BENZYLOXIME ETHERS

ETHERS DE BENZYLOXIMES

English Abstract

A B S T R A C T
Insecticidally-active compounds of the following
general formula:-
<IMG>
wherein
Rl is an optionally-substituted aryl or alkyl group;
R2 is an optionally-substituted cycloalkyl group;
X is an oxygen atom or a methylene group;
Y is a hydrogen or halogen atom, or alkyl or alkoxy group;
and
n is an integer of 1 to 5.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of general formula I:
<IMG> (I)
wherein R1 represents a naphthyl group, an optionally substituted phenyl
group of general formula II:
<IMG>
(II)
wherein Z is a hydrogen or halogen atom, or an alkyl or alkoxy group,
and m is an integer of 1 to 5, or an optionally-substituted alkyl group
of up to 10 carbon atoms, the substituents being one or more halogen
atoms, or alkoxy or aryl groups;
R2 represents cyclobutyl or an optionally substituted cyclopropyl
group of general formula III:
<IMG> (III)
22

wherein Ra and Rb both represent hydrogen atoms, alkyl groups having
from 1 to 6 carbon atoms, or halogen atoms, or Ra and Rb together
represent an alkylene group having from 2 to 6 carbon atoms; or Ra
represents a hydrogen atom and Rb represents an alkenyl group having
from 2 to 6 carbon atoms, or a haloalkenyl group having from 2 to 6
carbon atoms and from 1 to 3 chlorine or bromine atoms; Rc and Rd both
represent hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, or
RC is hydrogen and Rd is an alkenyl group having from 2 to 6 carbon
atoms, or a haloalkenyl group having from 2 to 6 carbon atoms and
from 1 to 3 chlorine or bromine atoms; or Rc and Rd together represent
an alkylene group having from 2 to 6 carbon atoms;
X is an oxygen atom or a methylene group;
Y is a hydrogen or halogen atom, or alkyl or alkoxy group;
and
n is an integer of 1 to 5.
2. A compound according to claim 1 wherein Y represents a
hydrogen atom or an alkyl or alkoxy group of 1 to 4 carbon atoms or a
halogen atom.
3. A compound according to claim 1 having the following general
formula:
<IMG> (IV)
23

wherein R1 is phenyl, chlorophenyl, dichlorophenyl, bromophenyl,
dibromophenyl, fluorophenyl, difluorophenyl, methylphenyl, dimethyl-
phenyl, methoxyphenyl, butylphenyl, ethylphenyl, or naphthyl; and Y is
hydrogen, chlorine, fluorine or bromine.
4. A compound according to claim 1,2 or 3 which is in the form of
its E-isomer or a mixture of the E- and Z-isomers in which the
E-isomer predominates.
5. A process for the preparation of a compound of formula I as
defined in claim 1, wherein the alkali metal salt of a ketoxime of
formula:
<IMG> (V)
wherein R1 and R2 are as defined in claim 1, is reacted with a
substituted benzyl halide of formula:
<IMG> (VI)
wherein X, Y and n are as defined in claim 1 and Q is a halogen atom.
6. A process according to claim 5 wherein the alkali metal salt
of the ketoxime is prepared by the reaction of an alkali metal hydride
with the ketoxime or by the reaction of aqueous potassium or sodium
hydroxide with the ketoxime.
7. A process according to claim 5 or 6 wherein the alkali metal
salt of the ketoxime is prepared in situ.
8. A method of combating insect, tick and/or acarid pests at a
locus which comprises applying to the locus a pesticidally effective
amount of a benzyl oxime ether according to claim 1,2 or 3.
24

9. A compound according to claim 1 having the following general
formula
<IMG> (IV)
wherein R1 is 4-fluorophenyl, 4-chlorophenyl or 4-bromophenyl.
10. A method of combatting Spodoptera littoralis pests at a locus
which comprises applying to the locus where Spodoptera littoralis is
present a pesticidally effective amount of a compound of claim 9.
11. A method of combatting Heliothis zea pests at a locus which
comprises applying to the locus where Heliothis zea is present a pesti-
cidally effective amount of a compound of claim 9.

12. A compound of the formula
<IMG>
wherein
A is naphthyl or a phenyl of the formula
<IMG>
B is cyclopropyl, halo substituted cyclopropyl, or cyclobutyl
D is -CH2- or -O-
E and G are separately hydrogen, halogen, alkyl or alkoxy
and a is an integer from 1 to 5.
13. A process for preparing a compound of the formula
<IMG>
wherein A, B, D, E and a are as defined in claim 12 which comprises reacting
an alkyl metal salt of a ketoxime of the formula
<IMG> = N - OH
with a benzyl halide of the formula
<IMG>
wherein K is a halogen atom.
14. A method for combatting insects which comprises contacting them
with an insecticidally effective amount of a compound of claim 12.
26

Description

1~tit;6S~
This invention relates to a group of compounds, which may be termed
benzyloxime ethers, having interesting pesticidal activity. It also relates
to a method of preparing the compounds and to a pesticidal composition compris-
ing one or more of the compounds.
The present invention provides compounds of the following general
formula: R2 X ~ ( )n
Rl _ C = N - 0 - CH2- ~ (I)
wherein Rl represents a naphthyl group, an optionally substituted phenyl
group of general formula II:
~ (II)
wherein Z is a hydrogen or halogen atom, or an alkyl or alkoxy group, and m
is an integer of 1 to 5, or an optionally-substituted alkyl group of up to
10 carbon atoms, the substituents being one or more halogen atoms, or alkoxy
or aryl groups;
R2 represents cyclobutyl or an optionally substituted cyclopropyl
group of the general formula III:
R R
a ~ b
c ~ H (III)
wherein Ra and Rb both represent hydrogen atoms, alkyl groups having from 1
to 6 carbon atoms, or halogen atoms, or Ra and Rb together represent an
alkylene group having from 2 to 6 carbon atoms; or Ra represents a hydrogen
atom and Rb represents an alkenyl group having from 2 to 6 carbon atoms, or
a haloalkenyl group having from 2 to 6 carbon atoms and from 1 to 3 chlorine
or bromine atoms; Rc and Rd both represent hydrogen atoms, alkyl groups
having 1 to 6 carbon atoms, or Rc is hydrogen and Rd is an alkenyl group
having from 2 to 6 carbon atoms, or a haloalkenyl group having from 2 to 6
-- 2 --

i6~i2
carbon atoms and from ] to 3 chlorine or bromine atoms; or Rc and Rd together
represent an alkylene group having from 2 to 6 carbon atoms;
X is an oxygen atom or a methylene group;
Y is a hydrogen or halogen atom, or alkyl or alkoxy group; and
n is an integer of 1 to 5.
The present invention also provides a process for the preparation
of a compound of formula I as defined above, wherein the alkali metal salt
of a ketoxime of formula: Rl
C = NOH ~V)
R2~
wherein Rl and R2 are as defined above, is reacted with a substituted benzyl
halide of formula: ~ (Y)n
Q - CH2- ~ ~VI)
wherein X, Y and n are as defined above and Q is a halogen atom.
The invention still further provides a method of combating insect,
tick and/or acarid pests at a locus which comprises applying to the locus a
pesticidally effective amount of a benzyl oxime ether of the invention .
Generally speaking, when Rl represents phenyl better insecticidal
activity has been observed when there is a substituent in the 4 position and
m is 1 or 2; e.g., Z may be chlorine, bromine, fluorine, methyl, ethyl,
tertiary-butyl or methoxy.
~ hen Rl represents an optionally-substituted alkyl group, it can be
a straight or branched-chain alkyl group and may have as substituent or sub-
s*ituents one or more halogen atoms, or alkoxy or aryl groups, e.g., chlorine,
bromine, fluorine, methoxy or phenyl. The alkyl group preferably contains
up to 10 carbon atoms.
The substituent Y preferably represents a hydrogen atom but can
also be an alkyl or alkoxy group of 1 to 4 carbon atoms or a halogen atom,
e.g., chlorine, fluorine or bromine atom.
Regarding group R , when Ra and Rb both represent alkyl they are
especially methyl, and when halogen they are especially chlorine or bromine
atoms.
- 3 -

1~ 2
When Ra and Rb together represent an alkylene group this preferably has 3 carbon
atoms. If Ra represents a hydrogen atom and Rb represents an alkenyl group this
is preferably an isobutenyl group, while a haloalkenyl group Rb is especially a
mono- or dichlorovinyl group. When Rc and Rd both represent alkyl groups they
are especially methyl. If Rc is hydrogen and Rd is an alkenyl group it is es-
pecially an isobutenyl groupJ while a haloalkenyl group Rd is especially a mono-
or dichlorovinyl group. When R and Rd together represent an alkylene group it
preferably has 3 carbon atoms. A better level of pesticidal activity has gener-
ally been noted where R2 in the general formula I represents an unsubstituted
cyclopropyl group.
Because of their high level of activity against the corn-ear worm
(Heliothis zea) the following group of compounds are preferred:
Rl _ C = N - 0 - CH2 ~ ~ ~IV)
wherein Rl is phenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl,
fluorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, methoxyphenyl, butyl-
phenyl, ethylphenyl or naphthyl, and Y is hydrogen, chlorine, fluorine or
bromine.
It will be appreciated that the compounds according to the invention
exhibit geometrical isomerism about the oximic double bond and, accordingly, the
invention also extends to these individual isomers and to mixtures thereof. It
has been found that, in general terms, the isomer in which R2 (the optionally-
substituted cyclopropyl group~ and the 3-substituted
-- 4 --

i6~2
-- 5 --
benzyloxy group in the compounds of formula I are in a
relationship about the double bond is more insecticidally-
active than the isomer in which ~he two groups are in _ti
relationship; more correctly the nomenclature of these two
geometric isomers should be referred to as the E- and z~isomers,
the E_isomer being the more active form. Accordingly, the
preferred form of the compounds according to the invention
is the E-isomer or a mixture of the two isomers in which
the E-isomer predominates.
The compounds according to the invention may be prepared
by methods known for the preparation of oxime ethers. A
ketoxime of formula:-
R1~ (V)
C = NOH
R2/
wherein R1 and R2 have the meanings previously defined, is a
preferred starting material~ A method for the preparation of
compounds of the invention comprises reacting an alkali metal
salt of a ketoxime of formula V with a substituted benzyl
halide of formula:- X ~ (Y)n
_I ~
Q - CH2 - ~ ~ (VI)
wherein X, Y and n have the meanings previously defined and Q
is a halogen, preferably bromine atom. The reaction is preferably
carried out in the presence of a polar aprotic solvent;

c)z
-- 6 --
particularly suitable solvents are anhydrou~ acetonitrile,
dimethylfor-mamide in toluene, or tetrahydrofuran. Reaction
temperatures are generally in the range 60-150C preferably
in the range 100-110C and reaction times of 2 to 10 hours
may be used. Alternatively the reaction of the alkali metal
salt of a ketoxime of formula V with a substituted benzyl
halide of formula VI may be carried out in a two-phase
organic/inorganic system in the presence of a phase transfer
catalyst. The phase transfer catalyst may be any reagent
which will accelerate interphase reactions in orgariic-
inorganic two phase systems. The alkali metal salt of the
ketoxime of formula V may be prepared by the reaction of
an alkali metal hydride with the ketoxime, for example,
sodium hydride, or by reaction of aqueous potassium or
sodium hydroxide with the ketoxime. Under normal conditions
the alkali metal salt of the ketoxime is prepared in situ.
The benzyl oxime ethers of the invention are of interest
as pesticides, in particular as insecticides, tickicides
and acaricides for agricultural and domestic outlets. The
invention therefore includes within its scope pesticidal
compositions comprising a carrier and/or a surface-active
agent together with, as active ingredient, a benzyl oxime
ether of formula I. The invention also includes a method
of combating insect, tick and/or acarid pests at a locus
which comprises applying to the locus a pesticidally ef-
fective amount of a benzyl oxime ether of the invention or
composition containing such a compound.

-- 7
The term 'carrier' .Is used herein means a material,
which may be inorganic or organic and of synthetic or natural
origin, with which the active compound is mixed or formulated
to facilitate its application to the plant, seed, soil or
other object to be treated, or its storage~ transport or
handling. The carrier may be a solid or a liquid. Any of
the materials usually applied in formulating pesticides,
herbicides, or ~ungicides may be used as the carrier.
Suitable solid carriers are natural and synthetic clays
and silicates, for example, natural silicas such as diatomaceous
earths; magnesium silicates, for example, talcs; magnesium
aluminium silicates, for example, attapulgites and vermiculites;
aluminium silicates, for example, kaolinites, montmorillinites
and micas; calcium carbonates; calcium sulphate; synthetic
hydrated silicon oxides and synthetic calcium or aluminium
silicates; elements for example, carbon and sulphur; natural
and synthetic resins such a~, for example, coumarone resins, poly-
vlnyl chloride and styrene polymers and copolymers; solid poly-
chlorophenols; bitumen; waxes such as for example, beeswax,
paraffin wax, and chlorinated mineral waxes; and solid
fertilisers, for example, superphosphates.
Suitable liquid carriers are water, alcohols, for example,
isopropanol and glycols; ketones for example, acetone, methyl
ethyl ketone, and cyclohexanone; ethers; aromatic hydro-
carbons, for example, benzene, toluene and xylene; petroleumfractions, for example, kerosine and light mineral oils;

- 8 --
chlorinated hydrocarbons, for examplc, carbon tetrachloride,
perchloroethylene, trichloroethane; and liquefied normally
vaporous, gaseous compounds. Mixtures of different liquids
are often suitable.
The surface-active agent may be an emulsifying agent
or a dispersing agent or a wetting agent; it may be nonionic
or ionic. Any of the surface-active agents usually applied
in formulating pesticides,herbicides or fungicides, may be
used. Examples of suitable surface-active agents are the
sodium or calcium salts of polyacrylic acids and lignin
sulphonic acids; the condensation produ~cts of fatty acids
or aliphatic amines or amides containing at least 12 carbon
atoms in the molecule with ethylene oxide and/or propylene
oxide; fatty acid esters of glycerol, sorbitan, sucrose
or pentaerythritol; condensates of these with ethylene oxide
and/or propylene oxide; condensation products of fatty alcohols
or alkyl phenols for example p-octylphenol or p-octylcresol,
with ethylene oxide and/or propylene oxide; sulphates or
sulphonates of these condensation products; alkali or alkaline
earth metal salts, preferably sodium salts, or sulphuric or
sulphonic acid esters containing at least 10 carbon atoms
in the molecule, for example, sodium lauryl sulphate, sodium
secondary alkyl sulphates, sodium salts of sulphonated castor
oil, and sodium alkylaryl sulphonates such as sodium dodecylbenzene
sulphate; and polymers of ethylene oxide and copolymers of
ethylene oxide and propylene oxide.

Z
The compositions of the invention may be formulated as
wettable powders, dusts, granules, solutions, emulsifiable
concentratesr emulsions, suspension concentrates and aerosols.
Wettable powders are usually compounded to contain 25 50
and 75% of toxicant and usually contain, in addition, to
solid carrier, 31-0% w of a dispersing agent and, where
necessary, 0-10% w of stabiliser(s) and/or other additives
such as penetrants or stickers. Dusts are usually formulated
as a dust concentrate having a similar composition to that
of a wettable powder but without a dispersant, and are diluted
in the field with further solid carrier to give a composition
usually containing ~-10% w of toxicant. Granules are usually
prepared to have a size between 10 and 100 BS mesh (1.676-0.152 mm)
and may be manufactured by agglomeration or impregnation
techniques. Generally, granules will contain ~-25% w toxicant
and 0-10% w of additives such as stabilisers, slow release
modifiers and binding agents. Emulsifiable concentrates usually
contain, in addition to the solvent and, when necessary,
co-solvent, 10-50% w toxicant, 2-20g w/v emulsifiers and
zo 0-20% w/v of appropriate additives such as stabilisers,
penetrants and corrosion inhibitors. Suspension concentrates
are compounded so as to obtain a stable, non-sedimenting flowable
product and usually contain 10-75% w toxicant, 0.5-15% w
of dispersing agents, 0.1-10% w of suspending agents such
as protective colloids and thixotropic agents, 0-10% w of
appropriate additives such as defoamers, corrosion inhibitors,

i6~
1 o
stabilisers, penetrants and stickers, and as carrier, water
or an organic liquid in which the toxicant is substantially
insoluble; certain organic solids or inorganic salts may
be dissolved in the carrier to assist in preventing sedimentation
or as antifreeze agents for water.
Aqueous dispersions and emulsions, for example, com-
positions obtained by diluting a wettable powder or a concen-
trate according to the invention with water, also lie within
the scope of the present invention. The said emulsions may
be of the water in-oil or of the oil-in-water type, and may
have a thick 'mayonnaise'like consistency.
The compositions of the invention may also contain
other ingredients, for example, other compounds possessing
pesticidal, herbicidal or fungicidal properties.
The invention is further illustrated in the following
examples.
Example 1
__ __
Preparation of cycl~rop~l-4-_luoro~hen~ ketoxime_3-~noxy-
benz~l ether
___ ._ _
Cyclopropyl-4-fluorophenyl ketoxime (2,4g) in dry acetonitrile
(50ml) and sodium hydride (0.64g of 50% dispersion in oil)
was qtirred at room temperature for 2 hours. 3-Phenoxybenzyl
bromide (3.5g) was added and the mixture refluxed for 3 hours.
The reaction mixture was cooled, filtered,evaporated and the
re9idue dis901ved in diethyl ether. The ether solution was
washed in turn with 7% sulphuric acid solution, 10% sodium
bicarbonate and water and dried over sodium sulphate. The
solvent was then removed under reduced pressure and the residue

was chromatographed on silica gel in hexane, u~;ng 4:1
toluene: hexane as elut~nt to give the desired product as
a colourless oil.
Analysis Calculated for C23H20N02F : C 76.4; H 5.5; N 3.8%
Found : C 76.8; H 5.7; N 3.8%
Example 2
Preparation of cycloprop~-2,4-xylyl ketox _e 3-phenoxy-
benzyl _ e
Cyclopropyl 2,4-xylyl ketoxime (1.89g) in dry acetonitrile
(50ml) and sodium hydride (0.5g of 50% dispersion in oil)
were stirred at room temperature for 1 hour. 3-Phenaxybenzyl
bromide (2.88g) was added and the mixture refluxed for 4 hours,
then stirred for a further 48 hours. The reaction product was
then filtered, the filtrate evaporated and the residue dissolved
in diethyl ether. The residue obtained after washing and removal
of solvent, as in the above preparation, was chromatographed
on silica gel in hexane using toluene as eluant to give the
desired product as a colourless oil.
Aralysis Calculated for C25H25N02 : C 80.8; H 6.8; N 3.8%
Found : C 80.7; H 6.9; N 3.6%
Ex_~le 3
__ __
Preparation of cyclopropyl-4-chl_rophenyl ketoxime 3-phenoxy-
benzyl ether
Cyclopropyl-4-chlorophenyl ketoxime (1.95g, 0.01 mole)
in 20% dimethylformamide/toluene (25ml) was added dropwise
to sodium hydride (1.0g of a 50% dispersion in oil) in
dimethylformamide/toluene (20ml) at 70-80C over 30 minutes.

-
3-Phenoxybenzyl bromide t2-9g, 0.01 mole) in 20% dimethyl-
formamide/toluene (25ml) was then added and the mixture refluxed
for 3 hours. After cooling 5m] of methanol was added and the
reaction mixture was poured onto ice/hydrochloric acid and
the product then extracted with diethyl ether, washed with 10%
sodium carbonate solution (X4) and dried over sodium sulphate.
The solvent was removed and the residue chromatographed on
silica gel using toluene as eluant. Two fractions were eluted
from the column. After removal of solvent the residue from
the first fraction, obtained as an oil, was identified as
isomer E, R.I. nD22 = 1.6078. The residue from the second
fraction, obtained as an oil, was identified as a 1:1 E:Z isomer
mixture, R.I. nD2 1.6059. The Z isomer was isolated with
an R.I. of nD7 1.5940.
Ana ~ Calculated for C2 H20H02Cl : C 73.1; H 5.3; N 3.7%
Found : C 73.1; H 5.5; N 3.4%
1:1 E:Z isomer mixture : C 72.1; H 5.4; N 3.5%
Z isomer : C 73.4; H 5.2; N 3.4%
Example 4
,_ _
Preparation of cyclobutyl-4-fluor_~enyl ketoxime 3-phenox~-
__ _ ___ _ _ ___. . _ __ __
benzyl ether
Cyclobutyl-4-fluorophenyl ketoxime (1.35g, 0.07 mole)
in 20% dimethylformamide/toluene (25ml) was added dropwise
to ~odium hydride (0.7g of 50% dispersion in oil) in dimethyl-
formamide/toluene (20ml) at 70-80C over 10 minutes. 3-Phenoxy-
benzyl bromide (1.85g, 0.07 mole) in 20% dimethylformamide/toluene

- 13 -
(20ml) was then added and the mixture refluxed for 3 hours
at 100-110C. The reaction mixture was then cooled to room
temperature, filtered and the filtrate evaporated and the
residue dissolved in diethyl ether. The residue obtained
after washings and removal of solvent was chromatographed
on silica gel using toluene as eluant to give the desired
product as an oil R.I. n20 1.5858.
Analysis Calculated for C24H22N02F : C 76.8; H 5.9; N 3.7%
Found : C 77.2; H 5.9; N 3.7%
Examples 5~10
.
Further examples of the compounds according to the
invention were prepared by the methods disclosed in the
preceding examples. The structure and physical data of
these ¢ompounds are shown in Table I.

tj~9.i"~,
~ - - -- -
o~o o~o op o\o o~o o~oo~o o~o o~o o~o o~o o~o
N N 1~ (5~ ~ ~ N ~r 1~ O 1~ 1~
~D ~ ~ ~ r~ I~ ~D ~ ~ I` ~
X ~ ~: X ~ X X ~q ~ ~ ~: X .
~ ~ . ~ . ~ N 1~ N O~ . ~ ~
O O L~') IS) ~ ~1 1` ~) --I
CO ~ ~ ~D OD CO I~ ~ a~ OD ~ 00
~ O ~ O ~ ~ ~ ~
1~ .. .. .. .. .. .. .. .. .. .. .. ..
N m oN o oN oN
caz~ æO z~ æ~ æ~ z~
~ U~N N N N N N
~/ ~>1~ ~ ~C~ X~r ~U~ ~Ln
1~N ~1 N ~ N N
~ ~ , ~ ~_) ~_) V V t.) ~)
O O lu O h O
~3 ~a
~ ~ ~ 1~ ~ ~
o ~ ~o ~~a ~~a ~ ~ ~ ~ ~ ~a
U ~j U ~ U ~j U ~ ,~ ~ U
I\ æ ~ ~ u ~ ~ ~ ~ ~ ~ ~ c~
~ _____ ___ _ _
/
~J~ . 15 N ~rl~) ~)
~3 ~D CO ~,~.~ a~
O _i ,_i ~i~1 ~i
H _1 ~1 ON a NO ~ ~ a
~: o __ _ ~_ ~
~,
~ ~I ~
~ ~ ~ '~ ~ s~
,m¢~ ~ ~ ~ ~' ~ ~ l ~
E~ ~ ~; ~ ~r ~ ~ ~ ~ ~r
_ ____ ~D r _ o

1~ 6~2
- 15 -
Examples 11-22
___ _ . _ _ _ _
Ele~en further compounds according to the invent;on
were prepared by the methods disclosed in Example~ 1 to 4.
The structure and physical data are shown in Table II.

6~
-- 16
_ _.
o\ d dO d d d d d d d
~ 7
z z æ z æ z z æ z z
f~ LO CO ~ 1~ I` 1~ ~ U~
~P ~r ~ ~ u, ~ ~r ~ ul u~
~ ~ X X ~ ~: X ~ ~
I` ~D r~ ~D O ~ O ~ ,~ u~
u ~ ~ ~r ~r ~ ~D ~9
~ V V V V V V V V U ~
O ~ ~ ¦ R ;~ ;~ U
5~ ~ ~U ~ ~ ~1~
O _ V ~ V ~ V V ~ ~
~;~V O O ~ O ~ 0
~; H E~ ~1 ~ ~D ~D
: 1~; ~Q ~ ~:
~ 1~ :~: tc ~ ~
_ r . _
N V N
H ¦ ~`I ~ N
O ~ O O
o~ o~ ~r~ o~
~r
__ _~_ _
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X ~1 ~1 N ~ L~)
1~1 Z ._.. _ ~ _~ __ _

-
r~ ~ - ~
Cl~ Ln ~ ~ ~ Ln :~ ~ ~ O 3 ~
~ tr~ ~ ~
Z Z I Z ~: I Z Z :Z ~ Z Z I I Z ~
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. I Ln 3 ! ~ . , o~ Ln I I a~ ~
o Ln ~n I Ln Ln ~ n ~ n ~o I
C X 1 1 r X ~ ' I X X i
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td' O O ! O .~ c) o
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¢ . ~) I N 0~ 0~ ICJ~ ' ~ ~ 1 ~ !
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a) ~ ~ q~ ~1 6 ! a~
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:1 ~a ~ a ~~ 1 3 ~ ! a~ ~: i 3
C~ S C1 ~ C ~ ¦ J~ o ! C~
3 ~ 3 ~ 3 1 ~ C~ I ~ 3 1 ii
' ~ o 1~ o I ~ o I n~ o I 1 o I E3 I td O I
I I O ~ 3
I~sr I ~ I Lr~ 1 3 1 ~O
. I -- I -- I N I N I ~ ~ I ~ I
A I ~ I ~ I ~ I ~ ~ I a
t~ ~ ~ 1 o
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I ~ar ! I I I l I I i I
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~_~tj~65~
~ 18 -
Exam~le 23
_ _ _ __ _
- The insecticidal and tickicidal activity of the compounds
according to the present invention was assessed employing
the following pests:
Insects:- Musca domestica (M.d.)
Spo_ptera littor_lis (S.l.)
Heliothis zea (H.z.)
Ticks:- B~hilus microplus (B.m.)
__ _ _ . . .
The test methods employed for each species appear below:-
(i) Musca domestica (M.d.)
__
A 0.4% by weight solution in acetone of the compound
to be tested was prepared and taken up in a micrometer
syringe. Two to three day old adult female houseflies
(musca domestica) were anaesthetized with carbon
dioxide, and 1 ~ul oP the test solution was applied to
the ventral side of the abdomen of each fly, 20 flies
being tested. The treated flies were held in glass jars
covered with paper tissue held by an elastic band.
Cotton-wool pads soaked in dilute sugar solution
were placed on top of the tissue as food. After 24 hours
the percentage of dead and moribund flies were recorded.
(ii) Spodoptera littoral_s (S.l.)
Pairs of leaves were removed from broad bean plants
and placed on filter paper inside plastic petri dishes.
The leaves were sprayed on the undersurface with a
formulation contalning 20% by weight of acetone,
0.05~ by weight of TRITON X-100 as wetting agent and

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0.4% by weight of the compound to be tested. Varying
concentrations were obtained by diluting the formulation.
After spraying the leaves were left to ~-1 hour drying
period and then each leaf pair was infested with ten
larvae of the Egyptian cotton leafworm (~_dop_era
littoralis). After 24 hours the percentage of dead
and moribund larvae were recorded.
(iii) Boophil_s mi~ s (B.m.)
The compounds to be tested were formulated as solutions
or fine suspensions in acetone containing 10% by
weight of polyethylene glycol having an average mole-
cular weight of 400. The formulations contained O.1%
by weight of the compound to be tested. 1 ml of the
above-mentioned solution was applied evenly to a
filter paper situated inside a petri dish. After the
paper was sufficiently dry it was folded in half and
partly crimped along the outer edge to form a packet.
About 80-100 larval ticks (Boophilus mlcroplus) were
transferred into the packet which was then sealed
completely. The packets were placed inside an incubator,
maintained at 27C and 80% relative humidity, before
assessing mortality 24 hours later.
(iv) Heliothis zea (H.z.)
A 0.2~ by weight solution of the compound to be tested
was prepared by adding 2 m] of a 1% acetone solution
to 8 ml of 0.05% AHOX 1045A solution. The cut broad
bean plant was sprayed with 4 ml of test solution

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using a hand sprayer. Immediately after spray;ng 5
larvae of the corn earworm (Heliothis zea) were
transferred to each plant which was inserted into
water through the centre hole of a test board and
covered with a wire screen. 44-46 hours after spraying
the percentage of dead and moribund larvae were
recorded.
The results are shown in Table III in which the test species
are identified by the initials noted above and the activity
of each compound is expressed in the form of their Toxicity
Index (T.I.) which is calculated from the following equation:-
Toxicity Index (T.I.) =LC50 of ethyl parathion
LC50 of test compoundwherein LC50 is the lethal concentration required to kill 50%
of the test species.

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TABLE_III
INSECTICIDAL AND TICKICIDAL ACTIVITY
_ Toxicity Index
Compound __ _ _ __ _ ___ __. _____ _ _____ _ ___ _ _
Example M d ___ _ __. B~m __ _ __ _ __
7 78 40 19
8 177 337o 349 56
2 108 40 6
3 94 17 284
6 77 210 200
31 54 72
59 23 175
8 35 46 76
. ___ 4B 68 ~ _ _ _