Chemosensor properties of mono-and bisthioureas based on 9-anthrylmethyl-substituted alkylamines and diamines

Article abstract of DOI:10.1134/S1070363210040146

Mono-and bisthioureas were synthesized based on N-(9-anthrylmethyl)- substituted alkylamines and diamines. Their luminescent and complexing properties were studied by the electronic, IR, and NMR ¹? spectroscopy. N-(9-Anthrylmethyl)-N-(6-{9-anthrylmethyl[(phenylamino) carbothioyl]amino}hexyl)-N'-phenyl-thiourea was shown to be a highly effective fluorescent chemosensor for Hg²⁺ cations. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070363210040146

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 4, pp. 765–770. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © I.E. Tolpygin, E.N. Shepelenko, Yu.V. Revinskii, A.V. Tsukanov, A.D. Dubonosov, V.A. Bren’, V.I. Minkin, 2010, published in
Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 4, pp. 603–608.
Chemosensor Properties of Mono- and Bisthioureas Based
on 9-Anthrylmethyl-Substituted Alkylamines and Diamines
I. E. Tolpygina, E. N. Shepelenkob, Yu. V. Revinskiia, A. V. Tsukanovb,
A. D. Dubonosovb, V. A. Bren’a,b, and V. I. Minkina,b
a Research Institute of Physical and Organic Chemistry of the Southern Federal University,
pr. Stachki 194/2, Rostov-on-Don, 344090 Russia
e-mail: dubon@ipoc.rsu.ru
b Southern Scientific Center of Russian Academy of Sciences, Rostov-on-Don, Russia
Received March 23, 2009
Abstract―Mono- and bisthioureas were synthesized based on N-(9-anthrylmethyl)-substituted alkylamines
1
and diamines. Their luminescent and complexing properties were studied by the electronic, IR, and NMR Н
spectroscopy. N-(9-Anthrylmethyl)-N-(6-{9-anthrylmethyl[(phenylamino)carbothioyl]amino}hexyl)-N'-phenyl-
thiourea was shown to be a highly effective fluorescent chemosensor for Hg2+ cations.
DOI: 10.1134/S1070363210040146
Fluorescent selective chemical sensors for determina-
tion of cations and anions in different media are the
subject of ongoing fundamental and practical interest
[1-3]. Most timely are the studies of chemosensors
sensitive to highly toxic cations such as Hg2+, Pb2+,
Cu2+, Ni2+, etc. [4–7]. The earlier prepared N-(9-
anthrylmethyl)-N-benzyl-N'-phenylthiourea proved to
be a selective fluorescent chemosensor to Hg2+ [8].
Aiming at further studies of the sensors on the basis of
N-(9-anthrylmethyl)-substituted alkylamines and di-
amines we synthesized a series of thioureas I–XIV
(Scheme 1).
Scheme 1.
R1NCX
X
N
HN
R
R
HN R1
I−VI
R1
RNCS
R = Et, Ph
H
H
N
N
N
N
X
X
S
HN
R2
VII−XIV
I, R = H, R1 = Ph, X = S; II, R = CH2CH2OH, R1 = Ph, X = S; III, R = H, R1 = All, X = S; IV, R = CH2Ph, R1 = All; V, R =
H, R1 = C6H4Cl-4, X=O; VI, R = CH2Ph, R1 = C6H4Cl-4, X = O; VII, X = (CH2)2, R1 = H, R2 = Ph; VIII, X = (CH2)3, R1 =
C(S)NHPh, R2 = Ph; IX, X = (CH2)4, R1 = C(S)NHPh, R2 = Ph; X, X = (CH2)6, R1 = C(S)NHPh, R2 = Ph; XI, X = (CH2)2,
R1 = C(S)NHEt, R2 = Et; XII, X = (CH2)3, R1 = C(S)NHEt, R2 = Et; XIII, X = (CH2)4, R1 = C(S)NHEt, R2 = Et; XIV,
X = (CH2)6, R1 = C(S)NHEt, R2 = Et.
765

766
TOLPYGIN et al.
Compounds I–IV possessing, apart from the
of the fluorescence spectra in the region of the
anthracene local fluorescence at 390 nm. Among the
studied thiourea derivatives, effective and selective
sensors for Hg2+ cations were found (Fig. 1).
nitrogen atom, a “soft” nucleophilic center, the sulfur
atom, were obtained by the reaction of the
corresponding 9-anthrylmethylamines [8] with phenyl
or allyl isocyanate (Scheme 1). The diamines used for
the synthesis of compounds VII–XIV have been
earlier shown to be highly effective fluorescent chemo-
sensors to zinc(II) cations [9], and phenyl or ethyl
isothiocyanate were taken in a two-fold excess to avoid
the formation of a mixture of the products of mono-
and bis-addition (Scheme 1). In the case of N,N'-bis(9-
anthrylmethyl)ethane-1,2-diamine regardless of the
reaction conditions or the amount of the used PhNCS
(but not EtNCS) only one fragment of thiourea can be
introduced (compound VII), apparently, due to the
arising steric hindrances for introduction of the second
thiourea residue.
Thus, the sensitivity and selectivity with respect to
Hg2+ ions increases in the series of molecules I < II <
III < IV, the N'-allyl-N-(9-anthrylmethyl)-N-benzyl-
thiourea (IV) having the best sensor parameters among
the prepared monothioureas (Fig. 1). Such a large
sensitivity of thiourea to the mercury cation is due to
high affinity of the sulfur-containing receptor to Hg2+
as well as to the possibility of complexes formation of
the chelate type (Scheme 2) [10, 11]. The composition
of the formed complexes with thioureas strongly
depends on the nature of the metal cation and the
substituents at the nitrogen atoms. Per one metal cation
there may be from 1 to 6 thiourea residues [10–13].
The sensory ability of compounds I–XIV with
respect to cations H+, Zn2+, Cd2+, Cu2+, Co2+, Ni2+,
Pb2+, Hg2+ in acetonitrile was estimated from the data
The replacement of a “soft” nucleophilic sulfur
atom in monothioureas by more “hard” oxygen atom
leads to ureas V, VI, respectively, which do not
I
II III IV
V
VI
12
10
8
6
4
2
0
H+
0.6
0.7
1.5
3.6
1.0
0.8
Zn2+
1.2
0.9
0.9
1.1
1.0
0.8
Cd2+
1.3
2.8
1.6
1.2
1.1
0.9
Cu2+
1.0
0.2
0.9
0.7
0.8
0.8
Co2+
0.8
0.7
0.8
1.4
0.5
0.7
Ni2+
Pb2+
0.9
1.1
1.0
0.9
0.9
1.0
Hg2+
2.5
4.6
5.0
11.3
0.9
0.9
1.0
1.1
1.0
0.8
0.9
I
II
III
IV
V
1.0
VI
Fig. 1. Relative variation of intensity of fluorescence of compounds I–VI (с = 5×10–6 M) in acetonitrile upon addition of
trifluoroacetic acid or acetates of various cations (с = 2.5×10–5 M).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 4 2010

CHEMOSENSOR PROPERTIES OF MONO- AND BISTHIOUREAS
767
Scheme 2.
H
S
Mn+/m
S
S
Mn+
R2
R2
+ H+
R
R
R
N
R1
N
N
R1
N
N
N
H
R2
R1
R, R1, R2 = H, Alk, Ar, m = 1, 2, 4, 6.
possess sensor properties with respect to any of the
cations studied (Fig. 1). This effect can be explained
by a sharp decrease in the ability of ureas to complex
formation and by decrease of the heteroatom (oxygen)
affinity to mercury cations.
series of cations is the reaction to Hg2+ ions, the
sensitivity of the sensors increases with the length of
the alkyl chain Х, and the most effective is compound
X on the basis of 1,6-diaminohexane (I/I0 = 34.0). A
similar effect is observed also for the series of
ethylthioureas XI–XIV: the maximum flaring of
fluorescence upon the reaction with mercury(II) ions
occurs in the case of N-(9-anthrylmethyl)-N-(6-{9-
anthrylmethyl[(ethylamino)carbothioyl]amino}hexyl)-
N'-ethylthiourea (XIV) (I/I0 = 14.0). As compared to
the phenyl derivatives, the selectivity and efficiency of
the ethyl derivatives with respect to mercury(II) ions
decreases, however, sharply increases the sensitivity to
Cd2+ ions (Fig. 2).
In the case of the thiourea derivatives VII–X the
efficiency of the sensor with respect to Zn2+ ions
decreases relative to that of the starting diamines [9],
and the dependence of the fluorescence on the pH of
the solution practically disappears. The sensitivity to
Hg2+ ions increases in the series VII < VIII < IX < X
as proved by the corresponding flaring of fluorescence
(Fig. 2). The relatively low sensitivity of sensor VII to
Hg2+ ions can be explained by the presence of only one
thiourea fragment in the molecule. Therefore, in the
case of thioureas VII–X the most selective for the
Therefore, thioureas on the basis of N-(9-
anthrylmethyl)derivatives of alkylamines and diamines
VII
VIII IX X XI XIIXIIIXIV
35
30
25
20
15
10
5
0
H+
13.0
1.7
3.0
1.2
4.7
1.6
1.0
0.7
Zn2+
11.8
1.1
0.9
1.1
1.6
1.2
1.0
1.0
Cd2+
Cu2+
0.5
1.1
0.8
1.2
1.1
0.8
1.1
1.0
Co2+
0.9
0.5
0.9
1.4
0.9
1.2
1.0
1.1
Ni2+
0.6
0.6
0.8
0.9
1.0
0.8
1.0
1.2
Pb2+
0.8
1.0
1.0
1.1
0.9
0.8
1.0
1.3
Hg2+
4.6
7.9
14.5
34.0
10.5
6.5
6.4
0.9
3.6
4.2
6.6
2.2
7.2
5.2
VII
VIII
IX
X
XI
XII
XIII
XIV
7.8
14.0
Fig. 2. Relative variation of intensity of fluorescence of compounds VII–XIV (с = 5×10–6 M) in acetonitrile upon addition of
trifluoroacetic acid or acetates of various cations (с = 2.5×10–5 M).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 4 2010

768
TOLPYGIN et al.
as chemosensors display sensor activity with respect to
a series of cations Zn2+, Cd2+, Hg2+, and N-(9-
anthrylmethyl)-N-(6-{9-anthrylmethyl[(phenylamino)-
carbothioyl]amino}hexyl)-N'-phenylthiourea (X) is a
highly effective chemosensor for Hg2+ cations.
С 74.65; Н 5.70; N 7.20; S 8.38. C24H22N2OS.
Calculated, %: С 74.58; Н 5.74; N 7.25; S 8.30.
N-Allyl-N'-(9-anthrylmethyl)thiourea (III) was
prepared from 9-aminomethylanthracene and allyl-
isothiocyanate. Yield 88%, mp 194–195ºС (1-butanol).
1
IR spectrum, ν, cm–1: 3300, 1550, 1475. Н NMR
EXPERIMENTAL
spectrum, δ, ppm: 3.73–3.94 m (2H, СH2); 5.00–5.20
m (2H, CH2); 5.58–5.85 m (4H, CH2 + NH + CH);
6.00 br.s (1H, NH); 7.40-8.50 m (9H, НAr). Spectrum
of fluorescence in acetonitrile, λmax, nm (c = 5×
10–5 M): 414. Found, %: С 74.54; Н 5.98; N 9.10; S
10.38. С19H18N2S. Calculated, %: С 74.47; Н 5.92; N
9.14; S 10.47.
1Н NMR spectra were taken on a Varian Unity 300
spectrometer (300 MHz). Residual signals of CHCl3
(δ = 7.25 ppm) and (CH3)2SO (δ = 2.50 ppm) were
used as an internal reference. Electron absorption
spectra were taken on a Specord M-40 spectro-
photometer, luminescence spectra were measured on a
Hitachi 650-60 and Varian Eclipse spectrofluorimeters.
Vibrational spectra were recorded on a Specord 75IR
instrument in mineral oil. Melting points were
determined in glass capillaries on a PTP(М) device.
The reactions were followed and the purity of the
obtained compounds was checked by TLC (Silufol
U254 plates, eluent–chloroform, development with
iodine vapors in a wet chamber).
N-Allyl-N'-(9-anthrylmethyl)-N'-benzylthiourea
(IV) was prepared from N-(9-anthrylmethyl)-N-
benzylamine and allyl isothiocyanate. Yield 75%, mp
140–141ºС (1-butanol). IR spectrum, ν, cm–1: 3315,
1
1465, 1370. Н NMR spectrum, δ, ppm: 4.25–4.40 m
(4H, 2CH2); 4.83–5.05 m (2H, CH2); 5.55 t (1H, NH,
J = 5.6 Hz); 5.65–5.85 m (1H, CH); 6.38 s (2H, CH2);
6.75–8.50 m (14H, НAr). Spectrum of fluorescence in
acetonitrile, λmax, nm (c = 5×10–5 M): 417. Found, %:
С 78.72; Н 6.10; N 7.00; S 8.18. C26H24N2S.
Calculated, %: С 78.75; Н 6.10; N 7.06; S 8.09.
General procedure for preparation of ureas and
thioureas. To the solution of 2.0 mmol of the
corresponding amine in 30 ml of benzene 2.2 mmol
(for I–VI) and 4.4 mmol (for VII–XIV) of the
corresponding isocyanate (for V, VI) or isothiocyanate
was added and the obtained mixture was heated on a
water bath for 2 h, cooled, the precipitate formed was
filtered off, washed with ether and crystallized from
the appropriate solvent, and dried in air.
N-(9-Anthrylmethyl)-N'-(4-chlorophenyl)urea (V)
was prepared from 9-aminomethylanthracene and
phenyl isocyanate. Yield 87%, mp >325ºС (subl., 1-
butanol–DMF). IR spectrum, ν, cm–1: 3300, 1627,
1
1555, 1464. Н NMR spectrum, δ, ppm: 5.30 d (2H,
CH2); 6.52 t (1H, NH); 7.05-8.60 m (14H, НAr + NH).
Spectrum of fluorescence in acetonitrile, λmax, nm (c =
5×10–5 M): 413. Found, %: С 73.16; Н 4.80; Cl 9.77;
N 7.84. C22H17ClN2O. Calculated, %: С 73.23; Н 4.75;
Cl 9.83; N 7.76.
N-(9-Anthrylmethyl)-N'-phenylthiourea (I) was
prepared from 9-aminomethylanthracene and phenyl -
isothiocyanate. Yield 82%, mp 191–192ºС (1-butanol).
IR spectrum, ν, cm–1: 3295, 3145, 1547, 1513, 1475.
1Н NMR spectrum, δ, ppm: 5.63 d (2H, CH2, J =
5.2 Hz); 6.97-8.62 m (15H, NH + НAr); 9.18 s (1H,
NH). Spectrum of fluorescence in acetonitrile, λmax, nm
(c = 5×10–5 M): 414. Found, %: С 77.18; Н 5.30; N
8.25; S 9.27. C22H18N2S. Calculated, %: С 77.16; Н
5.30; N 8.18; S 9.36.
N-(9-Anthrylmethyl)-N-benzyl-N'-(4-chloro-
phenyl)urea (VI) was prepared from N-(9-
anthrylmethyl)-N-benzylamine and phenyl isocyanate.
Yield 77%, mp 174–175ºС (1-butanol). IR spectrum,
ν, cm–1: 3287, 1625, 1460, 1367. 1Н NMR spectrum, δ,
ppm: 4.24 s (2H, CH2); 5.81 s (2H, CH2); 6.33 s (1H,
NH); 6.87–8.50
m
(18H, НAr). Spectrum of
N-(9-Anthrylmethyl)-N-(2-hydroxyethyl)-N'-phe-
nylthiourea (II) was prepared from 2-[(9-anthryl-
methyl)amino]ethanol and phenyl isothiocyanate.
Yield 70%, mp 183–184ºС (1-butanol). IR spectrum, ν,
fluorescence in acetonitrile, λmax, nm (c = 5×10–5 M):
414. Found, %: С 77.18; Н 5.20; Cl 7.90; N 6.28.
C29H23ClN2O. Calculated, %: С 77.24; Н 5.14; Cl
7.86; N 6.21.
1
cm–1: 3435, 3195, 1633, 1574, 1467, 1366. Н NMR
spectrum, δ, ppm: 2.92 q (2H, СH2); 3.41 t (2H, CH2);
5.65 t (1H, OH); 6.20 s (2H, CH2); 6.98–8.65 m (14H,
НAr); 10.14 s (1H, NH). Spectrum of fluorescence in
acetonitrile, λmax, nm (c = 5×10–5 M): 416. Found, %:
N-(9-Anthrylmethyl)-N-[2-(9-anthrylmethylamino)-
ethyl]-N'-phenylthiourea (VII) was prepared from
N,N'-bis(9-anthrylmethyl)ethane-1,2-diamine and phenyl
isothiocyanate. Yield 87%, mp 202–203ºС (1-butanol–
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 4 2010

CHEMOSENSOR PROPERTIES OF MONO- AND BISTHIOUREAS
769
DMF 2:1). IR spectrum, ν, cm–1: 1605, 1507, 1475,
1315. Н NMR spectrum, δ, ppm: 1.93–2.06 m (2H,
urea (XI) was prepared from N,N'-bis(9-an-
thrylmethyl)ethane-1,2-diamine and ethyl isothio-
cyanate. Yield 73 %, mp 213–214ºС (1-butanol–DMF
4:1). IR spectrum, ν, cm–1: 3250, 1600, 1500, 1475. 1Н
NMR spectrum, δ, ppm: 1.23 t (6Н, 2СН3, J = 6.5 Hz);
2.98–3.27 m (4H, CH2CH2); 3.54–3.76 m (4H, 2CH2);
5.50 s (4H, 2CH2); 7.20–8.33 m (20H, НAr + 2NH).
Spectrum of fluorescence in acetonitrile, λmax, nm (c =
5×10–5 M): 414. Found, %: С 74.28; Н 6.18; N 9.04; S
10.50. C38H38N4S2. Calculated, %: С 74.23; Н 6.23; N
9.11; S 10.43.
1
CH2); 3.38–3.55 m (2H, CH2); 4.00 s (2H, CH2); 6.28 s
(2H, CH2); 6.45–8.82 m (23H, НAr). Spectrum of
fluorescence in acetonitrile, λmax, nm (c = 5×10–5 M):
415. Found, %: С 81.34; Н 5.75; N 7.37; S 5.54.
C39H33N3S. Calculated, %: С 81.36; Н 5.78; N 7.30; S
5.56.
N-(9-Anthrylmethyl)-N-(3-{9-anthrylmethyl[(phe-
nylamino)carbothioyl]amino}-propyl)-N'-phenyl-
thiourea (VIII) was prepared from N,N'-bis(9-
anthrylmethyl)propane-1,3-diamine and phenyl
isothiocyanate. Yield 70%, mp 201–202ºС (1-butanol–
DMF 2:1). IR spectrum, ν, cm–1: 3250, 1600, 1505,
N-(9-Anthrylmethyl)-N-(3-{9-anthrylmethyl
[(ethylamino)carbothioyl]amino}-propyl)-N'-ethyl-
thiourea (XII) was prepared from N,N'-bis(9-
anthrylmethyl)propane-1,3-diamine and ethyl iso-
thiocyanate. Yield 68%, mp 190–191ºС (1-butanol).
1
1467. Н NMR spectrum, δ, ppm: 1.68–1.84 m (2H,
CH2); 2.86-3.11 m (4H, 2CH2); 5.80 s (4H, 2CH2);
7.02–8.57 m (28H, НAr); 8.95 s (2H, 2NH). Spectrum
of fluorescence in acetonitrile, λmax, nm (c = 5×
10–5 M): 416. Found, %: С 77.83; Н 5.60; N 7.77; S
8.80. C47H40N4S2. Calculated, %: С 77.86; Н 5.56; N
7.73; S 8.85.
1
IR spectrum, ν, cm–1: 3250, 1610, 1505, 1465. Н
NMR spectrum, δ, ppm: 1.18 t (6Н, 2СН3, J = 7.2 Hz);
1.28–1.48 m (2H, CH2); 2.72 t (4H, 2CH2, J = 7.0 Hz);
3.50–3.72 m (4H, 2CH2); 5.66 s (4H, 2CH2); 7.06–
8.54 m (20H, НAr + 2NH). Spectrum of fluorescence in
acetonitrile, λmax, nm (c = 5×10–5 M): 415. Found, %:
С 74.55; Н 6.35; N 8.97; S 10.13. C39H40N4S2.
Calculated, %: С 74.48; Н 6.41; N 8.91; S 10.20.
N-(9-Anthrylmethyl)-N-(4-{9-anthrylmethyl[(phe-
nylamino)carbothioyl]amino}butyl)-N'-phenyl-
thiourea (IX) was prepared from N,N'-bis(9-
anthrylmethyl)butane-1,4-diamine and phenyl
isothiocyanate. Yield 85%, mp187–188ºС(1-butanol–
DMF 2:1). IR spectrum, ν, cm–1: 3260, 1600, 1500,
N-(9-Anthrylmethyl)-N-(4-{9-anthrylmethyl
[(ethylamino)carbothioyl]amino}butyl)-N'-ethylthio-
urea (XIII) was prepared from N,N'-bis(9-
anthrylmethyl)butane-1,4-diamine and ethyl isothio-
cyanate. Yield 88%, mp 165–166ºС (1-butanol–DMF
4:1). IR spectrum, ν, cm–1: 3260, 1600, 1500, 1470,
1
1475, 1453, 1300. Н NMR spectrum, δ, ppm: 1.17–
1.37 m [4H, (CH2)2]; 2.85–3.07 m (4H, 2CH2); 6.00 s
(4H, 2CH2); 7.03–8.60 m (28H, НAr); 9.1 s (2H, 2NH).
Spectrum of fluorescence in acetonitrile, λmax, nm (c =
5×10–5 M): 419. Found, %: С 78.06; Н 5.74; N 7.50; S
8.70. C48H42N4S2. Calculated, %: С 78.01; Н 5.73; N
7.58; S 8.68.
1
1455, 1300. Н NMR spectrum, δ, ppm: 0.88–1.08 m
(4Н, 2СН2); 1.15 t (6Н, 2СН3, J = 6.5 Hz); 2.57–2.78
m (4H, 2CH2); 3.51–3.73 m (4H, 2CH2); 5.87 s (4H,
2CH2); 7.07–8.54 m (20H, НAr + 2NH). Spectrum of
fluorescence in acetonitrile, λmax, nm (c = 5×10–5 M):
415. Found, %: С 74.74; Н 6.64; N 8.72; S 9.90.
C40H42N4S2. Calculated, %: С 74.74; Н 6.58; N 8.71; S
9.97.
N-(9-Anthrylmethyl)-N-(6-{9-anthrylmethyl[(phe-
nylamino)carbothioyl]amino}-hexyl)-N'-phenyl-
thiourea (X) was prepared from N,N'-bis(9-an-
thrylmethyl)hexane-1,6-diamine and phenyl isothio-
cyanate. Yield 76%, mp 192–193ºС (1-butanol–DMF
2:1). IR spectrum, ν, cm–1: 3255, 1680, 1633, 1600,
N-(9-Anthrylmethyl)-N-(6-{9-anthrylmethyl
[(ethylamino)carbothioyl]amino}-hexyl)-N'-ethyl-
thiourea (XIV) was prepared from N,N'-bis(9-an-
thrylmethyl)hexane-1,6-diamine and ethyl isothio-
cyanate. Yield 84%, mp 197–198ºС (1-butanol–DMF
4:1). IR spectrum, ν, cm–1: 3255, 1670, 1600, 1535,
1
1533, 1467, 1447. Н NMR spectrum, δ, ppm: 0.17–
0.35 m [4H, (CH2)2]; 0.80–1.05 m (4H, 2CH2); 2.80–
3.05 m (4H, 2CH2); 6.10 s (4H, 2CH2); 7.05–8.75 m
(28H, НAr.); 9.15 s (2H, 2NH). Spectrum of fluore-
scence in acetonitrile, λmax, nm (c = 5×10–5 M): 416.
Found, %: С 78.22; Н 6.09; N 7.30; S 8.39. C50H46N4S2.
Calculated, %: С 78.29; Н 6.05; N 7.30; S 8.36.
1
1470. Н NMR spectrum, δ, ppm: 0.15–0.36 m (4H,
2CH2); 0.71–0.94 m (4H, 2CH2); 1.20 t (6Н, 2СН3, J =
7.6 Hz); 2.61–2.84 m (4H, 2CH2); 3.57–3.77 m (4H,
2CH2); 5.97 s (4H, 2CH2); 7.15–8.60 m (20H, НAr +
2NH). Spectrum of fluorescence in acetonitrile, λmax
,
N-(9-Anthrylmethyl)-N-(3-{9-anthrylmethyl-
[(ethylamino)carbothioyl]amino}ethyl)-N'-ethylthio-
nm (c = 5×10–5 M): 416. Found, %: С 78.09; Н 6.96;
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 4 2010

770
TOLPYGIN et al.
6. Beeby, A., Parker, D., and Williams, J.A.G., J. Chem.
Soc. Perkin Trans. 2, 1996, p. 1565.
N 8.40; S 9.55. C42H46N4S2. Calculated, %: С 75.18; Н
6.91; N 8.35; S 9.56.
7. Costero, A.M., Banuls, M.J., Aurella, M.J., and
Domenech, A., Tetrahedron, 2006, vol. 62, p. 11972.
ACKNOWLEDGMENTS
8. Tolpygin, I.E., Dubonosov, A.D., Bren’, V.A., Min-
kin, V.I., and Pybalkin, V.P., Zh. Org. Chem., 2003,
vol. 39, no. 9, p. 1435.
This work was performed with the financial support
from the Ministry of Education and Science of RF
9. Tolpygin, I.E., Pybalkin, V.P., Shepelenko, E.N.,
Makarova, N.I., Metelitsa, A.V., Revinskii, Yu.V.,
Tsukanov, A.V., Dubonosov, A.D., Bren’, V.A., and
Minkin, V.I., Zh. Org. Chem., 2007, vol. 43, no. 3,
p. 390.
[National
project
“Education”
(Program of
development of the Southern Federal University),
grant no. RNP.2.2.1.1.2348], CRDF (grant no. REC-
004/BP1M04) and Grant of the President of RF (grant
no. NSh-363.2008.3).
10. Toropova, V.F., Zh. Neorg. Khim., 1956, vol. 1, no. 5,
p. 930.
REFERENCES
11. Umland, F., Jansen, A., Tirig, D., and Wunsch, G.,
Kompleksnye soedimemiya
(Complexes in Analytical Chemistry), Мoscow: Mir,
1975.
v analiticheskoi khimii
1. Callan, J.F., de Silva, A.P., and Magri, D.C.,
Tetrahedron, 2005, vol. 61, p. 8551.
2. Bren, V.A., Usp. Khim., 2001, vol. 70, p. 1152.
3. Rurack, K. and Resch-Genger, U., Chem. Soc. Rev.,
2002, vol. 31, p. 116.
12. Yatsimirskii, K.B., Kostromina, N.A., Sheka, Z.A.,
Davidenko, N.K., Kriss, E.E., and Ermolenko, V.I.,
Khimiya kompleksnykh soedinenii redkozemel’nykh
elementov (Chemistry of Complex Compounds of Rate-
Earth Elements), Kiev: Naukova Dumka, 1966.
4. Kumar, S., Kaur, S., and Singh, G., Supramol. Chem.,
2003, vol. 15, p. 65.
5. Prodi, L., Bargossi, C., Montalti, M., Zaccheroni, N.,
Su, N., Bradshaw, J.S., Izatt, R.M., and Savage, P.B.,
J. Am. Chem. Soc., 2000, vol. 122, p. 6769.
13. Losev, V.N., Bakhtina, M.P., Bakhvalova, I.P.,
Trofimchuk, A.K., and Runov, V.K., J. Anal. Chem.,
2001, vol. 56, p. 341.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 4 2010