New chemosensor systems of the benzo-[de]Isoquinoline-1,3-dione series

Article abstract of DOI:10.1007/s10593-012-1140-x

New derivatives of the benzo[de]isoquinoline-1,3-dione system containing an amino group were synthesized by the reaction of 2-benzyl-6-bromobenzo[de] isoquinoline-1,3-dione with ethylenediamine and hydrazine. Further functionalization of the free amino groups leads to imines, amines, thioureas, and hydrazones. Some compounds exhibit high chemosensor selectivity in the determination of anions.

Full text of DOI:10.1007/s10593-012-1140-x

Chemistry of Heterocyclic Compounds, Vol. 48, No. 9, December, 2012 (Russian Original Vol. 48, No. 9, September, 2012)
NEW CHEMOSENSOR SYSTEMS OF THE BENZO-
[de]ISOQUINOLINE-1,3-DIONE SERIES
I. E. Tolpygin1*, E. N. Shepelenko2, Yu. V. Revinskii2,
A. D. Dubonosov2, V. A. Bren1, and V. I. Minkin1,2
New derivatives of the benzo[de]isoquinoline-1,3-dione system containing an amino group were
synthesized by the reaction of 2-benzyl-6-bromobenzo[de]isoquinoline-1,3-dione with ethylenediamine
and hydrazine. Further functionalization of the free amino groups leads to imines, amines, thioureas,
and hydrazones. Some compounds exhibit high chemosensor selectivity in the determination of anions.
Keywords: aminoethylamines, azomethines, benzo[de]isoquinoline-1,3-diones (1,8-naphthalimides),
hydrazines, hydrazones, chemosensor activity, fluorescence.
Earlier we reported that N,N'-bis(anthracen-9-ylmethyl)alkanediamines and their derivatives exhibit the
properties of highly effective fluorescent chemosensors for various cations: H+, Zn2+, Cd2+, Hg2+ etc. [1-5]. The
principal mechanism of the action of these sensor systems is the PET (photoinduced electron transfer) effect
[6-9].
Variation of the fluorophore structure present in such systems leads not only to a change in the sensor
properties, but also to a change of the working effect. Thus, PCT (photoinduced charge transfer) becomes
dominant in cases where derivatives of 1,8-naphthalimide are used as signal fragment [6, 9].
Naphthalimide systems are widely used as effective fluorescent and colorimetric sensors for cations and
anions [10-14]. Of special interest are compounds that contain a free amino group capable of further
transformation, particularly with the introduction of additional complex-forming fragments and/or fluorophores.
It is, thus, possible to vary the effectiveness, selectivity, and other parameters of the sensors.
Potential synthons for ionochromic sensors are benzo[de]isoquinoline-1,3-diones containing aminoalkyl
or hydrazine fragments [12, 13]. In order to investigate further chemosensors with polyamine receptors we
synthesized compounds 2-10. The diamine 3 was obtained by the reaction of the bromine derivative 1 with
1
ethylenediamine [12] or N-(2-aminoethyl)acetamide, followed by acidic hydrolysis of the amide 2. The H
NMR spectra of the derivatives 2 and 3 contain characteristic signals for the protons of the CH2CH2 fragment
and also for the amine and amide groups.
_______
*To whom correspondence should be addressed, e-mail: tolpygin@ipoc.sfedu.ru.
1Scientific-Research Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachki
Ave., Rostov-on-the-Don 344090, Russia.
2Southern Scientific Center, Russian Academy of Sciences, 41 Chekhova St., Rostov-on-the-Don 344010,
Russia; e-mail: dubon@ipoc.sfedu.ru.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1422-1429, September, 2012.
Original article submitted October 19, 2011.
0009-3122/12/4809-1325©2012 Springer Science+Business Media New York
1325

The reaction of aromatic aldehydes and 2-hydroxymethylenebenzo[b]thiophen-3-one with the amine 3
gave a series of imines 4a-c and also the derivative 5. The reactions are accompanied by disappearance of the
1
signal for the NH2 group protons in the H NMR spectra and by the appearance of signals for additional
aromatic and CH protons. Compounds 4a-c were also obtained by the reaction of the corresponding aldehydes
with the acetamide 2 upon heating in 1-butanol.
Ph
O
NHAc
N
O
N
O
H
N
N
Ph
O
H
N
H
RCHO
NH2
6
2
NHAc
H2N
(from 4с)
NaBH4
R
H
conc. HBr
Ph
N
O
O
N
O
O
N
O
N
H
Ph
NH2
N
Ph
RCHO
H2N
H
N
O
O
S
4а–c
3
OH
Br
1
PhNCS
H
Ph
O
Ph
O
O
O
O
N
N
H
H
N
H
N
N
N
S
N
Ph
H
H
H
S
5
7
4 a R = 2-HO-4-MeC6H3, b R = 2-HO-5-MeOC6H3, c R = anthracen-9-yl
Reduction of the azomethine 4c in a mixture of DMF and ethanol gave the diamine system 6 with a
1
double fluorophore. In the H NMR spectrum of this compound, the proton signals for the alkyl chain CH2
groups show a substantial upfield shift of 0.4 and 1.07 ppm, compared to the analogous signals of the derivative
4c, and there is also a signal for the protons of the CH2–Ant fragment at 4.70 ppm.
The amine 3 was modified by the introduction of a thiourea fragment. Irrespective of the reaction
conditions and of the amount of phenyl isothiocyanate used it was only possible to introduce one thiourea
molecule. This is probably due to steric hindrances.
Investigation of the luminescence spectral and chemosensor properties of the obtained derivatives
shows that, contrary to previously described derivatives of similar type [10-13], their chemosensor properties
are nonspecific. Thus, the addition of the divalent metal acetates (Zn2+, Cd2+, Cu2+, Co2+, Ni2+, Pb2+, Hg2+) to
acetonitrile solutions of the naphthalimides 4a-c, 5-7 leads to a 30-300% change in the fluorescence intensity,
but poor selectivity in the determination of ions is observed.
When compound 1 was heated with hydrazine hydrate, the previously unknown amine 8 was isolated as
the main reaction product instead of the expected 2-benzyl-6-hydrazinobenzo[de]isoquinoline-1,3-dione [14].
The structure of the amine 8 is confirmed by disappearance of the signals for the benzyl substituent
1
protons and by the appearance of signals for the NH2 and NH2NH fragment protons in the H NMR spectra.
Compound 8 was also obtained by heating 6-bromobenzo[de]isochromene-1,3-dione with hydrazine hydrate.
1326

In the reaction of the obtained naphthalimide 8 with anthracene-9-carbaldehyde, irrespective of the
reaction conditions and the amount of the aldehyde used in the reaction, only the hydrazine fragment enters into
condensation with the formation of the hydrazone 9, and the signal for the NH2 group protons remains in the
1H NMR spectrum. In contrast to this, 2-hydroxynaphthalene-1-carbaldehyde adds to the naphthalimide 8 at
both NH2 groups with the formation of the diimine 10.
NH2
N
NH2
N
1
O
O
O
O
9-OHC-C14H9
NH2NH2·H2O
O
O
O
HN
HN
NH2
N
8
Br
H
2-HO-1-OHC-C10H6
OH
9
O
N
HO
N
H
N
N
O
H
H
10
-6

Fig. 1. The variation of the fluorescence intensity (I/I0) of compounds 9 (■) and 10 ( ) (c 5.0×10 M) in MeCN
upon the addition of salts NBu4 A− (c 2.5×10-5 M).
+
According to the data from fluorescence spectra, the imines 9 and 10, like compounds 3-7, exhibit a
weak chemosensor activity with respect to cations. In both cases the most significant changes in luminescence
intensity are caused by Zn2+ (buildup) and Cu2+ (quenching).
1327

The ionochromic activity with respect to F−, Cl−, CN−, SCN−, NO3 , H2PO2 , ClO4 , HSO4 , and AcO−
ions was investigated for these compounds (Fig. 1). Addition of the corresponding tetrabutylammonium salts to
acetonitrile solutions of compounds 9 and 10 leads to quenching of the fluorescence, and the interaction is most
selective with F− (23 times (9) and 22 times (10)), CN− (15 times (9) and three times (10)), and AcO− anions (11
times (9) and 3 times (10)). The presented data indicate that the selectivity for fluoride ions increases in the
transition from the imine 9 to the diimine 10. At the same time, the interaction with F− anions gives rise to a
substantial hypsochromic shift by 55 and 63 nm, respectively (a change in the fluorescence color).
Thus, a series of new benzo[de]isoquinoline-1,3-dione derivatives containing additional complex-
forming fragments has been synthesized. The investigations of the chemosensor activity show that
2-[(2-hydroxynaphthalen-1-ylmethylene)amino]-6-[N'-(2-hydroxynaphthalen-1-ylmethylene)hydrazino]benzo-
[de]isoquinoline-1,3-dione is a highly selective reagent for F− ions.
−
−
−
−
EXPERIMENTAL
The IR spectra were recorded on a Varian Excalibur 3100 FT-IR instrument. The 1H NMR spectra were
recorded in DMSO-d6 on a Varian Unity 300 spectrometer (300 MHz) with the residual signals of the solvent as
internal standard (δ 2.50 ppm). The electronic absorption spectra were recorded on a Varian Cary 100
spectrophotometer, and the luminescence spectra were recorded on a Varian Cary Eclipse fluorescence
spectrometer. Element analysis was performed on a Euro Vector EA-3000 elemental analyzer. The melting
points were determined in glass capillaries on a PTP (M) instrument. The reaction progress and the purity of the
obtained compounds were monitored by TLC (Silufol UV-254 plates, eluent CHCl3, development with iodine
vapor in a humidity chamber).
N-[2-(2-Benzyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-ylamino)ethyl]acetamide (2). 2-Ben-
zyl-6-bromobenzo[de]isoquinoline-1,3-dione (1) (1.83 g, 5 mmol) was dissolved in EtOH (50 ml), N-(2-amino-
ethyl)acetamide (1.0 g, 10 mmol) was added, and the mixture was refluxed for 20 h. The solvent was
evaporated on a rotary evaporator, and the residue was recrystallized from a 1:2 mixture of benzene and
petroleum ether. Yield 1.20 (60%). Light-beige fibrous crystals, mp 256-257°C. IR spectrum, ν, cm-1: 3300,
1
3220 (NH), 1700, 1665, 1650 (С=O), 1600, 1545 (С=С), 1370 (C–N–C). H NMR spectrum, δ, ppm (J, Hz):
1.90 (3Н, s, СОСН3); 3.80 (1H, br. s, NHAr); 3.40-3.70 (4Н, m, (СН2)2); 5.15 (2Н, s, СН2Ph); 6.90 (Н, d, J = 8.2,
Н Аr); 7.10-7.84 (6Н, m, Н Аr); 8.41-8.67 (3Н, m, Н Аr); 10.40 (1H, br. s, CONH). Found, %: С 71.25;
Н 5.52; N 10.79. C23H21N3O3. Calculated, %: С 71.30; Н 5.46; N 10.85.
6-(2-Aminoethylamino)-2-benzyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (3). A. A 46% HBr
solution (2 ml) was added to a solution of the acetamide 2 (0.77 g, 2 mmol) in 2-PrOH (20 ml). The mixture
was heated for 2 h. It was then cooled, diluted with H2O (20 ml), and neutralized by adding Na2CO3; the amine
3 was extracted with CHCl3 (3×20 ml). The extract was evaporated, and the residue was crystallized from a 1:1
mixture of benzene and petroleum ether. Yield 0.52 g (75%). Light-cream colored powder, mp 239-240°С. IR
1
spectrum, ν, cm-1: 3320, 3150 (NH2, NH), 1705, 1655 (С=O), 1590, 1530 (С=С), 1380 (C–N–C). H NMR
spectrum, δ, ppm (J, Hz): 3.10-3.22 (3Н, m, NH2, NH); 3.23 (2Н, t, J =7.2, CH2СН2NH2); 3.60 (2Н, t, J = 7.2,
CH2СН2NH2); 5.17 (2Н, s, СН2Ph); 6.75 (1Н, d, J = 8.2, Н Аr); 7.15-7.90 (6Н, m, Н Аr); 8.46-8.75 (3Н, m,
Н Аr). Found, %: С 72.95; Н 5.61; N 12.22. C21H19N3O2. Calculated, %: С 73.03; Н 5.54; N 12.17.
B. The amine 3 was obtained through a direct reaction of the dione 1 with ethylenediamine under
conditions analogous to the production of compound 2. Yield 62%; mp 238-239°C. The spectral characteristics
agree with those of the compound produced by method A.
Compounds 4a-c, 5 (General Method). A. A mixture of the amine 3 (0.69 g, 2 mmol) with the
corresponding aldehyde (2 mmol) in EtOH (10 ml) (for the preparation of compounds 4a-c) or with 2-hydroxy-
methylenebenzo[b]thiophen-3-one (0.36 g, 2 mmol) in MeCN (10 ml) (for the preparation of compound 5)
1328

was heated for 2 h. The mixture was cooled, and the precipitate was filtered off and crystallized from a suitable
solvent.
B. The azomethines 4a-c were obtained by refluxing the acetamide 2 (2 mmol) for 10 h with an
equimolar amount of the corresponding aldehyde in 1-BuOH (20 ml). Yields 70-75%.
2-Benzyl-6-{2-[(2-hydroxy-4-methylbenzylidene)amino]ethylamino}-1H-benzo[de]isoquinoline-
1,3(2H)-dione (4a). Yield 0.75 g (81%). Yellow crystals, mp 203-204°С (PhMe). IR spectrum, ν, cm-1: 3200
1
(NH, ОН), 1695, 1655 (С=O), 1640 (C=N), 1610, 1550 (С=С), 1375 (C–N–C). H NMR spectrum, δ, ppm (J,
Hz): 2.28 (3Н, s, СН3); 3.10-3.25 (2Н, m, ArNHCH2); 3.60-3.80 (2Н, m, CH2N=C); 5.21 (2Н, s, СН2Ph); 6.80
(1Н, d, J = 8.4, Н Аr); 7.10-7.70 (7Н, m, Н Аr); 8.00 (1Н, s, NHAr); 8.20-8.52 (5Н, m, N=СН, Н Аr); 8.92 (Н,
d, J = 8.4, Н Аr). Found, %: С 75.20; Н 5.52; N 8.99. C29H25N3O3. Calculated, %: С 75.14; Н 5.44; N 9.07.
2-Benzyl-6-{2-[(2-hydroxy-5-methoxybenzylidene)amino]ethylamino}-1H-benzo[de]isoquinoline-
1,3(2H)-dione (4b). Yield 0.74 g (77%). Orange fibrous crystals, mp 232-233°С (PhMe). IR spectrum, ν, cm-1:
1
3150 (NH, ОН), 1700, 1660 (С=O), 1645 (C=N), 1600, 1560 (С=С), 1375 (C–N–C). H NMR spectrum, δ,
ppm (J, Hz): 3.60-4.00 (7Н, m, ОСН3, (СН2)2); 5.20 (2Н, s, СН2Ph); 6.63-6.90 (4Н, m, Н Аr); 7.10-7.42 (5Н,
m, Н Аr); 7.60 (1Н, t, J = 7.6, Н Аr); 7.82 (1Н, br. s, ArNH); 8.28 (1Н, d, J = 8.0, Н Аr); 8.34-8.50 (2Н, m,
N=СН, Н Аr); 8.61 (1Н, d, J = 8.0, Н Аr); 12.50 (1Н, s, ОН). Found, %: С 72.70; Н 5.30; N 8.70. C29H25N3O4.
Calculated, %: С 72.64; Н 5.25; N 8.76.
6-{2-[(Anthracen-9-ylmethylene)amino]ethylamino}-2-benzyl-1H-benzo[de]isoquinoline-1,3(2H)-
dione (4c). Yield 0.92 g (86%). Fine yellow crystals, mp 190-191°С (decomp., 1-BuОН). IR spectrum, ν, cm-1:
1
3320, 3210 (NH), 1690, 1670 (С=O), 1640 (C=N), 1620, 1550 (С=С), 1375 (C–N–C). H NMR spectrum, δ,
ppm (J, Hz): 3.88-4.00 (2Н, m, ArNHCH2); 4.27 (2Н, t, J = 7.2, CH2N=C); 5.22 (2Н, s, СН2Ph); 6.91 (1Н, d,
J = 8.2, Н Аr); 7.10-7.50 (9Н, m, Н Аr); 7.60 (1Н, t, J = 7.8, Н Аr); 7.88-8.08 (3Н, m, Н Аr, ArNH); 8.25 (1Н,
d, J = 8.6, Н Аr); 8.33-8.54 (5Н, m, Н Аr); 9.53 (1Н, s, N=СН). Found, %: С 81.11; Н 5.06; N 7.94.
C36H27N3O2. Calculated, %: С 81.03; Н 5.10; N 7.87.
2-Benzyl-6-{2-[(3-oxo-3H-benzo[b]thiophen-2-ylidenemethyl)amino]ethylamino}-2-benzyl-1H-benzo-
[de]isoquinoline-1,3(2H)-dione (5). Yield 0.69 g (68%). Red-brown amorphous crystals, mp 188-189°С
(toluene). IR spectrum, ν, cm-1: 3300, 3180 (NH), 1700, 1660 (С=O), 1600, 1545 (С=С), 1380 (C–N–C).
1H NMR spectrum, δ, ppm (J, Hz): 3.55-3.82 (4Н, m, (СН2)2); 5.20 (2Н, s, СН2Ph); 6.83 (1Н, t, J = 8.2, Н Аr);
7.10-7.84 (11Н, m, Н Аr); 8.02 (1Н, br. s, ArNH); 8.22-8.50 (2Н, m, Н Аr); 8.63 (1Н, t, J = 8.2, NHСН=);
10.60 (1Н, br. s, NHCH=). Found, %: С 71.35; Н 4.64; N 8.23; S 6.28. C30H23N3O3S. Calculated, %: С 71.27;
Н 4.59; N 8.31; S 6.34.
6-{2-[(Anthracen-9-ylmethyl)amino]ethylamino}-2-benzyl-1H-benzo[de]isoquinoline-1,3(2H)-dione
(6). NaBH4 (0.23 g, 6 mmol) was added over 5 min with stirring and heating (40-50°C) to a suspension of the
azo-methine 4c (1.10 g, 2 mmol) in EtOH (50 ml).. The solution was stirred for 2 h and diluted with H2O (100
ml), and the excess of the borohydride was neutralized by the addition of dilute AcOH. The mixture was cooled,
and the precipitate was filtered off, dried, and crystallized from 1-BuOH. Yield 0.95 g (88%). Light-orange
needle shaped crystals, mp 176-177°C (decomp.). IR spectrum, ν, cm-1: 3250, 3180 (NH), 1710, 1665 (С=O),
1
1600, 1550 (С=С), 1370 (C–N–C). H NMR spectrum, δ, ppm (J, Hz): 3.20 (2Н, t, J = 7.4, CH2CH2NHCH2);
3.48-3.61 (2Н, m, ArNHCH2); 4.70 (2Н, s, NHСН2Ar'); 5.22 (2Н, s, СН2Ph); 6.84 (1Н, d, J = 8.4, Н Аr); 7.10-
7.60 (11H, m, Н Аr); 7.90-8.05 (2Н, m, Н Аr); 8.24 (1Н, d, J = 8.4, Н Аr); 8.35-8.50 (5Н, m, Н Аr, ArNH).
Found, %: С 80.80; Н 5.40; N 7.90. С36Н29N3O2. Calculated, %: С 80.72; Н 5.46; N 7.84.
1-[2-(2-Benzyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-ylamino)ethyl]-3-phenylthiourea
(7). A mixture of the amine 3 (0.7 g, 2 mmol) and phenyl isothiocyanate (0.6 ml, 5 mmol) in benzene (10 ml)
was refluxed for 5 h. The mixture was cooled, and the precipitate was filtered off, then crystallized from
1-BuOH. Yield 0.8 g (83%). Light-yellow coarsely crystalline powder, mp 297-298°С. IR spectrum, ν, cm-1:
1
3375 (NH), 1705, 1660 (С=O), 1584, 1537 (С=С), 1375 (C–N–C). H NMR spectrum, δ, ppm (J, Hz):
3.52-3.67 (2Н, m, ArNHCH2); 3.81-3.97 (2Н, m, CH2NHCS); 5.20 (2Н, s, СН2Ph); 6.88 (1Н, d, J = 8.2, Н Аr);
7.00-7.43 (10H, m, Н Аr); 7.60 (1Н, t, J = 7.6, Н Аr); 7.72-7.93 (2Н, m, ArNH, NHCS); 8.27 (1Н, d, J = 8.2,
1329

Н Аr); 8.43 (1Н, d, J = 8.0, Н Аr); 8.64 (1Н, d, J = 8.2, Н Аr); 9.60 (1Н, s, NHPh). Found, %: С 70.05; Н 4.97;
N 11.52; S 6.60. C28H24N4O2S. Calculated, %: С 69.98; Н 5.03; N 11.66; S 6.67.
2-Amino-6-hydrazino-1H-benzo[de]isoquinoline-1,3(2H)-dione (8). A. 85% Hydrazine hydrate
(5 ml) was added to a solution of 4-bromonaphthalic anhydride (1.1 g, 4 mmol) in butyl cellosolve (40 ml). The
reaction mixture was refluxed for 2 h and cooled. The precipitate was filtered off and washed thoroughly with
MeOH. The product was crystallized from a 1:1 mixture of 1-BuOH and DMF and dried at 110-115°C. Yield
0.84 g (87%). Dark-yellow finely crystalline powder, mp >300°С (decomp.). IR spectrum, ν, cm-1: 3300, 3250
(NH2, NH), 1705, 1670 (С=O), 1700, 1655 (С=O), 1600, 1555 (С=С), 1375 (C–N). 1H NMR spectrum, δ, ppm
(J, Hz): 5.38 (2Н, s, NNH2); 7.20-7.35 (2Н, m, Н Аr); 7.48-7.58 (2Н, m, Н Аr); 7.77-7.90 (1Н, m, Н Аr);
8.48-8.72 (3Н, m, NHNH2). Found, %: С 59.43; Н 4.22; N 23.20. C12H10N4O2. Calculated, %: C 59.50; H 4.16;
N 23.13.
B. In the reaction of compound 1 with hydrazine hydrate under conditions similar to those described
above, the hydrazine 8 was obtained. Yield 78%; mp >300°C (decomp.). The spectral characteristics agree with
those of the compound obtained by method A.
2-Amino-6-[N'-(anthracen-9-ylmethylene)hydrazino]-1H-benzo[de]isoquinoline-1,3(2H)-dione (9).
The hydrazine 8 (0.48 g, 2 mmol) was dissolved in 1-BuOH (10 ml), anthracene-9-carbaldehyde (0.41 g,
2 mmol) was added, and the mixture was refluxed for 2 h. The mixture was cooled, and the precipitate was
filtered off, washed with MeOH, and crystallized from a 4:1 mixture of 1-BuOH and DMF. Yield 0.75 g (87%).
Dark-orange crystals, mp >330°С (decomp.). IR spectrum, ν, cm-1: 3210 (NH2, NH), 1690, 1655 (С=O), 1645
(C=N), 1590, 1500 (С=С), 1375 (C–N). 1H NMR spectrum, δ, ppm (J, Hz): 5.69 (2Н, s, NH2), 7.42-8.90 (14Н,
m, Н Аr); 9.67 (1Н, s, N=СН); 11.62 (1Н, s, NН). Found, %: С 75.40; Н 4.15; N 12.96. C27H18N4O2.
Calculated, %: С 75.34; Н 4.21; N 13.02.
2-[(2-Hydroxynaphthalen-1-ylmethylene)amino]-6-[N'-(2-hydroxynaphthalen-1-ylmethylene)hydra-
zino]-1H-benzo[de]isoquinoline-1,3(2H)-dione (10). This compound was obtained similarly to compound 9 in
the reaction of the hydrazine 8 (0.48 g, 2 mmol) and 2-hydroxynaphthalene-1-carbaldehyde (0.86 g, 5 mmol).
Yield 0.79 g (72%). Dark red-brown finely crystalline powder, mp >220°С (decomp., 1-BuОН–DMF, 3:1). IR
spectrum, ν, cm-1: 3300, 3220 (NH), 1695, 1660 (С=O), 1645, 1640 (C=N), 1600, 1500 (С=С), 1375 (C–N).
1H NMR spectrum, δ, ppm (J, Hz): 7.10-8.97 (17Н, m, Н Аr); 9.65 (1Н, s, CH=N); 9.93 (1Н, s, NHN=СН);
11.43-11.64 (2Н, m, ОН, NH); 12.80 (1Н, s, ОН). Found, %: С 74.25; Н 3.96; N 10.24. C34H22N4O4.
Calculated, %: С 74.17; Н 4.03; N 10.18.
The work was carried out with financial support from the Russian Foundation for Basic Research
(project No. 12-03-00120) and the Grants Council of the President of the Russian Federation (grant NSh-
927.2012.3).
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