Synthesis, cytotoxic and biological activities of new partly and fully mono- and dispiro-4-methoxybenzylaminophosphazenes.

WOS: 000505772703362

Phosphorus-nitrogen compounds. spiro- and crypta-phosphazene derivatives: synthesis and spectral investigations. Structure of butane-N,N '-bis(1,4-oxybenzyl)-spiro(propane-1,3-diamino) tetrachlorocyclo-2 lambda(5), 4 lambda(5), 6 lambda(5),-triphosphazatriene. Part VII

Hokelek, Tuncer/0000-0002-8602-4382; Asmafiliz, Nuran/0000-0002-9335-4101WOS: 000222521900015The condensation reactions between trimer, N3P3Cl6, and diamines, 2 and 4 and {1-{N-[1-(2-hydroxynaphthylmethyl)aminomethylidene]}-2(1H)-naphthalenone, 3, yielded the new spiro-cyclic- (5 and 8) and the novel spiro-phosphazene (7) derivatives, respectively. The fully substituted phosphazene (6) was also obtained from the reaction of 5 with the excess of pyrrolidine. Compounds (4-8) have been characterized by elemental analyses, FTIR, H-1-, C-13-, P-31-NMR, HETCOR, COSY and MS. The structure of crypta-phosphazene, 8, has been examined crystallographically. Compound 8 is the first example of the crypta-phosphazene derivatives. The P-31-NMR spectra of compounds 7 and 8 indicate that, both of the compounds have anisochronism because of the stereogenic centers. The pyramidal geometry of two spiro-cyclic nitrogen atoms in compound 8, gives rise to stereogenic property. The sums of the bond angles around N-4 and N-5 nitrogens are 350.6(2) and 349.6(3)degrees, respectively. Compound 8 crystallizes in the triclinic space group P (1) over bar with a = 8.798(3), b = 10.498(3) and c = 15.689(4) Angstrom; alpha = 91.35(2), beta = 103.39(4) and gamma = 102.88(4)degrees; V = 1369.9(7) Angstrom(3), Z = 2 and D-x = 1.491 g cm(-3). It consists of a non-centrosymmetric, non-planar phosphazene ring with a bulky dibenzo-diazacrown etheric side group. (C) 2004 Elsevier B.V. All rights reserved

Phosphorus-nitrogen compounds. spiro- and crypta-phosphazene derivatives: Synthesis and spectral investigations. Structure of butane-N,N?-bis(1,4- oxybenzyl)-spiro(propane-1,3-diamino)tetrachlorocyclo-2?5, 4?5, 6?5-triphosphazatriene. Part VII

The condensation reactions between trimer, N3P 3Cl6, and diamines, 2 and 4 and {1-{N-[1-(2- hydroxynaphthylmethyl)aminomethylidene]}-2(1H)-naphthalenone, 3, yielded the new spiro-cyclic- (5 and 8) and the novel spiro-phosphazene (7) derivatives, respectively. The fully substituted phosphazene (6) was also obtained from the reaction of 5 with the excess of pyrrolidine. Compounds (4-8) have been characterized by elemental analyses, FTIR, 1H-, 13C-, 31P-NMR, HETCOR, COSY and MS. The structure of crypta-phosphazene, 8, has been examined crystallographically. Compound 8 is the first example of the crypta-phosphazene derivatives. The 31P-NMR spectra of compounds 7 and 8 indicate that, both of the compounds have anisochronism because of the stereogenic centers. The pyramidal geometry of two spiro-cyclic nitrogen atoms in compound 8, gives rise to stereogenic property. The sums of the bond angles around N4 and N5 nitrogens are 350.6(2) and 349.6(3)°, respectively. Compound 8 crystallizes in the triclinic space group P1 with a=8.798(3), b=10.498(3) and c=15.689(4)Å; ?=91.35(2), ?=103.39(4) and ?=102.88(4)°; V=1369.9(7)Å3, Z=2 and Dx=1.491gcm-3. It consists of a non-centrosymmetric, non-planar phosphazene ring with a bulky dibenzo-diazacrown etheric side group. © 2004 Elsevier B.V. All rights reserved.2001-07-05-064The authors wish to acknowledge the purchase of the CAD-4 diffractometer and financial support of this work under grants DPT/TBAG1 and CHE-93250012 of the Scientific and Technical Research Council of Turkey and Ankara University Research Fund (grant number: 2001-07-05-064) for financial support

Phosphorus-nitrogen compounds: Part 46. The reactions of N3P3Cl6 with bidentate and monodentate ligands: The syntheses, structural characterizations, antimicrobial and cytotoxic activities, and DNA interactions of (N/N)spirocyclotriphosphazenes with 4-chlorobenzyl pendant arm

In the present study, the partly and fully-substituted monospiro (4–6, 4a-6d), cis-dispiro (7–9), trans-dispiro (10–15) cyclotriphosphazenes were synthesized for the investigations of their chemical, stereogenic and biological properties. The cis/trans phosphazenes (7–12) have two stereogenic P centers. They are expected to be in meso and racemic forms. In addition, the structures of four compounds were evaluated using X-ray crystallographic data. Compound 13 was found to be a single enantiomer (RR) in the solid state, as also proved with its CD spectrum. The antibacterial and antifungal activities of the phosphazenes were elucidated for against Gram-positive (G+) and Gram-negative (G?) bacteria, and yeast strains, respectively. Of the compounds, 14 exhibits strong antimicrobial activity against most of the tested organisms, especially B. cereus and E. hirae. MBC and MFC values of compounds on different bacterial and fungal species ranged from <9.8 µM to 2500 µM. Furthermore, the cytotoxic activities of 6, 4c, 10 and 14 were investigated against L929 fibroblast and DLD-1 cells, and 14 was the most cytotoxic compound against DLD-1. © 2019 Elsevier B.V.Hacettepe Üniversitesi: 013 D04 602 004Türkiye Bilimler AkademisiTürkiye Bilimsel ve Teknolojik Araştirma Kurumu, TÜBITAK: 116Z400The authors acknowledge the Scientific and Technical Research Council of Turkey Grant No. 116Z400. Z. K. thanks the Turkish Academy of Sciences ( TÜBA ) for partial support of this work. T. H. is grateful to Hacettepe University Scientific Research Project Unit (Grant No. 013 D04 602 004)

PHOSPHORUS-NITROGEN COMPOUNDS: PART 25. SYNTHESES, SPECTROSCOPIC,

The condensation reactions of hexachlorocyclotriphosphazene (N3P3Cl6) with mono (1 and 2) and bisferrocenyldiamines (3-5 and 7) resulted in the formation of tetrachloro mono- (8 and 9) and bisferrocenylspirocyclotriphosphazenes (10-13). In addition the tetramorpholino mono- (8a and 9a) and bisferrocenylphosphazenes (10a-12a) were obtained from the reactions of the corresponding tetrachlorophosphazenes (8-12) with excess morpholine. The structures of all the phosphazenes were determined using FTIR, MS, H-1, C-13, and P-31 NMR and 2-dimensional NMR techniques. The structures of 9a and 13 were determined by single crystal X-ray diffraction techniques. Cyclic voltammetric investigations of compounds 8a, 9a, and 11a revealed that ferrocene redox centers undergo reversible oxidation. These ferrocenylphosphazenes appear to be quite robust electrochemically. Interactions between the compounds 8a, 9a, 11a, and 12a and pBR322 plasmid DNA were investigated by agarose gel electrophoresis. [Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional text and figures.

Stereogenic Centers upon the Addition of Chiral Solvating Agents

The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6, with N/O-donor-type N-alkyl (or aryl)-o-hydroxybenzylamines (la-le) produce mono- (2a-2e), di- (3a-3d), and tri- (4a and 4b) spirocyclic phosphazenes. The tetrapyrrolidino monospirocyclic phosphazenes (2f-2i) are prepared from the reactions of partly substituted compounds (2a-2d) with excess pyrrolidine. The dispirodipyrrolidinophosphazenes (3e-3h) and trispirophosphazenes (3i-3k) are obtained from the reactions of trans-dispirophosphazenes with excess pyrrolidine and sodium (3-amino-1-propanoxide), respectively. Compounds 3a-3d have cis and trans geometric isomers. Only the trans isomers of these compounds are isolated. Compounds 3a-3h have two stereogenic P atoms. They are expected to be in cis (meso) and trans (racemic) geometric isomers. In the trans trispiro compounds (3i-3k), there are three stereogenic P atoms. They are expected to be in racemic mixtures. The stereogenic properties of 3a-3k are confirmed by P-31 NMR spectroscopy upon the addition of the chiral solvating agent; (S)-(+)-2,2,2-trifluoro-1-(9'-anthryl)ethanol. The molecular structures of 3i-3k, 4a, and 4b look similar to a propeller, where the chemical environment of one P atom is different from that of others. Additionally, 4a and 4b are also expected to exist as cis-trans-trans and cis-cis-cis geometric isomers, but both of them are found to be in cis-trans-trans geometries. The solid-state structures of 2a, 2e, 2f, 3e, and 31 are determined by X-ray crystallography. The compounds 2f-2i, 3e-3i, and 3k are screened for antibacterial activity against Gram-positive and Gram-negative bacteria and for antifungal activity against yeast strains. These compounds (except 3f) have shown a strong affinity against most of the bacteria. Minimum inhibitory concentrations (MIC) are determined for 2f-2i, 3e-3i, and 3k. DNA binding and the nature of interaction with pUC18 plasmid DNA are studied. The compounds 2f-2i, 3e-3i, and 3k induce changes on the DNA mobility. The prevention of BamHI and HindIII digestion (except 2g) with compounds indicates that the compounds bind with nucleotides in DNA