methanol

Journal

of Fkmrine

Chemistr),,

31 (1986)

337L240

237

Received: November 29,1985.accepted: January7. 1986

PRELIMINARY

Reaction

NOTE

of Hexafluoroisobutene

with

Hydrogen

Peroxide/Ferrous

Sulfate/Methanol

SUSUMU

MISAKI

Chemical 12-39,

Division,

Umeda

and KAZUHISA

Chemical

Daikin

I-chome,

Industries,

Kita-ku,

Osaka

Ltd. 530

(Japan)

TAKII

Division,

4-5, Kawahara-cho,

Okamura

Oil Mill,

Kashiwara-shi,

Ltd.

Osaka

582

(Japan)

SUMMARY

Hexafluoroisobutene hexanone

peroxide

hydrogen

peroxide)

methyl

ester

in fairly

of

in the presence

of ferrous

cycloand

ion to give the acid

good yield.

already

reactions

with

(formed in situ from cyclohexanone

Hexafluoroisobutene

process

in methanol

8-trifluoromethyl-9,9,9-trifluorononanoic

of fluoropolymers We have

was reacted

reported

of intermediates

of making

0022-1139/86/$3.50

is a useful

monomer

a synthetic

route

for the synthesis

[I].

which

were

[2] and some

obtained

during

the

the monomer [3]. 0 Elsevier Sequoia/Printed

in The Netherlands

230 In order reacted

to find further

it in methanol

presence

of ferrous

with

ion.

20-dioate

reported

peroxide

peroxide)

in

in situ

ferrous

ion in

8,12-eicosadiene-1,

being

and CF2=CFC1

peroxide

methyl

esters

in the same

of monobasic

151.

The reaction

between

peroxide,

and gave methyl

hexafluoroisobutene,

methanol

and ferrous

cyclohexanone,

ion proceeded

smoothly

8-trifluoromethyl-9,9,9-trifluorononanoate

as a

product.

Small

amounts

(n=2,3),

of a mixture

of H[C(CF3) 2CH2]n(CH2)5COOCH3,

(CF3)2C=CH[C(CF3)2CH21n(CH2~5COOCH3,

CH300C(CH2)5-[C(CF3)2CH21n-(CH2)5COOCH3, by MS spectra

suggested

by MS spectra previously

+

H202

&>

[

(n=1,2,3)

(n=1,2) were

and

detected

as the by-products.

the fact that CH3(CH2)4COOCH3

detected

and CH300C(CH2)10COOCH3

the main

by M. S. Kharasch

+ CH3OH

ffj$;j

and VPC,

--+'

(CF3)2C=CH2>

3

CH30H -

time

[41.

cyclohexanone

products

(formed

with

such as CF3CF=CF2

to react with

the major

hydrogen

From

in the

8-trifluoromethyl-

for the first

to give dimethyl

fluoromonomers

found

manner,

and hydrogen

of butadiene

has been

Some

main

was obtained

of cyclohexanone

from cyclohexanone the presence

acids

peroxide

methyl

we

good yield.

The reaction

were

of the monomer,

cyclohexanone

The product

9,9,9-trifluorononanoate fairly

applications

CH3pC~2CHcCF312

proceeded

et al. [4].

[ CH30000H)

(

reaction

+ H20

CH3acCH2k(CF3j2

]

were as

2.39

Methyl_8-trifluoromethyl-9,9,9-trifluorononanoate _____ To a solution was added

120 g

of 3.0 g of cont.

(1.22 mole)

120 g of 35 % hydrogen this

temperature

with

a mixture

peroxide

stirring

of 340 g

600 ml of methanol,

in 600 ml of methanol

of cyclohexanone,

peroxide

and stirred

The cyclohexanone dropwise

H2S04

was added

at O-5 "C.

to the mixture

at

for sixty minutes.

solution

thus prepared

at -10 'C over

a period

(1.83 mole)

of ferrous

and 300 g

(1.83 mole)

was added

of two hours

sulfate

to

heptahydrate,

of hexafluoroiso-

butene. After

completion

another

of the addition,

two hours

temperature.

Methanol

layer was washed sulfate.

BP.

with

The crude

fractionally

stirring

and the mixture

was distilled acid, water

product,

distilled

was continued

was warmed

off and the upper

and dried

102 "C/15 mm Hg, 96.3 g

organic

over magnesium

a light yellow

to give

for

up to room

oil

(410 g) was

(CF3),CH(CH2)6COOCH3,

(26.8 %, yield

based

on cyclohexa-

none). OH+ MS, m/e

= 294

(COOCH,), 2.30

(M+-0CH3),

(CF2), 'H NMR

50

3.65(3H,

74

(CDC13)

(2H, t, J = 7.3 Hz, CH3CO),

Hz, CH), ppm

(M+), 264

6 1.2-2.0

2.86

"F

s, 0CH3),

(CH2gOCH3),

NMR

ppm

(lH,e -sep,

69

(CF3), 59

(IOH, m, CH2), J = 6.0, 8.4

(CDC13, ext TFA)

6 100.2

(6F, d, J = 8.9 Hz, CF2). To extend

attempted with

the procedure

the reaction

C8F17CH=CH2

but the yield

C8F17CH2(CH2)6COOCH3 (CH2-sOCH3)]

to other

was

fluoroolefins,

by the previously

described

of the expected

[ MS, m/e = 576

(M+), 545

we procedure

ester (M+-0CH3),

74

low.

OH+

We would

like to express

of the Research their

help.

Department

We would

(Osaka University)

also

our appreciation

and the Technical like to thank

for his advice.

to the members Department

Professor

for

N. Sonoda

240 1

N. Vanderkooi,

2

S. Misaki

Jr. and H. J. Huthwaite,

US Pat.,

3 894 09

(1975). and S. Takamatsu,

J. Fluorine

Chem.,

-24

(1984)

531. 3

S. Misaki,

4

M. S. Kharasch

J. Fluorine

5

N. Sonoda,

Chem., -29 (1985) 471. and W. Nudenberg, J. Org. Chem.,

-19 (1954)

1921.

(1983).

S. Murai

and K. Hiroishi,

Jap.

Pat.

58-22130