Patent Description:
Compositions of fungicidal aminoindane amide compounds alone and in combination with fungicidal azole compounds are described in <CIT>. <CIT>, <CIT> and <CIT> disclose compositions comprising a compound of formula (I).

<CIT> discloses a plant disease control composition containing a tetrazolinone compound and an amide compound. In an embodiment, the composition comprises a tetrazolinone compound, <NUM>-(difluoromethyl)-N-(<NUM>,<NUM>-dihydro-<NUM>,<NUM>,<NUM>-trimethyl-<NUM>-inden-<NUM>-yl)-<NUM>-methyl-<NUM>-pyrazole-<NUM>-carboxamide (common name inpyrfluxam), and a mixture of N,N-dimethyloctanamide and N,N-dimethyldecanamide. The addition of the amide compound improves the permeability of the tetrazolinone compound into the plant.

Emulsifiable concentrates are widely used formulations in crop protection. The disadvantage of known emulsifiable concentrates is poor stability at cold temperatures, active ingredient crystallization, and low active ingredient concentration. The present invention provides an emulsifiable concentrate that addresses these disadvantages and surprisingly allows for high fungicide concentration without crystallization.

The present invention is directed to emulsifiable concentrates of compounds for the protection of agricultural crops, to formulations containing the same, and to methods of their preparation and use for treatment and protection of agricultural crops according to the attached claims.

According to the invention, an emulsifiable concentrate is provided with an aminoindane amide compound having the structure of formula (I):
<CHM>
and an amide having the structure of formula (II):
<CHM>
wherein R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, and n are as defined in claim <NUM>. In an embodiment, an emulsifiable concentrate is provided with an aminoindane amide compound of formula (I), an amide compound of formula (II), and an azole compound having fungicidal or insecticidal activity.

According to the invention, a formulation is provided wherein the emulsifiable concentrate is emulsified in water according to claim <NUM>.

According to the invention, a method of controlling pathogenic fungi in agricultural crops is provided by applying an effective dose of the emulsifiable concentrate or an effective dose of a formulation of the present invention on a plant to be protected, on seeds of a plant to be protected before sowing, or on the ground before sowing seeds of a plant to be protected according to claim <NUM>.

According to the invention, a method of controlling harmful insects in agricultural crops is provided by applying an effective dose of the emulsifiable concentrate or an effective dose of a formulation of the present invention on a plant to be protected, on seeds of a plant to be protected before sowing, or on the ground before sowing seeds of a plant to be protected according to claim <NUM>.

As mentioned above, the invention relates to emulsifiable concentrates of compounds for the protection of agricultural crops, to formulations containing the same, and to methods of their use for treatment and protection of agricultural crops. According to the invention, an emulsifiable concentrate is provided with:.

As used herein,"alkyl" means a straight chain or branched alkyl group having from <NUM> to <NUM> carbon atoms (i.e., C<NUM>-<NUM>alkyl), in some embodiments from <NUM> to <NUM> carbon atoms (i.e., C<NUM>-<NUM>alkyl), in some embodiments from <NUM> to <NUM> carbon atoms (i.e., C<NUM>-<NUM> alkyl), in some embodiments from <NUM> to <NUM> carbon atoms (i. e, C<NUM>-<NUM>alkyl), and in some embodiments from <NUM> to <NUM> carbon atoms (i.e., C<NUM>-<NUM>alkyl). Examples of straight chain alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and <NUM>,<NUM>-dimethylpropyl groups.

"Halo" or "halogen" refers to fluorine, chlorine, bromine, and iodine.

"Haloalkyl" refers to an alkyl as defined above with one or more hydrogen atoms replaced with halogen. Examples of haloalkyl groups include, but are not limited to, -CF<NUM>, -CHF<NUM>, -CH<NUM>F, -CH<NUM>CF<NUM> and the like.

"Alkoxy" refers to an alkyl as defined above joined by way of an oxygen atom (i.e., -O-(alkyl)). Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, n-butoxy, isopropoxy, sec-butoxy, tert-butoxy, and the like. "Haloalkoxy" refers to a haloalkyl as defined above joined by way of an oxygen atom (i.e., -O-(haloalkyl)). Examples of haloalkoxy groups include, but are not limited to, -OCF<NUM>, -OCHF<NUM>, -OCH<NUM>F, -OCH<NUM>CF<NUM>, and the like.

"Alkylthio" refers to an alkyl as defined above joined by way of a sulfur atom (i.e., - S- (alkyl)). Examples of alkylthio groups include, but are not limited to, -SCH<NUM> and -SCH<NUM>CH<NUM>.

"Haloalkylthio" refers to a haloalkyl as defined above joined by way of a sulfur atom (i.e., -S-(haloalkyl)). Example of haloalkylthio groups include, but are not limited to, -SCF<NUM>, -SCHF<NUM>, -SCH<NUM>F, -SCH<NUM>CF<NUM>, and the like.

"Cycloalkyl" refers to alkyl groups forming a ring structure, which can be substituted or unsubstituted, wherein the ring is either completely saturated, partially unsaturated, or fully unsaturated, wherein if there is unsaturation, the conjugation of the pi-electrons in the ring do not give rise to aromaticity. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group has <NUM> to <NUM> ring members (i.e., C<NUM>-<NUM>cycloalkyl), whereas in other embodiments the number of ring carbon atoms range from <NUM> to <NUM> members (i.e., C<NUM>-<NUM> cycloalkyl), <NUM> to <NUM> members (i.e., C<NUM>-<NUM>cycloalkyl), or <NUM> to <NUM> members (i.e., C<NUM>-<NUM> cycloalkyl). Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like.

"Halocycloalkyl" refers to a cycloalkyl as defined above with one or more hydrogen atoms replaced with halogen. Examples of halocycloalkyl groups include, but are not limited to, <NUM>-fluorocyclopropyl, <NUM>-fluorocyclobutyl, <NUM>-fluorocyclobutyl, <NUM>-fluorocyclopentyl, <NUM>-fluorocyclopentyl, <NUM>-fluorocyclohexyl, <NUM>-fluorocyclohexyl, <NUM>-fluorocyclohexyl, <NUM>,<NUM>,-difluorocyclopropyl, <NUM>,<NUM>-difluorocyclopropyl, and the like.

In another embodiment, an emulsifiable concentrate is provided, wherein R<NUM>, R<NUM>, R<NUM>, and R<NUM> are each, independently, C<NUM>-<NUM>alkyl; R<NUM>, R<NUM> and R<NUM> are each, independently, H, C<NUM>-<NUM>alkyl or C<NUM>-<NUM>haloalkyl; R<NUM> is F; and n is <NUM> to <NUM> of the structure of formula (I).

In another embodiment, an emulsifiable concentrate is provided wherein R<NUM>, R<NUM>, R<NUM>, and R<NUM> of the structure of formula (I) are each methyl. In one embodiment, R<NUM> is H. In another embodiment, an emulsifiable concentrate is provided wherein R<NUM> of the structure of formula (I) is methyl, difluoromethyl, or trifluoromethyl.

In another embodiment, an emulsifiable concentrate is provided wherein R<NUM> of the structure of formula (I) is H or methyl.

According to the invention, an emulsifiable concentrate is provided wherein n of the structure of formula (I) is <NUM> to <NUM>. According to the invention, R<NUM> is F.

In one embodiment, an emulsifiable concentrate is provided wherein the aminoindane amide of formula (I) is
<CHM>
<CHM>
or
<CHM>.

In a preferred embodiment, the aminoindane amide of formula (I) is fluindapyr:
<CHM>.

In another embodiment, an emulsifiable concentrate is provided comprising an amide having the structure of formula (II), wherein R<NUM> and R<NUM> are each methyl.

In another embodiment, an emulsifiable concentrate is provided comprising an amide having the structure of formula (II), wherein R<NUM> is C<NUM>-<NUM>alkyl.

In one embodiment, the amide having the structure of formula (II) is
<CHM>.

In one embodiment, an emulsifiable concentrate is provided comprising a mixture of at least two amide compounds of formula (II). In one embodiment, the mixture of at least two amide compounds of formula (II) is:
<CHM>
at ratio of <NUM>:<NUM> wt% to <NUM>:<NUM> wt%. In one embodiment, the two amide compounds of formula (II) are present at a ratio of <NUM>:<NUM> wt% to <NUM>:<NUM> wt%. In another embodiment, the two amide compounds of formula (II) are present at a ratio of <NUM>:<NUM> wt% to <NUM>:<NUM> wt%. In another embodiment, the two amide compounds of formula (II) are present at a ratio of <NUM>:<NUM> wt% to <NUM>:<NUM> wt%. In another embodiment, the two amide compounds of formula (II) are present at a ratio of <NUM>:<NUM> wt% to <NUM>:<NUM> wt%. In another embodiment, the two amide compounds of formula (II) are present at a ratio of <NUM>:<NUM> wt%.

In one embodiment, an emulsifiable concentrate is provided wherein the aminoindane amide of formula (I) is fluindapyr; and the amide of formula (II) is N,N-dimethyldecanamide or N,N-dimethyloctanamide, or a mixture thereof.

In one embodiment, an emulsifiable concentrate is provided comprising an aminoindane amide having the structure of formula (I), an amide having the structure of formula (II), and an azole compound having fungicidal or insecticidal activity. In one embodiment, the azole compound is cyproconazole, difenoconazole, epoxyconazole, flutriafol, penconazole, prochloraz, prothioconazole, tebuconazole, or tetraconazole. In a preferred embodiment, the azole compound is prothioconazole.

In one embodiment, an emulsifiable concentrate is provided with fluindapyr; N,N-dimethyldecanamide or N,N-dimethyloctanamide, or a mixture thereof; and prothioconazole.

In another embodiment, an emulsifiable concentrate is provided wherein the aminoindane amide of formula (I) is present from about <NUM> wt% to about <NUM> wt%. In one embodiment, the aminoindane amide of formula (I) is present from about <NUM> wt% to about <NUM> wt%. In one embodiment, the aminoindane amide of formula (I) is present at about <NUM> wt%. In one embodiment, the aminoindane amide of formula (I) is fluindapyr.

In another embodiment, an emulsifiable concentrate is provided wherein the aminoindane amide of formula (I) is present at a concentration of at least about <NUM>/L. In one embodiment, the aminoindane amide of formula (I) is present at a concentration of at least about <NUM>/L. In one embodiment, the aminoindane amide of formula (I) is present at a concentration of at least about <NUM>/L. In one embodiment, the aminoindane amide of formula (I) is fluindapyr.

In another embodiment, the emulsifiable concentrate is provided with an azole compound present from about <NUM> wt% to about <NUM> wt%. In one embodiment, the azole compound is present from about <NUM> wt% to about <NUM> wt%. In one embodiment, the azole compound is present at about <NUM> wt%. In one embodiment, the azole compound is prothioconazole.

In another embodiment, the emulsifiable concentrate is provided wherein the azole compound is present at a concentration of at least <NUM>/L. In one embodiment, the azole compound is present at a concentration of at least <NUM>/L. In one embodiment, the azole compound is present at a concentration of at least <NUM>/L.

In one embodiment, the azole compound is prothioconazole.

In one embodiment, an emulsifiable concentrate is provided with fluindapyr present at about <NUM> wt% and prothioconazole present at about <NUM> wt%.

In one embodiment, an emulsifiable concentrate is provided with fluindapyr present at a concentration of at least about <NUM>/L and prothioconazole present at a concentration of at least about <NUM>/L.

In another embodiment, the emulsifiable concentrate is a homogeneous solution. In one embodiment, the emulsifiable concentrate is emulsified in water. In one embodiment, the emulsifiable concentrate is emulsified in water with a dilution of at least <NUM>%. In another embodiment, the emulsifiable concentrate is emulsified in water with a dilution of at least <NUM>%. In another embodiment, the emulsifiable concentrate is emulsified in water with a dilution of at least <NUM>%. In one embodiment, the formulation in water is substantially free from crystal formation by the aminoindane amide of formula (I). In another embodiment, the formulation in water is substantially free from crystal formation by the azole compound.

According to the invention, a method of controlling pathogenic fungi in agricultural crops is provided by applying an effective dose of the emulsifiable concentrate of the present invention on a plant to be protected, on seeds of a plant to be protected before sowing, or on the ground before sowing seeds of a plant to be protected according to claim <NUM>. In one embodiment, the applying is done by spraying.

According to the invention, a method of controlling harmful insects in agricultural crops is provided by applying an effective dose of the emulsifiable concentrate of the present invention on a plant to be protected, on seeds of a plant to be protected before sowing, or on the ground before sowing seeds of a plant to be protected. In one embodiment, the applying is done by spraying according to claim <NUM>.

The invention furthermore relates to a method for controlling undesired vegetation and/or undesired attack by insects or mites and/or for regulating the growth of plants, where the concentrate according to the invention or the emulsion according to the invention is allowed to act on the respective pests, their environment or on the crop plants to be protected from the respective pests, on the soil and/or on undesired plants and/or on the crop plants and/or their environment. In general, the therapeutic treatment of humans and animals is excluded from the method for controlling phytopathogenic fungi and/or undesired vegetation and/or undesired attack by insects or mites and/or for regulating the growth of plants.

When employed in crop protection, the application rates of the active fungicides amount to from <NUM> to <NUM> per ha, preferably from <NUM> to <NUM> per ha, especially preferably from <NUM> to <NUM> per ha and in particular from <NUM> to <NUM> per ha, depending on the nature of the desired effect. In treatment of plant propagation materials such as seeds, e.g. by dusting, coating or drenching seed, amounts of active substance of from <NUM> to <NUM>, preferably from <NUM> to <NUM>, more preferably from <NUM> to <NUM> and most preferably from <NUM> to <NUM>, per <NUM> of plant propagation material (preferably seed) are generally required. When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are <NUM> × <NUM>-<NUM> kg to <NUM>, preferably <NUM> x <NUM>-<NUM> kg to <NUM>, of active substance per cubic meter of treated material.

Various types of oils, adjuvants, fertilizers or micronutrients and further pesticides (for example herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the emulsion in the form of a premix or optionally only shortly before use (tank mix). These agents can be admixed to the compositions according to the invention at a weight ratio of from <NUM>:<NUM> to <NUM>:<NUM>, preferably from <NUM>:<NUM> to <NUM>:<NUM>.

The user applies the composition according to the invention in one embodiment from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. In one embodiment, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. In one embodiment, <NUM> to <NUM> liters, preferably <NUM> to <NUM> liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

Advantages of the present invention are, inter alia, that the concentrate is highly stable to low temperatures (e.g. even below <NUM>); that the active ingredients do not precipitate, cream, or crystallize in the concentrate at low temperatures (e.g. even below <NUM>); that the active ingredients do not precipitate, cream, or crystallize in the emulsion obtained from the concentrate, e.g. at low temperatures (even below <NUM>); that high active ingredient concentrations in the concentrate can be employed; that an emulsion forms spontaneously upon dilution of the concentrate with water; that the concentrate is capable of being stored over prolonged periods; that the concentrate does not require the presence of water (e.g. because it might freeze below <NUM> or would favor bacterial growth during storage); that the concentrate forms a stable emulsion upon dilution with water; that adjuvants (such as alcohol alkoxylates) can be included in the concentrate formulations; that the pesticide dose in the emulsion obtained from the concentrate does not clog any spraying filters or nozzles, e.g. at low temperatures, or when diluted with hard water.

The invention is further illustrated by the following examples. The examples below are non-limiting and are merely representative of various aspects of the invention as defined in the attached claims. Solid and dotted wedges within the structures herein disclosed illustrate relative stereochemistry, with absolute stereochemistry depicted only when specifically stated or delineated.

In order to test the solubility of an active ingredient comprising an aminoindane amide active compound, fluindapyr was added into a test solvent at the concentration of <NUM>/L under sufficient agitation. The test solvents were selected based on Hansen Solubility Parameters with a Relative Energy Difference (RED) of between <NUM> and <NUM>. The completed dissolved solutions were further stored for one week at <NUM> to check if any crystals grew or not under the storage condition. A solution without crystal growth under the storage condition was considered a Pass, as indicated in Table <NUM>.

In order to test the solubility of an active ingredient combination comprising an aminoindane amide active compound and an azole active compound, <NUM> of fluindapyr and <NUM> of prothioconazole were added to a glass jar. For each sample, <NUM> of the respective solvents listed in Table <NUM> was added to the jar. Each sample was initially mixed using magnetic stirrers, and the samples were placed onto rollers to aid dissolution.

Solvents that appeared to dissolve the fluindapyr and prothioconazole at room temperature were transferred to an incubator overnight at -<NUM>.

Solvents that did not dissolve the fluindapyr and prothioconazole separated as soon as agitation was halted. These samples were transferred to an incubator at <NUM> overnight.

A solution containing both <NUM> wt% fluindapyr and <NUM> wt% prothioconazole was diluted in tap water at <NUM>%, or <NUM>% or <NUM>% v/v, respectively. The dilution was kept <NUM> hours at room temperature to evaluate for crystal growth. If there was no observed crystal growth, it was considered a Pass. Otherwise, a Failure, as indicated in Table <NUM>.

Claim 1:
An emulsifiable concentrate comprising:
a) an aminoindane amide having the structure of formula (I):
<CHM>
wherein
R<NUM>, R<NUM>, R<NUM>, and R<NUM> are each, independently, H, C<NUM>-<NUM>alkyl, C<NUM>-<NUM>haloalkyl, C<NUM>-<NUM> cycloalkyl, or C<NUM>-<NUM>halocycloalkyl;
R<NUM> and R<NUM> are each, independently, H, C<NUM>-<NUM>alkyl or C<NUM>-<NUM>haloalkyl; R<NUM> is C<NUM>-<NUM> alkyl, C<NUM>-<NUM>haloalkyl, C<NUM>-<NUM>cycloalkyl, C<NUM>-<NUM>halocycloalkyl, C<NUM>-<NUM>alkoxy, C<NUM>-<NUM> haloalkoxy, C<NUM>-<NUM> alkylthio, or C<NUM>-<NUM>haloalkylthio;
R<NUM> is F; and
n is <NUM> to <NUM>; and
b) an amide having the structure of formula (II):
<CHM>
wherein
R<NUM> is C<NUM>-<NUM>alkyl;
R<NUM> is C<NUM>-<NUM>alkyl; and
R<NUM> is C<NUM>-<NUM>alkyl.