Synthesis and characterization of chloropentaaryloxycyclotriphosphazene derivatives

Article abstract of DOI:10.1080/10426500802424006

Five chloropentaaryloxycyclotriphosphazene derivatives were synthesized by the reaction of hexachlorocyclotriphosphazene with potassium phenoxide in tetrahydrofuran. A satisfactory yield could be obtained when a 5.1: 1(KOC ₆H₄R:P

Full text of DOI:10.1080/10426500802424006

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Phosphorus, Sulfur, and Silicon
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Synthesis and
Characterization of
Chloropentaaryloxycyclotriphospha
Derivatives
a b
a c
a
Zhiyu Ju
, Yong Ye
, Le Wang , Xincheng Liao
a
a c
&
Yufen Zhao
a
Key Laboratory of Chemical Biology and Organic
Chemistry of Henan Province, Department of
Chemistry , Zhengzhou University , Zhengzhou,
China
b
College of Chemical and Chemical Engineering ,
Xunchang University , Xunchang, China
c
Key Laboratory of Bioorganic Phosphorus Chemistry
&
Chemical Biology, Ministry of Education,
Department of Chemistry , Tsinghua University ,
Beijing, China
Published online: 22 Jul 2009.
To cite this article: Zhiyu Ju , Yong Ye , Le Wang , Xincheng Liao & Yufen Zhao (2009)
Synthesis and Characterization of Chloropentaaryloxycyclotriphosphazene Derivatives,
Phosphorus, Sulfur, and Silicon and the Related Elements, 184:8, 2103-2108, DOI:
10.1080/10426500802424006
To link to this article: http://dx.doi.org/10.1080/10426500802424006
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Phosphorus, Sulfur, and Silicon, 184:2103–2108, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802424006
Synthesis and Characterization of
Chloropentaaryloxycyclotriphosphazene Derivatives
Zhiyu Ju,1,2 Yong Ye, Le Wang, Xincheng Liao,1
1,3
1
1
,3
and Yufen Zhao
1
Key Laboratory of Chemical Biology and Organic Chemistry of Henan
Province, Department of Chemistry, Zhengzhou University, Zhengzhou,
China
2
College of Chemical and Chemical Engineering, Xunchang University,
Xunchang, China
3
Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical
Biology, Ministry of Education, Department of Chemistry, Tsinghua
University, Beijing, China
Five chloropentaaryloxycyclotriphosphazene derivatives were synthesized by the re-
action of hexachlorocyclotriphosphazene with potassium phenoxide in tetrahydro-
furan. A satisfactory yield could be obtained when a 5.1: 1(KOC H R:P N Cl )
6
4
3
3
6
P
1
31
molar ratio was used. The new compounds were characterized by IR, H NMR,
13
NMR, C NMR, and ESI-MS, and for two of them by HR-MS.
Keywords Chloropentaaryloxycyclotriphosphazene derivatives; hexachlorocyclot-
riphosphazene; phenols; potassium carbonate
INTRODUCTION
Phosphazenes have received increasing interest, not only because of
their wide spectrum of chemical and physical properties, but also due
to their importance in synthetic chemistry. Different side-group struc-
tures affect the chemical and physical properties of ring systems and
1
−3
high polymers based on a phosphazene skeleton.
Specifically, the
properties of phosphazenes can be controlled by the organic groups
connected to the phosphazene ring. Accordingly, various phosphazenes
Received 8 July 2008; accepted 20 August 2008.
The authors would like to thank the National Natural Science Foundation of China
(No. 20602032, 20732004) and Zhengzhou University for financial support.
Address correspondence to Yong Ye and Yufen Zhao, Key Laboratory of Chemical
Biology and Organic Chemistry of Henan Province, Department of Chemistry, Zhengzhou
University, Zhengzhou 450052, China. E-mail: juz1696@yahoo.com.cn
2103

2104
Z. Ju et al.
have been successfully developed in a variety of applications, such as
flame retardants, elastomerics, and biomaterials, by controlling the
4
−6
side group.
In this article, we describe the reaction of hexachloro-
cyclotriphosphazene with phenols to gain potential intermediates as
potential functional materials.
RESULTS AND DISCUSSION
Compound 3 was synthesized according to a modified procedure re-
7
ported by McBee et al. The dangerous sodium alloy previously used
was replaced by potassium carbonate enabling a safer handling and an
easier filtration together with a lower cost.
In addition, we found that the reactant ratio had an important ef-
fect on the yield of the pentaarylcyclotriphosphazene by following the
3
1
reaction by P NMR tracking, as shown in Figure 1. The yields of
P3N3Cl(OC6H5)5 were, respectively, 52% (4.5:1), 72% (5:1), and 51%
(
(
5.5:1). The numbers in parentheses denote the reactant mole ratio
KOPh:P3N3Cl6). Consequently, a satisfactory yield of the expected
compounds can be obtained when an optimum 5.1:1 KOPh:P3N3Cl6
3
1
ratio was used. The percentages were measured by P NMR.
3 3 6
FIGURE 1 Yields of the different substituted phosphazenes vs KOPh:P N Cl
ratio (reaction temperature at room temperature).

Chloropentaaryloxycyclotriphosphazene Derivatives
2105
FIGURE 2 31P NMR spectrum of compound 1 in CDCl
at room temperature
3
at 162 MHz.
The 31P NMR spectrum of compound 1 is shown in Figure 2. It
shows that the two phosphorus nuclei are chemically equivalent, and
2
their chemical shifts are recorded as doublets ( JPP = 84.2 Hz) at high
magnetic fields. The only explanation for the absorption is that the
two phosphorus nuclei are substituted by four phenoxy groups. It can
be concluded that it may have the penta- or 2,2,4,4-tetra-substituted
2
structure (A or B in Figure 3). Because the coupling constant Jpp of the
2,2,4,4-tetra-substituted structure (B in Figure 3) is at approximately
FIGURE 3 Possible structures for 31P NMR spectrum of compound 1.

2106
Z. Ju et al.
8
6
0–70 Hz, it clearly supports the proposed A in Figure 3, the penta-
substituted structure.
CONCLUSION
An economical and safe synthetic route has been developed for the
synthesis of chloropentaaryloxycyclotriphosphazenes. The compounds
were obtained in good yields when a 5.1:1 KOC6H4R:P3N3Cl6 ratio was
1
used. The new compounds were characterized by means of IR, H NMR,
3
1
13
P NMR, C NMR, and mass spectrometry.
EXPERIMENTAL
All chemicals and materials were of analytical grade, and all solutions
were freshly dried by standard methods.
1
H NMR spectra and 13C NMR spectra were recorded using a Bruker
DTX-400 spectrometer. Samples were dissolved in CDCl3 and placed in
5
mm n.m.r. tubes. Measurements were carried out using a CDCl3 lock,
3
1
TMS as internal reference. P NMR spectra were recorded using a
Bruker DTX-400 spectrometer; 85% H3PO4 was used as an external
reference. Samples were dissolved in CDCl3 and placed in 5 mm n.m.r.
tubes. CDCl3 was used as a “lock” solvent, and chemical shifts were
measured relative to TMS (0 ppm).
Mass spectra were acquired in positive ion mode using a Bruker
ESQUIRE 3000 ion trap spectrometer equipped with a gas nebulizer
probe, capable of analyzing ions up to m/z 6000. Nitrogen was used
as drying gas at a flowrate of 4.5 L/min. The nebulizer pressure was
7.5 psi. Measurements and calculations are based on mass of most
abundant isotopes.
The high-resolution mass spectral data for compounds 2 and 3 were
TM
recorded on a Waters Q-Tof micro spectrometer by electrospray ion-
ization (ESI) mass spectrometer. The sample was analyzed as a solution
in methanol.
Preparation of Hexachlorocyclotriphosphazene
Hexachlorocyclotriphosphazene was prepared by the method described
9
previously. Specifically, a correct quantity of active carbon was added
to the reaction system under the reflux for 1 h after the reaction was
over. The product was purified by recrystallization from heptane to
give hexachlorocyclotriphosphazene as white crystals. Yield: 89%, mp
◦
◦
31
1
11–113 C (literature: 111.5–113.5 C), P NMR (162 MHz, THF): δ
20.44 ppm (s).

Chloropentaaryloxycyclotriphosphazene Derivatives
2107
Preparation of Chloropentaaryloxycyclotriphosphazenes
Hexachlorocyclotriphosphazene (1.44 mmol) and tetrahydrofuran (5
mL) were added to a three-neck flask. To this mixture, a solution of
potassium aryloxide, which was prepared by the reaction of phenols
(
(
7.33 mmol) with potassium carbonate (7.33 mmol) in tetrahydrofuran
20 mL) before the reaction, was added dropwise at room temperature
for 1 h. The reaction was kept at this temperature for 1–2 h and then fil-
tered. The solvent was removed by rotary evaporation, and the residue
was purified by chromatography on silica gel, for the compounds 1–4
using petroleum ether:ethyl acetate (20:1) as eluent, and for compound
5, petroleum ether:tetrahydrofuran (4:1) was selected (Scheme 1).
SCHEME 1 Synthetic route of chloropentaaryloxycyclotriphosphazenes.
Data of the title compounds are given below:
1
Compound 1: liquid, Yield: 71%;
H
NMR (400 MHz,
3
1
CDCl3)δ ppm 7.15∼6.76 (m, 20H, C6H4), 2.27 (s, 15H, CH3);
P
NMR (162 MHz, CDCl3)δ ppm 21.63 (t, 1P), 6.46 (d, 2P), J(PP) = 84.2
1
3
Hz; C NMR (100MHz, CDCl3)δ ppm 150.35, 139.61, 129.13, 125.95,
−1
1
2
21.76,118.11; IR (KBr) (cm ): 3033, 1610, 1586 and 1488 (Ar), 2920,
−1
856 and 1401 (CH3), 1278, 1210 and 1140 cm (P N), 545P-Cl);
+
ESI-MS: m/z 706.1[M+H] .
Compound 2: White solid, mp: 78∼80 C, Yield: 79%; 1H NMR
◦
(
400 MHz, CDCl3)δ ppm 7.04∼6.70(m, 20H, C6H4), 3.78(s, 15H, CH3);
3
1
P NMR (162 MHz, CDCl3)δ ppm 23.03 (t, 1P), 8.05 (d, 2P), J(PP)
1
3
=
81.0 Hz; C NMR (100 MHz, CDCl3)δ ppm 156.77, 143.83, 122.12,
14.37, 55.52; IR (KBr) (cm ): 3003, 1589 and 1444(Ar), 2958, 2835
and 1400 (CH3), 1210 and 1164cm (P N), 520 (P Cl); ESI-MS: m/z
−1
1
−1
+
+
7
86.1[M+H] . ESI-MS: m/z 636.1[M+H] . HR-MS(ESI): m/z calcd. for
+
C35H36ClN3O10P3 [M+H] : 786.1297, found 786.1298.
◦
◦
7
Compound 3: White solid, mp: 68∼70 C (literature: 69–71 C), Yield:
1
31
7
6%; H NMR (400 MHz, CDCl3)δ ppm 7.26∼6.91(m, 25H, C6H5);
P
NMR (162 MHz, CDCl3)δ ppm 22.93 (t, 1P), 7.63 (d, 2P), J(PP) =
1
3
8
2.8 Hz; C NMR (100 MHz, CDCl3)δ ppm 150.33, 129.52, 125.40,

2108
Z. Ju et al.
−
1
(
21.23; IR (KBr) (cm 1): 3060, 1591 and 1487(Ar), 1267, 1178 and 1152
+
P N), 500 (P Cl); ESI-MS: m/z 636.1[M+H] . HR-MS(ESI): m/z calcd.
+
for C30H26ClN3O5P3 [M+H] : 636.0768, found 636.0770.
Compound 4: White solid, mp: 92∼94 C, Yield: 85%; 1H NMR
◦
(
400 MHz, CDCl3)δ ppm 9.97(s, 5H, CHO), 7.83∼7.22 (m, 20H, C6H4);
3
1
P NMR (162 MHz, CDCl3)δ ppm 20.71 (t, 1P), 5.17 (d, 2P), J(PP)
1
3
=
85.8 Hz; C NMR (100 MHz, CDCl3)δ ppm 190.54, 154.28, 133.97,
31.47, 121.63; IR (KBr) (cm ): 3105, 1595 and 1499(Ar), 2825, 2741
−1
1
(
O C H), 1705 (C O), 1210, 1179 and 1148 (P N), 511 (P Cl); ESI-
+
MS: m/z 776.1[M+H] .
◦
1
Compound 5: White solid, mp: 169∼171 C, Yield: 54%; H NMR
3
1
(
400 MHz, CDCl3)δ ppm 8.22∼7.28(m, 20H, C6H4); P NMR (162 MHz,
13
CDCl3)δ ppm 21.19 (t, 1P), 4.87 (d, 2P), J(PP) = 87.5 Hz; C NMR
(100 MHz, CDCl3)δ ppm 153.95, 145.59, 125.71, 121.65; IR (KBr)
−
1
(cm ): 3118, 1614, 1589 and 1480 (Ar), 1527 and 1350 (NO2), 1203,
−1
+
1
183 and 1160 cm (P N), 498 (P Cl); ESI-MS: m/z 861.1 [M+H] .
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