KR840000084B1 - Method of preparing for heterocyclic compounds havin fungicidal herbicidal and palnt-growth regulating properties - Google Patents

Abstract

The title compds. I (R1,R2=optionally substituted aromatic ring contg. 1-2 N. ph; R3=acyl; R4=H, C1˜C4 alkyl) were prepd. Thus, 18.3g 3-(3'-pyridylaminomethyl)pyridine in 50mL toluene was refluxed with 98% formic acid to give 27% 3-(3'-pyridylmethyl)amino-pyridine, which was added to a soln. contg. 2.8g trimethylacetylchloride and treated with 2.6g triethylamine to give 65% N-t-butylcarbonyl-3(3'-pyridylmethyl)aminopyridine.

Description

Method for preparing heterocyclic compound having bactericidal, herbicidal and plant growth control properties

The present invention relates to a method for preparing heterocyclic compounds useful as fungicides, herbicides and plant growth regulators.

Mr. Carelli et al. Pharmaco (Pavia) Ed. Sci. The article in pages 16, pages 375-81 (1961) states that the N-acyl derivatives of N-pyridylmethylanaline have pharmaceutical properties. US Pat. No. 4,082,851 relates to compounds having pharmaceutical properties and describes certain benzylaminoheterocyclic compounds substituted with SO ₂ NH ₂ groups.

It has been found by the present invention that the N-acyl derivatives of certain heterocyclic compounds have useful bactericidal, herbicidal and plant growth regulating properties.

The present invention is a compound of the general formula (I) or acid addition salts thereof. Provided are methods for inhibiting bacteria, including application of N-oxides or metal salt complexes to sites, and methods for inhibiting or controlling plant growth.

^One of R ¹ and R ² in the above formula (I) represents an optionally substituted 6-membered heteroaromatic ring containing 1-2 nitrogen atoms and the other represents the ring or optionally substituted phenyl group; R ³ is an acyl group derived from carboxylic acid; R ⁴ is an alkyl group or hydrogen atom having 1-4 carbon atoms.

Unless otherwise stated, the aliphatic moieties shown in R ¹ , R ² and R ³ preferably have up to 6 carbon atoms and more preferably up to 4 carbon atoms.

The acyl group represented by R ³ is, for example, a formyl group, an alkoxycarbonyl carbonyl group or an optionally substituted alkanoyl, alkenoyl, cycloalkanoyl or aroyl group. R ³ is most preferably derived from aliphatic or aliphatic cyclic acids.

Suitable substituents that may be present in the substituted alkenoyl or alkanoyl groups include halogen atoms and alkoxy, phenyl, phenoxy, carboxy or alkoxycarbonyl groups. These groups are preferably unsubstituted or substituted with up to three halogen atoms or with phenyl, phenoxy, C ₁ -C ₄ alkoxy, especially methoxy, methoxy carbonyl or ethoxycarbonyl groups. Particularly preferred alkanoyl and alkenoyl groups are unsubstituted groups having up to 6 carbon atoms in the alkyl or alkenyl moiety. Alkanoyl groups are preferred and tertiary butylcarbonyl groups are particularly preferred.

Optionally substituted cycloalkanoyl groups include those containing 3-6 carbon atoms in the ring, in particular cyclopropylcarbonyl and cyclohexylcarbonyl groups. Suitable substituents are halogen atoms or alkyl groups, in particular methyl groups. Thus optionally substituted cycloalkanoyl groups are, for example, cyclopropylcarbonyl, 1-methylcyclopropyl carbonyl, 2,2-dichloro-3,3-dimethylcyclopropylcarbonyl or cyclohexylcarbonyl groups.

The optionally substituted aroyl group is preferably an optionally substituted benzoyl group. Preferred substituents which may appear in the phenyl ring are preferably the same substituents as described below for phenyl ring R ¹ or R ² .

Suitable alkoxycarbonylcarbonyl groups are preferably those having 1-6 carbon atoms in the alkoxy moiety, for example a C ₂ H ₅ .O.CO.CO- group or a CH ₃ .O.CO.CO- group.

Thus typical R ³ is formyl, alkanoyl such as t-butylcarbonyl or 2,2-dimethylpropylcarbonyl, alkoxyalkanoyl such as methoxymethylcarbonyl, cycloalkanoyl such as cyclopropylcarbonyl, alkylcyclo alkanoyl such as 1-methylcyclopropylcarbonyl, and optionally substituted aroyl such as benzoyl optionally substituted with an alkyl or halogen atom of 1-4 carbon atoms.

R ⁴ is preferably a methyl group or a hydrogen atom.

The heteroaromatic ring represented by R ¹ or R ² , which may be optionally substituted pyrimidinyl, pyridazinyl, is better if it is a pyridyl or pyrazinyl ring, and the heteroaromatic or phenyl ring represented by R ¹ or R ² may be substituted. It may be unsubstituted. Preferably, the heteroaromatic ring is unsubstituted and the phenyl ring is mono-di-substituted. Rings are, for example, halogen atoms and nitro, alkyl, haloalkyl, hydroxyalkyl, alkoxy, haloalkoxy, hydroxyalkoxy or hydroxyl groups as well as cyano, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, carboxy and alkylti It may be substituted with the same or different one or more substituents selected from the group. It is preferred to be unsubstituted or substituted with one or two substituents, identical or different, selected from halogen atoms and alkyl, alkoxy and nitro groups. Most preferred is di-substituted halogen atom, especially fluorine or chlorine atom and alkyl especially methyl group.

If one or both of R ¹ and R ² are a pyridine ring, it is preferably linked to the NR ³ .CHR ⁴ portion of the molecule at the 3-position to the nitrogen atom ring. First preferred among the compounds useful in the process of the invention are those wherein R ¹ is an optionally substituted phenyl group and R ² is an optionally substituted pyridyl group, in particular a 3-pyridyl group. The compounds have very useful bactericidal properties.

A second preferred group of compounds is a compound in which R ¹ represents an optionally substituted pyrazinyl group and R ² represents an optionally substituted phenyl group. The compound has very useful plant growth regulating properties. In such compounds, the pyrazinyl group is preferably unsubstituted and the phenyl group is preferably substituted or unsubstituted with one or two of the aforementioned substituents. Especially preferred are compounds of general formula (I) wherein R ¹ is a pyrazinyl group, R ² is a 4-chlorophenyl group, R ³ is a t-butylcarbonyl group and R ⁴ is a hydrogen atom, acid addition salts thereof, N-oxides or metal salt compounds to be.

The compound of formula (I) forms an N-oxide; Forms acid addition salts with inorganic acids such as sulfuric acid or hydrochloric acid or organic acids such as citric acid and tartaric acid; Complexes with metal salts such as halogens, salts of calcium, copper and iron, and compounds of formula (I) form complexes in a ratio of 2: 1, 1: 1, or 1: 2. The use of such derivatives is also part of the invention and the derivatives can be prepared by methods analogous to those known from the compounds of formula (I).

The compounds of the present invention can be used to inhibit bacteria, in particular barley powder powdery mildew. Furthermore, the present invention can be used for two purposes of controlling and inhibiting plant growth as a result of the range of plant growth regulation properties and herbicidal properties of the compound of formula (I). Among the properties that inhibit crop growth regulation by various compounds of formula (I) include plant growth restriction, enlarged placental and dark green leaf formation, and short and broad leaf formation. These properties can be applied to the following applications using specific compounds under certain conditions: plant growth restrictions to reduce stress in plant tissues or to prevent large crops such as grains from falling over; Increase in photosynthesis per unit area as a result of the formation of dark green leaves that have excellent growth under poor light conditions; Production of green grass crops with lower water content than normal; Morphological control in horticultural crops such as chrysanthemum and poinsettia; Inhibiting the growth of unproductive flowers or vines in crops such as tobacco, cotton, alfalfa, beet or strawberry; By inhibiting growth at the end of the season, sugar cane maturation and certain compounds play a role in increasing the yield of crops such as soybeans.

Certain compounds of formula (I) are useful as "herbistats": that is, the application of compounds to crop seeds or the soil in which the crops are to be grown limits plant growth. This is useful, for example, in controlling land plants, planting hydroponic plants such as grains in farms or orchards, and reducing weed frequency in weed areas.

Plant growth control effects of compounds of formula (I) that last for a long time under certain circumstances can be corrected or reversed by applying plant hormones such as oxins, cytokinin, phytosterols, particularly gibberellic acid. Possible uses of these effects are, for example, seed treatment, where the seeds of the crop are covered with gibberellic acid and planted normally. Treatment of crop areas with compounds of formula (I) having herbicide or weed weeding properties inhibits weed growth, but the growth of crop seeds is not affected by the local environment of gibberellic acid. This is useful for crops such as sugar beet. Annual beets that grow with weeds are virtually impossible to suppress with conventional weeding methods.

Some commercial plant growth regulators tend to grow plants that are very sensitive to bacterial penetration. Therefore, its use as a plant growth regulator of compounds having plant growth regulation and bactericidal properties is very advantageous.

The compound of the formula (I) according to the present invention, an acid addition salt thereof, N-oxide or metal salt compound was suitably applied to the site in order to set it in an amount of 0.1-3 kg / ha. Most conveniently, the compounds are applied in the form of compositions containing one or more suitable carriers. The compounds of formula (I) are novel and therefore the present invention also provides these compounds. The novel compounds are compounds of formula (I), acid addition salts thereof, N-oxides and metal salt compounds. Wherein R ¹ , R ² , R ³ and R ⁴ have the above meanings and if R ¹ is an optionally substituted pyridyl group R ² should be an optionally substituted heteroaromatic ring; When R ¹ is an optionally substituted phenyl group, R ³ is an acyl group derived from an acid other than an optionally substituted benzoic acid; When R ¹ is an unsubstituted phenyl group, R ² is an unsubstituted 2- or 3-pyridyl group and R ³ is a structural CH ₃ CO-, C ₂ H ₅ CO-, (phenyl) ₂ CHCO- or phenyl. CH = CH.CO-, and R ⁴ should be an alkyl group; When R ² is a phenyl group substituted with a SO ₂ NH ₂ group, R ⁴ must be an alkyl group.

The preferred meanings of R ¹ , R ² , R ³ , R ⁴ in the novel compounds according to the invention are as given in the above process according to the invention.

The present invention provides a process for the preparation of novel compounds consisting of acylating a compound of formula II according to the present invention with an appropriate acylating agent.

Wherein R ¹ , R ² and R ⁴ have the same meanings given for the novel compounds of formula (I).

As a suitable acylating agent, for example, carboxylic acid, an acid anhydride derived from carboxylic acid, or preferably an acid halide can be used. Acid chlorides are particularly suitable and the reaction is preferably carried out in the presence of an acid binder which may be organic or inorganic base. Organic amines such as triethylamine are very suitable acid binders. The reaction is preferably carried out at a temperature of 50-150 ° C., preferably 60-100 ° C., in the presence of an inert solvent such as a hydrocarbon such as benzene. The reaction is conveniently carried out under reflux.

The compound of formula (II) can be prepared by reducing the compound of formula (IV).

In the above, R ¹ , R ² and R ⁴ have the meaning given to the novel compounds of formula (I). The reduction reaction can be carried out, for example, using hydrogen gas, a catalyst or formic acid. When formic acid is used, the reaction conditions are those of formula (I) in which at least some of the compounds of formula (II) produced formylated at this position and R ³ represents a formyl group starting from the compound of formula (III). You can choose to create your own.

Compounds of formula (II) can be prepared in a similar manner to those known in the art, for example by coupling compounds of general formula R ¹ NH ₂ with general formula R ² COR.

As described above, the plant growth inhibition and control method according to the present invention is carried out using a composition composed of the active compound and a suitable carrier. The present invention therefore provides a biologically active compound consisting of a novel compound according to the invention and a suitable carrier. Preferably the amount of active ingredient in the composition is 0.05-95% by weight of the composition.

The carrier in the composition according to the invention can be any substance which facilitates application to the site to be treated with the active ingredient, ie crops, seeds or soil and which facilitates storage, transport and handling. The carrier may be a solid or liquid, including a substance which is usually gaseous and compressed to be a liquid, and carriers commonly used in agricultural compositions may be used. Suitable solid carriers include natural and synthetic clays and natural silicas such as silicates such as diatomaceous earth; Magnesium silicates such as talc; Magnesium aluminum silicates such as attapulgite and vermiculite; Aluminum silicates such as kaolin, montmorillon and macas; Calcium carbonate; Calcium sulfate; Synthetic hydrated silicon oxide and synthetic calcium or aluminum silicate; Elements such as carbon and sulfur; Copolymers with natural and synthetic resins such as coumarone resins, polyvinyl chloride and styrene polymers; Solid polychlorophenol; Bituminous coal; Waxes such as milltops, paraffin oaks and chlorinated mineral waxes; And solid fertilizers such as superphosphates.

Suitable liquid media include water; Alcohols such as isopropanol and glycol; Ketones such as acetone, methylethyl ketone, methyl isobutyl ketone, cyclohexanone; Ether; Aromatic and cycloaliphatic hydrocarbons such as benzene, toluene, xylene; Petroleum fractions such as kerosene and diesel; Chlorinated hydrocarbons such as carbon tetrachloride, ethylene perchlorate, ethane chloride and the like. Different liquid mixtures are also suitable.

Agricultural compositions are prepared and shipped in concentrated form, which is significantly diluted by the user before use. The presence of a small amount of a carrier which is a surface active agent facilitates the dilution process.

Surfactants can be emulsifiers, dispersants or wetting agents and are nonionic or ionic. Examples of suitable surfactants include sodium or calcium salts of polyacrylic acid and lignin sulfonic acid; Condensation products of fatty acids, aliphatic amines and amides containing at least 12 carbon atoms in a molecule with ethylene oxide or propylene oxide; Fatty acid esters of glycerol, sorbitan, fructose or pentaerythritol; Condensates of ethylene oxide and propylene oxide; Condensation products of aliphatic alcohols and alkylphenols such as p-octylphenol and p-octylcresol with ethylene oxide and propylene oxide; Sulfates and sulfides of these condensation products; Alkali or alkaline earth metal salts of sulfuric acid or sulfonic acid esters having at least 10 carbon atoms in the molecule, preferably sodium salts such as sodium lauryl sulfate, sodium secondary sulfate, sodium salts of sulfonated keter oils and alkylaryls such as sodium dodecylbenzene sulfate Sodium sulfonate; And copolymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The composition of the present invention can be prepared in the form of wet powder, powder, granule, solution, emulsion concentrate, emulsion, suspension concentrate and aerosol. Wet powders usually contain 5, 50, 75 W% of active ingredient and usually contain solid inert carriers, 3-10 W% of dispersant, if necessary 0-10 W% of stabilizer and adducts such as penetrants or tackifiers. Powders are powder concentrates with compositions similar to wet powders, usually without dispersants, which are diluted with a solid carrier in the field and usually used as a composition with an active ingredient of 1 / 2-10W%. Granules are usually prepared in a size of 10-100BS mesh (1.675-0.152mm) and can be prepared by agglomeration and impregnation method. Generally, the granules comprise 1 / 2-25W% of active ingredient, 0-10W% stabilizer, additives such as penetrant and binder. In addition to the solvent, the emulsion concentrate contains, if necessary, additives such as cosolvents, 10-50 W / V% active ingredient, 2-20 W / V% emulsifier and 0.20 W / V% stabilizer, penetrant and corrosion inhibitor. Suspension concentrates are compounds for obtaining a stable non-flowing product, usually 10-75W% of active ingredient, 0.5-15W% of dispersant, 0.1-10W% of suspending agents such as protective colloids and thixotropic agents, and 0-10W% of defoamers. Additives such as corrosion inhibitors, stabilizers, penetrants and tackifiers and water or organic liquids, in which the active ingredient is insoluble in nature; Any organic solid or inorganic salt may be dissolved with the composition as a precipitating or antifreezing agent of water.

An aqueous dispersion or emulsion is a composition obtained by diluting the wet powder and concentrate according to the present invention with water, which is also within the scope of the present invention. The emulsion may be in the form of steam or water-in-oil and may have a dark, mayonnaise shape.

The composition of the present invention also includes other components, such as other compounds having insecticidal, herbicidal, plant growth control and bactericidal properties.

The following examples are intended to illustrate the invention.

Example 1

N-t-butylcarbonyl-3- (3'-pyridylmethyl) aminopyridine

(a) Formic acid (98% 10.8 g) was added to a solution of 3- (3'-pyridylaminomethyl) pyridine (18.3 g, 0.1 mol) in dry toluene (50 ml) and the mixture was stirred and heated at reflux for 16 h. It was. Toluene and formic acid were removed in vacuo and 10% hydrochloric acid (100 ml) and toluene (100 ml) were added to the residue. After shaking, the aqueous layer was separated, and concentrated aqueous solution of potassium hydroxide was added to make alkaline. The product was extracted with methylene chloride and the extract was dried (MgSO ₄ ). After removal of the solvent the product was purified by column chromatography (neutral alumina / 5% methanol in diethyl ether) and distilled off. Pure 3- (3'-pyridylmethyl) amino-pyridine was obtained as a colorless material having a boiling point of 176-178 ° C and a melting point of 66-69 ° C under pressure of 1 mmHg in 27% yield.

[analysis]

Calcd for N ₃ C ₁₁ H ₁₁ : C 71.35% H 5.95% N 22.7%

Experimental Value: 71.7 6.3 23.0

(b) To a stirred solution of 3- (3'-pyridylmethyl) aminopyridine (3.7 g, 0.02 mol) in dry benzene (50 ml) of trimethyl acetylchloride (2.8 g, 0.024 mol) in dry benzene (15 ml). After the solution was added, a solution of dry triethylamine (2.6 g, 0.024 mol) in dry benzene (10 ml) was added. The mixture was stirred and heated at reflux for 7 hours. After cooling, the reaction mixture was washed three times with water and dried (MgSO ₄ ). The solvent was removed in vacuo and the residue was chromatographed on neutral alumina and eluted with 5% methanol in diethyl ether.

N-t-butylcarbonyl-3- (3'-pyridylmethyl-aminopyridine was obtained in 65% yield as a colorless solid at a melting point of 69-70 占 폚.

[analysis]

N ₃ OC ₁₆ H ₁₉ Calculated: C 71.38% H 7.06% N 15.61%

Experimental Value: 71.1 7.5 15.6

Example 2

N-benzoyl-4-fluoro-N '-(3'-pyridylmethyl) adilin

(a) Formic acid (98%, 36.18 g) was added to a solution of 3- (4'-fluorophenylamino methyl) pyridine (67.0 g, 0.335 mol) in dry toluene (200 ml) and the mixture was stirred and refluxed for 20 minutes. Heated. Toluene and formic acid were removed in vacuo and 10% hydrochloric acid (120 ml) was added to the residue. After extraction with toluene, the aqueous layer was separated, and concentrated aqueous solution of potassium hydroxide was added to make alkaline. The product was extracted with diethyl ether and the extract was dried (MgSO ₄ ). After the solvent was removed, the residue was subjected to column chromatography (neutral alumina / diethyl ether). Pure 4-fluoro N- (3'-pyridylmethyl) -aniline was obtained in 10% yield as a colorless solid with a melting point of 85-87 ° C.

[analysis]

Calcd for N ₂ FC ₁₂ H ₁₁ : C 71.29% H 5.45% N 13.86%

Experimental Value: 71.2 5.8 14.0

(b) To a stirred solution of 4-fluoro-N- (3'-pyridylmethyl) aniline (3.03 g, 0.015 mole) in dry benzene (50 ml) benzoyl chloride (2.4 g, 0.017 in dry benzene (15 ml) Mole) solution was added followed by a solution of dry triethylamine (1.8 g, 0.018 mole) in dry benzene (10 ml). The mixture was stirred and heated at reflux for 16 h. After cooling, the reaction mixture was washed with water (X3) and dried (MgSO ₄ ). The solvent was removed in vacuo and the residue was triturated with a small amount of ether. The solid product was filtered off, washed with a little ether and dried. The yield of pure N-benzoyl-4-fluoro-N- (3'-pyridylmethyl) aniline is 89% and the melting point is 162-163 ° C.

[analysis]

N ₂ OFC ₁₉ H ₁₅ calc .: C 74.51% H 4.90% N 9.15%

Experimental value: 74.0 4.8 9.1

Example 3

N-t-butylcarbonyl-N- (4'-chlorophenylmethyl) aminopyrazine

(a) Formic acid (98%, 10.8 g) was added to a 4-chloro- (pyraziniminomethyl) benzene (21.75 g, 0.1 mol) suspension in jotoluene (50 ml) and the mixture was stirred and heated under reflux for 16 h. . Toluene and formic acid were removed in vacuo and 10% hydrochloric acid (100 ml) was added to the residue. After extraction with 100 ml toluene, the aqueous layer was separated and made alkaline by adding concentrated aqueous solution of potassium hydroxide. The product was extracted with diethyl ether and the extract was dried (MgSO ₄ ). After removal of the solvent, the product was purified by column chromatography (neutral alumina / diethyl ether). Pure N- (4'-chlorophenethylmethyl) amino pyrazine was colorless at melting point 86-87 ° C. in 27% yield. Obtained.

[analysis]

Calcd for N ₃ ClC ₁₁ H ₁₀ : C 60.14% H 4.56% N 19.13% Cl 16.17

Experimental value: 60.4 4.8 19.2 16.0

(b) To a stirred solution of N- (4'-chlorophenylmethyl) aminopyrazine (2.2 g, 0.01 mol) in dry benzene (30 ml) was added a solution of trimethylacetyl chloride (1.4 g, 0.012 mol) in dry benzene. Then a solution of dry triethylamine (1.3 g, 0.013 mol) in dry benzene (10 ml) was added. The mixture was stirred and heated at reflux for 22 hours. After cooling, the reaction mixture was washed three times with water and dried (MgSO ₄ ). The solvent was removed in vacuo and the residue was column chromatographed on neutral alumina and eluted with diethyl ether / hexane (3: 1).

N-t-butylcarbonyl-N- (4'-chlorophenylmethyl) -aminopyrazine was obtained in 58% yield as a colorless solid with a melting point of 65.8 占 폚.

[analysis]

Calcd for N ₃ OCl ₁₆ H ₁₈ : C 63.26% H 5.93% N 13.84%

Experimental Value: 63.3 5.9 13.9

Example 4

N-formyl-N- (4'-chlorophenylmethyl) -3-aminopyridine

Formic acid (98%, 10.8 g) was added to a solution of 4-chloro- (3'-pyridylaminomethyl) benzene (21.63 g, 0.1 mol) in dry toluene (50 ml), and the mixture was stirred and heated at reflux for 16 hours. . Toluene and formic acid were removed in vacuo and 10% hydrochloric acid (100 ml) was added to the residue. After extraction with toluene (100 ml), the aqueous layer was separated and alkaline was added by adding a concentrated aqueous solution of potassium hydroxide. The product was extracted with diethyl ether and the extract was dried (MgSO ₄ ). After removing the solvent, the residue was column chromatographed (neutral alumina / diethyl ether). The fast eluent is N- (4'-chloro-phenylmethyl) -3-aminopyridine, whereas the desired product N-formyl-N- (4'-chlorophenylmethyl) -3-aminopyridine is a late eluent of oil. It was obtained in 13.5% yield.

[analysis]

Calcd for N ₂ OCl ₁₃ H ₁₁ : C 63.29% H 4.46% N 11.36%

Experimental Value: 63.3 4.8 11.4

¹ NHMR (CDCl ₃ ) 4.93 (2H, m); 7.0-7.67 (6H, m); 8.47 (m) and 8.53 (s) (total 3H), ppm

Example 5

N-t-Butylcarbonyl-N- (4'-chlorophenylmethyl) -3-aminopyridine

To a stirred solution of N- (4'-phenylmethyl) -3-aminopyridine (45 g, 0.0206 mol) in dry benzene (50 ml) was added trimethyl acetyl chloride (2.9 g, 0.024 mol) in dry benzene (15 ml). Then a dry triethylamine (2.6 g, 0.026 mol) solution in dry benzene (10 ml) was added.

The mixture was stirred and heated at reflux for 6 1/2 hours. After cooling the reaction mixture was washed three times and dried (MgSO ₄ ). The solvent was removed in vacuo and the residue was washed with a small amount of diethyl ether and dried. Recrystallization from hexane gave pure Nt-butylcarbonyl-N- (4'-chlorophenylmethyl) -3-aminopyridine as a colorless solid at a melting point of 100-102 DEG C in 41% yield.

[analysis]

N ₂ OCl C ₁₇ H ₁₉ calculated: C 67.44% H 6.28% N 9.26%

Experimental value: 67.6 6.4 9.2

Example 6-71

The following compounds were prepared using methods analogous to those described in Examples 1-5.

TABLE 1

Example 72-77

In a similar manner, the following derivatives were prepared from the compound of formula (1).

Example 78

The bactericidal properties of the compound of formula (1) were investigated by the following experiment.

(a) Activity against grape fluffy powder bottle (Plasmopera Viticola PV, a) This experiment is an anti-spore forming experiment sprayed on leaves. The lower surface of the leaves of the whole grape crop was inoculated by spraying with 10 ⁵ diffuser / ml aqueous suspension 4 days before the treatment with the experimental compound. The inoculated plants were stored for 24 hours in a room of high humidity, 48 hours in a glass house of ambient temperature and humidity, and then maintained for 24 hours at high humidity again. After the plants were dried, the infected leaves were removed and sprayed onto the bottom surface using a track sprayer at a dose rate of 1 kg of active ingredient per hectare. After drying, the sprayed leaf peptiol was immersed in water and the leaf was turned to high humidity for 72 hours before evaluation. The assessment is based on the percentage of leaf area covered with sporulation compared to the control leaf.

(b) Activity against grape fluffy powder (Plasmopera Viticola PV, t)

This experiment is a translamina protective agent experiment with leaves. 상단 The top surface of leaf of the whole grape crop was sprayed with a track sprayer at a dose rate of 1 kg of active substance per hectare. After treating the bottom surface of the leaves with the experimental compound, after 6 hours inoculated by spraying an aqueous suspension containing 10 ⁵ diffuser / ml. The inoculated plants were maintained for 24 hours in a room of high humidity and 4 days in a glass house of ambient temperature and humidity, followed by 24 hours of high humidity. The assessment is based on the percentage of leaf area covered by sporulation on the control leaf.

(c) active against grape gray fungus) Motritis cinerea B, C)

This experiment is a direct root experiment using leaf spray. The underside of the detached grape leaves was inoculated by pipetting 10 drops of an aqueous suspension containing 5 × 10 ⁵ congenital magnetic / ml. The inoculated side was left uncovered overnight for the time when visible necrotic lesions occurred where bacteria penetrated the leaves and dropped the drops. Infected sites were sprayed directly using a spray sprayer at a dose rate of 1 kg of active substance per hectare. When the spray was dried, the leaves were covered with petri dish lids and the bottles developed under humidified conditions. The proportion of necrotic lesions beyond the initial droplet with spore formation was compared with the control leaves.

(d) Activity against potato death test (Pitoptora infection p. i.e)

This experiment is a direct root experiment using leaf spray. The top surface of the leaves (potatoes 12-18 cm in height) was inoculated by spraying with an aqueous suspension containing 5 × 10 ³ runners / ml 16-18 hours before treatment with the experimental compound. Inoculated crops were left overnight at high humidity and dried, and then sprayed at a dose rate of 1 kg of active substance per hectare using a track sprayer. After the spray was over, the crop was left to stand again at high humidity for an additional 48 hours. Evaluation is made by comparing the extent of disease in the treated and control plants.

(e) Activity against potato death test (phytophthora infections p, i, p)

This experiment measures the protective activity of compounds using leaf spray. 1-15 cm tomato crop, cultiva Aalsa Craig in one pot was used. The whole plant was sprayed using a track sprayer at a dose rate of 1 kg of active substance per hectare. The plants were inoculated by spraying with 5 × 10 ³ diffuser / ml aqueous suspension containing 6 hours after treatment with experimental compounds. Inoculated plants were kept at high humidity for 3 days. The assessment is made by comparing the extent of disease in the treated and control plants.

(f) Activity against barley powdery white powder (Erispie Graminis Eg.)

This experiment measures the direct anti-spore forming ability of a compound applied by leaf spray. About 40 barley seedlings for each compound were grown from sterile plastic pots to lateral stages. Inoculation is eryspie graminis SSP. It was carried out by attaching to the leaves in the state of the Horde. 24 hours after seeding, the seedlings were sprayed using a track sprayer with a solution of a compound mixed with acetone (5%), surfactant (0.04%) and water. The application rate was used as 1 kg of active substance per hectare. First, the evaluation of the disease was compared with the control pollen level of spore formation in the potted plants 5 days after treatment.

(g) activity against wheat brown rust (Puccinian Lecandira p, r)

This experiment is an upright anti-spore forming experiment using leaf spray. The pollen containing 25 mil seedlings per pollen was inoculated by spraying the leaves at the first leaf stage with 10 ⁵ spores / ml plus a small amount of Triton X-155 (Trademark) aqueous suspension 20-24 hours before treatment with the experimental compound. The inoculated plants were kept in a high humidity room overnight, dried in a glass house at ambient temperature and sprayed at a rate of 1 kg of active substance per hectare using a track sprayer. After treatment, the plants were kept at the ambient temperature of the glass house, and the evaluation was performed 11 days after the treatment. The evaluation is carried out by comparing the control plants with respect to the comparative density of spore forming pustules per plant.

(h) activity against broad soybean rust (Euromises Pave u.f)

This experiment is a translamina anti-spore formation experiment using leaf spray. One plant per pot was inoculated by spraying 5 × 10 ⁴ spores / ml plus a small amount of Triton X-155 aqueous suspension on the underside of each leaf 20-24 hours before treatment with the experimental compound. The inoculated plants were kept overnight in a room of high humidity, dried at the ambient temperature of the glass house, and sprayed on the upper surface of the leaves at a dose rate of 1 kg / ha of the active substance using a track sprayer. After the treatment, the plants were stored at the glass house temperature and the evaluation was performed on 11 and 14 days after the treatment. Signs were assessed based on the density of spore forming pustules in the plant compared to the control plant.

(i) Activity against Rice Leaf Death Disease (Pycurularia aurises p, o)

This experiment is a direct root experiment using leaf spray. Rice leaves (about 30 steps per pot) were sprayed with an aqueous suspension containing 10 ⁵ spores / ml 20-24 hours before treatment with the experimental compounds. Inoculated plants were kept overnight at high humidity, dried and sprayed at a dose rate of 1 kg of active substance per hectare using a track sprayer. After treatment the plants were stored in bedbeds at 25-30 ° C. and high humidity. Evaluation is done 4-5 days after treatment and compares the density of necrotic lesions and the degree of death when compared to control plants.

(j) Activity against Rice Blight Death Disease (Pelicularia Sasaki p, s)

This experiment is a direct root experiment using leaf spray.

20-24 hours prior to treatment with the test compound, rice seedlings (approximately 30 mos per pot) were sprayed with 5 ml of an aqueous suspension containing 0.2 g of milled Skeletal rosa / mycelium per ml. Inoculated plants were stored in a humidification chamber maintained at 25-30 ° C. and then sprayed at a dose of 1 kg of active substance per hectare. Treated plants were kept again at high humidity for an additional 3-4 days. This brown lesion was observed to spread to the left, starting at the bottom of the cow. Evaluation is made on the number and extent of lesions in comparison to the control plant.

The degree of control was expressed as a control grade based on the following criteria.

0 = 50% or less control, 1 = 50-80% control, 2 = 80% or more control / S ₁ and / S ₂ show lineage activity using the same rating scale. The control grades obtained are reported in Table II.

TABLE II

Bactericidal

Example 79

The bactericidal properties of the same type described in Example 78 ° were tested except that the following two types of compounds of Structural Formula (1) were instead tested in the Feliclaria sandals test.

k) Activity against apple powder powder (Phosperia rucotrica P. I.)

This experiment specifies the anti-spore formation of a compound applied as leaf spray. Apple seedlings for each compound were grown in aseptic plastic pots to 3-5 leaf stages. The leaves were inoculated by spraying the suspension with water in the experimental state. 48 hours after seedling inoculation, a solution of a mixture of acetone (50%), surfactant (0.04%) and water was sprayed with a track sprayer. The application rate corresponds to 1 kg of active substance per hectare. Initial evaluation of the bottles was made 10 days after the treatment, and the overall criteria of the seed type in the treated pots were compared with the control pots.

l) activity against peanut leaf spots (Secosphora iragidi cola c. a)

The process (k) was repeated using peanut seedlings grown to a height of about 15 cm. The bottles were evaluated 14 days after treatment. The results of Example 79 are reported in Table III below.

TABLE III

Bactericidal

Example 80

Herbicidal properties

In order to evaluate herbicidal properties, the compounds according to the invention were tested using the following representative plant species. Corn, Jiamei (MZ): Rice, Orissasathiba (R): Blood, Echinocrecarcus galli (BG): Oats, Avenassa tea (O): Flax seed, Linnumusita thamum (L); Mushrooms, Cinapis alba (M); Beet, Betabulatis (SB) and Soybeans, Glycinemex (S)

Experiments were carried out by leaf spray experiments and seedlings were sprayed into the structures containing the experimental compounds.

The soil used for the experiment was prepared as horticultural soil.

The structure used in the experiment was diluted with a solution of the test compound dissolved in water, acetone containing 0.4 wt% of alkylphenol / ethylene oxide commercially available under the trade name Triton X-155. The acetone solution was diluted with the same amount of water and the resulting structure was applied at a dose rate equivalent to 5 Kg of halide per hectare in a volume equivalent to 650 1 per hectare. Untreated seedlings were used as controls.

The herbicidal effect of the test compound was visually evaluated 11 days after spraying on the leaves and was expressed as 0-9 grade. Grade 0 indicates growth in untreated control and 9 indicates death. An increase of 1 unit per scale indicates an effect increase of 10%. The results are reported in Table IV.

Table IV

Herbicide activity

In addition to the leaf spray experiment, the pre-germination experiment was carried out by treating the seeded soil of various plant types with the compound according to the present invention. Examples 3, 5, 8, 13, 23, 26, 28-30, 32-34, 38, 43-50, 53-59, 62 and 70-76 show herbicidal effect before germination.

Example 81

Plant growth regulation

The above-described effects were observed through the experiment described in Experimental Example 80 with the compound of the present invention. The following effects were observed.

1. All compounds showing activity in herbicides reduced growth in all kinds of plants. In other words, the stem height was reduced.

2. Many compounds showed increased absorption in experimental plants. That is, dark green leaves were produced. Several experiments have observed other signs, including enlarged cotyledons, shortened nodes and shortened, broadened leaves.

Example 82

Plant growth regulation activity

The compound of Example 3 was tested in detail the following plant growth control properties.

Seeds of various plant types were planted and treated with an aqueous solution of 1: 1 acetone / test compound.

The resulting growth was sprayed and measured in units of one week up to at least five weeks. The growth was measured at each stage with the hybrid seed and the new weight was recorded. All experiments were conducted using untreated crops as controls. The plant seeds tested were as follows.

Corn: Grain Sor; Wheat; barley ; Cultivated oats; Wild oats; Ricegrass; Tolspescue; Blackgrass; weed ; Brown top bend; Coachgrass; Bermuda Grass; Nut Seed; Convolbulus; Soybean; Sugar beet; Cotton; Lugerin; Kale ; Velvet leaf; mushroom ; Red shank; Cleaver; Fail Pericaria; Planttain; Corn marigold; Spurlay; Sepadpus; Mayweed; Four lanes; Pigweed.

The test compound has significant plant-growth control properties for all seeds except nut seed. The main signs are suppression (inhibition of plant size), increase in light absorption (dark green leaves), suppressed node lengths (proximity of leaves in the stem) and some plants have broader leaves (the leaves of treated plants are untreated plants). It has long, thin leaves, but short and wide leaves).

The overall effect is compressed into growth.

Compared to the untreated control, the new weight of harvested plants was reduced and the effect lasted for a long time. Furthermore, this experiment shows that the effect can be eliminated and normal growth can be regained by treatment with the plant hormone gibberellic acid.

Example 83

Chemical turf conditioning

The effect of the compound of Example 3 on the growth of various grasses was compared with the effect of the commercial growth retardant maleic acid hydrazide.

Full Baren Brom (Bromus Sterris, BB) Yorkshire Fogg (Holkers Lanaters, YO), Tall Pescue (Pestuka Arudinasea TF), Common Vent (Agros Tyster Lewis, BT) and Landing Ligras ( Loriumferene, LP) was propagated in plastic flowerpots, lawns were produced, pruned, grown 5 times and then treated.

The compound of Example 3 was prepared as a solution of acetone / water (25: 75) containing 0.2% Triton X 155 (trademark) as a surfactant and soaked and applied to the experimental seeds at a ratio of 5.0, 2.5, 1.0 kg / ha. . For comparison, maleic hydrazide, prepared as an aqueous solution containing 0.2% Triton X 155 (trademark), was applied in the same proportion by using leaf spray, which is a common method.

Two types of evaluation were obtained.

a) effect on the visual mold of the lawn;

Visual evaluation was performed after 25 days of treatment. Grades are on a straight 0-9 scale, with 0 representing good appearance and 9 representing completely unacceptable appearance. The results were converted to percentages for the control, with results greater than 100 indicating that the treated seeds had a better appearance than the untreated control plants.

b) effect on poncho frequency

Commercial use of maleic hydrazide usually stipulates that one bee weed is required until the chemical effect on growth rate becomes apparent after treatment. In the untreated pots of all the seeds, the grass grew to a height that would be weeded 11 days after treatment. After measuring the height, all the grass was weeded from the top to a height that would normally be 15 mm from the ground. After this initial cut, the grass was grown to the initial cut height of the untreated control grass without inspection. Seed height varies depending on the growth rate and is as follows.

These heights are considered to be good grasses that contain common vents that are usually kept shorter than the rough weeds covered by the roadside.

The number of days required to grow to cut height was recorded.

It can be seen that the compound of Example 3 produced the best dark green leaves. Male hydrazide showed signs of yellowing and necrosis. In one experiment all the plants died. The results are reported in Table V.

TABLE V

+ = Complete death of all treated plants

The results show that the compound of Example 3 is more useful as a "chemical turf regulator" than maleinhydride.

Claims (1)

A process for preparing the compound of formula (I) and acid addition salts, N-oxides or metal salts thereof, characterized in that the compound of formula (II) is reacted with an acylating agent to acylate.

Wherein one of R ¹ or R ² represents an aromatic ring of an optionally substituted 6-membered ring containing 1 or 2 nitrogen atoms and the other of R ¹ and R ² represents a ring or an optionally substituted phenyl group, R ³ represents an acyl group derived from carboxylic acid, R ⁴ represents a hydrogen atom or an alkyl group having 1-4 carbon atoms, and when R ¹ is an optionally substituted pyridyl group, R ² represents an optionally substituted heteroaromatic ring, R ¹ In the case of this optionally substituted phenyl group, R ³ represents an acyl group derived from an acid other than optionally substituted benzoic acid, and when R ¹ represents an unsubstituted phenyl group, R ² represents an unsubstituted 2- or 3-pyridyl group. R ³ represents CH ₃ CO, phenyl, CH = CHCO-, C ₂ H ₅ CO- or (phenyl) ₂ CHCO-, R ⁴ represents an alkyl group, and R ² represents a phenyl group substituted with SO ₂ NH ₂ group ⁴ should represent an alkyl group.