Note: Descriptions are shown in the official language in which they were submitted.
rrhi~ inven~ion relates to novel esters ? to processes
fvr preparing them, to compositions comprising them, and to
me~hods o combating insect pests using them.
Accordlngly the presen~ invention provides esters of
formulas-
CH.Co.oCH(R5)
R~R2C=CH.CE~
C(CH3)2 oCH=CR3R4
(I)
wherein Rl and R~ represen~ halogen radicals or lower alkyl
groups; R3 and R4 represent halogen radicals; and R5
represents a hydrogen atom or the cyano radical.
~y the term "halogen" as used herein is meant fluorine~ ;~
lo chlorine or brcmine; and ~y the term lower alkyl group is
meant arl alk~l group containing up to four carbon atoms.
~n a preferred ~orm the invention provides compounds
where~n Rl and R~ ars both methyl groups~ or both chlorine
radical~ or ~oth bromine radicals. An especially preferred
group o compounds within th~ invention are those wherein
Rl, R2, R3 and R4 are all chlorine radicaI~.
It will be readily appreciated that the compounds of
th~ in~entlon as set out hereinabove are described without
referenc~ tQ their stereochemical nature. Thus the above
formula does not diferentiate be~ween the cis and trans
- 2 -
' .' ' .', .-:
geometrical isomers which are possibly due to the substit-
ution pattern around the cyclopropane ring, nor does it
differentiate between the various stereoisomeric forms which
may be present, and the present invention includes within
lts scope all such geometric and optical stereoisomers.
Thus the term "compound" as used herein in relation to
esters of the invention refers both to an individual isomer
ln isolatlon, and to mixtures of isomers thereof e.g.
racemic mixture3, diastereoisomeric mixtures.
The following compounds are typical example~ o:E compounds
according to ~he invention.
3(2,2-dichlorovinyloxy)ben2yl (~) cis~trans-chrysanthemate
therelnafter referred to as Compound 1).
3(2,2-dichlorovinyloxy)benzyl (+~ cis/trana-2(2,2-dichloro-
vinyl)3,3-dimethylcyclopropane carboxylate (hereinafter
refe~red to as Compound 2).
3(2v2-dlchlorovinyloxy)benzyl (+) cis-2(2,2-dichlorovinyl)-
3,3-dLmethylcyclopropane carboxylate (hereinafter referred
to as Compound 3).
3(2,2-dichlorovinyloxy)benzyl (~) trans-2(2,~-dichlorovinyl)-
3,3--dimethylcyclopropane carboxylate (hereinafter referred
to a~ Compound 4). '
3 --
, . . .
o
~+) -cyano-3(2,Z-dichlorovinyloxy)benzyl (~
2(2,2-dichlorovinyl)3,3-dimethylcyclopropane carboxylate
(herelnafter re~erred to as Compound 5).
~ cyano-3(2,2 dichlorovinyloxy)benzyl ( ) cis-2(2,2-
dlchlorvvinyl)3,3-dlmethylcyclopropane carboxylate.
(~o~cyano-3(2,2dichlorovlnyloxy)benzyl (+) cis-2(2,2-
dichlorovlnyl)3,3-d~methylcyclopropane caxboxylate.
3(2,~-dichlorovinyloxy)benæyl (~) cis/trans-2(2,2-dibromo-
vinyl)3,3-d1methylcyclopropane carboxylate.
3~ dib~omovinyloxy)ben2yl t+) ~ -chrysanthemate.
3(2,2-dibromovinylo~y)benæyl (+) cis/trans-2(2,2-dichloro-
vinyi)3,3-dimethylcyclopropane carboxylate.
~ ~cyano-3(2,2-dichlorovinyloxy)benzyl (~) cis!trans-
chrysan~hemate.
;
lS (~ ~ yano 3(Z,2-dichlorovinyloxy)benzyl (+) cis/trans-
~2,2-dibromovinyl)3,3-dimethylcyclopropane carboxylate.
: , .
` ~S~8~
~he invention compounds may be prepared by ~everal
different processes. Thus a compound of formula:-
CH . CO . OH
R R C=CH . CH ~ ¦
( C~3 ) ;2
,
(II)
optionally ln the f?orm of a metal salt thereof, may be
reacted with a c~mpound of formula:-
XC~I~R5) ~
` 3 4
(ITI)
wherein X i5 a halogen atom, preferably a chlorine or
bromine atom, and Rl, R2, R3, R4 and R5 have any of the
meanings given hereinabove. Alternatively a compound of
f?ormula :--
,: '
CH.CO~Y
RlR2C=CH.CH / ¦
C(CE13)~
~,
~ - 5 -
.,. . . . ~. ,
, ~ : :'
- . I
;
'
, may be reacted wlth a compoulld of formula:-
, ~
'. , .
' HOCH(R5~ ~
~<
3 4
. .
tV)
erein ~ is a halogen atom, preferably a chlorine atom, and
1, ~2, R3, R4 a~d R5 have any of the meanings glven herein-
before~
: 5 In another process ~he invention esters may be obtained
by the;proc~s of transesteri~ication wherein the mixture of
~ a ~lmple e~ter (e.g. a lower alkyl ester such as the methyl
., i ,
`: or ethyl ester) of the acid of .formula II and the alcohol of
formula V is h~ated in a solvent or diluent, preferably in
the p~esence of a base ~e.g. a lower alkoxide such as sodium
me~hoxlde or e~hoxide).
These~processes may in some cases be carried o~t by
hea~ing the reactants together in the absence of a diluent
and~or a base, but preferably a solvent or diluent and a
base is pre~ent~ Suitable solvents include, for example,
non-hydroxylic materials such as allphatic ketones (e.g.
acetone), dimethylformamide, dimethylsulphoxide, sulpholane,
acetonitrlle an~ tetrahydrofuran. Of these an aliphatic
-- 6 --
- - ~ , . . . ~ .
~LlS~BO
ketone such a~, for example acetone is particularly preferred.
Hydroxylated solvent~, for example, methanol and ethanol,
may be used in certain clrcumstances when the presence of
the hyd~oxyl group does not interfere with the progress of
the reaction. Suitable bases include sodium hydride (although
not when a hydroxylated solvent or diluent is used), alkall
metal carbonates, such as potassium carbonate and alkali
metal hydroxides such as potassium hydroxideu The ~emperature
at which the reactlon may be carried out will depend upon
the choice of reactants, ~olvent or diluent and base. When
acetone and potassium carbonate are used the reaction
generally takes place at the ambient temperature. Hiyher
temperatures, up to 100C, may be employed when other bases
are employed. A typical process consists of dissolving or
suspending the reactants in a solvent in the presence o a
base. After allowing a period of time for the reaction to
occur' the product may be isolated by the removal of any
insoluble portion by filtxa~ion and evaporation of the
filtrate. The product may be purified by distillation under
reduced pressure, or by a suitable chromatographic technique.
When it is desired to produce a single geometrically isomeric
form o an invention ester this may be achieved either by
using a pure cis or trans acid or acid derivative of ~ormula
II or III above, or by us~ng a ~ rans mixture thereof and
~eparating the required isomer from the mixture of esters
' ' ~ '' ',
. ' " ' ''" "' '"' ' ' ". . .
: ' ;
w~
produced by for example a chromatographic technique.
The compounds of formula III and formula V which are
used in the above processes for the prsparation of the
invention es~ers are themselves novel compounds, and may be
prepared by the following processes.
Thu~ a compound o formula III whe:rein R5 is hydrogen
:~ may be prepared from a compound of the formula:-
:~ .
C~3 ~
o-CH(OH)CR3R4Z
(VI)
by su~ecting them to chemical or electrochemical reductive
dehydrohalogenatlon to give a compound of formula:-
C~3 ~
o-CH-CR3R4
(VII)
and thereafter halogenating the methyl group of compound VII
to produce the requlred compound of formula III~ Z in
~ormul.a VI i~ a halogen radical, and is preferably the ~ame
halogen radical aB that repre~ented by R3 and R4.
i9~
Compounds of formula VI may be prepared by a method
; analogous to ~hat of vcn Hesse and Moll, J. Prakt. Chemie,
1974, 3 (2), 304 in which anhydrous chloral or bromal is
reacted with m-cresol in the presence of an acyl halide.
The electrochemicaL reduction procedure may be carried
out ln organic solvents, for example lower alcohols, such as
methanol or ethanol, cyclic ethers such as dioxa~ or tetra-
hydrofuran, aliphatic ketones such as acetone or cyclohexanone,
or mlxtu.res of these ~olvents with water or water containing
O strong mineral acids such as sulphuric, hydrochloric or
phosphoric acids.
The reduction ls believed to occur principally at the
cathode with a high hydrogen overvoltage, for example a
m~rcury, lead amalgam or lead cathode. The reaction can be
: 15 conveniently carried out ln a cell fitted with a ceramic or
glass fritted diaphragm, a ~tirrer, a working electrode and
a reference electrode. ~he process may be adapted for
continuous production of the required product by use of a
~olvent system with which the product of the reaction may be
7.0 extracted, for example methylene chloride.
The metallic reductive dehydrohalogenation may be
carried out with a 3uitable reducing medium such as zlnc
dust and acetic acld.
Halogenation of the compound~ of formula VII may
conv~n:Lently be carried out with the aid of a source of
_ g _
.,
-. :. :, - .
j9~
po~itive hal~gen, for example an N-haloimide such as N-
bromosuccinimide, or N-chlorosuccinimide. The compounds of
formula V wherein R5 is hydrogen may conveniently be prepared
~rom the corresponding compounds of formula III by, for
example, treating them with an alkali metal hydroxde, or
alternatively converting them to the corxesponding tosylate
t~-toluenesulphonate) and subjecting the tosylate to hydrolysis.
Compound3 of formula III wherein R5 is hydrogen may be
converted to khe corresponding compounds wherein R5 is a
cyano raalcal by ~he proce s of treating a compound of
formula III whexein R5 18 hydrogen with a source of cyanide
ion, e.g. an alkali ~etal cyanide such as sodium cyanide,
and thereafter subjecting the compound of formula:-
NC . CH
o-cH=~R3R4
(VIII)
thus produced to further halogenation. The reaction with
cyanide may conveniently be perfoxmed in a polar aprotic
~olvent such as dimethylformamide~ at an elevated temperature
i.n the range 50 to 100C. The halogenation step may conveniently
b~ parEor~ed in the manner outlined above for the preparation
-- 10 --
. -
of compound of formula III whersin R5 is hydrogen. The
compouRds of ormula V wherein R5 is cyano may be obtained
from the compounds of formula III where R5 is cyano by
analogous processes to those set out above for the corres-
ponding compounds where R5 is hydrogen.
A preferred method for the preparation of compounds of
formula V where R5 is cyano is however based on a different
appxoach in which a comp~und of formula VII i5 selectively
oxidised to a cvmpound of formula:-
'~
OHC ~
O-CH=CR R
; (IX)
and this compound is then onverted to its cyanohydrin by
reaction with hydrogen cyanide, or, preferably, vLa the
bisulphite compound, with cyanide ion ~e.g. sodium cyanide).
An alternative process for preparing compound IX involves
the oxidation of compound V where R5 is hydrogen with
aluminium isopropoxide and acetone under the conditions of
the Oppenauer reaction.
In another aspect therefore the invention provides
compounds o formula III~ V, VII, VIII and IX, all use~ul as
intermediates ln the preparation of the invention esters of
-; ,
: .
:
formula I~ and processes for the preparation of the said
compound~ oE formula III, V, VII, VIII and IX.
A~ sta*ed above th~ invention esters of formula I are
useful as lnsecticides, and are most conveniently used as
such when formulated into compositions~ In another aspect
therefore the lnvention provi~es lnsecticidal compositions
which compxlse as an active ingredient an invention ester of
ormula I in assoclation with agriculturally and horticult
urally acceptable diluPnt or carrier materials.
lV In a pxeferment of thi~ aspect of the invention the.
actlve ingredient is selected from amongst the ~pe~ifically
named e~ters of the invention set out hereinabove.
The compositions are for use in ~griculture or hortl-
culture but the type of composition used in any in~tance
w~ depend upon the particular purpose for which it is to
be used.
The compoiitions may he in the form of granules or
powd~rs comprising the active ingredient and a solid diluent
or carrIer~ The compo6itions may also be in the ~orm of
liquid preparations to be used as dips or sprays which are
yenerally aqueous dlspersion~ or emulsions.
The composltions ~o be used as sprays may also be in
the form of aero~ols wherein the formulation is held in a
container under pressure in the presence of a propellant
~S such as fluorotrichlorometh~ne or dichloxodifluorom~thane.
- 12 -
For agricultural or horticultural purposes, an aqueous
preparation containing between 0.0001~ and 1.0% by weight of
~he active ingredient or ingredients may be used.
The composi.tions of the present invention may, if
S desired, al~o comprise in addition to a compound of the
present invention, at lea~t one other biologically active
ingredient, for example, an insecticide or a fungicide.
They may also comprise a ~ynergist of the type u~eful in
synergi~ing the activity of pyrethroids type insecticides~
In u~e, the inventlon compounds or compositions may be
used to combat insect~ in a variety of ways. Thus the
in~ects themselves r or the locus of the insects or the
habltat of the lnsects is treated with a compound or a
compo61tion according to the invention.
The lnventlon also provides a method of treating plants
to render them less susceptible to damage by insects, which
compr!ises treating the plants, or the seeds, corms, bulbs,
tubers, rhl20mes or other propagative parts of the plants,
or th~ medium in which the plants are growing with a compound
or composition according to the lnvention.
Thus the compounds of the invention are toxic towards a
wide variety of insect and other invertebrate pests, including
for example the following~-
.
0 ~ ~
Tetran~chus _larius Blatella ~ermanica
~his fabae Musca domestica
e~oura viceae Pieris brassicae
APdes ~X~ Plutella maculipennis
S The inven~lon is illustrated by ~he following Ex.amples.
E ~PLE 1
Thls Ex~mple illustrates the preparation of Compound
no. 1.
A mixture of dl-chrysanthemic acid (50:50t cis:trans;
lo~ g) ~ 3(2~2-dichlorovinyloxy)benzyl bromide (2.0 g),
anhydrou~ pota~sium carbonate ~1.0 g) and acetone (25 ml)
wa~ ~tirred at the ambient temperature (ca. 18-22C) for 1~
hours. The ln801tlble portion was removed by filtration and
the g11trate evaporated under reduced pressure to yield a
reqldual oll which was dissolved in chloroform and washed
lS wlth saturated sodium bicarbonate solution and then with
water. After arying the chloroform solution over anhydrous
magnesium sulphate the solvent was removed under reduced
pressure and the residual oil sub~ected to preparative thin
layer chromatographv using a mixture of chloroform (10% v/v)
/
and petroleum ether (boiling range 40-60C; 90% v/v) as
eluent. Th~ required product was identified by infra-red
and nuclear magnetic spectroscopy.
EXAMPLE 2
This Example illustrate~ the preparation of Compound
no. 2.
A mixture of dl~3(2,2-dichlorovinyl)2,2-dimethylcyclo-
propane carboxylic acid ~80:20, trans:cis; 0.75 g), 3(2,2--
dichlorovinyloxy)benzyl bromide (1.0 g), anhydrous po~assium
carbonate (0.5 g) and acetone (25 ml) was stirred at the
ambient temperature for 18 hours. The product was isolated
from the reaction mixture by a procedure similar to that
used in Example 1, except that diethyl ether was used in
place of chloroform as solvent, and the T.L.C. eluent
consisted of 20% v/~ chloroform and 80% v/v petroleum ether
(boiling range 40-60C).
EXAMPLE 3
This Example lllustrates the preparation of (-~) oC-
cyano-3(2,2-dichlorovinyloxy)benzyl (+) cis/trans-2(2,2-
dlchlorovinyl)3,3-dlmethylcyclopropane carboxylate, Compound
no. 5, (Formula I; Rl, R~, R3, R4 are chlorine radicals, R5
is a cyano radlcal).
15 -
. . .
~ ., . ~ . - . .. . :
- ~ , ;
'
- .
. ~ :
3~ 5~
2(2,2-Dichlorovinyl)3,3-dimethylcyclopropane carboxylic
acid ( ~ (40:60, 1.29 g) is added to thionyl chloride
(5.0 g) and the mixture heated at 100C (steam bath) for one
hour, after which the excess thionyl chloride is removed by
S azeotropic distillation with toluene. The residual acid
chloride thus produced is dissolved in n-hexane (3.0 ml) and
the solutlon ob~ained added dropwise at the ambient temperature
to a solution of 3(2,2-dlchlorovinyloxy) benzaldehyde
cyanohydrln (1.5 g) in a mixture of n-hexane (7.0 ml) and
pyrldlne tO.5 ml). After completing the addition the
mixture is stirr~d for two hours at the ambien~ temperature.
The solid precipitate which forms is then removed by filtration
and the filtrate washed with water t2 x 10 ml~, dried over
anhydrou~ magnesium sulphate and concentrated by evaporation
of the solvent under r~duced pressure. The residual oil is
subjected ta preparative thin layer chromatography using
~ a plates and as eluent a mixture of chloroform (2 parts
by ~olume) and petroleum ether (boiling range 60-80C, 3
p~rts by volume), to yield substantially pure (+) OC-cyano-
3(2,2-dichlorovinyloxy)benzyl (+) cis/trans-2t2,2-dichloro-
vinyl)3,3-dimathylcyclopropane carboxylate, consisting of
40% of the ci~ isomer and 60~ of the trans isomer.
. .
EXAMPLE 4
Thls Example illustrates the preparation of Compounds
No~ 3 and 4.
- 16 -
. .
., :
` --\
:
The product obtained by ~he process of ~xample 2
(250 mg) was subjected to preparative thin layer chromato-
graphy using a silica coated plate and a solvent mixture
comprising 35% v/v chloroform - 65% v/v petroleum ether (60-
80C). The required products were identified by infra-red
and nuclear magnetic spectroscopy as Compound 3 (70 mg; (+)
cis-i30mer) and Compound 4 (100 mg; (+) trans-isomer).
. .
EXAMPLE 5 . .
This Example illustrates the preparation of 3~2,2-
dichlorovinyloxy)benzyl bromide.
(aJ Preparation of 1(3-tolyloxy)-2,2!2-trichloroethyl
aceta~e.
: Tola solution of anhydrous chloral (37.0 gj in dry
ether (125 ml) was added meta-cresol (27.0 g) and the
mixture was stirred at ~he ambient temperature for 20
minutes, after which it wa~ cooled to 10C and a solution of
triethylamine (25.25 g) in dry ether (lO0 ml) was slowly
added. Acetyl chlorid (20.0 g) was then care~ully added to
the ~tirred mixture and stirr$ng was continued for one hour.
The insoluble material was removed by filtration and the
~lltrate drled over anhydrou~ magnesium ~ulphate. A~ter
r~moval of the ether by evaporation under reduced pressure
the re~ldual oil was di~tilled under high vacuum and the
,~ - 17 -
..
~L5~
fracticn boiling at 132-134/0.5 mm Hg collected. Infra-red
and nuclear magnetic spectroscopic analysis indicat~d that
this was 1(3-tolyloxy)-2,2,2-trichloroethyl acetate.
(b) ~reparation of 3 tolyI 2,2-dichlorovinyl ether.
(i) By a metallic reductive dehydrohydrogenation
method. 1(3-tolyloxy)-2,2,2-trichloroethyl acetate (14.2 g)
was dissolved in glacial acetic acid (40 ml) and zinc dust
(3.6 g) was slowly added to the solution with stirring at
the amblent temperature. The temperature rose to 60~C in
respon~e to the exothermic reaction which occurred, after~
which the mixture was heated at 50-60C for 4 hours. The
mixture was filtered and the filtrate poured in an excess of
water and extracted with chloroform. The extracts we:re
wa~hed twice with water, with saturated sodium bicarbonate
solut1on, and finally with water. After drying the chloroform
extracts over anhydrous magnesium~sulpha~e, the solvent was
removed by evapora~ion under reduced pressure and the
residual oil distilled to yleld crude 8-tolyl 2,2-dichloro-
vinyl ether, collected as a fraction boiling at 92-95C/0.3 mmi,
~0 which was red1stllled and the fraction boiling at 84C/0.2 mm
Hg collected.
(ii) By an electrochmical reductive dehydrohalogenation
method 1(3-tolyloxy)~2,2,2-trichloroethyl acetate (15.8 g),
concentrated ulphurlc acid t98~ w/v, 9.8 g) and methanol
~5 (220 ml) wai~ charged into an electrolytic cell, which was
- 18 -
.
.
: ' ' ~ ... ..
~'
surrounded by a cooling bath set to maintain the temperature
at about 15C, and fitted with a cylindrical diaphragm,
stirrer, reference electrode (SCE) and a working electrode.
The cathode was a lead plate (surface axea about 40 cm2).
Us~ng a current density in the range 5 to 10 mA/cm~ the
reaction was conducted in the potential range -1100 to 1700
mV (SCE)o When reduction was completed the cathodic elect-
rolyte was neutralised with caustlc soda and sxtracted with
methylene chloride~ the extracts dried over anhydrous sodium
~ulphate and evaporated to yield a residue of crude 3-tolyl
2,2-dichlorovinyl ether.
(c) Preparation of 3(2,2-dichlorovinyloxy)benzyl
bromide.
3-Tolyl 2,2-dichlorovinyl ether (12.2 g) was dissolved
in carbon tetrachloride (75 ml), and N-bromosuccinimide
; ~12.0 g) and a trace of wet benzoyl peroxide added, and the
mixture refluxed for 3 hours. After ~iltration the solvent
was evaporated from the f1ltrate~ and the residue dissolved
ln ether and extracted with 1~ w/v sodium hydroxide solution.
The ethereal solution was dried over anhydrous magnesi~m
sulphate, the solvent removed by evaporation under reduced
pressure, and the residual oil distilled to yield a fraction
boiling at 150C/0.5 mm Hg. This fraction was shown by ~MR
to contain about 65% of the required product together with
about 30~ of unchanged starting material~ the remainder
belng a small proportion of the dibromomethyl compound.
- 19 -
...
.
~L5~
EXAMPLE 6
This example illustrates the prepa:ration of 3~2,2-
dichlorovinyloxy)benzyl alcohol.
A mlxture 3(2,2-dichlorovinyloxy)benzyl bromide (2.8
: g), ~odium p-toluene sulphonate (2.0 g) and methanol (20 ml)iB warmed to 50C or 1 hour, after which water (20 ml) and
~ toluene (20 ml) is added with agitation. The toluene layer
; i~ separated, washed with water and concentrated by evaporation
of the ~olvent under reduced pressure. The concentrate is
then added dropwl~e to a 15% (w/v) aqueous solution of
pota~slum hydxoxide (100 ml) and the mixture warmed to 60C
for 1 hour, cooled to the ambient temperature and extracted
with a mixtuxe of toluene (10 ml) and methyl iso-butylketone
(10 ml), the extracts dried over anhydrous magnesium sulphate
and ~he solvent~ evaporated under reduced pressure to yield
3(2,2~dichlorovinyloxy)benzyl alcohol as a residual pale
yellow oil.
'
~ EXA~PLE 7
Thi~ Example illustra~e~ the conver~lon of 3t2~2-
dichlorovinyloxy)ben~aldehyde to lts cyanohydrin, via the
bisulphite compound.
~ 20
. .
.. ~ .
To a stirred solutlon of sodium metabisulphlte (3.2 g)
in a mixture of water (5.2 ml) and methanol (5.2 ml) at the
ambient temperature is added 3(2,2-dichlorovinyloxy) benz-
; aldehyde (2.0 g). After 30 minutes the white precipitate
which forms is collected by filtration/ washed with co~d
methanol and dried to yield the bisulphite compound of
3(2~2-dichlorovinyloxy)benzaldehyde (2.5 g). This is
suspended in water t5 ml) and to it is added a solution of
sodium cyanide (0.4 g) in water (5 ml) at the ambient
temperatureO The mixture is stirred for 2 hours and then~
extracted wlth diethyl ether (2 x 10 ml3. The extracts are
combined, washed with water (2 x 10 ml)~ dried over an
hydrous magnesium sulphate and evaporated under reduced
pressure to yield the cyanohydrin of 3(2,~-dichlorov~nyloxy)-
benzaldehyde as a yellow oil.
EXAMPLE 8
The activity of a number of the compounds was tested
against a variety of insect and other invertebrate pests.
The compounds were used in the form of a liquid preparation
containing 0.1~ by welght of the compound except in the
tests with Aedes ~Ye~ wh~re the preparations contained
0.01~ by weight of the compound. The preparations were made
by dissolving each of the compounds ln a mixture of solvents
~.
' ' : ' ~ ,
:
. . .
~5~
consisting of 4 parts by volume o~ acetone and 1 part by
volume of diacetone alcohol. The solutions were th~n
diluted with water containing 0.01% by weight of a wetting
~` agent sold under the trade name "LISSAPOL" NX until the
liquid preparations contained the requixed concentration of
the compound. "Lissapol" is a Trade Mark.
The test procedure adopted with regard to each pest was
basically the same and comprised supporting a number of the
pests on a medlum which WhS usually a host plant or a
foodstuff on which the pests feed, and treating either or
both the pe~ts and the medlum with the preparations.
The mortality of the pests was then assessed at periods
usually varying rom one to three days after the treatment.
~he results of the tests are given below in Table I.
1$ In th~s table the first column indlcates the name of the
pest spec~es. Each o the subsequent columns indicates the
host plant or medium on which it was supported, the number
o~ da~s which were allowed to elapse after the treatment
before asqe~sing the mortality o~ the pests, and the results
obtained for each of the compounds numbered as abo~e. The
a~se~ment is sxpre~sed in integers which range from 0-3.
0 represents less than 30~ kill
1 represents 30 - 49% kill
2S 2 represents 50 - 90~ kill
3 represents over 90~ kill
- ~ ,
3~3
A dash (-) in Table I indicates that no test was
carried out.
In Table I 'contact test' indicates that both the pest~
and the medium were treated and 'residual testl indicates
that the medium was treated before infestation with th~
pests .
~ - 23 -
'
- -
L~ I O
~ ~ ~ o
~ ~ o ~
o
~ ~ o ~ ~ ~ ~ ~ ~ ~
~ I--1~11 0 N ~) O ~) O
_ ~
~n
.
o a
Z
E~
~ ~ ~ ~ g ~ o
1~ ~ 3 ~ td ~ ~ 3
. 1~ 0 0 0 ~tl O 1~
. P ~ h ~ 0 ~1
~ ~ F~ m P~
~ .
^ ~ a) s, M
a
~ ia rl
- ~ I
U~ ~q ~ O rl
~ .~ ~ ~a
t~ ~ ~ 2 ~ ~ ~ a~
~ ~ ~ ~ d U rl
U~ ~ ~ _ ~I t) ~ ~ O
~ ~ ~ ~ U~ r1 ~ rl I ~ ~ ~ rl ~_ rlE~ ra ~ ~ ~ ~ ~ C) CJ ~ U~ ."
Ul u) h a~ .~ u .~ Q d la Ln 0 0 ~ ~ ~ n u~
~ ::1 ~ 0 ~ ~: ~ ~ al E~ ~ ~ ~ O ~ a)
P~ ~ 't) ~ P4 ~ t4 tr O f3 "~ ~ h ~ ~i ~1
~ r~ ~ ~ ~ ~ ~ O ~ ~ ~ O ~ ~ O
::~- P4 4-1 td ld ~1 ~1 4-1 ~t
. ~: u) ~ ~1 ~ 1 o ~ u~ ~d U ~1
(d tolo~ ~ u~ ~ ni ~q ~ ~ a rl ~ ~ ~ u,
~1 'C) rll~d O C) ~) M U ~ ) (~ O 1-1 ~ ~ V ::1
~1 ~ O U~ O ~ ~rl U (I) It~ 1 ~n O
~ E~ ~ ~ ~ ~ ~1 ~, UO ~ rC
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Q8~
~XAMPLE 9
This Example illustrates a dusting powder which may be
applied directly to plants or other surfaces and comprises
1~ by welght of Compound no. 1 and 99-~ by weight of talc.
EXAMPLE 10
~5 Parts by weight of Compound no~ 2, 65 parts by
weight of xylene a~d 10 parts of an alkyl aryl polyether
alcohol ~'Tr~ton' X-100; 'Triton' ls a Trade Mark) were
mlxed in a sultable mixer. There was thus obtained an
emulsion concentrate which can be mixed with water to
produ¢e an emulslon suitable for use in agricultural appli-
catlons.
EXAMPLE 11
10 Parts by weight of Compound no. 2, 10 parts of an
ethylene oxide-octylphenol condensate ('Lissapol' NX;
'Li~sapol' is a Trade Mark) and ~0 parts by weight of
diacetonP alcohol were thoroughly mixed. There was thus
obtained a concentrate which, on mixing with water, gave an
aqueous disperRion suitable for application as a spray in
the control of insect pests.
~ ; ~ 25 -
, '
;.
. . .
,
~5~
"LISSAPOL" NX is a condensate of 1 mole of nonyl
phenol with 8 moles of ethylene
; oxide.
EXAMPLE 12
This Example lllustrates the preparation of
3(2~2-dichlorovinyloxy)benzaldehyde.
3(~72-Dichlorovinyloxy)benzyl bromide (2.5 g) was
care~ully added to a stirred solution of hexamethylene
: t~txamine (2.1 g) in carbon tet.rachloride (20 ml) at the
amblent temperatuxe. ~fter five minutes the precipitate was
collected by filtration and washed with acetone. The solid
~hu~ o~tained was a~ded to aqueous acetic acid solution (50
by welght, 16 ml) and the mixture r~fluxed for one hour. A
mixture of water (16 ml) and concentrated hydrochloric acid
(4.5 ml) was thell added and the mixture refluxed for a
lS urther 15 minutes. After cooling the mixture was extracted
wlth chloroform, the extracts washed with water (twlce),
dried over anhydrous magnesium sulphate and the solvent
removed by evaporation under reduced pressure to yield a
re~idue o~ ~ubstantially pure 3(2,2-d~chlorovinyloxy)benz-
.~0 aldehyde, identification of which was confirmed by infra-red
and nuclear magnetic re~onance spectro~copy.
~ ~ 26 -
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