JPS58170793A - Novel cyclopropanecarboxamide derivative and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [R1 is H or halogen; R2 is H, lower alkyl, or (alkoxy-substituted)phenyl; R3 is lower alkyl; X is O or S]. EXAMPLE:O,O-diethyl-s-[1-(2,2-dichloro-1-methylcyclopropanecarbonylami no)-2, 2,2-trichloroethyl]-phosphorodithioate shown by the formula II. USE:An agricultural and horticultural fungicide showing improved controlling effect on blight of agricultural and horticultural plants, especially on bacterial leaf blight, powdery mildew, etc. of rice plant, exerting no bad influence such as phytotoxicity on plants, having effects by soil treatment and foliar application. PROCESS:A chloralamide derivative shown by the formula III is reacted with a halogenating agent, to give a compound shown by the formula IV(hal is halogen), which is reacted with a compound shown by the formula V(M is H, alkali metal such as Na, K, etc., ammonium, or tertiary alkylamine salt).

Description

[Detailed description of the invention] The present invention is based on the formula (In the formula, Rr is a hydrogen atom or a halogen atom.

is a hydrogen atom, a lower alkyl group, or a phenyl group.

Or a phenyl group substituted with a phenyl group.

R3 represents a lower alkyl group, and X is oxygen or sulfur η! show. The present invention relates to novel cyclopropane carboxamide derivatives represented by () and agricultural and horticultural fungicides containing one or more of them as active ingredients.

Traditionally, organic chlorine agents have been used as disinfectants for agriculture and horticulture.

Organic sulfur agents, antibiotic agents, organic nickel agents, copper agents, etc. have been used as dispersing agents, but organic chlorine agents tend to cause chemical damage and cannot be effective for control unless treated in high concentrations. For not.

When used in large quantities, chemicals tend to remain in crops and soil; organic sulfur agents can cause chemical damage and skin irritation; antibiotics can cause the development of resistant bacteria and residual effects. In addition, organic four-layer agents and copper agents have drawbacks such as insufficient control effects.

In addition, today, aromatic compounds other than those listed above are commercially available as agricultural and horticultural fungicides, but they are only effective against bacteria or bacteria, and the method of application is soil application or foliage spraying. There may be only one of the
There were few agricultural and horticultural fungicides that could be applied to a wide range of subjects and methods.

The present inventors have discovered that the novel compound represented by (1) overcomes the drawbacks of conventional fungicides as described above, and is effective against a wide range of agricultural and horticultural crop diseases caused by bacteria and fungi, especially rice blight and udon. The present invention was completed after discovering that it has an excellent control effect on mildew, etc., does not have any adverse effects such as phytotoxicity on plants, and is also effective in soil II application and foliage spraying. . The compound of the present invention represented by formula (1) is produced in the following manner.

(In the formula, R8 and R2 are the same as in the formula (1).) A chloralamide derivative represented by The compound represented by the formula (3) (in which R3 and X are the same as in formula (1); M is a hydrogen atom, an alkali metal such as sodium or potassium, or ,
Ammonium and tertiary alkylamine salts are shown. ) by reacting with a compound represented by

A compound represented by formula (1) can be obtained.

The compound represented by formula (2) can be prepared by a known method (Japanese Patent Publication No. 47
-39629).

It can be obtained by reacting an acid amide represented by 2 (where Rt and R2 are the same as in formula (1)) with chloral.

Examples of the halogenating agent to be reacted with the compound of formula (2) include thionyl chloride, thionyl bromide, and halogen ratios, but thionyl chloride is preferably 1%. The reaction between the compound represented by formula (2) and the above halogenating agent is carried out in an inert solvent, optionally in the presence of a halogenating catalyst such as dimethylformamide, at a temperature of 30C to 150C.
A reaction time of 30 minutes to several hours is sufficient for one reaction. The inert solvent referred to herein refers to aliphatic and aromatic optionally chlorinated hydrocarbons 1, for example,
benzene, toluene.

xylene, chlorobenzene, methylene chloride, 1°1,1
- 17 Chlorethane, chloroform, carbon tetrachloride, etc. can be used. In addition, the reaction of the compounds represented by formula (3) and formula (4) (in which R3 and X represent formula (1) and 1M represents the salt of formula (4)) can be performed in In addition, ethers 1 such as diethyl ether, dioxane and tetrahydrofuran, ketones 1 such as
Acetone and methyl ethyl ketone, esters 1 such as methyl acetate and ethyl acetate, nitriles 1 such as acetonitrile and propionitrile.

Amides 1 The reaction is carried out in a solvent such as dimethylformamide and dimethylacetamide at -10 to 80C for a period of minutes to hours. In addition, the reaction between the compound of formula (3) and the compound of formula (4) (wherein R3 and It can be done similarly. The base used here is preferably an inorganic base such as sodium carbonate or potassium carbonate, or an aliphatic, aromatic or heterocyclic amine (eg, triethylamine, NN-diethylaniline, pyridine, picoline). Also, formula (4) (in the formula,
R3 and M are the same as formula (11).

X indicates sulfur. ) The compound represented by % is obtained by a known method of reacting phosphorus pentasulfide with an alcohol represented by the formula % (6), and then ammonia, sodium hydroxide, or tertiary amine is added to this. Obtained by adding.

The compound represented by Formula 1 Formula (4) (wherein, R3 is the same as in Formula (1). The same can also be obtained by adding sulfur powder to a mixture of a dialkyl phosphite and trialkylamines (eg, triethylamine, tripropylamine, etc.) represented by the following formula with a solvent such as dimethylacetamide.

Table 1 shows examples of the invention compounds produced as described above.

Table 1: Cyclopropane carboxamide derivatives Next, the manufacturability of the compounds of the present invention will be shown in more detail with reference to Examples.

Example 1 0.0-diethyl-8-(1-(2,2-dichloro-1)
-methylcyclopropanecarbonylamino)-2,2,
2-) Lichlorethyl]-phosphorodithio-r--)(
rlkill) N-(1,2,2,2-tetrachloroethyl) -2,
2-Cyclo-1-methylcyclopropanecarboxamide 6.7? (0.02 mol) and 50 ml of acetone under stirring, keeping the temperature between 0° and 5°C.

0.0-Ammonium diethyldithiophosphate 4.71!
? (0,0232 mol) is added. After the addition, the mixture was reacted for 3 hours at a room source, and then poured into water and the precipitated crystals were filtered. 6.0? Obtain white crystals. Yield 62.0%.

The physical constants of the compound rkll of the present invention are as follows.

・Infrared absorption spectrum (KBr): 1670crIr" (C=0 stretching, 7mi)" absorption)
3250 crn (NH bending, amide absorption) Nuclear magnetic resonance spectrum (in CDCl2, ppm from TMS)
1.25ppm~1.40ppm (7H, m)・-
・F and A or Xl, 60 pI) m (
3H,s)-=B2.16 ppm
(I H, d)-A or A3.90 ppm to 4.4
0 ppm (4H,m)・-E6.22 ppm
(I H, d-d)・-D
・9.33 ppm (I H, d)-
--C Example 2゜0.0-diisopropyl-s-[1-(2,2-dichloro-1-methylcyclopropanecarbonylamino)
-2,2,2-)lychloroethyl]-phosphorothioate (Na7) 0,0-diisopropylphosphite 3.9 P(0,
0.754 (0.024 mol) of powdered sulfur at 10° to 15C in a mixed solution of 20 m/dimethylacetamide and 2.45 L (0.024 mol) of triethylamine.
mol) was added, being careful not to generate heat, and stirred at room temperature for 1 hour.

This reaction solution was kept at 0° to 5°C in ice water.

N-(1,2,2,2-tetrachloroethyl) -2,
2-dichloro-1-methylcyclopropanecarboxamide (6.710.02 mol) was added, stirred at room temperature for 2 hours, and poured into ice water. The precipitated crystals are filtered and recrystallized from a mixed solvent of rhohexane and ethyl acetate to obtain 6.9p white crystals. Yield: 69.6.

The physical constants of the compound Nn7 of the present invention are as follows.

・Infrared absorption spectrum (KBr): 1690 crn (C=O stretching, amide absorption) 32
00crn-(-NH bending angle, amide absorption)/Nuclear magnetic resonance spectrum (in CDCIs, ppm from TMS) (structural formula) %formula% ) ) ) ) ) Ropane force Rupoxamide 2,2-cyclo-1-methylcyclopropane Carboxamide is,5y(o,methyl)-1,1,1-)dichloroethane 100d and chloral 19.254(0,
1 mol x 1.3) is reacted for 4 hours under reflux and stirring.

The reaction solution was cooled to below 5C by cooling with ice water and the precipitated crystals were filtered to obtain white crystals of 26.87.

Yield 84.9%, melting point 116C-118C Reference example 2°N-(1,2,2,2-tetrachloroethyl) -2,
2-dichloro-1-methylcyclopropanecarboxamide N-(1-hydroxy-2,2,
2-) dichloroethyl) -2,2-dichloro-1-methylcyclopropane lupoxamit 31.6? (0,1
Thionyl chloride 15.5 P (0.1 mol x 1.3) is added dropwise into a mixture of 50 ml of dichloroethane (mol), 1,1.1-) and 0.5 ml of dimethylformamide.

Thereafter, the temperature is gradually raised and the reaction is carried out under reflux for 3 hours. After the reaction is completed, cool to below 1 oc by cooling with ice water,
When the precipitated crystals are filtered, white crystals of 28.4p are obtained. Yield: 85.0%, melting point: 176C to 177C The lower alkyl groups represented by R2 and R3 include groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, etc. Examples of the above halogen atoms include atoms such as chlorine, bromine, and heptanodine, and examples of the above alkoxy groups include methoxy groups,
Ethoxy groups, propoxy groups, etc., and examples of tertiary alkylamine salts include triethylamine, tripropylamine, etc.

By using the compound of the present invention as a fungicide for agricultural and horticultural purposes, by a method commonly used in the agricultural chemical manufacturing field,
It can be used in the form of powders, fine granules, irrigators, flowable tablets, emulsions, and the like.

These various formulations are used in actual use.

It can be used directly or diluted with water to the desired concentration.

The agrochemical auxiliaries mentioned here include carriers (diluents) and other auxiliaries such as spreading agents and emulsifiers.

Wetting agents 1 Dispersants, fixing agents, disintegrants, etc. can be mentioned.

Liquid carriers include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, and methylnaphthalene.

Examples include cyclohexane, animal and vegetable oils, fatty acids, and fatty acid esters.

Solid carriers include clay, kaolin, and talc.

Diatomaceous earth, silica, calcium carbonate, montmorillonite,
Examples include bentonite, feldspar 1 quartz, alumina, and sawdust.

In addition, surfactants are usually used as emulsifiers or dispersants, such as anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, and cationic surfactants. , nonionic surfactant 1 and amphoteric ionic surfactant.

All formulations can be used not only as they are, but also in combination with fungicides, insecticides, plant growth regulators, acaricides, herbicides, soil fungicides, soil conditioners, or nematicides. It can also be used in combination with other agricultural and horticultural fungicides.

What is the active ingredient compound content in the herbicide of the present invention?

It varies depending on the formulation form, method of application, and other conditions, and in some cases only the active ingredient compound may be used.
Usually 1-95% (weight) Preferably 2-90% (weight)
is within the range of And the preferred content varies depending on each form of Ifia agent.

For example, in the case of a powder, the content of the compound of the present invention is 1 to 20%.
The content of the auxiliary agent is 80 to 99 qb, and in the case of an emulsion, the content of one compound of the present invention is 2 to 40%, and the content of the auxiliary agent is 60 to 98%.

In the case of an irrigation agent, the content of the two compounds of the present invention is 20 to 95%, and the content of the adjuvant is 10 to 80 qb.

In the case of granules and fine granules, the content of the compound of the present invention is 1 to 20%.
and the content of adjuvant is 80-99%.

Furthermore, when used in the field, it is appropriate to use the compound of the present invention in a range of 0.5 ky to 80 kjl per 1 ha.

Next, formulation examples of the present invention will be explained in more detail.
The types and mixing ratios of agricultural chemical adjuvants are not limited to these, and can be used in a wide range.

Note that "parts" means "parts by weight."

Formulation Example 1 part Fine granules Compound of the present invention Nn1 (0,0-diethyl-5-(1-cyclopropanecarbonylamino-2,2,2-trichloroethyl)phosphorothioate) 5 parts and bentonite 6
1 part and 9 parts of clay were uniformly mixed and ground to form a thick powder. Separately 74~105μ oil well absorbent mineral coarse powder 8
0 part is placed in a suitable mixer and rotated once to moisten it by adding 20 parts of water, and the above-mentioned thick powder is added, coated and dried to form fine granules.

Formulation example 2. Powder Compound of the present invention 5 (0,0-dimethyl-5-[1-(1
-methyl-2,2-dichlorocyclopropanecarbonylamino) -2,2,2-) IJ chloroethyl]-phosphorothioate) 5 parts, talc 46 parts and clay 4
Mix and grind 9 parts to make a powder.

Formulation example 3. Irrigation agent Compound of the present invention Nn4 (0,0-diisopropyl-8-(
1-cyclopropanecarbonyl 7 mi/-2,2゜2
-trichloroethyl)-phosphorodithioate), 15 parts of kaolin, 3 parts of higher alcohol sodium sulfate, and 2 parts of sodium polyacrylate are mixed and ground to prepare an irrigation agent.

Formulation Example 41 granules Compound of the present invention 1'1 bll (0,0-diethyl-8-(
1-(1-methyl-2,2-dichlorocyclopropanecarbonylamino)-2,2,2-trichloroethyl]
- After mixing 10 parts of phosphorodithioate), 35 parts of diatomaceous earth, 23 parts of bentonite, 30 parts of talc and 2 parts of a disintegrant, 18 parts of water was added, the mixture was evenly moistened, and then extruded through an injection molding machine and granulated. Then, it is dried, passed through a crusher, and then sized with a sieve to obtain a particle size of 0.6 to 11! 1 granule.

Formulation example 5. Emulsion Compound of the Invention 14 (o, o-diethyl-5-[1
-[1-phenylcyclopropanecarbonylamino]
-2,2,2-)lichloroethyl]-phosphorodithioate) was dissolved in 63 parts of xylene.

To this was added a mixture of alkylphenol ethylene oxide condensate and calcium toalkylbenzenesulfonate (8:2
) are mixed and dissolved to form an emulsion.

The basic rule is to dilute it with water and use it as an emulsion.

First, agricultural and horticultural fungicides containing the compound of the present invention as an active ingredient are effective against bacteria (Experimental Examples 1 and 2) and fungi (Experimental Example 3), and are also effective when applied to soil and sprayed on foliage. The following experimental examples demonstrate that it is an excellent and versatile agricultural and horticultural fungicide.

Experimental example 1. Rice leaf blight control test 115 by soil application
．． 000 Al-Wagnerbot and secondary monthly rice (variety:
Zennanfu) was grown. For this rice, the method of Formulation Example 4,
A predetermined amount of the granules of the compound of the present invention prepared in step 3 was applied to the soil.
After a few days, rice leaf blight fungus (XanLhomon) appears on the leaves of rice.
as 7 pV, partially inoculated with 28C
Infect the plants by keeping them in a greenhouse for 24 hours.

The disease was then allowed to develop in the greenhouse.

Probenazole 8% granules (active ingredient: 1
．． The same procedure was carried out using 2-vanzisothiazol-3-one-1,1-dioxide). Lesion length was examined 14 days after inoculation.

The results are shown in Table-2.

Table-2 Experimental example 2. Rice leaf blight control test 115 by foliage spraying
,000 to R.Wagnerbot for two months.

Rice (variety: Kinnanfu) was grown. A predetermined amount of the irrigation agent of the present invention produced by the method of Formulation Example 3 was sprayed onto the rice, and 3 days later, the leaves of the rice were infected with
nas campestris pv, oryzae
) was inoculated with leaves and kept in a greenhouse at 28C for 24 hours to infect the plant, followed by disease development in the greenhouse.

The rate of diseased leaves was investigated 14 days after inoculation. The results are shown in Table-3.

Table-3 Experimental example 3. Cucumber powdery mildew control test 5 cucumber seeds (variety: Tokiwa Jirai) were sown in 10 crn pots, and after 14 days, the seedlings were sprayed with a predetermined amount of the irrigation agent of the present invention produced by the method of Formulation Example 3. , 5phaero-theca fuligin after air-drying.
ea) The spores were inoculated, and 14 days later, the disease index and control value were investigated. The results are shown in Table-4. disease index,
The control value was calculated as follows.

A: Number of strains with severe disease onset B: Number of strains that are significantly susceptible to disease C: Number of strains with slight disease onset D=Number of healthy stocks

Claims (1)

[Claims] (In the formula, Rr is a hydrogen atom or) a rogene atom. rL2 is a hydrogen atom, a lower alkyl group, or a phenyl group. Or an alkoxy-substituted phenyl group. R3 represents a lower alkyl group, and X represents oxygen or sulfur. ) A novel cyclopropane carboxamide derivative represented by 2) Formula (in the formula + R1 is a hydrogen atom or a halogen atom. R2 is a hydrogen atom, a lower alkyl group, a phenyl group, or an alkoxy-substituted phenyl group. R3 is a lower alkyl group, and X is oxygen or sulfur. An agricultural and horticultural fungicide characterized by containing one or more of the novel cyclopropane carboxamide derivatives represented by (a) as an active ingredient.