JPS60260561A - Imidazole derivative and agricultural and horticultural germicide - Google Patents

Abstract

NEW MATERIAL:An imidazole derivative expressed by formula II (X is halogen, lower alkyl or lower alkoxyl; m is 0, 1 or 2; n is 1, 2 or 3; R1 is lower alkyl; R2 is alkyl or cycloalkyl). EXAMPLE:N-1-( 1-Ethoxycarbonyl-2-methypropyl )-N-(1-imidazolycarbonyl)-p-methoxybenzylamine. USE:An agricultural and horticultural germicide, particularly seed disinfectant for bakanae diseases and helminthosporium leaf spot of rice plants. PREPARATION:A carbamoyl chloride expressed by formula I is reacted with imidazole in an inert solvent, e.g. dimethylformamide, in the presence of a base, e.g. potassium carbonate, to afford the aimed compound expressed by formulaII. The compound expressed by formula I can be easily synthesized from a compound expressed by formula III and phosgene, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (1) Field of Industrial Application The present invention relates to a novel imidazole derivative and an agricultural and horticultural fungicide containing the same as an active ingredient. Fudatsu J can be effectively used in the fields of chemical industry and agriculture and horticulture.

(2) Prior art Compounds related to the imidazole derivative of the present invention and their use as agricultural and horticultural fungicides are disclosed in Japanese Patent Application Laid-Open No. 58-1505.
It is described in Publication No. 90.

And there is a structural formula (in the formula, R1 represents a hydrogen atom, a methyl group, or an ethyl group, R2 represents a lower alkyl group, and X and Y each represent a carbon atom or a nitrogen atom, provided that X is a nitrogen atom). Togi is a nitrogen atom (Y represents a nitrogen atom or a carbon atom, and when X is a carbon atom, Y represents a nitrogen atom)
, N'-substituted azole carboxamide derivatives are shown. However, the imidazole derivative of the present invention is
There is a clear difference in chemical structure in that the general formula of the compound described in JP-150590 is used.

(6) Problems to be solved by the invention Conventional imidazole derivatives (Japanese Patent Application Laid-open No. 150590/1983
Refer to the publication, high concentration treatment (250-500 ppm) is used for cucumber powdery mildew, cucumber scab, etc.
However, a certain degree of pest control effect can be expected.

Low concentration treatment (100 to io, ppmt) shows almost no control activity. Also, it has almost no seed disinfection effect, so it cannot be used as a seed disinfectant against rice blight or rice sesame leaf blight.

The present invention provides a new agricultural and horticultural fungicide that can replace these 4 Midazur derivatives, particularly a seed disinfectant for rice blight and sesame leaf blight.

[Structure of the invention]

(1) Means for Solving the Problems The present inventors synthesized many new compounds to replace conventional imidazole derivatives, and as a result of intensive research, the general formula (1) (wherein, X is a halogen atom , represents a lower alkyl group or a lower alkoxy group, m represents ol 1 or 2, n
has been found to be effective.

(2) Action The compound of the general formula (11) can be used to treat rice blast, rice sesame leaf blight, rice sheath blight, tomato late blight, cucumber powdery mildew, cucumber gray mold, barley powdery mildew, and bean sclerotide. , wheat rust.

It shows control activity against beet seedling blight when sprayed or applied to soil, and also has a seed disinfection effect against rice blight and sesame leaf blight. The effects of the compounds of the present invention are not limited to these examples.

Sprays against various diseases such as rice, wheat, cane, and fruit trees.
It can be effectively controlled by soil treatment or seed disinfection treatment5.

Next, a method for producing the compound of general formula (1) of the present invention will be specifically illustrated using reaction formulas and examples.

(Reaction formula) (1) This reaction is carried out in a reaction-inert solvent such as acetone, methyl ethyl ketone, acetonitrile, dimethylformamide, dimethyl sulfoxide or dioxane, etc. using potassium carbonate, sodium hydrogen carbonate, sodium hydroxide, triethylamine or pyridine. is carried out in the presence of a base. The amount of imidazole used in this reaction is preferably 1.0 to 5.0 mol per mol of carbamoyl chloride indicated by the general formula symbol, and the amount of base used is 0 to 5.0 mol per mol of carbamoyl chloride indicated by the general formula symbol. .5 to 5.0 mol is preferred. This reaction is carried out at 20-150°C, preferably at 50-1
It is carried out at 20°C. The carbamoyl chloride represented by the above general formula can be easily synthesized by reacting a secondary amine (110) with phosgene or trichloromethylformate (III) (see the reaction scheme below).

(III) R.

[1] Example 1 N-1-(1-ethoxycarbonyl-2-methylpropyl)-N-(1-imidazolylcarbonyl)-p-methoxybenzylamine (compound 1'a6) N-1-(1 -ethoxycarbonyl-2-methylpropyl)-N-p-methoxybenzylcarbamoyl chloride (5jl (0,015 ml)) was dissolved in 50 ml of N,N-dimethylformamide, imidazole 39 (0,044 ml)
mol) and potassium carbonate 2p (0,015 mol),
Then, the mixture was heated and stirred at 80° C. for 1 hour. After the reaction was completed, water was added, extracted with toluene, and the organic layer was concentrated and purified by column chromatography to obtain 4.2 liters of the desired product as a yellow-orange liquid.

Example 2 N-1-(1-n-butoxycarbonylpropyk)-N
-(1-1 midazolylcarbonyl)-2,4-dichlorobenzylamine (compound N19) N-1-(1-n-butoxycarbonylprobyl) -N -7,4-:)chlorobenzylcarbamoylchlor2 id 3jI (0,00
79 moles) was dissolved in 50 μm of dimethyl sulfoxide, 25 p(0,037 moles) of imidazole and 0 μm of pyridine.
．． Add 4jlC Note 005 Morph and incubate at 100°C for 30
Heated for minutes. After the reaction was completed, the same operation as in Example 1 was carried out to obtain 2.1 p of a pale yellow liquid, which was the desired product.

Example 6 N-1-(1-n-propoxycarbonylbutyl)-
N-(1-imidazolylcarbonyl)-β-7enethylamine (compound Hn16)
Dissolved in 00 relatives.

1.5jl (0,022 mol) of imidazole and 7.8jl (0,077 mol) of triethylamine were added and heated at 60°C for 3 hours. After the reaction was completed, the same operation as in Example 1 was carried out and 4. A yellow-orange liquid of ijI was obtained.

Representative compounds of general formula (1) obtained by the same reaction as in Examples are illustrated.

Table 1 1 1 CH30% I C2H5C! 4H9-1nM'1
．． 52922 aH3-@)-1z niol, 526
53 041 z n,%'1.53764 @2
lt n, o 1.52345 012@2 # z
nj'1.53046 (E50e 105H7-1
02H5Jol, 52327 p 1 # 05H7-
n nDl, 52808 1 03H7-nz nP
1.5275904” I C2H504H2-n
nDl, 539210 e 3 # # % ' 1-
517911 011% 2 # # nn' 1.5
26312 01-D 2 C5H7-n 03H7-
n nM'1.52401306Iln name 91,517
8 14 0< 1 c3H7-i # nj'1.536
0i5 @ 202H5C4H9-n' nM81.
520416 2 03H7-n 05H7-n np
1.520817 r' 102H5C4H7-n
np 1.526918 1 05H7-n 04H7
-nnDl, 526419aH3°hi,. 2H5C
! 4Hp-n”D 1.528320 1 05H7
-n 03H7-n, nDl, 527721 a (5
0@102H5' 04H9-n nj71.526
422 O12105H7-ny nj81-528
223 bi',,,,IC3)I7-n 05
H7-n np 1.532224 e” I C2H
504H9-n nDl, 529825 0X min 1 1
05H11-n nB 1.527826 1 Evening 4
” 1-5403 27 1 z O,5H13-n nDl, 52702
8 0H4i z 04H9-n n, 1.5207
29 1 05H7-n 03H7-n nDl, 52
163Q 1 02H5C6H13-” nDl, 51
6251 a梠■103H7-n 05H7-n nM
8t5! +2552 1 02H504Hp-n np
1.530833 cH3be◇' 103H7-i
0285 nP 1.5114 When the compound according to the present invention is used as a fungicide for common use on farms, it can be used as a powder, wettable powder, emulsion, granule, fine granule, or other commonly used forms. be. The carrier used in the present invention may be either solid or liquid, and is not limited to a specific carrier. Examples of solid carriers include various clays, kaolin, clay, clay,
Talc, silica, etc. can be used as the liquid carrier, and any carrier that can serve as a solvent for the active ingredient compound according to the present invention or a non-solvent that can disperse or dissolve the active ingredient compound with an auxiliary agent can be used. . For example, benzene, xylene, toluene, Kesilon, alcohols,
Examples include ketones, nitrogen sulfoxide, dimethylformamide, and the like. This can be mixed with appropriate amounts of surfactants and other auxiliary agents, such as spreading agents and fixing agents, and used as a water bath liquid or emulsion. Furthermore, the compound of the present invention can be used in combination with other fungicides, insecticides, herbicides, plant growth regulators, etc. to ensure labor-saving and pesticidal effects.

Next, some examples of using the compounds according to the present invention as agricultural and horticultural fungicides will be shown, but the main compounds and additives are not limited to the following examples.

Example 4 (Powder) 2 parts of the compound N [L23 and 98 parts of clay are uniformly mixed and ground to obtain a powder containing 2% of the active ingredient.

Example 5 (Irrigation agent) 60 parts of compound No. 1, alkylbenze' 7,
, /l/o, oatsuu. 3i, 51. 5 parts of allen nonyl enyl ether and 62 parts of white clay are uniformly mixed and pulverized to obtain a wettable powder containing 30% of the active ingredient in the form of a fine powder with a uniform composition. When using this product, add 60% water
Dilute it 0 to 1000 times and spray it on plants.

Example 6 (Emulsion) 30 parts of compound No. 2 and methyl ethyl ketone 4
0 parts, polyoxyethylene nonylphenyl ether 30
By mixing and dissolving these parts, an emulsion containing 60% of the active ingredient is obtained. When using this product, add 600 to 100 with water.
Dilute to 1:0 and spray on plants.

Example 7 (Granules) 5 parts of compound N1124, 1.5 parts of lauryl sulfate,! J calcium geninsulfonate 1.5 parts,
15 parts of water was added to 25 parts of bentonite and 67 parts of white clay, kneaded in a mixer, granulated, and dried in a fluidized dryer to obtain 5.
% granules are obtained.

〔Effect of the invention〕

Next, the pest control effect when the uninvented compound is used as an agricultural and horticultural fungicide will be explained using test examples.

Test Example 1 Rice blast control effect test Paddy rice (variety:
A test chemical solution prepared by diluting an irrigation agent prepared according to Example 2 to a predetermined concentration was sprayed on seedlings at the third leaf stage of Asahi (Asahi). One day after the spraying, a spore suspension of rice blast fungus was spray inoculated. After inoculation - night under humid room conditions (humidity 95-100%, temperature 24-25%)
℃) K was maintained. Five days after inoculation, the number of rice blast lesions per leaf as shown in Table 3 was investigated, and the control value (%) was calculated using the following formula. In addition, chemical damage to rice was investigated using the deficiency index. The results are as shown in Table 2. Investigation index of drug damage 5: Severe 4: Severe 3: Much 2: Slight 1: Slightly None Table 2 1 200 100 0 2 200 100 0 3 200 100 0 4 200 100 D 5 200 100 0 6 200 100 0 7 2 [101000 8200980 22200950 25200970 26200850 27200980 28200990 29200970 Compound wm Spraying concentration Cppm) Control value (Hook, chemical damage level 3 0 200 98 0 Non-sprayed area 0 - Injection From P is S-benzyl thiophosphate It is a commercially available fungicide containing 0.0-diimpropyl.

Note 2) The numbers in parentheses indicate the average number of lesions per leaf in the unsprayed area.

Test example 2 Rice sesame leaf blight control effect test Diameter 9 in a greenhouse
A chemical solution diluted to a predetermined concentration was sprayed on the 4th true leaf stage seedlings of Mizu S (variety: Asahi) cultivated in soil in clay pots of 1.5 m, and a conidial suspension of the rice sesame leaf blight fungus was sprayed one day after the spraying. was inoculated by spraying.

Five days after inoculation, the number of beds per IM of the fourth leaf was investigated, and the control value was calculated using the following formula. In addition, phytotoxicity to rice was investigated using the same method as in Test Example 1. The results are shown in Table 6.

Table 3 12oo I GO0 22001000 5200990 52001000 82001000 1020Q 97 0 i 1 200 i oo.

12 200 100 0 13 200 100 0 14 200 98 0 15 200 100 0 16 200 1 DO0 172001000 182001Do 0 Compound cut NIL Spraying 64 degrees (ppm) Control side) Plant damage level 19 200, 100 D 20 200 100 0 2i 20fJ 100 0 23 200 100 0 24 200 1 DO0 25200990 26200930 27200950 28200970 29' 200 100 0 31 200 99 D Note 1 Iprodione is 3- (3,5-dipo
It is a commercially available fungicide containing 7e=k)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide.

Note 2) The numbers in parentheses indicate the average number of lesions per leaf in the unsprayed area.

Test Example 3 Barley udon and disease control effect test Barley cultivated in soil in a clay pot with a diameter of 9 cm in a waterfall chamber (Product S: 1st leaf stage seedling of Azuma Goldenn) Irrigation prepared according to Example 2 Dilute the agent to the specified concentration and apply IDmj per 2 pots.
Spread each i. The next day, the barley powdery mildew spores that had been caused to infect the barley Tojo in advance were sieved and inoculated onto the Tojo. Seven days after inoculation, the number of barley powdery mildew bacteria per leaf was investigated, and the following formula was used: The control value @) was calculated. In addition, drug damage to barley was tested in Test Example 1.
The survey was conducted using the same indicators.

The 116 rice is as shown in the fourth garment.

Table 4 1 100 100 0 2 1 DOI DO0 51001DO0 41001000 51001000 61001000 71 DOI DO0 81001DO0 91001000 1o ioo ioo.

ii　ioo　1oo　.

1 2 1 DO1000 1310CI 100 0 14 100 1 DO0 15 1 LID 100 0 16 100 100 0 Compound level Spraying concentration (ppm) Control value S) Phytotoxicity degree 1
7 100 100 0 18 100 100 0 19 100 100 0 20 1 DO1000 211001000 221001DO0 231001000 241001000 251001000 261001000 271001000 2 81001000 29100,1000 5010095υ 31 100 100 0 32 100 100 0 33 100 100 0 Note 1 Molestane is dithiocarbonate 81s-methylquinoxaline It is a commercially available fungicide containing -2,6-diyl.

Note 2) The numbers in the box indicate the average number of bacterial flora per leaf in the non-sprayed area.

Test Example 4 Rice sheath blight control effect test A chemical solution of a predetermined concentration was sprayed on 6-leaf stage seedlings cultivated in soil using unglazed pots with a diameter of 9cI11 to 40 females per 3 pots, and the seedlings were left in a glass room. To inoculate the fungi, one day after spraying the chemical solution, the fungi that had been cultured in advance on a potato agar medium supplemented with sucrose (48 hours at 27°C) were pasted onto the base of an agar desk leaf sheath punched out with a cork polar with a diameter of 10III, and kept in a greenhouse overnight. Ta. To investigate the onset of the disease, the length of the rice sheath blight lesion per stem was investigated 6 days after inoculation, and the control value (%) was determined by comparing it with the unsprayed area.

In addition, chemical damage to rice was investigated using the same method as in Test Example 1.

Next, the test results are shown in Table 5.O Table 5 11 200 100 0 23 200 100 0 24 200 1 DO0 31200980 Note 1) Palidamycin is a commercially available bactericide (antibiotic)
It is.

Note 22: The numbers in brackets indicate the lesion length in the non-sprayed area.

Test Example 5 Wheat rot disease control effect test No. 1 cultivated in soil in a clay pot with a diameter of 9 squares in a greenhouse
Example 2 on wheat seedlings (variety: Norin No. 61) at true leaf stage
A predetermined concentration dilution of an irrigation agent prepared according to the method was sprayed at a distance of 20 m per 6 pots. One day later, the summer spores of wheat rot fungus that had been formed in advance on wheat Tojo were placed under a microscope at 150x magnification using Tween 20 [Polyoxyethylene Rubitan manufactured by Kao Soap Co., Ltd.] so that the concentration of vacuoles per field of view was approximately 50. Monolaurate (trade name)] was suspended in sterilized water to which 50 ppm was added, and the suspension was sprayed and inoculated onto leaves sprayed with the drug.

- After being kept in a humid room at 20°C at night, they were transferred to a greenhouse at 20°C to induce disease onset. The plants were taken out 10 days after inoculation, and the number of infected wheat rot dya spores per leaf was investigated, and the control value (porridge) was calculated using the following formula. In addition, phytotoxicity to wheat was investigated using the same index as Test Example 1. The test was conducted using three pots at one concentration, and the average control value (chi) was calculated.The results are shown in Table 6.

Table 6 4 1 DO98D 7 100 95 0 18 100 97 0 24 100 99 0 Note 1) Neb is a commercially available disinfectant containing zinc ethylene bis(dithiocarbamate).

Note 2) The numbers in brackets indicate the average number of diaspores per leaf without spraying.

Test Example 6 Cucumber Gray Mold Control Effect Test Cucumbers (cultivar: Sumo Hanshiro) at the first true leaf stage grown in soil in a greenhouse with a diameter of 9 cm were prepared according to Example 2. A predetermined concentration solution of an irrigation agent containing the active ingredients shown in Table 1 was sprayed on 10 strips per potted insect. One day later, a piece of fungi-containing agar obtained by punching out the defined tip of the cucumber gray mold fungus, which had been cultured in advance on a potato decoction agar medium at 20°C for 2 days with a cork bosie with a diameter of 5 pieces, was placed at the center of each single leaf of the second true leaf. was inoculated. Thereafter, they were stored in a humid room at 20°C for 6 days to promote the onset of disease.

- The inspector measured the length of cucumber gray mold lesions with calipers 6 days after inoculation, and calculated the control side repair using the following formula. In addition, chemical damage to cucumbers was investigated using the same index as in Test Example 1.

The test was conducted at one concentration twice, and the average control value (%)
was calculated.

The results are shown in Table 7.

Table 7 3 200 100 0 4 200 100 0 Note 1) Procymidone is a commercially available fungicide containing N-(3,5-dichlorophenyl)-1,2-9methylcyclopropane-1,2-dicarboximide. be.

Note 2: The value in the box is the lesion length (b) in the non-sprayed area.

Test Example 7 Rice baka-seed disease seed disinfection effect test Rice (variety:
During the flowering period of Kinki No. 33), the rice fungus (Zalium 7)
obtained by spray inoculation with a concentrated spore suspension of -
The paddy infected with Nebaka Nae disease was used as the test paddy. For seed disinfection, a diluted solution with a predetermined concentration was prepared using an irrigation agent prepared according to Example 2, and the seed rice and the chemical solution were immersed at a ratio of 1:1 (V/V) for 24 hours at 20°C. Poisoned.

The sterilized rice seeds were soaked at 20℃ for 6 days, then germinated at 30℃ for 24 hours, and the pigeon-breasted seedlings were inoculated with Kumiai granular culture ± (manufactured by Kureha Kagaku Kogyo Co., Ltd.) K according to the box seedling method. did. After that, they were cultivated in a glass greenhouse.

The disease outbreak survey was carried out after 25 days of inoculation (4) by removing the plots from each treatment area and investigating the number of bacteria that caused rice baka-nae disease to determine the rate of diseased seedlings (
%), and the control value (%) was calculated from this. Furthermore, chemical damage to rice was investigated using the same criteria as in Test Example 1.

This test was conducted in 6 consecutive sessions per section, and the average seed disinfection rate (chi) was determined. The results are shown in Table 8.

Table 8 3 1000 100 D 8 1000 90 0 19 1000 99 0 20 1000 89 0 21 1000 99 0 24 1000 90 0 25 1000 93 0 28 1000 91 0 29 1000 99 0 Untreated area 0 - (57,3) Note 1 henomyl is 1-(n-butylcarbamoyl)-
A commercially available seed disinfectant containing 2-benzimidazole methylcarbamate.

Note 2) The numbers in parentheses are the diseased seedling rate in the untreated plot (2))
shows.

Test Example 8 Rice Sesame Leaf Blight Seed Disinfection Effect Test Rice grains infected with naturally occurring rice sesame leaf blight fungus (Cochliobolus myabeanus) were collected in the field and used as test rice. Seed disinfection method? and other operating procedures were carried out in the same manner as in Test Example 7. The disease onset investigation was carried out 20 days after inoculation, the number of bacteria causing rice sesame leaf blight was investigated, and the seed disinfection rate (chi) was calculated in the same manner as in the rice blight seed disinfection effect test. In addition, drug damage was investigated using the same criteria as in Test Example 1.

This test was conducted in 6 consecutive sessions per section, and the average seed disinfection rate (%) was determined. The results are shown in Table 9.

Table 9 2 1000 100 0 s　1oOo　90　0 11 1000 90 D I 2 1000 99 0 13 1000, 92 0 19 1000 91 0 20’10’OD 93 0 21 1000 95 0 25 1000’ 99 0 29 1000 90 0 Untreated area 〇　− (45) Note 1) Procymidone is the same as in Test Example 6.

Note 2) The numbers in brackets indicate the diseased seedling rate (%) in the untreated area.

Test Example 9 Beet seedling damping-off control effect test Beet seedling damping-off fungus [Rhizoctonia solani]
8o1ani)) 100 pieces of contaminated soil and a powder prepared in accordance with Example 1 were mixed to obtain a soil containing a drug at a predetermined concentration. This was filled into a plastic pot, and beet seeds (variety Sorolaben were added per pot). Ten seeds were sown at a time. After sowing, the seedlings were kept at 24° C. Ten days after sowing, the number of seedlings withering was investigated, and the control value was calculated using the following formula.

The test was conducted using a 3-pot system per district, and the control value was determined from the average seedling damping-off rate of the 3 pots. In addition, chemical damage to beets was investigated in the same manner as in Test Example 1.

The results are shown in Table 10.

Table 10 2 50 95 '0 3 50 95 0 4 50 95 0 5 50 100 0 11 50 950 15 50 95 0 16 50 95 0 24 50 100 0 Note 1) PCNB contains Ni/tachlornitrobenzene It is a commercially available disinfectant.

Note 2) The numbers in parentheses are the percentage of infected and dead seedlings in the untreated area)
shows.

Procedural amendment August 9, 1980 Commissioner of the Japan Patent Office Shiga Number of characters: 1, Indication of the case 1982 Patent Application No. 116800 Z Name of the invention Imidazole derivatives and agricultural and horticultural fungicides 3, Person making the amendment Related Patent Applicant Address 1-12-32 Nishihonmachi, Ube City, Yamaguchi Prefecture Name (
020) Ube Industries Co., Ltd. (1 other person) 4. Agent 5. Date of amendment order (spontaneous) Showa year, month, day (Ship date: Showa) Contents of amendment 1) Page 16, line 9, “60 " will be corrected to "50%".

2) "Example 2" on page 17, line 7 will be corrected to "Example 5."

3) Correct “Table 3” on page 17, line 12 to “No. 311.”

4) Correct “Example 2” on page 22, line 7 to “Example 5.”

5) Correct "desk" in lines 11-12 of page 25 to "disc."

6) Correct “Example 2” in the second line of page 27 to “Example 5.”

7) Correct “Example 2” on page 29, line 3 to “Example 5.”

Illusion Correct "2nd true leaf" t "1st true leaf" on page 29, line 8.

9) "Example 2" on page 51, line 2 will be corrected to "Example 5."

10) Correct "seeds" in lines 7-8 of page 61 to "seeds".

11) “Inoculation” in line 9 of page 61 will be corrected to “seeding”.

12) Correct “Example 1” on page 35, line 4 to “Example 4.”

that's all -nuji-

Claims (1)

[Claims] 1) General formula (X represents a haloken atom, lower alkyl group or lower alkoxy group, m represents an integer of 0.1 or 2, n represents an integer of 1.2 or 6 +R1 represents a lower alkyl group, and R2 represents an alkyl group or a cycloalkyl group). (X represents a halogen atom, a lower alkyl group or a lower alkoxy group, m represents an integer of 0.1 or 2, n represents an integer of 1, 2 or 6, b"1 represents a lower alkyl group, and An agricultural and horticultural fungicide characterized by containing as an active ingredient an imidazole derivative represented by R2 representing an alkyl group or a cycloalkyl group.