Synthesis and characterization of alkyl- and acyl-substituted oxime-phosphazenes

Article abstract of DOI:10.1139/v05-223

Two oxime-cyclophosphazenes were prepared from the hexakis(4-formylphenoxy) cyclotriphosphazene (2) and hexakis(4-acetylphenoxy)cyclotriphosphazene (8). The reactions of these oximes with ethyl bromide, allyl bromide, propanoyl chloride, and acriloyl chlo

Full text of DOI:10.1139/v05-223

2039
Synthesis and characterization of alkyl- and acyl-
substituted oxime–phosphazenes
Erol Çil, Mustafa Arslan, and Ahmet Orhan Görgülü
Abstract: Two oxime–cyclophosphazenes were prepared from the hexakis(4-formylphenoxy)cyclotriphosphazene (2)
and hexakis(4-acetylphenoxy)cyclotriphosphazene (8). The reactions of these oximes with ethyl bromide, allyl bromide,
propanoyl chloride, and acriloyl chloride were studied. Hexasubstituted compounds were obtained from the reactions of
hexakis{4-[(hydroxyimino)methyl]phenoxy}cyclotriphosphazene (3) with ethyl bromide (4), allyl bromide (5), and pro-
panoyl chloride (6), however, the oxime groups on 3 rearranged to nitrile (7) in the reaction of 3 with acriloyl chloride.
Hexasubstituted compounds were also obtained from the reactions of hexakis{4-[(1)-N-hydroxyethaneimidoyl]phen-
oxy}cyclotriphosphazene (9) with allyl bromide (11) and propanoyl chloride (12). Tetra- and penta-substituted products
were obtained from the reactions of 9 with ethyl bromide (10) and acriloyl chloride (13), respectively. All products
1
were generally obtained in high yields. The structures of the compounds were defined by elemental analysis, IR, H,
13C, and 31P NMR spectroscopy.
Key words: hexachlorocyclotriphosphazene, phosphazene, oxime, oxime derivatives, oxime–phosphazenes.
Résumé : On a préparé deux oximes de cyclophosphazènes à partir de l’hexakis(4-formylphénoxy)cyclotriphosphazène
(2) et de l’hexakis(4-acétylphénoxy)cyclotriphosphazène (8). On a étudié les réactions de ces oximes avec le bromure
d’éthyle, le bromure d’allyle, le chlorure de propanoyle et le chlorure d’acryloyle. Les réactions de l’hexakis{4-[(hy-
droxyimino)méthyl]phénoxy}cyclotriphosphazène (3) avec le bromure d’éthyle (4), le bromure d’allyle (5) et le chlo-
rure de propanoyle (6) conduit à la formation de produits hexasubstitués; toutefois, par réaction avec le chlorure
d’acryloyle, les groupes oximes du composé 3 se réarrangent en nitrile (7). On a aussi obtenu des produits hexasubsti-
tués lors des réactions de l’hexakis{4-[(1)-N-hydroxyéthaneimidoyl]phénoxy}cyclotriphosphazène (9) avec le bromure
d’allyle (11) et le chlorure de propanoyle (12). Les réactions du composé 9 avec le bromure d’éthyle (10) et le chlo-
rure d’acryloyle (13) conduisent respectivement à des produits tétra- et pentasubstitués. Tous les produits ont générale-
ment été obtenus avec des rendements élevés. Les structures des composés ont été définies par des analyses chimiques
1
et par les spectroscopies IR et RMN du H, 13C et 31P.
Mots clés : hexachlorocyclotriphosphazène, phosphazène, oxime, dérivés d’oximes, oxime de phosphazène.
[Traduit par la Rédaction] Çil et al. 2045
Introduction
polyphosphazenes, starting materials for the preparation of
cyclolinear and (or) cyclomatrix phosphazene substrates,
commercial polymers with carbon backbones containing
pending cyclophosphazene groups, inorganic hydraulic flu-
ids and lubricants, biologically important substrates such as
anticancer agents, insect chemosterilants, pesticides and fer-
tilizers, supports for catalysts, dyes, and crown ether phase-
transfer catalysts for nucleophilic substitution reactions, core
substrates for dendrimers, thermal initiators for anionic
polymerization reactions, and photosensitive materials (16).
The literature contains reports on the synthesis of different
linear, cyclic or polyphosphazenes (17–27). There are also a
large number of literature reports on reactions of the func-
tional groups on phosphazene substituents (10, 28). Typical
of these include coupling reactions of trimeric phosphazene
azides with aryloxy, alkoxy, and dialkylamino cosubstituents
(29), N-vinylic phosphazenes with azodicarboxylic and
The linear, cyclo- and poly-phosphazenes are the best
known and most intensively studied phosphorus–nitrogen
compounds (1–5). These compounds are reported to possess
interesting biomedical properties and promising applications
(6–9). Phosphazene polymers bearing flouroalkoxy or aryloxy
groups stimulated considerable interest in the past as biolog-
ically inert, water insoluble polymers for blood vessel or
heart valve construction (10). Cyclophosphazene derivatives,
substituted with aziridine groups, were investigated as bio-
medical products because of their strong antitumor activity
(11). Antimicrobial and biological effects of some phospha-
zenes on bacterial and yeast cells have been studied (12–14).
On the other hand, it is known that phosphorus and nitrogen
compounds are effective flame retardants for fibre materials
(15). Some other applications include model compounds for
Received 19 July 2005. Published on the NRC Research Press Web site at http://canjchem.nrc.ca on 28 January 2006.
E. Çil,1 M. Arslan, and A.O. Görgülü. Chemistry Department, Firat University, TR-23169 Elazig, Turkey.
1Corresponding author (e-mail: cilerol@yahoo.com).
Can. J. Chem. 83: 2039–2045 (2005)
doi: 10.1139/V05-223
© 2005 NRC Canada

2040
Can. J. Chem. Vol. 83, 2005
Reaction of 3 with allyl bromide
A solution of 0.50 mL (0.7 g, 5.77 mmol) allyl bromide in
acetone (10 mL), 3 (0.80 g, 0.84 mmol), and K2CO3 (1.60 g,
11.57 mmol) in acetone (30 mL) was used for the prepara-
tion of 5 as for 4. The reflux period was 48 h. The white
solid (5) was recrystallized from alcohol. Yield: 84% (0.85 g).
acetylenic esters (30), polymers from 4-formylphenoxy (31,
32), from maleic (33), and from 3,4-methylenedioxyphenoxy
substituents (34).
In this paper we have prepared oxime–cyclophosphazenes
from hexakis(4-formylphenoxy)cyclotriphosphazene and hexa-
kis(4-acetylphenoxy)cyclotriphosphazene, and studied their
reactions with alkyl and acyl halides such as ethyl bromide,
allyl bromide, propanoyl chloride, and acriloyl chloride.
Reaction of 3 with propanoyl chloride
A solution of 0.40 mL (0.42 g, 4.58 mmol) propanoyl
chloride in acetone (10 mL), 3 (0.60 g, 0.63 mmol), and
Et3N (2 mL) in acetone (30 mL) was used for the prepara-
tion of 6 as for 4. The reaction was carried out at room tem-
perature for 12 h. The white solid (6) was recrystallized
from alcohol. Yield: 74% (0.60 g).
Experimental
General remarks
Solvents and other liquids used in the experimental works
were dried by conventional methods. Hexachlorocyclotri-
phosphazene (N3P3Cl6) (1) was recrystallized from hexane.
Other chemicals were used as purchased. Hexakis(4-formyl-
phenoxy)cyclotriphosphazene (2) and hexakis(4-acetylphen-
oxy)cyclotriphosphazene (8) were prepared as described by
Carriedo et al. (25). The reactions of (N3P3Cl6) with the phe-
nols were carried out under dry nitrogen.
Reaction of 3 with acriloyl chloride
A solution of 0.40 mL (0.44 g, 4.86 mmol) acriloyl chlo-
ride in acetone (10 mL), 3 (0.60 g, 0.63 mmol), and Et3N
(2 mL) in acetone (30 mL) was used for the preparation of 7
as for 4. The reaction was carried out at room temperature
for 12 h. The orange colour solid (7) was washed with alco-
hol. Yield: 94% (0.50 g).
The IR spectra were recorded on an ATI Unicam Mattson
1000 FT IR spectrometer. H, 13C, and 31P NMR spectra
1
Synthesis of compound 8
were recorded using a Bruker DPX-300 spectrometer operat-
1
A mixture of 1 (7.00 g, 20.13 mmol), 4-hydroxyaceto-
phenone (16.72 g, 122.80 mmol), and K2CO3 (34.00 g,
245.99 mmol) was refluxed in acetone (250 mL) for 3 h.
The solvent was evaporated in vacuum and the residue was
extracted with CH2Cl2 (4 × 75 mL). After the evaporation of
the solvent in vacuum, a white solid (8) formed in 87%
(16.50 g) yield.
ing at 300.13, 75.46, and 121.49 MHz, respectively. The H
and 13C NMR chemical shifts were measured using SiMe4 as
an internal standard and the 31P chemical shifts were mea-
sured using 85% H3PO4 as an external standard. Chemical
shifts downfield from the standard were assigned positive δ
values. Microanalysis was carried out by a LECO 932
CHNS-O apparatus.
Synthesis of compound 9
Synthesis of compound 2
Hydroxylaminehydrochloride (4.50 g, 64.75 mmol) and 8
(10.00 g, 10.57 mmol) were used for the preparation of 9 as
for 3. After the reaction was complete, the mixture was al-
lowed to cool and the mixture was slowly poured into water
(100 mL) and reprecipitated twice from water. The white
solid (9) was obtained in 99% (10.89 g) yield.
A mixture of 1 (10.34 g, 29.74 mmol), 4-hydroxy-
benzaldehyde (22.05 g, 180.56 mmol), and K2CO3 (50.00 g,
361.76 mmol) was stirred in THF (250 mL) at 0 °C and then
was reacted at ambient temperature for 48 h. The solvent
was removed under vacuum. The residue was extracted with
CH2Cl2 (4 × 75 mL). After the solvent was removed, a white
solid (2) formed in 92% (23.57 g) yield.
Reaction of 9 with ethyl bromide
A solution of 0.40 mL (0.59 g, 5.43 mmol) ethyl bromide
in acetone (10 mL), 9 (0.60 g, 0.58 mmol), and K2CO3
(2.00 g, 14.47 mmol) in acetone (30 mL) was used for the
preparation of 10 as for 4. The oily product (10) was ob-
tained and dried under vacuum for 48 h. Yield: 62%
(0.41 g).
Synthesis of compound 3
A mixture of 2 (20.00 g, 23.21 mmol) and hydroxyla-
minehydrochloride (10.00 g, 143.90 mmol) was refluxed in
pyridine (15 mL) for 3 h. After the reaction was complete,
the mixture was allowed to cool and was slowly poured into
water (100 mL) and reprecipitated twice from water. The
white solid (3) was washed with alcohol and dried at 50 °C
in a vacuum. Yield: 83% (18.33 g).
Reaction of 9 with allyl bromide
A solution of 0.40 mL (0.55 g, 4.56 mmol) allyl bromide
in acetone (10 mL), 9 (0.60 g, 0.58 mmol), and K2CO3
(2.00 g, 14.47 mmol) in acetone (30 mL) was used for the
preparation of 11 as for 4. The reflux period was 48 h. The
oily product (11) was obtained and dried under vacuum for
48 h. Yield: 89% (0.65 g).
Reaction of 3 with ethyl bromide
A solution of 0.40 mL (0.74 g, 6.79 mmol) ethyl bromide
in acetone (10 mL) was slowly added dropwise to a stirred
and cooled (0–5 °C) mixture of 3 (0.80 g, 0.84 mmol) and
K2CO3 (2.00 g, 14.47 mmol) in acetone (30 mL). The reac-
tion was carried out at room temperature for 1 h and then
was refluxed for 24 h. After the reaction was complete, the
mixture was slowly poured into water (50 mL) and
reprecipitated twice from water. The white solid (4) was
recrystallized from chloroform. Yield: 59% (0.55 g).
Reaction of 9 with propanoyl chloride
A solution of 0.40 mL (0.42 g, 4.60 mmol) propanoyl
chloride in acetone (10 mL), 9 (0.60 g, 0.58 mmol), and
K2CO3 (2.00 g, 14.47 mmol) in acetone (30 mL) was used
for the preparation of 12 as for 4. The oily product (12) was
© 2005 NRC Canada

Çil et al.
2041
Scheme 1. The structures of compounds 2–13.
obtained and dried under vacuum for 24 h. Yield: 89%
(0.70 g).
ride in acetone (10 mL), 9 (0.60 g, 0.58 mmol), and Et3N
(2 mL) in acetone (30 mL) was used for the preparation of
13 as for 4. The reaction was carried out at room tempera-
ture for 24 h. The yellowish solid (13) was washed with al-
cohol three times. Yield: 59% (0.45 g).
Reaction of 9 with acriloyl chloride
A solution of 0.40 mL (0.44 g, 4.86 mmol) acriloyl chlo-
© 2005 NRC Canada

2042
Can. J. Chem. Vol. 83, 2005
Table 1. Physical properties and analytical data for 2–13.
Results and discussion
Compound
Yield (%)
92
Atom
Found
Calcd.
The reaction of 1 with 6 equiv. of 4-hydroxybenzaldehyde
and 4-hydroxyacetophenone in the presence of K2CO3 in
THF gave hexakis(4-formylphenoxy)cyclotriphosphazene (2)
and hexakis(4-acetylphenoxy)cyclotriphosphazene (8). Oxime
compounds hexakis{4-[(hydroxyimino)methyl]phenoxy}cyclo-
triphosphazene (3) and hexakis{4-[(1)-N-hydroxyethane-
imidoyl]phenoxy}cyclotriphosphazene (9) were synthesized
from the reactions of 2 and 8 with hydroxylaminehy-
drochloride in pyridine, respectively.
2
C
H
N
C
H
N
C
H
N
C
H
N
C
H
N
C
H
N
C
H
N
C
H
N
C
H
N
C
H
N
C
H
N
C
H
N
58.52
3.39
4.51
53.43
3.75
12.98
58.16
5.33
11.02
60.10
5.11
10.40
56.21
4.63
9.21
58.29
2.96
13.33
60.93
4.50
4.40
55.67
4.69
11.98
56.42
5.42
9.48
60.76
5.44
58.55
3.51
4.88
53.00
3.81
13.25
57.91
5.40
11.26
60.45
5.07
10.57
55.95
4.70
9.79
59.80
2.87
14.94
60.96
4.48
4.44
55.66
4.67
12.17
58.58
5.62
10.98
62.11
5.69
9.88
57.77
5.29
3
4
83
59
84
74
94
87
99
62
89
89
59
Hexasubstituted oxime derivatives were obtained from the
reactions of oxime compound 3 with ethyl bromide, allyl
bromide, and propanoyl chloride in acetone (in the presence
of K2CO3 for ethyl and allyl bromide, of Et3N for propanoyl
and acriloyl chloride) via replacement of all the oxime pro-
tons with ethyl, allyl and propanoyl groups. However, the
oxime groups on 3 rearranged to nitrile (7) in the reaction of
3 with acriloyl chloride via the dehydration of oximes (35,
36). Compound 7 was previously synthesized by Carriedo
(25). N3P3(OC6H4-CN)6 was directly obtained from the reac-
tion of N3P3Cl6 with 4-cyanophenol and characterized by el-
5
6
7
8
1
emental analysis and H, 13C, and 31P NMR spectra (25).
The analysis results of 7 are in good accordance with the lit-
erature values (25). Similar compounds, N3P3(O-
Ph)5(OC6H4-CN-p) and N3P3(OC6H4-R-4)5(OC6H4-CN-4)
(R = H or t-Bu), were synthesized by Allcock et al. (37) and
Carriedo et al. (38), respectively. Hexasubstituted derivatives
were obtained from the reactions of 9 with allyl bromide and
propanoyl chloride. Tetra- and penta-substituted products
were obtained from the reactions of 9 with ethyl bromide
and acriloyl chloride in acetone (in the presence of K2CO3
for ethyl bromide, of triethylamine for acriloyl chloride), re-
spectively.
9
10
11
12
13
8.92
57.27
5.19
8.38
58.28
4.45
The structures of the compounds were defined by elemen-
1
tal analysis, IR, and H, 13C, and 31P NMR spectroscopy
9.10
57.93
4.48
(structures 2–13 are shown in Scheme 1). Physical proper-
ties and analytical data for 2–13 are given in Table 1. Com-
pounds 2–13 were synthesized in high yields except 4, 10,
and 13. The solvents used for the purification of compounds
7, 10, and 11 could not be removed completely as observed
9.27
9.65
1
by H and 13C NMR spectra. Thus, the presence of these
for 3, 6, 9, and 11, respectively. It is assumed that the weak
peaks due to the cyn and anti isomerism of the -C=N-
groups. The effects of the cyn and anti isomerism are also
observed in the 13C NMR spectra of 3, 6, and 11 (Table 5).
This data demoinstrates that compounds 3, 6, 9, and 11 con-
sist of a mixture of two isomers, but others have one isomer.
Although there are the different phosphorus environments in
the molecules of 10 and 13, the main peak is observed as a
singlet. It is understood that the phosphorus peaks are not af-
fected by these changes because the substituted groups are
far off the phosphorus atoms.
trace amounts of solvent affect the elemental analysis, in
particular the carbon value.
The characteristic stretching peaks in the IR spectra of the
phosphazenes have been assigned as in Table 2. The P=N
stretching vibrations, which are observed between 1173 and
1208 cm–1, are characteristic of cyclophosphazenes.
Compared to 1, which appeared at 1218 cm–1, these peaks
are shifted to longer wavelengths for 2–13. The OH stretch-
ing vibrations in the IR spectra of 3, 9, 10, and 13 indicate
the oxime compounds. While 3 and 9 are initial oximes, all
hydrogen atoms of the OH groups of 10 and 13 could not be
replaced by the alkyl and acyl substituents.
1
The H and 13C NMR data also confirm the structures of
1
2–13 (Scheme 1). In the H NMR spectra (Table 4), the OH
The NMR data for 2–13 are presented in Tables 3–5. The
31P NMR shifts of 2–13 change between 8.05 and
17.21 ppm. Although there is only one peak in the 31P NMR
spectra of 1, 2, 4, 5, 7, 8, 10, 12, and 13 at 20.12, 8.33, 7.49,
9.49, 7.51, 8.05, 9.07, 8.80, and 8.73 ppm, respectively, two
peaks, with very weak second signals, are observed at δ 17.21,
17.26, δ 8.33, 8.21, δ 9.04, 9.01, and δ 9.01 and 8.98 ppm
protons are observed at 10.17, 11.25, 11.30, and 11.25 ppm
for 3, 9, 10, and 13, respectively. It is understood from the
integral intensities that there are six OH protons in 3 and 9,
which are original oxime–phosphazenes, two OH protons in
10, one OH proton in 13. This observation for 10 and 13 in-
dicates that alkyl or acyl groups have not replaced all OH
protons in 3 and 9. The aldehyde proton for 2 appears at
© 2005 NRC Canada

Çil et al.
2043
Table 2. Characteristic IR vibrations (in cm–1) for 2–13.
Compound
νOH
νC-Har.
νC-Hal.
νC=O
ν
νN-O-C
ν
P-O-C
P=N
2
3
4
5
6
7
8
9
10
11
12
13
—
3340
—
—
—
—
—
3460
3309
—
3040, 3100
3044, 3086
3059, 3100
2976, 3087
3060, 3097
3065, 3103
3067, 3105
3058, 3109
2978, 3065
2981, 3078
3058, 3104
3038, 3068
2732, 2820
2903, 2980
2881, 2981
2868, 2981
2883, 2991
2951, 2997
2927, 3002
2913, 2981
2886, 2931
2864, 2920
2937, 2981
2860, 2927
1706
—
—
—
1764
—
1685
—
—
—
1765
1755
1184
1187
1179
1179
1182
1188
1188
1208
1183
1183
1186
1173
—
—
1054
1039
1070
—
—
—
1048
1036
1068
1020
962
949
954
950
973
950
949
960
956
959
953
958
—
3410
Table 3. 31P NMR data for 1–13.
Compound
Main compound (ppm)
Minor isomer (ppm)
1
2
3
4
5
6
7
8
20.12
8.33
17.21
7.49
9.49
8.33
7.51
8.05
9.04
9.07
9.01
8.80
8.73
—
—
17.26
—
—
8.21
—
—
9.01
—
8.98
—
9
10
11
12
13
—
1
Table 4. H NMR data for 2–13.
Compound
1H NMR
7.10 (d) : H2 (4JPOCCH = 8.50), 7.60 (d) : H3 (5JPOCCCH = 8.56), 9.90 (s) : H5; H2:H3:H5 = 2:2:1
2
3
6.86 (d) : H2 (4JPOCCH = 8.45), 7.28(d) : H3 (5JPOCCCH = 8.50), 7.96 (s) : H5, 10.17 (s) : H6, 7.20 : H2 (is.), 7.77 :
H3 (is.); H2:H3:H5:H6 = 2:2:1:1
4
5
6.88 (d) : H2 (4JPOCCH = 8.54), 7.38 (d) : H3 (5JPOCCCH = 8.61), 7.97 (s) : H5, 4.08 (q) : H6, 1.16 (t) : H7
6.88 (d) : H2 (4JPOCCH = 8.47), 7.38 (d) : H3 (5JPOCCCH = 8.55), 8.03 (s) : H5, 4.55 (d) : H6 (J = 5.59), 5.90 (m) :
H7, 5.10 (d) : H8 (J = 10.23), 5.25 (d) : H8
(J = 16.28)
cis
trans
6
7
7.05 (d) : H2, 7.61 (d) : H3, 8.60 (s) : H5, 1.10 (t) : H8, 2.50 (k): H7
7.15 (d) : H2, 7.85 (d) : H3
7.05 (d) : H2, 7.85 (d) : H3, 2.45 (s) : H6; H2:H3:H6 = 2:2:3
8
9
6.85 (d) : H2, 7.50 (d) : H3, 2.10 (s) : H6, 11.25 (s) : H7; H2:H3:H6:H7 = 2:2:3:1
11.30 (s) : H15, 6.90 : H2, H10, 7.55 : H3, H11, 4.15 (q) : H7, 2.15 (s) : H6, H14, 1.25 (t) : H8
6.88 (d) : H2, 7.50 (d) : H3, 6.00 (m) : H8, 5.20 (d) : H9cis, 5.35 (d) : H9trans, 4.65 (d) : H7, 2.15 (s) : H6
7.00 (d) : H2, 7.65 (d) : H3, 2.60 (q) : H8, 2.30 (s) : H6, 1.15 (s) : H9
10
11
12
13
11.25 (s) : H16, 7.00 : H2, H11, 7.80 : H3, H12, 6.1 (d) : H9cis, 6.30–6.60 (m) : H8, H9trans, 2.3 (s) : H6, 2.10 (s) : H15
Note: For numbering see Scheme 1; coupling constants J (Hz). Acetone-d (for 3–5), CDCl3-d (for 2) and DMSO-d (for 6–13) were used as solvents in
NMR analyses. Isomer (is), singlet (s).
9.90 ppm. The azomethine protons for 3–6 are observed at
7.96 (H5), 7.97 (H5), 8.03 (H5), and 8.60 (H5) ppm, respec-
tively. The aromatic protons for all the compounds appear
between 6.85 and 7.85 ppm.
The detailed 13C NMR spectral data are given in Table 5.
The aldehyde carbon atom for 2 and ketone carbon atom for
8 are observed at 190.83 and 197.00 ppm, respectively, at
the lowest downfield of the carbon atoms. Compared to 3
© 2005 NRC Canada

2044
Can. J. Chem. Vol. 83, 2005
Table 5. 13C NMR data for 2–13.
Compound
13C NMR
121.60 : C2, 131.40 : C3, 134.14 : C4, 154.80 : C1, 190.83 : C5
2
3
4
5
6
121.50 : C2, 121.33 : C2 (is), 129.00 : C3, 129.37 : C3 (is), 131.00 : C4, 131.00 : C4 (is), 148.19 : C5, 151.70 : C1
14.46 : C7, 69.81 : C6, 121.57 : C2, 128.62 : C3, 130.46 : C4, 147.35 : C5, 151.63 : C1
151.63 : C1, 147.93 : C5, 134.92 : C7, 130.20 : C4, 128.72 : C3, 121.57 : C2, 117.33 : C8, 75.29 : C6
9.22 : C8, 25.85 : C7, 121.89 : C2, 121.58 : C2 (is), 128.13 : C4, 130.27 : C3, 134.93 : C3 (is), 152.16 : C1, 155.86 :
C5, 172.03 : C6
7
8
9
152.88 : C1, 135.07 : C3, 121.99 : C2, 118.85 : C4, 109.37 : C5
27.04 : C6, 120.96 : C2, 131.20 : C3, 134.54 : C4, 153.27 : C1, 197.00 : C5
11.90 : C6, 120.93 : C2, 127.36 : C3, 134.64 : C4, 150.39 : C1, 152.51 : C5
10
153.08 : C13, 152.48 : C5, 150.53 : C9, 150.27 : C1, 134.60 : C12, 133.72 : C4, 127.58 : C11, 127.33 : C3, 120.93 :
C2, C10, 69.53 : C7, 15.05 : C8, 12.63 : C14, 11.82 : C6
11
12.69 : C6, 74.88 : C7, 74.57 : C7 (is), 117.75 : C9, 117.47 : C9 (is), 120.99 : C2, 120.53 : C2 (is), 127.69 : C3,
133.53 : C4, 134.97 : C8, 150.67 : C1, 153.67 : C5, 152.34 : C5 (is)
12
13
9.29 : C9, 14.19 : C6, 26.12 : C8, 121.16 : C2, 128.94 : C3, 132.25 : C4, 151.68 : C1, 161.91 : C5, 171.88 : C7
163.38 : C7, 162.89 : C5, 152.55 : C14, 151.73 : C1, 150.22 : C10, 134.77 : C4, 133.31 : C13, 132.03 : C9, 129.02 :
C3, 127.43 : C8, 126.94 : C12, 121.16 : C2, 120.96 : C11, 14.35 : C6, 11.82 : C15
Note: For numbering see Scheme 1. Acetone-d (for 3–5), CDCl3-d (for 2), and DMSO-d (for 6–13) were used as solvents in NMR analyses. Isomer (is).
and 9, the azomethine carbon atoms in the substituted moi-
ety of the molecules are shifted to the lower downfield for
compound 6, 11, 12, and 13, except 4, 5, and 10 in which
the alkyl groups release an electron to the molecule. But the
azomethine resonances do not change or change very little
in the nonsubstituted moieties of 10 and 13. In addition, the
13C NMR data clearly show that compound 10 is referred to
as the geminal isomer. There are essentially two different
sets of carbon atoms within the geminal structures, but three
sets within the nongeminal structures for the tetrasubstituted
cyclotriphosphazenes. The resonances of two sets of carbon
atoms were observed in the 13C NMR spectrum of 10. These
results indicate the geminal structure. A triplet and a doublet
are expected in the 31P NMR spectra of geminal structures
for tetrasubstituted cyclotriphosphazene (10), but the main
peak was observed as a singlet. These results show that the
phosphorus signals are not affected from the binding groups
because the substituents at the end of the molecule are far
from the phosphorus atoms.
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