JPS62404A - Agricultural fungicide - Google Patents

Abstract

PURPOSE:To provide a fungicide containing a specific nitrogen-containing heterocyclic compound, exhibiting excellent effect to control rice blast and having remarkable activity to exterminate various rice blights such as sheath blight, stem rot, helminthosporium leaf spot, etc. CONSTITUTION:The objective agent contains the compound of formula I (R1-R6 are H, lower alkyl or lower alkenyl; R2 and R5 may be halogen; R1 and R2 together form a lower alkylene; R2 and R3 or R5 and R6 may together form a butadienylene), e.g. 2-(3,5-dimethyl-1-pyrazolyl)-4,5,6-trimethylpyrimidine, as an active component. The fungicide has the preventive activity to inhibit the infection of a plant with pathogens and protect the plant as well as the remedying activity to inhibit the propagation of plant blight by the application to the infected plant. The compound of formula I can be produced e.g. by reacting the 1,3-dicarbonyl compound of formula II with the 2-pyrimidylhydrazine compound of formula III.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a new agricultural fungicide.

Conventional techniques In rice cultivation, in recent years, advances have been made in technological reforms such as IaM and labor saving, as well as improvements in ridges and waterways, and leaf blight, one of the three major rice cultivation diseases, is gradually decreasing. On the other hand, rice blast, along with sheath blight, is increasingly reaching 5f1M. Various drugs have been researched and tested for the purpose of controlling this important disease, stone rot.

Problems to be Solved by the Invention The inventors of the present invention have devoted themselves to research for the purpose of controlling grass blight, and as a result, have discovered a nitrogen-containing heterocyclic compound that has a completely different structure from conventional agricultural fungicides. It was discovered that the agricultural fungicide contained as an active ingredient has an excellent effect on controlling blight, and has also been found to be effective against not only blight but also sheath blight, sheath blight,
It was discovered that the present invention is also highly effective in killing micrococcal rot, sesame leaf blight, and other rice cultivation diseases, and the present invention was completed based on these new findings.

Means for Solving the Problem The present invention provides a general formula R3 in which R1, R2, R3, R4, Rs and U Re
C2: Resol represents a hydrogen atom, a lower alkyl group or a lower alkenyl group, R2 and R6 each may further be a halogen atom, and R1 and R9 represent a lower alkylene group, R2, R3 and R5 and R6 may each form a butanoenylene group] This is an agricultural fungicide characterized by containing a nitrogen-containing heterocyclic compound as an active ingredient.

In the compound "1" which is the active ingredient of the agricultural fungicide of the present invention, the lower alkyl group is linear or branched and has 1 carbon number.
6 to 6 alkyl groups are preferred, such as methyl, ethyl, propyl, isopropyl.

butyl, isobutyl, 5ec-butyl, tert-butyl.

Pentyl, isopendel, neopendel, hexyl.

Examples include isohexinol and the like. Among the exemplified alkyl groups, methyl, edyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl are more preferred.

The lower alkenyl group in the compound [Concave] is preferably a linear or branched alkenyl group having 1 to 6 carbon atoms, such as vinyl, allyl, and 1-propenyl.

Methallyl, butenyl, l-ethylvinyl, 1. Examples include I-dimethylvinyl and I-methyl-2-propenyl. Among the exemplified alkenyl groups, allyl is more preferred.

Examples of the halogen atom in compound [l] include fluorine, chlorine, bromine, and iodine, with chlorine and bromine being more preferred.

In compound [+], the lower alkylene group is preferably alkylene JI having 3 to 5 carbon atoms, such as trimethylene, tetramethylene, and pentamethylene. Among the exemplified alkylene groups, trimethylene and tetramethylene are preferred. More preferred.

Compound [1] is defined as including its acid addition salts and quaternary salts in the claims and detailed description of the invention. Examples of the acid addition salt of compound [I] include organic acid addition salts and inorganic acid addition salts. Examples of acid addition salts include formate.

acetate, propionate, monochloroacetate, chloroacetate, trichloroacetate, trifluoroacetate, sulfate, fumarate, maleate, amuro, framate, p
-carboxylic acid salts such as chlorobenzene, frate, nicotinate and, for example, methanesulfonate.

Specific examples include sulfonates such as ethanesulfonate, benzenesulfonate, paratolsulfonate, as well as picrates and zacharin salts. Examples of inorganic acid addition salts include hydrochloride.

Examples include hydrobromide, sulfate, nitrate, phosphate, carbonate, and addition salts such as silver nitrate and paranrum chloride. Examples of the quaternary salt of compound [+] include N-alkylammonium halogenite and N-alkylammonium halosulfonate.

Examples of N-alkylammonium halogen atoms include N-methylammonium taloride, N-methylammonium b[lmite, N-methylammonium iodide[ζ], N-ethylammonium chloride, N-ethylammonium bromide, N-ethyl Examples include ammonium iodide. Examples of the N-alkylammonium halosulfonate include N-methylammonium chloride [10sulfonate,
Examples include -methylammonium fluorosulfonate, N-ethylammonium chlorosulfonate, and N-ethylammonium fluorosulfonate.

The nitrogen-containing heterocyclic compound, which is an active ingredient of the composition of the present invention represented by the general formula [1], is a new or known compound, and the present inventors have developed a composition containing the compound [(] as an active ingredient). It also has excellent bactericidal action as a pesticide, including blight, sheath blight, micrococcal core disease, and sesame leaves.
! It was discovered that this method is highly effective in controlling diseases caused by Phytophthora I and three types of Phytophthora.

In addition, the compound UI of the present invention not only has the therapeutic ability to inhibit the spread of diseased plants by treating it, but also has the therapeutic ability to inhibit the spread of diseased plants.
It was discovered that it has the ability to prevent pathogen infection and protect the plant body.

As a treatment method, even if it is simply sprayed on the stems and leaves of the plant body, due to its strong penetrating properties, it is absorbed into the plant body, moves through the body, and is widely distributed, and has the ability to maintain the concentration necessary for plant protection. What do you do?

Although Compound [+] has strong bactericidal activity, it has low skin irritation and oral toxicity to warm-blooded animals, and has little impact on the environment such as fish toxicity. Furthermore, it does not cause any or very slight phytotoxicity to various crops, and has no effect on subsequent growth or yield. These compounds are used because compound [+] has a strong affinity for plants and has moderate chemical stability. Therefore, the compound according to the present invention [■
] can be said to be a group of compounds that have extremely suitable qualities as a multi-purpose agricultural fungicide. The agricultural fungicide of the present invention will be explained in detail below.

The agricultural fungicide of the present invention may contain 1% of the compound represented by the general formula Ell, and may be used in combination with two or more of them. In addition, the compound [+] may be used alone, or, if necessary, various natural products, additives, solvents, etc. may be added.

More specifically, compound [1] can be used directly as a solid agent for the purpose of maintaining its efficacy over a long period of time, or it can be dissolved or dispersed in a suitable liquid carrier (for example, a solvent). , and also mixed with or adsorbed onto suitable solid carriers (eg diluents, fillers), as well as emulsifiers, dispersants, spreading agents, penetrating agents, and wetting agents.

Contains mucilage agents, stabilizers, oil agents, emulsions, and hydrating agents.

It can be used in four dosage forms such as a suspension, a single powder, a single fine granule, and a spray.

Examples of such solvents include water, alcohols (
For example, methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol, etc.), ketones (for example, acetin, methyl ethyl ketone, etc.)
, ethers (e.g., dioxane, tetrahydrofuran, cellosolve, etc.), aliphatic hydrocarbons (e.g., gasoline, kerosene, kerosene, fuel oil),
Aromatic hydrocarbons (e.g., benzene, toluene, kiln, solvent naphtha, methylnaphthaleno, etc.) and other organic bases (e.g., pyridine, aldehyde collidine, etc.) halogenated hydrocarbons (e.g., chloroporum).

carbon tetrachloride, etc.), acid amides (e.g., dimethylpolamide, etc.), esters (e.g., ethyl acetate, butyl acetate, glycerin esters of fatty acids), and nitrites (e.g., acetonitrile, etc.), sulfur-containing Compounds such as nomedyl sulfoxide, tetramedylene sulfon, etc. can be used, but in general, water-soluble solvents such as glycols, tumedyl formamide, dimedyl sulfoginde, etc. It is best to use it by dissolving it in

Solid carriers such as diluents and bulking agents include, for example, vegetable powders (for example, rice bran, soybean flour, tobacco powder, and wheat flour), mineral powders (for example, kaolin,
Bentonite, calcium phosphate, acidic white clays, /i'F stone powder, stone powder, stone wax, talc, silica (one powder per cloud, etc.), and alumina, sulfur powder, Activated carbon is used, and these may be used alone or in combination of two or more.

In addition, emulsifier, spreading agent 0. As a penetrating agent and a dividing agent,
Soaps, higher alcohol esters, argyl sulfonic acid, alkylaryl sulfonic acid.

Surfactants such as ammonium 1, salt 0, ochinoalkyl amine, fatty acid ester, polyalkylene ogizide type, and anhydrosorbitol type are widely used, and are generally 0.2 to 10% (% is weight) in the formulation. % (hereinafter the same applies) and the degree of inclusion is preferred. In addition, if necessary, use casein, gelatin, starch, alginic acid, agar, CMC, polyvinyl alcohol, pine bran (3, bran, 11°hentonite, cresol soap, etc.). (For example, chlorine-based fungicides, organic phosphorus-based fungicides, henzimidazole-based fungicides, copper-based fungicides, organic acid-based fungicides, phenolic fungicides,
antibiotics, etc.), insecticides (natural insecticides, carbamate insecticides, organophosphorus insecticides, etc.), acaricides, nematicides, herbicides, plant growth regulators, stabilizers, synergists, Attractants, repellents, fragrances.

Plant nutrients, fertilizers, various amino acids, low-molecular or high-molecular phosphates, etc. may be mixed as appropriate.

The agricultural fungicide of the present invention contains the above-mentioned compound [! ], a carrier, auxiliary ingredients, etc., are mixed by a known method or a method similar thereto.

Content ratio of compound [1] in the pesticidal agent in the present invention (
Appropriate weight percent) is approximately 10 to 90% for emulsions, wettable powders, etc., approximately 0.1 to 10% for oils, powders, etc., and approximately 5 to 50% for granules.

Note that emulsions, hydrating agents, and the like are preferably further diluted (for example, 50 to 5000 times) with water and the like before being sprayed.

The amount of compound [+1] to be used, the combination with other types of chemicals, and the ratio of these combinations will depend on various factors such as the growth stage of the target plant, growth status, type of disease, disease onset, timing of application of the chemical, and application method. Although it varies depending on the conditions, generally the compound [+] is 10 to 300 g per 10 ares.
You just have to adjust it so that it is within the range. In addition, the concentration of compound [11] may be in the range of 10 to too ppm, and the method of use may be by spraying, dusting, rinsing, or coating the seeds on the crops. As long as it is used safely and effectively, no limitations will be placed on the present invention no matter how much, how often, or how it is used.

Next, a method for producing the compound [H, which is an active ingredient] will be described. Compound [1] is described, for example, in Takeda Research Institute Annual Report, No. 22.
It can be easily produced by the method described in, vol., p. 19, p. 27 (1963), or by a method modified therefrom. That is, [l] [wherein RI-R8 has the same meaning as above] Method: C
l co(R2-hydrogen atom) + halogen other agent; [I](
R, -Halogen atom) R1 ->El-] [Wherein, R3 to R, have the same meanings as above, and X is I-I
[indicates a group or atom that leaves].

The monotony of the Δ method is 1,3-nocarbonyl compound [■ and 2-
This is a method for synthesizing compound [+] by reacting with pyrimidylhydrazine compound [111]. In its nature, the compound [nll may be used in its free form or may be subjected to the reaction in the form of an acid addition salt. Examples of such acid addition salts include organic acid addition salts and inorganic acid addition salts, with inorganic acid addition salts being more preferred. Examples of such inorganic acid addition salts include hydrochloride, hydrobromide, sulfate, and phosphate. This reaction usually involves compound [II]
This is done by mixing approximately equimolar amounts of the compound [[1] and the compound [[1], but in some cases one of them may be mixed in a slightly thicker manner, that is, [1] and the compound [[]] and [I[[] and [1].
The reaction may be carried out with a molar ratio of 1.001:l to 1.5:I, or when compound [11] is liquid, an excess amount of [11] with respect to [III] may be carried out. Rope F
A. It may also be used as a solvent by using 5 to 10 times the mole. In addition, if both are solids, the reaction may be carried out by heating to melt and liquefy them. However, it is generally preferable to carry out the reaction in an organic solvent in order to proceed smoothly, and any organic solvent may be used as long as it does not interfere with the reaction.

For example, methanol, ethanol, propatool, alcohols such as butanol, methyl cellosolve, ethyl cellosolve, diethyl ether. Ethers such as tetrahydrofuran, dioxane, dimethoxyethane, benzene, toluene.

Aromatic hydrocarbons such as cylene are particularly preferred.

These solvents can be used alone or as a mixed solvent of two or more at various mixing ratios. The amount of solvent used is not particularly limited, but [11] and [I[
A suitable amount is from the minimum amount that can dissolve the mixture of [I] to 20 times that amount. This reaction generally proceeds smoothly and does not necessarily require heating if accompanied by sufficient stirring and shaking, but heating may be necessary if the reaction is desired to be completed within a short period of time. The reaction temperature is usually 20°C to 15°C.
Although the temperature is preferably around 0°C, a higher temperature close to 200°C may be required. Generally, the reaction is carried out by stirring without heating, or by heating to the boiling point of the above-mentioned solvent and refluxing. Further, although the reaction is usually carried out under normal pressure, it is also possible to carry out the reaction under pressure using a closed container in some cases. Since the progress of the reaction can be followed by thin layer chromatography as described later, the end point of the reaction can be easily determined.

Therefore, the reaction time is not particularly limited. The reaction time also varies depending on the type of raw materials and solvent, reaction temperature, etc. It is usually completed within several tens of minutes to several tens of hours. This reaction is essentially a dehydration condensation reaction between a 1,3-dicarbonyl compound and a hydrazine to produce a pyrazole compound, but under normal conditions there is no need to be particularly careful about dehumidifying and dehydrating the reaction system. do not have. However, especially when you want to accelerate the reaction and improve the yield, use well-dried and dehydrated raw materials and solvents, pay attention to moisture-proofing during the reaction, and remove water generated in the reaction system from the solvent. If a dehydrating agent such as a molecular nitrogen is added to the system, the results may not be good. Although the presence of a catalyst is not essential for this reaction, the addition of an acid or base may significantly accelerate the reaction. The acid may be an organic acid or an inorganic acid, and examples of the organic acid that can be used include formic acid, acetic acid, and propionic acid, and these can also serve as a solvent. Examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, and polyphosphoric acid (P
Lewis acids such as PA), polyphosphoric acid ester (PPE), titanium tetrachloride, and boron trifluoride can be used, and sulfuric acid, polyphosphoric acid (PPA), etc. can also serve as a solvent and a dehydrating agent. As the base, for example, inorganic bases such as potassium hydroxide, sodium hydroxide, sodium medlate, and sodium edileate, and organic bases such as pyridine and triethylamine can be used, and the latter can also be used as a solvent. Moreover, an acidic or basic ion exchange resin can also be used as the solid catalyst. Furthermore, as mentioned earlier, the compound [11
When 1] is subjected to a reaction in the form of an acid addition salt, an acid as a catalyst is also added to the reaction system.

In general, acids give better results as catalysts in terms of reaction rate, yield, coloring, etc. The amount of the catalyst to be used may be a so-called catalytic amount, or it may be added in an equimolar amount to [1] or [■], or, as mentioned above, an excess amount may be used to serve as a solvent.

Method B is a method for synthesizing compound [I] (R, = halogen atom) by reacting compound [I] (R, -hydrogen atom) with a halogenating agent. The halogen atom (R1
) is usually chlorine, bromine, or iodine, and the halogenating agent used in the reaction is R, if = chlorine, chlorine gas 1N-chlorosuccinimide, sulfuryl chloride, etc.

When n t =bromine, bromine, N-bromosuccinimide (NBS), etc.

When n t = iodine, it is iodine, N-iodosuccinimide, iodine chloride, etc.

can be given. In the main cooking, the raw material compound [11(r(.

= hydrogen atom) is produced, for example, by the method A described above or the method C described below. Therefore, the raw material compound [
[ ] (R, = hydrogen atom) may be used in its free state, or may be subjected to the reaction in the form of the acid addition salt or quaternary salt described above. In this reaction, 1 to 5 mol of the halogenating agent is usually added to 1 mol of the compound [r] (It, = hydrogen atom).
Preferably, about 1 to 2 moles are used and the reaction is carried out in a solvent. When the halogenating agent is a gas, a method may be used in which the gas is continuously introduced into the reaction solution until the reaction is completed.

In addition, when the halogenating agent is liquid, compound [1] (+t,
= hydrogen atom) The liquid may be used in considerable excess, ie, about 3 to 200 moles, to serve as a solvent. Water or relatively inert organic solvents are frequently used as solvents. Examples of such organic solvents include dichloromethane, dichloroform, halogenated carbons such as carbon tetrachloride, and acetic acid. Although the amount of solvent used is not particularly limited, compound [1] (
R2-hydrogen atom) or a salt thereof is suitably used in an amount ranging from the minimum amount to 20 times that amount. This reaction usually proceeds satisfactorily at room temperature or under water cooling, but it may also be heated to reflux near the boiling point of the solvent. The reaction time varies depending on the type of raw materials and solvent, the degree of reaction layer, etc., and is usually completed within several tens of minutes to several tens of hours. The end point of the reaction can be confirmed by thin layer chromatography as described later.

Method C is a method in which a pyrazole compound [IV] and a pyrimidine derivative [V] are reacted to synthesize a compound [+]. X at the 2-position of the pyrimidine derivative [V] is a group or atom that can be eliminated as HX, such as a lower alkylthio group (methyldio, ethyldio, etc.), phenylthio group, lower alkylsulfonyl! (methanesulfonyl,
ethanesulfonyl, etc.).

Examples include -benzenesulfonyl group, nitroamino group, nitroamino group, and halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, but chlorine is often used. Compound [IV] in nature
and Compound [V] may each be used in its free form or may be subjected to the reaction in the form of an acid addition salt. Examples of such acid addition salts include organic acid addition salts and inorganic acid addition salts, with inorganic acid addition salts being more preferred. Examples of such inorganic acid addition salts include hydrochloride, hydrobromide, and sulfate.

Examples include phosphates. This reaction is usually carried out by treating the pyrazole compound [IV] with a strong base [rV] in an organic solvent.
], the pyrimidine derivative [
] to the reaction solution. Examples of solvents include alcohols such as methanol, ethanol, propatool, butanol, Medilce Solub, Edil Cellosolve, and dimethylpolamide. Particularly preferred are amides such as dimethylacetamide and hexamedylphosporamide, and sulfogints such as dimedylsulfoquinde. Examples of strong bases include strong inorganic bases such as sodium hydride, potassium hydroxide, and tert-2-doquine potassium, and diazabicyclononene (DBN).
.

Strong organic bases such as diazabicycloundecene (DBtl) are frequently used. The strong base is usually used in an amount of 1 mol or slightly in excess per 1 mol of compound [rV]. Compound [V
] is usually used in an amount of 1 mol, and in some cases about 0.5 to 2 mol, per 1 mol of compound [■]. Although the reaction temperature of this reaction is not particularly limited, better results are often obtained if the reaction is carried out at room temperature or a temperature lower than room temperature, for example, under water cooling. The reaction time varies depending on the type of raw materials and solvent, the degree of reaction layer, etc., and is usually completed within several tens of minutes to several tens of hours. The end point of the reaction can be confirmed by thin layer chromatography as described below.

In each of Methods A, B, and C, the end point of the reaction can be easily confirmed by, for example, thin layer chromatography. That is, on a thin layer of silica gel, a spot different from that of the raw material compound is irradiated with ultraviolet light (2536A).
Alternatively, the reaction may be terminated at the point where it can be detected by spraying Dragendorff's reagent.

The compound [1] produced in this way is usually a colorless or slightly colored crystalline solid or a viscous cloth at room temperature, and if it is extremely viscous, it is a syrup-like or glassy semi-solid. . Generally, they are almost insoluble in water and can be used in many organic solvents, such as alcohols, ethers, aromatic hydrocarbons, aliphatic halogenated hydrocarbons such as chloroform and dichloromethane, and ethyl acetate. . It dissolves well in esters such as butyl acetate, acid amides and nitriles such as tumedelformamide and acetonitrile.

Therefore, in the case of a crystalline solid, either cool it as it is after the reaction is complete, or add water if the reaction solvent is miscible with water, or distill off the reaction solvent, and recycle the resulting crude product from an appropriate solvent. Purify crystals.

In the case of a cloth-like material, a crude product obtained by the same treatment is purified using column chromatography.

If an acidic or basic catalyst is added or a solvent is used, it is necessary to perform neutralization treatment depending on the liquid properties, but in the case of an acidic catalyst or acidic solvent, the above treatment can be carried out as is. The reaction product can be isolated as an acid addition salt. In addition, if desired, after isolation as a free base, it is also possible to lead to addition salts of various organic and inorganic acids such as those listed in n.71, and the resulting acid addition salts are included in the target product [1] together with the free base. The structure of the resulting reaction product can be confirmed by elemental analysis, infrared absorption spectrum, ultraviolet absorption spectrum, mass spectrometry, nuclear magnetic resonance spectrum, etc.

Many of the raw material compounds [g], [[IT], [lV], and [V] used in the two-legged method A and C are known compounds and can be easily obtained. Alternatively, it can be easily synthesized by a synthesis method described in literature or a method analogous thereto. In addition, new starting compounds can be easily synthesized by following synthetic methods similar to those described in literature.

The 1,3-dicarbonyl compound [1] can be easily synthesized by a conventional method for synthesizing a 1,3-dicarbonyl compound, such as a general method such as an alkylation reaction of acetylacetone, or a method analogous thereto. Modern Nonsetake Reakn Yons (Modern 5ynthet)
ic Reactions) 2nd edition, pages 492, 73
Page 4 (1972): Complete Japanese Chemistry, Experimental Chemistry Course, Volume 19, Page 316 (1957): Same edition, New Experimental Chemistry Course, Volume 14 (H), Page 751 (1977); Organic Synthesis (Organic 5ynthe
ses), Volume 3, page 291 (1955), Volume 5,
Pages 785 and 848 (1973) 1 Japan Chemical Journal.

Volume 88, page +068 (1967), Journal of the American Chemical Society
of the American Chemical 5
68: 453 (1946), etc.].

The 2-pyrimidylhydranone compound [I11] has, for example, a halogen atom such as chlorine or bromine at the 2-position, a lower alkokynyl group such as methoxy or ethoxy group, a phenoquinol group,
Lower alkylthio groups such as mercapto groups, methyldio groups, ethylthio groups, phenylthio groups, methanesulfonyl groups, low-sensitivity alkylsulfonyl groups such as ethanesulfonyl groups, benzenesulfonyl groups, nitroamino groups, ananoamino groups, trimedelammonium, triethylammonium groups It can be easily synthesized by reacting a pyrimidine derivative having a cycloammonium group, etc., with hydrazine in the presence of an inorganic base [Pharmaceutical Journal, Vol. 73, pp. 159, 598 (1 , 953),
790.1477 (1959): Chemical and Pharmaceutical Bulletin
＆Pharmaceutical Bulleti
n), vol. 17, p. +479 (1969): Australian Journal of Chemistry
lian Journal of Chemistry
), Vol. 30, p. 2515 (1977)].

Representative examples of the compound [+] produced by the above reaction are shown in Table 1.

Table 1 (Note 4) Note 1) Compounds 1, 4, and 5.12 are known compounds described in the following literature.

Takeda Research Institute Annual Report, Vol. 22, p. 19 (1963): Chemische Be'/Chemische Be
Richte), Vol. 98, p. 3178 (1965); European Journal of Medicinal Chemistry (Furopean Journal of M.
(edicinal chemistry).

Volume 10, page 633 (1975); Antibacterial and antifungal: Volume 3.

3 pages (1975).

Note 2) Compound 12 is known as an anhydride and a dihydrate.

Note 3) It is undetermined which structure it has, and it is possible that it is a mixture of both.

Note 4) The abbreviations of the base names in the table are as follows.

Me Methyl Et Ethyl Pr Propyl iPr Isopropyl Bu Butyl iBu Isobutyl tBu Lert-Butyl Hero Allyl action, effect The plant disease control agent of the present invention has very few side effects;
Since it is simple, inexpensive, and can accurately produce excellent actions and effects, it has great utility in the industry.

Reference Example 1 Synthesis of 2-hydrazino-4,5,6-)limethylpyriminone 2-chloro-4,5,6-)-limethylpyrimidine 3''
'g, Fa water 3.00 g of hydrazihydrazine, 3.45 g of potassium acid were added to 25 ml of ethanol and boiled for 8 hours.

The solvent is distilled off, water is added to the residue, and the precipitated crystals are collected by filtration, washed with water, and dried. Melting point: 165°C. Yield 2゜0g0 Elemental analysis value (CtH + tNa) Calculated value: C, 55,24; H, 7,95; N,
36.82% actual value: C, 55,38; H, 7,8
9,N, 36.72% Reference Example 2 Synthesis of 5-chloro-4,6-dimethyl-2-hydrazinopyrimidine 2.5-dichloro-4,6-dimethylpyrimidine 10.
Add 3 g of hydrazine hydrate, 5.82 L of anhydrous potassium carbonate, and 8.0 g of anhydrous potassium carbonate to 100 ml of ethanol and boil for 25 hours.

The solvent is distilled off, water is added to the residue, and the precipitated crystals are collected by filtration, washed with water, and dried. Melting point 197-199°C. Yield 13.7g0
Elemental analysis value (CgH, N, CI) Calculated value: C141,75; 11.5.26. N
, 32.46% Experimental value: C, 41,42; I-r,
5.20. N, 32.67% Reference Example 3 Synthesis of 2-hydrazino-4-methylquinazoline 2-chloro-4-medylquinazoline a, gg, hydrazine hydrate 2
Add 2.5 g of anhydrous potassium carbonate to 40 ml of ethanol and boil for 2 hours. The solvent was distilled off, water was added to the residue, and the precipitated crystals were collected by filtration, washed with water, and dried. Melting point 183-1
84℃. Yield: 3.0g.

Reference example 4 1(3,5-dimethyl-1-pyrazolyl)-4°5.6
-Synthesis of trimethylpyrimidine (compound number 29 in Table 1) 2-hydrazino-4,5,6-trimethylpyrimidine 1
．． 52g and acedelacetone t, oog ethanol 2
0ml and boil for 8 hours. The solvent is distilled off, water is added to the residue, and the precipitated crystals are collected by filtration. This is recrystallized from dilute methanol. Melting point 83.5-85°C.

Yield fi1.96g0 Elemental analysis value (C12H18N 4・2H20) Calculated value:
C, 57, 11; H,? , 99. N, 22.2
1% actual value: C, 57,19; H, 7,91;
N, 22.37% or less, compound numbers 2-3, 6-1
Compounds 1.13-25.30-34 can be produced by the method of Reference Example 4. Their physicochemical data are as follows.

2-(5-ethyl-3-methyl-1-pyrazolyl)pyrimin)one or 2-(3-ethyl-5-methyl-1-pyrazolyl)pyrimidine (compound number 2) nioyl (purified by column chromatography) Elemental analysis Value (CIO812N 4) Calculated value: C, 63, 81; H, 6, 43, N, 29
．． 77% actual value: C, 63,16; H, 6,55,
N, 30.09% NMR spectrum (CDCl2.δ value) 1.25Q), 2.35 (s), 2.67 (s)
, 2.75(q).

3.15(q), 6.09(s), 7.12(t)
, 8.73(d) 2-(3,5-diethyl-1-pyrazolyl)pyrimidine (compound number 3) nioyl (purified by column chromatography) Elemental analysis value (C,, H1, N,) Calculated value: C , 65, 32; tl, 6.98. N
, 27.70% Actual value: C, 64, 90; Il, 7
．． +2. N, 27.94% 2-(5-ethyl-3-
Methyl-1-pyrazolyl)-4-methylpyrimidine or 2-(3-ethyl-5-methyl-1-pyrazolyl)-
4-Methylpyrimidine (compound number 6) nioyl (purified by column chromatography) Elemental analysis value (C,,H,,N,) Calculated value: C,65,32; f(,6,98,N,2
7.70% actual value: C, 65,16; H, 6,98
, N, 27.73%N M 11 spectrum (CDC1
,, δ value) 1.25 (L), 2.33 (S), 2.
60(S), 2.68(S), 2.75(q),
3.15(q), 6.08(s), 7.00(d)
, 8.58(d) 2-(3,5-diethyl-1-pyrazolyl)-4=medylpyrimicin (compound number 7) nioyl (purified by column chromatography) Elemental analysis value (CI2H16N4) Calculation (direct: C, 66 ,64: I-[,7,46,
N, 25.91% actual value, C, 66,37, H, 7,4
7, N, 26° 01% 4-Mejirou 2-(3,4,5-
Trimethyl-l-pyrazolyl)pyrimidine (Compound No. 8): Melting point approximately 86C 2-(3,5-dimethyl-1-pyrazolyl)-5-methylpyrimidine (Compound No. 9): Melting point 82-85°C 4.6-dimethyl- 2-(l-pyrazolyl)pyrimidine (compound number lO)nioyl (purified by column chromatography) Elemental analysis value (C,)I,ON,') Calculated value: C,6
2,05; I-1,5,79; N, 32.11
% Actual value: C, 61,95; H16,06; N
, 32.13% 4.6-dimethyl-2-(3-methyl-
l-pyrazolyl)pyrimidine (compound number 11) nioyl (purified by column chromatography) Elemental analysis value (C, H, N4) Calculated value: C, 63, 81: H, 6, 43, N, 29
．． 77% actual value: C, 63,84; H, 6,43,
N, 29.94% 2-(5-ethyl-3-methyl-■-
pyrazolyl)-4,6-dimethylpyrimidine or 2-
(3-ethyl-5-methyl-1-pyrazolyl)-4,,
6-nomethylpyriminone (compound number 13) nioyl (
Purified by column chromatography) Elemental analysis value (C, 211111N4) Calculated value: C, 66, 64; H, 7, 46, N, 25
．． 91% actual value・C, 66, Ol, I-1, 7, 4
4, N, 25.65% N M R7! , vector (CD
C1a, δ value) 1.25 (L), 2.35 (s),
2.53 (s), 2.67 (s), 2.77 (+1
), 3.15(Q), 6.08(S), 6.88
(S)2-(3,5-diezyru■-pyrazolyl)-4
,6-dimethylpyrimidi (compound number 14) nioyl (purified by column chromatography) Elemental analysis value (C,,H,,N,) Calculated value: C, 67,73; II, 7.88. N
, 24.33% Actual value: C, 67,83; ■1,7
．． 90. N, 24.13% 4.6-cymethyl-2-
(3,5-dipropyl-l-pyrazolyl)pyrimidine (
Compound No. 15) Nioil (purified by column chromatography) Elemental analysis value (C15tLtN-) Calculated value: C069,73; I-1,8,59;
N, 21.69% Actual value: C169,65; H,8
,64,N,21.58%2-(3,5-diisopropyl-1-pyrazolyl)=4,6-dimethylpyrimidine(
Compound No. 16) Nioil (purified by column chromatography) Elemental analysis value (C1d-122N4) Calculated value 2C, 69, 73, H, 8, 59, N, 21.
69% actual value: C, 69,97; I-1, 8,6g
, N, 21.56% 2-[3,5-n(tcrt~
butyl)-1-pyrazolyl]-4,6-dimethylpyrimidine (compound number 17): melting point 118°C 4.6-nomethyl-2-(3,4,5-1rimidyl=1
-pyrazolyl)pyrimidine (compound number 18): dihydrate, melting point 37.5-39°C 4,6-dimethyl-2-(3,5-tumethyl-4-ethyl-1-pyrazolyl)pyrimidine (compound number 19) ):
Dihydrate, melting point 72°C 1,6-dimethyl-1-(3,5-dimethyl-4-propyl-1-pyrazolyl)pyrimidine (Compound No. 20)
: Dihydrate, melting point 55℃ 4.6-methyl-1-
(3,5-dimethyl-4-butyl-1-pyrazolyl)pyrimidine (compound number 21): dihydrate, melting point 65°C 4,6-dimethyl-2-(3,5-dimethyl-4-isobutylene-1- pyrazolyl)pyrimidine (compound number 22
) Elemental analysis value (C
1, Ll 22N 4) Calculated value: C, 69, 73;
It, 8.59; N, 21.69% Actual value C, 69, 67: H18, 10, N, 22.10%
4.6-nomedyl-2-(3,5-dimethyl-4-allyl-1-pyrazolyl)pyrimidine (compound number 23),
dihydrate, melting point 608C 4,6-nomethyl-2-(3,4-trimethylene-5-
Methyl-1-pyrazolyl)pyrimidine (Compound No. 24
) Nioil elemental analysis value (Cl311 IQN, ・H, O) calculated value: C, 63, 39; H, 7, 36; N, 22
．． 79% actual value: C, 63,51; H, 7,42,
N, 22.66% 4,6-nomethyl-2-(3,4-tetramethylene-5-medy-1-pyrazolyl)pyrimidine (Compound No. 25): Melting point 67-69°C 4,5,6-trimethyl-2 -(3,4,5-1-tumethyl-1-pyrazolyl)pyrimidine (Compound No. 30)
, dihydrate, melting point 103-104°C5-chloro-2
-(3,5-dimethyl-1-pyrazolyl)pyrimidine (
Compound No. 31): Melting point 124-126°C 5-chloro-4,6-nomethyl-2-(3,5-tumethyl-1-pyrazolyl)pyrimidine (Compound No. 32),
Melting point 76-78°C 2-(3,5-dimethyl-1-pyrazolyl)quinazoline (compound number 33) Melting point 90-old °C 2-(3,5-
Dimethyl-I-pyrazolyl)-4-methylquinazoline (
Compound No. 34): Melting point 101-103°C Reference Example 5 Synthesis of 4.6-nomethyl-2-(1-indazole)pyrimidine (Compound No. 26) 05 g of 50% sodium hydride was suspended in 10 ml of dry trimethylformamide. Add 10 g of indazole little by little to this while stirring and cooling with water.

Then, 2-chloro-4,6-dimethylpyrimidine 1.
Add 43g little by little. Thereafter, it is left at room temperature overnight and then heated to 60 to 70°C. After cooling, pour into water,
Extract with chloroform. This extract is dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography on Noriyoku gel (eluted with a mixed solvent of l.luene and chloroporm), and the resulting crude product was recrystallized from noclohexane to obtain a colorless prism product 1 with a melting point of 138-139°C. Obtain .48g.

Elemental analysis value (Cl31112N 4) Calculated value C, 69, 62, Il, 5.39. N, 24
．． 99% actual value C, 69, 74, 1+, 5.29:
N, 24.86% Reference Example 6 2-(4-chloro-3,5-dimethylpyrazolyl)-4
, 6-Dimethylpyrimidine (Compound No. 27) Anhydrous 71.6-methyl-2-(3,5-methyl-1
-pyrazolyl)pyrimidine (compound number 112) 4.04
A solution of 297 g of sulfuryl chloride diluted with 2.5 ml of dry chloroform was slowly added dropwise to the solution while stirring at room temperature.

This is followed by boiling under reflux for 3 hours. After cooling, a small amount of insoluble matter is filtered off, and the filtrate is concentrated under reduced pressure.

The residue was recrystallized from nclohexane, melting point 73-7.
356 g of colorless needles at 4° C. are obtained.

Element minute hand value (C,,l-1,3CIN,) Calculated value C,5
5,81,■1.5.54; N, 23.67% actual value C, 55,8+, IT, 5.38. N, 2
3.86% Reference Example 7 Synthesis of 2-(4-bromo-3,5-tumethyl-1-pyrazolyl)-4,6-tumethylpyrimidine (Compound No. 28) 4.6-dimethyl-2-(3,5 -Tumedel-I-pyrazolyl)pyrimidine 4.04g in chloroform 20ml
Dissolve 3.20 g of bromine in this and 28 m of chloroform.
Slowly add the solution dissolved in 1 dropwise while stirring at room temperature. - Leave at room temperature overnight, filter out the precipitated crystals, wash with a small amount of ethyl acetate, and dry. Hydrobromide, melting point 15
3-155°C0 yield 6.60g0 elemental analysis value (C1l
H13I3rN4- HBr) Calculated value C, 36, 49,
il, 3.90. N, +5.47% actual value・C, 3
4,93,11,4,22,N, +5.30%'' The free base can be obtained by neutralizing the bipedal hydrobromide. Melting point 81.5-85°C.

Reference η Example 8 Synthesis of salt of 4.6-dimethyl-2-(3,5-tumedel-1-pyrazolyl)pyrimidine (Compound No. 12) The salt of the title compound (Compound No. 12) can be produced by a conventional method. .

Picrate ・Melting point 135-136°C Sasocalinate Melting point 129-130°C Silver nitrate (l
/2 mol) addition salt, melting point 158-159°C N-methylioguid Melting point! 60-16]'CN=Medylful sulponate: Melting point 175-176°C Examples 1 to 6 Preparation 1 of a step-setting agent composition containing compound [+1] Compound [l] (compound 12 of Table 1 dihydrate) 5
0%.

Thorium lignin sulfonate 2%, white carbon 3%, polyquinoethylene alkyl allyl ether 5%
, a hydrating agent made by mixing 40% clay.

Dilute 1,000 to 3,000 times with water and use 1 o1 per are (hereinafter abbreviated as a)! Gara2o9. Spread.

2. A powder prepared by mixing 3% of compound [I] (compound 15 in Table 1), 0.1% of aluminum stearate, and 969% of clay. Spray 300g to 500g directly per a.

3. Granules prepared by mixing and granulating 5% of compound [I] (compound 16 in Table 1), 5% of gum arabic, 30% of bentonite, and 60% of talc. Direct application of 300g to 500g per a.

4. Compound [I] (Compound 12 in Table 1) 20%, Kil
/L/:/75%, emulsion containing 5% polyoxine ethylene alkylaryl ether. Dilute 40 to 2000 times with water and spray directly on 109 per a.

5. A wettable powder prepared by mixing and pulverizing 30% of compound [+] (compound 21 in Table 1), 5% of sodium lignin sulfonate, 5% of polyoxine ethylene alkyl ether, and 60% of clay. 10 per a by dipping 40 to 2000 times in water
gSpray directly.

6 A granule prepared by adding water to a mixture of 10% of compound [l] (compound 22 in Table 1), 5% of sodium ligninsulfonate, and 85% of bentonite and kneading the mixture. Apply directly at 300g to 500g per a.

Test Example I Antibacterial activity tests were conducted on representative target compounds (indicated by the compound numbers listed in Table 1) and control compounds using the multiple dilution method using an agar medium as described below, and the results are summarized in Table 2. Ta.

l Assay medium Glucose broth agar medium 2 Drug,
Manufactured by J1-1 Test compound or pair 11 (i compound 40m
g was dissolved in a mixture of 0.5 ml of N,N-methylformamide and 95 ml of acetonate, and the solution was mixed with sterile water at a concentration of 1000 μg/ni1. : Dilute (concentration in medium is 1/10).

3. Test bacteria 1) Pyricularia oryza T- (Pyricularia
ia town - μ river) IFO5279, rice plant disease fungus 2) Helminthosborium nogmoideum (11e1min
thosporium sigmoidium) I
FO4867, Rice micrococcal fungus 4, Inoculation method: Test bacteria: Bacterial solution inoculation 5, Culture #28°C, 4 days 6, Judgment: Minimum growth inhibitory concentration (MIC μg/ml)
I asked for

7. Test Results Table 2 Test Example 2 The rice blast control effect when sprayed on foliage was investigated using the following test method, and the results are shown in Table 3.

The test compounds are shown by compound numbers in Table 1.

Test method: ■ Pathogen: Pyricularia oryzae P-2 mother fungus 2 Test plants: 1 rice variety Asahi No. 4, 10 9 cm pots
Main plant, approximately 328 seedlings 3, Inoculation: Natural infection from blast-damaged leaves 4, Chemical treatment: Test compound [I] (compound 12 in Table 1) prepared by the method of Example 4 was diluted to the specified concentration. A spreading agent (Dyne, trade name, manufactured by Takeda Pharmaceutical) was added at a rate of 0.2%, and sprayed 28 days after the start of inoculation. Example 4 for other test compounds
Similarly, an emulsion containing 20% of the compound, 75% of xylene, and 5% of polyoxyethylene alkylaryl ether is prepared and spread in the same manner.

5. Ward system: 1 ward, 2 pots 6. Survey: 7 days after inoculation, 6 bottles published by the Plant Protection Association” (S.

49.2.15) r Criteria for Infection Infection Infection Survey Criteria J (pages 4-7) for the diseased area rate of leaf blasts was used to investigate, and the control value was calculated using formula (1).

Table 3 Test results (treatment): Test Example 3 Emulsions of each sample were prepared according to the method described in Test Example 2, and the preventive effect on rice blast control was investigated, and the results are shown in Table 4.
It was shown to. The test compounds are shown by compound numbers in Table 1. However, inoculation was started after the spraying and air drying (3 hours later).

Table 4 Test Example 4 The effect of controlling rice sheath blight was investigated using the following test method, and the results are summarized in Table 5. The test compounds are shown by compound numbers in Table 1.

Test method: 1. Pathogen: Bellicularia sasakii (Rhizoctonia
Sorani-Sazaki type) [pelliculariasas
akii (Rhtzoctonia 5olani 5
asaki + type)] 2. Test plants: 1 rice variety Kinnanpu, 9 cm bot main planting, 80-90 days seedlings 3. Inoculation: periphery of bacterial flora cultured on potato sucrose agar medium at 28°C for 2 days. Punch out with a 10 mm cork pole and insert it between the stems of rice plants for inoculation.

25-35°C, 70-100% R11 until investigation after inoculation
held below.

4. Chemical treatment: Perform the treatment method described in Test Example 2.

However, inoculation should be done after spraying and air drying.

5. Ward system: 1 ward, 2 bottles 6. Survey: 10 days after inoculation, measure the height from the ground edge to the top of the lesion and calculate the rate of lesion expansion compared to the untreated area.

Table 5 Test Results: Test Example 5 The effect of controlling rice sesame leaf blight when sprayed on foliage was investigated using the following test method, and the results are summarized in Table 6. The test compounds are shown by compound numbers in Table 1.

Test method 1. Pathogen: Helminthos borium oryzae (2. Test plant: Based on test example 2. 3. Inoculated potato sucrose agar medium cultured at 28°C for 10 days to avoid formation of spores U!: Turbid liquid (cell F concentration I~2
105/ml) was sprayed and inoculated at 28℃ for 2 days after inoculation.
The specimen was kept under 00% R1+ (relative humidity), and then left in a greenhouse 4 and treated with chemicals: the treatment method described in Test Example 2 was performed. However, inoculation should be done after spraying and air-drying.

5 District system: 1 district, 2 bottles6, 7 days after survey and inoculation, published by the Japan Plant Protection Association (S,
49.2.15) Modified method of ``Separate severity of wheat rust, minor rust, and black rust'' of ``Standards for inspection of pest and disease outbreaks'' (
(page 27). The control value is the formula (1) of Test Example 2.
Calculated by.

Test results Table 6

Claims (1)

[Claims] General formula ▲ Numerical formulas, chemical formulas, tables, etc. indicates that each may further be a halogen atom, and R_1
and R_2 may form a lower alkylene group, and R_2 and R_3 and R_5 and R_6 may each form a butadienylene group. Fungicide.