SNH Arylamination of Nitroquinolines: Access to Nitro and Nitroso Derivatives of Arylaminoquinolines

Article abstract of DOI:10.1007/s10593-018-2368-x

[Figure not available: see fulltext.] S_N^H Arylamination of 5-, 6-, 7-, and 8-nitroquinolines in anhydrous DMSO gave not only the arylamino derivatives of the respective nitroquinolines, but also the arylamino derivatives of nitrosoquinolines. In the case of 6-nitroquinoline, the first representatives of polycyclic structures on the basis of pyrido[3,2-a]phenazine 7-oxide were isolated.

Full text of DOI:10.1007/s10593-018-2368-x

DOI 10.1007/s10593-018-2368-x
Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
H
SN Arylamination of nitroquinolines:
access to nitro and nitroso derivatives of arylaminoquinolines
Oleg P. Demidov1, Diana Yu. Pobedinskaya1, Elena K. Avakyan1,
Gulminat A. Amangasieva1, Ivan V. Borovlev1*
1 North-Caucasus Federal University,
1a Pushkina St., Stavropol 355009, Russia; е-mail: ivborovlev@rambler.ru
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2018, 54(9), 875–886
Submitted July 17, 2018
Accepted August 20, 2018
H
SN Arylamination of 5-, 6-, 7-, and 8-nitroquinolines in anhydrous DMSO gave not only the arylamino derivatives of the respective
nitroquinolines, but also the arylamino derivatives of nitrosoquinolines. In the case of 6-nitroquinoline, the first representatives of
polycyclic structures on the basis of pyrido[3,2-a]phenazine 7-oxide were isolated.
Keywords: nitroquinolines, phenazines, SNH arylamination, disproportionation, SNH methodology.
The quinoline system is often found in nature as a
structural motif in a large alkaloid family, many of which,
similarly to their synthetic analogs, show a broad spectrum
of biological and pharmaceutical effects, including
antimalarial, anticancer, antimycobacterial, antimicrobial,
anticonvulsant, anti-inflammatory, cardiovascular, and
antioxidant activity.1 As it has been pointed out in a recent
review article,2 there is a continued interest in searching for
new synthetic routes to quinoline derivatives. Current
developments of organic chemistry have enabled direct
functionalization of C–H bonds in aromatic compounds, in
particular the formation of C–N bonds,3 using procedures
that are in agreement with the principles of green chemistry
and atom economy.4
The goal of the current work was to study the
H
possibilities for oxidative SN arylamination of nitro-
quinolines containing a nitro group in the benzene ring of
the molecule. It is known that quinoline itself can be used
H
in oxidative SN amination reaction with potassium amide
in liquid ammonia – KMnO4 system, forming predominantly
2- or 4-aminoquinolines, depending on the reaction
conditions.8 However, the relatively π-electron poor 5-, 6-,
and 7-nitroquinolines already do not require KNH2 for the
introduction of an NH2 group, because ammonia itself is
sufficient as a nucleophile, but the regioselectivity of
oxidative amination is determined only by the location of
nitro group, regardless of its position in the pyridine or
benzene ring of the quinoline molecule.8,9 Vicarious
amination using 1,1,1-trimethylhydrazinium iodide as reagent
proceeded analogously,10 forming both o- and p-amino-
Reactions involving nucleophilic substitution of
hydrogen (SNH) are excellent examples of such procedures,
which are generally divided into two types: oxidative and
vicarious substitution reactions.5 Both types of reactions
proceed through an addition step that results in the
formation of σH-adduct, followed by its aromatization in
the presence of external oxidant or elimination of simple
nitroquinolines in both cases, with
predominance of the former.
a
significant
However, the amination reaction conditions were not
H
suitable for oxidative SN arylamination due to the lower
nucleophilicity of arylamide anions typically used in these
reactions and their high sensitivity toward traditional
oxidants. For these reasons, similar reactions are still quite
rare. They have been reported for such azines as 5-aza-
cinnoline,11 1,2,4-triazine,12 3-nitropyridine,7,13a 1,3,7-tri-
H
HX molecules. Such SN reactions have already been
implemented in chemical industry6 and in many cases offer
suitable alternatives for transition metal-catalyzed cross-
coupling reactions.7
0009-3122/18/54(9)-0875©2018 Springer Science+Business Media, LLC
875

Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
Scheme 1
azapyrene,14 as well as some nitroarenes.6,13 Suitable mild
oxidants for the oxidation of σH-adducts in these reactions
include air oxygen11,14 and nitrobenzene,7 while stable
intermediates can be subjected to anodic oxidation.15 In the
absence of external oxidant, the NO2 group13 or C=N bond
in the ring of substrate molecule12 can also act as hydride
ion acceptors.
Table 1, entry 1). Thus, the nucleophile at the first stage of
the reaction added at the ortho and para positions relative
to the NO2 group, with the para-σH-adduct further
undergoing oxidative aromatization with the formation of
nitroamine 2a, while its ortho analog was aromatized in
two directions, forming nitroamine 3a and nitrosoamine 4a.
Practically the same results were obtained by performing
this reaction under argon atmosphere (Table 1, entry 2).
This indicates that, similarly to the case of 3-nitro-
pyridine,17b nitroquinoline 1 exhibited two types of
reactivity, serving not only as substrate but also as the
oxidant of σH-adducts during the formation of nitroamines
2a and 3a. As a result, their yields were lower and products
from the reduction of substrate were observed, which had
oligomeric structures according to 1H NMR spectra.
During arylamination of nitroarenes, the oxidative
mechanism (Scheme 1, path a) is accompanied by another
route involving the aromatization of σH-adduct through its
disproportionation, leading to the respective nitroso
compounds (Scheme 1, path b).2,5d Thus, anions of primary
arylamines react with nitrobenzenes, forming ortho-σH-
adducts that under alkaline reaction conditions are
converted to N-aryl-2-nitrosoanilines.16a–d It is interesting
to note that para-σH-adducts were also formed, but they
were oxidized under the reaction conditions to the
respective 4-nitrodiarylamines.16b We recently used the
The anions of other para-substituted anilines, such as
p-toluidine, p-anisidine, p-bromoaniline, p-fluoroaniline,
and p-trifluoromethylaniline reacted analogously with the
formation of the respective compounds 2b–f, 3b–f, and 4b–f
(Table 1, entries 3–7). An exception was found in the case
H
example of 3-nitropyridine to demonstrate that the SN
reactions of carbamoylamination17a and arylamination17b
proceeded in anhydrous DMSO exclusively at the para
position relative to the NO2 group and this did not prevent
the formation of mixtures containing nitro and nitroso
derivatives. Furthermore, the major arylamination products
were specifically p-nitroso compounds.
Table 1. Product yields from
SNH arylamination reaction of 5-nitroquinoline (1)*
Product
Entry
Ar
(yield after chromatographic separation,
%)
Taking into account the aforementioned observations,
the interest in oxidative SNH-arylamination of 5-, 6-, 7-, and
8-nitroquinolines was motivated by the expected formation
of arylamino derivatives not only on the basis of the
respective nitroquinolines, but also nitrosoquinolines.
In the case of reaction between 5-nitroquinoline (1) and
aniline, it was found that it was optimal to use 2 equiv of
anilide anion for 1 equiv of substrate. The anion was
generated by treating aniline solution in anhydrous DMSO
with NaH at room temperature. The reaction was complete
within 1 h after the addition of 5-nitroquinoline (1), giving
a mixture of three products that were separated by
chromatography on silica gel. The products were identified
as 5-nitro-N-phenylquinolin-8-amine (2a), 5-nitro-N-phenyl-
quinolin-6-amine (3a), and 5-nitroso-N-phenylquinolin-
6-amine (4a) with the overall yield of 58% (Scheme 2,
1
2
Ph
2a (16)
2a (15)
2b (27)
2c (13)
2d (17)
2e (11)
2f (13)
2g (29)
2h (58)
2i (44)
3a (25)
3a (23)
3b (6)
3c (11)
3d (10)
3e (7)
3f (10)
3g (13)
3h (3)
–
4a (17)
4a (16)
4b (26)
4c (12)
4d (27)
4e (18)
4f (25)
–
Ph**
3
4-MeC6H4
4-MeOC6H4
4-BrC6H4
4-FC6H4
4
5
6
7
4-CF3C6H4
4-O2NC6H4
2-ClC6H4
2,4,6-Br3C6H2
8
9
–
10
–
* In all experiments, 2 equiv of the appropriate arylamine and 2 equiv of
NaH were used.
** The experiment was performed under argon atmosphere.
Scheme 2
O
NO2
NO2
NO2
H
N
N
1. ArNH2, NaH,
DMSO, rt, 1 h
ArNH
Ar
+
+
2. H2O
N
4a–f
N
N
N
1
3a h
–
NHAr
2a–i
876

Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
of p-nitroaniline, which, similarly to m-nitropyridine,17b
formed only nitro products 2g and 3g (entry 8). It is
probable that it itself acted as an oxidant toward the
respective intermediates. It was shown that o-chloroaniline
also did not form nitrosoamine, while the yield of nitro-
amine 3h reached only 3% (entry 9). In our opinion, this
indicated that the ortho substituent in aniline and the nitro
group at position 5 of quinoline ring created substantial
steric obstacles in the transition state during the formation
of the ortho-σH-adduct. Indeed, the presence of two ortho
substituents, as in the case of 2,4,6-tribromoaniline, led to
the formation of only p-nitroamine 2i (entry 10).
Figure 1. The molecular structure of compound 4b with atoms
represented by thermal vibration ellipsoids of 50% probability.
1
A characteristic feature in H NMR spectra of nitroso-
amines 4a–f that were acquired in CDCl3 solutions was the
pronounced downfield shift of NH proton signals (15.9–
16.0 ppm), pointing to a strong intramolecular NH···O=N
hydrogen bond. The structure of nitrosoamine 4b was
confirmed by X-ray structural analysis (Fig. 1).
Scheme 3
8-Nitroquinoline (5) under the same conditions formed a
mixture of 5-arylamino-8-nitroquinolines 6a–f and 7-aryl-
amino-8-nitrosoquinolines 7a–f, with the latter as the major
products (Scheme 3, Table 2, entries 1–6). The use of
p-nitroaniline resulted in a mixture of two nitro compounds
6g and 8, while o-chloroaniline and 2,4,6-tribromoaniline
gave only the para-substitution products 6h,i (Scheme 3,
Table 2, entries 7–9). Similarly to the case of compounds
1
4a–f, H NMR spectra of nitrosoamines 7a–f in CDCl3
solutions indicated the presence of a strong intramolecular
hydrogen bond (the chemical shifts of NHAr protons were
in the range of 15.7–15.8 ppm).
Table 2. Product yields from the SNH arylamination reaction of
8-nitroquinoline (5)*
It is known that SNH-arylamination reaction of substrates
lacking a free para position relative to the NO2 group, as in
para-substituted nitrobenzenes16a or 5-nitroindole,16e
produces only the respective o-nitrosoamines or products
of their subsequent transformations. Similar dispro-
portionation products were also expected from the
arylamination of 6- and 7-nitroquinolines. However, in
none of these two cases the respective nitroso compounds
could be detected or isolated. 7-Nitroquinoline (9) reacted
regio- and chemoselectively at position 8, forming 8-aryl-
amino-7-nitroquinolines 10a–g as the only reaction
products in 29–63% yields (Scheme 4).
Product
Entry
Ar
(yield after chromatographic separation,
%)
1
2
3
4
5
6
7
8
9
Ph
6a (12)
6b (14)
6c (8)
7a (48)
7b (44)
7c (42)
7d (36)
7e (45)
7f (16)
8 (8)
4-MeC6H4
4-MeOC6H4
4-BrC6H4
6d (6)
6e (9)
4-FC6H4
4-CF3C6H4
4-O2NC6H4
2-ClC6H4
6f (10)
6g (18)
6h (42)
6i (18)
6-Nitroquinoline (11) also reacted regioselectively at
position 5, forming oxidative arylamination products –
5-arylamino-6-nitroquinolines 12a–g in 23–61% yields
(Scheme 5). In several cases we were also able to isolate
and identify the minor products of these transformations.
Thus, in the case of p-anisidine, 9-methoxypyrido[3,2-a]-
phenazine 7-oxide (13c) was obtained in 6% yield, while
the use of p-bromo- and p-trifluoromethylanilines led to the
formation of 9-bromo-5-[(4-bromophenyl)amino]pyrido-
[3,2-a]phenazine 7-oxide (14d) and 9-(trifluoromethyl)-
5-{[4-(trifluoromethyl)phenyl]amino}pyrido[3,2-a]phenazine
7-oxide (14f) in 15 and 7% yields, respectively.
Dedicated experiments showed that nitroamines 12c,d,f
under the same reaction conditions were not converted to
compounds 13 and 14. However, it is known that N-aryl-
2-nitrosoanilines are readily cyclized with the formation of
phenazine derivatives.16c,18 Taking this into account, we
–
2,4,6-Br3C6H2
–
* All experiments were performed with 2 equiv of the respective
arylamine and 2 equiv of NaH.
Scheme 4
1. ArNH2, NaH,
DMSO, rt, 1 h
O2N
N
2. H2O
O2N
N
9
NHAr
10a–g
a Ar = Ph (61%), b Ar = 4-MeC6H4 (57%),
c Ar = 4-MeOC6H4 (63%), d Ar = 4-BrC6H4 (58%),
e Ar = 4-FC6H4 (49%), f Ar = 4-CF3C6H4 (37%),
g Ar = 4-O2NC6H4 (29%)
877

Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
R
Scheme 5
MeO
N
1. ArNH2, NaH,
DMSO, rt, 1 h
NHAr
O2N
N+
–O
O2N
N
+
+
2. H2O
N+
–O
N
N
N
11
12a–g
NH
N
13c
R
14d,f
12 a Ar = Ph (53%), b Ar = 4-MeC6H4 (61%), c Ar = 4-MeOC6H4 (41%), d Ar = 4-BrC6H4 (25%),
eAr = 4-FC6H4 (38%), f Ar = 4-CF3C6H4 (23%), g Ar = 4-O2NC6H4 (49%)
14 d R = Br; f R = CF3
proposed that the starting materials for the synthesis of
products 13 and 14 are the respective 5-arylamino-
6-nitrosoquinolines 15, which are formed in small amounts
during the arylamination of 6-nitroquinoline (11) and
further undergo cyclization, for example, according to
Scheme 6.
does not significantly solvate anionic species, thus
enhancing the nucleophilicity of arylamide ions, but
without stabilization of anionic intermediates. The strongly
polar nature of DMSO promotes the formation of more
polar anionic σH-adducts, which probably affects the
regioselectivity of the reaction. In our experiments it was
impossible to exclude the presence of oxidant, in order to
direct the reaction toward the formation of nitroso
compounds, since substrate itself acted as an oxidant
(Table 1, entry 2).
It could be expected that the cyclization of nitroso-
amines 15 should lead to N-oxides 13 as the final products.
However, in two cases out of three they were further aryl-
aminated while leaving the N-oxide functional group
unchanged, with the reaction proceeding regioselectively at
the benzene ring of phenazine oxide that is fused with
pyridine ring. The structure of N-oxide 14f was confirmed
by X-ray structural analysis (Fig. 2).
Taking into account the reversibility of the first step
involving the addition of nucleophile, such differences in
H
the outcome of SN arylamination reactions of isomeric
nitroquinolines can be explained by the different
thermodynamic stability of σH-adducts, as well as by the
competition between aromatization reaction rates in the
two directions (the kinetic factor). Compared to
nitroarenes, the π-electron poor pyridine ring certainly
facilitated the addition step, but probably did not
substantially improve the stability of the σH-intermediate,
since the delocalization of negative charge involving the
pyridine nitrogen atom that is possible in the case of 6- and
8-nitroquinolines would simultaneously disrupt the
aromaticity of two rings. As a polar aprotic solvent, DMSO
Figure 2. The molecular structure of compound 14f with atoms
represented by thermal vibration ellipsoids of 50% probability.
Scheme 6
878

Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
Thus, the use of arylamine anions as nucleophilic agents
288.0745 [М+Na]+. C15H11N3NaO2. Calculated, m/z:
288.0743.
5-Nitro-N-phenylquinolin-6-amine (3a). The second
in the reaction with 5-, 6-, and 8-nitroquinolines in
anhydrous DMSO produced mixtures of arylamino
derivatives of nitroquinolines and their nitroso analogs.
This result was explained by the aromatization of the
respective σH-adducts simultaneously in two directions,
which has not been previously observed in nitroquinoline
series. The nitroso products in the case of 6-nitroquinoline
participated in cyclization process with the formation of
pyrido[3,2-a]phenazine 7-oxide derivatives. The use of
7-nitroquinoline led only to 8-arylamino-7-nitroquinolines.
fraction of orange color, eluent PhMe. Yield 33 mg (25%),
light-orange crystals, mp 69–70°С (CHCl3). 1H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 7.29–7.35 (3H, m,
H-2',4',6' Ph); 7.45–7.50 (2H, m, H-3',5' Ph); 7.52–7.57
(2H, m, H-3,7 Quin); 8.03 (1H, d, J = 9.6, H-8 Quin); 8.75
(1H, dd, J = 4.3, J = 1.4, H-2 Quin); 9.05 (1H, br. d,
J = 8.7, H-4 Quin); 10.05 (1H, br. s, NH). 13C NMR
spectrum (CDCl3), δ, ppm: 120.2; 124.3; 124.5; 124.9;
126.8 (2C); 130.2; 131.8; 137.5; 138.1; 142.6; 143.7; 147.8.
Found, m/z: 266.0931 [М+H]+. C15H12N3O2. Calculated, m/z:
266.0924.
Experimental
1H and 13C NMR spectra (400 and 100 MHz,
respectively) were acquired, as well as two-dimensional
NMR experiments performed on a Bruker Avance HD 400
instrument for samples in DMSO-d6 or CDCl3 solutions. In
the case of DMSO-d6 solutions, the residual solvent signals
5-Nitroso-N-phenylquinolin-6-amine (4a). The third
fraction of brown color, eluent PhMe. Yield 21 mg (17%),
1
light-brown crystals, mp 106–107°С (CHCl3). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 7.31 (2H, d, J = 8.6,
H-2',6' Ph); 7.35–7.41 (2H, m, H-7 Qu, H-4' Ph); 7.46–7.50
(2H, m, H-3',5' Ph); 7.60 (1H, dd, J = 8.3, J = 4.4, H-3
Quin); 7.95 (1H, d, J = 9.8, H-8 Quin); 8.83 (1H, dd,
J = 4.4, J = 1.2, H-2 Quin); 9.43 (1H, dd, J = 8.3, J = 1.2,
H-4 Quin); 15.93 (1H, br. s, NH). 13C NMR spectrum
(CDCl3), δ, ppm: 119.7; 124.8; 125.3; 127.9; 129.6; 130.0;
130.3; 136.5; 136.6; 142.8; 143.3; 147.1; 149.6. Found, m/z:
272.0796 [М+Na]+. C15H11N3NaO. Calculated, m/z:
272.0794.
1
were used as internal standard (2.50 ppm for H nuclei,
40.45 ppm for 13С nuclei).19 TMS was used as internal
standard for NMR spectra acquired in CDCl3 solutions.
The signals of 13С NMR spectra for key compounds were
1
assigned on the basis of two-dimensional Н –13С HMBC
and 1H–13C HSQC experiments. High-resolution mass
spectra were recorded on a Bruker maXis Impact UHR-TOF
mass spectrometer (electrospray ionization). Melting points
were determined on a REACH Devices RD-MP apparatus.
The reaction progress and purity of the obtained
compounds were controlled by TLC using Silufol UV-254
plates.
5-Nitro-N-(p-tolyl)quinolin-8-amine (2b). The first
fraction of yellow color, eluent PhMe. Yield 38 mg (27%),
1
yellowish-orange crystals, mp 94–95°С (PhH). H NMR
Nitroquinolines and sodium hydride (60% suspension in
paraffin oil) were commercially available from abcr GmbH
and were used without additional purification.
spectrum (CDCl3), δ, ppm (J, Hz): 2.40 (3H, s, CH3); 7.13
(1H, d, J = 9.1, H-7 Quin); 7.27 (2H, d, J = 8.5, H-2',6' Ar);
7.31 (2H, d, J = 8.5, H-3',5' Ar); 7.69 (1H, dd, J = 8.8,
J = 4.1, H-3 Quin); 8.53 (1H, d, J = 9.1, H-6 Quin); 8.82
(1H, dd, J = 4.1, J = 1.5, H-2 Quin); 9.00 (1H, br. s, NH);
9.45 (1H, dd, J = 8.8, J = 1.5, H-4 Quin). 13C NMR
spectrum (DMSO-d6), δ, ppm: 21.2; 103.5; 123.3; 123.7;
125.1; 130.4; 130.5; 132.9; 133.8; 135.5; 136.2; 136.5; 145.4;
147.8. Found, m/z: 302.0914 [М+Na]+. C16H13N3NaO2.
Calculated, m/z: 302.0900.
5-Nitro-N-(p-tolyl)quinolin-6-amine (3b). The second
fraction of orange color, eluent PhMe. Yield 8 mg (6%),
dark-orange crystals, mp 91–92°С (PhH). 1H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 2.41 (3H, s, CH3); 7.19
(2H, d, J = 8.2, H-2',6' Ar); 7.27 (2H, d, J = 8.2, H-3',5'
Ar); 7.47 (1H, d, J = 9.6, H-7 Quin); 7.52 (1H, dd, J = 8.8,
J = 4.2, H-3 Quin); 7.97 (1H, d, J = 9.6, H-8 Quin); 8.72
(1H, dd, J = 4.2, J = 1.4, H-2 Quin); 9.06 (1H, br. d,
J = 8.8, H-4 Quin); 10.11 (1H, br. s, NH). 13C NMR
spectrum (CDCl3), δ, ppm: 21.2; 120.0; 124.2; 124.6;
125.3; 126.2; 130.7; 131.6; 135.3; 137.0; 137.8; 142.8;
144.4; 147.9. Found, m/z: 280.1082 [М+H]+. C16H14N3O2.
Calculated, m/z: 280.1081.
Preparation of compounds 2a–i, 3a–h, 4a–f, 6a–i, 7a–f,
8, 10a–g, 12a–g, 13c, 14d,f by arylamination of nitro-
quinolines 1, 5, 9, 11 (General method). Sodium hydride
(60% suspension in paraffin oil, 40 mg, 1.0 mmol) and the
appropriate nitroquinoline 1, 5, 9, or 11 (87 mg, 0.5 mmol)
were added to a solution of arylamine (1.0 mmol) in
anhydrous DMSO (2.0 ml) at room temperature. The
mixture was vigorously stirred at room temperature for 1 h
and then poured into saturated NaCl solution that was
cooled to 5°С. The obtained precipitate was filtered off,
washed with water, and dried. The obtained mixture was
separated into individual compounds by dry silica gel flash
chromatography.20
5-Nitro-N-phenylquinolin-8-amine (2a). The first
fraction of yellow color, eluent PhMe. Yield 21 mg (16%),
1
yellow crystals, mp 108–109°С (PhH). H NMR spectrum
(DMSO-d6), δ, ppm (J, Hz): 7.20 (1H, d, J = 9.1, H-7
Quin); 7.24 (1H, t, J = 7.4, H-4' Ph); 7.47 (2H, dd, J = 7.9,
J = 7.4, H-3',5' Ph); 7.51 (2H, d, J = 7.9, H-2',6' Ph); 7.90
(1H, dd, J = 8.8, H-3 Quin); 8.51 (1H, J = 9.1, H-6 Quin);
8.98 (1H, br. d, J = 4.1, H-2 Quin); 9.29 (1H, br. d, J = 8.8,
H-4 Quin); 9.95 (1H, br. s, NH). 13C NMR spectrum
(DMSO-d6), δ, ppm: 104.1 (C-7); 123.0 (C-4a); 123.5
(C-2',6' Ph); 125.1 (C-4' Ph); 125.6 (C-3); 129.5 (C-3',5'
Ph); 130.3 (C-6); 132.1 (C-5); 132.7 (C-4); 136.1 (C-8a);
139.1 (C-1' Ph); 148.3 (C-2); 148.4 (C-8). Found, m/z:
5-Nitroso-N-(p-tolyl)quinolin-6-amine (4b). The third
fraction of brown color, eluent PhMe. Yield 34 mg (26%),
light-brown crystals, mp 133–134°С (decomp., PhMe).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.42 (3H, s,
CH3); 7.19 (2H, d, J = 8.1, H-2',6' Ar); 7.29 (2H, d, J = 8.1,
H-3',5' Ar); 7.38 (1H, d, J = 9.8, H-7 Quin); 7.60 (1H, dd,
879

Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
J = 8.4, J = 4.4, H-3 Quin); 7.94 (1H, d, J = 9.8, H-8 Quin);
N-(4-Bromophenyl)-5-nitroquinolin-6-amine (3d).
The second fraction of orange color, eluent PhMe. Yield
17 mg (10%), light-red crystals, mp 166–167°С (PhMe).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.19 (2H, d,
J = 8.6, H-2',6' Ar); 7.52 (1H, d, J = 9.6, H-7 Quin); 7.50–
7.61 (3H, m, H-3 Qu, H-3',5' Ar); 8.05 (1H, d, J = 9.6, H-8
Quin); 8.77 (1H, dd, J = 4.2, J = 1.4, H-2 Quin); 8.98 (1H, br. d,
J = 8.8, H-4 Quin); 9.80 (1H, br. s, NH). 13C NMR spectrum
(CDCl3), δ, ppm: 119.7; 119.9; 124.3; 124.4; 126.2; 131.0;
131.6; 133.3; 137.4; 137.6; 142.6; 142.9; 148.3. Found, m/z:
365.9852 [М(79Br)+Na]+. C15H10BrN3NaO2. Calculated, m/z:
365.9849.
N-(4-Bromophenyl)-5-nitrosoquinolin-6-amine (4d).
The third fraction of brown color, eluent PhMe. Yield
44 mg (27%), brown crystals, mp 159–160°С (CHCl3).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.18 (2H, d,
J = 8.7, H-2',6' Ar); 7.32 (1H, d, J = 9.8, H-7 Quin); 7.58–7.63
(3H, m, H-3',5' Ar, H-3 Quin); 7.96 (1H, d, J = 9.8, H-8
Quin); 8.84 (1H, dd, J = 4.4, J = 1.6, H-2 Quin); 9.40 (1H,
dd, J = 8.4, J = 1.6, H-4 Quin); 15.91 (1H, br. s, NH).
13C NMR spectrum (CDCl3), δ, ppm: 119.4; 121.3; 124.9;
126.7; 129.8; 130.2; 133.2; 136.1; 137.0; 143.1; 143.5;
146.9; 149.9. Found, m/z: 328.0082 [М(79Br)+H]+.
C15H11BrN3O. Calculated, m/z: 328.0080.
8.83 (1H, dd, J = 4.4, J = 1.4, H-2 Quin); 9.43 (1H, dd,
J = 8.4, J = 4.4, H-4 Quin); 15.91 (1H, br. s, NH).
13C NMR spectrum (CDCl3), δ, ppm: 21.3; 119.9; 124.7;
125.2; 129.6; 130.4; 130.6; 133.6; 136.6; 138.1; 142.7;
143.2; 147.1; 149.5. Found, m/z: 286.0961 [М+Na]+.
C16H13N3NaO. Calculated, m/z: 286.0951.
N-(4-Methoxyphenyl)-5-nitroquinolin-8-amine (2c).
The first fraction of yellow color, eluent PhMe. Yield
19 mg (13%), yellow crystals, mp 148–149°С (PhMe).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 3.86 (3H, s,
CH3O); 6.97 (1H, d, J = 9.1, H-7 Quin); 7.00 (2H, d,
J = 8.8, H-2',6' Ar); 7.33 (2H, d, J = 8.8, H-3',5' Ar); 7.69
(1H, dd, J = 8.8, J = 4.1, H-3 Quin); 8.52 (1H, d, J = 9.1,
H-6 Quin); 8.81 (1H, dd, J = 4.1, J = 1.5, H-2 Quin); 8.90
(1H, br. s, NH); 9.46 (1H, dd, J = 8.8, J = 1.5, H-4 Quin).
13C NMR spectrum (DMSO-d6), δ, ppm: 55.7; 103.2;
115.1; 123.7; 125.2; 125.6; 130.5; 131.5; 132.7; 133.8;
136.3; 147.7; 149.2; 157.8. Found, m/z: 318.0854 [М+Na]+.
C16H13N3NaO3. Calculated, m/z: 318.0849.
N-(4-Methoxyphenyl)-5-nitroquinolin-6-amine (3c).
The second fraction of orange color, eluent PhMe. Yield
16 mg (11%), orange-red crystals, mp 127–128°С (PhH).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 3.88 (3H, s,
CH3O); 6.99 (2H, d, J = 8.8, H-2',6' Ar); 7.23 (2H, d, J = 8.8,
H-3',5' Ar); 7.38 (1H, d, J = 9.6, H-7 Quin); 7.53 (1H, dd,
J = 8.8, J = 4.2, H-3 Quin); 7.96 (1H, d, J = 9.6, H-8 Quin);
8.70 (1H, dd, J = 4.2, J = 1.0, H-2 Quin); 9.10 (1H, br. d,
J = 8.8, H-4 Quin); 10.14 (1H, br. s, NH). 13C NMR
spectrum (CDCl3), δ, ppm: 55.7; 115.3; 119.9; 124.3;
124.7; 125.6; 127.4; 130.6; 131.7; 137.9; 142.7; 145.2;
147.8; 158.7. Found, m/z: 318.0854 [М+Na]+.
C16H13N3NaO3. Calculated, m/z: 318.0849.
N-(4-Fluorophenyl)-5-nitroquinolin-8-amine (2e).
The first fraction of yellow color, eluent PhMe. Yield
16 mg (11%), yellow crystals, mp 231–232°С (CHCl3).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.05 (1H, d,
J = 9.0, H-7 Quin); 7.15–7.20 (2H, m, H-2',6' Ar); 7.36–7.41
(2H, m, H-3',5' Ar); 7.70 (1H, dd, J = 8.8, J = 4.2, H-3
Quin); 8.53 (1H, d, J = 9.0, H-6 Quin); 8.83 (1H, dd,
J = 4.2, J = 1.4, H-2 Quin); 8.94 (1H, br. s, NH); 9.45 (1H,
dd, J = 8.8, J = 1.4, H-4 Quin). 13C NMR spectrum
2
N-(4-Methoxyphenyl)-5-nitrosoquinolin-6-amine (4c).
The third fraction of brown color, eluent PhMe. Yield
17 mg (12%), dark-bordeaux crystals, mp 120–121°С
(CDCl3), δ, ppm (J, Hz): 103.3; 116.8 (d, JCF = 22.6);
3
123.6; 125.2; 125.4 (d, JCF = 8.2); 130.1; 133.4; 133.8;
134.9 (4JCF = 3.0); 136.4; 147.9; 148.4; 160.4 (d, 1JCF = 244.1).
Found, m/z: 306.0657 [М+Na]+. C15H10FN3NaO2.
Calculated, m/z: 306.0649.
1
(CHCl3). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 3.87
(3H, s, OCH3); 7.00 (2H, d, J = 8.8, H-2',6' Ar); 7.23 (2H, d,
J = 8.8, H-3',5' Ar); 7.35 (1H, d, J = 9.8, H-7 Quin); 7.59 (1H,
dd, J = 8.3, J = 4.3, H-3 Quin); 7.94 (1H, d, J = 9.8, H-8
Quin); 8.82 (1H, br. d, J = 3.2, H-2 Quin); 9.43 (1H, br. d,
J = 8.3, H-4 Quin); 15.92 (1H, br. s, NH). 13C NMR
spectrum (CDCl3), δ, ppm: 55.8; 115.2; 119.9; 124.7;
126.8; 128.8; 129.6; 130.4; 137.0; 142.7; 143.2; 147.1;
149.5; 159.2. Found, m/z: 302.0907 [М+Na]+.
C16H13N3NaO2. Calculated, m/z: 302.0900.
N-(4-Fluorophenyl)-5-nitroquinolin-6-amine (3e).
The second fraction of orange color, eluent PhMe. Yield
10 mg (7%), light-orange crystals, mp 144–145°С (PhH).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.15–7.21 (2H,
m, H-2',6' Ar); 7.25–7.31 (3H, m, H-3',5' Ar); 7.41 (1H, d,
J = 9.6, H-7 Quin); 7.55 (1H, dd, J = 8.8, J = 4.2, H-3
Quin); 8.01 (1H, d, J = 9.6, H-8 Quin); 8.75 (1H, dd,
J = 4.2, J = 1.2, H-2 Quin); 9.04 (1H, br. d, J = 8.8, H-4
Quin); 9.96 (1H, br. s, NH). 13C NMR spectrum (CDCl3),
δ, ppm (J, Hz): 117.1 (2JCF = 22.7); 119.6; 124.4; 124.5;
126.5; 127.3 (3JCF = 8.2); 131.6; 134.1; 137.9; 142.8;
144.0; 148.1; 161.3 (d, 1JCF = 245.8). Found, m/z: 306.0653
[М+Na]+. C15H10FN3NaO2. Calculated, m/z: 306.0649.
N-(4-Fluorophenyl)-5-nitrosoquinolin-6-amine (4e).
The third fraction of brown color, eluent PhMe. Yield
24 mg (18%), dark-brown crystals, mp 146–147°С
(CHCl3). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.16–
7.22 (2H, m, H-2',6' Ar); 7.31–7.25 (3H, m, H-3',5' Ar, H-7
Quin); 7.60 (1H, dd, J = 8.3, J = 4.4, H-3 Quin); 7.97 (1H,
d, J = 9.8, H-8 Quin); 8.83 (1H, br. d, J = 4.4, H-2 Quin);
9.42 (1H, br. d, J = 8.3, H-4 Quin); 15.90 (1H, br. s, NH).
N-(4-Bromophenyl)-5-nitroquinolin-8-amine (2d).
The first fraction of yellow color, eluent PhMe. Yield
29 mg (17%), dark-yellow crystals, mp 183–184°С (PhH).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.20 (1H, d,
J = 9.0, H-7 Quin); 7.31 (2H, d, J = 8.7, H-2',6' Ar); 7.57
(2H, d, J = 8.7, H-3',5' Ar); 7.71 (1H, dd, J = 8.8, J = 4.1,
H-3 Quin); 8.54 (1H, d, J = 9.0, H-6 Quin); 8.85 (1H, dd,
J = 4.1, J = 1.5, H-2 Quin); 9.03 (1H, br. s, NH); 9.44 (1H,
dd, J = 8.8, J = 1.5, H-4 Quin). 13C NMR spectrum
(CDCl3), δ, ppm: 103.8; 118.0; 123.5; 124.3; 125.2; 129.9;
133.0; 133.8; 133.9; 136.7; 138.2; 147.2; 148.0. Found, m/z:
365.9847 [М(79Br)+Na]+. C15H10BrN3NaO2. Calculated, m/z:
365.9849.
880

Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
13C NMR spectrum (CDCl3), δ, ppm (J, Hz): 117.1 (d,
PhMe. Yield 20 mg (13%), light-orange crystals, mp 297–
3
2JCF = 22.8); 119.4; 124.9; 127.2 (d, JCF = 8.5); 129.7;
298°С (PhH). 1H NMR spectrum (DMSO-d6), δ, ppm
(J, Hz): 7.70 (1H, d, J = 9.0, H-7 Quin); 7.78 (2H, d,
J = 9.1, H-2',6' Ar); 7.94 (1H, dd, J = 8.8, J = 4.0, H-3
Quin); 8.28 (2H, d, J = 9.1, H-3',5' Ar); 8.56 (1H, d,
J = 9.0, H-8 Quin); 9.05 (1H, br. d, J = 4.0, H-2 Quin);
9.25 (1H, br. d, J = 8.8, H-4 Quin); 10.37 (1H, br. s, NH).
13C NMR spectrum (DMSO-d6), δ, ppm: 108.1; 120.3;
122.5; 125.5; 125.6; 128.9; 132.8; 135.3; 137.4; 142.0;
145.2; 146.7; 149.2. Found, m/z: 333.0598 [М+Na]+.
C15H10N4NaO4. Calculated, m/z: 333.0594.
4
130.3; 132.6 (d, JCF = 3.2); 137.0; 143.0; 143.3; 147.0;
1
149.7; 161.8 (d, JCF = 247.2). Found, m/z: 290.0708
[М+Na]+. C15H10FN3NaO. Calculated, m/z: 290.0700.
5-Nitro-N-[4-(trifluoromethyl)phenyl]quinolin-8-amine
(2f). The first fraction of yellow color, eluent PhMe. Yield
22 mg (13%), pale-yellow crystals, mp 141–142°С (PhH).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.39 (1H, d,
J = 9.0, H-7 Quin); 7.53 (2H, d, J = 8.3, H-2',6' Ar); 7.58–
7.75 (3H, m, H-3 Qu, H-3',5' Ar); 8.57 (1H, d, J = 9.0, H-6
Quin); 8.87 (1H, br. d, J = 4.1, H-2 Quin); 9.24 (1H, br. s,
NH); 9.43 (1H, br. d, J = 8.8, H-4 Quin). 13C NMR
spectrum (CDCl3), δ, ppm (J, Hz): 104.5; 121.3; 123.3;
N-(2-Chlorophenyl)-5-nitroquinolin-8-amine (2h).
The first fraction of yellow color, eluent PhMe. Yield
87 mg (58%), dark-yellow crystals, mp 184–185°С (PhMe).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.18 (1H, dd,
J = 8.0, J = 7.8, H-5' Ar); 7.22 (1H, d, J = 9.0, H-7 Quin);
7.38 (1H, dd, J = 8.0, J = 7.8, H-4' Ar); 7.55 (1H, dd,
J = 8.0, J = 1.3, H-6' Ar); 7.68 (1H, dd, J = 8.0, J = 1.1,
H-3' Ar); 7.72 (1H, dd, J = 8.8, J = 4.2, H-3 Quin); 8.55
(1H, d, J = 9.0, H-6 Quin); 8.90 (1H, dd, J = 4.2, J = 1.4,
H-2 Quin); 9.27 (1H, br. s, NH); 9.43 (1H, dd, J = 8.8,
J = 1.4, H-4 Quin). 13C NMR spectrum (CDCl3), δ, ppm:
104.2; 122.8; 123.5; 125.2; 125.9; 127.8; 127.9; 129.7;
130.8; 133.7; 134.2; 136.2; 137.0; 146.7; 148.3. Found, m/z:
322.0343 [М(35Cl)+Na]+. C15H10ClN3NaO2. Calculated, m/z:
322.0354.
N-(2-Chlorophenyl)-5-nitroquinolin-6-amine (3h).
The second fraction of yellow-orange color, eluent PhMe.
Yield 5 mg (3%), yellow crystals, mp 154–155°С (CHCl3).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.23 (1H, dd,
J = 8.2, J = 7.8, H-5' Ar); 7.35 (1H, dd, J = 8.2, J = 7.8, H-4'
Ar); 7.43 (1H, dd, J = 8.2, J = 1.1, H-6' Ar); 7.49 (1H, d,
J = 9.5, H-7 Quin); 7.52–7.57 (2H, m, H-3 Qu, H-3' Ar);
8.06 (1H, d, J = 9.5, H-8 Quin); 8.78 (1H, dd, J = 4.2, J = 1.3,
H-2 Quin); 8.92 (1H, d, J = 8.8, H-4 Quin); 9.68 (1H, br. s,
NH). 13C NMR spectrum (CDCl3), δ, ppm: 120.1; 124.1;
124.3; 124.7; 127.1; 128.0; 128.6; 129.2; 130.9; 131.4;
135.8; 137.4; 141.5; 143.1; 148.5. Found, m/z: 322.0369
[М(35Cl)+Na]+. C15H10ClN3NaO2. Calculated, m/z: 322.0354.
5-Nitro-N-(2,4,6-tribromophenyl)quinolin-8-amine (2i).
The first fraction of yellow color, eluent PhMe. Yield
110 mg (44%), light-brown crystals, mp 196–197°С (PhH).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 6.36 (1H, d,
J = 8.8, H-7 Quin); 7.73 (1H, dd, J = 8.9, J = 4.1, H-3 Quin);
7.88 (2H, s, H-3',5' Ar); 8.49 (1H, d, J = 8.8, H-6 Quin); 8.66
(1H, br. s, NH); 8.90 (1H, dd, J = 4.1, J = 1.5, H-2 Quin);
9.42 (1H, dd, J = 8.9, J = 1.5, H-4 Quin). 13C NMR spectrum
(CDCl3), δ, ppm: 104.9; 121.8; 123.3; 125.0; 125.1; 129.2;
133.7; 134.8; 135.6; 136.1; 136.3; 146.8; 148.5. Found, m/z:
521.8053 [М(79Br)+Na]+. C15H8Br3N3NaO2. Calculated, m/z:
521.8059.
1
2
124.2 (q, JCF = 269.9); 126.4 (q, JCF = 32.8); 127.2 (q,
3JCF = 3.7); 129.5; 133.8; 134.6; 136.9; 142.5; 146.1; 148.2.
Found, m/z: 356.0629 [М+Na]+. C16H10F3N3NaO2. Calculated,
m/z: 356.0617.
5-Nitro-N-[4-(trifluoromethyl)phenyl]quinolin-6-amine
(3f). The second fraction of orange color, eluent PhMe.
Yield 17 mg (10%), dark-orange crystals, mp 146–147°С
1
(PhH). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.39
(2H, d, J = 8.2, H-2',6' Ar); 7.57 (1H, dd, J = 8.8, J = 4.2,
H-3 Quin); 7.67 (1H, d, J = 9.5, H-7 Quin); 7.70 (2H, d,
J = 8.2, H-3',5' Ar); 8.11 (1H, d, J = 9.5, H-8 Quin); 8.75
(1H, br. d, J = 4.2, H-2 Quin); 8.88 (1H, br. d, J = 8.8, H-4
Quin); 9.61 (1H, br. s, NH). 13C NMR spectrum (CDCl3),
δ, ppm (J, Hz): 120.2; 123.0; 123.9; 124.0 (q,
3
1JCF-= 270.1); 124.4; 127.3 (q, JCF = 3.6); 127.6 (q,
2JCF = 32.8); 129.4; 131.3; 137.4; 140.7; 142.0; 143.3;
148.8. Found, m/z: 356.0619 [М+Na]+. C16H10F3N3NaO2.
Calculated, m/z: 356.0617.
5-Nitroso-N-[4-(trifluoromethyl)phenyl]quinolin-6-amine
(4f). The third fraction of brown color, eluent PhMe. Yield
40 mg (25%), light-brown crystals, mp 144–145°С (PhH).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.34 (1H, d,
J = 9.8, H-7 Quin); 7.42 (2H, d, J = 8.2, H-2',6' Ar); 7.61
(1H, dd, J = 8.4, J = 4.4, H-3 Quin); 7.76 (2H, d, J = 8.2,
H-3',5' Ar); 7.98 (1H, d, J = 9.8, H-8 Quin); 8.86 (1H, br. d,
J = 4.4, H-2 Quin); 9.39 (1H, br. d, J = 8.4, H-4 Quin);
16.00 (1H, br. s, NH). 13C NMR spectrum (CDCl3), δ, ppm
(J, Hz): 119.3; 122.1; 123.0; 123.8 (q, 1JCF = 270.3); 125.0;
3
2
127.2 (q, JCF = 3.7); 129.5 (q, JCF = 32.9); 129.9; 137.5;
141.0; 143.3; 143.8; 146.7; 150.1. Found, m/z: 340.0679
[М+Na]+. C16H10F3N3NaO. Calculated, m/z: 340.0689.
4-Nitro-N-(4-nitrophenyl)quinolin-8-amine
(2g).
The first fraction of yellow color, eluent PhMe. Yield
45 mg (29%), dark-yellow crystals, mp 299–300°С (PhMe).
1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 7.70 (1H,
d, J = 9.0, H-7 Quin); 7.78 (2H, d, J = 8.7, H-2',6' Ar); 7.95
(1H, dd, J = 8.8, J = 4.1, H-3 Quin); 8.28 (2H, d, J = 8.7,
H-3',5' Ar); 8.56 (1H, d, J = 9.0, H-6 Quin); 9.07 (1H, br. d,
J = 4.1, H-2 Quin); 9.24 (1H, br. d, J = 8.8, H-4 Quin); 10.40
(1H, br. s, NH). 13C NMR spectrum (DMSO-d6), δ, ppm:
108.1; 120.3; 122.5; 125.5; 125.6; 128.9; 132.7; 135.2;
137.4; 141.9; 145.2; 146.7; 149.2. Found, m/z: 333.0603
[М+Na]+. C15H10N4NaO4. Calculated, m/z: 333.0594.
8-Nitro-N-phenylquinolin-5-amine (6a). The first
fraction of yellow color, eluent PhMe. Yield 16 mg (12%),
light-yellow crystals, mp 201–202°С (PhH). 1H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 6.58 (1H, s, NH); 7.15
(1H, d, J = 8.6, H-6 Quin); 7.21 (1H, t, J = 7.4, H-4' Ph);
7.25 (2H, d, J = 8.1, H-2',6' Ph); 7.40–7.46 (2H, m, H-3',5'
Ph); 7.52 (1H, dd, J = 8.6, J = 4.1, H-3 Quin); 8.15 (1H, d,
J = 8.6, H-7 Quin); 8.40 (1H, dd, J = 8.6, J = 1.5, H-4 Quin);
4-Nitro-N-(4-nitrophenyl)quinolin-6-amine
(3g).
The second fraction of yellowish-orange color, eluent
881

Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
9.13 (1H, dd, J = 4.1, J = 1.5, H-2 Quin). 13C NMR
H-4 Quin); 9.12 (1H, dd, J = 4.1, J = 1.4, H-2 Quin).
13C NMR spectrum (CDCl3), δ, ppm: 55.7; 105.1; 115.4;
118.2; 121.1; 126.0; 128.9; 129.3; 132.2; 138.5; 142.0; 147.3;
152.7; 157.9. Found, m/z: 296.1032 [М+H]+. C16H14N3O3.
Calculated, m/z: 296.1030.
spectrum (CDCl3), δ, ppm: 107.3; 119.6; 121.4; 122.1
(2С); 125.0; 128.1; 129.7; 130.1; 140.2; 141.9; 145.4;
152.8. Found, m/z: 266.0943 [М+H]+. C15H12N3O2.
Calculated, m/z: 266.0924.
8-Nitroso-N-phenylquinolin-7-amine (7a). The second
fraction of brown color, eluent EtOAc. Yield 60 mg (48%),
dark-green crystals, mp 137–138°С (PhH). 1H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 7.23 (1H, d, J = 9.6, H-6 Quin); 7.30
(2H, d, J = 7.5, H-2',6' Ph); 7.37 (1H, t, J = 7.5, H-4' Ph); 7.45–
7.51 (3H, m, H-3 Qu, H-3',5' Ph); 7.71 (1H, d, J = 9.6, H-5
Quin); 8.00 (1H, dd, J = 8.0, J = 1.6, H-4 Quin); 9.09 (1H, dd,
J = 4.5, J = 1.6, H-2 Quin); 15.78 (1H, br. s, NH). 1H NMR
spectrum (DMSO-d6), δ, ppm (J, Hz): 7.23 (1H, d, J = 9.6,
H-6 Quin); 7.41 (1H, t, J = 7.3, H-4' Ph); 7.45 (2H, d,
J = 7.6, H-2',6' Ph); 7.49–7.53 (2H, m, H-3',5' Ph); 7.61 (1H,
dd, J =8.0, J = 4.4, H-3 Quin); 8.03 (1H, d, J = 9.6, H-5 Quin);
8.29 (1H, dd, J = 8.0, J = 1.5, H-4 Quin); 8.98 (1H, dd,
J = 4.4, J = 1.5, H-2 Quin); 15.43 (1H, br. s, NH). 13C NMR
spectrum (CDCl3), δ, ppm: 117.6 (C-6); 121.5 (C-4a); 121.8
(C-3); 125.5 (C-2',6'); 127.8 (C-4'); 130.0 (C-3',5'); 136.4
(C-1'); 136.6 (C-4); 137.0 (C-7); 140.2 (C-5); 149.0
(C-8,8а); 152.7 (C-2). Found, m/z: 250.0973 [М+H]+.
C15H12N3O. Calculated, m/z: 250.0975.
N-(4-Methoxyphenyl)-8-nitrosoquinolin-7-amine (7c).
The second fraction of brown color, eluent EtOAc. Yield
58.6 mg (42%), dark-brown crystals, mp 134–135°С
(decomp., EtOAc). 1H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 3.86 (3H, s, CH3); 6.99 (2H, d, J = 8.8, H-2',6' Ar);
7.18 (1H, d, J = 9.6, H-5 Quin); 7.22 (2H, d, J = 8.8,
H-3',5' Ar); 7.46 (1H, dd, J = 8.0, J = 4.5, H-3 Quin); 7.69
(1H, d, J = 9.6, H-6 Quin); 7.99 (1H, dd, J = 8.0, J = 1.5,
H-4 Quin); 9.06 (1H, dd, J = 4.5, J = 1.5, H-2 Quin); 15.74
(1H, br. s, NH). 13C NMR spectrum (CDCl3), δ, ppm: 55.7;
115.2; 117.7; 121.3; 121.7; 126.9; 128.7; 136.5; 137.5;
140.0; 149.0; 149.1; 152.6; 159.1. Found, m/z: 280.1081
[М+H]+. C16H14N3O2. Calculated, m/z: 280.1081.
N-(4-Bromophenyl)-8-nitroquinolin-5-amine (6d).
The first fraction of yellow color, eluent PhMe. Yield
10 mg (6%), yellowish-orange crystals, mp 194–195°С (PhH).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 6.47 (1H, s,
NH); 7.11 (2H, d, J = 8.7, H-2',6' Ar); 7.15 (1H, d, J = 8.6, H-6
Quin); 7.50–7.56 (3H, m, H-3 Qu, H-3',5' Ar); 8.14 (1H, d,
J = 8.6, H-7 Quin); 8.38 (1H, dd, J = 8.6, J = 1.6, H-4
Quin); 9.13 (1H, dd, J = 4.2, J = 1.6, H-2 Quin). 13C NMR
spectrum (CDCl3), δ, ppm: 108.3; 117.2; 120.0; 121.6; 123.2;
127.6; 129.7; 133.1; 139.7; 140.7; 141.7; 144.6; 152.9.
Found, m/z: 344.0035 [М(79Br)+H]+. C15H11BrN3O2.
Calculated, m/z: 344.0029.
N-(4-Bromophenyl)-8-nitrosoquinolin-7-amine (7d).
The second fraction of brown color, eluent PhMe–EtOAc, 7:3.
Yield 59 mg (36%), brown crystals, mp 150–151°С
(decomp., PhMe). 1H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 7.15–7.20 (3H, m, H-2',6' Ar, H-5 Quin); 7.50 (1H,
dd, J = 8.0, J = 4.5, H-3 Quin); 7.60 (2H, d, J = 8.6, H-3',5'
Ar); 7.73 (1H, d, J = 9.6, H-6 Quin); 8.01 (1H, br. d,
J = 7.9, H-4 Quin); 9.09 (1H, br. d, J = 3.3, H-2 Quin);
15.73 (1H, br. s, NH). 13C NMR spectrum (CDCl3), δ, ppm:
117.2; 121.2; 121.7; 122.0; 127.0; 133.2; 135.8; 136.6;
137.0; 140.4; 148.8; 148.9; 152.9. Found, m/z: 328.0078
[М(79Br)+H]+. C15H11BrN3O. Calculated, m/z: 328.0080.
Found, m/z: 349.9921 [М(79Br)+Na]+. C15H10BrN3NaO.
Calculated, m/z: 349.9899.
8-Nitro-N-(p-tolyl)quinolin-5-amine (6b). The first
fraction of yellow color, eluent PhMe. Yield 20 mg (14%),
1
yellow crystals, mp 191–192°С (PhH). H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 2.39 (3H, s, CH3); 6.55 (1H, s,
NH); 7.02 (1H, d, J = 8.7, H-6 Quin); 7.16 (2H, d, J = 8.3,
H-2',6' Ar); 7.25 (2H, d, J = 8.3, H-3',5' Ar); 7.52 (1H, dd,
J = 8.7, J = 4.1, H-3 Quin); 8.16 (1H, d, J = 8.7, H-7 Quin);
8.38 (1H, dd, J = 8.7, J = 1.5, H-4 Quin); 9.13 (1H, dd,
J = 4.1, J = 1.5, H-2 Quin). 13C NMR spectrum (CDCl3),
δ, ppm: 21.1 (CH3); 106.2 (C-6); 118.9 (C-4a); 121.2
(C-3); 123.1 (C-2',6'); 128.5 (C-7); 129.5 (C-4); 130.7
(C-3',5'); 135.3 (C-4'); 137.2 (C-1'); 139.2 (C-8); 142.0
(C-8a); 146.3 (C-5); 152.7 (C-2). Found, m/z: 280.1087
[М+H]+. C16H14N3O2. Calculated, m/z: 280.1081.
8-Nitroso-N-(p-tolyl)quinolin-7-amine (7b). The second
fraction of brown color, eluent EtOAc. Yield 58 mg (44%),
light-brown crystals, mp 241–242°С (decomp., EtOAc).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.41 (3H, s,
CH3); 7.17 (2H, d, J = 8.2, H-2',6' Ar); 7.23 (1H, d, J = 9.6,
H-5 Quin); 7.27 (2H, d, J = 8.2, H-3',5' Ar); 7.47 (1H, dd,
J = 8.0, J = 4.4, H-3 Quin); 7.69 (1H, d, J = 9.6, H-6 Quin);
7.99 (1H, dd, J = 8.0, J = 1.6, H-4 Quin); 9.07 (1H, dd,
J = 4.4, J = 1.6, H-2 Quin); 15.76 (1H, br. s, NH).
13C NMR spectrum (CDCl3), δ, ppm: 21.3; 117.7; 121.4;
121.7; 125.4; 130.6; 133.5; 136.5; 137.1; 137.9; 140.0;
149.0; 149.1; 152.7. Found, m/z: 264.1148 [М+H]+.
C16H14N3O. Calculated, m/z: 264.1131.
N-(4-Methoxyphenyl)-8-nitroquinolin-5-amine (6c).
The first fraction of yellow color, eluent PhMe. Yield
12 mg (8%), orange crystals, mp 194–195°С (PhH).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 3.86 (3H, s,
CH3); 6.57 (1H, s, NH); 6.82 (1H, d, J = 8.7, H-6 Quin);
6.99 (2H, d, J = 8.8, H-2',6' Ar); 7.22 (2H, d, J = 8.8,
H-3',5' Ar); 7.51 (1H, dd, J = 8.6, J = 4.1, H-3 Quin); 8.15
(1H, d, J = 8.7, H-7 Quin); 8.36 (1H, dd, J = 8.6, J = 1.4,
N-(4-Fluorophenyl)-8-nitroquinolin-5-amine (6e).
The first fraction of yellow color, eluent PhMe. Yield
13 mg (9%), yellowish-green crystals, mp 215–216°С
1
(PhH). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 6.53
(1H, s, NH); 6.94 (1H, d, J = 8.6, H-6 Quin); 7.11–7.16 (2H,
m, H-2',6' Ar); 7.21–7.26 (2H, m, H-3',5' Ar); 7.53 (1H, dd,
J = 8.6, J = 4.2, H-3 Quin); 8.14 (1H, d, J = 8.6, H-7 Quin);
8.38 (1H, dd, J = 8.6, J = 1.3, H-4 Quin); 9.13 (1H, dd,
J = 4.2, J = 1.3, H-2 Quin). 13C NMR spectrum (CDCl3), δ, ppm
(J, Hz): 106.3; 117.0 (d, 2JCF = 22.7); 119.0; 121.4; 125.1 (d,
3JCF = 8.1); 128.2; 129.4; 135.9; 139.7; 141.8; 146.1; 152.8;
1
160.3 (d, JCF = 244.0). Found, m/z: 284.0839 [М+H]+.
C15H11FN3O2. Calculated, m/z: 284.0830.
N-(4-Fluorophenyl)-8-nitrosoquinolin-7-amine (7e).
The second fraction of brown color, eluent EtOAc. Yield
882

Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
60 mg (45%), orange-brown crystals, mp 127–128°С
J = 1.1, H-4 Quin); 9.08 (1H, dd, J = 4.2, J = 1.1, H-2
Quin); 9.84 (1H, br. s, NH). 13C NMR spectrum (DMSO-d6),
δ, ppm: 114.3; 116.4; 122.2; 122.4; 125.4; 126.0; 132.2;
140.0; 140.1; 141.3; 142.7; 149.8; 153.0. Found, m/z:
311.0768 [М+H]+. C15H11N4O4. Calculated, m/z: 311.0775.
(EtOAc). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.14
(1H, d, J = 9.6, H-5 Quin); 7.19 (2H, d, J = 8.2, H-2',6' Ar);
7.26–7.30 (2H, m, H-3',5' Ar); 7.49 (1H, dd, J = 8.0,
J = 4.4, H-3 Quin); 7.73 (1H, d, J = 9.6, H-6 Quin); 8.01
(1H, dd, J = 8.0, J = 1.6, H-4 Quin); 9.09 (1H, dd, J = 4.4,
J = 1.6, H-2 Quin); 15.68 (1H, br. s, NH). 13C NMR
N-(2-Chlorophenyl)-8-nitroquinolin-5-amine
(6h).
The fraction of yellow color, eluent PhMe. Yield 63 mg
2
1
spectrum (CDCl3), δ, ppm (J, Hz): 117.1 (d, JCF = 22.7);
(42%), orange crystals, mp 178–179°С (PhH). H NMR
3
117.2; 121.5; 121.9; 127.4 (d, JCF = 8.4); 132.4; 136.6;
spectrum (CDCl3), δ, ppm (J, Hz): 6.75 (1H, s, NH); 7.09
(1H, m, H-4' Ar); 7.26–7.30 (2H, m, H-6 Qu, H-5' Ar);
7.34 (1H, br. d, J = 7.5, H-6' Ar); 7.51 (1H, br. d, J = 8.0,
H-3' Ar); 7.58 (1H, dd, J = 8.6, J = 4.1, H-3 Quin); 8.15 (1H, d,
J = 8.5, H-7 Quin); 8.47 (1H, dd, J = 8.6, J = 0.8, H-4 Quin);
9.15 (1H, dd, J = 4.1, J = 0.8, H-2 Quin). 13C NMR
spectrum (CDCl3), δ, ppm: 110.3; 120.4, 121.2; 121.9;
124.4; 125.1; 127.1; 128.0; 130.2; 130.5; 137.9; 141.6
(2С); 143.4; 152.9. Found, m/z: 300.0542 [М(35Cl)+H]+.
C15H11ClN3O2. Calculated, m/z: 300.0534.
1
137.3; 140.4; 148.9; 149.0; 152.9; 161.7 (d, JCF = 247.0).
Found, m/z: 268.0882 [М+H]+. C15H11FN3O. Calculated, m/z:
268.0881.
8-Nitro-N-[4-(trifluoromethyl)phenyl]quinolin-5-amine (6f).
The first fraction of yellow color, eluent PhMe. Yield
17 mg (10%), bright-orange crystals, mp 199–200°С
1
(PhMe). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 6.54
(1H, s, NH); 7.22 (2H, d, J = 8.5, H-2',6' Ar); 7.38 (1H, d,
J = 8.5, H-6 Quin); 7.56 (1H, dd, J = 8.7, J = 4.1, H-3
Quin); 7.62 (2H, d, J = 8.5, H-3',5' Ar); 8.14 (1H, d,
J = 8.5, H-7 Quin); 8.41 (1H, dd, J = 8.7, J = 1.5, H-4
Quin); 9.14 (1H, dd, J = 4.1, J = 1.5, H-2 Quin). 13C NMR
spectrum (CDCl31), δ, ppm (J, Hz): 111.3; 119.1; 121.5;
8-Nitro-N-(2,4,6-tribromophenyl)quinolin-5-amine (6i).
The fraction of yellow color, eluent PhMe. Yield 45 mg (18%),
1
brown crystals, mp 190–191°С (PhMe). H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 6.38 (1H, d, J = 8.5, H-6 Quin); 6.44
(1H, br. s, NH); 7.61 (1H, dd, J = 8.6, J = 4.2, H-3 Quin); 7.85
(2H, s, H-3',5' Ar); 8.07 (1H, d, J = 8.5, H-7 Quin); 8.53
(1H, br. d, J = 8.4, H-4 Quin); 9.15 (1H, br. d, J = 3.2, H-2
Quin). 13C NMR spectrum (CDCl3), δ, ppm: 107.7; 119.5;
120.7; 121.8; 123.2; 127.2; 129.8; 135.7; 136.5; 141.1;
141.5; 143.6; 152.8. Found, m/z: 499.8222 [М(79Br)+H]+.
C15H9Br3N3O2. Calculated, m/z: 499.8239.
2
122.0; 124.2 (q, J = 269.7); 125.2 (q, J = 32.6); 126.8;
127.4; 130.4; 141.4; 142.2; 143.0; 144.7 (2С); 152.9.
Found, m/z: 334.0798 [М+H]+. C16H11F3N3O2. Calculated,
m/z: 334.0798.
8-Nitroso-N-[4-(trifluoromethyl)phenyl]quinolin-7-amine
(7f). The second fraction of brown color, eluent EtOAc.
Yield 25 mg (16%), dark-green crystals, mp 158–159°С
1
(PhMe). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.21
7-Nitro-N-phenylquinolin-8-amine (10a). The fraction
of yellow color, eluent PhMe. Yield 81 mg (61%), yellowish-
(1H, d, J = 9.6, H-6 Quin); 7.41 (2H, d, J = 8.2, H-2',6' Ar);
7.52 (1H, dd, J = 8.0, J = 4.5, H-3 Quin); 7.72–7.77 (3H,
m, H-5 Qu, H-3',5' Ar); 8.02 (1H, br. d, J = 7.7, H-4 Quin);
9.08–9.10 (1H, m, H-2 Quin); 15.80 (1H, br. s, NH).
13C NMR spectrum (CDCl3), δ, ppm (J, Hz): 117.0 (C-6);
122.0 (C-1'); 122.2 (C-3); 123.8 (q, 1J = 270.8, CF3); 125.2
(C-2',6'); 127.2 (q, 3J = 3.5, C-3',5'); 129.2 (q, 2J = 32.8, C-4');
136.7 (C-7); 136.9 (C-4); 140.5 (C-4a); 140.7 (C-5); 148.6
(C-8,8a); 152.9 (C-2). Found, m/z: 318.0847 [М+H]+.
C16H11F3N3O. Calculated, m/z: 318.0849.
1
orange crystals, mp 162–163°С (CHCl3). H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 7.03 (2H, d, J = 8.0, H-2',6' Ph);
7.11 (1H, t, J = 7.4, H-4' Ph); 7.25 (1H, d, J = 9.2, H-5 Quin);
7.32 (2H, m, H-3',5' Ph); 7.59 (1H, dd, J = 8.2, J = 4.2, H-3
Quin); 8.05 (1H, d, J = 9.2, H-6 Quin); 8.17 (1H, dd,
J = 8.2, J = 1.4, H-4 Quin); 8.84 (1H, dd, J = 4.2, J = 1.4, H-2
Quin); 9.37 (1H, s, NH). 13C NMR spectrum (CDCl3),
δ, ppm: 116.9; 119.4; 123.5; 124.4 (2С); 129.2; 130.6; 133.0;
136.5; 136.6; 140.9; 141.1; 148.8. Found, m/z: 288.0737
[М+Na]+. C15H11N3NaO2. Calculated, m/z: 288.0743.
7-Nitro-N-(p-tolyl)quinolin-8-amine (10b). The fraction
of yellow color, eluent PhMe. Yield 80 mg (57%), orange
crystals, mp 133–134°С (CHCl3). 1H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 2.33 (3H, s, CH3); 6.93 (2H, d,
J = 8.3, H-2',6' Ar); 7.12 (2H, d, J = 8.3, H-3',5' Ar); 7.21 (1H,
d, J = 9.2, H-5 Quin); 7.58 (1H, dd, J = 8.2, J = 4.2, H-3 Quin);
8.03 (1H, d, J = 9.2, H-6 Quin); 8.15 (1H, dd, J = 8.2, J = 1.5,
H-4 Quin); 8.82 (1H, dd, J = 4.2, J = 1.5, H-2 Quin); 9.33
(1H, s, NH). 13C NMR spectrum (CDCl3), δ, ppm: 21.1
(C-CH3); 116.4 (C-5); 119.5 (C-2',6'); 123.6 (C-6); 124.4
(C-3); 129.7 (C-3',5'); 130.6 (C-4a); 132.6 (C-7); 134.2 (C-4');
136.4 (C-4); 137.0 (C-8); 138.3 (C-1'); 141.1 (C-8a); 148.6
(C-2). Found, m/z: 302.0900 [М+Na]+. C16H13N3NaO2.
Calculated, m/z: 302.0898.
8-Nitro-N-(4-nitrophenyl)quinolin-5-amine
(6g).
The first fraction of yellow color, eluent PhMe. Yield
28 mg (18%), light-yellow crystals, mp 261–262°С (PhMe).
1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 7.32 (2H,
d, J = 9.2, H-2',6' Ar); 7.64 (1H, d, J = 8.4, H-6 Quin); 7.77
(1H, dd, J = 8.5, J = 4.2, H-3 Quin); 8.18 (2H, d, J = 9.2,
H-3',5' Ar); 8.28 (1H, d, J = 8.4, H-7 Quin); 8.38 (1H, dd,
J = 8.5, J = 0.8, H-4 Quin); 9.08 (1H, dd, J = 4.2, J = 0.8,
H-2 Quin); 9.84 (1H, br. s, NH). 13C NMR spectrum (DMSO-d6),
δ, ppm: 114.3; 116.4, 122.2; 122.4; 125.4; 126.0; 132.1;
140.0; 140.2; 141.3; 142.7; 149.8; 153.0. Found, m/z:
311.0774 [М+H]+. C15H11N4O4. Calculated, m/z: 311.0775.
8-Nitro-N-(4-nitrophenyl)quinolin-7-amine (8). The
second fraction of orange color, eluent PhMe. Yield 12 mg
(8%), dark-orange crystals, mp 271–272°С (PhMe).
1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 7.32 (2H, d,
J = 9.1, H-2',6' Ar); 7.64 (1H, d, J = 8.4, H-5 Quin); 7.77 (1H,
dd, J = 8.6, J = 4.2, H-3 Quin); 8.19 (2H, d, J = 9.1, H-3',5'
Ar); 8.28 (1H, d, J = 8.4, H-6 Quin); 8.73 (1H, dd, J = 8.6,
N-(4-Methoxyphenyl)-7-nitroquinolin-8-amine (10c).
The fraction of yellow color, eluent PhMe. Yield 93 mg
(63%), pale-yellow crystals, mp 118–119°С (CHCl3).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 3.80 (3H, s,
883

Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
OCH3); 6.86 (2H, d, J = 8.8, H-2',6' Ar); 7.00 (2H, d,
6-Nitro-N-phenylquinolin-5-amine (12a). The fraction
of yellow color, eluent PhMe. Yield 70 mg (53%), dark-
orange crystals, mp 129–130°С (CHCl3). 1H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 6.94 (2H, d, J = 7.9,
H-2',6' Ph); 7.09 (1H, t, J = 7.4, H-4' Ph); 7.18 (1H, dd,
J = 8.7, J = 4.2, H-3 Quin); 7.26 (2H, m, H-3',5' Ph); 7.69 (1H,
d, J = 9.5, H-8 Quin); 8.25 (1H, br. d, J = 8.7, H-4 Quin);
8.38 (1H, d, J = 9.5, H-7 Quin); 8.93 (1H, dd, J = 4.2,
J = 1.4, H-2 Quin); 9.72 (1H, s, NH). 13C NMR spectrum
(CDCl3), δ, ppm: 120.4 (C-3); 120.8 (C-2',6'); 121.9
(C-4a); 123.4 (C-8); 124.3 (C-4'); 125.1 (C-7); 129.8
(C-3'); 135.4 (C-6); 136.2 (C-4); 140.2 (C-5); 143.7 (C-1');
151.6 (C-8a); 153.4 (C-2). Found, m/z: 266.0929 [М+H]+.
C15H12N3O2. Calculated, m/z: 266.0924.
6-Nitro-N-(p-tolyl)quinolin-5-amine (12b). The fraction
of yellow color, eluent PhMe. Yield 85 mg (61%), dark-red
crystals, mp 110–111°С (CHCl3). 1H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 2.32 (3H, s, CH3); 6.87 (2H, d,
J = 8.3, H-2',6' Ar); 7.07 (2H, d, J = 8.3, H-3',5' Ar); 7.16
(1H, dd, J = 8.7, J = 4.2, H-3 Quin); 7.63 (1H, d, J = 9.5,
H-8 Quin); 8.24 (1H, br. d, J = 8.7, H-4 Quin); 8.37 (1H, d,
J = 9.5, H-7 Quin); 8.91 (1H, dd, J = 4.2, J = 1.5, H-2 Quin);
9.85 (1H, s, NH). 13C NMR spectrum (CDCl3), δ, ppm:
21.0; 120.1; 121.3; 121.7; 122.7; 125.2; 130.4; 134.3; 134.6;
136.3; 141.0; 141.1; 151.7; 153.3. Found, m/z: 280.1070
[М+H]+. C16H14N3O2. Calculated, m/z: 280.1081.
N-(4-Methoxyphenyl)-6-nitroquinolin-5-amine (12c).
The fraction of yellow color, eluent PhMe. Yield 61 mg
(41%), bright-red crystals, mp 141–142°С (CHCl3).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 3.80 (3H, s,
OCH3); 6.83 (2H, d, J = 8.8, H-2',6' Ar); 6.96 (2H, d,
J = 8.8, H-3',5' Ar); 7.14 (1H, dd, J = 8.6, J = 4.2, H-3 Quin);
7.58 (1H, d, J = 9.5, H-8 Quin); 8.22 (1H, br. d, J = 8.6,
H-4 Quin); 8.38 (1H, d, J = 9.5, H-7 Quin); 8.89 (1H, br. d,
J = 4.2, H-2 Quin); 10.02 (1H, br. s, NH). 13C NMR
spectrum (CDCl3), δ, ppm: 55.7; 115.1; 120.0; 121.3;
122.1; 123.5; 125.3; 133.7; 136.3; 136.6; 142.0; 151.9;
153.2; 157.0. Found, m/z: 296.1027 [М+H]+. C16H14N3O3.
Calculated, m/z: 296.1030.
J = 8.8, H-3',5' Ar); 7.18 (1H, d, J = 9.2, H-5 Quin); 7.57
(1H, dd, J = 8.2, J = 4.2, H-3 Quin); 8.01 (1H, d, J = 9.2,
H-6 Quin); 8.15 (1H, br. d, J = 8.2, H-4 Quin); 8.81 (1H, br. d,
J = 4.2, H-2 Quin); 9.32 (1H, s, NH). 13C NMR spectrum
(CDCl3), δ, ppm: 55.6; 114.4; 116.0; 121.3; 123.7; 124.4;
130.6; 132.1; 134.1; 136.4; 137.6; 141.1; 148.5; 156.7.
Found, m/z: 318.0853 [М+Na]+. C16H13N3NaO3.
Calculated, m/z: 318.0849.
N-(4-Bromophenyl)-7-nitroquinolin-8-amine (10d).
The fraction of yellow color, eluent PhMe. Yield 100 mg
(58%), yellowish-orange crystals, mp 188–189°С (CHCl3).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 6.90 (2H, d,
J = 8.7, H-2',6' Ar); 7.29 (1H, d, J = 9.2, H-5 Quin); 7.41
(2H, d, J = 8.7, H-3',5' Ar); 7.60 (1H, dd, J = 8.2, J = 4.2, H-3
Quin); 8.07 (1H, d, J = 9.2, H-6 Quin); 8.18 (1H, dd, J = 8.2,
J = 1.4, H-4 Quin); 8.84 (1H, dd, J = 4.2, J = 1.4, H-2
Quin); 9.32 (1H, s, NH). 13C NMR spectrum (CDCl3), δ, ppm:
116.9; 117.5; 121.1; 123.3; 124.6; 130.7; 132.1; 133.3;
136.4; 136.6; 140.2; 141.0; 148.9. Found, m/z: 365.9853
[М(79Br)+Na]+. C15H10BrN3NaO2. Calculated, m/z: 365.9849.
N-(4-Fluorophenyl)-7-nitroquinolin-8-amine (10e).
The fraction of yellow color, eluent PhMe. Yield 69 mg
1
(49%), orange crystals, mp 156–157°С (CHCl3). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 7.00–7.02 (4H, m,
H-2',3',5',6' Ar); 7.25 (1H, d, J = 9.2, H-5 Quin); 7.59 (1H,
dd, J = 8.2, J = 4.1, H-3 Quin); 8.04 (1H, d, J = 9.2, H-6
Quin); 8.17 (1H, dd, J = 8.2, J = 1.1, H-4 Quin); 8.83 (1H,
dd, J = 4.2, J = 1.1, H-2 Quin); 9.32 (1H, s, NH). 13C NMR
2
spectrum (CDCl3), δ, ppm (J, Hz): 116.0 (d, JCF = 22.7);
3
116.9; 121.5 (d, JCF = 8.1); 123.5; 124.5; 130.7; 132.7;
4
136.5; 137.2 (2С, d, JCF = 2.8); 140.9; 148.7; 159.7 (d,
1JCF
=
242.0). Found, m/z: 306.0642 [М+Na]+.
C15H10FN3NaO2. Calculated, m/z: 306.0649.
7-Nitro-N-[4-(trifluoromethyl)phenyl)]quinolin-8-amine
(10f). The fraction of yellow color, eluent PhMe. Yield 62 mg
(37%), orange crystals, mp 142–143°С (CHCl3). H NMR
1
spectrum (CDCl3), δ, ppm (J, Hz): 7.05 (2H, d, J = 8.4,
H-2',6' Ar); 7.38 (1H, d, J = 9.2, H-5 Quin); 7.55 (2H, d,
J = 8.4, H-3',5' Ar); 7.62 (1H, dd, J = 8.2, J = 4.1, H-3
Quin); 8.12 (1H, d, J = 9.2, H-6 Quin); 8.21 (1H, br. d,
J = 8.2, H-4 Quin); 8.87 (1H, dd, J = 4.2, J = 1.2, H-2
Quin); 9.42 (1H, s, NH). 13C NMR spectrum (CDCl3), δ, ppm
N-(4-Bromophenyl)-6-nitroquinolin-5-amine (12d).
The fraction of yellow color, eluent PhMe. Yield 43 mg
(25%), bright-yellow crystals, mp 142–143°С (petroleum
1
ether). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 6.79
1
(J, Hz): 118.6; 118.7; 123.2; 124.3 (q, J = 267.8); 124.7;
(2H, d, J = 8.7, H-2',6' Ar); 7.25 (1H, dd, J = 8.6, J = 4.2, H-3
Quin); 7.36 (2H, d, J = 8.7, H-3',5' Ar); 7.75 (1H, d, J = 9.5,
H-8 Quin); 8.24 (1H, br. d, J = 8.7, H-4 Quin); 8.37 (1H, d,
J = 9.5, H-7 Quin); 8.91 (1H, dd, J = 4.2, J = 1.5, H-2
Quin); 9.85 (1H, s, NH). 13C NMR spectrum (CDCl3),
δ, ppm: 116.6; 120.7; 121.9; 122.0; 124.2; 125.0; 132.8;
135.9; 136.1; 139.2; 142.9; 151.5; 153.6. Found, m/z:
344.0022 [М(79Br)+H]+. C15H11BrN3O2. Calculated, m/z:
344.0029.
2
3
125.7 (q, J = 25.2); 126.4 (q, J = 3.7); 130.8; 134.3;
135.5; 136.6; 141.1; 144.2; 149.2. Found, m/z: 356.0629
[М+Na]+. C16H10F3N3NaO2. Calculated, m/z: 356.0617.
7-Nitro-N-(4-nitrophenyl)quinolin-8-amine (10g).
The fraction of yellow color, eluent PhMe. Yield 45 mg
(29%), bright-yellow crystals, mp 152–153°С (CHCl3).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.00 (2H, d,
J = 8.9, H-2',6' Ar); 7.50 (1H, d, J = 9.2, H-5 Quin); 7.65
(1H, dd, J = 8.3, J = 4.2, H-3 Quin); 8.14–8.20 (3H, m, H-6
Quin and H-3',5' Ar); 8.25 (1H, br. d, J = 8.3, H-4 Quin);
8.90 (1H, br. d, J = 4.2, H-2 Quin); 9.46 (1H, br. s, NH).
13C NMR spectrum (CDCl3), δ, ppm: 118.0; 120.2; 122.9;
124.8; 125.3; 130.9; 134.4; 135.6; 136.7; 141.1; 143.0; 147.3;
149.7. Found, m/z: 333.0583 [М+Na]+. C15H10N4NaO4.
Calculated, m/z: 333.0549.
N-(4-Fluorophenyl)-6-nitroquinolin-5-amine (12e). The
fraction of yellow color, eluent PhMe. Yield 54 mg (38%),
1
orange crystals, mp 147–148°С (CHCl3). H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 6.91–6.99 (4H, m, H-2'3',5',6' Ar);
7.20 (1H, dd, J = 8.7, J = 4.2, H-3 Quin); 7.68 (1H, d,
J = 9.5, H-8 Quin); 8.19 (1H, br. d, J = 8.7, H-4 Quin);
8.38 (1H, d, J = 9.5, H-7 Quin); 8.93 (1H, dd, J = 4.2,
884

Chemistry of Heterocyclic Compounds 2018, 54(9), 875–886
J = 1.0, H-2 Quin); 9.73 (1H, br. s, NH). 13C NMR
second fraction of orange color, eluent PhMe. Yield 17 mg
2
spectrum (CDCl3), δ, ppm (J, Hz): 116.7 (d, J = 22.7);
(7%), orange crystals, mp 231–232°С (petroleum ether).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.65 (2Н, d,
J = 8.6, H-2',6' Ar); 7.72 (2Н, d, J = 8.6, H-3',5' Ar); 7.82
(1Н, s, H-6); 7.86 (1H, dd, J = 8.1, J = 4.5, H-2); 7.90 (1H,
dd, J = 8.8, J = 1.7, Н-10); 8.38 (1Н, d, J = 8.8, H-11); 8.47
(1Н, br. s, H-8); 9.10 (1Н, dd, J = 4.5, J = 1.6, H-3); 9.14
(1Н, br. s, NH); 9.67 (1Н, dd, J = 8.1, J = 1.6, H-1).
13C NMR spectrum (CDCl3), δ, ppm: 102.7; 116.8; 120.7;
120.9; 122.6; 123.0; 123.7 (2C); 123.8; 124.1 (2C); 125.3
(2C); 125.7 (2C); 126.7 (2C); 126.8; 127.0; 127.1 (3C);
128.4; 129.2; 129.3; 130.9; 131.8; 132.1; 132.2; 134.5; 140.6;
141.2; 142.0; 142.5; 143.2; 143.7; 146.5; 150.9. Found,
m/z: 475.0982 [M+H]+. С23Н13F6N4О. Calculated, m/z:
475.0988.
3
120.4; 121.6; 122.8 (d, J = 8.0); 123.4; 125.1; 135.1;
4
136.0; 139.8 (d, J = 2.9); 140.6; 151.7; 153.5; 159.6 (d,
1J = 242.9). Found, m/z: 284.0837 [М+H]+. C15H11FN3O2.
Calculated, m/z: 284.0830.
6-Nitro-N-[4-(trifluoromethyl)phenyl]quinolin-5-amine
(12f). The fraction of yellow color, eluent PhMe. Yield 38 mg
(23%), orange crystals, mp 113–114°С (petroleum ether).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 6.91 (2H, d,
J = 8.5, H-2',6' Ar); 7.33 (1H, dd, J = 8.7, J = 4.2, H-3 Quin);
7.48 (2H, d, J = 8.5, H-3',5' Ar); 7.87 (1H, d, J = 9.4, H-8
Quin); 8.23 (1H, br. d, J = 8.7, H-4 Quin); 8.39 (1H, d,
J = 9.4, H-7 Quin); 9.01 (1H, br. d, J = 4.2, H-2 Quin);
9.29 (1H, br. s, NH). 13C NMR spectrum (CDCl3), δ, ppm
1
(J, Hz): 118.8; 121.3; 122.5; 124.2 (q, J = 269.7); 124.6;
X-ray structural studies of compounds 4b and 14f
were performed on an Agilent SuperNova diffractometer
using microfocus X-ray source with copper anode and
Atlas S2 CCD detector. Crystals suitable for X-ray
structural analysis were obtained by slow evaporation of
chloroform solution at room temperature. The collection of
reflexes, determination and refinement of unit cell
parameters were performed by using the specialized
CrysAlisPro 1.171.38.41 software suite (Rigaku Oxford
Diffraction, 2015).21 The structures were solved by using
ShelXT program (Sheldrick, 2015),22 structure refinement
was also performed with ShelXL program (Sheldrick,
2015).23 Molecular graphics were rendered and prepared
for publication with the Olex2 version 1.2.10 software
suite.24 The complete X-ray diffraction datasets were
deposited at the Cambridge Crystallographic Data Center
(deposits CCDC 1854534 (compound 4b) and CCDC
1854919 (compound 14f)).
2
3
124.9; 125.3 (q, J = 23.6); 127.0 (q, J = 3.7); 135.6;
137.4; 137.5; 146.9; 151.1; 153.8. Found, m/z: 334.0805
[М+H]+. C16H11F3N3O2. Calculated, m/z: 334.0798.
6-Nitro-N-(4-nitrophenyl)quinolin-5-amine
(12g).
The fraction of yellow color, eluent PhMe. Yield 76 mg
(49%), bright-orange crystals, mp 199–200°С (CHCl3).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 6.83 (2H, d,
J = 9.0, H-2',6' Ar); 7.40 (1H, dd, J = 8.6, J = 4.2, H-3
Quin); 8.00 (1H, d, J = 9.4, H-8 Quin); 8.11 (2H, d, J = 9.0,
H-3',5' Ar); 8.22 (1H, br. d, J = 8.6, H-4 Quin); 8.39 (1H,
d, J = 9.4, H-7 Quin); 9.04–9.08 (2H, m, H-2 Quin, NH).
13C NMR spectrum (CDCl3), δ, ppm: 117.4; 121.9; 123.0;
124.7; 126.0; 127.1; 135.1; 135.2; 139.0; 142.4; 149.6; 150.9;
154.1. Found, m/z: 311.0766 [М+H]+. C15H11N4O4.
Calculated, m/z: 311.0775.
9-Methoxypyrido[3,2-a]phenazine 7-oxide (13c). The
third fraction of pale-yellow color, eluent PhMe–EtOAc, 7:3.
Yield 8 mg (6%), dark-orange crystals, mp 232–233°С
1
1
(CHCl3). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 4.08
A Supplementary information file containing Н and 13С
(3H, s, OCH3); 7.55 (1H, dd, J = 9.3, J = 2.5, H-10); 7.70
(1H, dd, J = 8.2, J = 3.0, H-2); 8.01 (1H, d, J = 2.5, H-8);
8.21 (1H, d, J = 9.3, H-11); 8.22 (1H, d, J = 9.8, H-6); 8.82
(1H, d, J = 9.8, H-5); 9.09 (1H, d, J = 3.0, H-3); 9.57 (1H,
d, J = 8.2, H-1). 13C NMR spectrum (CDCl3), δ, ppm: 56.6;
96.2; 120.1; 122.9; 126.1; 127.0; 131.9; 133.0; 133.2;
133.7; 136.4; 141.0; 141.6; 149.5; 152.3; 162.0. Found, m/z:
300.0729 [М+Na]+. С16Н11N3NaО2. Calculated, m/z: 300.0743.
9-Bromo-5-[(4-bromophenyl)amino]pyrido[3,2-a]phen-
azine 7-oxide (14d). The second fraction of yellow color,
eluent PhMe. Yield 37 mg (15%), orange-red crystals,
mp 257–258°С (petroleum ether). 1H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 7.45 (2Н, d, J = 8.8, H-2',6' Ar);
7.61 (2Н, d, J = 8.8, H-3',5' Ar); 7.76–7.87 (2H, m,
H-2,10); 8.11 (1Н, d, J = 9.0, H-11); 8.21 (1Н, s, H-6);
8.90 (1Н, d, J-= 2.1, H-8); 8.97 (1Н, br. s, NH); 9.06 (1Н,
dd, J = 4.5, J = 1.7, H-3); 9.61 (1Н, dd, J = 8.2, J = 1.7,
H-1). 13C NMR spectrum (CDCl3), δ, ppm: 92.0; 117.5;
121.5; 123.6; 124.1; 124.9; 127.2; 131.7; 133.1; 133.1; 134.6;
136.1; 137.3; 138.8; 140.4; 140.9; 143.0; 143.2; 151.0. Found,
m/z: 494.9447 [M(79Br)+H]+. С21Н13Br2N4О. Calculated, m/z:
494.9451.
NMR spectra of all synthesized compounds is available at
the journal website at http://link.springer.com/journal/10593.
This work was performed with financial support from
the Ministry of Education and Science of the Russian
Federation within the framework of State Assignment
(project No. 4.6306.2017/8.9).
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