GB2114002A - Improvements in or relating to fungicides - Google Patents

Abstract

The present invention relates to the use of a compound a), an oomycetes controlling fungicide having the structure element of formula I <IMAGE> in which X is CH or N, in association with a compound b), selected from CYMOXANIL and Phosetyl-Al in combatting or preventing fungal diseases, and fungicidal composition comprising such compounds.

Description

SPECIFICATION Improvements in or relating to fungicides The present invention relates to fungicides, more particularly to oomycetes controlling fungicides.

Although a wide variety of fungicides including various oomycetes controlling fungicides are known, the need exists for still more effective fungicides.

It has been found that the use of a) an oomycetes controlling fungicide having the structure element of formula I

in which X is CH or N, in association with b) a compound of formula II

hereinafter referred to by the common name CYMOXANIL or of formula III

hereinafter referred to by the common name Phosetyl-Al is particularly effective in combatting or preventing fungal diseases.

Aryl, as used in formula I, is intended to embrace any aromatic radical, unsubstituted or substituted, e.g. phenyl unsubstituted or substituted.

Acyl, as used in formula I, is intended to embrace any organic radical tied by a CO-group to the Natom.

An example of a group of oomycetes controlling fungicides having the structure element of formula I (hereinafter designated compounds of formula I) suitable for use in the invention are those of formula la

wherein P1, R2 and R3, independently, are H, C1~4alkyl, C,~4-alkoxy, C,~4alkylthio or halogen selected from F, CI and Br, A is selected from a group -CH(R4)-R5 or a group-N(R6)-COOR7, in which R4 is H or C~4alkyl, R5 is COZR8, CO-N(R9)OR10, CN, CHO,

C-C-P14, allene; or is 2,2-dihalo-1 -cyclopropyl unsubstituted or substituted by C~4-alkyl; or is phenyl unsubstituted or substituted, R6 is C1-3alkyl, R7 is C1-6alkyl, C3-6alkenyl or C3-6alkinyl, whereby R6 and R7 may be linked together to form CH2-CH 3; and wherein Z and Z' are 0 or S R8 is C1-6alkyl, C3~6alkenyl, or C3-6alkinyl, and whereby ZR8 may be linked with R4 to form the bridge ZCH(R15)-CH2 in which Z is as defined above and R15 is H or CH3; R9, R'9 and R"9 are H or C1-4alkyl, R10, R'10 and R"o are C1-4alkyl, whereby Rg may be linked with R,O, resp. R'g with R'1O, resp.R"9 with R"o and signify alkylene, to form a 5- or 6-membered heterocyclic ring, R1, R12, R13, independently, are H, C1-4-alkyl, or halogen selected from F, Cl or Br, R,4 is H, C1-4alkyl or halogen selected from CI, Br or I, and Y is H; a hydrocarbon selected from C1-6alkyl, C2-6alkenyl and C2-6alkinyl unsubstituted or substituted by halogen, selected from F, CI or Br, or by CN; C25epoxyalkylene; C3-6cycloalkyl; a 5-membered heterocyclic ring comprising 1 to 3 heteroatoms selected from 0, S and N, which is unsubstituted or substituted by C1-4alkyl or halogen selected from F, CI or Br; (A1)n-Az;(A1)n-Y1-NR9aR10a; (A1)nZ1H and esters or ethers thereof; benzyl u nsubstituted or substituted, in which Al is CH3 or CH(CH3) n is O or 1, Az is a 1-azolyl comprising 1 to 3 nitrogen atoms, Y, is a covalent bond or NH, R9a is H or C1-4alkyl, R10a is C1-4alkyl, Z1 is O or S.

Where any of P1, R2, R3 and R4 is or comprises C1-4alkyl, this is preferably CH3.

Where R5 is 2,2-dihalo-1-cyclopropyl both halogens comprised therein signify F, CI or Br, particularly Cl or Br, especially CI; both halogens are preferably identical. Any C1-4alkyl substituent of 2,2-dihalo-1 -cyclopropyl signifies preferably CH3.

Where R5 is substituted phenyl, it is conveniently mono- or disubstituted. Suitable substituents of phenyl are e.g. C1-4alkyl (CH3), C1-4alkoxy (OCH3) and halogen (F, Cl, Br).

R6 is preferably CH3.

Where any of R7 and R8 is C1-6alkyl, it is conveniently C1-3alkyl, preferably CH3.

Where any of R9, R'g, R"g, R,O, R'10 and R"o is C1-4alkyl, it is e.g. CH3.

Where R9 and R,O, resp. R'g and R'10 resp. R"9 and R"10 are linked together and represent alkylene, such alkylene is conveniently unbranched.

Where any of R11, R,2 and R,3 is C1-4alkyl, this is preferably CH3.

Where any of R11, R12 and R,3 is halogen, this is preferably CI or Br, particularly CI.

Where R,4 is C1-4alkyl, this may be straight or branched and signifies for example CH3.

Where Y is hydrocarbon substituted by halogen, such halogen is conveniently Cl or Br.

Where Y is substituted hydrocarbon, the hydrocarbon signifies preferably C1-6alkyl, particularly C1-3alkyl.

Where Y is C1-6alkyl, unsubstituted, it is preferably C3-5-alkyl, particularly unbranched C3~5alkyl or 2-methyl-i -butyl.

Where Y is C3-6alkenyl, it is preferably CH=CH-CH3.

Where Y is C3~6cycloalkyl, it is preferably cyclopropyl or cyclobutyl.

Where Y is a 5-membered heterocycle, this may be aromatic oder hydrogenated; examples of suitable heterocyclic radicals are furyl (e.g. 2-furyl), tetrahydrofuryl, thienyl, isoxazyl and thiadiazolyl.

Suitable substituents of such heterocyclic groups are particularly CI, Br, CH3. Any substituted heterocycle is particularly mono-substituted.

Suitable significances of Az are e.g. pyrazol-1-yl, imidazol-l -yI and 1 H-1,2,4-triazol-1-yl.

Where Rga is C1-4alkyl, this is especially CH3 or C2H5.

R10a signifies preferably CH3.

Suitable examples of compounds of formula la, wherein Y is esterified (A)nZ,H are esters with an alkane carboxylic acids (such as CH3COOH), an alkane sulfonic acid (e.g. CH3SO2OH), a dialkylsulfamic acid (e.g. (CH3)2NSO2OH), a functional derivative of a carbonic acid etc.

Suitable examples of compounds of formula la, wherein Y is etherified (A1)nZ1H are e.g.

compounds of formula la, wherein Y is (A,)nZ,W, in which A1, n and Z, are as defined above and W is a group selected from C1-8alkyl (particularly CH3, C2H5), C3-6-alkenyl (particularly CH2-CH=CH2), C3-6alkinyl (particularly CH2C#CH), C1-4alkoxy-C1-3alkyl (particularly CH2OCH3), C1-4alkylthio-C1-3alkyl (particularly CH2SCH3) unsubstituted or substituted by halogen (F, CI, Br) or a pyranyl group.

Preferred compounds of formula ta have one or more of the following features: -at least one of R1, R2, R3 is different from H, - P3 is hydrogen, 3-CI or 3-Br, - R1 is in the 2-position, - R1 and R2 are in the 2,6-position, -P1 and R2 are selected from H, CH3, CI and OCH3, -R1 and R2 are identical, -- R, and R2 are CH3 in the 2,6-position and R3 is H, 3-CI or 3-Br, - X is CH(R4)COZR8, N(CH3)-COOC1-6alkyl, or 2-oxo-3-oxazolidinyl, - Z and Z' are 0, -R8 is C1-6alkyl, -R8 is linked with R4 to form CH2CH2, -Y is CH2OH, CH2OCH3, CH2OC2H8, CH2O-CH2-CH=CH2, CH2O-CH2-C#CH, CH2-OCH2OCH3, CH2OSO2N(CH3)2, CH2CI, n-C4Hg, cyclopropyl, CH=CH-CH3, 24u ryl, benzyl, 2tetrahydrofuryl.

A preferred sub-group of compounds of formula la, are compounds of formula Ib

wherein X is as defined above, either Ra and Rb are both H or together form a covalent bond Ya is C3-5alkenyl; CH2OC1-5alkyl; CH2-OC3-6alkenyl; CH2-OC3-6alkinyl; furyl; benzyl; CH2Cl or C3-6cycloalkyl, either R'1 and P2, are both CH3 in the 2- and 6-positions or R,' is 3-CI and P2, is H, and P3, is H, CH3, CI or Br.

Where Ye is CH2OC1-5alkyl, this is preferably CH2OCH3.

Where Ya is C3-6cycloalkyl, this is preferably cyclopropyl.

Where Ya is furyl, this is preferably 2-furyl.

Where Ya is CH2OC3-5alkenyl, this is preferably CH2Oallyl or -CH2O-(2-butenyl).

Where Ya is CH2OC3-6alkinyl, this is preferably CH2O(2-propinyl).

Where in the compounds of formula I P3, is CI, Br or CH3 this is preferably in the 3-position, particularly when R'1 and P2, are 2- and 6-CH3 resp.

Examples of valuable oomycetes controlling fungicidal compounds of formula Ib are those wherein X, Ra, Rb, Ya, R,', R2' and P3, are i) CH, H, H, 24uryI, 2-CH3, 6-CH3 and H resp. (common name furalaxyl) ii) CH, H, H, CH2-OCH3, 2-CH3, 6-CH3 and H resp. (common name metalaxyl) iii) CH, H, H, benzyl, 2-CH3, 6-CH3 and H resp. (common name galben) iv) CH, covalent bound (Ra+Rb), CH2CI, 2-CH3, 6-CH3 and H (common name milfuram) v) N, covalent bound (Ra+Rb), CH2-OCH3, 2-CH3, 6-CH3 and H (hereinafter designated compound I) vi) N, covalent bound (Ra+Rb), CH2-OCH3, 2-CH3, 6-CH3, 3-CI vii) N, covalent bound (Ra+Rb), CH2-OCH3, 2-CH3, 6-CH3, 3-Br viii) CH, covalent bound (Ra+Rb), cyclopropyl, 3-CI, H and H.

ix) CH, covalent bound (Ra+Rb), CH2OCH3, 2-CH3, 6-CH3 and H.

Compounds of formula I are known or may be obtained according to known processes.

Cymoxanil and Phosetyl-Al are also known systemic fungicides having a fungicidal effect against Plasmopara spp and Phytophthora spp.

It has been found, that the use of Cymoxanil or Phosetyl-Al iii combination with a compound of formula I particularly one of formula la, more particularly one of formula Ib, e.g. one of the compounds i) to ix) indicated above, surprisingly and substantially enhances the effectiveness of the latter against such fungi, and vice versa. The risk of fungi developing resistance against oomycetes controlling having the structure element of formula I is also significantly decreased when using them in association with Cymoxanil or Phosetyl-Al. Moreover, the method of the invention is also surprisingly active against acylalanine resistant field strains of Phytophthora spp and Plasmopara spp as indicated i.a. by a significant decrease of the factor of resistance (the ratio of the fungicidal activity at the 90% level against resistan and sensitive strains). The term "acylalanine resistant field strains" as used herein means comycetes that developed resistance against acylalanine type fungicides (see e.g. Resistance to acylalanine-type fungicides in Peronosporales, Phytopathology 71 (5) 558 (1981). Finally, the method of the invention is effective against a wider spectrum of fungi than that that can be combatted with the active ingredients of this method when used solely.

Accordingly, the invention provides an improved method of combatting fungi, particularly fungi of the class Oomycetes such as Phytophthora spp., Plasmopara spp., Peronospora spp., Pseudoperonospora spp., Sclerophthora spp., Bremia spp. and Pythium spp., in crop locus, especially in grapevines, tomato, hops, cacao, tobacco, potato and lettuce cultures, and an eucalyptus locus which comprises applying to the locus, in admixture or separately, a fungicidally effective aggregate amount of a compound of formula I and Cymoxanil or Phosetyl-Al.

The term crop as used herein is intended to embrace any desired plant growth.

Preferably, the compounds of formula I are applied at a rate of 1 00-400 g/ha, particularly 1 50-300 g/ha, e.g. 200 g/ha in association with 40-1 60 g/ha, particularly 60-120 g/ha, e.g. 80 g/ha Cymoxanil or 750-2500 g/ha, particularly 10002000 g/ha, e.g. 1500 g/ha Phosetyl-Al.

Other pesticides e.g. fungicides, bactericides, insecticides, acaricides, herbicides or plant growth regulating agents may be used in addition to the above associated active ingredients, to enhance the activity of the association of the invention or to widen its spectrum of activity; it is particularly advantageous to use an additional contact fungicide in the method of the invention.

Contact fungicides particularly indicated for use together with the association of the invention are one or more fungicides selected from a copper fungicide, e.g. cuprous oxide, copper (II) oxychloride, cupric hydroxide, copper (II) calcium sulphate, copper (II) calcium oxychloride, Bordeaux mixture or Burgundy mixture; captan; dichlofluanid; folpet; mancozeb; maneb; zineb; chlorothalonil; propineb and dithianon or mixture thereof. Such additional contact fungicide(s) may in general be applied at a rate of 2002000 g/ha. Mancozeb is particularly appropriate for use in the method of this invention. It has an additional synergistic effect on the compound of formula I combinations with Cymoxanil or Phosetyl-Al.

The invention also provides fungicidal compositions comprising a compound of formula I and Cymoxanil or Phosetyl-Al.

In the composition of the invention the weight ratio compound of formula I:Cymoxanil lies preferably in the range of 10:1 to 1:3, more preferably 5:1 to 1:1, particularly 4:1 to 2:1 e.g. 2.5:1. The synergistic effect is evident from the various experimental data in the tables hereinafter, where synergism is i.a. illustrated for the weight ratio compound of formula l:Cymoxanil in the range 1:0.3 to 1:3.

In the compositions of the invention the weight ratio compound of formula l:Phosetyl-Al lies preferably in the range of 1:25 to 1:2, more preferably in the range of 1:15 to 1:3, particularly 1:10 to 1:5 e.g. 1:7.

Where the compositions of the invention comprise additionally a contact fungicide, the weight ratio compound of formula Contact fungicide lies preferably in the range of 1:2 to 1:10, and where Mancozeb, Folpet, Captan or Maneb are used, more preferably 1:4 to 1:9, particularly 1:5 to 1:8 e.g.

1:7. It is particularly advantageous to incorporate Mancozeb in the compositions of the invention.

The composition of the invention may be employed in any conventional form, for example in the form of a twin pack, an instant granulate, a flowable or a wettable powder in association with fungicidally acceptable diluents. Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with a diluent (carrier) and other formulating ingredients such as surfactants.

The term diluents as used herein means any liquid or solid agriculturally acceptable material which may be added to the active constituents to bring it in an easier or improved applicable form, respectively to a usable or desirable strength of activity. It can for example be talc, kaolin, diatomaceous earth, xylene, or water.

Particularly formulations to be applied in spraying forms such as water dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, an ethoxylated alkylphenol and an ethoxylated fatty alcohol.

In general, the formulations include form 0.01 to 90% by weight of active agent from 0 to 20% fungicidally acceptable surfactant and 10 to 99.99% solid or liquid diluent(s), the active agent consisting of at least one compound of formula I together with Cymoxanil or Phosetyl-Al, and optionally other active agents, particularly contact fungicides. Concentrate forms of compositions generaily contain between about 2 and 80%, preferably between about 5 and 70% by weight of active agent.

Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent.

The invention is illustrated by the following Examples wherein parts and percentages are by weight and temperatures are in "C.

TEST A: Fungicidal effect against Phytophthora infestans strains resistant against acylalanine type fungicides Young potted tomato or potato plants (3-5 leaf stage) are sprayed with an aqueous spray liquid of mixture A, containing 0.05 to 0.0002% compound of formula I and 0.05 to 0.0002% CYMOXANIL, or mixture B, containing 0.05 to 0.0002% compound of formula I and 2 to 0.2% Phosetyl-Al or mixture C, containing 0.05 to 0.0002% compound of formula I and 0.2 to 0.003% of a contact fungicide such as Mancozeb, Folpet, Captan, dichlofluanid, Maneb or copper fungicides.

Two hours (or 4, 8, 1 6, 32 or 64 hours later) the treated plants or leaves thereof are washed vigorously, e.g. by simulated rain washing at a rain rate of 1 0-50 mm/hour. Two hours after the washing procedure, the treated plants or leaves are inoculated with a spore suspension (1 05 sporangia/ml) of Phytophthora infestans strains that developed resistance against compounds of formula I. The plants are then transferred to a tent providing 100% relative atmospheric humidity at an ambient temperature of 16 and a day length of 1 6 hours. Disease control is evaluated 4-5 days thereafter, by comparing the treated plants (leaves) with untreated, similarly inoculated plants (leaves).

Where, with the mixtures A and B complete control of the fungal infestation is observed, the degree of fungicidal activity provided by mixture C is significantly less pronounced. Similar results are obtained in grape vines against Plasmopara viticola strains which are resistant against acylalanine type fungicides.

TEST B: Synergistic activity In this test, the fungicidal activity provided by the compounds of formula I, CYMOXANIL or Phosetyl-Al alone, is compared with the activity provided by a compound of formula I when used in association with CYMOXANIL or Phosetyl-Al. The presence of an eventual synergistic effect between twb active ingredients is then established with the aid of the Colby equation AxB p=A+ B 100 wherein A and B are the fungicidal activities of the active ingredients when used alone and p is the fungicidal activity that theoretically would have been obtained with the mixture if there was no interaction between the active ingredients. If p is lower than the experimentally established fungicidal effect, there is synergism.

Young potted potato plants are sprayed with an aqueous spray liquid containing either a compound of formula I, CYMOXANIL or Phosetyl-AI alone or in the association according to the invention. The compounds of formula I and CYMOXANIL are applied in concentrations of 0.0125 to 0.00002%, Phosetyl-Al in concentrations of 0.8 to 0.0125%, until the run-off.

Two hours later, the treated plants are inoculated with a spore suspension of Phytophthora infestans and the plants are then transferred to a tent providing 1 00% relative atmospheric humidity at an ambient temperature of 1 60C and a day length of 1 6 hours. Disease control is evaluated 4-5 days later by comparing the treated plants with untreated, similarly inoculated plants. Analogous tests are run using grape plants infested with Plasmopara viticola.

A more than additive effect is obtained as illustrated in the following tables, in which Comp. is Compound I, Cym is Cymoxanil, Phos. is Phosetyl-Al, M is Mancozeb, the underlined figures are p(Colby) and the non-underlined figures are the experimentally established fungicidal effect.

TABLE I Phytophthora/Tomato

Comp. 0 2 8 Cym.

0 0 60 80 100 2 10 8064 9082 100 8 40 10076 10088 100 32 60 10084 10092 100 ppm TABLE 11 Phytophthora/Tomato

Comp. ppm 0 0.2 0.6 1.8 5.4 Cym.

0 0 0 20 40 70 0.1 0 100 3020 5040 9070 0.6 0 200 3020 6040 9070 1.8 20 j 2020 4036 6552 10076 5.4 40 4040 6052 8064 10082 ppm TABLE ill Phytophthora/Tomato

Comp. ppm 0 2 8 32 Phos.

0 0 60 80 100 125 20 68 9084 100 500 50 9080 10090 100 2000 70 10088 10094 100 ppm TABLE IV Phytophthora/Potato

Comp. ppm Phos. 0 2 8 32 0 0 50 80 100 125 10 6054 8082 100 500 30 80 100 100 65 86 2000 80 10090 10096 100 ppm TABLE V Plasmopara/grape vine

Comp.

0 0.2 0.6 1.8 5.4 Cym.

0 0 0 30 50 60 0.2 0 300 4030 5550 7060 0.6 20 4020 5044 6060 8068 1.8 50 5050 8065 9075 10080 5.4 60 6060 9072 10080 10084 ppm TABLE Vi Plasmopara/grape vine

Comp.

0 0.2 0.6 1.8 5.4 0 0 0 0 40 50 10 10 1010 3028 5046 6055 30 20 2020 4036 6052 7060 90 40 4040 6052 7064 8070 270 50 5050 5060 8070 9075 ppm TABLE VII Phytophthora/Tomato

Comp. 0 0.125 0.375 1.13 3.38 ppm M 0 0.9 2.7 8.1 24.3 ppm û 1 0 10 20 40 60 0.1 0 2 510 3020 j 5040 8060 0.3 - 0 3510 4 20 6040 9 60 0.9 20 4528 5036 7052 10068 2.7 35 5041 5548 10061 10074 ppIn TABLE VIII Plasmopara/grape vine

Comp. 0 0.125 0.375 1.13 3.38 ppm M 0 0.9 2.7 8.1 24.3 ppm Cy 0 0 30 50 60 70 0,1 0 3030 605o 7060 10070 0.3 20 5044 7060 8068 10076 0 9 40 6 58 8070 10076 10082 2.7 60 8072 10080 10084 10088 ppm Based on the results in Table -VIII - which indicate a synergism - the factor of synergism can be calculated with the aid of the Wadley equations: EC 90 (theor.) = a + b +....

a b + EC90 EC90 and SF = EC 90 (theor.) EC 90 (exp.) wherein a, b, etc. are the weight ratios at which the active ingredients are used in the mixture; EC 90, EC 90 (exp.) and EC (theor.) the concentrations allowing a 90% fungicidal control resp. of the active ingredient when used alone as determined by experiment, of the tested composition as determined by experiment and of the tested composition as calculated. SF is the factor of synergism (in case of synergism it is > 1).

The factor of synergism (SF) found with mixtures of Compound 1/Cymoxanil and of Compound l/Cymoxanil/Mancozeb resp. tested on tomato (Phytophthora infestans) and grape vine (Plasmopara viticola) under greenhouse conditions, calculated according to Wadley, are given: TABLE IX Tomato (Phyt.) Grape vine (Plasm.) EC 90(2) EC 90(2) Comp./Cyml*) theor. exp. SF2 theor. exp. SFz 1:0 - 17 - 19 1:0.3 21 7 3.0 23 11 2.1 1:1 31 10 3.1 26 5 5.2 1:3 - 49 16 3.1 30 4 7.5 0:1 - 125 36 Comp./Cym/M 1:0.3:7 69 29 2.4 49 16 3.1 1:2.4::7 76 32 2.4 46 6 7.7 * weight ratio (2) see Wadley Formulation Examples (Wettable powders) A B C D E F G H % by weight Compound of formula 1 8 10 7 10 40 7 10 25 (e.g. Compound I) CYMOXANIL 3.2 5 - 10 24 - 5 10 Phosetyl-Al - - 50 - - 50 - Contact fungicide e.g.

Mancozeb . 56 25 - - 25 Copper (II) oxychloride - 10 - - 17.5 Copper (II) calcium sulphate - 5 - - 18.5 Folpet - - 23 30 Surfactant: Wetting agent (e.g.

Na alkyl naphthalene sulphonate) 1 1 1 1 1 1 1 1 Dispersing agent (e.g.

Na lignin sulphonate) 5 5 5 5 5 5 5 5 Diluent: Silica 5 5 5 5 5 5 5 5 Kaolin 21.8 34 9 39 25 28 13 54 Prussian blue - - - - - 4 - The formulations are obtained by mixing the components, subsequently milling the mixture and a second mixing in conventional manner.

or of formula III

in admixture or separateiy in a fungicidally effective aggregate amount.

2. A method according to Claim 1, wherein compound a) is of formula la

wherein R1, R2 and R3, independently, are H, C1-4alkyl, C1-4-alkoxy, C1-4alkylthio or halogen seelcted from F, Cl and Br, A is selected from a group -CH(R4)-R5 or a group -N(R6)-COOR7, in which R4 is H or C1-4alkyl, R5 is COZR8, CO-N(R9)OR10, CN, CHO,

C#-C-R14, all ene; or is 2,2-dihalo-1 -cyclopropyl unsubstituted or substituted by C1-4alkyl; or is phenyl unsubstituted or substituted, R6 is C1-3alkyl, R7 is C1-6alkyl, C3-6alkenyl or C3-6alkinyl, whereby R5 and R7 may be linked together to form CH2-CH 2; and wherein Z and Z' are 0 or S R8 is C1-6alkyl, C3-6alkenyl, or C3-6alkinyl, and whereby ZR8 may be linked with R4 to form the bridge ZCH(P15)-CH2 in which Z is as defined above and R,5 is H or CH3; R9, R'9 and R"9 are H or C1-4alkyl, R P' 10 and R"o are C1-4alkyl, whereby Rg may be linked with R,o, resp. R'g with R'O, resp.R"g with R"10 and signify alkylene, to form a 5- or 6-membered heterocyclic ring, R11, R,2, R13, independently, are H, C1-4-alkyl, or halogen selected from F, Cl or Br, R,4 is H, C1-4alkyl or halogen selected from CI, Br or I, and Y is H; a hydrocarbon selected from C1-6alkyl, C2-6alkenyl and C21-6alkinyl unsubstituted or substituted by halogen, selected from F, CI or Br, or by CN; C2-6epoxyalkylene; C3-6cycloalkyl; a 5-membered heterocyclic ring comprising 1 to 3 heteroatoms selected from 0, S and N, which is unsubstituted or substituted by C1-4alkyl or halogen selected from F, CI or Br; (A1)n-Az; (A1)n-Y1-NR9aR10a; (A1)nZ1H and esters or ethers thereof; benzyl unsubstituted or substituted, in which A, is CH2 or CH(CH3) nisOori, Az is a 1 -azolyl comprising 1 to 3 nitrogen atoms, Y, is a covalent bond or NH, Rga is H or C1-4alkyl.

H10a is C1-4alkyl, Z1 is O or S.

3. A method according to Claim 2, wherein compound a) is of formula Ib

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (34)

1. **WARNING** start of CLMS field may overlap end of DESC **.

   or of formula III

   in admixture or separateiy in a fungicidally effective aggregate amount.
2. 2. A method according to Claim 1, wherein compound a) is of formula la

   wherein R1, R2 and R3, independently, are H, C1-4alkyl, C1-4-alkoxy, C1-4alkylthio or halogen seelcted from F, Cl and Br, A is selected from a group -CH(R4)-R5 or a group -N(R6)-COOR7, in which R4 is H or C1-4alkyl, R5 is COZR8, CO-N(R9)OR10, CN, CHO,

   C#-C-R14, all ene; or is 2,2-dihalo-1 -cyclopropyl unsubstituted or substituted by C1-4alkyl; or is phenyl unsubstituted or substituted, R6 is C1-3alkyl, R7 is C1-6alkyl, C3-6alkenyl or C3-6alkinyl, whereby R5 and R7 may be linked together to form CH2-CH 2; and wherein Z and Z' are 0 or S R8 is C1-6alkyl, C3-6alkenyl, or C3-6alkinyl, and whereby ZR8 may be linked with R4 to form the bridge ZCH(P15)-CH2 in which Z is as defined above and R,5 is H or CH3; R9, R'9 and R"9 are H or C1-4alkyl, R P' 10 and R"o are C1-4alkyl, whereby Rg may be linked with R,o, resp. R'g with R'O, resp.R"g with R"10 and signify alkylene, to form a 5- or 6-membered heterocyclic ring, R11, R,2, R13, independently, are H, C1-4-alkyl, or halogen selected from F, Cl or Br, R,4 is H, C1-4alkyl or halogen selected from CI, Br or I, and Y is H; a hydrocarbon selected from C1-6alkyl, C2-6alkenyl and C21-6alkinyl unsubstituted or substituted by halogen, selected from F, CI or Br, or by CN; C2-6epoxyalkylene;C3-6cycloalkyl; a 5-membered heterocyclic ring comprising 1 to 3 heteroatoms selected from 0, S and N, which is unsubstituted or substituted by C1-4alkyl or halogen selected from F, CI or Br; (A1)n-Az; (A1)n-Y1-NR9aR10a; (A1)nZ1H and esters or ethers thereof; benzyl unsubstituted or substituted, in which A, is CH2 or CH(CH3) nisOori, Az is a 1 -azolyl comprising 1 to 3 nitrogen atoms, Y, is a covalent bond or NH, Rga is H or C1-4alkyl.

   H10a is C1-4alkyl, Z1 is O or S.

   3. A method according to Claim 2, wherein compound a) is of formula Ib

   In general, the active ingredients are used in technical form. An example of a formulation comprising technical active ingredients is as follows: EXAMPLE J Compound I technical (95%) 10.5% Cymoxanil -technical (95%) 5.3% Mancozeb -technical (80%) 31.3% Copperoxy (II) chloride (57% Cu) 17.5% Copper (II) calcium sulphate (27% Cu) 18.7% Surfactant and Silica 11.0% Kaolin 5.7% EXAMPLE K Flowable 440 g/l

   4.2% w/w Compound I techn. 95%

   1.7% w/w Cymoxanil techn. 80%

   35.0% w/w Mancozeb techn. 80%

   4.0% w/w Surfactant

   6.0% w/w 1 ,2-Propylene glycol (Anti-freezing) 0.3% w/w Sticker 0.5% w/w Stabilisator (e.g. citric acid)

   48.3% w/w Water 100.0% w/w The formulation is produced by mixing the components, wet grinding and mixing.

   EXAMPLE L Granules 67% w/w WG

   8.4% w/w Compound I techn. 95%
3. 3.4% w/w Cymoxanil techn. 95%

   70.0% w/w Mancozeb techn. 80% 10.0% w/w Dispersing/binding agent (e.g. Na-lignin-sulfonate)

   7.7% w/w Diluent (e.g. kaolin) 0.5% w/w Stabiiisator (e.g. citric acid).

   The formulation is produced by mixing and grinding the components followed by pan granulation or fluid bed-granulation.

   The granules disperse well in water, forming a sprayable suspension.

   1. A method of combatting fungi in a locus, which comprises applying to the locus a compound a) an oomycetes controlling fungicide having the structure element of formula I

   in which Xis CH or N, and a compound b), a compound of formula II

   in which Xis as defined in Claim 1, either Pa and Rb are both H or together form a covalent bond Ya is C3-5alkenyl; CH2OC1-5alkyl; CH2-OC3-6alkenyl; CH2-OC3-6alkinyl; furyl; benzyl; CH2Cl or C3 6cycloalkyl, either P1, and P2, are both CH3 in the 2- and 6-positions or R'1 is 3-CI and P2, is H, and R3' is H, CH3, CI or Br.
4. 4. A method according to Claim 3, wherein compound a) is a compound of formula Ib wherein X, Pa, Rb, Ya, R'1, R'2 and R'3 are i) CH, H, H, 2-furyl, 2-CH3, 6-CH3 a and H resp.

   ii) CH, H, H, CH2-OCH3, 2-CH3, 6-CH3and H H resp.

   iii) CH, H, H, benzyl, 2-CH3, 6-CH and H resp.

   iv) CH, covalent bound (Ra+Rb), CH2Cl, 2-CH3, 6-CH3 and H resp.

   v) N, covalent bound (Ra+Rb), CH2-OCH3, 2-CH3, 6-CH3 and H resp.

   vi) N, covalent bound (Ra+Rb), CH2-OCH3, 2-CH3, 6-CH3, 3-Cl resp.

   vii) N, covalent bound (Ra+Rb), CH2-OCH3, 2-CH3, 6CHj 3-Br resp viii) CH, covalent bound (Ra+Rb), cyclopropyl, 3-Cl, H and H resp.

   ix) CH, covalent bound (Ra+Rb), CH2OCH3, 2-CH3, 6-CH3 and H resp.
5. 5. A method according to any one of Claims 1 to 4 wherein compound b) is of formula II, as defined in Claim 1.
6. 6. A method according to any one of Claims 1 to 4 wherein compound b) is of formula Ill, as defined in Claim 1.
7. 7. A method according to Claim 5, which comprises applying from 100 to 400 g/ha of compound a) and from 40 to 1 60 g/ha of the compound of formula II.
8. 8. A method according to Claim 6, which comprises applying from 100 to 400 g/ha of compound a) and from 750 to 2500 g/ha of formula III.
9. 9. A method according to any one of Claims 7 and 8, which comprises, applying to the locus, in addition to the compounds a) and b) a contact fungicide.
10. 10. A method according to Claim 9, wherein the contact fungicide is selected from the group consisting of a copper fungicide, captan, dichlofluanid, folpet, mancozeb, maneb, zineb, chlorothalonil, propineb and dithianon, or a mixture thereof.
11. 11. A method according to Claim 10, wherein the contact fungicide is mancozeb.
12. 12. A method according to Claim 10, wherein the contact fungicide is folpet.
13. 13. A method according to Claim 1 0, which comprises applying mancozeb and a copper fungicide as contact fungicide.
14. 14. A fungicidal composition which comprises compound a) and compound b) as defined in Claim 1.
15. 15. A composition according to Claim 14, wherein compound a) is of formula la, as defined in Claim 2.
16. 1 6. A composition according to Claim 1 5, wherein compound a) is of formula Ib, as defined in Claim 3.
17. 17. A composition according to Claim 16, wherein compound a) is a compound of formula lb, wherein X, R,, Pb, Ya, R'1, R'2 and R'3 are i) CH, H, H, 2-furyl, 2-CH3, 6-CH3 a and H resp.

    ii) CH, H, H, CH2-OCH3, 2-CH3, 6-CH3 and H resp.

    iii) CH, H, H, benzyl, 2-CH3, 6-CH3 and H resp.

    iv) CH, covalent bound (Ra+Rb), CH2Cl, 2-CH3, 6-CH3 and H resp.

    v) N, covalent bound (Ra+Rb), CH2-OCH3, 2-CH3, 6-CH3 and H resp.

    vi) N, covalent bound (Ra+Rb), CH2-OCH3, 2-CH3, 6-CH3, 3-Cl resp.

    vii) N, covalent bound (Ra+Rb), CH2-OCH3, 2-CH3, 6-CH3, 3-Br resp.

    viii) CH, covalent bound (Ra+Rb), cyclopropyl, 3-Cl, H and H resp.

    ix) CH, covalent bound (Ra+Rb), CH2OCH3, 2-CH3, 6-CH3 and H resp.
18. 18. A composition according to any one of Claims 14 to 1 7, wherein compound b) is of formula II, as defined in Claim 1.
19. 19. A composition according to any one of Claims 14 to 1 7 wherein compound b) is of formula Ill, as defined in Claim 1.
20. 20. A composition according to Claim 18, wherein the weight ratio of compound a) to the compound of formula II is from 10:1 to 1:3.
21. 21. A composition according to Claim 20, wherein said ratio is from 1:0.3 to 1 :3.
22. 22. A composition according to Claim 19, wherein the weight ratio of compound a) to the compound of formula III is from 1:25 to 1 :2.
23. 23. A composition according to any one of Claims 1 8 to 22, including a contact fungicide.
24. 24. A composition according to Claim 23, wherein the contact fungicide is selected from the group consisting of a copper fungicide, captan, dichlofluanid, folpet, mancozeb, maneb, zineb, chlorothalonil, propineb and dithianon, or a mixture thereof.
25. 25. A composition according to Claim 24 wherein the contact fungicide is mancozeb.
26. 26. A composition according to Claim 24, wherein the contact fungicide is folpet.
27. 27. A composition according to Claim 24, wherein the contact fungicide is a mixture of mancozeb and a copper fungicide.
28. 28. A composition according to any one of Claims 23 to 27, wherein the weight ratio of compound a) to the contact fungicide is from 1:2 to 1:10.
29. 29. A composition according to any one of Claims 14 to 28 comprising from 0.01 to 90% by weight of active agents, from 0 to 20% by weight fungicidally acceptable surfactant and from 10 to 99.99% by weight of a fungicidally acceptable diluent.
30. 30. A concentrate form of a composition of Claim 29 comprising from 2 to 80% by weight of active agent.
31. 31.An application form of a composition of Claim 29 comprising from 0.01 to 20% by weight of active agent.
32. 32. A method according to Claim 1 substantially as described herein.
33. 33. A composition according to Claim 14 substantially as described herein.
34. 34. A process of preparing compositions according to any of the preceding Claims 1 4 to 33 which comprises mixing the active ingredients with a diluent and optionaily other formulating ingredients.