Synthesis of oxime bearing cyclophosphazenes and their reactions with alkyl and acyl halides

Article abstract of DOI:10.1002/hc.20176

Two novel cyclophosphazenes containing oxime groups were prepared from the hexakis(4-formylphenoxy)cyclotriphosphazene (2) and hexakis(4-acetylphenoxy) cyclotriphosphazene (7). The reactions of these oximes with acetyl chloride, chloroacetyl chloride, met

Full text of DOI:10.1002/hc.20176

Heteroatom Chemistry
Volume 17, Number 2, 2006
S
ynthesis of Oxime Bearing
Cyclophosphazenes and Their Reactions
with Alkyl and Acyl Halides
E. C¸ il, M. Arslan, and A. O. G o¨ rg u¨ l u¨
Chemistry Department, Firat University, TR-23169 Elazig, Turkey
Received 26 April 2005; revised 29 June 2005
INTRODUCTION
ABSTRACT: Two novel cyclophosphazenes contain-
ing oxime groups were prepared from the hexakis(4-
The chemistry of linear (short-chain), cyclic, and
formylphenoxy)cyclotriphosphazene (2) and hexakis-
polymeric phosphazenes has been a subject of ex-
tensive investigation [1–5]. These compounds are
reported to possess interesting biomedical proper-
ties and promising applications [6–8]. Phosphazene
polymers bearing flouralkoxy or aryloxy groups stim-
ulated considerable interest in the past as biologi-
cally inert, water insoluble, polymers for blood vessel
or heart valve construction [9]. Cyclophosphazene
derivatives substituted with aziridine groups were
investigated as biomedical products due to their
strongly antitumor activity [10]. Antimicrobial and
biological effects of some phosphazenes on bac-
terial and yeast cells have been studied [11–13].
On the other hand, it is known that phosphorus
and nitrogen compounds are effective flame retar-
dants for fiber materials [14]. The literature con-
tains reports on the synthesis of different linear,
cyclic, or polyphosphazenes [15–25]. There are also
a large number of literature reports on reactions of
the functional groups on phosphazene substituents
[9,26–30].
(4-acetylphenoxy)cyclotriphosphazene (7). The reac-
tions of these oximes with acetyl chloride, chloroacetyl
chloride, methyl iodide, propyl chloride, mono-
chloroacetone, and 1,4-dichlorobutane were studied.
Hexasubstituted compounds were obtained from the
reactions of hexakis(4-[(hydroxyimino)methyl]phen-
oxy)cyclotriphosphazene (3) with acetyl chloride
(4) and chloroacetyl chloride (5); however, tetra-
substituted product was obtained from methyl
iodide (6). Tetra- and trisubstituted products were
obtained from the reactions of hexakis(4-[(1)-N-
hydroxyethaneimidoyl]phenoxy)cyclotriphosphazene
(
(
8) with acetyl chloride (9) and chloroacetyl chloride
10), respectively. All products were obtained in high
yields. Pure and defined product could not be obtained
from the reaction of 8 with methyl iodide, and could
not be also obtained from the reactions of 3 and 8
with propyl chloride, monochloroacetone, and 1,4-
dichlorobuthane. The structures of the compounds
1
13
were defined by elemental analysis, IR, H, C, and
3
1
P NMR spectroscopy. ꢀC 2006 Wiley Periodicals, Inc.
In this paper, we have prepared new cyclophos-
phazenes bearing oxime groups from the hexakis(4-
formylphenoxy)cyclotriphosphazene and hexakis(4-
acetylphenoxy)cyclotriphosphazene. We were also
studied their reactions with alkyl and acyl halides.
Heteroatom Chem 17:112–117, 2006; Published online
in Wiley InterScience (www.interscience.wiley.com). DOI
10.1002/hc.20176
RESULTS AND DISCUSSION
Correspondence to: E. C¸ il; e-mail: cilerol@yahoo.com.
Contract grant sponsor: Firat University Research Found.
Contract grant number: FUBAP 923.
ꢀ
c 2006 Wiley Periodicals, Inc.
The reaction of 1 with 6 equiv. of 4-hydroxy-
benzaldehyde and 4-hydroxyacetophenone in the
1
12

Synthesis of Oxime Bearing Cyclophosphazenes and Their Reactions with Alkyl and Acyl Halides 113
presence of K
phenoxy)cyclotriphosphazene (2) and hexzakis-
4-acetylphenoxy)cyclotriphosphazene (7). Oxime
compounds hexakis(4-[(hydroxyimino)methyl]-
phenoxy)cyclotriphosphazene (3) and hexakis(4-
(1)-N-hydroxyethaneimidoyl]phenoxy)cyclotripho-
sphazene (8) were synthesized from the reactions
of 2 and 7 with hydroxlaminehydrochloride in
pyridine, respectively.
2
CO
3
in THF gave hexakis(4-formyl-
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
(
−
1
observed between 1172 and 1208 cm , are charac-
teristic of cyclophosphazenes. Compared to 1, which
−
1
[
appear at 1218 cm , these peaks are shifted to longer
wavelengths for 2–10. The OH stretching vibrations
in the IR spectra of 3, 6, 8, 9, and 10 indicate
the oxime compounds. Although 3 and 8 are initial
oximes, all hydrogen atoms of OH groups of 6, 9,
and 10 could not be replaced by the alkyl and acyl
substituents.
Hexasubstituted oxime derivatives were ob-
tained from the reactions of oxime compound 3 with
acetyl chloride and chloroacetyl chloride (in ace-
tone in the presence of K
2
CO
3
) via all of the oxime
The NMR data of 2–10 are presented in
Tables 3–5. The P NMR shifts of 2–10 change be-
3
1
protons replacement with acetyl and chloroacetyl
groups. However, tetrasubstituted product was ob-
tained from the reaction of 3 with methyl iodide
at the same conditions as for acetyl chloride and
chloroacetyl chloride. Tetra- and trisubstituted prod-
ucts were obtained from the reactions of 8 with
acetyl chloride and chloroacetyl chloride (in acetone
in the presence of triethylamine), respectively. Pure
or defined products could not be obtained from the
reactions of both oximes (3 and 8) with propyl chlo-
ride, monochloroacetone and 1,4-dichlorobutane,
and 8 with methyl iodide.
tween 8.05 and 17.21 ppm. Although there is only
3
1
one peak in the P NMR spectra of 1, 2, 7, 9, and
10 at 20.12, 8.33, 8.05, 8.77, and 8.75 ppm, two
peaks, where the second signals are very weak, are
observed at δ = 17.21, 17.26, δ = 9.06, 8.93, δ = 9.86,
10.30, δ = 9.28, 9.18, and δ = 9.04, 9.01 ppm for 3, 4,
5, 6, and 8, respectively. It is assumed that the weak
peaks due to the cyn and anti isomerism of C N
groups. The effects of the cyn and anti isomerism
1
3
are also observed at the C NMR spectra of 3, 5,
and 6 (Table 5). From this data, it is explained that
compounds 3–6 and 8 consist of a mixture of two iso-
mers, but others have one isomer. Although there are
different phosphorus environments in the molecules
of 6, 9, and 10, the main peak is observed as a sin-
glet. It is understood that the phosphorus peaks are
not affected from these changes because of the sub-
stituted groups are far off the phosphorus atoms.
The structures of the compounds were defined
1
13
31
by elemental analysis, IR, H, C, and P NMR spec-
troscopy (structures of 2–10 are shown in Scheme 1).
Physical properties and analytical data of 2–10 are
given in Table 1. Compounds 2–9 were synthesized
in high yields. The solvents used for the purification
of the compounds 9 and 10 could not be removed
1
13
1
13
completely as observed by H, C, and NMR spec-
tra. Thus, the presence of these trace amounts of sol-
vent affects the elemental analysis, in particular the
carbon value.
The H and C NMR data also confirm the struc-
1
tures of 2–10 (Scheme 1). In the H NMR spectra
(Table 4), the OH protons are observed at 10.17,
11.31, 11.25, 11.25, and 11.25 ppm for 3, 6, 8, 9,
and 10, respectively. It is understood from the inte-
gral intensities that there are six OH protons in 3 and
TABLE 1 Physical Properties, Molecular Weight, and Ana-
lytical Data of Compounds 2–10
8
, which are original oxime-phosphazenes, two OH
protons in 6 and 9, and three OH protons in 10. This
observation indicates that alkyl or acyl groups have
not replaced all OH protons in 3 and 8. Aldehyde
proton for 2 appears at 9.90 ppm. The azomethine
Yield (%)
Found Calcd
Yield (%)
Found Calcd
2
3
4
5
6
92
C 58.52 58.55 7
87
C 60.93 60.96
H
N
3.39 3.51
4.51 4.88
H
N
4.50 4.48
4.40 4.44
5
protons for 3, 4, 5, and 6 are observed at 7.96 (H ),
5
5
5
11
8
.00 (H ), 8.32 (H ), and 8.17 (H )–8.18 (H ), respec-
83
75
72
80
C 53.43 53.00 8
3.75 3.81
99
79
57
C 55.67 55.66
4.69 4.67
N 11.98 12.17
C 54.12 55.86
H
H
tively. The aromatic protons for all the compounds
appear between 6.85 and 7.85 ppm.
N 12.98 13.25
C 54.88 53.87 9
13
The detailed C NMR spectral data are given
H
4.05 4.02
H
N
4.96 4.69
8.34 10.47
in Table 5. Aldehyde carbon atom for 2 and ketone
carbon atom for 7 are observed at 190.83 and
197.00 ppm at the lowest downfield of the carbon
atoms. Compared to 3 and 8, the azomethine car-
bon atoms in the substituted moiety of the molecules
are shifted to the lower downfield for compound
N 10.47 10.47
C 45.98 47.92 10
C 49.37 51.26
H
N
3.00 3.25
8.94 9.09
H
N
3.69 4.06
7.40 9.96
C 54.37 54.82
4.64 4.40
N 11.12 12.51
H
4
, 5, 9, and 10 except 6, in which methoxy group

1
14 C¸ il, Arslan, and G o¨ rg u¨ l u¨
SCHEME 1 The structures of compounds 2–10.
releases electron to the molecule. But the azome-
thine resonances do not change in the nonsubsti-
substituted cyclotriphosphazenes. The resonances of
1
3
two sets of carbon atoms were observed in the
C
1
3
tuted moiety of 6, 9, and 10. In addition, the
C
NMR spectra of 6 and 9. These results indicate the
geminal structure. There are essentially two different
sets of carbon atoms in the nongeminal structure,
but four sets in the geminal isomer for the trisubsti-
tuted cyclotriphosphazene. The carbon resonances
for 10 are in accordance with the nongeminal
NMR data clearly show that compounds 6 and 9 are
referred to as geminal isomer, but 10 is nongeminal
isomer. There are essentially two different sets of car-
bon atoms within the geminal structures, but three
sets within the nongeminal structures for the tetra-

Synthesis of Oxime Bearing Cyclophosphazenes and Their Reactions with Alkyl and Acyl Halides 115
TABLE 2 Characteristic IR Vibrations (in cm 1) of Compounds 2–10
−
Compound
νOH
νC H ar om
νC H ali ph
νC
O
νP
N
νN
O
C
νP
O C
2
3
4
5
6
7
8
9
–
3340
–
–
3343
–
3460
3341
3440
3040, 3100
3044, 3086
3012, 3073
3069, 3098
3068, 3098
3067, 3105
3058, 3109
3069, 3103
3017, 3073
2732, 2820
2903, 2980
2941, 3000
2957, 3005
2895, 2935
2927, 3002
2913, 2981
2917, 2981
2854, 2956
1706
–
1768
1780
–
1685
–
1768
1774
1184
1187
1182
1183
1176
1188
1208
1188
1172
–
–
1051
1020
1057
–
962
949
965
954
954
949
960
953
958
–
1042
1082
10
TABLE 3 The 31P NMR Data of Compounds 1–10
TABLE 4 1H NMR Data of Compounds 2–10
2
4
3 5
Main
Compound
Minor
Isomer
Main
Compound
Minor
Isomer
2
3
7.10 (d): H ( J
8
: 8.50), 7.60 (d): H ( JPOCCCH:
POCCH
5
2
5
.56), 9.90 (s): H , H :H3:H = 2:2:1
2 4 3
5
6.86 (d): H ( J
: 8.45), 7.28 (d): H ( J
:
POCCH
5
POCCCH
2
1
2
3
4
5
20.12
8.33
17.21
9.06
–
–
6
7
9.28
8.05
9.04
8.77
8.75
9.18
–
9.01
–
6
8
7
.50), 7.96 (s): H , 10.17 (s): H , 7.20 (w): H (is),
3
2
3
5
6
.77 (w): H (is), H :H :H :H = 2:2:1:1
3 5
17.26
8.93
10.30
8
2
4
9
10
4
5
6
6.95 (d): H ( JPOCCH: 8.50), 7.50 (d): H ( JPOCCCH:
5
7
2
3
5
7
9.86
–
8.51), 8.00 (s): H , 2.19 (s): H , H :H :H :H =
2
:2:1:3
2
4
3 5
6.94 (d): H ( J
: 8.38), 7.50 (d): H ( J
:
POCCH
5
POCCCH
7
7
2
3
5
8
.40), 8.32 (s): H , 4.22 (s): H , H :H :H :H =
3
1
isomer. A triplet and a doublet are expected in the
P
2:2:1:2
1
2
11
5
NMR spectra of geminal structures for tetrasubsti-
tuted cyclotriphosphazenes (6 and 9), but the main
peak was observed as a singlet. These results show
that the phosphorus signals are not affected from the
binding groups because of the substituents at the end
of the molecule are far from the phosphorus atoms.
11.31 (s): H , 8.18 (s): H , 8.17 (s): H , 6.95:
2
8
3
9
6
6
H + H , 7.50: H + H , 3.96 (s): H , 3.79 (s): H
1
2
5
11
3
9
2
8
6
(
is), H :(H + H ):(H + H ):(H + H ):H =
1
:3:6:6:6
2
3
6
2
3
7
8
7.05 (d): H , 7.85 (d): H , 2.45 (s): H , H :H = 1:1
2 3 6 7
6.85 (d): H , 7.50 (d): H , 2.10 (s): H , 11.25 (s): H ,
2
3
6
7
H :H :H :H = 2:2:3:1
1
5
2
10
3
11
9
1
11.25 (s): H , 7.00: H + H , 7.60: H + H , 2.3 (s):
8 6 14 15 2 10
H , 2.10 (s): H , 1.96 (s): H , H :(H + H ):
EXPERIMENTAL
General Remarks
3
11
8
6
14
(
H + H ):H :H :H = 1:6:6:6:6:3
11.25 (s): H , 6.90: H + H , 7.50–7.70: H + H11,
15 2 10
3
0
.2 (s): H , 2.3 (s): H , 2.10 (s): H , H :(H + H10):
8
6
14
15
2
4
(
Solvents and other liquids used in the experimen-
tal works were dried by conventional methods. Hex-
3
11
8
6
14
H + H ):H :H :H = 1:4:4:2:3:3
achlorocyclotriphosphazene [N
3
P
3
Cl
6
] (1) was recry-
Notes: For numbering see Scheme 1; coupling constant J (Hz);
acetone-d (for 3), CDCl -d (for 2, 4, and 5), and DMSO-d (for
–10) were used as solvents in NMR analyses; is: isomer, s: singlet,
w: weak.
3
stallized from hexane. Other chemicals were used
as purchased. Hexakis(4-formylphenoxy)cyclotri-
phosphazene (2) and hexakis(4-acetylphenoxy)-
cyclotriphosphazene (7) were prepared as described
by Carriedo et al. [23]. The reactions of [N
with the phenols were carried out under dry
nitrogen.
6
values. Microanalysis was carried out by LECO 932
CHNS-O apparatus.
3
P
3
6
Cl ]
The IR spectra were recorded on an ATI Unicam
Synthesis of Compound 2. A mixture of
1
13
31
Mattson 1000 FTIR spectrometer. H, C, and
P
[N
3
P
3
6
Cl ] (10.34 g, 29.74 mmol), 4-hydroxybenzal-
NMR spectra were recorded using a Bruker DPX-
dehyde (22.05 g, 180.56 mmol), and K
2
CO
3
(50.00 g,
◦
3
00 spectrometer operating at 300.13, 75.46, and
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
1
13
1
21.49 MHz, respectively. The H and C chemical
as an internal stan-
dard; the P chemical shifts were measured using
5% H PO as an external standard. Chemical shifts
downfield from the standard are assigned positive δ
shifts were measured using SiMe
4
3
1
residue was extracted with CH
the solvent was removed, a white solid (2) formed
2
Cl
2
(4 × 75 mL). After
8
3
4
in 92% (23.57 g) yield.

1
16 C¸ il, Arslan, and G o¨ rg u¨ l u¨
TABLE 5 13C NMR Data of Compounds 2–10
were used for the preparation of 5 as for 4. The white
solid (5) was obtained in 72% (0.85 g) yield.
2
3
4
2
3
121.60: C , 131.40: C , 134.14: C , 154.80:
1
5
C , 190.83: C
Reaction of 3 with Methyl Iodide. The solution of
2
2
3
121.50: C , 121.33: C (is), 129.00: C , 129.37:
0
.40 mL (0.91 g, 6.42 mmol) methyl iodide in acetone
3
4
4
C (is), 131.00: C , 131.00: C (is), 148.19:
C5, 151.70: C
19.95: C , 121.62: C , 127.84: C , 130.17: C ,
52.91: C , 155.17: C , 168.90: C
40.23: C , 40.94: C (is), 121.81: C , 127.33: C ,
(
10 mL), 3 (0.80 g, 0.84 mmol), and K CO (2.00 g,
2
3
1
7
2
4
3
14.47 mmol) in acetone (30 mL) were used for the
preparation of 6 as for 4. After the reaction was com-
plete, the precipitated salt was filtered off and the sol-
vent was removed under vacuum. The oily residue
was solved in acetone and reprecipitated (as oily)
from hexane. Compound 6 was obtained as solid in
4
5
1
5
6
1
7
7
2
4
3
1
1
28.75: C (is), 130.45: C , 153.16: C , 156.56:
4
5
6
6
C , 165.51: C , 170.96: C (is)
7
1
11
5
6
151.44: C , 151.02: C , 148.38: C , 147.93: C ,
1
0
4
4
1
31.38: C , 130.12: C , 130.29: C (is), 129.16:
C , 128.69: C , 121.72: C , 121.16: C , 62.51:
C , 61.15: C (is)
27.04: C , 120.96: C , 131.20: C , 134.54: C ,
53.27: C , 197.00: C
11.90: C , 120.93: C , 127.36: C , 134.64: C ,
8
0% (0.68 g) yield after the solvent was removed in
9
3
8
2
vacuum for 24 h.
6
6
6
2
3
4
7
8
9
1
5
Synthesis of Compound 7. A mixture of [N
3
P
3
6
Cl ]
1
6
2
3
4
(7.00 g,20.13 mmol), 4-hydroxyacetophenone (16.72 g,
22.80 mmol), and K CO (34.00 g, 245.99 mmol)
1
5
1
2
3
1
50.39: C , 152.51: C
7
5
13
1
168.80: C , 161.74: C , 152.53: C , 151.73: C ,
was refluxed in acetone (250 mL) for 3 h. The sol-
vent was evaporated in vacuum, and the residue was
9
4
12
1
50.27: C , 134.77: C , 132.15: C , 128.90:
C , 127.40: C , 121.12: C , 120.93: C , 19.98:
3
11
2
10
extracted with CH
oration of the solvent in vacuum, a white solid (7)
2
Cl
2
(4 × 75 mL). After the evap-
8
6
14
C , 14.24: C , 11.84: C
7
5
13
1
1
0
165.95: C , 163.46: C , 152.52: C , 152.00: C ,
9
4
12
formed in 87% (16.50 g) yield.
1
50.29: C , 134.66: C , 131.56: C , 129.09:
C , 127.38: C , 121.16: C , 120.93: C , 41.94:
C , 14.46: C , 11.89: C
3
11
2
10
8
6
14
Synthesis of Compound 8. Hydroxlaminehy-
drochloride (4.50 g, 64.75 mmol) and 7 (10.00 g,
Notes: For numbering see Scheme 1; acetone-d (for 3), CDCl
3
-d (for
1
0.57 mmol) were used for the preparation of 8
2, 4, and 5), and DMSO-d (for 6–10) were used as solvents in NMR
analyses; is: isomer.
as for 3. After the reaction was complete, the mix-
ture was allowed to cool and the mixture was slowly
poured into water (100 mL) and reprecipitated twice
from water. The white solid (8) was obtained in 99%
Synthesis of Compound 3. A mixture of 2
(10.89 g) yield.
(20.00 g, 23.21 mmol) and hydroxlaminehydrochlo-
ride (10.00 g, 143.90 mmol) was refluxed in pyridine
15 mL) for 3 h. After the reaction was complete, the
Reaction of 8 with Acetyl Chloride. The solution
(
of 0.40 mL (0.46 g, 5.80 mmol) acetyl chloride in
acetone (10 mL), 8 (0.60 g, 0.58 mmol), and triethy-
lamine (2 mL) in acetone (30 mL) were used for the
preparation of 9 as for 4. The oily product (9) was
obtained in 79% (0.55 g) yield.
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 vacuum. Yield: 18.33 g, 83%.
Reaction of 3 with Acetyl Chloride. The solution
of 0.40 mL (0.45 g, 5.80 mmol) acetyl chloride in ace-
tone (10 mL) was slowly added dropwise to a stirred
Reaction of 8 with Chloroacetyl Chloride. The
solution of 0.40 mL (0.56 g, 5.02 mmol) acetyl chlo-
ride in acetone (10 mL), 8 (0.60 g, 0.58 mmol), and
triethylamine (2 mL) in acetone (30 mL) were used
for the preparation of 10 as for 4. The solid (10) was
obtained in 57% (0.42 g) yield.
◦
and cooled (0–5 C) mixture of 3 (0.80 g, 0.84 mmol)
and K
2
CO (1.55 g, 11.25 mmol) in acetone (30 mL).
3
The reaction was carried out at room temperature
for 12 h. After the reaction was complete, the mix-
ture was slowly poured into water (50 mL) and repre-
cipitated twice from water. The white solid (4) was
recrystallized from alcohol. Yield: 0.76 g, 75%.
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[
[
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and K
2
CO (1.60 g, 11.57 mmol) in acetone (30 mL)
3

Synthesis of Oxime Bearing Cyclophosphazenes and Their Reactions with Alkyl and Acyl Halides 117
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