JPS638105B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel 2-cyclopropylamino-4-
formylamino-6-amino-s-triazine-
The present invention relates to derivatives, salts thereof, methods for producing the same, and pest control agents containing the compounds. The 2-cyclopropylamino-4-formylamino-6-amino-s-triazine derivative has the following formula: (In the formula, R ₁ is a hydrogen atom, an unsubstituted or lower alkoxy-substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, a cyclo It represents a propyl 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 morpholinyl group, a pyrrolidinyl group or an imidazolyl group. , R ₃ represents a hydrogen atom) and its acid addition salt structure. The alkyl group for R ₁ may be a linear or branched unsubstituted group or a group substituted with, for example, an alkoxy group having 1 to 4 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- and tertiary-butyl, and 2-methoxyethyl. C3 -C4 alkenyl and C3 -C4 alkynyl consist of allyl and propargyl groups, respectively. The term "acid addition salt" of the 2-cyclopropylamino-4-formylamino-6-amino-s-triazine-derivative of the above formula is understood to mean salts with strong mineral acids, such as with hydrochloric acid or sulfuric acid. It should be. Among the compounds represented by the above formula, preferred compounds from the viewpoint of pesticidal action are those in which R ₁ is a hydrogen atom,
C 1 -C 4 alkyl group, unsubstituted or substituted with a lower alkoxy group, C 3
-4 alkenyl group, having 3 -4 carbon atoms
represents an alkynyl group, a 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 a 1-pyrrolidinyl group, 4-morpholinyl group or 1-imidazolyl group. is a compound in which R ₃ represents a hydrogen atom. Among these, particularly advantageous compounds are those in which 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
When R ₂ is combined with the nitrogen atom to which these are bonded, a 1-pyrrolidinyl group, a 4-morpholinyl group,
Alternatively, it represents a 1-imidazolyl group, and R ₃ represents a hydrogen atom. Furthermore, the most preferred compound is R ₁ in the above formula
represents a hydrogen atom, an ethyl group, an allyl group, or a propargyl group, R ₂ represents a hydrogen atom,
R ₃ represents a hydrogen atom, especially 2-cyclopropylamino-4-formylamino-6-
ethylamino-s-triazine, 2-cyclopropylamino-4-formylamino-6-allylamino-s-triazine, 2-cyclopropylamino-4-formylamino-6-propargylamino-s-triazine, and 2-cyclo These are four compounds of propylamino-4-formylamino-6-amino-s-triazine. The compounds represented by the above formula can be produced by the following methods, such as (a) the following formula: _{2 - cyclopropylamino represented by} -4-
A method of converting formamidino-6-amino-s-triazine into the corresponding 2-cyclopropylamino-4-formylamino-6-amino-s-triazine by hydrolysis, or (b) the following formula: (In the formula, R ₃ represents the meaning expressed in the above formula, and R ₁
and R ₂ have the meanings expressed in the above formula excluding the hydrogen atom. ) 2-cyclopropylamino-4.
This method involves reacting 6-diamino-s-triazine with a formylating agent. Hydrolysis (a) can also be carried out at 0° to 100°C under normal pressure by adding an acid such as hydrochloric acid. Advantageously, water is used as solvent or diluent and, if desired, organic solvents such as dioxane, alcohols, etc. are added. By doing so, the reaction product precipitates. The reaction (b) is preferably carried out by condensing the compound represented by the above formula with an orthoformate ester, preferably using formic acid and acetic anhydride as formylation reagents, or in the presence of a catalytic amount of a strong acid, and then partially This is done by hydrolyzing the In the former case, a solvent or diluent that is inert to the reactants can be used; in the latter case, the orthoester thereof is used as the solvent. The starting material represented by the above formula is the following formula: (In the formula, R ₁ , R ₂ and R ₃ have the meanings expressed in the above formula.) The triazine derivative represented by the following formula: (In the formula, R ₄ and R ₅ have the meanings expressed in the above formula.) The starting materials of the above formula can be prepared by conventional methods from chlorine-substituted s-triazine derivatives by replacing chlorine with one or several corresponding amino groups. Diamino-s-triazine and triamino-s
- Triazines are described in US Pat. No. 3,189,521 as chemical sterilization agents for adult house flies (Musca domestica). 2・
The chemical sterilization effect of 4,6-triamino-s-triazine derivatives (melamine derivatives) on insects was also reported by S. Nagasawa et al., Insect Control Science 39(4), 105.
(1974). Also, A.B.
A.B. Borkovec and A.B.
A.B. DeMilo [J.Med.Chem.
10(5), 457 (1967)] and GCLaBrecque, RLFye, A.B. Demilo and A.B. Bolkovec, [J.Econ.Entomol. 61 ,(6),
1621 (1968)], among other compounds 2-cyclohexylamino-4,6-diamino-s-triazine, 2-cyclohexylamino-4,6-
dihexylamino-s-triazine and 2.4.
Musca 6-tris-cyclohexylamino-s-triazine and its salts
describes the chemical sterilization effect on living worms (Domestica domestica). The chemical sterilization effect of acetylmelamine is described in US Pat. No. 3,520,974. In the present invention, the compound represented by the above formula is an insect larva, preferably Diptera.
It was found that it has a remarkable larvicidal effect against the larvae of Compared to the above insecticidal chemical sterilizers,
The compounds of the above formula act on the developmental stages of insects. The above actions consist of killing newly hatched larvae or preventing them from hatching into adults from pupae. The type of action of the compound represented by the above formula is similar to that of conventional insecticides,
It should not be compared to chemical sterilization agents or similar larval hormones. The active ingredient represented by the above formula is suitable for sanitary pests, in particular of the order Diptera, namely the families Culicidae, Simuliidae, Tipulidae, Muscidae and Calliphoridae. , and can be used to control external parasites on animals. The compounds of the above formula can be used as pure active ingredients or together with suitable carriers and/or additives. Suitable carriers and additives include:
They may be solid or liquid and correspond to the substances customary in the field of formulation, such as solvents and/or dispersants which are natural or recycled materials. The composition according to the present invention is prepared by uniformly mixing and/or polishing the active ingredient (compound) represented by the above formula with a suitable carrier and optionally a dispersant or solvent inert to the active ingredient. It is produced in a known manner by crushing. The active ingredient can be used in the following dosage forms. Solid formulations: Dusts, spreaders, granules (coated granules, impregnated granules and homogeneous granules) Premixes (feed additives) Liquid formulations: (a) Active ingredients dispersed in water: Wettable powders, pastes, emulsions (b) Solutions: Spraying agents (aerosols) To produce solid dosage forms (powders, dusting powders), the active ingredient is mixed with a solid carrier. Suitable carriers include, for example, kaolin, talc, bolus, loess, limestone, heavy calcium carbonate, atclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates,
Sodium silicates, potassium silicates, aluminum silicates (feldspar and mica), calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic substances, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, etc. Also cornmeal, bark flour, Examples include sawdust, nut shell meal, ground products of vegetable products such as cellulose flour, as well as residues of plant extracts, activated carbon, and the like. These substances can be used alone or in combination with each other. Granules are produced by dissolving the active ingredient represented by the above formula in an organic solvent, applying the resulting solution to granular minerals such as attapulgite, silicon dioxide, granular calcium, bentonite, etc., and evaporating the solvent. Therefore, it can be manufactured very easily. Polymer granules are also produced by mixing the active ingredient represented by the above formula with a polymerizable compound (urea/formaldehyde, dicyandiamide/formaldehyde, melamine/formaldehyde, etc.) and granulating the active ingredient while in a gel state. It can be produced by gentle polymerization without affecting. Alternatively, processed porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester, etc.) with a specific surface area and a predetermined preferred adsorption/decolorization rate may be loaded with the active ingredient in its solution in a low-boiling solvent, for example. This can be carried out more advantageously by impregnating the liquid as a solvent and then removing the solvent. Polymer granules of this type in the form of fine granules, preferably with a bulk density of 300 g/ to 600 g/, can also be produced with the aid of an atomizer. Granules can also be obtained by compressing the carrier together with the active ingredient and additives and pulverizing the product. Additives to these mixtures stabilize the active ingredients and/or nonionic, anionic and cationic surfactants, such as those ensuring good hydration (hydrating agents). It is also possible to add substances that ensure good dispersibility (dispersants). Examples of suitable substances include olein/
Hydroxyethyl glycol ethers of thioyoke mixtures, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), monoalkyl phenols having 5 to 15 ethylene oxide groups per molecule and having 8 to 9 carbon atoms in the alkyl moiety, and dialkyl phenols. ,
Lignosulfonic acid, its alkali metal salts and alkaline earth metal salts, polyethylene glycol ether (carbowax), each molecule having 5 to 20 ethylene oxide groups and the number of carbon atoms in the fatty alcohol moiety being 8 to 18. Mention may be made of fatty alcohol polyethylene glycol ethers, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, condensation products of urea and formaldehyde, and also latex products. Water-dispersible concentrates or wettable powders, pastes, and emulsifiable concentrates are compositions that can be diluted with water to achieve a desired concentration. The concentrates contain the active ingredient, a carrier, optionally an additive to stabilize the active ingredient and the surfactant,
It also comprises an antifoam agent and, if desired, a solvent. Wettable powders and pastes are obtained by mixing and grinding the active ingredients together with dispersants and powder carriers in suitable equipment until homogeneous. Suitable carriers are, for example, those mentioned above which are in solid dosage form at the time of application. In some cases it may be advantageous to use a mixture of different carriers. Examples of dispersants include condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, and alkali metal salts, ammonium salts of lignosulfonic acid, and alkaline earth metal salts, as well as alkylaryl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalene sulfonic acid, and fatty alcohols such as sulfated hexadecanol, sulfated heptadecanol, sulfated octadecanol. sulfates and sulfated fatty alcohol glycol ethers, sodium salts of oleyl methyl tauride, di-tertiary-ethylene glycol, dialkyl dilauryl ammonium chloride, and alkali metal salts of fatty acids;
and alkaline earth metal salts. Suitable antifoaming agents include, for example, silicone oil. The active ingredient is mixed with the above additives, crushed, sieved, and deformed to reduce the solid particle size in wettable powders.
For 0.02 to 0.04mm paste, it will be 0.03mm and will not be larger than that. Emulsifiable concentrates and pastes are prepared using dispersants, organic solvents, and water as described above. Examples of suitable solvents include alcohols, dimethyl sulfoxide, and mineral oil fractions with boiling points between 120° and 350°C. The solvent must be practically odorless and inert towards the active ingredient. Furthermore, the composition according to the invention can also be applied in the form of a solution. For this purpose, the active ingredient or several active ingredients, usually of the above formula, are dissolved in a suitable organic solvent or mixture of solvents. As organic solvents it is possible to use aliphatic and aromatic hydrocarbons, their chloride derivatives, alkylnaphthalenes and mineral oils alone or in admixture (with each other). The new active ingredient represented by the above formula can be made into the following dosage form. Parts represent parts by weight. Powders The following substances are used to produce (a) 0.5% and (b) 2% powders. (a) Active ingredient 0.5 part talc 99.5 parts (b) Active ingredient 2 parts highly dispersed silicic acid 1 part talc 97 parts The above active ingredients are mixed with a carrier and polished. 5 parts of the active ingredient of the dispersant are mixed with 95 parts of carbonate of lime and ground to an average particle size of 80μ. Granules 5 parts of active ingredient dissolved in a solvent such as methylene chloride, polyethylene glycol (“Carbowax”)
Mix with 2 parts. 91.5 parts of calcium carbonate are impregnated into the above mixture, and 1.5 parts of precipitated silicic acid are mixed. The solvent is then distilled off. Wettable powder active ingredient: 50 parts with a dispersing agent such as sodium ligninsulfonate
Mix with 5 parts. 5 parts of a lubricant such as dibutyl-naphthalene-sulfonic acid, 10 parts of silicic acid and 30 parts of kaolin are finely ground with the above mixture. 20 parts of the emulsifiable concentrate active ingredient are mixed with 20 parts of an emulsifier, such as a mixture of alkylaryl polyglycol ethers and alkylaryl sulfonates, and 60 parts of the solvent until the solution is completely homogeneous. By diluting this concentrate with water, an emulsion of the desired concentration can be obtained. Premix (feed additive) 0.25 parts of active ingredients and 4.75 parts of dibasic calcium phosphate or 4.75 parts of kaolin or 4.75 parts of lime aerosol or carbonate are uniformly mixed with 95 parts of animal feed such as poultry feed. Propellant To prepare a 2% propellant, the following materials are used: Active Ingredients 2 parts Kerosene 98 parts Other biocidal active ingredients and other biocides may be mixed into the above composition. Thus, in addition to the cited compounds usually represented by the above formula, the compositions according to the invention can, for example, contain insecticides with a broad spectrum of activity. The above-mentioned composition or active ingredient preferably has a controlling effect mainly on the development of larvae or pupae of insects of the order Diptera. Example 1 2-Cyclopropylamino-4-formylamino-6-morpholino-s-triazine 25 g of 2-cyclopropylamino-4-N'.N'-dimethylformamidino-6-morpholino-s-triazine was added to water. The resulting solution was treated with 100 ml of 1N hydrochloric acid. After stirring for 15 minutes at room temperature, 2-cyclopropyl-
Amino-4-formylamino-6-morpholino-
s-triazine began to precipitate. The crude product was recrystallized from dimethylformamide. Melting point 291−292
℃. The following compounds represented by the above formula are produced by the above production method. [Table] [Table] Example 2 Effect on house fly (Musca domestica) Freshly prepared CSMA medium for maggots was placed in a beaker. 2.5 ml of a 1% acetonic acid solution of each active ingredient was pipetted into the medium in the beaker. The medium was thoroughly mixed and then the solvent was distilled off. Twenty-five 1-, 2-, and 3-day-old house fly maggots and approximately 50 house fly eggs were placed in respective beakers containing treated media to be tested for their respective active ingredients. . After the maggots pupated, the pupae were separated from the medium by washing with water and counted. The number of flies hatched from pupa was counted after 10 days and any effects on metamorphosis were observed. In the above test, the compound of Example 1 showed good action against house flies. Example 3 Action against Lucilia sericata 1 ml of an aqueous solution containing 0.5% active ingredient
℃ and added to 9 ml of medium. Thereafter, approximately 30 newly hatched Lucilia sericata larvae were placed in the medium, and the insecticidal activity was determined by measuring the mortality rate after 48 and 96 hours, respectively. In the above test, the compound represented by the above formula acted well against Lucilia sericata. Example 4 Effect on the larvae of Ae des aegypti 150 in each of a fixed number of beakers
By pipetting a specified amount of a 0.1% acetone solution of the active ingredient into ml of water, solutions with concentrations of the active ingredient of 10, 5 and 1 ppm, respectively, were obtained.
After evaporating the acetone, 30 to 40 2-day-old Aedes aegypti larvae were placed into each beaker containing a solution of the active ingredient. 1 day later
The mortality rate was measured after 2 days and 5 days. In the above test, the compound represented by the above formula showed good action against Aedes aegypti. Example 5 Test A: Growth inhibition of Musca comeotica of the Order Diptera Test substance: 0.1% test compound in acetone Test control: House fly Test material: Maggot medium; Production method: 100 g yeast
Suspend in water 9. This suspension is added to 5 kg of a mixture of rice bran/Alfalfa (1:1) and mixed thoroughly. After 5 days material suitable for testing is obtained. ] Concentration: Active ingredient 0.01% Test method: Place 50g of culture medium in a 200ml polyethylene beaker. Pipette 5 ml of a 0.1% acetone solution of each test compound onto the medium in the beaker. After the medium is thoroughly mixed, the acetone is allowed to evaporate for at least 20 hours. After that, 25 2-day-old housefly eggs
The cells are placed in a beaker containing a test medium treated with each active ingredient and a beaker containing an untreated medium as a control group. Two beakers are used for each test. After 5 days, pupae are washed out of the medium with water, placed in a beaker and covered with a copper mesh lid. Evaluation method: After separation from the medium, count the number of normal and malformed pupae. In addition, 10 after the start of the test
Count the number of adults that emerge from pupae per day. Test B: Growth inhibition of the Egyptian bush mosquito of the Order Diptera Test substance: 0.1% test compound in acetone Test control substance: Egyptian bush mosquito Test material: Tap water Test concentration: 1 ppm test compound Test method: 200ml 150 polyethylene beakers
Fill with ml tap water and 0.01% of each test compound
1.5 ml of acetone solution was pipetted onto the surface of the water. After evaporating the acetone, 2 days old
Twenty aged Egyptian bush mosquito larvae were placed in each beaker containing the test compound solution. Then the ground dog biscuits were added to the beaker, and the beaker was covered with a copper mesh lid. Evaluation method: Observe the growth of larvae every 10 days, and measure the toxicity of the test compound to the larvae (mortality rate %) and the mosquito emergence rate (the rate of emergence into adults). [Table] [Table]

Claims (1)

[Claims] Primary formula: (wherein R ₁ is a hydrogen atom, an unsubstituted or lower alkoxy-substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, represents 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 morpholinyl group, a pyrrolidinyl group, and 2-cyclopropylamino- ₄ -formylamino-6-amino-s-triazine and its acid addition salt represented by: 2 In the above formula, R ₁ is a hydrogen atom, an unsubstituted or lower alkoxy group-substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, or an alkynyl group having 3 to 4 carbon atoms. , represents a cyclopropyl group, R ₂ is 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-morphonyl group or 1-imidazolyl group, and R ₃ represents a hydrogen atom. A compound according to claim 1 and an acid addition salt thereof. 3 In the above 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, A patent characterized in that 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 a 1-imidazolyl group, and R ₃ represents a hydrogen atom A compound according to claim 1 and its hydrochloride. 4 In the above formula, R ₁ is a hydrogen atom, an ethyl group,
Represents an allyl group or a propargyl group, R ₂
2. The compound according to claim 1, wherein R represents a hydrogen atom, and R ₃ represents a hydrogen atom. 5. The compound according to claim 1, which is 2-cyclopropylamino-4-formylamino-6-ethylamino-s-triazine. 6. The compound according to claim 1, which is 2-cyclopropylamino-4-formylamino-6-allylamino-s-triazine. 7. The compound according to claim 1, which is 2-cyclopropylamino-4-formylamino-6-propargylamino-s-triazine. 8. The compound according to claim 1, which is cyclopropylamino-4-formylamino-6-amino-s-triazine. 9 Formula: (wherein R ₁ is a hydrogen atom, an unsubstituted or lower alkoxy-substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, represents 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 morpholinyl group, a pyrrolidinyl group, and In order to produce 2-cyclopropylamino- ₄ -formylamino-6-amino-s-triazines represented by the following formula: _{2 - cyclopropylamino- _ _} By hydrolysis of 4-formamidino-6-amino-s-triazine, the corresponding 2-cyclo-propylamino-4-formylamino-6-amino-s-
2-cyclopropylamino-4-formylamino-6-amino-
Method for producing s-triazine. 10. The production method according to claim 9, wherein the formylating agent is formic acid and acetic anhydride or ortho-formic acid. 11 The following formula as the active ingredient: (wherein R ₁ is a hydrogen atom, an unsubstituted or lower alkoxy-substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, represents 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 morpholinyl group, a pyrrolidinyl group, and 2-Cyclopropylamino-4-formylamino-6-amino-s-triazine (representing an imidazolyl group, R ₃ represents a hydrogen atom). 12 The pest to be controlled is Diptera.
12. The pest control agent according to claim 11, which is an insect control agent of the order of insects. 13 Harmful insects to be controlled include Diptera, Culicidae, Simuliidae, Tipulidae, Muscidae, and Calliphoridae.
13. The pest control agent according to claim 12, wherein the pest control agent is an insect.