Substituted malonic acid diamide insecticides, compositions and use

Insecticidally active novel substituted malonic acid diamide insecticides of the formula ##STR1## wherein R.sup.1 represents aryl or heteroaryl, each of which can optionally be substituted, PA1 R.sup.2 represents hydrogen or trialkylsilyl, and represents alkyl, cycloalkyl, alkenyl, alkinyl, aralkyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulphenyl, arylsulphenyl, alkylsulphonyl, arylsulphonyl, alkylaminosulphonyl, dialkylaminosulphonyl, arylaminosulphonyl or arylalkylaminosulphonyl, each of which can optionally be substituted, and represents radicals of the formula EQU --CO--NR.sup.5 R.sup.6 wherein PA1 R.sup.5 and R.sup.6 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, alkylaminocarbonyl, arylaminocarbonyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulphonyl or arylsulphonyl, it being possible for these radicals to be optionally substituted, PA1 R.sup.3 represents hydrogen or the radical R.sup.4, PA1 R.sup.7 and R.sup.8 independently of one another represent hydrogen, alkyl or aryl, and PA1 R.sup.4 represents a radical of the formula EQU --CH.sub.2 --R.sup.9 and PA1 R.sup.9 represents hydroxyl, alkoxy or aryloxy, each of which is optionally substituted, and alkylamino, arylamino, aralkylamino, dialkylamino, diarylamino, cycloalkylamino, alkenylamino, or nitrogen-containing saturated heterocyclic radicals which are bonded via N and which optionally contain further hetero atoms.

The present invention relates to new substituted malonic acid derivatives, 
processes for their preparation, and their use as pest-combating agents. 
It has been disclosed that malonic acid derivatives, such as 
3,4-dichlorophenyl-malonic acid diamide, possess insecticidal activity 
(application Ser. No. 419,100, filed Sept. 16, 1982, corresponding to 
German Published Specification DE-OS 3,140,275). Their action is not 
always satisfactory when low concentrations are used. 
It has been found that the substituted malonic acid derivatives of the 
general formula I are outstandingly suitable for combating pests: 
##STR2## 
in which R.sup.1 represents aryl or heteroaryl, each of which can 
optionally be substituted, 
R.sup.2 represents hydrogen or trialkylsilyl, and represents alkyl, 
cycloalkyl, alkenyl, alkinyl, aralkyl, alkylcarbonyl, arylcarbonyl, 
alkoxycarbonyl, aryloxycarbonyl, alkylsulphenyl, arylsulphenyl, 
alkylsulphonyl, arylsulphonyl, alkylaminosulphonyl, dialkylaminosulphonyl, 
arylaminosulphonyl or arylalkylaminosulphonyl, each of which can 
optionally be substituted, and represents radicals of the formula 
EQU --CO--NR.sup.5 R.sup.6 
wherein 
R.sup.5 and R.sup.6 independently of one another represent hydrogen, alkyl, 
cycloalkyl, aryl, alkylaminocarbonyl, arylaminocarbonyl, alkylcarbonyl, 
arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulphonyl or 
arylsulphonyl, it being possible for these radicals to be optionally 
substituted, 
R.sup.3 represents hydrogen or the radical R.sup.4, R.sup.7 and R.sup.8 
independently of one another represent hydrogen, alkyl or aryl, and 
R.sup.4 represents the radical of the formula 
EQU --CH.sub.2 --R.sup.9 
wherein 
R.sup.9 represents hydroxyl, alkoxy or ayloxy, each of which can optionally 
be substituted, alkylamino, cycloalkylamino, arylamino, dialkylamino, 
alkenylamino, diarylamino, aralkylamino or nitrogen-containing saturated 
heterocyclic radicals which are bonded via N and which optionally contain 
further hetero atoms. 
It has furthermore been found that the compounds of the formula I 
##STR3## 
wherein R.sup.1 represents aryl or heteroaryl, each of which can 
optionally be substituted, 
R.sup.2 represents hydrogen or trialkylsilyl, and represents alkyl, 
cyloalkyl, alkenyl, alkinyl, aralkyl, alkylcarbonyl, arylcarbonyl, 
alkoxycarbonyl, aryloxycarbonyl, alkylsulphenyl, arylsulphenyl, 
alkylsulphonyl, arylsulphonyl, alkylaminosulphonyl, dialkylaminosulphonyl, 
arylaminosulphonyl or arylalkylaminosulphonyl, each of which can 
optionally be substituted, and represents radicals of the formula 
EQU --CO--NR.sup.5 R.sup.6 
wherein 
R.sup.5 and R.sup.6 independently of one another represent hydrogen, alkyl, 
cycloalkyl, aryl, alkylaminocarbonyl, arylaminocarbonyl, alkylcarbonyl, 
arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulphonyl or 
arylsulphonyl, it being possible for these radicals to be optionally 
substituted, 
R.sup.3 represents hydrogen or the radical R.sup.4, 
R.sup.7 and R.sup.8 represent hydrogen, alkyl or aryl, and 
R.sup.4 represents a radical of the formula 
EQU --CH.sub.2 --R.sup.9 
wherein 
R.sup.9 represents hydroxyl, alkoxy or aryloxy, each of which can 
optionally be substituted, alkylamino, arylamino, aralkylamino, 
dialkylamino, diarylamino, cycloalkylamino, alkenylamino, or 
nitrogen-containing saturated heterocyclic radicals which are bonded via N 
and optionally contain further nitro atoms, 
are obtained by a process in which compounds of the formula II 
##STR4## 
wherein R.sup.1, R.sup.2, R.sup.7 and R.sup.8 have the meaning given 
above, are reacted with formaldehyde or formaldehyde-donating compounds in 
the presence of an acid or base and, if appropriate, simultaneously or 
subsequently with alkylamines, cycloalkylamines, alkenylamines, 
arylamines, dialkylamines, diarylamines, aralkylamines or N-containing 
saturated heterocyclic compounds which optionally can contain further 
hetero atoms, or with aliphatic or aromatic OH compounds. 
The substituted malonic acid derivatives according to the invention are 
particularly suitable for combating insects and spider mites. Moreover, 
they are distinguished by a substantially better action than the compounds 
known for these indications from the prior art. They also possess 
advantageous properties in respect of toxicity to warm-blooded animals. 
Preferred new substituted malonic acid derivatives of the general formula I 
are those in which 
R.sup.1 represents phenyl which can optionally be substituted by one or 
more identical or different radicals from amongst the following radicals: 
halogen, in particular chlorine, bromine or fluorine, nitro, amino, OH, 
CN, C.sub.1-4 -alkyl, in particular methyl, C.sub.1-4 -halogenoalkyl, in 
particular trifluoromethyl, trichloromethyl or pentafluoroethyl, C.sub.1-4 
-alkoxy, methylenedioxy, ethylenedioxy, C.sub.1-4 -halogenoalkoxy, in 
particular trifluoromethoxy, pentafluoroethoxy, difluoromethylenedioxy, 
halogen-substituted ethylenedioxy, C.sub.1-4 -alkylthio, C.sub.1-4 
-halogenoalkylthio, in particular trifluoromethylthio, C.sub.2-8 
-alkoxyalkyl, C.sub.2-8 -halogenoalkoxyalkyl, C.sub.1-4 -alkylsulphonyl, 
in particular methylsulphonyl, C.sub.1-4 -halogenoalkylsulphonyl, 
carboxyl, carbalkoxy, in particular methoxycarbonyl, and the radical 
C.sub.1-4 -alkoxy-N.dbd.CH--, in particular CH.sub.3 O--N.dbd.CH--, or 
phenyl, phenoxy, thiophenyl which can optionally be substituted by halogen 
or C.sub.1-4 -alkyl, and carboxyalkoxy having 2-4 C atoms, such as 
carboxymethoxy. 
R.sup.1 furthermore preferably represents heteroaryl, such as pyridinyl, 
pyrimidinyl, triazinyl, isoxazolyl, thiazolyl, oxadiazolyl, imidazolyl, 
triazolyl, furanyl or thiophenyl, each of which can optionally be 
monosubstituted or polysubstituted by identical or different substituents 
from amongst halogen, in particular chlorine, C.sub.1-4 -alkyl, in 
particular methyl or ethyl, and C.sub.1-4 -alkoxy, in particular methoxy 
or ethoxy. 
R.sup.1 furthermore preferably represents 3-nitrophenyl, 3-iodophenyl, 
biphenyl, 4-trimethylsilyoxyphenyl, 4-chloro3-nitrophenyl, 
3-chloro-4-nitrophenyl, 3,4,5-trichlorophenyl, 
3,5-dichloro-4-fluorophenyl, 4-difluoromethylphenyl, 
3-nitro-4-fluorophenyl, 3-fluoro-4-nitrophenyl, 
3-trifluoromethyl-4-chlorophenyl, 4-trifluoromethyl-3-chlorophenyl, 
3-chloro-5-trifluoromethylphenyl, 3,4-(di(trifluoromethyl)-phenyl, 
3-trifluoromethyl-4,5-dichlorophenyl, 
4-trifluoromethyl-3,5-dichlorophenyl, 4-trifluoromethoxy-3-nitrophenyl, 
4-trifluoromethoxy-3-bromophenyl, 4-nitro-3-trifluoromethoxyphenyl, 
4-bromo-3-trifluoromethoxphenyl, 
3-nitro-4-trifluoromethoxy-5-chlorophenyl, 4-methoxy-3,5-dichlorophenyl, 
4-methyl-3,5-dichlorophenyl, 4-fluoro-3-bromophenyl, 
4-bromo-3-fluorophenyl, 4-chloro-3-methylphenyl, 
4-trifluoromethylmercaptophenyl, 4-trifluoromethoxy-3-chlorophenyl, 
3-trifluoromethyl-4-chlorophenyl, 4-chloro-difluoromethoxy-3-chlorophenyl, 
4-fluoro-3-chlorophenyl, pentafluorophenyl, 4-fluoro-3,5-dibromophenyl, 
4-fluoro-3-chloro-5-bromophenyl, 4-chloro-3,5-dibromophenyl, 
4-bromo-3,5-dichlorophenyl, 3-bromo-4,5-dichlorophenyl, 
3,4,5-trifluorophenyl, 3,4,5-tribromophenyl, 4-amino-3,5-dichlorophenyl or 
4-hydroxy-3,5-dichlorophenyl. 
Preferred compounds of the formula I are those in which 
R.sup.2 represents hydrogen, trialkylsilyl having 1-4 C atoms in the alkyl 
part, C.sub.1-4 -alkyl, C.sub.1-4 -alkylcarbonyl, benzoyl which can 
optionally be substituted by one or more identical or different radicals 
from amongst the following radicals (A). (A) represents halogen, in 
particular chlorine, bromine or fluorine, nitro, amino, CN, C.sub.1-4 
-alkyl, in particular methyl, C.sub.1-4 -halogenoalkyl, in particular 
trifluoromethyl or pentafluoroethyl, C.sub.1-4 alkoxy, C.sub.1-4 
-halogenoalkoxy, in particular trifluoromethoxy, pentafluoroethoxy, 
methylenedioxy, ethylenedioxy or difluoromethylenedioxy, 
halogen-substituted ethylenedioxy, such as trifluoroethylenedioxy, 
C.sub.1-4 -alkylthio, C.sub.1-4 -halogenoalkylthio, in particular 
trifluoromethylthio, C.sub.2-8 -alkoxyalkyl, C.sub.2-8 
-halogenoalkoxyalkyl, C.sub.1-5 -alkylsulphenyl or phenylsulphenyl, each 
of which can optionally be substituted, C.sub.1-4 -alkylsulphonyl, in 
particular methylsulphonyl, C.sub.1-4 -halogenoalkylsulphonyl, carbalkoxy, 
in particular methoxycarbonyl, and the radical C.sub.1-4 
-alkoxy-N.dbd.CH--, in particular CH.sub.3 -O-N.dbd.CH--, or represents 
phenyl, phenoxy or thiophenyl, each of which can optionally be substituted 
by halogen or C.sub.1-4 -alkyl, and represents carboxyalkoxy having 2-4 C 
atoms, such as carboxymethoxy; 
R.sup.2 furthermore preferably represents C.sub.1-4 -alkoxycarbonyl, 
phenoxycarbonyl which can optionally be substituted by one or more 
radicals (A), or preferably represents C1-4-alkylsulphonyl, 
phenylsulphonyl which can optionally be substituted by one or more 
radicals (A), or preferably represents C.sub.1-4 -alkylaminosulphonyl, 
C.sub.1-5 -alkylsulphenyl or phenylsulphenyl, each of which can optionally 
be substituted, di-C.sub.1-4 -alkylaminosulphonyl, phenylaminosulphonyl 
which can optionally be substituted by one or more radicals (A), or 
represents phenyl-C.sub.1-4 -alkylaminosulphonyl. 
Preferred compounds of the formula I are those in which 
R.sup.3 represents hydrogen or the radical R.sup.4. 
R.sup.7 and R.sup.8 preferably represent hydrogen or C.sub.1-4 -alkyl, or 
preferably represent phenyl which is optionally substituted by halogen. 
Hydrogen and methyl are very particularly preferred. 
R.sup.4 preferably represents 
EQU --CH.sub.2 --R.sup.9 
wherein 
R.sup.9 represents hydroxyl, C.sub.1-4 -alkoxy, phenoxy which can 
optionally be substituted by one or more radicals (A), or represents 
C.sub.1-8 -alkylamino, C.sub.5-6 -cycloalkylamino, phenylamino which is 
optionally substituted by one or more radicals (A), or represents 
di-C.sub.1-8 -alkylamino, phenyl-C.sub.1-4 -alkylamino, or saturated 
nitrogen-containing heterocyclic compounds which are bonded via N and have 
5-6 ring atoms, such as morpholine, pyrimidine or piperidine. 
Particularly preferred compounds of the formula I are those in which 
R.sup.1 represents phenyl which is optionally substituted by halogen, in 
particular fluorine or chlorine, C.sub.1-4 -alkyl, in particular methyl, 
C.sub.1-4 -alkoxy, C.sub.1-4 -halogenoalkoxy, C.sub.1-4 -halogenoalkyl, 
NH.sub.2, CH.sub.3 O-N.dbd.CH--or nitro. 
Compounds of the general formula I which may be very particularly mentioned 
are those in which 
R.sup.1 represents phenyl which is optionally monosubstituted to 
trisubstituted in the 3-, 4-, or 5-position by identical or different 
substituents from amongst halogen, in particular fluorine, chlorine, 
bromine or iodine, 
R.sup.2 represents C.sub.1-4 -alkyl, in particular methyl, optionally 
halogen-substituted C.sub.1-4 -alkylaminosulphonyl, C.sub.1-4 
-alkylcarbonyl, in particular methylcarbonyl, optionally 
halogen-substituted phenylcarbonyl, phenylsulphenyl, C.sub.1-4 
-alkylsulphenyl or trialkylsilyl, in particular trimethylsilyl, and 
represents --CO--NR.sup.5 R.sup.6, 
wherein 
R.sup.5 represents hydrogen and R6 represents optionally 
halogen-substituted phenyl or phenylcarbonyl, or represents C.sub.1-4 
-alkyl or C.sub.1-4 -alkylcarbonyl, 
R.sup.4 represents --CH.sub.2 --R.sup.9, 
wherein 
R.sup.9 represents C.sub.1-4 -alkylamino, phenylamino, C.sub.2-8 
dialkylamino, morpholino or piperidino. 
Compounds of the formula I which may be particularly mentioned are those in 
which 
R.sup.1 represents phenyl which is optionally monosubstituted or 
polysubstituted by chlorine, and 
R.sup.2 represents hydrogen or trimethylsilyl, 
R.sup.3 represents hydrogen or R.sup.4, and 
R.sup.4 represents methylamino, ethylamino, morpholino or piperidino. 
__________________________________________________________________________ 
##STR5## I 
R.sup.1 R.sup.2 
R.sup.3 R.sup.4 R.sup.7 
R.sup.8 
__________________________________________________________________________ 
##STR6## 
H H CH.sub.2 OCH.sub.3 
H H 
##STR7## 
H CH.sub.2 OCH.sub.3 
CH.sub.2 OCH.sub.3 
H H 
##STR8## 
CH.sub.3 
H CH.sub.2 OH 
H H 
##STR9## 
H CH.sub.3 CH.sub.2 NHC.sub.6 H.sub.5 
CH.sub.3 
CH.sub.2 NHC.sub.6 H.sub.5 
##STR10## 
H H CH.sub.2 OC.sub.2 H.sub.5 
H H 
##STR11## 
H CH.sub.2 OCH.sub.3 
CH.sub.2 OCH.sub.3 
H H 
##STR12## 
CH.sub.3 
CH.sub.2 OH 
CH.sub.2 OH 
CH.sub.3 
CH.sub.3 
##STR13## 
H CH.sub.2 OC.sub.2 H.sub.5 
CH.sub.2 OC.sub.2 H.sub.5 
H H 
##STR14## 
H CH.sub.2 N(CH.sub.3).sub.2 
CH.sub.2 N(CH.sub.3).sub.2 
CH.sub.3 
CH.sub.3 
##STR15## 
CH.sub.3 
##STR16## 
##STR17## H H 
##STR18## 
Si(CH.sub.3).sub. 3 
##STR19## 
##STR20## H H 
__________________________________________________________________________ 
The reaction of the compounds of the formula II with formaldehyde is 
carried out, if appropriate, in the presence of acid acceptors and, if 
appropriate, in the presence of a diluent. The course of the reaction can 
be represented by, for example, the following equation: 
##STR21## 
Formaldehyde is employed in amounts from an equimolar amount to about a 
10-fold excess. 
Preferably used compounds of the formula II are those in which the 
substituents R.sup.3 and R.sup.4 have the meanings mentioned as being 
preferred in the case of the compounds of the formula I. Compounds of the 
formula II are known (application Ser. No. 419,100, filed Sept. 16,1982, 
corresponding to German Published Specification DE-OS 3,140,27. They can 
be prepared by the process there. The following compounds of the formula 
II may be mentioned individually: Phenyl-hydroxy-malonic acid diamide, 2-, 
3- and 4-chlorophenylhydroxy-malonic acid diamide, 
2,3-dichlorophenylhydroxy-malonic acid diamide, 
3,4-dichlorophenyl-hydroxymalonic acid diamide, 
3,5-dichlorophenyl-hydroxy-malonic acid diamide, 
2,4-dichlorophenyl-hydroxy-malonic acid diamide, 
2,5-dichlorophenyl-hydroxy-malonic acid diamide, 
2,6-dichlorophenyl-hydroxy-malonic acid diamide, 2-, 3- and 
4-nitrophenyl-hydroxy-malonic acid diamide, 
2-chloromethylphenyl-hydroxy-malonic acid diamide, 2-, 3- and 
4-trifluoromethylphenyl-hydroxy-malonic acid diamide, 2-, 3- and 
4-methoxyphenyl-hydroxy-malonic acid diamide, 
2,6-dimethoxyphenyl-hydroxy-malonic acid diamide, 2-, 3- and 
4-tolyl-hydroxy-malonic acid diamide, 2-, 3- and 
4-trifluoromethoxyphenyl-hydrozy-malonic acid diamide, 2-, 3- and 
4-fluorophenyl-hydroxymalonic acid diamide, 
3,4-dichlorophenyl-hydroxy-malonic acid amide methylamide, 
phenyl-hydroxy-malonic acid diethylamide amide, 
3,5-dichlorophenyl-hydroxy-malonic acid amide morpholinylamide, 
3,4-dichlorophenyl-hydroxy-malonic acid-bis-isopentylamide, 
phenylhydroxy-malonic acid-bismethylamide, cyclohexyl-hydroxy-malonic acid 
diamide, 2,3,4-, 2,3,6- and 3,4,5-trichlorophenyl-hydroxy-malonic acid 
diamide, 2,3,4,5- and 2,3,5,6-tetrachlorophenyl-hydroxy-malonic acid 
diamide and pentachlorophenyl-hydroxy-malonic acid diamide. 
Formaldehyde-donating compounds which may be mentioned are polymeric 
formaldehyde, such as metaldehyde or paraldehyde, and formaldehyde 
acetals, such as formaldehyde diethyl acetal. 
Suitable diluents are all inert organic solvents. These include, in 
particular, aliphatic and aromatic, optionally halogenated hydocarbons, 
such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, 
ligroin, benzene, toluene, methylene chloride, ethylene chloride, 
chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, and 
furthermore ethers, such as diethyl and dibutyl ether, glycol dimethyl 
ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, and in 
addition esters, such as methyl acetate and ethyl acetate, or nitriles, 
such as, for example acetonitrile and propionitrile, benzonitrile and 
glutarodinitrile, and furthermore amides, such as, for example, 
dimethylformamide, dimethylacetamide and N-methylpyrrolidone, as well as 
dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric acid 
triamide. 
All customary acid-binding agents can be used as bases. These preferably 
include alkali metal carbonates, hydroxides or alcoholates, such as sodium 
carbonate or potassium carbonate, sodium hydroxide and potassium 
hydroxide, sodium methylate, potassium methylate, sodium ethylate and 
potassium ethylate, and further aliphatic, aromatic or heterocyclic 
amines, for example trimethylamine, triethylamine, tributylamine, 
dimethylaniline, dimethylbenzylamine and pyridine. 
Suitable acids are Lewis acids, such as boron trifluoride, aIuminum 
trichloride and titanium tetrachloride, and mineral acids, such as 
sulphuric acid, hydrogen halides and phosphoric acid. 
The reaction temperature is kept between about 0.degree.C. and 
130.degree.C., preferably between about 20.degree.C. carried out under 
atmospheric and 60.degree.C. The process is preferably carried out under 
atmospheric pressure. 
When the reaction is complete, the reaction mixture can be worked up in a 
customary manner in order to isolate the compounds of the formula I, in 
which R.sup.9 represents OH. However, the reaction mixture can also be 
used directly for further reaction with amines. 
For this purpose, as the reaction mixture, in one of the stated solvents, 
preferably in ethers, such as dioxane or dialkyl ethers, or in ketones, 
such as acetones, occupied by at least an equimolar amount of the amine 
components, acidic and basic catalysts being employed in the customary 
manner. The reaction is carried out to completion at between 0.degree.C. 
and 130.degree.C., preferably 40.degree.C.-80.degree.C., 1 to 6 hours 
usually being required for this. 
Catalysts which may be mentioned are the acidic and basic catalysts 
mentioned for carrying out the reaction with formaldehyde. The acidic 
catalysts are preferred. 
The following may be mentioned as amines which can be employed: 
methylamine, ethylamine, propylamine, isopropylamine, butylamine, 
iso-butylamine, tert.-butylamine, hexylamine, dodecylamine, 
2-ethylhexylamine, tetradecylamine, hexadecylamine, octadecylamine, 
allylamine, 2-methoxyethylamine, 2-ethoxypropylamine, 3-butoxypropylamine, 
2-methylpropyl 3-aminopropanoate, 6-aminohexanitrile, lysine esters, 
1,1-aminoundecanoates, cyclohexylamine, trimethylcyclohexylamine, 
2-borbornylmethylamine, aniline, o,m,p-chloroaniline, 2,3-, 2,4-, 2,5- and 
2,6-dichloroaniline, 3,4- and 3,5-dichloroaniline, p-o-nitroaniline, 
m,o,p-tolylamine, 3-trifluoromethylaniline, 3-chloro-4-methylaniline, 
4-chloro-3-methylaniline, benzylamine, phenylcyclohexylamine and 
naphthylamine, as well as sec.amines, for example dimethylamine, 
diethylamine, morpholine, piperidine, piperazine, pyrazole and imidazole. 
When the reaction is complete, the compounds of the formula I are isolated 
in a customary manner. 
The compounds of the formula I in which the radical R.sup.8 has the meaning 
other than hydroxyl can be prepared by a variant of the process. To do 
this, the compounds of the formula II are brought to reaction with 
formaldehyde and the amines in a single-stage synthesis. In this 
procedure, the reaction is carried out as follows: the components are 
stirred in at least an equimolar ratio, preferably with 3 to 6 times the 
amount, relative to the compounds of the formula II, of formaldehyde, and 
the same excess amount of amine, in one of the stated solvents, 
particularly preferably dioxane, diethyl ether, tetrahydrofuran or 
acetone, with the catalyst, for example potassium carbonate or boron 
trifluoride etherate, at temperatures between 30.degree.C. and 
100.degree.C. 
The active compounds are well tolerated by plants, have a favorable level 
of toxicity to warm-blooded animals, and are suitable for combating animal 
pests, especially insects and arachnida, which are encountered in 
agriculture, in forestry, in the protection of stored products and of 
materials, and in the hygiene field. They are active against normally 
sensitive and resistant species and against all or some stages of 
development. The abovementioned pests include: 
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium 
vulgare and Porcellio scaber. From the order of the Diplopoda, for 
example, Balniulus guttulatus. From the order of the Chilopoda, for 
example, Geophilus carpophagus and Scutigera spec. From the order of the 
Symphyla, for example, Scutigerella immaculata. From the order of the 
Thysanura, for example Lepisma saccharina. From the order of the 
Collembola, for example, Onychiurus armatus. From the order of the 
Orthoptera, for example, Blatta orientalis, Periplaneta americana, 
Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa 
spp., Locusta migratoria migratorioides, Melanoplus differentialis and 
Schistocerca gregaria. From-the order of the Dermaptera, for example, 
Forficula auricularia. From the order of the Isoptera, for example, 
Reticulitermes spp. From the order of the Anoplura, for example, 
Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, 
Haematopinus spp. and Linognathus spp. From the order of the Mallophaga, 
for example, Trichodectes spp. and Damalinea spp. From the order of the 
Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci. From 
the order of the Heteroptera, for example, Eurygaster spp., Dysdercus 
intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and 
Triatoma spp. From the order of the Homoptera, for example, Aleurodes 
brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, 
Brevicoryne brassicae , Cryptomyzus ribis, Doralis fabae, Doralis pomi, 
Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., 
Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, 
Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax 
striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, 
Pseudococcus spp. and Psylla spp. From the order of the Lepidoptera, for 
example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, 
Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, 
Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix 
thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia 
spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra 
brassicae, Panolis flammea, Prodenia Litura, Spodoptera spp., Trichoplusia 
ni, Carpocapsa pomenella, Pieris spp., Chilo spp., Pyrausta nubilalis, 
Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea 
pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capus 
reticulana, Cho-ristoneura fumiferana, Clysia ambiguella, Homona magnanima 
and Tortrix viridana. From the order of the Coleoptera, for example, 
Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, 
Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, 
Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., 
Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., 
Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus 
sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera 
postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., 
Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium 
psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus 
spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra 
zealandica. From the order of the Hymenoptera, for example, Diprion-spp., 
Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp. From the 
order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., 
Drosophila melanogaster, Musca spp., Fannia spp., Calliphora 
erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., 
Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma 
spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia 
spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula 
paludosa. From the order of the Siphonaptera, for example, Xenopsylla 
cheopis and Ceratophyllus spp. From the order of the Arachnida, for 
example, Scorpio maurus and Latrodectus mactans. From the order of the 
Acarina, for example, Acarus siro,Argas spp., Ornithodoros spp., 
Dermanyssus. gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilis 
spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., 
Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia 
praetiosa, Panonychus spp. and Tetranychus spp. 
The active compounds can be converted to the customary formulations, such 
as solutions, emulsions, suspensions, powders, foams, pastes, granules, 
aerosols, natural and synthetic materials impregnated with active 
compound, very fine capsules in polymeric substances and in coating 
compositions for seed, and formulations used with burning equipment, such 
as fumigating cartridges, fumigating cans, fumigating coils and the like, 
as well as ULV cold mist and warm mist formulations. 
These formulations are produced in known manner, for example by mixing the 
active compounds with extenders, that is, liquid solvents, liquefied gases 
under pressure, and/or solid carriers, optionally with the use of 
surface-active agents, that is, emulsifying agents and/or dispersing 
agents, and/or foam forming agents. In the case of the use of water as an 
extender, organic solvents can, for example, also be used as auxiliary 
solvents. As liquid solvents, there are suitable in the main: aromatics, 
such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or 
chlorinated aliphatic hydrocarbons, such as chlorobenzenes, 
chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as 
cyclohexane or paraffins, for example mineral oil fractions, alcohols, 
such as butanol or glycol as well as their ethers and esters, ketons, such 
as acetone, methyl ethyl ketone, methyl isoutyl ketone or cyclohexanone, 
strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, 
as well as water; by liquefied gaseous extenders or carriers are meant 
liquids which are gaseous at normal temperature and under normal pressure, 
for example aerosol propellants, such as halogenated hydrocarbons as well 
as butane, propane, nitrogen and carbon dioxide; as solid carriers, there 
are suitable: for example ground natural minerals, such as kaolins, clays, 
talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, 
and ground synthetic materials, such as highly dispersed silicic acid, 
alumina and silicates; as solid carriers for granules there are suitable: 
for example crushed and fractionated natural rocks such as calcite, 
marble, pumice, sepiolite and dolomite, as well as synthetic granules of 
inorganic and organic meats, and granules of organic material such as 
sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying 
and/or foam-forming agents there are suitable: for example non-ionic and 
anionic emulsifiers, such as polyoxyethylene-fatty acid esters, 
polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol 
ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as 
albumin hydrolysis products; as dispersin agents there are suitable: for 
example ligninsulphite waste liquors and methylcellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, can be used in the formulations. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, 
and trace nutrients such as salts of iron, manganese, boron, copper, 
cobalt, molybdenum and zinc. 
The formulations in general contain between 0.1 and 95 per cent by weight 
of active compound, preferably between 0.5 and 90%. 
The active compounds according to the invention can be present in their 
commercially available formulations and in the use forms, prepared from 
these formulations, as a mixture with other active compounds, such as 
insecticides, baits, sterilizing agents, acaricides, nematicides, 
fungicides, growth-regulating substances or herbicides.. The insecticides 
include, for example, phosphates, carbamates, carboxylates, chlorinated 
hydrocarbons, phenylureas, substances produced by microorganisms. 
The active compounds according to the invention can furthermore be present 
in their commercially available formulations and in the use forms, 
prepared from these formulations, as a mixture with synergistic agents. 
Synergistic agents are compounds which increase the action of the active 
compounds, without it being necessary for the synergistic agent added to 
be active itself. 
The active compound content of the use forms prepared from the commercially 
available formulations can vary within wide limits. The active compound 
concentration of the use forms can be from 0.0000001 to 95% by weight of 
active compound, preferably between 0.0001 and 1% by weight. 
The compounds are employed in a customary manner appropriate for the use 
forms. 
When used against hygiene pests and pests of stored products, the active 
compounds are distinguished by an excellent residual action on wood and 
clay as well as a good stability to alkali on limed substrates. 
The active compounds according to the invention are also suitable for 
combating ectoparasites and endoparasites, preferably ectoparasitic 
insects in the field of animal husbandry and animal breeding. 
The active compounds according to the invention are used in a known manner, 
such as by oral administration and by dermal application, for example in 
the form of dipping, spraying, pouring-on and spotting-on, and dusting. 
PREATION EXAMPLES 
Preparation of the starting substances 
Example a 
##STR22## 
30 g (0.114 mol) of 3,4-dichloro-phenyl-hydroxymalonic acid diamide in 60 
ml of dimethyl sulphoxide are initially taken. Thereafter, 6.38 g (0.144 
mol) of potassium hydroxide in 150 ml of water are added dropwise, 
followed by the dropwise addition of 16.1 g (0.114 mol) of methyl iodide. 
The reaction is exothermic, the temperature increasing to about 50.degree. 
C. The mixture is allowed to cool, and stirring is continued for 16 hours 
at 20.degree. C. The precipitated solid is filtered off under suction and 
washed with water and then with petroleum ether. 
After recrystallization from ethyl acetate, 14.1 g (44.3% of theory) of 
2-(3,4-dichlorophenyl)-2-methoxymalonic acid diamide of melting point 211 
to 213.degree. C. are obtained. 
Example b 
##STR23## 
13.1 g of 3,4-dichlorophenylhydroxymalonic acid diamide in 200 ml of 
benzoyl chloride were heated to 110.degree. C. for 9 hours. Thereafter, 
the mixture was cooled to 5.degree. C., and the precipitate was filtered 
off under suction, washed with toluene and then recrystallized from 550 ml 
of i-propanol. 10 g of 3,3-dichlorophenylbenzoyloxymalonic acid diamide 
were isolated: m.p. 225.degree. C., with decomposition. 
Example c 
##STR24## 
3 g (0.0114 mol) of 3,4-dichloro-phenyl-hydroxymalonic acid diamide, 1.12 g 
(0.0114 mol) of trimethylsilyl cyanide and 0.9 g (0.0114 mol) of pyridine 
are heated to 100.degree. C. (bath temperature) for 6 hours. After the 
pyridine dine has been removed under the vacuum from a water pump, the 
residue is recrystallized from petroleum ether. 
3.45 g (90.3 g of theory) of 
2-(3,4-dichlorophenyl)2-trimethylsilyloxy-malonic acid diamide of melting 
point 156.degree. C. are obtained.

EXAMPLE 1 
78 g (0.3 mol) of 3,4-dichlorophenyl-hydroxymalonic acid diamide and 27 g 
of paraformaldehyde (0.9 mol) in 1 liter of acetone are stirred under 
reflux with 0.5 g of potassium carbonate for 15 minutes, after which the 
mixture is filtered while hot. On cooling, 
N,N'-bishydroxymethylene-3,4-dichlorophenyl-hydroxymalonic acid diamide is 
precipitated. M.p. 118.degree.-120.degree. C., yield 43 g (49% of theory). 
The mother liquor predominantly contains the monohydroxymethylene product. 
EXAMPLE 2 1:1 mixture of mono- and bishydroxymethylene product: 
78 g (0.3 mol) of the starting material as in Example 1 are boiled with 27 
g of paraformaldehyde and 0.5g of calcium oxide in 1 liter of acetone for 
15 minutes, and the mixture is filtered while hot and then evaporated 
down. A colorless oil remains which is a 1:1 mixture of the mono- and 
bishydroxymethylene product of 3,4-dichlorophenyl-hydroxymalonic acid 
diamide. 
EXAMPLE 3 
Bis-piperidinomethylene product: 
5.2 g (0.02 mol) of 3,4-dichlorophenyl-hydroxymalonic acid diamide and 4 g 
of 37% strength aqueous formaldehyde maldehyde solution are stirred with 3 
g of piperidine and 3 drops of boron trifluoride etherate in 50 ml of 
dioxane at 50.degree. C. After approx. 7 hours, the reaction is 
interrupted with 0.5 ml of triethylamine, and the reaction mixture is 
evaporated down. The solid residue is taken up with ether, the mixture is 
stirred, and the product is filtered off under suction and rinsed with 
ether. Yield: 6.0 g of 
bis-piperidinomethylene-3,4-dichlorophenyl-hydroxymalonic acid diamide 
(66% of theory). Further product can be isolated from the mother liquor. 
M.p.: 159.degree.-160.degree. C. 
EXAMPLE 4 
2.5 g of bisdimethylaminomethylene-3,4-dichlorophenyl-hydroxymalonic acid 
diamide (33% of theory) are obtained analogously to Example 3, using the 
same amount of mixture, with 5.8 g of 50% strength aqueous dimethylamine 
solution. M.p.: 98.degree.-100.degree. C. When gaseous dimethylamine is 
used, 5.8 g of product are obtained (77% of theory). 
EXAMPLE 5 
3.21 g of bishydroxymethylene-3,4-dichlorophenyl-hydroxymalonic acid 
diamide (0.01 mol) are kept at 50.degree. C. with 3 g of piperidine and 3 
drops of boron trifluoride in 50 ml of dioxane for 8 hours. After the 
addition of 0.5 ml of triethylamine, the mixture is evaporated down, the 
residue is taken up with ether, and the product is filtered off under 
suction. 6.7 g of 
bis-piperidinomethylene-3,4-dichlorophenyl-hydroxymalonic acid diamide 
(73% of theory) of melting point 195.degree. C. are obtained. 
EXAMPLE 6 
5.2 g of the starting compound from Example 1 are stirred with 3.2 g of 37% 
strength aqueous formalin solution and 2 g of morpholine in 20 ml of 
dioxane and 2 ml of concentrated sulphuric acid for 6 hours at 40.degree. 
C. After 4 ml of triethylamine have been added, the mixture is evaporated 
down in vacuo, and the residue is taken up with 30 ml of diethyl ether. 
The precipitated solid is a 1 mixture of mono- and 
bis-morpholinomethylene-3,4-dichlorophenyl-hydroxymalonic acid diamide. 
Yield: 3.7 g. 
Example A 
Critical concentration test/root-systemic action 
Test insect: Phaedon cochleariae 
Solvent: 3 parts by weight of acetone 
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent, the stated 
amount of emulsifier is added and the concentrate is diluted with water to 
the desired concentration. 
The preparation of active compound is intimately mixed with soil. The 
concentration of the active compound in the preparation is of practically 
no importance, only the amount by weight of active compound per unit 
volume of soil, which is given in ppm (=mg/1), being decisive. The treated 
soil is filled into pots and these are planted with cabbage (Brassica 
oleracea). The active compound can in this way be taken up from the soil 
by the roots of the plants and be transported into the leaves. 
To demonstrate the root-systemic effect, exclusively the leaves are 
infested with the abovementioned test animals after 7 days. After a 
further 2 days, the evaluation is made by counting or estimating the dead 
insects. The root-systemic action of the active compound is deduced from 
the mortality figures. It is 100% if all the test insects have been killed 
and 0% if just as many test insects are still alive as in the case of the 
untreated control. 
In this test, for example, the following compounds from the preparation 
examples have a superior action compared to the prior art: 1 and 6 
TABLE A 
______________________________________ 
Root-systemic action 
Phaedon cochleariae Larvae 
Degree of destruction 
Active compound in % at an active compound 
(constitution) concentration in ppm 
______________________________________ 
##STR25## 2.5 ppm = 0% 
known 
##STR26## 2.5 ppm = 95% 
according to the invention 
##STR27## 2.5 ppm = 100% 
______________________________________ 
Example B 
Critical concentration test/soil insects 
Test insect: Phorbia antiqua grubs in the soil 
Solvent: 3 parts by weight of acetone 
Emulsifier: 1 part by weight alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent, the stated 
amount of emulsifier is added and the concentrate is diluted with water to 
the desired concentration. 
The preparation of active compound is intimately mixed with soil. The 
concentration of the active compound in the preparation is of practically 
no importance, only the amount by weight of active compound per unit 
volume of soil, which is given in ppm (=mg/liter) being decisive. The soil 
is filled into pots and the pots are left to stand at room temperature. 
After 24 hours, the test insects are introduced into the treated soil, and 
after a further 2 to 7 days the degree of effectiveness of the active 
compound is determined in % by counting the dead and live test insects. 
The degree of effectiveness is 100% if all the test insects have been 
killed and is 0% if just as many test insects are still alive as in the 
case of the untreated control. 
Active compounds, amounts applied and results can be seen in Table B: 
TABLE B 
______________________________________ 
Soil insecticides 
Phorbia antiqua maggots in the soil 
Degree of destruction 
Active compound at % in active compound 
(constitution) concentration in ppm 
______________________________________ 
##STR28## 20 ppm = 0% 
known 
##STR29## 20 ppm = 95% 
______________________________________ 
according to the invention 
It will be understood that the specification and examples are illustrative 
but not limitative of the present invention and that other embodiments 
within the spirit and scope of the invention will suggest themselves to 
those skilled in the art.