SYNTHESIS AND THE SPECTRAL INVESTIGATIONS OF N-PYRIDINYL-SPIRO-PHOSPHAZENES

1
SYNTHESIS AND THE SPECTRAL INVESTIGATIONS OF
N-PYRIDINYL-SPIRO-PHOSPHAZENES
Hakan Dala, Yasemin Süzena, Zeynel Kiliçb and
Tuncer Hökelekc a Department of Chemistry,
Faculty of Science, Anadolu University, 26470
Yenibaglar, Eskisehir, TURKEY b Department of
Chemistry, Faculty of Science, Ankara University,
06100 Tandogan, Ankara, TURKEY c Department of
Physics, Hacettepe University, 06800 Beytepe,
Ankara, TURKEY Abstract The condensation
reactions of N-?(2-hydroxyphenylmethyl)amino?-meth
ylpyridines (4-6) with trimer, N3P3Cl6, afford
partially substitued novel spiro-cyclic
phosphazene derivatives (7-9). The fully
substitued phosphazenes (10 and 11) have also
been obtained from the reactions of (9) with the
excess of pyrrolidine and morpholine. The solid
state structure of (8) has been determined by
X-ray crystallography. The spectral
investigations of all the compounds have been
made by FT-IR, 1H-,13C-, 31P-NMR, HETCOR and
MS. Introduction Cyclophosphazenes are an
important family of inorganic ring systems, which
traditionally have attracted attention for two
main reasons (i) to obtain small molecules of
phosphazen derivatives, (ii) and to produce
polymeric phosphazene derivatives . They also
play an important role in the chemistry of
heteroatom compounds. In resent years,
phosphazene polymers have attracted considerable
attention because they can be tailored to possess
a wide variety of physical and chemical
properties by changing the side groups 1. The
coordination chemistry of the various multi-site
ligands derived from cyclophosphazenes is
extremely interesting new area. Phosphazenes have
been proposed for a broader array of applications
including flame-retardants 2, rechargeable
lithium batteries microencapsulant membranes,
high performance fluids and ionic conductors, the
further design of the highly selective
anticancer, antibacterial, anti-HIV and
artificial bone 3 agents.
1H-NMR Spectrum in d 1-8 ppm. for a Compound 10
and b Compound 11
13C-NMR Spectrum in 10-160 ppm for 11
Scheme
Schiff Bases Corresponding Amine Corresponding Phosphazene R1 R2 R3
1 4 7 H CH3 H
2 5 8 CH3 H H
3 6 9 CH3 CH3 H
10 CH3 CH3
11 CH3 CH3
31P-NMR Spectrum a Compound 10 and b Compound
11
HETCOR Spectrum of (11)
Selected IR Bands
Compound ?(N-H) ?(C-H)arom. ?(C-H)alip. ?(CC) ?(PN) ?(P-Cl)
3 - 3061 m 2918 m 1544 vs - -
6 3421 vs 3049 m 29582924 m 1587 s - -
9 - 3089 m 29502853 m 1577 s 1189-1228 vs 516-578 s
10 - 3093 m 29622860 s 1560 s 1170-1225 vs -
11 - 3087 m 29642962 vs 1570 1088-1256 vs -
The conformations of (a) the spirocyclic system
and (b) The six-membered N/O ring in 8
An ORTEP-3 drawing of 8, with the atom-numbering
scheme
HMBC Spectrum of (11)
The possible stereoisomer structure of compound
11 at ambient temperature in CDCl3
HMBC correlations for 11

1. V. Chandrasekhar, K.R. Justin Thomas, Struct.
   Bonding. 81 (1993) 41.
2. J.E. Mark, H.R. Allcock, R.West, Inorganic
   Polymers Printince-Hall, Englewood Cliffs, NJ
   1992
3. Nair, Lakshmi S. Lee, Duron Laurencin, Cato T.
   Polyphosphazenes as novel biomaterials.Handbook
   of Biodegradable Polymeric Materials and Their
   Applications 1 (2006) 277
   

Contact hakandal_at_anadolu.edu.tr