Conjugates of polysaccharides with hydrophobic compounds as emulsion stabilizers.

Abstract

The present invention relates to a conjugate of a sugar compound selected from disaccharides, oligosaccharides and polysaccharides with at least one hydrophobic compound selected from terpenes, polyterpenes and polyterpene ethers, wherein the hydrophobic compound in the conjugate is either directly bound to an oxygen atom of the sugar or is bound to a group of formula (I) or (II): RO-(Y) k -A 1 -X 1 - (I)RO-(Y) k -A 1 -X 2 -A 2 -X 3 - (II) (In formulas (I) and (II), R is a radical of a terpene compound, a polyterpene, or a polyterpene ether compound, k is 0 or 1, Y is C(O) or C(O)NH, and A 1 is a direct bond or C1-C6 alkylene, and A 2 is C2~C 10 is alkylene, and X 1 is C(O) or k=1 and A 1 When is C1-C6 alkylene, it may be OC(O) or NHC(O), and X 1 is bonded to an oxygen atom of the sugar compound, and X 2 is C(O)NH or NHC(O)NH, and X 3 - is N= or NH-, and X in formula (II) 3 is attached to a carbon atom of a sugar compound). The present invention also relates to the use of such conjugates as stabilizers for aqueous emulsions of water-immiscible liquids.

Description

[Technical Field]

[0001] The present invention relates to conjugates of polysaccharides and hydrophobic compounds and their use as stabilizers for aqueous emulsions of water-immiscible liquids, in particular emulsions of water-immiscible liquids containing organic active substances, in particular agrochemical or cosmetic compounds. The present invention also relates to aqueous compositions of organic active compounds, in particular agrochemical compounds, which are aqueous emulsions of water-immiscible liquids containing at least one organic active substance, wherein the aqueous emulsion contains at least one conjugate as defined herein. [Background technology]

[0002] Aqueous emulsions play a central role in many everyday processes, such as washing and cleaning processes, the formulation and application of active ingredients in crop protection, pharmaceuticals, and cosmetics, and industrial processes involving aqueous emulsions. Emulsions are known as finely divided mixtures of an aqueous liquid and a water-immiscible or only slightly water-miscible liquid, in which one of the two liquid phases exists as a dispersed or internal phase distributed within the other. When the dispersed phase is aqueous, the emulsion is called a water-in-oil emulsion (w / o emulsion), while when a water-immiscible liquid forms the dispersed phase, the emulsion is called an oil-in-water emulsion (o / w emulsion). Emulsions are thermodynamically and kinetically unstable due to their high surface energy, and the dispersed phase tends to coalesce into a larger phase to reduce the surface energy. Therefore, surfactants are used to stabilize aqueous emulsions.

[0003] Many active ingredient formulations are emulsions or form emulsions when diluted with water.For example, agriculturally active compounds must be formulated in such a way that they can be applied safely and effectively.For this purpose, active compounds are often commercially available in the form of concentrated formulations that are diluted in water during application.In such formulations, surfactants play an important role.On the one hand, they ensure that they can be easily diluted in water without creaming or sedimentation and are evenly distributed in the aqueous phase, and at the same time, they stabilize the active ingredients that are finely distributed in the aqueous dilution.Similar requirements must be met in pharmaceutical compositions.

[0004] Cosmetic and pharmaceutical formulations such as creams and ointments often require the co-formulation of water-insoluble liquids with an aqueous phase.

[0005] In detergents and cleaning agents, surfactants are required to release soils, especially grease and oily contaminants, from soiled surfaces and to stabilize them in the aqueous cleaning phase, such as laundry suds or rinse liquor.

[0006] Surfactants are essential for many applications, but most conventional surfactants degrade only slowly, creating environmental problems even when used as directed. Therefore, there is a fundamental need for easily degradable surfactants.

[0007] M. H. Alves et al., Biomacromolecules 2014, 15, 242-251, described amphiphilic polymers with a dextran backbone and thio-functionalized terpene groups attached to the backbone. These amphiphilic polymers can be used to prepare oil-in-water miniemulsions. However, these amphiphilic polymers are difficult to prepare and are limited to terpenes with free double bonds. Their properties are not entirely satisfactory, and the presence of sulfur in these polymers can lead to toxic degradation products.

[0008] Organic active substances can be formulated as microcapsule formulations, e.g., as microcapsule suspensions, for several reasons, such as delayed release, toxicity, volatility, degradation, or compatibility with other active substances. In such formulations, the organic active compound is provided in the form of particles in which the organic active compound or a solution of the organic active compound in a water-immiscible solvent is encapsulated or embedded in a shell of a water-insoluble polymer (H. Mollet, A. Grubenmann "Formulation Technology" 1999). st ed., Wiley-VCH Verlag GmbH, Weinheim 2001, Chapter 6.4 and Chapter 14.2.2). Such polymers can be, for example, polyurethane, polyurea, polyamide, polyester, polycarbonate, urea / formaldehyde resin, melamine / formaldehyde resin, polystyrene, or acrylate polymer. Microencapsulation of organic active substances offers significant benefits by reducing the acute toxicity and phytotoxicity of the organic active substance or by reducing its volatility and degradation, but is often difficult to achieve. A major problem is the aggregation of organic active substances during or after encapsulation, especially when an encapsulation method that may work for a particular organic active compound does not necessarily work for another organic active compound. A further problem associated with microcapsule formulations is the large amount of microplastics released into the environment. In the environment, microplastics can accumulate in animals or plants and subsequently become nutrients for humans (see, for example, C.M. Rochmann, "The global odyssee of plastic pollution," Science 368 (2020) pp. 1184-1185). The use of synthetic polymer microcapsules is therefore raising increasing ecological concerns on the part of customers and regulatory authorities. There is therefore a need to provide delivery forms of organic active substances that can be produced without or with reduced amounts of non-degradable plastic material. Summary of the Invention [Means for solving the problem]

[0009] It has now been surprisingly found that the above-mentioned problems can be solved or at least ameliorated by conjugates of sugar compounds selected from disaccharides, oligosaccharides, and polysaccharides with at least one hydrophobic compound selected from terpenes, polyterpenes, and polyterpene ethers. When the conjugates are present in aqueous emulsions of water-immiscible liquids, particularly oil-in-water emulsions (hereinafter referred to as o / w emulsions), the stability of the emulsions is significantly improved, allowing the emulsions to remain stable for at least several weeks. Microscopic analysis of the emulsions has shown that the conjugate molecules aggregate at the phase boundary, thereby forming a stable layer surrounding the droplets present in the aqueous emulsion, regardless of whether the emulsion is an oil-in-water (o / w) emulsion in which the droplets are formed by a water-immiscible liquid or a water-in-oil (w / o) emulsion in which the droplets are formed by emulsifying water in a non-aqueous liquid. It has been observed that a stable layer forms whether or not the water-immiscible liquid contains a solid organic active material dissolved in a water-immiscible solvent.

[0010] The presence of the conjugate in an aqueous emulsion of a water-immiscible liquid stabilizes the droplets against coalescence and Ostwald ripening, and therefore against phase separation. Furthermore, the conjugate molecule also facilitates the emulsification of a non-aqueous phase in an aqueous phase and vice versa.

[0011] Thus, a first aspect of the present invention relates to a conjugate as described herein, formed by a sugar compound selected from disaccharides, oligosaccharides and polysaccharides and at least one hydrophobic compound selected from terpenes, polyterpenes and polyterpene ethers, which is either directly, i.e. covalently, bound to an oxygen atom of the sugar compound or to a group of formula (I) or (II): RO-(Y) k -A1 -X 1 - (I) RO-(Y) k -A 1 -X 2 -A 2 -X 3 - (II) (In formulas (I) and (II), R is a radical of a terpene compound, a polyterpene, or a polyterpene ether compound; k is 0 or 1; Y is C(O) or C(O)NH; A 1 is a direct bond or C1-C6 alkylene, A 2 is C2~C 10 is alkylene, X 1 is C(O) or k=1 and A 1 C1-C6 alkylene X 1 When X is 1 is attached to an oxygen atom of the polysaccharide, X 2 is C(O)NH or NHC(O)NH, X 3 - is N= or NH-, X in formula (II) 3 is attached to a carbon atom in a sugar compound) It exists as.

[0012] The conjugates of the present invention are particularly useful for stabilizing aqueous emulsions of water-immiscible liquids, especially oil-in-water emulsions.

[0013] A second aspect of the invention therefore relates to the use of the conjugate of the invention as a stabilizer for aqueous emulsions of water-immiscible liquids, in particular oil-in-water emulsions, and to a method for stabilizing aqueous emulsions of water-immiscible liquids, in particular oil-in-water emulsions, comprising incorporating into the aqueous emulsion of a water-immiscible liquid a conjugate of a sugar compound and at least one hydrophobic compound as described herein. A particular group of embodiments of the second aspect of the invention relates to the use of the method for stabilizing an o / w emulsion containing at least one organic active compound, such as an organic active selected from pesticides, aroma chemicals, pharmaceutically active compounds, vitamins, cosmetic actives and organic effective compounds.

[0014] Furthermore, a further aspect of the present invention is - an aqueous composition which is an aqueous emulsion of a water-immiscible liquid, containing at least one conjugate of the invention; - an aqueous composition of an organic active compound which is an aqueous emulsion of a water-immiscible liquid containing at least one conjugate of the invention, wherein the water-immiscible liquid contains the organic active compound of the invention; - a method for controlling plant pathogenic organisms, said method comprising the step of applying a pesticidally effective amount of said aqueous composition as defined herein and hereinafter; - washing and cleaning compositions containing the conjugates of the invention.

[0015] The present invention has several advantages. The conjugates described herein facilitate emulsifying a non-aqueous phase in an aqueous phase and stabilize the emulsion droplets against Ostwald ripening and coalescence, and thus against phase separation. Therefore, other emulsifiers typically required for emulsion stabilization can be omitted, or at least their amounts can be reduced. Furthermore, the conjugates of the present invention can be prepared in good yields by standard synthetic techniques of organic chemistry or polymer chemistry, respectively.

[0016] As mentioned above, conjugate molecules aggregate at the interface between the aqueous and non-aqueous phases of an emulsion to form a stable layer, thereby stabilizing the droplets against coalescence and, therefore, phase separation. In the case of an oil-in-water emulsion, the conjugate molecules form a stable layer surrounding the oil droplets present in the oil-in-water emulsion, regardless of whether the water-immiscible liquid itself forms the oil droplets or contains one or more organic active compounds, such as pesticides, dissolved in a water-immiscible solvent that forms the droplets. In the case of an inverse emulsion, i.e., a water-in-oil emulsion, the conjugate molecules form a stable layer surrounding the aqueous droplets present in the w / o emulsion, thereby allowing the inclusion of water-soluble pesticides dissolved in the aqueous phase. Thus, the conjugate molecules mimic the encapsulation of the pesticidal compound. For example, the presence of the conjugate in an aqueous emulsion of a pesticidal compound stabilizes the emulsion droplets, thereby improving the stability of the emulsion. At the same time, they provide good compatibility with other pesticides in aqueous emulsions. Furthermore, improved selectivity of pesticides toward target organisms can be achieved through conjugates. Because the conjugate molecules contain carbohydrate groups, they are biodegradable in the environment. Similarly, biologically derived terpenes, polyterpenes, and polyterpene ethers are also biodegradable under environmental conditions. Therefore, conjugates qualify as biodegradable surfactants. Furthermore, conjugates have been found to offer similar advantages to conventional microencapsulation. Therefore, they can replace conventional microencapsulation materials, thereby reducing the introduction of microplastics into the environment. DETAILED DESCRIPTION OF THE INVENTION

[0017] The term "conjugate of a polysaccharide and at least one hydrophobic compound" is understood to mean that the polysaccharide molecule has at least one hydrophobic molecule selected from terpenes, polyterpenes and polyterpene ethers, and the hydrophobic compound is directly attached to the saccharide compound, i.e., covalently linked to a carbon or oxygen atom of the saccharide compound by a covalent bond, or is attached by a covalent linker group, and together with the hydrophobic compound forms a group of formula (I) or (II), respectively.

[0018] Throughout this specification and application, the terms "organic active compound", "organic active substance" and "active compound" are used synonymously. These terms are understood by those skilled in the art to mean organic chemical compounds that cause a physiological effect in living organisms and plants, as well as substances that cause a chemical effect or catalyze a chemical reaction in the non-animal kingdom. Examples of active substances are aroma chemicals, organic crop protection agents, organic pharmaceuticals, organic cosmetic active substances, and organic active substances for use in the construction sector, referred to as construction chemicals, especially catalysts for products in the construction sector, such as crosslinking catalysts or polymerization catalysts. The term "organic active substance" also includes "metal-organic active substances".

[0019] In this specification and throughout the specification, the term "water-immiscible" refers to a material having a solubility in deionized water of at most 5 g / L, in particular at most 1 g / L, at 20°C and 1 bar. The solubility of a water-immiscible material in deionized water under the conditions given herein may be zero, i.e., below the detection limit. Herein and throughout the specification, the terms "water-immiscible liquid" and "water-immiscible organic liquid" are used synonymously.

[0020] The term liquid refers to a material that is in a liquid state at ambient conditions, i.e. a non-solid and non-gaseous material. In the context of the present invention, a liquid material preferably has a dynamic viscosity in the range of 0.2 to 2000 mPas, in particular in the range of 0.5 to 1000 mPas, at 20°C. Here and throughout this specification, ambient conditions refer to a temperature in the range of 20 to 25°C and atmospheric pressure, i.e. about 1 bar.

[0021] The term "low molecular weight organic active compound" generally refers to an organic or organometallic chemically active compound having a defined molecular weight Mn of less than 1000 daltons, typically in the range of 80 to 1000 daltons, and especially in the range of 100 to 500 daltons. The molecular weight can be determined by mass spectrometry.

[0022] The term "susceptible active" refers to organic active compounds that are not stable to their environmental conditions and are damaged or degraded, for example, due to the pH of their environment or by oxidation.

[0023] The terms "organic crop protection agent," "pesticide," "pesticidal compound," "pesticide," and "pesticidal compound" are used synonymously and refer to any physiologically active compound suitable for agricultural purposes. In particular, they refer to compounds suitable for combating plant pathogenic organisms such as harmful plants, native plants, plant pathogenic fungi, plant pathogenic arthropods, e.g., plant pathogenic insects and arachnids, plant pathogenic nematodes, and molluscs. Thus, the term "pesticidal compound" includes herbicides, fungicides, insecticides, nematicides, and molluscicides. The term "pesticidal compound" also includes plant growth regulators, i.e., compounds that retard or reduce the growth of crop plants, and herbicide antidotes, i.e., compounds that reduce the phytotoxic effects of herbicides on crop plants.

[0024] With respect to a pesticide compound, the term "water-insoluble or sparingly water-soluble" means that the pesticide compound is insoluble in deionized water, i.e., its solubility in deionized water is less than 0.1 g / L, or 5 g / L or less, or 3 g / L or less, particularly 2 g / L or less, for example, 0.1 to 5 g / L, particularly 0.1 mg / L to 3 g / L, or 0.1 mg / L to 2 g / L. The values ​​given herein refer to the solubility of the pesticide in deionized water as measured at 20°C and 1 bar. In this context, the term "water-soluble" means that the pesticide is soluble in deionized water, i.e., its solubility is greater than 5 g / L, particularly at least 10 g / L, and more particularly at least 20 g / L, as measured at 20°C and 1 bar, at least in deionized water. A water-soluble pesticide compound is also completely miscible with deionized water at 20°C and 1 bar.

[0025] The term "alkyl" refers to alkyl groups containing, for example, 1 to 40 carbon atoms (C1-C 40 Alkyl), especially those with 1 to 20 carbon atoms (C1 to C 20 alkyl), or 8 to 40 carbon atoms (C8 to C 40 alkyl), or 8 to 20 carbon atoms (C8 to C 20"C1-C4 alkyl" refers to a monovalent straight or branched chain saturated hydrocarbon group having one to four carbon atoms (C1-C4 alkyl). Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1 ,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, n-octyl, 2-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, 3,7-dimethyloctan-1-yl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and heneicosyldocosyl include their isomers, in the case of nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and heneicosyldocosyl. Examples of C1-C4 alkyl are, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl. The term "alkyl" also includes saturated hydrocarbon groups resulting from the oligomerization of C2-C4 olefins, such as ethylene, propene, 1-butene, and isobutene. These groups usually have 6 to 40 carbon atoms and are a mixture of different isomers.

[0026] The term "alkylene" refers to, for example, alkylenes having 2 to 40 carbon atoms (C 40Alkylene), especially those with 2 to 20 carbon atoms (C2 to C 20 alkylene), or 8 to 40 carbon atoms (C8 to C 40 alkylene), or 8 to 20 carbon atoms (C8 to C 20 alkylene), or 2 to 10 carbon atoms (C2 to C 10 "Alkylene" refers to a divalent, straight or branched chain saturated hydrocarbon group having the substituents (alkylene). Examples of alkylene include, but are not limited to, 1,2-ethanediyl, 1,2- or 1,3-propanediyl, 1,4-butanediyl, 2-methylpropane-1,3-diyl, 1,1-dimethylethane-1,2-diyl, 1,5-pentanediyl, 1,6-hexanediyl, 2,2-dimethylpropane-1,3-diyl, 1,2-octanediyl, 1,8-octanediyl, 1,10-decanediyl, 3,7-dimethyloctane-1,7-diyl, and 3,7-dimethyloctane-1,8-diyl.

[0027] The term "alkenyl" refers to, for example, an alkenyl group having 2 to 40 carbon atoms (C 40 alkenyl), especially those with 2 to 20 carbon atoms (C2 to C 20 alkenyl), or 8 to 40 carbon atoms (C8 to C 40 alkyl), or 8 to 20 carbon atoms (C8 to C 20

[0033] Alkenyl refers to a monovalent, straight or branched chain, olefinically unsaturated hydrocarbon group having 2 to 4 carbon atoms (C2-C4 alkenyl) and at least one, e.g., 1, 2, or 3, olefinically unsaturated double bond. Examples of alkenyl include, but are not limited to, vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, isotridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyldocosenyl, and the like. In the case of the aryl, undecenyl, dodecenyl, tridecenyl, isotridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, and heneicosenyldocosenyl, examples include their isomers, such as the decenyl isomers 3,7-dimethyloct-6-en-1-yl and 2,6-dimethyl-2,6-octadien-8-yl.

[0028] The term "cycloalkyl" refers to, for example, a group of 3 to 10 carbon atoms (C 10 "C5-C8 cycloalkyl" refers to a saturated cyclic hydrocarbon group having 5 to 8 carbon atoms (cycloalkyl) or 5 to 8 carbon atoms (C5-C8 cycloalkyl). Examples of cycloalkyl include, but are not limited to, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, and cyclohexadecyl.

[0029] The terms "bicycloalkyl" and "tricycloalkyl" refer to saturated bicyclic and tricyclic hydrocarbon groups. "Bicycloalkyl" typically refers to a ring structure having 6 to 12 carbon atoms (C6-C7). 12 Bicycloalkyl) and tricycloalkyl) typically have 8 to 12 carbon atoms. Examples of bicycloalkyl and tricycloalkyl include norbornyl (= bicyclo[2.2.1]heptyl), isobornyl (= 1,7,7-trimethylbicyclo[2.2.1]heptyl), decalinyl (= bicyclo[4.4.0]decyl), and adamantyl (= tricyclo[3.3.1.1]).3.7 ]decyl).

[0030] Herein and throughout the specification, the terms "wt%" and "% by weight" have the same meaning.

[0031] "Molecular weight Mn" or "molar mass Mn" refers to the number-average molecular weight or number-average molar mass. "Molecular weight Mw" or "molar mass Mw" refers to the weight-average molecular weight or weight-average molar mass. Unless otherwise specified, Mn and Mw were determined by size exclusion chromatography (SEC) performed by a method similar to that described in S. Chen et al., Polym. Chem., 2014, 5(18), 5310, using a polyester copolymer as the stationary phase, dimethylformamide + 0.5% LiBr as the eluent, and polymethyl methacrylate standards (molar mass range 800-2,200,000 g / mol) similar to standard methods disclosed in the art.

[0032] For lower molecular weights, 1 The number average molecular weight can also be determined by 1 H NMR spectroscopy.

[0033] The degree of substitution is determined as described by M. H. Alves et al. (ibid.) 1 The degree of substitution was determined by H NMR spectroscopy from the amount of anomeric hydroxyl relative to the methyl group in the terpene. The degree of substitution refers to the average number of hydrophobic compounds selected from terpenes, polyterpenes, and polyterpene ethers relative to the average number of sugar repeating units in the polysaccharide compound.

[0034] The conjugates used in accordance with the present invention comprise a sugar compound selected from disaccharides, oligosaccharides and polysaccharides. Preferably, the molecules of the conjugate comprise a single sugar compound per molecule.

[0035] For the purposes of the present invention, the term "disaccharide" is understood as a sugar compound whose molecule has two identical or different monosaccharide units linked by a glycosidic bond to form a disaccharide molecule.

[0036] For the purposes of the present invention, the terms "oligosaccharide" and "polysaccharide" refer to a sugar compound having, on average, at least 3, e.g., 3 to 1000, in particular 3 to 500 identical or different monosaccharide units linked by glycosidic bonds to form a linear or branched oligosaccharide or polysaccharide molecule. In this regard, the boundary between oligosaccharide and polysaccharide is not clearly defined. Typically, the term "oligosaccharide" refers to a sugar compound whose molecules have, on average, 3 to 10 identical or different monosaccharide units linked by glycosidic bonds to form a linear or branched oligosaccharide molecule. Typically, the term "polysaccharide" is understood as a sugar compound whose molecules have, on average, more than 10, e.g., 10 to 1000 or 10 to 500 identical or different monosaccharide units linked by glycosidic bonds to form a linear or branched polysaccharide molecule.

[0037] Preferably, the sugar compound of the conjugate has a number average of 2 to 1000, particularly 5 to 1000, and especially 10 to 500 repeating monosaccharide units. The number average of repeating monosaccharide units is related to the molecular weight of the sugar compound and can therefore be determined by size exclusion chromatography using a multi-angle light scattering detector, as described, for example, by S. Laemmche et al. in "Characterization of molecular parameters of dietary fiber components from pea and lupins with regard to their physico-chemical properties", Doctoral Thesis, pp. 31-36, TU Berlin, 2004. Alternatively, the number average molecular weight can be determined by osmometry, as described by Y. Rong, M. Sillick, and C M. Gregson in Journal of Food Science, 2009, 74(1), pp. C33-040 ("Determination of Dextrose Equivalent Value and Number Average Molecular Weight of Maltodextrin by Osmometry").

[0038] Suitable polysaccharides have a number average molecular weight (Mn) in the range of 1000 to 100000 daltons, in particular in the range of 1200 to 70000 daltons, especially in the range of 1300 to 50000 daltons, and a weight average molecular weight (Mn) in the range of 1100 to 1500000 daltons, in particular in the range of 1500 to 1000000 daltons, especially in the range of 2000 to 500000 daltons. W ) The dispersity, i.e., M W / M N The ratio is usually in the range of 1.5 to 20, particularly in the range of 1.5 to 12. The molecular weights indicated herein refer to values ​​determined by size exclusion chromatography as described above.

[0039] Typically, suitable polysaccharides are characterized in that a 2% by weight solution of their sodium salt in deionized water has a Brookfield viscosity in the range of 2 to 20,000 mPas, in particular in the range of 5 to 10,000 mPas, and especially in the range of 10 to 5,000 mPas. Viscosity values ​​herein refer to values ​​determined by a Brookfield rotational viscometer in accordance with DIN ISO 2555:2018-09 at 25°C and at a rotational speed of 20 revolutions per minute using spindle RV5.

[0040] In the case of oligosaccharides and polysaccharides, the sugar molecules may be linear or branched.

[0041] A sugar compound may be composed of repeating units of the same or different sugars. The repeating sugar units forming the sugar compound are typically selected from nonionic hexoses and nonionic deoxyhexoses, such as glucose, mannose, rhamnose, arabinose, and galactose, and combinations thereof. However, the repeating sugar units may also include anionic monosaccharide units, such as galacturonic acid, and / or basic monosaccharide units, such as glucosamine or N-acetylglucosamine.

[0042] The sugar compounds are typically non-ionic sugar compounds and are selected from non-ionic disaccharides, non-ionic oligosaccharides and non-ionic polysaccharides. In particular, the sugar compounds are non-ionic disaccharides, oligosaccharides or polysaccharide compounds formed by aldohexoses, especially glucose. In particular, the sugar compounds are selected from non-ionic oligosaccharides or polysaccharides, especially non-ionic oligosaccharides or polysaccharides formed by aldohexoses, especially glucose.

[0043] Suitable oligosaccharides are in particular starch degradation products having an average number of glucose units in the range of 3 to 10, which corresponds to a DE (dextrose equivalent) value in the range of 10 to 40. DE is a measure of the amount of reducing sugars present in the sugar product and is expressed as a percentage on a dry basis compared to dextrose. DE is usually determined according to the method of Lane and Eynon, expressed as % invert sugar, or according to the method of Luff-Schoorl, expressed as meq glucose / g. The respective methods are described in the Official Journal of the European Communities No. L / 239 / 24-52 of 22.09.1979 (79 / 78 6 / EEC), methods 6 (Luff-Schoorl) and 7 or 8 (Lane and Eynon).

[0044] In a preferred group of embodiments, the sugar compound of the conjugate is an oligosaccharide or polysaccharide compound having an average (number average) of 5 to 1,000 or 10 to 500 identical or different monosaccharide units linked by glycosidic bonds to form a linear or branched polysaccharide molecule. The polysaccharide is in particular a glucan, i.e., a polysaccharide made from glucose units. In particular, the glucan is an α-glucan, in particular selected from the group of starch degradation products (degraded starches), such as dextran, pullulan, and dextrin. Thus, the polysaccharide of the conjugate is a glucan, in particular selected from dextran, pullulan, dextrin, and combinations thereof. In a preferred group of embodiments, the polysaccharide of the conjugate is a dextran, i.e., an α-1,6-glucan containing α-1,3-branched chains.

[0045] The conjugate of the present invention comprises at least one hydrophobic compound. According to the present invention, the hydrophobic compound is selected from terpenes, polyterpenes, and polyterpene ethers. The hydrophobic compound may be directly bound to an atom of the sugar compound, such as a carbon or oxygen atom of the sugar compound, by a covalent bond or a bivalent linker group, or may be present as a group R derived from a terpene compound, a polyterpene, or a polyterpene ether compound.

[0046] Thus, the conjugate molecule comprises at least one group R that is a group of a terpene, polyterpene or polyterpene ether molecule.

[0047] The term "terpenyl group" refers to groups derived from terpenes, terpene alcohols and oxygenated terpene alcohols, in particular from acyclic, monocyclic or bicyclic monoterpenes or sesquiterpenes, or from monoterpene or sesquiterpene alcohols, as described herein.

[0048] The term "polyterpene group" refers to a group of polyterpenes.

[0049] The term "polyterpene ether group" refers to a group of polyterpene ethers.

[0050] The term "terpene alcohol" refers to a terpene having an alcoholic OH (hydroxyl) group.

[0051] Terpenes may be hydrocarbon terpenes, terpene alcohols, and oxidized terpene alcohols, in particular monoterpenes, sesquiterpenes, diterpenes, monoterpene alcohols (monoterpenols), sesquiterpene alcohols (sesquiterpenols), diterpene alcohols (diterpenols), oxidized monoterpene alcohols (monoterpenol oxidized), oxidized sesquiterpene alcohols (sesquiterpenol oxidized), or oxidized diterpene alcohols (diterpenol oxidized). In this context, the terms terpene and terpene compound refer to hydrocarbon terpene compounds, respectively. The term terpene alcohol refers to a terpene compound having a hydroxyl group, in particular a single hydroxyl group. The term oxidized terpene alcohol refers to a terpene alcohol in which the hydroxyl group has been converted to an aldehyde group, a keto group, or a carboxyl group. Respectively, monoterpenes, monoterpene alcohols and oxidized monoterpene alcohols have 10 carbon atoms, sesquiterpenes, sesquiterpene alcohols and oxidized sesquiterpene alcohols have 15 carbon atoms, and diterpenes, diterpene alcohols and oxidized diterpene alcohols have 20 carbon atoms. Terpenes from the group of monoterpenes, monoterpene alcohols, oxidized monoterpene alcohols, sesquiterpenes, sesquiterpene alcohols and oxidized sesquiterpene alcohols are preferred.

[0052] Terpene compounds may be saturated or may have an olefinic double bond. They may be acyclic or alicyclic. Preferred terpene compounds are acyclic terpene compounds and alicyclic terpene compounds having a single 5- or 6-membered hydrocarbon monocycle or a single 6- to 9-membered hydrocarbon bicycle. Particularly preferred terpene compounds have 10 to 15 carbon atoms and are selected from acyclic terpene compounds and alicyclic terpene compounds having a single 5- or 6-membered hydrocarbon monocycle or a single 6- to 9-membered hydrocarbon bicycle.

[0053] Examples of acyclic terpene compounds include, but are not limited to, citronellol, geraniol, nerol, linalool, myrcenol, lavandulol, ipsdienol, farnesol, and nerolidol. Examples of cyclic terpene compounds include, but are not limited to, menthol, terpineol, terpinene, pulegol, borneol, and isoborneol.

[0054] In a particular group (0) of embodiments, the hydrophobic compound is selected in particular from mono-, sesqui-, and diterpenols, oxidized mono-, sesqui-, and diterpenols, and polyterpene ether compounds, the terpene units of which are selected from terpenol compounds derived from mono-, sesqui-, and diterpenols. In a particular group (0) of this embodiment, the hydrophobic compound is selected in particular from monoterpenols, sesquiterpenols, oxidized monoterpinols, and oxidized sesquiterpenols. In this particular group of embodiments, preferred terpenol compounds and oxidized terpenol compounds are acyclic terpenol compounds, oxidized terpenol compounds, alicyclic terpenol compounds, and oxidized alicyclic terpenol compounds, the alicyclic terpenol compounds and oxidized alicyclic terpenol compounds having a single 5- or 6-membered hydrocarbon monocycle or a single 6- to 9-membered hydrocarbon bicycle. Particularly preferred terpenol compounds and oxidized terpenol compounds of group (0) of this embodiment have 10 to 15 carbon atoms and are selected from acyclic terpenol compounds, oxidized acyclic terpenol compounds, alicyclic terpenol compounds, and oxidized alicyclic terpenol compounds, where the alicyclic terpenol compounds and oxidized alicyclic terpenol compounds have a single 5- or 6-membered hydrocarbon monocycle or a single 6- to 9-membered hydrocarbon bicycle. In particular group (0) of this embodiment, the hydrophobic compound may also be a polyterpene ether compound, preferably derived from monoterpenols and sesquiterpenols, in particular from acyclic monoterpenols and acyclic sesquiterpenols.

[0055] In group (0) of this embodiment, the terpenols are, inter alia, citronellol, geraniol, nerol, linalool, myrcenol, lavandulol, ipsdienol, farnesol, nerolidol, menthol, terpineol, pulegol, borneol and isoborneol, with citronellol, nerol, geraniol, myrcenol, pulegol, menthol and combinations thereof being particularly preferred.

[0056] In group (0) of this embodiment, the polyterpene ether compounds are derived in particular from citronellol, geraniol, nerol, linalool, myrcenol, lavandulol, ipsdienol, farnesol, nerolidol, menthol, terpineol, pulegol, borneol and isoborneol, with citronellol, nerol, geraniol, myrcenol and combinations thereof being particularly preferred.

[0057] In a particular group (1) of embodiments, the group R in formulae (I) and (II) is selected from the group of terpenyl groups, in particular monoterpenyl and sesquiterpenyl groups. In this context, it is clearly understood that the terpinyl group R is derived from a terpinol or terpinol oxide of formula R-OH. The term "derived from" is therefore clearly understood to mean that the moieties R and R in formulae (I) and (II) are derived from ROH, which is a terpinol or terpinol oxide, respectively. In this particular group (1) of embodiments, the group R in formulae (I) and (II) is derived in particular from a monoterpenol or sesquiterpenol, in particular from an acyclic mono- or sesquiterpenol, or from an alicyclic mono- or sesquiterpenol having a single 5- or 6-membered hydrocarbon monocycle or a single 6- to 9-membered hydrocarbon bicycle. In group (1) of this embodiment, the group R is in particular citronellol, geraniol, nerol, linalool, myrcenol, lavandulol, ipsdienol, farnesol, nerolidol, menthol, terpineol, pulegol, borneol and isoborneol, with citronellol, nerol, geraniol, myrcenol, pulegol, menthol and combinations thereof being particularly preferred.

[0058] In group (1a) of a particular subgroup of group (1) of embodiments, the group R in formulas (I) and (II) is selected from 3,7-dimethyloct-6-en-1-yl, 3,7-dimethyloctan-1-yl, 2,6-dimethyl-2,6-octadien-8-yl and 5-methyl-2-(propan-2-yl)-cyclohexan-1-yl.

[0059] In another group (2) of embodiments, the group R in formulas (I) and (II) is a polyterpene ether group in which the terpene units of the polyterpene ether have 10, 15 or 20 carbon atoms, particularly 10 or 15 carbon atoms, and especially 10 carbon atoms. The polyterpene ether may have a terminal hydrogen atom or an alkyl or alkenyl group having 8 to 20 carbon atoms. In group (2) of embodiments, polyalkylene ether groups derived from acyclic terpenes, especially from acyclic mono- and sesquiterpenes, are preferred.

[0060] In particular, the terpene units in the polyterpenyl ether group have the formula Alk: [ka] (In the formula, R 1 represents a straight or branched chain alkylene group having 6, 11 or 16 carbon atoms, especially 6 or 11 carbon atoms, and the zigzag line indicates the point of attachment to the oxygen atom of the polyalkylene ether.

[0061] In particular, the polyterpenyl ether group has the formula PAE: [ka] (In the formula, R 1 represents a straight or branched chain alkylene group having 6, 11 or 16 carbon atoms, particularly 6 or 11 carbon atoms; n is an integer from 0 to 20, particularly from 0 to 10, and especially from 0 to 4; and the zigzag line indicates the point of attachment of the linker or sugar to the carbon atom.

[0062] The preferences indicated for the sugar compounds in the groups (1), (1a) and (2) of embodiments apply analogously. In particular, the sugar compounds are selected from disaccharide compounds, oligosaccharide compounds and polysaccharide compounds, and the polysaccharides are α-glucans, such as dextran, amylose, pullulan, starch and starch degradation products, such as dextrin. In the groups (1), (1a) and (2) of embodiments, the sugar is, in particular, dextran.

[0063] The weight ratio of the group R to the polysaccharide in the nonionic conjugate is often in the range of 20:1 to 1:80. When the polysaccharide is used as a stabilizer for an oil-in-water emulsion, the weight ratio of the group R to the polysaccharide in the nonionic conjugate is preferably in the range of 1:1.5 to 1:80, particularly preferably in the range of 1:2 to 1:60.

[0064] In the conjugates of the present invention, particularly in the embodiments (1) and (1a), the sugar compound is substituted with at least one hydrophobic compound selected from terpenes, polyterpenes, and polyterpene ethers. The sugar compound of the conjugate may have a single hydrophobic compound or a degree of substitution with the hydrophobic compound or group R in the range of up to 300 mol %, particularly in the range of 1 to 200 mol %, and especially in the range of 1 to 100 mol %, based on the monosaccharide unit of the sugar compound. When the conjugates of the present invention are used as oil-in-water emulsions, the sugar of the conjugate preferably has a degree of substitution in the range of 1 to 100 mol %, particularly in the range of 5 to 100 mol %, and especially in the range of 5 to 60 mol %, based on the monosaccharide unit of the sugar compound.

[0065] The group R may be covalently attached directly to one atom of the sugar, such as an oxygen atom, or may be covalently attached to the sugar via a linker, depending on the method used to generate the conjugate. Typically, the linker has one or two functional groups, such as a carbonyl, carboxyl, carbamide or urethane group, or a secondary amino or imine group, where one group results from the reaction of the hydrophobic compound with the carbohydrate, while the optional second group may result from functionalization or activation of the hydrophobic compound.

[0066] In particular groups (3) and (4) of embodiments of the present invention, the terpene compound has the formula (I) (group 3) or the formula (II) (group 4): RO-(Y) k -A 1 -X 1 - (I) (In formula (I), the variables R, k, Y, A 1 , X 1is as defined herein, wherein: R is in particular a terpenyl group; k is 0 or 1, in particular 1; Y is C(O) or C(O)NH, in particular C(O); A 1 is a direct bond or an alkylene having 1 to 6 carbon atoms (C1-C6 alkylene), in which case A 1 is in particular a C2-C6 alkylene; X 1 may be C(O) or OC(O) or NHC(O), in which case, in particular, k=1 and A 1 When is C2-C6 alkylene, X 1 is C(O), X 1 is attached to an oxygen atom of a sugar compound, especially an oxygen atom of a polysaccharide); RO-(Y) k -A 1 -X 2 -A 2 -X 3 - (II) (In formula (II), the variables R, k, Y, A 1 , A 2 , X 2 and X 3 is as defined herein, wherein: R is in particular a terpenyl, polyterpene or polyterpenyl ether group, k is 0 or 1, in particular 1; Y is C(O) or C(O)NH, in particular C(O), A 1 is a direct bond or an alkylene having 1 to 6 carbon atoms (C1-C6 alkylene), in which case A 1 is in particular a C2-C6 alkylene; X 2 is C(O)NH or NHC(O)NH, in particular C(O)NH, A 2 is an alkylene having 2 to 10 carbon atoms (C2 to C 10 Alkylene), especially C2-C10 alkylene, wherein 1, 2, or 3 non-adjacent carbon atoms of the alkylene are optionally replaced by oxygen atoms; X 3 - is N= or NH-, i.e., an imino or amino nitrogen; X 3 is attached to the oxygen atoms of sugar compounds, especially polysaccharides) The group is present in the conjugate molecule in the form of one of the following groups:

[0067] Particularly preferred are conjugates of group (3) of embodiments: RO-(Y) k -A 1 -X 1 - (I) (In formula (I), the variables R, k, Y, A 1 , X 1 is as defined herein, wherein: R is in particular a terpenyl group; k is specifically 1; Y is C(O); A 1 is in particular a C2-C6 alkylene; X 1 is C(O) is.

[0068] In groups (3) and (4) of embodiments, the group R is preferably according to groups (1), (1a) and (2). In groups (3) and (4) of embodiments, the preferences given for sugars apply analogously. In particular, polysaccharides that are α-glucans, such as dextran, amylose, pullulan, starch and starch degradation products, e.g., dextrins, are preferred. In groups (3) and (4) of embodiments, the sugar is, inter alia, dextran.

[0069] In particular, the sugars of the conjugates of embodiments (3) and (4) have a degree of substitution with the group of formula (I) or (II) in the range of 1 to 300 mol %, particularly in the range of 5 to 200 mol %, based on the monosaccharide units of the sugar. When the conjugates of embodiments (3) and (4) are used as o / w emulsions, it is preferred that the sugars of the conjugates have a degree of substitution with the group of formula (I) or (II) in the range of 1 to 100 mol %, particularly in the range of 5 to 100 mol %, and especially in the range of 5 to 60 mol %, based on the monosaccharide units of the sugar.

[0070] According to group (5) of embodiments, the conjugate is a polysaccharide graft copolymer. In this graft copolymer, the polysaccharide forms the backbone and the hydrophobic compound is linked directly or via a linker to the repeating monosaccharide units of the polysaccharide backbone, i.e., the group R is present as a group of formula (I) or (II), respectively. The graft copolymer generally can have a degree of substitution with the hydrophobic compound or group (I) or (II), respectively, in the range of 1 to 300 mol %, particularly in the range of 5 to 200 mol %, and especially in the range of 10 to 200 mol %, relative to the monosaccharide units of the polysaccharide. When the conjugate of group (5) of embodiments is used in an oil-in-water emulsion, the sugar of the conjugate preferably has a degree of substitution in the range of 1 to 100 mol %, particularly in the range of 5 to 100 mol %, and especially in the range of 5 to 60 mol %, relative to the monosaccharide units of the saccharide.

[0071] In group (5) of embodiments, the radical R is preferably according to groups (1), (1a) and (2) of embodiments. In particular, the radical R is a terpenyl group or a polyterpenyl ether group. In group (5) of embodiments, the radical R is preferably present as a radical of formula (I) as defined in group (3) of embodiments. In group (5) of embodiments, the preferences given for polysaccharides apply analogously. In particular, the polysaccharide is an α-glucan such as dextran, pullulan and starch degradation products, e.g., dextrin. In group (5) of embodiments, the polysaccharide is, in particular, dextran.

[0072] According to another group (6) of embodiments, the conjugate is a block copolymer. Such a block copolymer comprises a polysaccharide block and at least one block formed by a hydrophobic compound attached to at least one of the terminal saccharide units of the polysaccharide block. When the polysaccharide is linear, it has one or two hydrophobic compounds attached to its terminals.

[0073] In group (6) of embodiments, the group R is preferably according to groups (1), (1a) and (2) of embodiments. In particular, the group R is a polyterpenyl ether group. In group (5) of embodiments, the group R is preferably present as a group of formula (II) as defined in group (4) of embodiments. In group (6) of embodiments, the preferences given for polysaccharides apply analogously. In particular, the polysaccharide is an α-glucan such as dextran, pullulan, starch and starch degradation products, e.g., dextrin. In group (6) of embodiments, the polysaccharide is, in particular, dextran.

[0074] The weight ratio of the hydrophobic compound to the sugar compound in the conjugate is in the range of 3:1 to 1:80, particularly in the range of 2:1 to 1:60.

[0075] In one particularly preferred group (7) of embodiments, the hydrophobic compound in the conjugate is either directly bonded to an oxygen atom of the sugar or is present as a group of formula (I). When the hydrophobic compound in the conjugate is directly bonded to an oxygen atom of the sugar compound, the hydrophobic compound is preferably an oxidized terpenol having a carboxyl group that forms an ester group with the oxygen atom of the sugar compound.

[0076] In another particularly preferred group (8) of embodiments, the hydrophobic compound is present as a group of formula (II), in which R in formula (II) is, inter alia, a polyterpene ether group.

[0077] The conjugates of the present invention can be prepared by methods similar to known methods for producing conjugates of sugars and hydrophobic organic compounds, as described, for example, in CN112390834, JP03292301A, JP61069801A, L.Billon et al. Biomacromolecules (2014), 15(1), 242-251, S.Otto et al. Carbohydrate Polymers 254(2021) 117280, A.Durand et al. Langmuir (2004), 20, 6956-6963, Save et al. Biomacromolecules (2022), 23, 2536-2551.

[0078] For example, a compound of formula (III) RL (III) where R is as defined herein and L is a leaving group such as bromine, iodine, C1-C4 alkylsulfonate or tolylsulfonate, is reacted with a sugar, typically in the presence of a basic catalyst, thereby covalently attaching the group R to an oxygen atom of the sugar.

[0079] Also, the compound of formula (IV) R-OH (IV) It is also possible to start with compound (IV), where R is as defined herein, in which the OH group is activated to form a leaving group or is coupled with a compound bearing a further functional group capable of forming a covalent bond with one of the OH groups of the sugar or with another reactive group previously introduced on the sugar.

[0080] For example, compounds of formula (IV) can be converted to reactive esters such as chloroformate esters or carbonates of formula (IVa) or (IVb) which can react with OH groups of sugars. ROC(O)-Cl (IVa) ROC(O)-OR' (IVb)

[0081] In the compounds of formula (IVa) and (IVb), the group R is as defined herein, and the group R' in formula (IVb) is C1-C4 alkyl, for example methyl or ethyl, or hydrogen.

[0082] In a particularly preferred group of embodiments, compound (IV) is a compound of formula (V) RO-(Y) k -AZ (V) (In the formula, R is as defined herein; k is 0 or 1, in particular 1; Y is C(O) or C(O)NH, in particular C(O), A is a direct bond or a divalent hydrocarbon group, particularly an alkylene group having 1 to 6 carbon atoms; Z is either an isocyanate group, a COOH group, or an activated carboxyl group such as a reactive ester group, e.g., a COOR' group, or an anhydride group. is converted into

[0083] For example, a compound of formula (IV) may be reacted with an aliphatic dicarboxylic acid having 2 to 8 carbon atoms, or a di-C1-C4 alkyl ester thereof, under esterification conditions to give a compound of formula (V) where k=1, Y=C(O), and Z=COOH or C(O)-O-C1-C4 alkyl. Suitable dicarboxylic acids include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, and pimelic acid.

[0084] Alternatively, the compound of formula (IV) may be reacted with an aliphatic diisocyanate having 3 to 8 carbon atoms under urethane-forming reaction conditions to obtain a compound of formula (V) (wherein A is alkylene having 1 to 6 carbon atoms, k=1, Y=C(O)NH, and Z=N=C=O) under the conditions described, for example, in JP-A-03292301. Suitable diisocyanates include, for example, methane diisocyanate, ethane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, and hexane diisocyanate.

[0085] The compound of formula (IV) can be prepared by reacting a compound of formula (VI) LAC(O)-OR'' (VI) wherein L is a leaving group such as Br or I, A is alkylene having 1 to 6 carbon atoms, and R″ is H or C1-C4 alkyl. It may be reacted with

[0086] Obviously, the compounds of formulae (IVa), (IVb) and (V) thus obtained retain functional groups that react with the OH groups of the sugars and can therefore be coupled with sugars under suitable reaction conditions as described in the prior art or in the examples of this application, thereby obtaining conjugates of sugars with compounds of formulae (IVa), (IVb) and (V). In a preferred group of embodiments, these conjugates are in the form of graft polymers in which some of the OH groups of the polysaccharide compound have been replaced by groups bearing the group R, for example groups of formula (I).

[0087] Sugars can also be activated by introducing one or more reactive groups that can react with suitable compounds bearing the group R. For example, sugars can be activated by coupling them to diamino compounds bearing two primary amino groups, particularly those of the formula H2N-A'-NH2, where A' is C2-C 10 alkylene, in this case C2 to C 10 C2 to C2 of alkylene, 1, 2 or 3 non-adjacent carbon atoms of which may be replaced by oxygen atoms 10The terminal sugar unit may be reacted with an alkylenediamine, which converts the aldehyde carbon atom of the terminal sugar moiety to an imine, which is then hydrogenated to yield a sugar having an aminoalkylamino group on the terminal sugar moiety. The primary amino group of the aminoalkylamine group may be reacted with a compound of formula (IVa), (IVb), or (V), thereby yielding a conjugate in which the terminal sugar unit bears a group R in the form of a group of formula (II).

[0088] X 1 Preferred group (3) conjugates of the embodiment in which Z is C(O) are prepared by reacting a sugar compound with a compound of formula (V) (wherein Z is COOH) in the presence of an enzyme capable of catalyzing an esterification reaction, such as a lipase, especially an immobilized lipase. Similarly, conjugates can be prepared in which an oxidized terpenol compound having a carboxyl group is directly attached to a sugar compound. X 2 Preferred group (4) conjugates of the embodiment in which is C(O)NH are those which can be amidated by the addition of at least one group NH-A in the presence of an enzyme capable of catalyzing an amidation reaction, such as a lipase, particularly an immobilized lipase. 2 -X 3 - with a compound of formula (V) where Z is COOH. Similarly, conjugates can be prepared in which an oxidized terpenol compound having a carboxyl group is directly attached to a sugar compound. These processes have not yet been described in the art and are therefore part of the present invention.

[0089] Therefore, the present invention also provides a method for the preparation of a sugar compound or at least one group NH2-A in the presence of an enzyme capable of catalyzing an esterification or amidation reaction, such as a lipase, in particular an immobilized lipase. 2 -X 3 - with a compound of formula (V) wherein Z is COOH, or an oxidized terpene alcohol having a carboxyl group.

[0090] Preferably, the sugar compound used in the process of the present invention optionally contains at least one group NH2-A 2 -X 3 In particular, the polysaccharide compound is selected from α-glucans such as dextran, pullulan, starch and starch degradation products, e.g., dextrins. In particular, the polysaccharide compound optionally has at least one group NH2-A 2 -X 3 - is a dextran having the formula:

[0091] Suitable enzymes capable of catalysing esterification or amidation reactions, such as lipases, are commercially available, for example, from Novozyme.

[0092] The reaction is preferably carried out in an aprotic organic solvent such as dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, acetonitrile, tetrahydrofuran, dimethylpropylene urea, acetone, butanone, sulfolane, pyridine, triethylamine, hexamethylphosphoramide, or mixtures thereof.

[0093] Preferably, the water formed in the esterification or transesterification reaction is removed, for example, by distillation and / or by using molecular sieves.

[0094] As noted above, the conjugates of the present invention, preferably the non-ionic conjugates of the present invention, stabilize aqueous emulsions of water-immiscible liquids by incorporating a stabilizing amount of the conjugate into the emulsion of the water-immiscible liquid.

[0095] Preferably, the aqueous emulsion of a water-immiscible liquid is an oil-in-water emulsion (o / w emulsion). An oil-in-water emulsion is defined as a mixture containing two immiscible liquids, i.e., oil and water, with the oil distributed in the water. Thus, oil constitutes the dispersed phase of an o / w emulsion, while water constitutes the continuous phase. In a water-in-oil emulsion (w / o emulsion), water constitutes the dispersed phase in a continuous oil phase.

[0096] The droplet size can be controlled depending on the energy input to the mixture of the aqueous phase and the water-immiscible liquid. Furthermore, the type and amount of the dispersant described above influences the droplet size of the equilibrium emulsion. The appropriate amount can be routinely selected. For the purposes of the present invention, it has been found to be beneficial if the final average particle size D[v,0.5] of the microparticles does not exceed 400 μm, particularly 200 μm, and especially 100 μm.

[0097] In this specification and below, all figures for particle size, particle diameter, and particle size distribution, including the D[v,0.1], D[v,0.5], D[v,0.9], D[4,3], and D[3,2] values, are based on particle size distributions determined by static laser light scattering according to ISO 13320:2009 on small particle samples. The abbreviation SLS is also used hereinafter for the expression "Static Laser Light Scattering according to ISO 13320:2009." In this context, a D[v,0.1] value means that 10% by volume of the particles in the measured sample have a particle diameter less than the value reported as D[v,01]. Thus, a D[v,0.5] value means that 50% by volume of the particles in the measured sample have a particle diameter less than the value reported as D[v,0.5], and a D[v,0.9] value means that 90% by volume of the particles in the measured sample have a particle diameter less than the value reported as D[v,0.9]. The D[4,3] value is the volume-weighted average determined by SLS, also known as the De Brouckere average, which corresponds to the mass average of the particles of the present invention. The D[3,2] value is the surface-weighted average determined by SLS, also known as the Sauter mean diameter (SMD).

[0098] Agitation typically produces droplets with an average droplet size D[v,0.5] of at most 400 μm or less, but particularly at most 200 μm, more particularly at most 100 μm, for example in the range of 0.5 to 400 μm, particularly 1 to 200 μm, and especially 1 to 100 μm, achieved by devices for generating high shear fields. It is also possible to introduce sufficient shear energy by vigorous agitation to achieve average droplet sizes with D[v,0.5] values ​​in the range of 0.5 to 400 μm, preferably 1 to 200 μm, especially 1 to 100 μm. If even higher shear energy inputs are intended, it may be advantageous to use devices for generating high shear fields.

[0099] By controlling the droplet size and droplet size distribution of an emulsion, particularly an oil-in-water emulsion, it is possible to control the particle size and particle size distribution of the final droplets containing the organic active compound. In other words, a small average particle size of the droplets is achieved by providing an emulsion, particularly an oil-in-water emulsion, with a small average droplet size; similarly, a narrow droplet size distribution of an emulsion, particularly an oil-in-water emulsion, will result in the resulting droplets containing the organic active compound having a narrow particle size distribution.

[0100] Suitable agitator types include propeller agitators, impeller agitators, disk agitators, paddle agitators, anchor agitators, pitched blade agitators, cross beam agitators, helical agitators, screw agitators, and the like.

[0101] Suitable devices for shearing, i.e., generating a high shear field, are dispersers operating on the rotor-stator principle, i.e., rotor-stator mixers, such as toothed ring dispersers, also known as gear dispersers, colloid mills and disc mills, high-pressure homogenizers, also known as high-pressure mixers, and ultrasonic homogenizers. High shear can also be achieved by using single- or multi-stage dispersion disc or cross-blade agitators. Among shearing devices, dispersers operating on the rotor-stator principle to generate a shear field, particularly toothed ring dispersers, are preferred. The diameters of the rotor and stator typically range from 1 cm to 40 cm, depending on the size and dispersion performance of the machine. The rotation speed of such dispersers is generally in the range of 500 to 20,000 rpm, particularly 1,000 to 15,000 rpm (revolutions per minute), depending on the type of design. Naturally, machines with larger rotor diameters operate at the lower end of the rotational speed range, while machines with smaller rotor diameters usually operate at the upper end of the rotational speed range. The peripheral speed of the rotor is typically in the range of 5-50 m / s. The distance from the stationary to the rotating parts of the dispersion tool is generally 0.1-3 mm.

[0102] As mentioned above, the droplet size can be controlled by inputting shear energy into the mixture of the aqueous phase and the water-immiscible liquid. The shear energy input can be directly derived from the power consumption of the device for generating the shear field, taking into account heat losses. Therefore, the shear energy input into the oil-in-water emulsion is preferably 250 to 25,000 watts h / m. 3 Batch size. Calculated based on motor current, 500-15,000, especially 800-10,000 watt-h / m 3 Batch-sized energy input is particularly preferred.

[0103] In a preferred embodiment, the emulsification is carried out so that the emulsion droplets of the emulsion, particularly the oil-in-water emulsion, have an average diameter D[v,0.5] of at most 400 μm or less, as measured by light scattering, for example, in the range of 0.5 to 400 μm, particularly 1 to 200 μm, and especially 1 to 100 μm. To this end, the emulsification typically involves mixing the solution of step i. with an aqueous phase and homogenizing the mixture. Homogenization is typically achieved by subjecting the mixture to high shear using a suitable device such as those described above. Mixing and homogenization may be carried out sequentially or simultaneously.

[0104] In many cases, the conjugate is used in an amount in the range of 1 to 50% by weight, particularly in the range of 2 to 40% by weight, more particularly in the range of 5 to 35% by weight, especially in the range of 8 to 30% by weight, based on the weight of the water-immiscible liquid phase of an aqueous emulsion, particularly the oil phase of an oil-in-water emulsion containing the pesticidal compound.

[0105] The weight ratio of the conjugate to the water-immiscible liquid in the emulsion is in the range of 1:100 to 1:1, in particular in the range of 1:50 to 1:2, and especially in the range of 1:30 to 1:3.

[0106] For example, aqueous emulsions of water-immiscible liquids can be stabilized by dissolving a conjugate, particularly a nonionic conjugate, in the water used to emulsify the water-immiscible liquid. If the organic active compound is a solid at 22°C, it is preferable to dissolve the solid in a water-immiscible organic solvent and use the resulting solution to form the aqueous emulsion according to the present invention. It may also be possible to first mix the solid or its solution in a water-immiscible organic solvent with the conjugate, and then emulsify the mixture in water.

[0107] Emulsifying a water-immiscible liquid in water in the presence of a conjugate, particularly a non-ionic conjugate, can be achieved by mixing the emulsion-forming components, i.e., the water-immiscible liquid, water, then the conjugate, particularly a non-ionic conjugate, and optionally a water-immiscible organic solvent, in any order in a suitable mixing device. This can be beneficial if the emulsification includes a homogenization step to reduce the droplet size of the non-aqueous droplets of the emulsion. Homogenization can be achieved by well-known methods, for example, by using a microfluidizer or a high-pressure homogenizer.

[0108] The concentration of the water-immiscible liquid in the aqueous emulsion may vary and is typically in the range of 0.1 to 60% by weight, particularly in the range of 1 to 45% by weight, and especially in the range of 1.5 to 40% by weight, based on the total weight of the emulsion.

[0109] The conjugate can be used to stabilize any aqueous emulsion of any water-immiscible liquid.For this purpose, any water-immiscible liquid that can be emulsified in water can be used.For example, if the water-immiscible liquid is liquid at 22 ° C, it can be emulsified by itself without the need for a water-immiscible solvent.If the water-immiscible liquid is solid at 22 ° C, it is preferable to dissolve the solid compound in a water-immiscible solvent and emulsify the solution in water.

[0110] Therefore, suitable water-immiscible liquids are liquids at 22°C, or if solid at 22°C, they can be dissolved in a water-immiscible solvent. Typically, water-immiscible liquids are non-ionic organic compounds. In particular, water-immiscible liquids are non-ionic organic compounds whose molecules have 6 to 50 atoms other than hydrogen, particularly selected from C, O, S, N, P, and the halogens. The miscibility of water-immiscible liquids in water, when measured at 20°C and 1 mbar, generally does not exceed 5 g / l, or is at most 3 g / l, or is at most 2 g / l.

[0111] In particular, the water-immiscible liquid of the aqueous emulsion comprises at least one organic active compound, in particular at least one pesticidal compound, where it is immaterial whether the organic active compound itself is liquid at 22°C and forms non-aqueous droplets in the aqueous emulsion, or whether it is solid at 22°C and is dissolved in a water-immiscible solvent, thereby forming droplets in the emulsion.

[0112] Typically, the organic active compounds are non-ionic organic compounds. In particular, the organic active compounds are non-ionic organic compounds whose molecules have 6 to 50 atoms other than hydrogen, in particular selected from C, O, S, N, P and the halogens. The miscibility of the organic active compounds in water, measured at 20°C and 1 mbar, generally does not exceed 5 g / l, or at most 3 g / l, or at most 2 g / l.

[0113] Preferably, the organic active compound is a water-immiscible liquid at 22° C. and / or is dissolved in a water-immiscible organic solvent.

[0114] The concentration of organic active compound in the composition may vary and typically ranges from 10 to 800 g per kg of composition.

[0115] The organic active compounds are often selected from pesticides, especially pesticides, aroma chemicals, pharmaceutically active compounds, vitamins, cosmetic active substances and organic effective compounds. Pesticides, especially pesticides, are preferred.

[0116] In a preferred group of embodiments, the organic active material is an aroma chemical, especially an aroma chemical that is liquid at 22° C. and 1 bar, or a mixture of two or more aroma chemicals that are liquid at 22° C. and 1 bar. Preferred aroma chemicals are hydrophobic, especially having a water solubility of 1 g / L or less in deionized water at 25° C.

[0117] The term "aromachemicals" is understood by those skilled in the art to mean organic compounds that can be used as "odors" and / or "flavors." In the context of the present invention, "odorants" are understood to mean natural or synthetic substances with a distinctive odor. In the context of the present invention, "flavors" are understood to mean natural or synthetic substances with a distinctive flavor. In the context of the present invention, "odor" or "olfactory perception" refers to the sensory stimulation sent from the chemical receptors of the nose or other olfactory organs to the brain of an organism. Odors can be the result of nasal sensory perception of odorants generated during inhalation. In this case, air acts as an odorant carrier.

[0118] Preferred aroma chemicals are, for example, selected from the following compounds: α-Hexyl cinnamaldehyde, 2-phenoxyethyl isobutyrate (Phenirat 1 ), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably with a cis-isomer content of more than 60% by weight) (Hedione 9 , Hedione HC 9 ), 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]benzopyran (Galaxolide 3 ), tetrahydrolinalool (3,7-dimethyloctan-3-ol), ethyl linalool, benzyl salicylate, 2-methyl-3-(4-tert-butylphenyl)propanal (Lilial 2), cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5-indenyl acetate and / or 4,7-methano-3a,4,5,6,7,7a-hexahydro-6-indenyl acetate (Herbaflorat 1 ), citronellol, citronellyl acetate, tetrahydrogeraniol, vanillin, linalyl acetate, styrenyl acetate (1-phenylethyl acetate), octahydro-2,3,8,8-tetramethyl-2-acetonaphthone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene (Iso E Super 3 ), hexyl salicylate, 4-tert-butylcyclohexyl acetate (Oryclone 1 ), 2-tert-butylcyclohexyl acetate (Agrumex HC 1 ), α-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one), n-α-methylionone, α-isomethylionone, coumarin, terpinyl acetate, 2-phenylethyl alcohol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde (Lyral 3 ), α-amylcinnamaldehyde, ethylene brassylate, (E)- and / or (Z)-3-Methylcyclopentadec-5-enone (Muscenone 9 ), 15-pentadec-11-enolide and / or 15-Pentadec-12-enolide (Globalide 1 ), 15-cyclopentadecanolide (Macrolide 1 ), 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthalenyl)ethanone (Tonalide 10 ), 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol (Florol 9 ), 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (Sandolene 1), cis-3-hexenyl acetate, trans-3-hexenyl acetate, trans-2-cis-6-nonadienol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde (Vertocitral 1 ), 2,4,4,7-tetramethyloct-6-en-3-one (Claritone 1 ), 2,6-dimethyl-5-hepten-1-al (Melonal 2 ), borneol, 3-(3-isopropylphenyl)butanal (Florhydral 2 ), 2-methyl-3-(3,4-methylenedioxyphenyl)propanal (Helional 3 ), 3-(4-ethylphenyl)-2,2-dimethylpropanal (Florazon 1 ), tetrahydro-2-isobutyl-4-methyl-2H-pyran (Dihydrorosenon 4 ), 1,4-bis(ethoxymethyl)cyclohexane (Vertofruct 4 ), L-isopulegol (1R,2S,5R)-2-isopropenyl-5-methylcyclohexanol, pyranyl acetate (2-isobutyl-4-methyltetrahydropyran-4-yl acetate), nerol ((Z)-2,6-dimethyl-2,6-octadien-8-ol), neryl acetate, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one (Calone 19515 ), 3,3,5-trimethylcyclohexyl acetate (preferably containing at least 70% by weight of the cis isomer content), and 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol (Ambrinol S 1 ), tetrahydro-4-methyl-2-(2-methylpropenyl)-2H-pyran (rose oxide), 4-methyl-2-(2-methylpropyl)oxane or 4-methyl-2-(2-methylpropyl)-2H-pyran (Dihydrorosan 4), prenyl acetate (=3-methylbut-2-enyl acetate), isoamyl acetate, dihydromyrcenol (2,6-dimethyloct-7-en-2-ol) and methylheptenone (6-methylhept-5-en-2-one), and mixtures thereof, and mixtures thereof with one or more other aromas.

[0119] Therefore, in the context of the present invention, the aforementioned aromas or odorants are preferably combined with the mixtures of the present invention.

[0120] When trademark names are mentioned above, they refer to the following sources: 1 Trade name of Symrise GmbH, Germany; 2 Trademark of Givaudan AG, Switzerland; 3 Trademark of International Flavors & Fragrances Inc., USA; 4 Trademarks of BASF SE; 5 Trade name of Danisco Seillans SA, France; 9 Trademark of Firmenich SA, Switzerland; 10 PFW is a trademark of Aroma Chemicals BV, the Netherlands.

[0121] More particularly, the advantages of the present invention are evident in the case of aroma chemicals selected from volatile fragrances and aroma mixtures comprising at least one volatile fragrance. Volatile fragrances are understood to mean fragrances that have a high vapor pressure at room temperature. A fragrance is considered to be a volatile fragrance if it has, inter alia, the following property: when a drop of the volatile fragrance is applied to a piece of paper and left to evaporate under ambient conditions at room temperature (22°C), its odor is no longer perceptible to an experienced perfumer two hours after application. Volatile fragrances include, inter alia, the following compounds: rose oxide (tetrahydro-4-methyl-2-(2-methylpropenyl)-2H-pyran), 4-methyl-2-(2-methylpropyl)oxane or 4-methyl-2-(2-methylpropyl)-2H-pyran (Dihydrorosan®), prenyl acetate (=3-methylbut-2-enyl acetate), isoamyl acetate, dihydromyrcenol (2,6-dimethyloct-7-en-2-ol) and methylheptenone (6-methylhept-5-en-2-one). When used to fill aroma mixtures containing at least one volatile fragrance, the proportion of volatile fragrance is generally at least 1% by weight, in particular at least 5% by weight, for example 1% to 99% by weight, in particular 5% to 95% by weight, based on the total weight of the aromachemical mixture used for filling.

[0122] Further odorants or aroma chemicals that can be combined with the aforementioned odorants to obtain odorant compositions can be found, for example, in S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, NJ, 1969, Author's Edition, or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th Ed., Wiley-VCH, Weinheim 2001. In particular, the following may be mentioned:

[0123] Extracts from natural sources, for example, essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures, e.g., ambra tincture; amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; tree moss absolute; bay oil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; baco leaf oil; cabreuva oil; cade oil; calamus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassia absolute; cassia Sodium absolute; Cedar leaf oil; Cedarwood oil; Cistus oil; Citronella oil; Lemon oil; Copaiba balsam; Copaiba balsam oil; Coriander oil; Costus root oil; Cumin oil; Cypress oil; Davana oil; Dill oil; Dill seed oil; Eau de Blaucz absolute; Oakmoss absolute; Elemi oil; Estragon oil; Eucalyptus citriodora oil; Eucalyptus oil; Fennel oil; Spruce needle oil; Galbanum oil; Galbanum resin; Geranium oil; Grapefruit oil; Guaiakwood oil; Gurjan balsam; Gurji Balsam oil; Helichrysum absolute; Helichrysum oil; Ginger oil; Iris root absolute; Iris root oil; Jasmine absolute; Calamus oil; Blue camellia oil; Roman camellia oil; Carrot seed oil; Cascarilla oil; Pine needle oil; Spearmint oil; Cumin oil; Labdanum oil; Labdanum absolute; Labdanum resin; Lavandin absolute; Lavandin oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Distilled lime oil; Pressed lime oil; Linalool oil; Litose acicularia oil; Rhododendron amurense oil Rhubarb oil; Muss oil; Marjoram oil; Mandarin oil; Muss soya bark oil; Mimosa absolute; Musk seed oil; Mus tinkling; Clary sage oil; Nutmeg oil; Myrrh absolute; Myrrh oil; Myrtle oil; Clove leaf oil; Clove flower oil; Neroli oil; Olibanum absolute; Olibanum oil; Opopanax oil; Orange blossom oil; Orange oil; Oregano oil; Palmarosa oil; Patchouli oil; Perilla oil; Peruvian balsam oil; Parsley leaf oil; Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil; Allspice oil;Pine oil; Pauly oil; Rose absolute; Rosewood oil; Rose oil; Rosemary oil; Dalmatian sage oil; Spanish sage oil; Sandalwood oil; Celery seed oil; Spike lavender oil; Star anise oil; Styrax oil; Tagit oil; Fir needle oil; Tea tree oil; Turpentine oil; Thyme oil; Tolu balsam; Tonka absolute; Tuberose absolute; Vanilla extract; Violet leaf absolute; Verbena oil; Vetiver oil; Juniper berry oil; Wine yeast oil; Vermouth oil; Wintergreen oil; Ylang ylang oil; Hyssop oil; Civet absolute; Cinnamon leaf oil; Cinnamon bark oil; and fractions or components isolated therefrom.

[0124] The individual odorants may be, for example: - Hydrocarbons, such as 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane; aliphatic alcohols, for example, hexanol, octanol, 3-octanol, 2,6-dimethylheptanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, (E)-2-hexenol, (E)- and (Z)-3-hexenol, 1-octen-3-ol, a mixture of 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol, (E,Z)-2,6-nonadienol, 3,7-dimethyl-7-methoxyoctan-2-ol, 9-decenol, 10-undecenol, 4-methyl-3-decen-5-ol; - aliphatic aldehydes and their acetals, for example, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyloctanal, 2-methylnonanal, (E)-2-hexenal, (Z)-4-heptenal, 2,6-dimethyl-5-heptenal, 10-undecenal, (E)-4-decenal, 2-dodecenal, 2,6,10-trimethyl-9-undecenal, 2,6,10-trimethyl-5,9-undecadiene Heptanal diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; (E / Z)-1-(1-methoxypropoxy)-3-hexene; aliphatic ketones and their oximes; for example, 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one; - sulfur-containing aliphatic compounds, such as 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthen-8-thiol; - aliphatic nitriles, such as 2-nonenenitrile; 2-undecenenitrile; 2-tridecenenitrile; 3,12-tridecadienonitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile; - esters of aliphatic carboxylic acids, for example, (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E) and (Z)-3-Hexenyl isobutyrate; Hexyl crotonate; Ethyl isovalerate; Ethyl 2-methylpentanoate; Ethyl hexanoate; Allyl hexanoate; Ethyl heptanoate; Allyl heptanoate; Ethyl octanoate; (E / Z)-Ethyl 2,4-decadienoate; Methyl 2-octynoate; Methyl 2-noninoate; Allyl 2-isoamyloxyacetate; Methyl 3,7-dimethyl-2,6-octadienoate; 4-Methyl-2-pentylcrotonate; - acyclic terpene alcohols, for example, geraniol, nerol, linalool, lavandulol, nerolidol, farnesol, tetrahydrolinalool, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-ol, 2,6-dimethyl-5,7-octadien-2-ol, 2,6-dimethyl-3,5-octadiene 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates; acyclic terpene aldehydes and ketones, such as geranial, neral, citronellal, 7-hydroxy-3,7-dimethyloctanal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9-undecenal, geranyl acetone, and also the dimethyl and diethyl acetals of geranial, neral, and 7-hydroxy-3,7-dimethyloctanal; cyclic terpene alcohols, such as menthol, isopulegol, α-terpene Pineol; Terpineol-4; Menthan-8-ol; Menthan-1-ol; Menthan-7-ol; Borneol; Isoborneol; Linalool oxide; Nopol; Cedrol; Ambrinol; Vetiverol; Guajol; and its formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, and 3-methyl-2-butenoates; - cyclic terpene aldehydes and ketones, for example, menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethylionone; α-irone; α-damascone; β-damascone; β-damascenone; δ-damascone; γ-damascone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl) )-2-Buten-1-one;1,3,4,6,7,8a-Hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one;2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal;Nootkatone;Dihydronootkatone;4,6,8-Megastigmatrien-3-one;α-Sinensal;β-Sinensal;Acetylated Cedarwood Oil (Methyl Cedryl Ketone); - cyclic alcohols, for example 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; - alicyclic alcohols, such as α-3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5 -(2,2,3-Trimethyl-3-cyclopent-1-yl)pentan-2-ol;3-Methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol;3,3-Dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol;1-(2,2,6-Trimethylcyclohexyl)pentan-3-ol;1-(2,2,6-Trimethylcyclohexyl)hexan-3-ol; - cyclic and alicyclic ethers, for example, cineole; cedryl methyl ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; 1,4-bis(ethoxymethyl)cyclohexane; (ethoxymethoxy)cyclododecane; α-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane; - cyclic and macrocyclic ketones, for example, 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; cis-3-methylpent-2-en-1-ylcyclopent-2-en-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-Methylcyclopentadecanone;4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone;4-tert-pentylcyclohexanone;Cyclohexadec-5-en-1-one;6,7-Dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone;8-Cyclohexadecen-1-one;7-Cyclohexadecen-1-one;(7 / 8)-Cyclohexadecen-1-one;9-Cycloheptadecen-1-one;Cyclopentadecanone;Cyclohexadecanone aliphatic aldehydes, such as 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde; - alicyclic ketones, for example 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl(2,4-dimethyl-3-cyclohexen-1-yl) ketone; - esters of cyclic alcohols, for example, 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentylcrotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; deca Hydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or -6-indenyl isobutyrate; 4,7-methanooctahydro-5- or -6-indenyl acetate; - esters of alicyclic alcohols, for example, 1-cyclohexylethyl crotonate; - esters of alicyclic carboxylic acids, for example, allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; cis- and trans-methyldihydrojasmonate; cis- and trans-methyljasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-acetate; - aromatic aliphatic alcohols, for example, benzyl alcohol; 1-phenylethyl alcohol, 2-phenylethyl alcohol, 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol; - Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, for example, benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; α-trichloromethylbenzyl acetate; α,α-dimethylphenylethyl acetate; α,α-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; - aromatic aliphatic ethers, for example, 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydratropaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxine; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxine; - aromatic and araliphatic aldehydes, for example, benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropaldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal Cinnamaldehyde;α-Butylcinnamaldehyde;α-Amylcinnamaldehyde;α-Hexylcinnamaldehyde;3-Methyl-5-phenylpentanal;4-Methoxybenzaldehyde;4-Hydroxy-3-methoxybenzaldehyde;4-Hydroxy-3-ethoxybenzaldehyde;3,4-Methylenedioxybenzaldehyde;3,4-Dimethoxybenzaldehyde;2-Methyl-3-(4-methoxyphenyl)propanal;2-Methyl-3-(4-methylenedioxyphenyl)propanal; Aromatic and araliphatic ketones, such as acetophenone, 4-methylacetophenone, 4-methoxyacetophenone, 4-tert-butyl-2,6-dimethylacetophenone, 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone, 1-(2-naphthalenyl)ethanone, 2-benzofuranylethanone, (3-methyl-2-benzofuranyl)ethanone, benzophenone 1,1,2,3,3,6-Hexamethyl-5-indanyl methyl ketone;6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone;1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone;5',6',7',8'-Tetrahydro-3',5',5',6',8',8'-hexamethyl-2-acetonaphthone; - aromatic and araliphatic carboxylic acids and their esters, for example, benzoic acid, phenylacetic acid, methyl benzoate, ethyl benzoate, hexyl benzoate, benzyl benzoate, methyl phenyl acetate, ethyl phenyl acetate, geranyl phenyl acetate, phenylethyl phenyl acetate, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, cinnamyl cinnamate, allyl phenoxyacetate, methyl salicylate, isoamyl salicylate, hexyl salicylate, cyclohexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, phenylethyl salicylate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl 3-phenylglycidate, ethyl 3-methyl-3-phenylglycidate; - nitrogen-containing aromatic compounds, for example, 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 3-methyl-5-phenyl-2-pentenonitrile; 3-methyl-5-phenylpentanonitrile; methyl anthranilate; methyl N-methylanthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine; - phenols, phenyl ethers and phenyl esters, for example, estragole; anethole; eugenol; eugenyl methyl ether; isoeugenol; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresylphenyl acetate; heterocyclic compounds, for example, 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one; - lactones, for example 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 4-methyl-1,4-decanolide; 1,15-pentadecanolide; cis- and trans-11-pentadecanolide; cis- and trans-12-pentadecanolide They are derived from the group of tadecen-1,15-olide; 1,16-hexadecanolide; 9-hexadecen-1,16-olide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene 1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; and octahydrocoumarin.

[0125] Additionally, suitable aroma chemicals are macrocyclic carbaldehyde compounds such as those described in WO 2016 / 050836.

[0126] Particularly preferred are mixtures of L-menthol and / or DL-menthol, L-menthone, L-menthyl acetate, or L-isopulegol, which are highly desirable analogs or substitutes for what is known as synthetic dementholized mint oil (DMOS). Mixtures of these mint compositions are preferably used in weight ratios of 20-40% L-menthol or DL-menthol, 20-40% L-menthone, and 0-20% L-menthyl acetate, or in weight ratios of 20-40% L-menthone, 20-40% L-menthone, and 0-20% L-isopulegol.

[0127] The aforementioned aromas and aroma mixtures can be used by themselves or in solvents that are not themselves aromas. Typical solvents for aromas are, inter alia, those that have a boiling point above 150°C at standard pressure and do not dissolve the wall material, for example, diols such as propanediol and dipropylene glycol, C8-C8 alkyl esters such as isopropyl myristate, etc. 22 Fatty acid C1~C 10 Alkyl esters, di-C6-C 10 Alkyl esters, such as dicapryl ether (Cetiol® OE from BASF SE), di-C1-C6 alkyl esters of aliphatic, aromatic or cycloaliphatic di- or tricarboxylic acids. 10 Alkyl esters, for example dialkyl phthalates such as dimethyl and diethyl phthalate and mixtures thereof, dialkyl hexahydrophthalates, for example dimethyl cyclohexane-1,2-dicarboxylate, diethyl cyclohexane-1,2-dicarboxylate and diisononyl 1,2-cyclohexanedicarboxylate, and dialkyl adipates such as dibutyl adipate (for example Cetiol® B from BASF SE), C8-C 22 Fatty acid triglycerides, for example vegetable oils or cosmetic oils, such as octanoyl / decanoyl triglycerides (for example Myritol® 318, a commercial product from BASF SE), dimethyl sulfoxide and white oil.

[0128] In a further group of embodiments, the low molecular weight organic active substance is an active pharmaceutical ingredient, abbreviated as API. The active pharmaceutical ingredient is typically an active therapeutic ingredient, an active diagnostic ingredient, an active preventive ingredient, and corresponding combinations of active ingredients. The active pharmaceutical ingredient can be in an amorphous state, a crystalline state, or a mixture thereof. The active pharmaceutical ingredient may be labeled with a detectable label, such as a fluorescent label, a radioactive label, or an enzymatically or chromatographically detectable species, and can be used in combination with this label to load the microparticles.

[0129] The API may have a water solubility in deionized water of greater than 10 mg / mL at 25° C. Alternatively, the active substance may be an active pharmaceutical ingredient with low water solubility, for example, an active pharmaceutical ingredient with a water solubility in deionized water of less than 10 mg / mL at 25° C. In either case, the API should have a partition coefficient with respect to the water-immiscible liquid and the aqueous phase of at least 1.0, particularly at least 2.0.

[0130] Preferred active therapeutic, diagnostic and prophylactic components are APIs suitable for parenteral administration. Representative examples of suitable APIs include the following categories and examples of APIs and alternative forms of these APIs, such as alternative salt forms, free acid forms, free base forms and hydrates: analgesics / antipyretics; antiasthmatics; antibiotics; antidepressants; antidiabetics; anti-inflammatory / inflammation inhibitors; antihypertensives; inflammation inhibitors; antineoplastics; antianxiety drugs; immunosuppressants; antimigraine drugs; sedatives / hypnotics; antianginal drugs; antipsychotics; antimanic drugs; antiarrhythmic drugs; antiarthritic drugs; antigout drugs; anticoagulants; thrombolytic drugs; Antifibrinolytics; hemorheological agents; antiplatelet agents / platelet aggregation inhibitors; anticonvulsants; antiparkinsonian agents; antihistamines / antipruritics; calcium regulators; antibacterial agents; antiviral agents; antimicrobial agents; antiinfective agents; bronchodilators; corticosteroids; steroid compounds and hormones; hypoglycemic agents; lipid-lowering agents; proteins; nucleic acids; drugs useful in stimulating erythropoiesis; antiulcer / antireflux agents; antiemetic / antimosis agents; oil-soluble vitamins and other agents.

[0131] Suitable active pharmaceutical ingredients are mentioned, for example, in WO 2007 / 070852, especially on pages 15 to 19. In addition, suitable active ingredients and drugs are listed in Martindale: The Extra Pharmacopoeia, 30th edition, The Pharmaceutical Press, London 1993.

[0132] In another group of embodiments, the organic active substance is agrochemical compound, i.e., organic compound for crop protection, also called organic crop protection agent.Agrochemicals are, for example, pesticides selected from the group consisting of fungicides, insecticides, nematicides, herbicides, pheromones, but also safeners and growth regulators, which can be included as a single compound, but can also be included as a mixture of different agrochemical compounds, for example, a mixture of two or more herbicides, a mixture of two or more fungicides, a mixture of two or more insecticides, a mixture of an insecticide and a fungicide, a mixture of one or more herbicides and a safener, and a mixture of one or more fungicides and a safener.

[0133] Typically, pesticides are liquid or solid at 20°C and 1 bar and are usually non-volatile. The vapour pressure is typically less than 0.1 mbar, especially less than 0.01 mbar, at 20°C. Pesticides are particularly poorly water-soluble or even insoluble in water, especially having a water solubility of 5 g / L or less, especially 2 g / L or less in deionised water at 25°C.

[0134] Pesticides are known to those skilled in the art, for example from The Pesticide Manual, 17th edition, The British Crop Protection Council, London, 2015. Suitable crop protection agents are listed inter alia on pages 10 to 15 of WO 2018 / 019629.

[0135] Examples of suitable insecticides are carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosyns, avermectins, milbemycins, juvenile hormone analogues, alkyl halides, organotin compounds, nereistoxin analogues, benzoylureas, diacylhydrazines, compounds from the METI acaricide class, and unclassified insecticides such as chlorpicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or agriculturally acceptable salts and derivatives thereof.

[0136] Examples of suitable fungicides are dinitroaniline, allylamine, anilinopyrimidine, antibiotic fungicide, aromatic hydrocarbon, benzenesulfonamide, benzimidazole, benzisothiazole, benzophenone, benzothiadiazole, benzotriazine, benzyl carbamate, carbamate, carboxamide, carboxylic acid diamide, chloronitrile, cyanoacetamide oxime, cyanoimidazole, cyclopropanecarboxamide, dicarboximide, dihydrodioxazine, dinitrophenyl crotonate, dithiocarbamate, dithiolane, ethyl phosphonate, ethylaminothiazolecarboxamide, guanidine, hydroxy(2-amino)pyrimidine, hydroxyanilide, imidazole, imidazolinone, isobenzofuranone, methoxyacrylate, methoxycarbamate, morpholine, methyl methyl acrylate ... compounds from the classes of phosphorus, N-phenylcarbamates, oxazolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothioates, phthalamic acid, phthalimides, piperazines, piperidine, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinone hydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles, and agriculturally acceptable salts and derivatives thereof.

[0137] Examples of suitable herbicides are acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofurans, benzoic acids, benzothiadiazinones, bipyridinium salts, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanedione, dinitroanilines, dinitrophenols, diphenyl ethers, glycine, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinedione, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines. , phosphinic acids, phosphoramidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas, and agriculturally acceptable salts and derivatives thereof.

[0138] In a particular subgroup of this group of embodiments, the crop protection agent is a crop protection agent that is liquid at 22° C. and 1 bar, or a mixture of two or more crop protection agents that are liquid at 22° C. and 1 bar. Examples of room temperature liquid active ingredients are dimethenamide, especially its enantiomer, dimethenamide-P, clomazone, metolachlor, especially its enantiomer, S-metolachlor, alachlor and cinmethylin.

[0139] In a further particular subgroup of this group of embodiments, the crop protection agent is a crop protection agent or mixture of crop protection agents, or a mixture of such active ingredients, that has low water solubility and a melting point of 110° C. or less. These include, for example, pyraclostrobin (64° C.), prochloraz (47° C.), metrafenone (100° C.), alphacypermethrin (79° C.) and pendimethalin (58° C.).

[0140] In yet a further particular subgroup of this group of embodiments, the crop protection agent is a pheromone or a mixture of pheromones optionally in combination with one or more attractants.

[0141] Pheromones are well-known compounds used to control unwanted insects. For example, Metcalf, R.L. Lullmann's Encyclopedia of Industrial Chemistry 2000, keyword "Insect Control," lists suitable examples in Chapter 15.1 (Sex Pheromone Attractants) and Chapter 15.2 (Aggregation Pheromones), and the pheromones for Lepidoptera in Table 4 of this reference are highly suitable.

[0142] Examples of pheromones include volatile alkanols and alkenols having 5 to 18 carbon atoms, volatile alkanals and alkenals having 5 to 18 carbon atoms, alkanones having 6 to 18 carbon atoms, 1,7-dioxaspirononane and 3- or 4-hydroxy-1,7-dioxaspiroundecane, benzyl alcohol, Z-(9)-tricosene (muscarule), heneicosene, alkanoic acids having 5 to 16 carbon atoms such as diacetyl, caprylic acid, and lauric acid, α-pinene, methyl eugenol, ethyl dodecanoate, tert-butyl 4-(or 5-)chloro-2-ethylcyclohexane-carboxylate, mycrenone, cucurbitacin, trimedlure (commercially available as Capilure®), and (E,E)-8,10-dodecadien-1-ol (codlemone).

[0143] Further examples of known pheromones are: Z-5-decenyl acetate, dodecanyl acetate, Z-7-dodecenyl acetate, E-7-dodecenyl acetate, Z-8-dodecenyl acetate, E-8-dodecenyl acetate, Z-9-dodecenyl acetate, E-9-dodecenyl acetate, E-10-dodecenyl acetate, 11-dodecenyl acetate, Z-9,11-dodecadienyl acetate, E-9,11-dodecadienyl acetate, Z-11-tridecenyl acetate, E-11-tridecenyl acetate. E-7-tetradecenyl acetate, Z-8-tetradecenyl acetate, E-8-tetradecenyl acetate, Z-9-tetradecenyl acetate, E-9-tetradecenyl acetate, Z-10-tetradecenyl acetate, E-10-tetradecenyl acetate, Z-11-tetradecenyl acetate, E-11-tetradecenyl acetate, Z-12-pentadecenyl acetate, E-12-pentadecenyl acetate, hexadecanyl acetate, Z-7-hexadecenyl acetate Nyl acetate, Z-11-hexadecenyl acetate, E-11-hexadecenyl acetate, octadecanyl acetate, E,Z-7,9-dodecadienyl acetate, Z,E-7,9-dodecadienyl acetate, E,E-7,9-dodecadienyl acetate, Z,Z-7,9-dodecadienyl acetate, E,E-8,10-dodecadienyl acetate, E,Z-9,12-dodecadienyl acetate, E,Z-4,7-tri-decadienyl acetate, 4-methoxy-cinnamaldehyde, [β]-ionone, Es Tragol, eugenol, indole, 8-methyl-2-decylpropanoate, E,E-9,11-tetradecadienyl acetate, Z,Z-9,12-tetradecadienyl acetate, Z,Z-7,11-hexadecadienyl acetate, E,Z-7,11-hexadecadienyl acetate, Z,E-7,11-hexadecadienyl acetate, E,E-7,11-hexadecadienyl acetate, Z,E-3,13-octadecadienyl acetate, E,Z-3,13-octadecadienyl acetate, E,E-3,13-Octadecadienyl acetate, hexanol, heptanol, octanol, decanol, Z-6-nonenol, E-6-nonenol, dodecanol, 11-dodecenol, Z-7-dodecenol, E-7-dodecenol, Z-8-dodecenol, E-8-dodecenol, E-9-dodecenol, Z-9-dodecenol, E-9,11-dodecadienol, Z-9,11-dodecadienol, Z,E-5,7-dodecadienol, E,E-5,7-dodecadienol, E,E-8,10-dodecadienol, E,Z-8,10-dodecadienol Z,Z-8,10-dodecadienol, Z,E-8,10-dodecadienol, E,Z-7,9-dodecadienol, Z,Z-7,9-dodecadienol, E-5-tetradecenol, Z-8-tetradecenol, Z-9-tetradecenol, E-9-tetradecenol, Z-10-tetradecenol, Z-11-tetradecenol, E-11-tetradecenol, Z-11-hexadecenol, Z,E-9,11-tetradecadienol, Z,E-9,12-tetradecadienol, Z,Z-9,12-tetradecadienol, Z,Z-10,1 2-Tetradecadienol, Z,Z-7,11-hexadecadienol, Z,E-7,11-hexadecadienol, (E)-14-methyl-8-hexadecen-1-ol, (Z)-14-methyl-8-hexadecen-1-ol, E,E-10,12-hexadecadienol, E,Z-10,12-hexadecadienol, dodecanal, Z-9-dodecenal, tetradecanal, Z-7-tetradecenal, Z-9-tetradecenal, Z-11-tetradecenal, E-11-tetradecenal, E-11,13-tetradecadienal, E ,E-8,10-tetradecadienal, Z,E-9,11-tetradecadienal, Z,E-9,12-tetradecadienal, hexadecanal, Z-8-hexadecenal, Z-9-hexadecenal, Z-10-hexadecenal, E-10-hexadecenal, Z-11-hexadecenal, E-11-hexadecenal, Z-12-hexadecenal, Z-13-hexadecenal, (Z)-14-methyl-8-hexadecenal, (E)-14-methyl-8-hexadecenal, Z,Z-7,11-hexadecadienal, Z,E-7,11-Hexadecadienal, Z,E-9,11-Hexadecadienal, E,E-10,12-Hexadecadienal, E,Z-10,12-Hexadecadienal, Z,E-10,12-Hexadecadienal, Z,Z-10,12-Hexadecadienal, Z,Z-11,13-Hexadecadienal, Octadecanal, Z-11-Octadecenal, E-13-Octadecenal, Z-13-Octadecenal, Z-5-Decenyl-3-methylbutanoate Disparlure: (+)cis-7,8-epoxy-2-methyloctadecanoate Seudenol: 3-methyl-2-cyclohexen-1-ol, Sulcatol: 6-methyl-5-hepten-2-ol, Ipsenol: 2-methyl-6-methylene-7-octen-4-ol, Ipsdienol: 2-methyl-6-methylene-2,7-octadien-4-ol, Grandolure I: cis-2-isopropenyl-1-methylcyclobutane-ethanol, Grandolure II: Z-3,3-dimethyl-1-cyclohexane-ethanol, Grandolure III: Z-3,3-dimethyl-1-cyclohexane-acetaldehyde, Grandeur IV: E-3,3-dimethyl-1-cyclohexaneacetaldehyde, cis-2-verbenol: cis-4,6,6-trimethylbicyclo[3,1,1]hept-3-en-2-ol, cucurbitacin, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, cucurbitacin, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, [α]-pinene: 2,6,6-trimethylbicyclo[3,1,1]hepten-2-ene, [α]-caryophyllene: 4,11,11-trimethyl-8-methylene- Bicyclo[7,2,0]undecane, Z-9-tricosene, ([α]-multistriatin, 2-(2-endo,4-endo)-5-ethyl-2,4-dimethyl-6,8-dioxabicyclo[3,2,1]octane, methyleugenol: 1,2-dimethoxy-4-(2-propenyl)phenol, lineatin: 3,3,7-trimethyl-2,9-dioxatricyclo[3,3,1,0]nonane, chalcoglan: 2-ethyl-1,6-dioxaspiro[4,4]nonane, frontalin: 1,5-dimethyl-6,8-dioxabicyclo[3,2,1]octane, Endo-Brevicomin: Endo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1]octane, Exo-Brevicomin: Exo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1]octane, (Z)-5-(1-decenyl)dihydro-2-(3H)-furanone, Farnesol: 3,7,11-trimethyl-2,6,10-dodecatrien-1-ol, Nerolidol: 3,7,11-trimethyl-1,6,10-dodecatrien-3-ol, 3-methyl, 6-(1-methyl)- (Z)-3-methyl-6-(1-methylethenyl)-3,9-decadien-1-ol acetate, (E)-3,9-methyl-6-(1-methyl-ethenyl)-5,8-decadien-1-ol acetate, 3-methylene-7-methyl-octen-1-ol propionate, (Z)-3,7-dimethyl-2,7-octadien-1-ol propionate and (Z)-3,9-dimethyl-6-(1-methyl-ethenyl)-3,9-decadien-1-ol propionate.

[0144] Preferred pheromones are Z-9-dodecenyl acetate (commercially available as RAK® 1 from BASF SE), (E7,Z9)-dodecadienyl acetate (commercially available as RAK® 2 from BASF SE), (E,E)-8,10-dodecadien-1-ol (commercially available as RAK® 3 from BASF SE), and Z-8-dodecenyl acetate.

[0145] Particularly preferred pheromones include (E,E)-8,10-dodecadien-1-ol, which is also known as codlemone or codlure and is commercially available (e.g., as CheckMate® CM-F from Suterra LLC, USA; Isomate®-C Plus from Pacific Biocontrol Corp. USA; and RAK® 3 from BASF SE). Codlemone can be used in pure form, in technical quality, or in mixtures with other pheromones.

[0146] The aforementioned pheromones may be combined with one or more attractants. Attractants are non-pesticidal materials that can act in one or more of the following ways: a) attracting insects to approach the composition or materials treated with the composition; b) attracting insects to contact the composition or materials treated with the composition; c) attracting insects to ingest the composition or materials treated with the composition; and d) attracting insects to return to the composition or materials treated with the composition. Suitable attractants include non-food attractants and food attractants (also called feeding stimulants).

[0147] Suitable non-food attractants are usually volatile materials. Volatile attractants function as baits, and their types depend on the pests to be controlled in a known manner. Non-food attractants include, for example, flavors of natural or synthetic origin. Suitable flavors include meat flavor, yeast flavor, seafood flavor, milk flavor, butter flavor, cheese flavor, onion flavor, and fruit flavor, such as apple, apricot, banana, blackberry, cherry, currant, currant, grape, grapefruit, raspberry, and strawberry flavor.

[0148] Suitable food attractants include: Proteins, including animal and vegetable proteins, for example in the form of meat meal, fish meal, fish extract, seafood, seafood extract, or blood meal, insect parts, cricket meal, yeast extract, egg yolk, protein hydrolysates, yeast autolysates, gluten hydrolysates, etc.; Carbohydrates and hydrogenated carbohydrates, in particular mono- and disaccharides such as glucose, arabinose, fructose, mannose, sucrose, lactose, galactose, maltose, maltotriose, maltotetrose, maltopentose or mixtures thereof, such as molasses, corn syrup, maple syrup, invert sugar and honey; polysaccharides, including starch, such as potato starch, corn starch, and starch-based materials, such as cereal flours (e.g. wheat flour, corn flour, malt flour, rice flour, rice bran), pectin, and glycerol; hydrogenated mono- and oligosaccharides (sugar alcohols), such as xylitol, sorbitol, mannitol, isomaltose, trehalose, and maltitol, and maltitol-containing syrups. Examples include:

[0149] Preferred attractants are ethyl 3-methylbutanoate, methyl salicylate, amyl acetate, limonene, or fruit extracts (e.g., apple extract made from dried and extracted apples and containing fructose, glucose, sorbitol, and apple flavor). Mixtures of attractants are also suitable.

[0150] In a further group of embodiments, the organic active substance is an organic active substance suitable for cosmetic applications or an active mixture other than the aforementioned aromas. Preferred cosmetic active substances for loading the microparticles are, inter alia, active plant ingredients and plant extracts.

[0151] Examples of cosmetic active substances are skin and hair pigmentation agents, tanning agents, bleaching agents, keratin-hardening substances, antimicrobial active ingredients, light filter active ingredients, repellent active ingredients, hyperemic substances, keratolytic and keratinogenic substances, antidandruff active ingredients, inflammatory agents, keratinizing substances, antioxidant active ingredients and active ingredients which act as free radical scavengers, skin moisturizing or hydrating substances, refatting active ingredients, deodorizing active ingredients, soothing active ingredients, plant extracts, anti-lupus or anti-allergic active ingredients and mixtures thereof.

[0152] Suitable artificial tanning actives for tanning skin without natural or artificial UV irradiation include, for example, dihydroxyacetone, alloxan, and walnut shell extract. Suitable keratin-hardening agents are typically active ingredients found in antiperspirants, such as aluminum potassium sulfate, aluminum hydroxide, and aluminum lactate. Antimicrobial actives are used to kill and / or inhibit the growth of microorganisms, thus acting both as preservatives and as deodorants to reduce the formation or intensity of body odor. These include conventional preservatives known to those skilled in the art, such as p-hydroxybenzoic acid esters, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, and salicylic acid. Examples of such deodorants include zinc ricinoleate, triclosan, undecylenic acid alkylolamide, triethyl citrate, and chlorhexidine. Suitable light filter active ingredients are substances that absorb UV rays in the UV-B and / or UV-A range. Suitable UV filters are those mentioned above. In addition, suitable are p-aminobenzoic acid esters, cinnamic acid esters, benzophenones, and camphor derivatives, as well as pigments that block UV rays, such as titanium dioxide, talc, and zinc oxide. Suitable repellent active ingredients are compounds that can repel or repel certain animals, especially insects, from humans. These include, for example, 2-ethyl-1,3-hexanediol, N,N-diethyl-m-toluamide, etc. Suitable hyperemic substances that stimulate blood flow through the skin include, for example, essential oils such as dwarf pine, lavender, rosemary, juniper berry, and roasted chestnut extract, birch leaf extract, hay seed extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, and eucalyptus oil. Suitable keratolytic and keratinogenic substances are, for example, salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc. Suitable anti-dandruff active ingredients are, for example, sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc.Suitable anti-inflammatory agents to combat skin irritation include, for example, allantoin, bisabolol, dragosantol, chamomile extract, panthenol, and the like.

[0153] Further cosmetic active substances are aspalathin, glycyrrhizin, caffeine, proanthocyanidins, hesperetin, rutin, luteolin, polyphenols, oleuropein, theobromine, bioflavonoids and polyphenols.

[0154] Examples of plant extracts include acai extract (Euterpe oleracea), acerola extract (Malpighia glabra), horsetail extract (Equisetum arvense), agarius extract (Agarius blazei murill), aloe extract (Aloe vera, Aloe barbadensis), apple extract (Malus), artichoke leaf extract (Cynara scolymus), artichoke blossom extract (Cynara edulis), arnica extract (Arnica montana), oyster extract (Ostrea edulis), and others. edulis), Kanokosoul Root Extract (Valeriana officinalis), Bearberry Leaf Extract (Arctostaphylos uva-ursi), Bamboo Extract (Bambus vulgaris), Bitter Melon Extract (Momordica charantia), Bitter Orange Extract (Citrus aurantium), Nettle Leaf Extract (Urtica dioica), Nettle Root Extract (Urtica dioica), Broccoli Extract (Brassica oleracea), Watercress Extract (Rorippa nasturtium), Painted Nettle Extract (Coleus forskohlii) forskohlii), Capsaicin Extract (Capsicum frutescens), Centella asiatica (Gotu Kola) Extract, Cinchona Extract, Cranberry Extract (Vaccinium vitis-daea)vitis-daea), Turmeric Extract (Curcuma longa), Damiana Extract (Tunera diffusa), Dragon Fruit Extract (Pitahaya), Echinacea Purpurea Extract, Wheat Placenta Extract, Edelweiss Extract (Leotopodium alpinum), Ivy Extract (Hedera helix), Bindi Extract (Tribulus terrestris), Garcinia Cambogia Extract (Garcinia cambogia), Ginkgo Biloba Extract (Ginkgo biloba), Korean Ginseng Extract (Panax ginseng) ginseng), Pomegranate Extract (Punica granatum), Grapefruit Extract (Citrus paradisi), Griffonia Extract (Griffonia simplicifolia), Green Tea Extract (Camellia sinensis), Guarana Extract (Paullinia cupana), Cucumber Extract (Cucumis sativus), Dog Rose Extract (Rosa canina), Blueberry Extract (Vaccinium myrtillus), Hibiscus Extract (Malvacea), Mallow Extract, Honey Extract, Hop Extract (Humulus), Ginger Extract (Zingiber officinale) officinale), Iceland Moss Extract (Cetraria islandica), Jojoba Extract (Simmondsia chinensis), St. John's Wort Extract (Hypericum perforatum)perforatum), Coffee Concentrate, Cocoa Bean Extract (Theobroma cacao), Cactus Blossom Extract, Chamomile Blossom Extract (Matricaria recutita, Matricaria chamomila), Ginseng Extract (Daucus carota), Kiwi Extract (Aperygidae), Kudzu Extract (Pueraria lobata), Coconut Milk Extract, Pumpkin Seed Extract (Curcurbita pepo), Cornflower Extract (Centaurea cyanus), Lotus Flower Extract, Dandelion Extract (Taraxacum officinalis) officinale), Maca Extract (Lepidium peruvianum), Magnolia Blossom Extract, Mango Extract, Milk Thistle Extract (Silybum marianum), Marigold Extract (Calendula officiennalis), Yerba Mate Extract (Hex paraguariensis), Butcher's Broom Extract (Rugcus aculeatus), Seaweed Extract, Cranberry Extract (Vaccinium macrocarpon), Moringa Oleifera Extract, Moschus Malve Extract (Malva moschata), Evening Primrose Oil Extract (Azadirachta indica) indica), Nettle Extract (Urticaceae), Olive Leaf Extract (Olea europea), Orange Extract (Hesperidin), Orchid Extract, Papaya Extract (Carica papaya)papaya), Peppermint Extract, Carica Papaya Extract (Geissospermum), Bitter Orange Extract (Citrus aurantioum), Lingonberry Extract (Vaccinium vitas-ideea), African Cherry Extract (Prunus africana), Sugar Beet Extract, Resveratrol Extract (Polygonum cuspidatum), Rooibos Extract (Aspalasthus Linnearis), Rose Blossom Extract, Horse Chestnut Extract (Aesculus hippocastanum), Rosemary Extract (Rosemarinus oleracea) Officinalis), Red Clover Extract (Trifolium platense), Red Wine Extract (Vitis vinifera), Saw Palmetto Extract (Serenoa repens), Lettuce Extract (Lactuca sativa), Sandalwood Extract (Santalum rubrum), Sage Extract (Salvia officinalis), Horsetail Extract (Equisetum), Yarrow Extract (Achillea millefolium), Black Pepper Extract (Piper nigrum), Black Tea Extract, Water Lily Extract (Nymphaea), White Willow Bark Extract (Salix alba) Alba), Licorice Extract (Glycyrrhiza), Devil's Claw Extract (Harpagophytum procumbens), Thyme Extract (Thymus vulgaris), Tomato Extract (Lycopersicum esculentum)esculentum), Grape Seed Extract (Vitis vinifera), Grape Skin Extract (Vitis vinifera), Watercress (Rorippa amphibia), Willow Bark Extract (Salix alba), Mugwort Extract (Artemisia absinthium), White Tea Extract, Yam Root Extract (Dioscorea opposita), Yohimbe Extract (Pausinystalia yohimbe), Witch Hazel Extract (Hamamelis virginiana), Cinnamon Extract (Cinnamomum cassia purpurea) Presl), lemon extract (Citrus), and onion extract (Allium cepa).

[0155] In a further group of embodiments, the low molecular weight organic active substance is a vitamin, in particular a lipophilic vitamin, such as vitamin A, vitamin D, vitamin E or vitamin K, or a combination thereof.

[0156] In a further group of embodiments, the low molecular weight organic active substance is an organic effective compound. The effective compound is an organic active substance that does not belong to the following groups: pesticides, aroma chemicals, vitamins, AIDS, and cosmetic active substances. This group of active compounds is typically not approved for agricultural use, human administration, cosmetic or dietary use. These include, but are not limited to, compounds for construction chemicals, particularly catalysts, but also dyes, UV stabilizers, polymerization inhibitors, oxidation stabilizers, and the like. Preferred active substances encapsulated in microparticles for use in construction chemicals are, inter alia, polymerization catalysts.

[0157] Useful polymerization catalysts include those suitable for curing reactive resins, especially addition resins, condensation resins, or oxidatively cured resins. For this purpose, the polymerization catalyst is a catalyst for free-radical polymerization, polycondensation, and / or polyaddition. Suitable catalysts for free-radical polymerization include, inter alia, peroxide decomposers and catalysts known from the coating technology for oxidatively drying oil and alkyd resins as driers or siccatives. Suitable polycondensation catalysts are catalysts for silicone condensation and crosslinking. The polyaddition catalyst used can be, for example, a catalyst for curing epoxy resins. Additionally, the polyaddition catalyst used can be, for example, a urethanization catalyst conventionally used in polyurethane chemistry. These are compounds that promote the reaction of the reactive hydrogen atoms of the isocyanate-reactive component with the organic polyisocyanate.

[0158] Useful polymerization catalysts include tertiary amines, phosphines and organometallic salts, among others.

[0159] Tertiary amines useful as polymerization catalysts for polyaddition, among others, include, for example, triethylamine, tributylamine, N,N-dimethylcyclohexylamine (DMCHA), N-methyldicyclohexylamine, N,N-dimethylbenzylamine (BDMA), N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, 2,2'-dimorpholinodiethyl ether (DMDEE), N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutylenediamine, N,N,N',N'-tetramethylhexylene-1,6-diamine, N,N,N',N'',N'''-pentamethyldiethylenetriamine (PMDETA), N,N,N',N'',N'''-pentamethyldipropylenetriamine, ... amine (PMDPTA), N,N,N-tris(3-dimethylaminopropyl)amine, bis(2-dimethylaminoethyl)ether (BDMAEE), bis(dimethylaminopropyl)urea, 2,4,6-tris(dimethylaminomethyl)phenol, its salt with 2-ethylhexanoic acid and its isomers, 1,4-dimethylpiperazine (DMP), N-methylimidazole, 1,2-dimethylimidazole, 1-methyl-4-(2-dimethylaminoethyl)piperazine, 1-azabicyclo[3.3.0]octane, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and 1,5-diazabicyclo[4.3.0]non-7-ene (DBN).

[0160] Further useful polymerization catalysts, especially for polyaddition, include tris(dialkylamino)-s-hexahydrotriazines, especially 1,3,5-tris(3-[dimethylamino]propyl)hexahydrotriazine.

[0161] In particular, phosphines useful as polymerization catalysts for polyaddition are preferably tertiary phosphines such as triphenylphosphine or methyldiphenylphosphine.

[0162] The organometallic salts useful as polymerization catalysts preferably have the general formula Lm M n+ nA - (In the formula, Ligand L is an organic group or organic compound selected from alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl, and acyl, Ligand L has 1 to 20 carbon atoms, and m Ligands L are the same or different; m is 0, 1, 2, 3, 4, 5 or 6; M is a metal, n is 1, 2, 3 or 4, and Anion A - is a carboxylate ion, an alkoxylate ion, or an enolate ion).

[0163] The metal M is preferably selected from lithium, potassium, cesium, magnesium, calcium, strontium, barium, boron, aluminum, indium, tin, lead, bismuth, cerium, cobalt, iron, copper, lanthanum, manganese, mercury, scandium, titanium, zinc and zirconium; more particularly lithium, potassium, cesium, tin, bismuth, titanium, zinc and zirconium.

[0164] The ligand L is preferably alkyl having 1 to 20 carbon atoms. More preferably, L is alkyl having 1 to 10 carbon atoms, especially 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

[0165] The carboxylate ion preferably has the formula R 1 -COO - wherein R 1 is selected from H, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl, and acyl; R 1The group has up to 20 carbon atoms, preferably 6 to 20. Particularly preferred carboxylate ions are selected from the anions of natural and synthetic fatty acids, such as neodecanoate, isooctanoate and laurate, and the anions of resin acids and naphthenic acids.

[0166] The enolate ion preferably has the formula R 2 CH=CR 3 -O - wherein R 2 and R 3 are each selected from H, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl, and acyl; R 2 Groups and R 3 The groups each have up to 20 carbon atoms. Specific examples are ethyl acetonate, heptyl acetonate, or phenyl acetonate. The enolate ions are preferably derived from 1,3-diketones having 5 to 8 carbon atoms. Possible examples include acetyl acetonate, the enolate of 2,4-hexanedione, the enolate of 3,5-heptanedione, and the enolate of 3,5-octanedione.

[0167] The alkoxylate ion preferably has the formula R 4 -O - wherein R 4 is selected from alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, heteroaryl, heteroarylalkyl, alkylheteroaryl, and acyl; R 4 The group has a maximum of 20 carbon atoms.

[0168] In certain embodiments, the organometallic compound is - alkali metal carboxylates, for example, lithium ethylhexanoate, lithium neodecanoate, potassium acetate, potassium ethylhexanoate, cesium ethylhexanoate; alkaline earth metal carboxylates, for example calcium ethylhexanoate, calcium naphthenate, calcium octoate (available as Octa-Soligen® Calcium from OMG Borchers), magnesium stearate, strontium ethylhexanoate, barium ethylhexanoate, barium naphthenate, barium neodecanoate; aluminum compounds, such as aluminum acetylacetonate, aluminum dionate (for example K KAT® 5218 from King Industries); zinc compounds, such as zinc diacetate(ll), zinc ethylhexanoate(ll) and zinc octoate(ll), zinc neodecanoate, zinc acetylacetonate; tin compounds, such as tin(II) carboxylates, for example tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate, tin(II) neodecanoate, tin(II) isononanoate, tin(II) laurate, and dialkyltin(IV) salts of organic carboxylic acids, for example dimethyltin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis(2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate and dioctyltin diacetate, especially dibutyltin dilaurate; titanium compounds, for example, tetra(2-ethylhexyl) titanate; zirconium compounds, such as zirconium ethylhexanoate, zirconium neodecanoate, zirconium acetylacetonate (for example K-KAT® 4205 from King Industries); zirconium dionates (for example K-KAT® XC-9213; XC-A 209 and XC-6212 from King Industries); zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate; bismuth compounds, such as bismuth carboxylates, especially bismuth octoate, bismuth ethylhexanoate, bismuth neodecanoate or bismuth pivalate (for example K-KAT® 348, XC-B221, XC-C227, XC 8203, XK 651 from King Industries, TIB KAT 716, 716LA, 716XLA, 718, 720, 789 from TIB Chemicals, and those from Shepherd Lausanne); - manganese salts, for example, manganese neodecanoate, manganese naphthenate; - cobalt salts, such as cobalt neodecanoate, cobalt ethylhexanoate, cobalt naphthenate; - iron salts, for example, iron ethylhexanoate; - mercury compounds, e.g., phenylmercury carboxylate is selected from.

[0169] Preferred organometallic compounds are dibutyltin dilaurate, dioctyltin dilaurate, zinc(II) diacetate, zinc(II) dioctanoate, zirconium acetylacetonate and zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate, bismuth neodecanoate, bismuth dioctanoate and bismuth ethylhexanoate.

[0170] In a preferred group of embodiments, the aqueous emulsion is an oil-in-water emulsion (o / w emulsion) of a water-immiscible liquid, the water-immiscible liquid comprising at least one organic active compound, which is preferably a pesticide.

[0171] Particularly preferred are oil-in-water (o / w) emulsions, in which the droplets of the o / w emulsion are formed by a water-immiscible liquid and surrounded by at least one conjugate as defined herein.

[0172] Suitable water-immiscible liquids (water-immiscible solvents) for dissolving organic active compounds are primarily any organic solvent or solvent mixtures which have a solubility in deionized water of less than or equal to 50 g / l or less than or equal to 20 g / l, in particular less than or equal to 10 g / l.

[0173] Suitable water-immiscible liquids (water-immiscible solvents) for dissolving organic active compounds, in particular pesticides, are in particular hydrocarbon solvents with a boiling point of at least 100°C, C8-C 26 C1-C8 alkyl esters of fatty acids, C8-C 26 Mono- and di-C1-C4 alkyl amides of fatty acids, N-C5-C 18 Alkylpyrrolidones and mixtures thereof. Of these, solvents and solvent mixtures that are liquid at 20°C are preferred.

[0174] In this context, "liquid" means that the diluent typically has a dynamic viscosity at 20°C under standard conditions (measured as specified in ASTM D 445) of not more than 150 mPa·s, in particular not more than 100 mPa·s, especially not more than 50 mPa·s, in particular in the range from 1 to 150 mPa·s, preferably in the range from 2 to 100 mPa·s, in particular in the range from 3 to 50 mPa·s.

[0175] In this context, aliphatic hydrocarbon solvents having a boiling point of at least 100°C refer in particular to saturated and unsaturated hydrocarbons, such as linear, branched, and cyclic alkanes and alkenes, having a boiling point within the specified range and containing from 7 to about 18 carbon atoms, which may optionally contain non-aromatic carbon rings, and in particular also to mixtures of these aliphatic hydrocarbons. Such mixtures are commercially available, for example, under the trade name Exxsol, which refers to products containing primarily kerosene depleted of aromatic components, such as Exxsol™ D30, Exxsol™ D40, Exxsol™ D80, Exxsol™ D100, Exxsol™ D120, and Exxsol™ D220 / 230. An example of an aliphatic hydrocarbon with a carbon ring is limonene.

[0176] In the context of the present invention, aromatic hydrocarbon solvents having a boiling point of at least 100°C refer in particular to monocyclic or polycyclic aromatic compounds which may optionally have one or more aliphatic or araliphatic substituents, in particular alkyl and arylalkyl moieties, and which have a boiling point within the specified range. The aromatic hydrocarbon solvent is preferably a mixture of such aromatic compounds obtained by distillation, in particular as a fraction of a given boiling range from a crude oil product, such as Solvesso®, in particular Solvesso® 100, Solvesso® 150, Solvesso® 200, Solvesso® 150 ND and Solvesso® 200 ND, Aromatic®, in particular Aromatic® 150 and Aromatic® 200, Hydrosol®, in particular Hydrosol® A 200 and Hydrosol® A 230 / 270, Caromax®, in particular Caromax® 20 and Caromax® 28, Aromat K 150, Aromat K 200, Shellsol®, in particular Shellsol® A 100 and Shellsol® A The term "Fin FAS-TX" refers to the commercially available products known under the trade names Fin FAS-TX 150 and Fin FAS-TX 200. Particularly preferred are mixtures depleted of naphthalene, a potential carcinogen, such as Solvesso® 150 ND and Solvesso® 200 ND (ExxonMobil Chemical). Thus, Solvesso® 150 ND boils in the range of 175-209°C and contains primarily aromatic hydrocarbons with 10 or 11 carbon atoms, primarily consisting of alkylbenzenes, whereas Solvesso® 200 ND boils in the range of 235-305°C and contains primarily aromatic hydrocarbons with 10-14 carbon atoms, primarily consisting of alkylnaphthalenes.

[0177] Another example of such an aromatic hydrocarbon solvent is the product known under the trade name Hisol SAS-296, which consists of a mixture of 1-phenyl-1-xylylethane and 1-phenyl-1-ethylphenylethane.

[0178] C8~C 26 C1 to C8 alkyl esters of fatty acids, and C8 to C 26 In relation to mono- and di-C1-C4 alkylamides of fatty acids, "C8-C 26 The term "fatty acid" refers to a fatty acid or mixture of fatty acids having 8 to 26 carbon atoms. 26 Examples of fatty acids are the saturated fatty acids caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and cerotic acid; the monounsaturated fatty acids undecylenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, eicosenoic acid, cetoleic acid, erucic acid, and nervonic acid; and the polyunsaturated fatty acids linoleic acid, linolenic acid, arachidonic acid, thymnodonic acid, clupanodonic acid, and cervonic acid.

[0179] C8~C 26 Among C1-C8 alkyl esters of fatty acids, C1-C4 alkyl esters, especially C 12 ~C 22 C1-C4 alkyl esters of fatty acids, especially C 12 ~C 22 Methyl and ethyl esters of fatty acids are preferred. Saturated or monounsaturated C 12 ~C 22 The total amount of fatty acids is at least 80% by weight based on the total weight of the fatty acids in the fatty acid ester. 12 ~C 22 C1 to C4 alkyl esters of fatty acids are preferred. 26 C1-C8 alkyl esters of fatty acids are products obtained from methylated or ethylated vegetable oils, ie by transesterification of vegetable oils with methanol or ethanol.

[0180] C8~C 26Among mono- and di-C1-C4 alkylamides of fatty acids, C 12 ~C 22 Mono- and di-C1-C4 alkylamides of fatty acids are preferred, in particular the mono-methylamides, mono-ethylamides, dimethylamides and diethylamides thereof. 12 ~C 22 The total amount of fatty acids is C 12 ~C 22 C, which is at least 80% by weight based on the total weight of fatty acids in the mono- and di-C1-C2 alkylamides of fatty acids 12 ~C 22 Mono- and di-C1-C2 alkylamides of fatty acids are particularly preferred. 14 ~C 18 Mixtures of methyl esters of fatty acids are commercially available, for example, under the trade name Synative™ ES ME TI 05 (Cognis).

[0181] N-C5~C 18 Examples of alkylpyrrolidones are N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-isopropylpyrrolidone, N-butylpyrrolidone, N-isobutylpyrrolidone, N-pentylpyrrolidone, N-hexylpyrrolidone, N-(4-ethyl-pentyl)pyrrolidone, N-octylpyrrolidone, N-2-ethylhexylpyrrolidone, N-nonylpyrrolidone, N-decylpyrrolidone and N-(7-methyl-decyl)pyrrolidone, n-dodecylpyrrolidone and N-tetradecylpyrrolidone.

[0182] The aqueous composition of the present invention containing at least one pesticide, particularly a pesticide, is particularly suitable for controlling plant pathogenic organisms or suppressing plant growth. Therefore, the use of the aqueous composition of the present invention containing at least one pesticide, particularly a pesticide, is particularly preferred for controlling plant pathogenic organisms or suppressing plant growth.

[0183] In aqueous compositions of the invention, the relative amount of conjugate will generally be in the range of 1 to 50% by weight, particularly in the range of 2 to 40% by weight, more particularly in the range of 3 to 35% by weight, and especially in the range of 5 to 30% by weight, based on the weight of the water-immiscible liquid.

[0184] In a particular group of embodiments, the aqueous composition is an aqueous oil-in-water emulsion (o / w emulsion), in which the amount of oil phase may be in the range of 0.1 to 60% by weight, in particular in the range of 1 to 50% by weight, and more particularly in the range of 1.5 to 40% by weight, based on the total weight of the emulsion.

[0185] The conjugates of the present invention can also be used in applications requiring the stabilization of aqueous emulsions, particularly oil-in-water emulsions, and / or the stabilization of oily soils. Thus, the conjugates of the present invention can also be used as surfactants in surfactant-containing compositions, such as dishwashing detergents, including machine dishwashing compositions and hand dishwashing detergents, cleaner compositions (cleaners), such as household cleaners, industrial cleaners, and hard surface cleaners, and cleaning and washing compositions, including liquid and solid laundry detergents. In these compositions, the conjugates can replace a portion of the conventional surfactants contained therein, thereby improving the ecological compatibility of these compositions. [Example]

[0186] The present invention will now be described in further detail by the following examples.

[0187] material: - CT-COOH: 5-((3,7-dimethyloct-6-en-1-yl)oxy)-5-oxopentanoic acid - MT-COOH: 5-((2-isopropyl-5-methylcyclohexyl)oxy)-5-oxopentanoic acid - THG-COOH: 5-((3,7-dimethyloctyl)oxy)-5-oxopentanoic acid - Citropol® H: Polycitrinellol. 6-octen-1-ol, 3,7-dimethyl-, homopolymer. CAS=888224-71-3. P2 Science - Novozyme 435: Immobilized lipase. Novozymes - Dextran 4: Anhydroglucose. CAS=9004-54-0. Serva Electrophoresis GmbH - Dextran-NH2: reaction product of dextran 4 and hexylenediamine - DMSO: Dimethyl sulfoxide. CAS=67-68-5 - THF: Tetrahydrofuran. CAS=109-99-9 - Cinmethylin: exo-(±)-1-methyl 2-(2-methylbenzyloxy)-4-isopropyl-7-oxa-bicyclo[2.2.1]heptane. BASF - Xanthan gum: Xanthan gum, Rhodopol® G, Solvay SA.

[0188] synthesis (1) Synthesis of terpene derivatives Example 1: Synthesis of 5-((3,7-dimethyloct-6-en-1-yl)oxy)-5-oxopentanoic acid (CT-COOH) The synthesis was carried out in two steps: esterification (I) followed by transesterification (II).

[0189] (i) Esterification: To a 25 mL round-bottom flask equipped with a magnetic stirrer were added glutaric acid (1.00 g, 7.57 mmol), citronellol (2.36 g, 15.14 mmol), Novozyme 435 (0.169 g), and 8 mL of 2-methylbutan-2-ol solvent. The flask was sealed, and the reaction mixture was stirred (170 rpm) at 40 °C for 6 h, resulting in the formation of bis(3,7-dimethyloct-6-en-1-yl)glutarate. After completion of the reaction, the mixture was filtered, and the solvent was evaporated on a rotary evaporator to yield 1.86 g of bis(3,7-dimethyloct-6-en-1-yl)glutarate.

[0190] (ii) Transesterification: To a 25 mL round-bottom flask equipped with a magnetic stirrer, glutaric acid (2.00 g, 15.14 mmol), bis(3,7-dimethyloct-6-en-1-yl)glutarate (6.19 g, 15.14 mmol), and a few drops of concentrated H2SO4 (catalytic amount) were added. The flask was sealed, and the reaction mixture was stirred at 100 °C overnight. The monoester was purified by column chromatography using a mixture of hexane:ethyl acetate (90:10) as the mobile phase. 3.32 g of the transesterified monoester, 5-((3,7-dimethyloct-6-en-1-yl)oxy)-5-oxopentanoic acid (CT-COOH), was obtained.

[0191] Example 2: Synthesis of 5-((2-isopropyl-5-methylcyclohexyl)oxy)-5-oxopentanoic acid (MT-COOH) Using the same two-step procedure as in Example 1, 5-((2-isopropyl-5-methylcyclohexyl)oxy)-5-oxopentanoic acid was prepared.

[0192] (i) Esterification: Using menthol (2.36 g, 15.14 mmol) instead of citronellol, 1.92 g of bis(2-isopropyl-5-methylcyclohexyl) glutarate was obtained.

[0193] (ii) Transesterification: Using bis(2-isopropyl-5-methylcyclohexyl)glutarate (6.19 g, 15.14 mmol) instead of bis(3,7-dimethyloct-6-en-1-yl)glutarate, 1.98 g of 5-((2-isopropyl-5-methylcyclohexyl)oxy)-5-oxopentanoic acid (MT-COOH) was obtained.

[0194] Example 3: Synthesis of 5-((3,7-dimethyloctyl)oxy)-5-oxopentanoic acid (THG-COOH) Using the same two-step procedure as in Example 1, 5-((2-isopropyl-5-methylcyclohexyl)oxy)-5-oxopentanoic acid was prepared.

[0195] (i) Esterification: Tetrahydrogeraniol (2.40 g, 15.14 mmol) was used instead of citronellol to give 2.01 g of bis(3,7-dimethyloctyl) glutarate.

[0196] (ii) Transesterification: Using bis(3,7-dimethyloctyl)glutarate (6.25 g, 15.14 mmol) instead of bis(3,7-dimethyloct-6-en-1-yl)glutarate, 2.02 g of 5-((3,7-dimethyloctyl)oxy)-5-oxopentanoic acid (THG-COOH) was obtained.

[0197] Example 4: Synthesis of Citropol-COOH A 250 mL round-bottom flask equipped with a magnetic stirrer was charged with 21.12 g of glutaraldehyde, 10 g of Citropol® H, 1.55 g of Novozyme 435, 20 g of dried molecular sieves, and 45 mL of 2-methylbutan-2-ol solvent. The flask was sealed, and the reaction mixture was stirred (170 rpm) at 40 °C for 16 hours, resulting in the formation of Citropol-COOH. After the reaction was complete, the mixture was filtered, and the solvent was evaporated on a rotary evaporator. The crude mixture was then dissolved in 100 mL of water and added dropwise to 600 mL of water, resulting in phase separation of the desired material. The oily phase was dried over sodium sulfate and evaporated to yield 7.5 g of Citropol-COOH.

[0198] (2) Modification of dextran with terpene derivatives Example 5: Synthesis of dextran-graft-citronellol Dextran 4 (0.25 g), CT-COOH (0.25 g, 9.2 × 10 mol), and 3 mL of dry DMSO were added to a 10 mL round-bottom flask equipped with a magnetic stirrer. The mixture was stirred to obtain a homogeneous solution. Novozyme 435 (0.125 g) and dry molecular sieves (1.0 g) were then added, and the flask was sealed. The reaction mixture was heated at 40 °C for 24 h with stirring (170 rpm). After the reaction, the modified dextran was precipitated three times in acetone to remove free terpenes. After the drying process, 0.16 g of the dextran-grafted citronellol amphiphilic polymer was recovered as a powder.

[0199] Example 6: Synthesis of dextran-graft-menthol Dextran-graft-menthol was produced using the same procedure as in Example 5. Here, only the differences in terms of the raw materials or amounts used are listed. MT-COOH (0.50 g, 1.85 mmol) was used instead of CT-COOH. 5 mL of dry DMSO, 0.625 g of Novozyme 435, and 3 g of dry molecular sieves were added. After the drying process, 0.20 g of dextran-graft-menthol polymer was recovered as a powder.

[0200] The biodegradability of the compounds in soil was evaluated using the sandy soil Lihof C15 according to ISO 17556. The percentage of biodegradation was determined by the release of CO2 produced during mineralization. After 28 and 90 days, biodegradation was found to be 72% and 85%, respectively.

[0201] Example 7: Synthesis of Dextran-graft-Citropol Dextran 4 (0.40 g), Citropol-COOH (Example 4, 0.80 g), and 10 mL of dry DMSO were added to a 25 mL round-bottom flask equipped with a magnetic stirrer. The mixture was stirred to obtain a homogeneous solution. Novozyme 435 (0.30 g) and dry molecular sieves (1.60 g) were then added, and the flask was sealed. The reaction mixture was heated at 40°C for 24 hours with stirring (170 rpm). After the reaction, the modified dextran was precipitated three times in methanol to remove unreacted Citropol derivatives. After the drying process, 0.34 g of the dextran-graft-Citropol amphiphilic polymer was recovered as a waxy solid.

[0202] The biodegradability of the compounds in soil was evaluated using the sandy soil Lihof C15 according to ISO 17556. The percentage of biodegradation was determined by the release of CO2 produced during mineralization. After 28 and 90 days, biodegradation was found to be 59% and 75%, respectively.

[0203] Example 8: Synthesis of Dextran-block-Citropol The synthesis was carried out in two steps: amination (i) followed by amidation (ii).

[0204] (i) Amination: Dextran 4 (1.00 g), hexylenediamine (112 g, 9.63 mmol), and 2 mL of water were added to a 10 mL round-bottom flask equipped with a magnetic stirrer. The mixture was stirred for 2 h. Sodium cyanoborohydride (0.125 g, 1.99 mmol) was then added.

[0205] The flask was sealed and the reaction mixture was stirred (170 rpm) at room temperature overnight. The medium was precipitated twice in acetone and dried to give 0.91 g of end-aminated dextran (dextran-NH).

[0206] (ii) Amidation: Dextran-NH2 (0.40 g), Citropol-COOH (Example 4, 0.80 g), and 6 mL of dry DMSO were added to a 25 mL round-bottom flask equipped with a magnetic stirrer. After mixing, Novozyme 435 (0.15 g) and dry molecular sieves (1.00 g) were added to the solution. The flask was sealed, and the reaction mixture was stirred at 40 °C for 24 h. After the reaction, the modified dextran was precipitated three times in methanol to remove unreacted Citropol derivatives. After the drying process, 0.32 g of the dextran-block-Citropol amphiphilic polymer was recovered as a powder.

[0207] (3) Emulsion stability Example 9: Preparation of cinmethylin liquid emulsion containing dextran-graft-menthol To a plastic vial, 7.00 g of distilled water and 0.60 g of the dextran-graft-menthol produced in Example 6 were added. The medium was stirred to promote dissolution of the polymer. 2.40 g of cinmethylin was then added, and the vial was placed in an ice bath. The mixture was then subjected to high shear using an ultrasonic homogenizer UP400S (Hielscher Ultrasonics) at 80% amplitude for 1 minute using 0.5 cycles.

[0208] A homogeneous emulsion with a droplet diameter D[3,2] = 2.8 μm was obtained. No phase separation or segregation was observed over 24 h.

[0209] Example 10: Preparation of cinmethylin liquid emulsion containing dextran-graft-citropol To a plastic vial, 0.085 g of cinmethylin, 0.015 g of dextran-graft-citropol (synthesized in Example 7), and 9.90 g of phosphate buffer (pH 6, 0.5 M) were added. Finally, the mixture was blended by Ultraturax for 5 minutes to obtain a white emulsion.

[0210] No phase separation or change in turbidity was observed over 72 hours.

[0211] Example 11: Preparation of a cinmethylin liquid emulsion containing hydrophobic dextran (comparative example) To a plastic vial, 1 g of cinmethylin, 0.10 g of unmodified dextran 4, and 9.00 g of phosphate buffer (pH 5.8, 0.5 M) were added. The mixture was placed in a water bath and then subjected to high shear using an ultrasonic homogenizer, Vibra Cell 72408, at 30% amplitude for 5 minutes. A stable emulsion could not be obtained, and complete segregation was observed within a few hours.

[0212] (4) Herbicidal activity of the cinmethylin liquid emulsion of the present invention The following cinmethylin liquid emulsions according to the present invention, designated herein as Formulations 1 and 2 (hereinafter also designated F1 and F2) and having the compositions shown in Table 1, were evaluated for their herbicidal activity.

[0213] [Table 1]

[0214] Formulations 1 and 2 were prepared according to the procedure of Example 9 using the amounts shown in Table 1, with the further exception that water was first mixed with the dextran-grafted menthol as well as xanthan gum in the amounts shown in Table 1.

[0215] The herbicidal activity of Formulations 1 and 2 against various weeds and crops was demonstrated in the following pre-emergence greenhouse experiment: Formulations 1 and 2 of the present invention and a conventional cinmethylin formulation were applied, and the herbicidal effects of these treatments were compared.

[0216] Test plants were sown in plastic containers containing sandy loam soil containing 5% organic matter. For preemergence treatment, Formulations 1 and 2, as well as two conventional formulations for comparison purposes, polyurea capsule suspension (CS) and emulsifiable concentrate (EC), containing 400 g / L and 750 g / L cinmethylin, respectively, were applied immediately after sowing using a fine-dispersing nozzle at rates of 100, 50, 25, and 12.5 g ai / ha (ai = active ingredient; cinmethylin in this case). The containers were gently irrigated to promote germination and growth, and then covered with a transparent plastic hood until the plants were established. This cover allowed the test plants to germinate uniformly, unless adversely affected by the active compounds. The plants were grown at temperatures ranging from 10 to 35°C according to their individual requirements.

[0217] The herbicidal activity of each herbicidal formulation was evaluated 10 and 20 days after treatment (10 and 20 DAT). The results are summarized in Table 2. The damage caused by the formulations to undesirable weeds and crop plants was assessed compared to untreated control plants using a 0 to 100% scale, where 0% means no damage and 100% means complete plant death.

[0218] The plants used in the greenhouse tests belonged to the following species:

[0219] [Table 2]

[0220] [Table 3]

[0221] As can be seen from the results summarized in Table 2, formulations F1 and F2 according to the invention exhibit improved or at least similar activity against weeds and improved or at least similar selectivity against weeds over crops compared to conventional cinmethylin formulations.

Claims

1. A conjugate of a sugar compound selected from disaccharides, oligosaccharides and polysaccharides and at least one hydrophobic compound selected from terpenes, polyterpenes and polyterpene ethers, The hydrophobic compound in the conjugate is either directly attached to an oxygen atom of the sugar or is attached to a group of formula (I) or (II): R-O-(Y) ｋ -A １ -X １ - (I) ____) ｋ . １ ︹ ２ . ２ ︹ ３ (II)) (In formulas (I) and (II), R is a radical of a terpene compound, polyterpene or polyterpene ether compound; k is 0 or 1; Y is C(O) or C(O)NH; A １ is a direct bond or C １ ~C ６ is alkylene, A ２ is C ２ ~C １０ is alkylene, X １ is C(O), or k=1 and A １ is C １ ~C ６ When it is alkylene, it may be OC(O) or NHC(O), and X １ is attached to an oxygen atom of the sugar compound, X ２ is C(O)NH or NHC(O)NH, X ３ - is N= or NH-, X in formula (II) ３ is attached to a carbon atom of the sugar compound) or as a conjugate.

2. The sugar compound of the conjugate has the following properties 2.a to 2.d:

2. a) having an average number of 2 to 1000 monosaccharide repeating units; 2. b is a nonionic polysaccharide; 2. c glucan, 2. d Selected from dextran, pullulan, dextrin and combinations thereof 2. The conjugate of claim 1, wherein

3. 3. The conjugate of claim 1, wherein the hydrophobic compound is selected from mono-, sesqui-, and diterpenols, oxidized mono-, sesqui-, and diterpenols, and polyterpene ether compounds, the terpene units of which are derived from mono-, sesqui-, and diterpenols.

4. 4. The conjugate of claim 3, wherein the hydrophobic compound is selected from monoterpenols, sesquiterpenols, oxidized monoterpenols, and oxidized sesquiterpenols.

5. 5. The conjugate of claim 3 or 4, wherein the hydrophobic compound is a terpenol selected from citronellol, nerol, geraniol, myrcenol, pulegol, menthol, and combinations thereof.

6. The following properties 5.a or 5.b:

5. a) the weight ratio of the hydrophobic compound to the sugar compound in the conjugate is in the range of 3:1 to 1:80, in particular in the range of 2:1 to 1:60; 5. b The conjugate has a degree of substitution of the hydrophobic compound in the range of 1 to 300 mol % relative to the monosaccharide units of the sugar. The conjugate according to any one of claims 1 to 5, having at least one of:

7. 7. The conjugate of any one of claims 1 to 6, wherein the hydrophobic compound in the conjugate is either directly attached to an oxygen atom of the sugar or is present as a group of formula (I).

8. 7. The conjugate according to any one of claims 1 to 6, wherein the hydrophobic compound is present as a group of formula (II), in which R is in particular a polyterpene ether group.

9. Use of the conjugate of any one of claims 1 to 8 as a stabilizer for an aqueous emulsion of a water-immiscible liquid.

10. An aqueous composition which is an aqueous emulsion of a water-immiscible liquid, comprising at least one conjugate according to any one of claims 1 to 7.

11. 11. The use or composition according to claim 9 or 10, wherein the weight ratio of the conjugate to the water-immiscible liquid in the emulsion is in the range of 1:100 to 1:1, in particular in the range of 1:50 to 1:2, especially in the range of 1:30 to 1:

3.

12. The use or composition according to any one of claims 9 to 11, wherein the water-immiscible liquid comprises at least one organic active compound.

13. 13. The use or composition according to claim 12, wherein the organic active compound is a water-immiscible liquid at 22°C and / or is dissolved in a water-immiscible organic solvent.

14. 14. The use or composition according to claim 12 or 13, wherein the organic active compound is selected from pesticides, aroma chemicals, pharmaceutically active compounds, vitamins, cosmetic actives and organic beneficial compounds.

15. 15. The use or composition according to any one of claims 12 to 14, which is an oil-in-water (o / w) emulsion, droplets of said o / w emulsion formed by said water-immiscible liquid and surrounded by at least one conjugate according to any one of claims 1 to 8.

16. 16. The use or composition of any one of claims 9 to 15, wherein the relative amount of said conjugate is in the range 1 to 50% by weight, based on the weight of said water-immiscible liquid.

17. 10. A method for stabilizing an aqueous emulsion, in particular an oil-in-water emulsion of a water-immiscible liquid, comprising incorporating into said emulsion of said water-immiscible liquid a conjugate according to any one of claims 1 to 8.

18. Use of a composition according to any one of claims 10 to 16, containing at least one pesticide, for controlling plant pathogenic organisms or inhibiting plant growth.

19. 17. A method for controlling plant pathogenic organisms, comprising the step of applying a pesticidally effective amount of a composition according to any one of claims 10 to 16, comprising at least one pesticide, to the plant pathogenic organisms, or to the habitat of the plant pathogenic organisms, or to plants whose growth is to be controlled.

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