JPS5823687A - Novel arylphenyl ether derivative, manufacture, noxious microbe repellent and medicinal remedy - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to substituted arylphenyl ether-derived KMs represented by the following general formula I, 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 general formula I as an active ingredient, methods for producing such compositions or therapeutic agents, and uses thereof. It also relates to a method of treating plants for regulating or preventing attack of harmful microorganisms on plants.

The arylphenyl ether derivative of the present invention [wherein Y represents -CH= or -N=, and al and 几 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, Represents an alkoxy group or nitro group having 1 to 3 carbon atoms, and A is unsubstituted or one or several halogen atoms, an alkyl group having 1 to 7 carbon atoms, or an alkoxy group having 1 to 7 carbon atoms. , represents a phenyl group or a naphthyl group substituted by a nitro group and/or a CF group, and U and ■ may be independently unsubstituted or substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms. , represents an alkyl group having from 1 to 12 carbon atoms, or together represents the following formula: an alkyl group having 1 to 12 carbon atoms substituted with a halogen atom, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group having 1 to 3 carbon atoms; Represents a group represented by the formula: -0Hs-Z- (wherein 2 represents an oxygen or sulfur atom, and the island represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a group having 1 to 8 carbon atoms, or C1-C8 alkyl group substituted with one alkoxy group of 2, C3-C4
alkenyl group, 2-propynyl group, 3-halogen-2
-70 vinyl group, phenyl group, one or several halogen atoms, alkyl group having 1 to 30 carbon atoms, alkyl group having 1 to 5 carbon atoms, nitro group and/or CF,
phenyl group substituted with a phenyl group, unsubstituted or substituted with one or several halogen atoms, an alkyl group having 1 to 6 carbon atoms, and/or a phenyl group substituted with an alkoxy group having 1 to 3 carbon atoms; /zyl group), k, R4 and 4 each independently represent an alkyl group having 1 to 4 carbon atoms across a hydrogen atom; in this case, an island,
The total number of carbon atoms in electron and as does not exceed 6, and electron represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. its acid addition salts and metal complexes.

The substituent Ar group as an unsubstituted or weathered phenyl group or a 7-N group is, for example, represented by the following formula = (in the formula FLc,
fLd and ELe each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 70 carbon atoms, a nitro group, or CF, a group represented by It is.

Depending on the number of carbon atoms, Definition 1 "alkyl group" by itself or as another substituted moiety, may include the following groups:
Methyl group, ethyl group, propyl group, butyl μ, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Means a decyl group, a decyl group, a dodecyl group, and their isomers, such as isopropyl group, isobutyl group, tert-butyl group, sec-butyl group, isopentyl group, etc.
Ru. 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-5-yl group. In this specification, the term "no-rogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom! It means an atom or an iodine atom, and a chlorine atom or a bromine atom is preferred.

The present invention; 1. relates to the free compound* of the general formula (1) and its acid addition salts with inorganic and organic acids, and also relates to complexes thereof with metal salts.

The salts of the invention are especially addition salts with inorganic or organic acids which are physiologically acceptable for their usefulness.

Examples of physiologically acceptable/inorganic or organic acids for their usefulness as fungicides in plant prevention include hydrohalic acids such as hydrochloric acid, hydrobromic acid or hydroiodic acid, sulfuric acid, Unsaturated or halogenated fatty acids such as phosphoric acid, phosphorous acid, nitric acid, acetic acid, trichloroacetic acid and oxalic acid, or sulfonic acids such as benzenesulfonic acid and methanesulfonic acid.

Physiologically acceptable acids with respect to their medicinal utility;
That is, pharmaceutically acceptable salts include hydrohalic acids such as hydrochloric acid, hydrobromic acid, and hydroiodic acid, pharmaceutically acceptable inorganic acids such as nitric acid, sulfuric acid, or phosphoric acid, acetic acid, Aliphatic monocarboxylic acids such as 77-alic acid, maleic acid, malic acid or uratic acid, as well as optionally hydroxylated dicarboxylic acids, and methanesulfonic acid, ethanesulfo/acid, he/zenesulfo/acid, p-) Lower alkanesulfonic acids such as luenesulfonic acid and p-bromo/sulfonic acid or substituted or unsubstituted benzenesulfonic acids! Aliphatic or aromatic sulfo/! ! pharmaceutically acceptable carboxylic and sulfonic acids, and sulfamino acids such as N-cyclohexylsulfamic acid.

General ceremony! Metal complexes are composed of basic organic molecules and inorganic or organic metal salts such as copper, magnesium, iron, zinc, etc. or halides, nitrides, sulfides, phosphides, and oxidized oxides of other metals. configured. The metal cations can be present in different valences.

Compounds of general formula I are oily, resinous or solid, stable at room temperature and exhibit very valuable biological properties, such as microbial activity, such as phytoantifungal activity, and pharmacological properties. Its anti-fungal, anti-spasmodic and anti-anxiety properties have an anti-anxiety effect. Therefore, on the one hand, it can be used in the field of agrochemicals or related fields to prevent the pathogenesis of plant microorganisms, and on the other hand, in the pharmaceutical field, it can be used for antifungal and/or anticonvulsant and anxiolytic, For example, they can be used to control fungi that parasitize warm-blooded animals and/or to treat various epilepsy, anxiety, nervousness and excitability, and/or medical conditions. − An important group of fungicidal agents used in plant prevention are general formulas! , 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 represents a group, Ar represents the following formula: (wherein Rc, ad and Re each independently represent a hydrogen atom,
Halogen atom, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 3 carbon atoms, nitro group or CFs
represents a group), and U and ■ independently represent an alkyl group having 1 to 12 carbon atoms, or together represent a group represented by the following formula: a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with one or several halogen atoms,
Represents 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 group represented by the formula: -CH*-Z-Rv, However, in the formula, Z represents an oxygen or sulfur atom, and it is assumed that Z represents a hydrogen atom, a C1-C8 alkyl group, or a C1-C8 alkoxy group substituted with one C1-C8 alkoxy group. Alkyl group, number of carbon atoms: 3
-4 alkenyl group, 2-propynyl group, 3-halogen-2-propynyl group, phenyl group, one or several 7-Rogge/atom, alkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms 3 alkoxy groups, nitro groups and/or OF, phenyl groups substituted with groups, unsubstituted or one or several halogen atoms, alkyl groups having 1 to 5 carbon atoms and/or 1 to 5 carbon atoms; (3) represents a benzyl group substituted by an alkoxy group in
e "4 and R+, the total number of carbon atoms in does not exceed 6, and the islands contain hydrogen atoms or 1 carbon atom
to 3 alkyl group) which form an alkylene bridge, as well as acid addition salts and metal complexes thereof.

This subgroup is named group la.

Preferred fungicidal groups effective for agricultural use are:
In the general formula l, Y represents l= or -N=, Ra and Rb each independently represent a hydrogen atom, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, and Ar is Represents a group represented by the following formula: (wherein R1c, ad and R+e independently represent a hydrogen atom, a halogen atom, CF, or an alkyl group having 1 to 3 carbon atoms), and U and ■ Compounds having the meaning defined in formula I above, as well as acid addition salts and metal complexes thereof.

This group is named group lb.

Preferred fungicidal compounds in subgroup lb are those of the general formula I in which U and V independently of one another represent an alkyl group having from 1 to 30 carbon atoms, or together represent the following formula: (2, 2, R4 and - each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; in this case, the total number of carbon atoms in (not exceeding 6).

This group is named group lc.

A more preferable group of fungicidal groups effective for agricultural purposes is the general formula I, in which Y is 10H= or -N
=, Ar has the meaning defined in formula I above, and Ra
, fL, , FL, , ad, and R1, each independently represent a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a methyl group, a meFoxy group, or a nitro group, and U and ■ independently of each other represents an alkyl group having 1 to 3 carbon atoms, or together form an alkylene bridge as defined in formula I above;
Island, R3, electric.

Island and - independently of each other represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or have the formula:
-CH, -0-1(,7), where the formula Nakajima is an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 2 to 4 carbon atoms substituted with an alkoxy group having 1 to 31 carbon atoms. is a compound representing an alkyl group, an alkenyl group having 3 to 4 carbon atoms, or a phenyl group.

This glue/ is named group ld.

Among Group ld, those having particularly excellent bactericidal properties are compounds in which U and V together form unsubstituted or simply substituted ethylene or probile/bridge deprivation.

This group is named group le.

The following individual compounds (particularly preferred in the agricultural field are listed below)
It-1-L2.4-)riazolyl)methyl-4-methyl-t5-dioxane, 2-(p-(phenoxyphenyl)-2-(1-(IH
-s,z,4-triazolyl)methylcou-4-ethyl-t5-dioxane, 2-[p-(phenoxy)phenyl]-2-(1-(I
H-1,2,4-)riazolyl)methyl]-4-methyl-1,3-dioxolane, 2-(p-(phenoxy)phenyl)-2-(1-(IH-1,2,4-)riazolyl ) methyl]-4-ethyl-1,5-dioxolane.

Compounds of general formula I of interest for antifungal activity are group I
In the 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 Formula: (In the formula, R., Rd and R. each independently represent a hydrogen atom, a halogen atom, CF, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms) and U and V have the meanings defined in formula I above.

Among the subgroups if, preferred for antifungal activity are general formula I
A compound of the formula: where U and V are independently a C1-C6 alkyl group, a C2-C2 alkyl group which is unsubstituted or optionally substituted with a halogen or a C1-C2 alkoxy group; represents an alkyl group of from 1 to 4, or together represents the following formula:
in which the total number of carbon atoms in the islands, in the middle and in the middle must not exceed 6).

This group is named group tg.

In subgroup Ig, preferred compounds of the general formula I with respect to their antifungal activity are those of the formula group, 2 carbon atoms substituted with an alkoxy group of 1 or 2 carbon atoms
It is a compound representing an alkyl group represented by an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 5 or 4 carbon atoms, or a 2-propynyl group.

This group is named group lh.

A further preferred group of compounds of general formula I having antifungal activity is in which: , represents a hydrogen atom, a methyl group, a chlorine atom or a bromine atom, and FLo, Rd and Re each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a methyl group.

Represents a methoxy group, CF3 or nitro group, U and ■
are independently unsubstituted or one carbon atom! ! L1 or 2 represents an alkoxy group or an alkyl group having 1 to 3 carbon atoms substituted with a chlorine atom, or together, the above formula! represents an alkylene group represented by the formula given by, in this case, at, 'tLz, Kamoh,
R4゜ and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, or R1 has the formula -ct-5oR? In this case, the island represents a group having 2 carbon atoms substituted with an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 or 2 carbon atoms.
or 3 alkyl groups, or 5 or 4 carbon atoms
This is a compound representing an alkenyl group.

This group is named group li.

The following individual compounds are illustrative of particularly preferred compounds having antifungal activity.

2-(p-(phenoxy)phenyl)-2-[1-(I
H-1,2,4-') riazolyl]-4-methyl-5-methyl-3-dioxolane, 2-(p-(phenoxyphenyl)-2-(1-(I
H-L2,4-)riazolyl)methyl]t6-dioxane, 2-(p-(phenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1゜5-dioxo, ran, 2-( p-(2,4-dimethylphenoxy)7enyl)
-2-, (1-imidazolylmethyl)-4-ethyl-1
,3-dioxola/, 2-(p-(3-chloro)enoxy)phenyl]-2-
(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane, 2-(p-(4-chlorophenoxy)phenyl)-2-
(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane, 2-(p-(5-)lifluoromethylphenoxy)phenyl)-2-(1-imidazolylmethyl)-4-ethyl-R5-dioxolane , 2-(p-(4-chloro-3-
methylphenoxy)phenyl)-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane, 2-
(p-(3,4-dichlorophenoxy)7enyl)-2
-(1-imidazolylmethyl)-4-ethyl-1,3-
Dioxola/, 2-(p-(2,5-dichlorophenoxy)7enyl)
-2-(1-imidazolylmethyl)-4-ethyl-1,
3-dioxolane, 2-(p-(44-dichlorophenokidin-7enyl)-
2-(1-imidazolylmethyl)-4-methoxymethyl-1,3-dioxolane, 2-(p-(4-fluorophenoxy)phenyl)-2-(1-imidazolylmethyl)-4-nityl-t3-dioxola/ , 2-(p-(4-fluorophenoxy)phenyl)-2
-(1-imidazolylmethyl)-4-methyl-5-methyl-1,'5-dioxola/and their pharmaceutically acceptable acid addition salts, their production methods, preparations containing them, and their pharmaceuticals It is used for.

Interesting compounds of the general formula 1 that are related to convulsive or anxiolytic properties are classified in group 1g, in which Y represents 10 or -N=, and FLa and or are independent of each other. represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, Ar is unsubstituted or an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, C1, N, , or a phenyl group substituted with a halogen atom, and these and (■) represent the meanings defined in the formula iris above.

In subgroup tg, compounds of the general formula I having very useful anticonvulsant and anxiolytic properties are those in which Y represents 10= or -N= and Ra and ILb 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 CF, and U and ■ independently of each other, n 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 or 2 carbon atoms, or together with the following formula; (In the formula, al, a, , island, ru 4 and σ) each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but in this case, the sum of the carbon atoms of R, , B4 and the turtle shell The number must not exceed 4).

These groups are named group lk.

A group of compounds with distinct anticonvulsant and anxiolytic properties that are particularly suitable include: where Y represents -CH= or -N-, +(+a and R5 represent a hydrogen atom, and Ar is represents an unsubstituted or phenyl atom or a phenyl group substituted with a methyl group, and U and V together represent the following formula: or a dicarboxylic group, a hydroxy-C1-C3 alkyl group, such as a hydroxymethyl group or a 2-
Human 1J xyethyl group, or 1 or 2 carbon atoms
alkoxy - an alkyl group having 1 or 2 carbon atoms, such as a methoxymethyl group or an ethoxymethyl group.

This group is named group It.

The following individual compounds are illustrative of particularly preferred compounds with anticonvulsant and anxiolytic properties.

2-(p-(phenoxy)phenyl)-2-(1-(I
H-1,2,4-) Reasily/I/) Methyl2 1.3
-dioxane, 2-(p-(4-chlorophenoxy)phenyl]-2-
(1-imidazolylmethyl)-4-ethyl-t3-dioxolane, 2-(p-(4-″chloro-2-methylphenoxy)phenyl)-2-(1-imidazolylmethyl)-4-methoxymethyl-1,3 -dioxolane, 2-(p-(phenoxy)phenyl]-2-[1-(I
H-1,2,4-triazolylmethylcou-4-hydroxymethy/L/-1,5-dioxola/, 2-(p-(4
-fluorophenoxy)phenyl)-2-(1-imidazolylmethyl)-4-ethyl-1,6-dioxolane, 2-(p-(4-fluorophenoxy)phenyl)-2
-(1-imidazolylmethyl)-4-hydroxymethyl-t3-dioxolane, 2-(p-(4-fluorophenoxy)7enyl)-2-(1-(11(= 1.2.
4-)riazolyl)methyl)-1,3-dioxane and their corresponding pharmaceutically acceptable acid addition salts, their production methods, preparations containing them and their pharmaceutical uses.

Compounds of general formula I can be obtained by the following method. That is, A) General formula I: (wherein Me represents a hydrogen atom or a metal cation, Y
represents -CH= or -N=) bu----v (wherein FL, , Rb, Ar, U and V represent the meanings defined in the above formula!, and X is nucleophilic or B) a compound represented by the general formula (in which Y, Ra, Rb, and Ar represent the meanings defined in formula 1 above) C) General formula! A compound in which U and ■ together represent a group represented by the following formula: % formula %) (in the formula ~' represents a horse group defined in the above formula I excluding a hydrogen atom) General formula for manufacturing ■
: A compound represented by Ra and the following formula (■): For - ~ 罎.

[In the above formula, -Rb, Y, Ar and H have the meanings defined in the above formula I, and one of Xl and Z represents an oxygen or sulfur atom, Me represents a hydrogen atom or a metal cation), and the other represents a nucleophilic separating group, or A and X2 both represent a hydroxyl group] or D) a compound represented by the general formula ■: Ar-X3 (■) and a compound represented by the general formula ■: La [where Ar, Ra , Rb, Y, U and ■ represent the meanings defined in the notation formula I, and one of tae and ta is a group represented by the formula -〇-Me (wherein Me represents a hydrogen atom or a metal cation) and the other represents a group exchangeable with the aryloxy group] or (wherein Y, Ra, FL6, Ar, U and V are defined in formula I) The compound represented by (representing the meaning of
Substituting other compounds of formula I and/or
The free compounds obtained by these methods can be converted into acid addition salts, or the acid addition salts obtained by these methods can be converted into free compounds, or other acid addition salts can be obtained by these methods. It can be obtained by converting the free compound or acid addition salt 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; Lower alkanesulfonic acids such as meta/sulfonic acid, ethanesulfonic acid, he/zenesulfonic acid, p-)luene/sulfonic acid or fluorosulfonic acid, substituted or unsubstituted meta/zenesulfonic acid or Examples include hydroxyl groups esterified with acids and the like.

General formula...: (In the formula, Y represents -CH= or -N=, Me preferably represents a metal atom, particularly an alkali metal atom (In the formula, Ar,
f'La, R6, U and ■ represent the meanings defined in the above formula ■, and X is a halogen atom, especially a chlorine atom, a bromine atom or an iodine atom, or a benzene atomyloxy group, an artosyloxy group, a trifluoroacetyl group. oxy group or preferably a lower alkylsulfonyloxy group such as mesyloxy group), the reaction with a relatively polar but inert organic solvent such as N,N-dimethylformamide, 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, chlorine, nitrobenzene, etc. be.

If the group X is a chlorine or bromine atom, adding an alkali iodite (such as sodium or potassium iodide) is effective to accelerate 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 (2) is a hydrogen atom, the reaction is carried out in the presence of a base. Preferred bases include, for example, alkali metal and alkaline earth metal oxides,
Inorganic bases such as hydroxides, hydrides, carbonates and bicarbonates, and organic bases such as tertiary amines such as triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine, etc. It is a base.゛Col) & i left and continued! By lithography, the final product and the final product in the reaction medium can be isolated and, if desired, purified using any conventional means such as extraction, crystallization, IJ mudgraphy, distillation, etc. Ru.

In order to convert the carbonyl group in the compound of general formula (2) to a group of general formula ~', a carbonyl group having 1 to 12 carbon atoms, which is unsubstituted or substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms, is used. A trialkyl orthocarboxylic acid ester or at least 2 moles of an alcohol having one hydroxyl group of the following formula Va: U -OH (■a) is reacted in the presence of an acid, and U and ■ in the general formula are reacted. gives a compound which is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or formula (b): HO-U---V-OH (Vb).

react with a diol compound of the general formula I to obtain a compound in which U and ■ together form an alkylene bridge as initially defined.

In this case, Ar, Y, )ta, Rb, U and □V (, 7 (have the meaning defined in the above-mentioned general formula ①).

This ketal formation reaction can be carried out by a method similar to the already known ketalization reaction, for example, 2-bromomethyl-2,4-diphenyl-1,3-diogysola/[cy/thesis(5ynt
hesis) 1974 (1).

It can be carried out by a method similar to the production method of [23].

A particularly preferred method of ketalization is to bring both reactants together in a conventional organic solvent to form an azeotrope and heat under reflux for several hours. Preferred examples that cause azeotropy include benzene, toluene, xylene, chloroformal, and carbon tetrachloride. In order to accelerate the reaction, for example, p
- Preference is given to adding a strong acid such as toluenesulfonic acid. Organic solvents that can be used in this case include be/zeolite/
, aromatic hydrocarbons such as toluene and xylene, saturated hydrocarbons such as 11-hexane, or 1. t1-)
Examples include halogenated saturated hydrocarbons such as lychloroethane.

Furthermore, as another method of ketalization, for example, the ketone of the general formula (2) is ketalized with a γ-butyl alcohol or phenol different from the alkanol or diol compound of the formula Va or vb, and the alkanol Va or the diol vb is Efficient rearrangement ketalization by radical h) gives compounds of general formula 1. The starting materials are e.g.
(Dl and (V) can be obtained according to

In modified method (C), to obtain a compound of -CH2-CH(CI-1fZ~)- in which U and V of the general formula Xiachu are combined, for example, a compound of general formula (1) and a compound of general formula (1) (wherein Xl has the meaning defined by the group -ZH and X2 has the meaning defined by the group). 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-pe/tano/ and the like. Mixtures with other inert solvents, such as aromatic hydrocarbons such as Ebibe/Zene, toluene, xylene, etc. 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 certain cases to first convert the compound of general formula (1) into a preferred metal salt, in which case a sodium compound such as sodium hydride, sodium hydroxide, etc. This can be preferably achieved with This salt of the compound represented by the general formula (2) reacts with the compound of the general formula (2). In order to speed up the reaction rate, the reaction is carried out at elevated temperatures in some cases, preferably from 80 DEG to 130 DEG C. or below the boiling point of the solvent.

The general formulas ■ and ■ (wherein X1 is a group X
, X2 represents a group -ZH) can also be reacted.

A condensation reaction of the compounds of the general formulas ① and ② (in the formulas, Xl and te represent a hydroxyl group) gives a compound in which Z in the general formula 1 represents an oxygen atom, and the reaction is carried out by heating under reflux in a suitable solvent and at the same time This can be done by azeotropically removing water from the reaction mixture. Suitable such solvents include aromatic hydrocarbons such as toluene or HO-- itself alcohols. This reaction is e.g. p-)
It is advantageous to carry out the reaction in the presence of a strong acid such as luer/sulfone.

In variant (D), initially the general formulas , Ra, R
b, U, V, Y and Ar have the meanings defined in formula I above, and Me preferably represents a hydrogen atom). This reaction is advantageously carried out under the modified conditions.

In the modified method (El), a compound of the general formula A compound of OH(Xfl) is reacted with a difunctional derivative of a carboxylic acid such as, for example, phosgene, a lower alkyl ester of a halogenated acid, or a di-lower aryl or diphenyl carbonate, and further with a compound of the general formula xlnylb. or in a high boiling point solvent such as a high boiling point ether such as diphenyl ether or ethylene glycol dimethyl ether from 120° to 22°C.
It can be obtained by heating to 0°C.

The compounds obtained by the method of the present invention can be converted into other compounds having the general formula by methods known per se.

Thus, for example, compounds obtained by the method of the invention can be converted into other compounds of general formula 1 by rearrangement ketazolization reaction. For example, in the general formula (2), when U and V are unsubstituted or substituted with an alkyl group U having 1 to 12 carbon atoms, the group U is substituted with 1 molar amount of another unsubstituted or substituted carbon atom 1 Formulas V- to 12
OH(Vc ) can be substituted by a group V by reaction with an alkanol, or both groups U can be substituted by a divalent radical by reaction with a diol compound of the formula vb. The 2-rearrangement ketal reaction is carried out by conventional means,
Volatile, preferably by distillation or azeotropic distillation, in the presence of acid condensation reagents, such as inorganic acids, sulfonic acids or strong carboxylic acids, such as hydrochloric acid, hydrobromic acid, sulfuric acid, p-)luenesulfonic acid or F-fluoroacetic acid. This can be done while removing the reaction products.

Furthermore, according to the method of the present invention, a substituent can be introduced into the carbocyclic aryl moiety of the obtained compound.For example, the halogen atom can be iron-1zinc-, boron- The presence of a Lewis acid such as a halide can be achieved either by reacting the halogen or by introducing it 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 amine group is diazotized, for example with nitric acid, and the diazonium group is converted to a halogen atom by conventional means. Alternatively, it is substituted with 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.

Once the compound of the general formula I is obtained as a free base, it can be converted into the corresponding salt of the general formula I with inorganic or organic acids, or preferably by using equal amounts of the metal salt. It can also be converted into a metal complex of general formula 1 by.

On the other hand, the salt of general formula I can be converted to the free base of general formula I by reacting with a carbonaceous compound, an alkali dicarbonate, water, or an alkali oxide.

The starting ketal compound of the general formula (2) is a methylarylketone compound of the general formula (2), for example, a methyl aryl ketone compound of the general formula: can be obtained by reacting with a diol compound and simultaneously or subsequently halogenating. In this case, it is preferable to add p-)luenesulfonic acid to accelerate the reaction.

The ketones of the general formula (1) can be obtained by halogenating the starting ketones (XIV) to form a compound of the general formula (X): Lab, and then reacting W with an azole compound of the general formula in the same manner as in the modified method. It can be obtained by The halogen atom in the general formula is preferably a chlorine atom or a bromine atom.

Ketal compound 1. Vl, IX and X can be obtained in the same manner as in the modified process, for example by reacting the starting keto/ of the general formula (1) with the desired alcohol or diol compound.

The target substance of the present invention can be obtained in the same manner as the various modified methods described above.

α, β- or α substituted with the aforementioned ketones.

The ketalization reaction with the γ-diol forms primarily a diastereoisomeric mixture of the resulting ketals. Similarly, general expression! A mixture of the final product compounds can generally be obtained from the starting ketones. Compounds of general formula I can be obtained, for example, as two diastereoisomers: :The configuration of type A here indicates the 'trans' isomer (the same applies below)
.

The configuration of IibB here indicates the 'cis' isomer (the same applies hereinafter).

In addition, the symbols in the above three-dimensional structure have the following meanings: ・・・・ = Behind the depiction plane □ = Above the depiction plane - = In front of the depiction plane The two types of left-handed isomers are, for example, fractionated. Separation may occur by crystallization or by chromatography (thin layer chromatography, column chromatography, liquid high pressure chromatography).

The two isomers have different biological properties.

In practical applications, mixtures of heliolithic isomers are commonly used.

The present invention relates to all isomeric compounds represented by formula (2), their salts, and their gold complex salts.

The processes for preparing the compounds of formula I described under process 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 in which the Ar11-al group is a substituted phenyl or naphthyl group
-(I~arylenethemidazolyl ketals are described in the following documents: (U.S. Pat. Nos. 3,575,999, 5,956,470)
No. 410t664.

No. 4,101,666 and No. 4,156,008 as fungicides and bactericides.

Surprisingly, it has been found that the compound of formula ■ has a fungicidal spectrum that is practically very useful against phytopathogenic fungi and bacteria, as well as fungal and antispasmodic properties that indicate its use as a pharmaceutical. Ta. For example, compounds represented by EI have very effective curative, systemic and prophylactic properties and can be used for the protection of cultivated plants. When the compound of formula (1) is used, it is possible to inhibit or destroy microorganisms occurring on plants or plant parts (fruits, flowers, leaves, stems, roots of tubers) in various useful plants, and When the direction
Subsequently growing parts of the plant are also protected from damage by microorganisms.

The compounds of the class I are active against phytopathogenic fungi of the following classes: Deuteromycota [e.g. Botrytis (Botrytis)
rytis), Helminthosborium (Ilelmin)
thosporium), 7thalium (Fusa
rium), Septoria, Cercospora ('erco-spora and -Alternaria) + Basidiomycetes [e.g.
ia), Rhizocotonia (I)
), Buscinia (formerly Puccia)]; cystomycota [e.g. Venturia a, Podo X
77 x (Podasphaera), 11 Schiff (Erysiphe), Mo-linear (M
onilinia), un/nula (L) nclnula
) :]. Furthermore, the compounds of formula I have an osmotic effect. They are used as seed dressings for the protection of seeds (fruits, tubers, grains) and as plant cutting agents against fungal infections and against phytopathogenic fungi occurring in the soil.
It can also be used as utt-ings).

The invention therefore also provides fungicidal compositions and for the prophylactic treatment of M substances of formula I for controlling pathogenic microorganisms, in particular harmful fungi, and for protecting plants from damage by such microorganisms. It concerns the use of the compound.

Furthermore, the invention encompasses a process for the preparation of agrochemical compositions, characterized in that the compound OvJ of formula I 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 a compound of formula 1 or a novel composition to the plants.

Objects protected within the scope of the invention include, for example, the following plant species: Cereal a (wheat, barley, rye, oats, rice, sugar corn and related crops '1111)
, beets (sugar beets and beets), stone fruits, pears and soft fruits (apples, pears, plums, peaches, almonds,
Cherries, strawberries, raspberries and blackberries +7
), legumes (fava beans, lentils, peas,
soybean), oil plant (oil, bean, bobby, oil)
+ -'7', Sunflower, Coconut, Castor oil plant, Cocoa bean, Peanut, Cucurbitaceae (cucumber, marrows, meo 7), Minweishik'*
(cotton, hemp, hemp, jute), orange striped plants (orange, lemon, grapefruit, mandarin), ffW (
Spinach, lettuce, asparagus, cabbage, V-konshin, onion, tomato, horsetail, bagurica), Lauraceae (Aho-h”to, Nju7in, camphor), To'1
6 Rokoshi, cigarette, nuts, coffee, Tom, i,
Futu no vine, honogu, banana and daizen gum uyo, naribini shoga shokugi (Asteraceae plants).

The compounds of 2) are usually applied in the form of agricultural compositions,
It can be applied to the ground in the crop or to the treated clover plants, either at a time or in succession, together with another compound. These compounds are fertilizers or micronutrient providers, or 4I! There may also be other formulations that affect organisms. Selective herbicides, insecticides, fungicides,
It can be a bactericide, a nematocide, a molluscide, or a mixture of some of these preparations. Suitable carriers and auxiliaries can be solid or liquid and include substances commonly used in formulation technology, such as natural or recycled minerals, solvents, dispersants, wetting agents, thickening agents, tackifiers, etc. Corresponds to an agent or a binder.

Agricultural compounds of formula f or pesticides @ b! i, the preferred method of application to the infection pile is foliar spraying;! ,). The number of applications and the amount of application depend on the intensity of infection by the corresponding pathogen (dive of fungi). However, the compound of formula I can also be applied by topical impregnation of 1 tL'@ 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. Compounds of formula I can also enter the plant by passing through the soil through the roots (osmotic action). By covering,
Seeds can also be coated (coated). In special cases, other methods such as selective treatment of plant stems or buds are also available.

The compounds of formula I are used in unmodified form or preferably with auxiliaries customary in the pharmaceutical industry and are prepared by known methods into emulsion stock solutions, coatable pastes.
te), directly sprayable or dilutable solutions, diluted emulsions, wettable powders, aqueous solutions, powders, granules, and encapsulations, such as with bolomer substances. The method of application, such as spraying, atomizing, dusting, sprinkling or pouring, as well as the storage of the composition, will be chosen depending on the intended target and the general environment. Advantageous application rates are usually 509 to 5 Kp of active ingredient (a,i,) per hectare.

Preferably 100t 1h2 Kg a, i, /h
a, most preferably 200 II to 600 p a-
i,/ha.

Agricultural chemical preparations, i.e. compounds of Mr. I? ! Compositions or preparations containing I (active ingredient) and, if appropriate, solid or liquid auxiliaries, can be prepared by known methods, for example by combining the active ingredient with a solvent, a solid carrier and, where appropriate, a surface-active compound , 1rll) and/or milling.

Suitable solvents are: aromatic hydrocarbons, preferably from 8 to 120 carbon atoms, such as xylene mixtures or substituted naphthalenes; phthalates, such as dibutyl phthalate or dioctyl phthalate; aliphatics, such as cyclohexane or paraffins. Hydrocarbon: ethanol,
Alcohols and glycols such as ethylene glycol monomethyl or monoethyl ether and their ethyls and esters, ketones such as cyclohexane; strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide; and epoxidations. Epoxidized vegetable oils such as coconut oil or soybean oil; or water.

Solid carriers which can be used, for example in powders and dispersible powders, are usually natural mineral fillers such as calcite, melk, kaquilin, montmorillonite or attapulgite, highly dispersed silicic acid or highly dispersed absorbent polymers to improve the physical properties. It is also possible to add Suitable granulated absorbent carriers are of the porous type, such as silica, crushed brick, seviolite or bentonite; further suitable non-absorbent carriers are materials such as calcite or sand. Furthermore, a large number of pre-granulated gravel-free and organic materials can be used, especially dolomite or pulverized clay.

Depending on the nature of the compound of formula (1) to be formulated, the surfactant I11 is a nonionic, cationic and/or anionic surfactant with good emulsifying, dispersing and wetting properties. It is to be understood that the term β-surfactant' also includes mixtures of surfactants.

Suitable anionic surface-active agents can be both water-soluble soaps and water-soluble synthetic surface-active compounds.

The most suitable soaps are alkali metal salts, alkaline earth metal salts, or unsubstituted or substituted ammonium salts of higher fatty acids (C+o to Cm), such as stearic acid for oleic acid,
Alternatively, monofatty acid methyltaurine salts, which are sodium or potassium salts of natural fatty acid mixtures obtained, for example, from coconut oil or tallow, may also be mentioned.

However, so-called synthetic surfactants, especially aliphatic sulfonates, aliphatic sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonants,
is frequently used in history.

The aliphatic sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth salts or unsubstituted or substituted ammonium salts, and contain an alkyl group from 1 to 22 carbon atoms, which also includes an alkyl portion of an acyl group;
Examples are the sodium or calcium salts of lignosulfonic acid, dodenyl sulfate or mixtures of fatty alcohol sulfates obtained from natural fatty acids. These compounds include salts of sulfuric esters and aliphatic alcohols/
Also included are sulfonic acid salts of ethylene oxide adducts.

The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid group containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid/formaldehyde condensation products. the corresponding phosphate,
p containing, for example, 4 to 14 moles of ethylene oxide.
Salts of the phosphoric acid esters of -nonylphenol adducts are also suitable.

The nonionic surfactants are preferably BoIl glycol 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, (aliphatic 8 to 20 carbon atoms in the hydrocarbon portion of the phenol 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 and
a water-soluble adduct with an alkyl polypropylene glycol containing from 1 to 10 carbon atoms;
0 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol
Ether-based business. These compounds are A-propylene
Contains 1 to 5 ethylene glycol units per glycol unit.

Representative examples of nonionic surfactants are nonylphenol-polyethoxyethanol, castor oil polyethoxyethanol, polypropylene/polyethylene oxide adduct, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan triolate are also suitable nonionic surfactants.

The cationic surfactants preferably contain as N-substituent at least one C8-C22 alkyl group and as other substituents lower unsubstituted or halogenated alkyl groups, benzyl groups or lower hydrocarbon groups. It is a quaternary ammonium salt containing a xyalkyl group. The salt is preferably in the form of a halogenide, methyl sulfate or ethyl sulfate, for example, stearyltrimethylammonium chloride or benzyl di(2-chloroethyl)ethylammonium promitote.

Surfactants customary in the pharmaceutical industry include, for example, 2''McCutchan's Tergents, which are described in the following publications:
And Emulge Fires Annual A/ (MC
Cutcheon's Detergentsand
Emulsifiers Annual, etc., Mouse Publishing, Ringwood, New Chassis, 1979.
year; and Sisely and Wood.
d Wood) Author Sleep Encyclopedia Op Surface Actiip Agents (Encyclopedia
pediaof 5surface Active Ag
ents) - Chemical Publishers, New York, 19
80 years.

Pesticide layer agents usually contain 01 to 99% of the compound of formula 1, preferably 0.1 to 95%, and 999% of solid or liquid adjuvants.
It contains from 1% to 1%, preferably from 99.8% to 5% and from 25%, preferably from 0.1 to 25%, of surfactants.

Commercially available products are preferably formulated as Toyaku, although consumers will normally use diluted formulations.

The compositions may also contain other ingredients, such as stabilizers, consumables, toning agents, binders, tackifiers and fertilizers, or other active ingredients for obtaining special effects.

Such agrochemical compounds also constitute the object of the present invention.

The antifungal properties indicate the usefulness of the compound and its pharmacologically acceptable acid addition salts for controlling parasitic fungi in warm-blooded animals.
In vitro, conventional microbiological test methods are used to test strains that are parasites of warm-blooded animals, e.g.
n rrentagryphites), Microsporum canis, Sporotrichum
5chenkii), Aspergillus fumigatus (
Aspergillus fumiga-tus ) and Candida albicans (can+: Hdaalb
icans): and also in guinea pigs.
vivn), after oral or topical application,
On the skin of the back, there are genus Lepidoptera, such as Lepidoptera (T.
This was demonstrated by experimentally infecting C. rubrum and measuring its curative effect.

The antispasmodic properties of the compound of formula I and its pharmacologically acceptable acid addition have been shown to reduce pentatetrazole spasticity (in vivo in mice, for example, at doses of about 10 to 100 w/fp, O). pentatetrazo
le spasm) test, and also about 10
It may be demonstrated by an electroshock test at a dose of 1 ao q/Kpp-o-. Anxiolytic properties have been demonstrated in the Gellert test and Quatre-Plaque at doses of about 10 to 100 drops/kp p,o, for example in mice and other small mammals. Shown by testing. Taka, the 1rIL compound is an important anti-inflammatory compound.
Anic) It should also be mentioned that it has a % property.

Accordingly, the present invention also provides compounds of formula I and their pharmacologically acceptable acid addition salts for topical, topical (I nca I ) and all materials (sys-te+n
i c) For use in the control and, in particular, as an active ingredient in pharmaceutical preparations, for the systemic treatment of various epileptic conditions, anxiety and tension conditions and mental states, or for enteral administration. , and also to its use in the manufacture of pharmaceutical preparations for parenteral or topical application.

Pharmaceutical preparations (pharmaceutical preparations) containing the compound represented by formula (■) or a pharmacologically acceptable salt thereof may be for enteral administration, such as oral or rectal administration, 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 dosage of the active ingredient is 1 item, blood supplement, 1 course) Type 1. It depends on the person's age and medical condition and the method of use.

Oral administration (C
In this case, one dose is usually about 50 to 500 doses, which are administered in staggered doses, preferably divided into equal doses.

Pharmaceutical formulations may contain, for example, about 10 to 80%, preferably about 20 to 60%, of the active ingredient.

Pharmaceutical preparations for parenteral administration may be, for example, in dosage unit form, such as dragees, tablets, etc. There are capsules or tablets and also ambules. These are prepared per se by conventional methods, such as conventional mixing, granulation, dragee-coating, dissolving or freeze-drying. Pharmaceutical preparations for oral administration can therefore be prepared by mixing the active ingredient with a solid carrier, optionally granulating the resulting mixture and, if desired or necessary, adding suitable auxiliary agents. Suitable carriers for tablets and/or dragee coatings obtained by processing the mixed proboscis of granules into tablets or coating cores after addition of fillers, e.g. For example, lactose, sucrose, mannitol or sorbitol, cellulose products and/or calcium phosphates, such as tricalcium phosphate, calcium hydrogen phosphate, or binders, such as starch pastes, such as corn,
Grain scoops, rice or potato starch paste, gelatin,
Gum tragacanth, methyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose and/or polyvinyl pyrrolidone, or, if desired, a disintegrant, such as the above-mentioned starches, but also carboxydimethyl starch, cross-linked polyvinyl pyrrolidone, agar, alginate or Its salts are, for example, sodium alginate. Adjuvants include glidants and fA beaks, such as silicic acid,
Talc, stearic acid or its salts, such as magnesium stearate or calcium stearate,
and/or liquid forms, e.g. baths of the active ingredient in aqueous salts, and also suspensions of the active ingredient, e.g. Solvents or vehicles such as fatty oils, such as sesame oil, or synthetic fatty acid esters, such as ethyl oleate or triglycerides, may be used. or an aqueous injection suspension containing dextran and, optionally, stabilizers.

Pharmaceutical formulations for topical use include, for example, if--
ointments, pastes, foams, tinctures and solvents, which contain from about 0.5% to about 2.0%
Contains the active ingredient in an amount of 0%.

Ri l+-4+! oil-in-w
at-er: nfi) emulsion, which contains more than 50% water. , fatty skewers such as palmitic or stearic acid, liquid or solid waxes such as inopropyl mylstate, wool wax or beeswax, and/or hydrocarbons such as petrolatum or paraffin oil. Suitable emulsifiers are surface-active substances with predominantly hydrophilic properties, such as corresponding nonionic emulsifiers, such as fatty acid esters of polyalcohols or their ethylene oxide adducts, such as polyglycerol fatty acid esters or polyoxyethylene sorbitan fatty acids. ester〔
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; These are conventionally used in the presence of fatty alcohols, such as cetyl alcohol or stearyl alcohol. The feed agent to the aqueous phase is evaporation or polyethylene glycol. The core of the dragee-coated tablet is provided with a suitable coating resistant to gastric juices, the coating agent containing among others: acacia, gum arabic, talc, polyvinylpyrrolid/, polyethylene glycol and/or titanium dioxide. Condensed sugar solution, shellac solution in a suitable organic solvent or solvent mixture may be used and is resistant to gastric juices.
In the production of coatings suitable for example cellulose acetate phthalate or hydroxypropyl methylcellulose phthalate are used. 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 include gelatin and O
Dry-filled capsules and soft-encapsulated (s
Dry-filled capsules are in the form of granules, for example, fillers such as lactose, binders such as starch and/or lubricants such as talc or magnesium stearate, and stabilizers. , may contain active ingredients. In soft capsules, the active ingredient is dissolved or suspended in suitable liquids, for example fatty oils, paraffin oil or liquid polyethylene glycols, to which may also be added a stabilizer.

A dermal dosage form for direct administration is, for example, a suppository, the slurry consisting of a combination of the active ingredient and a slurry paste. Examples of suitable suppository bases are natural or sweet acid) +
1 Coulisse + 1 Coulisse + 1 Coulisse + 1 Coulisse + 1 Coulisse + 1 Coulisse + 1 Coulisse + 1 Coulisse Hydrocarbon, polyethylene glycol or higher alcohol. Gelatin intestinal capsules consisting of a combination of active ingredients and paste materials may also be used. Suitable pace materials include, for example:
Liquid triglycerides, polyethylene glycols or paraffin hydrocarbons.

Particularly suitable for parenteral administration are those which are water soluble and thus avoid water loss, such as polyalcohols, alcohols, glycerol, sorbitol, propylene glycol and/or polyethylene glycol, as well as preservatives, such as fragrances.

The ointment contains at least 70% water or an aqueous phase, preferably about 20%.
Water is dispersed in the oil, which accounts for 50% to 50% of the oil.
-in-oil: wlo) It is an emulsion.

The oil phase consists primarily of hydrocarbons, such as petroleum jelly, paraffin oil and/or hard halaffins, which are preferably combined with hydroxy compounds suitable for modifying water absorption, such as fatty alcohols or their esters, such as cetyl. Alcohol or wool 6') full:
Contains l-ru, or wool wax. Emulsifiers are corresponding lipophilic substances, such as the sorbitan fatty acids Nisdel (Spank), sorbitan oleate and/or sorbitan instearate. Additives to the aqueous phase include humectants such as polyalcohols such as glycerol, propylene glycol, sorbitol and/or polyethylene glycols, and preservatives, perfumes, and the like.

Fatty ointments are anhydrous and contain as a base, in particular hydrocarbons, such as oil jelly, petroleum jelly and/or liquid paraffin, as well as natural or partially synthesized fats, such as coconut fatty acid triglyceride-11, or preferably hydrogenated oils, such as aqueous peanut or castor oil, and also fatty partial esters of glycerol, such as glycerol mono- and distearates, and, for example, fatty alcohols, the emulsifiers used in ointments and/or &4-water. Contains additives to increase absorption rxU.

Pastes are creams and ointments containing powdered ingredients that absorb secretions, such as metal oxides, e.g.
Titanium oxide or oxidized chains, and talc and/or aluminum silicate (the purpose of their addition is to bind moisture or secretions to 4FC).

The form is a liquid O/W emulsion in the form of a four-way dispenser, and is a liquid O/W emulsion in the form of a propellant.
halogenated hydrocarbons used as
For example, chlorofluoro-lower alkanes, e.g.
Contains dichlorodifluoromethane R and dichlorotetrafluoroethane. In the oil phase, inter alia, hydrocarbons such as paraffin oil, fatty alcohols, cetyl alcohol, fatty acid esters, e.g.
Isopropyl listate and/or other waxes are used as emulsifiers, but also in pre-emulsifying mixtures which have hydrophilic properties, such as polyoxygenate.
Etelensolhitan fatty acid ester (Tweens),
and those having mainly lipophilic properties, for example, those having nrubitan fatty acid esters (Suvans) are used. Furthermore, customary additives such as preservatives and the like are used.

Tinctures and solvents are usually aqueous ethanol based, and to this base are added alcohols, such as glycerol, glycols, and/or polyethylene glycols, as wetting agents to reduce water loss. For example, lipid restoring substances such as fatty acid esters with lower polyethylene glycols, i.e.
Lipophilic substances soluble in the aqueous mixture 5 and, if necessary, other auxiliaries and additives are added as replacement components for the fatty components removed from the skin by ethanol.

Pharmaceutical compositions for topical application are obtained by any known method, eg by dissolving or suspending the active ingredient, if desired in or as part of the base.

When the active ingredient is in the form of a solution, one of the two phases is usually dissolved in VC before emulsification, and when the active ingredient is in the form of a suspension, a part of the base is dissolved before emulsification. and then add to the remaining ingredients.

The present invention will be explained in more detail with examples on the board.
401 etc. are not limited to this.

Here, parts and parts are indicated by Xt, and pressure is in mbar.

V-Building Example Example 1: 2-[p-(phenoxy)phenyl]-2 represented by the following formula:
-[1-(IH-1,2,4-triazole)methyl]
-Production of 4-methyl-1,6-dioxane An intermediate represented by: 2-[p-(phenoxy)phenyl)-2-7'lomomethyl-4-methyl-1
, 3-Dioxane production 2-[p-(phenoxinephenyl)-2-oxy-1
-10 parts of bromoethane and 4 parts of 1,5-butanediol
One part is heated under reflux in 40 m of anhydrous toluene in the presence of 12 parts of p-)luenesulfonic acid as catalyst for 5 hours, during which time the water of reaction is removed in a water separator. The reaction mixture is cooled to room temperature, dried with sodium sulfate salt and filtered. The solvent was removed by evaporation and the crude product was recrystallized from Improper Tools, melting point 96°-106°.
Obtain colorless crystals at °C.

b) Preparation of #terminal acid 1. 6.3 parts of sodium salt of 2.4-triazole and a catalytic amount of potassium iodide were mixed with 40 parts of dimethyl sulfoxide.
- in 2-(p-(phenoxy)phenyl)-2-7''lomomethyl=4-methyl-1. obtained in a).
6 with 7102 parts of 6-thioxa at a temperature of 120°C.
Stir for 0 hours. The reaction mixture is cooled to room temperature, then diluted with 500 nl of water and extracted five times with 50 d each of ethyl acetate.

Combine the extracts, wash twice with 20ml of water, and add sulfuric acid)
Dry over IIum, 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 was removed by evaporation and the oily residue was recrystallized from petroleum ether, melting point 99.5'-101°C.
Brownish crystals are obtained.

Example 2: 2-[:p-(4-chloro-2-methylphenoxy)phenyl]-2-(1-imidazolylmethyl,)-4-methoxymethyl-1,3-dioxolane represented by the following formula: Preparation 2-(p''(4-chloro-2-methylphenoxy)phenyljL2-(,t-imidazolylmethyl)-4- and droxymethyl-1,3-dioxolane 16s, N
, dissolved in 150 d' of N-dimethyl formamide,
Next, 1.9 parts of 1 ram dispersion (1.9 parts of 55% hydrogenated) was added with stirring while introducing nitrogen gas. This mixture was heated to 80℃2
Heat for 5 hours, then cool to room temperature and dropwise add 63 parts of methyl iodide with stirring over 1 hour, then heat at 60°C for 2 hours, dilute with 800 ad of ice water, and add 300 ad of ethyl acetate. Extract 6 times. Extract 50% water
twice with sodium sulfate, dried over sodium sulfate, filtered and the solvent is removed by evaporation. The residue is purified by column chromatography on silica gel with acetone/ethyl acetate (1:1) as solvent. Second, this eluate is removed by evaporation, and the mixture of monolithic isomers is recrystallized by treatment with hexane.
Beige crystals are obtained with a melting point of 92'-106°C.

Example 3: 2-,[p-(2-nitro-4-trifluoromethylphenoxy)phenyl)-2-(1-imida-zolylmethyl)-4-ethyl-1゜6-shiokidurane represented by the following formula: Preparation of 2-(p-(2-nitro-4-trifluoromethylphenoxy)phenyl)-2-(1-imidazolylmethyl)-4-ether-1,5-dioxolane a in 5001 L of dimethyl sulfoxide. When 1.84 parts of powdered potassium hydroxide is added to this solution, the temperature becomes 23.
The temperature rises to 3-36°C. After heating at 70° C. for 2 hours, 74 parts of 4-chloro-3-nitropenzotrifluoride in 100 tl of dimethyl sulfoxide were heated,
Continue stirring at 70°C for 6 hours. The reaction mixture is cooled to room temperature, poured into 2 portions of water, and extracted twice with 200 MI portions of diethyl ether. The combined extracts are washed twice with 1 portion of 70 IE of water, dried over sodium sulfate, and the solvent is removed by evaporation. This oily residue is purified by column chromatography on silica gel using ethyl acetate as solvent - this elution 9! When J is removed by #blasting, a mixture of heliolithic isomers remains as a residue in the form of a viscous substance.

Example 4: Synthesis of 2-(p-(5-chlorophenoxy)phenyl)-2-(1-imidazolylmethicine-4-ethyl-1,3-dioxolane) represented by the following formula: 41.2 parts of imidasilone sodium t , 2-(p-(3-chlorophenoxy)
phenyl)-2-7” romomether-4-ether-1.3
- 4 parts of dioxolane and a catalytic amount of potassium iodide are stirred in dimenalphamide bOs+j at a temperature of 125'C for 17:00. This brown reaction mixture was cooled to room temperature, diluted with 150 d of water, and diluted with 50 d of ethyl acetate.
Extract 3 times with one brew. This extract? -Water bO together
Wash twice with 100ml of sulfuric acid and dry with 20ml ram. The solvent was removed by evaporation and the crude product was
Chromatography was performed on a 351 column of silica gel with acetone/acetic acid (FK, 1:1) solvent. This eluate was removed by a source and the oily residue was crystallized from petroleum neal, melting point 69-71°C.
Obtain a yellowish crystalline substance with a yellowish color.

-J Example 5: 2-Cp.-(4-chlorophenoxyraphenyl), -2-(1-imidaso-1-methyl)-4- represented by the following formula:
Preparation of ethyl-1,3-dioxolane a) Synthesis of intermediate α) 2-(p-(4-chlorophenoquino)phenyl-2-methyl-4-ethyl-1,3-dioquinolane represented by the following formula: Production of 4-(p-chlorophenoxy)γmotophenone 3i
, 1. 18 parts of 2-7'tanediol and 2 parts of p-toluenesulfonic acid as a catalyst are heated under reflux for 14 hours in 400 d of anhydrous toluene with a moisture content of #I and F%.

The reaction mixture was cooled to room temperature and diluted with 400 g of water for 2 hours.
191, dried over sodium sulfate, and filtered. The solvent was removed by evaporation and the crude product, ligroin/hexane/ethyl acetate/toluene (5:
Purify on a 1 m column of silica gel using 3:1:ri as a solvent. This gives the product in the form of a slightly yellowish oil; nD: 1.5527.

Production of 2-Cp-(4-chlorophenoxy)phenyl)-2-prosemenal-4-ether-1,3-dioquinolane represented by α) 2-Cp-Ca-chlorophenoquino)phenyl]- 368 parts of 2-methyl-4-ether-1,3-dioxolane are heated to boiling temperature in chloroform 65OWJ. While illuminating with a 150 watt spot lamp, a solution of 194 parts of bromine in 50 g of chloroform was added, and the reaction mixture was subsequently forced under reflux for 2 hours, the reaction mixture was cooled to room temperature, and then water 200-
Washed with 2 [1 qJ each, dried with 11 μm of @fR sodium, filtered and filtered for t4. The solvent is then removed with a water pump.

This crude product was mixed with silica gel using toluene as a solvent.
Purification by chromatography on an m column. This product has a refractive index n. =1.5803
Have? Obtained in the 111I form.

b) Synthesis of the final product 4.4 parts of imidazole sodium salt, iodizing power, rum catalyst and 2-[p-(4-chlorophenoxy)-phenyl]-2-furomomenal obtained in step p) 14.7 parts of -4-ethyl-1,3-dioquinolane are stirred in dimethylformamide BOxl at a bath temperature of 125°C for 17 hours. The reaction mixture was cooled to room temperature, then diluted with 600 d of water and 200 d of ethyl acetate.
Extract 6 (9) with Tsutsude. The extracts are washed together (200 rnl each), dried over sodium sulfate, filtered and filtered. /'k(!1') is subjected to chromatag and roughy treatment on a silica gel 5061 column using acetone 7/acetic acid-[tyl (1:1) as a solvent.The solvent in this eluate is removed by evaporation to obtain the desired The product is obtained in the form of a brown oil with a refractive index of 1.5750.

Example 6: 2-Cp-(phenoxy)phenyl]-2 represented by the following formula:
-(IH-1,2,4-triazolylmethyl)-4-ethyl-1,,5-dioxolane sweet acid 2-[F+-(phenoxy)phenyl]-3-bromomethyl-4-ethyl-1,3 - 17 parts of dioxoraf, 84 parts of potassium carbonate,
j, 2. The mixture was stirred in 4.2 parts of 4-triazole and 100 g of dimethylformamide at a temperature of 125 DEG C. for 24 hours. The reaction mixture was cooled to room temperature and then mixed with Vero 00a+I! and extracted three times with 200 d of ethyl acetate.

The combined extracts are washed several times with 20 od of water, dried over sodium sulfate, and filtered.

The solvent is removed by evaporation and the oily residue is chromatographed on a 50 cm column of silica gel with chloroform/ether (1:1) as solvent. The solvent in this eluate is removed by evaporation and the oily residue is crystallized from a petroleum needle to give the product in the form of white crystals with a melting point of 81.5'-855°C.

Example 7: 2-4p-(phenoxy)phenyl]-2 represented by the following formula:
-(I H-1,2,4-)riazolylmethyl]-1,
Synthesis of 3-dioxane 14 parts of 2-(p-(phenoxyphenyl))-2-7” comomethyl-1,6-dioxaf, 7.2 parts of potassium carbonate
Part, 1°2.4-1 Riazol! L & part S and iodizing power I
A catalytic amount of Ium is stirred in 100 d of dimethylformamide at a temperature of 140° C. for 20 hours. The reaction mixture is cooled to room temperature, diluted with 600 g of water, extracted 3 times with 200 g each of ether. The combined extracts are washed with 200 111 portions of water, and
Dry with sodium and filter 8. Evaporate the solvent, leaving an oily residue. , chloroform/ether ('
Chromatography on a 51 column of silica gel with 1":1) as solvent. Evaporation of the solvent of the eluate and crystallization of the residue from petroleum ether yielded a product with a melting point of 129°-160° Obtained in the form of white crystals at °C.

Practical example 8: 2-4p-(phenoxy)phenyl)-2 represented by
-(IH-1,2,,4-triazolylmethyl)-4-
Synthesis of hydroquinomethyl-1,3-dioxolane 2-(p-(phenoxy)phenyl]-2-bromomethyl-4-hydroxymethyl-1,5-dioxolane 4,
5 parts of potassium carbonate, 2.2 parts of potassium carbonate, 161 parts of 1°2.4-) riazole and potassium iodide catalyst, and 50 Ill. of dimethyl sulfoxide! Stir for 4 hours at a temperature of 140°C. The reaction mixture was cooled to room temperature, then 60 ml of water
0d and extracted twice with 200 IIL of ethyl acetate.

The combined extracts are washed twice with 20 ml of water, dried over sodium sulfate, and filtered. The solvent is evaporated and the oily residue is chromatographed on a 501 column of silica gel with acetone solvent. Evaporation of the solvent and crystallization of the oil from petroleum ether gives the product in beige crystalline form, mp 111)-112°C θ).

Example 9: Synthesis of 1-(p-phenoxyphenyl)2-(1°2.4-triazo-11l)-ethanone σ nitrate 105 parts, 1.2
6.1 parts of -bentanediol, 6.9 parts of p-)luenesulfonic acid, 20 parts of 1-hair 4 /-k and 200 parts of xylene are heated under reflux in a water separator for 6 days. The anti-L6 mixture is then cooled to room temperature and washed twice with 200 d each of dilute sodium hydroxide@Q and twice with 200 d each of water. The organic phase is dried with 11 um of sodium sulfate and filtered with C. The solvent is evaporated and the oily residue is chromatographed on a 1 m column of silica gel with ethyl acetate as solvent. On evaporation of the solvent in this eluate, the oily residue IR gradually crystallizes to give the product in beige crystalline form with a melting point of 6a5°-71°C.

The following compounds of the formula (II) can also be prepared in a similar manner (unless stated in percentages, the xenolithic isomers still have different mixing ratios).

In the table below, the symbol A indicates the type A heliolithic isomer, and the symbol B indicates the type B heliolithic isomer. .

1=,, /” / − 〆/− (In the above formula, isomers are also included) Table 1 (continued) Table 1 (continued) Table 2 = The following formula (in the above formula Table 2 (Continued) Formulation Example Formulation Example for Pesticides Containing Liquid Active Ingredients Represented by Formula 1 (% is expressed by weight) 10) Emulsion Stock Solution a) b) c) Table Active ingredients 1 to 10 25% 40% 50% Calcium dodecylbenzenesulfonate 5% 8% 6
% castor oil polyethylene glycol ether (ethylene oxide 36-r=l) 5% --tributylphenol polyethylene glycol ether (ethylene oxide 50 mol) -12% 4% cyclohexanone -15% 20% xylene mixture 65% 25% 20% emulsion stock solution By diluting with water, emulsions of desired concentrations can be produced.

11) Solution a) b) c) d) Active ingredients in Tables 1 to 10 80% 10% 5%95
% ethylene glycol monomethyl ether 20%
---Polyethylene glycol MG400 -7
0% --Hemethyl-2-pyrrolidone-
20 curses -- epoxidized coconut oil
--1% 5% petroleum distillate (boiling range 160-190℃
) - 94% - (MG stands for molecular weight) These solutions are suitable for application in the form of microdroplets.

12) Granules a) b) Active ingredients from Tables 1 to 10 5% 10% Kaolin 94% - Highly dispersed silicic acid
1% - attapulgite
-90% active ingredient is dissolved in methylene chloride, this solution is sprayed onto the carrier and the solvent is subsequently distilled off.

13) Powder a) b) Active ingredients from Tables 1 to 10 2% 5% Highly dispersed silicic acid 1% 5% Talc
97 Curse -Kaolin-
By uniformly mixing 90% active ingredient and carrier,
A ready-to-use powder is obtained.

Examples of formulations for agricultural chemicals containing solid active ingredients represented by formula l (% expressed by weight) 1. Hydrating agents a) b) c) Active ingredients from Tables 1 to 10 25% 50% 75%
Sodium ligninsulfonate 5% 5%
- Sodium lauryl sulfate 5% -
5% Sodium diisobutylnaphthalene sulfonate-6
% 10% octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) -2
% - Highly dispersed silicic acid 5% 10%
10% Kaori 762% 27% - After the active ingredient is thoroughly mixed with the auxiliaries, the mixture is well milled in a suitable mill, which can be diluted with water to obtain a suspension of the desired concentration. A Japanese preparation is obtained.

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 Dotesylbenzenesulfonate
3% castor oil polyglycol ether (36 moles of ethylene oxide) 4
% cyclohexanone 30% xylene mixture 50% By diluting this emulsion stock solution with water, an emulsion of the desired concentration can be obtained.

16) Powder a) b) Active ingredients in Tables 1 to 10 5% 8% Talc
95% - Kaolin
- by mixing with a carrier containing 92% active ingredient and milling this mixture in a suitable mill;
A powder was obtained that could be used as is.

17) Extruded granules a) Active ingredients in Tables 1 to 10 10% Sodium ligninsulfonate 2% Carboxymethylcellulose 1% Kaolin 8
7% The active ingredient is mixed and milled with the auxiliaries and the mixture is subsequently moistened with water. The mixture is extruded and dried in a stream of air.

18) Coated granules Active ingredients in Tables 1 to 10 3% Polyethylene glycol M0200 3% Kaolin 94% (MG represents molecular weight) The finely ground active ingredient is added to kaolin moistened with polyethylene glycol in a mixer. Apply evenly.

This method results in dust-free coated granules.

19) Active ingredients in Tables 1 to 10 of 9 cloudy stock solution 40% ethylene glycol 10% nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6% sodium lignin sulfonate 10% carboxymethyl cellulose 1% 67% formaldehyde aqueous solution [12% 75% aqueous emulsion Shape silicone oil α8% water
By homogeneously mixing 32% finely ground active ingredient with auxiliaries and diluting with water, a suspendable concentrate is obtained, from which a suspension of the desired concentration can be obtained.

Formulation example 2α) for pharmaceutical preparations Ointment 2-(p-(4-chlorophenoxy)-phenyl)-2
An ointment containing 5% -(1-imidazolylmethyl)-4-ethyl-dioxolane is obtained as follows: Composition: Active ingredients 50% petrolatum 4, 0% paraffin oil
196% Cetyl Alcohol 50% Beeswax 5.0% Sorbitan Sesquioleate 5.0% p-hydroxybenzoic acid ester 02% in demineralized water
1000% fat and emulsifier are melted 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
A cream containing 10% of -imidazolylmethyl)-4-ethyl-1,3-dioxolane is obtained as follows: Composition Active ingredients ICLD%C 10% Valmitinlovir 80% Cetyl palmitate
1.5% silicone oil 100
α5% Sorbitan Monostearate 50
% Polysorbate 60 A5% 1
, 2-Flopylene glycol PH2α 0% acrylic acid polymer 05% triethanolamine [17% in demineralized water
10aO%.

The acrylic acid polymer is suspended in a mixture of demineralized water and 1,2-propylene glycol. Next, the mucilage was stirred in triethanolamine.
). A mixture of isopropyl palmitate, cetyl palmitate, silicone oil, sorbitan monostearate and polysorbate is then heated to about 75°C, added to the mucilage with stirring, and heated again to about 75°C. After cooling it to room temperature, the cream paste is used to prepare a concentrate containing the active ingredient.

This concentrate is homogenized continuously using a homogenizing agent and then added to the paste in portions.

2-(p-('rolophenoxy)phenyl]-2-(1
A cream containing 5% of -imidazolylmethyl)-4-ethyl-1,5-dioquinolane is obtained as follows: Composition Active ingredients 5.0% cetyl palmitate p) -12,0% cetyl alcohol PH2
,0% Triglyceride mixture of saturated medium fatty acids 5.0%
Stearic acid 50% chrycerol stear v-) PH4.0%ゞ1”po:/-y (
Ce to “acrogol) 1,.

000 Microcrystalline cellulose α5% 1.2-Propylene glycol (distillate) 2α0% Make 10α0% 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 paste and then incorporated into the rest of the cream.

22) Hydrogel 2-(p-(rioohue/#'/)-phenyl]-2-
A transparent hydrogel containing 5% of (1-imidazolylmethyl)-4-ethyldioxolane is obtained as follows: Composition Active ingredients 5% Glopyrene glycol 10-20% Isopropatol 20% Water
Diffuse 100% hydroxymethylcellulose in water. The active ingredient is dissolved in a mixture of Improno(nol and propylene glycol). This active ingredient solution is then mixed with the diffused cellulose derivative and, if desired, perfume is added.

23) Foaming spray 2-(p-(chlorophenoxy)phenyl)-2-(1
-4Mida7'Q-rumethyl)-4-ethyldioxolane 1
A foaming spray containing % is obtained as follows: Composition Active ingredients too% Cetyl alcohol PH 170% Liquid paraffin (viscous) t00% Isopropyl myristate z00% Cetamacroglu 140% Sorbitan Monostearate 150% 1.2 -Propylene glycol PHs, oo% methyl paraben
e) α18% propyl paraben
α02% Chemoderm
rm) 314 (with 110% demineralized water
10 (Cetyl alcohol as LOO%, liquid)
Melt together Kurafuin, isopropyl myristate, cetomacrogol and sorbitan stearate. Dissolve the methyl and propylene (lapene) in warm water. The melt and solution are then mixed. A suspension of the active ingredient in propylene glycol is incorporated into the paste. and water is added to the composition to bring it to final weight.

Fill composition 20- into an aluminum dispenser. Attach a power cap to this dispenser and fill it with foaming gas in the Kada state.

24) Capsule active ingredient (p-(phenoxy)phenyl)-1(
1-(IH-1,2,4-)riazolyl)methyl]-1
Two compositions (for 1000 capsules) of gelatin capsules containing 200 caps of ,5-dioxane obtained as follows: Active ingredient 1001 Lactose (ground) 1001 Active ingredient and lactose (ultra-finely ground) Mix thoroughly. The resulting powder is sieved and a2! Enclosed in a gelatin capsule.

25) Tablet active ingredient, for example, 2-[p-(phenoxy)phenyl)-2-(1-(IH-1,2,4-)riazolyl)
Two compositions (for 1000 tablets) of tablets containing methyl)-1,3-dioxane No. 25 obtained as follows: Active ingredient 25. OJ'lactose 10α7I starch
7.57 Polyethylene glycol 6000
5. OJl talc
5. OJ'Magnesium Stearate
18% Demineralized Water Mix thoroughly and pass all solid ingredients through a sieve having a mesh size of 0.6 m. Next, mix together the active ingredients, lactose, talc, magnesium stearate and half the starch.

The other half of the starch is suspended in 40 I/l of water, this suspension is added to a boiling solution of polyethylene glycol in 1000 d of water, and the mixture is mixed with water if necessary, Granulate. The granules were dried at 35° C. overnight, passed through 1.2 tssK, and shaped into biconcave tablets with a diameter of about 6 cm.

Active ingredients, such as 2-(p-(phenoxy)phenyl)-2-(1-(IH-1,2,4-triazolyl)
Tablets containing 75sF of methyl)-1,5-dioxane are obtained as follows: Composition (for 1000 tablets) Active ingredient 750! lactose
10α7. P starch
7.5 F polyethylene glycol 6000
ao 11 talc sa
p-milsteering nesium 1.87
1 Demineralized water Mix thoroughly and pass all solid ingredients through a sieve having a mesh size of C16m. Then mix together the 1 active ingredients, lactose, talc, magnesium stearate and half the starch.

The other half of the starch is suspended in 405 m of water, this suspension is added to a boiling solution of polyethylene glycol in 100 m of water, and the mixture is granulated, with addition of water if necessary. become The granules are dried overnight at 35°C, passed through a 1.2-sieve, and sieved into biconcave tablets approximately 6 in diameter.

Pharmaceutical preparations containing the other compounds shown in Tables 1 to 10 are obtained in a similar manner.

Biological Test Example 26: Wheat Pucciniagramini x
a) Residual Protection Wheat plants are treated 6 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (006%). 24
After 1 hour, the treated plants were infected with the fungus using a suspension of summer spores of the fungus, and the plants that had been infected with 1 fungus were heated to a relative humidity of 951.
0% at about 20°C for 48 hours, and then left in a greenhouse at about 22°C. The spread of rust warts is evaluated 12 days after infection.

b) Systemic action Wheat plants are treated 5 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.00/i% of the volume of soil breakage). After 48 hours, the treated plants were infected with N spores of the fungus I! The bacteria is transmitted through the cloudy liquid. The plants are incubated for 48 hours at about 20°C with relative humidity of 95-100% and then placed in a greenhouse at about 22°C. The spread of rust warts is evaluated 12 days after infection.

The compounds of Tables 1 to 10 are highly effective against Psinia. Psinia infection was 1 in untreated control plants.
It is 00%. In particular, compounds 1.17.1.24.2.
17. Δ1. A6. A7゜1j33. 5164. Al6
8. A220, 5267°1311. ! L314.4
．． 50.4.77, 4.81.4.90°4.91.4
．． 93.4.94.5.15.5.14.5.56.5
．． Residual protection treatment with 70°A8 and 17 suppresses fungal attack to 0-5%. Furthermore, compound 6.8 has 100
Sufficient osmotic action even when diluted to 6% concentration (0
% attack).

Example 27: Cercospora arachidicola (Cerco
Spora arachidicola) active ingredient 10 to 15 (1) active ingredient in peanut plants
Spraying a mixture of sougere prepared from a wettable powder formulation containing 2%, chrysanthemum conidia after 48 hours! Rinse the bacteria with 1P suspension. The infected plants are incubated for 72 hours at about 21° C. and high humidity in the dark and left in green grass 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 2100%)
Plants treated with the compounds of Tables 1 to 10 have a greatly reduced attack by Cercospora. For example, the compound 1.9,1.14°1.17.1.24.1
．． 26. , 1.27.2.17.36. A7. 511゜A133. 5162. ! L171. A172. 5176
, 5177°3221, Δ231. ! L232. M2
54. M314, 4.50°4°89.4.90.4.
91.492.4.95.4.94. A13゜5.1
4.5.56. &40.5.70. A71.5.7
5.5.75°5.76, 5.78. A1 and A8
almost completely suppresses spot formation in this test (5% attack).

Example 28: Barley Erysiphegr.
a) Residual protective effect A spray mixture prepared from the active ingredient formulated as a wettable powder (active ingredient α02
%). After 5 to 4 hours, the treated plants are sprinkled with conidia of the fungus. Next, remove infected barley plants from approx.
Leave it in a greenhouse at 2℃. The degree of infection is assessed after 10 days.

b) Spray powder prepared from the active ingredient formulated as a hydrating powder from barley plants at a height of about 8 osmotic action (α relative to the soil volume)
006%).

Be careful not to let the spray mixture touch any parts of the plant above the soil. After 48 hours of treated plants, the fungus is infected with a suspension of conidia of the fungus. The barley plants infected with M. were left in a greenhouse at about 22°C, and the degree of infection was evaluated after 10 days.

The compound of formula 1 shows a good residual protective effect against Erysiphe. Control plants infected without treatment were attacked by 100% by Erysiphae. For example, compound 1.
1.1.9.1.17゜1.23.1.24.1.25
．． 1.26.127.217. M1゜52.16. l
, 58. i11. 512. 526. 5127゜5133
．． 5164. 5168. 5172. 5176°5177
, 5193. 5226. 5251, 5.253゜526
7, 5274. 5311. 5514.4.50.4.7
8゜4.89.4.90.4.91.4.92.4.9
5.4.94.5.13゜5.14.5.56. A4
0.翫70.5.71. A75.5.75.5.76
゜5.7B, &1. /1w8.7.5.77 and 7.21 suppress bacterial attack to 5% or less. Compound 4
．． 50 is in soil treatment (osmotic action) and α00
It is effective even when diluted to 6% concentration.

Example 29: Venturia inaquaris (in apple cuttings)
Venturia 1nalquali) Spraying mixture prepared from a wettable powder formulation of the active ingredient (α0
6%). After 24 hours, the treated plants are infected with a conidial suspension of the fungus. Next, the relative humidity of the whole plant is 90
Culture at 100% to 100% for 5 days, and then leave in a green house at 20 to 24°C for another 10 days. Post-infection 1
Evaluate the degree of rot infection on the 5th day.

Compound 1.9.1.17.1.24.217. i6.
57. 511゜4.50.4.81.4.89.4.9
0.4.91.4.92.5.13゜514.556.
a40. ! 1t7(1, &1 and &8 inhibit infection to less than 10%. Penturia infection is 100% in untreated infected shoots.

Example 30: Botrytis cinerea in kidney beans
tis cinerea) A spray mixture prepared from the active ingredient formulated as an aqueous phase agent (concentration α02
%). After 48 hours, the plants are infected with the fungus using a suspension of fungal conidia. Plants infected with the fungus are cultured at 21° C. for 3 days at a relative humidity of 95 to 100%.

The compounds listed in Tables 1 to 10 often inhibit bacterial infections very strongly. [At a concentration of 102%, compounds 1.1, 1.9. 56.5.7. 5231.4.50゜4.78.5.13.5.56.5.40.5.70.
cL71.5.73°! 1L75.5.77, &1
and &8 are fully effective (mouth or 5% attack).

The degree of Botrytis infection in untreated infected standing plants is 100%.

Patent Applicant Chiver-Geigy Akchengesellschaft Representative Patent Attorney Zen Yumi '・°°, "'"'7'7 1 person) Continued from page 1 49100 317100 ) (C07D 405106 49100 319100) Priority claim @1982 April 21st ■Switzerland (CH)
■2428/82-1 (7 multiple cases Beter Liepli Switzerland 444
6 books 17

Claims (1)

[Claims] [In the formula, Y is 10) l=1 represents -N=, and Ra and RbF
i independently of each other, a hydrogen atom, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a nitro group, Arts unsubstituted or f or tj Several nitrogen groups, alkyl groups having 1 to 7 carbon atoms, carbon atoms #
! 1.1 to 7 alkoxy groups, nitro groups and/or F
i represents a phenyl 4 or naphthyl group ft substituted by a CFx group, and U and V independently of each other are
L or d represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a gun atom or an alkoxy group having 1 to 6 carbon atoms, or together represents the following formula: ( In the formula, Rt and Rs each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with one or several halogen atoms, and a phenyl group. , one 19 is a phenyl group represented by several halogen atoms and/or an alkyl group of carbon atoms #111 to #5, or a group tp represented by the formula CH3-Z-R, (wherein , 2 represents an i!It element or a sulfur atom, Rt is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carbon atom having 1 to 8 carbon atoms substituted by one alkoxy group having 1 to 2 carbon atoms. alkyl group, phenyl group or 2-propynyl group having 3 to 4 carbon atoms, 5-halogen-2-7''
phenyl substituted by a lopynyl group, a phenyl group, one or several halogen atoms, a C1-C5 alkyl group, a C1-C5 alkoxy group, a nitro group and/or a ticF group. R1, R4 and Rs independently of each other represent a hydrogen atom 19 representing an alkyl group having 1 to 4 carbon atoms, but the accounting lIL of the carbon atoms of this bottle base R1, R4 and 4 does not exceed 6, and &1 ! Forming an alkylene bridge represented by hydrogen or an alkyl group having 1 to 3 carbon atoms, acid addition salts thereof, and gold M complexes. (2) In the general formula l, Y is -Ci (='!9 represents -N=, Ra and Rb
Fi independently represents 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 is the following formula: (wherein Re e Rd and Re are Independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 5 to 5 carbon atoms, and a nitro group 19 are CF. However, U and V each independently represent an alkyl group of carbon atoms jli1 to 12, or together they represent the following formula: (In the formula, 8 凰 and island each independently represent hydrogen atoms, Alkyl group with 1 to 12 children, alkyl group with 1 to 12 carbon atoms substituted with 1 or several halogen atoms, phenyl group, 1!7'C is several halogen atoms and/or carbon atoms m1 to 5 represent a phenyl group substituted with an argyl group or a group represented by the formula 2CHs-Z-kty (wherein 2 represents a # element tfch yellow atom, and approximately 7 represents a water bulk atom , alkyl group having 1 to 8 carbon atoms, carbon
or C1-C8 alkyl group substituted with one cy group in 2 alkyl group, pseudoac5-4 alkyl group, 4.2-j robinyl &, 5-halogen-2-7
'Robinyl group, phenyl group, 1 9 is several halogen atoms, alkyl group having 1 to 3 carbon atoms, carbon atom el
-5'f alkoxy group nitro group and/or c i
, phenyl group substituted 11 by 13 groups, unsubstituted or 111 or several noroken atoms, number of carbon atoms 1
rJ11 is substituted by an alkyl group of 1 to 5 carbon atoms and/or an alkoxy group of 1 to 5 carbon atoms (representing a benzyl group), Rs e R4 and N are independently of each other a water bulk atom or a carbon atom W! 11 to 4 represent the Algill Fund,
This bottle stand R3,l? 4 and the carbon atom count in the chest is 6
t- not more than
If the compound described in item 1 is used to form the following alkylene tag, the acid salt and the metal complex. (3) - In Mosquito style supervision, Y represents -C1i='ffi or -N=t-, Km
and Kb each independently represent a hydrogen atom, a halogen atom, carbon, or an alkyl group having 1 to 3 atoms, and Ar is of the following formula: child, halogen atom, CF Hatake'l or carbon atom a1 to all3
represents a group represented by alkyl: IEi), where U and V are defined as mW in the above formula 1 #f represented by #f, and the chemical compound 1 according to claim 2, and acid addition salts thereof and global complexes. (4) In the general formula 1, U and V independently represent an alkyl group having 1 to 3 carbon atoms, but they also represent an alkyl group having 1 to 3 carbon atoms (provided that It+ e
Hz + Hs + kt4 and R8 independently represent a hydrogen atom or a carbon atom alkyl group, but in this case, the total number of carbon atoms in hs, tt4 and ~ cannot exceed 6. alkylene 4 represented by The adducts, acid addition salts and metal complexes thereof according to claim 6, wherein the group tx is represented by -Ci (=t or -N=). (5) In the general formula I, Y is -L'H= and -N represents gold, Ar represents the meaning defined in the above formula 1, Ra, Rb, kca, Rd and He are mutually expressed as a hydrogen atom, a hydrogen atom, a prefecture A wood atom, a fluorine atom, a methyl group, a methoxy group represents a 210 group, and U and V independently represent an alkyl group having 1 to 6 carbon atoms, or '29H- together. to form the alkylene bridge defined in formula 1 above, in which case %
RI*kJ eR@, kca*Rs and R each independently represent a hydrogen atom or a C1-C5 alkyl group, or R1 is represented by the formula C)l, -0-R, represents a group in which R
y is an alkyl group having 1 to 5 carbon atoms, carbon lIk atom a
Carbon X atom e, 2 substituted with 1 to 6 alkoxy groups
The compound according to claim 1, which represents an argyl group having 4 to 4 carbon atoms, an alkenyl group having 5 to 4 carbon atoms, or a phenyl group, as well as its acid salt and metal monomer. (6) In the general formula l, Y represents -('H=!μ-N-, Ra and itb
(wherein We, Rd and Re each independently represent a hydrogen atom, a halogen atom, or an alkyl group of carbon atoms a1 to 5), and Atom, clI゛3, number of carbon atoms 1
j') to 3 alkyl group, or having 1 to 3 carbon atoms
The alcoquine group of ゎゎゎゎゎゎゎゎ゜゜゜゜゜t゜t is represented by ゎゎゎゎゎゎ゜゜゜t゜t, and the symbol representing the meaning of the above formula ゎゎゎゎゎゎゎゎゎ゜゜゜t゜t, and the above formula ゎゎゎゎゎゎゎ゜゜゜゜゜゜t) represents the above formula. 'The compound according to claim 1, the acid addition of compound 7, and a metal complex. (7) In the general formula l, Y follows -Ck-1= or -N2, and Ra and l<
b independently represent a hydrogen atom, a halogeno atom, or an alkyl group having 1 to 5 carbon atoms; )・Rogen atom, CFs *Represents a group represented by an alkyl group having 1 to 5 carbon atoms (1 to 5 carbon atoms represents an alkoxy group having 1 to 5 carbon atoms), U and V are each independently an alkyl group having 1 to 5 carbon atoms. an alkyl group having 2 to 6 carbon atoms, which may be unsubstituted or substituted with an alkoxy group having 1 or 2 carbon atoms;
to 4 alkyl groups t-S or - together (in the formula Rh * RJ m R4 and B4 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) , in this case an island.The total number of carbon atoms in R4 and N must not exceed 6). and metal complexes. (8) In general formula I, Y represents -CH=ltake-N=, and Ra and Wb each independently represent a hydrogen atom, a halogen atom, a box, or an alkyl group having 1 to 6 carbon atoms. , Ar are the following formulas: (wherein Raw Rd and Re td, independently of each other,
Hydrogen atom, halogen atom, CF, 1 to 6 carbon atoms
(in the formula, & represents a carbon atom el to 4 carbon atoms);
an alkyl group having 2 to 4 carbon atoms substituted with an alkoxy group having 1 to 2 carbon atoms, carbon 1il
2. The compound according to claim 1, wherein e represents an alkenyl group having 3 or 4 atoms, or a 2-propynyl group; (9) In the general formula I, Y represents -CH=t-, Ar represents the meaning defined in the above formula I, and Ra and RbU independently represent a hydrogen atom, a methyl group, a chlorine atom and a bromine atom. Re, Rd and He independently represent a hydrogen atom, fluorine atom, chlorine atom, bromine atom, methyl group, methoxy group, cFsxfc represents a nitro group, and U and V independently represent an unsubstituted or an alkoxy group having 1 to 2 carbon atoms or an alkyl group having 1 to 6 carbon atoms substituted with a chlorine atom; At & Wasuka, this bottle stand R + + & I R
1e R4m k and 3 each independently represent a hydrogen atom or an alkyl group t' having 1 to 5 carbon atoms, or #iR1 represents a group t- grouped in the formula (JbORt);
Representation, Kome・ba@R7Fi An alkyl group having 1 to 3 carbon atoms, an alkyl group having 2 or 5 carbon atoms substituted with an alkoxy group of 11 carbon atoms, or an alkyl group having 3 or 4 carbon atoms. The alkenyl group t- of claim 1, and acid addition salts and metal complexes thereof. 4 In general formula 1, Y represents -CH= or -N=, Ra and Wb each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and Ar represents a terminal WL substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, CFbt or a halogen atom, and U and V are defined in the above formula 1 Compounds as claimed in claim 1, as well as acid addition salts and metal complexes thereof. Qυ In general formula 1, ゛ If Y brings -CH= j or -N=, Ra and Rb
independently of each other represent 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 a ciI', and U and V independently of each other Alkyl, MS or halogen atoms having 1 to 5 carbon atoms or 1 atom to 3 carbon atoms
or an alkyl group having 1 to 3 carbon atoms which may be substituted with 2 alkoxy groups, or - together (wherein kLt, kL鵞, R3, yen and - are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, in which case the number of carbon atoms in R4 and 4 must not exceed 4); A chemical compound according to item 1, as well as an acid addition salt and a metal complex thereof. Q4 In the general formula (■), Y represents -CH-4-N=, Ra and Wb represent a hydrogen atom, Ar is unsubstituted or a halogen atom, or Vumethyl≠
represents a phenyl group substituted with an alkyl group having 1 to 3 carbon atoms, such as a hydroxymethyl group or 2-hydroxyethyl group, or an alkoxy group having 1 or 2 carbon atoms, such as a methoxymethyl group or an ethyl group; 7 (representing a methyl group)
The conversion described in the section e! # and its acid addition salts and metal complexes. Q32-(p-(phenoxy)phenyl)-2-(1-
(1) 1-1.2.4-) methyl]-4
-Methyl-1,3-dioxane or a salt thereof
The compound described in item 1 of the scope of f-specifications. 042-[p-(phenoxy)phenyl]-2-(1-
(IH-1,2,4-triazolyl)methyl]-4-ethyl-1,5-dioxane 11'I:. The compound according to claim 1, which is a salt thereof. (to) 2-(p-(phenoxy)phenyl]-2-(
1-(tf(-1,z4-)゛riazolyl)methyl]-
Compound 8 according to claim 1, which is 4-methyl-1,6-dioxolane or a salt thereof. (2) 2-(p-(phenoxy)phenyl]-2-(
1-(I H-1,2,4-)riazolyl)methyl]-
The compound according to claim 1 which is 4-ethyl-1,5-dioxolane or 7-dioxolane → Of course. Q7+2-1. p-(phenoxy)phenyl]-2-(
+ -(IH-1,,2,4-)riazolyl)methyl J
The compound according to claim 1, which is -4-methyl-5-methyl-R5-dioxolane. 082-4p-(phenoxy)phenyl]-2-[1
-(1,H-1,2,4-)riazolyl)methyl J-1
, 5-dioxane or 7 salts %Iv! IF A compound according to claim 1. 4 2-(1)-(phenoxy)phenyl]-2-(1
-Imidazolylmethyl)-4-ethyl-1,5-dioxolane or a mound thereof. (E) 2-(p-(2,4-di,methylphenoxy)
The compound according to claim vJ1, which is phenyl)-2-(1-ibadazolylmethyl)-4-ethyl-1,5-dioquinolane or its feedstock. eυ 2-(p-(3-chlorophenoxy)phenyl)
-2-11-imidazolylmethyl)-4-ethyl-1,
The compound according to claim 1, which is 3-dioxolane 17tH. 4 2-(p-+4-chlorophenoxy)phenyl)-
2-(1-imidazolylmethyl)-4-ethyl-1,3
-Dioxolane or a salt thereof Claim 1
The monster described in the section. CA 2-(p-(3-to17fluoromenalphenoxy)phenyl J-2-(1-imidazolylmethyl)-4
-Ethyl-1,6-dioxolane 19 is a salt thereof. (j42-(p-(4-chloro-3-methylphenoxy)phenyl)-2-(1-ibadazolylylmethyl)-4
-Ethyl-1,6-dioxolane or a salt thereof. -2-[p-5,4-dichlorophenoxy/)ferol 3
-2-11-imidazolylmethyl)-4-ethyl-1,
Hypothesis according to claim 1 which is 3-dioquinrane or Seven Fortunes@2-(p-(2,5-dichlorophenoxy)phenyl)-2-(1-imidazolylmethyl)-4- The compound according to claim 1 which is ethyl-1,3-dioxolane or a salt of a (2-(p-(+4-dichlorophenoxy)phenyl)-2-11-imidazolylmethyl) -4-Methoxymethyl-1,6-dioxolane'J 1-imidazolylmethy711/)-4-ethyl-1,6-dioxolane 1d. )-2-(1-imidazolylmethyl)-4-methyl-5
-The compound according to claim 1, which is methyl-1,6-dioxolane or a salt thereof...2-(p-(4-chloro-2-methyl-phenoxy)phenyl,)-2-(1-imidazolyl) methyl)-4
-methoxymethyl-1,6-dioxolane, the compound 6υ 2-(p-(phenoxy)phenyl]-2-[1
-tin-1-1,2,4-)riazolyl)methyl"-
2-(p-(4-fluorophenoxy)phenyl 3-2(14mi))-7" Lil) Chill) -4-
2-(p-(4-fluorophenoki/)phenyl J -? -L 1- (1
H-1,2,4-triazolyl)-mer) -i,
Compound described in Section 4 of Section 1 of s-dioquiline Kari R1 - A) General formula: (In the formula, tvle [hydrogen atom or metal cation 7, Y is -C) l='! or -N=), and a compound having the general formula ill:a (wherein, Rat Rb+ Arm U and V are the above formula!
The meaning defined by Xri, the Xri-philic separating group) and all 11ils! 1 or the first order B) General formula ■: Ra (in the formula, Y, Ha, ktb, and Area represent the meaning defined in the following formula 1) Next (U in the formula
and V represent the meaning defined in the following formula (■)) A group Kf represented by -, l or C) General formula I
, U and V together form the following formula: -CHs-C
In order to produce a compound that follows the group represented by M (C-busizuke) - (in the formula R4n represents the other meaning excluding the hydrogen atom among the R1 groups defined in the following formula (■)), the general formula (■) is used.
: The compound represented by and the following formula■: Hmm-R? (■). [In the above formula, Ra, fib, Y, Ar and R? u
The formula below! and one of Xl and 9 represents a mercapto group, and the other represents a nucleophilic separating group t-fi, or Xt and both represent water fl groups], and the chemical e and are crossed each other, or lfc is D) A compound represented by the general formula ■: Ar -Xs (Mll) and the general formula ■: [in the formula, Ar, Ra, Rb, Y* U and vFi represent the meaning defined by the following formula!, and one of the two is the formula -〇-Ma1 in the formula MeI/'i water IA (representing a metal cation) and the other represents a group capable of being converted into an aryloxy group] are condensed with each other, or (formula Intra-molecular decarboxylation of the compound*1 (in which Y* Ra e K b e A r e U and ■ represent the meanings defined in formula I) is carried out, and if desired, the compounds obtained by these methods are The compound '@ can be converted into other compounds of formula I by converting it into an acid addition salt rc,j or the free compound obtained by these methods. The conversion of acid addition salts into free compounds, or into acid addition salts, or the free compounds or acid addition salts obtained by these methods into gold complexes is specifically described. Y fl -C)1=17t is -N-'f-represents L,
Ra and Wb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, 17'C represents a nitro group, and Ar represents a nitro group; , 111 or a phenyl group substituted by 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 CFx group 1 represents a naphthyl group, U and v each independently represent an alkyl group having 1 to 12 carbon atoms, which may be unsubstituted or substituted with a halokene atom or an alkoxy group having 1 to 6 carbon atoms, or together, The following formula: (wherein R1 and R1 are independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having carbon atoms a1 to 12 substituted with a halogen atom of 11161 or am, A phenyl group, a phenyl group substituted with one or more hydrogen atoms and/or an alkyl group having 1 to 3 carbon atoms, or a group represented by the formula: 1!!
In the formula, 2 represents an atom or a sulfur atom, and R? is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 1 carbon atom.
1 is substituted with one alkoxy group of 2, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, 2-propynyl, S-halogen-2-
7'lopynyl group, phenyl group, one or several halogen atoms, alkyl group having 1 to 5 carbon atoms, carbon 11. Alkoxy group having 1 to 3 atoms, nitro group and/or (
Phenyl group substituted by J+'S group, unsubstituted f11 or one or several halogen atoms, number of carbon atoms 1
to 3 alkyl group and /"fft is a benzyl group substituted by an alkoxy group having 1 to 3 carbon atoms;
, Wash), Rs, R4 and Rs each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; in this case, 3. The total number of carbon atoms in R4 and N is 6.
Without exceeding, and &t-j hydrogen gland hydrogen order alkyl group having 1 to 6 carbon atoms -? In the general formula 1, Y is -Ct4. represents -N=, and Ra and Rbtlj each independently represent a hydrogen atom, 710
Represented by a gen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a nitro group 1, Ar is represented by the following formula: (wherein Re, Rd, and Ret1 are each independently a hydrogen atom , halogen atom, alkyl group having 1 to 5 carbon atoms,
Alkoxy group having 1 to 5 carbon atoms, nitro group 17'c
represents a group of the following formula: (in the formula Rt and stone each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with 111! fld halokene atoms, a phenyl group, 1 ( 1111 phenyl group or a group of the formula CHz -l -Ry, which is substituted with several ]-logon atoms and/or alkyl groups having 1 to 5 carbon atoms, (
However, 2 in the formula is I! #Kvr, covered with yellow atoms
J water J atom, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted by one alkoxy group having 1 carbon atom or Fi2, an alkenyl group having 6 to 4 carbon atoms, 2-propynyl group, 3-halogen-
2-7'ropynyl group, phenyl group, one or several halogen atoms, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 5 carbon atoms, nitrot &/or C
Phenyl group substituted by F3 group VC, unsubstituted or one or several halogen atoms, number of carbon atoms 1 to 5
(represents a be/zyl group substituted by an alkyl group and/or an alkoxy group having 1 to 5 carbon atoms), kcs * R4 and Kl each independently represent a hydrogen atom 1 or a carbon atom 1 to 4 represents the alkyl fund of carbon atoms in 1 (a, ni? 4 and 4).
The number does not exceed 6, and R6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. To prepare a complex, A) General formula n: (In the formula, !V1e represents a hydrogen atom or a cation, and represents Y#goCH='f fctl -N=)
and a compound represented by the general formula m: (wherein Ra, Rh, Ar, U and vh have the meanings defined in the above formula l, and X represents a separating group) or carbonyl 4 in the compound represented by the following formula % formula % () (in the formula U and V represent the meanings defined in the above formula 1) to react with a diol represented by the following formula V: (wherein U and V represent the meanings defined in the above formula I) 17'cldC) In the general formula I, U and ■ come together to form the following formula
H(CkbZK4) - (wherein R4 represents a group other than a hydrogen atom among the R7 groups defined in Formula I, 2 represents oxygen or a cypress atom) To produce the compound represented by the general formula■
:, a and the general formula (■): X2-R7 (■). (In the formula, Ra, Rho Y* Un V and R1 have the meanings defined in the above formula, one of Xl and R is water #l'f and mercapto group 't'', and the side is X represents a nucleophilic separating group in place, or
(where both l and represents the meaning of
('1 formula - (J-Me (in the formula, Me is a hydrogen atom of 1st order)
1 Hi 8 cut expressed by (representing a metal cation) and −Makio ■: Ra (where Y, Ram Rb* U and Vij the following formula l
and the compounds represented by , converting the acid addition salts obtained by these methods into free compounds or other acidic palatable compounds, or converting the free compounds or acid addition salts obtained by these methods into metal complexes. The method according to claim 34, characterized in that Y represents -cn=v or -N=, and Ra and Rb each independently represent a hydrogen atom, a norogen atom, or the number of carbon atoms. 1 to 3 alkyl group, 1 carbon atom
represents an alkoxy group or a nitro group having 1 to 6 carbon atoms, Ar is unsubstituted or one or several ) rogen atoms, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a nitro shield and/or a phenyl group or naphthyl group substituted with a CF3 group; an alkyl group having 1 to 12 carbon atoms, t-
or (in the formula, 16 and the mountain are water Jc independently of each other)
iiA atom, an alkyl group having 1 to 12 carbon atoms, and several halogen atoms per narrow cylinder m! Ii number of carbon atoms 1
an alkyl group of 1 to 12, a phenyl group, a phenyl group substituted with one or several halogen atoms and/or an alkyl group of 1 to 6 carbon atoms, or a phenyl group substituted with the formula C1 (1-Z-R?); (wherein the formula zFi acid: , alkyl group having 11 to 8 carbon atoms, alkenyl group having 3 to 4 carbon atoms, 2-propynyl group, 3-haloken-2-propynyl group, phenyl group, one or several halogen atoms, carbon atom Alkyl group of number 1 to 5, alkoxy group of carbon atoms a1 to 5, nitro group and /1ft is CF, phenyl group substituted by group, unsubstituted or 1
J11! ! ``! or several halogen atoms, 1 carbon atom
(represents a benzyl group substituted with f11 by an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms), R8* R4 and - are VC independently of each other, and represent a hydrogen atom or a carbon atom number. 1 to 4 alkyl groups, but in this case, the accounting number of carbon atoms in G R3g R4 and Ra is 6
and the electron represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), acid addition salts thereof, and metal complexes thereof. Tomo-attn
A shoulder pest control agent for agricultural use for controlling or preventing damage caused by microorganisms, which is characterized by containing the agent as an active ingredient. @ As an active ingredient, the following compound group: 2-(p-(phenoxy)phenyl J-2-CI-(IH-1,2,4
-1-riazolyl)methyl)-4-mef-1,5-dioxane, the first is its salt, 2-(p-+7 enoxy)phenyl]-2-(1-+1
11-1.2.4-)riazolyl)methylcou 4-ethyl-1,3-dioxane 1fC is its salt, 2-(p-(phenoxy)phenyl)-2-(1-(I
H-1,2,4-)riazolyl)methyl]-4-methyl-1,5-dioxolane or its salt, 2-(p-(phenoxy)phenyl)-2-(1-(1
) 1-1.2.4-) riazolyl)methyl]-4-ethyl-1,5--/oxolane primary is characterized by containing at least one polarity from its salts. A pest control agent according to claim 1g56. Claim 5, characterized in that it contains an active ingredient represented by formula I from 99.9% to 99%, a solid or liquid additive from 99.9% to 1%, and a surfactant from 0 to 25%.
The pest control agent according to Section 67 of Section 6. ■ Active ingredients represented by formula l (Ll to 95%, solid or liquid additives 998 to 5%, and valve surface active All
A pest control agent according to claim g5a, characterized in that it contains α1 to α25. - Plant: The pest control agent according to claim 36, characterized in that the plant body t7c is applied to its cultivation area in order to control or prevent damage caused by harmful microorganisms. The pest control agent according to claim g40, wherein the microorganism harmful to plants is a fungus harmful to plants. [In the formula, Y is -CH=X or -N=t-, Ra and Rb are each independently a water-based atom, ), a rogene atom, an alkyl group having 1 to 6 carbon atoms, a carbon atom number 1 to 3 alkoxy groups or nitro groups, Ar is one or more carbon atoms, an alkyl group having 1 to 7 carbon atoms, a carbon a! 1
to 7 alkoxy groups, nitro groups and/or CF, phenyl groups or naphthyl groups substituted by 1 to 7 alkoxy groups, U and vh independently of each other are unsubstituted or unsubstituted or carbon atoms al to 6 An alkyl group having 1 to 12 carbon atoms that may be substituted with an alkoxy group? r represents or together represents the following formula: (wherein R1 and Rzi each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, one primary Fi carbon substituted with several halogen atoms; Alkyl group having 1 to 12 atoms, phenyl group, one or several halogen atoms and/or
It also represents a phenyl group substituted with an alkyl group having 1 to 3 carbon atoms or a group represented by the formula: (wherein, zVi oxygen or 71c represents a sulfur atom, and Ry represents Hydrogen atom, alkyl group having 1 to 8 carbon atoms, alkyl group having 1 to 8 carbon atoms substituted with one alkoxy group having 1 to 2 carbon atoms, 7 carbon atoms /
l/key = y, 2-7' robinyl &, 5-'' rhodan-2-propynyl group, phenyl group, one or several haloken atoms, alkyl group having 1 to 6 carbon atoms, 1 carbon atom to 5 alkoxy groups, nitro groups and/or C
F, a phenyl group substituted by a phenyl group or a halogen group or one or several halogen atoms, a C1-C5 alkyl group and/or a C1-C6 alkoxy group VL benzyl foundation), Rm * R4 and 1ζsr are independently of each other a water X atom or an alkyl group of carbon atoms ei1 to 4, in which case H3, & and h = the total number of carbon atoms in is 6
, and form an alkylene bridge represented by kL, Fi representing a hydrogen atom or an alkyl group having 1 to 3 carbon atoms], as well as its acid addition salts and metal complexes. A therapeutic agent for the human body or animals containing one kind of auxiliary agents and carriers that are commonly used. - The therapeutic agent according to claim 42, wherein the antifungal and/or anticonvulsant agent has an anxiolytic effect - The following compound group: 2-(p-(phenoxy)phenyl)-2- (1-(1
1-4-1,2,4-triazolyl)methyl]-4-methyl-5-methyl-1,3-dioxolaf, 2-(p-(phenoxy)phenyl]-2=CI -f
111-1.2.4=,-triazolyl)methyl)
-1,5-dioxane tfc is its name, 2-(p-(phenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,6-dioxolane 'f7'c is its salt, 2- (p-(2,4-dimethylphenoxy)phenyl)-2-(1-imidazolylmethyl)-4-ethyl-1,5-dioxolane or its salt, 2-[p-(3-chlorophenoxy)phenyl J- 2-
(1-ibadazolylmethyl)-4-ethyl-t5-dioxola/or salt thereof, 2-(p-(4-chlorophenoxy)phenyl)-2-(1-imidazolylmethyl)-
4-ethyl-t3-dioxolane or its salt, 2-
(p-(5-) IJ Fluoromethylphenoxy]phenyl J-2-(1-ibadazolylmethyl)-4-ethyl-1,3-dioxolane or its salt, 2-(p-14-chloro-5- methylphenoxy)phenyl)-2-(1-imidazolylmethyl)-4-ethyl-1,5-dioxolane tfI- is a salt of 7, 2-(p-(44-dichlorophenoxy)phenyl)
-2-(1-imidazolylmethyl)-4-ethyl-1,
5-dioxoraf or its salt, 2-(1)-(2,5-dichlorophenoxy)phenyl)-2-11-imidazolylmethyl)-4-ethyl-
1,5-dioxolane or its salt, 2-(p-(44-dichlorophenoxy)phenyl)-
2-(1-imidazolylmethyl)=4-methoxymethyl-t.3-dioxolane or its salt, 2-(p-(4-fluorophenoxy)phenik')
-2-(1-imidazolylmethyl)-4-ethyl-1
,5-dioxolane primary is its salt, 2-(p-(4-fluorophenoxy)phenyl)-2
-(1-1Mida7"J-methyl)-4-methyl-5-methyl-1,3-dioxoraf or its salt, 2-[p-(4-chloro-2-methyl-phenoxy/)phenyl)-2 -(1-ibadazolylmethyl)-4-methoxymethyl-1,5-dioxolane or its salt, 2-(p-(phenoxy)phenyl)-2-(1-+
IH-1,2,1-triazolyl)methyl]-4-bitroxymethyl-1,3-dioxolane, 2-(p-(4-fluorophenoxy)phenyl)-2
-(1-imidazolylmethyl)-4-hydroxymethyp
v -1,5-dioquinrane, 2'-(p-(4-fluorophenoxy)phenyl)-2-(:1-(1)1-
L2. Therapeutic agent according to item 42, which contains at least a compound selected from 4-triazolyl)-methyl)-1,5-dioxane as a seed ingredient - Train Animal V In order to control parasitic snails, and/
or constant epilepsy, anxiety, nervousness and excitement;
and/1. The therapeutic agent according to claim 42, which is used to treat a pre-existing condition.