—2.52
(2 s, 6 Н, ArМе, Ar´Ме); 3.48 (s, 3 Н, N(3)Ме); 3.92 (s, 3 Н,
N(1)Ме); 7.41—7.49 (br.d, 4 Н, H(3)Ar, H(5)Ar, H(3)Ar´
,
H(5)Ar´, J = 8.2 Hz); 7.75 (d, 2 Н, H(2)Ar´, H(6)Ar´, J = 7.9 Hz);
7.92 (s, 1 H, С(8)Н); 8.03 (d, 2 H, H(2)Ar, H(6)Ar, J = 8.21 Hz).
MS, m/z: 373 [М]+, 119 [СОС7Н7]+, 91 [С7Н7]+. IR, ν/cm–1
:
1090, 1100 (Cl—O); 1610, 1695 (С=О).
1,3ꢀDimethylꢀ7ꢀ(4ꢀmethylphenyl)ꢀ2,4ꢀdioxoꢀ5ꢀphenylꢀ
1,2,3,4ꢀtetrahydropyrano[4,3ꢀd]pyrimidinium perchlorate (5b)
was obtained similarly to compound 5a from diketone 2b (2 g,
5.31 mmol) and 70% aq. HClO4 (1 mL, 1.675 g, 11.7 mmol) in
HC(OEt)3 (20 mL). The yield was 1.43 g (59%), colorless crysꢀ
tals, m.p. 295—298 °C (AcOEt). Found (%): C, 57.23; H, 4.05;
Cl, 7.70. C22H19ClN2O7. Calculated (%): C, 57.59; H, 4.17;
Cl, 7.73. 1H NMR (CDCl3—CF3COOH), δ: 2.50 (s, 3 Н,
Ar´Ме); 3.49 (s, 3 Н, N(3)Ме); 3.97 (s, 3 Н, N(1)Ме); 7.47 (d,
2 Н, H(3)Ar´, H(5)Ar´, J = 8.1 Hz); 7.60—7.69 (m, 2 Н, H(3)Ar
,
H(5)Ar); 7.76—7.88 (m, 3 Н, H(4)Ar, H(2)Ar´, H(6)Ar´); 8.02 (s,
1 H, С(8)Н); 8.07 (d, 2 H, H(2)Ar, H(6)Ar, J = 8.1 Hz). MS,
m/z: 359 [М]+, 343 [М – О]+, 119 [СОС7Н7]+, 91 [С7Н7]+, 77
[С6Н5]+. IR, ν/cm–1: 1075, 1100 (Cl—O); 1615, 1700 (С=О).
5ꢀ(4ꢀBromophenyl)ꢀ1,3ꢀdimethylꢀ2,4ꢀdioxoꢀ1,2,3,4ꢀtetraꢀ
hydropyrano[4,3ꢀd]pyrimidinium perchlorate (5c). Perchloric
acid (1.2 mL of 70% aq. solution, 2.01 g, 14 mmol) was added
dropwise to a stirred suspension of enamine 3а (1 g, 2.3 mmol)
in HC(OEt)3 (15 mL). The warming up of the reaction mixture
and dissolution of the starting enamine were observed. The reacꢀ
tion mixture was refluxed for 5 min. The precipitate of light
yellow color that formed was filtered off, washed with AcOEt,
and dried at 100 °C to obtain 0.965 g (94%) of perchlorate 5c as
colorless crystals, m.p. 238—240 °C (AcOEt). Found (%):
C, 40.65; H, 2.50; Br + Cl, 25.62. C15H12BrClN2O7. Calcuꢀ
lated (%): C, 40.25; H, 2.70; Br + Cl, 25.77. 1H NMR
(CDCl3—CF3COOH), δ: 3.49 (s, 3 Н, N(3)Ме); 3.86 (s, 3 Н,
N(1)Ме); 7.63 (d, 2 Н, H(3)Ar, H(5)Ar, J = 8.49 Hz); 7.76 (d,
2 H, H(2)Ar, H(6)Ar, J = 8.49 Hz); 7.83 (d, 1 H, С(8)Н, J =
5.40 Hz); 8.95 (d, 1 H, С(7)Н, J = 5.40 Hz). MS, m/z: 349
[М]+, 347 [М]+, 185 [СОС6Н4Br]+, 183 [СОС6Н4Br]+, 157
5ꢀBenzoylꢀ1,3ꢀdimethylꢀ6ꢀ[2ꢀ(4ꢀmethylphenyl)ethenyl]pyriꢀ
midineꢀ2,4(1H,3H )ꢀdione (4a). A solution of ketone 1b (5 g,
19.4 mmol), 4ꢀtolualdehyde (4.5 mL, 4.6 g, 38.3 mmol), and
piperidine (1 mL, 0.87 g, 10.2 mmol) in EtOH (20 mL)
was refluxed for 10 h. After the reaction mixture was
cooled, the precipitate of light yellow color that formed was
filtered off, washed with EtOH, and dried at 110—120 °C
to obtain 6.45 g (92%) of compound 4a as yellow crystals,
m.p. 207—211 °C (EtOH). Found (%): C, 73.52; H, 5.70.
C
22H20N2O3. Calculated (%): C, 73.32; H, 5.59. 1H NMR
(CDCl3), δ: 2.27 (s, 3 Н, Ar´Ме); 3.37 (s, 3 Н, N(3)Ме); 3.44
(s, 3 Н, N(1)Ме); 6.46 (d, 1 Н, C(6)СH, J = 16.2 Hz); 6.77 (d,
1 Н, C(6)СHCH, J = 16.2 Hz); 7.06 (s, 4 Н, Ar´); 7.31—7.39
(m, 2 H, H(3)Ar, H(5)Ar); 7.48 (t, 1 H, H(4)Ar, J = 7.33 Hz);
7.81 (d, 2 H, H(2)Ar, H(6)Ar, J = 6.94 Hz). IR, ν/cm–1: 1635,
1650, 1695 (С=О).
5ꢀ(4ꢀBromobenzoyl)ꢀ6ꢀ[2ꢀ(4ꢀbromophenyl)ethenyl]ꢀ1,3ꢀdiꢀ
methylpyrimidineꢀ2,4(1H,3H )ꢀdione (4b) was obtained similarly
to compound 4a from ketone 1c (1.01 g, 3 mmol), 4ꢀbromoꢀ
benzaldehyde (0.72 g, 3.89 mmol), and piperidine (0.2 mL,
0.174 g, 2 mmol) in EtOH (10 mL). The yield was 1.25 g (83%),
yellow crystals, m.p. 206—210 °C (EtOH). Found (%): C, 50.24;
H, 3.31; Br, 31.22. C21H16Br2N2O3. Calculated (%): C, 50.03;
H, 3.20; Br, 31.70. 1H NMR (CDCl3), δ: 3.37 (s, 3 Н, N(3)Ме);
3.46 (s, 3 Н, N(1)Ме); 6.51 (d, 1 Н, C(6)СH, J = 16.2 Hz); 6.73
[С6Н4Br]+, 155 [С6Н4Br]+, 81 [Br]+, 79 [Br]+. IR, ν/cm–1
:
1075, 1100 (Cl—O); 1630, 1690 (С=О).
5ꢀ(2,4ꢀDichlorophenyl)ꢀ1,3ꢀdimethylꢀ2,4ꢀdioxoꢀ1,2,3,4ꢀ
tetrahydropyrano[4,3ꢀd]pyrimidinium perchlorate (5d) was obꢀ
tained similarly to compound 5с from enamine 3а (0.5 g,
1.18 mmol), HC(OEt)3 (10 mL), and 70% aq. HClO4 (0.61 mL,
1.02 g, 7.12 mmol). The yield was 0.496 g (96%), colorless
crystals, m.p. 288—290 °C (AcOEt). Found (%): C, 40.82;
H, 2.58; Cl, 24.09. C15H11Cl3N2O7. Calculated (%): C, 41.17;
1
(d, 1 Н, C(6)СHCH, J = 16.2 Hz); 7.08 (d, 2 Н, H(2)Ar´
,
H, 2.53; Cl, 24.30. H NMR (CDCl3—CF3COOH), δ: 3.45 (s,
H(6)Ar´, J = 8.49 Hz); 7.42 (d, 2 Н, H(3)Ar´, H(5)Ar´, J =
8.48 Hz); 7.54 (d, 2 H, H(3)Ar, H(5)Ar, J = 8.48 Hz); 7.67 (t,
2 H, H(2)Ar, H(6)Ar, J = 8.48 Hz). IR, ν/cm–1: 1630, 1650,
1700 (С=О).
3 Н, N(3)Ме); 3.87 (s, 3 Н, N(1)Ме); 7.51 (s, 2 Н, H(3)Ar,
H(5)Ar); 7.62 (s, 1 H, H(6)Ar); 7.95 (d, 1 H, С(8)Н, J = 4.73 Hz);
9.03 (d, 1 H, С(7)Н, J = 4.74 Hz). IR, ν/cm–1: 1100 br. (Cl—O);
1630, 1700 (С=О).

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Russ.Chem.Bull., Int.Ed., Vol. 56, No. 11, November, 2007
Tsupak et al.
1,3ꢀDimethylꢀ7ꢀ(4ꢀmethylphenyl)ꢀ2,4ꢀdioxoꢀ5ꢀphenylꢀ
1,2,3,4ꢀtetrahydropyrano[4,3ꢀd]pyrimidinium bromide (5e).
A solution of Br2 (0.141 mL, 0.445 g, 2.78 mmol) in CHCl3
(1 mL) was added dropwise to a preheated to 50—60 °C and
stirred solution of styryl 4a (1 g, 2.77 mmol) in CHCl3 (20 mL).
The suspension obtained was refluxed for 30 min. The reaction
mixture was cooled to 20 °C, the precipitate was filtered off,
washed with AcOEt, and dried at 100 °C to obtain 1.08 g (88%)
of salt 5e as yellow crystals, m.p. 275—278 °C (CHCl3).
Found (%): C, 60.29; H, 4.71; Br, 17.93. C22H19BrN2O3. Calꢀ
culated (%): C, 60.15; H, 4.36; Br, 18.19. 1H NMR
(CDCl3—CF3COOH), δ: 2.50 (s, 3 Н, Ar´Ме); 3.49 (s, 3 Н,
H(2)Ar´, H(6)Ar´, J = 8.49 Hz); 8.13 (s, 1 H, С(8)Н). MS, m/z:
505 [М]+, 503 [М]+, 501 [М]+, 489 [М – О]+, 487 [М – О]+,
485 [М – О]+, 185 [СОС6Н4Br]+, 183 [СОС6Н4Br]+, 157
[С6Н4Br]+, 155 [С6Н4Br]+, 81 [Br]+, 79 [Br]+. IR, ν/cm–1
:
1615, 1685 (С=О).
5ꢀArylꢀ1,3ꢀdimethylpyrido[4,3ꢀd]pyrimidineꢀ2,4(1H,3H )ꢀ
diones 6a—d (general procedure). Ammonia (0.5 mL of 22%
aq. solution) was added to a stirred suspension of pyraꢀ
no[4,3ꢀd]pyrimidinium salt 5 (100 mg) in EtOH (1 mL). The
solution was refluxed for 2 h. The precipitate, formed during
cooling, was filtered off, washed with EtOH, and dried at
100—110 °C (Tables 1 and 2). In the IR spectra of compounds 6,
two strong absorption bands of carbonyl groups at 1665—1670
and 1705—1715 cm–1 were observed.
N(3)Ме); 3.97 (s, 3 Н, N(1)Ме); 7.47 (d, 2 Н, H(3)Ar´, H(5)Ar´
,
J = 8.1 Hz); 7.60—7.69 (t, 2 Н, H(3)Ar, H(5)Ar, J = 7.3 Hz);
7.76—7.88 (m, 3 Н, H(4)Ar, H(2)Ar´, H(6)Ar´); 8.02 (s, 1 H,
С(8)Н); 8.07 (d, 2 H, H(2)Ar, H(6)Ar, J = 8.1 Hz). MS, m/z:
359 [М]+, 343 [М – О]+, 119 [СОС7Н7]+, 91 [С7Н7]+, 79 [Br]+.
IR, ν/cm–1: 1625, 1690 (С=О).
5,7ꢀBis(4ꢀbromophenyl)ꢀ1,3ꢀdimethylꢀ2,4ꢀdioxoꢀ1,2,3,4ꢀ
tetrahydropyrano[4,3ꢀd]pyrimidinium bromide (5f) was obtained
similarly to compound 5e from styryl 4b (0.25 g, 0.496 mmol) in
CHCl3, (4 mL) and Br2 (0.025 mL, 0.08 g, 0.5 mmol) in CHCl3
(1 mL). The yield was 0.234 g (81%), yellow crystals, m.p.
244—246 °C (CHCl3). Found (%): C, 43.32; H, 2.68; Br, 41.30.
5,6ꢀDiarylꢀ1,3ꢀdimethylꢀ2,4ꢀdioxoꢀ1,2,3,4ꢀtetrahydropyriꢀ
do[4,3ꢀd]pyrimidinium salts 7a—f (general procedure). Amine
(0.9 mmol) was added to a stirred suspension of salt 5 (0.3 mmol)
in AcOH (1 mL). The solution was refluxed for 15 min, after
cooling to ~20 °C, it was diluted with AcOEt (3 mL). After 1 h,
the precipitate formed was filtered off, washed with AcOE, and
dried at 100—110 °C (see Tables 1 and 2). In the IR spectra of
compounds 7, absorption maxima of carbonyl groups in the
regions 1610—1630 and 1680—1700 cm–1 were observed. In the
spectra of perchlorates 7a—d, there is a characteristic maximum
C
21H15Br3N2O3. Calculated (%): C, 43.26; H, 2.59; Br, 41.11.
of absorption of perchlorate ion at 1095—1100 cm–1
.
1H NMR (CDCl3—CF3COOH), δ: 3.51 (s, 3 Н, N(3)Ме); 4.00
(s, 3 Н, N(1)Ме); 7.72 (d, 2 Н, H(3)Ar, H(5)Ar, J = 8.48 Hz);
7.83 (d, 4 Н, H(2)Ar, H(6)Ar, H(3)Ar´, H(5)Ar´); 8.03 (d, 2 Н,
1,3ꢀDimethylꢀ5,8ꢀbis(4ꢀmethylphenyl)ꢀ1Hꢀpyrimidо[5,4ꢀd]ꢀ
[1,2]diazepineꢀ2,4(3H,9H )ꢀdione (8a). Salt 5a (100 mg,
0.21 mmol) and 80% hydrazine hydrate (0.039 mL, 0.039 g,
Table 1. Yields, melting points, and elemental analysis data for pyrido[4,3ꢀd]pyrimidineꢀ
2,4(1H,3H )ꢀdiones 6a—d and pyrido[4,3ꢀd]pyrimidinium salts 7a—f
Comꢀ
pound
Yield
(%)
M.p./°C
Found
Calculated
Molecular
formula
(%)
С
Н
Hal
6a
6b
6c
6d
7a
7b
7c
7d
7e
7f
77
76
66
55
81
91
67
63
48
83
233—236
253—256
226—228
170—172
290—295
214—216
302—304
256—260
205—207
190—192
74.05
74.37
73.67
73.93
52.33
52.04
53.26
53.59
63.43
63.56
54.69
54.88
50.04
50.16
42.45
42.63
64.26
63.98
49.62
49.89
5.61
5.70
5.34
5.36
3.44
3.49
3.38
3.30
4.62
4.78
3.88
3.78
3.68
3.84
2.49
2.56
4.93
4.81
3.65
3.78
—
—
C23H21N3O2
C22H19N3O2
22.73 a
23.08
C15H12BrN3O2
C15H11Cl2N3O2
C29H26ClN3O6
C28H23BrClN3O6
C23H21BrClN3O6
C21H15BrCl3N3O6
C29H26BrN3O3
C31H28Br3N3O4
20.65 b
21.09
6.52 b
6.47
18.50 c
18.82
20.25 c
20.95
31.08 c
31.49
14.35 a
14.68
31.77 a
32.12
a Hal = Br.
b Hal = Cl.
c Hal = Br + Cl.

Reactions of pyrano[4,3ꢀd]pyrimidinium salts
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 11, November, 2007 2335
Table 2. 1Н NMR spectra of pyrido[4,3ꢀd]pyrimidineꢀ2,4(1H,3H )ꢀdiones 6a—d (in CDCl3) and pyrido[4,3ꢀd]pyrimidinium salts 7a—f
Comꢀ
pound
δ (J/Hz)
1ꢀМе 3ꢀМе
3.68 3.25
5ꢀR1
6ꢀR3
7ꢀR2
C(8)H
6a
2.43 (s, 3 Н, ArМе); 7.25 (d,
2 Н, mꢀH arom., J = 8.13);
8.11 (d, 2 H, oꢀH arom.,
J = 8.2)
—
2.41 (s, 3 Н, ArМе);
7.17 (d, 2 Н, mꢀH arom.,
J = 7.98); 7.33 (d, 2 Н,
oꢀH arom., J = 7.91)
2.42 (s, 3 Н, ArМе);
7.28 (d, 2 H, mꢀH arom.,
J = 8.1); 7.99 (d, 2 H,
oꢀH arom., J = 8.1)
8.72 (d, 1 H, С(7)Н,
J = 5.90)
7.66 (s)
6b
3.70 3.38
7.42—7.53 (m, 5 Н, Ar)
—
7.40 (s)
6c
6d
3.66 3.39
3.66 3.38
7.32 (d, 2 H, mꢀH arom.,
J = 8.5); 7.58 (d, 2 H,
oꢀH arom., J = 8.5)
—
—
7.12 (d,
J = 5.91)
7.22 (d, 1 H, H(6)Ar, J = 7.0);
8.77 (d, 1 H, С(7)Н,
7.18 (d,
7.36 (dd, 1 H, H(5)Ar
,
J = 5.93)
J = 5.93)
Jo = 7.0, Jm = 2.05); 7.48 (d,
1 H, H(3)Ar, J = 2.05)
2.27 (s, 3 Н, ArМе);
6.93—7.20 (m, 4 Н, Ar)
7.08—7.39 (m, 5 Н, Ar)
7a a
7b a
3.88 3.44
3.84 3.39
6.93—7.20 (m, 5 Н, Ar)
7.08—7.39 (m, 4 Н, Ar)
2.29 (s, 3 Н, ArМе);
6.93—7.20 (m, 4 Н, Ar)
2.32 (s, 3 Н, ArМе); 6.85 7.83 (s)
(d, 2 Н, mꢀН arom.,
7.86 (s)
J = 8.53); 7.08—7.39
(m, 2 Н, oꢀH arom.)
8.71 (d, 1 H, С(7)Н,
J = 7.14)
7c a
7d a
7e b
3.87 3.43
3.85 3.42
3.60 3.25
7.01—7.08 (m, 2 Н,
mꢀH arom.); 7.49 (d, 2 H,
oꢀH arom., J = 8.1)
7.15—7.34 (m, 2 Н, H(5)Ar
H(6)Ar); 7.39 (d, 1 Н, H(3)Ar
J = 1.89)
2.26 (s, 6 Н, 2 ArМе);
6.78 (s, 2 Н, oꢀH arom.);
7.01—7.08 (m, 1 Н, pꢀH arom.)
7.98 (d,
J = 7.14)
,
7.15—7.34 (m, 2 Н, mꢀH arom.); 8.71 (d, 1 H, С(7)Н,
8.02 (d,
J = 7.27)
,
7.56 (d, 2 H, oꢀH arom.,
J = 8.84)
3.79 (s, 3 Н, OМе); 6.49 (d,
2 Н, mꢀH arom., J = 8.8);
J = 6.64)
7.18—7.30 (m, 5 Н, Ar)
2.31 (s, 3 Н, ArМе);
7.11 (d, 2 Н, mꢀH arom.,
8.03 (s)
7.18—7.30 (m, 2 Н, oꢀH arom.) J = 8.06); 7.36 (d, 2 Н,
oꢀH arom., J = 8.1)
7f b
3.56 3.23
7.85 (s, 4 Н, Ar)
2.48 (t, 2 Н, N(6)СH2СН2,
J = 7.91); 3.67 (s, 3 Н,
4ꢀOМе); 3.71 (s, 3 Н,
7.62 (d, 2 Н, mꢀH arom., 8.02 (s)
J = 8.43); 7.80 (s, 2 H,
oꢀH arom., J = 8.50)
3ꢀOМе); 4.13 (t, 2 Н,
N(6)СH2, J = 7.91); 5.70
(s, 1 Н, H(2)Ar, J = 1.68);
5.92 (d, 1 Н, H(6)Ar
,
Jo = 8.13, Jm = 1.68); 6.59
(d, 1 Н, H(5)Ar, J = 8.21)
a
In CDCl3—CF3COOH.
b In DMSOꢀd6.
0.62 mmol) in AcOH (1 mL) were refluxed for 15 min. The
precipitate, formed during cooling, was filtered off, washed with
AcOH, hydrolyzed with a mixture of 1% aq. NaOH (5 mL) and
CHCl3 (5 mL). The chloroform extract was separated and conꢀ
centrated. The product was dried at 100 °C to obtain 32 mg
(39%) of compound 8a as colorless crystals, m.p. 270—271 °C
(CHCl3). Found (%): C, 71.23; H, 5.58. C23H22N4O2. Calcuꢀ
lated (%): C, 71.48; H, 5.74. H NMR (CDCl3), δ: 2.32—2.39
(2 s, 6 Н, ArМе, Ar´Ме); 2.97 (d, 1 Н, C(9)Н, J = 13.27 Hz);
3.27 (s, 3 Н, N(3)Ме); 3.62 (s, 3 Н, N(1)Ме); 4.38 (d, 1 Н,
H(3)Ar´, H(5)Ar´); 7.58 (d, 2 Н, H(2)Ar´, H(6)Ar´, J = 8.21 Hz);
7.76 (d, 2 H, H(2)Ar, H(6)Ar, J = 8.43 Hz). IR, ν/cm–1: 1660,
1700 (С=О).
1,3ꢀDimethylꢀ8ꢀ(4ꢀmethylphenyl)ꢀ5ꢀphenylꢀ1Hꢀpyrimiꢀ
dо[5,4ꢀd][1,2]diazepineꢀ2,4(3H,9H )ꢀdione (8b) was obtained
similarly to compound 8a from salt 5b (300 mg, 0.654 mmol)
and 80% hydrazine hydrate (0.104 mL, 0.104 g, 1.67 mmol) in
AcOH (3 mL). The yield was 110 mg (45%), colorless crystals,
m.p. 260—265 °C (CHCl3). Found (%): C, 70.86; H, 5.30.
1
C
22H20N4O2. Calculated (%): C, 70.95; H, 5.41. 1H NMR
(CDCl3), δ: 2.41 (s, 3 Н, Ar´Ме); 3.00 (d, 1 Н, C(9)Н,
C(9)Н, J = 13.27 Hz); 7.19—7.28 (m, 4 Н, H(3)Ar, H(5)Ar
,

2336
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 11, November, 2007
Tsupak et al.
J = 13.36 Hz); 3.28 (s, 3 Н, N(3)Ме); 3.64 (s, 3 Н, N(1)Ме);
4. I. V. Korobka, Yu. V. Revinskii, and E. V. Kuznetsov, Khim.
Geterotsikl. Soedin., 1985, 910 [Chem. Heterocycl. Compd.,
1985, 21, 754 (Engl. Transl.)].
4.42 (d, 1 Н, C(9)Н, J = 13.33 Hz); 7.28 (d, 2 Н, H(3)Ar´
H(5)Ar´, J = 8.2 Hz); 7.42—7.45 (m, 3 Н, H(3)Ar, H(4)Ar
,
,
H(5)Ar); 7.70—7.73 (m, 2 Н, H(2)Ar, H(6)Ar); 7.78 (d, 2 H,
H(2)Ar´, H(6)Ar´, J = 8.2 Hz). MS, m/z: 372 [М]+, 357
[М – СН3]+, 344 [М – N2]+, 287 [М – N2 – MeNCO]+, 269
[М – C6H5CN]+, 255 [М – MeC6H4CN]+, 91 [С7Н7]+. IR,
ν/cm–1: 1670, 1705 (С=О).
5. S. V. Verin and E. V. Kuznetsov, Khim. Geterotsikl. Soedin.,
1992, 169 [Chem. Heterocycl. Compd., 1992, 28, 135 (Engl.
Transl.)].
6. I. V. Shcherbakova, V. G. Brovchenko, and E. V. Kuznetsov,
Khim. Prirodn. Soedin., 1985, 815 [Chem. Nat. Compd., 1985,
21, 774 (Engl. Transl.)].
6ꢀAminoꢀ5ꢀ(4ꢀbromophenyl)ꢀ1,3ꢀdimethylꢀ2,4ꢀdioxoꢀ
1,2,3,4ꢀtetrahydropyrido[4,3ꢀd]pyrimidinium perchlorate (9a)
was obtained similarly to salts 7a—f from salt 5с (0.16 g,
0.357 mmol) and 80% hydrazine hydrate (0.039 mL, 0.039 g,
0.62 mmol) in AcOH (2 mL). The yield was 0.14 g (85%),
colorless crystals, m.p. 320—324 °C (AcOH). Found (%):
C, 38.86; H, 3.05; Br + Cl, 24.65. C15H14BrClN4O6. Calcuꢀ
lated (%): C, 39.03; H, 3.06; Br + Cl, 24.99. 1H NMR
(DMSOꢀd6), δ: 3.18 (s, 3 Н, N(3)Ме); 3.66 (s, 3 Н, N(1)Ме);
7.19 (s, 2 Н, NH2); 7.31 (d, 2 Н, H(3)Ar, H(5)Ar, J = 8.4 Hz);
7.69 (d, 2 Н, H(2)Ar, H(6)Ar, J = 8.4 Hz); 8.03 (d, 1 H, С(8)Н,
J = 7.5 Hz); 8.94 (d, 1 H, С(7)Н, J = 7.5 Hz). MS, m/z: 361
7. K. Dimroth and H. Odenwälder, Chem. Ber., 1971,
104, 2984.
8. A. M. Thompson, A. J. Bridges, D. W. Fry, A. J. Kraker, and
W. A. Denny, J. Med. Chem., 1995, 38, 3780.
9. G. W. Rewcastle, B. D. Palmer, A. M. Thompson, A. J.
Bridges, D. R. Cody, H. Zhou, D. W. Fry, A. McMichael,
and W. A. Denny, J. Med. Chem., 1996, 39, 1823.
10. A. M. Thompson, D. K. Murray, W. L. Elliott, D. W.
Fry, J. A. Nelson, H. D. Hollis Showalter, B. J. Roberts,
P. W. Vincent, and W. A. Denny, J. Med. Chem., 1997,
40, 915.
11. J. B. Smaill, B. D. Palmer, G. W. Rewcastle, W. A. Denny,
D. J. McNamara, E. M. Dobrusin, A. J. Bridges, H. Zhou,
H. D. Hollis Showalter, R. T. Winters, W. R. Leopold, D. W.
Fry, J. M. Nelson, V. Slintak, W. L. Elliot, B. J. Roberts,
P. W. Vincent, and S. J. Patmore, J. Med. Chem., 1999,
42, 1803.
[М]+, 345 [М – NH2]+, 155 [С6Н4Br]+, 79 [Br]+. IR, ν/cm–1
:
1100 br (Cl—O); 1630, 1685 (С=О); 3255, 3340 (NH2).
6ꢀAminoꢀ5ꢀ(2,4ꢀdichlorophenyl)ꢀ1,3ꢀdimethylꢀ2,4ꢀdioxoꢀ
1,2,3,4ꢀtetrahydropyrido[4,3ꢀd]pyrimidinium perchlorate (9b)
was obtained similarly to salts 7a—f from salt 5d (0.1 g,
0.23 mmol) and 80% hydrazine hydrate (0.029 mL, 0.029 g,
0.46 mmol) in AcOH (1 mL). The yield was 55 mg (53%),
colorless crystals, m.p. 248—250 °C (AcOH). Found (%):
C, 39.71; H, 3.02; Cl, 23.24. C15H13Cl3N4O6. Calculated (%):
12. E. V. Kuznetsov, I. V. Shcherbakova, and A. T. Balaban,
Adv. Heterocycl. Chem., 1990, 50, 157.
13. E. B. Tsupak, M. A. Shevchenko, A. F. Pozharskii,
and Yu. N. Tkachenko, Khim. Geterotsikl. Soedin., 2003,
1096 [Chem. Heterocycl. Compd., 2003, 39, 953 (Engl.
Transl.)].
1
C, 39.89; H, 2.90; Cl, 23.55. H NMR (DMSOꢀd6), δ: 3.15 (s,
3 Н, N(3)Ме); 3.63 (s, 3 Н, N(1)Ме); 7.39 (d, 1 Н, H(6)Ar, J =
8.75 Hz); 7.42 (s, 2 Н, NH2); 7.65 (dd, 1 Н, H(5)Ar, Jo
=
8.59 Hz, Jm = 2.02 Hz); 7.69 (d, 1 Н, H(3)Ar, J = 2.02 Hz); 8.08
(d, 1 H, С(8)Н, J = 7.41 Hz); 8.99 (d, 1 H, С(7)Н, J = 7.41 Hz).
IR, ν/cm–1: 1100 br (Cl—O); 1640, 1690 (С=О); 3200,
3315 (NH2).
14. S. Senda, T. Asao, I. Sugiyama, and K. Hirota, Tetrahedron
Lett., 1980, 21, 531.
15. K. Hirota, T. Asao, I. Sugiyama, and S. Senda, Heterocycles,
1981, 15, 289.
16. K. Singh, S. Singh, and A. Mahajan, J. Org. Chem., 2005,
70, 6114.
17. K. Hirota, T. Asao, S. Senda, Y. Kitade, and Y. Maki,
J. Heterocycl. Chem., 1988, 25, 985.
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Received July 11, 2007;
in revised form September 27, 2007