Preparation and characterization of chromophor group containing cyclotriphosphazenes: III bis-azo chromophor carrying some cyclotriphosphazenes

Article abstract of DOI:10.1080/10426500307931

Some new substituted cyclotriphosphazenes were prepared by reaction of hexachlorocyclotriphosphazene and phenylazophenylazophenol compounds such as p-[p-phenylazo-phenylazo]phenol, p-[p-(o-chlorophenylazo)phenylazo]phenol, p-[p-(p-chlorophenylazo)-phenylazo]phenol, p-[p-(p-methylphenylazo)phenylazo]phenol, and tetrazobenzene-β-naphtol. They are characterized by UV-Vis, FT IR, elemental analysis, and TG, DTG, and DTA.

Full text of DOI:10.1080/10426500307931

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Phosphorus, Sulfur, and Silicon and the Related
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Preparation and Characterization of Chromophor
Group Containing Cyclotriphosphazenes: III Bis-Azo
Chromophor Carrying Some Cyclotriphosphazenes
a
a
a
a
Mustafa Odabaşoğlu , Şükriye Çakmak , Günseli Turgut & Hasan İçbudak
a
Ondokuz Mayts University, Samsan, Turkey
Version of record first published: 27 Oct 2010.
To cite this article: Mustafa Odabaşoğlu , Şükriye Çakmak , Günseli Turgut & Hasan İçbudak (2003): Preparation
and Characterization of Chromophor Group Containing Cyclotriphosphazenes: III Bis-Azo Chromophor Carrying Some
Cyclotriphosphazenes, Phosphorus, Sulfur, and Silicon and the Related Elements, 178:3, 549-558
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Phosphorus, Sulfur and Silicon, 2003, Vol. 178:549–558
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DOI: 10.1080/10426500390170705
PREPARATION AND CHARACTERIZATION OF
CHROMOPHOR GROUP CONTAINING
CYCLOTRIPHOSPHAZENES: III BIS-AZO
CHROMOPHOR CARRYING SOME
CYCLOTRIPHOSPHAZENES
Mustafa Odaba s¸ o g˘ lu, S¸ u¨ kriye C¸ akmak, G u¨ nseli Turgut,
˙
and Hasan I c¸ budak
Ondokuz Mayts University, Samsan, Turkey
(Received July 4, 2002; accepted August 20, 2002)
Some new substituted cyclotriphosphazenes were prepared by reac-
tion of hexachlorocyclotriphosphazene and phenylazophenyla-
zophenol compounds such as p-[p-phenylazo-phenylazo]phenol,
p-[p-(o-chlorophenylazo)phenylazo]phenol, p-[p-(p-chlorophenylazo)-
phenylazo]phenol, p-[p-(p-methylphenylazo)phenylazo]phenol, and
tetrazobenzene-�-naphtol. They are characterized by UV-Vis, FT IR,
elemental analysis, and TG, DTG, and DTA.
Keywords: Bis-azocompounds; cyclotriphosphazenes; MS; phenyla-
zophenoxycyclotriphosphazenes; thermal analysis
INTRODUCTION
Azobenzene derivatives have been the most widely used class of dyes
due to their versatile application in various fields, such as dyeing
textile fibers, biomedical studies, advanced applications in organic
synthesis, and high technology areas as laser, liquid crystalline dis-
plays, electro-optical devices, and ink-jet printers.1 Furthermore,
phophazene-bound dye systems are of interest in photochemical re-
search, in photographic processes, and in a number of biologically re-
–3
4
–7
lated applications.
As part of our general interest in the reaction of
cyclic phosphazenes, we have examined the possibility whether Schiff’s
The financial support given to research project by Research Projects Fund of Ondokuz
Mayıs University is gratefully acknowledged.
Address correspondence to Mustafa Odaba s¸ o g˘ lu, Department of Chemistry, Faculty
of Arts and Sciences, Ondokuz Mayıs University, 55139, Kurupelit, Samsun, Turkey.
E-mail: muodabas@omu.edu.tr
5
49

5
50
M. Odaba s¸ o g˘ lu et al.
8
9
bases-linked and monoazodyes-linked cyclic phosphazenes can be pre-
pared by side-group construction reactions carried out on a performed
cyclic organophosphazenes.
Although, azochromophors carrying some poly and cyclotriphosp-
hazenes have been synthesized and the structures have been identified
4,9
by a variety of techniques previously, bis-azo chromophore carrying
have not been reported. In this work, we report the synthesis of bis-azo
chromophore group carrying cyclotriphosphazenes with unsubstituted
ring and substituents like chloro and methyl on the ring. The new com-
pounds have been characterized by using FT IR and UV-Vis spectro-
scopic techniques, thin-layer chromatography, elemental analysis, and
thermal analysis techniques.
RESULT AND DISCUSSION
All bis-azo dyes were synthesized by azo-coupling reactions of substi-
tuted benzenediazonium salts and phenol. The prepared bis-azo dyes
and their cyclotriphosphazene derivatives are listed in Table I. The
dyes and their cyclotriphosphazene derivatives were purified by re-
crystallization from suitable solvents and their purity was examined
by thin-layer chromatography.
The FT IR spectra of substituted and unsubstituted hexakis[p-(p-
phenylazo)phenylazo-phenoxy]cyclotriphosphazene compounds have
four characteristic absorption bands. These bands are shown at 1468–
�
1
� 1
� 1
� 1
1
416 cm , 1253–1145 cm , 1269–1243 cm , and 971–950 cm
and are due to N N , P N , P N P (sym), and P N P (asym)
respectively (Table II).
TABLE I The Characterization and Elemental Analysis of VI–X
%
C Calculateda
(found)
% H Calculateda
(found)
�
Compound
m.p. ( C)
Yield (%)
60
VI
66.76
4.27
(4.31)
3.60
(3.97)
3.60
(3.94)
4.67
(5.06)
4.23
154b
185b
162b
150b
175
(
(
(
(
(
66.42)
60.54
58.67)
60.54
62.08)
67.52
69.05)
70.56
71.31)
VII
VIII
IX
45
55
60
40
X
(4.45)
a
Every compound has 1 mole THF.
Decomposition point.
b

Preparation and Characterization of Chromophor Group
551
TABLE II FT IR Bands of Compounds I–X (cm 1)
�
Compound
O H
N N
C N P N P(asym) P N P(sym)
P N
—
P OAr
—
I
VI
II
VII
III
VIII
IV
IX
V
3445–3164 1426
1468
3475–3075 1416
1442
3440–3040 1434
1442
3434–3018 1440
1460
3400–3334 1438
1455
1148
1112
1125
1110
1138
1112
1142
1122
1154
1154
—
1243
—
1269
—
1243
—
1253
—
—
960
—
954
—
950
—
971
—
—
1236–1145 1014
—
—
—
1222–1175 1017
—
—
—
1214–1177 1018
—
—
—
1253–1156 1029
—
—
X
—
1255
960
1236–1150 1019
When the FT IR spectra of p-(p-phenylazophenylazo)phenol (I) and
its derivative hexakis-[p-(p-phenylazo)phenylazophenoxy]cyclotripho-
sphazene (VI) are compared, it is seen that the OH vibration at 3445–
�
1
� 1
3
164 cm disappeared and a new band at 1014 cm due to P-OAr
appeared in the spectrum VI (Table II). Significant shifts in the absorp-
�
1
� 1
tions of N N at 1426 cm and C N at 1148 cm were observed
in the spectrum of VI. These changes are attributed to the replacement
of H with the P atom and the hindrance of the resonance between the
N N group and the phenyl ring. Similar observations were noted
for the other bis-azo compounds and their derivatives (Table II).
UV-Vis spectra of the bis-azo side group carrying compound synthe-
sized are found to be similar to the spectra of their cyclotriphosphazene
�
derivatives. The electronic transitions, were assigned as n → � and
�
�
→ � (Table III).
UV-Vis spectra of Sudan III (tetrazobenzene-�-naphtol) show an ab-
sorption of n → � and � → � at 518 and 356 nm respectively. The
�
�
TABLE III UV-Vis Absorption Bands
of Compounds I–X (nm)
Compound
n → ��
� → ��
I
VI
II
VII
III
VIII
IV
IX
V
—
402
368
401
396
414
405
390
387
356
350
450 (shoulder)
623
620
618
605
606
582
518
509
X

5
52
M. Odaba s¸ o g˘ lu et al.
FIGURE 1 DTA, TG, and DTG curves of VIII.
same transitions were observed at 509 and 350 nm for its cyclotriphos-
phazene derivative (X). The other bis-azo compounds and their deriva-
tives exhibit similar transitions.
The TG-DTG and DTA curves of hexakis {p-[p-(p-chlorophenylazo)-
phenylazo]phenoxy}-cyclotriphosphazene (VIII) and hexakis (tetra-
zobenzene-�-naphtoxy)-cyclotriphosphazene (X) are shown in Figures 1
FIGURE 2 DTA, TG, and DTG curves of X.

Preparation and Characterization of Chromophor Group
553
TABLE IV Thermoanalytical Results for the Cyclotriphosphazene
Compounds VI, VIII–X
Weight loss %
Temperature range
DTGmax
( C)
Removed
product
�
�
Compound
( C)
Found
Calculated
VI
1
2
3
4
29–110
126–173
173–292
292–415
52
3.87
31.28
14.46
10.59
3.57
31.29
—
C4H8O
C6H4N2
154
254
366
—
—
—
VIII
1
2
3
4
22–73
52
162
320
418
3.34
7.90
56.52
19.97
3.22
7.52
57.80
20.54
C4H8O
N2
C12H8N2Cl
C6H4
110–191
191–374
374–451
IX
1
2
3
4
24–130
130–191
191–450
350–600
46
150
270
521
3.52
32.50
3.43
34.05
C4H8O
C6H4N2
48.90
—
—
X
1
2
22–144
194–330
336–500
48
291
380
3.29
61.70
16.0
3.16
57.81
—
C4H8O
C12H8N4
—
3
and 2; temperature ranges, and experimental and calculated weight
losses of all compounds are summarized in Table IV.
When we look at the Figure 1 for the thermal decomposition of
the VIII four different decomposition steps have been observed. The
�
weight loss starts at low temperatures such as 22 C and continuous
�
to well above to 900 C. In the first step an endothermic weight loss
�
(
3.34%), which is seen as a peak minimum at 52 C in DTA curve,
can be attributed to removal of solvent (THF) which has been hold
on to the crystals. Also, the mass spectra, detects the mass due to
THF (m/e = 73). Similar decompositions have been observed by dif-
1
0–11
�
ferent researches.
For the second step 110–191 C calculations
indicate that the weight loss might be due to exothermic N2 loss
�
(
exp. 7.90%; calcd. 7.52%). In the 191–374 C step a weight loss cor-
responding to release of the C12H8N2Cl group that is the 56.52% of
the weight loss (calcd: 57.80%) has been observed. Two endothermic
�
�
processes have been observed at 412 C and 433 C in the DTA curve
which can be due to decompose remaining hydrocarbon parts of the
VIII.
Three decomposition steps have been observed for hexakis-
tetrazobenzene-�-naphtoxy)cyclotriphosphazene (X) (Figure 2). The
(

5
54
M. Odaba s¸ o g˘ lu et al.
�
first endothermic peak at 48 C corresponds to the removal of sol-
�
vent. The second endothermic peak at 175 C, without any weight loss,
clearly represents a physical process and is attributed to the melt-
ing of hexakis-(tetrazobenzene-�-naphtoxy)cyclotriphosphazene. In the
�
following step in the temperature range 194–330 C, the phenylazo
group (C12H8N4) is removed by giving exothermic effect (exp. 61.70%;
calcd. 57.81%). The mass spectrum is consistent with the TG-DTG/
DTA data. The mass spectrum shows that C12H8N4 (m/e = 209) is
detected.
Similar decompositions processes have been observed for the other
compounds, which are listed in the Table IV.
�
�
MS spectra of VI were recorded at 150 C and 250 C, and proba-
ble products are shown in Figures 3 and 4 respectively. These ob-
servations are consistent with the results reported by Enrico.12 The
MS data of compound VI are also in agreement with data obtained
by TG-DTG/DTA. Furthermore, the m/e values of IX and X are
consistent with the TG-DTG/DTA data. [(m/e values of IX: 77, 91,
�
�
1
(
2
05, 119, 167 at 150 C; 73, 91, 119, 135, 209, 223, 299 at 250 C);
�
m/e values of IX: 77, 105 at 150 C; 73, 91, 135, 149, 209, 335 at
�
50 C)].
According to thermal analysis and mass spectral studies, the de-
composition mechanism of bis-azo chromophore side group carry-
ing cyclotriphosphazenes in nitrogen atmosphere may be as shown
below.
SCHEME 1

Preparation and Characterization of Chromophor Group
555
�
FIGURE 3 MS spectrum of VI at 150 C.
�
FIGURE 4 MS spectrum of VI at 250 C.

5
56
M. Odaba s¸ o g˘ lu et al.
EXPERIMENTAL
Instrumentation
All melting points were taken with an electrothermal melting point
apparatus. FT IR spectra were recorded on a Mattson 1000 FT IR
spectrometer calibrated with polystyrene film using the KBr disc.
Absorption spectra in acetone were determined on a Unicam UV-Vis
spectrophotometer. TG, DTG, and DTA curves were recorded simulta-
neously on Rigaku TG 1810 thermal analyser combined with a TAS
1
00 thermogravimetric analyser. The experiments were performed in
�
1
� 1
nitrogen atmosphere (80 ml min ) with a heating rate of 10 K min
from room temperature to 1000 C in platinum crucibles. The samples
�
weighed approximately 10 mg and highly sintered �-Al2O3 was used
�
1
as a reference material. The DTG sensitivity was 0.05 mg s . Ele-
mental analysis and MS spectra were recorded by TUBITAK Marmara
Research Center.
Dye Synthesis and Purification
Diazoaminobenzenes and p-aminoazobenzenes, were prepared by the
1
3
method of Voge,
p-phenylazophenylazophenols by the method of
Saunders14 and Sudan III (tetrazobenzene-�-naphthol), (V) was pur-
chased from Merck company.
Synthesis of p-[p-Phenylazophenylazo]phenol (I)
A mixture of p-aminoazobenzene (4.925 g, 0.025 mol), 50 ml water
or water-alcohol) and 5 ml concentrated hydrochloric acid was heated
(
while stirring until a clear solution was obtained. This solution was
�
cooled to 0–5 C and a solution of sodium nitrite (2.070 g, 0.30 mol) in
�
water added dropwise, maintaining the temperature below 5 C. The
resulting mixture was stirred for 30 min in an ice bath. The excess
1
4
nitrite was destroyed by addition of urea. This solution was buffered
with solid sodium acetate.
All the other substituted p-aminoazobenzenes were diazotized in a
similar manner to that describe above.
The crystalline phenol (2.350 g, 0.025 mol) gradually was added to the
solution of the cooled p-aminoazobenzenediazoniumchloride prepared
�
as described above and the resulting mixture was stirred at 0–5 C for
6
0 min in an ice bath. The resulting product was recrystallized from an
absolute alcohol-benzene mixture to give solid p-[p-phenylazophenyl-
azo]phenol, m.p. 158 C (yield: 72%).
�

Preparation and Characterization of Chromophor Group
557
SCHEME 2
All other substituted p-[p-phenylazophenylazo]phenols were synthe-
sized in a similar manner to that describe above.
Preparation of Hexakis[p-(p-Phenylazophenylazo)-
phenoxy]cyclotriphosphazene (VI)
Hexakis[p-(p-phenylazophenylazo)phenoxy]cyclotriphosphazene was
prepared by modifying the method of Allcock and Kim using the fol-
lowing steps.12
SCHEME 3
A solution of hexachlorocylotriphosphazene (1.39 g, 0.004 mol)
in THF was added to a THF solution of p-[p-phenylazophenylazo]-
phenoxide which was prepared from p-[p-phenylazophenylazo]phenol
(
7.248 g, 0.024 mol) and sodium (0.552 g, 0.024 mol) in an atmosphere
of dry nitrogen. After 20 h at reflux, the reaction mixture was fil-
trated. The product (VI) was isolated by column chromatography and
�
was purified by recrystallization from acetonitrile (m.p. 154 C, yield
4
0%).
VI–IX were prepared by similar methods and hexakis(tetrazobenzene-
�
-naphtoxy)cyclotriphosphazene (X) was also prepared from tetra-
zobenzene-�-naphtol (V).

5
58
M. Odaba s¸ o g˘ lu et al.
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[
[
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