Oxidative fluorination in the Ph 2 SO–XeF 2 –Cl − system and fluorine exchange in the Ph 2 S(O)F 2 –Ph 2 S(O)F + system
Oxidative fluorination of diphenyl sulfoxide with xenon difluoride occurs under mild conditions in the presence of chloride ion to give Ph 2 S(O)F 2 in quantitative yield. Chloride ion appears to react with xenon difluoride to generate fluoride ion, and a mechanism of oxidative fluorination is propo...
Saved in:
Published in | Canadian journal of chemistry Vol. 74; no. 11; pp. 2002 - 2007 |
---|---|
Main Authors | , |
Format | Journal Article |
Language | English |
Published |
01.11.1996
|
Online Access | Get full text |
Cover
Loading…
Summary: | Oxidative fluorination of diphenyl sulfoxide with xenon difluoride occurs under mild conditions in the presence of chloride ion to give Ph
2
S(O)F
2
in quantitative yield. Chloride ion appears to react with xenon difluoride to generate fluoride ion, and a mechanism of oxidative fluorination is proposed that involves anionic Ph
2
S(O)F
−
and radical Ph
2
S(O)F
•
intermediates. Addition of cationic Ph
2
S(O)F
+
to Ph
2
S(O)F
2
initiates rapid fluorine exchange, presumably via a symmetrical fluorine-bridged intermediate, and this exchange process was monitored by
13
C and
19
F NMR spectroscopy. In the presence of chloride ion, Ph
2
S(O)Cl
2
is formed and can be identified by
13
C NMR and by its hydrolysis to Ph
2
SO
2
. Mechanisms are proposed for these reactions, and ab initio molecular orbital calculations (GAUSSIAN92) were carried out of the postulated intermediates. Key words: preparation of Ph
2
S(O)F
2
, Ph
2
S(O)F
+
, and Ph
2
S(O)Cl
2
; oxidative fluorination in the Ph
2
SO–XeF
2
–Cl
−
system; fluorine exchange in the Ph
2
S(O)F
2
–Ph
2
S(O)F
+
system. |
---|---|
ISSN: | 0008-4042 1480-3291 |
DOI: | 10.1139/v96-228 |