Synthesis and reactivity of monothiooxamides of the aminonitroarene series

Article abstract of DOI:10.1007/s11172-009-0167-3

Monothiooxamides containing aminonitrobenzene and aminonitropyridine fragments have been synthesized. A possibility to synthesize thioesters and fused imidazole and diazepine derivatives on their basis has been demonstrated. ; 2009 Springer Science+Busine

Full text of DOI:10.1007/s11172-009-0167-3

Russian Chemical Bulletin, International Edition, Vol. 58, No. 6, pp. 1276—1280, June, 2009
1276
Synthesis and reactivity of monothiooxamides
of the aminonitroarene series*
V. N. Yarovenko,a A. V. Polushina,a K. S. Levchenko,a I. V. Zavarzin,a
M. M. Krayushkin,a S. K. Kotovskaya,b and V. N. Charushinc
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 137 6939. Eꢀmail: yarov@iok.ac.ru
bUral State Technical University,
19 ul. Mira, 620002 Ekaterinburg, Russian Federation.
Fax: +7 (343) 374 0458
cI. Ya. Postovskii Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
22/20 ul. S. Kovalevskoi, 620041 Ekaterinburg, Russian Federation.
Fax: +7 (343) 374 1189
Monothiooxamides containing aminonitrobenzene and aminonitropyridine fragments have
been synthesized. A possibility to synthesize thioesters and fused imidazole and diazepine
derivatives on their basis has been demonstrated.
Key words: thiooxamides, αꢀchloroacetamides, dibenzodiazepines, benzimidazoles,
thioesters, sulfur.
Earlier, we have suggested methods for preparing a
base (aniline) has been used, the addition of triethylamine
or pyridine was necessary (see Scheme 1).
number of monothiooxamides and studied their reactivity.1
Monothiooxamide nitro derivatives are of significant
interest due to the fact that many bioactive compounds
contain a nitro group, which can be also used in various
transformations, including heterocyclization reactions.
The purpose of our work consisted in the synthesis
of new monothiooxamides of the aminonitrobenzene and
aminonitropyridine series and design of benzimidazole
and dibenzodiazepine derivatives on their basis.
The monothiooxamides were synthesized based on
aromatic vicinal nitro amines 1a—d using a method
developed by us earlier1 consisting in the reaction of
αꢀchloroacetamides with preꢀprepared solution of sulfur
in amines.
Scheme 1
The starting chloroacetamides 2a—d were obtained
by the reaction of chloroacetyl chloride with aminonitroꢀ
benzenes 1a—c and aminonitropyridine 1d in dimethylꢀ
formamide. The nitro group does not affect the acylation
process, the reaction proceeds smoothly in quantitative
yield (Scheme 1).
A preꢀprepared solution of elementary sulfur in amines
kept for 30 min was used in the Sꢀfunctionalization reacꢀ
tions of chloroacetamides. The process smoothly proꢀ
ceeds at room temperature with morpholine; when weaker
Compound
R
H
Cl
Me
H
X
a
b
c
d
CH
CH
CH
N
* Dedicated to Academician O. N. Chupakhin on the occasion
of his 75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1240—1244, June, 2009.
1066ꢀ5285/09/5806ꢀ1276 © 2009 Springer Science+Business Media, Inc.

Monothiooxamides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
1277
When all the components were mixed simultaneously,
the reaction is not that smooth and, along with monoꢀ
thiooxamides 4a,b, there are formed amines 5a,b in the
ratio 1 : 5, respectively (Scheme 2).
mation of monothiooxamides, which then are converted
to dibenzodiazepines (Scheme 3).
Modification of thioamide and nitro groups in the
monothiooxamide derivatives obtained allows one to synꢀ
thesize various compounds. Note that the nitro group in
monothiooxamides 4a—c does not considerably affect the
nucleophilicity of the thiocarbonyl group, which is conꢀ
firmed, in particular, by a possibility to obtain monothioꢀ
oxamic Sꢀesters 7a—c from monothiooxamides. The
former were synthesized by the reaction of monothioꢀ
oxamides with dimethyl sulfate and subsequent treatment
of isothioamides formed with water (Scheme 4).
Scheme 2
Scheme 4
R = H(a), Cl (b)
Thus, the sulfurization of nitro derivatives proceeds
similarly to the reactions with chloroacetamides described
by us earlier1 and can be used in designing heterocyclic
compounds.
We have shown that the reaction of chloroacetamides
2a,b,d with a preꢀprepared mixture of diphenylꢀ2,2´ꢀdiꢀ
amine, triethylamine, and elementary sulfur leads to
carbamoylꢀcontaining 5Hꢀdibenzo[d,f][1,3]diazepines
6a,b,d. The process apparently proceeds through the forꢀ
Scheme 3
R = H(a), Cl(b), Me(c)
Reduction of the nitro groups in orthoꢀposition to the
monothiooxamide fragment leads to the heterocyclization
with the formation of imidazole ring (Scheme 5).
In conclusion, the nitro group in monothiooxamides
creates additional possibilities for the synthesis of various
derivatives and can be involved into the heterocyclization
reaction.
Compound
R
X
a
H
b
Cl
d
H
N
CH CH

1278
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
Yarovenko et al.
Scheme 5
(s, 1 H, Ar); 10.55 (s, 1 H, NH). MS, m/z: 229 [M]+. Found (%):
C, 47.34; H, 3.82; N, 12.20; Cl, 15.48. C9H9ClN2O3. Calcuꢀ
lated (%): C, 47.28; H, 3.97; N, 12.25; Cl, 15.51.
Nꢀ(2ꢀNitropyridinꢀ3ꢀyl)ꢀ2ꢀchloroacetamide (2d) was obtained
from 1d (0.5 g, 3,6 mmol) similarly to compound 2a, the yield
1
was 0.73 g (95%), m.p. 178—179 °C. H NMR, δ: 4.38 (s, 2 H,
CH2); 7.85 (m, 1 H, Py); 8.30 (m, 1 H, Py); 8.42 (m, 1 H, Py,);
10.68 (s, 1 H, NH). MS, m/z: 215 [M]+. Found (%): C, 39.06;
H, 2.80; N, 19.43; Cl, 16.48. C7H6ClN3O3. Calculated (%):
C, 39.00; H, 2.81; N, 19.49; Cl, 16.44.
Compound
R
H
Х
Nꢀ(2ꢀNitrophenyl)ꢀ2ꢀphenylaminoꢀ2ꢀthioxoacetamide (3a).
Chloroacetanilide 2a (0.1 g, 0.47 mmol) was added to a suspenꢀ
sion of sulfur (0.045 g, 1,4 mmol), amine (aniline or morpholine,
0.94 mmol), triethylamine (in the case of aniline, 0.94 mmol) in
DMF (1 mL) that has been kept for 30 min. The reaction mixꢀ
ture was stirred for 7 h at room temperature, then the mixture
was poured into water, a precipitate was filtered off. To purify
the product from unreacted sulfur, it was dissolved in acetone,
the acetone solution was separated, the solvent was evaporated
in vacuo. The solid residue was recrystallized from ethanol to
obtain compound 3a (0.13 g, 93%), m.p. 158—160 °C. 1H NMR,
δ: 7.34 (m, 1 H, Ar); 7.46 (m, 3 H, Ar); 7.90 (m, 3 H, Ar); 8.22
(d, 1 H, Ar, J = 8.41 Hz); 8.51 (d, 1 H, Ar, J = 8,31 Hz); 12.10
(s, 1 H, NH); 12.45 (s, 1 H, NH). MS, m/z: 301 [M]+. Found(%):
C, 55.65; H, 3.74; N, 13.80; S, 10.85. C14H11N3O3S. Calcuꢀ
lated (%): C, 55.80; H, 3.68; N, 13.95; S, 10.64.
8а
8с
Me
9а
9b
H
Cl
9с
Me
Experimental
Nꢀ(4ꢀChloroꢀ2ꢀnitrophenyl)ꢀ2ꢀphenylaminoꢀ2ꢀthioxoacetꢀ
amide (3b) was obtained from 2b (0.1 g, 0.4 mmol) similarly
to compound 3a, the yield was 0.12 g (90%), m.p. 161—163 °C.
1H NMR, δ: 7.30 (m, 1 H, Ar); 7.56 (m, 3 H, Ar); 7.65 (m, 2 H,
Ar); 8.16 (m, 1 H, Ar); 8.60 (d, 1 H, Ar, J = 8.26 Hz); 11.95 (s,
1 H, NH); 12.3 (s, 1 H, NH). MS, m/z: 335 [M]+. Found (%):
C, 50.15; H, 2.87; N, 12.42; S, 9.60; Cl, 10.55. C14H10ClN3O3S.
Calculated (%): C, 50.08; H, 3.00; N, 12.51; S, 9.55; Cl, 10.56.
Nꢀ(4ꢀMethylꢀ2ꢀnitrophenyl)ꢀ2ꢀphenylaminoꢀ2ꢀthioxoacetꢀ
amide (3c) was obtained from 2c (0.1 g, 4.4 mmol) similarly
to compound 3a, the yield was 0.11 g (80%), m.p. 111—113 °C.
1H NMR, δ: 2.37 (s, 3 H, CH3); 7.32 (m, 1 H, Ar); 7.45 (m, 3 H,
Ar); 7.68 (m, 2 H, Ar); 8.10 (m, 2 H, Ar); 12.05 (s, 1 H, NH);
12.40 (s, 1 H, NH). MS, m/z: 315 [M]+. Found (%): C, 57.33;
H, 3.99; N, 13.40; S, 10.12. C15H13N3O3S. Calculated (%):
C, 57.13; H, 4.16; N, 13.33; S, 10.17.
Nꢀ(2ꢀNitropyridinꢀ3ꢀyl)ꢀ2ꢀphenylaminoꢀ2ꢀthioxoacetamide
(3d) was obtained from 2d (0.1 g, 4.6 mmol) similarly to
compound 3a, the yield was 0.09 g (65%), m.p. 163—165 °C.
1H NMR, δ: 7.39 (d, 1 H, Ar, J = 7.27 Hz); 7.46 (t, 2 H, Ar,
J = 7.24 Hz); 7.90 (m, 2 H, Ar); 7.95 (m, 1 H, Py); 8.45 (m, 1 H,
Py); 8.79 (d, 1 H, Py, J = 8.02 Hz); 11.85 (s, 1 H, NH); 12.50
(s, 1 H, NH). MS, m/z: 302 [M]+. Found (%): C, 51.54;
H, 3.26; N, 18.63; S, 10.83. C13H10N4O3S. Calculated (%):
C, 51.65; H, 3.33; N, 18.53; S, 10.61.
1H NMR spectra were recorded on a Bruker WMꢀ200
(200 MHz) and Bruker WMꢀ250 (250 MHz) spectrometers in
DMSOꢀd6. Mass spectra were obtained on a Varian MAT CHꢀ6
instrument with direct inlet of the sample into the ion source,
the energy of ionization, 70 eV, directing potential, 1.75 kV.
Melting points were determined on a Boetius heating stage and
are uncorrected. Analysis of reaction mixtures and monitoring
of isolated product purities were performed by TLC on Merck
UVꢀ254 plates.
Nꢀ(2ꢀNitrophenyl)ꢀ2ꢀchloroacetamide (2a). Chloroacetyl
chloride (0.4 mL (4.8 mmol) was slowly added to amine 1a
(0.5 g, 4 mmol) in DMF (3 mL) with stirring and iceꢀcooling in
such a way that to keep temperature below 5—7 °C, then, the
mixture was stirred for 1.5 h, poured into water, a precipitate
formed was filtered off to obtain compound 2a (0.76 g, 98%),
1
m.p. 109—111 °C (agrees with the data in Ref. 2). H NMR, δ:
4.33 (s, 2 H, CH2); 7.60 (m, 2 H, Ar); 7.78 (m, 1 H, Ar); 8.80
(m, 1 H, Ar); 11.6 (s, 1 H, NH). MS, m/z: 214 [M]+. Found (%):
C, 44.67; H, 3.35; N, 13.10; Cl, 16.58. C8H7ClN2O3. Calcuꢀ
lated (%): C, 44.77; H, 3.29; N, 13.05; Cl, 16.52.
Nꢀ(4ꢀChloroꢀ2ꢀnitrophenyl)ꢀ2ꢀchloroacetamide (2b) was
obtained from 1b (0.5 g, 2.9 mmol) similarly to compound 2a,
the yield was 0.68 g (97%), m.p. 140—141 °C (agrees with the
1
Nꢀ(2ꢀNitrophenyl)ꢀ2ꢀmorpholinoꢀ2ꢀthioxoacetamide (4a) was
obtained from 2a (0.1 g, 0.47 mmol) similarly to compound 3a,
the yield was 0.1 g (70%), m.p. 137—138 °C (agrees with the
data in Ref. 3). H NMR, δ: 4.30 (s, 2 H, CH2); 7.30 (m, 1 H,
Ar); 8.35 (m, 1 H, Ar); 8.60 (m, 1 H, Ar); 11.35 (s, 1 H, NH).
MS, m/z: 249 [M]+. Found (%): C, 38.62; H, 2.50; N, 11.16;
Cl, 28.50. C8H6Cl2N2O3. Calculated (%): C, 38.58; H, 2.43;
N, 11.25; Cl, 28.47.
Nꢀ(4ꢀMethylꢀ2ꢀnitrophenyl)ꢀ2ꢀchloroacetamide (2c) was
obtained from 1c (0.5 g, 3.3 mmol) similarly to compound 2a,
the yield was 0.72 g (96%), m.p. 199—121 °C (agrees with the
data in Ref. 4). 1H NMR, δ: 2.4 (s, 3 H, CH3); 4.35 (s, 2 H, CH2);
7.55 (d, 1 H, Ar, J = 8.36 Hz); 7.65 (d, 1 H, Ar, J = 8.3 Hz); 7.85
1
data in Ref. 5). H NMR, δ: 3.8 (m, 6 H, CH2); 4.15 (m, 2 H,
CH2) ; 7.5 (m, 1 H, Ar); 7.75 (m, 2 H, Ar); 8.0 (d, 1 H, Ar,
J = 8.13 Hz); 11.0 (s, 1 H, NH). MS, m/z: 295 [M]+. Found (%):
C, 48.61; H, 4.56; N, 14.35; S, 10.74. C12H13N3O4S. Calcuꢀ
lated (%): C, 48.80; H, 4.44; N, 14.23; S, 10.86.
Nꢀ(4ꢀChloroꢀ2ꢀnitrophenyl)ꢀ2ꢀmorpholinoꢀ2ꢀthioxoacetꢀ
amide (4b) was obtained from 2b (0.1 g, 0.4 mmol) similarly to

Monothiooxamides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
1279
compound 3a, the yield was 0.1 g (80 %), m.p. 155—156 °C.
1H NMR, δ: 3.75 (m, 6 H, CH2); 4.15 (d, 2 H, CH2, J = 8.34 Hz);
7.74 (d, 1 H, Ar, J = 8.74 Hz); 7.85 (d, 1 H, Ar, J = 8.71 Hz);
8.15 (s, 1 H, Ar); 11.0 (s, 1 H, NH). MS, m/z: 329 [M]+.
Found (%): C, 43.61; H, 3.52; N, 12.8; S, 9.91; Cl, 10.6.
C12H12ClN3O4S. Calculated (%): C, 43.71; H, 3.67; N, 12.74;
S, 9.72; Cl, 10.75.
ane (1 : 3) solvent system to obtain compound 6a (0.23 g, 65%),
m.p. 233—235 °C. H NMR, δ: 7.05 (d, 2 H, Ar, J = 7.67 Hz);
7.15 (m, 3 H, Ar); 7.3 (m, 3 H, Ar); 7.45 (m, 1 H, Ar); 7.85
(m, 1 H, Ar); 8.2 (d, 1 H, Ar, J = 8.14 Hz); 8.65 (d, 1 H, Ar,
J = 8.38 Hz); 9.8 (s, 1 H, NH); 10.4 (s, 1 H, NH). MS, m/z:
358 [M]+. Found (%): C, 67.20; H, 3.85; N, 15.69. C20H14N4O3.
Calculated (%): C, 67.03; H, 3.94; N, 15.63.
1
Nꢀ(4ꢀMethylꢀ2ꢀnitrophenyl)ꢀ2ꢀmorpholinoꢀ2ꢀthioxoacetꢀ
amide (4c) was obtained from 2c (0.1 g, 4.4 mmol) similarly
to compound 3a, the yield was 0.1 g (80%), m.p. 150—152 °C.
1H NMR, δ: 2.4 (s, 3 H, CH3); 3.75 (m, 6 H, CH2); 4.15 (s, 2 H,
CH2); 7.65 (t, 2 H, Ar, J = 7.98 Hz); 7.85 (s, 1 H, Ar); 10.85 (s,
1 H, NH). MS, m/z: 309 [M]+. Found (%): C, 50.36; H, 4.98;
N, 13.43; S, 10.6. C13H15N3O4S. Calculated (%): C, 50.47;
H, 4.89; N, 13.58; S, 10.37.
Nꢀ(2ꢀNitropyridinꢀ3ꢀyl)ꢀ2ꢀmorpholinoꢀ2ꢀthioxoacetamide
(4d) was obtained from 2d (0.1 g, 4.6 mmol) similarly to
compound 3a, the yield was 0.08 g (60%), m.p. 159—161 °C.
1H NMR, δ: 3.75 (t, 6 H, CH2, J = 10.35 Hz); 4.15 (t, 2 H, CH2,
J = 9.63 Hz); 7.87 (m, 1 H, Py); 8.25 (d, 1 H, Py, J = 8.1 Hz);
8.45 (m, 1 H, Py); 11.15 (s, 1 H, NH). MS, m/z: 296 [M]+.
Found (%): C, 44.43; H, 3.87; N, 18.99; S, 10.89. C11H12N4O4S.
Calculated (%): C, 44.59; H, 4.08; N, 18.91; S, 10.82.
Nꢀ(4ꢀChloroꢀ2ꢀnitrophenyl)ꢀ5Hꢀdibenzo[d,f][1,3]diazepinꢀ
6ꢀcarboxamide (6b) was obtained from 2b (0.25 g, 1 mmol)
similarly to compound 6a. The yield was 0.26 g (66%),
m.p. 220—222 °C. 1H NMR, δ: 7.05 (d, 2 H, Ar, J = 0.026 Hz);
7.2 (t, 2 H, Ar, J = 0.024 Hz); 7.35 (d, 3 H, Ar, J = 0.025 Hz);
7.4 (d, 2 H, Ar, J = 0.026 Hz); 7.9 (m, 1 H, Ar); 8.25 (m, 1 H,
Ar); 9.95 (s, 1 H, NH); 10.35 (s, 1 H, NH). MS, m/z: 393[M]+.
Found (%): C, 61.04; H, 3.47; N, 14.20; Cl, 9.16. C20H13ClN4O3.
Calculated (%): C, 61.16; H, 3.34; N, 14.26; Cl, 9.03.
Nꢀ(2ꢀNitropyridinꢀ3ꢀyl)ꢀ5Hꢀdibenzo[d,f][1,3]diazepineꢀ
6ꢀcarboxamide (6c) was obtained from 2c (0.23 g, 1 mmol)
similarly to compound 6a. The yield was 0.22 g (60%),
m.p. 245—247 °C. 1H NMR, δ: 6.75 (m, 1 H, Ar); 6.9 (m, 1 H,
Ar); 7.2—7.35 (m, 6 H, Ar); 7.9 (m, 1 H, Py); 8.45 (m, 1 H, Py);
8.9 (m, 1 H, Py); 9.8 (s, 1 H, NH); 10.25 (s, 1 H, NH). MS,
m/z: 359[M]+. Found (%): C, 63.41; H, 3.54; N, 19.60.
C19H13N5O3. Calculated (%): C, 63.51; H, 3.65; N, 19.49.
SꢀMethyl 2ꢀ(2ꢀnitrophenylamino)ꢀ2ꢀoxothioacetate (7a).
Freshly distilled dimethyl sulfate (0.2 g, 1.5 mmol) was added
to compound 4a (0.26 g, 1 mmol). The mixture was heated for
40 min at 100 °C, then, cooled to room temperature followed by
addition of water (2 mL). A precipitate formed was filtered off,
washed with cold water and recrystallized from ethanol to obꢀ
tain product 7a (0.18 g, 87%), m.p. 132—135 °C. 1H NMR, δ:
2.4 (s, 3 H, CH3); 7.48 (m, 1 H, Ar); 7.82 (m, 1 H, Ar); 8.15 (m,
2 H, Ar); 11.25 (s, 1 H, NH). MS, m/z: 240 [M]+. Found (%):
C, 45.16; H, 3.25; N, 11.60; S, 13.30. C9H8N2O4S. Calcuꢀ
lated (%): C, 45.00; H, 3.36; N, 11.66; S, 13.35.
SꢀMethyl 2ꢀ(4ꢀchloroꢀ2ꢀnitrophenylamino)ꢀ2ꢀoxothioacetate
(7b) was obtained from 4b (0.33 g, 1 mmol) similarly to comꢀ
pound 7a, the yield was 0.23 g (85%), m.p. 129—131 °C.
1H NMR, δ: 2.4 (s, 3 H, CH3); 7.95 (d, 1 H, Ar, J = 8.69 Hz);
8.0 (t, 1 H, Ar, J = 8.77 Hz); 8.2 (s, 1 H, Ar); 11.3 (s, 1 H, NH).
MS, m/z: 274 [M]+. Found (%): C, 39.15; H, 2.68; N, 10.12;
S, 11.78; Cl, 13.12. C9H7ClN2O4S. Calculated (%): C, 39.35;
H, 2.57; N, 10.20; S, 11.67; Cl, 12.91.
SꢀMethyl 2ꢀ(4ꢀmethylꢀ2ꢀnitrophenylamino)ꢀ2ꢀoxothioacetate
(7c) was obtained from 4c (0.31 g, 1 mmol) similarly to
compound 7a, the yield was 0.22 g (87%), m.p. 187—189 °C.
1H NMR, δ: 2.45 (s, 6 H, CH3); 7.6 (d, 1 H, Ar, J = 7.92 Hz);
7.95 (t, 2 H, Ar, J = 7.11 Hz); 11.2 (s, 1 H, NH). MS, m/z:
254 [M]+. Found (%): C, 47.12; H, 4.06; N, 11.06; S, 12.69.
C10H10N2O4S. Calculated (%): C, 47.24; H, 3.96; N, 11.02;
S, 12.61.
Nꢀ(2ꢀNitrophenyl)ꢀ2ꢀmorpholinoacetamide (5a). Chloroꢀ
acetanilide 2a (0.25 g, 1.2 mmol) in DMF (2 mL) was added to a
mixture of sulfur (0.1 g, 3.6 mmol) and morpholine (1.3 mmol).
The reaction mixture was stirred for 4 h at room temperature
(TLC monitoring showed formation of a mixture of products 4a
and 5a). Then the mixture was poured into water, a precipitate
was filtered off; to purify from the unreacted sulfur, the residue
was dissolved in acetone, the acetone solution was separated,
the solvent was evaporated in vacuo. The mixture of products
obtained was separated by preparative TLC (eluent, light petroꢀ
leum—ethyl acetate, 3 : 1) to obtain compound 4a (0.05 g, 14%),
m.p. 137—138 °C, MS, m/z: 295 [M]+ and compound 5a
(0.26 g, 82%), m.p. 133—135 °C (agrees with the data in Ref. 6).
1H NMR, δ: 2.1 (s,
2 H, CH2); 2.4 (s, 2 H, CH2);
3.2 (s, 2 H, CH2); 3.7 (d, 4 H, CH2, J = 3.72 Hz); 7.30 (t, 1 H,
Ar, J = 7.59 Hz); 7.8 (t, 1 H, Ar, J = 7.55 Hz); 8.2 (d, 1 H, Ar,
J = 8.23 Hz); 8.6 (d, 1 H, Ar, J = 8.26 Hz); 11.5 (s, 1 H, NH).
MS, m/z: 265 [M]+. Found (%): C, 54.21; H, 5.75; N, 15.76.
C12H15N3O4. Calculated (%): C, 54.33; H, 5.70; N, 15.84.
Nꢀ(4ꢀChloroꢀ2ꢀnitrophenyl)ꢀ2ꢀmorpholinoacetamide (5b)
was obtained from 2b (0.25 g, 1 mmol) similarly to compound
5a. There were isolated compound 4b (0.06 g, 18%), m.p. 155—
156 °C, MS, m/z: 329 [M]+ and compound 5b (0.24 g, 80%),
m.p. 265—267 °C. 1H NMR, δ: 3.21 (s, 2 H, CH2); 3.70 (s, 4 H,
CH2); 3.95 (s, 4 H, CH2); 7.20 (m, 2 H, Ar); 7.40 (m, 1 H, Ar);
12.18 (s, 1 H, NH). MS, m/z: 300 [M]+. Found (%): C, 47,89;
H, 4,86; N, 14.17. C12H14ClN3O4. Calculated (%): C, 48.09;
H, 4.71; N, 14.02.
Nꢀ(2ꢀNitrophenyl)ꢀ5Hꢀdibenzo[d,f][1,3]diazepinꢀ6ꢀcarboxꢀ
amide (6a). A suspension of 2,2´ꢀdiaminobiphenyl (0.22 g,
1.2 mmol), sulfur (0.19 g, 6 mmol), triethylamine (0.3 g,
3 mmol) in DMF (5 mL) was stirred at room temperature for
20 min, followed by addition of chloroacetanilide 2a (0.21 g,
1 mmol). The reaction mixture was heated for 6 h at 60—70 °C,
cooled to room temperatures, poured into water (100 mL), a
precipitate was filtered off, dissolved in acetone, and concenꢀ
trated in vacuo. The residue was recrystallized from ethanol or
purified by column chromatography in the ethyl acetate—hexꢀ
NꢀPhenylꢀ1Hꢀbenzoimidazoleꢀ2ꢀcarboxamide (8a). Comꢀ
pound SnCl2•2H2O (1.2 g, 5 mmol) was added to monothioꢀ
oxamide 3a (0.3 g, 1 mmol). The mixture was refluxed in ethanol
(7 mL) for 1 h, then cooled to room temperature, and the
solvent was evaporated in vacuo. Water (5 mL) and 15%
aq. NaOH were added to the residue. The mixture obtained was
extracted with ethyl acetate; the solvent was evaporated, the
residue was purified by preparative TLC (silica gel, eluent: ethyl
acetate—light petroleum 1 : 3) to obtain compound 8a (0.14 g,
58%), m.p. 234—235 °C (agrees with the data in Ref. 7).

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Yarovenko et al.
1H NMR, δ: 7.10 (m, 1 H, Ar); 7.20 (m, 3 H, Ar); 7.3 (m, 2 H,
Ar); 7.55 (m, 1 H, Ar); 8.15 (d, 2 H, Ar, J = 7.96 Hz); 10.8 (s,
1 H, NH); 12.4 (s, 1 H, NH). MS, m/z: 237 [M]+. Found (%):
C, 70.9; H, 4.61; N, 17.80. C14H11N3O. Calculated (%):
C, 70.87; H, 4.67; N, 17.71.
(s, 3 H, CH3); 3.1 (m, 2 H, CH2); 3.56 (m, 2 H, CH2); 3.8 (m,
2 H, CH2); 3.9 (m, 2 H, CH2); 7.07 (m, 1 H, Ar); 7.5 (m, 1 H,
Ar); 7.65 (m, 1 H, Ar); 11.3 (s, 1 H, NH). MS, m/z: 245 [M]+.
Found (%): C, 63.56; H, 6.27; N, 17.0. C13H15N3O2. Calcuꢀ
lated (%): C, 63.66; H, 6.16; N, 17.13.
NꢀPhenylꢀ6ꢀmethylꢀ1Hꢀbenzimidazoleꢀ2ꢀcarboxamide (8c)
was obtained from 3c (0.32 g, 1 mmol) similarly to compound
8a, the yield was 0.14 g (55%), m.p. 137—139 °C. H NMR, δ:
2.4 (s, 3 H, CH3); 6.5 (m, 1 H, Ar); 7.2 (m, 2 H, Ar); 7.3 (m,
2 H, Ar); 7.5 (m, 1 H, Ar); 7.65 (m, 2 H, Ar); 9.4 (s, 1 H, NH);
10.6 (s, 1 H, NH). MS, m/z: 251[M]+. Found (%): C, 71.57;
H, 5.33; N, 16.80. C15H13N3O. Calculated (%): C, 71.70;
H, 5.21; N, 16.72.
1HꢀBenzimidazoleꢀ2ꢀcarboxmorpholide (9a) was obtained
from 4a (0.3 g, 1 mmol) similarly to compound 8a, the yield was
0.14 g (60%), m.p. 129—131 °C. 1H NMR, δ: 3.1 (m, 2 H,
CH2); 3.7 (m, 2 H, CH2); 3.85 (m, 2 H, CH2); 4.05 (m, 2 H,
CH2); 7.2 (m, 2 H, Ar); 7.8 (m, 2 H, Ar); 11.2 (s, 1 H, NH).
MS, m/z: 231 [M]+. Found (%): C, 62.26; H, 5.80; N, 18.08.
C12H13N3O2. Calculated (%): C, 62.33; H, 5.67; N, 18.17.
6ꢀChloroꢀ1Hꢀbenzimidazoleꢀ2ꢀcarboxmorpholide (9b) was
obtained from 4b (0.33 g, 1 mmol) similarly to compound 8a,
the yield was 0.15 g (57%), m.p. 135—137 °C. 1H NMR, δ: 3.05
(m, 2 H, CH2); 3.58 (m, 2 H, CH2); 3.75 (m, 2 H, CH2); 4.0 (m,
2 H, CH2); 7.25 (m, 1 H, Ar); 7.6 (m, 1 H, Ar); 7.86 (m, 1 H,
Ar); 10.8 (s, 1 H, NH). MS, m/z: 265 [M]+. Found (%):
C, 54,45; H, 4.44; N, 15.96; Cl, 13,26. C12H12ClN3O2. Calcuꢀ
lated (%): C, 54.25; H, 4.55; N, 15.82; Cl, 13.34.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 07ꢀ03ꢀ12112)
and the Russian Federation President Council for Grants
(Program for the State Support of Leading Scientific
Schools, Grant NShꢀ9178.2006.3).
1
References
1. M. M. Krayushkin, V. N. Yarovenko, I. V. Zavarzin, Izv.
Akad. Nauk, Ser. Khim., 2004, 53, 491 [Russ. Chem. Bull., Int.
Ed., 53, 517].
2. H. Fuerst, J. Prakt. Chem., 1962, 17, 299.
3. N. Hall, A. Tumer, J. Chem. Soc., 1948, 1909.
4. H. Beckurts, G. Frerichts, Ark. Kemi, 1915, 253, 246.
5. A. K. M. S. Hug, A. C. Markides, J. Electrochem. Soc., 1965,
112, 756.
6. Ger. Offen 2129960; Chem. Abstr., 1972, 76, 72281.
7. P. A. Petyunin, A. M. Choudry, Chem. Heterocyclic. Compd.
EN, 1982, 519.
6ꢀMethylꢀ1Hꢀbenzimidazoleꢀ2ꢀcarboxmorpholide (9c) was
obtained from 4c (0.31 g, 1 mmol) similarly to compound 8a,
the yield was 0.15 g (60%), m.p. 176—179 °C. H NMR, δ: 2.4
Received July 26, 2007;
in revised form January 13, 2008
1