Synthesis and characterization of some new star-shaped polydentate ligands from 2,4,6-trichloro-1,3,5-triazine

Article abstract of DOI:10.1080/00397910903576628

Some new star-shaped polydentate ligands were synthesized using 2,4,6-tris(p-formylphenoxy)-1,3,5-triazine as a template and were characterized by infrared, 1H NMR, and 13C NMR spectra and elemental analysis. These products may form polynuclear complexes

Full text of DOI:10.1080/00397910903576628

This article was downloaded by: [University of California, San Francisco]
On: 01 September 2014, At: 00:42
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic Organic
Chemistry
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/lsyc20
Synthesis and Characterization of Some
New Star-Shaped Polydentate Ligands
from 2,4,6-Trichloro-1,3,5-triazine
Hongdong Duan a , Lizhen Wang a , Dawei Qin a , Xiaomeng Li a
Shixiao Wang a & Yi Zhang a
,
a Department of Chemical Engineering, Shandong Institute of Light
Industry , Jinan, China
Published online: 13 Jan 2011.
To cite this article: Hongdong Duan , Lizhen Wang , Dawei Qin , Xiaomeng Li , Shixiao Wang &
Yi Zhang (2011) Synthesis and Characterization of Some New Star-Shaped Polydentate Ligands
from 2,4,6-Trichloro-1,3,5-triazine, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 41:3, 380-384, DOI: 10.1080/00397910903576628
To link to this article: http://dx.doi.org/10.1080/00397910903576628
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Synthetic Communications1, 41: 380–384, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910903576628
SYNTHESIS AND CHARACTERIZATION OF SOME NEW
STAR-SHAPED POLYDENTATE LIGANDS FROM
2,4,6-TRICHLORO-1,3,5-TRIAZINE
Hongdong Duan, Lizhen Wang, Dawei Qin, Xiaomeng Li,
Shixiao Wang, and Yi Zhang
Department of Chemical Engineering, Shandong Institute of Light Industry,
Jinan, China
Some new star-shaped polydentate ligands were synthesized using 2,4,6-tris(p-formylphenoxy)-
1,3,5-triazine as a template and were characterized by infrared, 1H NMR, and 13C NMR
spectra and elemental analysis. These products may form polynuclear complexes with metal
ions, and the complexes may possess potential applications in the area of electromaterials,
optomaterials, magnetic materials, and bio-organic materials.
Keywords: Schiff base; star-shaped polydentate ligands; 1,3,5-triazine derivatives; triazole derivatives
INTRODUCTION
1,3,5-Triazine derivatives have been known for a long time. They have found
widespread applications in the pharmaceutical, textile, plastic, and rubber industries
and are used as pesticides, dyestuffs, optical bleaches, explosives, and surface active
agents.[1] These s-triazine derivatives are mostly synthesized from cyanuric chloride
because of the stability of triazine ring and the controllability of the nucleophilic
substitution reaction of its chlorine atoms. The reactivity of the three chlorine atoms
of cyanuric chloride is very high, which makes its substitution reaction very easy,
but the reactivity degree of the chlorine atoms is different: by controlling the
temperature, 2,4,6-mono, di-, or tri-substituted triazine derivatives can be obtained
in a one-pot synthesis by sequential selective addition of nucleophiles. Furthermore,
cyanuric chloride is a very inexpensive reagent and easily available, which are some
of the reasons that s-triazine derivatives are widely applied.
In recent years, there has been a growing interest in the design and synthesis of
supramolecular polynuclear mental complexes[2,3] because of their potential applica-
tions in magnetism, catalysis, electrical conductivity, and nonlinear optics.[4–8] The
preparation of polymetallic complexes can be achieved by using rationally designed
polydentate ligands.[9] 1,3,5-Triazine derivatives, where the heteroaromatic ring is
implicated in crucial supramolecular interactions, that is, hydrogen bonds and=or
Received August 24, 2009.
Address correspondence to Hongdong Duan, Department of Chemical Engineering, Shandong
Institute of Light Industry, Jinan 250353, China. E-mail: hdduan67@gmail.com
380

STAR-SHAPED POLYDENTATE LIGANDS
381
p interactions,[10] have found tremendous applications in the field of supramolecular
chemistry.[11] Some rigid and flexible polydentate 1,3,5-triazine-based ligands were
designed and synthesized as building blocks for (supramolecular) polymers. It is
worth mentioning that the use of a flexible building block with inherent conforma-
tional freedom may imply the existence of various supramolecular isomers.[12]
Our present aim was to prepare some new star-shaped polydentate ligands using
2,4,6-tris(p-formylphenoxy)-1,3,5-triazine (1) as the template. These compounds
may have the ability to form polynuclear complexes with different metal ions, and
the complexes may have potential applications in electromaterials, optomaterials,
magnetic materials, bio-organic materials, and so on.
RESULTS AND DISCUSSION
Some new star-shaped polydentate ligands 2, 3, and 4 were obtained using the
synthetic methods outlined in Scheme 1. 2,4,6-Tris(p-formylphenoxy)-1,3,5-triazine
(1) was prepared by the reaction of 3 equiv. excess of p-hydroxybenzaldehyde and
1 equiv. of 2,4,6-trichloro-1,3,5-triazine in dioxane at 90 ꢀC for 12 h: triethylamine
was used to trap the HCl formed during the substitution reaction. Compound 1
was isolated and recrystallized from ethyl acetate, and the yield reached 89%, higher
than with the published methods.
Compound 2 was synthesized by the reductive amination of 1 equiv. of 1 and 3
equiv. excess of 4-amino-1,2,4-triazole under refluxed condition in glacial acetic acid.
Infrared (IR) indicated the disappearance of aldehyde. However compounds 3 and 4
were not gained when we used the same synthetic method as used for compound 2.
Scheme 1. Synthesis of the polydentate ligands.

382
H. DUAN ET AL.
During the experiment, we found that controlling the reaction temperature was
important. When the temperature was decreased, compounds 3 and 4 were obtained
in good yields. After repeating the experiment, the best reaction conditions were
identified.
CONCLUSION
A simple method to synthesize some new star-shaped polydentate ligands has
been developed. These ligands were easily obtained in good yield starting from
low-cost, commercially available materials. The products were characterized by
1
Fourier transform (FT)–IR, H NMR, and 13C NMR spectra and elemental analy-
sis. The synthesis of complexes from these ligands and different metal ions is
currently in progress.
EXPERIMENTAL
Material and Physical Measurement
All reagents were obtained from commercial suppliers and used without
further purification. Solvents used for the reactions were purified and dried by
conventional methods. 4-Amino-1,2,4-triazole and its derivatives were synthesized
according to the published procedures.[13–15]
1
Melting points were taken on a SGW X-4 melting-point apparatus. H NMR
and 13C NMR spectra were obtained at 400 MHz using a Bruker Avance 400 NMR
instrument with tetramethylsilane (TMS, d ¼ 0 ppm) as internal standard. The
IR spectra were determined on a Bruker Tensor 27 FT-IR spectrometer using
KBr pellets. Elemental analysis was performed on a Elementar Vario EL III element
analyzer.
Syntheses
Synthesis of compound 1. 2,4,6-Trichloro-1,3,5-triazine (1.84 g, 0.01 mol)
was dissolved in dioxane (20 ml), and a solution of p-hydroxybenzaldehyde
(4.88 g, 0.04 mol) and triethylamine (5.05 g, 0.05 mol) in dioxane (40 ml) was added
dropwise at room temperature. The mixture was stirred at 90 ꢀC for 12 h. The reac-
tion mixture was then cooled, and the solid was removed by filtration. The filtrate
was concentrated, and a white powder was obtained. The white powder was washed
with 10% Na2CO3 and dried in vacuo. Then the powder was recrystallized from
40 ml of ethyl acetate to afford 3.92 g of a white fluffy precipitate: yield ¼ 89%, mp
1
174–176 ꢀC. IR (KBr) n 2833, 1701, 1568, 1361, 1211, 840 cmꢁ1. H NMR (CDCl3)
d 7.26 (d, 6H, J ¼ 8.4 Hz), 7.86 (d, 6H, J ¼ 8.4 Hz), 9.95 (s, 3H) ppm. 13C NMR
(CDCl3) d 122.2, 131.0, 134.0, 155.0, 172.6, 191.8 ppm. Elemental analyses found
(calcd.): C, 65.35 (65.31); H, 3.42 (3.43); N, 9.50 (9.51).
Synthesis of compound 2. 4-Amino-1,2,4-triazole (0.25 g, 3 ꢂ 10ꢁ3 mol)
was added to a solution of 2,4,6-tris(p-formylphenoxy)-1,3,5-triazine (0.22 g,
0.5 ꢂ 10ꢁ3 mol) in 10 ml of glacial acetic acid. The reaction mixture was heated under
reflux for 4 h. The solvent was then removed in vacuo, and the remaining residue was

STAR-SHAPED POLYDENTATE LIGANDS
383
washed with methanol and chloroform. After being dried in vacuo, a white solid was
1
obtained: yield 76%. IR (KBr) n 3103, 1560, 1498, 1365, 1211, 842 cmꢁ1. H NMR
(DMSO) d 7.47 (d, 6H, J ¼ 8.4 Hz), 7.92 (d, 6H, J ¼ 8.4 Hz), 9.09 (s, 3H), 9.12 (s, 6H)
ppm. 13C NMR (DMSO) d 122.3, 129.7, 130.0, 138.8, 153.9, 157.0, 172.7 ppm.
Elemental analyses, found (calcd.): C, 56.39 (56.34); H, 3.32 (3.31); N, 32.88 (32.85).
Synthesis of compound 3. The synthesis was identical to compound 2,
using 4-amino-3,5-dimethyl-1,2,4-triazole instead of 4-amino-1,2,4-triazole. The
mixture was heated at 70 ꢀC for 15 h, and the product was washed with methanol:
1
yield 88%. IR (KBr) n 3358, 1566, 1504, 1363, 1209, 848 cmꢁ1. H NMR (DMSO)
d 2.24 (s, 18H), 7.36 (d, 6H, J ¼ 8.4 Hz), 7.90 (d, 6H, J ¼ 8.4 Hz), 8.72 (s, 3H)
ppm. 13C NMR (DMSO) d 10.6, 122.2, 130.1, 130.9, 147.2, 154.3, 162.9,
172.8 ppm. Elemental analyses, found (calcd.): C, 59.77 (59.74); H, 4.59 (4.60); N,
29.08 (29.05).
Synthesis of compound 4. A mixture of 2,4,6-tris(p-formylphenoxy)-1,3,5-
triazine (0.22 g, 0.5 ꢂ 10ꢁ3 mol) and 4-amino-3,5-bis(hydroxymethyl)-1,2,4-triazole
(0.43 g, 3 ꢂ 10ꢁ3 mol) in 10 ml of glacial acetic acid was heated at 70 ꢀC for 15 h,
and a white precipitate was formed. Then the mixture was filtered, and the product
was washed with methanol. After being dried in vacuo, a white solid was obtained:
yield 84%. IR (KBr) n 3257, 3223, 1570, 1367, 1205 cmꢁ1. 1H NMR (DMSO) d 4.51
(d, 12H), 5.51 (t, 6H), 7.37 (d, 6H, J ¼ 8.8 Hz), 7.87 (d, 6H, J ¼ 8.8 Hz), 8.88 (s, 3H)
ppm. 13C NMR (DMSO) d 53.2, 122.1, 130.2, 130.3, 151.0, 154.2, 162.6, 172.8 ppm.
Elemental analyses, found (calcd.): C, 52.80 (52.75); H, 4.07 (4.06); N, 25.61 (25.63).
ACKNOWLEDGMENTS
The authors are grateful for the financial support of the Nature Science Foun-
dation of Shandong Province and the Outstanding Young Scientists Incentive Fund
of Shandong Province (Y2008B27 and 2007BS04021).
REFERENCES
1. Blotny, G. Recent applications of 2,4,6-trichloro-1,3,5-triazine and its derivatives in
organic synthesis. Tetrahedron 2006, 62, 9507–9522.
´
´
´
´
2. de la Hoz, A.; Dıaz-Ortiz, A.; Elguero, J.; Martınez, L. J.; Moreno, A.; Sanchez-Migallon, A.
Solvent-free preparation of tris-pyrazolyl-1,3,5-triazines. Tetrahedron 2001, 57, 4397–4403.
3. Dey, S. K.; Abedin, T. S. M.; Dawe, L. N.; Tandon S. S.; Collins, J. L.; Thompson, L. K.;
Postnikov, A. V.; Alam, M. S.; Mu1ller, P. Supramolecular self-assembled polynuclear
complexes from tritopic, tetratopic, and pentatopic ligands: Structural, magnetic and
surface studies. Inorg. Chem. 2007, 46, 7767–7781.
4. Jia, H.-P.; Li, W.; Ju, Z.-F.; Zhang, J. Synthesis, structure, and magnetism of metal–
organic framework materials with doubly pillared layers. Eur. J. Inorg. Chem. 2006, 21,
4264–4270.
5. Sun, X.-Z.; Sun, Y.-F.; Ye, B.-H.; Chen, X.-M. Hydrogen-bonding organization of (4,4)
coordination layers into a 3-D molecular architecture with channels clathrating guest mole-
cules [Cu(tdc)(bpy)(H2O)](bpy) (tdc ¼ hiophine-2,5-dicarboxylate; bpy ¼ 4,40-bipyridine).
Inorg. Chem. Commun. 2003, 6, 1412–1414.

384
H. DUAN ET AL.
6. Demessence, A.; Rogez, G.; Welter, R.; Rabu, P. Structure and magnetic properties of a
new cobalt(II) thiophenedicarboxylate coordination polymer showing unprecedented
coordination. Inorg. Chem. 2007, 46, 3423–3425.
7. Gao, L.; Zhao, B.-J.; Li, G.-H.; Shi, Z.; Feng, S.-H. Mixed solvothermal synthesis and
x-ray characterization of
a layered copper coordination polymer, Cu(H2O)(1,3-
BDC) ꢃ H2O (BDC¼enzenedicarboxylate). Inorg. Chem. Commun. 2003, 6, 1249–1251.
8. Gong, Y.; Wang, T.; Zhang, M.; Hu, C.-W. Synthesis, structure, and property of metal
thiophene 2,5-dicarboxylates: Novel three-dimensional coordination polymers. J. Mol.
Struct. 2007, 833, 1–7.
9. de Hoog, P.; Gamez, P.; Driessen, W. L.; Reedijk, J. New polydentate and polynucleating
N-donor ligands from amines and 2,4,6-trichloro-1,3,5-triazine. Tetrahedron Lett. 2002,
43, 6783–6786.
10. Gamez, P.; Reedijk, J. 1,3,5-Triazine-based synthons in supramolecular chemistry. Eur. J.
Inorg. Chem. 2006, 1, 29–42.
ˇ
11. Maheswari, P. U.; Modec, B.; Pevec, A.; Kozlevcar, B.; Massera, C.; Gamez, P.; Reedijk,
J. Crystallographic evidence of nitrate-p interactions involving the electron-deficient
1,3,5-triazine ring. Inorg. Chem. 2006, 45, 6637–6645.
12. Casellas, H.; Gamez, P.; Reedijk, J.; Mutikainen, L.; Turpeinen, U.; Masciocchi, N.;
Galli, S.; Sironi, A. moisture-triggered 1,3,5-triazine-based cuii molecular switch: A com-
bined x-ray single-crystal and powder diffraction study. Inorg. Chem. 2005, 44, 7918–7924.
13. Shi, Y.-Q.; Yu, Y.; Guan, Q.; Wang, Z.-X. A New method of preparation of
4-amino-1,2,4-triazole. Huagong Shikan. 2003, 17, 30–32.
14. Du, J.-Y. Two novel four-coordinated zinc(II) complexes [Zn(dmatrz)2Cl2] and
[Zn(dmatrz)2(SCN)2] exhibiting strong blue fluorescent properties. Transition Met. Chem.
2004, 29, 699–702.
15. Raidt, M.; Neuburger, M.; Kaden, T. A. Stability and structure of mono- and dinuclear
Cu(II), Ni(II), and Zn(II) complexes of pyrazole and triazole bridged bis-macrocycles.
Dalton Trans. 2003, 1292–1298.