Synthesis of 2-amino(alkylamino)-3-nitro-1,4-naphthoquinones

Article abstract of DOI:10.1134/S1070428014020110

The reaction of 2-amino(alkylamino)-1,4-naphthoquinones with nitrating mixture in concentrated sulfuric acid leads to the formation of 2-amino(alkylamino)-3-nitro-1,4-naphthoquinones.

Full text of DOI:10.1134/S1070428014020110

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 2, pp. 205−210. © Pleiades Publishing, Ltd., 2014.
Original English Text © L.M. Gornostaev, I.S. Kryukovskaya, T.I. Lavrikova, M.V. Vigant, Yu. V. Gatilov, 2014, published in Zhurnal Organicheskoi Khimii,
2014, Vol. 50, No. 2, pp. 214−218.
Synthesis
of 2-Amino(alkylamino)-3-nitro-1,4-naphthoquinones
L. M. Gornostaeva, I. S. Kryukovskayab, T. I. Lavrikovaa, M. V. Viganta,
and Yu. V. Gatilovc
aAstaf’ev Krasnoyarsk State Pedagogical University, Krasnoyarsk, 660049 Russia
bVoino-Yasenetskii Krasnoyarsk State Medical University, Krasnoyarsk, Russia
cVorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch, Russian Academy of Sciences, Novosibirsk, 660090 Russia
e-mail: gornostaev@kspu.ru, gatilov@nioch.nsc.ru
Received July 31, 2013
Abstract—The reaction of 2-amino(alkylamino)-1,4-naphthoquinones with nitrating mixture in concentrated
sulfuric acid leads to the formation of 2-amino(alkylamino)-3-nitro-1,4-naphthoquinones.
DOI: 10.1134/S1070428014020110
1,4-Naphthoquinone derivatives having a nitro group
in the quinoid part of the molecule are poorly understood.
The nitration of 1,4-naphthoquinone [1] and 2,3-dichloro-
1,4-naphthoquinone [2] in fairly stringent conditions
afforded the corresponding 5-nitro-1,4-naphthoquinones.
The nitration of 2-hydroxy-1,4-naphthoquinone and
its derivatives with conc. nitric acid or with nitrating
mixture results in the corresponding 2-hydroxy-3-nitro-
1,4-naphthoquinones [3]. When oxidation-sensitive frag-
ments are present in the benzene ring of the 2-hydroxy-
1,4-naphthoquinone the nitration into the position 3 is
carried out with nitronium tetraborate in acetonitrile [4].
The conversion Id → IIId is accompanied with ni-
trogen oxides liberation. Apparently this process like the
heterocyclization of 2-benzylamino-1,4-naphthoquinone
to 1-hydroxy-2-aryl-1Н-naphtho[2,3-d]-imidazole-4,9-
dione [6] occurs by the radical mechanism and is initiated
by the reaction of R-amino-1,4-naphthoquinones I with
nitronium cation (Scheme 3).
The structure of hydroxyimidazole IIId was con-
1
firmed by physicochemical methods. In its Н NMR
spectrum the proton signal of the hydroxy group appears
in the weak field (12.7 ppm) like in the spectrum of
1-hydroxy-2-phenyl-1Н-naphtho[2,3-d]imidazole-4,9-
dione (13.2 ppm).
2-Hydroxy-3-nitro-1,4-naphthoquinone was first ob-
tained [5] by a reaction of 2,3-dichloro-1,4-naphthoqui-
none with sodium nitrite in a water-alcohol environment.
1,4-Naphthoquinone containing nitro and amino groups
in the quinoid part of the molecule has not been known
up till now.
In the mass spectrm of hydroxyimidazole IIId the
most intensive peak (m/z 57) corresponds apparently
to the acylium cation C2H5CO+. The fragmentation of
Scheme 1.
We have found that 2-amino-1,4-naphthoquinone (Iа),
and also 2-alkyl(dialkyl)amino-1,4-naphthoquinones Ib–
Ig readily react with the nitrating mixture in conc. sulfuric
acid furnishing the corresponding 2-amino(alkylamino)-
3-nitro-1,4-naphthoquinones IIа–IIg (Scheme 1).
R1
R2
R1
R2
O
O
N
N
_
HNO H SO
4
3
2
NO2
The reaction of compounds Ia–Ig with nitrating
mixture in acetic acid is nonselective. For instance,
2-(propylamino)naphthoquinone (Id) gave as a main
product 1-hydroxy-2-ethyl-1Н-naphtho[2,3-d]imidazole-
4,9-dione (IIId) (Scheme 2).
O _
O
_
Ia–Ig
Ià Ig
IIa–IIg
IIà IIg
R1 = H, R2 = H (a), CH3 (b), C2H5 (c), CH2CH2CH3 (d),
C4H9 (e), CH2CH(CH3)2 (f); R1 = R2 = CH3 (g).
205

GORNOSTAEV et al.
206
Scheme 2.
O
O
O
OH
N
NHCH2CH2CH3
_
CH COOH, HNO H SO
3
3
2
4
CH2CH3
N
O
IIId
Id
Scheme 3.
O
O
OH
O
O
.
+NHCH2R
NHCH2R
N
+
NO
2
R
. . .
_
NO
2
N
O
O
molecular ions of 1-hydroxy-2-aryl-1Н-naphtho[2,3-d]-
imidazole-4,9-diones proceeds also with the formation
of aroyl cations [6].
Compounds IIа–IIg comprise a new group of quinoid
compounds. Their structure was investigated by X-ray
diffraction (XRD) (see the figure). According to XRD
data there is a steric strain in the IId molecule, the С1–С2
bond length of 1.523(2) Å is considerably longer than
this bond in the unsubstituted 1,4-naphthoquinone (1.472
and 1.476 Å [7]) and in 2-amino-1,4-naphthoquinone
(1.488 Å [8]). The atoms N1 and N2 deviate from the plane
of the bicyclic skeleton by +0.191(2) and –0.122(2) Å
respectively. The nitro group is strongly turned with re-
spect to the plane, the torsion angle C2C3N2O3 is 69.8(2)°,
resulting in a decrease in its conjugation with the naph-
thoquinone skeleton. The bond length С2–С3, 1.369(2) Å,
coincides with the length of its bond in the 2-[(3-methoxy-
carbonyl)propylamino]-1,4-naphthoquinone, 1.367 Å [9].
During the nitration of alkylaminoquinones I in conc.
sulfuric acid apparently the nitronium cations react with
protonated forms IV along the electrophilic substitution
process (Scheme 4).
The protonation of aminoquinones I occurs at the
carbonyl and not at the amino group as prove the data of
UV spectroscopy. In the UV spectrum of aminoquinone Ia
taken in ethanol the longwave band of the charge transfer
from the amino group to the carbonyl group is present
at 450 nm; in 30% sulfuric acid the absorption band in
the visible region is retained (λmax 450 nm), whereas the
spectral curves in the region 250–400 nm suffer notable
alterations. If the protonation of compound Ia occurred
at the amino group the UV spectrum of the protonated
amines would lack the longwave charge transfer band.
The absorption caused by the charge transfer from the hy-
droxy group to the immonium fragment is also observed
in the UV spectra of solutions of the other aminoquinones
Iа–Ig in sulfuric acid.
In the crystal IId molecules are connected into chains
along the b axis by the hydrogen bonds N1–H···O2
[N–H 0.86(2), H···O 2.53(2) Å, N–H···O 157(2)°].
Among the intermolecular interactions the interactions
of carbonyl groups C1=O1···C4=O2 [O1···C4 3.051(2) Å]
and N2–O4···π(C1–C4) [distance О–centroid 2.991(1) Å]
should be noted.
Scheme 4.
R1
R2
+ R1
N
R1
O
O
O
N
H SO
R2
R2
N
+
2
4
NO
2
NO2
O
OH
O
IV
I
II
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014

SYNTHESIS OF 2-AMINO(ALKYLAMINO)-3-NITRO-1,4-NAPHTHOQUINONES
207
in primary amides [11]. At heating to 60°С the effect of
these factors weakens (Scheme 5).
In compounds IIc–IIf the signal of the protons of the
methylene group linked directly to the amino group is a
broadened singlet both because of the fast intermolecular
proton exchange and the changes in the molecule con-
formation [12].
In the 13С NMR spectra of compounds IIa, IIf the
signals of the carbonyl carbon atoms are shifted upfield
by 2 and 8 ppm with respect to the signals in the spectra
of compounds Ia, If.
The structure of the molecule of 2-propylamino-3-nitro-1,4-
naphthoquinone (IId).
The electron absorption spectra of 2-amino-3-nitro-
naphthoquinones IIа–IIg are distinguished from the
spectra of initial amines Iа–Ig by the absorption band
at ~290 nm, and also by the blue shift of the longwave
absorption maxima by 20–50 nm. Evidently the blue
shift of the longwave absorption maxima in the spectra
of quinones IIа–IIg is caused by the displacement of the
amino group from the coplanarity with the naphthoquin-
oid moiety, and also by the electron-withdrawing effect
of the nitro group.
EXPERIMENTAL
NMR spectra were recorded on a spectrometer
Bruker DRX (500 MHz) in DMSO-d6, internal refer-
ence TMS. Mass spectra were taken on an instrument
Finnigan MAT 8200 (EI, 70 eV). Electron absorption
spectra were recorded on a spectrophotometer Evolution
300 (cells 10 mm) in EtOH (layer thickness 1 cm, с 2 ×
10–4 mol L−1). IR spectra were registered on a spectro-
photometer Shimadzu IRAffinity-1 from pellets with KВr.
Melting points were measured on a heating microblock
Boёtius. The elemental analysis was carried out on an
analyzer Euro EA 3000. In the synthesis of compounds
Iа–Ig commercial 1,4-naphthoquinone (Acros organ-
ics) was used. The reaction progress and the purity of
compounds obtained were monitored by TLC on Silufol
UV-254 plates (eluent toluene–acetone, 10 : 1). XRD
experiment was carried out on a diffractometer Bruker
APEX-II CCD [graphite monochromator, λ(MoKα)
0.71073 Å, φ,ω-scanning, 2θ° < 56.6°, 200 K].
In the IR spectra of compounds IIа–IIg the stretching
vibrations of the nitro group give rise to bands at 1516–
1521, 1338–1342 cm–1 in compliance with the IR spectra
of о-nitroanilines [10]. The bands of the stretching vibra-
tions of the carbonyl groups appear at 1680–1690 cm–1.
In the 1Н NMR spectra of compounds II the signals
of protons at the nitrogen atom are shifted downfield by
1–1.5 ppm with respect to analogous signals of initial
compounds, and the proton signals of the benzene ring
of the molecule, by 0.05–0.15 ppm. In the 1Н NMR spec-
trum of compound IIa at 20°С the protons of the primary
amino group are observed as two separate singlets (8.95
and 9.15 ppm), and at 60°С, as one signal at 8.75 ppm.
Evidently the protons of the primary amino group are
fixed due to the formation of intramolecular hydrogen
bonds with the carbonyl and the nitro groups. It is also
possible that the formation of two signals originates from
the contribution of polar structure Va, like it is observed
X-ray diffraction study of compound IId. Single
crystals of compound IId were obtained after passing
the benzene solution of compound IId through a column
packed with silica gel (layer thickness 15 cm) followed
by concentrating the eluate at 20–25°С and atmospheric
pressure. mp 196°С. C13H12N2O4. Monoclinic crystal
system, space group С2/с, a 20.2191(8), b 7.9146(2),
c 15.8395(7) Å, β 109.137(2)°, V 2394.7(2) Å3, Z 8,
Scheme 5.
d
calc 1.444 g/cm3, μ 0.109 cm–1, number of measured
reflections 10127, among them independent 2987
(Rint 0.0478), number of reflections with I ≥ 2σ(I) 2410.
The correction for absorption was performed empirically
using program SADABS (Tmin/Tmax 0.872/0.980). The
structure was solved by the direct method. The positions
and thermal parameters of atoms were refined in the
anisotropic approximation by full matrix least-squares
O
H
O
H
+
N H
N
H
NO2
NO2
O
IIa
O_
Va
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014

GORNOSTAEV et al.
208
procedure. The hydrogen atom of the amino group was
localized from the difference maps and refined isotropi-
cally, the other hydrogen atoms were placed in the geo-
metrically calculated positions and were included in the
refinement in the riding model. The number of refined
parameters 178, wR2 0.1325, S 1.012 (for all reflections),
R1 0.0456 [I ≥ 2σ(I)]. All calculations were carried out
applying SHELX software. The data obtained were
deposited in Cambridge Crystallographic Data Center,
CCDC 948698.
(Irel, %): 229 (26.6) [M]+, 186 (100), 43 (35.4). Found,
%: С 73.73; Н 6.48; N 6.22. С14Н15NO2. Calculated, %:
С 73.36; Н 6.55; N 6.11.
2-Amino-3-nitro-1,4-naphthoquinone (IIа). To the
cooled to 5°С solution of 1.73 g (0.01 mol) of 2-amino-
1,4-naphthoquinone (Iа) in 30 mL of 94% sulfuric acid
was added within 5 min the nitrating mixture prepared
from 1.6 mL of 60% nitric and 2.4 mL of 94% sulfuric
acids. After stirring for 30 min the reaction mixture was
poured into 150 g of water with ice. The orange precipitate
was filtered off, washed with water to neutral washings,
and dried. Yield 1.85 g (84%), mp 228°С (alcohol–ben-
zene, 1 : 1). UV spectrum, λmax, nm (logε): 249 (4.22),
291 (3.16), 399 (3.45). 1Н NMR spectrum, δ, ppm (20°С):
7.82 t [1Н, Н6(7), J 7.6 Hz], 7.93 t [1Н, Н7(6), J 7.6 Hz],
8.05 d [1Н, Н5(8), J 7.6 Hz], 8.08 d [1Н, Н8(5), J 7.6 Hz],
8.92 br.s (1Н, NH), 9.15 br.s (1Н, NH). 1Н NMR spec-
trum, δ, ppm (60°С): 7.82 t [1Н, Н6(7), J 7.6 Hz], 7.93 t
[1Н, Н7(6), J 7.6 Hz], 8.05 d [1Н, Н5(8), J 7.6 Hz], 8.08 d
[1Н, Н8(5), J 7.6 Hz], 8.80 br.s (2Н, NH2). 13C NMR
spectrum, δ, ppm: 179.4 (1С, С1), 172.8 (1С, С4). Mass
spectrum, m/z (Irel, %): 218 (59.4) [M]+, 89 (100), 76
(80.3), 50 (66.3). Found, %: С 55.64; Н 2.74; N 12.87.
С10Н6N2O4. Calculated, %: С 55.15; Н 2.75; N 12.84.
2-Amino-1,4-naphthoquinone (Iа) was obtained
from 1,4-naphthoquinone and sodium azide in acetic
acid [13]. UV spectrum, λmax, nm (logε), in EtOH: 226
(4.28), 330 (3.41), 444 (3.42); in 30% H2SO4: 227 (4.49),
263 (4.34), 300 (4.00), 356 (3.43), 468 (3.48). 1Н NMR
spectrum, δ, ppm: 5.80 s (1Н, Н3), 7.2 br.s (2Н, NH2),
7.72 t [1Н, Н6(7), J 7.5 Hz], 7.81 t [1Н, Н7(6), J 7.5 Hz],
7.92 d [1Н, Н5(8), J 7.6 Hz], 7.98 d [1Н, Н8(5), J 7.6 Hz].
Mass spectrum, m/z (Irel, %): 173 (80.6) [M]+, 105 (70.9),
76 (100), 50 (86.2), 41 (68.3).
2-Dimethylamino-1,4-naphthoquinone (Ig) and
2-alkylamino-1,4-naphthoquinones Ib–If were syn-
thesized along procedures described respectively in [14,
15]. The yield of 2-alkylamino-1,4-naphthoquinone Ib–Ig
can be increased by using as solvent 2-propanol instead
of methanol.
2-Methylamino-3-nitro-1,4-naphthoquinone (IIb).
To the cooled to 5°С solution of 1.87 g (0.01 mol) of
2-methylamino-1,4-naphthoquinone (Ib) in 30 mL of
94% sulfuric acid was added within 5 min the nitrating
mixture prepared from 1.6 mL of 60% nitric and 2.4 mL
of 94% sulfuric acids. After stirring for 30 min the reac-
tion mixture was poured into 150 g of water with ice. The
orange precipitate was filtered off, washed with water
to neutral washings, and dried. Yield 2.1 g (92%), mp
234°С. UV spectrum, λmax, nm (logε): 250 (4.30), 293
(3.96), 331 (3.48), 432 (3.47). 1Н NMR spectrum, δ, ppm:
2.80 s (3Н, СН3), 7.81 t [1Н, Н6(7), J 7.6 Hz], 7.92 t [1Н,
Н7(6), J 7.6 Hz], 8.05 d [2Н, Н5,8, J 7.6 Hz], 8.68 s (1Н,
NH). Mass spectrum, m/z (Irel, %): 232 (18.0) [M]+, 202
(14.5), 188 (5.1), 76 (83.9), 50 (57.4), 30 (100). Found,
%: С 57.08; Н 3.50; N 12.10. С11Н8N2O4. Calculated,
%: С 56.89; Н 3.44; N 12.07.
2-Isobutylamino-1,4-naphthoquinone (If). Into
50 mL of 2-propanol was charged 8 g (0.05 mol) of
1,4-naphthoquinone, to the solution 6 mL of isobutyl-
amine in 10 mL of 2-propanol was added. The reaction
mixture was heated at stirring at 40–50°С for 30 min,
then at the same temperature and stirring 40 mL of water
was added. The reaction mixture was heated to 70°С and
cooled to –10°С within 10 h. The separated precipitate
was filtered off, washed with 50 mL of 20% aqueous
ethanol, and dried. Yield 7.2 g (63%), mp 124°С. UV
spectrum, λmax, nm (logε): 273 (4.36), 328 (3.32), 457
(3.52). IR spectrum, ν, cm–1: 3323 s (NH), 1678 s (C=O).
1Н NMR spectrum, δ, ppm: 0.90 d (6Н, 2СН3, J 6.7 Hz),
1.98 septet (1Н, СН, J 6.7 Hz), 3.01 br.t (2Н, СН2,
J 6.7 Hz), 5.70 s (1Н, Н3), 7.59 br.t (1Н, NH, J 6.2 Hz),
7.72 t [1Н, Н6(7), J 7.6 Hz], 7.83 t [1H, H7(6), J 7.6 Hz],
7.94 d [1Н, Н5(8), J 7.6 Hz], 7.99 d [1Н, Н8(5), J 7.6 Hz].
13C NMR spectrum, δ, ppm: 20.2 (2С, 2СН3), 26.7 (1С,
СН), 49.2 (1С, СН2), 99.3 (1С, С3), 125.3 [1С, С8(5)],
125.8 [1С, С5(8)], 130.4 [1С, С4а(8а)], 132.0 [1С, С6(7)],
133.2 [1С, С8а(4а)], 134.8 [1С, С7(6)], 148.7 (1С, С2),
181.2 [1С, С1(4)], 181.6 [1С, С4(1)]. Mass spectrum, m/z
3-Nitro-2-ethylamino-1,4-naphthoquinone (IIc).
To the cooled to 5°С solution of 1.01 g (0.005 mol) of
2-ethylamino-1,4-naphthoquinone (Ic) in 15 mL of 94%
sulfuric acid was added within 5 min the nitrating mix-
ture prepared from 0.8 mL of 60% nitric and 1.2 mL of
94% sulfuric acids. After stirring for 20 min the reaction
mixture was poured into 150 g of water with ice. The
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014

SYNTHESIS OF 2-AMINO(ALKYLAMINO)-3-NITRO-1,4-NAPHTHOQUINONES
209
orange precipitate was filtered off, washed with water.
Yield 1.0 g (81%), mp 224°С (alcohol–benzene, 1 : 1).
UV spectrum, λmax, nm (logε): 251 (3.38), 295 (3.97),
431 (3.49). 1Н NMR spectrum, δ, ppm: 1.18 t (3Н, СН3,
J 7.1 Hz), 3.20 br.s (2Н, СН2), 7.81 t [1Н, Н6(7), J 7.1 Hz],
7.92 t [1Н, Н7(6), J 7.1 Hz], 8.40 s (1Н, NH). Mass spec-
trum, m/z (Irel, %): 246 (6.9) [M]+, 76 (40.8), 50 (29.0), 30
(100). Found, %: С 58.61; Н 3.92; N 11.86. С12Н10N2O4.
Calculated, %: С 58.53; Н 4.06; N 11.38.
0.8 mL of 60% nitric and 1.2 mL of 94% sulfuric acids
was added. After stirring for 20 min the reaction mixture
was poured into water with ice. The orange precipitate
was filtered off, washed with water. Yield 1.1 g (80%),
mp 174°С (from alcohol). UV spectrum, λmax, nm (logε):
257 (4.27), 295 (3.96), 331 (3.51), 432 (3.49). 1Н NMR
spectrum, δ, ppm: 0.85 d (6Н, 2СН3, J 6.6 Hz), 1.87
quintet (1Н, СН, J 6.6 Hz), 2.90 br.s (2Н, СН2, J 7.6 Hz),
7.82 t [1Н, Н6(7), J 7.6 Hz], 7.92 t [1Н, Н7(6), J 7.6 Hz],
8.03–8.08 m (2Н, Н5,8), 8.45 s (1Н, NН). 13C NMR
spectrum, δ, ppm: 19.87 (2С, 2СН3), 28.23 (1С, СН),
50.04 (1С, СН2), 126.07 [1С, С5(8)], 126.8 [1С, С8(5)],
128.18 [1С, С4а,(8а)], 129.74 [1С, С8а,(4а)], 131.11 (1С,
С2), 133.29 [1С, С6(7)], 135.72 [1С, С7(6)], 139.75 (1С,
С3). Mass spectrum, m/z (Irel, %): 274 (7.3) [M]+, 228
(6.8), 174 (19.6), 50 (8.6), 41 (100). Found, %: С 61.17;
Н 5.01; N 10.03. С14Н14N2O4. Calculated, %: С 61.31;
Н 5.11; N 10.22.
3-Nitro-2-propylamino-1,4-naphthoquinone (IId).
A solution of 1.08 g (0.005 mol) of 2-propylamino-
1,4-naphthoquinone (Id) in 15 mL of conc. H2SO4 was
cooled to 5°С and 2 mL of nitrating mixture prepared
from 0.8 mL of 60% nitric and 1.2 mL of 94% sulfuric
acids was added. After stirring for 20 min the reaction
mixture was poured into water with ice. The orange
precipitate was filtered off, washed with water. Yield
1.2 g (92%), mp 196°С (alcohol–benzene, 1 : 1). UV
spectrum, λmax, nm (logε): 251 (4.45), 289 (4.10), 434
2-Dimethylamino-3-nitro-1,4-naphthoquinone
(IIg). A solution of 0.8 g (0.004 mol) 2-dimethylamino-
1,4-naphthoquinone (Ig) in 15 mL of 94% sulfuric acid
was cooled to 5°С and 1.5 mL of nitrating mixture pre-
pared of 0.6 mLof 60% nitric and 0.9 mLof 94% sulfuric
acids was added. After stirring for 20 min the reaction
mixture was poured into water with ice. The orange
precipitate was filtered off, washed with ethanol. Yield
0.75 g (76%), mp 151°С. UV spectrum, λmax, nm (logε):
1
(3.57). Н NMR spectrum, δ, ppm: 0.85 t (3Н, СН3,
J 7.4 Hz), 1.59 sextet (2Н, СН2, J 7.3 Hz), 3.10 s (2Н,
СН2NH), 7.82 t [1Н, Н6(7), J 7.6 Hz], 7.92 t [1Н, Н7(6)
,
J 7.6 Hz], 8.05 t (2Н, Н5,8, J 7.6 Hz), 8.40 s (1Н, NH).
Mass spectrum, m/z (Irel, %): 260 (24.7) [M]+, 76 (70.1),
531.6), 41 (100). Found, %: С 59.85; Н 4.55; N 10.68.
С13Н12N2O4. Calculated, %: С 60.00; Н 4.62; N 10.70.
2-Butylamino-3-nitro-1,4-naphthoquinone (IIe).
A solution of 1.15 g (0.005 mol) of 2-butylamino-1,4-
naphthoquinone (Ie) in 15 mL of conc. H2SO4 was
cooled to 5°С and 2 mL of nitrating mixture prepared
from 0.8 mL of 60% nitric and 1.2 mL of 94% sulfuric
acids was added. After stirring for 20 min the reaction
mixture was poured into water with ice. The orange pre-
cipitate was filtered off, washed with water. Yield 1.2 g
(87%), mp 120°С (from alcohol). UV spectrum, λmax, nm
(logε): 260 (4.30), 292 (4.00), 330 (3.54), 432 (3.54).
1Н NMR spectrum, δ, ppm: 0.86 t (3Н, СН3, J 7.4 Hz),
1.27 sextet (2Н, СН2СН3, J 7.5 Hz), 1.55 quintet (2Н,
СН2СН2СН3, J 7.2 Hz), 3.12 br.s (2Н, NHCH2), 7.82 t
[1Н, Н6(7), J 7.0 Hz], 7.92 t [1Н, Н7(6), J 7.0 Hz], 8.04 t
(2Н, Н5,8, J 7.0 Hz). Mass spectrum, m/z (Irel, %): 274
(4.9) [M]+, 227 (30.0), 76 (32.6), 41 (100). Found, %:
С 61.02; Н 4.89; N 10.04. С14Н14N2O4. Calculated, %:
С 61.31; Н 5.11; N 10.22.
1
251 (4.35), 293 (3.97), 432 (3.49). Н NMR spectrum,
δ, ppm: 3.34 s (6Н, 2СН3), 7.81 t [1Н, С6(7), J 7.5 Hz],
7.88 t [1Н, С7(6), J 7.5 Hz], 7.96 d [1Н, С5(8), J 7.6 Hz],
8.00 d [1Н, С8(5), J 7.6 Hz]. Mass spectrum, m/z (Irel,
%): 246 (29.73) [M]+, 158 (45.1), 76 (100), 50 (52.2), 30
(60.9). Found, %: С 58.57; Н 3.88; N 11.17. С12Н10N2O4.
Calculated, %: С 58.54; Н 4.06; N 11.38.
1-Hydroxy-2-ethyl-1Н-naphtho[2,3-d]imidazole-
4,9-dione (IIId). To a solution of 1.08 g (0.005 mol) of
2-propylamino-1,4-naphthoquinone in 20 mL of acetic
acid was added within 5 min at 20°С nitrating mixture
prepared of 1.5 mL of 60% nitric and 2.5 mL of 94%
sulfuric acids. The reaction mixture was stirred for 30 min
while self-heating to 40°С. The liberation of nitrogen
oxides was observed. The reaction mixture was cooled
to 20°С and poured into ice mixture with water (~100 g),
the orange precipitate was filtered off, washed with water,
dried, and recrystallized from alcohol–benzene, 1 : 1.
Yield 0.54 g (44%), mp 291°С. UV spectrum, λmax, nm
2-Isobutylamino-3-nitro-1,4-naphthoquinone (IIf).
A solution of 1.15 g (0.005 mol) of 2-isobutylamino-
1,4-naphthoquinone (If) in 15 mL of concn. H2SO4 was
cooled to 5°С and 2 mLof nitrating mixture prepared from
1
(log ε): 280 (4.49), 375 (3.75), 461 (3.81). Н NMR
spectrum, δ, ppm: 1.29 t (3Н, СН3, J 7.6 Hz), 2.80 q (2Н,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014

GORNOSTAEV et al.
210
СН2, J 7.6 Hz), 7.82–7.86 m (2Н, Н6,7), 8.04–8.10 m (2Н,
Н5,8). Mass spectrum, m/z (Irel, %): 242 (6.3) [M]+, 186
(62.8), 57 (100). Found, %: С 64.03; Н 3.94; N 11.13.
С13Н10N2O3. Calculated, %: С 64.46; Н 4.13; N 11.57.
Org. Chem., 2013, vol. 49, p. 1354.
7. Thozet, A. and Gaultier, J., Acta Cryst., Sect. B, 1977,
vol. 33, 1052.
8. Gaultier, J. and Hauw, C., Acta Cryst., Sect. B, 1969, vol. 25,
p. 419.
9. Michael, J.P., Cirillo, P.F., Denner, L., Hosken, G.D., How-
ard, A.S., and Tinkler, O.S., Tetrahedron, 1990, vol. 46,
p. 7923.
10. Becker, H., Organikum, Berlin: Der Deutcsher Verlag, 1976.
11. Silverstein, R.M., Webster, F.X., and Kiemle, D.J., Spec-
trometric Identification of Organic Compounds, NewYork:
John Wiley & Sons, Inc., 2005.
REFERENCES
1. Wilbur, J.M. and Day, A.R., J. Org. Chem., 1960, vol. 25,
p. 753.
2. Chatterjee, S. and Kwalwasser, W.D., J. Chem. Soc., Perkin
Trans. 2, 1974, p. 873.
3. Buckle, D.R., Cantello, B.C.C., Smith, H., Smith, R.J., and
Spicer, D.A., J. Med. Chem., 1977, vol. 20, no. 8, p. 1059.
4. Min, Yu., Malinakova, H.C., and Stagliano, K.W., J. Org.
Chem. 2006, vol. 71, no. 17, p. 6648.
12. Pretsch, E., Bühlmann, P., and Affolter, C., Structure De-
termination of Organic Compounds, Springer, 2004.
13. Fieser, L.F. and Hartwell, J.L., J. Am. Chem. Soc., 1935,
vol. 57, p. 1482.
5. Ulrich, H. and Richer R., Meth. Org. Chem. 1977, vol. 7/3a,
p. 832.
6. Gornostaev, L.M., Vigant, M.V., Kargina, O.I., Kuznetso-
va, A.S., Khalyavina, Yu.G., and Lavrikova, T.I., Russ. J.
14. Grinev, A.N., Zaitsev, I.A., Venevtseva, N.K., and
Terent’ev, A.P., Zh. Obshch. Khim., 1960, vol. 30, p. 1914.
15. Rupert, A.C., Belgium Patent 614136, 1961; Chem. Abstr.,
1962, vol. 57, 15031.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014