JPS62273941A - Triazene derivative, production thereof and agricultural and horticultural fungicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:A triazene derivative of formula I (X is halogen; Y is lower alkyl, lower alkoxyl or OH; R is lower alkynyl). EXAMPLE:1,1-Dimethyl-3-(3-chloro-4,5-dipropargyloxyphenyl)triazene. USE:An agricultural and horticultural fungicide. It exhibits strong selective fungicidal effect against phytopathogenic fungus and other mold resistant to cyclic imide fungicides. PREPARATION:The compound of formula I can be produced by diazotizing the aniline derivative of formula II and reacting the obtained diazonium salt with the secondary amine of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein X represents a halogen atom, Y represents a lower alkyl group, a lower alkoxyl group or a hydroxyl group, and R represents a lower alkynyl group. The present invention relates to a triazene derivative represented by the formula (hereinafter referred to as the compound of the present invention), a method for producing the same, and an agricultural and horticultural fungicide containing the triazene derivative as an active ingredient.

The compounds of the present invention include benomyl [methyl 1-(butylcarbamoyl)benzimidazole-2-ylbamate], fuberidazole [2(2-furyl)benzimidazole], thiabendazole [2-thiazol-4-ylbenzimidazole], carpendazim [Methyl benzimidazole-2-ylbamate], thiophanate methyl [dimethyl 4.4-0-)unisine bis(3-thioallophanate)], thiofunate [diethyl 4.4-0-)unisine bis benzimidazole thione mononate fungicides such as (3-thioaromer mononate)] and procymidone [N-(3', 5'
-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboxylic acid 1, iprodione [3
-(3',5'-dichlorophenyl) -N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide], vinclozolin [3-(3',5'-dichlorophenyl)-5-methyl-5-vinyl -1,3-oxazolidine-2,4-dione], dicrosilinate [ethyl 3-(,1',s'-dichlorophenyl)-5-methyl-2,4-dioxoxazolidine-5-carboxylate], etc. It is characterized by selectively exhibiting a strong bactericidal effect against plant pathogenic bacteria and other filamentous fungi (hereinafter referred to as drug-resistant bacteria) that are resistant to imide-based fungicides.

The present inventors have conducted extensive studies on J1 official fungicides that exhibit bactericidal effects against drug-resistant patients, and as a result, have discovered the compound of the present invention represented by the general formula [1].

Examples of drug-resistant bacteria that exhibit the bactericidal effect of the compounds of the present invention include, for example, apple powdery mildew fungus ()'odosph.
aera 1eucotricha), Venturiainaequalis, Pear scab B (Venturianashicola)
, clerotinia mali (5clerotinia mali)
), Kerr F's anthracnose @ (Glo6osporium
kaki), peach gray blight fungus (5clerotini)
a cinerea), Cladosp.
rium carpophilum ), Botrytis cinerea ,
Black rot fungus (Eisinoeampel 1na),
Glomerella cingulata
), Cercospora be
ticola), peanut brown spot (Cerco
spora arachidicola), black astringent fungus (
Cercospora personata), oat eye strain fungus (k'5eudocercosporell)
a herpotrichoides), barley powdery mildew (Erysiphe graminis f.
.

sp hordei), Fusari
um n1vale), wheat powdery mildew @ (E
rysiphe graminis f.

sp, tritici), Powdery Mildew of Chieuri (5phaerotheca fuliginea)
, Mycosphaerella m.
elonis), gray mold fungus (Botrytis)
cinerea), Cladospor
Ciumcucumerinum), tomato rape fungus (C1adospo-rium), gray mold fungus (C1adospo-rium),
Botrytis cinerea), strawberry powdery mildew (5phaerotheca humuli)
), Botrytis cin
area), tobacco udon ζ disease @ (Erysip
he cichoracearum), rose scab fungus (Diplocarpon rosae), tangerine scab fungus (Mlsinoe fawcetii),
Penicillium italicu
m), Penicillium di
gitatum).

Examples of the compounds of the present invention include the compounds shown in Table 1.

Table 1 general formula Compound represented by Next, a manufacturing example of the compound of the present invention will be explained.

In the compound of the present invention, in the general formula 1, X and k have the same meanings as above. The aniline derivative represented by 1 is converted into a diazonium salt by a diazotization reaction, and in the general formula E, Y has the same meaning as above. It can be produced by reacting with the secondary amine shown in 1.

The diazotization reaction of the aniline derivative represented by the general formula [T1] can be carried out without a solvent or in a solvent such as water, dioxane, acetone, etc. with an inorganic acid (hydrochloric acid, sulfuric acid, hydrobromic acid, etc.) or an organic acid (formic acid, acetic acid, etc.). ) in the presence of an alkali metal nitrite salt (
This can be done by adding sodium nitrite, potassium nitrite, etc.), alkaline earth metal salts (barium nitrite, etc.), or nitrite lower alkyl esters (methyl nitrite, etc.). This reaction is typically completed in 10 minutes to 12 hours at -50°C to room temperature. The diazonium salt thus obtained is subjected to the next condensation reaction with an amine either singly or as a reaction solution, if necessary.

Diazonium salt and general formula [! The condensation reaction with a secondary amine represented by [I] is typically carried out at room temperature to 150°C for a period of time to
It will be completed in about 12 hours.

After the reaction is complete, the reaction solution is poured into ice water and subjected to normal post-treatments such as organic solvent extraction and shrinkage, and if necessary, subjected to operations such as chromatography, recrystallization, and distillation to obtain the desired product. Inventive compounds can be obtained.

The aniline derivative represented by the general formula [1[] is the following a
It can be produced by method, b method or a method.

[method a]

[NI[V]E In the formula, X and R represent the same meanings as above, and Z represents a halogen atom, mesyloxy group or tosyloxy group. ] That is, the nitrocatechol derivative represented by the general formula [IV] is reduced to form an aminocatechol derivative represented by the general formula [VJ], and then this is reacted with a compound represented by the general formula ['J] to form the general An aniline 0 conductor represented by formula [11] is obtained.

The aminocatechol derivative represented by the general formula [VJ] can be obtained by reducing the nitrocatechol derivative represented by the general formula LP/].

This reaction can be carried out in accordance with the usual reduction reaction of a nitro group to an amino group.

In addition, this reaction can be carried out, for example, in a solvent in the presence of a catalyst.
It is carried out by catalytic reduction with hydrogen gas at ~200''C and atmospheric pressure ~200 atmospheres.

Solvents used in the reaction include dimethylformamide, tetrahydrofuran, dioxane, toluene, rnf
Examples of the catalyst include platinum dioxide, palladium on carbon, and Raney nickel.

After the reaction is complete, the reaction solution is poured into ice water and subjected to standard post-treatments such as organic solvent extraction and saturation, and if necessary, subjected to operations such as chromatography, recrystallization, and distillation to obtain the desired compound. can be obtained.

Next Cζ, the reaction between the aminocatechol derivative represented by the general formula [Vi] and the compound represented by the general formula [V1] is typically carried out in a solvent in the presence of a base at 0 to 20"C, preferably at room temperature at 90°C. ℃, almost complete in 1 to 30 hours.

When using a solvent to complete the reaction, examples of the solvent include dimethylformamide, tetrahydrofuran, acetonitrile,
Examples include chloroform, toluene, water, etc., or mixtures thereof. Examples of the base include organic bases such as sodium hydride, triethylamine, and pyridine, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

After the reaction is complete, the reaction solution is poured into ice water and subjected to normal post-treatments such as organic solvent extraction and concentration, and if necessary, the desired compound can be isolated by subjecting it to chromatography, recrystallization, distillation, etc. Obtainable.

The nitrocatechol conductor represented by the general formula [M] is described in J, Org, Chem, 1981.16.38
It can be produced by the method described in 47-.

(Method b) [■l [Kl 1 In the formula, A represents a lower alkyl group, B represents a halogen atom, and X and R represent the same meanings as above. A catechol derivative and a compound represented by general formula [■] or [■'1 are reacted to obtain an anilide derivative represented by general formula [■], and this is reacted with a compound represented by general formula [VJ] By doing this, an anilide derivative represented by the general formula [xl] is obtained, and by hydrolyzing this, the anilide derivative represented by the general formula [111
An aniline derivative represented by is obtained.

The reaction between the aminocatechol derivative represented by the general formula [VJ] and the compound represented by the general formula [■J or the general formula [v1'] is carried out without a solvent or in a solvent, if necessary in the presence of a base.

The reaction temperature and reaction time for this reaction are typically room temperature to
The process is almost completed within the range of 120°C, from instantaneous to 12 o'clock.

When using a solvent, examples of the solvent include water, acetic acid,
Examples of bases include ethyl acetate, benzene, toluene, xylene, tetrahydrofuran, and dioxane.
Examples include pyridine, N,N-diethylaniline, triethylamine, and sodium hydroxide.

After the reaction is complete, the reaction solution is poured into ice water and subjected to normal post-treatments such as organic solvent extraction and concentration, and if necessary, the desired compound can be isolated by subjecting it to chromatography, recrystallization, distillation, etc. Obtainable.

The condensation reaction between the anilide derivative represented by the general formula [■l and the compound represented by the general formula [] is carried out using the general formula [V
The reaction can be carried out in the same manner as the reaction between the amine catechol derivative represented by J and the compound represented by the general formula (Wl).

J: Hydrolysis reaction 11 of an anilide derivative represented by the general formula [Kl], carried out in a standard solvent in the presence of a hydrolysis auxiliary agent. This reaction is almost completed within a range of room temperature to the reflux temperature of the medium, and within a range of 10 minutes to 12 hours. Examples of the solvent used in this reaction include water, methanol, ethanol, toluene, tetrahydrofuran, and dioxane.

As the hydrolysis aid, mineral acids such as ia*, sulfuric acid, Lewis acids such as boron trifluoride, and inorganic bases such as sodium hydroxide and potassium hydroxide can be used.

After the reaction is complete, the reaction solution is poured into ice water and subjected to normal post-treatments such as organic solvent extraction and condensation, and if necessary, subjected to operations such as chromatography, recrystallization, and distillation to achieve the desired result. compound can be obtained.

[Method C] EX] [In the formula, X and R represent ml and waste. 1 That is, the general formula [! A cross conductor is obtained by combining the nitrocatechol conductor represented by [1/] and a compound represented by the general formula CViJ, and by reducing this, an aniline derivative represented by the general formula [II] is obtained.

It can be carried out in the same manner as the condensation reaction between the nitrocatechol-derived tecol derivative represented by the general formula [N] and the compound represented by the general formula [V].

For the reduction reaction of the nitrobenzene derivative represented by the general formula [X], a usual reduction reaction of a nitro group to an amino group can be used. This reaction is similar to the following example: water, methanol,
It can be carried out in ethanol, propatool or a mixed solvent thereof, using sodium sulfide, sodium hydrogen sulfide, etc. as a reducing agent, at a temperature of 40°C to solvent reflux for instantaneous to 12 hours, or in acetic acid, sulfuric acid, or hydrochloric acid. The reaction can be carried out, if necessary, diluted with water and using iron, zinc, tin, etc. as a reducing agent, typically at a temperature of 40''C to core medium reflux temperature, for instantaneous to 12 hours.

After the reaction, after disposing of unreleased materials, if it is a water bath solution, yes! After extraction with 3 solvents, in the case of a non-aqueous solution, condensation is performed as it is, and if necessary, chromatography, reconsolidation, etc.
By adding ζ, the target object can be obtained from lζ.

Next, the manufacturability ξ of the present invention will be explained in more detail with reference to Examples.

Example 3-Chloro-4,5-dipropargyloxyaniline 1
．． (1, acetic acid to, of, [[1,01/CD mixture kept at O''QIr-, to which sodium nitrite 0.30f
was added and stirred for 30 minutes at O''C.The reaction solution was
50% dimethylamine aqueous solution 21. Of, 1O- of water and 21.0 l of sodium carbonate were added at room temperature. After stirring at room temperature for 12 hours, the reaction solution was poured into ice water and extracted with ethyl acetate. Organic! After washing m with water three times, it was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 1,1-dimethyl-3-(3-chloro-4,5-dipropargyloxyphenyl)triazene 1 I got .08.

nroo 1.6800 Some of the compounds of the present invention that can be produced by such a method are described in Section 2-A.

No. 22!2 general formula Triazene compound represented by Next, the method for producing compound [11] will be described using reference examples.

Reference Example 1 150 grams of iron powder, 620 grams of acetic acid and 1000 grams of water were stirred and kept at 40°C. Here, 78.51 of 3-chloro-4,5-dibropargyloxynitrobenzene was added to 2
A solution of 00- was added dropwise over 30 minutes. 7
After heating and stirring at 0°C for 15 minutes, insoluble matter was separated from P and lP
The liquid was extracted with ethyl acetate. After washing several layers with an aqueous potassium carbonate solution and water, they were dried over anhydrous magnesium sulfate.

The solvent was distilled off under reduced pressure to yield 56.11 G of 3-chloro-4,5-dipropargyloxyaniline.

4.62 (d, 2H), 8.58 (broad,
2H), 2.50(t, 1)1), 2.48(t
, 1) 1) Reference example 2 3-chloro-4,5-dihydroxyaniline 4.20f
1 dioxane 50. Anhydrous vinegar tl 12.701 was added to the mixture of d and acetic acid 50 at room temperature, and the mixture was stirred under reflux for 15 minutes. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was mixed with a 1=1 mixed F8 medium of chloroform and ethyl acetate, and then developed with ether.
3-Chloro-4,5-dihydroxyacetanilide was obtained by silica gel column chromatography used as '8B.

MS MVIRδL) Mso-d6:9.70(brOad,
3H), 7.05 (8, 2H), 2.00 (S, 3) 1
) Reference Example 3 3-chloro-4,5-dihydroxyacetanilide 2.
Put 02F into L) MF50- and place O'C here.
0.40jF of sodium hydride (60% oily) was added. Then, after raising the temperature to room temperature, propargyl bromide 1
．． Added 30F. After raising the temperature to 90°C, the mixture was cooled to 0°C, and 0.40% of sodium hydride was added.

The temperature was raised to room temperature, and 1.30 f of propargyl bromide was added. After raising the temperature to 90'C, the reaction solution was poured into ice water.

After extraction with ethyl acetate, washing with water J1, and drying with magnesium sulfate, the resulting residue was subjected to silica gel column chromatography using toluene and ethyl acetate to obtain 3-chloro-4,5-dibromer. 1.9 (l) of pargyloxyacetanilide were obtained.

IVIS 顯δ1xvtsu a, : 10.04 (broa
d-IH), 7.40 (d, IH), 7.30 (d,
1)i), 4.79(d.

2H), 4.65(d, 2)i), 3,30(t,
1) 1), 2.05 (S, 3) 1), Reference example 4 3-chloro-4,5-dipropargylacetanilide 5
．． 0Of, methanol 50- and boron trifluoride 10-
．． 0y+ mixed and stirred under reflux for 10 hours. The reaction solution was concentrated under reduced pressure, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and the resulting residue was subjected to EA-based alumina column chromatography using toluene and ethyl acetate, the solvent was distilled off under reduced pressure, and 3-chloro-4 , 5-dibropargyloxyaniline 8.80f was obtained.

When the compound of the present invention is used as an active ingredient in a fungicide for agriculture and horticulture, it may be used as is without adding any other ingredients, but it is usually used in combination with a solid carrier, liquid carrier, surfactant, or other formulation auxiliary agent. It is used by mixing with the compound and formulating it into emulsions, wettable powders, suspensions, powders, liquids, etc.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 1 to 95%, preferably 2 to 80%.

Solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyroferrite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene.
, alcohols such as isopropanol and ethylene glycol cellosolve, ketones such as acetone, cyclohexanone and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide acetonitrile, and water.

Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfate salts, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymer , sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and other nonionic surfactants.

As formulation aids, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), )'AP (isopropyl acid phosphate), and the like.

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 2. Parts are parts by weight. Formulation Example 1 50 parts each of the compounds (1) to (3) of the present invention, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide were thoroughly ground and mixed, and mixed with water. Obtain Japanese medicine.

Formulation Example 2 10 parts each of the compounds (1) to (3) of the present invention, 10 parts of polyoxyethylene styrylphenyl ether, and 80 parts of cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 3 2 parts each of the compounds (1) to (3) of the present invention, 4 parts of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 80 parts of bentonite and 65 parts of kaolin clay are thoroughly ground and mixed, and water may be added. After kneading, the mixture is granulated and dried to obtain granules.

Formulation Example 4 Compounds of the present invention (25 parts each of 13 to (3), 3 parts of polyoxyethylene sorbitan monooleate, CM Ca,
A suspension is obtained by mixing 69 parts of water and wet milling until the particle size is 5 microns or less.

Formulation Example 5 Two parts each of the compounds (1) to (3) of the present invention, 88 parts of kaolin clay, and 10 parts of talc are thoroughly ground and mixed to obtain granules.

Formulation Example 6 10 parts each of the compounds (1) to (3) of the present invention,
1 part of thiethylene styryl phenyl ether and 89 parts of water are mixed to obtain a liquid preparation.

Formulation Example 7 Compounds of the present invention (1), 2 parts each of (3), 88 parts of clay, and 10 parts of talc are thoroughly ground and mixed to obtain a powder. These preparations can be used as is or diluted with water, etc., and treated with foliage or soil. For soil treatment, spray the preparation on the soil surface (if necessary, crystallize with the soil after spraying).

) Seed treatment is also possible depending on the disease. Also,
By mixing it with other agricultural and horticultural fungicides, it can be expected to increase the control efficacy. In addition, insecticides, acaricides,
It can also be used in combination with nematocides, pest control agents, plant growth regulators, fertilizers, soil volume improvers, etc.

The compound of the present invention can be used as an active ingredient of a fungicide for agricultural and horticultural purposes such as paddy fields, fields, orchards, tea plantations, pastures, and lawns.

When the compound of the present invention is used as an active ingredient of a fungicide for agriculture and horticulture, the amount of application depends on the attenuation conditions, formulation form, treatment time,
Although it varies depending on the method, location, target disease, target crop, etc., it is usually 0.5I to 501 per are, and emulsions,
When applying wettable powders, clouding agents, liquid preparations, etc. diluted with water,
The application concentration is o, o o s% to 0.5%, and granules, powders, etc. are applied as they are without any dilution.

Next, test examples will show that the compounds of the present invention are useful as active ingredients for agricultural and horticultural fungicides. The compounds of the present invention are shown by the compound numbers in Table 2, and the compounds used for comparison are shown by the compound numbers in Table 3. Tsume and cucumber (product M: Sagami Hanshiro) were sown. This was cultivated in a greenhouse for 8 days to obtain chiecurly with expanded cotyledons. According to this Young Seedling 1ζ Preparation Example 2 or 1, the test drug in the form of an emulsion or a wettable powder was diluted with water to a predetermined concentration, and 1 liter per pot was prepared.
Sprayed on foliage. After air-drying the chemical solution, the young cup was infected with chemical-resistant or sensitive cucumber gray mold fungus (Botrytis cin).
A section (5-diameter) of the bacterial flora of M. rea) was pasted onto the leaf surface and inoculated. This was placed in a humid environment at 20"C for 8 days to develop the disease, and then the disease state was observed.

The disease severity was calculated by the following method.

That is, depending on the appearance of lesions on the surveyed vegetables, 0.0.5, 1
．． The disease was classified into an index of 2.4, and the disease severity was calculated using the following formula.

(Sickness index) (Sickness state) O...
No bacterial flora or lesions are observed on the leaf surface.

0.5: Bacterial flora or lesions are observed on the leaf surface in less than 5% of the leaf area.

1: Bacterial flora or lesions are observed on the leaf surface in less than 2,096 leaf areas.

2: Bacterial flora or lesions are observed on the leaf surface in less than 50% of the leaf area.

4...Bacterial flora or lesions are observed on the leaf surface over 50% of the leaf area.

Next, the control value was calculated using the following formula.

The results are shown in Table 4.

Table 4 Test Example 2 Antibacterial activity against wheat eye spot bacteria Pseudocercosporella herp, which is drug-resistant or drug-susceptible, was added to an agar medium.
otrichoides) was allowed to form. This was scraped into sterile water to prepare a spore suspension. On the other hand, a dimethyl sulfoxide solution of the test compound was added to the agar medium in the petri dish to a predetermined concentration. Here, the spore suspension described above was polarized and cultured at 23"C for 7 days.

The antibacterial activity was visually evaluated into four levels depending on the degree of mycelial growth.

1: No growth is observed with the naked eye.

±: Slight growth is observed.

+: Less growth than untreated.

+F: Growth is at the same level as untreated.

The results are shown in Table 5.

Table 5 Test Example 3 Phytotoxicity test on crops 150-volume plastic pots were filled with sandy loam soil, and wheat (variety: Norin No. 61), apple (variety: Kougyoku), and peanut (variety: Chiba Tetachi) were each grown. Seeds were planted and cultivated in a greenhouse. An aqueous dilution of the test compound in the form of an emulsion or wettable powder prepared according to the above-mentioned formulation example was sprinkled onto the obtained young vines. After spraying, the seeds were placed in the greenhouse again, and after culturing for 10 days, the presence or absence of phytotoxicity was investigated according to the following criteria.

Standards for degree of drug damage (Procedure:) (Symptoms) -No abnormality.

10. Abnormalities due to chemical damage are observed in some of the crops.

Abnormalities due to chemical damage are observed throughout the crop.

■ The plant will wither and die due to chemical damage.

The results are shown in Table 6.

Table 6

Claims (3)

[Claims] (1) General formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X represents a halogen atom, Y is Lower alkyl group, lower alkoxyl group or represents a hydroxyl group, R is a lower alkynyl group represents. ] A triazene derivative represented by (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X represents a halogen atom and R represents a lower alkynyl group. ] The aniline derivative represented by is converted into a diazonium salt by a diazotization reaction, and the general formula ▲ has a numerical formula, a chemical formula, a table, etc. ▼ [In the formula, Y represents a lower alkyl group, a lower alkoxyl group, or a hydroxyl group. ] A general formula characterized by reacting a secondary amine represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X, Y and R represent the same meanings as above. ] A method for producing a triazene derivative shown in (3) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X represents a halogen atom, Y represents a lower alkyl group, lower alkoxyl group, or hydroxyl group, and R represents a lower alkynyl group. ] An agricultural and horticultural fungicide characterized by containing the triazene derivative shown below as an active ingredient.