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Facile Synthesis of Cyclic Fluorosiloxanes

Naoki Oguri, Nobuhiro Takeda, and Masafumi Unno*

Advance Publication on the web August 21, 2015 by J-STAGE
doi:10.1246/cl.150692

© 2015 The Chemical Society of Japan
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1

Facile Synthesis of Cyclic Fluorosiloxanes
Naoki Oguri, Nobuhiro Takeda, and Masafumi Unno*
Department of Chemistry and Chemical Biology, Graduate School of Science and Technology, Gunma University, Kiryu 376-8515
E-mail: unno@gunma-u.ac.jp

Novel
1,3,5,7-tetrafluorocyclotetrasiloxanes
were
synthesized from cyclotetrasiloxanetetraol by facile synthetic
method. By adjusting the amount of the fluorinating reagent,
synthesis
of
single
isomer
of
1,3,5,7tetrafluorocyclotetrasiloxanes as well as the preparation of all
four isomers were accomplished. The products are expected to
serve as potential precursors to not only well-defined
silsesquioxanes but also asymmetric cyclic siloxanes.

Recently, ladder and cubic silsesquioxanes have
attracted considerable interests mainly due to their high
thermal stability. During the last decade, we have reported the
syntheses of ladder oligosilsesquioxanes with high thermal
stability starting from cyclic silanol, all-cis-cyclotetrasiloxanetetraol.1 Gunji’s group has also synthesized industry
favorable methyl-substituted ladder oligosilsesquioxanes and
polysilsesquioxanes.2 Kaneko et al. have developed the
preparation method for ladder polysilsesquioxanes with
ammonium group, which are soluble in water, by sol-gel
method.3
In these syntheses of well-defined materials, the
selection of suitable starting material is important. Among
possible starting compounds, cyclic silanols have been shown
to be most effective. Stereoselective synthesis of all-cis1,3,5,7-cyclotetrasiloxanetetraol with various substituents
have been reported by many groups.4 Gunji, Abe, and coworkers
have
synthesized
cis-trans-cis-1,3,5,7tetraisocyanato-1,3,5,7-tetramethylcyclotetrasiloxane.5 Quite
recently, Kaneko et. al. reported the selective preparation of
cis-trans-cis cyclic tetrasiloxanes with propylammonium
trifluoromethanesulfonate.6
Cage silsesquioxanes are also accessible from cyclic
silanols,
and
octcasilsesquioxanes4b,7
and
hexa1c
silsesquioxanes
have been synthesized from all-ciscyclotetrasiloxanetetraols. However, syntheses of cage
silsesquioxanes with different substitutes, which are expected
to show controlled macroscopic properties8, are still
challenging. Cyclic silanols are a half part of
octasilsesquioxanes, and then serve as a good starting material
for mixed-substituted cages. Suitable reaction counterparts of
cyclic silanols are cyclic halosiloxanes to afford cage
silsesquioxanes with different substituents. A decade ago, our
group has synthesized and separated all four isomers of (iPrSiClO)4, which were reacted with water to give the cyclic
silanol, however this synthesis demanded stepwise procedures
in addition to the stereoisomer separation with HPLC.9 Cyclic
bromosiloxane,
cis-trans-cis-tetrabromotetramethylcyclotetrasiloxane, has also been prepared.10 This bromosiloxane
spontaneously hydrolyzed in the air to afford ladder
polysilsesquioxane. As described above, chloro- and
bromosiloxanes are unstable to moisture, and synthetically

difficult to obtain. Therefore, utilization of these cyclic
halosiloxanes are not suitable for facile syntheses of welldefined silsesquioxanes. As expected, it is also difficult to
separate
these
cyclic
halosiloxanes
by
column
chromatography or by distillation because of high boiling
point. Hence, facile selective preparations of cyclic
halosiloxanes are strongly desired for selective Si–O–Si bond
formation.
Feher et al. have reported facile fluorination reaction of
incompletely-condensed siloxane bearing silanol groups with
high yields by use of HBF4 and BF3•OEt2.11 Fluorosilanes
could also be capable to be precursors to Si–O–Si bond
formation as reported by Klingebiel and Graalmann.12
In this paper, we report facile syntheses of cyclic
fluorosiloxanes by a ubiquitous fluorinating reagent, which
would be powerful method to prepare precursors to welldefined silsesquioxanes.
Fluorination reactions of silanols have been so far
reported with only HF13 or BF3•OEt2.14 Cleaving Si–O–Si
bond by HF is possible by generating naked fluoride ion.
Although Feher’s results indicated that BF3•OEt2 was deemed
the adequate fluorinating reagent for fluorination of silanols
with siloxane frameworks, additional application for silanols
was not known yet.
To ascertain that BF3•OEt2 is the adequate reagent, we
have conducted a series of experiments on the fluorinations of
simple silanols with BF3•OEt2 to give corresponding
fluorosilane (Table 1). We reacted the silanols with an
equivalent amount of BF3•OEt2 with stirring at room
temperature for 1 day. The results of MS and 1H, 19F, and 29Si
NMR spectra demonstrated the formation of corresponding
fluorosilane in each reaction, and conversion ratios of silanols
to fluorosilanes could be determined by 1H NMR spectrum.
These spectra were consisted with previously reported data.
The conversion ratio of t-BuPh2SiOH, a silanol with bulky
substituent, suggests the difficulty of fluorination of sterically
hindered silanols (Table 1, Entry 1).
Table 1. Fluorination of silanols by BF3•OEt2.

BF3 • OEt2

R3Si–OH

r.t., 1 d

R3Si–F

Entry

R3

Solvent

Conversion

1

t-BuPh2

Et2O

25%

2

MePh2

THF

quant.

3

Ph3

THF

quant.

2
R
R

HO

Si
O
Si O
HO

R
R

O Si
Si O OH
OH

R = Ph
R = i-Bu

R

R

4 eq. BF3 • OEt2
hexane / r.t., 10 min

R

F

Si
O
Si O
F

R

O Si
Si O F
F

all-cis

F

R
R

F

R

O Si
Si O R

Si
O
Si O
F

F

R

R

F

F

cis-cis-trans

Si
O
Si O
F

F

O Si
Si O R
R

R

F
R

F

F

O Si
Si O F

Si
O
Si O
R

cis-trans-cis

F

all-trans

Scheme 1.

The less hindered silanols, with triphenyl or methyldiphenyl
group, was converted to corresponding fluorosilane with
quantitative conversion ratio (Table 1, Entry 2 and 3). The
series of experiments indicated that BF3•OEt2 is assumed to
be the potent fluorinating reagent unless a silanol has bulky
substituents.
Next, we tried to fluorinate all-cis cyclic silanol. All-cis(PhSi(OH)O)4 and all-cis-(i-BuSi(OH)O)4 were synthesized
using the effortless hydrolysis reaction as previously
reported.4e The reactions with four molar equivalent of
BF3•OEt2 were completed within 10 minutes and the
formation of
1,3,5,7-tetrafluorocyclotetrasiloxane
was
confirmed by MS spectrum. In the reaction of all-cis phenylsubstituted cyclic silanol, six signals in 19F NMR were
observed at –133.11, –133.45, –133.79, –133.94, –134.28, and
–134.31 ppm, and six pairs of doublet peaks at –75.18, –75.25,
–75.35, –75.48, –75.57, and –75.65 ppm were observed in 29Si
NMR. The existence of six signals can be clearly explained by
the
formation
of
four
stereoisomers
of
tetrafluorocyclotetrasiloxanes (Scheme 1).
Cyclotetrasiloxanes with two different substituents have
four isomers, all-cis, cis-cis-trans, cis-trans-cis, and all-trans
structure, each shows one, three, one, and one peaks in 29Si
NMR, respectively. The ratio of all-cis, cis-cis-trans, and
other two isomers (cis-trans-cis or all-trans isomer) was 10 :
1 : 3 : 1 calculated by 19F NMR spectrum. Similarly in the
case of all-cis isobutyl-substituted cyclic silanol, six signals in
19
F NMR and six pairs of doublet peaks in 29Si NMR were
observed. The ratio of all-cis, cis-cis-trans, and other two
isomers (cis-trans-cis or all-trans isomer) was 10 : 5 : 2 : 1.
Fluoride ion derived from generated HF attacks the silicon
atom to form penta- and then hexa-coordinated silicon species,
following by racemization.2b,15 Separation of each isomer by
column chromatography was unsuccessful.
We presumed that excess amounts of BF3•OEt2, a Lewis
acid with the ability to scavenge F– ion, could prevent the
generation of HF from the racemization.11 As expected, only
single isomer was obtained in both cases of phenyl-substituted
(1, 27%) and case of isobutyl-substituted compound (2, 53%)
(Scheme 2), the structures of which were confirmed by 1H,
13
C, 19F, and 29Si NMR, IR, and MS spectra and elemental
analysis. It is assumed that the obtained compounds were allcis isomer with maintaining the stereostructure of the starting
compounds. Unfortunately, the X-ray structure analysis was
not conducted since both 1 and 2 were oily compound. Even
though polymeric reaction took place at the same time, which
was catalyzed boron trifluoride,16 the target cyclic
fluorosiloxanes were separated by GPC with moderate yield,
especially in the cases of 2. To our knowledge, this is the first
report of synthesis and of cyclic fluorosiloxane.

R

R
R

HO

Si

O
Si O
HO

O

R

R

R

exess BF3 • OEt2
hexane / r.t., 10 min

Si
Si O OH

R

F

OH

Si

O
Si O
F

O

R

Si
Si O F
F

R = Ph (1) : 27%
R = i-Bu (2) : 53%
Scheme 2.

Cyclic fluorosiloxane 1 and 2 were stable in air, and
surprisingly resistant to hydrolysis. By stirring in CDCl3 with
water for 1 day, 1 was not hydrolyzed. Similarly, 2 was also
unaffected by water for an hour. Even though the expected
hydrolysis was not occurred, stereoisomerization reaction was
preceded gradually (Scheme 3). Two weeks later, the
integration ratios for each of four isomers in 19F NMR became
approximately became unchanged. Apparently, the reaction
mechanism is identical with the mechanism for generating
four isomers in the synthesis of 1 and 2.
R
R

F

Si
O
Si O
F

R
R

O Si
Si O F

R

4 eq. H2O
CDCl3 / r.t., 14 d

R

F

F

Si
O
Si O
F

R
R

O Si
Si O F
F

4 isomers
Scheme 3.

Klement’ev et. al.17 and Kawakami group4e reported
promoting of isomerization reaction of all-cis-(PhSi(OH)O)4
by HCl or CH3COOH. Similarly, our group have observed the
stereoisomerization reaction of all-cis-(i-BuSi(OH)O)4 by
various acids including CF3COOH. When water and acid
were added to 1 and 2 in acetone-d6, isomerization was
observed in 1 hour. However, addition of CF3COOH and no
water did not affect the reaction rate, and no change was
observed in NMR spectra. This high stability ensures the easy
handling of these cyclic fluorosiloxanes. In the presence of
pyridine, hydrolysis did not occur and white solid precipitated.
The signals due to pyridine shifted to high magnetic field in
1
H NMR, and the signals derived from the cyclic compounds
moved to high magnetic field in 29Si NMR. After removing
pyridine and solvent, each spectrum showed the same
chemical shifts. These observations suggest formation of fivecoordinated
cyclic
fluorosiloxanes.
The
structure
determinations of these compounds are in progress now.
In summary, starting from easily accessible cyclic
silanols, cyclic fluorosiloxanes were synthesized by the facile

3

and rapid synthetic method in mild condition. Compared with
conventional method to obtain halosiloxanes, this method is
expected to be the shortest path to, especially, not only welldefined silsesquioxanes with different substitutes but also to
asymmetric cyclic siloxanes with different functional groups
on the same silicon. Further investigation starting from these
fluorosiloxanes will be shown in near future.

References and Notes
1

2

3

4

5
6
7
8

9
10
11
12
13
14
15
16
17
18

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