JPH0121147B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to substituted arylphenyl ether derivatives represented by the following general formula, as well as acid addition salts and metal complexes thereof. The present invention also relates not only to methods for producing these compounds, but also to agricultural compositions and therapeutic agents containing at least one compound of the general formula as an active ingredient, methods for producing such compositions or therapeutic agents, and uses thereof. Furthermore, it relates to a method for treating plants for regulating or preventing attack of harmful microorganisms on plants. The arylphenyl ether derivative of the present invention has the general formula: [In the formula, Y represents -CH= or -N=, and R _a and R _b each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a C 1 to 3 alkyl group. represents an alkoxy group or a nitro group, Ar is unsubstituted or one or several halogen atoms, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a nitro group and/or CF ₃ represents a phenyl or naphthyl group substituted by a group, U and V together represent the following formula:

【formula】

[expression] or

[Formula] {In the formula, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a group having 1 to 12 carbon atoms substituted with one or several halogen atoms.
an alkyl group, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group having 1 to 3 carbon atoms, or a formula:-
Represents a group represented by CH ₂ -Z-R ₇ (wherein Z represents an oxygen or sulfur atom, R ₇ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 1 or 2 carbon atoms). C1-C8 alkyl group substituted with one alkoxy group, C3-C4 alkenyl group, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, one or phenyl group substituted by several halogen atoms, C1-C3 alkyl group, C1-C3 alkoxy group, nitro group and/or _CF3 group, unsubstituted or one or more R ₃ , R ₄ and R ₅ are each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ does not exceed 6, and R ₆ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents an alkyl group having 1 to 3 carbon atoms} Forms an alkylene bridge represented by the following formulas], as well as acid addition salts and metal complexes thereof. The substituent Ar group as an unsubstituted or substituted phenyl group or naphthyl group is, for example, represented by the following formula:

[expression] or

[Formula] (In the formula, R _c , R _d and R _e are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a nitro group, or a CF ₃ groups). Depending on the number of carbon atoms, the definition "alkyl" by itself or as another substituent may include, for example, the following groups: methyl, ethyl, propyl,
Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group or dodecyl group and their isomers,
For example, it means isopropyl group, isobutyl group, tert-butyl group, sec-butyl group, isopentyl group, etc. The alkenyl group means, for example, a propen-1-yl group, an aryl group, a buten-1-yl group, a buten-2-yl group or a buten-3-yl group. In this specification, a halogen atom is a fluorine atom,
means a chlorine atom, a bromine atom or an iodine atom,
A chlorine atom or a bromine atom is preferred. The present invention relates to free compounds of the general formula and their acid addition salts with inorganic and organic acids, and also to their complexes with metal salts. The salts of the invention are in particular addition salts with inorganic or organic acids which are physiologically acceptable for their usefulness. Examples of physiologically acceptable inorganic or organic acids with regard to their usefulness as fungicides in plant prevention include hydrohalic acids such as hydrochloric acid, hydrobromic acid or hydroiodic acid, sulfuric acid, phosphoric acid, etc. acids, unsaturated or halogenated fatty acids such as phosphorous acid, nitric acid, acetic acid, trichloroacetic acid and oxalic acid, or sulfonic acids such as benzenesulfonic acid and methanesulfonic acid. With regard to their medicinal utility, physiologically acceptable acids, i.e., pharmaceutically acceptable salts, are:
hydrohalic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid; pharmaceutically acceptable inorganic acids such as nitric acid, sulfuric acid or phosphoric acid; acetic acid, fumaric acid, maleic acid, malic acid or tartaric acid; aliphatic monocarboxylic acids such as and optionally hydroxylated dicarboxylic acids, and lower alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and p-bromobenzenesulfonic acid or Pharmaceutically acceptable carboxylic acids and sulfonic acids such as substituted or unsubstituted benzenesulfonic acid or aromatic sulfonic acids, and sulfamic acids such as N-cyclohexylsulfamic acid. The metal complex of the general formula has a basic organic molecule and
It is composed of copper, magnesium, iron, subsalt, etc., or inorganic or organic metal salts such as halides, nitrides, sulfides, phosphides, tartrates, etc. of other metals. The metal cations can be present in different valences. Compounds of the general formula are oils, resins or solids that are stable at room temperature and have very valuable biological properties, such as microbial activity and pharmaceutical properties, such as phytoantifungal activity. , especially has antifungal, anticonvulsant or anxiolytic effects. Therefore, on the one hand, it can be used in the agrochemical or related field for the prevention of plant microbial pathogenesis, and on the other hand, in the pharmaceutical field, it can be used for antifungal and/or anticonvulsant and anxiolytic, e.g. It can be used to control fungi that parasitic animals and/or for the treatment of various epilepsy, anxiety, nervous and excited states, and/or manic states. _An important group _of fungicidal compounds used in plant protection are: Represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a nitro group, and Ar is the following formula:

[expression] or

[Formula] (In the formula, R _c , R _d and R _e are each independently a hydrogen atom,
(represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a nitro group or a CF ₃ group), and U and V taken together represent the following formula:

【formula】

[expression] or

[Formula] {In the formula, R ₁ and R ₂ are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and 1 to 12 carbon atoms substituted with one or several halogen atoms.
an alkyl group, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group having 1 to 3 carbon atoms, or a phenyl group of the formula:-
Represents a group represented by CH ₂ -Z-R ₇ (wherein Z represents an oxygen or sulfur atom, R ₇ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 1 or 2 carbon atoms). 1 alkyl group having 1 to 8 carbon atoms, alkenyl group having 3 to 4 carbon atoms, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, substituted with 1 alkoxy group or a phenyl group substituted with several halogen atoms, C1-C3 alkyl groups, C1-3 alkoxy groups, nitro groups and/or _CF3 groups, unsubstituted or one or represents a benzyl group substituted with several halogen atoms, an alkyl group having 1 to 3 carbon atoms and/or an alkoxy group having 1 to 3 carbon atoms), R ₃ , R ₄ and R ₅ are each independent represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ does not exceed 6, and R ₆ is a hydrogen atom. or represents an alkyl group having 1 to 3 carbon atoms} These are compounds that form an alkylene bridge, as well as acid addition salts and metal complexes thereof. This subgroup is named a. A preferred group of fungicidal compounds effective for agricultural use is the general formula in which Y represents -CH= or -N=, and R _a and R _b independently represent a hydrogen atom, a halogen atom, or the number of carbon atoms. Represents 1 to 3 alkyl groups, Ar is the following formula: (In the formula, R _c , R _d and R _e each independently represent a hydrogen atom, a halogen atom, CF ₃ or an alkyl group having 1 to 3 carbon atoms), and U and V represent the above-mentioned Compounds having the meaning defined in the formula, as well as acid addition salts and metal complexes thereof. This group is named group b. Preferred fungicidal compounds in subgroup b are:
In these general formulas, U and V together form the following formula:

[expression] or

[Formula] (However, in the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; in this case, R ₃ , R The total number of carbon atoms in ₄ and R ₅ does not exceed 6). This group is named group C. A more preferable group of fungicidal groups effective for agricultural purposes is: in the general formula, Y represents -CH= or -N=, Ar represents the meaning defined in the above formula, and R _a , R _b , R _c , R _d , and R _e independently of each other,
represents a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a methyl group, a methoxy group or a nitro group, and U and V together form an alkylene bridge as defined in the above formula, in which case,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other,
represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, or R ₁ is of the formula: -CH ₂ -O-R ₇
In the formula, R ₇ is an alkyl group having 1 to 3 carbon atoms, an alkyl group having 2 to 4 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 3 to 3 carbon atoms. This is a compound representing an alkenyl group or a phenyl group of 4. This group is named group d. Among Group d, those having particularly excellent bactericidal properties are compounds in which U and V together form an unsubstituted or simply substituted ethylene or propylene bridge. This group is named group e. Therefore, the following individual compounds are exemplified as particularly preferred in the agricultural field. 2-[p-(phenoxy)-phenyl]-2-[1
-(1H-1,2,4-triazolyl)methyl]-
4-methyl-1,3-dioxane, 2-[p-(phenoxyphenyl]-2-[1-
(1H-1,2,4-triazolyl)methyl]-4
-ethyl-1,3-dioxane, 2-[p-(phenoxy)phenyl]-2-[1-
(1H-1,2,4-triazolyl)methyl]-4
-Methyl-1,3-dioxolane, 2-[p-(phenoxy)phenyl]-2-[1-
(1H-1,2,4-triazolyl)methyl]-4
-Methyl-1,3-dioxolane. Compounds of the general formula of interest for antifungal activity are classified in group f, where Y represents -CH= or -N=, and R _a and R _b are independently of each other a hydrogen atom, a halogen atom or represents an alkyl group having 1 to 3 carbon atoms, and Ar is the following formula: (In the formula, R _c , R _d and R _e each independently represent a hydrogen atom, a halogen atom, CF ₃ , an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms) and U and V are compounds having the meanings defined in the above formula. Within subgroup f, compounds of the general formula preferred for antifungal activity are: where U and V taken together have the following formula:

[expression] or

[Formula] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; in this case, R ₃ , R ₄ and the total number of carbon atoms in R ₅ must not exceed 6). This group is named group g. In subgroup g, preferred compounds of the general formula with respect to their antifungal activity are:
U and V together form the following formula (In the formula, R ₇ is an alkyl group having 1 to 4 carbon atoms,
A compound representing an alkylene group represented by an alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 or 4 carbon atoms, or a 2-propynyl group substituted with an alkoxy group having 1 or 2 carbon atoms. be. This group is named group h. A further preferred group of compounds having antifungal activity of the general formula is: wherein Y represents -CH=, Ar represents the meaning defined in the above formula, and R _a and R _b independently of each other represent a hydrogen atom. , represents a methyl group, a chlorine atom or a bromine atom, and R _c , R _d and R _e each independently represent a hydrogen atom,
represents a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group, a _CF3 or a nitro group, and U and V together represent an alkylene group represented by the formula given in the above formula; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, or R ₁ is of the formula -CH ₂ OR ₇ ; In this case, R ₇ represents a group having 2 or 3 carbon atoms substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 or 2 carbon atoms.
or an alkenyl group having 3 or 4 carbon atoms. This group is named group i. The following individual compounds are illustrative of particularly preferred compounds having antifungal activity. 2-[p-(phenoxy)phenyl]-2-[1-
(1H-1,2,4-triazolyl)methyl]-4
-Methyl-5-methyl-1,3-dioxolane, 2-[p-(phenoxy)phenyl]-2-[1-
(1H-1,2,4-triazolyl)methyl]-1,
3-dioxane, 2-[p-(phenoxy)phenyl]-2-(1-
imidazolylmethyl)-4-ethyl-1,3-dioxolane, 2-[p-(2,4-dimethylphenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane , 2-[p-(3-chlorophenoxy)phenyl]
-2-(1-imidazolylmethyl)-4-ethyl-
1,3-dioxolane, 2-[p-(4-chlorophenoxy)phenyl]
-2-(1-imidazolylmethyl)-4-ethyl-
1,3-dioxolane, 2-[p-(3-trifluoromethylphenoxy)phenyl]-2-(1-imidazolylmethyl)
-4-ethyl-1,3-dioxolane, 2-[p-(4-chloro-3-methylphenoxy)phenyl]-2-(1-imidazolylmethyl-
4-ethyl-1,3-dioxolane, 2-[p-(3,4-dichlorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane, 2-[ p-(2,5-dichlorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane, 2-[p-(3,4-dichlorophenoxy)phenyl ]-2-(1-imidazolylmethyl)-4-methoxymethyl-1,3-dioxolane, 2-[p-(4-fluorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl -1,3-dioxolane, 2-[p-(4-fluorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-methyl-5-methyl-1,3-dioxolane and their pharmaceutical is an acceptable acid addition salt. Furthermore, methods for their preparation, formulations containing them and methods for their use as medicines are also particularly mentioned. Interesting compounds of general formula related to anticonvulsant or anxiolytic properties fall into group g, where Y represents -CH= or -N= and R _a and R _b are independent of each other. represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, Ar is unsubstituted or an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms,
It represents a phenyl group substituted with CF ₃ or a halogen atom, and U and V represent the meanings defined in the above formula. In subgroup g, compounds of the general formula having very useful anticonvulsant and anxiolytic properties are those in which Y represents -CH= or -N= and R _a and R _b are each independently represents a hydrogen atom, a methyl group, a chlorine atom or a bromine atom, Ar represents an unsubstituted or phenyl group substituted with a halogen atom, a methyl group or _CF3 , and U and V independently of each other represents an alkyl group having 1 to 3 carbon atoms or an alkyl group having 2 to 3 carbon atoms which may be substituted with an alkoxy group having 1 to 2 carbon atoms, or taken together to form the following formula:

[expression] or

[Formula] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; in this case, R ₃ , R ₄ and The total number of carbon atoms in R ₅ must not exceed 4). These groups are named group k. A further preferred group of compounds with distinct anticonvulsant and anxiolytic properties include those in which Y represents -CH= or -N=, R _a and R _b represent a hydrogen atom, and Ar is represents a substituted or halogen atom, or a phenyl group substituted with a methyl group, and U and V together represent the formula:

[expression] or

[In the above formula, R _a , R _b , Y, Ar and R ₇ represent the meanings defined in the above formula, and one of X ₁ and X ₂ may optionally be in the form of a salt, such as the formula -Z-Me (wherein Z represents an oxygen or sulfur atom and Me represents a hydrogen atom or a metal cation) represents a hydroxyl group or a mercapto group, and the other represents a nucleophilic separating group. , or both X ₁ and X ₂ represent a hydroxyl group]

or combine the compounds represented by
or (D) a compound represented by the general formula: Ar-X ₃ () and the general formula: [In the formula, Ar, R _a , R _b , Y, U and V represent the meanings defined in the above formula, and one of X ₃ and X ₄ is of the formula -O-Me (wherein Me is a hydrogen atom or a metal cation) represents a group represented by
and the other represents a group capable of exchanging the aryloxy group], or
Or (E) general formula: (In the formula, Y, R _a , R _b , Ar, U and V represent the meanings defined in the formula) The compounds obtained can be converted into other compounds of the formula and/or the free compounds obtained by these methods can be converted into acid addition salts or the acid addition salts obtained by such methods can be converted into free compounds. It can be obtained by converting the free compound or acid addition salt obtained by these methods into a metal complex. Examples of metal cations Me are alkali metal cations, such as lithium, sodium or potassium cations, or alkaline earth metal cations, such as magnesium, strontium or barium cations. Leaving groups include, for example, reactive esterified hydroxyl groups, such as hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid; Examples include hydroxyl groups esterified with lower alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or fluorosulfonic acid, substituted or unsubstituted benzenesulfonic acids, or halogenated sulfonic acids. It will be done. General formula: an azole compound of the general formula: (In the formula, Ar, R _a , R _b , U and V represent the meanings defined in the above formula, and (representing a trifluoroacetyloxy group or preferably a lower alkylsulfonyloxy group such as a mesyloxy group) may be carried out in a relatively polar but inert organic solvent, such as N,N-dimethyl Formamide, N,N-dimethylacetamide,
Preference is given to working in dimethyl sulfoxide, acetonitrile, benzonitrile and similar solvents. Solvents of this type can also be used in combination with other inert solvents, such as aliphatic or aromatic hydrocarbon solvents such as benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene and the like. If the group X is a chlorine or bromine atom, addition of an alkali iodide (such as sodium or potassium iodide) is effective in accelerating the reaction. The heating temperature is preferably 0 to 220°C, preferably 80 to 170°C. Preferably, the reaction mixture is heated under reflux. When the group Me in the general formula is a hydrogen atom,
The reaction is carried out in the presence of a base. Preferred bases include inorganic bases such as, for example, alkali metal and alkaline earth metal oxides, hydroxides, hydrides, carbonates and bicarbonates, as well as triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine. , 4
- Organic bases such as tertiary amines such as pyrrolidylpyridine. This variant and subsequent preparation make it possible to isolate intermediates and final products from the reaction medium and, if desired, to purify them using any conventional means such as extraction, crystallization, chromatography, distillation, etc. Ru. To convert a carbonyl group in a compound of the general formula to a group of the general formula, a carbon atom which is unsubstituted or whose alkyl moiety having 1 to 12 carbon atoms is substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms React with a trialkyl orthocarboxylic acid ester of number 1 to 12, or with at least 2 moles of an alcohol having one hydroxyl group of the following formula Va: U-OH (Va) in the presence of an acid. A compound in which U and V in the general formula are unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms is obtained, or reacted with a diol compound of the formula Vb: HO-U...V-OH (Vb), to give compounds in the general formula in which U and V together form an alkylene bridge as defined at the beginning. in this case,
Ar, Y, Ra, Rb, U and V have the meanings defined in the general formula above. This ketal-forming reaction is carried out by a method similar to the already known ketal-forming reaction, for example, a method similar to the method for producing 2-bromomethyl-2,4-diphenyl-1,3-dioxolane [Synthesis 1974 (), 23]. This can be done by A particularly preferred method of ketanolization is to heat both reactants with an azeotrope forming agent in a conventional organic solvent for several hours under reflux. Preferred examples of azeotrope forming agents include benzene, toluene, xylene,
Chloroform or carbon tetrachloride. In order to accelerate the reaction, it is preferable to add a strong acid such as p-toluenesulfonic acid. Organic solvents that can be used in this case include aromatic hydrocarbons such as benzene, toluene, and xylene, saturated hydrocarbons such as n-hexane, and 1,1,1-
Included are halogenated saturated hydrocarbons such as trichloroethane. Furthermore, as another method of ketalization, for example, a ketone of the general formula is ketalized with an alcohol or phenol different from the alkanol or diol compound of the formula Va or Vb, and an effective rearrangement ketal is obtained by using an excess amount of the alkanol Va or diol Vb. to obtain a compound of general formula.
The starting materials can be obtained, for example, according to process variants (A), (D) and (E). In modified method (C), to obtain a compound in which U and V in the general formula are combined to form -CH ₂ -CH(CH ₂ ZR ₇ )-, for example, a compound of the general formula and a compound of the general formula (wherein X ₁ has the group -ZH, X ₂ has the meaning defined for the group X). Preferably, the reaction is carried out in an inert organic solvent. Examples of preferred solvents for this reaction include N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphorotriamide, dimethylsulfoxide, 4-methyl-3-pentanone, and the like. Other inert solvents, such as benzene,
Mixtures with aromatic hydrocarbons such as toluene and xylene can also be used. In some cases it is advantageous to react in the presence of a base to accelerate the reaction. Examples of such suitable bases are alkali metal hydrides or alkali metal carbonates. It may also be advantageous in some cases to first convert the compound of the general formula into the preferred metal salt; this reaction may be carried out, for example, by converting the compound of the formula N with a sodium compound such as sodium hydride, sodium hydroxide, etc. This is preferably accomplished by reacting. A salt of a compound of this formula is then reacted with a compound of formula. In order to speed up the reaction rate, the reaction is carried out in some cases at elevated temperatures, preferably
80-130°C or below the boiling point of the solvent. The general formula and (in the formula X ₁
represents a group X and X ₂ represents a group -ZH) can also be reacted. The condensation reaction to obtain _a compound in which Z represents _an oxygen atom from a compound of the formula This can be carried out by azeotropically removing water from the reaction mixture. Such suitable solvents include aromatic hydrocarbons such as toluene or HO-R ₇ alcohol itself. This reaction is advantageously carried out in the presence of a strong acid, such as p-toluenesulfonic acid. In variant (D _{) , the} general formula _and (wherein Ra, Rb, U, V, Y and Ar have the meanings defined in the above formula, and Me preferably represents a hydrogen atom). This reaction is advantageously carried out under the conditions of process variant (A) above. In modified method (E), the compound of general formula X to be decarboxylated is general formula XI: The compound is obtained by the ketalization reaction in the same manner as described in (B), and this compound has the general formula
XII: A compound of Ar-OH (XII) is reacted with a difunctional derivative of a carboxylic acid such as phosgene, a lower alkyl ester of a halogenated formic acid or a di-lower allyl or diphenyl carbonate, and further with the general formula: or in a high boiling point solvent such as a high boiling point ether such as diphenyl ether or ethylene glycol dimethyl ether.
It can be obtained by heating to 120° to 220°C. The compounds obtained by the method of the invention can be converted into other compounds of the general formula by methods known per se. Thus, for example, the compounds obtained by the method of the invention can be converted into other compounds of the general formula by a rearrangement ketalization reaction. For example, U
and V are identical unsubstituted or substituted C1 -C12 alkyl radicals, the radical U is a molar amount of another unsubstituted or substituted C1 -C12 alkyl group V-OH (Vc) can be replaced by a group V by reaction with an alkanol, or both groups U can be replaced by a divalent radical by reaction with a diol compound of formula Vb. The rearrangement ketal reaction is carried out by conventional means, preferably in the presence of an acid condensation reagent of an inorganic acid, a sulfonic acid or a strong carboxylic acid, such as hydrochloric acid, hydrobromic acid, sulfuric acid, p-toluenesulfonic acid or trifluoroacetic acid. can be carried out while removing volatile reaction products by distillation or azeotropic distillation. Furthermore, if desired, a substituent can be introduced into the carbocyclic aryl moiety of the compound obtained by the method of the present invention. For example, halogen atoms can be introduced by reacting the halogen in the presence of Lewis acids such as iron, zinc, boron, or antimony halides, or by treatment with N-chlorosuccinimide. Additionally, the nitro group is reduced to an amino group by using a suitable hydrogenation complex such as lithium aluminum hydride, the amino group being diazotized, for example with nitrous acid, and the diazonium group being reduced by conventional means. Substituted with a halogen atom or an alkoxy group. Similarly, halogen atoms can be replaced by alkyl groups, for example by reaction with alkylmetal compounds such as alkyllithium or alkylmagnesium halides. If a compound of the general formula is obtained as a free base, it can be converted into the corresponding salt of the general formula with inorganic or organic acids, or preferably by using equimolar amounts of metal salts. It can also be converted into a metal complex. Conversely, a salt of the general formula can be converted to a free base of the general formula by reaction with an alkali metal carbonate, bicarbonate or hydroxide. The starting ketanol compound of the general formula is: Methyl aryl ketone compounds, such as halogenated hydrocarbons (methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, etc.)
can be obtained by reaction with the desired diol compound in an inert solvent such as and simultaneous or subsequent halogenation. In this case, it is preferable to add p-toluenesulfonic acid to accelerate the reaction. Ketones of the general formula can be obtained by halogenation of the starting ketones with the general formula: can be obtained by further reacting it with an azole compound of the general formula in the same manner as modified method (A). The halogen atom in the general formula is preferably a chlorine atom or a bromine atom. Ketal compounds and can be obtained in a similar manner to variant (B), for example by reacting a starting ketone of the general formula with the desired alcohol or di-o compound. Variants such as those described above constitute the object of the invention. Substituted with the aforementioned ketones α, β- or α, γ-
Ketanolization reactions with diols form predominantly diastereoisomeric mixtures of the resulting ketanols. Similarly, mixtures of final products of the general formula can generally be obtained from starting ketones. Compounds of the general formula can be obtained, for example, as the following two diasterene isomers. : The configuration of type A here indicates the "trans" isomer (the same applies hereinafter). The configuration of type B here indicates the "cis" isomer (the same applies hereinafter). The symbols in the above three-dimensional structure have the following meanings: ... = Rear of the depiction plane - = Above the depiction plane = = Front of the depiction plane The two types of diastereoisomers are, for example,
Separation may be carried out by fractional crystallization or by chromatography (thin layer chromatography, column chromatography, liquid high pressure chromatography). The two isomers have different biological properties. Mixtures of diastereoisomers are commonly used in practical applications. The present invention relates to all isomeric compounds of the formula, salts thereof and metal complex salts thereof. The preparation of the compounds of the formulas described in variants A, B, C and E likewise constitute an object of the invention. Some of the starting materials and intermediates used in process variants A, B, C, D and E are known, others can be prepared by methods known per se. Also, some are new and their preparation is described here. 1-(β-aryl)ethimidazolyl ketals in which the aryl group is a substituted phenyl or naphthyl group are described in the following documents: (U.S. Pat. No. 3,575,999;
No. 3936470, No. 4101664, No. 4101666 and No.
4156008 as a fungicide and bactericide. Surprisingly, it has been found that the compound of formula has practically a very useful bactericidal spectrum against phytopathogenic fungi and bacteria as well as fungal and antispasmodic properties indicating its use as a pharmaceutical. . For example, the compounds of the formula have very effective curative, systemic and prophylactic properties and can be used for the protection of cultivated plants. When using compounds of the formula, it is possible to prevent or destroy microorganisms that occur on plants or plant parts (fruits, flowers, leaves, stems, tuberous roots) in various useful plants, while at the same time preventing the growth of plants that subsequently grow. parts are also protected from microbial damage. The compounds of the formula are active against phytopathogenic fungi belonging to the following classes: Deuteromycetes [e.g. Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora ( Cerco-spora and Alternaria]; Basidiomycetes [e.g. Genera Hemileia, Rhizocotonia, Puccinia]; Cysticomycetes [e.g. Venturia, Podasphaera, Erysiphe, Monilinia, Uncinula. Furthermore, the compounds of the formula have osmotic properties. They can also be used as seed dressings to protect seeds (fruits, tubers, grains) and as plant cutt-ings against fungal infections and against phytopathogenic fungi occurring in the soil. The invention therefore also provides fungicidal compositions and compounds of the formula for the preventive treatment of plants for controlling pathogenic microorganisms, in particular harmful fungi, and for protecting plants from damage by such microorganisms. It concerns the use of. Furthermore, the present invention encompasses a process for the preparation of agrochemical compositions, characterized in that a compound of the formula is mixed homogeneously with one or more substances or substances as described herein. The invention further relates to a method for treating plants, characterized in that the method comprises applying to the plants a compound of the formula or a novel composition. Objects protected within the scope of the invention include, for example, the following plant species: cereals (wheat, barley, rye, oats, rice, sugar corn and related crops), beets (sugar beets and sugar beets). beets), stone fruits, pears and soft fruits (apples, pears,
Plums, peaches, almonds, cherries, strawberries,
raspberries and blackberries), legumes (fava beans, lentils, peas, soybeans), oil plants (oil, mustard, poppy, olive, sunflower, coconut, castor oil plants, cocoa beans, peanuts, cucurbits) plants (white cucumbers, marrows, melons), textile plants (cotton, flax,
Cannabis, jute), orange plants (orange, lemon, grapefruit, mandarin), vegetables (spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, horseradish, paprika),
Lauraceae (abogato, cinnamon, camphor), corn, tobacco, nuts, coffee, cane sugar,
Tea, grape vine, hops, banana and natural rubber plants, as well as ornamental plants (Asteraceae). The compounds of the formula are usually applied in the form of agricultural compositions and applied to the crop ground or the plants to be treated.
It may be applied simultaneously or sequentially with other compounds. These compounds are fertilizers or micronutrient providers,
Alternatively, it may be other formulations that affect plant growth. If desired, further carriers commonly used in the pharmaceutical industry,
In conjunction with surface-active agents or application promoting aids, they can be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of some of these formulations. Suitable carriers and auxiliaries may be solid or liquid and correspond to substances commonly used in formulation technology, such as natural or recycled minerals, solvents, dispersants, wetting agents, thickeners, tackifiers or binders. do. A preferred method of applying the agronomic compound or agrochemical composition to infected plants is foliar spraying. The number of applications and the amount of application depend on the intensity of infection by the corresponding pathogen (type of fungus). However, the compound of the formula can also be passed through the soil to the roots by impregnating the plant locally with the compound as a liquid composition or by applying it to the soil (soil application) in the form of a solid, e.g. in the form of granules. can enter the plant (osmotic action). A compound of the formula can also be applied to the seed (coating) by impregnating the seed with a liquid formulation containing the compound of the formula or by coating the seed with a solid formulation. In special cases other types of applications are also possible, for example selective treatment of plant stems or shoots. The compounds of the formula are used in unaltered form or preferably with auxiliaries customary in the pharmaceutical industry and can be prepared as emulsion stock solutions, coatable pastes, directly sprayable or dilutable solutions, dilutions, etc. by known methods. They are formulated into emulsions, wettable powders, aqueous solutions, powders, granules, and encapsulates, for example with polymeric substances. As well as the nature of the composition, spraying,
Application methods such as atomization, dusting, sprinkling or pouring are chosen depending on the intended target and the general environment. Advantageous application rates are usually 50 g to 5 Kg of active ingredient (AI) per hectare, preferably 100 g to 2 Kga.i./ha, most preferably 200 g to 600 g.
ga.i./ha. Agrochemical preparations, i.e. compositions or preparations containing a compound of the formula (active ingredient) and, if appropriate, solid or liquid auxiliaries, can be prepared, for example, by combining the active ingredient with a solvent, a solid carrier and, if appropriate, by known methods. It is produced by homogeneous mixing and/or milling with debulking agents such as surface-active compounds (surfactants). Suitable solvents are: aromatic hydrocarbons, preferably C8-C12 moieties, such as xylene mixtures or substituted naphthalenes; phthalates such as dibutyl phthalate or dioctyl phthalate; fats such as cyclohexane or paraffin. alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol monomethyl or monoethyl ether; ketones such as cyclohexane; strongly polar such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide a solvent; and an epoxidized vegetable oil such as epoxidized coconut oil or soybean oil; or water. Solid carriers which can be used, for example for dusts and dispersible powders, are usually natural mineral fillers such as calcite, talc, kaquilin, montmorillonite or attapulgite. It is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers to improve the physical properties. Suitable granulated absorbent carriers are of the porous type, for example pumice, crushed brick, sepiolite or pentonite; and suitable non-absorbent carriers are materials such as calcite or sand. Furthermore, a large number of pre-granulated inorganic and organic substances, especially dolomite or pulverized plant residues,
can be used. Depending on the nature of the compound of formula to be formulated, suitable surfactants are nonionic, cationic and/or anionic surfactants with good emulsifying, dispersing and wetting properties. “Surfactant”
It is to be understood that the term also includes mixtures of surfactants. Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds. Suitable soaps are obtained from alkali metal salts, alkaline earth metal salts, or unsubstituted or substituted ammonium salts of higher fatty acids (C ₁₀ -C ₂₂ ), such as oleic acid or stearic acid, or from coconut oil or tallow, for example. Sodium or potassium salts of natural fatty acid mixtures. Fatty acid methyltaurate salts may also be mentioned. However, more frequently so-called synthetic surfactants are used, especially fatty trisulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. The aliphatic sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts, and contain C8-C22 alkyl groups, including also the alkyl part of the acyl group, e.g. Sodium or calcium salts of lignosulfonic acid, dodecyl sulfate or mixtures of fatty alcohol sulfates obtained from natural fatty acids. These compounds also include salts of sulfuric acid esters and salts of sulfonic acids of aliphatic alcohol/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 or naphthalenesulfonic acid/formaldehyde condensation products. Corresponding phosphates, such as salts of the phosphoric esters of p-nonylphenol adducts containing 4 to 14 mol of ethylene oxide, are also suitable. The nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols or saturated or unsaturated fatty acids and alkylphenols, which derivatives contain from 3 to 30 glycol ether groups, (fatty or Group) 8 to 20 carbon atoms in the hydrocarbon portion and 6 to 18 carbon atoms in the alkyl portion of the alkylphenol. Other suitable nonionic surfactants are polyethylene oxide and polypropylene glycol,
Ethylene diamine polypropylene glycol is a water-soluble adduct with an alkyl polypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, the adduct containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol. Contains ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Typical examples of nonionic surfactants are nonylphenol-polyethoxyethanol, castor oil polyglycol ether, polypropylene/polyethylene oxide adduct, tributylphenoxypolyethoxyethanol, polyethylene glycol, and octylphenoxyethoxyethanol. be. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan triolate are also suitable nonionic surfactants. The cationic surfactants preferably contain at least one carbon atom as N-substituent.
It is a quaternary ammonium salt containing a lower unsubstituted or halogenated alkyl group, a benzyl group, or a lower hydroxyalkyl group as another substituent. The salt is preferably in the form of a halide, methyl sulfate or ethyl sulfate, such as stearyltrimethylammonium chloride or benzyl di-(2-chloroethyl)ethylammonium bromide. Surfactants customary in the pharmaceutical industry are described, for example, in the publication:
Annual (Mc Cutcheon's Detergents and
Emulsifiers Annual), Matsuku Publishers, Ringwood, New Jersey, 1979; and Sisely and Wood, Encyclopedia of Surf-Aces.
Active Aging Encyclopedia of
Surface Active Agents)”, Chemical Publishers, New York, 1980. Pesticide formulations typically contain between 0.1 and 99% of the compound of formula
Preferably 0.1 to 95%, solid or liquid adjuvant
It contains 99.9% to 1% preferably 99.8% to 5% and surfactant 0 to 25% preferably 0.1 to 25%. Although commercially available products are preferably formulated as neat solutions, consumers will typically use diluted formulations. The compositions may also contain other ingredients, such as stabilizers, consumables, viscosity modifiers, binders, tackifiers and fertilizers, or other active ingredients for obtaining special effects. Such agrochemical compositions also constitute an object of the present invention. Antifungal properties demonstrate the utility of the compounds of the formula and their pharmacologically acceptable acid addition salts for controlling parasitic fungi in warm-blooded animals, e.g. By conventional microbiological test methods, e.g.
Trichophyton mentagryphites,
Microsporum canis, Sporotrichum schenkii,
Aspergillus fumigatus
fumigatus) and Candida albicans; and also in vivo in guinea pigs, after oral or topical application, Trichophyton spp. , for example, by experimentally infecting Trichophyton rubrum (T. rubrum) and measuring its healing effect. The antispasmodic properties of the compound represented by the formula and its pharmacologically acceptable acid addition salts have been shown to induce, for example, pentatetrazole spasm in vivo in mice at doses of about 10 to 100 mg/Kgp.o. may be demonstrated by testing and also by electroshock testing at doses of about 10 to 100 mg/Kgp.o. Anxiolytic properties have been shown, for example, in mice and other small rodents, to
as shown by the Gellert test and the Quatre-Plaque test at doses between 100 mg/Kgp.o. It should also be mentioned that the new compounds have important antimanic properties. Accordingly, the present invention also provides compounds of the formula and their pharmacologically acceptable acid addition salts for use in topical, local applications of fungi that are parasites of warm-blooded animals. and systemic (sys
−temic) for pest control; and
Use in particular as an active ingredient in pharmaceutical preparations for the systemic treatment of various epileptic conditions, anxiety and catatonic states or manic states of mind, or in pharmaceutical preparations for enteral, parenteral or topical application. and also to said pharmaceutical formulations. Pharmaceutical preparations (pharmaceutical preparations) containing the compound represented by the formula or a pharmacologically acceptable salt thereof
for enteral administration, e.g. orally or rectally, and for parenteral administration;
as well as for topical application to warm-blooded animals, these preparations contain the pharmacologically active ingredient alone or together with a pharmacologically acceptable carrier therefor. The dose of active ingredient depends on the species of warm-blooded animal, the age and medical condition of the patient and the method of administration or application. For oral administration to warm-blooded animals weighing approximately 75 kg, the daily dose is usually approximately 50 to
500 mg, preferably administered in several equal doses. The pharmaceutical formulation of the present invention may contain, for example, an active ingredient of about
Pharmaceutical preparations for enteral or parenteral administration containing 10 to 80% preferably about 20 to 60%
For example, dosage unit forms such as dragees, tablets, capsules or suppositories and also ampoules. These are produced by methods known per se, for example by customary mixing, granulation, dragee-coating, dissolution or lyophilization. Pharmaceutical preparations for oral administration are therefore prepared by mixing the active ingredient with a solid carrier, optionally granulating the resulting mixture and, if desired or necessary, adding suitable auxiliaries. It is obtained by processing a granular mixture into tablet or dragee cores. Suitable carriers for tablets and/or dragees are in particular fillers, such as sugars, such as lactose, sutucarose, mannitol or sorbitol, cellulose products and/or calcium phosphates, such as tricalcium phosphate, calcium hydrogen phosphate, or binders. agents, such as starch pastes, such as corn, grains,
rice or potato starch paste, gelatin,
Gum tragacanth, methylcellulose, hydroxypropylmethylcellulose, sodium carboxymethylcellulose and/or polyvinylpyrrolidone, and/or optionally disintegrants, such as the starches mentioned above, but also carboxymethylstarch, crosslinked polyvinylpyrrolidone, agar, alginic acid or its salts, e.g. It is sodium. Auxiliary agents are glidants and lubricants, such as silicic acid, talc, stearic acid or its salts, such as magnesium or calcium stearate, and/or polyethylene glycols. The cores of the dragee tablets are provided with a suitable coating resistant to gastric juices, which may include, inter alia, gum arabic, talc, polyvinylpyrrolidone, polyethylene glycol and/or titanium dioxide. Sugar solutions, ceramic solutions in suitable organic solvents or solvent mixtures are used, and solutions of suitable cellulose preparations, such as acetylcellulose phthalate or hydroxypropylmethylcellulose phthalate, are used in the production of coatings that are resistant to gastric juices. do. Dyestuffs or pigments may be added to the core of the tablet or dragee, for example to distinguish or to identify different active ingredients. Other pharmaceutical preparations for oral administration are dry-filled and soft sealed capsules made of gelatin and a plasticizer, such as glycerol or sorbitol.
Dry-filled capsules are in the form of granules, e.g.
The active ingredient may be present in admixture with fillers such as lactose, binders such as starches, and/or lubricants such as talc or magnesium stearate, and stabilizers. In soft capsules, the active ingredients are dissolved or suspended in suitable liquids, for example fatty oils, paraffin oil or liquid polyethylene glycols, to which stabilizers can also be added. Suitable dosage forms for rectal administration are, for example, suppositories, which consist of a combination of the active ingredient and a suppository base. Suitable suppository bases are, for example, natural or synthetic triglycerides, paraffin hydrocarbons, polyethylene glycols or higher alcohols. Gelatin intestinal capsules consisting of a combination of active ingredient and base material may also be used. Suitable base materials are, for example, liquid triglycerides, polyethylene glycols or paraffin hydrocarbons. Particularly suitable for parenteral administration are water-soluble forms, e.g. aqueous solutions of the active ingredient in water-soluble salts, and also suspensions of the active ingredient, e.g. suitable oily injection suspensions (for this purpose). in a lipophilic solvent or vehicle such as a fatty oil, e.g. sesame oil,
Or synthetic fatty acid esters such as ethyl oleate or triglycerides can be used. )
or substances that increase viscosity, e.g. sodium
Carboxymethylcellulose is an aqueous injection suspension containing sorbitol and/or dextran and, optionally, stabilizers. Pharmaceutical preparations for topical application are, for example, creams, ointments, pastes, foams, tinctures and solvents, which contain the active ingredient in amounts of about 0.5% to about 20%. Creams are oil-in-water (o/w) emulsions;
It contains more than 50% water. Oily bases include mainly fatty alcohols, such as lauryl, cetyl or stearyl alcohol, fatty acids, such as palmitic or stearic acid,
Liquid or solid waxes, such as isopropyl myristate, wool wax or beeswax, and/or hydrocarbons, such as petrolatum or paraffin oil, are used.
Suitable emulsifiers are mainly surface-active substances with hydrophilic properties, such as corresponding non-ionic emulsifiers, such as fatty acid esters of polyalcohols or their ethylene oxide adducts, such as polyglycerol fatty acid esters or polyoxyethylene sorbitan fatty acid esters (Tweens). polyoxyethylene fatty alcohol ethers or esters, or corresponding ionic emulsifiers, such as alkali metal salts of fatty alcohol sulfates, such as sodium lauryl sulfate, sodium cetyl sulfate or sodium stearyl sulfate, which are commonly used Generally used in the presence of fatty alcohols, such as cetyl alcohol or stearyl alcohol. Additives to the aqueous phase are those that reduce water loss by evaporation, such as polyalcohols such as glycerol, sorbitol, propylene glycol and/or polyethylene glycol, as well as preservatives, fragrances, and the like. Ointments contain at least 70% water or an aqueous phase, preferably about
It is an emulsion in which water is dispersed in 20% to 50% oil (water-in-oil: w/o). The oil phase consists primarily of hydrocarbons, such as petroleum jelly, paraffin oil and/or hard paraffin, which are preferably combined with hydroxy compounds suitable for modifying water absorption, such as fatty alcohols or their esters, such as cetyl. Contains alcohol or wool wax. Emulsifiers are corresponding lipophilic substances,
For example, sorbitan fatty acid esters (Spans), such as sorbitan oleate and/or sorbitan isostearate. Additives to the aqueous phase include wetting agents, such as polyalcohols, such as glycerol,
Propylene glycol, sorbitol and/or
or polyethylene glycol, and preservatives,
This includes fragrances and the like. Oily ointments are anhydrous and contain especially hydrocarbons as a base, such as paraffin, petroleum jelly and/or liquid paraffin, and also natural or partially synthetic fats, such as coconut fatty acid triglycerides, or preferably hydrogenated oils, such as , hydrated peanut or castor oil, and also fatty acid partial esters of glycerol, such as glycerol mono- and distearates, and, for example, fatty alcohols, said emulsifiers used in ointments and/or additives to increase water absorption. contains. Pastes are creams and ointments containing powdered ingredients that absorb secretions, such as metal oxides, such as titanium oxide or zinc oxide, and talc and/or aluminum silicates, the purpose of which is to absorb moisture present or secretions. ). The foam is dispensed from a pressurized dispenser and is a liquid o/w emulsion in aerosol form, which emulsion contains a halogenated hydrocarbon used as propellant, e.g. , chlorofluoro-lower alkanes, such as dichlorodifluoromethane and dichlorotetrafluoroethane. In the oil phase, inter alia, hydrocarbons such as paraffin oil, fatty alcohols such as cetyl alcohol, fatty acid esters such as isopropyl myristate, and/or other waxes are used. As emulsifiers, among others,
Mixtures of emulsifiers with predominantly hydrophilic properties, such as polyoxyethylene sorbitan fatty acid esters (Tweens), and those with predominantly lipophilic properties, such as sorbitan fatty acid esters (Spanz), are used.
Furthermore, customary additives such as preservatives and the like are used. Tinctures and solvents are usually aqueous ethanol based, to which polyalcohols such as glycerol, glycols, and/or polyethylene glycols are added, inter alia, as wetting agents to reduce water loss, and, for example, lower polyethylene glycols. Lipophilic substances soluble in the aqueous mixture, such as fatty acid esters, i.e. as replacement components for the fatty components removed from the skin by ethanol, and, if necessary, other adjuvants and Additives are added. Pharmaceutical compositions for topical application can be prepared by known methods,
For example, it can be obtained, if desired, by dissolving or suspending the active ingredient in the base or in a part thereof. When the active ingredient is in the form of a solution, it is usually dissolved in one of the two phases before emulsification, and when the active ingredient is in the form of a suspension, it is usually dissolved in one of the two phases before emulsification. mix,
Then add to the remaining ingredients. The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, parts and percentages are expressed by weight, and pressure is in millibar (mbar). Manufacturing Examples Example 1 Formula: 2-[p-(phenoxy)phenyl] represented by
-2-[1-(1H-1,2,4-triazolyl)
Production of methyl]-4-methyl-1,3-dioxane (a) following formula: The intermediate represented by: 2-[p-(phenoxy)phenyl]-2-bromomethyl-4
-Preparation of methyl-1,3-dioxane 10 parts of 2-[p-(phenoxy)phenyl]-2-oxy-1-bromoethane and 4 parts of 1,3-butanediol were dissolved in 40 ml of anhydrous toluene as a catalyst. - Heating under reflux for 3 hours in the presence of 0.2 part of toluenesulfonic acid, during which time the water of reaction is removed in a water separator. The reaction mixture is cooled to room temperature, washed twice with 20 ml of water, dried over sodium sulfate and filtered. The solvent is removed by evaporation and the crude product is recrystallized from isopropanol to give colorless crystals, melting point 96°-109°C. (b) Manufacture of the final product Sodium salt of 1,2,4-triazole
3.3 parts and a catalytic amount of potassium iodide in 40 ml of dimethyl sulfoxide, the 2-
Stir with 10.2 parts of [p-(phenoxy)phenyl]-2-bromomethyl-4-methyl-1,3-dioxane at a temperature of 120 DEG C. for 30 hours. The reaction mixture was cooled to room temperature, then 300 ml of water
and extract three times with 30 ml each of ethyl acetate. Combine the extracts and wash twice with 20 ml of water.
Dry over sodium sulfate, filter and remove the solvent by evaporation. This oily residue is purified by column chromatography on silica gel using ethyl acetate as solvent. The eluate is removed by evaporation and the oily residue is recrystallized from petroleum ether to give brownish crystals with a melting point of 99.5°-101°C. Example 2 Formula: Production of 2-[p-(4-chloro-2-methylphenoxy)phenyl]-2-(1-imizolylmethyl)-4-methoxymethyl-1,3-dioxolane represented by 2-[p-(4-chloro- 2-methylphenoxy)phenyl]-2-(1-imidazolylmethyl)
-4-hydroxymethyl-1,3-dioxolane
16 parts to 150 ml of N,N-dimethyl formamide
Then dissolve in 55% sodium hydride dispersion
Add 1.9 parts with stirring while introducing nitrogen gas.
The mixture was heated to 80°C for 2 hours, then cooled to room temperature and heated to 6.3 methyl iodide over 1 hour with stirring.
1 part dropwise, then heated at 60°C for 2 hours, and soaked in ice water at 800°C.
ml and extracted three times with 300 ml of ethyl acetate. Combine the extracts and wash twice with 50 ml of water.
Dry over sodium sulfate, filter and remove the solvent by evaporation. This residue was mixed with acetone/
Purify by column chromatography on silica gel with ethyl acetate (1:1) as solvent. The eluting solvent is then distilled off and the resulting mixture of diastereoisomers is recrystallized by treatment with hexane to yield beige crystals having a melting point of 92°-106°C. Example 3 Formula: 2-[p-(2-nitro-4-trifluoromethylphenoxy)phenyl]-2-(1-
Production of 2-(p-hydroxyphenyl)-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane in 300 ml of dimethyl sulfoxide. When 1.84 parts of powdered potassium hydroxide is added to this solution, the temperature rises from 23° to 36°C. 70
After heating for 2 hours at °C, dimethyl sulfoxide
100 ml of 7.4 parts of 4-chloro-3-nitrobenzotrifluoride are added dropwise and stirring is continued at 70°C for 3 hours. The reaction mixture was cooled to room temperature and watered with 2
and extracted twice with 200 ml each of diethyl ether. The combined extracts are washed twice with 70 ml each of water, dried over sodium sulphate and the solvent is removed by evaporation. This oily residue is
Purify by column chromatography on silica gel using ethyl acetate as a solvent. When this eluate is removed by evaporation, a mixture of stereoisomers remains as a residue in the form of a viscous mass. Example 4 The following formula: 2-[p-(3-chlorophenoxy) represented by
phenyl]-2-(1-imidazolylmethyl)-4
-Synthesis of ethyl-1,3-dioxolane 1.2 parts of imidazolone sodium salt, 2-[p-
4 parts of (3-chlorophenoxy)phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane and a catalytic amount of potassium iodide are stirred in 50 ml of dimethylformamide at a temperature of 125 DEG C. for 17 hours.
Cool the brown reaction mixture to room temperature and add 150 ml of water.
and extracted three times with 50 ml each of ethyl acetate. The extract is condensed, washed twice with 50 ml of water each time, and dried over sodium sulfate. The solvent is removed by evaporation and the crude product is chromatographed on a 35 cm column of silica gel eluted with acetone/ethyl acetate (1:1). This eluate is removed by evaporation and the oily residue is crystallized from petroleum ether, resulting in a melting point of
A slightly yellowish crystalline product having a temperature of 69-71°C is obtained. Example 5 The following formula: 2-[p-(4-chlorophenoxy) represented by
phenyl]-2-(1-imidazolylmethyl)-4
-Production of ethyl-1,3-dioxolane (a) Synthesis of intermediate (α) Following formula: 2-[p-(4-chlorophenoxy)phenyl]-2-methyl-4-ethyl-
Preparation of 1,3-dioxolane 37 parts of 4-(p-chlorophenoxy)acetophenone, 18 parts of 1,2-butanediol and 2 parts of p-toluenesulfonic acid as a catalyst were placed in 400 ml of anhydrous toluene on a water separator. hand,
Heat under reflux for 14 hours. The reaction mixture was cooled to room temperature, washed twice with 400 ml of water,
Dry with sodium sulfate and filter.
The solvent is removed by evaporation and the crude product is purified on a 1 m column of silica gel eluted with ligroin/hexane/ethyl acetate/toluene (5:3:1:1). This gives the product in the form of a slightly yellowish oil; n _D ²² : 1.5527. (β) The following formula: Production of 2-[p-(4-chlorophenoxy)phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane represented by (α) c) 36.8 parts of phenyl]-2-methyl-4-ethyl-1,3-dioxolane are heated to boiling temperature in 350 ml of chloroform.
While irradiating with a 150 watt spot lamp,
A solution of 19.4 parts of bromine in 50 ml of chloroform is added dropwise and the reaction mixture is subsequently heated under reflux for 2 hours, the reaction mixture is cooled to room temperature and then washed twice with 200 ml of water and treated with sodium sulfate. Dry and strain. The solvent is then removed with a water pump. This crude product was dissolved in 1 m of silica gel using toluene as a solvent.
Purify by chromatography on a column. This product has a refractive index n _D
²³ : Obtained in oily form with 1.5803. (b) Synthesis of the final product 4.4 parts of imidazole sodium salt, a catalytic amount of potassium iodide and the 2-[p
-(4-chlorophenoxy)-phenyl]-2-
14.7 parts of bromomethyl-4-ethyl-1,3-dioxolane are stirred in 80 ml of dimethylformamide at a bath temperature of 125° C. for 17 hours. The reaction mixture is cooled to room temperature, then poured into 600 ml of water and extracted three times with 200 ml of ethyl acetate. The combined extracts are washed twice with 200 ml each of water, dried over sodium sulfate and filtered. The solvent is then removed by evaporation and the oily residue is chromatographed on a 50 cm column of silica gel with acetone/ethyl acetate (1:1) as solvent. The solvent in this eluate is removed by evaporation to obtain the desired product in the form of a brown oil with a refractive index of 1.5750. Example 6 The following formula: 2-[p-(phenoxy)phenyl] represented by
-2-(1H-1,2,4-triazolylmethyl)
Synthesis of -4-ethyl-1,3-dioxolane 2-[p-(phenoxy)phenyl]-3-bromomethyl-4-ethyl-1,3-dioxolane 17
8.4 parts of potassium carbonate, 4.2 parts of 1,2,4-triazole and a catalytic amount of sodium iodide in 100 ml of dimethylformamide at a temperature of 125°C.
Stir for an hour. The reaction mixture was cooled to room temperature, then poured into 600 ml of water and ethyl acetate.
Extract 3 times with 200ml each. The extract was concentrated, washed several times with 200 ml of water, dried over sodium sulfate, and filtered. The solvent was removed by evaporation and the oily residue was washed with 50 cm of silica gel solvated with chloroform/ether (1:1).
Subject to chromatography using a column. The solvent in this eluate is removed by evaporation and the oily residue is crystallized from petroleum ether to yield the product in the form of white crystals with a melting point of 81.5°-83.5°C. Example 7 The following formula: 2-[p-(phenoxy)phenyl] represented by
-2-(1H-1,2,4-triazolylmethyl)
-Synthesis of 1,3-dioxane 14 parts of 2-[p-(phenoxyphenyl)]-2-bromomethyl-1,3-dioxane, potassium carbonate
7.2 parts of dimethylformamide, 3.6 parts of 1,2,4-triazole, and potassium iodide catalyst amount.
ml for 20 hours at a temperature of 140°C. The reaction mixture was cooled to room temperature, diluted with 600 ml of water,
Then extract three times with 200 ml of ether each time. Combine these extracts and wash twice with 200ml of water each time.
Dry with sodium sulfate and filter. The solvent is evaporated and the oily residue is chromatographed on a 5 cm column of silica gel with chloroform/ether (1:1) as solvent. Evaporation of the solvent of this eluate and crystallization of the residue from petroleum ether gives the product in the form of white crystals with a melting point of 129°-130°C. Example 8 2-[p-(phenoxy)phenyl] represented by
-2-(1H-1,2,4-triazolylmethyl)
Synthesis of -4-hydroxymethyl-1,3-dioxane 2-[p-(phenoxy)phenyl]-2-bromomethyl-4-hydroxymethyl-1,3-dioxolane 4.5 parts, potassium carbonate 2.2 parts, 1,2, 4
- 1.1 parts of triazole and potassium iodide catalyst,
Stir in 50 ml of dimethyl sulfoxide at a temperature of 140° C. for 4 hours. The reaction mixture is cooled to room temperature, poured into 600 ml of water and extracted twice with 200 ml of ethyl acetate. The combined extracts are washed twice with 200 ml each of water, dried over sodium sulfate and filtered. The solvent is evaporated and the oily residue is chromatographed on a 50 cm column of silica gel with acetone as solvent. Evaporation of the solvent and crystallization of the oily residue from petroleum ether gave a melting point of 111°-112°C.
The product is obtained in beige crystalline form. Example 9 The following formula: 2-[p-(phenoxy)phenyl] represented by
-2-(1H-1,2,4-triazolylmethyl)
Synthesis of -4-n-propyl-1,3-dioxolane 1-(p-phenoxyphenyl)-2-(1,3,
10.3 parts of nitrate of 4-triazolyl)-ethanone,
6.1 parts of 1,2-pentanediol, 6.9 parts of p-toluenesulfonic acid, 20 parts of 1-pentanol and 200 parts of xylene are heated under reflux on a water separator for 6 days. The reaction mixture is then cooled to room temperature and washed twice with 200 ml each of dilute sodium hydroxide solution and twice with 200 ml each of water. The organic phase is dried over sodium sulfate and filtered. The solvent is evaporated and the oily residue is chromatographed on a 1 m column of silica gel with ethyl acetate as solvent. When the solvent in this eluate is evaporated, an oily residue gradually crystallizes and its melting point
The product is obtained in beige crystalline form at 68.5°-71°C. Example B1 The following formula: 2-[(2-methyl-4-phenoxy)-phenyl]-2-(1-imidazolylmethyl) represented by
Synthesis of -4-ethyl-1,3-dioxolane (a) The following formula: Synthesis of 2-methyl-4-phenoxy-phenacyl bromide, an intermediate represented by 36.6 parts of 2-methyl-4-phenoxy-acetophenone was dissolved in 160 ml of acetic acid and heated to 35°C.
Thereafter, 25.9 parts of bromine was added dropwise over 1.5 hours, and stirring was continued for an additional hour. Pour the reaction mixture into ice water.
and extract twice with 100 ml of ethyl ether. After washing the combined extracts with water, drying over sodium sulfate, filtration and evaporation of the solvent, the oily residue is crystallized from n-hexane, mp 60-61
℃ brown crystals are obtained. (b) The following formula: Intermediate represented by 2-[(2-methyl-4-
phenoxy)-phenyl]-2-bromomethyl-
Production of 4-ethyl-1,3-dioxolane 85.4 parts of 2-methyl-4-phenoxyphenacyl bromide and 25.2 parts of 1,2-butanediol
1 part is dissolved in 250 ml of anhydrous toluene in the presence of a catalytic amount (1 part) of P-toluenesulfonic acid.
The reaction mixture is refluxed for 24 hours on a water separator.
The reaction mixture is then cooled to room temperature, washed three times with 250 ml of water, dried over sodium sulfate and filtered. Evaporation of the solvent gives the product as a reddish-brown oil. (c) Synthesis of final product 9.5 parts of 2-[(2-methyl-4-phenoxy)-phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane obtained in (b), 2.4 parts of imizodal and 4.0 parts of potassium tert-butyrate in 50 ml of dimethyl sulfoxide at a temperature of 110°C.
Stir for 30 hours. Cool the reaction mixture to room temperature,
After diluting with 300 ml of water, extract three times with 150 ml of ethyl acetate. The combined extracts are washed neutral with water, dried over sodium sulfate and filtered. After distilling off the solvent, the crude product is purified on a 50 cm column of silica gel using ethyl acetate. The product is obtained as a reddish oil. ^n50D _: 1.5550. Example B2 Formula: 2-[p-(phenoxy)-phenyl] represented by
-2-[1-(1H-1,2,4-triazolyl)
Production of methyl]-1,3-dioxolane 2-[p-(phenoxycarbonyloxy)-phenyl]-2-(1-(1H-1,2,4-triazolyl)methyl)-1,3-dioxolane 11 parts in 200 ml of ethylene glycol diethyl ether, 130
Heat at a temperature of °C until carbon dioxide evolution stops (approximately 10 hours). Thereafter, the solvent is distilled off under reduced pressure. The oily crude product is cooled to room temperature, dissolved in 500 ml of diethyl ether, washed twice with 100 ml of water, dried over sodium sulphate and filtered. The solvent is distilled off. Recrystallization of the crude product from an ethyl acetate/cyclohexane solution in the presence of activated carbon gives a melting point of 100~
Colorless crystals at 102°C are obtained. Example B3 The following formula: 2-[p-(phenoxy)-phenyl] represented by
-2-[1-(1H-1,2,4-triazolylmethyl)-4-(p-chlorobenzyloxymethyl)
Preparation of A- and B-diastereoisomers of 1,3-dioxolane 2-[p-(phenoxy)-phenyl]-2-(1H
A solution of 14.1 parts of -1,2,4-triazolylmethyl)-4-hydroxymethyl-1,3-dioxolane dissolved in 100 ml of anhydrous dioxane and sodium hydride dispersed in 100 ml of anhydrous dioxane were prepared.
1.8 parts of the 55% dispersion are stirred at room temperature while nitrogen is introduced. The mixture is heated at 80 DEG C. for 3 hours, then cooled to room temperature, and a solution of 8.6 parts of p-chlorobenzyl bromide in 50 parts of anhydrous dioxane is added dropwise over the course of 30 minutes. The reaction mixture is heated at 50° C. for 3 hours, cooled to room temperature, diluted with 1200 ml of ice water and extracted three times with 200 ml each of ethyl acetate. The combined extracts are washed twice with 70 ml of water, dried over sodium sulfate, filtered and the solvent is evaporated. The remaining diastereoisomers are separated by column chromatography (silica gel/ethyl acetate).
The elution solvent was distilled off to obtain diastereoisomer B.
is obtained as crystals with a melting point of 83-85°C. Diastereoisomer A is obtained as a viscous, slightly brown oil by distilling off the elution solvent; n ²⁶ _D : 1.5865. Example B4: The following formula: 2-[p-(4-chlorophenoxy) represented by
-2-methylphenyl]-2-[1-(1H-1,
2,4-triazolyl)-methyl]-4-ethyl-
Production of 1,3-dioxolane 2-[p-(4-chlorophenoxy)-2-methylphenyl]-2-bromomethyl-4-ethyl-
30 parts of 1,3-dioxolane, 13.3 parts of sodium salt of 1,2,4-triazole and 1 part of sodium iodide in ml of hexamethylphosphoric triamide at 80°C.
Stir for 24 hours at a temperature of . After the reaction mixture has been cooled to room temperature, it is poured into 600 ml of water and extracted three times with 300 ml of ethyl acetate. The combined organic layers are washed with water until neutral, dried over sodium sulfate and filtered. The solvent is evaporated and the oily residue is column chromatographed on 50 cm of silica gel, eluting with ethyl acetate to give the product as a brown resin. ^n22D _: 1.5718. Example B5 The following formula: 2-[p-(4-chlorophenoxy) represented by
-2′-methylphenyl]-2-[1-(1H-1,
2,4-triazolyl)-methyl]-4-methyl-
Production of 1,3-dioxolane 2-[p-(4-chlorophenoxy)-2-methylphenyl]-2-bromomethyl-4-methyl-
51.4 parts of 1,3-dioxolane, 24.2 parts of sodium salt of 1,2,4-triazole and 0.8 parts of sodium iodide were mixed in 150 ml of sulfolane at a temperature of 220°C.
Stir for an hour. After cooling the reaction mixture to room temperature,
Pour into 300 ml of water and extract three times with 250 ml each of ethyl acetate. The combined organic layers are washed twice with 200 ml of water, dried over sodium sulfate and filtered. The solvent is evaporated under reduced pressure and the oily residue is subjected to column chromatography on silica gel, eluting with ethyl acetate.
When the elution solvent is distilled off, a mixture of diastereoisomers is obtained as a viscous product. ^n50D _:
1.5600 Example B6 The following formula: 2-[p-(4-trifluoromethylphenoxy)phenyl]-2-[1-(1H-1,
2,4-triazolyl)-methyl]-4-ethyl-
Production of 1,3-dioxolane Sodium salt of 1,2,4-triazole 7.4
2-[p-(4-trifluoromethylphenoxy)phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane in 150 ml of dimethylsulfoxide at a temperature of 100°C.
Stir with 27 parts. After cooling, pour the brown reaction mixture into 800 ml of water,
Extract 3 times with 200 ml of ethyl acetate. The combined organic layers are washed twice with 500 ml of water, dried over sodium sulfate and filtered. The solvent was distilled off, leaving an oily residue at 70%
The mixture was subjected to column chromatography on silica gel (cm) and developed with chloroform/ether (1:1). When the elution solvent is distilled off, the product has a melting point of 106−
Obtained as white crystals at 107°C. Example B7 The following formula: 2-[p-(4-chlorophenoxy) represented by
-2-chlorophenyl]-2-[[1-(1H-1,
2,4-triazolyl)-methyl]-4-ethyl-
Production of 1,3-dioxolane 2-[p-(4-chlorophenoxy)-2-chlorophenyl]-2-bromomethyl-4-ethyl-
5.4 parts of 1,3-dioxolane, 2.3 parts of sodium salt of 1,2,4-triazole, and a catalytic amount of sodium iodide were mixed with 20 parts of hexamethylphosphoric triamide.
Stir for 12 hours at a temperature of 160 °C in ml. After the reaction mixture has been cooled to room temperature, it is poured into 150 ml of water and extracted three times with 30 ml of ethyl acetate. The combined organic layers are washed with water until neutral, dried over sodium sulfate and filtered. The solvent is evaporated and the oily residue is subjected to column chromatography on 20 cm of silica gel and developed with ethyl acetate to give the product as a thick yellow oil. n ^21.5 _D : 1.5773 Example B8 Following formula: 2-[p-(4-chlorophenoxy) represented by
Production of phenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-4-methyl-1,3-dioxolane Sodium salt of 1,2,4-triazole 8.5
part, 1 part potassium iodide and 2-[p-(4-chlorophenoxy)phenyl]-2-bromomethyl-
18 parts of 4-methyl-1,3-dioxolane were dissolved in 80 ml of hexamethylphosphoric triamide at a temperature of 50°C.
Stir for days. The brown reaction mixture is poured into 500 ml of water and extracted three times with 200 ml each of ether. The combined organic layers are washed twice with 200 ml of water, dried over sodium sulfate and filtered. Distill the solvent and leave an oily residue.
Apply column chromatography on 35 cm of silica gel and develop with chloroform/ether (1:1) solution. The eluting solvent is distilled off and the oily residue is crystallized from petroleum ether to give yellow crystals with a melting point of 81-84°C. Example B9 The following formula: 2-[p-4-chlorophenoxy] represented by
phenyl]-2-[1-(1H-1,2,4-triazolyl)-methyl-4,5-dimethyl-1,3-
Production of dioxolane Sodium salt of 1,2,4-triazole 3.6
part and catalytic amount of potassium iodide to 2-[p-
(4-chlorophenoxy)phenyl]-2-bromomethyl-4,5-dimethyl-1,3-dioxolane with 8 parts of hexamethylphosphoric acid triamide 30 ml
Stir for 10 days at a temperature of medium 20 °C. The brown reaction mixture is diluted with 150 ml of water and extracted three times with 100 ml each of ethyl acetate. The combined organic layers were washed twice with 100 ml of water,
Dry with sodium sulfate and filter. After evaporation of the solvent and crystallization of the oily residue from ether, the melting point
Yellow crystals at 95-97°C are obtained. Example B10 The following formula: 2-[p-(4-bromophenoxy) represented by
-2-chlorophenyl]-2-[1-(1H-1,
2,4-triazolyl)-methyl]-4-methyl-
Production of 1,3-dioxolane 2-[p-(4-bromophenoxy)-2-chlorophenyl]-2-bromomethyl-4-methyl-
15.6 parts of 1,3-dioxolane, 6.2 parts of the sodium salt of 1,2,4-triazole and 0.3 parts of iodine were dissolved in 150 ml of 1-methyl-2-pyrrolidone.
Stir for 16 hours at a temperature of °C. After the reaction mixture was cooled to room temperature, it was diluted with 250 ml of water and 200 ml each of ethyl acetate.
Extract once in ml. The combined organic layers are washed with water until neutral, dried over sodium sulfate and filtered. The solvent was evaporated and the oily residue was subjected to column chromatography on silica gel and developed with ethyl acetate. Taking care of the elution solvent, a mixture of diastereoisomers is obtained as a viscous product. : n ^22.5 _D : 1.5897 Example B11 The following formula: 2-[p-(4-chlorophenoxy) represented by
-2-chlorophenyl]-2-[1-(1H-1,
2,4-triazolyl)-methyl]-4-methyl-
Production of 1,3-dioxane 2-[p-(4-chlorophenoxy)-2-chlorophenyl]-2-bromomethyl-4-methyl-
15 parts of 1,3-dioxane, 6.4 parts of the sodium salt of 1,2,4-triazole and a catalytic amount of sodium iodide are stirred in 50 ml of sulfolane at a temperature of 200 DEG C. for 7 hours. After cooling the reaction mixture to room temperature, add water
Pour into 200 ml and extract three times with 70 ml each of ethyl acetate.
The combined organic layers are washed with water until neutral, dried over sodium sulfate and filtered. Distill the solvent,
The oily residue is subjected to column chromatography on 25 cm of silica gel and developed with ethyl acetate. The eluting solvent is distilled off and the oily residue is crystallized from petroleum ether to give white crystals with a melting point of 104-106°C. Example B12 The following formula: 2-[p-(4-bromophenoxy) represented by
phenyl]-2-[1-(1H-1,2,4-triazolyl)-methyl]-4-n-propyl-1,3-
Production of dioxolane Sodium salt of 1,2,4-triazole 6.5
1 part of potassium iodide and 25 parts of 2-[p-(4-bromophenoxy)phenyl]-2-promomethyl-4-n-propyl-1,3-dioxolane in 150 ml of dimethyl sulfoxide at a temperature of 90°C for 60 minutes.
Stir for an hour. After cooling the reaction mixture to room temperature,
Pour into 800 ml of water and extract three times with 250 ml each of ethyl acetate. The combined organic layers are washed twice with 200 ml of water, dried over sodium sulfate and filtered. Distill the solvent,
The oily residue is subjected to column chromatography on silica gel and developed with chloroform/ether (1:1). The solvent is evaporated and the oily residue is crystallized from petroleum ether to give yellow crystals with a melting point of 81-83°C. Example B13 The following formula: 2-[p-(4-chlorophenoxy) represented by
Production of phenyl]-2-[1-(1H-1,2,4-triazolyl)-methyl]-4-methyl-1,3-dioxolane 2-[p-(4-chlorophenoxy)phenyl]
11.9 parts of -2-bromomethyl-4-methyl-1,3-dioxane, 3.1 parts of sodium salt of 1,2,4-triazole, 6.2 parts of sodium carbonate and 0.5 part of potassium iodide in 50 ml of dimethyl sulfoxide
Stir for 85 hours at a temperature of °C. After cooling the brown reaction mixture to room temperature, it was poured into 300 ml of water and diluted with ether.
Extract 3 times with 100ml. The combined organic layers are washed twice with 100 ml of water, dried over sodium sulfate and filtered. The solvent was evaporated and the oily residue was subjected to column chromatography on 40 cm of silica gel and developed with ethyl acetate. On evaporation of the solvent, a mixture of diastereoisomers is obtained as a viscous product: n ²⁵ _D : 1.5748 Example B14: 2-[p-(4-bromophenoxy) represented by
-2-chlorophenyl]-2-[1-(1H-1,
2,4-triazolyl)-methyl]-4-methyl-
Production of 1,3-dioxolane 2-[p-(4-bromophenoxy)-2-methylphenyl]-2-bromomethyl-4-ethyl-
13.9 parts of 1,3-dioxolane, 5.3 parts of sodium salt of 1,2,4-triazole and 0.2 parts of sodium iodide in 30 ml of 1-methyl-2-pyrrolidone.
Stir for 12 hours at a temperature of 155 °C. After the reaction mixture was cooled to room temperature, it was poured into 200 ml of water and added with ethyl acetate.
Extract 3 times with 100ml. The combined organic layers are washed with water until neutral, dried over sodium sulfate and filtered. The solvent is evaporated and the oily residue is subjected to column chromatography on silica gel and developed with ethyl acetate to give the product as a yellow resin.
n ²⁰ _D : 1.5778 Example B15 Following formula: 2-[p-(4-chlorophenoxy) represented by
-2-chlorophenyl]-2-[1-(1H-1,
Production of 2,4-triazolyl)-methyl]-4-n-propyl-1,3-dioxolane 2-[p-(4-chlorophenoxy)-2-chlorophenyl]-2-bromomethyl-4-n-propyl -1,3-dioxolane 3.7 parts, 1,2,4
- 1.5 parts of the sodium salt of the triazole and 0.1 part of sodium iodide are stirred in 25 ml of hexamethylphosphoric triamide at a temperature of 170 DEG C. for 14 hours. After the reaction mixture has been cooled to room temperature, it is poured into 100 ml of water and extracted twice with 40 ml each of ethyl acetate. The combined organic layers are washed with water until neutral, dried over sodium sulfate and filtered. The solvent is evaporated and the oily residue is subjected to column chromatography on silica gel and developed with ethyl acetate to give the product as a yellow resin. n ²¹ _D : 1.5707 Compounds of the formula shown below can also be produced by similar methods. (Unless otherwise specified, mixtures of diastereoisomers shall have various mixing ratios.) In the table below, "A" indicates the above-mentioned type A diastereoisomer, and "B" indicates the above-mentioned type B diastereoisomer. Indicates stereoisomers.

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[Table] Formulation example Formulation example for agricultural chemicals containing a liquid active ingredient represented by the formula (% is expressed by weight) (10) Emulsion stock solution

[Table] By diluting the emulsion stock solution with water, an emulsion with a desired concentration can be produced. (11) Solution agent

[Table] These solutions are suitable for application in the form of microdroplets. (12) Granules

[Table] The active ingredient is dissolved in methylene chloride, this solution is sprayed onto the carrier, and the solvent is subsequently distilled off under reduced pressure. (13) Powder

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[Table] By uniformly mixing the active ingredient and carrier, a powder that can be used as is is obtained. Examples of formulations for agricultural chemicals containing solid active ingredients represented by the formula (% expressed by weight) (14) Wettable powders

[Table] After thoroughly mixing the active ingredient with the auxiliary agent,
Thoroughly grinding the mixture in a suitable mill gives a wettable powder which can be diluted with water to obtain a suspension of the desired concentration. (15) Emulsion stock solution (a) Active ingredients in Tables 1 to 10 10% Octylphenol polyethylene glycol ether (4 to 5 moles of ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (36 moles of ethylene oxide) 4% Cyclohexane 30% xylene mixture 50% By diluting this emulsion stock solution with water, an emulsion of a desired concentration can be obtained. (16) Powder

[Table] By mixing the active ingredient with the carrier and milling the mixture in a suitable mill, a ready-to-use powder was obtained. (17) Extruded granules (a) Active ingredients listed in Tables 1 to 10 10% Sodium ligninsulfonate 2% Carboxymethylcellulose 1% Kaolin 87% The active ingredients are mixed and ground with the auxiliary agents, and then this mixture is mixed with water. Moisten. The mixture is extruded and dried in a stream of air. (18) Coated granules Active ingredients in Tables 1 to 10 3% Polyethylene glycol MG200 3% Kaolin 94% (MG represents molecular weight) Finely ground active ingredients were mixed in a mixer.
Apply evenly to kaolin moistened with polyethylene glycol. This method results in dust-free coated granules. (19) Active ingredients in suspension concentrate Tables 1 to 10 40% Ethylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6% Sodium lignin sulfonate 10% Carboxymethyl cellulose 1% 37% formaldehyde aqueous solution 0.2% 75% aqueous Emulsion type silicone oil 0.8% Water 32% A suspension concentrate is obtained by uniformly mixing the finely ground active ingredient with auxiliary agents and diluting with water to obtain a suspension of the desired concentration. Formulation Example for Pharmaceutical Preparation (20) Ointment An ointment containing 5% of 2-[p-(4-chlorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-dioxolane was prepared as follows. Composition: Active ingredients 5.0% Petrolatum 45.0% Paraffin oil 19.6% Cetyl alcohol 5.0% Beeswax 5.0% Sorbitan sesquioleate 5.0% p-hydroxybenzoic acid ester 0.2% Make up to 100.0% with demineralized water Fat and emulsifier melt together. The prophylactic drug is dissolved in water and this solution is emulsified in a fat melt at high temperature. After cooling, a suspension of the active ingredient in a portion of the fat melt is mixed into the emulsion. (21) Cream 2-[p-(chlorophenoxy)phenyl]-
2-(1-imidazolylmethyl)-4-ethyl-
A cream containing 10% of 1,3-dioxolane is obtained as follows: Composition Active ingredients 10.0% Isopropyl palmitate 8.0% Cetyl palmitate 1.5% Silicone oil 100 0.5% Sorbitan monostearate 3.0% Polysorbate 60 3.5 % 1,2-propylene glycol PH 20.0% Acrylic acid polymer 0.5% Triethanolamine 0.7% Make up to 100.0% with demineralized water. The acrylic acid polymer is suspended in a mixture of demineralized water and 1,2-propylene glycol. It is then stirred into a mucilage in triethanolamine. Next, a mixture of isopropyl palmitate, cetyl palmitate, silicone oil, sorbitan monostearate and polysorbate is heated to about 75°C and added into the viscous mass with stirring, again about
Heat to 75°C. After cooling it to room temperature, the cream base is used to prepare a concentrate containing the active ingredient. This concentrate is homogenized continuously using a homogenizer and then added to the base in portions. 2-[p-(chlorophenoxy)phenyl]-
2-(1-imidazolylmethyl)-4-ethyl-
A cream containing 5% of 1,3-dioxolane is obtained as follows: Composition Active ingredients 5.0% Cetyl palmitate PH 2.0% Cetyl alcohol PH 2.0% Triglyceride mixture of saturated medium fatty acids 5.0% Stearic acid 3.0% Glycerol Stearate PH 4.0% Cetomacrogol 1000 1.0% Microcrystalline cellulose 0.5% 1,2-propylene glycol (distillate)
20.0% Make 100.0% with demineralized water. Melt together the cetyl alcohol, cetyl palmitate, triglyceride mixture, stearic acid and glycerol stearate. Disperse microcrystalline cellulose in a portion of water. Dissolve the cetomacrogol in the remaining water and mix with it both the propylene glycol and the mucilage. The fat phase is then stirred into the aqueous phase and the mixture is stirred and cooled. Finally, the active ingredient is kneaded with a portion of this base and then incorporated into the rest of the cream. (22) Hydrogel 2-[p-(chlorophenoxy)-phenyl]-
A transparent hydrogel containing 5% of 2-(1-imidazolylmethyl)-4-ethyldioxolane is obtained as follows: Composition Active ingredients 5% Propylene Glycol 10-20% Isopropanol 20% Hydroxypropyl Methylcellulose 2% Water Diffuse 100% hydroxymethylcellulose in water. The active ingredient is dissolved in a mixture of isopropanol and propylene glycol. This active ingredient solution is then mixed with the diffused cellulose derivative and, if desired, perfume is added. (23) Foaming spray agent 2-[p-(chlorophenoxy)phenyl]-
A foaming spray containing 1% of 2-(1-imidazolylmethyl)-4-ethyldioxolane is obtained as follows: Composition Active ingredients 1.00% Cetyl alcohol PH 1.70% Liquid paraffin (viscous) 1.00% Isopropyl myristate 2.00% Cetamacrogol 2.40% Sorbitan monostearate 1.50% 1,2-propylene glycol PH 5.00% Methyl paraben 0.18% Propyl paraben 0.02% Chemoderm 314 0.10% Make up to 100.00% with demineralized water Cetyl alcohol, Liquid paraffin, isopropyl myristate, cetomacrogol and sorbitan stearate are melted together. Dissolve methyl and propylparaben in warm water. The melt and solution are then mixed. A suspension of the active ingredient in propylene glycol is incorporated into the base.
Chemoderm is then added and water is added to the composition to bring it to a final weight. Filling Fill 20 ml of the composition into an aluminum dispenser. A pressure cap is attached to this dispenser and it is filled with pressurized foaming gas. (24) Capsules Gelatin capsules containing 200 mg of [p-(phenoxy)phenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-1,3-dioxane as the active ingredient are as follows. Obtained as follows: Composition (for 1000 capsules) Active ingredient 100 g Lactose (ground) 100 g Active ingredient and lactose (ultra-finely ground) are mixed thoroughly. The resulting powder was sieved and 0.2g
encapsulated in gelatin capsules. (25) Tablet Active ingredient, for example, 2-[p-(phenoxy)phenyl]-2-[1-(1H-1,2,4-
triazolyl)methyl]-1,3-dioxane
Tablets containing 25 mg are obtained as follows: Composition (for 1000 tablets) Active ingredients 25.0 g Lactose 100.7 g Starch 7.5 g Polyethylene Glycol 6000 5.0 g Talc 5.0 g Magnesium stearate 1.8 g Demineralized water Mix thoroughly First, Pass all solid ingredients through a sieve with mesh size of 0.6 mm. Then mix together the active ingredients, lactose, talc, magnesium stearate and half the starch. The other half of the starch is suspended in 40 ml of water, this suspension is added to a boiling solution of polyethylene glycol in 1000 ml of water, and the mixture is mixed with water if necessary, Granulate. The granules are dried overnight at 35°C, passed through a 1.2 mm sieve, and compressed into biconcave tablets approximately 6 mm in diameter. Active ingredients, such as 2-[p-(phenoxy)phenyl]-2-[1-(1H-1,2,4-
triazolyl)methyl]-1,3-dioxane
Tablets containing 75 mg are obtained as follows: Composition (for 1000 tablets) Active ingredients 75.0 g Lactose 100.7 g Starch 7.5 g Polyethylene Glycol 6000 5.0 g Talc 5.0 g Magnesium stearate 1.8 g Demineralized water Mix thoroughly First, Pass all of the solid ingredients through a sieve with a mesh size of 0.6 mm. Then mix together the active ingredients, lactose, talc, magnesium stearate and half the starch. The other half of the starch was suspended in 40 ml of water, this suspension was added to a boiling solution of polyethylene glycol in 100 ml of water, and the mixture was
Add water if necessary and granulate. The granules are dried overnight at 35°C, passed through a 1.2 mm sieve, and compressed into biconcave tablets approximately 6 mm in diameter. Pharmaceutical preparations containing the other compounds listed in Tables 1 to 10 are obtained in a similar manner. Biological test example 26 Puccinia graminis of wheat
(a) Residual protective effect Wheat plants are treated 6 days after sowing with a spray mixture prepared from a hydrated preparation of the active ingredient (0.006). After 24 hours, the treated plants are infected with a suspension of fungal diaspores. Plants infected with the fungus are incubated at a relative humidity of 95-100% and approximately 20°C.
Incubate for 48 hours, then store in a greenhouse at approximately 22℃
Leave it there. Evaluate the spread of mildew on 12 days after infection. (b) Osmotic action Wheat plants are treated 5 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.06% by volume of soil). After 48 hours, the treated plants are infected with a suspension of fungal diaspores. The plant body is kept at a relative humidity of 95-100%, about 20%
Incubate for 48 hours at
Leave at 22℃. Evaluate the spread of rust warts 12 days after infection. The compounds in Tables 1 to 10 are highly effective against Psinia. Psinia infection is 100% in untreated control plants. In particular, compound 1.9,
1.17, 1.24, 1.26, 2.17, 3.1, 3.2, 3.6 or 3.8,
3.12, 3.26, 3.51, 3.52, 3.54, 3.55, 3.70, 3.75,
3.78, 3.83, 3.85, 3.86, 3.127, 3.133, 3.155,
3.156, 3.160, 3.162, 3.164, 3.168, 3.171,
3.172, 3.176, 3.177, 3.193, 3.212, 3.213,
3.220, 3.226, 3.227, 3.231 to 3.234, 3.263,
3.267, 3.274, 3.279, 3.287, 3.292, 3.311,
3.314, 3.340, 3.348, 3.373, 3.376, 3.384,
3.386, 4.2, 4.15, 4.23, 4.50, 4.55, 4.57, 4.66,
4.70, 4.77, 4.78, 4.81, 4.89 to 4.94, 4.113,
4.116, 4.136, 4.138 to 4.147, 5.13, 5.14,
5.36, 5.40, 5.70, 5.71, 5.76, 5.78, 5.105,
Residual protection treatments with 5.113, 5.117, 6.8, 6.93, 7.7, 7.33 and 8.66 suppress bacterial attack to 0-5%. Furthermore, compounds 6.8 and 6.82 exhibit sufficient penetration activity (0% attack) even when diluted to 0.006% concentration. Example 27 Effect of Cercospora arachidicola on groundnuts A spray mixture prepared from a wettable powder formulation of the active ingredient (concentration
0.002%), and 48 hours later, the bacteria are infected with a conidial suspension of the bacteria. The infected plants are incubated at approximately 21°C and high humidity for 72 hours and left in a greenhouse until typical spots appear on the leaves.
Bactericidal activity is evaluated by the number and size of spots 12 days after infection. Untreated infected control (number and size of spots =
100%), plants treated with the compounds of Tables 1 to 10 greatly reduce attack by Cercospora. For example, compounds 1.1, 1.4, 1.9,
1.14, 1.17, 1.24 or 1.27, 2.17, 3.1, 3.2,
3.6, 3.7, 3.11, 3.51, 3.52, 3.54, 3.55, 3.57,
3.78, 3.85, 3.86, 3.127, 3.133, 3.155, 3.156,
3.162, 3.171, 3.172, 3.176, 3.177, 3.212,
3.213, 3.220, 3.221, 3.226, 3.231, 3.232,
3.233, 3.234, 3.267, 3.292, 3.314, 3.348, 3.384
or 3.388, 4.15, 4.23, 4.50, 4.57, 4.59,
4.66, 4.89 to 4.94, 4.113, 4.116, 4.136 to 4.148, 5.13, 5.14, 5.36, 5.40, 5.70, 5.71,
5.73, 5.75 to 5.78, 5.105 to 5.110, 5.113
to 5.118, 6.1, 6.8, 6.93, 6.94, 7.33, 7.34 and 8.72 almost completely inhibit spot formation in this test (0 to 5% attack). Example 28 Action of barley against Erysiphegraminis (a) Residual protective action A spray mixture prepared from the active ingredient formulated as a wettable powder on barley plants approximately 8 cm in height (0.002% active ingredient) Spray. After 3 to 4 hours, the treated plants are sprinkled with conidia of the fungus. Next, the infected barley plants are left in a greenhouse at approximately 22°C. Assess the degree of infection after 10 days. (b) Osmotic action Barley plants approximately 8 cm in height are treated with a spray powder (0.006% of the soil volume) prepared from the active ingredient formulated as a hydrating powder. Be careful not to let the spray mixture touch any parts of the plant above the soil. The treated plants are infected with the fungus after 48 hours with a suspension of fungal conidia. Barley plants infected with the fungus are left in a greenhouse at approximately 22°C, and the degree of infection is evaluated after 10 days. The compound of the formula shows a good residual protective effect against Erysiphae. Control plants infected without treatment were attacked by 100% by Erysiphae. In particular, compounds 1.1, 1.4, 1.9, 1.14, 1.17, 1.23 to 1.27, 2.17, 3.1, 3.2, 3.6 to 3.8, 3.11,
3.12, 3.26, 3.51, 3.52, 3.54, 3.55, 3.70, 3.75,
3.78, 3.85, 3.86, 3.103, 3.127, 3.133, 3.156,
3.160, 3.162, 3.164, 3.168, 3.171, 3.172,
3.174, 3.176, 3.177, 3.193, 3.212, 3.213,
3.220, 3.221, 3.226, 3.227, 3.231, 3.232 or
3.234, 3.263, 3.267, 3.274, 3.279, 3.287,
3.292, 3.311, 3.314, 3.340, 3.348, 3.378, 3.383
or 3.388, 4.2, 4.15, 4.23, 4.50, 4.57, 4.59,
4.66, 4.77, 4.78, 4.81, 4.89 to 4.94, 4.113,
4.116, 4.137, 4.139, 4.140, 4.141, 4.146,
4.148, 4.150, 5.13, 5.14, 5.36, 5.40, 5.70,
5.71, 5.73, 5.75, or 5.78, 5.106 or more
5.114, 6.1, 6.8, 6.17, 6.79, 6.80, 6.82, 6.93,
7.3, 7.7, 7.21, 7.33, 7.34, 8.66, 8.69, 8.72 and 10.7 suppress bacterial attack to 5% or less. Compounds 4.50 and 6.82 are effective in soil treatment (osmotic action) and even when diluted to 0.006% concentration. Example 29 Residual protective effect against Venturia inaequalis on apple cuttings Apple cuttings with new branches 10 to 20 cm long were sprayed with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.06%) do. After 24 hours, the treated plants are infected with a conidial suspension of the fungus. Next, the plants are cultured for 5 days at a relative humidity of 90 to 100%, and then left in a greenhouse at 20 to 24°C for an additional 10 days. Assess the degree of infection with rotten disease 15 days after infection. Compounds 1.4, 1.9, 1.17, 1.24, 1.26, 2.17, 3.1,
3.6, 3.7, 3.11, 3.52, 3.55, 3.85, 3.86, 3.156,
3.160, 3.164, 3.172, 3.176, 3.177, 3.213,
3.221, 3.233, 3.314, 3.383 to 3.387, 4.15,
4.23, 4.50, 4.59, 4.66, 4.78, 4.81, 4.89, 4.90
or 4.94, 4.113, 4.116, 4.137 or 4.141,
4.146 to 4.150, 5.13, 5.14, 5.36, 5.40, 5.70,
5.73, 5.75, 5.76, 5.106 or 5.110, 5.112,
5.114, 5.118, 6.1, 6.8, 6.93, 10.7, etc. suppress infection to less than 10%. Ventiulia infection is 100% in untreated infected shoots. Example 30 Residual protective effect against Botrytis cinerea in kidney beans. Green beans plants approximately 10 cm in height are sprayed with a spray mixture (concentration 0.002%) prepared from the active ingredient formulated as a hydrating powder. After 48 hours, the plants are infected with the fungus using a suspension of fungal conidia. The infected plants should be kept at a relative humidity of 95 to 100.
%, and culture at 21°C for 3 days. The compounds listed in Tables 1 to 10 exhibit very strong inhibition of fungal infections in many cases. At a concentration of 0.02%, compounds 1.1, 1.4, 1.9, 1.17, 3.6, 3.7, 3.12,
3.51, 3.55, 3.86, 3.226, 3.231, 3.267, 3.311,
4.15, 4.50, 4.59, 4.66, 4.78, 4.90 to 4.93,,
4.113, 5.13, 5.36, 5.40, 5.70, 5.71, 5.73,
5.75, 5.76, 5.78, 6.1, 6.8, 7.3, 7.33 and 8.72
is sufficiently effective (0 to 5% attack). The degree of botrytis infection in untreated infected bean plants is 100%. Example 31 (Comparative Test Example) Comparative tests were conducted on the compounds X1 to X25 of the present invention and the compounds A to O of the prior art with respect to sterilization in plants. 1 Test Compounds 1.1 Prior Art Compounds

【table】

【table】

[Table] 1.2 Compounds of the present invention 2 Test method 2.1 Wheat Puccinia graminis
graminis) Spray solution prepared from wettable powder of active ingredient (200, 20 and 2 ppm of active ingredient) 6 days after sowing
Spray the wheat plants with. After 24 hours, the treated plants are infected with a suspension of fungal diaspores. Plants infected with fungi are kept at a relative humidity of 95 to 100.
%, cultured at about 25°C for 48 hours, and then left in a greenhouse at about 22°C. Evaluate the spread of rust warts 14 days after infection. The size and number of typical leaf spots present after the test serve as a basis for evaluating the effectiveness of the test substance. 2.2 Effect of Cercospora arachidicola on peanuts Peanut plants with a height of 10 to 15 cm are sprayed with a spray solution prepared from a wettable powder of the active ingredient (200, 20, and 2 ppm of the active ingredient). After about 12 hours, a conidial suspension of the fungus is sprayed. Plants infected with the fungus are incubated at 90% relative humidity for about 24 hours and then transferred to a greenhouse at about 22°C. Assess the extent of infection after 12 days. The size and number of typical leaf spots present after the test serve as a basis for evaluating the effectiveness of the test substance. 2.3 Residual protective effect of barley against Erysiphe graminis A spray solution prepared from a wettable powder of the active ingredient (the active ingredient,
200, 20 and 2ppm). After 3-4 hours, the treated plants are sprinkled with conidia of the fungus. Infected barley plants are transferred to a greenhouse at approximately 22°C and the degree of infection is assessed after 10 days. The typical fungal growth present on the leaves after the test serves as a criterion for evaluating the effectiveness of the test substance. 2.4 Residual protective effect against Venturia inalqualis on young apple trees.
Spray the spray solution (200, 20 and 2 ppm active ingredient). After 24 hours, the treated plants are sprayed with a conidial suspension of the fungus. Next, the plant body was heated to a relative humidity of 90
Culture at ~100% for 6 days, then another 10 days, then 20~
Leave it in a greenhouse at 24℃. After infection
Evaluate the degree of rot infection on the 15th. The size and number of typical leaf spots present after the test serve as a basis for evaluating the effectiveness of the test substance. 2.5 Evaluation scale: Sign % activity 1 >95 (complete inhibition) 3 80-95 (acceptable inhibition) 6 50-80 (insufficient inhibition) 9 <50 (no inhibition) In the above tests , was repeated three times in parallel for each test concentration. Therefore, in the following table, each symbol represents the average value of three test results. 3 Results

【table】

[Table] 4 Conclusion In the above-mentioned bactericidal tests 2.1 to 2.4 on plants, the phenoxy derivatives X1 to X25 of the present invention were
It can be seen that it exhibits significantly superior activity compared to the structurally similar phenyl derivatives A to O in the prior art.

Claims (1)

[Claims] 1. General formula: [In the formula, Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. or represents a nitro group, Ar is unsubstituted or has one or several halogen atoms, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a nitro group, and/or a CF ₃ group. thus represents a substituted phenyl group or naphthyl group, and U and V together represent the following formula: [Formula] [Formula] or [Formula] {wherein R ₁ and R ₂ independently of each other represent a hydrogen atom ,
Alkyl group having 1 to 12 carbon atoms, having 1 to 12 carbon atoms substituted with one or several halogen atoms
12 alkyl groups, phenyl groups, phenyl groups substituted with one or several halogen atoms and/or alkyl groups having 1 to 3 carbon atoms, or formula:-
Represents a group represented by CH ₂ -Z-R ₇ (wherein, Z represents an oxygen or sulfur atom, and R ₇ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 1 or 2 carbon atoms. Alkyl group having 1 to 8 carbon atoms substituted with 1 alkoxy group, alkenyl group having 3 to 4 carbon atoms, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, 1 or a phenyl group substituted with several halogen atoms, C1-C3 alkyl groups, C1-3 alkoxy groups, nitro groups and/or _CF3 groups, unsubstituted or one or represents a benzyl group substituted with several halogen atoms, an alkyl group having 1 to 3 carbon atoms and/or an alkoxy group having 1 to 3 carbon atoms), R ₃ , R ₄ and R ₅ are each independent represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms of R ₃ , R ₄ and R ₅ does not exceed 6, and R ₆ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents an alkyl group having 1 to 3 carbon atoms} Forms an alkylene bridge represented by the following formula: A compound represented by the following, and its acid addition salt and metal complex. 2 In the general formula, Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. group or nitro group, Ar represents the following formula: [Formula] or [Formula] (wherein Rc, Rd and Re each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a carbon represents an alkoxy group having 1 to 3 atoms, a nitro group or a CF ₃ group), and U and V together represent the following formula: [Formula] [Formula] or [Formula] {In the formula, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms substituted with one or several halogen atoms.
an alkyl group, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group having 1 to 3 carbon atoms, or a phenyl group of the formula:-
Represents a group represented by CH ₂ -Z-R ₇ (wherein Z represents an oxygen or sulfur atom, R ₇ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 1 or 2 carbon atoms). C1-C8 alkyl group substituted with one alkoxy group, C3-C4 alkenyl group, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, one or phenyl group substituted by several halogen atoms, C1-C3 alkyl group, C1-C3 alkoxy group, nitro group and/or _CF3 group, unsubstituted or one or more R ₃ , R ₄ and R ₅ are each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ does not exceed 6, and R ₆ represents a hydrogen atom or a carbon atom. The compound according to claim 1, which forms an alkylene bridge represented by } representing an alkyl group having 1 to 3 atoms, and its acid addition salt and metal complex. 3 In the general formula, Y represents -CH= or -N=, Ra and Rb each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and Ar represents the following formula: [ Formula] (wherein Rc, Rd and Re each independently represent a hydrogen atom, a halogen atom, CF ₃ or an alkyl group having 1 to 3 carbon atoms), and U and V represent a group represented by the above formula Compounds according to claim 2 having the meaning as defined in Claim 2, as well as acid addition salts and metal complexes thereof. 4 In the general formula, U and V together represent the following formula: [Formula] or [Formula] (However, in the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or represents an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ does not exceed 6), and Ar is Formula: [Formula] (However, in the formula, Rc, Rd and Re are mutually independent,
a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms), and Y represents -CH= or -N=; Acid addition salts and metal complexes. 5 In the general formula, Y represents -CH= or -N=, Ar represents the meaning defined in the above formula, and Ra, Rb, Rc, Rd and Re are independently of each other,
represents a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a methyl group, a methoxy group or a nitro group, and U and V together form an alkylene bridge as defined in the above formula, in which case,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other,
represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, or R ₁ is of the formula: -CH ₂ -O-R ₇
In the formula, R ₇ is an alkyl group having 1 to 3 carbon atoms, an alkyl group having 2 to 4 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 3 to 3 carbon atoms. 4. The compound according to claim 1, which represents an alkenyl group or a phenyl group, as well as acid addition salts and metal complexes thereof. 6 In the general formula, Y represents -CH= or -N=, Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a salt thereof, Ar is represented by the following formula: [Formula] (where Rc, Rd and Re are independently hydrogen atom, halogen atom, CF ₃ , alkyl group having 1 to 3 carbon atoms, or alkoxy group having 1 to 3 carbon atoms) 2. The compound according to claim 1, and its acid addition salts and metal complexes, wherein the compound represents a group represented by the following formula (representing a group), and U and V represent the meanings defined in the above formula. 7 In the general formula, Y represents -CH= or -N=, Ra and Rb each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and Ar represents the following formula: [ Formula] (In the formula, Rc, Rd and Re each independently represent a hydrogen atom, a halogen atom, CF ₃ , or a carbon atom number of 1 to 3.
represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms), and U and V together represent the following formula: [Formula] [Formula] (wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but in this case, the total number of carbon atoms in R ₃ , R ₄ and R ₅ is 6. 2. The compound according to claim 1, which forms an alkylene group represented by the formula (not exceeding 1), as well as acid addition salts and metal complexes thereof. 8 In the general formula, Y represents -CH= or -N=, Ra and Rb each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and Ar represents the following formula: [Formula] (wherein Rc, Rd and Re each independently represent a hydrogen atom, a halogen atom, CF ₃ , an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms) represents a group represented by the formula, and U and _V together represent the following formula:
A patent claim representing an alkylene group represented by an alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 or 4 carbon atoms, or a 2-propynyl group substituted with an alkoxy group having 1 or 2 carbon atoms Compounds according to item 1, as well as acid addition salts and metal complexes thereof. 9 In the general formula, Y represents -CH=, Ar represents the meaning defined in the above formula, Ra and Rb each independently represent a hydrogen atom, a methyl group, a chlorine atom or a bromine atom, Rc, Rd and Re are independently hydrogen atoms,
represents a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group, a _CF3 or a nitro group, and U and V together represent an alkylene group represented by the formula given in the above formula; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, or R ₁ has the formula: -CH ₂ OR ₇ represents a group represented by, in this case R ₇ is an alkyl group having 1 to 3 carbon atoms, or a group having 1 or 2 carbon atoms.
an alkyl group having 2 or 3 carbon atoms substituted with an alkoxy group, or an alkyl group having 3 or 4 carbon atoms;
The compound according to claim 1, which represents an alkenyl group, and its acid addition salts and metal complexes. 10 In the general formula, Y represents -CH= or -N=, Ra and Rb each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and Ar is unsubstituted or carbon an alkyl group having 1 to 3 atoms, an alkoxy group having 1 to 3 carbon atoms,
2. The compound according to claim 1, which represents a phenyl group substituted with CF ₃ or a halogen atom, and U and V have the meanings defined in the above formula, as well as acid addition salts and metal complexes thereof. 11 In the general formula, Y represents -CH= or -N=, Ra and Rb independently represent a hydrogen atom, a methyl group, a chlorine atom or a bromine atom, and Ar is unsubstituted or a halogen atom, a methyl group or represents a phenyl group substituted by CF ₃ and U and V together represent the following formula: [Formula] or [Formula] (wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ must not exceed 4) Claim 1 forming a group
Compounds described in Section 1, and their acid addition salts and metal complexes. 12 In the general formula, Y represents -CH= or -N=, Ra and Rb represent a hydrogen atom, Ar represents an unsubstituted or halogen atom, or a phenyl group substituted with a methyl group, and U and V together with the following formula: [Formula] or [Formula] (wherein R ₂ is an alkyl group having 1 to 4 carbon atoms,
For example, methyl or ethyl, hydroxy-C1-C3 alkyl, such as hydroxymethyl or 2-hydroxyethyl, or C1-C2 alkoxy-C1-C2 alkyl, 2. A compound according to claim 1, which represents a group represented by, for example, a methoxymethyl group or an ethoxymethyl group, as well as acid addition salts and metal complexes thereof. 13 2-[p-(phenoxy)phenyl]-2-
[1-(1H-1,2,4-triazolyl)methyl]
The compound according to claim 1, which is -4-methyl-1,3-dioxane or a salt thereof. 14 2-[p-(phenoxy)phenyl]-2-
[1-(1H-1,2,4-triazolyl)methyl]
The compound according to claim 1, which is -4-ethyl-1,3-dioxane or a salt thereof. 15 2-[p-(phenoxy)phenyl]-2-
[1-(1H-1,2,4-triazolyl)methyl]
The compound according to claim 1, which is -4-methyl-1,3-dioxolane or a salt thereof. 16 2-[p-(phenoxy)phenyl]-2-
[1-(1H-1,2,4-triazolyl)methyl]
The compound according to claim 1, which is -4-ethyl-1,3-dioxolane or a salt thereof. 17 2-[p-(phenoxy)phenyl]-2-
[1-(1H-1,2,4-triazolyl)methyl]
The compound according to claim 1, which is -4-methyl-5-methyl-1,3-dioxolane. 18 2-[p-(phenoxy)phenyl]-2-
[1-(1H-1,2,4-triazolyl)methyl]
The compound according to claim 1, which is -1,3-dioxane or a salt thereof. 19 2-[p-(phenoxy)phenyl]-2-
(1-imidazolylmethyl)-4-ethyl-1,3
- The compound according to claim 1, which is dioxolane or a salt thereof. 20 2-[p-(2,4-dimethylphenoxy)
phenyl]-2-(1-imidazolylmethyl)-4
-Ethyl-1,3-dioxolane or a salt thereof. 21 The compound according to claim 1, which is 2-[p-(3-chlorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane or a salt thereof. 22 The compound according to claim 1, which is 2-[p-(4-chlorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane or a salt thereof. 23 2-[p-(3-trifluoromethylphenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane or a salt thereof as described in claim 1 compound. 24 2-[p-(4-chloro-3-methylphenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane or a salt thereof according to claim 1 Compound. 25 2-[p-3,4-dichlorophenoxy)
phenyl]-2-(1-imidazolylmethyl)-4
-Ethyl-1,3-dioxolane or a salt thereof. 26 2-[p-(2,5-dichlorophenoxy)
phenyl]-2-(1-imidazolylmethyl)-4
-Ethyl-1,3-dioxolane or a salt thereof. 27 2-[p-(3,4-dichlorophenoxy)
phenyl]-2-(1-imidazolylmethyl)-4
The compound according to claim 1, which is -methoxymethyl-1,3-dioxolane or a salt thereof. 28 The compound according to claim 1, which is 2-[p-(4-fluorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane or a salt thereof . 29 2-[p-(4-fluorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-methyl-5-methyl-1,3-dioxolane or a salt thereof Claim 1 Compounds described in Section. 30 2-[p-(4-chloro-2-methyl-phenoxy)phenyl]-2-(1-imidazolylmethyl)-4-methoxymethyl-1,3-dioxolane according to claim 1 Compound. 31 2-[p-(phenoxy)phenyl]-2-
[1-(1H-1,2,4-triazolyl)methyl]
The compound according to claim 1, which is -4-hydroxymethyl-1,3-dioxolane. 32 The compound according to claim 1, which is 2-[p-(4-fluorophenoxy)phenyl]-2-(1-imidazolylmethyl-4-hydroxymethyl-1,3-dioxolane. 33 2 -[p-(4-fluorophenoxy)phenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-1,3-dioxane according to claim 1 Compound 34 2-[p-(4-chlorophenoxy)phenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-4-ethyl-1,3-dioxolane The compound according to item 1 in the range 35 2-[p-(3,4-dichlorophenoxy)
-phenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-4-methoxymethyl-1,
The compound according to claim 1, which is 3-dioxolane. 36 2-[p-(3,4-dichlorophenoxy)
-Phenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-4-ethyl-1,3-dioxolane. 37 2-[p-(phenoxy)-2-methylphenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-4-ethyl-1,3-dioxolane Compound according to item 1. 38 2-[p-(4-chlorophenoxy)-2-
Methylphenyl]-2-[1-(1H-1,2,4-
triazolyl)methyl]-4-methyl-1,3-
The compound according to claim 1, which is dioxolane. 39 Copper sulfate complex of 2-[p-(4-chlorophenoxy)-phenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-4-ethyl-1,3-dioxolane A compound according to claim 1. 40 2-[p-(4-chlorophenoxy)-2-
Methylphenyl]-2-[1-(1H-1,2,4-
triazolyl)methyl]-4-ethyl-1,3-
The compound according to claim 1, which is dioxolane. 41 2-[p-(phenoxy)-2-chlorophenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-4-ethyl-1,3-dioxolane Compound according to item 1. 42 Patent for 2-[p-(4-chlorophenoxy)-phenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-4,5-dimethyl-1,3-dioxolane A compound according to claim 1. 43 2-[p-(4-bromophenoxy)-phenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-4-ethyl-1,3-dioxolane Compound according to item 1. 44 2-[p-(phenoxy)-2-methylphenyl]-2-[1-(1H-1,2,4-triazolyl)methyl]-4-ethyl-1,3-dioxolane Compound according to item 1. 45 The compound according to claim 1, which is 2-[p-(phenoxy)-2-methylphenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane. 46 2-[p-(4-chlorophenoxy)-2-
The compound according to claim 1, which is methylphenyl]-2-(1-imidazolylmethyl)-4-methyl-1,3-dioxolane. 47 2-[p-(4-fluorophenoxy)-2
-methylphenyl]-2-(1-imidazolylmethyl]-4-methyl-1,3-dioxolane. 48 2-[p-(4-chlorophenoxy)-phenyl ]-2-[1-(1H-1,2,4-triazolyl)methyl]-4-methoxymethyl-1,3-dioxolane. 49 (A) General formula : (In the formula, Me represents a hydrogen atom or a metal cation, and Y represents -CH= or -N=) and a compound represented by the general formula: (In the formula, Ra, Rb, Ar, U and V represent the meanings defined in the following formula, and X represents a nucleophilic separating group.) and, if desired, an acid addition salt. or converting the acid addition salts obtained by such methods into free compounds, or into other acid addition salts, or the free compounds or acid addition salts obtained by these methods into metal complexes. A general formula, characterized by: [In the formula, Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. or represents a nitro group, Ar is unsubstituted or has one or several halogen atoms, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a nitro group, and/or a CF ₃ group. thus represents a substituted phenyl group or naphthyl group, and U and V together represent the following formula: [Formula] [Formula] or [Formula] {wherein R ₁ and R ₂ independently of each other represent a hydrogen atom,
Alkyl group having 1 to 12 carbon atoms, 1 carbon atom substituted with one or several halogen atoms
1 to 12 alkyl groups, phenyl groups, one or several halogen atoms and/or 1 carbon atom
-3 represents a phenyl group substituted with an alkyl group or a group represented by the formula: -CH ₂ -Z-R ₇ (wherein Z represents an oxygen or sulfur atom, and R ₇ is a hydrogen atom, a carbon atom Alkyl group having 1 to 8 carbon atoms, alkyl group having 1 to 8 carbon atoms substituted with one alkoxy group having 1 or 2 carbon atoms, alkenyl group having 3 to 4 carbon atoms, 2-propynyl group , 3-halogen-
2-propynyl group, phenyl group, one or several halogen atoms, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms,
Phenyl group substituted by nitro group and/or _CF3 group, unsubstituted or one or several halogen atoms, C1-C3 alkyl group and/or C1-C3 alkoxy group ), R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case R ₃ , R ₄ and the total number of carbon atoms in R ₅ does not exceed 6, and R ₆ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. and methods for producing acid addition salts and metal complexes thereof. 50 Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a nitro group. , Ar represents the following formula: [Formula] or [Formula] (where Rc, Rd and Re each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a C1 to 3 alkyl group; represents a group represented by the following formula: [Formula] [Formula] or [Formula] {in the formula, R ₁ and _{R 2} are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, and 1 to 12 carbon atoms substituted with one or several halogen atoms;
an alkyl group, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group having 1 to 3 carbon atoms, or a phenyl group of the formula:-
Represents a group represented by CH ₂ -Z-R ₇ (wherein Z represents an oxygen or sulfur atom, R ₇ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 1 or 2 carbon atoms). C1-C8 alkyl group substituted with one alkoxy group, C3-C4 alkenyl group, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, one or phenyl group substituted by several halogen atoms, C1-C3 alkyl group, C1-C3 alkoxy group, nitro group and/or _CF3 group, unsubstituted or one or more R ₃ , R ₄ and R ₅ are each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ does not exceed 6, and R ₆ is a hydrogen atom. or an alkyl group having 1 to 3 carbon atoms} The method according to claim 49. 51 General formula: (In the formula, Y, Ra, Rb and Ar represent the meanings defined in the following formula.) The carbonyl group in the compound represented by the following formula: (wherein U and V represent the meanings defined in the formula below) and, if desired, into an acid addition salt, or convert the acid addition salt obtained by such a method into a free compound. or into other acid addition salts, or by converting the free compounds or acid addition salts obtained by these methods into metal complexes, the general formula: [In the formula, Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. or represents a nitro group, Ar is unsubstituted or has one or several halogen atoms, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a nitro group, and/or a CF ₃ group. thus represents a substituted phenyl group or naphthyl group, and U and V together represent the following formula: [Formula] [Formula] or [Formula] {wherein R ₁ and R ₂ independently of each other represent a hydrogen atom, Alkyl group having 1 to 12 carbon atoms, substituted with 1 to 12 halogen atoms and having 1 to 12 carbon atoms
an alkyl group, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group having 1 to 3 carbon atoms, or a phenyl group of the formula:-
Represents a group represented by CH ₂ -Z-R ₇ (wherein Z represents an oxygen or sulfur atom, R ₇ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 1 or 2 carbon atoms). 1 alkyl group having 1 to 8 carbon atoms, alkenyl group having 3 to 4 carbon atoms, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, substituted with 1 alkoxy group or a phenyl group substituted with several halogen atoms, C1-C3 alkyl groups, C1-3 alkoxy groups, nitro groups and/or _CF3 groups, unsubstituted or one or represents a benzyl group substituted with several halogen atoms, an alkyl group having 1 to 3 carbon atoms and/or an alkoxy group having 1 to 3 carbon atoms), R ₃ , R ₄ and R ₅ are each independent represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ does not exceed 6, and R ₆ is a hydrogen atom. or represents an alkyl group having 1 to 3 carbon atoms} Forms an alkylene bridge represented by the following: A method for producing a compound represented by the following, and its acid addition salt and metal complex. 52 Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a nitro group. , Ar represents the following formula: [Formula] or [Formula] (where Rc, Rd and Re each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a C1 to 3 alkyl group; represents a group represented by the following formula: [Formula] [Formula] or [Formula] {in the formula, R ₁ and _{R 2} are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, and 1 to 12 carbon atoms substituted with one or several halogen atoms;
an alkyl group, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group having 1 to 3 carbon atoms, or a phenyl group of the formula:-
Represents a group represented by CH ₂ -Z-R ₇ (wherein Z represents an oxygen or sulfur atom, R ₇ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 1 or 2 carbon atoms). C1-C8 alkyl group substituted with one alkoxy group, C3-C4 alkenyl group, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, one or phenyl group substituted by several halogen atoms, C1-C3 alkyl group, C1-C3 alkoxy group, nitro group and/or _CF3 group, unsubstituted or one or more R ₃ , R ₄ and R ₅ are each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ does not exceed 6, and R ₆ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 52. The method according to claim 51, wherein the group represents an alkyl group having 1 to 3 carbon atoms. 53 In the general formula, U and V are combined to form the following formula: -CH ₂ -CH(CH ₂ ZR' ₇ )- (wherein R' ₇ is the R ₇ group defined in the following formula excluding hydrogen atoms) In order to prepare a compound representing a group represented by the general formula: _A compound _represented by _the following _formula :
Optionally in the form of a salt, e.g. formula: -Z-Me, where Z
represents a hydroxyl group or a mercapto group which may be present in the form of an oxygen or sulfur atom, Me represents a hydrogen atom or a metal cation), and the other represents a nucleophilic separating group, or X ₁ and _X2 both represent a hydroxyl group, _R7 is a hydrogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group substituted with one C1-C2 alkoxy group; an alkyl group having 3 to 4 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, a 2-propynyl group, a 3-halogen-2-propynyl group, a phenyl group, one or several halogen atoms, an alkyl group having 1 to 3 carbon atoms, Alkoxy groups having 1 to 3 carbon atoms, phenyl groups substituted by nitro groups and/or CF ₃ groups, unsubstituted or one or several halogen atoms, alkyl groups having 1 to 3 carbon atoms and/or or a benzyl group substituted by an alkoxy group having 1 to 3 carbon atoms] and, if desired, an acid addition salt or an acid obtained by such a method. General formulas characterized by converting addition salts into free compounds or other acid addition salts, or free compounds or acid addition salts obtained by these methods into metal complexes: [In the formula, Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. or represents a nitro group, Ar is unsubstituted or has one or several halogen atoms, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a nitro group, and/or a CF ₃ group. thus represents a substituted phenyl or naphthyl group, and U and V taken together form the following formula: -CH ₂ -CH
(CH ₂ ZR′ ₇ )− (wherein Z represents an oxygen or sulfur atom, and R′ ₇ represents a meaning other than the hydrogen atom among the R ₇ groups defined above)]; and Methods for producing acid addition salts and metal complexes thereof. 54 Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a nitro group. , Ar represents the following formula: [Formula] or [Formula] (where Rc, Rd and Re each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a C1 to 3 alkyl group; R ₇ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or _an alkoxy group having 1 or 2 carbon atoms. alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 3 to 4 carbon atoms, 2-
Propynyl group, 3-halogen-2-propynyl group, phenyl group, one or several halogen atoms, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group and/or CF phenyl group substituted by ₃ groups, unsubstituted or substituted by one or several halogen atoms, C1-C3 alkyl group and/or C1-C3 alkoxy group represents a benzyl group, and U and V together represent the following formula -CH ₂ -CH(CH ₂ ZR' ₇ )- (wherein Z represents an oxygen or sulfur atom,
54. The method according to claim 53, wherein R' ₇ represents a group other than the hydrogen atom in the definition of the R ₇ group. 55 A compound represented by the general formula: Ar-X ₃ () and the general formula: [In the formula, Ar, Ra, Rb, Y, U and V represent the meanings defined in the following formula, and one of X ₃ and X ₄ is the formula -O-Me (wherein Me represents a hydrogen atom or a metal cation) ) and the other represents a group exchangeable with the aryloxy group] are condensed with each other and, if desired, into acid addition salts or the compounds obtained in this way. A general formula characterized by converting an acid addition salt into a free compound or into another acid addition salt, or a free compound or acid addition salt obtained by these methods into a metal complex: [In the formula, Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. or represents a nitro group, Ar is unsubstituted or has one or several halogen atoms, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a nitro group, and/or a CF ₃ group. thus represents a substituted phenyl group or naphthyl group, and U and V together represent the following formula: [Formula] [Formula] or [Formula] {wherein R ₁ and R ₂ independently of each other represent a hydrogen atom, Alkyl group having 1 to 12 carbon atoms, substituted with 1 to 12 halogen atoms and having 1 to 12 carbon atoms
an alkyl group, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group having 1 to 3 carbon atoms, or a phenyl group of the formula:-
Represents a group represented by CH ₂ -Z-R ₇ (wherein Z represents an oxygen or sulfur atom, R ₇ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 1 or 2 carbon atoms). 1 alkyl group having 1 to 8 carbon atoms, alkenyl group having 3 to 4 carbon atoms, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, substituted with 1 alkoxy group or a phenyl group substituted with several halogen atoms, C1-C3 alkyl groups, C1-3 alkoxy groups, nitro groups and/or _CF3 groups, unsubstituted or one or represents a benzyl group substituted with several halogen atoms, an alkyl group having 1 to 3 carbon atoms and/or an alkoxy group having 1 to 3 carbon atoms), R ₃ , R ₄ and R ₅ are independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ does not exceed 6, and R ₆ is a hydrogen atom. or represents an alkyl group having 1 to 3 carbon atoms} Forms an alkylene bridge represented by the following.] A method for producing a compound represented by the following, an acid addition salt, and a metal complex. 56 Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a nitro group. , Ar represents the following formula: [Formula] or [Formula] (where Rc, Rd and Re independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a C1 to 3 alkyl group) represents a group represented by the following formula: [Formula] [Formula] or [Formula] {in the formula, R ₁ and _{R 2} are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, and 1 to 12 carbon atoms substituted with one or several halogen atoms;
an alkyl group, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group having 1 to 3 carbon atoms, or a formula:-
Represents a group represented by CH ₂ -Z-R ₇ (wherein Z represents an oxygen or sulfur atom, R ₇ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 1 or 2 carbon atoms). C1-C8 alkyl group substituted with one alkoxy group, C3-C4 alkenyl group, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, one or phenyl group substituted by several halogen atoms, C1-C3 alkyl group, C1-C3 alkoxy group, nitro group and/or _CF3 group, unsubstituted or one or more R ₃ , R ₄ and R ₅ are each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ does not exceed 6, and R ₆ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 56. The method according to claim 55, wherein the group represents an alkyl group having 1 to 3 carbon atoms. 57 General formula: [In the formula, Y represents -CH= or -N=, and Ra and Rb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. or represents a nitro group, Ar is unsubstituted or has one or several halogen atoms, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a nitro group, and/or a CF ₃ group. thus represents a substituted phenyl group or naphthyl group, and U and V together represent the following formula: [Formula] [Formula] or [Formula] {wherein R ₁ and R ₂ independently of each other represent a hydrogen atom, Alkyl group having 1 to 12 carbon atoms, substituted with 1 to 12 halogen atoms and having 1 to 12 carbon atoms
an alkyl group, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group having 1 to 3 carbon atoms, or a phenyl group of the formula:-
Represents a group represented by CH ₂ -Z-R ₇ (wherein Z represents an oxygen or sulfur atom, and R ₇ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, C1-C8 alkyl group, C3-C4 alkenyl group, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, substituted with one group or phenyl group substituted by several halogen atoms, C1-C3 alkyl group, C1-C3 alkoxy group, nitro group and/or _CF3 group, unsubstituted or one or more R ₃ , R ₄ and R ₅ are each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the total number of carbon atoms in R ₃ , R ₄ and R ₅ does not exceed 6, and R ₆ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Representing an alkyl group having 1 to 3 carbon atoms } Forming an alkylene bridge represented by } A microorganism characterized by containing as an active ingredient at least one of a compound represented by the following, an acid addition salt thereof, and a metal complex. A fungicide for agriculture and horticulture to control or prevent damage caused by. 58 As an active ingredient, the following compound group: 2-[p-(phenoxy)phenyl]-2-[1-
(1H-1,2,4-triazolyl)methyl]-4
-Methyl-1,3-dioxane or its salt, 2-[p-(phenoxy)phenyl]-2-[1-
(1H-1,2,4-triazolyl)methyl]-4
-ethyl-1,3-dioxane or its salt, 2-[p-(phenoxy)phenyl]-2-[1-
(1H-1,2,4-triazolyl)methyl]-4
-Methyl-1,3-dioxolane or its salt, 2-[p-(phenoxy)phenyl]-2-[1-
(1H-1,2,4-triazolyl)methyl]-4
58. The agricultural and horticultural fungicide according to claim 57, which contains at least one compound selected from -ethyl-1,3-dioxolane or a salt thereof. 59 Active ingredient expressed by formula 0.1 to 99%,
The agricultural and horticultural fungicide according to claim 57 or 58, characterized in that it contains 99.9 to 1% of a solid or liquid additive and 0 to 25% of a surfactant. 60 Active ingredient expressed by formula 0.1 to 95%,
The agricultural and horticultural fungicide according to claim 59, characterized in that it contains 99.8 to 5% of a solid or liquid additive and 0.1 to 25% of a surfactant. 61. The agricultural and horticultural fungicide according to claim 57, which is applied to plants or their cultivation areas in order to control or prevent damage caused by harmful microorganisms to plants. 62. The agricultural and horticultural fungicide according to claim 61, wherein the microorganism harmful to plants is a fungus harmful to plants.