AU2005242192B2 - Fungicide mixtures based on amide compounds and pyridine derivatives - Google Patents

Description

P001ool 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 onl amide compounds and pyridine derivatives The present specifIto discloses fungicidal mixtures for controlling harmful fungi, which mixtures comprise amide compounds of the formula

I

A,-C0-NR'

R'

in which tco o-rmtc -o A is an aryl group or an aromati or tolaoac 5- heorom 6 -mexnbered hjeterocycle which-has from1to3her aos selected fromi 0, N and

S;

where the aryl group 'or the heterocycle may or may not have 12 or 3 substituents whic h are selected, independently 'of one another, from alky'l, halogen,. CHF2,

CF

3 r akXY haloalkoxy, alkylthio, alkylsulfiyl and alky3lsulfonl.

R

1 is a hydrogen atom;.

R

2 is a phelyl or cycloalkYl gro up which may or may not have 1, 2 or 3 substituents which are selected from alkyl, alkenyl, alkJYl alkoxy, alkerlyloxy, alkyflyloXYI Cycloa]lkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxyI pheflyl and 'here the aliphatic. and cycloa13xphatic radicals may be partially or fully halogenkated and/or the cycloaliphatic radical .s .may be substituted by :from I. to 3 alkyl. groups and where the phefl'yl.group. may have from 1 to 5 halogen atoms and/or from 1 to.3 substituents which'are selected, independently of one anotherj from -alky-,. haloalkyl, alkoxy, haj.oalkoxy, alkylthio and haloalkylthio, and where the amidic phenyl group may or may not be condens.ed with- a 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 pyrimidile-derivative of the formula

III,

TI'

N4- in which R is methyl, propyn-1-yl or cyclopropyl, and/or at least one active ingredient of the f ormula IV or V,

CN

K0 0

H

F F

IV

V

I

CN

CI

and/or d) a phthalimide derivative selected from the group consisting of the compounds VIa, VIb and VII 0 0 0.

CI C N SCC1 2 CHC12 VIb q- SCC1 3 VIa 0 0 N SCC1 3 VII and/or e) a dinitroaniline of the formula VIII

F

3 C N 0N 2

CF

3

NH.

N0 2 C1

VIII

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

(CH

3 2

NSO

2 NSCCl 2

F

IXa.

(CH

3 2

NSO

2 NSCCl 2

F

IXb

CH

3 in a synergistically -effective amount.

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

A-CO-NR

1

R

2 0in which A is an aryl group or an aromatic or non-aromatic, 5- or 6-membered 1 heterocycle which has from 1 to 3 hetero atoms selected from O, N and S; where C 10 the aryl group or the heterocycle may or may not have 1, 2 or 3 substituents O which are selected, independently of one another, from alkyl, halogen, CHF 2 N" CF 3 alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl; is a hydrogen atom;

R

1 is a hydrogen atom;

R

2 is a phenyl or cycloalkyl group which may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, where the aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or the cycloaliphatic radicals may be substituted by from 1 to 3 alkyl groups and where the phenyl group may have from 1 to 5 halogen atoms and/or from 1 to 3 substituents which are selected, independently of one another, from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and where the amidic phenyl group may or may not be condensed with a saturated 5-membered ring which may or may not be substituted by one or more alkyl groups and/or may have a hetero atom selected from O and S, and b) a pyrimidine derivative of the formula III,

CH

3

N

H

in which R is methyl, propyn-1-yl or cyclopropyl, 0 In one aspect, the invention relates to a fungicidal mixture, comprising as cl active components a) an amide compound of the formula I S 5 A-CO-NR 1

R

2 in which

(N

C A is an aryl group or an aromatic or non-aromatic, 5- or 6-membered c heterocycle which has from 1 to 3 hetero atoms selected from O, N and S; where 0 10 the aryl group or the heterocycle may or may not have 1, 2 or 3 substituents cN which 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) an arylsulfamide of the formula IXa or IXb

I

(CH

3 2

NSO

2

NSCCI

2 F (CH 3 2

NSO

2

NSCCI

2

F

SIXb Xa

CH

3 Sin a synergistically effective amount.

SIn another aspect, the invention relates to a method for controlling harmful 0 5 fungi, which comprises treating the fungi, their habitat, or the materials, plants, ci 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].

SThe compound IV is.known from K. Gehmann, R. Nyfeler, (2 A.J. Leadbeater, D. Nevill and D. Sozzi, Proceedings of .the 0 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, (N Proceedings of the Brighton Crop Protection Conference, Pests and Diseases 1988, Vol. 1, p. 65 (common name: fenpiclonil).

0i US-A 2,553,770; 2,553,771; 2,553,776 describe the compounds Via (common name: captan) and VII (common name: folpet), .their 0 preparation and their activity against harmful fungi. The compound VIb (common name: captafo.) 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 VII.II simultaneously, that is either together or separately, or by applying the compounds I and the compounds II to VIII in succession than when the compounds I or II to VIII are applied on their own.

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

The term "halogen" used herein refers to fluorine, chlorine, bromine 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

I-C

12 -alky1 and in particular

C

1 i-C 6 -alkyl groups. Examples of alkyl groups are alkyl -such as in particular, methyl, ethyl, propyl, 1-methylethyl, butyl, 1l-methylPropyl, 2-methylpropyl, 1,1-di-nethylethyl, n-pentyl, I-~methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, 2, 2-dimeth ylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpeltyl, 3-xnethylpentyl, 4-methylpefltyl, 1, 2-dimethylb utyl, 1,3-dimethylbutyl, 2,3-.dimethylbutyl,.

1, l-dimethylbutyl, 2, 27dimethylbutyl, 3, 3 -dime thylbuty 1, 2-ethylbutyl, 1 -ethyl -2 -methylpropyl, n-heptyl, I-m ethylhexy1, l-ethylpentyl, 2-ethylpentyl, 1-propylbutyui octyl, decyl, dodecyl.

iialoalkyl is an. ailkyl group as defined above which is partially or fully -halogenated by one or more halogen atoms, in particular by fluorine and chlorine. Preferably, -ther-e a.re from 1 to 3 halogen atoms present, and the difluoromfethyl or the' rifluoromethyl 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, alkylsulfirlyl and alkylsulfoflYl.

The alkenyl group includes straight-chain and branched alkenyl groups. These are preferably straight-chain or br anched

C

3

-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, 1-mrethyl2'Propenyl, 2-methy1-2-propenyl, 27pentenyl, .3 -pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyN2"butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, '2-rmethyl .3-butenyl, 3-methy1-3-butenyl, 'i.-iehl2- -enl 1, 2-dimetthyl727propenyl, 1-ethyl-2-propenyl, 2,-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexerlyl, 1..methyl-2-.PentenYl, 2.-methyl-2-pentehll 3-methyl-2-peltenyl, 4-methylN>pentenyl1, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-ehl3pne~l 4-rnethyl-3-peltelyl, lrnethyl-~4-pefltenyl, 2-~methyl-4-peltenl, 3-methyl-4-peltel, 4 -iethyl-4-pentenyl, l.,1-direthyl1-butenyl, l,1-dimethyl-3-butenll 1, 2-dimethyl-2-butefl, l,2-dcirethy-3-butenyl, 2, 2-direthyl-3-butelyl, 2 -dimnethyl- 2-b~utelyl, 2 -ethyl- 2-butel 2-ethyl.-3-butenyl, 1,2-trimethyl-2-properiyl, 1 -~ethyl- 1-methyl-2 -propelyl and 1-ethyl-2-methyl-2-propel, In particular 2-,propenyl, 2-butenyl, 3-methyl-2-buteflYl and 3-mrethyl-2-pefltelyl.- The alkenyl group may-be partially or fully halogenlated by one or more halogen atoms, in particular by fluorine or chlorine. The CI alkenyl group preferably has from 1 to 3 halogen atoms.

The alkynyl group -includes straight-chain and branched alkynyl1 groups. These are preferably straight-chain and br .anched c 3

-C

1 2 -alkynyl groups and in particular

C

3

-C

6 -alkynyl groups.

Examples of alkynyl groups are 2-propynyl,.' 2-butynyl, 3-butyriyl, methyl-2-propynyl, 2-pentynyl, 3-pentyflyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-.methyl-2-butynyl, 1, 1-dimethyl-2-pro ylyli, I-ethyl-2-propynyl, 2-hexynyl, 3 -hexynyl, 4'-hexynyl, 5--hexynyl, i-methyl-2-peltyfll 1-mnethyl-3-pentynyl, 1-rnethyl-4-pentynly, 2-methyl-3-pefltynyl, 2-methyl-4-pentylyl, 3-methyl-4-peltyflyl, .4-methyl-2-pefltynyl, 1,2-dimethyl-2-butynyl, 1, 1-di-methyl-3-butynyl, 1, 2-dimethy-3-b2tyflyl, 2, 2-dimnethy1-3-butynyl.,- 1 -ethyl 2 -butynyl, 1 -ethyl -3 -butynyl, 2-ethyl-3-butynyl and 1 -ethyl- 1-methy1-2 propynyl.

The above statements for the alkenyl group and its halogen substit-uents and for the alkynyl grtoup 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, cycloperityl or cyclohexyl.. If the cycloalkyl group is substituted, it preferably has f rom 1 to 3 c 1

-C

4 -alkyl radicals as substituents.

is preferably a C 4

-C

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

8 8 C A cycloalkoxy group is preferably a C 5

-C

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

The cycloalkenyloxy group is preferably a C 5

-C

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

O A-tyl is preferably phenyl.

If A is a phenyl group, this may have one, two .or three of the abovementioned substituents in any position. These substituents are preferably selected, independently of one another, from alkyl, difluoromethyl, trifluoromethyl and halogen, in particular chlorine, bromine and iodine. Particularly preferably, the phenyl group has a substituent in the 2-position.

If A is a 5-membered heterocycle, it is in particular a furyl, thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl, triazolyl or thiadiazolyl radical or the corresponding dihydro or tetrahydro derivatives thereof. Preference is given to a thiazolyl or pyrazolyl radical.

If A is a 6-membered heterocycle, it is in particular a pyridyl radical or a radical of the formula: in which one of the radicals X and Y is 0,-S Or NR 23 where R 23 is H or alkyl, and the other of the radicals and Y is CH 2 S, SO,

SO

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

The 6-membered. aromatic heterocycle is particularly preferably a pyridyl radical, in particular a 3-pyridyl radical, or a radical of the formula 0 CH 3 (A3) a\ Oh in which X is CH 2 S, SO or S02- C The abovementioned heterocyclic radicals may or may not have 1, or 3 of the abovementioned substituents, ese substituents 8 are preferably selected, independently of one another from alkyl, halogen, difluoromethyl or trifluoromethyl, A is particularly preferably a radical of the formulae: R3 R4 (Al) (A2) SRR8 (AS) (A7) CH 3 in which

R

3

R

4

R

6

R

7 R and R 9 independently of one another are hydrogen, alkyi, in particular methyl, halogen, in particular chlorine,

CHF

2 or CF3.

The radical

R

l in the formula I is preferably a hydrogen atom.

The radical

R

2 in the formula I is preferably a phenyl radical.

R

2 preferably has at least one substituent which is particularly preferably in the 2-position. The subtituent (or the substituents) is (are) preferably selected from the group consisting of alkyl, cyclo.alkyl, cycloalkenyl, halogen or phenyl.

The substituents of the radical

R

2 may in turn be substituted again. The aliphatic or cycloaliphatic substituents may be partially or fully halogenated, in particular fluorinated or r chlorinated. They preferably have 1, 2 or 3 fluorineor chlorine c atoms. If the substituent of the radical

R

2 is a phenyl group, this phenyl group may preferably be substituted by irom 1 to 3 halogen atoms, in particular chlorine atoms, and/or by a radical which is preferably selected from alkyl and alkoxy. Particularly preferably, the phenyl group. is substituted with a halogen atom r0 in the p-position, i e. the particularly preferred substituent of ithe pdic 2 is a phalogen-substituted phenyl radical. The radical R2 may also be condensed with a saturated 5-membered ring, S where this ring for its part may have from 1 to 3 alkyl substituents-

R

2 is in this case, for example, indanyl, thiaindanyl and oxaindanyl- Preference is given to indanyl and 2-oxaindanyl which are attached to the nitrogen atom in particular via the 4-position- According to a preferred embodiment, the composition according to the invention comprises as amide compound a compound of the formula I in which A is as defined below: phenyl, pyridyl, dihydropyranyl, dihydrooxathiiynyl, dihydrooxathiiynyloxide, dihydrooxathiiynyldioxide, furyl, thiazolyl, pyrazolyl or. oxazolyl, where these groups may have i, 2 or 3 substituent which are selected, independently of one another, from-alkyl, halogen, difluoromethyl and trifluoromethyl- -According to a further preferred embodiment, A is one of the following groups: pyridin-3-yl, which may or may not. be substituted in the 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl 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-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 2- S 5 and/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; l-methylpyrazol-4-yl, which may or may not be substituted in the 3- and/or 5-position by methyl, chlorine, difluoromethyl or trifluoromethyl; or which may or may not be substituted in the 2- and/or 4-position by methyl or chlorine.

According to a further preferred embodiment, the compositions according to the invention comprise as amide compound a compound of the formula I in which R 2 is a phenyl group which may or may not be substituted by 1, 2 or 3 of the abovementioned substituents.

According to a further preferred embodiment, the compositions according to the invention comprise as amide compound a compound of the formula I in which R 2 is a phenyl group which has one of the following substituents in the 2-position:

C

3

-C

6 -alkyl, C 5

-C

6 -cycloalkenyl, Cs-C 6 -cycloalkyloxy, cycloalkenyloxy, where these groups may be substituted by 1, 2 or 3 Ci-C 4 -alkyl groups, phenyl, which is substituted by from 1 to 5 halogen atoms and/or from 1 to 3 groups which are selected, independently of one another, from CL-C 4 -alkyl, Ci-C 4 -haloalkyl, CI-C 4 -alkoxy,

C

1

-C

4 -haloalkoxy, C 1

-C

4 -alkylthio and C 1

-C

4 -haloalkylthio, indanyl or oxaindanyl which may or may not be substituted by 1, 2 or 3 C 1

-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 la,

U

A-CO-NH (Ia) in which A is (Al)

R

5

R

5

CH

3

(AM)

N v (A2)

R

7 (A5) 0CH3 (A3)

S

(A6)

R

R

9 C H 3 1- N

RO

(A7) Nl (A8) *X is

R

3 is or 4 0 R4 is

R

5 is

R

6 is

R

7 is RB is methylene, sulfur, sulfynyl or sulfoflyl (SO 2 methyl,. difluoromethyl, trifluoromfethYl, chlorine, bromine iodine, trifluoromethyl or chlorine, hydrogen or methyl, methyl, difluoromethyl, trifluoromfethyl or chlorine, hydrogen, methyl or Chlorine, methyl, difluorornethyl or trifluoromethyl, R 9 is hydrogen, mlethyl, difluoromethyl, trifurmehlo chlorine, loy jCalkItiorhogn

R

1 0 is

C

1

C

4 -alkyl, c 1

.C

4 rhlgn Also disclosed is a fungici~dal mixture comprisinlg as amide compound a compound of the formula lb N R 4

R

11 (1b) in which

R

4 is 4ialog'ef and

R

1 1 is phenyl whch is ubstituted by halogen- Aiecomnpounds of the formula ahic myentsed in theA fungicidal mixtures di iclOrpraed hereinmnin nEP- 545 099g and 589 301 which are icroae eeni hi entirety by reference.

The prprto o h d opunds of the f .ormula I is known, for example, from

EP-A-

5 4 5 099 or 589 301 orc0 b are u by similar Processes.

reerrd ubtitens 21 and

R

2 2 are hydrogen# F, methyl, ethyl, methoXY., thiomethyl and N-methylaminb Rafd 4 tghe may also form a grouping =0.

Pefered ungcide ofthe dicarboximide type are the Iha to Id: ethyl (RS) 3- 3 5 dich1orophY :Ta dioOO)C azolidine -ScarbOXYlate C1 0 CH 3

CO

2 CHZCH3 C11 14 TI.b: 3 -(3,5-dichlorophenylVN-isopropyl12,4dioxoimidazolidine- U 1 -carboxamide C1 0 II.b CIO N CONHCH(CH 3 2 or CIII.C: N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1, 2 dicarboximide CI0C CH 3 N

DC

or II.d:(R)-3-3,5-ihlrpey -5-tenl--mty-13oxazolidine- 2 4-dione -C1 0 H *N II.d.

ci 0 These compounds are commercially available as. fungicidally active ingredients and are described in the literature as follows: *II.a (common name: chiozolinate): CAS RN [84332-86-5], DE-A 29 06 574; II.b (common name: iprodione)p:'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:. vinclozoline): CAS*RN [50471-44-8], DE-A 22 07 576].

To unfold the synergistic activity, even a small amount of the amidecompound of the formula I is sufficient. Preference is to employing amide compound and active ingrediiEnt of the formula II and/or III t *o -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 dcompounds III to IX. In uch mixtures, the mixing ratio of the compounds II and III to IX with each other is usually in the range of from 50:1 to 1:50, preferably from 10:1 to 1:10.

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

trifloroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylsulfonic ranched arky dis lfonic acids (aromatic radicals, such as phenyl acids or aryldisulfonc acds groups), and naphthyl, which carry one or two sulfo groups), alkylphosphonic acids (phosphonic acids having straight-chain orbranched alkyl radicals of to 20 carbon atoms), arylphosphonic ranched aryl diphosph c l c acids (aromatic radicals, such as acids or aryldiphosphonic ac o phosphonic acid phenyl and naphthyl, which carry one or two phosphnaic acid radicals), it being possible for the alkyl or aryl radicals to radicals), it being possible for toueloiacid, salicylic carry further substituents, eg ptolueneulfonic acid, salicylic acid, p-aminosalicylic acid, henoxbenzoic 2-acetoxybenzoic acid, etc.

uitable metal ions are, in particular, the ionsof the elements Suitable metal ions are, a n p a r t l c u articular chromium, of.the first to eighth sub-group in particular chromium, t tcopper, zinc and furthermore of manganese, iron, cobalt, nickel, copper, nc and furmaneum, 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 varius valencies 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 orb growth-regulating active ingredients 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 8or separately, exhibit outstanding activity against a wide range O of phytopathogenic fungi, in particular from the classes of the SAscomycetes, Basidiomycete, Phycomycetes and Deuterpmycetes.

Some of them act systemically and can therefore be enployed as h foliar- and soil-acting fungicides.

They are especially important for controlling a large number of They are especially mp latssuch as cotton, vegetable fungi in a variety of crop plants, such as cotton, Vegetable c 10 species (eg. cucumbers, beans, tomatoes, potatoes and cucurbits), Sbarley, grass, oats bananas, coffee, maize, fruit species, rice, S rye oyagrapevine wheat, ornamentals, sugar cane, and a Svariety of seeds.

C-I 15

C

Theyare particularlY suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, rodosphaera 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, ycspaerela species in bananas and Fusarium and verticillium species.

The mixtures described herein may Botrytis spci particularlyproferably be employed for controlling Botrytis species particularlypr-feablband also .in ornamentals.

in crops of grapevines and vegetables and alsoin onmentals The compounds I and II and/or III to ix can be applied simultaneously, either together or separtely, or in succession, the sequence, in the case of separate application, generally not having any e.ffect 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.

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

Correspondingly, in the case of the compounds II and/or III to IX, the application rates are from 0.01 to 10 kg/ha, preferably 0.05 to .5 kg/ha, .in particular .0.0 5 to 2.0 kg/ha.

For seed treatment, the application rates of the mixture are Sgenerally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, in particular 0.01 to 50 g/kg.

SIf phytopathogenic harmful fungi are to be controlled, the 0 separate or joint application of the compounds I and II and/or III to IX or of the mixtures of the compounds I and II and/or III to IX is effected by spraying or dusting the seeds, the plants,or the soils before or after sowing of the plants, or before or after plant emergence.

The fungicidal synergistic mixtures described herein and according to the invention, or the compounds I and II and/or III to IX, can be formulated for example in the form of ready-to-spray solutions, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspensions dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting or granules, and applied by spraying, atomizing, dusting, broadcasting or watering. The use form depends on the intended purpose; in any case it should ensure as fine and uniform as possible a distribution of the mixtures described herein.

eg by The formulations are prepared in a known manner, eg by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants, it being possible also to use other organic solvents as auxiliary solvents if water is used as the diluent. Suitable auxiliaries for this purpose are essentially: solvents such as aromatics (eg. xylene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg mineral oil fractions), alcohols (eg methanol, butanol), ketones (eg cyclohexanone), amines (eg ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals '(eg kaolins, clays, talc, chalk) and ground synthetic minerals (eg finely divided silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.

18 alkaline earth suitable surfactants are the alkali metal sul al kli e Smetal salts and ammonium salts of aromatic sublfnia s e Sligno-, phenol-, naphthalene- and alkylarylsulfonates, alkyl, acid, and of fatty acids, alkyl- and salts of sulfated i lauryl ether and fatty alcohol sul fates,a alto l hexa-, hepta- and octadecanols, or of fatty alcohol glycoits dervatves Sethers, condensates of sulfonatednaphthalenete te with formaldehyde, condensates of aphthalene or ef the Snaphthalenesulfonic acids with phenol and formaldehyde, 1 polyoxyethylene octylphenol ether, ethoxylated isooctyl- octylor nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcoholS, isotridecyl alcohol, fatty alcohol/ethylene oxide codenates., ethoxylated Scastor oil, poyoxyethylene alkyl ethers or polyoxyrolene lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulo se owders, materials for broadcasting and dusts can be prepared by Sls~for b th n ounds I r and/or III.to mixing or jointly grinding the compounds II and/or III to IX o IX, or the mixture of the compounds I and II and/or III toIX, with a solid carrier.

Granules (eg- coated granules, impregnated granules or Granulesusuall prepared by binding the active homogeneous granules) are t o a soli carer ingredient, or active ingredients, to a solid carrier.

Fillers o lid carriers are, for example, mineral earths, such solid carrse. orr to 95% by weight, as silica gel, silicas, -9 a e ai c Skaolin limestone, lime, chalk, bole, oess, clay, dolomite, diatoaceous earth, calcium sulfate magnesium sulfate, magnesium •and fertilzers, Suc as oxide, ground synthetic materialsadients are et l oe d a r affonium sulfate ammonium h hatetrate re the 'mixtures, or the and products bf vegetable origini such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or. other solid carriers- The formulations generally comprise from to 95% by weight, corresponding formulations, a s ed sis eas, preferabl 05 to 90% by weight, f one f the compounds I a and/or III to IX or of the mixture Of the compounds I and

II

and/or III to IX. The active ingredients are employed in a purity of from 90%.to 100%, preferably 95% to 100% (according to-MIR or HPLC spectra.) The compounds I and II and/or Iii to IX, the.mxtures, or the corresponding formulations, are applied by treating the harmful fungi, their habitat, or the plants, seeds, soils, areas, materials or spaces to be kept free rom them with a fungicidally effective amount of the mixture, or of the compounds I and II and/or II to IX in the case of separate application.

S Application can be effected before or after infec by the harmful fungi.

Examples of such preparations comprising the active ingredients are: S A so lution of 90 parts by weight of the active ingredients and 10 parts by weight of N-methylpyrrolidone; this pa for use in the form of microdrops; solution is suitau' solution is su. the active ingredients, II- A mixture of 20 parts by weight of the acveht of the parts by weight of xylene i parts by weight of the adduct of 8 to 10 mol of ethylene oxide to 1 ol of ium acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbnenesulfonate' 5 parts by weight of the addct 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.

.rr An aqueous disperson iht of cyclohexanone, 30 parts ingredients, 40 parts by weight of cyclohexanone 30 parts by weight of isobutanol, 20 parts by weight of the adduct and 1 mol of castor oil; of 40 mol of ethylene IV. An aqueous dispersion of 20 parts by weight of the active ingredients, 25 parts by weight of cyclohexaol, pt by weight of a mineral oil fraction of boiling point 210 to 2800C, and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil; 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-sulfonatei 10 parts by weight of the. sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel; a spray mixture is obtained by finely distributing the mixture in water; __ht of the active

VI.

An intimate mixture of 3 parts by wei ingredients and 97 parts by weight of finely divided kaolin this dus comprises 3% by weiht f active ingredient; VII- An intimate mixture of 30 parts by weight of the active ingredients, 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel; this Sformulation imparts good adhesion to the active ingredient; formulation imparts g VIII. A stable aqueous dispersion of 40 parts by weight of the active ingredients, 10 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water; this dispersion may be diluted further; IX. A stable oily dispersion of 20 parts by weight of the active ingredients,- 2 parts by weight of the calcium salt of dodecylbenzenesulfonate 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate and 88 parts by weight of a paraffinic mineral oil.

Use Example The synergistic activity of the mixtures described herein .can be demonstrated by the following experiments: The active ingredients, separately or together, are formulated as a 10% emulsion in a mixture of 63% by weight 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 percent. These percentages are converted into efficacies. The 3 0 in percent. e uin g A b b o t s fo rm u la efficacy is calculated as follows using Abbot's formula: S= (1 a)-100/ a corresponds to the fungal infection of the treated plants in and S corresponds to the fungal infectionof the untreated 40 (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.

o o aU 5 c l In 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" 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 chamber with high atmospheric humidity at 22-240C. 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 O

NH

I.1 N Cl

F

0- NH 1.2 I 1.2 m 22 The results are shown in Tables 1 and 2 below.

Table 1 Ex.

2C Active I Concentration ingredient untreated* Compound I.1 the spray liquor in ppm.

0 infection) .31 16 Efficacy in of the untreated control 0 78 67 67 44 44 0 COrnpound .2 31 3C I I 8 4C- ICompound Vla 31 16 C Compound VI 31 6C jCmpound iXa 731 0 8 0 0 Table 2 Ex.- 7 8 9 r12 8cntn ppm 1.1 81 ppm I-1 31 ppm1.

31 ppm VIa 31 ppm 1.2 16 ppm VIa 31 ppm1.

31' ppm.VII 8 PPM'.

observed efficacy calculated efficacy*) 97 78 30 1 100 -67 .44 90 78 39 11 8 ppflVII I Mixtures the inver (content 31 ppm I.

31 ppm -VI 16 ppm I.

16 ppm 16 ppm VI: according to ition n nnm observed efficacy calculated efficacy*) l flt." I 2 93 67 2 90 44

U

8 ppm 1.2 8 ppm VTT 1 31 ppm I.1 95 78 31 ppm IXa 16 ppm I.1 90 67 16 ppm IXa 31 ppm 1.2 100 67 31 ppm IXa 16 ppm 1.2 99 -44 16 ppm IXa 8 ppm 1.2 90 44 +p 8 ppm IXA" 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 2 Activity against Botryis cinerea on bell peppers Disks of green bell peppers were 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. 2 hours after the spray coating had dried on, the fruit disks were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 10 6 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.

Table 3 I concentratiOn of Ex.

21C 22C 23C ingredient untreated compound. 1.1 Compound 1.2 in the spray liquor in ppm 0 (100% infection) 31 Efficacy in of the untreated control *0 C115 31 31 0 24C lCompound

IV

16 U 31 0 i6 C i7 C Compound VIa Compound

VII

Compound

VIII

31 0 16_ Table 4 lEx. Imixtures acording to the 2T8 29 32 33 34 31 ppm, IV1 31 ppm 1.2 16 ppm I.1 16 ppm 1.2 31 +m 31 p pm IV 16 ppm 1.2 31 ppm.IVa 31 ppm 1.2 31 ppm VII 31 ppm. I.1 31,ppm

VIII

16 ppm 1.2 observed efficacy calculated efficacy*) 0 20 0 70 20 0 20 0 16 ppm VIII calculated using Colby's formula 03 The test results show that for all mixing ratios the observed efficacy is C higher than the efficacy which had been calculated beforehand using Colby's formula.

USE EXAMPLE 3 CONTROL OF GREY MOULD (BOTRYTIS CINEREA) ON 0 FRUIT SLICES OF GREEN PEPPER The following compounds and compositions containing them were tested: 1. Amides 1.1, 1.2 O

O

/N

N

H

H

N Cl N Cl 1.1 1.2 2. Pyrimidifle derivatives Illa, Ilic CH 3

N

IIla CH 3 IIIc CH 3 3. Pyrrole derivate

IV

F

0-

F

0

CN

4. Dinitroaflilifle

VIII

VIII

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

In 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 Swas attacked was set at 100.

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

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

Colby formula: E x y (x e y: 100) E= Expected degree of action, expressed in of the untreated control, when active ingedients A and B are applied together, the concentration of A being and the concentration of B being [b] x degree of action of ingredient A, expressed in of the untreated control, when concentration of the active ingredient A is applied y= degree of action of ingredient B, expressed in of the untreated control, when concentration of the active ingredient B is applied As a general rule the comparison of the expected degree of action according to the 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: Ex 36 37 38 39 41 42 Compound control (untreated) Appln. Rate [ppm] degree of control (92 attack) 0 12,5 6,3 24 3.1 2 12.5 67 1.2 6.3 57 3.1 2 Ill.a 31 63 III.c ,i1 .o 1 i I

I

I

1 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 ite o o the Degree of action calculated Ex invention Degree of action observed (Colby) Application rate [ppm] 1.1 III.a 43 3.1 31 ppm 57 36 ratio 1 1.1 Ill.a 44 6.3 31 ppm 89 51 ratio 1 1.1 Ill.c 3.1 31 ppm 95 36 ratio 1 1.1 lll.c 46 6.3 63 ppm 95 51 ratio 1

Ex Mixture according to the Invention Application rate [ppm] I I Degree of action observed Degree of action calculated (Colby) 1.2 IIl.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 3 6.3 3.1 ppm 95 62 63 ratio 2 1 1.2 IV 64 6.3 1.6 ppm 88 72 ratio 4: 1 1.2 VIII 6.3 3.1 ppm 77 58 ratio 2: 1 1.2 VIII 66 12.5 6.3 ppm 88 68 ratio 2: 1 1.2 VIII 67 12.5 3.1 ppm 95 68 ratio 4 1 USE EXAMPLE 4 PROTECTIVE CONTROL OF OF GREEN PEPPER BOTRYTIS CINEREA ON LEAVES The compounds tested and compositions containing them were as per Use Example 3.

Young seedlings of green pepper of the 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 106 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 Degree of action calculated Ex invention Degree of action observed (Colby) Application rate [ppm] 1.1 lll.a 3.1 31 ppm 91 71 ratio 1:10 1.1 III.a 76 6.3 63 ppm 100 71 ratio 1 L i lI.c 77 3.1 31 ppm 100 13 ratio 1 1.1 Ill.c 78 6.3+63 ppm 100 42 ratio 1 .a II.c 79 6.3 31 ppm 100 13 ratio 1 1.1 II.c42 12.5 63 ppm 100 42 ratio 1 1.1+ IV 3.1 1.6 ppm 85 42 81 ratio 2 1 1.1 IV 82 6.3 3.1 ppm 100 71 ratio 2 1 Mixture according to the na~nenton egre ofacton bseved Degree of action calculated Ex Ineon Degre ofctlon observed(oly Ex Application rate [ppm] Cly E x 1.1

IV

84 12531pm ratio 4: 1 1.1 +IVI 32.1 1 ppm 7 ratio 4: 1 11+ Vill 6.3 +1.6 ppm 104 ratio 4 1 1.1 VIII 874 126.5+31.6 ppm 104 ratio 4: 1 I.2 illa 88 32.1 3.1 ppm 9 ratio 1 91 3.1 31 ppm 107 ratio 1 1.2 II.c 892 6.3 63 ppm 108 ratio 1 1.2 III-c 906.3 31 PPM 100 8 ratio 1: 1.2 +11IV 94 3.1 +1 ppm 100 ratio 2 F ~1.2 IV1- 92 6.3 16 ppm 91 66 ratio 4 1.2 IIIc 96 631+1 ppm 100 ratio 2 1.2 IVI 97 6.3 +31.6ppm 9100 ratio 2: 1

U

Mixture according to the invention Application rate [ppm] Degree of action observed Degree of action calculated (Colby) 9 -i 1.2 VIII 6.3 1.6 ppm ratio 4: 1

I

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 (12)

1. A fungicidal 'mixture, conpriSi ;ng as~ active components a) an amnide compound of -the formfula I.- A.;--CO-NR1R 2 I in which A is an aryl. group or an aromatic or non-aromatic,

5- or

6-mezbered heterocycle which has from 1 to 3 hetero atoms selected from 0, N and S; where the aryl gropup or the heterocycle may or may not have 1, 2 or 3 SUbstituents which are selected, independently of one another, from alkyl, halogen, cHm' 2 CF 3 alkoxy, haloalkoxy, alkylthlo,- 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 selec ted, independently of one another, from alkyl, alkenyl, alkyflyl,' alkoxy, alkyn yloxy.. cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkeflyloxy, phenyl1 and halogen, where the: al~iphatic and cycloaliphatic radicals may be partially-Or fully halogeflated and/or the cycloaliphatic radicals may be substituted .by from 1 to 3 alkyl groups -where the phenyl grouip may have -from 1 t6-5 halogen atoms and/or from 1 to 3 substituelts which are selected, independently of one another, from alkyl,.,. haloalkyl.- alkoxy, haloal .koxy, alkyJlthio and halcfalkylthio, and where. theii aiidic 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 grou1p*5 and/or may have a hetero atom selected f rom 0 and S anid b) .an arylsulfamfide of the formula IX a or IXb (CH 3 2 NSOZNSccl2F (CH 3 2 NS0 2 NSC12F b IXa CH 3 in a synergistically effective amount. U 2. A fungicidal mixture according to claim 1, further comprising as active components c) 'a pyrimidine derivative of *the formula III, CH 3 III in which R is methyl, propyn-l-.Yl or cyclopropyl., and/or at least one active ingredient of the formula IV or V, CN 0 I H F \F CN C1 and/or e) a phthalimide derivative selected from the group consisting of the compounds Vla, Vib and VII II N SCC1 3 N-SCC1 2 CHC1 2 o V Ib 0 VIa 0 -SCC13 I 0 and/or dinitroa line of the formula VIII F 3 G :I NO 2 C1 NH VII VIII N0 2 C1 in a synergistically effective amount. 3. A fungicidal mixture as claimed in claim Ilor 2,wherein in the formula I the radical A is one of the following groups:. phenyl, pyridyl, dihydropyranll dihydrooxathiiyrlyl,. dihydrooxathiiynyloxide, dihydrooxathiiyflyldi .oxide, f urya, thiazolyl, pyrazolyl or oxazolyl, where-these groups may have 1, 2 or 3 sbbstituentS which are selected, independently of one another, from alkyl, halogen, difluoromethyl1 and trif luoromethyl.' 4. A f urgicidal mixture as claimed in claim 1or 2, whereinlin the formula I the radical A is one of the following groups: n pyridin-3-yl, which may or may not be substituted in the O 2-position by halogen, methyl, difluoromethyl, C trifluoromethyl, methoxy, methylthio, methylsulfinyl or U methylsulfonyl; SS phenyl, which may or may not be substituted in the 2-position O by methyl, trifluoromethyl* chlorine, bromine or iodine; 2-methyl-5, 6-dihydropyran-3-yl; (Ni 2-methyl-5,6-dihydro-1,4-oxathiiyn-3-yl or the 4-oxide or 4,4-dioxide thereof; C 15 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; l-methylpyrazol-4-yli 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 1 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, Cs-Cs-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 from 1 to 5 halogen atoms and/or from 1 to '3 groups which are selected, independently of one another, from CI-C 4 -alky1, Cl-C 4 -haloalkyl, C 1 -C 4 -alkoxy,.C 1 -C 4 -haloalkoxy, Cl-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 Q. 1 -C 4 alkyl groups.

7. A fungicidal mixture as claimed in any one of claims 1 to 6, which comprises an amnide compound of the formula Ia below: A-CO-NH (Ia) in which OCR3 (Al) R 5 H (M4) N R 4 (A2) R7 S N R 6 (A5) 0 CH3 (A3) R7- S (A 6) R 4 R9 7-- C H 3- N N R8 (A7) R 5 0. (AB) X is methylene, sulfur, sulfynyl or sulfonyl (302), R 3 is methyl, difluoromethyl, trifluoromethyl, chlorine, bromine or iodine, R 4 is trifluoromethyl or chlorine, R 5 is hydrogen o~r methyl, R 6 is methyl, difluoromethYl, tr Ifluoromethyl or chlorine, R 7 is hydrogen, rnethyJ. or chlorine, U Re is methyl, dif luor ethyl -or trif luoromethy R 9 is hydrogen, methyl, :difluorolnethyl, triflubromethyl or chlorine, RIO is Cl-C 4 -alkyl, .C 1 -C 4 -alkoxy, C 1 -C 4 alkylthio or halogen. 8, A fungicidal mixture as claimed in any one of claims I. to 6 which comprises as amnide compound a compound of the formula Tb below: CO-NH (Ib) N R 4 R 11 iLn which R 4 is halogen and R 1 1 is pheriyL which is substituted by halogren.

9. A fungicidal mixture as claimed in claim 1 or 2, which comprises as amide compound a compound of the formulae below: 00 N IH. N .N HlN C N Cl 400 N IH N ci A fungicidal product which is in the form of two parts, one part comprising C 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 according to claim 1 in a solid or liquid carrier, the fungicidal product being 0 packaged so that in use the two parts are mixed to produce the synergistic fungicidal mixture according to any one of claims 1 to 9.

11. A fungicidal product which is in the form of two parts, one part comprising Sthe 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 C according to claim 1 and one or more of compounds of the formula III, 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.

17. A fungicidal product substantially as hereinbefore described with reference E to the accompanying examples. O

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