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Neue Phospholen‐ und Phosphepin‐Derivate aus λ 3 ‐Phosphorverbindungen und Hexafluoraceton oder perfluorierten α‐Diketonen
Author(s) -
Kadyrov Alexander,
Neda Ion,
Kaukorat Thomas,
Sonnenburg Ralf,
Fischer Axel,
Jones Peter G.,
Schmutzler Reinhard
Publication year - 1996
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19961290620
Subject(s) - chemistry , hexafluoroacetone , ring (chemistry) , medicinal chemistry , diketone , stereochemistry , crystal structure , molecule , carbonyl group , crystallography , organic chemistry
New Phospholene and Phosphepine Derivatives from λ 3 ‐Phosphorus Compounds and Hexafluoroacetone or Perfluorinated α‐Diketones The reaction of the bis(2‐chloroethyl)amino‐substituted benzoxazaphosphorinone 1 with hexafluoroacetone (HFA) proceeds with insertion of the carbonyl group of HFA into the heterocycle of 1 to form the oxazaphosphepinedione 2 . Triethyl phosphite ( 3 ) and triphenyl phosphite ( 4 ) react with the perfluorinated diketones 5 and 6 with formation of the pentaoxyphosphoranes 7–10 containing a dioxaphospholene ring system. The reaction of the (2‐chloroethyl)amino‐ and bis(2‐chloroethyl)amino‐substituted 1,3,5,2‐triazaphosphorinanediones 11–14 with the perfluorinated diketone C 2 F 5 C(:O)C(:O)CF 3 ( 15 ) furnishes spirophosphorane derivatives with the dioxaphospholene ring system, 16 and 17 , in two cases only. Compound 1 and 2‐[bis(2‐chloroethyl)‐amino]‐4 H ‐1,3,2‐benzodioxaphosphorin‐4‐one ( 18 ) react with the perfluorinated α‐diketones 5 and 6 with insertion of the diketones into the heterocycle of 1 and 18 with formation of compounds 19–22 containing dioxa‐ and oxazaphosphepinone ring systems. The expected oxidative addition of the diketones to λ 3 P with formation of spirophosphoranes was not observed. Compounds 19–22 were obtained as mixtures of isomers ( 19a/b–22a/b ). Single crystal X‐ray structure analyses were conducted on 2 and 9 . The seven‐membered ring of 2 displays a “tub” conformation, with the O and benzo C atoms lying out of the plane of the other four atoms. The two independent molecules of 9 are similar, but differ in the degree of distortion from trigonal‐bipyramidal geometry of phosphorus.