Phosphorus‐Nitrogen Compounds: Novel Spirocyclic Phosphazene Derivatives. Structure of 3,3″‐Propane‐1,3‐diylbis[4′,4′,6′,6′‐tetrachloro‐3,4‐dihydrospiro[1,3,2‐benzoxazaphosphorine‐2,2′λ⁵‐[4λ⁵,6λ⁵][1,3,5,2,4,6]triazatriphosphorine]]

Abstract

The reactions of N2O2‐donor‐type aminopodands 1–3 with trimer N3P3Cl6 led to the novel spirocyclic phosphazene derivatives 4–10 (Scheme). Compounds 4–7 and 8–10 are the first examples of the substituted spiro‐ansa‐spiro and spiro‐bino‐spiro phosphazene derivatives, respectively. The pyrrolidinyl‐substituted phosphazene derivatives 7 and 10 were synthesized from 5 and 9, respectively, with an excess of pyrrolidine. The reaction of aminopodand 3 (R(CH2)4) with N3P3Cl6 in dry THF afforded only spiro‐ansa‐spiro phosphazene 6. The molecular structure of compound 9 was determined by X‐ray diffraction: it shows the novel spiro‐bino‐spiro phosphazene architecture.

The reactions of hexachlorocyclotriphosphazatriene with pyridine derivatives

“…In the IR spectra of 6-10, the characteristic ν P N vibrations occur between 1194 and 1226 cm −1 . These data are in accordance with the reported values for phosphazene derivatives [21][22][23]. The indication of the partially substitutions for compounds 6-10 is given by the ν P Cl stretching bands observed at 592, 588, 592, 583, and 556 cm −1 , respectively.…”

Syntheses, structural characterization and biological activities of spiro-ansa-spiro-cyclotriphosphazenes

“…28 The partly substituted sbs phosphazenes {3,3 00propane-1,3-diylbis[4 0 ,4 0 ,6 0 ,6 0 -tetrachloro-3,4-dihydrospiro[1,3,2benzoxazaphosphorine-2,2 0 l 5 -[4l 5 ,6l 5 ] [1,3,5,2,4,6] triazatriphosphorine]] (5) and 3,3 00 -butane-1,4-diylbis[4 0 ,4 0 ,6 0 ,6 0 -tetrachloro-3,4-dihydrospiro[1,3,2-benzoxazaphosphorine-2,2 0 l 5 -[4l 5 ,6l 5 ]- [1,3,5,2,4,6]triazatriphosphorine]] (6)} and sas phosphazenes {meso-8,8-dichloro-18,19,20-trihydro-6l 5 ,8l 5 ,10l 5 -6,10-nitrilo-16H,22H [1,3,5,7,2,4,6]tetrazatriphosphecino[2,1-b:6,7-b 0 ]bis [1,3,2]benzoxazaphosphorine (7) and meso-8,8-dichloro-18,19,20,21tetraydro-6l 5 ,8l 5 ,10l 5 -6,10-nitrilo-16H,23H [1,3,5,7,2,4,6]tetrazatriphosphecino[2,1-b:6,7-b 0 ]bis [1,3,2]benzoxazaphosphorine (8)} were prepared using a method in which dibenzo-diaza-podands (3 and 4) and N 3 P 3 Cl 6 were refluxed in dry THF according to the published procedure by our research group. 29,30 The preparation and spectroscopic data of fully pyrrolidine substituted sas phosphazene {meso-8,8-18,19,20-trihydro-8,8-dipyrrolidine-1-yl-6l 5 ,8l 5 ,10l 5 -6,10-nitrilo-16H,22H [1,3,5,7,2,4,6]tetrazatriphosphecino[2,1-b:6,7-b 0 ]bis [1,3,2]benzoxazaphosphorine} (9a) were reported by our group…”

“…The formation of sas and sbs skeletons seems to proceed by SN 1 (P) and SN 0 (P) involving the intermediate (I) (Scheme 1). Evidence for the formation of the 6-membered spiro ring of the intermediate (I) with the geminal substitution in the first step arises from the formation of a bino bridge for the sbs skeleton 30 with an ansa ring for the sas skeleton. Generally, triethylamine or excessive amine has been used to remove the liberated HCl as NEt 3 ÁHCl or amineÁHCl, respectively, in the nucleophilic substitution reactions of chlorocyclophosphazenes with amines.…”

“…The asymmetric unit of a The values are taken from the literature. 30 b The spectral data are available in the literature 30 and were re-recorded for comparison purposes. a The spectral data are available in the literature 30 and were re-recorded for comparison purposes.…”

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

“…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. [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 .…”