Phosphorus-Nitrogen compounds part 47: The conventional and microwave-assisted syntheses of dispirocyclotriphosphazene derivatives with (4-fluoro/4-nitrobenzyl) pendant arms: Structural and stereogenic properties and DNA interactions

The Cl exchange reactions of hexachlorocyclotriphosphazene, N3P3Cl6, were carried out with the bidentate ligands to obtain the new phosphazene derivatives. The spectroscopic and crystallographic properties of the compounds were investigated in detail. The absolute configurations of the two compounds...

Full description

Saved in:
Bibliographic Details
Published in:Inorganica Chimica Acta 2019-05, Vol.490, p.179-189
Main Authors: İnci Tanrıkulu, Güler, Yakut Özgür, Mehtap, Okumuş, Aytuğ, Kılıç, Zeynel, Hökelek, Tuncer, Aydın, Betül, Açık, Leyla
Format: Article
Language:English
Subjects:
Crystal structure
Crystallography
Deoxyribonucleic acid
Diamines
Dispirocyclotriphosphazenes
DNA
Nitrogen compounds
NMR
Nuclear magnetic resonance
Nucleotides
Phosphazene
Plasmids
Single crystals
Spectroscopy
Stereoisomers
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The Cl exchange reactions of hexachlorocyclotriphosphazene, N3P3Cl6, were carried out with the bidentate ligands to obtain the new phosphazene derivatives. The spectroscopic and crystallographic properties of the compounds were investigated in detail. The absolute configurations of the two compounds were unambiguously established using X-ray crystallographic data. In addition, the interactions of the compounds with plasmid DNA indicated that these compounds caused a decrease in the mobilities and intensities of form I and form II DNA. The tested compounds inhibited enzyme cleavage indicating compound bindings to the specific G/G and A/A nucleotides. [Display omitted] •New dispirocyclotriphosphazenes were prepared.•The crystal structures of three compounds were established by X-ray crystallography.•The absolute configurations of the products were unambiguously determined.•The compounds caused the changes and damages in DNA conformation. The Cl exchange reactions of hexachlorocyclotriphosphazene, N3P3Cl6, with two equimolar amounts of N-alkyl-N′-mono(4-fluorobenzyl)diamines (1–3), FC6H4CH2NH(CH2)nNHR1 (n = 2 and 3, R1 = CH3 or C2H5), and N-alkyl-N′-mono(4-nitrobenzyl)diamines (4 and 5), NO2C6H4CH2NH(CH2)nNHR1 (n = 2, R1 = CH3 or C2H5), led to the formation of the mono(4-fluorobenzyl) (1a-3a) and mono(4-nitrobenzyl) (4a and 5a) spirocyclotriphosphazenes as minor products, and trans-bis(4-fluorobenzyl) (1b-3b) and trans-bis(4-nitrobenzyl) (4b and 5b) spirocyclotriphosphazenes as major products. The bis(4-fluorobenzyl)spirocyclotriphosphazene (1b) reacted with excess pyrrolidine to give fully substituted (1c) phosphazene. The structures of the new compounds were elucidated by elemental analyses, ESI-MS, FTIR, 1H, 13C, and 31P NMR techniques. The molecular and crystal structures of 1a, 3b and 6 were identified by single crystal X-ray crystallography. The absolute configurations of 3b and 6 were unambiguously established as SS and R respectively, using X-ray crystallographic data. On the other hand, the interactions of 1b, 1c, 3b-5b and 6 with plasmid DNA indicated that compounds 3b, 4b, and 5b caused a decrease in the mobilities and intensities of form I and form II DNA. Compounds 1b, 1c and 6 caused a double strand break of plasmid DNA. All of the tested compounds inhibited enzyme cleavage indicating compound bindings to the specific G/G and A/A nucleotides.
ISSN:0020-1693
1873-3255
DOI:10.1016/j.ica.2019.03.018