Synthesis, characterization, and spectroscopic properties of hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene and hexa(4-chloro-2-formyl- phenoxy)cyclotriphosphazene and fully substituted cyclotriphosphazene derivatives bearing a schiff base at room temperature

Article abstract of DOI:10.1080/10426507.2012.692132

Hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene (2) and hexa(4-chloro-2- formyl-phenoxy)cyclotriphosphazene (3) were obtained from the reactions of hexachloro- cyclotriphosphazene (1) with 5-bromosalicylaldehyde and 5-chlorosalicylaldehyde in the presence of (C2H5)3N and K2CO3 at room temperature, respectively. The new two organocyclotriphosphazenes bearing formyl groups were reacted with 4-cyano aniline, 2-phenyl aniline, 4-aceto aniline, 5-chloro-2-hydroxy aniline, 2-hydroxy aniline, 4-hydroxy aniline, 2-(4-morpholino)ethyl amine, 4-carboxy aniline, 4-carbomoyl aniline, 2-mercapto aniline, and 5-amino isoquonoline to prepare cyclotriphosphazene derivatives containing a Schiff base at room temperature. However, fully phenoxy-substituted cyclotriphosphazenes containing a Schiff base were isolated from the reactions of the compound 2 and 3 with 5-chloro-2-hydroxy aniline, 2-hydroxy aniline, 4-hydroxy aniline, and 2-(4-morpholino)ethyl amine. The structures of the synthesized compounds were characterized by elemental analysis, IR, and NMR (¹H, ¹³C, ³¹P) spectroscopy. According to the results of the analysis, all synthesized compounds were found to be fully substituted organocyclotriphosphazenes, such as hexa[4-bromo-2-(5-chloro-2- hydroxy-pheyliminomethyl)phenoxy]cyclotriphosphaze (2a). All cyclotriphosphazene derivatives synthesized gave fluorescence emission peaks in range between 300 nm and 410 nm.

Full text of DOI:10.1080/10426507.2012.692132

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Synthesis, Characterization,
and Spectroscopic Properties
of Hexa(4-Bromo-2-Formyl-
Phenoxy)Cyclotriphosphazene
and Hexa(4-Chloro-2-Formyl-
Phenoxy)Cyclotriphosphazene and
Fully Substituted Cyclotriphosphazene
Derivatives Bearing a Schiff Base at
Room Temperature
Ali İhsan Öztürk a , Fatih Aslan a , Ökkeş Yılmaz c , Mehmet Alğın a ,
Mustafa Arslan d & H. İbrahim Mutlu b
a Art & Science Faculty, Department of Chemistry , Harran
University , Şanlıurfa , Turkey
b Art & Science Faculty, Department of Physics , Harran University ,
Şanlıurfa , Turkey
c Art & Science Faculty, Department of Biology , Fırat University ,
Elazığ , Turkey
d Education Faculty , Yıldız Technical University , İstanbul , Turkey
Published online: 31 May 2013.
To cite this article: Ali İhsan Öztürk , Fatih Aslan , Ökkeş Yılmaz , Mehmet Alğın , Mustafa
Arslan & H. İbrahim Mutlu (2013) Synthesis, Characterization, and Spectroscopic Properties
of Hexa(4-Bromo-2-Formyl-Phenoxy)Cyclotriphosphazene and Hexa(4-Chloro-2-Formyl-
Phenoxy)Cyclotriphosphazene and Fully Substituted Cyclotriphosphazene Derivatives Bearing a Schiff
Base at Room Temperature, Phosphorus, Sulfur, and Silicon and the Related Elements, 188:5, 585-595,
DOI: 10.1080/10426507.2012.692132
To link to this article: http://dx.doi.org/10.1080/10426507.2012.692132
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Phosphorus, Sulfur, and Silicon, 188:585–595, 2013
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.692132
SYNTHESIS, CHARACTERIZATION, AND
SPECTROSCOPIC PROPERTIES OF HEXA(4-BROMO-2-
FORMYL-PHENOXY)CYCLOTRIPHOSPHAZENE AND
HEXA(4-CHLORO-2-FORMYL-
PHENOXY)CYCLOTRIPHOSPHAZENE AND FULLY
SUBSTITUTED CYCLOTRIPHOSPHAZENE DERIVATIVES
BEARING A SCHIFF BASE AT ROOM TEMPERATURE
1
1
3
˙
¨
¨
Ali Ihsan Oztu¨rk, Fatih Aslan, Okkes¸ Yılmaz,
1
4
2
˙
Mehmet Alg˘ın, Mustafa Arslan, and H. Ibrahim Mutlu
1Art & Science Faculty, Department of Chemistry, Harran University,
S¸anlıurfa, Turkey
2Art & Science Faculty, Department of Physics, Harran University,
S¸anlıurfa, Turkey
3Art & Science Faculty, Department of Biology, Fırat University, Elazıg˘, Turkey
4
˙
Education Faculty, Yıldız Technical University, Istanbul, Turkey
GRAPHICAL ABSTRACT
Br
Br
O
O
Cl
Cl
Cl
Cl
Br
O
N
P
O
O
N
P
P
P
N
O
O
THF, room temp.
(C2H5)3N
Br
P
P
N
6
+
N
O
Br
N
O
OH
Cl Cl
O
O
O
1
O
Br
Br
2
Abstract Hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene (2) and hexa(4-chloro-2-
formyl-phenoxy)cyclotriphosphazene (3) were obtained from the reactions of hexachloro-
cyclotriphosphazene (1) with 5-bromosalicylaldehyde and 5-chlorosalicylaldehyde in the
presence of (C2H5)3N and K2CO3 at room temperature, respectively. The new two organocy-
clotriphosphazenes bearing formyl groups were reacted with 4-cyano aniline, 2-phenyl
aniline, 4-aceto aniline, 5-chloro-2-hydroxy aniline, 2-hydroxy aniline, 4-hydroxy aniline,
Received 21 March 2012; accepted 4 May 2012.
The authors acknowledge the “Scientific and Technical Research Council of Turkey” grant No. 107T407
and Harran University Scientific Research Fund for Support (Project No: HUBAK 2009/058).
˙
¨
Address correspondence to Ali Ihsan Oztu¨rk, Art & Science Faculty, Department of Chemistry, Harran
University, S¸anlıurfa, Turkey. E-mail: aozturk@harran.edu.tr
585

˙
¨
¨
586
A. I. OZTURK ET AL.
2-(4-morpholino)ethyl amine, 4-carboxy aniline, 4-carbomoyl aniline, 2-mercapto aniline,
and 5-amino isoquonoline to prepare cyclotriphosphazene derivatives containing a Schiff base
at room temperature. However, fully phenoxy-substituted cyclotriphosphazenes containing a
Schiff base were isolated from the reactions of the compound 2 and 3 with 5-chloro-2-hydroxy
aniline, 2-hydroxy aniline, 4-hydroxy aniline, and 2-(4-morpholino)ethyl amine. The structures
of the synthesized compounds were characterized by elemental analysis, IR, and NMR (1H,
13C, 31P) spectroscopy. According to the results of the analysis, all synthesized compounds
were found to be fully substituted organocyclotriphosphazenes, such as hexa[4-bromo-2-(5-
chloro-2-hydroxy-pheyliminomethyl)phenoxy]cyclotriphosphaze (2a). All cyclotriphosphazene
derivatives synthesized gave fluorescence emission peaks in range between 300 nm and 410 nm.
Keywords Phosphazene; cyclotriphosphazene; organophosphazene; hexacholorocyclotriphos-
phazene; salicylaldehyde; Schiff base
INTRODUCTION
A large number of organocyclotriphosphazenes have been synthesized by the nucle-
ophilic substitution reactions of halophosphazenes with organic reagents such as alcohol,
phenol, amines, Grignard reagents, and thiols.1–8 It has been estimated that more than 5,000
different cyclic and linear phosphazene derivatives have been isolated and characterized.9
Organophosphazenes have been shown to possess a wide range of applications including in-
organic hydraulic fluids and lubricants, biologically important substrates such as anticancer
agents, insect chemosterilants, pesticides and fertilizers, and photosensitive materials.10–13
Furthermore, it was reported that the antiproliferative activity of cyclotriphosphazenes con-
taining Schiff bases was observed to be much higher against cancer cells than the normal
cells.14,15 Schiff bases also have a wide range of applications in several fields such as
antibacterial, antifungal, antitumor activities, catalysis, and coordination chemistry.16
Although a large number of fully phenoxy-substituted cyclotriphosphazenes have
been generated from the reactions of halophosphazenes with phenol and its derivatives,
fully aryloxy-substituted cyclotriphosphazenes containing functional groups such as
formyl, Schiff bases, and oximes are limited in the literature.17–19 Fully phenoxy-
substituted cyclotriphosphazenes bearing formyl groups were only obtained from the
reactions of hexachlorocyclotriphosphazene with 4-hydroxybezaldehyde, salicylaldehyde
(2-hydroxybenzaldehyde), 4-hydroxy-2-methoxy-benzaldehyde, and 4-hydroxy-3-
metoxy-benzaldehyde(vanillin).17,20–24 Organocyclotriphosphazenes containing Schiff
bases were also derived from the reactions of hexa(4-formyl-phenoxy)cyclotriphosphazene
and hexa(2-formyl-phenoxy)cyclotriphosphazene with some primary amines.22,24–26 The
organophosphazenes were reported to possess fluorescence properties.22,27–31
In this study, we report the synthesis of novel fully substituted hexa(4-bromo-
2-formyl-phenoxy)cyclotriphosphazene (2) and hexa(4-chloro-2-formyl-phenoxy)cyclotri-
phosphazene (3) from the reactions of hexachlorocyclotriphosphazene with 5-
bromosalicylaldehyde(5-bromo-2-hydroxy-benzaldehyde) and 5-chlorosalicylaldehyde
(5-chloro-2-hydroxy-benzaldehyde) at room temperature. In addition, fully phenoxy-
substituted cyclotriphosphazenes carrying Schiff base groups were derived from the
reactions of the compounds 2 and 3 with 5-chloro-2-hydroxy aniline, 2-hydroxy aniline,
4-hydroxy aniline, 2-(4-morpholino)ethyl amine, and 2-phenyl aniline. The fluorescence
spectra of all synthesized cyclotriphosphazene derivatives showed fluorescence emission
peaks in range 300–410 nm in tetrahydrofuran (THF) solution.

FULLY PHENOXY-SUBSTITUTED CYCLOTRIPHOSPHAZENES
587
Br
O
O
Br
Cl
Cl
Cl
Cl
Br
Br
O
O
N
P
O
O
N
P
P
P
N
O
THF, room temp.
P
P
N
6
+
N
O
(C2H5)3N
N
O
OH
O
Br
Cl Cl
O
Br
O
O
Br
Figure 1 The reaction equation of N3P3Cl6 with 5-bromosalicylaldehyde.
RESULTS AND DISCUSSION
5-bromosalicylaldehyde and 5-chlorosalicylaldehyde (10 equivalent of N3P3Cl6)
were used more than the amount of the reactions equation for the synthesis of fully
phenoxy-substituted cyclotriphosphazene (Figs. 1 and 2).15 Compounds (2 and 3) were
easily isolated in good yield as white solids by precipitation from diethyl ether.
Fully substituted cyclotriphosphazene derivatives containing Schiff base were not
isolated from all primary amines. Fully substituted cyclotriphosphazenes containing Schiff
base (2a–e and 3a–d) were only formed from the reactions of 5-chloro-2-hydroxy aniline,
2-hydroxy aniline, 4-hydroxy aniline, and 2-(4-morpholino)ethyl amine. Note that, 2a–e
and 3a–d were obtained with the yields in a range 40%–84% (Figs. 3 and 4). The structures
of the cyclotriphosphazenes derived from other primary amines were not characterized by
spectroscopic methods. These compounds were determined to be partially substituted from
the Fourier transform infrared (FT-IR) spectra which showed peaks of aldehyde group.
Therefore, these compounds were not evaluated.
The results of elemental analysis, FT-IR and NMR(1H, 13C, 31P) are appropriate to
the chemical structure for all compounds as shown in the figures. All spectroscopic results
were given in the experimental section. The synthesized organophosphazenes are solids and
Cl
O
Cl
Cl
Cl
Cl
Cl
Cl
O
N
P
Cl
O
O
O
P
P
N
O
THF, room temp.
N
P
O
6
+
P
P
N
N
O
K2CO3
OH
N
O
Cl Cl
O
Cl
O
Cl
O
O
Cl
Figure 2 The reaction equation of N3P3Cl6 with 5-chlorosalicylaldehyde.

˙ ¨ ¨
A. I. OZTURK ET AL.
588
Br
O
Br
R
N
O
Br
Br
Br
O
O
O
N
N
N
P
Br
R
R
O
O
R
O
P
P
N
P
THF, room temp.
O
O
P
P
R(Ar)-NH
6
+
2
N
O
N
O
HCOOH
O
Br
N
O
N
N
O
Br
O
Br
O
Br
N
O
R
Br
N
R
2
Br
(2a-2e)
Cl
HO
CH2
O
CH2
H
N
R(Ar):
OH
OH
a
b
c
d
e
Figure 3 The reaction equation of the compound 2 with primary amines.
soluble in common organic solvents such as CH2Cl2, acetone, and THF. Unlike the majority
of other similar studies, all of the reactions were carried out at room temperature.17,20,21
The FT-IR spectra of the compounds (2 and 3) exhibited strong two stretching
bands at 1203 cm−1 and 1160 cm−1 attributed to P N bonds of the cyclophosphazene
ring, while two PCl2 absorption peaks are not in spectra. Aldehyde carbonyl stretching
bands for compounds 2 and 3 are observed at 1693 cm−1 and 1698 cm−1, respectively.
In the IR spectra of the compounds (2a–e) and (3a–d) derived from compounds 2 and
3, the characteristic HC N stretching bands are observed in the range 1619–1640 cm−1
.
Cl
Cl
O
R
N
R
N
O
Cl
Cl
O
Cl
O
N
O
Cl
R
O
N
P
O
O
N
P
P
P
N
O
THF, room temp.
HCOOH
P
P
O
R(Ar)-NH
6
+
O
2
N
O
R
N
O
N
O
Cl
N
Cl
R
O
O
N
O
Cl
Cl
O
N
Cl
R
3
Cl
(3a-3d)
Cl
H
CH2
CH2
HO
O
N
R(Ar):
OH
OH
a
b
c
d
Figure 4 The reaction equation of the compound 3 with primary amines.

FULLY PHENOXY-SUBSTITUTED CYCLOTRIPHOSPHAZENES
589
Table 1 Characteristic IR peaks data of all derived compounds
Compound
νHC
O
νHC
N
νP
N
νP
O
C(Aryl)
1
—
—
1213
—
2
3
1693
1698
—
—
—
—
—
—
—
—
—
1203, 1192, 1177
1196, 1170
1201, 1164
1207, 1164
1188, 1163
1204, 1163
1187, 1162
1203, 1163
1206, 1163
1189, 1162
1204, 1163
959
956
960
960
959
956
957
960
961
950
956
2a
2b
2c
2d
2e
3a
3b
3c
3d
1619
1619
1619
1640
1619
1621
1619
1619
1640
—
—
Most significantly, the IR spectra of the compounds (2a–2e) and (3a–3d) did not show
stretching bands at 1693 and 1698 cm−1 belonging to aldehyde carbonyl (CH O).
The characteristic HC O, HC N, P N, and P O C(Aryl) stretching bands for all
of the compounds were given in Table 1.
The 31P NMR spectra of the compounds 2 and 3 show singlet peaks at 7.7 and
7.9 ppm. The (1H-decoupled) 31P NMR spectra for compounds (2a–e, 3a–d) exhibited a
peak in the range 7.5–8.5 ppm as a singlet. The results indicate that the same organic groups
are bond to phosphorus atoms. The spin systems for all compounds are interpreted as A3.
31P NMR spectra data of all derived cyclotriphosphazenes are given in Table 2.
The 1H and 13C NMR spectra of all synthesized cylotriphosphazenes derivates indicate
1
all peaks corresponding to the protons and carbons of organic groups. In the H and 13C
NMR spectra for 2a–e and 3a–d, imine (CH N) proton and carbon chemical shift were
observed at 8.0–8.3 ppm and 155–150 ppm, respectively. The formyl proton and carbon
peak for the compounds 2 and 3 were assigned at 9.9 ppm and 185 ppm. These results show
that all of the formyl groups were transformed into imines.
The absorption and fluorescence spectra results for all compounds were given in
Table 3.
Whereas the absorption spectra for 2d and 3d from aliphatic amines display two
strong bands between 230 nm and 300 nm, the other compounds derived from aromatic
amines display three strong bands between 220 nm and 360 nm. The absorptions might be
attributed to the π-π∗ transition of the cyclotiphosphazene bonded organic groups.22 The
absorption spectra for the compounds 2 and 3 derived from 5-bromosalicylaldehyde and
Table 2 The 1H-decoupled 31P NMR spectral data of all derived cyclotriphosphazenes
Compound
δ (P(OR)2) ppm
Compound
δ (P(OR)2) ppm
2
7.7
7.7
8.1
8.1
8.0
8.4
3
7.9
7.3
7.7
8.0
8.2
—
2a
2b
2c
2d
2e
3a
3b
3c
3d
—

˙
¨
¨
590
A. I. OZTURK ET AL.
Table 3 The wavelength data of electronic absorption and fluorescence peaks for all compounds
Absorption λmax.
nm (logε)
,
Excitation, λEx.
nm (logε)
,
Emission λEm.
nm (logε)
,
Stoke’s shift
ꢀλST
Compound
1
175 (4.0)a
—
2
3
228 (4.8), 304 (4.1)
241 (4.8), 303 (4.2)
228 (5.0), 270 (4.8), 375 (4.7)
226 (5.0), 269 (4.8), 365 (4.8)
244 (4.9), 283 (4.6), 354 (4.7)
227 (5.1), 296 (4.3)
292 (7.3)
292 (7.2)
284 (7.0)
294 (7.5)
265 (6.7)
293 (7.5)
335 (7.5)
284 (7.2)
301 (7.4)
309 (6.8)
293 (7.5)
322 (7.3)
320 (7.2)
317 (7.0)
328 (7.5)
316 (6.7)
314 (7.5)
410 (7.5)
318 (7.3)
329 (7.4)
408 (6.9)
311 (7.4)
30
28
33
34
51
21
75
34
28
99
18
2a
2b
2c
2d
2e
3a
3b
3c
3d
—
230 (5.2), 270 (5.1), 374 (4.9)
239 (5.0), 272 (4.9), 365 (4.9)
244 (5.1), 283 (4.8), 354 (5.0)
231 (5.0), 293 (4.5)
aReference [8].
5-chlorosalicylaldehyde display two strong bands between 220 nm and 305 nm caused by
the π-π∗ transition.
Fluorescence emission peaks for all of synthesized phosphazene derivatives were
observed in fluorescence spectra which were measured in dilute THF solutions (5 × 10−5
)
at room temperature. Fluorescence emission peaks appeared in the range 310–410 nm,
in the ultraviolet range. The compound 2e has the largest fluorescence emission peak
wavelength (410 nm). Fluorescence emission peaks for organophosphazenes carrying Schiff
bases derived from hexa(2-formyl-phenoxy)cyclotriphosphazene were detected in the range
300–550 nm.22 In another study, fluorescence emission peaks for hydroxyl substituted
hexa(phenoxy)cyclotriphosphazene derivatives were observed at around 298 nm.29 There
are also organophosphazene derivatives to given fluorescence emission peaks in the visible
region.31 Fluorescence emission peaks give organophosphazenes in the ultraviolet or visible
region. The Stoke’s shift values were also calculated. The values were found to have shifted
to 18–99 nm.
CONCLUSIONS
Fully phenoxy-substituted cyclotriphosphazenes bearing a formyl group were eas-
ily synthesized from the reactions of hexachlorocylotriphosphazene with phenol-bearing
formyl groups in the presence of K2CO3 or (C2H5)3N at room temperature. Then, fully
phenoxy-substituted cyclotriphosphazenes containing a Schiff base were also easily isolated
from the reaction of these compounds with some primary amines at room temperature.
Fully phenoxy substituted cyclotriphosphazenes containing Schiff bases were only
obtained from aliphatic primary amines or primary amines bearing electron donor groups
in the structure. All of the compounds were soluble in organic solvents such as chloroform,
dichloromethane, THF, and acetone.
EXPERIMENTAL
Hexachlorocyclotriphosphazene (N3P3Cl6), 5-bromosalicylaldehyde, 5-chlorosali-
cylaldehyde, 4-cyanoaniline, 4-acetoaniline, 2-phenylaniline, 5-chloro-2-hydroxyaniline,

FULLY PHENOXY-SUBSTITUTED CYCLOTRIPHOSPHAZENES
591
2-hydroxyaniline, 4-hydroxyaniline, 4-(2-aminoethyl)morpholine, 4-aminobenzoic acid, 4-
aminobezamide, 2-aminothiophenol, 5-aminoisoquinoline, 5-aminoindazole, 2-amino-
fluorene, and 2-aminobezothiazole were purchased form Aldrich and used without further
purification. The syntheses of hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene and
hexa(4-chloro-2-formyl-phenoxy)cyclotriphosphazene were carried out under an argon
atmosphere. Syntheses of the other phosphazene derivates were carried out under room
atmosphere. THF was distilled over metallic sodium in the presence of benzophenone
under an argon atmosphere.
The NMR (1H, 13C, 31P) spectra were recorded on a Bruker DPX FT-NMR (300 MHz)
spectrometer (SiMe4 as internal and 85% H3PO4 as external standards). IR spectra were
recorded on a Perkin-Elmer 1000 FTIR spectrometer in KBr disks. The elemental composi-
tions were determined on a LECO CHNS-O analyzer. The melting points were measured on
a Electrothermal IA 9200 apparatus in capillary. The data of fluorescence emission spectra
were obtained from Shimadzu RF-1504 spectrofluorometer using 1 cm cuvettes at room
temperature in 5 × 10−5 M THF solution. UV-vis. spectra were recorded on a Shimadzu
mini 1240 UV spectrophotometer.
Synthesis of Hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene (2)
A solution of 5-bromosalicylaldehyde (28.9 g, 143.8 mmol) in THF (50 mL) was
added to a stirred mixture of N3P3Cl6 (1) (5 g, 14.38 mmol) and triethylamine (20 mL,
143.8 mmol) in THF (200 mL) at room temperature. The mixture was stirred for 48 h and
then the precipitated triethylamine hydrochloride was filtered off. The solvent was evapo-
rated on a rotary evaporator under reduced pressure. The product mixture was dissolved in
dichloromethane (CH2Cl2) and compound 2 was obtained as white solid by precipitation
with diethyl ether. Yield: 15.42 g (80%). M.p.: 175 ◦C. Anal. Calc. for N3P3C42H24Br6O6:
C: 37.79, H: 1.81, N: 3.15. Found: C: 38,60, H: 2,03, N: 3,23. FTIR (KBr, cm−1): 3083
(C H aromatic), 2867 (H CO aldehyde), 1693 (HC O aldehyde), 1203, 1192, 1177
(P N), 959 (P OAr aryl). 1H NMR δ (ppm): 9.9 (s, HC O), 7.9 (d, 1H, J = 2.46 Hz.),
7.5 (dd, J = 2.54 Hz.), 6.9 (d, 1H). 13C NMR δ (ppm): 186.1 (s, C O), 149.8 (m, J =
2.65 Hz.), 138.2, 132.5, 128.8 (J = 2.1 Hz.), 122.8, 120.1. 31P NMR δ (ppm): 7.7.
Synthesis of Hexa(4-chloro-2-formyl-phenoxy)cyclotriphosphazene (3)
A solution of 5-chlorosalicylaldehyde (22.52 g, 143.8 mmol) in THF (50 mL) was
added to a stirred mixture solution of N3P3Cl6 (1) (5 g, 14.38 mmol) and K2CO3 (24 g,
143.8 mmol) in THF (200 mL) at room temperature. The mixture was stirred for 48 h, and
the precipitate was filtered off. The solvent was evaporated on a rotary evaporator under
reduced pressure. The product mixture was dissolved in dichloromethane (CH2Cl2) and
compound 3 was obtained as white solid by the precipitation in diethyl ether solvent. Yield:
9 g (59%). M.p.: 127 ◦C. Anal. Calc. % for N3P3C42H24Cl6O6: C: 47.22, H: 2.26, N: 3.93.
Found, %: C: 47.32, H: 2.39, N: 3.62. FTIR (KBr, cm−1): 3088 (C H aromatic), 2874
1
(H CO aldehyde), 1698 (HC O aldehyde), 1196, 1170 (P N), 956 (P OAr aryl). H
NMR δ (ppm): 9.9 (s, HC O), 7.7 (d, 1H, J = 2.50 Hz.), 7.4 (dd, J = 2.70 Hz.), 7.0 (d,
1H). 13C NMR δ (ppm): 186.2 (s, HC O), 145.3(m, J = 2.65 Hz.), 135.2, 132.7, 129.3,
128.6, 122.5. 31P NMR δ (ppm): 7.9.

˙
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¨
592
A. I. OZTURK ET AL.
General Method for the Synthesis of Fully Substituted
Cyclotriphosphazene Derivates Containing Schiff Base
from the Compound 2
Fully substituted cylotriphosphazene derivatives containing a Schiff base were ob-
tained from the reaction of the compound 2 (0.5 g, 0.38 mmol) with an excess of primary
amine (3.8 mmol) in THF (25 mL) at room temperature. The mixture of compound 2 and
primary amine was stirred for 2 days at room temperature. After the reaction was complete,
the solvent was evaporated under reduced pressure. The crude product was washed several
times with diethyl ether. The precipitate was filtered off and finally dried.
Synthesis of Hexa[4-bromo-2-(5-chloro-2-
hydroxy-pheyliminomethyl)phenoxy]cyclotriphosphaze (2a)
5-chloro-2-hydroxy-aniline (0.55 g, 3.8 mmol). Note that, 2a is a goldenrod solid
(0.63 g, 80%). M.p.: 148 ◦C. Anal. Calc. % for N9P3C78H48O12Br6Cl6: C: 44.86, H: 2.32,
N: 6.04. Found, %: C: 44.98, H: 2.47, N: 6.11. FTIR (KBr, cm−1): 3428 ( OH), 3070 (C H
aromatic), 2854 (H CN imine), 1619 (HC N imine), 1201, 1164 (P N), 960 (P OAr
aryl). 1H NMR δ (ppm): 8.70 (s, H CN), 8.41–6.81 (the peaks of aromatic protons). 13
C
NMR δ (ppm): 151.7 (s, HC N), 151.3, 149.7 (P O C(Aryl)) 136.7, 135.34, 131.9,
129.6, 128.5, 124.1, 123.0, 119.4, 117.0, 117.0. 31P NMR δ (ppm): 7.7.
Synthesis of Hexa[4-bromo-2-(2-hydroxy-pheyliminomethyl)
phenoxy]cyclotriphosphaze(2b)
2-hydroxy-aniline (0.42 g, 3.8 mmol). Note that, 2b is an olive solid (0.48 g, 67%).
M.p.: 131 ◦C. Anal. Calc. % for N9P3C78H54Br6O12: C: 49.79, H: 2.89, N: 6.70. Found, %:
C: 49.50, H: 2.96, N: 6.34. FTIR (KBr, cm−1): 3427 ( OH), 3070 (C H aromatic), 2849
(H CN imine), 1619 (HC N imine), 1207, 1164 (P N), 960 (P OAr aryl). 1H NMR δ
(ppm): 8.72 (s, H CN), 8.50–6.62 (the peaks of aromatic protons). 13C NMR δ (ppm):
153.0 (s, HC N), 149.5, 148.6 (P O C(Aryl)) 135.5, 134.9, 131.3, 130.1, 129.3, 123.1,
119.8, 119.4, 116.6, 115.8. 31P NMR δ (ppm): 8.1.
Synthesis of Hexa[4-bromo-2-(4-hydroxy-
pheyliminomethyl)phenoxy]cyclotriphosphaze(2c)
4-hydroxy-aniline (0.42 g, 3.8 mmol). Note that, 2c is a dark, olive-green solid
(0.45 g, 59%). M.p.: 144 ◦C. Anal. Calc. % for N9P3C78H54Br6O12: C: 49.79, H: 2.89, N:
6.70. Found, %: C: 50.93, H: 3.38, N: 7.02. FTIR (KBr, cm−1): 3383 ( OH), 3020 (C H
aromatic), 2813 (H CN imine), 1619 (HC N imine), 1188, 1163 (P N), 959 (P OAr
aryl). 1H NMR δ (ppm): 8.40 (s, H CN), 8.22–6.53 (the peaks of aromatic protons). 13
C
NMR δ (ppm): 157.0 (s, HC N), 150.6, 148.5 (P O C(Aryl)) 148.2, 142.3, 134.1, 130.4,
130.1, 122.7, 120.6, 115.7. 31P NMR δ (ppm): 8.1.

FULLY PHENOXY-SUBSTITUTED CYCLOTRIPHOSPHAZENES
593
Synthesis of Hexa[4-bromo-2-(2-(4-morpholine)-ethyliminomethyl)
phenoxy]cyclotriphosphaze (2d)
2-(4-morpholine)-ethylamine (0.50 mL, 3.8 mmol). Note that, 2d is a maroon solid
(0.56 g, 74%). M.p.: 82 ◦C. Anal. Calc. % for N15P3C78H96Br6O12: C: 46.65, H: 4.82, N:
10.46. Found, %: C: 47.62, H: 5.8, N: 11.06. FTIR (KBr, cm−1): 3070 (C H aromatic),
2954–2900 (C H alkyl), 2852 (H CN imine), 1640 (HC N imine), 1204, 1163 (P N),
956 (P OAr aryl). 1H NMR δ (ppm): 8.1 (s, H CN), 7.9(d), 7.47(dd), 6.9(d), 3.51–2.35
CH2 protons. 13C NMR δ (ppm): 154.2 (s, HC N), 148.1 (P O C(Aryl)) 134.8, 130.3,
129.9, 123.4, 119.3, 66.6, 58.8, 58.5, 53.8. 31P NMR δ (ppm): 8.0.
Synthesis of Hexa[4-bromo-2-(2-phenyl-pheyliminomethyl)
phenoxy]cyclotriphosphaze (2e)
2-phenylani◦line (0.65 g, 3.8 mmol). Note that, 2e is a yellow green solid (0.34 g,
40%). M.p.: 108 C. Anal. Calc. % for N9P3C114H78O6Br6: C: 61.06, H: 3.51, N: 5.62.
Found, %: C: 60.42, H: 3.495, N: 5.76. FTIR (KBr, cm−1): 3060 (C H aromatic), 2919
1
(H CN imine), 1619 (HC N imine), 1187, 1162 (P N), 957 (P OAr aryl). H NMR
δ (ppm): 8.4 (s, H CN), 8.0–6.7 aromatic proton peaks. 13C NMR δ (ppm): 153.2 (s,
HC N), 149.1 (P O C(Aryl)) 149.1 140.1, 136.77, 136.7, 135.7, 131.6, 130.9, 130.8,
129.4, 128.4, 127.7, 127.6, 124.2, 120.2, 118.8. 31P NMR δ (ppm): 8.4.
General Method for the Synthesis of Fully Substituted
Cylotriphosphazene Derivates Containing Schiff Base from the Compound 3
Fully substituted cylotriphosphazene derivates containing a Schiff base were obtained
from the reaction of the compound 3 (0.5 g, 0.47 mmol) with the excess of primary amine
(4.7 mmol) in THF (25 mL) at room temperature. The mixture of the compound 3 and
primary amine was stirred for 2 days under room atmosphere. After the reaction was
completed, the solvent was evaporated under reduced pressure. The crude product was
washed several times with diethyl ether. The precipitate was filtered off and finally dried.
Synthesis of Hexa[4-chloro-2-(5-chloro-2-hydroxy-pheyliminomethyl)
phenoxy]cyclotriphosphaze (3a)
5-chloro-2-hydroxy-◦aniline (0.68 g, 4.7 mmol). Note that, 3a is a goldenrod solid
(0.63 g, 80%). M.p.: 190 C. Anal. Calc. % for N9P3C78H48O12Cl12: C: 51.43, H: 2.66,
N: 6.92. Found, %: C: 52.93, H: 3.31, N: 6.45. FTIR (KBr, cm−1): 3422 ( OH), 3071
(C H aromatic), 2868 (H CN imine), 1621 (HC N imine), 1203, 1163 (P N), 960
(P OAr aryl). 1H NMR δ (ppm): 8.5 (s, H CN), 7.9–6.7 (the peaks of aromatic protons).
13C NMR δ (ppm): 151.2 (s, HC N), 150.7, 147.8 (P O C(Aryl)) 135.2, 132.3, 129.6,
129.1, 128.6, 125.0, 120.4, 116.7, 115.8. 31P NMR δ (ppm): 7.3.
Synthesis of Hexa[4-chloro-2-(2-hydroxy-pheyliminomethyl)
phenoxy]cyclotriphosphaze (3b)
2-hydroxy-aniline (0.52 g, 4.7 mmol). Note that, 3b is a olive solid (0.48 g, 67%).
◦
M.p.: 145 C. Anal. Calc. % for N9P3C78H54Cl6O12: C: 58.01, H: 3.37, N: 7.81. Found,

˙ ¨ ¨
A. I. OZTURK ET AL.
594
%: C: 58.85, H: 3.80, N: 7.95. FTIR (KBr, cm−1): 3422 ( OH), 3050 (C H aromatic),
1
2844 (H CN imine), 1619 (HC N imine), 1206, 1163 (P N), 961 (P OAr aryl). H
NMR δ (ppm): 8.5 (s, H CN), 8.0–6.6 (the peaks of aromatic protons). 13C NMR δ (ppm):
152.7 (s, HC N), 149.1, 147.7 (P O C(Aryl)) 134.5, 132.08, 131.8, 130.1, 129.1, 128.6,
122.3, 121.5, 115.6, 115.6. 31P NMR δ (ppm): 7.7.
Synthesis of Hexa[4-chloro-2-(4-hydroxy-pheyliminomethyl)
phenoxy]cyclotriphosphaze (3c)
4-hydroxy-aniline (0.52 g, 4.7 mmol). Note that, 3c is a dark olive solid (0.45 g, 59%).
M.p.: 185 ◦C. Anal. Calc. % for N9P3C78H54Cl6O12: C: 58.01, H: 3.37, N: 7.81. Found, %:
C: 57.03, H: 3.64, N: 7.49. FTIR (KBr, cm−1): 3309 ( OH), 3020 (C H aromatic), 2803
(H CN imine), 1619 (HC N imine), 1189, 1162 (P N), 950 (P OAr aryl). 1H NMR δ
(ppm): 9.5 (H O 8.1 (s, H CN), 8.0–6.6 (the peaks of aromatic protons). 13C NMR δ
(ppm): 157.5 (s, HC N), 148.1, 147.8 (P O C(Aryl)) 141.5, 131.5, 131.2, 130.0, 127.0,
123.1, 122.9, 116.0. 31P NMR δ (ppm): 8.0.
Synthesis of Hexa[4-chloro-2-(2-(4-morpholine)-ethyliminomethyl)
phenoxy]cyclotriphosphaze (3d)
2-(4-morpholine)-ethylamine (0.62 mL, 4.7 mmol). Note that, 3d is a maroon solid
(0.56 g, 74%). M.p.: 85 ◦C. Anal. Calc. % for N15P3C78H96Cl6O12: C: 53.80, H: 5.56, N:
12.07. Found, %: C: 54.34, H: 6.24, N: 12.09. FTIR (KBr, cm−1): 3070 (C H aromatic),
2954–2900 (C H alkyl), 2852 (H CN imine), 1640 (HC N imine), 1204, 1163 (P N),
1
956 (P OAr aryl). H NMR δ (ppm): 8.1 (s, H CN), 7.8(d), 7.36(dd), 7.0(d), 3.6–2.3
(the peaks of CH2 protons). 13C NMR δ (ppm): 154.3 (s, HC N), 147.6 (P O C(Aryl))
131.8, 131.2, 129.6, 127.3, 123.1, 66.6, 66.5, 53.9, 53.6. 31P NMR δ (ppm): 8.2.
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