Title of Invention

FUNGICIDAL MIXTURES BASED ON AMIDE COMPOUNDS AND MORPHOLINE OR PIPERIDINE DERIVATIVES

Abstract Funcficidal mixtures based on amide compounds and morpholine or piperidine derivatives. Abstract Fungicidal mixtures comprising as active components a) an amide compound of the formula I in which A is an aryl group or an aromatic or non-aromatic, 5- or 6-membered heterocycle vhich has from 1 to 3 hetero atoms se¬lected from 0, N and S; where the aryl group or the heterocycle may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, halogen, CHF2 CF3, alkoxy, haloalko-xy, alkylthio, alkylsulfynyl and alkylsulfonyl; R<SUP>1</SUP> is a hydrogen atom; R<SUP>2</SUP> is a phenyl or cycloalkyl group which may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cyclo-alkenyloxy, phenyl and halogen, where the aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or the cycloaliphatic radicals may be substituted by from 1 to 3 alkyl groups and where the phenyl group may have from 1 to 5 halogen atoms and/or from 1 to 3 substituents which are selected, independently of one another, from alkyl^ halo-alkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and where the amidic phenyl group may or may not be condensed with a saturated 5-membered ring which may or may not be sub¬stituted by one or more alkyl groups and/or may have a hetero atom selected from O and S, and ) a morpholine or piperidine derivative II selected from the group of the compounds IIa, IIb, and IIc in a synergisticaLly effective amount.
Full Text

Fungicidal mixtures based on amide compounds and morpholine or piperidine derivatives.
The present invention relates to fungicidal mixtures for control¬ling harmful fungi and also to methods for controlling harmful fungi using such mixtures.
WO 97/08952 describes mixtures of amide compounds of the formula
I

in which
A is an aryl group or an aromatic or non-aromatic, 5- or 6-mem-bered heterocycle which has from 1 to 3 hetero atoms selected from O, S and S;
where the aryl group or the heterocycle may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, halogen, CHF2, CF3, alkoxy, haloalko-xy, alkylthio, alkylsulfynyl and alkylsulfonyl;
R1 is a hydrogen atom;
R2 is a phenyl or cycloalkyl group which may or may not have 1, 2 or 3 substituents which are selected from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cyclo-alkenyl, cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, where the aliphatic and cycloaliphatic radicals may be par¬tially or fully halogenated and/or the cycloaliphatic radi¬cals may be substituted by from 1 to 3 alkyl groups and where the phenyl group may have from 1 to 5 halogen atoms and/or from 1 to 3 substituents which are selected, independently of one another, from alkyl, haloalkyl, alkoxy, haloalkoxy, al¬kylthio and haloalkylthio, and where the amidic phenyl group may be condensed with a saturated S-membered ring which may be substituted by one or more alkyl groups and/or may have a hetero atom selected from 0 and S, and the active ingredient fenazaquin known as an acaricide.
These mixtures are described as being particularly effective against Botrytis.

wo 97/40673 relates to fungicidal mixtures which inter alia com¬prise active ingredients of the formulae Ila, rib and/or lie, in addition to other fungicidally active ingredients from the group of the oxime ethers and/or the carbamates.

Other fungicidal mixtures comprising active ingredients of the formulae Ila to IIe are known from EP-A 797386, WO 97/06681, EP-B 425857, EP-B 524496, EP-A 690792, WO 94/22308 and EP-B 645087.
It is an object of the present invention to provide other parti¬cularly effective mixtures for controlling harmful fungi and in particular for certain indications.
Surprisingly we have found that this object is achieved by a mix¬ture which comprises as active ingredients amide compounds of the formula I defined at the outset and as further fungicidally acti¬ve component a fungicidally active ingredient from the group of the active morpholine and piperidine ingredients of the formulae ria to IIe.


The mixtures according to the invention have synergistic action and are therefore particularly suitable for controlling harmful fungi and in particular powdery mildew fungi.
In the context of the present invention, halogen is fluorine, chlorine, bromine and iodine and is in particular fluorine, chlo¬rine and bromine.
The term "alkyl" includes straight-chain and branched alJtyl groups. These are preferably straight-chain or branched C1-C12-alkyl and in particular__Ci-C6r^alkyl groups. Examples of_alkyl,_ groups are aLkyl such as, in particular, methyl, ethyl, propyl, 1-methylethyl, butyl, l-methylpropyl, 2-methylpropyl, 1,1-di-methylethyl, n-pentyl, l-methylbutyl, 2-methylbutyl, 3-methyl-butyl, 1,2-dijnethylpropyl, 1,1-dimethylpropyl, 2,2-dimethyl-propyl, l-ethylpropyl, n-hexyl, 1-metbylpentyl, 2-iiiethylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-diniethylbutyl, 1,3-dimethyl-butyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethyIpropyl, 1-ethylbutyl, 2-ethylbutyl, l-ethyl-2-methylpropyl, n-heptyl, l-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl.

Haloalkyl is an alkyl group as defined above which is partially or' fully halogenated by one or more halogen atoms, in particular by fluorine and chlorine. Preferably, there are from 1 to 3 halo¬gen atoms present, and the difluoromethyl or the trifluoromethyl group is particularly preferred.
The above statements for the alkyl group and the haloalkyl group apply in a corresponding manner to the alkyl and haloalkyl groups in alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfynyl and alkylsulfonyl.

The alkenyl group may be partially or fully halogenated by one or more halogen atoms, in particular by fluorine or chlorine. The alkenyl group preferably has from 1 to 3 halogen atoms.
The alkynyl group includes straight-chain and branched alkynyl groups. These are preferably straight-chain and branched C3-Ci2-alkynyl groups and in particular Ca-Cg-alkynyl groups. Examples of alkynyl groups are 2-propynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, l-methyl-2-butyny1, 1,l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 2-hexynyl, 3-hexyny1, 4-hexynyl, 5-hexynyl, 1-methy1-2-pentyny1, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl,

2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1; 2-diinethyl-2-butynyl, 1, l-dimethyl-3-butynyl, 1,2-di-methy1-3-butyny1, 2,2-dimethyl-3-butyny1, l-ethyl-2-butyny1, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-propynyl.
The above statements for the alkenyl group and its halogen sub-stituents and for the alkynyl group apply in a corresponding man¬ner to alkenyloxy and alkynyloxy.
The cycloalkyl group is preferably a Ca-Ce-cycloalkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. If the cycloalKyl group is substituted, it preferably has from 1 to 3 Ci-C4-alkyl radicals as substituents.
Cycloalkenyl is preferably a C4-C6-cycloalkenyl group, such as cy-clobutenyl, cyclopentenyl or cyclohexenyl. i£ the cycloalkenyl group is substituted, it preferably has from 1 to 3 Ci-C4-alkyl radicals as substituents.
A cycloalkoxy group is preferably a Cg-Cg-cycloalkoxy group, such as cyclopentyloxy or cyclohexyloxy. If the cycloalkoxy group is substituted, it preferably has from 1 to 3 Ci-C^-alkyl radicals as
substituents.
The cycloalkenyloxy group is preferably a Cs-Cg-cycloalkenyloxy group, such as cyclopentyloxy or cyclohexyloxy. If the cyclo¬alkenyloxy group is substituted, it preferably has from 1 to 3 Ci-C4-alkyl radicals as substituents.
Axyl is preferably phenyl.
If A is a phenyl group, this may have one, ^»>j uj. i-iixee ox tne abovementioned substituents in any position. These substituents are preferably selected, independently of one another, from al-kyl, difluoromethyl, trifluoromethyl and halogen, in particular chlorine, bromine and iodine. Particularly preferably, the phenyl group has a substituent in the 2-position.
If A is a S-membered heterocycle, it is in particular a furyl, thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl, triazoiyl or thiadiazolyl radical or the corresponding dihydro or tetrahydro derivatives thereof. Preference is given to a thiazolyl or pyra¬zolyl radical.

If A is a 6-membered heterocycle, it is in particular a pyridyl ra-dical or a radical of the formula:

in which one of the radicals X and Y is 0, S or NR^^, where R^^ is H or alkyl, and the other of the radicals X and Y is CH2, S, SO, SO2 or NR5. The dotted line means that a double bond may or may not be present.
The e-membered aromatic heterocycle is particularly preferably a pyridyl radical, in particular a 3-pyridyl radical, or a radical of the formula

in which X is CHj, S, SO or SOj.
The abovementioned heterocyclic radicals may or may not have 1, 2 or 3 of the abovementioned substituents, where these substituents are preferably selected* independently-of one another,—front— alkyl, halogen, difluoromethyl or trifluoromethyl.
A is particularly preferably a radical of the formulae:


in which R^, R^, R*, R'^, R^ and R^ independently of one another are hydrogen, alkyl, in particular methyl, halogen, in particular chlorine, CHF2 or CF3.
The radical R^ in the formula I is preferably a hydrogen atom.
The radical R2 in the formula I is preferably a phenyl radical. R2 preferably has at least one substituent which is particularly preferably in the 2-position. The substituent (or the substi-tuents) is (are) preferably selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, halogen and phenyl.
The substituents of the radical R^ may in turn be substituted again. The aliphatic or cycloaliphatic substituents may be par¬tially or fully halogenated, in particular fluorinated or chlori¬nated. They preferably have 1, 2 or 3 fluorine or chlorine atoms. If the substituent of the radical R2 is a phenyl group, this phe¬nyl group may preferably be substituted by from 1 to 3 halogen atoms, in particular chlorine atoms, and/or by a radical which is preferably selected from alkyl and alkoxy. Particularly prefera¬bly, the phenyl group is substituted with a halogen atom in the "p-positlorii i.e.^ERe particularry"~pteferred~~slibstiEueht of the radical R^ is a p-halogen-substituted phenyl radical. The radical R2 may also be condensed with a saturated 5-membered ring, where this ring for its part may have from 1 to 3 alkyl substituents.
R2 is in this case, for example, indanyl, thiaindanyl and oxa-indanyl. Preference is given to indanyl and 2-oxaindanyl which are attached to the nitrogen atom in particular via the 4-position.
^ccording to a preferred embodiment, the composition according to the invention comprises as amide compound a compound of the fot-nula I in which A is as defined below:

phenyl, pyridyl, dihydropyranyl, dihydrooxathiynyl, dihydrooxa-thiynyloxide, dihydrooxathiynyldioxide, furyl, thiazolyl, pyrazo-lyl or oxazolyl, where these groups may have 1, 2 or 3 substi-tuents which are selected, independently of one another, from al-kyl, halogen, difluoromethyl and trifluoromethyl.
According to a further preferred embodiment, A is:
pyridin-3-yl, which may or may not be substituted in the 2-posi-tion by halogen, methyl, difluoromethyl, trifluoromethyl, meth-oxy, methylthio, methylsuIfynyl or methylsulfonyl;
phenyl, which may or may not be substituted in the 2-position by methyl, trifluoromethyl, chlorine, bromine or iodine;
2-methyl-5,6-dihydropyran-3-ylf
2-methyl-5,6-dihydro-l,4-oxathiyn-3-yl or the 4-oxide or 4,4-dioxide thereof;
2-methylfuran-3-yl, which may or may not be substituted in the 4- and/or 5-position by methyl;
thiazol-5-yl, which may or may not be substituted in the 2-and/or 4-position by methyl, chlorine, difluoromethyl or trifluo¬romethyl;
thiazol-4-yl, which may or may not be substituted in the 2-and/or 5-position by methyl, chlorine, difluoromethyl or trifluo¬romethyl ;
. l-methzlpyrazol-4-ylj which_jiay or may nqt _he sub_atituted__in the.. 3- and/or S-position by methyl, chlorine, difluoromethyl or tri¬fluoromethyl; or
oxazol-5-yl, which may or may not be substituted in the 2- and/or 4-position by methyl or chlorine.
According to a further preferred embodiment, the compositions according to the invention comprise as amide compound a compound of the formula I in which R^ is a phenyl group which may or may not be substituted by 1, 2 or 3 of the abovementioned substi-
tuents.

According to a further preferred embodiment, the compositions ac¬cording to the invention comprise as amide compound a compound of the formula I in which R^ is a phenyl group which has one of the following substituents in the 2-position:
Ca-Cfi-alkyl, Cs-Cfi-cycloalkenyl, Cg-Ce-cycloalkyloxy, cycloalkeny-loxy, where these groups may be substituted by 1, 2 or 3 C1-C4-alkyl groups,
phenyl, which is substituted by from 1 to 5 halogen atoms and/or from 1 to 3 groups which are selected, independently of one an¬other, from Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-halo-alkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio,
indanyl or oxaindanyl which may or may not be substituted by 1, 2 or 3 Ci-C4-alk.yl groups.
according to a further preferred embodiment, the compositions ac¬cording to the invention comprise as amide compound a compound of the formula la.



X is methylene, sulfur, sulfynyl or sulfonyl (SO2),
R3 is methyl, difluoromethyl, trifluoromethyl, chlorine, bromine or iodine,
R* is trifluoromethyl or chlorine,
R5 is hydrogen or methyl,
Rfi is methyl, difluoromethyl, trifluoromethyl or chlorine,
R' is hydrogen, methyl or chlorine,
R8 is methyl, difluoromethyl or trifluoromethyl,
R3 is hydrogen, methyl, difluoromethvl. trifluoromethyl or chlo¬rine,
Rio is Ci-Ci-alkyl, Ci-C4-alkoxy, Ci-C4-alkylthio or halogen.
According to a particularly preferred embodiment, the composi¬tions comprise as amide compound a compound of the formula lb


in which
R^ is halogen and
Rii is phenyl which is substituted by halogen.
Particularly preferred mixtures according to the invention com¬prise as compounds of the formulae

Useful amide compounds of the formula I are mentioned in EP-A-545 099 and 589 301 which are incorporated herein in their entirety ty reference.
The preparation of the amide compounds of the foinnula I is Known, for example, from EP-A-545 099 or 569 301 or can be carried out by similar processes.
Also known are the morpholine and piperidine derivatives II (lla: common naae: fenpropiraorph, US-A 4,202,894; lib; common name: fenpropidin, US-A 4,202,894; lie: common name: tridemorph, 0E-A 11 64 152), their preparation and their action against harmful-fungi.

lu uiiiuj.a synergistic activity, even a small amount of amide com¬pound of the formula I is sufficient. Preference is given to employing amide compound and morpholine or piperidine derivative in a weight ratio in a range of from 20:1 to 1:20, in particular 10:1 to 1:10.
Owing to the basic character of their nitrogen atoms, the com¬pounds II are capable of forming salts or adducts with inorganic or organic acids or with metal ions.
Examples of inorganic acids are hydrohalic acids such as hydro¬fluoric acid, hydrochloric acid, hydrobromic acid and hydriodic acid, and furthermore carbonic acid, sulfuric acid, phosphoric acid and nitric acid.
Suitable organic acids are, for example, formic acid and alkanoic acids, such as acetic acid, triflucroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic ra¬dicals, such as phenyl and naphthyl, which carry one or two sulfo groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), aryl-phosphonic acids or aryldiphosphonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two phosphonic acid radicals), it being possible for the alkyl or aryl radicals to carry further substituents, eg, p-toluenesulfonic acid, sali¬cylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-ace-toxybenzoic acid, etc.
Suitable metal"ions are";~in" particular, the "ions of ttre "elements" of the first to eighth sub-group, in particular chromium, man¬ganese, iron, cobalt, nickel, copper, zinc and furthermore of the second main group, in particular calcium and magnesium, and of the third and fourth main group, in particular aluminum, tin and lead. The metals can exist in the various valencies which they can assume.
When preparing the mixtures, it is preferred to employ the pure active ingredients I and II, to which further active ingredients against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active in¬gredients or fertilizers can be admixed.

The mixtures of the compounds I and II, or the compounds I and II used simultaneously, jointly or separately, exhibit outstanding activity against a wide range of phytopathogenic fungi, in parti¬cular from the classes of the Aacomycetes, Basidiomycetes, Phyco-mycetes and Deuteromycetes. Some of them act systemically and can therefore be employed as foliar- and soil-acting fungicides.
They are especially important for controlling a large number of fungi in a variety of crop plants, such as cotton, vegetable spe¬cies (eg. cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in grapevines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporimn species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries, vegetables, ornamentals and grape¬vines, Cercospora arachidiccla in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzac in rice, Phytophthora infestans in potatoes and tomatoes, Plasmopara viti-cola in grapevines, Pseudoperonospora species in hops and cucum¬bers, Alternaria species in vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species.
They can also be used for protecting material (e.g. protecting wood) for example against Paecilomyces variotti.
The mixtures according to the invention may particularly prefer¬ably be employed for controlling powdery mildew fungi in crops of grapevines and cereals.
The compounds I and II can be applied simultaneously, either to¬gether or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
depending on the kind of effect desired, the application rates of ;he mixtures according to the invention are, in particular in jgricultural crop areas, from 0.01 to 8 kg/ha, preferably 0.1 to j kg/ha, in particular 0.2 to 3.0 kg/ha.

The application rates of the compounds I are from 0.01 to 2.5 kg/ha, preferably 0.05 to 2.5 kg/ha, in particular 0.1 to 1.0 kg/ha.
Correspondingly, in the case of the compounds II, the application rates are from 0.01 to 10 kg/ha, preferably 0.05 to 5 kg/ha, in particular 0.05 to 2.0 kg/ha.
For seed treatment, the application rates of the mixture are ge¬nerally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/ kg, in particular 0.01 to 50 g/kg.
If phytopathogenic harmful fungi are to be controlled, the sepa¬rate or joint application of the compounds I and II or of the mixtures of the compounds I and II is effected by spraying or du¬sting the seeds, the plants or the soils before or after sowing of the plants, or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention, or the compounds I and II, can be formulated for example in the form of ready-to-spray solutions, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspen¬sions, dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting or granules, and applied by spraying, atomizing, dusting, broadcasting or watering. The use form depends on the intended purpose; in any case, it should ensure as fine and uniform a distribution as possible of the mixture accor¬ding to the invention.
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 being possible also to use other organic solvents as auxiliary solvents if water is used as the diluenti Suitable auxiliaries for this purpose are essential¬ly: solvents such as aromatics (eg. xylene), chlorinated aroma-tics (eg. chlorobenzenes), paraffins (eg. mineral oil fractions), alcohols (eg. methanol, butanol), ketones {eg. cyclohexanone), amines (eg. ethanolamine, diniethylformamide) and water; carriers such as ground natural minerals (eg. kaolins, clays, talc, chalk) and ground synthetic minerals (eg. finely divided silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.

Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alJcylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphtha-lenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ ethylene oxide condensates, ethoxylated castor oil, polyoxyethy¬lene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alco¬hol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose.
Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds I or II, or the mixture of the compounds I and II, with a solid carrier.
Granules (eg. coated granules, impregnated granules or homoge¬neous granules) are usually prepared by binding the active ingre¬dient, or active ingredients, to a solid carrier.
Fillers or solid carriers are, for example, mineral earths, such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magneaium oxide, ground synthetic materials and fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of -vegetable origin, such- as-cereal meal, tree bark—meal,-wood meal and nutshell meal, cellulose powders or other solid carriers.
The formulations generally comprise from 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I or II or of the mixture of the compounds I and II. The active ingre¬dients arc employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum or HPLC).
The compounds I and II, the mixtures, or the corresponding formulations, are applied by treating the harmful fungi, their habitat, or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally effective amount of the mixture, or of the compounds I and II in the case of separate

application.
Application can be effected before or after infection by the harmful fungi.
Examples of such preparations comprising the active ingredients are;
I. A solution of 90 parts by weight of the active ingredients and 10 parts by weight of H-methylpyrrolidone; this solu¬tion is suitable for use in the form of microdropa;
II. A mixture of 20 parts by weight of the active ingredients, 80 parts by weight of xylene, 10 parts by weight of the ad-duct of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzeneaulfonic acid, 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil; a dispersion is obtained by finely distributing the solution in water;
III. An aqueous dispersion of 20 parts by weight of the active ingredients, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
IV. An aqueous dispersion of 20 parts by weight of the active ingredients, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280°C, and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
V. A mixture, ground in a hammer mill, of 80 parts by weight of the active ingredients, 3 parts by weight of the sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by weighiT^f the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel; a spray mixture is obtained by finely distribu¬ting the mixture in water;
i^l. An intimate mixture of 3 parts by weight of the active
ingredients and 97 parts by weight of finely divided kao¬lin; this dust comprises 3% by weight of active ingredient;

VII. An intimate mixture of 30 parts by weight of the active ingredients, 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel; this formulation imparts good adhesion to the active ingredient;
VIII. A stable aqueous dispersion of 40 parts by weight of the active ingredients, 10 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water; this dispersion may be diluted further;
IX. A stable oily dispersion of 20 parts by weight of the active ingredients, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate and 88 parts by weight of a paraffinic mineral oil.
Use Example
The synergistic activity of the mixtures according to the inven¬tion can be demonstrated by the following experiments:
The active ingredients, separately or together, are formulated as a 10% emulsion in a mixture of 63% by weight of cyclohexanone and 27% by weight of emulsifier, and diluted with water to the desired concentration.
Evaluation is carried out by determining the infected leaf areas in percent. These percentages are converted into efficacies. The efficacy (W) is calculated as follows using Abbot's formula:
_JW-» (1 - &)^XOO/p
a corresponds to the fungal infection of the treated plants in % and
p corresponds to the fungal infection of the untreated (con¬trol) plants in %
an efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.
rhe expected efficacies of the mixtures of the active ingredients were determined using Colby's formula {R.S. Colby, Weeds i5.,

20-22 (1967)J and compared with the observed efficacies. Colby formula: E » x + y - x-y/lOO
E expected efficacy, expressed in % of the untreated control, when using the mixture of the active ingredients A and B at the concentrations a and b
X efficacy, expressed in % of the untreated control, when using active ingredient A at a concentration of a
y efficacy, expressed in % of the untreated control, when using active ingredient B at a concentration of b
Use Example 1 - Curative activity against Puccinia recondita on
wheat (wheat leaf rust)
Leaves of potted wheat seedlings of the variety "Kanzler" were dusted with spores of leaf rust (Puccinia recondita). Thereafter, the pots were kept for 24 hours in a chamber of high atmospheric humidity (90 to 95%) and 20 to 22'C. During this time, the spores germinated and the germinal tubes penetrated into the leaf tissue. The next day, the infected plants were sprayed to runoff point with an aqueous formulation of active ingredient prepared from a stock solution consisting of 10% of active ingredient, 63% of cyclohexanone and 27% of emulsifier. After the spray coating had dried on, the test plants were cultivated in a greenhouse at from 20 to 22'C and from 65 to 70% of relative atmospheric humidity for 7 days. Thereafter, the extent of rust fungus development on the leaves was determined.
The compounds of the formula I used were the following components:


The resuirs are snown in Tables 1 and 2 below. Table 1

Ttie test results show that the observed efficacy in all mixing ratios is higher than the efficacy which had been calculated beforehand using Colby's formula

use Example 2 - Activity against powdery mildew of wheat
Leaves of potted wheat seedlings of the variety "Kanzler" were sprayed to runoff point with an aqueous formulation of active ingredient prepared from a stock solution consisting of 10% of active ingredient, 63% of cyclohexanone and 27% o£ emulsifier and 24 hours after the spray coating had dried on, the leaves were dusted with spores of powdery mildew of wheat (Erysiphe graminis forma specialis tritici). The test plants were subsequently kept in a greenhouse at 20 to 24°C and 60 to 90% relative atmospheric humidity. After 7 days, the extent of the mildew development was determined visually in % infection of the total leaf area.
The test results are shown in Tables 3 and 4 below.



rhe test results show that for all mixing ratios the observed efficacy is higher than the efficacy which had been calculated seforehand using Colby's formula


We claim:
1. A fungicidal mixture, comprising as active components a) an amide compound of the formula I

in which
A is an aryl group or an aromatic or non-aromatic, 5- or
6-inembered heterocycle which has from 1 to 3 hetero atoms selected from O, N and S;
where the aryl group or the heterocycle may or may not have 1, 2 or 3 substituents which are selected, indepen¬dently of one another, from alkyl, halogen, CHF2, CF3, alkoxy, haloalkoxy, alkylthio, alkylsulfynyl and alkyl-sulfonyl;
R1 is a hydrogen atom;
R2 is a phenyl or cycloalkyl group which may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cyclo-alkyloxy, cycloalkenyloxy, phenyl and halogen, where the aliphatic and eyelealiphatic radicals may be partially or fully halogenated and/or the cycloaliphatic radicals may be substituted by from 1 to 3 alkyl groups and where the phenyl group may have from 1 to 5 halogen atoms and/or from 1 to 3 substituents which are selected, indepen¬dently of one another, from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and where the —amidic phenyl" group""may or may""not~be condensed~with a saturated 5-membered ring which may or may not be substituted by one or more alkyl groups and/or may have a hetero atom selected from 0 and S, and
b) a morpholine or piperidine derivative II selected from the group of the compounds IIa, IIb, and IIc



in a synergistically effective amount.
2. A fungicidal mixture as claimed in claim 1, wherein in the
formula I the radical A is one of the following groups:
phenyl, pyridyl, dihydropyranyl, dihydrooxathiynyl, dihydro-oxathiynyloxide, dihydrooxatbiynyldioxide, furyl, thiazolyl, pyrazolyl or oxazolyl, where these groups may have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, halogen, difluoromethyl and trifluoro-methyl.
3. A fungicidal mixture as claimed in claim 1, wherein in the
formula I the radical A is one of the following groups:
pyridin-3-yl, which may or may not be substituted in the 2-position by ha^logen, methyl, dif luoromethyl, trifluoro-methyl, methoxy, methylthio, methylsuIfynyl or methyl-sulfonyl;
phenyl, which may or may not be substituted in the 2-position by methyl, trifluoromethyl, chlorine, bromine or iodine;
2-methyl-5,6-dihydropyran-3-yl;
2-methyl-5,6-dihydro-l,4-oxathiyn-3-yl or the 4-oxide or 4,4-dioxide thereof;

2-methylfuran-3-yl, which may or may not be substituted in the 4- and/or 5-position by methyl;
thiazol-5-yl, which may or may not be substituted in the 2- and/or 4-position by methyl, chlorine, difluoromethyl or trifluoromethyl;
t.hiazol-4-yl, which may or may not be substituted in the 2- and/or 5-position by methyl, chlorine, difluoromethyl or trifluoromethyl;
l-methylpyrazol-4-yl, which may or may not be substituted in the 3- and/or 5-position by methyl, chlorine, difluoromethyl or trifluoromethyl; or
oxazol-5-yl, which may or may not be substituted in the 2- and/or 4-position by methyl or chlorine.
H. A fungicidal mixture as claimed in one of the preceding
claims, which comprises a compound of the formula I in which R2 is a phenyl group which may or may not be substituted by 1, 2 or 3 of the substituents mentioned in claim 1.
5. A fungicidal mixture as claimed in claim 4, where R^ is a
phenyl group which has one of the following substituents in
the 2-position:

6. A fungicidal mixture as claimed in any of claims 1 to 5,
which comprises an amide compound of the formula la below:



R3 is hydrogen, methyl, difluoromethyl, trifluoromethyl or chlorine,
Rio is Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C^-alkylthio or halogen.
7. A fungicidal mixture as claimed in any of claims 1 to 5,
which comprises as amide compound a compound of the formula lb below:

9. A fungicidal mixture as claimed in any of the preceding
claims, which is conditioned in two parts, one part compri¬
sing the amide compound I in a solid or liquid carrier and
the other part comprising one or more compounds of the formu¬
lae Ila to lie in a solid or liquid carrier.
10. A method for controlling harmful fungi, which comprises
treating the fungi, their habitat, or the materials, plants,
seeds, soils, areas or spaces to be protected against fungal

attack with a fungicidal mixture as claimed in any of claims 1 to 9, where the application of the active ingredients amide compound I and one or more compounds of the formulae Ila to IIe may be carried out simultaneously, that is either toge¬ther or separately, or in succession.
11. A fungicidal mixture, substantially as herein described,
and exemplified.
12. A method for controlling harmful fungi, substantially
as herein described, and exemplified.


Documents:

2800-mas-1998 abstract original.pdf

2800-mas-1998 claims granted.pdf

2800-mas-1998 description (complete) granted.pdf

2800-mas-1998 abstract.pdf

2800-mas-1998 claims.pdf

2800-mas-1998 correspondence-others.pdf

2800-mas-1998 correspondence-po.pdf

2800-mas-1998 description(complete).pdf

2800-mas-1998 form-1.pdf

2800-mas-1998 form-19.pdf

2800-mas-1998 form-2.pdf

2800-mas-1998 form-26.pdf

2800-mas-1998 form-4.pdf

2800-mas-1998 form-5.pdf

2800-mas-1998 form-6.pdf

2800-mas-1998 others.pdf

2800-mas-1998abstract.jpg

2800-mas-99.rtf


Patent Number 242494
Indian Patent Application Number 2800/MAS/1998
PG Journal Number 36/2010
Publication Date 03-Sep-2010
Grant Date 30-Aug-2010
Date of Filing 15-Dec-1998
Name of Patentee BASF AKTIENGESELLSCHAFT
Applicant Address 67056 LUDWIGSHAFEN,
Inventors:
# Inventor's Name Inventor's Address
1 KLAUS SCHELLBERGER TRAMINERWEG 2, 67161 GONNHEIM,
2 MARIA SCHERER HERMANN-JURGENS-STR.30, 76829 LANDAU,
3 KARL EICKEN AM HUTTENWINGERT 12, 67157 WACHENHEIM,
4 MANFRED HAMPEL IM BIENGARTEN 15, 67435 NEUSTADT,
5 SIEGFRIED STRATHMANN DONNERSBERGSTR. 9, 67117 LIMBURGERHOF,
6 EBERHARD AMMERMANN VON-*GAGERN-STR.2, 64646 HEPPENHEIM,
7 GISELA LORENZ ERLENWEG 13, 67434 NEUSTADT,
PCT International Classification Number AOIN37/50
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 19756406.2 1997-12-18 Germany