CS196297B2 - Herbicide and fungicide - Google Patents

Abstract

1501811 Pesticidal application of pyridyltriazinones SUMITOMO CHEMICAL CO Ltd 20 Jan 1976 [21 Jan 1975 14 Feb 1975] 02231/76 Heading A5E [Also in Divisions A2 and C2] A method of controlling, innibiting or preventing the growth of plant-life or fungus comprises administering to the plant-life or fungus, or treating or impregnating a substrate on which the growth of plant-life or fungus is to be prevented with, a compound of the formula: wherein R is a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, a phenyl group or an alkoxycarbonylmethyl group whereof the alkoxy moiety contains from 1 to 3 carbon atoms. Optionally fungicides, insecticides, nematocides, acaricides, herbicides and fertilizers also may be present. Suitable compositions also are claimed.

Description

(54) Herbicidal and fungicidal composition

SUMMARY OF THE INVENTION The present invention provides a herbicidal and fungicidal composition for use in agriculture or industry, and not in medicine, containing as active ingredient at least one pyrldyltriazinone compound of formula I

where

A represents a group

R

I — NH — CH or

Whose nitrogen atom is bonded to the nitrogen atom in the above formula, and

R is hydrogen, C1 -C5 alkyl, for example methyl, ethyl, propyl, butyl or pentyl, alkoxycarbonylmethyl having an alkoxy moiety of 1 to 3 carbon atoms, for example methoxycarbonylmethyl, ethoxycarbonylmethyl or propoxycarbonylmethyl or phenyl.

Some of the pyridyltriazinone compounds of formula (I) are known [Nippon Kagaku Kaishi (Journal of the Japanese Chemical Society), 1973, pp. 1519-1522]. Some 1,2,4-triazin-5-one derivatives are also known to have herbicidal activity [Japanese Patents 315/1969 and 20 106/1970]. However, no one has studied the pyridyltriazinone compounds of formula I.

It has now been found that the pyridyltriazinone compounds of the formula I exhibit excellent herbicidal and fungidic activity. Their herbicidal activity is much greater than that of the known 1,2,4-triazin-5-one derivatives. As regards their fungicidal activity, they are effective against many species of phytopathogenic fungi. They also have considerable antimicrobial activity against various fungi and bacteria parasitizing on industrial and industrial products. It is preferred that the toxicity of the pyridyltriazinone compounds of formula I to mammals and fish is considerably low.

198297

Pyridyltriazinone compounds of the formula wherein the formula I comprises the two groups below, and the Ib and Ib compounds of the formulas Ia

R is as defined above.

A few specific examples of the pyrldyltrlazinone compounds of formula I are shown in the table below:

(Ia) (Ib)

Table I

CompoundNumber

Chemical formula

Melting point op

HIM

CH ₃

138—139

151—151,5

; Ύ · ν · _? ^? Λ5ί gc '- í;

182—164

167—168

217—219 (with decomposition)

124—126

19'6297

Compound Chemical formula - Melting point

Number ·. Noc: 2 ° C

The pyridyltriazinone compounds of formula I can be prepared by a variety of methods.

Process according to the invention for the production of pyridyltriazinone. The compounds of formula I are:. characterized in that picolinamdirazone of formula II is used

is reacted with a haloacetic acid or an ester thereof of formula III

R

AND

X — CH — COOR ’(ΠΙ) where

X represents a halogen atom, for example chlorine, bromine or iodine;

R 'represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, for example a methyl, ethyl or propyl group, and ·

R is as defined above, - in an inert solvent at a temperature from cooling to heating to give the pyridyltriazinone compound of formula Ia

an inert solvent to form a pyridyltriazinone compound of formula Ib

where

R is as defined above.

An inert solvent useful in the process of the present invention is, for example, benzene, chlorobenzene, toluene, xylene, ligroin, hexane, isopropyl ether, tetrahydrofirane, dioxane, chloroform, methanol, ethanol, isopropanol - or water; preferably, it is operated in the presence of an acid binding agent such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, pyridine, triethylamine, dimethylaniline, diethylaniline, over a wide temperature range, from cooling to heating.

The pyridyltriazinone compound of formula (Ib) can be prepared by oxidizing a pyridyltriazinone compound of formula (Ia). The oxidation can be carried out in an inert solvent such as methanol, ethanol, isopropyl ether, tetrahydrofuran, dioxane, acetone or chloroform, irradiated with light or an oxidizing agent such as chromic acid, perchromic acid, potassium permanganate, manganese dioxide, aqueous hydrogen peroxide or perbenoic acid.

The pyridyltriazinone compound of formula Ia or Ib thus obtained can be isolated from the reaction mixture by conventional methods, optionally followed by purification.

The following are a few specific examples of the preparation of the pyridyltriazinone compounds of Formula I.

where

R is as defined above, wherein - the compound is then optionally oxidized under irradiation with light, or - using an oxidizing agent in

He did

13.6 g of picolinamidrazone, 15 g of tri19 8 297 ethylamine and 100 ml of benzene are charged to a 200 ml 4-neck flask and the mixture is cooled to below 10 ° C with stirring. 18.4 g of ethyl bromoacetate are added dropwise with stirring at a temperature of 10 to 15 DEG C., followed by heating the mixture under reflux for 2 hours. The reaction mixture was then cooled and evaporated. the triethylaminated hydrobromide was filtered off. Removal of the solvent under reduced pressure gave 12.9 g of 3- (2-pyridyl) -1,4,5,6-tetrahydro-1,2,4-triazin-5-one as white crystals, m.p. 138-139. degrees Celsius.

Analysis for C8H8N4O:

calculated: 54.55% C, 4.55% / ο ·, 31.82% N; Found: C, 54.38; H, 4.63; N, 32.0.1. Example 2

A solution of 7.4 g of 3- (2-pyridyl) -6-methyl-1,4,5,6-tetrahydro-1,2,4-triazin-5-one in a 500 ml 4-neck flask is poured into 200 ml of acetone and a solution of 3.2 potassium permanganate in 200 ml of acetone are added dropwise at 10 to 15 ° C with stirring. The resulting mixture was stirred for 2 hours, then the manganese dioxide formed was filtered off. Distillation of the acetone under reduced pressure yields

6.5 g of 3- (2-pyridyl) -6-methyl-4,5-dihydrol-1,2,4-triazin-5-one as white crystals, m.p. 299-300 ° C.

Analysis for C9H8N4O:

calculated: 57.45 θ / ο C, 4.26 θ / ο H, 29.79 θ / ρ N; Found:% C, 57.31;% H, 4.22;% N, 29.95.

The pyridyltriazinone compounds of the formula I are characterized by a strong herbicidal action against grass weeds such as Echinochloa clus-gally and Digitaria sanguinalls, and against weeds on sloping and paddy fields, such as broadflower sp. (Cyperus difforuds), Amaranthus retroflexus, Chenopodium album, Stellaria media and Rotala (Rotsla indica Koehne). Their herbicidal effect is apparent in foliar application and also in pre-emergence use. Their selectivity is so remarkable that they do. many crops such as rice (plants), wheat, radish, soybean, cotton, flax, corn and canola do not have a detectable detrimental effect. Accordingly, the pyridyltriazinone compounds of formula I are useful as herbicides for fields, paddy fields, orchards, racecourses, pastures, forests and groves, non-agricultural soils, etc.

When the pyridyltriazinone compounds of the formula I are used as herbicides, they can be used as such or in the form of any formulations such as dusts, granules, fine granules, wettable powders and emulsifiable concentrates. in combination with solid and liquid carriers. Solid carriers include, for example, talc, bentont, clays, kaolin, diatomaceous earth, vermiculite, slaked lime, etc., while liquid carriers include, for example, benzene, alcohols, acetone, xylene, methylnaphthalene, dioxane, cyclohexanone, etc. applied in combination with surfactants for agricultural use, for example with auxiliaries to support and ensure their herbicidal effect, or they may. applied in combination with agricultural chemicals such as fungicides, insecticides and fertilizers. They can also be used together with any other herbicides.

In general, the pyridyltriazinone compounds of formula (I) may be present in the compositions of the invention for herbicidal use at a concentration of 0.1 to 95% by weight.

Very often, the pyridyltriazinone compounds of the formula I are formulated as concentrated formulations which are applied either to the soil or to the leaves in the form of aqueous dispersions or emulsions containing the active ingredient in an amount of 0.1 to 5% by weight. The water-dispersible or emulsifiable compositions are either solids, usually known as wettable powders, or liquids known as emulsifiable concentrates. These concentrated formulations may be used in% by weight of pyridyltriazinone.

compound of formula I 10 - 80 surfactant - 3 - 10 inert, carrier 87 - 10

The wettable powders comprise a intimately mixed, finely powdered mixture of the pyridyltriazinone compound of formula (I), an inert carrier and a surface. active substances. The concentration of active compound is usually in the range of 10 to 90% by weight. The inert carrier is usually selected from the group consisting of attapulgite clays, kaolin clays, montmorillonite clays, diatomaceous earths and purified silicates. Active surfactants comprising 0.5 to 10% by weight of wettable powder are sulfone lignins, condensed naphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates and nonionic surfactants such as phenol ethylene oxide adducts.

Typical emulsifiable concentrates of the pyridyltriazinone compounds of the formula I are characterized by a suitable concentration of the active compounds, for example 100-500 g / liter of liquid, which are dissolved in Inert.

the sulfur which is a mixture of water and the solvent. and emulsifiers. Suitable organic solvents are aromatics, especially xylenes, and petroleum fractions, especially high boiling naphthenic. and olefinic proportions of oil. Many other organic solvents, such as terpenic solvents, and complex alcohols, such as 2-ethoxyethanol, can also be used. Suitable emulsifiers for emulsifiable concentrates are selected from the same types as surfactants used for wettable powders.

If the pyridyltriazinone compounds of the formula I are to be applied to the soil, as in pre-emergence application, it is suitable to use them in granular form. Such a formulation typically comprises the active ingredient dispersed on a granular inert material such as coarse ground clay. The size of the granules is usually in the range of 0.1 to 3 mm. Conventional preparation of granules involves dissolving the active ingredient in a cheap solvent and applying the solution to the carrier in a suitable mixer. Granular compositions generally have a composition within the following range:

% by weight pyridyltrlazinone compound of the formula I 1 - 10 surfactant 0 -> 2 inert carrier 99 - 88

In a somewhat less economical process for preparing these compositions, the pyridyltriazinone compounds of formula (I) can be dispersed in wet clay or, in any other inert carrier, after which the resulting dispersion is dried and coarsely ground to give the desired granulate.

However, the most suitable application rate of the weed-effective pyrldyltriazinone compounds of the formula I varies according to the method of application, the climate, the soil type, the water content and the organic matter in the soil and other circumstances known to the agricultural expert. However, it has been found that the optimum usable amount in almost all cases is in the range of 25 g to 30 kg / ha. Optimum amounts will generally be in the preferred range of 25 g to 10 kg / ha.

The time at which the soil is to be treated with the pyridyltriazine compounds of the formula I or applied to the weeds is very variable, since these compounds are effective in both pre-emergence and post-emergence applications. Whether the weeds are in the growth or germination stage, at least partial results are always obtained by using the compounds according to the invention. The compositions of the invention may also be applied to the soil during rest periods to destroy the skin

1Д • size that germinates in the next warm season.

When the pyridyl triazinone compounds of the formula I are used against weeds in livestock plants with an annual vegetation cycle, it is usually best to apply them in the pre-emergence stage to the soil while the crop is sowing or planting. Soil is usually worked immediately before sowing or planting. If the composition is to be applied to the soil surface, it is easiest to treat the soil immediately after sowing or planting.

The following are some specific examples of herbicidal compositions of the present invention wherein the parts by weight of percent are parts by weight and the compound numbers used as active ingredient correspond to the compound numbers in Table 1:

Example A

A wettable powder of parts of Compound No. 6, 5 parts of a surfactant, i.e. polyoxyethylene alkyl ether, and 7 parts of talc are ground to a powder and mixed thoroughly to give a composition of the invention as a wettable powder containing 25% active ingredient.

Example В

Emulsifiable concentrate

30 parts of compound No. 9, 20 parts of surfactant, i.e. polyethylene glycol ether, and 50 parts of cyclohexanene were thoroughly mixed to give the composition of the invention. in the form of an emulsifiable concentrate containing the active ingredient at a concentration of 30%.

Example C.

Granulate parts of Compound No. 1, 40 parts of bentonttU; 5 parts of clay and 5 parts of sodium lignosulfonate are pulverized and mixed well. The resulting mixture is kneaded thoroughly with water, granulated and dried to give a granulate containing the active ingredient at 5% concentration.

Example D

The granulate parts of Compound No. 5 and 97 parts clay are finely pulverized and mixed intimately to produce a granulate containing the active ingredient in the clay.

3% concentration.

9 2 2 9 7 11

PTexample Es · ''. ··· Reinforced granulate · ’·

:. 5 parts of Compound No. 2, 4 parts of sodium lignosulfonates, 86 parts of clay and 5 parts of water are bent in a ribbon mixer. .Prohnětená ^{mixture, is} dried · 'and granulated to sev.získá formulation according, to the invention in the form of fine granules, containing the active ingredient in 5% -koncentraci.

. The pyridyl triazinone compounds of formula I can be used against plant diseases. They are particularly effective for reducing or completely eradicating the occurrence of plant diseases, such as cancer or root rot of vegetable root (Sclerotlnla sp.) And gray mold on vegetables (Botrytis sp.j.). They also have a strong protective effect against plant pathogenic microorganisms rot, blemishes and other diseases, for example against Pyricularia oryzae, Pellicularia saisakii, Cochliobolus miyabeanus, Pellicularla sasakii, Cochliobolus miyabenaus, Xanthomonas oryzae, Sclerotinia cinerca, Sclerotisia sp. Phytophthora Infestans, Alternaria kikuohiana, Alternaria mail, Glomecella cingulata, Alternaria solani, and Xanthombnus citrl, are therefore effective as fungicides in agriculture.

The pyridyltriazinone compounds of the formula I also exhibit a strong antimlrobial action against microorganisms other than the aforementioned pathogenic microorganisms. It can therefore be used in various industrial products or articles, such as plastic resins, paints, paper products and fiber products, to protect against attack or damage by bacteria or fungi. They can also be used as antimicrobial agents, detergents, antiseptics, etc. In addition, they are effective against tubers, algae and other harmful organisms that attach to various bodies in the sea and thereby damage them so that they can be used in various preparation farms, for the protection of industrial water, cooling water and paper production, as they prevent the formation and formation of slime, algae, etc., which are formed in water.

An advantageous property of the pyrldyltriazinone compounds of formula I is that they are very low in mammalian and fish toxic and almost non-irritating to the skin, even at concentrations in use. They are therefore very safe and practical.

They can be used to kill algae and microorganisms or to control harmful organisms in water in any of the usual dosage forms such as dusts, wettable powders, oil sprays, aerosols, tablets, emulsifiable concentrates, granules, fine granules and fumigants.

In general, the preferred content of active ingredient (optionally including other active ingredients) in the composition is from 0.1 to 95.0. % by weight, preferably 0.2 to 90.0% by weight, and a suitable application rate of active ingredient is usually in the range of 10 g to 30 kg / ha, preferably in the range of 100 g to 20 kg / ha. When used on the fields the active ingredient. usually used at a concentration of 1.0 to 0.01% by weight, depending on what is to be treated. The amount of concentration used depends on the dosage forms, the time of use, the methods of treatment, the locations and objectives of the treatment, etc., so that they can be varied arbitrarily regardless of the above range. The above compositions can be effectively used by any method of application, for example by dusting, spraying, granulating, spreading, soil treatment, coating, dipping and the like.

The pyridyltriazinone compounds of the formula I can also be used in the form of so-called economical sprays, for example in concentrations of up to 95% by weight of active ingredient or even 100% by weight of active ingredient. In the case of granules, particles of uniform size corresponding to a sieve of 10 mesh / mm are produced, the amount of which is adapted to the intended use.

The pyridyltriazinone compounds of formula (I) may also be used in combination with other chemical agents such as

Blasticldin-S, Kasugamycin, Polyoxin, Caldammycin, Cellocldin,

3- [2- (3,5-Dimethyl-2-oxocyclohexyl) -2-hydroxyethyl] -glutarimide, streptomycin, griseofluvin, pentachlorotrobenzene, pentachlorophenol, hexachlorobenzene, trichlorofluoromethane, 1,1,1-trichloro-2-nitroethane, dichlorodithromethane trlchlornltroethylen,

1,1,2,2-terachlornitroethane, methylene blsthocyanate,

2,6-dichloro-4-nitraniline, zinc ethylene-bls-dithiocarbamate, zinc dimethyldthiocarbamate, manganese ethylene bis-dithiocarbamate, bis (dimethylthlokarboamoyl) disulfide 1d,

2.4.5.6- tetrachloroisophthalonitrile,

2,3-dichloro-1,4-naphthoquinone, tetrachloro-p-benzoquinone, p-dimethylaminobenzenedlazonatrlumosolfonate,

2- (1-methylheptyl) -4,6-dinitrophenyl crotonate, 2-heptadecylimidazoline acetate,

2,4-dichloro-6-6 (o-chloroaniline) -S-trlazine, dodecylguanidine-acetate, 6-methyl-2,3-chloroxaline dithiol-1'-cyclic-S, S-dithiocarbonate,

2,3-chloroaldehyde-thiol-cyclictri-thiocarbonate,

6 219 7

N-Trifluoromethylthlo-4-cyclohexene-1,2-dlcarboxyimide

N- (1,1,2,2-tetrachloroethylthio) -4-cyclohexene-1,2-dicarboxyamide,

N- (dichlorofluoromethylthio) -N- (dimethylsulfamoyl) aniline,

1,2-bis- (3-methoxycarbonyl-2-trio ureido) benzene,

1,2-bis- (S-ethoxycarbonyl-4-thioureido) benzene,

2-amino-1,3,4-thiadiazole,

2-amino-5-mercapto-1,3,4-thiadlazole, O-phenylphenol,

N- (3,5-dichlorophenyl) maleimide, N- (3,5-dichlorophenyl) succinimide, N- (3,5-dichlorophenyl) imaconamide,

3- (3,5-dichlorophenyl) -5,5-dimethyloxazolidine-2,4-dione,

2,3-dihydro-5-carboxanilide-6-methyl-1,4-oxathiine-4,4-dioxide,

2,3-dihydro-5-carboxanilide-6-methyl-1,4-oxathiin,

1- (N-butylcarbamoyl) -2-methoxycarbonylaminobenzimidazole, b, O-diisopropyl-S-benzylphosphorothioate, O-ethyl-SS-diphenylphosphorothioate, O-butyl-S-benzyl-S-ethylphosphorothioate, O-ethyl- Of enyl-O- (2,4,5-trichlorophenyl) phosphate,

O, O-dimethyl-O- (3-methyl-4-nitrophenyl) -phosphorthloate,

S- [1,2-bis- (ethoxycarbonyl) ethyl] 0,0-dimethylphosphorothioate,

0,0-dimethyl-S- (N-methylcarbamoylmethyl) phosphorothioate,

O, O-dlethyl-O- (2-isopropyl-6-methyl-4-pyrimidyl) thiophosphate,

3.4-dimethylphenyl-N-methylcarbamate, magnesium methanarzomate, ferric methanarzonate,

2-chloro-4,6-bis- (ethylamino) -S-triazine,

2,4-dichlorophenoxyacetic acid (including salts and esters,

2-Methyl-4-chlorophenoxyacetic acid including salts and esters

2,4-dlchlorophenyl-4'-nitrophenyl ether, sodium pentachlorophenolate,

N- (3,4-dichlorophenyl) propionamide

3- (3,4-dichlorophenyl) -1,1-dimethylurea, α, α, α-trifluoro-2,6-dlnitro-N, N-di-n-propyl-

-p-toluidine, 2-chloro-2 ', 6'-diethyl N- (methoxymethyl) acetamide, 1-naphthyl-N-methylcarbamate, methyl N- (3,4-dichlorophenyl) -carbamate,

4-chlorobenzyl-N, N-dimethylthiolcarbamate, N, N-diallyl-2-chloroacetamide, O-methyl-O- (3-methyl-6-nitrophenyl) -N-sec-

-butylphosphorthioamidate,

5-n-Butyl-S '- (p-tert-butylbenzyl) -N-

- (3-pyridyl) pyrimidoclocarbonate a

Sn-heptyl-S ^{'(p-tert-butylben:} 1 zy] -N-3-pyridyl) imldodíthlokarbonát

In these cases, the individual active ingredients in the mixed composition are not characterized by a reduction in their own herbicidal or fungicidal action, so that these compositions can be used simultaneously against two different species of harmful organisms simultaneously.

In some combinations, a synergistic effect is observed due to the mixing, which is sufficiently effective. . · «

The pyridyltriazonone compounds of formula I can also be used in conjunction with other agricultural chemicals such as fungicides, nematicides and acaricides and / or fertilizers.

For industrial use, the pyridyltrlazonone compounds of formula I can be used in pure form without the addition of other inert ingredients. They are soluble in most solvents, so that suitable forms of preparation, such as solutions, can be formulated with other inert ingredients (various carriers) and used by mixing the industrial products with them or by applying them to the industrial products or injected or immersed in industrial products, etc., as is most appropriate in the present case.

When the pyridyltriazinone compounds of the formula I are applied for industrial purposes, they can be directly incorporated into the materials to be protected, for example, fibrous materials (especially cellulose or viscose composite materials), materials containing substrates of synthetic resins, such as are polyamide or polyvinyl chloride, in casein-containing paints or varnishes, in organic or inorganic pigments, in thickeners made from starch or cellulose derivatives, in animal viscous materials or oils, in polyvinyl alcohol-containing conditioning agents, in cosmetics such as soap or cream, in ointments, powders, in tooth powders and the like. Furthermore, the compounds of the invention may be used in the form of an aerosol, a chemical detergent, an organic solution for impregnating wood and an emulsified solution.

It is also possible ^! The pyridyltriazine compounds of the formula I can be used for the protection of perishable substances, such as leather, paper and the like, in the form of an aqueous suspension together with a wetting agent or dispersing agent.

A preferred use of the pyridyltriazinone compounds of formula I is to disinfect the washed articles and to protect them against attack by microorganisms. For this purpose, the pyridyltriazinone compounds of the formula I are preferably used in the form of a wash liquor which contains a concentration of 0.1 to 500 ppm. However, the concentration is not always limited to this range.

The pyridyltriazinone compounds of formula I are soluble in most organic solvents, whether hydrophilic or non-water-miscible, such as benzene, xylene, ether, dioxane, acetone, methylisobutylketone, cyclohexanone, isophorone, chloroform,

19829 7 trichloroethane, methylcellosolve, ethylcellosolve, butylcellosolve, dimethyiformamide, dlmethylsulfoxide, acetonitrile, methylnaphthalene and the like

The pyridyltriazinone compounds of the invention may be advantageously used in combination with the fungicides listed below, which are commonly used for industrial purposes; the effect of the individual active ingredients is not reduced by the combination, but on the contrary, a synergistic effect occurs; halogenated phenols such as pentachlorophenol, 2,4,5-trichlorophenol and their salts, copper compounds such as cuprous oxide, cupric oxide and copper naphthate, tin compounds such as blf- (tributyltin) oxide, bis (tributyltin chloride) , bis (tributyltin) acetate and bis (tributyltin) hydroxide (in which case the tributyl group may be replaced by a trialkyl or triphenyl group), aminobenzoic acid esters such as butyl p-amlnobenzoate, salicylic acid derivatives such as salicylanilide and halogenated salicylanilide , chlorhexidine, monoalkyl-bis- (aminoethyl) glycine and its salts, 1,2-benzisothlazolin-3-one, benzyl bromoacetate, 2- (4-thlazolyl) benzimidazole, p-chloro-m-xylenol, 2,2'-dihydroxy-5 5'-dichlorophenylmethane, dehydroacetic acid, formalin, nitrofurans, oxycholine, ο-phenylferiol-, biphenyl-, cresol soap, creosote, dimethylzinc, dithiocarbamates, benzthiazoles, methylene-bis-thiocyanate etc.

The following are some specific examples of a composition suitable for fungicidal use in which parts and percentages are by weight and the compound numbers used as active ingredient correspond to the compound numbers in Table 1.

Example O

A wettable powder of parts of Compound No. 1, 5 parts of a wetting agent, i.e. an alkylbenzene sulfonate and 45 parts of diatomaceous earth is pulverized and thoroughly mixed to give a composition according to the invention as a wettable powder containing the active ingredient in 50% concentration.

Example P .... ;

The dusting of parts of Compound No. 2 and 93 parts of clay is pulverized thoroughly mixed. thereby obtaining a composition according to the invention in a dusting farm comprising a component in 7%. concentration.

Example 1 a d Q

Pellets of parts of Compound No. 3, 35 parts of btontonite, 52 parts of clay and 5 parts of sodium lignin sulphonate are pulverized and mixed thoroughly. The mixture is bent with water and pellets containing the active ingredient in an 8% concentration are produced.

Claims (9)

Example 1 a d R Emulsifiable concentrate 20 parts of Compound No. 4, 15 parts of emulsifier, i.e. polyoxyethylene glycol ether and 65 parts of cyclohexanol are mixed intimately to give the composition of the invention in the form of an emulsifiable concentrate containing the active ingredient at 20% concentration. Example S Granulate 5 parts of Compound No. 5, 93.5 parts of clay and binder, i.e. polyvinyl alcohol, are sufficiently ground and mixed thoroughly. The resulting mixture is kneaded with water and granulated, and the resulting granulate is dried to give a composition of the invention containing the active ingredient in a 5% concentration. The results of several tests demonstrating the herbicidal and fungicidal effects of the pyridyl-triazinone compounds of formula I are shown in Table 2 below, where parts are by weight. In these examples, the compound numbers of the invention correspond to the compound numbers listed in Table 1, while the numbers of the known compounds listed for comparison correspond to those in the following table: 19B297 Table 2 Compound number Chemical formula Literature li ln iv? Japanese patent number 20106/1970 Japanese patent number 20106/1970 Japanese patent number 20106/1970 Japanese patent number 315/1969 Japanese patent number 20106/1970 See Japanese Patent No. 20106/1970 H ^^ posed Pre-emergence application Using Dlgitalia 'sanguinalis as a representative of grass weeds,' kindness. bent. '(Amaranthus' retroflexus) '' and 'white goosefoot' (Chenopcdium album) 'as' representatives of broadleaf 'weeds' and 'wheat and' radishes as 'representatives of crops' are 'transmitted by seeds' of grasses and 'crops individually' into. "Pots with a diameter of 10 cm and cover the soil with soil." Each of the emulsifiable concentrates containing the compound to be investigated was diluted with water and treated with potted soil by means of a hand sprayer. Flowerpots' with - 'sown' grasses and. The crop was placed in a greenhouse and 20 days after the treatment for the highly active herbicidal activity of the compound. Herbicidal efficacy is marked with 'one' of the values on the following scale 'pd 0 to' 5: · Value 'Percent' of Inhibition '' ('%) 0: 1 - ^: 2 -. · - ··. 40 3 60 · - ’··· '· 4 ··. · ··· · 80 5 ·; 400 '' ' The results are shown in the table. 3. 196237 2D Table 3 Compound number · Application rate (kg / ha) Tree frog ’ Radish Amaranth bent Wheat 1 2 5 1 5 2 2 ·. 5 1 5. 3 2 5 1 5 4 10 5 5 5 · 5 2 5 1 5 6 2 5 1 5 7 • 2 5 1 4 · 8 2 5 1 3 9 2 5 1 4. 10 10 5 _._.  5 ·: · .5 i γ-ν; 2. 4. 1 3 ’ in 2 4 1 3 she knows .: .., .. 1 · ,; Г ‘. -1 2 - Example 2 Application to water control A 14 cm diameter Vagner pot is filled with 1.5 kg of soil for irrigation (rice) polt and this is brought; to the state. Plants are planted in the pot, stalked in 3 leaves, and seedling of the hedgehog's feet (Echinochloa crus-galii) is sown. Twenty-five days after application, the herbicidal activity and the phytotoxicity of the test compound are examined on planted and sown plants and on spontaneously germinating / broadleaf weeds such as (Monochoría vlaginalis Presl.), (Llndernapyxidar). and Rotala indica Koehne). For p administration, pipettes are used to deliver a wettable powder containing a selected amount of the test compound at 15 ipl / pot. The herbicidal activity found is evaluated on a scale of 0-5. 0 5 0 0 5 0 2 5 0 O 5 0 1 5 0 •.-0 5 0 0 5 0 0 5 0 • 1 · 5 0 ..-O 5 0 2 5 0 0 5 0 0 5 0 0 3 0 0 5 0 0 3 0  0 5 0 0 3 0 0 5 0 . 0. 5 0 4 4 4 4 2 4 4. 4 1 3 2 0 4 3 4 .-: 4- ' 2 3 Value • Percentage inhibition (%) 0 0  : 1 - - 20 May 2 40 3 60 4 80 ..... 5 100 ALIGN! In assessing phytotoxicity, three factors are determined, grass height, number of shoots and total weight (dry matter), and for each factor the ratio of values obtained on treated and untreated soil is determined. Phytotoxicity is evaluated based on. the lowest value of the three ratios, and is indicated by a value from 0 to 5. 100 ALIGN! Comparison with untreated Degree of soil (%) Ό ^- 1. The results are shown in Table 4. 2?  Table 4 Compound. Applied, Herbicidal activity Phytotoxiclta number quantity. hedgehog broad-leaved (wheat) (kg / ha) corns foot weed  1 ' 2 5 5 1 г 5 5 0 2 2 5 '5 1 1 5 5 0 3 2 5 5 0 3 0 4 10 4 5 0 5 ; 4 4 0 5 2 -; ··. 5 5 1 1 5 5 0 , 6 2 5 5 1 .. _χ 5 5 0 7 5 4 1 -1 · ’'’ ··' 4 4 0 8 2- ^;; ' '5 4 1 . -.j, ·· ' 3 4 0 9 2 5 4 1 1 4 4 0 10 10 '' '5 5 0 5 5 5 0 1 2 3 2 2 1> .. -. / 2 1 1 in 2 3 . 3 3. 1 1 2 . 2 vi 2 · 3 3 2  1 ....... ·· ...... 3 2 .. ........ .......... 1 Example 3 containing the quantity selected compounds, se rice plants splatter in Protective; effect against Pyrlcularia orysae quantity 7 ml / flower pot. After one day he is the plants spray with a spore suspension of Pyricula- A 10 cm diameter pot is grown ria orysae and figs with fungicidal activity eats rice plants of the variety Wase-Asahi compounds of interest. Percentage of efficacy dia 3 sheets. Each of the investigated solutions, calculated from the following equation: 7 number of illnesses \ / number of diseases \ ( stains on plants) - I spots on plants j Percentage \ z neošetř. surfaces j у from treated areas j 100 ALIGN! efficiency = number of disease spots on plants ^л (° / o) from untreated surfaces The results are listed in Table 5. T a b u 1 k a 5 Compound Concentration Percent Phytotoxicity number active ingredient efficiency (PPm) (%) 1 100 ALIGN! 100.0 it is not 2 100 ALIGN! 100.0 it is not 3 100 ALIGN! 100.0 it is not 4 100 ALIGN! 93.7 it is not 5 100 ALIGN! 100.0 it is not -6 ................ 100 98.8 it is not 7 100 ALIGN! 99.2 it is not 8 100 ALIGN! 96.4 it is not 9 100 ALIGN! 97.5 it is not 10 ^; 100 ALIGN! 92.6 it is not and 100 ALIGN! 5.4 it is not untreated - 0 - - 199 29 7 Example 1 a d 4 Use in washing solution One part of the test compound, i.e., Compound No. 1, 2, 5, 6 or 9, is dissolved in 20 parts of dimethylsulfoxide and the resulting solution is added to a wash solution containing sodium soap at 1.5 g / liter. so as to obtain a concentration of 25 mg of the test compound in 1 liter of 'wash' solution. One part of a white cotton fabric is immersed in 20 parts of the washing solution so prepared and the washing solution containing the contents is heated to 80 DEG C., where it is left for 20 minutes. The fabric is then rinsed first for 40 minutes, then again for three minutes in soft water. After rinsing, the fabric is dehydrated in a centrifuge, then dried and ironed. The 20 mm diameter test discs were cut from the fabric so washed and placed on agar in a Petri dish inoculated with either Staphylococcus aureus 209 P or Escherichia coli K-12 and then placed in a 37 ° incubator. C for 24 hours. After incubation. to find that mlkroorga? nlsmy do not live on the test discs treated with the 'Compound' Compounds number 1, 2, 5 and 9 and that an area where the microorganism is not present is formed at the edge of the test discs placed on the agar. Example 1 a d 5 Protection of fresh fish from spoilage A 1% aqueous solution of the test compound is prepared and added to seawater to achieve the selected concentration of compound. The mackerel is then immersed in the sea water for about 30 minutes, then dried and left in the refrigerator at 5 ° C. Determination of the amount of volatile basic nitrogen contained in the fish by the Kjeldahl method determines the degree of freshness of the fish. . The results are shown in Table 8. Table 6 Compound Concentration number of the active ingredient in seawater. (PPm). The amount of volatile basic nitrogen (mg%) after 3 days after 8 days. after 12 days 1 5 10 18 28 2 . 5. 10 21 31 4 5 10 19 Dec 30 .5 5. 10. 17. 28 6 5 . 11 20 May 30 10 5 10 18 29 . i. • 5. 15 Dec 36 71 ili. 5 16 39. , 73 untreated 0 18 46 80 Example 6. Use in synthetic resin 65 parts of polyvinyl chloride powder, 35 parts of dibutyl sebacate, 2 parts of dibutyltin dilaurate and 0.5 parts of test compound, ie compound No. 1, 2, 5 or 6 are mixed and the resulting mixture is uniformly kneaded at 160 degrees. Celsia po. 10 minutes on mixing. calender, then 'extruded' into a 'foil' with a thickness of 0.3 mm. The test specimens in the form of 20 mm diameter wheels were cut from this film and processed in the same manner as in Example 4. The test specimens treated individually with Compounds Nos. 1, 2, 5 and 6, respectively. neither staphylococcus (Staphylococcus. aureus 209. P) nor bacteria (Eschirichia coli K-12) can be detected; around the edge of the test discs placed on the agar, an area where microorganisms are absent is formed. Example 1 a d 7 'Sieve water' protection 10 g of each of the compounds to be examined, i.e. compounds 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10, are dissolved or 'suspended' in 100 ml of water, and 5 ml of each of these solutions is diluted with 1 liter of sieve water from wood pulp production. 5 ml of each of the resulting solutions was further diluted with 2 liters of sieve water. To 100 ml of the 'test' solution thus obtained is added. 10 g of grape sugar, 1 g of peptone, 0.05 g of magnesium sulphate and 0.01 g of calcium chloride are obtained, the mixture is sterilized by heating and inoculated with a second. (Bacillus sp.), Isolated 'from' sludge resulting from the 'papermaking' process. Reproduction. microorganism cannot be detected at all. · Example Use in paint. Material parts test compound 10 zinc oxide 20 May iron oxide : .10 precipitated sulfate. . barium - 10 linseed oil . 10 rosin 20 May heavy gasoline 20 May Three grams of paint prepared in accordance with the above regulation,. are applied with a brush on a polyvinyl chloride chloride plate of 30 X 20 X 0.5 cm; Each of these plates is mounted in a wooden frame and dipped into the sea so that the lower half of the plate is below the surface (June 20). After two months, the plate is removed from the water and the protective effect is determined and evaluated according to how much of the surface area the marine organisms have taken up. The measure for evaluation was as follows: .. 28I •. i 'Scale for · -. . evaluation. . . Relative size ..areas 0 ^; without microorganisms 1 do ·. 2% 2 2 to 5% · '3 · ... 5 to 20% 4; '· -: · L.:. 4'20 to 60% 5 V ” over 60% The results 'are' shown in Table 7. Table 7 Marine organisms Compound suz · ^v t sea salad vilejš number. _v . Ulva lactuca ,. . stvolitý . 'i ^; ·. ' •. ' Q <'·' · · ’7 0. 2 0 1 · . . 1. • ·, ·. · -3 ? 0 1  1-r '- • -, 7: .4. ; 1 · ': 1 2 5 ··· ··. . . ·. , Ό.ν · ' 0. - 0 6 0 1 1 '7 .. 0 1 1 8 1 2, 2 9 '. . .. · - 1 2 2 10 1 1 2 1. /  / 3 4 4 11 · '. 4 4 5 lil 3 4 4 lv 4 4 5 check · '. ··· 5 ..... '. 5 5 Example 9 u: Antimicrobial efficacy The antimicrobial activity of the test compound (Compound No. 5) against the fungal fungi and bacteria was tested by the agar dilution method. In the case of filamentous fungi, the medium containing the test compound (potato agar) is inoculated with a 5 mm diameter disc and left at 27 ° C for a selected period of time. After that, the reproduction of the fungus is examined. In the case of bacteria, the medium containing the compound of interest (agar with cardiac muscle leach) is inoculated with a suspension of bacteria and left at a temperature. For 37 hours according to the Nippon Kagaku Ryoho Gakkai method. After this period has been determined. the degree of bacterial reproduction. The results are shown in Tables 8 and 9. Table 8 Types of fungi used in the experiment Incubation time (days) Minimal inhibitory. concentration (ppm) Aspergillus nlger 4 '··· - 100 Penlcillium citrinum 4 200 Rhyzopus nlgrlcans. 2 . 20 May Cládcoporium 'herbarium. 4 100 ALIGN! Chaetomium globosum ....... 3 10 18 8297 ' Table 9 The type of bacteria used in the experiment Minimum idle concentration (ppm) Sarcia lutea 50 Klebs-lella pneumonia 25 Proteus miřabilis 50 Proteus vulgaris 50 Pseudomona-s aerůginosa 50 Xanthomonas oryzae 10 SUBJECT . A herbicidal composition comprising, as active ingredient, at least one pyridyltrlazinone compound of the formula I wherein: VYNALEZU. an alkoxy moiety having 1 to 3 carbon atoms, or a phenyl group. pin. ·; 3. A process according to claim 2, wherein the active ingredient is a pyridyltriazinone compound of the formula: A represents a group of the formula 'R' • I-NH-CH or a group of the formula ...... -; · <*., —N = C -. ·, Jh; -v ·· - - R. the nitrogen atom of which is bonded to the nitrogen atom in the above formula, R represents a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, an alkoxycarbonylmethyl group having an alkoxy moiety having from 1 to 3 carbon atoms, or a phenyl group. On, - Ύ.- -. -. -._. - -. - - '.. 2. A composition according to claim 1, wherein the active ingredient comprises a pyridyltriazinone compound of the formula: 4. A composition according to claim 2, wherein the active ingredient is a pyridyltriazinone compound of the formula: 5. The composition of claim 1, wherein the active ingredient comprises a pyrldyltriazinone compound of the formula wherein: R represents a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, an alkoxycarbonylmethyl group having an alkoxy moiety having 1 to 3 carbon atoms, or a phenyl group. 6. A composition according to claim 5, wherein the active ingredient is a pyrldyltriazinone compound of the formula R is hydrogen, alkyl of 1 to 5 carbon atoms, alkoxycarbonyl or 196297 Н Г) has 1 to 3 carbon atoms or a phenyl group, characterized in that the plkolinamidrazone of the formula II 7. A composition according to claim 5, wherein the active ingredient is a pyrldyltriazinone compound of the formula and reacted with a haloacetic acid or an ester of the formula III. 8. A composition according to claim 5, wherein the active ingredient is a pyrldyltriazinone compound of the formula R AND X — CH — COOR ’(III) where X represents a halogen atom, R 'represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, and R is as defined above, in an inert solvent at a temperature of from cooling to heating to produce the pyrldyltriazinone compound of formula Ia for the preparation of pyrldyltriazinone A process for compounds of formula I (IJ) wherein where / A represents a group of formulas R is as defined above, which compound is then optionally oxidized under irradiation with light or using an oxidizing agent in an inert solvent to form a pyridyltriazinone compound of formula Ib or a group of formula whose nitrogen atom is bonded to the nitrogen atom in the above formula, and R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxycarbonylmethyl group having an alkoxy moiety