DE3638193A1 - Carbamoylated N-aminobarbituric acids, processes for their preparation, and their use as pesticides - Google Patents

Abstract

The present invention relates to novel carbamoylated N-aminobarbituric acids of the formula I <IMAGE> in which X and Y independently of one another represent 0 or 5, R<1> represents hydrogen, alkyl or aryl which can optionally be substituted, R<2> and R<3> independently of one another represent alkyl or aryl, each of which can optionally be substituted, or which, together with the adjacent nitrogen atom, form a saturated or unsaturated heterocycle which optionally contains further hetero atoms and which is optionally substituted, R<4> represents optionally substituted phenyl or alkyl, and processes for their preparation, and intermediates for carrying out these processes. The compounds of the formula I can be used in an outstanding manner as pesticides, in particular as endoparasiticides and ectoparasiticides in the field of veterinary medicine, but also as insecticides, acaricides and fungicides in the fields of agriculture and forestry, for domestic premises, in the hygiene field and in the field of the protection of stored products and materials.

Description

The present invention relates to new carbamoylated N-aminobarbituric acids, process for their preparation and their use as pesticides the areas of agriculture and forestry, household, hygiene, Storage and material protection as well as veterinary medicine.

Carbamoylated thiobarbituric acid derivatives are already known. They can be used to combat use animal-parasitic medicinal mints (EP-OS 1 67 491).

• 1. The new carbamoylated aminobarbituric acids of the formula I have been found in which
  X and Y independently of one another represent O or S,
  R¹ represents hydrogen, alkyl, aryl which may be substituted,
  R² and R³ independently of one another represent alkyl or aryl, which may optionally be substituted or which, together with the adjacent nitrogen atom, form a saturated or unsaturated heterocycle which optionally contains further heteroatoms and is optionally substituted,
  R⁴ represents optionally substituted phenyl or alkyl
  The compounds of the formula I can be present in the form of their various tautomers (keto / enol) and as mixtures of these tautomers, and in the form of their salts with bases.
• 2. It has been found that the compounds of the formula (I) in which
  X and Y independently of one another represent O or S,
  R¹ represents hydrogen, alkyl, aryl, which may optionally be substituted,
  R² and R³ independently of one another represent alkyl or aryl, which may optionally be substituted or which, together with the adjacent nitrogen atom, form a saturated or unsaturated heterocycle which optionally contains further heteroatoms and is optionally substituted,
  R⁴ represents optionally substituted phenyl or alkyl
  obtained by
  • a) Aminobarbituric acids of the formula II in which
    X, R¹, R², R³ have the meaning given above,
    with isocyanates of the formula III or primary carbamic acid chlorides of the formula IIIa in which
    Y and R⁴ have the meaning given above,
    implements, or
  • b) aminobarbituric acids of the formula II in which
    X, R¹, R², R³ have the meaning given above with compounds of the formula IV in which
    R⁴ has the meaning given above
    implements or
  • c) substituted aminobarbituric acids of the formula V in which
    X, R¹, R², R³ have the meaning given above,
    R⁵ is C _1-4 alkyl, phenyl which is optionally substituted by NO₂, with amines of the formula VIH₂N-R⁴ (VI) in which
    R⁴ has the meaning given above
    implements.
• 3. The new aminobarbituric acids of formula V were found in which
  X, R¹, R², R³, R⁵ have the meaning given under 2.
• 4. A process for the preparation of the aminobarbituric acids of the formula V has been found in which
  R¹, R², R³, R⁵ have the meaning given under 2,
  characterized in that aminobarbituric acids of the formula II in which
  X, R¹, R², R³ have the meaning given above,
  with chloroformate of formula VII in which
  R⁵ has the meaning given above
  in the presence of a base.

The compounds of formula I are excellent as a pesticide, in particular as an endoparasiticide and ectoparasiticides in the field of Veterinary medicine but also as insecticides, acaricides and fungicides in the fields of agriculture and forestry, Household, hygiene, storage and material protection deploy.  

Compounds of the formula I in which are preferred
X represents O or S, in particular O,
Y represents O or S, in particular O,
R¹ is hydrogen, C _1-6 alkyl, C _3-6 cycloalkyl, phenyl, which can optionally be substituted by one or more of the following radicals:
Alkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methyl, ethyl, n.- and i.-propyl and n.-, i.-, s.- and t.-butyl; Alkoxy preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n.- and i.-propyloxy and n.-, i.-, s.- and t.-butyloxy; Alkythio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n.- and i.-propylthio and n.-, i.-, s.- and t.-butylthio; Haloalkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, where the halogen atoms are identical or different and are halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl or fluorine -, chloroethyl; Haloalkoxy with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, the halogen atoms being identical or different and preferably being fluorine, chlorine, bromine, in particular fluorine, such as trifluoromethoxy; Haloalkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, the halogen atoms being the same or different and preferably being fluorine, chlorine, bromine, in particular fluorine, such as trifluoromethylthio; Alkylenedioxy with preferably 1 or 2 carbon atoms such as methylenedioxy or ethylenedioxy; halogen-substituted alkylenedioxy with preferably 1 or 2 carbon atoms and preferably 1 to 4, in particular 2 to 3 halogen atoms, where the halogen atoms are identical or different and are preferably fluorine or chlorine, in particular fluorine, such as difluoromethylene dioxy, trifluoroethylene dioxy, tetrafluoroethylene dioxy; Hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, especially chlorine and bromine; Cyano; Nitro; Amino; Monoalkyl- and dialkylamino with preferably 1 to 4, in particular 1 or 2 carbon atoms per alkyl group, such as methylamino, methylethylamino, n.- and i.-propylamino and methyl-n.-butylamino; Formyl; Carboxyl; Alkylcarbonyl preferably having 2-4 carbon atoms; Carbalkoxy preferably having 2 to 4, in particular 2 or 3, carbon atoms, such as carbomethoxy and carboethoxy; Sulfo (-SO₃H); Alkylsulfonyl preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methylsulfonyl and ethylsulfonyl; Arylsulfonyl preferably having 6 or 10 aryl carbon atoms, such as phenylsulfonyl; Phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, which in turn can be substituted.
R² represents C₁-C₄-alkyl, phenyl, benzyl, which may optionally be substituted by one of the radicals indicated above,
R³ represents C₁-C₄-alkyl, phenyl, benzyl, which may optionally be substituted,
R² and R³ together with the adjacent nitrogen atom represent a saturated heterocycle which optionally contains O or N as further heteroatoms and can optionally be substituted,
R⁴ represents straight-chain, branched or cyclic alkyl having up to 20 carbon atoms, which is optionally substituted by halogen, in particular chlorine, fluorine, bromine, C _1-4 alkoxy, in particular methoxy, ethoxy, and also represents phenyl, which is optionally substituted by alkyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n.- and i.-propyl and n.-, i.-, s.- and t.-butyl; Alkoxy preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n.- and i.-propyloxy and n.-, i.-, s.- and t.-butyloxy; Alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n.- and i.-propylthio and n.-, i.-, s.- and t.-butylthio; Haloalkyl with preferably 1 to 4, in particular 1 or 2, carbon atoms and preferably 1 to 5, in particular 1 to 3, halogen atoms, the halogen atoms being identical or different and preferably being fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl, fluorine, chloroethyl; Haloalkoxy with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, the halogen atoms being identical or different and preferably being fluorine, chlorine, bromine, in particular fluorine, such as trifluoromethoxy; Haloalkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, the halogen atoms being the same or different and preferably being fluorine, chlorine, bromine, in particular fluorine, such as trifluoromethylthio; Alkylenedioxy with preferably 1 or 2 carbon atoms such as methylenedioxy or ethylenedioxy; halogen-substituted alkylenedioxy with preferably 1 or 2 carbon atoms and preferably 1 to 4, in particular 2 to 3 halogen atoms, where the halogen atoms are identical or different and are preferably fluorine or chlorine, in particular fluorine, such as difluoromethylene dioxy, trifluoroethylene dioxy, tetrafluoroethylene dioxy; Hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, especially chlorine and bromine; Cyano; Nitro; Amino; Monoalkyl- and dialkylamino with preferably 1 to 4, in particular 1 or 2 carbon atoms per alkyl group, such as methylamino, methylethylamino, n.- and i.-propylamino and methyl-n.-butylamino; Formyl; Carboxyl; Alkylcarbonyl preferably having 2-4 carbon atoms; Carbalkoxy preferably having 2 to 4, in particular 2 or 3, carbon atoms, such as carbomethoxy and carboethoxy; Sulfo (-SO₃H); Alkylsulfonyl preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methylsulfonyl and ethylsulfonyl; Arylsulfonyl preferably having 6 or 10 aryl carbon atoms, such as phenylsulfonyl; Phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, pyridinoxy, which in turn can be substituted.
Compounds of the formula I in which are particularly preferred
X and Y stand for O,
R¹ is C _1-4 alkyl,
R² represents C _1-4 alkyl,
R³ is C _1-4 alkyl,
R² and R³ together with the adjacent nitrogen atom represent a 5- or 6-membered heterocycle which may contain O or N as further heteroatoms and optionally by C _1-4 -alkyl, C _1-4 -hydroxyalkyl, C _1-4 - Haloalkyl, C _1-4 -alkoxyalkyl is substituted,
R⁴ stands for phenyl, which is optionally substituted by C _1-4 alkyl, in particular methyl, C _1-4 alkoxy, in particular methoxy, ethoxy, C _1-4 haloalkoxy, in particular trifluoromethoxy, fluorochloroethoxy, C₁-C₄-haloalkylthio, especially trifluoromethylthio, fluorochloromethylthio, C₁-C₄-alkylthio, especially methylthio, halosulfonyl, especially fluorosulfonyl, chlorosulfonyl, C₁-C₄-alkylsulfonyl, especially methylsulfonyl, C₁-C₄-haloalkylsulfonyl, especially trifluoromethyl-halogeno-fluoronyl, C-C₄-alkyl₄, ₄ Ethylenedioxy, which are optionally substituted by fluorine or chlorine, halogen, in particular fluorine or chlorine, NO₂, phenoxy, pyridinoxy, which is optionally substituted by one of the radicals indicated above,
Compounds of the formula I in which are very particularly preferred
X and Y stand for O,
R¹ represents methyl,
R² and R³ represent methyl or ethyl or together with the adjacent nitrogen atom represent a pyrrolidine, piperidine or morpholine ring which is optionally substituted by methyl, ethyl, hydroxyethyl.
R⁴ represents phenyl, which is optionally substituted by halogen, in particular chlorine, NO₂, CF₃, OCF₃, SO₂F, SCF₃, SCF₂Cl, SOCF₃, SO₂CF₃, OCH₃, OCF₂CF₂H, phenoxy and pyridinoxy, which is substituted by trifluoromethyl, fluorine-chlorine-substituted Ethylenedioxy, methyl, ethyl.

In particular, the following compounds of formula I are called, in which X and Y is O and R¹ for Methyl is and R², R³, R⁴ have the following meanings to have:

1-dimethylamino-3-methyl-5-methylcarbamoyl barbituric acid, 1-dimethylamino-3-methyl-5- (4-chlorophenyl) carbamoyl barbituric acid, 1-dimethylamino-3-methyl-5- (4- (3'-trifluoromethylphenoxy ) -phenyl) -carbamoylbarbituric acid, 1-piperidino-3-methyl-5-cyclohexylcarbamoylbarbituric acid, 1-piperidino-3-ethyl-5- (4-trifluoromethylphenyl) carbamoylbarbituric acid, 1-piperidino-3-methyl-5- (4- bromphenyl) thio-carbamoylbarbituric acid, 1-piperidino-3-phenyl-5- (4- (4'-trifluoromethylphenoxy) phenyl) carbamoylbarbituric acid, 1-morpholino-3-methyl-5-s.-butyl-carbamoylbarbituric acid, 1 -Morpholino-3-i.-propyl- 5- (4-trifluoromethoxyphenyl) carbamoylbarbituric acid, 1-morpholino-3-methyl-5- (4- (3'-trifluoromethylphenoxy) phenyl) carbamoylbarbituric acid, 1-morpholino-3 -ethyl-5- (4-chlorophenyl) carbamoyl barbituric acid, 1- (N-methyl, N-phenyl) amino-3-methyl-5- (3,4-dichlorophenyl) carbamoyl barbituric acid, -1-dimethylamino-3- ethyl 5- (4- (3'-trifluoromethylphenoxy) phenyl) carbamoyl barbituric acid, 1-pyrrolidino-3-methyl-5- (4-trifluo rmethylphenyl) - carbamoylthiobarbituric acid, 1-dimethylamino-3-methyl-5- (4- (5'-trifluoromethyl-2'-pyridinoxy) phenyl) carbamoyl barbituric acid.

As bases with which the compounds of formula I can form salts, mention may be made of: alkali and alkaline earth metal hydroxides, ammonia, primary, secondary and tertiary amines. The following bases are particularly preferred:
Triethylamine, isopropylamine, t-butylamine, pyridine, picoline, trimethylamine, diisopropylamine, morpholine, pyrrolidine, hexamethyleneimine, piperazine, N-methylpiperazine.

If method 2 a is used to produce the new one carbamoylated N-aminobarbituric acids as a compound of Formula II 1-dimethylamino-3-methyl-barbituric acid and as Compound of formula III p-bromophenyl isocyanate, so the method can be represented by the following formula reproduced:

Compounds of the formula II are preferably used in which the substituents X, R 1, R 2, R 3 have the preferred and particularly preferred meanings given for the compounds of the formula I. The following compounds of the formula II may be mentioned in particular:
1-dimethylamino-3-methyl-barbituric acid, 1-dimethylamino-3-i-propyl-barbituric acid, 1-pyrrolidino-3-methyl-barbituric acid, 1-piperidino-3-methyl-barbituric acid, 1-morpholino-3-ethyl -barbituric acid, 1-diethylamino-3-ethyl-barbituric acid, 1-morpholino-3-methyl-thio-barbituric acid, 1-piperidino-3-ethyl-thiobarbituric acid, 1-dimethylamino-3-n-butyl-thiobarbituric acid.

Compounds of formula II are known or can be Manufacture analogously to known processes (cf. Kazmirowski et al J. Prakt. Chem (4) 26 (1964) pp. 101-112).

Isocyanates of the formula III are preferably used, in which the substituent
R⁴ represents straight-chain, branched or cyclic alkyl having up to 20 carbon atoms, which is optionally substituted by halogen, in particular chlorine, fluorine, bromine, C _1-4 alkoxy, in particular methoxy, ethoxy, and also represents phenyl, which is optionally substituted by alkyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n.- and i.-propyl and n.-, i.-s.- and t.-butyl; Alkoxy preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n.- and i.-propyloxy and n.-, i.- s.- and t.-butyloxy; Alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n.- and i.-propylthio and n.-, i.- s.- and t.-butylthio; Haloalkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, where the halogen atoms are identical or different and are halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl or fluorine -, chloroethyl; Haloalkoxy with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, the halogen atoms being identical or different and preferably being fluorine, chlorine, bromine, in particular fluorine, such as trifluoromethoxy; Haloalkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, the halogen atoms being the same or different and preferably being fluorine, chlorine, bromine, in particular fluorine, such as trifluoromethylthio; Alkylenedioxy with preferably 1 or 2 carbon atoms such as methylenedioxy or ethylenedioxy; halogen-substituted alkylenedioxy with preferably 1 or 2 carbon atoms and preferably 1 to 4, in particular 2 to 3 halogen atoms, where the halogen atoms are identical or different and are preferably fluorine or chlorine, in particular fluorine, such as difluoromethylene dioxy, trifluoroethylene dioxy, tetrafluoroethylene dioxy; Hydroxy; Halogen, preferably fluorine, chlorine, bromine or iodine, especially chlorine and bromine; Cyano; Nitro; Amino; Monoalkyl- and dialkylamino with preferably 1 to 4, in particular 1 or 2 carbon atoms per alkyl group, such as methylamino, methyl-ethyl-amino, n.- and i.-propylamino and methyl-n.-butylamino; Formyl; Carboxyl; Alkylcarbonyl preferably having 2-4 carbon atoms; Carbalkoxy preferably having 2 to 4, in particular 2 or 3, carbon atoms, such as carbomethoxy and carboethoxy; Sulfo (-SO₃H); Alkylsulfonyl preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methylsulfonyl and ethylsulfonyl; Arylsulfonyl preferably having 6 or 10 aryl carbon atoms, such as phenylsulfonyl; Phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, pyridinoxy, which in turn can be substituted.

Instead of the isocyanates, the corresponding ones can also be used primary carbamic acid chlorides of the formula IIIa used will.

Compounds of formulas II and III are in the presence of diluents and in the presence of bases as well optionally implemented in the presence of further catalysts.  

The following may be mentioned as bases: alkali, alkaline earth alcoholates and tertiary amines. The following are particularly preferred Called bases: triethylamine, pyridine, picoline, trimethylamine, N-methylmorpholine, N-ethylpyrrolidine, diazabicyclo (4,3,0) - undecene (DBU), 1,4-diaza-bicyclo-2,2,2- octane (DABCO), diazabicyclo (3,2,0) nonen (DBN).

All inert organic come as diluents Solvent in question. These include in particular aliphatic and aromatic, optionally halogenated Hydrocarbons, such as pentane, hexane, heptane, cyclohexane, Petroleum ether, petrol, ligroin, benzene, toluene, Methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, Chlorobenzene and o-dichlorobenzene, further Ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, furthermore ketones, such as acetone, methylethyl, methylisopropyl and methyl isobutyl ketone, also esters, such as Methyl acetate and ethyl acetate, also nitriles, such as B. acetonitrile and propionitrile, benzonitrile, Glutaronitrile, in addition amides, such as. B. Dimethylformamide, dimethylacetamide and N-methylpyrrolidone, as well as dimethyl sulfoxide, tetramethylene sulfone and Hexamethylphosphoric triamide.

The catalysts that come in reactions with isocyanates usual catalysts in question. As such called: metal catalysts of Zn, Sn, Pb such as dibutyltin dilaurate, Dibutyltin dioxide, tin octoate, lead octoate, Zinc octoate, zinc chloride, zinc acetate.  

The reaction is between 0 and 150 ° C, preferably between 20-50 ° C carried out. One prefers to work under normal pressure.

The compounds of formulas II and III are in equimolar amounts used, an excess of some or other component brings no significant advantages.

Processing takes place in a manner known per se, e.g. B. by adding dilute to the reaction mixture Acid, filter off the product or separate the organic phase and distilling off the solvent.

Is used in process 2b as compounds of the formula II (1- (N-methylanilino) -3-ethyl-barbituric acid and as Compound of formula IV benzoylazide, so Represent procedure 2b using the following formula:

In method 2b, the compounds of Formula II used in which the radicals X, R¹, R², R³ the preferred in the compounds of formula I mentioned and have particularly preferred meanings. Compounds of the formula IV are preferably used in which R⁴ mentioned in the compounds of formula I. preferred and particularly preferred meanings owns. Compounds of formula IV are known or can be produced analogously to known processes (see file, Chemistry of the Acido Groups Interscience Publishers New York pp. 503-554 (1971)).

Process 2b is carried out at temperatures of 50-200 ° C preferably carried out between 70 and 180 ° C. It will worked at normal pressure. They come as solvents in the case of solvents 2a mentioned. The Starting compounds are in an equimolar ratio used to each other. An excess of one or the other other component has no advantages. It can be in In the presence of a base. As such the usual inorganic or organic bases such as e.g. B. alkali or alkaline earth metal hydroxides, carbonates, -hydrogen carbonates, -alcoholates, furthermore amines such as in particular tertiary amines, e.g. B. trimethylamine, triethylamine as well as heterocyclic bases such as pyridine.

Is used in method 2 c as a compound of the formula V 1-methylethylamino-3-ethyl-5-carbethoxy-barbituric acid and as an amine of the formula VI, N-methyl-4-chloroaniline, the method can be described by the following formula represent:  

Compounds of formula V are new. Your manufacture is described below. The compounds are preferred of the formula V, in which X, R¹, R² and R³, which at the compounds of formula I as preferred and special preferably have meanings mentioned, and at which R⁵ is methyl, ethyl, p-nitrophenyl.

The amines of formula VI are known or can be produce analogous to known methods.

Amines of the formula VI are preferably used, in which the substituent R⁴ in the compounds of the formula I mentioned preferred and particularly preferred Has meanings.  

The following compounds of the formula VI may be mentioned in detail:
4-nitroaniline, 3-chloro-4-trifluoromethylaniline, 3-trifluoromethyl- 4-chloroaniline, 4-trifluoromethoxy aniline, 4-trifluoromethylmercaptoaniline, 3-chloro-4-trifluoromethoxy aniline, 3-chloro-4-trifluoromethylmercaptoaniline, 4-trifluoromethylaniline, trifluoromethyl-4-aminophenylsulfone, 4- (1,1,2,2-tetrafluoroethoxy) aniline, 2,6-dichloro-4-trifluoromethylmercapto-aniline, 4-amino-4'-trifluoromethyl-diphenyl ether, 4 -Amino-3'-trifluoromethyl diphenyl ether; 2- (4-aminophenoxy) -S-trifluoromethyl-pyridine.

The compounds of the formulas V and VI are reacted preferably in the presence of diluents as well as in the presence of bases.

All inert organic come as diluents Solvent in question. These include in particular aliphatic and aromatic, optionally halogenated Hydrocarbons, such as pentane, hexane, heptane, cyclohexane, Petroleum ether, petrol, ligroin, benzene, toluene, Methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, Chlorobenzene and o-dichlorobenzene, further Ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, furthermore ketones, such as acetone, methylethyl, methylisopropyl and methyl isobutyl ketone, also esters, such as Methyl acetate and ethyl acetate, also nitriles, such as B. acetonitrile and propionitrile, benzonitrile, Glutaronitrile, in addition amides, such as. B.  Dimethylformamide, dimethylacetamide and N-methylpyrrolidone, as well as dimethyl sulfoxide, tetramethylene sulfone and Hexamethylphosphorsäuretriamid, further alcohols such as Methanol, ethanol, propanol, butanol.

Alkali and alkaline earth metal hydroxides are particularly mentioned as bases, Alkali and alkaline earth alcoholates, in particular Sodium methylate or ethylate.

The reaction is preferred between 50 and 150 ° C performed between 60-110 ° C. One prefers to work under normal pressure.

The compounds of formulas V and VI are in equimolar Amounts used a small excess of one or other component brings no significant advantages.

Processing takes place in a manner known per se, e.g. B. by adding water to the reaction mixture, Separate the organic phase and distill off the Solvent.

Aminobarbituric acids of formula V are new. Prefers are aminobarbituric acids of formula V in which the substituents X, R¹, R² and R³ which in the compounds of Formula I have preferred meaning given and R⁵ has the meaning given under 3 (above). To their Production of barbituric acids of formula II with Chloroformic acid esters optionally in the presence of Diluents implemented in the presence of bases.  

The reaction takes place at temperatures of -50-50 ° C, preferably at 0 ° -30 ° C, particularly preferably at room temperature.

All inert organic come as diluents Solvent in question. These include in particular aliphatic and aromatic, optionally halogenated Hydrocarbons, such as pentane, hexane, heptane, cyclohexane, Petroleum ether, petrol, ligroin, benzene, toluene, Methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, Chlorobenzene and o-dichlorobenzene, further Ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, furthermore ketones, such as acetone, methylethyl, methylisopropyl and methyl isobutyl ketone, also esters, such as Methyl acetate and ethyl acetate, also nitriles, such as B. acetonitrile and propionitrile, benzonitrile, Glutaronitrile, in addition amides, such as. B. Dimethylformamide, dimethylacetamide and N-methylpyrrolidone, as well as dimethyl sulfoxide, tetramethylene sulfone and Hexamethylphosphoric triamide.

Inorganic and organic bases come as bases in question. Alkali and alkaline earth metal hydroxides are mentioned as bases, -carbonates, -hydrogencarbonates, -alcoholates, furthermore amines such as, in particular, tertiary amines, e.g. B. trimethylamine, Triethylamine, N-methylmorpholine, pyridine, Picoline, N-ethylpyrrolidine, diazabicyclo (4,3,0) -undecane (DBU), 1,4-diazabicyclo (2,2,2) octane (DABCO), Diazabicyclo (3,2,0) nonen (DBN).  

The reaction can also be carried out in a suitable solvent Base carried out without further solvents will.

The active substances are suitable for combating animal pests, especially insects, arachnids, nematodes, trematodes and cestodes that are found in agriculture, in the areas of household, hygiene, protection of stocks, materials and forestry, as well as in animal husbandry, with favorable toxicity to warm-blooded animals. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:
From the order of the Isopoda z. B. Oniscus asellus, Armadillium vulgare, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus.
From the order of the Chilopoda z. B. Geophilus carpopha gus, Scutigera spec.
From the order of the Symphyla z. B. Scutigerella immaculata.
From the order of the Thysanura z. B. Lepisma saccharina.
From the order of the Collembola z. B. Onychiurus armatus.
From the order of the Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Reticulitermes spp.
From the order of the Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.
From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.
From the order of the Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodaliphasumum bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.
From the order of the Lepidoptera z. B. 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 sppi, Trichoplapsia n., Trichoplusia n. , Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnidana, Homona magnidanana.
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajalus, 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 assimppis, Troest. Antagen spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis Costelytra zealandica.
From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera z. B. Aedes spp. Anopheles spp., Culex spp., Simulium spp., Drosophila melanogaster, Musca spp., Lyperosia spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca Stomoxys spp., Melophagus spp., Oestrus spp., Hypoderma spp., Dermatobia, Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paleae
From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp. Ctenocephalides spp., Echidnophaga spp.
From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.
From the order of Acarina z. B. Acarus siro, Argas spp., Otobius spec., Ornithodoros spp., Dermanyssus gallinae, Bdellonyssus spp., Eriophyes ribis, Phyllocoptruta oleivovra, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalxodes spp. Haemaphysalis spp., Dermacentor spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Demodex spp., Psorergates spp., Myobia spp., Myocoptes spp., Notoedres spp., Octodectes spp., Varroa spp., Tarsonem ., Bryobia praetiosa, Panonychus spp., Tetranychus spp.
From the order of the Pseudophyllidea z. E.g .: Diphyllobothrium spp., Spirometra spp., Schistocephalus spp., Ligula spp., Bothridium spp., Diplogonoporus spp.
From the order of the Cyclophyllidea z. For example: Mesocestodes spp., Anoplocephala spp., Paranoplocephala spp., Monieazaia spp., Thysanosoma spp., Thysaniezia spp., Avitellina spp., Stilesia spp., Cittotaenia spp., Andyra spp., Bertiella spp., Taenia spp. , Echinococcus spp., Hydatigera spp., Davainea spp., Raillietina spp., Hymenolepsis spp., Echinolepsis spp., Echinocotyle spp., Diochis spp., Dipylidium spp., Joyeuxiella spp., Diplopylidium spp.
From the subclass of Monogenea z. For example: Gyrodactylus spp., Dactylogyrus spp., Polystoma spp.
From the subclass of Digenea z. For example: Diplostomum spp., Posthodiplostomum spp., Schistosoma spp., Trichobilharzia spp., Ornithobilharzia spp., Austrobilharzia spp., Gigantobilharzia spp., Leucochloridium spp., Brachylaima spp.,
Echinostoma spp., Echinoparyphium spp., Echinochasmus spp., Hypoderaeum spp., Fasciola spp., Fasciolides spp., Fasciolopsis spp., Cyclocoelum spp., Typhlocoelum spp., Paramphistomum spp., Calicopotyl spphor., Calicopotyl spp ., Fischoederius spp., Gastrothylacus spp., Notocotylus spp., Catatropis spp., Plagiorchis spp., Prosthogonimus spp., Dicrocoelium spp., Eurytrema spp., Troglotrema spp., Paragonimus spp., Collyriclyetpp. Opisthorchis spp., Clonorchis spp., Metorchis spp., Heterophyes spp., Metagonimus spp.
From the order of the Enoplida z. For example: Trichuris spp., Capillaria spp., Trichomosoides spp., Trichinella spp.
From the order of the Rhabditida z. B. Micronema spp. Strongyloides spp.
From the order of Strongylida z. E.g .: Strongylus spp., Triodontophorus spp., Oesophagodontus spp., Trichonema spp., Gyalocephalus spp., Cylindropharynx spp., Poteriostomum spp., Cyclicocerus spp., Cylicostephanus spp., Oesophagostomia spp., Chab. , Ancylostoma spp., Uncinaria spp., Bunostomum spp., Globocephalus spp., Syngamus spp., Cyathostoma spp., Metastrongylus spp., Dictyocaulus spp., Muellerius spp., Protostrongylus spp., Neostrongylus., spp., Spicocaulus spp., Elaphostrongylus spp., Parelaphostrongylus spp., Crenosoma spp., Paracrenosoma spp., Angiostrongylus spp., Aelurostrongylus spp., Filaroides spp., Parafilaroides spp., Trichostia. spp., Trichostrong. , Marshallagia spp., Cooperia spp., Nematodirus spp., Hyostrongylus spp., Obeliscoides spp., Amidostomum spp., Ollulanus spp. .
From the order of the Oxyurida z. For example: Oxyuris spp., Enterobius spp., Passalurus spp., Syphacia spp., Aspiculuris spp., Heterakis spp.
From the order of the Ascaridida z. For example: Ascaris spp., Toxascaris spp., Toxocara spp., Parascaris spp., Anisakis spp., Ascaridia spp.
From the order of the Spirurida z. E.g .: Gnathostoma spp., Physaloptera spp., Thelazia spp., Gongylonema spp., Habronema spp., Parabronema spp., Draschia spp., Dracunculus spp.
From the order of the Filariida z. For example: Stephanofilaria spp., Parafilaria spp., Setaria spp., Loa spp., Dirofilaria spp., Litomosoides spp., Brugia spp., Wuchereria spp., Onchocerca spp.
From the order of the Gigantorhynchida z. For example: Filicollis spp., Moniliformis spp., Macracanthorhynchus spp., Prosthenorchis spp.

The active ingredients also have fungicidal properties especially against plant pathogenic fungi such as. B. Pyricularia oryzae in rice, Botrytis cinerea and Venturia mushrooms. They are systematically effective.

The active ingredients can be in the usual formulations are transferred, such as solutions, emulsions, Suspensions, powders, foams, pastes, granules, Aerosols, active ingredient-impregnated natural and synthetic Substances, fine encapsulation in polymeric substances and in coating compositions for seeds, also in formulations with Fuel sets, such as smoking cartridges, cans, spirals and. Ä., and ULV cold and warm fog formulations.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with Extenders, i.e. liquid solvents, under Pressurized liquefied gases and / or solid Carriers, optionally using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam generators Means. In case of using water as Extenders can e.g. B. also organic solvents can be used as auxiliary solvents. As a liquid Solvents are essentially possible: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated Aromatics or chlorinated aliphatic hydrocarbons,  such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, such as Butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers are meant such liquids, which in normal Temperature and under normal pressure are gaseous, for. B. Aerosol propellant, such as halogenated hydrocarbons as well Butane, propane, nitrogen and carbon dioxide; as fixed Carriers come into question: z. B. natural stone powder, such as kaolins, clays, talc, chalk, quartz, Attapulgite, montmorillonite or diatomaceous earth and synthetic Rock powder, such as highly disperse silica, Alumina and silicates; as solid carriers for Granules are possible; e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules inorganic and organic flours and granules organic material such as sawdust, coconut shells, Corn cobs and tobacco stalks; as an emulsifier and / or Foaming agents are possible: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene Fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, Aryl sulfonates and protein hydrolyzates; as a dispersant come into question: z. B. lignin sulfite and Methyl cellulose.  

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, Boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be in their commercially available Wording as well as in the from these Formulations prepared mixed use forms with other active ingredients, such as insecticides. Insecticides include, for example, phosphoric acid esters, Carbamates, carboxylic acid esters, chlorinated hydrocarbons, Phenylureas, through microorganisms manufactured fabrics u. a.

The active compounds according to the invention can also be used in their commercial formulations and in the from these Formulations prepared mixed use forms  with synergists. Synergists are connections which increases the effectiveness of the active ingredients becomes active without the added synergist itself must be effective.

The application takes place in one of the application forms adapted usual way.

The active compounds according to the invention are also suitable for Combat arthropods, agricultural Farm animals, such as B. cattle, sheep, goats, horses, Pigs, donkeys, camels, buffalos, rabbits, chickens, Turkeys, ducks, geese, bees, other pets such as B. Dogs, cats, house birds, aquarium fish and so-called. Laboratory animals, such as B. hamsters, guinea pigs, rats and infest mice, after all they are also suitable for Treatment of human pathogenic arthropods.

The active compounds according to the invention can be used to combat them such arthropods both prophylactically and can be used therapeutically. By fighting These arthropods are said to cause deaths and reduced performance (for meat, milk, wool, skins, eggs, etc.) can be reduced, so that by using the Active ingredients according to the invention a more economical Animal husbandry is possible.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral Administration in the form of, for example, tablets, capsules, Watering, drenching, granules, pastes, boluses, des  feed-through procedure, from suppositories, through parenteral Administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal u. a.), implants, by nasal application, by dermal Application in the form of, for example, diving or Bathing (dipping), spraying (spray), pouring (pour-on and spot-on), washing, powdering and with With the help of shaped articles containing active ingredients, such as collars, Ear tags, tail tags, limb bands, holsters, Marking devices etc.

The active compounds according to the invention are broadly effective against endoparasites such as nematodes, cestodes and Trematodes. They mainly work against nematodes, especially ruminant gastric and intestinal nematodes. In addition, they also act against such gastric and Intestinal nematodes that counter the common benzimidazole Anthelmintics resistant and therefore no longer are sufficiently treatable.

The effect was in animal experiments after oral, parenteral and dermal application for strong parasites infected test animals. The dosages used were tolerated very well by the experimental animals.

The active compounds according to the invention can be used as anthelmintics in both human and veterinary medicine be used.

The active compounds according to the invention can be used together with other common anthelmintics.  

The active compounds according to the invention can either be used as such or in combination with pharmaceutically acceptable Carriers are used. As dosage forms in combination with various inert substances Carriers come tablets, capsules, granules, aqueous Suspensions, injectable solutions, emulsions and Suspensions, elixirs, syrups, pastes and the like into consideration. Such carriers include solid diluents or fillers, a sterile, aqueous Medium as well as various non-toxic organic Solvents and the like. Of course you can that are considered for oral administration Tablets and the like with added sweeteners and the like be provided. The therapeutically effective compound should be in a concentration in the aforementioned case from about 0.5 to 90% by weight of the total mixture is present be d. H. in amounts sufficient to meet the above To achieve dosage scope.

The formulations are prepared in a known manner e.g. B. by stretching the active ingredients with Solvents and / or carriers, if appropriate using emulsifiers and / or dispersants, where z. B. in the case of the use of water optionally organic solvents as diluents can be used as auxiliary solvents.

Examples of auxiliary substances are: Water, non-toxic organic solvents such as Paraffins (e.g. petroleum fractions), vegetable oils (e.g.  Peanut oil, sesame oil), alcohols (e.g. ethyl alcohol, glycerin), Glycols (e.g. propylene glycol, polyethylene glycol); solid carriers, such as. B. natural stone powder (e.g. kaolins, clays, talc, chalk) synthetic Rock powder (e.g. highly disperse silica, silicates), Sugar (e.g. cane, milk and dextrose); Emulsifiers, such as non-ionic and anionic emulsifiers e.g. B. polyoxyethylene fatty acid esters, polyoxyethylene Fatty alcohol ethers, alkyl sulfonates and aryl sulfonates), Dispersant (e.g. methyl cellulose, starch and polyvinylpyrrolidone) and lubricants (e.g. magnesium stearate, Talc, stearic acid and sodium lauryl sulfate).

In the case of oral use, tablets can of course be taken in addition to the carriers mentioned, also additives such as sodium citrate, calcium carbonate and dicalcium phosphate, together with various additives, such as starch, preferably potato starch, gelatin and the like. Lubricants, such as magnesium stearate, sodium lauryl sulfate and talc, can also be used for tableting.

In the case of aqueous suspensions and / or elixirs, the The active ingredients can be used for oral use except with the above additives various flavor enhancers or colorants be transferred.

In the case of parenteral use, solutions can be found Dragees, ampoules, etc., also in the form of dosage units  be adjusted with each dosage unit is that they are a single dose of the active ingredient delivers.

The active compounds according to the invention can be used in the formulations also in mixtures with others in the veterinary and / or human medicine for the treatment of infections and / or diseases use known active ingredients are present, in particular L-2,3,5,6-tetrahydro-6-phenyl- imidazothiazole, benzimidazole carbamates, praziquantel, Febantel.

The active substances can be used in the usual way. The application is preferably oral, one parenteral, especially subcutaneous, but also one dermal applications (pour-on-spot-on) are possible.

In general, it has proven to be advantageous Amounts from about 1 to about 100 mg of the active ingredients per kg Body weight per day for effective results to administer.

Nevertheless, it may be necessary from deviate from the amounts mentioned, depending on the body weight of the test animal or the type the route of application, but also due to the animal species and their individual behavior towards the drug or the type of its formulation and the Time or interval at which the administration he follows. So in some cases it may be sufficient  to make do with less than the aforementioned minimum quantity, while in other cases the upper limit mentioned must be exceeded. In the case of the application larger quantities it may be advisable to put these in to distribute several individual doses throughout the day.  

Example A In vitro nematode test Caenorhabditis elegans

The active ingredient is in water or dimethyl sulfoxide (DMSO) dissolved and with water to the desired concentration diluted. 0.01 ml of this solution was added to a Given replica plate. 2 ml of an E. coli Suspension added to which 10-20 female animals or larvae of Caenorhabditis elegans in 0.5 ml sterile M9 has given buffer solution. The E. Coli suspension was made by mixing 300 ml of an overnight culture Uracil-needy E. coli strain with 1.8 l sterile M9 Buffer solution added.

The test batch was incubated at 22 ° C. for 7 days and then evaluated. The extent to which the Active substance affects reproduction and concentration stated in µg per ml at which the propagation is prevented to 95% (minimum effective dose). Here the following results were obtained:  

Active ingredient Minimum effective dose Example No.µg / ml 110 210 310 410 510 610 710 810 91 1010 1110 12100 131 1410 1510 1710 1810 1910 201 2210 231  

Example B In vivo nematode test Strongyloides ratti

Rats experimentally infected with Strongyloides ratti are seven days after infection on three consecutive Days orally treated with a throat tube. The Animals are killed 13 days after infection and the Number of parasites determined. It becomes the drug concentration specified at least 95% of the Parasites were killed (minimum effective dose):

Minimum effective dose of active ingredient Example Nr.mg/kg

710 1425 1525 1625 2210  

Example C In vivo nematode test Nematospiroides dubius

Experimentally infected with Nematospiroides dubius Mice were given four consecutive 10 days after infection Days orally treated with a throat tube. The animals are sacrificed 19 days after infection and determined the number of parasites. It becomes the drug concentration given at least 95% the parasites were killed (effective dose):

Drug effective dose Example Nr.mg/kg 350 910  

Example D In vivo nematode test Heterakis spumosa

Mice experimentally infected with Heterakis spumosa were on 32 consecutive 32 days after infection Days orally treated with a throat tube. The Animals are killed 39 days after infection and the Number of parasites determined. It becomes the drug concentration indicated at least 95% of the parasites were killed (effective dose):

Drug effective dose Example Nr.mg/kg 110 25th 35 510 610 75 82.5 910 125 1510 1610 202.5 225  

Example E Phaedon larval test

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the desired one Concentration.

Cabbage leaves (Brassica oleracea) are made by diving in the active ingredient preparation of the desired concentration treated and with horseradish leaf beetle larvae (Phaedon cochleariae) occupied while the leaves are still moist are.

After the desired time, the kill is determined in%. 100% means that all beetle larvae are killed were; 0% means that no beetle larvae were killed.

The following compounds of the examples show an effect of 100% at 0.01%.
1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 12, 15, 16, 17, 18, 19, 21, 22, 23.

Example F

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent and the specified amount Emulsifier and dilute the concentrate with water on the desired concentrations.

The aqueous active substance preparations are filled into glasses and then sets 20 mosquito larvae of the 4th larval stage (Aedes aegypti) in each glass.

After the desired time, the kill is determined in%. 100% means that all animals are killed were; 0% means that no animals have been killed.

In this test, e.g. B. the following compounds of the manufacturing examples in a concentration of 0.001% a 100% effect: 1, 2, 3, 4, 5, 6, 7, 8, 12, 14, 15, 16, 18, 19, 20, 21, 22, 23.

Examples

• a) General instructions for the preparation of the compounds of formula I according to method 2a.
  In each case 0.03 mol of compound II and of the isocyanate (III) are placed in 120 ml of dry TMF and a solution of 0.033 mol of "DBU" in 30 ml of THF is added at room temperature within 10 minutes. There is a slight build-up of heat. It is then stirred at reflux until conversion is complete (approx. 4-5 h), cooled and the entire batch is stirred into 400 ml of 10% hydrochloric acid. The solid which separates out is filtered off with suction, washed with water and dried.
• General instructions for making the connections of formula I according to method 2b. 0.05 moles of compound II and 0.05 moles of "DBU" are placed in 100 ml of toluene and at room temperature 0.05 mol of an azide (dissolved in 100 ml Toluene) was added dropwise in 10 min. Then at reflux temperature stirred until no nitrogen more escapes and the entire batch in 300 ml 10% hydrochloric acid stirred in. The separating one Solid is suctioned off, washed with water and dried.  
• c) General instructions for the preparation of the compounds of formula I according to method 2c.
  0.03 mol of the substituted aminobarbituric acid of the formula V and 0.03 mol of the amine of the formula VI are suspended in 100 ml of toluene and heated to the reflux temperature under nitrogen for about 10 hours, ethanol escaping. The reaction mixture is cooled and the solid is filtered off. The filtered product is washed with ethanol and then dried.

According to one of the above-mentioned processes a) -c) get the compounds of the following table:  

General instructions for making the connections Formula V

0.05 mol of aminobarbituric acid of the formula II are in 100 ml of chloroform dissolved, mixed with 0.06 mol of pyridine and cooled to 5 ° C. Then 0.06 mol of ethyl chloroformate dripped. The mixture is at 12 h 5 ° C stirred, warmed to room temperature and twice with Washed 500 ml of water. The organic phase is over Na₂SO₄ dried and then the solvent distilled off.

Claims (8)

1. Carbamoylated aminobarbituric acids of the formula I. in which
X and Y independently of one another represent O or S,
R¹ represents hydrogen, alkyl, aryl, which may optionally be substituted,
R² and R³ independently of one another represent alkyl or aryl, which may optionally be substituted or which together with the adjacent nitrogen atom form a saturated or unsaturated heterocycle which optionally contains further heteroatoms and is optionally substituted,
R⁴ represents optionally substituted phenyl or alkyl
The compounds of the formula I can be present in the form of their various tautomers (keto / enol) and as mixtures of these tautomers, and in the form of their salts with bases. 2. Process for the preparation of the compounds of formula I. in which
X and Y independently of one another represent O or S,
R¹ represents hydrogen, alkyl, aryl, which may optionally be substituted,
R² and R³ independently of one another represent alkyl or aryl, which may optionally be substituted or which together with the adjacent nitrogen atom form a saturated or unsaturated heterocycle which optionally contains further heteroatoms and is optionally substituted.
R⁴ represents optionally substituted phenyl or alkyl
obtained by

• a) Aminobarbituric acids of the formula II in which
  X, R¹, R², R³ have the meaning given above,
  with isocyanates of the formula III or primary carbamic acid chlorides of the formula IIIa in which
  Y and R⁴ have the meaning given above,
  implements, or
• b) aminobarbituric acids of the formula II in which
  X, R¹, R², R³ have the meaning given above with compounds of the formula IV in which
  R⁴ has the meaning given above
  implements or
• c) substituted aminobarbituric acids of the formula V in which
  X, R¹, R², R³ have the meaning given above,
  R⁵ is C _1-4 alkyl, phenyl which is optionally substituted by NO₂,
  with amines of the formula VIH₂N-R⁴ (VI) in which
  R⁴ has the meaning given above
  implements.

3. Aminobarbituric acids of formula V in which
X, R¹, R², R³, R⁵ have the meaning given in claim 2. 4. Process for the preparation of the aminobarbituric acids of the formula V in which
R¹, R², R³, R⁵ have the meaning given in claim 2,
characterized in that aminobarbituric acids of the formula II in which
X, R¹, R², R³ have the meaning given above,
with chloroformate of formula VII in which
R⁵ has the meaning given above
in the presence of a base. 5. Pest control, characterized by contains at least one carbamoylated N-aminobarbituric acid of formula (I), according to claim 1. 6. Use of carbamoylated N-aminobarbituric acids of formula (I) according to claim 1 for combating of pests. 7. method of manufacturing pesticides, characterized in that one carbamoylated N-aminobarbituric acids of the formula (I) according to claim 1 with extenders and / or surface-active Means mixed. 8. Use of carbamoylated N-aminobarbituric acids of formula I for the manufacture of pesticides.