JPS6245585A - Pyrimidine compound, its production, composition containing said compound, production of said composition and control ofbacteria - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to substituted aryldioquinane pyrimidines and aryldioxane biIJ midines represented by the following formula I and acid addition salts thereof. In particular, the present invention relates to processes for the preparation of these compounds, to compositions containing at least one compound of the formula I as an active ingredient, to processes for the preparation of these compositions, and to methods for the control of phytopathogenic microorganisms or Vi for said microorganisms. ■
The present invention relates to a method of protecting plants from damage.

(Structure of the Invention) In particular, the present invention relates to the general formula I: [wherein AII: t-phenyl group, phenoxyphenyl group, phenylthiotuunyl group, biphenyl group or hanaphthyl group, Ra, Rh and RCVi each independently So, hydrogen atom...
rogeno atom, cyano group, nitro group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, rogenoalkyl group having 1 to 4 carbon atoms, or rogenoalkyl group having 1 to 4 carbon atoms represents a noalkoxy group, and X represents the following bridging group: (wherein, It and TL2 independently represent a hydrogen atom, a carbon IQ
represents an alkyl number of 1,000 to 4, a halogenoalkyl group having 1 to 4 carbon atoms, or a C1,0- (alkyl group having 1 to 4 carbon atoms) group, R4 is a hydrogen atom, and R4 is a hydrogen atom, 4 alkyl group or C112011 group, and It, , 1- and rhVi each izC independently have a hydrogen atom or a carbon atom number of 1
The present invention relates to a compound represented by the following formula and an acid addition salt thereof.

In a narrower sense, the present invention relates to A, Ra, Rb.

to compounds of the formula I in which Rc, R4 and R have the meanings given above and R is a hydrogen atom and Rs, R4 and R are independently of each other a hydrogen atom or a C1-C4 alkyl group; Acid addition salt K jl (compound group 1a).

Depending on the number of carbon atoms indicated, the alkyl group itself or as the alkyl moiety of another substituent may be substituted with, for example, the following groups: methyl, ethyl, propyl, butyl, and isomeric groups. It will be understood to mean a propyl group, an isobutyl group, a 3-butyl group or a 5ec-butyl group.

...Ugen itself or other substituents...A halogen atom as a halogen moiety is a fluorine atom, a chlorine 1' heart, a bromine atom or an iodine atom, and a fluorine 1'1 (child, a chlorine atom or a bromine atom is preferred). “It’s delicious.

The bridging group X, together with an oxygen atom and a common carbon atom, forms diogy7nolane and dioxanya.

The present invention is directed to the free form of the compound No. 1 of the formula (1).
, , and their acid addition salts with organic or inorganic acids.

Examples of salt-forming acids include inorganic acids: halogen-free acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid, as well as sulfuric acid, phosphoric acid, phosphoric acid and nitric acid; and acetic acid, Trifluoroacetic acid, trichloroacetic acid, propionic acid, tartaric acid, glycolic acid, thiocyanic acid, lactic acid, co...
phosphoric acid, citric acid, benzoic acid, cinnamic acid,
Ren, quinzenesulfonic acid, halatoluenesulfone r, 2, -tansulfone (4, medium,: litine + 12,
Harami/Salicylic acid, ″-Fenogin′i Zozoic acid or Q
Examples include 22-alcokyne groups and organic acids such as aromatic acid.

At room temperature, the compound of formula I is stable as an oil, a resin, or a resin.
It is characterized by its solid, very strong IL f (j - certain microbicidal activity, especially the activity that attacks plants). Therefore, these compounds '1 are of course Preferably used for preventive or therapeutic control of plant pathogenic proboscis in agriculture or related fields.
1 saharu.

Preferred compounds of formula I because of their significant microbicidal activity are those containing the following substituents or combinations of substituents: A: a) phenyl 2□(, ), DiphenylAL Also, ij, nylthiophenyl group; Special Kl)) Phenyl group, 1"j, phenyl,:
5; Ra, R, b and lJ%c are each independently: a) hydrogen atom,...rogen atom, alkyl group having 1 to 2 carbon atoms, alkoxy group having 1 to 2 carbon atoms; , a halogenoalkyl group having 1 to 72 carbon atoms, a nitro group or an ano group having 1 to 72 carbon atoms: in particular b) a hydrogen atom, . . . , a hydrogen atom, having 1 to 2 carbon atoms;
an alkyl group having 1 to 2 carbon atoms, an alkyl group having 1 to 2 carbon atoms, a halogenoalkyl group having 1 to 2 carbon atoms, an alkyl group having 1 to 2 carbon atoms;
group or cyan group; as X: as R1 and R7 independently of each other: a) a hydrogen atom,
C1-C4 alkyl R-1 C1-C2 7-logenoalkyl T or C1-C2 alkoxymethyl group; especially 1]) hydrogen atom, C1-C4 alkyl Alkyl group or CHz OC) Is tiger; I (as 4: a) Hydrogen atom, alkyl group with 1 to 2 carbon atoms or C■IxOH group; Special K b) Hydrogen atom, methyl group or 1d C■LOH group; i
t, R and i are each independently: a) a hydrogen atom or a C1 -C2 alkyl A- group; in particular b) a hydrogen atom and/or a methyl group.

As compound group 1a, A, TLa, Rb and R
.
C11-2...logenoalkyl group or carbon a1, ? in 2 alphkyl dimethyl group; especially 1)) hydrogen atom, carbon
Cr) -r alkyl group or 11 CIT, QC) I, group; Preferably, within the range of combining t' of the above substituents (-2, lower -1
- substituent or fZf substituent 1↓1 combination of formula I
)"Pa 1 or compound group 1a is '$5 & very nice: A
As: Phenyllev, (7#17. Nogginfe r-
YLa R, b and Rc each independently: a chlorine atom or a methyl group, especially in the 2- and/or Vi4-position; as X: as R: with 1 to 3 carbon atoms; Alkyl group or C
H* 0CHs; as horse: hydrogen atom.

Also, A combines with Ra, Rh and Re to form Tera. 4-dichlorophenyl group, 2-fluoro-4-chlorophenyl group, 2-cyano-4-chlorophenyl group, 2-)thyl-4
- Chlorophenyl group, parachlorophenoxy group, 2-methyl-4-(p-chlorophenoxy) group or 2-chloro-4-(p-chlorophenoxy) group is
, to R6 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the compounds of the formula I are also preferred, in which one or more carbon atoms together do not contain more than 5 carbon atoms.

Compounds of formula I can be prepared as follows.

Method: By ketalization reaction, a ketone of the following formula ■: [In the formula, A, Ra R, b and nc represent the meanings defined in Formula 1] and a ketone of the following formula ■ HO-X-OH (book [Formula wherein X represents the meaning defined in formula (2)] in an inert solvent in the absence or presence of an acid.

Method B: A ketone of the following formula (1): ALK-C-ALK (1) [wherein ALK represents an alkyl group having 1 to 4 carbon atoms] and a diol of the above formula (1) are mixed in an inert solvent with an acidic inorganic acid. The reaction is carried out in the presence or absence of the compound to produce a compound represented by the following formula (1) [wherein ALK represents an alkyl group having 1 to 4 carbon atoms, and X represents the meaning defined in the above formula (2)] , directly without isolating the product compound of its progeny V, the ketone of formula (1) is ketalized with a compound of nuclear formula V in the presence of an acid.

These reactions include known ketalization reactions such as 'MMC synthesis (Synthesis) of 2-bromomethyl-2,4-diphenyl-1°3-dioxolane, +
974(1), p. 23].

In a preferred embodiment of ketalization, both reactants are heated together with an azeotropic additive in a conventional solution phase under reflux for several hours. Examples of suitable co-Me additives include benzene, toluene, xylene, couloloform or carbon tetrachloride. The addition of strong acids, such as para-toluenesulfonic acid, may be used to advantageously accelerate the reaction. In this case, suitable organic solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, etc. and saturated hydrocarbons such as n-hexane. Nothing(
Q acids or organic [λ] can also be used as reaction promoters. Examples of tangy acids include hydrochloric acid, hydrobromic acid, hydrogen collate, r-L sulfuric acid, phosphoric acid, phosphorous acid and nitric acid. Examples of organic acids include acetic acid, trichloroacetic acid, oxalic acid, benzenesulfonic acid, methanesulfonic acid, and para-toluenesulfonic acid.

Ketalization reaction reaction 111 degrees 620 degrees to 180 degrees
℃, preferably in the range of 40° to 150°C.

The above-mentioned manufacturing method constitutes the object of the present invention.

In the ketalization reaction of the above-mentioned ketone and substituted α, β- or α, r-diol, a mixture of diastereoisomers of ketul in which at least one of R1 to I(6 represents something other than a hydrogen atom) is produced. Generally, the final product diastereoisomeric mixture of Formula I is formed from the starting ketone.

The two diastereoisomers and enantiomers can be separated by conventional means. The diisomers may exhibit different microbicidal activities.

For practical purposes K is generally a mixture of diastereoisomers.

The present invention relates to all isomers of formula I and their salts.

The following individual compounds, both as individual isomers A or B or as a mixture of isomers, are preferred because of their biological activity.

5- (2-(2', 4'-dichlorophenyl)-
4-Ethyl-1,3-dioxolane-2H]pyrimidine [Compound 1.38. b; 1, 3; bow 1. ! +b〕5-
(2-(2', 4'-dichlorophenyl)-4-
Brovyl-1,3-dioquinran-2-yl]pyrimidine [Compound 1.4a; +, 4h; 1,4a, b) 5-
(2-(2′,4′-dichlorophenyl)-4-methoxymethyl-1,3-dioxolan-2yl)pyrimidine [Compound 1.7a;+, 7b;i, 7;+.

b] 5-(2-(2', 4'-dichlorophenyl)-
5-ethyl-5-methyl-1,S-,)oxan-2yl]pyridine [Compound 2.19; I, b;'+'fK2
．． 19;1) 5-(2-(2', 4'-dinoo7,
= /L, ) -4-methyl-1,3-dioxane-2
yl]pyrimidine [compound 3,6a,b) 5-(2-(2',41-dichlorophenyl)-4゜5
-Dinotyl-1,3-dioxolan-2yl]pyrimidine [Compound 1.6a: 1.61); 1.6a, b) 5-
(2-(2',4'-dichlorophenyl)-5゜5-dimethyl-1,3-dioxan-2yl]pyrimidine [Compound 2.2] 5-(2-(2',4'-dino.lophenyl) )-4゜6
-Simethyl-1,3-dioxan-2yl]pyrimidine [Compound 3.1] 5-(2-(2',4'-dichlorophenyl)-4!5
．． 6-Dorimethyl-1,5-dioxan-2yl]pyrimidine [Compound 3.2] 5-(2-(2'-cyano-41-rioophenyl)-
5-ethyl-5-methyl-1,5-dioxane-2yl]
Pyrimidine (compounds 2, 23a, b) 5-(2-(2'
, 4'-dichlorophenyl)-4-ethyl-1,3-dioxan-2yl]hyrimidine [compound 3.11a, b
] 5-(2-(2′-chloro-41-p-chlorophenoxyphenyl)-4-ethyl-1,3-dioxan-2yl)pyrimidine [Compound 2.25a.

b].

Some of the starting materials of formula (2) used for the preparation of the final product of formula (1) are novel and constitute the object of the present invention. They can be prepared by methods known per se, for example, by the following formula [wherein ALK is an alkyl group having 1 to 4 carbon atoms,
preferably represents a methyl group or an ethyl group, and A
, TL; I, R, l) and R, c represent the meanings defined in formula 1] A carboxylic acid ester represented by the following formula [in the formula, ) (
;+l represents a rogen atom, preferably a chlorine atom or a bromine atom] with lopyrimidine in an inert solvent in the presence of n-butyllithium and at a temperature range of -150° to 25°C. By reacting! A can be built.

The compound CH30 of the following formula is described in the literature as an aryldioquinyl pyrimidine derivative (for example, 1''; see Japanese Patent Publication No. 48-49776). Curing force enhancer of sulfonamides and 17
It is known for.

Surprisingly, the compounds of the present invention are useful for practical field use and oral administration, and are effective against harmful microorganisms Vζ1, i+, VC phytopathogenic 1'+'4%. ! It has been found that the microbicidal activity spectrum has a very wide range of VC against bacteria. Compounds of formula I have favorable therapeutic, permeation and retention properties, and
Cultivation of 〜detan'otsu 4. ! f1P to protect things
You can use a compound represented by formula 1.
(, Siri, Seed/Z useful crop plant' or part thereof (
It is possible to suppress or kill microorganisms infesting fruits, flowers, leaves, stems, tubers, roots) and at the same time protect later growing plant parts from attack by such microorganisms.

The compounds of formula I are effective against phytopathogenic fungi belonging to the following classes: Deuteromycota [e.g. Hylocycota, Ilelminthosporium, Fusarium, Septoria, Cercospora, Virulicularia ( Pyr
icularia), Deuteromycota] Basidiomycetes [] e.g. Hemi Ieia
Genus of fungi, Rhizoctonia (11,1 zocot
onia), Puccinia) and Puccinia) and Puccinia (Puccinia) and Puccinia (Puccinia) and Puccinia (Puccinia);
rIa), Podosphaera
), Erysiphe x, Monilinia, Uncinul
a)) Furthermore, the compound Vi represented by formula (2) has a penetrating action. They can also be used as dressings for seeds (fruits, tubers, grains) and plant cuttings against infections of stones and against phytopathogenic microorganisms occurring in the soil. .

The compounds of the invention are particularly well tolerated by plants Vζ.

Accordingly, the present invention also provides for the use of biological compositions and compounds of formula I for controlling phytopathogenic microorganisms, in particular fungi, and to be protected from attack by such microorganisms. Use of VC for preventive treatment of plants, gate.

Furthermore, the present invention also includes a process for producing Fji ML compositions by homogeneously combining the active ingredient with one or more compounds or compounds as described herein. '). This is method 1 for treating plants by applying a compound of formula I to piraphylla (also referred to as J-7 regulated compositions).

Crops that are kept within the scope of duty 1iIJ include the following plants: cereals (wheat, barley, rye, oats,
rice, corn and l', single crop); beets (
sugar beet and fodder beet); stone fruit, pear fruit and 1
Fruits (apples, raspberries, plums, peaches, berries, cherries, strawberries, raspberries, and blackberries)
; Legumes (fava beans, lentils, peas, soybeans)
; Oil fountains (oil, mustard, hobby, olive, sunflower, coconut, castor oil, fucoa beans, peanuts): Cucurbitaceae plants (cucumber, pumpkin, etc.)
Melon) ; Senkumi plant (ζ'self, Wholesale 1 臥 dog 1 (Jade, jute) S
fH genus tFf products (orange, lemon, grapefruit, mantarin); J vegetables (spinach, lettuce, "r"
Subaras, A: 1. N;-h, 1 pub); Camphor tree (1 (
Avoca 1゛, nnamon, disability ij, 4): , 1-corn, tobacco, nuts, 1-heat, 1t, +η; sugar, tea, fudo vine, hops, bananas? 1? So (flowers,
Shrubs, DoS'4'J II and Mari-! ¥tA': Of course)
. This record El is ljj: but it is not (7).

The active ingredient of formula I is usually applied in the form of abrasions and applied simultaneously to the crop ground or the plant to be treated in continuous succession [7]. Possible 1
These other compounds may also be fertilizers or micronutrient providers, or other formulations that affect plant growth. Selective herbicides, insecticides, fungicides, bactericides, nematode killers, mollusc killers or There may be mixtures of some of these formulations.

Suitable carriers and auxiliaries can be solid or liquid and include substances commonly used in formulation technology, such as natural or recycled minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Equivalent to.

A preferred method of application of a compound of formula I or an agrochemical composition comprising at least one of said compounds is foliar application. The number of applications and the amount of application depend on the signs of infection by the corresponding pathogen (bacterial species) VC. However, the compound of formula 1 can also be applied through the soil by impregnating the plant area as a liquid preparation or by spreading it over the soil (soil spraying) in the form of a solid, e.g. in the form of granules. It can enter the plant through the roots (l!2 dialysis).

Compounds of formula I can also be applied to seeds (wrinkling) by impregnating the seeds with a liquid formulation containing a compound of formula I or by coating the seeds with a solid formulation. Still other types of applications, such as selective treatment of plant stems or buds, are also possible.

The compound of formula I is also preferably in its trench form, u!
By using the auxiliaries commonly used in the P2 agent industry, it is possible to prepare, for example, rj' emulsion JQ solution, I°υ base,
Directly sprayable or dilutable liquids, dilute emulsions, water agents, powders, powders, and encapsulated agents, for example with polymeric substances.

The method of application, such as spraying, atomization, dusting, dripping or pouring, as well as the type of composition, will depend on the intended audience and environment of use. Advantageous application rates are usually 50 yr or 5 k of active ingredient (a, i,) per hectare;
Preferably 100 fft to 2 to 7H1,i, /
ha, most preferably 2002 to 600f:r,i
, /I+a.

The formulation, i.e. the compound of formula I (active ingredient) and if appropriate! Compositions or formulations containing solid or liquid adjuvants are prepared by mixing the active ingredient intimately with a solvent, a solid carrier and, if appropriate, a bulking agent such as a surface-active compound (surfactant) by known methods. and/or molded by straddle grinding.

Suitable solvents are aromatic hydrocarbons, preferably C8-C12 moieties, such as xylene mixtures or (negative naphthalene: ionaphthal ν ester of dibutyl phthalate or bedioctyl phthalate: cyclohexane: i fcr, 1 aliphatic hydrocarbons such as paraffin; alcohols and glyfurs and their ethers and esters such as ethanol, ethylene glycol monomethyl- or monoemyl ether; ketones such as nclohexanone; N-methyl-2
- strongly polar f, 1 solvents such as pyrrolidone, dimethylsulfoxide or dimethylformamide; 11: and epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

Solid carriers which can be used, for example for dusts and bulk powders, are usually ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. It is also possible to add highly dispersed silicic acid or highly dispersed absorbent poly 1- to improve the physical properties. Suitable granulated absorbent carriers are of the porous type, such as pumice, crushed brick, bentonite over sepiolite, and suitable non-absorbent carriers are materials such as stone or sand. . In addition, a large amount of pre-granulated inorganic matter and A〕←! The material '+tf' codyllomite or pulverized waste material can be used.

In particular, it is advantageous to use adjuvants to aid in the application of the natural (mineral extracted rJ f+'auto)*#''
i Synthetic phospholipids, such as phosnoanadylethanolamine, phosphatide, phosphatidylcholine, sphingomyelin, phosphatidylinisotol, phosphatidyl f + ), phospholecithin, plasmalogen or cardiolipin, -7 These can be obtained, for example, from animal or plant cells, in particular from brain, heart, liver, egg yolk, or soybean.

An example of a useful natural form is a phosphatidylcholine mixture. Examples of synthetic phospholipids are dioct/ylphosphatidylcholine and dipalmitoylphosphatidylcholine.

Depending on the nature of the formulated compounds of formula I, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants with good emulsifying, dispersing and hydrating properties. The term "surfactant" is also understood to include mixtures of surfactants.

Suitable anionic surfactants can be so-called bath soaps or water-soluble synthetic surfactant compounds.

Suitable soaps are alkali metal salts, alkaline earth metal salts, or unsubstituted or substituted ammonium salts of higher fatty acids (CIO to C22), such as Aleic acid or stearic acid, or natural soaps obtained, for example, from coconut oil or tallow. Sodium or potassium salts of fatty acid mixtures. Fatty acid methyllauric salts are also suitable.

However, more frequently so-called synthetic surfactants are used, especially aliphatic sulfonates, aliphatic sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.

The aliphatic sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metals or unsubstituted ammonium salts, and contain C8-C22 alkyl groups, which also include the alkyl portion of acyl groups. , for example the sodium or calcium salts of lignosulfonic acid, dodecyl sulfate or mixtures of fatty alcohol sulfates obtained from natural fatty acids. Also included are the salts of these compounds Kf-j sulfate esters and the sulfonic acid salts of aliphatic alkyl/ethylene oxide adducts. The sulfonated benzimidazole derivative preferably has two sulfonic acid groups and 8 to 22
one fatty acid group containing 5 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 1fcn naphthalenesulfonic acid/formaldehyde condensation product. Corresponding sulfosphates, such as the salts of the phosphoric esters of 4 to 14 mol of ethylene oxide kfitr p-nonylphenol adduct, are also suitable.

The non-ionic surfactant is preferably an aliphatic or aliphatic surfactant.
Cycloaliphatic alcohols, also polyglycol ether/l-dimerates of saturated or unsaturated fatty acids and alkylphenols, the derivatives containing 3 to 30 glycol ether groups, (aliphatic) hydrocarbons 8 to 20 carbon atoms in the moiety and 6 to 18 carbon atoms in the alkyl portion of the alkylphenol.

Suitable nonionic surfactants of Sen are water-soluble adducts of polyethylene-Oquindo and polypropylene Hatake glycol, ethylenediamine Φ polypropylene-glycol and alkyl polypropylene glycols containing 1 to 10 carbon atoms in the alkyl chain. and the adduct contains 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. Their compounds typically contain 1 to 5 ethylene glycol units per propylene glycol unit.

A substitute for nonionic surfactants! (1) is noni) b phenol-polyethoxyethanol, man oil polyglycol ether, polybucubylene/polyethylene oxide adduct, It is octylphenoxypolyethoxyethanol. Fatty acid ester of polyethylene sorbitan and polyoxyethylene rubitan triolate moma. It is an artificial nonionic surfactant.

The cationic surfactant is preferably N-! as IL substituent at least one alkyl group having 8 to 22 carbon atoms and further as lower unsubstituted or...
It is a quaternary ammonium salt containing a rogogenated alkyl group, a benzyl group, or a lower hydroquine alkyl group.

The salt is preferably in the form of a chloride, methyl sulfate or ethyl sulfate, for example steryltrimethylammonium chloride or penzyl di(2-chloride).
IJ ethyl) ethyl ammonium oxide.

In the field of storage protection, auxiliaries that are acceptable for human and animal food are preferred.

Pesticide formulations usually contain a compound of formula 1 (11 to 99%, preferably 117< is α1 to 95%, solid or liquid adjuvant 9
9.9 to 1 yen, special VC99, 8 to 5 chi, and surfactant ('
Including chi.

However, since end users generally use diluted compositions, it is preferable to formulate them as concentrates for commercial products, which may include additives, defoamers, viscosity agents, etc. to achieve special effects. Other auxiliaries such as regulators, binders, tackifiers as well as fertilizers, or other active ingredients may also be included.

Such agrochemical formulations also constitute an object of the present invention.

(Example) The following example explains the present invention in more detail, but is not limited to VC.

Production example 1] In the production water separator, 41.6r of acetone dimethyl acetal (
[1,4 mol) and 1,2-butanediol 56? (α
4 mol) and (j fM Trace M of para-toluenesulfonic acid are stirred in 300 me of 1,1,1-trichloroethane under reflux for 2 hours. After cooling, 5-(2,4-dichlorophenyl)ketopyrimidine 1α1? (0.04 mol) and hyvaradoluenesulfonate 1s, 2r (α08 mol)
was added, and the reaction mixture was stirred at boiling temperature for 24 hours in a water separator. Then 1,2-butanediol 122 (0.08 mol) and 4 drops of sulfuric acid were added to the mixture, and the mixture Stir under reflux overnight. Then another 7.21 (alpha) of 1,2-butanediol and 4 drops of concentrated sulfuric acid are added and the mixture is stirred under reflux overnight followed by another 7.21 (alpha) of 1,2-butanediol ,2
y (add α08 morph and 4 drops of silicic acid and the mixture in a water drainer).

Stir #i, L for an additional 16 hours at Nago temperature. Cooling cage.

The reaction mixture is subsequently extracted three times with f j N caustic Noda solution and 11 times with water. Dry the shell layer over sodium goldate, filter, and concentrate the foam. The crude product was purified by passing it through a flash column packed with glue gel (developing solvent/Stone 71L ether: ethyl vinegar = 3:1).
, isomer A (n401.5528Jα6) and isomer B (n''L5654nα352 and a mixture of isomers (n'o 1.5654 ) 1.5■) 2 are formed.

Production Molecular, in a three-necked flask connected to a Knoxley condenser filled with sieve '100r (0.5 sieves)
5-(2+4-dichlorobenzoyl)pyrimidine a91
i' ([1035 mol), 1,2-bentanediol 5
．． 5r (l10525 mol), paratoluene sulfone installed 4y (α0755 mol) and n-butanol 55m
1 in 300 ml of toluene (bath temperature)
Stir at 160° C. for 20 hours. After the anti-I6 mixture was cooled to room temperature, it was extracted five times with water, and then the organic layer was dried over sodium sulfate, filtered, and washed with 100 ml of water at 100 ml of water. Completely packed with composition biological and glue gel,
Complete Furano Sea Column 1 (1) 1. By separating the isomers (developing solvent/ethyl acetate:petroleum ether-1:6), different 1'L isomer A (n" 1.5522) 11t, isomer B (n" 1.5578) 54th and Isomer mixture A
/ B (njo 1.5551) α61 is reduced. The total yield is 11 f (60% of theory).

Tetrahydrofuran 400% Ethyl ether 200%
- in the mixture of methyl 2,4-dichlorobenzoate 61B? (α5 mol) and 5-bromopyrimidine 57L
2? (α33 mol) is dissolved. Molecular, Sieve 60? After adding .

The reaction mixture was stirred at room temperature for 1/2 hour, then about -
Butyllithium 187.2 mZ (α3 mol) dissolved in 0 hexane as 1.6 mol ha with VC cooling at 120°C
Add dropwise at this temperature.

The reaction mixture is then stirred for 1.5 hours at a temperature ranging from -100° to -160°C. While allowing the temperature to rise to room temperature, stirring is continued until the reaction is complete. Then, 60% of a 10% ammonium chloride solution was added dropwise, and the reaction mixture was diluted with ethyl acetate for 31%.
Extract 7xJ and dry the solution with sodium sulfate and filter.

Then, the filtrate is completely concentrated. Thereafter, the resulting crude product was passed through a 5-year-old flash column of silica gel and then mixed with a developing solvent (petroleum ether:ethyl vinegar (3:1)).
Compound 45 with a melting point of 75-78°C? (Theoretical value of 593
%) is a:I.

) According to a method similar to that of Examples 1.1 and 1.2, the compounds listed in the table below were prepared in different proportions, unless otherwise specified. 〇I 1 U-mer A that can be produced with a diastereoisomer mixture of
, 13 and C are characterized by the data of one cow. The data do not allow any inference regarding the absolute configuration of these isomers.

゛ 1 1ze1 ・ , :q :I: z='z=c''211 □ (, 工 = = え く ＝ 11
・
1: =1 = :! : blasphemy
= = Engineering 2 1:, Ql L, −:,, −−−−,,, −, −−−−−−−−,
−−−−−−−−−, −−−−−−−−−−)□ ゝヱ: :I: +I+1 + +−t +Fl +
p m -1++n +m :l-lower--111-1-
,-----1-----------:1--
−■−−−−−−−−−−−−−−−−−−−−−−−
−−−−−−−−−−−−−−−−−−−−−−− −
---I■-r-'-'------Ki-Ding 1--i ・----u--
--1--1・・-1 2 Examples of formulations of liquid active ingredients represented by formula I (all numbers are Nitt%) a) b) c Tables 1 to 5
Compound of 25% 40% 50% dodenlebenzenesulfone Il [5% 8% loticalcium mol) (ethylene oquinide 307) tetracyclohexanone -15% 20% xylene mixture 65% 25% 20% emulsion stock solution in water By diluting it with the following, an emulsion of the desired mystery 1# can be produced.

a) b) c) d)
Compounds of Tables 1 to 3 80% 10% 5v95≠Ethylene glycol monomethyl 20% --- Ether polyethylene glycol 400 - 70 俤 -
- N-Methyl-2-pyrrolidone - 20% - Epoxidized coconut oil - 1% 5% petroleum distillate (boiling range - 94°C - 160-190°C) These solutions are applied in the form of microdroplets. suitable for

a) b) Cloth 1 to 6 monsters Section 5 10 Chikao
Li 7 9
4% - Highly dispersed silicic acid
1% of the active ingredient of attapulgite-90 is dissolved in methylene chloride and sprayed onto the entire carrier bath, followed by distilling off the solvent under reduced pressure.

a) b) Compound of 4 and 1 to 5 2% 5 multi-tubular dispersed silicic acid 1% 5 moiety
97th cycle - Kaolin
-90 By thoroughly mixing the active ingredient with the carrier, a ready-to-use powder is obtained.

All are heavy duty) Sodium lignosulfonate 5φ 5th section
-Sodium lauryl sulfate 3%
-54 diisobutylnaphthalene sulfur -
Section 6 10ζ6ponj combined sodium tyrene oxide 7 to 8 moles) Dispersion of ribs Keijishun Section 5 10ki 1o-
6 kaolin
62% 27% - Thoroughly mixed with active ingredient separation aid.

By thoroughly grinding the mixture in a suitable mill, a wettable powder is obtained which can be diluted with 1 to form a suspension of desired rotation.

2, & Emulsion stock solution ether (4-5 moles of ethylene oxide) calcium dotesylbenzenesulfonate 5% chlorohexanone 30 thixylene mixture
By diluting this emulsion stock solution by 50% with water, the desired concentration of emulsion can be increased by 4.

Tarri
95 Cheap J Ori /
By mixing the 9296 active ingredient with a carrier and milling the mixture in a suitable mill, a ready-to-use powder is obtained. Sulfone aqueous sodium 2 pieces Carboxymethylcellulose 1
I'm sorry.
87. The active ingredient is mixed with the auxiliary agents, and the mixture is subsequently ground and moistened with water.
The mixture is extruded and dried in a stream of air.

polyethylene glycol 200
5% power orin
94% finely ground active ingredient in a mixer.

Apply uniformly to kaolin moistened with polyethylene glycol ◇ This method gives non-dusting coated granules.

Ethylene glycol 10 Tirigutsulfonate sodium 10 Ticarboxymethylcellulose 1 Tyro 7% formaldehyde aqueous solution α2
%75 water-based emulsion type 1
8g/licorn oil water
32%: UI The thus ground active ingredient is thoroughly mixed with the auxiliary ingredients and a suspendable concentrate is obtained which can be diluted with water to obtain a suspension of the desired formulation.

Effect on the wheat plant body, 6 days later, a spray solution (active ingredient: 102 cm) prepared from the water use agent of the test compound was sprayed.
After 24 hours, the treated plants are infected with a suspension of fungal diaspores. The relative humidity of this plant is 95-10
0%, cultured at about 20℃ for 48 hours and then heated to about 22℃ for the first time.
Leave at ℃. On the 12th day after infection, evaluate the spread of mildew.
Section 6) will process it.

After 48 hours, the treated +It' proboscis is infected with a suspension of bacterial spores. The plants A, 4- are cultured for 48 hours at about 20° C. under a relative humidity of 95-100° C. and then left to warm at about 22° C. for 14 hours.

On the 12th day after infection, the diseased warts spread lff'j
“Mh.

The compounds in the table showed excellent resistance against Gucinia bacteria.

71 Teruensis that infected orchids without treatment was reduced to 1 by Gushua.
Section 00 was attacked. Compound I proboscis 1.3a:t3b:
t4a: 1.4a, b: 1.5; 1.7; +; 1.7b
:i, 7a, b: t6a: 1.6b: 1.
6a, b: 1.22: 1.24: +, 54:
1.36: t37; 1.40; 1.42
; 1.44:1.45:1.54;1.58:2.2
;2.19a,b;2.20;2.7;2.9;212
:2.14:2.15:2.23a, b:2.24a,
b:2.25a, b:56a, b:i8a, b:A10
a, b; 511a, b; A12a, b shows the effects of the test compound on groundnut plants with a residual protective effect of 10 to 15 L: r, which suppressed the attack of gucinia to 0 to 5 fleas. Spray mixtures prepared from wettable powders (the compound Q
, 006), and 48 hours later, the bacteria were infected with a conidial suspension of the bacteria. Approximately 2 plants infected with fungi
Incubate for 72 hours at 1°C under high humidity, then leave in a greenhouse until typical spots appear on the leaves. After 12 days of infection, evaluate bactericidal activity by the number and size of spots. do.

The attack of Cercospora on peanut plants treated with the compounds of Table 1 compared to untreated infected control plants (number and size of spots = i00%) was significantly reduced. I regret it. Thus for example the compound 1.3 a', 1
．． 4 b: 1.4 a r b ;1.6a:
1.6b:1.6a,b:1.34:1.37:1
．． 44:1.45;i,54;2.7:2.9:2.1
? a,b:2.2OS2.23a,b;i6a,b:A
8a, b; 3.11a, b;
A spray mixture prepared from the test compound formulated as a wettable powder (active ingredient α0
Spray 02ch). After 6 to 4 hours, the treated plants are sprinkled with conidia of the fungus. The infected barley plants are then placed in a greenhouse at approximately 22°C. The degree of infection is assessed after 10 days.

b) A spray solution prepared from a hydrating powder of the active ingredient (active ingredient [LO
Pour O2%. Be careful not to let the spray solution touch any parts of the plant above the soil.

After 48 hours, the treated plants were sprinkled with fungal conidia.◇The infected barley plants were kept in a greenhouse at approximately 22°C and
Bacterial spread is assessed after day 0.

The compounds in the table show good action against Erysiphe.

On the other hand, untreated and infected S. 1sho plants show 100 Eri 7-hue infections. Thus for example compound 1.1;
13a: 1.3b; 1.3a, b: 1.4
a; 1.4b; 1.4a, b; 1.5 voice 1.6a: 1.
6b; 1.6a, b: 1.7a: 1.7b: 1.7a,
b:1.22:1.24;1.34:t37:1.40
:1.42:1.44:1.45;1.54:1.58
;2.2:2.7;2.9:2.12:2.14:2.
15:2-19a, b; 2.19a; 2.23a, b;
2.24a, b; 2.25a, b; 3.6a, b; 3h
8a,b:3.9a,bHAloa,b;! L11a,
b: A12a,b reduces fungal infection on barley to 0-5%.

Inaqual (Venturia 1naequal)
i) with a length of 10 to 20. A spray solution prepared from a hydrating agent of the active ingredient (active ingredient α06) is sprayed onto the apple seedlings, which have a new coat. To the treated plants,
After 24 hours, the entire plant was sprayed with a conidial suspension of the fungus.Next, the plants were cultured for 5 days at a relative humidity of 90 to 100, and further 1
1 of 0 infections kept in a greenhouse at 20 to 24°C for 0 days
Evaluate the extent of corruption spread after 5 days.

The compounds of Tables 1 and 2, especially compounds 1.6 and 1.12, clearly reduce infection. - force, the untreated infected cloth is stained by Penturia at 100'A m<0, thus e.g. compounds 1.3a:1.34:j, 40:t
42;2.1? a, b: 2.25a, b; 2.24a,
b:2.25a, b:5.6a, b:i8a, b:A9
a, b: 3.10a, b: 3.11a, b; 5.12
A and b suppress the attack of bacteria on apples to 5 or 5 inches.

Residual Protection Fava bean plants approximately 10 mouths high are sprayed with a spray solution prepared from a wettable powder of the active ingredient (active ingredient α02). The plants are infected after 48 hours with a conidial suspension of the fungus. The degree of fungal infection is evaluated after culturing the infected plants for 5 days at 21° C. and relative humidity of 95 to 100° C. The compounds in the table inhibit bacterial infection very strongly. Thus, for example, compounds 1.3a; t3b: 1.3a, b: 1.4a
:i, 4b; t4a, b: 1.6a; 1.6b; 1.6
a, b; 1.7a; 1.7b; 1.7a, b
and 2.2:2. I2; 2.24a, b: 2-25a,
b: &6a, b:3h11a, b reduces bacterial attack to mouth or 5.

After growing for two weeks, the rice crop was treated with an active ingredient irrigation agent.
I4 Spray with depleted spray liquid (active ingredient 0.002%). After 48 hours, the treated plants are infected with a suspension of fungal conidia. Relative humidity 95-100%, 24
Incubate at ℃ for 5 days and evaluate bacterial attack.

b) A spray prepared from an irrigation agent of the infarction test compound (1006 g of active ingredient per soil volume).

Pour into a two-week-old rice plant in a ceramic pot, usually used for flowers.Then fill with clean water until the lowest stem of the rice plant stands in the water. [;I
After 1, the treated product was dyed with a suspension of conidia of the fungus at 95-100 degrees of relative humidity, about 24°C.
The infected plants were cultured for 5 days and the fungal attack was fully evaluated. The compounds in the coating show excellent effects against the B. pyricularia ◇ On the other hand, control plants infected without treatment are attacked by the Phyllicularia 100%. Thus, compounds 1.3a, 1ib; 1.4; and 1.6a inhibit bacterial attack from the mouth to the 5 hairs.

Lani (几hizoctonia 5olani) (
Spray solution prepared from the formulation of the test compound (active ingredient α0
06ch) is poured onto 12-day-old rice plants without contaminating the plant parts above the soil. to infect the treated plants.

A suspension of Rhizoctonia solani mycelia and membranes was applied to the surface of the soil. Climate: 227℃ (daytime) and 25℃ (night).

Incubation for 6 days at 100% relative humidity (humidity box) 1. After that, the surface attack on the first leaf sheath, the fifth leaf and the stem is evaluated.

b) Protective local foliar application Twelve-day-old rice plants are sprayed with a spray solution prepared from the formulation of the test compound. Infect with fluid. 27°C (daytime) and 25°C (nighttime) in the climatic chamber.

After 6 days of cultivation at 100% relative humidity (humidity box), fungal attack on leaf sheaths, single leaves and stems is evaluated.

The compounds listed in the table showed excellent activity in inhibiting the total attack of Diphthonia.On the other hand, the attack on control plants infected without treatment was 100 mm.

For example (-1' compound 1.5 a; 1.3
+); 14 a; 1.4a, b: 1.6a; 1.
6b: L6a, b; 1.7a: t7b: 1.7a, b:
and 22, the bacterial attack %' [is suppressed to 0 to 5%.

Claims (19)

[Claims] (1) General formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, A represents a phenyl group, phenoxyphenyl group, phenylthiophenyl group, biphenyl group, or naphthyl group, and Ra, Rb and Rc each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, or Represents a halogenoalkoxy group having 1 to 4 carbon atoms, and X is the following bridging group: ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, or a CH_2O- (alkyl group having 1 to 4 carbon atoms) group, R_4 is a hydrogen atom, represents an alkyl group having 1 to 4 carbon atoms or a CH_2OH group, and R_3, R_5 and R_6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] Compound or its acid addition salt. (2) In formula I, A, Ra, Rb, Rc, R_1
and R_2 have the above meanings, R_6 represents a hydrogen atom, and R_3, R_4 and R_5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, according to claim 1 compound. (3) In formula I, A represents a phenyl group, phenoxyphenyl group or phenylthiophenyl group, Ra,
Rb and Rc each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a halogenoalkyl group having 1 to 2 carbon atoms, or a halogenoalkyl group having 1 to 2 carbon atoms; 2 represents a halogenoalkoxy group, nitro group, or cyano group, and X represents the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are independent of each other. hydrogen atom,
C1-C4 alkyl group, C1-C2 halogenoalkyl group or CH_
2O- (alkyl group having 1 to 2 carbon atoms) group, R_4 represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms or a CH_2OH group, and R_3,
The compound according to claim 1, wherein R_5 and R_6 each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. (4) In formula I, A represents a phenyl group, phenoxyphenyl group or phenylthiophenyl group, Ra,
Rb and Rc each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a halogenoalkyl group having 1 to 2 carbon atoms, or a halogenoalkyl group having 1 to 2 carbon atoms; 2 represents a halogenoalkoxy group, nitro group, or cyano group, and X represents the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are independent of each other. hydrogen atom,
C1-C4 alkyl group, C1-C2 halogenoalkyl group or CH_
2O- (alkyl group having 1 to 2 carbon atoms) group, and R_3, R_4 and R_5 each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms) The second claim representing
Compounds described in Section. (5) In formula I, A represents a phenyl group or a phenoxyphenyl group, and Ra, Rb and Rc are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 2 carbon atoms, or a C 1 to 2 alkyl group. 2 represents an alkoxy group, a halogenoalkoxy group having 1 to 2 carbon atoms, a nitro group, or a cyano group, and R_1 and R_2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a C
Represents H_2OCH_3 group, and R_4 is a hydrogen atom,
represents a methyl group or a CH_2OH group, and R_3,
4. The compound according to claim 3, wherein R_5 and R_6 independently represent a hydrogen atom or a methyl group. (6) In formula I, A represents a phenyl group or a phenoxyphenyl group, Ra, Rb and Rc independently of each other represent a chlorine atom and/or a methyl group in the 2- and/or 4-position, and A patent representing a bridging group represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 3 carbon atoms or a CH_2OCH_3 group, and R_2 represents a hydrogen atom) A compound according to claim 5. (7) In formula I, A represents a phenyl group or a phenoxyphenyl group, Ra, Rb and Rc independently of each other represent a chlorine atom or a methyl group in the 2- and/or 4-position, and X is A patent claim representing a bridging group represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. A compound according to scope item 4. (8) In formula I, A combines with Ra, Rb and Rc to form a 2,4-dichlorophenyl group, 2-fluoro-4-
Chlorophenyl group, 2-cyano-4-chlorophenyl group, 2-methyl-4-chlorophenyl group, p-chlorophenoxy group, 2-methyl-4-(p-chlorophenoxy)
or 2-chloro-4-(p-chlorophenoxy) group, and R_1 to R_6 represent a hydrogen atom or a C1 to C4 alkyl group, and R_1 to R
The compound according to claim 1, in which the total number of carbon atoms in _6 is not 5 or more. (9) The compound of formula I is 5-[2-(2',4'-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl]pyrimidine, 5-[2-(2',4' -dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl)pyrimidine 5-[2-(2',4'-dichlorophenyl)-4-methoxymethyl-1,3-dioxolan-2-yl]pyrimidine 5-[2-(2',4'-dichlorophenyl)-4,5
-dimethyl-1,3-dioxolan-2-yl]pyrimidine, 5-[2-(2',4'-dichlorophenyl)-5,5
-dimethyl-1,3-dioxan-2-yl]pyrimidine, an isomer or a mixture of isomers of the compound according to claim 1. (10) The compound of formula I is 5-[2-(2',4'-dichlorophenyl)-4,6
-dimethyl-1,3-dioxan-2-yl]pyrimidine, 5-[2-(2',4'-dichlorophenyl)-4,5
, 6-trimethyl-1,3-dioxan-2-yl]pyrimidine, 5-[2-(2',4'-dichlorophenyl)-5-ethyl-5-methyl-1,3-dioxan-2-yl] Pyrimidine, 5-[2-(2',4'-dichlorophenyl)-4-methyl-1,3-dioxolan-2-yl]pyrimidine, 5-[2-(2'-cyano-4'-chlorophenyl)-
5-ethyl-5-methyl-1,3-dioxolane-2-
yl]pyrimidine, 5-[2-(2',4'-dichlorophenyl)-4-ethyl-1,3-dioxan-2-yl]pyrimidine, 5-[2-(2'-chloro-4'-p -chlorophenoxyphenyl)-4-ethyl-1,3-dioxane-2-
2. An isomer or a mixture of isomers of the compound according to claim 1, which is pyrimidine. (11) A) The following formula II: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, A, Ra, Rb and Rc represent the meanings defined in the following formula I] In an active solvent, ketalize with a diol represented by the following formula III: HO-X-OH (III) [wherein X represents the meaning defined in the following formula I] or B) the following formula IV: ▲Math. , chemical formulas, tables, etc. ▼ (IV) [In the formula, ALK represents an alkyl group having 1 to 4 carbon atoms] A ketone represented by the following formula is reacted with a diol of formula III in an inert solvent, and the following formula is obtained. V: ▲Mathematical formulas, chemical formulas, tables, etc.▼(V) to form a compound of formula V, followed by reaction with a compound of formula V in an inert solvent without isolating the compound of formula V from the reaction mixture. , consisting of ketalizing the ketone of formula III, the following formula I
: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, A represents a phenyl group, phenoxyphenyl group, phenylthiophenyl group, biphenyl group, or naphthyl group, and Ra, Rb, and Rc each independently , a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, or a halogenoalkyl group having 1 to 4 carbon atoms. represents a halogenoalkoxy group, and X is the following bridging group: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are independently hydrogen atoms , represents an alkyl group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, or a CH_2O- (alkyl group having 1 to 4 carbon atoms) group, and R_4 is a hydrogen atom, and R_4 is a hydrogen atom, and R_4 is a hydrogen atom, and , and R_3, R_5 and R_6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. (12) The method according to claim 11, which comprises adding an acid during the ketalization reaction. (13) As an active ingredient, the following formula I: ▲Mathematical formula, chemical formula, table, etc.▼(I) [In the formula, A represents a phenyl group, phenoxyphenyl group, phenylthiophenyl group, biphenyl group, or naphthyl group, Ra, Rb, and Rc each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a 1 to 4 carbon atom. represents a halogenoalkyl group or a halogenoalkoxy group having 1 to 4 carbon atoms, and X is the following bridging group: ▲There are mathematical formulas, chemical formulas, tables, etc.▼or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, or a CH_2O- (alkyl group having 1 to 4 carbon atoms) group, and R_4 represents a hydrogen atom, a C1-C4 alkyl group or a CH_2OH group, and R_3, R_5 and R_6 each independently represent a hydrogen atom or a C1-C4 alkyl group) ] A microbicidal composition for controlling microorganisms or for protecting plants from attack by the microorganisms, comprising at least one of the compounds represented by the following. (14) The composition according to claim 13, which contains at least one compound of formula I according to claim 2, 4, 7, or 9 as an active ingredient. (15) Claims 3, 5, 6 as active ingredients,
14. A composition according to claim 13, comprising at least one compound of formula I according to claim 8 or 10. (16) General formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, A represents a phenyl group, phenoxyphenyl group, phenylthiophenyl group, biphenyl group or naphthyl group, and Ra, Rb and Rc each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, or a carbon atom. represents a halogenoalkoxy group of numbers 1 to 4, and X
is the following crosslinking group: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 are independently hydrogen atoms, alkyl having 1 to 4 carbon atoms, R_4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a CH_2OH group, and R_3, R_5 and R_6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A method of controlling pathogenic microorganisms or protecting cultivated plants from attack by said microorganisms. (17) Formula according to claim 2, 4, 7 or 9
17. A method according to claim 16, which comprises applying a compound of I. (18) A method according to claim 17, which comprises applying a compound of formula I according to claim 3, 5, 6, 8 or 10. (19) General formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, A represents a phenyl group, phenoxyphenyl group, phenylthiophenyl group, biphenyl group or naphthyl group, Ra, Rb and Rc each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, or a carbon atom. Represents a halogenoalkoxy group having 1 to 4 atoms, and X is the following bridging group: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are mutually independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, or a CH_2O- (alkyl group having 1 to 4 carbon atoms) group, and R_4 is a hydrogen atom, a carbon represents an alkyl group having 1 to 4 atoms or a CH_2OH group, and R_3, R_5 and R_6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] A method for producing an agrochemical composition, which comprises homogeneously mixing at least one of the above with appropriate solid or liquid auxiliaries and surfactants.