Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Case 5-11781/1+2/A
The present invention relates to cyclopropanecarboxylic
acid esters, to processes for producing them, and to
their use in combating pests.
The cyclopropanecarboxylic acid esters have the
formula
/CzCH-CH - CH-C-O-CH-t~ \--0--~ ~ ~
Xl /C\ C
3 3 C
CH3
in which
Xl is fluorine, chlorine or bromine, and
Y is methoxy, methyl, fluorine, chlorine or bromine.
Compounds of the formula I which are of particulaLr
importance by virtue of their action are those in whi.ch
Xl i9 fluorine, chlorine or bromine, and Y is p-methoxy,
p-methyl, p-fluorine, p-chlorine or p-bromine.
' '
: . ', '
~15'~
2 --
The compounds of the formula I are produced by methods
known per se, i-or example as follows:
CH~
1) Xl C
~C=CH-CH - CH-COOH C
Xl H3 CH3+ X-CH-I~ y~O~i~ i
(II) (III)
acid-binding
~ I
CH3 agent
2) Xl C
~C=CH-CH - CH-COX ~C . y
~C~+ HO-CH--~ \~_o_~ X.
3 CH3 1~ ~Y
(IV) (V)
acid-binding
. agent
_
3) Xi C
~C=CH-CH- CH-COOH111
Xl ~C~ + HO-CH--~ \~_o_~ X.
H3 CH31~ /Y 1~ ~Y
(II) (V)
water-bindin~
agent
CH
4) Xl C 3
~C=CH-CH - CH-COOR C
1~C~ ~ HO-CH--~ o_~ X-
CH3 CH3 ~ ~Y
~VI) -ROH
- ~ I
_ . ., . . . _ . . .
- -_ .
~ ~S ~ 9 ~
In the formulae II to VI, the symbols Xl and Y have
the meanings given under the formula I.
In the formulae III and IV, X is a halogen atom,
particularly chlorine or bromine, and in the formula VI,
R is Cl-C4 alkyl, especially methyl or ethyl. Suitable
acid-binding agents for the processes 1 and 2 are in
particular tertiary amines such as trialkylamine and
pyridine, also hydroxides, oxides, carbonates and
bicarbonates of alkali metals and alkaline-earth metals,
as well as alkali metal alcoholates, such as potassium
tert-butylate and sodium methylate. The water-binding
agent used for Process 3 can be, for example, dicyclo-
hexylcarbodiimide. The processes 1 to 4 are perform,ed
at a reaction temperature of between -10 and 120C,
usually between 20 and 80C, under normal or elevated
pressure and preferably in an inert solvent or diluent.
Suitable solvents or diluents are, for example, ethers
and ethereal compounds such as diethyl ether, diFropyl
ether, dioxane, dimethoxyethane and tetrahydrofuran;
amides such as N,N-dialkylated carboxylic acid amides;
aliphatic, aromatic and halogenated hydrocarbons, par.-
ticularly benzene, toluene, xylenes, chloroform and
chlorobenzene; nitriles such as acetonitrile; dimethyl-
sulfoxide, and ketones such as acetone and methyl ethyl
ketone.
The starting materials of the formulae II to VII
are known, or they can be produced by methods analogous
to known methods.
If the starting materials used for producing the
compounds of the formula I are not homogeneous op~ically
active materials, the said compounds are obtained as
mixtures of various optically active isomers. The diif-
ferent isomeric mixtures can be separated by known methods
11S2
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into the individual isomers. It is to be understood
that the term 'compounds of the formula I' embraces
both the individual isomers and the mixtures thereo.E.
The compounds of the formula I are suitable for
combating various animal and plant pests.
The compounds of the formula I are particularly
suitable for combating 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. The compounds of the formula I are su-itable
in particular for combating insects that damage plants,
especially insects that damage plants by eating, in
crops of ornamental plants and useful plants, particularly
in cotton crops (for example against Spodoptera lit~oralis
and Heliothis virescens), and in crops of vegetables (for
example against Leptinotarsa decemlineata and Myzus
persicae). Active substances of the formula I have a
very good action also against flies, such as Musca
domestica, and against mosquito larvae.
The acaricidal and insecticidal action can be s~lbstan-
tially broadened and adapted to suit given circumstclnces
by the addition of other insecticides and/or acaricides.
Suitable additives are for example: organic phosphorus
compounds; nitrophenols and derivatives thereof; for-
mamidines; ureas; other pyrethrin-like compounds; as well
as carbamates and chlorinated hydrocarbons.
Compounds of the formula I are combined particularly
advantageously also with substances which have a syner-
gistic or intensifying effect on pyrethroids. Exampl~s
of such compounds are, inter alia, piperonylbutoxide,
propynyl ethers, propynyl oximes, propynyl carbamates and
.. . . . ..
1~5~
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propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-
3,6,9-trioxaundecane (Sesamex or Sesoxane), S,S,S-
tributylphosphorotrithioates and 1,2-methylenedioxy 4-
(2-(octylsulfinyl)-propyl)-benzene.
~ ompounds 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 substances common in formulation
practice, such as natural or regenerated substances,
solvents, dispersing agents, wetting agents, adhesives,
thickeners, binders and/or fertilisers.
The compositions according to the invention are
produced in a manner known per se by the intimate mixing
and/or grinding of the active substances of the form.ula 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:
olid preparations: dusts, scattering agents, granules
(coated, impregnated and homogeneous
granules);
liguid preparations-
.
a) water-dispersible concentrates of active substance:
wettable powders, pastes or emulsions;
b) solutions.
The content of active substance in the compositi.ons
described is between 0.1 and 95%; it is to be mentioned
in this respect that with application from an aeroplane,
or from other suitable devices, concentrations of UE) to
99.5% or even the pure active substance can be used.
The active substances of the formula I can be formu-
lated for example as follows (parts are by weight):
. .... ..
115~4
Dusts
The following substances are used to produce a) a
5% dust and b) a 2% dust:
a) 5 parts of active substance, and
parts of talcum;
b) 2 parts of active substance,
1 part of highly dispersed silicic acid, and
97 parts of talcum.
The active substance is mixed and ground with the
carriers.
Granulate
The following ingredients are used to produce a 5%
granulate:
parts of active substance,
0.25 part of epichlorohydrin,
0.25 part of cetyl polyglycol ether,
3.50 parts of polyethylene glycol, and
91 parts of kaolin (particle size 0.3 - O.i3 mm).
The active substance is mixed with epichlorohydrin
and dissolved in 6 parts of acetone; the polyethylene
glycol and cetyl polyglycol ether are then added. The
solution thus obtained is sprayed onto kaolin, and the
acetone is subsequently evaporated off in vacuo.
Wettable ~owders
The following constituents are used to produce a) a
40% wettable powder, b) and c) a 25~/9 wettable powder
and d) a 10% wettable powder:
a) 40 parts of active substance,
parts of sodium lignin sulfonate,
1 part of sodium dibutyl-naphthalene sulfonate,
and
.. . , . . . . ,.. . ~ . .. _ . . ,.. . . . . _ , ........... . .
,
.
~15~:(39
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54 parts of silicic acid;
b) 25 parts of active substance,
4.5 parts of calcium lignin sulfonate,
1.9 parts of Champagne chalk/hydroxyethyl
cellulose mixture (1:1),
1.5 parts of sodium dibutyl-naphthalene sulfonate,
19.5 parts of silicic acid,
19.5 parts of Champagne chalk, and
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 mixture (1:1),
8.3 parts of sodium aluminium silicate,
16.5 parts of kieselguhr, and
46 parts of kaolin; and
d) 10 parts of active substance,
3 parts of a mixture of the sodium salts o:E
saturated fatty alcohol sul~ates,
parts of naphthalenesulfonic acid/
formaldehyde condensate, and
82 parts of kaolin.
The active substance is intimately mixed in suitable
mixers with the additives, and the mixture is then
ground in the appropriate mills and rollers to obtain
wettable powders which can be diluted with water to give
suspensions of the concentration desired.
Emulsifiable concentrates
The following substances are used to produce a) a
10% emulsifiable concentrate, b) a 25% emulsifiable
.. . . . . . . .. . .. . .. . . .. . ..... . ... . .. . ....... . .. .
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concentrate 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 alkyl-
arylsulfonate calcium salt,
parts of dimethylformamide, and
43.2 parts of xylene;
b) 25 parts o~ active substance,
2.5 parts of epoxidised vegetable oil,
parts of alkylarylsulfonate/fatty alcohol
polyglycol ether mixture,
parts of dimethylformamide, and
57.5 parts of xylene; and
c) 50 parts of active substance,
4.2 parts of tributylphenol-polyglycol ether,
5.8 parts of calcium-dodecylbenzenesulfonate,
parts of cyclohexanone, and
parts of xylene.
Emulsions of the required concentration can be
prepared from these concentrates by dilution with water.
SPrays
The following constituents are used to produce a)
a 5% spray and b) a 95% spray:
a) 5 parts of active substance,
1 part of epichlorohydrin, and
94 parts of ligroin (boiling limites 160-190C);
b) 95 parts of active substance, and
parts of epichlorohydrin.
The invention is further illustrated by the Examples
which follow.
~s~
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Example 1
a) Production of a-prop-l-ynyl-3-p-chlorophenoxybenzyl
alcohol
A Grignard solu~ion, freshly prepared from 4 g of
magnesium and 20 g of ethyl bromide in 20 ml of tetra-
hydrofuran, is slowly added at 0C to a solution of
8 g of methylacetylene in 100 ml of tetrahydrofuran, and
the mixture i5 stirred under argon for 15 minutes. There
is then added dropwise to this mixture at 0 to 5C a
solution of 33.6 g of o-p-chlorophenoxybenzaldehyde in
100 ml of tetrahydrofuran. After being stirred for 14
hours at room temperature, the reactîon mixture is cooled
to 0C with 50 g of ice; 25 ml of conc. hydrochloric acid
is subsequently slowly added, and extraction is performed
with ether. The ether extract is washed twice with water
and twice with saturated sodium chloride solution; it is
then dried over sodium sulfate, filtered, and concentrated
by evaporation. The product is chromatographed through
silica gel with ethyl acetate/hexane (1:4) as the eluant
to thus obtain the compound of the formula
HO-C~ -o-t~
111
c
CH3
having a re~ractive index of n20 = 1.5844.
b) Production of Prop-l-ynYl-3-phenoxybenzyl-2,2-dimethyl-
3-(2',2'-dichlorovinYl)-cYclopropane-l-carboxyla~e
A solution of 4.5 g of a-prop-1-ynyl-3-p-chlorophenoxy-
benzyl alcohol in 20 ml of toluene is added dropwise to
an ice-cooled solution of 3.82 g of 2,2-dimethyl-3-(2',2'-
~15;~
- 10
dichlorovinyl)-cyclopropanecarboxylic acid chloride
and 1.8 ml of pyridine in 50 ml of toluene. The reaction
mixture is stirred for 14 hours at room temperature,
and ether is then added. The ether extract is washed
once with water, once with 2N hydrochloric acid and
three times with a saturated sodium chloride solution;
it is subsequently dried over sodium sulfate, filtered,
and concentrated by evaporation. The product is chromato-
graphed through silica gel with ether/hexane (1:3) as
the eluant. There is obtained the compound of the
formula
C-CH-CH -CH-C00-CH--~ .-o-.
Cl/ ~ ¢ ~ C
3 3 C'C-CH
as a diastereoisomeric mixture having a refractive index
of n20 = 1.5712.
The following compounds are obtained in an analogous
manner:
~ C~ ~ Cl
ca3 ca3 'C~C-C~3
\C-C~CH -c~-Coo C~ T~ ' ' 20
C~3 ca3 C~C- ~
\c-c~-ca-ca-coo-c~-T~ il~-T il 20
¢ ~ -F = ~ = 1,5291
3 3 C-~-Ca3
. , . ~ . .. ., .. . .. . .. . .. , , . . . , . , ., . . . .. . .. .... , .. . , _ . . .. .. . . ..
.. ...
l15z~9~
/C\ ~ / 3
C~3 C~3 C~C-CH3
C~
/c3~a-c~ coo-~-ti `d--I~ = 1,5581
Ca3 Ca3 C~C-C83
Br
r,c-c~-ca -ca-coo-ls-t li- l i~_ClnD = 1,5397
ca3 ca3 C~C-CH3
C~CH-C8 -cH-coo-cH~ li-o-t~ 1,5832
Ca3 Ca3 C C-C~3
Br
,c-c~-c~ -c~-coo ca t li t l'_ F nD ' 1,5740
C~3 C~3 C C-C~3
\c-CH-CH -CH-COO-CH-t il- t il nD - 1,5981
Br \ ¢ ~ Br
~3 ~3 ~-C~
l,`c-ca-ca -ca-coo-l ~l li I~ ,li Br nD0 3 1,5819
C~3 3 C-C-C~3
115ZO9~L
F
,cYc~-ca - ca--coo--c~--~ \ --o-- ~ 1, 5400
C~I3 CH3 C~-CH3
- F
~C-CH-CH -CH-COO-CH-~ il-- i~ i~ nD ' 1, 5420
3 3 C-C-CH3
C3~ . .
~C-CH-CH -CH-COO-CH~ -O-î~ ~il-F n20 = 1,5598
3 3 C-C-CH3
~C-CH-CH-CH-C00-CH-i~ -iSS \i ~ = 1,5695
3 3 ~=~-Ca3
Br
~C-CH-CH-CH-C00-CH~ il--i~ ~il nD ~ 1,5850
C~3 C~3 ~ -CH3
Example 2
a) Insecticidal stomach-Poison action
Cotton plants were sprayed with a 0.05% aqueous
active-substance emulsion (obtained from a 10% emulsi-
fiable concentrate). After drying of the coating,
larvae of Spodoptera littoralis in the L3-stage and of
-
, . .. :
.
1 ~5;;~9
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Heliothis virescens in the L3 stage were placed on~o
the cotton plants. The test was carried out at 24C
with 60% relative humidity.
Compounds according to Example 1 exhibited in the
above test a good insecticidal stomach-poison action
against Spodoptera littoralis and ~eliothis virescens
larvae.
Example 3
Acaric;dal action
Phaseolus vulgaris plants were infested, 12 hours
before the test 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 overflow of the spray-
liquor. An assessment was made after 2 and 7 days, by
examination under a binocular microscope, of the living
larvae and of the dead larvae, adults and eggs, and the
results were expressed as percentages. The treated
plants were kept during the "holding time" in greenhouse
compartments at 25C.
Compounds according to Example l were effective in
the above test against adults, larvae and eggs of
Tetranychus urticae.
Example 4
a) RhipicePhalus burs_
For each concentration, 5 adult ticks and 50 tick
larvae, respectively, were counted into a small glass
test tube, and immersed for 1 to 2 minutes in 2 ml of an
aqueous emulsion from a dilution series of 100, 10, 1 and
.. . . .. .
~15~(~99
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O.1 ppm of test substance. The tubes were then sealed
with a standardised cotton plug, and inverted so that
the active-substance emulsion could be absorbed by the
cotton wool.
The evaluation in the case of the adults was made
after 2 weeks and in the case of the larvae after 2
days. There were two repeats for each test.
b) Boophilus microplus (larvae~
With a dilution series analogous to that of Test A,
tests were carried out with 20 sensitive larvae and OP-
resistant larvae, respectively (resistance is with
respect to diazinon compatibility).
Compounds according to Example 1 were effective in
these tests against adults and larvae of Rhipicephalus
bursa and against sensitive and OP-resistant larvae~
respectively, of Boophilus microplus.
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