PHOSPHORUS-NITROGEN COMPOUNDS. REACTIONS OF
CYCLOCHLOROTRIPHOSPHAZATRIENE WITH 2-MERCAPTOETHANOL.
IR AND NMR SPECTROSCOPIC INVESTIGATIONS OF THE PRODUCTS.
Derya ÇIRAK, Sedat TURE, Necibe KILIÇER
Bilecik Şeyh Edebali University, Faculty of Arts & Sciences, Department of Chemistry, 11230, Bilecik
[email protected]
Reactions of hexachlorocyclotriphosphazatriene, N 3P3Cl6 [1] with 2-mercaptoethanol [2], in (1:1:2
and 1:3:6) mole ratios, in THF and dichloromethane solutions, at room temperature and under
refluxing conditions yield a total of 5 novel products: one monospiro derivative, N 3P3Cl4[O-CH2-CH2-S]
[3]; three parallel- and antiparallel substituted dispiro isomers, N3P3Cl2[O--CH2-CH2-S]2 [4, 5 and 6]
and one thris-spiro derivative, N3P3[O-CH2-CH2-S]3 [7]. The structures of the derived compounds were
detected by elemental analysis, HPLC-MS, 31P and 1H NMR spectral data. Spectroscopic data,
product types and relative yields are compared witht hose of the previously investigated derivatives of
N3P3Cl6 [1] with 1-amino-2-propanol and difunctional reagents. A large variety of cyclophosphazene
derivatives through Cl replacement of N3P3Cl6 with monodentate and bisdentate nucleophiles, leads to
fully substituted cyclophosphazenes. The introduction of chiral derivatizing reagent has greatly
facilitated the determination of enantiomeric purity by NMR. The premise, first verified by Pirkle for
otically active solutes in chiral solvents, that the NMR spectra of enantiomers are nonequivalent in a
dissymmetric environment. Since the magnitude of the chirality induced shift, ∆ δ, has proven to be a
sensitive probe of steric enironment, it is expected tat chiral shift reagents C 4, where + denotes one
optical isomer of the chelate, will produce a differential shift, ∆ ∆ δ, between the resonances of
equivalent nuclei in an enantiometric pair (R, S).
Figure 1. Proton decoupled 31P NMR spectrum of single-brideged derivative derived from the
reactions of N3P3Cl6 (1) with [HS-CH2-CH2-OH], in CDCl3 at 162.00 MHz, room temperature,
referenced to external 85% H3PO4.
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