KR870001614B1 - Pasteurize composition - Google Patents

Abstract

Formamidoxime derivs. (I) [X=halogen, nitro, cyano, carboxy, C1-6 alkoxy; B=oxygen, sulfur; Y=hydrogen, halogen, cyano, C3-6 cycloalkyl; m,n=0-5 integer, 0<=m+n<=5, R=cyano, C1-6 alkoxy! are prepd. by reaction of compd.(II) with compd.(III). The compd.(I) has sterilizing and insecticidal power. The germicidal compsition is composed of 50 wt. part of compd. (I), 12.5 wt. part of benzimidazol- thiofanite compd., 32.5 wt. part of white carbon, 3 wt. part of sodium aliphatate and 2 wt. part of calcium ligninsulfonate.

Description

Bactericidal composition

The present invention is a divided application of Patent Application No. 84-4165, which relates to a novel formamidoxime derivative and its salts or complexes with a disintegrating carrier or solvent, sterilizing, insecticidal compositions in the form of emulsions or solutions.

The present invention relates to a bactericidal composition containing an effective amount of a compound of formula (I) and an inert additive and / or a carrier.

(R'은 수소 또는 C_1~6알킬)기이고 ;Wherein X is halogen, nitro, cyano, formyl, C _2-8 alkylcarbonyl, carboxy, C _2-8 alkoxycarbonyl, C _3-8 alkanyloxycarbonyl, C _3-8 alkynyloxycarbon Hexyl, carbamoyl, C _2-6 alkylcarbamoyl, heterocyclic radicals containing oxygen and cyano, hydroxy, halogen C _1-6 alkoxy, C _1-6 alkoxy substituted C _1-6 alkoxy, C _2-6 alkanyloxy, C _2-6 alkynyloxy, C _3-8 alkynyloxycarbonyloxy, C _1-6 alkylthio, C _1-6 alkylsulfinyl, C _1-6 alkylsulfonyl, C _{1 6} alkyl-substituted amino, hydroxyimino, C _1-6 alkoxyimino, and or C _{2 ~ 8} alkoxycarbonyl same selected from a saturated or unsaturated C _1-6 hydrocarbon radical which may be substituted with a group or as Other substituents, -B- is -O-, -S-, -SO-, -SO ₂ -or

(R 'is hydrogen or a C _1-6 alkyl) group;

Y is hydrogen or halogen, cyano, C _3-6 cycloalkyl, C _2-8 alkylcarbonyloxy, C _2-8 alkylcarbonyl, C _2-8 alkoxycarbonyl, hydroxy, C _1-6 alkoxy, The same or different substituents selected from the group consisting of saturated or unsaturated C _1-6 hydrocarbon radicals which may be substituted with C _1-6 alkylthio, ureido and or heterocyclic radicals containing oxygen;

(BY) _n part is C _1-6 alkoxy, -O- (CH ₂ ) lO (CH ₂ ) l'- and -O- (CH ₂ ) lO-CO- (l and l 'are 1 to 3, respectively) Integer) represents a di-substituted modified radical (BY) selected from the group consisting of C _1-3 alkylenedioxy;

m+n

5의 조건하에 0 내지 5의 정수를 표시하고, "이"를 취하는 이-치환변형-B-Y 형태인 (B-Y)기를 제외하고는 위에 보여준 치환체는 "하나"를 취하고;each of m and n is 0

m + n

Under the condition of 5, the substituents shown above take the "one" except for the (BY) group, which is an bi-substituted-BY form which takes an integer of 0 to 5 and takes "this";

R is a substituent selected from the group consisting of saturated or unsaturated C _1-18 hydrocarbon radicals which may be substituted by halogen, cyano, C _1-6 alkoxy, C _1-6 alkyltimo, C _1-6 alkoxycarbonyl;

"C-number" indicates the range of total carbon number of the substituent or radical directly following.

When farming plants in agriculture or horticulture, many preventive chemicals are used to prevent bacteria, insects and / or mites harmful to the plant or crop, but sometimes their preventive effects are insufficient and the plant and crop are contaminated by its weakness. And many adverse chemicals are not satisfactory compounds and are not suitable for commercial use in plants.

Therefore, there has been a great desire for the emergence of prophylactic compounds which can be used safely from the above weaknesses.

Attention to the above-mentioned weaknesses, the inventors conducted investigations on many compounds, and found that the compounds of the general formula (I) exhibited excellent bactericidal effects against various plant pathologies.

Formamidoxime derivatives having a hydrogen atom at the R position of the general formula (I) have no bactericidal action in such a compound in US Pat. No. 4,237,168 and show only insecticidal action.

The so-called "benzamidazole-thiophanates bactericidal compounds" we have developed for agriculture and horticulture are world-renowned as fungicides since 1970.

The fungicides include benomyl [methyl 1- (butylcarbamoyl) -benzimidazol-2-yl carbamate], fuberidazole [2- (2-furyl) benzamidazole], thibendazole [2- ( 4-thiazoline) benzamidazole], carbendazim [methyl benzamidazol-2-yl-carbamate], thiophanate methyl [1, 2-bis (3-methoxycarbonyl-2-thiou) Rado) benzene] and thiophanate [1, 2-bis (3-ethoxycarbonyl-2-thioureido) benzene], etc., to various germs which are parasites of plants and crops of agriculture and horticulture It showed an excellent control effect and contributed to double the production of crops (hereinafter collectively as a compound of benzamidazole-thiophanates).

However, if the same fungicide is continuously sprayed on plants and crops of the same land for a long time, the treated bacteria will develop resistance to the compounds of benzamidazole-thiophanates; Increasingly, farmers who are users of these fungicides will have to use another effective fungicide to control chemical resistant bacteria.

However, any bactericide that is relatively effective as a bactericide of benzamidazole-thiaphanate before the chemical resistant bacteria prevails has not yet appeared on the market because it is difficult to obtain appropriate preventive measures against plant diseases.

Considering the above situation, the present inventors have synthesized many novel compounds and increased the bactericidal action of the fungicide against chemical resistant bacteria. This is because, in order to exhibit a strong selective bactericidal action against chemical resistant bacteria, a high preventive effect is expected on the plants of the land where the chemical resistant bacteria dominate.

It was found that at least one compound of the general formula (I) having a -B-Y group (hereinafter referred to as "B-Y compound") has a selective prophylactic effect on plant diseases caused by chemically resistant bacteria. In other words, the compound has a selective bactericidal action against chemical resistant bacteria.

In contrast to the higher bactericidal action against chemically resistant bacteria, BY compounds are harmful diseases caused by bacteria that are sensitive to compounds of benzamidazole-thiophanates (hereinafter referred to as "chemically sensitive bacteria") in the following specified tests. There was no or almost no preventive effect on. Thus, B-Y chemicals have a high and sensitive selective bactericidal action against chemical resistant bacteria.

Regarding the strength of the selective bactericidal action against chemically resistant bacteria of the BY compound, a compound having a -BY group at the 3 and or 4-position of the phenyl group of the compound has a strong selective bactericidal action, but the BY group is only at the 2-position. Having compound has weaker activity. Compared to B-Y compounds in which -B- is not -O-, the selective activity of compounds with -B- is -O- is greatest.

Considering the conditions of actual application land where chemical resistant and chemically sensitive bacteria are mixed and spread in plants, many kinds of mixtures of compounds selected from BY compounds and compounds selected from compounds of benzamidazole-thiophanates (hereinafter " "Compounds" are compared with the single mixture before mixing for the preventive effect against various plant diseases, by infection with chemical resistant bacteria, chemically sensitive bacteria or mixtures thereof (hereinafter referred to as "mixed bacteria"). It has been found that the mixing of the above chemicals unexpectedly excellent efficacy in preventing plant diseases caused.

Therefore, it can be said that due to the infection of the mixed bacteria, almost incurable plant diseases can be completely cured by using a mixed disinfectant, i.e., a mixed compound, of a combination of two special kinds of active ingredients shown above.

Furthermore, it is surprising that mixed compounds have shown unexpectedly superior efficacy in controlling chemically sensitive bacteria as well as individually grown chemically resistant bacteria. For example, a mixed compound may have a bactericidal activity of 5 to 10 times the activity of the BY compound against chemically resistant bacteria and the activity of the compounds of benzamidazole-thiophanate against chemically sensitive bacteria. Indicates.

Therefore, the mixed compounds of the present invention showed their excellent bactericidal power under various conditions of bacteria in practical agricultural and horticultural industries.

For example, sugar beet brown pattern bottle (set cosphora beticola), peanut's chef cosphora leaf spot (cer cosphora arachidola) and brown pattern bottle (cer cosphora persona), cucumber powder powder (spa) Erodeca Pullignia), Vine Blight (Micosparerella Melonis), White Silk Disease (Sclerotinia sclerothiorum), Gray Mold Disease (Botrytis Ceria), and Black Patterned Disease (Crado) Sporium Cucumber Head), Tomato Blight Disease (Botrytis Ceria) and Leaf Fungus (Crasporium Fulbum), Eggplant Greymould (Botrytis Ceria), Black Lot (Corrinespora Melo) Genesis) and powdery mildew (Erisupe Sicoracearum), frosty mildew disease (Botrytis cineraria) and powdery Mildew (Spaeroceca hummus) on strawberries, gray rot of disease (Botrytis ali) and gramo Melancholy (Botrytis Ceria), Dame Powdery mildew (Erysipiferous syrupaceum), sclerotinian lot of green beans (Sterrotinian screrothiorum) and ash fungus (Botrytis cineraria), powdery mildew of apples (grape sperifera) Cottrica), Black Star Plaque (Venturia Inequaris), and Flower Mixture (Screllatinia Mali), Persimmon Powdery Mildew (Philactinian Khaki Cola), Anthrax (Gloesporium Khaki) Patterned deciduous disease (Sercospora khaki), grayish-eyed disease of peach and cherries (Sclerotinian cineraria), gray mold of grapes (Botrytis cineraria), powdery mildew (Uncinula necator) or life lot (clone) Merella singurata), pear's black star pattern (Venturia nasichola), tea tree's gray blight (Pescalotea theae) and anthracnose (colletotriac thea-cinensis), orange beetle Bottle (Elcino Paceti), Blue Mould (Pensilium) Talicom), and the Common Green Mould (Penisium Digitatum), Barley Grain Bottle (Ericife Graminis f. Sp.Horday), Eye Spot (Sederocospoela Herporticoides) and Fusarium Snow Bright (Fusarium nibail), Wheat Flour Disease (Ericifer Graminis f. Sp.

Moreover, as mentioned above, farmers who are users of preventive fungicides face increased difficulties due to the widespread chemical resistant bacteria, plants and crops caused by chemical resistant bacteria or mixtures of chemical resistant bacteria and chemical sensitive bacteria, ie mixtures. We cannot guarantee prevention of disease.

Since about 1980, N- (3 ', 5'-dichlorophenyl) -1, 2-dimethyl cyclopropane-1, 2-dicarboxyimide, 3- (3', 5'-dichlorophenyl) -2-iso Of cyclic imides such as propylgarbamoylimidazolidine-2, 4-dione or 3-) 3 ', 5'-dichlorophenyl) -5-methyl-5-vinyloxazolidine-2,4dione Fungicides containing compounds are traded on the market.

Compounds of cyclic imides exhibit strong bactericidal activity against chemically sensitive bacteria as well as chemically resistant bacteria. In particular they show good bactericidal activity against gray moulds (botrytis cineraria) of grapes or vegetables and ashes of peach or cherry (sclerotinian cieria).

In the past, farmers have gained trial success in taking preventive measures against chemically resistant bacteria using fungicides containing cyclic imides. However, bacteria resistant to the compounds of the cyclic imide were formed, and the preventive effect against the bactericidal activity of the plants was lowered.

In consideration of the above case, the present inventors used four kinds of complex bacteria (Brittis cineria), that is, benzamidazole-thiophanate, for the test for confirming the bactericidal action of the compound according to the present invention against mixed bacteria. Microorganisms sensitive to compounds of the above mentioned compounds and cyclic imides (hereinafter referred to as "BT / S & CI / S"), bacteria which are sensitive to compounds of benzimidazole-thiophanates and resistant to compounds of cyclic imides (Hereinafter referred to as "BT / S & CI / R"), bacteria resistant to compounds of benzimidazole-thiophanates and sensitive to compounds of the cyclic imides (hereinafter referred to as "BT / R & CI / S") ) And bacteria resistant to compounds of benzimidazole-thiophanates (hereinafter referred to as "BT / R & CI / R") (hereinafter collectively referred to as "composite") ) Adopted.

As a hook, the compounds of the present invention which have a very high selective bactericidal action against bacteria having the properties of BT / R are irrespective of whether the bacteria are resistant or sensitive to the compounds of the cyclic imides or to the compounds of other fungicides. Extremely high bactericidal activity against mixed bacteria having BT / R properties.

Nevertheless, contrary to the above-mentioned facts, BY compounds are prevented against plant diseases such as blasts, cucumber rot, etc., regardless of whether the bacteria causing the disease are resistant or sensitive to the compounds of benzimidazole-thiophanates. Effect.

Compounds having the general formula (I) are capable of insecticidal and / or acaricide against harmful mites such as pests and spotted mites, such as moths, aphids or cicadas.

The compound of formula (I) according to the present invention is prepared as follows.

X, -B-, Y, R, m and n used below are the same as described in general formula (I).

Where r is C _1-4 alkyl (hereinafter referred to as “manufacturing method A”).

Formimidates having formula (II) react with hydroxyamines having formula (III) in an inert organic solvent. As the inert organic solvent, polar solvents such as lower alcohols, ethers, esters and halogenated hydrocarbons are used.

The reaction is generally carried out for 0.1 to 1.0 hours from room temperature to the boiling point of the solvent used. Formimidate taking the general formula (II) can be prepared by the following scheme (2) in which aniline corresponding to formimidate and ortho C _1-4 alkylform mate are reacted.

Wherein Hal is halogen and r 'is C _1-4 alkyl and phenyl in which methyl may be substituted.

(Hereinafter referred to as 'manufacturing method B-b')

Wherein Y '' may be substituted with a heterocycle containing halogen, cyano, cycloalkyl, alkylcarbonyloxy, alkylcarbonyl, alkoxycarbonyl, hydroxy, alkoxy, alkylthio, ureido and or oxygen Demonstrating identical or different substituents of saturated or unsaturated C _1-6 hydrocarbon groups;

m 'is a collection from 0 to 4.

n 'is a collection from 1 to 5.

m'+n'+n''

5의 조건을 만족하는 0에서부터 4까지의 징수를 나타낸다.n '' is 1

m '+ n' + n ''

Represents a collection from 0 to 4 that satisfies the condition of 5.

The raw material having the general formula (V) or (IX) may be prepared according to the production method A wherein R is hydrogen (for compound (V)) or Y is hydrogen (for compound (IX)).

Compounds having the general formula (V) or (IX) include halogen compounds, sulfate compounds or sulfonate compounds having the general formulas (VI), (VII), (VIII), (X), (XI) or (XII) Respond.

The reaction is generally carried out in an inert organic solvent in the presence of an acid binder for 0.5 to 3 hours at a temperature within the boiling range of the solvent used at 0 ° C.

In the inert organic solvent, polar organic solvents such as acetone, dimethylformamide, tetrahydrobutane, acetonitrile, chloroform, toluene and the like can be used.

As the acid binder, for example, organic or inorganic bases such as sodium hydride, triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate may be used.

Also in the preparation method of the raw material and the preparation method A, if the starting material (IV) has an OH substituent at the 2 or 6 position of the phenyl group, such reactions can be carried out in part according to the following reaction scheme.

In the formation of organic or inorganic acid salts or metal salt complexes of compounds of general formula (I), the compounds are reacted with organic or inorganic acids or metal salts in an inert organic solvent such as chloroform, ether, acetone, acetonitrile, benzene at room temperature Or the complex is obtained by precipitation.

Inorganic acids are hydrochloric acid, bromic acid, phosphoric acid, nitric acid, and the like, and organic acids include acetic acid, oxalic acid, maleic acid, muxic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, p-toluenesulfonic acid, methanesulfonic acid, 1, 5 -Naphthalene-disulfonic acid, picric acid, phenylhaksonic acid and the like can be used.

In metal salt complexes, the cations include aluminum, silicon, manganese, iron, cobalt, nickel, copper, zinc, cadmium, tin, mercury, lead, etc., and the counter anions include chlorine, bromine, iodine, sulfonic acid, phosphoric acid, nitric acid, and carbonic acid. Anions such as oxalic acid and citric acid can be used.

The chemical structure of the compound is determined by the results of spectral analysis of IR., NMR and / or Mass and, if necessary, other analyses.

In the present invention, the salt or complex is dissolved in water in which the acid or metal salt is molten to the compound of the salt or complex, and determined by elemental analysis or other method, and the dissociated free compound having the general formula (I) is filtered off and the residue is acidified. Or chelate titration, neutralization titration or redox titration to determine the molar ratio of the metal salt.

Compounds having the general formula (I) have the form of tautomers as shown in the general formulas (I) and (It), and each compound corresponding to the structure of each tautomer is an “E isomer” and a “Z isomer” The invention consists in the compaction of all isomers and mixtures thereof.

2.6 g of 3, 4-diethoxy-5-methylaniline, 3.9 g of ortho ethyl formate and 30 ml of ethyl acetate are mixed under stirring and the resulting solution is heated to 70-80 ° C.

Ethanol produced by the reaction process is distilled to an azeotropic mixture with ethyl acetate at atmospheric pressure.

When the distillation is slow, the reaction temperature is raised to 100 ° C. or higher and the distillation is continued for about 1 hour under the same heating temperature and stirring.

The excess ortho ethyl pressuremate was then distilled off under reduced pressure of 15-20 mm / Hg and a bath temperature of 50-60 ° C. to give 3.2 g of crude intermediate ethyl N- (3,4-diethoxy-5 as a residue. -Methylphenyl) -Pressimidate is obtained.

The crude intermediate was dissolved in 20 ml of chloroform, and 1.95 g of an aqueous solution containing 45% of ethoxyamine was added while stirring at room temperature. After stirring for 1 hour, the resulting solution was washed with water and dehydrated with anhydrous magnesium sulfate, and then chloroform was distilled from the filtrate of the dehydrated solution.

The obtained crystals were recrystallized with a mixed solvent of n-hexane and ethyl acetate (9: 1 v / v) to give 2.8 g of the target substance N- (3,4-diethoxy-5-methylphenyl) -N'-ethoxy-formami Dean (melting point, 89-91 ° C.) is obtained.

[Reference 2 (Manufacturing Method B-b)]

27.9 g of 4-amino-2, 6-diethylphenol, 50.0 g of ortho ethylformate and 100 ml of ethyl acetate are mixed with stirring, and the resulting solution is heated to 70-80 ° C.

Ethanol produced during the reaction is distilled to an azeotrope with ethyl acetate at atmospheric pressure.

When the distillation is slow, the reaction temperature is raised to 100 ° C. or higher and the distillation is continued for one hour under the same heating temperature and stirring.

The excess ortho ethylformate was then distilled under reduced pressure of 15-20 mmHg and a bath temperature of 50-60 ° C. to give 37.3 g of crude intermediate ethyl N- (3,5-diethyl-4-hydride as residue. Oxyphenyl) -formimidate is obtained.

Dissolve in 150 ml of the crude intermediate above and add 11.2 g of ethoxyamine dropwise into the solution at room temperature under stirring. After stirring for 3 hours, the methanol obtained by distilling methanol was washed with a mixed solvent of ether and n-hexane (1: 1v / v), and 37.8g of N- (3,5-diethyl-4-hydroxyphenyl A light brown matrix (melting point, 70-73 ° C.) of) -N'-ethoxy-formamidine is precipitated.

9.0 g of the obtained base, 5.3 g of potassium carbonate and 6.55 g of ethyl iodine are mixed with 50 ml of acetone and the mixture is heated under reflux and stirring for 2 hours. The reaction mixture is cooled to room temperature, iodine and potassium and potassium hydrogencarbonate are removed by filtration and washed with a small amount of acetone.

The filtrate is collected and acetone is distilled off from the filtrate. The obtained gallbladder was purified by regluting with methanol to give 9.9 g of the target substance N- (3,5-diethyl-4-ethoxyphenyl) -N'-ethoxy-formamidine as a white gallbladder (melting point 69-). 71 ° C.).

Reference Example 3 (Manufacturing Method B-a)

Sodium methylate solution prepared by dissolving 1.1 g of hydroxyamine hydrochloride in heated 10 ml ethanol and reacting 10 ml of methanol and 0.36 g sodium metal at room temperature is added dropwise to the solution to neutralize.

The resulting solution is cooled to about 5 ° C. and sodium chloride is filtered off.

The filtrate was filtered from 3.1 g of crude intermediate ethyl N- (3-chloro-4-ethoxy-, prepared from 2.4 g of 3-chloro-4-ethoxy-5-methylaniline by a similar method as in Example 1. Mix with 5-methylphenyl) -formimidate and the resulting mixture is stirred at room temperature for 2 hours.

Next, methanol is distilled off and 2.9 g of crude intermediate N- (3-chloro-4-ethoxy-5-methylphenyl) -N'-hydroxy-formamidine is precipitated.

The intermediate is dissolved in 20 ml of N, N-dimethylformamide and 1.6 g of triethylamine is added to the solution.

The resulting solution is then stirred at room temperature, 1.9 g bromine allyl is added and stirring continued for 3 hours.

The reaction solution is poured into 100 ml of ice water and extracted with ethyl acetate.

The extracted solution was dehydrated with anhydrous magnesium sulfate, ethyl acetate was filtered off, and the obtained residue was purified by silica gel column chromatography to give 2.0 g of the target substance N- (3-chloro-4-ethoxy-5-methylphenyl)-. N'-allyloxy-formamidine (melting point: 81-83 ° C) is precipitated.

Reference Example 4 (Manufacturing Method B-a)

25 g of N, N-dimethylformamide was mixed with 2.0 g of potassium carbonate and 3.5 g of N- (3,5-dichloro-4-ethoxyphenyl) -N'-hydroxy-formamidine, and 2.4 g Diethyl sulfate is added. The mixture is stirred at room temperature for 1 hour and at about 90 ° C. for 2 hours.

Pour the mixture into ice water and extract with ethyl acetate.

The extract dehydrated with magnesium sulfate is evaporated under reduced pressure. The residue was purified by silica gel column chromatography to precipitate 2.4 g of N- (3,5-dichloro-4-ethoxyphenyl-N'-ethoxy-formamidine (melting point 119.5-120.5 ° C).

Reference Example 5 (Manufacturing Method B-b)

20 ml of N, N-dimethylformamide were mixed with 0.45 g sodium hydroxide and 3.0 g N- (3-bromo-5-chloro-4-hydroxyphenyl) -N'-methoxy-formamidine 2.8 g of beta-chloroethyl-p-toluenesulfate are added.

The mixture is stirred at room temperature for 5 hours. The mixture is added to ice water and extracted with ethyl acetate. The extract dehydrated on magnesium sulfate is evaporated under reduced pressure. The residue was purified by silica gel column chromatography to give 3.1 g of N- [3-bromo-5-chloro-4- (β-chloroethoxy) -phenyl-N'-methoxy-formamidine (melting point 112.5). -114.0 ° C).

Reference Example 6

An excess of hydrochloric acid gas was introduced into a solution of 1.0 g of N- (3-chloro-4-ethoxy-5-methylphenyl) -N'-allyloxy-formamidine dissolved in 15 ml of chloroform at room temperature with stirring. Master settles down.

The above isolated gallbladder was collected by filtration, and dried in vacuo, and 1.0 g of white trichloromethane N- (3-chloro-4-ethoxy-5-methylphenyl) -N'-allyloxy-formamidine hydrochloric acid ( Melting point 122-123.5 ° C., decomposition).

Molar ratio analysis of hydrochloric acid:

Approximately 0.2 g of N- (3-chloro-4-ethoxy-5-methylphenyl) -N'-allyloxy-formamidine hydrochloric acid is accurately weighed and placed in 30 ml distilled water. The distilled water is stirred for 30 minutes at 50 ° C to dissociate the hydrochloride. Dissociated free material is separated, collected by filtration and washed with 70 ml of distilled water.

The filtrate is collected in a 100 ml volumetric flask, filled with distilled water to a total volume of 100 ml and shaken to obtain a clean solution.

Take an aqueous solution with a 25 ml hole pipette and analyze the amount of hydrochloric acid by titration neutralization with 0.01 N aqueous sodium hydroxide solution.

The free material obtained by the above filtration is dried and discriminated by IR spectrum.

Sample collected = X _g

Amount of hydrochloric acid added to the neutralization diameter = Y mol

Reference Example 7

A solution of 1.7 g of N- (4-allyloxy-3, 5-dimethylphenyl) -N'-ethoxy-formamidine dissolved in 20 ml of acetone was added to 1.4 g of hydrated cupric acetate under stirring at room temperature. Let's do it. Immediately, a clean solution is formed and precipitation is continued after about 10 minutes with continued stirring at room temperature.

Filtering the gallbladder and drying in vacuo yielded 2.1 g of pale green banung N- (4-allyloxy-3, 5-dimethylphenyl) -N'-ethoxy-formamidine cupric acetate salt (melting point 159-160 ° C). Get)

Analysis of cupric acetate molar ratio:

Approximately 0.16 g of N- (4-allyloxy-3, 5-dimethylphenyl) -N'-ethoxy-formamidine cupric acetate salt is accurately weighed, added to 300 ml distilled water, and the resulting aqueous solution is added at 30C at 30 ° C. Stir for minutes to dissociate the salt.

The dissociated free material is separated from the solution, collected by filtration and washed with 70 ml of distilled water. The filtrate is collected in a 100 ml volumetric flask and added to the total volume of 25 ml with complementary distilled water to give a clear solution by shaking.

The aqueous solution is taken with a 25 ml hole pipette, chelate titrated by classical methods using 0.01 N EDTA as standard solution and the amount of copper is analyzed.

Dry the free material obtained for the above filtration and identify the material by IR spectrum.

Amount of sample collected = X _g

Amount of copper measured by chelate titration = Y mnl

Reference Example 8

0.86 g of hydrated p- in a solution of 1.6 g of N- (3-bromo-4-ethoxy-5-trifluoromethylphenyl) -N'-ethoxy-formamidine dissolved in 30 ml of ethyl ether. Toluenesulfonic acid is added with stirring at room temperature. Immediately a clear solution is formed and the gallbladder precipitates after about 3 minutes with continued stirring at room temperature.

When collected by filtration and dehydrated in vacuo, 2.3 g of a white tablet N- (3-bromo-4-ethoxy-5-trifluoromethylphenyl) -N'-ethoxy-formamidine p-toluenesulfonate ( Melting point 146-147.5 ° C.).

Each compound within the scope of the invention, which can be prepared by a similar method, including the compound of the above reference example, is tabulated in the first table.

[Table 1]

As already mentioned, compounds having the general formula (I) and mixed compounds show significant efficacy of bactericidal, insecticidal and / or acaricides, and may contain a composition containing one of the compounds or a mixed compound as an active ingredient, such as a hydrating agent, an emulsifying thickener, and a water-soluble compound. It can be prepared by mixing appropriate carriers and / or additives commonly used in pesticides such as powders, powders, granules, suspension concentrates and the like.

As the solid carrier, there may be used minerals such as grain flour such as soy flour and flour, diatomaceous earth, apatite, gypsum, talc, bentonite, clay and the like.

Liquid carriers include vegetable oils, mineral oils, petroleum (e.g. kerosene and solvent naphtha), xylenes, cyclohexane, cyclohexa, dimethylformamide, dimethylsulfoxide, tricholoethylene, methyl isobutyl ketone and water. Can be.

If necessary, surfactant is added to form a homogeneous and stable preparation.

The concentration of the active ingredient in the composition varies depending on the type of preparation, such as in the range of 5-80% by weight of the hydrating agent, preferably 10-70% by weight, and 5-30% by weight of the emulsifier, preferably 10-20. % By weight, water-soluble powder is 5-80% by weight, preferably 30-60% by weight, powder is 1-10% by weight, preferably 2-5% by weight, suspension concentrate is 5-40% by weight, preferably Is 10-30% by weight, granules are 1-10% by weight, preferably 2-5% by weight.

Hydrated powder, emulsifying thickener, water soluble powder and suspending thickener are diluted with water to a certain concentration and used as an aqueous suspension or aqueous emulsion to spray plants.

Powders and sesame are used for powdering or application directly to plants.

Examples of the compositions of the present invention are mentioned below, but the scope of the present invention is not limited to the following examples.

Example 1 Hydration Powder

50 parts by weight of a compound of the present invention

12.5 parts by weight of the compound of benzimidazole-thiophanates

White carbon 32.5 parts by weight

High Fatty Acid Sodium Salt 3 parts by weight

Calcium lignin sulfonate 2 parts by weight

The compounds are mixed to provide a hydrating agent containing 62.5% of the active ingredient. In use, dilution with water gives a suspension of the compound in the desired concentration.

Example 2 Hydration Powder

25 parts by weight of a compound of the present invention

25 parts by weight of the compound of benzimidazole-thiopanites

45 parts by weight of white carbon

Higher fatty acid sodium salt 3 parts by weight

Calcium lignin sulfonate 2 parts by weight

The above compound is mixed to provide a hydrating agent containing 50% of the active ingredient. In use, dilution with water gives a suspension of the compound in the desired concentration.

Example 3 Hydration Powder

50 parts by weight of a compound of the present invention

10 parts by weight of the compound of benzimidazole-thiopanites

White Carbon 35 parts by weight

Higher fatty acid sodium salt 3 parts by weight

Calcium lignin sulfonate 2 parts by weight

The above compounds are mixed to provide a hydrating agent containing 60% of the active ingredient. In use, dilution with water gives a suspension of the compound in the desired concentration.

In addition, the compounds or mixed compounds of the present invention need not be said to exhibit sufficient efficacy of the bactericidal, insecticidal or acaricide, but may be mixed with one or more compounds of the bactericidal, insecticidal or acaricide in the above composition (hereinafter, Referred to as "mixed composition". This is because the compounds or mixed compounds of the present invention may exhibit insufficient or inferior effects in certain kinds of bacteria, insects or mites.

Representative bactericidal, pesticidal or acaricides that may be used with the compounds of the present invention or mixed compounds in the mixed compositions are examples of compounds.

〔disinfectant〕

Captan, TMTD, Geneb, Manneb, Manzab, TPN, Phenram, Furabex, Aliete, Prothiocarb, Triadimethone, Triadimenol, Polyoxine, Tridemorph, Metalaxin, Furalaxin, Tree Porin, Isoprothioran, Provanazol, Brastigidin-S, Kasugamycin, Validamicin A. PCNB, Iprodione, Vinclozoline, Prosmidone, Basic Copper Chloride, Basic Copper Sulfate, Triphenyltinhydride Roxide, quinomethionate, propamocarb, vinazacryl.

[Pesticides and Acaricides]

BCPE, Chlorobenzylate, Chloropropylate, Proclonol, Phenyl Sobromorate, Dicopol, Chlorophenamidine, Amitraz, BPPS, PPPS, Benzomate, Cyhexatin, Polynactin, Thioquinox, CPCBS, tetradipon, tetrasul, cycloplate, phenoxide, kayakhof, lime-polysulfide, 3-n-dodasil-1, 4-naphthoquinone-2-yl acetate, pention, phenythrothione , Diazinone, chloropyriphos, ESP, bamidothione, pentcoate, thimethoate, pomomothione, malathion, DEP, thionmethone, phosmet, menazone, dichlorbose, acetate, EPBP. Dialilipot, methylparathion, oxydamageton-methyl, ethion, aldicarm, propulsulin, fermethrin, cipermethrin, degamatrine, fenvallate, phenpropatrine, pyrethrin, alletrin, Detramethrin, resmethrin, dimethrin, propartrine, protrin, 3-phenoxybenzyl-2, 2-dichloro-1- (4-ethoxyphenyl) -1-cyclo propanecarboxylate, α -Cyano-3-phenoxybenzyl- (RS) -2- (4-trichloromethoxyphenyl) -3-methylbutylate, (RS) -α-cyano-3-phenoxybenzyl- (RS)- 2- (2-chloro-4-trichloromethylanilino) -3-methylbutylate, petroleum.

The following tests illustrate the bactericidal, pesticidal and acaricide activity of the compound or mixed compound.

Trial 1 Ginseng Mildew Disease (Botritis Ceria)

About three weeks of seedlings of Gangnam beans (variety: Nagajujura) are grown, and the leaves obtained therefrom are medicated in an aqueous solution having a characteristic concentration of active ingredient prepared from a hydrated powder grown according to the method of Example 3 (mutatitis mutantis). Soak for 30 seconds and air dry.

The dried leaves are inoculated with mycelium of chemical resistant bacteria, chemically sensitive bacteria, mixed bacteria and complex bacteria of gray fungus disease of Gangnam beans (Botrytis cieria) and stored in a 20 ° C wet room.

The incidence of each leaf treated with the aqueous solution is investigated on the fourth day after inoculation.

According to the following investigation standard, the disease index is measured and the preventive value of each compound or mixed compound is calculated by the formula of preventive value (%).

Diameter of lesion (mm) 0 1-4 5-10 11-18 19-29 30

Disease Index 0 0.5 1 2 3 4

Hangings are shown in the following 2nd table (2-1 to 2-3).

[Table 2]

[Table 2]

[Table 2]

Comparative Compound 1: Thiophanate Methyl

〃 2: carbendazim

〃 3: vinclozoline

〃 4: Iprodione

Test 2 Cucumber powdery mildew (Spaeroteca polyguinea):

Sufficient amount of chemical solution having a specific concentration prepared from the hydrated powder of each test compound is sprayed on the seedlings of cucumbers (variants: Satsuki midori) grown for about three weeks in a pot of greenhouse.

The hairs are air dried and then inoculated with conidia of chemically resistant, chemically sensitive or mixed bacteria of powdery mildew (Spaerocateca polyguinea).

Store each parent pot separately in a greenhouse at approximately 25 ° C.

Onset is examined 10 days after inoculation.

The disease index is calculated by the following method. In other words, the disease index is 0, 1, 2, 3,... According to the disease spot on each leaf. Classify as 10.

The preventive value of each compound or mixed compound is calculated by the following preventive calculation formula.

Development of lesion index or spot

0… No lesions or spots appear at all on the leaf surface.

One… One to five spots appear on the leaf surface.

2… 6 to 10 spots appear on the front surface.

3... 30% of the leaf surface is infected with lesions or stains.

4… 31-40% of leaf surface is infected with lesions or stains.

5... 41-50% of leaf surface is infected with lesions or stains.

6... 51-60% of leaf surfaces are infected with lesions or stains.

7... 61-70% of the leaf surface is infected with lesions or stains.

8… 71-80% of leaf surfaces are infected with lesions or stains.

9... 81-90% of leaf surfaces are infected with lesions or stains.

10... 91-100% of the leaf surface is infected with lesions or stains.

The gal was shown in the following 3rd table | surface (3-1 and 3-2).

[Table 3]

Comparative Compound 1: Thiophanate Methyl

〃 2: carbendazim

(미합중국 특허 제4,237,168호)〃 3:

(U.S. Patent No. 4,237,168)

[Table 3]

Trial 3 Brown Beet (Sercospora Beticola):

A sufficient amount of an aqueous solution having a specific concentration prepared in the hydrated powder of each test compound is sprinkled on young hairs of beets (variety: monohill, 5 to 6 leaf stages) grown in porous backcountry pots having a diameter of 9 cm.

The leaves are air dried and sprayed with a conidia of resistant or sensitive brown pattern disease (Sercospora berry cola) to a compound or mixture thereof of benzimidazole-thiophanates.

Inoculated young beets are placed in high humidity at 24-26 ° C for one day and stored in a greenhouse at 23-28 ° C for 12 days. Then check the occurrence of spots. According to the following standard method, the diseased number of each treated area is investigated as the following indication, and the preventive value (%) is calculated by the following preventive calculation formula.

Development of lesion index or spot

0… No outbreak was found.

0.5... 3-5 spots found on leaves.

One… 3-5 spots found on leaves.

2… 10-25% of leaf surface is infected with spots.

3... 51-75% of the leaf surface is infected with spots.

4… More than 75% of leaf surface is infected with spots.

The hook was shown to the following 4th table | surface (4-1 and 4-2).

[Table 4]

Comparative Compound 1: Thiophanate Methyl

〃 2: pentine hydroxide

(미합중국 특허 제4,237,168호)〃 3:

(U.S. Patent No. 4,237,168)

[Table 4]

BT-4 to BT-1: same as test 1 or test 2

Trial 4 Apple's Black Star Plague (Venturia Inaqualis)

Aqueous solutions with specific concentrations, prepared from each test compound, are sprayed onto the young mothers of apples in three to four mouth stages (variant: coke) grown in porous backcountry pots.

The hairs are dried and inoculated with a conidia of benzidiazole-thiophanates, which are resistant or susceptible to black star pattern disease (Venturia in Aqualis).

Bottles are inoculated when each inoculated seedling is separated in a humidified room at 16 ° C and stored in a greenhouse at 15-20 ° C.

After 2 weeks, the incidence of each inoculated mock leaf is investigated according to the following survey standard, and the percentage of prevention of the treated area is calculated by the following formula.

Survey standard:

The gal was shown in the following 5th table | surface (5-1 and 5-2).

[Table 5]

Comparative Compound 1: Thiophanate Methyl

〃 2: Captan

(미합중국 특허 제4,237,168호)〃 3:

(U.S. Patent No. 4,237,168)

[Table 5]

BT-1 and BT-2: same as test 1

Test 5 cucumber germ disease (seufererospora cuvensis):

Aqueous solutions with specific concentrations prepared in the hydrated powder of each test compound are sprayed onto young hairs of cucumbers (variety: Sagami Hanjiro) grown for about two weeks.

The hairs are dried and inoculated by spraying a liquid suspension containing juiceporanium of ceudoferronospora cobensis collected from cucumber leaves infected with Downy mildew.

The hairs are placed in an inoculation box having 100% relative humidity at 5 ° C.

On the second day after inoculation, cucumbers are transferred to a room at 23 to 28 ° C.

Seven days after inoculation, the incidence of each cucumber leaf is examined according to the following standard.

Survey standard:

The preventive value in the treated area is calculated by the following formula:

The gal is shown in the following 6th table | surface.

[Table 6]

Comparative Compound 1: Chlorotaronyl

〃 2: Geneb

Trial 6 Activity of pesticides against ganglia moths.

The hydrated powder (in the case of metal salts of the compound) prepared according to the above example is diluted with water to obtain a solution or emulsion having a concentration of 500 ppm of the test compound.

Corn leaves are soaked in the liquid composition for 30 seconds and air dried.

The treated leaves are placed on a glass plate containing 5/3 young larvae of perilla moths and covered with a glass plate. Place a glass plate in a room kept at 25 ° C and 65% relative humidity and examine mortality after 120 hours. The result obtained by repeating twice is shown in Table 7.

[Table 7]

(미합중국 특허 제4,237,168호)Comparative Compound A:

(U.S. Patent No. 4,237,168)

Cotton aphid

Test 7 activity of pesticides against cotton aphids:

Dilution with water with a hydrated powder of the test compound prepared according to the above example yields a solution or suspension of 500a.i.ppm (ppm of active ingredient).

Cotton aphids inoculated in young cucumbers in pots are sprayed with an aqueous solution of the compound and stored in a room at 25 ° C. and 65% state humidity. Aphid activity is assessed 7 days after treatment. The control effect (%) is calculated by the formula (1-B / A) × 100. Where A is the rate of increase in untreated pots (aphid number 7 days after treatment of aphids before treatment) and B is the rate of increase in treated pots.

The girl is shown in the eighth table.

[Table 8]

Comparative Compound A: Compound identical to that shown in Test 6.

Cicada cicada

Insecticides and activities against Test 8 cicada larvae:

The hydrated powder (in the case of metal salts of the compound) prepared according to the above example was diluted to give a solution or suspension of 125a.i.ppm.

The young rice containing female adult larvae's eggs is immersed in the above aqueous solution and stored in a room at 25 ° C. and 65% relative humidity.

Live larvae are counted 13 days after treatment.

The activity (%) of the pesticide is calculated by the formula (1-B / A) × 100. Where A means the number of larvae in the untreated port and B means the number of larvae in the treated port.

The girl is shown in the ninth table.

[Table 9]

Comparative Compound A: Compound identical to that shown in Test 6.

Claims (5)

As a compound represented by the following general formula (I), or a salt of an organic inorganic acid and a compound of the general formula (I), or a complex of a metal salt with a compound of the general formula (I), and a benzimidazole-thiopatate crab bactericidal compound A bactericidal composition, characterized by consisting of an inert carrier and an amount of a mixture with a compound selected from the group consisting of:

Wherein X is halogen, nitro, cyano, formyl, C _2-8 alkylcarbonyl, carboxy, C _2-8 alkoxycarbonyl, C _3-8 alkenyloxycarbonyl, C _3-8 alkynyloxy Carboxyl, carbamoyl, C _2-6 alkylcarbamoyl, oxygen containing heterocyclic radicals and cyano, hydroxy, halogen C _1-6 alkoxy, C _1-6 alkoxy substituted C _1-6 alkoxy , C _2-6 alkanyloxy, C _2-6 alkynyloxy, C _3-8 alkynyloxycarbonyloxy, C _1-6 alkylthio, C _1-6 alkylsulfinyl, C _1-6 alkylsulfonyl , C _1-6 ; The same or different substituents selected from the group consisting of saturated or unsaturated C _1-6 hydrocarbon radicals which may be substituted with a substituted, amino, hydroxyimino, C _1-6 alkoxyimino and or C _2-8 alkoxycarbonyl. -B- is -O-, -S-, -SO-, -SO ₂ -or

(R 'is hydrogen or C _1-6 alkyl); Y is hydrogen or halogen, cyano, C _3-6 cycloalkyl, C _2-8 alkylcarbonyloxy, C _2-8 alkylcarbonyl, C _2-8 alkoxycarbonyl, hydroxy, C _1-6 alkoxy, The same or different substituents selected from the group consisting of C _1-6 alkylthio, ureido or oxygen-containing heterocyclic radicals (BY) _n part is C _1-6 alkoxy, -O- (CH ₂ ) lO (CH ₂ ) l'- and -O- (CH ₂ ) lO-CO- (l and l 'are 1 to 3, respectively) Integer) represents this substituted radical -BY- selected from the group consisting of C _1-3 alkylenedioxy which is substituted by: each of m and n is 0

m + n

Under the condition of 5 is an integer from 0 to 5, the substituent taking on "one" except for this substituted modified radical -BY type which takes "this": R is one substituent selected from the group consisting of saturated or unsaturated C _1-18 hydrocarbon radicals which may be substituted by halogen, cyano, C _1-6 alkoxy, C _1-6 alkylthio, C _1-6 alkoxycarbonyl: "C number-number" represents the range of the total carbon number of a substituent or a radical. 2. An inert carrier and an effective amount of a mixture of a compound selected from the group consisting of a compound wherein the at least one -BY substituent is present in the phenyl radical of formula (I) with a benzimidazole-thiophanate germicide compound Sterilizing composition, characterized in that consisting of. The sterilizing composition according to claim 2, which comprises an inert carrier and an effective amount of a mixture of a compound wherein -B- is -O- and a benzimidazole-thiophanate compound selected from the group consisting of bactericidal compounds. The effective amount and inactivity of a mixture of a compound selected from the group consisting of a compound wherein Y is a halogen-substituted saturated or decompressed C _1-6 hydrogen carbonate radical with a benzimidazole-thiophanate sterile compound A bactericidal composition, characterized in that consisting of a carrier. 2. A compound according to claim 1, wherein one of the -BY substituents is a compound selected from the group consisting of a benzimidazole-thiophanate sterile compound and a compound present at the 3 or 4 position of the phenyl radical of the general formula (I). A sterilizing composition comprising an effective amount of the mixture and an inert carrier.