Synthesis and reaction chemistry of fluoroxydifluoromethyl fluoroformyl peroxide

Article abstract of DOI:10.1016/s0022-1139(01)00536-x

The reaction of bis(fluoroformyl) peroxide 1 with F₂ in the presence of CsHF₂ of KHF₂ produces FOCF₂OOC(O)F 2 in 60% yield. The previously known FOCF₂OOCF₂OF is also obtained as a byproduct along with small amounts of the new compounds FOCF₂OOC(O)OOC(O)F 3 and FOCF₂OOC(O)OOCF₂OF 4. Hydrolysis of 2 affords either FOCF₂OOC(O)OOCF₂OF 4 or FOCF₂OOH 5 in low yield, depending on the reaction conditions. Fluorination of peroxides 3-5 provides the corresponding fluoroxy compounds in high yields and provides further proof of structure.

Full text of DOI:10.1016/s0022-1139(01)00536-x

Journal of Fluorine Chemistry 112 )2001) 363±368
Synthesis and reaction chemistry of ¯uoroxydi¯uoromethyl
¯uoroformyl peroxide
Qun Huang, Darryl D. DesMarteau*
Department of Chemistry, Clemson University, P.O. Box 340973, Clemson, SC 29634-0973, USA
Received 27June 2001; accepted 31 August 2001
Abstract
The reaction of bis)¯uoroformyl) peroxide 1 with F2 in the presence of CsHF2 of KHF2 produces FOCF2OOC)O)F 2 in 60% yield. The
previously known FOCF2OOCF2OF is also obtained as byproduct along with small amounts of the new compounds
a
FOCF2OOC)O)OOC)O)F 3 and FOCF2OOC)O)OOCF2OF 4. Hydrolysis of 2 affords either FOCF2OOC)O)OOCF2OF 4 or FOCF2OOH 5
in low yield, depending on the reaction conditions. Fluorination of peroxides 3±5 provides the corresponding ¯uoroxy compounds in high
yields and provides further proof of structure. # 2001 Published by Elsevier Science B.V.
Keywords: Fluoroxy compounds; Peroxygen compounds; Cesium bi¯uoride; Novel structures
1. Introduction
method for a variety of geminal bis)fluoroxy) compounds by
reaction of fluorinated carboxylic acids with fluorine in the
presence of cesium fluoride which gave the corresponding
1,1-bis)fluorooxy)perhaloalkanes in high yield [16].
Recently, Zedda and DesMarteau reported a new preparative
method for 2,2-bis)fluoroxy)perfluoropropane based on the
fluorination of )CF3)2C)OH)2 in the presence of CsF or KF
[17].
Since, the commercial developments in late 1980s, the
reactions of per¯uoroalkyl hypohalites with ole®ns have
been extensively studied. The recent discovery of reactions
of CF2)OF)2 or CF3OOCF2OF to prepare novel dioxoles
[18±20], increased interest in the synthesis and reactivity of
geminal bis)¯uoroxy) compounds and geminal ¯uoroxy
peroxy compounds.
Hypo¯uorites are a class of high-energy oxidizers which
are among the most reactive compounds in chemistry
[1±3]. The relatively weak O±F bond, coupled with high
bond energies of oxygen and ¯uorine to many elements,
accounts for their reactivity. Hypo¯uorites can be used for
selective electrophilic ¯uorination [4±7] and for the pre-
paration of ¯uorinated vinyl ethers in a process developed
by Ausimont [8,9]. The commercial use of CF3OF and
other hypo¯uorites was based in part on early research
that showed that CF3OF could be added to a variety of
alkenes [10].
Zn
RfOH ‡ ClFCˆCFCl ! RfOCFClÀCF2Cl!RfOCFˆCF2
The first fluorocarbon bis)fluorooxy) compound, CF2)OF)2
was reported by several groups in 1967[11±14]. Other
geminal compounds including CF3CF)OF)2 and )CF3)2-
C)OF)2 were synthesized in the same year but in low yields
[15]. Sekiya and DesMarteau developed a better preparative
The work presented in this paper was part of a study
of the chemistry of bis)¯uoroformyl) peroxide. Previously,
only ®ve compounds containing both the peroxy and
the ¯uoroxy functional groups on the same carbon had
been reported. They are CF3OOCF2OF, )CF3OO)2CFOF,
FOCF2OOCF2OF, SF5OOCF2OF and )CF3)3COOCF2-
OF and were ®rst prepared by the following reactions
[21±24].
* Corresponding author. Tel.: ‡1-864-656-4705; fax: ‡1-864-656-0627.
E-mail address: fluorin@clemson.edu )D.D. DesMarteau).
0022-1139/01/$ ± see front matter # 2001 Published by Elsevier Science B.V.
PII: S 0 0 2 2 - 1 1 3 9 ) 0 1 ) 0 0 5 3 6 - X

364
Q. Huang, D.D. DesMarteau / Journal of Fluorine Chemistry 112 *2001) 363±368
system as described in the literature [30]. The bi¯uorides
CsHF2 and KHF2 were activated before use by exposure to
1 atm F2 at 22 8C. After several hours, the ¯uorine was pum-
ped out by vacuum through a soda lime column. The remain-
ing CsHF2 or KHF2 was then kept under vacuum until use.
2.1. Preparation of FOCF2OOC*O)F 2
The reaction of peroxide 1 with ¯uorine in the presence of
metal ¯uorides was carried out under a variety of conditions
in attempting to optimize the yield of 2. The procedure used
involved condensing 1 into a 150 ml stainless steel reactor
containing 5 g of dry metal ¯uoride at À196 8C, and then
adding the desired amount of F2. The vessel was then
warmed to the desired reaction temperature by placing it
in a CFCl3 or ethanol cold bath. After reaction had pro-
ceeded for the appropriate time, the vessel was cooled to
196 8C and F2 and O2 were removed. The remaining mate-
rial was then transferred to the glass vacuum line and
separated by vacuum fractional condensation through traps
at À70, À95, À110, and À196 8C as the sample warmed
from À196 8C in an empty dewar initially at 22 8C. The
À70 8C trap retained a small quantity of FOCF2OO-
Recent research on the chemistry of di¯uorodioxirane and
bis)¯uoroformyl) peroxide has led to several additional
analogous compounds, including CF3OOCF2OOCF2OF,
CF3O)OCF2O)nOCF2OF, FOCF2OOCF2OOCF2OF and l-
¯uoroxy-1,4,4-tri¯uoro-2,3,5,6-tetraoxacylohexane [25,26].
This paper describes the synthesis and chemistry of
¯uoroxydi¯uoromethyl ¯uoroformyl peroxide FOCF2OO-
C)O)F, the ®rst example of a compound having the peroxy,
¯uoroformyl and hypo ¯uorite function in one molecule.
The synthesis of FOCF2OOC)O)F was based in part on the
research work of DesMarteau and Anderson [27] who
showed that monohypo¯uorites FOCF2)CF2)nC)O)F could
be obtained by CsHF2 or KHF2 catalyzed addition of F2 to
one carbonyl group of the diacyl ¯uorides [27].
C)O)OOCF2OF
4
and FC)O)OOC)O)OOCF2OF 3.
Unreacted 1 was retained in the À95 8C trap. The FOC-
F2OOC)O)F 2 and FOCF2OOCF2OF were retained in the
À110 8C trap and other low boiling products such as COF2,
CF3OF were collected in the À196 8C trap. The data for
several representative reactions are summarized in Table 1.
FaOCAFb2OOCBꢀO†Fc 2 )94% pure, with small amounts
of 1 and FOCF2OOCF2OF): IR )3 Torr): 1920.3 )s, C=O),
1294.6 )m), 1255.9 )s), 1196.7)vs), 1162.8 )vs), 1001.6 )w),
2. Experimental section
933.0 )vw), 748.9 )vw), 598.5 )vw) cmÀ1
,
19F NMR,
3
Caution! the chemicals employed in this work are hazar-
dous and should only be used by experienced personnel
familiar with the safe handling of toxic strong oxidizers.
Volatile compounds were handled in a Pyrex vacuum
system equipped with glass-Te¯on valves. Pressures were
measured on an MKS Baratron Type 223B Pressure Trans-
ducer and Type PDR-D-l Digital Readout. Quantities of
reactants and products were measured by direct weighing
and by PVT measurements. Temperatures were measured
with a Fluke 51 K/J thermometer. Molecular weights were
obtained by gas density measurements. IR spectra were
recorded on a Perkin-Elmer Spectrum 2000 with a 7500
data station using a 10 cm glass cell ®tted with AgCl
windows. NMR spectra were recorded on an IBM NR-
200 AF instrument )19F, 188 MHz) using CCl4 as solvent,
CFCl3 as an internal reference and D20 as external lock.
Fluorine was purchased from Air Products and Chemicals
and was passed through an NaF scrubber to remove HF
before use. Cesium ¯uoride was fused in a platinum dish and
then ground to ®ne powder and stored in the dry box. Cesium
bi¯uoride was prepared by using a modi®ed literature
procedure [28,29]. Bis)¯uoroformyl) peroxide was prepared
by reaction of CO, F2 and O2 at room temperature in a ¯ow
da ˆ 160:1 )t, 1F, JaÀb ˆ 36:0 Hz), db ˆ À80:8 )d-d, 2F,
5JbÀc ˆ 2:1 Hz), dc ˆ À31:6 )s, 1F) ppm; 13C NMR )CCl4
solvent & reference, external D20 lock, 75.5 MHz) dA ˆ
125:9 )t, d, 1JAÀb ˆ 275:4 Hz, 2JAÀa ˆ 6:1 Hz), dB ˆ 141:1
2
)d, JBÀc ˆ 303:7Hz) ppm.
FaOCFb2OOCꢀO†OOCꢀO†Fc 3 )from the mixture of 3 and
3
4): 19F NMR da ˆ 161:1 )t, 1F, JaÀb ˆ 36:3 Hz), db ˆ
À80:6 )d, 2F), dc ˆ À31:4 )s, 1F) ppm.
2.2. Preparation of *FOCF2OO)2CFOF 6
The mixture of 3 and 4 )0.3 mmol) was condensed onto
activated CsF )1.0 g) held at À196 8C, and then F2
)1.0 mmol) was added. The mixture was allowed to warm
to À20 8C and remained at À20 8C for 16 h. Excess F2 was
pumped out at À196 8C and destroyed. The products were
transferred to vacuum line for measurement. Compound 6
)0.27mmol, 90%) was obtained pure ꢀFaOCF2bOO†2CFc-
OFd: mp. À86:5 ꢁ À89:0 8C; IR )3 Torr): 1257.4 )s),
1195.4 )s), 1155.9 )s), 1120.2 )vs), 944.2 )vw) cmÀ1 19F
.
3
6
NMR: da ˆ 158:8 )t-d, 2F, JaÀb ˆ 36:7Hz, JaÀc ˆ 2:4
5
Hz), db ˆ À80:0 )d-d, 4F, JbÀc ˆ 4:2 Hz), dc ˆ À89:9
3
)d-m, 1F, JcÀd ˆ 22:6 Hz), dd ˆ 170:7)d, 1F) ppm.

Q. Huang, D.D. DesMarteau / Journal of Fluorine Chemistry 112 *2001) 363±368
365
Table 1
Reactions of FC)O)OOC)O)F with F2
Reactants )mmol)
FC)O)OOC)O)F
Conditions
Products )mmol)
F2
Time )h)
Temperature )8C)
À50
Catalyst
CsHF2
1
2
0.5
0.5
1.11
10
FOCF2OOC)O)F )0.19)
FOCF2OOCF2OF )0.28)
FOCF2OOC)O)F )0.31)
FOCF2OOCF2OF )0.06)
FC)O)OOC)O)F )0.08)
FOCF2OOC)O)F )0.19)
FOCF2OOCF2OF )0.007)
FC)O)OOC)O)F )0.17)
FOCF2OOC)O)F )0.62)
FOCF2OOCF2OF )1.07)
FOCF2OOC)O)F )0.25)
FOCF2OOCF2OF )0.15)
FC)O)OOC)O)F )0.12)
FOCF2OOC)O)F )0.2)
FOCF2OOCF2OF )0.004)
FC)O)OOC)O)F )0.14)
Other peroxides )0.2)
0.5
0.5
24
5
À50
CsHF2
CsHF2
3
1.0
À40
4
5
2
4.5
0.5
12
16
À15
À40
KHF2
KHF2
0.5
6
2
0.5
12
À30
KHF2
2.3. Preparation of FOCF2OOC*O)OOCF2OF 4
FaOCFb2OOH: IR )3 Torr): 3568 )m, OH), 1386.0 )m),
1229.8 )vs), 1168.4 )s), 1112.3 )w) cmÀ1
;
19F NMR
3
Compound 4 can be obtained by reaction of 2 with water.
The mixture of 2 )0.2 mmol) and FOCF2OOCF2OF
)0.1 mmol) was condensed into a 50 ml ¯ask and then
H2O )0.3 mmol) was added. The mixture was allowed to
warm to 22 8C in 4 h and remained at 22 8C for another
4 h. The products were separated by vacuum fractional
condensation through traps at À50, À85 and À196 8C.
Compound 4 )0.08 mmol, yield 40%) was obtained pure
in À85 8C trap. The À196 8C trap contained SiF4, CO2 and
unreacted FOCF2OOCF2OF. Water was retained in À50 8C
trap.
da ˆ 141:2 )t, 1F, JaÀb ˆ 30:9 Hz), db ˆ À81:1 )d, 2F)
1
ppm; H NMR )200.1 MHz): dH ˆ 9:52 )s) ppm.
2.5. The reaction of 5 with F2 in the presence of KHF2
The reaction was carried out in order to probe the
possibility of the synthesis of di¯uorotrioxirane, a poten-
tially interesting but unknown compound. The hydroper-
oxide 5 )0.3 mmol) and F2 )0.3 mmol) were condensed into
a 10 ml stainless steel cylinder which contained 1 g dry
KHF2 at À196 8C. The mixture was allowed to warm to
À78 8C over 2 h and remained at À78 8C for another 4 h.
Excess F2 was pumped out at À196 8C and destroyed. The
products were then transferred to vacuum line and
0.18 mmol of material was obtained in the À196 8C trap.
19F NMR showed the latter to be a mixture of FOCF2OOF,
CF2)OF)2, CF3OF and FOCF2OOCF2OF, easily identi®ed
from each other by 19F NMR.
FaOCFb2OOCꢀO†OOCF2bOFa: IR )2 Torr): 1925.3 )m,
C=O), 1297.6 )w), 1246.9 )s), 1214.6 )m), 1189.9 )m),
19F
1112.0 )s), 945.9 )vw), 861.9 )vw), 774.0 )vw) cmÀ1
;
3
NMR da ˆ 160:6 )t, 2F, JaÀb ˆ 36:5 Hz), db ˆ À80:6 )d,
4F) ppm.
2.4. Preparation of FOCF2OOH 5
FaOCF2bOOFc )mixture): 19F NMR: da ˆ 160:9 )t, d, 1F,
5
The hydroperoxide 5 can be obtained by reaction of 2 with
water in ¯ow system. The mixture of 2 )0.54 mmol) and
FOCF2OOCF2OF )0.36 mmol) was passed through a
20 ft  1/4 in. stainless steel column packed with Chromo-
sorb P 80/100 over 40 min at room temperature.
3JaÀb ˆ 36:3 Hz, JaÀc ˆ 3:2 Hz), db ˆ À80:2 )d-d, 2F,
4JbÀc ˆ 3:8 Hz), dc ˆ 293:5 )q, 1F) ppm.
2.6. The reaction of 2 with CIF in the presence of CsF
Compound 2 was hydrolyzed by the water which was
absorbed on the Chromosorb. The products were collected in
a À196 8C trap and separated by vacuum fractional con-
densation through traps at À90, À115 and À196 8C. The
À90 8C trap contained 5 )0.11 mmol, yield 20%) along with
a trace of 4. The À115 8C trap contained 0.26 mmol of a
mixture of 2, FOCF2OOCF2OF, and 5. Low boiling com-
pounds SiF4, COF2 and CO2 were collected at À196 8C.
The mixture )0.5 mmol) of 2 )60%) and FOCF2OOCF2OF
)40%) was condensed into a 10 ml stainless steel cylinder
which contained 3 g dry CsF at 196 8C. Chlorine mono-
¯uoride )0.5 mmol) was added and the mixture was then
allowed to warm to À78 8C and remained at that tempera-
ture for 15 h. The products were separated by vacuum
fractional condensation through traps at À107, À120,
À133 and À196 8C. The products were COF2, CF3OOCl,

366
Q. Huang, D.D. DesMarteau / Journal of Fluorine Chemistry 112 *2001) 363±368
FOCF2OCl and unreacted FOCF2OOCF2OF by IR and 19F
NMR.
and CsHF2 gave similar results. The KHF2 is preferred
because it is inexpensive and commercially available. The
quality of KHF2 is essential for a good yield. The KHF2 must
be powdered and dried by pumping under vacuum at 22 8C
for at least 6 h before using. The ratio of starting material is
also an important factor. Excess F2 will increase the quantity
of the bis)fluoroxy) derivative which is very difficult to be
separate from 2. Although, excess 1 can limit the amount of
FOCF2OOCF2OF, this results in the generation of 3,3
difluoro-2,4,5,trioxacyclopentanone and a large quantity
of unreacted FC)O)OOC)O)F which are also difficult to
separate from the desired product. A 1:1 ratio of F2 to
FC)O)OOC)O)F gave the best result, limiting the FOC-
F2OOCF2OF to 20±30%,while giving a yield of 2 up to
50±60%. The separation of 2 from FOCF2OOCF2OF was
not successful by fractional condensation. The two com-
pounds always collected in the same traps during trap to trap
distillation. As mentioned above, a 1 to 1 ratio of 1 to F2 gave
the best yield of 2. But the resulting product always con-
tained 30±40% FOCF2OOCF2OF impurity. Increasing the
ratio of 1 to F2 will decrease the quantity of FOCF2OOC-
F2OF. In an extreme situation, when the ratio of 1 to F2 is 4±
1, the resulting 2 can be purified up to 94%.
3. Results and discussion
Per¯uoroalkoxjde anions are postulated as intermediates
in the metal ¯uoride catalyzed reactions leading to the
¯uoroxy compounds from acid ¯uorides. Generally, organic
¯uoroxy derivatives can be prepared from acid ¯uorides by
the action of metal ¯uorides and elemental ¯uorine [31].
F2
RfCꢀO†F ‡ MF!RfCF2OF; M ˆ Cs; K
a,o-diacyifluorides can also be fluorinated to the bis)fluor-
oxy) derivatives catalyzed by active CsF or KF and the
bis)fluoroxy) product is always the only product observed.
No monohypofluorites of the type FC)O)RfF2OF had been
isolated in these syntheses in spite of considerable efforts to
do so. Recently, DesMarteau and Anderson developed a new
process and successfully obtained these potentially impor-
tant compounds by using less active metal fluorides KHF2 or
CsHF2 as catalysts in the fluorination of perfluorodiacyl
fluorides FC)O)Rf)O)F2 [27]. For example perfluorosucci-
nyl fluoride underwent reaction with F2 in the presence of
CsHF2 producing FC)O)CF2CF2CF2OF in 80.6% yield.
Compound 2 is easily identi®ed by its 19F NMR with
characteristic chemical shifts for the OF )160.9), OCF2OO
)À80.8) and C)O)F )À31.6) in the expected 1:2:1 intensities,
3
5
F2
FCꢀO†RfCꢀO†F ‡ MHF2!FCꢀO†RfCF2OF; M ˆ Cs; K
and JFF and JFF coupling constants of 36 and 2.1 Hz,
respectively. Similarly, the 13C NMR showed the two
1
expected carbon signals with characteristic large J13
coupling constants )275.4 and 303.7 Hz) and a small
Compound 2 can be obtained in yields as high as 60% from
the reaction of FC)O)OOC)O)F with F2 in the presence of
MHF2 )M ˆ Cs, K). The data summarized in Table 1 clearly
show that CsHF2 or KHF2 is necessary for the formation of
the monofluoroxy derivative. Substitution of CsF for MHF2
)M ˆ Cs, K) yields FOCF2OOCF2OF as the only product,
whereas the absence of alkali metal fluorides results in
essentially no reaction at low temperature. Both KHF2
CÀF
2J13 ˆ 6:1 Hz.
CÀF
All of the observed products can be explained by
Scheme 1, based on the known chemistry of CF3OOC)O)F
and the behavior of carbonyl compounds in the presence of
CsF and F2 [32]. The thermal stability of 1 is quite good and
the compound )mixture of 60% FOCF2OOC)O)F and 40%
Scheme 1.

Q. Huang, D.D. DesMarteau / Journal of Fluorine Chemistry 112 *2001) 363±368
367
of FOCF2OOCF2OF) has shown no tendency to undergo
explosive decomposition in the vapor )1 atm, 22 8C) or in the
condensed state during routine handling.
®rst example of a molecule containing both the OF and OH
functions.
The reaction of 5 with F2 in the presence of KHF2 gave a
mixture of FOCF2OOF 7, CF2)OF)2, CF3OF and FOC-
F2OOCF2OF. This mixture was not separated but the four
products were easily identi®ed in the mixture by 19F NMR.
The 19F NMR of the mixture shows a high-®eld doublet±
doublet assigned to the OCF2OO group of 7 and two low-
®eld signals assigned to the OOF group and the OF group of
7. The OOF shift is very characteristic, because it is shifted
about 150 ppm down®eld from a typical OF signal [38±42].
Compound 7 is the ®rst example of a molecule contain both
OF and OOF functions.
The formation of a small quantity of 4 and 3 is interesting.
Compound 2 was expected to decompose to FOCF2OOÀ and
COF2 in the presence of CsF. The resulting anion
FOCF2OOÀ may react with 2 or 1 to give 4 or 3. The
formation of 4 was also observed in the reaction of 3 with
CsF. Higher yields )40%) of FOCF2OOC)O)OOCF2OF
could be obtained by the reaction of 3 with H2O. The
structures of 4 and 3 were further con®rmed by reacting
the mixture with F2 and CsF which gave a rare example of a
tris)¯uoroxy) derivative )FOCF2OO)2CFOF 6 [33].
Compounds 3 and 4 exhibit characteristic n)C=O) near
1920 cmÀ1 and the 19F NMR contains the appropriate
resonances for the OF, OCF2OO and C)O)F functions with
4. Summary
3
the expected intensities and large JFF coupling constants
The selective mono¯uorination of FC)O)OOC)O)F pro-
vides the ®rst example of a trifunctional compound contain-
ing the ¯uoroformyl, peroxide and ¯uoroxy function in the
same molecule. A number of other unusual peroxides were
also identi®ed further illustrating the remarkable diversity of
simple ¯uorocarbon peroxygen compounds that can be
synthesized.
)36 Hz) for the FOCF2± groups. For compound 6, the
n)C=O) is absent and the unique ±CF)OF)± function is
easily identi®ed by dCF ˆ À89:9 and dOF ˆ 170:7with
the expected coupling constants and intensities, as well as
the signals for the two FOCF2OO groups.
Acknowledgements
We are grateful to Ausimont SpA )Italy) for ®nancial
support of this work and we also thank Dr. Walter Navarrini
of Ausimont for technical support.
The chemistry of FOCF2OOC)O)F bears some analogy
to CF3OOC)O)F. It is well known that hydrolysis of tri-
¯uoromethyl peroxy ester CF3OOC)O)F forms two inter-
esting peroxides, tri¯uoromethyl hydroperoxide CF3OOH
and bis)tri¯uoromethyl) peroxycarbonate )CF3OO)2C=O
[21,34,35].
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hypo¯uorites, ¯uorooxy di¯uoromethyl hydroperoxide
FOCF2OOH 5 and bis)¯uorooxydi¯uoromethyl) peroxycar-
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