NZ620688B2 - Use and agrochemical composition of carboxylic acid dibutylamides - Google Patents

Use and agrochemical composition of carboxylic acid dibutylamides Download PDF

Info

Publication number
NZ620688B2
NZ620688B2 NZ620688A NZ62068812A NZ620688B2 NZ 620688 B2 NZ620688 B2 NZ 620688B2 NZ 620688 A NZ620688 A NZ 620688A NZ 62068812 A NZ62068812 A NZ 62068812A NZ 620688 B2 NZ620688 B2 NZ 620688B2
Authority
NZ
New Zealand
Prior art keywords
methyl
dibutyl
carboxamide
penetration
alkyl
Prior art date
Application number
NZ620688A
Other versions
NZ620688A (en
Inventor
Thomas Auler
Peter Baur
Alison Daniels
Rolf Pontzen
Martin Steinbeck
Ingo Wetcholowsky
Original Assignee
Bayer Intellectual Property Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Intellectual Property Gmbh filed Critical Bayer Intellectual Property Gmbh
Priority claimed from PCT/EP2012/065685 external-priority patent/WO2013021045A1/en
Publication of NZ620688A publication Critical patent/NZ620688A/en
Publication of NZ620688B2 publication Critical patent/NZ620688B2/en

Links

Classifications

    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A01N37/40—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 having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same 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
    • 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
    • A01N37/44—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 nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—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 nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • 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
    • A01N43/88—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 three ring hetero atoms
    • 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
    • A01N45/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring
    • A01N45/02—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring having three carbocyclic rings
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof

Abstract

Disclosed is the use of N,N-dibutylcarboxamides of formula (I): R1-CO-NR2-R3 in agrochemical formulations as a tank mix additive for promoting the penetration of active agrochemical ingredients into plants, wherein R1 is C16-C18-alkyl or C16-C18-alkeny and R2 and R3 are C4-alkyl. Also disclosed is an agrochemical formulation in the form of an emulsion concentrate or dispersion oil comprising a C16-C18-carboxylic acid dibutylamide and at least one active agrochemical ingredient which is solid at room temperature is selected from the group consisting of cyproconazole, epoxiconazole, metconazole, propiconazole, prothioconazole, tebuconazole, azoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, isopyrazam, indaziflam, fluopyram, fluxapyroxad, bixafen, amidosulfuron, bromoxynil, cyprosulfamide, 2,4-D, glufosinate, glyphosate, iodosulfuron-methyl, isoxadifenethyl, mefenpyr, mesosulfuron, mesotrione, metamitron, phenmedipham, sulcotrione, tembotrione and thiencarbazone-methyl. n agrochemical formulation in the form of an emulsion concentrate or dispersion oil comprising a C16-C18-carboxylic acid dibutylamide and at least one active agrochemical ingredient which is solid at room temperature is selected from the group consisting of cyproconazole, epoxiconazole, metconazole, propiconazole, prothioconazole, tebuconazole, azoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, isopyrazam, indaziflam, fluopyram, fluxapyroxad, bixafen, amidosulfuron, bromoxynil, cyprosulfamide, 2,4-D, glufosinate, glyphosate, iodosulfuron-methyl, isoxadifenethyl, mefenpyr, mesosulfuron, mesotrione, metamitron, phenmedipham, sulcotrione, tembotrione and thiencarbazone-methyl.

Description

_ 1 - Use and agrochemical composition of carboxylic acid dibutylamides The invention relates to the use of N,N-dibutylcarboxamides in agrochemical formulations and crop protection compositions, to agrochemical formulations and crop tion compositions comprising such compounds, and to use as a tankmix ve.
EP-A 0 453 899 ses the use of N,N—dimethyl—C5—C19-alkylcarboxamides as crystallization inhibitors for particular azole fungicides having a cy to crystallize, such as tebuconazole. The use of N,N—dibutylcarboxamides for this purpose or for improvement of the action of agrochemicals after deployment to the plant is neither disclosed nor suggested in this document.
USZOOS/104844 discloses that the N,N-dimethyl-C5-C1g—alkylcarboxamides are penetrants for particular active ingredients, for example prothioconazoles. The use of N,N-dibutylcarboxamides for this purpose or for improvement of the action of agrochemicals after deployment to the plant is neither disclosed nor suggested in this document.
US2011/0124505 claims compositions comprising N,N-dimethy1-C5-C19-alkylcarboxamides as solvents for biocides and pesticides and various emulsifiers. The use of N,N-dibutylcarboxamides for this purpose or for improvement of the action of agrochemicals after deployment to the plant is neither disclosed nor suggested in this document.
In 998/02216, 41986 and WO—A-2008/l45063, N,N—dialkylalkyl- or —alkenylcarboxamides are used in agrochemical formulations for prevention of crystal formation in spray liquors. The teaching to use N,N—dialkylalkyl— or ylcarboxamides as penetrants is not given in WO-A-l 998/02216, DEA-4341986 and WO—A—2008/l45063.
WO-A—l98 8/02216 teaches the use of N,N-dialkylalkylcarboxamides for promotion of the ation of medicaments through the human or animal skin. 988/02216, however, does not disclose any emical use, nor the use of the N,N—dibutyl-Cl6—Cl8-alkyl/all WO—A—2010/078852 teaches agrochemical formulations in the form of suspoemulsions. WO-A— 2010/078852, however, does not teach the use of the N,N—dibutyl-Cl6—C18-alkyl/alkenylcarboxamides used according to the invention in EC or OD formulations.
It has now been found that, surprisingly, the butylcarboxamides used according to the invention are very much poorer solvents than the N,N—dimethylalkylcarboxamides. In spite of this, they are excellent and actually better additives for ing the penetration of active agrochemical ingredients with very different physicochemical properties h the cuticle of the plant than the known N,N— dimethylcarboxamides (see examples 16 and 17). They are thus suitable for enhancing the biological efficacy of crop protection compositions. At the same time, they are l orders of magnitude less volatile from the leaf surface than the N,N-dimethylalkylcarboxamides.
In the case of the N,N-dibutylcarboxamides used in accordance with the invention, depending on the ylic acids or fatty acids of chain lengths C8—lO, Cl2—14 (based on coconut fat) and C15—18 (based on tallow fat) present, some differences were discernible in the influence on the active ingredient penentration over the course of time. More particularly, it is found that the N,N—dibutyl-Cl6-C18- alkyl/alkenylcarboxamides in EC formulations lead to a distinct improvement in penetration over the N,N—dimethylcarboxamides (examples 16, 18 and 21).
In addition, it is found that the N,N—dibutyl-Cl6—C18-alkyl/alkenylcarboxamides have distinctly different penetration characteristics than the N,N—dibutyl-Cl2—Cl4-alkyl/alkenylcarboxamides and very particularly than the analogous N,N—dimethylcarboxamides. The butyl-Cl6-C18— alkyl/alkenylcarboxamides are absorbed into the leaf cuticle, but do not penetrate further into the leaf interior; as a result, they can ensure the ation—enhancing effect over a long period. Especially the analogous N,N-dimethylcarboxamides have much higher penetration into the leaf, as a result of which the penetration-enhancing effect is restricted to the first few hours after spray application (example 22).
A further advantage of the N,N—dibutyl-Cl6—Cl8-alkyl/alkenylcarboxamides over the N,N—dibutyl—C8- kyl/alkenylcarboxamides is the substantial lack of volatility f.
The invention therefore provides for the use of amides of the formula (I) R1 -Co—NR2R3 (I) in which R1 is C16-C18—alkyl or C16—C18-alkenyl and R2 is C4-alkyl and R3 is yl for promoting the penetration of active agrochemical ingredients from the group of the ides or herbicides into plants.
In this context, the penetration of the active agrochemical ingredient into plants means the penetration of the active agrochemical ingredient through the surface of the leaf into the plant.
R2 and R3 are preferably the same or different, more ably identical alkyl groups having 4 carbon atoms, more preferably n-butyl, l-methylpropyl or 2-methylpropyl, most preferably l.
R1 has 16 — 18 carbon atoms (tallow carboxylic acid dibutyl amide). In this context can be C16'C18' alkyl or C16-C18-alkenyl.
The N,N—dibutylcarboxamides are easy to prepare. A suitable preparation method is disclosed, for example, in WO-A—1995/015685 in example 1 on page 26 for N,N—di-n-propylhexanamide, which can also be applied analogously to the N,N—dibutylcarboxamides (e.g. example 16 on page 28 of WO-A— 1995/015685).
Preference is given to using a mixture of at least two amides of the formula (I). Preference is given to using a mixture based on the fatty acid composition of tallow. A typical raw material source is fatty acids from bovine tallow.
More ably, the mixture used in accordance with the ion comprises both at least one carboxamide of the formula (I) in which R1 is C16-C18-alkyl and at least one carboxamide of the formula (I) in which R1 is C16-C18—alkenyl.
Particular ence is given to a mixture based on the fatty acid composition in bovine tallow. This comprises predominantly saturated and unsaturated fatty acids having an even number of carbon atoms.
Fatty acids having an odd number of carbon atoms such as pentadecanoic acid (C15) or margaric acid (C17) are present only in small proportions.
Typically, bovine tallow contains more than 80% by weight, generally even more than 90% by weight, based on the sum of the weights of the fatty acids, of saturated and unsaturated C16 — C18 — fatty acids, especially palmitic acid (C16 ted), palmitoleic acid (C16 partly unsaturated), ic acid (C17 saturated), stearic acid (C18 saturated) and oleic acid (C18 partly rated). Margaric acid and palmitoleic acid are present here only in relatively small amounts (of typically less than 10% by weight in total).
The N,N-dibutylcarboxamides have a volatility from the leaf surface reduced by several orders of magnitude compared to the N,N—dimhlcarboxamides used as solvents. The N,N—dibutylcarboxamides having an alkyl chain length R1 of C3 - C10, however, still have a considerable volatility of cal relevance. Even shorter chain lengths are generally unsuitable because of their volatility for use as a ical efficacy-enhancing additive in agrochemical formulations. Even in the case of the N,N— dibutylcarboxamides having an alkyl chain length R1 of C12 - C14, a certain volatility still exists. On the other hand, the N,N—dibutylcarboxarnides having an alkyl chain length R1 of greater than C18 i.e. C20, C22, or greater than C22, are only of limited suitability because of their molecular size for significant penetration into the cuticle of plants and are thus ruled out as penetrants at the plant level. What are ideal are thus the N,N—dibutylcarboxamides having an alkyl chain length R1 of C16 - C18.
The carboxamides of the formula (I) are used individually or in the form of mixtures. If carboxamides are mentioned in the description or the claims, What is meant is explicitly dual compounds or mixtures of several carboxamides.
The amount of one or more compounds of the formula (I) in the case of the ive use in crop tion compositions can vary Within wide limits according to the active ingredient and formulation type. The compounds of the formula (I) can be used in all standard agrochemical formulations, preferably in liquid formulations. The present invention also provides for the use of the carboxamides of the formula (I) for improving efficacy at the plant level as a tankmix additive, meaning that the carboxamides are added to a spray liquor ed from a concentrated formulation only directly before ment. In principle, the compounds can also be introduced into solid ations.
The inventive use of the carboxamides of the formula (I) is effected, for example, in formulations of active agrochemical ingredients and from ready-to-use crop protection compositions produced therefrom by dilution (preferably with water) (spray liquors).
The invention also relates to formulations in the form of emulsion trates (BC) or of dispersions in oil (OD) comprising 0 at least one active agrochemical ingredient which is solid at room temperature (20°C) and is from the group of the fungicides or herbicides and 2O 0 at least one carboxamide of the formula (I) Rl-co-NR2R3 (1) in which R1 is C16-C18-alkyl or 8-alkenyl and R2 is C4—alkyl and R3 is C4-alkyl, and 0 at least one solvent and/or oil.
Preferably, the content of the at least one carboxamide of the a (I) in the formulation is o l to 50% by weight, 0 more preferably 2 to 40% by weight, 0 most preferably 5 to 25% by weight.
Because of their physical properties, such as state of matter, viscosity and melting point, N,N- dibutylcarboxamides are not very suitable for use in solid formulations such as granules (WG, WP).
Suitable formulation types are liquid formulations. Because the amides have some dissolution ty, but it is not significant, use in suspoemulsions (SE), which comprise active ients in liquid and solid form, is not preferred.
Particular preference is given to use in emulsion concentrates (EC) in which the N,N- dibutylcarboxamides are distributed homogeneously in the homogeneous formulation and are applied to the leaf of the target crop in very intimate contact with the dissolved active ingredients by means of spray application. Particular preference is se given to use in dispersions in oil (OD) in which the N,N—dibutylcarboxamides are in direct contact with the active ingredient in the oil phase in the formulation and on the leaf after spray application.
The invention also s to ready-to-use crop protection compositions comprising 0 at least one active agrochemical ingredient which is solid at room temperature (20°C) and is from the group of the fungicides or herbicides and 0 at least one carboxamide of the formula (I) R1 —co—NR2R3 (I) in which R1 is C16—C18—alkyl or C16-C18—alkenyl and R2 is yl and R3 is C4-alkyl, and 0 at least one solvent and/or oil and 0 water. ably, the content of the at least one carboxamide of the formula (I) in the crop protection composition is o 0.01 to 10% by weight, 0 more ably 0.02 to 2% by weight, 0 most preferably 0.05 to 0.2% by weight.
If a formulation/a crop protection composition comprises a plurality of carboxamides of the formula (I), the stated amount should be understood as the total t of all the carboxamides of the formula (I).
The radical definitions, value ranges and ations given above, in general terms or in areas of preference, can be combined with one r as desired, i.e. including combinations between the particular ranges and ranges of preference.
Suitable oils are especially vegetable oils or esters f or l oils or other c solvents.
Particularly suitable oils are sunflower oil, rapeseed oil or rapeseed oil methyl ester, and also paraffin oil or white oil, and aromatic arbon mixtures (preferably naphthalene-reduced), e. g. Solvesso TM.
Suitable solvents in the t of this invention are especially also organic solvents such as N,N— dimethyldecanamide, N,N—dimethyloctanamide, N,N—dimethyldodedecanamide, gamma-butyrolactone, Rhodiasolv Polarclean TM (methyl ethylamino)methyl—5~oxopentanoate) N-methylpyrrolidone or aromatic hydrocarbon mixtures (preferably naphthalene-reduced), e.g. Solvesso TM. Further suitable solvents are, for example, aromatic hydrocarbons, for example xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons, for e chlorobenzene, chloroethylene, or methylene chloride, aliphatic hydrocarbons, for example cyclohexane, alcohols, for example methanol, ethanol, isopropanol, butanol or glycol and the ethers and esters thereof (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides, lactams (such as N—alkylpyrrolidones) and lactones, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as yl sulfoxide.
The active agrochemical ingredient used is more preferably prothioconazole. Particularly suitable formulations are those comprising 0 15 — 35% by weight of prothioconazole and o 25 — 45% by weight of N,N—dimethyldecanamide and 0 10 — 40% by weight of one or more emulsifiers, preferably castor oil ycol ether esters or a mixture of ethoxypropoxytristyrylphenol (block copolymer) and tristyrylphenol late having an average of 16 BO units or a mixture of 2-ethy1hexanol propylene ethylene glycol ether, ethoxypropoxytristyrylphenol (block copolymer), alkoxylated ethylenediamine having an average of 16 EO and 16 PO units and rylphenol ethoxylate having an average of 16 EO units or a mixture of the emulsifiers mentioned in another combination and • 0.01 – 1.0% by weight of defoamer, preferably silicone antifoam emulsion, and • 5 – 30% by weight of N,N-dibutyl-C16-C18-alkylcarboxamide and N,N-dibutyl-C16-C18- alkenylcarboxamide (in .
The present invention as claimed herein is described in the following items 1 to 7: 1. The use of carboxamides of the formula (I) R1-CO-NR 2R3 (I) in which R1 is C16 -C18 -alkyl or C16 -C18 -alkenyl and R2 is C4-alkyl and R3 is C4-alkyl for promoting the penetration of prothioconazole into plants. 2. The use of item 1, in which the carboxamides of the formula (I) are added to the prothioconazole as a tankmix additive. 3. An agrochemical formulation in the form of an emulsion concentrate or dispersion in oil, sing o prothioconazole and o at least one carboxamide of the formula (I) NR 2R3 (I) in which R1 is C16 -C18 -alkyl or C16 -C18 -alkenyl and R2 is C4-alkyl and R3 is C4-alkyl, and o at least one solvent and/or oil. 7_1 (GHMatters) P95895.NZ JENNYP - 7a - 4. The agrochemical ation of item 3, in which the content of the at least one amide of the formula (I) in the agrochemical formulation is o 1 to 50% by weight. 5. The agrochemical formulation of item 3, comprising o 15 - 35% by weight of prothioconazole and o 25 - 45% by weight of N,N-dimethyldecanamide and o 10 - 40% by weight of one or more emulsifiers and o 0.01 - 1.0% by weight of er and o 5 - 30% by weight of N,N-dibutyl-C16 -C18 -alkylcarboxamide and butyl-C16 -C18 - alkenylcarboxamide (in total). 6. A method for promoting the ation of prothioconazole into a plant, comprising applying to the plant a carboxamide of the formula (I) R1-CO-NR 2R3 (I) in which R1 is C16 -C18 -alkyl or C16 -C18 -alkenyl and R2 is C4-alkyl and R3 is C4-alkyl. 7. The method of item 6, in which the carboxamide of the formula (I) is added to the prothioconazole as a tankmix additive.
The mechanism of action of the carboxamides as penetrants is essentially independent of the type of active agrochemical ingredient used. Therefore, the use thereof in ations and crop protection compositions comprising at least one active ingredient from the group of the fungicides or herbicides, the biological efficacy of which can be increased by increased penetration into a crop plant or weed plant, is an option.
Examples of fungicides include: (1) erol thesis inhibitors, for example aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamid, fenpropidin, 7680907_1 (GHMatters) P95895.NZ JENNYP - 7b - fenpropimorph, fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, utanil, naftifin, nuarimol, oxpoconazole, paclobutrazole, pefurazoate, penconazole, piperalin, prochloraz, propiconazole, prothioconazole, ticarb, pyrifenox, quinconazole, simeconazole, amine, tebuconazole, afine, tetraconazole, triadimefon, triadimenol, orph, triflumizole, triforine, triticonazole, uniconazole, uniconazole-p, viniconazole, voriconazole, 1-(4-chlorophenyl)(1H-1,2,4- triazolyl)cycloheptanol, methyl 1-(2,2-dimethyl-2,3-dihydro-1H-indenyl)-1H-imidazole carboxylate, (difluoromethyl)methyl[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N- methylimidoformamide, l-N-methyl-N'-{2-methyl(trifluoromethyl)[3- (trimethylsilyl)propoxy]phenyl}imidoformamide and O-[1-(4-methoxyphenoxy)-3,3-dimethylbutan yl] 1H-imidazolecarbothioate. (2) Respiration inhibitors (respiratory chain inhibitors), for example bixafen, boscalid, carboxin, diflumetorim, fenfuram, fluopyram, anil, fluxapyroxad, furametpyr, yclox, isopyrazam mixture of the syn-epimeric racemate 1RS,4SR,9RS and of the anti-epimeric racemate 1RS,4SR,9SR, isopyrazam (anti-epimeric racemate), isopyrazam (anti-epimeric enantiomer 1R,4S,9S), isopyrazam (anti-epimeric enantiomer 1S,4R,9R), isopyrazam (syn-epimeric racemate 1RS,4SR,9RS), isopyrazam (syn-epimeric enantiomer 1R,4S,9R), isopyrazam (syn-epimeric enantiomer 9S), mepronil, 7680907_1 (GHMatters) P95895.NZ JENNYP oxycarboxin, penflufen, penthiopyrad, sedaxane, thifluzamid, 1-methy1-N-[2—(1,1,2,2— tetrafluoroethoxy)phenyl](trifluoromethyl)-1H-pyrazole—4-carboxamide, 3 -(difluoromethy1)-l - methyl—N—[2-(1 ,1 ,2,2—tetrafluoroethoxy)phenyl]—1H-pyrazole-4—carboxamide, 3 -(difluoromethyl)-N—[4- fluoro-Z-(l l ,2,3 ,3 ,3 -hexafluor0propoxy)phenyl] -1 —methyl- 1 zolecarboxamide, , 2,4- dichlorophenyl)-1 —meth0xypropany1]—3 —(difluor0methy1)—1 —methy1—1H—pyrazolecarboxamide, 5 ,8— difluoro-N—[2-(2—f1uoro {[4-(trifluoromethyl)pyridin-2~yl]oxy}phenyl)ethy1]quinazolineamine, N- [9-(dichloromethylene)—1 ,2,3 ,4—tetrahydro-1 ,4-methan0naphthaleny1] (difluoromethyl)-1 -methyl- 1H—pyrazole—4—carboxamide, N—[( 1 S,4R)(dichloromethylene)-1 ,2,3 ,4-tetrahydro-1 ,4— methanonaphthalen-S—y1]—3-(difluoromethyl)—1 -methy1—1H—pyrazole-4—carboxamide and N—[(1R,4S) (dichloromethylene)-1 ,2,3 ,4—tetrahydr0-1 ,4-methanonaphthaleny1] (difluoromethy1)-1 -methyl-1H- pyrazolecarboxamide. (3) Respiration tors (respiratory chain tors) acting on complex III of the respiratory chain, for example ametoctradin, amisulbrom, azoxystrobin, cyazofamid, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, famoxadone, fenamidone, fenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb, trifloxystrobin, (2E)-2—(2—{[6-(3-chloro~2—methylphenoxy)—5— pyrimidiny1]oxy}phenyl)—2—(methoxyimino)-N-methylethanamide, (2E)-2—(methoxyimino)-N— methyl(2- { [( 1 —[3 ~(trifluoromethyl)phenyl]ethylidene} amino)oxy]methyl}phenyl)ethanamide, (2E)(methoxyimino)—N—methyl-2— {2-[(E)-( { l -[3- (trifluoromethyl)phenyl]ethoxy} imino)methy1]phenyl} ethanamide, (2E) {2—[( { [(1 E)-1 —(3- { [(E)—1 - fluoro-2—phenyletheny1]oxy}pheny1)ethy1idene]amino} oxy)methy1]pheny1} —2—(methoxyimino)—N— methylethanamide, (2E) {2—[( { [(2H,3E)—4-(2,6-dichloropheny1)but—3-en ylidene]amino} oxy)methyl]phenyl} -2—(methoxyimino)-N-methylethanamide, ro-N-( 1 , l ,3 - trimethy1—2,3-dihydro-l H-indeny1)pyridinecarboxamide, 5—methoxy—2—methyl—4-(2- {[( {(1 E)—1 -[3 - (trifluoromethy1)phenyl]ethylidene} amino)oxy]methy1}pheny1)-2,4-dihydro-3H-1 ,2,4-triazol—3-one, methyl (2E)-2— {2—[( {cyclopropyl [(4-methoxypheny1)imino]methyl} sulfany1)methy1]phenyl} —3— methoxyprop-Z-enoate, N—(3-ethy1-3,5,5-trimethylcyclohexy1)(formylamino)hydroxybenzamide, 2- {2-[(2,5-dimethy1phenoxy)methyl]phenyl} methoxy-N-methy1acetamide and (2R)-2— {2—[(2,5- ylphenoxy)methy1]phenyl } methoxy—N—methy1acetamide. 3O (4) s and cell division tors, for example benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fluopicolide, fuberidazole, pencycuron, thiabendazole, anate-methyl, thiophanate, zoxamide, 5—chloro-7~(4-methylpiperidiny1)—6—(2,4,6-trifluoropheny1)[1 ,2,4]triazolo[1 ,5- a]pyrimidine and 3—chloro(6-chloropyridin—3-yl)-6—methyl(2,4,6-trifluoropheny1)pyridazine. (5) Compounds with multisite activity, for example Bordeaux mixture, captafol, captan, chlorothalonil, copper ations such as copper hydroxide, copper naphthenate, copper oxide, copper oxychloride, copper sulfate, dichlofluanid, dithianon, dodine, dodine free base, ferbam, fluorofolpet, folpet, guazatine, guazatine acetate, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, metiram zine, oxine-copper, propamidine, propineb, sulfur and sulfur preparations, for e calcium polysulfide, thiram, tolylfluanid, zineb and ziram. (6) Resistance inductors, for example acibenzolar—S-methyl, isotianil, probenazole and tiadinil. (7) Amino acid and protein biosynthesis inhibitors, for example andoprim, blasticidin—S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil and 3—(5-fluoro-3,3,4,4— tetramethy1-3 ,4-dihydroisoquinolin-1 -y1)quinoline. (8) ATP production inhibitors, for example fentin acetate, fentin chloride, fentin hydroxide and silthiofam. (9) Cell wall sis inhibitors, for example benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamid, polyoxins, polyoxorim, validamycin A and valifenalate. (10) Lipid and membrane synthesis inhibitors, for example biphenyl, chloroneb, dicloran, edifenphos, azole, rb, iprobenfos, isoprothiolane, propamocarb, propamocarb hloride, prothiocarb, pyrazophos, zene, tecnazene and fos—methyl. (ll) Melanin biosynthesis inhibitors, for example carpropamid, diclocymet, fenoxanil, fthalide, pyroquilon, tricyclazole and 2,2,2-trifluoroethy1 {3-methyl—l-[(4—methylbenzoy1)amino]butan—2— yl} carbamate. (12) Nucleic acid synthesis inhibitors, for example benalaxyl, xyl—M (kiralaxyl), bupirimate, clozylacon, dimethirimol, mol, furalaxyl, hymexazol, metalaxyl, metalaxyl-M (mefenoxam), ofiirace, oxadixyl and ic acid. (13) Signal transduction inhibitors, for example chlozolinate, lonil, fludioxonil, iprodione, procymidone, quinoxyfen and Vinclozolin. (l4) Decouplers, for example binapacryl, dinocap, one, am and meptyldinocap. (15) Further compounds, for example azole, bethoxazin, capsimycin, carvone, chinomethionat, pyriofenone (chlazafenone), cufraneb, cyflufenamid, cyrnoxanil, cyprosulfamide, dazomet, debacarb, rophen, diolomezine, oquat, difenzoquat methylsulfate, diphenylamine, , fenpyrazamine, flumetover, fluoromide, flusulfamide, flutianil, fosetyl—aluminium, fosetyl—calcium, l—sodium, hexachlorobenzene, ycin, methasulfocarb, methyl isothiocyanate, metrafenon, mycin, natamycin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, octhilinone, oxamocarb, oxyfenthiin, pentachlorophenol and salts thereof, phenothrin, phosphoric acid and salts thereof, ocarb-fosetylate, propanosine-sodium, proquinazid, pyrimorph, (2E)(4-tert-butylphenyl)—3—(2— chloropyridinyl)—1 —(morpholinyl)prop—2-en-l -one, (ZZ)-3 -(4-tert-butylphenyl)—3-(2-chloropyridin- 4-yl)—l~(morpholinyl)prop-2—en—l—one, nitrin, tebufloquin, tecloftalam, anid, triazoxide, trichlamide, zarilamide, (3 S,6S,7R,8R)benzyl[({3-[(isobutyryloxy)methoxy] methoxypyridin—2- yl}carbonyl)amino]—6-methyl-4,9-dioxo-1,5-dioxonanyl 2—methylpropanoate, l-(4-{4-[(5R)(2,6- difluorophenyl)-4,5-dihydro—l ,2—oxazolyl]-l azolyl}piperidin-l -yl)[5-methyl—3- oromethyl)—1H—pyrazol-l -yl]ethanone, 1-(4- {4—[(5 S)-5—(2,6-difluorophenyl)—4,5~dihydr0—l ,2- oxazol—3—yl] -l ,3 -thiazolyl}piperidin-l -yl)[5~methyl—3—(trifluoromethyl)— l H—pyrazol-l -yl]ethanone, l—(4- {4-[5—(2,6—difluorophenyl)-4,5-dihydro-1 ,2—oxazolyl] -1 ,3 -thiazol-2—y1}piperidin—l —yl)—2—[5— methyl(trifluoromethyl)-lH-pyrazol-l —yl]ethanone, 1 —(4-methoxyphenoxy)-3 ,3 -dimethylbutan-2—yl lH—imidazole-l -carboxylate, 2,3,5 ,6—tetrachloro~4-(methylsulfonyl)pyridine, 2,3-dibutyl thieno[2,3-d]pyrimidin—4(3H)-0ne, 2,6-dimethyl- l H,5H—[l ,4]dithiino[2,3-c:5,6-c']dipyrrole— 1 ,3 ,5 ,7(2H,6H)—tetrone, 2—[5-methyl—3-(trifluoromethy1)-lH—pyrazol—l -yl]-l -(4- {4-[(5R)-5—phenyl-4,5 - dihydro-l ,2-oxazolyl]— l ,3-thiazol—2—yl } piperidin-l —yl)ethanone, 2—[5-methyl(trifluoromethyl)- 1 H- pyrazol-l -yl](4-{4-[(5 S)-5—phenyl-4,5-dihydro—l ,2-oxazol-3 —yl]—1,3-thiazol—2-yl}piper1'din yl)ethanone, 2—[5—methyl(trifluoromethyl)— l H—pyrazol— 1 -y1]-1 — {4-[4—(5-phenyl-4,5-dihydro-l ,2- oxazol—3—yl)—l,3-thiazolyl]piperidin—l-yl}ethanone, 2-butoxyi0do—3-propyl-4H-chromen-4—one, 2- chloro—S-[Z-chloro— l —(2,6—difluoro-4—methoxyphenyl)methyl—l H—imidazol-S —yl]pyridine, 2- phenylphenol and salts thereof, 3-(4,4,5—trifluoro-3,3~dimethyl-3,4-dihydroisoquinolinyl)quinoline, 3 ,4,5—trichloropyridine~2,6-dicarbonitrile, 3—[5-(4-chlorophenyl)—2,3-dimethyl-1 ,2-oxazolidin—3— yl]pyn'dine, 3—chloro(4-chlorophenyl)—4-(2,6-difluorophenyl)methylpyridazine, 4—(4- chlorophenyl)(2,6-difluorophenyl)-3,6—dimethylpyridazine, 5—amin0-1,3,4-thiadiazole-2—thiol, 5- chloro-N’-phenyl—N'—(prop~2-yn-l -yl)thiophene-Z-sulfonohydrazide, 5-fluoro[(4— fluorobenzyl)oxy]pyrimidineamine, 5—fluoro—2—[(4—methylbenzyl)oxy]pyrimidine-4—amine, 5-methyl- 6-octyl[l,2,4]triazolo[l,5-a]pyrimidineamine, ethyl -amino—2-cyanophenylprop—2-enoate, N'—(4— { [3-(4-chlorobenzyl)-l ,2,4-thiadiazol-5—yl] oxy} -2,5-dimethylphenyl)-N-ethyl-N- methylimidoformamide, N—(4—chlorobenzyl)[3-methoxy-4—(propyn-l-yloxy)phenyl]propanamide, N—[(4-chlorophenyl)(cyano)methyl]-3 -[3 -methoxy—4-(propyn-l )pheny1]propanamide, N-[(5 — 3-chloropyridinyl)methyl]-2,4-dichloropyridinecarboxamide, N-[l -(5-br0mo—3 - chloropyridin—Z—yl)ethyl]-2,4—dichloropyridinecarboxamide, N—[l —(5—bromo-3 —chloropyridin yl)ethyl]~2—flu0roiodopyridine-3—Carboxamide, N- {(E)-[(cyclopropylmethoxyflmino] [6— (difluoromethoxy)-2 ,3 -difluorophenyl]methyl} phenylacetamide, N— {(2)— [(cyclopropylmethoxy)imino] [6-(difluor0methoxy)-2,3-difluorophenyl]methyl} -2—phenylacetarnide, N'— -tert—buty1—4—cyano—1 azol—5~y1)oxy] chloromethylpheny1} —N—ethy1—N— imidofonnamide, N-methyl-2—( 1 - { [5—methy1—3 -(trifluoromethy1)- 1 H—pyrazol y1]acety1}pipeiidin—4-y1)-N-(1 ,2,3,4-tetrahydronaphtha1en—1 -y1)—1 ,3—thiazolecarboxamide, N—methyl- 2-(1-{[5-methyl(trifluoromethy1)—1H—pyrazol—l-y1]acety1}piperidiny1)-N—[(1R)—1 ,2,3 ,4- tetrahydronaphthalen—1 -y1] — 1 ,3—thiazolecarboxamide, N-methy1—2—( 1 - { [5-methyl-3 -(trifluoromethyl)- 1H-pyrazol-1 -y1]acetyl}piperidiny1)-N—[(1 S)—1 ,2,3,4-tetrahydr0naphtha1en— 1 -yl] -1 ,3-thiazole carboxamide, pentyl {6-[({[(1-methyl—1H-tetrazo1~5— yl)(pheny1)methy1idene]amino}oxy)methyl]pyridinyl} carbamate, phenazine-l -carboxylic acid, quinolin-S—ol, quinolin01 sulfate (2: 1) and tert~buty1 {6-[({[(1-methy1-1H-tetrazol-5 - yl)(phenyl)methylene]amino } oxy)methyl]pyridin-2—yl} carbamate. (1 6) Further compounds, for example 1 -methyl(trifluoromethy1)-N—[2'~(trifluoromethyl)bipheny1 y1]-1H-pyrazo1e-4—carboxamide, N—(4'-chlorobipheny1—2-y1)-3 oromethyl)-l -methyl-1H—pyrazole- 4—carboxamide, N-(2‘,4'-dichlorobipheny1~2-yl)—3~(difluoromethyl)—1 -methyl—1H—pyrazole carboxamide, 3-(difluoromethy1)-1 -methy1-N—[4'—(trifluoromethy1)bipheny1—2—y1] - 1 H—pyrazole—4- carboxamide, N-(2‘,5'-difluorobiphenyl-2—yl)-1 —methy1—3 -(trifluoromethy1)-1H—pyrazolecarboxamide, 3 -(difluoromethy1)-1 —methyl-N—[4'—(prop— 1 —yn— 1 -y1)bipheny1y1]—1H—pyrazole-4—carboxamide, 5 — fluoro—l ,3 -dimethyl-N-[4'-(prop-1 -yn- 1 —y1)bipheny1—2—y1]—1H—pyrazole-4—carboxamide, 2-chloro-N-[4'yn—1 —y1)bipheny1—2-y1]pyridine—3~carboxamide, 3-(difluoromethy1)—N—[4'-(3 ,3-dimethylbut— 1 -yn- 1 —y1)bipheny1-2—y1] -1 -methy1-1H—pyrazole-4—carboxamide, N—[4’—(3,3-dimethy1but—1 -yn-1 —y1)bipheny1—2— flu0ro-1 ethyl— l H—pyrazole—4—carboxamide, 3 —(difluoromethyl)—N—(4'-ethyny1bipheny1—2—y1)methyl- 1 zole—4-carboxamide, N—(4'-ethynylbiphenylyl)—5-fluoro-1 ,3-dimethy1—1H—pyrazole- 4-carboxamide, 2-ch1oro-N-(4‘~ethyny1bipheny1y1)pyridinecarboxamide, 2-chloro-N-[4'-(3,3 - ylbut—l —yn— 1 —yl)biphenylyl]pyridine-3 -carboxamide, 4—(difluoromethy1)methy1—N—[4'- oromethy1)bipheny1—2-y1] -1 ,3 -thiazolecarboxamide, 5—fluoro-N—[4'—(3-hydroxymethy1but-1 — yn-l —y1)biphenylyl] -1 ,3-dimethy1—1H—pyrazole—4-carboxamide, 2—ch10ro—N—[4'-(3—hydroxy—3- methylbut-l -yn-1 —yl)biphenyl—2-y1]pyridinecarboxamide, 3 -(difluoromethy1)—N—[4'—(3-methoxy-3 - methylbut—l -yn—1 —y1)bipheny1—2—yl]-1 —methy1-1H—pyrazole—4-carboxamide, o—N—[4'—(3-methoxy methylbut-l -yn- 1 —y1)biphenyl-2—y1] -1 ,3-dimethy1—1H—pyrazo16—4-carboxamide, 2-chloro—N—[4'-(3 — methoxy—3-methylbut— 1 -yn-l -y1)bipheny1-2—yl]pyridine—3-carboxamide, (5-bromomethoxy methylpyridiny1)(2,3 ,4—trimethoxy-6—methy1pheny1)methanone, N—[2—(4- { [3 -(4-chloropheny1)prop—2— yn-l -y1]oxy} -3 -meth0xypheny1)ethy1]-N2—(methylsulfonyl)valinamide, 4-oxo[(2- phenylethy1)amino]butanoic acid and but—3 —yn-1—y1 {6-[( { [(Z)-(1 -methy1-1H-tetrazol y1)(phenyl)methylene]amino} oxy)methyl]pyridin—2-y1} carbamate.
A11 mixing ents mentioned in classes (1) to (16) can, if they are capable on the basis of their functional groups, optiona11y form salts with suitable bases or acids.
Examples of herbicides include: Usable combination partners for the inventive compounds in mixture formulations or in a tankmix are, for e, known active ingredients based on inhibition of, for e, acetolactate synthase, — CoA carboxylase, cellulose synthase, enolpyruvylshikimatephosphate synthase, glutamine synthetase, oxyphenylpyruvate dioxygenase, phytoendesaturase, photosystem I, photosystem H, protoporphyrinogen oxidase, as described, for example, in Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 15th edition, The British Crop Protection Council and the Royal Soc. of try, 2006 and literature cited therein. Examples of known herbicides or plant growth regulators which can be combined with the inventive compounds include the active ingredients which follow (the compounds are designated by the "common name" ing to the International Organization for Standardization (ISO) or by the chemical name or by the code number) and always encompass all use forms, such as acids, salts, esters and isomers, such as stereoisomers and optical isomers. One administration form or else, in some cases, more than one administration form is mentioned: acetochlor, acibenzolar, zolar—S—methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryne, amicarbazone, amidochlor, amidosulfuron, yclopyrachlor, aminocyclopyrachlor—potassium, aminocyclopyrachlor-methyl, aminopyralid, amitrole, ammonium sulfamate, ancymidol, os, asulam, atrazine, aviglycine, azafenidin, lfuron, aziprotryne, beflubutamid, benazolin, benazolin—ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfuron, bensulfuron-methyl, bentazone, benzfendizone, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzyladenine, bicyclopyrone, x, bilanafos, bilanafos- sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, bromuron, buminafos, busoxinone, butachlor, butafenacil, butamifos, chlor, butralin, ydim, butylate, cafenstrole, carbaryl, carbetamide, carfentrazone, carfentrazone-ethyl, carvone, chlorocholine chloride, thoxyfen, chloramben, zifop, chlorazifop-butyl, chlorbromuron, chlorbufam, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, muron-ethyl, chlormequat-chloride, chlornitrofen, 4—chlorophenoxyacetic acid, chlorophthalim, chlorpropham, chlorthal-dimethyl, chlortoluron, chlorsulfuron, cinidon, cinidon—ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop, afop-propargyl, clofencet, clomazone, clomeprop, cloprop, clopyralid, cloransulam, cloransulam-methyl, cloxyfonac, cumyluron, cyanamide, cyanazine, 3O cyclanilide, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyprazine, ole, cytokinine, 2,4—D, 2,4—DB, daimuron/dymron, dalapon, daminozide, dazomet, n— decanol, desmedipham, desmetryn, detosyl—pyrazolate (DTP), diallate, diaminozide, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop~methyl, diclofop—P-methyl, diclosulam, diethatyl, diethatyl-ethyl, difenoxuron, difenzoquat, nican, diflufenzopyr, diflufenzopyr—sodium, dikegulac-sodium, dimefuron, perate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimetrasulfuron, dinitramine, dinoscb, dinoterb, diphenamid, diisopropylnaphthalene, dipropetryn, diquat, diquat-dibromide, dithiopyr, diuron, DNOC, eglinazineethyl , endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethyl naphthylacetate, ethcphon, ethidimuron, ethiozin, ethofumesate, ethoxyfen, ethofoen—ethyl, ethoxysulfuron, etobenzanid, F—53 31 , Le. h10r0-4—fluoro[4-(3—flu0ropropy1)-4,5-dihydr0—5-OXO- 1H—tetrazol—1—y1]pheny1]ethanesulfonamide, F-7967, i.e. 3-[7—chlor0fluoro-Z—(trifluoromethyl)-1H— benzimidazoly1]—1—methy1(trifluor0methy1)pyrimidine-Z,4(1H,3H)-dione, fenoprop, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, prop-P-ethyl, fenoxasulfone, fentrazamide, fenuron, flamprop, flamprop—M-isopropyl, flamprop—M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop— butyl, fluazifop—P-butyl, fluazolate, flucarbazone, flucarbazone-sodium, flucctosulfuron, ralin, flufenacct (thiafluamide), flufenpyr, flufenpyr—ethyl, flumetralin, flumetsulam, flumiclorac, flumiclorac- pentyl, azin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoroglycofcn-ethyl, m, flupropacil, flupropanate, flupyrsulfuron, flupyrsulfiiron-methyI-sodium, flurenol, flurenol— butyl, ne, flurochloridone, fluroxypyr, fluroxypyr—meptyl, flurprimidol, flurtamone, fluthiacet, fluthiacet-methyl, fluthiamide, fomesafen, foramsulfilron, forchlorfenuron, fosamine, furyloxyfen, gibberellic acid, glufosinate, glufosinate-armnonium, glufosinate—P, glufosinate—P—ammonium, glufosinate-P-sodium, glyphosate, glyphosate—isopropylammonium, H—9201, i.e. O-(2,4-dimethyl—6— henyl) O-ethyl isopropylphosphoramidothioate, halosafen, halosulfuron, halosulfuron—methyl, haloxyfop, haloxyfop-P, haloxyfop—ethoxyethyl, haloxyfop—P—ethoxyethyl, haloxyfop-methyl, haloxyfop—P—methyl, hexazinone, HW—O2, ie. 1 —(dimeth0xyphosph0ry1)ethyl (2,4- dichlorophenoxy)acetate, imazamethabenz, imazamethabenz—mcthyl, imazamox, imazamox—ammonium, ic, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-annnonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, inabenfide, fan, indaziflam, indoleacetic acid (1AA), 4- ind01ylbutyric acid (IBA), iodosulfuron, iodosulfuronqncthyl-sodium, iofensulfuron, iofensulfuron- sodium, ioxynil, ipfencarbazone, bamid, palin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, KUH—O43, i.e. —(difluor0methy1)methy1 (trifluoromethy1)—1H—pyrazol—4-y1]methy1}sulfony1)—5,5-dimethyl-4,5—dihydr0-1 ,2-oxazole, karbutilate, iradox, lactofen, lenacil, linuron, maleic ide, MCPA, MCPB, MCPB—methyl, -ethy1 and - sodium, mecoprop, mecoprop-sodium, mecoprop—butotyl, mecoprop-P—butotyl, mecoprop-P- ylammonium, mecoprop—P—Z—ethylhexyl, mecoprop-P-potassium, mefenacet, ide, mepiquat—chloride, mesosulfuron, mesosulfuron-methyl, mesotrione, enzthiazuron, metam, metamifop, tron, chlor, metazasulfuron, methazole, methiopyrsulfuron, methiozolin, methoxyphenone, methyldymron, 1-methy1cyclopropcne, methyl isothiocyanate, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, mctoxuron, metribuzin, furon, metsulfuron-methyl, molinate, monalide, monocarbamide, monocarbamide dihydrogensulfate, monolinuron, monosulfuron, monosulfuron ester, monuron, MT—128, i.e. 6-chloro—N-[(2E)—3- chloroprop-Z-en-l-y1]methy1~N—phenylpyridazineamine, MT—5950, i.e. N-[3-chloro-4~(1— methylethyl)phenyl]methylpentanamide, NGGC-Ol 1, 1—naphthylacetic acid (NAA), ylacetamide (NAAm), 2-naphthoxyacetic acid, naproanilide, napropamide, naptalam, NC-310, i.e. 4—(2,4-dichlorobenzoyl)—1—methylbenzyloxypyrazole, neburon, nicosulfuron, clofen, nitralin, nitrofen, nitroguaiacolate, nitrophenolate—sodium (isomer mixture), nitrofluorfen, ic acid, norflurazon, arb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paclobutrazole, paraquat, paraquat dichloride, pelargonic acid (nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, picloram, picolinafen, pinoxaden, piperophos, pirifenop, pirifenop—butyl, pretilachlor, primisulfuron, primisulfuron-methyl, probenazole, profluazole, procyazine, mine, prifluraline, profoxydim, prohexadione, prohexadione—calcium, prohydrojasmone, on, prometryn, propachlor, il, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, prynaehlor, pyraclonil, pyraflufen, fen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, mbenz-isopropyl, pyribambenz-propyl, nzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, orac, quinmerac, quinoclamine, quizalofop, quizalofop—ethyl, quizalofop—P, quizalofop—P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, secbumeton, sethoxydim, siduron, simazine, simetryn, SN-106279, i.e. methyl (2R)({7—[2-chloro-4—(trifluoromethyl)phenoxy]—2— naphthyl}oxy)propanoate, rione, sulfallate (CDEC), sulfentrazone, sulfometuron, sulfometuron— methyl, sulfosate (glyphosate—trimesium), sulfosulfuron, SW—065, SYN-523, SYP-249, i.e. 1-ethoxy-3— methyl—1—oxobut-3—en—2—yl hloro(trifluoromethyl)phenoxy]~2-nitrobenzoate, SYP—300, i.e. l-[7— fluoro—3-oxo—4-(prop—2—yn—1-yl)-3,4-dihydro-2H-l ,4-benzoxazin—6-yl]—3 -propy1thioxoimidazolidine- 4,5-dione, tebutam, tebuthiuron, tecnazene, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, ryne, thenylchlor, thiafluamide, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone—methyl, thifensulfuron, thifensulfuron—methyl, thiobencarb, tiocarbazil, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, triaziflam, triazofenamide, uron, uron-methyl, tribufos, trichloroacetic acid (TCA), pyr, tridiphane, trietazine, trifloxysulfuron, trifloxysulfiiron-sodium, trifluralin, ulfuron, triflusulfuronmethyl , trimeturon, trinexapac, trinexapac-ethyl, tritosulfuron, ef, uniconazole, uniconazole—P, vemolate, ZJ-0862, Le. 3,4—dichloro—N-{2-[(4,6—dimethoxypyrimidin-2~yl)oxy]benzyl}aniline, and the following compounds: Preferred active agrochemical ingredients are triazoles and strobilurins, especially cyproconazole, epoxiconazole, azole, propiconazole, prothioconazole, tebuconazole, and also azoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin and trifloxystrobin.
Likewise preferred are isopyrazam, indaziflam, fluopyram, fluxapyroxad and bixafen. se preferred are all systemic leaf-applied or post—emergence herbicides and safeners, especially amidosulfuron, bromoxynil, cyprosulfamide, 2,4—D, glufosinate, glyphosate, iodosulfuron—methyl, isoxadifen-ethyl, mefenpyr, mesosulfuron, mesotrione, metamitron, phenrnedipham, sulcotrione, tembotrione and thiencarbazone-methyl.
The present invention further relates to formulations and use forms prepared therefrom as crop protection itions and/or pesticides, for example drench, drip and spray liquors, comprising at least one of the inventive N,N-dibutylcarboxamides. The use forms optionally comprise further crop protection agents and/or pesticides and/or action-improving adjuvants, such as penetrants, e.g. vegetable oils, for example rapeseed oil, er oil, l oils, for example n oils, alkyl esters of vegetable fatty acids, for e rapeseed oil methyl ester or soybean oil methyl ester, or alkanol alkoxylates, and/or Spreaders, for example iloxanes, and/or salts, for example organic or inorganic ammonium or phosphonium salts, for example ammonium sulfate or diammonium hydrogenphosphate, and/or retention promoters, for example dioctyl sulfosuccinate or hydroxypropyl guar polymers, and/or humectants, for example ol, and/or fertilizers, for example amrnonium-, potassium— or phosphorus-containing fertilizers.
The formulations optionally comprise, as well as one or more inventive active ingredients, further active agrochemical ingredients.
These are preferably formulations or use forms which comprise auxiliaries, for example extenders, ts, spontaneity promoters, rs, emulsifiers, dispersants, eezes, biocides, thickeners -16— and/or further auxiliaries, for example adjuvants. An adjuvant in this context is a component which enhances the biological effect of the formulation, without the component itself having any biological effect. Examples of adjuvants are agents which promote retention, ing, adhesion to the leaf surface or ation.
These formulations are produced in a known manner, for e by mixing the active ingredients with auxiliaries, for example extenders, solvents and/0r solid carriers and/or further auxiliaries, for example surfactants. The formulations are produced either in suitable facilities or else before or during application.
The auxiliaries used may be substances suitable for imparting special properties, such as certain physical, technical and/or biological properties, to the formulation of the active ingredient, or to the use forms prepared from these formulations (for example ready-to-use crop tion compositions such as spray liquors or seed dressing products).
Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for e from the classes of the aromatic and omatic hydrocarbons (such as paraffins, alkylbenzenes, aphthalenes, chlorobenzenes), the alcohols and polyols (which may ally also be tuted, etherified and/or esterified), the ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, the unsubstituted and substituted amines, amides, lactams (such as N— alkylpyrrolidones) and lactones, the sulfones and sulfoxides (such as dimethyl sulfoxide), and also N,N- dimethyldecanamide, N,N—dimethyloctanamide, N,N—dimethyldodedecanamide, Rhodiasolv Polarclean TM (methyl 5-(dimethylamino)methyloxopentanoate).
If the extender utilized is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Useful liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated tic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene de, aliphatic hydrocarbons such as cyclohexane or paraffins, for e mineral oil fractions, mineral and vegetable oils, ls such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylfonnamide and yl sulfoxide, and also water.
In principle, it is le to use all suitable solvents. Examples of suitable solvents are aromatic hydrocarbons, for example xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated 3O aliphatic hydrocarbons, for example benzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, for example cyclohexane, paraffins, petroleum fractions, mineral and vegetable oils, alcohols, for example methanol, ethanol, panol, butanol or glycol and the ethers and esters thereof, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulfoxide, and water.
In principle, it is possible to use all suitable carriers. Useful carriers include especially: for example ammonium salts and ground natural ls such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic materials such as finely divided silica, alumina and natural or tic silicates, resins, waxes and/or solid fertilizers. Mixtures of such carriers can likewise be used. Useful carriers for granules e: for e crushed and onated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic meals, and also granules of organic material such as sawdust, paper, coconut shells, corn cobs and tobacco stalks.
Liquefied gaseous extenders or solvents can also be used. Particularly suitable extenders or carriers are those which are gaseous at standard temperature and under standard re, for example aerosol propellant gases, such as halohydrocarbons, and also butane, propane, nitrogen and carbon e.
Examples of emulsifiers and/or foam formers, dispersants or wetting agents with ionic or nonionic properties, or mixtures of these surfactants, include salts of polyacrylic acid, salts of lignosulfonic acid, salts of sulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, with substituted phenols (preferably alkylphenols or arylphenols), salts of uccinic esters, e derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated ls or phenols, fatty acid esters of polyols, and derivatives of the nds containing sulfates, sulfonates and phosphates, for example alkylaryl polyglycol ethers, alkyl sulfonates, ulfates, arylsulfonates, protein hydrolysates, lignosulfite waste liquors and methylcellulose. The presence of a surfactant is advantageous when one of the active ingredients and/or one of the inert carriers is insoluble in water and when application is effected in water.
Further auxiliaries which may be t in the formulations and the use forms derived therefrom include dyes such as inorganic pigments, for example iron oxide, titanium oxide and an Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and nutrients and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Additional components may be izers, such as cold stabilizers, preservatives, antioxidants, light stabilizers, or other agents which improve chemical and/or physical stability. Foam formers or antifoams may also be present.
In addition, the formulations and the use forms derived therefrom may also comprise, as additional auxiliaries, stickers such as carboxymethyl cellulose and natural and synthetic rs in the form of s, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as ins and lecithins and synthetic phospholipids. Further auxiliaries may be mineral and vegetable oils.
Optionally, further auxiliaries may be present in the formulations and the use forms derived therefrom.
Examples of such additives include fragrances, tive colloids, binders, adhesives, thickeners, thixotropic agents, penetrants, retention promoters, izers, sequestrants, complexing agents, humectants, Spreaders. In general, the active ingredients can be combined with any solid or liquid additive which is commonly used for formulation purposes.
Useful retention promoters include all those substances which reduce the c surface n, for example l sulfosuccinate, or increase the lasticity, for example hydroxypropylguar polymers.
Useful penetrants in the present context are all those substances which are typically used to improve the penetration of active agrochemical ingredients into plants. Penetrants are defined in this context by their ability to penetrate from the (generally aqueous) application liquor and/or from the spray coating into the cuticle of the plant and thereby increase the mobility of active ingredients in the cuticle. The method described in the literature (Baur et al., 1997, Pesticide Science 51, 2) can be used to determine this property. Examples include alcohol alkoxylates such as coconut fatty ethoxylate (10) or decyl ethoxylate (12), fatty acid esters, for example rapeseed oil methyl ester or soya oil methyl ester, fatty amine alkoxylates, for example amine ethoxylate (15), or ammonium and/or phosphonium salts, for example ammonium sulfate or diammonium hydrogenphosphate.
The formulations contain preferably between 0.00000001% and 98% by weight of active ient or more preferably n 0.01% and 95% by weight of active ingredient, more preferably between 0.5% and 90% by weight of active ingredient, based on the weight of the ation.
The active ingredient content of the use forms (crop protection compositions) prepared from the ations can vary within wide limits. The active ingredient concentration of the use forms may typically be between 0.00000001% and 95% by weight of active ingredient, preferably between 0.00001% and 1% by weight, based on the weight of the use form. Application is accomplished in a customary manner appropriate for the use forms.
The content of the individual components in the inventive ations can be varied within a relatively wide range.
The inventive formulations are produced, for e, by mixing the components with one another in the particular ratios desired. If the active agrochemical ingredient is a solid nce, it is generally used either in finely ground form or in the form of a solution or suspension in an organic solvent or water. If the active agrochemical ingredient is liquid, there is ntly no need to use an organic solvent. It is also possible to use a solid active agrochemical ingredient in the form of a melt.
The temperatures can be varied within a particular range in the course of performance of the process. In l, working temperatures are between 0°C and 80°C, preferably n 10°C and 60°C.
In the performance of the process according to the invention, the procedure is generally to mix the N,N— dibutylcarboxamides of the formula (I) with one or more active ingredients and optionally with additives. The sequence in which the components are mixed with one another is ary.
Useful equipment for performance of the process ing to the invention is customary ent which is used for production of agrochemical formulations.
Examples of administration forms include all the processes known as commonly used to the person skilled in the art: spraying, dipping, misting and a number of specific processes for direct treatment below or above ground of whole plants or parts (seed, root, stolons, stem, trunk, leaf), for example trunk injection in the case of trees or stem bandages in the case of perennial plants, and a number of c indirect application processes.
The term "harmful organisms" encompasses all forms of organisms which cause economic and/or health damage in the particular field of use. Preference is given to organisms harmful to vegetables and animals, and to organisms which cause diseases, particular preference being given to terrestrial and aquatic weed s and broad—leaved weeds, algae, , insects, mites, nematodes, rodents, fungi, bacteria and viruses.
The tive area- and/or object-based application rate of the crop protection compositions of a wide variety of different formulation types for control of the harmful organisms mentioned here varies very greatly. In general, the application media known to the person skilled in the art to be commonly used for the respective field of use are used for this e, for example several hundred liters of water per hectare in the case of standard spraying processes through a few liters of oil per hectare in the case of 'ultra low volume‘ aircraft application down to a few milliliters of a physiological solution in the case of injection processes. The concentrations of the inventive crop tion compositions in the particular application media ore vary within a wide range and are dependent on the tive field of use.
In general, concentrations known to the person skilled in the art to be commonly used for the respective field of use are used. Preferred concentrations are from 0.01% by weight to 99% by weight, more preferably from 0.1% by weight to 90% by weight.
The inventive crop protection compositions can be deployed, for example, in the formulation forms customary for liquid preparations, either as such or after prior dilution with water, i.e., for example, as emulsions, suspoemulsions, suspensions or solutions. Application is effected by customary s, i.e., for example by ng, pouring or injecting.
The application rate of the inventive crop protection compositions can be varied within a relatively wide range. It is guided by the active agrochemical ingredients in question and by the content thereof in the crop protection compositions. ing to the invention, it is possible to treat all plants and plant parts. Plants are understood here to mean all plants and plant populations, such as desired and red wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, ing the transgenic plants and including the plant cultivars which are protectable and non-protectable by plant breeders’ rights. Plant parts are understood to mean all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples of which include leaves, needles, stalks, stems, s, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes. Plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.
As already ned above, it is possible to treat all plants and parts f in accordance with the invention. In a red embodiment, wild plant s and plant cultivars, or those obtained by tional biological breeding, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms), and parts thereof are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above. More preferably, plants of the plant cultivars which are cially available or are in use are treated in accordance with the invention. Plant ars are understood to mean plants which have new properties ("traits") and have been ed by conventional breeding, by nesis or by recombinant DNA techniques. They may be cultivars, varieties, es or genotypes.
The preferred transgenic plants or plant cultivars (those obtained by genetic engineering) which are to be treated in accordance with the invention include all plants which, through the genetic modification, received genetic material which imparts particular advantageous useful traits to these . Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased 3O tolerance to drought or to levels of water or soil salinity, enhanced flowering performance, easier harvesting, accelerated ripening, higher yields, higher quality and/or a higher nutritional value of the harvested products, longer storage life and/or processability of the harvested products. Further and ularly emphasized examples of such properties are an improved defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or s, and also increased tolerance of the plants to certain herbicidally active ingredients. Examples of transgenic plants include the important crop plants, such as cereals (wheat, rice), maize, soybeans, potatoes, sugarbeet, es, peas and other vegetable types, , tobacco, oilseed rape, and also fruit plants (with the fruits of apples, pears, citrus fruits and grapes), particular is being given to maize, soybeans, potatoes, cotton, tobacco and oilseed rape. Traits that are particularly emphasized are improved e of the plants against insects, arachnids, nematodes, slugs and snails by toxins formed in the plants, ally those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIL/X, CryIIIBZ, Cry9c, Cry2Ab, Cry3Bb and CrylF, and also combinations thereof) (referred to hereinafter as "Bt plants"). Traits that are also particularly emphasized are the improved defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and also resistance genes and correspondingly expressed ns and toxins. Traits that are additionally particularly emphasized are the increased tolerance of the plants to certain active herbicidal ingredients, for example imidazolinones, sulfonylureas, sate or phosphinothricin (for example the "PAT" gene). The genes which impart the desired traits in question can also be present in combinations with one another in the transgenic plants. Examples of "Bt plants" include maize varieties, cotton varieties, soya ies and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya), KnockOut® (for e , StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). es of herbicide-tolerant plants which may be mentioned are maize varieties, cotton ies and soybean ies which are sold under the trade names Roundup Ready® (tolerance against sate, for example maize, cotton, soybeans), Liberty Link® (tolerance against phosphinothricin, for example oilseed rape), lMI® (tolerance against imidazolinones) and STS® (tolerance against sulfonylurea, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) also include the varieties sold under the Clearfield® name (for example maize). Of course, these statements also apply to plant cultivars which have these genetic traits or genetic traits which are still to be developed and will be developed and/or marketed in the future.
Preferred plants are those from the group of the usefiil plants, ornamental plants, turfgrass types, commonly used trees which are ed as ornamentals in public and domestic areas, and forestry 3O trees. Forestry trees include trees for the production of , cellulose, paper and products made from parts of the trees.
The term useful plants as used here refers to crop plants which are employed as plants for obtaining foods, animal feeds, fuels or for industrial purposes.
The useful plants which can be treated in accordance with the invention include, for e, the following plant species: turf, vines, cereals, for example wheat, barley, rye, oats, rice, maize and millet/sorghum; beet, for example sugar beet and fodder beet; fruits, for example pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries and berries, for example strawberries, raspberries, blackberries; legumes, for example beans, lentils, peas and soybeans; oil crops, for example oilseed rape, d, poppies, , sunflowers, coconuts, castor oil plants, cacao beans and peanuts; cucurbits, for example pumpkin/squash, ers and melons; fiber plants, for example cotton, flax, hemp and jute; citrus fruit, for example, oranges, lemons, grapefruit and ines; vegetables, for example spinach, lettuce, asparagus, cabbage species, s, onions, tomatoes, potatoes and bell peppers; Lauraceae, for example avocado, Cinnamomum, r, or also plants such as tobacco, nuts, , aubergine, ane, tea, pepper, grapevines, hops, bananas, latex plants and ornamentals, for example flowers, shrubs, deciduous trees and coniferous trees. This enumeration does not constitute a limitation.
The ing plants are considered to be particularly suitable target crops for the application of the process according to the invention: cotton, aubergine, turf, pome fruit, stone fruit, soft fruit, maize, wheat, barley, cucumber, tobacco, vines, rice, cereals, pear, beans, soybeans, oilseed rape, tomato, bell pepper, melons, cabbage, potatoes and apples.
The plants treated in accordance with the invention are, where the use of herbicides is concerned, all kinds of weeds, With regard to the protection of crop plants through application of, for example, fungicides and insecticides, preference is given to application in ically important crops, for e ing transgenic crops, of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, millet/sorghum, rice, manioc and corn, or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables.
The invention is illustrated in detail by the examples but is not restricted thereto. tion examples Penetration test In this test, the penetration of active ingredients though enzymatically isolated cuticles of apple tree leaves was measured. Leaves which had been cut off in the fully ped state from apple trees of the Golden Delicious variety were used. The cuticles were isolated by first filling leaf disks, which had been marked with dye on the underside and punched out, with a pectinase solution (0.2 to 2% th) buffered to a pH between 3 and 4 by means of vacuum infiltration, then adding sodium azide and leaving the leaf disks thus treated to stand until the original leaf ure has dissolved and the non— cellular cuticle has become detached.
Thereafter, only the cuticles of the upper leaf sides which were free of stomata and hairs were used in the further procedure. They were repeatedly washed alternately with water and a buffer solution of pH 7. The clean cuticles ed were finally applied to Teflon sheets and smoothed and dried with a gentle air stream.
In the next step, the cuticular membranes thus obtained were placed into stainless steel diffusion cells (= transport chambers) for membrane transport studies. For this purpose, the cuticles were positioned using tweezers centrally onto the edges of the diffusion cells which had been smeared with silicone grease and sealed with a ring which had se been greased. The arrangement was selected such that the morphological outer side of the cuticles was directed d, i.e. toward the air, while the original inner side faced the interior of the diffusion cell. The diffusion cells were filled with water or with a mixture of water and solvent.
In the case of formulated samples, the active ingredients were made up in tap water and the test additive was added. When ulated active ingredients were used, a e of acetone/tap water was used.
The acetone contents varied between 20% (m/m) and 30% (m/m). This mixture was then added to the initial charge of additive/emulsifier mixture, which gave a transparent solution or an emulsion. In the cases where no t or emulsifier was used, an applicable emulsion has been produced by ultrasound homogenization.
To determine the penetration, 10 ul in each case of a spray liquor of the composition specified in the es were applied to the outer side of a cuticle. After the application of the spray liquors, the water was allowed to vaporize in each case, then the chambers were turned round in each case and placed into thermostated tanks, while blowing air at a defined temperature and air humidity onto the outer side of the cuticle. The penetration which set in therefore took place at a ve air humidity of 60% and a set temperature of 25°C. The active ingredient penetration was measured by means of HPLC or radiolabeled active ingredient.
As is apparent from the examples listed in the table, the presence of N,N—dibutylcarboxamides leads to a ct rise in the penetration of all the active ingredients . The control used here in each case was the variant without N,N—dibutylcarboxamides, which was either the active ingredient or the formulation alone, or else, when an emulsifier was used in the mixture with N,N~dibutylcarboxamide, the active ingredient or the formulation with this emulsifier.
The dimethyl— and dibutylcarboxamides used in the examples are the respective mixtures of the corresponding carboxamides. For e, Cl6-l8 dibutyl amide means a mixture consisting essentially of N,N—dibutyl—C l 6— and -Cl 8-carboxamides.
Table, example 1 The bromoxynil active ingredient was made up formulated as WP 20 in tap water (1 g/l bromoxynil) and applied with castor oil ethoxylate emulsifier alone (0.5 g/l) or different spray liquor concentrations of N,N—dibutyl-C12-14—carboxamide (emulsified with a castor oil ethoxylate emulsifier), and the penetration of bromoxynil was measured. The table shows the penetration after 3 and 24 hours at 20°C and 60% relative air ty.
Mean penetration of bromoxynil" in % (n= 4-8) bromoxynil WP20 Additive concentration without/with (g/1) bromoxynil WP20 in water without additive castor oil ethoxylate emulsifier** C12-14 dibutyl amide** C12—l4 dibutyl amide* * C 1 2-14 dibutyl amide* * * 1.0 g/l bromoxynil; **with 0.5 g/l castor oil ethoxylate as emulsifier The on of butyl-C12carboxarnide has led to a distinct rise, which has low dependence on concentration above 1 g/l, in the ation of bromoxynil. —26- Table, example 2 The bromoxynil octanoate active ingredient was made up formulated as EC225 in water (1.5 g/l bromoxynil octanoate) and applied with castor oil ethoxylate emulsifier alone (0.5 g/l) or different spray liquor concentrations of N,N—dibutyl-C12—14—carboxamide (emulsified with a castor oil ethoxylate emulsifier), and the penetration of bromoxynil octanoate was measured. The table shows the penetration after 3 and 24 hours at 20°C and 60% ve air humidity.
Mean penetration of bromoxynil ate* in % (n= 4-8) bromoxynil octanoate Additive 3 h 24 h concentration without/with (g/l) bromoxynil octanoate EC225 in 49 water Without additive castor oil ethoxylate 5 51 fier* * C 12 14 dibutyl amide' ' ** 1 2 53 C12 14 dibutyl amide‘ ‘ >1: >2: 1 3 70 C12 ' ‘ * >x< _ 1 4 l amide 1 8 68 * 1.5 g/l bromoxynil octanoate; **with 0.5 g/l castor oil ethoxylate as emulsifier The addition of N,N—dibutyl-C12carboxamide has led to a distinct, tration—independent rise in the penetration of bromoxynil octanoate, particularly immediately after application.
Table, example 3 The bromoxynil active ingredient was made up in acetone/water (1.5 g/l bromoxynil) and applied with castor oil ethoxylate emulsifier alone (0.5 g/l) or different spray liquor concentrations of N,N-dibutyl- C12-l4-carboxamide (emulsified with a castor oil ethoxylate emulsifier), and the penetration of bromoxynil was ed. The table shows the penetration after 3 and 24 hours at 20°C and 60% relative air humidity.
Mean penetration of bromoxynil" in % (n= 4-8) bromoxynil without/with Additive 3 h 24 h concentration (g/1) castor oil ethoxylate 0.5 1 9 emulsifier* * C12 14 dlbutyl amide' ‘ >z< >i< _ l 29 70 C12 14 l amide' ' * >i< _ 3 9 85 C12 14 dibutyl amide. . ** _ 5 61 8 3 * 1.5 g/l bromoxynil; **with 0.5 g/l castor oil ethoxylate as fier The addition of N,N—dibutyl-C12—14-carboxamide has led to a distinct, coneentration-independent rise in the ation of bromoxynil. —28— TableI example 4 The bromoxynil active ingredient was made up in acetone/water (1.5 g/l ynil) and applied with castor oil ethoxylate emulsifier alone (0.5 g/l) or different spray liquor trations of N,N—dibutyl- C8carboxamide (emulsified with a castor oil ethoxylate emulsifier), and the penetration of bromoxynil was measured. The table shows the penetration after 3 and 24 hours at 20°C and 60% relative air humidity.
Mean penetration of bromoxynil" in % (n= 4-8) ynil without/with ve concentration (g/l) castor oil ethoxylate 10 emulsifier* * C8~10 dibutyl amide* * C8-10 dibutyl amide** (38—10 dibutyl amide** * 1.5 g/l bromoxynil; **With 0.5 g/l castor oil ethoxylate as emulsifier The addition of N,N-dibutyl—C12—l 4-carboxamide has led to a distinct, concentration—independent rise in the penetration of bromoxynil. -29..
Table, example 5 The bromoxynil active ingredient was made up in acetone/water (1.5 g/l bromoxynil) and applied with castor oil ethoxylate emulsifier (0.5 g/l) alone or er with N,N—dibutyl—C8—l0-carboxamide, N,N- dibutyl-Cl2—l4-carboxamide or N,N—dibutyl—C16—l8—carboxamide (emulsified with a castor oil ethoxylate emulsifier) at a spray liquor concentration of 3 g/l, and the penetration of bromoxynil was measured. The table shows the penetration after 3 and 24 hours at 20°C and 60% relative air humidity.
Mean penetration of bromoxynil* in % (n= 4-8) bromoxynil Without/with ve 3 h 24 h tration (g/1) castor oil ethoxylate 0.5 1 6 emulsifier** C8—10 dibutyl amideHos 3 1 6 39 C12 14 dibutyl amide' ' ** _ 3 8 31 Cl 6 . . M _ l 8 dibutyl amide 3 7 32 * 1.5 g/l bromoxynil; **with 0.5 g/l castor oil ethoxylate as emulsifier The addition of the N,N—dibutylcarboxamides has led to a ct rise in the penetration of bromoxynil.
Table, example 6 The bromoxynil active ingredient was made up in acetone/water (1.5 g/l bromoxynil) and applied with castor oil ethoxylate emulsifier (0.5 g/l) alone or together with noninventive N,N—dimethyl—C8-C10- amide or ive N,N—M—C8~ClO-carboxamide or N,N—gi‘b_t_1tyl-Cl2-C l4-carboxamide (emulsified with a castor oil ethoxylate emulsifier) at a spray liquor concentration of l or 3 g/l, and the penetration of bromoxynil was measured. The table shows the penetration after 5 and 24 hours at 20°C and 60% ve air humidity.
Mean penetration of bromoxynil* in % (n= 4—8) bromoxynil variant N,N— 5 h 24 h without/with dialkylcarboxarnide concentration (g/l) bromoxynil in acetone/water with 0.5 g/l castor oil 4 20 ethoxylate emulsifier C8-10 dimethyl * 20 30 C8—10 dimethyl amide** 45 57 C8—1 0 dibutyl amide** 32 72 C8—10 dibutyl amide** 67 86 C12—l4 dibutyl amide** 29 70 Cl2—l4 dibutyl amide** 59 85 * 1.5 g/l bromoxynil ** with 0.5 g/l castor oil ethoxylate emulsifier The addition of the N,N—dibutylcarboxamides has led to a distinct, tration-independent rise in the penetration of bromoxynil. In all cases, the effect was distinctly superior to that of the dimethyl—C8- C10—carboxamides.
Table, example 7 The spirotetramat active ingredient was dissolved in acetone/water (0.3 g/l spirotetramat) and applied alone or together with different spray liquor concentrations of N,N-dibutyl-Cl2carboxamide (emulsified with a castor oil ethoxylate emulsifier), and the penetration of spirotetramat was measured.
The table shows the penetration after 3 and 24 hours at 20°C and 60% ve air humidity.
Mean penetration of spirotetramat* in % (n= 4-8) spirotetramat without/with N,N— 3 h 24 h lcarboxamide tration spirotetramat in 0 l acetone/water t N,N— dibutylcarboxamide C12—14 dibutyl amide** 2 23 c1244 dibutyl amide** 2 25 (312—14 dibutyl amide** 8 39 C12—14 dibutyl amide* * l 3 65 * 0.3 g/l spirotetramat; **with 0.5 g/l castor oil ethoxylate as emulsifier The addition of N,N—dibutyl—C12—14—carboxamide has led to a distinct, concentration-independent rise in the penetration of spirotetramat.
Table, e 8 The etramat active ingredient was made up ated as SC240 in tap water (0.3 g/l spirotetrarnat) and applied alone or together with N,N—dibutyl—C8~10—carboxamide, N,N—dibutyl-C12- l4-carboxamide 0r N,N-dibuty1-C16~18-carboxamide at a spray liquor concentration of 1 g/l (homogenized by ultrasound treatment), and the penetration of spirotetramat was measured. The table shows the penetration after 3 and 24 hours at 20°C and 60% relative air humidity.
Mean penetration of spirotetramat* in % (n= 4-8) spirotetramat without/with N,N- 3 h 24 h dibutylcarboxamide concentration (g/l) spirotetramat SC240 without - 1 2 N,N—dibutylcarboxamide C8—l 0 dibutyl amide l l 13 C 1 2-14 dibutyl amide 4 10 C] 6-1 8 dibutyl amide 4 16 * 0.3 g/l spirotetramat The addition of the three N,N—dibutylcarboxamides has led to a distinct rise in the penetration of spirotetramat.
Table, example 9 The kresoxim—methyl active ingredient was made up in acetone/tap water (0.3 g/l kresoxim-methyl) and applied alone or together with butyl-C8-l0—carboxamide, N,N-dibutyl-Cl2~l4—carboxamide or N,N-dibutyl—Cl6carboxamide at a spray liquor concentration of l or 3 g/l (emulsified with 0.4 g/l tristyrylphenyl ethoxylate), and the penetration of kresoxim—methyl was measured. The table shows the penetration after 3 and 24 hours at 20°C and 60% relative air ty.
Mean penetration of kresoxim—methyl * in 0/o (I): 4-8) kresoxirn—methyl N,N— 3 h 24 h dibutylcarboxamide tration (g/l) kresoxim-methyl in — acetone/water without N‘,N- 1 3 dibutylcarboxamide C8-10 dibutyl * 60 66 C12 14 dibutyl amide' ‘ ** 51 82 C12 14 dibutyl amide' ' ** 68 99 C16-18 dibutyl amide** 52 76 * 0.3 g/l kresoxim—methyl, **with 0.4 g/l tristyrylphenol ethoxylate The addition of the three N,N—dibutylcarboxamides has led to a distinct rise in the penetration of kresoxim-methyl.
Table, example 10 The azoxystrobin active ingredient was made up in acetone/tap water (0.3 g/l azoxystrobin) and applied alone or together with N,N—dibutyI-CS-l0-carboxamide, N,N—dibutyl-Cl2carboxamide or N,N- dibutyl-C16—l8—carboxamide at a spray liquor concentration of l or 3 g/l (emulsified with 0.4 g/l tristyrylphenyl ethoxylate), and the penetration of azoxystrobin was ed. The table shows the penetration after 3 and 24 hours at 20°C and 60% relative air humidity.
Mean ation of azoxystrobin * in % (n= 4-8) azoxystrobin variant N,N- without/With dibutylcarboxamide concentration (g/l) azoxystrobin in e/water without N,N— lcarboxamide C8-l O dibutyl amide** 34 46 C12 14 dibutyl amide. . *4: 7 1 4 C12 14 dibutyl amide’ ' * >z< 9 37 Cl 6-1 8 dibutyl amide** 6 36 * 0.3 g/l azoxystrobin, **with 0.4 g/l tristyrylphenol ethoxylate The addition of the three N,N-dibutylcarboxamides has led to a distinct rise in the penetration of azoxystrobin.
Table, example 11 The epoxiconazole active ingredient was made up in acetone/tap water (0.3 g/l epoxiconazole) and applied alone or together with N,N—dibutyl-C8—l0—carboxamide, butyl—Cl2-14—carboxamide or N,N-dibutyl—Cl6—18—carboxarnide at a spray liquor concentration of l or 3 g/l (emulsified with 0.4 g/l tristyrylphenyl ethoxylate), and the penetration of epoxiconazole was measured. The table shows the penetration after 3 and 24 hours at 20°C and 60% relative air humidity.
Mean penetration of epoxiconazole * in % (n= 4—8) epoxiconazole variant N,N- 3 h 24 h without/With dibutylcarboxamide concentration (g/l) epoxiconazole in — e/water Without N,N- 1 2 lcarboxamide C8-10 dibutyl amide** 67 73 C12 14 l amide. . ** 52 96 C12 14 dibutyl amide' ' *4: 54 95 C16-18 dibutyl amide** 17 95 * 0.3 g/l epoxiconazole, **with 0.4 g/l tristyrylphenol ethoxylate The addition of the three N,N—dibutylcarboxamides has led to a distinct rise in the penetration of epoxiconazole.
Table, example 12 The propiconazole active ingredient was made up in acetone/tap water (0.3 g/l propiconazole) and applied alone or together with N,N—dibutyl-C12carboxamide or N,N-dibutyl-Cl6—18-carboxamide at a spray liquor concentration of 1 or 3 g/l (emulsified with 0.4 g/l tristyrylphenyl ethoxylate), and the penetration of propiconazole was measured. The table shows the penetration after 3 and 24 hours at °C and 60% relative air humidity.
Mean penetration of propiconazole * in % (n= 4-8) propiconazole t N,N- without/with dibutylcarboxarnide concentration (g/l) propiconazole in acetone/water t N,N- dibutylcarboxamide C12-14 dibutyl amide* * 53 85 C12 14 dibutyl amide' ’ ** 72 89 C16-18 dibutyl amide* * * 0.3 g/l propiconazole, **with 0.4 g/l tristyrylphenol ethoxylate The on ofN,N—dibutyl-C12carboxamide or butyl-Cl6-l 8-carboxamide has led to a distinct rise in the penetration of propiconazole.
Table, example 13 The isopyrazam active ingredient was made up in acetone/tap water (0.3 g/l isopyrazam) and applied alone or together with N,N-dibutyl-C8-l0-carboxamide, N,N—dibutyl-C12-l4-carboxamide or N,N— dibutyl-C1648-carboxamide at a spray liquor concentration of 1 or 3 g/l (emulsified with 0.4 g/l tristyrylphenyl ethoxylate), and the penetration of isopyrazam was measured. The table shows the penetration after 3 and 24 hours at 20°C and 60% relative air humidity.
Mean penetration of isopyrazam * in % (n= 4-8) isopyrazam variant N,N— without/with lcarboxamide concentration (g/l) isopyrazam in acetone/water without N,N- dibutylcarboxamide C8-10 dibutyl amide** 37 87 C12 14 l amide- ' ** 11 54 C12 14 dibutyl amide‘ ' ** 12 49 Cl6—l8 l amide** 10 35 * 0.3 g/l isopyrazam, **with 0.4 g/l tristyrylphenol late The addition of the three N,N-dibutylcarboxamides has led to a distinct rise in the penetration of isopyrazam. -38— Table, example 14 The flam active ingredient (formulated as SCSOO) was made up in tap water (0.3 g/l indaziflam) and applied alone or together with N,N—dibutyl-C8—10—carboxamide, N,N—dibutyl-C12—14—carboxarnide or N,N—dibutyl-Cl6—18—carboxamide at a spray liquor concentration of 2.5 g/l (emulsified with castor oil ethoxylate or tristyrylphenol ethoxylates), and the penetration of indaziflam was measured. The table shows the penetration after 24 and 48 hours at 20°C and 60% relative air humidity.
Mean ation of indaziflam * in % (n= 4—8) indaziflam variant N,N— 24 h 48 h Without/with dibutylcarboxamide concentration (g/l) indaziflam SC500 in water - Without N,N- 3 6 dibutylcarboxamide C8-10 dibutyl amide' ' 26 34 C12 14 clibutyl amide' ' ** 27 49 C16—1 8 dibutyl amide* * 8 17 C16-18 dibutyl amide*** 14 70 C16—18 dibutyl amide**** 40 77 * 0.3 g/l indaziflam, ** with 0.5 g/l castor oil ethoxylate *** with 0.5 g/ rylphenol as emulsifier, ethoxylate 16 (***) or 29 BO (****) The on of the three N,N—dibutylcarboxamides has led to a distinct rise in the penetration of indaziflam.
Table, example 15 The oconazole active ingredient was made up in acetone/tap water (0.3 g/l prothioconazole) and applied alone or together with N,N-dibutyl-C12—14-carboxamide or N,N—dibutyl-Cl6carboxamide at a spray liquor concentration of 1 g/l (emulsified by ultrasound ent), and the penetration of prothioconazole was measured. The table shows the penetration after 3 and 24 hours at 25°C and 60% relative air humidity.
Mean penetration of prothioconazole* in % (n= 4—8) prothioconazole variant N,N- lcarboxamide without/with concentration (g/l) prothioconazole in acetone/water C12-14 dibutyl amide C 1 6—1 8 dibutyl amide * 0.3 g/l prothioconazole The addition of the two N,N-dibutylcarboxamides has led to a distinct rise in the penetration of prothioconazole.
Table, example 16 Comparison of the N,N—dibutylcarboxamides used in accordance with the invention with the N,N- dimethylcarboxamide from theprior art The table which follows shows the comparison of the penetration of prothioconazole from the commercial formulation or of a novel inventive composition where 20% of the methyl-CS-IO- carboxamide solvent has been replaced by N,N—dibutyl-C16—l8-carboxamide (figures in percent by mass), with 25% prothioconazole.
Formulation A: 20% KS emulsifier % N,N-dibutyl-C16-1 8-carboxamide 34.9% N,N—dibutyl—C8-lO-carboxamide 0.1% defoamer The prothioconazole active ient was made up formulated as the commercial standard EC250 or with the inventive formulation in tap water (0.3 g/l prothioconazole), and the ation of prothioconazole was measured in an experiment in which 15°C and 80% relative air humidity were set on the first day, and 25° and 60% on the second day. The table shows the penetration after 12 and 24 hours at 25°C and 60% relative air humidity.
Mean penetration of oconazole* in % (n= 4-8) Variant 12 h 24 h 36 h 48 h rd EC250 formulation 3 4 6 8 Inventive EC250 ation A 6 10 19 23 * 0.3 g/l prothioconazole The example shows that the N,N-dibutylcarboxamides used in accordance with the invention lead to enhanced penetration compared to the N,N-dimethylcarboxamide from the prior art.
Table, example 17 ison of the N,N-dibutylcarboxamides used in accordance with the ion with the N,N— dimethylcarboxamide from theprior art The prothioconazole active ingredient was made up in acetone/tap water (0.8 g/l prothioconazole) and applied together with N,N—dimethyl-C8carboxamide (1.5 g/l) alone or with addition (0.5 g/l or 1 g/l in the mixture) of inventive N,N—dibutyl-C8carboxamide, N,N-dibutyl-C12carboxamide or N,N— dibutyl-Cl6carboxamide (in each case with with 0.4 g/l tristyrylphenol ethoxylate), and the penetration of prothioconazole was ed. The table shows the penetration after 3 and 24 hours at 20°C and 60% relative air humidity.
Mean penetration of prothioconazole* in % (n= 4—8) prothioconazole variant N,N— 3 h 24 h dibutylcarboxamide without/With concentration (g/l) oconazole in acetone/water with 1.5 g/l N,N-dimethyl-C8—C10- carboxamideW 13 (11:21) 3 .7 (n=21) C8-10 l amide** 2.1 6.3 C8-10 dibutyl amide** 2.5 9.3 C12-14 dibutyl amide** 2.0 9.4 C12-14 dibutyl amide** 4.2 16.6 C16-18 dibutyl amide** 2.1 7.4 C16-18 dibutyl amide** 3.2 17.9 * 0.8 g/l prothioconazole, **with 0.4 g/l tristyrylphenol ethoxylate The addition of the three N,N—dibutylcarboxamides to a solution of oconazole already containing a relatively high amount of N,N-dimethy1~C8-C10—carboxamide has led to a distinct, more significant and concentration—dependent rise in the penetration of prothioconazole.
Table, example 18 Enhancement of the fungicidal action of Proline in wheat with N,N-dibutyl-C16—18—carboxamide In two field trials, the influence of N,N—dibutyl—Cl6—18-carboxarnide on the fungicidal efficacy of Proline EC250 against several pathogenic harmful fungi was . The field trials were set up in winter wheat in a field near eid, Germany. The trials were randomized with three repetitions, and one trial plot had an area of 6 m2. The planting dates were 10.20.2009 and 2009. Other fertilization and crop protection es were in accordance with agricultural practice.
The test substances were applied twice in succession at the wheat growth stages EC32 and EC39. The interval was 2 or 3 weeks. Prothioconazole was used in the form of an EC 250 formulation (trade name: Proline), and the N,N-dibutyl-C16—l8-carboxamide in the form of an EC500. Proline was used either alone or with tankmix addition of N,N-dibuty1—C16-1 8-carboxamide. The water application rate in the spray application was 300 l/ha.
The level of disease on the ears of wheat and the e control n) were rated on June 30 and July 1, 2010, i.e. about 4 weeks after the second fungicide application. The influence of N,N—dibutyl-C16- lS—carboxamide on the enhancement of efficacy of Proline is shown in the table below.
Trial 1 Trial 2 Pathogen Leptosphaeria Puccina Pyrenophora m recondita teres Variant Amount of active ingredient Action as per Abbott (%) per hectare Untreated — l4 ‘ 5 tation) Proline 75 67 72 ‘ 70 Proline + 0.1% N,N— 75 dibutyl-C16-l 8- carboxamide * * 0.2% N,N-dibuty1-C 1 6-1 8-carboxamide EC500 is an N,N—dibutyl-C16carboxamide The result shows that even a concentration of 0.1% N,N—dibutyl—Cl6-l8-carboxarnide significantly enhances the fungicidal action of Proline.
Table, example 19 Enhancement of the herbicidal efficacy of indaziflam with butyl-C12-14—carboxamide: Two field trials were conducted in order to study the influence of C12-14 dibutyl amide on the herbicidal efficacy of the ide indaziflam. The field trials were set up (1) in Fresno (California, USA) and (2) Mereville (France). The two products were deployed on a natural mixture of weeds. The plot size in trial 1 was 9.3 m2 and that in trial 2 was 6 m2. The weed plants were treated with the products at an early development stage (the plant height measured ing to the weed species was 2 cm to 7 cm). For this purpose, the products to be applied were dissolved and d in water and then sprayed with 187 liters per hectare (trial 1) and 250 liters per hectare (trial 2) as a spray solution directly onto the weed plants.
In both field trials, indaziflam SC500 as a single product was tested in comparison to indaziflam SCSOO in a tankmix with 0.5 liter per hectare of N,N—dibutyl-C12carboxamide. In trial 1, the ation rate of indaziflam (formulated as SCSOO) was 50 grams of active substance per hectare, and in trial 2 it was 75 grams of active substance per hectare. The weed mixture consisted of the following monocotyledonous weeds: Digitaria sanguinalis (DIGSA), Lolium multiflorum (LOLMU), Setaria glauca (PESGL) and Setaria illata (SETVE), and of the ing dicotyledonous weeds: Amaranthus retroflexus (AMARE), Abutilon theophrasti (ABUTH), Chenopodium album (CHEAL), Fallopia convolvulus (POLCO).
The herbicidal action of the products was rated visually compared to the untreated control. The herbicidal action was expressed in percent (%): 100% herbicidal action = weed plants have died off completely; 0% action = like control plants). Trial 1 was rated 7 days after the application of the products, and trial 2 was rated 28 days after the application. The tive results of the field trials are shown in table 1 (field trial 1) and in table 2 (field trial 2).
Table 19a: Weed control as Amount of AMARE CHEAL PESGL LOLMU ABUTH per Abbott (%) active ingredient per hectare (g/ha) indaziflam 50 46 28 43 53 55 indaziflam + 50 88 73 82 83 85 C12-14 dibutyl amide Table 19b: Weed l as per Amount of active POLCO CHEAL SETVE DIGSA Abbott (%) ingredient per hectare !. (g/ha) indaziflam 75 15 10 45 15 indaziflam + 75 + 0.5 l/ha 63 86 55 80 C12-14 dibutyl amide In both field trials, it was shown that the addition of 0.5 liter per hectare of N,N—dibutyl—C12-14— amide to the indaziflam herbicide significantly enhances the efficacy on weeds. —46- Example 20: Coverage It has also been found that, surprisingly, the water-insoluble butylcarboxamides distinctly increase the coverage ~ the proportion of the plant surface wetted with the spray liquid in the spray application — after emulsion with various emulsifiers. For instance, in the case of spray application with an air injector nozzle (TeeJet A111003, 200 l/ha) to maize with 2 g/l of an on of N,N-dibutyl— C12—14—carboxamide 0r N,N—dibutyl—C16—l8—carboxamide (emulsified with 0.5 g/l sorbitan ester late), the coverage was from 1.1% (proportion of the area wetted in relation to the plant area treated) for water to 18.5% (N,N-dibuty1—C12carboxamide) or 17.9% (N,N-dibutyl-C16 carboxamide). The value for the emulsifier alone was 7.3%.
Table, example 21 The active ingredient fluopyram was made up as an EC formulation in the laboratory: fluopyram is dissolved in a preliminary mixture of solvent and emulsifier (dimethylacetamide + Tanemul P816) and diluted with water to give the ready—to—use test solution. The test solution contains 0.5 g/l active ingredient, 0.5 g/l emulsifier and 2% by weight of solvent. It is applied alone or together with N,N- dibutyl-Cl6-l8-carboxamide or N,N-dimethyl-Cl8-carboxamide at a spray liquor concentration of 1.5 g/l ified by ultrasound treatment) to isolated apple leaf cuticles and the penetration of fluopyram is ed. The table shows the penetration after 6 and 24 hours at 25°C and 60% relative air humidity.
Mean ation of fluopyram in "/0 (n = 8— Test solution Carboxamide concentration (g/l) fluopyram (0.5 g/l) 20 53 fluopyram & Cl 6-1 8 dibutyl amide fluopyram 34 5 l & C18 dimethyl amide The addition of the N,N—dibutyl-Cl6-Cl 8-carboxamide compared to the ponding dimethyl amide led to more significant enhancement of the ation of fluopyram.
Table, example 22 Intrinsic penetration of the NLN;dibutylcarboxamides The N,N—dibutyl-Cl6—Cl8— and —Cl2—Cl4—alkyl/alkenylcarboxamides and the analogous dimethyl amides were made up as EC formulations in the laboratory: they are dissolved in a preliminary e of solvent and emulsifier (dimethylacetamide + Tanemul P816) and diluted with water to give the ready-to-use test solution (emulsified by ultrasound treatment). The test solutions each contain 1.5 g/l carboxamide, 0.5 g/l fier and 2% by weight of solvent. They are applied to isolated apple leaf cuticles and then the intrinsic ation of the carboxamides is measured. The table shows the penetration after 6 and 24 hours at 25°C and 60% relative air humidity.
Penetration of carboxamide in % (n = 8-10) Test solution Carboxamide concentration (g/l) Cl 6-l 8 dibutyl amide l .5 O 0 C1 8 dimethyl amide l .5 22 61 C12-l4 dibutyl amide 1.5 2 4 C12 dimethyl amide l .5 49 47 The intrinsic penetration of the methylcarboxamides is much greater than that of the analogous dibutyl amides. The C1 6—1 8 dibutyl amide has no able penetration at all. _ 49 _ Formulation examples The inventive formulations which follow were produced by mixing the individual components.
Formulation example 1 To produce the proper invention with the active ingredient tebuconazole, the ing are first mixed at room temperature with ng: g of tebuconazole with 56 g dimethyldecanamide and then with g of ethoxypropoxytristyrylphenol (block copolymer), 4 g of water and g of N,N—dibutyl—C16~C18-carboxamide.
After on has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 2 To produce the proper invention with the active ingredient tebuconazole, the following are first mixed at room temperature with stirring: g of tebuconazole with 51 g of N,N—dimethyldecanamide and then with 10 g of ethoxypropoxytristyrylphenol (block copolymer), 4 g of water and g of N,N—dibutyl-Cl 6—C 1 oxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained. _ 50 _ Formulation e 3 To produce the proper ion with the active ingredient tebuconazole, the ing are first mixed at room temperature with stirring: g of tebuconazole with 52 g of N,N-dimethyldecanamide and then with 3 g of ethoxypropoxytristyrylphenol (block copolymer), g of castor oil polyglycol ether ester and g of N,N-dibutyl-Cl 6—Cl 8-carboxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained. ation example 4 To produce the proper invention with the active ient epoxiconazole, the following are first mixed at room temperature with stirring: 10 g of epoxiconazole with 65 g of benzyl alcohol and then with 7.5 g of ethoxypropoxytristyrylphenol (block copolymer), 7.5 g of castor oil polyglycol ether ester and g of N,N—dibutyl-C 1 6-Cl 8-carboxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 5 To produce the proper invention with the active ingredient epoxiconazole, the following are first mixed at room temperature with stirring: g of onazole with 50 g of benzyl l and then with 10 g of 2—sec-butylphenol, 7.5 g of ethoxypropoxytristyrylphenol (block copolymer), 7.5 g of castor oil polyglycol ether ester and g of N,N—dibutyl-C16-C l 8-carboxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 6 To produce the proper invention with the active ingredient fluoxastrobin, the following are first mixed at room ature with stirring: 10 g of fluoxastrobin with g of gamma—butyrolactone and then with g of 2-ethylhexanol propylene/ethylene glycol ether, g of ethoxypropoxytristyrylphenol (block copolymer), g of alkoxylated ethylenediamine having an average of 16 E0 and 16 PO units, 5 g of rylphenol ethoxylate having an average of 16 BO units and g ofN,N—dibutyl—C16-C18-carboxamide.
After addition has ended, the mixture is d at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained. -52_ Formulation example 7 To produce the proper invention with the active ingredient fluoxastrobin, the following are first mixed at room temperature with stirring: g of fluoxastrobin with g of gamma—butyrolactone and then with g of 2-ethylhexanol propylene/ethylene glycol ether, g of ethoxypropoxytristyrylphenol (block copolymer), g of lated ethylenediamine having an average of 16 E0 and 16 PO units, g of tristyrylphenol ethoxylate having an average of 16 E0 units and 15 g of N,N-dibutyl-C1 6-C1 oxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 8 To produce the proper invention with the active ingredient azoxystrobin, the following are first mixed at room temperature with stirring: g of azoxystrobin with g of butyrolactone and then with g of 2-ethylhexanol propylene/ethylene glycol ether, 15 g of ethoxypropoxytristyrylphenol (block copolymer), g of alkoxylated ethylenediamine having an e of 16 E0 and 16 PO units, g of tristyrylphenol ethoxylate having an e of 16 E0 units and g of N,N-dibutyl-C16—C18-carboxamide.
After on has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 9 To produce the proper invention with the active ingredient azoxystrobin, the following are first mixed at room temperature with stirring: g of azoxystrobin with g of butyrolactone and then with g of 2—ethy1hexanol propylene/ethylene glycol ether, 15 g of ethoxypropoxytristyrylphenol (block mer), g of alkoxylated ethylenediamine having an average of 16 E0 and 16 PO units, g of tristyrylphenol ethoxylate having an average of 16 E0 units and 1 5 g of N,N—dibutyl-C 1 6-C1 8-carboxamide.
After addition has ended, the mixture is stirred at room ature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 10 To produce the proper invention with the active ingredient trifloxystrobin, the following are first mixed at room temperature with stirring: 10 g of trifloxystrobin with 44.97 g of N-methylpyrrolidone and then with g of tristyrylphenol ethoxylate having an average of 16 E0 units, 2.5 g of tristyrylphenol ethoxylate salt having an average of 16 BO units, 12.5 g of butoxypolyethylene—propylene glycol (block copolymer) 0.03 g of silicone antifoam emulsion and g of N,N-dibutyl—C16—Cl 8—carboxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained. ation example 11 To produce the proper invention with the active ingredient prothioconazole, the following are first mixed at room temperature with stirring: g of prothioconazole with 34.9 g of N,N—dimethyldecanamide and then with 20 g of castor oil polyglycol ether ester, 0.1 g of silicone antifoam emulsion and g of N,N—dibuty1—Cl6—Cl 8-carboxarnide.
After addition has ended, the mixture is d at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 12 To produce the proper invention with the active ingredient prothioconazole, the following are first mixed at room temperature with stirring: g of oconazole with 39.9 g of N,N—dimethyldecanamide and then with g of ethoxypropoxytristyrylphenol (block copolymer), g of rylphenol ethoxylate having an average of 16 E0 units and 0.1 g of silicone antifoam emulsion and g of butyl-Cl 6-Cl 8-carboxarnide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 13 To e the proper invention with the active ingredient bixafen, the following are first mixed at room temperature with stirring: g of bixafen with 45 g of N,N-dimethyldecanamide and then with g of aromatic hydrocarbon mixture, naphthalene-reduced, 10 g of lhexanol ene/ethylene glycol ether, g of castor oil ycol ether ester, g of ethoxypropoxytristyrylphenol (block copolymer) and g of N,N—dibutyl-C l 6-Cl 8-carboxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is ed.
Formulation example 14 To produce the proper invention with the active ingredient bixafen, the following are first mixed at room temperature with stirring: 10 g of bixafen with 40 g of N,N—dimethyldecanamide and then with g of aromatic hydrocarbon mixture, naphthalene—reduced, g of 2-ethylhexanol propylene/ethylene glycol ether, g of castor oil polyglycol ether ester, 5 g of ethoxypropoxytristyrylphenol (block copolymer) and -56.. g of N,N-dibutyl-C16-C1 8-carboxamide.
After addition has ended, the mixture is d at room temperature for a r 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 15 To produce the proper invention with the active ingredient bixafen, the ing are first mixed at room temperature with stirring: g of bixafen with 40 g of N,N—dimethyldecanamide and then with 5 g of aromatic hydrocarbon mixture, naphthalene—reduced, g of 2—ethy1hexanol propylene/ethylene glycol ether, g of castor oil polyglycol ether ester, g of ethoxypropoxytristyrylphenol (block copolymer) and g of butyl-C1 6—C1 8—carboxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained. ation example 16 To produce the proper invention with the active ingredient isopyrazam, the following are first mixed at room temperature with stirring: g of isopyrazam with 45 g ofN,N-dimethyldecanamide and then with g of aromatic hydrocarbon mixture, naphthalene—reduced, g of 2-ethy1hexanol propylene/ethylene glycol ether, g of castor oil polyglycol ether ester, g of ethoxypropoxytristyrylphenol (block copolymer) and g of N,N—dibutyl-Cl 6-Cl 8-carboxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 17 To produce the proper invention with the active ingredient isopyrazam, the following are first mixed at room temperature with stirring: 10 g of isopyrazam with 40 g of N,N—dimethyldecanamide and then with g of aromatic hydrocarbon mixture, naphthalene—reduced, g of 2-ethylhexanol propylene/ethylene glycol ether, g of castor oil polyglycol ether ester, 5 g of ethoxypropoxytristyrylphenol (block copolymer) and g of N,N—dibutyl—C16-C18—carb0xamide.
After addition has ended, the mixture is stirred at room ature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation e 18 To produce the proper invention with the active ingredient fluxapyroxad, the following are first mixed at room temperature with stirring: g of roxad with 45 g of N,N—dimethyldecanamide and then with 10 g of aromatic arbon mixture, naphthalene—reduced, _5g_ g of 2-ethylhexanol propylene/ethylene glycol ether, g of castor oil polyglycol ether ester, g of ethoxypropoxytristyrylphenol (block copolymer) and g of N,N—dibutyl-C l 6-Cl 8-carboxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 19 To e the proper invention with the active ingredient roxad, the following are first mixed at room temperature with stirring: g of fluxapyroxad with 40 g of N,N-dimethyldecanamide and then with g of aromatic hydrocarbon mixture, naphthalene-reduced, g of 2—ethylhexanol ene/ethylene glycol ether, 10 g of castor oil polyglycol ether ester, g of ethoxypropoxytristyrylphenol (block copolymer) and g of N,N—dibutyl-C l 6—Cl 8-carboxamide.
After addition has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.
Formulation example 20 To produce the proper invention as a x additive, the following are first mixed at room temperature with ng: 50 g of N,N—dibutyl—C l 6—Cl 8—carboxamide with 25 g of castor oil polyglycol ether ester and then with g of benzyl alcohol.
After on has ended, the mixture is stirred at room temperature for a further 2 hours. In this way, a homogeneous solution is ed.
Formulation example 21 To produce the proper invention with the active ingredient prothioconazole, the following are first mixed at room temperature with stirring: g of prothioconazole with 44.9 g of N,N—dimethyldecanamide and then with 15 g of 2-ethylhexanol propylene/ethylene glycol ether, g of castor oil polyglycol ether ester, g of ethoxypropoxytristyrylphenol (block copolymer), 0.1 g of silicone antifoam emulsion and g of N,N—dibutyl-C l 6-Cl 8—carboxamide.
After on has ended, the mixture is stirred at room temperature for a further 4 hours. In this way, a homogeneous solution is obtained.

Claims (7)

1. The use of carboxamides of the formula (I) R1-CO-NR 2R3 (I) 5 in which R1 is C16 -C18 -alkyl or C16 -C18 -alkenyl and R2 is C4-alkyl and R3 is C4-alkyl for promoting the penetration of prothioconazole into plants.
2. The use as claimed in claim 1, in which the carboxamides of the formula (I) are added to the oconazole as a tankmix additive.
3. An agrochemical ation in the form of an emulsion concentrate or dispersion in 15 oil, comprising o prothioconazole and o at least one carboxamide of the formula (I) R1-CO-NR 2R3 (I) in which 20 R1 is C16 -C18 -alkyl or C16 -C18 -alkenyl and R2 is C4-alkyl and R3 is C4-alkyl, and o at least one solvent and/or oil. 7329422_1 (GHMatters) P95895.NZ KARENM
4. The agrochemical formulation as claimed in claim 3, in which the content of the at least one carboxamide of the formula (I) in the agrochemical formulation is o 1 to 50% by weight.
5.5. The agrochemical formulation as claimed in claim 3, comprising o 15 - 35% by weight of prothioconazole and o 25 - 45% by weight of N,N-dimethyldecanamide and o 10 - 40% by weight of one or more emulsifiers and o 0.01 - 1.0% by weight of defoamer and 10 o 5 - 30% by weight of butyl-C16 -C18 -alkylcarboxamide and N,N-dibutyl- C16 -C18 -alkenylcarboxamide (in total).
6. A method for promoting the penetration of oconazole into a plant, comprising applying to the plant a carboxamide of the formula (I) 15 R1-CO-NR 2R3 (I) in which R1 is C16 -C18 -alkyl or C16 -C18 -alkenyl and R2 is C4-alkyl and R3 is yl.
7. The method as claimed in claim 6, in which the carboxamide of the formula (I) is added to the prothioconazole as a tankmix additive. 7680907_1 ters) P95895.NZ JENNYP
NZ620688A 2011-08-11 2012-08-10 Use and agrochemical composition of carboxylic acid dibutylamides NZ620688B2 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP11177196 2011-08-11
EP11177196.0 2011-08-11
US201161522798P 2011-08-12 2011-08-12
US61/522,798 2011-08-12
PCT/EP2012/065685 WO2013021045A1 (en) 2011-08-11 2012-08-10 Use and agrochemical composition of carboxylic acid dibutylamides

Publications (2)

Publication Number Publication Date
NZ620688A NZ620688A (en) 2016-05-27
NZ620688B2 true NZ620688B2 (en) 2016-08-30

Family

ID=

Similar Documents

Publication Publication Date Title
AU2012293612B2 (en) Use and agrochemical composition of carboxylic acid dibutylamides
US20200323206A1 (en) Use of n-substituted pyrrolidones to promote the penetration of agrochemical active agents
US20230172197A1 (en) High spreading ulv formulations for agrochemical compounds ii
US20240032532A1 (en) Agrochemical composition with improved drift, uptake and rainfastness properties
JP2023548489A (en) Low drift, rain resistant, high uptake and ULV tank mix adjuvant formulation
AU2012288947B2 (en) Etherified lactate esters, method for the production thereof and use thereof for enhancing the effect of plant protecting agents
US20240000074A1 (en) Low drift, rainfastness, high spreading, high uptake and ulv tank mix adjuvant formulation
NZ620688B2 (en) Use and agrochemical composition of carboxylic acid dibutylamides
AU2018348303A1 (en) Active ingredient compositions comprising N-alkenoyl-N-alkylglucamides and the use thereof
ES2665450T3 (en) Etherified tributyl phenol alkoxylates, procedure for their preparation and their use in phytoprotective agents
US20220411370A1 (en) Solvates Of Abscisic Acid And Liquid Compositions Containing Abscisic Acid
ES2715834T3 (en) Use and agrochemical composition of dibutylamides of carboxylic acids
EA045989B1 (en) COMPOSITIONS CONTAINING HERBICIDES BASED ON PYRIDINE CARBOXYLATE WITH HERBICIDES REPRESENTING PHOTOSYSTEM II INHIBITORS AND OPTIONALLY HPPD