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.
BF3 OEt2
R3SiOH
r.t., 1 d
R3SiF
Entry
R3
Solvent
Conversion
t-BuPh2
Et2O
25%
MePh2
THF
quant.
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
Si
O
Si O
F
O Si
Si O F
F
all-cis
R
R
O Si
Si O R
Si
O
Si O
F
cis-cis-trans
Si
O
Si O
F
O Si
Si O R
R
F
R
O Si
Si O F
Si
O
Si O
R
cis-trans-cis
all-trans
Scheme 1.
R
R
HO
Si
O
Si O
HO
Si
Si O OH
OH
Si
O
Si O
F
Si
Si O F
F
R = Ph (1) : 27%
R = i-Bu (2) : 53%
Scheme 2.
Si
O
Si O
F
R
R
O Si
Si O F
4 eq. H2O
CDCl3 / r.t., 14 d
Si
O
Si O
F
R
R
O Si
Si O F
F
4 isomers
Scheme 3.
5
6
7
8
9
10
11
12
13
14
15
16
17
18