Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
105;~Z4~
The present invention relates to dicarboxinides, to
processes for their preparation, and to their use for
the control of insects.
The dicarboximides correspond to the formula
O
~ N-R (I)
wherein o
R represents a phenyl mono- to trisubstituted,
identically or differently, by fluorine,
chlorine, bromine, iodine, trifluoromethyl,
nitro, cyano, Cl-C4-alkyl, methoxy or methylthio,
or monosubstituted by a methylenedioxy group,
and
Zl and Z2 each represent hydrogen, or together with the
carbon atoms to which they are bound they -
represent a carbon-carbon bond.
As substltuents of the phenyl group, the Cl~C4-alkyl
groups can be branched-chain or straight-chain, and are
preferably the methyl or ethyl group.
Compounds of formula I preferred by virtue of their
action are those wherein
R represents a phenyl mono- to trisubstituted9
identically or differently, by fluorine, chlorine,
~ .
' ~ ~ ' ' ' ' ', '' .: ' . ~' .
1~53Z9t4
bromine, iodine, trifluoromethyl, methyl, ethyl, methoxy, methylthio, nitro,
or cyano, or monosubstituted by a methylenedioxy group, and Zl and Z2
each represent hydrogen, or together with the carbon atoms to which they are
bound they represent a carbon-carbon bond.
Paritcularly preferred compounds of formula I are those wherein
R represents a phenyl mono- to trisubstituted, identically or differently,
by fluorine, chlorine, bromine, iodine, trifluoromethyl, ethyl, methyl,
methylthio, nitro or cyano, or monosubstituted by a methylenedioxy group,
and Zl and Z2 together with the carbon atoms to which they are bound re-
present a carbon-carbon bond.
The present invention also relates to a process for the preparation
of compounds of the formula
~ / - R
wherein R represents a phenyl mono- to trisubstituted, identically or different-
ly, by fluorine, chlorine, bromine, iodine, trifluoromethyl, nitro, cyano,
Cl-C4-alkyl, thoxy or methylthio, or mono substituted by a methylene dioxy
group, and Zl and Z2 each represent hydrogen, or together with the carbon
atoms to which they are bound they ~represent a carbon-carbon bond5 in which
process a compound of the formula
<~X\
o ' ~'
is reacted
_ 3 - ~:
~.. . :...
~)S;~Z44
with a compound of the formula
H2N-R
wherein R, Zl and Z2 have the meanings given for formula I.
The reaction is performed under normal pressur~,
at a temperature of 60 - 150C, preferably 80 - 120C,
and in a high-boiling solvent, such as, e.g. glacial
acetic acid, benzene, toluene or xylene.
The starting materials of formula II are known, and
can be prepared by a method analogous to that described
in Ber. 86, 1528-39 (1953).
The compounds of formula I are suitable for the
control of insects. To be particularly emphasised is
their high degree of effectiveness against Lepidoptera.
In the U S Patent Specifications Nos. 2,462,835 and
2,545,283, dicarboximides are described as synergists.
Reference is made to, inter alia, their insecticidal
action.
The insecticidal, herbicidal and fungicidal action
of dicarboximides is described in the U S Patent Specification
No. 3,654,302.
Compared with the compounds described in the above-
mentioned patent specifications, the dicarboximides of
formula I exhibit an unexpectedly better larvicidal action,
especially in the case of larvae of Lepidoptera.
_ 4 _
.
1(~53;~44
The insecticidal action of the dicarboximides of
formula I can be appreciably broadened and adapted to
suit given circumstances by the addition of other
insecticides. Suitable additives are, for example:
organic phosphorous compounds~
nitrophenols and derivatives thereof,
formamidines,
carbamates and
chlorinated hydrocarbons.
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~0 5 3Z ~ ~
The compo~mds of formula I can be used on their own
or ~ogcther with suitable carriers and/or additives.
Suitable carriers and additives may be solid or liquid,
and they correspond to the substances common in forrnulation
practice, such as, e.g. natural or regenerated substances,
solvents, dispersing agents, wetting agents, adhesives,
thickeners, binders and/or fertilisers.
For application, the compo~mds of formula I can be
processed into the form of dusts, emulsion concentrates,
granulates, dispersions, sprays or solutions, the
formulation of these preparations being e~fected in a
manner commonly kno~n in practice. Also to be mentioned
are cattle dips and spray races, in which aqueous
preparations are used. - -
The agents according to the invention are prepared
in a manner known per se by the intimate mixing and/or
grinding of active substances of formula I with
suitable carrlers, 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:
_ Ld ions:- dusts, scattering agents, granulates,
coated granulates, impregnated
granulates and homogeneous granulates;
~ (~53Z44
liquid preparat;ons:-
a) water-dispersible active-substance concentrates:
wettable powders, pastes or emulsions;
b~ solutions.
The content of active substance in the described
agents is between 0.1 and 95 %.
The active substances of ormula I can be formulated,
for example, as follows:
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,
9S parts of talcum;
b) 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.
11~53Z44
Granula~e:
Tlle followlng subs~ances are used to prepare a
5% granulate:
S par~s o active substance,
0.25 part of epichlorohydrin,
0.25 part of cetyl polyglycol ether,
3.50 parts o polye~hylene 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
10 glycol and cetyl polyglycol ether are then added. The
solution thus obtained is sprayed onto kaolin, and
the acetone subsequently evaporated off in vacuo.
Wettable powder:
The follo~ing constituents are used for 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 sodiun lignin sulphonate,
1 part of sodium dibutyl~naphthalene sulphonate,
54 parts of silicic acid;
20 b) 25 parts of active substance,
4,5 parts of calcium lignin sulphonate,
1.9 parts of Champagne chalk/hydroxyethyl cellulose
mix~ure (1:1),
1.5 parts of soclium dibutyl naphthalene sulphonate,
19.5 parts of silicic acid,
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: .. - ~. ' ' : .'
1053244
19.5 parts of Champagne chalk,
28.1 parts of kaolin;
c) 25 par~s of active substance~
2.5 parts of isooctylphenoxy polyoxyethylene-ethanol,
S 1.7 parts of Clampagne chalk/hydroxyethyl
cellulose mixture (1:1),
8.3 parts of sodium aluminium silicate,
16.5 parts of kieselguhr,
46 parts of kaolin;
d) 10 ?arts of active substance,
3 parts of a mixture of the sodium salts of
saturated fatty alcohol sulphates,
Sparts of naphthalenesulphonic acid/formaldehyde
condensate,
.15 82parts of kaolin.
The active substances are intimately mixed~ in suitable
mixers, with the additives, the mixture being then
ground in the appropriate mills and rollers. ~ettable
powders are obtained which can be diluted with water to
give suspensions of any desired concentration~
Emulsifiable concentrates:
The.following substances are used to prepare a) a 10%
and b) a 25% emulsifiable concentrate: . -
a) 10 parts of active substance,
3,4 parts of epoxidised vegetable oi.l,
. 9
.
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IL(~5;~4
3..4 par~s of a combination emulsifier consisting
oE f~ty alcohol polyglycol e~her and alkylaryl-
sulpllonate calcium salt,
40 parts of dimethylformamide5
43.2 parts of xylene;
b) 25 parts of active substance,
2.5 parts of epoxidised vege~able oil,
10 parts of an alkylarylsulphonate/fatty alcohol
polyglycol ether mixture,
5 parts of dimethylformamide,
57.5 par~s of xylene.
From these concentrates it is possible to prepare~ .-
by dilution with water, emulsions of any desired
concen.tration.
,
~:
The following constituents are used to prepare a
5% spray:
S parts of active substance,
1 part of epichlorhydrin,
94 parts of ligroin (boiling limits 160 - 190C).
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l(~S3244
Exampl e 1
a) ~ r ~ion of N-(4'-nitrophen~ tricyclo-
[4.2.2.02-4]-non-8-ene-6`7-dicarboximide.
_ _ _ _ _ _ _ _ _ _ _ . _ . _ _ _ . _ _ _
250 g of tricyclo-[4.2.2.02-4]-non-8-ene-6,7-dicarboxylic
acid anhydride (prepared from cycloheptatriene and
m~leic acid anhydride, K. ~lder, Ber. 86, 1528-39 (1953))
and 200 g of 4-nitroaniline are refluxed in 1500 ml of
glacial acetic acid for 3 hours. The reaction mixture
cooled to 60C is poured into 2000 ml of hot water,
whereupon the crude product precipitates. After cooling,
the crude product is filtered off, dried, and recrystallised
from ethyl acetate; M.P. 210 - 212C.
b) Preparation of N-(3',5'-dichlorophenYl)-tricyclo-
l4.2.2. o2 4 ~ -nonane-6~7-dicarboximide.
__ .
19.2 g of tricyclo-[4.2.2.02 4l-nonane-6,7-dicarboxylic
acid anhydride (prepared from the cycloheptatriene/maleic
acid anhydride adduct (see Ex. la) by catalytic
hydrogenation, K. Alder, Ber. 86, 1528-39 (1953) and
19.4 g of 3,5-dichloroaniline are refluxed in 1000 ml of
toluene for 16 hours, whereby the water orming during
the reaction is separated with a water separator. After
cooling, the toluene is removed in vacuum, and the
residue recrystallised from ethyl acetate, M.P. 145 - 153C.
- . . . . ~ .
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105~2~4
The following addi~ional compounds are prepared in an
analogous manner:
o/
.. ~ .
_ _ R= _ M.P ~C _
3,4-dichlo,ophenyl 204 - 206C
4-bromophenyl 206 - 207C
~-fluorophenyl 184C
4-chlorophenyl 203C
3-txi~lu~romethyl-phenyl 20GC
3-methylthio-phenyl 186 - 188C
3,5-dichlorophenyl 167 - 169C
2,4,5-trichlorophenyl 168 - 170C
275-dibromophenyl 191 - 192C
2,5-dichlorophenyl 195 - 196C
3-chlorophenyl 182 - 183C
3-nitrophenyl 204 - 206C .-
. 3,5-bis~trifluoromethyl-phenyl 100 - 101C
. 2-chloro-5-trifluoromethyl-phenyl 126 - 127C
2-ethyl-phenyl ` 152 ~ 154C
. 4-cyano-phenyl 190 - 191C .
202-methyl-4-chlorophenyl 179 - 180C
. .... .. ~ . ,. __
- 12 -
'. -' ',. ' ,. ,. ' " ' , ' . , :
1053Z4~
R= _ _ M.P. C~
2-methyl-5-chlorophenyl 184 - 190C :
3-trifluorclnethyl-4-chlorophenyl 189 - 190C
2-methyl-5-nitrophenyl 189 - 190C
2-nitrophenyl 168 - 170C
4-methoxy-phenyl 198 - 200C
2-fluorophenyl 148 - 149C
3-fluorophenyl 152 - 154C
2-iodophenyl 149 - lSlC
4-iodophenyl 216 - 218C
2-chloro-4-bromophenyl 208 - 210C
2,5-dimethoxy-4-chlorophenyl 196 - 198C
4-methylthio-phenyl 186 - 188C
. 3,5-dinitro-phenyl 178 - 180C
2-nitro-4-methyl-phenyl 202 - 204C
. 2,4-dichlorophenyl . 162 - 164C
2-trifluoromethyl-phenyl 128C
: 2-methyl-3-chlorophenyl 157C
3,4-methylenedioxy-phenyl 217C
4-trifluoromethylphenyl 218C
.
- 13 -
..... . ..
~0532~
.
~o~
_
R-- M.P. C
. _ _
2-methoxy-4-ohlorophenyl 170C
2,4-dibromophenyl 207C
2,4-difluorophenyl 135C
.5 2,5-difluorophenyl 135C
2-methyl-4-bromophenyl 198C
3-fluoro-4-methyl-phenyl 202C
3-bromo-5-trifluoromethyl-phenyl 141C
3,4,5-trichlorophenyl 186 - 187C
2-methyl-3-nitrophenyl 210C
- 14 -
~0S3;~
<¦ ~ N--R
R- M . P . C
,
4-bromophenyl 230 - 240C
2-chloro-5-trifllloromethyl-phenyl 157C
2,4-dichlorophenyL 175C
Exa~ 2 105;~244
-tSecticLdal action a~ains~ Spodoptera littoralis
Cotton plants 15 cm in height were sprayed with
25 ml of a solu~ion (acetone/~ater 1:1) containing 0.2%
of active substance. After drying of the coating~ 5
Spodoptera littoralis caterpillars (L3 stage) were placed
on each plant. A plastic cylinder was put over the
plant and closed with a copper gauze lid. A mortality
determination was made after 2 days. The compounds
according to Example 1 exhibited in ~his test a good
action against Spodoptera littoralis.
Example 3
Insecticidal action aga]nst Lep~inotarsa decemlineata
Potato plants 15 cm in height were sprayed with 25 ml
o a solution (acetone/water 1:1) containing 0.1% of
active substance. After drying o~ the coating, 10
Leptinotarsa larvae (L3 stage) were placed on each plant.
A plastic cylinder was put over the plant and closed with
a copper gauze lid. A mortality evaluation was made a~ter
2 days.
The compounds according to Example 1 exhibited in this
test a good action against Leptinotarsa decemlineata.
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