The reactions of N$_{3}$P$_{3}$Cl$_{6}$ with monodentate and bidentate ligands: the syntheses and structural characterizations, in vitro antimicrobial activities, and DNA interactions of 4-fluorobenzyl(N/O)spirocyclotriphosphazenes

Abstract

Abstract:The Cl replacement reactions of 4-fluorobenzyl(N/O)spirocyclotriphosphazene (2) with excess monoamines led to the formation of 4-fluorobenzylspiro(N/O)tetraaminocyclotriphosphazenes (2a-2d). The partly substituted dispiro 3b and dispiro 3c and fully substituted trispirocyclotriphosphazenes (trans 4a, cis 4c, 4d, and 4e) were obtained, respectively, from the reactions of 2 with one equimolar and two equimolar amounts of diamines, aminoalcohol, and diols. Although efforts were made for the separation of the cis/trans and optical isomers of the dispiro phosphazenes, only one set of diastereomers (RR/RS or SS/SR) of dispiro 3b and dispiro 3c was isolated, respectively. The 31 P NMR spectral data of the other dispiro phosphazenes were evaluated from the 31 P NMR spectra of the reaction mixtures. The reactions of 2 with excess N-methylethylenediamine gave trans 4a as a racemic mixture. While trans 4b(racemic) and cis 4b (meso) occurred from the reaction of 2 with excess N-methyl-1,3-propanediamine, they were not isolated separately. Some of the phosphazenes were screened against bacteria and fungi. The activities of the compounds against anaerobic and microaerophilic gram-negative bacteria were evaluated. It was found that compounds 2, 2b, and trans 4a exhibited tolerable toxic effects on fibroblast cells and had the highest toxicity against MCF-7 cells.

The Spectroscopic and Thermal Properties, Antimicrobial Activities and DNA Interactions of 4-(Fluorobenzyl)Spiro(N/O) Cyclotriphosphazenium Salts

“…The amino alcohol, 3-(4-fluorobenzylamino)-1-propanol, was prepared from the reaction of 4fluorobenzaldehyde with 3-amino-1-propanol in methanol according to the published procedure (21). The partly (1) and fully substituted cyclotriphosphazene derivatives (2a-2d) were also synthesized with respect to the literature (18,22).…”

“…The 31 P { 1 H} NMR spectral data and the spin systems of the tetrachloro-4fluorobenzyl(N/O)spirocyclotriphosphazene ( 1) and its tetraamino derivatives (2a-2d) [22] for comparison and their salts (3a-3d) were tabulated in Table 1. and 3d) due to the salt formation with the bulky organic acid.…”

Phosphorus-nitrogen compounds (Part 51): the relationship betweenspectroscopic and crystallographic data of mono- and di-spirocyclophosphazenederivatives with 4-fluoro/nitrophenylmethyl pendant arm/arms

“…Besides this, our research group has long focused on performing substituent exchange reactions of Cl-atoms in partly substituted derivatives with heterocyclic amines {pyrrolidine, piperidine, morpholine, 1,4-dioxa-8-azaspiro [4,5]decane, 1-(2aminoethyl)pyrrolidine, 1-(2-aminoethyl) piperidine, 4-(2-aminoethyl)morpholine}and vanillin side groups, aiming at investigating spectral properties, cytotoxic, antituberculosis and antimicrobial activities, and DNA interactions of the obtained fully substituted cyclophosphazenes. In the last decade, 4-fluorobenzyl pendant armed monospiro and dispiro phosphazenes were prepared from the separate reactions of N 3 P 3 Cl 6 and N 4 P 4 Cl 8 with 4-fluorobenzyl-NN/NO donor type ligands [47][48][49][50][51][52]. The phosphezenium salts (protic ionic liquids, PILs or protic molten salts, PMOSs) of fully substituted 4-fluorobenzyl spirocyclotriphosphazenes were also synthesized via reactions of free phosphazene bases with bulky organic acids [53][54][55].…”

“…The phosphezenium salts (protic ionic liquids, PILs or protic molten salts, PMOSs) of fully substituted 4-fluorobenzyl spirocyclotriphosphazenes were also synthesized via reactions of free phosphazene bases with bulky organic acids [53][54][55]. The spectroscopic and stereogenic properties, and biological activity (antibacterial, antifungal, and cytotoxic activities) of all the (4-fluorobenzyl)spirocyclophosphazenes and some of their phosphazenium salts have been investigated by our research groups [47][48][49][50][51][52][53][54][55].…”

Syntheses and spectroscopic investigations of 2-pyridyl(N/N)spirocyclotriphosphazenes

“…Hexachlorocyclotriphosphazene, N3P3Cl6, is the best-known starting compound used for the preparation of the new phosphazene derivatives in the field of phosphazene chemistry (3). Hence, its Cl substitution reactions with monodentate (4,5) and bidentate reagents (6,7) have been thoroughly examined for years on account of the formation of various structural isomers and stereoisomers. The replacement reactions of N3P3Cl6 with monoamines and diamines led to the formation of partly and fully substituted aminocyclotriphosphazenes (8).…”