JPH03871B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel family of substituted imidazole and triazole compounds. More particularly, this invention relates to a novel class of substituted imidazole and triazole compounds useful as mold control agents. The use of fungicides has affected plants and resulted in economic losses, and the development of new compounds as fungicides is therefore ongoing. It is desired to develop a fungicide with a wide range of efficacy that is effective against all types of fungi that damage plants and crops.Therefore, the development of new compounds as fungicides is It continues to this day without any decline. Among the considerable variety and types of compounds that have been developed for use as mold control agents are the various types of imidazole and triazole compounds. For example, European Patent Application No. 29355 describes azole compounds that are outside the scope of the present invention. European Patent Application No. 92158 teaches a family of triazolidine compounds that are described for use as mold control agents. European Patent Application No. 61789 and European Patent Application No. 61789, which are substantially identical
No. 61794 teaches azole-substituted mold control agents. British Patent Application No. 2098607 describes a group of arylphenyl ether derivatives and antifungal and/or anticonvulsant and anxiolytic pharmaceutical agents useful in the control of plant harmful microorganisms. British Patent No. 3575999 describes a family of imidazole derivatives with fungicidal activity. Other substituted triazole compounds have been disclosed in the prior art as useful as antimicrobial agents. for example,
US Pat. Nos. 4,079,062 and 4,402,963 describe triazole-substituted compounds that have utility in this application. A rather unique problem of the compounds known in the prior art is that, in addition to having fungicidal properties, they also exhibit plant growth regulation. In many cases, such properties are desirable properties. However, fungicides have as their purpose the control of plants or crops by eliminating attack from fungi. Compounds that are effective as mold control agents and are also effective as plant growth regulators inhibit plant growth. It is easy to see that in such cases, the treatment will not make the disease any better, if not worse than the disease. There is a clear need in agrochemical technology for a new class of fungicidal agents that are effective against a wide variety of fungi. Particularly desirable are compounds that not only attack a wide range of fungi, but also do not exhibit any deleterious effects on plant growth. The present invention relates to a new class of imidazole and triazole substituted compounds that have a greater spectrum of fungal activity than prior art imidazole and triazole substituted compounds. Furthermore, the compounds according to the invention are characterized by the absence of plant growth regulating activity. Plants and crops that are controlled against fungi by the compounds of the invention therefore do not suffer from any harmful effects due to the fungicidal presence of these compounds. The compound according to the invention has the following formula: [In the formula, Z and Z ¹ are the same or different, oxygen,
Sulfur, SO or SO ₂ ; with Z and Z ¹
are not simultaneously oxygen; Y is nitrogen or CH; R is linear or branched _C2 - _C12 alkylene; ^R1 is hydrogen, _C1 - _C4 alkyl or phenyl; R ² is phenyl, phenoxy, phenylthio, phenoxy with halo, _C1 - _C4 alkyl, nitro, cyano or trihalomethyl as substituent, or halo, C1- _C4 as substituent
phenyl having _C4 alkyl, _C1 - _C4 alkoxy, trihalomethyl or dihalomethoxy]. The present invention further relates to a method for controlling mold by applying a mold-controlling effective amount of said compound. The invention further features a composition containing the compound together with a pharmaceutical carrier. This composition is effective as a mold control agent. Another aspect of the invention is a method of producing the compounds of the invention. In this method, the expression An azole ketone compound of the formula HZ-R-Z 1 H (wherein Y, R ¹ and R ² have the meanings given above for the compound produced in this reaction) is prepared by formula HZ-R-Z ¹ H (wherein R, Z and Z ¹ are Z and with the meaning given above for the compounds of the invention), with the restriction other than that Z ¹ cannot be SO or SO ₂ . The present invention is based on the formula [In the formula, Z and Z ¹ are the same or different, oxygen,
sulfur, _SO2 ; provided that Z and ^Z1 are not simultaneously oxygen; Y is nitrogen or CH; R is linear or branched _C2 - _C12 alkylene;
R ¹ is hydrogen, C ₁ -C ₄ alkyl or phenyl; R ² is phenyl, phenoxy, phenylthio,
Substituents include halo, _C1 - _C4 alkyl, nitro,
phenoxy with cyano or trihalomethyl, or halo, _C1 - _C4 alkyl as substituents,
phenyl with _C1 - _C4 alkoxy, trihalomethyl or dihalomethoxy]. More preferably, the compounds of the invention are such that Y is nitrogen; Z is oxygen; Z ¹ is sulfur or SO ₂
R is _C2 - _C5 linear or branched alkylene; ^R1 is hydrogen, methyl or phenyl; and ^R2 is phenyl, phenoxy,
Phenylthio, phenoxy having fluorine, chlorine, bromine, methyl, trifluoromethyl as a substituent, or fluorine, chlorine, bromine as a substituent,
A compound of the formula phenyl with methyl, methoxy, trifluoromethyl or dichloromethoxy. Most preferred compounds of the invention are those in which Y is nitrogen; Z is oxygen; Z ¹ is sulfur or SO ₂ ; R is C ₂ -alkylene; R ¹ is hydrogen; and R ² is phenyl , phenoxy, phenylthio, phenyl substituted with bromine, or phenoxy substituted with bromine. Compounds of the invention, i.e. compounds, can be prepared by the following method: Formula A compound having the formula HZ-R- ^{Z 1} H () (wherein R, Z and ^{Z 1 are} Z and Z ² are SO or with the meanings and limitations given above for the compound except that it cannot be SO ₂ ). In this method, at least 1 mole, preferably an excess of the compound is reacted with 1 mole of the compound. The reaction is usually carried out in the presence of an acid catalyst. The acid catalyst used in this reaction is a Lewis acid. Among the Lewis acids included within the meaning of this invention are methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, aluminum chloride, aene chloride, tin chloride, and the like. Among these, p-toluenesulfonic acid is most preferred. Furthermore, the reaction is preferably carried out in a solvent mixture, the solvent being an inert organic liquid. Among the suitable inert organic solvents within the meaning of this invention are hexane, cyclohexane, heptane, benzene,
There are hydrocarbons such as toluene, xylene, etc.
Other suitable solvents include lower alcohols, namely 1-butanol. Furthermore, G-,
Chlorinated hydrocarbons such as tri- and tetra-chloromethane, dichloroethane, trichloroethane, tetrachloroethane, etc. can also be used. Furthermore, ethers such as tetrahydrofuran and 1,4-dioxane are other solvents within the contemplation of this invention. Among these solvents, a solvent mixture of toluene and a lower alcohol, preferably 1-butanol, is particularly suitable. This reaction, which takes place over a period of 1 to 4 days, usually
It is carried out at the reflux temperature of the solvent used. Azeotropic removal of water takes place during the reaction period. The final isolation of the product of this reaction, the compound, is carried out by conventional methods by precipitated salts of the compound. Alternatively, the product can also be isolated from the mother liquor of the reaction mixture. It should be noted that the products of this reaction do not include all of the compounds of the invention. In particular, the meaning of Z and Z ¹ is restricted to oxygen, sulfur or NR ³ . At least one of Z and Z ¹ is sulfoxide or sulfone (respectively
Further processing is necessary to obtain the compounds of the invention which are SO and SO ₂ ). In a preferred embodiment of producing the sulfoxide, the reaction product produced according to the method described above is reacted with an oxidizing agent. Oxidizing agents within the scope of this process include periodate salts, such as sodium periodate, potassium periodate, etc.; peroxides, such as hydrogen peroxide, sodium peroxide, etc.; peroxyacids, such as peroxybenzoate. acids and meta-chloroperoxybenzoic acid. Among these oxidizing agents, m-chloroperoxybenzoic acid is particularly preferred. In this reaction to form the sulfoxide compounds of the compounds of the invention, the product formed in the first step, i.e. the compound in which Z and Z ¹ are not SO or SO ₂ , is combined with one equivalent of the above-mentioned oxidizing agent, preferably m- React with chloroperoxybenzoic acid. The time and temperature of this reaction are 1 to 24 hours and 0°C to room temperature, respectively. The reaction is carried out in the presence of a solvent, such as a chlorinated hydrocarbon. The mode of producing sulfone, i.e. Z or
In embodiments producing products in which at least one of Z ¹ is SO ₂ , the same reaction is carried out except that at least 2 equivalents, and preferably more, of the oxidizing agent, preferably m-chloroperoxybenzoic acid, are used. As in the case of sulfoxide production, this step is carried out in the presence of a solvent, again with chlorinated hydrocarbons being preferred. Among the chlorinated hydrocarbon solvents that can be used in the present invention, chloroform or dichloromethane are particularly preferred. Unlike the case with sulfoxides, the reaction to form sulfones is carried out at elevated temperatures, preferably at the reflux temperature of the solvent. The reaction is also run for 1 to 24 hours. More preferably, the reaction to produce the sulfone takes 16 to 20 hours. In a preferred embodiment of the process of the invention, the reactants are Y is nitrogen; Z is oxygen; Z ¹ is sulfur;
R is linear or branched _C2 - _C5 alkylene; ^R1 is hydrogen, methyl or phenyl; and ^R2 is phenyl, phenylthio, phenyl or as a substituent fluorine, chlorine, bromine, and compounds that are phenoxy with methyl, methoxy, trifluoromethyl or trichloromethyl. In a further preferred embodiment of the process of the invention, the reactants are such that Y is nitrogen; Z is oxygen; Z ¹ is sulfur; R is C ₂ -alkylene; R ¹ is hydrogen; and R ² is phenyl, phenylthio,
Phenoxy, a compound that is phenyl substituted with bromine or phenoxy substituted with bromine, and has the structural formula. The compounds of the present invention have particular use as fungicides for controlling fungal growth in plants and crops. It is of particular value that the compounds of the invention are effective against phytotoxic fungi that have penetrated systemically or deeply into plant tissue. Among the diseases effectively controlled by the compounds of the invention are barley (Erysiphe graminis) and cucumber (Erysiphe graminis).
Powdery mildew and bean rust (Uromyces cichoracearum)
There are rust diseases such as Certain compounds of the invention have also been shown to be effective against other fungi that cause plant diseases, including, for example, the following fungi: Alternaria solani, Cercospora arachidicola. (Cercospora arachidicola),
Phytophthora infestans, Sclerotinia sclerotiorum, Sclerotium rolfutsii
rolfsii), Fusarium oxysporum, Helminthosporium maydis and Piricularia oryzae.
oryzae). In order to effectively use the compounds of the invention in their primary use as mold control agents, these compounds may be mixed alone or as an inert carrier and/or as an additive to form mold control active compositions. Can be applied. In one embodiment of such compositions, the compound is combined with a solid inert carrier. Among the inert carriers within the contemplation of this invention are mineral silicates such as mica, talc, pyrophyllite and clay. Other solid carriers within the contemplation of this invention are vermiculite, charcoal and corn cob. The solid compositions prepared by combining the active compounds with the inert carriers mentioned above are applied by methods well known in the art, such as spraying, root application, soil formulation and seed treatment. Another preferred embodiment of the composition of the invention uses a liquid composition comprising the compound and a liquid inert carrier. In this embodiment, the liquid carrier can be a solvent or suspending agent for the active compound. It is emphasized that the carrier itself is inert in terms of imparting fungicidal activity. Among the liquid carriers within the contemplation of this invention are water, alkanols and aromatic solvents such as substituted and unsubstituted phenols, benzene, kerosene, toluene and xylene. Another preferred embodiment of the liquid composition of the present invention is an emulsion formed by dissolving the compound in a suitable organic solvent and then adding water to this solution. It goes without saying that suitable emulsifiers, anionic agents, surfactants which can be nonionic or cationic are added to the formation of the emulsion. In yet another embodiment of the liquid composition of the invention, the compound is combined with water to form a dispersion in the absence of an organic solvent. In this case also surface-active dispersants are used for the preparation of the suspension. Surfactants effective in preparing compositions containing liquid phases are known in the art. For example, U.S. Pat.
No. 2,547,734 provides detailed examples of such auxiliaries for use in the emulsions and dispersions of the present invention. Another liquid composition of the invention prepares solutions for aerosol application of the compounds of the invention. These compositions are prepared by dissolving the compound directly into a liquid aerosol solvent at elevated pressure. This aerosol method involves discharging an aerosol solution into the atmosphere at a pressure where the carrier is a gas. Alternatively, the aerosol solution is prepared by first dissolving the compound in a low volatility solvent, then mixing the solution thus produced with a highly volatile liquid aerosol carrier and then processing as described above. . According to another embodiment of the composition of the invention, a two-phase composition is provided. In this case, the compound is first adsorbed onto the surface of an inert solid support. As mentioned above, various mineral silicates are particularly suitable for this composition. These inert silicates are then treated with a suitable non-solvent medium in the presence of a dispersant,
Usually dispersed in water. The following examples are intended to illustrate the invention without limiting its scope. The invention is not, and should not be considered to be, limited in presentation or content to these examples. Example 1 1-[(2-[1,1'-biphenyl]-4-yl-
1,3-oxathiolan-2-yl)methyl]
-1H-1,2,4-triazole (compound 1) 175 ml anhydrous toluene and 70 ml 1-butanol
1-[1,1'-biphenyl]-4-yl-2-
A slurry of 13.1 g of (1H-1,2,4-triazol-1-yl)ethanone was added with 7.8 g of 2-mercaptoethanol and 12.3 g of p-toluenesulfonic acid.
Add g while stirring. The resulting thickened slurry is refluxed for 72 hours using a Dean-Stark trap. At this point, no more water is collected. After the reaction mixture is allowed to cool, the solids are filtered off, slurried in dichloromethane, and then shaken once with 10% aqueous sodium hydroxide and then once with water. dry the organic phase;
Evaporation yields an oil that solidifies under high vacuum and pressure. This solid is triturated with petroleum ether and the product of this reaction, 1-[(2-[1,1
6.7 g of -biphenyl]-4-yl-1,3-oxathiolan-2-yl)methyl]-1H-1,2,4-triazole are obtained. The melting point of this compound is 85
~90℃. Example 2 1-[(2-[1,1'-biphenyl]-4-yl-
1,3-oxathiolan-2-yl)methyl]
-1H-1,2,4-triazole S,S-dioxide (compound 2) A solution of 5.1 g of 80-85% m-chloroperoxybenzoic acid in 80 ml of dichloromethane was added to 40 ml of dichloromethane.
ml of 1-[(2-[1,1'-biphenyl]-4-yl-1,3-oxathiolan-2-yl)methyl]-1H-1,2,4-triazole at room temperature. Add it dropwise. After the addition is complete, the reaction mixture is refluxed for 24 hours. The volume is then reduced by half and the precipitate formed is filtered off. The filtrate was diluted three times with 5% aqueous sodium bicarbonate and once with water.
Washed twice, dried and evaporated to 1-
[(2-[1,1′-biphenyl]-4-yl-1,3
-oxathiolan-2-yl)methyl]-1H-
3.1 g of 1,2,4-triazole S,S-dioxide product are obtained; melting point: 145-155°C. Example 3 1-[(2-[1,1'-biphenyl]-4-yl-
1,3-oxathiolan-2-yl)methyl]
-1H-1,2,4-triazole S-oxide (compound 3) A solution of 6.1 g of 80-85% m-chloroperoxybenzoic acid in 60 ml of dichloromethane was added to 45 ml of dichloromethane.
0 to a solution of 9.7 g of 1-[(2-[1,1'-biphenyl]-4-yl-1,3-oxathiolan-2-yl)methyl]-1H-1,2,4-triazole in ml of Add dropwise at °C. After the addition is complete, the reaction mixture is allowed to warm up to room temperature and then stirred overnight. The solution is washed three times with 5% aqueous sodium bicarbonate solution and once with water, dried and evaporated to give a white solid. Thoroughly mix this solid with ether, 1-[(2-
[1,1'-biphenyl]-4-yl-1,3-oxathiolan-2-yl)methyl]-1H-1,2,
8.5 g of 4-triazole S-oxide are obtained; melting point: 149-153°C. Example 4 Preparation of Compounds 4 to 13 According to the methods described in Examples 1 to 3, further compounds within the scope of the present invention are prepared. These compounds, compounds 4-13, are tabulated in Table 1 below. Table 1 also includes compounds 1-3 obtained according to the methods of Examples 1-3, respectively.

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Table Further compounds are prepared according to the method of Examples 1-3. These compounds are illustrated by the structure of the compound, where each group has the meaning shown in Table 1(A) below.

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[Table] Example 5 Powdery Mildew Fungus
(systemic root uptake) The compound of the present invention is used for the protection or control of powdery mildew of barley (Erysiphe graminis) and powdery mildew of cucumber (Erysiphe cichoracearum) by systemic root uptake. They were tested to evaluate their effectiveness. Several barley plants ('Herta' variety) and cucumbers ('Marketmore 70')
The seeds were planted in pots and allowed to grow for 6 and 10 days, respectively. Once this stage of growth is reached, 45 ml of an emulsion of a compound of the invention is added to each pot. This 45 ml volume saturates the soil by penetrating into the saucer below the pot without concomitant significant loss of emulsion. Emulsions are made by dissolving the pure compound in 5 to 7 ml of acetone or other suitable solvent and adding an emulsifier [i.e. Triton (trade name) x -100].
Add 1-2 drops and then water to release the active compound.
Manufactured by producing a corresponding concentration of parts per million (ppm). Additionally, an equal number of pots planted with the same barley and cucumber plants are left untreated. These pots are used as controls. Twenty-four hours after treatment, both barley and cucumber plants are inoculated with the powdery mildew pathogen by sprinkling leaves from infected barley or cucumber plants onto treated and untreated plants, respectively. After 6 days, disease control is evaluated on a rating scale of 0-6. A rating of 0 indicates when no disease was proven, and a rating of 6 is given for severe disease. Percent control is calculated by comparing ratings of treated and untreated plants. The results of these tests are summarized in Table 2.

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[Table] Example 6 Control of barley powdery mildew by leaf application 6 to 10 "rakers" per pot
(Lerker) 7-10 day old plants of seed barley are sprayed with a compound of the invention at the specified application rate. The compounds are applied by first dissolving them in acetone and then suspending this in water using a surfactant or suspending agent. The suspension is then sprayed into the pot two or three times. A significant number of pots used as controls are not treated. After the sprayed pots have dried, these and control pots are placed in a greenhouse maintained at 21°C.
All pots are inoculated with spores of powdery mildew pathogenic fungus by distribution from leaves from plants already infected with powdery mildew. On the fifth day after inoculation, the plants are rated on a scale of 0 to 6 with 0 and 6 indicating no disease and severe disease, respectively. Percent control is calculated by comparing the treated and untreated control scores. The results of these tests are summarized in Table 3.

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[Table] Example 7 Control of rice leaf blight (Blast disease) by leaf treatment Four to six 3- to 4-week-old Bellemont rice plants per pot were treated with the compound of the present invention at the concentrations shown in the following table. Spray. The spray liquid is prepared according to the method described in Example 6. Both sprayed and unsprayed pots of the plants are inoculated with Pyricularia oryzae spores. 1ml
Prepare the inoculum to contain 20,000 to 30,000 spores per plant and apply this inoculum to the plants along with 1 to 2 drops of Tween 20 (trade name) to ensure proper wetting of the plant leaves. Spray on top. Plants were grown in a humidity-controlled room maintained at 21 °C for 24 hours.
Incubate for ~48 hours to allow infection. Plants are moved to a greenhouse for 5-7 days to allow the disease to develop. The disease is evident by dead areas on the leaves. Percent disease control was calculated by counting the number of lesions if the infection was mild or as assessed by the 0-6 rating scale system as defined in the example above. The results of this test are tabulated in Table 4.

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[Table] Example 8 Control of bean rust fungus (Ruet Fungus) Spore suspension was applied to 7-day-old French bean plants (P. vulgaris) susceptible to rust at the stage of primary leaf growth. Spray the solution (20000 spores/ml). The plants were then kept in a high humidity controlled environment room at 21°C.
Incubate for 24 hours to infect. The plants are then removed from the incubator and allowed to dry. On the second day after incubation, the majority of infected plants are sprayed with a compound of the invention at an application rate of 1000 ppm. Do not spray remaining infected plants. This is used as a control. All infected plants are then placed in a 70° greenhouse for 5 days to allow any disease expression to occur. Disease control was evaluated by comparing treated and untreated plants, using a scale of 0 to 6 as described in the previous example, with results expressed as % disease control. These results are tabulated in Table 5.

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[Table] Example 9 Control of Cercospora Leafspot in groundnut beans by leaf treatment Three to four 4-week-old Virginia groundnut bean plants per pot were treated with the compound of the present invention at 1000, 500,
Spray at application rates of 250 and 125 ppm. The test composition is applied by spraying a suspension of the compound in water directly onto the leaves of the plants. After the plants have been sprayed and then dried, they are infected with the peanut bean Cercospora spot pathogen [Cercospora arachidicola].
inoculate with spores. The inoculum costs 20,000~ per ml.
Crafted to contain 30,000 spores. This inoculum is sprayed with 1-2 drops of Tween 20 surfactant to aid in leaf wetting. The same number of pots that have not been treated with the compounds of the invention are inoculated with the spot pathogen spores described above. All inoculated peanut bean plants were kept at 24°C in a temperature-humidity controlled room.
Incubate for 36 hours. The plants are then placed in a greenhouse to allow the disease to develop. After 18-21 days in the greenhouse, the symptoms developed are evaluated on a disease rating scale system of 0-6. Percent control is calculated by comparing the scale of treated and untreated pots. The results of this test are summarized in Table 6.

[Table] Example 10 Control of Barley Blast A suspension of the compound of the present invention was applied to approximately 6-day-old barley "Herta" seed plants in pots (approximately 8 plants/pot). Spray. These plants and an equal number of unsprayed control plants were treated with Pyricularia oryzae according to the method of Example 7.
inoculate with spores. Plants are incubated, disease is allowed to develop, and then evaluated according to the method of Example 7. The results of this test are tabulated in Table 7.

[Table] Example 11 Control of 8 types of molds The compounds of the present invention are dissolved in acetone at the concentrations shown in Table 8 below. Antibiotic Test Disk (11
mm) in each of these test acetone solutions. The disks are dried to evaporate the acetone solvent. An equal number of discs are not treated and are used as controls. The treated and untreated disks are placed on an agar plate and the test microorganism is added to the center of each test disk in the form of a culture plug in contact with the treated paper and mold pine of the test disk. These agar plates are incubated and then evaluated by measuring the diameters of the mold colonies on the treated disks and the diameters of the mold colonies on the untreated disks. Calculate % inhibition of growth. The data obtained from this test are shown in Table 8 below.

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Table: Example 12 Phytotoxic Effects All plants treated with compounds of the invention were evaluated to determine whether their growth was adversely affected by such treatment. To determine this effect, the size and growth effect of all plants treated with any of the compounds of the invention were recorded. The foregoing examples and embodiments will make apparent to those skilled in the art other embodiments and examples that are within the scope and spirit of the invention. These other embodiments and examples are within the contemplation of the invention. Accordingly, the invention should be limited only by the scope of the appended claims. Example 13 The mold control effects of the compound of the present invention and a conventional compound were compared as follows. That is, the compound of the present invention and the West German Patent Application Publication No.
Example 11 or
An experiment similar to that in 10 was conducted to compare the effects of controlling mold and barley leaf blight. The results are shown in Tables 9 to 11 below.

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[Table] Example 14 Various compounds of the present invention were produced in the same manner as in Examples 1 to 3, and in the same manner as in Example 5, Example 8, and Example 9, the effects of controlling powdery mildew on barley (BMS) and udon on cucumber were determined. The effectiveness of controlling powdery mildew (CMS), bean rust (BR), and Cercospora spot on peanut beans (CA) was investigated. The results are shown in Table 12 below.

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Claims (1)

[Claims] 1. Structural formula [In the formula, Z and Z ¹ are the same or different, oxygen,
Sulfur, SO or SO ₂ ; with Z and Z ¹
are not simultaneously oxygen; Y is nitrogen or CH; R is linear or branched _C2 - _C12 alkylene; ^R1 is hydrogen, _C1 - _C4 alkyl or phenyl; R ² is phenyl, phenoxy, phenylthio, phenoxy with halo, _C1 - _C4 alkyl, nitro, cyano or trihalomethyl as substituent, or halo, C1- _C4 as substituent
C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl with trihalomethyl or dihalomethoxy]. 2 Y is nitrogen; Z is oxygen; Z ¹ is sulfur or SO ₂ ; R is linear or branched
_C2 - _C5 alkylene; ^R1 is hydrogen, methyl or phenyl; and ^R2 is phenyl, phenylthio, phenoxy, fluorine as a substituent;
phenyl with chlorine, bromine, methyl, methoxy, trifluoromethyl or dichloromethoxy;
Alternatively, the compound according to claim 1 is phenoxy having fluorine, chlorine, bromine, methyl or trifluoromethyl as a substituent. 3 R is C ₂ -alkylene; R ¹ is hydrogen; and R ² is phenyl, phenylthio, phenoxy, phenyl substituted with bromine or phenoxy substituted with bromine, Compound of item 2. 4 Structural formula [In the formula, Z and Z ¹ are the same or different, oxygen,
Sulfur, SO or SO ₂ ; with Z and Z ¹
are not simultaneously oxygen; Y is nitrogen or CH; R is linear or branched _C2 - _C12 alkylene; ^R1 is hydrogen, _C1 - _C4 alkyl or phenyl; R ² is phenyl, phenoxy, phenylthio, phenoxy with halo, _C1 - _C4 alkyl, nitro, cyano or trihalomethyl as substituent, or halo, C1- _C4 as substituent
A mold control agent comprising a compound having _C4 alkyl, C1 _{- C4} alkoxy, phenyl having trihalomethyl or dihalomethoxy, and a pharmaceutical carrier. 5 Y is nitrogen; Z is oxygen; Z ¹ is sulfur or SO ₂ ; R is linear or branched
_C2 - _C5 alkylene; ^R1 is hydrogen, methyl or phenyl; and ^R2 is phenyl, phenylthio, phenoxy, fluorine as a substituent;
phenyl with chlorine, bromine, methyl, methoxy, trifluoromethyl or dichloromethoxy;
The mold control agent according to claim 4, further comprising a phenoxy compound having fluorine, chlorine, bromine, methyl or trifluoromethyl as a substituent. 6 Claims containing compounds in which R is C ₂ -alkylene; R ¹ is hydrogen; and R ² is phenyl, phenylthio, phenoxy, phenyl substituted with bromine or phenoxy substituted with bromine The mold control agent according to item 4. 7 formula [wherein Z and Z ¹ are the same or different and are oxygen or sulfur; provided that Z and Z ¹ are not simultaneously oxygen; Y is nitrogen or CH; R is a linear or branched chain C ₂ ~ C ₁₂ alkylene; R ¹
is hydrogen, _C1 - _C4 alkyl or phenyl; ^R2 is phenyl, phenoxy, phenylthio,
phenyl with halo, _C1 - _C4 alkyl, _C1 - _C4 alkoxy, trihalomethyl or dihalomethoxy as a substituent, or halo as a substituent,
a phenoxy having _C1 - _C4 alkyl, nitro, cyano or trihalomethyl, the method comprising: (wherein Y, R ¹ and R ² have the above meanings)
A method comprising reacting a substituted azole compound of formula HZ-R- ^Z1H with a second compound of formula HZ-R-Z1H, in which Z, ^Z1 and R have the meanings and conditions given above. 8 Y is nitrogen; Z is oxygen; Z ¹ is sulfur; R is C ₂ -C ₅ linear or branched alkylene; R ¹ is hydrogen, methyl or phenyl; and R ² is phenyl, phenylthio, phenoxy, phenyl having fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or dichloromethoxy as a substituent, or fluorine, chlorine, bromine, methyl or trifluoromethyl as a substituent 11. The method of claim 10, wherein the phenoxy has the following properties: 9 R is _C2 -alkylene; ^R1 is hydrogen; and ^R2 is phenyl, phenoxy, phenylthio, phenyl substituted with bromine or phenoxy substituted with bromine. Claim 8 Section method. 10 At least 1 mole of the second compound
9. The method of claim 8, wherein the reaction is carried out with mol of said azole compound and said reaction is carried out in the presence of an acid catalyst. 11. The method of claim 8, wherein the reaction is carried out in an inert hydrocarbon solvent. 12 formula [In the formula, Z and Z ¹ are the same or different, oxygen,
Sulfur, SO or SO ₂ ; with Z and Z ¹
is not oxygen at the same time and at least one of Z and Z ¹ is SO or SO ₂ ; Y is nitrogen or CH
R is linear or branched _C2 - _C12 alkylene; ^R1 is hydrogen, _C1 - _C4 alkyl or phenyl; ^R2 is phenyl, phenoxy,
phenylthio, phenyl with halo, _C1 - _C4 alkyl, C1- _{C4 alkoxy, trihalomethyl or dihalomethoxy as substituent, or with halo, C1-C4 alkyl , nitro} , cyano or trihalomethyl as substituent A method for producing a compound having the formula A compound of the formula [wherein Z and Z ¹ are the same ^or different and are oxygen or sulfur; provided that Z and ^{Z 1} are not simultaneously oxygen; A method comprising reacting in the presence of a carbonized hydrocarbon solvent. 13. The method of claim 12, wherein said chlorinated hydrocarbon solvent is selected from the group consisting of chloroform and dichloromethane, and said oxidizing agent is selected from the group consisting of peroxides and peroxyacids. 14 m- in which the above oxidizing agent is present at a concentration of 1 equivalent
13. The method of claim 12, wherein the chlorperoxybenzoic acid is chloroperoxybenzoic acid. 15. The method of claim 12, wherein the concentration of m-chloroperbenzoic acid is at least 2 equivalents.