New syntheses of N,N′-diaryl-substituted quinone diimines: I. Synthesis of N,N′-bis(4-aminophenyl)-1,4-benzoquinone diimine

Article abstract of DOI:10.1134/S1070428017060252

Oxidative condensation of p-phenylenediamine by the action of K₂S₂O₈ in acetic acid afforded N,N′-bis(4-aminophenyl)-1,4-benzoquinone diimine which underwent self-condensation on heating. Acetylation of the title compound

Full text of DOI:10.1134/S1070428017060252

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 6, pp. 955–958. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © A.A. Durgaryan, R.A. Arakelyan, N.A. Durgaryan, N.Sh. Martikyan, 2017, published in Zhurnal Organicheskoi Khimii, 2017,
Vol. 53, No. 6, pp. 938–941.
SHORT
COMMUNICATIONS
New Syntheses of N,N′-Diaryl-Substituted Quinone Diimines:
I. Synthesis of N,N′-Bis(4-aminophenyl)-
1,4-benzoquinone Diimine
A. A. Durgaryan,* R. A. Arakelyan, N. A. Durgaryan, and N. Sh. Martikyan
Yerevan State University, ul. A. Manukyana 1, Yerevan, 0025 Armenia
e-mail: durgaran@ysu.am
Received August 26, 2015; revised May 25, 2017
2 2 8
Abstract—Oxidative condensation of p-phenylenediamine by the action of K S O in acetic acid afforded
N,N′-bis(4-aminophenyl)-1,4-benzoquinone diimine which underwent self-condensation on heating. Acetyla-
tion of the title compound with acetic anhydride in acetic acid gave more stable diacetyl derivative.
DOI: 10.1134/S1070428017060252
The emeraldine base form of polyaniline contains
benzoquinone diimine fragments and is one of the
most important conducting polymers [1, 2]. Polymers
and oligomers containing quinone diimine fragments
structurally similar to polyaniline (also known as
pernigraniline) were synthesized by condensation of
aromatic amines only with those quinones which can-
not be involved in Michael reaction [3–5], as well as
by reaction of N,N′-dichloro-1,4-benzoquinone diimine
with organometallic compounds [6]. Oxidative con-
densation of N-phenyl-p-phenylenediamine by the
action of FeCl ·6H O gave aniline tetramer with
a quinone diimine fragment [7]. N,N′-Diaryl-1,4-
benzoquinone diimines were obtained in 28–42% yield
by oxidation of p-phenylenediamine in the presence of
aniline and substituted anilines in aqueous ethanol in
the presence of an acid [8]. Aniline oligomers includ-
ing three to eight rings were prepared by reaction of
N,N′-bis(4-aminophenyl)-1,4-benzoquinone diimine
with substituted diphenylamines on exposure to air [9].
Enzymatic oxidation of p-phenylenediamine with hy-
drogen peroxide was reported [10] to produce 2,5-di-
amino-N,N′-bis(4-aminophenyl)-1,4-benzoquinone
diimine; however neither procedure for the isolation of
3
2
Scheme 1.
NH2
NH2
K S O
2
2
8
H N
H N
2
2
NH2
NH3
p-C H (NH )
H N
2
NH
2
H N
2
NH
2
6
4
2 2
N
N
H
H
H
H
N
N
–
NH3
–H+
H N
2
H N
2
NH2
NH2
NH2
N
NH2
K S O
8
2
2
2
n + 1
+ 2n NH3
H N
2
H N
2
N
n
9
55

9
56
DURGARYAN et al.
Scheme 2.
N
NH2
n + 1
H N
2
N
NH2
H N
2
NH
N
N
NH2
N
N
H
H
n
the pure compound nor its spectral parameters were
given. The same compound in the salt form was
formed in the oxidation of p-phenylenediamine with
silver(I) ions[11]. Aniline oligomers containing benzo-
quinone diimine fragments were also obtained by
oxidation of the corresponding amines that are dif-
ficultly accessible [12–17].
phenyl)-1,4-benzoquinone diimine takes up water by
~90% under the action of 0.5 N H SO .
2
4
With the goal of minimizing side reactions pro-
moted by strong acids, we have developed a new
procedure for the synthesis of low- and high-molec-
ular-weight quinone diimines via oxidation of
p-phenylenediamines with potassium peroxodisulfate
in acetic acid [23]. The reaction of p-phenylenedi-
amine with K S O at a molar ratio of 4:1 in acetic
Cataldo [18] reported that the oxidation of
p-phenylenediamine with potassium peroxodisulfate in
aqueous HCl gives polyquinoxaline. However, we
previously showed that the oxidative polymerization of
p-phenylenediamine in aqueous HCl follows mainly
Scheme 1 and yields poly(1,4-benzoquinone diimine-
N,N′-diyl-1,4-phenylene) [19–21]. Under these condi-
tions (22–25°C, aqueous HCl), the product undergoes
further transformations, in particular bisulfate ion adds
to the quinone diimine units [19, 20]. It is also known
that treatment of pernigraniline with 1 N HCl leads to
addition of hydrogen chloride to 50% of the quinoid
rings [22]. According to our data, N,N′-bis(4-amino-
2
2
8
acid at 15°C afforded two fractions, one of which was
soluble in methanol while the other was not.
Recrystallization of the first fraction from ethanol
gave compound 1 (Scheme 1, n = 1) with mp 257–
2
58°C. The melting point may change depending on
the rate of heating due to thermal self-condensation
(
mp 172°C [8]).
The UV spectrum of 1 in DMSO displayed two
absorption maxima at λ 341 and 496 nm (see figure). A
solution of 1 in methanol showed the third maximum
at λ 250 nm. According to published data, compound 1
absorbs at λmax 572 nm in DMF, at 556 nm in THF, and
at 532 nm in methylene chloride [8]. It should be noted
for comparison that the UV spectrum of 2,5-dimethyl-
N,N′-bis(4-methylphenyl)-1,4-benzoquinone diimine in
DMF contains absorption maxima at λ 310 and 457 nm
and that the absorption maximum of N,N′-bis(4-meth-
ylbenzenesulfonyl)-1,4-benzoquinone diimine is locat-
D
1
1
0
.5
.0
.5
0
1
1
ed at λ 484 nm [6]. In the H NMR spectrum of 1
we observed signals from protons of the amino groups
and quinone and benzene rings with the expected
intensity ratio.
2
When compound 1 was extracted from the reaction
mixture with hot ethanol, the amounts of the soluble
and insoluble fractions were irreproducible, presum-
ably because of self-condensation of 1 (Scheme 2).
This assumption was checked as follows. A solution of
3
00
400
500
600
700
λ, nm
UV spectra of N,N′-bis(4-aminophenyl)-1,4-benzoquinone
diimine (1) and its acetyl derivative 2 in DMSO.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 6 2017

NEW SYNTHESES OF N,N′-DIARYL-SUBSTITUTED QUINONE DIIMINES: I.
957
Scheme 3.
H
N
NH2
N
N
Ac O
2
Ac
Ac
H N
2
N
N
N
H
1
2
1
in ethanol was heated under reflux. As a result,
soluble fraction 0.50 g (75%), mp 257–258°C. IR
–
1
a compound insoluble in methanol was formed. The
same product was obtained when compound 1 was
heated at 260°C. Obviously, the reaction involves
spectrum, ν, cm : 3462, 3418, 3337 (NH ), 3034
2
(C–H), 1605 (C=Carom), 1544 (NH ), 1502 (C=C,
2
quinone), 1384 and 1237 (=N–C), 1275 (N–C), 1166
1
1
,4-addition of primary amino group to the quinone
(C–H), 833 (δC–Harom). H NMR spectrum, δ, ppm:
diimine fragment (Scheme 2) with formation of oligo-
mers and a polymer. The IR spectrum of the product
obtained by heating, assumingly poly[imino-1,4-phe-
nyleneimino-4-(4-aminoanilino)-1,3-phenylene], dif-
fered from the spectrum of initial compound 1. Instead
5.00 s and 5.75 s (4H, NH ), 6.20 s (4H, quinone),
2
1
3
6.65 d (8H, Harom, J = 8 Hz). C NMR spectrum, δ ,
C
ppm: 90.6, 114.2, 122.1, 140.0, 144.8, 148.2, 153.2.
Found, %: C 74.81; H 5.71; N 19.35. C H N . Calcu-
18
16
4
lated, %: C 75.0; H 5.59; N 19.44.
–
1
1
of absorption bands at 3337, 3418, and 3462 cm
typical of 1, a broadened band appeared at 3448 cm
Polycondensation of compound (1). A 0.04965-g
sample of 1 was heated for ~1.5 h at 250–260°C in
a test tube. After cooling, the product was treated with
–
due to NH and NH stretching vibrations. The NH
2
2
1
–
bending vibration band of 1 is observed at 1544 cm
2
0 mL of methanol, the mixture was kept for 24 h and
–
1
against 1630 cm in the spectrum of the product, pre-
stirred for 3 h, and the precipitate was filtered off and
dried in a vacuum desiccator over P O (0.2 kPa).
sumably due to coordination of NH groups to quinone
2
2
5
diimine fragments; in addition, the bands at 1237 and
Yield 0.04 g (80%). The isolated compound was
insoluble in ethylene glycol, DMSO, DMF, acetic acid,
and N-methylpyrrolidin-2-one and poorly soluble in
formic acid.
–
1
1
275 cm in the spectrum of 1 strongly decrease in
intensity. This reaction will be studied in detail in
future works.
In order to obtain a more stable compound, the
amino groups of 1 were acylated with acetic anhy-
dride; as a result, we isolated and identified diacetyl
derivative 2 (Scheme 3), which provided an additional
support to the structure of 1. Compound 2 is insoluble
in methanol, ethanol, and chloroform and soluble in
DMSO, DMF, and ethylene glycol at room tem-
perature.
N,N′-[Cyclohexa-2,5-diene-1,4-diylidenebis(aza-
nylylidenebenzene-4,1-diyl)]diacetamide (2). A solu-
tion of 0.05005 g (0.174 mmol) of compound 1 in
a mixture of 2 mL of acetic acid and 0.08 mL
(0.787 mmol) of 93% acetic anhydride was stirred for
7 h at 15°C. The mixture was treated with 10%
aqueous sodium carbonate to pH 9 and stirred for 4 h
at 2°C. The precipitate was filtered off, washed on
a filter with ice water until neutral washings, dried in
air, treated with methanol at 15°C, and dried in
a vacuum desiccator over P O (0.2 kPa). Yield 0.05 g
4
,4′-[Cyclohexa-2,5-diene-1,4-diylidenediaza-
nylylidene]dianiline (1). Potassium peroxodisulfate,
.62 g (2.3 mmol), was added to a solution of 0.75 g
2
5
0
–
1
(
(
(
77%), mp >290°C. IR spectrum, ν, cm : 3431, 3249
N–H), 3034 (C–Harom), 2925, 2848 (C–Haliph), 1631
C=O), 1605 (C=Carom), 1564 (C=N), 1500 (C=C,
(
(
7 mmol) of p-phenylenediamine and 0.476 g
2.3 mmol) of p-phenylenediammonium sulfate in
6
mL of glacial acetic acid at 15–16°C, and the mixture
quinone), 1384, 1306 (=N–C), 1213 (N–C), 1096,
was stirred for 21 h. The mixture was kept in a refrig-
erator at 6°C each time when the stirring was inter-
rupted. It was then treated with 10% aqueous sodium
carbonate to pH 9, and stirred for 4 h at 2°C. The pre-
cipitate was filtered off, washed on a filter with cold
water until neutral washings and the absence of sulfate
ions therein, dried in air, treated first with methanol at
1
1
024 (C–Harom), 815 (δC–Harom). H NMR spectrum, δ,
ppm: 2.00 s (6H, CH ), 5.40 s, 6.15 s (4H, quinone),
3
6
.65 d and 7.50 d (4H each, Harom), 9.80 s (2H, NH).
Found, %: C 70.85; H 5.50; N 14.93. C H N O .
2
2
20
4
2
Calculated, %: C 70.97; H 5.38; N 15.05.
The IR spectra were recorded in KBr on a Nicolet
Nexus spectrometer with Fourier transform. The UV
spectra were measured on a Specord 50 spectropho-
1
5–16°C and then with diethyl ether, and dried under
reduced pressure over P O (0.2 kPa). Yield of the
2
5
1
13
insoluble (in methanol) fraction 0.11 g (20%); yield of
tometer. The H and C NMR spectra were obtained
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 6 2017

9
58
DURGARYAN et al.
on a Varian Mercury 300 spectrometer (300 MHz for
10. Jiao, K., Sun, W., Zhang, S.S., and Sun, G., Anal. Chim.
Acta, 2000, vol. 413, p. 71.
1
H) using DMSO-d as solvent.
6
1
1. Ćirić-Marjanović, G., Marjanović, B., Bober, P.,
p-Phenylenediamine was purified by sublimation
mp 143–145°C), p-phenylenediammonium sulfate
was recrystallized from water. Potassium peroxodisul-
fate and acetic acid were analytical grade chemicals.
Rozlivková, Z., Stejskal, J., Trchová, M., and Prokeš, J.,
J. Polym. Sci., Part A: Polym. Chem., 2011, vol. 49,
p. 3387.
(
1
1
1
1
1
1
2. Honzl, J. and Tlustakova, M., J. Polym. Sci., Part C:
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This study was financially supported by the State
Committee of the Ministry of Education and Science
of Armenia Republic (research contract no. SCS 13-
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