Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~O~ZiL~L5
The present invention relates to cyclopropanecarboxylic
acid esters, to processes for their produc~ion, and to
their use in pest control.
The said cyclopropanecarboxylic acid esters have the
formula
x2/ CH y ~ ~ (I)
C~13
wherein
Xl and X2 each represent fluorine, chlorine or bromine, and
Y represents hydrogen, cyano or ethynyl.
Compounds of the formula I that are of particular
importance by virtue of their action are those wherein
Xl is identical to X2 and represents fluorine or chlorine,
and Y represents hydrogen, cyano or ethynyl.
The compounds of the formula I are produced by methods
-known per se, for example as follows:
X ~ O Y acid-binding
C=CH-CH - CH-C~Hal + HO-CH~-O~ agent - ~ I
CH3 ~III)
(II)
`~
~Z~4S
Xl. o Y acid-binding
2) ~ C=CH-C\ /CH-C-OH + Hal-CH ~ -O ~ agent ~ I
. CH3 ~V)
~IV)
X~' O
3) ~ C=CH-C ~ -/CH-C-OH ~ HO-CH ~ -O ~ water-bindin~
CH3 (III)
(IV)
In the ~ormulae II to V, the symbols Xl, X2 and Y
have the meanings given for the formula I, and Hal stands
for a halogen atom, especially for chlorine or bromine.
Suitable acid-binding agents for the processes 1 and 2
are, in particular, tertiary amines such as trialkylamines
a~d pyridine, also hydroxides, oxides, carbonates and
bicarbonates of alkali metals and alkaline-earth metals,
as well as alkali metal alcoholates such as potassium-t.
butylate and sodium methylate.~The water-binding agent used
for the process 3 can be, for example, dicyclohexylcarbo-
diimide. The processes 1 to 4 are performed at a reaction
temperature of between -10 and ~100C~ usually between 20
and 80C, at normal or elevated pressure, and preferably
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in an inert solvent or diluent.
Suitable solvents or diluents are, e.g., ethers and
ethereal compounds such as diethyl ether, dipropyl ether,
dioxane, dimethoxyethane and tetrahydrofuran; amides such
as N,N-dialkylated carboxylic acid amides; aliphatic,
aromatic as well as halogenated hydrocarbons, especially
benzene, toluene, xylene, chloroform and chlorobenzene;
nitriles such as acetonitrile; dimethylsulphoxide and
ketones such as acetone and methyl ethyl ketone. The
process 2 can be performed also in an aqueous solution.
The starting materials of the formulae II to IV are
known or can be produced by methods analogous to known methods.
The compounds of the formula I are obtained as mixtures
of various optically active compounds and cis/trans isomers,
unless the starting materials used to produce the said
compounds are homogeneous optically active compounds or
- cis/trans isomers. The ~ferent stable isomeric mixtures can
be separated by ~nown methods into the homogeneous isomers.
It is understood that compounds of the formula I embrace
both the individual isomers and the mixtures thereof.
The compo-mds of the formula I are suitable for the
control of various animal and plant pests. They are suitable
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~09Z~4~
in particular for controlling insects and members of
~he order Acarina. They can be used, for example, against
insects of the families: Tettigoniidae, Gryllidae,
Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae,
Cimicîdae, Delphacidaeg Aphididae, Diaspididae, Pseudo-
coccidae, Scarabaeidae, Dermestidae, Coccinellidae,
Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae,
Lymantriidae 3 Pyralidae, Culicidae, Tripulidae, Stomoxydae,
Trypetidae, Muscidae, Calliphoridae and Pulicidae; as well as
against acarids of the families: Tetranychidae and
Dermanyssidae.
The compounds of the formula I are especially suitable
for combatting insects that damage plants, particularly
insects tnat damage plants by eating, in crops of ornamental
plants and useful plants, especialLy in cotton crops (e.g.
against Spodoptera littora]is and Heliothis virescens) and
in crops of vegetables (e.g. against Leptinotarsa decemlineata
and ~Iyzus persicae). The active substances of the formula I
have a very good action also against flies, such as Musca
domestica and mos~uito larvae.
The acaricidal or insecticidal action can be substantially
broadened and adapted to suit given circumstances by the
addition of other insecticides and/or acaricides. Suitable
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z~
additives are for example:
organic phosphorus compounds,
nitrophenols and derivatives thereof,
formamidines,
ureas,
o-ther pyrethrin-like compounds, as well as
carbamates and chlorinated hydrocarbons.
Compounds of the formula I are combined particularly
advantageously with substances that have a synergistic or
intensifying effect on pyrethroids. Examples of such
compo~mds are, inter alia, piperonylbutoxide, propynyl ether
and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-
3,6,9-trioxaundecane (Sesamex or Seso~ane), S,S,S-tributyl-
phosphorotrithioates and 1,2-methylenedioxy-4-(2 (octyl-
1~ sulphinyl)-propyl)-benzene.
The compounds of the formula I can be used on their
own or together with suitable carriers and/or additives.
Suitable additives can be solid or liquid and they
correspond to the substcmces common in formulation practice,
such as natural or regenerated substances, solvents,
dispersing agents, wetting agents, adhesives, thickeners~
binders and/or fertilisers.
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The compositions according to the invention are
produced in a manner known per se by the intimate mixing
and/or grinding of active substances of the formula I
with suitable carriers, optionally with the addition
of dispersing agents or solvents which are inert to the
active substances. The active substances can be obtained
and used in the following forms:
solid preparations: dust, scattering agents, granulates
(coated granulates, impregnated
granulates and homogeneous granulates);
liquid preparations:
a) water-dispersible active-substance concentrates:
wettable powders, pastes or emulsions;
b) solutions.
The content of active substance in the described
compositions is between 0.1 and 95%; in this connection
it is to be mentioned that in the case of application from
an aeroplane, or by means of other sui~able devices, con-
centrations of up to 99.5% may be used, or even the pure
2Q active substance.
The active substances of the formula I can be
formulated, for example, as follows ['parts' denote parts
by weight].
Dusts:
The following substances are used in the preparation
of a) a 5% dust, and b) a 2% dust:
a) 5 parts of active substance,
95 parts of talcum;
~) 2 parts of active substance,
1 part of highly dispersed silicic acid,
97 parts of talcum.
The active substances are mixed and ground with the
carriers.
Granulate:
The following substances are used to produce a 5%
granulate:
5 parts of active substance,
0.25 part of epichlorohydrin,
0.25 part of cetyl polyglycol ether,
3.50 parts of polyethylene glycol,
91 parts of kaolin ~particle size 0.3 - 0.8 mm).
The active substance is mixed with epichlorohydrin
and dissolved with 6 parts of acetone; the polyethylene
glycol and cetyl polyglycol ethcr are then added. The
. ~
1~31Z~
solution thus obtained is sprayed onto kaolin, and the
acetone is subsequently evaporated off in vacuo.
Wettable powder:
The following constituents are used to prepare
a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a~ ~0 parts of active substance,
parts of sodium lignin sulphonate,
1 part of sod~um dibutyl-naphthalene sulphonate,
54 parts of silicic acid;
10b) 25 parts of active substance,
4.5 parts of calcium lignin sulphonate,
1.9 parts of Champagne chalk/hydroxyethyl cellulose
mixture (1:1),
1.5 parts of sodium dibutyl naphthalene sulphonate,
19.5 parts of silicic acid,
19.5 parts of Champagne chalk,
28.1 parts of kaolin;
c~ 25 parts of active substance,
2.5 parts of isooctylphenoxy-polyoxyethylene-
2Q ethanol,
1.7 parts of Champagne chalk/hydroxyethyl cellulose
mixture ~1:1),
_ g _
3L~9~5
8.3 parts of sodium aluminium silicate,
16.5 parts of kieselguhr,
46 parts of kaolin;
d) 10 parts of active substance,
3 parts of a mix~ure of the sodium salts of
saturated fatty alcohol sulphates,
parts of naphthalenesulphonic acid/formaldehyde
condensate,
82 parts of kaolin~
The active substances are intimately mixed in suitable
mixers with the additives, and the mixture is then ground in
the appropriate mills and rollers. Wettable powders are obtained
which can be diluted with water to give suspensions of any
desired concentration.
Emulsifiable concentrates:
-
The following substances aTe used to produce a) a 10%,
b~ a 25%, and c) a 50% emulsifiable concentrate:
a) 10 parts of active substance,
3.4 parts of epoxidised vegetable oil,
3.4 parts o a combination emulsifier consisting
of fatty alcohol polyglycol ether and
alkylarylsulphonate calcium salt,
40 parts of dimethylformamide,
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43.2 parts of xylene;
b) 25 parts of active substance,
2.5 parts of epoxidised vegetable oil,
parts of alkylarylsulphonate/fatty alcohol
polyglycol ether mixture,
parts of dimethylformamide,
57.5 parts of xylene;
c) 50 parts of active substance,
4.2 parts of tributylphenol-polyglycol ether,
5.8 parts of calcium-dodecylbenzenesulphonate,
parts of cyclohexanone,
parts of xylene.
It is possible to prepare from these concentrates, by
dilution with water, emulsions of any desired concentration.
Spray:
The following constituents are used to prepare a) a
5% spray, and b) a 95% spray:
a) 5 parts of active substance,
1 part of epichlorohydrin,
2~ 94 parts of ligroin ~boiling limits 160 - 190C);
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b) 95 parts of active substance,
. par~s of epichlorohydrin.
The invention is further illustrated by the following
Examples.
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_ ample 1
Production of 2-methyl-3~ dichlorovinyl)-cyclopr
carboxylic acid-(3-phenoxy-benzyl)-ester
_.
To a solution of 3.5 g of 2-methyl-3-(~,~-dichloro-
vinyl)-cyclopropanecarboxylic acid (b.p.: 102-104C/0.07 Torr)
in 15 ml of ~ethyl ethyl ketone there are added dropwise at
15-20C, with stirring, firstly 2.92 g of triethylamine
and then 5.25 g of 3-phenoxybenzyl bromide. The reaction
mixture is stirred for 5 hours at 70-80QC, and subsequently
poured into 100 ml of ice water. The crude product is
extracted with ether, the resulting ether solution is
washed with sodium bicarbonate solution and with water
and dried over sodium sulphate.
After removal of the ether by distillation, there is
obtained the compound of the formula
~C=CH-CH - CH COOCH2 ~ ~
CH3
in the form of colourless oil having a refractive index
of nD= 1~5739.
The following compounds are produced in an analogous
manner: / CH=CH-CH -/ H - C00-CH ~ -o
CH3
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~0~3~ S
Xl X2 _ Physical data
.. .. ~
- Cl Cl CN nD = 1,5702
- F F CN nD = 1,5403
F F H nD = 1,5424
F F ~C_CH nD = 1,5402
Cl Cl -C-=CH nD = 1,5748
A) Insecticidal stomach poison action
Tobacco and potato plants were sprayed with a 0.05%
aqueous active-substance emulsion ~obtained from a 10%
emulsifiable concen~rate).
After drying of the coating, caterpillars of Spodoptera
littoralis in the L3-stage and of Heliothis virescens
in the L3-stage were placed onto the tobacco and potato
plants, The test was carried out at 24C with 60%
relative humidity.
Compounds according to Example 1 exhibited in the
ahove test a good insecticidal stomach poison action against
Spodoptera littoralis and Heliothis virescens caterpillars.
B) Insecticidal contact action
.
One day before application of the active-substance
emulsion, broad beans (Vicia faba) grown in pots were infested
with about 200 bean aphids (Aphis fabae) per plant. The
spray emulsion at a concentration of 1000 ppm (prepared
from a 25% wettable powder) was applied, by means of a
compressed~air sprayer, to the leaves infested with bean
aphids. An evaluation was made 24 hours after application.
Compounds according to Example 1 exhibited in the above
test a good contact action against Aphis fabae.
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~ 9 ~ ~ 5
Example 3
Action against Acarina
Phaseolus vulgaris (bush beans) were infested, 12 hours
before the ~est for acaricidal action, with an infested
piece of leaf from a mass culture of Tetranychus urticae.
The transferred mobile stages were sprayed with the
emulsified test preparations from a chromatography-sprayer
in a manner ensuring no overflowing of the spray liquor.
An assessment was made after 2 to 7 days, by examination
under a binocular, of living larvae and dead larvae, adults
and eggs, and the results were expressed in percentages.
The treated plants were kept during the "holding time"
in greenhouse compartments at 25C.
Compounds according to Example 1 were effective in
the above test against eggs, larvae and adults o~
Tetranychus urticae.
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