CA1222766A - Aromatic oxiranes - Google Patents

Abstract

Case 5-14227/+/DIV

ABSTRACT OF THE DISCLOSURE
Aromatic oxiranes of the formula II

II

in which Ar is phenyl, biphenyl, phenoxyphenyl or naphthyl, R2 is hydrogen, fluorine, or C1-C6 alkyl and R3 is hydrogen, fluorine, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl, phenoxy, phenylthio or C3-C1 cycloalkyl, and in which any aromatic groups can be mono- or poly-substituted with halogen, C1-C4-alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, nitro, and/or cyano are described. These compounds find use in the preparation of 1-azolyl-2-aryl-3-fluoro-alkan-2-ols, which are microbicides.

Description

27~;~

_ L 21489-6415D
Aromatic Oxiranes Case 5-14227/+/DIV
This Application is a divisional from Application 4~3,044, filed December 12, 1983.
Application 443,044 relates to substituted 1-azolyl-2-aryl-3-fluoroalkan-2-ols and ethers thereof, of the formula I below; to acid addition salts, quaternary azolium salts and metal complexes thereof;
to the preparation of these substances; to microbicidal compositions containing at l.east one o:E these compounds as the active substance;
to the preparation of the above compositions; and to the use of ~he active substances or of the compositions for the control of harmful microorganisms, preferably fungi which are harmful to plants.
The compounds according to Application 443,044 are those of the general formula I
OR R
Az - CH2 - C - - C - F (I) Ar R3 in which Az is lH-1,2,4-triazole, 4H-1,2,4-triazole or lH-imidazole; Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, biphenyl, phenoxyphenyl and naphthyl; Rl is hydrogen, Cl-C4-alkyl, C3-C5-alkenyl or benzyl; R2 is hydrogen, fluorine or Cl-C6-alkyl and R3 is hydrogen, fluorine,Cl-C6-alkyl, Cl-C6-haloalkyl, Cl-C6-alkoxy, Cl-C6-alkylthio, phenyl, phenoxy, phenylthio or C3-C7-cycloalkyl, and each aromatic substituent or aromatic moiety of a substituent is unsubstituted or mono- or poly-substituted by halogen, Cl-C~-alkyl, Cl-C

~, 3L~2~7~;

alkoxy, Cl-C4-haloalkyl, nitro and/or cyano; including the acid addition salts, quaternary azolium salts and metal complexes.
The term alkyl by itself or as a constituent of another substituent is to be understood as meaning, for example, one of the following groups, depending on the number of carbon atoms stated: methyl, ethyl, propyl, butyl, pentyl, hexyl and the like and their isomers, for example isopropyl, isobutyl, tert.-butyl, isopentyl and the like. Haloalkyl is a monohalogenated to perhalogenated alkyl substituent, for example CHC12, CHF2CH2Cl, CC13, CH2F, CH2CH2Cl CH2Br and the like, in particular CF3. Here and in the following text, halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. ~lkenyl is 9 for example, prop-l-enyl, allyl, but-l-enyl, but-2-enyl or but-3-enyl. Naphthyl is ~- or ~- naphthyl.
Examples of salt-forming acids are inorganic acids, such as hydrogen halide acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid ? as well as sulfuric acid, phosphoric acid, phosphorous acid and nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, or methanesulfonic acid.
Metal complexes of the formula I consist of the basic organic molecule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates~ trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates and the like of the elements of the third and fourth main group, such as aluminium, tin or lead, and of the first to eighth sub-group, such as chromium, manganese, iron, cobalt, nickel, zirconium, copper, zinc, silver, mercury and the like.
The sub-group elements of the ~th period are preferred. The metals can be in the various valences with which they are associated. The metal 76~i complexes of the formula I can be mononuclear or polynuclear, i.e. they can contain one or more organic molecule components as ligands. Complexes with the metals copper, zinc, manganese, tin and zirconium are preferred.
The compounds of the formula I are oils, resins or, chiefly solids, which are stable at room temperature and are distinguished by very useful microbicidal properties. They can be used preventively and curatively in the agricultural sector or related fields for controlling micro-organisms which damage plants, the triazolylmethyl derivatives in the context of the formula I
being preferred. The active substances of the formula I according to the invention are distinguished by a very good phytofungicidal action and problem-free application when used in low concentrations. Moreover, they also have a growth-regulating action, in particular a growth-inhibiting action, especially on tropical cover crops.
According to Application 443,044, the following groups of substances are preferred, because of their marked microbicidal action, in particular their phytofungicidal action: compounds of the formula I in which Az is lH-1,2,4-triazole or lH-imidazole; Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, biphenyl and phenoxy-phenyl, ~1 is hydrogen; R2 is hydrogen, fluorine or Cl-C3-alkyl; and ~3 is hydrogen, fluorine, Cl-C4-alkyl, Cl-C3-haloalkyl, Cl-C3-alkoxy, Cl-C3-alkylthio, phenyl, phenyloxy or phenylthio, each phenyl moiety being unsubstituted or substituted by fluorine, chlorine, bromine, methyl, methoxy, CF3, N02 and/or cyano; including the acid addition salts, quaternary azolium salts and metal complexes.
Particularly preferred compounds of the formula I within this group are those in which Az is lH-1,2,4-triazole; Ar is phenyl or phenoxyphenyl which is unsubstituted or, preferably, substituted in the 2- and/or 4-position ~2~2t76~

by methyl or halogen, preferably fluorine or chlorine; Rl is hydrogen;
R2 is hydrogen, fluorine or methyl; and R3 is hydrogen, fluori.ne, Cl-C4-alkyl or a radical from the series comprising phenyl, phenoxy and phenylthio which is substituted by fluorine, ch.Lorine and/or bromine.
Examples of specific particularly preferred substances from a fllngicidal point of view are: l-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluorobutan-2-ol, 1-(lH-1,2,4-triazo].-1-yl)-2-(2-chloro-4-fluorophenyl)-3-fluorobutan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluoro-pentan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluoro-4-methylpentan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(2-chloro-4-fluorophenyl)-3-fluoropentan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-(4-chlorophenoxy)-3-fluoropropan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-[p-(4-chloro-phenoxy)phenyl]-3-fluoropropan-2-ol,l-(lH-1,2,4-triazol-1-yl)-2-(4-fluoro-phenyl)-3,3,3-trifluoropropan-2-ol, :L-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichloro-phenyl)-3,3,3-trifluoropropan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(4-chloro-phenyl)-3-fluorohexan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluorohexan-2-ol, 1-~lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl-3,3-difluoropentan-2-ol,l-(lH-1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-3-fluoro-4-methylpentan 2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-[p-(4-bromophenoxy)phenyl]-3,3-difluoropropan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-[p-4-fluorophenoxy)phenyl]-3,3-difluoro-propan-2-ol, 1-(lH-1,2,4-triazol-1-yl)-2-[p-(4-chlorophenoxy) phenyl]-3,3-difluoropropan-2-ol and 1-(lH-1,2,4-triazol-1-yl)-2-[p-(4-chloro-phenoxy)-2-methylphenyl]-2-hydroxy-3-fluoropropane.
According to Application 443,044, the compounds of the formula I are prepared by a process which comprises first reacting an oxirane of theformulca II

Ar- ~ ~CH2 (II) F

;27~

with an azole of the formula III
~Az (III) to give a compound of the formula Ia OH
. Ar-C-CR -Az (Ia) and, if required, converting the alcohol Ia into an ether of the formula I ;n the conventional manner, for example by re-act;on with a compound of the formula IV
R1 ~ W (IV) in which formulae Ia, II, III and IV, the substituents R1, R2, R~, Ar and Az are as defined under formula I, M is hydrogen or, preferably, a metal atom, in particular an alkali metal atom, such as Li, Na or K, and W is OH or a con-ventional leaving group. Conventional leaving groups are known from the literature.
If appropriate, the reaction of II with III to give Ia is carried out in the presence of condensing agents or acid-binding agents. Suitable agents are organic and inor-ganic bases, for example tertiary amines, such as trialkyl-amines (trimethylamine, triethylamine, tripropylamine and the like), pyridine and pyridine bases (4-dimethylaminopyri-dine, 4-pyrrolidylaminopyridine and the like), oxides, hyd-rides and hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals tCaO, BaO, NaOH, KOH, NaH, CatOH)2, KHC03, NaHC03, CatHC03)2, K2C03, and Na2C03) and alkali metal acetates, such as CH3COONa or CH3COOK. Moreover, alkali metal alcoholates~ such as C2H50Na, C3H7-nONa and the like, are also suitable~
In some cases, it may be advantaseous if the free azole III
tM = hydrogen) is first converted into the corresponding salt, for example in situ with an alcoholate, and then to react the salt with the oxirane of the formula II. In the preparation of the 1~2,4-triazole derivatives, 1,3,4-triazolyl isomers are generally also formed in a parallel reaction, and these ~Z27~6 can be separated from one another in a conventional manner, for example with different soLvents.
The reaction (II with III to give Ia) is preferably carried out in an organic solvent which is relatively polar but inert in the reaction, for example N,N dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, acetonitrile, benzo-nitrile and the like~ Such solvents can be used in combina-tion with other solvents which are inert in the reaction, for example benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene and the like. The reac-tion temperatures are in a temperature range from 0 to 150C, preferably 20 to 100C.
This reaction (II with III to give Ia) can further-more be carried out analogously to reactions which are al-ready known for other oxiranes with azoles (cf. German Offen-legungsschrift 2,912,288).
In the part reactions mentioned, the intermediates can be isolated from the reaction medium and, if desired, purified by one of the generally conventional methods, for example by washing, digestion, extraction, crystallisation, chromatography, distillation and the like, before the further reaction.
In cases where W in formula IV is a conventional leaving group, the further reaction of Ia to give I is car-ried out in the absence or, preferably, in the presence of asolvent which is inert in the reaction.
Examples of suitable solvents are the following:
N,N-dimethylformamide, N,~-dimethylacetamide, hexamethyl-phosphoric acid triamide, dimethylsulfoxide, 2-methyl-2-pen-tanone and the like. Mixtures of these solvents with oneanother or with other conventional inert organic solvents, for example with aromatic hydrocarbons, such as benzene, toluene, the xylenes and the like, can also be used. In some cases it may prove advantaseous to carry out the reaction in the presence of a base, for example an alkali metal hydride, hydroxide or carbonate, in order to accelerate the rate of reaction. However, it may also be advantageous first to convert the alcohol of the Formula Ia (R1 = OH) into a sui-table metal salt ;n a manner which is known per se, for ex-ample by reaction w;th a strong base.
Examples of su;table strong bases are alkali metal hydr;des and alkaline earth metal hydr;des (NaH, KH, CaH2 and the like) and alkali metal-organic compounds, for ex-ample butyl-l;th;um or an alkali metal tert.-butoxide, and alkali metal hydroxides, such as NaOH or KOH, can moreover also be used if the reaction is carried out in an aqueous two-phase system ;n the presence of a phase transfer cata-lyst.
However, it is also possible first to convert the alcohol of the formula Ia into an alkali metal alcoholate in a conventional manner before the further reaction, and then to react the alcoholate with a compound of the formula IV (in wh;ch W is a leaving group>, the reaction advanta-geously being carried out in the presence of a crown ether.
If M = K, 18-crown-6, in particular, is present; and if M =
Na, 15-crown 5, in particular, is present. The reaction is ZO advantageously carried out in a medium which is inert in the reaction. Examples of suitable solvents are ethers and ether-like compounds, for example di-lower alkyl ethers (di-ethyl ether, diisopropyl ether, tert.-butyl methyl ether and the like), tetrahydrofuran and dioxane, and aromatic hydro-carbons, such as benzene, toluene or the xylenes.
The following solvents are examples of the organicwater-immiscible phase: aliphatic and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, petroleum ether, lig-roin, benzene, toluene, the xylenes and the like, halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, 1,Z-dichloroethane, tetrachloroethylene and the like, or aliphatic ethers, such as diethyl ether, diisopropyl ether, t-butyl methyl ether and the like. Examples of suitable phase transfer catalysts are: tetraaLkYlammon;um halides, bisulfates or hydroxides~
such as tetrabutylammonium chloride, bromide or iodide; tri-ethylbenzylammon;um chloride or bromide; tetrapropylammonium ~2~766 chloride, bromide or iodide; and the like. Possible phase transfer catalysts include phosphonium salts. The reaction temperatures are in general between 30 and 130C, or at the boiling point of the solvent or solvent mixture.
In cases where W in formula IV is a hydroxyl group, a condensation reaction is advantageously carried out. The two reactants are refluxed in a suitable solvent.
In principle, any solvent which is inert towards the reactants and, advantageously, forms an azeotrope with water can be used here. ~xamples of suitable solvents here are aromatic hydrocarbons, such as benzene, toluene and the xylenes, or halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetra-chloroethylene and chloro-benzene, as well as ether-like compounds, such as tert.-butyl methyl ether, dioxane and the like. In some cases, the compound of the formula III itself can be used as the solvent. This condensation reaction is advantageously carried out in the presence of a strong acid, for example paratoluenesulfonic acid, at the boiling point of the azeotropic mixture.
To prepare the ethers of the formula I, it is also possible first to replace the free OH group in the compounds of the formula Ia by one of the above conventional leaving groups W and then to react the product with a compound of the formula IV twhere W = OH).
The starting substances of the formula III are generally known, or they can be prepared by methods which are known per se.
The oxiranes of the formula II are novel, and are intermediates which have been developed particularly for the preparation of the useful active substances of the formula I. Because of their structural nature, they can be converted in-to the compounds of the formula Ia in a simple manner, and, moreover, some of the compounds of the formula II have a fungicidal activity towards harmful fungi from the families of Ascomycetes, Basidiomycetes or Fungi 27~6 - 8a -imperfecti.
Thus this invention provides aromatic oxiranes of the formula II

Ar-C - CH2 II

in which Ar is an unsubstituted or substituted aromatic radical chosen from phenyl, biphenyl, phenoxy-phenyl and naphthyl;
R2 is hydrogen, fluorine or Cl-C6 alkyl; and R3 is hydrogen, fluorine, Cl-C6 alkyl, Cl-C6 haloalkyl, Cl-C6 alkoxy, Cl-C~ alkylthio~ phenyl~
phenoxy, phenylthio or C3-C7 cycloalkyl, wherein each aromatic radical or moiety is unsubstituted or mono- or poly-substituted by halcgen, Cl-C4 alkyl, Cl-C4 alkoxy, Cl-CL haloalkyl, nitro and/or cyano.
Epoxides of the formula II can be prepared Erom ~L~2Z~766 ketones o-f the formula V

~r~C-C-F (V) Il I
o ~3 in a manner which is known per se by reaction with dimethyl-sul-Fonium methyLide or dimethyloxosulfonium methylide (Corey and Chaykovsky, JACS, 1962, 84, 3782).
The ketones of the formula V are accessible by me-thods which are known per se from the literature (cf. J. Le-roy, J. Org. Chem. 46, 2û6 (1981) or Houben-Weyl, volume V/3, page 211), from the corresponding known a-bromo-ketones by conventional replacement of the bromine by fluorine, or they can also be prepared by acylation of the aromatic on which they are based with fluorinated carboxylic acid deri-vat;ves, for example by a Friedel-Crafts reaction.
In principle, unless expressly specified in a parti-cular case, one or more solvents or diluents which are inertin the reaction can be present in the preparation of all the starting substances, intermediates and end products mentioned here. Examples of suitable solvents or diluents are alipha-t;c and aromatic hydrocarbons, such as benzene, toluene, the xylenes and petroleum ether; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene;
ethers and ether-like compounds, such as dialkyl ethers (di-ethyl ether~ diisopropyl ether, tert.-butyl methyl ether and the like), anisole, dioxane and tetrahydroFuran; nitriles, such as acetonitrile and propionitrile; N,N-dialkylated amides, such as dimethylformamide; dimethylsulfoxide; ke-tones, such as acetone, diethyl ketone and methyl ethyl ke-tone, and mixtures of these solvents with one another. In some cases, it may also be advantageous to carry out the re-action or part steps of a reaction under a protective gas at-mosphere and/or in absolute solvents. Suitable protective gases are inert gases, such as nitrogen, helium, argon or, in certain cases, also carbon dioxide.

~ 2766 - 10 ~
The compounds of the formula I

ORl R2 I* I' Az- C~2 f _ c ~
Ar R3 always have an asymmetric C atom C* in the pos;tion adjacent to the substituents Ar and OR1 and can therefore exist in two enantiomeric forms. In general, a mixture of the two enantiomers is formed in the preparation of these substances, and this can be split into the pure optical antipodes in a conventional manner, for example by fractional crystall;sa-t;on of salts with strong optically active acids. The enan-tiomers can have different biological actions; thus, forexample, the fungicidal action can be in the Foreground in one form and the plant growth-regulating action can be in the foreground ;n the other form. A gradual difference in ac-tiv;ty may also occur in the same action spectrum. If the radicals R2 and R3 are different, the molecule contains a further centre of asymmetry ( ), which leads to the exis-tence of diastereomer;c m;xtures (threo- and erythro-forms), which can be separated by means of physical methods.
The present invention relates to all the pure enan-tiomers and diastereomers and mixtures thereof with one ano-ther.
The preparation process described, including all the part steps' is an ;mportant component of the present ;nven-tion.
Application 443,044 discloses that compounds of the formula I
have a microbicidal spectrum against phytopathogenic fungi and bacteria which is very favourable for practical requirements. They have very advantageous curative, systemic and, in particular, preventive properties and can be used for protecting numerous crop plants. The microorganisms which occur on plants or parts of plants (fruit, blossom, foliage, stems, tubers and roots) of various useful crops can be checked or destroyed with the active substances of the formula I, the additional future growth of parts of plants also remaining protected from such microorganisms~
The active substar~Ps of the formula I are effective against phytopathogenic tungi belonging to the following classes: Fungi imperfecti (for examp-le, Botrytis, Helmin-thosporium, Fusarium, Septoria, Cercospora and Alternaria);
and Basidiomycetes (for example the genera Hemileia, Rhizoco-tonia and Puccinia~; and they are particularly active against the class of Ascomycetes ~for example Venturia, Podosphaera, Erysiphe, Monilinia and Uncinula). Moreover, the compounds of the formula I have a systemic action. They can further-more be used as dressings for the treatment of seed (fruit, tubers and seed) and plant seedlings, for protection from fungal infections and against phytopathogenic fungi which occur in the soil.

~22Z~7~6 - -The examplrs which follow serve to illustrate the invention in more detail without restricting it. Tempera-tures are in degrees centigrade. Percentages and parts are S by weight. In addition, the following symbols are used: h =
hour; d = day; ,nin. = minute; RT = room temperature; N = nor-mality; abs = absolute, anhydrous; D~lS0 = dimethylsulfoxide;
and DllF = dimethylformamide. Pressures are given in milli-bar mb or bar b.
1û Preparation examDles Example H1: Preparation of ~C 1 o Cl~ rJ--C.ir-C H
'=' C~

Il 11 1-(1H-1r2r4-Triazol-1-yl) 2-~2,4-dichloroDhenyl)-3-fluoro-pentan-2-ol a) Preparation of 1-(2.4-dichlorophenyl?-2-fluorobutanone Cl--~ ~--C-CX~-C ~

31 9 of dry potassium fluoride were added to a mix-ture of 77 9 of 1-(2,4-dichlorophenyl)-2-bromobutanone and 500 mg of 18-crown-6 in 750 ml of absolute acetonitrile and the mixture was slowly heated to 100 to 110C, while stirring. After about 48 hours, the reaction had ended (checked by gas chromatography or by N~1R). The reaction solu-tion was then poured onto 2 litres of ice-water and extracted several times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and evaporated.
Yield: 57 9 of the oily product. (H-F coupling constant S0 Hz) Boiling point: 77-78/0.008 mbar.
I

Preparation of 2-(2~4=diclllorophenyl)-2~ f1~lorop C1~ IF-C21l5 8 9 of 80% sodium hydride were suspended in 300 ml of absolute D~lS0. 68 9 of trimethyloxosulfonium iodide were introduced ;nto this suspension in portions under a nitrogen atmosphere, while stirring. When the evolution of hydrogen had ended and the exothermic reaction had subsided, the mixture was stirred at RT for a further 2 hours. A solution of 57 9 of 1-t2,4-dichlorophenyl)-2-fluorobutanone in 100 ml of tetrahydrofuran was then added dropwise in the course of 30 minutes, and the resulting mixture was stirred for 3 hours and then diluted to five times its volume with ice-water and extracted several times with diethyL ether. The combined extracts were washed with water, dried over sodium sulfate and freed from the solvent in vacuo. Yield: 55 9 in the form of a brown oil.
c) Preparation of the end product A mixture of 55 9 of 2-(2,4-dichlorophenyl)-2-(1-fluoropropyl)-oxirane, 30 9 of 1,2,4-triazole and 3.5 9 of potassium tert.-butylate in 500 ml of DilF was stirred at 80C for 20 hours. The reaction solut;on was then cooled to RT, poured onto 2 litres of ice-water and extracted seve-ral times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and concentra-ted. Yield of 1-(1H-1,2,4-triazol-1-yl)-2-(2,4-dichloro-phenyl)-3-fluoropentan-Z-ol: 26 9 in the form of colourless crystals. Melting point: 204-206C.
Example HZ: Preparation of l-(lH-1,2,4-triazole-1-yl~-2-(2,4-dichlorophenyl)-3-(4-chlorophenoxy-3-fluoropropan-2-ol Cl Cl-~ ~o- I-CHF-O--\ ~--Cl =- CH2 --~-a) Preoaration of l-(2,4-cllcllloro~ ellyl?-2-bromo-2-fluoroetl1anone --- --- F
Cl-~ C--CE' O ~r A solution of 16 9 of bromine in 100 ml f carbon tetrachloride was added to a solution of 20.7 9 of a-fluor

2,4-dichloroacetophenone in 1ûO ml of carbon tetrachloride at 40 to 45C. After about 1 hour, the brown solution had decolourised. Stirring was continued for another hour and the mixture was then extracted by shaking with aqueous sodium bicarbonate solution and evaporated in vacuo. The oily residue was then distilled under a high vacuum. Yield:
17 9. ~oiling point: 89-92C/0.02 mbar.
15 b) Preparation of 1-(2,4-dichloropllenyl)-2-(4-ch1Orophenoxy)--2 -f luoroe thanone ~_ O
C1--.~ ~---C--C'.-~--O--~\ ~.--C1 . -- . . _ ~

12.8 9 of chlorophenol and 13.8 9 of potassium car-bonate were stirred in 200 ml of acetone for 1 hour. 28 9 of 1-t2~4-dichlorophenyl)-2-bromo-2-fluoroethanone in 50 ml of acetone were added dropwise to this suspension and the mixture was refluxed for 3 hours. After cooling to RT, the colourless salt precipitate was filtered off, the acetone was removed in vacuo and diethyl ether was added. The ether solution was washed with water, dried over sodium sulfate and filtered and the filtrate was concentrated. The oily crude product crystallises after digestion with n-hexane.
Yield: 21.5 9 in the form of yellowish crystals. ~lelting point: 85-87C.

c) Preparation of 2-(2.4-dichl~ L~ =
phelloxyrluoromethy])-oxirane Cl-~ iF-0 \ _ /

S 1 9 of 80% sodium hydride was stirred in 80 ml of DMS0 under a n;trogen atmosphere and 10.3 9 of trimethyloxo-sulfonium iodide were added in portions. After the exother-mic reaction had subsided, the mixture was s-tirred at RT
for a further hour, a solution of 2-(2,4 dichlorophenyl)-2-(4-chlorophenoxy)-2-fluoroethanone in 30 ml of tetrahydro-furan was then added dropwise and the resulting mixture was stirred at 25 to 30C for a further 5 hours and then poured onto 1 litre of water. The product was extracted with diethyl ether, the extracts were washed with water, dried over sodium sulfate and filtered and the filtrate was concen-trated~ Yield: 15 9 as a yellowish oil.
d) Preparation of the end product:
A solution of 13 9 of 2-(2,4-dichlorophenyl)-2-(4-chlorophenoxyfluoromethyl)-oxirane, 4 9 of 1,2,4-triazole and 0.5 9 of potassium tert.-butylate in 100 ml of DMF was stirred at ~0 to 100C for 15 hours. After cooling to RT, the reaction solution was poured into 500 ml of water, whereupon the crude product separated out as an oil. The m;xture was extracted with diethyl ether, the combined ex-tracts were washed with water, dried over sodium sulfate and filtered and the filtrate was concentrated. Yield: 11 9 of an oily crude product, which crystallised on digestion with n-hexane. Yield of the purified product: 7 9. Melting point: 155-157C.
The oxiranes required for the preparation of the compounds shown below in Table 1 can also be prepared in an analogous manner.

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l~iolo~ical e:;amr~les (taken from Application 443 ,044) Example B1- Action aqainst Puccinia sraminiS on wheat . . _ . .
a) Residual-protective action _ _ .
6 days after sowing, wheat plants were sprayed with a spray liquor (0.02% of active substance) prepared from a wettable powder of the artive substance. After 24 hours, the treated plants were infected with a uredospore suspension of the fungus. After incubation at 95-100% relative atmos-'7~6 -- 25 --pheric humidity and about 20C for 48 hours, the infected plants were placed in a greenhouse at about 22C. The development of rust pustules was evaluated 12 days after the infection.
5 b) Systemjc action 5 days after sowing, wheat plants were watered with a spray liquor (0.006% of active substance, based on the volume of soil) prepared from a wettable powder of the active substance After 48 hours, the treated plants were infected 10 with a uredospore suspension of the fungus~ After incuba-tion at 95-100% relative atmospheric humidity at about 20C
for 48 hours, the infected plants were placed in a green-house at about 22C. The development of rust pustules was evaluated 12 days after the infection.
Compounds from the table had a very good action against Puccinia fungi. Untreated but infected control plants displayed a Puccinia attack of 100%~ Inter alia, the compounds 1 to 10, 14, 15, 17, 19, 20, 25, 33 - 35, 45 - 51 and 53 - 57 inhibited the Puccinia attack to 0 to 5%~
20 Examole s2: Action anainst Cercospora arac_idicola_on ground-nut plants Residual-protective action Groundnut plants 10 - 15 cm high were sprayed with a spray liquor (0.006% of active substance) prepared from 25 a wettable powder of the active substance, and 48 hours later were infected with a conidia suspension of the fungus~ The infected plants were incubated at about 21C at a high atmospheric humidity for 72 hours and were then placed in a greenhouse until the typical leaf spots appeared. The fun-30 gicidal action was evaluated, on the basis of the number andsize of the spots which had appeared, 12 days after the in-fection.
In comparison with untreated but infected control plants (number and size of spots = 100%~, groundnut plants 35 which had been treated with active substances from the table showed a greatly reduced Cercospora attack. Thus, compounds 1 to 9, 14, 19, 20, 25, 33, 38, 45-51 and 54-58 almost J~2~

completely prevented the occurrence of spots in the above experiments (0-10%).
Examole B3: Action aqainst ErysiDhe graminis on barley a) Residual-protective action Barley plants about 8 cm high were sprayed with a spray liquor (0.002% of active substance) prepared from a wettable powder of the active substance~ After 3-4 hours, the treated plants were dusted with conidia of the fungus.
The infected barley plants were placed in a greenhouse at about 22C and the fungal attack was evaluated after 1û
days.
b) SYstemic action . . .
Barley plants about 8 cm high were watered with a spray liquor (0.006% of active substance, based on the volume of soil) prepared from a wettable powder of the active sub-stance. Care was thereby taken that the spray liquor did not come into contact with the above-ground parts of the plants. After 48 hours, the treated plants were dusted with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22C and the fungal attack was evaluated after 10 days.
Cornpounds of the formula I showed a good action against Erysiphe fungi. Untreated but infected control plants displayed an Erysiphe attack of 100%. Amongst other compounds from the table, compounds 1 to 10, 14, 15, 17, 19, 20, 25, 33, 35, 38, 45 - 51 and 53 - 5a inhibited the fungal attack on barley to 0 to 5%, and, in particular, compound No. 2 effected complete reduction of attack.
Example B4: Residual-protective action against Venturia inaequalis on apple shoots Apple seedlings with fresh shoots 10 - 20 cm long were sprayed with a spray liquor (0.006% of active substance) prepared from a wettable powder of the active subs-tance.
After 24 hours, the treated plants were infected with a conidia suspension of the fungus. The plants were then incu-bated at 90 - 100% relative atmospheric humidity for 5 days and placed in a greenhouse at 23-24oc for a further 10 days.

-~LZ2'~766 The scab attack was evaluated 15 days after the infection.
Compounds 1 to 6, 8, 9, 14, 17, 19, 20, 33, 45, 47, 49 - 51 and 53 - 57 inhibited the disease infestation to less than 10%. In contrast, untreated but infected control shoots showed 100% attack.

Example B5: Action acJainst Botrytis cinerea on beans Residual-protective action Bean plants about 10 rm high were sprayed with a spray liquor (0.02r~ of active substance) prepared from a wettable powder of the active substance. After 48 hours, the treated plants were infected with a conidia suspension of the fungus. After incubation of the infected plants at 95-100% relative atmospheric humidity at 21C for 3 days, the fungal attack was evaluated. The compounds frorn the table in many cases very greatly inhibited the fungal infec-tion. At a concentration of 0.02%, compounds 1 to 6, 8, 9, 14, 15, 20, 25, 33, 35, 45, 47, 49, 50, 51 and 53-57, for example, proved to be completely effective. The disease in-festation was 0 to 8~o~
The Botrytis attack of untreated but infected bean plants was 100%.
Example B6: Action a~ainst Piricularia oryzae on rice plants Residual-~rotective action After being grown for two weeks, rice plants were sprayed with a spray liquor (0.002% of active substance) prepared from a wettable powder of the active substance.
After 48 hours, the treated plants were infected with a conidia suspension of the fungus. After incubation at 95-100% rela-tive atmospheric humidity at 24C for 5 days, the fungal attack was evaluated.
Rice plants which had been treated with a spray li-quor containing one of the compounds from Table 1, such as, for example, No. 14 or 33, as the active substance, showed a fungal attack of less than 10%, in comparison w;th the untreated control plants (100% attack).

Claims (5)

Case 5-14227/+/DIV
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Aromatic oxiranes of the formula II

II

in which Ar is an unsubstituted or substituted aromatic radical chosen from phenyl, biphenyl, phenoxy-phenyl and naphthyl;
R2 is hydrogen, fluorine, or C1-C6 alkyl; and R3 is hydrogen, fluorine, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl, phenoxy, phenylthio or C3-C7 cycloalkyl, wherein each aromatic radical or moiety is unsubstituted or mono- or poly-substituted by halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, nitro, and/or cyano.

2. Aromatic oxiranes of the formula II according to claim 1 in which Ar is an aromatic radical chosen from phenyl, biphenyl and phenoxyphenyl R2 is hydrogen, fluorine, or C1-C3 alkyl, and R3 is hydrogen, fluorine, C1-C4 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 alkylthio, phenyl, phenoxy, or phenylthio, wherein each aromatic radical or moiety is unsubstituted or substituted with fluorine chlorine, bromine, methyl, methoxy, CF3-, NO2, and/or cyano.

3. Aromatic oxiranes of the formula II according to claim 1 in which:
Ar is phenyl or phenoxyphenyl which is unsubstituted or substituted in the 2- and/or 4- positions by methyl or halogen;
R2 is hydrogen, fluorine, or methyl; and R3 is hydrogen, fluorine, C1-C4 alkyl or a radical chosen from phenyl, phenoxy, and phenylthio which is substituted by fluorine, chlorine, and/or bromine.

4. 2-(2,4-Dichlorophenyl)-2-(4-chlorophenoxy fluoromethyl)-oxirane.

5. 2-(2,4-Dichlorophenyl)-2-(1-fluoropropyl)-oxirane.