Synthesis of tripodal naphthylacetamide derivatives

Article abstract of DOI:10.1002/jccs.200500026

Atripodalnaphthylacetamide derivative (land II) usedasanewenhancementfluorescence chemical sensor for detection of transition metal ions has been synthesized in this work. Two new derivatives were prepared in good yields according to the proposed method.

Full text of DOI:10.1002/jccs.200500026

Journal of the Chinese Chemical Society, 2005, 52, 169-172
169
Synthesis of Tripodal Naphthylacetamide Derivatives
Yanjie Dong* (
Department of Chemistry, Longdong University, Qingyang City, Gansu, 745000, P. R. China
) and Ke Gai (
)
A tripodal naphthylacetamide derivative (I and II) used as a new enhancement fluorescence chemical sen-
sor for detection of transition metal ions has been synthesized in this work. Two new derivatives were pre-
pared in good yields according to the proposed method. The products were characterized by elemental analy-
1
sis, H NMR spectra, and mass spectrometry (MS).
Keywords: Synthesis; Tripodal naphthylacetamide; Fluorescence; Transition metal ion.
In past years, the study of fluorescence chemical sen-
sors in which a fluorescence emission group and a foreign ob-
ject receiving group compose a fluorescence signal system
for detection of foreign objects, has been highly regarded by
it combines with transition metal ions. Recently, fluores-
7
cence chemical sensors (substance) were reported by Ghosh
8
and Samanta, respectively. In this paper, a tripodal naphthyl-
acetamide derivative (I and II) used as a new enhancement
fluorescence chemical sensor for detection of transition
metal ions has been synthesized. The synthesis of compounds
is summarized as follows.
1
,2
chemists. Fluorescence intensity receiving objects of some
3
d orbit full transition metal ions were reported by Fabbizzi
4
and Czarnik. As we know, transition metal ions play an im-
portant role in biochemistry and environmental chemistry,
and transition metal ions have stronger extinguishments of
The overall yield of the products is 69.6% (I) and
69.5% (II), respectively. During the synthesis, only a little
solvent was used and no protecting groups were introduced.
5
,6
fluorescence intensity. So people have attempted to find
easier and better methods for synthesizing a fluorescence
chemical sensor of enhancement fluorescence intensity after
1
The compounds were characterized by elemental analysis, H
NMR spectra, and mass spectrometry (MS).
OH
COOH
DMAP 0 °C, 1h
CH Cl2 / DCA
+
O
2
NO2
O
NO2
tri(2-aminoethyl)amine
CH Cl ,2h
O
2
2
NH
O
O
HN
N
HN
I
*
Corresponding author. E-mail: huaxx@ldxy.com.cn

1
70 J. Chin. Chem. Soc., Vol. 52, No. 1, 2005
Dong and Gai
OH
NO2
COOH
DMAP 0 °C, 1h
CH Cl / DCA
+
O
2
2
NO2
O
NO2
NO2
NO2
NO2
tri(2-aminoethyl)amine
CH Cl
NO2
O
2
2
NH
O
O
HN
N
HN
II
The compound (I and II) shows excellent complexing
lution was separated by silica gel column, washed with
dichloramethane (CH Cl ) and finally dried in vacuum over
anhydrous CaCl . m.p.: 76-78 °C. yield: 87%. Elemental
analysis calculated for C18
properties and enhancement fluorescence towards some tran-
sition metal ions. For example, the compound clearly en-
hances fluorescence intensity after introduction of the transi-
2
2
2
H
13NO
1
4
(Found): C 70.36 (69.99);
2
+
2+
2+
3+
2+
tion metal ions Cu , Ni , Co , Cr , Mn .
H 4.23 (4.20); N 4.56 (4.60); H NMR (300 MHz, DMSO): d:
7
2
.2-8.4 (m, 11H, ArH), 4.5 (s, 2H, ArCH ).
EXPERIMENTAL
Tri(1-naphthylacetamideethyl)amine (I)
TAEA (0.195 mL, 1.33 mmol), p-nitrophenyl-1-naph-
thylacetate (1.228 g, 4 mmol) were dissolved in 20 mL dry
4
-Dimethylaminopyridine (DMAP, Shanghai, China),
N,N-dicyclohexanemethanamide (DCA, Shanghai, China),
tri(2-aminoethyl)amine (TAEA, Shanghai, China), 1-naphth-
ylacetic acid (Xian, China); all other reagents and solvents
dichloramethane (CH
(CH CH . The solution mixture was whisked for 2 h; the so-
lution changes to yellow. The solution was separated by silica
gel column, washed with dichloramethane (CH Cl ) and fi-
nally dried in vacuum over anhydrous CaCl . m.p.: 221 °C.
yield: 80%. Elemental analysis calculated for C42
2 2
Cl ), and then added to 1 mL N
2
3 3
)
1
used were analytical grade. H NMR data were obtained on a
2
2
Varian Gemini (300 MHz) instrument. Elemental analyses
were performed by a Heraeus CHN Elemental Analyzer. MS
spectra were recorded on a Finnigan 4021c Gc-MS mass
spectrometry Instrument.
2
H
42
N
4
O
1
3
(Found): C 77.51 (76.52); H 6.50 (6.46); N 8.61 (8.63); H
3
NMR (300 MHz, CDCl ): d: 7.78 (m, 21H, ArH), 6.02 (s, 3H,
CONH), 3.95 (s, 6H, ArCH
2
), 2.77 (t, 6H, 3NHCH
2
), 2.16 (t,
+
p-Nitrophenyl-1-naphthylacetate
6H, 3CH
2
N), m/z: 650 (M ), 452 (2.5%), 212 (31.92%), 168
1
-Naphthylacetic acid (1.86 g, 10 mmol), p-nitrophenol
1.39 g, 10 mmol), and DMAP (70 mg) were dissolved in 40
mL dry dichloramethane (CH
Cl ) and the mixture was
(56.62%), 141 (100%), 115 (31.88%).
(
2
2
p-Nitrophenyl-5-nitro-1-naphthylacetate
cooled to 0 °C. Then DCA (2.11 g, 10.2 mmol) was added to
the mixture. The reaction solution was whisked for 1 h; the
mixture was heated to room temperature. The reaction solu-
tion was whisked for 4 h again. The mixture was filtered; so-
5-Nitro-1-naphthylacetic acid (2.31 g, 10 mmol), p-
nitrophenol (1.39 g, 10 mmol), and DMAP (80 mg) were dis-
solved in 40 mL dry dichloramethane (CH
2 2
Cl ), and the mix-
ture was cooled to 0 °C. Then DCA (2.11 g, 10.2 mmol) was

Synthesis of Tripodal Naphthylacetamide Derivatives
J. Chin. Chem. Soc., Vol. 52, No. 1, 2005 171
added to the mixture. The reaction solution was whisked for
nm and 350 nm; the wavelength of profile and value are quite
similar to naphthalene. The fluorescence intensity of com-
pound (I) is less than the fluorescence intensity of naphtha-
1
.5 h; the mixture was heated to room temperature. The reac-
tion solution was whisked for 5 h again. The mixture was fil-
tered; the solution was separated by silica gel column,
2
+
lene at the same concentration of naphthyl. The Cu can en-
hance fluorescence intensity of compound (I).
washed with dichloramethane (CH
vacuum over anhydrous CaCl . m.p.: 86-87 °C. yield: 88%.
Elemental analysis calculated for C18
2 2
Cl ) and finally dried in a
2
In this work, the effect of various transition metal ions
to fluorescence intensity of the compounds (I, II) were stud-
ied. Fig. 2 shows fluorescence intensity of the compound (I)
at 340 nm and Fig. 3 shows fluorescence intensity of the com-
H
12
N
2
O
6
(Found): C
1
6
1.36 (61.69); H 3.41 (3.60); N 7.96 (8.00); H NMR (300
2
MHz, DMSO): d: 7.85 (m, 10H, ArH), 4.6 (s, 2H, ArCH ).
Tri(5-nitro-1-naphthylacetamideethyl)amine (II)
TAEA (0.195 mL, 1.33 mmol), p-nitrophenyl-5-nitro-
-naphthylacetate (1.408 g, 4 mmol) were dissolved in 20 mL
1
dry dichloramethane (CH
CH CH . The solution mixture was whisked for 3 h; the so-
lution changes to yellow. The solution was separated by silica
gel column, washed with dichloramethane (CH Cl ) and fi-
nally dried in a vacuum over anhydrous CaCl . m.p.: 252 °C.
yield: 79%. Elemental analysis calculated for C42
2 2
Cl ), and then added to 1 mL N
(
2
3 3
)
2
2
2
H
39
N
7
O
1
9
(
Found): C 64.18 (64.52); H 4.97 (5.03); N 12.48 (12.60); H
3
NMR (300 MHz, CDCl ): d: 7.80 (m, 18H, ArH), 6.02 (s, 3H,
CONH), 3.95 (s, 6H, ArCH
2
), 2.80 (t, 6H, 3NHCH
2
), 2.18 (t,
+
6
H, 3CH
2
N), m/z: 785 (M ), 542 (3.2%), 257 (33.02%), 203
(
55.02%), 186 (100%), 160 (34.86%).
Fig. 2. Fluorescence intensity of compound (I) at 340
nm as a function of concentration of various
Enhanced fluorescence of the Tri(1-naphthylacetamide-
ethyl)amine (I)
2
+
2+
2+
transition metal ions. 1-Zn ; 2-Cu ; 3-Ni ;
2
+
2+
3+
2+
4
-Co ; 5-Fe ; 6-Cr ; 7-Mn .
The fluorescence spectra of compound (I) are shown
Fig. 1 in acetonitrile. Excitation wavelength is between 325
Fig. 3. Fluorescence intensity of compound (II) at 345
nm as a function of concentration of various
Fig. 1. Fluorescence spectra of compounds in aceto-
-
5
nitrile. (a) compound (I): 5 ´ 10 mol/L; (b)
2
+
2+
2+
-
5
2+
transition metal ions. 1-Co ; 2-Zn ; 3-Mn ;
compound (I) + 5 ´ 10 mol/L Cu ; (c) naph-
2
+
2+
2+
3+
-
5
4
-Cu ; 5-Ni ; 6-Fe ; 7-Cr .
thalene 1.67 ´ 10 mol/L.

1
72 J. Chin. Chem. Soc., Vol. 52, No. 1, 2005
Dong and Gai
pound (II) at 345 nm as a function of concentration of various
transition metal ions. From Fig. 2 and Fig. 3, we can know
various transition metal ions as the effect of fluorescence in-
tensity of the compound (I) and compound (II) are not the
same, but they all can enhance fluorescence intensity of com-
pound (I) and compound (II).
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ACKNOWLEDGMENT
This research is supported by the Natural Science Foun-
dation of the Longdong University.
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