Synthesis and characterization of chalconesubstituted phosphazenes

Article abstract of DOI:10.1139/V10-057

A series of mono[(E)-1-(4-alkyloxyphenyl)-3-(4-hydroxy-phenyl)prop-2-en-1- one]cyclotriphosphazenes and hexakis[(E)-1-(4-alkyloxy-phenyl)-3-(4-hydroxy- phenyl) prop-2-en-1-one]cylotriphosphazenes have been synthesized. A convenient synthetic method was pe

Full text of DOI:10.1139/V10-057

654
Synthesis and characterization of chalcone-
substituted phosphazenes
Zainab Ngaini and Norashikin I. Abdul Rahman
Abstract: A series of mono[(E)-1-(4-alkyloxyphenyl)-3-(4-hydroxy-phenyl)prop-2-en-1-one]cyclotriphosphazenes and
hexakis[(E)-1-(4-alkyloxy-phenyl)-3-(4-hydroxy-phenyl) prop-2-en-1-one]cylotriphosphazenes have been synthesized. A
convenient synthetic method was performed from the reaction of hexachlorocyclotriphosphazenes with 1 and 6 equiv. of
(E)-1-(4-alkyloxyphenyl)-3-(4-hydroxy-phenyl)prop-2-en-1-one (2a–2c) to afford (3a–3c) in 17%–19% and (4a–4c) in
70%–82%, respectively. The compounds differ in the length of alkyl groups, CnH2n+1, where n = 10, 12, and 14.
Key words: hexachlorocyclotriphosphazenes, chalcones, alkyloxy, condensation.
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Resume : On a realise la synthese d’une serie de mono[(E)-1-(4-alkyloxyphenyl)-3-(4-hydroxyphenyl)prop-2-en-1-one]cyclo-
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triphosphazenes et de hexakis[(E)-1-(4-alkyloxyphenyl)-3-(4-hydroxyphenyl)prop-2-en-1-one]cyclotriphosphazenes. On a
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execute une methode de synthese appropriee par reaction d’hexachlorocyclotriphosphazenes avec 1 et 6 equiv. de (E)-1-(4-
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alkyloxyphenyl)-3-(4-hydroxyphenyl)prop-2-en-1-one (2a–2c) qui ont conduit respectivement aux produits (3a–3c) avec
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des rendements allant de 17 a 19 % et aux produits (4a–4c) avec des rendements allant de 70 a 82 . Les composes diffe-
rent par la longueur des groupes alkyles, CnH2n+1, dans lesquels n = 10, 12 et 14.
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Mots-cles : hexachlorocyclotriphosphazenes, chalcones, alkyloxy, condensation.
(2a–2c), which could be used as model reactions for various
crystalline electro-optical devices.
Introduction
Phosphazenes are compounds containing a framework of
alternating phosphorus and nitrogen atoms, either in cyclic
or linear form.1 Linear, cyclic, and poly phosphazenes have
been widely investigated. These compounds are reported to
possess interesting biomedical properties2 and promising ap-
plication as effective flame retardants for fiber materials.3
Nucleophilic substitution reactions on hexachlorocyclotri-
phosphazenes have been widely reported.4–6 The synthesis
of cyclotriphosphazenes, bearing 4-oxychalcones6 as side
groups, has been studied for photosensitive phosphazenes
that could undergo photo-cross-linking reaction under UV ir-
radiation.
In photochemistry, chalcone derivatives were reported to
possess outstanding nonlinear optic property for optical
communications and optical electronics,7 liquid crystal dis-
plays,8,9 and alignment film.10 Chalcones were also reported
to promote excellent blue-light transmittance and good crys-
tallability,11,12 high photosensitivity, and thermal stability for
various crystalline electro-optical devices.
Recently, we reported a very convenient method for the prep-
aration of trimeric aryloxyphosphazenes directly from [N3P3Cl6]
and (E)-3-(4-(alkyloxy)phenyl)-1-(4-hydroxyphenyl)prop-2-en-1-
one using K2CO3 in acetone.13 This prompted us to try the re-
action of cyclotriphosphazenes with other para-substituted
hydroxy chalcones. We herein describe the synthesis of cy-
clotriphosphazenes incorporated with hydroxylated chalcones
(E)-1-[4-(alkyloxy)phenyl]-3-[4-hydroxyphenyl] prop-2-en-1-one
Results and discussion
The series of chalcone derivatives (E)-1-[4-(alkyloxy)-
phenyl]-3-[4-hydroxyphenyl] prop-2-en-1-one (2a–2c) was
prepared via Claisen–Schmidt condensation of 1a–1c and 4-
hydroxybenzaldehyde by the route depicted in Scheme 1.
The structural assignments of compounds 2a–2c were
based on the analytical and spectral data. The IR spectra of
the hydroxylated chalcones 2a–2c showed the presence of
bands at 2921–2852 cm–1, which were attributed to the in-
troduction of the long alkyl chain via etherification of 4-hy-
droxyacetophenone. The presence of a new C=O stretching
frequency at 1651 cm–1 substantiated the formation of the ti-
tle compound. The chemical structures of 2a–2c were found
1
to be consistent with H NMR and 13C NMR spectroscopic
data and showed the peaks corresponding to the structures. In
1H NMR spectra, the coupling constant, Jab = 15.0 –16.0 Hz,
indicated all chalcones obtained were in trans-configuration.
The synthetic route for the preparation of mono-
(N3P3Cl5[OC6H4CH=CHC(O)C6H4OCnH2n+1]) (3a–3c) and
hexa-substituted cyclotriphosphazenes (N3P3[OC6H4CH=CH-
C(O)–C6H4OCnH2n+1]6) (4a–4c) is illustrated in Scheme 2.
Mono-subsubstituted cyclotriphosphazenes 3a–3c were
obtained from the reaction of hexachlorocyclotriphospha-
zenes with 1 equiv. of chalcone derivatives 2a–2c in the
presence of K2CO3 in acetone. The higher polarity of the
Received 29 November 2009. Accepted 21 April 2010. Published on the NRC Research Press Web site at canjchem.nrc.ca on 18 June
2010.
Z. Ngaini1 and N.I. Abdul Rahman. Department of Chemistry, Faculty of Resource Science and Technology, Universiti Malaysia
Sarawak 94300, Kota Samarahan, Sarawak, Malaysia.
1Corresponding author (e-mail: nzainab@frst.unimas.my).
Can. J. Chem. 88: 654–658 (2010)
doi:10.1139/V10-057
Published by NRC Research Press

Ngaini and Abdul Rahman
655
Scheme 1.
Scheme 2.
acetone14 was believed to increase the rate of reaction com-
pared with THF6 and dioxane.15 The IR spectra showed P=N
stretching vibrations at 1183 cm–1, which are characteristic
of cyclotriphosphazenes.16,17 The absorption bands observed
at 871 cm–1 were attributed to the presence of the P–O–C
bond.18 31P NMR spectra showed two resonances as a triplet
and a doublet at 12.74 ppm and 23.27 ppm, respectively,
with a coupling constant, J = 60 Hz, which implied the re-
placement of one chlorine from the cyclotriphosphazenes
ring for the mono-substituted phosphazenes.19 1H and 13C
NMR data also confirmed the substitution of 2a–2c, with
the chemical shifts moving slightly downfield.
and hexakis{(E)-1-[4-(alkyloxy)phenyl]-3-[4-hydroxyphenyl]-
prop-2-en-1-one}cyclotriphosphazenes (4a–4c). Compounds
3a–3c gave lower melting points, whereas compounds 4a–
4c possessed higher melting points than the hydroxylated
chalcones (2a–2c). These findings could potentially be used
as model reactions for various crystalline electrooptical de-
vices.
Experimental
General
4-Hydroxybenzaldehyde, 4-hydroxyacetophenone, and 1-
bromoalkanes were obtained from Merck Company and
used as received. Hexachlorocyclotriphosphazenes was pro-
vided by Aldrich and were recrystallized from hexane. Ace-
tone was distilled from calcium hydride under nitrogen
before use. All other reagents and solvents were used as re-
ceived. The reactions were performed under dry nitrogen.
Melting points were determined in open capillaries and are
uncorrected. Infrared spectra were recorded on (FTIR) 1605
The reaction of hexachlorocyclotriphosphazenes with 6
equiv. of 2a–2c under the same conditions afforded 4a–4c
in high yields. The IR spectra showed the characteristic ab-
sorption bands at 1180 cm–1, which were attributed to P=N
stretching vibrations. The absorption bands observed at
881 cm–1 in 4a–4c were attributed to the presence of P–O–
C bond. 31P NMR showed a single resonance at d 8.84 ppm,
which implied complete chlorine replacement.19 The data
1
1
obtained from elemental analysis, H, and 13C NMR showed
Shimadzu Spectrometer using KBr pellets. H NMR spectra
were recorded on a 500 MHz Jeol Delta 2-NMR, and 13C
NMR was recorded on a 125.77 MHz using TMS as the in-
ternal standard.
good agreement to the corresponding structures.
Conclusion
In summary, this research has demonstrated the nucleo-
philic substitution of (E)-1-[4-(alkyloxy)phenyl]-3-[4-hydrox-
yphenyl] prop-2-en-1-one (2a–2c) onto cyclotriphosphazenes,
which afforded new mono{(E)-1-[4-(alkylyloxy)phenyl]-3-[4-
hydroxyphenyl]prop-2-en-1-one}cyclotriphosphazenes (3a–3c)
Synthesis of alkyloxyphenyl-ethanone (1a–1c)
General procedure
Bromoalkane (72 mmol), 4-hydroxyacetophenone (72 mmol),
K2CO3 (72 mmol), and TBAI (6 mmol) in MEK (200 mL)
Published by NRC Research Press

656
Can. J. Chem. Vol. 88, 2010
were heated at reflux for 5 h. The mixture was filtered and
cooled to room temperature. Water (30 mL) was added to
the filtrate, and the layers separated. The aqueous layer was
extracted with dichloromethane (2 Â 30 mL). The combined
layers were washed with water (2 Â 20 mL), dried
(MgSO4), filtered, and concentrated in vacuo. The crude
was recrystallized from ethanol to give 1a–1c.
3195 (OH), 2921, 2852 (C–H), 1651 (C=O), 1581 (aro-
matic), 1223 (alkyl aryl ether), 990 (C=C). 1H NMR
(500 MHz, CDCl3) dH: 0.81 (3H, t, 1 Â CH3), 1.21–1.87
(20H, m, 10 Â CH2), 3.95 (2H, t, OCH2), 6.83 (2H, d, J =
8.6 Hz, Ar–H), 6.86 (2H, d, J = 8.6 Hz, Ar–H), 7.32 (1H, d,
J = 15.45 Hz, 1 Â olefinic H), 7.45 (2H, d, J = 8.0 Hz, Ar–
H), 7.67 (1H, d, J = 15.45 Hz, 1 Â olefinic H), 7.94 (2H, d,
J = 8.0 Hz, Ar–H). 13C NMR (125.77 MHz, CDCl3) dC:
14.10, 22.67, 25.96, 29.08, 29.33, 29.55, 29.58, 29.61,
30.96, 31.89, 68.29, 114.30, 116.09, 119.03, 127.24, 130.45,
130.84, 144.66, 158.75, 163.12, 189.62. Anal. calcd.
C27H36O3: C, 79.37: H, 8.88. Found (%): C, 79.52; H, 8.90.
1-(4-Decyloxyphenyl)-ethanone (1a)
Compound 1a was obtained as colorless crystals. Yield:
89. FTIR and NMR data were consistent with the reported
literature.20
1-(4-Dodecyloxyphenyl)-ethanone (1b)
(E)-1-[4-(Tetradecyloxy)phenyl]-3-[4-hydroxyphenyl]prop-
2-en-1-one (2c)
Compound 1b was obtained as colorless crystal. Yield:
78%; mp 52–53 8C. FTIR (thin films, cm–1) ymax: 2954,
2918, 2849 (C–H), 1676 (C=O), 1606 (aromatic), 1253
Compound 2c was obtained as yellow crystals. Yield:
39%; mp 107–108 8C. FTIR (thin films, cm–1) ymax: 3208
(OH), 2918, 2850 (C–H), 1646 (C=O), 1585 (aromatic),
1
(alkyl aryl ethers). H NMR (500 MHz, CDCl3) dH: 0.85
1
(3H, t, 1 Â CH3), 1.24–1.77 (20H, m, 8 Â CH2), 2.52 (3H,
s, 1 Â CH3), 3.98 (2H, t, OCH2), 6.87 (2H, d, J = 9.2 Hz,
Ar–H), 7.88 (2H, d, J = 9.2 Hz, Ar–H). 13C NMR
(125.77 MHz, CDCl3) dC: 14.06, 22.63, 25.91, 26.24, 29.03,
29.29, 29.50, 29.53, 39.58, 29.60, 29.60, 31.86, 68.19,
114.06, 130.01, 130.50, 163.06, 196.71. Anal. calcd. (%)
C20H32O2: C, 78.90; H, 10.59. Found (%): C, 78.73; H, 10.45.
1223 (alkyl aryl ether), 990 (C=C). H NMR (500 MHz,
DMSO-d6) dH: 0.82 (3H, t, 1 Â CH3), 1.24–1.71 (24H, m,
12 Â CH2), 4.04 (2H, t, OCH2), 6.81 (2H, d, J = 8.6 Hz,
Ar–H), 7.02 (2H, d, J = 9.15 Hz, Ar–H), 7.61 (1H, d, J =
15.45 Hz, 1 Â olefinic H), 7.69 (1H, d, J = 15.45 Hz, 1 Â
olefinic H), 7.70 (2H, d, J = 9.15 Hz, Ar–H), 8.09 (2H, d, J =
8.60 Hz, Ar–H), 10.04 (1H, s, OH). 13C NMR (125.77 MHz,
DMSO-d6) dC: 13.93, 22.09, 25.42, 28.54, 28.72, 28.97,
28.97, 29.02, 29.02, 29.05, 30.67, 31.29, 67.81, 114.28,
115.76, 118.36, 125.90, 130.60, 130.65, 130.81, 143.52,
159.92, 162.44, 187.12. Anal. calcd. (%) C29H40O3: C,
79.77; H, 9.23. Found (%): C, 78.83; H, 9.04.
1-(4-Tetradecyloxyphenyl)-ethanone (1c)
Compound 1c was obtained as colorless crystals. Yield:
94%; mp 58–59 8C. FTIR (thin films, cm–1) ymax: 2954,
2917, 2849 (C–H), 1676 (C=O), 1605 (aromatic), 1253
(alkyl aryl ether). 1H NMR (500 MHz, CDCl3) dH: 0.84
(3H, t, 1 Â CH3), 1.23–1.76 (24H, m, 10 Â CH2), 2.50 (3H,
s, 1 Â CH3), 3.96 (2H, t, OCH2), 6.86 (2H, d, J = 8.0 Hz,
Ar–H), 7.87 (2H, d, J = 8.0 Hz, Ar–H). 13C NMR
(125.77 MHz, CDCl3) dC: 14.02, 22.60, 25.88, 26.16, 29.01,
29.28, 29.28, 29.47, 29.51, 29.57, 29.57, 29.59, 31.83,
68.13, 114.00, 129.97, 130.44, 163.02, 196.55. Anal. calcd.
C22H36O2: C, 79.46; H, 10.91. Found (%): C, 79.23; H, 10.51.
Synthesis of mono-substituted cyclotriphosphazene (3a–3c)
General procedure
A mixture of hexachlorocyclotriphosphazenes (2.01 mmol),
2a (2.01 mmol), and K2CO3 (4.02 g) in acetone (60 mL)
was heated at reflux for 1 h. The mixture was allowed to
cool to room temperature and filtered. The filtrate was dried,
filtered, and concentrated in vacuo. The crude solid was re-
crystallized from acetone to afford 3a–3c.
Synthesis of (alkyloxy)phenyl-hydroxyphenyl]prop-2-en-
1-one (2a–2c)
Preparation of N3P3Cl5[OC6H4CH=CHC(O)C6H4OC10H21]
(3a)
General procedure
Compound 3a was obtained as pale yellow solid. Yield:
A mixture of 4-hydroxybenzaldehyde (12.5 mmol) and 1a
(12.5 mmol) in 35 mL of methanol was added under stirring
to a solution of KOH (2.52 g) in methanol (10 mL). The
mixture was heated at reflux for 10 h. The reaction was
cooled to room temperature and acidified with cold diluted
HCl (2 N). The resulting precipitate was filtered, washed,
and dried. The crude was recrystallized from hexane:ethanol
(7:1) to give 2a–2c.
17%; mp 74–75 8C. FTIR (thin films, cm–1) ymax: 1183
1
(P=N), 871 (P–O–C). H NMR (500 MHz, CDCl3) dH: 0.81
(3H, t, 1 Â CH3), 1.21–1.75 (16H, m, 8 Â CH2), 3.97 (2H, t,
OCH2), 6.89 (2H, d, J = 9.15 Hz, Ar–H), 7.24 (2H, d, J =
8.0 Hz, Ar–H), 7.44 (1H, d, J = 16.05, 1 Â olefinic H),
7.60 (2H, d, J = 8.55 Hz, Ar–H), 7.68 (1H, d, J = 15.50
Hz, 1 Â olefinic H), 7.95 (2H, d, J = 8.60 Hz, Ar–H). 13C
NMR (125.77 MHz, CDCl3) dC: 14.09, 22.65, 25.96, 29.08,
29.29, 29.33, 29.52, 31.86, 31.91, 68.30, 114.34, 121.86,
122.71, 129.85, 130.55, 130.82, 133.78, 141.98, 150.31,
163.23, 188.25. 31P NMR (200 MHz, CDCl3) dP: 12.74 (t, J =
60.0 Hz, Pa–P), 23.27 (d, J = 60.0 Hz, Pb–P). Anal. calcd.
(%) N3P3Cl5C25H31O3: C, 43.41; H, 4.52; N, 6.07. Found
(%): C, 43.06; H, 4.44; N, 6.03.
(E)-1-[4-(Decyloxy)phenyl]-3-[4-hydroxyphenyl]prop-2-en-
1-one (2a)
Compound 2a was obtained as yellow crystals. Yield: 34.
FTIR and NMR data were consistent with the reported liter-
ature.20
(E)-1-[4-(Dodecyloxy)phenyl]-3-[4-hydroxyphenyl]prop-2-
en-1-one (2b)
Preparation of N3P3Cl5[OC6H4CH=CHC(O)C6H4OC12H25]
(3b)
Compound 3b was obtained as pale yellow solid. Yield:
Compound 2b was obtained as yellow crystals. Yield:
44%; mp 110.6–111.2 8C. FTIR (thin films, cm–1) ymax
:
Published by NRC Research Press

Ngaini and Abdul Rahman
657
19%; mp 60–62 8C. FTIR (thin films, cm–1) ymax: 1183
(P=N), 871 (P–O–C). H NMR (500 MHz, CDCl3) dH: 0.86
Preparation of N3P3[OC6H4CH=CHC(O)–C6H4OC12H25]6
(4b)
Compound 4b was obtained as pale yellow solid. Yield:
1
(3H, t, 1 Â CH3), 1.26–1.80 (20H, m, 10 Â CH2), 4.02 (2H,
t, OCH2), 6.94 (2H, d, J = 8.60 Hz, Ar–H), 7.29 (2H, d, J =
8.60 Hz, Ar–H), 7.48 (1H, d, J = 15.45 Hz, 1 Â olefinic H),
7.65 (2H, d, J = 8.0 Hz, Ar–H), 7.74 (1H, d, J = 15.45 Hz, 1 Â
olefinic H), 8.01 (2H, d, J = 8.0 Hz, Ar–H). 13C NMR
(125.77 MHz, CDCl3) dC: 14.12, 22.68, 25.97, 29.00, 29.09,
29.25, 29.34, 29.42, 29.49, 29.58, 31.90, 68.32, 114.36,
121.87, 122.70, 129.86, 130.58, 130.83, 133.80, 141.95,
151.24, 163.25, 188.27. 31P NMR (200 MHz, CDCl3) dP:
12.74 (t, J = 60.0 Hz, Pa–P), 23.27 (d, J = 60.0 Hz, Pb–P).
Anal. calcd. (%) N3P3Cl5C27H35O3: C, 45.06; H, 4.90; N,
5.84. Found (%): C, 45.03; H, 4.83; N, 5.76.
72%; mp 141–143 8C. FTIR (thin films, cm–1) ymax: 3064
(C–H in aromatic), 1180 (P=N), 883 (P–O–C). 1H NMR
(500 MHz, CDCl3) dH: 0.86 (3H, t, 1 Â CH3), 1.25–1.78
(20H, m, 10 Â CH2), 3.97 (2H, t, OCH2), 6.87 (2H, d, J =
7.45 Hz, Ar–H), 7.00 (2H, d, J = 8.00 Hz, Ar–H), 7.41 (1H,
d, J = 16.00 Hz, 1 Â olefinic H), 7.46 (2H, d, J = 8.00 Hz,
Ar–H), 7.71 (1H, d, J = 16.00 Hz, 1 Â olefinic H), 7.91
(2H, d, J = 7.45 Hz, Ar–H). 13C NMR (125.77 MHz,
CDCl3) dC: 14.09, 22.66, 25.99, 29.12, 29.33, 29.38, 29.56,
29.59, 29.61, 29.64, 31.89, 68.25, 114.29, 121.36, 121.88,
129.58, 130.47, 130.73, 132.34, 142.19, 120.64, 163.13,
188.03. 31P NMR (200 MHz, CDCl3) dP: 8.84 (s, 3P, N3P3
ring). Anal. calcd. (%) N3P3C162H210O18: C, 75.41; H, 8.20;
N, 1.63. Found (%): C, 74.87; H, 8.17; N, 2.16.
Preparation of N3P3Cl5[OC6H4CH=CHC(O)C6H4OC14H29]
(3c)
Compound 3c was obtained as pale yellow solid. Yield:
18%; mp 68–71 8C. FTIR (thin films, cm–1) ymax: 1184
Preparation of N3P3[OC6H4CH=CHC(O)–C6H4OC14H29]6
(4c)
1
(P=N), 871 (P–O–C). H NMR (500 MHz, CDCl3) dH: 0.87
(3H, t, 1 Â CH3), 1.25–1.80 (24H, m, 12 Â CH2), 4.03 (2H,
t, OCH2), 6.95 (2H, d, J = 8.60 Hz, Ar–H), 7.29 (2H, d, J =
8.60 Hz, Ar–H), 7.49 (1H, d, J = 16.00 Hz, 1 Â olefinic H),
7.66 (2H, d, J = 8.60 Hz, Ar–H), 7.73 (1H, d, J = 15.45 Hz,
1 Â olefinic H), 8.00 (2H, d, J = 8.05 Hz, Ar–H). 13C NMR
(125.77 MHz, CDCl3) dC: 14.09, 22.66, 25.95, 29.08, 29.33,
29.33, 29.53, 29.50, 29.62, 29.62, 29.63, 29.66, 31.89,
68.31, 114.34, 121.89, 122.71, 129.85, 130.56. 130.81,
133.78, 141.97, 150.32, 163.23, 188.26. 31P NMR
(200 MHz, CDCl3) dP: 12.74 (t, J = 60.0 Hz, Pa–P), 23.27
(d, J = 60.0 Hz, Pb–P). Anal. calcd. (%) N3P3Cl5C29H39O3:
C, 46.58; H, 5.26; N, 5.62. Found (%): C, 46.43; H, 5.14;
N, 5.59.
Compound 4c was obtained as pale yellow solid. Yield:
70%; mp 137–138 8C. FTIR (thin films, cm–1) ymax: 3068
(C–H in aromatic), 1177 (P=N), 880 (P–O–C). 1H NMR
(500 MHz, CDCl3) dH: 0.87 (3H, t, 1 Â CH3), 1.25–1.80
(24H, m, 12 Â CH2), 4.03 (2H, t, OCH2), 6.95 (2H, d, J =
8.60 Hz, Ar–H), 7.29 (2H, d, J = 8.60 Hz, Ar–H), 7.49 (1H,
d, J = 16.00 Hz, 1 Â olefinic H), 7.66 (2H, d, J = 8.60 Hz,
Ar–H), 7.73 (1H, d, J = 15.45 Hz, 1 Â olefinic H), 8.00
(2H, d, J = 8.05 Hz, Ar–H). 13C NMR (125.77 MHz,
CDCl3) dC: 14.09, 22.66, 25.95, 29.08, 29.33, 29.33, 29.53,
29.50, 29.62, 29.62, 29.63, 29.66, 31.89, 68.31, 114.34,
121.89, 122.71, 129.85, 130.56. 130.81, 133.78, 141.97,
150.32, 163.23, 188.26. 31P NMR (200 MHz, CDCl3) dP:
8.86 (s, 3P, N3P3 ring). Anal. calcd. (%) N3P3C174H234O18:
C, 76.03; H, 8.58; N, 1.53. Found (%): C, 75.90; H, 8.31;
N, 1.70.
Synthesis of hexasubstituted cyclotriphosphazene (4a–4c)
General procedure
A mixture of hexachlorocyclotriphosphazenes (2.01 mmol),
2a (12.06 mmol), and K2CO3 (24.12 g) in acetone (60 mL)
was heated at reflux for 1 h. The mixture was allowed to
cool to room temperature and filtered. The filtrate was dried,
filtered, and concentrated in vacuo. The crude solid was re-
crystallized from acetone to afford 4a–4c.
Acknowledgements
We are grateful to the Universiti Malaysia Sarawak and
the Ministry of Science, Technology, and Innovation
(MOSTI) for the financial support through FRGS/01(03)/
608/2006(41).
Preparation of N3P3[OC6H4CH=CHC(O)–C6H4OC10H21]6
(4a)
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Compound 4a was obtained as pale yellow solid. Yield:
82%; mp 143–145 8C. FTIR (thin films, cm–1) ymax: 3067
(CH in aromatic), 1180 (P=N), 881 (P–O–C). 1H NMR
(500 MHz, CDCl3) dH: 0.81 (3H, t, 1 Â CH3), 1.22–1.71
(16H, m, 8 Â CH2), 3.97 (2H, t, OCH2), 6.89 (2H, d, J =
9.15 Hz, Ar–H), 7.20 (2H, d, J = 8.60 Hz, Ar–H), 7.25 (1H,
d, J = 15.45 Hz, 1 Â olefinic H), 7.41 (2H, d, J = 8.60 Hz,
Ar–H), 7.62 (1H, d, J = 15.45 Hz, 1 Â olefinic H), 7.95
(2H, d, J = 9.15 Hz, Ar–H). 13C NMR (125.77 MHz,
CDCl3) dC: 14.09, 22.66, 25.99, 29.12, 29.31, 29.38, 29.55,
30.92, 31.87, 68.25, 114.29, 121.37, 121.88, 129.58, 130.47,
130.73, 132.35, 142.18, 151.65, 163.12, 188.01. 31P NMR
(200 MHz, CDCl3) dP: 8.86 (s, 3P, N3P3 ring). Anal. calcd.
(%) N3P3C150H186O18: C, 74.69; H, 7.77; N, 1.74. Found
(%): C, 73.86; H, 7.60; N, 1.83.
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