AU612155B2 - Novel phenyl ether derivatives as microbicides, their preparation and the use thereof - Google Patents

Description

'TO: THE COMMISSIONER OF PATENTS OUR REF: 59370 S&F CODE: 52760

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U-c

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5845 /2 '4 S F Ref: 59370 FORMA

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COMMONWEALTH OF AUSTRALIA PATENTS ACT 952 2 "19 COMPLETE SPECIFICATIQY0

(ORIGINAL)

FOR OFFICE USE: Class Int Class Complete Specification Lcdcqpd: Accepted: Published: pri or ity: Related Art: S. S S

SS

0 S 0 *5 0 0 *5

S

*5 *5 5 0 5@ *5 S S

S

S

S '4 of Applicant: Address for Service: Ciha-Geig.li AG Klybeckstrasse 141 4002 Basle SWHIT Z ERLAND Spruson &q Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydnoy, New South Hales, 2000, Australia Complete Specification for the invention entitled: Nove't Phenyl Eth,,r- Derivatives as Microbicides, Their Pri 'paration and the Use Thereof The following statement is a full description of this invention, incidiingj the best method of per-Forming it known to me/us 5845/3 DECLARED at Basle, Switzerland on I'ily -LI CIBA-GEIGY AG Werner Waldegg Single Signature, by special pov,- r To: Tho Commissioner of Patents 2.88 5 21 1W '.1I- MAb-,i?' 1 of the Disclosure There are disclosed compound of formula I UO0/CH 2 <iT

V-

wherein X is a 2-pyridinyl radical which is unsuostituted or -ubstituted by one or two identical or different membqrs selected from the 'Up consisting of methoxy, halogen, nitro and-trifluoromethyl; or is the 2-thienyl radical, the 2-thiazolyl radical or the 5-nitro-2-thiazole radicNJ, the pyrazinyl radical, the 2-pyrimidinyl radical or the 4,5,6-trichloro-2- pyrimidinyl radical, QO Iis hydrogen, halogen, C 1 -C 3 alkyl or C 1

C

3 haloalkoxy, and U and V are each independently of the other Cl-C 12 aklo C 1

-C

12 alkyl which is substituted by halogen or 12 -C alkoxy, or, taken together, are an alkylene bridge of formula R2\ /R3

R

4

/R

wherein Rand R 3 are each independently of the other hydrogen, C 1 -C 6 alkyl, C -G 6 alkyl which is substituted by one or more halogen atoms; phenyl or phenyl which is substituted by one or more halogen atoms and/or C 1

-C

2 aikyl groups; or are the group -CH 2 Z-R 7 or wherein Rand R 3 when taken together, are an unsubstituted tetramethylene "210o bridge or a tetramethylene brid& which 's substituted by C -C ,Alkyl; and Z is oxygen or sulfur, Ris hydrogen, C 1 -C 0 lkyl, C 1

C

6 alkyl which is substituted by one or.more halogen atoms or C 1

C

3 alkoxy groups; or is

C

3 -C 4 alkenyl, 2-propynyl, 3-halo--2-propynyl, or also pheny' o~r benz 'vl, each unsubstituted or substituted in the aromatic ring by one or more identical or different members selected from the group consisting of halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, nitro and/or trifluoromethyl, XK#27 7r' 7E~ la

R

4

R

5 and R 6 are each Independently hydrogen or Cl-C 6 alkyl, with the proviso that the total number of carbon atoms in R 4

R

5 and R 6 may not exceed 6, or an acid addition salt r- metal complex thereof.

The invention further relates to the preparation of these compounds and to agrochemical compositions which contain at least one such compound as active component, as well as to the preparation of these compositions and to the use thereof. The novel compounds and compositions containing them can be used for controlling phytopathogenic microorganisms.

*e S 1-

S

9 #65 i_ i I Slb The present invention relates to substituted phenyl ether derivatives of formula I below and to the acid addition salts and metal complexes thereof. The invention further relates to the preparation of these coimpounds and to agrochemical compositions containing, as active component, at least one compound of formula I, to the preparation of said compositions and to the use thereof. The invention also relates to a method of controlling phytopathogenic microorganisms or of preventing infestation of plants by such microorganisms.

Specifically, the invention relates to a cor.ound of formula I U--O CH2--

<I

S-

0

/R

6x 9 C0 0 e 0 *4F wherein X is a 2-pyridinyl radical which is unsubstituted or substituted by one or two identical o> different members selected from the group consisting of methoxy, halogen, nitro and trifluoromethyl, or is the 2-thienyl radical, the 2-thiazolyl radical or the 5-nitro-2-thiazole radical, the pyrazinyl radical, the 2-pyrimidinyl radical or the 4,5,6-trichloro-2- pyrimidinyl radical, R1 is hydrogen, halogen, C 1

-C

3 alkyl or C -C 3 haloalkoxy, and U and V are each independently of the other C 1

-C

12 alkyl or C.-C,alkyl which is substituted by halogen or C,-C 6 alkoxy, or, wheii taken together, are an alkylone bridge of formula 0C CC Ra\ R I +R6 u

C

wherein R 2 and R 3 are each independently of the other hydrogen,

C

1

-C

6 alkyl, C 1

-C

6 alkyl which is substituted by one or more halogen atoms; phenyl or phenyl which is substituted by one or more halogen atoms -2and/or C 1

-C

2 alkyl groups; or are the group -CH 2

-Z-R

7 or wherein

R

2 and R3, when taken together, are an unsubstituted tetramethylene bridge or a tetramethylene bridge which is substituted by C 1

-C

4 alkyl; and Z is oxygen or sulfur, R7 is hydrogen, C 1

-C

6 alkyl, C 1

-C

6 alkyl which is substituted by one or more halogen atoms or C 1

-C

3 alkoxy groups; or is

C

3

-C

4 alkenyl, 2-propynyl, 3-halo-2-propynyl, or also phenyl or benzyl, each unsubstituted or substituted in the aromatic ring by one or more identical or different members selected from the group consisting of halogen, C 1

-C

3 alkyl, C,-C 3 alkoxy, nitro and/or trifluoromethyl,

R

4

R

5 and R6 are each independently hydrogen or C 1

-C

6 alkyl, with the proviso that the total number of carbon atoms in R 4

R

5 and R 6 may not exceed 6, or an acid addition salt or metal complex thereof.

Depending on the indicated number of carbon atoms, alkyl by itself or as moiety of another substituent denotes, for example, the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl and the isomers thereof such as isopropyl,

C.

isobutyl, tert-butyl, sec-butyl, isopentyl and the like. Alkenyl may be 1-propenyl, allyl, 1-butenyl, 2-butenyl or 3-butenyl. Throughout this S specification, halogen shall be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

The present invention also relates to the free compounds of formula I and to the acid addition salts thereof with inorganic acids, as well as to the'metal complexes thereof with metal salts.

V:'

Qe A I^o ;77) r r 3 Salts of this invention are preferably addition salts with inorganic or organic acids which are physiologically tolerable with respect to the intended utility, for example hydrohalic acids such as hydrochloric, hydrobromic or hydriodic acid, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, fatty acids or halogenated fatty acide such as acetic acid, trichloroacetic acid and oxalic acid; or sulfonic acids such as benzenesulfonic acid and methanesulfonic acid; or also addition salts with suitable salts, for example calcium chloride.

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

The compounds of formula I are oils, resins or solids which are stable at room temperature and have very valuable physiological properties, such as microbicidal, for example fungicidal, properties. They can therefore be used in agriculture or in related fields for controlling phytopathogenic microorganisms.

An important group of microbicides for use in plant protection comprises compounds of formula I, wherein X is a 2-pyridinyl radical which is unsubstituted or substituted by one or two identical or different members selected from the group consisting of methoxy, halogen, nitro and 9.

trifluoromethyl; or is the 2-thienyl radical, Ine 2-thiazolyl radical or the5-nitro-2-thiazole radical, the pyrcainyl radical, the 2-pyrimidinyl radical or the 4 ,5,6-trichloro-2-pyrimidinyl radical, RI is hydrogen, halogen, methyl, ethyl or dilfuoromethoxy, and U and V are each independently of the other Ci-C 12 alkyl or Ci-Ci1alkyl which is substituted by chlorine or trifluoromethyl or, when taker.

togttihr, are an alkylene bridge of formula

/R

3 or i \I +-Rk 6 4wherein Ra and R 3 are each independently of the other hydrogen, pheny], halogen-substituted phenyl, C 1

-C

3 alkyl or Ci-C 3 alkyl which is substituted by halogen, Ci-Caalkoxy, Ci-C 2 haloalkoxy, allyloxy or propargyloxy.

Among this group of compounds, a preferred group of agriculturally useful microbicides is that in which X is an unsubstituted 2-pyridinyl radical or a 2-pyridinyl radical which is substituted by one or two identical or different members selected from the group consisting of fluorine, chlorine, bromine, nitro or trifluoromethyl; or is the 2-thienyl radical, the 2-thiazolyl radical, the pyrazinyl radical, the 2-pyrimidiiyl radical or the 4,5,6-trichloro-2-pyrimidinyl radical, RI is hydrogen, chlorine, methyl or difluoromethoxy, and U and V are each independently of the other methyl, ethyl or propyl or, when taken together, are an alkylene bridge of formula R2\ /R3

R

X I

R

or i -R6 wherein R 2 and Ra are each independently of the other hydrogen, Ci-Caalkyl, methoxymethyl, ethoxymethyl or trifluoroethoxymethyl, R4 is methyl, Rs is hydrogen or methyl, and R6 is hydrogen.

Among the above defined compounds, those compounds are particularly preferred in which X is an unsubstituted 2-pyridinyl radical or a 2-pyridinyl radical which is substituted by one or two identical or different members selected from the group consisting of chlorine, bromine and trifluoromethyl, or is the 2-pyrazinyl radical, R is methyl or chlorine, and U and V are each independently of the other the methylethylene radical, the ethylethylene radical or the n-propylethylene radical.

Among this last mentioned group of compounds, the following compounds are to be singled out for special mention: 2-[P-(pyridin-2-yloxy)-2'--iiietylpenyl-2-[iH-i,2,4-triazolylmetbyll-4ethyl- 3-dioxo lane, 2-[p-(5-chloro-3-fluoropyridin-2-yloxy)-2'-chlorophenyl]-2-iiH-.2,4-triazoiylmethyl]-4-methyl-i ,3-dioxolane, 2-['p-(5-chloro-3-fluoropyridin-2-yloxy)-2'-methvlphienyl]-2-[IH-i,2,4-triazolylmethyll-4-methyl-i ,3-dioxolane, 2-P'-rfuooehlyidn2yoy '-methylphenyl]-2-[iH-i,2,4-triazolylmethyl ]-4-methyl-i ,3-dioxo lane, 2-[p-(5-bromopyridin-2-yloxy)-2'-methylphenyl]-2-[IH-1,2,4-triazolylmethyl 1-4-methyl-i ,3-dioxolane, 2-I[p-(5-cloropyridin-2-yloxy)-2'-methylphenyl]-2-[lH-i,2,4-triazolylmethyl]-4-ethyl-i ,3-dioxolane, :2-[p-(5-bromiopyridin-2-yloxy)-2'-methylphenyl]-2-[iH-1,2,4-triazolylmethylil-4-ethyl-i 3-dioxolamie, 2-'ip-(pyridin-2-yloxy)-2 t -chlorophenyl]-2-[iH-i,2,4-triazolylmetyl]-4etflyl-1,.S-dioxolane, *****2-[p-(5-trifluoromethylpyrridin-2-yloxy)-2'-chlorophenyl]-2-[iH-i,2,4-triazolyl.methyl]-4-methyl-i ,3-dioxolane, 2-[h>,(5-trifluoromethylpyridin-2-yloxy)-2'-chlorophenyl]-2-[IH-1,2,4-tri- 99 azolylmey-'-enyl-i ,3-uioxolane, 2[-(pyrazin-2-yloxy) ''-chloroplhenyl]-2-[lH-1,2,4-triazolylnethyl]-4ethyl-i 3-dioxo lane.

The compounas of formula I can be prepared by A) condensing a compound of formula II

X-A

3 (i with a compound of formula III UO0 /CH 2 N=o V-O /R 14i(II 6 in which formulae one of the substituents A 3 and A4 is a -0-Me group, wherein Me is hydrogen or, preferably, a metal cation, and the other is a radical which can be replaced by a substituted hydroxyl group as defined herein; or B) condensing a compound of formula IV Ne-N( (IV), wherein Me is hydrogen or a metal cation, with a compound of formula V U-0. CH 2

-A

i o -0 /R (v) 0 wherein A is a leaving group; or C) converting the carbonyl group in a compound of formula VI X-0-

(VI),

j= into a group of formula VII V (VII) or -7- 7 D) condensing a compound of formula VIII 0

N=*

(VIII)

/R1 0 Ri Ha-A 1 V II 6x with a compound of formula IX

A-R

7

(IX)

in which formulae one of the substituents Ai and A 2 is a hydroxyl or mercapto group in salt for.., for example of formula -Z-Me, and the other is a leaving group A, or Ai as well as A 2 are hydroxyl groups, to give compounds of formula I, wherein U and V, when taken together, are a group of formula -CHa-CH(CH 2

ZR

1 and R) is a radical R 7 which is different S from hydrogen, and, if desired, converting a resultant compound f formula I into another compound of formula I and/or converting a free compound into an acid addition salt, an acid addition salt into the free t, compound or another acid addition salt, or a free compound or acid *0 addition salt into a metal complex.

Examples of metal cations Me are alkali metal cations, for example lithium, sodium or potassium cations, or alkaline earth metal cations, for example magnesium, calcium, strontium or barium cations.

The preferred process variant is variant which comprises starting from compounds of formulae II and III, wherein A 3 is a group -0-Me and A4 is a leaving group or, preferably, As is the leaving group and A4 is the group 0-Me.

Leaving groups are, for example, reactive esterified hydroxyl groups such as hydroxyl groups which are esterified with a hydrohalic acid, e.g. with hydrofluoric, hydrochloric, hydrobromic or hydriodic acid, or with a lower alkanesulfonic acid, an unsubstituted or substituted benzenesul- _i I 8 fonic or halosulfonic acid, e.g. with methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or fluorosulfonic acid.

The substituents Ri, U, V and Ar are as defined for formula I. Me is preferably hydrogen. The reaction is preferably carried out in a relatively polar but inert organic solvent, for example N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, acetonitrile, benzonitrile and the like. Such solvents can be used in conjunction with other inert solvents such as aliphatic or aromatic hydrocarbons, for example benzene, toluene, xylene, hexane, pctroleum ether, chlorobenzene, S nitrobenzene and the like.

9@ The reaction of an azole of formula IV a M-N'l (IV), wherein Me is preferably a metal atom, especially an alkali metal atom, according to variant B with a compound of formula V U7-0 \CHB-A I (V) .985 I wherein X, RI, U and V are as defined for formula I, is preferably conducted, like the reaction of variant in a relatively polar but inert organic solvent.

If A is chlorine or bromine, an alkali metal iodide (such as Nal or KI) may conveniently be added to speed up the reaction. Elevated temperatures in the range from 0' to 22000, preferably from 120° to 17000, are advantageous. It is convenient to heat the reaction mixture under reflux.

Where M in formula IV 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

F

E!IIZZ7'~ I r C-- ~==rcl ;Li .ni. i i i- 9 alkali metals and alkaline earth metals, as well as rg, as, e.g.

tertiary amines such as triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine and the like.

In this process variant, and in the others described herein, 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 and the like.

The conversion of the carbonyl group in compounds of formula VI into the group of formula VII is carried out by reaction with an orthocarboxylic acid Ci-Ci2trialkyl ester, the Ci-Clealkyl groups of which may be substituted by halogen or C1-C6alkoxy, or in the presence of an acid, with at least 2 moles of a monohydric alcohol of formula U-OH (VII), to give compounds of formula I in which U and V are identical unsubstituted or substituted Ci-Ciaalkyl groups, or by reaction with a diol of the formula VIIb HO--U--V-OH (VIIb) to give compounds of the forula I, wherein U and V together are one of the alkylene bridges defined at the outset. In the foregoing, X, R 1

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- ,3-dioxolane [Synthesis, 1974 23].

In the ketalisation, both reactants are heated for several hours under reflux together with an entrainer in a conventional organic solvent.

Examples of suitable entrainers are benzene, toluene, 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 suitable U and V are each independently of tha other C -C 12 alkyl or

C

1 -C 2alkyl which is substituted by halogen or C 1

-C

6 alkoxy, or, when taken together, are an alkylene bridge of formula /2 Nw i. .I i organic solvents are in this case aromatic hydrocarbons such as benzene, toluene, xylene and the like, saturated hydrocarbons such as n-hexane, or saturated halogenated hydrocarbons such as 1,1,1-trichloroethane.

The ketalisation may also be carried out by other methods, e.g. by reacting a ketone (VI) which has been ketalised with an alcohol zr phenol which differs from the alkanol or diol of the formula Vila or VIIb respectively, and effecting transketalisation with an excess of alkanol VIIa or diol VIIb to a compound The starting material may be obtained e.g. by process variant A).

Comp.ounds of formula 1, wherein U and V in variant D) are together

-CH-CH(CH

2

ZR

7 are obtained e.g. by reaction of a compound of formula VIII with a compound of formula IX, wherein A, is an -SH group and As is a group A. The reaction is preferably carried out in an inert Si'. orgaic solvent. Examples of suitable solvents for this reaction are N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoric triamide, dirsthy' sulfoxide, 4-methyl-3-pentanone and the like. Mixtures with other inert solvents, e.g. with aromatic hydrocarbon? such as benzene, tolueras, xylene and others, may also be used. In some casos it may be convenient to carry out the reaction in the presence of a base to speed up the reaction rate. Examples of suitable bases are alkali metal hydrides or alkeli metal carbonates. It may also be advantageous in certain cases to convert the compound of the formula VIII first into a suitable metal salt. This is preferably accomplished by reaction of VIII with a sodium compound, e.g. sodium hydride, sodium hydroxide and the 9 like. This salt of the compound of formula VIII is subsequently reacted with the compound of formula IX. To increase the reaction rate, the process may also be carried out in some cases at elevated temperature, preferably in thu range from 80° to 130"C or at the boiling point of the solvent.

Coapouttus of the formulaa VIII and IX, wherein AI is a group A and A2 is an -ZH group, may also be reacted in similar manner.

K

11 In the condensation reaction of compounds of formulae VIII and IX, wherein Ai and As are hydroxy, to give compounds of formula I wherein Z is oxygen, the reactants may be heated in a suitable solvent under reflux, while simultaneously distilling off water from the reaction mixture as an azeotrope. Suitable solvents are aromatic hydrocarbons such as toluene or the alcohol HO-.7 itself. This reaction is conveniently carried out in a strong acid, e.g. p-toluenesulfonic acid.

Compounds obtainable by the process of the invention may be converted into other compounds of the formula I by methods which are known per se.

Accordingly, for example, compounds obtainable by the process of the invention may be transketalised to other compounds of the formula I. For example, in compounds of formula I, wherein U and V are identical unsubstituted or substituted C 1

-C

1 2 alkyl radicals U, a group U may be replaced by a group VII by reaction with 1 mole of another unsubscituted or substituted C-C 1 aalkano7 of the formula VII -OH (VIIc), or both groups U may be replaced by a divalent radical by reaction with a diol of formula VIIb. The transketalisation is carried out in conventional manner, for example in the presence of an acid condensing agent such as a mineral acid, a sulfonic acid or a strong carboxylic acid, e.g. hydrochloric or hydrobromic acid, sulfuric acid, p-toluenesulfonic acid or trifluoroacetic acid, preferably while removing readily volatile reaction *oo products by distillation or azeotropic distillation.

Further, additional substituents may be introduced, if desired, into the 5 cyclic aryl moieties of compounds obtained by the process of the invention. For example, halogen can be introduced by reaction with a halogen in the presence of a Lewis acid, e.g. an iron, zinc, boron or itimony halide, or by treatment with N-chlorsuccinimide.

In addition, nitro groups can be reduced to amines, e.g. by means of suitable complex hydrides, e.g. with lithium aluminium hydride, which amines may then be diazotised, e.g. with nitrous acid, and the diazonium group replaced in customary manner by hai'en 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.

5845/3 12 If the compounds of formula I are obtained as bases, then they can be converted into corresponding salts of formula I with inorganic or organic acids, or into metal complexes of formula I by using preferably equimolar amounts of metal salts. Conversely, salts of the formula I can be converted into the free bases n:f formula I by rea ion with an alkali carbonate or bicarbonate or an alkali hydroxide.

The intermediates III, V and VI can be obtained by co,.ventonal methods of pteparative organic chemistry. Thus, for example, the phenol derivative III (A4 -OH) used in variant A) can be prepared by catalytic hydrogenolysis of the benzyl ether III (At Cs6HCH20-) obtainable by reaction of the triazole IV with the brominated ketal of formula X

C

6 Hs-CH 2 -CHBr 1 The brominated ketal X can be prepared starting from the acetophenone derivative of formula XI 9.

SCHs-CHa-O-\ ,--CO-CH 3

(XI),

Rit by side chain bromination and acetalisation, the sequence of which operations can be varied.

9 The ether of formula V used in variant B) can be prepared, if A Br, by bromination and acetalisation of the ether of formula XII X-o- -CH3 (XII), eR 1 the sequence of wlhich operations can be varied, identical or di fferent members selected from the group consisting of halogen, C 1

-C

3 alkyl, C 1 -C 3 alkoxy, nitro and/or trifluoromethyl, 412 7P E 13 The ether of formula XII can be with the phi:; I XIV: obtained by reaction of the halide XIII X Hal

XIII

3

XIV

4 XII.

The ether of formula VI used in variant C) can obtained by condensation of the bromoketone of formula XV with the~ triazole VI: uH 2 Br Me-N"I 4 -r N 00 :The starting materials II, IV, XIV and the alcohols and glycols employed for the acetalisation are known chemical compounds.

The described prccess variants alao fall within the scope of this invention.

eAll the abovPe described ketalisation reactions of a ketone with a .substituted N,I3-diol nr aj,-diol result in the formation pr,.,iar'Liy of :94 mixtures of diastereoisomers of the resultant ketal. The -,-=pounds of se* formula I may be obtained e.g. in the following two diasteroisomeric forms, 9 0 S. S 99 54 X-0

N=

OdiZR 7

H

-types (x VII) X-0O d/ R1 C. N 3_ *'H

(XV]

The configuration of the A type shall be designated here and subsequently m~ the "trans "-isomer or "trans-racemate't: -14 X-0= X-0 _C C R C B-types R

C

(XVIII) C ZRH (XIX)

H

The configuration of type B will be correspondingly designated as "cis"-isomer or "cis-racemate".

The symbols in the three-dimensional structures reproduced above have the following meanings: *0 behind the drawing plane in the drawing plane in front of the drawing plane.

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 and the like). The preparation of the four optically pure isomers is also Spossible. The four isomers as well as the two "trans- and cis"-racemates have different biological activity. As a rule, the mixtures of diastereoisomers will, for practical purposes, be used as obtained from the synthesis without resolution.

Surprisingly, it has been found that compounds of formula I have for practical purposes a very useful microbicidal spectrum against phytopathogenic fungi and bacteria. They have very useful curative, preventive and systemic 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 occur in plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack by such microorganisms.

15 The compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula): Basidiomycetes the genera Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti Botrytir, 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 against fungus infections as well as against phytopathogenic furgi which occur in the soil. The compounds of the invention are especially well tolerated by plants.

Accordingly, the invention also relates to microbicidal compositions and *Prr to the use of compounds of the formula I for controlling phytopathogenic microorganisms, especially harmful fungi, and for the preventive treat- J ment of plants to protect them from attack by such microorganisms.

e* SThe invention further embraces the preparation of agrochemical compositions, which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds described herein. The Sinvention furthermore relates t' a method of treating plants, which comprises applying thereto the compounds of the formula I or the novel compositions.

Without i mplying any limitation, target crops to be protected within the scope of the present invention comprise e.g. the following species of S plants: cereals (wheat, barley, rye, oats, rice, sorghum and related crops), beet (sugar beet and fodder beet), drupes, poses and soft fruit (apples, pea's, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries), 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, lemons, gj:apefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae A. 7' I I T 16 (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 (flowers, shrubs, deciduous trees and conifers).

The compounds of formula I are normally applied in the fo:m of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds. These compounds can be fertilisers or micronutrient donors as well as other preparations that influence plant growth. They can also be selective herbicides, fungicides, bactericides, nematicides, molluscicidas or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation. Suitable carriers and adjuvants of all formulations can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.

A preferred method of applying a compound of formula I nr an agrochemical composition which contains at least one of said compounds, is application to the growing parts of plants, especially the leaves (foliar applica- Stion). The number of applications and the rate of application depend on the risk of infestation by the pathogen (type of fungus). However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the S soil, e.g. in granular form (soil application). The compounds of formula I can also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation containing a compound of the formula I, or coating them with a solid formulation. In special cases, further types of application are also possible, e.g. selective treatment of the buds or fruit.

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 tc emulsifiable concentrat&s, coatable pastes, directly sprayable or dilutable solutions,

X

or 4-R 6 ALl i I- i dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating cr 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 per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 100 g to 600 g a.i./ha.

The formulations, i.e. the compositions 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 extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol s monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils *oo such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. 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, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a t ,Lat number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues. Particularly advantageous application promoting adjuvants which are able to reduce substantially the rate of application are also natural i. f U tC o i e to be singled out for special mention: i- I I 18 (animal or vegetable) or synthetic phospholipids of the series of the cephalins and lecithins, e.g. phosphatidyl ethanolamine, phosphatidyl serine, phosphatidyl choline, sphingomyeline, phosphatidyl inisotol, phosphatidyl 'glycerol, lysolecithin, plasmalogenes or cardiolipin, which can be obtained e.g. from animal or plant cells, in particular from the brain, heart, liver, egg yokes or soya beans. Examples of useful physical forms are phosphatidyl choline mixtures. Examples of synthetic phospholipids are dioctanoylphosphatidyl choline and dipalmitoylphosphatidyl choline.

Depending on the nature of the compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic sufactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

9 SSuitable anionic surfactants can be both water-soluble soaps and watersoluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Clo-C 22 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 methyltaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulforites.

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 contain a Cs-Caaalkyl 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 of sulfuric acid esters and sulfonic acids of fatty 19 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 triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensate. Also suitable are corresponding phosphates, e.g.

salts of the phosphated adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants 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 alkylpolypropylene 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 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/ polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N,-substltuent, at least one Ce-Ca 2 alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzylbis(2-chloroethyl)ethylammonium bromide.

i 20 The surfactants customarily oyed in the art of formulation are known to the skilled person and described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ringwood, New Jersey, 1981; Helmut Stache, "Tensid-Taschenbuch" (Surfactant Handbook) Carl Hanser Verlag, Munich/Vienna, 1981.

The agrochemical compositions usually contain 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 0 to 25 preferably 0,1 to 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 for obtaining special effects.

Such agrochemical compositions also constitute an object of the present invention.

The invention is illustrated in more detail by the following Examples, without implying any restriction to what is described therein. Parts and percentages are by weight.

Preparatory Examples Examples PI: Preparation of *9 9.

9 4~ *4 a a.

*9 a a.

a 49~ a

F

2 0 /CH 2

NK-

H- a /Cl FC1 C 1 (compound 1.3), Leaving groups are, for example, reactive esterified hydroxyl groups such as hydroxyl groups which are esterified with a hydrohalic acid, e.g. with hydrofluoric, hydrochloric, hydrobromic or hydriodic acid, or with a lower alkanesulfonic acid, an unsubstituted or substituted benzenesul- 1 21 2-[p-5-Chloro-3-fluoropyridin-2-ylxyloxyl)-2'-chlorphenyl]-2-[lH-,2,4-triazolylmethyl]-4-methyl-1,3-dioxolane 2.88 g (16 mmol) of 30 sodium methylate in 10 ml of absolute methanol are added dropwise at room temperatur to a solution of 4.5 g (15.2 mmol) of 2-(4-hydroxy-2-chlorophenyl)-2-(1H-1, 2 ,4-triazolylmethyl)-4-methyl- 1,3-dioxolane in 30 ml of absolute methanol. The mixture is stirred for 1/2 hour at 60°C, then the methanol is removed on a rotary evaporator and to the crystalline sodium salt are added 40 ml of dimethyl formamide.

Then 2.5 g (16.7 mmol) of 5-chloro-2,3-difluoropyridine in 10 ml of absolute dimethyl formamide are added dropwise over 10 minutes to the above mixture, followed by the addition of 0.3 g of potassium iodide as catalyst. The reaction mixture is stirrr- for 16 hours at 100°C, then cooled to room temperature and poured into 150 ml of water. After extraction with 3 x 50 ml of ethyl acetate, the combined organic phases are washed with 2 x 50 ml of water, dried over sodium sulfate, filtered, and the solvent is evaporated. The pale brown oily residue is chromatographed through a 30 cm column of silica gel using a 1:1 4 xture of chloroform/diethyl ether as eluant. The solvent is removed by evaporation to give i yellow oil with a refractive index n 24 1.5794.

D

*4 Example P2: Preparation of the intermediate /CH3 HO-/ C CH- \cl 2-(4-Hydroxy-2-chlorophenyl)-2-(1H-1,2,4-triazolylmethyl)-4-methyl-1,3dioxolane 42.8 g (0.11 mol) of 2-( 4 -benzyloxy-2-chlorophenyl)-2-(lH-1,2,4-triazolylmethyl)-4-methyl-1,3-dioxolane are hydrogenated in a 15 solution of ethanol in the presence of 5 palladium on carbon at room temperature. The catalyst is subsequently removed by filtration and the solvent is evaporated. Recrystallisation of the residue from Y~'UCL Lr;~llln Where M in formula IV 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 ~Y 1 I ir I I; i 22 toluene/petroleum ether (50°-70C) gives a white crystalline powder with a melting poi.nt of 201 0 -203 0 C. The following final products of formula I (obtained as mixtures of diastereoisomers in varying mixture ratios) can also be prepared in analogous manner: 4* 4.

4 4 4.

*4 4 4 44 V 4 4 4.

4 4 a.

4 4.

4 a.

S

S..

5. 4 C .54 C. S S 5 C S S C a

S

C S C CC C S S S C S S S 2 5 SOS

S

Table 1: Compounds of formula

R

3 C? N/

R

2 0\

/R

1 Couipound 1.1 1-2 1.3 1.4

H

CR3

C;\/F

I ii Cl- I

CH

3

R

2

H

H

H

CH

3

R

3

-C

2 Hs -C 3 H.-n

CH

3

CR

3 Physical data m.p. 100-103'C H-4 1.5794 3:1.5672 U 4

S

4 454 4

C

4 S S S eQ S S 4 C 4 S. 4 5 0 5 4 o 9 S S S 4 5 4 4 5*S S S S S n P Table 1: (continuation) Compound X R j R2 J R3 L Physical data I II CH 3 -c 2

H

5 23 nD 1. 5 667 4 4 4 I

F

3 /0 CH3- -0215 23 nD 1.5416 R~ /l 28 1.7 OH 3 11 -CH 2 0CH 3 n D: 1.5639

/F

1.8 1 i ICH 3

OH

3 I -C 2

H

5 1 1.9

F

3

C-\

1

Y.\

CH

3 -02115 n23 :154 D 54 .1- 1.10 CH3- -CHIOCI Tablp- 1* cninain Copon 1.11

CH

1.1 CH3 1.114

CH

3 1.122 N \1 iH- 1.41 CH 02N"\ /3 1.16 R /C1 C 1.16 I II Gi 3 a a a @4 4 a a a a a a a 4 a. a 4 a a a t; a a 4 a eta

R

2 J R 3 Physical data 1 -1 1

H

H

H

H

H

H

OH

3

CH

3 C3-

CR

3

-C

2

H

5 23 1.5705

D.

n25 :1.5834 Tp.43 A'' nf23: 1.5795 4 5 4 45 5 4 0 06 aaa so 0 a5 S 5 S. 5 S S S S 5 8 S S See 0 55. Table 1: (continuation) 4 0 4 4 4.

6 9 4 0 4 6 *64 00* **A 4 S 4 .4 9 4 9 S 0 0 4 S S 4 0 4 644 .69 69 9 Table 1: (continuation) Compound) X R R 3 Phy,:cal data F 3 C\ 1.23 CHI i 3 H -CH 2

OCH

3 1-12C 1.24 Cl- H CH 3 m.p. 102-105%C C ,/F 1.25 1 I CR 3 H -CH 2

OC

2

H

1.26 R i T I CH 3 H CH 3 n 4:1.5812 1.27 I iI CH 3 H -CH1 2

OCH

3 n 5:1.5831 CJ~ 1.28 CH3- 1.28CR 3

CH

2

OCH

2

CF

3 n2:1.5769 e C US 0 S0 5 w e 0g~ 0H Tabl 1:(continuati.n) Compound x D3 w

R

2

R

3 Physical dataV'M Nc C D r 1.29 *C -HGH

H'

C3 H

(D

0 M 1.30 I H

CH

3 H'd P3H

N

1.31- H

C

00

DC

1.31 lCf 3 H -CH20CH 2

CH=CH

2 0 2 N /NO2

E

34 0 H -C 3

C

0r

(D

(rt a a a U a. a a -a C a a a a a a. a a a a a a a. a a a C a *.a a a a a a a ata a Table 1: (continuation) Compound XRI2 R 3 Physical data 1.35 RT I I CH 3 H CH 3 nD2 1. 5689 1.36 if Cl 3 H -C 2 11 1.37 Cl! 3 H -C 2

S

1.3 R if I CH 3 H -CH 2

OCH

3 n25 1 79 1.39 ICH 3 H -CH 2 0CH 2

C-CH

1.40 I 1 Cl- H -C 2

H

i

_I

ably, together with the adjuvants conventionally employed in the art of formulation, and are therefore, formulated in known manner tc emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions,

I

0~ S. 4* 4* 4. 5 S S

S.

S.

S S *5 SS S a S S 4 ~.S 45 S S 55 5 *545 *555S5 5* 9 5 .5 4-i U In U UI

NN

I I 0 r'r 0 organic nature can be used, e.g. especially dolomite or pulverised plant residues. Particularly advantageous application promoting adjuvants which are able to reduce substantially the rate of application are also natural a. a a *5 a a a.

a.

a.

a a a.

a.

a.

ha a a a a 9a a a a

.J

COr- U C'4C 1 o Co4 In 0 I-el,

C-O

0 rlignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty

CO

'4 .9 9 9.

*9 9 9.

9 9 9 999*99 9 9* 99 C 9 99 9.

9 99 9 9* 004

I-)

-IjCZ r.

U,

I\ .1 .rI

CO

0 aa 7 w

'-I

C-,

4,-

'-V

C-,

U-

4 a a a C a a a as a a a a C e C a a a baa a a a a a Ca. a a Table 1: (continuation) Compound. X R 2R Physical data I C /F- 1.59 IICl- H 1.60 B Gil C 3 H CH 3 n 2 1.5887 1.61 11 Cl- H

CH

3 0/*y~ 0 2 N\ 1.62 1 IICl- H CH 3 1.31 II 0113- H -CU 2 0CH 3 n28 153 1.64 1 *Cl- H -C11 2 0C 2

H

__j

I

4* V*

S

S S S S 55 S S S S S S S S S *4 S

S

5. Table 1: (continuation) ii- 0 Not of ethanol in the presence of 5 palladium on carbon at room temperature. The catalyst is subsequently removed by filtration and the solvent is evaporated. Recrystallisation of the residue from S I co w CO rCO P4 r- r. I~ 0 00 In *0 0 U) L) U p CJ .0p..

600 0 0 U m'a C'J N (I I m N 0 N U3 I U U I u *6

S

*1*5 5*I tr

*PSP

0N 11r I" I I K. 2$>UU r1

'-VC.

C-,

r I l 0 r- ~4 1 ,fl C.)I h I a.

a U U. U S U a a U a S a a a.

S a U U U U U S a U U U U -a a S U U U S U **U S U U U S sea Table 1: (continuation) Compound x 1.77 \*F

\N

1.78 Cx 1.79

/A

1.80 1.821H RI R 2 F H Cl- H

-OCHF

2

H

Cl- H Br- R- F H R3 Physical data

CH

3 -C2H5 24 :1.5764

-C

2

H

-C

2

H

5 n 4:1.5730

-CH

3

-C

2

H

C

C

C

0CC 4..

C. C Ca- a a C C a.

a C C C. C C

CC

C C C a a CC *CC

C

I

Tabl 1:(continuation) Table 1: Coa 0 0 a *00 *S* a. a a a. a a a a a a a a a a a C sa a a a a 9 a a so a a a a a a 000 a a a 0 a 000 0 Table 1:.(continuation) Comoud XR 1

R

2 Physical data 1.89 Cl- H CH 3 n 4:1.5822 Table 1 Compo 1.8 1.10 r.

Tal a Copond of foml R3 0 CC C C/-

R

2 0 /Rl C C C 6' CC C C C C 0 P C C C C 0 C C C C C CCC CCC C CCC C CCC CCC C salt Table 1: Compoi 1.11 1.12 1.13 1.14 1.16 1/ I

S

4~ 99 4 9 .9.

99 0 9 4 494 9 4 0 9 44 9 4 9 9 9 0 4 *e 9 0 4 *44 90 4 9 499 9 099 .99 9

V

It Table 2: Compounds of formula

CR

II

6x Compound X F j R 5

R

6 Salt Physical data 2.1 I i CH 3 4-CR 3 H H 22 1.5802 2.2 t Ii Cl- 5-CH 3 5-CH 3

H

2.3 rCH 3 5-C 3 5-CR 3 H n- n 1.5873 2.4 CR 3 4-CH 3 H H 1 ii Cl- 4-CH3- H H I_ Table 1: Compou 1.17 1.18 1.19 1.20 11 1.22 rn S 8 6 *S

S

S

*SS

S S S S Si 9e 9 S 5O*~ *s S S S S S S 5 5* 5 6 5 S q a I. S*S S 5 0 555 SR* S S *55 555 Table 2: (continuation) Compound X RI R 4 RR6 Salt Physical data 2.6 FC\iHCR 3 4-CH 3 H H n 26 1.5728 2.7 ,I CR 3 4-CH 3 5-CR 3 6-CH 3

F

3 C\ 2.8 1 iiCl- 5-CH 3 5-CH 3

H--

2.9 Cl- 4-CH 3 H H--

S

F 3 C\ 2.10 1 CH 3 5-CR 3 5-CH 3

H

2.11 i Cl- 4-CH 3 H H-- Table Compound 1.23 1.24 1.25 1.26 1.27 1.28 S S S S S S S S S S S S S S 55 5 5 5 4. 5 S S S S S 555 5 5, 5 5 555 5 955 Table 2: (continuation) Table 1: Compoun 1.29 1.30 1.31 1.34 0* 0 0 0 a a a a a a a a a aa* a a Table 3: Compounds of formula i Ccrmpound X R U V Salt Physical date 3.1 11 Cl- -CH 3

-CH

3 n~ 1.5789 3.2 ICi- -C 2

H

5

-C

2

H

3.3 F3 C\ Ui CH 3

-CH

3

-CH

3 79 C\ if Cl- -C 2

H

5

-C

2 H 11N0 3 Table 1: Compour 1.35 1.36 1.37 1.38 1.39 1.40 Copon x R1 U Sal Phsia dat Tal 1: Comp undX 11V S lt hysi al ataCompound 3.6 C~\/FCl-

-C

2 Ii 5

-C

2 11 5 1.41 3.7

CH-

3

-CH

2

CF

3

-CH

2

CF

3 -14 3.8 1 if Cl- -C 3 1 7 -C311 7 -n 3.9 I Cl- -CHf 2

CH

2 Cl -CHaCHzCl-- 3.10 CH 3 -C0 20 2 C1 -CH 2

CI

2 C1 1.44___ ~/1.45 ii C l-HCH 3.1C 3 Cl-.1vV \I 2 HC 1.46 1 77, Tabl 3: coninuaion Copon x R. v Salt Physical dataa F a. 3.1 Cl -CaF aC2F aaaa 3.123 I Cl- -CzHzCF 3

-CH

2 5F 3 3.13 0 I Cl3- -C 12

H

25 -n -Cl 2

HZ

5 -n 3.145 CH- -C 2

H

5 -C2Hs 3.16 11f Cl- -Ci4H 9 -sek -C 4 11 9 -sek-- 3.17 CH 3

-CH

3 -CI13-- 04 6% 4- 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 .4 4 4 4 4 0 4 4 4 4 4 4 **4 .4 4 V 4 TIable 3: (continuation) Compound X Ri U V Salt Physical data F3 C\ 3.18 Cl- -CH2CF 3

-CH

2

CF

3 3.19 1 it Cl- -CH 3

-CH-

3 Table 1: Compound 1.53 1.54 1.55 1.56 1.57 1.58 0 o -1 0 ,fl Q\ I Qr HL l\ l bV D~ i I 47 Formulation Examples Formulation Examples for liquid active ingredients of the formula I (throughout, percentages are by weight) Fl Emulsifiable concentrates a a compound of Tables 1 to 3 25 calcium dodecylbenzenesulfonate 5 castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 tributylphenol polyethylene glycol ether moles of ethylene oxide) cyclohexanone xylene mixture 65 b) 40 8 c) 50 6% 12 15 25 4% 20 20 9* *9 9 6 o e Emulsions of any required concentration can be produced from such concentrates by dilution with water.

F2 Solutions a) b) c) d) a compound of Tables 1 to 3 80 10 5 95 ethylene glycol monomethyl ether 20 polyethylene glycol 400 (mol wt.) 70 N-methyl-2-pyrrolidone 20 epoxidised coconut oil 1 5 petroleum distillate (boiling range 160-190) 94 These solutions are suitable for application in the form of microdrops.

F3 Granulates a compound of Tables 1 t? 3 kaolin highly dispersed silicic acid attapulgite a) 5% 94 1% b) 10 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.

I m,0 011ii 48 F4 Dusts a compound of Tables 1 to 3 highly dispersed silicic acid talcum kaolin a) b) 2% 1 97 -90 Ready-for-use dusts are obtained by intimately mixing the carriers with the acitve ingrodient.

Formulation examples for solid active ingredients of formula I (throughout, percentages are by weight) Wettable powders a compound of Tables 1 to 3 sodium lignosulfonate sodium lauryl sulfate sodium diisobutylnaphthalenesulfonate o octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) highly dispersed silicic acid kaolin a) b) c) 25 50 75 5 5% 3 5 6 10 2% 5 10 62 27 10 I 0 *0 9 0* 0i The active ingredient is thoroughly mixed with the adjuvants and the mixtures is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

F6 Emulsifiable concentrate a compound of Tables 1 to 3 octylphenol polyethlene glycol ether moles of ethylene oxide) calcium dodecylbenzenesulfonate castor oil polyglycol ether (36 moles of ethylene oxide) cyclohexanone xylene mixture 10 3% 3% 4 30 50 v r- 0 C- C'J Lno d) r-

H

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

F7 Dusts a) b) a compound of Tables 1 to 3 5 8 talcum 95 kaolin 92 Ready-for-use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.

F8 Extruder granulate a compound of Tables 1 to 3 10 sodium lignosulfonate 2 S carboxymethylcellulose 1% kaolin 87 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 strem of air,

S

F9 Coated granulate a compound of Tables 1 to 3 3 polyethylene glycol 200 (mol wt.) 3 kaolin 94

S

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

e* 0 Suspension concentrate a compound of Tables 1 to 3 40 ethylene glycol 10 nonylphenol polyethylene glycol moles of ethylene oxide) 6 sodium lignosulfonate 10 carboxymethylcellulose 1% 37 aqueous formaldehyde solution 0,2 O I I I- r r- o C o *1 50 silicone oil in the form of a 75 aqueous emulsion 0.8 water 32 The finely ground active ingredient is intimately mixed with the aduvants, giving a suspension concentrate from which suspencions of any desired concentration can be obtained by dilution with water.

Biological Examples Example Bl: Action against Puccinia graminis on wheat a) Residual-protective action Wheat plants were treated 6 days after sowing with a spray mixture prepared from a wettable powder formulation of the active ingredient (0.06 After 24 hours the treated plants were infected with a uredospore suspension of the fungus. The infected plants were incubated for 48 hours at 95-100 relative humidity and about 20°C and then stood in a greenhouse at about 220C. Evaluation of rust pustule development was made 12 days after infection.

*f b) Systemic action Wheat plants were treated 5 days after sowing with a spray mixture S prepared from a wettable powder formulation of the test compound (0.006 based on the volume of the soil). After 48 hours the treated plants were infected with a uredospore suspension of the fungus. The plants were then incubated for 48 hours at 95-100 relative humidity and about 20 C and then stood in a greenhouse at about 22°C. Evaluation of rust pustule development was made 12 days after infection.

Compounds of Table I were very effective against Puccinia fungi. Puccinia

I

infestation on untreated and infected control plants was 100 For example compounds 1.3, 1.6; 1.9, 1.20; 1.23, 1.27, 1.35, 1.48, 1,63; and 1.65 inhibited Puccinia infestation to 0-5 In addition, compounds 1.3 and 1.65 exhibited full systemic action (0 infestation) even when diluted to a concentration of 0.006 -51 Exnmple B2: Action against Cercospora arachidicola in groundnut plants Residual protective action Groundnut plants 10-15 cm in height were sprayed with a spray mixture (0,02 prepared from a wettable powder formulation of the test compound, and infected 48 hours later with a conidia suspension of the fungus. The infected plants were incubated for 72 hours at about 210C and high humidity and then stood in a greenhouse until the typical leaf specks occurred. Evaluation of the fungicidal action was made 12 days after infection and was based on the number and size of the specks.

Compared with untreated and inrected controls (number and size of the specks 100 Cercospora infestation on groundiut plants treated with compounds of Table 1 was substantially reduced. In the above test, compounds 1.3, 1.5, 1.9, 1.12, 1.16, 1.20, 1.26; 1.27, 1.32, 1.35, 1.41, 1.44, 1.48, 1.52, 1.56, 1.60, 1.65, 1.69, 1.74, 1.76, 1.78, 1.80 and 1.87 inhibited the occurrence of specks almost completely (0-10 Example B3: Action against Erysiphe graminis on barley a) Residual protective action Barley plants about 8 cm in height were sprayed with a spray mixture S(0,02 prepared from a wettable powder formulation of the test compound. The treated plants were dusted with conidia of the fungus after 3-4 hours. The infected barley plants were then stood in a greenhouse at about 220C. The extent of che infestation was evaluated after 10 days.

b) Systemic action Barley plants about 8 cm in height were treated with a spray mixture (0.006 based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care was taken that the spray mixture did not come in contact with the growing parts of the plants. The treated plants were infected 48 hours later with a conidia suspension of the fungus. The infected barley plants were then stood in a greenhouse at about 220C and evaluation of infestation was made after 10 days.

Compounds of Table 1 were very effective against Erysiphe fungi. Erysiphe infestation was 100 on untreated and infected control plants. Compounds 1.1, 1.5, 1.6, 1.9. 1.13, 1.16, 1.20, 1.23, 1.56, 1.63, 1i. .4nd 1.87 52 inhibited fungus attack on barley to 0-5 In addition, compounds 1.20 and 1.41 exhibited systemic action (0 infestation) when diluted to a concentration of 0.006 Example BA: Residual-protective action against Venturia inaequalis on apple shoots Apple cuttiugs with 11-20 cm long fresh shoots were' sprayed with a spray mixture (0.02 prepared from a wettable powder formulation of the test compound. The plants were infected 24 hours later with a conidia suspension of the fungus. The plants were then incubated for 5 days at 90-100 relative humidity and stood in a greenhouse for a further 10 days at 2 0 2 4 Scab infestation was evaluated 15 days after infection.

Compounds of Tables 1 ard 2 effected a marked inhibition of infestation.

Compounds 1.3, 1.5, 1.9, 1.12, 1.20, 1.23, 1. 1.32, 1.35, 1.38, 1.41, 1.44, 1.48, 1.52, 1.56, 1.60, 1.65, 1.69, 1.76, 1.78, 1.80 and 1.87 inhibited fungus infestation almost completely -5 Venturia attack on untreated and infecte,d control shoots was 100 9* Example B5: Action against Botrytis cinerea on apples Residual protective action Artificially damaged apples were treated by dropping a spray mixture (0.02 prepared from the spective test compound formulated as wettable powder onto the injury sites. The treated fruit was then o inoculated with a spore suspension of Botrytis cinerea and incubated f.r the number of injury sites attacked by rot and deducing the fungicidal action of the test compound therefrom. Compounds 1.3, 1.5, 1.48, 1,60, 1.63, 1.76, and 1.80 innibited fungus attack to 0-5 (full inhibition).

0S 0 00

Claims (14)

1. A compound of formula I consisting of mothoxy, halogen, nitro and trifluoromethyl; or is the SU-, h CH when taken together, are an alkylene bridge of formula R- 0 /R S4I (I) wherein X is a 2-pyridinyl radical which is unsubstituted or substituted by one or two identical or different members selected from the group consisting of mthoxy, halogen, nitro and trifluoromethyl; or is the 4 2-thienyl radical, the 2-thiazolyl radical or the 5-nitro-2-thiazole radical, the pyrazinyl radical, the 2-pyrimidinyl radical or the 4,5,6-trichloro-2- pyrimidinyl radical, t' R 1 is hydrogen, halogen, C l-C alkyl or C -C haloalkoxy, and U and V are each independently of the other C-Cp alkyl or C -Cl 2 alkyl which is substituted by halogen or Cl-C 6 alkoxy, or, Sc when taken together, are an alkylen e bridge of formula R 2 R o I wherein R2 and R 3 are each independently of the other hys agen, C 1 -C 6 alkyl, C 1 -C 6 alky1 which is substituted by one or mor halogen atoms; phenyl or phenyl which is substituted by one or more halogen and/or C-C 2 alkyl groups; or are the group -CH 2 -Z-R 7 or wherein R and R 3 when taken together, are an unsubstituted tetramethylene bridge or a tetramethylene bridge which is substituted by Ci-C 4 alkyl; 4 and Z is oxygen or sulfur, R is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alky1 which is substituted by one or more halogen atoms or C 1 -C 3 alkoxy groups; or is C3-C 4 alkeny1, 2-propynyl, 3-halo-2-propynyl, or also phenyl or benzyi, each unsubstituted or substituted in the aromatic ring by one or more identical or d'fferent members selected from the group consisting of halogen, C -C 3 alkyl, Cl-C 3 alkoxy, nitro and/or trifluoromethyl 1 31 0 0 H-J0- o I N C N NC C CN EH 54 R 4 R 5 and R 6 are eanc independently hydrogen or C 1 -C 6 alkyl, with the proviso that the total number of carbon atoms in R 4 R 5 and R 6 may not exceed 6, or an acid addition salt or metal complex thereof.

2. A compound according to claim 1, wherein X is a 2-pyridinyl radical which Is unsubstituted or substituted by one or two identical or different members selected from the group consisting of methoxy, halogen, nitro and trifluoromethyl, or is the 2-thienyl radical, the 2-thiazolyl radical or the 5-nitro-2-thiazole radical, the pyrazinyl radical, the 2-pyrimidinyl radical or the 4,5,6-trichloro-2-pyrimidinyl radical, R, is hydrogen, halogen, methyl, ethyl or difluorometho)y, and U and V are each independently of the other C 1 -C 12 alkyl or C 1 -C 12 alkyl which is substituted by chlorine or, when taken together, are an alkylene bridge of forqiula Ra\ or R4,yZ or i R6 wherein R and R 3 are each independently of the other hydrogen, phenyl, S halogen-substituted Dhenyl, C -C 3 alkyl or C 1 -C alkyl which is NO substituted by halogen.

3. A compound according to claim 2, wherien X is an unsubstituted 2-pyridinyl radical or a 2-pyridinyl radical which is substituted by one or two identical or different members selected from the group consisting of fluorine, chlorine, bromine, nitro or trifluoromethyl, or Is the 2-thienyl radical, the 2-thiazolyl radical, the pyrazinyl radical, the 2-pyrimidinyl radical or the 4,5,6-trichloro-2-pyrimidinyl radical, R 1 is hydrogen, chlorine, methyl or difluoromethoxy, and U and V are each independently of the other methyl, ethyl or propyl or, S* when taken together, are an elkylene bridge of formula R /R3 RU\X., or or I Rs wherein R 2 and R 3 are each independently of the other hydrogen, C 1 -C 3 alkyl, methoxymethyl, ethoxymethyl or trifluoromethoxymethyl, R 4 is methyl, R is hydrogen or methyl, and LIAAR6 is hydrogen. i v 3 55

4. A compound according to claim 3, wherein X is an unsubstituted 2-pyridinyl radical or a 2-pyridinyl radical which is substituted by one or two identical or different members selected from the group consisting of chlorine, bromine and trifluoromethyl, or is the 2-pyrazinyl radical, R 1 is methyl or chlorine, and U and V are each independently of the other the methylethylene radical, the ethylethylene radical or the n-propylethylene radical. An agrochemical composition for preventing infestation by microorganisms, wherein at least one active component is a compound of formula I according to claim 1 together with a suitable carrier, adjuvant and/or diluent.

6. A composition according to claim 5, wherein at least one .Active component is a compound of formula I as claimed in any one of claims 2 to 4.

7. A composition according to either 5 or claim 6, which contains 0.1 to 99% of a compound of formula I, 99.9% to 1% of a solid or liquid adjuvant, and 0 to 25% of a surfactant.

8. A composition according to claim 7, which contains 0.1 to 95% of a compound of formula I, 99.8 to 5% of a solid or liquid adjuvant, and 0.1 to 25% of a surfactant.

9. A process for the preparation of an agrochemical composition, which comprises intimately mixing at least one compound of formula I as claimed in any one of claims 1 to 4 with suitable solid or liquid adjuvants and surfactants.

10. A method of controlling microorganisms or of preventing infestation of cultivated plants by such microorganisms, which comprises applying to said plants or to the locus thereof a pesticidally effective amount of a compound of formula I as claimed in any one of claims 1 to 4 or a composition as claimed in any one of claims 5 to 8.

11. A method according to claim 10, wherein the microorganisms are phytopathogenc fungi. S" 12. A phenyl ether derivative, substantially as hereinbefore described with reference to any one of compounds 1.1 to 1.94, 2.1 to 2.17 or 3.1 to 3.19.

13. A process for preparing a phenyl ether derivative substantially as hereinbefore described with reference to Example PI.

14. An agrochemical composition for preventing infestation by iicroorganisms substantially as hereinbefore described with reference to any one of the Formulation Examples F1 to I I jla i i 56 An agrochemical composition for preventing infestation by microorganisms, comprising a compound as claimed in claim 12 together with a suitable carrier, adjuvant and/or diluent.

16. A method of controlling phytopathogenic microorganisms or of preventing infestation of cultivated plants by such organisms, which comprises applying to said plants or to the locus thereof a pesticidally effectiva amount of a compound of formula I as claimed in claim 12 or a composition as claimed in claim 14 or

17. A phenyl ether derivative whenever prepared by the process of claim 13. 0*SO 0S S S S. @6 6 6* S. @6 6 0@ @6655S DATED this TWENTY-SEVENTH day of MARCH 1991 Ciba-Geigy \G Patent Attorneys for the Applicant SPRUSON FERGUSON 05@556 S S 0S S S 5 S. S S*