New Synthesis of the Acid Moiety of Pyrethroids

12 New Synthesis of the Acid Moiety of Pyrethroids KIYOSI KONDO, KIYOHIDE MATSUI, and AKIRA NEGISHI

Downloaded by CORNELL UNIV on June 18, 2017 | http://pubs.acs.org Publication Date: June 1, 1977 | doi: 10.1021/bk-1977-0042.ch012

Sagami Chemical Research Center, 4-4-1 Nishi-Ohnuma, Sagamihara, Kanagawa 229 Japan

Since the discovery of permethrin (l) and its bromo analogue (2), interest in the structural modifi cation of natural pyrethroids has been renewed owing to their potential use as agricultural pesticides as well as household insecticides. The reaction of ethyl diazoacetate with 1,1-dichloro-4-methyl-1,3-pentadiene was originally used by Farkas (3) in the synthesis of the acid moiety of permethrin. Most of the acid moi eties, however, were usually prepared by the ozonolysis of the parent chrysanthemate followed by conden sation of the resulting 2-formyl-3,3-dimethylcyclopropanecarboxylate (caronaldehyde) with appropriate Wittig reagents (4,5) .

We have developed a new and generally applicable meth od for the preparation of these potentially useful synthetic pyrethroids. The method is based on the reaction between a l l y l i c alcohol and orthoester to produce γ-unsaturated carboxylate, followed by the addition of carbon tetrahalide to the double bond, or a l l y l i c bromination with N-bromosuccinimide. The dehydrolhalogenation of the resulting halides afforded the desired cyclopropanecarboxylates. Synthesis of the Dihalovinyl Analogues of Chrysanthe mate The condensation of 3-methyl-2-butenol

(I) with

128 Elliott; Synthetic Pyrethroids ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

12.

KONDO

ET

Synthesis of the

AL.

t r i e t h y l

o r t h o a c e t a t e

c a t a l y s t

was

method

( l i a )

p e r f o r m e d

d e s c r i b e d

by

Acid

at

in

Moiety the

presence

li+0-l60°

Johnson

(6)

to

give

3 , 3 - d i m e t h y l - ^ - p e n t e n o a t e

( i l i a )

s i m i l a r l y

c o n d e n s a t i o n

of

of

III

I

can

w i t h

of

a c c o r d i n g

t u t e d

analogue

129

the

e t h y l

(7.).

The be

a p p r o p r i a t e

a c i d

to

α - s u b s t i

p r e p a r e d

by

the

o r t h o c a r b o x y l a t e s

(8,9). 0

Λ Α

+ R

C H

1

2

c a t .

C ( O E t )

r

OH

R


II a:

R

b;

R =Me

1

III

=H

1

:

R- H 1

b:

1

R

-Me

C X ^ / c a t .

X

base

A R

a:

R ^ H ,

b:

R

c:

R =Me,

The

e f f e c t

the

y i e l d

Table R

1

1 =

X=C1

of

X=C1

the III

v a r i a t i o n is

of

of

p h e n o l

1:1.05 1:2

p h e n o l

H3PO4

Me

1:3 1:2 1:2 1:2 1:2 1:2

E t * *

1:1.5

Η Η Η

*

The based

**

R ^ H , R =H,

X = B r ,

c:

R*=H,

X=X

d:

R

H

3

1

=

in

X=X =Cl f

f

M e ,

r e a c t i o n

X=C1

=Br

T

X=X =Cl f

c o n d i t i o n

Table

Time

P 0 * a c i d

i - b u t y r i c

a c i d

I.

Y i e l d

of

amount

of

25 25 6 k

76 60 81

27

III

65 70

93

23

p h e n o l

23 23 2k

69 51 70

p h e n o l

25

57

H g ( 0 A c )

2

h y d r o q u i n o n e

T r i m e t h y l

X

^ - P e n t e n o a t e s

o x a l i c

on

2

(hr)

1:2

Η

CX 1

a:

C a t a l y s t *

Η Η

X

b:

1:11

Η Η

of

summarized

P r e p a r a t i o n

m o l . r a t i o

IV

X=Br

1

of

I.

=H,

1

c a t a l y s t

was

usually-

1-5

mole

I o r t h o b u t y r a t e

was

u s e d .

Elliott; Synthetic Pyrethroids ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

%

on

130

SYNTHETIC

t u r e

When

t h e

o f

a n d l i a , t h e r e

I

r e a c t i o n

3 - m e t h y l - 2 - b u t e n y l p r o d u c t the

in

a c e t a t e can,

must

t h e

t h e

a d d i t i o n

o f


T h u s ,

h e a t i n g

p e r o x i d e 80°

hexanoate When

in

(AIBN),

e t h y l

89%

o f

t h e

c a r b o n

b . p .

a d d i t i o n

b . p .

u s e d .

Some

Table

I I .

R

CX 4

o r

o f

t o

e i t h e r by

I l i a

h-

t h e in

a n d

t h e

p r e s

b e n z o y l -

f o r

m m . ,

20

h r s

at

in

86%

y i e l d .

b r o m o t r i c h l o r -

y i e l d .

as

t o

examples a r e

o f

Other

CX4

t o

(l^viS^iJi) > f o r

t h e

c a n a l s o t h e in

be

r e s u l t s

Table

w i t h

I I .

U-Pentenoates Temp.

C a t a l y s t

l i g h t

I V c ,

i n i t i a t o r s ,

o l e f i n s ,

c o l l e c t e d

c a r b o n

v i s i b l e

c a t a l y s t s

i n c l u d i n g

o b t a i n e d o f

analogue

complexes

effective

analogues

w i t h

t e t r a b r o m o

p o l y h a l o a l k a n e s t y p i c a l

m m . , was a d d i t i o n

i r r a d i a t i o n

60%

in

r a d i c a l

m e t a l - a m i n e

A d d i t i o n

Time

Y i e l d IV

H

C C U

BPO

H

CCI 4

F e C l

H

e c u

C u ( O A c )

H

e c u

C u

H

C B r C U

AIBN

H

C B r C l

3

BPO

H

C B r C l

3

H

CBr 4

AIBN

H

C B r

hV

Me

e c u

Me

C B r C l

Me

e c u

F e C l

3

6 H

2

0 - B u N H

E t *

CCI 4

F e C l

3

6 H

2

0 - B u N H

4

2

3

6 H

2

2

0 - B u N H - B u N H

0 - B u N H

F e C l

3

6 H

2

2

80

20

86

120

20

87

90

20

87

90

20

85

100

10

89

80

20

87

120

15

52

5

45

10

60

2

2

0 - B u N H

2

120^130 r.

t .

20

70

100

10

81

2

120

10

49

2

120

10

80

BPO 3

t o

i r r a d i a t i o n .

w i t h

1 0 2 - 1 0 5 ° / 0 . 1 by

w e l l - k n o w n

α - s u b s t i t u t e d

1

I l i a

m m . ,

o f

r a t e .

a z o b i s i s o b u t y r o n i t r i l e

S i m i l a r l y ,

t r a n s i t i o n

a r e

seems

a n d r e a c t i o n

t e t r a h a l i d e

o f

c o r r e s p o n d i n g

which

o r t h o -

o r t h o e s t e r d i s t i l l a t i o n .

t r e a t e d

p r o d u c e d as

a t t a i n

o f

a c i d

t e t r a c h l o r i d e

t o

lkk°/0.2

t o

amount

o f

b y

f r a c t i o n a l

(10)

t e t r a b r o m i d e

such

o r d e r

as

p h o s p h o r i c

1 0 T - 1 0 8 ° / 0 . 3

was

p r e s e n c e

( i V b ) ,

b . p .

m i x

3 , 3 - d i m e t h y l - 4 - b r o m o - 6 , 6 , 6 - t r i c h l o r o -

y i e l d . t h e

molar f o r m a t i o n

3 , 3 - d i m e t h y l - U , 6 , 6 , 6 - t e t r a c h l o r o -

I l i a

t h e

1:1

t h e

excess

a c h i e v e d

s o l u t i o n c a r b o n

t h e

y i e l d

e a s i l y

a

in

e s t e r

hexanoate

o f

e t h y l

methane

in

o f

( i V a ) ,

t h e

o f by

i n i t i a t o r

(BPO)

a f f o r d e d

Most

in

excess

examined,

was

r a d i c a l

an

r e c o v e r e d

view

I I I

from

o b s e r v e d

T h u s ,

I I I ,

u s e d .

be in

pentenoate ence

y i e l d . o f

c a t a l y s t s

b e s t

The

20$

be

s t a r t e d

was

3 , 3 - d i m e t h y l - 4 - p e n t e n o a t e

y i e l d

however,

Among be

c a .

maximum

was

PYRETHROIDS

130^140

BPO

Me-es t e r


o f

12.

KONDO

Synthesis of the Acid

E TAL.

Treatment l e n t s t i o n

o f

base

t h e

s i m u l t a n e o u s l y

c a r b o x y l a t e e s t e r

V

u s e d .

T a b l e


o f

V .

w i t h

a f f o r d

examples

on

R e a c t i o n

h a l i d e

base

shown

t h e

in

t-BuOK

THF

IVa

t-BuOK

THF

IVa

t-BuONa

THF

IVa

NaOEt

EtOH

r .

k 3

t .

3. 5 3

5°

2

r . t .

80° IVa

KOEt

IVa

NaNH

IVc

NaOEt

EtOH

IVd

NaH

DME

The

under

EtOH

t h e

sequence

was

1. 5 5- 5 18 20

80°

o f

w i t h

c o n d i t i o n

The

c h l o r i d e

t o

BPO c a t a l y z e d t h e

above

e s t e r

70

Va

50/50

73

Va

50/50

92

Va

3k/66

9h

Va

26/74

96

Va

50/50 20/80

9k

Vb

as

a

v i s c o u s

t o

has

c h r o m a t o g r a p h y . two

molar

THF

t o

give

s p e c t r u m c i s

The

e s t e r

e q u i v a l e n t s

o f

produce

p e r m e t h r i n

i n d i c a t e s

a n d t r a n s

t h a t

was

V I I

V I I I it

in

been

was 75$

1 5 5 - 1 5 8 ° /

c a r b o n

t e t r a

3-phenoxybenzyl

p u r i f i e d then

y i e l d . o f

( V I I ) by

1:1

in

in

82$

column

t r e a t e d

t - b u t o x i d e

c o n s i s t s

T h u s , a l c o h o l

3 - p h e n o x y

b . p .

o f

a f f o r d e d

sodium

now

p e r m e t h r i n .

( V I ) ,

a d d i t i o n

o i l , w h i c h

79 55

-

Vc

o f

V η y i e l d ! t of-\

^5/5.5

3 , 3 - d i m e t h y l - 4 , 6 , 6 , 6 - t e t r a c h l o r o h e x a n o a t e y i e l d

V

3-phenoxybenzyl

3 - , 3 - d i m e t h y l - U - p e n t e n o a t e

mm.

I I I .

Va

r e a c t i o n s

p r e p a r a t i o n

t r e a t e d

e s t e r - e x c h a n g e

b e n z y l

80° 22° r . t .

d i r e c t

I l i a

1. 5 2

r . t .

THF-EtOH

2

above

t o

e s t e r

r e s u l t i n g

- P r o d u c t c i s / t r a n s

time

60° 60°

a p p l i e d

e q u i v a

c o n d i t i o n s

T a b l e

C o n d i t i o n s

s o l v e n t

IVb

0.3

o f

r e a c t i o n

r

i n g

molar

d e h y d r o h a l o g e n a -

D i h a l o v i n y l c y c l o p r o p a n e c a r b o x y l a t e s

S t a r t

the

two

a n d

r a t i o

t h e

a r e

131

d i h a l o v i n y l c y c l o p r o p a n e -

c i s i t r a n s

depending

T y p i c a l

IV

c y c l i z a t i o n

t o

The

v a r i e d

I I I .

e s t e r

i n d u c e d

Moiety

w i t h anhydrous

The nmr m i x t u r e

i s o m e r s .


o f


132

SYNTHETIC

PYRETHROIDS

V I I I

At

t h e

was

m i d d l e

o b s e r v e d

m e d i a t e s ,

As

t h e

stage t h e

I X ,

X ,

r e a c t i o n

d i s a p p e a r , excess

in

t h e

r e a c t i o n o f

a l l

from

t h r e e

t h e s e

c o n v e r t e d

t h e

system

d e h y d r o h a l o g e n a t i o n

o f

V

t o

t h e

f i n a l

by

t r e a t m e n t

The w i t h

l i n k a g e

t h e

tons

c o u p l i n g

in

t h e

nmr

t e t r a c h l o r i d e room

o f

tends t o

t h e

i n t e r m e d i a t e

p i p e r i d i n e

olefinic on

stage o f

t h e

V ,

t h e r e i n t e r -

in

IX

t o

i n d u c e

a f f o r d

in

IX

c a n

was

s p e c t r u m .

2 , 2 - d i m e t h y l - 3 - ( 2 ( X I I ) ,

s e l e c t i v e l y

a t

80°

f o r

a s s i g n e d

(15

Hz)

The

I V a w i t h

a f f o r d e d

o f

f u r t h e r e s p e c i a l l y

r e a c t i o n .

benzene

c o n s t a n t

u s u a l l y

The p r e s e n c e

be

b r o m o t r i c h l o r o m e t h a n e

adduct

t e m p e r a t u r e

t o

i n t e r m e d i a t e s

V .

c h l o r o e t h y n y l ) e y e l o p r o p a n e c a r b o x y l a t e at

IV

p o s s i b l e

a n d X I .

p r o c e e d s ,

b e i n g

base

o f

f o r m a t i o n

t h e

o f

15

t o

h r s .

be

t h e

r e a c t i o n

p r e p a r e d

adduct

o f

p y r r o l i d i n e i n t e r m e d i a t e

IVb

The

t r a n s

based

olefinic

p r o -

t h e

c a r b o n

in

DMF a t

X


12.

KONDO

ET


AL.

s e l e c t i v e l y . mediate

XI

p o t a s s i u m was

used

c i s -

the

s t a r t i n g

t r a n s - X I c o u l d

w i t h d i r e c t

of

t r a n s f o r m e d

the


d i e n y l

of

to

of

the

homologues of

can

c o n -

t h e s e

i n t e r -

i n t o

V

by

b e i n g

t r e a t -

used

in

Chrysanthemate group

1 - b u t e n y l ,

i n c r e a s e s

be

was

IVb o f

V .

o f

(15)..

or

When

IVa

c o n d i t i o n

to

i n t e r -

sodium

m i x t u r e

A l l

d i m e t h y l v i n y l

a l s o

activity

sequence

IV

the

1:1

smoothly

same

1 - p r o p e n y l ,

s u b s t i t u e n t

insecticidal t h e s e

the

Homologues

M o d i f i c a t i o n c h r y s a n t h e m a t e

w h i l e

t r a n s - X I .

o f w i t h

s o l v e n t .

almost

o b t a i n e d ,

under

IV

h y d r o c a r b o n

to

c o n v e r s i o n

S y n t h e s i s

t r e a t i n g

m a t e r i a l ,

was

be

base

p r e p a r a t i o n

by

in

p r e d o m i n a n t l y

mediates ment

s e l e c t i v e

a t t a i n e d

t - b u t o x i d e as

and

v e r t e d

The was

133

Moiety

in

or

1 , 3 - b u t a -

s i g n i f i c a n t l y

The

a c i d

p r e p a r e d

by

the

m o i e t i e s

the

o f

f o l l o w i n g

r e a c t i o n s .

OH R /%J\/

+

R

1

C H

C ( O R

2

2

)

Ï

v

—

3

R

1

XIV

X I I I NBS

,2

0 0

R

R

1

Y

V/

R

3

The the

s t a r t i n g by

XV

p r i a t e above

G r i g n a r d a l c o h o l

p r e s e n c e e s t e r s

of

XIV

b r o m i n a t e d c h l o r i d e

in

XV

o f

p h e n o l in

good

w i t h the

w i t h

of

a l c o h o l

m e s i t y l

X I I I

o x i d e

was

p r e p a r e d

w i t h

LAH

3 - m e t h y l c r o t o n a l d e h y d e

r e a g e n t s .

X I I I

γ, (S-unsaturated e s t e r

a l l y l i c

r e d u c t i o n


Br

1

XVI

e i t h e r

Y - R /

and at

H e a t i n g

t r i e t h y l l V o °

y i e l d s .

of

the

e s t e r

was

in

p r e s e n c e

produce

p o t a s s i u m

of

XV.

BPO

to

Treatment

t - b u t o x i d e

in

of

in

the

the

γ , ô - u n s a t u r a t e d

XIV

N - b r o m o s u c c i n i m i d e e s t e r s

by a p p r o -

m i x t u r e


a f f o r d e d The

a

or

w i t h

c a r b o n o f THF

t h e n t e t r a -

ε - b r o m o -

the

r e s u l t i n g

gave


f i n a l l y

134

SYNTHETIC

the

d e s i r e d

t u t e d as

c y c l o p r o p a n e c a r b o x y l a t e

analogues

d e s c r i b e d

X I I I

and

The

c y c l i z a t i o n

R a

I V . R

1

H

"were

above,

t r i e t h y l

b u t y r a t e .

T a b l e

( l é )

s t a r t i n g

step

a r e

and

R

Et

o f

P r o d u c t

3

w i t h

t h e

a l l y l i c or

in


H

Et

Yield(JÏ)

XV

XVI

6k

91

85

Table

H

Et

88

Et

for

92*

Me

Et

t - B u O K / T H F k

k h r

t - B u O K / T H F

77**

1 h r

t - B u O K / T H F

-10°C: e

Et

Me

k8

H

22

83

1.5

Crude step

**

y i e l d s . w i t h o u t

I s o l a t e d The

y i e l d s

c y c l i z e d i s o m e r s .

the

crude

p r o d u c t

was

almost

1:1

at

m e r i z a t i o n

o f

e s t e r s

XVIb^and

96Ο-965

c m " " .

a t t a c h e d

though c o u l d

the not

Two t i o n

o f

XV

to

o f

to

the

the

a

c i s

XVIa

i s o m e r s . in

i s o -

t h e r m o d y n a m i c a l l y

s t r o n g

geometry

isomer

o f

t h a t

smooth

s p e c t r a

c y c l o p r o p a n e o f

c i s

t - b u t o x i d e

the

t h e

o f

o f

o f

t h e

r i n g

would

as

minor

a

t h e

a b s o r p t i o n

at olefinic

be

t r a n s ,

component

e x c l u d e d . X V I .

bromide

r e a c t i o n

s t i t u t i o n

next

s p e c t r u m

t r a n s

w i t h

i n d u c e d

e x h i b i t e d

T h e r e f o r e , to

in

m i x t u r e nmr

r e v e a l e d

a n d

I n f r a r e d

s i d e - r e a c t i o n s

hydrogen the

XVIc

XVa

c i s

a

t h e

m i x t u r e

isomer

( ΐ χ ) .

p r e s e n c e be

o f

t h i s

c i s

XVIa

u s u a l l y

from

however,

t h e

t r a n s

bond

m i x t u r e

80°,

s t a b l e

used

X I V .

example,

d e r i v e d o f

on

was

F o r

t r e a t m e n t

t - b u t a n o l

based

e s t e r

t r a n s

a

6 h r

p u r i f i c a t i o n .

and

F u r t h e r

were

p r o d u c t s

Crude

h r

t - B u O K / T H F

0^5°C:

*

h r

t - B u O K / T H F

69**

86*

60

H

C o n d i t i o n s

C y c l i z a t i o n

-30°C: d

f o r

I V .

0^5°C: c

o r t h o -

c o n d i t i o n s

R e a c t i o n

66**

91*

85

Me

manner,

a l c o h o l

t r i m e t h y l

60°C: b

a - s u b s t J U

s i m i l a r

Chrysanthemate

XIV H

The

a

r e a c t i o n

summarized

Homologues

2

in

o r t h o p r o p i o n a t e

r e s u l t s

X V I ,

p r e p a r e d

PYRETHROIDS

w i t h

The

were one

l e a d i n g XVb

h a l o g e n

t o

and by

o b s e r v e d was

t h e

d i e n e ,

X V c .

t - b u t o x y

The

in

t h e

c y c l i z a

1 , 2 - e l i m i n a t i o n w h i c h o t h e r

a n i o n

to

o c c u r r e d was

t h e

g i v e


t h e

o f in s u b

12.

KONDO

e s t e r

ET


AL.

X V I I .

c i a l l y

The

when

exposed

to

p e t i t i v e

the the

the

r e s u l t

in

bromoester

of

ι.

\

a c i d i t y in

XVd

c o u l d

r e a c t i o n

e s p e

XV

were

The

com

r e a c t i o n s of

and

the

might

α-hydrogen

XVe.

e f f e c t i v e l y

Both

be

s u p

t e m p e r a t u r e .

OBu

R

of

u n d e s i r e d

e s p e c i a l l y the

o b s e r v e d

c y c l i z a t i o n .

t h e s e

however,

l o w e r i n g

R


of

was

analogues

i n s u f f i c i e n t

XV,

s i d e - r e a c t i o n s , by

r e a c t i o n

a f o r e m e n t i o n e d

o c c u r r e n c e

be

p r e s s e d

l a t t e r

a - s u b s t i t u t e d

135

Moiety

1

d:

R

1

=

M e ,

R

= Et

e:

R

A

= E t ,

R =Me

and

s t y r y l

2

2

XVII

For

the

a n a l o g u e s , p r e p a r e d w i t h ( R

3

syntheses

of

b u t a d i e n y l

γ , ό - u n s a t u r a t e d

by

the

a l l y l i c

= p h e n y l )

e s t e r s


a l c o h o l s in

87

and

X H I f 75$

of

X l V f

and

t r i e t h y l

( R 3 = v i n y l )

y i e l d s ,

X l V g

and

X H I g

r e s p e c t i v e l y .

t -BuOK

Br

were


V

S

Λ

V v X l V f

,

Ph

v

Ph

NBS

»

v V

o f

(9k% XIX

o f

p r o d u c t y i e l d ) (85$

of

p r o d u c t s

u n s a t u r a t e d

I n s p e c t i o n major

A>\X

>

Ph XXI

XIX

s t r u c t u r e t h e s e

t-BuOK

I Br

XlVg

The

XX

XVIII

t h e i r from

and

y i e l d ) .

nmr X l V f

t h a t

o b t a i n e d

e s t e r s

was

by

not

the

so

b r o m i n a t i o n

s i m p l e .

s p e c t r a

suggested

was

ω-bromoester

from

the

X l V g

Treatment

of

was

the

t h e s e

t h a t

the XVIII

γ-bromoester

crude

b r o m i n a t i o n


136

SYNTHETIC

PYRETHROIDS

products with potassium t-butoxide in THF below 0° produced the expected cyclopropanecarboxylates XX, b.p.

62-65°/0.1 mm., and XXI, b.p. 112-ll8°/0.1 mm., in 59 and 58$ yields based on XIV, respectively. Acknowledgements. The authors are grateful to Mr.


Miss

T .

T a k a s h i m a ,

Y .

Takahatake

M r . f o r

T .

K o i z u m i ,

t h e i r

M r .

c a p a b l e

K.

Sugimoto,

a n d

a s s i s t a n c e .

Literature Cited, 1. Elliott, M., Farnham, A.W., Janes, N.F., Needham, P.H., Pulman, D.A., and Stevenson, J.H., Nature (1973) 246, 169. 2. Elliott, M., Farnham, A.W., Janes, N.F., Needham, P,H., and Pulman, D,A., Nature (1974) 248, 710. 3. Farkas, J., Kourim, P., and Sorm, F., Coll. Czech. Chem. Commun. (1959) 24, 2230. 4. Crombie, L., Doherty, C.F., and Pattenden, G., J. Chem. Soc. (C) (1970), 1076. 5. Elliott, Μ., Janes, N.F., and Pulman, D.A., J. Chem. Soc., Perkin I (1974), 2470. 6. Johnson, W.S,, Werthman, L., Bartlett, W.B., Brocksom, T.J., Li, T., Faulkner, D.J., and Petersen, M.R., J. Amer. Chem. Soc., (1970) 92, 7 4 l . 7. Babler, J.H. and Tortorello, A.J., J. Org. Chem. (1976) 4 1 , 885. 8. Harrison, R.G. and Lythgoe, B., Chem. Commun. (1970), 1513. 9. Bolton, I.J., Harrison, R.G., and Lythgoe, B., J. Chem. Soc. (C) (1971), 2950. 10. Kharasch, M.S., Jensen, E.V., and Urry, W.H., J. Amer. Chem. Soc. (1947) 69, 1100. 11. Kharasch, M.S., Jensen, E.V., and Urry, W.H., J. Amer. Chem. Soc. (1946) 68, 154. 12. Asscher, M. and Vofsi, D., J. Chem. Soc. ( 1 9 6 1 ) , 2261. 13. Suzuki, T. and Tsuji, J., Tetrahedron Lett. (1968), 913; J. O r g . Chem. (1970) 35., 2982. 14. Matsumoto, H., Nakano, T., and Nagai, Y., Tetrahedron Lett. (1973), 5l47. 15. Elliott, Μ., Farnham, A.W., Janes, N.E., Needham, P.H., and Pulman, D.A., Nature (1973) 244, 456. 16. Itaya, N., Okuno, Y., Horiuchi, F., Higo, Α., Honda, T., Mizutani, T., Ohno, N., Kitamura, S., and Matsuo, T., Japan kokai 74-75725, Chem. Abst. (1975) 82, 81723f. 17. Julia, Μ., Julia, S., Bemont, Β., and Tchernoff, G., C. R. Acad. Sci. (1959) 248, 242.


New Synthesis of the Acid Moiety of Pyrethroids

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