The copper(I) chloride-ethanolamine catalyzed addition of polyfluorinated alkanes to olefins

Tetrahedron Letters No.42, Printed in Great Britain.

pp. 5163-5168, 1966. Pergamen Press Ltd.

THE COPPER(I) CHLORIDE-ETHANOLAMINE CATALYZED ADDITICCJ Oi= POLYPLUORINATED ALKANES TO OLEP INS Donald J. Burton and Lawrence J. Department of Chemistry, University Iowa City, Iowa (Received The peroxide

addition or

radical

in

initiation

isolation

more

difficult;

employed

to

be

costly more

since

the

difficult

reaction

to

using

(2,3).

This

to

minimize

formation

chloride

these

and

and

copper

synthetic

the

competing

similar

alkanes reactions

can to

are

more (c)

ins.

5163

be

and

and

has

of

the

in Table

chloro-

been

been

peroxide

The results

summarized

can

necessary.

has

using in

alkane

vigorous

processes

catalysis

and makes

this

often

route

with

(a)

expensive

catalysis

be employed

olef

the -

are

associated

that

of

two methods

tetrachloride

chloride

elegant

eliminate

found

carbon

by

subject

adduct of

obtain;

apparatus

of

ethanolamine

luor inated addition

special

1:l

formation the

to

the these

excess

generally

olefins

disadvantages: the

a large

polymerization

Ke have

ysis.

polyf

or

of

telomer

addition

been

following

material

and

olefins

reported

is

to

However,

yield

minimize

conditions the

the

(b)

alkane

has

( 1).

the

starting

Recently, form

years have

decreases

alkanes

initiation

recent

telomerization

must

25 July 1966)

polyfluorinated

photochemical

much research of

of

Kehoe of Iowa

shown

telomer catal-

copper(I) addition of 1.

some

of of

CF2ClCFC12 CF3CClBr2 CF3CC13

l-octene

1-octene

1-octene

CF2BrCFClBr

CF3CC1Br2

2-octene

Ally1 chloride

Adduct

CF3CClBrCH2CHBrCH2C1

+ CH3CHBrCH(CFClCF2Br)(CH2)SCH3

CH3CH(CFClCF2Br)CH8r(CH2)5CH3

CF2BrCFClCH2C!H13rCH20CH2CH3

CF3CF2CF2CH2CHI(M2)SM3

CF3CSr2CH2CABr(CH2)SCK3

CF3cc12CH2CHc1(CH2)5CH3

CF3CC1BrCH2CHBr(CH2)SCH3

CF2c1CFc1CH2CHc1(CH2)SCH3

CF2BrCFClCH2CHRr(CH2)SCH3

I

47

86c

78

57b

74

83

98

62

94

77

68

% Yield a

-

-

-

-

-

-

--

-

._

(a) The yield was determined by GLC on a Silicone Rubber Column. All reactions were carried out using a mole ratio of alkane/olefin of 2:l except where noted. (b) The ratio of halide to olefin was 1:l. In addition to the 1:l adduct, a 42% yield of CF3CF2CF2CH=CH(CH2)gCH3 was also found. (c) A mixture of both isomers.

CF2BrCFClRr

CF3CF2CR21

Ethyl ally1 ether

1-octene

CF3CBr3

CF2BrCETlBr

l-octene

1-octene

CF2BrCF2Br

CFZB=2

Halide

1-octene

1-octene

Olefin

TABLE

i

P

%

U

5165

No.42

A typical g.

(0.2

procedure

mole)

of

(CF2BrCFClBr ), mole)

is as follows:

11.2 g.

(0.1

and 100 ml.

with

for

layer

rubber

the pure 1:l for

adduct

of 3.0

g.

After

cooling

was diluted

88”

with ether

of

and the

the adduct

b.p.

of

on a silicone

27.0

mm.), nr

CF2BrCFC1cX2CHBr(CH2)$H3 (5):

mole)

(0.001

were ref luxed

yielded

(0.4

g.

to room tempera-

GLC analysis

fractionation

0.1

(0.05

alcohol

a 94x yield

b.p.

1-octene,

t-butyl

was separated.

Subsequent

.

of

mixture

column indicated

1-octene

(4),

24 hours.

the reaction

organic

mole)

chloride

ethanolamine,

ture,

of 55.3

1,2-dlbromo-I-chloro-1,2,2-trifluoroethane

of copper

stirring

A mixture

based on g.

(7C%) of

1.4612.

84” (0.3

Repor ted mm.),

n:4

1.4612. Structural elemental spectra

assignments

analysis,

of

infrared

and on chemical

dehydrohalogenation

the 1:l

adducts

and proton

evidence.

are based on

magnetic

The latter

and dehalogenatlon

of

resonance

Includes

the adducts

both where

appropriate. Although

I-octene

initial

survey

olefins

have been used successfully.

olef ins,

Also,

have given

Telomer formation reactions.

the scope

such as E-octene

successfully. ether

of

was used as a model olefln of

this

reaction,

good yields

olefins of

other

In addition,

and cyclohexene,

reactive

for

was not of consequence

terminal internal

have been employed

such as ethyl

the 1:l

the

addition

ally1

adduct.

in any of

these

5166

NO.12

The data

in Table

I also

method can be used successfully

with

reactive

listed

chlorine,

bromine,

While most of undergo

this

worthy

of note.

chloroethane

contrast

conditions

alkanes

the catalyst

gave only

the 1:l

adduct

with

The reactant

for

to 1-octene

starting

under these

conditions.

simplicity carried

olefin

Although ratio

results

apparatus

required.

Also,

using

is

large

since

that

excesses

offer

pressure

the disappearance by sampling

the reaction

Another

the expensive

halogen

of halogen

compound olefin,

we have found

these

reactants.

the

important

can be carried

out successfully

of

of

by GLC,

can be carried

ratio

addition

extreme

the reaction

with a 2:1

reaction

can be generally

to a minimum.

of

to

gave only unchanged

and no special

followed

times can be reduced

in some cases

without

1:l

glass

can be conveniently

reaction point

Is

in all

and gave no

must be stable

additions

The reactions

of procedure. out

apparatus

catalyzed

(CF2BrCF2Br)

the attempted

luorobutane

halide

In

the addition

of 2,3-dibromooctaf

These copper

I-octene.

1-octene

alkane

Also,

out successfully.

materials

are

tetrachloroethylene

luoroethane

and to the ethanolamine

to be carried

some others

1,2-dibromo-1,1,2,2-tetra-

1,2-dibromo-1,1,2,2-tetraf of

a

we have examined

and no 1:1 adduct with

luoroethylene.

this

compounds containing

successfully,

For example,

gave a 77% yield tetraf

reaction

(CCl2BrCCl2Br)

under these

that

or iodine.

the halogenated

addition

illustrates

out reactant. using

best

Even with

the

a

5167

NO.12

1:l

ratio,

however,

no signif

icant

tclomer

formation

has

been

observed. This

simple

preparing studies

polyfluorinated are

reaction igate

catalysis

this

other

This

Acknowledgment:

from

the

Public

with

Health

the

alkanes

scope

for

of this

and also

polyfluorinated

to invest-

olefins.

work was supported Service

much promise

and additional

to investigate

fluorinated

reaction

offers

hydrocarbons,

in progress

with

technique

in part

by a grant

(GM 11809-03).

References

(1)

For an extensive Free

Radicals

1957,

Chapter

G. Sosnovsky, Organic 1964,

review b

Solution,

this

work,

John Wiley

cf.

C. Walling,

6 Sons,

New York,

6. Free Radical --

Chemistry, Chapter

of

Reactions

The Macmillian

&

Preparative

Company, New York,

2.

(2)

M. Asscher

and D. Vofs i,

J. w.

*.,

1887 ( 1963).

(3)

M. Asscher

and D. Vof si,

J. M.

E.,

3921

(4)

For the

SE*,

preparation

2 1 (1946). =g

of Copper(I)

Chloride,

cf.

( 1963).

a.

5168

The CuCl is slowly yield this

a green partially

was found

oxidized,

compound CuC12.j oxidized

mixture

to be an effective

by moist cU(OH)z. of

catalyst

air,

to

However,

Cu(I) for

and Cu(II), these

additions. (5)

P. Tarrant

( 1954).

and E. Gilman,

J. &.

&.

a.,

j’6, -

‘54%