JPS5995274A - Phenylacetylimidazole compound, preparation thereof, agricultural and horticultural germicide, herbicide or plant growth regulating agent containing the same as active constituent - Google Patents

Abstract

NEW MATERIAL:A phenylacetylimidazole compound expressed by formula I [X is halogen, alkyl, haloalkyl or alkoxyl; R<1> and R<2> are alkyl, alkoxyalkyl, alkenyl, alkoxyl, haloalkyl or halogen or R<1> and R<2> represent alkylene chain which may be substituted; n is 0, 1 or 2, provided that R<1> and R<2> are not (CH2)4 when Xn are 2,4-dichloro]. EXAMPLE:1-(alpha-Ethyl-alpha-methyl-2,4-dichlorophenylacetyl)imidazole. USE:An agricultural and horticultural germicide, herbicide or plant growth regulating agent. PROCESS:A phenylacetic acid compound expressed by formula II or a reactive derivative thereof is reacted with imidazole to give the aimed compound expressed by formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (Il [wherein,
It does not represent an alkenyl group, an alkoxyl group, a haloalkyl group, or a halogen atom, or an alkylene chain optionally substituted with k and . n represents 0, 1 or 2. However, when xn is a 2,4-dichloro group, and k are not -(CI(2)4-).] A phenylacetylimidazole compound represented by the following, its production method, and containing it as an active ingredient. Related to agricultural and horticultural fungicides, herbicides, or plant growth regulators.

This will be explained in more detail below.

The plant diseases targeted by the compound of the present invention include rice leaf blight (Cochliobolus mlyabean).
us), apple powdery mildew (Podosphaera
1eucotricha), scab (Venturi)
a 1naequal is), Monilia disease (5cl
erotinia mal i), black spot disease (Myco
sphaerellapomi), pear black spot (Al
ternaria kikuchiana), powdery mildew (Phyllactinia pyri), Gymnosporangium Ltaraean
um), Venturianash 1col
a), citrus blue mold (Penicillium
italicum), green mold (Penicilliu)
m digitatum), oyster powdery mildew (Phy.
llactinia kakicola), leaf fall disease (M
ycosphaerella nawae, Cer
cospora kaki), grape powdery mildew (
Uncinula necator ), Rust (P
hakopsora ampelopsidis),
Powdery mildew of barley (Erysiphe grnm)
inis fl1sp, bordei), Rhynchosporium 5ecalis
), Puccinia hordei
, black rust (Puccinia graminis)
, Pyrenophora graminea
), Pyrenophora teres,
Wheat rust (Puccinia recondi)
ta), yellow rust (Puccinia strii-f
ormis), black rust (Puccinia gram)
inis f, sp.

tritici), powdery mildew (Erytipbe
graminis f.

sp atrici ), eye spot (Pse
udocercosporellaherporell
a herpocrichoides), leaf blight (5
eptoria tritici ), blight ( Lepc
osphaeria nodorum), bovine powdery mildew (5phaerotbeca fuligin)
ea), vine blight (Mycosphaerella m.
elonis), tomato powdery mildew (Erysi
phe cickoracearum), varicose disease (Al
ternaria 5olani), powdery mildew of eggplant (Erysiphe cichoracerum), powdery mildew of green pepper (Levillula taur)
ica), powdery mildew (5phaerothe
ca humuli), tobacco powdery mildew (Er.
ysiphe cichoracerum), Akaboshi disease (
Ccrcospora arach i d
i cola), Botrytis blight (Botr) of various crops
ytis cinerea), Sclerotinia (5clerot)
inia scleroti-orum), gray layer disease of stone fruit trees (5clerotinia cine-rea
) etc.

The compound of the present invention can also be used as a plant growth regulator, and is applied to useful plants to suppress their growth. For example, by applying the compound of the present invention at an appropriate time, it is possible to appropriately control the plant height of rice and wheat to prevent lodging, and to prevent the growth of lawns, hedge trees, fruit trees, etc. Also,
It can also be used to soften garden crops such as potted chrysanthemums, and to prevent axillary buds of tobacco.

Furthermore, the compounds of the present invention exhibit particularly strong efficacy as herbicides against grass and broad-leaved upland weeds, paddy field weeds, and perennial weeds.

In the case of fields, it can be used as a soil treatment before weeds emerge or as a foliage treatment in the early stage of growth, and in the case of rice fields, it can be used before weeds germinate or in the early growing season.

Therefore, the compounds of the present invention are useful as herbicides not only for paddy rice but also for various grains, vegetables, orchards, lawns, pastures, tea gardens, mulberry gardens, rubber gardens, forests, non-agricultural lands, and the like.

The present invention also includes salts of the compounds of the present invention, such as inorganic acids such as hydrobromic acid, hydrochloric acid, hydroiodic acid, sulfuric acid, nitric acid, etc., or acetic acid that is physiologically acceptable to plants. , carboxylic acids such as trichloroacetic acid, maleic acid, and succinic acid, or salts of l)-toluenesulfonic acid with toxsulfonic acid or phosphoric acids.

Next, the method for producing the compound of the present invention will be described.

The compound of the present invention represented by the general formula CI) can be produced by reacting a phenylacetic acid compound represented by the following general formula [■] or a reactive derivative thereof with imidazole.

[In the formula, X, R1, R2 and n are the same as above]
It has the meaning of degree. ] 1
In this case, the reaction solvent is benzene, toluair,
A, 2nd class. Carbonized water 1. . sex i, g 7
-W 7, Salt Ihi, f, 7, .

. O 7. ,,, □ Halogenated hydrocarbons such as carbon chloride, ethers such as diethyl ether and tetrahydrofuran, nitriles such as acetonitrile, ketones such as acetone, methi/I/x thyl ketone, dimethyl pol 1
General solvents such as amide, di, thia□/lz, i; kid, 1, 7, etc. can be used.

Reaction, yoie l"/-/□yoki lysisi R:Dissolution ah, y
The charcoal is suspended and preferably dissolved in acetonitrile to give an amount of 0.4 to 1.5 equivalents, preferably 0.5 to 1.1
5 u co, H = a general formula [□] 7 ゎ67 z -”
), or add an acetic acid-based compound or its reactive derivative (Yo-reverse (.7 z = /L/Acetic acid-based compound Aoi (yoe)) Dissolve or suspend the reactive derivative in the above-mentioned solvent. Then add imidazole and carry out the reaction.

The reaction can be carried out at any temperature from the freezing point to the boiling point of the solvent, preferably from 0°C to the boiling point of the solvent.

In this reaction, the reactive derivative of the phenylacetic acid compound is an acid halide or an acid anhydride in the case of an acid chloride or an acid bromide.

In the case of the reaction of these reactive derivatives with imidazole,
As a reaction aid, for example, sodium ethylate, sodium methylate, tritylamine, pyridine, quinoline, isoquinone, N,N-dimethylaniline, N-methylluforine, sodium acetate, sodium carbonate, potassium sulfate, etc. are added in a catalytic amount to 1. 5 equivalents may be used. The sodium or potassium salt of imidal can also be used as a base for imidazole.

In addition, when combining a phenylacetic acid compound with imidazole, a reaction aid such as dicyclohexylcarbodiimide may be used as a reaction aid, or a reactive derivative of imidazole may be used instead of imidazole, such as N, go carbonyl diimidazole or N, R- Thiocarbonyldiimidazole and the like can also be used.

After carrying out the reaction as described above, the reaction aid or its reaction product is removed by filtration or washing with water, and the solvent is removed to obtain the compound of the present invention. This can be further purified by a general purification method such as column chromatography.

The compounds of the present invention thus obtained are shown in Table 1.

Next, a manufacturing example will be shown.

Production Example 1 (Compound No. 2) α-ethyl-α-notyl-2,4-dichlorophenylacetic acid 19 g (0,077 mol), thionyl chloride 40 m/,
) After heating a mixture of 100 d of toluene under reflux for 1 hour,
By distilling under reduced pressure, α-ethyl-α-methyl-2,
4-dichlorophenylacetic acid chloride 19 f (b,
p.

115-120°C 1O-2-=s) was obtained. Next, imidazole I OF (0,147 mol), triethylamine 9.39 (0,092 mol), dichloromethane 1
The above acid chloride 19f in 50 ml of mixed solution
(0,072 mol) was added and stirred for 1 hour. Pour the reaction solution into 200 rnl of ice water and add 200 rnl of dichloromethane.
t was added and extracted. The extract was concentrated under reduced pressure and subjected to silica gel column chromatography (eluent, acetone:
By purifying with n-hexane = 1:20), 1-(
α-Ethyl-α-methyl-2,4-dichlorophenylacetyl)imidazole 20F (yield: 94 cm) was obtained.

nDl, 5711 Production Example 2 (Compound No. 38) 7 g of α-methoxy-α-n-propyl-2,4-dichlorophenylacetic acid chloride was dropped into a mixture of 2.3 v of imidazole sodium salt and 20 ml of acetonitrile at room temperature.

After stirring for 2 hours, the reaction solution was poured into 200 rnl of ice water and extracted with 300 mL of chloroform.

After distilling off the solvent, the oily residue was subjected to silica gel chromatography (developing system: acetone: n-hexane = 1:20).
1-(α-methoxy-α-n-propyl-2
,4-dichlorophenylacetyl)imidazole 2゜5
(yield: 32 cm).

m, p, 99-101°C When the compound of the present invention represented by the above general formula CI) is used as a fungicide, herbicide or plant growth regulator, it may be used as it is without adding any other ingredients, Alternatively, preparations can be made by mixing with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries, such as powders, granules, wettable powders, sol preparations, emulsions, fine granules, aqueous solutions, oil solutions, tablets, and aerosol preparations. It may also be used as

Each preparation can contain the compound of the present invention as an active ingredient in a weight ratio of O01 to 99.9%, preferably 0.2 to 80.0%.

These formulations can be prepared according to conventional methods. In this case, the carrier is a vegetable carrier (for example, wheat flour, tobacco stem flour, soybean flour, walnut flour, wood flour, sawdust, bran, bark powder, fiber cord powder, residue after extracting the plant extract).
, textile products (e.g. paper, cardboard, furukire),
Crushed synthetic resins, clays (e.g. clay, kaolin, bentonite, acid clay, diatomaceous earth), talcs, and other inorganic minerals (e.g. pyrophyllite, sericite, pumice,
Examples include fine powders such as sulfur powder, activated carbon), and fine powders of chemical fertilizers (such as ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, and ammonium chloride). Liquid carriers include water, alcohols (Tatoe is methyl alcohol, ethyla/L, :I-
/I/ ), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. ethyl ether,
dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, kerosene), esters, nitriles, acid amides (eg, methylformamide, dimethylacetamide), halogenated hydrocarbons (eg, dichloroethane, trichloroethylene, carbon tetrachloride), etc. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, polyoxyethylene ethers, and polyhydric alcohol esters. In addition, usable fixing agents and dispersing agents include gelatin, starch powder, CMC1 arabic pine oil, agar, etc. Stabilizers include PAP (isopropyl acid phosphate), TCP (phosphoric acid), etc. (tricresyl acid), tall oil, epoxidized oil, various surfactants, various fatty acids or their esters, etc.

Furthermore, the compounds of the present invention may be used as other fungicides, insecticides, nematicides,
It can also be used in combination with acaricides, pest repellents, plant growth regulators, herbicides, fertilizers, or soil conditioners.

Examples of formulations are shown below. In addition, parts mean parts by weight.

Formulation Example 1 Powder Compound 1 (0.2 parts) of the present invention and clay (99.8 parts) are thoroughly ground and mixed to obtain a 0.2% powder. When used, it may be applied as is or mixed with soil.

Formulation Example 2 Emulsion Compound 2 of the present invention (10 parts), cyclohexanone (80 parts) and a surfactant, polyoxyethylene alkylaryl ether (10 parts) were mixed to obtain a 10% emulsion. When used, it may be diluted with water or applied as is.

Formulation Example 3 Wettable powder Compound 10 of the present invention (40 parts), surfactant, sodium lauryl sulfate (3 parts), dispersant, calcium lignosulfonate (2 parts), white carbon (15 parts), and diatomaceous earth (40 parts) ) can be thoroughly ground and mixed to obtain a 40-chi permanent agent. When used, it may be diluted with water or mixed with soil.

Formulation Example 4 Granules Compound 13 of the present invention (5 parts), bentonite (40 parts),
Clay (50 parts) and sodium ligninsulfonate (5 parts) were thoroughly ground and mixed, water was added, and the mixture was thoroughly kneaded to obtain granules with a dryness of 5%. When used, it may be applied as is or mixed with soil.

When the compound of the present invention is applied as a fungicide, herbicide, or plant growth regulator, the amount of application depends on weather conditions, the type of target plant, the growth stage, the growth situation, the type of disease, the state of disease onset, the time of application of the chemical, or the amount of application. Although it varies depending on the method, dosage form, and other conditions, the active ingredient usually contains 10 ares and 2 to 200 mg.
5009 is appropriate. Furthermore, the concentration of the active ingredient is preferably in the range of 0.001% to 1.0%.

Application methods include foliage treatments such as spraying, dusting, and coating on crops, soil mixed layer treatment, soil mixed layer treatment, root immersion treatment, and seed treatment.

Next, test examples will be given to show that the compounds of the present invention are useful as active ingredients of fungicides, herbicides, or plant growth regulators. The compounds used as controls in the test examples are shown in Table 2.

Table 2 Table 3 Test Example 2 Cucumber Gray Mold Control Effect Test Diameter 5cz
Cotyledon stage cucumbers grown in plastic pots (
A water diluted solution of a hydrating powder prepared according to Formulation Example 3 was sprayed on the cultivar (Sagami Hanjiro Bushusei) at a rate of 10 ml per post.

One day later, a edible agar piece (5-J in diameter) of Botrytis cinerea was inoculated onto the cotyledons and left in a humid environment at 20°C for 3 days to induce disease.

Calculation of control value is the same as in Test Example 1.

The results are shown in Table 4, and all of the compounds of the present invention showed superior pest control value compared to the comparative control compounds.

Table 84 Test Example 3 Wheat blight control effect test Water dilution of an emulsion prepared according to Formulation Example 3 on second true leaf stage wheat (variety: Norin No. 73) grown in a plastic pot with a diameter of 501. was sprayed at a rate of 10 parts per bot.

One day later, the spore solution of the blight fungus was spray inoculated, and the mixture was incubated at 20°C and humid for 3 days.
After keeping it for 1 day, it was cultivated in a greenhouse for 2 weeks. Calculation of control value is the same as in Test Example 1.

The results are shown in Table 5, and all of the compounds of the present invention showed superior pesticidal effects compared to the comparative control compound.

Table 5 Test Example 4 Weeding test for paddy fields A 115,000 RWagner pot was filled with 1.5 ml of paddy soil to create a paddy field, rice seedlings at the 3-leaf stage were transplanted, and barnyard grass seeds and bulrush seeds were sown. A water-diluted solution of the hydrating powder prepared according to Formulation Example 3 was poured into a 10-mj pot per pot using a pipette. On the 25th day after the chemical treatment, the level of herbicidal efficacy was investigated for the sown plants and naturally occurring broad-leaved weeds.

The results are shown in Table 6.

Evaluation of herbicidal efficacy was expressed as a number from 0 to 5 as shown below.

0: Weed suppression rate 0-9% 1: 0 10-29 2: // 30-49 3: // 50-69 4: * 70-89 5: /l 90-100 @6 table No chemical damage such as oxidation, chlorosis, or chlorosis was observed.

Procedural Amendment (Voluntary) December 1980, Director-General of the Patent Office Kazuo Wakasugi 1 Display of Case 1987 Inter-Patent No. 205806 2, Title of Invention: Phenylacenal imitazole compound, method for producing the same, and the same Relation to the case of a person who removes agricultural and horticultural fungicides, herbicides, or plant growth regulators containing as an active ingredient Patent applicant -12' 4 Agent
, ):・' and Address: 5-15 Kitahama, Higashi-ku, Osaka Sleeve n2 Subject: Detailed description of the invention in book I +++ Description 8, page 7, line 4 says "brown cypress" is corrected to 1゛brown spot disease.''

(2) Add the following to 713 people after Table 1 on page 16.

(3) On page 28 of the same page, insert the letter f between column 38 of the test compound in Table A and the column of control compound (at).

[ ” that's all

Claims (1)

Claims: (1) General formula [wherein, X represents a halogen atom, an alkyl group, a haloalkyl group, or an alkoxyl group; It represents an alkoxyl group, a haloalkyl group, a halogen atom, or an alkylene chain optionally substituted with 1 and R2. n is 0,
Represents 1 or 2. However, when Xn is a 2,4-dichloro group, K and K are not -(oI2)4-. ] A phenylacetylimidazole compound represented by i) General formula [In the formula, x represents a 10-gen atom, an alkylhaloalkyl group, or an alkoxyl group, R1 and R2 are the same or different dialkyl group, alkoxyalkyl group, alkenyl group, alkoxyl group, noheroalkyl group, or halogen represents an atom or 1 and R2
represents an alkylene chain that may be substituted with. n
represents 0.1 or 2. However, when Xn is a 2,4-dichloro group, R1 and R2 are -(CI(2)4-
isn't it. [In the formula, X, R1, R2 and n have the same meanings as in MiJ. ] 67"Nia'7-t=%Ju (: Tacy" system,. Method for producing a compound. (3) General formula [wherein, X represents a halogen atom, an alkyl group, a haloalkyl group or an alkoxyl group; , R1 and R2 are the same or different, an alkyl group, an alkoxyalkyl group,
It represents an alkenyl group, an alkoxyl group, a haloalkyl group, a halogen atom, or an alkylene chain optionally substituted with R1 and R2. n represents 0, 1 or 2. However, when Xn is a 2,4-dichloro group, R1 and R2 are not -(CI(2)4-).] An agricultural and horticultural fungicide containing a phenylacetylimidazole compound represented by the following as an active ingredient: Herbicides or plant growth regulators.