Fungicidal Compositions

The present invention relates to novel fungicidal compositions for the treatment of phytopathogenic diseases of useful plants, especially phytopathogenic fungi, and to a method of controlling phytopathogenic diseases on useful plants.

It is known from EP 2522658A1 that certain quinoline derivatives have biological activity against phytopathogenic fungi. On the other hand various fungicidal compounds of different chemical classes are widely known as plant fungicides for application in various crops of cultivated plants. However, crop tolerance and activity against phytopathogenic plant fungi of the single fungicides do not always satisfy the needs of agricultural practice in many incidents and aspects.

The present invention therefore relates to a composition suitable for control of diseases caused by phytopathogens comprising as component (A) the compound of formula I

wherein R is hydrogen or fluoro;

and as component (B) a compound selected from the group consisting of

acibenzolar-S-methyl, aspergillus flavus NRRL 21882, azoxystrobin, benzovindiflupyr, chlorothalonil, cyproconazole, cyprodinil, difenoconazole, fenpropidin, fenpropimorph, fluazinam, fludioxonil, hexaconazole, isopyrazam, mandipropamid, metalaxyl, metalaxyl-M, oxadixyl, oxathiapiprolin, paclobutrazol, penconazole, propiconazole, pyrifenox, pyroquilon, sulfur, bacillus subtilis var.

amyloliquefaciens Strain FZB24, thiabendazole and tricyclazole; and agrochemically acceptable salts thereof.

It has been found that the use of components (B) in combination with component (A) surprisingly and substantially may enhance the effectiveness of the latter against fungi, and vice versa. Additionally, the method of the invention is effective against a wider spectrum of such fungi that can be combated with the active ingredients of this method, when used solely.

In general, the weight ratio of component (A) to component (B) is from 1000: 1 to 1 :1000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10: 1 to 1 : 10, very especially from 5:1 and 1 :5, special preference being given to a ratio of from 2: 1 to 1 :2, and a ratio of from 4: 1 to 2:1 being likewise preferred, above all in a ratio of 1 : 1 , or 5: 1 , or 5:2, or 5:3, or 5:4, or 4: 1 , or 4:2, or 4:3, or 3: 1 , or 3:2, or 2: 1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 : 150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 :1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750.

It has been found, surprisingly, that certain weight ratios of component (A) to component (B) are able to give rise to synergistic activity. Therefore, a further aspect of the invention are compositions, wherein component (A) and component (B) are present in the composition in amounts producing a synergistic effect. This synergistic activity is apparent from the fact that the fungicidal activity of the composition comprising component (A) and component (B) is greater than the sum of the fungicidal activities of component (A) and component (B). This synergistic activity extends the range of action of component (A) and component (B) in two ways. Firstly, the rates of application of component (A) and component (B) are lowered whilst the action remains equally good, meaning that the active ingredient mixture still achieves a high degree of phytopathogen control even where the two individual components have become totally ineffective in such a low application rate range. Secondly, there is a substantial broadening of the spectrum of phytopathogens that can be controlled.

A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows

(COLBY, S.R. "Calculating synergistic and antagonistic responses of herbicide combination", Weeds, Vol. 15, pages 20-22; 1967):

ppm = milligrams of active ingredient (= a.i.) per liter of spray mixture

X = % action by active ingredient (A) using p ppm of active ingredient

Y = % action by active ingredient (B) using q ppm of active ingredient.

According to COLBY, the expected (additive) action of active ingredients (A)+(B) using p+q ppm of

X ^■ Y

active ingredient is L = X + Y

100

If the action actually observed (O) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms, synergism corresponds to a positive value for the difference of (O-E). In the case of purely complementary addition of activities (expected activity), said difference (O-E) is zero. A negative value of said difference (O-E) signals a loss of activity compared to the expected activity.

However, besides the actual synergistic action with respect to fungicidal activity, the compositions according to the invention can also have further surprising advantageous properties. Examples of such advantageous properties that may be mentioned are: more advantageuos degradability;

improved toxicological and/or ecotoxicological behaviour; or improved characteristics of the useful plants including: emergence, crop yields, more developed root system, tillering increase, increase in plant height, bigger leaf blade, less dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds needed, more productive tillers, earlier flowering, early grain maturity, less plant verse (lodging), increased shoot growth, improved plant vigor, and early germination.

Some compositions according to the invention have a systemic action and can be

used as foliar, soil and seed treatment fungicides.

With the compositions according to the invention it is possible to inhibit or destroy the

phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms.

The compositions according to the invention can be applied to the phytopathogenic microorganisms, the useful plants, the locus thereof, the propagation material thereof, storage goods or technical materials threatened by microorganism attack. The compositions according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, storage goods or technical materials by the microorganisms.

A further aspect of the present invention is a method of controlling diseases on useful plants or on propagation material thereof caused by phytopathogens, which comprises applying to the useful plants, the locus thereof or propagation material thereof a composition according to the invention. Preferred is a method, which comprises applying to the useful plants or to the locus thereof a composition according to the invention, more preferably to the useful plants. Further preferred is a method, which comprises applying to the propagation material of the useful plants a composition according to the invention.

The compound of formula I, wherein R is hydrogen, is represented by the compound of formula la. The compound of formula I, wherein R is fluoro, is represented by the compound of formula lb. The compound of formula la, which chemical designation is

2-[2-fluoro-6-(8-fluoro-2-methyl-quinolin-3-yloxy)-phenyl]-p ropan-2-ol, and its preparation is described in EP2522658A1. The compound of formula lb, which chemical designation is 2-[2-[(7,8-difluoro-2- methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol, and its preparation is also described in

EP2522658A1.

The components (B) are known. The number in brackets relates to the Chemical Abstract Registry Number: acibenzolar-S-methyl [135158-54-2], aspergillus flavus NRRL 21882, (available from Circle One Global, Inc, P.O. Box 28, One Arthur Street, Shellman, GA 39886-0028, U.S.A. and known under the trade name afla-guard®), azoxystrobin [131860-33-8], benzovindiflupyr [1072957-71-1], chlorothalonil [1897-45-6], cyproconazole [94361-06-5], cyprodinil [121552-61-2], difenoconazole [119446-68-3], fenpropidin [67306-00-7], fenpropimorph [67564-91-4], fluazinam [79622-59-6], fludioxonil [131341-86-1], hexaconazole [79983-71-4], isopyrazam [881685-58-1], mandipropamid [374726-62-2], metalaxyl [57837-19-1], metalaxyl-M [70630-17-0], oxadixyl [77732-09-3], oxathiapiprolin [1003318-67-9], paclobutrazol [76738-62-0], penconazole [66246-88-6], propiconazole [60207-90-1], pyrifenox [88283-41-4], pyroquilon [57369-32-1], sulfur [7704-34-9], bacillus subtilis var. amyloliquefaciens Strain FZB24 (available from Novozymes Biologicals Inc., 5400 Corporate Circle, Salem, VA 24153, U.S.A. and known under the trade name Taegro®), thiabendazole [148-79-8] and tricyclazole [41814-78-2].

Throughout this document the expression "composition" means the various mixtures or combinations of components (A) and (B), for example in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank- mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the components (A) and (B) is not essential for working the present invention.

The following binary mixtures of the compounds of formula I and the use of said mixtures are preferred:

the compound of formula la + acibenzolar-S-methyl, especially against pyricularia oryzae;

the compound of formula la + azoxystrobin, especially against pyricularia oryzae and altaernairia spp.; in particular against pyricularia oryzae;

the compound of formula la + benzovindiflupyr, especially against venturia inaequalis, powdery mildew and alternaria spp.; in particular against venturia inaequalis;

the compound of formula la + cyprodinil, especially against botrytis cinerea and venturia inaequalis; the compound of formula la + difenoconazole, especially against pyricularia oryzae, venturia inaequalis, powdery mildew and alternaria spp., in particular against pyricularia oryzae and venturia inaequalis; the compound of formula la + fenpropidin, especially against powdery mildew;

the compound of formula la + fenpropimorph, especially against powdery mildew;

the compound of formula la + fluazinam, especially against botrytis cinerea and sclerotinia spp., in particular against botrytis cinerea;

the compound of formula la, + fludioxonil, especially against botrytis cinerea, venturia inaequalis and sclerotinia spp.; in particular against botrytis cinerea;

the compound of formula la + hexaconazole, especially against pyricularia oryzae;

the compound of formula la + isopyrazam, especially against venturia inaequalis, sclerotinia spp., powdery mildew and alternaria spp.; in particular against venturia inaequalis, alternaria spp. and sclerotinia spp.;

the compound of formula la + penconazole, in particular against venturia inaequalis and powdery mildew;

the compound of formula la + propiconazole, in particular against pyricularia oryzae;

the compound of formula la + pyroquilon, in particular against pyricularia oryzae;

the compound of formula la + sulfur, in particular against powdery mildew;

the compound of formula la + bacillus subtilis var. amyloliquefaciens Strain FZB24, in particular against botrytis cinerea, pyricularia oryzae, powdery mildew and alternaria spp.;

the compound of formula la + thiabendazole, in particular against powdery mildew; and the compound of formula la + tricyclazole, in particular against pyricularia oryzae;

the compound of formula lb + acibenzolar-S-methyl, especially against pyricularia oryzae;

the compound of formula lb + azoxystrobin, especially against pyricularia oryzae and altaernairia spp.; in particular against pyricularia oryzae;

the compound of formula lb + benzovindiflupyr, especially against venturia inaequalis, powdery mildew and alternaria spp.; in particular against venturia inaequalis;

the compound of formula lb + cyprodinil, especially against botrytis cinerea and venturia inaequalis; the compound of formula lb + difenoconazole, especially against pyricularia oryzae, venturia inaequalis, powdery mildew and alternaria spp., in particular against pyricularia oryzae and venturia inaequalis;

the compound of formula lb + fenpropidin, especially against powdery mildew;

the compound of formula lb + fenpropimorph, especially against powdery mildew;

the compound of formula lb + fluazinam, especially against botrytis cinerea and sclerotinia spp., in particular against botrytis cinerea;

the compound of formula lb + fludioxonil, especially against botrytis cinerea, venturia inaequalis and sclerotinia spp.; in particular against botrytis cinerea;

the compound of formula lb + hexaconazole, especially against pyricularia oryzae;

the compound of formula lb + isopyrazam, especially against venturia inaequalis, sclerotinia spp., powdery mildew and alternaria spp.; in particular against venturia inaequalis, alternaria spp. and sclerotinia spp.; the compound of formula lb + penconazole, in particular against venturia inaequalis and powdery mildew;

the compound of formula lb + propiconazole, in particular against pyricularia oryzae;

the compound of formula lb + pyroquilon, in particular against pyricularia oryzae;

the compound of formula lb + sulfur, in particular against powdery mildew;

the compound of formula lb + bacillus subtilis var. amyloliquefaciens Strain FZB24, in particular against botrytis cinerea, pyricularia oryzae, powdery mildew and alternaria spp.;

the compound of formula lb + thiabendazole, in particular against powdery mildew; and

the compound of formula lb + tricyclazole, in particular against pyricularia oryzae.

Especially preferred compositions comprise

a) the compound of formula la and benzovindiflupyr; in particular against venturia inaequalis, powdery mildew and alternaria spp.; in particular against venturia inaequalis; and

b) the compound of formula la and isopyrazam, especially against venturia inaequalis, sclerotinia spp., powdery mildew and alternaria spp.; in particular against venturia inaequalis, alternaria spp. and sclerotinia spp.

A further preferred embodiment of the invention relates to composition suitable for control of diseases caused by phytopathogens consisting of as fungicidally active ingredients as component (A) the compound of formula I

and as component (B) a compound selected from the group consisting of

acibenzolar-S-methyl, aspergillus flavus NRRL 21882, azoxystrobin, benzovindiflupyr, chlorothalonil, cyproconazole, cyprodinil, difenoconazole, fenpropidin, fenpropimorph, fluazinam, fludioxonil, hexaconazole, isopyrazam, mandipropamid, metalaxyl, metalaxyl-M, oxadixyl, oxathiapiprolin, paclobutrazol, penconazole, propiconazole, pyrifenox, pyroquilon, sulfur, bacillus subtilis var.

amyloliquefaciens Strain FZB24, thiabendazole and tricyclazole; and agrochemically acceptable salts thereof.

Said further preferred embodiment consists as fungicially active ingredients the following binary mixtures of the compound of formula la with component (B):

the compound of formula la + acibenzolar-S-methyl, especially against pyricularia oryzae; the compound of formula la + azoxystrobin, especially against pyricularia oryzae and altaernairia spp.; in particular against pyricularia oryzae;

the compound of formula la + benzovindiflupyr, especially against venturia inaequalis, powdery mildew and alternaria spp.; in particular against venturia inaequalis;

the compound of formula la + cyprodinil, especially against botrytis cinerea and venturia inaequalis; the compound of formula la + difenoconazole, especially against pyricularia oryzae, venturia inaequalis, powdery mildew and alternaria spp., in particular against pyricularia oryzae and venturia inaequalis;

the compound of formula la + fenpropidin, especially against powdery mildew;

the compound of formula la + fenpropimorph, especially against powdery mildew;

the compound of formula la + fluazinam, especially against botrytis cinerea and sclerotinia spp., in particular against botrytis cinerea;

the compound of formula la + fludioxonil, especially against botrytis cinerea, venturia inaequalis and sclerotinia spp.; in particular against botrytis cinerea;

the compound of formula la + hexaconazole, especially against pyricularia oryzae;

the compound of formula la + isopyrazam, especially against venturia inaequalis, sclerotinia spp., powdery mildew and alternaria spp.; in particular against venturia inaequalis, alternaria spp. and sclerotinia spp.;

the compound of formula la + penconazole, in particular against venturia inaequalis and powdery mildew;

the compound of formula la + propiconazole, in particular against pyricularia oryzae;

the compound of formula la + pyroquilon, in particular against pyricularia oryzae;

the compound of formula la + sulfur, in particular against powdery mildew;

the compound of formula la + bacillus subtilis var. amyloliquefaciens Strain FZB24, in particular against botrytis cinerea, pyricularia oryzae, powdery mildew and alternaria spp.;

the compound of formula la + thiabendazole, in particular against powdery mildew; and

the compound of formula la + tricyclazole, in particular against pyricularia oryzae.

Especially preferred compositions consists of as fungicidally active ingredients

a) the compound of formula la and benzovindiflupyr; in particular against venturia inaequalis, powdery mildew and alternaria spp.; in particular against venturia inaequalis; and

b) the compound of formula la and isopyrazam, especially against venturia inaequalis, sclerotinia spp., powdery mildew and alternaria spp.; in particular against venturia inaequalis, alternaria spp. and sclerotinia spp.

Mixtures of the compound of formula la with a component (B) selected from the group consisting of azoxystrobin, benzovindiflupyr, chlorothalonil, cyprodinil, difenoconazole, fluazinam, fludioxonil, hexaconazole, isopyrazam , propiconazole, pyroquilon and tricyclazole and agrochemically acceptable salts thereof are also preferred. The following mixtures are especially preferred:

1 ) The compound of formula la + azoxystrobin, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium and Pyricularia oryzae, preferably at mixing ratios of

la : azoxystrobin of 1 : 21 to 1 : 2.5.

2) The compound of formula la + benzovindiflupyr, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of la : benzovindiflupyr of 1 : 31 to 1 : 5.

3) The compound of formula la + chlorothalonil, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of la to chlorothalonil of 2 : 1 to 1 : 200.

4) The compound of formula la + cyprodinil, in particular against Alteria solani, Botrytis cinera,

Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of la to cyprodinil of 1 : 4 to 1 : 25.

5) The compound of formula la + difenoconazole, in particular against, Botrytis cinera, Colletotrichum lagenarium, and Pyricularia oryzae, preferably at mixing ratios of la to difenoconazole of 1 : 25 to 1 : 420.

6) The compound of formula la + fluazinam, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of la to fluazinam of 1 : 2 to 1 : 40.

7) The compound of formula la + fludioxonil, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of la to fludioxonil of 1 : 2.5 to 1 : 42.

8) The compound of formula la + hexaconazole, in particular against Alteria solani, Colletotrichum lagenarium, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of la to

hexaconazole of 1 : 25 to 1 : 104.

9) The compound of formula la + isopyrazam, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of la to isopyrazam of 1 : 25 to 1 : 313.

10) The compound of formula la + propiconazole, in particular against Alteria solani, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of la to propiconazole of 1 : 25 to 1 : 420. 1 1 ) The compound of formula la + pyroquilon, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of la to pyroquilon of 1 : 200 to 1 : 2000.

12) The compound of formula la + trizyclazole, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium and Venturia inequalis, preferably at mixing ratios of la to trizyclazole of 1 : 26 to 1 : 2000.

Mixtures of the compound of formula lb with a component (B) selected from the group consisting of azoxystrobin, benzovindiflupyr, chlorothalonil, cyprodinil, difenoconazole, fluazinam, fludioxonil, hexaconazole, isopyrazam, propiconazole, pyroquilon and tricyclazole and agrochemically acceptable salts thereof are also preferred.

The following mixtures are especially preferred:

13) The compound of formula lb + azoxystrobin, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici and Pyricularia oryzae, preferably at mixing ratios of lb : azoxystrobin of 1 : 42 to 1 : 2.5.

14) The compound of formula lb + benzovindiflupyr, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of lb : benzovindiflupyr of 1 : 31 to 1 : 2.5.

15) The compound of formula lb + chlorothalonil, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of lb to chlorothalonil of 1 : 25 to 1 : 400.

16) The compound of formula lb + cyprodinil, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of lb to cyprodinil of 1 : 2.5 to 1 : 20.

17) The compound of formula lb + difenoconazole, in particular against, Botrytis cinera,

Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of lb to difenoconazole of 1 : 26 to 1 : 400.

18) The compound of formula lb + fluazinam, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of lb to fluazinam of 1 : 2.5 to 1 : 40.

19) The compound of formula lb + fludioxonil, in particular against Alteria solani, Botrytis cinera, Colletotrichum lagenarium, Septoria tritici, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of lb to fludioxonil of 1 : 2.5 to 1 : 40.

20) The compound of formula lb + hexaconazole, in particular against Alteria solani, Botrytis cinera and Venturia inequalis, preferably at mixing ratios of lb to hexaconazole of 1 : 208 to 1 : 416. 21 ) The compound of formula lb + isopyrazam, in particular against Alteria solani, Botrytis cinera and Venturia inequalis, preferably at mixing ratios of lb to isopyrazam of 1 : 26 to 1 : 313.

22) The compound of formula lb + propiconazole, in particular against Alteria solani, Botrytis cinera, Septoria tritici and Pyricularia oryzae, preferably at mixing ratios of lb to propiconazole of 1 : 26 to 1 : 416.

23) The compound of formula lb + pyroquilon, in particular against Alteria solani, Botrytis cinera, Pyricularia oryzae and Venturia inequalis, preferably at mixing ratios of lb to pyroquilon of 1 : 260 to 1 : 1000.

24) The compound of formula lb + trizyclazole, in particular against Botrytis cinera and Venturia inequalis, preferably at mixing ratios of lb to trizyclazole of 1 : 260 to 1 : 1000.

The active ingredient combinations are effective against harmful microorganisms, such as microorganisms, that cause phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria.

The active ingredient combinations are effective especially against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia,

Mycosphaerella, Uncinula); Basidiomycetes (e.g. the genus Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti (also known as Deuteromycetes; e.g. Botrytis,

Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella); Oomycetes (e.g. Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, Plasmopara).

According to the invention "useful plants" typically comprise the following species of plants: grape vines; cereals, such as wheat, barley, rye or oats; beet, such as sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as marrows, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceae, such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee; sugar cane; tea; vines; hops; durian; bananas; natural rubber plants; turf or ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example conifers. This list does not represent any limitation.

The term "useful plants" is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl- shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding

(mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names

RoundupReady® , Herculex I® and LibertyLink®. The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus. Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood by δ-endotoxins, for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ). An example for a truncated toxin is a truncated CrylA(b), which is expressed in the Bt1 1 maize from Syngenta Seed SAS, as described below. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D- recognition sequence is inserted into a CrylllA toxin (see WO 03/018810) Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type

deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm®

(maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I ® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N- acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B ® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a

CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT ® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); NatureGard® and Protecta®. Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylA(b) toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium. 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylA(b) toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified CrylllA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cryll IB(b1 ) toxin and has resistance to certain Coleoptera insects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1 160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cryl F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.

7. NK603 * MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150

Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 * MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain

Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fiir Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003,

(http://bats.ch).

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called

"pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).

Useful plants of elevated interest in connection with present invention are cereals; soybean; rice; oil seed rape; pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vines and vegetables, such as tomatoes, potatoes, cucurbits and lettuce.

The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.

The term "plant propagation material" is understood to denote generative parts of a plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.

A further aspect of the instant invention is a method of protecting natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms against attack of fungi, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a combination of components (A) and (B) in a synergistically effective amount.

According to the instant invention, the term "natural substances of plant origin, which have been taken from the natural life cycle" denotes plants or parts thereof which have been harvested from the natural life cycle and which are in the freshly harvested form. Examples of such natural substances of plant origin are stalks, leafs, tubers, seeds, fruits or grains. According to the instant invention, the term "processed form of a natural substance of plant origin" is understood to denote a form of a natural substance of plant origin that is the result of a modification process. Such modification processes can be used to transform the natural substance of plant origin in a more storable form of such a substance (a storage good). Examples of such modification processes are pre-drying, moistening, crushing, comminuting, grounding, compressing or roasting. Also falling under the definition of a processed form of a natural substance of plant origin is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.

According to the instant invention, the term "natural substances of animal origin, which have been taken from the natural life cycle and/or their processed forms" is understood to denote material of animal origin such as skin, hides, leather, furs, hairs and the like.

The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.

A preferred embodiment is a method of protecting natural substances of plant origin, which have been taken from the natural life cycle, and/or their processed forms against attack of fungi, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a combination of components (A) and (B) in a synergistically effective amount.

A further preferred embodiment is a method of protecting fruits, preferably pomes, stone fruits, soft fruits and citrus fruits, which have been taken from the natural life cycle, and/or their processed forms, which comprises applying to said fruits and/or their processed forms a combination of components (A) and (B) in a synergistically effective amount.

The combinations of the present invention may also be used in the field of protecting industrial material against attack of fungi. According to the instant invention, the term "industrial material" denotes non-live material which have been prepared for use in industry. For example, industrial materials which are intended to be protected against attack of fungi can be glues, sizes, paper, board, textiles, carpets, leather, wood, constructions, paints, plastic articles, cooling lubricants, aquaeous hydraulic fluids and other materials which can be infested with, or decomposed by, microorganisms. Cooling and heating systems, ventilation and air conditioning systems and parts of production plants, for example cooling-water circuits, which may be impaired by multiplication of microorganisms may also be mentioned from amongst the materials to be protected. The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.

The combinations of the present invention may also be used in the field of protecting technical material against attack of fungi. According to the instant invention, the term "technical material" includes paper; carpets; constructions; cooling and heating systems; ventilation and air conditioning systems and the like. The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold. The combinations according to the present invention are particularly effective against powdery mildews; rusts; leafspot species; early blights and molds; especially against Septoria, Puccinia, Erysiphe, Pyrenophora and Tapesia in cereals; Phakopsora in soybeans; Hemileia in coffee;

Phragmidium in roses; Alternaria in potatoes, tomatoes and cucurbits; Sclerotinia in turf, vegetables, sunflower and oil seed rape; black rot, red fire, powdery mildew, grey mold and dead arm disease in vine; Botrytis cinerea in fruits; Monilinia spp. in fruits and Penicillium spp. in fruits.

The combinations according to the present invention are furthermore particularly effective against seedborne and soilborne diseases, such as Alternaria spp., Ascochyta spp., Botrytis cinerea, Cercospora spp., Claviceps purpurea, Cochliobolus sativus, Colletotrichum spp., Epicoccum spp., Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium solani, Fusarium subglutinans, Gaumannomyces graminis , Helminthosporium spp., Microdochium nivale, Phoma spp., Pyrenophora graminea, Pyricularia oryzae, Rhizoctonia solani, Rhizoctonia cerealis, Sclerotinia spp., Septoria spp., Sphacelotheca reilliana, Tilletia spp., Typhula incarnata, Urocystis occulta, Ustilago spp. or Verticillium spp.; in particular against pathogens of cereals, such as wheat, barley, rye or oats; maize; rice; cotton; soybean; turf; sugarbeet; oil seed rape; potatoes; pulse crops, such as peas, lentils or chickpea; and sunflower.

The combinations according to the present invention are furthermore particularly effective against post harvest diseasese such as Botrytis cinerea, Colletotrichum musae, Curvularia lunata, Fusarium semitecum, Geotrichum candidum, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Mucor piriformis, Penicilium italicum, Penicilium solitum, Penicillium digitatum or Penicillium expansum in particular against pathogens of fruits, such as pomefruits, for example apples and pears, stone fruits, for example peaches and plums, citrus, melons, papaya, kiwi, mango, berries, for example strawberries, avocados, pomegranates and bananas, and nuts.

The amount of a combination of the invention to be applied, will depend on various factors, such as the compounds employed; the subject of the treatment, such as, for example plants, soil or seeds; the type of treatment, such as, for example spraying, dusting or seed dressing; the purpose of the treatment, such as, for example prophylactic or therapeutic; the type of fungi to be controlled or the application time.

The mixtures comprising a compound of formula I selected from table 1 and 2 and one or more active ingredients as described above can be applied, for example, in a single "ready-mix" form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a "tank-mix", and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying the compounds of formula I selected from table 1 and the active ingredients as described above is not essential for working the present invention.

Some of said combinations according to the invention have a systemic action and can be

used as foliar, soil and seed treatment fungicides. With the combinations according to the invention it is possible to inhibit or destroy the

phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of plants which grow later are also protected from attack by phytopathogenic microorganisms. The combinations of the present invention are of particular interest for controlling a large number of fungi in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.

The combinations according to the invention are applied by treating the fungi, the useful plants, the locus thereof, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials threatened by fungus attack with a combination of components (A) and (B), preferably in a synergistically effective amount.

The combinations according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials by the fungi.

The combinations according to the invention are particularly useful for controlling the following plant diseases:

Alternaria species in fruit and vegetables,

Ascochyta species in pulse crops,

Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes,

Cercospora arachidicola in peanuts,

Cochliobolus sativus in cereals, Colletotrichum species in pulse crops,

Erysiphe species in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Fusarium species in cereals and maize,

Gaumannomyces graminis in cereals and lawns,

Helminthosporium species in maize, rice and potatoes,

Hemileia vastatrix on coffee,

Microdochium species in wheat and rye,

Phakopsora species in soybean,

Puccinia species in cereals, broadleaf crops and perrenial plants,

Pseudocercosporella species in cereals,

Phragmidium mucronatum in roses,

Podosphaera species in fruits,

Pyrenophora species in barley,

Pyricularia oryzae in rice,

Ramularia collo-cygni in barley,

Rhizoctonia species in cotton, soybean, cereals, maize, potatoes, rice and lawns,

Rhynchosporium secalis in barley and rye,

Sclerotinia species in lawns, lettuce, vegetables and oil seed rape,

Septoria species in cereals, soybean and vegetables,

Sphacelotheca reilliana in maize,

Tilletia species in cereals,

Uncinula necator, Guignardia bidwellii and Phomopsis viticola in vines,

Urocystis occulta in rye,

Ustilago species in cereals and maize,

Venturia species in fruits,

Monilinia species on fruits,

Penicillium species on citrus and apples. The combinations according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention which are partially known for their insecticidal action act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the combinations according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate, a good activity corresponding to a destruction rate (mortality) of at least 50 to 60%.

Examples of the abovementioned animal pests are:

from the order Acarina, for example,

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;

from the order Coleoptera, for example,

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.;

from the order Diptera, for example,

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp.,

Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;

from the order Heteroptera, for example,

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;

from the order Homoptera, for example,

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp.,

Nilaparvata spp., Parlatoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp.,

Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;

from the order Hymenoptera, for example, Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.;

from the order Isoptera, for example,

Reticulitermes spp.;

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiela, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.;

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

from the order Thysanoptera, for example,

Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii, Taeniothrips spp., Thrips palmi and Thrips tabaci;

from the order Thysanura, for example,

Lepisma saccharina;

nematodes, for example root knot nematodes, stem eelworms and foliar nematodes;

especially Heterodera spp., for example Heterodera schachtii, Heterodora avenae and Heterodora trifolii; Globodera spp., for example Globodera rostochiensis; Meloidogyne spp., for example Meloidogyne incoginita and Meloidogyne javanica; Radopholus spp., for example Radopholus similis; Pratylenchus, for example Pratylenchus neglectans and Pratylenchus penetrans; Tylenchulus, for example Tylenchulus semipenetrans; Longidorus, Trichodorus, Xiphinema, Ditylenchus,

Aphelenchoides and Anguina;

crucifer flea beetles (Phyllotreta spp.);

root maggots (Delia spp.) and

cabbage seedpod weevil (Ceutorhynchus spp.).

The combinations according to the invention can be used for controlling, i. e. containing or destroying, animal pests of the abovementioned type which occur on useful plants in agriculture, in horticulture and in forests, or on organs of useful plants, such as fruits, flowers, foliage, stalks, tubers or roots, and in some cases even on organs of useful plants which are formed at a later point in time remain protected against these animal pests. When applied to the useful plants the component (A) is applied at a rate of 5 to 2000 g a.i./ha, particularly 10 to 1000 g a.i./ha, e.g. 50, 75, 100 or 200 g a.i./ha, in association with 1 to 5000 g a.i./ha, particularly 2 to 2000 g a.i./ha, e.g. 100, 250, 500, 800, 1000, 1500 g a.i./ha of component (B), depending on the class of chemical employed as component (B). In agricultural practice the application rates of the combination according to the invention depend on the type of effect desired, and typically range from 20 to 4000 g of total combination per hectare.

When the combinations of the present invention are used for treating seed, rates of 0.001 to 50 g of a compound of formula I per kg of seed, preferably from 0.01 to 10g per kg of seed, and 0.001 to 50 g of a compound of component (B), per kg of seed, preferably from 0.01 to 10g per kg of seed, are generally sufficient.

The invention also provides fungicidal compositions comprising a combination of components (A) and (B) as mentioned above in a synergistically effective amount, together with an agriculturally acceptable carrier, and optionally a surfactant. In said compositions, the weight ratio of (A) to (B) is preferably between 1000 : 1 and 1 : 1000, especially from 50: 1 to 1 :50, more especially in a ratio of from 20: 1 to 1 :20, even more especially from 10: 1 to 1 : 10, very especially from 5: 1 and 1 :5, special preference being given to a ratio of from 2:1 to 1 :2, and a ratio of from 4: 1 to 2: 1 being likewise preferred, above all in a ratio of 1 :1 , or 5: 1 , or 5:2, or 5:3, or 5:4, or 4: 1 , or 4:2, or 4:3, or 3: 1 , or 3:2, or 2: 1 , or 1 :5, or 2:5, or 3:5, or 4:5, or 1 :4, or 2:4, or 3:4, or 1 :3, or 2:3, or 1 :2, or 1 :600, or 1 :300, or 1 : 150, or 1 :35, or 2:35, or 4:35, or 1 :75, or 2:75, or 4:75, or 1 :6000, or 1 :3000, or 1 : 1500, or 1 :350, or 2:350, or 4:350, or 1 :750, or 2:750, or 4:750. The compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra- low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). Also conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules.

In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), the active agent consisting of at least the compound of formula I together with component (B) and (C), and optionally other active agents, particularly microbiocides or conserva- tives or the like. Concentrated forms of compositions generally contain in 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. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.

The Examples which follow serve to illustrate the invention, "active ingredient" denoting a mixture of compound I and compounds of component (B) in a specific mixing ratio.

Formulation Examples

Wettable powders a) b) c) active ingredient [I : comp (B) = 1 :3(a), 1 :2(b), 1 : 1 (c)] 25 % 50 % 75 % sodium lignosulfonate 5 % 5 %

sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % phenol polyethylene glycol ether - 2 %

(7-8 mol of ethylene oxide)

highly dispersed silicic acid 5 % 10 % 10 %

Kaolin 62 % 27 %

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

Powders for drv seed treatment a) b) c) active ingredient [I : comp (B) = 1 :3(a), 1 :2(b), 1 : 1 (c)] 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % -

Kaolin 65 % 40 % -

Talcum 20

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Emulsifiable concentrate

active ingredient (I : comp (B) = 1 :6) 10 %

octylphenol polyethylene glycol ether 3 %

(4-5 mol of ethylene oxide)

calcium dodecylbenzenesulfonate 3 %

castor oil polyglycol ether (35 mol of ethylene oxide) 4 %

Cyclohexanone 30 % xylene mixture 50 %

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

Dusts a) b) c)

Active ingredient [I : comp (B) = 1 :6(a), 1 :2(b), 1 :10(c)] 5 % 6 % 4 % talcum 95 %

Kaolin - 94 %

mineral filler - - 96 %

Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

Extruder granules

Active ingredient (I : comp (B) = 2: 1 ) 15 %

sodium lignosulfonate 2 %

carboxymethylcellulose 1 %

Kaolin 82 %

The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Coated granules

Active ingredient (I :comp (B) = 1 : 10) 8 %

polyethylene glycol (mol. wt. 200) 3 %

Kaolin 89 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Suspension concentrate

active ingredient (I : comp (B) = 1 :8) 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %

Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 %

Water 32 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. Flowable concentrate for seed treatment

active ingredient (I : comp (B) = 1 :8) 40 % propylene glycol 5 % copolymer butanol PO/EO 2 % tristyrenephenole with 10-20 moles EO 2 %

1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 %

Silicone oil (in the form of a 75 % emulsion in water) 0.2 %

Water 45.3 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of a combination of the compound of formula I and a component (B), or of each of these compounds separately, are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.

The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

Biological Examples

Botrvtis cinerea (gray mould):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96- well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 72 hours.

Glomerella lagenarium (svn. Colletotrichum lagenarium, anthracnose of cucurbits):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96- well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 72 hours at 620nm. Pyricularia orzyae (rice blast):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96- well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 72 hours.

Venturia inequalis (apple scab):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96- well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 7 days at 620nm.

Alternaria solani (early blight tomato/potato):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96- well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 48 hours.

Septoria tritici (leaf blotch):

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96- well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24 C and the inhibition of growth was determined photometrically after 72 hours.

Results:

The compound of formula I, wherein R is hydrogen, is represented by the compound of formula la. The compound of formula I, wherein R is fluoro, is represented by the compound of formula lb.

Example B1 : Compositions comprising the compound of formula la and azoxystrobin as component

Alternaria solani Azoxystrobin Formula la observed expected

ppm ppm % activity action (colby)

0.0063 31

0.0125 59 0.0250 71

0.0003 7

0.0006 0

0.0012 0

0.0025 0

0.0050 0

0.0063 0.0003 54 36

0.0063 0.0006 49 31

0.0063 0.0012 51 31

0.0063 0.0025 48 31

0.0125 0.0025 71 59

0.0125 0.0050 80 59

0.0250 0.0006 79 71

0.0250 0.0012 79 71

0.0250 0.0025 80 71

0.0250 0.0050 85 71

Botrytis cinerea

Colletotrichum

lagenarium

Pyricularia oryzae Azoxystrobin Formula la observed expected

ppm ppm % activity action (colby)

0.0004 17

0.0008 0

0.0016 5

0.0031 34 0.0063 62

0.0125 78

0.0001 0

0.0002 0

0.0003 46

0.0006 87

0.0004 0.0002 44 17

0.0008 0.0003 68 46

0.0016 0.0002 46 5

0.0016 0.0003 62 49

0.0016 0.0006 97 88

0.0031 0.0001 52 34

0.0031 0.0002 78 34

0.0031 0.0003 97 64

0.0063 0.0002 97 62

0.0063 0.0003 97 79

0.0125 0.0003 100 88

Venturia inequalis

Example B2: compositions comprising the compound of formula I and benzovindiflupyr as component (B):

Alternaria solani Benzovindiflupyr Formula la observed expected

% action ppm ppm activity

0.0125 5

0.0250 64

0.0003 0

0.0006 0

0.0012 0

0.0050 4

0.0125 0.0003 41

0.0125 0.0006 49 0.0250 0.0012 81 64

0.0250 0.0050 73 65

Botrytis cinerea Benzovindiflupyr Formula la observed expected

% action ppm ppm activity (col by)

0.0125 55

0.0006 13

0.0125 0.0006 79 61

Colletotrichum

lagenarium Benzovindiflupyr Formula la observed expected

% action ppm ppm activity (col by)

0.0500 41

0.1000 76

0.0012 2

0.0025 6

0.0050 0

0.0100 10

0.0500 0.0012 50 42

0.0500 0.0100 67 47

0.1000 0.0025 89 78

0.1000 0.0050 85 76

Septoria tritici Benzovindiflupyr Formula la observed expected

% action ppm ppm activity (col by)

0.0250 33

0.0500 56

0.0006 0

0.0012 1

0.0250 0.0006 45 33

0.0500 0.0012 65 57

Pyricularia oryzae Benzovindiflupyr Formula la observed expected

% action ppm ppm activity (col by)

0.0016 25

0.0031 44

0.0000 0

0.0001 0

0.0002 16

0.0016 0.0000 54 25

0.0016 0.0001 44 25

0.0031 0.0001 75 44

0.0031 0.0002 73 53

Venturia inequalis Benzovindiflu Formula la observed expected ppm ppm % action activity (col by)

0.0031 32

0.0063 76

0.0001 0

0.0002 5

0.0003 0

0.0006 0

0.0012 0

0.0031 0.0001 61 32

0.0031 0.0002 61 36

0.0031 0.0003 60 32

0.0031 0.0012 43 32

0.0063 0.0002 93 77

0.0063 0.0006 84 76

Example B3: compositions comprising the compound of formula la and chlorothalonil as component Alternaria

solani Chlorothalonil Formula la observed expected

Botrytis cinerea Chlorothalonil Formula la observed expected

Chlorothalonil Formula la observed expected

% action ppm ppm activity (colby)

0.5000 51

0.0025 8 0.0050 0

0.0100 1

0.5000 0.0025 61 55

0.5000 0.0050 76 51

0.5000 0.0100 83 51

Septoria tritici Chlorothalonil Formula la observed expected

% action ppm ppm activity (col by)

0.2500 74

0.0012 6

0.2500 0.0012 90 76

Pyricularia

Venturia

inequalis Chlorothalonil Formula la observed expected

Example B4: compositions comprising the compound of formula la and cyprodinil as component

Alternaria solani Cyprodinil Formula la observed expected

% action ppm ppm activity (colby) 0.0100 30

0.0250 0.0100 46 30

Botrytis cinerea Cyprodinil Formula la observed expected

% action ppm ppm activity (col by)

0.0031 3

0.0012 53

0.0031 0.0012 65 55

Pyricularia

Cyprodinil Formula la observed expected

% action ppm ppm activity (col by)

0.0016 10

0.0006 84

0.0016 0.0006 98 85

Venturia

inequalis Cyprodinil Formula la observed expected

% action ppm ppm activity (colby)

Example B5: compositions comprising the compound of formula la and difenoconazole as component (B):

Botrytis cinerea Difenoconazole Formula la observed expected

% action ppm ppm activity (colby)

Colletotrichum Difenoconazole Formula la observed expected lagenarium

% action ppm ppm activity (colby)

Difenoconazole Formula la observed expected

% action ppm ppm activity (colby)

Example B6: compositions comprising the compound of formula la and fluazinam as component Alternaria

solani Fluazinam Formula la observed expected

% action ppm ppm activity (colby)

0.0125 0

0.0250 19 0.0500 42

0.0006 2

0.0012 9

0.0025 0

0.0050 17

0.0100 28

0.0125 0.0050 51 17

0.0250 0.0006 44 21

0.0250 0.0100 58 41

0.0500 0.0012 73 48

0.0500 0.0025 69 42

0.0500 0.0100 64 58

Fluazinam Formula la observed expected

% action ppm ppm activity (col by)

0.0016 3

0.0031 5

0.0125 22

0.0250 61

0.0006 13

0.0012 56

0.0016 0.0006 40 16

0.0031 0.0012 73 59

0.0125 0.0006 41 32

0.0250 0.0006 90 66

Fluazinam Formula la observed expected

% action ppm ppm activity (colby)

0.0250 1 1

0.0500 45

0.0012 1

0.0025 5

0.0050 0

0.0100 3 0.0200 72

0.0250 0.0100 94 13

0.0500 0.0012 100 46

0.0500 0.0025 94 48

0.0500 0.0050 94 45

0.0500 0.0100 100 47

0.0500 0.0200 100 85

Septoria tritici Fluazinam Formula la observed expected

% action ppm ppm activity (colby)

Pyricularia

oryzae Fluazinam Formula la observed expected

% action ppm ppm activity (colby)

0.0004 0

0.0008 0

0.0063 0

0.0125 63

0.0002 37

0.0003 59

0.0004 0.0002 45 37

0.0008 0.0003 68 59

0.0063 0.0002 56 37

0.0063 0.0003 76 59

0.0125 0.0003 100 85 Venturia

inequalis Fluazinam Formula la observed expected

% action ppm ppm activity (colby)

Example B7: compositions comprising the compound of formula la and fludioxonil as component Alternaria

solani Fludioxonil Formula la observed expected

% action ppm ppm activity (colby)

0.0125 27

0.0250 33

0.0500 41

0.1000 56

0.0003 2

0.0012 0

0.0025 0

0.0050 5

0.0100 30 0.0125 0.0003 44 29

0.0125 0.0012 49 27

0.0125 0.0025 44 27

0.0125 0.0050 53 30

0.0250 0.0012 46 33

0.0250 0.0025 46 33

0.0250 0.0050 47 36

0.0250 0.0100 61 53

0.0500 0.0012 56 41

0.0500 0.0025 51 41

0.0500 0.0050 50 43

0.1000 0.0025 73 56

0.1000 0.0050 77 58

0.1000 0.0100 81 69

Fludioxonil Formula la observed expected

% action ppm ppm activity (col by)

0.0031 10

0.0063 3

0.0125 27

0.0250 65

0.0006 6

0.0012 56

0.0031 0.0012 68 60

0.0063 0.0012 65 57

0.0125 0.0006 58 31

0.0125 0.0012 80 67

0.0250 0.0006 87 67

0.0250 0.0012 99 85

Fludioxonil Formula la observed expected

% action ppm ppm activity (colby)

0.0250 1

0.0500 2 0.1000 0

0.2000 3

0.0100 0

0.0200 70

0.0250 0.0100 71 1

0.0500 0.0100 67 2

0.0500 0.0200 99 71

0.1000 0.0200 97 70

0.2000 0.0100 74 3

0.2000 0.0200 97 71

Fludioxonil Formula la observed expected

% action ppm ppm activity (col by)

0.2000 53

0.0050 0

0.2000 0.0050 64 53

Fludioxonil Formula la observed expected

% action ppm ppm activity (colby)

0.0008 0

0.0016 0

0.0031 5

0.0063 0

0.0125 0

0.0250 0

0.0002 29

0.0003 55

0.0006 85

0.0008 0.0003 61 55

0.0016 0.0006 95 85

0.0031 0.0006 95 86

0.0063 0.0002 46 29

0.0063 0.0003 70 55

0.0063 0.0006 95 85 0.0125 0.0003 94 55

0.0125 0.0006 98 85

0.0250 0.0006 98 85

Venturia

inequalis Fludioxonil Formula la observed expected

% action ppm ppm activity (colby)

Example B8: compositions comprising the compound of formula la and hexaconazole as component (B):

Alternaria

solani Hexaconazole Formula la observed expected

% action ppm ppm activity (colby)

Colletotrichum

lagenarium Hexaconazole Formula la observed expected ppm ppm % action activity (colby)

Hexaconazole Formula la observed expected

% action ppm ppm activity (colby)

Venturia

inequalis Hexaconazole Formula la observed expected

% action ppm ppm activity (colby)

Example B9: compositions comprising the compound of formula la and isopyrazam as component Alternaria Isopyraza

solani m Formula la observed expected

% action

ppm ppm activity (colby)

0.0078 7

0.0000 0

0.0078 0.0000 48 7 Isopyraza

Botrytis cinerea m Formula la observed expected

% action ppm ppm activity (colby)

Colletotrichum Isopyraza

lagenarium m Formula la observed expected

% action ppm ppm activity (colby)

Isopyraza

Septoria tritici m Formula la observed expected

% action ppm ppm activity (colby)

0.0313 44

0.0625 59

0.1250 81

0.0001 0

0.0002 0

0.0003 0

0.0006 0 0.0050 0

0.0313 0.0001 48 44

0.0313 0.0002 55 44

0.0625 0.0002 70 59

0.0625 0.0003 72 59

0.0625 0.0006 70 59

0.1250 0.0050 93 81

Pyricularia Isopyraza

oryzae m Formula la observed expected

% action ppm ppm activity (col by)

0.0078 23

0.0156 63

0.0000 0

0.0078 0.0000 63 23

0.0156 0.0000 69 63

Venturia Isopyraza

inequalis m Formula la observed expected

% action ppm ppm activity (col by)

0.0313 36

0.0625 56

0.1250 88

0.2500 90

0.0002 0

0.0003 0

0.0006 0

0.0012 0

0.0025 14

0.0313 0.0002 94 36

0.0625 0.0002 73 56

0.0625 0.0003 94 56

0.0625 0.0025 75 62

0.1250 0.0006 100 88

0.1250 0.0012 100 88 0.2500 0.0006 100 90

0.2500 0.0012 100 90

Example B10: compositions comprising the compound of formula la and propiconazole as component (B):

Alternaria

solani Propiconazole Formula la observed expected

Colletotrichum

lagenarium Propiconazole Formula la observed expected

Example B1 1 : compositions comprising the compound of formula la and pyroguilon as component

Alternaria

solani Pyroguilon Formula la observed expected

% action PPm PPm activity (col by)

Colletotrichum

lagenarium Pyroguilon Formula la observed expected % action ppm ppm activity (col by)

5.0000 1

10.0000 2

20.0000 6

0.0100 0

0.0200 66

5.0000 0.0200 82 66

10.0000 0.0200 81 67

20.0000 0.0100 48 6

20.0000 0.0200 86 68

Pyricularia

Pyroquilon Formula la observed expected

% action ppm ppm activity (col by)

0.0391 5

0.0002 22

0.0391 0.0002 49 27

Venturia

inequalis Pyroquilon Formula la observed expected

Example B12: compositions comprising the compound of formula la and trizyclazole as component Alternaria

solani Trizyclazole Formula la observed expected

% action ppm ppm activity (colby) 5.0000 3

0.0100 29

5.0000 0.0100 42 31

Botrytis cinerea Trizyclazole Formula la observed expected

% action ppm ppm activity (col by)

0.3125 0

0.0012 49

0.3125 0.0012 58 49

Colletotrichum

lagenarium Trizyclazole Formula la observed expected

% action ppm ppm activity (col by)

10.0000 0

20.0000 6

0.0100 0

0.0200 67

10.0000 0.0200 75 67

20.0000 0.0100 56 6

20.0000 0.0200 79 69

Venturia

inequalis Trizyclazole Formula la observed expected

% action ppm ppm activity (col by)

5.0000 0

10.0000 0

20.0000 0

0.0050 36

0.0100 36

0.0200 66

5.0000 0.0100 50 36

5.0000 0.0200 74 66

10.0000 0.0100 74 36

20.0000 0.0050 66 36

20.0000 0.0100 86 36

20.0000 0.0200 83 66

Example B13: compositions comprising the compound of formula lb and azoxystrobin as component

Alternaria solani Azoxystrobin Formula observed expected

lb % action (colby)

ppm ppm activity

0,0063 1

0,0125 35 0,0003 0

0,0006 0

0,0012 0

0,0025 0

0,0050 22

0,0063 0,0012 47 1

0,0063 0,0025 52 1

0,0125 0,0003 59 35

0,0125 0,0006 60 35

0,0125 0,0012 60 35

0,0125 0,0025 74 35

0,0125 0,0050 86 49

Botrytis cinerea Azoxystrobin Formula observed expected lb % action (colby) ppm ppm activity

0,0063 0

0,0125 0

0,0250 0

0,0500 0

0, 1000 14

0,0006 35

0,0012 74

0,0025 84

0,0063 0,0006 45 35

0,0125 0,0006 56 35

0,0250 0,0006 72 35

0,0500 0,0012 88 74

0,0500 0,0025 93 84

0, 1000 0,0025 95 86

Colletotrichum lagenarium Azoxystrobin Formula observed expected lb % action (colby) ppm ppm activity

0,0500 45

0,0012 0

0,0025 0

0,0050 0

0,0100 0

0,0200 0

0,0500 0,0012 84 45

0,0500 0,0025 84 45

0,0500 0,0050 61 45

0,0500 0,0100 59 45

0,0500 0,0200 76 45

Septoria tritici Azoxystrobin Formula observed expected lb % action (colby) ppm ppm activity

0,0125 47 0,0250 74

0,0003 7

0,0006 1

0,0012 0

0,0050 0

0,0125 0,0003 61 51

0,0125 0,0012 53 47

0,0125 0,0050 55 47

0,0250 0,0006 87 74

Pyricularia oryzae Azoxystrobin Formula observed expected

lb % action (colby) ppm ppm activity

0,0016 15

0,0031 10

0,0063 41

0,0125 84

0,0002 2

0,0003 0

0,0006 3

0,0012 60

0,0016 0,0006 57 17

0,0031 0,0006 71 13

0,0031 0,0012 88 64

0,0063 0,0002 72 42

0,0063 0,0003 82 41

0,0063 0,0006 91 43

0,0063 0,0012 93 76

0,0125 0,0006 96 85

Example B14: compositions comprising the compound of formula lb and benzovindiflupyr as component (B):

Alternaria solani BenzovinFormula observed expected

diflupyr lb % action

ppm ppm activity (colby)

0,0125 26

0,0006 0

0,0125 0,0006 52 26

Botrytis cinerea BenzovinFormula observed expected

diflupyr lb % action

ppm ppm activity (colby)

0,0031 0

0,0012 68

0,0031 0,0012 77 68

Colletotrichum BenzovinFormula observed expected lagenarium diflupyr lb % action ppm ppm activity (col by)

0,0500 19

0,0012 0

0,0500 0,0012 60 19

Septoria tritici Benzovin- Formula observed expected diflupyr lb % action ppm ppm activity (col by)

0,0250 40

0,0500 56

0,0012 0

0,0100 0

0,0200 0

0,0250 0,0012 45 40

0,0250 0,0100 44 40

0,0500 0,0012 67 56

0,0500 0,0100 65 56

0,0500 0,0200 67 56

Pyricularia oryzae Benzovin- Formula observed expected diflupyr lb % action ppm ppm activity (col by)

0,0016 30

0,0031 66

0,000039 9

0,0002 0

0,0016 0,000039 40 36

0,0031 0,0002 73 66

Venturia inequalis Benzovin- Formula observed expected diflupyr lb % action ppm ppm activity (col by)

0,0016 15

0,0031 48

0,0125 77

0,0001 0

0,0006 0

0,0050 6

0,0016 0,0001 51 15

0,0016 0,0006 46 15

0,0031 0,0001 68 48

0,0031 0,0006 55 48

0,0125 0,0050 92 79

Example B15: compositions comprising the compound of formula lb and chlorothalonil as component (B):

Alternaria solani Chlorothalonil Formula lb observed expected

% activity action ppm ppm (col by)

2,0000 55

0,0050 50

2,0000 0,0050 94 78

Botrytis cinerea Chlorothalonil Formula lb observed expected

% activity action ppm ppm (col by)

0,0156 7

0,0313 5

0, 1250 1

0,2500 40

0,0006 24

0,0012 65

0,0156 0,0006 42 30

0,0313 0,0012 86 66

0, 1250 0,0006 58 25

0, 1250 0,0012 78 65

0,2500 0,0006 90 55

0,2500 0,0012 90 79

Colletotrichum Chlorothalonil Formula lb observed expected lagenarium % activity action ppm ppm (col by)

0,5000 7

0,0025 0

0,5000 0,0025 42 7

Septoria tritici Chlorothalonil Formula lb observed expected

% activity action ppm ppm (col by)

0, 1250 62

0,0003 0

0, 1250 0,0003 77 62

Pyricularia Chlorothalonil Formula lb observed expected oryzae % activity action ppm ppm (col by)

0,0313 0

0,0625 3

0, 1250 44

0,0003 0

0,0006 1

0,0012 61

0,0025 85

0,0313 0,0012 68 61

0,0625 0,0025 95 85 0, 1250 0,0003 99 44

0, 1250 0,0006 99 44

0, 1250 0,0012 99 78

Venturia Chlorothalonil Formula lb observed expected inequalis % activity action

ppm ppm (col by)

0,0625 49

0,0002 0

0,0003 0

0,0625 0,0002 61 49

0,0625 0,0003 57 49

Example B16: compositions comprising the compound of formula lb and cyprodinil as component (B):

Example B17: compositions comprising the compound of formula lb and difenoconazole as component (B):

Alternaria Difenoconazole Formula lb observed expected solani % activity action (colby) ppm ppm

0,0313 38

0,0625 58 0,0003 12

0,0006 6

0,0025 0

0,0313 0,0006 46 41

0,0625 0,0003 74 63

0,0625 0,0025 65 58

Botrytis cinerea Difenoconazole Formula lb observed expected

% activity action (colby) ppm ppm

0,2500 39

0,0006 35

0,2500 0,0006 80 61

Colletotrichum Difenoconazole Formula lb observed expected lagenarium % activity action (colby) ppm ppm

1 ,0000 29

0,0025 4

1 ,0000 0,0025 73 32

Septoria tritici Difenoconazole Formula lb observed expected

% activity action (colby) ppm ppm

0,0156 39

0,0313 69

0,000039 1

0,0001 1

0,0003 0

0,0006 2

0,0156 0,000039 55 39

0,0156 0,0003 47 39

0,0156 0,0006 47 40

0,0313 0,0001 80 69

Pyricularia Difenoconazole Formula lb observed expected oryzae % activity action (colby) ppm ppm

0,0313 0

0,5000 70

0,0012 59

0,0313 0,0012 68 59

0,5000 0,0012 100 88

Venturia Difenoconazole Formula lb observed expected inequalis % activity action (colby) ppm ppm

0,0078 35

0,0156 62

0,000039 7

0,0001 0

0,0002 9

0,0006 15

0,0078 0,0000 51 40

0,0156 0,000039 100 65

0,0156 0,0001 79 62

0,0156 0,0002 89 66

0,0156 0,0006 90 68

Example B18: compositions comprising the compound of formula lb and fluazinam as component (B):

Alternaria Fluazinam Formula lb observed expected solani % activity action (colby) ppm ppm

0,0250 0

0,0500 55

0,0012 14

0,0025 0

0,0100 46

0,0200 59

0,0250 0,0012 46 14

0,0250 0,0100 79 46

0,0500 0,0012 88 61

0,0500 0,0025 84 55 0,0500 0,0200 95 82

Botrytis cinerea Fluazinam Formula lb observed expected

% activity action (colby) ppm ppm

0,0125 4

0,0250 14

0,0006 42

0,0012 70

0,0125 0,0006 62 44

0,0250 0,0006 87 50

0,0250 0,0012 88 74

Colletotrichum Fluazinam Formula lb observed expected lagenarium % activity action (colby) ppm ppm

0,0250 5

0,0500 62

0,0012 8

0,0025 0

0,0050 0

0,0100 2

0,0200 0

0,0250 0,0100 95 7

0,0500 0,0012 100 65

0,0500 0,0025 100 62

0,0500 0,0050 73 62

0,0500 0,0100 79 63

0,0500 0,0200 100 62

Septoria tritici Fluazinam Formula lb observed expected

% activity action (colby) ppm ppm

0,0250 13

0,0500 29

0, 1000 57

0,0012 1 0,0025 0

0,0050 1

0,0100 0

0,0200 2

0,0250 0,0100 41 13

0,0500 0,0012 53 29

0,0500 0,0025 41 29

0,0500 0,0200 65 30

0, 1000 0,0025 84 57

0, 1000 0,0050 67 58

Pyricularia Fluazinam Formula lb observed expected oryzae % activity action (colby) ppm ppm

0,0063 0

0,0125 10

0,0250 45

0,0003 0

0,0006 4

0,0012 57

0,0063 0,0012 69 57

0,0125 0,0003 57 10

0,0125 0,0006 45 13

0,0125 0,0012 75 62

0,0250 0,0006 100 47

0,0250 0,0012 100 77

Venturia Fluazinam Formula lb observed expected inequalis % activity action (colby) ppm ppm

0, 1000 0

0,2000 38

0,0025 5

0,0050 19

0,0100 21

0,0200 32

0, 1000 0,0025 49 5 0, 1000 0,0100 49 21

0, 1000 0,0200 54 32

0,2000 0,0050 72 50

0,2000 0,0100 72 51

0,2000 0,0200 87 58

Example B19: compositions comprisinq the compound of formula lb and fludioxonil as component (B):

Alternaria Fludioxonil Formula lb observed expected solani % activity action (colby) ppm ppm

0,0063 14

0,0125 0

0,0250 19

0,0500 21

0, 1000 60

0,0012 0

0,0025 16

0,0050 41

0,0100 42

0,0200 72

0,0063 0,0025 42 28

0,0125 0,0025 43 16

0,0125 0,0050 54 41

0,0250 0,0050 63 52

0,0250 0,0100 79 53

0,0500 0,0012 76 21

0,0500 0,0025 64 34

0,0500 0,0050 61 54

0,0500 0,0100 84 54

0,0500 0,0200 88 78

0, 1000 0,0025 76 67

0, 1000 0,0100 86 77

Botrytis Fludioxonil Formula lb observed expected cinerea % activity action (colby) ppm ppm 0,0016 5

0,0031 0

0,0063 0

0,0125 0

0,0250 60

0,0003 9

0,0006 42

0,0012 71

0,0025 86

0,0016 0,0006 63 45

0,0031 0,0006 62 42

0,0031 0,0012 84 71

0,0063 0,0006 74 42

0,0063 0,0012 85 71

0,0125 0,0003 81 9

0,0125 0,0006 86 42

0,0125 0,0012 94 71

0,0125 0,0025 98 86

0,0250 0,0006 98 77

0,0250 0,0012 99 88

Septoria tritici Fludioxonil Formula lb observed expected

% activity action (colby) ppm ppm

0,2000 46

0,0050 1

0,2000 0,0050 53 46

Pyricularia Fludioxonil Formula lb observed expected oryzae % activity action (colby) ppm ppm

0,0016 12

0,0031 0

0,0063 0

0,0125 0

0,0250 1 1

0,0500 20 0,0006 12

0,0012 78

0,0016 0,0006 53 22

0,0031 0,0012 90 78

0,0063 0,0012 90 78

0,0125 0,0006 53 12

0,0125 0,0012 92 78

0,0250 0,0006 81 21

0,0250 0,0012 92 80

0,0500 0,0012 98 82

Example B20: compositions comprising the compound of formula lb and hexaconazole as component (B):

Alternaria Hexaconazole Formula lb observed expected solani % activity action (colby) ppm ppm

0, 1250 52

0,0003 19

0, 1250 0,0003 69 61

Botrytis Hexaconazole Formula lb observed expected cinerea % activity action (colby) ppm ppm

0, 1250 10

0,0003 0

0,0006 27

0, 1250 0,0003 54 10

0, 1250 0,0006 56 35

Venturia Hexaconazole Formula lb observed expected inegualis % activity action (colby) ppm ppm

0,0625 90

0,0002 6

0,0625 0,0002 100 90 Example B21 : compositions comprising the compound of formula lb and isopyrazam as component

Alternaria Isopyrazam Formula lb observed expected

solani % activity action (colby)

ppm ppm

0,0078 41

0,0000 0

0,0001 0

0,0002 0

0,0003 0

0,0078 0,0000 49 41

0,0078 0,0001 45 41

0,0078 0,0002 54 41

0,0078 0,0003 59 41

Botrytis Isopyrazam Formula lb observed expected

cinerea % activity action (colby)

ppm ppm

0,0156 46

0,0000 4

0,0001 3

0,0156 0,0000 67 48

0,0156 0,0001 54 48

Venturia Isopyrazam Formula lb observed expected

inequalis % activity action (colby)

ppm ppm

0,0313 31

0,0625 68

0, 1250 76

0,2500 83

0,0001 20

0,0003 0

0,0006 0

0,0012 0

0,0025 9

0,0050 13 0,0313 0,0001 56 45

0,0313 0,0003 57 31

0,0313 0,0006 47 31

0,0625 0,0003 75 68

0, 1250 0,0006 88 76

0, 1250 0,0025 90 78

0,2500 0,0006 96 83

0,2500 0,0012 100 83

0,2500 0,0025 93 84

0,2500 0,0050 95 85

Example B22: compositions comprising the compound of formula lb and propiconazole as component (B):

Alternaria Propiconazole Formula lb observed expected solani % activity action (colby) ppm ppm

0,5000 49

0,0012 2

0,0025 21

0,5000 0,0012 59 50

0,5000 0,0025 73 59

Botrytis Propiconazole Formula lb observed expected cinerea % activity action (colby) ppm ppm

0,2500 60

0,0006 28

0,2500 0,0006 87 71

Septoria tritici Propiconazole Formula lb observed expected

% activity action (colby) ppm ppm

0, 1250 36

0,2500 69

0,0003 2

0,0006 0

0, 1250 0,0003 51 37 0,2500 0,0006 80 69

Pyricularia Propiconazole Formula lb observed expected oryzae % activity action (colby) ppm ppm

0,0313 0

0,0012 69

0,0313 0,0012 84 69

Example B23: compositions comprisinq the compound of formula lb and pvroquilon as component (B):

Alternaria Pyroquilon Formula lb observed expected solani % activity action (colby) ppm ppm

5,0000 3

0,0100 42

5,0000 0,0100 51 44

Botrytis Pyroquilon Formula lb observed expected cinerea % activity action (colby) ppm ppm

0, 1563 0

2,5000 0

0,0006 30

0, 1563 0,0006 42 30

2,5000 0,0006 40 30

Pyricularia Pyroquilon Formula lb observed expected oryzae % activity action (colby) ppm ppm

0,3125 0

0,0012 76

0,3125 0,0012 87 76

Venturia Pyroquilon Formula lb observed expected inequalis % activity action (colby) ppm ppm 10,0000 0

20,0000 0

0,0200 29

10,0000 0,0200 44 29

20,0000 0,0200 45 29

Example B24: compositions comprising the compound of formula lb and tricyclazole as component (B):

Alternaria Trizyclazole Formula lb observed expected solani % activity action (colby) ppm ppm

Botrytis Trizyclazole Formula lb observed expected cinerea % activity action (colby) ppm ppm

0,3125 0

0,0012 62

0,3125 0,0012 70 62

Venturia Trizyclazole Formula lb observed expected inegualis % activity action (colby) ppm ppm

20,0000 0

0,0200 35

20,0000 0,0200 78 35