The Reactions of 1,2-Dihalofluorocycloalkenes with Trivalent Phosphorus

(1)

iDAEHAN HWAHAK HWOEJEE

(Journal of the Koren Chemical Society) Vol. 17, No. 1, 1973

-Printed in Republic of Korea

Note

1, 2・Dihaloaiiorocycloalkenes

와 삼가 인과의 반응

박 달 조* ・

Otto K. Furuta

미국 콜로라대학교 화학과

(1973. 1. 18

접수)

The Reactions of 1, 2-Dihalofluorocycloalkenes with Trivalent Phosphorus

Joseph D. Park*and Otto K. Furuta

Department of Chemistry, University, of Colorado, Boulder, Colorado^ U*S. A.

(Received Jan. 18, 1973)

The

reactions

of nucleophiles

with

halocyclo-

^Ikenes

have been

studied

in

detail.

Discussions

of the mechanism

and

the

characterization of

the products

from

the

reactions with alkoxide-

ion

and

Grignard

reagents have

been

reported.

Studies

of nucleophilic reactions of

phosphorus

compounds with

halocycloalkenes, however,

have

not

been studies to

any

extent.

Nucleophilic

attack

of trialkyl

phosphites

on alkyl halides

has been known

for

many

years and

appears to be

one

of

the most

useful met

hods of

preparing phosphonic acids and their derivatives.

The

reaction

involves a nucleophi

lic substitution on

the

alkyl

halide

by the

phosphorus atom. Subsequent elimination o£

alkyl halide leads

to an alkyl-dialkyl phospho-

nate

ester:

RX+

00)

3PTRP

(OR')

3*

tRP0(0R〃)2+R'X (1)

'The

success

of

the

reactions

depends

on

the reactivity

of the

alkyl

halide (RX)

toward nucleophilic substitution

and on the

volatility

Present Address: The Korea Advanced Institute of Science, Seoul, Korea.

—

—6

0 t

0 0

p—jpP(OCH； CH3) 2 '一^P(OCH2CH3)2

^X^P(OCH2CH3)2

*一^P(OCH2CH3)a

（。마lch$）

L、/七＞（och：；（가用）

1

0 0 0

I II III

0 I

9 ,CH3 P(0CH )2 E「p （。。거2。出"

*^-ch；ch（ch3）2

Y

〔或、r

zCH3

3。앳压 ” IV

of

the alkyl

halide eliminated(R'X).

We wish

to

report

the first

successful synth

esisofanalogous phosphonate

esters

with

halog

enated

cycloalkenes:

The synthesis

is

accomplished by refhixin잉

the

Table 1. Yield Data

Starting Olefin Product %Yield (a)

□L： I 29.0

立：

¹¹ ^31.9

III

也

^XV ^ai.4

Cti2CH(CH3)2

V 41.9

(a) Yield based oa trlalkyl phosphite

7 —

(2)

68 박 달

trialkyl phosphite

with

an excess

of

the appro

priate olefin

and a trace

of toluene.

The toluene

is

used

as an in temal

standard as the progress

of

the reaction

is followed

by g.

1.

c.

The

reaction mixture isrefluxed until the trialkyl phosphite

is

consumed. The yeild data

and spectra

data are

summarized in Tables

1 and

2.

5 (a)

Yield

based

on

trialkyl phosphite The mass

spectra

of

the

diphosophpnates show

three

modes of

fragmentation. The

two

조

major

modes are by

loss of an

alkoxy radical

and

by

loss of

the

diethylphosphonate

radical;

the minor

mode is

by

loss

of

the

ethenyl radical

with the

transfer

of

two

hyd

호

ogens.

The

latter mode has

been previously

reported for

the

hydrocarbon

analogues4.

The

nuclear magnetic resonance

spectra

for the

diethyl phosphonate group consists

of

eleven lines:

an

unsymmetrical

triplet

for

the —

CHs；

and

an

eight

line

multiplet for

the

methylene

t further fragmentation.

further fragmentation

Methylene-poorly resolve

Table 2. Nuclear Magnetic Resenance and Mass Spectra

Compound Mult. J. vic (cps) Group Chem. Shift Molec. Ion

I £(u) H-H-7.0

- ch 3

8.62

m H—H=7.0

- ch 8

5.78 398

P—OCH2—8.6

II $(u) H-H=7.1

- ch 3

8.63

m H-H=7.l

- ch 2

5.73 448

P—0CHa=9.0

III *(u) H-H-7.1

- ch 3

8.62

m —― ——

- ch 2

5.73 498

Journal of the Korean Chemical Society

IV m — — -CHa

一

M —, — -CH 5.10 504

poorly resolved spectrum

V d(u) H—H=6.0

- ch 3

8.96

£(u) H-H=7.1 -CHa 8. 61

m — — -CH 7.91 318

m — —

- ch 2

7.46

m HH—H=7.1

- ch 2

5.83

P—OCH2=9.0

(3)

1,2・Dih이ofhiorocycloalkenes와 삼기의 인과의 반응 69

U Q

I

一-

n*(°R)2 L*P(

。)

(OR) 2

F + (RO)3P：-*

f

e —*

1一一

*ci

1一1 S( or )3

Cl

［回。)(財-一回編)

2 + RX (3)

L1

一

^(0R)3 J

J"2群

OR)z

protons.

The

products

can

be

rationalized by assuming

carbanion

formation,

as in

the

case with the

alkoxide ion

and

the Grignard

reagents:

III 幻 + (RO)

3

Continued

work

in the study of nucleophilic phosphorous reactions is in progress.

Reactions

with

various

halogens in

the vinylic

positions and with

other

phosophorous

nucleophiles

have been

completed,

and a

more detailed discussion

of

reaction rates and

mechanisms

will

be disc

ussed

in

a

later

publication.

Acknowledyements

The authors wish

to express

their

gratitude to

Mr. Scott

Williams,

who helped

in

the

synthesis

of some of

the compounds.

References

1. a) R. J. McMurtry, Ph. D. Thesis, University of Colorado, 1966.

b) T. S. Croft, Ph. D. Thesis, University of Col

orado, 1966.

2. a) A. Michaelis and R. Kaehne, Ber., 31, 1048 (1898).

b) A. Arbuzov., J. Russ. Phys. Chem. Soc., 42, 395 (1940).

3. 15 ft. 25% Carbowax 20M/Chromoscorb P60/80.

4. J. L. Occolowitz and J. M. Swan, Aust. J.

Chem., 19, 1187 (1966).

Vol. 17, No. 1, 1973

The Reactions of 1,2-Dihalofluorocycloalkenes with Trivalent Phosphorus

와 삼가 인과의 반응

박 달 조* ・

미국 콜로라대학교 화학과

접수)

The

of nucleophiles

halocyclo-

^Ikenes

studied

detail.

of the mechanism

the

the products

the

ion

Grignard

been

Studies

phosphorus

halocycloalkenes, however,

not

any

Nucleophilic

of trialkyl

on alkyl halides

for

years and

one

the most

­

preparing phosphonic acids and their derivatives.

reaction

­ lic substitution on

alkyl

by the

alkyl halide leads

nate

00)

(OR')

success

the

depends

the reactivity

alkyl

toward nucleophilic substitution

volatility

the alkyl

We wish

report

successful synth­

esters

halog­

enated

The synthesis

accomplished by refhixin잉

立：

也

trialkyl phosphite

an excess

the appro­

and a trace

The toluene

used

standard as the progress

the reaction

by g.

c.

reaction mixture isrefluxed until the trialkyl phosphite

consumed. The yeild data

data are

1 and

Yield

on

spectra

the

three

fragmentation. The

modes are by

alkoxy radical

lic substitution on

successful synth

halog

the appro

［回。)(財-一回編)

ussed