Hexafluoropropene oxide - a fluorinating reagent for the formation of element-fluorine bonds

Article abstract of DOI:10.1016/S0022-1139(98)00285-1

Hexafluoropropene oxide (HFPO) is shown to be a good reagent for the nucleophilic formation of the element-fluorine bond in organoelement compounds. Fluorides of Bi, Sb, Se, Te and I were prepared from appropriate oxygen compounds.

Full text of DOI:10.1016/S0022-1139(98)00285-1

Journal of Fluorine Chemistry 93 (1999) 103±105
Hexa¯uoropropene oxide ± a ¯uorinating reagent for
the formation of element±¯uorine bonds
S.A. Lermontova,*, I.M. Rakova, N.S. Ze®rova, P.J. Stangb
aInstitute of Physiologically Active Substances, Rus. Acad. Sci., Chernogolovka, Moscow Region 142432, Russia
bDepartment of Chemistry, University of Utah, Salt Lake City, UT 84112, USA
Received 6 May 1998; accepted 8 September 1998
Abstract
Hexa¯uoropropene oxide (HFPO) is shown to be a good reagent for the nucleophilic formation of the element±¯uorine bond in
organoelement compounds. Fluorides of Bi, Sb, Se, Te and I were prepared from appropriate oxygen compounds # 1999 Elsevier Science
S.A. All rights reserved.
Keywords: Hexa¯uoropropene oxide; Nucleophilic ¯uorination; Fluorides
1. Introduction
corresponding bismuth ¯uorides when treated with 1 in
re¯uxing benzene (reaction (2)). In contrast, triphenylbis-
muth dichloride does not react with 1.
Hexa¯uoropropene oxide (HFPO, 1) is widely used in
industry for the preparation of ¯uorinated polyethers [1].
Earlier we have published data concerning the ¯uorination
of tri- and pentavalent organophosphorus compounds by
HFPO, the key step being an extremely smooth substitution
of oxygen of a very stable phosphoryl group by two ¯uorine
atoms [2,3] (reaction (1)).
1;C6H6
Á
Ph3Bi ˆ X
2a
!
Ph3BiF2
3
c
(2)
a: X ˆ CO3
b: X ˆ ꢀOAc†
c: X ˆ Cl2
41%
45%
no reaction
2
Analogously, triphenylantimony oxide, 4, afforded the
corresponding di¯uoride 5 upon treatment by HFPO, 1, in
a steel bomb (reaction (3)).
(1)
Ph3SbˆO 1;CH Cl
!
2 Ph3SbF2
(3)
2
These reactions proceed at ambient temperature and
normal pressure to give usually a high yield of the corre-
sponding di¯uorides. The ease of this transformation is quite
remarkable and the only known analogous reaction is the
interaction of phosphoryl compounds with the hazardous
SF4 upon heating [4], while HFPO is a stable, easy to store
and nontoxic compound. Hence we decided to examine this
reagent for the purposes of ¯uorination of different types of
organo element compounds.
rt; 9 h
4
5 31%
2.2. Group VI elements
In general, selenium and tellurium oxides react with
HFPO, 1, readily affording the corresponding ¯uorides in
CH2Cl2 at an ambient temperature (reactions 4 and 5).
Ph2SeˆO 1;CH Cl
!
2 Ph2SeF2
7 42%
(4)
(5)
2
rt;4h
2. Results and discussion
6
ꢀp-CH3C6H4† TeˆO 1;CH Cl
!
ꢀp-CH3C6H4†2TeF2
2
2
2.1. Group V elements
2
rt;2:5h
8
9 43%
Recently we have shown that PhSeF3 is an oxidative
¯uorinating reagent for some ole®ns [5,6]. We carried out
the reaction of phenylseleninic anhydride, 10, with HFPO, 1,
in order to obtain PhSeF3, but we have not been able to
We have found that pentavalent bismuth compounds
containing the Bi±O bond are readily transformed into
*Corresponding author. Fax: +7959-390-290.
0022-1139/99/$ ± see front matter # 1999 Elsevier Science S.A. All rights reserved.
P I I : S 0 0 2 2 - 1 1 3 9 ( 9 8 ) 0 0 2 8 5 - 1

104
S.A. Lermontov et al. / Journal of Fluorine Chemistry 93 (1999) 103±105
isolate this tri¯uoride. However, if the reaction was carried
out in the presence of trans-stilbene (to trap intermediate
PhSeF3), the formation of di¯uoride 12 was observed, which
proves the intermediacy of PhSeF3 (reaction 6).
references, respectively. The chemical shifts are reported
in ppm, with negative values being up®eld from the
standard (ꢀF(CFCl3)=ꢀF(CF3COOH)‡76). 1 was com-
mercially available. Other starting materials were pre-
pared as described previously: Ph3BiCO3 [10], Ph3Bi(OAc)2
[11], Ph3BiCl2 [12], Ph3SbO [13], Ph2SeO [14], (p-CH3-
C6H4)2TeO [15], (PhSeO)2O [16] and PhI(OAc)2 [17].
ꢀPhSeO†2O 1;CH Cl
!
‰PhSeF3Š
!
trans-PhCHˆCHPh PhCHF-CHFPh
2
2
rt; 85 h
12 15%erythro:threoˆ11:1
11
10
(6)
3.1. The reaction of HFPO, 1, with Ph3BiCO3, 2a
2.3. Group VII elements
HFPO, 1, was passed through the reaction mixture, which
contained 5.24 g (1.05Á10 2 mol) of 2a and 50 ml of dry
C6H6 at re¯ux for 14 h until 2a dissolved. The solvent was
evaporated in vacuo. C6F6 was added as internal standard for
NMR integration to a small part of the reaction mixture. The
19F NMR spectrum showed the presence of 41% of
Ph3BiF2. ꢀF 82.73 (s). (Lit. [18] ꢀF 83 (s)). The reaction
mixture was washed with hot n-hexane three times and the
washings were evaporated to dryness. The residue was twice
re-precipitated from concentrated benzene solution by n-
hexane and 0.08 g (1.6%) of Ph3BiF2 was obtained. Mp
148±1538C (Lit.[19] mp 158.5±1598C). Anal. Found %. C
45.19. H 3.30. Calcd. for C18H15BiF2, %. C 45.20. H 3.16.
19F NMR. ꢀF 83.69 (s).
PhIF2 is known as a ¯uorinating reagent for a number of
ole®ns. This reagent is very labile towards hydrolysis. Thus,
because we expected its formation in the reaction of
PhI(OAc)2, 13, with HFPO, we decided to use the above-
mentioned trapping method for this case. Indeed, reactions
of 13 with 1, performed in the presence of either styrene or
1,1-diphenylethylene in a steel bomb proceed to give rear-
ranged ¯uorinated products, 14 and 15, respectively [7,8]
(reaction 7).
(7)
3.2. The reaction of HFPO, 1, with Ph3Bi(OAc)2, 2b
HFPO, 1, was passed through a solution of 0.067 g
(1.2Á10 4 mol) of 2b in 10 ml of dry C6H6 at re¯ux during
2 h. The solvent was evaporated in vacuo and C6F6 was
added as internal standard for NMR integration. The
19F NMR spectrum showed the presence of 45% of Ph3BiF2
(ꢀF 83.3) and was similar to that for a sample prepared by
independent procedure from Ph3Bi and XeF2 [18].
The above data show that hexa¯uoropropene oxide, 1, is
an interesting and unusual nucleophilic ¯uorinating reagent,
capable in some cases of substitution for the hazardous SF4.
We presume that the mechanism of ¯uorination to be similar
to that postulated by Martini [9] for the ¯uorination of
phosphoryl group as outlined for Se=O (reaction 8).
3.3. The reaction of HFPO, 1, with Ph3SbO, 4
HFPO, 1, was passed through the reaction mixture, which
contained 0.192 g (5.2Â10 4 mol) of 4 and 15 ml of dry
CH2Cl2, at rt over 9 h until 4 dissolved. The solvent was
evaporated in vacuo. m-Fluorotoluene was added as internal
standard for NMR integration. The 19F NMR spectrum
showed the presence of 31% of Ph3SbF2 (ꢀF 75.1 (s)
Lit. [20], ꢀF (CFCl3) 153.2 (s)) and was similar to that for
a sample prepared from Ph3Sb and XeF2 [21]. The reaction
mixture was evaporated in vacuo. The residue was washed
with small portions of n-heptane four times. The washings
were combined and evaporated in vacuo. The solid residue
was crystallized from n-heptane. 0.018 g (8.8%) of Ph3SbF2
were obtained. Mp 114±1158C (Lit. [21]: mp 121±1228C).
(8)
We did not make attempts to isolate the product of HFPO
de¯uorination ± probably ¯uoroanhydride CF3COCOF (see
reactions (1) and (8)). This substance is known to react
immediately with an excess of HFPO to form complex
mixtures of oligomeric poly¯uorinated substances [9] and
we suppose that in our case the products are the same.
3.4. The reaction of HFPO, 1, with Ph2SeO, 6
3. Experimental
HFPO, 1, was passed through the solution of 0.086 g
(3.45Â10 4 mol) of 6 in 7 ml of dry CH2Cl2 at rt during 4 h.
The solution was concentrated in vacuo and m-¯uorotoluene
1H and 19F NMR spectra were recorded on a Bruker
CXP-200 spectrometer using TMS and CF3COOH as

S.A. Lermontov et al. / Journal of Fluorine Chemistry 93 (1999) 103±105
105
was added as internal standard for NMR integration. The
19F NMR spectrum showed the presence of 42% of Ph2SeF2
in vacuo. C6F6 was added as internal standard for NMR
integration. The 19F NMR spectrum showed the presence of
77
19
(ꢀF 10.3 (t), Jꢀ Se-19F† ˆ 539 Hz† (Lit. [22]: ꢀF (CFCl3)
77
16% of PhCH2CF2H. ꢀF 37.3 (dt, Jꢀ F-1H† ˆ 58 Hz,
77
66.8, Jꢀ Se-19F† ˆ 525 Hz†. The 19F NMR chemical
19
Jꢀ F-1H† ˆ 17:5 Hz) (Lit. [7] ꢀF (CFCl3) 115(dt)).
shift and Jꢀ Se-19F† were similar to that for a sample
The reaction mixture which contained 0.17 g
(5.28Á10 4 mol) of 13, 0.204 g (1.13Á10 3 mol) of
Ph2C=CH2, 6 g (3.6Á10 2 mol) of 1, 4 ml of dry CH2Cl2
was kept at 80±908C during 6 h in a steel bomb with internal
¯uoropolymer coating. The solvent was evaporated in
vacuo. C6F6 was added as internal standard for NMR
integration. The 19F NMR spectrum showed the presence
prepared by the reaction of Ph2Se with XeF2 (0.053 g
(3.14Á10 4 mol) of XeF2 was added to the solution of
0.066 g (2.83Á10 4 mol) of Ph2Se in 5 ml of dry CH2Cl2
under stirring and cooling with cold water. The reaction mix-
ture was stirred at rt over 0.5 h. The solvent was evaporated
in vacuo. The 19F NMR spectrum showed the presence of
77
19
Ph2SeF2 signal. ꢀF 11.46, Jꢀ Se-19F† ˆ 532 Hz†:
of 23% of PhCH2CF2Ph. ꢀF 16.97(t), Jꢀ F-1H† ˆ 16 Hz.
19
(Lit. [8] ꢀF (CFCl3) -96.75(t), Jꢀ F-1H† ˆ 15 Hz).
3.5. The reaction of HFPO, 1, with p-tolyl2TeO, 8
Acknowledgements
HFPO, 1, was passed through the reaction mixture, which
contained 0.095 g (2.9Á10 4 mol) of 8 and 4 ml of dry
CH2Cl2, at rt during 2.5 h. The solvent was evaporated in
vacuo. C6F6 was added as internal standard for NMR
integration. The 19F NMR spectrum showed the presence
This work was supported by the Russian Foundation of
Basic Research (grant no. 98-03-32997) and by the FIRCA
of NIH (R03TW00437)
125
of 43% of p-tolyl2TeF2 (ꢀF 50.5, Jꢀ Te-19F† ˆ 573 Hz†.
References
The reaction mixture was dissolved in n-heptane and ®l-
tered. The ®ltrate was evaporated in vacuo and the residue
was crystallized from n-heptane two times. 0.015 g (14.8%)
of p-tolyl2TeF2 was obtained (mp 159±1618C, lit. [23] mp
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125
1638C). The 19F NMR chemical shift and Jꢀ Te-19F† were
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p-tolyl2Te with XeF2 (0.042 g (2.49Á10 4 mol) of XeF2 was
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125
Jꢀ Te-19F† ˆ 569 Hz†.
3.6. The reaction of HFPO, 1, with (PhSeO)2O, 10
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(2.7Á10 4 mol) of 10, 0.145 g (8.06Á10 4 mol) of trans-
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3.7. The reaction of HFPO, 1, with PhI(OAc)2,13
The reaction mixture, which contained 0.168 g
(5.2Á10 4 mol) of 13, 0.136 g (1.3Á10 3 mol) of
PhCH=CH2, 3.8 g (2.29Á10 2 mol) of 1 and 4 ml of dry
CH2Cl2 was kept at 70±808C during 3 h in a steel bomb with
internal ¯uoropolymer coating. The solvent was evaporated
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