Reactions of 2-(4-hydroxyanilino)-1,4-naphthoquinones with cerium ammonium nitrate and pyridinium chlorochromate

Article abstract of DOI:10.1134/S1070428012020121

Reactions of 2-(4-hydroxyarylamino)-1,4-naphthoquinones with cerium ammonium nitrate or pyridinium chlorochromate depending on the structure of initial substrate and the type of reagent led to the formation of 2-chloro-3-(4-cyclohexa-2,5-dienylideneamino)

Full text of DOI:10.1134/S1070428012020121

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 2, pp. 234−240. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.E. Devyashina, L.M. Gornostaev, Yu.V. Gatilov, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 2, pp. 214−220.
Reactions of 2-(4-Hydroxyanilino)-1,4-naphthoquinones
with Cerium Ammonium Nitrate and Pyridinium
Chlorochromate
A. E. Devyashinaa, L. M. Gornostaeva, and Yu. V. Gatilovb
aAstaf’ev Krasnoyarsk State Pedagogical University, Krasnoyarsk, 660049 Russia
e-mail: gornostaev@kspu.ru
bVorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division,
Russian Academy of Sciences Novosibirsk,630090 Russia
e-mail: gatilov@nioch.nsc.ru
Received June 28, 2011
Abstract—Reactions of 2-(4-hydroxyarylamino)-1,4-naphthoquinones with cerium ammonium nitrate or
pyridinium chlorochromate depending on the structure of initial substrate and the type of reagent led to the
formation of 2-chloro-3-(4-cyclohexa-2,5-dienylideneamino)-1,4-dihydronaphthalene-1,4-diones, 2-(4-hydroxy-
3-nitrophenylamino)-1,4-naphthaquinones, and also to simultaneous oxidation and chlorination.
DOI: 10.1134/S1070428012020121
Both polycyclic quinones and quinone imines possess
practically important properties [1], but the information
on polycyclic compounds containing in a single molecule
both quinoid and quinone imine fragments is virtually
absent. In this study we examined the experimental ap-
proaches to this type compounds.
chlorochromate, which had been successfully applied
formerly to the preparation of some quinones and quinone
imines [2, 3].
The oxidation of 2-chloro-3-(4-hydroxyphenylamino)-
1,4-naphthoquinones IIа–IIc with cerium ammonium
nitrate led to the formation of the corresponding
2-chloro-3-(4-oxocyclohexa-2,5-dienylideneamino)-1,4-
dihydronaphthalene-1,4-diones IIIа–IIIc (the substitu-
ents are listed according to the Latin alphabet in order to
conserve the numeration of atoms) (Scheme 1).
By the reaction of 2,3-dichloro-1,4-naphthoquinone
(Iа), 5-hydroxy-2,3-dichloro-1,4-naphthoquinone (Ib)
with p-aminophenols, and also by the direct amination
of 1,4-naphthoquinone (Ic) 2-(4-hydroxyarylamino)-1,4-
naphthoquinones IIа–IIf were obtained and their behav-
ior with respect to oxidants was investigated. We used
as oxidants cerium ammonium nitrate and pyridinium
2-Chloro-8-hydroxy-3-(4-hydroxyphenylamino)-1,4-
naphthoquinone (IId) was oxidized to the corresponding
quinone imine (IIId) with pyridinium chlorochromate
Scheme 1.
R2
R2
R2
O
O
O
NH
OH
(NH4)2Ce(NO3)6
Cl H2N
Cl
OH
N
O
Cl
Cl
R1
O
R1
O
Iа, Ib
R1
O
IIа_IId
IIIа_IIIc
I, R1 = H (a), OH (b); II, R1 = R2 = H (а); R1 = H, R2 = Me (b); R1 = OH, R2 = Me (c), H (d); III, R1 = R2 = H (а), R1 =
H, R2 = Me (b), R1 = OH, R2 = Me (c).
234

REACTIONS OF 2-(4-HYDROXYANILINO)-1,4-NAPHTHOQUINONES
235
Scheme 2.
ClCrO3_
O
+
N
H
N
O
IId
Cl
OH
O
IIId
since the reaction of compound IId with cerium
ammonium nitrate took another route (Scheme 2).
According to XRD analysis the molecules of com-
pounds IIIa, IIId are nonplanar, the angles between the
naphthoquinone and iminocyclohexadienone fragments
equal 73.1(1) and 75.9(1), 76.6(1)° respectively (two
crystallographically independent molecules are present
in IIId) (Fig. 1). In molecules IIIa, IIId the alternating
of bond lengths characteristic for enones was observed
in agreement with the published data on 2-chloro-3-
triphenylphosphinimino-1,4-naphthoquinone [4] and
2-amino-3-bromo-5-chloro-4-(4-chlorophenylimino)
cyclohexa-2,5-dien-1-one [5]. In molecules IIId intramo-
lecular hydrogen bonds are present, namely O4–H⋯O1
[H⋯O 1.60(4), 1.85 Å, angles O–H⋯O 156(4), 146°].In
the crystals of compoundIIIa stacks of molecules form due
to the π-stacking interactions π(С5–С10)–π(С1–С4,С9,С10)
[intercentroid distance Cg–Cg 3.770(2), interplanar dis-
tance 3.30 Å] and π(С5–С10)–π(С5–С10) [3.769(2), 3.35
Å]; С1–О1⋯π(С1–С4,С9,С10) [O-Cg 3.275(2) Å] and С16–
H16⋯O1 (Н–О 2.50 Å, angle С–Н⋯О 172°). In the crystal
of compound IIId stacks of molecules are also present due
Fig. 1. Structures of molecules 2-chloro-3-(4-oxocyclohexa-
2,5-dienylideneamino)-1,4-dihydronaphthalene-1,4-dione
(IIIа) and 2-chloro-8-hydroxy-3-(4-oxocyclohexa-2,5-
dienylideneamino)-1,4-dihydronaphthalene-1,4-dione (IIId)
according to XRD data.
1,4-naphthoquinones IVа–IVc was confirmed by
physicochemical methods. Their electron absorption
spectra in the visible region are little distinguished from
the absorption spectra of the initial substances IId–IIf,
whereas the oxidation of 2-(4-hydroxyphenylamino)-1,4-
naphthoquinones IIа–IId to quinone imines IIIа–IIId
causes deep changes in the electron absorption spectra
(Fig. 2, 3). The spectra of compounds IIIа–IIId lack the
longwave absorption band characteristic of aminophenols
IIа–IId which corresponds evidently to the charge trans-
fer from the arylamino to carbonyl group. The electron
absorption spectra of compound IId and product of its
nitration IVa differ only slightly.
to the interactions С1–О1⋯π(С5А–С10А
) [O–Cg 3.325(3)],
С1–О4⋯π(С1А–С4А,С9А,С10А) [3.286(3) Å], dipole-dipole
interactions С1–О1⋯О4А–С8А [distances С–О 3.173(5),
3.169(5) Å], С8–О4⋯О1А–С1А [3.192(5), 3.207(6) Å]
and С16–Н16⋯О4А (2.48 Å, 172°), С16А–Н16А⋯О4 (2.47
Å, 168°). In the crystal of compound IIId considerably
shortened interstack contacts of clorine atoms were ob-
served: Cl1⋯O3A [3.022(4)] and Cl1A⋯O3 [3.004(5) Å],
sum of van der Waals radii 3.34 Å [6].
The reaction of compounds IId–IIf with cerium am-
monium nitrate resulted in the nitration of the arylamino
fragments of the initial substances.
It was stated previously that toluene reaction with
cerium ammonium nitrate in acetic acid resulted in
nitration with the formation of a mixture of isomeric
nitrotoluenes [7].
An additional confirmation of the validity of the
structure of 2-(4-hydroxy-3-nitrophenylamino)-1,4-
naphthoquinone (IVc) was the identity of this compound
to the product of compound IIe nitration with the nitrat-
ing mixture.
The structure of 2-(4-hydroxy-3-nitrophenylamino)-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

DEVYASHINA et al.
236
The analysis of 1Н NMR spectra of 2-(4-hydroxy-3-
nitroarylamino)-1,4-naphthoquinones IVа–IVc confirms
that the nitro group is introduced in the ortho-position
to the hydroxy group at the treatment of compounds
IId–IIf with cerium ammonium nitrate. In the 1Н NMR
spectrum of compound IIe the downfield signals of pro-
tons linked to the nitrogen atoms appear at 9.58 and 9.00
ppm respectively. In the nitro derivative IVc the signal
of the NH is observed at 9.21 ppm, and the signal of the
proton of the hydroxy group forming an intromolecular
hydrogen bond with the ortho-located nitro group appears
at 11.00 ppm (the proton signal of the hydroxy group
in the spectrum of the ortho-nitrophenol is present at
10.5 ppm [8]). In [9] 1Н NMR spectra were reported of
2-(nitroanilino)-3-chloro-1,4-naphthoquinones. In these
spectra the signals of protons bound to nitrogen atoms
Fig. 2. Electron absorption spectra of compounds IIа (1), IIIа
(2) in DMF.
Scheme 4.
O
NH
OH
O
IIe
NO2
OH
O
NH
IVc
HNO3, H2SO4
Fig. 3. Electron absorption spectra of compounds IId (1), IIId
(2), IVа (3) in DMF.
O
Scheme 3.
R3
Scheme 5.
O
NH
OH
NO2
OH
O
O
R2
NH
R1
O
IId_IIf
R3
O
O
IVc
(NH4)2Ce(NO3)6,
20_25oC, CH3COOH
NH
R2
OH
NO2
NO2
OCOCH3
O
NH
(CH3CO)2O
R1
IVa_IVc
R1 = OH, R2 = Cl, R3 = H (IId, IVа); R1 = R2 = R3 = H
(IIe, IVb); R1 = R2 = H, R3 = Me (IIf, IVc).
O
V
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

REACTIONS OF 2-(4-HYDROXYANILINO)-1,4-NAPHTHOQUINONES
237
Scheme 6.
in 2-(4-nitroanilino)-3-chloro-1,4-naphthoquinone and
2-(2,4-dinitroanilino)-3-chloro-1,4-naphthoquinone were
observed at 9.7 and 9.84 ppm. Hence the introduction of
a nitro group in the ortho-position to the amino group
weakly affected the position of the proton of the second-
ary amino group.
In the prepared by us 4-[(1,4-dioxo-1,4-dihydronaph-
thalen-2-yl)amino]-2-nitrophenyl acetate (V) the proton
signal of the ОН group is absent, and the signal of the
proton of the NH group appears at 9.5 ppm.
R1
O
O
NH
OH
IId, IIf
O
R1
Pyridinium
chlorochromate,
25oC
The acetylation of compound IVc at the hydroxy and
not the amino group was confirmed by changes in the
electron absorption spectrum and also by the absorption
band of the ester carbonyl group (ν 1766 cm–1) in the IR
spectrum of quinone V.
N
O
CH3COOH
Cl
O
IIIа, IIIb
The oxidation of compounds IIe, IIf with pyridinium
chlorochromate is accompanied with the introduction of
the chlorine atom in the position 3 of the naphthoquinone
fragment.
R1 = H (IIe, IIIa), CH3 (IIf, IIIb).
pound IIId was localized from the difference synthesis
and was isotropically refined, we failed to localize the
analogous atom H of the second independent molecule,
and its position was geometrically calculated. All calcu-
lations were peformed using software SHELX-97. The
data obtained were deposited into the Cambridge Cris-
tallographic Data Center (CCDC nos. 821950, 821951).
EXPERIMENTAL
1Н NMR spectra were registered on a spectrometer
Bruker DRX (500 MHz), solvent DMSO-d6, internal
reference TMS. The reaction progress was monitored
and the purity of compounds obtained was checked by
TLC on Silufol UV-254 plates. Melting points were mea-
sured on Boёtius heating microblock. Mass spectra were
obtained on an instrument Finnigan MAT-8200. Electron
absorption spectra were recorded on a spectrophotometer
Evolution 300 in DMF at the cell thickness 1 cm and the
concentration 1 × 10–4 mol l−1. IR spectra were taken on
a spectrophotometer Tensor 27 from pellets with KBr. We
used in the study commercially available 2,3-dichloro-1,4-
naphthoquinone and 1,4-naphthoquinone purchased from
Across, 5-hydroxy-2,3-dichloro-1,4-naphthoquinone
was obtained from 5-hydroxy-1,4-naphthoquinone by
procedure [10].
2-Chloro-3-(4-hydroxyphenylamino)-1,4-
naphthoquinone (IIa). To 4 g (0.017 mol) of 2,3-dichloro-
1,4-naphthoquinone (Iа) in 40 ml of ethanol was added
2.5 g (0.022 mol) of p-aminophenol, the mixture was
stirred at 50–60°С for 20 min, then the solution was heat-
ed to boiling and cooled. The dark-violet precipitate was
filtered off and recrystallized from ethanol. Yield 3.42 g
(77%), mp 240–241°С. UV spectrum, λmax, nm (lgε): 502
(3.52). 1Н NMR spectrum, δ, ppm: 6.71 br.d (2Н, Н2',6'
,
J 8.7 Hz), 6.97 br.d (2Н, Н3',5', J 8.7 Hz), 7.78 br.t (1Н,
Н6(7), J 7.5 Hz), 7.85 br.t (1Н, Н7(6), J 7.5 Hz), 8.01 d
(1Н, Н5(8), J 4.5 Hz), 8.03 d (1Н, Н8(5), J 4.5 Hz), 9.15 s
(1Н, ОH), 9.40 s (1Н, NН). Mass spectrum, m/z (Irel, %):
299 (72.97) [M]+, 264 (68.57), 105 (55.96), 94 (45.55),
76 (100), 65 (86.39), 39 (93.69). Found, %: C 64.26;
H 3.49; N 4.71. C16H11СlNO3. Calculated, %: C 64.10;
H 3.33; N 4.67.
XRD experiments were carried out on a diffractom-
eter Bruker Kappa Apex II [graphite monochromator,
λ(MoKα) 0.71073 Å, ω,φ-scanning, 296 K]. Correction
for absorption was done with the program SADABS. The
structures were solved by the direct method. The posi-
tions and thermal parameters of nonhydrogen atoms were
refined in the anisotropic approximation of full-matrix
least-squares method. The positions of hydrogen atoms
were determined geometrically and refined using the rider
model. The hydrogen atom of the hydroxy group of com-
2-Chloro-3-(4-hydroxy-3-methylphenylamino)-
1,4-naphthoquinone (IIb). To 2.3 g (0.01 mol) of com-
pound Ia in 30 ml of ethanol was added 2 g (0.016 mol)
of 4-amino-2-methylphenol, the mixture was stirred at
50–60°С for 20 min, then the solution was heated to
boiling and cooled. The dark-red precipitate was filtered
off and recrystallized from ethanol. Yield 2.13 g (75%),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

DEVYASHINA et al.
238
mp 232–234°С. UV spectrum, λmax, nm (lgε): 508 (3.49).
1Н NMR spectrum, δ ppm: 2.10 s (3Н, СН3), 6.71 br.d
(1Н, Н5', J 8.0 Hz), 6.80 d.d (1Н, Н6', J 8.0, J 2.5 Hz),
6.88 d (1Н, Н2', J 2.5 Hz), 7.75 br.t (1Н, Н6(7), J 7.5 Hz),
7.85 br.t (1Н, Н7(6), J 7.5 Hz), 7.93 d.d (1Н, Н5(8), J 9.0,
J 3.0 Hz), 8.10 d.d (1Н, Н8(5), J 9.0, J 3.0 Hz), 9.05 s
(1Н, ОН), 9.30 s (1Н, NH). Mass spectrum, m/z (Irel, %):
313 (49.25) [M]+, 278 (55.46), 105 (36.54), 77 (100), 76
(51.15), 51 (30.53). Found, %: C 64.59; H 3.95; N 4.48.
C17H12ClNO3. Calculated, %: C 65.07; H 3.82; N 4.46.
p-aminophenol, the mixture was stirred at 50–60°С for
20 min, then the solution was heated to boiling and cooled.
The dark-red precipitate was filtered off and recrystallized
from ethanol. Yield 3.24 g (57%), mp 258–260°С. UV
spectrum, λmax, nm (log ε): 482 (3.56). 1Н NMR spectrum,
δ, ppm: 5.85 s (1Н, Н3), 6.83 d (2Н, Н2',6', J 8.0 Hz), 7.15 d
(2Н, Н3',5', J 8.0 Hz), 7.78 t (1Н, Н6(7), J 7.0 Hz), 7.83 t
(1Н, Н7(6), J 7.0 Hz), 7.93 d (1Н, Н5(8), J 7.0 Hz), 8.03 d
(1Н, Н8(5), J 7.0 Hz), 9.00 s (1Н, ОH), 9.51 s (1Н, NН).
Mass spectrum, m/z (Irel, %): 265 (100) [M]+, 236 (28.23),
220 (27.03), 105 (29.83), 76 (34.73), 65 (19.92). Found,
%: C 72.60; H 3.95; N 5.39. C16H11NO3. Calculated, %:
C 72.45; H 4.15; N 5.28.
2-Chloro-8-hydroxy-3-(4-hydroxy-3-methyl-
phenylamino)-1,4-naphthoquinone (IIc). To 1 g
(0.0044 mol) of 2,3-dichloro-5-hydroxy-1,4-naphtho-
quinone (Ib) in 20 ml of ethanol was added 0.79 g
(0.0065 mol) of 4-amino-2-methylphenol, the mixture
was stirred at 50–60°С for 35 min, then the solution was
heated to boiling and cooled. The dark-violet precipitate
was filtered off and recrystallized from ethanol. Yield
0.78 g (58%), mp 243–245°С. UV spectrum, λmax, nm
(log ε): 397 (3.57), 527 (3.74). 1Н NMR spectrum, δ, ppm:
2.10 s (3Н, СН3), 6.72 br.d (1Н, Н5', J 8.0 Hz), 6.82 d.d
(1Н, Н6', J 8.0, J 2.0 Hz), 6.90 d (1Н, Н2', J 2.0 Hz), 7.31 d
(1Н, Н7, J 8.0 Hz), 7.56 d (1Н, Н5, J 8.0 Hz), 7.64 t (1Н,
Н6, J 8.0 Hz), 9.40 s (2Н, NH, 4'-OH), 12.40–13.00 br.s
(1Н, 8-ОН). Mass spectrum, m/z (Irel, %): 329 (90.19)
[M]+, 294 (100), 121 (22.72), 92 (26.33), 77 (82.38), 63
(32.43), 39 (33.53). Found, %: C 61.33; H 3.51; N 4.04.
C17H12ClNO4. Calculated, %: C 61.91; H 3.64; N 4.24.
2-(4-Hydroxy-3-methylphenylamino)-1,4-naphtho-
quinone (IIf). To 2 g (0.012 mol) of 1,4-naphthoquinone
(Ic) in 20 ml of ethanol was added 2.21 g (0.018 mol) of
4-amino-2-methylphenol, the mixture was stirred at
50–60°С for 20 min, then the solution was heated to boil-
ing and cooled. The dark-violet precipitate was filtered
off and recrystallized from ethanol. Yield 1.65 g (82%),
mp 298–300°С. UV spectrum, λmax, nm (log ε): 494
1
(3.55). Н NMR spectrum, δ, ppm: 2.15 s (3Н, СН3),
5.85 s (1Н, Н3), 6.85 br.d (1Н, Н5', J 8.0 Hz), 6.98 d
(1Н, Н6', J 8.0 Hz), 7.06 s (1Н, Н2'), 7.75 t (1Н, Н6(7)
J 7.4 Hz), 7.84 t (1Н, Н7(6), J 7.4 Hz), 7.93 d (1Н, Н5(8)
,
,
J 7.4 Hz), 8.03 d (1Н, Н8(5), J 7.4 Hz), 8.95 s (1Н, ОН),
9.45 s (1Н, NH). Mass spectrum, m/z (Irel, %): 279 (100)
[M]+, 264 (40.64), 234 (30.73), 105 (55.56), 104 (39.74),
77 (92.09), 76 (68.77), 51 (33.83). Found, %: C 73.55;
H 4.52; N 4.96. C17H13NO3. Calculated, %: C 73.11;
H 4.65; N 5.01.
2-Chloro-8-hydroxy-3-(4-hydroxyphenylamino)-
1,4-naphthoquinone (IId). To 0.5 g (0.002 mol) of
compound Ib in 20 ml of ethanol was added 0.5 g
(0.0045 mol) of p-aminophenol, the mixture was stirred
at 50–60°С for 30 min, then the solution was heated to
boiling and cooled. The dark-red precipitate was filtered
off and recrystallized from ethanol. Yield 0.39 g (65%),
mp 269–270°С. UV spectrum, λmax, nm (log ε): 397
2-Chloro-3-(1,4-oxocyclohexa-2,5-dienylidene-
amino)-1,4-dihydronaphthalene-1,4-dione (IIIа). а.
To 3 g (0.01 mol) of compound IIa in 25 ml of concn.
AcOH was added 9 g (0.017 mol) of cerium ammonium
nitrate dissolved in 50 ml of 50%AcOH, the mixture was
stirred at 25°С for 25 min. The red-orange precipitate
was filtered off and recrystallized from toluene. Yield
2.5 g (83%), mp 228–230°С. 1Н NMR spectrum, δ, ppm:
6.70 br.s (2Н, Н2',6'), 7.40 br.s (2Н, Н3',5'), 7.87–7.94 m
(1Н, Н6,7), 8.04 d.d (1Н, Н5(8), J 7.4, J 1.5 Hz), 8.12 d.d
(1Н, Н8(5), J 7.4, J 1.5 Hz). Mass spectrum, m/z (Irel, %):
297 (100) [M]+, 262 (90.39), 154 (84.08), 76 (53.65), 63
(37.04). Found, %: C 72.60; H 3.95; N 5.39. C16H11NO3.
Calculated, %: C 72.45; H 4.15; N 5.28.
1
(3.46), 522 (3.63). Н NMR spectrum, δ, ppm: 6.71 d
(2Н, Н2',6', J 9.0 Hz), 7.00 d (2Н, Н3',5', J 9.0 Hz),
7.32 d.d (1Н, Н7, J 8.0, J 1.0 Hz), 7.57 d.d (1Н, Н5, J 8.0,
J 1.0 Hz), 7.65 t (1Н, Н6, J 8.0 Hz), 9.45 s (2Н, NH,
4'-OH), 12.65 s (1Н, 8-ОН). Mass spectrum, m/z (Irel, %):
315 (100) [M]+, 280 (68.57), 160 (23.52), 121 (27.33),
65 (49.85), 44 (64.56), 39 (53.45). Found, %: C 60.85;
H 3.16; N 4.43. C16H10ClNO4. Calculated, %: C 60.98;
H 3.23; N 4.14.
XRD analysis of compound IIIa. Triclinic crys-
tal system, space group P-1, a 7.026(1), b 8.210(1),
c 12.2072(15) Å, α 82.173(5), β 84.870(6), γ 68.299(5)°,
2-(4-Hydroxyphenylamino)-1,4-naphthoquinone
(IIe). To 4 g (0.025 mol) of 1,4-naphthoquinone (Ic)
on 40 ml of ethanol was added 3.8 g (0.035 mol) of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

REACTIONS OF 2-(4-HYDROXYANILINO)-1,4-NAPHTHOQUINONES
239
V 647.6(2) Å3. C16H8ClNO3. Z 2, dcalc 1.527 g/cm3,
μ 0.304 cm–1. Intensities of 6587 reflections were
measured, 2θ < 52°, among them 2506 independent
(Rint 0.0370). Parameters of refinement: wR2 0.1791,
S 1.049 (for all reflections), R1 0.0597 [for 1849 reflec-
tions with I ≥ 2σ(I)].
(1Н, Н2', J 9.0 Hz), 7.20 br.d (1Н, Н5', J 9.0 Hz),
7.32 br.d (1Н, Н6', J 9.8 Hz), 7.41 d.d (1Н, Н7,
J 8.0, J 1.0 Hz), 7.57 d.d (1Н, Н5, J 8.0, J 1.0 Hz), 7.75 t
(1Н, Н6, J 8.0 Hz), 11.75 br.s (1Н, ОН). Mass spectrum,
m/z (Irel, %): 327 (72.97) [M]+, 292 (91.39), 132 (48.85),
106 (80.38), 92 (34.93), 78 (100), 77 (73.07), 51 (46.15).
Found, %: C 62.70; H 2.93; N 4.06. C17H10ClNO4.
Calculated, %: C 62.29; H 3.05; N 4.27.
b. To 0.3 g (0.001 mol) of compound IIe in 10 ml of
concn.AcOH was added 0.97 g (0.005 mol) of pyridinium
chlorochromate dissolved in 15 ml of 50% AcOH, the
mixture was stirred at 25°С for 30 min. The red-orange
precipitate was filtered off and purified by column
chromatography on silica gel eluting with benzene. Yield
0.17 g (57%). 1Н NMR spectrum and melting point were
identical to those of the sample obtained by procedure а.
2-Chloro-3-(4-oxocyclohexa-2,5-dienylidene-
amino)-8-hydroxy-1,4-dihydronaphthalene-1,4-dione
(IIId). To 0.53 g (0.0016 mol) of compound IId in 15 ml of
concn.AcOH was added 3.2 g (0.014 mol) of pyridinium
chlorochromate dissolved in 25 ml of 50% AcOH, the
mixture was stirred at 25°С for 35 min. The orange precip-
itate was filtered off and recrystallized from toluene. Yield
0.44 g (83%), mp 226–228°С. UV spectrum, λmax, nm
(lgε): 435 (3.64). 1Н NMR spectrum, δ, ppm: 6.73 d (2Н,
Н2',6', J 9.0 Hz), 7.35 d (2Н, Н3',5', J 9.0 Hz), 7.42 d (1Н,
Н7, J 8.0 Hz), 7.58 d (1Н, Н5, J 8.0 Hz), 7.76 t (1Н, Н6,
J 8.0 Hz), 11.70 s (1Н, ОН). Mass spectrum, m/z (Irel, %):
313 (72.87) [M]+, 278 (83.48), 207 (39.34), 92 (37.24),
63 (100), 38 (30.93). Found, %: C 60.92; H 2.41; N 4.23.
C16H8ClNO4. Calculated, %: C 61.24; H 2.55; N 4.46.
2-Chloro-3-(3-methyl-4-oxocyclohexa-2,5-
dienylideneamino)-1,4-dihydronaphthalene-1,4-
dione (IIIb). а. To 0.6 g (0.0019 mol) of compound IIb
in 15 ml of concn. AcOH was added 1.1 g (0.002 mol)
of cerium ammonium nitrate dissolved in 10 ml of 50%
AcOH, the mixture was stirred at 25°С for 25 min. The
red-orange precipitate was filtered off and recrystal-
lized from toluene. Yield 0.49 g (82%), mp 192–194°С.
1Н NMR spectrum, δ, ppm: 1.95 с (3Н, СН3), 6.75 br.s
(1Н, Н2'), 7.3 br.d (2Н, Н5',6' , J 8.0 Hz ), 7.87–7.95 m
XRD analysis of compound IIId. Orthorhombic
crystal system, space group Pna21, a 27.132(1), b
6.7687(3), c 14.8065(6) Å, V 2719.1(2) Å3. C16H8ClNO4.
Z 8, dcalc 1.532 g/cm3, μ 0.299 cm–1. Intensities of 24561
reflections were measured, 2θ < 51°, 5071 among them
independent (Rint 0.0646). Parameters of refinement: wR2
0.1436, S 1.023 (for all reflections), R1 0.0435 [for 3288
reflections with I ≥ 2σ(I)]. The program PLATON sug-
gests the space group Pbcn. Yet the refinement along this
group results in R1 0.1094 [for 1807 reflections with I ≥
2σ(I)]. Besides among 740 reflections of 0kl type there are
311 errors in the systematic absorptions characteristic of
this space group [average ratio I:σ(I) 6.6]. Hence the space
group Pbcn is not consistent with the experimental data.
(1Н, Н6,7), 8.3 d (1Н, Н5(8), J 7.0 Hz), 8.15 d (1Н, Н8(5)
,
J 7.0 Hz). Mass spectrum, m/z (Irel, %): 311 (82.28)
[M]+, 276 (51.05), 132 (39.44), 106 (84.68), 78 (100),
77 (76.48), 76 (81.08), 51 (62.46),39 (46.35). Found, %:
C 65.85; H 3.28; N 4.56. C17H10ClNO3. Calculated, %:
C 65.48; H 3.21; N 4.49.
b. To 0.22 g (0.00079 mol) of compound IIf in 10 ml
of concn.AcOH was added 2.3 g (0.01 mol) of pyridinium
chlorochromate dissolved in 15 ml of 50% AcOH, the
mixture was stirred at 25°С for 30 min. The red-orange
precipitate was filtered off and purified by column
chromatography on silica gel eluting with benzene. Yield
0.15 g (68%). 1Н NMR spectrum and melting point were
identical to those of the sample obtained by procedure а.
2-Chloro-3-(4-hydroxy-3-nitrophenylamino)-
8-hydroxy-1,4-naphthoquinone (IVа). To 0.56 g
(0.0017 mol) of compound IId in 15 ml of concn. AcOH
was added 1.1 g (0.002 mol) of cerium ammonium nitrate
dissolved in 10 ml of 50%AcOH, the mixture was stirred
at 25°С for 35 min. The red-orange precipitate was filtered
off and recrystallized from toluene. Yield 0.45 g (70%),
mp 279–280°С. UV spectrum, λmax, nm (log ε): 401
(3.58), 497 (3.67). 1Н NMR spectrum, δ, ppm: 7.10 br.d
(1Н, Н5', J 8.8 Hz), 7.34 d (1Н, Н7, J 8.0 Hz), 7.39 d.d
(1Н, Н6', J 6.0, 3.0 Hz), 7.58 br.d (1Н, Н5, J 7.0 Hz),
2-Chloro-3-(3-methyl-4-oxocyclohexa-2,5-di-
enylideneamino)-8-hydroxy-1,4-dihydronaphthalene-
1,4-dione (IIIc. To 0.35 g (0.001 mol) of com-
pound IIc in 20 ml of concn. AcOH was added 1.1 g
(0.002 mol) of cerium ammonium nitrate dissolved in
15 ml of 50% AcOH, the mixture was stirred at 25°С
for 35 min. The orange precipitate was filtered off and
recrystallized from toluene. Yield 0.32 g (91%), mp
225–227°С. UV spectrum, λmax, nm (lgε): 435 (3.71).
1Н NMR spectrum, δ, ppm: 2.00 s (3Н, СН3), 6.75 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

DEVYASHINA et al.
240
7.67 br.t (1Н, Н6, J 8.0 Hz), 7.72 d (1Н, Н2', J 3.0 Hz),
9.60 s (1Н, NH), 11.00 s (1Н, 3'-ОН), 12.65 s (1Н, 8-ОН).
Mass spectrum, m/z (Irel, %): 360 (45.55) [M]+, 92 (49.65),
89 (43.14), 63 (100), 53 (71.97), 43 (92.49), 39 (53.45).
Found, %: C 53.25; H 2.48; N 7.78. C16H9ClN2O6.
Calculated, %: C 53.25; H 2.49; N 7.76.
was added dropwise 10 ml of water. The red precipitate
was filtered off and purified by column chromatography
on silica gel eluting with benzene. Yield 0.5 g (29%).
1Н NMR spectrum and melting point were identical to
those of the sample obtained by procedure а.
4-[(1,4-Dioxo-1,4-dihydronaphthalen-2-yl)amino]-
2-nitrophenyl acetate (V). In 8 ml of pyridine was
dissolved 0.6 g (0.005 mol) of ccompound IVc and
1.5 ml of acetic anhydride was added, the mixture
was stirred at 25°С for 10 min, and 7 ml of water was
added dropwise. The orange precipitate was filtered off
and recrystallized from toluene. Yield 0.55 g (80%),
mp 173–175°С. UV spectrum, λmax, nm (log ε): 452
2-(4-Hydroxy-3-methyl-5-nitrophenylamino)-
1,4-naphthoquinone (IVb). To 0.57 g (0.002 mol) of
compound IIf in 15 ml of concn. AcOH was added 1.1 g
(0.002 mol) of cerium ammonium nitrate dissolved in
10 ml of 50% AcOH, the mixture was stirred at 25°С
for 30 min. The red precipitate was filtered off and re-
crystallized from a mixture DMF–ethanol, 3 : 1. Yield
0.45 g (73%), mp 293–295°С. UV spectrum, λmax, nm
(lgε): 456 (3.69). 1Н NMR spectrum, δ, ppm: 2.27 s (3Н,
СН3), 6.01 s (1Н, Н3), 7.55 s (1Н, Н2'), 7.79 br.t (1Н,
1
(3.63). IR spectrum, ν, cm–1: 1766 (С=О). Н NMR
spectrum, δ, ppm: 2.30 s (3Н, СН3), 6.30 s (1Н, Н3),
7.51 br.d (1Н, Н5', J 9.0 Hz), 7.82 t (1Н, Н6(7), J 7.5 Hz),
7.85 d.d (1Н, Н6', J 8.5, J 3.0 Hz), 7.88 br.t (1Н,
Н7(6), J 7.5 Hz), 7.98 br.d (1Н, Н8(5), J 7.5 Hz), 8.09 br.d
(1Н, Н5(8), J 7.5 Hz), 8.15 d (1Н, Н2', J 3.0 Hz), 9.50 s
(1Н, NН). Mass spectrum, m/z (Irel, %): 310 (97.30) [M]+,
234 (27.03), 105 (33.83), 102 (36.34), 76 (32.93), 43
(100). Found, %: C 61.48; H 3.41; N 7.85. C18H12N2O6.
Calculated, %: C 61.36; H 3.40; N 7.95.
Н6(7), J 7.0 Hz), 7.79 s (1Н, Н6'), 7.87 br.t (1Н, Н7(6)
,
J 7.0 Hz), 7.96 br.d (1Н, Н5(8), J 7.0 Hz), 8.07 br.d (1Н,
Н8(5), J 7.0 Hz), 9.20 s (1Н, NН), 10.50–11.00 br.s (1Н,
ОН). Mass spectrum, m/z (Irel, %): 324 (100) [M]+, 249
(33.63), 102 (67.37), 76 (67.27), 51 (40.64). Found, %:
C 62.95; H 3.52; N 7.96. C17H12N2O5. Calculated, %:
C 62.96; H 3.70; N 8.64.
2-(4-Hydroxy-3-nitrophenylamino)-1,4-naphtho-
quinone (IVc). а. To 0.6 g (0.002 mol) of com-
pound IIe in 15 ml of concn. AcOH was added 1.1 g
(0.002 mol) of cerium ammonium nitrate dissolved in
10 ml of 50% AcOH, the mixture was stirred at 25°С
for 25 min. The red precipitate was filtered off and
recrystallized from toluene. Yield 0.44 g(75%), mp
291–293°С. UV spectrum, λmax, nm (lgε): 464 (3.61).
1Н NMR spectrum, δ, ppm: 6.00 s (1Н, Н3), 7.20 d
(1Н, Н5', J 8.0 Hz), 7.55 d.d (1Н, Н6', J 8.0, J 3.0 Hz),
REFERENCES
1. Venkataraman, K., Khimiya sinteticheskikh krasitelei
(Chemistry of Synthetic Dyes), Leningrad: Goskhimizdat,
1954, p. 17.
2. Carreno, M.C. and Ribagorda, M., Science of Synthesis,
2006, vol. 28, p. 647.
3. Willis, J.P., Gogins, K.A.Z., and Miller, L.L., J. Org. Chem.,
1981, vol. 46, p. 3215.
4. Sun, D., Krawiec, M., Campana, C.F., and Watson, W.H.,
7.78 br.t (1Н, Н7(6), J 7.0 Hz), 7.87 br.t (1Н, Н6(7)
J 7.0 Hz), 7.88 d (1Н, Н2', J 3.0 Hz), 7.95 d (1Н, Н8(5)
,
,
J. Chem. Cryst., 1997, vol. 27, p. 577.
5. Ma, H.C. and Jiang, X.Z., Synlett., 2007, p. 1679.
J 7.0 Hz), 8.06 d (1Н, Н5(8), J 7.0 Hz), 9.20 s (1Н, NH),
11.00 br.s (1Н, ОН). Mass spectrum, m/z (Irel, %): 310
(100) [M]+, 235 (32.83), 105 (62.66), 102 (53.25),
76 (86.29), 51 (38.64). Found, %: C 62.08; H 3.20;
N 8.85. C16H10N2O5. Calculated, %: C 61.93; H 3.22;
N 9.03.
6. Rowland, R.S. and Taylor, R.J., Phys. Chem., 1996,
vol. 100, p. 7384.
7. Makhon’kov, D.I., Cheprakov, A.V., Rodkin, M.A., and
Beletskaya, I.P., Zh. Org. Khim., 1986, vol. 22, p. 30.
8. Pretsch, E., Buhlmann, P., and Affolter, C., Structure De-
termination of Organic Compounds, Springer-Verlag, 2000.
9. Win, T., Yerushalmi, S., and Bittner, S., Synthesis, 2005,
b. To a solution of 0.3 g (0.0011 mol) of compound
IIe in 10 ml of concn. AcOH was added while stirring at
cooling to 5–10°С 1.5 ml of nitrating mixture prepared
from 1.4 ml of 95% H2SO4 and 0.1 ml of 62% HNO3, then
vol. 10, p. 1631.
10. Wheeler, A.S., Dawson, P.R., and Mcewen, J.L., J. Am.
Chem. Soc., 1923, vol. 45, p. 1970.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012