On the Reaction of 2-Benzylamino-1,4-naphthoquinones with Nitrosylsulfuric Acid

Article abstract of DOI:10.1134/S1070428019050051

The reaction of 2-benzylamino-1,4-naphthoquinone with nitrosylsulfuric acid in acetic acid results in preferential formation of 2,1- and 2,3-heterocyclization products: (E)-4-(hydroxyimino)-2-phenylnaphtho [2,1-d]oxazol-5(4H)-one and 2-phenyl-1-hydroxy-1H-naphtho[2,3-d]imidazole-4,9-dione. In addition, 2-phenylnaphtho[2,1-d]oxazol-4,5-dione and N-(3-nitro-1,4-dioxo-1,4-dihydronaphthalen-2-yl)benzamide are also formed. The reaction of 2-benzylamino-3-chloro-1,4-naphthoquinone with nitrosylsulfuric acid in acetic acid gives 3-diazonapthalene-1,2,4(3H)-trione and benzaldehyde.

Full text of DOI:10.1134/S1070428019050051

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 5, pp. 608–614. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 5, pp. 701–708.
On the Reaction of 2-Benzylamino-1,4-naphthoquinones
with Nitrosylsulfuric Acid
L. M. Gornostaeva,*, E. V. Nuretdinovaa, T. I. Lavrikovaa, Yu. G. Khalyavinaa,
O. I. Fominykha, and Yu. V. Gatilovb,c
a Astaf’ev Krasnoyarsk State Pedagogical University, ul. А. Lebedevoy 89, Krasnoyarsk, 660049 Russia
*e-mail: gornostaev@kspu.ru
b Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, pr. Akad. Lavrentieva 9, Novosibirsk, 630090 Russia
c Novosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090 Russia
Received October 12, 2018; revised December 10, 2018; accepted December 20, 2018
Abstract—The reaction of 2-benzylamino-1,4-naphthoquinone with nitrosylsulfuric acid in acetic acid results
in preferential formation of 2,1- and 2,3-heterocyclization products: (E)-4-(hydroxyimino)-2-phenylnaphtho
[2,1-d]oxazol-5(4H)-one and 2-phenyl-1-hydroxy-1H-naphtho[2,3-d]imidazole-4,9-dione. In addition, 2-
phenylnaphtho[2,1-d]oxazol-4,5-dione and N-(3-nitro-1,4-dioxo-1,4-dihydronaphthalen-2-yl)benzamide are
also formed. The reaction of 2-benzylamino-3-chloro-1,4-naphthoquinone with nitrosylsulfuric acid in acetic
acid gives 3-diazonapthalene-1,2,4(3H)-trione and benzaldehyde.
Keywords: 2-benzylamino-1,4-naphthoquinone, hydroxyimidazole, naphtho-1,2-oxazole, oximes, 2,3-diazido-
1,4-naphthoquinone, nitrosylsulfuric acid
DOI: 10.1134/S1070428019050051
2-Amino-1,4-naphthoquinones exhibit diverse
biological activity [1–3]. Of interest are also nitrogenous
heterocycles derived from 2-amino-1,4-naphthoquinones.
For example, the substitution of the chlorine in 2-ace-
tylamino-3-chloro-1,4-naphthoquinone by an amino group
followed by cyclization gave 1,2-substituted 1H-naphtho-
[2,3-d]imidazole-4,9-diones [4]. Such fused imidazoles
showed antitumor effects [5, 6]. 2-Alkyl-amino-3-chloro-
1,4-naphthoquinones 1 was used as the starting materials
to prepare 1-alkyl-4,9-dioxo-1H-naphtho[2,3-d][1,2,3]-
triazole 2-oxides 2 and their oximes 3, which were
found to be efficient cytostatics [7, 8] (Scheme 1).
Scheme 1.
O
R
O
R
O
O
N
N
O
O
N
N
H
N
R
NaNO2
AcOH
NaN3
EtOH/DMF
Cl
Cl
N3
O
O
1
O
O
R
R
N
N
t
HONH2HCl
N+
O
N+
O
C5H5N, 115°C
C6H6
N
N
O
N
OH
2
3
R = Me, Bu, Bn.
608

ON THE REACTION OF 2-BENZYLAMINO-1,4-NAPHTHOQUINONES
609
Scheme 2.
R
N
R
H
R
O
O
O
N
N
NaNO2 / H2SO4
AcOH, 20_22oC
''O''
H
...
...
OH
N
O
O
O
4a_4d
5
6a_6d
(78_87%)
R = Me, Et, Pr, i-Pr.
We earlier found that 2-alkylamino-1,4-naphtho-
quinones 4a–4d react with nitrosylsulfuric acid to form
2-alkylnaphtho[2,1-d][1,3]oxazole-4,5-dione 4-oximes
6a–6d in high yields [9] (Scheme 2).
11d (Scheme 5) compared to radical 5 (Scheme 2)
predetermines changes toward reactions of 2-benzyl-
amino-1,4-naphthoquinone (4e) and 2-alkylamino-1,4-
naphthoquainones 4a–4d.
At the same time, treatment of 2-benzylamino- and
2-alkylamino-1,4-naphthoquinones 4a–4g with
nitration mixture in acetic acid afforded 2-R-1-
hydroxy-1H-naphtho[2,3-d]imidazole-4,9-diones 7a–7g
as the main products [10, 11] (Scheme 3).
We established that 1-hydroxy-2-phenyl-1H-
naphtho[2,3-d]imidazole-4,9-dione (7e) and (Е)-4-
(hydroxyimino)-2-phenylnaphtho[2,1-d]oxazole-5
(4H)-one (8) are formed in a high total yield on
treatment of 2-benzylamino-1,4-naphthoquinone (4e)
with nitrosylsulfuric acid at 10–12°С. Treatment of
hydroxyimidazole 7e or oxazole 8 with sulfuric acid in
acetic acid at 20–60°С does not lead to their intercon-
versions. Consequently, hydroxyimidazole 7e and oxazole
8 are formed from intermediates 11 concurrently by
independent pathways. Treatment of 2-benzylamino-
1,4-naphthoquinone (4e) with nitrosylsulfuric acid at
40–50°С produces, along with compounds 7e and 8,
small amounts of 2-phenylnaphtho[2,1-d]oxazole-4,5-
dione (9) and N-(3-nitro-1,4-dioxo-1,4-dihydronaphth-
len-2-yl)benzamide (10). These compounds are not
formed by the reaction of hydroxyimidazole 7e or oxazole
8 with sulfuric acid in acetic acid. Apparently, com-
pounds 9 and 10 are formed directly from precursors
11 or azoles 7e and 8, when they are treated with
nitrogen oxides at an elevated temperature (50°С).
The reaction of 2-benzylamino-1,4-naphthoquino-
nes with nitrosylsulfuric acid has never been studied.
We found that 2-benzylamino-1,4-naphthoquinone 4e
reacts with nitrosylsulfuric acid in acetic acid to form
products 7–10 (Scheme 4).
Under these conditions, like in the case of treatment
of 2-benzylamino-1,4-naphthoquinone 4e with
nitration mixture, the main reaction product is 2-
phenyl-1-hydroxy-1H-naphtho[2,3-d]imidazole-4,9-
dione (7e) rather than 2-alkylnaphtho[2,1-d][1,3]-
oxazole-4,5-dione 4-oxime (8) (Scheme 2). We
suggest that the transformations of compound 4e,
shown in Scheme 4, occur by a radical cation
mechanism involving intermediates 11a–11d
(Scheme 5). Apparently, the higher stability of radical
Scheme 3.
R
H
O
O
OH
N
N
HNO3 + H2SO4
AcOH, 20_22oC
R
N
O
O
4a_4g
7a_7g
(54_74%)
R = Me, Et, Pr, i-Pr, Ph, 4-Me-Ph, 4-Cl-Ph.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 5 2019

GORNOSTAEV et al.
610
Scheme 4.
O
O
OH
O
H
N
N
N
NOHSO4
AcOH
+
N
N
OH
O
O
O
7e
8
4e
49% (10oC), 45% (50oC)
40% (10oC), 15% (50oC)
O
O
H
N
N
O
+
+
NO2
O
O
O
10
9
23% (50oC)
5% (50oC)
The products of these reactions were characterized
by spectral methods and X-ray diffraction (XRD)
analysis. The crystal structures of compounds 9 and 10
are shown in the figure.
The bond lengths in the naphthalenedione fragment
in compound 9 are close to those in 6-methoxy-2-
methylnaphtho[1,2-b]furan-4,5-dione [12]. The
dihedral angle between the naphthalene core and
Scheme 5.
H
N
H
O
O
O
H
N
N
NOHSO4
AcOH
NO
N
O
H
O
O
O
4e
11a
11b
O
OH
N
N
...
H
N
O
O
H
N
O
O
7e
H2SO4
AcOH
N
O
N
O
O
O
N
11c
11d
...
OH
N
O
8
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 5 2019

ON THE REACTION OF 2-BENZYLAMINO-1,4-NAPHTHOQUINONES
(a) (b)
O2
611
O4
O5
O3
C5
C10
C2
N2
N1
C11
O1
C1
C2
O1
C10
N3
C9
C9
C11
C4
O2
O3
Structures of (a) 2-phenylnaphtho[2,1-d]oxazole-4,5-dione (9) and (b) N-(3-nitro-1,4-dioxo-1,4-dihydronaphthalen-2-yl)benzamide (10) by
XRD data (50% thermal ellipsoid drawing).
phenyl planes is 14.5(3)°. The bond lengths in
molecule 10 are close to the respective bond lengths in
N-(1,4-dioxo-1,4-dihydronaphthalen-2-yl)benzamide
[13]. The nitro and amido groups are turned out of the
nathphalene core plane. The corresponding dihedral
angles are 62.4(1) and 30.7(1)°. In the absence of the nitro
group 13], the amido group is almost coplanar to the
naphthalene core plane (angle 4.0°).
diazonaphthalene-1,2,4(3H)-trione (14). As the by-
product we isolated benzaldehyde (yield 76%). In view
of such results, we can propose a mechanism of the
formation of compound 14, which involves the
oxidation of the N-nitroso compound to an alcohol
with nitrogen oxides (Scheme 6).
Note that other 2-alkylamino-3-chloro-1,4-
naphthoquinones did not react with nitrosylsulfuric
acid in acetic acid under such conditions (~40°С).
These results can suggest that for the 1,2-annelation of
the oxazole ring of 2,3-annelation of the hydroxy-
The reaction of 2-benzylamino-3-chloro-1,4-
naphthoquinone (12) with nitrosylsulfuric acid proceeds
in a different way. We found that the reaction gives 3-
Scheme 6.
O
O
O
O
N
N
O
N
N
H
N
NOHSO4
"O"
AcOH, 40oC
OH
Cl
Cl
Cl
O
O
O
13b
12
13a
O
O
O
N
N
OH
N2
H2O
_C6H5COH
H2SO4
Cl
O
O
13c
14
(87%)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 5 2019

GORNOSTAEV et al.
612
imidazole ring to 2-R-amino-1,4-naphthoquinones 4a–4g,
the 3 position in the latter should be free (Schemes 2–4).
carrier atoms. The hydrogen atom of the amido group
in compound 10 was located by difference synthesis
and refined with isotropic displacement parameters
with bond length constraints. Absorption correction
was applied using SADABS program. The crystal data
were deposited in the Cambridge Crystallographic
Data Center (CCDC 1853605 and 1853606 for 9
and 10, respectively) and can be requested by
www.ccdc.cam.ac.uk/data_request/cif. The starting
aminonaphthoquinones 4e and 12 were prepared as
described in [18, 19].
Apparently, 2-benzylamino-3-chloro-1,4-naphtho-
quinone (12) transforms into diazoquinone 14 by a
pathway involving N-nitrosation followed by oxidation
of the methylene group. The resulting N-nitrosamine
13b eliminates a molecule of benzaldehyde to form 3-
chloro-2-diazohydrate 13с, which hydrolizes to diazo
quinone 14. Note that the first convenient synthetic
approach to diazoquinone 14 via the reaction of 2-
amino-3-chloro-1,4-naphthoquinones with nitrosylsul-
furic acid was described by Моsby and Silva [14];
other authors [15–16] reported other methods of
synthesis of this compound.
Reactions of 2-(benzylamino)-1,4-naphtho-
quinone 4e and 2-(benzylamino)-3-chloro-1,4-naph-
thoquinone 12 with nitrosylsulfuric acid (general
procedure). а. Nitrosylsulfuric acid (10 mL), prepared
from NaNO3 (0.80 g) and 92% H2SO4 (8 mL), was
added to a stirred suspension of 1.32 g (5 mmol) of 2-
(benzylamino)-1,4-naphthoquinone (4e) in CH3COOH
(25 mL) at 20°С. As this took place, the reaction
mixture warmed up to 50°С and was held at this
temperature for 1 h, after which it was cooled to 20°С
and poured into 500 g of ice with water. The orange
precipitate that formed was filtered off, washed with
water, and dried. The resulting dry material, 1.22 g, was
added to 40 mL of chloroform, and the mixture was
refluxed for 20 min, cooled to 20°С, and filtered. The
precipitate on the filter was practically pure 1-hydroxy-
2-phenyl-1H-naphtho-[2,3-d]imidazole-4,9-dione (7e).
Yield 0.60 g (45.3%). The filtrate was chromatog-
raphed on silica gel (eluent chloroform) to isolate 0.20 g
(15.2%) of (Е)-4-(hydroxyimino)-2-phenylnaphtho-
[2,1-d]oxazol-5(4H)-one (8), 0.30 g (22.7%) 2-phenyl-
naphtho[2,1-d]oxazole-4,5-dione (9), and 0.07 g
(5.3%) of N-(3-nitro-1,4-dioxo-1,4-dihydronaphthalen-
2-yl)benzamide (10).
Thus, we found that 2-benzylamino-1,4-naphtho-
quinone and 2-benzylamino-3-chloro-1,4-naphthoqui-
none differently react with nitrosylacetic acid in acetic
acid, even though these two reactions have a common
feature, specifically, increased activity of the benzyl
methylene group.
EXPERIMENTAL
1
The H and 13С NMR spectra were recorded on a
Bruker DRX spectrometer (500 and 125 МHz) in
DMSO-d6, internal reference TMS. The UV spectra
were obtained on a Thermo Evolution 300 spectro-
photometer (cells 10 mm) in 10–4 M toluene solutions.
The IR spectrum of compound 14 was measured on a
Thermo Nicolet iN10 spectrophotometer. The mass
spectra were obtained on a Finnigan MAT 8200 instru-
ment (EI, 70 eV). The high-resolution mass spectra of
compounds 10 and 14 were obtained on a Bruker
microOTOF II instrument in the positive mode with
electrospray ionization (capillary voltage 4500 V) [17].
Scan range m/z 50–3000. The samples were injected in
acetonitrile solutions, flow rate 3 µL/min. Nebulizer
gas nitrogen (4 L/min), interface temperature 180°С.
Elemental analysis was performed on an EURO EA
3000 automatic CHNS analyzer. The melting points
were determined on a Boetius hot stage. Reaction
progress and purity of compounds were controlled by
TLC on Silufol UV-254 plates (eluent toluene–
acetone, 4 : 1).
b. The reaction of 1.32 g (5 mmol) of 2-benzylamino-
1,4-naphthoquinone (4e) in CH3COOH (30 mL) with
nitorsylsulfuric acid prepared from NaNO2 (0.80 g)
and 92% H2SO4 (8 mL) for 10 min with external
heating (10–12°С) and stirring for 20 min followed by
the workup similar to that described in procedure a gives
0.64 g of hydroxyimidazole 7e (48.5%) and 0.53 g of
oxazole 8 (40.2%).
c. 2-Benzylamino-3-chloro-1,4-naphthoquinone (12),
5.95 g (20 mmol), was added to CH3COOH (100 mL),
and nitrosylsulfuric acid prepared from NaNO2 (3 g)
and 94% H2SO4 (30 mL) was added with stirring to the
resulting suspension. The reaction mixture warmed up
to 40–45°С and was stirred at this temperature for 2 h.
The XRD analysis of compounds 9 and 10 was
performed on a Bruker Kappa Apex II diffractometer
(MoKα radiation, graphite monochromator). All calcu-
lations were performed using SHELX97 program
suite. The hydrogen atoms were refined riding on their
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 5 2019

ON THE REACTION OF 2-BENZYLAMINO-1,4-NAPHTHOQUINONES
613
The solution changed color from red to pale yellow. It
was poured into a mixture of ice with water (800 g).
The pale yellow precipitate that formed was filtered
off, washed with water, and dried to obtain 3.5 g
(87.5%) of 3-diazonaphthalene-1,2,4(3H)-trione (14). The
filtrate was extracted with chloroform (3 × 100 mL), and
the extract was evaporated to isolate 1.62 g (76.4%) of
benzaldehyde.
d (1H, H6, J 7.2 Hz), 7.96 d (1H, H9, J 7.2 Hz), 7.83 d.t
(1H, H8, J 7.6 Hz), 7.67–7.63 m (4H, H3',4',5',7). 13C
NMR spectrum, δ, ppm: 178.83 (1С, C5), 172.35 (1C,
C4), 161.50 (1С, C2), 157.53 (1С, C9b), 135.02 (1С,
C3a), 134.98 (1С, C8), 132.08 (1С, C4'), 130.99 (1С,
C7), 130.19 (1C, C1'), 129.58 (1С, C6), 129.44 (2С,
C3',5'), 126.88 (2С, C2',6'), 125.44 (1С, C5a), 125.38 (1С,
C9a), 122.84 (1С, C9). Mass spectrum, m/z (Irel, %):
275 (37.14), 247 (22.02), 172 (6.01), 114 (6.61), 104
(27.93), 89 (20.72), 88 (41.44), 77 (38.24), 76 (100),
74 (10.21), 63 (20.52), 62 (26.23), 51 (23.22), 50
(33.43). Found, %: С 74.63; H 3.68; N 4.68.
С17H9NO3. Calculated, %: С 74.18; H 3.30; N 5.09. M
275.26.
1-Hydroxy-2-phenyl-1H-naphtho[2,3-d]imida-
zole-4,9-dione (7e) was identical to the product
synthesized in [11]. Yield 0.64 g (48.5%) at 10°С and
0.60 g (45.3%) at 50°С, pale yellow crystals; mp 248–
250°С. UV spectrum (toluene), λmax (log ε), nm: 286
1
(4.39), 343 (3.60), 544 (3.19). H NMR spectrum, δ,
ppm: 7.55–7.63 m (3H, H3',4',5'), 7.86 s [1H, H5(8)], 7.85
s [1H, H5(8)], 8.10 s (2H, H6,7), 8.20 s (2H, H2',6'), 13.25
br.s (1H, ОH). 13C NMR spectrum, δ, ppm: 178.02
[1С, C4(9)], 173.87 [1С, C4(9)], 147.69 (1С, C2), 138.01
[1С, C9a(3a)], 134.01 [1С, C5(8)], 133.86 [1С, C5(8)],
133.02 [1С, C4a(8a)], 132.62 [1С, C4a(8a)], 130.75 [1C,
C9a(3a)], 130.67 (1С, C4'), 128.84 (2С, C3',5'), 128.24
(2С, C2',6'), 127.24 (1С, C1'), 126.45 [1С, C6(7)], 126.09
[1С, C6(7)]. Found, %: С 70.81; H 3.48; N 9.60.
С17H10N2O3. Calculated, %: С 70.34; H 3.47; N 9.65.
M 290.28.
Rhombic crystals, temperature 200 K, a 24.505(8),
b 6.881(3), c 7.350(4) Å, Z 4, space group Pca21, dcalc
1.475 g/cm3, µ 0.103 mm–1, θ ≤ 25.2°, measured
reflections 2143 (unique 1726), R 0.0346 on 1332
reflections with I > 2σ(I), wR2 0.0880 on all reflections.
N-(3-Nitro-1,4-dioxo-1,4-dihydronaphthalen-2-
yl)benzamide (10). Yield: 0.07 g (5.3%), light yellow
crystals; mp 217–218°С. UV spectrum (toluene), λmax
1
(log ε), nm: 286 (4.05). H NMR spectrum, δ, ppm:
10.4 s (NH), 8.13 d (1H, H8, J 6.8 Hz), 8.11 d (1H, H5,
J 6.8 Hz), 8.00 d (2H, H2',6', J 7.6 Hz), 7.97 t (1H, H7, J
7.4 Hz), 7.94 t (1H, H6, J 7.4 Hz), 7.72 t (1H, H4', J
7.5 Hz), 7.6 t (2H, H3',5', J 7.4 Hz). 13C NMR spectrum,
δ, ppm: 179.79 (1С, C1), 175.42 (1С, C4), 165.71 (1С,
CONH), 137.76 (1С, C3), 135.68 (1С, C7), 134.78 (1С,
C6), 133.75 (1С, C2), 133.63 (1С, C4'), 131.93 (1С,
C1'), 130.13 [1С, C4a(8a)], 130.10 [1С, C4a(8a)], 128.88
(2С, C3',5'), 128.68 (2С, C2',6'), 126.82 (1С, C8), 126.60
(1С, C5). Mass spectrum, m/z (Irel, %): 276 (8.31), 106
(7.51), 105 (100), 77 (46.25), 76 (9.21), 51 (11.91).
High-resolution mass spectrum, m/z: 345.0474 [M +
Na]+. Found, %: С 63.67; H 3.17; N 8.51. С17H10N2O5.
Calculated, %: С 63.36; H 3.13; N 8.69. M 322.27,
M + Na 345.0482.
(Е)-4-(Hydroxyimino)-2-phenylnaphtho[2,1-d]-
oxazol-5(4H)-one (8). Yield 0.53 g (40.2%) at 10°С and
0.20 g (15.2%) at 50°С, yellow orange crystals; mp 206–
208°С. UV spectrum (toluene), λmax (log ε), nm: 313
(4.25), 429 (3.46). 1H NMR spectrum, δ, ppm: 13.67 s
(NOH), 8.18–8.15 m (2H, H2',6'), 8.10 d (1H, H6, J 7.5 Hz),
7.92 d (1H, H9, J 7.5 Hz), 7.84 d.t (1H, H8, J 7.5, J
1.2 Hz), 7.63–7.60 m (3H, H3',5',4'), 7.58 d.t (1H, H7, J
7.5, J 1.2 Hz). 13C NMR spectrum, δ, ppm: 180.61
(1С, C5), 160.90 (1С, C2), 146.81 (1С, C9b), 141.83
(1С, C4), 134.91 (1С, C8), 131.42 (1С, C4'), 129.61
(1С, C1'), 129.50 (1С, C9a), 129.31 (1С, C7), 129.26
(2С, C3'), 128.48 (1С, C6), 126.59 (2С, C2'), 126.43
(1С, C3a), 126.12 (1С, C5a), 121.56 (1С, C9). Mass
spectrum, m/z (Irel, %): 290 (30.83) [М]+, 274 (2.90),
158 (5.31), 129 (7.71), 114 (11.31), 106 (10.81), 105
(100), 103 (10.11), 102 (5.01), 101 (13.01), 77 (21.52),
76 (8.91), 75 (6.51), 30 (6.51). Found, %: С 70.48.; H
3.47; N 9.20. С17H10N2O3. Calculated, %: С 70.34; H
3.47; N 9.65. M 290.28.
Monoclinic crystals, temperature 296 K, a 5.2751(3),
b 13.4961(9), c 20.5594(12) Å, β 97.109(2)°, Z 4, space
group P21/n, dcalc 1.474 g/cm3, µ 0.111 mm–1, θ ≤ 26.1°,
measure reflections 25189 (unique 2877), R 0.0466 on
2015 reflections with I > 2σ(I), wR2 0.1648 on all
reflections.
3-Diazonaphthalene-1,2,4(3H)-trione (14). Yield:
3.5 g (87.5%), pale yellow crystals; mp 119–121°C
(CHCl3) (121–122°C [16]). UV spectrum (toluene),
λmax (log ε), nm: 284 (3.90). IR spectrum, ν, cm–1:
2-Phenylnaphtho[2,1-d]oxazole-4,5-dione (9).
Yield 0.30 g (22.7%), mp 138–140°С. UV spectrum
1
(toluene), λmax (log ε), nm: 296 (4.25), 438 (3.08). H
NMR spectrum, δ, ppm: 8.21–8.19 m (2H, H2',6'), 8.03
2120–2200 (N=N). H NMR spectrum, δ, ppm: 8.13
1
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GORNOSTAEV et al.
614
d.t [1H, H6(7), J 7.6, J 1.3 Hz], 8.08–8.11 m [1H, H5(8)],
7.95 d.t [1H, H6(7), J 7.6, J 1.3 Hz], 7.89–7.92 m [1H,
H5(8)]. 13C NMR spectrum, δ, ppm: 177.54 (1С, C1),
176.82 (1С, C4), 172.36 (1С, C2), 142.81 (1С, C3),
135.34 (1С, C6), 135.04 (1С, C8a), 134.85 (1С, C7),
128.46 (1С, C8), 127.45 (1С, C4a), 126.56 (1С, C5).
Mass spectrum, m/z (Irel, %): 200 (3.40) [М]+, 172
(69.07), 104 (89.19), 88 (21.12), 77 (13.51), 76 (100),
74 (18.12), 68 (10.31), 62 (19.92), 50 (41.64). High-
resolution mass spectrum, m/z 223.0111 [M + Na]+.
Found, %: С 59.95; H 2.02; N 13.68. С10H4N2O3.
Calculated, %: С 60.01; H 2.01; N 14.00. M 200.15,
M + Na 223.0114.
Anti-Cancer Agents Med. Chem., 2017, vol. 17, p. 1814.
doi 10.2174/1871520617666170327112216
8. Shtil’, A.A., Glazunova, V.A., Lavrikova, T.I.,
Khalyavina, Yu.G., and Gornostaev L.M., RF Patent
no. 2545091, 2014; Byull. Izobret., 2015, no. 9.
9. Gornostaev, L.M., Khalyavina, Yu.G., Lavrikova, T.I.,
Gatilov, Yu.V., Stashina, G.A., and Firgang, S.I., Russ.
J. Org. Chem., 2014, vol. 50, p. 1814. doi 10.1134/
S1070428014120173
10. Gornostaev, L.M., Nuretdinova, E.V., Lavrikova, T.I.,
Khalyavina, Yu.G., Kryukovskaya, I.S., and Gatilov, Yu.V.,
Russ. J. Org. Chem., 2015, vol. 51, p. 1733. doi
10.1134/S107042801512012X
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Kuznetsova, A.S., Khalyavina, Yu.G., and Lavrikova, T.I.,
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CONFLICT OF INTEREST
The authors declare no conflict of interest.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 5 2019