AU2005242193B2 - Fungicide mixtures based on amide compounds and pyridine derivatives - Google Patents

Description

I

P001 Section 29 Regulation 3.2(2)

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: Invention Title: Fungicide 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 specifi cation discloses fungicidal mixtures for controlling harmful fungi, which mixtures comprise amride compounds of the formula

I

A _CO-NR'

R

2 in which ra rmtcO o-rmtc -o A is an aryl group ora rmtco of0rmtc -o 6 -mnemrbered heterocycle which.-has from* 1 to hetero atom's selected from 0, N and

S;

where the aryl. group *or 'the heterocycle may or may not have 12 or 3 substitUents which are selectedr independently 'of one another, from alkyl-, halogene. CHF2," CF3. alkoxy, ha3loalkoxy, alkylthio, alkylsulfiy adalysufny.

RI is a hydrogen atom;.

R

2 is a pheflyl. or cycloaJlkyl group which may or may not have 1, 2 or 3 substituents w~hich are selected from alkyl, alkenyl, alkyny)-' alkoxy, alkeflyloxy, alkyfllOXYI cycloalkYui cy 'Joalkenylt cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, whvfiere the aliphatic- and cycloal2.phatic rad-icals may be partially or fully halo 0 genated and/or the cycloalipha-tic radicals may be substituted by *froml 1 to 3 alkyl groups and *where the phefyl.group, may have from 1 to 5 halogen atoms and/or from 1 to.3 substituents which* are selected, independently of one another1 from -alkyl,. halaalkyl, alkoxy, haloalkoXY, 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 Sr and 2 aprimidifederivative of the formula

III,

CH

3 in which R is me thyl, .Propyf-llY1 or cyclopropyl, and/or -1 at least one active igeenofte formula IV or

V,.

e ingredi n ft 0

H

F

F

CN

I I C1

H

and/or d) a phtha imide der ivative selected from the group consisting of the compounds VIa, Vib andVII p0 CC N-SCCl .3 0 VIa C N

-SCC

2 CHC12 vib 0 N-SCC1 3 0.

and/or e) a dinitroariiline of the formula VIII

VII

F

3 C N0 2

CF

3 CI NH.

VIII

and/or f) an arylsulfamiide of the formula IX a or IXb

(CH

3 2

NSO

2 NSCCl 2

F

IXa.

(CH

3 2 NS0 2 NSCC1 2

F

IXb GCl 3 in a synergistically 'effective amou .nt.

I

In one aspect, the invention relates to a fungicidal mixture, comprising as

C

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 Sheterocycle 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 Swhich are selected, independently of one another, from alkyl, halogen, CHF 2

CF

3 alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl;

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) at least one active ingredient of the formula IV or V, r

U

lN

F

0 N

IV

F

I

CCN

l N V

I

H

in a synergistically effective amount.

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).

4b 0 Fungicides from the group of the dicarboximides are known to the person NC skilled in the art and are commercially available.

0 Also known are the pyrimidine derivatives III, their preparation and their activity against harmful fungi [R methyl: DD-A 151 404 (common name: O 5 pyrimethanil); R 1-propynyl: EP-A 224 339 (common name: mepanipyrim); R=cyclopropyl: EP-A 310 550].

I 1 The compound IV is.known from K. Gehmann, R. Nyfeler, D A.J. Leadbeater, D. Nevill and D. Sozzi, Proceedings of the U 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 v (common name: captan) and VII (common name: folpet), their Spreparation and their activity against harmful fungi: The C 15 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 objectof 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 VI, I simul aneously, 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 "halog<en." used herein refers to fluorine, chlorine, br .omine and iodine and is in particular fluorine, c-I chlorine and bromine.

S 5 The term "alkyl", includes straight-chain and branched alkyl groups. These are preferably' straight-chain or branched

C

1

I.C

1 2 alkyl and in particular Cl C 6 -alkyl groups. Examples of alkyl groups are alkyl 'such as, in particular, methyl, ethyl, propyl, 1-methylethyi, butyl, 1-ethYlpropyl, 2-methyipropyl, 3-mnethylbutyl, 1,2-dimethylpropyl, 1, 1-dimtethylpropyl, c-I 2, 2dimethylpropyl, 1ethylpropyl, n-hexyl, 1methylpentyl, 2-~methylpentyl, 3-methylpenty)-I 4.-methylpentyl, 1,1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1l-ethyl -2 methylpropyl, n-heptyl, 1-methylhexyl, 1-typetl 2.-ethylpentyl, i-propylbutyl, octyl, decyl, dodecyl.

HaloalkYl is an. a lkyl group as defined above which is partially or f.lly-halogenated by one or more halogen atoms, in particular by fluorine and chlorine, preferably,- there apre from 1 to 3 halogenl atoms present, and the difluoro-methYl or the' trifluoromethyl group is particula~rly 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, alkylsulfirlyl and alkylsulfoflYl.

The alkenyl group includes straight-chain and branched alkenyl groups. These are preferablY straight-chain or branched

C

3

-C

12 -alkenyl groups and in particular

C

3

-C

6 -alkenyl groups.

Examples of alkenyl groups are 2 -propeflyl,2-butenYl, 3-butenyl, l-methyl-propenyl, 2-methyl-2.-propenyl, 27pentell .3 -penteriyl, 4-pentenyl, 1-methyl.-2-butenyl, 2 -methyi-2"butenyl, 3-methyl-2-butenyl, 1.-methyl-3-butenyl, 2.!-ethyfl-3butenyl, 3-mrethyl..3butenyl, l,l-dilethyl2-p ropenYl, 1,2.-dimetIyl72-propenyl, 1 -ethyl-2 propenyl, 2T-hexenyl, 3-hexenyl,, 4-hexenyl, 5-hexenyl,* l7methyl.-2.pentenyl, 2.-methyl-2-pentell 3 methyl~2-pentenyl, 4.-methyl-2.-peftenyl1, l.-methyl-3-pentenYl, 2 -rethyl-3pentenyl, 3-ehl3-etnl 4-~methyl-3-peltenl)' l-rethyl4pentenyl, 2-~methyl-4-peltenli 3-methyl.-4-petenyl, 4 -methyl4-Pentenyl, l*I-dimethy1-2-butenyl, 1, 2-di.Tnethyl-2-butelyl, 1,2-diImethyl-3-butell 1, 3.-dimethyl-2-butelyl, 1,3-dimethyl-3-butelyl, c-I2, 2-.dimethyl-3-butelyl, 2 1 3-dimethyl-2butenyl, 2 -ethyl- 2-butelyl, 2-ethyl-3-butenll 1,2-trimethyl-2-properiyl, 1l-ethyl- 1-methyl-2 propenyl and 1 -ethyl -2 -me thyl-2 -Propenyl, in particular 2-propenyl, 2-buteflyl, 3-methyl-2-butenyl and 3-miethyl-2-peltelyl.- The alkenyl group may-be partially or fully halogenated by one or c-I more halogen atoms, in particular by fluorine or chlorine. The c-I alkenyl group preferably has from 1 to 3 halogen atoms.

The alkynyl group includes straight-chain and branched alkynyl1 cI 15 groups. These are preferably straight-chain and branched

C

3

-C

1 2 -alkynyl groups and in particular

C

3

-C

6 -alkyflyl groups.

Examples of alkynyl groups are 2-propyflyl,' 2-butynyl, 3-butyny'l, .1-methyl-2-propynyl, 2-pentynyl, 3-pefityflyl, 4-pentynyl, i-methyl- 3 -butynyl, 2 -methyl-3 -butynyl, 1-methyl-2-butyflyl, 1, 1-djmethyl-2-pr pylyliJ 1 -ethyl- 2 propynyl, 2-hexynyl, 3 -hexyflYl, 4-hexynyl, 5--hexylyl, l-methyl-2-peltyn~yl 1-methyl-3pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-peltyflyl, 2-methyl-4pentynyl, 3-metbyl-4-pentynyl, .4-methyl-2-peltylyl, ,2-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3-but'nyl, 2,2-iehy -uyn2.- 1-ethyl-2-butynyl, 1 -ethyl -3 -butynl, 2-ethyl-3-butyflyl and 1 -ethyl- 1-metl yl-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 cyclohexyl.. If the cycloalkyl group is substituted, it preferably has from 1 to 3

C

1

I-C

4 -alkyl radicals as substituents.

cycloalkenyl. is preferably a C4C-Yl~ley group, such as cyclob~utenyl, cyclopentenyl or cyclohexelYl. If the cycloalkerlyl.

group is -substituted, it preferably has from 1.to 3 Cl-C 4 alkyl radicals as substituents.

I A cycloalkoxy group is preferably a C 5

-C

6 -cycloalkoxy group, such as cyclopentyloxy or. cyclohexyloxy. If the cycloalkoxy group is SS substituted, it preferably..has from 1 to 3 C 1

-C

4 -alkyl radicals as Ssubstituents.

O

The cycloalkenyloxy group is preferably a Cs-C 6 -cycloalkenyloxy group, such as cyclopentyloxy or cyclohexyloxy. If the Scycloalkenyloxy'group is substituted, it preferably has from 1 to 3 CI-C 4 -alkyl radicals as substituents.

1 Ajryl is preferably phenyl.

If A is a phenyl group, this may have one, two or three of the

I

n abovementioned substituents in any position. These substituents S 15 are preferably selected, independently of one another, from e C N 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:

Y

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 cxr c-I0

>CH

3 (A3) in which X is CH 2 ,S rS 2 The abovementioned heterocyc~ic 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, difluorornethyl or trifluoromethyl.' .A is particularly preferably. a radical of the formulae: 023 N

R

4 (Al) (A2)

R

7

I

I N

R

6 (A5) (A7)

CH

3 in which p 3 4 6 7

R

8 and

R

9 -independently of one another are hydrogen, alkyl, in particular methyl, halogen, in particular chlorine,

CHF

2 or CF3.

The radical Rl"in the formula IliS preferably a hydrogen atom.

radical

R

2 in the formula I is preferably a phenyl radical.

R

2 preferably has at least one 5 ~ubstituent which is particularly preferably in the 2-position. The sub~stituent (or the subst2-tuents) is (are) preferably selected from the group consistinlg of alkyl, cyclo.alkvl, cycloalkefyl, halogen or phenyl.

The subst-ituents of the radical R2 may I n turn be subst Ituted again- The aliphatic or cycloaliphatic substituents may be partially or fully halogenlated, in particular fluorinated or chlorinated. They preferably have 1, 2 or 3 fluorine or chlorine atoms. if -the substituent of the radical R2 is a phenyl group, U this phenyl group may' preferably be substituted by .from I 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 (Ni substituents.

R

2 is in this case, for example, indanyl, thiaildalyl and oxaindal Preference is given. to indanYl...and 2-oxaindaflyl which are attached to the 'nitrogen atom -in particular-via the 4 -positiofl.

According to a preferred embodiment, the composition according to the invention comprises as amiide compound a -compound of the formula I'ih which A is as defined below: phenyl, pyridyl, dihydropyranyl, dihydrooxathiiynYl, dihydroxathiiyi~yloxide., dihydrooxathiiyy.1ydioxide, furyl, thiazolYl, pyrazolYl or. tixazolyl, where these groups may have 1, 2 or 3 substituents which are selected, independently of one 3~n another, from alkyl halogen, difluoromethYl and trifluOromethYl.

According to a further preferred embodiment, A is one of the following groups: pyridifl-3-yl, which may or may not be substituted in the 2poitiofl by hAlogen, methyl, difltloromethyl, trifluoromethyl, methoxy, methylthio, methylsulfiflor metehylsulfonyi; phenyl, which may or may not be substituted .in the 2-position by 4methyl, trifluoromethyl, chlorine, boieor iodine; 2 -methyl- 5 ,6--dihydropyran-3-yl; 2 -methyl-5,6-dihydro-1, 4-oxathiiyfl-3yl or the 4-oxide or.

4 4dioxide thereof; 2 -nethylftran- 3 -Yl which may or may not be substituted in the 4 and/or 5 -positiofl by methyl; which may or may not be substituted in the 2and/or 4 -position by methyl, chlorine, .difluoromethyl Ior trjfflororflethyl; thiazol-4-Yl' which may or may not be substituted in the 2and/or 5 -positibn by .methyl, chlorine, diflubrom ethyl or trjf luorotflethyl; I -methylpyrazol-4-yl which may or may not be substitu .ted in the 3- and/or 5-position by methyl, chlorine, difluo .romethyl or trifluoromnethyl; or which may or may not be substituted in the 2- and/or 4_positiofl by methyl or chlorine.

Accordinlg to a further preferred embodiment, the compositions accor .dinlg 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 aboveUmentioned substituernts According to a further preferred embodimX~ent, the compositionls 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 3the following substituents in the 2-position: 3

-C

6 alkyl

C

5

-C

6 -CYCloalkenyl 5 -C6 -CYCloal kcyloxy cycloalkenyloxy, -where these groups may be substituted by 1, 2 or 3 C,-C 4 -alkyl groups, phenyl, which is substituted by from 1 to 5 halogen atoms and/or from 1 to 3 gro .ups which are selected, independently .of one 'another, fr:om c 1

-C

4 -alkyl,

C

1 4 -haoalkyl, Cl-C 4 -alkoxy, 14 .haoakoxy, CC 4 alkylthio and

C

1

C

4 haloalkylthio, or oxaindanyl. which may or may n ot 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 (a (Ia) in which A is (Al)

R

RS:::

5

CH

3 (M4) N

R

4 (A2) N R 6 (A5) 0 CH 3 (A3)

S

(A6)

RI

R

9 (A7)

R

9 (A8)

R

3 mnethylene, sulfur, sulfyflyl or sulfoflYl

(SO

2 methyl,. difluoromethyl, trifluoromethYl, chlorine, bromine iodine, trifluoromethyl or chlorine-, hydrogen or methyl, methyl, difluoromethyl, trifluoromethyl or chlorine, hydrogen, methyl or chlorine, methyl, difluorornethyl or trifluoromethyl,

R

9 is hydrogen, methyl, difluoromnethY 11 trif luoromethyl or chlorineIhoo aoe

R

1 0 is

C

1

C

4 -alkyl,

C

1

-C

4 alkoxyi C1

C

4 -alkylt- rhlgn Also disCl~osed is a fungici~dal mixture comprising as amide compound a compound of tefruaT

U

0

CO-NH

N R 4

R

1 1 (Ib) in which

R

4 is -halogen and

R

1 i heflYl which is ubstituted by halogen- Amd 0 pud fthe formula iwhich may-be used 'in the fungicida mitures disclosed herein,ar metif inE- 54S099 and 589 301 which are jnorporae hrin nthi entirety by reference.

preparation -of the amide compounso h fruaii nout.

for example, from EP-A-5 4 5 099 or 589 301 or can be car riedot by similar processes.

Preferred substituents

R

21 and

R

22 n-R toghyrgniF C, etherethyl, methOXY., thiolnethyl and N-nethylamino 3 ad 4 tgte may also form a grouping =0_ preferre funIdes of the dicarboxcimide type are the compounds hja to Id- .Ila:etyl 3 $mthl24 dioxooxazOlidine--abxlt'.

0 CH 3 CO 2 CH 2 CH3 14 II.b:

J

3 1 1-carboxamfide o It.b C1 l or 3 ,5-dichorophel)1 )1, 2 detylyclpoae1 dicarboximfide C1 O H 3 'n 15

I~

I

H

3 CI 0 0 or II.d: (Rs) 3 (3,5 -dichlorophenyl) -5 e h n l 5 m t y oxazo]lidine- 2 4-dione CI 0 OH 3

~CH=CH

2 IId 0 These compounds are commercially available as. fungicidally active ingredients and are described in the literature as follows: *II.a (comml~on name: chlozoliflate) GAS RN [84332-86-5], DE-A 29 06 574; 1 I. b (comm~fonlame: iprodiofle) 'CAS RNq ~367 3 4-19

US-A

3,755,350; II.c (commufon name: procymidone): CAS RN [32809-16-81,

US-A

3,903,090; Ii.d (common name:vinclozoline): CASRN [50471-44-8], DE-A 22 07 576].

To unfold the synergistic activity, even a small amount of the ajnide.Compound of the formula I is sufficient- Preference is given to employing amide compound and active ingredii-flt 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 aide copounds I comprise both compounds II and one or more amide compounds I, cps mtures, the mixing ratio of the compounds III to IX. In such mixtures, the mixing ratio of the compounds II and III to IX with each other is usually n the range of from 50:1 to 1:50, preferably from 10:1 to 1:10.

to the basic character of their nitrogen atoms, the compounds III; I, V and VIII are capable of forming salts or adductmpouns with inoran or organic acids or with metal ions.

adducts with inorganic orgn 0 'cisre hydrohalic acids such as 1 0 Examples of inorganic acids ar, hydrohalic acid uch as hydrofluoric acid, hydrochloric acid, hydrobromic acid acind hydriodic acid, sulfuric acid, phosphoric acid and n uitable organic acids are, for example, formic acid, carbonic S u i t a b l e o rganic acids are, a c e t i c acid,.

and alkanoic acids, such as and propionic acidcid,.

trifl oroacetic acid, trichloroacetic acidand propionic acid, and also glycolic acid, thiocyannac acic acid succini acid, citric acid, benzoic acid, cinnaic acid oxalic acid, alkylsulfonic acids (sulfonic acids having s)traight-chai or 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 branched arlyl adioshonic acids (aromatic radicals, such as acids or arydiphosphoncid phenyl and naphthyl, which carry one or two phosphonic radicals), it being possible for the alkyl or aryl radicalicylis to carry further substituents, eg. p-toluenesulfonic acid, alicy c 3 acid, p.aminosalicylic acid, 2-phenoxvbenzoi acid, 2-acetoxybenzoic acid, etc.

in particular, the ions of the elements Suitable metal ions are, in p in particular chromium, of the first to eighth sub-group n partzinc and furhermore of mangafnese, iron, cobalt, nickel, copper, zinc and furthermre of the second main group, in particular calcium and magnesium, and the second main group, in particular aluminum, tin of the third and fourth main gr th rius valencies which and lead. The metals can exist i the variou valencies which they can assume.

referred to'employ the pure When preparing the mixtures, it s preferred toemploy 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 ing admixed.

The mixtures of the compounds I and II and/or III to IX, or the h compounds I and II and/or III to IX used simultaneously, jointly or separatel exhibit outstanding activity against a wide range U of phytopathogenic fungi, in particular from the classes of the Ca of phytopathogenic fungi,

P

hcmeesnd Deuteromycetes.

Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromyceteas S 5 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 Sefungi in a variety of crop plants1 such as cotton, vegetable p fn gi in a viembe, cbeans, tomatoes, potatoes and cucurbits), Sspecies (eg- cucumbers, maize, fruit species, rice, barley, grass, oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a V variety of seeds.

STheyare particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Eodosphaera 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, Vnturia 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 inestans 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 for controlling Botrytis peces particularlypreferably.be employed and also in ornamentals.

in crops of grapevines and vegetables, 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 crop areas, from 0.01 to 8 kg/ha, preferably 0.1 to kg/ha, in particular 0.2 to 3.0 kg/ha.

I

The application rates of the compounds I are from 0.01 to l^ 2.5 kg/ha, preferably 0.05 to 2.5 kg/ha, in particular 0.1 to 0 1.0 kg/ha.

U 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\ 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 01 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.

1 If phytopathogenic harmful fungi are to be controlled, the S separate or joint application of the compounds I and II and/or SIII to IX or of the mixtures of the compounds I and II and/or III CN 15 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.

eg by The formulations are prepared in a known manner, eg by extending the active ingredient with solvents and/or carriers, i- 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.

U

18r h lai ea at alkaline earth Sui-table Surf actants arec the alkal aetal saltS meta sals and a-monilUn salts of aromac I~ fncais g metal salt lerfe-and dibutYlnaphthalnsfoi ligno-, phenl-, naphthalel acid an offatty acids, alkyJ- and alkylarylsulfonates, alky]-, lauryl ether and fatty alcohl sulfts n at slae hexa-, hepta- and octadecanols or of fatty alcohol glycol ehrcondensates of sfoaed.nptlneand its derivatives with formaldehyde condensateofnptaneo naphthalenesu lfoni c acids wjth, phenol and formaldehyde, polyoyethene octyiphenol ether, ethoXYlated isooctYl-i octyl ornonylpheno"l alkyiphenol polYglycol etes rbtyipenyl polyglycol ethers, alkylaryl polyether alcohols, ISotiey alcohol, fatty alcohol /ethylene oxide condensates.. ethoxylated ca~so i, polyoxyethYlene alkyl ethers or polyoxypropylene l*aur aoho poyglycol e ther acetate, sorbitol e s ters, waste liquors o ehlells PowerS maerils or 0 acasifl an dutscan be prepared by mixing or jointy grinding th compond II and/or III to-X ix or he mxtue of the compoundSiadian/ri tIX with a solid carrier.

coatd grnule, ipregnated granules or teatv Grnues(eg coated brabindeng Gr nu es usgranules) are usually Prepare od y ing te ctv homOgeneou solid inarrier., Ingredient, oratieinrchnslt Fillrs r 5 oid arriers are, for example, mineral earths, sc a sF il ic a r g e 1 d cil s il ic a te s t a lc as ka li ca gi elst e l imef chalk, bole., .,beSS, clay, doloc mite, diatoacestearh lcium sufae magnes ium sulfate, magnesium oidemaground sytheti maerials and fertilizrfs~ha and rout syntheetabl mra in ucasealmu nirea, tres o xn ni e sulfate, a m mironium phosphate ,h a s l n u nitr mate, re e ak mal, produt meal and nutshell meal, cellulose powders o~te solid carriers.

Th omuain gnrlY opie fro, 'U to 95% by weight, preeralYo,5to90%by weight, of onend Iftecmpud and

II

ran d r a l 0 5 t o x o f t e m i x t u r e o f t h e C O m p u d p a dri t I I, to IX.o The ative ingredients are employed in a prt of fro m .901 to 10 preferably 95% to 1 00%(codn Ro HPLC sp .ectra.) The co po nd I and ii and/or I ,,to I h thea m u 4 5 T he c p o un d s Io m l t o a re a p p lie d b y tre a t 'n h a m u ungi, their habtat, Or the planl~ ed~ olaes 19 materials or spaces to be kept free from them with a fungicidally aterive amount of the mixture, or of the compounds I and II S effective amou"t o case of separate application.

C and/or III to IX in the case of separate alication U 5 Application can be effected before or after infection by the harmful fungi.

SExamples of such preparations comprising the active ingredients are: 1 0 the active ingredients I. A solution of 90 parts by weight of l rrli e; this Sand 10 parts by weight of N-methylpyrrolidone; this Sh land 10 par for use in the form.of microdrops; solution is su±LQ-'olution ht of the active ingredients, A mixture of 20 parts by weight o t by weight of the parts by weight of xylene, 0 parts by weight of e adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleic adduct of 8 to 10 prtesby weight Of the calcium acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonate, 5 parts by weight ofthe adduct of 40 ol 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 y weight of isobutanol, 20 parts by weight of the adduct Sbye and 1 mo 1 of castor oil; exode and 1 mol of castor oil; of 40 mo 1 of etnyle of 40 mol o etny--ts y weight of the active Iv. An aqueous dispersion of 20 parts by wght exaol, 65 parts ingredients, 25 parts by weight of cy clohexanfol 6 p aont by weight of a mineral oil fraction of boiling point 210 to 280 y C, and 10 parts by weight of the adduct of 40 mol of 280oC, and 10 parts o castor oil; ethylene oxide and 1 mol of castor o il; 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 0 parts by weight of the. sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 partsby weight of pulverulent silica gel; a spray mixture is obtained by finely distributing the mixture in water; S..z vh of the active

VI.

An intimate mixture of 3 parts Dy we g.

An intimat of finely divided ingredients and 97 parts by weight iv kaolin; this dust comprises 3% by weight of active ingredient; VII An intimate mixture of 30 parts by weight of the active SAn ingredients, 92 parts by weight of pulverulent silica gel ingredients, 92 parts affin oil which had been and 8 parts by weight of paraffin il i e sprayed onto the surface of this silica gel; this formulation imparts good adhesion to the active ingredient; VIII. A stable aqueous dspersion of 40 parts by weight of the VIII. A stable aqueous dispersnthe sodium salt active ingredients, 10 parts by weight of the sodium sat of a phe ngsufoni, acid/urea/formaldehyde condensate, 2 Sa phenolsulf b o silica gel and 48 parts by weight of parts by weight may be diluted further;

IX-

water; this disper- p A stable ily dispersion of 20 parts by weight of the active ingre d i entsi 2 parts by weight of the calcium salt active ing r e d i e n t s P 8 parts by weight of fatty of dodecylbenzenesulfon ate parts by weight of fatty um alcohol polyglycol ether, 20 parts by weight of the sodium alcohol polyglycol ether, acid/urea/formaldehyde condensate salt of ars by weight of a paraffinic mineral oil.

and 88 parts by weight of a p Use Example c of the mixtures described herein The synergistic actvithe following experiments .can be demonstrated by the fg experiment The active ingredients, separately or together, are formulated as The active ingredients, separatey e ght of cyclohexanone and a 10% emulsion in a mixture of 63% by weight o r ccloheanne a 27% by weight of emulsifier, and diluted with water to the desired concentration.

Evaluation is carried out by ermining the infected leaf areas Evaluation is carried out by effcacies The in percent These percentages areAbbots formula: efficac is calculated assing Abbt's ormula: S= (1 -)100/P corresponds to the fungal infection of the treated plants in corresponds to the fungal infection-f 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 h ex dete d u e f fi cac i es S were determined using. Colby's formula Colby, Weeds O 20-22 (1967)] and compared with the observed efficacieS.

la x x-y/100' O Colby formula: E x E expected eficacy, expressed in f the untreated control, Swhen 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 Sactive ingredient A at a concentration of a Sefficacy, expressed in of the untreated control, when using y efficacy, expressed i V) active ingredient B at a concentration of b e E Activity against Botrytis cinerea on bell C| Use Example 1 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 whichhad 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 chanber 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 components: of the formula I used were the following 0- NH Il.1 N Cl

F

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

,Table 2 Mixtures according to the invention (content in. ppm) 31 ppm 1.2 i-ng Ibv's formula calculated using..Colb s fthe observed e ts show that for all.mixing ratios te obsered The test results higher than the efficacy whih had been calculated efficacy is higher formula.

beforehand using Colby' formulaon bell Use Examle 2 Activity against Botryis cinerea Use Example 2 peppers runoff point Sof reen bell peppers were sprayed reent h had Disks of gre% of active with an aqueous preparation of active ingredient which had been prepared from a stock solution comprising 10% of active been prepare 3% of cyclohexanone and 27% of emulsifier. 2 hours after the spray coating had dried on, the frucinerea were inoculated with a spore suspension of Botrytis i a were ino 1.7 x 10 spores per ml of a 2% strength Biomalz contain.nghe inoculated fruit disks wee susequently solution. Th C over 4 y he incubated in moist chambers at 18C over 4 days the Botrytis infection on the diseased fruit dis evaluated visually.

The resultS re shown in Tables 3 and 4 below.

The results ao w

I

Table 3 Efficacy in of IConcentration. of Ex. kc U V ingredient active ingredient in the spray liquor in ppm 0 (100% infection) tEfcc untreate control 0 21C 22C untreated Compound-1.1I 0 1 2 0 23C I Compound 1. 2 24C Compound IV- j310 16 I0 :2 6C 27C Compound VIa Compound

VII

Compound

VIII

*31 31 31 16 0 0 0 Table 4 Ex.

r 28 29 32 33 16ntn pp n 1.1 31 ppm IV1 31 ppm I.2 16 ppm I.1 31 ppm 1.2 16 ppm'IV 31 ppm 1.2 31 ppm.IVa 31 ppm 1.2 31 ppm VII 31 pPM I1 31 ppm VIII 16 ppm 1.2 16 ppm VIII observed efficacy 20 0 70 0 50 40 30 0 20 0 calculated efficacy*) 0 calculated using Colby's formula In 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 0 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: S1. Amides 1.1, 1.2 2. Pyrimidifle derivatives Ilila, 111c

N-

lil C H CHc 3. Pyrrole derivate

IV

4. Dinitroafliline. Vill VI iI The biological activity of the compounds and compositions containing them were tested as follows: o Fruit slices of green pepper were sprayed to run-off with an aqueous suspension, containing O the concentration of active ingredient or their mixture mentioned in the table below, prepared Sfrom 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 ¢q 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 Suntreated 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 S 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 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 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: 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 43 Mixture according to the invention Application rate [ppm] Ill.a 3.1 31 ppm ratio 1 1.1 Ill.a 6.3 31 ppm ratio 1 1.1 IIl.c 3.1 31 ppm ratio 1 1.1 III.c 6.3 63 ppm ratio 1 10 Degree of action calculated Degree of action observed (Colby) 57 36 89 51 95 36 95 51 mixtre-acoring o, te LDegree of action calculated SEX invention Degree of action observed (Colby) Application rate [ppm] lII~c 47 6.3 +31 ppm 78 51 ratio 1 I III-c 48 12.5 63 ppm ratio 1

IV

S3.1 1.6 ppm 3 49 ratio 2 1 S 50 6.3 3.1 ppm673 ratio 2 1 6 51 63 .6 pm 4626 1.1 +:IVI 5212.5 +3.1 ppm 6784 ratio 4 36 1.1 Vll~ 56 63.1+31 ppm 1002 ratio 1: 103 1.2 ill~ 57 62.3+ 63 ppm 93 ratio 1.2+ ill~ 558 32.1 3.1 ppm783 ratio 1:10 .2 II.a 66 .3 3 ppm 99 3 ratio 1 7 1.2 II-c 6.3+ 31 ppm 107 ratio 1 57 Mixture according to the Invention Dre Degree of action calculated 0 EX invention Degree of action observed (Colby) Application rate [ppm] 1.2 Ill.c 61 12.5 63 ppm 100 79 Q ratio 1 1.2 IV 62 3.1 1.6 ppm 67 ratio 2: 1 S1.2 IV 6.3 3.1 ppm 95 62 63 6 ratio 2: 1 CI 1.2 IV 6n 6.3 1.6 ppm 88 72 6 4 ratio 4: 1 -N 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 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 variety "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°C and a relative humidity close to 100 the extent of fungal attack on the leaves was visually assessed as diseased leaf area.

The test results are listed in the following tables: 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 Dge fato ac Ex invention Degree of action observed Dereo(Ctonlb) A, pliratiofl rate [ppm] C ly lated 76 77 78 79 81 82 1.1 IlLl 9 7 3.1 31 PPM ratioI 6.3 63 ppm 107 ratio 1 6.3 31 PPM ratio 1 Li+ III .c 6.3 63 ppm 100 42 ratio 1: 1.1 IVl~ 42 1 ratio 2:15 1.1 IV 4 63.31 PPm IV100 I7 Id". ra Mixtre according to the Ex invention Application rate [pprnl Degree of action observed Degree of action calculated (Colby) I I I 83 84 86 87 88 89 91 9 9 1.1 +IV 63 1.6 ppm 10( ratio4:l 1.1 +I V 62.3 31 ppm 10 ratio 4. 1 LI1 Vill 1. .1 ppm 1 ratio 4 1 1.2 Villa 6 3 +31.6ppm 1 ratio 1:10 1.2 ill 62.3 3 ppm ratio 1 :10 1.2 II-a 6.3 63 ppm ratio 1 0 71 0 42 00 42 7 71 00 74 100 83 100 83 97 66 3 5 1.2 111-C 6.3 31 ppm ratio 1 1.2 IV 3.1 1.6 ppm ratio 2: 1 1.2 IV 6.3 1 .6 ppm ratio 4 1 1.2 Vill 3.1 1.6 ppm ratio 2: 1.2 Vill 6.3 3.1 ppm ratio 2: 100 91 66 100 100 8 96 Mixture accordinlg to the anenc Dere obere Degree of action calculated of action (Colby) kipplicationl rate [ppm] U)9 6 3 +1.6 ppm 100 66 These test results clearly demonstrate that compositions comprising compounds 1.1, 1.2, Illa, 111c, IV, and Vill exhibit synergism at different application rates.

Claims (8)

1. A f ungicidal mixture# comprising as. active components a) an amnide compound of the formula I A.;C0-NRlR 2 I 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 at'oms selected from Or N and S; the aryl group or the heterocycle may or may not have 1, 2 or 3 substituents which .are selected, independently of one another, from. al-kyl, .halogen, CHF2, CF3, alkoxy, haloalkoxY, alkyithio,. alky1lsulfiflyl an 3 d alkylsulfonl; RI is a hydrogen atom; R 2 is a Phenyl or cycloaJcy 1 group which may or may not have 12 or 3 Substituents which are selected, independently of one another, from alkyl, alkenyl, alkynyl, alkoXY, aJlkenyloxy, alkylJoxy, cycloalkyl, clycJoalkenyl. cycloalkYloxy, cycloalkenyloxy, phenyl and halogen., where the al*iphatic and cycloaliphatic radicals may be partially or fully halogenated and/or the cycloa]liphatic radicals may be substituted. by from I to 3 alkyl grouxps *andwhere the phenyl group may have from 1 t65 halogen atoms and/or from 1 to 3 substitUents which are selected, independently of one another, from aJlcyI, haloalkY,' alkoXY, haloal .koxyr alkyJlthio and haJ-oalkylthia, and where, the amidic phenyl .group may or 'may not b~e condensed with a saturated 5-membered' ring which may or' may not be substituted by one or more alkyl grou ps and/or may have a hetero-atom selected from 0 and S kanld -O b) at least one active ingredient of the formula IV or V, F F H H in a synergistically effective amount. U I 2. A fungicidal mixture according to claim 1, further comprising as active components c) apyrimidine derivative of 'the formula III, CH 3 III in which R is I-methyl, propyn-J.-yl or cyclopropyl, d) a phthaJlimide derivative selected from the group consisting of the compounds VIa, VIb and VII ICY 0 11 CN SCC1 2 CHC1 2 II~ SCC1 3 a VIa 28a 0 N -SCC13 I 0 and/or e) a: dinitroalilifle of the formula VIII VII VIII and/or .an arylsulfamide of the formula IX a or IXb (CH 3 2 l4SONSCCl2F IXa (CH 3 2 NSO 2 NSCl2F IXb in a synergistically effective amount. 3.A fungicidal mixture as claimed in claim 1 or 2, wherein in the fqr-mula' I the radical A is one of the foilbwing groups:. phenyl, pyridyl, dihydropyranyl, dihydrooxathitynyl, dihydrooxathiiynylOxide, dihydrooxathiiyflyldi~oxide,- f ur-yl thiazolyl, pyrazolyl or oxazo-yl, where-these groups may have 401 2 or 3 substituents which 'are selected, independently o one another, from alkyl, halogen, difluoromethy'l and trif luoromethyl.' 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: pyridin-3-yl, which may or may not be substituted in the VS 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or C methylsulfonyl; phenyl, which may or may not be substituted in the 2-position by methyl, trifluoromethyl 1 chlorine, bromine or iodine); 10 2-methyl-5,6-dihydropyran-3-yl; Cc 10 Fy 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 CI 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 25 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. A fungicidal mixture as claimed in any one of the preceding claims, which comprises 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 substituents mentioned-'in claim lor2.

6. A fungicidal mixture as claimed. in claim 5, where R 2 is a phenyl group which has one of the following substituents in the 2-position: C 3 -C 6 -alkyl, C 5 -C 6 -cycloalkenyl, C 5 -C 6 -cycloalkyloxy, cycloalkenyloxy, where these groups may be substituted by 1, 2 or 3 C 1 -C 4 -alkyl groups, phenyl which is substituted by f rom 1 to 5 halogen atoms and/or from 1 to '3 groups which. are selected, independently of one another., from Cl-C 4 -alkyl, Cl-C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halqalkoxy, C 1 -C 4 -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 Cl-C 4 -alkyl groups. 7 is A fungicidal mixture as claimed in any one of. claims 1 to 6, which comprises an amide compound of the formula Ia below: A-CO-NH (Ia) in which A R 3 (Al) N R (A2) 0 CH3 (A3) CH3 (M4) R 7 S >1>1 R S. (A6) R 9 C 1 3 N. N RS (M7) (A5) (A8) x is methylene, sulfur, sulfynyl or sulfonyl (SO 2 R 3 is methyl, difluoromethyl, trifluoromethyl, chlorine, b romine or iodine, R 4 is trifluoromethyl or chlorine, S R 5 is hydrogen or methyl, R 6 is methyl, difluoromet .hyl, trif luoromethYl or chlorine, R 7 is hydrogen, methyl or. chlorine, R 8 is me thyl', dif luoromethyl .or trif luoromlethy R 9 is hydrogen, methyl,.difluoromethyl, triflubromethyl or chlorine., R 10 is Cl-C' 4 -alkyl, -Cl-C 4 .alkoxy, Cl-C 4 -alkylthio or halogen. A fungicidal mix ture as claimed in any one of claims 1 to 6, which c'mrie aaxide compound a compound *of the formula lb below: M 1 8 LS co-NH R 4 R 1 1 in which R 4 is halogen and lge- R11 is phenyl wh~ich is substituted. by halgn 9, 'A f ungicidal mixture as claimed in claimf 1lor 2,which compnses as amide compound a compound of the formul'ae below: 0 Q Cl 0 N N lH !T O 10. A fungicidal product which is in the form of two parts, one part comprising N the amide compound of formula I according to any one of claims 1 to 9 in a solid o or liquid carrier and the other part comprising compound of the formula IV or V Saccording to claim 1 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. S 11. A fungicidal product which is in the form of two parts, one part comprising the r 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 IV or V according to claim S1 and one or more of compounds of the formula Ill, 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 at least one active ingredient of the formulae IV or V, according to claim 1, which mixture is substantially as herein described with reference to examples 24C, 28 to 31, 49 to 52, 62 to 64, 81 to 84 and 94 to

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 9, 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. The use of the fungicidal mixture as claimed in any one of claims 1 to 9 in the manufacture of a product for the control of harmful fungi.

16. A fungicidal mixture substantially as hereinbefore described with reference to the accompanying examples. 33 N 17. A fungicidal product substantially as hereinbefore described with reference o to the accompanying examples. O

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