DD207143A5 - AGROCHEMICAL SHAED LABORATORY AGENT - Google Patents

Abstract

The invention relates to an agrochemical Schaedlingsbekaempfungsmittel for the control of phytopathogenic fungi in agriculture. The aim of the invention is to provide a new agent with a broad microbicide spectrum. As an active component in the novel compositions according to the invention new arylphenyl ether derivatives of the formula I are used, wherein, for example: Y is -CH = or -N =; R below a and R below b independently of one another represent hydrogen, halogen, C below 1-C below 3-alkyl, C below 1-C below 3-alkoxy or nitro; Ar optionally polysubstituted phenyl or naphthyl; U and V independently of one another for C optionally substituted by halogen or C below 1-C below 6-alkoxy C below 1-C below 12-alkyl u.a. The compounds according to the invention can be used on the one hand in the agricultural sector or related fields for the control of phytopathogenic microorganisms and on the other hand as antifungal and / or anticonvulsive and anxiolytic drugs, for example for combating parasitic fungi on warm-blooded animals and / or for the treatment of various forms of epilepsy, anxiety , Voltage and excitation states and / or manic Gemuetszustaenden use.

Description

Berlin, 28.10.1982 AP С 07 D / 239 803 (60 854/12)

Agrochemicals Pesticides Field of application of the invention

The present invention relates to agrochemical pesticides containing substituted Arylphenyletherderivaten and their acid addition salts and metal complexes · It also relates to the preparation of these compounds, the preparation of agrochemical compositions or preparations and their use and a method for controlling or preventing an attack of plants by phytopathogenic microorganisms ,

Characteristic of the known technical solutions

1- (β-Aryl) ethyl-midazolyl ketals in which aryl is substituted

Phenyl or ilaphthyl are listed below

cited as fungicides and bactericides »US Pat. Nos .: 3,575,999, 3,936,470, 4,101,664, 4,101,666, 4,156,008.

Object of the invention

The aim of the invention is the provision of new agents with a broad microbicide spectrum.

Explanation of the essence of the invention

The invention has for its object to find new compounds with microbicidal activity, which are suitable as an active component in agrochemical pesticides.

-1- 28.10.1982

iJ ^J G 07 U / 239 (60 854/12)

ОітіііЗ be in the new agents as active two-component arylphenyl ether derivatives of the formula I.

U ₄

/ ⁴ V

. -t-c ο γ

Ar-O-. · -G -0

CH "-U

applied, in which

for -GH = or -14 = stands; and each independently represent hydrogen, halogen, G ₁ -G ₃ -alkyl, G ₁ -G ₃ -alkoxy or nitro; unsubstituted or substituted by halogen, GJC ₇ alkyl, O ₁ -J ^ -Akoxy, nitro and / or GiV mono- or polysubstituted phenyl or ilaphthyl;

U and V, independently of one another, are C -C -alkyl optionally substituted by halogen or C 1 -C 4 -alkoxy, or together represent one of the following alkylene bridges

or

form, where

R and R independently of one another represent hydrogen,

Alkyl, one

or C-C "alkyl which is monosubstituted by halogen, phenyl, phenyl which is monosubstituted or polysubstituted by halogen and / or C 2 -C 4 -alkyl or represents the group -CH-ZR ₇ , where

Z means oxygen or sulfur and

R, is hydrogen, C ₁ -C -alkyl, substituted by C ₁ -C -alkoxy

C 1 -C 4 alkyl, C 1 -C 4 alkenyl, 2-propynyl, 3-halo-2-propynyl, Io J4

Phenyl, a halogen, C -C alkyl, C ₁ -C alkoxy, nitro and / or

Lj Lj

CF_ is mono- or polysubstituted phenyl, benzyl or benzyl mono- or polysubstituted by halogen, C.sub.1-C.sub.4-alkyl and / or C.sub.1-C.sub.-alkoxy;

R, R, and R ₁ . independently of one another denote hydrogen or C.sub.1 -C.sub.4, -alkyl, where the total number of carbon atoms in R, R and R_ does not exceed 6 and

R is hydrogen or C ₁ -C 6 alkyl; Ij

including their acid addition salts and metal complexes.

The substituent Ar has as optionally substituted phenyl or naphthyl, for example, the formula

X =.

R-s

or R, -

D

-3- 28.10.1932

лР С 07 D / 239 303 (60 854/12)

wherein R, R ₁ and Λ are independently hydrogen, halogen, C ₁ -G ₇ -AIkJiI, C ₁ -G ₇ -Akoxy, nitro or GF ₃ .

The term alkyl itself or as a constituent of another substituent, depending on the number of carbon atoms given, for example, the following groups to understand: LethyI ₁ χ-ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl as well as their isomers such. As isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl, etc. Alkenyl is z. As for propenyl-d), allyl, butenyl (1), butenyl (2) or butenyl (3) halogen is here and below fluorine, chlorine, bromine or iodine, preferably chlorine or bromine, mean.

The invention relates both to the free compounds of formula I and their addition salts with inorganic and organic acids, as well as their complexes with metal salts.

Salts according to the invention are in particular addition salts with physiologically acceptable inorganic or organic acids in accordance with the .uinu at ζ purpose.

It has surprisingly been found that compounds of the formula I have a very favorable for practical needs Likrobizid spectrum against phytophathogenic fungi and bacteria as well as their usefulness as active ingredients based antifungal and / or anticonvulsive properties.

-За- 28.10.1982

Л * ü 07 іѴ239 ВОЗ (ЬО 854/12)

with respect to the use of uikrobicides in plant protection physiologically acceptable inorganic and organic acids are, for example, hydrohalic acids, eg, hydrochloric, bromic or Iodwaseerstoffsäure, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, optionally halogenated fatty acids such as acetic acid, irichloroacetic acid and oxalic acid, or Sulfonic acids, such as benzenesulfonic acid and hethanesulfonic acid.

With regard to the use of a pharmaceutically active substance physiologically acceptable acids, d. H. pharmaceutically acceptable acids are, for example, pharmaceutically usable mineral acids, such as hydrohalic acids, eg. As hydrochloric, hydrobromic or hydroiodic acid, nitric acid, sulfuric acid or phosphoric acid, pharmaceutically acceptable carbon

and sulfonic acids, such as aliphatic mono and optionally hydroxylated dicarboxylic acids, e.g. Acetic acid, fumaric acid, maleic acid, malic acid or tartaric acid, as well as aliphatic or aromatic sulfonic acids such as lower alkane or optionally substituted benzenesulfonic acid, e.g. Methane, ethane, benzene, p-toluene and p-bromobenzenesulfonic acid, further sulfamic acids, e.g. N-Cyclohexylsulphamic.

Metal complexes of formula I consist of the underlying organic molecule and an inorganic or organic metal salt, e.g. halides, nitrates, sulphates, phosphates, tartrates, etc. of copper, manganese, iron, zinc and other metals. The metal cations can be present in the various valences that belong to them.

The compounds of formula I are stable at room temperature oils, resins or solids, which are characterized by very valuable physiological, such as microbicidal, such as plant-fungicidal and pharmacological, in particular antiraykotic and anticonvulsant and anxiolytic properties. They can therefore be used on the one hand in the agricultural sector or related fields for the control of phytopathogenic microorganisms and on the other hand as antifungal and / or anticonvulsive and anxiolytic drugs, for example, to control parasitic fungi on warm-blooded animals and / or for the treatment of various forms of epilepsy, anxiety, Voltage and excitation states and / or manic mental states, use.

A group of microbicides important for use in plant protection consists of compounds of formula I wherein Y is -CH = or -N =; R and R 1 independently of one another represent hydrogen, halogen, C 1 -C -alkyl, C 2 -C -alkoxy or nitro; Ar for the group

VV

R - С

or R-

S \

• stm

stands; in which

R, R and R are independently hydrogen, halogen, C-C-c d e Ij

Alkyl, C.-C alkoxy, nitro or CF;

U and V independently of one another are C -C -alkyl or together represent one of the following alkylene bridges

or

⁶ V;

form, where

R. and R independently of one another are hydrogen, C 1 -C 4 -alkyl, C 1 -C 8 -alkyl substituted one or more times by halogen, alkyl, phenyl, mono- or polysubstituted by halogen and / or C 1 -C 6 -alkyl Phenyl or the group -CH ₅ -ZR ₇ , where

Z means oxygen or sulfur and

R ₇ is hydrogen, C, -C _o alkyl, substituted by C ₁ -C alkoxy C.-C alkyl, С -Сд-alkenyl, 2-propionyl, 3-halo-2-propynyl, phenyl, by halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, nitro and / or CF. phenyl which is monosubstituted or polysubstituted, benzyl or a benzyl mono- or polysubstituted by halogen, C 1 -C -alkyl and / or C 1 -C -alkoxy;

R, R, and R ₁ . independently of one another are hydrogen or C.-C-alkyl, the total number of carbon atoms in R, R and R ₅ not exceeding 6 and

R is hydrogen or C 1 -C 4 alkyl;

including their acid addition salts and metal complexes. This subgroup should be referred to here and below as Cruppe Ia.

A preferred group of agriculturally useful microbicides are compounds of formula I, including their salts and metal complexes, wherein Y is -CH = or -N =; R and R 1 independently of one another represent hydrogen, halogen or C 1 -C 4 -alkyl; Ar for the group

wherein R, R and R independently of one another are hydrogen, halogen, CF or C.-C "-alkyl; and U and V have the meanings given under formula I; this group should be called Ib.

Within subgroup Ib, preference is given to those compounds of the formula I as microbicides in which U and V, independently of one another, are C 1 -C -alkyl or together represent one of the following alkylene groups

• - ·

in which R, R ", R, R, and R_ independently of one another represent hydrogen or C ₁ -C -alkyl, the total number of carbon atoms in R_, R, and R not exceeding 6; this group should be called Ic.

Another preferred group of agriculturally advantageous microbicides are compounds of formula I wherein Y is -CH = or -N =; Ar has the meanings given under formula I; R, R, R, R and R independently of one another represent hydrogen, chlorine, bromine, fluorine, methyl, methoxy or nitro; U and V independently of one another represent C 1 -C -alkyl or together form one of the alkylene groups mentioned under formula I, where R, R, R, R 1, R ₅ and R 4 independently of one another represent hydrogen or C 1 -C 4 -alkyl or R. for

- 7 -

-CH ₂ -OR ₇ where R is C ₁ -C 4 alkyl, C ₁ -C ₃ alkyl substituted by C ₁ -C ₃ alkoxy, C ₃ -C alkenyl or phenyl; this group should be called Id.

Among the microbicides of subgroup Id, those are particularly preferred in which U and V together form an unsubstituted or monosubstituted ethylene or propylene bridge; this group should be called Ie.

For example, the following substances belong to the particularly preferred agriculturally useful individual substances:

2- [p- (phenoxy) phenyl] -2- [l- (lH-l, 2,4-triazolyl) methyl] -4-methyl-1,3-dioxane,

2- [p- (phenoxy) phenyl] -2- [l- (lH-l, 2,4-triazolyl) methyl] -4-ethyl-1,3-dioxane,

2- [p- (phenoxy) phenyl] -2- [l- (lH-l, 2,4-triazolyl) -raethyl] -4-methyl-1,3-dioxolane,

2- [p- (phenoxy) phenyl] -2- [l- (lH-l, 2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane.

With respect to the antifungal activity, the group If is of compounds of the formula I in which Y is -CH = or -N =, R and R ^ independently of one another are hydrogen, halogen or C ₁ -C -alkyl; Ar for the group

R с

wherein R, R and R independently of one another are hydrogen, halogen, CF ", C ₁ -C -alkyl, C ₁ -C -alkoxy; and U and V have the meaning given under the formula I, in the foreground.

Within the subgroup If, those compounds of the formula I are preferred by their antifungal effect, wherein U and V independently of one another are C 1 -C 8 -alkyl, C 1 -C -alkyl which is optionally substituted by halogen or CC ₂ -alkoxy, or together one of them following alkylene groups

^R i \ Л _A ³ V / ⁴

/ ° the j

in which R, R ", R, R and R independently of one another represent hydrogen or C -C -alkyl, the total number of carbon atoms in R, R and R being ₁ . the number 6 should not exceed; this group should be called Ig.

Within the subgroup If, those compounds of the formula I are preferred by their antifungal activity, wherein U and V together represent the alkylene group CH OR

• - ·

wherein R ₇ is C 1 -C 4 alkyl, C 1 -C 4 alkyl substituted by C 1 -C 6 alkoxy, C 1 -C 4 alkenyl or 2-propynyl; this group should be called Ih.

Another preferred group of antifungal compounds of formula I are those in which Y is -CH =; Ar has the meaning given under formula I; R and R independently of one another represent hydrogen, methyl, chlorine or bromine, R, R, and R independently of one another represent hydrogen, fluorine, chlorine, bromine, methyl, methoxy, CF or nitro; U and V, independently of one another, are C ₁ -C -alkyl optionally substituted by C ₁ -C 4 -alkoxy or chlorine or together form one of the alkylene groups mentioned under formula I, where R, R ₇ , R_, R, R ₁ . and R 4, independently of one another, are hydrogen or C 1 -C 4 -alkyl or R 4 is -CH_OR, where R is C 1 -C 4 -alkyl, C 1 -C -alkyl substituted by C 1 -C 4 -alkoxy or C 1 -C 4 -alkyl, C, alkenyl; this group should be called Ii.

For example, the following compounds belong to the particularly preferred antimycotically active individual substances:

2- [p- (phenoxy) phenyl] -2- [l- (lH-l, 2,4-triazolyl) -raethyl] -4-methyl-5-methyl-1,3-dioxolane; 2- [p- (phenoxy) phenyl] -2- [l- (lH-l, 2,4-triazolyl) methyl] -l, 3-dioxane; 2- [p- (phenoxy) phenyl] -2- (l-imidazolylmethyl) -A-ethyl-l, 3-dioxolane; 2- [p- (2,4-dimethylphenoxy) phenyl] -2- (l-imidazolylmethyl) -4-ethyl-1,3-dioxolane; 2- [p- (3-chlorophenoxy) phenyl] -2- (l-imidazolylmethyl) -4-ethy1-1,3-dioxolane; 2- [p- (4-chlorophenoxy) phenyl] -2- (l-imidazolylmethyl) -4-ethy1-1,3-dioxolane;

2- [p- (3-trifluoromethylphenoxy) phenyl] -2- (l-imidazolylmethyl) -4-ethyl-

1,3-dioxolane;

2- [p- (4-chloro-3-methylphenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethy1-

1,3-dioxolane;

2- [p- (3,4-dichlorophenoxy) phenyl] -2- (l-imidazolylmethyl) -4-ethy1-1,3-

dioxolane;

2- [p- (2,5-dichlorophenoxy) phenyl] -2- (l-imidazolylmethyl) -4-ethy1-1,3-

dioxolane;

- 10 -

2- [p- (3,4-dichlorophenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-methoxy-1-yl 1-1, 3-d, loxo; m; 2- [p- (4-fluorophenoxy) phenyl] -2- (l-imidazolylmethyl) -4-ethy1-1,3-dioxolane;

2- [p- (4-fluorophenoxy) phenyl] -2- (l-imidazolylmethyl) -4-methyl-5-methyl-1,3-dioxolane;

and each of their pharmaceutically acceptable acid addition salts, processes for their preparation, pharmaceutical compositions containing them and their use as excipients.

With regard to the anticonvulsive and anxiolytic activity, the group Ij of compounds of formula I, wherein Y is -CH = or -N =, R and R independently of one another are hydrogen, halogen or C.-C-alkyl and wherein Ar is unsubstituted or phenyl which is substituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, CF, or halogen and U and V have the meaning given under formula I, in the foreground.

Within subgroup Ij, especially the compounds of formula I are to be emphasized with markedly favorable anticonvulsant and anxolytic activity, in which Y is -CH = or -N =, R and R 1 independently of one another are hydrogen, methyl, chlorine or bromine, and Ar unsubstituted or by halogen, methyl or CF. substituted phenyl and U and V are independently C, -C alkyl, optionally substituted by halogen or C.-C_ alkoxy-substituted C »-C alkyl or together one of the following alkylene groups

^R 1X / 2

in which R, R ₂ , R ₃ , R ₄ and R ₅ independently of one another represent hydrogen or C 1 -C 4 -alkyl, the total number of carbon atoms in R ₃ , R and R not being to exceed 4 ; this group should be called Ik.

-M-

A further preferred group of markedly anticonvulsive and anxiolytic compounds are those in which Y is -CH = or -N =, R and R, are hydrogen, Ar is unsubstituted or substituted by halogen, methyl-substituted phenyl and U and V together a group of the formula

Λ / \

/ \ or J j

in which R _{1 is} C ₁ -C 4 -alkyl, such as methyl or ethyl, or hydroxy-C ₁ -C 4 -alkyl, such as hydroxymethyl or 2-hydroxyethyl, or C ₁ -C -alkoxy-C ₁ -C 4 -alkyl. Alkyl such as methoxymethyl or ethoxymethyl; this group should be called Il.

The following compounds are among the particularly preferred anticonvulsant and anxiolytic single substances:

2- [p- (phenoxy) -phcnyl] -2- [l- (lH-l, 2,4-triazolyl) methyl] -l, 3-dioxane;

2- [p- (4-Chlorphencxy) phenyl] -2- (l-imidazolylmethyl) -4-ethyl-l, 3-dioxolane;

2- [p- (4-chloro-2-methyl-phenoxy) -phenyl] -2- (l-imidazolylmethyl) -4-methoxymethyl-l, 3-dioxolane;

2- [p- (phenoxy) -phtnyl] -2- [l- (lH-l, 2,4-triazolyl) methyl] -4-hydroxymethyl-1,3-dioxolrn;

2- [p- (4-fluorophenoxy) phenyl] -2- (l-imidazolylmethyl) -4-ethyl-l, 3-dioxolane;

2- [p- (4-fluorophenoxy) phenyl] -2- (1-imidazolylmethy1) -4-hydroxymethy1-

1,3-dioxolane;

2- [p- (4-Fluorphencxy) -phenyl] -2- [l- (lH-l, 2,4-triazolyl) methyl] -1,3-dioxane

and in each case their pharmaceutically usable acid addition salts,

- 12 -

for their preparation, the same containing pliarm.izeutischo preparations and their use as Arzneimittelverstoffc.

The compounds of the formula I can be prepared as follows

A) a compound of formula II

Me-N I (II),

wherein Me represents hydrogen or a metal cation, with a compound of formula III

и ν

wherein X represents a nucleofuge leaving group, condensed or

B) in a compound of formula IV

R yes

Ar-O- / Vc-CH ₀ -N ^ I (IV)

I

the carbonyl group into a group of the formula V

O ⁷ \ (V)

I i

и ν

convicted, or

C) for the preparation of compounds of formula I, wherein U and V together represent a group of the formula -CH ₉ -CH (CH ₉ ZR ') - and R' is a radical other than hydrogen R ₇ , compounds of

- 13 -

Formulas VI and VII

(VII)

wherein one of the radicals X .. and X "optionally present in salt hydroxy or mercapto, for example of the formula -Z-Me, and the other a nucleophilic leaving group X, or both X. and X _? Represent hydroxy groups, fused together or

D) Compounds of the formulas VIII I \ and IX R l ^a Ar-X ₀ (VIII) and X , -. 3 ч ^ \ I U-- I V

(IX),

wherein one of the radicals X and X, a group -O-Me, in which Me is hydrogen or preferably a metal cation, and the other is an aryloxy-exchangeable radical, condensed together or E) a compound of the formula

(X)

decarboxylated intramolecularly and, if desired, converts a compound obtainable according to the method into another compound of the formula I and / or a free compound obtainable in accordance with the method in an acid addition salt, an acid addition salt obtainable according to the method into the free compound or into another acid addition salt, or a free obtained according to the process Compound or a Verfahrensfahrenswss available acid addition salt converted into a metal complex.

- 14-

Metal cations Me are, for example, alkali metal, e.g. Lithium, sodium or potassium cations, or alkaline earth metal, e.g. Magnesium, calcium, strontium or barium cations.

Nucleofuge leaving groups are, for example, reactive esterified hydroxy groups, such as with a hydrohalic acid, e.g. with fluoro, chloro, bromo, or hydroiodic acid, or a lower alkane, optionally substituted benzene or halosulfonic acid, e.g. with methane, ethane, benzene, p-toluene or fluorosulfonic acid, esterified hydroxy groups.

The reaction of an azole of the formula II

Me- / I (II),

wherein Y = -CH = or -N and Me is preferably a metal atom, in particular represents an alkali metal atom, is reacted with a compound of formula * _а

* T *

Ar-O- / 4 -C-CH, -X (III),

T o ⁿ o

^D и ν

wherein Ar, R, R, U and V have the meanings given under formula I and X is, for example, halogen, in particular chlorine, bromine or iodine, or benzenesulfonyloxy, p-tosyloxy, trifluoroacetyloxy or preferably lower alkylsulfonyloxy, such as e.g. Mesyloxy, is preferably carried out in a relatively polar but reaction-inert organic solvent, e.g. N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetonitrile, benzonitrile and others. Such solvents may be used in combination with other reaction inert solvents such as aliphatic or aromatic hydrocarbons, e.g. Benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene, and the like. be used.

- 15 -

If X is chlorine or bromine, it is possible to add alkali iodide (such as NaI or KI) to accelerate the reaction. Elevated temperatures of 0 to 22O ° C, preferably 80-17O ⁰ C, are advantageous. The reaction mixture is expediently heated under reflux.

In cases where in formula II Me is hydrogen, the process is carried out in the presence of a base. Examples of such bases are inorganic bases such as the oxides, hydroxides, hydrides, carbonates and bicarbonates of alkali and alkaline earth metals and e.g. tert. Amines such as triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine, etc.

In this and the following preparation variants, the intermediate and final products can be isolated from the reaction medium and, if desired, purified by one of the commonly used methods, e.g. by extraction, crystallization, chromatography, distillation etc.

The conversion of the carbonyl group in compounds of formula IV into the group of formula V is carried out by reaction with an orthocarboxylic acid tri-C.-C - alkyl, whose C.-C-alkyl groups optionally substituted by halogen or C, -C, alkoxy substituted or in the presence of an acid with at least 2 moles of a monohydric alcohol of the formula U-OH (Va), wherein compounds of formula I are obtained, wherein U and V are the same, optionally substituted C.-C. alkyl groups, or by reaction with a diol of the formula Vb

HO-U V-OH (Vb),

wherein compounds of formula I are obtained, wherein U and V together represent one of the above-defined alkylene bridges. there

Ar, Y, R, R, U and V have the meanings given under formula I, a b

This ketalization reaction can be carried out analogously to previously known ketalization reactions, for example analogously to the preparation of 2-bromomethyl-2,4-diphenyl-1,3-dioxolane [Synthesis, 1974 (D, 23].

- 16 -

In the preferred embodiment of ketalization, both reactants are refluxed for several hours together with an azeotrope former in one of the common organic solvents. As azeotrope formers, e.g. Benzene, toluene, xylene, chloroform or carbon tetrachloride, with the addition of a strong acid, e.g. p-toluenesulfonic acid, may be advantageous. Useful organic solvents in this case are e.g. aromatic hydrocarbons, such as benzene, toluene, xylene, etc., saturated hydrocarbons, such as η-hexane or saturated halogenated hydrocarbons, e.g. 1,1,1-trichloroethane.

Other ways of ketalization are also feasible, e.g. by reacting a ketone IV, which is ketalized with an alcohol or phenol other than alkanols or diols of the formulas Va or Vb, and reprecipitates this by reaction with excess alkanol Va or the diol Vb to give (I). The starting product is e.g. according to one of the process variants A), D) and E) accessible.

The preparation of compounds of the formula I in which substituents U and V according to variant C) together represent TCH ₉ -CH (CH ₅ ZR ₇ ) -, for example, by reaction of a compound of formula VI with a compound of formula VII, wherein X is a group -ZH and X- means a group X. The reaction is preferably carried out in reaction-inert organic solvents. For this purpose, for example, N, N-Dimethy1formamid, Ν, Ν-dimethylacetamide, hexamethylphosphoric triamide, dimethyl sulfoxide, 4-methyl-3-pentanone, etc. Also mixtures with other reaction-inert solvents, for example with aromatic hydrocarbons such as benzene, toluene, xylene, etc. can be be used. In some cases it may be advantageous to work to accelerate the reaction rate in the presence of a base. Examples of such bases are alkali metal metal hydrides or alkali metal carbonates. In certain cases, it may also be advantageous that the compound VI is first converted in a known manner into a suitable metal salt.

- 17 -

This is preferably done by reaction of VI with a Na compound, for example, sodium hydride, sodium hydroxide, etc. Subsequently, this salt of VI is reacted with the compound of formula VII. To increase the reaction rate can be used in some cases, even at elevated temperature, preferably 80 ⁰ C to 130 ⁰ C, or at the boiling point of the solvent.

In an analogous manner to compounds of the formulas VI and VII, wherein X ₁ is a group X and X is a group -ZH implement.

In the case of the condensation reaction of compounds of the formulas VI and VII in which Z is oxygen to give compounds of the formula I in which X is oxygen, in which X ₁ and. X- represent hydroxy, the reactants can be heated under reflux in a suitable solvent, at the same time the resulting water is distilled off azeotropically from the reaction mixture. Suitable solvents are aromatic hydrocarbons, such as toluene or alcohol HO-R- in question. In this reaction, it is expedient to work in the presence of a strong acid, for example p-toluenesulfonic acid.

In variant D), preference is given to compounds of the formulas VIII and IX in which X- is a group -OMe and X, a nucleofugic leaving group or vice versa, X- represents the nucleofuge leaving group and X, the group -OMe. Here, R, R, U, V, Y and Ar have the meanings given under formula I; Me is preferably hydrogen. The reaction is advantageously carried out under the conditions described in variant A).

In variant E), the compound of the formula X to be decarboxylated, obtainable by ketalization of a compound of the formula XI, is described analogously to B),

[ ^a 0 _M

Ar-OCO- Γ VC-CH ₂ -H ^ I

⁰ X

\ .ι

- 18 -

which in turn is prepared by reacting a compound of the formula Ar-OH XII with a difunctional derivative of carbonic acid, e.g. with phosgene, a Halogenameiscnsäureniederalkylester or a Dinicdernllyl- or diphenyl carbonate and further reaction with a compound of formula XIII R

HO-V ,, - C-CH-N (XIII)

can be obtained, dry or in a high boiling solvent, such as a high boiling ether, e.g. Diphenyl ether or ethylene glycol dimethyl ether, heated to about 120 ° to 22O ° C.

Compounds obtainable by the process can be converted into other compounds of the formula I by methods known per se.

Thus, for example, it is possible to transketalize compounds obtainable according to the method to other compounds of the formula I. For example, in compounds of the formula I in which U and V are identical, optionally substituted, C 1 -C 4 -alkyl radicals U, by reaction with 1 mole of another, optionally substituted C 1 -C 4 -alkanol of the formula V-OH (Vc), a group U replaced by a group V or by reaction with a diol of the formula Vb both groups U by a bivalent radical Umketalisierung in a conventional manner, for example in the presence of an acid condensing agent, such as a mineral, sulfonic or strong carboxylic acid, for example of chloro or hydrobromic acid, sulfuric acid, p-toluenesulfonic acid or trifluoroacetic acid, advantageously with distillative or azeotropic distillation removal of volatile reaction products.

Further, in the carbocyclic aryl parts according to the method available: compounds optionally additional substituents

- 19 -

into the radical Ar and / or the groups R and R, respectively. So you can, for example by reaction with a halogen in the presence of a Lewis acid, such as an iron, zinc, boron or antimony halide, or by treatment with N-chlorosuccinimide, halogen.

Furthermore, nitro groups, e.g. by means of suitable complex hydrides, e.g. with lithium aluminum hydride, reduce to amines, these, e.g. by means of nitrous acid, diazotize and replace the diazonium group formed in the usual way by halogen or alkoxy. Similarly, halogen may be reacted by reaction with an alkyl metal compound, e.g. with an alkyl lithium or alkyl magnesium halide, replace with alkyl.

If the compounds of the formula I are obtained as bases, then they can be converted by inorganic or organic acids into corresponding salts or by preferably equimolar amounts of metal salts into metal complexes of the formula I. Conversely, salts of the formula I can be converted into the free bases of the formula I, for example, by reaction with alkali metal (hydrogen) carbonate or alkali metal hydroxide.

The Ausgangssketalc of formula III can be derived from the underlying Methylai-yl-ketone of formula XIV

Ar - O - ^ - CO - CH (XIV) T ^R b

by reaction with the desired diol in an inert solvent, e.g. a halogenated hydrocarbon (such as methyl chloride, ethylene chloride, chloroform, carbon tetrachloride, etc.) and concomitant or subsequent halogenation win. To accelerate the reaction, an addition of p-toluenesulfonic acid before geous.

- 20 -

The ketones of formula IV can be obtained by halogenation of the starting

ketone XIV to XV R i ^a

Ar-O-> - »CO-CH-Hal (XV)

and further reaction of XV, analogously to variant A, be prepared with an azole of the formula II. Here, shark is preferably chlorine or bromine.

The ketals III, VI, IX and X are obtained analogously to variant B by reaction of the starting ketone, e.g. of the formula IV with a suitable alcohol or diol.

The described production variants are part of the invention.

The starting materials of the formulas III, IV, VI, X and XI, which

have been specially developed for the preparation of the novel compounds of formula I, are still new and also form an object of the invention.

In all of the described ketalization reactions of a ketone with a substituted α, β or α, γ-diol, predominantly mixtures of diastereomers of the resulting ketal are formed. Correspondingly, diastereomer mixtures of the end products I are generally formed from the starting ketones. The compounds of the formula I can be present, for example, in the following two diastereomeric forms:

- 21 -

Лг-0

Λ '

(XVI)

• «MM ·

J * '" ³

Ar-O ₄ R

Α types

 N =

'а ' -в

(XVII)

The configuration of type A is here and hereinafter referred to as the "trans" isomer.

working

• -N

B grades

Ar-O

, Л

(XVIII) CH ₂ ZR ₇

(XIX)

The symbols in the spatially rendered structures should have the following meanings:

.... = behind - = in ► = in front of the drawing plane.

The configuration of type B shall accordingly be referred to as the "cis" isomer . The separation of the two diastereomers can be carried out, for example, by fractional crystallization or by chromatography (thin-layer, thick-layer, column chromatography, high-pressure liquid chromatography, etc.). The two isomers show different biological effects. In general, the diastereomeric gums are used for practical purposes.

-22- 28.10.1982

AP С 07 D / 239 809 (60 854/12)

The invention relates to all! isomeric compounds of Formula I, their salts and metal complexes ·

The preparation process of compounds of the formula I in its variants A, B, G, D and h is part of the invention.

Some of the starting materials and intermediates used in the processes A ₁ B, C, D and B are known, others can be prepared by methods known per se. Some are new; their preparation is described herein.

The compounds according to the invention have very advantageous curative, preventive and systemic plant therapeutic properties and can be used for the protection of crop plants. With the active compounds of formula 1, the occurring microorganisms can be contained or destroyed on plants or parts of plants (fruits, flowers, foliage, stems, tubers, roots) of different useful cultures, whereby later growing plant parts are spared from such microorganisms »

The active substances are effective in particular against the phytopathogenic fungi belonging to the following groups: Ascomycetes (eg Venturia,

= 23 -

Podosphaera, Erysiphe, Monilinia, Uncinula); Basidiomycctes (e.g., the genera Herai le Li, Rhizocton Li, Puccinia); Fungi imperfecti (e.g., Botrytis, Helmintliosporiura, Fu-lg., Septoria, Cercospora and Alternaria). Moreover, the compounds of the formula I act systemically. They may also be used as mordants for the treatment of seeds (fruits, tubers, grains) and insect plaques for protection against fungal infections and against phytopathogenic fungi occurring in the soil. The active compounds according to the invention are distinguished by particularly good plant tolerance.

The invention thus also relates to microbicidal agents and the use of the compounds of the formula I for controlling phytopathogenic microorganisms, in particular plant-damaging fungi or the preventive prevention of infestation of plants.

Moreover, the present invention also includes the preparation of agrochemical agents which is characterized by the intimate mixing of the active substance with one or more substances or substance groups described herein. Also included is a method for the treatment of plants which is distinguished by the application of the compounds of the formula I or of the novel agents.

As target cultures for the indication areas disclosed herein, for example, the following plant species apply in the context of this invention: cereals: (wheat, barley, rye, oats, rice, sorghum and relatives); Beets: (sugar and fodder beet), pome, stone and berry fruit: (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries) Legumes: beans, lentils, peas Oilseed crops: (rapeseed, mustard, poppy, olives, sunflowers, coconut, castor, cocoa, peanuts); cucumber plants: (squash, cucumbers, melons); fibrous plants: (cotton, flax, il.mf, jute); Citrus fruits: (oranges, lemons, grapefruit, M.ukLu Liu-u); Vegetables: (spinach, lettuce, asparagus, cabbage, carrots, duck-in, tomatoes, potatoes, peppers); Laurel family: (avocado, cinnamonum, camphor) or plants such as maize, tobacco, nuts, coffee, sugar, vines, hops, banana and natural rubber gums, and ornamental plants (composites).

- 24 -

Active ingredients of the formula I are usually used in the agricultural sector in the form of compositions and can be applied simultaneously or successively with further active ingredients to the surface, plants or plant part to be treated. For pesticides, these further active ingredients may be fertilizers, trace element mediators or other preparations which influence plant growth. However, they may also be selective herbicides, insecticides, fungicides, bactericides, nematocides, molluscicides or geraniums of several of these preparations, together with optionally further customary in formulation technology excipients, surfactants or other application-promoting additives.

For all formulations, suitable carriers and adjuvants may be solid or liquid, and will be consistent with the non-toxic materials useful in the art of formulation, such as, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners or binders.

An agricultural preferred method for applying an active ingredient of the formula I or an agrochemical agent on an affected plant is the application to the foliage (foliar application). Number of applications and application rate depend on the infestation pressure for the corresponding pathogen (mushroom strain). However, the active substances of the formula I can also enter the plant via the soil through the root system (systemic action) by impregnating the location of the plant with a liquid preparation or introducing the substances into the soil in solid form, e.g. in the form of granules (soil application). But the compounds of formula I can also be applied to seeds (coating) by the

- 25 -

Grains either with a liquid preparation of the active ingredient soaks or coated with a solid preparation. Moreover, in special cases, other types of application are possible, e.g. the targeted treatment of plant stems or buds.

The compounds of the formula I are used in unchanged form or preferably together with the auxiliaries customary in agrochemical formulation technology and are therefore used, for example. to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, by encapsulation in e.g. processed polymeric substances in a known manner. The application methods such as spraying, misting, dusting, scattering, brushing or pouring are chosen in the same way as the type of means according to the desired goals and given conditions. Cheap application rates are generally from 50 g to 5 kg of active substance (aa) per ha; preferably 100 g to 2 kg of AS / ha, in particular from 200 g to 600 g of AS / ha.

The agrochemical formulations, i. the compositions, preparations or compositions containing the active substance of the formula I and, where appropriate, a solid or liquid additive are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with diluents, e.g. with solvents, solid carriers, and optionally surface-active compounds (surfactants).

Suitable solvents are: Aromatic hydrocarbons, preferably fractions C_ to C, such as e.g. Xylene or substituted naphthalenes, phthalic esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters, such as ethanol, ethylglycol, ethylenep.-glycol monomethyl or ethyl ether,

- 26 -

Ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and, if appropriate, epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

As solid carriers, e.g. For dusts and dispersible powders, ground natural minerals are generally used, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. As granular, adsorptive granule carriers are porous types such. Pumice, broken brick, sepiolite or bentonite, as non-sorptive carrier materials e.g. Calcite or sand in question. In addition, a variety of pre-granulated materials of inorganic or organic nature, in particular dolomite or crushed plant residues can be used.

Depending on the nature of the active compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also surfactant mixtures.

Suitable anionic surfactants may be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

As soaps are the alkali, alkaline earth or optionally sub

The ammonium salt of higher fatty acids ( ^C 1 _O 2 ^C 22) ^w * ^{e Z} ' ^{B # is} the Na or K salt of OeI or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut oil or tallow oil are also the fatty acid methyllaurinsalz to mention.

-27 -

More frequently, however, so-called synthetic surfactants are used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkali radical of 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, e.g. the Na or Ca salt of ligninsulphonic acid, of dodecylsulphuric acid ester or of a fatty alcohol sulphate mixture prepared from natural fatty acids, including the salts of sulfuric acid esters and sulphonic acids of fatty alcohol / ethylene oxide adducts.The sulphonated benzimidazole derivatives preferably contain 2-sulphonic acid groups and a fatty acid radical having 8-22 C atoms.Alkylaryl sulphonates are, for example, the Na, Ca or triethanolamine salts of dodecylbenzenesulphonic acid, of dibutylnaphthalene sulphonic acid, or of a naphthalenesulphonic acid-formaldehyde condensation product.

Further, there are also corresponding phosphates, e.g. Salts of Phosphorsäureestei s of a p-nonylphenol (4-14) -Ethylenoxyd adduct in question.

Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) radiosilyl radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols ,

Other suitable nonionic surfactants are the water-soluble, from 20 to 250 Aethylcnglykoläthergruppcn and 10 to 100 Propylenglykoiethergruppen containing l'olyctliylonoxidnddukte of polypropylene glycol, Aethylendiaminopolypropylenglykol and alkylpolypropylene

- 28 -

kol rait 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain ^propropylene glycol unit 1 to 5 ethylene glycol units.

As examples of nonionic surfactants, there may be mentioned nonylphenolpolycthoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Further, копвпеп also includes fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethylene sorbitan trioleate.

The cationic surfactants are, above all, quaternary ammonium salts which contain as N-substituents at least one alkyl radical having 8 to 22 carbon atoms and have as further sulfo substituents lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. the stearyltrimethylammonium chloride or the benzyldi (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in agrochemical formulation technology

are u.a. described in the following publications:

"McDeckcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ringwood New Jersey, 1980 Sisely and Wood, "Encyclopaedia of Surface Active Agents", Chemical Publishing Co., Inc. New York, 1980.

The agrochemical preparations generally contain 0.1 to 99%, in particular 0.1 to 9SZ active ingredient of the formula I, 99.9 to 1%, in particular 99.8 to 5Z of a solid or liquid additive, including 0 to 25Z, in particular 0.1 to 2SZ, a surfactant.

- 29 -

While merchandise tends to be more conspicuous, the end user typically uses diluted funds.

The agrochemical compositions may also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

Such agrochemical agents are part of the present invention.

The antimycotic properties of the usefulness of the compounds of the formula I and their pharmaceutically usable acid addition salts for controlling warm-blooded parasitic fungi can be determined, for example, in vitro by means of conventional microbiological examination methods, eg by their toxic effect on felt strains parasitizing warm-blooded animals, such as Trychophyton mentagryphites, Microsporum canis, Sporotrichum schenkii, Aspergillus fumigatus and Candida albicans, as well as in vivo on the guinea pig on the basis of the healing effect on experimental infestations of the dorsal skin with Trychophyton, eg T. rubrum, after peroral or local application.

The anticonvulsant activity of the compounds of formula I and their pharmaceutically acceptable acid addition salts can be in vivo in, for example, the mouse in the pentatetrazole spasm test in the dose range of about 10 to about 100 mg / kg po, as well as in the electroshock test in the dose range of about 10 to about 100 mg / kg po. The anxiolytic activity can be demonstrated, for example, on the mouse and other small rodents by means of the Gellert test and the Quatre plaque test in the dose range from about 10 to about 100 mg / kg po. It is also possible to conclude that the new compounds have a significant antimanic effect.

- 30 -

The invention thus likewise relates to the use of compounds of the formula I and their pharmaceutically usable acid addition salts for topical or local and systemic control of warm-blooded parasitic fungi or for the systemic treatment of various forms of epilepsy, states of anxiety and tension and manic states of mind in particular as active ingredient in or for the preparation of pharmaceutical preparations for enteral, parenteral, topical or local administration, as well as such pharmaceutical preparations.

The pharmaceutical compositions according to the invention which contain compounds of the formula I or pharmaceutically acceptable salts thereof are accordingly those for enteral, such as oral or rectal, and parenteral administration and for topical administration to warm-blooded animals, which alone are the pharmacologically active substance or together with a pharmaceutically acceptable carrier material. The dosage of the active ingredient depends on the species of warm-blooded animals, age and individual condition, as well as the mode of administration.

Normally, an approximately daily dose of about 50-500 mg, advantageously distributed in several equal sub-doses, is to be estimated for a warm-blooded animal weighing about 75 kg when administered orally.

The new pharmaceutical preparations contain e.g. from about 1OZ to about 8OZ, preferably from about 20% to about 6OZ of the active ingredient. Pharmaceutical preparations according to the invention for oral or parenteral administration are e.g. those in dosage unit forms such as dragees, tablets, capsules or suppositories, further ampoules. These are produced in a manner known per se, e.g. produced by conventional mixing, granulation, coating, solution or lyophilization process. Thus, one can obtain pharmaceutical preparations for oral use by combining the active ingredient with solid carriers, a received

- 31 -

Granulated if appropriate, and the mixture or granules, if desired or necessary, after addition of suitable excipients, processed into tablets or dragee cores.

Suitable carriers are, in particular, fillers, such as sugars, e.g. Lactose, sucrose, mannitol or sorbitol, cellulose preparations and / or calcium phosphates, e.g. Tricalcium phosphate or calcium hydrogen phosphate, further binders such as starch pastes using e.g. corn, wheat, rice or potato starch, gelatin, tragacanth, methylcellulose and / or polyvinylpyrrolidone, and / or, if desired, disintegrating agents such as the abovementioned starches, furthermore carboxymethyl starch, cross-linked polyvinylpyrrolidone, agar, alginic acid or a salt thereof, like sodium alginate. Auxiliaries are primarily flow regulators and lubricants, e.g. Silica, talc, stearic acid or salts thereof, such as magnesium or calcium stearate, and / or polyethylene glycol. Dragee cores are provided with suitable, optionally gastric juice-resistant Überzugen, u.a. concentrated sugar solutions which may contain arabic gum, talc, polyvinylpyrrolidone, polyethylene glycol and / or titanium dioxide, lacquer solutions in suitable organic solvents or solvent mixtures or, for the preparation of enteric coatings, solutions of suitable cellulose preparations, such as acetylcellulose phthalate or hydroxypropylmethylcellulose phthalate. The tablets or dragee coatings may contain dyes or pigments, e.g. for the identification or labeling of different doses of active substance.

Other orally applicable pharmaceutical preparations are gelatin capsules, as well as soft, closed capsules of gelatin and a plasticizer, such as glycerol or sorbitol. The capsules may contain the active ingredient in the form of granules, e.g. in admixture with fillers, such as lactose, binders, such as starches, and / or lubricants, such as talc or magnesium stearate, and optionally stabilizers,

- 32 -

contain. In soft capsules, the active ingredient is preferably dissolved or suspended in suitable liquids, such as fatty oils, paraffin oil or liquid polyethylene glycols, and stabilizers may also be added.

As rectally applicable pharmaceutical preparations are e.g. Suppositories which consist of a combination of the active ingredient with a suppository base. As suppository base, e.g. natural or synthetic triglycerides, paraffin hydrocarbons, polyethylene glycols or higher alkanols. Furthermore, gelatin rectal capsules containing a combination of the active ingredient with a matrix may also be used; as basic materials there are e.g. liquid triglycerides, polyethylene glycols or paraffinic hydrocarbon in question.

For parenteral administration, aqueous solutions of an active ingredient in water-soluble form, e.g. a water-soluble salt, further suspensions of the active ingredient, such as corresponding oily injection suspensions, whereby suitable lipophilic solvents or vehicles such as fatty oils, e.g. Sesame oil, or synthetic fatty acid esters, e.g. Ethyl oleate, or triglycerides, or aqueous injection suspensions containing viscosity increasing agents, e.g. Sodium carboxymethyl cellulose, sorbitol and / or dextran and optionally also stabilizers.

As topically applicable pharmaceutical preparations are primarily cream, ointments, pastes, foams, tinctures and solutions in question, which contain from about 0.5 to about 20% of the active ingredient.

Creams are oil-in-water emulsions containing more than 50% water. The oily base used is primarily fatty alcohol, e.g. Lauryl, cetyl or stearyl alcohol, fatty acids, e.g. Palmitin or

- 33 -

Stearic acid, liquid to solid waxes, e.g. Isopropyl myristate, WoIlwnchs or beeswax, иікі / оікт Коііісііѵглк.мткСоГГс, z.H. V.isol in «(petrolatum) or paraffin oil. Suitable emulsifiers are surface-active substances with predominantly hydrophilic properties, such as corresponding nonionic emulsifiers, e.g. Fatty acid esters of polyhydric alcohols or ethylene oxide adducts thereof, such as polyglycerol fatty acid esters or polyoxyethylene fatty alcohol ethers or fatty acid esters, or corresponding ionic emulsifiers, such as alkali metal salts of fatty alcohol sulfates, e.g. Sodium lauryl sulphate, sodium cetyl sulphate or sodium stearyl sulphate, usually in the presence of fatty alcohols, e.g. Ceryl alcohol or stearyl alcohol used. Additives to the water phase are u.a. Agents which reduce dehydration of the cream, e.g. Polyalcohols such as glycerol, sorbitol, propylene glycol and / or polyethylene glycols, preservatives, fragrances, etc.

Ointments are water-in-oil emulsions containing up to 70%, but preferably from about 20% to about 50% water or aqueous phases. The fatty phase is primarily hydrocarbons, e.g. Vaseline, paraffin oil and / or hard paraffins in question, the preferably water-binding capacity suitable hydroxy compounds, such as fatty alcohols or esters thereof, e.g. Ceryl alcohol or wool wax alcohols or wool wax included. Emulsifiers are corresponding lipophilic substances, such as sorbitan fatty acid esters (Spans), e.g. Sorbitan oleate and / or sorbitan isostearate. Additives to the water phase are u.a. Humectants, such as polyalcohols, e.g. Glycerol, propylene glycol, sorbitol and / or polyethylene glycol, as well as preservatives, fragrances etc.

Fatty ointments are anhydrous and contain, in particular, hydrocarbons, e.g. Paraffin, vaseline and / or liquid paraffins, further natural or partially synthetic fats, e.g. Coconut fatty acid triglyceride, or preferably hardened oils, e.g. hydrogenated peanut or castor oil, and fatty acid partial esters of glycerine,

- 34 -

e.g. Glycerol mono- and distearate, as well as e.g. the oily receptors mentioned above, fatty acid-increasing fatty alcohols, emulsifiers and / or additives.

Fasting is cream and ointments with secretion-absorbing feed components, such as metal oxides, e.g. Titanium oxide or zinc oxide, further talc and / or aluminum silicates, which have the task to bind existing moisture or secretions.

Foams are administered from pressure vessels and are aerosolized liquid oil-in-water emulsions wherein halogenated hydrocarbons such as chlorofluoro-lower alkanes, e.g. Dichlorodifluoroethane and dichlorotetrafluoroethane, ale blowing agent can be used. The oil phase used u.a. Hydrocarbons, e.g. Paraffin oil, fatty alcohols, e.g. Cetyl alcohol, fatty acid esters, e.g. Isopropyl myristate, and / or other waxes. As emulsifiers u.a. Mixtures of those having predominantly hydrophilic properties, such as polyoxyethylene sorbitan fatty acid esters (Tweens), and those having predominantly lipophilic properties, such as sorbitan fatty acid esters (Spans). There are also the usual additives, such as preservatives, etc.

Tinctures and solutions mostly have an aqueous-ethanolic base, which i.a. Polyalcohols, e.g. Glycerin, glycols, and / or poly-ethylene glycol, as humectants to reduce evaporation, and replenishers such as fatty acid esters with low poly-ethylene glycols, i. lipophilic substances which are soluble in the aqueous mixture as a substitute for the fatty substances removed from the skin with the ethanol and, if necessary, other auxiliaries and additives are added.

The preparation of the topically usable pharmaceutical preparations is carried out in a manner known per se, e.g. by dissolving or suspending the active ingredient in the base or in a part thereof, if

-35- 28.10.1982

AP С 07 D / 239 803 (60 854/12)

necessary. When processing the active ingredient as a solution, it is usually dissolved in one of the two phases before the emulsification; when processed as a suspension, it is mixed with a portion of the base after being inoculated and then added to the remainder of the formulation.

embodiment

The following examples serve to illustrate the invention without limiting it. Temperatures in degrees Celsius, pressures expressed in mbar · Percentages and parts are by weight · RT means room temperature, h stands for hour ·

Preparation Examples: Example 1 : Preparation of CH,

.-. * - * CC / I У 4-0-. " ⁴ · -c '~ CH- / I ⁽⁶ ' ⁸⁾

2- / p- (Phenoxy) -phenyl-7-2- / T- (1H-1,2,4-triazolyl) -methyl7-4-methyl-1,3-dioxane

a) Preparation of the intermediate product

I i

sy ^ //% ч • (XX)

- 36 -

2 [ ρ- (phenoxy) phenyl] -2-bromomethyl-4-me thy1-1 . 3-dioxane

10 parts of 2- [p- (phenoxy) phenyl] -2-oxi-l-bromoethane and 4 parts of 1,3-butanediol are in 3 0 h in 40 ml of absolute toluene in the presence of 0.2 parts of catalytically active p-toluenesulfonic under Reflux, wherein formed water is separated with a water separator. After cooling to RT, the reaction mixture is washed twice with 20 ml of water, dried over sodium sulfate, filtered, the solvent evaporated and the crude product recrystallized from isopropanol. Colorless crystals. Mp 96-106 °.

b) Preparation of the final product

3.3 parts of 1,2,4-triazole sodium salt and a catalytic amount of potassium iodide are dissolved in 40 ml of dimethyl sulfoxide together with 10.2 parts of prepared according to a) 2- [p- (phenoxy) -phenyl] -2-bromomethyl 4-methyl-1,3-dioxane for 30 h at an internal temperature of + 120 °. After cooling to room temperature, 300 ml of water are added, extracted three times with 30 ml of ethyl acetate, the combined extracts washed twice with 20 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The oily residue is purified by column chromatography (silica gel / ethyl acetate). After evaporation of the eluent, the oily residue crystallizes after addition of petroleum ether. Brownish crystals. Mp. 99.5-101 °.

- 37 - Example 2 : Production of

0th

('") V ~ - ^ _r - <' ⁼ f (3.226)

2- [p- (4-chloro-2-methyl-phenoxy) -phenyl] -2- (1-imidazolyl! Methyl) -4-methoxymethyl-1,3-dioxolane

16 parts of 2- [p- (4-chloro-2-methylphenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-hydroxymethyl 1-1,3-dioxolane are dissolved in 150 ml of N, N-dimethylformamide and taken under Passing through nitrogen and stirring with 1.9 parts of 55% sodium hydride dispersion and heated for 2 h at 80 °. After cooling to RT, 6.3 parts of methyl iodide are added dropwise with stirring within 1 h, the reaction mixture heated to 60 ° for 2 h and diluted with 800 ml of ice water and extracted three times with 300 ml of ethyl acetate. The combined extracts are washed twice with 50 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The residue is purified by column chromatography (silica gel / acetone-ethyl acetate (1: 1)). After evaporation of the mobile phase mixture, the mixture of diastereomers is crystallized by treatment with hexane. Beige crystals; Mp. 92-106 °.

Example 3 ; Production of

N0

2- [p- (2-nitro-4-trifluoromethylphenoxy) phenyl] -2- (l-imidazolylmethyl) -4-ethyl-l, 3-dioxolan

8.3 parts of 2- (p-hydroxyphenyl) -2- (l-imidazolylmethyl) -4-ethyl-l, 3-dioxolaa are dissolved in 300 ml of dimethyl sulfoxide and treated with 1.84 parts of ground potassium hydroxide, the temperature of 23 ° rises to 36 °. After heating for 2 hours at 70 ° C., 7.4 parts of 4-chloro-3-nitrobenzotrifluoride in 100 ml of dimethylformamide are added, with stirring, at 70 ° C.

- 38 -

sulfoxide added dropwise and stirred for 3 h at 70 °. After cooling to RT, the reaction mixture is poured into 2000 ml of water and extracted twice with 200 ml of diethyl ether. The combined extracts are washed twice with 70 ml of water, dried over sodium sulfate and the solvent evaporated. The oily residue is purified by column chromatography (silica gel / ethyl acetate). After evaporation of the eluent, the mixture of diastereomers remains as a viscous mass.

Example 4 : Synthesis of "

· - · »- · о о · = ·

egg

2- [p- (3-chlorophenoxy) phenyl] -2- (l-imidazolyl! Methyl) -4-ethyl-l, 3-dioxolan

1.2 parts of imidazole sodium salt and a catalytic amount of potassium iodide are dissolved in 50 ml of dimethylformamide together with 4 parts of 2- [p- (3-chlorophenoxy) -phenyl] -2-bromomethyl-1-yl-ethyl-1,3-dioxolane 17h stirred at an internal temperature of 125 °. After cooling, the brown reaction mixture is mixed with 150 ml of water, extracted three times with 50 ml of ethyl acetate, the combined extracts washed twice with 50 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The oily crude product is chromatographed over a 35 cm long silica gel column using acetone / ethyl acetate (1: 1). After evaporation of the eluent, the oily residue crystallizes after addition of petroleum ether. Slightly yellowish crystals. M.p. 69-71 ⁰ C.

- 39 -

Example 5: Preparation of

· - · · - ♦ Ωίϊ

2- [ρ- (4-chlorophenoxy) phenyl] -2- (1-imidazolyl! Methyl) -4-ethyl-1,3-dioxolane

a) Synthesis of intermediates

α) Preparation of

/ ^CH 2 ^CH 3

/ -Ч / -у к)

Cl-- '/ * ~ ° ~ * \ / ^{c CH} ₃

• sS · · Ss ·

2- [p- (4-chlorophenoxy) phenyl] -2-methyl-4-ethyl-l, 3-dioxolan

37 parts of 4- (p-chlorophenoxy) acetophenone and 18 parts of 1,2-butanediol are refluxed in 400 ml of absolute toluene in the presence of 2 parts of catalytically active p-toluenesulfonic acid on a water separator. After cooling to RT, the reaction mixture is washed twice with 400 ml of water, dried over sodium sulfate, filtered, the solvent evaporated and the crude product for purification over a 1 m silica gel column using ligroin / hexane / ethyl acetate / toluene (5: 3: 1 : 1) chromatographed. The product is considered light

22 yellowish OeI obtained, η: 1.5527.

β) Preparation of CH CH

_cl _ / ~ \ _ _Q _ / '\ _t _K _c ) _ _c ^ _ _Br

2- (p- (4-chlorophenoxy) -phenyl] -1-bromomethyl-ethyl-1-1,3-dioxolane

36.8 parts of the product prepared under α) 2- [p- (4-chlorophenoxy) phenyl] -2-methyl-4-ethyl-l, 3-dioxolans are heated to boiling in 350 ml of chloroform. Under illumination by means of a 150 watt spot lamp 19.4 parts of 3rom dissolved in 50 ml of chloroform are added dropwise and then heated under reflux for 2 h. After cooling to RT, the

- 40 -

Washed reaction mixture twice with 200 ml of water, dried over sodium sulfate, filtered and the solvent removed in a water jet vacuum. For purification, the crude product is over a 1 m long

Silica gel column chromatographed by means of toluene. The product is called

23 yellow OeI obtained, η: 1.5805.

b) Synthesis of the final product

4.4 parts of imidazole Natriurasalz and a catalytic amount of potassium iodide are in 80 ml of dimethylformamide together with 14, 7 parts of prepared according to ß) 2- [p- (4-chlorophenoxy) phenyl] -2-bromomethyl-4-ethyl -l, 3-dioxolane for 17 h at a bath temperature of 125 ° C stirred. After cooling to room temperature, the reaction mixture is poured into 600 ml of water, extracted three times with 200 ml of ethyl acetate, the combined organic phases washed twice with 200 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The oily residue is chromatographed over a 50 cm long silica gel column using acetone / ethyl acetate (1: 1). After evaporation of the eluent, the product is as brown

25 OeI received; η: 1.5750.

Example 6 ; Synthesis of

/ H ₂ CH ₃

2- [p- (phenoxy) -phenyl3-2- (lH-l, 2,4-triazolylmethyl) -4-ethyl-l, 3-dioxolan

17 parts of 2- [p- (phenoxy) -phenyl] -3-bromomethyl-4-ethyl-l, 3-dioxolane, 8.4 parts of potassium carbonate, 4.2 parts of 1,2,4-triazole and a catalytic amount Sodium iodide are stirred in 100 ml of dimethyl sulfoxide for 24 h at an internal temperature of 125 °. After cooling to RT, the reaction mixture is poured into 600 ml of water, extracted three times with 200 ml of ethyl acetate, the combined extracts twice with

- Al -

washed 200 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The oily residue is chromatographed over a 50 cm long silica gel column using chloroform / ether (1: 1). After evaporation of the eluent, the oily residue crystallizes after addition of petroleum ether. White crystals; Mp. 81.5-83.5 °.

Example 7 : Synthesis of y '^

• · · · · η η · = μ

г <11 ^(6Л)

"si

'2 2- [р- (Рpепоху) -рпепу1} -2- (1Н-1,2,4- ^ іаго1у1те ^ у1) -1,3-аіохап

14 parts of 2- [p-phenoxyphenyl] -2-bromomethyl-l, 3-dioxane, 7.2 parts of potassium carbonate, 3.6 parts of 1,2,4-triazole and a catalytic amount of potassium iodide are dissolved in J.00 ml of dimethyl sulfoxide Stirred for 20 h at an internal temperature of 140 °. After cooling to RT, 600 ml of water are added, extracted three times with 200 ml of ether, the combined extracts washed twice with 200 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The oily residue is chromatographed on a 50 cm long silica gel column using chloroform / ether (1: 1). After evaporation of the eluent, the residue crystallized after addition of petroleum ether. White crystals; Mp. 129-130 °.

CH OH Example 8 : Synthesis of _ш / 2

(1.23)

2- [p- (Phenoxy) -phenyl] -2- (IH-I, 2,4-triazolylmethyl) -4-hydroxymethyl- 1,3-dioxolane

4.5 parts of 2- [p-phenoxyphenyl] -2-bromomethyl-4-hydroxymethyl-l, 3-dioxolane, 2.2 parts of potassium carbonate, 1.1 parts of 1,2,4-triazole and a catalytically effective amount of K. iliumjodid be in 50 ml of dimethyl sulfoxide

- 42 -

Stirred for 4 h at an internal temperature of 140 °. After cooling to RT, 600 ml of water are added, extracted twice with 200 ml of ethyl acetate, the combined extracts washed twice with 200 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The oily residue is chromatographed over a 50 cm long silica gel column using acetone. After evaporation of the eluent, the oily residue crystallizes after addition of petroleum ether. Beige crystals; Mp 111-122 °.

Example 9 ; Synthesis of CHjCH-CH

SZ ^α · ¹⁷⁾

2- [ρ- (Phenoxy) -phenyl] -2- (IH-1,2,4-triazolylmethyl-4-n-propyl-1,3-dioxolane

10.3 parts of the nitrate of 1- (p-phenoxyphenyl) -2- (l, 2,4-triazolyl-1-yl) -ethanone, 6.1 parts of 1,2-pentanediol, 6.9 parts of p-toluenesulfonic acid , 20 parts of 1-pentanol and 200 parts of xylene are heated under reflux for 6 days on a water and washed after cooling to RT twice with 200 ml of dilute sodium hydroxide solution and twice with 200 ml of water. The organic phase is dried over sodium sulfate, filtered and the solvent evaporated. The oily residue is chromatographed on a 1 m silica gel column using ethyl acetate. After evaporation of the eluent, the oily residue crystallizes out slowly. Beige crystals; M.p. 68.5-71 °.

In an analogous manner, the following end products (if not particularly noted diastereomer mixtures with different mixing ratios) of the formula I can be prepared:

- 43 -

In the tables below, the symbol A stands for a type A and B diastereomer corresponding to a type B diastereomer.

Table 1; Compounds of the formula

(XXI)

wherein isomeric forms are to be included:

Verb. ^R 10 H Y salt 3 2 FeCl ₃ Physics. constant No. JL \ J H - 1.1 H N - CuCl ₂ Mp. 100-102 ° 1.2 CH ₃ N ENT ₃ - 1.3 CH ₃ CH - - 1.4 CH ₃ N - ZnCl ₂ Mp 76.5-81 ° 1.5 CH ₃ N HCl HCl 1.6 CH ₃ N CuCl ₂ 1.7 C ₂ H ₅ CH - 1.8 C ₂ H ₅ N Mn (NO ₃ ) ₂ 1.9 C ₂ H ₅ N - Mp. 81.5-83.5 ° 1.10 C ₂ H ₅ N ENT ₃ 1.11 C ₂ H ₅ N ZnCl ₂ 1.12 C ₂ H ₅ N 1.13 C ₂ H ₅ N 1.14 CH light brown OeI 1.15 C ₃ H ₇ -n CH 1.16 C ₃ H ₇ -H CH 1.17 N M.p. 68.5-71 ° 1.18 N 1.19 N

- 44 -

Continuation of Table 1 :

Verb no. ^R io -Cl Y salt Physics. constant A 1.20 C ₄ H ₉ -H \ -Cl N - B 1.21 C ₄ H ₉ -n 4 -CH ₃ CH - A 1.22 CH ₂ Cl 4 -CH ₃ N - B 1.23 CH ₂ OH N - Mp 111-122 ° 1.24 CH ₂ OCH ₂ - ^ N - Tough OeIf ^ η = 1.5865 1.25 CH ₂ OCH ₂ - ^ N - Mp. 83-85 ° 1.26 CH ₂ O- ^ CH ₂ OC ₂ H ₅ CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₂ OCH ₃ N - Mp. 107-109 ° 1.27 CH ₂ O - (^ N - Mp. 90-94 ° 1.28 CH ₂ OH CH - 1.29 CH ₂ OCH ₃ CH - 1.30 C ₂ H ₅ N 1 / 2CuSO ₄ 1.31 1.32 1.33 N N N -

- 45 -

Table 2; Compounds of the formula

/ ⁴ R

(XXII)

wherein the isomeric forms are to be included:

Verb. ^R u R ₁₂ Y salt Physics. constant No. X A, 2.1 CH ₃ C ₂ H ₅ CH - 2.2 CH ₃ C ₂ H ₅ N - 2.3 CH ₃ C ₂ H ₅ CH ENT ₃ 2.4 CH ₃ C ₂ H ₅ N ENT ₃ 2.5 CH ₃ C ₃ H ₇ -n CH - 2.6 CH ₃ C ₃ H ₇ -n N - 2.7 CH ₃ C ₃ H ₇ -n N ENT ₃ 2.8 CH ₃ C ₃ H ₇ -n N Mn (NO ₃ ) ₂ 2.9 CH ₃ CH ₃ CH - 2.10 CH ₃ CH ₃ CH CuCl ₂ 2.11 CH ₃ C ₂ H ₅ CH Mn (NO ₃ ) ₂ 2.12 CH ₃ C ₂ H ₅ CH CuCl ₂ 2.13 CH ₃ C ₂ H ₅ N CuCl ₂ 2.14 CH ₃ C ₂ H ₅ N ZnCl ₂ 2.15 CH ₃ C ₂ H ₅ N Mn (NO ₃ ) ₂ 2.16 CH ₃ C ₂ H ₅ N FeCl ₃ 2.17 CH ₃ CH ₃ N - oil; Пр ³ = 1.5643 2.18 CH ₃ CH ₃ N ENT ₃ 2.19 C ₂ H ₅ CH ₃ CH MnCl ₂ 2.20 C ₂ H ₅ CH ₃ N MnCl ₂ 2.21 C ₂ H ₅ CH ₃ CH H ₂ SO ₄ 2.22 C ₂ H ₅ CH ₃ CH ZnCl ₂

Continuation of Table 2 :

Verb no. ^R u ^R 12 Y salt 2.23 C ₂ H ₅ C ₂ H ₅ CH - 2.24 C ₂ H ₅ C ₂ H ₅ CH H ₂ SO ₄ 2.25 C ₂ H ₅ C ₂ H ₅ N - 2.26 C ₂ H ₅ C ₂ H ₅ N ENT ₃ 2.27 C ₂ H ₅ C ₂ H ₅ N HCl 2.28 C ₂ H ₅ N - 2.29 C ₂ H ₅ C ₃ H ₇ -I N - 30.2 C ₂ H ₅ C ₃ H ₇ -H CH - 2.31 C ₂ H ₅ C ₃ H ₇ -H N HCl 2:32 C ₂ H ₅ C ₂ H ₅ N Mn (NO ₃ ) ₂ 2:33 CH ₃ C ₂ H ₅ N (COOH) ₂ 2:34 CH ₃ C ₂ H ₅ CH (COOH) ₂ 2:35 CH ₃ c ₃ H ₇ -i N - 2:36 CH ₃ c ₃ H ₇ -i N H ₂ SO ₄ 2:37 - (CHj) ₄ - CH - 2:38 - (CHj) ₄ - CH ENT ₃ 2:39 - (CHj) ₄ - N - 2:40 N Mn (NO ₃ ) ₂ 2:41 - (CH ₂ ) ₄ - N (COOH) ₂ 2:42 - (CHj) ₄ - N ZnCl ₂ 2:43 " ^(CH 2 ⁾ 4" N HCl 2:44 - (CHj) ₄ - CH ZnCl ₂

Table 3 ; Compounds of the formula

16

(XXIII)

wherein the isomeric forms are to be included:

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3.1 H C ₂ H ₅ Cl H Cl H N - oil; Пр ³ -1.5778 3.2 H C ₂ H ₅ CH ₃ H CH ₃ H N - Mp. 74-76 ° 3.3 H C ₂ H ₅ CH ₃ H CH ₃ H N ENT ₃ 3.4 H C ₂ H ₅ Cl H Cl H CH - 3.5 H C ₂ H ₅ Cl H Cl H N CuCl ₂ 3.6 H C ₂ H ₅ H H Cl H N - Mp. 74-80 ° 3.7 H C ₂ H ₅ H H Cl H CH - oil; n * ⁵ «1.5750 3.8 H C ₂ H ₅ H Cl H 5-Cl N - Mp 111.5-114 ° 3.9 H C ₂ H ₅ H Cl H 6-Cl CH - 3.10 CH ₃ CH ₃ H Cl H 5-Cl N Mn (NO ₃ ) ₂ 3.11 H C ₂ H ₅ H Cl H H N - Mp. 96-98 °

Continuation of Table 3 ;

Verb no. ^R U ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3.12 H C ₂ H ₅ H Cl H H CH - Mp. 69-71 * 3.13 H CH ₃ H br H H N - 3.14 CH ₃ CH ₃ Cl H Cl H N - 3.15 CH ₃ CH ₃ Cl H Cl H CH - 3.16 H C ₃ H ₇ (n) H Cl H H N - 3.17 H C ₃ H ₇ (n) H Cl H 5-Cl N - 3.18 H C ₃ H ₇ (I) H Cl H 5-Cl N - 3.19 H C ₃ H ₇ (X) H Cl H 5-Cl CH - 3.20 H C ₃ H ₇ (I) H Cl H H N ENT ₃ 3.21 C ₂ H ₅ C ₂ H ₅ H H CH ₃ H N - 3.22 C ₂ H ₅ C ₂ H ₅ CH ₃ H CH ₃ H N - 3.23 CH ₃ CH ₃ CH ₃ H CH ₃ H N - 3.24 H CH ₃ H (CH-CH) ₂ H N - 3.25 3.26 H H CH ₃ C ₂ H ₅ H H (CH-CH) ₂ (CH-CH) ₂ H H CH N 23 OeI; n_ »1.6086 3.27 H C ₂ H ₅ H (CH-CH) ₂ H CH - 3.28 H C ₂ H ₅ H (CH-CH) ₂ H N HCl 3.29 H C ₂ H ₅ H (CH-CH) ₂ H N (COOH) ₂

Continuation of Table 3 :

Verb no. ^R ll ^R 12 ^R 13 ^R 14 F H ^R 15 ^R 16 Y salt 3.30 H C ₂ H ₅ Cl (CH = F H CH) ₂ H N - 3.31 CH ₃ CH ₃ CH ₃ (CH = H F CH) ₂ H N - 3:32 CH ₃ CH ₃ H (CH = CH) ₂ H N CuCl ₂ 3:33 H CH ₃ (CH = CH) ₂ H 2-Cl N - 3:34 H C ₂ H ₅ (CH-CH) ₂ H 3-Cl N - 3:35 H C ₂ H ₅ (CH = CH) ₂ H H N - 3:36 H C ₂ H ₅ (CH-CH) ₂ H H CH - 3:37 H C ₂ H ₅ (CH = CH) ₂ H H N Mn (NO) ₃ 3:38 H C ₂ H ₅ (CH = CH) ₂ H 2-CH ₃ N - 3:39 CH ₃ CH ₃ (CH-CH) ₂ H H N - 3:40 CH ₃ CH ₃ (CH = CH) ₂ H H CH - 3:41 H c ₃ H ₇ -i (CH = CH) ₂ H H N - 3:42 H C ₂ H ₅ (CH = CH) ₂ H 2-CH ₃ CH HCl 3:43 C ₂ H ₅ C ₂ H ₅ (CH = CH) ₂ H H N - 3:44 H C ₂ H ₅ H H CH - 3:45 H C ₂ H ₅ H H N - 3:46 H C ₂ H ₅ H H CH -

Continuation of Table 3 :

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3:47 H C ₂ H ₅ H F H H N - 3:48 H CH ₂ OCH ₃ F H H H CH - 3:49 H CH ₂ OCH ₃ H F H H CH - 3:50 H CH ₂ OCH ₃ H F H H N - 3:51 H C ₂ H ₅ H H F H CH - Oei 3:52 H C ₂ H ₅ H H F H N - 3:53 H CH ₂ OH Cl H H H CH - 3.54 H CH ₂ OH H H F H CH - 3:55 H CH ₂ OCH ₃ H H F H N - tough mass 3:56 H C ₂ H ₅ Cl H H H CH - 3:57 H CH ₂ OCH ₃ Cl H H H CH - 3:58 H CH ₂ OCH ₃ Cl H H H N - 3:59 H C ₂ H ₅ Cl H H H N - 3.60 H CH ₃ H Cl H H CH - 3.63 H CH ₂ OH H Cl H H CH - 3.64 H CH ₂ OC ₂ H ₅ H Cl H H CH - 3.65 H CH ₂ OCH ₃ H Cl H H N - 3.66 CH ₃ CH ₃ H Cl H H CH -

Continuation of Table 3 ;

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3.67 H C ₃ H ₇ -n H Cl H H CH - 3.68 H CH ₂ OCH ₃ H Cl H H CH - 3.69 H ^c 6 ^H i3- ⁿ H H Cl H CH - 3.70 CH ₃ CH ₃ H H Cl H CH - Oei 3.71 H ^C 6 ^H 5 H H Cl H CH - 3.72 H CH ₂ OC ₂ H ₅ H H Cl H CH - 3.73 H CH ₂ OH H H Cl H CH - 3.74 H H H H Cl H CH - 3.75 H C ₃ H ₇ -H H H Cl H CH - tough mass 3.76 H CH ₃ H H Cl H CH - 3.77 H CH ₂ Cl H H Cl H CH - 3.78 H CH ₂ OCH ₃ H H Cl H CH - Oei 3.79 H CH ₂ OCH ₂ CH = CH ₂ H H Cl H CH - 3.80 H CH ₂ OCH ₂ C ⁵ CH H H Cl H CH - 3.81 H CH ₃ H H Cl H N - 3.82 H C ₂ H ₅ H H Cl H N ENT ₃ 3.83 H CH ₂ OCH ₃ H H Cl H N - Oei 3.84 H CH ₂ O (CH ₂ ) ₂ and ₃ H H Cl H CH -

Continuation of Table 3 ;

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. Smp.85-90 ° 3.85 CH CH ₃ H H Cl H N - Oei 3.86 H «τ C ₂ H ₅ H H Ό Cl H N M 1 / 2CuSO ₄ · η ₂ ο 3.87 H C ₃ H ₇ -n H H Cl H N 3.88 H CH ₂ OC ₂ H ₅ H H Cl H N - 3.89 H CH ₂ OCH ₂ CH-CH ₂ H H Cl H N - 3.90 H CH ₂ O (CH ₂ ) ₂ and ₃ H H Cl H N - 3.91 H CH ₂ OCB ₃ br H H H CH - 3.92 H CH ₂ OCH ₂ C ² CH H H Cl H N - 3.93 H CH ₂ O (CH ₂ ) ₂ and ₃ H H Cl H N 1 / 2CuSO ₄ 3.94 H CH ₂ OCH ₃ br H H H N - 3.95 H C ₂ H ₅ H br H H CH - 3.96 H CH ₂ OCH ₃ H H br H N - 3.97 H CH ₂ OCH ₃ H H J H CH - 3.98 H C ₂ H ₅ H H J H N - 3.99 H CH ₂ OCH ₃ H br H H CH - 3100 H C ₂ H ₅ H br H H N - 3101 H CH ₂ OH H H br H CH - 3102 H CH ₂ OCH ₃ H H br H CH -

Continuation of Table 3 :

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt 3103 H C ₂ H ₅ H H br H N - 3104 H C ₂ H ₅ CH ₃ H H H N - 3105 H C ₂ H ₅ H CH ₃ H H N - 3106 H CH ₂ OCH ₃ H H CH ₃ H CH - 3107 CH ₃ CH ₃ CH ₃ H H H CH - 3108 H CH ₂ OCH ₃ H CH ₃ H H CH - 3109 H CH ₂ OCH ₃ H CH ₃ H H N - 3110 H CH ₂ OH H H CH ₃ H CH - 3111 H C ₂ H ₅ H H CH ₃ H N - 3112 H CH ₂ OCH ₃ C ₂ H ₅ H H H CH - 3113 H C ₂ H ₅ C ₂ H ₅ H H H N - 3114 H CH ₂ OCH ₃ H C ₂ H ₅ H H CH - 3115 H C ₃ H ₇ -n H C ₂ H ₅ H H N - 3116 H CH ₂ OH H H C ₂ H ₅ H CH - 3117 H C ₂ H ₅ H C ₂ H ₅ H H CH - 3118 H CH ₂ OCH ₃ H H C ₂ H ₅ H CH - 3119 H CH ₂ OCH ₃ H H C ₂ H ₅ H N - 3120 H CH ₂ OCH ₃ C ₃ H ₇ -H H H H CH -

- 54 -

ι-Ι-Ι

* I аз I р · ^ I г>. I I OO CTi 33 S3 υ I I (N ₄ I I σ " см I C σ> I Ο \ • • I I W δ S3 о S3 SS S3 Z O S3 S3 33 υ S3 cj S3 Z Z ι-Ι CN Q Z 33 δ 33 33 о δ 33 О Z с СО со ui sr Г- » CO Il I SJ о 33 S3 υ S3 о X S3 Ui υ U 1 UI CM S3 33 υ S3 S3 33 Z υ 33 CJ S3 33 33 33 ік. ui 33 S3 r-4 CM W S3 S3 CM CM CO S3 S3 33 S3 СО ^ ₁ см cj co 33 S3 S3 CMQ S3 33 S3 33 S3 υ IXi С Vf) U ne ** N--І со • и со см • Η • Η 33 ° S3 СО I I I r-l ci I ui I UI I CJ аз CM CM δ co ui S3 U 33 см VO ι S3 ill S3 CM S3 I см δ 33 tu 33 υ S3 CM O CO U 33 • τ * см S3 со S3 S3 S3 S3 υ 33 S3 CJ S3 X <t υ 33 X • rl 33 со "Д. 4J σ> I U I CO CO S3 CM CM S3 I S3 см 33 CO S3 Ο \ 33 CO гН з: S3 33 33 CO аз " гЧ r-4 I-t υ ο ⁴ * 1-4 СО S3 о о со CO 4Y з> S3 CO S3 33 33 CO i 33 СО OCHj CM и CJ * ^ аз ι CO зз " со 33 СО аз зГ UI U 8th UI о о UI CJ о υ о in 33 X CM см -Γ * 33 CM CM 33 CM CM ψ-t CM CM 33 δ 33 см 33 33 CM 33 33 tu о CM υ S3 υ CJ O CJ υ CJ υ S3 t-l S3 00 33 S3 33 ЗІ 33 S3 33 1-4 tu 1-4 <о Ui CM O 1-4 CM UI NO г ". OO см см 1-4 co CO CO СО со со СО СО і-Ч r-4 r-l CO ι-Ι ι-Ι ι-Ι і-І гН г-4 1-4 CO CO CO CO со со СО СО СО CM r-l od r-l r-l you _# U ·

Continuation of Table 3 t

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3,139 3,140 H H CH ₂ OCH ₃ CH ₂ OCH ₃ H H H H OC ₄ H ₉ -n OC ₇ H ₁₅ -H H H CH CH - 3141 H C ₂ H ₅ OCH ₃ H H H N - 3..142 CH ₃ CH. H H OC.Hq-п H N - 3143 H C ₂ H ₅ H H OC ₇ H ₁₅ -H H N - 3144 H C ₂ H ₅ NO ₂ H H H CH - 3,145 3,146 H H CH ₂ OCH ₃ C ₃ H ₇ -n NO ₂ NO ₂ H H H H H H CH N _ 3147 H C ₂ H ₅ H NO ₂ H H N - 3,148 3,149 H H CH ₂ OCH ₃ CH ₂ OCH ₃ H CF ₃ H H NO ₂ H H H CH CH : 3150 H C ₃ H ₇ -n H CF ₃ H H CH - 3151 H CH ₂ OCH ₃ H NO ₂ H H CH - 3152 H C ₂ H ₅ H H NO, H CH - 3153 H C ₂ H ₅ H H NO ₂ H N - 3154 H CH ₂ OCH ₃ H CF ₃ H H CH - 3155 H C ₂ H ₅ H CF ₃ H H CH - tough mass 3156 H C ₂ H ₅ H CF ₃ H H N - Mp. 80-83 °

Continuation of Table 3 ;

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. constant 3157 H CH ₂ OCH ₃ H CF ₃ H H N - 3158 H CH ₂ OCH ₃ H H ^CF 3 H CH - 3159 H CH ₂ OCH ₃ H H CF ₃ H N - 3160 H C ₂ H ₅ H H CF ₃ H CH - 3161 H CH ₂ OCH ₃ Cl H Cl H CH - 3162 H C ₂ H ₅ Cl H H 5-Cl CH - η * ³ - 1.5837 3,163 3,164 H H CH ₂ OCH ₃ C ₂ H ₅ Cl Cl H H H Cl 5-Cl H N CH nj; ² - 1.5779 3165 H H Cl H Cl H N - 3,166 3,167 3,168 H H H CH ₂ OCH ₃ CH ₂ OCH ₃ C ₂ H ₅ Cl Cl Cl H H H Cl H H H 5 Cl 5 Cl N CH N - η * ³ - 1.5788 3169 H CH ₂ OCH. Cl H H 6-Cl CH - 3170 H CH ₂ OCH ₃ Cl H H 6-Cl N - 3171 H C ₂ H ₅ H Cl Cl H CH - nj ³ = 1.5835 3172 H C ₂ H ₅ H Cl Cl H N - Mp. 90-97 ° 3173 H C ₂ H ₅ H Cl H 5-Cl CH - 3174 H C ₂ H ₅ Cl H H 6-Cl CH -

Continuation of Table 3 ;

Verb no. ^R ll ^R 12 ^R 13 ^R 1A ^R 15 ^R 16 Y salt Physics. Const. 3,175 3,176 H H C ₂ H ₅ CH ₂ OCH ₃ Cl H H Cl H Cl 6-Cl H N CH : rip ³ »1.5836 3177 H CH ₂ OCH ₃ H Cl Cl H N - Srap. 48-60 ° 3178 H CH ₃ H Cl H 5-Cl CH - 3179 H CH ₂ OCH ₃ H Cl H 5-Cl CH - 3180 H CH ₂ OCH ₃ H Cl H 5-Cl N - 3181 H CH ₂ OH br H br H CH - 3182 H C ₂ H ₅ br H br H CH - 3183 H C ₂ H ₅ br H br H N - 3184 H C ₂ H ₅ br H Cl H CH - 3185 H C ₂ H ₅ br H Cl H N - 3186 CH ₃ CH ₃ br H br H CH - 3187 CH ₃ CH ₃ F H H H CH - 3188 H CH ₂ OCH ₃ br H br H N - 3189 H CH ₂ OCH ₃ br H Cl H CH - 3190 H CH ₂ OCH ₃ br H Cl H N - 3191 H CH ₂ OCH ₃ Cl H br H CH - 3192 H CH ₂ OCH ₃ Cl H br H N -

Continuation of Table 3;

Verb no. ^R U ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3193 H C ₂ H ₅ CH ₃ H CH ₃ H CH - Mp. 84-90 ° 3194 H C ₂ H ₅ Cl H br H CH - 3195 H C ₂ H ₅ Cl H br H N - 3196 H CH ₂ OCH ₃ CH ₃ H CH ₃ H CH - 3197 H CH ₂ OCH ₃ CH ₃ H CH ₃ H N - 3198 H CH ₂ OC ₂ H ₅ CH ₃ H H 5-CH ₃ N - 3199 H C ₂ H ₅ H CH ₃ H 5-CH ₃ CH - 3200 H CH ₂ OCH ₃ c ₄ H ₉ -t H CH ₃ H CH - 3201 H C ₂ H ₅ c _A H ₉ -t H c ₄ H ₉ -t H N - 3202 H CH ₂ OCH ₃ C ₃ H ₇ -X H H 5-CH ₃ CH - 3203 H CH ₂ O (CH ₂ ) ₂ and ₃ NO ₂ H NO ₂ H CH - 3204 H CH ₂ OC ₂ H ₅ CH ₃ H H 5-CH ₃ CH - 3205 H C ₂ H ₅ H CH ₃ H 5-CH ₃ N - 3206 H CH ₂ OCH ₃ c ₄ H ₉ -t H CH ₃ H N - 3207 H CH ₂ OCH ₃ ^C 4 ^H 9 ^fc H c ₄ H ₉ -t H CH - 3208 H CH ₂ OCH ₃ C ₃ H ₇ -I H H 5-CH ₃ N - 3209 H CH ₂ OC ₂ H ₅ NO ₂ H NO ₂ H N - 3210 H CH ₂ OCH ₃ H Cl Cl 6-Cl CH -

Continuation of Table 3 ;

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3211 H CH ₂ OCH ₃ H Cl Cl 6-Cl N - 3212 H C ₂ H ₅ H Cl Cl 6-Cl CH - tough mass 3213 H C ₂ H ₅ H Cl Cl 6-Cl N - oil; n ^ - 1.5863 3.21Ί и rv r »CH Cl H Cl 6-Cl CH - 3215 H CH ₂ OCH ₃ H Cl Cl 5-Cl CH - 3216 H CH ₂ OCH ₃ H Cl Cl 5-Cl N - 3217 CH ₃ CH ₃ br H br 6-Br N - 3218 H CH ₂ OCH ₃ br H br 6-Br N - 3219 H CH ₂ OCH ₃ CH ₃ CH ₃ H 6-CH ₃ N - 3220 H C ₂ H ₅ CH ₃ H Cl H CH - Mp 94-96 ° 3221 H C ₂ H ₅ CH ₃ H Cl H N - Mp. 78-80 ° 3222 H CH ₂ OCH ₃ Cl H Cl 6-Cl N - 3223 H CH ₂ OH H Cl Cl 5-Cl CH - 3224 H CH ₂ OCH ₃ br H br 6-Br CH - 3225 H CH ₂ OCH ₃ CH ₃ CH ₃ H 5-CH ₃ CH - 3226 H CH ₂ OCH ₃ CH ₃ H Cl H CH - Mp. 92-106 ° 3227 H CH ₂ OCH ₃ CH ₃ H Cl H N - Mp. 101-103 ° 3228 CH ₃ CH ₃ H CH ₃ Cl H N -

Continuation of Table 3:

Verb no. "11 ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3229 H CHjOCH ₃ c ₄ H ₉ -t H Cl H N - 3,230 3,231 H H CHjOCH ₃ CHjOCH ₃ H H CH ₃ Ch ₃ H Cl G-Cl H CK CH η ²² ' ⁵ - 1.5752, OeI 3232 H C ₂ H ₃ H CH ₃ Cl H CH - njp ⁵ - 1.5748.OeI 3233 H CH ₂ OCH ₃ H CH ₃ Cl H N - Mp. 88-93 ° 3234 H C ₂ H ₅ H CH ₃ Cl H N - Mp. 72-75 ° 3235 H C ₃ H ₇ -n ^C 4 ^H 9 " ^t H Cl H CH - 3236 H CHjOCH ₃ c ₄ H ₉ -t H Cl H CH - 3237 H CH ₂ OCH ₃ H CH ₃ H 6-Cl N - 3238 H CH ₂ OCH ₃ br H CH ₃ H CH - 3239 H CH ₂ OCH ₃ br H CH ₃ H N - 3240 H CH ₂ OCH ₃ CH ₃ H br H CH - 3241 H CH ₂ OCH ₃ CH ₃ H br H N - 3242 H CHjOCHjCH-CHj H OCH ₃ H 6-Cl CH - 3243 H CH ₂ OCH ₃ Cl H NOj H CH - 3244 H CHjOCH ₃ Cl H NOj H N - 3245 H H br H CH ₃ H N - 3246 H CHjCl br H br H CH -

Continuation of Table 3 ;

Verb no. ^R U ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physik.Konst. 3247 H ^C 6 ^H 5 CH ₃ H br H N - 3248 H CH ₂ OCH ₃ H OCH ₃ H 6-Cl CH - 3249 H CH ₂ OCH ₃ H OCH ₃ H 6-Cl N - 3250 H CH ₂ OCH ₂ C = CH Cl H NO ₂ H CH - 3251 H CH ₂ OC ₆ H ₅ NO ₂ H Cl H CH - 3252 H C ₂ H ₅ NO ₂ H Cl H CH - 3253 H C ₂ H ₅ NO ₂ H Cl H N - 3254 H CH Cl H CF ₃ H CH - 3,255 3,256 3,257 H H H CH ₂ OCH ₃ CH ₂ OCH ₃ CH ₉ OCH, Cl Cl NO ₂ H H H CF ₃ CF ₃ ^CF 3 H H H CH N CH - 3258 H CH ₉ OCH- NO ₂ H Cl H CH - 3259 H Sm J CH ₂ OCH ₃ NO ₂ H Cl H N - 3260 H C ₂ H ₅ H H CF ₃ H N - 3261 H C ₂ H ₅ H H NO ₂ H CH - 3262 H C ₂ H ₅ H H NO ₂ H N - 3263 H C ₂ H ₅ NO ₂ H CF ₃ H CH - viscous mass 3264 CH ₃ CH ₃ NO ₂ H CF ₃ H N -

Continuation of Table 3 ;

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3265 H CH ₂ OCH ₃ NO ₂ H CF ₃ H N - 3266 H CH-OCH. CF ₃ H NO ₂ H CH - 3267 H C ₂ H ₅ H CH ₃ Cl 5-CH ₃ CH - Mp. 75-78 * 3268 H CH ₂ OCH ₃ H CH ₃ Cl 5-CH ₃ CH - 3269 H CH ₂ OCH ₃ H CH ₃ Cl 5-CH ₃ N - 3270 H C ₂ H ₅ H CH ₃ br 5-CH ₃ CH - 3271 H C ₂ H ₅ NO ₂ H CF ₃ H N - 3272 H CH ₂ OCH ₃ CF ₃ H NO ₂ H N - 3273 H CH ₂ OC ₆ H ₅ H CH ₃ Cl 5-CH ₃ CH - 3274 H C ₂ H ₅ H CH ₃ Cl 5-CH ₃ N - Smp.64-73 ° 3275 H CH ₂ OCH ₃ H CH ₃ Cl 5-CH ₃ CH - 3276 H C ₂ H ₅ H CH ₃ br 5-CH ₃ N - 3277 H CH ₂ OCH ₂ C ² CH H CH ₃ br 54JH ₃ N - 3278 H C ₂ H ₅ Cl H Cl 5-CH ₃ N - 3279 H C ₂ H ₅ Cl H Cl 6-CH ₃ CH - Mp. 70-74 ° 3280 H CH ₂ OCH ₃ Cl H Cl 6-CH ₃ N - 3281 H CH ₃ Cl H Cl 6-CH ₃ N - 3282 H C ₂ H ₅ CH ₃ H br 6-Cl CH -

Continuation of Table 3 :

Verb no. ^R U ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3283 H CH ₂ OCH ₃ H CH ₃ br 5-CH ₃ N - 3284 H C ₂ H ₅ Cl H Cl 5-CH ₃ CH - 3285 H CH ₂ OC ₆ H ₅ Cl H Cl 5-CH ₃ N - 3286 H CH ₂ OCH ₃ Cl H Cl 6-CH ₃ CH - 3287 H C ₂ H ₅ Cl H Cl 6-CH ₃ N - Mp. 98-101 ° 3288 H C ₃ H ₇ -H Cl H Cl 6-CH ₃ N - 3289 H CH ₂ OCH ₃ CH ₃ H br 6-Cl CH - 3290 H CH ₂ OCH ₃ CH ₃ H br 6-Cl N - 3291 H CH ₂ OCH ₃ CF ₃ H NO ₂ 6-CF ₃ CH - 3292 H C ₂ H ₅ NO ₂ H NO ₂ 6-CF ₃ CH - 3293 H C ₂ H ₅ NO ₂ H NO ₂ 6-CF ₃ N - 3294 H C ₂ H ₅ CH ₃ H br 6-Cl N - 3295 CH ₃ CH ₃ CF ₃ H NO ₂ 6-CF ₃ CH - 3296 H CH ₃ CF ₃ H NO ₂ 6-CF ₃ N - 3297 H CH ₂ OCH ₃ CF ₃ H NO ₂ 6-CF ₃ N - 3298 CH ₃ CH ₃ NO ₂ H NO ₂ 6-CF ₃ CH - 3299 H H NO ₂ H NO ₂ 6-CF ₃ N - 3300 H CH ₂ OCH ₃ NO ₂ H NO ₂ 6-CF ₃ N -

Continuation of Table 3 :

Verb no. H ^R 12 ^R 13 ^R 14 H ^R 15 H) ₂ H ^R 16 Y salt Physics. Const. 3301 H CH ₂ OH (CH-CH) ₂ H Cl H H H CH - 3302 H CH ₂ OCH (CH = CH) ₂ Cl H H H H CH - 3303 H C ₃ H ₇ -n (CH ₂ -CH) ₂ Cl Cl H H H N - 3304 H CH ₂ OCH ₃ (CH ₂ -CH) ₂ Cl H H H N - 3305 H CH ₂ OH (CH ₂ -CH) ₂ CH ₃ Cl H H CH - 3306 H C ₂ H ₅ (CH ₂ -CH) ₂ CH ₃ Cl br H N - 3307 H CH ₂ OCH ₃ (CH ₂ -CH) ₂ Cl Cl H CH - 3308 H CH ₂ OCH ₃ (CH ₂ -CH) ₂ Cl H N - 3309 H H CH ₂ OCH ₃ (CH-CH) ₂ H CH - 3,310,311 сн ₃ CH ₂ OCH ₃ C ₂ H ₅ (CH-C Cl H H N CH 23 OeI; n _D -1.5832 3312 H H CH ₃ Cl H CH - 3,313,314 H CH ₂ OCH ₃ C ₂ H ₅ Cl Cl H H CH N - oil; Пр ³ -1.5796 3315 H CH ₂ OCH ₃ Cl H N - 3316 H CH ₂ OCH ₃ CH ₃ H CH - 3317 CH OCH CH ₃ H N - 3318 - (CH ₂ ), - H H N -

Continuation of Table 3 t

Verb no. ^R u R ₁₂ ^R 13 ^R 14 ^R 15 ^R 16 Y salt 3,319 H C ₂ H ₅ CH ₃ CH ₃ H H CH - 3320 H CH ₂ OCH ₃ CH ₃ CH3 H H N - 3321 H C ₂ H ₅ Cl Cl Cl H CH - 3322 H C ₂ H ₅ Cl Cl Cl H N - 3323 H CH ₂ OCH ₃ Cl Cl Cl H CH - 3324 H CH ₂ OCH ₃ Cl Cl H 6-Cl CH - 3325 H CH ₂ OCH Cl Cl H 6-Cl N - 3326 CH ₃ CH ₃ Cl Cl H 6-Cl CH - 3327 H CH ₂ OCH ₃ Cl Cl H 6-Cl N - 3328 H CH ₂ OCH ₃ H CH ₃ H 5-CH ₃ N - 3329 H C ₃ H ₇ -H F H H H CH - 3330 H CH ₂ OH F H H H CH - 3331 H CH ₂ OC ₂ H ₅ F H H H CH - 3332 H C ₃ H ₇ -U F H H H N - 3333 H CH ₂ OCH ₃ F H H H N - 3334 H CH ₃ H F H H CH - Ϊ.335 CH ₃ CH ₃ H F H H CH - 3336 H C ₃ H ₇ -n H F H H CH -

Continuation of Table 3 :

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3337 H CH ₂ OH H F H H CH - 3338 H C ₃ H ₇ -U H F H H N - 3339 H CH ₂ OH H F H H N - 3340 H CH ₂ OCH ₃ H H F H CH - Oei 3341 H H H H F H CH - 3342 H CH ₃ H H F H CH - 3343 CH ₃ CH ₃ H H F H CH - 3344 H C ₃ H ₇ -n H H F H CH - 3345 H H H H F H N - 3346 H CH ₃ H H F H N - 3347 CH ₃ CH ₃ H H F H N - 3348 H CH ₂ OH H H F H N tough mass 3349 H CH ₂ OC ₂ H ₅ H H F H N - 3350 H CH ₂ OC ₂ H ₅ Cl H H H CH - 3351 H CH ₃ Cl H H H N - 3352 CH ₃ CH ₃ Cl H H H N - 3353 H CH ₃ br H H H CH - 3354 CH ₃ CH ₃ br H H H CH -

Continuation of Table 3 ;

Verb no. ^R U ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt 3355 H C ₂ H ₅ br H H H CH - 3356 H CH ₂ OH br H H H CH - 3357 H CH ₃ br H H H N - 3358 CH ₃ CH ₃ br H H H N - 3359 H C ₂ H ₅ br H H H N - 3360 H CH ₂ OH br H H H N - 3361 H CH ₂ OC ₂ H ₅ br H H H CH - 3362 H CH ₂ OC ₂ H ₅ br H H H N - 3363 H H H br H H CH - 3364 H CH ₃ H br H H CH - 3365 H C ₃ H ₇ -H H br H H CH - 3366 H CH ₂ OH H br H H CH - 3367 H CH ₃ H br H H N - 3368 CH ₃ CH ₃ H br H H N - 3369 H C ₃ H ₇ -Il H br H H N - 3370 H CH ₂ OH H br H H N - 3371 H CH ₂ OCH ₃ H br H H N -

Continuation of Table 3 :

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. J.372 H C ₂ H ₅ H H br H CH - Oei 3373 H C ₃ H ₇ -H H H br H CH - 3374 H CH ₂ OC ₂ H ₅ H H br H CH - 3375 CH ₃ CH ₃ H H br H N - 3376 H C ₃ H ₇ -H H H br H N - Oei 3377 H CH ₂ OH H H br H N - 3378 H CH ₂ OC ₂ H ₅ H H br H N - 3379 H C ₂ H ₅ H H J H CH - 3380 H CH ₂ OH H H J H CH - 3381 H CH ₂ OCH ₃ H H J H N - 3382 H CH ₂ OH H H J H N -

Continuation of Table 3:

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y salt Physics. Const. 3383 H C ₂ H ₅ CF ₃ H H 5-NO ₂ CH - OeI, h ^ 1.5572 3384 H C ₂ H ₅ Cl H NO ₂ H CH - OeI, rip 1.5941 3385 H C ₂ H ₅ H H OCH ₃ H N - 27 tough mass, η 1.5641 3386 H C ₂ H ₅ Cl H NO ₂ H N - OeI, η? ⁸ 1.5942 3387 H C ₂ H ₅ H H CF ₃ H N - Mp. 106-107 ° 3388 H C ₂ H ₅ C ₂ H ₅ H H H CH ENT ₃ Mp. 99-101 °

Table 4; Compounds of the formula

Щ m

^R 15 ~ * ^R 16

(XXIV)

wherein the isomeric forms are to be included:

Verb no. ^R u ^R 12 ^R 13 ugh ^R 15 ^R 16 Y ^R 17 ^R 18 salt 4.1 H C ₂ H ₅ Cl H Cl H N 3-NO ₂ H - 4.2 H ^C 2 ^H 5 CH ₃ H H H N 2-CH ₃ H - 4.3 H C ₂ H ₅ CH ₃ H CH ₃ H N 3-CH ₃ H ENT ₃ 4.4 H C ₂ H ₅ Cl H Cl H CH 2-CH ₃ 6-CH ₃ - 4.5 H ^C 2 ^H 5 Cl H Cl H N 2-Cl H CuCl ₂ 4.6 H C ₂ H ₅ H H Cl H N 3-NO ₂ H - 4.7 H C ₂ H ₅ H H Cl H CH 3-NO ₂ H - 4.8 H C ₂ H ₅ H Cl H 5-Cl N 2-Cl H - 4.9 C ₂ H. H H Cl H 6-Cl CH 2-NO ₂ H - 4.10 CH ₃ CH ₃ H Cl H 6-Cl N 2-NO ₂ H Mn (NO ₃ ) ₂ 4.11 H C ₂ H ₅ Cl H H H N 2-Cl H -

Continuation of Table 4 ;

Verb no. ^R u ^R 12 ^R 13 ^R 14 CH) ₂ CH) ₂ ^R 15 ^R 16 Y ^R 17 ^R 18 salt Physics. constant 4.12 H C ₂ H ₅ H Cl (CH-CH) ₂ CH) ₂ H H CH 2-Br H - 4.13 H CH ₃ H br (CH (CH-CH) ₂ H H N 2-CH ₃ H - 4.14 CH ₃ CH ₃ Cl H (CH Cl H N 2-Cl 6-Cl - 4.15 H CH ₃ H H Cl H CH 2-CH ₃ H - resin 4.16 H C ₃ H ₇ -n Cl H H H N 2-Cl H - 4.17 H C ₃ H ₇ -H H Cl H 6-Cl N 2-Cl H - 4.18 H c ₃ H ₇ -i H Cl H 6-Cl N 2-OCH ₃ H - 4.19 H C ₃ H ₇ -X H Cl H 5-Cl CH 2-OCH ₃ 6-OCH ₃ - 4.20 H c ₃ H ₇ -i H Cl H H N 2-Cl H ENT ₃ 4.21 C ₂ H ₅ C ₂ H ₅ H H CH ₃ H N 2-Cl H - 4.22 C ₂ H ₅ C ₂ H ₅ CH ₃ H CH ₃ H N 2-Cl H - 4.23 CH ₃ CH ₃ H F H H N 2-CH ₃ H - brown yellow resin 4.24 H CH ₃ (CH-CH) ₂ H H N 2-Cl H - 4.25 H C ₂ H ₅ (CH H H N 2-Cl 6-Cl - 4.26 H CH ₃ H H CH 2-NO ₂ H - 4.27 H C ₂ H ₅ H H N 2-Cl H - 4.28 H C ₃ H ₇ -X H H N 2-Cl H - 4.29 CH ₃ CH ₃ H H N 3-Cl H -

Continuation of Table 4 ;

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y ^R 17 ^R 18 salt 4.30 CH ₃ CH ₃ (CH = CH) ₂ H H N 2-Cl H - 4.31 CH ₃ CH ₃ (CH-CH) ₂ H 2-Cl N 2-Br H - 4:32 H ^C 2 ^H 5 (CH-CH) ₂ H H N 2-Cl H HCl 4:33 H CH ₃ (CH-CH) ₂ CH ₃ H N 3-Cl H - 4:34 H CH ₃ (CH-CH) ₂ H 2-CH ₃ N H H HCl 4:35 H CH ₃ (CH-CH) ₂ H H N H H - 4:36 H CH ₃ (CH-CH) ₂ H H CH H H - 4:37 H CH ₃ H (CH-CH) ₂ H N 3-NO ₂ H - 4:38 H CH ₃ H (CH-CH) ₂ H CH 3-NO ₂ H - 4:39 H CH ₃ H (CH-CH) ₂ H N H H CuCl ₂ 4:40 H CH ₃ Cl (CH-CH) ₂ H N 2-Cl H - 4:41 CH ₃ CH ₃ Cl (CH-CH) ₂ H N 2-Cl H - 4:42 H C ₂ H ₅ Cl (CH-CH) ₂ H N 3-Cl H - 4:43 H C ₃ H ₇ -I CH ₃ (CH-CH) ₂ H N H H - 4:44 H CH ₃ CH ₃ (CH-CH) ₂ H N 2-Cl 6-Cl - 4:45 H CH ₃ Cl (CH-CH) ₂ 3-Cl N 2-Cl H - 4:46 H CH ₃ CH ₃ (CH = CH) ₂ 3-CH ₃ N H H - 4:47 H CH ₃ CH ₃ (CH = CH) ₂ H N 2-Cl H -

Continuation of Table 4 ;

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y ^R 17 ^R 18 salt Physics. constant 4:48 CH ₃ H CH ₃ H H H N 2-CH ₃ H - dark yellow resin 4:49 CH ₃ CH ₃ CH ₃ H OCH ₃ H N 2-CH ₃ H - 4:50 CH ₃ H H H OCH ₃ H N 2-CH ₃ H - resin 4:51 C ₃ H ₇ -H H CH ₃ H H H N 2-CH ₃ H - 4:52 C ₃ H ₇ -n H CH ₃ H OCH ₃ H N 2-CH ₃ H - 4:53 C ₂ H ₅ H CH ₃ H OCH ₃ H N 2-CH ₃ H - 4:54 H CH ₂ OCH ₃ F H H H CH 2-Cl H - 4:55 H C ₂ H ₅ F H H H N 2-CH ₃ H - resin 4:56 H CH ₂ OCH ₃ H F H H CH 2-Cl H - 4:57 H C ₂ H ₅ H H F H N 2-CH ₃ H - light brown resin 4:58 H C ₂ H ₅ H F H H N 2-Cl H - 4:59 H C ₂ H ₅ H H F H CH 2-CH ₃ H - brown resin 4.60 H C ₂ H ₅ H H F H CH 2-Cl H - 4.61 H CH ₂ OCH ₃ Cl H H H CH 2-Cl H - 4.62 H CH ₂ OCH ₃ Cl H H H N 2-Cl H - 4.63 H CH ₂ OH H Cl H H CH 2-Cl H - 4.64 H C ₂ H ₅ H H Cl H CH 2-CH ₃ H - 4.65 H CH ₃ H H F H N 2-CH ₃ H - viscous oil

Continuation of Table 4 :

Verb no. "11 ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y ^R 17 ^R 18 salt Physics. constant 4.66 H CH ₃ H H F H CH 2-CH ₃ H - 4.67 H CH ₂ OCH ₃ H H Cl H N 2-Cl H - 4.68 H C ₂ H ₅ H br H H CH 2-CH ₃ H - 4.69 H C ₂ H ₅ F H H H CH 2-CH ₃ H - 4.70 H CH ₃ H H F H CH 2-CH ₃ H - light brown resin 4.71 4.72 4.73 4.74 H H H H CH ₂ OCH ₃ CH ₂ OCH ₃ CH ₂ OCH ₃ C ₂ H ₅ Br H H H H Br H H H Br Br Br H H H H N CH CH N 2-Cl 2 Cl 2 Cl 2 Cl H H H H - 4.75 H CH ₂ OCH ₃ H H J H CH 2-Cl H - 4.76 It.77 H H CH ₂ OCH ₃ C ₃ H ₇ -H H CH ₃ H H J H H H N N 2-Cl 2-CH ₃ H H ENT ₃ Mp. 105-110 ° 4.78 H CH ₃ CH ₃ H H H N 2-CH ₃ H ENT ₃ Mp. 92-95 ° B 4.79 H H CH ₃ H H CH 2-Cl H - 4.80 H CH ₂ OCH ₃ CH ₃ H H H CH 2-Cl H - 4.81 H CH ₃ CH ₃ H H H N 2-CH ₃ H ENT ₃ Mp 129-134 ° A 4.82 H CH ₂ OCH ₃ H H CH ₃ H N 2-Cl H - 4.83 H CH ₂ OCH ₃ H H CH ₃ H CH 2-CH ₃ H -

Continuation of Table 4 ;

Verb no. ^R u R ₁₂ ^R 13 ^R 14 ^R 15 ^R 16 Y ^R 17 ^R 18 salt Physics. constant 4.84 H C ₂ H ₅ H H C ₂ H ₅ H N 2-Cl H - 4.85 H CH ₂ OCH ₃ ⁰ J ¹ T " H H H CH H H - 4.86 H CH ₂ OCH ₃ C ₃ H ₇ - H H H CH 2-NO ₂ H - 4.87 H CH ₂ OCH ₃ H C ₂ H ₅ H H CH 3-CH ₃ H - 4.88 H CH ₂ OCH ₃ H C ₂ H ₅ H H N 2-Cl H - 4.89 CH ₃ CH ₃ H H OCH ₃ H N 2-CH ₃ H - Resin B 4.90 H C ₃ H ₇ -n H H OCH ₃ H N 2-CH ₃ H - Oei 4.91 H C ₃ H ₇ -H H H OCH ₃ H N 2-CH ₃ H - OeI B 4.92 CH ₃ CH ₃ H H OCH ₃ H N 2-CH ₃ H - Resin A 4.93 H C ₂ H ₅ H H OCH ₃ H N 2-CH ₃ H - resin 4.94 H C ₃ H ₇ -n H H OCH ₃ H N 2-CH ₃ H - OeI A 4.95 H CH ₂ OC ₂ H ₅ NO ₂ H H H CH 2-Br H - 4.96 H CH ₂ OCH ₃ H H NO ₂ H CH 2-Cl H - 4.97 H CH ₂ OH H CF ₃ H H CH 3-CH ₃ H - 4.98 H CH ₂ OCH ₃ H H CF ₃ H CH 2-Cl H - 4.99 H CH ₂ OCH ₃ H Cl H H CH 2-Cl H - 4100 H CH ₂ OCH ₃ br H br H CH 2-Cl H - 4101 H CH ₂ OCH ₃ Cl H Cl H CH 2-Cl H -

Continuation of Table 4:

Verb no. hl ^R 12 »4 H ^R 13 ^R 14 H ^R 15 H Cl ^R 16 Y ^R 17 ^R 18 salt 4102 CH ₂ OH H H (CH-CH) ₂ (CH-CH) ₂ H Cl Cl H CH 2-Cl H - 4103 C ₂ H ₅ H H CH ₃ (CH-CH) ₂ Cl H Cl H CH 2-OCH ₃ 6-OCH ₃ - 4104 C ₂ H ₅ H H (CH-CH) ₂ H H H H CH 2-Cl H - 4105 CH ₂ OCH ₃ H H H H H Cl H CH 2-Cl H - 4106 CH ₂ OCH ₃ H CH ₃ H H H Cl H N H H - 4107 C ₂ H ₅ H CH ₃ (CH-CH) ₂ H Cl H CH 2-Cl H - 4108 C ₂ H ₅ H C ₂ H ₅ (CH-CH) ₂ H Cl H N 2-Cl H - 4109 C ₂ H ₅ H (CH-CH) ₂ H F H CH 2-Cl H - 4110 C ₂ H ₅ H (CH-CH) ₂ F H N 2-Cl H - 4111 (CH ₂ ] H F H CH H H - 4112 CH ₂ OCH ₃ Cl H CH 2-Cl H - 4113 CH ₃ H H N 2-CH ₃ H - 4114 C ₂ H ₅ H H N 2-OCH3 6-OCH ₃ - 4115 C ₂ H ₅ H H CH 2-OCH ₃ 6-OCH ₃ - 4116 C ₂ H ₅ H H N 2-CH ₃ H - 4117 CH ₃ H H N 2-CH ₃ H - 4118 CH ₃ H H CH 2-GH ₃ H - 4119 CH ₃ H H N 2-CH H -

Continuation of Table 4 ;

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y ^R 17 ^R 18 salt Physics. constant 4120 CH ₃ C ₂ H ₅ H H F H CH 2-CH ₃ H - 4121 H H H H F H N 2-CH ₃ H - 4122 H H H H F H CH 2-CH ₃ H - 4123 H -C ₃ H ₇ -U H H F H N 2-CH ₃ H - resin 4124 H -C ₃ H ₇ -n H H F H CH 2-CH ₃ H - resin 4125 H CH ₂ OCH ₃ H H F H N 2-CH ₃ H - 4126 H CH ₂ OCH ₃ H H F H CH 2-CH ₃ H - 4127 H H H H Cl H N 2-CH ₃ H - 4128 H H H H Cl H CH 2-CH ₃ H - high-viscosity oil 4129 H CH ₃ H H Cl H N 3-CH ₃ H - 4130 H C ₂ H ₅ H H Cl H N 3-CH ₃ H - 4131 H H H H Cl H N 3-CH ₃ H - 4132 H CH ₃ H H Cl H CH 3-CH ₃ H - 4133 H C ₂ H ₅ H H Cl H CH 3-CH ₃ H - 4134 H C ₃ H ₇ -H H H Cl H CH 3-CH ₃ H - 4135 H CH ₂ OCH ₃ H H Cl H CH 3-CH ₃ H -

Continuation of Table 4;

Verb no. ⁸ U ^R 12 ^R 13 ^R 14 ^R 15 H Y ^R 17 ^R 18 salt Physics. constant 4136 сн ₃ CH ₃ H F H H CH 2-CH ₃ H ENT ₃ Mp 131-140 ° 4137 H C ₂ H ₅ H H Cl H N 2-Cl H - Resin, η? ² 1.5631 4138 H C ₂ H ₅ H H Cl H CH 2-CH ₃ H ENT ₃ Mp 124-126 ° 4139 H CH ₃ F H H H N 2-CH ₃ H - Resin, n ^ ² 1.5587 4140 H C ₂ H ₅ H H Cl H N 2-CH ₃ H ENT ₃ Mp. 140-141 · 4141 H H OCH H H H N 2-Cl H - oil; nj ^ ² 1.5762 4142 H H OCH ₃ H H H CH 2-Cl H - oil; n £ ² 1.5830 4143 H C ₂ H ₅ H F H H CH 2-CH ₃ H HBr Mp. 175-177 · 4144 H CH ₃ H H Cl CH 2-CH ₃ H HBr Mp 180-184 °

Continuation of Table 4;

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y "17 ^R 18 salt Physics. constant 4145 CH ₃ CH ₃ H F H H CH 2-CH ₃ H - Oei 4146 CH ₃ CH ₃ H H Cl H N 2-CH ₃ H - viscous oil 4147 H C ₂ H ₅ H H F H CH 2-OCH ₃ 3-Cl ^H - Visc. oil; α ²⁰ ' ⁵ 1.5570 4148 H ^C 2 ^H 5 H H Cl H N 3-Cl I H - oil; τζ ¹ 1.5793 4149 H ^C 2 ^H 5 H H Cl H CH 3-Cl H - oil; nj ² 1.5832 4150 H C ₂ H ₅ H H H 5-Cl N 3-Cl H - oil; τζ ² 1.5787 4151 H C ₂ H ₅ H H H 5-Cl CH H oil; nj ² 1.5827

- 77 -

Table 5: Compounds of the formula

fl8

¹⁷

wherein the isomeric forms are to be included:

Verb. R _n R ₁₂ ^R 17 ^R 18 Y salt Physics. constant No. 5.1 сн ₃ C ₂ H ₅ 2-Cl H CH - 5.2 CH ₃ C ₂ H ₅ 2-Cl H N - 5.3 сн ₃ C ₂ H ₅ 2-Cl 6-Cl CH ENT ₃ 5.4 CH ₃ C ₂ H ₅ 2-CH ₃ H N ENT ₃ 5.5 сн ₃ ^C 3 ^H 7 ~ ⁿ 2-Cl H CH - 5.6 сн ₃ C ₃ H ₇ -n 2-Cl H N - 5.7 сн ₃ C ₃ H ₇ -n 3-Cl H N ENT ₃ 5.8 сн ₃ ^C 3 ^H 7 ~ ⁿ 3-Cl 6-Cl N Mn (NO ₃ ) ₂ 5.9 сн ₃ CH ₃ 2-Cl H CH - 5.10 сн ₃ CH ₃ 2-Cl 6-Cl CH CuCl ₂ 5.11 сн ₃ C ₂ H ₅ 2-Cl H CH Mn (NO ₃ ) ₂ 5.12 сн ₃ C ₂ H ₅ 2-CH ₃ 6-CH ₃ CH CuCl ₂ 5.13 сн ₃ CH ₃ 2-CH ₃ H N ENT ₃ Mp 158-160 ° 5.14 сн ₃ CH ₃ 2-CH ₃ H N HBr Mp 192-204 ° 5.15 сн ₃ C ₂ H ₅ 2-CH ₃ H N Mn (NO ₃ ) ₂ 5.16 сн ₃ C ₂ H ₅ 2-NO ₂ H N FeCl ₃ 5.17 сн ₃ CH ₃ 2-Cl H N - 5.18 сн ₃ CH ₃ 2-Cl 5-Cl N ENT ₃ 5.19 C ₂ H ₅ CH ₃ 3-Cl H CH MnCl ₂ 5.20 C ₂ H ₅ CH ₃ 2-CH ₃ H N MnCl ₂ 5.21 CH ₃ 2-CH ₃ H N CuCl ₂ 5.22 C ₂ H ₅ CH ₃ 2-Cl 5-Cl N ZnCl ₂ 5.23 C ₂ H ₅ C ₂ H ₅ 2-Br H CH - 5.24 H C ₂ H ₅ 2-UCIl ₃ 6-OCH ₃ CH -

- 78 -

Continuation of Table 5 :

Verb. ^R ll ^R 12 ^R 17 ^R 18 Y salt Physics. constant No. 5.25 H H 2-Cl H N - 5.26 H H 2-Cl H CH - 5.27 H H 2-Cl 6-Cl CH - 5.28 H H 2-Cl H N Mn (NO ₃ ) ₂ 5.29 H H 2-Cl 6-Cl N - 30.5 H CH ₃ 2-Cl H N - 5.31 H CH ₃ 2-Cl H N ENT ₃ 5:32 H CH ₃ 2-Cl 6-Cl N - 5:33 H CH ₃ 2-Cl H CH - 5:34 H CH ₃ 2-OCH ₃ 6-OCH ₃ CH - 5:35 H CH ₃ 3-Cl H N - 5:36 H CH ₃ 2-CH ₃ H N ENT ₃ Mp 132-134 ° 5:37 H CH ₃ 3-CH ₃ H N - 5:38 H C ₂ H ₅ 3-CH ₃ H CH CuCl ₂ 5:39 H ^C 2 ^H 5 2-CH ₃ 6-CH ₃ N - 5:40 H C ₂ H ₅ 2-CH ₃ H N ENT ₃ Mp. 108-110 ° 5:41 H C ₂ H ₅ 2-Br 5-Br N - 5:42 H C ₂ H ₅ 2-Cl H N - 5:43 H C ₃ H ₇ -n 2-Cl H N - 5:44 H C ₃ H ₇ -n 2-Cl 6-Cl N - 5:45 H C ₃ H ₇ -X 2-CH ₃ H N - 5:46 H c ₃ H ₇ -i 2-CH ₃ H CH - 5:47 H C ₃ H ₇ -X 2-OCH ₃ ) -OCH ₃ N MnCl ₂ 5:48 C ₂ H ₅ C ₂ H ₅ 2-Cl H N - 5:49 C ₂ H ₅ C ₂ H ₅ 2-Cl H N ENT ₃ 5:50 ^C 2 ^H 4 C ₂ H ₅ 2-Cl 6-Cl N HCl 5:51 H H 2-OCH ₃ > -och ₃ CH - 5:52 C ₂ H ₅ C ₃ H ₇ -I 2-CH ₃ H N

'9 -

Continuation of Table 5 :

Verb no. ^R u ^R 12 C ₂ H ₅ H ^R 17 ^R 18 6-CH ₃ Y salt Physics. constant 5:53 H C ₂ H ₅ C ₂ H ₅ CH ₃ 2-OCH ₃ 6-OCH ₃ H N - 5:54 H C ₂ H ₅ C ₃ H ₇ -I C ₃ H ₇ -Ii 2-OCH ₃ 6-OCH ₃ 6-Cl N - 5:55 H H C ₃ H ₇ -I CH ₂ OCH ₃ 2-OCH ₃ 6-OCH ₃ H N - 5:56 CH ₃ CH ₃ 3-Cl H H N (COOH) ₂ 5:57 CH ₃ - (CH ₂ ) ₄ - C ₂ H ₅ 2-CH ₃ H CH (COOH) ₂ 5:58 CH ₃ - (CH ₂ ), - CH ₂ OH 2-Cl H N - 5:59 CH ₃ - (CH ₂ V CH ₂ OCH ₃ 2-Cl 6-Cl N H ₂ SO ₄ 5.60 - (CH ₂ V C ₂ H ₅ 2-Cl 5-Cl CH - 5.61 - (ch ₂ ) ₄ - H 2-Cl 6-Cl CH ENT ₃ 5.62 - (CH ₂ ), - C ₃ H _? -n 2-Cl H N - 5.63 - (CH ₂ ), - CH ₂ OH 3-Cl H N Mn (NO ₃ ) ₂ 5.64 H C ₂ H ₅ 3-Cl H N (COOH) ₂ 5.65 CH ₃ C ₂ H ₅ 3-Cl H N ZnCl ₂ 5.66 H 3-Cl H N HCl 5.67 H 2-Cl H CH ZnCl ₂ 5.68 H 2-CH ₃ H CH - 5.69 H 2-CH ₃ H CH - 5.70 H 2-CH ₃ H CH - yellow resin 5.71 H 2-CH ₃ H CH - resin 5.72 H 2-CH ₃ H CH - 5.73 H 2-CH ₃ H CH - 5.74 H 2-CH ₃ H CH - 5.75 H 2-CH ₃ H N - Oei 5.76 H 2-CH ₃ H N - resin 5.77 H 2-CH ₃ N - Mp. 103-105 ° 5.78 2-CH ₃ N - resin 5.79 2-Cl CH - 5.80 2-Br CH - 5.81 2-Cl CH -

Continuation of Table 5 :

Verb no. ^R u ^R 12 ^R 17 ^R 18 Y salt 5.82 H CH ₂ OCH ₃ 2-Cl H CH - 5.83 H CH ₂ OCH ₃ 2-Cl H N - 5.84 H CH ₂ OH 2-Br H CH - 5.85 H CH ₂ OCH ₃ 2-Br H CH - 5.86 CH ₃ CH ₃ 2-Br H N - 5.87 H CH ₂ OCH ₃ 2-Br H N - 5.88 H CH ₂ OH 3-NO ₂ H CH - 5.89 H C ₃ H ₇ -D 3-NO ₂ H N - 5.90 H C ₂ H ₅ 2-Br H N - 5.91 H C ₂ H ₅ 3-NO ₂ H CH - 5.92 H CH ₃ 3-NO ₂ H CH - 5.93 H C ₂ H ₅ 3-NO ₂ H N - 5.94 H CH ₃ 3-NO ₂ H N - 5.95 H CH ₂ OH 3-CH ₃ H CH - 5.96 H CH ₂ OCH ₃ 3-CH ₃ H N - 5.97 H C ₂ H ₅ 2-NO ₂ H CH - 5.98 H CH ₂ OCH ₃ 2-NO ₂ H CH - 5.99 H CH ₂ OCH ₃ 2-NO ₂ H N - 5100 H C ₂ H ₅ 3-CH ₃ H CH - 5101 H CH ₂ OCH ₃ 3-CH ₃ H CH - 5102 H C ₂ H ₅ 3-CH ₃ H N - 5103 H CH ₂ OH 2-NO ₂ H CH - 5104 H C ₂ H ₅ 2-NO ₂ H N

- 80a -

Continuation of Table 5:

Verb no. 2-CH ₃ ^R 12 ^R 17 ^R 18 Y salt Physics. constant 5105 H H 2-CH ₃ 5-CK ₃ CH - tough mass, n ° 1.5463 5106 H C ₃ H ₇ -H 2-CH ₃ H N - OeI, n ^ ² 1.5461 A 5107 H C ₃ H ₇ -H 2-CH ₃ H N - vise.OeI. n ~ 1.5468 B 5108 H C ₂ H ₅ 3-CH ₃ H N - Resin, n ⁵⁰ 1.5638 5109 H ^C 2 ^H 5 3-CH ₃ H CH - Resin, n ° 1.5732 5110 H C ₂ H ₅ 2-C ₂ H ₅ H N ENT ₃ Mp 132-134 ° 5111 H C ₂ H ₅ 2-CH ₃ H CH (COOH) ₂ Mp. 115-118 ° 5112 H C ₂ H ₅ 2-C ₂ H ₅ H N - oil; n ^ ² 1.5642 5,113 H C ₂ H ₅ 3-CH ₃ H N - oil; τζ ² 1.5631; A 5114 H ^C 2 ^H 5 3-CH ₃ H N - oil; n ^ ² 1.5633 5115 H C ₂ H ₅ 2-C ₂ H ₅ H CH - brown resin 5116 H CH ₃ 2-C ₂ H ₅ H CH ENT ₃ Mp. 105-119 ° 5117 H CH ₃ 2-C ₂ H ₅ H CH - viscous oil 5118 CH ₃ 2-C ₂ H ₅ H N ENT ₃ Mp 136-138 °

Table 6 ; Compounds of the formula R,

^l 14 \

⁴ T

(XXVI)

16

18

wherein isomeric forms are to be included:

Verb no. ^R 13 ^R 14 ^R 15 ^R 16 ^R 17 ^R 18 ^R 19 Y salt Physics. constant 6.1 H H H H H H H N - Mp. 129-130 ° 6.2 H H H H H C ₂ H ₅ H N - 6.3 H H Cl H H CH ₃ H CH - 6.4 H H H H CH ₃ CH ₃ H N - 6.5 H H H H CH ₃ CH ₃ H N ENT ₃ 6.6 H H H H CH ₃ CH ₃ CH ₃ N - 6.7 H H H H CH ₃ CH ₃ CH ₃ N ENT ₃ 6.8 H H H H CH ₃ H H N - Mp. 99.5-101 * 6.9 Cl H Cl H CH ₃ CH ₃ CH ₃ N Mn (NO ₃ ) ₂ 6.10 CH ₃ H CH ₃ H CH ₃ CH ₃ CH ₃ N CuCl ₂

Updating of Table 6 ;

Verb no. ^R 13 ^R 14 ^R 15 ^R 16 ^R 17 ^R 18 ^R 19 Y salt Physics. constant 6.11 CH ₃ H CH ₃ H CH ₃ CH ₃ CH ₃ N (COOH) ₂ 6.12 Cl H H 6-Cl CH ₃ CH ₃ CH ₃ CH ENT ₃ 6.13 Cl H H 5-Cl CH ₃ CH ₃ CH ₃ CH CuCl ₂ 6.14 Cl H Cl 6-Cl CH ₃ CH ₃ CH ₃ CH FeCl ₃ 6.15 Cl H Cl H CH ₃ H CH ₃ N - 6.16 Cl Cl Cl H CH ₃ H C ₂ H ₅ N - 6.17 H H H H C ₂ H ₅ H H N - Mp. 103-109 ° 6.18 CH ₃ H H H CH ₃ H H N - 6.19 CH ₃ H H 6-CH ₃ CH ₃ H H N ENT ₃ 6.20 H H H 5-CH ₃ CH ₃ C ₂ H ₅ H N - 6.21 H Cl H 6-Cl CH ₃ C ₂ H ₅ H CH - 6.22 H Cl H 6-Cl C ₂ H ₅ C ₂ H ₅ CH ₃ N - 6.23 6.24 H H H H CH ₃ H H H C ₂ H ₅ C ₃ H ₇ -n C ₂ H ₅ H C ₂ H ₅ C ₃ H ₇ -n N N Mn (NO ₃ ) ₂ 6.25 H CH ₃ H H C ₃ H ₇ -n H C ₃ H ₇ -n CH - 6.26 Cl H H H C ₃ H ₇ -n C ₃ H ₇ -n H N - 6.27 Cl H Cl H C ₃ H ₇ -n C ₂ H ₅ CH ₃ N - 6.28 Cl Cl Cl 6-Cl C ₃ H ₇ -H C ₂ H ₅ CH ₃ CH -

Continuation of Table 6 ;

Verb no. R ₁₃ ^R 14 ^R 15 ^R 16 ^R 17 ^R 18 R ₁₉ H Y salt 6.29 H H Cl H C ₃ H ₇ -H C ₂ H ₅ CH ₃ H N ZnCl ₂ 30.6 H H br H C ₃ H ₇ -H CH ₃ C ₂ H ₅ H N - 6.31 сн ₃ H CH ₃ H C ₂ H ₅ C ₃ H ₇ -H CH ₃ H N - 6:32 H H CH ₃ H C ₄ H ₉ -Tl CH ₃ H H N - 6:33 Cl H H 6-Cl C ₄ H ₉ -H H CH ₃ H N FeCl ₃ 6:34 Cl H H 6-Cl C ₃ H ₇ -H H CH ₃ H CH - 6:35 H H Cl H CH ₃ H C ₄ H ₉ -H H N - 6:36 F H H H H H C ₄ H ₉ -H CH - 6:37 H H H H C ₄ H ₉ -H H H CH - 6:38 H H H H л У H H N ENT ₃ 6:39 Cl H H H H C ₄ H ₉ -H N - 6:40 Cl H Cl CH ₃ H C ₄ H ₉ -H CH HCl 6:41 H Cl H H сн ₃ C ₄ H ₉ -H N - 6:42 H Cl H H H C ₄ H ₉ -SeIc N ENT ₃ 6:43 H Cl Cl H H C ₄ H ₉ -Seites N - 6:44 H br H H CH ₃ C ₄ H ₉ -Seites N - 6:45 H br H 6-Br сн ₃ C ₃ H-SeIe CH - 6:46 сн ₃ H H 5-Br сн ₃ с ₃ н ₇ -і N -

Continuation of Table 6:

Verb no. ^R 13 ^R 14 (CH = " ^R 15 ^R 16 ^R 17 ^R 18 ^R 19 Y salt 6:47 H H CH ₃ H CH ₃ c ₃ H ₇ -i H N Mn (NO ₃ ) ₂ 6:48 H Cl H H CH ₃ C ₃ H ₇ -X CH ₃ N - 6:49 Cl H Cl H C ₂ H ₅ C ₃ H ₇ -X H N 6:50 (CH = CH) ₂ H H H H H N - 6:51 (CH = CH) ₂ H H H CH ₃ H CH Mn (NO ₃ ) ₂ 6:52 (CH = CH) ₂ H 6-Cl H CH ₃ H N - 6:53 (CH-CH) ₂ H 6-CH ₃ CH ₃ CH ₃ H N - 6:54 (CH-CH) ₂ Cl 6-Cl H CH ₃ H N - 6:55 (CH-CH) ₂ H 6-Cl CH ₃ CH ₃ CH ₃ N - 6:56 (CH = CH) ₂ H 6-Cl CH ₃ CH ₃ CH ₃ CH - 6:57 (CH = CH) ₂ Cl 6-Cl C ₃ H ₇ -X H H N HCl 6:58 (CH-CH) ₂ H 6-Cl H C ₂ H ₅ H N - 6:59 (CH-CH) ₂ H H CH ₃ CH ₃ CH ₃ N - 6.60 (CH-CH) ₂ H H CH ₃ CH ₃ CH ₃ CH - 6.61 H  CH) H H H H N - 6.62 H (CH = CH) ₂ H H H H N CuCl ₂ 6.63 H (CH H H CH ₃ H N - 6.64 H 'CH) ₂ H CH ₃ H H N - (CH = CH) ₂

Continuation of Table 6 :

Verb no. ^R 13 ^R 14 ^R 15 H ^R 16 ^R 17 ^R 18 ^R 19 Y salt Physics. constant 6.65 H (CH-CH) ₂ Cl H CH ₃ CH ₃ CH ₃ N - 6.66 H (CH-CH) ₂ H H H H H CH - 6.67 Cl (CH-CH) ₂ H H H H H N - 6.68 Cl (CH-CH) ₂ H H CH ₃ CH ₃ CR ₃ N - 6.69 Cl (CH-CH) ₂ F H C ₂ H ₅ H H N - 6.70 Cl (CH-CH) ₂ F 6-Cl CH ₃ CH ₃ CH ₃ N - 6.71 H (CH-CH) ₂ F 6-Cl CH ₃ CH ₃ CH ₃ N ENT ₃ 6.72 br (CH-CH) ₂ H H CH ₃ C ₂ H ₅ CH ₃ N - 6.73 CH ₃ (CH-CH) ₂ H CH ₃ CH ₃ CH ₃ N - 6.74 Cl Cl 5-Cl H H H N - 6.75 Cl H 5-Cl H H H N - 6.76 CH ₃ CH ₃ H H H H CH - 6.77 F H H CH ₃ H H N - 6.78 H F H H H H N - 6.79 H H H H H H CH - Oei 6.80 H H H CH ₃ H H CH - tough mass 6.81 H H H CH ₃ H H N - 6.82 Cl H H CH ₃ H H N -

Continuation of Table 6:

Verb no. ^R 13 ^R 14 ^R 15 ^R 16 ^R 17 ^R 18 ^R 19 Y salt 6.83 br H H H CH ₃ H H N - 6.84 br H H H H H H N - 6.85 H br H H H H H CH - 6.86 H br H H H H H N - 6.87 H H br H H H H CH - 6.88 H H br H CH ₃ H H CH - 6.89 H H br H H H H N - 6.90 H H J H H H H CH - 6.91 H H J H H H H N

Continuation of Table 6;

Verb no. ^R 13 "u ^R 15 ^R 16 ^R 17 ^R 18 ^S 19 Y salt Physics. constant 6.93 6.94 H H H H F H H H H CH ₃ H H H H N CH Mp 105-107 ° Mp. 82-84 °

- 87 -

Table 7: Compounds of the formula

14 \

Аз

R - ^x . 15 \, /

[R ₁₃ - R ₁₄ = н]

wherein isomeric forms are to be included:

(XXVII)

Verb no. R ₂₂ ^R 23 ^R 24 ^R 15 ^R 16 Y salt Physics. Const. 7.1 H CH ₃ H H H N - 7.2 H H H H CH - 7.3 CH ₃ CH ₃ H H H N - Mp 122-124 ° 7.4 CH ₃ H H H N ENT ₃ 7.5 CH ₃ CH ₃ CH ₃ H H N Mn (NO ₃ ) ₂ 7.6 7.7 CH ₃ CH ₃ CH ₃ CH ₃ H H Cl H 6 Cl CH oil; njj ³ = 1.5782 7.8 CH ₃ C ₂ H ₅ H H H N - 7.9 CH ₃ C ₂ H ₅ H H H N CuCl ₂ 7.10 CH ₃ C ₂ H ₅ CH ₃ CH ₃ 6-CH ₃ CH (COOH) ₂ 7.11 C ₂ H ₅ C ₂ H ₅ H H H N ENT ₃ 7.12 C ₂ H ₅ C ₂ H ₅ H H H N - 7.13 C ₂ H ₅ C ₂ H ₅ H H H CH HCl 7.14 C ₂ H ₅ C ₂ H ₅ H H H CH FeCl ₃ 7.15 C ₂ H ₅ C ₂ H ₅ H H H CH - 7.16 H C ₂ H ₅ II CH ₃ H N - 7.17 H C ₂ H ₅ U II H N ENT ₃ 7.18 H C ₂ H ₅ II U H CH - 7.19 H C ₃ H ₇ -n II H H N CuCl ₂ 7.20 H C ₃ H ₇ -n H H H CH - 7.21 CH ₃ CH ₃ C ₃ H ₇ -n и H N - Mp 119-121 ° 7.22 H H H 11 H CH - 7.23 CH ₃ CH ₃ H H H CH -

- 88 -

Continuation of Table 7:

Verb no. R ₂₂ ^R 23 ^R 24 ^R 15 ^R 16 Y salt Physics. Const. 7.24 H H CH ₃ H H CH - 7.25 H H CH ₃ H H N 1/2 CuSO. 4 7.26 H H H H 6-F N 7.27 H H H F H N - 7.28 H H H H 6-Cl N - 7.29 H H CH ₃ H 6-Cl CH - 7.30 H H H H 5-Cl CH - 7.31 H H H H 5-Cl N - 7:32 H H CH ₃ Cl H CH - 7:33 H H H Cl H CH - tough mass 7:34 H H H Cl H N - Oei 7:35 H H CH ₃ Cl H N - 7:36 H H H CH ₃ H N - 7:37 H H H C ₃ H ₇ -I H N - 7:38 H H H NO ₂ H N - 7:39 H H H H 6-CF ₃ N - 7:40 H H CH ₃ H 5-CF ₃ N - 7:41 H H H CF ₃ H N - 7:42 H H H Cl 5-Cl N - 7:43 H H H Cl 5-CH ₃ CH - 7:44 CH ₃ C ₂ H ₅ H NO ₂ 5-CH N - 7:45 CH ₃ CII ₃ H CF ₃ 6-Cl CH - 7:46 CH ₃ CH ₃ C ₃ H ₇ -H CF ₃ 6-NO ₂ CH -

Table 8 : Compounds of the formula

^R 14 \ _# / ^R 13 JlI

R, - r Vo- <ch ₂ <

16

(XXVIII)

18

wherein the isomeric forms are to be included:

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 ^R 17 ^R 18 ^R 19 Y salt 8.1 2-Cl H CH ₃ H H H H H H N - 8.2 2-Cl H H H H H H C ₂ H ₅ H N - 8.3 2-Cl H H H H H H CH ₃ H CH - 8.4 2-Cl 5-Cl H H H H CH ₃ CH ₃ H N - 8.5 2-CH ₃ H Ή H H H CH ₃ H H M ENT ₃ 8.6 2-CH ₃ H H F H H H H H N - 8.7 2-Cl H Cl H H H CH ₃ CH ₃ CH ₃ N ENT ₃ 8.8 2-Cl 6-Cl Cl H Cl H CH ₃ H H N - 8.9 2-Br H H H H H CH ₃ CH ₃ CH ₃ N Mn (NO ₃ ) ₂ 8.10 2-CH ₃ H CH ₃ H H H CH ₃ H H N - 8.11 2-OCH ₃ 6-OCH ₃ H H Cl H H H H CH -

Continuation of Table 8;

Verb no. ^R ll ^R 12 ^R 13 ^R 14 CH) ₂ ^R 15 ^R 16 ^R 17 ^R 18 ^R 19 Y salt 8.12 2-Cl H H Cl (CH-CH) ₂ Cl 6-Cl CH ₃ CH ₃ CH ₃ CH ENT ₃ 3.13 3-Cl H H H H H CH ₃ rw ~ "3 CH ₃ CH CuCl ₂ 8.14 3-Br H H H H H CH ₃ CH ₃ CH ₃ CH FeCl ₃ 8.15 3-Br 5-Br H H H H CH ₃ H CH ₃ N - 8.16 2-Cl H H H H H CH ₃ H C ₂ H ₅ N - 8.17 2-Cl 6-Cl H Cl H H C ₂ H ₅ H C ₂ H ₅ N - 8.18 2-Cl 6-Cl H H H H CH ₃ H H N - 8.19 2-Cl 5-Cl H Cl H H CH ₃ H H N ENT ₃ 8.20 2-OCH ₃ 6-OCH ₃ H и Cl H H H H N - 8.21 2-CH ₃ 6-CH ₃ CH ₃ H CH ₃ H CH ₃ C ₂ H ₅ H CH - 8.22 2-Br 6-CH ₃ H H H C ₂ H ₅ C ₂ H ₅ CH ₃ N - 8.23 2-Cl H Cl H Cl H C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ N Mn (NO ₃ ) ₂ 8.24 3-Cl H (CH-CH) ₂ H H H H H N - 8.25 H H (CH-CH) ₂ H H H H H CH Mn (NO ₃ ) ₂ 8.26 2-Cl H (CH-CH) ₂ H H H H H N - 8.27 2-Cl H (CH-CH) ₂ H 2-Cl H CH ₃ H N - 8.28 2-Cl 6-Cl (CH Cl H CH ₃ CH ₃ CH ₃ N - 8.29 2-Cl H H H CH ₃ CH ₃ CH ₃ N -

Continuation of Table 8 :

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 ^R 17 ^R 18 ^R 19 Y salt 8.30 2-Cl 6-Cl (CH 'CH) ₂ H H CH ₃ CH ₃ CH ₃ N CuCl ₂ 8.31 2-CH ₃ H (CH * 'CH) ₂ H H CH ₃ CH ₃ CH ₃ N - 8:32 2-CH ₃ 6-CH ₃ (CH -CH) ₂ H H CH ₃ CH ₃ CH CH HCl 8:33 2-Br H (CH 'CH) ₂ H 2-Br H CH ₃ H N - 8:34 2-Cl 5-Cl (CH-CH) ₂ H H CH ₃ CH ₃ CH ₃ N - 8:35 2-Cl 5-Cl (CH-CH) ₂ H H CH ₃ CH ₃ H N 8:36 H H H (CH-CH) ₂ H H H H CH MnCl ₂ 8:37 3-Cl H H (CH-CH) ₂ H H H H N - 8:38 2-Cl H H (CH-CH) ₂ H CH ₃ H H N - 8:39 2-Cl H H (CH = CH) ₂ H CH ₃ CH ₃ H N - 8:40 2-Cl H Cl (CH-CH) ₂ 3-Cl H CH ₃ H N - 8:41 2-Cl 6-Cl H (CH-CH) ₂ 4-Cl CH ₃ CH ₃ H CH - 8:42 2-Cl H Cl (CH-CH) ₂ H CH ₃ CH ₃ CH ₃ N - 8:43 2-Cl 5-Cl H (CH-CH) ₂ H CH ₃ CH ₃ CH ₃ N - 8:44 2-Cl 3-Cl H (CH = CH) ₂ 4-Br CH ₃ H CH ₃ N - 8:45 2-CH ₃ 3-Cl Cl (CH-CH) ₂ H CH ₃ CH ₃ CH ₃ H - 8:46 2-CH ₃ 5-CH ₃ H (CH = CH) ₂ H CH ₃ CH ₃ H N HCl 8:47 2-CH ₃ H CH ₃ (CH = CH) ₂ H CH ₃ H CH ₃ N -

Continuation of Table 8 :

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 ^R 17 ^R 18 ^R 19 Y salt 8:48 2-Cl H Cl (CH ' ѴІ1 / η H H C ₂ H ₅ H N - 8:49 2-Cl H Cl (CH ' ^ \ * El / ty H C ₂ H ₅ CH ₃ H N - 8:50 2-CH ₃ H H H H H H H H CH - 8:51 2-CH ₃ H H H H H CH ₃ H H CH - 8:52 2-CH ₃ H H H H H CH ₃ H H N - 8:53 2-CH ₃ H H H H H H H H N - 8:54 2-Cl H H H H H H H H CH - 8:55 2-Cl H H α H H H H H N - 8:56 2-Cl H ti H H H CH ₃ H H R - 8:57 3-NO ₂ H H H H H H H H CH - 8:58 2-Br H H H H H H H H CH - 8:59 2-Br H H H H H H H H N - 8.60 3-CH ₃ H H H H H H H H CH - 8.61 3-CH ₃ H H H H H H H H N - 8.62 2-NO ₂ H a H H H H H H N - 8.63 2-Cl H H H Cl H H H H N - 8.64 H H Cl H H 5-Cl H H H N - 8.65 H H H Cl H 5-Cl H H H N -

Continuation of Table 8 :

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 ^R 17 ^R 18 ^R 19 Y salt Physics. constant 8.66 2-CH ₃ H H F H H H H H CH - brown resin 8.67 2-CH ₃ H F H H H H H H N - 8.68 2-CH ₃ H H H Cl H H H H N - 8.69 2-CH ₃ H H H Cl H H H H CH - brown resin 8.70 2-CH ₃ H H H Cl H CH ₃ H H N - 8.71 2-CH ₃ H H H Cl H CH ₃ H H CH - 8.72 2-CH ₃ H H H F H H H H N - resin 8.73 2-CH ₃ H H H F H H H H CH - 8.74 2-CH ₃ H H H F H CH ₃ H H N - 8.75 2-CH ₃ H H H F H CH ₃ H H CH

- 94 -

Table 9: Compounds of the formula

^R 14 \ / ^R 13 ^R l

»No 9« 5

wherein isomeric forms are to be included:

(XXlX)

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 R ₂₂ ^R 23 ^R 24 Y salt 9.1 2-Cl H H H H H H CH ₃ H N - 9.2 2-Cl H H Cl H 6-Cl H CH ₃ H CH - 9.3 2-Br H br H H H CH ₃ CH ₃ H N - 9.4 2-CH ₃ 6-CH ₃ H H H H CH ₃ CH ₃ H N ENT ₃ 9.5 2-Cl 6-Cl Cl H H 6-Cl CH ₃ CH ₃ CH ₃ N Mn (NO ₃ ) ₂ 9.6 2-Cl 6-Cl H Cl H H CH ₃ CH ₃ CH ₃ CH - 9.7 2-Cl 5-Cl H H Cl H CH ₃ CH ₃ H - 9.8 2-Cl H H Cl Cl H CH ₂ C ₂ H ₅ H N - 9.9 2-Cl H Cl H H H CH ₃ , C ₂ H ₅ H N CuCl ₂ 9.10 3-Cl 5-Cl Cl H H 6-Cl CH ₃ C ₂ H ₅ CH ₃ CH (COOH) ₂ 9.11 2-Cl 6-Cl H H Cl H C ₂ H ₅ C ₂ H ₅ H N ENT ₃ 9.12 3-CHj 5-CH ₃ H H H H C ₂ H ₅ C ₂ H ₅ H N - 9.13 ² ~ ^CH J H CH ₃ CH ₃ H H C ₂ H ₅ C ₂ H ₅ H CH HCl 9.14 2-Cl H H CH ₃ H H C ₂ H ₅ C ₂ H ₅ H CH FeCl ₃ 9.15 2-Cl 5-Cl Cl H H H C ₂ H ₅ C ₂ H ₅ H CH - 9.16 2-Cl H Cl Cl Cl 5-Cl H C ₂ H ₅ H N - 9.17 2-Cl H H Cl Cl H H C ₂ H ₅ H N ENT ₃ 9.18 2-CHj 5-CH ₃ CH ₃ H H 6-CH ₃ H C ₂ H ₅ H CH - 9.19 2-CHj 6-CH ₃ H H CH ₃ H H C ₃ H ₇ -n H N CuCl ₂ 9.20 2-Cl 6-Cl H H CH ₃ H H C ₃ H ₇ -n H CH - 9.21 3-NO ₂ H H H Cl H H H CH ₃ N - 9.22 H H Cl H Cl 6-CH ₃ CH ₃ CH ₃ H N - 9.23 H H CH ₃ H br 6-Cl CH ₃ CH ₃ ^C 3 ^H 7 ~ ⁿ CH - 9.24 H H CH ₃ и br 6-Cl CH ₃ C ₂ H ₅ H N

Table 10: Compounds of the formula R-

1A \

R - ' ^Ν · -0-15 \ I /

fl. ' ). -C-CH - <

ll

(XXX)

46 12 wherein the isomeric forms are to be included:

Verb no. H ^R 12 Cl ^R 14 ^R 15 ^R 16 H Y U CH ₃ V CH ₃ salt - 10.1 H H Cl H Cl H N CH ₃ CH ₃ Mn (NO ₃ ) ₂ 10.2 H H CH ₃ H Cl H N CH ₃ C ₂ H ₅ - 10.3t H H CH ₃ H CH ₃ 5-CH CH C ₂ H ₅ C ₂ H ₅ - 10.4 H H H H CH ₃ 5-Cl N C ₄ H ₉ -H C ₄ H ₉ -H - 10.5 H H H Cl H 6-Cl N C ₃ H ₇ -I C ₃ H ₇ -I CuCl ₂ 10.6 H H H Cl H H N CH ₃ CH ₃ - 10.7 H H H H H H N CH ₃ CH ₃ - 10.8 H H H H F H CH C ₃ H ₇ -n C ₃ H ₇ -n (COOH) ₂ 10.9 2-Cl H H H H H N CH ₃ CH ₃ - 10:10 2-Cl H H H Cl H N CH ₃ CH ₃ - 10:11 3-Cl 6-Cl H H H H N C ₂ H ₅ C ₂ H ₅ - 10:12 2-Cl H H H H H N ^C 8 ^H 17- ^{n C} 8 ^H 17- ⁿ - 10:13 6-Cl H Cl N

Continuation Table 10:

Verb no. 2-CH ₃ ^R 12 ^R 13 ^R 1A H H ^R 15 ^R 16 H Y U C ₂ H ₅ V C ₂ H ₅ salt 10:14 2-CH ₃ H H CH ₃ H H H H CH c ₃ H ₇ -i C ₃ H ₇ -I HCl 10:15 2-CH ₃ 6-CH ₃ CH ₃ H H H H H N ^С 5 ^Н іГ ^П - 10:16 2-Cl H CH ₃ CH ₃ H H H 6-Cl N CH ₃ CH ₃ - 10:17 2-Cl 5-Cl Cl H H H H H N C ₄ H ₉ -S - 10:18 2-Cl 5-Cl H H H H Cl 6-Cl N CH ₃ CH ₃ - 10:19 2-Cl 6-Cl Cl Cl H H Cl H CH CH ₃ CH ₃ - 10:20 2-CH ₃ H (CH-CH) ₂ H H H H N CH ₃ - 10:21 H H (CH-CH) ₂ H H H H N CH ₃ CH ₃ ⁷ - 10:22 H H H H H H CH C ₂ H ₅ ^C 2 ^H 5 - 10:23 H H H H CH - 10:24 H H H H CH (ch ₂ ) ₂ and ₃ (СЧЛ \ ЛГП - 10:25 H H H H CH (CH ₂ J ₂ OC ₂ H ₅ (CH ₂ J ₂ OC ₂ H ₅ - 10:26 H H H H CH ^C 8 ^H 17 ~ ⁿ - 10:27 H H H H CH (CH m / aOCH- (CH ₂ ) ₂ осн ₃ - 10:28 2-CH ₃ H H H N CH ₃ CH ₃ - 10:29 2-CH ₃ H H H CH ( PU ^ APU 2 2 3 ( Pu Ч при 2 2 3 10:30 2-Cl H H H N (CH ₂ J ₂ OCH ₃ / лц ^ Пси - 10:31 H H CH

Continuation Table 10;

Verb no. ^R ll H H ^R 14 ^R 15 ^R 16 Y U CH ₃ V CH ₃ salt 10:32 2-CH ₃ H H H H H N CH ₃ CH ₃ - 10:33 2-Cl H H H H H CH (CH ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - 10:34 2-Cl H H H H H N CH ₃ CH ₃ - 10:35 2-Br H H H H H CH C ₂ H ₅ C ₂ H ₅ - 10:36 2-Br H H H H H N C ₂ H ₅ C ₂ H ₅ - 10:37 3-NO ₂ H H H H H CH (CH ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - 10:38 2-Br H H H H H N CH ₃ CH ₃ - 10:39 3-CH ₃ H Cl H H H CH CH ₃ CH ₃ - 10:40 H H Cl H H H CH (CH ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - 10:41 H H Cl H H H CH C.H-n 4 9 C ₄ H ₉ -U - 10:42 H H Cl H H H CH (CH ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - 10:43 H H H H H H N CH ₃ CH ₃ - 10:44 H H H Cl H H CH C ₄ H ₉ -U C ₄ H ₉ -U - 10:45 H H H Cl H H CH ^C 8 ^H 17- ^{n C} 8 ^H 7- ⁿ - 10:46 H H Cl Cl H H CH C ₄ H ₉ -U C ₄ H ₉ -H - 10:47 H H H H H H N C ₂ H ₅ C ₂ H ₅ - 10:48 H H H Cl H H CH (CH ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - 10:49 H Cl H H CH -

Continuation Table 10;

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y U V salt 10:50 H H H Cl H H CH <сн ₂ ) ₂ осд (CH ₂ ) ₂ oc ₂ h ₅ - 10:51 H H H H Cl H CH CH ₃ CH ₃ - 10:52 H H H H Cl H CH C ₄ H ₉ -H C ₄ H ₉ -U - 10:53 H H H H Cl H CH (CHj) ₂ OCH ₃ (CH ₂ ) ₂ ocH ₃ - 10:54 H H H H Cl H CH C ₂ H ₅ C ₂ H ₅ - 10:55 H H H H Cl H CH C ₂ H ₄ Ci C ₂ H ₄ Cl - 10:56 H H H H Cl H CH (CH ₂ ) ₂ oc ₂ h ₅ (CH ₂ ) ₂ oc ₂ h ₅ - 10:57 H H H H Cl H N C ₂ H ₅ C ₂ H ₅ - 10:58 H H H H Cl H N CH ₃ CH ₃ - 10:59 H H H H Cl H N (CH ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - 10.60 H H H H br H CH (CH ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - 10.61 H H H H br H CH CH ₃ CH ₃ 10.62 H H CH ₃ H H H CH CH ₃ CH ₃ - 10.63 H H NO ₂ H H H CH CH ₃ CH ₃ - 10.64 H H H CF ₃ H H CH CH ₃ CH ₃ - 10.65 H H H CF ₃ H H CH (CH ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - 10.66 H H Cl Cl H H CH CH ₃ CH ₃ - 10.67 H H Cl H Cl H CH C ₂ H ₅ ^C 2 ^H 5 -

Continuation Table 10 :

Verb no. ^R u ^R 12 ^R 13 ^R 14 ^R l5 ^R 16 Y U C ₂ H ₅ V ^С 2 ^Н 5 salt 10.68 H H Cl H H 5-Cl N CH ₃ сн ₃ - 10.69 H H Cl H H 5-Cl CH C ₄ H ₉ -U - 10.70 H H Cl H H 6-Cl CH CH ₃ сн ₃ - 10.71 H H H Cl Cl H N CH ₃ сн ₃ - 10.72 H H H Cl H 5-Cl CH CH ₃ сн ₃ - 10.73 H H H Cl Cl H CH CH ₃ CH ₃ 10.74 H H br H br H CH C ₂ H ₅ C ₂ H ₅ - 10.75 H H Cl H br H CH CH ₃ сн ₃ - 10.76 H H CH ₃ CH ₃ H H CH C ₂ H ₅ ^С 2 ^Н 5 - 10.77 H H CH ₃ H H 5-CH ₃ CH C ₂ H ₅ ^С 2 ^Н 5 - 10.78 H H C / H -t 4 9 H H CH (CH ₂ ) ₂ осн ₃ (CH ₂ ) ₂ осн ₃ - 10.79 H H H CH ₃ 5-CH ₃ CH CH ₃ сн ₃ 10.80 H H C ₃ H ₇ -I Cl 5-CH ₃ CH C ₂ H ₅ ^С 2 ^Н 5 - 10.81 H H Cl H Cl 5-Cl CH VwM _n / пѵѵПд 2 1 э (CH ₂ ) ₂ осн ₃ - 10.82 H H Cl Cl i H CH C ₂ H ₅ C ₂ H ₅ - 10.83 H H Cl Cl br 5-Cl CH (CH ₂ ) ₂ ос ₂ н ₅ (CH ₂ ) ₂ ос ₂ н ₅ - 10.84 H H br H Cl 6-Br CH сн ₃ сн ₃ - 10.85 H H CH ₃ H H CH -

Continuation Table 10:

Verb no. ^R ll ^R 12 ^R 13 ^R 14 ^R 15 ^R 16 Y U CH ₃ V CH ₃ salt 10.86 H H H CH ₃ Cl H CH (ch ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - 10.87 H H H CH ₃ Cl H N CH ₃ CH ₃ - 10.88 H H c ₄ H ₉ -t H Cl H CH C ₂ H ₄ Cl C ₂ H ₄ Ci - 10.89 H H c _A H ₉ -t H Cl H N ^C 8 ^H 17- ^{n C} 8 ^H 17- ⁿ - 10.90 H H br H CH ₃ H CH CH ₃ CH ₃ - 10.91 H H NO ₂ H CF ₃ H CH ^C 7 ^H 18 ~ ^{n C} 7 ^H 18- ⁿ - 10.92 H H H CH ₃ Cl 5-CH ₃ CH CH CH ₃ - 10.93 H H CF ₃ H NO ₂ H CH C ₂ H ₄ Ci C ₂ H ₄ Ci - 10.94 H H H CH ₃ Cl 5-CH ₃ CH CH ₃ CH ₃ - 10.95 H H CF ₃ H NO ₂ 6-CF ₃ CH C ₂ H ₅ C ₂ H ₅ - 10.96 H H CF ₃ H NO ₂ 6-CF ₃ N C ₂ H ₅ C ₂ H ₅ - 10.97 H H CF ₃ H NO ₂ 6-NO ₂ CH C ₂ H ₄ Cl C ₂ H ₄ Ci - 10.98 H H br H CH ₃ H CH C ₄ H ₉ -H C ₄ H ₉ -H - 10.99 H H H H F H CH (CH ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - lo.iob H H H H F H CH C ₂ H ₄ Cl C ₂ H ₄ Ci - 10101 H H H H F H CH C ₂ H ₅ C ₂ H ₅ - 10102 H H H H F H CH (CH ₂ ) ₂ and ₃ (CH ₂ ) ₂ and ₃ - 10103 H H H H F H N -

- K) I -

Formulation Examples of Agrochemical Agents Containing Liquid Active substances of the formula I (% by weight)

10.Emulsions-Concentrates a) b) c)

Active ingredient from Tables 1 to 10 25% 40% 50% Ca-dodecylbenzenesulfonate 5% 8% 6%

Castor oil polyethylene glycol ether 5% - - (36 mol ethylene oxide)

Tributylphenoyl polyethylene glycol - 12% 4% better (30 mol ethylene oxide)

Cyclohexanone - 15% 20% Xylene mixture 65% 25% 20%

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

11.Lösungen

Active ingredient from Tables 1 to 10 Ethylene glycol ether monoraethyl Polyethylene glycol M G 400 N-methyl-2-pyrrolidone Epoxidized coconut oil Gasoline (boiling limit 160-19O ⁰ C)

(MW = molecular weight)

a) b) c) d) 5% 80% 10% 5% 95% 20% - - - - 70% - - - 20% - - - - 1% 94%

- 102 -

The solutions are suitable for use in the form of very small drops.

12. Granulates a) b)

Active ingredient from Tables 1 to 10 5% 10%

Kaolin 94%

Highly disperse silica 1% -

Attapulgite - 90%

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated in vacuo.

13.Stäubenuttel a) b) Active ingredient from Tables 1 to 10 2% 5% Highly dispersed silicic acid 1% 5% talc 97% - kaolin 90%

Intimate mixing with excipients with the active ingredient gives ready-to-use dusts.

Formulation Examples of Agrochemical Agents Containing Solid Active Ingredients of Formula I (% by Weight)

16. Spray Powder a) b) c)

Active ingredient from Tables 1 to W Na lignosulfonate

Na lauryl sulfate

Na Diisobutylnaphthalinsulfonat

Octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) Highly dispersed silica kaolin

25% 50% 75 5% 5% - 3% - 5% - 6% 10% - 2% - 5% 10% 10% 62% 27%

- КГ} -

The active ingredient is mixed with the ingredients and milled well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

15. Emulsion Concentrate

Active ingredient from Tables 1 to 10 10%

Octylphenol polyethylene glycol ether 3%

(4-5 moles of ethylene oxide)

Ca-dodecylbenzenesulfonate 3%

Castor oil polyglycol ether (35 mol ethylene-4% oxide)

Cyclohexanone 30%

Xylene mixture 50%

From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

16. Dust a) b) Active substance from Tables 1 to 10 5% 8% talc 95% kaolin - 92%

Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding on a suitable mill.

1 7.Extruder granules

Active ingredient from Tables 1 to 10 10%

Na lignosulfonate 2%

Carboxymethylcellulose 1%

Kaolin 87%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

- 104 -

14. Envelope granules

Active ingredient from Tables 1 to 10 3%

Polyethylene glycol (M G 200) 3%

Kaolin 94%

(MW = molecular weight)

The finely ground active substance is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

1 9. Suspension Concentrate

Active ingredient from Tables 1 to 10 40% ethylene glycol 10%

Nonylphenol polyethylene glycol ether 6% (15 moles of ethylene oxide)

N-lignin sulfonate 10%

Carboxymethylcellulose 1%

37% aqueous formaldehyde solution 0.2%

Silicone oil in the form of a 75% aqueous emulsion 0.8%

Water 32%

The finely ground active substance is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by Verdiinnen with water.

Formulation Examples of Pharmaceutical Preparations ;

20. Ointments :

An ointment containing 5% of 2- [p- (4-chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-dioxolane can be prepared as follows:

Composition :

Active ingredient 5.0%

Vaseline 45.0%

Paraffin oil 19.6%

- 105 - ceryl 5 OZ beeswax 5.0% Sorbitan sesquioleate 5.0% p-hydroxybenzoic acid 0.2% Water, entraineralized up to 100.0%

The fatty substances and emulsifiers are melted together. The preservative is dissolved in water and the solution emulsified into the fat melt at elevated temperature. After cooling, a suspension of the active ingredient in a portion of the fat melt is incorporated into the emulsion.

21 . Cream ;

Cream containing 10% of 2- [p- (chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane can be obtained as follows:

Composition :

Active substance 10.0%

Isopropyl palmitate 8.0% Cetyl palmitate 1.5%

Silicone oil 100 0.5%

Sorbitan monostearate 3.0% Polysorbate 60 3.5%

1,2-propylene glycol PH 20.0%

Acrylic acid polymer 0.5% Triethanolamine 0.7% Water, demineralized up to 100.0%

The acrylic acid polymer is suspended in a mixture of demineralized water and 1,2-propylene glycol. Triethanolamine is then added with stirring, whereby a mucus is obtained. A mixture of isopropyl palmitate, cetyl palmitate, silicone oil, sorbitan monostearate and polysorbate is heated to about 75 ° and incorporated with stirring in the likewise heated to about 75 ° slime. The

- 106 -

Cooled to room temperature cream Crundlap.e is then to Hcrsto 1 I iiuj: ciiii · :; Kon -out r.it <* :; mil иЧчіі Wirki; lolf vi'i'woiulcL. D.is Коч / лмі- stepped is homogenized by means of its continuous homogenizer and then added portionwise to the base.

Cream containing 5% of 2- [p- (chlorophenoxy) -phenyl] -2- (1-imidazolyl-ethyl) -4-ethyl-1,3-dioxolane can be prepared as follows:

Composition: 5.0% active substance 2.0% Cetyl palmitate PH 2.0% Cetyl alcohol PH 5.0% Triglyceride-geraic saturated medium fatty acids 3.0% stearic acid 4.0% Glycerine stearate PH 1.0% Cetomacrogol 1000 0.5% microcrystalline cellulose 20.0% 1,2-propylene glycol, dist. 100.0% Water, demineralized up to

Cetyl alcohol, cetyl palmitate, the triglyceride mixture, stearic acid and glycerol stearate are melted together. The microcrystalline cellulose is dispersed in a part of the water. Cetomacrogol is dissolved in the remaining part of the water and the propylene glycol and mucus are mixed. The fat phase is then added with stirring to the water phase and stirred cold. Finally, the active ingredient is ground with a portion of the base and then incorporated into the remainder of the cream.

22. Hydrogels :

A transparent hydroclc containing 5% 2- [p- (chlorophenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-ethyl-dioxolane is prepared as follows:

- 107 - Composition: 5% active substance 10-20% propylene glycol 20% isopropanol 2% Hydroxypropyl methylcellulose ad 100% water

The hydroxypropyl methylcellulose is swollen in the water. The active ingredient is dissolved in a mixture of isopropanol and propylene glycol. Subsequently, the drug solution is mixed with a swollen cellulose derivative and, if desired, added with fragrances (0.1%).

23. Foam sprays

A foam spray containing 1% 2- [p- (chlorophenoxy) -phenyl] -2- (1-imidazole)

dazolylmethyl) -4-ethyl-1,3-dioxolane, can be prepared as follows

become:

Composition :

Active ingredient 1.00%

Ceryl alcohol PH 1.70% Paraffin oil, viscous 1.00% Isopropyl myristate 2.00% CetamacrogoJ. 2.40% Sorbitan monostearate 1.50%

1,2-propylene glycol PH 5.00%

Methylparaben 0.18% Propylparebene 0.02%

Chemoderm 314 0.10%

Water, demineralized up to 100.00%

Cetyl alcohol, paraffin oil, isopropyl myristate, cetomacrogol and sorbitan stearate are melted together. Methyl and propylparaben are dissolved in hot water. The melt and the solution are then mixed. The active ingredient, suspended in propylene glycol, is dissolved in

- 108 -

incorporated the foundation. Subsequently, Chemoderm is added and supplemented with water to the final weight.

filling:

20 ml of the mixture are poured into an aluminum block. The can is provided with a valve and the propellant is filled under pressure.

24. Capsules

Gelatin capsules containing 200 mg of [p- (phenoxy) phenyl] -2- [1- (IH-1,2,4-triazolyl) methyl] -1,3-dioxane as active ingredient can be prepared, for example, as follows :

Composition (for 1000 capsules)

Active ingredient 100 g

Lactose, ground 100 g

The active ingredient and the lactose (finely ground) are mixed well with each other. The resulting powder is sieved and bottled in portions of 0.20 g each in gelatine capsules.

25th tablets

Tablets containing 25 mg of active ingredient, e.g. 2- [p- (Phenoxy) -phenyl] -2- [1- (UI-I, 2,4-triazolyl) -methyl] -l, 3-dioxane can be obtained as follows:

Ingredients (for 1000 tablets)

Active ingredient 25.0 g

Lactose 100.7 g

Wheat starch 7.5 g

Polyethylene glycol 6000 5.0 g

Talc 5.0 g

Magnesium stearate 1.8 g

demineralised water q.s.

- 109 -

Preparation: All solid ingredients were initially forced through a sieve of 0.6 mm mesh size. Then the active ingredient, the lactose, the talc, the magnesium stearate and half of the starch are mixed. The other half of the starch is suspended in 40 ml of water and this suspension is added to a boiling solution of the polyethylene glycol in 100 ml of water and the mixture is granulated, if necessary adding water. The granules are dried overnight at 35 °, forced through a sieve of 1.2 mm mesh size and pressed on both sides concave tablets of about 6 mm in diameter.

Tablets containing 100 mg of active ingredient, e.g. 2- [p- (Phenoxy) -phenyl] -2- [l- (IH-I, 2,4-triazolyl) -methyl] -l, 3-dioxane can be prepared as follows:

Ingredients (for 1000 tablets)

Active ingredient 100.0 g

Lactose 50.7 g

Wheat starch 7.5 g

Polyethylene glycol 6000 5.0 g

Talc 5.0 g

Magnesium stearate 1.8 g

demineralised water q.w.

Preparation : All solid ingredients are first driven through a sieve of 0.6 mm mesh size. Then the active ingredient, lactic acid, talc, magnesium stearate and half of the starch are mixed. The other half of the starch is suspended in 40 ml of water and this suspension is added to a boiling solution of the polyethylene glycol in 100 ml of water and the mixture is granulated, if necessary adding water. The granules are dried overnight at 35 °, forced through a sieve of 1.2 mm mesh size and pressed on both sides concave tablets of about 6 mm in diameter.

- 110 -

Tablets containing 75 m ;; Active ingredient, e.g. 2- [p- (1-carboxy) -phenyl] -2- [1- (1H-l, 2,4-triazolyl) -methyl] -l, 3-dioxane can be prepared as follows:

Ingredients (for 1000 tablets)

Active ingredient 75.0 g

Lactose 100.7 g

Wheat starch 7.5 g

Polyethylene glycol 6000 5.0 g

Talc 5.0 g

Magnesium stearate 1.8 g

demineralised water q.s.

Production : All solid ingredients are first driven through a sieve of 0.6 mm square. Then the active ingredient, the lactose, the talc, the magnesium stearate and half of the starch are mixed. The other half of the starch is suspended in 40 ml of water and this suspension is added to a boiling solution of the polyethylene glycol in 100 ml of water and the mixture is granulated, if necessary adding water. The granules are dried overnight at 35 °, forced through a sieve of 1.2 mm mesh size and pressed on both sides concave tablets of about 6 mm in diameter.

In an analogous manner, it is also possible to produce pharmaceutical preparations containing another compound according to tables 1 to 10 available compounds.

- Ill -

Biological examples:

Example 26 ; Action against Puccinia graminis on wheat

^a ^ Residual-protective effect

Wheat plants were sprayed 6 days after sowing with a spray mixture prepared from wettable powder of the active ingredient (0.006% active substance). After 24 hours, the treated plants were infected with a uredospore suspension of the fungus. After incubation for 48 hours at 95-100% relative humidity and about 20 ⁰ C, the infected plants were placed in a greenhouse at about 22 ° C. The assessment of rust pustule development was made 12 days after infection.

b) Systemic effect

For wheat plants, a spray mixture prepared from wettable powder of the active ingredient was poured 5 days after sowing (0.006% active substance based on the soil volume). After 48 hours, the treated plants were infected with a uredospore suspension of the fungus. After incubation for 48 hours at 95-100% relative humidity and about 2O ⁰ C, the infected plants were placed in a greenhouse at about 22 ° C. The assessment of rust pustule development was made 12 days after infection.

Compounds from Tables 1 to 10 showed a good action against Puccinia fungi. Untreated but infected control plants showed a Puccinia infestation of 100%. Among others, compounds Nos. 1.9, 1.17, 1.24, 1.26, 2.17, 3.1, 3.2, 3.6 to 3.8, 3.12, 3.26, 3.51, 3.52, 3.54, 3.55, 3.70, 3.75, 3.78, 3.83, 3.85, 3.86, 3.127 , 3.133, 3.155, 3.156, 3.160, 3.162, 3.164, 3.168, 3.171, 3.172, 3.176. 3.177, 3.193, 3.212.3.213.3.220, 3.226, 3.227, 3.231 to 3.234, 3.263, 3.267, 3.274, 3.279, 3.287, 3.292, 3.311, 3.314, 3.340, 3.348,

- 112 -

3.373, 3.376, 3.384, 3.386, 4.2, 4.15, 4.23, 4.50, 4.55, 4.57, 4.66, 4.70, 4.77, 4.78, 4.81, 4.89 to 4.94, 4.113, 4.116, 4.136, 4.138 to 4.147, 5.13, 5.14, 5.36, 5.40, 5.70, 5.71, 5.76, 5.78, 5.105, 5.113, 5.117, 6.8, 6.82, 6.93, 7.7, 7.33 and 8.66 in the case of residual-protective treatment, the mushroom area to 0 to 5%. In addition, Compound No. 6.8 showed full systemic effect (OZ infestation) even at a dilution to 0.006%.

Example 27 ; Action against Cercospora arachidicola on peanut plants

10-15 cm high peanut plants were sprayed with a spray liquor prepared from spray powder of the active substance (0.002 Z active substance) and infected 48 hours later with a conidia suspension of the fungus. The infected plants were incubated for 72 hours at about 21 * C and high humidity and then placed in a greenhouse until the appearance of the typical leaf spots. The evaluation of the fungicidal activity was made 12 days after the infection based on the number and size of the spots.

Compared to untreated but infected control plants (number and size of spots * 100%), peanut plants treated with active substances from Tables 1 to 10 showed a greatly reduced Cercospora infestation. Thus, compounds Nos. 1.1, 1.4, 1.9, 1.14, 1.17, 1.24 to 1.27, 2.17, 3.1, 3.2, 3.6, 3.7, 3.11, 3.51, 3.52, 3.54, 3.5f>, 3.57, 3.78, 3.85, 3.86, 3,127, 3,133, 3,155, 3,156, 3,162, 3,171, 3,172, 3,176, 3,177, 3,212, 3,213, 3,220, 3,221, 3,226, 3,231, 3,232, 3,233, 3,234, 3,267, 3,292, 3,314, 3,348, 3,384 to 3,388, 4.1. , 4.23, 4.50, 4.57, 4.59, 4.66, 4.89 to 4.94, 4.113, 4.116, 4.1316 to 4..148, 5.13, 5.14, 5.36, 5.40, 5.70, 5.71, 5.73, 5.75 to 5.78, 5.105 to 5.110, 5.113 to 5.118, 6.1, 6.8, 6.93, 6.94, 7.33, 7.34 and 8.72 in the above experiment the occurrence of patches fas completely (0 to 5Z).

- 113 -

Example 28 : Action against Erysiphe graminis on barley

a) Residual-protective action

Approximately Barley plants 8 cm in height were sprayed with a spray mixture (0.002% active substance) prepared from spray powder of the active ingredient. After 3-4 hours, the treated plants were pollinated with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22 ° C and assessed the fungal infection after 10 days.

b) Systemic effect

To barley plants about 8 cm high, a spray mixture prepared from wettable powder of the active ingredient was poured (0.006% active substance based on the volume of the soil). Care was taken to ensure that the spray mixture did not come into contact with the aboveground plant parts. After 48 hours, the treated plants were pollinated with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22 ° C and assessed the fungal infection after 10 days.

Compounds of the formula I showed a good residual-protective activity against Erysiphe fungi. Untreated but infected control plants showed an Erysiphe infestation of 100%. Among other compounds of Tables 1 to 10, the following compounds inhibited Nos. 1.1, 1.4, 1.9, 1.14, 1.17, 1.23 to 1.27, 2.17, 3.1, 3.2, 3.6 to 3.8, 3.11, 3.12, 3.26, 3.51, 3.52, 3.54 , 3.55, 3.70, 3.75, 3.78, 3.85, 3.86, 3.103, 3.127, 3.133, 3.156, 3.160, 3.162, 3.164, 3.168, 3.171, 3.172, 3.174, 3.176, 3.177, 3.193, 3.212, 3.213, 3.220, 3.221, 3.226 , 3.227, 3.231, 3.232 to 3.234, 3.263, 3.267, 3.274, 3.279, 3.287.3.292, 3.311, 3.314, 3.340, 3.348, 3.378, 3.383 to 3.388, 4.2, 4.15, 4.23, 4.50, 4.57, 4.59, 4.66, 4.77 , 4.78, 4.81, 4.89 to 4.94, 4.113, 4.116, 4.137, 4.139, 4.140, 4.141, 4.146, 4.148, 4.150, 5.13, 5.14, 5.36, 5.40, 5.70, 5.71, 5.73, 5.75 to 5.78, 5.106 to 5.114, 6.1, 6.8, 6.17, 6.79, 6.80, 6.82, 6.93, 7.3, 7.7, 7.21, 7.33, 7.34, 8.66, 8.69, 8.72

- 114 -

and 10.7 the fungus on barley to less than 5%. Compound No. 4.50 also showed this effect in the soil treatment (systemic action) and at a dilution to 0.006%.

Example 29: Residual-protective action against Venturia inaequalis apple shoots

Apple cuttings with 10-20 cm long fresh shoots were sprayed with a spray mixture of active ingredient prepared spray powder (0.06% active ingredient). After 24 hours, the treated plants were infected with a conidia suspension of the fungus. The plants were then incubated for 5 days at 90-100% relative humidity and placed for 10 more days in a greenhouse at 2O-24 ° C. Scab infestation was assessed 15 days after infection.

Compounds Nos. 1.4, 1.9, 1.17, 1.24, 1.26, 2.17, 3.1, 3.6, 3.7, 3.11, 3.52, 3.55, 3.85, 3.86, 3.156, 3.160, 3.164, 3.172, 3.176, 3.177, 3.213, 3.221, 3.233, 3.314 , 3.383 to 3.387, 4.15, 4.23, 4.50, 4.59, 4.66, 4.78, 4.81, 4.89, 4.90 to 4.94, 4.113, 4.116, 4.137 to 4.141, 4.146 to 4.150, 5.13, 5.14, 5.36, 5.40, 5.70, 5.73, 5.75 , 5.76, 5.106 to 5.110, 5.112 to 5.114, 5.118, 6.1, 6.8, 6.93 and 10.7 inhibited the disease infestation to less than 10%. untreated but infected shoots showed a 100% Venturia infestation.

Example 30; Action against botrytis cinerea on beans Residual-protective effect

Approximately 10 cm high bean plants were sprayed with a spray mixture of active ingredient prepared from spray powder (0.002% active ingredient). After 48 hours, the treated plants were infected with a conidia suspension of the fungus. After incubation of the infected plants for 3 days at 95-100% relative humidity and 21 ° C was the assessment of fungal infestation. The compounds from Tables 1 to 10 inhibited the fungal infection in many cases. At a concentration of 0.002%, e.g. the

- iodine

Connections Nos. 1.1, 1.4, 1.9, 1.17, 3.6, 3.7, 3.12, 3.51, 3.55, 3.86, 3.226, 3.231, 3.267, 3.311, 4.15, 4.50, 4.59, 4.66, 4.78, 4.90 to 4.93, 4.113, 5.13, 5.36 , 5.40, 5.70, 5.71, 5.73, 5.75, 5.76, 5.78, 6.1, 6.8, 7.3, 7.33 and 8.72 as fully effective (disease 0 to 5%). The Botrytis bole of untreated but infected bean plants was 100%.

Case 5-13393 / + / АР

Added or corrected physical data:

Verb no. Physical constant 1.4 Mp. 85-92 ° 1.28 Mp 118-123 ° 3:51 M.p. 67-69 ° 3:52 Mp. 64-69 ° 3:54 Mp. 101-103 ° 3:55 Mp. 70-71 ° 3:56 Mp. 65-67 ° 3:57 Mp. 95-106 ° 3:58 Mp. 90-98 ° 3:59 Mp. 71-73 ° 3.70 τξ ⁶ 1.5713 3.75 nj ³ ' ⁵ 1.5693 3.78 ny ⁸ 1.5745 3.83 Mp. 78-85 ° 3.85 Mp. 95-97 ° 3103 Mp. 83-86 3160 tough mass 3174 n £ ⁸ 1,5808 3263 Smp, 96-102 ° 3292 Mp 154-156 ° 3340 Mp. 69-78 ° 3343 n £ ³ 1.5723 3348 Mp. 93-97 ° 3372 n ^ ³ 1.5856 3373 nj ³ 1.5795 3376 Mp. 81-83 ° 4.2 Mp 127-128 °

г _

-Jt-

Verb no. Physical constant 4.15 τζ ° 1.5581 4.23 njj ° 1.5472 4:50 χζ ° 1.5628 4:59 njj ° 1.5450 4.64 22n £ 1.5735 4.66 τζ ° 1.5493 4.89 Resin, B, mp 48-58 ° 4.93 njj ° 1.5579 4.94 OeI, A, njj ° 1.5511 4113 njj ° 1.5600 4116 n ^ ² 1.5718 5:42 n ²² 1.5620 5.68 Mp. 103-106 ° 5.70 njj ° 1.5476 5.73 njj ° 1.5557 5.75 njj ° 1.5482 5.76 rL ° 1.5502 5.78 n ° 1.5467 5.81 njj ° 1.5765 5100 nj ^{0 '5} 1.5692 5102 22 five 1.5577 6.79 Mp. 95-98 ° 6.80 n ^ ⁴ 1.5656 6.82 nj ⁴ ' ⁵ 1.5551

с / -

Verb no. Physical constant 7.27 Mp 105-107 ° 7:33 Mp. 116-118 ° 7:34 Mp. 101-103 ° 8.72 Mp 127-137 ° 10.7 Mp 59-60 °

Claims (38)

-115- 28.10.1982 AP С 07 D / 239 803 (60 854/12)  ärfindungsanspruoh 1. An agrochemical pesticide for controlling or preventing infestation by microorganisms, characterized in that it contains as at least one active component, a compound of formula ». л .J-. Q ν ff Γιχ «j Ar - о - ·.-Σ-о (D contains, in which Ϊ stands for -CH = or -N =; R _a and R 1 independently of one another represent hydrogen, halogen, C ₁ -C 4 -alkyl, C ₁ -C ₃ -alkoxy or nitro} Ar is unsubstituted or substituted by halogen, C ₁ -C alkyl, C ₁ -Cy alkoxy, nitro and / or CF mono- or polysubstituted phenyl or naphthyl; U and V, independently of one another, represent C ₁ -C ₁ -alkyl optionally substituted by halogen or C ₁ -C 6 -alkoxy, or together form one of the following alkylene bridges >: 4 or · H «, where -116- 28.10.1982 AP С 07 D / 239 (60 854/12) and R ₂ independently of one another are hydrogen, C 1 -C 6 -alkyl, C 1 -C ₁₂ -alkyl which is monosubstituted or polysubstituted by halogen, phenyl, phenyl which is monosubstituted or polysubstituted by halogen and / or C 1 -C 4 -alkyl or Group -CH ₂ -ZR-, where oxygen or sulfur and represents hydrogen, C ₁ -C 6 -alkyl, a C ₁ -C ₂ -alkoxy-substituted C ₁ -C 6 -alkyl, C ₃ -C ₄ -alkenyl, Propinyl, 3-halo-2-propynyl, phenyl, a by halogen, C ^ -C, alkyl, C ₁ -C ₃ -alkoxy, nitro and / or Cj? - mono- or polysubstituted phenyl, benzyl or a through Halogen, C ^ C ₃ alkyl and / or C ₁ -C ₃ alkoxy mono- or polysubstituted benzyl; R ₃₁ R ₄ and Rc independently of one another denote hydrogen or C 1 -C ₄ -alkyl, where the total number of carbon atoms in R ₃ , R ₄ and Rc does not exceed 6 and R ^ is hydrogen or C 1 -C 6 alkyl; including their acid addition salts and metal complexes, together with carriers or additives. 2. Composition according to punction "1", characterized in that in the compounds of the formula IY is -CHa or -Ns, R and R _b independently of one another represent hydrogen, halogen, CJ-C ₃ -alkyl, C ₁ -C ₃ - AIkOXy or nitro; Ar for the G ₃ group R. - or stands; in which -117- 28.10.1982 AP С 07 D / 239 803 (60 854/12) R, R and R _Q independently of one another are hydrogen, halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, nitro or CP ₃ ; U and V independently of one another are C ₁ -C 4 -alkyl stand or together one of the following Alkylenbrüoken 4, / ^{2 3} ^ x ⁵ ° У "\ • - · 7 j or · H · form, / \ i i- R ₅ ⁴ ^ in which R ₁ and Rp independently of each other are vVaseerstoff, ^c -j- ^c -j2 "alkyl, mono- or polysubstituted by halogen-substituted C ₁ -C ₁ p-alkyl, phenyl, one or mehrfaoh by halogen and / or C ^ C- Alkyl substituted phenyl or the group -CH ₂ -ZR- *, wherein Z means oxygen or sulfur and R _{7 is} hydrogen, C 1 -C ₆ -alkyl, a C ₁ -C 8 -alkoxy-substituted C ₁ -C ₆ -alkyl, C ₃ -C ₄ -alkenyl, 2-propionyl, 3-halo-2-propynyl, phenyl, by halogen , C ₁ -C ₃ -Älkyl, C ₁ -C ₃ -alkoxy _{1 is} nitro and / or ₃ CJF singly or multiply substituted phenyl, benzyl or substituted by halogen, C -JC ₃ alkyl and / or C ₁ -O ₃ -Aikoxy is mono- or poly-substituted -benzyl; R ₃ , R and Rc are independently hydrogen or O ₁ -C.-alkyl, wherein the total number of carbon atoms in R ₃ , H ₄ and Rj- does not exceed the number б and R _{6 is} hydrogen or C 1 -C 4 -alkyl; including their acid addition salts and metal complexes. -118- 28.10.1932 AP С 07 D / 239 803 (60 854/12) Composition according to item 2, characterized in that in the compounds of the formula IY is -CH = or -H =, R and A ^ independently of one another represent hydrogen, halogen or G ₁ -C 6 -alkyl; Ar for the group in which R ₀ , R 1 and R _e, independently of one another, mean "hydrogen, halogen, GF- or C 1 -C -alkyl, and U and V have the meanings given under formula I" 4. A composition according to item 3, characterized in that in the compounds of formula IU and V independently of one another are C _1. -C - alkyl or together one of the following alkylene groups R., R ₀ R- R. ^' .vV ^N t- * or У * · form, wherein Д ^, Rp, R, R. and R ₅ are independently .Vassarstoff or C.-C.-alkyl wherein the total number of carbon atoms in as t off R., R, and R. ₁ the number 6 does not exceed} Ar for the group ^R d -119- 20.10.1982 AP С 07 D / 239 303 (60 854/12) wherein R, R and R _{6 are} independently hydrogen, halogen or C ₁ -C ₆ -alkyl; and Ϊ stands for -CHs or -Hs · A compound according to item 2, characterized in that in the compounds of the formula I Ϊ is -CHs or -Hs; Ar has the meanings given under formula I; R. d, R, R and R independently of one another represent hydrogen, chlorine, bromine, fluorine, methyl, methoxy or nitro; U and V independently of one another represent C ₁ -C 4 -alkyl or together form one of the alkylene groups mentioned under formula I, where R ₁ , R ₂ , R ₁ , R ₂ , R c and R g independently of one another represent hydrogen or C ₁ C is -alkyl or R _{1 is} -CH ₂ -OR ₇ , where R _{7 is} C ₁ -C -alkyl, C ₂ -C ₄ -alkyl substituted by C ₁ -C ₃ -alkoxy, Cv-C- Alkenyl or phenyl. A mixture according to item 1, characterized in that in the compounds of the formula I I is -CHs or -N *, R and R independently of one another represent hydrogen, halogen or C 1 -C 5 -alkyl or a salt thereof; Ar for the group where R _c , A. and R _{e are} independently hydrogen, halogen, Ci? C ₁ -G -alkyl, C ₁ -C ₃ -alkoxy; and U and V have the meaning given under formula I « -120- 28.10.1932 AP G 07 D / 239 803 (60 854/12) 7. Means according to item 1 », characterized in that In the compounds of formula IY is -CH» or -N =, R and U ^ independently of one another are hydrogen, halogen or O ₁ -G - alkyl; Ar for the group R .v wherein R _c , R, and R _{ß are} independently hydrogen, halogen, CP, C ₁ -C ₃ -AlJCyI, C ₁ -C; and U and V independently of one another are C ₁ -C 6 -alkyl, optionally C ₁ -C 4 -alkyl substituted by halogen or C ₁ -CG alkoxy or together one of the following alkylene groups RT) Ro # Ri% / or · · where d * _t Rp, R ~, Й. and R ₁ - independently of one another represent hydrogen or C ₁ -C 4 -alkyl, the total number of carbon atoms in R 1, R ₄ and R ₁ not exceeding the number 6 8. A composition according to item 1, characterized in that in the compounds of formula IY is -CHa or -K «, R _fi and R ^ are independently hydrogen, halogen or C ^ C - alkyl; Ar for the group -12V 28.10.1932 AP С 07 D / 239 (60 854/12) wherein R ₀ , R ^ and R independently of one another are hydrogen, halogen, GJP ₃ , C ₁ -C -alkyl , G-Gly- alkoxy; and U and V together represent the alkylene group CH ₅ OR ₇ ^{2 7} where R _{7 is} C ₁ -C -alkyl, C ₁ -C ₂ -substituted C ₁ -C -alkyl, C ₁ -C -alkenyl or prop-2-ynyl. 9 "agent according to item 1, characterized in that in the compounds of formula I Ϊ is -CH =; Ar has the meaning given under formula I; R and Rv independently of one another represent hydrogen, methyl, chlorine or bromine, R _Q , R ^ and R _Q independently of one another represent hydrogen, fluorine, chlorine, bromine, methyl, methoxy, CF 3 or nitro; U and V are independently optionally substituted by C ₁ -C ₂ -alkoxy or chlorine, C ₁ -C.-alkyl or together form one of the mentioned under formula 1 Älkylengruppen, wherein R _1, R _2, R _3, R *, Ra uad R ^ independently • » 'asaerstoff odar -O C _{1 3} alkyl, and R ₁ is -CH ₂ OR ₇ where R _{7 is} C ₁ ¹ J. alkyl, by C -C ₂ -alkoxy-substituted C ₃ -C -alkyl or C - C ₄ -alkenyl. 10 * Means according to item 1, characterized in that in -122- 28.10.1932 AP С 07 D / 239 803 (60 854/12) the compounds of the formula I Ϊ is -GH »or -N =, R and R ^ are each independently hydrogen, halogen or G-C-alkyl and in which Ar is unsubstituted or by C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, CP- or halogen-substituted phenyl and U and V have the meaning given under the formula I. 11. A composition according to item 1, characterized in that in the compounds of formula I Ϊ is -CH = or -Na, R and R ^ are independently hydrogen, methyl, chlorine or bromine, and wherein Ar is unsubstituted or halogen, methyl or CF substituted phenyl and U and V are independently C.-C - alkyl, optionally substituted by halogen or C ₁ -C ₂ -alkoxy-substituted C - C - alkyl or together represent an alkylene deqfolgenden ^R i / 2 V / 4_ / or \ I in which R ₁ , R-, R-, R and R ₁ - independently of one another represent hydrogen or C ₁ -C -alkyl, the total number of carbon atoms in R, R and R _{c being} the number 4 3 4 5 should not exceed · 12. Composition according to item 1, characterized in that in the compounds of formula I Ϊ is -CH »or -H =, R and R ^ are hydrogen, Ar is unsubstituted or substituted by halogen, methyl-substituted phenyl and U and V together form a group of the formula / / X · - * \ or (ι -123- 28.10.1982 AP С 07 D / 239 803 (60 854/12) in which Rp represents C ₁ -C ₄ -alkyl, such as methyl or ethyl, or hydroxy-C ₁ -C ₄ -alkyl, such as hydroxymethyl or 2-hydroxyethyl, or C ₁ -C ₂ -alkoxy-C C ₂ alkyl, such as methoxymethyl or thethoxymethyl. 13. A composition according to item 1, characterized in that it contains as active component 2- / p- (phenoxy) -phenyl7-2 - / - (1H-1,2,4-triazolyl) -methyl7-4-methyl-1 , 3-dioxane or a salt thereof. 14 · Composition according to item 1, characterized in that éв as active component 2- / p- (phenoxy) -phenyl7-2- / i- (1H-1,2,4-triazolyl) -methyl7-4-ethyl-1 , 3-dioxane or a salt thereof. Composition according to item 1, characterized in that the active component is 2- / p- (phenoxy) -phenyl-7-2- / T- (1H-1,2,4-triazolyl) -methyl] -7-4- raethyl-1,3-dioxolane or a salt thereof. 16. A composition according to item 1, characterized in that it contains as active component 2- / p- (phenoxy) -phenyl.7-2- / 3H-1,2,4-triazolyl) -methyl7-4-ethyl-1, 3-dioxolane or a salt thereof. 17 * Means according to Funk 1, characterized in that it contains as active component 2- / p- (phenoxy) phenyl7-2- / T- (1H-1,2,4-triazolyl) -methyl7-4-niethyl-5- contains methyl-1,3-dioxolane. 18. Composition according to item 1, characterized in that it contains as active component 2- / p- (phenoxy) -phenyl7-2- / T- (1H-1,2,4-triazolyl) -methyl7-1,3-dioxane or a salt thereof. -124- 23.10.1932 Af С 07 D / 239 803 (60 854/12) 19 A composition according to item 1, characterized in that it contains ala active component 2- / p- (phenoxy) -phenyl7-2- (imidazolylmethyl) -4-ethy1-1,3-dioxolane or a salt thereof. 20. Means according to sparks 1, characterized in that it contains as active component 2- / p- (2,4-dimethylphenoxy) -phenyl7-2- (i-.i.midazolylmethyl-4-ethyl-1,3-dioxolane or contains a salt thereof · 21. A composition according to sparks 1, characterized in that it contains as active component 2- / p- (3-chlorophenoxy) -phenyl7-2- (i-imidazolylmethyl) -4-ethyl-1,3-dioxolane or a salt thereof , 22. A composition according to item 1, characterized in that it contains as active component 2- / p- (4-chlorophenoxy) -phenyl7-2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane or a salt thereof , A composition as claimed in 1, characterized in that it contains 2- / p- (3-rifluoromethylphenoxy) phenyl 7-2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane or a salt thereof as the active component contains. Compound 1 according to 1, characterized in that it contains as its active component 2- / p- (4-chloro-3-methylphenoxy) -phenyl] .7-2- (1-imidazolylmethyl) -4-ethyl-1,3 dioxolane or a salt thereof · 25 · agent according to FUNC 1, characterized in that it as the active component p- ^ 2- (3 '4-dichlorophenoxy) -phenyl7-2- (i-imidazolylmethyl) -4-ethyl-dioxolane or a 1-1.3 Contains salt thereof. -125- 28.10.1982 AP С 07 D / 239 803 (60 854/12) 26. A composition according to item 1, characterized in that it as the active component 2- / i> -12 »5-Diohlor phenoxy) -pheny3.7-2- (i-imidazolylmethyl) -4-ethyl-1,3-dioxolane or a salt thereof. 27. Composition according to item 1, characterized in that ea as the active component 2- / p- (3 »4-dichlorophenoxy) -phenyl7-2- (1-imidazolylmethyl) -4-methoxymethyl-1,3-dioxolane or a salt of which contains · 28. A composition according to item 1, characterized in that it contains as active component 2- / p- (4-l? Luorphenoxy) -phenyl-7-2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane or a salt of which contains. 29. A composition according to item 1, characterized in that it is 2- / p- (4- ₄ 4uorphenoxy) -phenyl ^ -2- (1-imidazolylmethyl) -4-methyl-5-ni3thyl-1,3-dioxolane or a Contains salt thereof · 30. A composition according to item 1, characterized in that it contains as active component 2- / p- (4-chloro-2-methyl-phenoxy) -phenylJ-2- (1-imidazolylmethyl) -4-methoxymethyl-1,3- dioxolane contains · 31. A composition according to item 1, characterized in that it is active component 2- / p- (phenoxy) -phenyl] j7-2- / ΪΉ-1,2,4-tr iazolyl) -me thy] .7-4 contains hydroxymethyl-1,3-dioxolane « 32. Medium according to item 1, characterized in that it contains as active component 2- / p- (4-l ^f luorphenoxy) -phenyl _<^ 7-2- (1-imidazolylmetiiyl) -4-hydroxymethyl-1,3-dioxolane contains. -126- 2Ö.10.1932 AP С 07 i; / 239 (60 854/12) 33. Composition according to item 1, characterized in that it contains as active principle 2-p-p- (4-fluorophenoxy) -phenyl-7-2- (1H-1,2,4-triazolyl) -methyl7-1,3- dioxane contains · Composition according to item 1, characterized in that it contains as at least one active component a compound of the formula I according to one of the items 2 to 5 and 13 to 16 35. Composition according to one of the items 1 to 34, characterized in that os contains 0.1 to 99 % of an active compound of the formula I, 99.9 to 1 % of a solid or liquid additive and 0 to 25 % of a lenside · 36. Means according to item 35, characterized in that 0.1 to 95 io a - contains "'irkstoffes of formula I, 99.8 to 5% of a solid or liquid adjuvant and 0.1 to 25% of a iensides · Process for the preparation of an agrochemical agent, characterized in that at least one compound of the formula I according to one of the items 1 to 5 and 13 to 16 is intimately mixed with suitable solid or liquid additives and surfactants η. 38. A method for controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, characterized by applying a compound of formula I according to any one of items 1 to and 13 to 16 on the plant or its location · AP С 07 D / 239 803 60 854 12 - 127 - 39. Use of compounds of the formula I according to item 1, characterized in that they are used for controlling and / or for the preventive prevention of infestation of microorganisms on plants. 40. Use according to item 39, characterized in that compounds of the formula 2 according to one of the items 2 to 15 and 13 to 16 are used. 41. Use according to item 39, characterized in that the microorganisms are phytopathogenic fungi. 42. The method according to item 37, characterized in that the compound using conventional excipients and carriers in a suitable application form überfuhrt. 43. Composition according to item 1, characterized in that it contains 2-.zp-0 * ^f -chlorophenoacy) -phenyl? _ -? - (1H-1,2,4-triazolyI) -methyj7-4-ethyl- 1,3-dioiolane (Compound No. 3.6) contains · 44. Composition according to item 1, characterized in that it comprises 2- / p- (3% 4-dichlorophenoxy) -phenyl-27-2- / T- (i H-1,2,4-triazolyl) -methylS-7-methoxymethyl -1,3-dioxolane (Compound Nr, 3.177). 45. Composition according to item 1, characterized in that it contains 2- / p- (3 ¹ , 4'-) ісЫогр1іепоху) -r1іепуІ7-2- / Т- (іН-1,2,4-triazolyl) -methyl7- ^ -ethyl-1,3-dioxolane (Compound No. 3.172). 46. Composition according to item 1, characterized in that it 2- / p- (4 • -Chlorphenoxy) ^ ^l -methylphenyl7-2- / T (i H-1,2,4-triaeolyl) -methyj £ 7- 4-methyl-1,3-dioxolane (Compound No. 4,113) contains · - 128 - AP С 07 D / 239 60 854 12 47. Means according to item 1, characterized in that it 2- / p- (4'-chlorophenoxy) -phenyl-7-2- / f-0H-1,2,4-triazolyl) -methylT- ^ -benzyl-1,3-dioxolane-copper sulfate complex (Compound No. 3 * 86) contains · 48. Means according to item 1, characterized in that it contains 2 - ^ - (4-chlorophenoxy) -2 ^l -methylphenyl 7-2 <- / T- (iH-1,2,4-triazolyl) -methyj7-4-ethyl -1,3-dioxolane (compound Br. 4.116). 49. Composition according to item 1, characterized in that it contains 2- / p- (phenoxy) -2 • -orЬЗ-orphenyi7-2- ^ T- (i H-1,2,4-triazolyl) -methy ^ -4- ethyl-i, 3-ioxolane (Compound No. 5.42). 50. Composition according to item 1, characterized in that it contains 2- / 5- (4-chlorophenoxy ) -phenyl17-2- / F- (1H-1,2,4-triazolyI) -ffiethyj7-4,5- ! iiiiiethy contains 1-1,3-dioxolane (Compound No. 3.85). 51 у Means according to item 1, characterized in that it 2-Zp- (4-bromophenoxy) -phenyl 17-2- / T- (1 H-1,2,4-triazolyl) -methoxy) -4-ethyl-1,3-ee. i oxo lan (compound No 3.103). 52. Means according to item 1, characterized in that it contains Z-β- (phenoxy) -2 »n-enylphenyl-7-2- / T- (iH-1,2,4-triazolyl) -methyl7-4-ethyl-1, 3-dioxolane (Compound No. 5.76), 53. Composition according to item 1, characterized in that it comprises 2- _d 5- (phenoxy) -2 ^l -mei-hylpheny _i i7-2- (i-imidazolyl-ethyl) -4-ethyl-1,3-dioxolane (compound no 5.73). 54. Composition according to item 1, characterized in that it contains 2-2? - (4'-chlorophenoXs) -2 '-methylphenyl-2- (i-imidazolylmethyl) -4-methyl-1,3-dioxolane (compound no 4.15). AP С 07 D / 239 803 60 854 12 - 129 - 55 · Means according to item 1, characterized in that it 2k / p- (4 '-Fluorphenoxy) -2 ~ ^f -methylphenyj7 ² - ⁽¹ -imidazolylmethyl) contains -4-methyl-1,3-dioxolane (Compound Mr. 4.66). 56 _f Means according to item 1, characterized in that it 2 - ^ - (4-chlorophenoxy) -pheny37-2-ZT- (i H-1,2,4-triazolyl) -propyl-7-4-methoxy-methyl-1,3-dioxolane (Compound No. 3 * 83 ) contains · 57. The method according to item 37 », characterized in that a compound of points 43 to 56 is used. 58 «Method according to point 38, characterized in that a compound of points 43 to 56 is used. 59 · Use according to point 39 »characterized by» that a connection of points 43 to 56 is used.