ChemInform Abstract: An Answer to the Spiro versus Ansa Dilemma in Cyclophosphazenes. Part 4. Reaction of Spermidine and Spermine on N₃P₃CI₆.

Abstract

Spermidin (I) reagiert mit dem Cyclotriphosphazen (II) zum Produkt (III), dessen Struktur mit "Spirobino" bezeichnet wird (MS, NMR).

The reactions of cyclotriphosphazene with 2-(2-hydroxyethylamino)ethanol. Spectroscopic studies of the derived products

“…The reactions with spermidine (as a triamine) gave only one product, N 3 P 3 Cl 4 NH[(CH 2 ) 3 NH(CH 2 ) 4 NH] 2 N 3 P 3 Cl 5 . This was confirmed by single crystal Xray diffraction to have a 6-membered spiro ring, involving one N 3 P 3 moiety and a bridge to a second such unit [49,50].…”

“…The reactions of cyclotriphosphazene (1) with tri-functional nucleophilic reagents have been previously studied [49][50][51][52][53]. The reactions with spermidine (as a triamine) gave only one product, N 3 P 3 Cl 4 NH[(CH 2 ) 3 NH(CH 2 ) 4 NH] 2 N 3 P 3 Cl 5 .…”

Electrophoresis and Biosensor-Based DNA Interaction Analysis of the First Paraben Derivatives of Spermine-Bridged Cyclotriphosphazenes

“…In this context, spermine-bridged cyclotriphosphazene 1 was synthesized as a starting material according to the literature . Reactions of compound 1 with methyl-, ethyl-, propyl-, butyl-, and benzyl paraben were then performed in the presence of sodium hydride and tetrahydrofuran to obtain full paraben-substituted dispirobinospermine derivative cyclotriphosphazenes 2 – 6 .…”

“…In this context, spermine-bridged cyclotriphosphazene 1 was synthesized as a starting material according to the literature. 41 Reactions of compound 1 with methyl-, ethyl-, propyl-, butyl-, and benzyl paraben were then performed in the presence of sodium hydride and tetrahydrofuran to obtain full parabensubstituted dispirobinospermine derivative cyclotriphosphazenes 2−6. All the synthesized compounds were purified by column chromatography and the identification of isolated compounds were carried out by MALDI−TOF mass spectrometry, DCS curves, and 1 H and 31 The 1 H NMR chemical shifts and coupling constants for compounds 2−6 were given in the Experimental Section.…”

“…The asymmetric unit of all compounds includes only one molecule and the cyclotriphosphazene rings are fully substituted with octamethyl-, ethyl-, propyl-, butyl-, and benzylparabens, as shown in ball−stick represantations in Figures 3 and 4 14)°, and are somewhat larger than those of the above-mentioned N−P− N angles. Analysis of previously reported crystallographic studies on spermine-bridged cyclophosphazene derivatives showed that a free rotation around single C−C bound in the flexible alkyl-chain could lead to the two conformations, which is identified as syn (CSD refcode: COPTUW01, 42 PAJVUS, 43 GUZPOG, 44 GUZPIA 44 or anti (CSD refcode: COPTUW, 41 BADJEW, 45 BADJIA, 45 CEGNEI, 46 CEGNIM, 46 GIFBAA 34 ) conformations of the cyclophosphazene moiety with respect to each other. In all compounds, two cyclotriphosphazenes stand in anti-conformation to each other, possibly under the influence of crowded paraben groups.…”