Phenylacetic acid derivatives, process and intermediate products for their preparation, and their use as fungicides and pesticides

Phenylacetic acid derivatives of the formula I where the variables are as disclosed herein, their salts, processes and intermediates for their preparation, and their use for controlling harmful fungi and animal pests.

The present invention relates to phenylacetic acid derivatives of the formula I

where the variables have the following meanings:

Y is O or NZ, Z being hydrogen or C 1 -C 4 -alkyl;

m is 0, 1 or 2, it being possible for the radicals R 2 to be different if m is 2;

R 4 is C 1 -C 4 -alkylenedioxy, the alkylene groups being partially or fully halogenated, or is one of the radicals:

C( NOR a ) A p R b ,

NR c (C O) A p R a ,

O (C O) NR a R b or

N(R c ) OR d , where

R a , R b independently of one another are hydrogen or in each case unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocyclyl, aryl or hetaryl,

R c , R d independently of one another are hydrogen or in each case unsubstituted or substituted alkyl, alkenyl, alkynyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, cycloalkyl, cycloalkylcarbonyl, cycloalkyloxycarbonyl, arylcarbonyl or hetarylcarbonyl,

p is 0 or 1 and

A is oxygen, sulfur or nitrogen, the nitrogen having attached to it hydrogen or C 1 -C 6 -alkyl;

n is 1 or 2, it being possible for the radicals R 4 to be different if n is 2;

R 5 is hydrogen,

C 3 -C 6 -cycloalkyl, which can be partially or fully halogenated and/or, independently of each other, can have attached to it one to three of the following groups: cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy and C 1 -C 6 -alkylthio,

and to salts thereof.

Moreover, the invention relates to processes and intermediates for the preparation of these compounds and to their use for controlling animal pests and harmful fungi.

Phenylacetic acid derivatives for pest control have been disclosed in the literature (cf. WO-A 95/18789, WO-A 95/21153, WO-A 95/21154), but they are not yet satisfactory with a view to their activity.

It is an object of the present invention to provide novel compounds of this type which have an improved activity.

We have found that this object is achieved by the phenylacetic acid derivatives I defined at the outset. Moreover, we have found processes and intermediates for their preparation, compositions comprising them for controlling animal pests and harmful fungi, and their use for these purposes.

The compounds I are accessible via various routes by processes known per se.

When synthesizing the compounds I, it is, in principle, irrelevant whether the group C(X) CO Y R 1 or the group

is first synthesized.

When synthesizing the group

a procedure is generally followed in which a benzyl derivative of the formula II is reacted with a hydroxyimine of the formula III.

The reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base, eg. sodium hydride, potassium hydroxide, potassium carbonate or triethylamine, following the methods described in Houben-Weyl, 4th Edition, Vol. E 14b, p. 370 et seq. and ibd. Vol. 10/1, p. 1189 et seq.

The hydroxyimine III which is required is obtained, for example, by reacting a corresponding dihydroxyimine IV with the compound of the formula VI

Those compounds of the formula IV which are not already known can be prepared by methods known per se (cf. Gazz. Chim. Ital. 59 (1929), 719; Collect. Bull. Soc. Chim. Fr. 17 (1897), 71).

Alternatively, the compounds I can also be obtained by reacting the benzyl derivative II first with the dihydroxyimino derivative IV to give a corresponding benzyl oxime of the formula V, V subsequently being reacted with a compound of a sic formula VI to give I.

Similarly, it is also possible to prepare the hydroxyimine sic of the formula III which is required from a carbonylhydroxyimine VII by reacting the latter with a hydroxylamine IXa or a salt thereof IXb.

Q in formula IXb is the anion of an acid, in particular of an inorganic acid, eg. halide, such as chloride.

The reaction is carried out in a manner known per se in an inert organic solvent following the methods described in EP-A 513 580; Houben-Weyl, 4th Edition, Vol. 10/4, p. 73 et seq., Vol. E 14b, p. 369 et seq. and p. 385 et seq.

Those compounds of the formula VII which are not already known can be prepared by methods known per se (J. Am. Pharm. Assoc. 35 (1946), 15).

Alternatively, the compounds I can also be obtained by reacting the benzyl derivative II first with the carbonylhydroxyimino derivative VII to give a corresponding benzyloxyimine of the formula VIII, VIII subsequently being reacted with the hydroxylamine IXa or the salt thereof IXb to give I.

The reaction is carried out in a manner known per se in an inert organic solvent following the methods described in Houben-Weyl, 4th Edition, Vol. E 14b, p. 369 et seq., Vol. 10/1, p. 1189 et seq. and Vol. 10/4, p. 73 et seq. or EP-A 513 580.

A further possibility of preparing the compounds I where R 3 is not C 1 -C 4 -alkoxy is to react the benzyl derivative II with N-hydroxyphthalimide, subsequently subjecting the product to hydrazinolysis to give the benzylhydroxylamine IIa and further reacting IIa with a carbonyl compound X.

The reaction is carried out in a manner known per se in an inert organic solvent following the methods described in EP-A 463 488 and EP-A 585 751.

The carbonyl compound X which is required is obtained, for example, by reacting a corresponding hydroxyiminocarbonyl compound VIIa with a compound of the formula VI

or by reacting a corresponding dicarbonyl compound XI with a hydroxylamine IXa or a salt thereof IXb

Those compounds of the formula VIIa or XI which are not already known can be prepared by methods known per se (J. Chem. Soc., 3094 (1955); Bull. Soc. Chim. Fr., 2894 (1969); Tetrahedron 40 (1984), 2035).

Similarly, the compounds I can also be obtained by first reacting the benzylhydroxylamine IIa with the hydroxyimino derivative VIIa to give the corresponding benzyloxyimino derivative of the formula V, V subsequently being reacted with a compound of the formula VI as described above to give I.

Similarly, the compounds I can also be prepared by first converting the benzylhydroxylamine IIa with the dicarbonyl derivative of the formula XI to give the benzyloxyimino derivative of the formula VIII and subsequently reacting VIII with the hydroxylamine IXa or a salt thereof IXb as described above to give I.

Furthermore, the compounds I are also obtained by first converting a compound III with a lactone XII following the methods described in EP-A 493 711 to give the corresponding benzoic acid XIII and converting XIII into the cyanocarboxylic acids XIV via the corresponding halides, and the cyanocarboxylic acids XIV are converted into the -ketoesters XV via a Pinner reaction (Angew. Chem. 94 (1982), 1) and, if desired, the -ketoesters XV are reacted further to give the -ketoamides XVI (cf. EP-A 348 766, DE-A 37 05 389, EP-A 178 826, DE-A 36 23 921, Houben-Weyl, 4th dition, Vol. E5, p. 941 et seq.).

Compounds I where R 1 is hydrogen are obtained by this process by means of hydrolyzing the esters XV and subsequent reaction to give I.

The compounds I where R 4 is C( NOR a ) R b , NR c (C O) A p R a , O (C O) NR a R b or N(R c ) OR d are preferably synthesized by generally known methods starting from the compounds XVII, XVIII, XIX or XX.

The compounds I where Y is NH can also be obtained from the corresponding esters (Y O) by reacting the latter with amines of the formula R 1 NH 2 .

Owing to their C C and C N double bonds, the compounds I can be obtained from their preparation as E/Z isomer mixtures, which can be separated into the individual compounds in the customary manner, for example by crystallization or chromatography.

If isomer mixtures are obtained from the synthesis, however, a separation is generally not absolutely necessary since in some cases the individual isomers can be converted into each other during formulation for use or upon use (eg. when exposed to light, acids or bases). Similar conversions can also take place after use, for example in the case of the treatment of plants in the treated plants or in the harmful fungus or animal pest to be controlled.

As regards the C X double bond, the E isomers of the compounds I are preferred with a view to their activity (configuration based on the OCH 3 or the CH 3 group relative to the CO Y R 1 group).

As regards the C(R 3 ) NOCH 2 double bond, the cis isomers of the compounds I are preferred with a view to their activity (configuration based on the radical R 3 relative to the OCH 2 group).

In the definitions of the compounds I given at the outset, collective terms were used which generally represent the following groups:

Alkylamino: an amino group which has attached to it a straight-chain or branched alkyl group having 1 to 6 carbon atoms as mentioned above;

Dialkylamino: an amino group which has attached to it two straight-chain or branched alkyl groups which are independent of each other and have in each case 1 to 6 carbon atoms as mentioned above;

Alkylcarbonyl: straight-chain or branched alkyl groups having 1 to 10 carbon atoms which are linked to the skeleton via a carbonyl group ( CO );

Alkylsulfonyl: straight-chain or branched alkyl groups having 1 to 6 or 10 carbon atoms which are linked to the skeleton via a sulfonyl group ( SO 2 );

Alkylsulfoxyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms which are linked to the skeleton via a sulfoxyl group ( S( O) );

Alkylaminocarbonyl: alkylamino groups having 1 to 6 carbon atoms as mentioned above which are linked to the skeleton via a carbonyl group ( CO );

Dialkylaminocarbonyl: dialkylamino groups having in each case 1 to 6 carbon atoms per alkyl radical as mentioned above which are linked to the skeleton via a carbonyl group ( CO );

Alkylaminothiocarbonyl: alkylamino groups having 1 to 6 carbon atoms as mentioned above which are linked to the skeleton via a thiocarbonyl group ( CS );

Dialkylaminothiocarbonyl: dialkylamino groups having in each case 1 to 6 carbon atoms per alkyl radical as mentioned above which are linked to the skeleton via a thiocarbonyl group ( CS );

Haloalkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, eg. C 1 -C 2 -haloalkyl, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

Alkoxycarbonyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms which are linked to the skeleton via an oxycarbonyl group ( OC( O) );

Haloalkoxy: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, and these groups being linked to the skeleton via an oxygen atom;

Alkylenedioxy: divalent branched or unbranched chains of 1-4 CH 2 groups which may be partially or fully halogenated, and both valencies are linked to the skeleton via an oxygen atom, eg. OCH 2 O, O CH 2 CH 2 O, O CHCl CHCl O or O (CH 2 ) 3 O;

Alkenyloxy: straight-chain or branched alkenyl groups having 2 to 6 carbon atoms and a double bond in any position which are linked to the skeleton via an oxygen atom ( O );

Alkenylthio and alkenylamino: straight-chain or branched alkenyl groups having 2 to 6 carbon atoms and a double bond in any position which are linked to the skeleton via a sulfur atom (alkenylthio) or a nitrogen atom (alkenylamino);

Alkenylcarbonyl: straight-chain or branched alkenyl groups having 2 to 10 carbon atoms and a double bond in any position which are linked to the skeleton via a carbonyl-group ( CO );

Alkynyloy, or alkynylthio and alkynylamino: straight-chain or branched alkynyl groups having 2 to 6 carbon atoms and a triple bond in any position which are linked to the skeleton via an oxygen atom (alkynyloxy), via a sulfur atom (alkynylthio) or via a nitrogen atom (alkynylamino).

Alkynylcarbonyl: straight-chain or branched alkynyl groups having 3 to 10 carbon atoms and a triple bond in any position which are linked to the skeleton via a carbonyl group ( CO );

Cycloalkenyl, or cycloalkenyloxy, cycloalkenylthio and cycloalkenylamino: monocyclic alkenyl groups having 3 to 6 carbon ring members which are linked to the skeleton directly or via an oxygen atom (cycloalkenyloxy) or a sulfur atom (cycloalkenylthio) or via a nitrogen atom (cycloalkenylamino), eg. cyclopropenyl, cyclobutenyl, cyclopentenyl or cyclohexenyl;

Cycloalkyloxy, or cycloalkylthio and cycloalkylamino: monocyclic alkyl groups having 3 to 6 carbon ring members which are linked to the skeleton via an oxygen atom (cycloalkyloxy) or a sulfur atom (cycloalkylthio) or via a nitrogen atom (cycloalkylamino), eg. cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;

Cycloalkylcarbonyl: cycloalkyl groups as defined above which are linked to the skeleton via a carbonyl group ( CO );

Cycloalkyloxycarbonyl: cycloalkyloxy groups as defined above which are linked to the skeleton via a carbonyl group ( CO );

Alkenyloxycarbonyl: alkenyloxy groups as defined above which are linked to the skeleton via a carbonyl group ( CO );

Alkynyloxycarbonyl: alkynyloxy groups as defined above which are linked to the skeleton via a carbonyl group ( CO );

Aryl, or aryloxy, arylthio, arylcarbonyl and arylsulfonyl: aromatic mono- or polycyclic hydrocarbon radicals which are linked to the skeleton directly, or (aryloxy) via an oxygen atom ( O ), or (arylthio) via a sulfur atom ( S ), or (arylcarbonyl) via a carbonyl group ( CO ) or (arylsulfonyl) via a sulfonyl group ( SO 2 ), eg. phenyl, naphthyl and phenanthrenyl, or phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals;

Arylamino: aromatic mono- or polycyclic hydrocarbon radicals which are linked to the skeleton via a nitrogen atom;

Hetaryl, or hetaryloxy, hetarylthio, hetarylcarbonyl and hetarylsulfonyl: aromatic mono- or polycyclic radicals which, besides carbon ring members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom and which are linked to the skeleton directly, or (hetaryloxy) via an oxygen atom ( O ) or (hetarylthio) via a sulfur atom ( S ), (hetarylcarbonyl) via a carbonyl group ( CO ) or (hetarylsulfonyl) via a sulfonyl group ( SO 2 ), eg.

5-membered hetaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom: 5-membered hetaryl ring groups which, besides carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or sulfur atom as ring members, eg. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl;

benzo-fused 5-membered hetaryl containing one to three nitrogen atoms or one nitrogen atom and/or one oxygen or sulfur atom: 5-membered hetaryl ring groups which, besides carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom as ring members, and in which two adjacent carbon ring members or one nitrogen and an adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group;

5-membered hetaryl, linked via nitrogen and containing one to 4 nitrogen atoms, or benzo-fused 5-membered hetaryl linked via nitrogen and containing one to three nitrogen atoms: 5-membered hetaryl ring groups which, besides carbon atoms, can contain one to four nitrogen atoms, or one to three nitrogen atoms, respectively, as ring members and in which two adjacent carbon ring members or one nitrogen and an adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group, these rings being linked to the skeleton via one of the nitrogen ring members;

benzo-fused 6-membered hetaryl containing one to four nitrogen atoms: 6-membered hetaryl ring groups in which two adjacent carbon ring members can be bridged by a buta-1,3-diene-1,4-diyl group, eg. quinoline, isoquinoline, quinazoline and quinoxaline,

and the corresponding oxy, thio, carbonyl or sulfonyl groups.

Netarylamino: aromatic mono- or polycyclic radicals which, besides carbon ring members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom and which are linked to the skeleton via a nitrogen atom.

The term partially or fully halogenated is intended to express that some or all of the hydrogen atoms in thus characterized groups can be replaced by identical or different halogen atoms as mentioned above.

Compounds I which are preferred for their biological activity are those where R a and R b independently of one another are:

Other preferred compounds I are those where R c and R d independently of one another are:

C 3 -C 6 -cycloalkyl, cycloalkylcarbonyl, cycloalkyloxycarbonyl, it being possible for these radicals to be partially or fully halogenated and/or to have attached to them one to three of the following groups: cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy and C 1 -C 6 -alkylthio;

Moreover, preferred compounds I are those where R 5 is:

C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, it being possible for these radicals to be partially or fully halogenated or to have attached to them one to three of the following groups: cyano, hydroxyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkylthio, C 3 -C 6 -cycloalkyl or oxiranyl, it being possible for the cyclic groups, in turn, to have attached to them one to five of the following substituents: halogen and C 1 -C 4 -alkyl.

Especially preferred compounds I are those where R a and R b independently of one another are:

Furthermore, especially preferred compounds I are those where R c and R d independently of one another are:

C 3 -C 6 -cycloalkyl, cycloalkylcarbonyl, cycloalkyloxycarbonyl, it being possible for these radicals to be partially or fully halogenated and/or to have attached to them one to three of the following groups: cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy and C 1 -C 6 -alkylthio;

Furthermore, preferred compounds of the formula I are those where m is 0.

Equally, preferred compounds of the formula I are those where R 1 is methyl.

Other preferred compounds I are those where R 1 is hydrogen.

Especially preferred compounds I are those where R 3 is methyl.

Furthermore, preferred compounds I are those where R 3 is methoxy.

Moreover, preferred compounds I are those where R 3 is cyano.

Furthermore, preferred compounds I are those where R 3 is trifluoromethyl.

Furthermore, preferred compounds I are those where n is 1.

Moreover, preferred compounds I are those where R 4 is (C O) R a .

Furthermore, preferred compounds I are those where R 4 is C 1 -C 4 -alkylcarbonyl.

Moreover, preferred compounds I are those where R 4 is C( NOR a ) A p R b .

Furthermore, preferred compounds I are those where R 4 is C( NOR a ) R b .

Moreover, preferred compounds I are those where R 4 is NR c (C O) A p R a .

Moreover, preferred compounds I are those where R 4 is O (C O) NR a R b .

Furthermore, preferred compounds I are those where R 4 is N(R c ) OR d .

Furthermore, preferred compounds I are those where R a or R b is C 1 -C 6 -alkyl or C 2 -C 6 -alkenyl.

Furthermore, preferred compounds I are those where R 4 is C 1 -C 4 -alkylenedioxy, the alkylene groups being partially or fully halogenated, preferably fluorinated.

Especially preferred compounds I are those where R 4 is difluoromethylenedioxy.

Especially preferred compounds I are those where R 5 is C 1 -C 6 -alkyl.

Very especially preferred compounds I are those where R 5 is methyl or ethyl.

Furthermore, preferred compounds I are those where R 5 is C 1 -C 6 -alkylsulfonyl.

Besides, preferred compounds of the formula I are those where X is NOCH 3 .

Besides, preferred compounds of the formula I are those where X is CHOCH 3 and Y is O.

Besides, preferred compounds of the formula I are those where X is CHCH 3 and Y is O.

Moreover, preferred compounds of the formula I are those where Y is O.

Furthermore, preferred compounds of the formula I are those where Y is NH or N CH 3 .

Especially preferred compounds of the formula I are those where Y is NH and R 1 is methyl.

Especially preferred compounds of the formula I are those where Y is O and R 1 is methyl.

Compounds I which are particularly preferred with a view to their use are those compiled in the tables which follow.

The tables which follow (1 to 596) are based on the formulae I.1, I.2, I.3 and 1.4, the double bonds marked E having the E configuration:

The compounds I are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidiomycetes. Some of them act systemically and can be employed as foliar- and soilacting fungicides.

They are especially important for controlling a large number of fungi on a variety of crop plants such as wheat, rye, barley, oats, rice, maize, grass, cotton, soybeans, coffee, sugar cane, grapevines, fruit species, ornamentals and vegetable species such as cucumbers, beans and cucurbits, and on the seeds of these plants.

Specifically, they are suitable for controlling the following plant diseases: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Podosphaera leucotricha on apples, Uncinula necator on grapevines, Puccinia species on cereals, Rhizoctonia species on cotton, rice and lawns, ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, grapevines, vegetables and ornamentals, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium and Verticillium species on a variety of plants, Plasmopara viticola on grapevines, Pseudoperonospora species in hops and cucumbers, Alternaria species on vegetables and fruit.

The compounds I are applied by treating the fungi, or the plants, seeds, materials or the soil to be protected against fungal infection, with a fungicidally active amount of the active ingredients. Application is effected before or after infection of the materials, plants or seeds by the fungi.

Using formulation auxiliaries known per se, they can be converted into the customary formulations (compositions), such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the intended purpose; in any case, it should guarantee fine and uniform distribution of the compounds I. The formulations are prepared in a known manner, eg. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible for other organic solvents to be used as auxiliary solvents if water is used as the diluent. Suitable auxiliaries are essentially: solvents such as aromatics (eg. xylene), chlorinated aromatics (eg. chlorobenzenes), paraffins (eg. mineral oil fractions), alcohols (eg. methanol, butanol), ketones (eg. cyclohexanone), amines (eg. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (eg. kaolins, clays, talc, chalk) and ground synthetic minerals (eg. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.

In general, the fungicidal compositions comprise between 0.1 and 95, preferably between 0.5 and 90, % by weight of active ingredient.

Depending on the nature of the desired effect, the rates of application are between 0.01 and 2.0 kg of active ingredient per ha.

In the treatment of seed, amounts of active ingredient of from 0.001 to 0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram of seed.

In the use form as fungicides, the agents according to the invention can also be present together with other active ingredients, the sic eg. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.

A mixture with fungicides frequently results in a widened spectrum of fungicidal action.

The following list of fungicides together with which the compounds according to the invention can be used is intended to illustrate the possible combinations but not to impose any limitation:

Phenylpyrroles, such as 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile.

Cinnamamides, such as N-3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-acryloylmorpholine.

Moreover, the compounds of the formula I are suitable for efficiently controlling pests from the classes of the insects, arachnids and nematodes. They can be employed as pesticides in crop protection and in the hygiene, stored-product and veterinary sectors.

The compounds I, as such, in the form of their formulations (compositions) which have been obtained using formulation auxiliaries known per se or in the form of the use forms prepared therefrom, can be applied by spraying, atomizing, dusting, spreading or pouring, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading, or granules. The use forms depend entirely on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.

The concentrations of active ingredient in the ready-to-use preparations can be varied within substantial ranges.

They are in general between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used very successfully in the ultra-low volume method (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even the active ingredient without additives.

The rate of application of active ingredient for controlling pests is from 0.1 to 2.0, preferably 0.2 to 1.0, kg/ha under field conditions.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, and strongly polar solvents, eg. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, if desired, oil or solvent, and these concentrates are suitable for dilution with water.

Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances together with a solid carrier.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

The following are examples of formulations:

I. 5 parts by weight of a compound I according to the invention 25 are mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dust which comprises 5% by weight of the active ingredient.

II. 30 parts by weight of a compound I according to the invention are mixed intimately with a mixture of 92 parts by weight of puverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel. This gives a preparation of the active ingredient with good adhesion properties (comprises 23% by weight of active ingredient).

III. 10 parts by weight of a compound I according to the invention are dissolved in a mixture composed of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 2 parts by weight of calcium dodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 9% by weight of active ingredient).

IV. 20 parts by weight of a compound I according to the invention are dissolved in a mixture composed of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil (comprises 16% by weight of active ingredient).

V. 80 parts by weight of a compound I according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill (comprises 80% by weight of active ingredient).

VI. 90 parts by weight of a compound I according to the invention are mixed with 10 parts by weight of N-methyl- -pyrrolidone, resulting in a solution which is suitable for use in the form of microdrops (comprises 90% by weight of active ingredient).

VII. 20 parts by weight of a compound I according to the invention are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

VIII. 20 parts by weight of a compound I according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene- -sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active ingredient.

Various types of oils, or herbicides, fungicides, other pesticides, or bactericides, can be added to the active ingredients, if desired only immediately prior to use (tank mix). These agents can be admixed with the agents according to the invention in a weight ratio of 1:10 to 10:1.

SYNTHESIS EXAMPLE 1

Synthesis of Compound I.11 of Table 1

1a) Synthesis of

162 g (1.2 mol) of AlCl 3 were added, a little at a time, to a stirred mixture of 82 g (0.45 ml) of pivalanilide and 40 g (0.43 mol) of propionyl chloride, during which process the temperature of the reaction mixture climbed to approximately 100 C. and hydrochloric acid was evolved.

The reaction mixture was subsequently stirred for 6 hours at 80 C. The reaction mixture was carefully poured onto ice, and the aqueous phase was extracted with methyl t-butyl ether and ethyl acetate.

The combined organic phases were extracted 2 with water, and the aqueous phase was dried over MgSO 4 and concentrated. The residue was purified by column chromatography with cyclohexane/ethyl acetate mixtures. This gave 22.3 g (22%) of the title Compound 1a as a colorless solid (m.p. 121 C.).

1b) Synthesis of

A mixture of 22 g (94 mmol) of Compound la in 200 ml of toluene was treated at 20 C. with 80 ml of hydrochloric acid solution in ether (approximately 4N) and 12 g (115 mmol) of n-butyl nitrite in 50 ml of ether are subsequently added dropwise. The mixture was then stirred overnight at room temperature. The title compound crystallized out of the reaction mixture. The solid which had precipitated was filtered off with suction, washed with methyl t-butyl ether, ethyl acetate and methylene chloride and dried in a stream of nitrogen. This gave 17 g (69%) of the title Compound 1b as a colorless solid (m.p. 198 C.). Work-up of the mother liquor yielded a second crystal fraction of 3.5 g (14%).

1c) Synthesis of

A mixture of 16 g (61 mmol) of Compound 1b, 12 g (150 mmol) of pyridine and 6.5 g (78 mmol) of O-methylhydroxylamine hydrochloride in 100 ml of methanol was stirred overnight at room temperature. The reaction mixture was subsequently concentrated and the residue taken up in methylene chloride. The organic phase was washed with dilute hydrochloric acid and water, dried over MgSO 4 and concentrated. The residue crystallized and was obtained by stirring with methylene chloride. This gave 3.6 g (20%) of the title Compound 1c as a colorless solid (m.p. 208 C.). Work-up of the mother liquor yielded a second crystal fraction of 5.2 g of 1c (29%).

Synthesis of I.11

A mixture of 2 g (6.8 mmol) of the Compound 1c and 0.25 g (10 mmol) of sodium hydride in 20 ml of dimethylformamide was stirred for 15 minutes at room temperature. 2 g (7 mmol) of methyl 2-bromomethylphenylglyoxylate trans-O-methyloxime (EP 254 426) were subsequently added, and the mixture was stirred for one hour at room temperature. The reaction mixture was then diluted with water and the aqueous phase extracted with methyl t-butyl ether. The combined organic phases were washed with water, dried over MgSO 4 and concentrated. The residue crystallized, and the crystals were filtered off with suction and dried in a stream of nitrogen. This gave 2.8 g (83%) of the title Compound I.11 as a pale yellow solid (m.p. 114-116 C.).

SYNTHESIS EXAMPLE 2

Synthesis of Compound I.12 of Table 1

A mixture of 1.5 g (3 mmol) of Compound I.11 of Synthesis Example 1 and 0.1 g (4 mmol) of sodium hydride in 20 ml of dimethylformamide was stirred for 10 minutes at room temperature. 0.7 g (5 mmol) of methyl iodide was subsequently added and the mixture was stirred at room temperature for approximately 2 hours. The reaction mixture was subsequently diluted with water and the aqueous phase extracted with methyl t-butyl ether. The combined organic phases were extracted with water, dried over MgSO 4 and concentrated. The residue was purified by column chromatography with cyclohexane/ethyl acetate mixture. This gave 1.2 g (78%) of the title Compound I.12 as pale yellow crystals (m.p. 111-113 C.).

SYNTHESIS EXAMPLE 3

Synthesis of Compound I.10 of Table 1

A mixture of 0.9 g (1.8 mmol) of Compound I.12 of Synthesis Example 2 and 3 ml of tetrahydrofuran in 20 ml of 40% strength methylamine solution was stirred for 1 hour at 50 C. Excess methylamine was subsequently evaporated in vacuo and the remaining aqueous phase was extracted with methylene chloride. The combined organic phases were washed with water, dried over MgSO 4 and concentrated. The residue crystallized and was obtained by stirring with methyl t-butyl ether. This gave 0.7 g (76%) of the title Compound I.10 as a colorless solid m.p. 168-170 C.).

SYNTHESIS EXAMPLE 4

Synthesis of Compound I.52 of Table 1

4a. Synthesis of

17.5 g (0.21 mol) of O-methylhydroxylamine hydrochloride were added to a solution of 20 g (0.14 mol) of 4-cyanoacetophenone in 200 ml of methanol, and the mixture was first stirred for 2 hours at room temperature and subsequently for 2 hours at 60 C. The reaction mixture was poured onto water and extracted with methyl tert-butyl ether. The combined organic phases were washed with water, dried over Na 2 SO 4 and concentrated. The residue was purified by column chromatography on silica gel (n-hexane). This gave 23.3 g (97% yield) of Compound 4a as a white powder (m.p. 58-60 C.).

4b. Synthesis of

At 15 C., 53 ml (0.15 mol) of an ethylmagnesium bromide solution (3M in diethyl ether) was added dropwise to a solution of 17.6 g (0.10 mol) of Compound 4a in 200 ml of tetrahydrofuran, and the reaction mixture was allowed to come to room temperature and was subsequently heated for 2.5 hours at 40 C. The reaction mixture was cooled to 0-5 C., hydrolyzed with 100 ml of ice-water and brought to pH 6 with glacial acetic acid. After a further addition of water, the mixture was extracted with methyl tert-butyl ether, and the organic phase was washed with water, dried over Na 2 SO 4 and concentrated. The residue was purified by column chromatography on silica gel (n-hexane). This gave 13.9 g (67% yield) of Compound 4b as a pale yellow powder (m.p. 75-77 C.).

4c) Synthesis of

80 ml of saturated HCl solution in ether were added at 20 C. to 13.2 g (0.064 mol) of Compound 4b in 150 ml of toluene. At this temperature, a solution of 7.3 g (0.071 mol) of n-butyl nitrite in 60 ml of diethyl ether was subsequently added dropwise. The mixture was stirred for 1 hour at 10 C. and subsequently allowed to come to room temperature. After a total of 16 hours, the reaction batch was washed with ice-water and subsequently extracted with 1M sodium hydroxide solution. The alkaline phase was separated off and rendered neutral with 20% strength sulfuric acid. The batch was subsequently extracted with methylene chloride, and the organic phase was washed with water, dried over Na 2 SO 4 and concentrated. The residue was dissolved in a small amount of methylene chloride and purified by column chromatography on silica gel (n-hexane). This gave 13.2 g (88% yield) of Compound 4c as a colorless oil.

4d) Synthesis of

5 g (0.021 mol) of Compound 4c in 100 ml of methanol and 5 g of pyridine were treated with a solution of 2.7 g (0.032 mol) of O-methylhydroxylamine hydrochloride in 20 ml of methanol. The reaction mixture was stirred for 16 hours at room temperature and subsequently for 2 hours at 60 C. The reaction batch was poured into a mixture of methyl tert-butyl ether and 10% strength hydrochloric acid and extracted with methyl tert-butyl ether. The combined organic phases were washed with 10% hydrochloric acid and water, dried over Na 2 SO 4 and concentrated. The residue was dissolved in 100 ml of toluene and treated with 0.9 g (6.3 mmol) AlCl 3 . After 5 hours at 40 C. and a further 12 hours at room temperature, the reaction mixture was added to a mixture of ethyl acetate and 10% hydrochloric acid. The mixture was extracted with ethyl acetate and the organic phase was washed with water, dried over Na 2 SO 4 and concentrated. After triturating the residue with methanol, 3.7 g (66% yield) of Compound 4d were obtained as a pale yellow powder (m.p. 162-165 C.).

4e) Synthesis of Compound I.51 of Table 1

A solution of 3.0 g (11.4 mmol) of Compound 4d in 50 ml of N,N-dimethylformamide was treated with 2.1 g (11.4 mmol) of 30% strength sodium methoxide solution (in methanol) and stirred for 15 minutes at room temperature. After the addition of 3.3 g (11.4 mmol) of methyl 2-bromomethylphenylglyoxylate trans-O-methyloxime (EP 254 426) in 30 ml of N,N-dimethylformamide, the mixture was stirred for 0.5 hour at room temperature. The mixture was subsequently poured into ice-water and extracted with methyl tert-butyl ether. The organic phase was washed with water, dried over Na 2 SO 4 and concentrated. Crystallization of the residue from methanol gave 4.7 g (88% yield) of the title Compound I.51 as colorless crystals (m.p. 112-114 C.).

4f) Synthesis of Compound I.52 of Table 1

A solution of 2.0 g (4.3 mmol) of Compound 4e in 50 ml of tetrahydrofuran was treated with 3.3 g of 40% strength aqueous monomethylamine solution and stirred for 24 hours at room temperature. The resulting reaction mixture was treated with water and extracted with methyl tert-butyl ether. The organic phase was washed, dried and concentrated under reduced pressure. Purification of the residue by column chromatography on silica gel (methyl tert-butyl ether/n-hexane 1/1) gave 1.7 g (85% yield) of the title compound as a colorless oil.

Compounds I.1-I.9, I.13-I.50 and I.53-I.59, which are listed in Table 1 below, were prepared by similar methods.

The melting points (m.p.) are given in C., the IR bands in cm 1 and the 1 H NMR data in ppm relative to CDCl 3 as the standard.

The fungicidal activity of the compounds of the formula I is demonstrated by the following experiments:

The active ingredients are formulated as a 20% strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil LN (Lutensol AP6, wetting agent having emulsifier and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Emulphor EL (Emulan EL, emulsifier based on ethoxylated fatty alcohols) and diluted with water to give the desired concentration. The experiments were evaluated visually.

The activity of the compounds of the general formula I against animal pests is demonstrated by the following experiments.

The active ingredients are formulated

a) as a 0.1% strength solution in acetone or

b) as a 10% strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil LN (Lutensol AP6, wetting agent with emulsifier and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Emulphor EL (Emulan EL, emulsifier based on ethoxylated fatty alcohols)

and diluted to give the desired concentration, using acetone in the case of a) and water in the case of b).

USE EXAMPLE 1

Efficacy Against Powdery Mildew of Wheat

Leaves of wheat seedlings cv. Fr hgold in pots were sprayed with aqueous spray mixture comprising 80% of active ingredient of Table 1 and 20% of emulsifier in the dry matter and, 24 hours after the spray coating had dried on, dusted with oidia (spores) of powdery mildew of wheat (Erysiphe graminis var. tritici). The test plants were subsequently placed in a greenhouse at from 20 to 22 C. and a relative atmospheric humidity of 75 to 80%. After 7 days, the extent of mildew development was determined.

Efficacy Against Leaf Rust of Wheat

Leaves of wheat seedlings cv. Kanzler in pots were dusted with leaf rust spores (Puccinia recondite). The pots were then placed for 24 hours in a chamber with high atmospheric humidity (90 to 95%) at from 20 to 22 C. During this time, the spores germinated, and the germ tubes penetrated the leaf tissue. The infected plants were subsequently sprayed to runoff point with aqueous spray mixtures comprising 80% of active ingredient of Table 1 and 20% of emulsifier in the dry matter. After the spray coating had dried on, the test plants were placed in a greenhouse at from 20 to 22 C. and a relative atmospheric humidity of 65 to 70%. After 8 days, the extent of rust development on the leaves was determined.