Pest control agents

There are disclosed novel substituted N-amino-1,2,4-triazinones of formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.12 alkyl or C.sub.3 -C.sub.7 cycloalkyl, PA0 R.sub.2 and R.sub.3 are each independently of the other hydrogen or C.sub.1 -C.sub.6 alkyl, PA0 R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are each independently of one another hydrogen, halogen, C.sub.1 -C.sub.3 alkyl, ##STR2## C.sub.1 -C.sub.3 alkoxy or C.sub.1 -C.sub.3 alkylthio, and n is 0 or 1, or a salt thereof, with the proviso that n is 1, if simultaneously the pyridine ring is attached via the 3-position to the methylidene group and R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are each hydrogen; their use in pest control and pesticidal compositions which contain a compound of formula I as active component. The preferred utility is the control of pests of animals and plants.

The present invention relates to novel insecticidal 
N-amino-1,2,4-triazinones, to their preparation and to intermediates for 
their preparation, to compositions which contain said aminotriazines, and 
to the use thereof in pest control. 
The aminotriazines of this invention have the formula I 
##STR3## 
wherein R.sub.1 is C.sub.1 -C.sub.12 alkyl or C.sub.3 -C.sub.7 cycloalkyl, 
R.sub.2 and R.sub.3 are each independently of the other hydrogen or C.sub.1 
-C.sub.6 alkyl, 
R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are each independently of one another 
hydrogen, halogen, C.sub.1 -C.sub.3 alkyl, 
##STR4## 
C.sub.1 -C.sub.3 alkoxy or C.sub.1 -C.sub.3 alkylthio, and n is 0 or 1, 
and to the salts thereof, with the proviso that n is 1, if simultaneously 
the pyridine ring is attached via the 3-position to the methylidene group 
and R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are each hydrogen. 
The compounds of formula I can also be obtained in the form of acid 
addition salts. Suitable acids for forming such salts are organic and 
inorganic acids, for example hydrochloric acid, hydrobromic acid, nitric 
acid, different phosphoric acids, sulfuric acid, acetic acid, propionic 
acid, butyric acid, valeric acid, oxalic acid, malonic acid, maleic acid, 
fumaric acid, lactic acid, tartaric acid or salicyclic acid. 
The alkyl groups by themselves or as moieties of other substituents may be 
straight-chain or branched. Typical of such alkyl groups are methyl, 
ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl or 
pentyl, hexyl, octyl, decyl, dodecyl and the like, and the isomers 
thereof. 
Suitable alkoxy and alkylthio groups may be straight-chain or branched and 
are e.g., typically, methoxy, methylthio, ethoxy, ethylthio and propoxy. 
Cycloalkyl groups may be e.g., cyclopropyl, cyclobutyl, cyclopentyl or 
cyclohexyl. 
Halogens are suitably fluoro and chloro and also bromo and iodo. Preferred 
halogens are fluoro and chloro. 
Preferred compounds of formula I are those wherein R.sub.1 is C.sub.1 
-C.sub.4 alkyl; those wherein R.sub.1 is methyl, ethyl, isopropyl or 
cyclopropyl; and those wherein n is 1. 
Also preferred are the compounds of formula Ia 
##STR5## 
wherein R.sub.1 to R.sub.7 have the above given meanings. 
In formulae I and Ia above, the substituents R.sub.2 and R.sub.3 are 
conveniently each independently of the other hydrogen or methyl, 
preferably hydrogen. 
Among the compounds of formula I, those of formula Ib 
##STR6## 
wherein R.sub.1, R.sub.4 to R.sub.7 and n are as defined above, may also 
be highlighted. 
On account of their biological activity, those compounds of formula Ib are 
preferred in which R.sub.1 is methyl or ethyl, R.sub.5 is hydrogen, 
R.sub.4, R.sub.6 and R.sub.7 are each independently of one another chloro, 
methyl, methoxy or amino. 
Particularly preferred compounds of this invention are those of formulae I, 
Ia and Ib wherein R.sub.6 is hydrogen; or wherein R.sub.4, R.sub.5, 
R.sub.6 and R.sub.7 are hydrogen and n is 1; or wherein R.sub.1 is methyl. 
Further preferred compounds of formula Ib are those in which R.sub.4, 
R.sub.5 and R.sub.6 are each independently of one another methyl or fluoro 
and R.sub.7 is hydrogen, methylthio or dimethylamino, and n is 0. 
Among the compounds of formula I, those compounds of formula Ic 
##STR7## 
wherein R.sub.1, R.sub.2 and R.sub.3 are as defined above, also merit 
special mention. 
On account of its biological activity, 
2,3,4,5-tetrahydro-3-oxo-4-[(pyridin-N-oxide-3-yl)methyleneimino]-6-methyl 
-1,2,4-triazine of formula 
##STR8## 
is to be singled out for special mention. 
The compounds of formula I can be prepared by processes which are known per 
se, for example by reacting an aminotriazinone of formula II 
##STR9## 
wherein R.sub.1 is C.sub.1 -C.sub.12 alkyl or C.sub.3 -C.sub.7 cycloalkyl, 
R.sub.2 and R.sub.3 are each independently of the other hydrogen or C.sub.1 
-C.sub.6 alkyl, 
with an aldehyde of formula III 
##STR10## 
wherein R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are each independently of 
one another hydrogen, halogen, C.sub.1 -C.sub.3 alkyl, 
##STR11## 
C.sub.1 -C.sub.3 alkoxy or C.sub.1 -C.sub.3 alkylthio, and n is 0 or 1, 
with the proviso that n is 1, if simultaneously the pyridine ring is 
attached via the 3-position to the methylidene group and R.sub.4, R.sub.5, 
R.sub.6 and R.sub.7 are each hydrogen, 
and isolating the reaction product. If desired, the resultant compounds can 
be converted into their salts in conventional manner. 
The process is ordinarily carried out under normal pressure in the presence 
of a catalytic amount of a strong acid and in a solvent. The reaction 
temperature is in the range from +10.degree. to 100.degree. C., preferably 
from +40.degree. to 80.degree. C. Suitable acids are strong inorganic 
acids such as mineral acids, preferably hydrochloric acid. Suitable 
solvents are alcohols, ethers and ethereal compounds, nitriles or also 
water. 
The starting aminotriazinones of formula II are known or can be prepared in 
a manner which is known per se, for example by cyclic rearrangement with 
hydrazine hydrate, i.e. reacting an oxadiazolone of formula IV 
##STR12## 
with hydrazine hydrate (H.sub.2 N--NH.sub.2.H.sub.2 O), wherein R.sub.1, 
R.sub.2 and R.sub.3 are as defined above. The process for the preparation 
of the aminotriazinones of formula II is ordinarily carried out under 
normal pressure and with or without a solvent. The reaction temperature is 
in the range from +15.degree. to 120.degree. C., preferably from 
+20.degree. to 80.degree. C. Suitable solvents are typically water, 
nitriles such as acetonitrile, alcohols, dioxane or tetrahydrofuran. 
The above mentioned oxadiazolones of formula IV can be prepared by 
processes which are known per se, for example by reacting 
5-trifluoromethyl-1,3,4-oxadiazol-2(3H)-one of formula V 
##STR13## 
with a ketone of formula VI 
##STR14## 
in which formulae the substituents R.sub.1, R.sub.2 and R.sub.3 are as 
defined above and X is halogen. The process for the preparation of the 
oxadiazolones of formula IV is carried out under normal pressure and in 
the presence of a base and in a solvent. The reaction temperature is in 
the range from 0.degree. to +150.degree. C., preferably from +20.degree. 
to 100.degree. C. Suitable bases are organic and inorganic bases such as 
trimethylamine, alcoholates, sodium hydroxide or sodium hydride. Suitable 
solvents are typically alcohols, halogenated hydrocarbons such as 
chloroform, nitriles such as acetonitrile, tetrahydrofuran, dioxane, 
dimethyl sulfoxide or also water. 
Among the aminotriazinones of formula II, 
4-amino-6-phenyl-1,2,4-triazin-3-one is known (Liebigs Annalen der Chemie, 
749, 125 (1971), i.e. the compound of formula II in which R.sub.1 is 
phenyl, and R.sub.2 and R.sub.3 are each hydrogen. The compounds of 
formulae V and VI are known or can be prepared by processes which are 
known per se. The aldehydes of formula III, wherein n is 0, are known or 
can be prepared by processes which are known per se [Z. Chemie 184 (1970), 
J. Org. Chem. 46, 4836 (1981), Eur. J. Med. Chem. 12, 531 (1977), 
Heterocycles 26, 4836 (1981), J. Org. Chem. 53, 5320 (1988)]. The 
compounds of formula III (n=1) are usually prepared starting from the 
corresponding aldehyde (n=0) by reaction with a suitable oxidising agent 
such as m-chloroperbenzoic acid, whereby the aldehyde group is temporarily 
protected with a suitable protective group. To this end the aldehyde group 
can, for example, be acetylised. 
The process of this invention is suitable for the preparation of compounds 
of formula I using pyridine derivatives (n=0) as well as pyridine-N-oxides 
(n=1) as starting materials. Depending on the desired final compound, a 
suitable free pyridine aldehyde (n=0) or the N-oxide thereof (n=1) is 
used. 
It has now been found that the instant compounds of formula I are better 
tolerated by warm-blooded animals and have greater stability than known 
phosphoric acid esters and carbamates, while being well tolerated by 
plants. They are therefore most suitable for use as pest control agents, 
especially for controlling pests of plants, in particular insects. 
The compounds of formula I are particularly suitable for controlling 
insects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, 
Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, 
Thysanura, Isoptera, Psocoptera and Hymenoptera, as well as 
representatives of the order Acarina. 
Most particularly, plant-injurious insects, especially plant-injurious 
insects in ornamentals and crops of useful plants, in particular in 
cotton, vegetable, rice and fruit crops, can be controlled with the 
compounds of formula I. In this connection, particular attention is drawn 
to the fact that the compounds of formula I have a strongly pronounced 
systemic as well as contact action against sucking insects, especially 
against insects of the Aphididae family (e.g. against Aphis fabae, Aphis 
craccivora, Myzus persicae and Bemisia tabaci) which can only be 
controlled with difficulty using known pesticides. 
The good pesticidal activity of the compounds of formula I corresponds to a 
mortality of at least 50-60% of the above pests. 
The activity of the compounds employed and of the compositions containing 
them can be substantially broadened and adapted to prevailing 
circumstances by addition of other insecticides and/or acaricides. 
Examples of suitable additives include: organophosphorus compounds, 
nitrophenols and derivatives thereof, formamidines, ureas, carbamates, 
pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis 
preparations. 
The compounds of formula I are used as pest control agents in unmodified 
form, or preferably together with the adjuvants conventionally employed in 
the art of formulation, and are therefore formulated in known manner to 
emulsifiable concentrates, directly sprayable or dilutable solutions, 
dilute emulsions, wettable powders, soluble powders, dusts, granulates, 
and also encapsulations in e.g. polymer substances. As with the 
compositions, the methods of application such as spraying, atomising, 
dusting, scattering or pouring, are chosen in accordance with the intended 
objectives and the prevailing circumstances. 
The formulations, i.e. the compositions, preparations or mixtures 
containing the compound (active ingredient) of formula I or combinations 
thereof with other insecticides or acaricides, and, where appropriate, a 
solid or liquid adjuvant, are prepared in known manner, e.g. by 
homogeneously mixing and/or grinding the active ingredients with 
extenders, e.g. solvents, solid carriers and, in some cases, 
surface-active compounds (surfactants). 
Suitable solvents are: aromatic hydrocarbons, preferably the fractions 
containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted 
naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, 
aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and 
glycols and their ethers and esters, such as ethanol, ethylene glycol, 
ethylene glycol monomethyl or monoethyl ether, ketones such as 
cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, 
dimethyl sulfoxide or dimethyl formamide, as well as vegetable oils or 
epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; 
or water. 
The solid carriers used e.g. for dusts and dispersible powders are normally 
natural mineral fillers such as calcite, talcum, kaolin, montmorillonite 
or attapulgite. To improve the physical properties it is also possible to 
add highly dispersed silicic acid or highly dispersed absorbent polymers. 
Suitable granulated adsorptive carriers are porous types, for example 
pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent 
carriers are materials such as calcite or sand. In addition, a great 
number of pregranulated materials of inorganic or organic nature can be 
used, e.g. especially dolomite or pulverised plant residues. 
Depending on the nature of the compound of formula I to be formulated, or 
of combinations thereof with other insecticides or acaricides, suitable 
surface-active compounds are non-ionic, cationic and/or anionic 
surfactants having good emulsifying, dispersing and wetting properties. 
The term "surfactants" will also be understood as comprising mixtures of 
surfactants. 
Suitable anionic surfactants can be both water-soluble soaps and 
water-soluble synthetic surface-active compounds. 
Suitable soaps are the alkali metal salts, alkaline earth metal salts or 
unsubstituted or substituted ammonium salts of higher fatty acids 
(C.sub.10 -C.sub.22), e.g. the sodium or potassium salts of oleic or 
stearic acid, or of natural fatty acid mixtures which can be obtained, 
e.g. from coconut oil or tallow oil. Further suitable surfactants are also 
the fatty acid methyltaurin salts as well as modified and unmodified 
phospholipids. 
More frequently, however, so-called synthetic surfactants are used, 
especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole 
derivatives or alkylarylsulfonates. 
The fatty sulfonates or sulfates are usually in the form of alkali metal 
salts, alkaline earth metal salts or unsubstituted or substituted ammonium 
salts and generally contain a C.sub.8 -C.sub.22 -alkyl radical which also 
includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium 
salt of lignosulfonic acid, of dodecylsulfate, or of a mixture of fatty 
alcohol sulfates obtained from natural fatty acids. These compounds also 
comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide 
adducts. The sulfonated benzimidazole derivatives preferably contain 2 
sulfonic acid groups and one fatty acid radical containing about 8 to 22 
carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or 
triethanolamine salts of dodecylbenzenesulfonic acid, 
dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic 
acid and formaldehyde. Also suitable are corresponding phosphates, e.g. 
salts of the phosphated adduct of p-nonylphenol with 4 to 14 moles of 
ethylene oxide. 
Non-ionic surfactants are preferably polyglycol ether derivatives of 
aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty 
acids and alkylphenols, said derivatives containing 3 to 30 glycol ether 
groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 
6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further 
suitable non-ionic surfactants are the water-soluble adducts of 
polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene 
glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in 
the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether 
groups and 10 to 100 propylene glycol ether groups. These compounds 
usually contain 1 to 5 ethylene glycol units per propylene glycol unit. 
Representative examples of non-ionic surfactants are 
nonylphenolpolyethoxyethanols, castor oil thioxilate, 
polypropylene/polyethylene oxide adducts, 
tributylphenoxypolyethoxyethanol, polyethylene glycol and 
octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene 
sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable 
non-ionic surfactants. 
Cationic surfactants are preferably quaternary ammonium salts which 
contain, as N-substituent, at least one C.sub.8 -C.sub.22 alkyl radical 
and, as further substitutents, unsubstituted or halogenated lower alkyl, 
benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the 
form of halides, methylsulfates or ethylsulfates, e.g. 
stearyltrimethylammonium chloride or benzyl 
bis(2-chloroethyl)ethylammonium bromide. 
The surfactants customarily employed in the art of formulation are 
described e.g. in the following publications 
"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., 
Ridgewood, N.J., 1979; Dr. Helmut Stache, "Tensid Taschenbuch" (Handbook 
of Surfactants), Carl Hanser Verlag, Munich/Vienna, 1981. 
The pesticidal compositions usually contain 0.1 to 99%, preferably 0.1 to 
95%, of a compound of formula I, 1 to 99.9% of a solid or liquid adjuvant, 
and 0 to 25%, preferably 0.1 to 25%, of a surfactant, the percentages 
being by weight. 
Whereas commercial products are preferably formulated as concentrates, the 
end user will normally employ diluted formulations of substantially lower 
concentration, for example 0.1 to 1000 ppm. In general, the concentration 
of compound of formula I--especially for crop areas--is 0.025 to 1.0 
kg/ha, preferably 0.1 to 0.5 kg/ha, for example 0.1 to 0.25 kg/ha. 
The compositions may also contain further ingredients, such as stabilisers, 
antifoams, viscosity regulators, binders, tackifiers as well as 
fertilisers or other chemical agents for obtaining special effects.

EXAMPLES 
1. Preparation of the Compounds of Formula I and their Intermediates 
Example H1:2-Oxo-5-trifluoromethyl-2,3-dihydro-1,3,4-oxadiazole-1-3-acetone 
15 g (0.5 mol) of an 80% dispersion of NaH in oil are washed free of oil 
with petroleum ether and added to 125 ml of dimethyl formamide. Then 77 g 
(0.5 mol) of 5-trifluoromethyl-1,3,4-oxadiazole-2(3H)-one in 250 ml of 
dimethyl formamide are added dropwise to this suspension at room 
temperature over 1 hour, and the mixture is stirred for 3 hours. After 
addition of 55.5 g (0.6 mol) of chloroacetone, the reaction mixture is 
stirred for 16 hours at room temperature and then concentrated by 
evaporation. Upon addition of 1000 ml of water to the residue, the solid 
precipitate is filtered with suction and dried, to give the title compound 
of formula 
##STR15## 
in the form of a colourless solid; m.p. 85.degree. C. (yield: 96 g; 
91.7%). 
The following compounds of formula IV are prepared in analogous manner. 
TABLE 1 
______________________________________ 
##STR16## (IV) 
Compound R.sub.1 R.sub.2 R.sub.3 
Physical data 
______________________________________ 
1.01 CH.sub.3 H H m.p. 85.degree. C. 
1.02 i-C.sub.3 H.sub.7 
H H m.p. 74-75.degree. C. 
1.03 C(CH.sub.3).sub.3 
H H m.p. 67.degree. C. 
1.04 C.sub.6 H.sub.5 
H H m.p. 100-102.degree. C. 
1.05 CH.sub.3 CH.sub.3 
H oil 
1.06 CH.sub.3 CH.sub.3 
CH.sub.3 
oil 
1.07 C.sub.2 H.sub.5 
H H m.p. 76-77.degree. C. 
1.08 
##STR17## 
H H m.p. 77-78.degree. C. 
1.09 H H H 
1.10 C.sub.2 H.sub.5 
CH.sub.3 
H 
1.11 n-C.sub.3 H.sub.7 
H H 
1.12 
##STR18## 
CH.sub.3 
H 
1.13 H CH.sub.3 
H 
1.14 i-C.sub.3 H.sub.7 
CH.sub.3 
H 
1.15 i-C.sub.3 H.sub.7 
CH.sub.3 
CH.sub.3 
1.16 C(CH.sub.3).sub.3 
CH.sub.3 
H 
1.17 CH.sub.3 C.sub.2 H.sub.5 
H 
1.18 CH.sub.3 C.sub.2 H.sub.5 
CH.sub.3 
1.19 
##STR19## 
CH.sub.3 
CH.sub.3 
1.20 
##STR20## 
C.sub.2 H.sub.5 
CH.sub.3 
______________________________________ 
Example H2:2,3,4,5-Tetrahydro-3-oxo-4-amino-6-methyl-1,2,4-triazine 
With cooling, 210 g (1.0 mol) of 
2-oxo-5-trifluoromethyl-2,3-dihydro-1,3,4-oxadiazole-3-acetone are added 
to 250 ml of hydrazine hydrate. The resultant clear brown solution is 
stirred for 2 hours and then concentrated by evaporation under vacuum. The 
residue is chromatographed over silica gel (elution with a 9:1 mixture of 
methylene chloride/methanol), and the solvent is removed by evaporation. 
The title compound of formula 
##STR21## 
crystallises from the residual oil after addition of ether, m.p. 
117.degree.-119.degree. C. (yield: 64 g; 50%). 
The following compounds of formula II are prepared in analogous manner: 
TABLE 2 
______________________________________ 
##STR22## (II) 
Compound R.sub.1 R.sub.2 R.sub.3 
m.p. .degree.C. 
______________________________________ 
2.01 CH.sub.3 H H 117-119 
2.02 CH.sub.3 CH.sub.3 
H 172-174 
2.03 CH.sub.3 CH.sub.3 
CH.sub.3 
138-139 
2.04 C.sub.2 H.sub.5 
H H 143-145 
2.05 i-C.sub.3 H.sub.7 
H H 79-81 
2.06 C(CH.sub.3).sub.3 
H H 148-150 
2.07 
##STR23## H H 94-95 
2.08 C.sub.6 H.sub.5 
H H 199-202 
2.09 4-ClC.sub.6 H.sub.4 
H H 208-210 
2.10 H H H 
2.11 CH.sub.3 C.sub.2 H.sub.5 
H 
2.12 C.sub.2 H.sub.5 
CH.sub.3 
CH.sub.3 
2.13 C.sub.2 H.sub.5 
CH.sub.3 
H 
2.14 n-C.sub.3 H.sub.7 
H H 
2.15 n-C.sub.3 H.sub.7 
CH.sub.3 
H 
2.16 n-C.sub.3 H.sub.7 
CH.sub.3 
CH.sub.3 
2.17 i-C.sub.3 H.sub.7 
CH.sub.3 
H 
2.18 C(CH.sub.3).sub.3 
CH.sub.3 
H 
2.19 C(CH.sub.3).sub.3 
CH.sub.3 
CH.sub.3 
2.20 
##STR24## CH.sub.3 
CH.sub.3 
2.21 
##STR25## CH.sub.3 
H 
______________________________________ 
Example H3: 
2,3,4,5-Tetrahydro-3-oxo-4-[(2-methylpyridin-3-yl)-methyleneamino]-6-methy 
l-1,2,4-triazine 
To a solution of 0.5 g (4 mmol) of 
2,3,4,5-tetrahydro-3-oxo-4-amino-6-methyl-1,2,4-triazine in 250 ml of 
ethanol are added, at room temperature, 0.48 g (4 mmol) of 
2-methylpyridine-3-carbaldehyde and 1 drop of concentrated HCl. The 
reaction mixture is stirred for 1/2 hour and then filtered. The isolated 
solid is washed with ether and dried, affording the title compound of 
formula 
##STR26## 
in the form of a colourless solid; m.p. 226.degree.-229.degree. C. (yield: 
0.6 g; 64%). 
Example H4: 
2,3,4,5-tetrahydro-3-oxo-4[(pyridin-N-oxide-3-yl)-methyleneamino]-6-methyl 
-1,2,4-triazine 
To a solution of 2.56 g (0.02 mol) 
2,3,4,5-tetrahydro-3-oxo-4-amino-6-methyl-1,2,4-triazine in 25 ml of 
ethanol are added 2.44 g (0.02 mol) of pyridine-3-carbaldehyde-N-oxide. 
The reaction mixture is refluxed for 1/2 hour, then cooled, and the 
precipitated solid is isolated by filtration, washed with ether and dried. 
The title compound of formula 
##STR27## 
is obtained in the form of a white solid; m.p. 242.degree.-244.degree. C. 
(yield: 3.6 g; 84%). 
The following compounds of formulae Ia, Ib and Ic are also prepared as 
described above: 
TABLE 3 
______________________________________ 
##STR28## (Ia) 
Compound R.sub.1 R.sub.2 R.sub.3 
Physical data 
______________________________________ 
3.01 CH.sub.3 
H H m.p. 249-250.degree. C. 
3.02 CH.sub.3 
CH.sub.3 
CH.sub.3 
m.p. 162-163.degree. C. 
______________________________________ 
TABLE 4 
__________________________________________________________________________ 
##STR29## (Ib) 
Compound 
R.sub.1 
R.sub.4 
R.sub.5 
R.sub.6 
R.sub.7 
n Physical data 
__________________________________________________________________________ 
4.01 CH.sub.3 
H H H Cl 0 m.p. 227-228.degree. C. 
4.02 CH.sub.3 
Cl H Cl Cl 0 m.p. 248-249.degree. C. 
4.03 C.sub.2 H.sub.5 
H H H Cl 0 m.p. 226-227.degree. C. 
4.04 CH.sub.3 
H H H CH.sub.3 O 
0 m.p. 193-196.degree. C. 
4.05 CH.sub.3 
CH.sub.3 O 
H H CH.sub.3 O 
0 m.p. 241-243.degree. C. 
4.06 CH.sub.3 
Cl H H H 0 m.p. 240-241.degree. C. 
4.07 CH.sub.3 
H H H CH.sub.3 
0 m.p. 220-223.degree. C. 
4.08 CH.sub.3 
NH.sub.2 
H H H 0 m.p. &gt;250.degree. C. 
4.09 CH.sub.3 
H H H H 1 m.p. 242-244.degree. C. 
4.10 CH.sub.3 
H H CH.sub.3 
H 0 m.p. 229-230.degree. C. 
4.11 CH.sub.3 
H CH.sub.3 
H H 0 
4.12 CH.sub.3 
H H F H 0 
4.13 CH.sub.3 
F H H H 0 
4.14 CH.sub.3 
H H H F 0 
4.15 CH.sub.3 
H F H H 0 
4.16 CH.sub.3 
H H H CH.sub.3 S 
0 
4.17 CH.sub.3 
H H H (CH.sub.3).sub.2 N 
0 
4.18 CH.sub.3 
CH.sub.3 
H H H 1 m.p. 238-240.degree. C. 
4.19 CH.sub.3 
CH.sub.3 
H H H 0 m.p. 226-229.degree. C. 
4.20 CH.sub.3 
SCH.sub.3 
H H H 0 m.p. 225.degree. C. 
4.21 C.sub.4 H.sub.9 (t) 
H H H H 1 m.p. 129-132.degree. C. 
4.22 C.sub.3 H.sub.7 (i) 
H H H H 1 m.p. 120-121.degree. C. 
__________________________________________________________________________ 
TABLE 5 
______________________________________ 
##STR30## (Ic) 
Compound R.sub.1 R.sub.2 R.sub.3 
Physical data 
______________________________________ 
5.01 CH.sub.3 H H m.p. 242.degree. C. 
5.02 (CH.sub.3).sub.2 CH 
H H m.p. 168-170.degree. C. 
5.03 CH.sub.3 CH.sub.3 
CH.sub.3 
m.p. 234-235.degree. C. 
______________________________________ 
EXAMPLE 2: FORMULATION EXAMPLES 
Formulations for Compounds of Formula I or Combinations Thereof with other 
Insecticides or Acaricides (Throughout, Percentages ary by Weight) 
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F1. Wettable powders a) b) c) 
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compound of formula I or combination 
25% 50% 75% 
sodium ligninsulfonate 
5% 5% -- 
sodium laurylsulfate 3% -- 5% 
sodium diisobutylnaphthalenesulfonate 
-- 6% 10% 
octylphenol polyethylene glycol ether 
-- 2% -- 
(7-8 mol of ethylene oxide) 
highly dispersed silicic acid 
5% 10% 10% 
kaolin 62% 27% -- 
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The active ingredient or combination is thoroughly mixed with the adjuvants 
and the mixture is thoroughly ground in a suitable mill, affording 
wettable powders which can be diluted with water to give suspensions of 
the desired concentration. 
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F2. Emulsifiable concentrate 
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compound of formula I or combination 
10% 
octylphenol polyethylene glycol ether 
3% 
(4-5 mol of ethylene oxide) 
calcium dodecylbenzenesulfonate 
3% 
castor oil polygycol ether 
4% 
(36 mol of ethylene oxide) 
cyclohexanone 30% 
xylene mixture 50% 
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Emulsions of any required concentration can be obtained from this 
concentrate by dilution with water. 
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F3. Dusts a) b) 
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compound of formula I or combination 
5% 8% 
talcum 95% -- 
kaolin -- 92% 
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Ready for use dusts are obtained by mixing the active ingredient with the 
carrier, and grinding the mixture in a suitable mill. 
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F4. Extruder granulate 
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compound of formula I or combination 
10% 
sodium ligninsulfonate 2% 
carboxymethylcellulose 1% 
kaolin 87% 
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The active ingredient or combination is mixed and ground with the 
adjuvants, and the mixture is subsequently moistened with water. The 
mixture is extruded and then dried in a stream of air. 
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F5. Coated granulate 
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compound of formula I or combination 
3% 
polyethylene glycol (mol. wt. 200) 
3% 
kaolin 94% 
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The finely ground active ingredient or combination is uniformly applied, in 
a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty 
coated granulates are obtained in this manner. 
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F6. Suspension concentrate 
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compound of formula I or combination 
40% 
ethylene glycol 10% 
nonylphenol polyethylene glycol ether 
6% 
(15 mol of ethylene oxide) 
sodium lignosulfonate 10% 
carboxymethylcellulose 1% 
37% aqueous formaldehyde solution 
0.2% 
silicone oil in the form of a 75% 
0.8% 
aqueous emulsion 
water 32% 
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The finely ground active ingredient or combination is intimately mixed with 
the adjuvants, giving a suspension concentrate from which suspensions of 
any desired concentration can be obtained by dilution with water. 
3. BIOLOGICAL EXAMPLES 
Example B.1: Contact action against Aphis craccivora 
Before the start of the test, 4- to 5-day-old pea seedlings (Pisum satirum) 
reared in pots are each populated with about 200 insects of the species 
Aphis craccivora. The treated plants are sprayed direct to drip point 24 
hours later with an aqueous formulation containing 400 ppm of the test 
compound. Two plants are used for each test compound, and a mortality 
count is made after a further 24 and 72 hours. The test is carried out at 
21.degree.-22.degree. C. and a relative humidity of about 55%. 
Compounds according to Tables 3, 4 and 5 exhibit good activity in this 
test. 
Example B.2: Systemic action against Myzus persicae 
Pimenta plants are infected with well populated pea seedlings. The soil is 
treated 4 days later with 25 ml of a 0.1% spray mixture prepared from a 
10% emulsifiable concentrate and water, such that the concentration of 
test compound in the soil is 12.5 ppm (amount by weight, based on the 
volume of the soil). The plants are enveloped in a paper frill. 
Evaluation of mortality is made 3 and 7 days after the start of the test. 
Two plants, each in a separate pot, are used for each test compound. The 
test is carried out at 25.degree. C. and ca. 65% relative humidity. 
After 1, 2 and 4 weeks the plants are populated anew and fresh mortality 
counts are made after 3 and 7 days following treatment. 
Compounds according to Tables 3, 4 and 5 exhibit good activity in this 
test. 
Example B.3: Contact action against Myzus persicae, direct spray test 
4 days before treatment, pipmenta plants (in the 6-leaf stage, in pots) are 
infested with a population of Myzus persicae (R strain) by placing pea 
seedlings 2-3 cm long and well populated with aphids on the pimenta 
plants. As soon as the pea seedlings begin to wither, the aphids migrate 
onto the test plants (pimenta). The treated plants are sprayed direct to 
drip point 24 hours later with an aqueous suspension prepared from a 25% 
wettable powder, containing 100 ppm of the test compound. Four plants are 
used for each test compound. A mortality count is made 7 days after 
application. The test is carried out at 21.degree.-22.degree. C. and ca. 
60% relative humidity. 
The compounds according to Tables 3, 4 and 5 exhibit good activity in this 
test. In particular, compound 4.09 effects over 80% kill. 
Example B.4: Test of long-term action against Myzus persicae 
Peperoni plants (in the 6-leaf stage, in pots) are treated by spray 
application with the test solutions and, 2 days after the treatment, the 
test plants are infested with a population of Myzus persicae (R strain) as 
described in Example B.3. An evaluation of the percentage mortality is 
made 5 days after populating the plants. 
The compounds according to Tables 3, 4 and 5 exhibit good activity against 
myzus persicae in this test. In particular compound 4.09 effects over 80% 
kill. 
Example B.5: Contact action against Bemisia tabaci 
Bean plants in pots (Phaseolus vulgaris, Autan variety) are populated in 
the 2-leaf stage with Bemisia tabaci (40 adults per plant). After a 3-day 
period for oviposition, the adults are removed. Ten days after population, 
when ca. 2/3 of the nymphs are in the late first nymphal stage and 1/3 are 
already in the second nymphal stage, the plants are treated in a spray 
chamber with a spray mixture (prepared from a 10% emulsifiable concentrate 
and water) in different concentrations. 
A count of dead nymphs, pupae and adults of the F.sub.1 generation is made 
24 days after population. The test is carried out at 25.degree. C. and 
50-60% relative humidity. 
Compounds according to Tables 3, 4 and 5 exhibit good activity at a 
concentration of 3 ppm. In particular, compound 4.09 effects over 80% 
kill.