Chemosensors based on N-(2-aminophenyl)-N-(9-anthrylmethyl)amine: II

Article abstract of DOI:10.1134/S1070428009020018

A series of N-(9-anthrylmethyl)arylimines was prepared by condensation of N-(2-aminophenyl)-N-(9-anthrylmethyl)amine with aromatic aldehydes. The study of the luminescent and complexing properties of compounds obtained showed that 2-{[2-(9-anthrylmethylam

Full text of DOI:10.1134/S1070428009020018

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 2, pp. 161−164. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © I.E. Tolpygin, E.N. Shepelenko, Yu.V. Revinskii, A.V. Tsukanov, A.D. Dubonosov, V.A. Bren’, V.I. Minkin, 2009, published in
Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 2, pp. 175−178.
Chemosensors Based
on N-(2-Aminophenyl)-N-(9-Anthrylmethyl)amine: II.*
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
aResearch Institute of Physical and Organic Chemistry at Southern Federal University, Rostov-on-Don, 344090 Russia
e-mail: dubon@ipoc.rsu.ru
bSouthern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
Received January 9, 2008
Abstract—A series of N-(9-anthrylmethyl)arylimines was prepared by condensation of N-(2-aminophenyl)-N-(9-
anthrylmethyl)amine with aromatic aldehydes. The study of the luminescent and complexing properties of
compounds obtained showed that 2-{[2-(9-anthrylmethylamino)phenylimino]methyl}-1-naphthol and 1-{[2-(9-
anthrylmethylamino)phenylimino]methyl}-6-bromo-2-naphthol were efficient highly selective chemosensors of
cations Hg2+.
DOI: 10.1134/S1070428009020018
The designing of efficient fluorescent chemosensors
requires special attention to the choice of the receptor
part governing the selectivity of the created analytical
reagent [1–3]. Previous investigations [4–7] demonstrated
the fundamental possibility to use N-(9-anthrylmethyl)sub-
stituted polyamines and their derivatives as fluorescent
chemosensors.
Owing to the presence in the composition of com-
pounds under study of 9-aminomethylanthracene frag-
ment the main mechanism of the sensor action is PΕT-
effect [10, 11].
The sensor ability of compounds I–VII was estimated
from the fluorescence spectra. To this end to the solution
of compounds I–VII (c 5 × 10–6 mol l−1) was added a cal-
culated five-fold excess of a metal acetate (H+, Zn2+,
Cd2+, Co2+, Ni2+, Cu2+, Pb2+, Hg2+) or of their mixtures
(for compound II).
This study is an extension of the research of sensor
systems based on N-(2-aminophenyl)-N-(9-anthryl-
methyl)amine [8] aiming at the search for more efficient
and selective fluorescent chemosensors for Hg2+ cations.
The intensity of fluorescence of compounds I, II, IV,
V, and VII increased 67, 591, 262, 3.7, and 3.6 times
respectively on addition of mercury acetate (see the
figure). At the addition of CF3COOH to the solutions of
the same compounds the fluorescence increased 13, 96,
9.7, 1.8, and 3-fold. In the case of imine III the
fluorescence intensity increased only at the addition of
cations of mercury(II) (I/I0 5.1); at the addition of the
other cations no fluorescence was observed.
By reactions of N-(2-aminophenyl)-N-(9-anthryl-
methyl)amine with a number of aldehydes we obtained
a series of N-(9-anthrylmethyl)imines I–V (see the
scheme). Compound VI was prepared with the use of
2-(hydroxymethylene)-1-benzothiophen-3(2H)-one as
a “carbonyl” component.
In order to study the coordination center we obtained
tosyl derivative VII by a reaction of equimolar amounts
of 9-anthraldehyde and N-(2-aminophenyl)-4-methyl-
benzenesulfonamide [9] followed by reduction of the
obtained N-[2-(9-anthrylmethyleneamino)phenyl]-4-
methylbenzenesulfonamide with sodium borohydride in
a mixture ethanol–DMF (see the scheme).
The presence of a rigid coordination center in all
compounds synthesized made it possible to form stable
complexes of chelate type. The addition of acetates of
zinc, lead, and copper in the molar ratio 1:5 to the aceto-
nitrile solutions of compounds I, IV, and VII respectively
resulted in the appearance of new fluorescence bands
(λmax 505, 505, and 465 nm) characteristic of complexes
* For communication I, see [8].
161

TOLPYGIN et al.
162
Scheme.
O
NH
HN
OH
S
S
O
VI
RCHO
(1) 9-anthraldehyde, H+
(2) NaBH4, EtOH_DMF
H2N
HN
N
HN
H2N
NH2
R
TsCl
I_V
(1) 9-anthraldehyde, H+
(2) NaBH4, EtOH_DMF
Ts
HN
NH
H2N HN Ts
VII
OH
OH
~
~
HO
HO
(II),
(I),
R =
(V).
HO
(IV),
(III),
Br
HO
of chelate type [12]. In the case of azomethine II the
changes in the fluorescence spectrum occurred at the
action of more cations (Zn2+, Cd2+, and CO2+). At the
interaction of dianthryl derivative V with Hg2+ the classic
type of the anthracene spectrum was recovered, λmax
415 nm (three individual maxima in the region 390–440
nm) apparently due to the destruction of the excimer
structure on the complex formation [13, 14]. In the
spectrum of compound VI possessing fluorescence, λmax
547 nm, the addition of cations Zn2+ and Cd2+ resulted
not only in the intensification of the fluorescence (19 and
4.2-fold), but also to a blue shift of the fluorescence
maximum by 30 nm. The selectivity of the most efficient
among the compounds obtained, 2-{[2-(9-anthrylmethyl-
amino)phenylimino]methyl}-1-naphthol (II), was shown
by adding to its acetonitrile solution (c 5 × 10–6 mol l−1)
a mixture of cations; therewith each cation was taken in
a five-fold molar excess with respect to compound II. In
this case the relative fluorescence intensity increased 570
times. Thus the deviation of the fluorescence intensity of
the compound II solution at the addition of the mixture
of cations from the fluorescence intensity of the
compound II solution at the addition of only mercury
acetate was ~3% demonstrating the high selectivity of
this fluorescence chemosensor with respect to ions Hg2+
in neutral environment.
Thus new fluorescent chemosensors based on the
derivatives of N-(2-aminophenyl)-N-(9-anthrylmethyl)-
amine show the sensor activity with respect to a number
of cations, and 2-{[2-(9-anthrylmethylamino)phenyl-
imino]methyl}-1-naphthol and 1-{[2-(9-anthrylmethyl-
amino)phenylimino]methyl}-6-bromo-2-naphthol are
efficient highly selective chemo-sensors with respect to
Hg2+ cations.
EXPERIMENTAL
1H NMR spectra were registered on a spectrometer
Varian Unity 300 (300 MHz) in CDCl3 or DMSO-d6. As
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CHEMOSENSORS BASED ON N-(2-AMINOPHENYL)-N-(9-ANTHRYLMETHYL)AMINE: II.
163
Relative change in the intensity of fluorescence (I/I0) of compound I (C 5 × 10–6 mol l−1) in acetonitrile on addition of various
cations (C 2.5 × 10–5 mol l−1), “–” means the absence of fluorescence.
13.0
96.0
–
9.7
1.8
1.6
2.1
1.3
1.3
–
6.8
1.0
4.2
0.2
0.2
0.5
–
0.6
0.8
–
1.7
0.7
–
0.8
1.5
–
2.9
1.2
–
0.9
1.2
–
1.3
1.1
–
1.8
1.2
–
I
II
III
IV
V
VI
VII
67.0
591.0
5.1
262.0
3.7
–
11.6
7.5
19.0
0.3
–
–
3.0
1.9
0.2
0.2
0.9
3.6
internal references served residual signals of CHCl3 and
DMSO (δ 7.25 and 2.50 ppm respectively). IR spectra
were obtained on a spectrophotometer Specord 75IR
(from mulls in mineral oil). Electron absorption spectra
were recorded on a spectrophotometer M-40, fluores-
cence spectra, on a spectrofluorimeter Hitachi 650-60.
Melting points were measured in glass capillaries on
a PTP (M) device. The completion of reaction was
monitored and the purity of compounds obtained was
checked by TLC on Silufol UV-254 plates, eluent chloro-
form, development by iodine vapor in a moist chamber.
(2H, CH2), 5.26 s (2H, CH2), 5.63–5.88 m (1H, CH),
6.64–8.76 m (17H, Harom + CH), 12.58 s (1H, OH). Fluores-
cence spectrum in acetonitrile: λmax 415 nm (c 5 ×
10–5 mol l−1). Found, %: C 84.05; H 5.97; N 6.30.
C31H26N2O. Calculated, %: C 84.13; H 5.92; N 6.33.
2-{[2-(9-Anthrylmethylamino)phenyl-
imino]methyl}-1-naphthol (II) was obtained from
N-(2-amino-phenyl)-N-(9-anthrylmethyl)amine and
1-hydroxy-2-naphthaldehyde. Yield 88%, mp 236–237°C
(1-butanol–DMF). IR spectrum, ν, cm–1: 1605, 1460,
1
1375. H NMR spectrum, δ, ppm: 5.04 s (1H, NH),
N-(9-Anthrylmethyl)arylimines. General proce-
dure. In 5 ml of 1-butanol was dissolved 0.3 g (1 mmol)
of N-(2-aminophenyl)-N-(9-anthrylmethyl)amine, 2–3
drops of glacial acetic acid, and 1 mmol of an appropriate
aldehyde was added. The mixture was heated for 30 min,
cooled, the precipitate was filtered off and crystallized
from an appropriate solvent.
5.24 s (2H, CH2), 6.77–8.80 m (19H, Harom + CH),
14.05 s (1H, OH). Fluorescence spectrum in acetonitrile:
λ
max 531 nm (c 5 × 10–5 mol l−1). Found, %: C 84.86;
H 5.42; N 6.25. C32H24N2O. Calculated, %: C 84.93;
H 5.35; N 6.19.
1-{[2-(9-Anthrylmethylamino)phenylimino]-
methyl}naphthalene-2,3-diol (III) was obtained from
N-(2-aminophenyl)-N-(9-anthrylmethyl)amine and 2,3-di-
hydroxy-1-naphthaldehyde. Yield 90%, mp 242–243°C
(1-butanol–DMF). IR spectrum, ν, cm–1: 3400, 1625,
2-Allyl-6-{[2-(9-anthrylmethylamino)phenyl-
imino]methyl}phenol (I) was obtained from N-(2-
aminophenyl)-N-(9-anthrylmethyl)amine and 3-allyl-2-
hydroxybenzaldehyde. Yield 79%, mp 230–231°C (1-
butanol). IR spectrum, ν, cm–1: 1600, 1465, 1380. 1H NMR
spectrum, δ, ppm: 3.00–3.24 m (2H, CH2), 4.76–5.00 m
1
1605, 1560, 1480. H NMR spectrum, δ, ppm: 4.20 s
(1H, NH), 5.27 s (2H, CH2), 6.97 s (1H, NH), 6.80–
8.95 m (18H, Harom + CH), 14.71 s (1H, OH). Fluores-
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TOLPYGIN et al.
164
cence spectrum in acetonitrile: λmax 555 nm (c 5 ×
10–5 mol l−1 ). Found, %: C 82.00; H 5.22; N 5.93.
C32H24N2O2. Calculated, %: C 82.03; H 5.16; N 5.98.
stirring by small portions 0.48 g (12.5 mmol) of sodium
borohydride. The mixture was stirred for 2 h, cooled,
diluted with 200 ml of water, and the excess borohydride
was decomposed by diluted acetic acid. The separated
precipitate was filtered off, washed with water, and dried
in air. Yield 2.0 g (89%), mp 276–277°C (1-butanol). IR
1-{[2-(9-Anthrylmethylamino)phenylimino]-
methyl}-6-bromo-2-naphthol (IV) was obtained from
N-(2-aminophenyl)-N-(9-anthrylmethyl)-amine and
2-hydroxy-6-bromo-1-naphtaldehyde.Yield 83%, mp 275–
276°C (toluene). IR spectrum, ν, cm–1: 1600, 1465, 1385.
1H NMR spectrum, δ, ppm: 4.52 s (1H, NH), 5.24 s (2H,
CH2), 6.80–8.55 (18H, Harom), 9.27 s (1H, CH), 14.30 s
(1H, OH). Fluorescence spectrum in acetonitrile:
1
spectrum, ν, cm–1: 3440, 1610, 1460, 1385. H NMR
spectrum, δ, ppm: 2.31 s (3H, CH3), 4.51 s (1H, NH),
5.07 d (2H, CH2, J 4.8 Hz), 5.77 s (1H, NH), 6.53–
8.60 m (17H, Harom). Fluorescence spectrum in
acetonitrile: λmax 405 nm (c 5 × 10–5 mol l−1 ). Found, %:
C 74.35; H 5.30; N 6.14; S 7.16. C28H24N2O2S.
Calculated, %: C 74.31; H 5.35; N 6.19; S 7.09.
λ
max 416 nm (c 5 × 10–5 mol l−1 ). Found, %: C 72.40;
H 4.33; Br 15.11; N 5.30. C32H23BrN2O. Calculated, %:
C 72.32; H 4.36; Br 15.04; N 5.27.
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant no.
05-03-32470), Ministry of Education and Science of the
Russian Federation [national project “Education” (the
program of development of the Southern Federal
University), RNP.2.2.2.2.5592 and RNP.2.2.1.1.2348], of
Foundation CRDF (grants REC-004/BP1M04 and REC-
004/BF5M04), and a grant of the President of Russian
Federation (NSh-363.2008.3).
2-{[2-(9-Anthrylmethylamino)phenylimino]-
methyl}-1-anthrol (V) was obtained from N-(2-amino-
phenyl)-N-(9-anthrylmethyl)amine and 1-hydroxy-
anthracene-2-carbaldehyde. Yield 91%, mp 315–316°C
(DMF). IR spectrum, ν, cm–1: 3410, 1620, 1460, 1390.
1H NMR spectrum, δ, ppm: 5.20 d (2H, CH2, J 4.1 Hz),
5.65 t (1H, NH, J 3.5 Hz), 6.75–8.78 m (22H, Harom
+
CH), 13.64 C (1H, OH). Fluorescence spectrum in
acetonitrile: λmax 545 nm (c 5 × 10–5 mol l−1 ). Found, %:
C 85.96; H 5.25; N 5.55. C36H26N2O. Calculated, %:
C 86.03; H 5.21; N 5.57.
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CHEMOSENSORS BASED ON N-(2-AMINOPHENYL)-N-(9-ANTHRYLMETHYL)AMINE: II.
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