INSECTICIDAL STYRYL- AND SUBSTITUTED- STYRYLCYCLOPROPANECARBOXYLATES

STYRYLCYCLOPROPANECARBOXYLATES ET DERIVE DE SUBSTITUTION, INSECTICIDES

English Abstract

ABSTRACT
New insecticidal styryl- and substituted-styrylcyclo-
propanecarboxylates of the formula:
<IMG>
wherein X is halogen, cyano, nitro, aryl, aralkyl, aryloxy,
arylthio, alkyl, alkoxy, alkylthio, haloalkyl, dialkylamino
or methylenedioxy; Y is hydrogen, halogen, cyano, alkyl,
haloalkyl, carbomethoxy or carboethoxy; n is 0, 1, 2 or 3
and R is an alcohol residue, the ester from which provides
an insecticidally active cyclopropanecarboxylate.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. An insecticidal compound characterized by the formula:
<IMG>
in which X is halogen, cyano, nitro, aryl, aralkyl, aryloxy,
arylthio, alkyl of C1-C4, alkoxy of C1-C4, alkylthio of C1-C4,
haloalkyl of C1-C2, dialkylamino in which alkyls are C1-C2, or
methylenedioxy; Y is hydrogen, halogen, cyano, alkyl of C1-C4,
haloalkyl of C1-C2,carbomethoxy, or carbethoxy; n is 0, 1, 2 or
3; and R is an alcohol residue selected from the group consisting
of:
(a) a benzyl or phenoxy substituted benzyl group of the
formula:
<IMG>
wherein Z is hydrogen, cyano or phenyl and A is -0- or CH2-; and
(b) 5-benzyl-3-furylmethyl.
2. The compound of claim 1 characterized in that R is 3-
phenoxybenzyl, .alpha. -cyano-3-phenoxybenzyl, or 5-benzyl-3-
furylmethyl.
-28-

3. The compound of claim 1 characterized in that X is
chloro, cyano, methyl, methoxy, or methylenedioxy; Y is hydrogen,
chloro, bromo, cyano, methyl, carbomethoxy or carbethoxy; n is 0,
1 or 2, and R is 3-phenoxybenzyl, .alpha.-cyano-3-phenoxy-benzyl, or 5-
benzyl-3-furylmethyl.
4. The compound of claim 3 characterized in that X is
chloro, Y is hydrogen or chloro, and n is 0 or 1.
5. The compound of claim 1 characterized in that the
compound is 3-phenoxybenzyl 2,2-dimethyl-3-(.beta.-phenylvinyl)-
cyclopropane-carboxylate.
6. The compound of claim 5 characterized in that the
predominant isomer is the cis (Z) form.
7. The compound of claim 1 characterized in that the
compound is .alpha.-cyano-3-phenoxybenzyl 3-[3-(4-chlorophenyl)vinyl]-
2,2-dimethylcyclopropanecarboxylate.
8. The compound of claim 7 characterized in that the
predominant isomer is cis.
9. The compound of claim, 1 characterized in that the
compound is 3-phenoxybenzyl 3-(.beta.-chloro-3-phenylvinyl)-2,2-
dimethylcyclopropanecarboxylate.
10. The compound of claim 1 characterized in that the
compound is 5-benzyl-3-furylmethyl 3-(.beta.-chloro-.beta.-phenylvinyl)-
2,2-dimethylcyclopropanecarboxylate.
11. The compound of claim 1 characterized in that the
compound is .alpha.-cyano-3-phenoxybenzyl 3-(.beta.-chloro-.beta.-phenylvinyl)-
2,2-dimethylcyclopropanecarboxylate.
-29-

12. A method of controlling insects characterized in
applying to the locus where control is desired an insecticidally
effective amount of a compound of claim 1.
13. A process for the preparation of insecticidal styryl-
or substituted-styrylcyclopropanecarboxylates characterized by
the formula:
<IMG>
wherein X is halogen, cyano, nitro, aryl, aralkyl, aryloxy,
arylthio, alkyl of C1-C4, alkoxy of C1-C4, alkylthio of C1-C4,
haloalkyl of C1-C2, dialkylamino in which alkyls are C1-C2, or
methylenedioxy; Y is hydrogen, halogen, cyano, alkyl of C1-C4,
haloalkyl of C1-C2,carbomethoxy, or carbethoxy; n is 0, 1, 2 or
3; and R is an alcohol residue selected from the group consisting
of:
(a) a benzyl or phenoxy substituted benzyl group of the
formula:
<IMG>
wherein Z is hydrogen, cyano or phenyl and A is -0- or CH2-; and
(b) 5-benzyl-3-furylmethyl;
characterized by reacting a compound of the formula:
-30-

<IMG>
wherein R' is alkyl of C1-C4 with a phosphonium salt of partial
formula:
<IMG>
wherein X, Y and n are as defined above in the presence of a
strong base in an essentially anhydrous inert solvent under an
inert atmosphere to give an ester of the formula:
<IMG>
wherein X, Y, n and R' are as defined above, hydrolyzing the
ester and reesterifying by conversion to the acid halide and
treatment with an alcohol of the formula R-OH wherein R is as
defined above.
14. A compound of the formula:
-31-

<IMG>
in which X is hydrogen, halogen or methyl, Y is hydrogen or cyano
and n is 1 or 2.
15. A compound of the formula:
<IMG>
16. A compound of the formula:
<IMG>
17. A process for the production of compounds as defined in
claim 14 which comprises reacting a compound of the formula:
-32-

<IMG>
in which X and n are as defined in claim 14 and Hal is halogen
with a compound of the formula:
<IMG>
in which Y is as defined in claim 14.
18. A method of controlling insects comprising applying an
insecticidally effective amount of a compound of claim 14 to the
insects or to a locus where control is desired.
19. A compound of the formula:
<IMG>
-33-

in which X is hydrogen, halogen or alkyl of 1 to 4 carbon atoms,
Z is halogen, Y is hydrogen or cyano and n is 1, 2 or 3.
20. A compound of the formula:
<IMG>
21. A process for the production of a compound as defined
in claim 19 which comprises reacting a compound of the formula:
<IMG>
in which X, Z and n are as defined in claim 19 and Hal is halogen
with a compound of the formula.
<IMG>
in which Y is as defined in claim 19.
-34-

22. A method of controlling insects comprising applying an
insecticidally effective amount of a compound of claim 19 to the
insects or to a locus where control is desired.
23. A compound of the formula:
<IMG>
in which R3 is phenyl or phenyl carrying at least one alkyl group
or halogen atoms and R4 is hydroxy or halogen.
24. A compound of the formula:
<IMG>
in which R3 is phenyl carrying at least one alkyl group or
halogen atom and R4 is alkoxy of 1 to 4 carbon atoms.
25. A compound of the formula:
-35-

<IMG>
in which Z is halogen, R3 is phenyl or phenyl carrying at least
one alkyl group or halogen atom R4 is hydroxy or halogen.
26. An insecticidal compound characterized by the formula:
<IMG>
in which X is cyano, nitro, aryl, aralkyl, aryloxy, arylthio,
alkyl of C1-C4, alkoxy of C1-C4, alkylthio of C1-C4, haloalkyl of
C1-C2, dialkylamino in which alkyls are C1-C2, or
methylenedioxy; Y is hydrogen, halogen, cyano, alkyl of C1-C4,
haloalkyl of C1-C2, carbomethoxy, or carbethoxy; n is 1, 2 or 3;
and R is an alcohol residue selected from the group consisting
of:
(a) a benzyl or phenoxy substituted benzyl group of the
formula:
<IMG>
-36-

wherein Z is hydrogen, cyano or phenyl and A is -0- or CH2-; and
(b) 5-benzyl-3-furylmethyl.
27. An insecticidal compound characterized by the formula:
<IMG>
in which X is halogen, cyano, nitro, aryl, aralkyl, aryloxy,
arylthio, alkyl of C1-C4, alkoxy of C1-C4, alkylthio of C1-C4,
haloalkyl of C1-C2, dialkylamino in which alkyls are C1-C2, or
methylenedioxy; Y is halogen, cyano, alkyl of C1-C4, haloalkyl of
C1-C2,carbomethoxy, or carbethoxy; n is 0, 1, 2 or 3; and R is an
alcohol residue selected from the group consisting of:
(a) a benzyl or phenoxy substituted benzyl group of the
formula:
<IMG>
wherein Z is hydrogen, cyano or phenyl and A is -0- or CH2-; and
(b) 5-benzyl-3-furylmethyl.
28. A method of controlling insects characterized in
applying to the locus where control is desired an insecticidally
effective amount of a compound of claim 26.
29. A method of controlling insects characterized in
applying to the locus where control is desired an insecticidally
effective amount of a compound of claim 27.
-37-

Description

FMC 4289
~60~6
This invention relates to new insecticidal styryl- and
substituted-styrylcyclopropanecarboxylates which are useful
in agriculture to protect crops and animals, and are also
useful to control household pests.
Ever since the structures of naturally occurring
pyrethroids were elucidated, synthesis efforts have been
directed toward the preparation of related compounds of
enhanced insecticidal activity and improved stability
toward air and light. A noteworthy advance in this area
was the discovery by Elliott and co-workers of certain
highly active compounds remarkably resistant to photo-
oxidative degradation, for example, 3-phenoxybenzyl 3-
~ -dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,
Nature, 246, 169 (1973), Belgian Patents 800,006 and
818,811.
Despite extensive research in the field of
insecticidal cyclopropanecarboxylates, insecticidal
styrylcyclopropanecarboxylates of the type described
herein have not been described prior to the present
invention.
In accordance with the present invention there i8
provided new styryl- and substituted-styrylcyclopropane-

1 ~6 ~4~U~
carboxylate compounds and a process for their production.
Typical styryl- and substituted-styrylcyclopropane-
carboxylate compounds of the present invention include
insecticidal esters of 2,2-dimethyl-3-(~-phenylvinyl)cyclo-
propanecarboxylic acid, 2,2-dimethyl-3-[~-(substituted-
phenyl)vinyl]cyclopropanecarboxylic acid, 2,2-dimethyl-3-
(~-phenyl-~-substituted-vinyl)cyclopropanecarboxylic acid,
and 2,2-dimethyl-3-[~-(substituted-phenyl)-~-(substituted)-
vinyl]cyclopropanecarboxylic acid, and are characterized
by the formula-
CH3\~CH3
Xn ~ = CH- ~ COOR (I)
in which X is halogen, such as fluoro, chloro, or bromo;
cyano; nitro: aryl, such as phenyl, thienyl, furyl, or
pyridyl; aralkyl, such as benzyl; lower alkyl; lower halo-
alkyl; lower alkoxy; lower alkylthio; aryloxy; arylthio;
di(lower alkyl)amino; and methylenedioxy; Y ls hydrogen;
halogen, for example, chloro, bromo, or fluoro; lower alkyl;
cyano; lower haloalkyl; carbomethoxy; or carboethoxy; n is
0, 1, 2, or 3, more commonly 0, 1, or 2; and R is the
residue of an alcohol which in combination with an
appropriate acid moiety yields an insecticidal cyclo-
propanecarboxylate. A wide range of alcohol moieties
are known in the insecticide art and are useful in the
present invention, for example:

1260486
( 1 ) a benzyl-or phenoxy-substituted benzyl group of
the formula: z
-CH
~ A - ~
wherein z is hydrogen, methyl, cyano, ethynyl, or phenyl,
and A is -0- or -CH2-;
(2) a benzyl-or phenoxy-substituted furylmethyl group
such as 5-benzyl-3-furylmethyl;
(3) an imidomethyl group such as maleimidomethyl,
phthalimidomethyl, and tetrahydrophthalimidomethyl;
(4) a benzyl group substituted in at least two ring
positions with chloro, methyl, or methylenedioxy
groups, for example 3,4-methylenedioxybenzyl,`
2-chloro-4,5-methylenedioxybenzyl, and 2,4-
dimethylbenzyl7
(53 a substituted cyclopentenonyl group such as
allethrolonyl.
The commonly used R groups which give active insecti-
cides of the preqent invention are: 3-phenoxybenzyl,
a-cyano-3-phenoxybenzyl, and 5-benzyl-3-furylmethyl.
In the substituents X and Y, lower, as applied to
2~ alkyl groups, means having 1-4 carbon atoms, preferably
having one or two carbon atoms. Examples of haloalkyl
substituents include trichloromethyl and trifluoromethyl
groups.
One aspect of the present invention relates to a
process for the preparation of insecticidal styryl- and
--3--

1~260486
substituted-st~rylcyclopr~panecarboxylates of formula I,
above, which comprises reacting a compound of the formula:
CH~ ~ CH3
/ \ (II)
OHC ' - ` ~COOR'
wherein R' is alkyl of Cl-C4, with a phosphonium salt of
partial formula:
Xn ~ CH - P \ (III)
wherein X, Y, and n are as defined above, in the presence
of a strong base, preferably conducted in the presence of
an essentially anhydrous inert solvent, preferably under
an inert atmosphere to give an ester of the formula:
CH3 ~ H3
Xn ~ Cl = CH / \ COOR' (Ia)
wherein X, Y! n, and R' are as defined above, hydrolyzing
the ester and reesterifying by conversion to the acid
halide and treatment with an alcohol of the formula R-OH
wherein R i8 as defined above.
In the above process, the phosphonium salt is con-
verted in the presence of the strong base to the corre-
spondlng phosphorane:
Xn ~ C = P''' (IIIa)
which species reacts with the cyclopropanecarboxaldehyde.
The strong base used in the above process may be an
alkyllithium such as n-butyllithium, or an alkali metal
hydride, amide, or alcoholate.

1260486
The inert solvent employed in the reaction of the
cyclopropanecarboxaldehyde may be any of the solvents
commonly used in Wittig-type reactions, including benzene,
tetrahydrofuran, dimethoxyethane, dimethylformamide, and
the like. The reaction may suitably be carried out at
0-35C for 1-24 hours,
The hydrolysis of the resulting ester in the above
described process may be effected with base.
Reesterification of the resulting acid in the above
process may be accomplished by treatment with thionyl
chloride in an anhydrous inert solvent under an inert
atmosphere in the presence of a base such as pyridine at
ambient temperature, followed by the addition of the
alcohol R-OH.
Certain of the intermediates, those of formula Ia
above, wherein Y i8 cyano or halo, may optionally be pre-
pared by the following metho,ds. The compounds wherein Y is
cyano may be readily prepared by the base catalyzed conden-
sation of an appropriately substituted benzyl cyanide with
a cyclopropanecarboxaldehyde of formula II, The compounds
wherein Y i6 halo may be readily prepared by the treatment
of a dialkyl benzylphosphonate, appropriately substituted
on the phenyl ring, with a strong base such as n-butyl-
lithium at low temperature (about -78), followed by the
addition of first carbon tetrahalide then a cyclopropane-
carboxaldehyde of formula II.
_5_

48~
The preparation and insecticidal properties of the
compounds of this invention are illustrated in the follow-
ing specific examples. Unles otherwise specified all
temperatures are in degrees centigrade, and concentration
of liquid volume was carried out under the reduced pressure
produced by a water aspirator.
Example l
Synthesis of 3-Phenoxybenzyl 2,2-Dlmethyl-3-(~-phenylvinyl)-
_ _ cyclopropanecarboxylate _ _
A. Preparation of Ethyl 2,2-dimethyl-3-(~-phenyl-
vinyl)cyclopropanecarboxylate
Under a nitrogen atmosphere and anhydrous conditions
43 ml of an approximately 2.5 M solution of n-butyllithium
in hexane was added to a suspension of 41.81 g benzyl-
triphenylphosphonium chloride in 200 ml anhydrous benzene.
During the addition of the n-butyllithium solution in small
portions the reaction temperature was maintained at about
25 by intermittent cooling with an ice-water bath. After
addition of the n-butyllithium solution was completed, the
reaction mixture was stirred at room temperature for 2.75
hours. The reaction mixture was then added, in 10-20 ml
portions via a glass tube, to an anhydrous, ice cold,
stirred solution of 16.7 9 ethyl caronaldehyde in 50 ml of
benzene. During the addition, the reaction mixture was
cooled with an ice-water bath. The reaction mixture was
allowed to warm to room temperature over a period of

1Z60486
0.5 hr and then stirred for an additional hour. The
reaction mixture was filtered, and the filtrate was washed
sequentially with two 200 ml portions of water and two 100
ml portions of saturated brine and then dried over anhydrous
magnesium sulphate. The solvent was removed and the residue
dried under reduced pressure to yield 27.71 g amorphous
white solid. The solid was triturated with 150 ml anhydrous
hexane, filtered and concentrated to yield 20.59 g of
viscous liquid. The nmr and ir spectra were consistent with
the expected mixture of geometric isomers of ethyl 2,2-
dimethyl-3-(~-phenylvinyl)cyclopropanecarboxylate.
B. Preparation of 2,2-dimethyl-3-(~-phenylvinyl)-
cyclopropanecarboxylic acid
A mixture of 30.68 g of ethyl 2,2-dimethyl-3-
(~-phenylvinyl)cyclopropanecarboxylate, 5 g of sodium
hydroxide, 29 ml of ethanol and 300 ml of water was heated
at 50~ for 35 hours. After ~tanding at room temperature
- for 12 hours, the reaction mixture was concentrated under
reduced pressure. The concentrate was diluted with 450 ml
of dry benzene, then taken to dryness under reduced pres-
sure. The re~idue was shaken with a mixture containing
400 ml of water and 100 ml saturated brine, and the
resulting mixture was then extracted with chloroform. The
aqueous phase was made acidic (pH 3) with 320 ml of 3~
hydrochloric acid and extracted with a 500 ml portion of
diethyl ether followed by two 1200 ml portions of diethyl
ether. The ethereal extracts were washed with four 300 ml
--7--

~:~6048~
portions o~ water and then dried over anhydrous magnesium
chloride. The dried ethereal solution was filtered and the
solvent removed to yield 22.34 9 of 2,2-dimethyl-3-
(~-phenylvinyl)cyclopropanecarboxylic acid. The nmr and ir
spectra were consistent with the expected isomeric mixture.
C. Preparation of 3-phenoxybenzyl 2,2-dimethyl-3-
(~-phenylvinyl)cyclopropanecarboxylate
To a stirred mixture of 6.10 g of 2,2-dimethyl-3-
(~-phenylvinyl)cyclopropanecarboxylic acid in 50 ml of dry
benzene, under a nitrogen gas atmosphere and at ~5, was
added 1.2 ml of pyridine (4.0% excess), then 1.1 ml of
thionyl chloride (7.0% excess). The exothermic reaction
caused the reaction mixture temperature to rise to 35-40.
coplous amount of white pyridine hydrochloride precipi-
tated from the reaction mixture. Stirring at ambient tem-
perature was continued for 7 hours. To the above suspension
containing 2,2-dimethyl-3-(~rphenylvinyl)cyclopropane-
carbonyl chloride and pyridine hydrochloride was added
1.7 ml of pyridine and 100 ml of dry benzene; then, with
stirring, 3.07 g (7.0% excess) of 3-phenoxybenzyl alco-
hol in 50 ml of dry benzene. The reaction mixture was
stirred at ambient temperature for 13.3 hours. Thin layer
chromatographic analysis of the reaction mixture indicated
the reaction was complete. The reaction mixture was fil-
tered, and the filtrate was concentrated, diluted with
hexane, and refiltered. The filtrate was concentrated
under reduced pressure to a pale yellow oil and then further
concentrated by use of a vacuum pump. The oil was dissolved
,
--8--

1260486
in 30 ml diethyl ether and washed with two 700 ml portions
of water. The ether layer was washed with a saturated brine
solution, then dried over magnesium sulfate. The mixture was
filtered and the filtrate evaporated to a residual 5.66 g of
oil. The oil was filtered through a column containing 51 g
of silica gel and with pentane and pentane-ether as eluent
to give 4.1 g (72%) of 3-phenoxybenzyl 2,2-dimethyl-3-
(~-phenylvinyl)cyclopropanecarboxylate. The nmr and the ir
spectra were consistent with the proposed structure.
Analysis calc'd for C27H2603: C 81.38; H 6.58
Found: C 81.30; H 6.59,
D. Separation of Isomers
A sample of 3-phenoxybenzyl 2,2-dimethyl-3-
(~-phenylvinyl)cyclopropanecarboxylate was separated into
three isomers by use of a medium pressure liquid chroma-
tographic unit. The separation, with 50 parts hexane, 1
part ethyl acetate as eluent~ was carried out on a silica gel
column and gave sixty 25 ml fractions. Fractions 24-27 were
combined and evaporated under reduced pressure to give 0.40 g
of 3-phenoxybenzyl 2,2-dimethyl-cis-3-(~-(Z)-phenylvinyl)
cyclopropanecarboxylate. In the same manner, fractions 30-37
were combined to give 0.94 g of 3-phenoxybenzyl 2,2-dimethyl-
trans-3-(~-(E)-phenylvinyl)cyclopropanecarboxylate. Frac-
tions 28-29 were combined to give 0.25 g of 3-phenoxybenzyl
2,2-dlmethyl-trans 3-(~-(Z)-phenylvinyl)cyclopropanecarboxy-
late. The nmr and lr spectra were consistent with the struc-
ture assigned to each isomer.

~260486
The structure assignments of the isomers were based
on the following nmr data in which d means doublet, dd means
doublet of doublets, and m means multiplet. Tetramethyl-
silane was used as an internal standard. Values reported
are ppm for deuterated chloroform solutions. Hl and H3
are respectively on the 1- and 3- carbons of the cyclo-
propane ring, and Hl and H3 are re~pectively on the vinyl
group a and ~ to the cyclopropane ring.
trans (E) cis (Z) trans (z)
Hld, 1.73) m 1.70-2.32 d, 1.60
H3dd, 2.21 dd, 2.43
Hadd, 5.90 dd, 5.96 dd, 5.40
H~d, 6.50 d, 6.58 d, 6.57
Ha H~16 Hz 11 Hz 11 Hz
By the methods exemplified above may be prepared
other insecticidal esters of 2,2-dlmethyl-3-(~-phenyl-
vinyl)cyclopropanecarboxyliclacid ~uch as a-cyano-3-
phenoxybenzyl 2,2-dimethyl-3-(~-phenylvinyl~cyclopropane-
carboxylate and 5-benzyl-3-furylmethyl 2,2-dimethyl-3-
(~-phenylvinyl)cyclopropanecarboxylate.
Example 2
Synthesis of a-Cyano-3-phenoxybenzyl 3-[~-(4-chlorophenyl)-
vinyl]-2,2-dimethylcyclopropanecarboxylate
A. Preparation of Ethyl 3-1~-(4-chloropbenyl)vinyl]-
2,2-dimethylcyclopropanecarboxylate
Under a nitrogen atmosphere and anhydrous con-
ditions 81 ml of an approximately 2.5 M solution of n-butyl-
~"/ -1 0--
~ ,

~260486
lithium in hexane was added to a suspension of 84.54 g of
4-chloroben~yltriphenylphosphonium chloride in 200 ml an-
hydrous benzene over a period of 20 min. The n-butyllithium
solution was added in small portions, and the reaction
temperature was maintained at about 25 by intermittent
cooling with an ice-water bath. After addition of the n-
butyllithium solution was completed, the reaction mixture
was stirred at room temperature for 2.75 hours. This mix-
ture was added, in 10-20 ml portions via a glass tube, to an
anhydrous, ice cold, stirred solution of 32.20 9 ethyl
caronaldehyde in 50 ml of benzene. During the addition the
reaction mixture was cooled in an ice-water bath. The
reaction mixture was allowed to warm to room temperature
over a period of 0.5 hr and then stirred for an additional
hour. The reaction mixture was filtered, and the filtrate
was washed with two 200 ml portions of water, then with two
100 ml portions of saturated,brine, and dried over anhydrous
magnesium sulphate. The solvent was removed and the resi-
due dried under reduced pressure to yield an amorphous white
solid. The solid was triturated with 150 ml anhydrous
hexane, filtered and concentrated to yield 44.88 g of
viscous liquid. The nmr and ir spectra were consistent
with the expected mixture of geometric isomers of ethyl
3-[~-(4-chlorophenyl)vinyl]-2,2-dimethylcyclopropane-
carboxylate.
B. Preparation of 3-[~-(4-Chlorophenyl)vinyll-2,2-
dimethylcyclopropanecarboxylic acid
A mixture of 37.90 g of ethyl 3-[~-(4-chloro-

~OJ.~
phenyl)vinyl~-2,2-dimethylcyclopropanecarboxylate, 6.56 g
of sodium hydroxide, 371 ml of ethanol, and 21.5 ml of water
was heated at 55 for 60 hours~ After the mixture had stood
at room temperature for 12 hours, the reaction mixture was
concentrated under reduced pressure. The concentrate was
diluted with 450 ml of dry benzene, then taken to dryness
under reduced pressure. The residue was shaken with a
mixture containing 400 ml of water and 100 ml saturated
brine, then the resulting mixture was extracted with
chloroform. The aqueous phase was made acidic (pH 3) with
320 ml of 3% hydrochloric acid, and extracted with a 500 ml
portion of diethyl ether followed by two 1200 ml portions
of diethyl ether. The ethereal extracts were washed with
four 300 ml portions of water and then dried over anhydrous
magnesium chloride. The dried ethereal solution was
filtered and the solvent removed under reduced pressure to
yield as an oil 33.06 g of 3~[~-(4-chlorophenyl)vinyl]-
2,2-dimethylcyclopropanecarboxylic acid. The nmr and ir
spectrum were consistent with the expected isomeric
mixture.
C. Preparation of trans-3-[~-(E)-(4-Chlorophenyl)-
__ _
vinyl]-2,2-dimethylcyclopropanecarboxylic acid
A mixture (33.06 g) of geometric isomers, pre-
pared as described above, was stirred for 15 min. at room
temperature in 200 ml of pentane and filtered. The residue
was collected and dried to yield 5.75 g of solid, m.p. 106,
identified by its nmr spectrum as trans-3-[~-(E)-(4-chloro-
phenyl)vinyl]-2,2-dimethylcyclopropanecarboxylic acid. An
-12-

~Z~04~36
additional 2.79 g of this isomer was obtained by reducing
the volume of the filtrate by about 1/2 and cooling the
concentrated filtrate to 0. (The filtrate, containing
other isomeric acids, was reserved). The nmr spectrum was
definitive for the assigned structure.
D. Preparation of a-cyano-3-phenoxybenzyl trans-3-
[~-(E)-(4-chlorophenyl)vinyl]-2,2-dimethylcyclo-
propanecarboxylate
Trans-3-[~-(E)-(4-chlorophenyl)vinyl]-2,2-dimethyl-
-
cyclopropanecarboxylic acid (8.34 g) was heated under
reflux for 3 hours with 5 ml of thionyl chloride in 35 ml
of benzene. The excess thionyl chloride and benzene was
distilled from the reaction mixture. Additional benzene
was added to the reaction mixture to bring the volume of
the solution to 100 ml. A 24 ml portion of this solution
containing 2.14 g of trans-3-[~-(E)-(4-chlorophenyl)vinyl]-
2,2-dimethylcyclopropanecarbonyl chloride was treated with
a mixture of 1.79 g of a-cyano-3-phenoxybenzyl alcohol, and
1.59 ml of pyridine in 10 ml of benzene. The addition of
the alcohol mixture to the acid chloride was done at 0.
Upon complete addition the reaction mixture was stirred at
ambient temperature for 24 hours; then was filtered to remove
pyridine hydrochloride. The filtrate was evaporated under
reduced pressure to a residual 3.50 g of oil. The oil was
purified on a chromatographic column of 17.5 g of silica
gel. Elution of the oil from the column was accomplished
with diethyl ether/pentane mixtures. The yield was 2.60 g
-13-

~.2604~6
~71.0%) of ~-cyano-3-phenoxybenzyl trans-3-[~-( E ) - ( 4-
chlorophenyl)vinyl]-2,2-dimethylcyclopropanecarboxylate.
Analysis: Calc'd for C28~24ClNO3: C 73.43; H 5.28; N 3.06
Found: C 73.18; H 5.32; N 2.98.
E. Preparation of a-cyano-3-phenoxybenzyl cis,trans-
3-[~-(E,Z)-(4-chlorophenyl)vinyl]-2,2-dimethyl-
cyclopropanecarboxylate
The final filtrate of Example 2-C contained mixed
isomeric acids depleted as to the trans (E~ isomer. A por-
tion of thi~ acid, 5.60 9 of cis,trans-3-[~-(E,Z)-(4-chloro-
phenyl)vinyl]-2,2-dimethylcyclopropanecarboxylic acid, was
esterified by the method of Example 2-D with 2.73 9 of
thionyl chloride, 5.18 g of a-cyano-3-phenoxybenzyl alcohol,
and 3.5 ml of pyridine in benzene. The crude product was
pur~fied on a chromatographic column of 54.5 9 of silica
gel. Elution was accomplished using 20% methylene chlor-
ide - 80% pentane to give 6.~5 g (72%) of a-cyano-3-phenoxy-
benzyl cls,trans-3-[~-(E,Z)-(4-chlorophenyl)vinyll-2,2-
dimethylcyclopropanecarboxylate.
Analysis: Calc'd for C28H24ClN03: C 73.43; H 5.28; N 3.06
Found: C 73.20; H 5.32; N 3.01.
Example 3
Synthesis of 3-phenoxybenzyl 3-(~-Chloro-~-phenylvinyl)-
2,2-dimethylcyclopropanecarboxylate
A. Preparation of Ethyl 3-(~-chloro-~-phenylvinyl)-2,
2-dimethylcyclopropanecarboxylate
To a solution of 28.35 g of diethyl benzylphospho-
nate in tetrahydrofuran at -78 was added one equivalent of
-14-

~a~o 4~
n-butyllithium in hexane. After the reaction mixture was
stirred at -70 for 40 minutes, 124 ml of carbon tetra-
chloride was added and stirring at -70 was continued for an
additional 40 minutes. To this mixture was added 23.6 g of
ethyl caronaldehyde. The mixture was allowed to warm to
room temp~rature, and 27 ml of water was added. The
reaction mixture was extracted with diethyl ether. The
ethereal extract was concentrated, treated with 200 ml of
pentane at -50, triturated, and the pentane decanted. The
residue was treated with 200 ml of pentane at -30, tri-
turated, and the pentane decanted. The combined decantates
were concentrated to an oil, which was treated with 19 g
of sodium bisulfite in 50 ml of water. The mixture was
extracted with 50 ml of diethyl ether. The extract was
washed with 50 ml of saturated aqueous sodium chloride
solution, dried over anhydrous magnesium sulfate~ and con-
centrated to yield 19.71 g of oil. The oil was purified
by chromatography on 98.5 g of silica gel, with 95:5
hexane:ether as eluent. The solvents were removed under
reduced pressure to yield 14.4 g of ethyl 3-(~-chloro-~-
phenylvinyl)-2,2-dimethylcyclopropanecarboxylate as a
mixture of isomers containing cis, trans, (E), and (Z)
forms. The nmr and ir spectra were consistent with the
assigned structure.
B. Preparation of 3-(~-chloro-~-phenylvinyl)-2,2-
dimethylcyclopropanecarboxylic acid
A mixture of 16.91 g of ethyl 3-(~-chloro-~-phenyl-
vinyl)-2,2-dimethylcyclopropanecarboxylate, 2.57 g of
-15-

12~50 4~
sodium hydroxide, 4.6 ml of water, and 72 ml of ethanol was
heated at 55 for 17 hours. The mixture was allowed to cool
and was concentrated to near dryness. A saturated aqueous
sodium chloride solution was added to the concentrate and
the mixture thus formed was washed with chloroform. The
aqueous phase was acidified with 3~ hydrochloric acid and
extracted with diethyl ether. The ethereal extract was
concentrated to yield approximately 14.57 g of 3-(~-chloro-
~-phenylvinyl)-2,2-dimethylcyclopropanecarboxylic acid.
The nmr and ir spectra were ~onsistent with the assigned
structure.
C. Preparation of 3-(~-chloro-~-phenylvinyl)-2,2-
dimethylcyclopropanecarbonyl chloride
A 14.57 g portion of 3-(~-chloro-~-phenylvlnyl)-
2,2-dimethylcyclopropanecarboxylic acid was dried by twice
azeotropically distilling the contained water with benzene.
The acid was then diluted with 52 ml of benzene, and 9 ml
of thionyl chloride was added to the solution. The mixture
was heated under reflux for 3 hours. The excess thionyl
chloride was removed by distillation. More benzene was
added, and further distillation removed all traces of
thionyl chloride. The reaction mixture was diluted to a
volume of 100 ml with benzene.
D. Preparation of 3-phenoxybenzyl 3-(~-chloro-~-
phenylvinyl)-2,2-dimethylcyclopropanecarboxylate
A 33.3 ml portion of the 3-(~-chloro-~-phenylvinyl)-
2,2-dimethylcyclopropanecarbonyl chloride solution in ben-
; zene of Example 3-C was added at 0C to a stirred solution of
:
~ -16-
.
.

1~;~48fi
4.0 g of 3-phenoxybenzyl alcohol and 4 ml of pyridine
in 26 ml of benzene. The reaction mixture was stirred at
ambient temperature for 14 hours. The pyridine hydro-
chloride was removed by filtration. The filtrate was
evaporated under reduced pressure to give 8.6 g of
residual oil. The residual oil was purified on a chroma-
tographic column of 42.5 9 silica gel. Elution was
accomplished with 860 ml of 20~ methylene chloride/80%
pentane to give 6.41 g (77%) of 3-phenoxybenzyl
3-(~-chloro-~-phenylvinyl)-2,2-dimethylcyclopropane-
carboxylate.
Analysi~: Calc'd for C27H25C103: C 74.90; H 5.82;
Found: C 74.81; H 5.83.
Example 4
Synthesis of 5-benzyl-3-furylmethyl 3-(~-chloro-~-phenyl-
_ _ vinYl)-2,2-dimethylcyclopropanecarboxylate
This compound was prepared by the method of Example
3-D, with 33.3 ml of the 3-(~-chloro-~-phenylvinyl)-2,2-
dimethylcyclopropanecarbonyl chloride/benzene solution from
Example 3-C, 3.75 g of 5-benzyl-3-furylmethyl alcohol and
4 ml of pyridine in 26 ml of benzene. The yield was 6.14
g ~46%) of^5-benzyl-3-furylmethyl 3-(~-chloro-~-phenyl-
vinyl)-2,2-dimethylcyclopropanecarboxylate.
Analysis: Calc'd for C26H25C103: C 74.19; H 5.99;
Found: C 74.10; H 6.03.
-17-
~,
.~ '.

4~
Example 5
Synthesis of a-cyano-3-phenoxybenzyl 3-(~-chloro-~-phenyl-
vinyl)-2,2-dimethylcyclo ropanecarboxylate
This compound was prepared by the method of Example
3-D, with 33.3 ml of the 3-~-chloro-~-phenylvinyl)-2,2-
dimethylcyclopropanecarbonyl chloride/benzene solution of
Example 3-C, 4.50 g of a-cyano-3-phenoxybenzyl alcohol and
4 ml of pyridine in 26 ml of benzene. The yield was 7.12
g (81%) of ~-cyano-3-phenoxybenzyl 3-(~-chloro-~-phenyl-
vinyl)-2,2-dimethylcyclopropanecarboxylate.
Analysis: Calc'd for C28H24ClN03: C 73.43; ~ 5.28; N 3.06;
Found: C 73.60; H 5.31; N 3.08.
Example 6
Toxicity to Insects and Mites
Initial Contact Activity: One quarter gram of test compound
was dissolved in 20 ml of acetone and this solution was dis-
persed in 180 ml of water co,ntaining one drop of isooctyl-
phenyl polyethoxyethanol. Aliquots of this solution, which
corresponds to 1250 ppm of active ingredient, were diluted
with an appropriate amount of water to provide solutions
containing 312 ppm or 156 ppm of active ingredient. Test
organisms and techniques were as follows: the activities
against the Mexican bean beetle (Epilachna varivestis
Muls.) and the southern armyworm (Spodoptera eridania
[Cram.~) were evaluated by dipping the leaves of pinto bean
plants into the test solution and infesting the leaves with
the appropriate immature-form insects when the foliage had
-18-

~ O 4~5
dried; the activity against the pea aphid ~Acyrthosiphon
~isum ~Harris]) was evaluated on broad bean plants whose
leaves were dipped before infestation with adult aphids;
the activity against two-spotted spider mites (Tetranychus
urticae Koch) was evaluated on pinto bean plants whose
leaves were dipped after infestation with adult mites; the
activities against the milkweed bug (Oncopeltus fasciatus
[Dallas]), the boll weevil (Anthonomus grandis Boheman), and
the plum curculio (Conotrochelus menuphar [Herbst]) were
evaluated by spraying the test solutions into glass dishes
or jars containing the adult insects; the activities against
the confused flour beetle (Tribolium confusum [duVal]) and
granary weevil [Sitophilus granarius (Linnaeus)] were
evaluated by introducing the insects into glass dishes which
had been previously sprayed with test solution and allowed
to dry. All organisms in the test were maintained in a
holding room at 80F and 50%, relative humidity for an
exposure period of 48 hours (96 hours for the confused flour
beetle). At the end of this time, the dead and living
insects or mites were counted, and the percent kill was
calculated. Results of these tests are summarized in
Table 1.
Residual Contact Activity: The residual contact activity
of the compounds was determined on the same organisms using
the techniques described above, except that in each case
the treated surface was allowed to dry and was exposed to
normal light and air for seven days before introduction of
--19--

i2~iO4t36
the mites or insects. Results of these tests are summarized
in Table 2.
Example 7
InsecticidaI Activity Against House Flies and German
Cockroaches
In this test the compounds of this invention
were tested for insecticidal activity against three or four
day old female houseflies (resistant) (Musca domestica
Linnaeus) and male German cockroaches [Blattella ~ermanica
(Linnaeus)]. A number of insects was anesthetized with
carbon dioxide and placed in a container for about 2 hours,
during which time the insects recovered to normal activity.
The container confining the insects was fitted with a
plunger which is used to force the insects against a nylon
mesh at one end of the container. For the Level I test one
microliter of an acetone solution containing five micro-
grams of the candidate insecticide, for the Level II test
one microliter of an acetone solution containing one micro-
gram of the candidate insecticide, was applied topically to
each insect. The plunger was withdrawn and the insects were
allowed to move freely about the container. ~nockdown
counts were recorded 10 minutes after treatment of house-
flies and 30 minutes after treatment of cockroaches. Percent
mortality readings were made after 18-24 hours. Test
results are set forth in Table 3.
It is anticipated that, in the normal use of the com-
pounds of the present invention as insecticides, the com-
pounds will usually not be employed free from admixture or
-20-
:

1~41g6
dilution, but will ordinarily be used in a suitable formu-
lated state compatible with the method of application. The
insecticidal cyclopropanecarboxylates of this invention may
be formulated with the usual additives and extenders used
in the preparation of pesticidal compositions. The toxi-
cants of this invention, like most pesticidal agents, are
incorporated with the adjuvants and carriers normally
employed for facilitating the dispersion of active
ingredients, recognizing the accepted fact that the formu-
lation and mode of application of a toxicant may affect the
activity of the material. The present compounds may be
applied, for example, as a spray, dust, or granule, to the
area in which pest control is desired, the choice of appli-
cation varying of course with the type of pest and the
environment. Thus, the compounds of this invention may be
formulated as granules of large particle size, as powdery
dusts, as wettable powders, as emulsifiable concentrates,
as solutions, and the like.
Dusts are admixtures of the active ingredients with
finely divided solids such as talc, attapulgite clay,
kieselguhr, pyrophyllite, chalk, diatomaceous earths, cal-
cium phosphates, calcium and magnesium carbonates, sulfur,
flours, and other organic and inorganic solids which act
as dispersants and carriers for the toxicant. These finely
divided solids have an average particle size of less than
about 50 microns. A typical dust formulation useful herein
contains 10.0 parts of a-cyano-3-phenoxybenzyl 3-[~-(4-
:,
:

1:2604a6
chlorophenyl)vinyl]-2,2-dimethylcyclopropanecarboxylate,
30.0 parts of bentonite clay, and 60.0 parts of talc.
The compounds of the present invention may be made into
liquid concentrates by solution or emulsion in suitable
liquids, and into solid concentrates by admixtures with talc,
clays, and other known solid carriers used in the pesticide
art. The concentrates are compositions containing about
5-50~ toxicant, and 95-50~ inert material which includes
dispersing agents, emulsifying agents, and wetting agents.
The concentrates are diluted for practical application, with
water or other liquid for sprays or with additional solid
carrier for use as dusts. Typical carriers for solid
concentrates (also called wettable powders) include fuller's
earth, kaolin clays, silicas, and other highly absorbent,
readily wet inorganic diluents. A solid concentrate formu-
lation useful herein contains 1.5 parts each of sodium
lignosulfonate and sodium laprylsulfate as wetting agents,
25.0 parts of a-cyano-3-phenoxybenzyl 3-~-chloro-~-phenyl-
vinyl)-2,2-dimethylcyclopropanecarboxylate and 72.0 parts
of bentonite clay.
Useful liquid concentrates include the emulsifiable
concentrates, which are homogeneous liquid or paste
compositions readily dispersed in water or other dispersant,
and may consist entirely of the toxicant with a liquid
or solid emulsifying agent, or may also contain a liquid
carrier such as xylene, heavy aromatic napbthas, iso-
phorone and other nonvolatile organic solvents. For
-22-
~, .. .
~, ' , .
,

~2~04~36
application, these concentrates are dispersed in water or
other liquid carrier, and normally applied as a spray to
the area to be treated.
Typical wetting, dispersing or emulsifying agents used
in pesticidal formulations include, for example, the alkyl
- and alkylaryl sulfonates and sulfates and their sodium
salts; alkylamide sulfonates, including fatty methyl
taurides; alkylaryl polyether alcohols, sulfated higher
alcohols, polyvinyl alcohols; polyethylene oxides; sul-
fonated animal and vegetable oils; sulfonated petroleum
oils; fatty acid esters of polyhydric alcohols and the
ethylene oxide addition products of such esters; and the
addition products of long-chain mercaptans and ethylene
oxide. Many other types of useful surface-active agents
are available in commerce. The surface-active agent, when
used, normally comprises from 1-15% by weight of the
pesticidal composition but may comprise up to 30%.
Other useful formulations include simple solutions of
the active ingredient in a solvent in which it is completely
soluble at the desired concentration, such as acetone or
other organic solvents.
The concentration of the toxicant in the dilution
generally used for application is normally in the range of
about 2% to about 0.001%, but the composition may con-
tain up to 99.5% toxicant, from 0 to 99.5% of an agri-
culturally acceptable extender, and up to 30% of a surface-
active agent, the sum of these not to exceed 100%. Prior
.~
-23-

~ 2604S6
to dilution formulations may contain like amounts. Many
variations of spraying and dusting compositions in the art
may be used, by substituting a compound of this invention
into compositicns known or apparent to the art.
Pesticidal compositions may be formulated and applied
with other active ingredients, including other insecticides,
nematicides, acaricides, fungicides, plant growth regulators,
fertilizers, etc. In applying the chemicals, it is obvious
that an effective amount and concentration of the compound
of the invention should be employed. For agricultural ap-
plication the active ingredient of the invention may be
applied at a rate of 75 to 4000 g per hectare, preferably
150 to 3000 g per hectare.
-24-

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