CA1115288A - .alpha.-CYANO-M-(SUBSTITUTED PHENOXY) BENZYL CARBOXYLATE - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
.alpha.-Cyano-m-(substituted phenoxy)benzyl carboxylate of the formula,

Description

52~3 1 This invention relates to ~-cyano-m-(substituted phenoxy)benzyl carboxylate [hereinafter referred to as "cyanobenzyl carboxylate(s)"] of the formula, O (I) g CHoc-R
CN
,, wherein R2 is a 3-(2,2-dichlorovinyl)-2,2-dimethylcyclo-propyl or 1-(4-chlorophenyl)isobutyl group, Rl is a 3-chlorine or 4-chlorine atom, 3-methoxy~ 4-methoxy, 3-C2 4 alkyl or 4-C2 4 alkyl group when R2 is a 3-(2,2-dichloro-vinyl)-2,2-dimethylcyclopropyl group, and Rl is a 3-chlorine or 4-chlorine atom, 3-methoxy, 4-methoxy, 3-C1 4 alkyl or 4-C2 4 alkyl group when R2 is a 1-(4-chloro-phenyl)isobutyl group, and their preparation and use as an insecticide and/or acaricide.
An insecticide is one of the indispensable ' products for maintaining the agricultural products at a high level through the eradication of a wide variety of ; insect pests which inflict injuries upon agricultural crops. Further, an insecticide provides a most effective means for achieving the ob~ect of preventing infectious diseases from spreading by the extermination of those insects which transmit most of such diseases. Thus, the role played by the insecticide in maintaining an expected higher living standard of mank]nd is of great signifi-cance. Numerous eminent inseGticides have heretofore been ~l ~J~
~P',)?~

, 52i~3 1 invented and successfully put into actual use in various fields. On the other hand, however, organochlorine insecticides such as BHC (benzene hexachloride) and DDT [l,l,l-trichloro-2,2-bis(p-chlorophenyl)ethane] have become markedly restricted in their uses on account of the emergence of insect pests resistant to these compounds as well as the problems of environmental pollution and their toxi.city to various nontarget orga-nisms. The problem o~ resistant insects has become increasingly urgent also in other insecticides such as those of the organic phosphate ester type and the carba-mate type, which were expected to replace the organo-chlorine insectieides. Under the circumstances, advent of a new and more improved insecticides has been eagerly awaited.
Among the properties characteristic of an improved insecticide, those especially required at present, apart from a high inseeticidal activity, are eonsldered to be a low toxicity to nontarget organisms including men and animals, and substantial nonpersistence in order to minimize an environmental pollution~ Natural pyrethrin possesses a part of the characteristic properties required for an improved insectieide mentioned above, , because it has a low toxicity to men and animals and is ~easily decomposable under outdoor environmental condi-tions. Howe~er, as compared with organic phosphate esters and carbamate compounds, the natural pyrethrin is inferior in insecticidal activity, poorer in residual activity ,

- 2 -"

because of too rapid decomposition, and more expensive.
For these reasons, the use of natural pyrethrin is limited to such fields as household insect control and the like [E.M. Mrak (1973), "Advantages and Disadvantages 5 of Pyrethrum," in "PYRETHRUM" (J.E. Casida), Academic Press, New York and London, 1973, pp. 307-311].
A large number of researches were undertaken to make up ~or the defects of natural pyrethrin and, as the result, several superior synthetic pyrethroid 10 insecticides have been brought forth. Of these, especially those described in Nature, 248, 710 (1974) by M. Elliott et al., Brit. Pat. No. 1,413,491, and U.S. Pat. No.

3,996,244 are characterized by (1) outstandingly high insect~cidal activity and quick onset, (2) sufficient 15 resldual actlvity without environmental persistence as long-lasting as that of an organochlorine insecticide, (3) comparatively low toxicity to men and animals, and

(4) outstanding insecticidal activity against organic phosphate esters- and/or carbamate-resistant insect 20 pests. Consequently, investigations on the worldwlde scale are now being undertaken ln order to put these synthetic pyrethroids into practical use; in a few districts where the spreàding of resistant pests is becoming more significant, the actual use has already 25 begun.
However, as shown by J. Miyamoto in 13nviron-.mental Health Perspectives, I4, 15 (1976), pyrethroid insecticides including natural pyrethrin exhibit, in ~5;2~B

1 general, a high toxicity to fishes. Insecticides in no small proportion are used for controlling insect pests in paddy field, for controlling aquatic insect pests such as larvae of mosquitos and gnats, and for aerial application over the area scattered with lakes, ponds or rivers. It is predictable that application of the superior synthetic pyrethroid insecticides to the above-noted areas-will be restricted owing to their toxicity -to fishes. For this reason, reduction of the toxicity of pyrethroids agalnst fishes seems to be an urgent problem.
Considering that it might mark a great step toward a so-called ideal insecticide if it is successful to develop an insecticide having excellent properties inherent in pyrethroid insecticides together with a low toxicity to fishes, the present inventors conducted extensive studies and, as a result, found that the compounds represented by the general formula (I) have the characteristics which meet the requirements ~or the intended insecticide. Based on this finding, the present invention has been accomplished.
Although a part of the compounds o~ this invention have been disclosed, in a broad sense, in Brit.
Pat. No. 1,413,491, no specific description is found therein with respect to structural formula, physical constant, insecticidal activity, toxicity to fish, and - mammalian toxicity of the compounds o~ this invention.
While having outstanding insecticidal and L

' .

2~

1 acaricidal activities, the compounds of this invention are low in the toxicity to fishes (for example, carp, rainbow trout and bluegill). Accordingly, they are suitable for the control of aquatic insect pests such as those inhabiting, for example, paddy fields, lakes and marshes, ponds and pools, rivers, or forest regions scattered therewith. Since they exhibit also a low toxicity to warm-blooded mammals (for example, mice and rats) and a low phytotoxisity to crops, their use fields are very wide. Because of their high insecticidal activity and high residual activity, they are useful in controlling the following wide variety of insect pests, particularly in controlllng Nephotettix cincticeps which is resistant to conventional insecticides and requires for its control a new insecticide.
(1) In paddy field:
Hemiptera;
Delphacidae (planthoppers, delphacids) (for example, Sogatella furcifera, Nilaparvata lu~ens, Laodelphax str~atellus) Deltocephalldae (leafhoppers) (for example, Nephatettix cincticeps,-Tettigella viridis, Inazuma dorsalis) Aphididae (aphids) (for~example, Rhopalosiphum rufiabdominalis, Rhopalosiphum padi) Pentatomidae (stink bugs, shield bugs) ~for example, Nezara antennata, Aeschynteles maculatus, Leptoco_ixa corbetti, Eysarcoris ventralis) Lepidopt~ra (moths and bu~terflles); (for example, :
., ~:' 1 Chilo suppressalis, Tryporyza incertulas, Susumia . .
exiqua Cnaphalocrocis medinalis, Sesamia interens, ~ .
Parnara guttata) Coleoptera (beetles); (for example, Oulema oryzae, Echinocnemus squameus) Diptera (flies); (for example, Agromyza oryzae, chlorops oryzae, Hylemya platura) Orthoptera; (for example, Oxya yezoensis) Tetranychidae (spider mites); (for example, Oligonychus shin~y ii) (2) In lakes, marshes, ponds, pools, rivers:
For example, Aedes aegypti, Anopheles stephansi, Culex pipiens molestus, Culex pipiens pallens, Culioides -arakawae.
(3) In forest:
For example~ Dendrolimus spectabilis, Monochamus alternatus, Archips fumiferana, Oli~onychus hondoensis.
(4) Vegetables, fruit trees, woods:
Lepidoptera (for example, Plutella xylostella, Spod_ptera litura, Mamestera brassicae, Leucania separata, __ Ostrinia nubilalis, Pieris rapae, Papilio xuthus, Adoxophyes orana, A~rotis fucosa) A Hemiptera, (for example, M~ pers1cae, ~ gossypii, Brevicoryne brassicae, Toxoptera-citricidus, Diaphorina citri) Coleoptera (beetles); (for example, Phaedon brassicae, Oxycetonia ~ucunda, Anomala cuprea, Anomala rufocuprea) Diptera (flies); (for example, Hylemya platus, ~emya , ; 6 -:

j- 1 antiqua) Isoptera (termites), (for example, Coptotermes formosanus, Leucotermes speratus) Tetranychidae (spider mites); (for example, Tetranychus J~L e,in~ ar~n~

5 clnnavarinus, T. ulticae, T. kanzawai, Panonychus citri, P. ulmi, Aculus pelekassi) (5) Livestock:
For example, Boophilus microplus, Stomoxys calcitraus, Callitroga hominivorax.
, .

(6) Sanitary pests:
Mosquitos; (for example, Culex pipiens molestus, ulex pipiens pallens, Aedes aegypti, Anophelos stephansi) Flies; (for example, Musca domestica, Lucilia cae_ar, .
Boettcherisca peregrina) ;
15 Cockroaches; (for example, Periplaneta americana, .
P. fuliginosa, Blattella germanica) Gnats; (for example, Prosimulium hirtipes, Simulium aokii) ~ .
Fleas; (for example, Pulex irritans) Lice; (for example, _diculus humanus, Phthirus pubis) : ~ (7) Stored crops:
Coleoptera; (for example, Sitophilus zeamais, Tribolium i~ castaneum, Tenebrio _olitor) .
Lepidoptera; (for example, Ephestia cautella) ` 25 Acarina; (for example, Tyrophagus dlmidiatus) ~:
The esters of this invention represented by the general formula (I) exist in the form of geometric isomer due to the steric con~iguration of the carboxylic .

- 7 -- ~ .

~SZ~38 1 acid and in the form of optical isomer due to the asymmetric carbon atoms in both carboxylic acid and alcohol components. An ester prepared by ordinary methods is a mixture of such isomers. All of the isomers are included within the scope o~ this invention.
A main object of this invention is to provide a novel cyanobenzyl carboxylate (I) which is useful as insecticide and acaricide.
Another object of this invention is to provide a procedure for preparing such a cyanoberizyl carboxylate (I)-A ~urther object o~ this invention is toprovide an insecticidal and/or acaricidal composition containing such a cyanobenzyl carboxylate (I).
These and other objects and advantages of the ;~
invention will become apparent from the foregoing and the subsequent descriptions.
The cyanobenzyl carboxylate (I) of the present in~rention may be prepared by various methods, of which typical examples will be described below.
Synthetic method A,~ by the reactlon between an alcohol and a carboxylic acid halide.

An alcohol represented by the general formula, .
~o~
` 1 CHOH
:; I
CN

: ': ~

, ~ ,

- 8 -.

: . : .

2~8 ., .

1 (wherein Rl is as defined above) and an acyl halide, preferably acyl chloride, represented by the general . formula, O

'' ' (wherein R2 is as defined above and X represents a halogen ~ 5 atom) are allowed to react in the presence of an organic .:
tertiary base (for example, triethylamine, pyridine) in an inert solvent (for example, benzene, toluene, ether or hexane) at 30 to 100C. for 30 minutes to 10 hours to obtain the intended ester.
Synthetic method B, by the reaction between an .. ~.:
alcohol and a carboxylic anhydride.
: _ .
A mixture of an alcohol represented by the general formula, CN

. ~ . (wherein Rl is as defined above) and a carboxylic anhydride represented by the general formula, O ,. ,:
2 - C)2 .. . ~

~ (wherein R2 1s as defined above) is allowed to ........

: - 9 - :.
, , . . .
'' :

1 react in an inert solvent (for example, benzene, toluene, hexane or acetone) at -20 to 100C. for 1 to 10 hours to obtain the intended ester.
Synthetic method C, by_the reaction between an alcohol and a carboxylic acid.
A mixture of an alcohol represented by the general formula, - .
~0~
Rl CHOH

CN

.
(wherein Rl is as defined above) and a carboxylic acid represented by the general formula, ' ':

O
.11 ' '.
R2 ~ C - OH
' ' .

(wherein R2 is as defined above) is allowed to react in an inert solvent (for example, benzene, toluene or xylene) in the presence of a dehydrating and condensing agent (e.g., dicyclohexy]carbodiimlde) at -30 to 100C. for 30 minutes to 10 hours to obtain the intended ester.
3ynthetic method D, by the reaction between a_halide and an organic tertiary base salt of a carboxylic acid.
A mixture of a halide represented by the general formula, .
' ~ 52~3~

e~O ~ .
R ~
l CH-Y
CN

1 (wherein Rl is as defined above and Y represents a halogen atom) and a carboxylic acid represented by the general formula, ~ ' :

O ,.
I~ :''''.
R2 ~ C - OH

(wherein R2 is as defined above) is allowed to react with an organic tertiary base (e.g., triethylamine or trimethylamine) in an inert solvent (for example, . .
acetone, benzene or dioxane) to convert the carboxylic -acid into its salt and the whole mixture is allowed to react at 0 to 150C. for 30 minutes to 10 hours to obtain the intended ester.
, Synthetic method E, by the reaction between .
. .;, . .
a halide and an alkali metal salt of a carboxylic acid A mixture of a halide represented by the .. ... .
~ general formula, ~ ~
~0 ~ ' ' ~' '.
. .
~l CH-Y
I
CN

- .

.

l (wherein Rl and Y are as defined above) and an alkali metal salt of a carboxylic acid represented by the general formula, R2 ~ C - OM

(wherein R2 is as defined above and M represents an alkali metal) is allowed to react with heating in a two-phase system of water and an inert solvent (for .
example~ toluene, heptane or benzene) in the presence of a phase transfer catalyst (for example, tetra-n-butyl-ammonium bromide or benzyltriethylammonium chloriùe) at : 0 to 150C. for 30 minutes to 10 hours to obtain the intended ester.
Synthetic method F, by the reaction among an aldehyde, an alkali metal cyanide and an acyl halide.
F-l. A mixture of an aldehyde represented by the general formula, ~~ ' , ' : ' ~ Rl CHO

':
(wherein Rl is as defined above), an alkali metal cyanide and an acyl hal'de represented by the general formula, ' ~ ' '.

- 12 ~

~sz~s : : ~

1 (wherein R2 and X are as defined above) is allowed to react in an inert solvent (e.g., benzene or toluene) in the presence of a phase transfer catalyst (e.g., dibenzo-18-crown-6 or dicyclohexyl-18-crown-6) at -30 to 150C.
for 30 minutes to 10 hours to obtain the intended ester.
F-2. A mixture of an aldehyde represented by the ;
general formula, ., ~~\ ''''.
Rl CH0 . . .
(wherein Rl is as defined above), an alkali metal cyanide and an acyl halide represented by the general ~ormula, ~. "....

O
Il . '. .

(wherein R2 and X are as deflned above) is allowed to react in a two-phase system of water and an inert solvent (for example, benzene, hexane or toluene) in the presence of a phase transfer catalyst (e.g., tetra-n-butylammonium bromlde or benzyltriethylammonium chloride) at -30 to 100C. for 30 minutes to 10 hours to obtain the intended ester.

.
The cyanobenzyl carboxylates obtained by any : .

' ' ~s~

1 of the above methods can be purified, if necessary, by such a means as chromatography or distillation.
The ~-cyanobenzyl alcohol, one of the starting materials, is easily obtained from a corresponding aldehyde by the method described by C. Hilgetag e~ al.
ln "Preparative Organic Chemistry", p. 875. The halide can be obtained in good yield from the above alcohol by using a halogenating agent such as phosphorus halide according to the procedure described in "Organic Synthesis", Coll. Vol. III, p. 793. The carboxylic acid chloride and the carboxylic anhydride can be obtained in good yields from the carboxylic acid by the method described by R.B. Wagner et al~ in "Synthetic Organic Chemistry", p. 546 and p. 558.
In Table 1 are shown specific examples of the cyanobenzyl carboxylates ~I) synthesized by the above methods.
, :
' .-, ' ~ '' :' .. - : - -. . : ...... , .. , . , , :: : . , .

~s~

~ ~o ~ ~o tq a\ L~
.~ ~ ~o ~ ~ o ~ - :
u~ . ~. ~ . r~
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^~ ^ ~, a~
CO~D ~ ~ O ~D
. ~. ~ . ~ . ~1 0~ .CC~ ) . 03 .
: U~~ U~ L
,~
vz~ ~z ~ væ ~ væ
o ~ o ~, V ~ C~ : , _ ~
o . 00 o o r~
~ X o O . ,.. ~
o o "
~1 ~ ~ ~ ~ C) V ~ ~1 V V >, ~ \ / ~, ~ ..
a) a~ \ / N ~ ~ ~ N
~1 ~ V S~ V
~ X ~ O ~ ' ~ O
E-~ ~ \~ ~ ~ O \X~

~ ~ ' V ~ ~ ~ V V ~ ~ ~
Ei = V ~ ^ X
~ 0 0~ 0~ 0 ~ ~ , h ~ V--V .~ V--C~ S l c) ~ ~ ' $o~
~ ~ O S ~ ,~ ~;
.~, u~ ~ O :," ' C~ ~ C) V ~ ~ ,, "
_, ~ _ - ' ' :' ra ~, ~i ~ ' ' ':
. O o O
V P~ ,, . ~ ~ , , .'.
,~ ~ S
C~
~-rl .
` ~ ':
- 15 - ; ;:

~ 521~3 _ 3 ~J 3 ~ 3 r~l3 r-~ 3 r-l 3 ~

V V V V V V
~0 ~ ~ ~D ~) oo~ ~ O C03 ~VZ~-1VZ '~VZI--IVZ ~V~Zr~lVZ :' O a:~ O ~ O
V ~ ~ V
_ ~ ~ ~ .

O O O
~ O O
~ a ~ .. A . ...
~, ~ 1. V V
V V o \ / ~,--~ V V
V ~ ~ ~ /
\ / , ~ O It N ~ V N

V ~ ~ C XO O \ ~ O
X~ ~ ~ ~V~ /V
V V ~ V ;~, ~ \ / ~1 ^ ?~ S I V C) S
V' c) ~U O ~C /\:~ I c) (I) ~ \
X/ \~ ~ d V V I ~ ~ - -C~ VI ~ ~ O--V ,~
~~ I C) I ~ t~l :~, O a V
O = V ~ O X ^ ~C I X ^ ~ :
O ~ O O O ~ O
q ~ ~ ~ (.)--VZ S I ~ ~ z a) o ~ ,~ v--v ~V--V ~ ~ h O O ~ ~ ~ o .~

'o ~I c)i .C ~ 1:~ ~ ~ Q- :' ~ a ~
~ I ~ I ~ o ,1 ~0 , ,, ~ iJ ~,-~ ~ O ~ I ~ o :: ~ V ~ ~ ~ V ~ V
-; ~ ~
~ . .

: ' .

. ... . .. - ., . - .- .. .. , . .'-- , .
... . . . . . ... . .. .. ~ ... . ... . :. . ....

~52~

_ . , ,1 ~ ~ ~ ~ o ~" ~ ~ a~ ~
N~ I . O t_ _ 0. IS~ . 3 ~ ~ ~
~I L~ ~

~1 V V V V V
~` V ^ ~
~o C~ o, I cc~ o .~ .~ Ø~ .0 .
~O (~1 ~ ~O ~ ~O ~) ~ ~O ~ ~O tr~ ~5 ~3 N
~ vz ,I vz ~ væ ,~ vz ~ vz ~ vz o ~ o ~ o V ¢I V ~, V
.
~
o o ~o ~o ~ , L~ o LS~
; ~J o LP ~ p N ~
v\ v l v ~ l v v v ^ ~ / ^ v ~`
Il ~V ~1 11 V.~ X ` ~ ~ V t~ N rl V ~,r ~ .
V~ /V~ ~ V, X ~ ~ V V
V '' h \ / R S ~ I v ~ ~
~ ~ ~ o o I V O o / \ ~ ~d O
V Vtd ~ ~ / \ ~:c,r td ~ v V t~ S
~ v v:" c~ a.) I I ~ o O--V C) ~ 1 ~0_~. V
I N ~ O--V I N ?~I ~ 7 X I ~ ~ x ~ æ
V---V~N O ~ Z?~N O V--V O N O
v_ v ~) I C.) ~ tl~ I C) t~
O ~ ~I tl) I ~ ~1 ~) O ~1 ~1 (1) ' .
~1 ~ td ~1 ~ tdt~ ~ ~ td ~, ~ ~, ,~ ~ o ~ ~ ~ o N ~ ~rl Q, N O ~rl ~ V Q~
v ~7 ~ v E~ ~ ~ '~ ~ ~ ~
N ~ t~ --~ N ~ t~ ' N C~
V~. ~; ~ C) v t~ C~ V E~ t~
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N
m ¢~
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~o ~ ~ ~ ~ ~
L~ CO~O O C~ 3 '~O ~D ~I L
3 L~ . LS~ . Lr~ LS~. LS~
L5~ ~--1 LS~ l 3 r-l S r-l 3 r-l C~ V ~ V

C) ~ OCOCO ~ Oo~
. o. ~ . o D . Lr~ . ~D .LS~ . ~ .

::~ V Z; ~I C~l Z ~ C) Z r~l V Z ~ C~ Z ~ C~ Z O ~ O ~ O

00 ~ '~
Lr~ ~O
~ t-- . r--Lr~ Lr~ LS~

O O O

v\ v v ~l^
~ N ~i ~ ~ : `
C~ N N
V V ~ ~' ~ ~ ~ ~ ' -\ / O Or-l 3 ~ ~ ,a ~
V ~ ~iV NO a:l V o ~1 -r m ~,j i~ r ~
~ v c~ ~d ~ L ~ c~
o~ r 1 ~ ~ m ~ ~ o I ~- ~ 0 ^ ~ x m I cq "--" o ~ o I X ~ o=v _3 0~ ~ ~ o ~ m ~a~ a) I ~ a) o ~ ~ ~ ~' ~ ~ v--v ~ ~ ~ R. ~ J ~ o o v~ ~ ~ s o s s r I ~ ~
V ~ /~ ~ _ --~ ~ ~ C) V ~ ~ V

_. _ _ _ _ .
~ O ~
~ _ .

~ ~, v ~ `

_ 18 -zl~

v v v v v v o ~ ~ ~ ~ ~ ~ r--c~O Oco ~ ~r ,1 . ~ . o 5 v ~;~ v z :~s v z ~ c~ v ~ v z O ~ O ~ O ~d ¢, c~
-~D O ~

u`~ o o :
N N
N a N 1~ N a S:~ ~

~1 N N
V N ~ O ~ ~ ~ (1) . .

v o ~ o ,l ~D x ?. ~
-- I U~ V -- V
V--V I ~~ O =V~~ u~ Y ,~
rl O _ V
O = V ~ 0~ 50~ ~ o X ,~
O O O P~ Z;S:~ ~ I .
CP ~D,V-V p~ V pp ~ ~

0 ~1 C) ~ ~ ~ _ , ~ ,~

V ~ V N U ~ N

N (Y) .

~ N~ m ¢

.
___ _ _ __ _ .

.

, - - -L~ r~ ~o o u~ r~ ~ ~ ) ~ -0 u~r~o ~ ~ o ~ v v v v v ~ V Z -1 V Z~ V z~V z ~ V z -1 V Z
1~ V l:'~ V ~ V
r.~O r.~O ~ . ' ' ~o 3 ~D :
U~ ~ ,U~
.~ .~ .
o o U~
o ,~
.

N N
V ~ -1. Q ~ ~C (I~
~O t~ V ~I O ~ . ~ , V ,g ~d .
~ ~v ~ v~-v '~
~ ~V V C~
V-- V ~ o ~ ~ ~ o I I o 1 0~ V--C) I U~ 0 O--V ^-.-1 1 ~-.~ I I .-1 ~^O--V ~-- ~ Z ^ ~`
OX ' o O '~ 1~ V--V X
x_ z D,v_ . o ~ s ~ ~ ~ P. V ~2, .,~.
V ~i ~ V ~ t~, V

.~ .~ .~
. ..

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. . :
~ .

3 ~ Lr~
O ~ ~ ~3 V V V V
~1 o~ ~n ~ co ~`I~1 3 ~ . ~ .~ . .. ..
. .
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O ~ o ~
ti; V ~ V
o o . ....
~D
U~
~i .

~i ~ : :
a ~
' '. ~.
. .:
~I
~I V ~J N
~1 ~ 1 v ~I N ~ ~ a>
I ~ ~ (L) 0~~ V 0~ ,. .
~, ' V o ~,X ~ ~d V--V
~ ~ ~ I C~
V--V ~ td0--V I ~d O--V I o O I o ;~ . `
I rl~C Z ~rl ~ v--v ~
~ - z ~
~ o ~ s T ~ Q. 1 ~ ~l o ~

~, ~ , a) c) ~ ~ ~

~C I I V I I
v E~

r-l _ ~_ . - .
,.. ~ ~' Z~8 l Practical and presently preferred embodiments og the preparation of the cyanobenzyl carboxylate (I) are illustratively shown in the following examples.

Example l (Synthetic method A) To a solution of 1.02 g (4.0 mmoles) of m-(m-methoxyphenoxy)-a-cyanobenzyl alcohol in lO ml of anhydrous benzene, was added 0.63 g (8-.o mmoles) of pyridine. To the resulting mixture, with stirring and maintaining a temperature below 5~. in an ice bath, was added dropwise a solution of 0.97 g (4.2 mmoles) of 2-(p-chlorophenyl)-isovaleryl chloride in 5 ml of anhydrous benzene. After the addltion was completed the reaction mixture was allowed to react at room temperature and stirred overnight. After dissolution of the precipitated pyridine hydrochloride by addition of water to the reaction mixture the aqueous layer was separated. The organic layer was washed with 5% hydrochloric acid, saturated aqueous sodium hydrogen-carbonate solution and then saturated aqueous sodium chloride solution. After drying over anhydrous sodium sulfate, the organic layer was concentrated under reduced pressure. The residue was chromatographed on silica gel to glve 1.50 g of m-(m-methoxyphenoxy)-~-cyanobenzyl 2-(p-chlorophenyl)isovalerate as a pale yellow liquid (yleld 84%; n22 0 1.5663).

Example 2 (Synthetic method B) To a solution of 1.27 g (5.0 mmoles) of m-(m-. ~ ,-' .

- 2~ ~

~ sz~

1 ethylphenoxy)-~-cyanobenzyl alcohol in 10 ml of toluene, was added 2.00 g (5.0 mmoles) of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid anhydride.
The resulting mixture was stirred at room temperature for 3 hours and then heated under reflux for an hour.
After cooling, the reaction mixture was washed with 5% sodium hydroxide aqueous solution to remove the carboxylic acid. The organic layer was washed with saturated aqueous sodium chloride solution and dried over 10 anhydrous sodium sulfate. The solvent was evaporated ~
under reduced pressure to give 1.82 g of m-(m-ethylphenoxy)- ;
a-cyanobenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclo-propanecarboxylate as a pale yellow liquid (yield 82%;
n20 0 1.5600).

Example 3 (Synthetic method C) To a solution of 1.02 g (4.0 mmoles~ of m-(p-methoxyphenoxy)-~-cyanobenzyl alcohol and o.84 g (4.0 mmoles) of 2,2-dimethyl-3-(2,Z-dichlorovinyl)cyclopropanecarboxylic acid in 10 ml of anhydrous benzene, was added 1.65 g (8.o mmoles) of dicyclohexylcarbodiimide. ~he mixture was stirred overnight. The precipitated dicyclohexylurea was ~ -removed by filtration and the filtrate was concentrated.
The residue was purified on silica gel to give 1.55 g of m-(p methoxyphenoxy)-a-cyanobenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate as a pale yellow liquid (yield 87g; nD 1.5552).

::
' " '.
' .

28~3 1 Example 4 (Synthetic method D) To a solution of 1.51 g (5.0 mmoles) of m-(m-methylphenoxy)-a-cyanobenzyl bromide and 1.28 g (6.0 mmoles) of 2-(p-chlorophenyl)isovaleric acid in 10 ml of acetone, with stirring at 15 to 20C., was added dropwise a solution of 0.81 g (8.0 mmoles) of triethylamine in 5 ml of acetone. Thereafter, the mixture was refluxed for 2 hours and allowed to cool to room temperature. The reaction mixture was filtered to remove the precipitated triethylamine hydrochloride and the filtrate was concent-rated under reduced pressure. The residue was admixed with 10 ml of benzene and treated in the same manner as in Example 1 to give 1.99 g of m-(m-methylphenoxy)-a-cyanobenzyl 2-(p-chlorophenyl)isovalerate as a pale yellow liquid (yield 92%; n21 0 1.5648).

Example 5 (Synthetic method E) A solution of 1.72 g (5.0 mmoles) of m-(m-tert-butylphenoxy)-a-cyanobenzyl bromide in 10 ml of toluene and a solution of 1.27 g (5.5 mmoles) of sodium 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate in 7 ml of water were mixed. After addition of 0.081 g (0.25 mmoles) of tetra-n-butylammonium bromide~ the mixture was~stirred for 4 hours at 70 to 80C. The reaction mixture was washed with satur~ted aqueous sodium chloride 25 -solution~ dried over anhydrous sodium sulfate. The solvent was e~aporated under reduced pressure to give 2.24 g of m-(m-tert-butylphenoxy)-~-cyanoben~yl 2,2-dimethyl-3-- 2~

': ;

:
.. . - .. .. . .

~s~

(2,2-dichlorovinyl)cyclopropanecarboxylate as an orange liquid (yield 95%; n21 0 1.5518).

Example 6 (Synthetic method F-l) To a suspension of 0.37 g (7.5 mmoles) of sodium cyanide and 0.09 g of dibenzo-18-crown-6 in 10 ml of anhydrous benzene, was added dropwise, with stirring at room temperature, a solution of 1.16 g (5.0 mmoles) of m-(p-chlorophenoxy)benzaldehyde and 1.19 g (5.25 mmoles) of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride in 10 ml of anhydrous benzene. Thereafter, the mixture was further stirred overnight. The reaction mixture was washed with a saturated aqueous sodium chloride solution and the solvent was evaporated under reduced pressure. The residue was chromatographed on sllica gel 15 ~ to give 1.92 g of m-(p-chlorophenoxy)-cl-cyanobenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate as a pale yellow liquid (yield 85%; n20 0 1. 5700).
'~

Example 7 (Synthetic mekhod F-Z) To a solution of 0.37 g (7.5 mmoles) of sodium , cyanide and 00012 g (0.037 mmoles) of m-phenoxybenzyl-.
triethylammonium chlcride in 5 ml ~of water, was added dropwise with stirring at room~temperature a solution of 1.16 g (5.0 mmoles) of m-(p-chlorophenoxy)benzaldehyde and 1.19 g (5~.25 mmoles) of d-cis-2,2-dlmethyl-3-(2,2-dlchloro-;~ 25 vinyl)cyclopropanecarbonyl chloride in 10 ml of toluene.
The resulting mixkure was stirred for 5 hours at room ::
: :.

.

52~

1 temperature and then washed with saturated aqueous sodium chloride solution. ~he organic layer was dried over anhydrous sodium sulfate and concentrated to give 2.05 g of m-(p-chlorophenoxy)-~-cyanobenzyl d-cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclo~ropanecarboxylate as a pale yellow liquid (yield 91%; n23 1.5712).
In applying the compound of this invention as an insecticide or acaricide, it can be employed as such without blending with other ingredients, but generally it is used in the form of pesticidal composition by blending with a carrier to improve its handling quality as a pest controlling agent; and such a composition may be further diluted prior to use, if necessary.
In preparing pesticldal compositions, the 15 compound of this invention may be formulated in a manner `
similar to that used in customary pesticides by use of techniques well known to those skilled in the art and no other special precautions are necessary. The compound of this invention may be employed for the intended use in any of the forms such as emulsifiable concentrate, wettable powder, dust, granule, flne granule, oil preparation, aerosol, heating fumigant (mosquito coil, electrically heating mosquito mat), fuming preparation such as fogging~
non-heating fumigant, poisonous bait, etc.
The compounds of this lnvention may be used in combinations of two or more members to enhance the insec-:
ticidal and acaricidal activity. The actlvity may also be ~ ~-enhanced by incorporating with synergists~for pyrethroids, ,:' l such as ~-[2~(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene (referred to as "piperonyl butoxide"), l,2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benzene, 4-(3,4-methylenedioxyphenyl)-5-methyl-1,3--dioxane, N-(2-ethylhexyl)-bicyclo[2,2,1]hepta-5-ene-2~3-dicarboxyimicle, octachlorodipropyl ether, isobornyl thiocyanoacetate, and other known synergists effective for allethrin and pyrethrin.
Although highly resistant to light, heat and oxi-dation, the compound of this invention may be further stabi-lized against severe oxidative conditions by incorporating with a suitable amount of stabilizers. Suitable stabilizers are antioxidants and ultraviolet absorbers including phenol derivatives and bisphenol derivatives such as BHT (2,6-di-tert-butyl-4-methylphenolj and BHA (2-tert-butyl-4-methoxy- . :
phenol); arylamines such as phenyl-a-naphthylamine, phenyl-~-naphthylamine and phenetidineacetone condensate; and benzophenone compounds.
The compound of this invention may be formulated to provide multipurpose compositions with desirable .
activities and, in some cases, even synergistic activities b~ mixing with various physiologically active substances including~ for example, allethrin, N-(chrysanthemoxymethyl)-3, L~, 5,6-tetrahydrophthalimide, 5-benzyl-3-furylmethyl chrysanthemate (referred to as "Chrysron"), 3-phenoxybenzyl chrysanthemate, 5-propargylfurfuryl chrysanthemate, 2-methyl-5-propargyl-3-furylmethyl cArysanthemate, d-trans-, ; :
.
d-cis,trans-chrysanthemates thereof~ pyrthrum extract~
d-trans- or d-cis,trans-ester of d~allethrolone, ZB~

1 other known cyclopropanecarboxylate esters; organophosphorus insecticides such as 0,0-dimethyl-0-(3-methyl-4-nitrophenyl) phosphorothioate (referred to as "Sumithion"), 0,0-dimethyl-0-4-cyanophenyl phosphorothioate, and 3,0-dimethyl-0-(2,2-dichlorovinyl) phosphate (referred to as dichlorvos); carbamate insecticides such as l-naphthyl-N-methylcarbamate, 3,4-dimethylphenyl-N-methylcarbamate, m-tolyl-N-methylcarbamate, 0-sec-butylphenyl-~-methyl-carbamate, 0-isopropoxyphenyl-N-methylcarbamate, 3-methyl 4-dimethylaminophenyl-N-monomethylcarbamate, and 4-dimethylamino-3,5-xylylmethylcarbamate; other insecti-cides, fungicides, nematocides, acaricides, herbicides, plant growth regulating agents, fertilizers, microbial pesticides described in E.S. Raun et al., J: Eco. Ento., 59 (3), 620 (1966), insect hormones, and other agricultural chemicals.
The insecticidal and/or acaricidal compositions accordin~ to this invention contain 0.001 to 80.0%, pre-ferably 0.01 to 50% by weight of an active ingredient.
~ Practical embodiments of the insecticidal or acaricidal composition according to this inven~lon are illustratively shown in the following examples, wherein parts and percents are by weight.

:' Formulation Example 1 25 ~ Each 10 parts of the compounds (1) to (19) of this invention were mixed with 15 parts of "Sorpol 3005X"

(a mixture of nonionic surfactant (polyoxyethylene phenyl , .

~s~

1 phenol derivative and anionic surfactant (alkyl aryl sul-fate)) and 75 parts of xylene. The mixture was thoroughly stirred, mixed, and dissolved to obtain respective 10% emul-sifiable concentrates.

Formulation Example 2 Each 0.3 part of the compound (1), (2)~ (3) and (10) of this invention was dissolved in 20 parts of acetone, admixed with 99.7 parts of 300-mesh clay, stirred thoroughly, and freed from the acetone by evaporation to yield 0.3 %
dust preparat:Lons of each compound.

:
Formulation Rxample 3 Each 0.2 part of the compounds (1~, (2), (3) and (10) of this invention was mixed with 2 parts of m-tolyl-N-methylcarbamate, dissolved in 20 parts of acetone, admixed with 97.8 parts of 300-mesh clay, mixed by thorough stirring, and freed from acetone by evaporation to obtain 2.2% dust preparation of each compound.

,~
Formulation Example 4 Each 50 parts of the compounds (1), (2), (3), (4), (8), (10) and (12) of this invention was well mixed with 5 parts of "Sorpol 5029-0" (anionic surfactant), admixed with 45 parts of 300~mesh diatomaceous earth, and thoroughly mixed in a~grinding mill to obtain 50% wettable powder of each compound.

~.

~5~

1 Formulation Example 5 Each 10 parts of the compounds (1), (2), (3), (Ll), (8), (9), (10) and (12) of this invention was admixed with 5 parts of "Sumithion", mixed thoroughly with 5 parts of "Sorpol 5029 0", admixed with 80 parts of 300-mesh diatomaceous earth, and thoroughly blended in a grinding mill to obtain 15% wettable powder of each compound.

Formulation Example 6 To each 2 parts of the compounds (1) and (10) of this invention, was added 2 parts of sodium ligninsul-fonate (a binder) followed by 96 parts of clay (an extend-er). The mixture was thoroughly blended in a grinding mill, admixed with water in an amount of 10% of the resulting mixture, again mixed thoroughly, then granulated by means of a granulator, and dried in air stream to obtain 2% granule of each compound.
~' ', Formulation Example 7 0.5 Part of the compound (1) of this invention was dissolved in illuminating kerosene to make a total of 100 parts to obtain a 0.5% oil spray.

Formulation Example 8 A mixture of 0.5 part of the compound (1) o~
this invention and 0.5 part of piperonyl butoxide was dissolved in purified kerosene to make a total of 100 parts to obtain a 0.5% oil spray.

.
_ 30 _ , , . . .. .. . . ., , ;.: - . , : ., . . ~, .

1 Formulation Example 9 A mixture of 0.1 part of the compound (1) of this invention and 0.2 part of dichlorvos was dissolved in purified kerosene to make a total of 100 parts to obtain a 0.1% oil spray.

Formulation Example 10 Each 0.4 part of the compounds (1), ~4), (10) and (15) of this invention, 0.2 part of "Chrysron", 7 parts of xylene and 7.4 parts of deodorized kerosene were mixed to form a solution. An aerosol container was filled with the above solution and fitted with a ~alve portion through which 85 parts of a propellant (liquefied petroleum gas) was filled under pressure into the container to obtain an -aerosol preparation containing o.6% of active ineredient.

Formulation Example 11 Each 0.4 part of the compounds (3), (13~ and (15) of this invention, 0.5 part of "Sumithion"~ 7 parts of xylene and 7.1 parts of deodorized kerosene were mixed to form a solution. In the same manner as in Formulation Example 10, an aerosol preparation containing 0.9% of active ingredient was obtained from the above solution.

Formulation Example 12 0.4 Part of the compound (1) of this in~ention, 2.0 parts of piperonyl butoxide, 6.2 parts of xylene and 7 parts of deodorized kerosene were mixed to form a ~$~

1 solution. An aerosol preparation containing 0.4% active ingredient was obtained in the same rnanner as in Formula-tion Example 10.
The outstanding insecticidal and acaricidal activity and surprisingly low toxicity to mammals and ~ishes of the compounds of this invention are illust-rated below with reference to Test Examples. In Test Examples, reference compositions were prepared similarly to the test compositions using known compounds shown in Table 2.

.

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Z; ~; Z; Z:

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V . ..... ...
r l C~ O
C~ r--l r~ V

~/ m ~' ' / \ '`' ~/ ~C ~\0/ V V
X V V / V ~ V
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X
X~ o~O 0~o 0~ O
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1 Test Example 1 Each of the emulsifiable concentrates, described ln Formulation Example 1~ containing the present compounds (1), (3), (4), (6), (10), (12), (13) and (15) was diluted with water to an active ingredient content of 10 ppm. One hundred milliliters of each emulsion was placed in a 180-ml plastic cup and 30 third-instar larvae of Aedes aegypti were released in each cup. After 24 hours, 100~ mortality was observed in every cup.

Test Example 2 Each of the emulsifiable concentrates containing the present compounds (1), (2), (4)` and (10), described in ~ormulation Example 1, was diluted with water to ~our levels of active compound content. Using a turn-table, each emulsion was sprayed over 180-ml plastic cup planted with rice plant at a rate of 15 cc/2 cups. After air-drying, the rice plant was covered with a wire-screen cage and 15 female adult Nephotettix cincticeps resistant to carbamate compounds were released in the cage. After 24 hours, the dead and alive were observed to determine . .
the mortality. Median lethal concentration (LC50 (ppm)~
-was estimated from the mortality obtained by the tests repeated three times.

.
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- ~ ~
, l~lL5Z8B

Compound LC50 (ppm) Compound of this invention " (1) 5.0 " (2) 6.2 " (4) 7.0 ~ (10) 15.0 Reference compound (B) 18.0 " (K) 350.0 1 Test Example 3 Each of the emulsifiable concentrates containing the present compounds (1~ to (19), described in Formulation Example 1, was diluted with water to an active ingredient content of 500 ppm. Kldney bean plant leaves were immersed ln the emulsion for one minute, air dried and placed in a polyethylene cup of 10 cm in diameter and 4.5 cm high, together with 10 second-instar larvae of Spodoptera litura After 2 days, the leaf area fed by the insect was estimated and found that the injury was less than that of untreated.
:
:
Test Example 4 Each of the emulsifiable concentrates containing the present compounds of (1), (2), (10) and (11), -~
described in Formulation Example 1, was diluted with water to an active ingredient content of 500 ppm. The emulsion (50 cc) was sprayed over a mandarin orange seedl-ing planted in a 9 cm pot and parasitized by Panonychus o~tri in every growth stage After 10 days, the number of - 37 - :-:

~ 52~ ~

l female adults on the plant was counted and rated according to the following criteria:
++: 0-9 female adults are parasitic on one plant, +: 10-30 female adults are parasitic on one plant, -: 31 or more female adults are parasitic on one plant.

Compound Rating Compound of this invention (1) t+
(2) ++
(10) +~
( 11 ) ++
Reference compound (D) ~ .
(E) - . :
( 1~ ) - ' ' (G) (H) (J) (K) (L) - :' Test Example 5 Each of the dust preparations described in Formulation Examples 2 and 3 was applied at a rate of ;:~
3kg/lO are to rice plant grown in a 1/100,000-are Wagner : :~
: 10 pot. The plant was covered with a wire-screen cage and 15 female adults of Nephotettix cincticeps resistant to ;~ - 38 _ l carbamate compounds were released in the cage. The pot was kept in a greenhouse and after 24 hours, the dead and alive were observed. Mortalities in mean values of three repeated tests for each compound were as shown below.

Compound Mortality (%) Compound of this invention (1) 100 (2) lO0 (3) lO0 (10) 100 ' '' Reference compound (K) 3 Test Example 6 Each of the wettable powders containing the present compounds (l) - (4), (10) and (12), described in Formulation Example 4, was diluted with water to an active ingredient content of 400 ppm. The diluted preparation was applied to rice plant grown in a 180-ml cup a~ a rate of 15 cc/2 cups. After air-drying, the plant was covered with a wire screen cage and 15 female adults of Laodelphax striatellus were released in the cage. After 24 hours, the .
dead and alive were observed and a mean mortality of three repeated tests was obtalned.

: ' . . : ~ ' ~

~S2~

Compound Mortality (%) Compound of this invention (1 ) ' 100 (2) lO0 (3~ lO0 (4) lO0 (lO) I00 (12~ lO0 Reference compound (F) lO
.
(G) lO

(H) lO
'~ .
l Test Example 7 Each of the wettable powders described in Formulation Examples 4 and 5 was diluted with water to an active ingredient content of 500 ppm. Five rice seedling, 5 lO days after sowing, were dipped in the preparation for ;
one minute and air dried. The treated seedlings and lO
third-instar larvae o~ Chilo suppressalis were placed in a plastic cup of 55 cm in diameter and 3~5 cm high. After ~lO days, 100% mortality wa~s observed in every case.

Test Example 8 To a lO0-cc beaker containing lOO ml of distilled water, was added 50 mg of each of the granule preparations described in Formulation Example 6. 30 Third-instar larvae of Aedes aegypti were released in each beaker.

.

: : . .. : .

1 After 24 hours, 100% mortality was observed in every case.

Test Example 9 According to Campbel's turn-table method [Soap and Sanitary Chemicals, 14, No. 6, p. 119 (1938)], to a group of about 100 adult houseflies was sprayed 5 ml of each of the oil preparations described in Formulation Examples 7, 8 and 9 to expose to the descending mist for 10 minutes. After 24 hours, 100% kill was observed in every case. ~-..
Test ~xample 10 A glass Petri dish of 21 cm in diameter, with a thin coating of margarin on the inside wall was sprayed with each of the aerosol preparations described in Formulation Examples 10, 11 and 12 for 2 seconds from a distance Or 10 cm. Ten male adults of Blattella Q__manica were released in each treated dish and covered with gauze. Qfter 24 hours, 100% kill of the cockroaches was observed in every case.
' ~, .

Test ~xample 11 (Residual activity test) The emulsifiable concentrate containing the present compound (1), described in Formulation Example 1, was diluted with water to an active lngredient content of ; 400 ppm. Rice plant grown in a Wagner pot was sprayed with 20 cc of the emulsion. After air-drying, the plant was covered with a wire-screen cage and 15 female adults of Nephotettix cincticeps were released in the cage. The _ L~

~ .

l mortality after 24 hours was determined. In order to test the residual activity, the pot with grown rice plant was treated in the same manner as mentioned above and left standing for 7 days. In the same manner as mentioned , above, the test insect was released and the mortality after 24 hours was determined. The above tests were carried out in a greenhouse.

Mortality (%) , CompoundImmedlately 7 Days after after treatment treatment Present compound (l) 100 100 Re~erence compound (K) 70 0 .
Test Example 12 (Test for ,toxicity to fish) Each of the present compounds (l), (2), (4), (6), (7), (8), (9), (10), (ll), (12), (13), (15), (17), (18) and (19) was dissolved or suspended in "Tween 80" and diluted successively with dechlorinated tap water. ~en Oryzias latipes (0.2 - 0.3 g per fish) were released in a lO-liter glass vessel containing 10 liters of each pre-paration. After 48 hours, the dead and alive were observedto determine median tolerance limit (48 hours) [TLm48 (ppm)].

' ' ':

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Compound TLm48 (ppm) Compound of this invention (l) 0.15 (2) 0.1 (4) 0.1 (6) l.0 - 5.0 ~ :
(7) 1.0 - 5.0 (8) > 5.0 ~.

(9) - 5

(10) 5

(11) 0 3

(12) 0 3

(13) 5 ~ :
(15) 0.2 (17) 1.0 - 5.0 (18) l.0 - 5.0 (19) ~ 3 0 Reference compound (A) 0.026 (B) 0.027 .
(C) < 0.01 (D) 0.02 ~ (I) 0.018 1 Test Example 13 (Mammalian toxicity test) Male mice (18 - 22 g) were orally administered - ~
wi~h~each of the corn oil solutions of the present compounds (1) to (l9), the dosage having been 0.2 ml/lO g body weight.
, _ ~3 - :
,:, :
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1 The mortality after 24 hours was observed and median lethal dose iLD50 (mg/kg)) was calculated.

Compound LD5~ (mg/kg) Compound of this invention (1) > 800 -.
(2) > 800 (3) > 800 (4) 800 (5) > 800 (6) > 800 (7) > 800 (8) > 800 (9) > 800 (10) > 800 (11) > 800 (12) > 800 (13) > 80o

(14) > 800

(15) > 800

(16) ~> 80o

(17) ? 800

(18) ~ > 800 (19~) . > 800 .
Reference compound :~
(A) 112 ~ ~ (B) 650 :
:~ (I) 270 ~. -- . - : . .
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(G) 370 (K) 60 ."~, '.
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Claims (11)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula, wherein R2 is a 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropyl or 1-(4-chlorophenyl)isobutyl group, R1 is a 3-chlorine or 4-chlorine atom, 3-methoxy, 4-methoxy, 3-C2-4 alkyl or 4-C2-4 alkyl group when R2 is a 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropyl group, and R1 is a 3-chlorine or 4-chlorine atom, 3-methoxy, 4-methoxy, 3-C1-4 alkyl or 4-C2-4 alkyl group when R2 is a 1-(4-chlorophenyl)isobutyl group.

2. The compound according to Claim 1, wherein R1 is a 4-chlorine atom and R2 is a 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropyl group.

3. The compound according to Claim 1, wherein R1 is a 3-chlorine atom and R2 is a 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropyl group.

4. The compound according to Claim 1, wherein R1 is a 4-chlorine atom and R2 is a 1-(4-chlorophenyl)-isobutyl group.

5. The compound according to Claim 1, wherein R1 is a 3-chlorine atom and R2 is a 1-(4-chlorophenyl)iso-butyl group.

6. A method for preparing the compound according to Claim 1, which comprises (a) reacting the .alpha.-cyano-m-(substi-tuted phenoxy) benzyl alcohol of the formula, wherein R1 is defined in Claim 1, with an acid halide of the formula, wherein X is a halogen atom and R2 is as defined in Claim 1, in the presence of an organic tertiary base in an inert solvent, or (b) reacting the .alpha.-cyano-m-(substituted phenoxy) benzyl alcohol of the formula, wherein R1 is as defined in Claim 1, with a carboxylic acid anhydride of the formula, wherein R2 is as defined in Claim 1, in an inert solvent, or (c) reacting the a-cyano-m-(substituted phenoxy) benzyl alcohol of the formula, wherein R1 is as defined in Claim 1, with a carboxylic acid of the formula, wherein R2 is as defined in Claim 1, in the presence of a dehydrating and condensing agent in an inert solvent, or (d) reacting the halide of the formula, wherein R1 is as defined in Claim 1 and Y is a halogen atom, with a carboxylic acid of the formula, wherein R2 is as defined in Claim 1, in the presence of an organic tertiary base in an inert solvent or (e) reacting the halide of the formula, wherein R1 is as defined in Claim 1 and Y is a halogen atom, with an alkali metal salt of carboxylic acid of the formula, wherein R2 is as defined in Claim 1 and M is an alkali metal, in the presence of a phase transfer catalyst in two phase system of water and an inert solvent, or (f) reacting the aldehyde of the formula, wherein R1 is as defined in Claim 1, with an alkali metal cyanide and an acyl halide of the formula, wherein X is a halogen atom and R2 is as defined in Claim 1, in the presence of a phase transfer catalyst in an inert solvent, or (9) reacting the aldehyde of the formula, wherein R1 is as defined in Claim 1, with an alkali metal cyanide and an acyl halide of the formula, wherein X is a halogen atom and R2 is as defined in Claim 1, in the presence of a phase transfer catalyst in two phase sys-tem of water and an inert solvent.

7. A method for controlling an insect and/or acarid which comprises applying an insecticidally and/or acaricidally effective amount of the compound according to Claim 1 to the insect and/or acarid.

8. The method according to Claim 7, wherein the insect is those living in an aquatic place.

9. The method according to Claim 7, wherein the insect is Nephotettix cincticips.

10. A method according to Claim 7, in which the compound is according to claim 2 or 3.

11. A method according to claim 7 in which the compound is according to claim 4 or 5.