Bromination of deactivated polycyclic aromatic nitro compounds

Article abstract of DOI:10.1134/S1070428013100126

Bromination of 2,7-dinitro-9,10-phenanthrenequinone, 2,5-dinitro-9,10- phenanthrenequinone, and 2,4,7-trinitrofluorenone with bromine in concentrated sulfuric acid in the presence of acetic acid gave, respectively, 4-bromo-2,7-dinitro-9,10-phenanthrenequinone, 2-bromo-4,7-dinitro-9,10- phenanthrenequinone, and 5-bromo-2,4,7-trinitrofluorenone. No bromination occurred in the absence of nitric acid. The same brominated polynitro compounds can be obtained under analogous conditions directly from unsubstituted 9,10-phenanthrenequinone and fluorenone.

Full text of DOI:10.1134/S1070428013100126

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 10, pp. 1474–1481. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.M. Andrievskii, M.V. Gorelik, R.V. Linko, M.K. Grachev, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49,
No. 10, pp. 1496–1502.
Bromination of Deactivated Polycyclic
Aromatic Nitro Compounds
a
a
b
c
A. M. Andrievskii , M. V. Gorelik , R. V. Linko , and M. K. Grachev
a
State Scientific Center “Research Institute of Organic Intermediate Products and Dyes,”
ul. Bol’shaya Sadovaya 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 November 10, 2012
Abstract—Bromination of 2,7-dinitro-9,10-phenanthrenequinone, 2,5-dinitro-9,10-phenanthrenequinone, and
2
,4,7-trinitrofluorenone with bromine in concentrated sulfuric acid in the presence of acetic acid gave,
respectively, 4-bromo-2,7-dinitro-9,10-phenanthrenequinone, 2-bromo-4,7-dinitro-9,10-phenanthrenequinone,
and 5-bromo-2,4,7-trinitrofluorenone. No bromination occurred in the absence of nitric acid. The same
brominated polynitro compounds can be obtained under analogous conditions directly from unsubstituted
9
,10-phenanthrenequinone and fluorenone.
DOI: 10.1134/S1070428013100126
Aromatic bromo derivatives [1] are important for
organic synthesis as intermediate products capable of
entering into a number of bromine exchange reactions.
The significance of bromoaromatics considerably in-
creased in the past decades due to development of
cross-coupling reactions catalyzed by palladium com-
pounds [2, 3]. Therefore, studies in the field of syn-
thesis of bromoarenes are quite urgent. The main meth-
od for introduction of a bromine atom into aromatic
ring is based on substitution of hydrogen by electro-
philic brominating agent [4]. Electrophilic bromination
readily occurs if an aromatic ring contains activating
electron-donating groups. The presence of electron-
withdrawing substituents that deactivate aromatic
system requires special bromination procedures [5].
We previously developed [6] a new procedure for
the bromination of deactivated aromatic compounds
with bromine in sulfuric acid in the presence of nitric
acid and examined its applicability to compounds of
the benzene series [7]. In the present work the devel-
oped procedure was tested on deactivated polycyclic
aromatic systems, nitro-substituted 9,10-phenanthrene-
quinones and fluorenone.
and 4-nitrophenanthrenequinones, whereas treatment
of the same compound with 65% HNO in 98% H SO
3
2
4
at 50°C afforded a mixture of 2,7- and 2,5-dinitro
derivatives [8]. The bromination of 2-nitro-9,10-phe-
nanthrenequinone with bromine in acetic acid at 140°C
under pressure or in nitrobenzene under photochemical
initiation in the presence of benzoyl peroxide was
reported to produce 3-bromo-7-nitro-9,10-phenan-
threnequinone [9]. 4-Nitro-, 2,7-dinitro-, and 2,5-di-
nitro-9,10-phenanthrenequinones failed to undergo
bromination under the above conditions. No other
methods for bromination of nitro-substituted 9,10-phe-
nanthrenequinones have been reported so far.
By heating 2,7-dinitro-9,10-phenanthrenequinone
(
I) and 2,5-dinitro-9,10-phenanthrenequinone (II) with
bromine and nitric acid in concentrated sulfuric acid at
0–55°C we obtained 4-bromo-2,7-dinitro-9,10-phe-
5
nanthrenequinone (III) and 2-bromo-4,7-dinitro-9,10-
phenanthrenequinone (IV), respectively (Scheme 1).
A mixture of compounds III and IV was also formed
in analogous reaction with unsubstituted 9,10-phenan-
threnequinone (V). These findings suggest that a com-
bination of brominating and nitrating agents promotes
nitration of phenanthrenequinone and mononitrophe-
nanthrenequinones derived therefrom and that the re-
sulting dinitrophenanthrenequinones I and II undergo
As substrates we selected 2,7- and 2,5-dinitro-9,10-
phenanthrenequinones I and II. The nitration of phe-
nanthrenequinone with boiling 65% nitric acid gave 2-
1
474

BROMINATION OF DEACTIVATED POLYCYCLIC AROMATIC NITRO COMPOUNDS
1475
Scheme 1.
O
O
O
O
Br , HNO , H SO
2
3
2
4
5
0–55°C
O N
2
NO2
O N
2
NO2
Br
III
I
O
O
O
O
Br , HNO , H SO
2
3
2
4
5
0–55°C
NO2
Br
NO2
NO2
NO2
II
IV
O
O
Br , HNO , H SO
2
3
2
4
5
0–55°C
III
+ IV
V
bromination. 2,4,7-Trinitro-9,10-phenanthrenequinone
remained unchanged under analogous conditions.
trinitrobiphenyl-2,2′-dicarboxylic acid (IX) in boiling
dimethylformamide. Apart from compounds VI and
VII, the reaction mixture obtained from I contained
three more products, assumingly resulting from mono-,
di-, and tribromination of VII. The bromination of VII
with bromine in the presence of nitric acid in
The position of the bromine atom in molecule III
was determined by X-ray analysis of its solvate with
H O and DMF [10], and the structure of IV was
2
1
1
proved by H NMR. The H NMR spectrum of IV
contained three doublets at δ 8.83 (8-H), 8.60 (6-H),
and 7.85 ppm (5-H). Analogous signals were observed
from protons in positions 1, 3, and 4 of 2,5-dinitro-
2
0% oleum at 80–100°C gave 1,3,6,8-tetrabromo-2,7-
dinitrochromeno[5,4,3-cde]chromene-5,10-dione (X)
in 52% yield.
9
,10-phenanthrenequinone (II). The latter also dis-
Most probably, 2,7-dinitro-9,10-phenanthrene-
quinone (I) is initially converted into 4-bromo deriv-
ative III which is oxidized to 6-bromo-4,4′-dinitrobi-
phenyl-2,2′-dicarboxylic acid, and bromination of the
latter yields compound VI. The reverse reaction
sequence, i.e., dibromination of I followed by oxida-
tion, is hardly possible, for introduction of two substit-
uents into positions 4 and 5 of phenanthrenequinone is
hindered for steric reasons. The subsequent cyclization
of VI leads to dinitrodioxapyrene VII.
We also examined bromination of 2,7-dinitro- and
2,4,7-trinitrofluorenones. The nitration of fluorenone
(XV) with concentrated nitric acid at room temperature
gives 2-nitrofluorenone, while the reaction at the
boiling point leads to 2,7-dinitrofluorenone [12]. The
nitration of XV with a mixture of fuming nitric acid
and concentrated sulfuric acid on heating for 2 h
produces 2,4,7-trinitrofluorenone [13], while
2,4,5,7-tetranitrofluorenone is formed on prolonged
heating (8.5 h) [14].
played a triplet at δ 7.92 ppm (7-H), which was absent
in the spectrum of IV. Two doublets at δ 8.50 (1-H)
and 8.44 ppm (3-H) in the spectrum of IV appeared in
a weaker field relative to the 8-H and 6-H signals of II
(
δ 8.43 and 8.22 ppm, respectively). Thus the position
of signals, their intensity and multiplicity, and coupling
constants indicated the presence of substituents in
positions 2, 4, and 7.
Treatment of 2,7-dinitro-9,10-phenanthrenequinone
(
I) with bromine and nitric acid in sulfuric acid under
more severe conditions (75–80°C, 3 h) lead to the
formation of 6,6′-dibromo-4,4′-dinitrobiphenyl-2,2′-di-
carboxylic acid (VI) and 2,7-dinitrochromeno-
5,4,3-cde]chromene-5,10-dione (VII) (Scheme 2).
Compound VI was also synthesized by bromination of
,4′-dinitrobiphenyl-2,2′-dicarboxylic acid. Bis-lactone
[
4
VII was described previously [11]; it was prepared by
bromination of 4,4′,6-trinitrobiphenyl-2,2′-dicarbox-
ylic acid (VIII), followed by heating 6-bromo-4,4′,6′-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013

1
476
ANDRIEVSKII et al.
Scheme 2.
O
O
HO(O)C
NO2
Br , HNO , H SO
Br COOH
2
3
2
4
7
5–80°C
O N
2
NO2
O N
2
NO2
NO2
COOH
VIII
O N
2
HO(O)C Br
I
VI
O
Br
O
O
HO(O)C
Br
NO2
NO2
NO2
O
Br , HNO
2 3
2
0% SO /H SO
4
DMF, Δ
3
2
Br
Br
O
O
NO2
COOH
O N
2
O N
2
O N
2
Br
O
O
X
VII
IX
By heating 2,4,7-trinitrofluorenone (XI) with
bromine and nitric acid in concentrated sulfuric acid at
0–85°C we obtained 5-bromo-2,4,7-trinitrofluorenone
XII) in 96% yield (Scheme 3). Compound XII was
synthesized previously by nitration of 4-bromofluor-
enone with fuming nitric acid in a mixture of sulfuric
and acetic acids [15]. Perepichka et al. [16] modified
our procedure described in [7]; initially, fluorenone
was nitrated with a nitrating mixture, and the resulting
trofluorenone (XI), while cleavage of the fluorenone
ring system occurred under more severe conditions. In
the latter case, apart from unreacted tetranitrofluore-
none XVI, 6′-bromo-2′,4,4′,6-tetranitrobiphenyl-2-car-
boxylic acid (XVII) was isolated from the reaction
mixture. Acid XVII was also synthesized from
2′,4,4′,6-tetranitrobiphenyl-2-carboxylic acid (XVIII)
by the action of bromine in a nitrating mixture.
8
(
2
,7-Dinitrofluorenone (XIII) as less deactivated
2
,4,7-trinitrofluorenone (XI) without isolation was
substrate than 2,4,7-trinitrofluorenone (XI) underwent
simultaneous nitration and bromination. When the
reaction mixture was heated at 60–65°C, we isolated
treated with bromine on heating for 2 h at 55–60°C; as
a result, 5-bromo-2,4,7-trinitroflurenone (XII) was ob-
tained in 91% yield.
6
0% of 5-bromo-2,4,7-trinitrofluorenone (XII) and
2
,4,5,7-Tetranitrofluorenone (XVI) remained un-
20% of 4,5-dibromo-2,7-dinitrofluorenone (XIV)
changed under the conditions of bromination of trini-
(Scheme 3). Monitoring of the reaction course by TLC
Scheme 3.
O
O
O
Br , HNO
Br , HNO
2 3
2
3
H SO
H SO
2 4
2
4
O N
2
NO2
O N
2
NO2
O N
Br O N
2
2
XI
XII
XV
O
O
Br , HNO
2
3
H SO
2
4
O N
2
NO2
O N
2
NO2
Br
Br
XIV
XIII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013

BROMINATION OF DEACTIVATED POLYCYCLIC AROMATIC NITRO COMPOUNDS
1477
Scheme 4.
O
O
O
CuCl, DMF, Δ
O N
2
NO2
O N
NO2
2
Br
III
Br
XIX
1
and H NMR revealed the presence of 4-bromo-2,7-
dinitrofluorenone and 2,4,7-trinitrofluorenone in the
initial period, and these compounds were then convert-
ed into 4,5-dibromo-2,7-dinitrofluorenone (XIV) and
brominating agent is likely to be the reaction of nitro-
nium cation with bromine. The overall bromination
stoichiometry corresponds to consumption of 0.5 mol
of Br per 1 mole of aromatic substrate in the reduction
2
5
-bromo-2,4,7-trinitroflurenone (XII). The latter
of nitronium ion to nitrosonium [7] (Scheme 5).
became the only reaction product after prolonged
heating. Thus 5-bromo-2,4,7-trinitroflurenone (XII)
can be synthesized directly from unsubstituted fluore-
none (XV) by treatment with bromine and nitric acid
in sulfuric acid until disappearance of 4,5-dibromo-
Scheme 5.
2ArH + Br2 + NO2 HSO4
2ArBr + NO HSO4 + H O
2
Prevalence of nitration over bromination for moder-
ately deactivated aromatic compounds is not related to
the low rate of generation of brominating agent. Pro-
longed keeping of a mixture of bromine with nitric and
sulfuric acids before addition of aromatic substrate
does not favor bromination instead of nitration.
2
,7-dinitrofluorenone (XIV). The transformation of
XIV into XII under the bromination conditions was
confirmed by special experiment with preliminarily
isolated 4,5-dibromo-2,7-dinitrofluorenone. Obviously,
this transformation involves elimination of bromine
from the 4-position (hydrodebromination) and subse-
quent nitration. Hydrodebromination was also observed
in the nitration of 2-bromophenanthridinone [17].
The fact that the brominating agent is less reactive
than nitrating agent toward moderately deactivated
compounds but is more reactive toward strongly
deactivated substrates may be rationalized by its lower
sensitivity to electronic structure of substrates. Intro-
duction of electron-withdrawing substituents into sub-
strate molecule hinders nitration to a considerably
greater extent as compared to bromination, i.e., the
substrate selectivity in the bromination is lower than in
the nitration. As the number of electron-withdrawing
nitro groups in a substrate molecule increases, at some
step of structural variations the substrate becomes
deactivated toward electrophilic attack by nitronium
ion more strongly than toward attack by brominating
agent. As a result, the ratio of the nitration and
bromination rates changes to the opposite, and the
bromination becomes the dominant process.
The sensitivity of a reaction to variation of the
substrate structure is quantitatively characterized by
the ρ value [22, 23]. The nitration in sulfuric acid is
generally highly sensitive to electronic effects of sub-
stituents (ρ = –9.7 for benzene derivatives [24]).
Insofar as there are no corresponding kinetic data, the
reduction of the reactivity toward nitration may be
assessed qualitatively by comparing the experimental
conditions. Mononitro phenanthrenequinones are con-
verted into dinitro derivatives by the action of 65%
4
,5-Dibromo-2,7-dinitrofluorenone (XIV) and
4
-bromo-2,7-dinitrofluorenone (XIX) were synthe-
sized previously by bromination of 2,7-dinitrofluore-
none in concentrated sulfuric acid in the presence of
silver sulfate [18, 19]. We also prepared 4-bromo-2,7-
dinitrofluorenone (XIX) by rearrangement of 4-bromo-
2
,7-dinitro-9,10-phenanthrenequinone (III) on heating
in DMF in the presence of CuCl by analogy with the
rearrangement of 2,4,7-trinitro-9,10-phenanthrene-
quinone into 2,4,7-trinitrofluorenone [20] (Scheme 4).
Thus, as in the benzene series [7], the action of
bromine and nitric acid in concentrated sulfuric acid on
moderately deactivated polycyclic aromatic com-
pounds initially brings about their nitration, and the
resulting strongly deactivated compounds undergo
bromination. The question arises as to the nature of the
brominating agent. The presence of nitric acid is
essential for the bromination, otherwise no reaction
occurs. The concentration of sulfuric acid is also
important. The brominating power of the system in
~
90% sulfuric acid is considerably lower, and it dis-
appears completely in going to 85% sulfuric acid [7].
Insofar as nitric acid in ≥90% sulfuric acid exists as
nitronium salt [21], the key step in the formation of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013

1
478
ANDRIEVSKII et al.
HNO in concd. H SO in 30 min at 50°C, whereas the
TLC on Silufol UV-254 plates; spots were visualized
3
2
4
transformation of 2,7-dinitrophenanthrenequinone into
,4,7-trinitro derivative requires prolonged (14.5 h)
heating with fuming HNO in concd. H SO at 100°C,
by treatment with a mixture of solutions of SnCl and
2
2
4-dimethylaminobenzaldehyde in aqueous ethanol
acidified with HCl. Silicagel L (40–100 μm,
Chemapol, Czechia) was used for preparative column
chromatography. The melting points were determined
on a Boetius micro hot stage. The mass spectra were
recorded on an MKh-1320 mass spectrometer.
3
2
4
1
6% of the initial dinitro compound remaining un-
changed [8].
The high sensitivity to structural variation in the
substrate upon nitration with nitronium ion is deter-
mined by the formation of a polar transition state
whose structure is similar to an ionic σ complex bearing
a whole positive charge [23]. The lower sensitivity of
the bromination to electronic properties of substituents
indicates that the corresponding transition state is less
polar and that it results from attack by less polar
reagent. The reaction of bromine with nitronium ion is
unlikely to involve complete electron transfer with
formation of a solvated species like bromonium
hydrogen sulfate but it is limited to polarization of
bromine molecule due to association. The brominating
agent may be represented as complex A of bromine
molecule with nitronium ion, which is stabilized by
solvation with sulfuric acid. The electron-deficient
bromine atom in the polarized Br–Br fragment of
complex A acts as electrophilic species, and further
transformations occur with participation of the sub-
strate. However, special studies are necessary to
identify elementary steps of the examined process.
4-Bromo-2,7-dinitro-9,10-phenanthrenequinone
(III). a. Compound I, 10 g (34 mmol), was dissolved
in 120 ml of H SO (d = 1.84), 12.4 g (80 mmol) of
2
4
bromine and 4.0 ml of HNO (d = 1.51) were added,
3
and the mixture was heated to 50–55°C and stirred for
2 h at that temperature. The mixture was cooled and
poured onto ice, and the precipitate was filtered off,
washed with water, dried, and recrystallized from
acetic acid. Yield 8.0 g (63%), yellow crystals, R 0.45
f
(benzene–acetone, 7:1), mp >300°C (decomp., from
–
1
AcOH–dioxane, 2:1). IR spectrum, ν, cm : 1700
(C=O); 1515, 1340 (NO ). Found, %: C 44.29; H 1.58;
2
Br 21.32; N 7.62. C H BrN O . Calculated, %:
1
4
5
2
6
C 44.59; H 1.34; Br 21.19; N 7.43.
2
-Bromo-4,7-dinitro-9,10-phenanthrenequinone
IV). a. Compound II, 8.0 g (27 mmol), was dissolved
in 100 ml of H SO (d = 1.84), 12.4 g (80 mmol) of
(
2
4
bromine was added, the mixture was heated to 40–
5°C, 2.0 ml (45 mmol) of HNO (d = 1.51) was
4
3
added, and the mixture was heated to 55°C and stirred
for 30 min at that temperature. The mixture was cooled
and poured onto ice, and the precipitate was filtered
off, washed with water, dried, and recrystallized from
(
Br—Br · · · NO HSO )·nH SO
2 4 2 4
A
The concept of complex A as brominating agent
allows us to understand the lack of correlation between
the oxidizing power (which is given by standard redox
potential) and bromination efficiency [7]. The oxida-
acetic acid. Yield 5.4 g (53%), yellow crystals, R 0.60
f
(
benzene–acetone, 7:1), mp 253.5–254.5°C (from
–1
AcOH). IR spectrum, ν, cm : 1685 (C=O); 1525, 1350
1
(
NO ). H NMR spectrum, δ, ppm: 7.85 d (1H, 5-H,
2
ox
3
4
tion potential E measured electrochemically relative
J = 8.2 Hz), 8.43 d (1H, 3-H, J = 2.0 Hz), 8.52d (1H,
4
3
4
to standard hydrogen electrode does not reflect the
ability of oxidant to donor–acceptor interaction with
bromine, which determines generation of brominating
agent. Nitronium ion activates bromine molecule mak-
ing the latter electrophilic Lewis acid, and it acts as
oxidant in some further steps.
1
1
-H, J = 2.0 Hz), 8.60 d.d (1H, 6-H, J = 8.2, J =
4
.8 Hz), 8.84 d (1H, 8-H, J = 1.8 Hz). Found, %:
C 44.39; H 1.90; Br 20.92; N 7.40. C H BrN O . Cal-
1
4
5
2
6
culated, %: C 44.59; H 1.34; Br 21.19; N 7.43.
b. 9,10-Phenanthrenequinone, 2.08 g (10 mmol),
was treated as described above in a. The precipitate
was dissolved in a mixture of 160 ml of benzene and
EXPERIMENTAL
2
0 ml of acetone, and isomers III and IV were sepa-
1
rated by column chromatography on silica gel using
benzene–acetone (8:1) as eluent. From the first frac-
tion we isolated 0.98 g (26%) of IV, and from the
second, 1.47 g (39%) of III.
The H NMR spectra were recorded on a Jeol ECX-
00 spectrometer at 400.13 MHz using DMSO-d as
solvent; the chemical shifts are given relative to tetra-
methylsilane. The IR spectra were obtained in KCl on
a Perkin Elmer 598 instrument. The progress of reac-
tions and the purity of products were monitored by
4
6
6,6′-Dibromo-4,4′-dinitrobiphenyl-2,2′-dicarbox-
ylic acid (VI) and 2,7-dinitrochromeno[5,4,3-cde]-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013

BROMINATION OF DEACTIVATED POLYCYCLIC AROMATIC NITRO COMPOUNDS
1479
+
chromene-5,10-dione (VII). a. Compound I, 1.05 g
C 36.60; H 1.48; Br 17.83; N 8.88. m/z 455/457 [M] .
(
3.5 mmol), was dissolved in 20 ml of H SO (d =
C H BrN O . Calculated, %: C 36.84; H 1.33;
2
4
14
6
3
10
1
.84), 2 ml (40 mmol) of bromine and 1 ml of HNO
Br 17.52; N 9.21.
3
(
d = 1.51) were added, and the mixture was heated to
1
,3,6,8-Tetrabromo-2,7-dinitrochromeno-
5
5–60°C and stirred for 1.5 h at that temperature. The
[
3
2
5,4,3-cde]chromene-5,10-dione (X). Compound VII,
mixture was then heated to 75–80°C, stirred for 3 h,
cooled, and poured onto 100 g of ice. The precipitate
was filtered off, washed with water, dried, and recrys-
tallized from acetic acid. Yield of VII 0.38 g (33%),
.0 g (9 mmol), was dissolved in 100 ml of
0% oleum, 6 ml (116 mmol) of bromine and 15 ml of
HNO (d = 1.51) were added, and the mixture was
3
heated to 95–100°C and stirred for 15 h at that tem-
perature. By the end of the reaction strong foaming
was observed, and a solid precipitated. The mixture
was cooled to room temperature, and the precipitate
was filtered off through a glass filter, washed with
water, dried, and recrystallized from DMSO. Yield
yellow crystals, R 0.36 (benzene), mp 333–335°C
f
(
decomp., from AcOH); published data [11]: mp 331–
–
1
3
1
32°C (decomp.). IR spectrum, ν, cm : 1770 (C=O);
+
544, 1358 (NO ). Mass spectrum: m/z 328 [M] .
2
Found, %: C 51.18; H 1.19; N 8.45. C H N O . Cal-
culated, %: C 51.24; H 1.23; N 8.54.
14
4
2
8
3
.1 g (53%), colorless crystals, R 0.87 (benzene),
f
–1
The mother liquor was diluted with water, and the
precipitate was filtered off, washed with water, dried,
and recrystallized from benzene. Yield of VI 0.14 g
mp 350°C (from DMSO). IR spectrum, ν, cm : 1755
(C=O); 1558, 1377 (NO ). Found, %: C 26.26;
2
+
Br 49.42; N 4.23. m/z 640/642/644/646/648 [M] .
(
8%), colorless crystals, R 0.83 (25% aq. ammonia–
C Br N O . Calculated, %: C 26.12; Br 49.65; N 4.35.
f
14
4
2
8
dioxane, 1:3), mp 303–304°C (in a sealed capillary;
5
-Bromo-2,4,7-trinitrofluorenone (XII).
–
1
from benzene). IR spectrum, ν, cm : 3200–2400
OH); 1710 (C=O); 1534, 1346 (NO ). Found, %:
a. 2,4,7-Trinitrofluorenone (XI), 3.15 g (10 mmol),
was dissolved in 60 ml of H SO (d = 1.84), 10 ml of
(
2
2
4
C 34.23; H 1.23; Br 32.27; N 5.89. m/z 488/490/492
HNO (d = 1.51) and 1 ml of bromine were added, and
3
+
[
M] . C H Br N O . Calculated, %: C 34.29; H 1.23;
1
4
6
2
2
8
the mixture was heated for 2 h at 80–85°C. The mix-
ture was cooled and poured onto 200 g of ice, and the
precipitate was filtered off, washed with water, dried,
and recrystallized from ethanol. Yield 3.78 g (96%),
Br 32.61; N 5.72.
b. 4,4′-Dinitrobiphenyl-2,2′-dicarboxylic acid,
.65 g (5 mmol), was dissolved in 15 ml of H SO (d =
1
1
2
4
.84), 2 ml (40 mmol) of bromine and 2 ml of HNO
light yellow crystals, R 0.6 (benzene), mp 192–193°C
3
f
(
d = 1.51) were added, and the mixture was heated to
0°C and stirred for 1 h at that temperature. The mix-
(from EtOH); published data [15]: mp 191–192°C.
–
1
5
IR spectrum, ν, cm : 1729 (C=O); 1533, 1343 (NO ).
2
1
4
ture was then heated to 65°C, stirred for 2 h, cooled,
and poured onto 100 g of ice. The precipitate was
filtered off, washed with water, dried, and recrystal-
lized from acetic acid. Yield of VI 1.8 g (73%). The
product was identical to a sample isolated as described
H NMR spectrum, δ, ppm: 8.15 d (1H, 8-H, J
=
8
,6
4
1.3 Hz), 8.62 d (1H, 1-H, J = 1.4 Hz), 8.75 d (1H,
1
,3
4
4
6-H, J = 1.3 Hz), 9.80 d (1H, 3-H, J = 1.4 Hz).
6
,8
3,1
1
3
8
5
C NMR spectrum, δ, ppm: 118.4 (C ), 121.0 (C ),
1
3
6
7
122.0 (C ), 126.1 (C ), 135.6 (C ), 149.6 (C ), 150.1
2
4
4a
4b
in a in the IR spectrum, melting point, and R value.
(C ); 138.9, 139.7, 139.8, 144.6, 146.1 (C , C , C ,
8a 9a 9
f
C , C ); 185.3 (C ). Found, %: C 39.58; H 1.05;
Br 20.26; N 10.35. C H BrN O . Calculated, %:
A mixture of 0.2 g of compound VI or IX and 6 ml
of DMF was heated for 3 h under reflux. The solution
was cooled to room temperature and poured into
1
3
4
3
7
C 39.62; H 1.02; Br 20.28; N 10.66.
2
00 ml of water acidified with hydrochloric acid to
b. Compound XV, 2.14 g (5 mmol), was dissolved
in 60 ml of H SO (d = 1.84), 10 ml of HNO (d =
1.51) and 1 ml of Br were added, and the mixture was
pH 1–2. The precipitate of compound VII was filtered
off, washed with water, dried, and recrystallized from
acetic acid. Yield 82% (from VI), 83% (from IX).
2
4
3
2
treated as described above in a. Yield 1.38 g (70%).
6
-Bpomo-4,4′,6′-trinitrobiphenyl-2,2′-dicarbox-
c. A mixture of 2.14 g (5 mmol) of 4,5-dibromo-
2,7-dinitrofluorenone (XIV), 60 ml of H SO (d =
ylic acid (IX) was synthesized in a similar way from
compound VIII. Yield 1.4 g (77%), light yellow
2
4
1.84), 10 ml of HNO (d = 1.51), and 1 ml of bromine
3
needles, R 0.76 (25% aq. ammonia–dioxane, 1:3),
was heated for 4 h at 60–65°C until the initial com-
pound disappeared (TLC). The mixture was poured
onto ice, and the precipitate was filtered off and recrys-
tallized to isolate 1.18 g (60%) of XII.
f
mp 284–285°C (in a sealed capillary; from 10% aque-
–
1
ous acetic acid). IR spectrum, ν, cm : 3200–2400
(
OH); 1712 (C=O); 1536, 1346 (NO ). Found, %:
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013

1
480
ANDRIEVSKII et al.
d. Compound XIII, 2.7 g (10 mmol), was dissolved
the precipitate was filtered off, washed with water,
dried, and recrystallized from acetic acid. Yield 0.70 g
in 60 ml of H SO (d = 1.84), 10 ml of HNO (d =
2
4
3
1
.51) and 1 ml of bromine were added, and the mixture
(15%), light yellow crystals, R 0.26 (benzene–acetone,
f
1
was heated for 4 h at 60–65°C. The mixture was
cooled to room temperature, and the precipitate was
filtered off, washed with water, dried, and recrystal-
lized from acetic acid. Yield 2.36 g (60%).
10:1), mp 123–125°C (from AcOH). H NMR spec-
4
trum, δ, ppm: 8.96 d (1H, 5′-H, J = 2.3 Hz), 8.98 d
4
4
(1H, 3′-H, J = 2.3 Hz), 9.00 d (1H, 3-H, J = 2.3 Hz),
4
9.17 d (1H, 5-H, J = 2.3 Hz), 12.5 br.s (1H, COOH).
1
3
5′
3′
C NMR spectrum, δ , ppm: 119.7 (C ), 124.0 (C ),
4
,5-Dibromo-2,7-dinitrofluorenone (XIV). The
C
6
′
3
5
2
1
(
24.7 (C ), 130.0 (C ), 132.5 (C ), 134.2 (C ), 136.5
1′ 1 4 6
filtrate obtained after separation of compound XII was
poured onto 200 g of ice, and the precipitate was
filtered off, washed with water, dried, and recrystal-
lized from acetic acid. Yield 0.86 g (20%), yellow
C ), 137.7 (C ); 148.5, 148.5, 148.6, 148.7 (C , C ,
2′ 4′
C , C ); 163.4 (C=O). Found, %: C 33.95; H 1.15;
Br 17.47; N 12.05. C13 BrN 10. Calculated, %:
C 34.16; H 1.10; Br 17.48; N 12.26.
H
O
5
4
crystals, R 0.7 (benzene), mp 228–229°C (from
f
AcOH); published data [19]: mp 226–227°C. IR spec-
The residue obtained after treatment of the product
–
1
trum, ν, cm : 1739 (C=O); 1533, 1344 (NO ).
2
with a solution of NaHCO was washed with water and
3
1
4
H NMR spectrum, δ, ppm: 8.35 d (2H, 1-H, 8-H, J =
dried. We thus isolated 3.02 g (84%) of unreacted
4
1
.8 Hz), 8.72 d (2H, 3-H, 6-H, J = 1.8 Hz). Found, %:
2
,4,5,7-tetranitrofluorenone (XVI).
C 36.58; H 1.08; Br 37.42; N 6.35. C H Br N O .
1
3
4
2
2
5
b. 2′,4,4′,6-Tetranitrobiphenyl-2-carboxylic acid
Calculated, %: C 36.48; H 0.94; Br 37.34; N 6.55.
-Bromo-2,7-dinitrofluorenone (XIX). Copper(I)
chloride, 0.2 g (2 mmol), was added to a solution of
.20 g (0.53 mmol) of compound III in 8 ml of DMF,
and the mixture was heated to 90–95°C and stirred for
h at that temperature. The mixture was then filtered,
(
XVIII), 3.78 g (10 mmol), was dissolved in 60 ml of
4
concentrated sulfuric acid, 10 ml of HNO (d = 1.51)
3
and 1 ml of bromine were added, and the mixture was
heated to 65°C and stirred for 2 h at that temperature.
The mixture was cooled to room temperature and
poured onto 200 g of ice, and the precipitate was
filtered off, washed with water, dried, and recrys-
tallized from acetic acid. Yield 3.38 g (74%); the prod-
uct was identical to a sample of XVII prepared as
described in a.
0
4
the filtrate was poured into 50 ml of water acidified
with hydrochloric acid to pH 1–2, and the precipitate
was filtered off, washed with water, dried, and recrys-
tallized from acetic acid. Yield 0.10 g (54%), light
brown needles, R 0.7 (benzene), mp 262–264°C (from
f
–
1
AcOH). IR spectrum, ν, cm : 1735 (C=O), 1520
1
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NO , asym.), 1344 (NO , sym.). H NMR spectrum, δ,
2
2
4
ppm: 8.32 d (1H, 1-H, J = 2.1 Hz), 8.37 d (1H, 8-H,
1
,3
4
3
4
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8
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6,5
6,8
3
2
3
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13
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8
6
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3
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6
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013