CN107708421B - Reagent and method for reducing E/Z isomerization of dimethomorph - Google Patents

Reagent and method for reducing E/Z isomerization of dimethomorph Download PDF

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CN107708421B
CN107708421B CN201680032793.2A CN201680032793A CN107708421B CN 107708421 B CN107708421 B CN 107708421B CN 201680032793 A CN201680032793 A CN 201680032793A CN 107708421 B CN107708421 B CN 107708421B
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dimethomorph
isomer
composition
fosetyl
aluminum
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CN107708421A (en
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詹姆斯·蒂莫西·布里斯托
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Jiangsu Rotam Chemical Co Ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

A method of reducing E/Z isomerization of dimethomorph is provided comprising administering dimethomorph in conjunction with fosetyl-aluminum. Also provided is a method of reducing the instability of dimethomorph in fungicidal activity in the presence of light, comprising contacting dimethomorph with fosetyl-aluminum. Further provided are methods of preventing or reducing fungal infestation of plants at a locus comprising applying dimethomorph and fosetyl-aluminum to the locus. The composition comprises dimethomorph and fosetyl-aluminum.

Description

Reagent and method for reducing E/Z isomerization of dimethomorph
Cross Reference to Related Applications
This application claims priority to uk patent application GB1515894.2 filed on 8/9/2015, the contents of which are incorporated herein by reference in their entirety.
The present invention provides agents for reducing the E/Z isomerization of dimethomorph. The invention further relates to a composition comprising the E and/or Z isomer of dimethomorph and a conversion reagent. The invention also relates to a method for reducing the E/Z isomerization of dimethomorph.
Agrochemically active compounds such as pesticides are often exposed to solar radiation after outdoor application. For some active compounds this results in a reduction of their pesticidal activity.
(EZ) -4- [3- (4-chlorophenyl) -3- (3, 4-dimethoxyphenyl) acryloyl ] morpholine, commonly known as dimethomorph, is a known fungicide. Dimethomorph can exist as E and Z isomers, as shown below.
Figure GDA0002644133510000011
However, only the Z isomer of dimethomorph is intrinsically active as a fungicide. Upon irradiation with light, the Z isomer initially administered isomerizes to the E isomer.
It has been found that dimethomorph is inactive after light irradiation. More specifically, the effect of light irradiation of dimethomorph is to convert the Z isomer to the E isomer, resulting in loss of fungicidal activity.
Therefore, techniques are needed to increase the stability of dimethomorph when exposed to light. In particular, there is a need for techniques that reduce isomerization of dimethomorph after exposure to light, more particularly E/Z isomerization.
Surprisingly, it has now been found that the E/Z isomerization of dimethomorph after exposure to light can be reduced by the use of agents, in particular fosetyl-aluminum. In particular, it has been found that the application of dimethomorph and fosetyl-aluminum (e.g. by means of a composition comprising both dimethomorph and fosetyl-aluminum) to the locus to be treated significantly reduces the isomerization of dimethomorph after exposure to light, in particular the conversion of the Z isomer to the E isomer. This in turn maintains the fungicidal activity of the dimethomorph active ingredient.
Accordingly, in a first aspect, the present invention provides a method of reducing the E/Z isomerization of dimethomorph comprising administering dimethomorph in conjunction with fosetyl-aluminum.
In a second aspect, the present invention provides a method of reducing the instability of fungicidal activity of dimethomorph in the presence of light, the method comprising contacting dimethomorph with fosetyl-aluminum.
In a further aspect, the invention provides a method of preventing or reducing fungal infestation of plants at a locus, the method comprising applying to the locus dimethomorph and fosetyl-aluminum.
In a further aspect, the present invention provides a composition comprising dimethomorph and fosetyl-aluminum.
Still further, the present invention provides the use of fosetyl-aluminum in reducing the E/Z isomerization of dimethomorph.
E/Z isomerization of dimethomorph is understood to mean the double bond conversion from the E isomer to the Z isomer or from the Z isomer to the E isomer. It has been found that the presence of fosetyl-aluminum significantly reduces the conversion of the Z isomer to the E isomer of dimethomorph. Furthermore, it has been found that in the case of a mixture of E and Z isomers of dimethomorph, the presence of fosetyl-Al can increase the amount of Z isomer present over time.
The reduction in the E/Z isomerization of dimethomorph is achieved if the weight ratio of Z isomer to E isomer of dimethomorph in the presence of fosetyl-Al decreases more slowly than the change in said ratio in the absence of fosetyl-Al, or the weight ratio of Z isomer to E isomer remains the same or increases compared to its starting value.
In the present invention, dimethomorph can be employed or present as the E isomer, the Z isomer, or a combination of the two isomers. The E and Z isomers may be present in the dimethomorph component in any relative amount. The E or Z isomer of dimethomorph may each be present in the composition in an amount of at least 5 wt.%, preferably at least 10 wt.%, more preferably at least 20 wt.%, still more preferably at least 30 wt.%, still more preferably at least 40 wt.%, more particularly preferably at least 50 wt.%, based on the total amount of dimethomorph E and Z isomers. These values relate to the amount of isomers of dimethomorph initially (i.e., when dimethomorph is combined with or contacted with fosetyl-aluminum).
In one aspect, the present invention provides a composition comprising dimethomorph and fosetyl-aluminum. The dimethomorph may be present in the composition in any amount suitable to provide the desired fungicidal activity. The dimethomorph may be present in the composition in an amount of at least 0.1 wt.%, more preferably at least 1 wt.%, still more preferably at least 2 wt.%, more preferably at least 3 wt.%. The dimethomorph may be present in an amount of up to 99 wt.%, preferably up to 90 wt.%, more preferably up to 80 wt.%, still more preferably up to 75 wt.%. The amount of dimethomorph may be 0.1 to 99 wt.%, preferably 1 to 70 wt.%, more preferably 1 to 50 wt.%, still more preferably from 1 to 30 wt.%, still more preferably 1 to 10 wt.% of the composition. In one embodiment, dimethomorph is present in the composition in an amount of 7 wt.% of the composition.
As discussed above, the presence of fosetyl-aluminum reduces or prevents the conversion of the Z isomer to the E isomer of dimethomorph and can facilitate the conversion of the E isomer to the Z isomer. Without wishing to be bound by any particular theory, it is believed that fosetyl-aluminum is capable of generating groups that attack the double bond of the dimethomorph E isomer and allow rotation of the single bond. Fosetyl-aluminum can be used in pure form as a technical grade mixture.
As noted above, in one aspect of the present invention, compositions comprising dimethomorph and fosetyl-aluminum are provided. In the compositions of the present invention, fosetyl-aluminum may be present in any amount suitable to maintain the desired fungicidal activity of the dimethomorph fungicide. Fosetyl-aluminum may be present in an amount of from 0.1 wt.%, preferably from 1 wt.%, more preferably from 5 wt.%, still more preferably from 10 wt.%, still more preferably from 20 wt.% of the composition. Fosetyl-aluminum may be present in an amount of up to 99 wt.%, preferably up to 90 wt.%, more preferably up to 80 wt.%, still more preferably up to 75 wt.%, still more preferably up to 70 wt.%. Fosetyl-aluminum may be present in the composition in an amount of from 0.1 wt.% to 99 wt.%, preferably from 1 wt.% to 80 wt.%, more preferably from 30 wt.% to 70 wt.%, still more preferably from 50 wt.% to 60 wt.%.
As noted above, in the present invention, fosetyl-aluminum functions to reduce the conversion of the Z isomer of dimethomorph to the E isomer and to increase the conversion of the E isomer to the Z isomer. In the present invention, initially, dimethomorph can be used in the form of the Z isomer, the E isomer or a mixture of the two isomers. In the case where the Z isomer of dimethomorph was present in the original dimethomorph material, fosetyl-aluminum functions to maintain the presence of the Z isomer. In the case where the E isomer of dimethomorph was present in the original dimethomorph material, fosetyl-al functions to convert the E isomer to the Z isomer, thereby maintaining or increasing the amount of Z isomer present.
Preferably, dimethomorph is used in a form at least partially comprising the Z isomer. In this way, from the start of use, dimethomorph has fungicidal activity.
Preferably, the initial dimethomorph material comprises at least 10 wt.% of the Z isomer, more preferably at least 20 wt.%, still more preferably at least 30 wt.%, still more preferably at least 40 wt.%, particularly preferably at least 50 wt.%. The initial dimethomorph material may contain higher amounts of Z isomer, for example at least 60 wt.%, 70 wt.%, 80 wt.%, or 90 wt.%. The initial dimethomorph material may consist essentially of the Z isomer. Alternatively, the initial dimethomorph material may consist essentially of the E isomer, although this is not a preferred embodiment.
The amount of the Z isomer generally varies, more preferably increases, under the action of fosetyl-aluminum. Preferably, fosetyl-aluminum is used in an amount such that, after contact with dimethomorph, the Z isomer of dimethomorph is present in an amount of at least 50 wt.%, more preferably in an amount of at least 60 wt.%, still more preferably in an amount of at least 70 wt.%, still more preferably in an amount of at least 80 wt.%, with at least 85 wt.%, and at least 90 wt.% being particularly preferred. The Z isomer having higher pesticidal activity is preferably present in excess.
Compositions comprising dimethomorph and fosetyl-aluminum may be employed in the present invention. Alternatively, or in addition, the present invention may employ dimethomorph and fosetyl-aluminum provided in separate compositions.
The compositions used in the present invention may be formulated into any type conventional for agrochemical formulations, such as solutions, emulsions, suspensions, dusts, pastes and granules. The type of formulation depends on the particular intended use and should provide a fine and homogeneous distribution of the active ingredients fosetyl-aluminum and dimethomorph. Examples of suitable types of compositions are soluble Solutions (SL), Emulsifiable Concentrates (EC), aqueous Emulsions (EW), Microemulsions (ME), Suspensions (SC), oil-based suspensions (OD), Flowable Suspensions (FS), water dispersible granules (WG), water-Soluble Granules (SG), Wettable Powders (WP), soluble powders (WP), water-Soluble Powders (SP), Granules (GR), microencapsulated granules (CG), Fine Granules (FG), Macroemulsions (MG), macroemulsions (CS), and microencapsulated suspensions (MG). Preferred formulation types are water dispersible granules (WG) and suspending agents (SC).
As noted above, as an alternative to the compositions of the present invention, fosetyl-aluminum and dimethomorph may be used separately, for example by being applied to the locus as separate formulations, or by being combined prior to application to the locus (for example when preparing a tank mix). In this case, fosetyl-aluminum and dimethomorph may each be used in one of the above formulation types.
The formulations may further comprise adjuvants known in the art as being conventional for plant protection compositions, the choice of adjuvant depending on the type of formulation and its intended use. Typical adjuvants include extenders, carriers, solvents, surfactants, stabilizers, defoamers, antifreeze, preservatives, antioxidants, colorants, thickeners, solid stickers, and inert fillers. Such adjuvants are known in the art and are commercially available. Their use in the formulation of the compositions of the present invention will be apparent to those skilled in the art.
The composition may further comprise one or more inert fillers. Such inert fillers are known in the art and are commercially available. Suitable fillers include, for example, natural ground minerals such as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth; or synthetic ground minerals such as highly dispersed silicic acid, alumina, silicates, and calcium and hydrogen phosphates. Suitable inert fillers for granules include, for example, crushed and fractionated natural minerals such as calcite, marble, pumice, sepiolite and dolomite; or synthetic particles of inorganic and organic floor materials; and particles of organic materials such as sawdust, coconut shells, corn cobs, and tobacco stalks.
The composition optionally comprises one or more surfactants, preferably nonionic, cationic and/or anionic in nature; and surfactant mixtures having good emulsifying, dispersing and wetting properties. The choice of surfactant will depend on the type of formulation and the intended use. Suitable surfactants are known in the art and are commercially available.
Suitable anionic surfactants may be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds. Soaps which may be used are higher fatty acids (C)10To C22) Alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of, for example, oleic or stearic acid or the sodium or potassium salts of natural fatty acid mixtures. The surfactant may be an emulsifier, dispersant or wetting agent of ionic or non-ionic type. Examples which may be used are salts of polyacrylic acids, salts of lignosulfonic acids, salts of benzenesulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (especially alkylphenols), sulfosuccinate esters, taurine derivatives (especially alkyl taurates) or phosphoric esters of polyethoxylated phenols or alcohols. The presence of at least one surfactant is generally required when the active compound and/or inert carrier and/or adjuvant/adjuvant is not soluble in water and the final vehicle of administration of the composition is water.
The composition optionally further comprises one or more polymeric stabilizers. Suitable polymeric stabilizers that may be used in the present invention include, but are not limited to, polypropylene, polyisobutylene, polyisoprene, copolymers of mono-and diolefins, polyacrylates, polystyrene, polyvinyl acetate, polyurethanes, or polyamides. Suitable stabilizers are known in the art and are commercially available.
The surfactants and polymeric stabilizers mentioned above are generally believed to impart stability to the composition, thereby allowing the composition to be formulated, stored, transported, and applied.
Suitable antifoams include all substances which can generally be used for this purpose in agrochemical compositions. Suitable defoamers are known in the art and are commercially available. Particularly preferred defoamers are mixtures of polydimethylsiloxanes and perfluoroalkylphosphonic acids, such as silicone defoamers available from GE or Compton.
Suitable organic solvents are selected from all customary organic solvents which dissolve the active compounds used sufficiently. Likewise, suitable organic solvents for dimethomorph and fosetyl-aluminum are known in the art. The following may be mentioned as preferred: n-methylpyrrolidone, N-octylpyrrolidone, cyclohexyl-1-pyrrolidone; or SOLVESSOTM200, a mixture of paraffinic, iso-paraffinic, cyclo-paraffinic and aromatic hydrocarbons. Suitable solvents are commercially available.
Suitable preservatives include all materials which may be conventionally used for such purposes in agrochemical compositions of this type and are likewise well known in the art. Suitable examples which may be mentioned include
Figure GDA0002644133510000071
(from Bayer AG) and
Figure GDA0002644133510000072
(from Bayer corporation).
Suitable antioxidants are all substances which can be used for this purpose in agrochemical compositions in general, as is known in the art. Butylated hydroxytoluene is preferred.
Suitable thickeners include all substances which can be used for this purpose in agrochemical compositions in general. Such as xanthan gum, polyvinyl alcohol (PVOH), cellulose and its derivatives, clay hydrous silicates, magnesium aluminum silicates, or mixtures thereof. Likewise, such thickeners are known in the art and are commercially available.
The composition may be applied by methods known in the art. These methods include spraying (misting), dusting, spreading, brushing, pouring, coating, spraying (spraying), dipping, soaking, injecting, and irrigating.
Fosetyl-aluminum can be contacted with dimethomorph at any stage during the preparation and use of the invention. For example, the two components may be combined in a single composition. Alternatively, the two components may be applied separately and combined at the site. As another alternative, the two components may be brought into contact with each other just prior to use, for example by way of being a tank mix.
The application (use) rates of fosetyl-aluminum and dimethomorph in the present invention may vary, for example, depending on the type of use, the type of crop, the particular active compound employed, the type of plant, but should be such that the active compounds in the combination are applied in an effective amount to provide the desired effect (e.g., disease or pest control). The amounts of the components applied for a given set of conditions can be readily determined by experimentation.
Suitable application rates for each of dimethomorph and fosetyl-aluminum are in the range of from 50 to 5000 grams per hectare. A preferred combined application rate of both dimethomorph and fosetyl-aluminum is from 500 to 5000 grams per hectare.
In general, satisfactory results will be obtained when 100 to 400 g/ha, for example 210 g/ha, of dimethomorph and 750 to 3000 g/ha, for example 1500 or 1800 g/ha, of fosetyl-aluminum are employed.
The present invention may be used to prevent and/or treat diseases caused by a wide range of fungal pathogens such as, but not limited to:
pseudoperonospora cubensis (downy mildew); phytophthora (Phytophthora); pseudoperonospora cubensis in the cucurbitaceae family, such as melon, watermelon, zucchini, squash and cucumber;
fruits such as apples, avocados, raspberries, blackberries, blueberries, citrus, cranberries, grapes, vines, peaches, pineapples, raspberries, rubies and strawberries are Phytophthora on which grape branch is common (Phomopsis viticola), pseudoperonospora velutipes (pseudoperonospora rosea), papulosis (Pseudomonas syringae herpetiformis pv. papulona), Phytophthora root rot (strawberry blight fragaria), Phytophthora root rot (Phytophthora species), red root heart disease (strawberry blight), Phytophthora root rot (Phytophthora root rot), Phytophthora root rot (Phytophthora capsicum), Phytophthora rot (Phytophthora capsici), Phytophthora root rot (Phytophthora capsicum gloeosporioides), Phytophthora canker (Phytophthora rot (Phytophthora), Phytophthora root rot (Phytophthora), Phytophthora (Phytophthora) and Phytophthora (Phytophthora) on), Phytophthora rot (Phytophthora) on (Phytophthora) and Phytophthora root rot (Phytophthora) on) Crown rot (phytophthora infestans), root rot (phytophthora species);
phytophthora root rot on ginseng;
pythium (phytophium), Phytophthora, crown and root rot (Phytophthora species), Phytophthora root rot (Phytophthora cinnamomi), Phytophthora aerata (Phytophthora capsici), Phytophthora aerata (Phytophthora species including oak sudden death pathogen (Phytophthora ramorum), dreadenia (Phytophthora drechsleri), Phytophthora nicotianae (Phytophthora nicotianae), and Phytophthora parasitica (Phytophthora parasitica)), Phytophthora roots, crowns and stalk rot (Phytophthora species), downy mildew (stemona (Bremia), pseudodowny mildew (Pseudoperonospora), downy mildew (Peronospora), and Plasmopara (Plasmopara), downy mildew (Peronospora), Pseudoperonospora (Pseudoperonospora), downy mildew (Peronospora Pseudoperonospora));
penicillium on tobacco (Peronospora tabacina);
pythium rot, leaf and base rot anthracnose, and pythium nodosum (bentgrass dead spot) on turf;
alternaria species (Alternaria spp.) on vegetables, anthracnose (Colletotrichum spp.), Colletotrichum anthracnose (Colletotrichum spp.), Colletotrichum (Colletotrichum coccoides), Colletotrichum orbiculare (Colletotrichum debium), Colletotrichum gloeosporioides (Colletotrichum gloeosporioides), periphytolacca species (glomerita) [ sexually ], Colletotrichum lactucae (Marssonina pansoniana), Botrytis cinerea (Botrytis Bunthraustrine), downy mildew (Bremia lactuca), downy mildew (Botrytis cinerea), Phytophthora parasitica (Phytophthora parasitica), Phytophthora infestans (Phytophthora parasitica), Phytophthora parasitica (Phytophthora parasitica), Phytophthora infestaphylum f.sp.), Phytophthora parasitica (Phytophthora parasitica), Phytophthora parasitica (Phytophthora parasitica), Phytophthora parasitica) on (Phytophthora parasitica), Phytophthora parasitica) and phytophth, Phytophthora infestans (Botrytis squamosal), leaf spot (addigo stemma andrina var andena (Phoma andiagena var. anatina)), phytophthora root rot (phytophthora species, phytophthora cryptica (p. cryptotogora), porphyra (Alternaria solani), Septoria leaf spot (Septoria leaf spot), white rust (Albugo occidentalis), vegetables such as chinese cucumber, balsam pear, bitter melon, chicory, pakchoi, kalanchoe, broccoli, cabbage (napa), cabbage (chinese mustard), cantaloupe, broccoli, lochia, white gourd, melon, cucumber, garlic, kohlrabi (garlic), cabbage (chinese mustard), cucurbits (chinese mustard greens sativa), cucumis melo, broccoli, cucurbita, watermelon, garlic, kohlrabi, ko, Melons, onions (dry balls), onions (green), onions (Welch), melons, peppers, potatoes, rutabaga, shallots, spinach, zucchini, green tomatoes, and winter squash.
Furthermore, the present invention may be used for the prevention and/or treatment of diseases caused by fungal pathogens such as, but not limited to:
downy mildew on fruits such as grapes (downy mildew);
phytophthora infestans (late blight) on vegetables such as tomatoes, eggplants and peppers; and
the cucurbitaceae family is, for example, the cucumber downy mildew (downy mildew) on melons, watermelons, cucumber bugs, pumpkins and cucumbers.
The invention has a series of advantages. First, the rate of isomerization of Z to E of dimethomorph is significantly reduced. As a result, the applied dimethomorph material remained active longer in the sun. As a further result, the application rate of dimethomorph can be reduced.
The dimethomorph and fosetyl-aluminum can be applied simultaneously or consecutively at short time intervals, e.g., on the same day, to the plants, plant parts and/or surroundings that are desired to be controlled. The dimethomorph and fosetyl-aluminum may be applied to, one or more parts of, or around the plant (e.g., leaves or seeds) in any order. Each compound may be administered only once or more than once. Preferably, dimethomorph and fosetyl-aluminum are each applied a plurality of times, in particular from 1 to 5 times, more preferably 2 times.
The dimethomorph and fosetyl-aluminum may be administered in any desired order, in any combination, sequentially or simultaneously. Where dimethomorph and fosetyl-aluminum are administered simultaneously in the present invention, they may be administered as compositions comprising dimethomorph and fosetyl-aluminum, in which case dimethomorph and fosetyl-aluminum may each be obtained from separate formulation sources and mixed together (known as tank mix, ready-to-use, spray liquor, or slurry), optionally with other pesticides; or dimethomorph and fosetyl-aluminum can be provided as a single formulation mixture source (known as a premix, concentrate, formulated compound (or product)) and optionally mixed together with other pesticides.
The compositions according to the invention are distinguished by the fact that: they are particularly well tolerated by plants and are environmentally friendly.
The invention will be further described by the following specific examples, which are presented for illustrative purposes only.
In the following examples, the indicated percentages are by weight, unless otherwise indicated.
Examples
EXAMPLE 1 preparation of the composition
The following compositions were prepared. Compositions 8 and 9 were prepared for comparative purposes and are not examples of the present invention.
Composition 1: WDG 10% phosethyl-Al
A Water Dispersible Granule (WDG) formulation was prepared having the following composition:
7% dimethomorph; 10% fosetyl-aluminum; 5% sodium lauryl sulfate; 5% fatty alcohol polyglycol ether; 2% lignosulfonic acid, sodium salt, sulfomethylated; 8% ammonium sulfate; 1% of a defoaming agent; 25% sucrose and 37% lactose.
The dimethomorph used to form the composition comprises a mixture of the E and Z isomers.
Composition 2: WDG 20% phosethyl-Al
A Water Dispersible Granule (WDG) formulation was prepared having the following composition:
7% dimethomorph; 20% fosetyl-aluminum; 5% sodium lauryl sulfate; 5% fatty alcohol polyglycol ether; 2% lignosulfonic acid, sodium salt, sulfomethylated; 8% ammonium sulfate; 1% of a defoaming agent; 20% sucrose and 32% lactose.
The dimethomorph used to form the composition comprises a mixture of the E and Z isomers.
Composition 3: WDG 30% phosethyl-Al
A Water Dispersible Granule (WDG) formulation was prepared having the following composition:
7% dimethomorph; 30% fosetyl-aluminum; 5% sodium lauryl sulfate; 5% fatty alcohol polyglycol ether; 2% lignosulfonic acid, sodium salt, sulfomethylated; 8% ammonium sulfate; 1% of a defoaming agent; 17% sucrose and 25% lactose.
The dimethomorph used to form the composition comprises a mixture of the E and Z isomers.
Composition 4: WDG 50% phosethyl-Al
A Water Dispersible Granule (WDG) formulation was prepared having the following composition:
7% dimethomorph; 50% fosetyl-aluminum; 5% sodium lauryl sulfate; 5% fatty alcohol polyglycol ether; 2% lignosulfonic acid, sodium salt, sulfomethylated; 8% ammonium sulfate; 1% of a defoaming agent; 9% sucrose and 13% lactose.
The dimethomorph used to form the composition comprises a mixture of the E and Z isomers.
Composition 5: WDG 70% phosethyl-Al
A Water Dispersible Granule (WDG) formulation was prepared having the following composition:
7% dimethomorph; 70% fosetyl-aluminum; 5% sodium lauryl sulfate; 5% fatty alcohol polyglycol ether; 2% lignosulfonic acid, sodium salt, sulfomethylated; 8% ammonium sulfate; 1% of a defoaming agent; 1% sucrose and 1% lactose.
The dimethomorph used to form the composition comprises a mixture of the E and Z isomers.
Composition 6: SC 50% phosethyl-Al
A Suspension Concentrate (SC) formulation was prepared having the following composition:
7% dimethomorph; 50% fosetyl-aluminum; 10% propylene glycol; 5% of a tristyryl polyoxyether; 1% sodium lignosulfonate; 1% carboxymethyl cellulose; 1% silicone oil (in the form of a 75% emulsion in water); water (equilibrium to 1L).
The dimethomorph, as used to form the composition, comprises a mixture of E and Z isomers.
Composition 7: WDG 0% phosethyl-Al
A Water Dispersible Granule (WDG) formulation was prepared having the following composition:
7% dimethomorph; 5% sodium lauryl sulfate; 5% fatty alcohol polyglycol ether; 2% lignosulfonic acid, sodium salt, sulfomethylated; 8% ammonium sulfate; 1% of a defoaming agent; 30% sucrose and 42% lactose.
The dimethomorph used to form the composition comprises a mixture of the E and Z isomers.
Composition 8: SC 0% phosethyl-Al
A Suspension Concentrate (SC) formulation was prepared having the following composition:
7% dimethomorph; 10% propylene glycol; 5% of tristyrylphenol polyoxyethylene ether; 1% sodium lignosulfonate; 1% carboxymethyl cellulose; 1% silicone oil (in the form of a 75% emulsion in water); water (equilibrium to 1L).
The dimethomorph used to form the composition comprises a mixture of the E and Z isomers.
Example 2 irradiation of Dimethomorph and analysis of the isomerization
The effect of irradiation with light on the composition in example 1 was tested as follows:
the compositions prepared in example 1 were each diluted with water. Three samples of 20mg of the resulting dilution were taken and dropped onto a glass plate and left to dry at room temperature. Three dried samples were then irradiated with UV light for 0, 25 and 100 minutes. After irradiation, the samples were washed from the glass plate with 4mL of dimethyl sulfoxide (DMSO) by applying ultrasound. The sample was separated by HPLC into the E and Z isomers of dimethomorph. The amount of E and Z isomers of dimethomorph was measured by peak area and the percentage of Z isomer of dimethomorph present was determined for each sample. These results are shown in table 1 below.
TABLE 1
Figure GDA0002644133510000141
Figure GDA0002644133510000151
As can be seen from the data presented in table 1, the presence of fosetyl-al in the composition reduced the conversion of the Z isomer of dimethomorph to the E isomer and resulted in an increase in the amount of Z isomer over the time of the experiment.
Example 3 field test on grapevine (downy mildew)
Young grapevine plants were sprayed with a conidia suspension of downy mildew and incubated at 20 ℃ and 100% relative atmospheric humidity for 48 hours.
The following compositions were prepared, then each diluted with water and sprayed on the plants.
Composition A:
7% dimethomorph (Z isomer); 50% fosetyl-aluminum; 5% sodium lauryl sulfate; 5% fatty alcohol polyglycol ether; 2% lignosulfonic acid, sodium salt, sulfomethylated; 8% ammonium sulfate; 1% of a defoaming agent; 9% sucrose and 13% lactose.
Composition B:
7% dimethomorph (Z isomer); 5% sodium lauryl sulfate; 5% fatty alcohol polyglycol ether; 2% lignosulfonic acid, sodium salt, sulfomethylated; 8% ammonium sulfate; 1% of a defoaming agent; 30% sucrose and 42% lactose.
Composition B was used for comparative purposes only and is not an embodiment of the present invention.
A control composition prepared according to composition a (but without dimethomorph and fosetyl-aluminum) was also prepared, again for comparative purposes.
One group of plants was stored in the dark and the other group of plants was stored in the sunlight. Both groups of plants were kept in a greenhouse at 15 ℃ and 80% relative atmospheric humidity for 7 days.
After this, the plants were examined for severity of fungal infestation. Severity was determined as the percentage of plants exhibiting visible fungal infestation. The results are set forth in table 2 below.
TABLE 2
Figure GDA0002644133510000161
As can be seen from the data in table 2 above, composition B, as well as the control, exhibited a significantly reduced fungicidal effect when the treated plants were irradiated with sunlight. In contrast, the presence of both dimethomorph and fosetyl-aluminum in composition a provided a high degree of fungicidal activity, both under dark conditions and when irradiated with sunlight.

Claims (34)

1. A method of reducing and/or promoting the conversion of a Z isomer of dimethomorph to and/or from an E isomer of dimethomorph, comprising administering dimethomorph in conjunction with fosetyl-aluminum.
2. The method of claim 1, wherein the dimethomorph is present as the E isomer, the Z isomer, or a combination of the E and Z isomers.
3. The process according to any preceding claim, wherein the dimethomorph comprises the E isomer or the Z isomer in an amount of at least 5% by weight of the total amount of dimethomorph present.
4. The process according to claim 3, wherein the dimethomorph comprises the E isomer or the Z isomer in an amount of at least 10% by weight of the total amount of dimethomorph present.
5. The process according to claim 4, wherein the dimethomorph comprises the E isomer or the Z isomer in an amount of at least 40% by weight of the total amount of dimethomorph present.
6. The process according to claim 1 or 2, wherein the dimethomorph initially comprises at least 10% by weight of the Z isomer.
7. The process of claim 6, wherein the dimethomorph initially comprises at least 30% by weight of the Z isomer.
8. The method of claim 1 or 2, wherein the method employs a composition comprising dimethomorph and fosetyl-aluminum.
9. The process according to claim 1 or 2, wherein dimethomorph and fosetyl-aluminum are applied separately to the locus to be treated.
10. A method of reducing the instability of dimethomorph in its fungicidal activity in the presence of light, comprising contacting dimethomorph with fosetyl-aluminum, wherein fosetyl-aluminum reduces and/or promotes the conversion of the Z isomer of dimethomorph to the E isomer of dimethomorph.
11. The method of claim 10, wherein the dimethomorph is present as the E isomer, the Z isomer, or a combination of the E and Z isomers.
12. The process according to any one of claims 10 or 11, wherein the dimethomorph comprises the E isomer or the Z isomer in an amount of at least 5% by weight of the total amount of dimethomorph present.
13. The method of claim 12, wherein the dimethomorph comprises the E isomer or the Z isomer in an amount of at least 10% by weight of the total amount of dimethomorph present.
14. The method of claim 13, wherein the dimethomorph comprises the E isomer or the Z isomer in an amount of at least 40% by weight of the total amount of dimethomorph present.
15. The process according to claim 10 or 11, wherein dimethomorph initially comprises at least 10% by weight of the Z isomer.
16. The method of claim 15, wherein the dimethomorph initially comprises at least 30% by weight of the Z isomer.
17. The method of claim 10 or 11, wherein the method employs a composition comprising dimethomorph and fosetyl-aluminum.
18. The process according to claim 10 or 11, wherein dimethomorph and fosetyl-aluminum are applied separately to the locus to be treated.
19. A composition comprising dimethomorph initially comprising at least 60 wt.% of the Z isomer and fosetyl-aluminum.
20. The composition of claim 19, wherein dimethomorph is present in the composition in an amount of at least 1% by weight.
21. The composition of claim 20, wherein dimethomorph is present in the composition in an amount of at least 3% by weight.
22. The composition of any one of claims 19 to 21, wherein dimethomorph is present in the composition in an amount of up to 90% by weight.
23. The composition of claim 22, wherein dimethomorph is present in the composition in an amount of up to 75% by weight.
24. The composition of any one of claims 19 to 21, wherein fosetyl-aluminum is present in the composition in an amount of at least 1% by weight.
25. The composition of claim 24, wherein fosetyl-aluminum is present in the composition in an amount of at least 10% by weight.
26. The composition of any one of claims 19 to 21, wherein fosetyl-aluminum is present in the composition in an amount of up to 90% by weight.
27. The composition of claim 26, wherein dimethomorph is present in the composition in an amount of up to 75% by weight.
28. The composition according to any one of claims 19 to 21, wherein dimethomorph is present as the E isomer, the Z isomer, or a combination of the E and Z isomers.
29. The composition according to any one of claims 19 to 21, wherein the dimethomorph comprises the E isomer or the Z isomer in an amount of at least 5% by weight of the total amount of dimethomorph present.
30. The composition according to claim 29, wherein the dimethomorph comprises the E isomer or the Z isomer in an amount of at least 10% by weight of the total amount of dimethomorph present.
31. The composition according to claim 30, wherein the dimethomorph comprises the E isomer or the Z isomer in an amount of at least 40% by weight of the total amount of dimethomorph present.
32. The composition according to any one of claims 19 to 21, wherein the dimethomorph initially comprises at least 10% by weight of the Z isomer.
33. The composition of claim 32, wherein the dimethomorph initially comprises at least 30% by weight of the Z isomer.
34. Use of fosetyl-aluminium to reduce and/or promote the conversion of the Z isomer of dimethomorph to the E isomer of dimethomorph.
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