Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~5~
The present invention relates to cyclopropanecarboxylic acid
esters, to a process for their manufacture and to their use in pest control.
The cyclopropanecarboxylic acid esters have the formula
I 1 IX4 Yl
2 I CH Cl\ / H C O IH ~ ~ Y2 (I)
wherein
Xl and X2 represent methyl, fluorine, chlorine or bromine,
X3 and X4 represent chlorine or bromine, and
Rl represents hydrogen or ethyl, or
Xl and X2 represent methyl or fluorine, with one proviso that Xl and X2
are not both fluorine,
X3 and X4 represent chlorine or bromine, and
Rl represents methyl,
R2 represents hydrogen, methyl, cyano or ethynyl, and each of
Yl and Y2 represents hydrogen, halogen, methyl or trifluoromethyl.
The compounds of the formula I are prepared by methods which are
known per se, for example as follows:
1 1X4 0 Yl
3 / \ 2 Y2
(II) (III)
acid acceptor>
,i, ,~;
1152~
Xl X4 O Yl
X2 ,C CH C~-- CH-C-Z + Ho-CH~3-o~ 2
CH3 Rl (V)
(IV) acid acceptor ~ I .
~ 1 X4 o Y
2 , ~ ~CH C -OH + HO-CH~-O~ 2
CH3 Rl
(II) (V)
hydrophilic age~t I
,
3 / \ 2
CH3 Rl
(VI ) (V)
-ROH
S ) ~C =C H -C H - C H - C -O -C H~O ~ bromi~
CH3. Rl
(VII) (each of X3 and X4 is bromine)
In the formulae II to VII, Rl, R2, Xl.to X4, Yl and Y2
are as defined in formula I.
~2~Z
In the formulae III and IV, ~ represents a halogen atom,
especially a chlorine or bromine atom, and in formula VI
R represents Cl-C~alkyl, especially methyl or ethyl.
Suitable acid aCceptors for processes 1 and 2 are in par-
ticular tertiary amines, such as trialkylamine and pyridine,
and also hydroxides, oxides, carbonates and bicarbonates of
alkali metals and alkaline earth metals, and in addition
alkali metal alcoholates, for exampIe potassium tert-butyl-
ate and sodium methylate. As hydrophilic agent for process
3, dicyclohexylcarbodiimide can be used for example. Processes
l to 5 are carried out at a reaction tetnperature between -10
and 120C, usua]ly between 20 and 80C, under normal or
elevated pressure and preferably in an inert solvent or di-
luent. Examples of suitable solvQnts or diluents are: ether
and ethereal compounds, for example diethyl ether, dipropyl
ether, dioxane, dimethoxy ethane and tetrahydrofurane; amides,
such a~ N,N-dialkylated carboxamides; aliphatic, aromatic and
halogenated hydrocarbons, especially benzene, toluene, xy-
lenes, chloroform and chlorobenæene; nitriles, such as ace-
tonitrile; dimethyl sulphoxide; and ketones, such as acetone
and methyl ethyl ketone.
The starting materials of the formulae II to VII are known
or they can be prepared by methods analogous to known ones.
The co~pounds of the formula I are in the form of a mixture
of different optically active isomers if individual opti-
cally active starting materials are not used in the reaction.
The di~ferent isomer mixtures can be separated into the in-
dividual isomers by known methods. The compound of the for-
mula I is to be understood as comprising both the indivi-
dual isomers and the mixtures thereof.
~lS2(~92
~he con~pounds of the formula I are suitable for controllin~
a variety of animal and plant pests. In particular, the com-
pounds of the formula I are suitable or controllin~ insects,
phyt~pathogenic mites and ticks, for example o the orders:
Lepidoptera, Coleootera, Homoptera, Heteroptera, Diptera,
Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera,
Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.
In particular, the compounds of the formula I are suitable
for controlling insects which are harmful to plan~s, especial-
ly insects which damage plants by eating, in ornamentals
and crops of useful plants, especially in cotton plantations
(e.g. Spodoptera littoralis and Heliothis virescens) and in
vegetable crops (for example Leptinotarsa decemlineata
and Myzu8 persicae).
The active compounds of the formula I also have a very
good action against flies, for example Musca domestica and
mosquito larvae.
The insecticidal and/or acaricidal action can be substan-
tially bxoadened and adapted to prevailing circumstances by
addition of other insecticides and/or acaricides. Examples
of-suitable additives include: organic phosphorus compounds,
nitrophenols and derivatives thereof, ~ormamidines, ureas,
pyethroids, carbamates, and chlorinated hydrocarbons.
Compounds of the formula I are also combined with parti-
cular advantage with substances which exert a synergistic or
potentiating effect on pyrethroids. Examples of such com-
pounds include: piperonyl butoxide, propynyl ether, propynyl
oximes, propynyl carbamates and propynyl phosphonates, 2-
(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamex
or Sesoxane), S,S,S-tributylphosphorotrithioate, 1,2-Methy-
lenedioxy-4(2-(octylsulphonyl)-propyl)-benzene.
,,
-- 5 --
1 ~5~
The compounds o~ the formula I ~ay be used as pure acti-
ve substance or together with suitable carriers and/or addi-
tives~ Suitable carriers and additives can be solid or liquid
and correspond to the substances conventionally used in the
art of fonnulation, for example natural or r~generated sub-
stances, solvents, dispersants, wetting agents~ tackifiers,
thickeners, binders and/or fertilisers.
The compositions of the present invention are manufac-
tured in known manner by homogeneously mixing and/or grin-
ding active substances of the foL~ula I with the suitable
carriers, with or without the addition of dispersants or
solvents which are inert to the active substances.
The compounds of the formula I may be processed to the
following formulations:
Solid formulations:
Dusts, tracking powders and granules (coated granules,
impregllated granules and homogeneous granules).
Liquid formulations:
a) active substances which are dispersable in water:
wettable powders, pastes and emulsions;
b) solutions.
The content of active substance in the above described
compositions is generally between 0.1% and 95%, though con-
centrations of up to 99.5% or even pure active substance can
also be used if the compositions are applied from an aircraft
or other appropriate application devices.
The compounds (active substances) of the ~ormula I can,
for example, be formulated as follows (throughout the pre-
sent specification all parts and percenkages are by weight):
-- 6 --
.
,
llSZ(~Z
Dus~s
The following substances are used to produce
a) a 5% and b) a 2% dust:
a) S parts of active substance,
parts of talc;
b) 2 parts of active substance,
1 part of highly disperse silicic acid,
97 parts of talc.
~ he active substances are mixed with the carriers and
ground.
Granules
The following substances are used to produce 5%
granules:
S parts of active substance
0.25 parts of epichlorohydrin,
0.25 parts o~ 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
the mixt~re is dissolved in 6 parts of acetone; the poly-
ethylene glycol and cetyl polyglycol ether are then added.
The resultant solution is sprayed on kaolin, and the ace-
tone is qubsequently evaporated in vacuo.
115~(~92
W able powders_
The following constituents are used for the preparation
o a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a) -40 parts of active substance,
5 parts of sodium ligninsulphonate,
1 part of sodium dibutylnaphthalenesulphonate,
54 parts parts of silic~c acid.
b) 25 parts of active substance,
4~5 parts of calcium ligninsulphonate,
1.9 parts of Champagne chalk/hydroxyethyl cellulose
mixture (1:1),
1,5 parts of sodium dibutylnaphthalenesulphonate,
19,1 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-
ethanol,
1,7 parts of Champagne chalk/hydroxyethyl cellulose
~ixture (1:1),
8~3 parts of sodium alumlnium silicate,
16,5 parts of kieselguhr,
46 parts of kaolin;
d) 10 parts of active substance, f
3 parts of a mixture of the sodium salts of
saturated fatty alcohol sulphates,
parts of naphthalenesulphonic acid/formaldehyde
condensate,
82 parts of kaolin.
,
-- 8 --
~15~
The active substances are homogeneously mixed with the
additive~ in suitable mixers and the mixture i~ then ground
in appropriate mills and rollers. Wettable powders are ob-
tained which can be diluted with water to give suspensions
of the desired concentration.
Emulsiiable concentrates.
The following substances are 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 of a combination emulsifier consisting of
fatty alcohol polyglycol ether and
alkylarylsulphonate calcium salt,
parts of dimethyl formamide,
43~2 parts of xylene;
b) 25 parts of active substance,
2,5 parts of epoxidised vegetable oil,
parts of alkylarylsulphonatetfatty alcohol
polyglycol ether mixture,
parts of dimethyl formamide,
57~5 parts of xylene;
c) 50 parts of active substance,
4~2 parts of tributylphenol-polyglycol ether,
5~8 parts of cylcium dodecylbenzenesulphonate,
parts of cyclohexanene,
parts of xylene.
By diluting these concentrates with water it is possible
to obtain emulsions of the required concentration.
g _
2~9Z
Sprays:
The ollowing ingredients are used to prepare a) a 5%
spray, and b) a 95% spray:
a) 5 parts of active substance,
1 part of epichlorohydrin,
94 parts of ligroin (boiling range 160-190C);
b) 95 parts of active substance,
parts of epi.chlorohydrin.
The invention is further illustrated by the following
Examples.
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~.521~9Z
Example 1
Preparation of ~-cyano-m-phenoxybenzyl 3-(2',2l-dichloro-1',
2'-dibromoethyl-2-methylcyclopropanecarboxylate
. _ . . .
12 g of ~-cyano-m-phenoxybenzyl 3-(2',2'-dichloro-
vinyl)-2,2-dimethylcyclopropanecarboxylate are dissolved in
100 ml of carbon tetrachloride. To this solution are added
dropwise 4.77 g of Br2 at 20-30C. The carbon tetrachloride
is then distilled off, yielding the compound of the formula
Cl Br 0 CN
C~ ~CH-C-O-CH~-O~
- CH3
with a refractive index of n40. 1.5776 (isomer mixture).
The following compounds are prepared in analogous manner:
CH3-C - CH-CH - CH-C00-CH ~ -0 ~ nD : 1.5675
~ \ isomer mixture
C~13 CH3
CH3 Br
3 , CH\ - CH - C00-CH ~ 0 ~ n40 : 1.5605
/ \ isomer mixture
CH3 CH3
~S2~92
Cl Br
Br CH ~ ~3 nD : 1 . 5 8 2 8
' isomer mixture
CH3
Cl- C - CH-CH ~ CH-COO-CH~-O~ nD :1,.5639
~ ~ isomer mixture
CH3 C2H5
Example 2
Insecticidal stomach pois~n action
.. . . ~
Cotton plants were sprayed with a 0.05% aqueous emulsion of
active substance (obtained from a 10% emulsifiable concen-
trate). After the spray coating had dried, the cotton plants
were populated with Spodoptera li~toralis and Heliothis vi-
rescens in the L3-stage. The text was carried out at 24C
and 60% relative humidity.
In this teqt, the compounds of Example 1 exhibited a good in-
secticidal stomach poison action against Spodoptera and He-
liothis larvae.
,
'
~ ~5Z~ 9Z
Example 3
Action against Chilo suppressalis
.. . . ....
Rice seedlings of the variety Caloro were transplanted into
plastic pots (6 plants per pot) having a diameter of 17 cm
at the top and reared to a height of about 60 cm. Inf~sta-
tion with Chilo suppressalis larvae (Ll-stage, 3 to 4 mm in
length) took place two days after the addition of active
substance in granule form (rate of application: 8 kg of ac-
tive ingredient per hectare) to the paddy water. Evaluation
of the insecticidal action was made 10 days after addition
of the granules. In this test, the compounds of Example 1
acted against Chilo suppressalis.
Example 4
. . .
Acaricidal action
-
Twe~ e hours before the tes~ for acaricidal action, Phaseolus
vulgaris plants were populated with an infested piece of
leaf from a mass culture of Tetranychus urticae. The mobile
stages which had migrated to the plants were sprayed with
the emulsified test preparations from a chromatography ato-
miser in such a way that the spray broth did not run off. The
number of living and dead larvae, adults and eggs was eva-
luated under a stereoscopic microscope after 2 and 7 days
- 13 -
,. ~ . .... . . . . .. . .
~'1 5;~(~92
and the result expressed in percentage values. During the
test run, the plants stood in greenhouse compartments at
25 ~C .
In this test, the compounds of Eæample 1 acted against adults,
larvae and eggs of Tetranychus urticae.
xample 5
Action against ticks
,
A) Rhipicephalus bursa
Five adult ticks and 50 tick larvae were counted into each of
a number of test tubes and immersed for 1 to 2 minutes in 2
ml of an aqueous emulsion containing a concentration of 100,
10, 1 or 0.1 ppm of test substance. Each test tube was then
sealed with a cotton-wool plug and placed on its head to
enable the co~ton wool to absorb the active substance emul-
sion. Evaluatioh of the action against adults was made after
2 weeks and of that against larvae after 2 days. Each test
was repeated twice.
B) Boophilus microplus (larvae)
Test were carried out with 20 OP-sensitive and 20 OP-resist-
ant larvae using aqueous emulsions similar to those used in
Test A. (The resistance refers to the tolerance towards dia-
zinone). The compounds of Exampl-_ 1 acted in these tests
against adults and larvae of Ehipicephalus bursa and OP-sen-
sitive and OP-resistant larvae of Boophilus microplus.
- 14 -
.
llS~092
Action against Erysiphe graminis on Hordeum vulgare
Barley plants about 8 cm in height were sprayed with a spray
broth (0.05% of active ingredient~ prepared from a wettable
powder of the active compound. 48 hours later, the treated
plants were dusted with conidia of the fungus. The infected
barley plants were stood in a greenhouse at about 22C and
the fungus attack was evaluated after 10 days. In this test,
the compounds of Example 1 acted against Erysiphe graminis.
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.. . , , . . . . . . . . . . ~
