R E A C T I O N O F T R I M E T H Y L I O D O S I L A N E
A L K Y L A R Y L E T H E R S
W I T H
M. G. V o r o n k o v , ~.. I. D u b i n s k a y a ,
S. F. Pavlov,* and V. G. G o r o k h o v a
UDC 542.91:547.1'128
The reaction oftrimethyllodosilane (I) with alkyl aryl ethers has not been studied. The reaction of t r i -
methylbromosllane with anisole under pressure, at 170-180.C, i n t h e presence of C5H3N-HBr, has been de-
scribed, which leads to CHsBr and trimethylphenox~silane (61% yield) [1]. Anlsole and phenetole when reacted
with SiC14 at 200-300" were converted to tetraphenoxystlane and the corresponding alkyl chloride. Migration
of the alkyl radical to the benzene nucleus was observed when the higher alkyl aryl ethers are treated with
SiCl4, with the formation of tetraphenoxysilane,
phenoxy(alkylphenoxy)silanes, and HCI [2].
It was shownby us that the cleavage of the Si--O--C [3-4] and C - - O - - C bonds in cyclic ethers by (I)
proceeds under mill conditions i n t h e absence of a catalyst [5-6]. The reaction of (I) with anisole derivatives
proceeds at 120-135° by the following scheme:
ArOCJ-I s + (GHs)sSiI ~ ArOSi(CHs), + CH,I
The reaction of (1) with a,/~-methoxynaphthalenes proceeds in a s i m i l a r manner. In all cases the duration of
reaction was checked by GLC @he process was stopped when the amount of starting ether was less than 5%).
In all cases the yields of the trimethylaroxysilanes were ~100%.
An increase i n t h e length of the alkyl radical i n t h e all~yI aryl ethers makes t h e i r cleavage by (1) more
difficult. Substltuents that are ortho to the alkoxy group also lower the yield of the corresponding trimethyl-
siloxy derivative. Thus, when anlsole and phenetole are reacted with (1) under identical conditions the yield
of trimethylphenoxysilane in 7 h was, respectively, 80 and 50%. Donor subetltuents in the aromatic nucleus
accelerate the cleavage of the O--CH~ bond, while acceptor substituents, in co~rast, retard it.
The purity of the trimethylaroxysilanes (Table 1) was shown by GI~ to be over 99%, while the structure
was proved by ]11 and NMR spectroscopy (~he data will be published separately).
~Deceased.
TABLE i. T r imethyfaroxysilanes ArOSI(CHs)3
]~ne,~Zc" i n ~. .
~Fo5tmd. ~ CaJlculated. '/.
Ar
9e.o
9,.o
I
i
~ 1 ~
t
.
u
t
e
~
.
S
O
:
l
-
I ~ . ~ l , . W , l , , . ~ l - _
o~.r,s~ I t . ~ o
~
~
I~:~ i .~:.~
Ih),S
I
el(i)
i~O'-..o, i t . ~
t o ~ . ~ il~t ,',-',~,~ i ~ . ~
I¢,o.~14.It Il~io;~,~z Im.~
I
~.o
I
sW,O I i~(i}
I
t
:
5
1
"
~
t
~
l
? Ir~,oe Ise.sz 12,~1 $,~ I m,Q
~.o
i
"
~
"
~;~i "=: I ~:~
tM,O
m,o
|
ti9(2)
2-C~H,
I
~(t)
.
~
ItS.m~.- , I n ~ I'~,~sBg,u
I
-
-
I r k ~ s k Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR. T r a n s -
lated from Izvestiya Ahademii Nauk SSSR, Seriya ghimicheskaya, No. 10, pp. 2355-2356, October, 1976.
Original article submitted January 27, 1976.
7"Ms inertial is protected by copyrt~t re~tered in tht name of Plenum Pubtishi~ Corpcwatton. 227 West 17th Street, Nov York, N.Y. 10011. No ~rf I
o f tab imbll~tLon moy be nqwo~ced, stored in •
mloolt6ntng, e e a w d l ~ g o r ot~tvdse, w i t h o u tw r l n e n o e r m l n i o n o f Otc l~bll~er.
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2198
Voronkov et al.
