Synthesis and metal ion probe properties of four 1,8-naphthalimides

Article abstract of DOI:10.14233/ajchem.2013.13649

Four 1,8-naphthalimide derivatives (3a-3d) were designed and synthesized from 1,8-naphthalic anhydride and their structures were characterized by 1H NMR and MS. Their recognition ability to metal ions was then investigated. The results showed the quenchin

Full text of DOI:10.14233/ajchem.2013.13649

13649
Asian Journal of Chemistry; Vol. 25, No. 6 (2013), 3325-3327
http://dx.doi.org/10.14233/ajchem.2013.13649
Synthesis and Metal Ion Probe Properties of Four 1,8-Naphthalimides
1
2
3
3,*
QIAN LIU , YILIN FANG , XIANGHUI YI , RUI CHEN4,* and YE ZHANG
1Department of Mathematics and Physics, Wuzhou College, Guangxi 543002, P.R. China
2School of Chemistry and Chemical Engineering, Guangxi Normal University, Guangxi 541004, P.R. China
3Department of Chemistry, Guilin Normal College, Guangxi 541001, P.R. China
4College of Chinese Medical Science, Guangxi University of Chinese Medicine, Nanning 530222, P. R. China
*Corresponding author: Fax: +86 77 32806321; Tel: +86 77 32823285; E-mail: zhangye_81@yahoo.com.cn
(Received: 23 February 2012;
Accepted: 19 December 2012)
AJC-12577
Four 1,8-naphthalimide derivatives (3a-3d) were designed and synthesized from 1,8-naphthalic anhydride and their structures were
1
characterized by H NMR and MS. Their recognition ability to metal ions was then investigated. The results showed the quenching
constants (KCV) and binding constants (Ka) values were found in the range of 102-104 M-1, indicating important metal ions recognition
abilities of compounds 3a-3d. All the compounds showed recognition of ferric ion, while compounds 3a-3d showed the best recognition
ability of silver, cadmium, ferric and ferrous ions, respectively.
Key Words: 1,8-Naphthalimides, Synthesis, Recognition, Metal ions.
INTRODUCTION
NH2
O
O
O
It is well known that metal ions play an important role in
many foundamental physiological processes of organisms. As
rich element (K, Ca, Mg, etc.) and trace elements (Co, Ni, etc)
are essential elements for human body, the balance of their
absorption and need do much to human's health. Whereas some
metal ions, such as lead and cadmium are heavy metal pollutants,
can deposit in organism body through various ways and do
harm to organism body1,2. Therefore, it is important to effectively
detect metal ions and that lead to the presence of metallic ion
probes. Among many kinds of metallic ion probes, fluore-
scence probe which can selectively detect, signal and recognize
the presence of metallic ions by the change of their fluore-
scence emission has attracted considerable interest3-9. Thus
design and synthesis of novel fluorescent molecular probe had
become hot subject in bioorganic chemistry.
O
N
N
O
N
N
NH2
Br
Br
R
1
3
2
3a: R=
N
H
3b: R= HO
3c: R=
N
H
H
N
3d: R=
O
Scheme-I
BRUKER AVANCE 500 instrument and the mass spectral
studies were done using BRUKER ESQUIRE HCT instrument.
Melting points were recorded using an electrothermal-WRS-
1A melting point apparatus and were uncorrected. UV-VIS
absorption spectrums were measured in the TU-1901 spectro-
photometer. Fluorescence spectra were recorded in the RF-
5301 fluorospectrophotometer.
1,8-Naphthalimides showed good fluorescence and excellent
photostability, were usually introduced as fluorophore
group10,11 and widely used for high sensitivity fluorescent tracer
and optical chemical sensors. So in this paper, four 1,8-
naphthalimide were designed and synthesized and their metal
ion recognition properties were also studied (Scheme-I).
General procedure
EXPERIMENTAL
Synthesis of compound 2: The mixture of 4-bromo-1,8-
naphthalic anhydride (10 mmol) (1) and o-phenylenediamine
(11 mmol) was refluxed in glacial acetic acid (50 mL) for 6 h.
All reagents for synthesis were commercially available
and employed as received or purified by standard methods
1
prior to use. The H NMR studies were carried out by the
1

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3326 Liu et al.
Asian J. Chem.
RESULTS AND DISCUSSION
Crude product was washed by anhydrous ethanol and was
filtered to give compound 2 as yellow crystals.
2:Yields 87 %, 1H NMR (CDCl3, 500 MHz) δ: 8.92 (dd,
J = 7.5 Hz, 1H, ArH), 8.71 (t, J = 7.5 Hz, 1H, ArH), 8.57 (dd,
J = 7.5 Hz, 2H,ArH), 8.14 (dd, J = 7.5 Hz, 1H, ArH), 7.92 (m,
2H, ArH), 7.52 (dd, J = 2.5 Hz, 2H, ArH).
Illustrated by the case of compound 3b, the fluorescence
spectra of the compound 3b in the presence of various
concentrations of metal ion was shown in Fig. 1. As shown in
Fig. 1(A), it showed no recognition to Na+, K+, Mg2+, Ni2+,
Cu2+. And Pb2+, Zn2+, Fe2+, Ag+ had a little effect on the fluore-
scence of compound 3b. The adding of Co2+ caused fluore-
scence of compound 3b reduced without regularity, while
adding of Fe3+, Cd2+ caused fluorescence linear weak, as shown
in Fig. 1(B).
Synthesis of compound 3: The mixture of compound 2
(10 mmol) and different amine or benzyl alcohol (12 mmol)
was refluxed in ethylene glycol monomethyl ether (50 mL)
with copper sulphate as catalyzer for 6 h, then the crude
produce was purified by column chromatography to give 3 as
yellow-purple crystals.
3a: Yields 70 %, m.p. 200.2-202.8 ºC, 1H NMR (CDCl3,
500 MHz) δ: 8.87(d, J = 5 Hz, 1H, ArH), 8..64 (d, J = 5 Hz,
1H, ArH), 8.00 (d, J = 5 Hz, 1H, ArH), 7.91(dd, J = 5 Hz, 1H,
ArH), 7.69 (dd, J = 7.5 Hz, 1H, ArH), 7.48 (d, J = 5 Hz, 1H,
ArH), 6.77(dd, J = 2.5 Hz, 1H, ArH), 3.42(d, J = 7.5 Hz, 2H,
CH2), 1.82 (q, J = 7.5 Hz, 2H, CH2), 1.36-1.39 (m, J = 12.5
Hz, 1H, NH), 1.29-1.32 (m, J = 10 Hz, 4H, CH2), 1.07(d, J =
7.5 Hz, 3H, CH3), MS m/z (%): 342 (M + H).
3b: Yields 80 %, m.p. 230.6-232.2 ºC, 1H NMR (CDCl3,
500 MHz) δ: 8.28 (d, J = 7.5 Hz, 1H, ArH), 8.16 (d, J = 7.5
Hz, 1H, ArH), 8.01 (d, J = 7.5 Hz, 1H, ArH), 7.64 (dd, J = 7.5
Hz, 1H, ArH), 7.59 (d, J = 7.5 Hz, 1H, ArH), 7.22 (dd, J = 7.5
Hz, 2H, ArH), 7.18 (d, J = 7.5 Hz, 1H, ArH), 4.0 (t, 1H, NH),
3.65 (s, 1H, OH), 3.58 (q, J = 7.1 Hz, 2H, CH2) 3.48 (q, J =
7.1 Hz, 2H, CH2). MS m/z (%): 330 (M + H).
3c: Yields 72 %, m.p. 260.1-261.8 ºC, 1H NMR (CDCl3,
500 MHz) δ: 8.28 (d, J = 7.5 Hz, 1H, ArH), 8.16 (d, J = 7.5
Hz, 1H, ArH), 8.01 (d, J = 7.5 Hz, 1H, ArH), 7.64 (dd, J = 7.5
Hz, 1H, ArH), 7.59 (d, J = 7.5 Hz, 1H, ArH), 7.28 (d, J = 7.55
Hz, 1H, ArH), 7.22 (dd, J = 7.5 Hz, 2H, ArH), 7.20 (dd, J =
7.5 Hz, 2H, ArH), 7.18 (d, J = 7.5 Hz, 1H, ArH), 6.81 (dd, J =
7.5 Hz, 1H, ArH), 4.0 (s, 1H, NH). MS m/z(%): 374(M-H).
3d: Yields 60 %, m.p. 270.3-272.1 ºC, 1H NMR (CDCl3,
500 MHz) δ: 8.28 (d, J = 7.5 Hz, 1H, ArH), 8.23 (d, J = 7.5
Hz, 1H, ArH), 8.16 (d, J = 7.5 Hz, 1H, ArH), 8.01 (d, J = 7.5
Hz, 1H, ArH), 7.64 (d, J = 7.5 Hz, 1H, ArH), 7.58 (d, J = 7.5
Hz, 1H, ArH), 7.49 (d, J = 7.5 Hz, 1H, ArH), 7.42 (d, J = 7.5
Hz, 1H, ArH), 7.21 (d, J = 7.5 Hz, 1H, ArH), 7.20 (dd, J = 7.5
Hz, 2H, ArH), 7.18 (dd, J = 7.5 Hz, 1H, ArH), 6.51 (d, J = 7.5
Hz, 1H, ArH), 6.48 (d, J = 7.5 Hz, 1H, ArH), 3.52 (s, 2H,
CH2), 3.19 (s, 2H, CH2). MS m/z (%): 377 (M + H).
400
(A)
300
200
100
0
450
500
550
600
650
Wavelength (nm)
Wav el engt h
1
9
a
400 (B)
300
200
100
0
450
500
550
600
6500
Wavelength (nm)
Wavel engt h
Fig. 1. Fluorescence spectra of the compound 3b in the presence of various
concentrations of sodium (A) and ferric (B) ions. The concentrations
of Fe3+: 1 → 9 were 0, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0 × 10-4 mol
L-1, respectively
Fluorescence quenching of compound 3 by metal ions
was confirmed by the Stern-Volmer eqn.12,13 1 and modified
Stern-Volmer eqn.12,13 2 as shown in Fig. 2 and the values of
Stern-Volmer quenching constant (KCV) and binding constants
(Ka) were showed in the Tables 1 and 2, respectively.
Recognition ability to metal ions detected by fluore-
scence spectroscopy: The metallic ion recognition properties
of the compounds 3 were investigated by fluorescence quenching
spectroscopy. At room temperature, compounds 3 and metal
ions nitrate (NaNO3, KNO3, Mg(NO3)2, Fe(NO3)2, Fe(NO3)3,
Cd(NO3)2, Pb(NO3)2, Co(NO3)2, Cu(NO3)2, AgNO3, Ni(NO3)2
and Zn(NO3)2) were dissolved in DMF-water (7:3, v:v) to
proper concentration, respectively. The fluorescence spectro-
scopy was scanned in the RF-5301 fluorospectrophoto meter
after mixed solution reached a steady state.
F0
= 1+ Kq τ0c(Q) = 1+ Kcv c(Q)
(1)
F
F0
F0
1
1
=
F0 − F ∆F faKa c(Q) fa
=
+
(2)
As shown in Tables 1 and 2, all the compounds showed
recognition to ferric ion and the quenching constant (KCV) and
binding constants (Ka) values were in the range of 102-103 M-1.
The order was: 3c > 3b > 3a > 3d. It was possibly due to that
ferric ion had strong oxidative which made the fluorescence
quenching phenomenon stronger. In addition, the electron
Recognition ability to metal ions confirmed by UV-
visible spectrum: At room temperature, compounds 3 and
metal ions nitrate [KNO3 and Fe(NO3)3] were dissolved in
DMF-water (7:3, v:v) to proper concentration, respectively.
The UV-visible spectrum was scanned in the TU-1901 spectro-
photometer after mixed solution reached a steady state.
2

13649
Synthesis and Metal Ion Probe Properties of Four 1,8-Naphthalimides 3327
Vol. 25, No. 6 (2013)
1.7
1.6
1.5
1.4
1.3
1.2
1.1
0
3+
Fe
(A)
1.0
0.8
0.6
0.4
0.2
0.0
5(Aa)
1
2
3
4
5
6
7
8
9
400
450
Wavelength (nm)
500
Wav el engt h
3+
C( Fe ) / 10
- 4 - 1
M
1.0
0.8
0.6
0.4
0.2
0.0
9
8
7
6
5
4
3
2
0
+
K
(B)
(B)
(B)
400
450
Wavelength (nm)
500
2
4
6
8
10
wav el engt h
- 1
3+
( Fe ) / 10
3
- 1
M
C
Fig. 3. UV-VIS absorption spectra of the compound 3a with ferric (A) and
potassium (B) ions
Fig. 2. Stern-volmer plots (A) and Modifed Stern-volmer plots (B) for the
quenching of 3b by ferric ion
Conclusion
TABLE-1
Four naphthalimeds 3a-3d were synthesized and their
metal ions recognition was evaluated. The results showed that
compounds 3a-3d displayed important metal ions recognition
abilities.
THE QUENCHING CONSTANTS OF COMPOUND 3
3+
2+
+
2+
KCV /Fe
KCV / Fe
(L mol-1)
KCV/Ag
(L mol-1)
KCV /cd
(L mol-1)
Compound
(L mol-1)
8.00 × 102
8.13 × 102
1.38 × 103
2.87 × 102
–
3.40 × 102
–
3a
3b
3c
3d
–
–
–
–
–
2.74 × 103
–
–
ACKNOWLEDGEMENTS
3.99 × 103
This study was supported by the Fund of Guangxi Key
Laboratory of Functional Phytochemicals Research and
Utilization (No. FPRU2011-6) and the Guangxi Department
of Education research project (No. 201012MS201).
TABLE-2
THE BINDING CONSTANTS OF COMPOUND 3
3+
2+
+
2+
Ka/Fe
Ka/Fe
(L mol-1)
Ka/Ag
(L mol-1)
Ka/cd
(L mol-1)
Compound
(L mol-1)
4.63 × 102
1.41 × 103
4.61 × 103
3.03 × 102
–
1.68 × 103
–
3a
3b
3c
3d
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8.48 × 104
–
–
–
–
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–
–
–
2.04 × 103
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The UV-visible absorption spectra of the compounds
3a-3d with ferric and potass ions system were also selectively
measured to further confirmed the metal ions recognition. As
shown in Fig. 3(A), it can be seen that the UV-visible absorp-
tion spectra 3a-3d decreased as the addition of ferric ion, while
that of 3a-3d with potassium ion displayed no change as shown
in Fig. 3(B). The phenomenon was consistent with that in fluore-
scence quenching spectroscopy, confirming the metal ions
recognition of compounds 3a-3d.
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3