Reduction of 7-R derivatives of 7H-tris[1,2,5]oxa-diazolo[3,4-b:3′, 4′-d:3″,4″-f]azepine 1-oxide with furoxan ring opening. preparation of 4-R-4H-bis-[1,2,5]oxadiazolo[3,4-b:3′,4′-f]azepine-8, 9-diamines

Article abstract of DOI:10.1007/s10593-013-1345-7

It was shown that the reduction of derivatives of 7-R-7H-tris[1,2,5] oxadiazolo[3,4-b:3′,4′-d:3″,4″-f]azepine 1-oxide by hydrazine hydrate or hydrogen in the presence of palladium on carbon is accompanied by opening of the furoxan ring of the starting com

Full text of DOI:10.1007/s10593-013-1345-7

Chemistry of Heterocyclic Compounds, Vol. 49, No. 7, October, 2013 (Russian Original Vol. 49, No. 7, July, 2013)
REDUCTION OF 7-R DERIVATIVES OF 7H-TRIS[1,2,5]OXA-
DIAZOLO[3,4-b:3′,4′-d:3″,4″-f]AZEPINE 1-OXIDE WITH
FUROXAN RING OPENING. PREPARATION OF 4-R-4H-BIS-
[1,2,5]OXADIAZOLO[3,4-b:3′,4′-f]AZEPINE-8,9-DIAMINES
A. I. Stepanov1*, D. V. Dashko,1 and A. A. Astrat'ev1
It was shown that the reduction of derivatives of 7-R-7H-tris[1,2,5]oxadiazolo[3,4-b:3′,4′-d:3″,4″-f]-
azepine 1-oxide by hydrazine hydrate or hydrogen in the presence of palladium on carbon is
accompanied by opening of the furoxan ring of the starting compound to the two amino groups and
leads to the production of 4-R-4H-bis[1,2,5]oxadiazolo[3,4-b:3′,4′-f]azepine-8,9-diamines. Some
chemical properties of the obtained diamino compounds are discussed.
Keywords: azepine, furazan, furoxan, 1,2,5-oxadiazole, catalytic hydrogenation.
Reduction of the 1,2,5-oxadiazole-2-oxide (furoxan) ring to two vicinal amino groups is typical
primarily for benzofuroxan derivatives [1]. However, the reaction has not found practical application as a
method for the synthesis of vicinal diamino derivatives of aromatic compounds containing benzene rings.
In the previous article [2], we examined Pd/C-catalyzed reduction with opening of the furoxan ring to
two oxime groups in 4,4"-R,R derivatives of 3,3':4',3"-ter[1,2,5]oxadiazole 2'-oxide (3,4-bis(4-R-furazan-
3-yl)furoxan). In the present work, we investigated the reduction of the cyclic analogs of these compounds,
7-substituted derivatives of 7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepine 1-oxide 1a-k, using a
palladium catalyst. Unlike the compounds with linear structure reduction of the furoxan ring in the azepine
derivatives 1a-j, like the reduction of benzofuroxans [1], proceeded further and led to the production of
previously unknown 4-R-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamines 2a-j, and the tetraamino
derivative 2k was formed as a result of reduction of 1,2-bis(7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]-
azepin-7-yl)ethane 1,1'-dioxide (1k). In the case of compounds 1c,f, we showed that the reduction proceeded
through the intermediate formation of the corresponding 1,2-dioximes 3a-j.
The starting 7-substituted derivatives of azepine 1a-k can be synthesized fairly easily by reaction of the
synthetically available 4,4"-dinitro-3,3':4',3"-ter[1,2,5]oxadiazole 2'-oxide (3,4-bis(4-nitrofurazan-3-yl)furoxan,
BNFF) (4) [3-5] with an excess of a highly basic primary amine (1,2-diaminoethane in the case of compound
(1k), ammonia, or hydrazine and also by alkylation of the azepine 1a unsubstituted at the nitrogen atom, e.g.,
with chloroacetamide (compound 1j) [6-8].
_______
*To whom correspondence should be addressed, e-mail: stepanoff@pisem.net.
1Special Design and Construction Bureau SDCB "Technolog", 33-A Sovetskii Ave., Saint Petersburg 192076,
Russia.
_______________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1145-1159, July, 2013. Original
article submitted August 21, 2012; revision submitted May 26, 2013.
1068
0009-3122/13/4907-1068©2013 Springer Science+Business Media New York

O
O
O
N
N
N
N
N
N
R
R
R
6
6
6
[H]/Pd/C
2-PrOH
[H]/Pd/C
2-PrOH
N
N
1
N
1
5
5
5
1
4
O
HO
4
4
N+
O
N
H2N
2
3
N
N
N
2
2
3
3
O
O
O
H2N
N
N
HO
N
N
N
1a–j
3a–j
2a–j
O
O
N
O
O
N
N
N
N
N
N
N
N
N
NH2
NH2
O
O
[H]/Pd/C
2-PrOH
N+
H2N
N+
N
N
O
N
O
O
N
H2N
N
N
N
N
N
N
N
N
O
O
O
1k
2k
a R = H, b R = NH2, c R = Me, d R = CH2CH2OH, e R = CH2CH2NH2, f R = CH2Ph,
g R = furfuryl, h R = tetrahydrofurfuryl, i R = CH2CH2C6H3(OMe)2-3,4, j R = CH2CONH2
N
O
O2N
N
RNH2
NO2
1a–i,k
O
N+
O
MeCN
N
O
N
N
4
The reduction of azepines 1a-k is conveniently realized in lower alcohols (methanol, ethanol,
2-propanol) as solvents. In this case, the formed diamines 2a-k precipitate from the reaction mixture. After
filtration of the reaction mixture, they can be separated from the catalyst by extraction with hot DMF.
Hydrazine hydrate in the presence of 5-10% Pd/C can be used for reduction. The use of hydrogen in this
reaction under the pressure 2-10 atm leads to a substantial increase in the yields of the diamines 2a-k.
By stopping the hydrogenation process before the absorption of the amount of hydrogen theoretically
required for opening of the furoxan ring to two amino groups it is possible to isolate the intermediate in the
reduction of the azepine 1c, i.e., the dioxime 3c. Unlike the corresponding amine precipitated from the reaction
mixture, the dioxime is readily soluble in alcohols (methanol, ethanol, 2-propanol) and can be isolated by
distillation of the solvent at reduced pressure after removal of precipitated diamine 2c from the filtrate.
Dissolution of the obtained residue in a 5% aqueous solution of alkali followed by treatment with acetic
anhydride at reduced temperature leads to closure of the vicinal oxime groups into a furazan ring and the
formation of 7-methyl-7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepine (5c). The formation of the
trisfurazanoazepine 5f, isolated as a result of analogous treatment of the filtrate from the reaction mixture after
hydrogenation of the azepine 1f, indicates intermediate formation of the corresponding dioxime 3f. The ease of
formation of the furazan ring from the dioximes 3c,f and also the data from NMR spectroscopy of compound 3c
(two signals for the protons of the oxime groups, the magnetic nonequivalence of all six carbon atoms of the
azepine ring) indicate in favor of the preferential formation of the (Z,E) isomer (the amphi form) of the dioxime
3c,f. Thus, the initial mutual orientation of the oxygen atoms of the furoxan ring is preserved during reduction
of this ring in compound 1c. It should be noted that the isolation and purification of the dioxime 3c by
recrystallization or reprecipitation during acidification of its aqueous alkaline solution is accompanied by partial
isomerization of the (Z,E) isomer of the dioxime to the (Z,Z) isomer (the anti form). Thus, whereas according to
1H NMR spectroscopy the ratio of the two isomers in the unpurified dioxime 3c isolated from the reaction
mixture was in the order of 5-6:1, after recrystallization from methanol or reprecipitation this ratio decreased to
2.6:1 and 1.8:1, respectively. Methylation of the unpurified (Z,E)-dioxime 3c with dimethyl sulfate leads to
1069

production of the corresponding O-methyl derivative 6 with retention of the initial geometric configuration of
the isonitroso groups in the final product. The cyclic derivatives of trifurazan 5c,f can also be obtained by direct
reduction of their N-oxides 1c,f by tin(II) chloride in an acidic medium.
O
N
1c,f
N
R
SnCl2, HCl,
AcOH
H2, Pd/C,
2-PrOH
N
(R = Me)
1. OH–
2. H+
HO
N
N
O
O
N
O
N
N
N
N
1. NaOH
2. Ac2O
N
R
R
OH
(Z,Z)-3c
6
N
N
5
(R = Me)
Me2SO4
K2CO3
1
HO
4
O
N
N
O
N
2
N
O
N
3
N
Me
O
N
HO N
N
N
N
DMF
5c,f
(Z,E)-3c,f
MeO
N
N
O

H2, Pd/C,
– NH3
c R = Me,
f R = CH2Ph
MeO
N
N
1b
2a
6
During the hydrogenation of 7-amino-7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepine 1-oxide
(1b) the absorption of hydrogen exceeds the theoretically required amount for the formation of two amino groups
on account of parallel deamination of the exocyclic 7-amino group (cleavage of the hydrazine N–N bond) with the
formation of the diamine 2a (yield about 50%). In this case, despite the lower yield of the required product, it is
advisable to use hydrazine hydrate in the presence of Pd/C for reduction of the azepine 1b.
We note the hydrogenation of oxepino[2,3-c:4,5-c':6,7-c"]tris[1,2,5]oxadiazole 1-oxide (7) [8-10], obtained
by heating BNFF (4) in aprotic solvents in the presence of K2CO3, leads to the formation of oxepino[2,3-c:6,7-
c']bis[1,2,5]oxadiazole-8,9-diamine (8). The low yield of the diamine 8 confirms our previously mentioned less
stability of the oxepine ring in the investigated heterocyclic systems compared with azepine [8].
O
O
N
N
N
N
6
O
H2, Pd/C
2-PrOH
O
K2CO3
MeCN,
– N2O3
5
4
1
O
4
N+
2

H2N
N
O
3
N
O
O
H2N
N
N
N
7
8
The chemical properties of the diamines 2a-k make it possible to use them for the production of various
polycondensed heterocyclic systems containing two 1,2,5-oxadiazole fragments. For example, during
nitrosation of the diamines 2a(or b), 2c,d,f by NaNO2 in AcOH we obtained the corresponding 1,2,3-triazole
derivatives 9a,c,d,f. Reaction of the diamine 2c with triethyl orthoformate, acetic or propionic anhydride leads
to closure of the vicinal amino groups to the imidazole ring with the formation of 2-R-7-alkyl-1H,7H-
imidazo[4,5-d]bis([1,2,5]oxadiazolo[3,4-b:3',4'-f]azepines) 10a-c. The 2-phenyl-substituted imidazole derivative
11 is formed upon the action of benzaldehyde on the diamine 2c. The reaction probably proceeds through the
intermediate formation of the corresponding 2-phenyldihydroimidazole, which is readily oxidized to an
imidazole derivative under the reaction conditions. The signals of the carbon atoms in the imidazole and 1,2,3-
triazole rings in the 13C NMR spectra are broadened and in a number of cases cannot be detected on account of
tautomeric transitions of the hydrogen atom in the NH group of the heterocycle (Tables 3, 4). The
2-mercaptoimidazole derivative 12 is formed upon the action of carbon disulfide on the diamine 2c. According
to 13C NMR spectroscopy data, in solution in DMSO the mercaptoimidazole 12 exists in the tautomeric thione
1070

form [11]. (In this case the very strong absorption band at 1560 cm-1 in the IR spectrum can be assigned to the
NC=S fragment vibrations characteristic of the thione form of 2-mercaptoimidazole [12].) The thiol form of
compound 12 enters into condensation with chloroacetic acid and benzaldehyde, in the course of which the
annelated 5-benzylidenethiazol-4-one 13 (a 1:3 mixture of (E, Z) isomers) is formed.
(R1CO)2O
or
HC(OEt)3
O
O
N
N
N
Me
N
N
R
6a
6
7N
7a
3b
3a
10b
NaNO2
N
1
5
2a,c,d,f
4
.
AcOH
H2O
10°C, 
BF3 Et2O
N3
2
N
N
N
2
3
10a
1
N
O
O
R1
N
N
N
9a,c,d,f
10a–c
O
O
N
N
N
N
CS2
NaOH
Me
PhCHO
O2
Me
6a
6a
7N
7N
7a
3b
3a
10b
10a
3b
3a
10b
2c
7a
EtOH, 
EtOH, 
HN3
N
O
N3
2
N
O
10a
2
1
1
N
N
N
N
S
Ph
H
11
12
O
O
O
N
PhCHO
ClCH2CO2H
NaOAc, Ac2O
AcOH, 
N
Me
4a
4N
3a
O
7a
7b
N8
DMF, 
EtOH
3N
2O
14b
9
O
N
N
14a
1
N
10
11
1N4
8a
R1COCOR2
8b
Me
13a
13
N
8
12a
12
O
O
14a
N
N
N
N
N
Me
O
N
7a
8N
8a
4b
4a
1
S
3
2
N
N
O
11a
11b
4
O
R1
1
N
3
Ph
N
2
R2
13
14b–e
9 a R = H, c R = Me, d R = CH2CH2OH, f R = CH2Ph; 10 a R1 = H, b R1 = Me, c R1 = Et;
14 b R1 = R2 = H, c R1 = R2 = Me, d R1 = 4-ClC6H4, R2 = H, e R1 = R2 = Ph
Condensation of the diamine 2c with 2,2-dihydroxyindane-1,3-dione (ninhydrin) leads to the formation
of the condensed pyrazine 14a. Condensation takes place in a similar way with such α-dicarbonyl compounds as
glyoxal (in the form of its bishemiacetal), diacetyl, p-chlorophenylglyoxal, or dibenzyl (products 14b-e,
respectively).
1
The structure of the obtained compounds was confirmed by methods of instrumental analysis. The H,
13C NMR, and mass spectra of the obtained compounds are given in Tables 1-5.
Thus, the reduction of the 7-substituted 7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepine 1-oxide
derivatives, that have become synthetically available, in the presence of palladium on carbon is a convenient and,
very likely, currently the only method for the production of 4-substituted 4-R-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]-
azepine-8,9-diamines. The vicinal arrangement of the amino groups makes it possible to use the synthesized
diamines for the production of a wide range of polyheterocyclic compounds containing two 1,2,5-oxadiazole rings.
1071

1072

1073

1074

1075

EXPERIMENTAL
1
The IR spectra were recorded in pellets with KBr on an FSM-1201 Fourier spectrometer. The H and
13C NMR spectra were recorded in DMSO-d6 on a Bruker DRX-400 spectrometer (400 and 100 MHz,
1
respectively). The H and 13C chemical shifts were determined with reference to the solvent signal (δ 2.51 and
39.96 ppm, respectively). The mass spectra were recorded on a Finnigan MAT INCOS 50 spectrometer (EI,
70 eV). Elemental analysis was performed on a Perkin-Elmer 2400 elemental analyzer. The melting points were
determined on a Kofler hot bench.
Compounds 1a-d,f were obtained according to [7], and compounds 1e,k according to [8]. The synthesis
of oxepino[2,3-c:4,5-c':6,7-c″]tris[1,2,5]oxadiazole 1-oxide was described in [8].
7-(Furan-2-ylmethyl)-7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepine 1-Oxide (1g). The
compound was obtained by the method in [8] from BNFF (4) and furfurylamine. Yield 1.1 g (35%), mp
155-156°C (EtOH). IR spectrum, ν, cm-1: 3150, 3120, 3005, 2965, 2925, 1655, 1615, 1610, 1595, 1565, 1530,
1480, 1390, 1350, 1240, 1215, 1160, 1150, 1090, 1065, 1015, 1010, 990, 980, 970, 925, 910, 900, 820, 755,
740, 725, 660, 590. Found, %: С 42.01; H 1.72; N 31.05. C11H5N7O5. Calculated, %: C 41.92; H 1.60; N 31.11.
7-(Tetrahydrofuran-2-ylmethyl)-7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepine
1-Oxide
(1h). The compound was obtained according the method in [8] from BNFF (4) and tetrahydrofurfurylamine.
Yield 2.2 g (73%), mp 155.5-156.5°C. IR spectrum, ν, cm-1: 3585-3545, 3510-3460, 3440, 2985, 2960, 2880,
2860, 1650, 1610, 1590, 1565, 1530, 1480, 1455, 1390, 1355, 1290, 1230, 1165, 1130, 1085, 1065, 990, 965,
900, 835, 820, 785, 730, 660, 590, 510, 475, 435. Found, %: С 41.11; H 2.86; N 30.52. C11H9N7O5. Calculated,
%: C 41.39; H 2.84; N 30.71
7-[2-(3,4-Dimethoxyphenyl)ethyl]-7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepine 1-Oxide
(1i). The compound was obtained according to the method in [8] from BNFF (4) and homoveratrylamine. Yield
3.4 g (80%), mp 253-254°C (DMF–AcOH). IR spectrum, ν, cm-1: 3010, 2970, 2940, 2910, 2875, 2840, 1650,
1610, 1590, 1565, 1530, 1510, 1480, 1450, 1355, 1265, 1235, 1160, 1140, 1025, 990, 970, 845, 820, 590. Found,
%: С 48.27; H 3.33; N 24.35. C16H13N7O6. Calculated, %: C 48.12; H 3.28; N 24.55.
7-(2-Amino-2-oxoethyl)-7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepine
1-Oxide
(1j).
Compound 1a (2.35 g, 0.01 mol) was dissolved in DMF (25 ml); anhydrous K2CO3 (2 g, 0.015 mol) and
chloroacetamide (1.05 g, 0.011 mol) were added, and the mixture was stirred at 50°C for 24 h. The reaction
mixture was poured with stirring into cold water (100 ml), and the formed precipitate was filtered off, washed
with water, and recrystallized from a 2:1 EtOH–AcOH mixture. Yield 2.1 g (72%), mp 173°C. IR spectrum, ν,
cm-1: 3445, 3240, 3190, 3010, 2955, 2925, 2850, 1705, 1640, 1610, 1600, 1565, 1535, 1485, 1390, 1360, 1300,
1235, 1165, 995, 975, 900, 830, 785, 740, 725, 610, 590, 560, 540, 500, 435. Found, %: С 32.65; H 1.52;
N 38.14. C8H4N8O5. Calculated, %: C 32.89; H 1.38; N 38.35.
Preparation of 4-Substituted 4H-Bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamines 2a-k
(General Method). A. Reduction with hydrazine hydrate. Corresponding compound 1a-c (0.04 mol) was added
to 2-PrOH (100 ml) that had been heated to 40°C; 5-10% Pd/C [13] (0.5 g) was added, and hydrazine hydrate
(7.6 ml, 0.16 mol) was then added in small portions at such a rate that the temperature of the reaction mixture
did not rise above 60°C. The mixture was stirred at this temperature for 4-6 h and cooled to 20°C. The
precipitated dark-green product was filtered off together with the catalyst, washed with EtOH, and separated
from the catalyst by extraction with hot DMF. Water was added to the hot filtrate drop by drop until
precipitation began. After the obtained mixture had cooled to room temperature the finely crystalline yellow-
greenish precipitate was separated by filtration.
B. Hydrogenation by hydrogen under pressure. 5-10% Pd/C (0.5 g) was added to a solution of the
starting compound 1a-k (0.04 mol) in 2-PrOH (100 ml). The mixture was hydrogenated at 45-65°C at 2-10 atm
until the absorption of hydrogen had stopped (6-8 h). The reaction mixture was then treated according to
method A.
1076

4H-Bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamine (2a). The compound was obtained by
reduction of compound 1a. Yield 4.5 g (45%, method A), 4.8 g (70%, method B), mp 294-295°C (EtOH–DMF,
2:1). IR spectrum, ν, cm-1: 3560, 3415, 3375, 3335, 3270, 3220, 3175, 3138, 1640, 1595, 1575, 1515, 1485,
1425, 1135, 1040, 1000, 980, 940, 855, 800, 765, 680, 635, 610, 575, 530, 475. Found, %: C 34.56; H 2.75;
N 47.57. C6H5N7O2. Calculated, %: С 34.78; H 2.42; N 47.34.
Hydrogenation of compound 1b. Compound 1b (10.0 g, 0.04 mol) was reduced by method B for 24-26 h
until the absorption of hydrogen had stopped. The reaction mixture poured from the autoclave had a strong
smell of ammonia. The product 2a was isolated as described above. Yield 4.2 g (51%).
4H-Bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-4,8,9-triamine (2b). The compound was obtained by
reduction of compound 1b. Yield 4.6 g (52%, method A), 5.6 g (63%, method B), at 30°C after absorption of
the theoretical amount of H2, mp 239-240°C (EtOH-DMF, 1:1). IR spectrum, ν, cm-1: 3415, 3375, 3340, 3270,
3220, 3175, 3145, 1640, 1570, 1510, 1185, 1130, 1040, 975, 860, 765, 675, 575, 530, 475. Found, %: C 32.70;
H 2.88; N 50.17. C6H6N8O2. Calculated, %: С 32.43; H 2.72; N 50.45.
4-Methyl-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamine (2c). The compound was
obtained by reduction of compound 1c. Yield 5.4 g (61%, method A), 6.6 g (74%, method B), mp 207-208°C
(EtOH–DMF, 1:1). IR spectrum, ν, cm-1: 3420, 3345, 3265, 3220, 3005, 2935, 1645, 1590, 1520, 1190, 1010,
990, 925, 850, 640, 575, 480. Found, %: C 37.88; H 3.26; N 44.55. C7H7N7O2 Calculated, %: С 38.01; H 3.17;
N 44.34.
4-(2-Hydroxyethyl)-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamine (2d). The compound
was obtained by reduction of compound 1d. Yield 7.3 g (73%, method B), mp 218-219°C (EtOH–DMF, 3:1).
IR spectrum, ν, cm-1: 3440, 3355, 3270, 1650, 1580, 1515, 1455, 1435, 1340, 1190, 1065, 1020, 875, 845, 820,
580, 480. Found, %: C 38.09; H 3.70; N 39.17. C8H9N7O3. Calculated, %: С 38.25; H 3.61; N 39.03.
4-(2-Aminoethyl)-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamine (2e). The compound
was obtained by reduction of compound 1e. Yield 7.1 g (71%, method B), mp 227-228°C (EtOH–DMF, 1:1). IR
spectrum, ν, cm-1: 3440, 3365, 3125, 3120, 2960, 2920, 2850, 1655, 1630, 1610, 1585, 1555, 1510, 1455, 1430,
1410, 1375, 1325, 1210, 1195, 1100, 1025, 995, 930, 905, 870, 840, 630, 575, 525, 485. Found, %: C 38.49; H
4.14; N 44.67. C8H10N8O2. Calculated, %: С 38.40; H 4.03; N 44.78.
4-Benzyl-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamine (2f). The compound was
obtained by reduction of compound 1f. Yield 8.7 g (73%, method B), mp 211-212°C (EtOH–DMF, 2:1). IR
spectrum, ν, cm-1: 3425, 3345, 1640, 1605, 1585, 1580, 1510, 1190, 1040, 1020, 970, 895, 845, 765, 665, 590,
570, 480. Found, %: C 52.75; H 3.89; N 32.74. C13H11N7O2. Calculated, %: С 52.52; H 3.73; N 33.00.
4-(Furan-2-ylmethyl)-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamine
(2g).
The
compound was obtained by reduction of compound 1g. Yield 7.3 g (64%, method B), mp 215-216°C (EtOH–
DMF, 5:1). IR spectrum, ν, cm-1: 3420, 3350, 3340, 1645, 1610, 1580, 1510, 1425, 1340, 1185, 1150, 1115,
970, 840, 830, 760, 745, 665, 600, 570. Found, %: C 45.93; H 3.20; N 34.19. C11H9N7O3. Calculated, %:
С 46.00; H 3.16; N 34.13.
4-(Tetrahydrofuran-2-ylmethyl)-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamine (2h). The
compound was obtained by reduction of compound 1h.Yield 8.9 g (77%, method B), mp 236-238°C (EtOH). IR
spectrum, ν, cm-1: 3435, 3365, 3270, 3205, 2980, 2930, 2885, 1650, 1640, 1600, 1585, 1520, 1190, 1070, 1030, 980,
860, 810, 575. Found, %: C 45.42; H 4.67; N 33.48. C11H13N7O3. Calculated, %: С 45.36; H 4.50; N 33.66.
4-[2-(3,4-Dimethoxyphenyl)ethyl]-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamine (2i).
The compound was obtained by reduction of compound 1i. Yield 8.9 g (77%, method B), mp 233-234°C
(EtOH–DMF, 2:1). IR spectrum, ν, cm-1: 3425, 3350, 3320, 2965, 2940, 2930, 1645, 1585, 1515, 1465, 1450,
1420, 1265, 1230, 1180, 1140, 1125, 1110, 930, 855, 840, 580, 565. Found, %: C 51.64; H 4.72; N 26.31.
C16H17N7O4. Calculated, %: С 51.75; H 4.61; N 26.40.
2-(8,9-Diamino-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepin-4-yl)acetamide (2j). Yield 8.0 g (73%,
method B), mp 323-325°C (EtOH–DMF, 1:1). Found, %: C 36.24; H 3.12; N 42.54. C8H8N8O3. Calculated, %:
С 36.37; H 3.05; N 42.41.
1077

4,4'-Ethane-1,2-diylbis(4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-diamine)
(2k).
The
compound was obtained by reduction of compound 1k. Yield 72% (method B, hydrogenation conducted with
the addition of 30-40% of DMF), mp >300°C (DMF). Found, %: C 38.26; H 2.98; N 44.27. C14H12N14O4.
Calculated, %: С 38.19; H 2.75; N 44.53.
Oxepino[2,3-c:6,7-c']bis[1,2,5]oxadiazole-8,9-diamine 8. The compound was obtained similarly to
compounds 2a-k by method B from compound 7. Yield 2.9 g (35%), mp 204-205°C (2-PrOH). IR spectrum, ν,
cm-1: 3420, 3340, 1645, 1605, 1555, 1525, 1200, 1180, 1030, 1000, 845, 615, 580, 575, 555, 480. Found, %:
C 34.75; H 2.05; N 40.31. C6H4N6O3. Calculated, %: С 34.62; H 1.94; N 40.38.
4-Methyl-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-dione Dioxime (3c). The azepine 1c (10 g,
0.04 mol) was hydrogenated as described above for the production of the diamine 2c (method B). The reaction
mixture was then cooled to 20°C and filtered from the mixture of the precipitated diamine 2c and the catalyst.
The solvent was distilled from the filtrate under vacuum to one third of the initial volume and diluted with water
until crystallization of the dioxime 3c began. The precipitated product was filtered off, dissolved in boiling
methanol (50 ml), and purified with activated carbon (1 g). The hot solution was filtered through a filter paper.
The filtrate was heated to boiling and slowly diluted until the product began to crystallize. The mixture was
cooled to room temperature, and the precipitated product was filtered off. Yield 2.4 g (24%), mp 217-218°C,
mixture of amphi and anti isomers, 2.6:1. IR spectrum, ν, cm-1: 3575, 3490, 3300, 3180, 3025, 3010, 2905,
1625, 1590, 1530, 1510, 1485, 1425, 1365, 1185, 1065, 995, 940, 885, 590. 1H NMR spectrum, δ, ppm (J, Hz):
13.39 (0.73Н, s, NOH-amphi); 13.23 (0.55Н, s, 2NOH-anti); 13.06 (0.74Н, s, NOH-amphi); 3.62 (3H, s, CH3)
13C NMR spectrum, δ, ppm: 154.1; 153.9; 153.8; 142.6; 141.6; 136.4; 135.9; 133.9; 131.2; 38.3 and 38.2 (2:1,
NCH3). Mass spectrum, m/z (Irel, %): 251 [M+H]+ (0.5), 251 [M]+ (10), 235 [M-NO]+ (1.3), 234 [M-OH]+ (13),
221 [M-2NO]+ (1.5), 83 (15), 67 (24), 42 (20), 30 [NO]+ (100). Found, %: C 34.02; H 2.35; N 38.86. C7H5N7O4.
Calculated, %: С 33.47; H 2.01; N 39.04.
For purification by reprecipitation, the raw product 3c isolated from the reaction mixture was dissolved in
2% aqueous solution NaOH (50 ml) at 20°C, stirred at this temperature for 30 min with activated carbon (1.5 g),
and filtered through a filter paper. The filtrate was acidified to pH 3 by the addition of conc. HCl. The precipitate
was separated by filtration. Yield 2.7 g (27%), mp 216-217°C, mixture of amphi and anti isomers, 1.8:1.
Production of 7-Substituted 7H-Tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepines 5c,f (General
Method). A. Reduction of Furoxans 1c,f with SnCl2. Corresponding azepine 1c,f (0.05 mol) and SnCl2·2H2O
(22.6 g, 0.10 mol) in conc. HCl (50 ml) were added to AcOH (50 ml). The mixture was stirred at 60-70°C for
6 h, and the excess of the solvent was then distilled under vacuum. The precipitate was filtered off, washed with
10% HCl, and recrystallized from AcOH–EtOH, 1:3.
B. Hydrogenation of Furoxans 1c,f. Starting compound 1c,f (0.04 mol) was hydrogenated as described
above for the preparation of the diamines 2a-k by method B, but the reaction was stopped when approximately
half of the calculated amount of hydrogen for the formation of compound 2 had been absorbed. The reaction
mixture was quickly cooled to 20°C by delivering cold water to the jacket of the autoclave and filtered from the
catalyst and the precipitated diamine 2. The filtrate was evaporated to dryness under vacuum, and the residue
was treated with 5% NaOH (200 ml). The obtained solution was filtered, the filtrate was cooled to 10°C, and
Ac2O (2.5 g, 0.025 mol) was added at this temperature with vigorous stirring. The precipitate was filtered off
and recrystallized from DMF–EtOH.
7-Methyl-7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepine (5c). The compound was obtained by
reduction of compound 1c. Yield 7.5 g (65%, method A), 2.6 g (27%, method B), mp 160-161°C (EtOH–DMF, 3:1).
IR spectrum, ν, cm-1: 3430, 1590, 1550, 1500, 1420, 1200, 1000, 980, 900, 880. 1H NMR spectrum, δ, ppm: 3.72
(3H, s, CH3). 13C NMR spectrum, δ, ppm: 150.7; 144.5; 139.5; 22.9 (CH3). Mass spectrum, m/z (Irel, %): 233
[M]+ (100), 203 [M-NO]+ (25), 173 [M-2NO]+ (1), 143 [M-3NO]+ (3). Found, %: C 35.95; H 1.34; N 41.88.
C7H3N7O3. Calculated, %: С 36.05; H 1.29; N 42.06.
7-Benzyl-7H-tris[1,2,5]oxadiazolo[3,4-b:3',4'-d:3",4"-f]azepine (5f). The compound was obtained by
reduction of compound 1f. Yield 7.3 g (47%, method A), 2.4 g (20%, method B), mp 143-144°C (EtOH–DMF, 3:1).
1078

IR spectrum, ν, cm-1: 3070, 3020 (С–H Ar), 2990, 2920 (CH2), 1630 (N→O), 1600, 1590, 1570, 1520, 1480,
1
1430, 1370, 1220, 1160, 1000, 980, 900, 600. H NMR spectrum, δ, ppm: 7.53-7.51 (2H, m, H Ph); 7.38-7.27
13
(3H, m, H Ph); 5.41 (2H, s, CH2). C NMR spectrum, δ, ppm: 154.4; 144.5; 137.1; 134.4 (C-1'); 128.9 (C-3');
128.2 (C-4'); 127.6 (C-2'); 55.1 (CH2). Mass spectrum, m/z (Irel, %): 309 [M]+ (6), 91 [PhCH2]+ (100). Found, %:
C 50.27; H 2.48; N 31.53. C13H7N7O3 Calculated, %: C 50.48; H 2.26; N 31.71.
4-Methyl-4H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]azepine-8,9-dione
Bis(O-methyldioxime)
(6).
Dioxime 3c (1.0 g, 4 mmol) was dissolved in DMF (35 ml), K2CO3 (2.5 g, 23.6 mmol) was added, and dimethyl
sulfate (1.5 g, 12.0 mol) was added dropwise at 10-15°C. The mixture was stirred at room temperature for 4 h
and poured into water (100 ml). After 24 h, the precipitate was filtered off and washed with water. The product
1
was recrystallized from MeOH. Yield 0.7 g (65%), mp 126-127°C. H NMR spectrum, δ, ppm: 4.12 (3H, s,
ОСН3); 4.10 (3H, s, ОСН3); 3.66 (3H, s, NСН3). Mass spectrum, m/z (Irel, %): 279 [M]+ (26), 249 [M-NO]+ (2),
83 (21), 67 (40), 53 (11), 42 (14), 30 [NO]+ (100), 29 (28). Found, %: C 38.38; H 3.32; N 34.91. C9H9N7O4.
Calculated, %: С 38.71; H 3.25; N 35.12.
Preparation of 7-Substituted 1H,7H-Bis[1,2,5]oxadiazolo[3,4-b:3',4'-f][1,2,3]triazolo[4,5-d]-
azepines 9a,c,d,f (General Method). The corresponding diamine 2a,c,d,f (0.01 mol) was suspended in AcOH
(50 ml), and a solution of NaNO2 (1 g, 0.014 mol) in water (5-10 ml) was then added dropwise at 10°C. The
reaction mixture was stirred at this temperature for 1 h, after which the mixture was heated slowly to boiling.
The reaction mixture was left to cool to room temperature in air, and the yellow precipitate was filtered off,
washed with water, and recrystallized.
1H,7H-Bis[1,2,5]oxadiazolo[3,4-b:3',4'-f][1,2,3]triazolo[4,5-d]azepine (9a). This compound was
obtained from the diamine 2a or triamine 2b. (When compound 2b was used twice the amount of NaNO2 was
added.) Yield 1.48 g (68% from compound 2a) and 1.55 g (71% from compound 2b), mp >350°C (subl.)
(AcOH). IR spectrum, ν, cm-1: 3290, 3200, 3155, 3090, 2990, 1640, 1590, 1520, 1480, 1435, 1405, 1360, 1185,
1135, 1015, 980, 895, 805, 730, 660, 585, 450.
7-Methyl-1H,7H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]triazolo[4,5-d]azepine (9c). This compound was
obtained from the diamine 2c. Yield 1.74 g (75%), mp 320°C (begins to sublime), 345°C (decomp.) (DMF–
EtOH, 1:2). IR spectrum, ν, cm-1: 3255, 3160, 3010, 2930, 2870, 1605, 1575, 1545, 1510, 1415, 1375, 1355,
1170, 1150, 1060, 1010, 980, 885, 820, 580, 465.
7-(2-Hydroxyethyl)-1H,7H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f][1,2,3]triazolo[4,5-d]azepine
(9d).
This compound was obtained from the diamine 2d. Yield 1.68 g (63%), mp 245-246°C (AcOH). IR spectrum, ν,
cm-1: 3450, 3125, 3115, 3100, 2930, 2870, 2830, 2800, 2775, 2710, 2645, 1600, 1575, 1540, 1460, 1370, 1365,
1335, 1195, 1180, 1060, 1035, 980, 890, 865, 815, 580, 570, 530.
Benzyl-1H,7H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f][1,2,3]triazolo[4,5-d]azepine (9f). This compound was
obtained from the diamine 2f. Yield 2.20 g (71%), mp 266-267°C (AcOH). IR spectrum, ν, cm-1: 3290, 3200, 3155,
3090, 2990, 1640, 1590, 1520, 1480, 1435, 1405, 1360, 1185, 1135, 1015, 980, 895, 805, 730, 660, 585, 450.
7-Methyl-1H,7H-imidazo[4,5-d]bisfurazano[3,4-b:3',4'-f]azepine (10a). Diamine 2c (2.2 g, 0.01 mol)
was added with vigorous stirring to (EtO)3CH (20 ml), BF3·Et2O (2-3 drops, about 50 mg, ~0.35 mmol) was added,
and the mixture was slowly heated to 120°C with simultaneous distillation of the ethanol that formed. The mixture
was stirred at this temperature for 1 h and cooled to room temperature. After 24 h, the precipitate was filtered off
and recrystallized from DMF. (The product was very insoluble in the usual organic solvents.) Yield 1.7 g (74%),
mp >350°C. IR spectrum, ν, cm-1: 3435, 3150, 3140, 2990, 2930, 2795, 2760, 2715, 2685, 2660, 2605, 2550, 1850,
1805, 1775, 1590, 1565, 1545, 1505, 1460, 1355, 1275, 1135, 1045, 1010, 960, 955, 875, 820, 640, 615, 580, 450.
Found, %: C 41.68; H 2.23; N 42.34. C8H5N7O2. Calculated, %: С 41.56; H 2.18; N 42.41.
2,7-Dimethyl-1H,7H-imidazo[4,5-d]bisfurazano[3,4-b:3',4'-f]azepine (10b). The diamine 2c (2.2 g,
0.01 mol) was added with vigorous stirring to acetic anhydride (20 ml), BF3·Et2O (2-3 drops, about 50 mg,
~0.35 mmol) was added, and the mixture was then heated slowly to boiling and refluxed for 1 h. It was then
cooled to room temperature and poured into H2O (100 ml). After 24 h, the precipitate was filtered off and
recrystallized from a 1:2 DMFEtOH mixture. Yield 1.9 g (78%), mp 243-245°C (subl.). IR spectrum, ν, cm-1:
1079

3120, 3090, 3010, 2920, 2880, 2825, 2795, 2700, 2610, 2535, 2455 (NH+CH3), 1815, 1780, 1760, 1726, 1655,
1570, 1540, 1490, 1400, 1145, 1050, 1030, 1010, 965, 910, 875, 815, 720, 575, 465. Found, %: C 43.94;
H 2.95; N 40.14. C9H7N7O2. Calculated, %: С 44.09; H 2.88; N 39.99.
2-Ethyl-7-methyl-1H,7H-imidazo[4,5-d]bisfurazano[3,4-b:3',4'-f]azepine (10c). This compound was
obtained similarly to compound 10b using propionic anhydride (20 ml). Yield 1.63 g (63%), mp 258-259°C. IR
spectrum, ν, cm-1: 3590, 3410, 3090, 2985, 2940, 2900, 2850, 2820, 2780, 2735, 2615, 1655, 1570, 1545, 1480,
1455, 1420, 1150, 1050, 1005, 970, 880, 820, 580. Found, %: C 46.47; H 3.35; N 37.91. C10H9N7O2.
Calculated, %: С 46.33; H 3.50; N 37.82.
7-Methyl-2-phenyl-1H,7H-imidazo[4,5-d]bisfurazano[3,4-b:3',4'-f]azepine (11). Diamine 2c (2.2 g,
0.01 mol) was suspended in EtOH (100 ml); benzaldehyde (1.2 ml, 1.25 g, 12.00 mmol), and conc. HCl (2-3
drops) were added, and the mixture was refluxed for 6 h. After cooling, the precipitate that separated was
filtered off and washed with EtOH and H2O. Yield 2.1 g (68%), mp 261-262°C (AcOH). IR spectrum, ν, cm-1:
3450, 3080, 3070, 2970, 2905, 2840, 2775, 2720, 2642, 1640, 1590, 1580, 1565, 1540, 1465, 1440, 1160, 1100,
1050, 970, 880, 820, 780, 710, 695, 620, 575. Found, %: C 54.86; H 2.87; N 32.03. C14H9N7O2. Calculated, %:
С 54.72; H 2.95; N 31.91.
7-Methyl-1H,7H-imidazo[4,5-d]bisfurazano[3,4-b:3',4'-f]azepine-2-thiol (12). NaOH (1.2 g,
0.03 mol) and CS2 (1.3 g, 0.03 mol) were added to a suspension of diamine 2c (2.2 g, 0.01 mol) in EtOH
(50 ml). The mixture was refluxed for 6 h. The reaction mixture was then evaporated to a third of the initial
volume, and H2O (100 ml) and NaOH (5 g) were added. The obtained solution was filtered, the filtrate was
acidified to pH 6 with AcOH, and the precipitate was filtered off and recrystallized from AcOH. Yield 1.8 g
(69%), mp 347-348°C (decomp.). IR spectrum, ν, cm-1: 3420, 3330, 3090, 3040, 3010, 2960, 2915, 2865, 2820,
2625, 2795, 2540, 1645, 1590, 1560, 1555, 1530, 1495, 1450, 1400, 1360, 1220, 1200, 1140, 1045, 980, 965,
910, 875, 815, 780, 750, 716, 645, 580, 460, 420. Found, %: C 36.39; H 2.03; N 37.12. C8H5N7O2S. Calculated,
%: С 36.50; H 1.91; N 37.25.
(E,Z)-2-Benzylidene-8-methyl-8H-bisfurazano[3,4-b:3',4'-f]thiazolo[2',3':2,3]imidazo[4,5-d]azepin-
3(2H)-one (13). Thiol 12 (1.3 g, 5 mmol), chloroacetic acid (1.0 g, about 10 mmol), anhydrous NaOAc, (3.0 g),
and benzaldehyde (0.75 g, 7 mmol) were added to AcOH (30 ml) and heated to boiling. After 1 h, Ac2O
(20 ml) was added, and the refluxing was continued for 10 h. The formed precipitate was filtered off, washed
with EtOH and H2O, and recrystallized from a DMF–AcOH mixture. Yield 1.0 g (52%), mp 342-343°C
(decomp.). IR spectrum, ν, cm-1: 3100, 2995, 2935, 1765, 1735 (CO), 1630, 1590, 1555, 1500, 1485, 1440, 1355,
1255, 1210, 1135, 1105, 1060, 1035, 960, 880, 770, 680, 655, 605, 580, 545, 520. 1H NMR spectrum, δ, ppm: 8.29
(0.24H, s) and 8.23 (0.76H, s, =CHPh); 7.82-7.74 (2H, m, Н-2,6 Ph); 7.66-7.57 (2H, m, Н-3,5 Ph); 7.43-7.39 (1H, m,
Н-4 Ph); 3.54 (3H, s, CH3). Mass spectrum, m/z (Irel, %): 392 [M+H]+ (16), 391 [M]+ (100), 361 [M-NO]+ (10), 261
(11), 134 (43), 102 (55), 90 (10), 89 (20), 83 (11), 76 (11), 44 (16), 40 (10), 30 (31). Found, %: C 52.51; H 2.44;
N 24.93. C17H9N7O3S. Calculated, %: С 52.17; H 2.32; N 25.05.
4-Methyl-4H,13H-indeno[1',2':5,6]pyrazino[2,3-d]oxadiazolo[3,4-b:3',4'-f]azepin-13-one
(14a).
Diamine 2c (1,1 g, 5 mmol) was dissolved in DMF (10 ml) at 50-60°C. The solution obtained was poured into a
boiling solution of ninhydrin (0.89 g, 5 mmol) in EtOH (10 ml), and the mixture was maintained at boiling
point for 10 min. It was then cooled to 60-70°C and diluted with of 2-PrOH (30 ml). After cooling to 20°C, the
precipitate was filtered off, washed with EtOH and water, and recrystallized from AcOH. Yield 1.58 g (92%),
mp >350°C. IR spectrum, ν, cm-1: 3440, 3100, 3095, 2930, 1730 (CO), 1595, 1565, 1550, 1525, 1500, 1385, 1360,
1215, 1175, 1160, 1025, 1005, 925, 865, 770, 750, 620, 590, 425. Found, %: C 55.47; H 2.42; N 28.32.
C16H7N7O3 Calculated, %: С 55.66; H 2.04; N 28.45.
8-Methyl-8H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]pyrazino[2,3-d]azepine (14b). BF3·Et2O (two or three
drops, about 50 mg, ~0.35 mmol) was added to a mixture of the diamine 2c (2.3 g, 0.01 mol) and 1,4-dioxane-
2,3-diol [14] (1.5 g, 0.0125 mol) in 2-PrOH (50 ml). The mixture was stirred at boiling point for 2 h and cooled,
and the precipitate was filtered off. The product was recrystallized from AcOH. Yield 2.3 g (94%), mp
270-271°C. IR spectrum, ν, cm-1: 3040, 2965, 2955, 2925, 1595, 1545, 1530, 1510, 1435, 1375, 1320, 1310,
1080

1180, 1155, 1135, 1025, 1005, 940, 905, 875, 840, 645, 615, 590. Found, %: C 44.58; H 2.39; N 40.01.
C9H5N7O2. Calculated, %: С 44.45; H 2.07; N 40.32.
2,3,8-Trimethyl-8H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]pyrazino[2,3-d]azepine (14c). A mixture of
the diamine 2c (2.3 g, 10 mmol), AcOH (50 ml), and diacetyl (1 g, 11.6 mmol) was refluxed for 1 h. Water was
added to the boiling solution drop by drop until crystallization began. The mixture was cooled to room
temperature in air, and the precipitate was filtered off and recrystallized from EtOH–AcOH. Yield 2.5 g (92%),
mp 186-187°C. IR spectrum, ν, cm-1: 2990, 2960, 2920, 1590, 1545, 1510, 1440, 1425, 1410, 1390, 1375, 1340,
1220, 1200, 1045, 1010, 975, 950, 925, 885, 590, 420. Found, %: C 48.36; H 3.50; N 36.04. C11H9N7O2.
Calculated, %: С 48.71; H 3.34; N 36.15.
2-(4-Chlorophenyl)-8-methyl-8H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]pyrazino[2,3-d]azepine (14d).
This compound was obtained from of the diamine 2c (1.15 g, 5 mmol) and p-chlorophenylglyoxal (1.0 g,
5.36 mmol) similarly to the synthesis of compound 14b. Yield 1.3 g (74%), mp 298-299°C. IR spectrum, ν, cm-1:
1590, 1535, 1505, 1450, 1355, 1205, 1140, 1090, 1010, 1000, 930, 910, 850, 590, 510, 500. Found, %: C 50.60;
H 2.41; N 27.53. C15H8ClN7O2. Calculated, %: С 50.93; H 2.28; N 27.72.
8-Methyl-2,3-diphenyl-8H-bis[1,2,5]oxadiazolo[3,4-b:3',4'-f]pyrazino[2,3-d]azepine (14e). This
compound was obtained from the diamine 2c (1.15 g, 5.0 mmol) similarly to the synthesis of compound 14b
(condensation with dibenzyl (1.09 g, 5.2 mmol)). Yield 1.65 g (80%), mp 288-289°C (AcOH). IR spectrum, ν,
cm−1: 3435, 3350, 3055, 2990, 2960, 2925, 2850, 2360, 2340, 1585, 1530, 1515, 1450, 1425, 1410, 1380, 1365,
1340, 1325, 1025, 1005, 915, 970, 775, 700, 590, 555. Found, %: C 63.88; H 3.44; N 24.61. C21H13N7O2.
Calculated, %: С 63.79; H 3.31; N 24.80.
REFERENCES
1.
2.
3.
4.
5.
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