A. Kadyrov et al., NEW PHOSPHOLENE AND PHOSPHEPINE DERIVATIV ES FROM LAMBDA(3)-PHOSPHORUS COMPOUNDS AND HEXAFLUOROACETONE OR PERFLUORINATED ALPHA-DIKETONES, Chemische Berichte, 129(6), 1996, pp. 725-732
The reaction of the bis (2-chloroethyl)amino-substituted benzoxazaphos
phorinone 1 with hexafluoroacetone (HFA) proceeds with insertion of th
e carbonyl group of HFA into the heterocycle of 1 to form the oxazapho
sphepinedione 2. Triethyl phosphite (3) and triphenyl phosphite (4) re
act with the perfluorinated diketones 5 and 6 with formation of the pe
ntaoxyphosphoranes 7-10 containing a dioxaphospholene ring system. The
reaction of the (2-chloroethyl)amino- and bis(2-chloroethyl)amino-sub
stituted 1,3,5,2-triazaphosphorinanediones 11-14 with the perfluorinat
ed diketone C2F5C(:O)C(:O)CF3 (15) furnishes spirophosphorane derivati
ves with the dioxaphospholene ring system, 16 and 17, in two cases onl
y. Compound 1 and 2-[bis (2-chloroethyl) amino]-4H-1,3,2-benzodioxapho
sphorin-4-one (18) react with the perfluorinated alpha-diketones 5 and
6 with insertion of the diketones into the heterocycle of 1 and 18 wi
th formation of compounds 19-22 containing dioxa- and oxazaphosphepino
ne ring systems. The expected oxidative addition of the diketones to l
ambda(3)P with formation of spirophosphoranes was not observed. Compou
nds 19-22 were obtained as mixtures of isomers (19a/b-22a/b). Single c
rystal X-ray structure analyses were conducted on 2 and 9. The seven-m
embered ring of 2 displays a ''tub'' conformation, with the O and benz
o C atoms lying out of the plane of the other four atoms. The two inde
pendent molecules of 9 are similar, but differ in the degree of distor
tion from trigonal-bipyramidal geometry of phosphorus.