EP2480071A1

EP2480071A1 - Pesticide preparations containing derivatives of pyrrolidone-4-carboxylic acid

Info

Publication number: EP2480071A1
Application number: EP10755112A
Authority: EP
Inventors: Andreas Wacker; Joachim Hess; Robert Milbradt; Franz-Xaver Scherl
Original assignee: Clariant Finance BVI Ltd
Current assignee: Clariant Finance BVI Ltd
Priority date: 2009-09-25
Filing date: 2010-09-18
Publication date: 2012-08-01
Also published as: WO2011035873A1; US20120264611A1; BR112012006569A2; CN102595883A; AU2010297634A1

Abstract

The invention relates to pesticide preparations that contain one or more pesticides and one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives and to the use of said pesticide preparations for controlling and/or combating weeds, fungal diseases, or insect infestation. The N-substituted 2-pyrrolidone-4-carboxylic acid derivatives act as adjuvants, emulsifiers, dispersants, and/or wetting agents in the pesticide preparations.

Description

description

PESTICIDE PREPARATIONS CONTAINING DERIVATIVES OF PYRROLIDONE-4-CARBOXYLIC ACID

The present invention relates to pesticide preparations which

Pyrrolidoncarbonsäurederivate and their use, in particular for the control and / or control of weeds, fungal diseases or

Insect infestation. Pesticides are commonly used in the form of a preparation to achieve better utilization of the active ingredient. Such preparations are also referred to as formulations and are generally present in solid or in liquid form. The formulations contain at least one but mostly several excipients that take on a variety of functions.

Examples of auxiliaries according to their function are solvents, emulsifiers,

Wetting agents, dispersants, crystallization inhibitors, defoamers,

Preservatives, Antioxidants, Thickeners, Antifreeze,

Humectants, colorants and adjuvants. Adjuvants are understood to mean auxiliaries which increase the biological effectiveness of the active ingredient without itself having a biological effect, for example by improving wetting, retention or uptake into the plant or the target organism.

Examples of liquid preparations ("formulation types") are aqueous

Solutions (SL), suspension concentrates (SC), suspo-emulsions (SE), emulsifiable concentrates (EC), oil dispersions (OD), emulsions in water (EW) or microemulsions (ME).

Examples of solid formulations ("formulation types") are water-soluble powders or granules (SP, SG) or water-dispersible powders or granules (WP, WDP, WG, WDG). Many effective adjuvants used in pesticide preparations are of concern from a toxicological or ecotoxicological point of view, such as

Nonylphenol ethoxylates (due to their endocrine effect), fatty amine ethoxylates (ecotoxic properties) or N-methylpyrrolidone (reprotoxic)

Properties).

A requirement for new excipients in pesticide preparations is therefore their toxicological and ecotoxicological safety. Another important basic requirement for excipients in

Pesticidal preparations are those that have no harmful effect on the crop (phytotoxicity). This is especially important for fungicides, insecticides and selective herbicides, but also for non-selective ones

Herbicides when used, for example, in genetically modified crops that are resistant to the corresponding nonselective herbicides.

It was therefore an object of the present invention to provide pesticide preparations comprising auxiliaries which are distinguished by good activity, toxicological and ecotoxicological safety and low phytotoxicity.

Surprisingly, it has now been found that this object is achieved by the use of N-substituted 2-pyrrolidone-4-carboxylic acid derivatives in pesticide preparations and in particular N-substituted

2-pyrrolidone-4-carboxylic acids, and their salts, esters and amides are useful as active adjuvants for pesticide preparations.

The present invention therefore relates to pesticide preparations containing

a) one or more pesticides and

b) one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives. In the context of the present invention, "N-substituted 2-pyrrolidone-4-carboxylic acid derivatives" include both the N-substituted 2-pyrrolidone-4-carboxylic acids and also other derivatives, in particular the salts, esters and amides of the N-substituted 2 Pyrrolidone-4-carboxylic acids understood.

No. 2,757,125 describes N-alkyl-4-carboxy-2-pyrrolidone and its salts, certain alkyl esters and alkylamides which are used as antibacterial components in cosmetic formulations or cleansing compositions. US 2,977,309 describes a lubricating oil which comprises a reaction product

Itaconic acid and branched primary aliphatic amines with 10-24 C atoms, contains.

No. 3,224,975 describes lubricant compositions comprising N-alkyl-4-carboxy-2-pyrrolidone in which the alkyl radical comprises 8-25 C atoms.

GB 1323061 discloses certain N-substituted-4-carboxy-2-pyrrolidones and their use in functional fluids such as

Hydraulic fluids.

EP 2 022 781 describes dimeric N-alkyl-4-carboxy-2-pyrrolidone derivatives which are linked via a bridge to the carboxy group and their use as gas hydrate inhibitors. EP 2 028 247 describes the use of N-alkyl-2-pyrrolidone-4-carboxylic acid esters as gas hydrate inhibitors.

WO 2009/086872 and WO 2009/086873 describe the use of N-alkyl-2-pyrrolidone-4-carboxylic acid ammonium salts as corrosion inhibitors.

The use of Pyrrolidoncarbonsäurederivaten as auxiliaries in

However, pesticide formulations will not be described. In the context of the present invention, pesticides are herbicides, fungicides, insecticides, acaricides, bactericides, molluscides, nematicides and

Rodenticides and phytohormones understood. Controlling phytohormones

physiological reactions, such as growth, stinging rhythm, cell division and

Seed maturation. An overview of the most relevant pesticides can be found

for example, in "The Pesticide Manual" of the British Crop Protection Council, 14th Edition 2006, Editor: C D S Tomlin.

The one or more pesticides of component a) of

Pesticidal preparations according to the invention are preferably selected from the group consisting of herbicides, insecticides and fungicides.

Preferred fungicides are aliphatic nitrogen fungicides, amide fungicides such as acylamino acid fungicides or anilide fungicides or benzamide fungicides or strobilurin fungicides, aromatic fungicides, benzimidazole fungicides,

Benzothiazole fungicides, carbamate fungicides, conazole fungicides such as imidazoles or triazoles, dicarboximide fungicides, dithiocarbamate fungicides, imidazole fungicides, morpholide fungicides, oxazole fungicides, pyrazole fungicides, pyridine fungicides,

Pyrimidine fungicides, pyrrole fungicides, quinone fungicides.

Preferred herbicides are amide herbicides, anilide herbicides, aromatic

Acid herbicides such as benzoic acid herbicides or picolinic acid herbicides,

Benzoylcyclohexanedione herbicides, benzofuranyl alkyl sulfonate herbicides,

Benzothiazole herbicides, carbamate herbicides, carbanilatherbicide,

Cyclohexenoxime herbicides, cyclopropylisoxazole herbicides, dicarboximide herbicides, dinitroaniline herbicides, dinitrophenol herbicides, diphenyl ether herbicides,

Dithiocarbamate herbicides, imidazolinone herbicides, nitrile herbicides,

Organophosphorus herbicides, oxadiazolone herbicides, oxazole herbicides,

Phenoxy herbicides such as phenoxyacetic acid herbicides or

Phenoxybutanoic acid herbicides or phenoxypropionic acid herbicides or

Aryloxyphenoxypropiosäureherbizide, Pyrazolherbizide like

Benzoylpyrazole herbicides or phenylpyrazole herbicides, pyridazinone herbicides, pyridine herbicides, thiocarbamate herbicides, triazine herbicides, triazinone herbicides, Triazole herbicides, triazolone herbicides, triazolopyrimidine herbicides, uracil herbicides, urea herbicides such as phenylurea herbicides or sulfonylurea herbicides.

Preferred insecticides are carbamate insecticides, such as

Benzofuranylmethylcarbamate insecticides or dimethylcarbamate insecticides or oximecarbamate insecticides or phenylmethylcarbamate insecticides,

Diamidine insecticides, insect growth regulators, macrocyclic

Lactone insecticides such as avermectin insecticides or milbemycin insecticides or spinosyn insecticides, nereistoxin analogous insecticides, nicotinoid insecticides such as nitroguanidine nicotinoid insecticides or pyridylmethylamino nicotinoid insecticides, organophosphorus insecticides such as organophosphate insecticides or

Organothiophosphate insecticides or phosphonate insecticides or

Phosphoramidothioate insecticides, oxadiazine insecticides, pyrazoline insecticides, pyrethroid insecticides such as pyrethroid ester insecticides or pyrethroid ether insecticides or pyrethroid oxime insecticides, tetramic acid insecticides,

Tetrahydrofurandione insecticides, thiazoline insecticides.

The one or more pesticides of component a) of the pesticide preparations according to the invention are particularly preferably selected from the group consisting of aryloxyphenoxypropionic acid herbicides,

Benzoylcyclohexanedione herbicides, triazolopyrimidine herbicides, strobilurin fungicides, triazole fungicides, nicotinoid insecticides and pyrethroid insecticides.

More preferably, the one or more pesticides of component a) of the pesticide formulations according to the invention are selected from the group consisting of malathion, cypermethrin, glyphosate in the acid form and glyphosate in the form of salts. Among them, preferred are glyphosate in the acid form and in the form of salts. Among the salts of glyphosate, glyphosate isopropylammonium is preferred.

An overview of the pesticides and their classification in the corresponding pesticide classes can be found for example in "The Pesticide Manual" of the British Crop Protection Council, 14th Edition 2006, Editor: CDS Tomlin. The biological activity of a pesticide can be determined by the plant growth or the damage to the plants by the action of the active ingredient on the leaf as a function of the time of action and the active ingredient concentration.

The one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives of component b) of the pesticidal preparations according to the invention are preferably the N-substituted, preferably N-alkyl or N-alkenyl-substituted, 2 Pyrrolidone-4-carboxylic acids and their salts, esters and amides.

Most preferably, the one or more N-substituted ones

2-pyrrolidone-4-carboxylic acid derivatives of component b) of the pesticide preparations according to the invention selected from the compounds of the formula (Z)

wherein

R1 Cs to C ₃₀ alkyl or C ₈ - to C _ß o-alkenyl,

Y is OM, -O- [AO] _{n is} -X or NR2R3,

M is hydrogen, alkali or alkaline earth metal, ammonium NH ₄ ⁺ or substituted ammonium, wherein the substituted ammonium is preferably selected from mono-, di- and trisubstituted

Ammonium and the substituents on the N atom of the substituted

Ammonium are in turn selected from alkyl groups having 1 to 4 carbon atoms and CH ₂ CH ₂ OH,

AC ₂ - to C ₄ -alkylene or C ₆ H ₅ - (CH-CH ₂ ),

n is a number from 0 to 100

X is C to C ₂ o-alkyl, benzyl or a substituted aryl radical, wherein the substituted aryl radical is preferably selected from phenyl, the is substituted with 1 to 3 substituents, and these substituents are in turn selected from alkyl groups having 1 to 4 carbon atoms and styryl and in the event that n is not 0, X can also be hydrogen,

R ₂ and R 3 independently of one another are hydrogen, C ₁ - to C ₂ o-alkyl or

(C ₂ H ₄ 0) _P H are and

p is a number from 1 to 20.

In a particularly preferred embodiment of the invention, the one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives of component b) of the pesticidal formulations according to the invention are selected from the compounds of the formula (1)

C ₈ to C ₃₀ alkyl or C ₈ to C ₃ o alkenyl and

Is hydrogen, alkali or alkaline earth metal, ammonium NH ₄ ⁺ or substituted ammonium, wherein the substituted ammonium is preferably selected from mono-, di- and trisubstituted ammonium and the substituents on the N-atom of the substituted ammonium are in turn selected from alkyl groups having 1 to 4 carbon atoms and CH ₂ CH ₂ OH. In a further particularly preferred embodiment of the invention, the one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives of component b) of the pesticide formulations according to the invention are selected from the compounds of the formula (2)

C _{8 is} - to C 30 -alkyl or C 30 - to C 30 -alkenyl,

C ₂ - to C ₄ -alkylene or C ₆ H ₅ - (CH-CH ₂ ),

a number from 0 to _. 100 is and

C is C 2 to C 20 alkyl, benzyl or a substituted aryl radical, wherein the substituted aryl radical is preferably selected from phenyl substituted with 1 to 3 substituents, and these substituents are in turn selected from alkyl groups having 1 to 4 carbon atoms and styryl and in the If n is not 0, then X can also be hydrogen.

In a further particularly preferred embodiment of the invention, the one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives of component b) of the pesticide formulations according to the invention are selected from the compounds of the formula (3)

wherein

R 1 is C ₈ - to C ₃₀ -alkyl or C ₈ - to C ₃₀ -alkenyl,

R2 and R3 are independently hydrogen, C to C ₂ o-alkyl or

(C ₂ H ₄ 0) _p H are and

p is a number from 1 to 20.

In the formulas (Z) and (1) to (3), R1 is preferably a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms,

in particular for a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms. R1 particularly preferably represents a linear or branched octyl radical, a cocoyl radical or an oleyl radical.

In formulas (Z) and (1), M is preferably hydrogen, Na, K, Ca,

Ammonium, iso-propylammonium, N, N-diethyl (2-hydroxyethyl) ammonium, mono-, di- or triethanolammonium. In the formulas (Z) and (2), A is preferably ethylene or propylene and particularly preferably ethylene. X is preferably hydrogen (when n is not zero), C ₄ -C ₄ -alkyl and particularly preferably methyl, n is preferably from 1 to 40 and particularly preferably from 5 to 25. If X in the formulas (Z) and ( 2) represents a substituted aryl radical, this is preferably 2,4,6-tri-secondary-butylphenyl or 2,4,6-tristyrylphenyl.

In the formulas (Z) and (3), R 2 and R 3 are preferably hydrogen,

C to C ₄ alkyl or (C ₂ H ₄ 0) _p H. Particularly preferred are R2 and R3 is methyl or -CH ₂ -CH ₂ -OH.

Because of the many possibilities, the chemical structure of the N-substituted contained in the pesticide formulations according to the invention

2-pyrrolidone-4-carboxylic acid derivatives of component b) to vary and thus adapt the physical and physico-chemical properties of the molecules, the N-substituted 2-pyrrolidone-4-carboxylic acid derivatives in the inventive preparations can perform a variety of tasks ,

The N-substituted 2-pyrrolidone-4-carboxylic acid derivatives of component b) of the pesticide preparations according to the invention and in particular the compounds of the formulas (Z) and (1) to (3) are preferably suitable as adjuvants,

Emulsifiers, dispersants or wetting agents. Another object of the present invention is therefore the use of one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives and preferably one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives selected from the formulas (Z) and ( 1) to (3) as adjuvant,

preferably in a pesticide preparation according to the invention.

The present invention also provides the use of one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives and preferably one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives selected from the formulas (Z) and ( 1) to (3) as an emulsifier, preferably in a pesticide preparation according to the invention.

Particularly preferred emulsifiers are compounds of the formula (1) in which M is not hydrogen (anionic emulsifiers) or compounds of the formula (2) in which n is 5 (nonionic emulsifiers).

Compounds of formula (2) wherein X is other than hydrogen and n is 5 are particularly preferred as emulsifiers for pesticide formulations containing an active ingredient which is sensitive to water or to OH groups, such as sulfonylureas (SUs).

The present invention also provides the use of one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives and preferably one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives selected from the formulas (Z) and ( 1) to (3) as a wetting agent, preferably in a pesticide preparation according to the invention.

Compounds of the formula (1) in which M represents Na, K, ammonium, NH ₄ ⁺ or substituted ammonium, are particularly suitable as wetting agents.

Another object of the present invention is the use of one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives and preferably one or more N-substituted 2-pyrrolidone-4-carboxylic acid Derivatives selected from the formulas (Z) and (1) to (3) as a dispersant, preferably in a pesticide preparation according to the invention.

Compounds of the formula (1) in which M is Na, K, ammonium, NH ₄ ⁺ or substituted ammonium, are particularly suitable as dispersants.

In a preferred embodiment of the invention, the

Pesticidal preparations according to the invention as liquid preparations

("Formulation types") selected from aqueous solutions (SL),

Suspension concentrates (SC), suspo-emulsions (SE), emulsifiable

Concentrates (EC), oil dispersions (OD), emulsions in water (EW) or microemulsions (ME) are present.

Compounds of the formula (1) in which M is not hydrogen or

Compounds of the formula (2) in which n> 10 are particularly preferred for use in water-containing compounds because of their solubility

Formulations like SLs, SCs, EWs, SEs and MEs.

Compounds of formula (1) in which M is hydrogen or

Compounds of the formula (2) in which n <9 or compounds of the formula (3) have a low solubility in water and are therefore particularly preferably used as auxiliaries for solvent- or oil-containing preparations such as ECs, EWs, SEs, MEs and ODs. In a further preferred embodiment of the invention are the

Pesticide preparations according to the invention as solid preparations

("Formulation types") selected from water-soluble powders or granules (SP, SG) or water-dispersible powders or granules before (WP, WDP, WG, WDG).

Compounds of the formulas (Z) and (1) to (3) which are distinguished by a melting point of preferably> 30 ° C. and particularly preferably> 40 ° C., are particularly preferably suitable for use in solid preparations. The present invention also provides the use of one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives and preferably one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives selected from the formulas (Z) and ( 1) to (3) for the preparation of pesticide preparations according to the invention.

Depending on the type of formulation, the preparation of the pesticide formulations according to the invention is possible in various ways and is well known to the person skilled in the art.

The N-substituted 2-pyrrolidone-4-carboxylic acids of component b) of the pesticide formulations according to the invention are obtained by reacting

Itaconic acid with primary amines and can be prepared as described in EP 0 069 512, US 3,224,975 and US 4,127,493.

The preparation of the corresponding salts is by reaction of

N-substituted 2-pyrrolidone-4-carboxylic acids with a base possible. Suitable bases are preferably NaOH, Ca (OH) ₂ , CaC0 ₃ , KOH and amines such as

Ammonia, iso-propylamine, mono-, di- or triethanolamine.

The preparation of the corresponding esters can, for example, by addition of alkylene oxides to the N-substituted 2-pyrrolidone-4-carboxylic acids or by condensation of N-substituted 2-pyrrolidone-4-carboxylic acids with

optionally substituted polyglycol ethers. It may, for example, by the skilled artisan esterifications of N-substituted

2-pyrrolidone-4-carboxylic acids with alkyl alcohols, benzyl alcohol or other aromatic alcohols. The corresponding amides are by condensation of the N-substituted

2-pyrrolidone-4-carboxylic acids accessible with amines.

The pesticide preparations of the invention contain one or the a plurality of N-substituted 2-pyrrolidone-4-carboxylic acid derivatives of component b), preferably in amounts of from 0.1 to 50% by weight, more preferably from 0.5 to 30% by weight and especially preferably from 1 to 20 wt .-%. These quantities are based on the entire pesticide preparation according to the invention.

The pesticidal preparations according to the invention contain the one or more pesticides of component a), preferably in amounts of from 1 to 90% by weight, more preferably from 2 to 80% by weight and especially preferably from 4 to 70% by weight. These quantities are based on the entire pesticide preparation according to the invention.

The pesticide preparations according to the invention are particularly suitable for controlling and / or controlling weeds, fungal diseases or insect infestation.

Another object of the present invention is therefore also the use of a pesticide preparation according to the invention for the control and / or control of weeds, fungal diseases or insect infestation.

The pesticide preparations according to the invention are preferably applied to the fields in the form of spray liquors. In this case, a spray mixture is prepared by dilution of the concentrate formulation with a defined amount of water.

In a preferred embodiment of the invention, the pesticide preparation according to the invention is present as a spray mixture and contains from 0.001 to 10% by weight, preferably from 0.02 to 3% by weight and particularly preferably from 0.025 to

2 wt .-% pesticide of component a) and from 0.001 to 3 wt .-%, preferably from 0.005 to 1 wt .-% and particularly preferably from 0.01 to 0.5 wt .-% of N-substituted 2 Pyrrolidone-4-carboxylic acid derivative of component b). These quantities are based on the entire spray mixture. The weight ratio of the one or more N-substituted

2-pyrrolidone-4-carboxylic acid derivatives of component b) to the one or more pesticides of component a) in the spray mixture is preferably from 1: 100 to 10: 1 and more preferably from 1:20 to 4: 1.

Pesticide amounts are preferably applied in the range of 0.005 to 5 kg per hectare. The proportion of N-substituted 2-pyrrolidone-4-carboxylic acid derivatives is in the range of preferably 0.002 to about 2.0 kg / ha. The volume of the spray mixture used for the application is preferably in the range from 50 to 1000 l / ha.

In this case, the one or more pesticides and the one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives may also be present in the form of a so-called "tank-mix" preparation

Preparation, both the one or more pesticides and the one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives are initially present separately from each other. Both preparations are before

Application, usually shortly before, mixed together to form a preparation according to the invention.

In the "tank-mix" process, one or more pesticides are present before mixing as a formulation in water and / or in a solvent or as a solid formulation. In the "tank-mix" process, the one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives are present before mixing in solution in water or in a solvent or a water-solvent mixture.

The preparations according to the invention may contain thickeners, solvents, dispersants, emulsifiers, preservatives, adjuvants, binders, thinners, disintegrants, wetting agents, penetrants, cold stabilizers, colorants, defoamers and antioxidants. As thickening agents, all commonly used for this purpose in agrochemical formulations substances such as xanthan gum and / or cellulose, for example carboxy, methyl, ethyl or propyl cellulose or (optionally modified) bentonites in the amounts by weight of 0.01 to 5%, based on the finished agent, are used. Suitable solvents are all substances customarily usable for this purpose in agrochemical formulations, such as, for example, aromatic and aliphatic hydrocarbons, N-methylpyrrolidone, cyclohexanone, butyrolactone,

Acetophenone, lactic acid esters such as ethyl hexyllactate, esters of carbonic acid such as propylene carbonate, fatty acid amides such as decanoic acid, esters of phosphorous acid or phosphoric acid such as Ethylhexylphosphonsäure- (ethylhexyl) ester or tris (ethylhexyl) phosphate, glycols, polyethylene glycols, propylene glycol, natural and mineral oils and Esters of fatty acids. Suitable dispersants and emulsifiers are all substances customarily usable for this purpose in agrochemical formulations, such as nonionic, amphoteric, cationic and anionic (polymeric) surfactants. When

Preservatives can all usually be used for this purpose

substances which can be used in agrochemical formulations, such as organic acids and their esters, for example ascorbic acid, ascorbic palmitate, sorbate, benzoic acid, methyl and propyl 4-hydroxybenzoate, propionates, phenol, for example 2-phenylphenate, 1,2-benzisothiazolin-3-one, formaldehyde, Sulfurous acid and its salts are used. As an adjuvant all commonly used for this purpose in agrochemical formulations substances such as optionally crosslinked polyglycerol esters, alcohol alkoxylates such. As alcohol ethoxylates, alkyl polysaccharides, fatty amine ethoxylates, esters of phosphorous acid or phosphoric acid such as Ethylhexylphosphonsäure- bis (ethylhexyl) ester or tris (ethylhexyl) phosphate, sorbitan and

Sorbitolethoxylatderivate and derivatives of alk (en) ylsuccinic be used. Suitable penetration enhancers are all substances that are commonly used to prevent the penetration of pesticides into plants or in plants

To improve target organisms. Penetration enhancers can be defined, for example, by adding them from the aqueous spray mixture and / or from a spray coating on the plant surface into the cuticle of the plant and thereby increase the tissue mobility (mobility) of active ingredients in the cuticle. The method described in the literature can be used to determine this property (Baur et al., 1997, Pesticide Science 51, 131-152).

For solid formulations, all binders customarily used for this purpose in agrochemical formulations are suitable, such as

Polyvinyl pyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, sugar,

For example, sucrose, sorbitol or starch. Suitable thinners, absorbers or carriers are all substances customarily usable for this purpose in agrochemical formulations, such as carbon black, tallow, kaolin, aluminum, calcium or magnesium stearate, sodium tripolyphosphate,

Sodium tetraborate, sodium sulphate, silicates and sodium benzoate. As disintegrants, it is possible to use all substances customarily usable for this purpose in agrochemical formulations, such as cellulose, for example carboxymethylcellulose, polyvinylpyrrolidone, sodium or potassium acetate, carbonates, bicarbonates, sesquicarbonates, ammonium sulphate or potassium hydrogenphosphate.

As wetting agents, it is possible to use all substances customarily used for this purpose in agrochemical formulations, such as alcohol ethoxylates,

Alcohol alkoxylates, EO / PO block copolymers (EO: ethylene oxide unit; PO:

Propylene glycol unit) or optionally ethoxylated alkylsulfonic acids. As cold stabilizers, it is possible to use all substances which can usually be used for this purpose in agrochemical formulations.

Examples include urea, glycerol and propylene glycol. Suitable colorants are all usually in agrochemical for this purpose

Formulations usable substances such as water or oil-soluble dyes, as well as organic or inorganic pigments. Suitable defoamers are all substances customarily usable for this purpose in agrochemical formulations, such as fatty acid alkyl ester alkoxylates; Organopolysiloxanes such

Polydimethylsiloxanes and their mixtures with microfine, optionally signed silica; Perfluoroalkyl phosphonates and phosphinates; paraffins; Waxes and microcrystalline waxes and their mixtures with signed Silica. Also advantageous are mixtures of various foam inhibitors, for example those of silicone oil, paraffin oil and / or waxes. Suitable antioxidants are all substances customarily usable for this purpose in agrochemical formulations, for example BHT (2,6-di-tert-butyl-4-methylphenol).

The preparations according to the invention may additionally contain one or more agrochemical salts, preferably potassium or ammonium salts. Examples:

In the following, the invention will be clarified by way of examples, which are by no means to be regarded as limiting. In the examples, percentages% by weight (% by weight) unless explicitly stated otherwise.

General procedure for the preparation of the N-substituted 2-pyrrolidone-4-carboxylic acids:

In a 2-liter stirred apparatus with reflux condenser and change-over, primary amine is initially charged and heated to 100 ° C. under nitrogen. At this temperature, the corresponding amount of itaconic acid is added in five equal portions with slow stirring. The mixture reacts exothermically, after each serving is stirred for 30 minutes. Thereafter, the reaction mixture is heated until reflux is reached (about 120 ° C) and held under reflux for 6 hours. Subsequently, the changeover thrust is changed over to a decrease in the water of reaction. The temperature is gradually increased within 4 hours to 180 ° C and the reaction water collected in the template.

Example 1 :

According to the above instructions, 773.1 g of primary oleylamine (M = 264.7 g / mol, Genamin OL 100D from Clariant) and 400.0 g of itaconic acid (M = 130.1 g / mol). This 50.2 g of water are discharged. The product obtained has an acid number of 142.3 mg KOH / g

(Theory: 148.9 mg KOH / g). The water content is <0.05%. This gives 1072.7 g of N-oleyl-2-pyrrolidone-4-carboxylic acid (compound 1).

Example 2:

According to the above rule, 683.5 g of primary coconut fatty amine are added

(M = 195.5 g / mol, Genamin ^® CC 100D from Clariant), and 478.8 g

Itaconic acid (M = 130.1 g / mol) reacted. This 66.9 g of water are discharged. The product obtained has an acid number of 173.0 mg KOH / g (theory: 182.4 mg KOH / g). The water content is <0.05%. This gives 1050.1 g of N-cocoyl-2-pyrrolidone-4-carboxylic acid (compound 2). Procedure for the preparation of N-substituted 2-pyrrolidone-4-carboxylic esters:

In a 1 liter stirrer with reflux condenser, changeover thrust and

Nitrogen transfer, the N-substituted 2-pyrrolidone-4-carboxylic acid and polyethylene glycol monomethyl ether (Polyglykol M types from Clariant) in a molar ratio of 1: 1 and heated to 200 ° C with stirring. At this temperature, stirring is continued for a further 4 hours and water of reaction is distilled off. Then a gentle water jet vacuum (22 mbar) is applied and heated to 220 ° C. When the desired residual acid number has been reached, the vacuum is released with nitrogen and allowed to cool. The individual experiments are summarized in Table 1. Table 1: Reactions of N-substituted 2-pyrrolidone-4-carboxylic acids with polyethylene glycol monomethyl ethers

Example Pyrrolidone Use Polyglycol M Molecular Weight Use Residual Acid Number Hydroxyl Number Yield Appearance Carboxylic Acid Amount Polyglycol M Amount Final Product End Product End Product

[g] [g / mol] [g] [mg KOH / g] [mg KOH / g] [g] at RT

Example 3

Compound 1 420.0 250 283-295 303.2 2.1 not determined 682.7 liquid (compound 3)

Example 4

Compound 1 380.0 350 330-370 329.0 2.3 not determined 664.2 liquid (compound 4)

Example 5

Compound 1 387.5 500 470-530 312.5 1, 7 4.2 665.0 liquid (compound 5)

Example 6

Compound 1 238.7 750 720-780 462.3 0.6 4.7 676.5 pasty (compound 6)

Example 7

Compound 1 193.8 1000 970-1060 506.2 0.3 not determined 677.1 solid (compound 7)

Example 8

Compound 2 279.2 500 470-530 420.7 1, 3 4.9 643.3 liquid (compound 8)

Example 9

Compound 2 208.7 750 720-780 491, 2 0.7 6.0 653.7 pasty (compound 9)

Example 10

Compound 2 167.7 1000 970-1060 532.4 1, 1 5.8 663.4 pasty (compound 10)

Procedure for the preparation of salts of N-substituted 2-pyrrolidone-4-carboxylic acids:

Example 11:

379 g of N-oleyl-2-pyrrolidone-4-carboxylic acid (compound 1) is mixed with 61 g

Monoethanolamine implemented. There are obtained 440 g of N-oleyl-2-pyrrolidone-4-carboxylic acid monoethanolammonium salt (compound 11) with acid number = 125 mg KOH / g and basic nitrogen N = 3.3%. Example 12:

311 g of N-cocoyl-2-pyrrolidone-4-carboxylic acid (compound 2) is mixed with 117 g

Ν, Ν-Diethylaminoethanol reacted. There are obtained 428 g of N-cocoyl-2-pyrrolidone-4-carboxylic acid N, N-diethyl (2-hydroxyethyl) ammonium salt (compound 12) with acid number = 125 mg KOH / g and basic nitrogen N = 3.3%.

Example 13: Reaction of the N-substituted 2-pyrrolidone-4-carboxylic acids with

dimethylamine:

2 mol of the N-substituted 2-pyrrolidone-4-carboxylic acid are initially introduced into a 1 liter stirred apparatus with reflux condenser and alternating projection and gaseous dimethylamine is introduced with heating to 180 ° C. and the reaction water formed is distilled off continuously. Once the residual acid number on

<5 mg KOH / g has fallen (after about 20 hours), the initiation of the

Dimethylamine stopped and the excess dimethylamine through

Nitrogen discharge expelled under vacuum. Subsequently, the

Reaction mixture cooled under nitrogen transfer.

Example 14: Determination of phytotoxicity

The determination of phytotoxicity is made on tomato plants (cv.Astona F1), a species known to be sensitive to phytotoxic substances absorbed via the leaf surface ("Phytotoxicity of different classes of adjuvants", H. de Ruiter, et al., Proceedings Fifth International

Symposium on Adjuvants for Agrochemicals, 1998, Ed. P. McMullan,

pp. 204-209). plants

Tomato plants (cv. Astona F1) are housed in a greenhouse

14 hours of light irradiation at a temperature of 18/12 (± 0.5) ° C

(Day / night) and a relative humidity of 70/80 (± 5)% (day / night). 12 days after germination, the seedlings are placed in 11 cm diameter plastic pots (one plant per pot) filled with a mixture of sand and soil (Soil no. 12, Colent bv, Lent, The Netherlands) in the volume ratio of sand: soil = 1: 2, exposed.

The pots are placed on an underwater watering mat that has been moistened daily with a medium nutrient solution.

application

The plants are treated 28 days after seeding at the 4-leaf stage at a size of 15 - 7 cm per plant. The content of excipient in the spray solution is 0.5% (v / v or volume%).

The spray solutions are applied to the plants with an air pressure operated laboratory sprayer, so that an application amount of 200 l / ha results.

The treated plants are visually assessed after 2 and 8 days (DAT: days after treatment) and evaluated on the basis of a qualitative classification (1 to 5). 1 = no discoloration or necrosis of the leaves until 5 = complete necrosis of the treated leaf surface. In addition, the plant mass above the ground is determined after 8 days (Fresh Weight). In each case, the average values are calculated based on the number of treated plants. As reference substance is a

Fatty alcohol alkoxylate used, as it is used in pesticide formulations. The results are shown in Table 2. Table 2: Results of treatment of the plant cv. Astona F1 with

N-substituted 2-pyrrolidone-4-carboxylic acid derivatives and

Fatty alcohol alkoxylate, but without pesticide

Compounds 1 and 5 show at most minimal signs of

phytotoxic reaction of the tomato plants, while the reference substance causes significant reactions. The plant mass produced is not reduced when using Compounds 1 and 5 compared to the untreated plant, while the plants treated with the reference substance are weaker, i. H. have a lower plant mass.

Example 15: Pesticidal Preparations, Increasing the Biological Activity of

glyphosate

Spray solutions

Compound 1 and compound 5 are tested for their suitability as adjuvants for the herbicide glyphosate in the so-called tank-mix method. In this case, 50% solutions are used. In the case of compound 1 is in addition

Triethanolamine added to bring the acid into solution.

By mixing these tank-mix solutions with a commercially available aqueous solution of glyphosate isopropylammonium (with 62% by weight of active ingredient glyphosate IPA salt, IPA: isopropylammonium) and further addition of water, a preparation according to the invention is formed. The ratio of glyphosate (based on the acid equivalent) to adjuvant corresponds to that which is also to be found quite thoroughly in commercially available glyphosate formulations.

For a better check of the adjuvant effects glyphosate is underdosed, the application amount is 135.2 g a.e./ha glyphosate IPA salt (corresponding to 4.0 mmol or 0.68 g a.e./l at a liquid volume of 200 l / ha). The abbreviation "a.e." means "acid equivalent".

The spray solutions contain the following concentrations of adjuvant: 0.0141% (v / v).

plants

Wild oats (Avena Fatua, AVEFA) are exposed to light irradiation in a greenhouse under 14 hours light at a temperature of 18/12 (± 0.5) ° C (day / night) and a relative humidity of 70/80 (± 5)% (day / Night). The light is supplied via high-pressure mercury lamps and fluorescent tubes, so that an output of 70 W / m ² (PAR, photosynthetically active radiation (400-700 nm)) results at the leaf level. The plants are in plastic pots with 11 cm diameter, filled with a mixture of sand and soil (Soil no. 12, Colent bv, Lent, Netherlands) in volume ratio

Sand: Soil = 1: 2, bred.

The pots are placed on an underwater watering mat, which is moistened daily with a medium nutrient solution. After emergence, the AVEFA sprouts are thinned to six plants per pot for efficacy testing.

herbicide application

Greenhouse experiments are carried out with the spray solutions. The influence of the adjuvants on the efficacy of glyphosate is tested.

The spray solutions are applied to the plants with an air pressure operated laboratory sprayer, so that an application amount of 200 l / ha results. Wild oat (AVEFA) is treated after reaching the 2-3 leaf stage. Results

After 21 days, the herbicidal efficacy is assessed. For this, the mass of the remaining above-ground parts of the plant (so-called fresh weight (FW) in grams) is determined. This is shown in Table 3 together with the calculated relative residual to the untreated plant (in wt%).

Table 3: Influence of the adjuvant on the efficacy of glyphosate

(AVEFA)

Example 16: Pesticide Preparations, EC Formulations

Compound 3 and compound 5 are tested for their suitability as emulsifier in EC emulsions (emulsifiable concentrates). For this purpose, pesticide preparations according to the invention are prepared with the active ingredients malathion and cypermethrin (Table 4). Table 4: Malathion and cypermethrin EC formulations

Phenylsulfonate CA (Clariant): calcium dodecylbenzenesulfonate in iso-butanol

(70%)

Emuslogen ^® 3510 (Clariant): EO / PO block copolymer

Emuisogen ^® EL 360 (Clariant): Castor oil ethoxylate

Xylene: organic solvent

Solvesso ^® 150 (Exxon): organic solvent

All three preparations give shelf-stable EC formulations. To assess the quality of the formulations, 5% aqueous emulsions are prepared in soft (20 ppm) and hard (342 ppm) CIPAC standard water and evaluated at 30 ° C for a period of 2, 4, and 24 hours. All emulsions are stable over this period of time, no phase separation is observed.

Claims

claims

1. Pesticide preparation containing

a) one or more pesticides and

b) one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives.

2. A pesticide preparation according to claim 1, characterized in that the one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives of component b) are selected from the compounds of formula (Z)

wherein

R 1 is C ₈ - to C ₃ o-alkyl or C ₈ - to C ₃₀ -alkenyl,

Y is OM, -O- [AO] _{n is} -X or NR2R3,

M is hydrogen, alkali or alkaline earth metal, ammonium NH ₄ ⁺ or substituted ammonium, wherein the substituted ammonium is preferably selected from mono-, di- and trisubstituted ammonium and the substituents on the N-atom of the substituted ammonium are in turn selected from alkyl groups with 1 to

4 carbon atoms and CH ₂ CH ₂ OH,

AC ₂ - to C ₄ -alkylene or C ₆ H5- (CH-CH ₂ ),

n is a number from 0 to 100,

X is C ₂₀ alkyl, benzyl or a substituted aryl radical, wherein the substituted aryl radical is preferably selected from phenyl which is substituted with 1 to 3 substituents, and these substituents are in turn selected from alkyl groups having 1 to 4 carbon atoms and styryl and in in the case where n is not 0, it may also be hydrogen,

R2 and R3 are independently hydrogen, C to C ₂ o-alkyl or

(C ₂ H ₄ 0) _p H are and P is a number from 1 to 20.

3. Pesticide preparation according to claim 1 or 2, characterized in that the one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives of component b) are selected from the compounds of formula (1)

R 1 is C ₈ - to C ₃₀ -alkyl or C ₈ - to C ₃ o-alkenyl and

M is hydrogen, alkali or alkaline earth metal, ammonium NH ₄ ⁺ or substituted ammonium, wherein the substituted ammonium is preferably selected from mono-, di- and trisubstituted ammonium and the substituents on the N-atom of the substituted ammonium are in turn selected from alkyl groups with 1 to 4 carbon atoms and CH ₂ CH ₂ OH.

4. A pesticide preparation according to claim 1 or 2, characterized in that the one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives of component b) are selected from the compounds of formula (2)

wherein

R 1 is C ₈ - to C _ß o-alkyl or C ₈ - to C ₃₀ alkenyl,

AC ₂ - to C ₄ -alkylene or C ₆ H ₅ - (CH-CH ₂ ), n is a number from 0 to 100 and

X is C ₂ to C ₂ o-alkyl, benzyl or a substituted aryl radical, wherein the substituted aryl radical is preferably selected from phenyl which is substituted with 1 to 3 substituents, and these substituents are in turn selected from alkyl groups having 1 to 4

Carbon atoms and styryl and in the event that n is not 0, may also mean hydrogen.

5. A pesticide preparation according to claim 1 or 2, characterized in that the one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives of component b) are selected from the compounds of

Formula (3)

wherein

R 1 is C ₈ - to C ₃₀ -alkyl or C ₈ - to C ₃ o-alkenyl,

R2 and R3 independently of one another are hydrogen, C to C20-alkyl or

(C ₂ H ₄ 0) _p H are and

p is a number from 1 to 20.

6. Use of one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives as adjuvant, preferably in a pesticide preparation according to one or more of claims 1 to 5.

7. Use of one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives as emulsifier, preferably in a pesticide preparation according to one or more of claims 1 to 5.

8. Use of one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives as wetting agents, preferably in a pesticide preparation according to one or more of claims 1 to 5.

9. Use of one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives as dispersants, preferably in one

A pesticide preparation according to one or more of claims 1 to 5.

10. Use of one or more N-substituted 2-pyrrolidone-4-carboxylic acid derivatives for the preparation of a pesticide preparation according to one or more of claims 1 to 5.

11. Use of a pesticide preparation according to one or more of claims 1 to 5 for the control and / or control of weeds,

Fungal diseases or insect infestation.