AU2003200295B2 - Fungicidal mixtures based on amide compounds and pyridine derivatives - Google Patents

Description

P/00/011 28/5/91 Regulation 3.2(2)

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: Invention Title: FUNGICIDAL MIXTURES BASED ON AMIDE COMPOUNDS AND PYRIDINE

DERIVATIVES

The following statement is a full description of this invention, including the best method of performing it known to us Fungicidal mixtures based on amide compounds and pyridine derivatives The present specification discloses fungicidal mixtures for controlling harmful fungi, which mnixtures comprise amnide compounds of the formula

I

0~

LS

A-CO -1R 1

R

2

(I)

in which A is an aryl group or an aromatic or non-aromatic, 5- or 6-mnembered heterocycle which -has from 1 to 3 hetero atom-s selected 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, .independenlt ly o)f one another, from alkyl,. halogen,. CHF2,*

CF

3 alkoxy, haloalkoXY, alkylthio, alkylsuJlf inl and alkylsulf'ofl; RI is a hydrogen atom;

R

2 is a phenyl or cycloalkyl group which may or may not have -1, 2 or 3 substituents which are selected from alkyl, alkenyl, alkynll alkoxy, alkenyloxy alkyhlloxy, cycloalkyl, cycloalkenyl, cycloalkyloxyi cycloalkenyloxy, phenyl and halogen, where the aliphatic .and cycloali~phatic radicals may be partially or fully halogenated and/or the cycloaliphatic radicails may be substituted by f rom 1 to 3 alkyl groups and where the pheniyl. group. may have from 1 to 5 halogen atoms and/or from 1 to.3 substitueflts, which-are selected, in dependently of one anotherz from -alkyl-, halakyl, alkoxy, haloalkOxy, alkcylthio 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 2 b) a pyrimidine. derivative of the formula III,

J~II

in which R is methyl, propyn-1--yl or cyclopropyl, and/or c) at least one active ingredient of the formula, IV or V,

~CN

CN

CI.

C1 and/or d) a phthalimide derivative selected from the group consisting of the compounds VIa, VIb and VII I CN-SCC1 3 11 C C N-SCC 2 CHC12 VIb VIa 0 0.

VII

and/or a dinitroaniline of the formula VIIi vtii N0 2 cI and/or f) an arylsulfamide of the formula IX a-or IXb (CH3)2NSO 2 NSCC1 2 F

(CH

3 )2 IXa :3 in a synergistically effective amount.

~NS0 2 NSCC1 2

F

CH. 3 EXb nIn one aspect, the invention relates to a fungicidal mixture, comprising as

O

0 active components a) an amide compound of the formula I 1,O 5 A-CO-NR 1

R

2 in which c A is an aryl group or an aromatic or non-aromatic, 5- or 6-membered 0heterocycle which has from 1 to 3 hetero atoms selected from O, N and S; where rn 10 the aryl group or the heterocycle may or may not have 1, 2 or 3 substituents 0 which are selected, independently of one another, from alkyl, halogen, CHF 2

CF

3 alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl; is a hydrogen atom;

R

1 is a hydrogen atom;

R

2 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, cycloalkenyloxy, 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, 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 O and S, and b) a pyrimidine derivative of the formula In,

CH

3 NN R

H

in which R is methyl, propyn-1-yl or cyclopropyl, I n In another aspect, the invention relates to a method for controlling harmful 0fungi, which comprises treating the fungi, their habitat, or the materials, plants, Sseeds, soils, areas or spaces to be protected against fungal attack with a fungicidal mixture as claimed in any one of claims 1 to 11, where the application O 5 of the active components may be carried out simultaneously or in succession.

As employed above and throughout this disclosure (including the claims), I the following terms, unless otherwise indicated, shall be understood to have the c following meanings: "Comprises/comprising" when used in this specification is taken to specify Cc 10 the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

WO 97/08952 describes fungicidal mixtures which, in addition to compounds of the formula I, also comprise fenazaquin as further components.

These are described as being very effective against Botrytis.

The amide compounds of the formula I are known per se and are described in the literature (EP-A 545 099).

Fungicides from the group of the dicarboximides are known to the person skilled in the art and are commercially available.

Also known are the pyrimidine derivatives III, their preparation and their activity against harmful fungi [R methyl: DD-A 151 404 (common name: pyrimethanil); R 1-propynyl: EP-A 224 339 (common name: mepanipyrim); R=cyclopropyl: EP-A 310 550].

The compound IV is known from K. Gehmann, R. Nyfeler, A.J. Leadbeater, D..Nevill and D. Sozzi, Proceedings of .the Brighton Crop Protection Conference, Pests and Diseases 1990, Vol. 2, p. 399 (common name: fludioxinil) and is commercially available from Novartis.

The compound V is known from D. Nevill, R. Nyfeler, D. Sozzi, Proceedings of the Brighton Crop Protection Conference, Pests and Diseases 1988, Vol. 1, p. 65 (common name: fenpiclonil).

US-A 2,553,770; 2,553,771; 2,553,776 describe the compounds VIa (common name: captan) and VII (common name: folpet), their preparation and their activity.against harmful fungi; The compound VIb (common name: captafo1) is described in Phytopathology 52(1962), 52, 754.

Likewise, the compound VIII, -its preparation and its use (CAS:RN 79622-59-6, common name: fluazinam) are described in the literature.

The compounds IXa and IXb are known under the common names dichlofluanid and tolylfluanid, respectively, and are described in the German patent 1193498.

It is an object of the present invention to provide mixtures which have an improved activity against harmful fungi combined with a reduced total amount of active ingredients applied (synergistic mixtures), with a view to reducing.the application rates and to improving .the activity spectrum of the known compounds.

We have found that this object is achieved -by the mixtures of the invention defined above.

Better control of harmful fungi is possible by applying the compounds I and the compounds II to VIII simultaneously, that is either together or separately, or by applying the compounds I and the compounds II .to VIII in succession than when the compounds I or II to VIII are applied on their own.

The mixtures described herein have synergistic action and are therefore particularly suitable for controlling harmful fungi, in particular of Botrytis species.

The-term "halogen" used herein refers to fluorine, chlorine, br omine and iodine and is in'particular fluorine, chlorine and bromine.

The term "alkyl" includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched Cl-C 12 -alkyl and in particular Cl-C 6 -alkyl groups. Examples of alkyl groups are alkyl-such as, in particular, methyl, ethyl, propyl, 1-methylethyl, butyl, 1I-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n'-pentyl, I-inethylbuti'l, 2-methylbutyl, 3-xnethylbutyl, 1, 2-dimethyipropyl, 1, 1-dimethylpropyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 151, 2 -dime thylbutyl, 2, 32-dime thylbutYl, 3, 3-dimethylbutyl, 1,1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, I -ethyl -2 -methylpropyl, n-heptyl, .1-m ethylhexyl, 1-ethylpentyl, 2-ethylpentyl,* 1-propylbutyl, octyl, decyl, dodecyl.

Haloalkyl is an aikyl group as defined above which is partially or fully halogenated by one or more halogen atoms, in particular by fluorine and chlorine. Pref erably, -there are from I to 2S 3 halogen 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, alkylsulfinyl and alkylsulfonyl.' The alkenyl group includes straight-chain and branched alkenyl groups. These are preferably straight-chain or branched C3-C 12 -alkenyl groups and in particular C 3

-C

6 -alkenyl-groups.

Examples of alkenyl groups are 2-propenyl, .2-butenyl; 3-butenyl, 1l-met hyl-2 -propenyl, 2-methyl-2-propenyl, 2-pentenyl, .3 -pentenyl, 4 -pentenyl, 1-methyl-2 -butenyl, 2-methyl-2"butelyl, 3-methyl-2-butenyl, 1-iethyl-3-butiEnyl, '2-methyl-'3-butenyl, 3-methyl-3-butenyl, 1,.1-dimethyl--2-propenyl, 1, 2-dimethiYl727propenyl, 1 -ethyl -2 -propenyl, 2T-hexenyl, 3-hexenyl,- 4-hexenyl, 5-hexenyl;' 1.methyl-2-pentenyl, 2 -methyl-2-pentefiyl, 3-methyl-2-pentenyl,~ 4-methyl-2-penteflyl, l-methyl-3-pentenyl, 2-methyl-3-penten~l, 3-methyl-3-penteflyl, 4 -methyl-3-pentenyl, 1-methyl-4-penteflyl, 2-methyl-4-peftefl, 3 -Inethyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, l,1-dinethyl-]-butenyl, 1, 2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenYl, 1, 3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2, 2-diinethyl-3-butenyl, 2,.3 -dimethyl-2 -1-utenyl, 2, 3-dimethyl-3-butenyl, 1-ethyl-2-butelyl, 1-ethyl-3-butenyl, 2 -ethyl- 2-butenyl, 2-ethyl-3-butenyl, 1, 2-trimethyl-2-propenyl, 1l-ethyl- 1-methyl-2 -propenyl and l-ethyl-2-methyl-2--propenyl, in particular 2-,propenyl, 2-butenyl, 3-methyl-2-butenyl and 3-methyl-2-pentenyl.- The alkenyl group ma y, be parially 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 1groups. These are preferably straight-chain and br anched

C

3 -C1 2 -alkynyl groups and in particular C 3 -c 6 -alkynyl groups.

Examples of alkynyl groups are 2-propynyl,~ 2-butynyl, 3-butynyl, J-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 201, 1-dimethyl-2-propynyl*1 1 -ethyl- 2-propynyl, 2-hexynyl, 3-hexynyl, 4 hexynyl, 5-hexynyl, l-methyl-2-pentynyl 1-rnethyl-3-pentynyl, 1-methyl-4 -pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, .4-methyl-2-pentynyl, 1,2-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2, 2-dimethyl-3-butynyl 1 -ethyl-2-butynyl, I -ethyl- 3-butynyl, 2-ethyl-3-butynyl and 1 -ethyl- 1-methyl-2-propynyl.

The-above statements for the alkenyl group and its halogen substituents and for the alkynyl group apply in a corresponding manner to alkenyloxy and alkynyloxy.

The cycloalkyl group is preferably, a c 3

-C

6 ;-cycloalkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl or cyplohexyl. If the cycloalkyl group is substituted, it preferably has f rom 1 to 3

**C

1

-C

4 -alkyl radicals as substituents.

Cycloalkenyl is preferably a C 4

-C

6 -CYCloalkenyl group, such as cyclobutenyl, cyclopentenyl or cyclohexenyl. If the cycloalkenyl group is *substituted, it preferably has from 1,to 3 Cl-C 4 -alkyl radicals as substituents.

A cycloalkoxy group is preferably a Cs-C 6 -cycloalkoxy group, such as cyclopentyloxy or. cyclohexyloxy. If the cycloalkoxy group is substituted, it preferably has from 1 to 3 Cl-C 4 -alkyl radicals as substituents.

The cycloalkenyloxy group is preferably a C 5

-C

6 -cycloalkenyloxy group, such as cyclopentyloxy or cyclohexyloxy. If the cycloalkenyloxy-group is substituted, it preferably has from 1 to 3 Ci-C 4 -alkyl radicals as substituents.

Aryl is preferably phenyl.

If A is a phenyl group, this may have one, two or three of the abovementioned substituents in any position. These substituents are preferably selected, independently of one another, from alkyl, 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 5-membered heterocycle, it is in particular a furyl, thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl, triazolyl or thiadiazolyl radical or the corresponding dihydro or tetrahydro derivatives thereof. Preference is given to a thiazolyl or pyrazolyl radical.

If A is a 6-membered heterocycle, it is in particular a pyridyl radical or a radical of the formula: in which one of the radicals X and Y is O, -S or NR 23 where R 23 is H or alkyl, and the other of the radicals X and Y is CH 2 S, SO,

SO

2 or NR 23 The dotted' line means that a double bond may or may not be present.

The 6 -membered.aromatic heterocycle is particularly preferably a pyridyl radical, in particular a 3-pyridyl radical, or a radical of the formula 0 "CH3 (A3) in which X is CH 2 S, SO or S02- 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, from alkyl, halogen, difluoromethyl or trifluoromethyl, A is particularly preferably a radical of the formulae: .105Z* ICR3 (Al) -R6 Q R 4 (A2) R8 (A7) CH 3 in which R 3

R

4

R

6

R

7

R

E and R 9 independently of one another are hydrogen, alkyl, in particular methyl, halogen, in particular chlorine, CHF 2 or CF 3 The radical R 1 in the formula I is preferably a hydrogen atom.

The radical R 2 in the formula I is preferably a phenyl radical. R 2 preferably has at least one substituent which is particularly preferably in the 2-position. The substituent (or the substituents) is (are) preferably selected from the group consisting of alkyl, cycloalkyl, cycloalkenyl, halogen or phenyl.

The substituents of the radical R 2 may in turn be substituted again. The aliphatic or cycloaliphatic substituents may be partially or fully halogenated, in particular fluorinated or chlorinated. They preferably have 1, 2 or 3 fluorine or chlorine atoms. If the substituent of the radical R 2 is a phenyl group, this phenyl 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 preferably, the phenyl group is substituted with a halogen atom in the p-position, i.e. the particularly preferred substituent of the radical

R

2 is a p-halogen-substituted phenyl radical. The radical R 2 may also be condensed with a saturated 5-membered ring, where this ring for its part may have from 1 to 3 alkyl substituents.

R

2 is in this case, for example, indanyl, thiaindanyl and oxaindanyl. Preference is given to indanyl.and 2-oxaindanyl which are attached to the nitrogen atom in particular via the 4-position.

According to a preferred embodiment, the composition according to the invention comprises as amide compound a compound of the formula I in which A is as defined below: phenyl, pyridyl, dihydropyranyl, dihydrooxathiiynyl, dihydrooxathiiynyloxide, dihydrooxathiiynyldioxide, furyl, thiazolyl, pyrazolyl or. 5xazolyl, where these groups may have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, halogen, difluoromethyl and trifluoromethyl.

.According to a further preferred embodiment, A is one of the following groups: pyridin-3-yl, which may or may not be substituted in the 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinylor met'hylsulfonyl; 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-1, 4-oxathiiyn-3-yl or the 4-oxide or 4,4-dioxide thereof; 2-methylfuran- 3 -yl, which may or may not be substituted in the 4and/or 5-position by methyl; which may or may not be substituted in the 2and/or 4-position by methyl, chlorine, difluoromethyl or trifluoromethyl; thiazol-4-yl, which may or may not be substituted in the 2and/or 5-position by methyl, chlorine, difluoromethyl or trifluoromethyl; 1-methylpyrazol- 4 -yl, which may or may not be substituted in the 3- and/or 5-position by methyl, chlorine, difluoromethyl or trifluoromethyl; or 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

2 is a phenyl group which may or may not be substituted by 1, 2 or 3 of the abovementioned substituents.

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

2 is a phenyl group which has one of the following substituents in the 2-position:

C-C

6 -alkyl,

C

5

-C

6 -cycloalkenyl,

CS-C

6 -cycloalkyloxy, cycloalkenyloxy, where these groups may be substituted by 1, 2 or 3 Ci-C 4 -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 another, from C 1

-C

4 -alkyl, Cl-C 4 haloalkyl,

C

1 -C4-alkoxy,

CL-C

4 -haloalkoxy, Cl-C4-alkylthio and Cl-C4-haloalkylthio, indanyl or oxaindanyl which may or may not be substituted by 1, 2 or 3 Ci-C 4 -alkyl groups.

According to a further preferred embodiment, the compositions according to the invention comprisea amide compound a compound of the formula Ia, A-CO-NH/ (Ia) in which A is (Al) QNCR 4 (A2) 0 (M3)

R

5

R

7

R

5

CH

3 (M4) (M7) (A5)

R

5

N:]

(A8) (A6) X is methylene, sulfur, sulfynyl or sulfonyl (SO 2

R

3 is methyl, 'difluoromethyl, trifluorotnethfiyl, chlorine, bromine or iodine, 4R 4 is trifluoromethyl or chlorine,

R

5 is hydrogen or methyl,

R

6 .is methyl, difluoroniethyl, trifluoromethYl or chlorine,

R

7 is hydrogen, methyl or Chlorine, R8 is methyl, difluoromethyl or trifluoroinethyl,

R

9 is hydrogen, methyl, dif luoromethyl1, trif lUoromethyl or chlorine, RIO is CI-C 4 -alkyl,

C

1

-~C

4 -alkoxy, Ci-C 4 -alkylthio or halogen- Also disclosed is a fungicidal- mixture comprising as amide compound a compound of the formula lb

CO-,NH

L L ZN J(Ib) N~R4 R11 in which

R

4 ishalog'el and

R

11 is phenyl which is substituted by halogen.

Amide compounds. of the formula 1, which -may- be used in the fungicidal mixtures disclosed herein, are mention in E:P-A- 545 099 and 589 301 which are incorporated hereinl in their entirety by reference.

The preparation -of the amide compounds of the f ormula I is known, for example, f rom EP-A-5 4 5 099 or 589 301 or can be carried out by similar processes.

Preferred substituents

R

2 1 and .R 22 are hydrogen, F, Cl, methyl, ethyl, methocy., thiomethyl and N-M'ethylamfino. R3'and-R 4 together may also f orm a grouping =0.

3. 'Preferred fungicides of the dicarboximide type are the co~ppounds Iha to Id: ethyl 3 ,S~dichloroheyeY.l)S7etyl2 dioxoox .azolidine- -carboxylate* C1 0 CH 3 C0 2

CH

2 CH3 t~

C

II.b: 3 -(3,5-dichlorophenyl)Nisopropyl- 2 ,4doomdaoii 1 -carboxamide CI 0 II.b CI -o COHHCI1) or II.c: 5-dichlorophelyl)-l1 2-dimethycyclopropale-l, 2dicarboxilnide CI 0

H

3 II.c

OH

3 CI 0 or II.d: (RS)- 3 3 ,-dichlorophenyl)5ethenyl5-ethyl-1, 3 oxazolidine- 2 4-diane CI 0 CH 3 Y-CHCH2 II.d.

CIO 01 These compounds are commercially available as. fungicidally active ingredients and are described in the literature as follows: *II.a (common name: chlozolilate): CAS RN [84332-86-5], DE-A 29 06 574; II.b (common-name: iprodione): GCAS RN [36734-19-7],

US-A

3,755,350; *II.c (common name: procymidone): CAS RN [32809-16-8],

US-A

3,903,090; *II.d (common name: vinclozoline): CAS*RN (50471-44-8], DE-A 22 4007 576].

To unfold the synergistic activity, even a small amount of the amide compound 'of the formula I is sufficient. Preference is to employing amide compound and active ingrediint of the formula Ii and/or III to.IX in a weight ratio in the range of from 50:1 to 1:50, in particular from 10:1 to 1:10. It is also possible here to employ ternary mixtures which, -in addition to amide compounds I, comprise both compounds II and one or more compounds III to IX. In such mixtures, the mixing ratio of the compounds II and III to IX with each other is usually in the range of from 50:1 to 1:50, preferably from 10:1 to 1:10.

wing to the basic character "of their nitrogen atoms, the compounds III, I, V and VIII are capable of forming salts or adducts with inorganic or organic acids or with metal ions.

0 Examples of inorganic acids are hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydriodic acid, sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids, such as acetic acid,. trifltoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lacticacid, 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 aryldisulfo n i c acids (aromatic radicals, 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), arylphosphonic 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, salicylic acid, p-aminosalicylic acid, 2 -phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

Suitable metal ions are, in particular, the ions f the elements of.the first to eighth sub-group, in particular chromium,ore of manganese, iron, cobalt, nickel, copper, zinc and furthermre 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 variosvalencies which they can assume.

When preparing the mixtures, it is preferred to'employ the-pure active ingredients I and II to IX, to which further active ingredients against harmful.fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active-ingredients or fertilizers,an be admixed.

The mixtures of the. compounds I and II and/or III to IX, or the compounds I and II and/or III to IX used simultaneously, jointly or separately, exhibit outstanding activity against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Basidiomycetes, Phycomycetes 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 species (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 (powder 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, HelminthospOrium species in cereals, Septoria nodorum in wheat, Botrytis cinrea (gray.mold) in strawberries, vegetables, ornamentals and -grapevines, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia.oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in grapevines, Pseudoperonospora species in hops and cucumbers, Alternaria species in vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species.

The mixtures described herein may Sparticulaly preferably be employed for controlling Botrytis species in crops o grapevines and vegetables, and also in ornamentals.

The compounds I and II and/or III to IX can be applied simultaneously, either together 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 the fungicidal mixtures are, in. particular in agricultural 4 5 crop areas, from 0.01 to 8 kg/ha, preferably 0.1 to kg/ha,, in particular 0.2 to 3.0 kg/ha.

The application rates of the compounds I are from 0.01 to kg/ha, preferably 0.05 to 2.5 kg/ha, in particular 0.1 to kg/ha.

Correspondingly, in the case of the compounds II and/or III to IX, 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 generally 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 separate or joint application of the compounds I and II and/or III to IX or of the mixtures of the compounds I and II and/or III to IX.is effected by spraying or dusting the seeds, the plants, or the soils before or after sowing of the plants, -or before or: after plant emergence.

The fungicidal synergistic mixtures described herein and according to the invention, or the compounds I and II and/or III to IX, 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 suspensions, 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 as possible a distribution of the mixtures described herein.

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 diluent. Suitable auxiliaries for this purpose 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 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.

tant are the alkali metal salts, alkaline earth Suitable surfactants are ic sulfonic acids, eg.

metal salts and ammonium salts of aromaticu ulnaphalnesuln ligno-, phenol-, naphthalene- and dibutylnaphthalenes alfonic acid, and of fatty acids, alkyl- and alkylar s ofsulfatekyl, lauryl ether and fatty alcohol sulfates alcohol glycol hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates f naphthalene or of tdehyde, naphthalenesulfonic acids with pheol a isooctyl-, octylpolyoxyethylene octylphenol ether, ethoxylated istbutyl phenyl or.nonylphenol, alkylphenol polyglycol etherols, tributypheyl polyglycol ethers, alkylaryl polyether alcohols, ethoxylated alcohol, fatty alcohol/ethylene oxide condensates: lae castor oil, polyoxyethylene alkyl ethers or polyoxypropylene lauryl alcohol 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 II or I and/or III to IX, or the mixture of the compounds I and I and/or to with a solid carrier.

Granules (eg. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active ingredient, or active ingredients, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths, such silicates, ta^l.

as silica gel, silicas, silicates, talc, kaolin, limestonelime, halk bole, loess, clay, dolomite, kaolin, limestone, lime, c h a e 'anesium sulfate, magnestum diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials and fertilizers, such as oxide, ground synthetic matera mmonium nitrate, ureas, ammonium sulfate, ammonium phosphate, ammoniu nitrate, ureas, and products of vegetable originsuch as cpereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders orother solid carriers- The formulations generally comprise from o to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I and II and/or III to IX or of the mixture f the compounds I and II and/or III to IX. The active ingredients are employed in a purity .of from 90% to 100%, preferably 95% to 100% (according toNMR or HPLC spectra.) The compounds I and II and/or III to IX the mixtures or the corresponding formulations, are.applied bytreating the harmful fungi, their habitat, or the plants, seeds, soils, areas, 19 materials or spaces to be kept free from them with a fungicidally effective amount of the mixture, or of the compounds I and II and/or III to IX 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 N-methylpyrrolidone; this solution is suitable for use in the form of microdrops; II. A mixture of 20 parts by weight of the active ingredients, parts by weight of xylene, 10 parts by weight of the adduct 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 dodecylbenzenesulfonate, 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 2800C, 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-l-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; a spray mixture is obtained by finely distributing the mixture in water; VI. An intimate mixture of 3 parts by weight of the active ingredients and 97 parts by weight of finely divided kaolin; 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, 0 iparts 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 dodecylbenzenesulfonate, 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 described herein .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 o.f 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 effcaces. The efficacy is calculated as follows using Abbot's formula: w a)-100/ a corresponds to the fungal infection of the treated plants in and p corresponds to the fungal infection of the untreated (control) 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.

The expected efficacies of the mixtures of the active ingredients were determined using Colby's formula Colby, Weeds 20-22 (1967)] and compared with the observed efficacies.

Colby formula: E x y x-y/1 0 0 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 Activity against Botrytis cinerea on bell pepper leaves Bell pepper seedlings of the variety "Neusiedler Ideal Elite" were, after 4-5 leaves were well developed, sprayed to runoff point with an aqueous preparation of active ingredient which.had been prepared from a stock solution comprising 10% of active ingredient, 63% of cyclohexanone and 27% of emulsifier. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 106 spores per ml of a 2% strength aqueous Biomalz solution. The test plants were subsequently placed in a climatized chamber with high atmospheric humidity at 22-24oC. After 5 days, the extent of the fungal infection on the leaves could be determined visually in The compounds of the formula I used were the following components:

NH

N Cl

F

NH

1.2 The results are shown in Tables 1 and 2 below.

Table 1 Ex. Active ingredient untreated Compound I.1 Concentration of active ingredient in the spray liquor in ppm 0 infection) 31 16 Efficacy in of the untreated control 0 78 67 1C 2C 3C Compound 1.2 31 67 16 44 4C- Compound VIa 1 I 0 Compound VII 31 0 I 0 6C Compound IXa 31 16 8 0 0 0 Table 2 Ex. Mixtures according to the invention (content in ppm) 7 31 ppm I.1 31 ppm VIa 8 8 ppm I.1 8 ppm VIa 9 31 ppm 1.2 31 ppm Via 16 ppm 1.2 16 ppm Via .11 31 ppm 1 31 ppm.VII 12 8 ppm I.1 observed efficacy 97 calculated efficacy*) 7B 30 11 100 67 70 44 90 78 39 11 8 ppm VII_ Ex.

13 14 16 17 18 19 Mixtures according to observed the invention efficacy (content in ppm) 31 ppm 93 31 ppm I-2 calculated efficacy*) 67 31 ppm VII 16 ppm 1.2 8 ppm I. 2 8 ppm VII- 31 ppm I. 1 31 ppm IXa 16 ppm I.1 16 ppm IXa 16 ppm 1.2 16 ppm IXa ppm 1.2 44 90 44 78 95 67 90 100 99 67 44 44 calculated using Colby's formula S l ixing ratios the observed The test results show that for all ixing ratios been alculated efficacy is higher than the efficacy which had been alculated beforehand using Colby's formula.

Use Example 2 Activity against Botryis cinerea on bell peppers Disks of green bell peppers were sprayed to runoff point Disks of green bell peppers werac ve ingredient which had with an aqueous preparation of active ingridient which had been prepared from a stock solution comprising 10% of active ingredient, 63% of cyclohexanone and 27% of emulsifier. 2 hours after the spray coating had dried on, the fruit disks hours after the spray coainnsion of Botrytis cinerea were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 106 spores per ml of a 2% strength Biomalz solution. The inoculated fruit disks were subsequently incubated in moist chambers at 18' C over 4 days. The Botrytis infection on the diseased fruit disks was then evaluated visually.

The results are shown in Tables 3 and 4 below.

Table 3 Ex. Active Concentration of Efficacy in of ingredient active ingredient the untreated in the spray control liquor in ppm 21C untreated 0 (100% infection) 0 22C Compound.I.1 31 0 16 0 23C Compound 1.2 31 16 0 24C Compound IV 31 0 16 0 Compound VIa 31 0 26C Compound VII 31 0 27C Compound VIII 31 0 16 0 Table 4 Ex. Mixtures acording to the observed calculated invention efficacy efficacy*) (content in ppm) 28 31 ppm I.1 50 0 31 ppm IV 29 16 ppm I.1 20 0 16 ppm IV 31 ppm 1.2 70 31 ppm IV 31 16 ppm 1.2 20 0 16 ppm IV 32 31 ppm 1.2 50 31 ppm IVa 33 31 ppm 1.2 40 S 31 ppm VII 34 31 ppm I.1 30 0 31 ppm VIII 35 16 ppm 1.2 20 0 16 ppm VIII on calculated using Colby's formula 0 The test results show that for all mixing ratios the observed efficacy is Shigher than the efficacy which had been calculated beforehand using Colby's formula.

'O 5 USE EXAMPLE 3 CONTROL OF GREY MOULD (BOTRYTIS CINEREA) ON FRUIT SLICES OF GREEN PEPPER to The following compounds and compositions containing them were tested: 1. Amides 1.1, 1.2 2. Pyrimidine derivatives Ilila, 111c Mia CH 3 9N IIIC CH 3 3. Pyrrole derivate IV

#F

0 4. Dinitroaniline Vill viii The biological activity of the compounds and compositions containing them were tested as follows: Fruit slices of green pepper were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below, prepared from a stock solution containing 10 of the active ingredient, 85 cyclohexanone and 5 emulsifier. After 2 hours the sprayed-on layer had dried, the disks were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 106 spores per ml in 2 wt. aqueous biomalt solution. The infected fruit slices were then incubated in chambers with high humidity for four days at 18-200 C. The fruit slice area under fungal attack was then assessed visually in percent.

These figures were then converted into degrees of control. The degree of control in the untreated fruit slices was set at 0. The degree of control when 0% of the fruit slice area was attacked was set at 100.

The degree of control was calculated in accordance with the Abbott formula as follows: Abbott formula: W (1 a/P) 100 a fungus attack of treated fruit slices and P fungus attack of untreated control fruit slices The expected degrees of action of the active ingredient compositions were determined in accordance with the Colby formula (Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, 15, p. 20 22, 1967) and compared with the degrees of action observed.

The values for the fungicidal action varied between the individual experiments because the plant material in the individual experiments exhibited varying degrees of attack; for this reason, only the results within the same experiment can be compared with each other.

Colby formula: E x y (x e y 100) E Expected degree of action, expressed in of the untreated control, when active ingedients A and B are applied together, the concentration of A being and the concentration of B being [b] x degree of action of ingredient A, expressed in of the untreated control, when concentration of the active ingredient A is applied y= degree of action of ingredient B, expressed in of the untreated control, when concentration of the active ingredient B is applied As a general rule the comparison of the expected degree of action according to the Z Colby formula) with the degree of action found shows whether the effect is synergistic or j not, the correlation being as follows: D degree of action found synergism degree of action found no synergism The test results are listed in the following tables: X Compound Appln. Rate [ppm] degree of control 36 control (untreated) (92 attack) 0 12,5 S]37 1.1 6,3 24 3.1 2 12.5 67 38 1.2 6.3 57 3.1 2 39 Ill.a 31 63 Ill.c 31 31 3.1 13 41 IV 1.6 2 1.6 2 6.3 2 42 I 3.1 2 The same experiments were carried out with mixtures in accordance with the instant invention. The results achieved with these compositions are listed in the following table: Mixture according to the inuention Degree of action calculated EX nvention Degree of action observed Degree of acton calculated Application rate [ppm] (Colby) 1.1 Ill.a 43 3.1 31 ppm 57 36 ratio 1 1.1 Ill.a 44 6.3 31 ppm 89 51 ratio 1 1.1 lll.c 3.1 31 ppm 95 36 ratio 1 1.1 lll.c 46 6.3 63 ppm 95 51 ratio 1 Mixture according to the Dereo cincluae Exinvention Dge Degree of action caeve C lculte Ex Application rate [ppm] o cinosre Cly 1.1 III.c 47 6.3 +31 ppm 78 51 ratio 1 1.1 IlI.c 48 12.5 63 ppm 89 58 ratio 1 5 1.1 IV 3 493.1 1.6 ppm 3 ratio 2 1 1.1 +IV 6.3 +3.1 ppm 67 34 ratio 2 1 1.1 IV 51 6.3 +1.6 ppm 46 26 ratio 4 1 1.1 +.11V 52 12.5 3.1 ppm 67 43 ratio 4 1 1.1 Vill 53 6.3 3.1 ppm 45 26 ratio 2 1 1.1 Vill 54 12.5 +6.3 ppm 89 36 ratio 2 1 1.1 Vill 5512.5 +3.1 ppm 78 36 ratio 4 1.2 lIa 56 3.1 31 ppm 100 36 ratio 1 1.2 III- 59 6.3+3 PPM 990 72 ratio 1 1.2 IlI.c 6.3+3 ppm 99 72 ratio 1 Mixture according to the Ex Invention Degree of action observed Degree of action calculated Application rate [ppm] (Colby) 1.2 Ill.c 61 12.5 63 ppm 100 79 ratio 1 1.2 IV 62 3.1 1.6 ppm 67 ratio 2: 1 1.2 IV 63 6.3 3.1 ppm 95 62 ratio 2 1 1.2 IV 64 6.3 1.6 ppm 88 72 ratio 4: 1 1.2 VIII 6.3 3.1 ppm 77 58 ratio 2 1 1.2 VIII 66 12.5 6.3 ppm 88 68 ratio 2: 1 1.2 VIII 67 12.5 3.1 ppm 95 68 ratio 4: 1 USE EXAMPLE 4 PROTECTIVE CONTROL OF OF GREEN PEPPER BOTRYTIS CINEREA ON LEAVES The compounds tested and compositions containing them were as per Use Example 3.

Young seedlings of green pepper of the vanety "Neusiedler Ideal Elite" were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below, prepared from a stock solution containing 10 of the active ingredient, 85 cyclohexanone and 5 emulsifier. The next day the treated plants were inoculated with a spore suspension of Botrytis cinerea, containing 1.7 x 10 6 spores/ml in a 2 aqueous biomalt solution. Then the trial plants were immediately transferred to a humid chamber.

After 5 days at 22 to 24 0 C and a relative humidity close to 100 the extent of fungal attack on the leaves was visually assessed as diseased leaf area.

C The test results are listed in the following tables: CN Ex Compound Appln. Rate [ppm] degree of control 1 38 control (untreated) (85 attack) 0 12,5 0 O 69 1.1 6,3 0 3.1 0 6.3 42 1.2 3.1 13 63 71 S71 IIl.a 31 71 S63 42 Q 72 Il.c3113 31 13 0 3.1 71 73 I 1.6 42 3.1 71 74 1.6 42 The same experiments were carried out with mixtures in accordance with the instant invention. The results achieved with these compositions are listed in the following table: Mixture according to the Ex Invention e o i Degree of action calculated Ex invention Degree of action observed (Colby) Application rate [ppm] (Colby) 1.1 III.a 3.1 31 ppm 91 71 ratio 1 1.1 Ill.a 76 6.3 63 ppm 100 71 ratio 1 1.1 II.c 77 3.1 31 ppm 100 13 ratio 1 1.1 IIl.c 78 6.3 63 ppm 100 42 ratio 1 79 6.3 31 ppm 100 13 ratio 1 1.1 III.c 12.5 63 ppm 100 42 ratio 1 1.1 IV 81 3.1 +1.6 ppm 85 42 ratio 2 1 1.1 IV 82 6.3 +3.1 ppm 100 71 ratio 2 1 Mixture according to the Ex Invention Degree of action observed IDegree of action calculated Application rate [ppm] i.(Colby) 1.1 IV- 836.3 +1.6 ppm 100 42.

8125+31pm100 71 100i 42: 1.1 VilI 3. 1.6 ppm 100 42 ratio 1 1.1 VilI 87 1.5+31.1 ppm 970 71 ratio 4: 1 1.2 ill~ 88 32.1 +31 ppm 100 74 ratio 1: 10 1.2 III.a 889 3.1+631ppm 100 83 ratio 1 1.2 III.a 89 6.3+3 ppm 100 83 ratio 1 1.2 III.c 91 63 31 ppm 107 24 ratio 1 :1 1.2 +III.c 92 6.3 +3 ppm 97 66 ratio 1 1.2 IlI.c 93 6.3+3 ppm 100 ratio 1 10 94 631+1 ppm 100 ratio 2 1.2 IV 6.3 1.6 ppm 1 66 ratio 4 1 1.2 IVI 96 63 1.6 ppm 1 56 ratio 2: 1 1.2 Vill 66 .3 3.1 ppm 100 53 ratio 2 1 O Mixture according to the Mi t r acc d ngt o h Degree of action calculated x invention Degree of action observed Degree of a calulated 0 Application rate [ppm] S1.2 VIII )8 6.3 +1.6 ppm 100 66 ratio 4:1 n These test results clearly demonstrate that compositions comprising compounds 1.1, 1.2, C Ilia, IIIc, IV, and VIII exhibit synergism at different application rates.

Claims (1)

1. 51. A fungicidal mixture, compriSiflg as. active components a) an amide compound of the formula Il A.-CO NRlR 2 inw 2S hich A is an aryl group or an aromatic or non-~aromatic, 5- or 6-membered heterocycle which has from I to 3 hetero atoims selected from 0, N and St where the aryl group or the heterocycle may or may not have 1, 2 or 3 substituelts which are selected, independently of one another, from alkyl,.halogen, CHF2, CF 3 alkoxy, haloalkoxy, alkylthio,.' alkylsulfinYl and alkylsulfofl; RI is a hydrogen atom; R 2 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, alkeflyl, alkyflyl, alkoXY, alkenyLXy, Alkynyloxy, cycloalkyl, cycloalkenyl,. cycloalkyloxy, cycloalkenyloxY, phenyl and halogen, where the iliphatic and cycloaliphatic radicals may be partially or~i fully halogenlated and/or the cycloaliphatic radicals may be substituted by from 1 to 3 alkyl groups and-where the phenyl grou.. may have-from 1 t6-5 halogen atoms and/or from 1 to 3 substitueflts which are selected, independently of one another, from alkyl,,,haloalkylo, alkoxy, haloal .koxy, alkylthio and halaalkylthio, and where,t the .amidic phenyl group may ormay not be condenSed with a saturated 5-membered'ring which may or may niot be, substituted by one or more al~kyl gro%1p.s and/or may have a hetero atom selected from 0~ and St and a pyrimidifle derivative of the formula II CH 3 NH N N R H in which R is methyl, propyn-1-yl or cyclopropyl, 2. A fungicidal mixture, comprising as active components a) an amide compound of the formula I according to claim 1, and b) a pyrimidine derivative of the formula III according to claim 1, and c) at least one active ingredient of the formula IV or V, CN H F F F F SCN c I I V Cl i H and/or d) a phthalimide derivative selected from the group consisting of the compounds VIa, VIb and VII II )I 4- scc1 3 11 N SCCl 2 CHC1 2 nVIb 0 VIa 0 II N SCC13 0 and/or -a dinitroaniline of the formula VIII VII VIII NO 2 CI and/or .an arylsulfamide of the formula IX a or IXb (CH 3 2 NSO2NSCC12F IXa (CH 3 2 NSO 2 NSCCl2F IXb CH 3 in a synergistically effective amount. 3. A fungicidal mixture as claimed in claim 1 or 2, wherein in the formula I the radical A is one of the following groups: phenyl, pyridyl, dihydropyranyl, dihydrooxathiiynyl, dihydrooxathiiynyloxide, dihydrooxathiiynyldioxide, 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 trifluoromethyl. 4. A fungicidal mixture as claimed in claim 1 or 2, wherein in the formula I the radical A is one of the following groups: pyridifl- 3 -Yl, which may or may not be substituted in the 2-positiofl by halogen, methyl, difluoromethyl, trjfluoromethyl, methoxy, methyithio, methylsulfinyl or methylsulfolyl; phenyl, which may or may not be substituted in the 2-position by methyl, trjfluoromethyli. chlorine, bromine or iodine; .0 2-methyl-S ,6-dihydropyrafl 3 -yl; 2-methyl-Si 6-dihydro-1, 4-oxathiiyfl-3-y or the 4-oxide or 4 ,4-dioxide thereof; LS 2-methylfura~- 3 -yl, which may'or may not be substituted in the 4- and/or 5-position by methyl; which may or may not be substituted in the 2- and/or 4-position by methyl, chlorine, difluoromfethyl or zo trifluoromflthyl; thiazol- 4 -yl, which may or may not be substituted in the 2- and/or 5-positi on by methyl, chlorine, difluoromethyl or. zS trjfluoromethyl; 1-methylpyrazol-4-yli. which may or may not be substituted in the 3- and/or 5-positiOn by methyl, chlorine, difluoromlethyl or trif luoromethyl; or oxazol-S-yl, which may or may not be substituted in the 2- and/or 4-position by methyl or chlorine. A fungicidal-mixture as claim ed in any one of the preceding claims, which comprises a compound of the formula'! in which R 2 is a phenyl group which may or may not be substituted by 1, 2 or 3 of. the substituetits mentioned'in claim 1lor 2. 6. A fungicidal mixture as claimed 'in claim 5, where R 2 is a phenyl group which has one of the following s~ubstituefits in the 2-positiofl: C 3 -C 6 alkyl, C 5 -C 6 -CYCloalkenyl, C 5 -C. 6 CYCloalkyloxy, cycloalkeflyloxy, where these groups may be substituted by 1, Ar, 2 or 3 Cl-C 4 -alkyl groups, (D 0 CL l n 0 0D mq 0D CD t phenyl which is substituted by from 1 to 5 halogen atoms and/or from I to 3 groups which are selected, independently of one another, from Ci-C 4 -alkyl, Cl-C4-haloalkyl, C:-C 4 -alkoxy, C1-C 4 -haloalkoxy, Cl-C4-alkylthio and Cl-C 4 -haloalkylthio, or where R 2 is indanyl or oxaindanyl which may or may not be substituted by 1, 2 or 3 C 1 -C 4 -alkyl groups. 7. A fungicidal mixture as claimed in any one of claims 1 to 6, which comprises an amide compound of the formula a below: A-CO-NH' (Ia) in which EXR3 N R 4 ut)% 0 CH 3 (A3) (Al) R 5 RU 7 CH3 (A4) R9Ha (A7) A2) S N R 6 (A5) R 9 (A6) (A8) X is methylene, sulfur, sulfynyl or sulfonyl (SO 2 R 3 is methyl, difluoromethyl, trifluoromethyl, chlorine, bromine or iodine, R 4 is trifluoromethyl or chlorine, 31 R 5 is hydrogen or methyl, R 6 is methyl, difluoromethYl, trifluoromethyl or chlorine, RI is hydrogen, methyl or chlorine, oe.ty R 8 is methyl', difluoromety o rf~rmtY R 9 is hydrogen, methyl, -difluromnethyl, trifiubromethyl or chlorine., IND is c 1 lc, 1 -akyl, Cl- 4 .alkoxyi C 1 lC 4 alkylthio or haloge n. 8.A fungicidal mixture as claimed in any one of claims 1 to 6 which comprises as ainide compound a .compound of h oml lb below: CI ~CO-NH.(b N R 4 R 1 1 in which R 4 is halogen and 1 is phenyL wh~ich is substituted by halogen- 9. Afunicial ixtre s claimed in claim 1lor 2,which compses as amide compound a compound of the formuleblw 0 0 0 NN CNJ N Cl N Cl F C 0 N H/ N Ci N 10. A fungicidal product which is in the form of two parts, one part comprising the Samide compound of formula I according to any one of claims 1 to 9 in a solid or liquid carrier and the other part comprising compound of the formula III according to claim 1 in INO a solid or liquid carrier, the fungicidal product being packaged so that in use the two parts are mixed to produce the synergistic fungicidal mixture according to any one of claims 1 to 9. 11. A fungicidal product which is in the form of two parts, one part comprising the S amide compound of formula I according to any one of claims 1 to 9 in a solid or liquid carrier and the other part comprising compound of the formula III according to claim 1 N 10 and one or more of compounds of the formulae IV, V, Via, VIb, VII, VIII, IXa or IXb according to claim 2 in a solid or liquid carrier, the fungicidal product being packaged so that in use the two parts are mixed to produce the synergistic fungicidal mixture according to any one of claims 1 to 9. 12. A fungicidal mixture comprising as active components an amide compound of the formula I and a pyramidine derivative of the formula III, according to claim 1, which mixture is substantially as herein described with reference to examples 43 to 48, 56 to 61, 75 to 80 and 88 to 93. 13. 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 one of claims 1 to 11, where the application of the active components may be carried out simultaneously or in succession. 14. A method as claimed in claim 13, wherein the simultaneous application is either together or separate. DATED this 5 th day of December 2005 BASF AKTIENGESELLSCHAFT WATERMARK PATENT TRADE MARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA P17666AU01