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

-

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