Hydrothermal syntheses of some derivatives of tetraazatriphenylene

Article abstract of DOI:10.1080/00397910600781323

Some derivatives of tetraazatriphenylene can be synthesized readily by a hydrothermal synthetic method. Compared with the traditional technique, this method is effective and simple process, and much high yields of products with higher purity can be harvested. Copyright Taylor & Francis Group, LLC.

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Hydrothermal Syntheses of Some Derivatives
of Tetraazatriphenylene
Guangbo Che a b , Wenlian Li a , Zhiguo Kong a b , Zisheng Su a b , Bei Chu a ,
Bin Li b , Zhiqiang Zhang c , Zhizhi Hu c & Haijun Chi c
a Key Laboratory of the Excited States Process, Changchun Institute
of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences,
Changchun, China
b Graduate School of the Chinese Academy of Sciences, Beijing, China
c Organic Photoelectronic Material Research and Development Center,
Anshan University of Science and Technology, Liaoning, China
Version of record first published: 27 Oct 2006.
To cite this article: Guangbo Che, Wenlian Li, Zhiguo Kong, Zisheng Su, Bei Chu, Bin Li, Zhiqiang Zhang,
Zhizhi Hu & Haijun Chi (2006): Hydrothermal Syntheses of Some Derivatives of Tetraazatriphenylene,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
36:17, 2519-2524
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Synthetic Communicationsw, 36: 2519–2524, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600781323
Hydrothermal Syntheses of Some
Derivatives of Tetraazatriphenylene
Guangbo Che
Key Laboratory of the Excited States Process, Changchun Institute of
Optics, Fine Mechanics and Physics, Chinese Academy of Sciences,
Changchun, China and Graduate School of the Chinese Academy of
Sciences, Beijing, China
Wenlian Li
Key Laboratory of the Excited States Process, Changchun Institute of
Optics, Fine Mechanics and Physics, Chinese Academy of Sciences,
Changchun, China
Zhiguo Kong and Zisheng Su
Key Laboratory of the Excited States Process, Changchun Institute of
Optics, Fine Mechanics and Physics, Chinese Academy of Sciences,
Changchun, China and Graduate School of the Chinese Academy of
Sciences, Beijing, China
Bei Chu
Key Laboratory of the Excited States Process, Changchun Institute of
Optics, Fine Mechanics and Physics, Chinese Academy of Sciences,
Changchun, China
Bin Li
Graduate School of the Chinese Academy of Sciences, Beijing, China
Zhiqiang Zhang, Zhizhi Hu, and Haijun Chi
Organic Photoelectronic Material Research and Development Center,
Anshan University of Science and Technology, Liaoning, China
Received ???
Address correspondence to Wenlian Li, Key Laboratory of the Excited States
Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese
Academy of Sciences, Changchun 130033, China. E-mail: wllioel@yahoo.com.cn
2519

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G. Che et al.
Abstract: Some derivatives of tetraazatriphenylene can be synthesized readily by a
hydrothermal synthetic method. Compared with the traditional technique, this
method is effective and simple process, and much high yields of products with
higher purity can be harvested.
Keywords: Derivatives of tetraazatriphenylene, high yield, hydrothermal, 1,10-
phenanthroline-5,6-dione
INTRODUCTION
One of the earliest and most extensively studied N-heterocyclic chelating
agents is the bidentate 1,10-phenanthroline. It and related N-heterocycles
are widely employed as metal-binding components in all aspects of
coordination chemistry. It is one of the most important derivatives of the
phenanthroline ligand, and use of the complexes of tetrazatriphenylene
ligand derivatives with transition or rare earth metal ions for display
devices, solar-energy conversion, biological probing, and chemical sensors
has become one of the most important subjects in the past few years. Those
of Re(I), Ru(II), Rh(III), and Os(II) have been proposed as luminescent
DNA probes on the basis of their strong binding to double helical DNA and
a negligible background emission of any unbound complex.[1] Recently,
Sun et al. further extended the practical application of derivatives of
tetrazatriphenylene. They reported some new europium complexes
with these ligands, and utilization of these complexes as red emitters in
EL (electroluminescence) devices was explored.[2,3] Commonly used
derivatives of tetrazatriphenylene ligands include PyPhen (pyrazino[2,3-
f][1,10]phenanthroline), DPPz (dipyrido[3,2-a:20,30-c] phenazine), Dicnq
(6,7-dicyanodipyrido [2,2-d: 20,30-f] quinoxaline), and BDPz (benzo[i]
dipyrido [3,2-a:20,30-c]phenazine). The synthesis of the ligands was
conducted by
a condensation of 1,10-phenanthroline-5,6-dione and
1,2-diamine.[4–8] Although the preparation method of the derivatives of
tetrazatriphenylene was very mature, the yield and purity of the
harvested products were relatively lower, and after-treatment of the product
is difficult. Hydrothermal synthesis has rapidly developed over the past
several years because of its effectiveness and simplicity. In organic
synthesis, hydrothermal synthesis has become very useful route to
organic compounds, which are difficult to obtain by routine synthetic
methods.[9–11] Therefore, researchers have directed their attention to this
synthetic method to exploit some organic compounds. In this article, we
extend the synthetic technique to prepare derivatives of tetrazatriphenylene
and report a more convenient synthesis method of hydrotherm using
1,10-phenanthroline as starting material. High yields and purity of products
are obtained.

Hydrothermal Syntheses of Tetraazatriphenylene
EXPERIMENTAL
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Synthesis of 1,10-Phenanthroline-5,6-dione
1,10-Phenanthroline-5,6-dione was prepared according to a slightly modified
method reported in Ref. 12. 1,10-Phenanthroline (2.00 g, 1.01 ꢀ 1022 mol)
and potassium bromide (3.00 g, 2.52 ꢀ 1022 mol) were mixed with cold
concentrated sulphuric acid (20 ml, 98%) at 08C in a three-necked, round-
bottomed flask with reflex condenser. Fuming nitric acid (68%, w/w, 10 ml)
was added dropwise with stirring under 308C. The mixture was heated to
408C for 3 h when fuming nitric acid drop over and then heated to 80–
908C for 1 h. Under the same temperature, the reflex condenser was moved
to let bromine volatilize (about 3 h), and the mixture was cooled and poured
onto a mixture of ice and water. The pH was adjusted to 6–7 with aqueous
sodium hydroxide saturated solution, and the solution was extracted with
dichloromethane. The dichloromethane layer was dried with anhydrous
magnesium sulfate, and the solvent was removed. The residue was recrystal-
lized from methanol to afford yellow needles of 1,10-phenanthroline-5,6-
1
dione (Scheme 1), mp 257–2588C (lit.[5] mp 2588C), yield 86%. H NMR
(CDCl3): d 9.13 (q, 2H, J ¼ 4.8 Hz), 8.52 (q, 2H, J ¼ 8.0 Hz), 7.60 (q, 2H,
J ¼ 4.8 Hz, 8.0 Hz); IR (KBr): 2362, 1681, 1575, 1455; MS: m/z 211.6
(Mþ þ 1). Anal. calcd. for C12H6N2O2: C, 68.57; H, 2.88; N, 13.33. Found:
C, 66.94; H, 2.65; N, 13.06.
Condensation of 1,10-Phenanthroline-5,6-dione and Diamine
A mixture of 1,10-phenanthroline-5,6-dione (5.00 mmol) and diamine
(6.00 mmol) in a mixed solution of 90 ml of H2O and 10 ml of 95% ethanol
were heated at 1808C for 1 day in a sealed 150-ml Teflonw-lined stainless
steel vessel under autogenous pressure. After the reaction mixture was
slowly cooled down to room temperature, needle crystals that precipitated
from the solution were filtered off, washed with cold ethanol, and suction
dried to obtain the desired product in pure form with yield of 89–93%
based on 1,10-phenanthroline-5,6-dione. Scheme 2 summarizes the reaction
Scheme 1. Reaction scheme for the preparation of 1,10-phenanthroline-5,6-dione.

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G. Che et al.
Scheme 2. Syntheses of the derivatives of tetraazatriphenylene.
conditions, reagents used, and the core structures of the reactants and products.
The structures of several substituted phenanthrolines (PyPhen, Dicnq, DPPz,
and BDPz) are shown in Fig. 1. These derivatives of tetrazatriphenylene
were characterized by NMR, IR, MS, and elemental analysis.
Data
PyPhen. Colorless needles, mp 253–2548C (lit.[7] mp 253–2558C), yield:
89%. 1H NMR (CDCl3): d 9.51(d, 2H, J ¼ 8.0 Hz), 9.31 (d, 2H,
J ¼ 8.0 Hz), 9.01 (s, 2H), 7.82 (dd, 2H, J ¼ 8.0, 8.0 Hz). IR (KBr): 1638,
1400, 1080, 561. MS: m/z 233.1 (Mþ þ 1). Anal. calcd. for C14H8N4: C,
72.41; H, 3.45; N, 24.14. Found: C, 72.24; H, 3.48; N, 23.98.
Dicnq. Brownish-yellow needles, yield: 91%. 1H NMR (CDCl3): d 9.47
(q, 2H, J ¼ 8.4, 1.8 Hz), 9.42 (q, 2H, J ¼ 4.4, 1.8 Hz), 7.93 (q, 2H, J ¼ 8.4,
4.4 Hz). IR (KBr): 3400, 3069, 2338, 2240, 1580, 1453. MS: m/z
283.3(Mþ þ 1). Anal. calcd. for C16H6N6: C, 68.08; H, 2.14; N, 29.77.
Found: C, 67.99; H, 2.19; N, 29.53.
DPPz. Yellowish needles, mp 251–2528C (lit.[5] mp 2508C), yield: 93%. This
1
compound had H NMR (CDCl3): d 9.65 (d, 2H, J ¼ 8.0 Hz), 9.27 (d, 2H,
J ¼ 8.0 Hz), 8.35 (d, 2H, J ¼ 6.4 Hz), 7.91 (d, 2H, J ¼ 6.4 Hz), 7.80 (dd,

Hydrothermal Syntheses of Tetraazatriphenylene
2523
Figure 1. The structures of several substituted phenanthrolines.
2H, J ¼ 8.0, 8.0 Hz). IR (KBr): 1638, 1617, 1400, 1074, 739, 616. MS: m/z
283.1 (Mþ þ 1). Anal. calcd. for C18H10N4: C, 76.60; H, 3.55; N, 19.86.
Found: C, 75.95; H, 3.61; N, 19.81.
BDPz. Rufous needles, yield: 91%. 1H NMR (CDCl3): d 9.69 (d, 2H,
J ¼ 8.0 Hz), 9.28 (d, 2H, J ¼ 8.0 Hz), 8.99 (s, 2H), 8.23 (d, 2H,
J ¼ 8.0 Hz), 7.82 (dd, 2H, J ¼ 8.0, 8.0 Hz), 7.65 (d, 2H, J ¼ 8.0 Hz). IR
(KBr): 1618, 1400, 1112, 619. MS: m/z 333.1 (Mþ þ 1). Anal. calcd. for
C22H12N4: C, 79.52; H, 3.61; N, 16.87. Found: C, 79.30; H, 3.74; N, 16.79.
RESULTS AND DISCUSSION
The hydrothermal synthetic method, as a novel approach for synthesizing
some derivatives of tetraazatriphenylene, has been presented. Compared
with traditional synthetic methods, the technique has the following benefits:
(1) It is a simple synthetic procedure. The traditional synthesis of derivatives of
tetraazatriphenylene was conducted by a condensation of 1,10-phenanthroline-
5,6-dione and 1,2-diamine in ethanol at the refluxing temperature. Some prep-
arations need to be processing under a nitrogen atmosphere,[3,13] and the
products obtained on cooling were recrystallized from aqueous ethanol.
These procedures can be simplified by using the hydrothermal synthetic
method. Furthermore, it is well known that organic amines, especially
aromatic amine chemicals, are volatile and toxic. In traditional methods, it
is inevitable that these toxic amido compounds can easily be volatilized into
the air and pollute the environment. (2) The products obtained by our

2524
G. Che et al.
technique are easily isolated and purified. Slow formation of the product will
ensure the growth of crystals sufficiently large isolate pure products from the
reaction mixtures by simple filtration. Hydrothermal reactions carried out in
sealed Teflonw bombs and in the temperature range 120–2008C under autoge-
nous pressure (generally 10–30 atm) exploit the self-assembly of the product
from soluble precursors. The reduced viscosity of solvents under these
conditions enhances the diffusion processes so that crystal growth from
solution is favored.[9] Thus, under such nonequilibrium crystallization con-
ditions, highly pure products must be obtained. (3) The products are formed
in excellent yields. Amine can be oxidated easily in air by traditional
synthetic means, especially under the conditions of heating and no nitrogen
protection, which leads to reduced yields of product. Nevertheless, the
phenomenon can be avoided using hydrothermal reactions because of the
sealed system. Hydrothermal reactions of 1,10-phenanthroline-5,6-dione
with the various diamines gave the corresponding tetraazatriphenylenes in
89–93% yields, which are higher than results previous reported.[3,14,15] The
copper complexes were synthesized using those ligands and have already
been applied for designing and fabricating the organic light-emitting diode
fields; the corresponding results will be reported elsewhere. The hydrothermal
synthetic method can be expanded to synthesis of other organic ligands of
metal complexes as well.
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