JPH0373538B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel halogenopropargylformamides, a method for producing the same, and a method for using the same as a pest control agent. Heavy metal salts of ethylene-1,2-bis(dithiocarbamic acid), particularly zinc ethylene-1,2-bis(dithiocarbamic acid), have long been used as plant pathogen control agents for agriculture and horticulture. [R.
Wegler, “Chemie der Pflantzenschutz−und
Scha¨dlings−beka¨mpfungsmittel” (Chemistry
of Plant Protection Agents and Pest−
Combating Agents), Vol. 2, p. 65, Springer-
Verlag.Berlin/Heidelberg/New York
(1970)]. Furthermore, it has long been known that compounds containing an N-trihalogenomethylthio group are useful as agricultural and horticultural fungicides. Thus, for example, N-(trichloromethylthio)-tetrahydrophthalimide has been used in practice for disease control in fruit and grape cultivation. (German Patent Specification No. 887506 and Angew.Chem. 76 , 807
[1964]). Furthermore, inorganic compounds of copper are known that have a broad spectrum of fungicidal action. (KHBa¨chel,
“Pflanzenschutz und Scha¨dlingsbeka¨mpfung”
[Plant Protection and Pest-combating], 121
and 122 pages, Georg Thieme Verlag Stuttgart),
Still further, iodopropargyl compounds such as N-
Butyl iodo-propargyl carbamate is known as a paint disinfectant. (DE-OS [German Open Gazette] No. 3116653), formula () In the formula, R represents hydrogen, alkyl, halogenoalkyl, cycloalkyl, alkenyl, alkynyl, halogenoalkynyl, optionally substituted aralkyl, and optionally substituted aryl,
And Hal represents halogen, and new halogenopropargylformamides were discovered. expression () In the formula, R represents hydrogen, alkyl, halogenoalkyl, cycloalkyl, alkenyl, alkynyl, halogenoalkynyl, optionally substituted aralkyl and optionally substituted aryl, and Hal represents halogen. Halogenopropargylformamides have the formula () where R has the meaning given above, propargyl formamides and a halogenating reagent are mixed in a diluent in the presence of a basic substance from -30 to +
It is obtained by reaction at temperatures up to 50°C. The novel halogenopropargylamides of formula () have strong bactericidal and bactericidal properties. Surprisingly, these halogenopropargylamides exhibit superior activity compared to known compounds. These compounds according to the invention represent a valuable development in the art, since the compounds of the invention can be used in a large number of possible applications due to their excellent biological properties. Among the halogenopropargylformamides of formula () according to the invention, preferred compounds are those in which R is hydrogen, alkyl having 1 to 20 carbon atoms, 1 to 5 halogen atoms and 1 to 8 carbon atoms. Halogenoalkyl with carbon atoms, cycloalkyl with 5 to 10 carbon atoms, alkenyl with 2 to 6 carbon atoms, alkynyl with 2 to 6 carbon atoms, 1 to 3 halogen atoms and 2
halogenoalkynyl having ~6 carbon atoms,
or the alkyl group has 1 to 6 carbon atoms, the aryl group has 6 to 10 carbon atoms, and the aryl moiety is the same or selected from alkyl having 1 to 6 carbon atoms and halogen. Different substituents 1
aralkyl optionally substituted with ~5 or alkyl having 1 to 6 carbon atoms;
halogen, nitro, alkoxy with 1 to 6 carbon atoms, halogenoalkyl with 1 to 5 halogen atoms and 1 to 6 carbon atoms, 1 to 5 halogen atoms and 1 to 6 carbon atoms represents aryl optionally substituted with 1 to 5 of the same or different substituents selected from halogenoalkylthio having , and Hal represents fluorine, chlorine, iodine and bromine. Particularly preferred compounds according to the invention among the halogenopropargylformamides of formula () are those in which R is hydrogen, alkyl having 1 to 18 carbon atoms, such as methyl, ethyl, n- and iso-propyl, n -, sec.-, tert., - and iso-butyl,
pentyl, hexyl, 2-ethyl-hexyl, octyl, undecyl, dodecyl and stearyl, halogenoalkyl with 1 to 5 halogen atoms and 1 to 4 carbon atoms, cycloalkyl with 5 to 7 carbon atoms , such as cyclopentyl, cyclohexyl and cycloheptyl, 2-
Alkenyl with 4 carbon atoms, such as vinyl, propenyl or butenyl, alkynyl with 3 to 4 carbon atoms, such as propynyl or butynyl, with 1 or 2 halogen atoms and 3 to 5
halogenoalkynyl having 1 to 4 carbon atoms, or 1 or 2 carbon atoms in the alkyl portion and 6 carbon atoms in the aryl portion, the R group having 1 to 4 carbon atoms; Alkyl, such as methyl, ethyl, n- or iso-propyl,
can be preferably substituted by 1 to 5 identical or different substituents selected from n-, sec-, tert- or iso-butyl and halogens, such as fluorine, chlorine or bromine, represents optionally substituted aralkyl, such as benzyl or phenethyl, and phenyl optionally further substituted by 1 to 5 identical or different substituents; , halogens such as fluorine, chlorine, bromine and iodine, nitro, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, 1 to 5 halogen atoms and 1 to 4 carbon atoms Halogenoalkyl having atoms such as trifluoromethyl, trichloromethyl and trichloroethyl, and halogenoalkylthio having 1 to 5 halogen atoms and 1 to 4 carbon atoms; and Hal represents iodine and bromine. It is something. More particularly preferred compounds of formula () are
R represents hydrogen, alkyl having 1 to 18 carbon atoms, or phenethyl or benzyl, optionally substituted with 1 to 3 identical or different substituents selected from methyl, ethyl and chlorine; , or nitro, methyl, ethyl, n- and iso
- identical or different substituents 1 to 1 selected from propyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, trifluoromethylthio and trichloromethylthio;
It represents phenyl which may be optionally substituted with 3, and Hal represents iodine and bromine. In addition to those shown in the production examples, examples of halogenopropargylformamides include bromopropargylformamide, iodopropargylmethylformamide, iodopropargyl octylformamide, iodopropargyldecylformamide, iodopropargylformanilide, 2-chloro-iodo Propargylformanilide, 3-chloro-iodopropargylformanilide, 4-chloro-iodopropargylformanilide, 2,3-dichloro-iodopropargylformanilide, 2,4-dichloro-iodopropargylformanilide, 3,4-dichloro- Iodopropargylformanilide, 3,5
-dichloro-iodopropargylformanilide, 2,4,6-trichloro-iodopropargylformanilide, 2-methyl-iodopropargylformanilide, 3-methyl-iodopropargylformanilide, 4-methyl-iodopropargylformanilide, 2, 3-dimethyl-iodopropargylformanilide, 2,6-dimethyl-iodopropargylformanilide, 2-
Methyl-6-ethyl-iodopropargylformanilide, 3-trifluoromethyl-iodopropargylformanilide, 3,5-bis-trifluoromethyl-iodopropargylformanilide, 3-nitro-iodopropargylformanilide, bromopropargylformanilide , 3-
Chloro-bromopropargylformanilide and 4-chloro-bromopropargylformanilide are mentioned, respectively. For example, the reaction pathway in the process according to the invention when propargylformamide and iodine are used as starting materials can be represented by the following equation. Formula () provides a definition of the propargylformamides used as starting materials in carrying out the invention. Most of these propargyl formamides are known, and can be obtained by known methods, e.g. by reacting a suitable formamide with e.g. potassium tert-butyrate to obtain the potassium salt of formamide, which is then reacted with a propargyl halide. can be synthesized by but,
It can also be obtained by reacting a primary amine with a propargyl halide in the presence of a base and formylating the resulting propargyl amine with formic acid or a formic acid ester. (For example, Bull.Soc.Chim.Fr.
1967 [2], pp. 588-596]). Furthermore, the halogenating agents, such as halogens, used as starting materials are commercially available and readily available products. Suitable diluents in the process of the invention are water and polar organic solvents. Suitable polar organic solvents are those that are inert under the reaction conditions. It is advantageous to use organic solvents that have a certain degree of dissolving power for the reaction components. Preferably, solvents having hydroxyl groups, such as alcohols, are used. Particularly suitable alcohols are the typical lower aliphatic alcohols, such as methanol, ethanol and iso
-propanol, and di- or polyhydroxy compounds such as ethylene glycol and polyethylene glycol. The reaction is particularly preferably
Performed in methanol and water. Suitable basic substances are alkali metal hydroxides and alkaline earth metal hydroxides, but preference is given to using alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide. Suitable halogenating agents are elemental halogens or hypohalites. Hypohalite is
It is produced when a halogen is added to the above-mentioned alkaline solution, but it may also be made from a halogen and an alkali prior to the halogenation reaction and added to the substance to be halogenated. Particular mention may be made of iodine and bromine. The reaction temperature can be from -30 to 50°C, but preferably ranges from 0 to 20°C. The manufacturing method according to the present invention can be carried out, for example, as follows. First, propargylformamide of formula () is placed in one of the above diluents and a 1-3 molar, preferably 1.5 molar amount of alkali is added. A halogenating agent in an amount of at least 1 molar is then added in portions. An excess of halogenating agent is not disadvantageous, and stirring is continued while maintaining the temperature in the range of 0 to 20°C. The reaction is monitored by thin layer chromatography. After the reaction has ended, the reaction mixture is worked up in the usual manner, for example by adding water to precipitate or extract the final product. The active compounds according to the invention exhibit a strong microbicidal action and can be used in practice for the control of undesirable microorganisms. The active compounds are suitable for use as plant protection agents and as microbicides for the protection of industrial materials. Fungicides for plant protection include Plasmodiophoromycetes, Oomycstes, Chytridiomycetes,
Zygomycetes, Ascomycetes, Basidiomycetes
and Deuteromycetes. Plant protection bactericides include Pseudomonas, Rhizobium, Enterobacteriaceae, and COrynebacteriaceae. ) and Streptomycetaceae.The active compounds according to the invention are well tolerated by plants at the concentrations required for plant disease control and can be used in the aboveground parts of plants, in parent plants for vegetative propagation. (Vegetative propagation
stock), seeds, and even soil. As plant protection agents, the active compounds according to the invention are used in particular against Leptosphaeria nodorum and Fusarium nivale in cereals and against Venturia in apples and Xanthomonas oryzae in rice. ) and is highly effective. Furthermore, agar plate culture tests showed broad bactericidal activity. If the amount used is appropriate,
Acaricidal action is also observed. The active compounds according to the invention can be used, for example, in solutions, emulsions,
Preparations of suspensions, powders, foams, liniments, granules, aerosols, natural or synthetic impregnating agents, microcapsules in polymeric substances and in seed coating compositions, smoked cartridges, fumigation cans, It can be made into formulations for use in fumigators such as smoked coils (incense sticks) and formulations for ULV cold atomization or heat atomization. These formulations are prepared in a known manner, for example by combining the active compounds of the invention with bulking agents, i.e. liquid solvents, gases which are liquefied under pressure, and/or solid carriers, optionally with surfactants, i.e. emulsifiers and/or solid carriers. Alternatively, it is produced by mixing with a dispersant and/or blowing agent. When using water as a bulking agent, organic solvents may be used as co-solvents. Liquid solvents are mainly aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride,
Aliphatic hydrocarbons, such as cyclohexane or paraffins, such as mineral oil fractions, alcohols, such as butanol or glycols, and their ethers, esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethylsulfoxide, as well as water, are suitable. By liquefied gaseous bulking agent or carrier is meant a liquid that is a gas at standard temperature and pressure, such as aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. As a solid carrier,
Natural mineral mills such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic mineral mills such as highly dispersed silicic acid, alumina and silicates are suitable. Examples of solid carriers for granules include calcite,
Marble, pumice, sepiolite, dolomite, as well as synthetic granules or organic materials such as sawdust, coconut shells, corn cobs, tobacco stalks are suitable. Emulsifiers and/or blowing agents include, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl- Sulfates, arylsulfonates and albumin hydrolysis products are suitable. Suitable dispersants are, for example, lignin sulfite waste liquor and methylcellulose. Adhesives such as carboxymethylcellulose in the form of powders, granules or latexes and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the formulations. Colorants such as inorganic pigments such as iron oxide, titanium oxide, and Persian blue and organic dyes such as alizarin dyes, azo dyes and phthalocyanine metal salt dyes and micronutrients such as iron, manganese,
It is possible to use salts of boron, copper, cobalt, molybdenum and zinc. This preparation usually contains 0.1 to 95% by weight, preferably 0.5% by weight.
Contains ~90% by weight of active compound. The active compounds according to the invention can be used in combination with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, It can be present as a mixture with growth factors, plant nutrients and soil structure improvers. The active compounds can be used as such or in the form of their preparations or in application forms prepared by further diluting the active compounds, such as prepared solutions, emulsions, suspensions, powders, liniments, and It can be used as granules. The active ingredient may be applied by conventional methods such as liquid application, dipping, spray application, atomization, vaporization, jetting, slurry formation, brushing, powder application, granulation, dry dressing, drop application. (moist
It can be used by dressing, wet dressing, slurry dressing or encrusting. When treating parts of plants, the concentration of the active compound in the application form can be varied within a considerable range. Generally, the concentration is between 1 and 0.0001% by weight, preferably between 0.5 and 0.01%. In the treatment of seeds, the amount of active compound is generally from 0.001 to 50 g/kg of seed, preferably from 0.01 to 50 g/kg of seed.
10g is required. For soil treatment, the concentration of the active compound is
Generally from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight, is required at the site of action. The compounds according to the invention are also suitable for the protection of industrial materials. Within the scope of the present invention, industrial materials refer to materials that do not themselves occur in nature, but are made from natural or artificial raw materials. Within the scope of the present invention, protected products refer to industrial materials that can be attacked and degraded by microorganisms. Examples of industrial materials that are protected from deterioration and destruction by microorganisms by the substance of the present invention include:
Adhesives, glue, paper, cardboard, fibers, leather, wood, paint,
Compositions, plaster products, cooling lubricants, sealing compositions and plastic products which can be attacked and degraded by microorganisms. The scope of materials to be protected further includes parts of manufacturing plants such as cooling water circulation systems and cooling circulation agent circulation systems.
These microorganisms can adversely affect operational efficiency. Preferably, the active compounds according to the invention can be used to protect adhesives, paper, cardboard, paint films, wood, etc. Microorganisms that can cause decomposition or deterioration of industrial materials are, for example, bacteria, fungi, yeast, algae, and slime-forming organisms. Preferably, the substances according to the invention have a strong and widespread action against fungi. In other words, this bactericidal action is effective against not only molds but also fungi that destroy and discolor wood. Examples include the following types of microorganisms: Alternaria, e.g. Alternaria tenuis, Aspergillus, e.g. Aspergillus niger, Aureobasidium, e.g. Aureobasidium pullulans , Chaetomium, e.g. Chaetomium globosum, Coniophora, e.g. Coniophora cerebella, Lentinus, e.g. Lentinus tigrinus, Penicillium ), e.g. Penicillium glaucum, Polyporus, e.g. Polyporus versicolor, Sclerophoma genus, e.g. Sclerophoma
pityophila), Trichoderma, e.g. Trichoderma viride. Depending on the field of application, the substances according to the invention can be converted into customary formulations such as solutions, emulsions, suspensions, powders, liniments and granules. These formulations can be prepared in known manner, for example by mixing the active compounds with liquid solvents and/or solid carriers, fillers, optionally emulsifiers and/or surfactants such as dispersants. If appropriate, organic solvents can be used as auxiliary solvents, for example when using extenders. Organic solvents for the active compounds are, for example, alcohols, such as lower alcohols, preferably ethanol, isopropanol, or benzyl alcohol, ketones, such as acetone, methyl ethyl ketone, liquid hydrocarbons, such as petroleum fractions, and chlorinated carbs. Hydrogen, for example 1,2-dichloroethane. The microbicides according to the invention generally contain from 10 to 100% by weight, preferably from 50 to 80% by weight, of halogenopropargylformamides as active compounds. The application concentration of the substance according to the invention is determined by the type and occurrence of the microorganism to be controlled and the composition of the material to be protected. The optimum amount to use can be determined by conducting a series of tests. Generally the application concentration is from 0.001 to 5% by weight, preferably from 0.01 to 5% by weight.
It is in the range of 1% by weight and is related to what material is being protected. The novel active compounds according to the invention can also exist in mixtures with other known active compounds. The following active compounds, namely benzimidazolyl carbamates, trihalogenomethylthio compounds,
For example, N-fluoro-dichloromethylthio-phthalimide and N,N-dimethyl-N'-phenyl-N'(fluorodichloromethylthio)-sulfamide, compounds that separate and release formaldehyde,
For example, hemiformals, phenol derivatives such as p-chloro-m-cresol, 2-phenylphenol and (2,2'-dihydroxy-5,5'-
Examples are dichloro)-diphenylmethane, dithiocarbamates, thiazolylbenzimidazole, isothiazolones and benzisothiazolone derivatives, dinitrile tetrachloroisophthalate, mercaptobenzothiazole and mercaptopyridine. Manufacturing Examples Example 1 Propargylformanilide, 32g (0.2mol)
was dissolved in 600 ml of methanol, and a solution of 10 g (0.25 mol) of sodium hydroxide in 30 ml of water was added.
Add at ~5°C. Then iodine 51g (0.2 mol)
was added in several portions over 1 hour at 0°C,
Stir for a further 4 hours at 0°C. Thin layer chromatogram shows complete conversion of starting material. The reaction mixture is stirred into a mixture of 2 ml of ice water and 10 ml of 40% strength sodium bisulfate solution (to decolorize the remaining iodine).
Crystallization occurs after some time. The crystals are suctioned off, washed with water and dried. Beige colored N-
Iodopropargyl-formanilide crystals 44g
(Yield, 77%) is obtained. After recrystallization from methanol, its melting point is 78°C. The starting material used in Example 1 was prepared in the following manner. Formanilide, 97 g (0.8 mol) was dissolved in 400 ml of tetrahydrofuran, potassium tert.
-butyrate, a solution of 90 g (0.8 mol) in 400 ml of tetrahydrofuran is added. After the exothermic reaction (salt formation) has ceased, the mixture is evaporated to dryness in a rotary evaporator. The residue was added little by little to a solution of 60 g (0.8 mol) of propargyl chloride dissolved in 500 ml of dimethylformamide.
The mixture is then slowly warmed to room temperature and stirring is continued for a further 20 hours until complete conversion of the starting material is determined by thin layer chromatography. The reaction mixture was reduced in weight by evaporation, extracted by shaking with methylene chloride water, and the organic layer was separated and concentrated by evaporation.
Then vacuum distillation is performed. 105~120℃/1.5mmH
The fraction g is propargyl formanilide.
The yield is 96 g (yield, 75%). The product is used in the iodination reaction without further purification. Example 2 Propargylformamide, 42g (0.5 mole)
Dissolved in methanol 1, sodium hydroxide,
A solution of 25g (0.6mol) dissolved in 80ml of water,
Add in portions while keeping at 0° C., and add iodine, 130 g (0.5 mol), in portions at the same temperature. The mixture was then stirred for a further 4 hours at 0°C, 5 ml of 40% strength sodium bisulfite solution was added under stirring to the solution of 2 in water, and the mixture was extracted by shaking three times with 300 ml of methylene chloride. death,
The organic layer is separated, dried over sodium sulfate and evaporated. The crude product, yield 45 g, is chromatographed on a silica gel column using ethyl acetate as mobile phase. 31 g (yield, 57%) of lightly colored crystals of iodopropargylformamide are obtained, recrystallized from water, with a melting point of 86-88°C. Propargylformamide used in Example 2 is produced by the following method. Into 600 ml of dimethylformamide, first 45 g (1 mole) of freshly distilled formamide were introduced, then 172 g (1.25 mole) of potassium carbonate.
and 186 g (2.5 moles) of chloropropyne are added and the mixture is heated. The exothermic reaction started at about 80-90°C, continued the reaction at 100°C with slight cooling, and then the reaction mixture was kept for another 15 hours.
Stir at 100°C. It is then concentrated by evaporation in a rotary evaporator and the residue is fractionated by silica gel column chromatography using ethyl acetate as mobile phase. 42 g (yield, 56%) of a pale liquid is obtained, which can be distilled at 120-125° C./20 m bars. The formula described below () The halogenopropargylformamides can be produced in the same manner as in Production Example 1 or 2 above. [Table] [Table] [Table] Formulas () used as starting compounds The propargylformamides were prepared analogously to Examples 1b) and 2b). [Table] [Table] [Table] The known compounds shown below are used as comparative substances in the following examples. 3×Cu(OH) ₂ ×CuCl ₂ ×H ₂ O (C) Example A Leptosphaeria nodorum
Nodorum test (wheat) / Protective solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether To prepare suitable preparations of the active compound, 1 part by weight of the active compound is mixed with the solvent in the above-mentioned amount. Mixed with emulsifier, the concentrate was diluted with water to the desired concentration. To test the protective activity, wheat seedlings were sprayed with the active compound preparation until mist droplets formed. After the sprayed mist droplets had dried, the seedlings were sprayed with a suspension of Leptosphaeria nodorum conidia and then placed in an incubation room at 20°C and relative humidity >100 for 48 hours. The seedlings were placed in a greenhouse at a temperature of approximately 15°C and a relative humidity of approximately 80%. Evaluation was performed 10 days after inoculation. In this test, the compounds according to the following Preparation Examples, for example, showed clearly superior activity compared to known compounds. Examples 5, 7, 6, 9, 12,
13, 14, 15 and 16, [Table] ＼

｜ Zn (A)
0.025 100
/

_CH2 -NH-C-S

‖

S

TABLE TABLE Example B Fusarium nivale test (rye)/seed treatment The active compound was used as a dry spray. These preparations were prepared by enriching the specific active compounds with mineral mills. It was a fine powder mixture and was reliably spread evenly over the seed surface. For smearing, infected seeds were shaken with the smear in a closed glass flask for 3 minutes. Two batches of 100 rye grains were sown in standard soil at a depth of 1 cm, and grown in a greenhouse at approximately 10°C and 95% relative humidity.
The seeds were grown in seed boxes exposed to light for 15 hours a day. Rye seedlings were evaluated for snow rot symptoms approximately 3 weeks after sowing. In this test, for example, it was shown that the compound according to the following production example clearly has superior activity compared to known compounds. Examples 5 and 9, [Table] [Table] Example C Venturia test (apple) / Protective solvent: Acetone 4.7 parts by weight Emulsifier: Alkylaryl polyglycol ether 0.3 parts by weight Appropriate formulations of active compounds For the preparation, 1 part by weight of the active compound was mixed with the above amounts of solvent and emulsifier and the concentrate was diluted with water to the desired concentration. To test the protective activity, young apple seedlings were sprayed with the active compound preparation until dripping. After the sprayed preparation had dried, it was inoculated with an aqueous suspension of molecular spores of the apple scab pathogen (Venturia inaequalis) and incubated at 20°C and 100% relative humidity.
The cells were placed in a culture room for one day. The young seedlings were then placed in a greenhouse at 20°C and approximately 70% relative humidity. Evaluation was performed 12 days after incubation. In this test, for example, the compound according to the following production example showed clearly superior activity compared to known compounds. Examples 15, 13 and 17, [Table] [Table] Example D Xanthomonas oryzae) test/Bacterial disease/Rice/Systemic solvent: Acetone 121.25 parts by weight Emulsifier: Alkylaryl polyglycol ether 3.75 parts by weight To prepare suitable formulations of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration. To test the systemic nature, 100 ml of the active compound preparation were sprinkled onto the standard soil on which rice seedlings had been grown.
Three days after the treatment, an aqueous suspension of the bacterial leaf blight pathogen was inoculated by injection. Then the rice seedlings were placed in the greenhouse for 24 hours.
It was kept at ~26°C and 70-80% relative humidity for 14 days and then evaluated. This test showed, for example, that the compounds according to the following Preparation Examples are clearly superior to known compounds. Examples 1, 16, 12 and 9. Table: Example E: Effect on fungi The compounds according to the invention were added to an agar medium made from beer wort and peptone in stepwise concentrations from 1 to 500 mg per test sample. After the agar had solidified, pure cultures of various test fungi were added to the agar samples thus prepared. After storage for 2 weeks at 28° C. and 60-70% relative humidity, evaluation was performed. Minimum inhibitory concentration
The Inhibitory Concentration (MIC), ie the lowest concentration of active substance present in the agar medium at which the microorganisms used no longer grow, was obtained. In this test, compounds that showed clearly superior activity compared to known compounds were, for example, compounds according to the following Preparation Examples. Examples, 11, 12, 13,
15, 17, 18, 5, 7, 14, 3, 4, 6 and 19. [Table] [Table] [Table]

Claims (1)

[Claims] 1 Formula () In the formula, R is hydrogen, alkyl, halogenoalkyl, cycloalkyl, alkenyl, alkynyl,
Halogenopropargyl formamides, wherein Hal represents halogenoalkynyl, optionally substituted aralkyl, and optionally substituted aryl, and Hal represents halogen. 2 In the formula () in claim 1,
R is hydrogen, alkyl with 1 to 20 carbon atoms, 1 to 5 halogen atoms and halogenoalkyl with 1 to 8 carbon atoms, cycloalkyl with 5 to 10 carbon atoms, 2 to 6 alkenyl having 2 to 6 carbon atoms, alkynyl having 2 to 6 carbon atoms, 1 to 3 halogen atoms and halogenoalkynyl having 2 to 6 carbon atoms, or 1 to 6 carbon atoms in the alkyl moiety having 6 to 10 carbon atoms in the aryl moiety, and the aryl moiety contains 1 identical or different substituents selected from alkyl groups having 1 to 6 carbon atoms and halogens. represents an aralkyl optionally substituted with ~5, or 1 to 6
Acyl with 1 to 6 carbon atoms, nitro, halogen, alkoxy with 1 to 6 carbon atoms, 1
The same or different selected from halogenoalkyl having ~5 halogen atoms and 1 to 6 carbon atoms, and halogenoakylthio having 1 to 5 halogen atoms and 1 to 6 carbon atoms 2. Halogenopropargylformamides according to claim 1, wherein Hal represents aryl optionally substituted with 1 to 5 substituents, and Hal represents fluorine, chlorine, iodine and bromine. 3 In the formula () in claim 1,
R represents hydrogen, alkyl having 1 to 18 carbon atoms, or phenethyl and benzyl, optionally substituted by 1 to 3 identical or different substituents selected from methyl, ethyl and chlorine; or the same or different groups 1 to 1 selected from nitro, methyl, ethyl, n- and iso-propyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, trifluoromethylthio and trichloromethylthio
Halogenopropargylformamides according to claim 1, wherein 3 represents phenyl optionally substituted, and Hal represents iodine and bromine. 4 formula () In the formula, R represents hydrogen, alkyl, halogenoalkyl, cycloalkyl, alkenyl, alkynyl, halogenoalkynyl, optionally substituted aralkyl, and optionally substituted aryl; -30 to 50 in a diluent in the presence of a basic substance
Characterized by the reaction at a temperature of °C, the formula () A process for producing halogenopropargylformamides, wherein R has the meaning given above and Hal represents a halogen. 5 formula () In the formula, R is hydrogen, alkyl, halogenoalkyl, cycloalkyl, alkenyl, alkynyl,
A pest control agent characterized by containing at least one type of halogenopropargylformamide, wherein Hal represents halogenoalkynyl, optionally substituted aralkyl, and optionally substituted aryl, and Hal represents halogen. .