AU2006201406B2 - Fungicide mixtures based on amide compounds and pyridine derivatives - Google Patents

Description

P001 Section 29 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: Furngicidal mixtures based-on amide -compounlds and pyridine derivatives The present specification discloses fungicidal mixtures for controlling harmful fungi, which mixtures comprise amide compounds of the formula I a)A-CO-NR 1

R

2

.(I

.0 a in which A .is an aryl group or an aromatic or non-aromaLtic, 5- or 6-mnembered heterocycle which -has from' 1 to 3 hetero at-oms; selected from 0, N and S; *where the aryl group or 'the heterocycle may or may not ha-ve 1, 2 or 3 substituentS which Are selected, ijndepenldently o one another, from alkyl,- halogepr.

CHF

2

CF

3 alkoxy, ha&loalkoxy, alkylthio, alkylsu3.fi'yl and alkylsulf'ofl l.

RI is a hydrogen atom;.

R

2 is a pheniyl or cycloalkyl group which may or may not have 1, 2 or 3 substituents which are selected from alkyl, alkenyl, alkyfll alkoxy, alkenyloxy alkyhyloxy, cycloalkyl, cycloalkenll cycloalkyloxyi cycloalkenloxy, phenyl. and halogen, 4here the aliphatic and cicloalxphatic radicals may be partially or f~lly halogenated and/or the cycloaliphatilc radicAls may be substituted by from I to 3 alkyl groups and *where the. phenyi.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, haiLoalko'xy, alkylthio and haloaJlkylthio, and where the amidic phenyl group may or may not be condeqnSed with a sauae 5mmee 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 pyrimidine derivative of the formula III,

CH

3

III.

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

Cl.2 C1 and/or d) a phtha limide derivative selected of the co *ounds VIa, VIb and VII fromx 'the group consisting 0.

0 VIa CCN SCC1 2

CC

2 A VIb.

0 0

II

N

II

0.

-SCC1 3

VII

and/or a dinitroaniline of the formula VIIT viii and/or f) an arylsulfamide of the formula IX a .or IXb

(CR

3 ZNSOzNSCCl 2

F

IXa in a -synergistically 'effective

(CH

3 )2NSO 2 NSCCl 2

F

~*.*IXb

CH

3 amount.

In one aspect, the invention relates to a fungicidal mixture, comprising as active components a) an amide compound of the formula I

A-CO-NR'R

2 in which A is an aryl group or an aromatic or non-aromatic, 5- or 6-membered 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, 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, haloalkyi, 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 i N R in which R is methyl, propyn-1-yl or cyclopropyl, In another aspect, the invention relates to 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.

As employed above and throughout this disclosure (including the claims), the following terms, unless otherwise indicated, shall be understood to have the following meanings: "Comprises/comprising" when used in this specification is taken to specify 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, 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.. 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: captafol) 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 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.

C

1

-C

12 -alkyl and in particular CI-C 6 -alkyl groups. Examples of alkyl groups are alkyl 'such as, in particular, methyl, ethyl, propyl, I-methylethyl, butyl, 1-methylpropyl, -2-methylpropyl, I,l-dimethylethyl, 'n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 2 -dime thylpropyl, 1, 1-dimethylpropyl, 2, 2-dimethylpropyl, I-ethylpropyl, n-hexyl, 1-methylpentyl, 2-met hylpentyl, 3-methylpentyl, 4-methylpentyl,', 1, 2-dime thylbutyjl, 1,3 -dime thy lbutyl, 2, 3 -dime thylbu tyl, 1-dimet -hylbutyl, 2, 27dimethylbutyl, 3, 3 -dime thyl butyl, 1,1, 2-trimethyipropyl, 1,2, 2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, I-ethyl-2-methylpropyl, n-heptyl,.1-methylhexyl, I-ethylpentyl,' 2-ethylpentyl; 1-propylbutyl, octyl, decyl, dodecyl.

Haloalkyl is an. alkyl group -as def ined'above which is partially or fully -halogenated by one or more halogen atoms, in particular by fluorine and chlorine. Pref erably, -there are from 1 to 3 halogen atoms present, and the difluoromethyl .or the' trif luoromethyl 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 brainched C4-C 1 2 -alkenyl groups and in particular C 3

-C

6 -alkenyl groups.

Examples of alkenyl groups are 2-propenyl, .2-butenyl,, 3-butenyl, l-methyl-2-p ropenyl, 2-methyl-2-propenyi, 2-pentenyl, .3-pentenyl, 4-pentenyl, l-methyl-2-butenyl, 2-methyl-2-buitenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, -ehl-utn, 3 -methyl-3 -butenyl, 1,idmty--rpnl 1, 2-dimethiYl727propenyl, 1-ethyl-2-propelyl, 2-hexenyl, 3-hexenyl,. 4-hexenyl., 5-hexenyl,* l-methyl-2- pentenyl, 2 -methyl-2-pentefiyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, .3-methyl-3-penteflyl, 4 -methyl-3-pentenyl, l-inethyl-4 -pentenyl, 2-methyl-4 -pentenyl, 3 -inethyl-4-pentenyl, 4-methyl-4-pentenyl, 1;1-dimethyl-2-butenyl, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dixnethyl-.2-butenyl, 1, 3-dimethyl-3-butenyl, 2, 2-dimethyl-3-butenyl, 2,3-dimethyl-2-b.utenyl, 2, 3-dirnethyl.-3-butenyl, 1-ethyl-2-butenyl, l-ethyl-3-butenyl, 2 -ethyl- 2-butenyl1, 2 -ethyl- 3-bu teniyl, 1, 2 -trimethyl-2-propenyl, -ethyl-1-methyl-2-propenyl and l-ethy1-2-methyl.-2- ropenyl, In particular 2-.gropenyl, 2-butenyl, 3-methyl-2-butenyl and *3-niethyl-2-pentenyl.; 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 alkyny1 groups. These are preferably straight-chain and br anched C3-C 1 2 -alkynyl groups. and in particular C 3

-C

6 -alkynyl groups.

Examples of alkynyl groups are 2-propynyl,. 2-butynyl, 3-butynyl1, 1-iethyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, -methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1, 1-dimethyl-2-propynyl, I1-ethyl- 2-propynyl, 2-hexynyl, .3-hexynyl, 4 hexynyl, 5-hexynyl, 1-methyl-2-pentynyl l-methyl-3-pentynyl, 1-rnethyl-4 -pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, -methyl- 2-pentynyl, 1, 2-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethy.-3-butynyl, 2, 2-dixnethyl-3-butynyl~,* 1 -ethyl -2 -butynyl, I-ethyl-3-butynyl, 2 -ethyl -3-butynyl 'and I -ethyl- I-methyl-2-propyniyl.

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

The cycloalkyl group is preferably, a C 3 -CGI-CYCloalkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl., If the cycloalkyl group is substituted, it preferably has f rom 1 to 3 .Ci-C 4 -alkyl radicals as substituents.

Cycloalkenyl is preferably a C 4

-C

6 -dycloalkehyl 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.

8 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 C 1

-C

4 -alkyl radicals as substituents.

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

Atyl is preferably phenyl.

If A is a phenyl group, this may have one, two -ori 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 25 pyrazolyl radical.

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

Y

in which one of the radicals X and Y is O, NR 2 3 where R 2 3 is H or alkyl, and the other of the radicals-X and Y is CH 2 S, SO,

SO

2 or NR 2 3 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

CH

(A3) in which X is CH 2 S, So or S0 2 The abovementioned het~erocyclic 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, difluoronethyl or trifluoromethyl,' A is particularly preferably a radical of the formulae: O R3 (Al)

R

7

,S

N::

QrCR 4 (A2) R8'

R

9 (A7) CH 3 in which R 3

R

4

R

6

R

7

R

8 and R 9 -i ndependently hydrogen,. alkyl, in particular methyl, halogen, chlori'ne, CHF 2 or dF 3 of one another are in particular The radical RI in the formula I-is preferably ;a hydrogen atom.

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 sulbstituent (or the substituents) is (are) prefe'rably selected-from the group consisting of alkyl, cycloalkyl, cycloalkenyl,- halogen or phenyl.

The substituents of the radical R 2 may in turn be substituted Sagain. The aliphatic or cycloaliphatic. substituents may be partially or fully halogenated, in particular fluorinated or EL chlorinated. They preferably have 1, 2 or 3 fluorine or chlorine atoms. If the substituent of the radical R 2 is a phenyl group, t 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 3 preferably, the phenyl group is substituted with a halogen atom in the p-position, 1*e. the particularly preferred substituent of Sthe 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: pyridyl, dihydropyranyl, dihydrooxathiiynyl, dihydrooxathiiyiyloxide., 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.

-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 haiogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinylor 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-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 R2 is a phenyl group which has one of the following substituents in the 2-position:

C

3

-C

6 -alkyl, Cs-Cg-cycloalkenyl, Cs-C6-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,

CI-C

4 -alkoxy,

CL-C

4 -haloalkoxy,

C

1 -C4-alkylthio and C1-C 4 -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 comprise as amide compound a compound of the formula Ia,

A-CO-NH

R

10 (Ia) 10 'in which A is R3 (Al)

RS

R

5 Iii77 CH 3 (A4) (A2) R7 S

R

6 (A5) CH3 (A3) R7 (A6) R 4

R

9 CH3N.SN2

R

8 (A7) RS\O(A8 (A8) R3 R4

RS

R

6 R7

RO

is methylene, sulfur, sulfynyl or sulfonyl (SO 2 is methyl,. difluoromethyl, trifluoromethyl, chlorine, bromine or iodine, is trifluororethyl or chlorine, is hydrogen or methyl, is methyl, difluoromethyl, trifluoromethyl or chlorine, is hydrogen, methyl or chlorine, is methyl, difluoromethyl or trifluoromethyl,

R

9 is -hydrogen, methyl, dif luoromethyl, trif luoromethyl or chlorine,

R

10 is Cl-C 4 -alkyl,

C

1 l-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 inl which

R

4 is'halogen and

R

11 is phenyl which ii substituted by halogen.

compoundsof the formula I, whic h may- be u sea in the fungicidal mixtures disclosed herein, are mention in EP-A- 545 p099-and 589 301 which are incorporated herein in their entirety by reference.

The preparation of the amide compounds of the formula I is known, for example, from. EP.-A-54S 099 or 589 301 or can be carried out by similar pro:esSeS.

Preferred substituents

R

21 and. R 22 are hydrogen, F, ci methyl, ethyl, methoxy., thioinethyl and N.-zethylamino. R3anR 4 together may also form a grouping =0.

erred fungicides of the dicarboximide type are the co~pounds Iha to Id: -11.a: ethyl (RS) 3 ,S-dichlorophenyl).5methyl24 dioxoox C1 CH 3

COD

2

CH-

2

CH

3

I~

1/.

C1 0r or II.b: 3 3 ,S-dichlorophefyl)Nisopropyl2,4dioxoimidazolidine- 1 -carboxamide CI 0

N

CIO '-CONHCH(CH 3 2

I~

or II.c: N-( 3 ,5-dichlorophenyl)-l,2-dimethylcyclopropane-, 2 dicarboximide

CI

CH

3 or II.d: (RS)- 3 -(3,5-dichloropheflyl)5ethenyl5methyl-1,3.

oxazolidine- 2 4-dione C! 0\ CH 3 Y-4-CH=CH 2 NI II.d.

C 6 These compounds are commercially available as. fungicidally active ingredients and are described in the literature as follows: *II.a (common name: chlozolilate): CAS RN (84332-86-51, DE-A 29 06 574; II.b (common name: iprodione):-CAS 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:.vinclozolile): CAS'RN (50471-44-8), DE-A 22 07 576].

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 a ctive ingredient 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.

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

1 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,.

trifl0oroacetic 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 I to 20 carbon atoms), arylsulfonio acids or aryldisulfonic 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 -phenoxybenzoc acid, 2-acetoxybenzoic acid, etc.

Suitable metal ions are, in particular, the ions. of the elements of.the first to eighth sub-group, in particular chromium, manganese, 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 variousvalencies 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 active-ingredients or fertilizers, can 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.

SSome 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 0fungi 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.

1 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, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (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 be employed for controlling Botrytis species in crops of 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 II 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/of 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, it 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 aronmatics '(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 S such as lignosulfite waste liquors and methylcellulose.

18 S uitable surf actants are the alkali metal salts, alkaline earth metal salts and .ammrnfitm saltS of aromatic sulfofliC acids, eg.

ligno-, phenol-, naphthalele- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- arnd alkylarylsulfonates, alkyl, lauryl ether and fatty achlsfteand salts of sulfated hexa-, hepta- and octadecalold, or of fatty alcohol glycol ethers, conden'sates of sulfonated. naphthalenle and its derivatives with formaldehyde, condensates of naphthalene or of the naphthaleflesulfonic acids with phenol and formaldehyde, polyoxyethylele octylphef.lol ether, ethoxylated isooctyl-, octyl or. nonylphell alkylpheflol *polyglycol ethers, tributypheflyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alco hol1/ethylene oxide conldenlsates.., ethoXYlated castor oil, polyoxyethylene alkyl ethers or poiyoxypropylene lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellu lose.

Powders, materials -for broadcastin .g and dusts can be preparedl by mixing or jointly grinding the compounds 1. or II and/or III to IX, or. the mixture of the compounds I and.11 and/or III to *IX, with a solid carrier.

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

Fillers or s6l.Id carriers are, for example, mineral earths, such as silica gel, silica sicts, talc, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous, earth, calcium sulfaite, magnesium sulfate, magnesium oxide, ground synthetic materials and fertilizers, such as anunrilum sulfate, ammonlium phosphate, am~monjim nitrate, ureas, and products bf vegetable origin, such as cereal meal, tree bark meal, Wood mealI and nutshell meal, cellulose powders or-other solid carriers.

The formulations generally comprise fromt to 95% by weight, preferably 0,.5 to 90% by- weight, of one df the compounds I and 11 and/or III to IX or of the .mixture of the compounds I and II and/or'III to IX. The active ingredients are empl'oyed in a purity of from 90%.t'o 100%, preferably 95%- to 100%- (according to NM1R or HPLC spectra.) compounds I and II ain'd/or III to IX, the miix tures, or the corresponding formulationis, 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 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 280C, 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 weght of th sodum salt of.diisobutylnaphthalene-l-sulfonate, 10 parts by 3 5 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; SVII. 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 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; S 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 1 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 described herein The synergistic activity of the mixtures described herein .can.be demonstrated by the following experiments: The active ingredients, separately or together, are formulated as 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 is calculated as follows using Abbot's formula: w (1 )-l100/ 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.

21 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/100" 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" 2were, 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 22-24c°. After 5 days, the extent of the fungal infection on the leaves could be determined visually in The compounds components: of the formula I used were the following 0- NH I.1 N Cl I

F

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

Table 1 Ex. IActive ingredient untreated Compound I.1 Concentration of active ingredient the spray liquor in ppm Efficacy in of the untreated control i ,q 1.

0

IC

2C 0 infection) 31 1 0 78 67 11 67 44 44 3C Compound 1.2 31 4C- Compound VIa 31 0 16 0 8 0 Compound VII 31 0 16 0 6C Compound IXa 31 0 0 8 0 Table 2

EX.

7 8 9 .11 12 Mixtures according to the invention (content in*ppm) 31 ppm I.1 31 ppm Via 8 ppm I.1 8 ppm VIa 31 ppm 1.2 31 ppm VIa 16 ppm 1.2 16 ppm Via 31 ppm 1.1 31 ppm VII 8 ppm I.1 8 ppm VII observed efficacy calculated efficacy*) 97 78 30 11 100 67 70.. 44 78 39 11 23

LO

0D Ex.

13 14 16 17 18 19 Mixtures according to the invention (content in ppm) 31 ppm I.2.

16 ppm I.2 16 ppm VII 8 ppm 1-2 8 ppm VII 31 PPm

I

.1 31 ppm IXa 16 ppm 1-1 16 ppm IXa 31 ppm 1.2 3i ppm IXa 16 ppm 1.2 16 ppm IXa 8 ppm I.2 8 ppm IXal observed efficacy "67 93 67 44 7 44 944 78 95 67 90 67 100 calculated efficacy*) 44 99 90 44 calculated using..Colby's formula- The tet rsul show that for all mixing ratios the observed The test results show that for a i h abeen calculated 0 efficacy is higher than the efficay h had bee lculated 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 e i n g redient which had with an aqueous preparation of active ingrieient which had been prepared from a stock solution comprising 10% of active ingredient, 63% of cyclohexanoe and 27% of emulsifier. 2disks hours after the spray coating had dried on, the fruit disks 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 0 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.

24 Table 3 Ex. Active Concentration of Efficacy in of ingredient active ingredient the untreated in the .pray 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 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 31 ppm VII 34 31 ppm I.1 30 0 31.ppm VIII 35 .16 ppm 1.2 20 0 16 ppm 16 ppm VIII calculated using Colby's formula The test results show that for all mixing ratios the observed efficacy is higher than the efficacy which had been calculated beforehand using Colby's formula.

USE EXAMPLE 3 CONTROL OF GREY MOULD (BOTRYTIS CINEREA) ON FRUIT SLICES OF GREEN PEPPER The following compounds and compositions containing them were tested: 1. Amides 1.1, 1.2 2. Pyrimidine derivatives Ilila, I1ic K~~CH3 Mia CH 3

N-

IIIC

CH

3 3. Pyrrole derivate IV 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 18-20o 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 o/l) 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

\O

k e, r, \o r, As a general rule the comparison of the expected degree of action according to the Colby formula) with the degree of action found shows whether the effect is synergistic or not, the correlation being as follows: 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 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 III.c 31 31 3.1 13 41 IV 1.6 2 6.3 2 42 VIII 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 Ex Invention Degree of action observed Degree of action calculated Application rate [ppm] (Colby) 1.1 Ill.a 43 3.1 31 ppm 57 36 ratio 1 1.1 III.a 44 6.3 31, ppm 89 51 ratio 1 1.1 ll.c 3.1 31 ppm 95 36 ratio 1 1.1 Ill.c 46 6.3 63 ppm 95 51 ratio 1 Ex nvntonDegree of action observed Degree of action calculated Application___rate_____I (Colby) 1.i Ill.c 48 6.+3ppm 78 58 ratio 1 5 1.1 IV~ 351.5+6 pm8 58 ratio 2 1 ratio 2: 1 1.1 IV 51 6.3 31ppm 6 26 ratio 4 1 1.1 IV ratio 4: 1 1.1 +JVI ratio 2 1.1 Vill 54 6. +3.1ppm 89 36 ratio 2: 1 1.1 ViIl 12.5 +3.1 ppm 78 3 ratio 4 :1 56 3.1 31 ppm100 3 ratio 1 1.2 IIl.a 56.+31pm100 72 ratio 1 1.2 +Ill.c 58 3.1 +31 ppm 84 36 ratio 1 1.2 II.c 59 6.3 63 ppm 99 72 ratio 1 1.2 Ill.c 6.3 31 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 31 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 VIll 67 12.5 3.1 ppm 95 68 ratio 4: 1 USE EXAMPLE 4 PROTECTIVE CONTROL OF BOTRYTIS CINEREA ON LEAVES OF GREEN PEPPER 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 108 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.

0 The test results are listed In the following tables: :X Compound Appin. Rate [ppm] degree of control[% 38 control (untreated) (85 attack) 0 F12,5 0 69 .16,3 0 3.1 0 11 01.2 6.3 42 703.1 13 71 ll~a63 71 31 71 7 lI~c63 42 231 13 -3.1 71 7IV1.6 42 Vill 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: Ex Invention I Degree of action observed Degree of action calculated Application rate [ppm] (Colby) 73.+31pm91 71 1.1 +III~a 76 6.3 +63 ppm 100 71 ratio 1 :10 1.1 IlI.c.

7731+3 pn100 13 ratio 1 78 6.3 +63 ppm 100 42 H- ratio 1 1.1 III.c 76.+31pm100 13 ratio 1 5 1.1 III.c 125+G63ppm 100 42 8131 .6pm85 42 826. 31ppn100 71 Mixture according to the Ex Invention Degree of action observed Degree of action calculated Application rate (ppm] (Colby) 1.1 IV 8363+16pm100 42.

100i 42 1.1 IV 864 12.53.1ppm 100 42 ratio 4: 1 1.1 Vill 87 31. +31.6 ppm 107 71 ratio 4: 1 88 3.16. +31 ppm 100 4 ratio 4: 10 889 3.131 ppm 100 83 ratio 1 :10 1.2 Ifla 89 6.3 +3 ppm 100 83 *rato 1:51 1.2 +IlLac 91 63 31 ppm 970 24 ratio 1 :1 1. 2+ IlI.c 92 6.3 +3 ppm 97 66 ratio 1 1I.+ II.c 93 6.3+3 ppm 100 ratio 1 1 .2 IVI 94 63 +1 ppm 100 ratio 2 1.2 IV 6.3 1.6 ppm 1 66 ratio 4 1 1.2 IV 96 63 1.6 ppm 1 ratio 2 1 1.2+ Vill 97 6.3+31.1 ppm 100 83 ratio 2 1 il Mixture according to the invention Degree of action calculated ;xvention Degree of action observed Application rate [ppm] C y) 1.2 VIII )8 6.3 +1.6 ppm 100 66 ratio 4: 1 These test results clearly demonstrate that compositions comprising compounds 1.1, 1.2, Ilia, Illc, IV, and VIII exhibit synergism at different application rates.

Claims (7)

1. A fungicidal mixture, comprising as active components a) an amide compound of the formula I A-CO-NRIR 2 in which A is an aryl group or an aromatic or non-aromatic, 5- or

6-membered heterocycle which has from 1 to 3 hetero atoms 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, independently of one another, from alkyl, halogen, CHF 2 CF 3 alkoxy, haloalkoxy, alkylthio, alkylsulfynyl and alkylsulfonyl; Rl R2 is a hydrogen atom; 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 0 and S, and a dinitroaniline of the formula VIII VIII NO 2 CI in a synergistically effective amount. I 2. A fungicidal mixture as claimea 7 in claim 1, wherein in the o formula I the radical A is one of the following groups: ci Sphenyl, pyridyl, dihydropyranyl, dihydrooxathiynyl, dihydrooxathiynyloxide, dihydrooxathiynyldioxide, furyl, thiazolyl, pyrazolyl or oxazolyl, where these groups may have S1, 2 or 3 substituents which are selected, independently of one another, from alkyl, halogen, difluoromethyl and trifluoromethyl. \D 10 3. A fungicidal mixture as claimed in claim 1,.wherein in the o formula I the radical A is one of the following groups: cO o 15 pyridin-3-yl, which may or may not be substituted in the Ci 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfynyl 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-yl; 2-methyl-5,6-dihydro-1,4-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; which may or may not be substituted in the 2- and/or 4-position by methyl, chlorine, difluoromethyl or trifluoromethyl; thiazol-4-yl, which may or may not be substituted in the 2- and/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 4S oxazol-5-yl, which may or may not be substituted in the 2- and/or 4-position by methyl or chlorine. 4. A fungicidal mixture as claimed in one of the preceding VO claims, which comprises a compound of the formula I in which SR 2 is a phenyl group which may or may not be substituted by 1, 2 or 3 of the substituents mentioned in claim 1. A fungicidal mixture as claimed in claim 4, where R 2 is a Sphenyl group which has one of the following substituents in the 2-position: ID 10 C 3 -C 6 -alkyl, Cs-C6-cycloalkenyl, Cs-C6-cycloalkyloxy, o cycloalkenyloxy, where these groups may be substituted by 1, S2 or 3 C 1 -C 4 -alkyl groups, o phenyl which is substituted by from 1 to 5 halogen atoms ND and/or from 1 to 3 groups which are selected, independently of one another, from C1-C4-alkyl, Ci-C 4 -haloalkyl, C-i Ci-C 4 -alkoxy, C1-C4-haloalkoxy, C-C 4 -alkylthio and Ci-C4-haloalkylthio, or where R 2 is indanyl or oxaindanyl which may or may not be substituted by 1, 2 or 3 Ci-C4-alkyl groups. 6. A fungicidal mixture as claimed in any of claims 1 to which comprises an amide compound of the formula la below: A-CO-NB (1a) RIO in which A is Va 0 0, ci KXR (Al) R (A CH4 (A4) SR 4 (A2) (AN) (A5) (R3 (A3 CB (M) (A6) R R 9 R 9 AR (A7) R5 0 (AS) X is methylene, sulfur, sulfynyl or sulfonyl (S02), R 3 is methyl, difluoromethyl, trifluoromethyl, chlorine, bromine or iodine, R 4 is trifluoromethyl or chlorine, R 5 is hydrogen or methyl, R 6 is methyl, difluoromethyl, trifluoromethyl or chlorine, R 7 is hydrogen, methyl or chlorine, R 8 is methyl, difluoromethyl or trifluoromethyl, R 9 is hydrogen, methyl, difluoromethyl, trifluoromethyl or chlorine, R 0 l is C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, Ci-C 4 -alkylthio or halogen.

7. A fungicidal mixture as claimed in any of claims 1 to which comprises as amide compound a compound of the formula Ib below: CO-NH N R 4 R 11 (Ib) in which R 4 is halogen and R 11 is phenyl which is substituted by halogen.

8. A fungicidal mixture as claimed in claim 1, which comprises as amide compound a compound of the formulae below:

9. A fungicidal product, which is in the form of two parts, one part comprising the amide compound I according to any of claims 1 to 8 in a solid or liquid carrier and the other part comprising the compound of the formula VIII 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 of claims 1 to 8. 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 8, where the application of the active ingredients amide compound I and the compound of the formula VIII may be carried out simultaneously or in succession. \\MERCURY2\Cases\2\17666\Au\04\20060404 amended claim page.doc\\ S11. The method of claim 10, wherein the simultaneous application is either 0 together or separately. c- 12. A fungicidal mixture substantially as hereinbefore described with reference to the examples.

13. The use of the fungicidal mixture as claimed in any one of claims 1 to 8 in Sthe manufacture of a product for the control of harmful fungi. ID

14. A fungicidal product substantially as hereinbefore described with reference to the accompanying examples. A method for controlling harmful fungi substantially as hereinbefore described with reference to the accompanying examples.