Phosphorus−Nitrogen Compounds. 14. Synthesis, Stereogenism, and Structural Investigations of Novel N/O Spirocyclic Phosphazene Derivatives

Abstract

The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6, with N/O donor-type N-alkyl-o-hydroxybenzyl- and o-hydroxynaphthylamines result in novel mono- (3a, 4a and 4b), di- (5a and 5b), and tri- (3b, 6a, and 6b) spirocyclic phosphazene derivatives. The tetrakis-pyrrolidinophosphazene, 3b, has been obtained from the reaction of partly substituted compound 3a with the excess pyrrolidine in tetrahydrofuran. The relationship between the endocyclic NPN (alpha) and exocyclic NPO (alpha') bond angles of the analogous spirocyclic phosphazenes with the deltaP shifts of NPO phosphorus atoms have been presented. It was observed that there is a linearity between alpha angles and deltaP shifts, while no linear relationship has been observed for alpha' angles. In addition, we have found the correlation between Delta(P-N) and deltaNPO shifts, which implies a linear relationship. Delta(P-N)=(a-b), where a and b are the average lengths of two adjacent P-N bonds. The structural investigations of all of the compounds have been made by elemental analyses; mass spectrometry; Fourier transform infrared spectroscopy; one-dimensional 1H, 13C, and 31P NMR; distortionless enhancement by polarization transfer; and two-dimensional correlation spectroscopy, heteronuclear shift correlation, and heteronuclear multiple-bond correlation homo- and heteronuclear correlation techniques. The solid-state structures of 3a, 4a, 4b, and 5a have been determined by X-ray crystallographic techniques. The asymmetric units of compounds 3a and 4a contain two independent molecules, and 3a has strong intermolecular N-H...N hydrogen bonds linking three phosphazene rings. The molecular structure of 6a looks like a propeller where the chemical environment of P1 is different from that of P2 and P3. On the other hand, compounds 5a and 5b are expected to exist as cis- or trans-geometric isomers and to be in cis (meso) or trans (racemic) configurations. The crystallographic and preliminary chiral solvating agents results show that both of them are trans (racemic). In addition, 6a and 6b are also expected to exist as cis-trans-trans- and cis-cis-cis-geometric isomers; both of them are found to be in cis-trans-trans geometries. According to the two-dimensional spectroscopic data, the possible conformations of 3a and 4a in CDCl3 are the same with the solid-state structures.

Phosphorus-nitrogen compounds: Part 15. Synthesis, anisochronism and the relationship between crystallographic and spectral data of monotopic spiro-crypta phosphazenes

“…However, a linearity between the δP-shifts and α angles has been observed for spirocyclic phosphaza lariat ethers 25 and spiro-cyclic (NPO) phosphazene derivatives. 49 The order of α-values are; N 3 P 3 Cl 6 > the compounds in region B cycle > the compounds in region A cycle in figure 5a.…”

The Syntheses and Structural Characterizations, Antimicrobial Activity and in Vitro Dna Binding of 4-Fluorobenzylspiro(n/O)cyclotriphosphazenes and Their Phosphazenium Salts

“…The microorganisms used in antimicrobial screening included three bacteria {Escherichia coli ATCC 25922 (G-), Klebsiella pneumoniae ATCC 13883 (G) and Enterobacter faecalis ATCC 29212 (G+)} and a fungus (Candida albicans ATCC 10231). The MIC values were determined in benzo- (1,2,3)-thiadiazole-7-carbothioic acid S-methyl ester (BTH) broth using serial dilution of the compounds ranging from 3000-15,63 µM with adjusted bacterial and fungal concentration (1x10 6 CFU/mL, 0,5 McFarland's standard). Bacterial strains were grown in nutrient agar medium and incubated at 37 ⁰C for 24 h. The yeast cells were cultured on Sabouraud dextrose agar (SDA) medium and incubated at 30 ⁰C for 48 h. Ampicillin (Amp, 10 µg/mL) and Chloramphenicol (C, 30 µg/mL) (antibacterial), and Ketoconazole (K, 50 µg/mL) (antifungal) were used as controls.…”

“…The condensation reactions of N3P3Cl6 with excess monodentate and bidentate ligands resulted in the formation of fully substituted cyclotriphosphazenes [3]. For instance, there are several studies in the literature on the reactions of cyclotriphosphazenes with NO donor type difunctional reagents [4][5][6]. Some of the cyclotriphosphazene derivatives are used as liquid crystals [7,8], rechargeable lithium-ion batteries [9,10], OLEDs [11,12], and lubricants [13,14].…”

Chiral configurations in cyclophosphazene chemistry

“…Some crystallographic examples are given as meso and/or racemic forms for Type II(3) meso-cis (6 [36], 12a [46], 40a [87], 40b* [88], 40c [89], 41a* [90], 41b,c [ (3) rac-trans (5 [36], 9a [62], 11a,d [46], 51 [97], 52a,b [98], 53 [36], 54* [99]). It is not possible meso form for Type II(4), Type II(5), Type II(7) Type II (8) and Type II (9) configurations.…”