CA1192203A - Microbicidal arylphenyl ether derivatives, production thereof and use thereof - Google Patents

Abstract

Abstract of the Disclosure The invention relates to novel arylphenyl ether derivatives of the formula (I), wherein Y is -CH= or -N=, Ra and Rb, each independently of the other, are hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy or nitro, Ar is phenyl or naphthyl, each unsubstituted or mono- or polysubstituted by halogen, C1-C7alkyl, C1-C7alkoxy, nitro and/or CF3, U and V, each independently of the other, are C1-C12alkyl which is unsubstituted or substituted by halogen or C1-C6alkoxy, or together form one of the following alkylene bridges

Description

y o~

polysubstituted by halcgen and/or Cl-C3alkyli or are the -CH~-Z-R7 group, wherein Z is oxygen or sulfur and R7 is hydrogen, Cl-C8alkyl or Cl-C8alkyl which is sub-stituted by Cl-C2alkoxy; C3-C4alkenyl, prop-2-ynyl, 3-haloprop-2-ynyl~ phenyl or phenyl which is mGnO- or polysubstituted by halogen, Cl-C3alkyl, Cl-C3alkoxy, nitro andlor CF3i benzyl or benzyl which is mono- or polysubstituted by halogen, Cl-C3alkyl and/or Cl-C3alkoxy, R3, R4 and R5, each independently of the other,~re hydrogen or Cl-C4alkyl, the total number of carbon atoms in R3, R4 and R5 not exceeding 6, and R6 is hydrogen or Cl C3alkyl, together with the acid addition salts and metal complexes thereof. The invention also relates to the production of these compounds and as well as to agrochemical compositions and pharmaceutical preparations which contain at least one compound of the formula I as active ingredient, to the production of these compositions and preparations and to the use thereof. They may be used, on the one hand, in agriculture or related fields for controlling phytopathogenic micro-organisms and, on the other, as antimycotic and/or anti-convulsive and anxiolytic agents in the pharmaceutical field, for example for controlling parasitic fungi in warm-blooded animals and/or for treating different forms of epilepsy, states of anxiety, tension and excitation, andlor manic states of mind.

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Case 5-13393/~/AP

Novel microbicidal arylphenyl ether derivatives, production thereof and use thereof The present invention relates to substituted arylphenyl ether derivatives of the formula I below, and to the acid addition salts and metal complexes thereof. The invention also relates to the production of these compounds as well as to agrochemical compositions and pharmaceutical preparations which contain at least one compound of the formula I as active ingredient, to the production of these compositions and preparations and to the use thereof, and further to a method of treating plants for controlling or preventing attack by phytopathogenic microorganisms.

The arylphenyl ether derivatives of this invention have the formula u~
Ar--O~
Cll2-N~ !

wherein Y is -CHa or -N=, Ra and Rb, each independently of the other9 are hydrogen, halogen, Cl-C3alkyl, Cl-C3alkoxy or nitro, Ar is phenyl or naphthyl, each unsubstituted or mono-or polysubstituted by halogen, Cl-C7alkyl, Cl-C7alkoxy, nitro and/or CF3, U and V, each independently of the other, are Cl-C12alkyl which is unsubstituted or substituted by halogen or Cl-C6alkoxy, or together form one of the following alkylene bridges Rl R2 3~- ~ 4 R6\X--~
/ \ ~ i t R5 or \ H

wherein Rl and R2, each independently of the other, are hydrogen, Cl-C12alkyl or Cl-C12alkyl which i9 mono- or poly substituted by halogen; phenyl or phenyl which is mono- or polysubstituted by halogen and/or Cl-C3alkyl;
or is the -CH2-Z-R7 group, wherein Z is oxygen or sulfur and R7 is hydrogen, Cl-C8alkyl or Cl-C8alkyl which is substituted by Cl-C2alkoxy, C3-C~alkenyl, prop-2-ynyl, 3-haloprop-2-ynyl, phenyl or phenyl which is mono-or polysubstituted by halogen Cl-C3alkyl, Cl-C3alkoxy nitro and/or CF3; benzyl or benzyl which is mono-or polysubstituted by halogen, Cl-C3alkyl and/or Cl-C3alkoxy, R3, R4 and R5, each independently o the other,are hydrogen or Cl-C4alkyl, the total number o carbon atoms in R3, ~4 and R5 not exceeding 6, and ~6 is hydrogen or Cl-C3alkyl~
together with the acid addition salts and metal complexes thereo~

As unsubstituted or substituted phenyl or naphthyl, the substituent Ar has e.g. ~he formula R ~C c ~ ~.
>< / d R R ~
e e --wherein Rc, Rd and Re, each independently of the other, are hydrogen, halogen, Cl-C7alkyl, Cl-C7alkoxy, nitro or CF3.

Depending on the number o~ indicated carbon atoms, the ~erm "alkyl" by itself or as moiety of another substituent will be understood as meaning e.g. the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl~
and the isomers thereof, e.g. isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl etc. Alkenyl denotes e.g.
propen-l-yl, allyl, buten~l-yl, buten-2-yl or buten-3-yl.
Throughout this specifiration, halogen denotes fluorinea chlorine, bromine or iodine~ with chlorine or bromine being preferred.

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

Salts of this invention are in particular addition salts with inorganic or organic acids which are physiologi-cally tolerable with respect to the envisaged utility.

Examples of inorganic and organic acids which are physiologically tolerable with respect to ~he utility as microbicides in plant protection, are hydrohalic acids, e.g. hydrochloric, hydrobromic or hydriodic acid, sulfuric .

acid, phosphoric acid, phosphorous acid, nitric acid, unsubstituted or halogenated fatty acids such as acetic acid, trichloroacetic acid and oxalic acid, or sulfonic acids such as benzenesulfonic acid and methanesulfonic acidO

Acids which are physiologically tolerable in respect of the utility as medicament, i.e. pharmaceutically acceptable acids, are eOg. pharmaceutically acceptable mineral acids such as hydrohalic acids~ e.g. hydrochloric, hydrobromic or hydriodic acid, nitric acid, sulfuric acid or phosphoric acid, pharmaceutically acceptable carboxylic and sulfonic acids such as aliphatic monocarboxylic acids and optionally hydroxylated dicarboxylated acids, e.g.
acetic acid, fumaric acid, maleic acid, malic acid or tartaric acid, and also aliphatic or aromatic sulfonic acids such as lower alkanesulfonic acid or unsubsti~uted or substituted benzenesulonic acid, e.g. methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluene-sulfonic acid and p-bromoben2enesulfonic acid, as well as sulfamic acids, e.g. N~cyclohexylsulfamic acid.

Metal complexes of formula I consist of the basic organic molecule and an inorganic or organic metal salt, e.g. the halides, nitrates, sulfates, phosphates, tartrates etc. of copper, manganese, iron, zinc and other metals.
The metal cations may exist in different valence statesO

The compounds of formula I are oils 9 resîns or solids which are stable at room temperature and which possess very valuable physiological properties, such as microbicidal, e.g. phytofungicidal and pharmacological proper~ies, in particular antimycotic as well as anticonvulsive and anxioly~ic properties. They may therefore may be used, on the one hand, in agriculture or related fields for con-Z~ 3 trolling phytopathogenic microorganisms and, on the other,as antimycotic and/or anticonvulsive and anxiolytic agents in the pharmaceutical field, for example for controlling parasitic fungi in warm-blooded animals and/or for treating different forms of epilepsy, states of anxiety, tension and excitation3 and/or manic s-tates of mindO

An important group of microbicides for use in plant protection comprises compounds of the formula I, wherein Y is -CH= or -N=, eac:h of Ra and Rb independently of the other is hydrogen, halogen, Cl-C3alkyl, Cl-C3alkoxy or nitro; Ar is the group R ~ C d R /~-= Re~

wherein Rc, Rd and Re, each independently of the otherg are hydrogen, halogeng C.l-C3alkyl, Cl-C3alkoxy, nitro or CF3~
U and V, each inrlependently of the other,are Gl-C12alkyl or together form one of the following alkylene bridges Rl R2 R3~ 4 R6 / \ ~ i t R5 or wherein Rl and R2, each independently of the other, are hydrogen, Cl-C3alkyl or Cl-C12alkyl which is mono or poly-substituted by halogen, orare phenyl or phenyl which is mono or polysubstituted by halogen and/or Cl-C3alkyl, or are the -CH2-Z-R7 group, in which q~

~ is oxygen or sulfur and R7 is hydrogen, Cl-C8alkyl or Cl-C8alkyl which is subs~ituted by Cl-C2alkoxy, or is C3-C4alkenyl, prop-2-ynyl, 3-haloprop-2-ynyl, phenyl or phenyl which is mono- or polysubstituted by halogen, Cl-C3alkyl, Cl-C3alkoxy~ nitro and/or CF3~ or is benzyl or benzyl which is mono- or polysubstituted by halogen, Cl-C3alkyl and/or Cl-C3akoxy, R3, R4 and R5, each independently of the other, are hydrogen or Cl-C4alkyl 7 the total number of carbon atoms in R3, R4 and R5 not exceeding 6, and R6 is hydrogen or Cl-C3alkyl, and the acid addition salts and metal complexes thereof.
This subgro~lp will be designated group Ia.

A preferred group of agriculturally useful microbicides comprises compounds of the formula I, including their salts and metal complexes, wherein Y is -CH= or -N=, each of Ra and Rb independently of the other is hydrogen, halogen or Cl-C3alkyl, Ar is the group E~
d~
~ <, _./
e wherein each of Rc, Rd and Re independently of the other is hydrogen, CF3 or Cl-C3alkyl, and U and V are as defined for formula I. This group will be designated group Ib.

Preferred microbicides within subgroup Ib are those compounds of the formula I, wherein each of U and V
~independently of the other is Cl-C3alkyl or together form one of the following alkylene groups ~ ~a3z;~3 or 3\X ~ 4 i ~~~~ 5 wherein each of Rl, R2, R3, R4 and R5 independently of the other is hydrogen or Cl-C4alkyl, the total number of carbon atoms in R3, R4 and R5 not exceeding 6. This group will be designated group Ic.

A further preferred group of agriculturally useful microbicides comprises compounds of the formula I, wherein Y is -CH= or -N=, Ar is as defined for formula I, each of Ra~ Rb, Rc, Rd and Re independently of the other is chlorine, bromine, fluorine, methyl, methoxy or nitro;
each of U and V independently of ~he other is Cl-C3alkyl or together form one of the alkylene groups as defined for formula I, wherein each of Rl, R2~ R3, R~, R5 and R6 independently of the other is hydrogen or Cl-C3alkyl~ or Rl is -OEI2-0-R7, in which R7 is Cl-C3alkyl, C2~C4alkyl which is substituted by Cl-C3alkoxy, or is C3-C4alkenyl or phenyl. This group will be designated group Id Particularly preferred microbicides within group Id are those in which U and V together form an unsubstituted or a simply substituted ethylene or propylene bridge. This group will be designated group Ie.

Accordingly, the following individual compounds may be cited as exemplifying particularly preferred compounds for use in agriculture:

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

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

Interesting compounds of the formula I in respect of their antimycotic activity are those belonging to the group If, wherein Y is -C~= or -N-, each of Ra and Rb independently of the other is hydrogen, halogen or Cl-C3alkyl, Ar is the group d~o.~
~.=./
Rc wherein each of Rc, Rd and Re independently of the other is hydrogen, halogen3 CF3~ Cl-C3alkyl, Cl-C3alkoxy, and U
and V are as defined for formula I.

Within subgroup If, preferred compounds of the formula I in respect of their antimycotic activity are those in which each of U and V independently of the other is Cl-C6alkyl, C2-C~alkyl which is unsubstituted or substituted by halogen or Cl~C2alkoxy, or together form one of the following alkyl.ene groups ~ \ or I t R

wherein ea~h of ~1' R2, P'3~ R4 and R5 independentl~ o~ the other is hydrogen or Cl-C4alkyl, the total number of carbon atoms in R3, R4 and R5 not exceeding 6. This group will be designated group Ig.

9r~3 g Within subgroup Ig, preferred compounds of the formula I in respect of their antimycotic activity are those in which U and V together are the alkylene group wherein R7 is Cl-C4alkyl~ C2-C4alkyl which is suhstituted by Cl-C2alkoxy, or is C3-C~alkenyl or prop-2-ynylO This group will be designated group Ih.

A further preferr~d group of compounds of the formula I
having antimycotic activity comprises those in which Y is -CHa, Ar is as defined for formula I, each of Ra and Rb independently of the other is hydrogen, methyl, chlorine or bromine, each of Rc, Rd and Re independently of the other is hydrogen, fluorine, chlorine, bromine, methyl, methoxy, CF3 or nitro, each of U and V independently of the other is Cl-C3alkyl which is unsubsituted or substituted by Cl-C2alkoxy or chlorine, or together form one of the alkylene groups as defined for formula I, wherein each of Rl, R2, R3, R~, R5 and R6 independently of the other is hydrogen or Cl-C3alkyl~ or Rl is -CH20R7, wherein R7 is Cl-C3alkyl, C2-C3alkyl which is substituted by Cl-C2alkoxy, or is C3-C4alkenyl. This group will be designated group Ii.

The folLowing individual compounds may be cited as exemplifying particularly preferred compounds having antimycotic activity:
2-[p-(phenoxy)phenyl]-2~ (lH-1,2,4-triazolyl)methyl]-4-methyl-5-~.ethyl-1,3-dioxolane;
2-[p-(phenoxy)phenyl3-2-[1-(1ll-1,2a4-triazolyl~methyl]-1~3-dioxane;
2-[p-(phenoxy)phenyll-2-(1-imidazolylmethyl)-4-ethyl-1,3 dioxolane;

2-[p-(2,4-dimethylphenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane;
2-[p-(3-chlorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane;
2-[p-(4-chlorophenoxy)phenyl~-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane;
2-[p-(3-trifluoromethylphenoxy)phenyl]-2-(1-imidazolyl-methyl)-4-ethyl-1,3-dioxolane;
2-[p-~4-chloro-3-methylphenoxy)phenyl~-2-(1-imidazolyl-methyl)-4-ethyl-13 3-dioxolane;
2-[p-~3,4-dichlorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane;
2-[p-(2,5-dichlorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane;
2-[p~(3,4-dichlorophenoxy)phenyl~-2-(1-imidazolylme~hyl)-4-methoxymethyl-1,3-dioxolane;
2-[p-(4-fluorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane;
2-[p-~-fluorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-methyl-5-methyl-1,3-dioxolane;

including their respective pharmaceutically acceptable acid addition salts, processes for their production, phaLma-ceutical preparations containing them, and their use as medicaments.

Interesting compounds of the formula I in respect of their anticonvulsive and anxiolytic activity are those belonging to the group Ij, wherein Y is -CH= or -N=, each of Ra and ~ independently of the other is hydrogen, halogen or Cl-C3alkyl, Ar is phenyl or phenyl which is substi~u~ed by Cl-C3alkyl, Cl-C3alkoxy, CF3 or halogen, and U and V are as defined for formula I.

., Within subgroup Ij~ compounds of the formula I having distinctly useful anticonvulsive and anxiolytic properties are those in which Y is -CH= or -N=, each of ~a and Rb independently of the other is hydrogen, methyl, chlorine or bromine, Ar is phenyl or phenyl which is substituted by halogen, methyl or CF3, and each of U and V independently of the other is Cl-C3alkyl, C2-C3alkyl which is unsubstituted or substituted by Cl-G2alkoxy~ or together form one of the following alkylene groups l\ _ /R2 R3~ R4 / \ or i t-R

wherein each of Rl, R2, R3, R4 and R5 independently of the other is hydrogen or Cl-C~alkyl, the total number of carbon a~oms in R3, R4 and R5 not exceeding 40 This group will be designated group Ik/

A ~urther preferred group of compounds having pronounced anticonvulsive and anxiolytic properties comprises those in which Y is -CH= or -N=, Ra and Rb are hydrogen, Ar is phenyl or phenyl which is substituted by halogen or methylg and U and V together are a group of the formula .

~2 j/ \j wherein R2 is Cl-C4alkyl such as methyl or ethyl, or Cl-C3hydroxyalkyl such as hydroxymethyl or 2-hydroxyethyl, or Cl-C2alkoxy-Cl-C2alkyl such as methoxymethyl or ethoxy methyl This group will be designated group Il.

The following individual compounds may be cited as exemplifying particularly preerred compounds having anticonvulsive and anxiolytic properties:
2-[p-(phenoxy)phenyl]-2-[1-(lH-1,2,4-triazolyl)methyl]-1~3-dioxane;
2-[p-(4-chlorophenoxy)phenyl3-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane;
2-[p-~4-chloro-2-methylphenoxy)phenyl]-2-(1-imidazolyl methyl)-4-methoxymethyl-1,3-dioxolane;
2-[p-(phenoxy)phenyl~-2-[l-(lH-192~4-triazolyl~methyl]-4-hydroxymethyl-1,3-dioxolane;
2-[p-(4-fluorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane;
2-[p-(4-~luorophenoxy)phenyl]-2-(1 imidazolylmethyl)-~-hydroxymethyl-1,3-dioxolane;
2-[p-(4-fluorophenoxy)phenyl~-2-[1-(lH-1,2,4-triazolyl)-methyl]-1,3-dioxane together with their respective pharmaceutically acceptable acid addition salts, processes for their produc~ion, pharma-ceutical preparations con~aining them, and their use as medicaments.

The compounds of formula I may be obtained by A) condensing a compou-nd of the ormula II

Me-N~S~ ~ (II), wherein Me is hydrogen or a metal cation, with a compound of the ormula III

Ar-O- ~ 2-X

wherein X is a leaving group, or B) in a compound of the Eormula IV
a / = N

Ar _ O ~ -,C, 2 \ (IV) converting the carbonyl group into a group of the formula V

O O
(V) U------------V
or C) condensing compounds of the formulae VI and VII
Ra -N

Ar - o_ ~ / C ~ - CH2- N ~ (VI) and X2 - R7 (VII), O /0 Y~
Rb CH2~ CH-CH2-X

wherein one of the radicals Xl and X2 is hydroxyl or mercapto which may be in salt orm, e.g. of the formula -Z-Me, and the other is a leaving group X, or both Xl and X2 are hydroxyl groups, with each other to give compounds of the formula I, wherein U and V together are a group of the formula -CH2-CH(CH2ZR7)-and R7 is a radical which differs from hydrogen, or D) condensing compounds of the formulae VIII and IX

Ar-x3 (VIII) and X4 ~ C _ CH ~ (IX), Rb U-----V
~;~ wherein one of the radicals X~ and X~ is an O-Me group, in ~lich Me is hydrogen or preferably a metal cation, and , ~ ~ ~3 the other is a radical which is replaceable by aryloxy, with each other, or E) subjecting a compound of the formula Ar-O-C-O-~ C~CH2-N~ (X) R, I I
D ~ V
to intramolecular decarboxylation and, if desired, converting a resultant compound into another compound of the formula I
and/or converting a free compound into an acid addition salt, an acid addition salt into the free compound or lnto another acid addition salt, or converting a free compound or acid addition salt into a metal complex.

Examples of metal cations Me are alkali metal cations, e.g. lithium, sodium or potassium cations, or alkaline earth metal cations, e.g. magnesium, strontium or barium cations.

Leaving groups are e.g. reactive esterified hydroxyl groups, such as hydroxyl groups which are esterified wi~h a hydrohalic acid, e.g.wîthhy~o~uoricahydrochloric, hydrobromic or hydriodic acid, or with a lower alkanesulfonic acid,an unsubstituted or substituted benzenesulfonic or a halo-sulfonic acid, e.g. with methanesulfonic acid, ethane-sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or fluorosulfonic acid The reaction of an azole of the formula II
,~=N
M N/ ! (II), ~9~3 wherein Y is -CH= or -N- and Me is preferably a metal atom, especially an alkali metal atom9 with a compound of the formula III
R
Ar-O- ~ H2--X ( I I I ), U~ V
wherein Ar, Ra, Rb, U and V are as defined for formula I
and X is e.g. halogen, in particular chlorine, bromine or iodine, or benzenesulfonyloxy, p-tosyloxy, trifluoroacetyl-oxy or, preferably, lower a~kylsulfonyloxy, e.g. mesyloxy, is preferably conducted in a relatively polar but inert organic solvent, e.g. N,N dimethyl formamide, N,N-dimethyl acetamide, dimethyl sulfoxide, acetonitrile, benzonitrile and the like. Such solvents may be employed in combination with other inert solvents such as aliphatic or aromatic hydrocarbons, e.g. benzene, toluene, xylene, hexane, petroleum ethera chlorobenzene, nitrobenæene, e~c.

If X is chlorine or bromine, an alkali iodide (such as NaI or KI) may conveniently be added in order to speed up the reaction, Elevated temperatures in the range rom 0 to 220C, preferably from 80 to 170C, are advantageous.
It is advantageous to heat the reaction mixture under reflux.

Where Me in formula II is hydrogen, the process is carried out in the presence of a base. Examples of suitable bases are inorganic bases such as the oxides, hydroxides, hydrides, carbonates and bicarbonates of alkali metals and alkaline earth metals, as well as organic bases e9g.
tertiary amines such as triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, ~-pyrrolidyl-pyridine etc.

- 16 ~

In this process variant, and in the subsequent ones, the intermediates and final products may be isolated from the reaction medium and, if desired, purified by one of the methods conventionally employed, e.g~ by extraction, crystallisation, chromatography, distillation etc.

The conversion of the carbonyl group in compounds of the formula IV into the group of the formula V is carried out by reaction with an orthocarboxylic acid Cl-C12trialkyl ester~ the Cl-C12alkyl groups of which may be substituted by halogen or Cl-C6alkoxy, or in the presence of an acid, with at least 2 moles of a monohydric alcohol of the formula U-OH (Va), to give compounds of the formula I in which U and V are identical unsubstituted or substituted Cl-C12alkyl groups, or by reaction with a diol of the formula Vb HO - U-~-V-- OH (Vb) to give compounds of the formula I, wherein U and V together are one of the alkylene bridges defined at the outset. In the foregoing, Ar, Y, Ra, Rb, U and V are as defined for formula I.

This ketalisation reaction may be carried out in similar manner to already known ketalisation reactions, e.g. in similar manner to the preparation of 2-bromomethyL-2,4-diphenyl-1,3-dioxolane [Synthesis, 1974 (I), 23].

In the preferred embodiment of the ketalisation, both reactants are heated for several hours under reflux together with an azeotrope former in a conventional organic solvent. Examples of suitable azeotrope formers are benzene, ~oLuene, xylene, chloroform or carbon tetrachloride. To hasten the reaction it may be convenient to add a strong acid, e.g. p-toluenesulfonic acid. Examples of organic solvents which may be used are in this case aromatic hydrocarbons such as benzene, toluene, xylene etc., saturated hydrocarbons such as n-hexane, or saturated halogenated hydrocarbons such as 17 1 ~ 1- trichloroethane.

The ketalisation may also be carried out by other methods, e.g. by reacting a ketone (IV) which has been ketalised wi~h an alcohol or phenol which differs from the alkanol or diol of the Eormula Va or Vb respectively, and effecting transketalisation with an excess of alkanol Va or diol Vb to a compound (I). The starting rnaterial may be obtained by one of process variants A), D) and E).

Compounds of the formula I, wherein U and V in variant C) are together -CH2-CH(CH2ZR7)-, are obtained e.g. by reaction of a compound of the formula VI with a compound of the formula VII, wherein Xl is a -ZH group and X2 is a group X. The reaction is preferably carried out in an inert organic solvent. Examples o suitable solvents for this reaction are N,N-dimethyl formamide, N,N-dimethyl acetamide, hexamethylphosphoric triamide, dimethyl sulfoxide, 4-methyl-3-pentanone etcO Mixtures with other inert solvents, e.g. with aromatic hydrocarbons such as benzene, toluene~
xylene etc., may also be used. In some cases it may be convenient to carry out the reaction in the presence o a base in order to speed up the reaction rate. Examples of suitable bases are alkali metal hydrides or alkali metal carbonates~ It may also be advantageous in certain cases to convert-the compound of the formula VI first into a suitable metal salt. This is preferably accomplished by reaction of VI with a sodium compound, e.g. sodium hydride, sodium hydroxide etc. This salt of the compound of formula VI is subsequently reacted with the compound of formula VII. In order to increase the reaction rate the process may also becarried outin some cases at elevated temperature, preferably in the range from 80 to 130C
or at the boiling point of the solvent.

Compounds of the formulae VI and VII, wherein Xl is a group X and X2 is a -ZH group, may also be reacted in similar manner.

In ~he condensation reaction of compounds of the formulae VI and VIIg wherein Xl and X2 are hydroæyl, to give compounds of the formula I in which Z is oxygen, the reactants can be heated under reflux in a suitable solvent, while simultaneously distilling off water from the reaction mixturP as an a2eotrope~ Suitable solvents are aromatic hydrocarbons such as toluene or the alcohol HO-R7 itself. This reaction is conveniently carried out in the presence of a ~trong acid, e.g. p toluenesulfonic acid.

In variant D~, a start is preferably made from compounds of the formulae VIII and IX, wherein X3 is an OMe group and X4 is a leaving group, or conversely X3 is the leaving group and X~ is the -OMe group, whilst Ra, Rb~
U, V~ Y and Ar are as defined for formula T and Me is preferably hydrogen. It is advantageous to carry out ~he reaction under the conditions described for variant A).

In variant E), the compound to be decarboxylated of the formula X, which may be ohtained by ketalisation of a compound of the formula XI
R

-T (XI), ~L

in a manner similar to that described in B)~ which compound may in turn be obtained by reaction of a compound of the formula Ar OH (XII) with a difunctional derivative of carbonic acid, e.g. with phosgene, a lower alkylester of haloformic acid or with a di-lower allyl or diphenyl carbamate, and further reaction with a compound of the formula XIII

a o HO-~ -C-CH2-N~ 11 (XIII) is heated dry or in a high boiling solvent such as a high boiling ether, e, g. diphenyl ether or ethylene glycol dimethyl e~her, to about 120 to 220C.

Compounds obtained by the process of the inven~ion may be converted into other compounds of the formula I by methods which are known per se.

Accordingly, for example, compounds obtained by th~
process of the invention may be transketalised to o~her compounds of the formula Io For e~ample, in compounds of the formula I, wherein U and V are identical unsubstituted or substituted Cl-C12alkyl radicals U, a group U may be replaced by a group V by reaction with 1 mole of another unsubstituted or substituted Cl-C12alkanol of the formula V-OH (Ve), or both groups U may be replaced by a divalent radieal by reaction with a diol of the formula Vb. The transketalisation is ~arried out in eonventional manner, for example in the presenee of an acid eondensing agent sueh as a mineral aeid 3 sulfonic acid or strong carboxylic acid, e~g. hydrochloric or hydrobromic acid, sulfuric acid, p-toluenesulfonic acid or trifluoroacetic aeid, preferably while removing readily volatile reaction products by distillation or azeotropic distillation.

Further, additional substituents may be introduced, if desired, into the carbocyclic aryl moieties of compounds obtained by the process of the invention. For example, halogen can be introduced by reaction with a halogen in ~he presence of a Lewis acid, e.g. an iron, zincg boron or antimony halide~ or by treatment with N-chlorosuccinimide.

In addition, nitro groups can be reduced to amines~
e.g. by means of suitable complex hydride3, e.g. with l-Lthium aluminium hydride, which amines may then be diazotised, e.g. with nitrous acid, and the diazonium group replaced in customary manner by halogen or alkoxy.
Likewise, halogen may be replaced by alkyl by reaction with an alkyl metal compound, e.g. with an alkyl lithium or alkyl magnesium halide.

If the compounds of Eormula I are obtained as bases, then they can be converted into corresponding salts o the formula I with inorganic or organic acids, or into metal complexes of the formula I by using preferably e~uimolar amounts of metal salts. Conversely~ salts of the formula I
can be converted into the free bases oE the formula I by reaction with an alkali carbonate or bicarbonate or an alkali hydroxide.

The starting ketals of the formula III can be obtained from the methyl aryl ketone of the formula XIV

Ar-O- .\ $ ~--CO-CH3 (XIV) R

by reaction wi~h the desired diol in an inert solvent, e.g.
a halogenated hydrocarbon (such as methylene chloride, ethylene chloride, chloroform9 carbon tetrachloride etc.), and simultaneous or s~lbsequent halogenation. It is advantageous to add p-toluenesulfonic acid in order to speed up the reaction.

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

Ar-O-o~ ~ CO-CH2-Hal (XV) .~-Rb and further reaction of XV, in similar manner to variant A), with an azole of the formula II. Hal in ormula XV is preferably chlorine or bromine.

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

The process vaiants described ahove likewise constitute an object of the present invention.

~ 11 the above described ketalisation reactions of a ketone with a substituted ~ or ~,y-diol result in the formation primarily of mixtures of diastereoisomers of the resultant ketal. Likewise, mixtures of diastereoisomers of the final products of the formula I are generally obtained from the starting ketones. The compounds of formula I may be obtained eOg. in the two following diastereoisomeric forms:

Ar-~a ~02N Ar-O,~ /N/ N

~c~ type A
7 ~ ~
(XVI) C112ZR7 (XVII) R3 The configuration of type A will be designated here and referred to subsequently as ~Itrans~-isomer.

Ar-,~Ra =N type B Ar-O~R c~ y ~ '? 1 ~

(XVIII) C112~R; (XIX) R ~

The symbols in the three-dimensional s~ructures reproduced above have the following meanings:
..~. = behind _ = in ~æ~ - in front of the drawing planeO

The configuration of type B will be correspondingly designated as "cis"-isomer. The separation of the two diastereoisomers may be effected e.g. by fractional crystallisation or by chromatography ~thin-layer chromatography, column chromatography, liquid high-pressure chromatography etc.~. The two isomers have different biological properties~ For practical purposes the mixtures of diastereoisomers will normally be used.
. ;

The invention relates to all isomeric compounds of the formula I, and the salts and metal complexes thereof.

The process for obtaining compounds of the formula I
as described in variants A, B, C, and E likewise constitutes an object of the invention.

Some of the starting materials and intermediates employed in process variants A, B, C, D and E are known, and others can be prepared by methods which are known per se~ Some are novel and théir preparation is described herein.

~ Aryl)~thimidazolyl ketals, wherein aryl denotes substituted phenyl or naphthyl, are described as fungicides and bactericides in the following references: US patent specifieations 3 575 999, 3 936 470, 4 lOl 664, 4 lOl 666 and 4 156 008.

Surprisingly, it has been found that compounds of the formula I have for practical purposes a very advantageous microbicidal spectrum against phytopathogenic fungi and baeteria, as well as antimycotie and/or anticonvulsive properties whieh indicate their use as medicaments, For example, the compounds of formula I have very advantageous eurative, preventive and systemic phytotherapeutic properties and can be used for protecting cultivated plants, With the compounds of formula I it is possible to inhibit or destroy the microorganisms which oceur in plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the sam~ time the parts of plants whieh grow later are also protected from attack by such mieroorganisms.

The compounds of ~ormula I are effective in particular against the phytopathogenic fungi belonging to the following groups: Ascomycetes (e~g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidomycetes (e.g. the genera Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (e.g Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria). In addition, the compounds of formula I have a systemic action. They can also be used as seed dressing agents for protecting seeds (fruit, tubers, grains~ and plant cuttings aga;nst fungus infections as well as against phytopathogenic micro-organisms which occur in the soil. The compounds of the invention are also es;pecially well tolerated by plants.

Accordingly, the invention also relates to micro-bicidal compositions and to the use of compounds of the formula I for controlling phytopathogenic microorganisms, especially harmful fungi,and for the preventive treatment of plants to protect them from attack by such micro-organisms.

In addition, the invention rela~es to the preparation of agrochemical compositions, comprising intimately mixing a compound of the formula I with one or more substances or groups oi substances described herein. The invention further relates to a method of treating plants, which comprises applying thereto compounds of the formula I or novel compositions containing theml Target crops to be protected within the scope of the present invention comprise e.g. the following species of plants: cereals (wheat, barley, rye,oats, rice9 sorghum and related crops), beet (sugar beet and fodder beet)) drupes, ';~;

pomes and soft fruit (apples, pears, plums~ peaches, almonds, cherries, strawberries, rasberries and black-berries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy~ olives, sunflowers, coconuts, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows~ melons) fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemonsg grapefruit, mandarins), vegetable (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor)~ or plants such as maize~, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as ornamentals (composites).

The compounds of formula I are normally applied in agriculture in the form of compositions and may be applied to the crop area or plant to be treated, simultanPously or in succession, with further compounds.
These compounds can be both fertilisers or micronutrient donors or other preparations that influence plant growth.
They can also be selective herbicides, insecticides, fungicides, bactericides~ nematicides, mollusicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application-promoting adjuvants customarily employed in the art o~ formulation~ Suitable carriers and adjuvants for all formulations can be solid or liquid and correspond to the useful non~toxic substances ordinarily employed in formulation technology, e.g natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners or binders~

A preferred method in agriculture of applying a compound of the formula I or an agrochemical composition to an infested plant, is foliar (leaf) application. The number of applications and the rate of application depend on the intensity of infestation by the corresponding pathogen (type of fungus). However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). The compounds of formula I may also be applied to seeds (coating), by impregnating the seeds either with a liquid formulation containing a compo~nd of the formula I, or coating them with a solid formulation.
In special cases, further types of application are also possible3 e.g. selective treatment of the plank stems or buds.

The compounds of the formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substancesO Like the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are normally from 50 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a i /ha, most preferably from 200 g to 600 g a.i./ha.

The agrochemical formulations, i.e. the compositions or preparations containing the compound (active ingredient) of the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with e~tenders, e g. solvent, solid carriers and, where appropriate, surface-active compounds (sur~actants).

Suitable solvents are: aromatic hydrocarbons, preferably ~he fractions containing 8 to 12 carbon atoms, e.g. xylene ~lixtures or substituted naphthalenes, phthalates such as dibutyl phthalates or dioctyl phthalate, aliphatic hydrocarbons such as c~clohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vegetable oils such as epoxidised coconut oi] or soybean oil; or water.

The solid carriers used e.gO for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum,kaolin, montmorillonite or attapulgite.
In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers ! Suitable granulated adsorptive carriers are porous types, far example pumice, broken brick, sepolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the 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. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Suitable anionic surfactants can be both water~
soluble soaps and water-soluble synthetic surface-active compounds D

Sui-table soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22~, e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyl taurin salts.

More frequently, however, so-called synthetic surfactan~s are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkyl-arylsulfonates~

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and con~ain a C8-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts o~ sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or ~2~

triethanola~ine salts of dodecylbenzenesulfonic acid, dibutylnaph~halenesulfonic acid, or of a naphthalene-sulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphatesg e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic sur~actants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpoly-propylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 prpylene glycol ether groups, These compounds us~ally contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylenelpolyethylene oxide adducts, tributyl-phenoxypolyethoxyethanol, polyethylene glycol and octyl phenoxyethoxyethanol. Fatty acid esters o:E polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl 7 benzyl or lower hydroxy-alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. s~earyl-trimethylammonium chloride or benzyldi(2-chloroethyl)-ethylammonium bromide~

The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual''g MC Publishing Corp. Ringwood, New Jersey, 1979, and Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc.
New York, 1980.

The agrochemical compositions usually con~ain 0.1 to 99%, preferably 0.1 to 95%, of a compound of the formula I, 99.9 to 1%, preferably 99.8 to 5%, of a solid or liquid adjuvant, and among the adjuvants 0 ~o 25%, preferably 0.1 to 25% of a surfactant.

Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also contain further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.

Such agrochemical compositions also constitute an object of the presen~ invention.

~ ~h~W ~9 The antimycotic properties which indicate the utility of the compo~lnds of the formula I and their pharmaceutically acceptable acid addition salts for controlling parasitic fungi in warm-blooded animals, may be demonstrated e.g.
in vitro by means of conventional microbiological test methods, e g by determining their toxic action against fungus strains which are parasites of warm-blooded animals, for example against Trychophyton mentagryphites, Microsporum canis, Sporotrichum schenkii, Aspergillus fumigatus and Candida albicans; and also in vivo in guinea pigs by de~ermining the curative effect on experimental infestations on the dorsal skin with Trichophyton, e.g. T. rubrum, after peroral or local application.

The anticonvulsive properties of the compounds of formula I and their pharmaceutically acceptable acid addition salts may be demonstrated in vivo e.gO in mice by means of the pentatetrazole spasm test in the dose range from about 10 to 100 mg/kg p.o., and also by means of the electroshock test in the dose range from about 10 to 100 mg/kg p.o~ The anxiolytic properties can be demonstrated e.g. in mice and other small rodents by means of the Gellert test and the Quatre-Plaque test in the dose range from about 10 to 100 mg/kg p.o. It may also be inferred that the novel compounds have significant antimanic properties.

Accordingly, the present invention also relates to the use of compounds of the formula I and their pharma ceutically acceptable acid addition salts for the topical, local and systemic control of fungi which are parasites of warm-blooded animals, and for the systemic treatment of different forms of epilepsy, of states of anxiety and tension and of manic states o mind, in particular as active ingredients of pharmaceutical preparations, or for the production of pharmaceutical preparations, for enteral or parenteral or topical or local application, and relates also to such pharmaceutical preparations.
The pharmaceutical preparations of this invention which contain compounds of the formula I or pharmaceutically acceptable sal~s thereof, are accordingly ~hose for enteral, such as oral or rectal, and parenteral, administration, as well as for topical application to warm~blooded animals, which preparations contain the pharmacological active ingredient alone or together with a pharmaceutically acceptable carrier therefor. The dosage of the active ingredient depends on the species of warm-blooded animalg on the age and individual condition of the patient, and on ~he mode of administration or application.

For oral administration to a warm-blooded animal having a body weight of about 75 kg the approximate daily dose will normally be from 50 to 500 mg, conveniently distributed over several equal partial doses.

The pharmaceutical preparations of this invention contain e~g. from about 10% to 80%, preferably from about 20% to 60%, of active ingredient. Pharmaceutical preparations for enteral or parenteral administration are e.g. those in dosage unit form such as dragées, tablets, capsules or suppositories and also ampoules. These are prepared in a manner known per se, e.g. by conventional mixing, granulating, sugar-coating, dissolving or lyophilising methods. Thus pharmaceutical preparations for oral administration may be obtained by combining the active ingredient with solid carriers, optionally granulating the resultant mixture and, if desired or necessary, after addition of suitable adjuncts, processing the mi~ture or granulate to tablets or dragée cores.

Suitable carriers for tablets and/or dragées are in particular fillers such as sugar, for example, lactose, saccharose, mannitol or sorbitol, cellulose preparations and/or calcium phosphates, e.g. tricalcium phosphate or calcium hydrogen phosphate, also binders such as starch pastes, for example maiæe, corn, rice or potato starch paste, gelatin, tragacanth, methyl celluloseg hydroxy~
propylmethylcellulose, sodium carboxymethylcellulose and/or polyvinylpyrrolidone, and/or, if desired, disintegrators, such as the above starches, also carbogymethyl starch, crosslinked polyvinylpyrrolidone, agar, alginic acid or a salt ~hereof, such as sodium alginate. Adjuncts are chiefly glidants and lubricants, for example, silicic acid, talc, stearic acid or salts thereof, such as magnesium stearate or calcium stearate, and/or polyethylene glycol.
Sugar-coated tablet cores are provided with suitable coatings that can be resistant to gastric juices, using, inter alia, concentrated sugar solutions which may contain gum arabic, talc, polyvinylpyrrolidone, polyethylene glycol and/or titanium dioxide, shellac solutions in suitable organic solvents or solvent mixtures or, for the preparation of coatings resistant to gastric juices, solutions of suitable cellulose preparations, such as acetylcellulose phthalate or hydroxypropylmethylcellulose phthalate. Dyes or pigments can be added to the tablets or dragees cores, for example to identify or indicate different doses of active ingredient.

Further pharmaceutical preparations for oral administration are dry-filled capsules, and also soft sealed capsules made from gelatin and a plasticiser, such as glycerol or sorbitol. The dry-filled capsules may contain the active ingredient in the form of granules, for example in admixture with fillers such as lactose, binders such as starch and/or lubricants such as talcum or magnesium stearate, and optionally stabilisers. In soft capsules, the active ingredient is pre~erably dissolved or suspended in suitable liquids, for e~ample in fatty oils, paraffin oil or liquid polyethylene glycols, to which stabilisers can also be added.

Suitable dosage forms for rectal administration are for example suppositories, which consist of a combination of the active ingredient with a suppository base. Examples of suitable suppository bases are natural or synthetic triglycerides, paraffin hydrocarbons, polyethylene glycols or higher alcohols. Gelatin rectal capsules, which consist of a combination of the active components with a base material, can also be employed. Suitable base materials are for example liquid triglycerides, polyethylene glycols or paraffin hydrocarbons.

Particularly suitable ~or parenteral administration are aqueous solutions of an ac~ive ingredient in water-soluble form, e.g. a water-soluble salt, and also suspensions of the active ingredient such as suitable oily injection suspensions for which suitable lipophilic solvent~ or vehicles such as fatty oils, e.g. sesame oil, or synthetic fatty acid esters, e.g. ethyl oleate or triglycerides, are used, or aqueous injection suspensions which contain substances which increase the viscosity, e.g. sodium carboxymethylcellulose, sorbitol and/or dextrane~ and, if desired, also stabilisers.

Pharmaceutical preparations for topical application are e.g~ creams, ointments, pas~es, foams~ tinctures and solutions, which contain the acti-ve ingredient in an amount from about 0.5% to about 20%.

3~ ~

Creams are oil-in-water emulsions which contain more than 50% of water. Fatty alcohols are chiefly used as oleaginous base, for example lauryl~ cetyl or stearyl alcohol, fatty acids, for example palmitic or stearic acid, liquid to solid waxes, for example isopropyl myristate, wool wax or bees-wax, and/or hydrocarbons, for example petroleum jelly (petrolatum) or paraffin oil. Suitable emulsifiers are surface-active substances with primarily hydrophilic properties, such as corresponding non-ionic emulsifiers, for example fatty acid esters of polyalcohols or ethylene oxide adducts thereof, such as polyglycerol fatty acid esters or polyoxyethylene sorbitan fatty acid esters (Tweens~; polyoxyethylene fatty alcohol ethers or esters, or corresponding ionic emulsifiers, such as alkali metal salts of fatty alcohol sulfates, for example sodium lauryl sulfate, sodium cetyl sulfate or sodium stearyl sulfate, which are customarily used in the presence o fatty alcohol, for example cetyl alcohol or stearyl alcohol.
Additives to the water phase include agents which reduce water loss through evaporation, for example polyalcohols, such as glycerol, sorbitol, propylene glycol and/or poly-ethylene glycols, as well as preservatives, perfumes etc.

Ointments are water-in-oil emulsions which contain up to 70%, but preferably from about 20% to 50%9 of water or aqueous phase. The oleaginous phase comprises chiefly hydrocarbons, for example petroleum jelly~
paraffin oil and/or hard paraffins, which contain preferably hydroxy compounds suitable for improving the water-absorption, such as fa~ty alcohols or esters thereof, for example cetyl alcohol or wool wax alcohols, or wool wax.
Emulsifiers are corresponding lipophilic substances~ such as sorbitan fatty acid esters (Spans)g for example sorbitan oleate and/or sorbitan isostearate. Additives to the water phase include humectants, such as polyalcohols, for example glycerol, propylene glycol, sorbitol and/or polyethylene glycol, and preservatives, perfumes etc.

Greasy ointments are anhydrous and contain as base in particular 'nydrocarbons, for example paraffin, petroleum jelly and/or liquid paraffins, furthermore natural or partially synthetic fat, for example coconut fatty acid triglycerides, or preferably hardened oils, for example hydrated ground nut or castor oil, and also fatty acid partial esters of glycerol, for example glycerol mono- and distearate, and~ for example, the fatty alcohols, emulsifiers and/or additives for increasing the water-absorption mentioned in connection wîth the ointments.
Pastes are creams and ointments containing powdered ingredients which absorb secretions, such as metal oxides9 for example titanium oxide or zinc oxide, and talc and/or aluminium silicates whose purpose it is to bind moisture or secretion present.

Foams are administered from pressurised dispensers and are liquid oil-in-water emulsions in aerosol form, with halogenated hydrocarbons such as chlorofluoro-lower alkanes, for example dichlorodifluoromethane and dichloro-tetrafluoroethane, being used as propellants. For the oleaginous phas~ there are used, inter alia, hydrocarbons, for example paraffin oil, fatty alcohols, for example cetyl alcohol, fatty acid esters, for example isopropyl myristate~
and/or other waxesO As emulsifiers there are used, inter alia, mixtures of these emulsifiers with primarily hydrophilic properties, such as polyoxyethylene sorbitan fatty acid esters (Tweens), and those with primarily lipophilic properties, such as sorbitan fatty acid esters (Spans~. In addition, the conventional additives are used, such as preservatives etc.

Tinctures and solutions generally have an aqueous ethanolic base to which are added, inter alia, polyalcohols, for example glycerol, glycols, and/or polyethylene glycol, as humectants for reducing water loss, and fat-restoring substances, such as ~atty acid esters with lower poly-ethylene glycols, i.e lipophilic subs~ances which are soluble in the aqueous mixture as substitute for fatty substances which are taken from the skin with the ethanol, and, if necessary, other assistants and additives.

The pharmaceutical compositions for topical application are obtained in known manner, for example by dissolving or suspending the active ingredient in the base or in a part thereof, if necessary. When processing the active ingredient in the form of a solution, it is usually dissolved in one of the two phases be~ore the emulsi~ication, and when processing the active ingredient in the form of a suspension, it is mixed wi~h a part of the base before the emulsification and then added to the remainder of the formulation The following Examples will serve to illustrate the invention in more detail, but without implying any restriction to what is described therein. Parts and percentages are by weight and pressures are in millibars (mbar).

Preparatory Examples Example 1: Preparation of / \ / 3 .

o~ c ~12 ~ I
=. = =--2-[p-(Phenoxy)phenyl]-2-[l-(lH-1,2~4-triazolYl)methyll-4 methyl-1,3-dioxane a) Preparation of the intermediate / \ /C~l3 t I (.

/ \ /- C---CH2Br .=, .= .
2-[p-(Phenoxy)phenyl]-2-bromomethyl-4-methyl-1,3-dioxane 10 parts of 2-[p-(phenoxy)phenyl]-2-oxy-l-bromoethane and

4 parts of 1,3-butanediol are heated under reflux for 3 hours in 40 ml of absolute toluene in the presence of 0.2 part of p-toluenesulfonic acid as catalyst~ while removing the water of reaction with a water separator. The reaction mixture is cooled to room temperature, then washed with two 20 ml portions of water, dried over sodium sulfate and filtered. The solvent is removed by evaporation and the crude product is recrystallised from isopropanol to give colourless crystals with a melting point of 96-106C.

b) Preparation of the final product 3.3 parts of the sodium salt of 1,2,4-triazole and a catalytic amount of potassium iodide are stirred in 40 ml of dimethyl sulfoxide together with 10.2 parts of the 2-[p-(phenoxy)phenyl]-2-bromomethyl-4-methyl-1,3-dioxane ~3 obtained in a) for 3~ hours at a temperatur~ of 120C. The reaction mixture is cooled to room temperature, then diluted with 300 ml of water and extracted with three 30 ml portions of ethyl acetate. The combined extracts are w~shed with two 20 ml portions of water, dried over sodium sulfate, filtered, and the solvent is removed by evaporationO
The oiiy residue is purified by column chromatography over silica gel with ethyl acetate. The eluant is removed by evaporation and the oily residue crystallises from~
petrolèum ether to give brownish crystals with a melting point of 99,5-lOl~C.

Example 2: Preparation of ' Cl~ -0--~ ^~-~C/--CII~N/ I (3.226) --. ~ = . =--2-[p-(4-Chloro-2-methylphenoxy)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-1,3-dioxolane are dissolved in 150 ml of N,N-dimethyl formamide and then 1.9 parts of 55% sodium hydride dispersion are stirred in while introducing nitrogen. The mixture is heated for 2 hours to 80C, then cooled to room temperature, treated dropwise, with stirring, with 6.3 parts o~ methyl iodide over 1 hour, then heated for 2 hours to 60C, diluted with 800 ml of ice-water and extracted with three 300 ml portions o~ ethyl acetate. The combined extracts are washed with two 50 ml portions of water, dried over sodium sulfate, filtered, and the solvent is removed by evaporation. The residue is purified by column chromatography over silica gel with acetone/ethyl acetate (1:1). The eluant is then removed by evapora~ion and the mixture of diastereoisomers is crystallised by treatment with hexane~ giving beige-coloured crystals with a melting point of 92-106C

ExamplQ 3: Preparation of N0 _ / 2 5 CF3~ 0- ~ C/0 CH2-N~ 3 0 263) 2-[p-(2-Nitro-4-trifluoromethylphenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1~3-dioxolane 8,3 parts of 2-~p-(2-nitro-4-trifluoromethylphenoxy)phenyl]-2-~1-imidazolylmethyl)-4-ethyl-1,3-dioxolane are dissolved in 300 ml of dimethyl sulfoxide and to the solution are added 1.84 parts of ground potassium hydroxide, whereupon the temperature rises from 23 to 36C. Ater heating for 2 hours to 70C, 7.4 parts of 4-chloro-3-nitrobenzotrifluoride in 100 ml of dimethyl sulfoxide are added dropwise and stirring is continued for 3 hours at 70C. The reaction mixture is cooled to room temperature, poured into 2 litres of water and extracted with two 200 ml portions of diethyl ether. The combined extracts are washed with two 70 ml portions of water, dried over sodium sulfate, and the solvent is removed by evaporation. The oily residue is purified by column chromatography over silica gel with ethyl acetate. The eluant is removed by evaporation, leaving as residue a mixture of diastereoisomers in the form of a viscous mass.

- 41 ~

Example 4: Synthesis of &H2CE13 CH 2-N~ i ( 3 .1 2 ) 2-[p-(3-Ghlorophenoxy)phenyl3-2-(l~imidazolylmethyl)-4-ethyl-1,3-dioxolane 1.2 parts of imidazole sodium salt, 4 parts of 2-[p-(3-chlorophenoxy~phenyl]-2-bromomethyl-4-ethyl-l 3 3-dioxolane and a catalytic amount of potassium iodide are stirred in 50 ml o dimethyl formamide for 17 hours at a temperature of 125C, The brown reaction mixture is cooled to room tempera~ure, diluted with 150 ml of water and extrac~ed with three 50 ml portions of ethyl acetate. The comblned extracts are washed with two 50 ml portions of water, and dried over sodium sulfate. The solvent is removed by evaporation and the crude product is chromatographed over a 35 cm column of silica gel with acetone/ethyl acetate (1:1). The eluant is remcved by evaporation and the oily residue is crystallised from petroleum ether in the form of slightly yellowish crystals with a melting point of 69-71Co Example 5: Preparation of / ~ C/ CEI ~ (3 7) =- .=~ .=.

2~U~

2-[p-(4-Chlorophenoxy)phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane a) Synthesis of the intermediates K) Preparation of Cl--\ /--o-~ C~3 =. .=.

2-[p-(4-Chlorophenoxy)phenyl]-2-methyl-4 ethyl-1,3-dioxolane 37 parts of 4-(p-chlorophenoxy)acetophenone, 18 parts of 1,2-butanediol and 2 parts of p-toluenesulfonic acid as catalyst are heated under reflux in 400 ml of absolute toluene for 14 hours on a water separator. The reaction mixture is cooled to room temperature, washed with two 400 ml portions of water, dried over sodium sulfate and filtered. The solvent is removed by evaporation and the crude product is purified over a 1 m column of silica gel with ligroin/hexane/ethyl acetate/toluene (5:3~ The product is obtained in the form of a slightly yellowish oil; nD : 1.5527.

~) Preparation of Cl ~ o- ~ C~2-.=. .=.
2-[p-(4-Chlorophenoxy)phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane 36.8 parts of 2~[p-(4-chlorophenoxy)phenyl]-2-methyl-4-ethyl-1,3-dioxolane obtained in K) are heated to the boil .:

- ~3 -in 350 ml of chloroformO Under irradiation with a 150 watt spot lamp~ a solution of 19.4 parts of bromine in 50 ml of chloroform is added dropwise and the reaction mixture is subsequently heated under reflux for 2 hours. The reaction mixture is cooled to room temperature, then washed with two 200 ml portions of water, clried over sodium sulfate and filtered. The solvent is then stripped off under a water jet vacuum~ The crude product is purified by chromatography over a 1 m column of silica gel with toluene. The product is obtained in the form of an oil with a refractive index of n23: 1.5803, b) Synthesis of the inal product 4.4 parts of imidazole sodium salt, a catalytic amount of potassium iodide and 14.7 parts of 2-[p-(4-chlorophenoxy)-phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane obtained in ~) are s~irred in 80 ml of dimethyl formamide for 17 hours at a bath ~emperature of 125C. The reaction mixture is cooled to room temperature, then poured into 600 ml of water and extracted with three 200 ml portions of ethyl acetate. The combined extrac~s are washed with two 200 ml portions o water, dried over sodium sulfate and filtered.
The solvent is then removed by evaporation and the oily residue is chromatographed over a 50 cm column of silica gel with acetone/ethyl acetate (1:1). The eluant is removed by evaporation and the product is obtained in the orm of a brown oil with a refractive index of 1.5750 Example 6: Synthesis of &H2CH3 .. ._. ~ o o_ ~ ~-~/ CH -N/ T (1 9, . = . . . = .

2-[p-(Phenoxy)phenyl]-2-(1ll-1,2,4-triazolylmethyl)-4-ethyl-1,3-dioxolane 17 parts of 2-[p-(phenoxy)phenyl]-3-bromomethyl-4-ethyl-1,3-dioxolane, 8.4 parts of potassium carbonate, 4.2 parts of 1,2,4-triazole and a catalytic amount of sodium iodide are stirred in 100 ml of dimethyl formamide for 24 hours at a temperature of 125~C. The reaction mixture is cooled to room temperature, then poured into 600 ml of water and extracted with three 200 ml portions of ethyl acetate. The combined extracts are washed with 200 ml portions of water, dried over sodium sulfate and filtered~ The solvent is removed by evaporation and the oily residue is chroma~ographed over a 50 cm column of silica gel with chloroform/ether (1:1). The eluant is removed by evaporation and the oily residue is crystallised from petroleum ether in the form of wllite crystals with a melting point of 81.5-83.5C.

Example 7: Synthesis of .

/ \

~--0-~ C~CH2 N~
r = ~

2-~p-(Phenoxy)phenyl~-2-(lH-1,2,4-~riazolylmethyl)-1,3-dioxane 14 parts of 2~[p-(phenoxyphenyl~-2-bromomethyl-1,3-dioxane, 7.2 parts of potassium carbonate, 3.6 parts o 1~2,4-triazole and a catalytic amount of potassium iodide are stirred in 100 ml of dimethyl formamide for 20 hours at a temperature of 140C. The reaction mixture is cooled to room temperature, diluted with 600 ml of water and extracted with three 200 ml portions of ether~ The combined extracts are washed with two 200 ml portions of wa~er, dried over sodium sulfate and filtered. The solvent is evaporated and the oily residue is chromatographed over a 50 cm column of silica gel with chloroform/ether (1:1). The eluant is evaporated and the residue is crystallised from petroleum ~ther in the form o-f white crystals with a melting point o~ 129-130C

Example 8: Synthesis of ~CH20H

~ ~ CH2-N~N ~ (1. 23) _ . . = = .

2-[p-(Phenoxy)phenyl]~2-tlH 1,2,4-triazolylmethyl)-4-hydroxymethyl-1,3-dioxolane 4.5 parts of 2-[p~(phenoxy)phenyl]-2-bromomethyl-4-hydroxymethyl-1,3~dioxolane, 2.2 part 9 0f po tassium carbonate, 1.1 parts of 1,2,4-triazoLe and a catalytic amoun~ of potassium iodide are stirred in 50 ml of dimethyl sulfoxide for 4 hours at a temperature of 140C.
The reaction mixture is cooled to room ~empera~ure, then poured into 600 ml of wa er and extracted with two 200 ml portions of ethyl acetate~ The combined ex-~racts are washed with two 200 ml portions of water, dried over sodium sulfate and filtered. The solvent is evaporated and the oily residue is chromatographed over a 50 cm column of silica gel with acetone. The solvent is evaporated and the oily residue is crystallised from petroleum ether in the form of beige-coloured crystals with a melting point of 111-112C.

~ 2 ~xample 9: Synthesis of ,-o ~ c~H2 N~ T (1 17) , = . . = . .

2-~p-(Phenoxy)phenyl~2-(lH-1,2,4-triazolylmethyl)-4-n-propyl-1,3-dioxolane lU.3 parts of the nitrate of 1-(p-phenoxyphenyl)-2w(1,2,4 triazolyl)-ethanone, 6.1 parts of 1,2-pentanediol~ 6.9 parts of p-toluenesulfonic acid, ~0 parts of l-pentanol and 200 parts of xylene, are heated under reflux for 6 days on a water separator. The reaction mixture is then cooled to room temperature and then washed with two 200 ml portions of dîlute sodium hydroxide solution and with two 200 ml portions of waterO The organic phase is dried over sodium sulfate and filtered. The solvent is evaporated and the oily residue is chromatographed over a 1 m column of silica gel with ethyl acetate. The eluant is evaporated and the oily residue crystallises slowly in the form of beige-coloured crystals with a melting point of 68.5-71C, The following compounds of the formula I can also be prepared in analogous manner (unless otherwise specified, mixtures of diastereoisomers having different mixture ratios):

In the ollowing Tables 3 the symbol A stands for a diastereoisomer of type A, and B stands for a diastereo-isomer of type B.

Table 1: Compounds of the formula.

~ --\ /-7~ CH2 N\y T (XXI) \Rlo including isomeric forms:

Com- R Y Salt Physical data po~md 10 1.1 H N - m.p.100~102 1.2 H N HN03 1.3 H CH
1.4 CH3 N - m.p. 76.5-8l 1.5 CH3 N HCl 1.6 CH3 N CuC12 1.7 CH3 CH
1.8 CH3 N Mn(N03)2 1.9 C2H5 N - m.p. 81.5-83-5 1.10 C2HS N HN03 1.11 C2H5 N ZnC12 1.12 C2H5 N Mn(N03)2 1.13 C2H5 N FeCl3 1.14 C2H5 CH - light brown oil 1.15 C2H5 CH ~uC12 1.16 3 7 C}l 1.17 3 7 N - m.p. 68.5-71 - 1.18 C3ll7~n N ZnC12 1 .1 9 3 7 N HCl .~,., , '~ ~D ~f,~ q Table 1 (cont . ) Com- Rlo Y Sal t Physical data po~md 1.20 C4H9-n N --1.21 C~Hg-n CH
1.22 CH2Cl N
1.23 CH20H N - m.p, 111-122 1.24 ~-~' 011 ; nD =1.5865 . = .

1.25 ~ m-p- 83-85 B
.= .
_ .
1.26 2 \ / 3 m.p. ]07-109 A
.= .

1.27 2 \ / 3 m-p- 90-94 B
.= .
1.28 CH20H CH
1.29 CH20CH3 CH
1.30 C2H5 N 1/2CuS04 1.31 CH20C2H5 N
1.32 CH20CH3 N
1.33 CH20CH2CH20CH3 N

. .~."~.

3~ 3 Table 2: Compounds of the formula ~0~~ C - CH N/ T (XXII) including ~he isomeric forms:

Com- R R Y Salt Physical data pound 11 12 (C) 2.1 CH3C2H5 CH
2.2 CH3C2H5 N
2.3 CH3C2H5 CH HN03 2.4 CH3C21~5 N HN03 2.5 CH3 3 7 CH
2.6 CH3 3 7 N
2.7 CH3 3 7 N HN03 2.8 CH3 3 7 N Mn(No3)2 2.9 CH3 CH3 CH
2.10 CH3 CH3 CH C~ICl2 2.11 CH3C2H5 CH Mn(N03)2 2.12 CH3C2H5 CH CuCl2 2.13 CH3C2H5 N CuC12 2.14 CH3 2 S N ZnC12 2.15 CH3C2H5 N Mn(N03)2 2.16 CH3C2H5 N FeC13 23 2.17 CH3 CH3 N - oil ; nD = 1.5643 2.18 CH3 CH3 N HN03 2.19 C2H5CH3 CH MnC12 2.20 C2H5CH3 N MnC12 2.21 C2H5CH3 CH H2S04 2.22 C2H5CH3 CH ZnC12 Table 2 (cont.) Com- R R Y Salt pound 11 12 2.23 C2H5 C2H5 CH
2.24 C2H5 C2H5 CH H2SO4 2.25 C2H5 C2H5 N
2.26 C2H5 C2H5 N HNO3 2.27 C2H5 C2H5 N HCl 2.28 C2H5 3 7 N
2.29 C2H5 3 7 N .
2.30 C2H5 3 7 CH
2.31 C2H5 C3H7-n N HCl 2.32 C2H5 C2H5 N Mn(N03)2 2.33 CH3C2H5 N (COOH) 2 2.34 CH3C2H5 CH (COOH)2 2.35 CH33 7 N
2.36 CH3C3H7-i 2 4 2.37 -(CH2)4- CH
2.38-(CH2)4- CH HNO3 2.39-(CH2)4- N
2.40-(CH2)4- N Mn (NO3)2 2.41-(CH2)4- N (COOH)2 2.42-(CH2)4- N ZnC12 2.43( 2)4 N HCl 2.44-(CH2)4- CH ZnC12 ~, ~ o o . o. , o ~D o ~1 u o . ~
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. , Table 3 (cont . ) Com- 12 R13 14 15 16 Salt Physical data 3.157 H CH20GH3 H CF3 H H N
3.158 H CH20CH3 H H CF3 H CH
3.159 H CH20CH3 H H CF3 H N
3.160 H C2H5 H H CF3 H CH -3.161 H CH2OCH3 Cl H Cl H CH - , 3.162 H C2H5 Cl H H 5-Cl CH -nD = 1.5837 3.163 H CH20CH3 Cl H H 5-Cl N - 22 3.164 H C2H5 Cl H Cl H CH -nD = 1.5779 3.165 H H Cl H Cl H N
3.166 H CH20CH3 Cl H Cl H N
3.167 ~- CH20CH3 Cl H H 5-ClCH
3.168 H C2H5 Cl H H 5-Cl N - nD = 1.5788 3.169 H CH20CH3 Cl H H 6-ClCH
3.170 H CH20CH3 Cl H H 6-Cl N - 23 3.171 H C2'~5 H Cl Cl H CH - nD = 1.5835 3.172 H C2H5 H Cl Cl H N - m.p. 90-97 3.173 H C2H5 H C] H 5-Cl CH
3.174 H C2H5 Cl H H 6-Cl CH

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Table 4: Compounds of the fo-rmula Rl4~ /Rl3 ~18 R ~ ~~-\ ~i 7 C\O 2 ~ _~ (XXI~) includlng the isomeric forms:

pound 11 R12 R13 R14 Rl5 R16 YR17 R Salt , ;~
4.1 2 5 Cl H Cl H N 3-N2 H -4.2 2 5 3 H H N 2-CH3 H
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4.8 2 5 H Cl H 5-Cl N 2-Cl H
4.9 C2H5 H H Cl H 6-Cl CH 2-N02 H
4.10 CH3 CH3 ~ Cl H 6-Cl N 2-N02 H ~In(N03)2 4.11 H C2H5 Cl H H H N 2-Cl H

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~l o u o u u u u o o ~ u ~ C~ ~ C~ C~ C~ C~ C~ C~ C~
o ~ ~
--' I` t" u~
~I rY) ~rr~ ,3 r_ ~C
C~ C~ C~ C~ C~ X ~C ,,,~ _ a), ~

r.~o r ~ O ~ r,~l r.") ~t L~ r~ C~ O ~ r.~ ~'1 ~ U~
O ~ u~ u~ u~ u~ u~ u~ U~ u~

Table~ 4 (cont . ) Com- R RL2 R13 R14 R15 R16 Y Rl7 Rl8 Salt ( ~C) 4. 6 6 H CH3 H H F H CH 2-CH3 H
4.67 H CH20CH3 H H Cl H N 2-C1 H
4. 6 8 H C2H5 H Br H H CH 2-CH3 H
4. 6 9 H C2H5 F H H H CH 2-CII3 H -4.70 H CH3 H H F H CH 2-CII3 H _ light broT.~Tn resin 4.71 H CH20CH3 Er H H H N 2-Cl H -4.72- H CH20CH3 H Br H ~ CH 2-Cl H -4.73 H 2 3 H Br H CH 2-C1 H
4.74 H C2H5 H H Br H N 2-C1 H -4.75 H CH20CH3 H H J H CH 2-C1 H
4.76 H CH20CH3 H H J H N 2-C1 H
4-77 H 3 7 3 H ~I N 2-CH3 H H~3 m.p, 105-110 4.78 H CH3 3 H ~T ~T 2-CH3 H HNO3 m . p . 92-95 B
4-79 H C2H7_n ~- CH3 H H CH 2-C1 H
4-80 H CH20CH3 CH3 H H ~ CH 2-C1 H
4.81 H CH3 3 H 11 N 2-CH3 H HNO3 m.p. 129-134~ A
4.82 H CH20CH3 H H CH3 H ~T 2-C1 H
4.83 H CH20CH3 H H CH3 H CHT 2-CH3 H

Table 4 (cont.) Com- R R R R R R Y R R Salt Physical data pound 11 12 13 14 15 16 17 18 ( C) 4.84 H C2H5 H H C2H5 H N 2-C1 H
4.85 H 2 -3 C3H7i H H CH H ~ _ 4.86 H CH20CH3 C3H/i H H El CEI 2-NO2 H
4.87 H 2 3 2 5 1I CH 3-CH3 H -4.88 H 2 3 2 5 H N 2-Cl H _ 4.89 CH3 CH3 H H OCH3 E~ N 2-CH3 H - resin B
4,90 H 3 7 H H OCH3 H N 2-C113 H - oil ;~
4.91 H C3H7-n H H OCH3 H N 2-CH3 H - oil B
4.92 CH3 C~13 H H 3 N 2-C113 H - resin A
4.93 H C2El5 1~ El 3 N 2-CE~3 H - resin 4.94 El 3 7 H H OCH3 H N 2-CH3 El - oil 4.95 H CH OC H NO H H 11 CH 2-Br H
4.96 H CH20CE13 H El No2 1I Cll 2-Cl H
4.97 H CH2ll 3 ll Cll 3-Cll3 H
4.98 H CH2CH3 H H CF3 H Cll 2-C1 ll 4.99 H CH20CH3 H C1 H H CH 2-C1 H
4.100 H CH20CH3 B~ H B~ H Cll 2-C1 H
4.101 1I CH20CH3 C1 H Cl H CH 2-C1 ll Table 4 (cont . ~

Con~- R R12 R13 R14 R15 R16 Y R17 R18 Salt !.102 CH20H H (CH=CH)2 H H CH 2-Cl H
4.103 C2H5 H CH3 ¦ H Cl H CH 2-OCH3 6-ocH3 4.104 C2H5 H (CH=CH) H H CH 2-Cl H
4.105 CH~QCH3 H (CH=CH)2 H H CH 2-Cl H _ 4.106 CH20CH3 H (CH=CH)2 H H N H H -4.107 C2H5 H H (CH=CH)2 H CH 2-Cl H _ 4.108 C2H5 H H (CH=CH)2 H N 2-Cl H _ 4.109 C2H5 E~. (CH=CH)2 Cl H CH 2-Cl H _ 4.110 C2H5 H (CH=CH)2 Cl H N 2-Cl H
4.111 (CH2)4 H H Cl H CH H H
4.~12 CH20CH3 H Cl Cl H H CH 2-Cl H
'.113 C113 H H H Cl H N 3 4.114 C H H H H Cl H N 2-OCH3 6-ocH3 4.115 C2H5 H H H Cl H CH 2-OCH3 6-oCH3 '.116 C2H5 H H H Cl H N 2-CH3 H
4.117 CH3 CH3 H H F H N 2-CH3 H
'.118 CH3 CH3 H H F H CH 2-CH3 H
4.119 CH3 C2H5 H H ~ H N 2-CH3 H

~P ~U ~.D
- ~0 u r~ _ I ) (3 ~ ~C
r~
r~
C) o h rl r S~ h I

oo $ $ ~ ~: $ ~ ~ $ P: ~ ~ S
~a ~ ~ ~ $ $ ~ ~ ~ ~ x $ ~ $ $ $

$ ~d $ ~ ~ ~ ~;
Z ~ Z C~ Z ~) Z ~ Z Z Z

~o :~$$$X$$~ $$$$$:C$
U~

~
P~ ~ $ $ m $ ~ tc $ $ $ ~
r-l P~ ~ ~ $ $ ~ ~ ~ ~ ~ ~ ~ $ $ $ ~ X

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$ ~ ~ ~I ~ ~ $ ~ ~
C~ $ ~ Y y ~ ~ $ ~ ~ ~

~ X $ $ $ $ ~ $ $ $ ~ $

' 'r~fJ!Ai~ ~
~ 81 -Table 5: Compounds of the formula 2-N\y ;

including the isomeric forms:

Com- ~11 R12 Rl7 18 SaltPhysical data pounc ( C) 5.1 CH3 C2H5 2-Cl H CH
5.2 CH3 C2H5 2-Cl H N
5.3 CH3 C2H5 2-C1 6-Cl CH HN03 5.4 CH3 C2H5 2-CH3 H N HN03 5.5 CH3 C3H7~n 2-Cl H CH
5.6 CH C H -n 2-Cl H N
5-7 CH3 c3H7-n 3-Cl H N ~N03 5.8 CH3 C3H7-n 3-C1 6-Cl N Mn(N03)2 5.9 CH3 CH3 2-Cl H CH
5.10CH3 CH3 2-C1 6-Cl CH CuC12 5.11CH3 C2H5 2-Cl H CH Mn(N03)2 5.12C~13 C2H5 2-CH3 6~CH3 CH CuC12 5.13CH3 CH3 2-CH3 H N HN03 m.p. l58-160 5~14CH3 CH3 2-CH3 H N HBr m.p. 192-204 5.15CH3 C2H5 2-CH3 H N Mn(N03)2 5.16CH3 C2H5 2-N02 H N FeC13 5.17 CH3 CH3 2-Cl H N
5.18CH3 CH3 2-C1 5-Cl N HN03 5.192 5 3 3-Cl H CH MnC12 2 5 3 2-CH3 H N MnC12 5.21C2H5 CH3 2-CH3 H N CuC12 2 5 3 2-C1 5-Cl N ZnC12 2 5 2 5 2-Br H Cll 5.24 HC2H5 2-OCH3 6-OCH3 CH

3~

- ~32 -Table 5 (cont . ) ''om- ~ R R R Y Salt Physical data pound 11 12 1/ l8 (C) 5.25 H H 2-C1 11 N
5.2G H H 2-C1 ~I Cll 5.27 H H 2-C1 G-C1 Cll 5.28 H H 2-C1 H N Mn(;NO ) 5.29 11 H 2-C1 6-C1 N
5.30 H CH3 2-C1 H N
5.31 H CH3 2-C1 1I N IL~03 5.32 H CH3 2-C1 6-C1 N
5.33 H CH3 2-C1 H CH
5.34 H CH3 2-OCH 6-OCII CH
5.35 H CH3 3-C1 H N
5.36 ~ CH3 2-CH3 H N HN03 m.p.132-134"
5.37 H CH3 3-CH3 H N
5.38 H C2H53-CH3 H CH CuC12 5.39 H C2H52-CH3 6-CH3 N
5.40 H C2H52-CH3 H N HN03 m.p.108-110 5.41 H C2H5 2-Br 5-Br N
5.42 H C2H5 2-C1 H N
5 43 H C H -n2-C1 H N
5.44 H 3 7 2-C1 6-C1 N
5.45 H C3H7-i2-CH3 H N
5.46 H C3H7-i?--CH3 H CH
5.47 H C3H7-i2-OC113 '~-OCH3 N MnC12 5.49C2H5 C2H5 2-C1 H N HN03 5.51 H H 2-OCII ;-OCII CH
5.52C2H5 C3H7 i 2 C113 N

~.~
._~

Table 5 (cont.) Com- 1~ R R17 ~18 Salt Physical data 5.53 H C2115 2-oCH G-OCll N
5.54 H C2H5 2-OC~13 G-OC113 ~ -5.55 H 1-1 2-OCli G-OCH N
5.56 C~13 C2H5 3-Cl H N (COOH)2 5.57 CH3 C2H5 2-CU3 6-C113 CH (COOH)2 5.58 CH3 C3H7-i 2-Cl H N
5.59 CH C 11 -i 2-C1 6-Cl N H2S4 5.60 -(CH2)4- 2-Cl H CEI
5.61 -(CH2)4- 2-Cl H CH HN03 5.62 -(CH2)4- 2-Cl H N
5.63 -(CH2)4- 3-Cl H N ~In(N03)2 5.64 -(CH2)4- 3-C1 6-Cl N (COOH)2 5.65 -(CH2~4- 3-C1 5-Cl N ZnC12 5.66 -(CH2)4- 3-C1 6-Cl N IICl 5.67 -(CH2)4- 2-Cl H CH ZnC12 5.68 H H 2-CH3 H CH
5.69 CH3 CH3 2-CH3 H CH
5.70 H C3~17-n 2-CH3 H CH ~ yellow resin 5.71 H CH2CH3 2-CH3 H CH - resin 5.72 11 CH3 2-CH3 H CH
5.73 H C2H5 2-CH3 H CH
5.74 H CH2H 2-CH3 11 CH
5.75 H 2 3 3 N - oil 5.76 11 C2H5 2-C113 ~ N - resin 5.77 H H 2-C~13 ~I N - m .p . 103-loi 5.78 H C3117-n 2-C1~3 11 N - resin 5.79 ~I C1120~1 2-Cl 11 Cll 5.80 H C2~15 2-Br 11 Cll 5.81 11 C21-15 2-Cl 11 Cll O O O O O 'D 0~ n ~ W ~ ~ O ~D Co ~J O~ ~A ~ W ~ _ ~ y w ~ 1-- 0 _. (D
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:

Table 6 ~cont.) Com- R R R R R R R Y Salt Physical data poun~ 13 14 15. 16 17 18 19 (C)

6.65 H (CH=CH)2 H CH3 CH3 CH3 N
6.66 H (CH=CH)2 H H H H CH
6.67 Cl (CH=CH)2 H H H H N - , 6.68 Cl (CH=CH)2 H CH3 CH3 CH3 N - ~ 3b 6.69 Cl (CH=CH)2 H C2H5 H H N - ' .
6.70 Cl (CH=CH)2 6-Cl CH3 CH3 CH3 N -6.71 H (CH=CH)2 6-Cl CH3 CH3 CH3 N HN0 6.72 Br (CH=CH)2 H CH3 C2H5 CH3 N -6.73 CH3 (CH=CH)2 ~ CH3 C113 CH3 N
6.74 Cl Cl H 5-Cl H H H N
6.75 Cl H Cl 5-Cl H H H N
6.76 CH3 CH3 H H H H H CH
6.77 F H H H CH3 H H N
6.78 H F H H H H H N
6.79 H H F H H H H CH - oil 6.80 H H F H Cll3 il ~ CH - viscous mass 6.8i H H F H Cl13 H 11 N
6.82 Cl H H H C113 H 11 N

~9~

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m x ~

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h O ~ ~ ~ ~ ~ ~ ~ $ P: ~d ~~ .

~ O ~D

2~ ?

Table 7: Compounds o~ the formula 14\ / 13 C\ - CU2-N/ ~ (XXVII) 16 R2/ \ /

[R13 = R14 = H]
including the isomeric forms:

Com- R 2 R R24 R15 R16 Y Salt Physical data

7.1 H CH3 H H H N
7.2 H CH3 H H H CH -7.3 CH3 CH3 H H H N - m.p. 122-124 7.4 CH3 CH3 H H H N HN03 7.5 CH3 CH3 CH3 H H N Mn(N03)2 7.6 CH3 CH3 CH3 H H CH -7.7 CH3 CH3 H Cl 6-Cl - oil; nD = 1.5782 3 C2HS H H H N CuC12 7.10 CH3 C2H5 CH3 CH3 6-CH3 CH (COOH)2 7.11 C2H5 C2H5 H H H N HN03 7.12 C2H5 C2H5 H H H N
7.13 C2H5 C2H5 H H H CH HCl 7.14 C2H5 C2H5 H H H CH FeC13 7.16 H C2H5 H 3 N
7.17 H C2H5 H H H N HN03 7.18 HC2H5 H H H ` CH -7.19 H3 7 H H N CuC12 7.20 HC3H7 n H H H CH -7.21 CH3 C113 C31]7 n H H N - m.p. 119-121 7.22 HH H H H CH -7.23 CH3 CH3 H H H CH -~ ~3 Tablc 7 (cont . ) Com- 1~22 23 R24 r~l5 ~ Salt Physical data pound 7 . 24 H H C113 ll H CH -7 . 25 ll H C113 ll 11 N 1/2 C~ISO
7 . 2G H H 1-1 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 CH3 H 6-Cl Cll -7 . 30 H H H H 5-Cl Cll -7 . 31 H H H il 5-Cl N
7 . 32 H H CE13 Cl H Cll -7.33 H H H Cl H Cll - viscous mass 7.34 H H H Cl ~ N - oil 7 . 35 H H CH3 Cl H N
7 . 36 H H H CH3 H N
7 . 3 7 H H H 3 7 N
7 . 38 H H H N02 H N
7 . 39 H H H H 6-CF3 N
7 . 40 H H CH3 H 5-CF3 N
7 . 41 H H H CF3 H N
7 . 42 H H H Cl 5-Cl N
7 . 43 11 H H Cl 5-C113 CH -3 2 5 No2 5-C113 N -7 . 45 CH3 C113 H C~3 6-Cl Cll -7.46 C113 CH3 C 117-1~ C~ N 2 2~

o o '_ ~_ - C~ I I I I $ I Z I ~ I I

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a.~ r 1 Table 8 ~cont.) pound 11 Rl2 R13 R14 R15 R16 17 18 19 Physical data

8.66 2-CH3 H H E' H H H H H CH - brown resin 8.67 2-CH3 H F H H H H H H N
8.68 2-CH3 E~ H H Cl H H H H N -8 69 2-CH H H H Cl l~ H H H CH - brown resin 8.70 2-CH3 H H H Cl H CH3 H H N -8.71 2-CH H H H Cl H CH3 EL H CH - -~
8.72 2-CH H H H F H H H H N - resin . ~U

8.73 2-CH3 H H H F H H H H CH -8.74 2-CH3 H H H F H CH3 El H N
8.75 2-CH3 H H H F H Cl13 H H CH

Table 9: Compounds of the formula 14\ ~13 ~11 R -o~ ~a-O~ 9 - C - C~l -N/ T (XXIX) 16 12 ~\
2 ~ \
R `R
including the isomeric forms:
~ound 11 12 13 R14 R15 R16 R22R23 R24 Y Salt

9.1 2-Cl H H H H H H CH3 H N
9.2 2-Cl H 11 Cl H 6-Cl H CH3 H CH -9.3 2-Br H Br H H H 3 3 H N
9.4 2-CH3 6-CH3 H H H H 3 3 H N HN03 9.5 2-C1 6-Cl Cl H H 6-Cl CH3CH3 CH3 N Mn(N03)2 9.6 2-Cl o-Cl H Cl H H 33 CH3 CH -9.7 2-C1 5-Cl H H Cl H 3CH3 H
9.8 2-Cl H H Cl Cl H 2 2 5 N
9.9 2-Cl H Cl H H H CH3 C2H5 H N CuC12 9.10 3-C1 5-Cl Cl H H 6-Cl CH3 C2H5 CH3 CH (COOH)2 9.11 2-C1 6-Cl H H Cl H C2H5 C2H5 H N HN03 9.13 2-CH3 ll CH3 CH3 H H C2H5 C2H5 H CH HCl 9.14 2-Cl H 3 H H C2H5 C2H5 H CH FeC13 9.15 2-C1 5-Cl Cl H H H C2H5 C2H5 H CH -9.16 2-Cl H Cl Cl Cl 5-Cl H C2H5 H N
9.17 2-Cl H H Cl Cl H H C2H5 H N HN03 9.1S 2-CH3 5-CH3 CH3 ~I H 6 3 C2H5 H CH -9.19 2-CH3 6-CH3 H H CH3 H 3 7 N CuC12 9.20 2-C1 6-Cl H H CH3 H H C3H7 n H CH -9.21 3-N02 H H H Cl H H H CH3 N
9.22 H H Cl H Cl 6-CH3 CH3 CH3 H N
9.23 H H CH H Br 6-Cl CH CH C H -n CH -9.24 ~I H CH3 H Br 6-Cl CH3 C2H5 H N

Tabl.e 10 :. Compounds of the formula ~C~ 2 ~:T ~xxx~

including the isomeric forms:

pound 11 R12 R13 R14 R15 16 U V Salt

10.1 H H C1 H C1 H N CH3 CH3 10.2 H . H C1 H C1 H N C1~3 CH31 ( 3)2 10. 3 H H CH3 3 Cll Cl-l 2 5 10. 4 H H CH3 H Ci~3 S-CH3 N C2~15 ~ C2Hs -10.5 H H H C1 H 5-Cl N C 1-1 -n 4 9 10. 6 H H H Cl ~1 6-Cl ~ C3i~7-i 3 7 CuC12 10. 7 H H H H H H i~l C~13 3 10. ~ H H T,~ H :~ 11 CH C1~3 C~13 10. 9 H H H H 11 ~E ~ C3H7~n C3H7-n (COOH) 2 10.10 2-C1 H H H C1 H iY C~13 C~3 10. 11 2-C1 6-Cl 1~ Cil3 C~13 10.12 3-C1 H H H 1-1 1i ~' C21~5 C,H5 10.13 2-C1 6-C1 H H C1 H . 8 17 8 17 Table 1() (cont . ~
Com- Rll R12 R13 R14 R15 16 U V Salt pound 10.14 2-CH3 H H CH3 H H 2 5 C2H5 HCl 10.15 2-CH 6-CH CH H H H N C3H7-i 3 7 10.16 2-CH3 H CH3 CH3 H H N C5Hll-n 5 11 10.17 2-C1 5-Cl Cl H H 6-Cl N CH3 3 10.18 2-C1 5-Cl H H Cl H N C4Hg-s C4Hg-s ~
10.19 2-C1 6-Cl Cl Cl Cl 6-Cl CH CH3 3 , _ 10.20 2-Cl H (CH=CH)2 H H N CH3 3 10.21 2-CH3 H (CH=CH)2 H H N CH3 3 7 10.22 H H 77. H H H CH CH3 3 10.23 H H H H H H 2 5 C2H5 10.24 H H H H H H 4 9 4 9 10.25 H 7i H H 7d 2 2 3 2 2 3 10.26 H H H H H H ~ 2 2 2 5 2 2 2 5 10.27 7d H H H H 8 17 8 17 10.28 H H H H H H N (CH2)20CH3 (CH2)20 3 10.29 2-CH3 H H H H H CH CH3 CH3 10.3G 2-CH3 H H H H H N ~CH2)2~CH3 (CH2)20 3 10.31 2-Cl H H H H H CH (CH2)20CH3(CH2)20CH3 - lOL -$ - ~ $ X $
O O O O R O
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a~ , o E~~ oooooooooooooooooo Formulation Examples for a~rochemical compositions containin~ liquid active in~redients of the formula I
(throughout, percentages are by weight) 10. Emulsifiable concentrates a) b) c) compound of Tables 1 to 10 25% 40% 50%
calcium dodecylbenzenesulfonate 5% 8% 6%
castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5% - -tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) - 12% 4%
cyclonexane - 15% 20%
xylene mixture 65% 25% 20%

Emulsions of any required concentration can be produced from such concentrates by dilution with water.

11. Solutions a) b) c) d) compound of Tables 1 to 10 80% 10% 5% 95%
ethylene glycol monomethyl ether 20% - - -polyethylene glycol 400- - 70%
N-methyl-2-pyrrolidone - 20%
epoxidised coconut oil - - 1% 5%
ligroin (boiling range 160-190C) - - 94%

These solutions are suitable for application in the form of microdrops.
.

2~

12. Granulates a) b) compound of Tables 1 to 10 5% 10%
kaolin 94%
highly dispersed silicic acid 1%
attapulgite - 90%

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

13. Dusts a) b) compound of Tables 1 to 10 2% 5%
highly dispersed silicic acid .1% 5%
talcum 97%
kaolin - 90%

Ready for use dusts are obtained by intimately mixing ~he carriers with the active ingredient.

Formulation examples for agrochemical compositions containing solid active ingredients of the formula I
(throughout, percentages are by weight)

14. Wettable powders a) b) c) compound of Tables 1 to 10 25% 50% 75%
sodium lignosulfonate 5% 5%
sodium laurylsulfate 3% - 5%
sodium diisobutylnaphthalene-sulfonate - 5% 10%
octylphenol polyethylene glycol ether (7-8 moles o ethylene oxide) - 2%
highly dispersed silicic acid 5% 10% 10%
kaolin 62% 27%

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

15. Emulsifiable concentrates compound of Tables 1 to 10 10%
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3%
calcium dodecylbenzenesulfonate 3~/0 castor oil polyglycol ether (36 moles of ethylene oxide) 4%
cyclohexanone 20%
xylene mixture 50%
coconut oil 10%.

Emulsions of any required concentration can be obkained from this concentrate by dilution with water.

16. Dusts a) b) : compound of Tables 1 to 10 5% 8%
talcum 95%
kaolin - 92%

Ready for use dusts are obtained by mixing the active ingredient with the carriers, and grinding ~he mixture in a suitable mill.

17. Extruder ~ranulate compound of Tables 1 to 10 10%
sodium lignosulfonate 2%
carboxymethylcellulose 1%
kaolin 87%.

;

?3 The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.

18. Coated ~ranulate compound of Tables 1 to 10 3%
polyethylene glycol 200 3%
kaolin 9~%

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.
Non-dusty coated granulates are obtained in this manner.

19. Suspension concentrate compound of Tables 1 to 10 ~0 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 %
sodium lignosulfonate 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 ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Formulation Examples for Pharmaceutical Preparations

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

- log -Composition Active ingredient 5.0%
white petroleum jelly45-0%
liquid paraffin 19.6%
cetyl alcohol 5.0%
beeswax 5-0%
sorbitan sesquloleate5.0%
p-hydroxybenzoate 0.2%
demineralised water to make up 100.0%

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

21. Cream A cream con~aining 10% of 2-[p-(chlorophenoxy)phenyl~-2~
imidazolylmethyl)-4-ethyl-1,3-dioxolane may be prepared as follows:

Composition active ingredient 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%
demineralised water to make up 100.0%

The acrylic acid polymer is suspended in a mixture of demineralised water and 1,2~propylene glycol. Triethanolamine is then stirred in to give a mucilage. A mixture of iso-propyl palmitate, cetyl palmitate, silicone oil, sorbitan monostearate and polysorbate is heated to about 75C and then stirred into the mucilage, which is also heated to about 75C. After it has cooled to room temperature, the cream base is used to prepare a concentrate with the active ingredient. This concentrate is homogenised using a continuous homogenisex, and then added in portions to ~he base.

A cream containing 5% of 2-[p-(chlorophenoxy)phenyl~-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane may be prepared as follows:

Composition active ingredient 5.0%
cetyl palmitate PH 2.0V/~
cetyl alcohol PH 2.0%
triglyceride mixture of saturated medium fatty acids 5.0%
stearic acid 3.0%
glycerol stearate PH ~.0%
Cetomacrogol 1000 1.0%
microcrystalline cellulose 0.5%
1,2-propylene glycol (dist.) 20.0%
dem-Lneralised water to make up 100.0%

The cetyl alcohol, cetal palmitate, triglyceride mixture, stearic acid and glycerol stearate are melted together. The microcrystalline cellulose is dispersed in a portion of the water. The Cetomacrogol is dissolved in the remainder o~ the water and both the propylene glycol and the mucilage are blended therewith. The fatty phase is ~hen stirred into the aqueous phase and the mix is st-Lrred cold. Finally, the active ingredient is milled with a portion of the base and ~2~U3 then incorporated in the rest of the cream.

22. Hydro~e~s A transparent hydrogel containing 5% of 2-[p-(chlorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyldioxolane is prepared as follows:

Composition active ingredient 5%
propylene glycol 10-20%
isopropanol 20%
hydroxypropyl methyl cellulose2%
water to make up 100%

The hydroxypropyl methyl cellulose is expanded in water. The active ingredient is dissolved in a mixture of isopropanol and propylene glycol. The active ingredient solution is then blended with an expanded cellulose derivative and~ if desired, perfume (0.1%) is added.

23. Foam sprays A foam spray containing 1% of 2-[p-(chlorophenoxy)phenyl]-2-(l-imidaæolylmethyl)-4-ethyldioxolane may be prepared as follows:

Composition active ingredient 1.00%
cetyl alcohol PH 1.70%
liquid paraffin (viscous) 1.00%
isopropyl myristate 2.00%
Cetamacrogol 2.40%
sorbitan monostearate 1.50%
1,2-propylene glycol PH 5.00%
me~hyl parabene 0.18%

- 112 ~
propyl parabene 0.02%
Chemoderm 314 0.10%
demineralised water to make up 100.00%

The cetyl alcohol, liquid paraffin, isopropyl myristate, Cetomacrogol and sorbitan stearate are fused together. The methyl and propyl parabene are dissolved in hot water. The melt and the solution are then blended. A swspension of the active ingredient in propylene glycol is incorporated in the base. Chemoderm is then added and the composition is bulked with water to the final weigh~.

Fillin~
20 ml of the composition are filled into an aluminium dispenser. The dispenser is fitted with a pressure cap and filled with propellant gas under pressure.

24. Capsules Gelatin capsules containing 200 mg o~ [p-(pheno~y)phenyl]-2-[l-tlH-1,23~ riazolyl)methyl]-1,3-dioxane as active in-gredient may be prepared as follows:

Composition (for 1000 capsules) active ingredient 100 g lactose (gound) 100 g The active ingredient and the lactose ~micronised) are well mixed. The resultant powder is sieved and packed into gelatin capsules of 0.2 g.

25. Tablets Tablets containing 25 mg o~ active ingredient, e.g. 2-[p-(phenoxy)phenyl[-2-~1-(lH-1,2,~-triazolyl)methyl]-1,3-dioxane, may be prepared as follows:
....

~ 2~ 3 Composition (for 1000 tablets) active ingredient 25.0 g lactose 100.7 g corn starch 7.5 g polyethylene glycol 60005.0 g talcum 5.0 g magnesium stearate 1.8 g demineralised water q.s.

Preparation All the solid ingredients are first passed through a sieve having a mesh size of 0.6 mm. Then the active ingredient, the lactose, talcum, magnesium stearate and half of the starch are blended together. 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 1000 ml of water and the mixture is granulated, if necessary with the addition of water. The granulate is dried overnight at 35C, passed through a 1.2 mm sieve and compressed to biconcave tablets of about 6 mm diameter.

Tablets containing 75 mg of active ingredient, e.g. 2-~p-(phenoxy)phenyl]-2-[1-(lH-1,2,~-tria~olyl)methyl] 1,3-dioxane, may be prepared as follows:

Composition ( for 1000 tablets) active ingredient 75.0 g lactose 100.7 g corn starch 7.5 g polyethylene glycol 60005.0 g talcum 5.0 g magnesium stearate 1.8 g demineralised water q.s~

Preparation All the solid ingredients are first passed through a sîeve having a mesh size of 0.6 mm. Then the active ingredient, the lactose, talcum, magnesium stearate and half of the starch are blended together. The other half of the starch is sus-pended 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 with the addition of water. The granulate is dried overnight at 35C, passed through a 1. 2 mm sieve and compressed to biconcave tablets of about 6 mm diameter.

Pharmaceutical preparations containing another compound of Tables 1 to 10 may laso be prepared in analogous manner.

Biolo~ical Examples Example 26 Ac~ion a~ainst Puccinia ~ramini~ on wheat a) Residual-protec~ive action Wheat plants are treated 6 days after sowing with a spray mixture prepared from a wettable powder formulakion of the active ingredient (0~06%)o After 24 hours the treated plants are infected with a uredospore suspension of the fungus.
The infected plants are incubated for 48 hours at 95-lOOa/o relative humidity and about 20~C and then stood in a green-house at about 22C. Evaluation of rust pustule development is made 12 days after infection.

b) Systemic action Wheat plants are treated 5 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0~06% based on the volume of the soil).
After 48 hours the treated plants are infected with a uredos-pore suspension of the fungus. The plants are then incubated for 48 hours at 95-100% relative humidity and about 20C
and then stood in a greenhouse at about 22C. Evaluation ~ P~u of rust pustule development is made 12 days after infection.

Compounds of Tables 1 to 10 are very effective against Puccinia fungi. Puccinia infestation is 100 ~ on untreated, infected control plants. Residual-protective treatment with compounds 1.17, 1.24, 2.17, 3.1, 3.6, 3.7, 3.133, 3.164, 3.168, 3.220, 3.267, 3.311, 3.314, 4.50, 4.77, 4.81, 4.90, 4.91, 493, 4.94, 5.13, 5.14, 5.36, 5.70, 6.8 and 7.7 among others, inhibits fungus attack to 0-5%. In addition, compound 6.8 has a full systemic action (0% attack3 even when diluted to a concentration of 0.006%.
xample 27: Action a~ainst Cercospora arachidicola in ~roundnut plants Groundnut plants 10-lS cm in height are sprayed with a spray mix~ure prepared from a wettable powder formulation of the active ingredient (concentration 0.02%) and infected 48 hours la~er with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at about 21C and high humidity and then stood in a greenhouse until the typical lea~
specks occur. Evaluation of the fungicidal action is made 12 days af~er infection, and is based on the number and size of the specks.

Compared with untreated and infected controls (number and size of the specks = 100%), the plants treated with compounds of Tables 1 to 10 exhibit greatly reduced attack by Cercospora. For example, compounds 1.9, 1.14, 1.17, 1.24, 1~26, 1.27, 2.17, 3.6, 3.7, 3.11, 3.133, 3.162, 3.171, 3.172, 3.176, 3.177, 3.221, 3.231, 3.232, 3.234, 3.314,4050, 4.89, 4.90, 4.91, 4.92, 4.93. 4.94, 5.13, 5.14, 5.36, 5.40, 5.70, 5.71, 5.73, 5.75, 5.76, 5.78, 6.1 and 6.8 inhibit the formation of specks in tis test almost completely (0 to 5 %
attack).

~A~U ~

Example 28: Ac~ion a~ainst Erysiphe ~raminis on barley a) Residual protective ac~ion Barley plants about 8 cm in height are sprayed with a spray mixture (0.02%) prepared from the ac~ive ingredient formulated as a wettable powder. The treated plants are dus~ed with conidia of the fungus af~er 3-~ hours. The infected barley plants are then stood in a greenhouse at about 22~C. The f~mgus a~tack is evaluated after 10 days.

b) Systemic action Barley plants about 8 cm in height are ~rea~ed with a spray mixture (o.006%, based on the volume of the soil) prepared from the ~c~ive ingredient formulated as we~able powder.
Care is taken that the spray mixture does not come in contac~ with the parts of the plants above the soil. The treated plants are infected 48 hours later with a conidia suspension of the fungus. The infected barley plants are then stood in a greenhouse a~ about 22~C and evaluation of fungus infestation is ~ade after 10 days.

Compounds of the formula I have a good residual-protective action against Erysiphe fungi. Erysiphe infestation of untreated, infected control plants is 100%. Among others, compounds 1.1, 1.9, 1.17~ 1.23~ 1.24~ 1.25~ 1.26~ 1.27~ 2.17 3.1 t 3.2 ~ 3.6 ~ 3.7 ~ 3.8, 3.11, 3.12 ~ 3.26 3.127 r 3.133 ~
3.164, 3.168~ 3.172~ 3.176, 3.177, 3.193~ 3.226~ 3.231, 3.233, 3.267, 3.274, 3.311, 3.314, 4.50, 4.78, 4.~9, 4.90, ~.91~ 4.92~ 4.93~ 4.94~ 5.13~ 5.14~ 5.36~ 5.~0~ 5.70~ 5.7 5.73, 5.75, 5.76~ 5.78~ 6.1/ 6.8, 7.3~ 7.7 and 7.21 inhibit fungus attack to less than 5 % . Compound 4.50 iS also effective in soil treatment (systemic action~ and when diluted to a concentration of 0.006%.

Example 29: Residual-protective action a~ainst Venturia inaequalis on apple shoots Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.06%. After 2~ hours the treated plants are infected with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100% relative humidity and stood in a greenhouse for a further 10 days at 20-24C. Scab infestation ls evaluated 15 days after infection. Compounds 1.9, 1.17, 1.24, 2.17, 3.6, 3.7, 3.11, 4.50, 4.81, 4.89, 4.90, 4.91, 4.92, 5.13, 5.14, 5.36, 5.40, 5.70, 6.1 and 6.8 and others inhibit infestation to less than 10%. Venturia infestation is 100%
on untreated, infected shoots.

Example 30: Action a~ainst Botrytis cinerea on beans a) Residual protective action Bean plants abcut 10 cm in height are sprayed with a spray mixture (0.02%) prepared from the ac-tive ingredient ~ormulated as wettable powder. After 48 hours, ~he treated plants are infected with a conidia suspension of the fungus.
The infec~ed plants are incubated for 3 days at 95-100%
relative humidity and 21C, and evaluation of the fungus attack is then made. Compounds of Tables 1 to 10 very strongly inhibit fungus infestation in many cases. At a concentration of 0.02 %, compounds l.l, l.9, 3.6, 3.7, 3.231, 4.50, 4.78, 5.13, 5.36, 5.40, 5.70, 5.71, 5.73, 5.75, 5.77, 6.1 and 6.8 are fully effective (0 to 5 % attack). sotrytis infestation of untreated, inf~cted bean plants is loO gd.

Claims (50)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the preparation of an aryl phenyl ether derivative of the formula I, and the acid addition salts and the copper, manganese, iron, organic complexes thereof, wherein Y is -CH= or -N=, Ra and Rb, each independently of the other, are hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy or nitro, Ar is phenyl or naphthyl, each unsubstituted or mono- or polysubstituted by halogen, C1-C7alkyl, C1-C7alkoxy, nitro and/or CF3, U and V, each independently of the other, are C1-C12alkyl which is unsubstituted or substituted by halogen or C1-C6alkoxy, or together form one of the following alkylene bridges wherein R1 and R2, each independently of the other, are hydrogen, C1-C12alkyl or C1-C12alkyl which is mono- or polysubstituted by halogen;
phenyl or phenyl which is mono- or polysubstituted by halogen and/or C1-C3alkyl; or are the -CH2-Z-R7 group, wherein Z is oxygen or sulfur and R7 is hydrogen, C1-C8alkyl or C1-C8alkyl which is substituted by C1-C2 alkoxy; C3-C4alkenyl, propyn-2-yl, 3-halo-propyn-2-yl, phenyl or phenyl which is mono- or polysubstituted by halogen C1-C3alkyl and/or C1-C3 alkoxy, nitro and/or CF3; benzyl or benzyl which is mono- or polysub-stituted by halogen, C1-C3alkyl and/or C1-C3alkoxy, R3, R4 and R5, each independently of the other, are hydrogen or C1-C4alkyl, the total number of carbon atoms in R3, R4 and R5 not exceeding 6, and R6 is hydrogen or C1-C3alkyl, which process comprises:
A) condensing a compound of the formula II

(II) , wherein Me is hydrogen or a metal cation, with a compound of the formula III

(III) , wherein X is a leaving group, or B) in a compound of the formula IV

(IV) converting the carbonyl group into a group of the formula V

(V) C) condensing compounds of the formulae VI and VII

(VII), wherein one of the radicals X1 and X2 is hydroxyl or mercapto which may be in salt form, e.g. of the formula -Z-Me, and the other is a leaving group X, or both X1 and X2 are hydroxyl groups, with each other, to give compounds of the formula I, wherein U and V together are a group of the formula -CH2-CH(CH2ZR?)- and R? is a radical which differs from hydrogen, or D) condensing compounds of the formulae VIII and IX

(IX), wherein one of the radicals X3 and X4 is an O-Me group, in which Me is hydrogen or preferably a metal cation, and the other is a radical which is replaceable by aryloxy, with each other, or E) subjecting a compound of the formula (X) to intramolecular decarboxylation; and F) if desired, converting the obtained compound of formula I into an acid addition salt thereof, and/or G) if desired, converting the obtained compound of formula I into the copper, manganese, iron or zinc complex thereof.

2. Aryl phenyl ether derivatives of formula I as defined in claim 1, whenever prepared by the process of claim 1 or by an obvious chemical equivalent thereof.

3. A process according to claim 1A, 1B, 1D, or 1E
wherein Y is -CH= or -N=, each of Ra and Rb independently of the other is hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy or nitro; Ar is the group wherein Rc, Rd and Re, each independently of the other, are hydrogen, halogen, C1-C3 alkyl, C1-C3alkoxy, nitro or CF3, U and V, each independently of the other, are C1-C12alkyl or together form one of the following alkylene bridges wherein R1 and R2, each independently of the other, are hydrogen, C1-C12alkyl or C1-C12 alkyl which is mono- or polysubstituted by halogen, or are phenyl or phenyl which is mono- or polysubstituted by halogen and/or C1-C3alkyl, or are the -CH2-Z-R7 group, in which Z is oxygen or sulfur and R7 is hydrogen, C1-C8alkyl or C1-C8alkyl which is substituted by C1-C2alkoxy, or is C3-C4alkenyl, propyn-2-yl, 3-halopropyn-2-yl, phenyl or phenyl which is mono- or polysubstituted by halogen, C1-C3alkyl, C1-C3alkoxy, nitro and/or CF3, or is benzyl or benzyl which is mono- or polysubstituted by halogen, C1-C3alkyl and/or C1-C3-alkoxy, R3, R4 and R5, each independently of the other, are hydrogen or C1-C4alkyl, the total number of carbon atoms in R3, R4 and R5 not exceeding 6, and R6 is hydrogen or C1-C3alkyl.

4. Aryl phenyl ether derivatives of formula I as defined in claim 3, whenever prepared by the process of claim 3 or by an obvious chemical equivalent thereof.

5. A process according to claim 1A, 1B, 1D or 1E
wherein Y is -CH= or -N=, each of Ra and Rb independently of the other is hydrogen, halogen or C1-C3alkyl, Ar is the group wherein each of Rc, Rd and Re independently of the other is hydrogen, halogen, CF3, C1-C3alkyl, C1-C3alkoxy and U and V are as defined in claim 1.

6. A process according to claim 1C wherein Y, Ra, Rb, Ar, U and V are as defined in claim S with the proviso that R1 or R2 is -CH-Z-R7 in which Z
and R7 are as defined in claim 1.

7. A process according to claim 1A, 1B, 1D or 1E
wherein Y is -CH= or -N=, each of Ra and Rb independently of the other is hydrogen, halogen or C1-C3alkyl, Ar is the group wherein each or Rc, Rd and Re independently of the other is hydrogen, halogen, CF3, C1-C3alkyl, C1-C3alkoxy and in which each of U and V independently of the other is C1-C6-alkyl, C2-C4alkyl which is unsubstituted or substituted by halogen or C1-C2alkoxy, or together form one of the following alkylene groups wherein each of R1, R2, R3, R4 and R5 independently of the other is hydrogen or C1-C4alkyl, the total number of carbon atoms in R3, R4 and R5 not exceeding 6.

8. A process according to claim 1C wherein Y, Ra, Rb, Ar, U, and V
are as defined in claim 3 with the proviso that R1 or R2 is -CH-Z-R7 in which Z and R7 are as defined in claim 1.

9. A process according to claim 1A, 1B, 1C, 1D or 1E
wherein Y is -CH= or -N=, each of Ra and Rb independently of the other is hydrogen, halogen or C1-C3alkyl, Ar is the group wherein each of Rc, Rd and Re independently of the other is hydrogen, halogen CF3, C1-C3alkyl, C1-C3alkoxy and in which U and V together are the alkylene group wherein R7 is C1-C4alkyl, C2-C4alkyl which is substituted by C1-C2alkoxy, or is C3-C4alkenyl or propyn-2-yl.

10. A process according to claim 1A, 1B, 1D or 1E
wherein Y is -CH=, Ar is the group each of Ra and Rb independently of the other is hydrogen, methyl, chlorine or bromine, each of Rc, Rd and Re independently of the other is hydrogen, fluorine, chlorine, bromine, methyl, methoxy, CF3 or nitro,each of U and V independently of the other is C1-C3alkyl which is unsubstituted or substituted by C1-C2 alkoxy or chlorine, or together form one of the alkylene groups as defined for formula I, wherein each of R1, R2, R3, R4, R5 and R6 independently of the other is hydrogen or C1-C3alkyl, or R1 is -CH2OR7, wherein R7 is C1-C3 alkyl, C2-C3alkyl which is substituted by C1-C2alkoxy, or is C3-C4alkenyl.

11. A process according to claim 10, wherein Y, Ar, Ra, Rb, U and V
are as defined in claim 10, with the proviso that R1 or R2 is -CH2-Z-R7 in which Z and R7 are as defined in claim 1.

12. A process according to claims 1A, 1B, 1D, or 1E wherein Y is -CH= or -N=, each of Ra and Rb independently of the other is hydrogen, halogen or C1-C3alkyl, Ar is phenyl or phenyl which is substituted by C1-C3alkyl, C1-C3alkoxy, CF3 or halogen, and U and V are as defined in claim 1.

13. A process according to claim 1C wherein Y, Ar, Ra , Rb U and V are as defined in claim 12, with the proviso that R1 or R2 is -CH2-Z-R7 in which Z and R7 are as defined in claim 1.

14. A process according to claims 1A, 1B, 1D, or 1E
wherein is -CH= or -N=, each of Ra and Rb independently of the other is hydrogen, methyl, chlorine or bromine, Ar is phenyl or phenyl which is substituted by halogen, methyl or CF3, and each of U and V independently of the other is C1-C3alkyl, C2-C3alkyl which is unsubstituted or substituted by C1-C2 alkoxy, or together form one of the following alkylene groups wherein each of R1, R2, R3, R4 and R5 independently of the other is hydrogen or C1-C4alkyl, the total number of carbon atoms in R3, R4 and R5 not exceeding 4.

15. A process according to claims 1A, 1B, 1D, or 1E
wherein Y is -CH= or -N=, Ra and Rb are hydrogen, Ar is phenyl or phenyl which is substituted by halogen or methyl, and U and V together are a group of the formula wherein R2 is C1-C4alkyl such as methyl or ethyl, or C1-C3hydroxyalkyl such as hydroxymethyl or 2-hydroxyethyl, or C1-C2alkoxy-C1-C2alkyl such as methoxy-methyl or ethoxymethyl.

16. A process according to claim 1C wherein Y, Ar, Ra , Rb, U and V are as defined in claim 15 with the proviso that R1 or R2 is -CH2-Z-R7 in which Z and R7 are as defined in claim 1.

17. A process for the preparation of 2-[p-(phenoxy)-phenyl]-2-[1-(1H-1,2,4-triazolyl)-methyl]-4-methyl-5methyl-1,3-dioxolane which comprises reacting 1,2,4-triazole with2-[p-(p-phenoxy)-phenyl]-2-bromoethyl-4-methyl-5-methyl-1,3-dioxolane.

18. 2-[p-(Phenoxy)-phenyl]-2-[1-(1H-1,2,4-triazolyl)-methyl]-4-methyl-5-methyl-1,3-dioxolane whenever prepared by the process of claim 17 or by an obvious chemical equivalent thereof.

19. A process for the preparation of 2-[p-(phenoxy)-phenyl]-2-[1-(1H-1,2, 4-triazolyl)-methyl]-1,3-dioxane which comprises reacting together 2-[p-phenoxy) phenyl]-2-bromomethyl-1,3-dioxane in the presence of potassium carbonate and potassium iodide.

20. 2-[p-(Phenoxy)-phenyl]-2-[1-(1H-1,2,4-triazolyl)-methyl]-1,3-dioxane whenever prepared by the process of claim 19 or by an obvious chemical equivalent thereof.

21. A process for the preparation of 2-[p-(phenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane which comprises condensing imidazole sodium salt with2-[p-(phenoxy)-phenyl]-2-bromomethyl-4-ethyl-1,3,dioxolane.

22. 2-[p-(Phenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-etthyl-1,3-dioxolane whenever prepared by the process of claim 21 or by an obvious chemical equivalent thereof.

23. A process for the preparation of 2-[p-(2,4-dimethylphenoxy)-phenyl]-2-(1-imidazolylmethyl-4-ethyl-1,3-dioxolane which comprises condensing imidazole sodium salt with2-[p-(2,4-dimethylphenoxy)-phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane.

24. 2-[p-(2,4-Dimethylphenoxy)-phenyl]-2-(1-imidazolyllmethyl-4-ethyl-1,3-dioxolane whenever prepared by the process of claim 23 or by an obvious chemical equivalent thereof.

25. A process for the preparation of 2-[p-(3-chlorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane which comprises condensing imidazole sodium salt with2-[p-(3-chlorophenoxy)-phenyl]-2-bromomethyl-4-ethhyl-1,3-dioxolane in the presence of sodium iodide.

26. 2-[p-(3-Chlorophenoxy)-phenyl]-2-(1-imidazolylmethhyl)-4-ethyl-1, 3-dioxolane whenever prepared by the process of claim 25 or by an obvious chemical equivalent thereof.

27. A process for the preparation of 2-[p-(4-chlorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane which comprises condensing imidazole sodium salt with2-[p-(4-chlorophenoxy)-phenyl]-2-bromomethyl-4-ethhy1-1,3-dioxolane in the presence of sodium iodide.

28. 2-[p-(4-Chlorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1, 3-dioxolane whenever prepared by the process of claim 27 or by an obvious chemical equivalent thereof.

29. A process for the preparation of 2-[p-(3-trifluoromethylphenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane which comprises condensing imidazole sodium salt with 2-[p-(3-trifluoromethylphenoxy)-phenyl]-2-bromo-methyl-4-ethyl-1,3-dioxolane.

30. 2-[p-(3-Trifluoromethylphenoxy)-phenyl]-2-(1-imidazolyl-methyl)-4-ethyl-1,3-dioxolane whenever prepared by the process of claim 29 or by an obvious chemical equivalent thereof.

31. A process for the preparation of 2-[p-(4-chloro-3-methyl-phenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane which comprises condensing imidazole sodium salt with 2-[p-(4-chloro-3-methyl)-phenoxy)-phenyl]-2-bromo-methyl-4-ethyl-1,3-dioxolane.

32. 2-[p-(4-Chloro-3-methyl-phenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane whenever prepared by the process of claim 31 or by an obvious chemical equivalent thereof.

33. A process for the preparation of 2-[p-(3,4-dichlorophenoxy)-phenyl]
-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane which comprises condensing imidazole sodium salt with 2-[p-(3,4-dichloro-phenoxy)-phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane.

34. 2-[p-(3,4-Dichlorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane whenever prepared by the process of claim 33 or by an obvious chemical equivalent thereof.

35. A process for the preparation of 2-[p-(2,5-dichlorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane which comprises condensing imidazole sodium salt with 2-[p-(2,5-dichlorophenoxy)-phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane.

36. 2-[p-(2,5-Dichlorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane whenever prepared by the process of claim 35 or by an obvious chemical equivalent thereof.

37. A process for the preparation of 2-[p-(3,4-dichlorophenoxy)-phenyl]
-2-(1-imidazolylmethyl)-4-methoxymethyl-],3-dioxolane which comprises condensing imidazole sodium salt with 2[p-(3,4-di-chlorophenoxy)-phenyl]-2-bromomethyl-4-methoxymethyl-1,3-dioxolane.

38. 2-[p-(3,4-Dichlorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-methoxymethyl-1,3-dioxolane whenever prepared by the process of claim 37 or by an obvious chemical equivalent thereof.

39. A process for the preparation of 2-[p-(4-fluorophenoxy-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane which comprises condensing imidazole sodium salt with 2-[p-(4-fluorophenoxy)-phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane.

40. 2-[p-(4-Fluorophenoxy-phenyl]-2-(1-imidazolylmethyl)-4-ethyl-1,3-dioxolane whenever prepared by the process of claim 39 or by an obvious chemical equivalent thereof.

41. A process for the preparation of 2-[p-(4-chloro-2-methyl-phenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-methoxymethyl-1,3-dioxolane which comprises reacting 2-[p-(4-chloro-2-methyl-phenoxy)-phenyl]-2-(1-imidazolylmethyl-4-hydroxymethyl-1,3-dioxolane in sequence with sodium hydride and with methyl iodide in sequence.

42. 2-[p-(4-Chloro-2-methyl-phenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-methoxymethyl-1,3-dioxolane whenever prepared by the process of claim 41 or by an obvious chemical equivalent thereof.

43. A process for the preparation of 2-[p-(phenoxy)-phenyl]-2-[1-(1H-1,2,4-triazolyl)-methyl]-4-hydroxymethyl-1,3-dioxolane which comprises condensing 1,2,4-triazole in the presence of pot-assium carbonate and potassium iodide with 2-[p-(phenoxy)-phenyl]-2-bromomethyl-4-hydroxymethyl-1,3-dioxolane.

44. 2-[p-(Phenoxy)-phenyl]-2-[1-(1H-1,2,4-triazolyl)-methyl]-4-hydroxymethyl-1,3-dioxolane whenever prepared by the process of claim 43 or by an obvious chemical equivalent thereof.

45. A process for the preparation of 2-[p-(4-fluorophenoxy)-phenyl]-2-(1-(lH-1,2,4-triazolyl)-methyl)-1,3-dioxane which compri-ses condensing 1,2,4-triazole with 2-[p-(4-fluorophenoxy)-phenyl]-2-bromomethyl-1,3-dioxane.

46. 2-[p-(4-Fluorophenoxy)-phenyl]-2-(1-(1H-1,2,4-triazolyl)-methyl)-1,3-dioxane whenever prepared by the process of claim 45 or by an obvious chemical equivalent thereof.

47. A process for the preparation of 2-[p-(4-fluorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-hydroxymethyl-1,3-dioxolane which comprises condensing imidazole sodium salt with 2-[p-(4-fluoro-phenoxy)-phenyl]-2-bromomethyl-4-hydroxymethyl-1,3-dioxolane.

48. 2-[p-(4-Fluorophenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-hydroxymethyl-1,3-dioxolane whenever prepared by the process of claim 47 or by an obvious chemical equivalent thereof.

49. A method of controlling or preventing attack on crop plants by phytopathenogenic micro-organisms which method comprises a microbiocidally effective amount of a compound of formula I as defined in claim 1 to the plants or to the locus thereof.

50. A method of controlling phytopathogenic micro-organisms or protecting cultivated plants from attack by said micro-organisms, which method comprises applying to said plants, to parts of said plants, or to a locus to be protected, a microbio-cidally effective amount of an aryl phenyl ether derivative of formula I as defined in claim 1.