JPS638106B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides novel 2-cyclopropylamino-4-
The present invention relates to a formamidino-6-amino-s-triazine derivative, a method for producing the same, and a composition for controlling pests containing the same. The 2-cyclopropylamino-4-formamidino-6-amino-s-triazine derivative of the present invention has the following formula: (In the formula, R ₁ is a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms substituted with a lower alkoxy group, an alkenyl group having 3 to 4 carbon atoms, a carbon represents an alkynyl group or cyclopropyl group having 3 to 4 atoms, R ₂ represents a hydrogen atom, a methyl group or an ethyl group, or R ₁ and R ₂ are combined with the nitrogen atom to which they are bonded; , morpholinyl group, pyrrolidinyl group, and imidazolyl group, R ₃ represents a methyl group or ethyl group, R ₄ represents a methyl group or ethyl group, and R ₅ represents a hydrogen atom). The alkyl group represented by R ₁ can be straight-chain or branched and can be unsubstituted or substituted, for example by a C 1 -C 4 lower alkoxy group. Examples of such alkyl groups are methyl, ethyl, n-
These are propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and 2-methoxyethyl groups. Examples of C3 -C4 alkenyl and C3 -C4 alkynyl for R ₁ are allyl and propargyl, respectively. Preferable compounds for this action include, in the formula, R ₁ is a hydrogen atom, an unsubstituted C1-C4 alkyl group, a C1-C4 alkyl group substituted with a lower alkoxy group, a C1-C4 alkyl group substituted with a lower alkoxy group, a C3 represents an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, a cyclopropyl group,
R ₂ represents a hydrogen atom, a methyl group or an ethyl group, or R ₁ and R ₂ together with the nitrogen atom to which they are bonded represent a 1-pyrrolidinyl group, 4
- represents a morpholinyl group or a 1-imidazolyl group, R ₃ represents a methyl group or an ethyl group,
R ₄ represents a methyl group or an ethyl group, and
R ₅ is a compound representing a hydrogen atom. In the formula, R ₁ represents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a 2-methoxyethyl group, an allyl group, a propargyl group, or a cyclopropyl group, and R ₂ represents a hydrogen atom or a methyl group, or R ₁ and R ₂ together with the nitrogen atom to which they are bonded represent a 1-pyrrolidinyl group, 4-morpholinyl group or 1-imidazolyl group, R ₃ represents a methyl group, R ₄ represents a methyl group, R ₅ represents a hydrogen atom, and
Particularly useful are compounds in which when R ₁ represents a propargyl group, R ₂ preferably represents a hydrogen atom. Particularly outstanding compounds are those in which R ₁ represents a hydrogen atom, a methyl group or an ethyl group, and R ₂
represents a hydrogen atom, R ₃ represents a methyl group,
R ₄ represents a methyl group, and R ₅ represents a hydrogen atom. Particularly preferred are the following compounds: 2-cyclopropylamino-4-dimethylformamidino-6-amino-s-triazine, 2-cyclopropylamino-4-dimethylformamidino-6-ethylamino-s-triazine , 2-cyclopropylamino-4-dimethylformamidino-6-methylamino-s-triazine, and 2-cyclopropylamino-4-dimethylformamidino-6-propargylamino-s-triazine. A compound of the formula can be prepared by methods known per se.
For example, (a) the following equation: (In the formula, R ₁ , R ₂ and R ₅ have the meanings defined in the above formula.) 2-cyclopropylamino-4.
6-diamino-s-triazine is expressed by the following formula: (In the formula, R ₃ and R ₄ represent the meanings defined in the above formula.) or (b) react with a carboxamide acetal or ketal represented by the following formula: (In the formula, R ₃ , R ₄ and R ₅ have the meanings defined in the above formula.) 2-cyclopropylamino-4-
Formamidino-6-chloro-s-triazine is expressed by the following formula: (In the formula, R ₁ and R ₂ represent the meanings defined in the above formula.) It can be obtained by reacting with ammonia or a primary or secondary amine represented by the formula. Reactions (a) and (b) above are preferably carried out in a solvent or diluent that is inert to the reactants, such as an aliphatic or aromatic hydrocarbon, a halogenated hydrocarbon, an ether or an ethereal compound or a ketone. A catalyst such as p-toluenesulfonic acid can also be added to the reaction mixture, but is not required. The reaction temperature is between 30°C and 130°C. Starting materials of formula and can be prepared by replacing the chlorine atom of a chlorinated s-triazine derivative with one or several corresponding amino groups according to known methods. 2-diallylamino-4-amino-6-(N・
A method for preparing N-dimethylformamidino)-s-triazine is described in US Pat. No. 3,073,851. Diamino- and triamino-s-triazines are described in US Pat. No. 3,189,521 as chemical sterilization agents for adult Musca domestica. The chemical sterilization effect of 2,4,6-triamino-s-triazine derivatives (melamine derivatives) on insects was reported by S. Nagasawa.
Also described in: Insect Control Science, Vol. 39 (4), p. 105 (1974). ABBorkovec and ABDeMilo: Journal of
Medicinal Chemistry (J.Med.Chem.) 10
Volume (5), page 457 (1967), and Labrecz (G.C.
LaBrecque), RLFye, De Milo (A.
B.DeMilo) and ABBorkovec:
Journal of Economic Entomol, Volume 61(6), Page 1621 (1968)
In particular, 2-cyclohexylamino-4,6-
Chemical sterilization effects of diamino-s-triazine, 2-cyclohexylamino-4,6-dihexylamino-s-triazine, 2,4,6-tris-cyclohexylamino-s-triazine and their salts on adult house flies are described. has been done. It has surprisingly been found that compounds of the formula have a pronounced larvicidal action against insect larvae, especially against Diptera larvae. In contrast to the insect chemical sterilizers described above, the compounds of the formula act on insect developmental stages. Its action is to kill newly hatched larvae or to prevent the hatching of adults from pupae. The mode of action of compounds of formula should not be compared to that of classical insecticides, chemical sterilizers or juvenile hormone analogs. The active ingredients of the formula can be used for the control of sanitary pests and animal ectoparasites, in particular of the Diptera, such as the families Moscidae, Gnafidae, Craneidae, Muscatidae and Thinflies. The compounds of the formula can be used as pure active ingredients or together with suitable carriers and/or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances customary in formulation technology, such as natural or recycled substances, solvents and/or dispersants. The compositions according to the invention are obtained by homogeneously mixing and/or grinding the active ingredients of the formula with suitable carriers, with or without the addition of inert dispersants or solvents to the active ingredients, by known methods. Manufactured by The active ingredients of the invention can be processed into the following preparations: solid preparations: powders, tracking agents and granules (coated granules, impregnated granules and homogeneous granules), premixes (feed additives), liquid preparations: (a) active ingredient concentrates dispersible in water: hydrating agents;
Pastes and emulsions; (b) Solutions: propellants (aerosols). For producing solid preparations (powders, tracking agents), the active ingredient is mixed with a solid carrier. Examples of suitable carriers include: kaolin, talc, china clay, loess, chalk, limestone, ground calcium carbonate, atakulay, dolomite, diatomaceous earth, precipitated silica, alkaline earth metal silicates, aluminum silicates. Sodium and potassium (feldspar and mica), calcium and magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as flour, bark flour, sawdust, nuts. shell powder, cellulose powder,
Plant extraction residue, activated carbon, etc. These substances can be used alone or in mixtures. Granules are made by dissolving the active ingredient of the formula in an organic solvent,
It can be produced very easily by applying the resulting solution to particulate minerals such as attapulgite, _SiO2 , granicalcium, bentonite, etc. and then evaporating the solvent. The active ingredient of the formula is mixed with a polymerizable compound (urea/formaldehyde, dicyandiamide/formaldehyde, melamine/formaldehyde, etc.) to perform mild polymerization that does not affect the active ingredient, and during the process, granulation is performed during gel formation. By carrying out this process, polymer granules can also be produced.
a certain specific surface area and a suitable predeterminable adsorption/
The resulting porous particulate polymer (urea/formaldehyde resin, polyacrylonitrile, polyester, etc.) with a desorption ratio is impregnated with the active ingredient, for example in the form of a solution (in a low-boiling solvent), and the solvent is removed. , is more advantageous. preferably 300
Polymer granules of this type in the form of microparticles with a bulk density of from 600 to 600 g/g can also be produced by using an atomizer. Granules can also be obtained by compressing the carrier with the active ingredient and additives and then crushing the product. These mixtures contain additives to stabilize the active ingredients and/or nonionic, anionic and cationic active agents, for example to ensure better wetting properties (wetting agents) and dispersing properties (dispersing agents). can also be added. Examples of suitable materials include: oleic/chalk mixtures, cellulose derivatives (methylcellulose, carboxymethylcellulose), monomers with 5 to 15 ethylene oxide groups per molecule and 8 to 9 carbon atoms in the alkyl moiety. Hydroxyethyl glycol ethers of alkyl and dialkyl phenols, lignin sulfonic acid and its alkali metal and alkaline earth metal salts, polyethylene glycol ether (carbowax), 5 to 20 ethylene oxide groups per molecule and 8 to 18 in the fatty alcohol moiety. fatty alcohol polyethylene glycol ethers having carbon atoms, ethylene oxide, condensation products of propylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, condensation products of urea and formaldehyde, and latex products. Water-dispersible concentrates, ie wettable powders, pastes and emulsifiable concentrates, are compositions that can be diluted with water to the desired concentration. They consist of the active ingredient, a carrier, optionally additives that stabilize the active ingredient, surfactants, antifoaming agents and, if appropriate, solvents. Wettable powders and pastes are obtained by mixing and grinding the active ingredient with the dispersant and carrier powder in suitable equipment until homogeneous. Suitable carriers are, for example, those already mentioned for solid preparations. In some cases it may be advantageous to use mixtures of different carriers. Examples of dispersants are:
Condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, alkali metal, ammonium and alkaline earth metal salts of lignin sulfonic acid, alkali arylsulfonates, dibutyl Alkali metal and alkaline earth metal salts of naphthalene sulfonic acid, salts of fatty alcohol sulfates such as sulfated hexadecanol, heptadecanol, octadecanol, salts of sulfated fatty alcohol glycol ethers, sodium salt of oleyl methyl tauride. , ditertiary ethylene glycol, dialkyl dilauryl ammonium chloride and alkali metal and alkaline earth metal salts of fatty acids. Suitable antifoaming agents are, for example, silicone oils. The active ingredient is mixed with the above additives, ground, sieved and filtered so that the solid particle size does not exceed 0.02 to 0.04 mm in the case of wettable powders and 0.03 mm in the case of pastes. Make sure not to. Emulsifiable concentrates and pastes may contain dispersants, such as those mentioned above,
Manufactured using organic solvents and water. Examples of suitable solvents are alcohols, dimethyl sulfoxide and mineral oil fractions with a boiling point of 120 to 350°C. The solvent must be substantially odorless and inert to the active ingredient. Furthermore, the composition according to the invention can be applied in the form of a solution. For this purpose, one or more of the active ingredients of the formula are dissolved in a suitable organic solvent or mixed solvent. As organic solvents it is possible to use aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkylnaphthalenes and mineral oils, alone or in mixtures. An example of the formulation of the new active ingredient of the formula is described below.
"Parts" indicate parts by weight. Powders: The following substances are used in the manufacture of (a) 0.5% and (b) 2% powders. (a) Active ingredient 0.5 parts Talc 99.5 parts (b) Active ingredient 2 parts Highly dispersed silicic acid 1 part Talc 97 parts The active ingredient is mixed with the carrier and ground. Tracking agent: 5 parts of the active ingredient are ground in lime with 95 parts of carbonate to an average particle size of 80μ. Granules: Dissolve 5 parts of the active ingredient in a solvent such as methylene chloride and add polyethylene glycol (Carbowax).
Mix with 2 parts. This mixture was impregnated with 91.5 parts of calcium carbonate,
Then 1.5 parts of precipitated silicic acid is mixed. The solvent is then evaporated. Wettable powder: 50 parts of active ingredient, 5 parts of powder, such as sodium lignosulfonate, 5 parts of wetting agent, such as dibutylnaphthalene sulfonic acid, 10 parts of silicic acid, and 30 parts of white clay are mixed together and the mixture is pulverized. Emulsifiable Concentrate: 20 parts of the active ingredient are mixed with 20 parts of an emulsifier, such as a mixture of alkylaryl polyglycol ether and alkylaryl sulfonate, and 60 parts of solvent to give a completely homogeneous solution. By diluting this concentrate with water, an emulsion of the desired concentration can be obtained. Premix (feed additive): 0.25 parts of active ingredient and 4.75 parts of dicalcium phosphate or carbonate of terra alba, aerosil or lime are mixed homogeneously with 95 parts of animal feed, for example poultry feed. Propellant: The following ingredients are used for the preparation of the 2% propellant: Active ingredient 2 parts Kerosene 98 parts It is also possible to mix other biocidal substances or biocides with the above composition. For example, in addition to the compounds of the above formula, the compositions of the invention can contain insecticides to widen the spectrum of action. The composition of the present invention or the active ingredient contained therein mainly has the effect of inhibiting the growth of insects, particularly the larvae and pupae of Diptera. Example 1 2-cyclopropylamino-4-N'/N'-dimethylformamidino-6-morpholino-s-
triazine. 2-cyclopropylamino-4-amino-6-
20 g of morpholino-s-triazine and 200 g of benzene
ml and this suspension was treated with 13 g of N.N-dimethylformamide dimethyl acetal with the addition of 0.5 g of p-toluenesulfonic acid (catalyst). The reaction mixture was refluxed for 10 hours. The solvent was then removed under reduced pressure and the residue was suspended in ether. The precipitated solid was recrystallized from isopropanol.
Melting point 160-162℃. The following compounds were prepared by the above procedure:

[Table] Triazine

[Table] Example 2 Effect on house fly (Musca domestica).
Two beakers were filled with 50 g each of freshly prepared CSMA culture medium for maggots. Add 2.5 ml of a 1% acetone solution of each active ingredient to the culture medium in each beaker.
was added with a pipette. The culture medium was then thoroughly mixed and the solvent stripped off. Fifty one-day-old housefly maggots were placed in each beaker containing test culture medium treated with each active ingredient. After the maggots pupated, the pupae were separated from the culture medium by flushing with water and counted. Next, we counted the number of flies that hatched from the pupa after 10 days to examine the effect on metamorphosis.

[Table] Example 3 Effect on Lucilia sericata. 1 ml of a 0.5% aqueous solution of the active ingredient was added to 9 ml of the medium at 50°C. Next, the insecticidal effect was examined by placing approximately 30 newly hatched black fly larvae in the medium and determining the mortality rate after 48 and 96 hours, respectively. In this test, the compound of the formula worked well against the yellowtail fly. Example 4 Action against Aedes aegypti. A predetermined amount of a 0.1% acetone solution of the active ingredient was pipetted onto the surface of 150 ml of water in a series of beakers to give an active ingredient concentration of 10 ppm each. After the acetone had evaporated, 30 to 40 2-day-old Aedes aegypti larvae were placed in each beaker containing the active ingredient solution. Mortality rate was examined after 5 days.

【table】

Claims (1)

[Claims] Primary formula: (In the formula, R ₁ is a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms substituted with a lower alkoxy group, an alkenyl group having 3 to 4 carbon atoms, a carbon represents an alkynyl group or cyclopropyl group having 3 to 4 atoms, R ₂ represents a hydrogen atom, a methyl group or an ethyl group, or R ₁ and R ₂ are combined with the nitrogen atom to which they are bonded; , morpholinyl group, pyrrolidinyl group, and imidazolyl group, R ₃ represents a methyl group or ethyl group, R ₄ represents a methyl group or ethyl group, and R ₅ represents a hydrogen atom) Propylamino-4-formamidino-6-amino-s-triazine. 2 _R1 is a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms substituted with a lower alkoxy group, an alkenyl group having 3 to 4 carbon atoms, a carbon atom number 3 to 4 alkynyl group, cyclopropyl group, R ₂ represents a hydrogen atom, methyl group or ethyl group, or R ₁ and R ₂ together with the nitrogen atom to which they are bonded represent 1 - pyrrolidinyl group, 4morpholinyl group or 1-imidazolyl group, R ₃ represents a methyl group or ethyl group, R ₄ represents a methyl group or ethyl group, and R ₅ represents a hydrogen atom. 1
Compounds described in Section. 3 _R1 is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a 2-methoxyethyl group, an allyl group,
represents a propargyl group or a cyclopropyl group, R ₂ represents a hydrogen atom or a methyl group, or R ₁ and R ₂ together with the nitrogen atom to which they are bonded represent a 1-pyrrolidinyl group, a 4-morpholinyl group, or represents a 1-imidazolyl group,
R ₃ represents a methyl group, R ₄ represents a methyl group,
3. A compound according to claim 1 or 2, wherein R ₅ represents a hydrogen atom and, when R ₁ represents a propargyl group, R ₂ preferably represents a hydrogen atom. 4 R ₁ represents a hydrogen atom, a methyl group or an ethyl group, R ₂ represents a hydrogen atom, R 3 represents a methyl group, R ₄ represents a methyl group, and _{R 5 represents} a hydrogen atom. A compound according to any one of the ranges 1 to 3. 5. The compound according to claim 3, which is 2-cyclopropylamino-4-dimethylformamidino-6-propargylamino-s-triazine. 6. The compound according to claim 4, which is 2-cyclopropylamino-4-dimethylformamidino-6-amino-s-triazine. 7. The compound according to claim 4, which is 2-cyclopropylamino-4-dimethylformamidino-6-methylamino-s-triazine. 8. The compound according to claim 4, which is 2-cyclopropylamino-4-dimethylformamidino-6-ethylamino-s-triazine. 9 Formula: (In the formula, R ₁ is a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms substituted with a lower alkoxy group, an alkenyl group having 3 to 4 carbon atoms, a carbon represents an alkynyl group or cyclopropyl group having 3 to 4 atoms, R ₂ represents a hydrogen atom, a methyl group or an ethyl group, or R ₁ and R ₂ are combined with the nitrogen atom to which they are bonded; , morpholinyl group, pyrrolidinyl group, and imidazolyl group, R ₃ represents a methyl group or ethyl group, R ₄ represents a methyl group or ethyl group, and R ₅ represents a hydrogen atom) Propylamino-4/6
-diamino-s-triazine, with the following formula: (In the formula, R ₃ represents a methyl group or an ethyl group, and R ₄ represents a methyl group or an ethyl group.) (In the formula, R ₁ to R ₅ have the above meanings.) A method for producing 2-cyclopropylamino-4-formamidino-6-amino-s-triazine represented by: 10 As an active ingredient, the following formula: (In the formula, R ₁ is a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms substituted with a lower alkoxy group, an alkenyl group having 3 to 4 carbon atoms, a carbon represents an alkynyl group or cyclopropyl group having 3 to 4 atoms, R ₂ represents a hydrogen atom, a methyl group or an ethyl group, or R ₁ and R ₂ are combined with the nitrogen atom to which they are bonded; , morpholinyl group, pyrrolidinyl group, and imidazolyl group, R ₃ represents a methyl group or ethyl group, R ₄ represents a methyl group or ethyl group, and R ₅ represents a hydrogen atom) A pest control composition containing propylamino-4-formamidino-6-amino-s-triazine. 11. The composition according to claim 10, wherein the pest to be controlled is an insect of the order Diptera. 12. The composition according to claim 11, wherein the insect of the order Diptera is an insect of the family Moscidae, the family Gnatidae, the family Craneidae, the family Muscatidae, and the family Asteridae.