Oxidative fluorination of S, Se and Te compounds

Article abstract of DOI:10.1016/S0022-1139(99)00171-2

The synthesis and mechanism of formation of cis- and trans-Ph₂SF₄ is described. Starting compounds are Ph₂S or Ph₂SF₂ and the oxidizing agent is XeF₂ in the presence of Et₄NCl. Also described is the synthesis of related chalcogen(IV and VI) fluorides such as t-butylSF₃, difluorodibenzothiophene, PhSeF₃, Ph₂SeF₂, PhSF₅, p-MeC₆H₄SF₅, PhSeF₅, and PhTeF₅. The reactions of Ph₂S(O)F₂ with alcohols and with the H₂O-HF-glass system are briefly described.

Full text of DOI:10.1016/S0022-1139(99)00171-2

Journal of Fluorine Chemistry 101 (2000) 279±283
Oxidative ¯uorination of S, Se and Te compounds$
Xiaobo Ou, Alexander F. Janzen*
Department of Chemistry, University of Manitoba, Winnipeg, MB, Canada R3T 2N2
Received 9 May 1999; accepted 4 June 1999
Abstract
The synthesis and mechanism of formation of cis- and trans-Ph2SF4 is described. Starting compounds are Ph2S or Ph2SF2 and the
oxidizing agent is XeF2 in the presence of Et4NCl. Also described is the synthesis of related chalcogen(IV and VI) ¯uorides such as
t-butylSF3, di¯uorodibenzothiophene, PhSeF3, Ph2SeF2, PhSF5, p-MeC6H4SF5, PhSeF5, and PhTeF5. The reactions of Ph2S(O)F2 with
alcohols and with the H2O±HF-glass system are brie¯y described. # 2000 Elsevier Science S.A. All rights reserved.
Keywords: Cis- and trans-Ph2SF4; S, Se and Te ¯uorides; Oxidative ¯uorination with XeF2 and Cl ; The H2O±HF-glass system; Conversion of alcohols to
¯uorides with Ph2S(O)F2
1. Results and discussion
agent CF3OF for the preparation of trans-Ph2SF4 [6], and F2
for the preparation of cis- and trans-Ph2SF4 [7].
Oxidative ¯uorination with xenon di¯uoride is catalyzed
by halide ion, as demonstrated recently by the preparation of
sulfur(VI) and tellurium(VI) ¯uorides such as Ph2S(O)F2
[1,2], PhSF4Cl [3], and Ph2TeF4 [4]. As a continuation of
these studies we wish to report the synthesis of cis- and
trans-Ph2SF4, and related ¯uorides of sulfur, selenium and
tellurium, and the reactions of Ph2S(O)F2 with alcohols and
with the H2O±HF-glass system.
In the absence of Et4NCl, oxidation of Ph2S with excess
XeF2 in CD2Cl2 stops at the sulfur(IV) stage to give Ph2SF2,
consistent with our earlier report [5]. On adding Et4NCl to
this mixture, oxidation to the sulfur(VI) stage occurs to give
cis- and trans-Ph2SF4 in a 2.5 : 1 ratio in a combined yield of
30%. This preparation can be carried out more conveniently
in one stage according to Eq. (1), without the isolation of
Ph2SF2. These reactions always produce some trans-
PhSF4Cl, DF, FDF , and CD2F2. In solution, cis-Ph2SF4
slowly isomerizes to trans-Ph2SF4 and after 45 days the
cis : trans ratio is 1 : 6. Other workers have used the oxidiz-
ing
Arylsulfur penta¯uorides have been made previously by
the reaction of AgF2 with aryl disul®des or arylsulfur
tri¯uorides [8,9]. With XeF2 and Et4NCl, arylsulfur penta-
¯uorides PhSF5 and p-MeC6H4SF5 were prepared at 258C
within 10±30 min, Eq. (2). These products could also be
obtained by oxidizing ArSF3, prepared according to Eq. (3),
with XeF2 and Et4NCl.
ArSSAr ‡ XeF2 ‡ Et4NCl ! ‰ArSF3Š ! ArSF5
‡ Xe
Ar ˆ Ph; p-MeC6H4
(2)
Although previous studies in this laboratory have shown
that chloride ion is not necessary for the XeF2 oxidation to
sulfur(IV) ¯uorides [5], nevertheless, several experiments
were carried out which showed that chloride ion facilitates
the synthesis of sulfur(IV) ¯uorides, Eq. (3). For example, in
one experiment, XeF2 was added to (t-butylS)2 in CD2Cl2 in
a ptfe-lined NMR tube. Reaction and decomposition was
evident but the desired product t-butylSF3 was not detected.
When the reaction was repeated in the presence of Et4NCl,
t-butylSF3 was formed in ꢀ90% yield within 10 min and
identi®ed by 19F NMR.
Ph2S ‡ XeF2 ‡ Et4NCl ! ‰Ph2SF2Š
! cis - and trans - Ph2SF4 ‡ Xe
(1)
RSSR ‡ XeF2 ‡ Et4NCl ! RSF3 ‡ Xe
R ˆ Ph; p-MeC6H4; t-butyl
(3)
In another experiment, it was found that dibenzothio-
phene did not react with XeF2 in CD2Cl2 in a ptfe-lined
NMR tube within 30 min, but reaction occurred on adding
Et4NCl to this mixture to give di¯uorodibenzothiophene in
$Dedicated to Professor C.J. Willis on the occasion of his 65th
birthday.
*Corresponding author. Tel.: ‡1-204-474-9731; fax.: ‡1-204-474-7608.
E-mail address: ajanzen@cc.umanitoba.ca (A.F. Janzen)
0022-1139/00/$ ± see front matter # 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 1 7 1 - 2

280
X. Ou, A.F. Janzen / Journal of Fluorine Chemistry 101 (2000) 279±283
ꢀ95% yield (Eq. (4)), identi®ed by 19F and 13C NMR.
Further addition of XeF2 and Et4NCl failed to bring about
oxidation to a sulfur(VI) ¯uoride.
(4)
Using similar procedures, XeF2 and Et4NCl was found to
be suitable for the preparation of PhSeF3 or PhTeF3. With an
excess of XeF2, the chalcogen(VI) ¯uorides PhSeF5 or
PhTeF5 were formed (Eq. (5)), and identi®ed by their known
19F NMR spectra [10,11].
PhEEPh ‡ XeF2 ‡ Et4NCl
! ‰PhEF3Š ! PhEF5 ‡ Xe E ˆ Se; Te
(5)
A recently proposed mechanism of oxidative ¯uorination
of sulfur(IV) compounds by XeF2 and Cl [1±3] can be
extended in a straightforward manner to the oxidation of
chalcogen(IV) ¯uorides; it is applied in Scheme 1 to account
for the formation of cis-Ph2SF4.
Fig. 1. Calculated (3±21G*) structures and relative energies of phenyl-
sulfur fluorides.
According to Scheme 1, and using the N±X±L notation
[12], the oxidation of Ph2SF2 to cis-Ph2SF4 involves the
sequence of steps: 10-S-4 ! 12-S-5 ! 11-S-5 ! 12-S-6,
and the cleavage of the xenon±¯uorine bond involves a
radical intermediate, namely, R±F±Xe±Fꢁ, where
R ˆ Ph2SF3, consistent with previous suggestions
[3,13,14]. The cis geometry of the ®nal product implies a
cis arrangement of phenyl substituents in the intermediates
Ph2SF3 and Ph2SFꢁ3. Ab initio calculations (3±21G*) were
carried out which showed that the lowest energy isomer of
anionic Ph2SF3 has a cis arrangement of phenyl groups,
with one phenyl trans to a lone pair of electrons, as seen in
Fig. 1. Other isomeric structures are 66.7 and 72.0 kJ higher
in energy. Similarly, the radical intermediate Ph2SFꢁ3 of
lowest energy adopts a cis arrangement with one phenyl
trans to the unpaired electron, Fig. 1, while other isomeric
structures are ‡33.6 and ‡66.6 kJ higher in energy. The
calculations also show a general shortening (strengthening)
of S±F and S±C bonds as the anion is oxidized to the radical
intermediate.
Catalysis by trace amounts of Lewis acids, perhaps derived
from the H2O±HF-glass system [15], is another possible
explanation because Lewis acids such as SbF5 or PF5
catalyze cis±trans isomerization of chalcogen(VI) ¯uorides,
e.g., F2S[C6H4C(CF3)2O]2 [16], F2Te[C6H4C(CF3)2O]2
[17], F2TePh3Cl [18], and Ph2TeX4 [4].
The interaction of the H2O±HF-glass system with
Ph2S(O)F2 was brie¯y investigated to see if Ph2S(O)F2
could be used for monitoring the presence of common
impurities in ¯uorination reactions. In one experiment, a
Pyrex glass capillary was dried overnight at 1108C and
added to a solution of Ph2S(O)F2 in CD2Cl2 in a ptfe-lined
NMR tube. There was no reaction with dry Pyrex glass for at
least 18 h at ambient temperature, and the four C1±C4 peaks
in the 13C NMR spectrum of Ph2S(O)F2 remained
unchanged.
In another experiment, a Pyrex glass capillary was ®rst
dipped into water and then added to a solution of Ph2S(O)F2
in CD2Cl2 in a ptfe-lined NMR tube. A slow reaction
occurred over a period of 2±48 h as the surface water
converted Ph2S(O)F2 to sulfone Ph2SO2 and two equivalents
of HF, Eq. (7). Integration of the C1±C4 peaks of sulfone
The slow isomerization of cis- to trans-Ph2SF4 in solution
is not explained by the mechanism of Scheme 1. It is
possible that radical intermediates are involved, as sug-
gested for the formation of cis- and trans-PhSF4Cl [3].
Scheme 1. Proposed mechanism of formation of cis-Ph2SF4.

X. Ou, A.F. Janzen / Journal of Fluorine Chemistry 101 (2000) 279±283
281
Ph2SO2 gives a direct measure of the amount of surface
water introduced into the reaction mixture.
Et4NCl was recrystallized from dry CH3CN and stored in
a desiccator over P2O5. Solvents were dried by distillation
and stored over molecular sieve, and polytetra¯uoroethy-
lene (ptfe) equipment was dried at 1008C for several days.
XeF2 (Air products), CD2Cl2 (Aldrich), CD3CN (Aldrich)
and other reagents were commercial samples and used
without further puri®cation.
PhSeSePh was prepared with slight modi®cation accord-
ing to the literature method for the corresponding disul®de
[21]. Solid phenylselenol (1.58 g, 10 mmol) was added to a
stirred solution of CH2Cl2 (10 mL) and 10% aq. potassium
hydrogen carbonate. The reaction ¯ask is immersed in a
water bath and a solution of bromine (0.8 g, 5 mmol) is
added slowly to the stirred solution. During the addition of
bromine the colour disappears. After addition is completed,
the CH2Cl2 phase is separated and the aqueous phase
extracted with CH2Cl2 (10 mL). The CH2Cl2 phases are
combined and dried (MgSO4) and the solvent evaporated to
give yellow solid PhSeSePh.
If this sample is kept at room temperature for several
weeks, a very slow reaction sets in between HF and Pyrex
glass, which liberates boron and silicon ¯uorides and water,
Eq. (6). Water, slowly liberated in Eq. (6), produces more
sulfone Ph2SO2. As demonstrated previously (1), Lewis
‡
acids such as BF3 produce the cation Ph2S(O)F , Eq. (8),
and the latter cation undergoes rapid ¯uorine exchange with
Ph2S(O)F2, Eq. (9). In the presence of Lewis acids, the 13
C
NMR spectrum thus shows eight peaks, of which four C1-
C4 peaks can be assigned to ``rigid'' sulfone Ph2SO2. The
remaining four C1±C4 peaks are averaged because of the
rapid equilibrium of Eq. (9), but from the averaged 13C
chemical shifts, or from low-temperature 19F NMR spectra,
it is possible to estimate the ratio of Ph2S(O)F2 to
‡
Ph2S(O)F according to the method described previously
[1]. Consequently, by measuring the relative concentrations
‡
of Ph2SO2, Ph2S(O)F2 and Ph2S(O)F it is possible to
monitor the effect of the H2O±HF-glass system.
The above procedure was used for the preparation of
(p-MeC6H4S)2 from p-thiocresol.
HF ‡ borosilicate glass ! BF3 ‡ H2O ‡ Á Á Á ꢂslow† (6)
2.1. Reaction of XeF2 with Ph2S (without Et4NCl)
H2O ‡ Ph2SꢂO†F2 ! Ph2SO2 ‡ 2HF ꢂfast†
(7)
Liquid Ph2S (40 mL, 0.24 mmol) in a microsyringe was
added to a solution of XeF2 (120 mg, 0.71 mmol) in CD2Cl2
(0.25 mL) at 308C in a ptfe-lined NMR tube. Reaction
occurred on warming to about 58C with vigorous evolu-
tion of xenon gas. The tube was constantly shaken and the
reaction was complete within 10 min. No colour change was
observed in this reaction. Ph2SF2 was formed in essentially
quantitative yield, and identi®ed by 13C and 19F NMR [5],
but no phenylsulfur(VI) ¯uoride was detected.
‡
BF3 ‡ Ph3SꢂO†F2 ! Ph2SꢂO†F ‡ BF4
ꢂvery fast†
(8)
‡
‡
Ph2SꢂO†F2 ‡ Ph2SꢂO†F „Ph2SꢂO†F F SꢂO†FPh2F
ꢂvery fast†
(9)
The fact that hydrolysis readily converts Ph2S(O)F2 to
sulfone Ph2SO2 and HF, Eq. (7) [1,19], implies that
Ph2S(O)F2 has a high af®nity for oxygen and is a good
¯uoride donor. These properties are potentially useful for
the deoxo¯uorination of alcohols, as brie¯y described by
Ruppert [19]. Reactions of a variety of alcohols with
Ph2S(O)F2 were carried out and examples of the conversion
of alcohols to ¯uorides are described in Eq. (10).
2.2. Cis- and trans-Ph2SF4
Adding Et4NCl (40 mg, 0.24 mmol) to the above freshly
made Ph2SF2 caused rapid gas evolution and the solution
turned yellow. The reaction mixture was shaken for 30 min
and the colour faded to nearly colourless. 19F NMR con-
®rmed the formation of cis- and trans-Ph2SF4 in a 2.5 : 1
ratio in a combined yield of 30%. In solution, cis-Ph2SF4
slowly isomerized to trans-Ph2SF4; after 45 days cis : trans
ratio was 1 : 6. Also formed in this reaction was trans-
PhSF4Cl, identi®ed by 19F NMR [3], and ¯uorides such as
FHF , FDF , and CD2F2. Cis-Ph2SF4. 19F NMR (CD2Cl2)
ꢀ ‡ 44t, ‡ 105t (J ˆ 100 Hz). Trans-Ph2SF4 19F NMR
(CD2Cl2) ꢀ ‡ 64.3s.
Ph2SꢂO†F2 ‡ ROH ! R F ‡ Ph2SO2 ‡ HF
R ˆ Me; Et; p-MeC6H4; PhꢂCF3†CH; Et3Si
(10)
2. Experimental
NMR spectra were recorded on a Bruker AM300 spectro-
meter at 282.4 (19F) and 75.47 (13C) MHz, and chemical
shifts were measured relative to internal C6F6 ( 162.9 ppm
w.r.t. CFCl3) and SiMe4, respectively. Yields were deter-
mined by integration of NMR peaks but no attempt was
made to optimize yields of products. Ab initio molecular
orbital calculations were performed with the GAUSSIAN92
system of programs [20] at the 3±21G* level with full
optimization, except for the phenyl substituent where a
®xed standard geometry was chosen.
2.3. ArSF3 and ArSF5
Solid XeF2 (70 mg, 0.42 mmol) was added to a solution
of PhSSPh (30 mg, 0.14 mmol) in CD2Cl2 in a ptfe-lined
NMR tube at 258C to give, after 24 h, PhSF3 in ꢀ60% yield.
19F NMR (CD2Cl2) ꢀ 57.5d, 40.2t, (J ˆ 59 Hz). 13C NMR
(CD2Cl2) ꢀ C1 146.4, C2 126.8, C3 129.6, C4 134.2.

282
X. Ou, A.F. Janzen / Journal of Fluorine Chemistry 101 (2000) 279±283
A similar method was used to prepare p-MeC6H4SF3 in
ꢀ90% yield. 19F NMR (CD2Cl2) ꢀ
colour change or gas evolution. On adding Et4NCl (2 mg,
0.012 mmol) to this solution, there was immediate gas
evolution and the solution turned yellow. After 30 min
gas evolution ceased and the solution became colourless
again. The product, di¯uorodibenzothiophene, was formed
in essentially quantitative yield and characterized by 19F and
13C NMR. Further addition of XeF2 and Et4NCl failed to
bring about oxidation to a sulfur(VI) compound.
37.4t, 55.3d
(J ˆ 54.3 Hz).
To PhSSPh (17 mg, 0.078 mmol) in CD2Cl2 (0.3 mL) in a
ptfe-lined NMR tube was added Et4NCl (2 mg,
0.012 mmol) at 258C. Solid XeF2 (82 mg, 0.48 mmol)
was then added slowly to the reaction mixture and the
colourless solution turned yellow, with gas evolution. After
30 min, another batch of Et4NCl (6 mg, 0.036 mmol) was
added. Gas evolved vigorously and the solution turned deep
yellow and back to colourless, to give PhSF5 (25%), iden-
ti®ed by 19F NMR [3], along with some trans-PhSF4Cl. A
similar procedure was used to prepare p-MeC6H4SF5, iden-
ti®ed by 19F NMR [3].
An attempt to prepare Cl2SF4 was unsuccessful. Dark red
sulfur dichloride (10 mL, 0.16 mmol) in a microsyringe was
added to a solution of XeF2 (56 mg, 0.33 mmol) in CD2Cl2
at 258C in a ptfe-lined NMR tube. Et4NCl (2 mg,
0.012 mmol) was added and a rapid exothermic reaction
occurred with vigorous evolution of gas. The tube was
constantly shaken, and reaction appeared complete after
10 min. The colour of the solution became lighter when the
reaction was completed. The 19F NMR spectrum showed
two broad peaks characteristic of SF4 as well as DF and
FDF , but no evidence of a sulfur(VI) ¯uoride such as
Cl2SF4.
2.6. Reaction of XeF2 with Ph2SeCl2
Solid XeF2 (100 mg, 0.59 mmol) was added to a solution
of Ph2SeCl2 (70 mg, 0.23 mmol) in CD2Cl2 (0.3 mL) in a
ptfe bottle. The reaction mixture was stirred for 30 min, but
no reaction occurred, as judged by the absence of xenon gas
evolution. Adding Et4NCl (8 mg, 0.048 mmol) to this reac-
tion mixture produced gas evolution and changed the col-
ourless solution to yellow. After gas evolution ceased, the
solution turned colourless within 10 min. 19F and 13C NMR
spectra con®rmed the presence of Ph2SeF2, but there was no
evidence for the formation of phenylselenium(VI) ¯uorides,
even after two weeks at room temperature.
2.7. Preparation of PhSeF3and PhSeF5
Solid XeF2 (35 mg, 0.21 mmol) was added to a solution
of PhSeSePh (28 mg, 0.12 mmol) in CD3CN at 258C in a
ptfe-lined NMR tube. Negligible reaction occurred within
30 min. To this mixture was added Et4NCl (2 mg,
0.012 mmol), and a rapid reaction occurred with vigorous
evolution of xenon gas. The reaction was completed within
15 min during which time the original colourless solution
turned yellow and then back to colourless. The product
PhSeF3 was formed in ꢀ90% yield and identi®ed on the
basis of its broad 19F NMR peak [23].
PhSeF3 was also prepared by the method of Maxwell and
Wynne [24]. A mixture of PhSeSePh and AgF2 was gently
re¯uxed for 4 h at 478C in 1,1,2-trichlorotri¯uoroethane
with stirring under N2 atmosphere to give PhSeF3 in 32%
yield.
Adding another batch of Et4NCl (25 mg, 0.18 mmol) to
the freshly prepared solution of PhSeF3, described above,
caused rapid gas evolution. The solution turned yellow, then
back to colourless, and the reaction was complete within
15 min. PhSeF5 was formed in 25% yield, 19F NMR
(CD3CN) ꢀ 86.9q, 45.9d (J ˆ 191 Hz). Also formed in this
reaction was an unknown compound SeXF5 (10%), 19F
NMR (CD3CN) ꢀ 123q, 79.9d (J ˆ 227 Hz).
2.4. Preparation of t-butylSF3
Without Et4NCl: (tert-butylS)2 (10 mL, 0.052 mmol) was
syringed into a solution of XeF2 (45 mg, 0.26 mmol) in
CD2Cl2 (0.3 mL) in a ptfe-lined NMR tube. Gas evolution
took place after shaking for a few minutes and the solution
turned yellow. A deep blue viscous solution was eventually
obtained. The 19F and 13C NMR spectra of this sample
indicated that (tert-butylS)2 had decomposed into various
unidenti®ed products, but no t-butylSF3 was detected.
With Et4NCl: Solid XeF2 (70 mg, 0.41 mmol) was added
to a mixture of (tert-butylS)2 (10mL, 0.052 mmol) and
Et4NCl (10 mg, 0.06 mmol) in CD2Cl2 (0.3 mL) in a
ptfe-lined NMR tube at 258C. Gas evolved immediately
and the solution turned yellow. The tube was shaken and gas
evolution ceased after 10 min. and the solution turned back
to colourless. 19F NMR showed the formation of t-butylSF3
(ꢀ90% yield). 19F NMR (CD2Cl2) d-63.7t, 32.5d
(J ˆ 53 Hz).
Adding excess XeF2 and more Et4NCl caused oxidation
of t-butylSF3, but the major product was SF5Cl, identi®ed by
19F NMR [22].
2.8. Preparation of PhTeF5
2.5. Difluorodibenzothiophene
As reported previously, the formation of PhTeF5 occurs
slowly over a period of 4 h in modest yield in the absence of
Et4NCl [10]. The synthetic procedure was therefore mod-
i®ed to include the addition of Et4NCl.
Dibenzothiophene (22 mg, 0.12 mmol) was added to a
solution of XeF2 (40 mg, 0.24 mmol) in CD2Cl2. There was
no reaction within 30 min, as judged by the absence of

X. Ou, A.F. Janzen / Journal of Fluorine Chemistry 101 (2000) 279±283
283
Solid XeF2 (50 mg, 0.30 mmol) was added to a suspen-
Acknowledgements
sion of red orange Ph2Te2 (24 mg, 0.06 mmol) in CD3CN
(0.5 mL) in a 5 mL ptfe bottle at 108C. Gas evolved and
the solution turned yellow, and solid particles gradually
disappeared. At this stage, Et4NCl (2 mg, 0.012 mmol) was
added to the reaction mixture, more xenon gas evolved, and
the solution turned light yellow. After 15 minutes the
solution became nearly colourless and PhTeF5 was formed
in ꢀ90% yield, and identi®ed by its known 19F NMR
spectrum [10].
We thank the University of Manitoba for a graduate
fellowship award (to X.O.). Dr. R.G. Syvret (Air Products,
Allentown, PA) is thanked for a sample of XeF2.
References
[1] A.F. Janzen, X. Ou, J. Fluorine Chem. 71 (1995) 207.
[2] X. Ou, A.F. Janzen, Can. J. Chem. 74 (1996) 2002.
[3] X. Ou, G.M. Bernard, A.F. Janzen, Can. J. Chem. 75 (1997) 1878.
[4] M. Jang, A.F. Janzen, J. Fluorine Chem. 52 (1991) 45.
[5] R.K. Marat, A.F. Janzen, Can. J. Chem. 55 (1977) 3031.
[6] D.B. Denney, D.Z. Denney, Y.F Hsu, J. Am. Chem. Soc. 95 (1973)
8191.
2.9. Reaction of Ph2S(O)F2 with water and glass
A standard Pyrex test tube (Corning #9800) was drawn
into a capillary, and a small segment of dimensions
4 mm  1 mm was dried overnight at 1108C. The chemical
composition (weight percent) of this glass is [24]: 80.6%
SiO2, 13% B2O3, 4% Na2O, 2.3% Al2O3.
In a typical reaction with water, aliquots of water (usually
1±3 mL) were added to a solution of freshly prepared
Ph2S(O)F2 (72 mg, 0.30 mmol) in CD2Cl2 (0.3 mL) at
258C in a ptfe-lined NMR tube and the reactions monitored
by 13C and 19F NMR.
[7] I. Ruppert, J. Fluorine Chem. 14 (1979) 81.
[8] W.A. Sheppard, J. Am. Chem. Soc. 84 (1962) 3058.
[9] W.A. Sheppard, J. Am. Chem. Soc. 84 (1962) 3064.
[10] K. Alam, A.F. Janzen, J. Fluorine Chem. 27 (1985) 467.
[11] S.A. Lermontov, S.I. Zavorin, I.V. Bakhtin, A.N. Pushin, N.S.
Zefirov, P.J. Stang, J. Fluorine Chem. 87 (1998) 75.
[12] C.W. Perkins, J.C. Martin, A.J. Arduengo, W. Lau, A. Alegria, J.K.
Kochi, J. Am. Chem. Soc. 102 (1980) 7753.
[13] A.F. Janzen, X. Ou, M.G. Sowa, J. Fluorine Chem. 83 (1997) 27.
[14] A.F Janzen, Chem. & Eng. News, 12 October 1998, p. 8
[15] A.F. Janzen, Coord. Chem. Rev. 130 (1994) 355.
[16] R.S. Michalak, J.C. Martin, J. Am. Chem. Soc. 104 (1982) 1683.
[17] R.S. Michalak, S.R. Wilson, J.C. Martin, J. Am. Chem. Soc. 106
(1984) 7529.
2.10. Reaction of Ph2S(O)F2 with alcohols
[18] A.F. Janzen, M. Jang, Can. J. Chem. 67 (1989) 71.
[19] I. Ruppert, Chem. Ber. 113 (1980) 1047.
To Ph2S(O)F2 (60 mg, 0.30 mmol) in CD2Cl2 (0.3 mL) at
258C in a ptfe-lined NMR tube was added an equivalent
amount of alcohol, e.g., Ph(CF3)CHOH (52 mg, 0.3 mmol)
and the PhCH(CF3)F identi®ed by 13C NMR (CD2Cl2): ꢀ
(Ph) 127.5 ppm, 6.6 Hz, 129.1 ppm, 130.8 ppm, ꢀ (CF)
122.8 ppm, q,d 29.2, 281 Hz, ꢀ (CF3) 89 ppm, q, d 34.5,
185 Hz. A similar reaction with p-MeC6H4OH gave p-
MeC6H4F: ꢀC(CF) 93 ppm, d 166 Hz. Reactions with
MeOH, EtOH and Et3SiOH gave CH3F, CH3CH2F and
Et3SiF, respectively, identi®ed by 19F and 13C NMR.
[20] Gaussian 92, Revision: C.M.J. Frisch, G.W. Trucks, M. Head-
Gordon, P.M.W. Gill, M.W. Wong, J.B. Foresman, B.G. Johnson,
H.B. Schlegel, M.A. Robb, E.S. Replogle, R. Gomperts, J.L. Andres,
K. Raghavachari, J.S. Binkley, C. Gonzalez, R.L. Martin, D.J. Fox,
D.J. Defrees, J. Baker, J.J.P. Stewart, J.A. Pople. Gaussian,
Pittsburgh, PA, 1992.
[21] J. Drabowicz, M. Mikolajczyk, Synthesis (1980) 32.
[22] R.K. Harris, K.J. Parker, J. Chem. Soc. (1961) 4736.
[23] W.M. Maxwell, K.J. Wynne, Inorg. Chem. 20 (1981) 1707.
[24] Corning Technical Information Center.