1076135
.
-- 2 --
This invention relates to cyclopropane carboxylic
acid esters and their use as pesticides.
According to the present invention, there are
provided compounds of the formula I
~ C=CH-CH - CH-COOCH~-CII=C-C~2 ~ (1
ÇH3 C~3
: '
wberein Xl represents a chlorine, fluorine or bromine
atom and X2 represents a fluorine or bromine atom.
The compounds of formula I can be prepared by
.
process analogaus to ~nown methods for example by reacting
a compound of the formula II
X
C=CH-CH - CH-COOH
~: X2 cl~3 CH -
:~ 3
;~ wherein Xl and X2 have the sa~e meanings as given for
formula I, with a compound of the formula .
~:
X-CH -CH-C-CH ~ ~III)
Cl
':
~ . ,,;, '.
'~"D
~."' .
. ... ; .. , .. , . . ,, . ., ., , .... ... ~ " ,. , .. , . .
,., . . ;. .. . . ... .. . .. . .. .. . . .. .
~7 61 3 5
-- 3 --
wherein X represents a halogen atom, i~ particular a
chlorine or bromine atom, in the presence of a base
such as a tertiary amine, for example a trialkylamlne
or pyridine, or a hydroxide, oxide, carbonate or
b~carbonate of an alkali metal and alkaline earth metal,
or an alkali metal alcoholate, for exa~ple potassium ~;
tert.butylate or sodium methylate.
The process is carried out at a reaction
temperature generally between -10 and 100C, pre~erably
between 20 and 80C, at normal or elevated pressure, ~ ~
and preferably in a solvent or diluent which is inert ~ `
: .:
to the reactants.
~ xamples of suitable solvents or diluents
that may be used are: ethers and ethereal compounds,
for example diethyl ether, dipropyl e her, dioxan,
d~methoxy ethane, tetrahydrofuran; amides, for example
N,N-diethylated carboxy amides; aliphatic, aromatic and
halogenated hydrocarbons, especially b~nzene, toluene,
xylene, chloroform, chlorobenzene; nitriles, for example
acetonitrile; dimethyl sulfoxide; and ~etones, for
example acetone, methylethyl ketone.
The starting materials of formulae II and III are
known and can be prepared by methods analogous to known
methods.
The compounds of formula I occur in different
optically active and cis/trans-isomeric forms. If therefore
individual isomers are not used asstarting materials, then
1~37f~13S
"_ ~
_ 4 _
racemic and/or cis/trans-iso~eric mixtures are r.ecessarily
obtained.
The different isomeric mixtures obtained can be
separated into the individual isomeric for~s t for example
by recrystallis~tion or by means of chromatographic
separating met~ods, for example by gas chro~atography
or by adsorption o~ a separating material with selective
~adsorption activity, such as silica gel or aluminium
oxide, and subsequently eluting the separated iso~ers
with a suitable sol~ent.
T~e compounds of formula I co~prise both the
lndividual optically active isomers and cis- or trans-
isomers 2nd mixtures thereof~
The compounds of the formuIa I are suitable for
controlling a variety of animal and plant pests. In partic-
ular, the compounds of the formula I are suitable for con-
trolling insects, phytopathogenic mites and ticks, for
example of the orders: Lepidoptera, Coleoptera, 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 plants,
especially insects which damage plants by eating, in ornam-
entals 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 Myzus persicae).
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? : ~ ~
0'76~ 3 5
, ~ :
-- 5 --
The active compounds of the formula I also have a very
good action against flies, for example Musca do~estica and
mosquito larvae.
The insecticidal and/or acaricidal action can be substan-
tially broadened 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, form~midines, 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 Seso~ane), S,S,S-tributylphosphorotrithioate, 1,2-Methy-
lenedioxy-4(2-(octylsulphonyl)-propyl)-benzene.
The compounds of the formula I may be used as pure acti-
ve substance or together with suitable carriers and/or addi-
tives. Suitable carriers and additives can be solid or liquld
and correspond to the substances conventionally used in the
art of formulation, for example natural or regenerated sub-
stances, solvents, dispersants, wetting agents, tackifiers,
thickeners, binders and/or fertilisers.
~; The compositions of the pr~sent invention are m~tnufac-
tured in known manner by homogeneously mixing and/or grin-
ding active substances of the formula 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 for~ula I may be processed to the
following formulations:
: ., :
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.. . ..
.. ., , - . .. . .
-- ~076135
. ~ .
-- 6 --
Solid formulations:
Dusts, tracking powders and granules (coated granules,
impregnated granules and homogeneous granules).
Liquid formulations:
a) active substances which are dispersable in water:
wettable powders, pastes and emulsions;
b ) so lutions.
The content of active substance in the above described
co~positions is generally between 0.1% and 95%, though con-
centrations of up to 99.5% or even pure active substance
aIso be used if the co~positions are applied from an aircraft
or other appropriate application devices.
The compounds (active substances) of the formula I can,
for example, be formulated as follows (throughout the pre-
~ sen~ specification all parts and percentages are by weight):
: , '
~ I)UBt8
The following substances are used to produce
a) a 5% and b) a 2% dust: -
a) 5 parts of active substance,
parts of talc;
b) 2 parts of active substance,
1 part of highly disperse silicic acid, ~ ;~
97 parts o~ talc.
The active substances are mixed with the carriers and
ground.
Granules
.,, ,-.~
The following substances are used to produce 5%
granules:
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.", ' ' .'" , ,' '- ',, ' ' . ', ' ' ',, ,. , . " , ' ' '' '. ',, ' ,: ' " . .: ,"
1(~7613S ~ ~
.
- 7
5 parts of active substance -
0.25 parts of epi~hlorohydrin, .
0.25 parts 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 .
the mixture is dissol~ed 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 subsequently evaporated in vacuo.
Wettable ~owders:
The ollowing constituents are used or the preparation
of a~ a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of active substance,
parts of sodium ligninsulphonate,
1 part of sodium dibutylnaphthalenesulphonate,
: 54 parts parts of silicic 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 aluminium silicate, ..
.~,, '
11~ .
, .. , ~ ;. ,. ... . ., .. . ' ' : : ' :
.. . , ~ , , ~ .
.
07~35
-- 8 --
16~5 parts of kieselguhr,
46 parts of kaolin;
d) 10 parts of active substance,
3 parts of a mixture of the sodium salts of
saturated fatty alcohol sulphates,
parts of naphthalenesulphonic acid/formaldehyde
condensate,
82 parts of kaolin.
The active substances are homogeneously ~ixed with the
~ additives in suitable mixers and the mixture is then ground
;~ in appropriate ~ills and roLlers. Wettable powders are ob-
tained which can be diluted with water to give suspensions
of the desired concentration.
Emulsifiable 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 o~ alkylarylsulphonate/fatty alcohol
polyglycol ether mixture,
5 parts of dimethyl forma~ide, -
57.5 parts of xylene;
.: :
'; ."'' :" ' , ' . ' - ":" ;' '. ; :
,, . ~ . .. .
` 1~7 ~1 3 5
. .
_ 9 _
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 ispo~ible
to obtain emulsions of the required concentration.
Sprays:
The following ingredients are used to prepare a) a 5%
spray, and b) a 95% spray:
a) 5 parts of active substance,
1 part o~ epichlorohydrin~
94 parts of ligroin (boiling range 160 190C),
b~ 95 parts of active substance,
5 parts of epichlorohydrin. -~
The invention is further illustrated by the following
Exa~pIes.
,
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. : , . .: . . . . . .
' .. , " ' '~
:,:, , ~ , ,; ,
-- 10 --
- ~xam~le 1
Manufacture of 2,2-dimethyl-3-(2,2-dibromovinyl)-
cyclopropanecarboxylic acid-4-phenyl-3-chloro-2-butene
ester of formula
<IMG>
- 9.95 ~ of 2,2-dimethyl-3-(2,2-dibromovinyl)-
cyclopropanecarboxylic acid are added by small amounts
to a solution of 3.4 g of potassium tert. butylate in
50 ml of methyl ethyl ketone. Then 9.5 g of 2,4-dichloro-
butenyl(2)-benzene is added to the reaction mixture, whichis
stirred for 8 hours at 70 - 80C.
After it has cooled, the reaction mixture is poured
onto ice water. The product is extracted into ether and the
etherealextract is washed with 3 x 100 ml of 3~ Na2C03
solution. The ether solution is dried over sodium sulphate,
the ether i~ distilled of~ and the c~ de product ~ractionated
in a high ~acuum. The desired product is obtained as a
yellowish li~uid with a boiling point of 179 - 180C/0.015
Torr.
The following compounds of formula I are obtained
in analogous manner:
~ 6~L35
-- 11 --
. .
C = CH - CH - CH - COOCH~-CH = I - CH2 _9
~3 H3
Boiling point 130 - 1~2C/0.02 Torr.
. ~:
Cl
C = CH - CH - CH - COOCH2-CH = C - CH
Br /C\ Cl
3 3
Boiling point 160 - 1?0C/0.15 Torr.
.
. .
Insecticidal Stomach poison action
Tobacco and potato plants were sprayed with a
0.05% aqueous emulsion ~obtained from a 10~ emulsifiable
conoentrate). After the coating had dried, the tobacco
plants were populated with Spodoptera littoralis larvae.L
and Heliothis virescens larvae L3 and the potatoe plants
wlth Colorado potato beetle larvae L3 (Le~tinotarsa decem-
lineata). The test was carried out at 24C and 60% relative
humidity. In the above test, the compounds of Example 1 -
exhibited good stomach poison action against S~odoptera ::
littoralls, Heliothis virescens and Leptinotarsa decem- ` -
llneata.
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" " '' . , ' ' ~ .
.. .. . . .... . ... .
, ~()76~3S
- 12 -
Example 3
::
Insecticidal action against Musca domestica
A given amount of a solution of the active
substance in acetone (concentration of active substance =
0.05%) was pipetted onto 50 g of maggot substrate in
beakers. After the treated substrate had been thoroughly -
mixed, the acetone was allowed to evaporate off over the
course of at least 20 hours.
25 one day-old maggots were then put into each ~ -
beaker. After 5 days the pupae were flushed out and --
deposited in the same beaker. Mortality was determined
after 10 days. In this test the compounds of Example 1
acted well against Musca domestica. ~ -
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''': , ,. ' ' ' ,.,"., '", ', ', ' '" .',' ' '~
