Synthesis and reactions of trinitro-9,10-phenanthrenequinone derivatives

Article abstract of DOI:10.1134/S1070428013070117

The reaction of 2,4,7-trinitro-9,10-phenanthrenequinone with CuCl in aqueous dimethylformamide or dimethyl sulfoxide at room temperature, followed by acidification, gave a stable red complex of 2,4,7-trinitro-9,10- dihydroxyphenanthrene with a solvent molecule. On heating in a polar aprotic solvent in the presence of CuCl or other metal salt, 2,4,7-trinitro-9,10- phenanthrenequinone underwent benzilic acid rearrangement with formation of 2,4,7-trinitrofluorenone. The nitration of 9,10-sulfuryldioxyphenanthrene and subsequent decomposition of cyclic sulfates afforded previously unknown 1,3,6-trinitro- and 1,8-dinitro-9,10-phenanthrenequinones.

Full text of DOI:10.1134/S1070428013070117

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 7, pp. 1025–1030. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.M. Andrievskii, R.V. Linko, M.K. Grachev, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 7,
pp. 1041–1045.
Synthesis and Reactions of Trinitro-9,10-phenanthrenequinone
Derivatives
A. M. Andrievskiia, R. V. Linkob, and M. K. Grachevc
a Research Institute of Organic Intermediate Products and Dyes, Bol’shaya Sadovaya ul. 1-4, Moscow, 123995 Russia
e-mail: info@cemess.ru
b Peoples’Friendship University of Russia, Moscow, Russia
c Moscow State Pedagogical University, Moscow, Russia
Received August 30, 2012
Abstract—The reaction of 2,4,7-trinitro-9,10-phenanthrenequinone with CuCl in aqueous dimethylformamide
or dimethyl sulfoxide at room temperature, followed by acidification, gave a stable red complex of 2,4,7-tri-
nitro-9,10-dihydroxyphenanthrene with a solvent molecule. On heating in a polar aprotic solvent in the
presence of CuCl or other metal salt, 2,4,7-trinitro-9,10-phenanthrenequinone underwent benzilic acid
rearrangement with formation of 2,4,7-trinitrofluorenone. The nitration of 9,10-sulfuryldioxyphenanthrene and
subsequent decomposition of cyclic sulfates afforded previously unknown 1,3,6-trinitro- and 1,8-dinitro-9,10-
phenanthrenequinones.
DOI: 10.1134/S1070428013070117
Nitro derivatives of 9,10-phenanthrenequinone tend
to react with nucleophiles at the carbonyl groups [1, 2].
2,4,7-Trinitro-9,10-phenanthrenequinone (I) in polar
aprotic solvents undergoes hydration at the carbonyl
groups via addition of one or two water molecules,
depending on the solvent nature. In DMF or DMSO,
the addition of one water molecule gives 2,4,7-trinitro-
10,10-dihydroxy-9,10-dihydrophenanthren-9-one
solvates II and III with two solvent molecules [3]
(Scheme 1).
nitro groups remaining intact. 2,7-Dinitro-9,10-phen-
anthrenequinone was not reduced under analogous
conditions.
No reaction occurred in anhydrous DMF or DMSO.
Presumably, the presence of water weakens solvation
by aprotic solvent, and the equilibrium between
quinone I and solvate II or III is displaced toward the
former. The reduction of I yields hydroquinone which
is stabilized as complex IV or V. These complexes are
stronger than solvates II and III. Unlike hydrated
quinone solvates II and III, the H-chelate ring in
hydroquinone solvate complexes IV and V lies in the
phenanthrene ring plane, which ensures conjugation
with the aromatic system. Electronic interaction be-
tween the chelated hydroxy groups and the aromatic
phenanthrene core bearing three nitro groups is respon-
sible for the color-determining absorption band
(λmax 465 nm) in the electronic absorption spectrum,
which is likely to be a charge-transfer band. In the
electronic spectra of solutions of IV and V in an inert
solvent, the absorption intensity in the visible region
gradually decreases due to decomposition of the
solvate structure and oxidation of hydroquinone with
atmospheric oxygen. The spectra of IV and V in
acetonitrile become identical to the spectrum of the
initial quinone approximately in one hour.
After addition of CuCl to a solution of 2,4,7-tri-
nitro-9,10-phenanthrenequinone (I) in aqueous DMF
or DMSO at room temperature and subsequent acidi-
fication, a red solid separated almost immediately.
According to the elemental analysis data, the product
contained no metal and the phenanthrene fragment was
bound to one solvent molecule. The product displayed
in the IR spectrum a strong band in the region 3200–
3300 cm–1, which may be assigned to stretching vibra-
tions of hydroxy groups involved in hydrogen bond.
Treatment of both compounds with acetic anhydride
led to the formation of 9,10-diacetoxy-2,4,7-trinitro-
phenanthrene (VI). Therefore, they were assigned the
structure of 1:1 2,4,7-trinitro-9,10-dihydroxyphenan-
threne solvates with DMF (IV) and DMSO (V). Thus
the quinone is selectively reduced to hydroquinone, the
1025

ANDRIEVSKII et al.
1026
Scheme 1.
M
O
OH
O
O
COOH
O2N
O2N
O2N
OH
NO2
NO2
O2N
NO2
O2N
O2N
A
VII
MX, DMF
Δ
CHNMe2
SMe2
O
H
O
H
CHNMe2
SMe2
O
O
O
O
O
O
H
O
H
O2N
O2N
O
O2N
O
O
H2O, DMF
H2O, DMSO
O2N
NO2
O2N
NO2
O2N
NO2
II
I
III
DMF, H2O
CuCl, HCl
DMSO, H2O
CuCl, HCl
CHNMe2
SMe2
O
O
H
H
H
H
O
O
OAc
O
O
O2N
O2N
OAc
O2N
Ac2O
Ac2O
O2N
NO2
O2N
VI
NO2
O2N
NO2
IV
V
M = Cu(I), Cu(II), Ni, Cr, Al; X = Hlgn (n = 1–3).
Heating of 2,4,7-trinitro-9,10-phenanthrenequinone
(I) in DMF in the presence of CuCl gave 2,4,7-trini-
trofluorenone (VII) in 76% yield, obviously as a result
of benzilic acid rearrangement [4] (Scheme 1). No
fluorenone VII was detected in the absence of copper
salt, whereas only traces of VII were formed in ethanol
or acetonitrile. Copper(I) salt can be replaced by salts
of other metals, such as copper(II), nickel, chromium,
or aluminum.
formed by the hydroxy group of hydrate molecule II
with metal ion in reaction complex A. Decarboxylation
of intermediate 9-hydroxyfluorene-9-carboxylic acid
yields 9-hydroxyfluorene which is oxidized to fluore-
none VII with atmospheric oxygen.
The presence of three nitro groups in molecule I is
a significant factor determining its ability to undergo
hydration at the carbonyl groups, reduction to hydro-
quinone complex, and benzilic acid rearrangement un-
der atypical conditions. 2,7-Dinitro-9,10-phenan-
threnequinone does not undergo analogous trans-
formations.
Conventional mechanism of benzilic acid rear-
rangement of 1,2-diketones involves addition of hy-
droxide ion to carbonyl group, which induces valence
electron transfer with formation of α-hydroxy carbox-
ylic acid. In our case, the transferred electron pair is
supplied not by the anionic center but by the bond
2,4,7-Trinitro-9,10-phenanthrenequinone (I) is the
only known phenanthrenequinone derivative contaning
more than two nitro groups. We made an attempt to
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SYNTHESIS AND REACTIONS OF TRINITRO-9,10-PHENANTHRENEQUINONE
1027
Scheme 2.
O
O
O
O
O
O
O
O
O
S
S
S
O
O
O
HNO3 (d = 1.40)
O2N
NO2
+
O2N
NO2
VIII
O
O
O
O
O2N
NO2
200–250°C
+
O2N
NO2
IX
X
O
O
O
O
O
O
S
S
S
O
O
O
O
O
O
HNO3 (d = 1.51)
NO2
O2N
NO2
+
O2N
NO2
O2N
NO2
VIII
XI
O
O
NO2
NO2
O2N
XII
synthesize new polynitro-substituted phenanthrene-
quinones according to the procedure proposed in [5],
starting from 9,10-sulfuryldioxyphenanthrene (VIII).
Schenck and Schmidt-Thomée [5] prepared cyclic sul-
fate VIII by photochemical reaction of phenanthrene-
quinone with sulfur dioxide, and the nitration of VIII,
followed by thermal decomposition of the nitration
products gave 3-nitro- and 3,6-dinitro-9,10-phenan-
threnequinones. Judging by the electronic absorption
spectra of the corresponding charge-transfer com-
plexes and polarographic reduction potentials, 3,6-di-
nitro-9,10-phenanthrenequinone is superior to its 2,7-
and 2,5-dinitro isomers in acceptor power [6].
heated to 200–250°C; by fractional crystallization we
isolated 3,6-dinitro-9,10-phenanthrenequinone (IX)
and 1,8-dinitro-9,10-phenanthrenequinone (X) in 24
and 6% yield, respectively (Scheme 2).
The position of nitro groups in molecules IX and X
1
was determined on the basis of the H NMR data. The
1H NMR spectrum of IX contained a doublet at
δ 8.23 ppm (1-H, 8-H), a doublet of doublets at
δ 8.43 ppm (2-H, 7-H), and a doublet at δ 9.22 ppm
(4-H, 5-H) with coupling constants typical of 3,6-di-
nitro-9,10-phenanthrenequinone (IX), and the melting
point of IX coincided with that given in [5]. Com-
pound X had the same elemental composition, and it
1
By heating a suspension of sulfate VIII in HNO3
(d = 1.40 g/cm3) at the boiling point for 3 min we
obtained a mixture of dinitro derivatives, which was
displayed in the H NMR spectrum doublets of dou-
blets at δ 7.73 (4-H, 5-H), 8.09 ppm (3-H, 6-H), and
8.68 ppm (2-H, 7-H); the coupling constants were
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 7 2013

ANDRIEVSKII et al.
1028
typical of 1,8-dinitro derivative. The formation of
4,5-dinitro-9,10-phenanthrenequinone can be ruled out
for steric reasons. Thus the H NMR spectrum con-
formed to the structure of previously unknown 1,8-di-
nitro-9,10-phenanthrenequinone (X).
9,10-phenanthrenequinone (XII); obviously, it was
formed via thermal decomposition of the correspond-
ing cyclic sulfate during the nitration process. The
yield of XII was about ~50%, which makes 1,3,6-tri-
nitro-9,10-phenanthrenequinone an accessible sub-
strate for further study.
1
With a view to introduce more than two nitro
groups into 9,10-phenanthrenequinone molecule,
a suspension of VIII in concentrated nitric acid
(d = 1.51) was heated for 10 min at the boiling point.
The solid product separated from the reaction mixture
by filtration contained four nitro groups and a sulfur
atom (according to the elemental analysis data) and
was identified as tetranitro-9,10-sulfuryldioxyphenan-
threne (XI). Its mass spectrum lacked molecular ion
peak, but a ion peak with m/z 388 [M – SO2]+ was
observed, which was assigned to tetranitro-9,10-phen-
anthrenequinone. No carbonyl absorption was present
in the IR spectrum of XI. The bands at 1436 and
1226 cm–1 were assigned to νs(SO2) and νas(SO2),
respectively, indicating cyclic sulfate structure. These
bands appeared at higher frequencies relative to the
corresponding bands in the spectrum of sulfate VIII,
which may be due to strong acceptor effect of the nitro
groups. Antisymmetric and symmetric stretching vibra-
tions of the nitro groups were observed at 1546, 1538,
and 1346 cm–1, and the doublet character of the
νas(NO2) band indicated nonequivalence of the nitro
groups. These findings, as well as the results of elec-
trophilic substitution in molecule VIII with formation
of dinitro derivatives, allowed us to assign the struc-
ture of 1,3,6,8-tetranitro-9,10-sulfuryldioxyphenan-
threne to product XI. However, we failed to isolate
1,3,6,8-tetranitro-9,10-phenanthrenequinone: thermal
decomposition of XI led to the formation of a complex
mixture of products which were difficult to separate.
EXPERIMENTAL
The 1H NMR spectra were recorded on a Jeol ECX-
400 spectrometer at 400.13 MHz from solutions in
acetone-d6; the chemical shifts were determined rela-
tive to tetramethylsilane. The IR spectra were obtained
on a Perkin Elmer 598 spectrometer from samples
prepared as KCl pellets. The mass spectra were
recorded on an MKh-1320 instrument. The melting
points were measured on a Boetius melting point
apparatus. The progress of reactions and the purity of
products were monitored by TLC on Silufol UV-254
plates; spots were visualized by treatment with a solu-
tion of SnCl2 and 4-dimethylaminobenzaldehyde in
aqueous ethanol acidified with HCl. Silicagel L (40–
100 and 100–160 μm; Chemapol, Czechia) was used
for preparative column chromatography.
2,4,7-Trinitro-10,10-dihydroxy-9,10-dihydro-
phenanthren-9-one–DMF solvate (II). A solution of
1.0 g (2.9 mmol) of 2,4,7-trinitro-9,10-phenanthrene-
quinone (I) in 5 ml of DMF was left to stand in
an open beaker. After two weeks, the crystals were
filtered off and washed with DMF and CCl4. Light
yellow crystals, mp 89–90°C. IR spectrum, ν, cm–1:
3200–2600 (OH), 1740 (C=O), 1660 (N–C=O), 1526
(NO2), 1350 (NO2). Found, %: C 47.41; H 4.12;
N 13.77. C14H7N3O9· 2C3H7NO. Calculated, %:
C 47.34; H 4.14; N 13.81.
2,4,7-Trinitro-10,10-dihydroxy-9,10-dihydro-
phenanthren-9-one–DMSO solvate (III). A solution
of 0.5 g (1.45 mmol) of compound I in 5 ml of DMSO
was left to stand for 3 weeks in an open beaker. The
light orange crystals were filtered off, washed with
CCl4, and dried in air. mp 94–96°C. IR spectrum, ν,
cm–1: 3350–2600 (OH), 1736 (C=O), 1526 (NO2),
1350 (NO2), 1008. Found, %: C 42.05; H 3.46; N 8.36;
S 11.98. C14H7N3O9 · 2 C2H6OS. Calculated, %:
C 41.78; H 3.68; N.12; S 12.38.
After separation of XI, we isolated from the filtrate
a yellow–orange substance which showed in the IR
spectrum a carbonyl absorption band at 1688 cm–1 and
absorption bands at 1564, 1532, and 1352 cm–1 due to
stretching vibrations of nitro groups. In keeping with
the elemental composition and mass spectrum (m/z 343
[M]+), the product was identified as trinitro derivative
1
of 9,10-phenanthrenequinone. Its H NMR spectrum
contained a doublet at δ 8.32 ppm (8-H), a doublet of
doublets at δ 8.52 ppm (7-H), a doublet at δ 8.68 ppm
(3-H), a doublet at δ 9.34 ppm (5-H), and a doublet at
δ 9.50 ppm (4-H). The position of signals, their multi-
plicities and intensity ratio, and the coupling constants
allowed us to conclude that the nitro groups occupy
positions 1, 3, and 6 of the phenanthrene core. Thus
the product was assigned the structure of 1,3,6-trinitro-
2,4,7-Trinitro-9,10-dihydroxyphenanthrene–
DMF complex (IV). A solution of 0.2 g (0.06 mmol)
of compound I in 10 ml of aqueous DMF (3:1) was
added under stirring at room temperature to a solution
of 0.3 g (3.0 mmol) of copper(I) chloride in 30 ml of
aqueous DMF (2:1) acidified with concentrated aque-
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SYNTHESIS AND REACTIONS OF TRINITRO-9,10-PHENANTHRENEQUINONE
1029
ous HCl to pH 1–2. After 1 h, the precipitate was
filtered off, washed with water, dried in a vacuum
desiccator over P2O5, and reprecipitated from DMF.
Yield 0.19 g (78%), red crystals, mp 173–174°C
(decomp.), Rf 0.21 (benzene–acetone, 8:1). IR spec-
trum, ν, cm–1: 3306 (OH), 3100 (CH), 1662 (N–C=O),
1620 (C=C), 1512 (NO2), 1344 (NO2). Found, %:
C 49.10; H 3.55; N 13.19. C14H7N3O8·C3H7NO. Cal-
culated, %: C 48.80; H 3.34; N 13.40.
1.8 Hz), 8.97 d (1H, 3-H, 4J = 2.3 Hz). 13C NMR spec-
trum (DMSO-d6), δC, ppm: 119.7 (C8), 122.6 (C1),
126.6 (C3), 128.4 (C5), 131.2 (C6), 136.7 (C7), 138.4
(C4), 139.5 (C2); 143.9, 145.6, 149.4, 150.2 (C4a, C4b,
C8a, C9a); 186.7 (C9).
When the reaction was carried out under analogous
conditions in the presence of copper(II) nitrate instead
of CuCl, the yield of VII was 51%.
3,6-Dinitro-9,10-phenanthrenequinone (IX)
and 1,8-dinitro-9,10-phenanthrenequinone (X).
9,10-Sulfuryldioxyphenanthrene (VIII) [5], 0.6 g
(2.2 mmol), was added to 25 ml of nitric acid (d = 1.4)
heated to 120°C, and the mixture was quickly heated
to the boiling point, kept boiling for 3 min, and cooled
to room temperature. The precipitate was filtered off,
washed with 5 ml of nitric acid (d = 1.4) and water,
dried over P2O5, and treated with boiling chloroform
(2×10 ml). The product was filtered off, dried, and
heated to 240–250°C under stirring for 20 min
(thermal decomposition). Fractional crystallization
from acetic acid gave compounds IX and X.
2,4,7-Trinitro-9,10-dihydroxyphenanthrene–
DMSO complex (V). A solution of 0.35 g (3.5 mmol)
of copper(I) chloride in 20 ml of aqueous DMSO (1:1)
acidified with concentrated aqueous HCl to pH 1–2
was mixed with a solution of 0.24 g (0.07 mmol) of
compound I in 20 ml of aqueous DMSO (1:1). After
1 h, the precipitate was filtered off, washed with water,
dried over P2O5, and reprecipitated from DMSO. Yield
0.25 g (84%), red crystals, mp 191–193°C (decomp.,
sealed capillary), Rf 0.21 (benzene–acetone, 8:1). IR
spectrum, ν, cm–1: 3226 (OH), 3102 (CH), 1624
(C=C), 1514 (NO2), 1346 (NO2), 1000 (S=O). Found,
%: C 45.19; H 3.32; N 10.54; S 7.30. C14H7N3O8 ·
C2H6OS. Calculated, %: C 45.39; H 3.07; N 9.93;
S 7.57.
Compound IX. Yield 0.16 g (24%), yellow–orange
crystals, mp 290–292°C (from AcOH); published data
[4]: mp 293–295°C; Rf 0.67 (benzene–acetone, 8:1).
IR spectrum, ν, cm–1: 1688 (C=O), 1528 (NO2), 1354
2,4,7-Trinitrophenanthrene-9,10-diyl diacetate
(VI). Complex IV or V, 0.1 g (0.2 mmol), was dis-
solved in 5 ml of acetic anhydride, and the solution
was heated for 1 h at 90°C and cooled to room tem-
perature. The precipitate was filtered off and dried
under reduced pressure. Yield 85–88%, thin yellow
needles, mp 255–257°C (decomp.), Rf 0.86 (benzene–
acetone, 8:1). IR spectrum, ν, cm–1: 3092 (CH), 1782
(C=O), 1616 (C=C), 1524 (NO2), 1348 (NO2). Found,
%: C 50.14; H 2.58; N 9.49. C18H11N3O10. Calculated,
%: C 50.35; H 2.56; N 9.79.
1
(NO2). H NMR spectrum, δ, ppm: 8.23 d (2H, 1-H,
3
3
8-H, J = 8.7 Hz), 8.43 d.d (2H, 2-H, 7-H, J = 8.7,
4J = 1.8 Hz), 9.22 d (2H, 4-H, 5-H, 4J = 1.8 Hz). Mass
spectrum: m/z 298 [M]+. Found, %: C 56.77; H 2.16;
N 9.26. C14H6N2O6. Calculated, %: C 56.37; H 2.01;
N 9.40.
Compound X. Yield 0.04 g (6%), yellow–green
crystals, mp 355–357°C (from AcOH), Rf 0.21
(benzene–acetone, 8:1). IR spectrum, ν, cm–1: 1702
1
(C=O), 1544 (NO2), 1370 (NO2). H NMR spectrum,
δ, ppm: 7.73 d.d (2H, 4-H, 5-H, 3J = 8.6, 4J = 1.8 Hz),
2,4,7-Trinitrofluorenone (VII). Compound I,
0.31 g (0.09 mmol), was dissolved in 20 ml of DMF,
0.6 g (6 mmol) of copper(I) chloride was added, and
the mixture was heated for 5 h on a boiling water bath.
The mixture was filtered, and the filtrate was poured
into 150 ml of water acidified with aqueous HCl to pH
1–2. The precipitate was filtered off, washed with
water, dried, and recrystallized from acetic acid. Yield
0.22 g (76%), yellow needles, mp 173–174°C, Rf 0.75
(benzene–acetone, 30:1). The product showed no de-
pression of the melting point on mixing with a sample
of VII synthesized by nitration of fluorenone [7].
3
8.09 d.d (2H, 3-H, 6-H, J = 8.7 Hz), 8.68 d.d (2H,
3
4
2-H, 7-H, J = 8.6, J = 1.8 Hz). Mass spectrum:
m/z 298 [M]+. Found, %: C 56.66; H 2.22; N 9.74.
C14H6N2O6. Calculated, %: C 56.37; H 2.01; N 9.40.
1,3,6,8-Tetranitro-9,10-sulfuryldioxyphenan-
threne (XI) and 1,3,6-trinitro-9,10-phenanthrene-
quinone (XII). Compound VIII, 0.6 g (2.2 mmol),
was added to 25 ml of nitric acid (d = 1.51) heated to
75°C, and the mixture was quickly heated to the
boiling point, kept boiling for 8 min, and cooled. The
precipitate of XI was filtered off, washed with 5 ml of
nitric acid (d = 1.4) and water, dried, and recrystallized
from acetic acid–dioxane (2:1). The filtrate was
poured onto 100 g of ice, and the precipitate of XII
3
1H NMR spectrum, δ, ppm: 8.17 d (1H, 5-H, J =
4
8.7 Hz), 8.41 d (1H, 8-H, J = 1.8 Hz), 8.59 d (1H,
4
3
4
1-H, J = 2.3 Hz), 8.60 d.d (1H, 6-H, J = 8.7, J =
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 7 2013

ANDRIEVSKII et al.
1030
was filtered off, washed with water, dried, and recrys-
tallized from acetic acid.
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Compound XI. Yield (27%), white crystals,
mp >300°C (decomp.), Rf 0.79 (benzene–acetone,
8:1). IR spectrum, ν, cm–1: 1538 (NO2), 1436 (SO2),
1343 (NO2), 1226 (SO2). Mass spectrum: m/z 388
[M – SO2]+. Found, %: C 36.91; H 1.09; N.35; S 7.45.
C14H4N4O12S. Calculated, %: C 37.17; H 0.88;
N 12.39; S 7.08.
Compound XII. Yield 0.36 g (48%), yellow–orange
crystals, mp 261–263°C, Rf 0.53 (benzene–acetone,
8 : 1). IR spectrum, ν, cm–1: 1688 (C=O), 1532
1
(νasNO2), 1352 (νsNO2). H NMR spectrum, δ, ppm:
3
3
8.32 d (1H, 8-H, J = 8.7 Hz), 8.52 d.d (1H, 7-H, J =
5. Schenck, G.O. and Schmidt-Thomée, G.A., Justus Liebigs
Ann. Chem., 1953, vol. 584, p. 199.
8.7, 4J = 1.8 Hz), 8.68 d (1H, 3-H, 4J = 1.8 Hz), 9.34 d
4
4
(1H, 5-H, J = 1.8 Hz), 9.50 d (1H, 4-H, J = 1.8 Hz).
Mass spectrum: m/z 343 [M]+. Found, %: C 49.25;
H 1.42; N 12.34. C14H5N3O8. Calculated, %: C 48.98;
H 1.46; N 12.24.
6. Mukherjee, T.K., J. Phys. Chem., 1976, vol. 71, p. 2277.
7. Woolfolk, E.O. and Orchin, M., Organic Syntheses,
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