NZ623848B2 - Agricultural formulations with amides and acyl morpholines - Google Patents

Abstract

The disclosure relates to a formulation is provided comprising an agriculturally active ingredient, an amide of formula (I), and an acyl morpholine according to the formula (II), wherein the groups are as defined in the specification. The formulation may further provide a polar aprotic solvent. The acyl morpholine may be N-formyl morpholine and a polar aprotic solvent may be propylene carbonate. The disclosure also relates to a method for treating a plant or seed using said formulation. acyl morpholine may be N-formyl morpholine and a polar aprotic solvent may be propylene carbonate. The disclosure also relates to a method for treating a plant or seed using said formulation.

Description

AGRICULTURAL FORMULATIONS WITH AMIDES AND ACYL LINES Field of Invention The present invention s to a solvent system comprising an amide, an acyl morpholine, and optionally r components, as a solvent for agriculturally active ingredients. The invention also relates to a formulation comprising an lturally active ingredient and such a solvent system.

Background of the Invention Agriculturally active ingredients, such as pesticides and plant growth regulators, have conventionally been provided to the end-user in different concentrated forms to be 1O diluted in water or other le medium to form a dilute ready-to—use formulation by the end-user. Such concentrated forms e solid formulations, e.g. powders, and liquid formulations. In many applications, liquid formulations are preferred as problems of dusting of toxic powders and slow dissolution in the diluent may be avoided.

An emulsion concentrate lly comprises an agricultural active ingredient, a water- insoluble solvent, and an emulsifier, and when added to the water, it neously, or after active mixing, e.g. stirring, forms an oil-in-water emulsion, the agricultural active ingredient primarily being present in the emulsion ts. This type of concentrated formulation is especially suitable for agricultural actives that are water insoluble/have low water solubility, and where the recommended concentration in the ready-to—use formulation exceeds the solubility of the agricultural active ingredient.

It is important that the agriculturally active ingredient is stably dissolved in the emulsion concentrate. Precipitation of the agriculturally active ingredient may result in a loss of cy. Should the agriculturally active ingredient be concentrated to the precipitates, it is prevented from being evenly distributed when sprayed on a field.

There is thus a need in the field to find new and improved solvents/solvent systems for agriculturally active ingredients, which can be used in agricultural ations, especially in form of emulsion concentrates.

Summary of the Invention One object of the present invention is to meet the needs in the art and to provide a solvent that can be used in agricultural formulations.

Another object of the invention is to provide a solvent for agricultural actives that allows for a concentrated formulation of solvent and agricultural active, in which the agriculturally active ingredient have a reduced tendency to form precipitates.

Another object of the invention is to provide a solvent for agricultural active ingredients that allows for a trated formulation of solvent and agricultural active to be mixed with an aqueous medium without or with only minor precipitation of the active ingredient.

The foregoing objects should be read ctively with the object of at least providing the public with a useful choice.

The present inventors have now surprisingly found that certain combinations comprising 1O amides and acyl morpholines are suitable as solvent systems for agriculturally active ingredients. These combinations have been useful in emulsfiable concentrated formulations.

In a first , the present ion relates to a ation comprising a) an agriculturally active ingredient, b) at least one amide of formula (I): O R R3 R2 wherein R1 is selected from the group consisting of a non-aromatic hydrocarbyl group having from 1 to 16 carbon atoms and benzyl; R2 is selected from the group ting of a hydrocarbyl group having from 1 to 4 carbon atoms and benzyl; and R3 is selected from the group ting of hydrogen and a hydrocarbyl group having from 1 to 16 carbon atoms, whereby when R1 is a hydrocarbyl group having from 1 to 4 carbon atoms or benzyl, then R3 is a non-aromatic hydrocarbyl group having from 5 to 16 carbon atoms, and when R1 is a hydrocarbyl group having from 5 to 16 carbon atoms, then R3 is hydrogen, methyl or ethyl; c) an acyl morpholine of formula (ll), N O R \_/ (ll) wherein R is H, CH3 or CQH5, d) optionally a polar c solvent different from the amide of formula (I) and an acyl morpholine of formula (II), and e) optionally additional ents.

The formulation may be a fully or essentially anhydrous formulation or may be an aqueous formulation, such as an emulsion.

In a second aspect, the present ion s to a method for treating a plant, by contacting said plant with a formulation of the invention.

In a third aspect, the present invention relates to the use of a solvent system comprising an amide of formula (I) and an acyl morpholine of formula (II) and optionally a polar c solvent, as a solvent for an agricultural active.

These and further aspects will now be described further.

Detailed Description of the Invention The agriculturally active ingredients contemplated for use in the present ion, also ed to in the art as agricultural actives, are preferably selected from the group consisting of pesticides and plant growth regulators.

The agriculturally active ingredients are preferably selected amongst those having low water solubility, and most preferably amongst those being water insoluble.

The term “agriculturally active ingredient” as used herein is to be taken as assing any organic compound being agriculturally active. However, to the extent that the amides of formula (I), the acyl morpholines of the a (II) or the polar aprotic co-solvents as defined herein, are lturally active, these are not considered as agriculturally active ingredients.

The term “compound having low water solubility" as defined herein, relates to a nd having a solubility of at most 5, such as at most I g/l, for example at most 0.7 9/! in water.

In the context of the present invention, water solubility shall be interpreted as being measured according to ASTM E 1148-87 “Standard Test Method for Measurements of Aqueous Solubility”.

As used herein, the term “pesticide" refers to a compound that will prevent, destroy, repel, or mitigate any pest.

As used herein, the term “plant growth regulator" refers to a compound, which through physioiogical action wiii accelerate or retard the rate of growth or rate of maturation or otherwise alter the behaviour of ornamental or crop plants or the ts thereof.

Pesticides and plant growth regulators especially contemplated for use in the present ion are organic compounds, preferably synthetic organic compounds.

Pesticides contempiated for use in the present invention include fungicides, herbicides, insecticides, miticides, nematicides, acaricides, and moiluscicides.

Preferred agriculturaiiy active ingredients plated for use in the present invention include ides and plant growth tors of the classes triazoles, strobiiurins, 1O aikyienebis(dithiocarbamate) compounds, idazoles, phenoxy carboxyiic acids, benzoic acids, suifonyiureas, triazines, pyridine yiic acids, neonicotinides, es, organophosphates, and pyrethroids.

Examples of suitable fungicides of the (present) invention include fungicides of the classes triazoles (e.g. tebuconazoie, tetraconazole, cyproconazole, epoxiconazole, difenconazoie, onazole, prothioconazoie), strobiiurins (e.g. trifioxystrobin, azoxystrobin, fluoxastrobin, pyraclostrobin), nebis(dithiocarbamate) compounds (e.g. mancozeb) and benzimidazoles (e.g carbendazim).

Examples of suitable herbicides of the (present) invention include phenoxy carboxyiic acids (e.g. 2,4-D—acid, MCPA), benzoic acids (e.g. a-acid), sulfonylureas (e.g. methyisulfuron—methyl, rimsulfuron), triazines (e.g. atrazine and simazine), triazolinones (e.g. amicarbazone) and pyridine carboxyiic acids (e.g. triclopyr).

Examples of suitable insecticides of the nt) invention include neonicotinides (e.g. thiamethoxam, ciothianidin, thiacloprid, dinotefuran, acetamiprid, nitenpyram, imidacloprid), amidines (e.g. amitraz), organophosphates (e.g. chlorpyrifos) and pyrethroids (e.g. permethrin, bifenthrin, deltamethrin).

For a detailed description of each of the above-mentioned pesticides and plant growth regulators, reference is made to handbooks, 8.9. “The e—Pesticide Manual v4.0” from BCPC Publications Ltd, Alton, Hampshire. (iSBN 1 901396 42 8).

Formulations of the present invention comprise at ieast one amide of formula (1): WO 20131076200 5 O R R3 R2 (1) wherein R1 is ed from the group consisting of a non-aromatic hydrocarbyl group having from 1 to 16 carbon atoms and benzyl; R2 is selected from the group consisting of a hydrocarbyl group having from 1 to 4 carbon atoms and benzyl; and R3 is selected from the group consisting of hydrogen and a arbyl group having from 1 to 16 carbon atoms.

Preferably, when R1 is a hydrocarbyl group having from 1 to 4 carbon atoms or benzyl, 1O then R3 is a non—aromatic hydrocarbyl group having from 5 to 16 carbon atoms.

Preferably, when R1 is a hydrocarbyl group having from 5 to 16 carbon atoms, then R3 is hydrogen, methyl or ethyl in embodiments of the present invention, R1 and R2 are independently methyl or ethyl, preferably methyl, and R3 is a hydrocarbyl group, preferably a straight or branched alkyl or alkenyl group having from 6 to 12 carbon atoms, preferably 7 to 10 carbon atoms. Examples include methyl decanamide and N,N~dimethyl octanamide.

Such amides are known and cially available or can be synthesized by reacting the appropriate organic acid and an amine according to methods well known in the art.

In embodiments of the present invention, in the amide of formula (l), R1 is a hydrocarbyl group, preferably a straight or ed alkyl or alkenyl group, having from 6 to 12, ably 8 to 11 carbon atoms, R2 is , ethyl or benzyl, preferably methyl, and R3 is hydrogen, methyl or ethyl, preferably hydrogen. Examples include N— methyl—N-(2-propylheptyl)—formamide, N-methyl-N-(2—propylheptyl)-acetamide, N- methyl-N-(n-decyl)~acetamide, N-methyl-N—(n—decyl)-formamide, N—methyl-N- (monomethyl substituted Cg-1oa|kyl)-acetamide and N-methyI-N-(monomethyl substituted C940 alkyI)-f0rmamide.

Such amides are known and commercially available or can be synthesized ing to known methods, eg. as described in A1 to Akzo Nobel Chemicals international B.V.

WO 20131076200 6 The acyl morpholines contemplated for use in a formulation of the present ion include 4-formyl morpholine (R = H, also referred to as N-formyl morpholine or NFM), 4—acetyl morpholine (R = CH3, also referred to as N-acetyl morpholine or NAM), 4~ propionyl morpholine (R = Csz, also ed to as N—propionyl line or NPM) and mixtures thereof. Preferably, a formulation of the present invention comprises 4- formyl morpholine, and more ably, 4—formyl morpholine ents at least 50, most preferably at least 90, such as 100 wt% of the acyl morpholines of formula (ll) present in the formulation. However, for formulations comprising the pesticide N,N’-bis— [(1~formamid0-2,2,2—trichloro)ethy|]piperazine, it is preferred that the acyl morpholine is selected from among 4—acetyl morpholine and ionyl morpholine.

The acyl morpholines as such are well known compounds and are commercially available from standard al suppliers.

Polar aprotic solvents, which are different from amides of formula (I) and acyl morpholines of formula (II), herein referred to as “polar aprotic ts” may be included in formulations of the invention, The polar aprotic t is preferably selected from those polar aprotic ts having a flash point of at least 65°C, as measured according to ASTM D93.

The polar aprotic solvent is preferably selected from the group consisting of a sulfoxide, an amide, a hydrocarbyl— or hydrocarbylene carbonate, and mixtures of two or more thereof. Preferred sulfoxides include dimethyl sulfoxide. Preferred hydrocarbyl carbonates include di-alkyl carbonates, such as those with C1-C3 alkyl chains.

Preferred hydrocarbylene-carbonates include alkylene carbonates, more preferably C2- C4-alkylenecarbonates, most preferably propylene carbonate. More preferably, the polar c co—solvent is selected from the group consisting of dimethyl sulfoxide, propylene carbonate and a mixture thereof, most preferably propylene carbonate.

Additional components may be t in the formulation of the ion. Examples of such additional components include one or more adjuvants, such as bioefficacy enhancers that increase the bioefficacy of ltural actives, humectants, wetting agents, rheology modifiers, surfactants, emulsifiers, stickers, drift reducers and/or other additional components tionally used in agricultural compositions.

Water is not contemplated for use as a member of the above “additional components.

A formulation of the present invention may be a fully or ially anhydrous formulation, such as comprising less than 10, preferably less than 1 wt% of water, or WO 76200 7 may be an aqueous ation, such as an emulsion, typically an oil—in-water emulsion, usually comprising at least 90, such as at least 99 wt% water, based on the total weight of the formulation of the invention.

The concentration of such one or more agriculturally active ient in a formulation of the present invention is typically within the solubility range of the specific compound in the specific solvent .

The concentration of the agriculturally active ingredient in a ation of the present invention is typically from about 0.1, such as from about 10, for example from about 20, to about 950, such as to about 500, for example to about 300 g/l based on the total volume of an anhydrous formulation of the invention. in representative formulations of the t invention, the concentration of the at least one agriculturally active ingredient in such a composition is from 50 to 250 g/I.

The concentration of the amide of the formula (l) in a ation of the present invention is typically from 25, such as from 50, for example from 100, to 900, such as to 700, for example to 500 g/l based on the total volume of an anhydrous formulation of the invention.

When a polar aprotic solvent is present, the weight ratio between acyl morpholine of formula (II) and polar aprotic solvent is typically from 5:95, from 30:70, from 50:50, from 70:30, or from 75:25, to 95:5, to 90:10, or to 85:15. For example, the weight ratio between acyl line of formula (II) and polar aprotic solvent may be about 80:20.

A ation of the present invention typically comprises from about 10, such as from 50, for example 100, to about 600, such as to about 400, for example to about 250 g/I of the total of c) acyl morpholine of the formula (II) and, if t, d) polar aprotic co- solvent, based on the total volume of an anhydrous formulation of the invention.

If present, the concentration of additional components in a formulation of the present invention is typically from 10, such as from 20, for example from 50, to 250, such as to 150, for example to 100 g/I based on the total volume of an anhydrous formulation of the invention.

The formulations according to the invention are typically prepared in such a manner that the components are mixed with one another in the desired ratios and to the desired concentrations. in general, the formulations are prepared at a temperature of between 10 and 50°C. Suitable apparatuses that are employed for the preparation of agricultural formulations are suitable as apparatuses for the preparation of the formulations of the present ion.

The composition of the present invention may be an emulsifiable concentrated composition, hereinafter and in the art commonly ed to as an “emulsifiable concentrate”, or “EC”, comprising a formulation as defined herein, including an emulsifying agent. Hence, such an emulsifiable concentrate comprises an agriculturally active ingredient, an amide of the formula (I), an acyl morpholine of the formula (ll), optionally a polar aprotic co-solvent, and an emulsifier.

In an emulsifiable concentrate, the concentration of agriculturally active ingredient is typically too high for end—use, and the emulsifiable concentrate is intended to be diluted with an aqueous medium into a work—composition.

An emulsifiable concentrate of the invention preferably comprises water in an amount below the amount at which an oil-in-water on is formed. Preferably, the emulsifiable concentrate comprises less than about 10, more preferably less than about 1 wt% of water, based on the total weight of the emulsifiable concentrate. Most preferably, the emulsifiable concentrate of the present invention is essentially free from water in the sense that the emulsifiable concentrate does not n water beyond what is inevitable from the equilibrium with the nding atmosphere.

Emulsifiers contemplated for use in the t invention e surfactants known as emulsifying agents by those skilled in the art, such as, anionic surfactants, non-ionic surfactants, polymers, and blends of two or more thereof, especially blends comprising anionic and non-ionic surfactants.

Examples of non—ionic surfactants contemplated for use as emulsifying agents in the present invention include alkoxylated, preferably ethoxylated and/or propoxylated alcohols, ably containing from 8 to 22 carbon atoms; alkyl(poly)glycosides, such as straight or branched C4—C10 alkyl(poly)glycosides; lated, preferably ethoxylated, sorbitan or sorbitol esters; castor oil ethoxylates; and tristyrylphenol alkoxylates. red ethoxylated alcohols have a degree of lation of from 1 to 50, more preferably 2 to 20, most preferably 3 to 10. Some alkoxylated alcohols plated for use in the present invention include those based on branched alcohols, such as the Guerbet alcohols, e.g. 2-propylheptanol and 2—ethylhexanol, and C10- or C13—OXO— alcohols, i.e. an alcohoi mixture whose main component is formed by at least one branched 010— or C13—alcohol, and the alcohols commercially available as Exxal alcohols from Exxon Mobile Chemicals and Neodol alcohols from Shell Chemicals.

Examples of anionic surfactants contemplated for use as emulsifying agents in the t invention include sulfosuccinates, alkylbenzene sulfonic acid salts, such as calcium or sodium dodecylbenzene sulfonate, alkyl sulphonates, alkyl ether sulphates, phosphate esters of optionally alkoxylated, preferably ethoxylated and/or ylated, alcohols, xylene and cumene sulfonate salts, and naphthalene or alkylnaphthalene sulfonates, which may be condensated, or combinations thereof. es of polymers for use alone or in combination as emulsifying agent include ne oxide—propylene oxide block co—polymers, acrylic acid based comb polymers, and xanthan gum.

In an emulsifiable concentrate of the present invention, the concentration of emulsifier is typically from 10, such as from 50, to 200 such as to 150 g/I based on the total volume of an anhydrous formulation of the invention.

The present invention also relates to an s, lly oil-in-water, emulsion comprising an aqueous medium, at least one agriculturally active ingredient, ably having low water solubility, an amide of formula (I), an acyl morpholine according to the formula (ii), an emulsifier and, optionally, a polar aprotic solvent and/or additional components.

For example, such an emulsion may be obtained by mixing an aqueous medium and an fiable concentrate as previously defined herein or by separately mixing the components.

As used herein, the term “emulsion” shall be interpreted to e macro emulsions, nano emulsions, micro emulsions and suspoemulsions, Le. ons in which a particulate solid is suspended.

The aqueous medium that is a component of the emulsion of the t invention typically comprises water as the major component. Preferably, water constitutes at least 50 wt% such as at least 75 wt%, for example at least 90 wt% of the aqueous medium. The aqueous medium may further comprise other components, such as salts, buffering , pH-controlling agents, such as acids or bases, fertilizers, etc.

When the emulsifiable concentrate is mixed with the s medium, an emulsion is formed, the emulsion typically being the work composition that will be used by the end— 1O 2012/073368 user, with the advantage that the end-user does not have to handle and store large quantities of work composition, but can prepare the amounts necessary for the moment.

Emulsions of the present invention typically are prepared by mixing an emulsifiable concentrate of the invention with an aqueous medium at a volume ratio n the fiable concentrate and aqueous medium of from about 1:25, preferably from about 1:50, more preferably from about 1:100; to about 1:1000, ably to about 1:500, more preferably to about 1:300. In a entative emulsion of the present ion, the volume ratio emulsifiable concentratezaqueous medium is about 1:200. 1O An age of the present invention is that the agriculturally active ingredient exhibit a lower, or no, tendency to precipitate or crystallise when the ation is in concentrated form, i.e. comprising less than 10 wt% water, preferably less than 1 wt% water Another advantage of the present invention is that even at high ons in the emulsion, i.e. at low ratios between the ations and the aqueous medium, the tendency of the agriculturally active ingredient to precipitate or crystallise is low, also at temperatures significantly below room temperature, such as at 5°C. This is advantageous for many reasons. Should it be necessary for the end-user to stop spraying before having consumed a full batch of emulsion, the unused emulsion will be possible to use later, for example the next day, even if the unused emulsion was stored at reduced temperatures.

In a further aspect, the present invention provides a method for treating a plant or seed, wherein the plant or seed is contacted with a formulation of the invention. The desired amount of agriculturally active ingredient to be contacted with a plant or seed by means of such method depends on several parameters, such as the biological ty of the agriculturally active, but generally, the amount is adjusted to be sufficient for the agriculturally active ingredient to perform its d activity.

As used herein, ”plant” includes all parts of a plant, including roots, stems, leaves, flowers and fruits.

In one embodiment of the treatment method, the plant or seed is contacted with a formulation of the present invention, usually an oil-in-water emulsion, by means of spraying.

In another embodiment of the treatment method, a plant or a seed, usually a seed, is ted with a formulation of the invention by dipping or soaking the plant or seed in the formulation.

Experiments ment 1 To obtain the formulations disclosed in tables 1 to 3, agriculturaily active ients (Al) was added to a measuring flask along with N-formyl morpholine (NFM), propylene carbonate (PC) and emulsifier to the ted amounts. methyl decanamide or N-decyl-N-methyl formamide was then added so that the whole mixture amounted to “H.

The emulsifier was 2-ethyl hexanol alkoxylated with 35 moles propylene oxide and 32 moles ethylene oxide per mole alcohol (2EH+35PO+32EO) and Calcium l bensen sulfonated in a 5:3 weightweight ratio.

The mixture was stirred with a magnetic stirrer until the active dissolved in the formulation. Finished formulations were put into a refrigerator for seven days at 0°C.

All formulations were judged by the naked eye if it contained any crystals after the storing. The composition of each formulation and the results are summarized in the tables 1-3 below.

Table 1 NFM PC N,N- N-decyl- . Al Emulsifier Crystals dimethyl N-methyl Q“ 9 ill formed decanamide formamide 100 9/1 1* Fenbu- 65 9/1 0 0 Up to 1 I Yes conazole _.._L_ 100 g/I 2 Fenbu- 65 g/l 100 0 Up to 1 I No 100 9/! 3 Fenbu— 659/1 80 20 Upt01l No conazole 100 9/! 4 Fenbu— 65 9/! 6O 40 Up to 1 | No conazole 100 9/! ' * Fenbu- 65 9/! 0 0 Up to 1 I Yes conazole 100 9/! 6 Fenbu- 65 9/! 100 0 Up to 1 I No conazole 100 g/l 7 Fenbu— 65 g/I 80 20 Up to 1 I No conazole 100 9/! 8 Fenbu— 65 g/l 6O 40 Up to 1 I No conazole * Comparative experiment Table 2 Formul. Pesticide Emulsifier gig-ethyl ls L— 9/1 9/1 ormed decanamide 9* £219;thoprid 65 9/1 0 0 Up to ‘ Yes llrggii/Ichloprid 65 g/I 500 0 Up to 1 I No 11 hlopfid 65 g/l 400 100 Up to 1 I No 12 'cmoprid 65 9/1 300 200 Up to 1 I No 13* magi/moped 65 g/l 0 500 Up to 1 I Yes * Comparative experiment Table 3 N,N- Formul. Pesticide Emulsifier Crystals dimethyl . formed decanamlde 3509fl 14* fop- Up to 1 I Yes butyl 3509/l Cyhalofop- Up to 1 I No butyl 350gll 16 Cyhalofop- Up to 1 i No butyl * Comparative experiment From the results, it is evident that the inclusion of acyl morpholine and optionally polar aprotic solvent in the amide solvent reduces the formation of crystals, and that leaving out the acyl morpholine does not give satisfactory results. 14 2012/073368 Experiment 2 - Emulsion dilution Formulations ning 100 g/I of Fenbuconazoie were formulated together with 65 g/l of surfactant blend (47 wt% ypropylene polyoxyethylene block copolymer, 56 PO/60 E0, 20 wt% dodecyl benzene sulfonate, 33 wt% HD ocenol (60/65) ethoxylate, 23 E0) and diluted as follows: 1) N-formylmoriolin : ene carbonate (in the weight ratio 4:1) up to 1 liter 2) N—formylmorfolin : propylene carbonate (in the weight ratio 4:1) 100g/I and up to 1 liter with N,N dimethyl decanamide Each formulation was emulsified into water (342 ppm CaCOg-eq) at ambient temperature (~22°C) in the volume ratio (formulation:water) 5 ml:95 ml dilution. The emulsions were poured into 100 ml glass test tubes and evaluated for stability by measuring the volume of creaming/oil/sedimentation visible in the test tubes after 2 hours. The ance was judged by ocular inspection with the naked eye and the results can be seen in table 4 Table 4 Formulation , Appearance after 2 hrs J 17* I 5 ml oil } 18 I No cream/oil or sedimentation * Comparative experiment

Claims (1)

1. Claims ‘l. A formulation comprising: a) at least one agriculturally active ingredient; b) at least one amide of formula (I): O R R3 R2 (I) wherein R1 is selected from the group consisting of a non-aromatic hydrocarbyl group having from 1 to 16 carbon atom and benzyl; R2 is selected from the group consisting of a hydrocarbyl group having 10 from 1 to 4 carbon atoms and benzyl; and R3 is selected from the group consisting of en and a hydrocarbyl group having from 1 to 16 carbon atoms, whereby when R1 is a hydrocarbyl group having from 1 to 4 carbon atoms or benzyl, then R3 is a non—aromatic hydrocarbyl group having 15 from 5 to 16 carbon atoms, and when R1 is a hydrocarbyl group having from 5 to 16 carbon atoms, then R3 is hydrogen, methyl or ethyl; c) at least one acyl line according to the formula (ll), ° /_\ N O R ‘—’ wherein R is H, CH3 or CZH5. 20 2. A formulation according to claim 1, wherein said agriculturally active ingredient is selected from the group consisting of pesticides and plant growth regulators. 3. A formulation according to claim 2, wherein the pesticides are ed from the group ting of fungicides, herbicides, insecticides, des, nematicides, acaricides, molluscicides and mixtures thereof. 25 4. A formulation according to any one of the preceding claims, wherein said agriculturally active ingredient is selected from the group consisting of triazoles, strobilurins, alkylenebis(dithiocarbamate) compounds, benzimidazoles, phenoxy carboxylic acids, benzoic acids, sulfonylureas, nes, pyridine carboxyiic acids, neonicotinides, amidines, organophosphates, pyrethroids and mixtures thereof. A formulation according to any one of the ing claims, wherein R1 and R2 independently are methyl or ethyl and R3 is a hydrocarbyi having from 6 to 12 carbon atoms. . A formulation according to any one of the preceding claims, wherein R1 is a hydrocarbyi having from 8 to 12 carbon atoms, R2 is methyl, ethyl or benzyl, 10 and R3 is hydrogen, methyl or ethyl. A formulation according any one of the preceding , further comprising d) at least one polar aprotic solvent different from an amide of formuia (i) and an acyl morpholine of formula (ii). A formulation according to claim 7, wherein said polar aprotic solvent different 15 from an amide of formula (i) and an acyl morphoiine of a (ll) is ed from the group consisting of a suifoxide, an amide, a hydrocarbyi carbonate, a hydrocarbylene carbonate and es thereof. A formulation according to claim 8, wherein said polar aprotic solvent ent from an amide of formula (l) and an acyl morphoiine of formula (II) is selected 20 from the group consisting of dimethyl suifoxide, propyiene carbonate and a mixture thereof. 10. A formulation according to any one of the preceding claims, comprising an acyl morphoiine of formula (Ii) which is N-formyl morpholine and a polar aprotic solvent ent from an amide of formuia (l) and an acyl line of formula 25 (ll), which is propylene carbonate. 11. A formulation ing to any one of the claims 7 to 10, wherein the weight ratio n acyl morpholine ing to the formula (II) and polar aprotic solvent different from an acyl morpholine of formuia (ii) is from 70:30 to 90:10. 12. A formulation according to claim 11, wherein the weight ratio between acyl 30 morpholine according to the formuia (ii) and polar aprotic solvent different from an acyl morpholine of formula (ii) is from 75:25 to 85:15. 13. A formulation according to any one of the preceding , further comprising e) at least one additional component selected from the group consisting of adjuvants, surfactants, fiers, wetting agents, rheology modifiers and mixtures of two or more thereof. 14. A formulation according to any one of the preceding claims, comprising: from 10 to 800 g/l of a); from 50 to 900 g/l of b); from 10 to 600 g/l of the total of c) and d); and from 0 to 250 g/l of e); 10 based on the total volume of an anhydrous formulation. 15. A formulation according to any one of the preceding claims, sing from 10 to 200 g/l of emulsifier, based on the total volume of an anhydrous formulation. 16. A formulation according to any one of the preceding claims comprising at most 10 wt% water based on the total weight of the formulation. 15 17. A formulation according to claim 16, comprising at most 1 wt% water based on the total weight of the formulation. 18. A formulation according to any one of the claims 1 to 15 sing at least 90 wt% water based on the total weight of the formulation. 19. A formulation according to claim 18, in the form of an oil-in-water emulsion. 20 20. A formulation according to claim'18 or 19, sing at least 99 wt% water based on the total weight of the formulation. 21. A method for treating a plant or seed, comprising contacting said plant or seed with a formulation according to any one of the claims 1 to 20. 22. The use of a solvent system comprising: 25 (i) at least one amide of formula (I): O R R3 R2 (I) R1 is selected from the group consisting of a hydrocarbyl group having from 1 to 16 carbon atoms and benzyl; R2 is selected from the group consisting of a hydrocarbyl group having from 1 to 4 carbon atoms and benzyl; and R3 is selected from the group consisting of hydrogen and a hydrocarbyl group having from 1 to 16 carbon atoms, with the proviso that: when R1 is a hydrocarbyl group having from 1 to 4 carbon atoms or benzyl, then R3 is a non—aromatic hydrocarbyl group having from 5 to 16 carbon atoms, and that when R1 is a arbyl group having from 5 to 16 carbon atoms, then R3 is hydrogen, methyl or ethyl; 10 (ii) an acyl morpholine according to the formula (ll), ° /_\ N O R \__/ wherein R is H, CH3 or CZH5, (iii) optionally a polar aprotic solvent different from an amide of formula (I) and an acyl morpholine of formula (ll), and 15 (iv) optionally additional components; as a solvent for an agriculturally active ingredient. 23. A formulation according to claim 1, substantially as herein described with nce to any one of the Examples thereof. 24. A formulation according to any one of claims 1 to 20, substantially as herein 20 described. 25. A method according to claim 21, substantially as herein described. 26. A use according to claim 22, substantially as herein described.