Macroheterocyclic compounds with p-diamines of the diaryl series

Article abstract of DOI:10.1007/s11176-005-0352-5

The reactions of indane-1,3-dione with 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, and 4,4′-diaminodiphenyl ether were used to synthesize symmetrical macroheterocyclic compounds.

Full text of DOI:10.1007/s11176-005-0352-5

Russian Journal of General Chemistry, Vol. 75, No. 6, 2005, pp. 961 965. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005,
pp. 1017 1021.
Original Russian Text Copyright
2005 by Berezina, Vorob’ev, Vorob’eva, Sadova.
Macroheterocyclic Compounds with p-Diamines
of the Diaryl Series
G. R. Berezina, Yu. G. Vorob’ev, S. M. Vorob’eva, and M. V. Sadova
Ivanovo State University of Chemical Technology, Ivanovo, Russia
Received February 16, 2004
Abstract The reactions of indane-1,3-dione with 4,4 -diaminodiphenyl sulfone, 4,4 -diaminodiphenyl
sulfide, and 4,4 -diaminodiphenyl ether were used to synthesize symmetrical macroheterocyclic compounds.
Along with phthalonitrile and isoindoline-1,3-di-
imine, indane-1,3-dione (I) can undergo cyclizations
to form macroheterocyclic compounds [1 4]. Dione I
and its derivatives are reactive compounds susceptible
to various chemical transformations. The chemical
properties of dione I have been exemplified by a great
variety of reactions: with acids, halogens, secondary
amines, ammonium acetate, etc. [5].
amine, 2,6-diaminopyridine, and 2,5-diamino-1,3,4-
thiadiazole residues.
At the same time, of interest are macroheterocyclic
compounds in which p-diamines of the diphenyl series
contain groups that uncouple the phenylene residues.
We set ourselves the task to synthesize macrohetero-
cyclic compounds on the basis of dione I and p,p -di-
aminobiphenyl and its derivatives and to study their
properties.
We have synthesized macroheterocyclic com-
pounds on the basis of dione I and m-phenylenedi-
amine, 2,6-diaminopyridine, and 2,5-diamino-1,3,4-
thiadiazole [6 8]. Macroheterocyclic compounds on
the basis of p-phenylenediamine and benzidine [4]
have also been obtained, that differ in their properties
from macroheterocycles containing m-phenylenedi-
As objects for synthesis and study we took dione
I, as well as p-diamines, such as 4,4 -diaminodiphenyl
sulfone (II), 4,4 -diaminodiphenyl sulfide (III), and
4,4 -diaminodiphenyl ether (IV). Dione I was prepared
by the procedure in [5]. Macroheterocyclic com-
pounds were synthesized by the scheme given below.
X
O
NH
HN
CH
2
CH2 + H2N X NH2
HC
O
O
O
I
II IV
V VII
X
X
N
N
N
N
2PhCOCl
2EtONa
H2NXNH2
CH
HC
CH HC
NH
HN
Ph C O
O
O C Ph
O
X
VIII X
XI XIII
X = p-C6H4 SO2 C6H4-p (II, V, VIII, XI), p-C6H4 S C6H4-p (III, VI, IX, XII), p-C6H4 O C6H4-p (IV, VII, X, XIII).
As seen from the scheme, the synthesis involved
three stages. First dione I was reacted with sulfone II,
sulfide III, or ether IV (molar ratio 2:1) in methanol
under reflux for 8 h to synthesize diamines V VII.
They are dark blue or violet powders melting above
150 C. When heated in conc. H2SO4, they hydrolyze
into the starting compounds.
Diamines V VII are soluble in most organic
solvents. They also dissolve in conc. H2SO4 at room
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962
BEREZINA at al.
X
D
HN
O
NH
O
0.6
HC
CH
2
0.4
0.2
XIV XVIII
1
3
X = m-C6H4 (XIV), pyridine-2,6-diyl (XV), 1,3,4-thiadi-
azol-2,5-diyl (XVI), p-C6H4 (XVII), p-C6H4 C6H4-p
(XVIII).
350 400 450 500 550 600 650
Inspection of the electronic absorption spectra of
diamines V VII and XIV XVIII showed that repla-
cement of the m phenylene (compounds XIV XVI)
by p-phenylene (compound XVII) and diphenylene
(compounds V VII and XVIII) fragments produces a
, nm
Fig. 1. Electronic absorption spectra in ethanol of di-
amines (1) V, (2) VI, and (3) VII.
strong bathochromic shift (470
long-wave bands due to extension of the conjugation
chain in the molecule.
610 nm) of the
temperature; therewith, the color of the solution
change: Blue and violet substances form orange and
yellow solutions. On dilution of the solutions, the
compounds are recovered unchanged. Apparently,
diamines V VII take up four protons to form tetraca-
tion A [9].
The presence between the phenyl rings in the di-
phenylene residue of the S , >S=O, and O groups
favors more intense coloration of compounds. The
principal absorption band in the electronic absorption
spectra shifts hypsochromically by 25, 14, and 25 nm
for compounds V VII, respectively, compared to
compound XVIII. This fact is explained by that the
>S=O, S , and O group uncouple the conjugation
chain in the molecule.
+
HN
+
NH
X
2SO42
H2C
CH2
+
OH
HO+
A
1
The H NMR spectra of compounds XIV and XVI
in HMPA display a fairly narrow one proton signal.
Substituents of the benzidine series make this signal
to vanish.
The electronic absorption spectra of diamines V
VII in organic solvents show characteristic bands in
the UV and visible ranges: 370 400 and 550 600 nm
(Fig. 1). The bands at 370 400 nm relate to the con-
jugated -aminovinylcarbonyl system HN C=C C=O.
The long-wave band is responsible for the color of
X
N
N
H2C
H
CH
the compounds and is formed by
* transitions in
the conjugation system. The electronic absorption
spectra of diamines V VII in sulfuric acid display a
characteristic band at 400 420 nm.
O
O
B
X
For structural assessment of compounds V VII we
measured their IR spectra. The diketone form of dione
I gives a doubled band at 1770 1705 and a band at
N
O
N
O
HC
CH2
1
1600 1580 cm . The first range relates to two car-
bonyl group and the second, to the aromatic system
[9, 10]. The doublet disappears upon reaction of di-
ketone I with diamines II IV. The IR spectra shows
well-defined vibration bands groups intervening the
phenylene nuclei of the diamine residues (see Experi-
mental).
H
C
The large chemical shift and lack of multiplicity
allow this signal to be assigned to the hydroxyl proton
in keto enol form B or C stabilized by hydrogen bond.
We compared the spectral properties of diamines
V VII and XIV XVIII.
Introduction of substituents of the benzidine series,
i.e. enlargement of the phenylene bridge, gives rise to
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MACROHETEROCYCLIC COMPOUNDS WITH p-DIAMINES
963
steric hindrances or intramolecular hydrogen bonding.
Form B C is unlikely to exist because of
destroyed conjugation; had they been formed, the
compounds would have changed their color, but this
phenomenon was observed neither visually nor spec-
trophotometrically.
(a)
1.2
1.0
0.8
1
3
Benzoylation of diamines V VII was performed
in boiling benzoyl chloride for 6 h. Benzoyl deriva-
tives VIII X are brown powders, they are not hyd-
rolyzed by conc. H2SO4, and are readily cleaved with
sodium ethylate to starting compounds V VII. Al-
kaline hydrolysis involve cleavage of the acyl oxygen
bond. By comparing the electronic absorption spectra
of diamines V VIII and benzoyl derivatives V VII
one can see that benzoylation renders compounds
stronger colored.
2
0.6
0.4
0.2
0
D
300 350 400 540
(b)
The electronic absorption spectra of benzoyl deri-
vatives VIII X characteristically contain a single
absorption band at 300 400 nm (Fig. 2a). The long-
wave absorption band of benzoyl derivatives VIII X
is shifted hypsochromically compared to compounds
V VII (by 200 nm) (Figs. 1 and 2a). A possible
explanation for this fact is that ketone carbonyl
stronger withdraws and delocalizes electrons that ester
carbonyl, which, in its turn, is associated with the
presence of an internal effect in ester carbonyl, ad-
versely affecting the electron-acceptor ability of the
C=O group [10]. The elemental analyses and IR spec-
tra provide evidence for the composition and structure
of benzolylated diamines VIII X.
1.6
1.4
1.2
1.0
3
1
2
0.8
0.6
0.4
0.2
250 300 350 400 450 , nm
Macroheterocycles XI XIII were prepared in
glacial acetic acid under reflux. They are variously
shaded brown substances. They are soluble in DMF,
chloroform, and acetone (under heating). Macrocycle
XIII is insoluble in ethanol, unlike macrocycles XI
and XII. The electronic absorption spectra characteris-
tically contain a single absorption band at 305, 416,
and 293 nm (compounds XI XIII, respectively]. The
formation of a macroheteroring with a lacking con-
jugation system produces no changes into the elec-
tronic absorption spectrum of compounds XI and XIII,
whose p-phenylene fragments are intervened by an
SO2 group and an oxygen atom, unlike compound XII
that has a sulfur bridge (Fig. 2b). This fact can be
explained by that the coordinately unsaturated sul-
fur(II) atom serves to combine the weak chromo-
phores into a single one. The oxygen atom and the
SO2 group do not possess such an ability.
Fig. 2. Electronic absorption spectra. (a) Benzoylated
diamines (1) VIII, (2) IX, and (3) X (ethanol); and
(b) macroheterocyclic compounds (1) XI, (2) XII, and
(3) XIII (DMF).
benzene, and chloroform in quartz cells (l 1 cm) at
20 C. IR spectra were obtained on an Avatar-360 FT-
IR-ESP in KBr.
Purity control was performed by TLC on Silufol
UV-254
1:19 v/v).
plates
(eluent
methanol chloroform,
3-[4-(4-[(1-Oxo-1H-inden-3-yl)amino]phenyl-
sulfonyl)anilino]-1H-inden-1-one (V). A mixture of
0.01 mol of dione I and 0.005 mol of sulfone II was
heated in 20 ml of methanol under reflux for 8 h.
After cooling, a precipitate formed and was filtered
off, washed with ethanol, and dried in air. Product V
was purified by column chromatography on alumina
(Brockmann II), eluent methanol chloroform, 1:1 v/v,
yield 86%, dark blue crystals, mp 228 C, Rf 0.87,
EXPERIMENTAL
The electronic absorption spectra were measured
on a Specord M-400 instrument in DMF, acetone,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

964
BEREZINA at al.
soluble in benzene, ethanol, DMF, chloroform, and
acetone; insoluble in hexane, heptane, and 20% alkali.
UV spectrum, max, nm (ethanol): 376, 585; (benzene):
382, 558; (DMF): 536; (chloroform): 378, 562;
(CH) 826. Found N, %: 3.6. C44H28N2O4S. Cal-
culated N, %: 4.1.
1-(4-[(4-[3-(Benzoyloxy)-1H-inden-1-yliden]-
aminophenoxy]phenylimino)-1H-inden-3-yl
benzoate (X), yield 22%, brown crystals, does not
melt up to 300 C, Rf 0.92. UV spectrum, max, nm
1
(acetone): 381, 569. IR spectrum, cm : (NH) 3382,
(NH) 1505, (C=O) 1658, (CN) 1208, (CC) 1106,
(CS) 728, (CH) 2921, (CH) 833, (S=O) 1145.
Found N, %: 5.3. C30H20N2O4S. Calculated N, %:
5.6.
1
(DMF): 300 (log 4.5). IR spectrum, cm : (C=O)
1716, (CC) 1093, .(C=N) 1616, (CH) 2920, (CH)
842, (CO) 1236. Found N, %: 4.4. C44H28N2O5.
Calculated N, %: 4.2.
Compounds VI, VII, and XIV XVIII were pre-
pared in a similar way.
1,7(1,3)-Di-1H-indena-3,5,9,11(1,4)-tetrabenzola-
2,6,8,12-tetraaza-4,10-dithiacyclododecaphane-1,6-
diene-4,10-dione (XI). A mixture of 0.0003 mol of
compound V and 0.002 mol of sulfone II was heated
in 15 ml of glacial acetic acid under reflux for 3 h.
After cooling, the reaction mixture was poured into
hexane. A precipitate formed and was filtered off and
dried at 100 C, yield 87%, light brown crystals, mp
225 C, Rf 0.6, soluble in DMF, acetone, ethanol and
chloroform (under heating), and insoluble in hexane
and HCl. UV spectrum, max, nm· (ethanol): 305. IR
3-[4-(4-[(1-Oxo-1H-inden-3-yl)amino]phenylsul-
fanyl)anilino]-1H-inden-1-one (VI), yield 75%, dark
green crystals, mp 176 C, Rf 0.6. UV spectrum,
,
max
nm (ethanol): 385, 596; (benzene): 376, 575; (DMF):
385,585; (acetone): 377, 582; (chloroform): 378, 512,
1
584. IR specrum, cm : (NH) 3373, (NH) 1547,
(C=O) 1649, (CN) 1207, (CC) 1102, (CS) 735,
(CH) 2918, (CH) 817. Found N, %: 6.1. C30H20
N2O2S. Calculated N, %: 5.9.
3-(4-4-[(1-Oxo-1H-inden-3-yl)amino]phenoxy-
anilino)-1H-inden-1-one (VII), yield 77%, violet
crystals, mp 256 C, Rf 0.77. UV spectrum, max, nm
(DMF): 394 (log 4.5), 585 (log 4.2). IR spectrum,
1
spectrum, cm : (NH) 3373, (NH) 1522, (CN)
1401, (CC) 1073, (C=N) 1675, (CS) 734, (CH)
2920, (CH) 833, (S=O) 1148, 1320. Found N, %:
8.2. C42H28N4O4S2. Calculated N, %: 7.8.
1
cm : (NH) 3437, (NH) 1549, (C=O) 1654, (CN)
1448, (CC) 1093, (CH) 2921, (CH) 833, (CO)
1204. Found N, %: 5.5. C30H20N2O3. Calculated N,
%: 6.1.
1,7(1,3)-Di-1H-indena-3,5,9,11(1,4)-tetrabenzola-
2,6,8,12-tetraaza-4,10-dithiacyclododecaphane-1,6-
diene (XII), yield 29%, dark brown crystals, does not
melt up to 250 C, Rf 0.65, soluble in acetone, ethanol,
and chloroform. UV spectrum, max, nm (DMF): 416
1-(4-[(4-[3-(Benzoyloxy)-1H-inden-1-yliden]-
aminophenyl)sulfonyl]phenylimino)-1H-inden-3-yl
benzoate (VIII). A mixture of 0.02 mol of compound
V, 13 ml of benzoyl chloride, and 5 ml of pyridine
was heated under reflux for 6 h. After cooling, a
precipitate formed and was filtered off, washed with
benzene, dissolved in 5% alkali, filtered off, and dried
at 100 C. Organic admixtures were extracted in a
Soxhlet apparatus with benzene. Yield 52%, brown
crystals, does not melt up to 250 C, Rf 0.9, soluble in
chloroform, acetone, and DMF (under heating), and
insoluble in benzene. UV spectrum, max, nm (chlo-
1
(log 4.7). IR spectrum, cm : (NH) 3415, (NH)
1540, (CN) 1398, (CC) 1049, (C=N) 1606, (CS)
747, (CH) 2923, (CH) 830. Found N, %: 7.9.
C42H28N4S2. Calculated N, %: 8.6.
1,7(1,3)-Di-1H-indena-3,5,9,11(1,4)-tetrabenzola-
2,6,8,12-tetraaza-4,10-dioxacyclododecaphane-1,6-
diene (XIII), yield 38%, dark brown crystals, does not
melt up to 300 C, Rf 0.7, soluble in DMF and in-
soluble in ethanol, acetone, and chloroform. UV spec-
trum, max, nm (DMF): 293 (log 4.6). IR spectrum,
1
1
roform): 299. IR spectrum, cm : (C=O) 1720,
cm : (NH) 3416, (NH) 1538, (CN) 1405, (CC)
(CC) 1072, (C=N) 1664, (CS) 710, (CH) 2918,
(CH) 794, (S=O) 1152. Found N, %: 3.8.
C44H28N2O6S. Calculated N, %: 33.9.
1093, .(C=N) 1614, (CH) 2920, (CH) 834, (CO)
1219. Found N, %: 8.5. C42H28N4O2. Calculated N,
%: 9.03.
Compounds IX and X were prepared in a similar
way.
N,N -Bis(1-oxo-1H-inden-3-yl)-m-phenylenedi-
amine (XIV), yield 88%, red crystals, mp 291 293 C,
Rf 0.7. UV spectrum, max, nm (ethanol): 470 (log
1-(4-[(4-[3-(Benzoyloxy)-1H-inden-1-yliden]-
aminophenyl)sulfanyl]phenylimino)-1H-inden-3-yl
benzoate (IX), yield 44%, brown crystals, does not
melt up to 250 C, Rf 0.85. UV spectrum, .max, nm
1
3.77). IR spectrum, cm : (NH) 3370, (NH) 1540,
(C=O) 1680, (CN) 1240, (CC) 1120, (CH) 2920,
(CH) 796. Found N, %: 8.0. C24H16N2O2. Calculated
N, %: 7.7.
1
(ethanol): 401. IR spectrum, cm : (C=O) 1713,
(CC) 1084, (C=N) 1656, (CS) 752, (CH) 2973,
N,N -Bis(1-oxo-1H-inden-3-yl)pyridine-2,6-di-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

MACROHETEROCYCLIC COMPOUNDS WITH p-DIAMINES
amine (XV), yield 85%, dark brown crystals, mp
965
REFERENCES
259 260 C, Rf 0.8. UV spectrum, ma1x, nm (ethanol):
480 (log 3.61). IR spectrum, cm : (NH) 3340,
(NH) 1530, (C=O) 1680, (CN) 1280, (CC) 1150,
(CH) 3160, (CH) 825, (piridin) 475. Found N, %:
11.1. C23H15N3O2. Calculated N, %: 11.5 [7].
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Melson, G.A., Ed., New York: Plenum, 1979.
2. Yatsimirskii, K.B., Kol’ginskii, A.G., Pavli-
shchuk, V.V., and Talanova, G.G., Sintez makrotsikli-
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pounds), Kiev: Naukova Dumka, 1987.
N,N -Bis(1-oxo-1H-inden-3-yl)-1,3,4-thiadiazole-
2,5-diamine (XVI), yield 63%, yellow crystals, mp
197 C, Rf 0.4. UV spectrum, max, nm (ethanol): 328,
3. Smirnov, R.P., Berezina, G.R., Kolesnikov, N.A., and
Berezin, B.D., Izv. Vyssh. Uchebn. Zaved., Khim.
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1
358, 527. IR spectrum, cm : (NH) 3320, (NH)
1510, (C=O) 1650, (CN) 1150, (CC) 1130, (CH)
2950, (CH) 850, (CS) 692. Found, %: N 13.9; S 8.5.
C20H12N4O2S. Calculated, %: N 15.0; S 8.6.
4. Vorob’eva, S.M., Cand. Sci. (Tech.) Dissertation,
Ivanovo, 1976.
N,N -Bis(1-oxo-1H-inden-3-yl)-p-phenylenedi-
amine (XVII), yield 81%, dark green crystals, does
not melt up to 350 C, Rf 0.6. UV spectrum, max, nm
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Diketones), Riga: Akad. Nauk Latv. SSR, 1961, p. 5.
1
(ethnol): 600 (log 3.73). IR spectrum, cm : (NH)
6. Berezina, G.R., Vorob’ev, Yu.G., and Smirnov, R.P.,
3180, (NH) 1550, (C=O) 1640, (CN) 1280, (CC)
1140, (CH) 2980, (CH) 737. Found N, %: 7.4.
C24H16N2O2. Calculated N, %: 7.7.
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Zh. Org. Khim., 1999, vol. 35, no. 5, p. 808.
N,N -Bis(1-oxo-1H-inden-3-yl)benzidine
(XVIII), yield 85%, dark green crystals, does not melt
up to 350 C, Rf 0.5. UV spectrum, m1ax, nm (ethanol):
610 (log 4.1). IR spectrum, cm : (NH) 3330,
(NH) 1540, (C=O) 1640, (CN) 1250, (CC) 1190,
(CH) 2990, (CH) 814. Found N, %: 6.1. C30H20
N2O2. Calculated N, %: 6.3.
8. Berezina, G.R., Vorob’ev, Yu.G., and Smirnov, R.P.,
Zh. Obshch. Khim., 1999, vol. 69, no. 11, p. 1915.
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Chemistry, 2nd ed., London: Longmans, 1966.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005