Preparation and characterization of chromophore group containing cyclotriphosphazenes: IV spectroscopic and thermal investigation of some hexakis(p-phenylazo-o-allylphenoxy)cyclotriphosphazenes

Article abstract of DOI:10.1016/j.molstruc.2003.12.034

Some new substituted cyclotriphosphazenes were prepared by the reaction of hexachlorocyclotriphosphazene and 3-allyl-4-hydroxyazo compounds such as 3-allyl-4-hydroxyazobenzene, 4′-chloro-3-allyl-4-hydroxyazobenzene, 4′-methyl-3-allyl-4-hydroxyazobenzene,

Full text of DOI:10.1016/j.molstruc.2003.12.034

Journal of Molecular Structure 691 (2004) 249–257
www.elsevier.com/locate/molstruc
Preparation and characterization of chromophore group containing
cyclotriphosphazenes: IV spectroscopic and thermal investigation of some
hexakis( p-phenylazo-o-allylphenoxy)cyclotriphosphazenes
*
Mustafa Odabasoglu , Gu¨nseli Turgut, Hasan Icbudak
Department of Chemistry, Faculty of Science, Ondokuz Mayıs University, TR-55139, Samsun, Turkey
Received 5 September 2003; revised 5 December 2003; accepted 18 December 2003
Abstract
Some new substituted cyclotriphosphazenes were prepared by the reaction of hexachlorocyclotriphosphazene and 3-allyl-4-hydroxyazo
compounds such as 3-allyl-4-hydroxyazobenzene, 40-chloro-3-allyl-4-hydroxyazobenzene, 40-methyl-3-allyl-4-hydroxyazobenzene, 40-
bromo-3-allyl-4-hydroxyazobenzene, 40-acetyl-3-allyl-4-hydroxyazobenzene, 30,40-dimethyl-3-allyl-4-hydroxyazobenzene and 40-iodo-3-
1
allyl-4-hydroxyazobenzene. They are characterized by UV–VIS, FT-IR, H-NMR, 13C-NMR, elemental analysis, TG, DTG and DTA.
q 2004 Elsevier B.V. All rights reserved.
Keywords: Cyclotriphosphazenes; Azo dyes; UV–VIS; IR; NMR; Thermal analysis
1. Introduction
We report herein the synthesis of 3-allyl-4-hydroxyazoben-
zene compounds and their cyclotriphosphazene derivatives
such as methyl, acetyl, chloro, bromo, iyodo and unsub-
stituted ring. The new compounds have been characterized
Azo compounds are the oldest and largest class of
industrial synthesized organic dyes. There are about 3000
azo dyes currently in use all over the world. The great
majority of them are monoazo compounds, which have the
common structure unit of the azo chromophore, –NyN–,
linking two aromatic systems. The textile industry is
the largest consumer of dyestuffs. Some azo dyes have
been reported to be toxic but five of the nine synthetic
colorants permitted in food in the United States are
monoazo dyes [1,2]. Dozens of additional monoazo dyes
are permitted in drugs and cosmetics [1]. Furthermore, azo
compounds have been utilized as analytical reagents [3] and
they can also be used as materials for non-linear optics and
for storage optical information in laser disks [4]. The
research of synthesizing azo compounds has received much
attention over the years. Though many kinds of azo dyes
have been synthesized, cyclotriphosphazene derivatives are
relatively rare. Monoazo [5,6] and bis-azo [7] chromophore
group carrying some cyclotriphosphazene derivatives were
synthesized and some of their properties were investigated.
1
by using UV–VIS, FT-IR, H-NMR, 13C-NMR, elemental
and thermal analysis techniques.
2. Results and discussion
2.1. Synthesis
Azo chromophore carrying o-allylphenoxycyclotripho-
sphazenes 5 were synthesized by the cyclotriphosphazene 4
and p-phenylazo-o-allylphenol dyes 3 which are syn-
thesized with azo-coupling reactions of substituted benze-
nediazonium salts and o-allylphenol shown in Scheme 1 and
Table 1. Substituted anilines 1 were diazotized using
sodium nitrite in the presence of hydrochloric acid followed
by coupling with o-allylphenol substrate 2 to produce p-
phenylazo-o-allylphenol dyes 3 in good yield. The dyes 3
and their cyclotriphosphazene derivatives 5 were purified by
recrystallization from suitable solvents and their purity was
examined by thin-layer chromatography.
*
Corresponding author. Tel.: þ362-45760205196; fax: þ362-4576080.
E-mail address: muodabas@omu.edu.tr (M. Odabasoglu).
0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2003.12.034

250
M. Odabasoglu et al. / Journal of Molecular Structure 691 (2004) 249–257
Scheme 1.
Table 1
Synthesized and properties of p-phenylazo-o-allylphenols 3 and its cyclotriphosphazene derivatives 5 (Ar 00, o-allylphenol)
Compound
Ar0
Yield (%)a
Mp (8C)
%C calculated (found)
–
%H calculated (found)
–
%N calculated (found)
–
3a
75
89–91
5a
3b
5b
3c
5c
3d
5d
3e
62
82
55
85
64
78
66
78
53–55b
98–99
69.94 (69.45)
5.01 (4.97)
13.49 (12.95)
–
–
–
56–58b
84–85
61.22 (61.38)
4.08 (4.18)
11.90 (11.21)
–
–
–
44–46b
105–107
58–60b
114–115
70.20 (69.97)
5.48 (5.57)
12.80 (11.93)
–
–
–
53.17 (53.57)
–
3.54 (3.60)
–
10.33 (9.94)
–
5e
3f
68
80
63–65b
67.66 (67.43)
4.97 (5.35)
11.61 (11.08)
131–133
–
–
–
5f
76
60–62b
70.95 (71.05)
5.91 (5.95)
12.17 (11.74)
3g
5g
77
66
134–136
62–64b
–
–
–
46.69 (46.43)
3.11 (3.69)
9.08 (8.73)
a
Isolated yields.
b
Decomposition point.

M. Odabasoglu et al. / Journal of Molecular Structure 691 (2004) 249–257
251
Table 2
derivatives. The lmax values of p-phenylazo-o-allylphenols
and its cyclotriphosphazene derivatives were also affected
by substituted group at phenyl ring.
UV–VIS absorption bands of p-phenylazo-o-allylphenols 3 and its
cyclotriphosphazene derivatives 5 in CHCl3
Compound
n ! p* nm (1)
p ! p* nm (1)
2.3. IR absorption spectra
3a
5a
3b
5b
3c
5c
3d
5d
3e
5e
3f
445 (2950)
439 (3500)
455 (3223)
437 (4029)
451 (2580)
434 (4230)
457 (2430)
430 (4190)
471 (2620)
446 (3690)
449 (3228)
432 (6456)
452 (2857)
443 (3210)
350 (26950)
326 (26525)
357 (30320)
332 (33685)
353 (23800)
333 (25400)
358 (27390)
335 (32430)
368 (33430)
336 (36500)
355 (22168)
338 (24383)
364 (28525)
342 (34456)
The characteristic IR absorption bands of p-phenylazo-o-
allylphenols 3 and p-phenylazo-o-allylphenoxycyclotripho-
sphazenes 5 are determined in KBr disk. As shown in
Table 3, the p-phenylazo-o-allylphenoxycyclotriphospha-
zene compounds have four characteristic absorption bands.
These bands are shown at 1412–1438, 1151–1202, 1232–
1241 and 950–961 cm21 are due to NyN, PyN, P–N–
P(asym), and P–N–P(sym), respectively.
When the IR spectra of p-phenylazo-o-allylphenols 3 and
5f
3g
5g
its derivatives p-phenylazo-o-allylphenoxycyclotriphospha-
zenes 5 are compared, it is seen that the OH vibration at
3125–3530 cm21 region disappeared and a new band
appeared at 1066–1081 cm21 region of the spectrum
because of P–OAr absorption (Table 3). The absorption
frequency’s of NyN and C(aryl) –N of p-phenylazo-o-
allylphenols 3 changed a few cm21 in p-phenylazo-o-allyl
phenoxycyclotriphosphazenes 5. These changes are attrib-
uted to the replacement of H with the P atom and the
hindrance of the resonance between the NyN group and the
phenyl ring. Similar observations were reported for some
bis-azo compounds and their derivatives [7].
2.2. UV–VIS absorption spectra
Typical characteristic UV–VIS absorption bands of p-
phenylazo-o-allylphenols 3 and its cyclotriphosphazene
derivatives 5 in CHCl3 are given in Table 2. UV–VIS
spectra of the azo side group carrying o-allylphenols 3 are
found to be similar to the spectra of their cyclotripho-
sphazene 5 derivatives. Thus, delocalization effects between
the substituents and phosphazene ring were not detected as
previous researches [7–10]. Cyclotriphosphazene ring
themselves do not absorb in near UV region [11], but if
there were delocalization, an absorption would be seen in
this region. The electronic transitions, were assigned as n !
p* and p ! p* according to absorption of similar azo dyes
[12]. The absorption maxima ðlmaxÞ were observed in the
range of 430–471 and 326–368 nm for n ! p* and
p ! p*, respectively (Table 2). The hypsochromic shift is
observed in UV–VIS absorptions, when the p-phenylazo-o-
allylphenols are converted to their cyclotriphosphazene
2.4. NMR investigations
In the 1H-NMR spectra, all azo dyes 3 show one peak at
9.05–9.34 ppm which belongs to the hydroxyl group as
cited in the previous works [5,7,8]. After the reactions
mentioned above are carried out this peak disappears in this
range. The 1H-NMR spectra of the synthesized compounds
show dd peaks at 5.07–5.19 ppm and d at 3.47–3.57 ppm
and ddt at 5.97–6.09 ppm, which are attributed to allyl
Table 3
FT-IR bands (cm21) of p-phenylazo-o-allylphenols 3 and p-phenylazo-o-allylphenoxycyclotriphosphazenes 5 (KBr disk)
Compound
OH
NyN
Ar–Ny
CyC (allyl)
P–N–P (asym)
P–N–P (sym)
PyN
P–OAr
CyO
3a
5a
3b
5b
3c
5c
3d
5d
3e
5e
3f
3350–3250
1425
1437
1412
1418
1428
1435
1425
1432
1412
1422
1430
1438
1432
1436
1137
1120
1125
1122
1130
1128
1135
1133
1145
1142
1125
1123
1138
1133
1639
1636
1642
1639
1644
1638
1646
1638
1637
1645
1634
1638
1635
1638
–
–
–
–
–
–
1235
–
950
–
1191–1165
–
1072
–
–
3520–3275
–
–
1233
–
957
–
1193–1165
–
1066
–
–
3490–3125
–
–
1232
–
956
–
1196–1151
–
1075
–
–
3460–3125
–
–
1232
–
952
–
1191–1155
–
1080
–
–
3530–3272
1675
–
1234
–
956
–
1197–1164
–
1081
–
1682
3522–3187
–
–
–
–
5f
–
1241
–
961
–
1202–1164
–
1079
–
3g
5g
3351–3180
–
1236
953
1192–1163
1078

252
M. Odabasoglu et al. / Journal of Molecular Structure 691 (2004) 249–257
Table 4
1H-NMR spectral data of 3a–g compounds in aceton-d6
3a
3b
3c
3d
3e
3f
3g
–OH
HA
9.25 (s)
9.34 (s)
9.30 (s)
9.30 (s)
9.34 (s)
9.05 (s)
9.31 (s)
5.15 (dd)
5.16 (dd)
5.18 (dd)
5.16 (dd)
5.16 (dd)
5.16 (dd)
5.15 (dd)
JA,B ¼ 2.95
JA,B ¼ 1.96
JA,B ¼ 1.92
JA,B ¼ 1.92
JA,B ¼ 1.91
JA,B ¼ 1.97
JA,B ¼ 1.98
JA,C ¼ 16.92
5.08 (dd)
JA,C ¼ 17.62
5.09 (dd)
JA,C ¼ 17.13
5.09 (dd)
JA,C ¼ 17.05
5.07 (dd)
JA,C ¼ 17.04
5.08 (dd)
JA,C ¼ 15.45
5.08 (dd)
JA,C ¼ 17.10
5.08 (dd)
HB
HC
JB,A ¼ 2.95
JB,A ¼ 1.96
JB,A ¼ 1.92
JB,A ¼ 1.92
JB,A ¼ 1.91
JB,A ¼ 1.97
JB,A ¼ 1.98
JB,C ¼ 10.17
6.09 (ddt)
JB,C ¼ 10.05
6.08 (ddt)
JB,C ¼ 10.11
6.08 (ddt)
JB,C ¼ 10.07
6.05 (ddt)
JB,C ¼ 10.21
6.09 (ddt)
JB,C ¼ 10.13
6.08 (ddt)
JB,C ¼ 10.12
6.07 (ddt)
JC,CH ¼ 6.65
JC,CH ¼ 6.60
JC,CH ¼ 6.64
JC,CH ¼ 6.64
JC,CH ¼ 6.62
JC,CH ¼ 6.63
JC,CH ¼ 6.64
2
2
2
2
2
2
2
JC,A ¼ 16.92
JC,A ¼ 17.62
JC,A ¼ 17.13
JC,A ¼ 17.05
JC,A ¼ 17.04
JC,A ¼ 15.45
JC,A ¼ 17.10
JC,B ¼ 10.17
3.49 (d)
JC,B ¼ 10.05
3.49 (d)
JC,B ¼ 10.11
3.50 (d)
JC,B ¼ 10.07
3.49 (d)
JC,B ¼ 10.21
3.50 (d)
JC,B ¼ 10.13
3.48 (d)
JC,B ¼ 10.12
3.49 (d)
–CH2–
JCH ,C ¼ 6.65
–
JCH ,C ¼ 6.60
–
JCH ,C ¼ 6.64
2.42 (s)
JCH ,C ¼ 6.64
–
JCH ,C ¼ 6.62
2.64 (s)
JCH ,C ¼ 6.63
2.35 (s) and 2.32 (s)
7.28 (dd)
JCH ,C ¼ 6.64
–
2
2
2
2
2
2
2
CH3–
H2
7.60–7.44 (m)
7.46 (dd)
J2,3 ¼ 8.36
J2,6 ¼ 1.96
7.36 (dd)
J2,3 ¼ 8.42
J2,6 ¼ 1.90
7.52 (dd)
J2,3 ¼ 8.39
J2,6 ¼ 1.90
7.76 (dd)
J2,3 ¼ 8.40
J2,6 ¼ 1.96
7.34 (dd)
J2,3 ¼ 8.38
J2,6 ¼ 1.96
J2,3 ¼ 8.43
J2,6 ¼ 1.95
7.02 (d)
H3
7.06 (d)
7.06 (d)
7.05 (d)
7.05 (d)
7.07 (d)
7.05 (d)
J3,2 ¼ 8.37
7.60–7.44 (m)
J3,2 ¼ 8.36
7.76 (d)
J3,2 ¼ 8.42
7.70 (d)
J3,2 ¼ 8.39
7.77 (d)
J3,2 ¼ 8.40
7.83 (d)
J3,2 ¼ 8.43
7.56 (d)
J3,2 ¼ 8.38
7.75 (d)
H6
J6,2 ¼ 1.96
7.58 (dd)
J6,2 ¼ 1.90
7.79 (dd)
J6,2 ¼ 1.90
7.81 (dd)
J6,2 ¼ 1.96
7.94 (dd)
J6,2 ¼ 1.95
J6,2 ¼ 1.96
7.66 (dd)
H20, H60
7.88 (m)
0
7.75 (d) (H20)
0
0
0
0
0
0
0
0
0
0
00
0
0
J2 ,3 ¼ 8.19
J2 ,3 ¼ 8.70
J2 ,3 ¼ 8.37
J2 ,3 ¼ 8.99
J2 ,3 ¼ 8.55
J2 ,6 ¼ 2.37
J2 ,3 ¼ 8.65
0
0
0
0
0
0
0
0
0
0
0 0
J2 ,6 ¼ 1.98
J2 ,6 ¼ 2.06
J2 ,6 ¼ 2.06
J2 ,6 ¼ 2.00
J2 ,6 ¼ 2.00
7.64 (dd) (H60)
J2 ,6 ¼ 1.83
0
00
J5 ,6 ¼ 7.61
0
0
J6 ,2 ¼ 2.37
7.71 (d)
H30, H50
7.75 (m)
0
7.87 (dd)
0
7.75 (dd)
0
7.72 (dd)
0
8.14 (dd)
0
7.94 (dd)
0
0
0
0
0
0
0
0
0
J3 ,2 ¼ 8.19
J3 ,2 ¼ 8.70
J3 ,2 ¼ 8.37
J3 ,2 ¼ 8.99
J3 ,2 ¼ 8.55
J5 ,6 ¼ 7.61
J3 ,2 ¼ 8.65
0
0
0
0
0
0
0
0
0
0
0 0
J3 ,5 ¼ 1.98
7.75 (m)
J3 ,5 ¼ 2.06
J3 ,5 ¼ 2.06
J3 ,5 ¼ 2.00
J3 ,5 ¼ 2.00
J3 ,5 ¼ 1.83
H40
–
–
–
–
–
–
0
0
J3 ,2 ¼ 8.19
0
0
J3 ,5 ¼ 1.98
group. The phenyl groups were also observed in the
7.02–8.14 ppm region, as given in Tables 4 and 5. Various
protons of azo dyes 3 have appeared in their usual pattern
[5] but with a slight chemical shift compared to the
phosphazene derivatives 5. The peaks of substituted methyl
groups are also given in Tables 4 and 5.
The 13C-NMR spectra of azo dyes 3 have shown
the characteristic chemical shift with slight shift compared
to its phosphazene derivatives 5 (Tables 6 and 7).
Considering all dyes synthesized, it is clearly seen that
p-hydroxyazobenzene derivatives exist exclusively in the
azo form and do not form any intramolecular hydrogen bond
[12–14]. As can be observed from the values of C4 atoms of
the dyes that the chemical shift values are 158.76–
159.87 ppm and it is in 151.01–152.16 ppm region for the
phosphazene derivatives depending on the chemical
environment of the carbon [12]. In addition, the C4 carbon
signals in p-phenylazo-o-allylphenoxycyclotriphospha-
zenes (5a–g) appear as false doublet which this
carbon atoms are coupled with the nearest phosphorus.

M. Odabasoglu et al. / Journal of Molecular Structure 691 (2004) 249–257
253
Table 5
1H-NMR spectral data of 5a–g compounds in aceton-d6
5a
5b
5c
5d
5e
5f
5g
HA
HB
HC
5.14 (dd)
5.14 (dd)
5.17 (dd)
5.15 (dd)
5.19 (dd)
5.15 (dd)
5.17 (dd)
JA,B ¼ 2.94
JA,B ¼ 1.98
JA,B ¼ 1.90
JA,B ¼ 1.90
JA,B ¼ 1.94
JA,B ¼ 1.95
JA,B ¼ 1.93
JA,C ¼ 17.58
5.09 (dd)
JA,C ¼ 17.97
5.08 (dd)
JA,C ¼ 17.43
5.08 (dd)
JA,C ¼ 16.98
5.09 (dd)
JA,C ¼ 16.98
5.12 (dd)
JA,C ¼ 16.58
5.09 (dd)
JA,C ¼ 16.99
5.08 (dd)
JB,A ¼ 2.94
JB,A ¼ 1.98
JB,A ¼ 1.90
JB,A ¼ 1.90
JB,A ¼ 1.94
JB,A ¼ 1.95
JB,A ¼ 1.93
JB,C ¼ 10.91
5.98 (ddt)
JB,C ¼ 10.05
5.98 (ddt)
JB,C ¼ 10.23
5.97 (ddt)
JB,C ¼ 10.16
5.98 (ddt)
JB,C ¼ 10.23
5.97 (ddt)
JB,C ¼ 10.22
6.02 (ddt)
JB,C ¼ 10.03
5.98 (ddt)
JC,CH ¼ 6.66
JC,CH ¼ 6.62
JC,CH ¼ 6.62
JC,CH ¼ 6.68
JC,CH ¼ 6.64
JC,CH ¼ 6.62
JC,CH ¼ 6.68
2
2
2
2
2
2
2
JC,A ¼ 17.58
JC,A ¼ 17.97
JC,A ¼ 17.43
JC,A ¼ 16.98
JC,A ¼ 16.98
JC,A ¼ 16.58
JC,A ¼ 16.99
JC,B ¼ 10.91
3.52 (d)
JC,B ¼ 10.05
3.53 (d)
JC,B ¼ 10.23
3.47 (d)
JC,B ¼ 10.16
3.48 (d)
JC,B ¼ 10.23
3.57 (d)
JC,B ¼ 10.22
3.47 (d)
JC,B ¼ 10.03
3.50 (d)
–CH2–
JCH ,C ¼ 6.66
–
JCH ,C ¼ 6.62
–
JCH ,C ¼ 6.62
2.43 (s)
JCH ,C ¼ 6.68
–
JCH ,C ¼ 6.64
2.66 (s)
JCH ,C ¼ 6.62
2.36 (s) and 2.31 (s)
JCH ,C ¼ 6.68
–
2
2
2
2
2
2
2
CH3–
H2
7.50–7.33 (m)
7.40 (dd)
7.31 (dd)
7.49 (dd)
7.52 (dd)
7.25 (dd)
7.32 (dd)
J2,3 ¼ 8.40
J2,3 ¼ 8.43
J2,3 ¼ 8.36
J2,3 ¼ 8.43
J2,3 ¼ 8.46
J2,3 ¼ 8.41
J2,6 ¼ 1.95
7.16 (d)
J2,6 ¼ 1.90
7.15 (d)
J2,6 ¼ 1.89
7.14 (d)
J2,6 ¼ 1.95
7.20 (d)
J2,6 ¼ 1.97
7.17 (d)
J2,6 ¼ 1.95
7.11 (d)
H3
7.18 (d)
J3,2 ¼ 8.30
7.50–7.33 (m)
J3,2 ¼ 8.40
7.68 (d)
J3,2 ¼ 8.43
7.66 (d)
J3,2 ¼ 8.36
7.68 (d)
J3,2 ¼ 8.43
7.76 (d)
J3,2 ¼ 8.46
7.49 (d)
J3,2 ¼ 8.41
7.73 (d)
H6
J6,2 ¼ 1.95
7.53 (dd)
J6,2 ¼ 1.90
7.75 (dd)
J6,2 ¼ 1.89
7.79 (dd)
J6,2 ¼ 1.95
7.85 (dd)
J6,2 ¼ 1.97
J6,2 ¼ 1.95
7.56 (dd)
H20, H60
7.80 (m)
0
7.75 (d) (H20)
0
0
0
0
0
0
0
0
0
0
00
0
0
J2 ,3 ¼ 8.21
J2 ,3 ¼ 8.68
J2 ,3 ¼ 8.35
J2 ,3 ¼ 8.96
J2 ,3 ¼ 8.57
J2 ,6 ¼ 2.35
J2 ,3 ¼ 8.68
0
0
0
0
0
0
0
0
0
0
0 0
J2 ,6 ¼ 1.96
J2 ,6 ¼ 2.05
J2 ,6 ¼ 2.04
J2 ,6 ¼ 1.98
J2 ,6 ¼ 1.98
7.58 (dd) (H60)
J2 ,6 ¼ 1.85
0
00
J5 ,6 ¼ 7.65
0
0
J6 ,2 ¼ 2.35
7.70 (d)
H30, H50
7.67 (m)
0
7.80 (dd)
0
7.70 (dd)
0
7.64 (dd)
0
8.07 (dd)
0
7.88 (dd)
0
0
0
0
0
0
0
0
0
J3 ,2 ¼ 8.21
J3 ,2 ¼ 8.68
J3 ,2 ¼ 8.35
J3 ,2 ¼ 8.96
J3 ,2 ¼ 8.57
J5 ,6 ¼ 7.65
J3 ,2 ¼ 8.68
0
0
0
0
0
0
0
0
0
0
0 0
J3 ,5 ¼ 1.96
7.67 (m)
J3 ,5 ¼ 2.05
J3 ,5 ¼ 2.04
J3 ,5 ¼ 1.98
J3 ,5 ¼ 1.98
J3 ,5 ¼ 1.85
H40
0
0
J3 ,2 ¼ 8.21
–
–
–
–
–
–
0
0
J3 ,5 ¼ 1.96
The chemical shifts of the other C atoms show similar
behavior and this changing are presented in Fig. 1 as
examples.
TG-DTG, DTA methods simultaneously in the temperature
range of 20–1000 8C in static air atmosphere.
The thermoanalytical results obtained are given in Table 8.
Thermal analysis curves of 5a are presented in Fig. 2 as an
example. All compounds under investigation showed three-
stage decomposition as a common feature. The first
decomposition stage of the compounds occurs in tempera-
ture range of 172–343 8C (DTG curve) by giving
2.5. Thermal decomposition studies
The thermal behavior of the studied compounds except to
5d were investigated by employing thermoanalytical

254
M. Odabasoglu et al. / Journal of Molecular Structure 691 (2004) 249–257
Table 6
13C-NMR chemical shifts 3a–g compounds in aceton-d6
3a
3b
3c
3d
3e
3f
3g
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C10
C20
C30
C40
C50
C60
147.29
123.13
116.09
159.11
128.36
125.52
34.76
137.43
116.24
–
147.14
124.11
116.15
159.35
128.41
125.66
34.72
136.26
116.21
–
147.28
123.15
116.05
158.88
128.29
123.68
34.78
147.16
124.18
116.15
159.53
125.66
124.89
34.73
137.37
116.33
–
147.40
123.12
116.20
159.87
125.89
124.49
34.72
147.38
120.84
116.06
158.76
131.05
123.61
34.80
147.14
124.21
116.16
159.50
128.49
125.72
34.72
137.36
116.29
–
137.50
116.20
21.31
137.33
116.37
26.83
138.16
116.19
19.81
–
–
–
–
197.34
156.15
128.60
130.18
138.99
130.18
128.60
19.69
–
153.76
123.89
129.96
131.06
129.96
123.89
152.30
124.63
130.11
137.36
130.11
124.63
151.84
130.54
125.36
141.46
125.36
130.54
152.66
133.18
124.61
128.51
124.61
133.18
152.21
128.28
137.53
140.13
125.39
124.22
153.23
124.97
139.11
96.66
139.11
124.97
Table 7
13C-NMR chemical shifts of 5a–g compounds in aceton-d6
5a
5b
5c
5d
5e
5f
5g
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C10
C20
C30
C40
C50
C60
150.74
122.64
121.83
151.42
130.05
126.06
35.08
136.36
117.38
–
151.03
122.77
122.59
151.76
130.26
126.29
35.15
136.15
117.50
–
150.75
123.56
121.97
151.30
128.97
124.15
35.14
150.58
122.77
121.85
151.75
126.22
125.95
35.10
136.30
117.46
–
150.87
122.98
121.88
151.52
126.45
123.59
35.17
150.91
121.78
121.33
151.01
131.10
122.34
35.14
151.03
122.90
122.37
152.16
129.96
126.29
35.15
136.13
117.52
–
136.42
117.31
21.47
136.28
117.54
26.88
138.26
117.38
19.81
–
–
–
–
197.32
155.49
130.13
134.24
139.76
134.24
130.13
19.67
–
153.43
123.64
132.03
134.07
132.03
123.64
151.82
125.06
133.30
137.58
133.30
125.06
151.47
130.46
125.28
142.56
125.28
130.46
152.20
134.16
125.25
133.31
125.25
134.16
151.92
125.95
136.32
141.29
124.69
122.47
152.62
125.26
139.41
98.39
139.41
125.26

M. Odabasoglu et al. / Journal of Molecular Structure 691 (2004) 249–257
255
Fig. 1. The 13C-NMR spectra of p-phenylazo-o-allylphenol (3a) and hexakis(p-phenylazo-o-allylphenoxy)cyclotriphosphazene (5a).
exothermic effect (DTA curve). This exothermic effect on
the DTA curves (Fig. 2) was also observed in the dynamic
nitrogen atmosphere (80 ml min21). Calculations indicated
that the observed weight loss (around 10%) might be
attributed to liberation of exothermic N2 in the first
decomposition stage [7]. Calculated weight loss for the
first stage was close to the found values (Table 8). Despite
the similarity of the chemical structure of compounds, 5g
shows a different thermal behavior in the curves. The weight
loss observed in the first decomposition stage of 5g is
actually a combination of two sub-steps (DTGmax: 189 and
271 8C). The second decomposition stages for the all
compounds were observed in the temperature range of
330–530 8C in static air atmosphere. In this endothermic
stage, some volatile products are liberated. The third stage
of decomposition is associated with an exothermic oxi-
dation process in the temperature range of 527–588 8C
(DTA curve). In this stage, the organic part of the
compounds is oxidized and turned into colorless and
stable final products from 730 to 1000 8C depending on
the compound. The releasing of the volatile products
such as aliphatic and aromatic substituents and then
oxidation in static air atmosphere results in to the
polymerization of the compounds. The polymerization of
the similar compounds was also observed by Levchik et al.
in previous studies [15].
3. Experimental
3.1. 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 chloroform were determined on UV–VIS spec-
trometer. The 1H-NMR and 13C-NMR spectra were
taken on a BRUKER AC 200 MHz spectrometer,
reference tetramethylsilane as internal standard. TG,

256
M. Odabasoglu et al. / Journal of Molecular Structure 691 (2004) 249–257
Table 8
Thermoanalytical results for 5 compounds in static air atmosphere
Compound
Temperature range (8C)
DTGmaxa (8C)
Weight loss %
Found
Total weight loss
Calculated
10.79
C96H78N15 O6P3 (5a)
1
2
3
226–343
380–530
531–900
280 (2)
488 (þ)
565 (2)
11.33
18.93
57.46
87.72
C90H72N15Cl6 O6P3 (5b)
1
2
3
4
225–333
330–450
451–570
571–900
270 (2)
400 (þ)
527 (–)
–
11.33
9.85
9.52
10.48
47.08
78.74
81.85
C96H90N15 O6P3 (5c)
1
2
3
215–314
360–520
521–900
280 (–)
485 (þ)
563 (–)
8.43
10.24
20.46
52.96
C102H90N15 O12P3 (5e)
1
2
3
4
208–282
403–522
523–654
655–950
254 (2)
439 (þ)
588 (2)
2
2.09
12.32
18.09
52.45
9.30
9.74
84.95
78.18
C
1
2
3
4
102H102N15O6P3 (5f)
25–70
36 (þ)
1.21
228–332
355–495
496–730
287 (2)
454 (þ)
542 (2)
10.22
20.35
46.40
C90H72N15I6 O6P3 (5g)
1
2
3
30–65
55 (þ)
150 (þ)
189 (2)
271 (2)
2
1.37
2.34
8.96
1.94
26.04
46.60
103–171
172–256
256–360
362–444
445–753
7.25
4
5
549 (2)
87.25
a
Exothermic and endothermic processes are denoted by (2) and (þ), respectively.
DTG and DTA curves were recorded simultaneously on
Rigaku TG 1810 thermal analyser combined with a TAS
100 thermogravimetric analyser. The experiments were
performed in static air atmosphere with a heating rate of
10 8C min21 from room temperature to 1000 8C in
platinum crucibles. The samples weighed approximately
10 mg and highly sintered a-Al2O3 was used as a
(2.21 g, 0.032 mol) in water added dropwise, maintaining
the temperature below 5 8C. The resulting mixture was
stirred for 30 min in an ice bath. The excess nitrite was
buffered with solid sodium acetate.
reference material. The DTG sensitivity was 0.05 mg s21
.
Elemental analysis was recorded by TUBITAK Marmara
Research Center.
3.2. Dye synthesis and purification
3-Allyl-4-hydroxyazobenzene compounds were pre-
pared by the method of Saunders [16]. A mixture of
aniline (2.79 g, 0.03 mol), 30 ml water and concentrated
hydrochloric acid (7.5 ml, 0.09 mol) was heated while
stirring until a clear solution was obtained. This solution
was cooled to 0–5 8C and a solution of sodium nitrite
Fig. 2. Thermoanalytical curves of the hexakis( p-phenylazo-o-allylphe-
noxy)cyclotriphosphazene (5a) in static air atmosphere.

M. Odabasoglu et al. / Journal of Molecular Structure 691 (2004) 249–257
257
All the other substituted anilines were diazotized in a
similar manner to that describe above.
Other compounds were prepared by similar methods and
identified by UV–VIS, FT-IR, 1H-NMR, 13C-NMR,
elemental and thermal analysis techniques.
The 2-allylphenol (4.02 g, 0.03 mol) was gradually
added to the solution of cooled benzenediazoniumchloride
prepared as described above and the resulting mixture was
continually stirred at 0–5 8C for 2 h in an ice bath. The
resulting product was recrystallized from ethyl alcohol–
water or glacial acetic acid–water mixture to give a solid
(3a), Mp 89–91 8C (yield: 75%).
References
[1] D.M. Marmion, Handbook of US Colorants, third ed., Wiley, New
York, 1991, p. 23.
All the other dyes were synthesized in a similar manner
to that described above (Table 1).
[2] R.K. Jhonson, F.J. Lichlenberger, in: J. Walford (Ed.), Developments
Food Colours, Applied Science, London, 1980, p. 53.
[3] H.W. Russ, H. Tappe, Eur. Pat. Appl. EP. 629 (1994) 667.
[4] H. Nakazumi, J. Soc. Dyers Colourists 104 (1988) 121.
3.3. Preparation of hexakis( p-phenlyazo-o-
allylphenoxy)cyclotriphosphazene (5a)
˘
[5] M. Odabas¸oglu, G. Turgut, H. Kocaokutgen, Phosphorus, Sulfur, and
Silicon 152 (1999) 27.
[6] G. Facchin, M. Gleria, F. Minto, R. Bertani, M. Guglielmi, G.
Hexakis( p-phenlyazo-o-allylphenoxy)cyclotriphospha-
zene (5a) was prepared by modifying the method of Allcock
and Kim using the following steps [17];
Brusatin, Macromol. Rapid Commun. 16 (1995) 211.
˙
˘
[7] M. Odabas¸oglu, S. C¸ akmak, G. Turgut, H. Ic¸budak, Phosphorus,
Sulfur, and Silicon 178 (2003) 549.
˘
[8] M. Odabas¸oglu, G. Turgut, H. Karaer, Phosphorus, Sulfur, and Silicon
A solution of hexachlorocyclotriphosphazene (1.04 g,
0.003 mol) in THF was added to a THF solution of
sodium p-phenylazo-o-allylphenoxide which was prepared
from 3-allyl-4-hydroxyazobenzene (4.28 g, 0.018 mol)
and sodium (0.414 g, 0.018 mol) in an atmosphere of
dry nitrogen. After 96 h at reflux, the reaction mixture
was filtrated. The product isolated by column chroma-
tography and was purified by recrystallization from
acetonitrile–aceton (2:1). Physical properties of
compound 5a and other cyclotriphosphazenes are given
in Table 1.
152 (1999) 9.
[9] H.R. Allcock, J. Am. Chem. Soc. 86 (1964) 2591.
[10] H.R. Allcock, R.L. Kugel, Inorg. Chem. 2 (1963) 896.
[11] H.R. Allcock, R.L. Kugel, K.J. Valan, Inorg. Chem. 5 (1966) 1709.
˘
[12] H. Kocaokutgen, I.E. Gu¨mru¨kc¸u¨oglu, Tr. J. Chem. 19 (1995) 219.
[13] A. Lycka, D. Snobl, Org. Magn. Reson. 15 (1981) 390.
[14] L.W. Reeves, Can. J. Chem. 38 (1960) 748.
[15] S.V. Levchik, G. Camino, L. Costa, A. Lindsay, D. Stevenson, J. Appl.
Polym. Sci. 67 (1998) 461.
[16] K.H. Saunders, R.L.M. Allen, Aromatic Diazo Compounds, 3rd ed.,
Edward Arnold, London, 1985, p. 889.
[17] H.R. Allcock, C. Kim, Macromolecules 22 (1989) 2596.