Organocyclotriphosphazenes with poly Schiff bases and aldehydes from hexachlorocyclotriposphazene, 5-chloro-salicylaldehyde and 5-bromo-salicylaldehyde under the room conditions without using Ar or N2 atmosphere

Article abstract of DOI:10.1016/j.ica.2019.119308

In this study, the reactions of hexachlorocyclotriphosphazene with 5-chloro-salicylaldehyde and 5-bromo-salicylaldehyde were separately performed in the presence of K₂CO₃ and triethylamine as a base without using Ar or N₂ atmosphere for the preparation of the organocyclotriphosphazene derivatives bearing six formyl groups (2 and 3) again. These reactions were monitored by ³¹P NMR spectroscopy to determine the formation time of the compounds (2 and 3). The result of this analysis showed that the compounds (2 and 3) occurred within 3 h under the above reaction conditions after the reactions begun. The ³¹P NMR spectra of the mixtures clearly displayed only singlet signal in the range of 8–9 ppm corresponding to characteristic phosphorus signals of cyclotriphosphazenes. Moreover, these two compounds were obtained in high yields even under such mild reaction conditions. In addition, the compounds (2 and 3) were reacted with aniline and some aniline derivatives for the production of new organocyclotriphosphazene derivatives bearing poly Schiff bases (2a–2k and 3a–3k). Although all the primary amines in these reactions were used more than necessary, it was detected that the organocyclotriphosphazene derivative including both formyl and Schiff base moieties (2k and 3k) occurred from only 4-nitro-aniline. Most importantly of all, hydrolysis of hexachlorocyclotriphosphazene in THF solution was also studied. It was determined that hexachlorocyclotriphosphazene did not hydrolysis under these conditions.

Full text of DOI:10.1016/j.ica.2019.119308

Journal Pre-proofs
Organocyclotriphosphazenes with poly Schiff bases and aldehydes from hexa-
chlorocyclotriposphazene, 5-chloro-salicylaldehyde and 5-bromo-salicylalde-
hyde under the room conditions without using Ar or N2 atmosphere
Faith Aslan, Ali İhsan Öztürk, Mustafa Binici
PII:
S0020-1693(19)31374-X
https://doi.org/10.1016/j.ica.2019.119308
ICA 119308
DOI:
Reference:
Inorganica Chimica Acta
To appear in:
Received Date:
Revised Date:
Accepted Date:
8 September 2019
29 October 2019
25 November 2019
Please cite this article as: F. Aslan, A. İhsan Öztürk, M. Binici, Organocyclotriphosphazenes with poly Schiff bases
and aldehydes from hexachlorocyclotriposphazene, 5-chloro-salicylaldehyde and 5-bromo-salicylaldehyde under
the room conditions without using Ar or N2 atmosphere, Inorganica Chimica Acta (2019), doi: https://doi.org/
10.1016/j.ica.2019.119308
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Organocyclotriphosphazenes with poly Schiff bases and aldehydes from
hexachlorocyclotriposphazene, 5-chloro-salicylaldehyde and 5-bromo-salicylaldehyde
under the room conditions without using Ar or N2 atmosphere
Faith ASLAN*, Ali İhsan ÖZTÜRK**, Mustafa BİNİCİ*
*Harran University, Art&Science Faculty, Department of Chemistry, Şanlıurfa, Turkey.
** Osmaniye Korkut Ata University, Art&Science Faculty, Department of Chemistry, Osmaniye,
Turkey.
Corresponding author: E-Mail:faslan33@yahoo.com
Adress: Department of Chemistry, Harran University, Şanlıurfa, Turkey
Abstract
In this study, the reactions of hexachlorocyclotriphosphazene with 5-chloro-
salicylaldehyde and 5-bromo-salicylaldehyde were separately performed in the presence of
K2CO3 and trietylamine as a base without using Ar or N2 atmosphere for the preparation of the
organocyclotriphosphazene derivatives bearing six formyl groups (2 and 3) again. These
31
reactions were monitored by P NMR spectroscopy to determine the formation time of the
compounds (2 and 3). The result of this analysis showed that the compounds (2 and 3) occurred
31
within3 h under the above reaction conditions after the reactions begun. The P NMR spectra
of the mixtures clearly displayed only singlet signal in the range of 8-9 ppm corresponding to
characteristic phosphorus signals of cyclotriphosphazenes. Moreover, these two compounds
were obtained in high yields even under such mild reaction conditions. In addition, the
compounds (2 and 3) were reacted with aniline and some aniline derivatives for the production
of new organocyclotriphosphazene derivatives bearing poly Schiff bases (2a-2k and 3a-3k).
Although all the primary amines in these reactions were used more than necessary, it was
detected that the organocyclotriphosphazene derivative including both formyl and Schiff base
moieties (2k and 3k) occurred from only 4-nitro-aniline. Most importantly of all, hydrolysis of
hexachlorocyclotriphosphazene in THF solution was also studied. It was determined that
hexachlorocyclotriphosphazene did not hydrolysis under these conditions.
Key Words. Cyclotriphosphazene, organophosphazene, salicylaldehyde, Schiff base.
1

1. Introduction
One from the best known and most studied compounds in the family of phosphazene is
also hexachlorocyclotriphosphazene which is the stable and performs nucleophilic substitution
reactions very well under the room conditions [1-5]. The derivation of the
organocyclotriphosphazenes from hexachlorocyclotriphosphazene begun with famous
researchers’ works such as Allcock, Shaw and Allen between 1950 and 1960 years [6-8].
Currently, the number of the reported organocyclotriphosphazenes is estimated to be more than
15,000 [9]. Although a lot of hydroxybenzaldehyde and primary amine derivatives are
available, the reported organocyclotriphosphazenes bearing aldehyde and imine groups are
rather rare among the published studies. The works related to Schiff base without phosphazene
which was discovered in 1864 by Hugo Schiff has been still continued to attract attention
among chemists [10]. Both Schiff bases and phosphazenes have been known to have a large
variety of useful applications.
In the literature, the organocyclotriphosphazene derivatives having formyl groups are
produced by using two different methods. First, hexachlorocylotriphsophazene is treated with
hydroxybenzaldehyde derivatives in the presence of a base such as K2CO3, Cs2CO3 or
triethylamine in the solvent, generally using K2CO3 [11]. These bases, which are used to hold
HCl formed in the reaction, are weak bases. In these reactions, all of the reagents are present in
the same reaction bubble. In other words, the reaction is performed in one step. Therefore,
NaH, one of the strongest bases known, should not be used in such reactions performed in one
step. Because, halophosphazene reacts with hydride instead of phenol derivatives. Thus, the
desired product could not be obtained. However, NaH can be used in the second reaction
method. In addition, such reactions should be carried out under Ar or N2 gas atmosphere and
the solvent used should be used after purification under Ar or N2 gas atmosphere, too. Second,
hexachlorocylotriphsophazene is reacted with sodium salt of hydroxybenzaldehyde derivatives
2

in the solvent [12]. The salt of phenol derivatives is obtained from the reaction of the phenol
derivative with metallic sodium or sodium hydride.
In the recent years, the first method has been preferred more than the second for the
synthesis of organocyclotriphosphazene derivatives bearing formyl groups, because the first
method is both the easiest and the most economical. The second method must be definitely
performed under the airless conditions. This kind of compounds are possible to achieve in good
yield with both methods. The effect of the base on the yield of organocyclotriphosphazene
derivatives is not known with certainty, according to studies in literature. In fact, we do not
come across a study in this field in literature either. As it is known, the synthesis of
organocyclotriphosphazene derivatives is generally carried out under Ar or N2 gas atmosphere.
Although the synthesis of organocyclotriphosphazene derivatives was performed without the
use of Ar or N2 gas atmosphere in previous our study, it was determined that the
hexasubstituted compounds formed with very good yield [13]. In previous our study, the
hydrolysis product of hexachlorocylotriphosphazene from atmospheric moisture and a very
small amount water in used solvent were not determined. If the hydrolysis product had
occurred, it would be possible to determine spectroscopically or the yield of the prepared
products would be significantly less. However, hexachlorocyclotriphosphazene is known to
hydrolyze fairly rapidly in water solution [19]. In this study, hydrolysis of
hexachlorocyclotriphosphazene in THF solvent was also studied.
Some works have been reported regarding the synthesis of the
organocyclotriphosphazene derivatives bearing Schiff base units in the literature. Three
different methods for the derivation of such compounds are known [14-16]. Moriya et al. firstly
prepared such compounds from the reactions of organocyclotriphsophazene derivatives
carrying formyl groups with primary amines [15]. This method has been preferred more than
the others to produce such compounds. There is not enough information in the literature about
the chemical, physical and biological properties of these compounds. In previously our studies,
3

it was reported that a great number of new organocyclotriphosphazene derivatives including six
imine units were derived from the reactions of hexa(2-formyl-phenoxy)cyclotriphosphazene,
hexa(4-formyl-phenoxy)cyclotriphosphazene,
hexa(4-formyl-3-metoxy-
phenoxy)cyclotriphosphazene, hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene and
hexa(4-chloro-2-formyl-phenoxy)cyclotriphosphazene with aniline, some aniline derivatives
and a few aliphatic primary amine derivatives [17-18]. Moreover, we firstly identified to occur
some organocyclotriphosphazene derivatives containing both imine and formyl units from
some aniline derivatives [13].
In the present study, hexa(4-chloro-2-formyl-phenoxy)cyclotriphosphazene(2) and
hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene(3) synthesized in our previous study
were prepared in the presence of K2CO3 and triethylamine in room conditions without using Ar
or N2 atmosphere again. The formation of the compounds 2 and 3 during the reactions were
monitored by 31P NMR spectroscopy. According to the result of this analyse, it was understood
that the compounds 2 and 3 occurred within 3 hours. When these reactions were continued for
24 hours using K2CO3 as a base, the compounds 2 and 3 were definitely not obtained. The
reactions of the compounds 2 and 3 with aniline (a) and selected aniline derivatives (b-j) were
also performed to derive the organocyclotriphosphazenes carrying six imine units. However, it
was found that such organocyclotriphosphazene derivatives did not occur from all aniline
derivatives. In contrast to our previous work, the organocyclotriphosphazene derivatives (2k
and 3k) carrying both formyl and Schiff base groups were produced from only 4-nitro-aniline.
2. Experimental section
2.1. Materials
Hexachlorocyclotriphosphazene (N3P3Cl6), the other chemicals and solvents were procured
from Aldrich and Merck. All of the chemicals and solvents were used as received without
4

further purification. All reactions were carried out under room conditions. N2 or Ar gas
atmosphere was certainly not used in this study.
2.2. Measurements
The NMR (1H, 31P) spectra were recorded on a Varian VNMRS (400 MHz ) spectrometer
(SiMe4 as internal and 85% H3PO4 as external standards) in (CD3)2SO, (CD3)2CO or CDCl3
solvent. IR spectra were recorded on a Perkin-Elmer spectrum two FTIR spectrometer with
ATR. The elemental analyses were performed on a LECO (CHNS-932) elemental analyzer.
Melting points were measured on an Electrothermal IA 9200 apparatus in capillary.
2.3. Hydrolysis research experiment of phosphazenes at THF
The solution of the compound 1 in THF solvent was mixed under three room
conditions. At the end of this period, NMR spectroscopy analysis of the solution was
1
performed. Furthermore, NMR analysis of the solvent THF was also performed. H NMR (the
1
solution of the compound 1, CDCl3): 3.62 (O-CH2- of THF), 1.73 (-CH2- of THF). H NMR
(THF, CDCl3): 3.62 (O-CH2-), 1.73 (-CH2-). 31P NMR (the solution of the compound 1,
CDCl3): 19.84 (a sharp singlet).
2.4. Synthesis
2.4.1. Synthesis of hexa(4-chloro-2-formyl-phenoxy)cyclotriphosphazene (2) in the presence of
(C2H5)3N
In a 250-mL single-necked flat-bottom flask equipped with magnetic mixing, N3P3Cl6
(1) (1.00 g, 2.876 mmol), THF (150 mL), (C2H5)3N (4.80 mL, 34.512 mmol) and 5-chloro-
salicylaldehyde (5.403 g, 34.512 mmol) were added sequentially. The mixture reaction was
maintained at room temperature for 3 h and then, 31P NMR analysis of the mixture was
performed. From this analysis, it became clear that the reaction was over. At the end of the
reaction, the insoluble matter of the reaction mixture was filtered off (with produced
5

(C2H5)3N.HCl). The filtered triethylamine hydrochloride [(C2H5)3N.HCl] was dried in room
conditions and weighed (experimental/calculated: 2.20 g / 2.38 g). The solution was
concentrated under reduced pressure. Then, the residue was dropped into solvent of ethyl
alcohol. The white powder was collected by filtration. In this way, the compound 2 was
achieved as a white solid and pure (81.4% yield, 2.50 g, 3.073 g, mp 115). Anal. Calc. for
N3P3C42H24Cl6O6: C, 47.22; H, 2.26; N, 3.93%. Found: C, 47.32; H, 2.39; N, 3.62%. FTIR (ʋ,
cm-1): 1699 and 1678 (HC=O), 1208, 1196, 1176, 1169 and 1155 (P=N), 964, 954 and 944 (P-
31
OAryl).1H NMR (, ppm ((CD3)2CO): 10.0(s, HC=O), 7.8-7.4 (Aryl H). P NMR (, ppm):
7.81 (s).
2.4.2. Synthesis of hexa(4-chloro-2-formyl-phenoxy)cyclotriphosphazene (2) in the presence of
K2CO3
In a 250-mL single-necked flat-bottom flask equipped with magnetic mixing, N3P3Cl6
(1) (0.25 g, 0,719 mmol), THF (75 mL), K2CO3 (1.20 g, 8.629 mmol) and 5-chloro-
salicylaldehyde (1.346 g, 8.629 mmol) were added sequentially. The mixture reaction was
maintained at room temperature for 3 h and then, 31P NMR analysis of the mixture was
performed. From this analysis, it became clear that the reaction was over. At the end of the
reaction, the insoluble matter of the reaction mixture was filtered off (with K2CO3, produced
KCl and KHCO3). The solution was concentrated under reduced pressure. Then, the residue
was dropped into solvent of ethyl alcohol. The white powder was collected by filtration. In this
way, the compound 2 was achieved as a white solid and pure (52% yield, 0.40 g, 3.073 g, mp
115). Anal. Calc. for N3P3C42H24Cl6O6: C, 47.22; H, 2.26; N, 3.93%. Found: C, 47.32; H, 2.39;
N, 3.62%. FTIR (ʋ, cm-1): 1699 and 1678 (HC=O), 1208, 1196, 1176, 1169 and 1155 (P=N),
964, 954 and 944 (P-OAryl).1H NMR (, ppm ((CD3)2CO): 10.0(s, HC=O), 7.8-7.4 (Aryl H).
31P NMR (, ppm): 7.81 (s).
2.4.3. Synthesis of the compound 4 in the presence of K2CO3 for 24 h
6

In a 250-mL single-necked flat-bottom flask equipped with magnetic mixing, N3P3Cl6 (1)
(0.25 g, 0,719 mmol), THF (75 mL), K2CO3 (1.20 g, 8.629 mmol) and 5-chloro-salicylaldehyde
(1.346 g, 8.629 mmol) were added sequentially. The mixture reaction was maintained at room
temperature for 24 h. At the end of the reaction, the insoluble matter of the reaction mixture
was filtered off (with K2CO3, produced KCl and KHCO3). The solution was concentrated under
reduced pressure. Then, the residue was dropped into solvent of ethyl alcohol. The black
powder was collected by filtration. In this way, the compound 4 was achieved as a black solid.
FTIR (ʋ, cm-1): 1688, 1679, 1658 and 1634 (HC=O), 1201, 1179, 1166 and 1146 (P=N), 946
31
and 932 (P-OAryl).1H NMR (, ppm ((CD3)2CO): 10.20-9.80 (-HC=O), 7.6-6.4 (Aryl H). P
NMR (, ppm): 10.20 (doublet), -0.55 (triplet).
2.4.4. Synthesis of hexa(4-chloro-2-formyl-phenoxy)cyclotriphosphazene (2) in the presence of
(C2H5)3N for 24 h
In a 250-mL single-necked flat-bottom flask equipped with magnetic mixing, N3P3Cl6
(1) (1.00 g, 2.876 mmol), THF (150 mL), (C2H5)3N (4.80 mL, 34.512 mmol) and 5-chloro-
salicylaldehyde (5.403 g, 34.512 mmol) were added sequentially. The mixture reaction was
maintained at room temperature for 24 h. At the end of the reaction, the insoluble matter of the
reaction mixture was filtered off (with produced (C2H5)3N.HCl). The filtered triethylamine
hydrochloride [(C2H5)3N.HCl] was dried in room conditions and weighed
(experimental/calculated: 2.20 g / 2.38 g). The solution was concentrated under reduced
pressure. Then, the residue was dropped into solvent of ethyl alcohol. The white powder was
collected by filtration. In this way, the compound 2 was achieved as a white solid and pure
(81.4% yield, 2.50 g, 3.073 g, mp 115).
2.4.5. General synthetic procedure for the compounds 2a-2k from the compound 2
In a 100-mL single-necked flat-bottom flask equipped with magnetic mixing, the
compound 2 (0.40 g, 0.375 mmol), THF (30 mL), two drops of formic acid and primary amine
derivative (4.50 mmol) were added sequentially. The reaction was continued for 24 hours under
7

room conditions. After the solution was reduced to approximately 5 mL under reduced
pressure, the solution was dropped into diethyl ether or alcohol for the removal of free primary
amine. The precipitate was filtered off and the color solid was dried under room conditions.
The compounds 2a-2k were obtained from the compound 2.
2.4.5.1. Synthesis of hexa[4-chloro-2-(phenyliminomethyl)phenoxy]cyclotriphosphazene (2a)
The compound 2a occurred from aniline (0.41 mL, 4.50 mmol) as a peach-orange color
solid (0.50 g, 87,7%, mp. 185 ºC). Anal. Calc. for N9P3C78H54Cl6O6: C, 61.68; H, 3.58; N,
8.30%. Found: C, 61.71; H, 3.66; N, 8.46%. FTIR (ʋ, cm-1): 1620 (HC=N), 1187 and 1159
(P=N), 977, 958 and 942 (P-OAryl). 1H NMR (, ppm (CDCl3): 8.34 (H-C=N), 8.10-6.70 (Aryl
H). 31P NMR (, ppm): 8.13 (s).
2.4.5.2. Synthesis of hexa[4-chloro-2-(1-naphthyliminomethyl)phenoxy]cyclotriphosphazene
(2b)
The compound 2b occurred from 1-naphthylamine (0.65 g, 4.50 mmol) as a maize color
solid (0.65 g, 95,6%, mp 118 ºC). Anal. Calc. for N9P3C102H66Cl6O6: C, 67.34; H, 3.66; N,
6.93%. Found: C, 66.99; H, 3.89; N, 6.96%. FT IR (ʋ, cm-1: 1620 (HC=N), 1204 and 1161
1
31
(ʋ=N), 958 (P-OAryl). H NMR (, ppm, (CD3)2CO): 8.36 (H-C=N), 8.20-6.70 (Aryl H). P
NMR (, ppm): 8.03 (s).
3.3.5.3. Synthesis of hexa[4-chloro-2-(3,4-bischloro-pheyliminomethyl)phenoxy]
cyclotriphosphazene (2c)
The compound 2c occurred from 3,4-dichloroaniline (0.73 g, 4.50 mmol) as a peach-
orange color solid (0.66g, 91.2%, mp 98 ºC). Anal. Calc. for N9P3C78H42Cl18O6: C, 48.48; H,
2.19; N, 6.52%. Found: C, 49.05; H, 2.51; N, 6.47%. FTIR (ʋ, cm-1): 1620 (HC=N), 1190 and
1162 (P=N), 959 (P-OAryl). 1H NMR (, ppm, (CD3)2CO): 8.35 (H-C=N), 8.00-6.50 (Aryl H).
31P NMR (, ppm): 7.87 (s).
2.4.5.4. Synthesis of hexa[4-chloro-2-(2-mercapto-
pheyliminomethyl)phenoxy]cyclotriphosphazene (2d)
8

The compound 2d occurred from 2-mercapto-aniline (0.50 mL, 4.50 mmol) as a peach-
yellow color solid (0.63 g, 98.3%, mp136 ºC). Anal. Calc. for N9P3C78H54Cl6O6S6: C, 54.74; H,
3.18; N, 7.37: S, 11.24%. Found: C, 55.18; H, 3.22; N, 7.63: S, 12.29%. FTIR (ʋ, cm-1): 1614
1
(HC=N), 1188 and 1163 (P=N), 954 (P-OAryl). H NMR (, ppm, (CD3)2SO): 8.25 (HC=N),
8.0-6.0 (Aryl H), 5.40 (H-S-). 31P NMR (, ppm):7.50 (s).
2.4.5.5. Synthesis of hexa[4-chloro-2-(2-mercapto-benzimidazol-5-
yliminomethyl)phenoxy]cyclotriphosphazene (2e)
The compound 2e occurred from 5-amino-2-mercaptobenzimidazole (0.74g, 4.50 mmol)
as a princeton orange color solid (0.62 g, 85%,
mp 202 ºC). Anal. Calc. for
N21P3C84H54Cl6O6S6: C, 51.70; H, 2.79; N, 15.07: S, 9.86%. Found: C, 49.76; H, 3.62; N,
17.05: S, 12.42%. FTIR (ʋ, cm-1): 3200 (O-H), 1636 (C=N), 1613 (HC=N), 1186, 1158, 1114
1
(P=N), 953 (P-O-Aryl). H NMR (, ppm, (CD3)2SO): 12.0 and 12.5 (N-H and SH), 8.96 (H-
C=N), 8.0-6.4 (Aryl H). 31P NMR (, ppm):7.61 (s).
2.4.5.6. Synthesis of hexa[4-chloro-2-(1H-indazol-6-yl-
iminomethyl)phenoxy]cyclotriphosphazene (2f)
The compound 2f occurred from 6-amino-1H-indazol (0.60 g, 4.50 mmol) as an atomic
tangerine color solid (0.53 g, 80.5%, mp 166 ºC). Anal. Calc. for N21P3C84H54Cl6O6: C, 57.35;
H, 3.09; N, 16.72%. Found: C, 56.14; H, 3.32; N, 17.16: %. FTIR (ʋ, cm-1): 3272 (O-H), 1631
(HC=N), 1608 (HC=N), 1199, 1159 (P=N), 960, 947 (P-O-Aryl). The NMR analysis of the
compound was not performed because insoluble in any solvent, such as (CD3)2CO, CDCl3,
DMSO-D.
2.4.5.7. Synthesis of hexa[4-chloro-2-(fluorine-2-yliminomethyl)phenoxy]cyclotriphosphazene
(2g)
The compound 2g occurred from 2-aminofluorene (0.65 g, 4.50 mmol) as an orange color
solid (0.65 g, 84.9%, mp 130 ºC). Anal. Calc. for N9P3C120H78Cl6O6: C, 70.39; H, 3.84; N,
6.16%. Found: C, 65.62; H, 4.03; N, 5.57 %. FTIR (ʋ, cm-1): 1622 (HC=N), 1194, 1161 (P=N),
9

959 (P-O-Aryl). The NMR analysis of the compound was not performed because insoluble in
any solvent, such as (CD3)2CO, CDCl3, DMSO-D.
2.4.5.8. Synthesis of hexa[4-chloro-2-(4-mercapto-
pheyliminomethyl)phenoxy]cyclotriphosphaze (2h)
The compound 2h occurred from 4-mercapto-phenyl amine (0.50 mL, 4.50 mmol) as a
peach-yellow color solid (0.57 g, 89.0%, mp 185 ºC). Anal. Calc. for N9P3C78H54Cl6O6S6: C,
54.74; H, 3.18; N, 7.37: S, 11.24%. Found: C, 54.01; H, 3.426; N, 6.955; S, 12.18 %. FTIR (ʋ,
cm-1): 1619 (HC=N), 1188, 1158 (P=N), 957 (P-O-Aryl). The NMR analysis of the compound
was not performed because insoluble in any solvent, such as (CD3)2CO, CDCl3, DMSO-D.
2.4.5.9. Synthesis of hexa[4-chloro-2-(4-cyano-pheyliminomethyl)phenoxy]cyclotriphosphaze
(2i)
The compound 2i occurred from 4-cyano-aniline (0.532 g, 4.50 mmol) as a peach-yellow
color solid (0.53 g, 84.8%, mp 167 ºC). Anal. Calc. for N15P3C84H46Cl6O6: C, 60.395; H, 2.756;
N, 12.582%. Found: C, 59.98; H, 3.341; N, 12.37%. FTIR (ʋ, cm-1): 2225 (C≡N), 1624
1
(HC=N), 1192, 1164 (P=N), 958 (P-O-Aryl). H NMR (, ppm, acetone-D): 9.50 (H-C=O,
integral area: 1.0), 8.52 (H-C=N, integral area: 1.13), 8.28 (H-C=N, integral area: 5.44), 8.19-
6.61 (Aryl H). 31P NMR (, ppm): 8.20-8.05 (weak peaks), 7.97 (severe singlet).
2.4.5.10. Synthesis of hexa[4-chloro-(2-(4-carboxy-phenyliminomethyl)phenoxy)]-
cyclotriphosphazene (2j)
The compounds 2j occurred from 4-carboxy-aniline (0.617 g, 4.50 mmol) as a peach-
yellow color solid (0.56 g, 84.0%, mp 213 ºC). Anal. Calc. for N9P3C84H54Cl6O18: C, 56.58; H,
3.05; N, 7.07%. Found: C, 54.26; H, 3.306; N, 6.694%. FTIR (ʋ, cm-1): 1682 (HCOOH), 1624
(HC=N), 1188, 1160 (P=N), 957 (P-O-Aryl). 1H NMR (, ppm, (DMSO): 12.5 (-COOH), 9.72
(H-C=O, integral area: 1.0), 9.63 (H-C=O, integral area: 1.94),8.24 (H-C=N, integral
area:3.10), 8.20 (H-C=N, integral area:1.89), 8.00-6.5 (Aryl H). 31P NMR (, ppm): 7.60
(triplet), 7.43 (medium singlet) and 7.27 (severe singlet).
10

2.4.5.11. Synthesis of 2,2,4,4-tetra[4-chloro-(2-(4-nitro-phenyliminomethyl)phenoxy)]-6,6-
di[4-
chcloro-(2-formyl-phenoxy)]-cyclotriphosphazene (2k).
The compound 2k occurred from 4-nitro-aniline (0.622 g, 4.50 mmol) as a peach-yellow
color solid (0.52 g, 89.7%, mp 173 ºC). Anal. Calc. for N9P3C60H36Cl6O15: C, 50.400; H, 2.520;
N, 8.820%. Found: C, 51.15; H, 3.112; N, 11.98%. FTIR (ʋ, cm-1): 1694 (HC=O), 1627
1
(HC=N), 1188, 1162 (P=N), 955 (P-O-Aryl). H NMR (, ppm, acetone-D): 10.00-9.80 (H-
31
C=O, the integral area: 3.52), 8.60-8.30 (H-C=N, integral area: 3.86), 8.2-6.0 (Aryl H). P
NMR (, ppm): 8.10-7.90 (multiple).
2.4.6. Synthesis of hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene (3) in the presence of
(C2H5)3N
In a 250-mL single-necked flat-bottom flask equipped with magnetic mixing, N3P3Cl6
(1) (1.00 g, 2.876 mmol), THF (150 mL), (C2H5)3N (4.80 mL, 34.512 mmol) and 5-bromo-
salicylaldehyde (6.937 g, 34.512 mmol) were added sequentially. The mixture reaction was
maintained at room temperature for 3 h and then, 31P NMR analysis of the mixture was
performed. From this analysis, it became clear that the reaction was over. At the end of the
reaction, the insoluble matter of the reaction mixture was filtered off (with produced
(C2H5)3N.HCl). The filtered triethylamine hydrochloride [(C2H5)3N.HCl] was dried under room
conditions and weighed (experimental/calculated: 2.20 g / 2.38 g). The solution was
concentrated under reduced pressure. Then, the residue was dropped into solvent of ethyl
alcohol. The white powder was collected by filtration. In this way, the compound 3 was
achieved as a white solid and pure (81.4% yield, 3.10 g, mp 172 ºC). Anal. Calcd for
N3P3C42H24Br6O6: C, 37.79; H, 1.81; N, 3.5%. Found: C, 38.60; H, 2.03; N, 3.23%. FTIR (ʋ,
1
cm-1): 1703 and 1960 (HC=O), 1204, 1190, 1176, 1171 (P=N), 978, 962, 952 (P-O-Aryl). H
NMR (, ppm, (CD3)2CO): 10.0 (s, HC=O), 8.0-7.0 (Aryl H). 31P NMR (, ppm): 7.58 (s).
2.4.7. Synthesis of hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene (3) in the presence of
11

K2CO3
In a 100-mL single-necked flat-bottom flask equipped with magnetic mixing, N3P3Cl6
(1) (0.25 g, 0,719 mmol), THF (75 mL), K2CO3 (1.20 g, 8.629 mmol) and 5-bromo-
salicylaldehyde (1.734 g, 8.629 mmol) were added sequentially. The mixture reaction was
maintained at room temperature for 3 h and then, 31P NMR analysis of the mixture was
performed. From this analysis, it became clear that the reaction was over. At the end of the
reaction, the insoluble matter of the reaction mixture was filtered off ((with K2CO3, produced
KCl and KHCO3).). The solution was concentrated under reduced pressure. Then, the residue
was dropped into solvent of ethyl alcohol. The white powder was collected by filtration. In this
way, the compound 3 was achieved as a white solid and pure (80% yield, 0.77 g, mp 172 ºC).
Anal. Calcd for N3P3C42H24Br6O6: C, 37.79; H, 1.81; N, 3.5%. Found: C, 38.60; H, 2.03; N,
3.23%. FTIR (ʋ, cm-1): 1703 and 1960 (HC=O), 1204, 1190, 1176, 1171 (P=N), 978, 962, 952
1
31
(P-O-Aryl). H NMR (, ppm, (CD3)2CO): 10.0 (s, HC=O), 8.0-7.0 (Aryl H). P NMR (,
ppm): 7.58 (s).
2.4.8. Synthesis of the compound (5) in the presence of K2CO3 for 24 h
In a 250-mL single-necked flat-bottom flask equipped with magnetic mixing, N3P3Cl6 (1)
(0.25 g, 0,719 mmol), THF (75 mL), K2CO3 (1.20 g, 8.629 mmol) and 5-bromo-
salicylaldehyde (1.734 g, 8.629 mmol) were added sequentially. The mixture reaction was
maintained at room temperature for 24 h. At the end of the reaction, the insoluble matter of the
reaction mixture was filtered off (with K2CO3, produced KCl and KHCO3). The solution was
concentrated under reduced pressure. Then, the residue was dropped into solvent of ethyl
alcohol. The black powder was collected by filtration. In this way, the compound 5 was
achieved as a black solid. FTIR (ʋ, cm-1): 1689, 1682, 1649, 1632 (HC=O), 1198, 1178, 1166,
1
1153 (P=N), 957, 943, 925 (P-O-Aryl). H NMR (, ppm, (CD3)2CO): 10.50-9.900 (HC=O),
8.0-6.50 (Aryl H). 31P NMR (, ppm): 10.20 (doublet), -0.50 (triplet).
2.4.9. Synthesis of hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene (3) in the presence of
12

(C2H5)3N for 24 h
In a 250-mL single-necked flat-bottom flask equipped with magnetic mixing, N3P3Cl6
(1) (1.00 g, 2.876 mmol), THF (150 mL), (C2H5)3N (4.80 mL, 34.512 mmol) and 5-bromo-
salicylaldehyde (6.937 g, 34.512 mmol) were added sequentially. The mixture reaction was
maintained at room temperature for 24 h. At the end of the reaction, the insoluble matter of the
reaction mixture was filtered off (with produced (C2H5)3N.HCl). The filtered triethylamine
hydrochloride [(C2H5)3N.HCl] was dried under room conditions and weighed
(experimental/calculated: 2.20 g / 2.38 g). The solution was concentrated under reduced
pressure. Then, the residue was dropped into solvent of ethyl alcohol. The white powder was
collected by filtration. In this way, the compound 3 was achieved as a white solid and pure
(81.4% yield, 3.10 g, mp 172 ºC).
2.4.10. General synthetic procedure for the compounds 3a-3k from the compound 3
In a 100-mL single-necked flat-bottom flask equipped with magnetic mixing, the
compound 2 (0.40 g, 0.375 mmol), THF (30 mL), two drops of formic acid and primary amine
derivative (4.50 mmol) were added sequentially. The reaction was continued for 24 hours under
room conditions. After the solution was reduced to approximately 5 mL under reduced
pressure, the solution was dropped into diethyl ether or alcohol for the removal of free primary
amine. The precipitate was filtered off and the color solid was dried under room conditions.
The compounds 3a-3k were obtained from the compound 3.
2.4.10.1. Synthesis of hexa[4-bromo-2-(phenyliminomethyl)phenoxy]cyclotriphosphazene (3a)
The compound 3a occurred from aniline (0.41 mL, 4.50 mmol) as a Peach-orange color
solid (0.47 g, 87.9%, mp. 192ºC). Anal. Calc. for N9P3C78H54Br6O6: C, 52.46; H, 3.05; N,
7.06%. Found: C, 52.75; H, 3.44; N, 7.27%. FTIR (ʋ, cm-1): 1619 (HC=N), 1186, 1161 (P=N),
1
971, 955, 938 (P-O-Aryl). H NMR (, ppm, (CD3)2CO): 8.34 (H-C=N), 8.25-6.70 (Aryl H).
31P NMR (, ppm): 7.90 (s).
2.4.10.2. Synthesis of hexa[4-bromo-2-(1-naphthyliminomethyl)phenoxy]cyclotriphosphazene
13

(3b)
The compound 3b occurred from 1-naphthylamine (0.65 g, 4.50 mmol) as a maize color
solid (0.58 g, 92.8%, mp. 146 ºC). Anal. Calc. for N9P3C102H66Br6O6: C, 58.73; H, 3.19; N,
6.04%. Found: C, 58.76; H, 3.44; N, 6.19%. FTIR (ʋ, cm-1): 1619 (HC=N), 1201, 1162 (P=N),
1
957 (P-O-Aryl). H NMR (, ppm, (CD3)2CO): 8.35 (H-C=N), 8.25-6.60 (Aryl H), 2.84
(strong, H2O), 2.05 (strong, (CD3)2CO) .31P NMR (, ppm): 8.75 (s).
2.4.10.3. Synthesis of hexa[4-bromo-2-(3,4-bischloro-pheyliminomethyl)phenoxy]
cyclotriphosphazene (3c)
The compound 3c occurred from 3,4-dichloroaniline (0.73 g, 4.50 mmol) as a peach-
orange color solid (0.56 g, 85.0%, mp. 125 ºC). Anal. Calc. for N9P3C78H42Cl6Br6O6: C, 42.60;
H, 1.93; N, 5.73%. Found: C, 43.00; H, 2.23; N, 5.83%. FTIR (ʋ, cm-1): 1622 (HC=N), 1188,
1
1162 (P=N), 957 (P-O-Aryl). H NMR (, ppm, (CD3)2CO): 8.33 (H-C=N), 8.15-6.90 (Aryl
H), 2.84 (strong, H2O), 2.05 (strong, (CD3)2CO) .31P NMR (, ppm): 7.64 (s).
2.4.10.4. Synthesis of hexa[4-bromo-2-(2-mercapto-pheyliminomethyl)phenoxy]
cyclotriphosphazene (3d)
The compound 3d occurred from 2-mercapto-aniline (0.50 mL, 4.50 mmol) as a peach-
yellow color solid (0.48 g, 81.0%, mp. 235 ºC). Anal. Calc. for N9P3C78H54S6Br6O6: C, 47.36;
H, 2.75; N, 6.37; S, 9.73%. Found: C, 48.68; H, 3.28; N, 6.68; S, 9.81%. FTIR (ʋ, cm-1): 1608
1
(HC=N), 1215, 1167 (P=N), 945 (P-O-Aryl). H NMR (, ppm, (CD3)2SO): 7.57 (H-C=N),
7.00-6.30 (Aryl H), 5.36 (H-S-), 2.47 ((CD3)2SO), 3.40 (H2O). 31P NMR (, ppm): 8.96 (s).
2.4.10.5. Synthesis of hexa[4-bromo-2-(2-mercapto-benzimidazol-5-yliminomethyl)phenoxy]
cyclotriphosphazene (3e)
The compound 3e occurred from 5-amino-2-mercaptobenzimidazole (0.74g, 4.50 mmol)
as a princeton orange color solid (0.60 g, 90.2%, mp. 278 ºC). Anal. Calc. for
N21P3C84H54S6Br6O6: C, 45.48; H, 2.45; N, 13.26; S, 8.67%. Found: C, 40.76; H, 3.18; N,
12.44; S, 7.92%. FTIR (ʋ, cm-1): 3119 (O-H), 1635 (C=N), 1614 (HC=N), 1218, 1202, 1161
14

1
(P=N), 974, 959 (P-O-Aryl). H NMR (, ppm, (CD3)2SO): 12.5 (N-H ve SH), 8.08 and 7.80
(H-C=N), 7.20-6.50 (Aryl H). 31P NMR (, ppm): 7.48 (s).
2.4.10.6. Synthesis of hexa[4-bromo-2-(1H-indazol-6-yl-iminomethyl)phenoxy]
cyclotriphosphazene (3f)
The compound 3f occurred from 6-amino-1H-indazol (0.60 g, 4.50 mmol) as tangerine
color solid (0.53 g, 87.5%, mp. 168 ºC). Anal. Calc. for N21P3C84H54Br6O6: C, 49.80; H, 2.69;
N, 14.52%. Found: C, 49.66; H, 3.34; N, 15.03%. FTIR (ʋ, cm-1): 3211 (O-H), 1631 (HC=N),
1608 (HC=N), 1199, 1159 (P=N), 960, 947 (P-O-Aryl). The NMR analysis of the compound
was not performed because insoluble in any solvent, such as (CD3)2CO, CDCl3, DMSO-D.
2.4.10.7. Synthesis of hexa[4-bromo-2-(fluorine-2-yliminomethyl)phenoxy]cyclotriphosphazene
(3g)
The compound 3g occurred from 2-aminofluorene (0.65 g, 4.50 mmol) as an orange color
solid (0.61 g, 88.0%, mp. 183 ºC). Anal. Calc. for N9P3C120H78Br6O6: C, 62.28; H, 3.40; N,
5.25%. Found: C, 51.14; H, 3.62; N, 5.08%. FTIR (ʋ, cm-1): 1622 (HC=N), 1213, 1196, 1161
(P=N), 966, 955, 942 (P-O-Aryl). The NMR analysis of the compound was not performed
because insoluble in any solvent, such as (CD3)2CO, CDCl3, DMSO-D.
2.4.10.8. Synthesis of hexa[4-bromo-2-(4-mercapto-pheyliminomethyl)phenoxy]
cyclotriphosphaze (3h)
The compound 3h occurred from 4-mercapto-phenyl amine (0.50 mL, 4.50 mmol) as a
peach-yellow color solid (0.50 g, 84.4%, mp. 238 ºC). Anal. Calc. for N9P3C78H54S6Br6O6: C,
47.36; H, 2.75; N, 6.37; S, 9.73%. Found: C, 47.45; H, 2.881; N, 6.022; S, 10.24%. FTIR (ʋ,
cm-1): 1619 (HC=N), 1191, 1160 (P=N), 958 (P-O-Aryl). The NMR analysis of the compound
was not performed because insoluble in any solvent, such as (CD3)2CO, CDCl3, DMSO-D.
2.4.10.9. Synthesis of hexa[4-bromo-2-(4-cyano-pheyliminomethyl)phenoxy]cyclotriphosphaze
(3i)
15

The compound 3i occurred from 4-cyano-aniline (0.532 g, 4.50 mmol) as a peach-yellow
color solid (0.50 g, 86.2%, mp. 164 ºC). Anal. Calc. for N15P3C84H48Br6O6: C,52.07; H, 2.480;
N, 10.85%. Found: C, 53.32; H, 2.976; N, 12.34%. FTIR (ʋ, cm-1): 2215 (C≡N), 1612 (HC=N),
1
1190, 1161 (P=N), 954 (P-O-Aryl). H NMR (, ppm, acetone-D): 8.53-8.25 (H-C=N), 8.13-
6.61 (Aryl H). 31P NMR (, ppm): 8.00-7.85 (weak peaks), 7.75 (server singlet).
2.4.10.10. Synthesis of hexa[4-bromo-(2-(4-carboxy-phenyliminomethyl)phenoxy)]
cyclotriphosphazene (3j)
The compound 3j occurred from 4-carboxy-aniline (0.617 g, 4.50 mmol) as a peach-
yellow color solid (0.55 g, 89.6%, mp. 216 ºC). Anal. Calc. for N9P3C84H54Br6O18: C, 49.22; H,
2.66; N, 6.15%. Found: C, 48.08; H, 2.915; N, 6.105%. FTIR (ʋ, cm-1): 1682 (HCOOH), 1624
1
(HC=N), 1188, 1160 (P=N), 957 (P-O-Aryl). H NMR (, ppm, DMSO): 12.12 (-COOH),
8.28-82.0 H-C=N, weak multi peaks), 7.7-6.0 (Aryl H). 31P NMR (, ppm): 7.50 (weak triplet),
7.26 (medium singlet), 7.11 (server singlet).
2.4.10.11. Synthesis of 2,2,4-tri[4-bromo-(2-(4-nitro-phenyliminomethyl)phenoxy)]-4,4,6-tri[4-
bromo-(2-formyl-phenoxy)]cyclotriphosphazene (3k)
The compound 3k occurred from 4-nitro-aniline (0.622 g, 4.50 mmol) as a peach-yellow
color solid (0.43 g, 84.3%, mp. 167 ºC). Anal. Calc. for N9P3C60H36Br6O15: C, 42.470; H,
2.123; N, 7.432%. Found: C, 44.93; H, 2.884; N, 10.79%. FTIR (ʋ, cm-1): 1690 (ʋHC=O),
1
1624 (HC=N), 1185, 1162 (P=N), 952 (P-O-Aryl). H NMR (, ppm, acetone-D): 10.00-9.80
(three peaks, H-C=O, the sum of the integral area of peaks: 2.01), 8.60-8.20 (multi-peak, H-
C=N, the sum of integral area: 2.57), 8.13-6.00 (Aryl H). 31P NMR (, ppm): 8.00-7.70
(multiplet).
3. Results and discussion
3.1.
Synthesis
16

In our previous study, hexa(4-chloro-2-formyl-phenoxy)cyclotriphosphazene (2) and
hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene (3) were derived in 59% and 80% yield
from the reaction of hexachclorocyclotriphosphazene (1) with 5-chloro-2-hydroxy-
benzaldehyde in the presence of K2CO3 and 5-bromo-2-hydroxy-benzaldehyde in the presence
of (C2H5)3N under Ar atmosphere, sequentially [13]. In the present study, the same reactions
were carried out separately for the derivation of the compounds 2 and 3 in the presence of both
K2CO3 and (C2H5)3N without using Ar or N2 atmosphere. The synthesis reactions of the
compounds (2-5) were performed as seen in Schemes 1-3. All these reactions were followed by
31P NMR spectroscopy to determine the replacement of all the chlorine atoms in the compound
31
1. While the reactions were continuing, the first P NMR analysis was performed for 3 hours
31
after the reactions begun. The PNMR spectra of all the mixtures showed only one signal
supporting the hexasubstitution on the cyclotriphosphazene ring. Thus, it was decided that the
replacement of all the chlorine atoms in the compound 1 is over and the purification process
was started.
X
O
O
X
Cl
Cl
Cl
Cl
X
O
O
N
P
N
P
O
P
P
THF
O
O
O
P
P
6 BASE
6 X
OH
+
+
N
N
room condition,
3 h
N
N
Cl Cl
O
X
X
O
O
1
2
3
X: Cl( ), Br( )
BASE
O
O
X
(C2H5)3N
K2CO3
2
3
Comp. and
2
Yield of the comp.
Yield of the comp.
:
:
81.4%
81.4%
52%
80%
3
Scheme 1. The Clear Structures and the Synthetic Route of the Compounds 2 and 3 for 3 h in
the
Presence of a Base
Moreover, these reactions were continued for 24 h in the presence of K2CO3 and (C2H5)3N.
While compounds 2 and 3 cannot be obtained in the presence of K2CO3 (Scheme 3), it is
17

determined that the compounds 2 and 3 occurred in good yields in the presence of (C2H5)3N
(Scheme 2). The compounds 4 and 5 are estimated to consist of coordination between
compounds 2 and 3 and K2CO3 and three different structures (A, B and C) were proposed for
the compound 4 and 5, too (Scheme 3). The structures of the obtained compounds 4 and 5 are
one of three different structures proposed. The exact structure of the compounds 4 and 5 were
not characterized because our goal was to obtain the compounds 2 and 3. Unlike this study,
although the reactions between the compound 1 and some formyl substituted phenol derivatives
such as 4-formyl-phenol, 2-formyl-phenol and 4-formyl-2-methoxy-phenol were sustained for
24 hours in the presence of K2CO3, the organocyclotriphosphazenes bearing six formyl groups
(such as the compounds 2 and 3) were obtained with high yield as pure. [13, 16]. Compared the
results of this and similar studies in the literature, it is the right decision to conclude that the
proposed coordination for the compounds 4 and 5 occurs between the metal (K+) and halogen
(Cl, Br), which depend on a phosphorus in the cyclotriphosphazene ring. Doublet and triplet
31
peaks in the P NMR spectra of the compounds 4 and 5 also support this assessment. This
result defined from two studies is quite interesting information for phosphazene chemistry.
X
O
O
X
Cl
Cl
Cl
Cl
X
O
O
N
P
N
P
O
P
P
THF
O
O
O
P
P
6 (C2H5)3N
X
OH
6
+
+
N
N
room condition,
24 h
N
N
Cl Cl
O
X
X
O
O
1
2
3
X: Cl( ), Br( )
O
O
X
2
3
Comp. and
(
81% yield)
Scheme 2. The clear structures and the synthesis route of the compounds 2 and 3 for 24 h in the
presence of (C2H5)3N
18

X
O
O
X
O
O
X
N
O
O
O
O
P
P
A
N
N
P
X
X
O
O
K+
O
O
X
X
K+
O
O
X
O
O
X
N
O
Cl
Cl
Cl
Cl
O
O
O
P
P
N
P
P
P
THF
B
N
N
X
OH
6
6 K2CO3
+
+
N
N
P
room condition,
24 h
X
X
O
O
Cl Cl
K+
O
1
X: Cl(4), Br(5)
O
O
X
X
O
O
X
O
O
X
N
O
C
O
O
O
P
P
K+
N
N
P
X
X
O
O
O
O
X
Comp. 4 and 5
Scheme 3. The Predicted Structures (A, B and C) and the Synthesis Pathway of the
Compounds 4 and 5 for 24 h in the Presence of K2CO3
To determine whether hexachlorocyclotriphosphazene is hydrolysis at THF, the solution
of hexachlorocyclotriphosphazene in THF solvent was stirred with a magnetic mixer for 24
hours under room conditions as we perform the reactions. At the end of this period, 1H and 31P
1
NMR analysis of the mixture and H NMR analysis of THF was carried out. Two sharp peaks
1
at 3.62 and 1.73 ppm were detected in the H NMR spectrum of the compound 1 solution.
These two peaks were determined to belong to –CH2- protons in THF because these two peaks
1
1
were also seen in the THF H NMR spectrum. That is, the same peaks were seen in both H
31
NMR spectra. One sharp peaks at 19.84 ppm were detected in the P NMR spectrum of the
compound 1 solution. This peak value has the same value as the peak of
hexachlorocyclotriphosphazene. As a result of these analyses, it was concluded that there was
no hydrolysis of hexachlorocyclotriphosphazene in THF solvent under room conditions.
19

For the derivation of new organocyclotriphosphazenes containing six imine groups, 1
equiv. of the compounds 2 and 3 were treated with 12 equiv. of aniline (a) and some aniline
derivatives (b-k) in THF in room conditions without using Ar or N2 atmosphere. Several drops
of formic acid were used as a catalyst to make quickly these reactions. Although the excessive
amounts of the selected primary amines were used in all the reactions, the
organocyclotriphosphazene containing six imine groups did not occur from only 4-nitro-aniline
(k) (Scheme 4 and 5). In previously our study, the organocyclotriphsophazene derivatives
containing both formyl and Schiff base groups were firstly identified to occur from the
reactions of hexa(4-formyl-pheoxy)cyclotriphosphazene and hexa(4-formyl-2-metoxy-
pheoxy)cyclotriphosphazene with 4-cyano-aniline and 4-aminobenzoic acid [13]. 4-nitro-
aniline was never used in previously our works and the others works in the literature. Unlike
our previous work, the formation of the organocylotriphosphazene derivatives bearing six
Schiff base groups from 4-cyano-aniline and 4-amino-benzoic acid in the current study is a
very interesting result. The structures of the synthesized organocyclotriphospahzene derivatives
13
31
were determined using FTIR, NMR (1H, C and P) and elemental analyses as described in
the experimental section. The results obtained in the elemental analyses of all the compounds
support the proposed structures.
20

Ar
Ar
X
X
N
X
N
X
O
O
O
O
X
O
O P
O
P O
X
N
P
N
P
N
O
P
P
O
N
THF
O
Ar
N
N
O
6
Ar NH
+
N
N
2
Ar
2 drops of formic acid
room condition,
24 h
X
O O
X
O
O
X
O
X
Ar
N
O
N
Ar
X: Cl(2), Br(3)
X
2a-2j
3a-3j
X
Comp. 2, 3
CH
CH
3
CH
3
3
CH
3
H N
HS
Cl
N
2
Ar:
SH
N
H
Cl
a
b
e
c
d
CH
CH
CH
3
3
3
N
NH
2
N
H
H3C
C
SH
OH
O
N
g
h
f
j
i
Scheme 4. The clear structures and the reaction equation for organocyclotriphosphazenes
carrying six imine
X
Ar
X
X
O
X
O
N
O
O
O
X
N
P
O
O P
O
P O
X
N
P
O
P
P
O
N
Ar
THF
O
O
O
6
Ar
NH
N
N
+
N
N
2
2 drops of formic acid
room condition,
24 h
X
O O
O
O
X
O
X
X
O
Ar
N
O
X: Cl(2), Br(3)
X
O
X
2k, 3k
N
NH2
Ar:
Comp. 2, 3
O
k
Scheme 5. The clear structures and the reaction equation for organocyclotriphosphazenes
carrying both three imine and three formyl groups
3.2.
Characterization
21

The characteristic P=N, HC=O, P-OAr absorption peaks for the compounds (2, 3, 4 and
5) were appeared and detected in the FTIR spectra (Fig 1 and Fig 2). These peaks in Fig. 1 ve
Fig. 2 spectra are seen as distinct from each other. While HC=O absorption for the compounds
2 and 3 were shown at 1698 -1678 cm-1 and 1702-1689 cm-1 as the double peaks in the FTIR
spectra (Fig. 1), the same peak for the compounds 4 and 5 were observed in the range 1690-
1630 cm-1 as multi-peaks (Fig. 2). Comparing the FTIR spectra in Fig. 1 and Fig. 2, it was
clearly understood that the compounds (2-3) and the compounds (4-5) differ from their spectra.
Hence, it was determined that the compounds (4-5) were a phenoxy substituted
organophosphazene derivatives bearing formyl groups, but were not pure. The characteristic
peak in the region of 3400 cm-1 for free Ph-OH was not seen in the spectra of the compounds (2
and 3). In the FTIR spectra of the compounds (2-3), the characteristic absorption peaks due to
P=N and P-O-Ar appeared in the region of 1200-1150 cm−1 and 960-940 cm−1, respectively.
While the FTIR spectra of all the compounds (2a-2j and 3a-3j) exhibit characteristic
peaks attributed to C=N, P=N and P-OAryl, the characteristic peak in the region of 1700-1680
cm-1 for C=O have vanished. The absence of the peak for C=O showed that six formyl groups
of the compounds (2 and 3) react with primary amines (a-j). This result is one of the most
important indication for the formation of these organocyclotriphosphazene derivatives
containing six imine groups. In the FTIR spectra (Fig. 3) of the compounds 2k and 3k, in
addition to the characteristic C=N, P=N and P-O-Ar stretching vibrations were observed a peak
in the range 1700-1680 cm-1. This peak corresponds to the stretching vibrations of the HC=O
bond. Therefore, both formyl and imine groups exist in the structures of the compound 2k and
3k. The FTIR spectra of all the compounds (2a-2k and 3a-3k) were not observed two bands at
around 3300 cm-1 for free primary amine due to N-H stretching vibrations.
1
31
Both H and P NMR spectroscopies are the most important methods for verifying the
1
correct structure of the compounds synthesized in this study. From H NMR spectra of
compounds 2 and 3, all peaks corresponding to organic groups bound to the phosphazene ring
22

were identified. Three peaks belonging to all aromatic protons for the compounds 2 and 3 in the
spectrum were observed in the range of 8.00−7.00 ppm, which is a typical region for the
benzene rings. Additionally, the characteristic proton peak of aldehyde groups (H-C=O) were
observed at 10.00 ppm as a singlet. No other proton peaks have been detected in the spectra. In
1
the H NMR spectra of the compounds 4 and 5, the proton peak of the aldehyde groups were
observed at around 10.00 ppm as two signals (Fig. 4). The results of this analysis showed that
the structures of the compounds (2, 3) and the compounds (4, 5) synthesized at different
periods under the same reaction conditions were different.
The most important information about the structure of the compounds (2a-2k, 3a-3k)
derived from aniline and aniline derivatives were obtained from 1H NMR spectroscopy, expect
2f-2g and 3f-3g. Since 1H NMR spectra of the compounds (2f-2g and 3f-3g) are not taken, the
evaluations are not for these compounds. The signals of all the aromatic protons of these
compounds appeared in the region 8.20-6.50 ppm. In their spectra, the signal belonging to the
1
imine and formyl group are the most characteristic peaks. In the H NMR spectra of the
compounds (2a-2j, 3a-3j) bearing six Schiff base groups, the imine proton peak for these
compounds were observed in the range 8.30-8.10 ppm as a singlet. However, the proton signal
of aldehyde groups was not seen at around 10.00 ppm in the same spectra, expect the
compounds 2i, 2j, 3i and 3j. The spectra of four compounds appeared fairly weak proton peak
1
corresponding to aldehyde, according azomethine proton peak. In the H NMR spectra of the
compounds (2k and 3k), the characteristic peaks belonging to both aldehyde and Schiff base
groups were determined at 8.30-8.10 ppm and 10.00-9.50 ppm, respectively. The structure of
the compounds (2k and 3k) were also confirmed by obtaining ratios of the integrals of the
signals corresponding to the two functional groups. The ratio of the integral area of the proton
peaks (HCN/HCO) for the compounds 2k and 3k are 3.86/3.52:1.09 and 2.57/2.10:1.27. The –
NH2 protons were not observed between 6.0 and 5.0 ppm in all the spectra of the compounds
(2a-2k, 3a-3k).
23

31
While the proton-decoupled P NMR spectra of the compounds 2 and 3 derived for 3
hours in the presence of K2CO3 and (C2H5)3N and 24 hours in the presence of (C2H5)3N were
observed a singlet peak at 7.81 and 7.58 ppm, the signals were appeared a doublet at 10.0 and a
triplet at -1.0 ppm in the 31P NMR spectra of the compounds 4 and 5 derived for 24 hours in the
31
presence of K2CO3 (Fig 6). The P NMR spectra of the compounds 4 and 5 exhibit A2X type
spin system due to two different phosphorus environments. The 31P NMR spectra of the
compounds (2a-2j and 3a-3j) consist of only a sharp peak between 7.0 and 8.0 ppm for the
connection of the same substituents on phosphazene ring. However, the 31P NMR spectra of the
compounds (2k and 3k) were appeared multiplet peaks in the region 7.0-8.5 ppm because
different phosphorus environments (Fig. 7). Since the signals belonging to phosphors in the
compounds (2k and 3k) appear in very small chemical shift ranges, it is not possible to suggest
the explicit structure of these compounds from these signals. As noted, it is easily determined
from these signals that the phosphors in these compounds do not have the same chemical
environment.
4. Conclusions
In this study, we identified valuable and very interesting results for phosphazene
chemistry. The simplest of these, organocyclotriphosphazenes, which carry six formyl groups
from hydroxybenzaldehyde derivatives, were found to form at good yield even under mild
conditions without the use of an Ar or N2 atmosphere. We found the same result in our previous
work. The another, it is determined that organocyclotriphosphazene derivatives containing six
fromyl groups from 5-chlorosalicylaldehyde and 5-bromosalicylaldehyde occur within 3 h in
the presence of both K2CO3 and (C2H5)3N. If the reaction is to continue for 24 h in the presence
of K2CO3, it is not possible to obtain organocyclotriphosphazene derivatives containing six
formyl groups as pure. When (C2H5)3N was used as a base in this reaction, derivatives of
organocyclotriphosphazene containing six formyl groups are obtained, whether the reaction
24

time is 3 h or 24 h. This second result applies for only 5-chlorosalicylaldehyde and 5-
bromosalicylaldehyde. Therefore, if the reactions between hexacholorocylotriphosphazene and
31
organic nucleophiles are monitored by P NMR analysis, the waste of time and energy is
avoided for the synthesis of organocyclotriphosphazene derivatives.
The organocyclotriphosphazene derivatives derived from 5-chlorosalicylaldehyde and 5-
bromosalicylaldehyde were reacted with aniline and selected aniline derivatives for the
organocyclotriphosphazene derivatives containing six imine groups. The selected aniline
derivatives include some organic structures such as aromatic, heterocyclic, –CN, -COOH, -
NO2, SH and Cl. Although the excess of all the primary amine was used in the reaction, it was
determined that it was composed of organophosphazene derivatives which carries both formyl
and imine groups from alone 4-nitro-aniline. According to the results determined from this and
previous studies, it was determined that both organophosphazene derivatives bearing six formyl
groups and primary amine will affect the structure of the organophosphazene derivatives to
occur from the reactions between the organophosphazene derivative containing six formyl units
and the primary amine. This result is the other most important information that we have
identified for phosphazene chemistry in this study.
Acknowledgements
The authors acknowledge the “Scientific and Technical Research Council of Turkey”
(107T407) and Harran University Scientific Research Fund for Support (13123).
References
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26

Graphical Abstract
ORGANOCYCLOTRIPHOSPHAZENES WITH POLY SCHIFF BASES
X
X
O
O
O
O
X
N
P
O
P
P
O
O
O
ORGANOCYCLOTRIPHOSPHAZENES WITH POLY ALDEHYDES
N
N
X
O
O
O
O
X
O
X
X
OH
X
O
O
O
X
N
P
Other Selected
Aniline Derivatives
O
O
O
P
N
P
N
O
O
X
H2N
NO2
THF
X
X
Ar
X
O
O
(C2H5)3N
Ar
O
O
X
N
X Ar
X
Cl
Cl
Cl
Cl
X
N
3 h
O
N
P
X
X
K2CO3
K2CO3
O
O
O
O
O
X
N
P
N
P
N
O
O
O
N
P
N
P
N
3 h
O
O
O
X
N
P
(C2H5)3N
O
O
O
Ar
X
P
24 h
N
P
P
P
O
Ar
N
O O
X
O
P
P
X
X
O
O
N
O
O
X
N
N
N
N
N
Cl Cl
24 h
O
O
O
O
X
X
O
O
Ar
X
O
O
X
N
N
X
K+
O
O
P
P
X
O
O
Ar
N
N
Ar
N
P
N
X
X
X
O
O
X
2k, 3k
Ar
2a-2j and 3a-3j
O
O
X
27

Highlights
When the reactions of hexacholorocyclotriphosphazene are also performed under room
conditions, expected organocyclotriphosphazene derivatives is obtained with very good
efficiency.
There is no need to provide airless media in reactions of hexacholorocyclotriphosphazene with
nucleophiles, except for organometallic compounds.
The reactions between hexacholorocyclotriphosphazene and nucleophiles should be monitored
by 31P NMR spectroscopy and the reaction should be completed according to the results of this
analysis.
The formation of organocyclotriphosphazene derivatives bearing six Schiff base depends on the
structures of the aniline derivative and organocyclotriphosphazene derivatives containing six
imines.
28