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

Tanrıkulu, Güler İnci; Özgür, Mehtap; Okumuş, Aytuğ; Kılıç, Zeynel; Hökelek, Tuncer; Aydın, Betül; Açık, Leyla

doi:10.1016/j.ica.2019.03.018

Cited by 26 publications

(11 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…N -H-R ′ -N ′ -mono(4-fluoro/nitrophenylmethyl)diamines [49,57] and bis(4-fluorophenylmethyl)diamines [51] were prepared via reducing the corresponding Schiff bases obtained from the reactions between 4-fluoro/nitrobenzaldehyde and the appropriate N -alkyldiamines and N , N ′bisalkyldiamines in MeOH. The Cl-replacement reactions of N 3 P 3 Cl 6 with 4 equimolar amounts of N -H-R ′ -N ′ -mono(4-fluoro/nitrophenylmethyl)diamines in dry THF at ambient temperature to produce 2 different types of products, namely partly substituted mono(4-fluoro/nitrophenylmethyl)spirocyclotriphosphazenes (I) [49,50,57] and cis/trans-bis(4-fluoro/nitrophenylmethyl)dispirocyclotriphosphazenes (III) [50]. The monospiro (I) and bisdi spiro (III) derivatives were separated via column chromatography.…”

Section: Synthesismentioning

confidence: 99%

“…However, the same trend is not observed for 5-membered Ia and IIa. This is due to the fact that Ia has 2 independent molecules in the asymmetric unit [50].…”

Section: ∆(P-n)mentioning

confidence: 99%

“…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].…”

Section: Introductionmentioning

confidence: 99%

“…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].…”

Section: Introductionmentioning

confidence: 99%

“…It was found out that in cyclotriphosphazene derivatives, variations in the 31 P NMR shifts depend primarily on the electronic, steric and conformational factors (e.g., electron-releasing and withdrawing powers of substituents, the steric hindrance between the exocyclic groups), and on the differences in the bond lengths and bond angles around the phosphorus atoms, particularly endocyclic ( α) and on exocyclic ( α ′ ) bond angles. As a particular interest in our ongoing studies on phosphazene-based chemistry, the present study primarily focuses on a number of correlations established among the structural parameters in mono-and di-spirocyclophosphazene derivatives with 4-fluoro/nitrophenylmethyl pendant arm/arms of the compounds previously synthesized and published by our research group (Table 1) [49][50][51][52][57][58][59]. In this context, here we report our findings on the relationship among the δ P spiro shifts with endocyclic and exocyclic NPN bond angles, and electron density transfer parameters, and a brief description of the synthesis methods of 5 types and a total of 19 cyclotri/tetraphosphazenes containing 4-fluoro/nitrophenylmethyl pendant arm and 5-to 7-membered spiro-rings.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

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

Okumuş¹,

Elmas²,

Asmafiliz³

et al. 2020

Turk J Chem

Self Cite

View full text Add to dashboard Cite

A great wealth of structural information about phosphazenes can be gleaned from the combined spectroscopic and crystallographic data. When data from 31 P NMR spectroscopy and X-ray crystallography are put together like pieces in a puzzle, a number of correlations can be obtained for phosphazene derivatives. A systematic study concerning the correlations among the structural parameters (e.g., 31 P NMR data, endocyclic/exocyclic NPN bond angles and bond lengths) revealed some characteristics of mono-and di-spirocyclophosphazene derivatives bearing 4fluoro/nitrophenylmethyl pendant arm/arms. These correlations include the relationship between the δ P spiro shifts, the values of electron density transfer parameters ∆ (P-N), and the endocyclic and exocyclic NPN bond angles of the cyclophosphazenes. The structural parameters were compared with each other for 19 compounds of 5 different architectural types of cyclophosphazenes with 5-to 7-membered spiro-rings.

show abstract

Section: Synthesismentioning

confidence: 99%

“…However, the same trend is not observed for 5-membered Ia and IIa. This is due to the fact that Ia has 2 independent molecules in the asymmetric unit [50].…”

Section: ∆(P-n)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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

Okumuş¹,

Elmas²,

Asmafiliz³

et al. 2020

Turk J Chem

Self Cite

View full text Add to dashboard Cite

show abstract

The comparative reactions of 2‐cis‐4‐ansa and spiro cyclotetraphosphazenes with difunctional ligands: Structural and stereogenic properties, electrochemical, antimicrobial and cytotoxic activity studies

Okumuş

Elmas

Kılıç

et al. 2021

Applied Organom Chemis

Self Cite

View full text Add to dashboard Cite

In this study, two kinds of compounds, namely, mono‐ferrocenyl‐2‐cis‐4‐dichloro‐ansa‐ (2,4‐ansa; 3) and mono‐ferrocenyl‐spiro‐ (spiro; 4) hexachlorocyclotetraphosphazenes, were obtained by the Cl replacement reaction of N4P4Cl8 (1) with an equimolar amount of sodium 3‐(N‐ferrocenylmethylamino)‐1‐propanoxide (2). The reactions of 2,4‐ansa (3) with excess diamines and dialkoxides resulted in the formation of ansa‐cyclotetraphosphazenes (3a–3e). Spiro (4) was reacted with excess diamines and dialkoxides to give the mono‐ferrocenyl‐spiro‐cyclotetraphosphazenes (4a–4d). Although 2,4‐ansa (3) produced the dispiro (3a) with N‐(4‐fluorobenzyl)‐N′‐methylethane‐1,2‐diamine, it afforded both monospiro (3b) and dispiro (3c) with N‐(4‐fluorobenzyl)‐N′‐methylpropane‐1,3‐diamine. However, spiro (4) yielded a trispiro (4a) with N‐(4‐fluorobenzyl)‐N′‐methylethane‐1,2‐diamine and 2,6‐dispiro (4b) with N‐(4‐fluorobenzyl)‐N′‐methylpropane‐1,3‐diamine. The structures of the phosphazenes were elucidated by FTIR, ESI‐MS and/or HRMS, spectroscopic and crystallographic (for 3f and 4b) data. Furthermore, the electrochemical findings of cyclotetraphosphazenes exhibited electrochemically reversible one‐electron oxidation of Fe‐redox centre. As an example, the chirality of 3c was investigated by 31P NMR spectroscopy on the addition of (R)‐(+)‐2,2,2‐trifluoro‐1‐(9′‐anthryl)‐ethanol, chiral solvating agent (CSA). The circular dichroism (CD) (for 3d and 3e), HPLC (for 3d, 3e and 3f) and X‐ray (for 3f) display that these compounds have chirality (RS′ or SR′) in the solution and solid state. This paper also focuses on the antimicrobial activities, the interactions with pBR322 DNA, in vitro anticancer activity against L929 fibroblast and MCF7 breast cells, and antituberculosis activity against Mycobacterium tuberculosis H37Rv of the cyclotetraphosphazenes.

show abstract

Phosphorus‐nitrogen compounds part 59. The syntheses of tetrachloro and tetraamino‐2‐pyridylmethylspiro(N/N)ethylenediaminocyclotriphosphazenes: Structural characterization, bioactivity, and molecular docking studies

Bozkurt

Elmas

Yakut

et al. 2021

J Chinese Chemical Soc

Self Cite

View full text Add to dashboard Cite

In this study, primarily, tetrachloro-2-pyridylmethylspiro-N/N-ethylenediaminocyclotriphosphazenes (4 and 5) were prepared from the reactions of equimolar amounts of N-alkyl-N 0 -2-pyridylmethylethylenediamines, [PyCH 2 NH(CH 2 ) 2 NHR (R:CH 3 , 2 and R:C 2 H 5 , 3)], and hexachlorocyclotriphosphazene [(HCCP, trimer), N 3 P 3 Cl 6 (1)]. Compounds 4 and 5 react with secondary amines to yield the fully substituted tetraamino-2-pyridylmethylspiro-N/N-ethylenediaminocyclotriphosphazenes (4a-5c) in dry THF, respectively. These derivatives were obtained by both conventional and microwave-assisted reactions, and their yields were compared. In addition, it should also be noted that these cyclotriphosphazenes were obtained for use in the investigation of their spectral, crystallographic, antimicrobial, and anticancer properties. The structures of the compounds were elucidated by spectral data. The crystal structures of 4, 5a, and 5c were clarified by the single crystal X-ray diffraction technique. Antibacterial activities and biofilm preventions of 4a-c and 5a-c against bacteria, and their antifungal activities against fungi were investigated. According to broth microdilution method, the results showed that all compounds were highly effective against C. albicans. The interactions of these compounds with DNA and their cytotoxic activities against L929 fibroblast and A549 lung cancer cell lines were investigated. In addition, Density Functional Theory (DFT) calculations of 4, 5a, and 5c were made, and molecular docking studies with DNA and cytochrome P450 enzyme were presented.

show abstract

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

Cited by 26 publications

References 46 publications

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

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

The comparative reactions of 2‐cis‐4‐ansa and spiro cyclotetraphosphazenes with difunctional ligands: Structural and stereogenic properties, electrochemical, antimicrobial and cytotoxic activity studies

Phosphorus‐nitrogen compounds part 59. The syntheses of tetrachloro and tetraamino‐2‐pyridylmethylspiro(N/N)ethylenediaminocyclotriphosphazenes: Structural characterization, bioactivity, and molecular docking studies

Contact Info

Product

Resources

About