WO2025131902A1

WO2025131902A1 - Methods for protecting plants using mixtures comprising sulfur, selected terpenes and phosphites.

Info

Publication number: WO2025131902A1
Application number: PCT/EP2024/085587
Authority: WO
Inventors: Raffaello ZITO; Ulla HILSINGER; Annett KUEHN
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2023-12-21
Filing date: 2024-12-11
Publication date: 2025-06-26
Anticipated expiration: 2026-06-21

Abstract

The present invention relates to mixtures comprising sulfur, selected terpenes and phosphites as well as to methods for protecting plants using such mixtures.

Description

Methods for protecting plants using mixtures comprising sulfur, selected terpenes and phosphites.

Field of the Invention

The present invention relates to mixtures comprising sulfur, selected terpenes and phosphites, as well as to methods for protecting plants using such mixtures.

Background of the Invention

Crop plants are under constant threat by plant pathogens and plant pests. Thus, there is a constant need to develop a broad toolkit of alternative pesticides to protect crop plants and to improve on the shortcomings of existing pesticides. One interest is to develop pesticides based on natural compounds, which show the same performance and ease of application as comparable pesticides based on synthetic compounds.

One of the oldest natural occurring fungicides, which is still widely used, is elemental sulfur. It is considered to have a very low impact on the environment and is one of the few compounds allowed as pesticide in organic agriculture. Sulfur is mainly used to protect fruits, vegetables and grapevines against phytopathogenic fungi, mites and insects, like aphids. Sulfur fungicides are generally formulated as wettable powders or water dispersible granules. Sulfur wettable powder formulations are dusty and pose a risk to the user, mostly because of eye irritation, inhalation risk and skin irritation. Granular formulations are less dusty, but more expensive in production. An improved formulation type are suspension concentrates. However, water-based suspension concentrates of sulfur frequently show sedimentation during storage which is difficult to re-suspend and tend to form a supernatant serum. Sulfur particles formed during storage may block spray nozzles. Another problem of water-based suspension concentrates is a low pourability and a high viscosity, which reduces the ease of application for the user of these formulations. Variants of water-based suspension concentrates comprising different kinds of fatty acid or terpene-based plant oils have been described in W003/086073, which describes a composition to control grapevine powdery mildew (Uncinula necator), comprising sulfur and a 40% soybean oil in water emulsion.

Sulfur has limited applications in crops like wheat, barley, rye, triticale, oat, sugar and fodder beets. While sulfur protects these crops well against powdery mildews, like Blumeria graminis (also known as Erysiphe graminis), it requires high application rates of 6 to 8 kg of sulfur per hectare (ha) per treatment. Even at these high rates, sulfur shows insufficient effects against other phytopathogenic fungi of these crops. Accordingly, there is a need in the art to improve the protective effects of sulfur-based fungicides against other phytopathogenic fungi of these crops and/or to identify ways to apply sulfur in these crops which allow for a lower application rate per hectare and year.

Another type of compounds which have been used as natural fungicides are terpenes. Terpenes are a diverse group of natural compounds and are parts of many plant essential oils. Their basic structure can be visualized as the result of linking isoprene (CsHs) units "head to tail" to form chains and rings. They are further classified depending on the amount of isoprene units used for their basic structure. Examples for these subgroups are monoterpenes, sesquiterpenes and diterpenes. Monoterpenes comprise two isoprene units and C10H16 in their basic structure, sesquiterpenes comprise three and diterpenes four isoprene units.

WO2022/101613 describes a bio-fungicide composition comprising microencapsulated essential oils or isolated terpenes. Despite the fact, that sulfur and terpenes have been used as pesticides since a long time, it is less known about their combined effects and the conditions to achieve positive effects or to overcome technical hurdles arising from their combination. WO2019/207112 describes a fungicidal mixture of limonene, cinnamaldehyde and one or more terpinenes, which can be used to replace other fungicides and thereby reduce the amount of other fungicides, like sulfur and copper, in spray regimes to protect plants. It describes that using the particular mixture in spray regimes has the potential to reduce the total amount of sulfur from 100 to 120 kg to 10 to 12 kg per season.

WO2016/004326 discloses a seed, soil, or plant treatment composition, comprising one or more essential oils and one or more emulsifiers, wherein the one or more essential oils are present as an emulsion and the average particle size of the one or more essential oils in the emulsion is less than about 25 microns. WO2016/004326 also describes that this plant treatment composition can be combined with several pesticides, including fungicides, such as sulfur. While these documents describe effects of sulfur and terpenes for protecting plants against fungal attack, they do not describe, how these compounds can be used together, without reducing the effectiveness of sulfur against fungal or insect pests and or to avoid enhanced phytotoxicity effects based on the combination of these compounds. These documents do also not describe for which fungal plant pathogens the combination of sulfur and terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol provides synergistic antifungal effects.

Combinations of sulfur and terpenes have been produced. FR2599592 describes an antifungal composition (Helio- sulfre®), comprising suspended micronized sulfur in in an emulsion of pine oil and water and one or more surfactants. One liter of this suspension concentrate comprises typically 60 to 170 g of pine oil; 25 to 70 g of surfactants; 400 to 1000 g of micronized or finely ground sulfur. A combination of nanoparticulated sulfur with essential orange oil has been described as Oro Solve®. Cesar et al. 2019, ""Nanoparticulated Sulfur and Essential Orange Oil (Oro Solve®) Increases Efficiency of Euschistus heros Control", Egypt. Acad. J. Biolog. Sci., 12(6): 111-120, describes that Oro Solve® is composed of orange essential oil + 45% nanoparticulate elemental sulfur, giving a concentration of 585 g per liter.

However, Oro Solve® has not been commercially successful and discontinued, which points to a general problem in the art, which is the difficulty to create stable formulations comprising particulate sulfur and mineral or plant oils, e.g., see paragraph [0007] of EP2904903, lines 33 to 55 in the right column of US6835719 and paragraphs [0006] to [0017] of US2014/0044765, these problems include stability of the formulation itself, reduced effectiveness of sulfur against fungal or insect pests, enhanced phytotoxicity and degradation of organic oils. For these reasons many labels of sulfur products advise not to use them as a tank mix with oil comprising products and to avoid applying sulfur and oil independently during a time frame of 30 days on plants. In addition to the well-known problems of liquid sulfur comprising formulations are low storage stability, due to sedimentation, crystal growth and phase separation, further problems can be expected for combinations of sulfur with terpenes, as they are prone to oxidation, while sulfur promotes oxidation of other compounds.

A further type of natural fungicides are compounds derived of phosphorous acid (H3PO3) and are usually called phosphites. Phosphites are known as environmental benign fungicides with a low toxicity towards users and consumers but require a high dose to be effective. Their antifungal effect relies partly on a direct toxicity to oomycetes like Phy- tophthora and Pythium, and partly on a stimulation of plant defense. One disadvantage of phosphites is that the high dose required for an antifungal effect can also result in phytotoxicity. Accordingly, it would be of advantage to identify combinations of phosphites with other antifungal substances, such as sulfur and terpenes, to reduce the dose required for the antifungal effect. However, it is generally known that phosphite products are not compatible with alkaline materials such as lime, sulfur or spray oils. It has also be considered, that high concentrations of sulfur usually lead to high viscosity and poor pourability of formulations, which, especially when combined with sedimentation of sulfur, can cause severe problems during preparation and application of the spraying suspension and can cause uneven application of the active compounds on the crop and blocking of valves and spray nozzles of the crop protection sprayer One additional problem is that terpenes usually have a high vapor pressure, so that a combined action of terpenes and sulfur on the respective plant pathogen or pest may be too short lived to provide any additional positive effect for plant protection.

The present invention provides solutions to these problems. In addition thereto, it was also found, that the combination of sulfur with selected terpenes provides for a synergistic effect for controlling plant pathogenic fungi. of the invention

Described herein are mixtures comprising: a) sulfur, b) one or more terpenes, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, and c) phosphites.

Sulfur:

The sulfur comprised in the compositions can be elemental sulfur. Elemental sulfur can occur in several different allotropic forms, such as plastic (amorphous) sulfur, monoclinic sulfur, rhombic sulfur composed of ring molecules. The most common form is a ring structure of 8 atoms (S8) usually accompanied by smaller rings of 7 (S7) or 6 (S6) atoms. Elemental sulfur can be mined from fossil-based sulfur deposits of salt domes or from volcanic emissions but is most frequently produced as byproduct of desulfurization of natural gas and petroleum. The most important process for desulfurization is the Claus process, which includes an oxidation step of hydrogen sulfide (H2S) to sulfur dioxide (SO2) and a catalyzed reaction of H2S with SO2 to form elemental sulfur (S°) (Schreiner, B. 30 2008. Chemie in un- serer Zeit 42: 378). Another form of elemental sulfur is flowers of sulfur, which is a very fine, bright yellow sulfur powder that is produced by sublimation and deposition of sulfur.

A further source of elemental sulfur is the oxidation of hydrogen sulphide, e.g. from gas streams, by microorganisms, which produce small particles of elemental sulfur. This type of sulfur is called "biosulfur” and is distinguished from chemically produced sulfur by having a lower density compared to orthorhombic sulfur. Biosulfur particles have also hydrophilic properties whereas orthorhombic sulfur is known to be hydrophobic.

The sulfur used in the invention can either be chemically produced sulfur, preferably orthorhombic sulfur, or can be biosulfur.

The particle diameter of sulfur is important for the efficacy of the product as a pesticide on crops. The particulate sulfur has preferably a D50 particle size diameter of less than 100 micrometers, preferably less than 50 micrometer, more preferred less than 10 micrometer and even more preferred less than 8 micrometer, most preferred less than 3 micrometer. The Dw particle size diameter and the D90 particle size diameter is usually 1 micrometer for D and 80 micrometer for D90, preferably 1 micrometer for D 10 and 50 micrometer for D90, more preferred 1 micrometer for D10 and 30 micrometer for D90, even more preferred 1 micrometer for D10 and 20 micrometer for D90, and most preferred 1 micrometer for D and 10 micrometer for D90. Particles with a diameter between 1 and 8 microns are optimal, particles with a larger diameter are much less toxic for fungi and particles smaller than 1 micron can easily cause phytotoxic effects like chlorosis and necrosis (Emmett et al., 2003. "Sulphur formulations, particle size and activity - a review" in "Strategic Use of Sulphur in Integrated Pest and Disease Management (IPM) Programs for Grapevines". Accordingly, in a very preferred embodiment, the sulfur has a diameter particle size with an Dw value of 1 micrometer and a D90 value of 8 micrometer and even more preferred with an D50 value of less than 3 micrometer.

The D [4;3] value of the particles is preferably between 1 and 8 micrometer, more preferred between 1 and 4 micrometer.

The average diameter particle size of biosulfur particles is usually smaller. Biosulfur particles of less than 1 micrometer average diameter are also less phytotoxic than orthorhombic sulfur particles of a similar size. Preferably, the D50 of diameter particle sizes for biosulfur is less than 10 micrometer, more preferred less than 9 micrometer, more preferred less than 8 micrometer, more preferred less than 7 micrometer, more preferred less than 6 micrometer, less than 5 micrometer, less than 4 micrometer, less than 3 micrometer, more preferred less than 2.5 micrometer, more preferred less than 2 micrometer, more preferred less than 1 micrometer, most preferred less than 0.8 micrometer. Preferably the biosulfur has a Dw of 0.1 micrometer and D90 of 8 micrometer average diameter particle size.

The Dw, D50, D90 and D[4;3] value are commonly used in the art to describe the size distribution of particles. Methods for determining these values are known in the art and include, for example, the actual size and morphology of the particles using a camera system, and the use of laser diffraction and dynamic light scattering. A preferred method employs laser diffraction, for example by the use of an ANALYSETTE 22 MicroTec plus particle size analyser. Methods available in the art, such as milling, can be used to adapt the average particle size of the sulfur particles to the distribution of particle sizes intended.

Selected Terpenes:

The suspoemulsion or suspension concentrate formulations of the invention comprise at least one terpene, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol. A reference to the name of terpene also includes a reference to the naturally occurring enantiomers of the respective terpene, e.g. a reference to limonene will comprise a reference to D-Limonene, which is the (R)-enantiomer, and L-limonene, which is the (S)- enantiomer.

The selected terpenes can be chemically synthesized or isolated from essential plant oils. Methods to synthesize the selected terpenes are well known in the art. However, the selected terpenes can also be isolated e.g. via centrifugal separation or steam distillation from plant essential oils.

The skilled person knows which essential plant oil comprises one or more of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol. Examples for suitable essential plant oils are: orange oil, tangerine oil, grapefruit oil, lemon oil, mandarin oil, which comprise high amounts of D-limonene. Thyme oil, which usually comprises thymol with 23% to 60%, y-terpinene with 18% to 50%, p-cymene with 8% to 44% and carvacrol with 2% to 8%. Oregano oil comprises high amounts of thymol and carvacrol. Pinene can be isolated from pine oil. P-cymene can be found in the oils of cumin and thyme. Eugenol can be isolated from cinnamon oil. Geraniol is a component of citronella oil, rose oil and palmarosa oil. The content of a given terpene in a certain essential oil can vary and will depend on the source of the plant material, such as genotype of the plant, environmental conditions during growth of the plant, harvesting conditions of the plant material, method of extraction and other factors.

In one embodiment of the invention the limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol or carvacrol has been isolated from an essential plant oil or is provided as part of an essential plant oil. In case it is provided as part of an essential plant oil, the amount of the limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol or carvacrol or if more than one of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol or carvacrol is present, the combined sum of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol in the final mixture and not the amount of the respective essential oil will be decisive for the amount of the selected terpenes in the methods to control phytopathogenic fungi.

The mixtures used in the described methods may comprise only one of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol or carvacrol, for example only limonene, preferably D-limonene, but may also comprise more than one of the selected terpenes.

Preferred mixtures of the selected terpenes are: a) mixtures of limonene, preferably D-limonene, with at least one of a-terpinene, p-cymene, carvacrol, eugenol, geraniol and thymol- b) mixtures of limonene, preferably D-limonene, with at least one of a-terpinene, p-cymene and carvacrol. c) mixtures of limonene, preferably D-limonene, with at least one of eugenol, geraniol and thymol.

Preferably the weight/weight ratio between limonene, preferably D-limonene, and one terpene selected from terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is between 75 to 1 and 1 to 1, or between 50 to 1 and 1 to 1, or between 25 to 1 and 1 to 1, or between 10 to 1 and 1 to 1, or between 8 to 1 to 1 to 1, or between 5 to 1 and 1 to 1 , or between 2 to 1 and 1 to 1 .

Preferably the weight/weight ratio between limonene, preferably D-limonene, and the combined amount of the one or more of terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is between 75 to 1 and 1 to 1, or between 50 to 1 and 1 to 1, or between 25 to 1 and 1 to 1, or between 10 to 1 and 1 to 1, or between 8 to 1 to 1 to 1, or between 5 to 1 and 1 to 1 , or between 2 to 1 and 1 to 1.

Further preferred mixtures of the selected terpenes are: a) mixtures of a-terpinene, p-cymene and limonene. b) mixtures of at least two of eugenol, geraniol and thymol.

The terpenes, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol may be accompanied by other terpenes, in particular if at least one of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is provided as part of an essential plant oil.

Preferably, the weight/weight ratio between the combined amounts of the terpenes, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, and the combined amounts of other terpenes is between 75 to 1 and 1 to 1, or between 50 to 1 and 1 to 1, or between 25 to 1 and 1 to 1, or between 10 to 1 and 1 to 1, or between 8 to 1 to 1 to 1, or between 5 to 1 and 1 to 1, or between 2 to 1 and 1 to 1. In one embodiment, the weight/weight ratio between limonene, preferably D-limonene, and the combined amount of terpenes other than, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is between 75 to 1 and 1 to 1 , or between 50 to 1 and 1 to 1 , or between 25 to 1 and 1 to 1 , or be-tween 10 to 1 and 1 to 1 , or between 8 to 1 to 1 to 1 , or between 5 to 1 and 1 to 1 , or between 2 to 1 and 1 to 1 .

In one embodiment, the weight/weight ratio between limonene, preferably D-limonene, and the combined amount of terpenes including terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol is between 75 to 1 and 1 to 1, or between 50 to 1 and 1 to 1, or between 25 to 1 and 1 to 1 , or be-tween 10 to 1 and 1 to 1 , or between 8 to 1 to 1 to 1 , or between 5 to 1 and 1 to 1 , or between 2 to 1 and 1 to 1 and preferably more than 90 to 1 or higher, 100 to 1 or higher, 300 to 1 or higher, 500 to 1 or higher or 1000 to 1 or higher.

Phosphites:

Examples of phosphites are phosphorous acid and its (alkali metal or alkaline earth metal) salts such as potassium phosphites e.g. KH2PO3 and K2HPO3, sodium phosphites and ammonium phosphites, and (C-C4) alkyl esters of phosphorous acid and their salts such as aluminum ethyl phosphite (fosetyl-AI), calcium ethyl phosphite, magnesium isopropyl phosphite, magnesium isobutyl phosphite, magnesium sec-butyl phosphite and aluminum N-butyl phosphite. Preferred are KH2PO3, K2HPO3, Nab^POs, Na2HPC>3, (NH^HPOs, (NH^PC , and mixtures of these compounds.

Mixtures:

Peferably the weight/weight ratio of a) the amount of sulfur to the combined amounts of the terpenes, selected from limonene, terpinene, pinene, p-cy- mene, eugenol, geraniol, thymol and carvacrol is between 100 to 1 and 1 to 1 , or between 70 to 1 and 1 to 1 , or between 65 to 1 and 1 to 1 , or between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1 , or between 25 to 1 and 2 to 1 , or between 25 to 1 and 3 to 1 , or between 25 to 1 and 4 to 1 , or between 25 to 1 and 5 to 1 , or between 25 to 1 and 6 to 1 , or between 25 to 1 and 7 to 1 , or between 25 to 1 and 8 to 1, or between 25 to 1 and 9 to 1, or between 15 to 1 and 7 to 1 , or between 12 to 1 and 7 to 1 , or between 10 to 1 and 7 to 1 , or between 12 to 1 and 8 to 1 , or between 11 to 1 and 9 to 1, or b) the amount of sulfur to the amount of limonene, preferably D-limonene, is between 100 to 1 and 1 to 1 , or between 70 to 1 and 1 to 1 , or between 65 to 1 and 1 to 1 , or between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1, or between 30 to 1 and 1 to 1 , or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1 , or between 25 to 1 and 2 to 1, or between 25 to 1 and 3 to 1 , or between 25 to 1 and 4 to 1, or between 25 to 1 and 5 to 1 , or between 25 to 1 and 6 to 1 , or between 25 to 1 and 7 to 1, or between 25 to 1 and 8 to 1, or between 25 to 1 and 9 to 1 , or between 15 to 1 and 7 to 1 , or between 12 to 1 and 7 to 1 , or between 10 to 1 and 7 to 1 , or between 12 to 1 and 8 to 1, or between 11 to 1 and 9 to 1, c) the amount of sulfur to the combined amounts of the phosphites, preferably KH2PO3 and/or K2HPO3, is between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 20 to 1 and 1 to 1 , or between 10 to 1 and 1 to 1, or between 5 to 1 and 1 to 1, or between 10 to 1 and 2 to 1, or between 8 to 1 and 2 to 1, or between 7 to 1 and 2 to 1 , or between 6 to 1 and 3 to 1 , d) the amount of sulfur to the amount of limonene, preferably D-limonene, is between 100 to 1 and 1 to 1, or between 70 to 1 and 1 to 1, or between 65 to 1 and 1 to 1, or between 50 to 1 and 1 to 1, or between 40 to 1 and 1 to 1, or between 30 to 1 and 1 to 1 , or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1 , or between 25 to 1 and 2 to 1, or between 25 to 1 and 3 to 1, or between 25 to 1 and 4 to 1, or between 25 to 1 and 5 to 1, or between 25 to 1 and 6 to 1, or between 25 to 1 and 7 to 1, or between 25 to 1 and 8 to 1, or between 25 to 1 and 9 to 1, or between 15 to 1 and 7 to 1, or between 12 to 1 and 7 to 1, or between 10 to 1 and 7 to 1, or between 12 to 1 and 8 to 1, or between 11 to 1 and 9 to 1 and the amount of sulfur to the combined amounts of the phosphites, preferably KH2PO3 and/or K2HPO3, is between 50 to 1 and 1 to 1, or between 40 to 1 and 1 to 1, or between 30 to 1 and 1 to 1, or between 20 to 1 and 1 to 1, or between 10 to 1 and 1 to 1, or between 5 to 1 and 1 to 1, or between 10 to 1 and 2 to 1, or between 8 to 1 and 2 to 1 , or between 7 to 1 and 2 to 1 , or between 6 to 1 and 3 to 1 .

Suspoemulsion and suspension concentrate formulations comprising sulfur, selected terpenes and phosphites.

A further embodiment of the invention are suspoemulsion and suspension concentrate formulations comprising: a) sulfur b) one or more terpenes, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, c) phosphites, d) one or more carrier oils and e) optionally further components.

Agrochemical suspoemulsions are also known as "SE" type agro formulations. The suspoemulsion usually comprises a continuous aqueous phase, a dispersed oil phase, and a suspended solid phase. The oil phase usually forms droplets within the aqueous phase. The oil phase usually comprises the water-immiscible active ingredient. The oil phase usually comprises at least one pesticide, which may be dissolved in a water-immiscible solvent. The solid phase usually consists of solid particles within the aqueous phase. The solid phase may comprise at least one pesticidal substance, which is suspended in a continuous aqueous phase. A further pesticidal substance is dissolved in the water- immiscible solvent. Preferably, the further pesticidal substance is present at least in the dispersed oil phase of the suspoemulsion. The first pesticidal substance is suspended in the continuous aqueous phase. Preferably, the first pesticidal substance is present at least in the solid phase of the suspoemulsion.

Agrochemical suspension concentrates (also known as "SC" type formulations) typically relates to compositions, which comprise solid particles, which are homogenously dispersed in a continuous aqueous phase. Agrochemical suspension concentrate is usually preformed in the commercial product and is conventionally diluted with a carrier, such as water, when making up the spray mixture (also called the tank mix). The continuous aqueous phase of the suspension concentrate is usually free of other dispersed phases beside the pesticide particles.

The suspoemulsion and suspension concentrate formulations preferably comprise a) sulfur b) at least one terpene, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, in a weight/weight ratio of sulfur to the combined amount of limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol and c) phosphites, in weight/weight ratios as described for the mixtures above. Suitable carrier oils should have a low solubility in water. Preferably the solubility at 20°C is less than 1 gram/l iter, preferably less than 0.1 gram/liter. They may comprise only one type of carrier oil or a mixture of at least two carrier oils. The carrier oils are preferably selected from one or more of the following groups.

One preferred group of carrier oils are terpenes, which are liquid at 20°C and are not limonene, terpinene, pinene, p- cymene, eugenol, geraniol, thymol or carvacrol.

Another preferred group of carrier oils comprises plant oils and alkyl esters of such plant oils. Preferably the ester is selected from methyl, ethyl, propyl, isopropyl and butyl esters. The plant oil is preferably selected from soybean oil, rape oil, sunflower oil, peanut oil, linseed oil, cottonseed oil, corn oil, castor oil, neem oil, olive oil. Preferred mixtures of alkyl esters are C6 to C10 fatty acid methylester, C8 to C10 fatty acid methyl ester and C16 to C18 fatty acid methyl ester.

Preferred alkyl ester of single fatty acids are methyl oleate, methyl octanaoate, methyl decanoate, metyl linolenate, ethyl hexanoate, ethyl octanoate, ethyl decanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, myristyl myristate and butyl stearate. In one embodiment the carrier oil is or comprises ethoxylated castor oil. In one embodiment the carrier oil is or comprises methyl oleate. In one embodiment the carrier oil is or comprises isopropyl myristate. In one embodiment the carrier oil is or comprises soybean oil, rape oil, sunflower oil, peanut oil, linseed oil, cottonseed oil, corn oil or castor oil. In one embodiment the carrier oil is or comprises rape oil and/or sunflower oil. A further group of carrier oil comprises C11 to C14 alkyl acetate, and decyl acetate, isobornyl acetate and 2- ethylhexyl acetate.

A further group comprises C12 - C20 fatty alcohols, octanol, decyl alcohol, tridecanol, 2-ethylhexanol, oleyl alcohol, cetyl alcohol and lauryl alcohol.

A further group comprises dibutyl adipate, diisobutyl adipate, diisopropyl adipate, diethylhexyladipate, diisodecyl adipate, didisotridecyl adipate, diethylhexyl sebacate, dibutyl sebacate.

A further group comprises ethyl cinnamate and propyl cinnamate.

A further group comprises benzyl benzoate, benzyl acetate, benzyl butyl ester, isopropyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, propylene glycol dibenzoate, dipropylene glycol dibenzoate,

A further group comprises tall oil fatty acids, oleic acid, palmitic acid, 2-ethylhexyl octanoate, coco caprylate, tex- anoldiiosbutyrate, 1 ,2-cyclohexanedicarbolixylic acid diisononylester, di-n-butylcarbonate, alkyl naphthalenes, dioctyl ether.

Another group comprises aromatic solvent napthat (Solvesso grades), decane, petroleum, cyclohexane, methyl cyclohexane, kerosine, tris-(2-ethylhexyl)phosphate, tris-(2-butoxyethyl)phosphate, 2-ethylhexyllactate, tributylcitrate, acetyltributylcitrate, tris-(ethylhexyl)trimellitate, dimethyl octanaminde, dimethyldecanamide, dimethyldodecanamide and mineral oil, preferably a dewaxed mineral oil (CAS No. 64742-56-9). In one embodiment the carrier oil is or comprises dewaxed mineral oil (CAS No. 64742-56-9).

In one embodiment the carrier oil comprises a mixture of at least two of methyl oleate, isopropyl myristate, rape oil and sunflower oil, or a mixture of at least two of methyl oleate, rape oil and sunflower oil. The suspoemulsion or suspension concentrate formulations comprise, in a rising degree of preference, between 300 and 900 gram/li ter, between 300 and 800 gram/liter, between 350 and 750 gram/li ter, or between 400 and 700 gram/l iter of elemental sulfur particles,

The combined amount of all terpenes, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, is preferably between 10 and 300 gram/liter, 10 and 250 gram/liter, between 10 and 200 gram/liter, between 15 and 150 gram/liter, between 20 and 150 gram/liter, between 20 and 130 gram/liter, between 20 and 70 gram/liter or between 30 and 60 gram/liter.

The amount of limonene, preferably D-limonene, is preferably between 10 and 300 gram/liter, 10 and 250 gram/liter, between 10 and 200 gram/liter, between 15 and 150 gram/liter, between 20 and 150 gram/liter, between 20 and 130 gram/liter, between 20 and 70 gram/liter or between 30 and 60 gram/liter.

The combined amount of all phosphites, preferably KH2PO3 and/or K2HPO3, is preferably between 50 and 600 gram/liter, between 100 and 600 gram/liter, between 200 and 500 gram/liter, between 100 and 600 gram/liter, between 100 and 500 gram/liter, between 100 and 400 gram/liter, between 100 and 300 gram/liter, or between 100 and 200 gram/liter.

The combined amount of all carrier oils is preferably between 50 and 300 gram/liter, between 70 and 250 gram/liter, between 70 and 200 gram/liter, between 80 and 250 gram/liter, between 80 and 200 gram/liter, between 80 and 170 gram/liter, between 80 and 150 gram/liter, between 80 and 120 gram/liter, between 80 and 110 gram/liter, between 90 and 250 gram/liter, between 90 and 200 gram/liter, between 90 and 170 gram/liter, between 90 and 150 gram/liter, between 90 and 120 gram/liter, between 90 and 110 gram/liter.

Non limiting examples for the amounts of sulfur, combined amount of terpenes, and the combined amount of phosphites of suspoemulsion or suspension concentrate formulations are provided in Tables 1 to 3:

Table 1: amounts are provided in gram/liter

Table 2: amounts are provided in gram/liter

Table 3: amounts are provided in gram/liter

The selected terpenes and carrier oils used in the suspoemulsion or suspension concentrate formulations described in Table 1 to 3 are preferably selected limonene, a-terpinene, p-cymene, eugenol, geraniol, thymol and carvacrol and carrier oils, in particular preferred are formulations comprising a combination of limonene and methyl oleate or limonene and isopropyl myristate or limonene and one or more carrier oils selected from soybean oil, rape oil, sunflower oil, peanut oil, linseed oil, cottonseed oil, corn oil or castor oil.

Preferably the oil phase has an average oil droplet size of less than 25 microns, less than 15 microns, less than 10 microns or less than 5 microns.

The suspoemulsion or suspension concentrate formulations usually have a pH from 5.5 to 8.5, preferably form 6.5. to 7.5.

The suspoemulsion or suspension concentrate formulations described herein are selected based on their good storage stability.

Preferably after two weeks of storage at 40°C, the change of the value for the percentage of sulfur particles larger than 2 micrometer, the D50, the D90 and/or the D[4;3] value should not be larger than plus or minus 15%, preferably plus or minus 10%, more preferred plus or minus 5%.

Preferably after two weeks of storage at 50°C, the change of the value for the percentage of sulfur particles larger than 2 micrometer, the D50, the D90 and/or the D[4;3] value should not be larger than plus or minus 15%, preferably plus or minus 10%, more preferred plus or minus 5%.

Preferably after two weeks of storage at 12 hour cycling temperatures between minus 10°C and plus 10°C, the change of the value for the percentage of sulfur particles larger than 2 micrometer, the D50, the D90 and/or the D[4;3] value should not be larger than plus or minus 25%, preferably plus or minus 20%, more preferred plus or minus 15%, even more preferred plus or minus 10%.

Further components

The suspoemulsion or suspension concentrate formulations may comprise further components, such as auxiliaries known to be suitable for agrochemical formulations,.

Examples for suitable auxiliaries are liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wet- ters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, antioxidants, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foam- ing agents, colorants, tackifiers and binders.

The liquid carrier is preferably water.

Preferably, the suspension concentrate or suspoemulsion formulations comprise one or more of the following auxiliaries: a) 70 to 10 gram/liter of one or more dispersants, b) 70 to 20 gram/liter of one or more antifreeze, c) 50 to 1 , or 50 to 20 gram/liter of one or more anionic surfactants, d) 100 to 1, or 10 to 1 gram/liter of one or more nonionic surfactants, e) 10 to 2 gram/liter of one or more biocides, f) 10 to 1 gram/liter of one or more antifoams, g) 10 to 1 gram/liter of one or more antioxidants, h) 10 to 1 gram/liter of one or more thickener

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof. Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents ethylene oxide and/or propylene oxide and/or butylene oxide may be employed for the alkoxy lation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkyl- polyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vi ny I alcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazoli- nones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

Antoxidants are a preferred suspension concentrate or suspoemulsion formulations, if it is intended to enhance their antioxidant capacity above the level provided by the other components, e.g. provided by terpenes which are liquid at 20°C and/or the carrier oils. Such additional antioxidants are preferably selected from tocopherols, e.g. vanillin, a- tocopherol, ascorbic acid, ascorbate, carotenoids, e.g. beta-carotene, n-propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), tert-Butylhydroquinone (TBHQ).

More preferred are: n-propyl gallate, ascorbic acid, sodium sulfite, tocopherol-acetate and butylated hydroxyanisole (BHA).

The antioxidant capacity can be measured by methods known in the art, for example methods discussed in Munte- anu and Apetrei, Int. J. Mol. Sci.; Analytical Methods Used in Determining Antioxidant Activity: A Review; 2021, 22, 3380. https://doi.org/10.3390/ijms22073380.

Preferably the suspoemulsion or suspension concentrate formulations comprise from 20 to 0,5, or from 15 to 1, or from 10 to 1, or from 8 to 1, or from 5 to 1, gram/liter of one or more antioxidants, which are not terpenes which are liquid at 20°C as pure substance or carrier oils. In one embodiment the antioxidant is vanillin.

In one embodiment the suspension concentrate or suspoemulsion formulations comprise a) to f) a) 50 to 20 gram/liter of one or more dispersants (e.g. Morwet D 425, CAS 577773-56-9), and b) 50 to 20 gram/liter of one or more antifreeze (e.g. 1 ,2-Propylene glycol) and c) 50 to 1, or 50 to 20 gram/liter of one or more anionic surfactants (e.g. Wettol NT1 CAS 211565-27-4 or Wettol EM 1, CAS 26264-06-2 ) and d) 100 to 1, or 10 to 1 gram/liter of one or more nonionic surfactants (e.g. Agnique SPO 40 and Wettol EM 31, CAS 61791-12-6) and e) 5 to 3 gram/liter of one or more biocides (e.g. Acticide MV and Acticide B 20) and f) 10 to 1 gram/liter of one or more antifoams (e.g. SRE-PFL).

CAS Numbers are defined by the Chemical Abstracts Service (CAS).

In one embodiment the suspension concentrate or suspoemulsion formulations comprise a) to g) and preferably also h) a) 70 to 10, or 50 to 20 gram/liter of one or more dispersants, b) 70 to 20, or 50 to 20 gram/l iter of one or more antifreeze, c) 50 to 1, or 50 to 20 gram/liter of one or more anionic surfactants, d) 100 to 1, or 10 to 1 gram/liter of one or more nonionic surfactants, e) 10 to 2, or 5 to 3 gram/liter of one or more biocides, f) 10 to 1 gram/liter of one or more antifoams, g) 10 to 1 gram/liter of one or more antioxidants, h) 10 to 1 gram/liter of one or more thickener g) 10 to 1 gram/liter of one or more antioxidants, h) 10 to 1 gram/liter of one or more thickener

In one embodiment, the auxiliaries in the suspension concentrate or suspoemulsion formulations, comprise auxiliaries selected from the following groups: a) fatty alcohol alkoxylates, b) silicone adjuvants, c) sulphosuccinates, or d) mixtures of at least two of a to c).

Preferred fatty alcohol alkoxylates are Plurafac LF 221 (CAS 208350-19-0), Plurafac LF 901 (CAS 166736-08-9), Lutensol TO 8 and Lutensol ON 60 (CAS 123897-56-3),

Preferred silicone adjuvants are Silwet HS 604 (CAS 2524826-13-7) and Silwet HS 312 (CAS 1012786-03-6)

A preferred sulphosuccinate is Lutensit A-BO (CAS 577-11-7),

In some embodiment the auxiliaries selected from groups a) to c) or combinations thereof are:

1) One or more sulphosuccinates, preferably at least one sulphosuccinate is a salt of bis(2-ethylhexyl) sulfosuccinate, more preferred it is sodium bis(2-ethylhexyl) sulfosuccinate, even more preferred it is Lutensit A-BO.

2) One or more fatty alcohol alkoxylates, preferably at least one fatty alcohol alkoxylate is selected from Plurafac LF 221, Plurafac LF 901, Lutensol TO 8 and Lutensol ON 60.

3) One or more silicone adjuvants, preferably selected from Silwet HS 604 and Silwet HS 312

4) A mixture of one or more sulphosuccinates and one or more fatty alcohol alkoxylates, preferably a mixture comprising a salt of bis(2-ethylhexyl) sulfosuccinate, more preferred comprising sodium bis(2-ethylhexyl) sulfosuccinate, even more preferred comprising Lutensit A-BO. Preferred fatty alcohol alkoxylates are selected from Plurafac LF 221, Plurafac LF 901, Lutensol TO 8 and Lutensol ON 60.

5) A mixture of one or more fatty alcohol alkoxylates and one or more silicone adjuvants. Preferably at least one of the fatty alcohol alkoxylates is selected from Plurafac LF 221, Plurafac LF 901, Lutensol TO 8 and Lutensol ON 60. Preferably at least one of the silicone adjuvants is selected from Silwet HS 604 and Silwet HS 312.

Preferably, the weight/weight ratio between the combined amounts of sulphosuccinates and the combined amounts of fatty alcohol alkoxylates is between 5 to 1 and 1 to 5 or between 3 to 1 and 1 to 3 or between 2 to 1 and 1 to 2 or is 1 to 1. Preferably, the weight/weight ratio between the combined amounts of fatty alcohol alkoxylates and the combined amounts of silicone adjuvants is between 5 to 1 and 1 to 5 or between 3 to 1 and 1 to 3 or between 2 to 1 and 1 to 2 or is 1 to 1 .

The total amount of the auxiliaries selected from the following groups: fatty alcohol alkoxylates, silicone adjuvants and sulphosuccinates, in the suspension concentrate or suspoemulsion formulations, is preferably in an amount of 100 to 1 gram/liter, 80 to 1 gram/liter, 70 to 1 gram/liter, 60 to 1 gram/liter, 50 to 1 gram/liter, 40 to 1 gram/liter, 30 to 1 gram/liter, 20 to 1 gram/liter or 10 to 1 gram/liter.

The total amount of the auxiliaries selected from the following groups: fatty alcohol alkoxylates, silicone adjuvants and sulphosuccinates, in the suspension concentrate or suspoemulsion formulations, is preferably in an amount of 100 to 10 gram/liter, 90 to 15 g/liter, 80 to 20 gram/liter, 75 to 20 gram/liter or 60 to 40 gram/liter.

The suspension concentrate or suspoemulsion formulations of the invention usually have a good pourability, a low viscosity and a low phytotoxicity.

The pourability of the suspension concentrate or suspoemulsion formulations, can be determined according to Cl- PAC Method MT 148 - Pourability of suspension concentrates. COLLABORATIVE INTERNATIONAL PESTICIDES ANALYTICAL COUNCIL (CIPAC) is an international, non-profit-oriented organization for the promotion of uniform methods for the analysis of pesticides and physico-chemical test methods for pesticide formulations.

The amount of product that remains in the packaging after emptying is preferably below 15%, more preferred below 10%, most preferred below 5%.

The viscosity of the suspoemulsion can be measured using a rheometer. A typical value for the viscosity of such a suspoemulsion is below 300 mPas at 100 s ¹, more preferred less than 250 mPas at 100 s ¹, more preferably less than 200 mPas at 100 s ¹ , even more preferred less than 150 mPas at 100 s ¹ or even less than 100 mPas at 100 S’¹.

The invention furthermore relates to a spraying suspension obtainable by mixing water and the suspension concentrate or suspoemulsion according to the invention. The spraying suspension normally arises spontaneously upon mixing. The mixing weight/weight ratio of water to concentrate can be in the range of from 1000 to 1 up to 1 to 1 , preferably 400 to 1 up to 3 to 1, more preferred 200 to 1 up to 3 to 1 .

Methods to prepare:

The suspension concentrate or suspoemulsion formulations of the invention can be produced using methods known in the art, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

One method to prepare suspension concentrate or suspoemulsion formulations of the invention is performed by milling crystalline sulfur in water with suitable wetting agents and dispersants with a bead mill as known to those skilled in the art. The resulting Suspension is stabilized by addition of further additives like antifreeze agents, antifoam, biocides, thickeners and optionally further additives like buffer salts. To such a suspension the one or more terpenes, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, preferably limonene, are added by an emulsion process. The one or more selected terpenes, preferably limonene, can be emulsified as such into the suspension concentrate, if the dispersants and wetting agents that are used for preparing the sulfur suspension are also suited to emulsify the one or more selected terpenes. Otherwise, further emulsfiers specific to be used with the one or more selected terpenes, are added to the one or more selected terpenes to form an oil phase, which is then added to the sulfur suspension using shear energy and thus emulsifying the oil phase comprising the one or more selected terpenes into the sulfur suspension.

Customary mixing devices which, if appropriate, can be heated may be used for preparing the mixtures. For the preliminary milling step, it is possible to use, for example, mills which operate on the rotor-stator principle, such as Ultra- turax homogenizers, for example from I KA, or toothed colloid mills, for example from Puck. Apparatus which can be used for the fine-grinding step can be, for example, batchwise-operating bead mills, for example from Drais, or continuously-operating bead mills, for example from Bachofen. Depending on the properties of the components employed, and on process-engineering and safety aspects and economic reasons, the preparation process can be adapted and, if appropriate, a pre-grinding step or else a fine-grinding step can be dispensed with.

Method for controlling phytopathogenic fungi using the mixtures described herein or using suspension concentrates or suspoemulsions comprising these mixtures:

The invention comprises a method for controlling phytopathogenic fungi comprising contacting the fungi, the plant, or the plant parts to be protected against fungal attack with a fungicidal effective amount of a spraying suspension obtained by mixing water and the suspension concentrate or suspoemulsion described herein. Accordingly, the invention comprises a method for controlling phytopathogenic fungi, comprising the steps of a) identifying a plant or a plurality of plants infected or in danger of being infected with at least one fungus and b) contacting the fungi, the plant, or the plant parts to be protected against fungal attack with a fungicidally effective amount of a spraying suspension obtained by mixing water and the suspension concentrate or suspoemulsion described herein.

A plant may be in danger of being infected for several reasons, for example, if a neighboring plant of the same species is already infected or if a part of the same crop is infected, or if season and weather conditions make it likely that a plant or crop will be infected by a certain fungus.

The suspension concentrates or suspoemulsions and the spraying suspensions prepared therefrom, respectively, are suitable as fungicides effective against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, in particular from the classes of Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridio- mycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (syn. Fungi imperfecti). They can be used in crop protection as foliar fungicides, fungicides for seed dressing, and soil fungicides.

The suspension concentrates or suspoemulsions and the spraying suspensions prepared therefrom are preferably useful in the control of phytopathogenic fungi on various cultivated plants, such as cereals, e.g. wheat, rye, barley, triticale, oats, or rice; beet, e.g. sugar beet or fodder beet; fruits, e.g. pomes (apples, pears, etc.), stone fruits (e.g. plums, peaches, almonds, cherries), or soft fruits, also called berries (strawberries, raspberries, blackberries, gooseberries, etc.); leguminous plants, e.g. lentils, peas, alfalfa, or soybeans; oil plants, e.g. oilseed rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts, or soybeans; cucurbits, e.g. squashes, cucumber, or melons; fiber plants, e.g. cotton, flax, hemp, or jute; citrus fruits, e.g. oranges, lemons, grapefruits, or mandarins; vegetables, e.g. spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits, or paprika; lauraceous plants, e.g. avocados, cinnamon, or camphor; energy and raw material plants, e.g. corn, soybean, oilseed rape, sugar cane, or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants; or ornamental and forestry plants, e.g. flowers, shrubs, broad-leaved trees, or evergreens (conifers, eucalypts, etc.); on the plant propagation material, such as seeds; and on the crop material of these plants.

More preferably, the suspension concentrates or suspoemulsions and the spraying suspensions prepared therefrom, respectively are used for controlling fungi on field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as apples, peaches, pears, cherries, cucumbers, tomatoes, beans or squashes.

The term "plant propagation material" is to be understood to denote all the generative parts of the plant, such as seeds; and vegetative plant materials, such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants; including seedlings and young plants to be transplanted after germination or after emergence from soil.

Preferably, treatment of plant propagation materials with the suspension concentrates or suspoemulsions and the spraying suspensions prepared therefrom, respectively, is used for controlling fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton, sunflower, rape seed, soybeans and fruits and fruit trees like apples, pears and peaches.

According to the invention all of the above cultivated plants are understood to comprise all species, subspecies, variants, varieties and/or hybrids which belong to the respective cultivated plants, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc, further including dwarf, semi-dwarf and full-dwarf varieties and/or hybrids with reduced height and thicker and shorter stems, e.g. short stature corn (also called ‘smart corn'), semi-dwarf wheat and dwarf rice.

Corn is also known as Indian corn or maize (Zea mays) which comprises all kinds of corn such as field corn and sweet corn. According to the invention all maize or corn subspecies and/or varieties are comprised, in particular flour corn (Zea mays var. amylacea), popcorn (Zea mays var. evert a), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high amylose Zea mays varieties), pod corn or wild maize (Zea mays var. tunicata) and striped maize (Zea mays var. japonica).

Most soybean cultivars are classifiable into indeterminate and determinate growth habit, whereas Glycine soja, the wild progenitor of soybean, is indeterminate (PNAS 2010, 107 (19) 8563-8568). The indeterminate growth habit (Maturity Group, MG 00 to MG 4.9) is characterized by a continuation of vegetative growth after flowering begins whereas determinate soybean varieties (MG 5 to MG 8) characteristically have finished most of their vegetative growth when flowering begins. According to the invention all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties. The term "cultivated plants" is to be understood as including plants which have been modified by mutagenesis or genetic engineering to provide a new trait to a plant or to modify an already present trait. Mutagenesis includes random mutagenesis using X-rays or mutagenic chemicals, but also targeted mutagenesis to create mutations at a specific locus of a plant genome. Targeted mutagenesis frequently uses oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases. Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant to add a trait or improve or modify a trait. These integrated genes are also referred to as transgenes, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, which differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific "event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.

Herbicide tolerance has been created by using mutagenesis and genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by mutagenesis and breeding are e.g. available under the name Clearfield®. Herbicide tolerance to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitors and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione, has been created via the use of transgenes.

Transgenes to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621, goxv247; for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1, aad-12; for tolerance to dicamba: dmo; for tolerance to oxynil herbicies: bxn; for tolerance to sulfonylurea herbicides: zm-hra, csr1 -2, gm-hra, S4-HrA; for tolerance to ALS inhibitors: csr1 -2; and for tolerance to HPPD inhibitors: hppdPF, W336, avhppd-03.

Transgenic corn events comprising herbicide tolerance genes include, but are not limited to, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHGOJG, HCEM485, VCO-01981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275. Transgenic soybean events comprising herbicide tolerance genes include, but are not limited to, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS- 81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127. Transgenic cotton events comprising herbicide tolerance genes include, but are not limited to, 19-51 a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211 , BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40. Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHYU, PHY23, PHY35, PHY36, RF1. RF2 and RF3.

Transgenes to provide insect resistance preferably are toxin genes of Bacillus spp. and synthetic variants thereof, like cry 1 A, cry 1 Ab, cry1Ab-Ac, crylAc, cry1 A.105, cry 1 F, cry 1 Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1 , cry34Ab1, cry35Ab1, cry9C, vip3A(a), vip3Aa20. In addition, transgenes of plant origin, such as genes coding for protease inhibitors, like CpTI and pinll, can be used. A further approach uses transgenes such as dvsnf7 to produce double-stranded RNA in plants.

Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA include, but are not limited to, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098. Transgenic soybean events comprising genes for insecticidal proteins include, but are not limited to, MON87701, MON87751 and DAS-81419. Transgenic cotton events comprising genes for insecticidal proteins include, but are not limited to, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Eventl, COT67B, COT102, T303-3, T304-40, GFM Cry1 A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.

Cultivated plants with increased yield have been created by using the transgene athb17 (e.g. corn event MON87403), or bbx32 (e.g. soybean event MON87712).

Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj ,D6D, Nc.Fad3, fad2-1 A and fatbl -A (e.g. soybean events 260-05, MCN87705 and MON87769).

Tolerance to abiotic conditions, such as drought, has been created by using the transgene cspB (corn event MCN87460) and Hahb-4 (soybean event IND-00410-5).

Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process resulting in a cultivated plant with stacked traits. Preferred combinations of traits are combinations of herbicide tolerance traits to different groups of herbicides, combinations of insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, combinations of herbicide tolerance with one or several types of insect resistance, combinations of herbicide tolerance with increased yield as well as combinations of herbicide tolerance and tolerance to abiotic conditions.

Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art. For example, detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations "International Service for the Acquisition of Agri-biotech Applications (ISAAA)” (http://www.isaaa.org/gmapprovaldatabase) and the "Center for Environmental Risk Assessment (CERA)” (http://cera-gmc.org/GMCropDatabase). Further information on specific events and methods to detect them can be found for canola events MS1, MS8, RF3, GT73, MCN88302, KK179 in WC01/031042, WC01/041558, WC01/041558, WC02/036831, WO11/153186, WC13/003558; for cotton events MON1445, MON15985, MON531 (MON15985), LLCotton25, MON88913, CCT102, 281-24-236, 3006-210-23, COT67B, GHB614, T304-40, GHB119, MCN88701, 81910 in WC02/034946, WC02/100163, WC02/100163, WC03/013224, WC04/072235, WC04/039986, WC05/103266, WC05/103266, WO06/128573, WC07/017186, WC08/122406, WC08/151780, WC12/134808, WO13/112527; for corn events GA21, MCN810, DLL25, TC1507, MON863, MIR604, LY038, MCN88017, 3272, 59122, NK603, MIR162, MCN89034, 98140, 32138, MCN87460, 5307, 4114, MON87427, DAS40278, MON87411, 33121, MCN87403, MON87419 in WC98/044140, US02/102582, US03/126634, WC04/099447, WC04/011601, WC05/103301, WC05/061720, WC05/059103, WC06/098952, WC06/039376, US2007/292854, WC07/142840, WC07/140256, WC08/112019, WC09/103049, WC09/111263, WC10/077816, WO11/084621, WO11/062904, WO11/022469, WO13/169923, WO14/116854, WO15/053998, WO15/142571 ; for potato events E12, F10, J3, J55, V11, X17, Y9 in WO14/178910, WO14/178913, WO14/178941, WO14/179276, WO16/183445, WO17/062831, WO17/062825; for rice events LLRICE06, LLRICE601, LLRICE62 in WO00/026345, WO00/026356, WO00/026345; and for soybean events H7-1, MON89788, A2704-12, A5547-127, DP305423, DP356043, MON87701, MON87769, CV127, MON87705, DAS68416-4, MON87708, MON87712, SYHT0H2, DAS81419, DAS81419 x DAS44406-6, MON87751 in WO04/074492, W006/130436, W006/108674, W006/108675, WO08/054747, W008/002872, WO09/064652, W009/102873, W010/080829, W010/037016, WO11/066384, WO11/034704, WO12/051199, WO12/082548, WO13/016527, WO13/016516, WO14/201235.

The use the suspension concentrates or suspoemulsions and the spraying suspensions prepared therefrom, respectively, on cultivated plants may result in effects which are specific to a cultivated plant comprising a certain transgene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.

The suspension concentrates or suspoemulsions and the spraying suspensions prepared therefrom, respectively, are particularly suitable for controlling the following causal agents of plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. Candida) and sunflowers (e.g. A. tragopogonis),' Alter- naria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. pom), oilseed rape (A. brassicicola or brassicae), sugar beets (A. tenuis), fruits (e.g. A. grandis), rice, soybeans, potatoes and tomatoes (e.g. A. solani, A. grandis or A. alternata), tomatoes (e.g. A. solani or A. alternata) and wheat (e.g. A. triticina),' Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e.g. A. tritici (anthracnose) on wheat and A. hordei on barley; Aureobasidium zeae (syn. Kapatiella zeae) on corn; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e.g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e.g. spot blotch (B. sorokin- iana) on cereals and e.g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e.g. strawberries), vegetables (e.g. lettuce, carrots, celery and cabbages); B. sguamosa or B. allii on onion family), oilseed rape, ornamentals (e.g. B eliptica), vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e.g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e.g. C. beticola), sugar cane, vegetables, coffee, soybeans (e.g. C. sojina or C. kikuchii) and rice;

Cladobotryum (syn. Dactylium) spp. (e.g. C. mycophilum (formerly Dactylium dendroides, teleomorph: Nectria alber- tinii, Nectria rosella syn. Hypomyces rosellus) on mushrooms; Cladosporium spp. on tomatoes (e.g. C. fulvum: leaf mold) and cereals, e.g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (ana- morph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e.g. C. sativus, anamorph:

B. sorokiniana) and rice (e.g. C. miyabeanus, anamorph: H. oryzae),' Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e.g. C. gossypii), corn (e.g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e.g.

C. coccodes: black dot), beans (e.g. C. lindemuthianum), soybeans (e.g. C. truncatum or C. gloeosporioides), vegetables (e.g. C. lagenarium or C. capsici), fruits (e.g. C. acutatum), coffee (e.g. C. coffeanum or C. kahawae) and

C. gloeosporioides on various crops; Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans, cotton and ornamentals; Cycloconium spp., e.g. C. oleaginum on olive trees; Cylindrocar- pon spp. (e.g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e.g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e.g.

D. teres, net blotch) and wheat (e.g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (formerly Phaeo- acremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa,' Elsinoe spp. on pome fruits (E pyri), soft fruits (E veneta: anthracnose) and vines (E ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E betae), vegetables (e.g. E pisi), such as cucurbits (e.g. E cichoracearum), cabbages, oilseed rape (e.g. E cruciferarum),' Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e.g. E turcicum),' Fusarium (teleomorph: Gibber- ella) spp. (wilt, root or stem rot) on various plants, such as E graminearum or E culmorum (root rot, scab or head blight) on cereals (e.g. wheat or barley), E oxysporum on tomatoes, E solani (f. sp. glycines now syn. E virguliforme ) and E tucumaniae and E brasiliense each causing sudden death syndrome on soybeans, and E verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e.g. wheat or barley) and corn; Gibberella spp. on cereals (e.g. G. zeae) and rice (e.g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnospo- rangium spp. on rosaceous plants and junipers, e.g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals, potatoes and rice; Hemileia spp., e.g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e.g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e.g. M. laxa, M. fructicola and M. fructigena (syn. Monilia spp.: bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e.g. M. graminicola (anamorph: Zymoseptoria tritici formerly Septoria tritici: Septoria blotch) on wheat or M. fijiensis (syn. Pseudocercospora fijiensis: black Sigatoka disease) and M. musicola on bananas, M. arachidicola (syn. M. arachidis or Cercospora ara- chidis), M. berkeleyi on peanuts, M. pisi on peas and M. brassiciola on brassicas; Peronospora spp. (downy mildew) on cabbage (e.g. P. brassicae), oilseed rape (e.g. P. parasitica), onions (e.g. P. destructor), tobacco (P. tabacina) and soybeans (e.g. P. manshurica),' Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialo- phora spp. e.g. on vines (e.g. P. tracheiphila and P. tetraspora) and soybeans (e.g. P. gregata: stem rot); Phoma lingam (syn. Leptosphaeria biglobosa and L. maculans: root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; Phomopsis spp. on sunflowers, vines (e.g. P. viticola: can and leaf spot) and soybeans (e.g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum),' Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e.g. P. capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e.g. P. infestans: late blight) and broad-leaved trees (e.g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, oilseed rape, radish and other plants; Plasmopara spp., e.g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits (e.g. P. leucotricha on apples) and curcurbits (P. xanthii , Poly- myxa spp., e.g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (syn. Oculimacula yallundae, 0. acuformis: eyespot, teleo- morph: Tapesia yallundae) on cereals, e.g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e.g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or .rotbrenner’, ana- morph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e.g. P. triticina (brown or leaf rust), P. strii- formis (stripe or yellow rust), P. horde! (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e.g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenopeziza spp., e.g. P. brassicae on oilseed rape; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea: rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, oilseed rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e.g. P. ultimum or P. aphani- dermatum) and P. oligandrum on mushrooms; Ramularia spp., e.g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley, R. areola (teleomorph: Mycosphaerella areola) on cotton and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, e.g. R. solan! (root and stem rot) on soybeans, R. solan! (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis and R. commune (scald) on barley, rye and triticale; Saro- cladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables (S. minor and S. sclerotiorum) and field crops, such as oilseed rape, sunflowers (e.g. S. sclerotiorum) and soybeans, S. rolfsii (syn. Athelia rolfsii) on soybeans, peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (syn. Zymoseptoria tritici, Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tucker!) on vines; Setosphaeria spp. (leaf blight) on corn (e.g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e.g. S. reiliana, syn. Ustilago reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (syn. Podosphaera xanthii: powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e.g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum, syn. Septoria nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e.g. T. basicola (syn. Chalara elegans),' Tilletia spp. (common bunt or stinking smut) on cereals, such as e.g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Trichoderma harzianum on mushrooms,' Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e.g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e.g. U. appendiculatus, syn. U. phaseoli), sugar beets (e.g. U. betae or U. beticola) and on pulses (e.g. U. vignae, U. pisi, U. viciae-fabae and U. fa- bae)', Ustilago spp. (loose smut) on cereals (e.g. U. nuda and U. avaenae), corn (e.g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e.g. V. inaegualis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e.g. V. longisporum on oilseed rape, V. dahliae on strawberries, oilseed rape, potatoes and tomatoes, and V. fungicola on mushrooms; Zymosepto- ria tritici on cereals.

The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases: rusts on soybean and cereals (e.g. Phakopsora pachyrhizi and P. meibomiae on soy; Puccinia tritici and P. striiformis on wheat); molds on specialty crops, soybean, oil seed rape and sunflowers (e.g. Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, S. minor and S. rolfsii on oil seed rape, sunflowers and soybean); Fusarium diseases on cereals (e.g. Fusarium culmorum and F. graminearum on wheat); downy mildews on specialty crops (e.g. Plasmopara viticola on vines, Phytophthora infestans on potatoes); powdery mildews on specialty crops and cereals (e.g. Uncinula necatoron vines, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals); and leaf spots on cereals, soybean and corn (e.g. Septoria tritici and S. nodorum on cereals, S. glycines on soybean, Cercospora spp. on corn and soybean).

It has been observed that populations of phytopathogenic fungi apparently consisting of non-resistant strains can readily develop resistance. The compounds can be applied under such conditions, too, to prevent the formation of resistance and the spread of resistant strains altogether. In this regard it is useful that they have strong activity also against non-resistant phytopathogenic fungi.

Fungicide-resistant strains of various phytopathgenic fungi have been reported, with strains resistant to one or more fungicides from various mode of action classes being observed by target-site mutations in the genes of the respective proteins (e.g. Qol (C3, according to FRAC convention, for details www.frac.info), quinone outside stig- matellin binding subsite inhibitors (QoSI; C8), and quinone inside inhibitors (Qil; C4): CytB target protein; sterol de- methylaition (DMI, G1): Cyp51/Erg11 ; carboxylic acid amides (CAA, H5): CesA3; SDHI (C2): SdhB, SdhC and SdhD; dicarboximides (E3): Os-1 (including Bos1, Daf1 etc.); keto reductase inhibitors (KRI; Class III SBIs; G3): Erg27; and oxysterol binding protein inhibitors (OSBPI; F9): ORP1.

Preferably the fungi to be controlled are selected from the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon.

The invention furthermore relates to a method for controlling phytopathogenic fungi selected from the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon, comprising contacting the fungi, the plant, or the plant parts to be protected against fungal attack with a fungicidally effective amount of a spraying suspension prepared from one of the suspension concentrates or suspoemulsions, described herein.

Preferably at least one fungus is selected from the species Puccinia triticina, Erysiphe graminis, Fusarium graminearum, Sclerotinia sclerotiorum, Cercospora beticola, Cercospora sojina, Septoria tritici, Ramularia collo-cygni or Venturia inegualis.

Preferably, the spraying suspension is applied when the phytopathogenic fungi is present. Accordingly, the invention comprises a method for controlling phytopathogenic fungi, comprising the steps of a) identifying a plant or a plurality of plants infected or in danger of being infected with at least one fungus selected from the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon and b) comprising contacting the fungi, the plant, or the plant parts infected or in danger of being infected with a fungicidally effective amount of a spraying suspension prepared form a suspension concentrate or suspoemulsion described herein. Preferably the plant is infected or is in danger of being infected by a fungus of the genus Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon. Even more preferred, the plant is infected or is in danger of being infected by a fungus of the species Puccinia triticina, Erysiphe graminis, Fusarium graminearum, Sclerotinia sclerotiorum, Cercospora beticola, Cercospora sojina, Septoria tritici, Ramularia collo-cygni, or Venturia inegualis.

Method for controlling phytopathogenic fungi:

The invention comprises a method for controlling phytopathogenic fungi selected from the genera, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon, comprising contacting the fungi, the plant or the plant parts to be protected against fungal attack with a fungicidally effective amount of a mixture comprising sulfur, at least one terpene, selected from limonene, terpinene, pinene, p- cymene, eugenol, geraniol, thymol and carvacrol and at least one phosphite, wherein the weight/weight ratio of the amount of sulfur to the combined amounts of the selected terpenes, is between 100 to 1 and 1 to 1, or between 70 to

I and 1 to 1 , or between 65 to 1 and 1 to 1 , or between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1 , or between 25 to 1 and 2 to 1 , or between 25 to 1 and 3 to 1 , or between 25 to 1 and 4 to 1 , or between 25 to 1 and 5 to 1 , or between 25 to 1 and 6 to 1, or between 25 to 1 and 7 to 1, or between 25 to 1 and 8 to 1, or between 25 to 1 and 9 to 1, or between 15 to 1 and 7 to 1, or between 12 to 1 and 7 to 1, or between 10 to 1 and 7 to 1, or between 12 to 1 and 8 to 1, or between

I I to 1 and 9 to 1 and the weight/weight ratio of the amount of sulfur to the combined amounts of the phosphites, preferably KH2PO3 and/or K2HPO3, is between 50 to 1 and 1 to 1, or between 40 to 1 and 1 to 1, or between 30 to 1 and 1 to 1, or between 20 to 1 and 1 to 1, or between 10 to 1 and 1 to 1, or between 5 to 1 and 1 to 1, or between 10 to 1 and 2 to 1 , or between 8 to 1 and 2 to 1 , or between 7 to 1 and 2 to 1 , or between 6 to 1 and 3 to 1 .

The term "fungicidally effective amount" denotes an amount of the composition, which is sufficient for controlling harmful fungi and which does not result in a substantial damage to the treated plants, the treated stored products or harvest, or to the treated materials. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant, stored product, harvest or material and the climatic conditions.

Preferably, the method comprises the steps of a) identifying a plant or a plurality of plants infected or in danger of being infected with at least one fungus selected from the genera, Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon and b) comprising contacting the fungi, the plant, or the plant parts to be protected against fungal attack with a fungicidally effective amount of a mixture comprising sulfur, least one terpene, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, and at least one phosphite, wherein the weight/weight ratio of the amount of sulfur to the combined amounts of the selected terpenes, is between 100 to 1 and 1 to 1 , or between 70 to 1 and 1 to 1 , or between 65 to 1 and 1 to 1 , or between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1, or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1, or between 25 to 1 and 2 to 1 , or between 25 to 1 and 3 to 1 , or between 25 to 1 and 4 to 1, or between 25 to 1 and 5 to 1, or between 25 to 1 and 6 to 1 , or between 25 to 1 and 7 to 1 , or between 25 to 1 and 8 to 1 , or between 25 to 1 and 9 to 1 , or between 15 to 1 and 7 to 1, or between 12 to 1 and 7 to 1 , or between 10 to 1 and 7 to 1 , or between 12 to 1 and 8 to 1 , or between 11 to 1 and 9 to 1 and the weight/weight ratio of the amount of sulfur to the combined amounts of the phosphites, preferably KH2PO3 and/or K2HPO3, is between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 20 to 1 and 1 to 1 , or between 10 to 1 and 1 to 1, or between 5 to 1 and 1 to 1, or between 10 to 1 and 2 to 1, or between 8 to 1 and 2 to 1 , or between 7 to 1 and 2 to 1 , or between 6 to 1 and 3 to 1 .

Preferably, the mixture comprises limonene, preferably D-limonene, wherein the weight/weight ratio between sulfur and limonene is between 100 to 1 and 1 to 1 , or between 70 to 1 and 1 to 1 , or between 65 to 1 and 1 to 1, or between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1 , or between 25 to 1 and 2 to 1 , or between 25 to 1 and 3 to 1 , or between 25 to 1 and 4 to 1 , or between 25 to 1 and 5 to 1 , or between 25 to 1 and 6 to 1 , or between 25 to 1 and 7 to 1 , or between 25 to 1 and 8 to 1 , or between 25 to 1 and 9 to 1, or between 15 to 1 and 7 to 1, or between 12 to 1 and 7 to 1 , or between 10 to 1 and 7 to 1 , or between 12 to 1 and 8 to 1 , or between 11 to 1 and 9 to 1.

More preferred at least one fungus is of a genus selected from: Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon.

Preferably at least one fungus is from a species selected from: Puccinia triticina, Puccinia striiformis, Erysiphe grami- nis, Septoria tritici, Cercospora beticola, Cercospora sojina, Sclerotinia sclerotiorum, Ramularia collo-cygni, Fusarium graminearum, Pyrenophora teres and Venturia inegualis. More preferred at least one fungus is from a species selected from: Puccinia triticina, Puccinia striiformis, Erysiphe graminis, Septoria tritici, Cercospora beticola, Cercospora sojina, Sclerotinia sclerotiorum, Ramularia collo-cygni and Fusarium graminearum.

Preferably, the mixture is applied when the phytopathogenic fungi is present or infections are likely due to the weather conditions.

The invention comprises also a method for controlling or reducing Fusarium head blight (FHB) in wheat, barley, rye or oat, comprising a) identifying a plant or a plurality of plants infected or in danger of being infected by Fusarium head blight and b) contacting the fungi, the plant or the plant parts infected or in danger of being infected by Fusarium head blight with a fungicidally effective amount of a mixture comprising sulfur, at least one terpene, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, and at least one phosphite, wherein the weight/weight ratio of the amount of sulfur to the combined amounts of the selected terpenes, is between 100 to 1 and 1 to 1 , or between 70 to 1 and 1 to 1, or between 65 to 1 and 1 to 1 , or between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1 , or between 25 to 1 and 2 to 1, or between 25 to 1 and 3 to 1, or between 25 to 1 and 4 to 1 , or between 25 to 1 and 5 to 1 , or between 25 to 1 and 6 to 1 , or between 25 to 1 and 7 to 1 , or between 25 to 1 and 8 to 1, or between 25 to 1 and 9 to 1 , or between 15 to 1 and 7 to 1 , or between 12 to 1 and 7 to 1 , or between 10 to 1 and 7 to 1, or between 12 to 1 and 8 to 1, or between 11 to 1 and 9 to 1 and the weight/weight ratio of the amount of sulfur to the combined amounts of the phosphites, preferably KH2PO3 and/or K2HPO3, is between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 20 to 1 and 1 to 1 , or between 10 to 1 and 1 to 1 , or between 5 to 1 and 1 to 1 , or between 10 to 1 and 2 to 1, or between 8 to 1 and 2 to 1 , or between 7 to 1 and 2 to 1, or between 6 to 1 and 3 to 1 .

In one embodiment at least one of the selected terpenes is limonene, preferably D-limonene, wherein the weight/weight ratio between sulfur and limonene is between 100 to 1 and 1 to 1 , or between 70 to 1 and 1 to 1 , or between 65 to 1 and 1 to 1 , or between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1, or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1, or between 25 to 1 and 2 to 1 , or between 25 to 1 and 3 to 1 , or between 25 to 1 and 4 to 1, or between 25 to 1 and 5 to 1, or between 25 to 1 and 6 to 1 , or between 25 to 1 and 7 to 1 , or between 25 to 1 and 8 to 1 , or between 25 to 1 and 9 to 1 , or between 15 to 1 and 7 to 1, or between 12 to 1 and 7 to 1 , or between 10 to 1 and 7 to 1 , or between 12 to 1 and 8 to 1 , or between 11 to 1 and 9 to 1.

Fusarium head blight is caused by several species of the fungal genus Fusarium. Fusarium graminearum is the species that causes the most serious damage to crops. Fungi of the genus Fusarium are known to produce mycotoxins. For example, Fusarium graminearum frequently produces zearalenone and trichothecenes, such as nivalenol, deox- ynivalenol (DON) and/or acetylated derivatives of DON such as 3-acetyl-DON and 15-acetyl-DON. Fungi of the genus Cercospora are known to produce mycotoxins called cercosporins.

Accordingly, the invention comprises a method to reduce the amount of mycotoxins present in plant material, comprising the steps of a) identifying a plant or a plurality of plants infected or in danger of being infected by mycotoxin producing fungi, preferably the mycotoxin producing fungi belong to the genus Fusarium or Cercospora, and b) contacting the fungi, the plant or the plant parts infected or in danger of being infected by mycotoxin producing fungi with a fungicidal ly effective amount of a mixture comprising sulfur, at least one terpene, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, and at least one phosphite, wherein the weight/weight ratio of the amount of sulfur to the combined amounts of the selected terpenes, is between 100 to 1 and 1 to 1 , or between 70 to 1 and 1 to 1, or between 65 to 1 and 1 to 1, or between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1, or between 25 to 1 and 2 to 1 , or between 25 to 1 and 3 to 1 , or between 25 to 1 and 4 to 1 , or between 25 to 1 and 5 to 1, or between 25 to 1 and 6 to 1 , or between 25 to 1 and 7 to 1, or between 25 to 1 and 8 to 1 , or between 25 to 1 and 9 to 1 , or between 15 to 1 and 7 to 1, or between 12 to 1 and 7 to 1, or between 10 to 1 and 7 to 1 , or between 12 to 1 and 8 to 1 , or between 11 to 1 and 9 to 1 and the weight/weight ratio of the amount of sulfur to the combined amounts of the phosphites, preferably KH2PO3 and/or K2HPO3, is between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 20 to 1 and 1 to 1 , or between 10 to 1 and 1 to 1 , or between 5 to 1 and 1 to 1, or between 10 to 1 and 2 to 1, or between 8 to 1 and 2 to 1, or between 7 to 1 and 2 to 1, or between 6 to 1 and 3 to 1 .

In one embodiment at least one of the selected terpenes is limonene, preferably D-limonene, in a weight/weight ratio between sulfur and limonene between 100 to 1 and 1 to 1, or between 70 to 1 and 1 to 1, or between 65 to 1 and 1 to 1, or between 50 to 1 and 1 to 1, or between 40 to 1 and 1 to 1, or between 30 to 1 and 1 to 1, or between 30 to 1 and 5 to 1, or between 25 to 1 and 1 to 1, or between 25 to 1 and 2 to 1, or between 25 to 1 and 3 to 1, or between 25 to 1 and 4 to 1, or between 25 to 1 and 5 to 1, or between 25 to 1 and 6 to 1, or between 25 to 1 and 7 to 1, or between 25 to 1 and 8 to 1, or between 25 to 1 and 9 to 1, or between 15 to 1 and 7 to 1, or between 12 to 1 and 7 to 1, or between 10 to 1 and 7 to 1, or between 12 to 1 and 8 to 1, or between 11 to 1 and 9 to 1.

The phytopathogenic fungi of the genus Puccinia are preferably selected from the species Puccinia triticina, Puccinia graminis f. sp. avenae, Puccinia graminis f. sp. poae, Puccinia graminis f. sp. secalis, Puccinia graminis f. sp. tritici, Puccinia graminis subsp. graminicola, Puccinia helianthi, Puccinia hordei, Puccinia sorghi, Puccinia striiformis f. sp. hordei and Puccinia striiformis f. sp. tritici. In one embodiment the phytopathogenic fungi are from the species Puccinia triticina.

The phytopathogenic fungi of the genus Podosphaera are preferably selected from the species Podosphaera fuligi- nea, Podosphaera leucotricha, Podosphaera clandestina, Podosphaera pannosa, Podosphaera tridactyla, Podosphaera xanthii, Podosphaera mors-uvae and Podosphaera aphanis or are selected from Podosphaera leucotricha, Podosphaera clandestina, Podosphaera pannosa, Podosphaera tridactyla, Podosphaera xanthii, Podosphaera mors- uvae and Podosphaera aphanis. In one embodiment the phytopathogenic fungi are from the species Podosphaera leucotricha. In another embodiment the phytopathogenic fungi are from the species Podosphaera fuliginea. The phytopathogenic fungi of the genus Erysiphe and Blumeria are preferably selected from the species Blumeria graminis, also known as Erysiphe graminis, Blumeria graminis f. sp. avenae, Blumeria graminis f. sp. hordei, Blumeria graminis f. sp. secalis, Blumeria graminis f. sp. tritici Erysiphe cruciferarum, Erysiphe necator, Erysiphe cichoracearum and Erysiphe betae. In one embodiment the phytopathogenic fungi are from the species Blumeria graminis.

The phytopathogenic fungi of the genus Septoria are preferably selected from the species Zymoseptoria tritici, also known as Septoria tritici, Septoria betae, Septoria glycines, Septoria helianthi and Septoria secalis. In one embodiment the phytopathogenic fungi are from the species Zymoseptoria tritici.

The phytopathogenic fungi of the genus Cercospora are preferably selected from the species Cercospora beticola, Cercospora brassicicola, Cercospora janseana, Cercospora sojina, Cercospora kikuchii, Cercospora concors, Cercospora solani, Cercospora solani-tuberosi, Cercospora sorghi and Cercospora zeae-maydis. In one embodiment the phytopathogenic fungi are from the species Cercospora beticola. In one embodiment the phytopathogenic fungi are from the species Cercospora sojina.

The phytopathogenic fungi of the genus Sclerotinia are preferably selected from the species Sclerotinia sclerotiorum. The phytopathogenic fungi of the genus Ramularia are preferably selected from the species Ramularia collo-cygni and Ramularia beticola. In one embodiment the phytopathogenic fungi are from the species Ramularia collo-cygni. The phytopathogenic fungi of the genus Fusarium are preferably selected from the species Fusarium graminearum, Fusarium culmorum, Fusarium avenaceum, Microdochium nivale, Fusarium verticilloides, Fusarium oxysporum and Fusarium poae.

In one embodiment the phytopathogenic fungi is from the species Fusarium graminearum.

The phytopathogenic fungi of the genus Pyrenophora are preferably selected from the species Pyrenophora teres, Pyrenophora tritici-repentis, Pyrenophora graminea and Pyrenophora avenae. In one embodiment the phytopathogenic fungi are selected from the species Pyrenophora teres and Pyrenophora tritici-repentis.

The phytopathogenic fungi of the genus Venturia are preferably selected from the species Venturia inaegualis, Venturia carpophila, Venturia cerasi, Venturia nashicola, Venturia pyrina, Venturia oleaginea. In one embodiment the phytopathogenic fungi are selected from the species Venturia inaegualis.

The phytopathogenic fungi of the genus Diplocarpon are preferably selected from the species Diplocarpon mali (ana- morph Marssonina coronaria), Diplocarpon mespili and Diplocarpon fragariae. In one embodiment the phytopathogenic fungi are selected from the species Diplocarpon mali.

In one embodiment the plant or the plant parts to be protected is from the genus Triticum, preferably of the species Triticum aestivum or Triticum durum, more preferred from the species Triticum aestivum, and the phytopathogenic fungi is from a species selected from Puccinia triticina, Puccinia graminis f. sp. tritici, Puccinia striiformis f. sp. tritici, Erysiphe graminis, Blumeria graminis f. sp. tritici, Zymoseptoria tritici and Pyrenophora tritici-repenti. Preferably, the plant or the plant parts are protected from Puccinia triticina and Erysiphe graminis. More preferred, the plant or the plant parts are protected from Puccinia triticina, Erysiphe graminis, and at least one of Zymoseptoria tritici and Pyrenophora tritici-repentis.

In one embodiment the plant or the plant parts to be protected is from the species Hordeum vulgare and the phytopathogenic fungi is from a species selected from Pyrenophora teres, Blumeria graminis f. sp. hordei and Ramularia collo-cygni. Preferably, the plant or the plant parts are protected from at leat two of Pyrenophora teres, Blumeria graminis f. sp. hordei and Ramularia collo-cygni.

In one embodiment the plant or the plant parts to be protected is from the species Secale cereale and the phytopathogenic fungi is from a species selected from Puccinia graminis f. sp. secalis, Blumeria graminis f. sp. secalis and Septoria secalis. Preferably, the plant or the plant parts are protected from Puccinia graminis f. sp. secalis and Blumeria graminis f. sp. secalis.

In one embodiment the plant or the plant parts to be protected is from the species Avena sativa and the phytopathogenic fungi is from a species selected from Puccinia graminis f. sp. avenae, Blumeria graminis f. sp. avenae, and Pyrenophora avenae. Preferably, the plant or the plant parts are protected from Puccinia graminis f. sp. avenae and Blumeria graminis f. sp. avenae.

In one embodiment the plant or the plant parts to be protected is from the species Zea mays and the phytopathogenic fungi is from a species selected from Puccinia sorghi and Cercospora zeae-maydis.

In one embodiment the plant or the plant parts to be protected is from the species Beta vulgaris and the phytopathogenic fungi is from a species selected from Cercospora beticola, Septoria betae and Ramularia beticola. Preferably, the plant or the plant parts are protected from Cercospora beticola and at least one of Septoria betae and Ramularia beticola.

In one embodiment the plant or the plant parts to be protected is from the species Brassica napus and the phytopath- ogenic fungi is from a species selected from Sclerotinia sclerotiorum and Erysiphe cruciferarum. Preferably, the plant or the plant parts are protected from Sclerotinia sclerotiorum.

In one embodiment the plant or the plant parts to be protected is from the species Glycine max and the phytopatho- genic fungi is from a species selected from Cercospora kikuchii, Cercospora sojina, Septoria glycines and Sclerotinia sclerotiorum. Preferably, the plant or the plant parts are protected from Sclerotinia sclerotiorum. or Cercospora sojina. In one embodiment the plant or the plant parts to be protected is from the species Solanum tuberosum and the phy- topathogenic fungi is from a species selected from Erysiphe cichoracearum, Cercospora concors, Cercospora solani, Cercospora solani-tuberosi, and Sclerotinia sclerotiorum. Preferably, the plant or the plant parts are protected from Sclerotinia sclerotiorum.

In one embodiment the plant or the plant parts to be protected is from the species Helianthus annuus and the phyto- pathogenic fungi is from a species selected from Puccinia helianthi, Septoria helianthi, and Sclerotinia sclerotiorum. Preferably, the plant or the plant parts are protected from Sclerotinia sclerotiorum.

In one embodiment the plant or the plant parts to be protected is from the genus Triticum, Hordeum, Secale or Zea, preferably of the species Triticum aestivum, Triticum durum, Hordeum vulgare, Secale cereale or Zea mays, more preferred from the species Triticum aestivum, and the phytopathogenic fungi is from a species selected from the genus Fusarium, preferably from the species Fusarium graminearum, Fusarium culmorum, Fusarium avenaceum, Fusarium verticilloides, Fusarium oxysporum and Fusarium poae, more preferred from the species Fusarium graminearum.

In one embodiment the plant or the plant parts to be protected is from the genus Malus, preferably of the species Ma- lus domestica and the phytopathogenic fungi is from the species Venturia inaequalis, Podosphaera leucotricha.or Diplocarpon mali.

In one embodiment the plant or the plant parts to be protected is from the genus Pyrus, preferably of the species Py- rus communis or Pyrus pyrifolia and the phytopathogenic fungi is from the species Venturia pyrina, Venturia nash- icola or Diplocarpon mespili.

In one embodiment the plant or the plant parts to be protected is from the genus Malus, Prunus, Pyrus or Olea, preferably of the species Malus domestica, Prunus persica, Prunus domestica, Prunus domestica, Prunus armeniaca, Prunus avium, Prunus cerasus, Pyrus pyrifolia, Pyrus communis or Olea europaea, and the phytopathogenic fungi is from a species selected from the genus Venturia, preferably of the species Venturia inaegualis, Venturia carpophila, Venturia cerasi, Venturia nashicola, Venturia pyrina, or Venturia oleaginea.

In one embodiment the plant or the plant parts to be protected is from banana or plantain and the phytopathogenic fungi is from a species selected from Mycosphaerella fiijiensis, Mycosphaerella musicola, Cercospora hayi, Sclerotinia sclerotiorum, or Septoria eumusae.

The plant species named above are understood to comprise all subspecies, variants, varieties and/or hybrids which belong to the respective plant species, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc, further including dwarf, semi-dwarf and full-dwarf varieties and/or hybrids with reduced height and thicker and shorter stems. Corn is also known as Indian corn or maize (Zea mays) which comprises all kinds of corn such as field corn and sweet corn. According to the invention all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties.

The mixtures may be combined with biopesticides. The biopesticides may be added to the mixtures as a tank mix to prepare the spraying suspensions or may be directly added as integral part of the agrochemical formulation comprising the mixtures. Alternatively, the biopesticides can be applied to the fungi, the plant or the plant parts to be protected against fungal attack shortly before or after the spraying suspension comprising the mixtures is applied.

The following list of biopesticides can be used in combination with the mixtures described herein. The list is intended to illustrate the possible combinations but does not limit them:

Biopesticides

L1) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelo- myces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliquefaciens ssp. plantarum (also referred to as B. velezensis), B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, B. velezensis, Candida oleophila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonosta- chys rosea f. catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioti- cus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus epiphyticus, P. polymyxa, Pantoea vagans, Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus,

S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile,

T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacor- rhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);

L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract;

Another embodiment of the invention are the mixtures described above to be used in the methods for controlling phy- topathogenic fungi. Preferably the mixtures comprise sulfur, at least one terpene, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol and at least one phosphite, wherein the weight/weight ratio of the amount sulfur to the combined amounts of the selected terpenes, is between 100 to 1 and 1 to 1, or between 70 to 1 and 1 to 1, or between 65 to 1 and 1 to 1, or between 50 to 1 and 1 to 1, or between 40 to 1 and 1 to 1, or between 30 to 1 and 1 to 1 , or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1 , or between 25 to 1 and 2 to 1 , or between 25 to 1 and 3 to 1 , or between 25 to 1 and 4 to 1 , or between 25 to 1 and 5 to 1 , or between 25 to 1 and 6 to 1 , or between 25 to 1 and 7 to 1, or between 25 to 1 and 8 to 1, or between 25 to 1 and 9 to 1 , or between 15 to 1 and 7 to 1 , or between 12 to 1 and 7 to 1 , or between 10 to 1 and 7 to 1 , or between 12 to 1 and 8 to 1, or between 11 to 1 and 9 to 1 and the weight/weight ratio of the amount of sulfur to the combined amounts of the phosphites, preferably KH2PO3 and/or K2HPO3, is between 50 to 1 and 1 to 1, or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 20 to 1 and 1 to 1 , or between 10 to 1 and 1 to 1 , or between 5 to 1 and 1 to 1 , or between 10 to 1 and 2 to 1 , or between 8 to 1 and 2 to 1 , or between 7 to 1 and 2 to 1 , or between 6 to 1 and 3 to 1..

Preferably the mixture comprises limonene, more preferred D-limonene, in a weight/weight ratio of sulfur to limonene between 100 to 1 and 1 to 1 , or between 70 to 1 and 1 to 1, or between 65 to 1 and 1 to 1 , or between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1 , or between 25 to 1 and 2 to 1, or between 25 to 1 and 3 to 1, or between 25 to 1 and 4 to 1 , or between 25 to 1 and 5 to 1 , or between 25 to 1 and 6 to 1 , or between 25 to 1 and 7 to 1 , or between 25 to 1 and 8 to 1, or between 25 to 1 and 9 to 1 , or between 15 to 1 and 7 to 1 , or between 12 to 1 and 7 to 1 , or between 10 to 1 and 7 to 1, or between 12 to 1 and 8 to 1 , or between 11 to 1 and 9 to 1.

The invention comprises also the use of a mixture comprising sulfur, at least one terpene, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol and at least one phosphite, wherein the weight/weight ratio of the amount of sulfur to the combined amounts of the selected terpenes, is between 100 to 1 and 1 to 1 , or between 70 to 1 and 1 to 1, or between 65 to 1 and 1 to 1, or between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 30 to 1 and 5 to 1 , or between 25 to 1 and 1 to 1, or between 25 to 1 and 2 to 1 , or between 25 to 1 and 3 to 1 , or between 25 to 1 and 4 to 1 , or between 25 to 1 and 5 to 1, or between 25 to 1 and 6 to 1 , or between 25 to 1 and 7 to 1, or between 25 to 1 and 8 to 1 , or between 25 to 1 and 9 to 1 , or between 15 to 1 and 7 to 1, or between 12 to 1 and 7 to 1, or between 10 to 1 and 7 to 1 , or between 12 to 1 and 8 to 1 , or between 11 to 1 and 9 to 1 and the weight/weight ratio of the amount of sulfur to the combined amounts of the phosphites, preferably KH2PO3 and/or K2HPO3, is between 50 to 1 and 1 to 1 , or between 40 to 1 and 1 to 1 , or between 30 to 1 and 1 to 1 , or between 20 to 1 and 1 to 1 , or between 10 to 1 and 1 to 1 , or between 5 to 1 and 1 to 1 , or between 10 to 1 and 2 to 1 , or between 8 to 1 and 2 to 1 , or between 7 to 1 and 2 to 1 , or between 6 to 1 and 3 to 1 , to control phytopathogenic fungi selected from the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon.

Preferably at least one fungus species to be controlled is selected from Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon. The methods for controlling phytopathogenic fungi described herein do not include the prophylactic or therapeutic treatment of the animal or human body. Typically, the mixtures are diluted with water to obtain spraying suspensions, which are then applied in the methods for controlling phytopathogenic fungi.

Preferably the mixtures are comprised in agrochemical formulations, which are then diluted with water to prepare the spraying suspensions. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Claims

1. A mixture comprising: a) sulfur b) one or more terpenes selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol, and c) phosphite.

2. The mixture of claim 1 , wherein the weight/weight ratio of sulfur to the combined amounts of terpenes is between 25 to 1 and 9 to 1 .

3. The mixture of claim 1 or 2, wherein the weight/weight ratio of sulfur to the amount of phosphite is between 10 to 1 and 1 to 1 .

4. The mixture of any one of claims 1 to 3, wherein the weight/weight ratio of the combined amounts of terpenes to the amount of phosphite is between 8 to 1 and 1 to 1 .

5. The mixture of any one of claims 1 to 4, wherein the mixture comprises limonene.

6. The mixture of any one of claims 1 to 5, wherein the weight/weight ratio of limonene to the combined amounts of other terpenes is 90 to 1 or higher.

7. The mixture of any one of claims 1 to 6, wherein the mixture comprises KH2PO3 and/or K2HPO3

8. The mixture of any one of claims 1 to 7, wherein the weight/weight ratio of KH2PO3 to the combined amounts of other phosphites is 90 to 1 or higher.

9. A method for controlling phytopathogenic fungi comprising contacting the fungi, the plant or the plant parts to be protected against fungal attack with a fungicidal ly effective amount of a mixture as claimed in any one of claims 1 to 8.

10. A method as claimed in claim 9, comprising the steps of a) identifying a plant or a plurality of plants infected or being in danger of being infected with at least one phytopathogenic fungus and b) contacting the fungus, the plant, or the plant parts to be protected against fungal attack with a fungicidally effective amount of a mixture as claimed in any one of claims 1 to 8.

11. A method as claimed in claim 9 or 10, wherein at least one phytopathogenic fungi is selected from the genera Puccinia, Erysiphe, Blumeria, Podosphaera, Septoria, Cercospora, Sclerotinia, Pyrenophora, Ramularia, Fusarium, Venturia, and Diplocarpon.

12. A method as claimed in any one of claims 9 to 10, wherein the fungi to be controlled is from a species selected from: Puccinia triticina, Puccinia striiformis, Erysiphe graminis, Septoria tritici, Cercospora beticola, Cercospora sojina, Sclerotinia sclerotiorum, Ramularia collo-cygni, Fusarium graminearum, Pyrenophora teres and Venturia inegualis.

13. A suspension concentrate or suspoemulsion formulation comprising: a) a mixture as claimed in any one of claim 1 to 8 and b) one or more carrier oils and c) optionally further components.

14. A suspension concentrate or suspoemulsion formulation as claimed in claim 13, comprising: a) 400 to 700 gram/liter sulfur, b) 100 to 200 gram/liter of phosphite, c) 30 to 60 gram/liter of terpenes, selected from limonene, terpinene, pinene, p-cymene, eugenol, geraniol, thymol and carvacrol d) 10 to 300 gram/liter of one or more carrier oils and e) optionally further components, wherein the amounts of a), b), c), d) and optionally e) add up to a volume of 1 liter.

15. The use of a mixture as claimed in any one of claims 1 to 8 or of a suspension concentrate or suspoemulsion formulation as claimed claims 13 or 14 to control phytopathogenic fungi.