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Transition metal reactions of silanes II. The reaction of cycloalkenes with various hydrosilanes and carbon monoxide catalyzed by Co2(CO)8
Journal of Orgfmometdiic
Chemisby, 110 (1977) 361-318 8 ElsevierSequoiaS.A..Iausanne-PrintedinThe~etherlands
TRANSITION
METAL
CYCLOALKENES CATALYZED
YOSHIO
REACTIONS
WITH --
VARIOUS
SEKI,
AKIHIKO
HIDAKA,
SONODA
Department
of Petroleum -
University,
(Received
July
The
6th.
cycloheptene, norbornene)
Osaka
AND CARBON --I___
EtZMeSiH
of Co2(CO)S
following
MAKINO,
Faculty
565
gave
cyclohexene,
and
carbon
monoxide
the
corresponding In such
gave
diethylmethyl-
reactions
Et3SiH,
Effects
of the
and
the molar
The
yield
increased
pressure ratio
of cyclohexene,
the corresponding EtMeZSiH,
Ph2MeSiH.
and in the
Me3SiH,
conditions(the
*
Japan
1-methylcyclohexene,
hydrosilanes
PhMe$iH,
MURAI,
of Engineering, -
siloxymeth$lenecyclohexanes:
of carbon
reaction
monoxide,
of cyclohexene
to
Et2MeSiH,
the
EtZMeSiH)
temperature, were
examined_
of diethylmethylsiloxymethylenecyclohexane remarkably
cyclohexene of the
OF -
MONOXIDE
SHINJI
of cycloalkenes(cyclopentene,
siloxymethylenecycloalkanesthe
REACTION
1977)
cyclooctene, with
SHIGEO
Chemistry,
Suita -'-_f
reaction
presence
HYDROSImES
THE
II:
BY - COAX-
and NOBORU
Osaka
OF - SILANES ---
361
with
to Et$?eSiH.
isomerization
cyclohex-1-ene,
increasing
At higher
product,
molar
ratio
temperature,
of
the yield
l-(diethylmethylsiloxymethyl)-
increased.
Introduction
It is well f -Por.part .
known
that
the metal-catalyzed
1, see
ref,
[l).
reactions
of a
362 hydrosilane case
of
parallels
oz.&dative
hydrosilane[2]
addition
relatedC2,
between
reactions
of olefins no such
Chalk
has
and Harrod
was
details
were
complex
mixture
ranging
from
fractions alkoxy
reported,
reaction The
reported
In the case
was
of the
of our
with
complex"
and
and
no
however,
with
boiling
into
a points
thirty
three
unsaturated
(C2H513
which
propionaldehyde
of
by
triethylsilane
to contain
C3H50Si
However,
described
of ethylene,
found
reaction
the dicobalt
fractionated
formula
formal
of pent-l-ene
products
of
in transition
reaction
"very
to be
to 300°C
The
monoxide.
of olefins
of the reaction
90°C
addition
the catalyzed
studied
reaction
and one of them was
gave
on treatment
the hydrasine, Beside
have
to an
to be very
to the best
They
the 2,4_dinitrophenylhydrazone with
about
and carbon
in 1967161,
given.
silane(s1
seem
and hydrogen
for an interesting
monoxide.
cyclohexene
*-adducts.
involves
us curious
been
octacarbonyl-catalyzed and carbon
reactions
a hydrosilane
except
knowledge,
of a
hydrogenationl31.
to olefinsl53.
a hydrosilane
reaction
in the
both
of R3SiH
to catalytic
monoxide
has made
with
to give
addition
hydroformylation
and carbon
similarity
react
these
example,
3, Sal_
The well-known hydrogen
For
complex,
axi Ir(i)
analogous
mechanistically
closely
metal
to
the catalyzed
is formally
Moreover,
of hydrogen.
and hydrogen13al
Eiydrosilylation[41, olefin,
those
been
reported compounds examples
made
mentioned
and somewhat
on the reaction
seem
or the reaction
surprisingly
discouraging
limited
results
monoxide
of transition
to be mostly reaction
work,
of carbon
in the presence
the catalyzed monoxide
the above
with
metals.
to studies
few studies have
been
organosilicon The
dealing
scattered with
involving
a hydrosilane
and
carbon
between
the complexes
containing
363 silicon-metal
bonds
reported
that
no direct
occurred
at
pressures has
reported
the
with
co-workers 4000
carried
atm of carbon
carbon
monoxide
It has
been
reported
as of phosphines, addition
that
reaction
inhibited
reacts
use
and hydrosilanes
dicobalt
gave
only
one
product,
been
obtained
remarkably the
by direct Haqen
with
insertion
bond
was
of
observed[lO].
monoxide,
as well
octacarbonyl-catalyzed
work,
smoothly
clean
cases
of the catalyzed
we have
with
found
that
cycloalkenes The
of COAX. results.
_
From
catalytic
cycloalkenes,
studied.
reaction
and carbon
monoxide
In.this
paper,
of cycloalkenes under
various
has the-
with
reaction
l
conditions
Results
and -
Reaction carbon
are
Chalk
*
described.
discussion
of cycloalkenes -
with
diethylmethylsilane
and
monoxide
Contrary and
to the
Harrod
A portion
preliminary-form,
"very
for the of this see
and
trialkylsiloxymethylenecycloalkane,
in most
hydrosilanes
but-no
It
insertion
to acrylonitrile[ll]
in the presence
reaction
bonds
of carbon
previous
very
carbonyf
of MeSiClzCo(CO)4
at 90°C.
the
monoxide
unsuccessful.
the silicon-cobalt
to this
monoxide
results
the
Harrod
of Co2(CO)8[6].
Si-Rh[9]
were
of dimethylchlorosilane
.In contrast carbon
monoxide
and
carbon
to induce
and
monoxide
into
and
in the presence
attempts
out
Chalk
of triethylsilane
up to 300%
Si-Mn[S],
carbon
monoxide.
carbonylation
psi
that
Si-Col7],
reaction
carbon
temperatures
up to 1700
been
into
and
complex"
reaction
work ref,
results
of cyclohexene
has been [l].
reported
published
with in
by
364 triethylsilane as mentioned
and carbon
monoxide
we have
above,
in the presence
found
that
this
triethylsiloxymethylenecyclohexane0 product
in a good
a similar reaction
result
was
proceeds
in a formally
assumes
similar
that
way
I f HSiR3 + CO
be expected. The
in eq.
of
product(I) The
l
since
monoxide
results
from
in the
All
results
are
into
found
incorporated the carbon
which
no experimental
hydrogen used.
reacticn
possible
details
were
and
*
in the
cycloalkenes
equivalent) reactions
Harrod
given
group
l
using
to explain
the
and oxygen
in the oxymethylene
known
of Chalk
found.
as shown
the catalytic
it is not
was
can be presented
that
for the
(1)
(ill), may
compounds
and diethylmethylsilane(1 1.
(ll) and
the hydrosilane
obtained
Unfortunately,
See ref-
are
it is not yet
in the Table
difference
reactants
it is obvious
has come
(3 equivalents)
of these
of the reaction
While
carbon
of products,
neither
1, and all three
of the product,
given
types
However,
product(I). atoms
OSiR3
two
stoichiometry
the
as
cl
hydrofonnylation.
gave
diethylmethylsilane.
If one
found-
reaction
as a sole
For
yield;*
of Co2(CO)3,
are
were
the
and ours,
in their
paper.
161.
tt Ueuterium
labeling
experiments
are
now
in progress.
:
365 TABLE1 REACTION
OF VARIOUS
OLEFINS WITH _ -___-.Catalyst
Olefin
co2
Et2MeSiH
AND
COa)
Product
yield(%) (GLC)
(CO) 8
-.
48 OSiEt2Me(IV)
co2
(CO) *
Ru3 (CO)
71
OSiEt2Me(Ic)
1.4
12
Rhcl(PPh313
co*
0.5
CT
(CO) *
74
OSiEt*Me(V)
CF
co* (CO) 8
69
OSiEt+Me(VI)
co2 (CO) *
22 OSiEt2Me(VJI) &
co* a) Reaction
cat.
(10 mmol) s CO{80
benzene(20
out
45
conditions:
Et2MeSiH
carried
(CO) *
using
a 100 ml
a solution
(10 mmol),
and Co2(CO)6(0.2
under
to give The
20 h, in
stainless
steel
mmol)
of carbon
autoclave. mmol),
in benzene(20 monoxide
Et2MeSiH ml) was
at 140°C
diethylmethylsiloxymethylenecycloalkanes(Ic
then
finally
140°C,
of a cycloalkene(30
a pressure
pressure
25-C.
kg/cm2),
of carbon reached
76-79
completed. -.
monoxide
105-108
kg/cm2
While
-.
mmol),
ml)
Generally,
heated
olefin(30
(0.2 mmol),
kg/cm2
at 25*C
simple
was
after
cyclic
initialy
at 19O"C,
for 20 h and
80 kg/cm2 and
the reaction
IV-VDI). at
it was had been
olefins(cyclohexene,
cycloheptene,
366
except
and cyclooctene), product
in good
expected were
olefin,
product_ only
accompanied
disiloxane When
in 5-15% Ru3(C0)12
were
gave
in moderate
the expected
of 1-methylcyclohexene, a bicyclic
and norbornene,
All
yieldof the
the
olefin,gave reactions
corresponding
yield. and
were
RhCl(PPh5)5
only
of cyclohexene, This
obtained-
hydroformylation yields
reaction
by the .formation
for the reaction ether(Ic1
the
yield,
a trisubstituted
for cyclopentene,
traces
result
of cyclohexene
has
used
of the enol
interesting,
is
been
of cyclohexanecarboxaldehyde
as catalysts
known
silyl
since
to give
in the presence
good
of Ru3(CO)12
c121Reaction
of cyclohexene -
Cyclohexene carbon
monoxide
corresponding eq.
1,
The
reacted
yield.
with
hydrosilanes
various
hydrosilanes
of Co2(CO)S
results
were
summarized
except
yielded
the yield
having
of the products(Ie
a phenyl and
in the order
PhMe2SiH>Ph2MeSiH>PhjSiH.
following
hydrosilanes
did
give
siloxymethylenecyclohexanez
Ph$iH,
The
gave
reaction
without
of
recovery
that hydrosilanes have
good
(MeO12MeSiH
reactivity
for the low yield
Ph2SiH2,
very
in the case
The
(Me0)2MeSiH,
results,
results
show
substituents
reaction,
of Me$iH
and
complex These
electron-donating
in the present
If)
the corresponding
of the hydrosilane. with
the in good
decreased
not
in
2,
siloxymethylenecyclohexanes(Ib-Id) of hydrosilanes
the
as shown
in Table
for Me$SiH,
and
to give
siloxymethylenecyclohexanes(1)
In the case
substituent,
various
in the presence
Trialkylsilanes, corresponding
with
The
reason
is not clear.
It may be intrinsic or due to the different experimental procedurekee
Experimental
Part).
the
367
TABLE
2
REACTION
OF CYCLOHEXRNE
WITH
Yield Hydrosilane
the product(I)
AND
COa'
(R3Si)20b)
hydrosilane(%)
(Ia)
4
88
0
EtMe2SiH
(Ib)
57
36
5
Et2MeSiH
(ICI
71
5
8
Et3SiH
(Id)
74
0
23
PhMe2SiH
(Ie)
51
29
18
Ph2MeSiH
(If)
26
57
6
Ph2SiH2
0
39
18
Ph3SiH
0
88
0
(!4eO)2MeSiH
0
0
0
COAX
(0.2 mmoll.
conditions:
(30 mmol), 20 h,
Effects
(I) was
corresponding
a three
the
reactions
hydrosilane obtained
to I
these
140°C,
used.
(eq. 3).
and
was
used,
a single
reactions
another
as
product
were
carried
and a product
was
The product
may
isomerizaticn
of the
distribution
of the products
CO OSiEt2Me
cat.
only
of a cycloalkene
double-bond
The yield
Et2MeSiH,
above,
temperature,
by catalyzed
product(
of cyclohexene
when
amounts
in addition
formed
excess
However,
at higher
kg/cm2),
to hydrosilanes
described
equimolar
CO(80
conditions
fold
obtained_
using
mmol),
cyclohexene
ml).
of -- the reaction
When in all
hydrosilane(l0
in benzene(20
b) Disiloxanes
be
HYDROSILANES
Recovered
Me3SiH
a) Reaction
out
VARIOUS
of
Co2KO)g
OSiEt2Me
+ r
>m (IC)
(IX)
(3)
368 were
found
as molar
to
be
ratio
of carbon
The
monoxide.
monoxide
by
the
of reactants,
of cyclohexene
TABLE
affected
with
conditions
reaction
results
in the Table
the pressure
for the
obtained
diethylmethylsilane
are shown
and
temperature,
and
such
reaction
carbon
3.
3
EFFECT
OF THE
REACTION
Eeaction Cyclohexene
CONDITIONSa
conditions
Et2MeSiH
CO pressurec'
OC
ILUUOl
mmol
Combinedb'
Temp.
yield
distribution
(Ic+Ix)(%)
kg/cm*
Ic
I IX(%)
140
30
12
99:
1
140
60
36
97:
3
10
140
80
37
98:
2
20
10
140
80
51
98:
2
30
10
140
80
71
100
:
0
30
10
200
80
84
80
z
20
10
10
10
10
10
a) All
reactions
b) The
yields
-
were
and
carried
out
the product
in 20 ml of benzene
distribution
were
for 20 h-
determined
by
GLC. cl Initial
The
pressure
combined
in the pressure very
small
yield
at 60-80 with
Et,WSiH_
The
combined
The
fact
cyclohexene
that
The molar
product
of the initial
IX increased
monoxide,
kg/cm2.
increasing
the isomerization
temperature_
of Ic and
of carbon
remarkably
the yield
at room
ratio yield
an increase
the difference
combined
product(Ic1
product
but
with
yield
increased
of cyclohexene was
best
decreased
was
to
at 200°C, and
that
but of
increased_
the use of a higher
to the hydrosilane
has
molar
resulted
of the product
suggested
the
tetracarbonyl,
EIcoKOIq,
as the active
importance
ratic
of
in a higher
of hydrocobaltcatalyst
in the
yield
369
present
reaction, has
coz(Co)8
The
(eq. 4)initiate amount
been
The known
to give
Co2(CO)S
trialkylsilanes
HCo(C0]4 may
cycle(eq.
of the olefin
+
of
hydrocobaltcarbonyl
a catalytic
R3SiH
reaction
5)
->
and R3SiCo(C0)4
react
However,
is not present
with
with
olefins
when
a sufficient
in the system,
R3SiCo(C0)4
(6. 131
+
to
it reacts
HCo(CO)4
(4)
(5)
HCO(CO) 4
~/
with
R3SiH
the hydrosilane
(eq. 6). cycle.
This The
to give
complex
the product(I)
an acylsilane reaction.
are
many
interesting
reaction metal Are
related
complexes
the effective
or hydrosilylation
then
reacts
we have
needed
in eq.
5 may-give
with
a hydrosilane
thdt
questions.
metal
we can understand
reaction
How closely
catalysts3
raised
is the present
What
kind the
kind
.
of reaction?
hydroformylation
What
the
reactions.
has
in catalyzing
complexes
or
all possibilities.
to hydroformylation? are effective
an aldehyde
in the present
of the present
of the present
131
of hydrocobaltcarbonyl.
stated
before
cycle
(6)
the. catalytic
regeneration
reexamining
of the catalytic
The discovery
stop
formed
i- H2
and hydrogen(6,
not be an intermediate
We are now
experiments
nature
with
report,
may
6) would
complex which
R3SiCo(CO)4
R3SiCo(CO)4
reaction(eq_
In a preliminary
More
to give
alkylcobalt
an acylcobalt
>
of olefins
catalysts can be
370 Is the present
used? All
these
questions
It should highly that
reaction
will
be dealt
be pointed
versatile
appliciable
out
that
intermediates
the present
reaction
for the synthesis
with
silyl
for organic
silyl
to olefinsl
in forthcoming
enol
represents
of enol
only
the
ethers
papers_
ethers
are
synthesis[l41 first
from
and
method
olefins.
Experimental
General
comments
All
temperatures
recorded
with
measured
on a Japan
with was
Me4Si
a Shimazu
Mass
spectra
Model
with
were
RBU-CE_
High RMU-7M.
were
out
carried
equipped
with
used were
6mx3mm 60-80
mesh
cromosorb
using
a Varian
commercially was
. SA molacular
dried
commercially
(A) 6mx
over
methods
GC-3BF
of the
standard
compound_
mass
and
spectrometer were
recorded
a Shimazu
detecters,
The
3mm stainless mesh
Dniport
gas
sodium-lead
purified and
prepared
Authentic
ES;
(B) on
carried
out
were
samples
Olefins
by distillation. stored
over
according
and RhCl(PPh$9
Hydrosilanes
containing
chromatograph,
alloy
were
columns
supported
GLC was
90-P
GC-6A
GLC
steel
15% DEGS
and were
Ru3(CO)12
1161.
spectrum
spectra
Preparative Model
of .hIe4Si
gas chromatography(GLCZ
containing
Co2KO)*
available.
recording
were
spectrometer
The position
on 60-80
available
sieves.
the literature[l5].
standard
ionization
Aerograph
JNM-PS-100
mass
were
spectra
the signal
Analytical
W.
H-NNR
on a Hitachi
resolution
steel
1
of a organosilicon
supported
stainless
Benzene
that
on a Shimazu
flame
OV-1
it after
Otherwise
as follows:
5% Silicon
Optics
standard_
recorded
on a Hitachi
were
Electron
by adding
may be confused
The
IR-400_
the standard.
IR spectra
uncorrected.
as an internal
recognized
without
are
were
prepared
by
of disiloxanes
to
3i1
were
prepared
by RhCl(PPh313
with
appropriate
for the --
and --
carbon
with
pressure
30 mm01
0.2 mm01 was
heated
with
with
to
pressure
opened. with
Analysis
n-pentadecane, -_ (I and
IV-IX)
and
of the products each
case.
slowly
was
appropriate mixture
and
standard
internal
of the
preparative
GLC
was
temperature
to 76-79
cooled kg/cmL. was
by GLC(column
retention
A)
the products time)
is sho-&n below
A and Bl with
Distillation
for
time
The
standard,
afforded
1 h,
then
time)=retention
by GLC(column standard.
The
it to contain
to an internal
time
After
then
l-tetradecane,
showed
retention
was
the autoclave
mixture
RRT(relative
analyzed
and/or
The vessel decreased
then
vessel
bath_
(R3Si)20_
RRT(relative
charged
autoclave
(50 kg/cm2),
(n-tridecane, -
a-300
bar was
at 140°C.
released
n-eicosane)
the compounds/retention recovered
reaction
reaction
standard or
The
pressure
with
The
CO
kg/cm2
(COj8
of the hydrosilane,
and
for 20 h_
of the
an internal
10 mm01
in an oil
105-108
The
was
stirring
with of Co --2-
equipped
20 ml of benzene-
kg/cm2)
at 140°C
temperature_
The gas
and
stirring
reached
maintained room
autoclave
and a magnetic
N2(80
magnetic
the pressure was
steel
CO to 80 kg/cm2.
with
reflux
of cycloalkenes in the p resence --
the cycloalkene,
of co2(co)8
flushed
charged
gauge
of
as solvent,
reaction
monoxide
A 100 ml stainless kg/cm2
of water
yields)_
procedure
hydrosilanes
silylation
hydrosilanes(benzene
48 h, quantitative
General
catalyzed
of
hydrosilane an
of the reaction
the analytical
samples.
Diethylmethylsiloxymethylenecyclohexane(IC) Analysis
by GLC(column
internal
standard(RRT
(8%. RRT
O-29)_
1450,
1380,
1260,
1)):
A, 130°c, Ic(71%,
.Ic: bp 130-138°C(28 1240,
1220,
1160.
n-tetradecane
RRT
0.79)
I&): 1090,
and
(Et2MeSi120
IR(neat) 1070,
as an
2924,
1010,
1680,
970.
372 910,
820,
800,
1.,36-1_6O(c
O-96 (m 6H1, (s 1~); mass X01(9$,
760 cm-':
spectrum
89(100$-
Anal, N, 11.38.
NMk(Cb14) 6R$,
5 0.08b
1.88b
ZHJ,
3H$,
2.1Ob
nt/e(rel. intensity).
0.58b 2H1,
2121331,
4H$,
5.88
X83(401,
.
Calcd
for C12H240Si:
Found:
P+,
212.1561;
P+, C,
212.1595;
67.80;
C, 67-85;
H, 11-40.
RiethylmethyLsiloxymethylenecyelopentane(fV) Analysis internal
by GLC(column
standardCRRT
800,
1415,
760 cm-';
1_58(m
4H$,
intensity$
~tw(cC14)
2,12&x
CaXcd
F&k?:
11.18.
Iv(488,
11)~
1250,
4H$,
1170,
6_04(s
X98-1409:
P+,
O-80)
mm);
3x$,
and
960,
0,60(m
lzf$_rmass
P*,
aS an CEt2MeSi120
IR(neat$
1005,
103{9$,
for C11H220Si:
n-tridecane
RRT
1120,
5 0.08(s
169(39),
198(30$,
&al_
120°C,
IV; bp 98-300°c(15
(8% RR!i?0.46;. X.685, 1460,
A,
2950, 950,
4H$,
spectrum
2875,
840-820, 0.96(m
6R$,
xtfe(rel.
89(100$198.X438:
C, 66-35:
C, 66.59:
H,
X, -iO.94_
DiethyLmethyJ_siloxymethyhylenecycXoheptane(V$ Analysis
by GLCCcoluxnn
internal_ standardfm V; bp
(9%)-
0.08&z
3H),
intensity)
IL.57,
4H1,
C&&cd
Found:
P+,
197(35),
RRT
1.29)
810,
6H$,
2950,
76C cm-':
as an
(Et2MeSi$20
1660,
spectrum
lOl(ll$, P+,
and
X-40-1.7Ofc
.?_H$;mass
for Cx3H260Si: 226,X731:
fl-tetradecane
IR(neat)
870,
0.96fm
Z'iif,5,92Cs
226(13$,
Anal,
mm);
3.000. 960,
0.58cm
2,20(m
(m 2H$,
140°C,
I)$.: V(748,
155-L6S°C(50
X3.90, 13.60, X130,
A,
1450,
1260,
NMR(CC14Q) 5 SE),
i-99
m/ekel.
89(100$226.1750;
C, 68-97:
C, 68.95;
H,
a, 1X-70-
Diethylmethylsikxqmf&hylenecyclooctane(IVI) Analysis internal
by GLcicolumn
sia.nMfREzT
A=
EOW,
X33; VX[69%.
z-tetiadecane
RR!P X.963
and
as
ax%,
~Bt2MeSi~20~
-
3i3
(ll%)_ 1250,
VI;
bp
1235,
126-13S°C(25
1200,
cm -1: NMR(CC14) l-36-1_72(c
m/e
lOl(18).
89(100)_
Anal.
Analysis an
internal
not of
and
VII
3H).
i_98(m
intensity)
1060,
240
240.1914;
structure
A,
the
it is not
1.521,
1010.
2950,
960,
2900,
880,
- (s 3H), 0_60(m
820,
1680,
1460,
0_88-1_20(m
4H),
1.86-2_12(c
2.8O(c
1H).
5.88(s
mass
Spectrum
11.57,
Calcd
Found:
P+,
compound
211(S).
226-1731;
GLC)
0.08
.
2.60-
(rd.
lOl(ll),
89(lOO)-
P +, 226.1751:
C, 68-59:
mm);
with
2H),
m/e
197(U),
for C13H260Si:
is
1100,
6H)overlapped
6H),
Anal.
as
(Et2MeSij20
N&!R(CC14) &
1_20-1_86(c
226(11).
C, 68.95;
H, 11.75.
2-Diethylmethylsilo-~ymethylenenorbornene(Vm) Analysis
by GLC(column
an internal
standsrd
(Et2xeSi)20
(7%).
JAI;
2940,
1690,
1250,
810,
2860,
760 cm-l;
A,
150°C,
(RRT 1)); Vm(45%,
NMR(CC14)
bp
130-140°c(10
1160, a
1140,
0.08(s
H,
1.641,
1150,
3H),
intensity)
C, 69-92:
120-12S°C(17
0_96(s
1H);
mass
2-diethylmethyl-
1260,
770 cm-';
770
121(21),
of an 1-l mixture(by
VII ; bp
800,
1H);
n-tridecane
and
with
800,
H, 11.64.
unidentified
consistent
1480,
6H),
5-94k
VII (22%. RRT
siloxyethenyl-l-cyclohexane. IR(neat)
1660, 860,
211(33),
(131,
13O"C,
RRT
of
960,
2H).
C, 69.88;
spectrum
NMR
1000,
•t P , 240_1908;
1));
compoundi5%,
2920,
0.58(m'4H),.0.97(m
for C14H280Si:
P*,
but
IR(neat)
2Ii). 2.24(m
standard(RRT
The
clear,
5 O-08&
by.GLC(column
unidentified (15%)*
1090,
Calcd
Found:
11.73.
1160,
10H).
spectrum
mm):
n-tetradecane RRT mm);
1100,
3H).
l-71)
and
IR(neat)
1000,
0.57(m
as
850,
4R),
H,
:,<
0_90(m
6H).
1_12-1_32(c
4~1,
1_86(m
lH),
2_04(m
2_31(m
In addition,
small
spectnxn
may
1H).
lH),
absorptions
The product
observed. mess
la),
1.47(m
1H).
1R).
and
two
(rel, intensity)
m/e
2-55(m
at 3-06
contain
1.61(m
6,02(m
S-79 were
stereo
224(39).
lh);
also
iSOmerS-
195(100),
101
(441, 89(39)_ Calcd
Anal, C, 69-41:
for C13R240Si:
internal
standard(RRT
(5%, RRT
O-13)-
840,
1450,
mass
Ib;
1380.
780 cm-':
(m 3H).
H, 10.77,
Found:
H, 10.91.
imalysis by GLC(column
1680,
C, 69.57;
bp
2
6~), (rel-
RRT
o.ll(s
1.88(m
O-70)
mm);
1080.
1150,
NXR(CC~~)
m/e
Ib(57%.
82-8S°C(13
1250.
1,35-1_59(c
spectrum
1)):
ytridecarze
A. llO°C.
6H),
2H).
intensity)
and
IR(neat)
1060,
0.57(m
(EtMe2Si)2G 2910,
1000,
2.1O(m
960,
2850. 900.
2H), 0.96
2H).
198(25),
as an
5.84(s
169(22),
1H);
89(14),
75(100)Anal. 11_18.
Calcd
Found:
for C12H220Si:
P+,
198-1428;
P+,
198-1438: H,
C. 66-87:
C, 66.59;
H,
11-18.
Triethylsiloxymethylenecyclohexane(Id1 Analysis internal
by GLC(column
standard
(23%. RRT 0.44). 2895, 820,
1675,
1,74(c
6~1,
spect-
Anal. C, 69-05:
1260,
Id(74%.
1240,
NXR(CC_~~)
2H).
4
Calcd
1220,
0_70(m
2_22(m
(rel, intensity)
87(17),
135"C,
Id; bp 135-139°C(20
2.Ol(m
m/e
103(100),
(RRT 11):
1445,
740 cm-';
A,
g-pentadecane
RRT
mm); 1150,
6H),
2H).
O-77)
226(24).
(Et3Sij20
IR(neat) 1090,
l.O9(m
6.02(s
and
as an
2920,
1010,
9H).
910.
l-44-
1l-l);mass
197(41),
169tll).
75(55)for C13H260Sit
H. 11-62,
C, .68.95: El, 11.57.
Found:
375 Dimethylphenylsiloxymethylenecyclohexane(Ie) Analysis internal
standard
(18%,
RRT
2910,
2850,
1120,
970,
1680, 830.
Anal.
1430,
720,
1_86(m
2H):
231(4),
Ie(518,
Calcd
2H).
mass
168(10).
700
n-pentadecane
RRT
150-151°C(16
1590,
780,
6H).
7.44tm
(m 3H),
Ie; bp
160°C,
A,
(RRT 1));
2.19).
l-35-1_59(c
(42),
by GLC(column
1.97)
mm); 1200,
cm-l:
NMR(CC14)
spectrum
153(19),
2H),
m/e
for C15H220Si:
P+.
3050,
1150, 5 0.39(s
5.88(s
(rel.
137(78),
(PhMe2Si)20
IR(neat)
1250,
2.16(m
and
as an
lH),
6H),
7.26
intensity)
246
135(100) -
246_1439_
Found:
PC,
246-l-462_
Diphenylmethylsiloxymethylenecyclohexane(If) Analysis
by GLC(column
internal
standard
(6%, RRT
6.31).
2910, 900.
2850, 830,
A, 220°C,
(RRT 1)); If; bp
1680,
If(26%,
1430,
790,
720,
700 cm-l;
(c 6H).
1_91(m
2H).
2.25(m
(m 4H);
mass
199(63),
197(100).
Anal. C, 77-58:
Calcd
RRT
150-156°C(0.55
1590,
spectrum
E-eicosane
m/e
1250,
1.65)
mm); 1140;
NMR(CC14)
2H), (rel.
6.01(s
as an
and
o?h2MeSi)20
IR(neat); 1120.
0 0.63(s lH),
intensity)
3050,
1080,
1060,
3H),
7_34(m 308(38),
1.53
6H);7.55 215(33).
137(91)-
c,
for C20H240Si:
77-87:
H, 7_84..Found:
H. 7-68.
Trimethylsiloxymethylenecyclohexane(Ia) A solution
of cyclohexene(30
mmol)
in 20 ml of benzene
steel
autoclave.
and
CO(50
(10 mn01)
kS/cm2) was
was
autoclave
and
cooled
introduced under
vacume
charged
CO to 80 kg/cm2
(0.2
in a 100 ml
stainless
was
flushed
to -7ooc.
to the
distillation with
placed
The
and COAX
mmol)
mm)
at 25OC
N2(80
kg/cm2)
Trimethylsilane
autoclave and
with
then
by trap-to-trap the autoclave
and heated
was
at 140°C.
3'76 The GLC
retention
time
of the product
trimethylsilpxymethylenecyclohexane prepared
from
by House's
(RRl! 1));
(23
IR(neat)
2950,
900.
1.84&
840,
2H).
2.04(m
that
Of
independently
trimethylchlorosilane
2H),
n-dodecane
RRT
0.65).
1675,1445,
NMR(CC14)
5.80(s
184(44),
Calcd
Ia(48,
2850,
740 cm-l:
(rel. intensity) Anal.
and
A, 100°C,
by GLC(column
standard
1080.
was
to
[171.
internal mu);
identical
which
cyclohexanecarboxaldehyde
method
Analysis
was
1H); mass
for C10H200Si:
1210,
9H),
1150,
1.44(C
spectrum
155(21),
P*.
Ia: bp 91°C
1250,
$_ 0.14(S
169(42),
as an
m/e
75(100)
184.1282.
6H).
73(98).
Found:
P+.
184.1279.
I-(Diethylmethylsiloxymethyl)-cyclohex-l-ene(IX) T‘ne experimental procedure
except
internal and
1460,
760 cm-'; (m 4H), m/e
(156, RFT
1420,
1255,
NMR(CC14)
5
(rel. intensity;
11.38.
Calcd
Found=
A,
1160,
IX:
3H).
212(14).
0.811,
at 2OO“C.
1070,
5.50(m
183(31),
2020,
1010, 4H),
RRT
0.791,
2870,
965,
840,
800,
0.93(m
6H),
1.60
1H); mass
103(7),
, 212.1594:
C, 67.83:
as an
Ic(678,
IR(neat);
2H),
P
out
E-tetradecane
0.53(m
t
as the..general
carried
RRT
1090,
3.85(s
212.1560;
was
100°C,
0.29).
for C12H240Si:
P+,
the same
1X(17%,
O.Ol(s
4H),
was
reaction
(RRT 1));
1.80-2.12(c
Anal.
the
GLC(column
standard
(Et2MeSi)20
1675,
that
by
Analysis
procedure
spectrum
89(100). C. 67.85:
H,
H. 11_.44.
Acknowledgments This in-Aid
was
generously
for Scientific
of Japan. supply
work
We thank
Research Shin-Etsu
of organosilanes.
supported
in part
by the Ministry Industry
Co.,
by a Grantof Education
Ltd.
for the
-
3ii References
1
Y.
Seki,
Chem. 2
A. Hidaka,
Int.
Ed.
J. F. Harrod, S. Chem.,
3
47
(1969)
73
Metal
Chemistry
(1973)
York,
a Mechanistic p 55;
by Metal
New
York.
1974.
50
(1974)
Synthesis,
Press,
of Homogeneous
7
Press,
Transition Dekker,
New
Syntheses
Press,
with
Noble
New York,
1973,
Vol.
p 274;
Homogeneous
2, Academic Top.
Press,
Curr.
Chem.,
F.
Harrod,
Adv.
(b) J. Falbe,
Carbon
Springer-Verlag.
Catal. Metal New
Rev., Rev.,
6
(1972)
Catalysis,
1967;
Boston,
1910.
in
1970;
49:
(d) M. Orchin
85;
(e) C. W.
in Organic
(f) R. Ugo, 2. D. Reidel
Vol.
and J. F. H?rrod,
Monoxide
Berlin.
(19721
Intermediates
York,
and
6
Organomet.
Synthesis,
Aspects Publishing
1974. J. Amer.
Chem.
Sot.,
1640.
B. J. Aylett (1969)
Academic
Marcel
(c) F. Hofler,
Catal.
Dordrecht
A. J. Chalk (1967)
Approach,
Complexes,
119;
Transition
Company.
Chem.
Organotransition
and A. E. Martell,
and J.
(1968)
and W. Rupilus,
Academic
Can.
129.
(c) F. E. Paulk,
6
Organic
p 66:
(a) A. J. Chalk
Bird,
D. J. Brown,
Catalysis,
Khan
Catalysis
Organic
and
(c) J. Kwiatek,
Academic
(b) M. M. Taqui
6
R. Charls,
p 13.
Catalysts,
Chem.,
and
(b) R. C. Heck,
(a) P. N. Rylander, Metal
174.
S. K. Gupka, 21;
1974,
1971,
(1977)
Angew.
2205.
in Homogeneous
York,
5
16
and N. Sonoda,
D. F. R. Gilson,
Rev.,
Metals
4
Engl.,
(a) R. F. Harmon,
New
S. Murai,
and 3. M. Campbell,
J. Chem.
Sot.
(A),
89
3?s 8
la) B. J. Aylett Chem.
(A), 9
F.
de
137:
Sot.
L.
(1968)
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11
A. J. Chalk,
J. Organometal.
12
G. Sbrana,
Chin.
Ind.
Y. L. Baay,
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J. K. Rasmussen,
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26
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(Hilan),
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Chemisby, 110 (1977) 361-318 8 ElsevierSequoiaS.A..Iausanne-PrintedinThe~etherlands
TRANSITION
METAL
CYCLOALKENES CATALYZED
YOSHIO
REACTIONS
WITH --
VARIOUS
SEKI,
AKIHIKO
HIDAKA,
SONODA
Department
of Petroleum -
University,
(Received
July
The
6th.
cycloheptene, norbornene)
Osaka
AND CARBON --I___
EtZMeSiH
of Co2(CO)S
following
MAKINO,
Faculty
565
gave
cyclohexene,
and
carbon
monoxide
the
corresponding In such
gave
diethylmethyl-
reactions
Et3SiH,
Effects
of the
and
the molar
The
yield
increased
pressure ratio
of cyclohexene,
the corresponding EtMeZSiH,
Ph2MeSiH.
and in the
Me3SiH,
conditions(the
*
Japan
1-methylcyclohexene,
hydrosilanes
PhMe$iH,
MURAI,
of Engineering, -
siloxymeth$lenecyclohexanes:
of carbon
reaction
monoxide,
of cyclohexene
to
Et2MeSiH,
the
EtZMeSiH)
temperature, were
examined_
of diethylmethylsiloxymethylenecyclohexane remarkably
cyclohexene of the
OF -
MONOXIDE
SHINJI
of cycloalkenes(cyclopentene,
siloxymethylenecycloalkanesthe
REACTION
1977)
cyclooctene, with
SHIGEO
Chemistry,
Suita -'-_f
reaction
presence
HYDROSImES
THE
II:
BY - COAX-
and NOBORU
Osaka
OF - SILANES ---
361
with
to Et$?eSiH.
isomerization
cyclohex-1-ene,
increasing
At higher
product,
molar
ratio
temperature,
of
the yield
l-(diethylmethylsiloxymethyl)-
increased.
Introduction
It is well f -Por.part .
known
that
the metal-catalyzed
1, see
ref,
[l).
reactions
of a
362 hydrosilane case
of
parallels
oz.&dative
hydrosilane[2]
addition
relatedC2,
between
reactions
of olefins no such
Chalk
has
and Harrod
was
details
were
complex
mixture
ranging
from
fractions alkoxy
reported,
reaction The
reported
In the case
was
of the
of our
with
complex"
and
and
no
however,
with
boiling
into
a points
thirty
three
unsaturated
(C2H513
which
propionaldehyde
of
by
triethylsilane
to contain
C3H50Si
However,
described
of ethylene,
found
reaction
the dicobalt
fractionated
formula
formal
of pent-l-ene
products
of
in transition
reaction
"very
to be
to 300°C
The
monoxide.
of olefins
of the reaction
90°C
addition
the catalyzed
studied
reaction
and one of them was
gave
on treatment
the hydrasine, Beside
have
to an
to be very
to the best
They
the 2,4_dinitrophenylhydrazone with
about
and carbon
in 1967161,
given.
silane(s1
seem
and hydrogen
for an interesting
monoxide.
cyclohexene
*-adducts.
involves
us curious
been
octacarbonyl-catalyzed and carbon
reactions
a hydrosilane
except
knowledge,
of a
hydrogenationl31.
to olefinsl53.
a hydrosilane
reaction
in the
both
of R3SiH
to catalytic
monoxide
has made
with
to give
addition
hydroformylation
and carbon
similarity
react
these
example,
3, Sal_
The well-known hydrogen
For
complex,
axi Ir(i)
analogous
mechanistically
closely
metal
to
the catalyzed
is formally
Moreover,
of hydrogen.
and hydrogen13al
Eiydrosilylation[41, olefin,
those
been
reported compounds examples
made
mentioned
and somewhat
on the reaction
seem
or the reaction
surprisingly
discouraging
limited
results
monoxide
of transition
to be mostly reaction
work,
of carbon
in the presence
the catalyzed monoxide
the above
with
metals.
to studies
few studies have
been
organosilicon The
dealing
scattered with
involving
a hydrosilane
and
carbon
between
the complexes
containing
363 silicon-metal
bonds
reported
that
no direct
occurred
at
pressures has
reported
the
with
co-workers 4000
carried
atm of carbon
carbon
monoxide
It has
been
reported
as of phosphines, addition
that
reaction
inhibited
reacts
use
and hydrosilanes
dicobalt
gave
only
one
product,
been
obtained
remarkably the
by direct Haqen
with
insertion
bond
was
of
observed[lO].
monoxide,
as well
octacarbonyl-catalyzed
work,
smoothly
clean
cases
of the catalyzed
we have
with
found
that
cycloalkenes The
of COAX. results.
_
From
catalytic
cycloalkenes,
studied.
reaction
and carbon
monoxide
In.this
paper,
of cycloalkenes under
various
has the-
with
reaction
l
conditions
Results
and -
Reaction carbon
are
Chalk
*
described.
discussion
of cycloalkenes -
with
diethylmethylsilane
and
monoxide
Contrary and
to the
Harrod
A portion
preliminary-form,
"very
for the of this see
and
trialkylsiloxymethylenecycloalkane,
in most
hydrosilanes
but-no
It
insertion
to acrylonitrile[ll]
in the presence
reaction
bonds
of carbon
previous
very
carbonyf
of MeSiClzCo(CO)4
at 90°C.
the
monoxide
unsuccessful.
the silicon-cobalt
to this
monoxide
results
the
Harrod
of Co2(CO)8[6].
Si-Rh[9]
were
of dimethylchlorosilane
.In contrast carbon
monoxide
and
carbon
to induce
and
monoxide
into
and
in the presence
attempts
out
Chalk
of triethylsilane
up to 300%
Si-Mn[S],
carbon
monoxide.
carbonylation
psi
that
Si-Col7],
reaction
carbon
temperatures
up to 1700
been
into
and
complex"
reaction
work ref,
results
of cyclohexene
has been [l].
reported
published
with in
by
364 triethylsilane as mentioned
and carbon
monoxide
we have
above,
in the presence
found
that
this
triethylsiloxymethylenecyclohexane0 product
in a good
a similar reaction
result
was
proceeds
in a formally
assumes
similar
that
way
I f HSiR3 + CO
be expected. The
in eq.
of
product(I) The
l
since
monoxide
results
from
in the
All
results
are
into
found
incorporated the carbon
which
no experimental
hydrogen used.
reacticn
possible
details
were
and
*
in the
cycloalkenes
equivalent) reactions
Harrod
given
group
l
using
to explain
the
and oxygen
in the oxymethylene
known
of Chalk
found.
as shown
the catalytic
it is not
was
can be presented
that
for the
(1)
(ill), may
compounds
and diethylmethylsilane(1 1.
(ll) and
the hydrosilane
obtained
Unfortunately,
See ref-
are
it is not yet
in the Table
difference
reactants
it is obvious
has come
(3 equivalents)
of these
of the reaction
While
carbon
of products,
neither
1, and all three
of the product,
given
types
However,
product(I). atoms
OSiR3
two
stoichiometry
the
as
cl
hydrofonnylation.
gave
diethylmethylsilane.
If one
found-
reaction
as a sole
For
yield;*
of Co2(CO)3,
are
were
the
and ours,
in their
paper.
161.
tt Ueuterium
labeling
experiments
are
now
in progress.
:
365 TABLE1 REACTION
OF VARIOUS
OLEFINS WITH _ -___-.Catalyst
Olefin
co2
Et2MeSiH
AND
COa)
Product
yield(%) (GLC)
(CO) 8
-.
48 OSiEt2Me(IV)
co2
(CO) *
Ru3 (CO)
71
OSiEt2Me(Ic)
1.4
12
Rhcl(PPh313
co*
0.5
CT
(CO) *
74
OSiEt*Me(V)
CF
co* (CO) 8
69
OSiEt+Me(VI)
co2 (CO) *
22 OSiEt2Me(VJI) &
co* a) Reaction
cat.
(10 mmol) s CO{80
benzene(20
out
45
conditions:
Et2MeSiH
carried
(CO) *
using
a 100 ml
a solution
(10 mmol),
and Co2(CO)6(0.2
under
to give The
20 h, in
stainless
steel
mmol)
of carbon
autoclave. mmol),
in benzene(20 monoxide
Et2MeSiH ml) was
at 140°C
diethylmethylsiloxymethylenecycloalkanes(Ic
then
finally
140°C,
of a cycloalkene(30
a pressure
pressure
25-C.
kg/cm2),
of carbon reached
76-79
completed. -.
monoxide
105-108
kg/cm2
While
-.
mmol),
ml)
Generally,
heated
olefin(30
(0.2 mmol),
kg/cm2
at 25*C
simple
was
after
cyclic
initialy
at 19O"C,
for 20 h and
80 kg/cm2 and
the reaction
IV-VDI). at
it was had been
olefins(cyclohexene,
cycloheptene,
366
except
and cyclooctene), product
in good
expected were
olefin,
product_ only
accompanied
disiloxane When
in 5-15% Ru3(C0)12
were
gave
in moderate
the expected
of 1-methylcyclohexene, a bicyclic
and norbornene,
All
yieldof the
the
olefin,gave reactions
corresponding
yield. and
were
RhCl(PPh5)5
only
of cyclohexene, This
obtained-
hydroformylation yields
reaction
by the .formation
for the reaction ether(Ic1
the
yield,
a trisubstituted
for cyclopentene,
traces
result
of cyclohexene
has
used
of the enol
interesting,
is
been
of cyclohexanecarboxaldehyde
as catalysts
known
silyl
since
to give
in the presence
good
of Ru3(CO)12
c121Reaction
of cyclohexene -
Cyclohexene carbon
monoxide
corresponding eq.
1,
The
reacted
yield.
with
hydrosilanes
various
hydrosilanes
of Co2(CO)S
results
were
summarized
except
yielded
the yield
having
of the products(Ie
a phenyl and
in the order
PhMe2SiH>Ph2MeSiH>PhjSiH.
following
hydrosilanes
did
give
siloxymethylenecyclohexanez
Ph$iH,
The
gave
reaction
without
of
recovery
that hydrosilanes have
good
(MeO12MeSiH
reactivity
for the low yield
Ph2SiH2,
very
in the case
The
(Me0)2MeSiH,
results,
results
show
substituents
reaction,
of Me$iH
and
complex These
electron-donating
in the present
If)
the corresponding
of the hydrosilane. with
the in good
decreased
not
in
2,
siloxymethylenecyclohexanes(Ib-Id) of hydrosilanes
the
as shown
in Table
for Me$SiH,
and
to give
siloxymethylenecyclohexanes(1)
In the case
substituent,
various
in the presence
Trialkylsilanes, corresponding
with
The
reason
is not clear.
It may be intrinsic or due to the different experimental procedurekee
Experimental
Part).
the
367
TABLE
2
REACTION
OF CYCLOHEXRNE
WITH
Yield Hydrosilane
the product(I)
AND
COa'
(R3Si)20b)
hydrosilane(%)
(Ia)
4
88
0
EtMe2SiH
(Ib)
57
36
5
Et2MeSiH
(ICI
71
5
8
Et3SiH
(Id)
74
0
23
PhMe2SiH
(Ie)
51
29
18
Ph2MeSiH
(If)
26
57
6
Ph2SiH2
0
39
18
Ph3SiH
0
88
0
(!4eO)2MeSiH
0
0
0
COAX
(0.2 mmoll.
conditions:
(30 mmol), 20 h,
Effects
(I) was
corresponding
a three
the
reactions
hydrosilane obtained
to I
these
140°C,
used.
(eq. 3).
and
was
used,
a single
reactions
another
as
product
were
carried
and a product
was
The product
may
isomerizaticn
of the
distribution
of the products
CO OSiEt2Me
cat.
only
of a cycloalkene
double-bond
The yield
Et2MeSiH,
above,
temperature,
by catalyzed
product(
of cyclohexene
when
amounts
in addition
formed
excess
However,
at higher
kg/cm2),
to hydrosilanes
described
equimolar
CO(80
conditions
fold
obtained_
using
mmol),
cyclohexene
ml).
of -- the reaction
When in all
hydrosilane(l0
in benzene(20
b) Disiloxanes
be
HYDROSILANES
Recovered
Me3SiH
a) Reaction
out
VARIOUS
of
Co2KO)g
OSiEt2Me
+ r
>m (IC)
(IX)
(3)
368 were
found
as molar
to
be
ratio
of carbon
The
monoxide.
monoxide
by
the
of reactants,
of cyclohexene
TABLE
affected
with
conditions
reaction
results
in the Table
the pressure
for the
obtained
diethylmethylsilane
are shown
and
temperature,
and
such
reaction
carbon
3.
3
EFFECT
OF THE
REACTION
Eeaction Cyclohexene
CONDITIONSa
conditions
Et2MeSiH
CO pressurec'
OC
ILUUOl
mmol
Combinedb'
Temp.
yield
distribution
(Ic+Ix)(%)
kg/cm*
Ic
I IX(%)
140
30
12
99:
1
140
60
36
97:
3
10
140
80
37
98:
2
20
10
140
80
51
98:
2
30
10
140
80
71
100
:
0
30
10
200
80
84
80
z
20
10
10
10
10
10
a) All
reactions
b) The
yields
-
were
and
carried
out
the product
in 20 ml of benzene
distribution
were
for 20 h-
determined
by
GLC. cl Initial
The
pressure
combined
in the pressure very
small
yield
at 60-80 with
Et,WSiH_
The
combined
The
fact
cyclohexene
that
The molar
product
of the initial
IX increased
monoxide,
kg/cm2.
increasing
the isomerization
temperature_
of Ic and
of carbon
remarkably
the yield
at room
ratio yield
an increase
the difference
combined
product(Ic1
product
but
with
yield
increased
of cyclohexene was
best
decreased
was
to
at 200°C, and
that
but of
increased_
the use of a higher
to the hydrosilane
has
molar
resulted
of the product
suggested
the
tetracarbonyl,
EIcoKOIq,
as the active
importance
ratic
of
in a higher
of hydrocobaltcatalyst
in the
yield
369
present
reaction, has
coz(Co)8
The
(eq. 4)initiate amount
been
The known
to give
Co2(CO)S
trialkylsilanes
HCo(C0]4 may
cycle(eq.
of the olefin
+
of
hydrocobaltcarbonyl
a catalytic
R3SiH
reaction
5)
->
and R3SiCo(C0)4
react
However,
is not present
with
with
olefins
when
a sufficient
in the system,
R3SiCo(C0)4
(6. 131
+
to
it reacts
HCo(CO)4
(4)
(5)
HCO(CO) 4
~/
with
R3SiH
the hydrosilane
(eq. 6). cycle.
This The
to give
complex
the product(I)
an acylsilane reaction.
are
many
interesting
reaction metal Are
related
complexes
the effective
or hydrosilylation
then
reacts
we have
needed
in eq.
5 may-give
with
a hydrosilane
thdt
questions.
metal
we can understand
reaction
How closely
catalysts3
raised
is the present
What
kind the
kind
.
of reaction?
hydroformylation
What
the
reactions.
has
in catalyzing
complexes
or
all possibilities.
to hydroformylation? are effective
an aldehyde
in the present
of the present
of the present
131
of hydrocobaltcarbonyl.
stated
before
cycle
(6)
the. catalytic
regeneration
reexamining
of the catalytic
The discovery
stop
formed
i- H2
and hydrogen(6,
not be an intermediate
We are now
experiments
nature
with
report,
may
6) would
complex which
R3SiCo(CO)4
R3SiCo(CO)4
reaction(eq_
In a preliminary
More
to give
alkylcobalt
an acylcobalt
>
of olefins
catalysts can be
370 Is the present
used? All
these
questions
It should highly that
reaction
will
be dealt
be pointed
versatile
appliciable
out
that
intermediates
the present
reaction
for the synthesis
with
silyl
for organic
silyl
to olefinsl
in forthcoming
enol
represents
of enol
only
the
ethers
papers_
ethers
are
synthesis[l41 first
from
and
method
olefins.
Experimental
General
comments
All
temperatures
recorded
with
measured
on a Japan
with was
Me4Si
a Shimazu
Mass
spectra
Model
with
were
RBU-CE_
High RMU-7M.
were
out
carried
equipped
with
used were
6mx3mm 60-80
mesh
cromosorb
using
a Varian
commercially was
. SA molacular
dried
commercially
(A) 6mx
over
methods
GC-3BF
of the
standard
compound_
mass
and
spectrometer were
recorded
a Shimazu
detecters,
The
3mm stainless mesh
Dniport
gas
sodium-lead
purified and
prepared
Authentic
ES;
(B) on
carried
out
were
samples
Olefins
by distillation. stored
over
according
and RhCl(PPh$9
Hydrosilanes
containing
chromatograph,
alloy
were
columns
supported
GLC was
90-P
GC-6A
GLC
steel
15% DEGS
and were
Ru3(CO)12
1161.
spectrum
spectra
Preparative Model
of .hIe4Si
gas chromatography(GLCZ
containing
Co2KO)*
available.
recording
were
spectrometer
The position
on 60-80
available
sieves.
the literature[l5].
standard
ionization
Aerograph
JNM-PS-100
mass
were
spectra
the signal
Analytical
W.
H-NNR
on a Hitachi
resolution
steel
1
of a organosilicon
supported
stainless
Benzene
that
on a Shimazu
flame
OV-1
it after
Otherwise
as follows:
5% Silicon
Optics
standard_
recorded
on a Hitachi
were
Electron
by adding
may be confused
The
IR-400_
the standard.
IR spectra
uncorrected.
as an internal
recognized
without
are
were
prepared
by
of disiloxanes
to
3i1
were
prepared
by RhCl(PPh313
with
appropriate
for the --
and --
carbon
with
pressure
30 mm01
0.2 mm01 was
heated
with
with
to
pressure
opened. with
Analysis
n-pentadecane, -_ (I and
IV-IX)
and
of the products each
case.
slowly
was
appropriate mixture
and
standard
internal
of the
preparative
GLC
was
temperature
to 76-79
cooled kg/cmL. was
by GLC(column
retention
A)
the products time)
is sho-&n below
A and Bl with
Distillation
for
time
The
standard,
afforded
1 h,
then
time)=retention
by GLC(column standard.
The
it to contain
to an internal
time
After
then
l-tetradecane,
showed
retention
was
the autoclave
mixture
RRT(relative
analyzed
and/or
The vessel decreased
then
vessel
bath_
(R3Si)20_
RRT(relative
charged
autoclave
(50 kg/cm2),
(n-tridecane, -
a-300
bar was
at 140°C.
released
n-eicosane)
the compounds/retention recovered
reaction
reaction
standard or
The
pressure
with
The
CO
kg/cm2
(COj8
of the hydrosilane,
and
for 20 h_
of the
an internal
10 mm01
in an oil
105-108
The
was
stirring
with of Co --2-
equipped
20 ml of benzene-
kg/cm2)
at 140°C
temperature_
The gas
and
stirring
reached
maintained room
autoclave
and a magnetic
N2(80
magnetic
the pressure was
steel
CO to 80 kg/cm2.
with
reflux
of cycloalkenes in the p resence --
the cycloalkene,
of co2(co)8
flushed
charged
gauge
of
as solvent,
reaction
monoxide
A 100 ml stainless kg/cm2
of water
yields)_
procedure
hydrosilanes
silylation
hydrosilanes(benzene
48 h, quantitative
General
catalyzed
of
hydrosilane an
of the reaction
the analytical
samples.
Diethylmethylsiloxymethylenecyclohexane(IC) Analysis
by GLC(column
internal
standard(RRT
(8%. RRT
O-29)_
1450,
1380,
1260,
1)):
A, 130°c, Ic(71%,
.Ic: bp 130-138°C(28 1240,
1220,
1160.
n-tetradecane
RRT
0.79)
I&): 1090,
and
(Et2MeSi120
IR(neat) 1070,
as an
2924,
1010,
1680,
970.
372 910,
820,
800,
1.,36-1_6O(c
O-96 (m 6H1, (s 1~); mass X01(9$,
760 cm-':
spectrum
89(100$-
Anal, N, 11.38.
NMk(Cb14) 6R$,
5 0.08b
1.88b
ZHJ,
3H$,
2.1Ob
nt/e(rel. intensity).
0.58b 2H1,
2121331,
4H$,
5.88
X83(401,
.
Calcd
for C12H240Si:
Found:
P+,
212.1561;
P+, C,
212.1595;
67.80;
C, 67-85;
H, 11-40.
RiethylmethyLsiloxymethylenecyelopentane(fV) Analysis internal
by GLC(column
standardCRRT
800,
1415,
760 cm-';
1_58(m
4H$,
intensity$
~tw(cC14)
2,12&x
CaXcd
F&k?:
11.18.
Iv(488,
11)~
1250,
4H$,
1170,
6_04(s
X98-1409:
P+,
O-80)
mm);
3x$,
and
960,
0,60(m
lzf$_rmass
P*,
aS an CEt2MeSi120
IR(neat$
1005,
103{9$,
for C11H220Si:
n-tridecane
RRT
1120,
5 0.08(s
169(39),
198(30$,
&al_
120°C,
IV; bp 98-300°c(15
(8% RR!i?0.46;. X.685, 1460,
A,
2950, 950,
4H$,
spectrum
2875,
840-820, 0.96(m
6R$,
xtfe(rel.
89(100$198.X438:
C, 66-35:
C, 66.59:
H,
X, -iO.94_
DiethyLmethyJ_siloxymethyhylenecycXoheptane(V$ Analysis
by GLCCcoluxnn
internal_ standardfm V; bp
(9%)-
0.08&z
3H),
intensity)
IL.57,
4H1,
C&&cd
Found:
P+,
197(35),
RRT
1.29)
810,
6H$,
2950,
76C cm-':
as an
(Et2MeSi$20
1660,
spectrum
lOl(ll$, P+,
and
X-40-1.7Ofc
.?_H$;mass
for Cx3H260Si: 226,X731:
fl-tetradecane
IR(neat)
870,
0.96fm
Z'iif,5,92Cs
226(13$,
Anal,
mm);
3.000. 960,
0.58cm
2,20(m
(m 2H$,
140°C,
I)$.: V(748,
155-L6S°C(50
X3.90, 13.60, X130,
A,
1450,
1260,
NMR(CC14Q) 5 SE),
i-99
m/ekel.
89(100$226.1750;
C, 68-97:
C, 68.95;
H,
a, 1X-70-
Diethylmethylsikxqmf&hylenecyclooctane(IVI) Analysis internal
by GLcicolumn
sia.nMfREzT
A=
EOW,
X33; VX[69%.
z-tetiadecane
RR!P X.963
and
as
ax%,
~Bt2MeSi~20~
-
3i3
(ll%)_ 1250,
VI;
bp
1235,
126-13S°C(25
1200,
cm -1: NMR(CC14) l-36-1_72(c
m/e
lOl(18).
89(100)_
Anal.
Analysis an
internal
not of
and
VII
3H).
i_98(m
intensity)
1060,
240
240.1914;
structure
A,
the
it is not
1.521,
1010.
2950,
960,
2900,
880,
- (s 3H), 0_60(m
820,
1680,
1460,
0_88-1_20(m
4H),
1.86-2_12(c
2.8O(c
1H).
5.88(s
mass
Spectrum
11.57,
Calcd
Found:
P+,
compound
211(S).
226-1731;
GLC)
0.08
.
2.60-
(rd.
lOl(ll),
89(lOO)-
P +, 226.1751:
C, 68-59:
mm);
with
2H),
m/e
197(U),
for C13H260Si:
is
1100,
6H)overlapped
6H),
Anal.
as
(Et2MeSij20
N&!R(CC14) &
1_20-1_86(c
226(11).
C, 68.95;
H, 11.75.
2-Diethylmethylsilo-~ymethylenenorbornene(Vm) Analysis
by GLC(column
an internal
standsrd
(Et2xeSi)20
(7%).
JAI;
2940,
1690,
1250,
810,
2860,
760 cm-l;
A,
150°C,
(RRT 1)); Vm(45%,
NMR(CC14)
bp
130-140°c(10
1160, a
1140,
0.08(s
H,
1.641,
1150,
3H),
intensity)
C, 69-92:
120-12S°C(17
0_96(s
1H);
mass
2-diethylmethyl-
1260,
770 cm-';
770
121(21),
of an 1-l mixture(by
VII ; bp
800,
1H);
n-tridecane
and
with
800,
H, 11.64.
unidentified
consistent
1480,
6H),
5-94k
VII (22%. RRT
siloxyethenyl-l-cyclohexane. IR(neat)
1660, 860,
211(33),
(131,
13O"C,
RRT
of
960,
2H).
C, 69.88;
spectrum
NMR
1000,
•t P , 240_1908;
1));
compoundi5%,
2920,
0.58(m'4H),.0.97(m
for C14H280Si:
P*,
but
IR(neat)
2Ii). 2.24(m
standard(RRT
The
clear,
5 O-08&
by.GLC(column
unidentified (15%)*
1090,
Calcd
Found:
11.73.
1160,
10H).
spectrum
mm):
n-tetradecane RRT mm);
1100,
3H).
l-71)
and
IR(neat)
1000,
0.57(m
as
850,
4R),
H,
:,<
0_90(m
6H).
1_12-1_32(c
4~1,
1_86(m
lH),
2_04(m
2_31(m
In addition,
small
spectnxn
may
1H).
lH),
absorptions
The product
observed. mess
la),
1.47(m
1H).
1R).
and
two
(rel, intensity)
m/e
2-55(m
at 3-06
contain
1.61(m
6,02(m
S-79 were
stereo
224(39).
lh);
also
iSOmerS-
195(100),
101
(441, 89(39)_ Calcd
Anal, C, 69-41:
for C13R240Si:
internal
standard(RRT
(5%, RRT
O-13)-
840,
1450,
mass
Ib;
1380.
780 cm-':
(m 3H).
H, 10.77,
Found:
H, 10.91.
imalysis by GLC(column
1680,
C, 69.57;
bp
2
6~), (rel-
RRT
o.ll(s
1.88(m
O-70)
mm);
1080.
1150,
NXR(CC~~)
m/e
Ib(57%.
82-8S°C(13
1250.
1,35-1_59(c
spectrum
1)):
ytridecarze
A. llO°C.
6H),
2H).
intensity)
and
IR(neat)
1060,
0.57(m
(EtMe2Si)2G 2910,
1000,
2.1O(m
960,
2850. 900.
2H), 0.96
2H).
198(25),
as an
5.84(s
169(22),
1H);
89(14),
75(100)Anal. 11_18.
Calcd
Found:
for C12H220Si:
P+,
198-1428;
P+,
198-1438: H,
C. 66-87:
C, 66.59;
H,
11-18.
Triethylsiloxymethylenecyclohexane(Id1 Analysis internal
by GLC(column
standard
(23%. RRT 0.44). 2895, 820,
1675,
1,74(c
6~1,
spect-
Anal. C, 69-05:
1260,
Id(74%.
1240,
NXR(CC_~~)
2H).
4
Calcd
1220,
0_70(m
2_22(m
(rel, intensity)
87(17),
135"C,
Id; bp 135-139°C(20
2.Ol(m
m/e
103(100),
(RRT 11):
1445,
740 cm-';
A,
g-pentadecane
RRT
mm); 1150,
6H),
2H).
O-77)
226(24).
(Et3Sij20
IR(neat) 1090,
l.O9(m
6.02(s
and
as an
2920,
1010,
9H).
910.
l-44-
1l-l);mass
197(41),
169tll).
75(55)for C13H260Sit
H. 11-62,
C, .68.95: El, 11.57.
Found:
375 Dimethylphenylsiloxymethylenecyclohexane(Ie) Analysis internal
standard
(18%,
RRT
2910,
2850,
1120,
970,
1680, 830.
Anal.
1430,
720,
1_86(m
2H):
231(4),
Ie(518,
Calcd
2H).
mass
168(10).
700
n-pentadecane
RRT
150-151°C(16
1590,
780,
6H).
7.44tm
(m 3H),
Ie; bp
160°C,
A,
(RRT 1));
2.19).
l-35-1_59(c
(42),
by GLC(column
1.97)
mm); 1200,
cm-l:
NMR(CC14)
spectrum
153(19),
2H),
m/e
for C15H220Si:
P+.
3050,
1150, 5 0.39(s
5.88(s
(rel.
137(78),
(PhMe2Si)20
IR(neat)
1250,
2.16(m
and
as an
lH),
6H),
7.26
intensity)
246
135(100) -
246_1439_
Found:
PC,
246-l-462_
Diphenylmethylsiloxymethylenecyclohexane(If) Analysis
by GLC(column
internal
standard
(6%, RRT
6.31).
2910, 900.
2850, 830,
A, 220°C,
(RRT 1)); If; bp
1680,
If(26%,
1430,
790,
720,
700 cm-l;
(c 6H).
1_91(m
2H).
2.25(m
(m 4H);
mass
199(63),
197(100).
Anal. C, 77-58:
Calcd
RRT
150-156°C(0.55
1590,
spectrum
E-eicosane
m/e
1250,
1.65)
mm); 1140;
NMR(CC14)
2H), (rel.
6.01(s
as an
and
o?h2MeSi)20
IR(neat); 1120.
0 0.63(s lH),
intensity)
3050,
1080,
1060,
3H),
7_34(m 308(38),
1.53
6H);7.55 215(33).
137(91)-
c,
for C20H240Si:
77-87:
H, 7_84..Found:
H. 7-68.
Trimethylsiloxymethylenecyclohexane(Ia) A solution
of cyclohexene(30
mmol)
in 20 ml of benzene
steel
autoclave.
and
CO(50
(10 mn01)
kS/cm2) was
was
autoclave
and
cooled
introduced under
vacume
charged
CO to 80 kg/cm2
(0.2
in a 100 ml
stainless
was
flushed
to -7ooc.
to the
distillation with
placed
The
and COAX
mmol)
mm)
at 25OC
N2(80
kg/cm2)
Trimethylsilane
autoclave and
with
then
by trap-to-trap the autoclave
and heated
was
at 140°C.
3'76 The GLC
retention
time
of the product
trimethylsilpxymethylenecyclohexane prepared
from
by House's
(RRl! 1));
(23
IR(neat)
2950,
900.
1.84&
840,
2H).
2.04(m
that
Of
independently
trimethylchlorosilane
2H),
n-dodecane
RRT
0.65).
1675,1445,
NMR(CC14)
5.80(s
184(44),
Calcd
Ia(48,
2850,
740 cm-l:
(rel. intensity) Anal.
and
A, 100°C,
by GLC(column
standard
1080.
was
to
[171.
internal mu);
identical
which
cyclohexanecarboxaldehyde
method
Analysis
was
1H); mass
for C10H200Si:
1210,
9H),
1150,
1.44(C
spectrum
155(21),
P*.
Ia: bp 91°C
1250,
$_ 0.14(S
169(42),
as an
m/e
75(100)
184.1282.
6H).
73(98).
Found:
P+.
184.1279.
I-(Diethylmethylsiloxymethyl)-cyclohex-l-ene(IX) T‘ne experimental procedure
except
internal and
1460,
760 cm-'; (m 4H), m/e
(156, RFT
1420,
1255,
NMR(CC14)
5
(rel. intensity;
11.38.
Calcd
Found=
A,
1160,
IX:
3H).
212(14).
0.811,
at 2OO“C.
1070,
5.50(m
183(31),
2020,
1010, 4H),
RRT
0.791,
2870,
965,
840,
800,
0.93(m
6H),
1.60
1H); mass
103(7),
, 212.1594:
C, 67.83:
as an
Ic(678,
IR(neat);
2H),
P
out
E-tetradecane
0.53(m
t
as the..general
carried
RRT
1090,
3.85(s
212.1560;
was
100°C,
0.29).
for C12H240Si:
P+,
the same
1X(17%,
O.Ol(s
4H),
was
reaction
(RRT 1));
1.80-2.12(c
Anal.
the
GLC(column
standard
(Et2MeSi)20
1675,
that
by
Analysis
procedure
spectrum
89(100). C. 67.85:
H,
H. 11_.44.
Acknowledgments This in-Aid
was
generously
for Scientific
of Japan. supply
work
We thank
Research Shin-Etsu
of organosilanes.
supported
in part
by the Ministry Industry
Co.,
by a Grantof Education
Ltd.
for the
-
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