13882-05-8Relevant academic research and scientific papers
Synthesis, crystal structure and hydrolysis of novel isomeric cage (P-C/P-O)-phosphoranes on the basis of 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane and hexafluoroacetone
Khasiyatullina, Nadezhda R.,Mironov, Vladimir F.,Krivolapov, Dmitry B.,Mironova, Ekaterina V.,Gnezdilov, Oleg I.
, p. 85745 - 85755 (2016)
The reaction of 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane with hexafluoroacetone leads to the simultaneous formation of regioisomeric cage (P-C/P-O)-phosphoranes, the structures of which are unequivocally confirmed by XRD. The rearrangement of the P-C-isomer to P-O-isomer with high stereoselectivity (>96%) takes place in methylene chloride solution with the retention of the phosphorus coordination. It was found that the stepwise hydrolysis of the P-O-isomer initially gives 2-(2,3-dihydroxy-1,2-diphenyl-3-trifluoromethyl-4,4,4-trifluorobutyloxy)-4,4,5,5-tetramethyl-2-oxo-1,3,2-dioxaphospholane as the only stereoisomer whose structure is also confirmed by XRD. Further hydrolysis of this compound leads to the formation of 2,3-dihydroxy-3-trifluoromethyl-4,4,4-trifluoro-1,2-diphenylbutylphosphate and pinacol, which forms the solvate in the crystal. Hydrolysis of the P-C-isomer yields 2-hydroxy-4,4,5,5-tetramethyl-2-oxo-1,3,2-dioxaphospholane, benzoin and hexafluoroisopropanol.
STRUCTURE AND REACTIVITY OF 2-HYDROXYIMINOBENZYL-2-OXO-4,4,5,5-TETRAMETHYLDIOXAPHOSPPHOLANES
Breuer, E.,Karaman, R.,Gibson, D.,Goldblum, A.
, p. 433 - 438 (2007/10/02)
The reaction of 2-benzoyl-2-oxo-4,4,5,5-tetramethyldioxaphospholane (3) with hydroxylamine yields the corresponding E oxime (E-4) and benzonitrile (5), which arises from fragmentation of the Z oxime via an intramolecular attack of the N-OH on the phosphorus.
α CETOPHOSPHONATES ET ESTERS CYCLIQUES D'HYDROXYMETHYLENES DIPHOSPHONATES SYNTHESES, STRUCTURES ET HYDROLYSE
Tromelin, Anne,El Manouni, Driss,Burgada, R.
, p. 301 - 312 (2007/10/02)
Synthesis of symmetrical diesters derived from hydroxy methylene diphosphonic acids 1 to 8 is described either in one step or via the corresponding α ketophosphonate 1a to 8a.Study of the diphosphonates (1 to 6) -> phosphate-phosphonates (1b to 6b) isomerization has been realized.Results related to peculiar cases in connection with nonsymmetrical esters 10, 11, 17 and study of the hydrolysis reaction of diphosphonates are presented.
