Novel phosphazene derivatives: Synthesis, anisochronism and structural investigations of mono- and ditopic spiro-crypta phosphazenes

Asmafiliz, Nuran; İlter, Elif Ece; Işıklan, Muhammet; Kılıç, Zeynel; Tercan, Barış; Çaylak, Nagihan; Hökelek, Tuncer; Büyükgüngör, Orhan

doi:10.1016/j.molstruc.2006.08.017

Cited by 19 publications

(14 citation statements)

References 29 publications

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“…2,6-Dioxa-14,18-diazatricyclo-[18⋅4⋅0⋅0 7,12 ]-tetracosa- 7,9,11,20,22,24(1)-hexaene 1, 2,6-dioxa-14, 19-diazatricyclo-[19⋅4⋅0⋅0 7,12 ]-pentacosa- 7,9,11,21,23,25(1)-hexaene 2 and 2,7-dioxa-15,19-diazatricyclo-[19⋅4⋅0⋅0 8,13 ]-pentacosa-8, 10, 12, 21, 23, 25(1)-hexaene 3 40,41 were prepared according to the cited procedures. Also compound 4 was obtained from the reaction of 1 with N 3 P 3 Cl 6 according to the reported method.…”

Section: Synthesis Of Compoundsmentioning

confidence: 99%

“…Also compound 4 was obtained from the reaction of 1 with N 3 P 3 Cl 6 according to the reported method. 24 2.2a Synthesis of 7,12-[propane-1,3-diyldioxydi-ophenylene-dimethylene]-2,2,4,4-tetrachloro-2λ 5 , 4λ 5 , 6λ 5 -tri phosphaza(6-P v )-1,3,5,7,12-pentazaspiro[6⋅5] trideca-1,3,5-triene (5): A solution of N 3 P 3 Cl 6 (3⋅34 g, 9⋅60 mmol) in dry THF (50 mL) and Et 3 N (2⋅67 ml, 19⋅20 mmol) were slowly added to a solution of coronand 2 (3⋅00 g, 9⋅60 mmol) in THF (100 mL). The mixture was stirred for 2 days and the solvent was evaporated.…”

Section: Synthesis Of Compoundsmentioning

confidence: 99%

“…The proton decoupled 31 P-NMR spectral data of 4, 24 5, 6 and 7, and analogous spiro-crypta phosphazenes (I-VII) 23,24,26,48 are listed in table 3. The 31 P-NMR spectra of 5, 6 and 7 are interpreted as ABX, ABX and AMX, respectively.…”

Section: Spectroscopic Analysesmentioning

confidence: 99%

“…[10][11][12] Hence, researchers have focused on the replacement reactions of halogen atoms of halophosphazenes by different nucleophiles, e.g. primary and secondary amines, [13][14][15] diamines, [16][17][18] diphenols, [19][20][21][22] diaza-crown ethers (coronands) [23][24][25][26] and aminophenols. 27 In addition, chlorophosphazene derivatives have attracted increased attention and a new class of chiral phosphazene bases have been synthesized and characterized.…”

Section: Introductionmentioning

confidence: 99%

“…27 In addition, chlorophosphazene derivatives have attracted increased attention and a new class of chiral phosphazene bases have been synthesized and characterized. [28][29][30] In recent years, our group has focused on the reactions of bulky bifunctional reagents, such as aromatic diamines, 31 aminophenols, 27 diphenols 32-33 and diaza-crown ethers [23][24][25][26] with N 3 P 3 Cl 6 . While the reactions of aminophenols and diaza-crown ethers with N 3 P 3 Cl 6 lead respectively, to the formation of spiro-and spiro-crypta phosphazene derivatives, as major products, the condensation reaction of methylenebis(4-nitrophenol) with N 3 P 3 Cl 6 yields the ansacompound, as the major product among the spiro-, spiro-spiro-and spiro-ansa-skeletons.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2008

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The reactions of hexachlorocyclotriphosphazatriene, N 3 P 3 Cl 6 , with N 2 O 2 -donor type coronands,, respectively. The reaction of 4 with excess pyrrolidine leads to the formation of geminal. The 31 P-NMR spectra of 5 and 6 indicate that these compounds have anisochronism. The structures of 5, 6 and 7 were investigated by X-ray crystallography. For 7, the sums of the bond angles around the N atoms were 348⋅6(2)° and 349⋅7(2)° indicating that the N atoms have pyramidal configurations and are stereogenic. The relationship between the chemical shift values δP (spiro) and the Δ(P-N) (electron density transfer parameters) of 4, 5, 6, 7 and the analogous compounds as well as the relationship between the Δ(δP) values and the above mentioned Δ(P-N) are presented respectively. In addition, the relationship between the endocyclic NPN bond angles of these compounds and the 31 P-NMR chemical shifts of the spiro-phosphorus atoms were investigated. The spectroscopic and structural investigations of the compounds were made by elemental analyses, MS, FTIR, one-dimensional 1 H-, 13 C-, 31 P-NMR, DEPT and two-dimensional COSY, HETCOR, HMBC, homo-and heteronuclear correlation techniques.

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Section: Synthesis Of Compoundsmentioning

confidence: 99%

Section: Synthesis Of Compoundsmentioning

confidence: 99%

Section: Spectroscopic Analysesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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

et al. 2008

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Phosphorus‐nitrogen compounds. Part 39. Syntheses and Langmuir‐Blodgett thin films and antimicrobial activities of N/N and N/O spirocyclotriphosphazenes with monoferrocenyl pendant arm

Asmafiliz

Civan

Özben

et al. 2018

Applied Organom Chemis

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The Cl substitution reactions of the N/N (1-3) and N/O (4 and 5) spirocyclic monoferrocenylphosphazenes with 1,4-dioxa-8-azaspiro [4,5]decane (DASD) produce the mono-(1a-5a), geminal-(1b-5b) and tetrakis-DASD-substituted ferrocenylspirocyclotriphosphazenes (1c-5c). The mono-and geminal-DASDsubstituted phosphazenes have two and one stereogenic P-centers, respectively. The structures of the compounds were established by spectroscopic techniques.The molecular structures of 3a and 2b were evaluated using X-ray crystallography. Additionally, the ultrathin and highly ordered Langmuir-Blodgett (LB) films of 3a and 2b were also prepared. The characterizations of the LB films were done using p-polarized grazing angle (GAIR) and horizontal attenuated total reflectance (HATR) techniques. On the other hand, the antimicrobial activities of the eight phosphazene derivatives against G(+) and G(-) bacteria and fungi were investigated. Furthermore, the interactions between the compounds and plasmid DNA were studied by agarose gel electrophoresis. isomers may cause to the possibilities of optical isomers.On the other hand, phosphazene derivatives and polyorganophosphazenes are very useful compounds in technological and medicinal areas. They are used as flame retardant additives, [5] electrolytes for lithiumion batteries, [6,7] liquid crystals, [8,9] lubricants, [10] fluorescence chemosensor [11,12] and elastomers. [13] Recently, cyclotriphosphazene derivatives have also attracted a quite of interest for the preparation of the selective anticancer agents, [14] antibacterial and antifungal reagents, [15] and biomedical materials such as synthetic bones. [16] Furthermore, the potential anticancer activities of some of the mono and polyamino substituted cyclotriphosphazenes were reported. [17,18] Besides, the ultrathin films of the obtained inorganic or organic compounds have attracted much interest for applications as industrial materials, as well, such as detectors, sensors, and electronic circuit components. [19] The thin films were prepared using a solid substrate with different methods e.g. thermal evaporation, adsorption from solution, electrodeposition, sputtering, self-assembly molecular beam epitaxy, and Langmuir-Blodgett (LB) techniques. [20,21] There is only one report in the literature about the LB thin films of the phosphazene derivatives published by our group. [22] This study focused on the consecutive Cl replacement reactions of the tetrachloro monoferrocenylphosphazenes (1-5) with DASD for the aim of the obtaining of electronrich reservoir phosphazenes. Thereof, the mono-(1a-5a), geminal (1b-5b) and tetra-DASD-substituted (1c-5c) ferrocenylphosphazenes were synthesized by the reaction of 1-5 with DASD. In addition, the successive substitution reactions of Cl atoms from the pendant armed tetrachloroferrocenylphosphazenes (1-5) emerges a number of different possibilities in terms of regio-and stereoisomer selections. Eventually, we strongly stated that these compounds have been synthesized to investigate their biol...

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Synthesis of a melamine‐cyclotriphosphazene derivative and its application as flame retardant on cotton gauze

Yao

Yang

et al. 2016

J of Applied Polymer Sci

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The halogen-free flame retardance of natural fiber is an everlasting challenge due to the well-known poor solubility of phosphazene in water. In this case, a new cyclotriphosphazene derivative (MCP) was synthesized. It was etherized hexamethylolmelamine (HMMM) and hexachloro-cyclotriphosphazene (HCCP) by one pot reaction. It was characterized by 1 H NMR, 13 C NMR, 31 P NMR, FT-IR, TGA, SEM, limited oxygen index (LOI) and vertical flame testing. The MCP has good solubility in water and thermosetting MCP has compact structure which can expand several times after burning. Cotton gauze was soaked in six different concentration of aqueous solutions of MCP (0 wt %, 5 wt %, 10 wt %, 15 wt %, 20 wt % and 25 wt %, respectively) to obtain the flame retardant cloth. The cloth was soaked in 20 wt % MCP solution had higher char yield and LOI. They had no any afterflame and afterglow, and gauze 2-gauze 5 cannot be burned out in 12s ignition time.

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Novel phosphazene derivatives: Synthesis, anisochronism and structural investigations of mono- and ditopic spiro-crypta phosphazenes

Cited by 19 publications

References 29 publications

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

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

Phosphorus‐nitrogen compounds. Part 39. Syntheses and Langmuir‐Blodgett thin films and antimicrobial activities of N/N and N/O spirocyclotriphosphazenes with monoferrocenyl pendant arm

Synthesis of a melamine‐cyclotriphosphazene derivative and its application as flame retardant on cotton gauze

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