Method for producing polyol-based esters of ketocarboxylic acids

Abstract

To provide an efficient method for producing physiologically suitable or physiologically compatible precursors and / or metabolites of acetoacetate or eventually 3-hydroxybutyric acid (i. e. beta-hydroxybutyric acid or BHB or 3-BHB) or their salts.SOLUTION: In a method for producing polyol esters, especially polyglycerol esters, of 3-oxobutyric acid, at least one compound of the general formula (I): CH3-C(O)-CH2-C(O)OR1, wherein the radical R1 represents C1-C4-alkyl, is reacted with at least one polyol (II) comprising at least two, especially at least three, hydroxy groups (OH groups), especially polyglycerol, so that, as a reaction product, one or more 3-oxobutyric acid polyol esters (III) are obtained.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to the field of ketobodies and related metabolism and the treatment of related diseases.

[0002] In particular, the present invention relates to a method for producing polyol esters of 3-oxobutyric acid (also synonymously referred to as "3-oxobutanoic acid", "beta-oxobutyric acid", "beta-oxobutanoic acid", etc.), in particular a method for producing polyglycerol esters of 3-oxobutyric acid, as well as the reaction products thus obtained or thus produced (i.e. the polyol esters of 3-oxobutyric acid, in particular the polyglycerol esters of 3-oxobutyric acid) and their functionalized derivatives, as well as their uses, in particular their use in pharmaceutical compositions, drugs or medicines, etc., or in food and / or food products, as well as further applications or uses thereof.

[0003] Furthermore, the present invention relates to pharmaceutical compositions, in particular drugs or pharmaceutical products, comprising the reaction products (i.e. polyol esters of 3-oxobutyric acid, in particular polyglycerol esters of 3-oxobutyric acid) obtained or produced according to the process of the present invention, their applications or uses.

[0004] Finally, the present invention relates to food and / or food products, in particular food supplements, functional foods, novel foods, food additives, food supplements, diet foods, power snacks, appetite suppressants, and strength and / or endurance sports supplements, comprising the reaction products obtained or produced by the process of the present invention (i.e. polyol esters of 3-oxobutyric acid, in particular polyglycerol esters or functionalized derivatives thereof), and applications or uses thereof. [Background technology]

[0005] In human energy metabolism, glucose is a short-term available energy carrier and is metabolized to energy in mitochondria by releasing water and carbon dioxide. Liver glycogen stores are already emptied during the nighttime sleep period. However, the human central nervous system (CNS) and heart, in particular, require a permanent energy supply.

[0006] Physiological substitutes for glucose that can be utilized primarily by the central nervous system are the so-called keto bodies (also synonymously called ketone bodies).

[0007] The term keto bodies is a general term for three compounds that are primarily formed under catabolic metabolic conditions (fasting, weight loss diets, low carbohydrate diets, etc.) to produce ketosis. The term keto bodies specifically includes three compounds, acetoacetate (also synonymously referred to as acetacetate or 3-oxobutyrate) and acetone, as well as 3-hydroxybutyrate (hereinafter also referred to as beta-hydroxybutyrate or BHB or 3-BHB) or a salt thereof (i.e., 3-hydroxybutyrate or beta-hydroxybutyrate).

[0008] These keto bodies are also provided in physiologically large quantities from lipids stored in the body by lipolysis during fasting or starvation and almost completely replace glucose as an energy source.

[0009] Keto bodies are formed in the liver from acetyl-coenzyme A (=acetyl-CoA) derived from beta-oxidation; they represent a transportable form of acetyl-coenzyme A in the human body. However, to utilize keto bodies, the brain and muscles must first adapt to express the enzymes required to convert keto bodies back to acetyl-coenzyme A. Especially during fasting, keto bodies contribute a significant amount of energy production. For example, after a while the brain can only take up one-third of the daily glucose amount.

[0010] Physiologically, keto bodies are synthesized from two molecules of activated acetate in the form of acetyl-coenzyme A, a normal intermediate product of fatty acid degradation, which is elongated to the intermediate product 3-hydroxy-3-methyl-glutaryl-CoA (HMG-CoA) using acetyl-coenzyme A alone and the enzyme HMG-CoA synthase, and finally HMG-CoA-lyase cleaves acetoacetate. These three steps are carried out exclusively in the liver mitochondria (linen cycle), and 3-hydroxybutyrate is finally formed in the cytosol from acetoacetate by the enzyme D-beta-hydroxybutyrate dehydrogenase. HMG-CoA is also the end product of the degradation of the amino acid leucine, while acetoacetate is formed during the degradation of the amino acids phenylalanine and tyrosine.

[0011] Thus, acetoacetate is reductively converted under physiological conditions to the physiologically relevant form 3-hydroxybutyric acid or 3-hydroxybutyrate.

[0012] 3-Hydroxybutyrate is currently used in weight training and is commercially available as the sodium, magnesium, or calcium salt.

[0013] However, because plants do not produce 3-hydroxybutyrate, and because 3-hydroxybutyrate in animal organisms occurs only in emaciated and dead animals that have entered ketosis, 3-hydroxybutyrate itself is evolutionarily unknown to humans or exists in very small amounts, so that oral administration of 3-hydroxybutyrate causes nausea. Also, 3-hydroxybutyrate in the free acid or salt form has a very bitter taste and causes severe vomiting and nausea.

[0014] Furthermore, patients, especially newborns, but even adults, cannot permanently tolerate large amounts of salts of 3-hydroxybutyric acid, as these compounds can damage the kidneys.

[0015] Furthermore, the plasma half-life of 3-hydroxybutyric acid and its salts is very short, since ketosis only lasts for about 3-4 hours, even when a few grams are ingested, meaning that patients cannot continuously benefit from treatment with 3-hydroxybutyric acid or its salts, especially at night. In the case of metabolic diseases, this can lead to a life-threatening situation.

[0016] Therefore, in the case of such metabolic diseases, so-called medium chain triglycerides, also known as MCTs, are currently used for ketogenic therapy, i.e. saturated linear C6-, C8-, C9-, C10-, C11-, C12-, C13-, C14-, C15-, C16-, C17-, C18-, C19-, C20-, C21-, C22-, C33-, C34-, C35-, C36-, C37-, C38-, C49-, C49-, C49-, C49-, C50-, C51-, C52-, C53-, C54-, C55-, C60-, C61-, C62-, C63-, C64-, C65-, C66-, C67-, C68-, C71-, C72-, 10 -Metabolic transformation of fatty acids) is intended.

[0017] But basically, from a pharmaceutical and clinical point of view, acetoacetate, as a physiological precursor of 3-hydroxybutyric acid, is a more effective drug-pharmacological target molecule, which according to the prior art could in principle be used for the treatment of a large number of diseases (e.g. diseases associated with dysfunction of energy metabolism, in particular keto body metabolism, or dementia, neurodegenerative diseases such as Alzheimer's disease, Parkinson's disease, lipid metabolic diseases, etc.), but which cannot be used due to lack of physiological compatibility.

[0018] The following table shows purely exemplary, but by no means limiting, potential therapeutic options or possible indications for the active ingredient acetoacetate or 3-hydroxybutyric acid or its salts (i.e. 3-hydroxybutyric acid) obtained by physiological reduction of acetoacetate.

[0019] [Table 1] Summary of the Invention [Problem to be solved by the invention]

[0020] It is therefore desirable from a pharmaceutical and clinical point of view to be able to find effective precursors or metabolites that allow direct or indirect access physiologically to acetoacetate (and also physiologically to 3-hydroxybutyric acid or its salts), especially in the physiological metabolism of the human or animal body.

[0021] As a result, the prior art is not lacking in attempts to find physiologically relevant precursors or metabolites of 3-hydroxybutyric acid or its salts. However, so far, no efficient compounds have been found in the prior art. Moreover, access to such compounds is not possible or easily possible according to the prior art.

[0022] Thus, the problem underlying the present invention is to provide an efficient method for producing physiologically relevant or physiologically compatible precursors and / or metabolites of acetoacetate or ultimately 3-hydroxybutyrate (i.e., beta-hydroxybutyrate or BHB or 3-BHB) or salts thereof.

[0023] Such methods should, in particular, produce acetoacetate or the respective BHB precursors and / or BHB metabolites in accessible, particularly large, amounts in an efficient manner, and without significant amounts of toxic by-products. [Means for solving the problem]

[0024] The Applicant has discovered in a completely surprising manner that polyol esters of 3-oxobutyric acid, in particular polyglycerol esters, represent efficient and physiologically effective or physiologically compatible precursors and / or metabolites of the keto forms acetoacetate or 3-hydroxybutyric acid, and has been able to find or develop efficient methods for producing these compounds, which are produced therefrom under physiological conditions or their salts, and in this regard allow direct and effective, in particular economically and industrially feasible access to these compounds.

[0025] Therefore, in order to solve the above mentioned problems, the present invention proposes according to a first aspect a method for producing polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid according to claim 1; further particularly special and / or advantageous embodiments of the inventive method are the subject of the associated process dependent claims.

[0026] Furthermore, the present invention relates according to a second aspect to a process for the functionalization of 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid), in particular for the preparation of fatty acid functionalized polyol esters, in particular polyglycerol esters, according to claim 40; further particularly special and / or advantageous embodiments of the process according to the invention are the subject of the associated process dependent claims.

[0027] Furthermore, the present invention relates according to a third aspect to a reaction product obtainable according to the inventive process according to the independent claims (claims 57, 58, 65, 66, 72 or 73) or to a polyol ester, in particular a polyglycerol ester, of 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid) or a mixture thereof according to the respective claims (claims 84 to 107); further particularly special and / or advantageous embodiments of this aspect of the invention are the subject of the associated dependent claims.

[0028] Similarly, the present invention relates according to a fourth aspect to a pharmaceutical composition, in particular a drug or medicament, according to the respective independent claim (claim 108); further particularly special and / or advantageous embodiments of this aspect of the invention are the subject matter of the associated dependent claims.

[0029] Furthermore, the present invention relates according to a fifth aspect to a reaction product according to the invention or a polyol ester of 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid), in particular a polyglycerol ester or a mixture thereof, according to the invention for use in the preventive and / or therapeutic treatment or the preventive and / or therapeutic treatment of diseases of the human or animal body according to the respective independent claim (claim 110).

[0030] Furthermore, the present invention relates according to a sixth aspect to the use of the inventive reaction products according to the related independent claim (claim 111) or mixtures thereof of the inventive polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid), for the manufacture of a medicament for the prophylactic and / or therapeutic treatment of diseases of the human or animal body or for the prophylactic and / or therapeutic treatment of diseases of the human or animal body.

[0031] Furthermore, the present invention relates according to a seventh aspect to the use of the inventive polyol esters, in particular polyglycerol esters, of the inventive 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid) according to the inventive reaction products or the inventive 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid) according to the related independent claim (claim 112) or mixtures thereof.

[0032] Furthermore, the present invention relates, according to an eighth aspect of the present invention, to a food product and / or food product according to the associated independent claim (claim 113); further particularly special and / or advantageous embodiments of the food product and / or food product according to the invention are the subject of the associated dependent claims.

[0033] Finally, the present invention relates according to a ninth aspect to the use of the inventive reaction products or the inventive polyol esters of 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid), in particular polyglycerol esters or mixtures thereof, in food and / or food products according to the relevant independent claims (claim 115); further particularly special and / or advantageous embodiments of the uses according to the invention are the subject of the relevant dependent use claims.

[0034] It goes without saying that the following features, embodiments, advantages, etc. are listed below only with respect to one aspect of the invention in order to avoid repetition, but of course also apply to other aspects of the invention without the need for separate mention.

[0035] Furthermore, it goes without saying that individual aspects and embodiments of the present invention are also considered to be disclosed in any combination with other aspects and embodiments of the present invention, in particular in any combination of features and embodiments resulting from all backward references, and the claims are also considered to be broadly disclosed with respect to all resulting combination possibilities.

[0036] It is further noted that with regard to all relative or percentage weight-based data provided below, in particular relative amounts or weight data, within the scope of the present invention, these should always be selected by the skilled artisan such that the total amounts up to 100% or 100% by weight, respectively, including all ingredients or contents, in particular as defined below; however, this is self-evident to the skilled artisan.

[0037] Moreover, those skilled in the art can deviate from the range specifications set forth below, if desired, without departing from the scope of the present invention.

[0038] Furthermore, it applies that all values ​​or parameters etc. specified below can in principle be determined or identified using standardized or explicitly specified measurement methods or determination or measurement methods well known to the person skilled in the art.

[0039] With this being said, the present invention will now be described in more detail.

[0040] The subject of the present invention therefore, according to a first aspect thereof, is a process for the preparation of polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid), comprising: Radical R 1 denotes C1-C4-alkyl, in particular methyl or ethyl, preferably ethyl, of the general formula (I) CH3-C(O)-CH2-C(O)OR 1 (I) with at least one polyol (II) having at least two, in particular at least three, hydroxyl groups (OH groups), in particular polyglycerol, to obtain as reaction product one or more 3-oxobutyric acid polyol esters (III), in particular 3-oxobutyric acid polyglycerol esters.

[0041] As mentioned above, the Applicant has very surprisingly discovered that the polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid) thus produced - also synonymously referred to as "3-oxobutyric acid polyol esters, in particular 3-oxobutyric acid polyglycerol esters" - are effective since the physiologically compatible precursors and / or metabolites of 3-hydroxybutyric acid or its salts are physiologically compatible and therefore can also be used in large quantities for pharmaceutical or clinical applications.

[0042] The above-mentioned polyol esters, in particular the polyglycerol esters, of 3-oxobutyric acid, which are accessible in an efficient manner for the first time through the preparation process according to the invention, represent physiologically and pharmacologically relevant alternatives to free 3-hydroxybutyric acid or its salts.

[0043] The preparation of polyol esters of 3-oxobutyric acid, in particular polyglycerol esters, by conventional organic synthesis is complicated and expensive due to the instability and decomposition of 3-oxobutyric acid.Within the scope of the present invention, it has been possible for the first time to provide an efficiently functioning preparation method by which polyol esters of 3-oxobutyric acid, in particular polyglycerol esters, can be prepared in a single step and without undesirable side reactions.

[0044] The process of the invention therefore makes it possible for the first time to provide non-toxic polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid from known, commercially available and in particular physiologically harmless components or reactants (starting compounds). The resulting polyol esters, especially polyglycerol esters, of 3-oxobutyric acid can be physiologically degraded, especially in the stomach and / or intestines, to ultimately release or generate the target molecule "acetoacetate" from this "3-hydroxybutyric acid" or a salt thereof as the active ingredient or substance.

[0045] Furthermore, the aforementioned polyol esters, particularly the polyglycerol esters, of 3-oxobutyric acid also contain an acceptable taste to ensure suitability even when administered orally in large amounts over an extended period of time (e.g., daily doses of 50 g or more).

[0046] Likewise, the preparation process according to the invention makes it possible to provide optionally acylated polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid which are free from toxic impurities.

[0047] Furthermore, the process according to the invention, including any further processing or purification steps, can be economically operated and carried out on a large scale.

[0048] In particular, the process of the present invention uses commercially available starting compounds, making it economically efficient even when implemented on a large scale, yet allowing for relatively simple process control.

[0049] In contrast to the prior art manufacturing methods, the manufacturing method according to the present invention does not use complex starting materials and uses only a single step. Nevertheless, according to the present invention, excellent productivity is achieved and the formation of by-products is minimized or avoided. In particular, dimerization can be prevented by the proprietary reactants used to form 3-hydroxybutyric acid precursors or metabolites.

[0050] Moreover, the method of the invention is simple and economical. In particular, the method according to the invention is usually carried out in the absence and / or without solvent (i.e. as a mass reaction or as a reaction in a substance or as a so-called bulk reaction); as a result, the reaction products obtained are not contaminated with solvents and, after the method or reaction has been carried out, there is no need to remove and dispose of the solvent or reuse it in a costly and energy-consuming manner. Furthermore, no toxic by-products are formed.

[0051] The preparation process according to the invention usually results in a mixture of different polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid, so-called mixtures of at least two, in particular at least three different polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid. The resulting raw reaction products or raw mixtures can be purified by known methods, in particular by removing remaining starting compounds and / or by-products present, and further, if necessary, separated by known methods, in particular by distillation and / or chromatography (such as fractionation into the individual polyol esters of 3-oxobutyric acid, i.e. mono-, di-, tri-, etc. polyol esters, or into fractions containing enriched and depleted portions of the individual fractions).

[0052] Furthermore, the process of the present invention does not require enantioselective reaction control since the formation or release of the active ingredient 3-hydroxybutyric acid in the gastrointestinal tract always occurs in the physiologically relevant form of the R-enantiomer.

[0053] According to the invention, in the general formula (I), the radical R 1 It is preferred if represents ethyl.

[0054] In other words, according to the invention, as compound of general formula (I), it is preferred to use 3-oxobutyric acid ethyl ester (ethyl 3-oxobutyrate) of formula CH3-C(O)-CH2-C(O)OC2H5.

[0055] This allows for particularly efficient process control and high productivity, with the formation of by-products being minimized or suppressed. Moreover, 3-oxobutyric acid ethyl ester is also commercially available in large quantities and, moreover, in contrast to the free acid (i.e., 3-oxobutyric acid), is stable and can therefore be used with less effort. In particular, 3-oxobutyric acid ethyl ester can be obtained on a large scale as starting compound, for example, by Claisen condensation of ethyl acetate.

[0056] In particular, in the method of the present invention, the reaction is carried out in the absence and / or without a solvent. This means that the reaction is carried out as a mass reaction or as a material reaction or as a so-called bulk reaction. This has the advantage that the reaction product obtained is not contaminated with the solvent and there is no need to remove and dispose or recycle the solvent after the method or reaction is carried out in a costly and energy-intensive manner. Surprisingly, the method or reaction nevertheless proceeds with high conversion and productivity, at least essentially, without significant formation of by-products.

[0057] According to a particular embodiment of the invention, the reaction can be carried out in the presence of a catalyst, in particular an enzyme and / or a metal-containing and / or metal-based acidic or basic catalyst, in which case the catalyst is preferably recycled after the reaction.

[0058] As mentioned above, according to a particular embodiment of the production method of the invention, the reaction can be carried out in the presence of an enzyme as a catalyst.

[0059] In this context, the enzymes may in particular be chosen from synthetases (ligases), catalases, esterases, lipases, and combinations thereof. According to the invention, synthetases (synonym ligase) are in particular enzymes from the class of ligases; ligases are enzymes that facilitate the joining of two or more molecules by covalent bonds. Catalases in the sense of the invention are in particular enzymes capable of converting hydrogen peroxide into oxygen and water. The term esterases in particular denotes enzymes capable of hydrolytically decomposing esters into alcohols and acids (saponification); they are therefore in particular hydrolases, and lipolytic esterases are also called lipases. Lipases in the sense of the invention are in particular enzymes capable of decomposing free fatty acids from lipids such as glycerides (lipolysis).

[0060] Within the scope of the present invention, the enzymes used as catalysts are those derived from Candida antarctica, Mucor miehei (Rhizomucor miehei), Thermomyces lanuginosus, Candida rugosa, Aspergillus oryzae, Pseudomonas cepacia, Pseudomonas fluorescens, Rhizopus derema and Pseudomonas bacteria and combinations thereof, preferably Candida antarctica, Mucor miehei (Rhizomucor miehei) and Thermomyces lanuginosus.

[0061] According to a particular embodiment, the enzymes can be used in immobilized form, immobilized on a support, preferentially on a polymeric support, preferably on a polymeric organic support, more preferably on a hydrophobic and even more preferably on a poly(meth)acrylic resin-based carrier.

[0062] As explained above with respect to the use of catalysts generally, when an enzyme is used as a catalyst, it is preferable to recycle the enzyme after the reaction.

[0063] Within the framework of the production method of the present invention, when the reaction is carried out in the presence of an enzyme as a catalyst, it is particularly preferable to carry out the reaction at a temperature in the range of 10°C to 80°C, in the range of 20°C to 80°C, preferably in the range of 25°C to 75°C, more preferably in the range of 45°C to 75°C, and even more preferably in the range of 50°C to 70°C.

[0064] When an enzyme is used as a catalyst, the amount of enzyme used can vary over a wide range. In particular, the enzyme can be used in an amount ranging from 0.001% to 20% by weight, in particular ranging from 0.01% to 15% by weight, preferably ranging from 0.1% to 15% by weight, preferably ranging from 0.5% to 10% by weight, based on the total amount of starting compounds (I) and (II). Nevertheless, it may be necessary to deviate from the above amounts in individual cases or for specific applications, without departing from the scope of the invention.

[0065] According to a particular embodiment of the present invention, when the reaction is carried out in the presence of an enzyme as a catalyst, the applied pressure range can also vary within a wide range. In particular, when the reaction is carried out in the presence of an enzyme as a catalyst, the reaction can be carried out at a pressure in the range of 0.0001 bar to 10 bar, in particular in the range of 0.001 bar to 5 bar, preferably in the range of 0.01 bar to 2 bar, more preferably in the range of 0.05 bar to 1 bar, and even more preferably at about 1 bar.

[0066] According to an alternative embodiment of the invention, the reaction may be carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst.

[0067] According to this alternative embodiment of the invention, the reaction is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst, which may be selected from (i) basic catalysts, for example selected from NaOH, KOH, LiOH, Ca(OH)2, NaOMe, KOMe and Na(OBu-tert.), in particular alkali or alkaline earth hydroxides and alkali or alkaline earth alcoholates, (ii) acidic catalysts, in particular mineral and organic acids, such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid, methanesulfonic acid, paratoluenesulfonic acid, carboxylic acids, etc., (iii) Lewis acids, in particular Lewis acids based on titanium, tin, zinc, aluminum compounds, such as titanium tetrabutylate, stannic acid, zinc acetate, aluminum trichloride, aluminum triisopropyl, and (iv) heterogeneous catalysts, in particular heterogeneous catalysts based on mineral silicates, such as zeolites, montmorillonite, mordenite, hydrotalcite, alumina, germanates, carbonates, aluminum oxide, and combinations thereof.

[0068] According to this embodiment, in particular alkali or alkaline earth alcoholates can be used as catalysts.

[0069] In particular, and according to this embodiment, it is preferred if the catalyst based on a metal-containing and / or metal-based acidic or basic catalyst is recycled after the reaction.

[0070] According to a particular embodiment of the present invention, when the reaction is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst, the temperature can be varied within a wide range. In particular, the reaction can be carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst at a temperature in the range of 20°C to 150°C, in particular in the range of 50°C to 140°C, preferably in the range of 70°C to 130°C, more preferably in the range of 80°C to 125°C, even more preferably in the range of 100°C to 120°C.

[0071] Furthermore, and also according to this embodiment, the catalyst (i.e. metal-containing and / or metal-based acidic or basic catalyst) can also be varied within a wide amount range: for example, catalysts based on metal-containing and / or metal-based acidic or basic catalysts can be used in an amount in the range of 0.01 to 30% by weight, in particular in the range of 0.05 to 15% by weight, preferably in the range of 0.1 to 15% by weight, preferably in the range of 0.2 to 10% by weight, based on the total amount of starting compounds (I) and (II). Nevertheless, it is possible to deviate from the above amounts for specific applications or individual cases without departing from the scope of the invention.

[0072] According to this particular embodiment of the invention, when the reaction is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst, the pressure range may equally vary within wide limits; in particular, the reaction may be carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst at a pressure in the range of 0.0001 bar to 10 bar, in particular in the range of 0.001 bar to 5 bar, preferably in the range of 0.01 bar to 2 bar, more preferably in the range of 0.05 bar to 1 bar, and even more preferably at a pressure of about 1 bar.

[0073] As far as the amounts of starting materials or starting compounds are concerned, these can also be varied within wide limits.

[0074] Taking into account the process economy and the optimization of the course of the method, especially with regard to the minimization of by-products, it is advantageous when the polyol (II), in particular the compound of general formula (I) based on the hydroxyl groups of the polyglycerol, is used in a molar amount ranging from an equimolar amount to a molar excess of more than 200 mol %, in particular from an equimolar amount to a molar excess of 150 mol %, preferably from an equimolar amount to a molar excess of 100 mol %.

[0075] Likewise, taking into account the process economy and optimization of the process steps, in particular with regard to the minimization of by-products, it is advantageous to use compounds of general formula (I) and polyols (II), in particular polyglycerol, in a molar ratio of compounds of general formula (I) / polyols (II) in the range of 1:1 to 10:1, in particular in the range of 2:1 to 8:1, preferably in the range of 3:1 to 6:1.

[0076] As far as the polyols (II) which can be used in the process according to the invention are concerned, it is particularly preferred when the polyols (II) contain at least three hydroxyl groups (OH groups).

[0077] According to a particular embodiment of the process of the invention, the polyol (II) is General formula (IIa) (HO) m -(X)-(OH) n (IIa) It may in particular be provided that corresponds to In addition, in the general formula (IIa), X especially contains from 4 to 21 carbon atoms, optionally containing from 1 to 9 oxygen atoms, and is preferably selected from alkyl radicals or (poly)alkyl ether radicals, in particular (poly)alkylene glycol radicals, more preferably C4-C 21 -Alkyl radical or C4-C 21 -(Poly)alkyl ether radicals, especially C4-C 21 - represents an organic radical selected from (poly)alkylene glycol radicals; and The variables m and n are independent of each other and represent integers from 1 to 10.

[0078] In particular, according to the invention, it is preferred in this respect that the hydroxyl groups of the polyol (II) are located at any position of the radical X, preferably at least one hydroxyl group is terminal (i.e. a primary hydroxyl group). This means in particular that the hydroxyl group can be located or provided at any position of the organic radical X (provided, however, that preferably at least one hydroxyl group is terminal and / or a primary hydroxyl group).

[0079] In particular, the polyols (II) which can be used within the scope of the process of the invention are polyether polyols and alkane polyols and combinations thereof, in particular C4-C 21 -Polyether polyols and C4-C 21 -Alkane polyols, preferably C4-C 21 -Polyether polyols and C4-C 21 -alkanediols, more preferably polyether polyols, even more preferably C4-C 21 - polyether polyols.

[0080] According to a particular embodiment of the process according to the invention, the polyol (II) is a polyether polyol, in particular a C4-C 21 polyether polyols, preferably of the general formula (IIb) HO-CH2-CH(OH)-CH2-[O-CH2-CH(OH)-CH2] p -OH (IIb) The polyglycerol may be selected from the polyglycerols listed below. In the general formula (IIb), the variable p represents an integer of 1 to 6, particularly 1 to 4, preferably 1 or 2, and more preferably 1.

[0081] According to another particular embodiment of the process according to the invention, the polyol (II) has the general formula (IIc) HO-CH2-CH(OH)-CH2-O-CH2-CH(OH)-CH2-OH (IIc) diglycerol.

[0082] According to a further particular embodiment of the process according to the invention, the polyol (II) is an alkanediol, in particular a C4-C 21 -Alkanediols, preferably linear or branched alkanediols, preferably linear or branched C4-C 21 -Alkanediol Linear C4-C 21 -Alkanediols, even more preferably linear C4-C having at least one terminal and / or primary hydroxyl group 21 -alkanediols, even more preferably pentanediols, in particular 1,2 pentanediol.

[0083] According to a preferred embodiment of the process of the present invention, polyol (II) is not propane-1,2,3-triol, i.e. polyol (II) is not glycerol.

[0084] According to an alternative preferred embodiment of the process of the invention, polyol (II) is propane-1,2,3-triol, i.e. polyol (II) is glycerol.

[0085] According to a preferred embodiment of the invention, the invention according to this aspect of the invention relates to a process for the preparation of polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid), in particular a process as described below, Radical R 1 represents C1-C4-alkyl, in particular methyl or ethyl, preferably ethyl, of the general formula (I) CH3-C(O)-CH2-C(O)OR 1 (I) At least one compound of The polyol (II) is a polyether polyol, in particular a C4-C 21 polyether polyols, of general formula (IIb), in which the variable p is an integer from 1 to 6, in particular from 1 to 4, preferably 1 or 2 and more preferably 1 HO-CH2-CH(OH)-CH2-[O-CH2-CH(OH)-CH2]p -OH (IIb) with at least one polyol (II), in particular a polyglycerol, having at least two hydroxyl groups (OH groups), selected from the polyglycerols As reaction product, one or more 3-oxobutyric acid polyol esters (III), in particular 3-oxobutyric acid polyol esters, are obtained.

[0086] According to another preferred embodiment of the invention, the invention according to this aspect of the invention relates to a process for the preparation of polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid), in particular a process as described below, Radical R 1 represents ethyl, CH3-C(O)-CH2-C(O)OR 1 (I) At least one compound of The polyol (II) is a polyether polyol, in particular a C4-C 21 polyether polyols, of general formula (IIb) in which the variable p is the integer 1 or 2, preferably 1 HO-CH2-CH(OH)-CH2-[O-CH2-CH(OH)-CH2] p -OH (IIb) with at least one polyol (II), in particular a polyglycerol, having at least two hydroxyl groups (OH groups), selected from the polyglycerols As reaction product, one or more 3-oxobutyric acid polyol esters (III), in particular 3-oxobutyric acid polyol esters, are obtained.

[0087] The following reaction or synthesis schemes illustrate approaches that are particularly preferred according to the present invention (depending on the reaction control, either individual esters or mixtures of two or more of them can be obtained):

[0088] [ka]

[0089] In the process according to the invention, during the reaction, the radical R 1 represents C1-C4 alkyl, in particular methyl or ethyl, preferably ethyl, of the general formula (IV) R 1 -OH (IV) is simultaneously formed.

[0090] In particular, it is preferred in this respect if the compound according to general formula (IV) is recovered from the reaction, in particular continuously recovered, in particular continuously removed by distillation. In this way, the reaction equilibrium is effectively shifted towards the reaction product. Also, in this way, the formation of by-products is minimized or prevented.

[0091] Within the scope of the inventive preparation process, the reaction products, in particular the composition of the reaction products, in particular the presence of various 3-oxobutyric acid polyol esters (III), in particular 3-oxobutyric acid polyglycerol esters, and their ratio in the case of mixtures, are preferably controlled and / or regulated by the reaction conditions, in particular by selecting the reaction temperature (conversion temperature), and / or by selecting the reaction pressure (conversion pressure), and / or by providing a catalyst and selecting such catalyst in terms of type and / or amount, and / or by selecting the amount of starting compounds (reactants), and / or by providing for the removal of the compounds according to the general formula (IV) defined above.

[0092] After the reaction, the resulting reaction product may be subjected to further purification or work-up steps.

[0093] In this connection, the reaction products obtained can be fractionated after the reaction has been carried out, in particular by distillation.

[0094] Also, unreacted starting compounds (I) and / or (II) may be separated from the reaction product and then recycled.

[0095] According to a particular embodiment of the preparation process according to the invention, it is particularly possible to proceed in such a way that the hydroxyl groups still present in the reaction product after the reaction has taken place are at least partially, preferably completely, functionalized, in particular esterified. In particular, the reaction can be followed by a partial, in particular complete functionalization, in particular esterification, of the hydroxyl groups still present.

[0096] In this particular embodiment of the process of the invention, in particular the functionalization, in particular the esterification, of the hydroxyl groups still present in the reaction product after the reaction has taken place is carried out by means of a compound of the general formula (V) R 3 -OR 3 (V) The reaction can be carried out using at least one carboxylic acid anhydride of In this general formula (V), each independently of the other radicals R 3 are of type linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)-; and / or In this general formula (V), the radical R 3 are identical or different fatty acid radicals, each of which is independent of the other, especially C5-C 34 - Fatty acid radical, preferably C8-C 34 -Fatty acid radical.

[0097] Furthermore, in this particular embodiment of the process according to the invention, the carboxylic acid anhydride of general formula (V) is a fatty acid anhydride, in particular a C5-C 34 -Fatty acid anhydrides, preferably C8-C 34 It is preferred if the compound is a fatty acid anhydride.

[0098] In particular, as the carboxylic acid anhydride of general formula (V), the radical R 3In other words, as the carboxylic acid anhydride of the general formula (V), a symmetrical carboxylic acid anhydride is used.

[0099] According to an alternative embodiment, the carboxylic acid anhydride of general formula (V) is provided by the radical R 3 In other words, as the carboxylic acid anhydride of the general formula (V), an asymmetric carboxylic acid anhydride is used.

[0100] According to the invention, the functionalization of the hydroxyl groups still present in the reaction product after the reaction with at least one carboxylic anhydride of general formula (V) can be carried out at temperatures in the range of 60 to 150°C, in particular in the range of 70 to 120°C, preferably in the range of 80 to 100°C.

[0101] The inventive functionalization of the hydroxyl groups still present in the reaction product after the reaction with at least one carboxylic anhydride of general formula (V) has taken place can be carried out at a pressure in particular in the range from 0.0001 bar to 10 bar, in particular in the range from 0.001 bar to 5 bar, preferably in the range from 0.01 bar to 2 bar, more preferably in the range from 0.05 bar to 1 bar, and even more preferably at a pressure of about 1 bar.

[0102] In particular, the functionalization of the hydroxyl groups still present in the reaction product after the reaction with at least one carboxylic anhydride of general formula (V) has taken place is carried out in the absence of and / or without solvent. The so-called reaction is carried out as a reaction of mass or as a reaction of substance or as a so-called bulk reaction. This has the advantage that the reaction product obtained is not contaminated with solvent, and after the process or reaction has been carried out, the solvent does not have to be removed and disposed of or recycled in a costly and energy-intensive manner. Surprisingly, the process or reaction nevertheless proceeds with high conversion and productivity, at least essentially, without significant formation of by-products.

[0103] In the course of the inventive functionalization of the hydroxyl groups still present in the reaction product after the reaction with at least one carboxylic anhydride of general formula (V) has taken place, radicals R 3 has the above defined meaning, R 3 -OH (VI) The compound is formed simultaneously.

[0104] In particular, it is preferred in this context if the compound according to general formula (VI) is recovered during or after the reaction has taken place, in particular after the reaction has taken place, preferably by distillation.

[0105] Following the inventive functionalization of the hydroxyl groups still present in the reaction product after the reaction with at least one carboxylic acid anhydride of general formula (V) has taken place, the product obtained can be subjected to further purification or work-up steps which are conventional or known per se.

[0106] In this context, it is preferred that the functionalization is followed by distillation and / or chromatography, preferably by distillation.

[0107] In particular, reactants and reaction by-products still present, in particular the compounds according to general formula (VI), are distilled off.

[0108] In the process of functionalization according to the invention, in general formula (V) the radical R 3 are different from each other and / or in the general formula (V) the radical R 3 where each represents an alkyl radical having two or more carbon atoms, a carboxylic acid anhydride of the general formula (V) can be prepared by reacting with an acetic anhydride of the general formula (VI) in which the radical R3 has the meaning defined above. R 3 -OH (VI) with at least one carboxylic acid, in particular a fatty acid.

[0109] In this connection, the reaction of acetic anhydride with at least one carboxylic acid of general formula (VI), in particular a fatty acid, takes place according to the reaction scheme shown below: where the radical R 3 has the meaning defined above, but the radical R 3 are different from each other and / or the radicals R 3 each independently represent an alkyl radical having two or more carbon atoms.

[0110] [ka]

[0111] According to a particular embodiment of the method of the invention, a symmetrical carboxylic acid anhydride of general formula (V) is produced. In other words, in general formula (V), the radical R 3 are identical and represent alkyl radicals having more than two carbon atoms.

[0112] According to an alternative particular embodiment of the process of the invention, an asymmetric carboxylic acid anhydride of general formula (V) is produced. Thus, in general formula (V), the radical R 3 are different from each other, preferably in the general formula (V) the radical R 3 each represents an alkyl radical having three or more carbon atoms.

[0113] According to an alternative embodiment of the functionalization, in particular esterification, of the hydroxyl groups still present in the reaction product after the reaction has taken place, it is preferred that they are represented by the general formula (VII) R 3 -OR 4 (VII) with at least one carboxylic acid and / or carboxylic acid ester of Here, in the general formula (VII), Radical R 3 are of type linear (straight-chain) or branched, saturated or mono- or polyunsaturated (C1-C 33-alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)- radical, Radical R 4 represents hydrogen or C1-C4-alkyl, in particular methyl or ethyl, preferably hydrogen.

[0114] In this respect, the carboxylic acids and / or carboxylic acid esters of general formula (VII) are fatty acids and / or fatty acid esters, in particular C5-C 34 -Fatty acids and / or C5-C 34 -fatty acid esters, preferably C8-C34-fatty acids and / or C8-C34-fatty acid esters.

[0115] In particular, in this embodiment according to the invention, after the reaction with at least one carboxylic acid and / or carboxylic acid ester of general formula (VII) has taken place, the functionalization of the hydroxyl groups still present in the reaction product is carried out in the absence and / or without solvent. The so-called reaction is carried out as a reaction of mass or as a reaction of substance or as a so-called bulk reaction. This has the advantage that the reaction product obtained is not contaminated with solvent and that after the process or reaction has been carried out, the solvent does not have to be removed and disposed of or recycled in a costly and energy-intensive manner. Surprisingly, the process or reaction nevertheless proceeds with high conversion and productivity, at least essentially, without significant formation of by-products.

[0116] According to a preferred embodiment, the functionalization of the hydroxyl groups still present in the reaction product after the reaction with the at least one carboxylic acid and / or carboxylic ester of general formula (VII) has taken place is carried out in the presence of a catalyst, in particular an enzyme and / or a metal-containing and / or metal-based acidic or basic catalyst.

[0117] In this connection it is particularly preferred if the catalyst is recycled after the reaction.

[0118] As mentioned before, according to a preferred embodiment, after the reaction has been carried out with at least one carboxylic acid and / or carboxylic ester of general formula (VII), the functionalization of the hydroxyl groups still present in the reaction product is carried out in the presence of an enzyme as catalyst.

[0119] In particular, the enzymes are preferably selected from synthetases (ligases), catalases, esterases, lipases and combinations thereof. According to the invention, synthetases (synonym ligases) are in particular enzymes from the class of ligases; ligases are enzymes that facilitate the joining of two or more molecules by covalent bonds. Catalases in the sense of the invention are in particular enzymes capable of converting hydrogen peroxide into oxygen and water. The term esterases in particular denotes enzymes capable of hydrolytically decomposing esters into alcohols and acids (saponification); these are therefore in particular hydrolases, and lipolytic esterases are also called lipases. Lipases in the sense of the invention are in particular enzymes capable of decomposing free fatty acids from lipids such as glycerides (lipolysis).

[0120] In this particular embodiment, the enzymes used as catalysts are those derived from Candida antarctica, Mucor miehei (Rhizomucor miehei), Thermomyces lanuginosus, Candida rugosa, Aspergillus oryzae, Pseudomonas cepacia, Pseudomonas fluorescens, Rhizopus derema and Pseudomonas bacteria and combinations thereof, preferably Candida antarctica, Mucor miehei (Rhizomucor miehei) and Thermomyces lanuginosus.

[0121] In this context, it is particularly preferred if the enzyme is used in immobilized form, in particular on a support, preferably on a polymeric support, more preferably on a polymeric organic support, more preferably on a hydrophobic, even more preferably on a poly(meth)acrylic resin-based support.

[0122] As already mentioned in connection with catalysis in general, it is preferred if the enzyme is recycled after the reaction.

[0123] It is preferred if the reaction is carried out at a temperature in the range of 10° C. to 80° C., in particular in the range of 20° C. to 80° C., preferably in the range of 25° C. to 75° C., more preferably in the range of 45° C. to 75° C., even more preferably in the range of 50° C. to 70° C., as long as the functionalization of the hydroxyl groups still present in the reaction product after the reaction has been carried out with at least one carboxylic acid and / or carboxylic acid ester of general formula (VII) is carried out in the presence of an enzyme as a catalyst.

[0124] When enzymes are used as catalysts, the amount of enzyme used can vary over a wide range. In particular, the enzymes can be used in an amount ranging from 0.001% to 20% by weight, in particular ranging from 0.01% to 15% by weight, preferably ranging from 0.1% to 15% by weight, more preferably ranging from 0.5% to 10% by weight, based on the total amount of starting compounds. Nevertheless, it may be necessary to deviate from the above amounts in individual cases or for specific applications without leaving the scope of the invention. In this context, the starting compounds are 3-oxobutyric acid polyol esters (III) and carboxylic acids and / or carboxylic acid esters of general formula (VII).

[0125] According to a particular embodiment of the invention, when the functionalization of the hydroxyl groups still present in the reaction product after the reaction with at least one carboxylic acid and / or carboxylic acid ester of general formula (VII) is carried out in the presence of an enzyme as a catalyst, the pressure range applied can also vary within a wide range. In particular, when the reaction is carried out in the presence of an enzyme as a catalyst, it is preferred to carry out the reaction at a pressure in the range of 0.0001 bar to 10 bar, in particular in the range of 0.001 bar to 5 bar, in the range of 0.01 bar to 2 bar, more preferably in the range of 0.05 bar to 1 bar, and even more preferably at a pressure of about 1 bar.

[0126] According to an alternative embodiment of the inventive functionalization of the hydroxyl groups still present in the reaction product after the reaction has taken place with the at least one carboxylic acid and / or carboxylic ester of general formula (VII), the functionalization is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst.

[0127] According to this alternative embodiment of the functionalization according to the invention, the functionalization is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst, which may in particular be selected from (i) basic catalysts, for example selected from NaOH, KOH, LiOH, Ca(OH)2, NaOMe, KOMe and Na(OBu-tert.), in particular alkali or alkaline earth hydroxides and alkali or alkaline earth alcoholates, (ii) acidic catalysts, in particular mineral and organic acids, such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid, methanesulfonic acid, paratoluenesulfonic acid, carboxylic acids, etc., (iii) Lewis acids, in particular Lewis acids based on titanium, tin, zinc and aluminum compounds, such as titanium tetrabutylate, stannic acid, zinc acetate, aluminum trichloride and triisopropylaluminum, and (iv) heterogeneous catalysts, in particular based on mineral silicates, such as zeolites, montmorillonite, mordenite, hydrotalcite, alumina, germanates, carbonates, aluminum oxides and combinations thereof.

[0128] In this embodiment, alkali or alkaline earth alcoholates can in particular be used as catalysts.

[0129] In particular, in this embodiment of the functionalization, it is also preferred if the catalyst, which is based on a metal-containing and / or metal-based acidic or basic catalyst, is recycled after the reaction.

[0130] According to this particular embodiment of the invention, if the functionalization of the hydroxyl groups still present in the reaction product after the reaction has been carried out with at least one carboxylic acid and / or carboxylic acid ester of general formula (VII) is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst, the temperature can be varied within a wide range. In particular, the reaction can be carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst at a temperature in the range of 20°C to 150°C, in particular in the range of 50°C to 140°C, preferably in the range of 70°C to 130°C, more preferably in the range of 80°C to 125°C, even more preferably in the range of 100°C to 120°C.

[0131] Moreover, also in this embodiment, the catalyst (i.e. metal-containing and / or metal-based acidic or basic catalyst) can be varied within a wide amount range: Thus, the metal-containing and / or metal-based acidic or basic catalyst can be used in an amount in the range of 0.01% by weight to 30% by weight, in particular in the range of 0.05% by weight to 15% by weight, preferably in the range of 0.1% by weight to 15% by weight, preferably in the range of 0.2% by weight to 10% by weight, based on the total amount of starting compounds. Nevertheless, it is possible to deviate from the above amounts for specific applications or individual cases without leaving the scope of the invention. In this respect, the starting compounds are 3-oxobutyric acid polyol esters (III) and carboxylic acids and / or carboxylic acid esters of the general formula (VII).

[0132] According to this particular embodiment of the invention, if the functionalization of the hydroxyl groups still present in the reaction product after the reaction has taken place with the at least one carboxylic acid and / or carboxylic ester of general formula (VII) is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst, the pressure range can equally vary within a wide range: in particular, the reaction can be carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst at a pressure in the range from 0.0001 bar to 10 bar, in particular in the range from 0.001 bar to 5 bar, preferably in the range from 0.01 bar to 2 bar, more preferably in the range from 0.05 bar to 1 bar, and even more preferably at a pressure of about 1 bar.

[0133] In this particular embodiment of the functionalization of the hydroxyl groups still present in the reaction product after the reaction with at least one carboxylic acid and / or carboxylic acid ester of general formula (VII) has taken place, Radical R 4 has the above defined meaning, R 4 -OH (VIII) is simultaneously formed.

[0134] In particular, in this regard, it is preferred if the compound of general formula (VIII) is recovered during or after the reaction, in particular during the reaction, preferably by distillation. In this way, the reaction equilibrium is effectively shifted to the side of the reaction product. Also, in this way, the formation of by-products is minimized or prevented.

[0135] According to a particular embodiment of the process according to the invention, the ester group introduced into the reaction product (III) by the aforementioned method can be subjected to a partial transesterification with a compound of general formula (VII) as defined above. In other words, the ester group introduced into the reaction product (III) by the aforementioned method can be subjected to a partial transesterification with a compound of general formula (VII) as defined above. 3 It is preferred that the ester is partially exchanged by transesterification with

[0136] In this context, the transesterification according to this particular embodiment of the invention is carried out under reaction conditions such as those described above for the inventive functionalization of the hydroxyl groups still present in the reaction product after the reaction has been carried out with at least one carboxylic acid and / or carboxylic acid ester.

[0137] Particularly preferred procedures according to the invention intended for the functionalization, in particular esterification, of the hydroxyl groups still present after the reaction are illustrated by the following reaction or synthesis schemes, in which, depending on the reaction sequence during the reaction, either individual esters or mixtures of two or more of them are obtained, and in the following reaction or synthesis schemes, the radical R is a hydroxyl group of the formula CH3-(CH2) x=0-28 Represents the radical -C(O)-:

[0138] [ka]

[0139] Furthermore, the present invention relates to a process for the preparation of functionalized, in particular fatty acid-functionalized, polyol esters, in particular polyglycerol esters, of 3-oxobutyric acid (beta-oxobutyric acid, 3-oxobutanoic acid), comprising the steps of: (A) According to the (first) synthetic route (A), first in a first process step, a radical R 1 represents C1-C4-alkyl, in particular methyl or ethyl, preferably ethyl, CH3-C(O)-CH2-C(O)OR 1 (I) At least one compound of reacting with at least one polyol (II) having at least two hydroxyl groups (OH groups), in particular as defined above, in particular a polyglycerol, This is then followed by a second process step, which comprises: (i) by at least one fatty acid and / or its ester or anhydride, in particular by at least one C5-C 34 - by fatty acids, preferably at least one C8-C 34 at least partial functionalization, in particular at least partial esterification, of the still present hydroxyl groups by fatty acids and / or their esters or anhydrides, and / or (ii) by at least one fatty acid and / or its ester, in particular by at least one C5-C 34 - by fatty acids and / or their esters, preferably C8-C 34 - having a partial transesterification of the ester groups introduced in the first process step by fatty acids and / or esters thereof, or (B) (Second, alternative to (A)) According to synthetic route (B), first in a first process step, at least one polyol (II), in particular a polyglycerol, comprising at least two hydroxyl groups (OH groups), in particular as defined above, is reacted with at least one fatty acid and / or its ester or anhydride, in particular at least one C5-C 34 - fatty acids and / or their esters or anhydrides, preferably at least one C8-C 34 - reacting with fatty acids and / or their esters or anhydrides, This is followed by a second process step, which comprises: (i) at least partial esterification of the still present hydroxyl groups by a compound of general formula (I) as defined above, and / or (ii) having a partial transesterification of the ester groups introduced in the first process step with a compound of general formula (I) as defined above, This results in the production of in each case one or more functionalized, in particular fatty acid-functionalized, preferably C5-C 34 -Fatty acid functionalized, preferably C8-C 34- fatty acid functionalized 3-oxobutyric acid polyol esters (III'), preferably one or more functionalized, in particular fatty acid functionalized, preferably C5-C 34 -Fatty acid functionalized, preferably C8-C 34 -fatty acid functionalized 3-oxobutyric acid polyglycerol esters are obtained.

[0140] In particular, the inventive preparation process according to synthetic route (A) can be carried out according to the inventive method described above.

[0141] According to a particular embodiment of this aspect of the invention, according to synthetic route (B), polyol (II) is a polyether polyol, in particular a C3-C 21 polyether polyols, preferably of general formula (IIb'), in which the variable q represents an integer from 0 to 6, in particular an integer from 0 to 4, preferably an integer from 0 to 4, preferably an integer 0 or 1, more preferably an integer 1 HO-CH2-CH(OH)-CH2-[O-CH2-CH(OH)-CH2] q -OH (IIb') It is particularly provided that the polyglycerol is selected from the polyglycerols

[0142] According to a further particular embodiment of the process of the invention, according to the synthetic route (B), the polyol (II) is of formula (IIc) HO-CH2-CH(OH)-CH2-O-CH2-CH(OH)-CH2-OH (IIb') It is preferable that the diglycerol is diglycerol of the formula:

[0143] According to yet another particular embodiment of the process of the invention, according to synthetic route (B), polyol (II) is preferably propane-1,2,3-triol (glycerol).

[0144] According to an alternative particular embodiment of the process of the invention, according to synthetic route (B), polyol (II) is not propane-1,2,3-triol (glycerol).

[0145] With regard to the fatty acids and / or fatty acid esters which can be used in the process of the invention according to the synthesis route (B), it is preferred that the fatty acids and / or fatty acid esters are carboxylic acids and / or fatty acids of the general formula (VII) R 3 -OR 4 (VII) It is particularly preferred that the carboxylic acid ester of the formula: In this general formula (VII), Radical R 3 are of type linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)- radical, Radical R 4 represents hydrogen or C1-C4-alkyl, in particular hydrogen, methyl or ethyl, more preferably hydrogen.

[0146] Furthermore, with regard to the fatty acid anhydrides which can be used in the process of the invention according to the synthesis route (B), it is preferred that the fatty acid anhydride has the general formula (V) R 3 -OR 3 (V) It is particularly preferred when the carboxylic acid anhydride is a carboxylic acid anhydride of the formula: In addition, in the general formula (V), Radical R 3 are of type linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)- radical.

[0147] In particular, in the method of the invention, according to the synthetic route (B), in the first process step, the reaction is carried out in the absence and / or without a solvent. As mentioned above, this means that the reaction is carried out as a reaction of mass or as a reaction of substance or as a so-called bulk reaction. This has the advantage that the reaction product obtained is not contaminated with solvent and there is no need to remove the solvent in a costly and energy-intensive manner to dispose of or recycle it after the method or reaction has been carried out. Surprisingly, the method or reaction nevertheless proceeds with high conversion and productivity and, at least essentially, without significant formation of by-products.

[0148] According to a particular embodiment of the method of the invention, according to synthetic route (B), in the first process step, when fatty acids and / or esters thereof are used as starting materials, it is preferred that the reaction is carried out in the presence of a catalyst, in particular a metal-containing and / or metal-based acidic or basic catalyst.

[0149] In this regard, it is particularly preferred if the catalyst is recycled after the reaction.

[0150] Alternatively to this particular embodiment, according to synthetic route (B), when using fatty acid anhydrides as starting materials, the reaction is carried out in the absence and / or without a catalyst.

[0151] As mentioned above, according to a particular embodiment of the inventive preparation method, according to synthetic route (B), when fatty acids and / or esters thereof are used as reactants in the first process step, the reaction is preferably carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst.

[0152] The catalyst may be selected from (i) basic catalysts, for example selected from NaOH, KOH, LiOH, Ca(OH)2, NaOMe, KOMe and Na(OBu-tert.), in particular alkali or alkaline earth hydroxides and alkali or alkaline earth alcoholates, (ii) acidic catalysts, in particular mineral and organic acids, such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid, methanesulfonic acid, paratoluenesulfonic acid, carboxylic acids, etc., (iii) Lewis acids, in particular Lewis acids based on titanium, tin, zinc and aluminum compounds, such as titanium tetrabutylate, stannic acid, zinc acetate, aluminum trichloride and triisopropylaluminum, and (iv) heterogeneous catalysts, in particular based on silicate minerals, germanates, carbonates and aluminum oxides, such as zeolites, montmorillonite, mordenite, hydrotalcite and alumina, as well as combinations thereof.

[0153] In this embodiment, alkali or alkaline earth alcoholates can in particular be used as catalysts.

[0154] In particular, as mentioned above, it is preferred in this regard to recycle the catalyst after the reaction.

[0155] According to this particular embodiment, when the reaction is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst, it is preferred if the reaction is carried out at a temperature in the range of 20°C to 150°C, in particular in the range of 50°C to 140°C, preferably in the range of 70°C to 130°C, more preferably in the range of 80°C to 125°C, even more preferably in the range of 100°C to 120°C.

[0156] In particular, according to this embodiment, it is preferred if the catalyst is used in an amount in the range of 0.01% by weight to 30% by weight, in particular in the range of 0.05% by weight to 15% by weight, preferably in the range of 0.1% by weight to 15% by weight, more preferably in the range of 0.2% by weight to 10% by weight, based on the total amount of starting compounds.

[0157] Furthermore, according to this embodiment, it is preferred that the reaction is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst at a pressure in the range of 0.0001 bar to 10 bar, in particular in the range of 0.001 bar to 5 bar, preferably in the range of 0.01 bar to 2 bar, more preferably in the range of 0.05 bar to 1 bar, even more preferably at a pressure of about 1 bar.

[0158] Within the scope of the inventive process, when synthetic route (B) is followed and fatty acids and / or esters thereof are used as starting materials, radicals R 4 has the above defined meaning, R 4 -OH (VIII) are simultaneously formed.

[0159] In this connection it is particularly preferred if the compound of general formula (VIII) is recovered during or after the reaction, in particular during the reaction, preferably by distillation.

[0160] Within the scope of the process of the invention, according to synthesis route (B), when fatty anhydrides are used as starting materials, radicals R 3 has the above defined meaning, R 3 -OH (VI) are simultaneously formed.

[0161] In particular, it is preferred if the compound of formula (VI) is recovered during or after the reaction, preferably by distillation.

[0162] In particular, in the method of the invention, according to synthetic route (B), the second process step is also carried out in the absence and / or without a solvent.

[0163] Furthermore, in the method of the invention, according to synthetic route (B), the second process step is also carried out in the presence of a catalyst, in particular a metal-containing and / or metal-based acidic or basic catalyst.

[0164] In this regard, it is also preferred that the catalyst is recycled after the reaction.

[0165] According to another particular embodiment of the invention, the process according to synthetic route (B) is preferred, when the second process step is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst.

[0166] The catalyst is preferably selected from (i) basic catalysts, for example selected from NaOH, KOH, LiOH, Ca(OH)2, NaOMe, KOMe and Na(OBu-tert.), in particular alkali or alkaline earth hydroxides and alkali or alkaline earth alcoholates, (ii) acidic catalysts, in particular mineral and organic acids, such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid, methanesulfonic acid, paratoluenesulfonic acid, carboxylic acids, etc., (iii) Lewis acids, in particular Lewis acids based on titanium, tin, zinc and aluminum compounds, such as titanium tetrabutylate, stannic acid, zinc acetate, aluminum trichloride and triisopropylaluminum, and (iv) heterogeneous catalysts, in particular based on silicates, germanates, carbonates and aluminum oxides, such as zeolites, montmorillonite, mordenite, hydrotalcite and alumina, as well as combinations thereof.

[0167] In this connection, the catalysts used are in particular alkali or alkaline earth alcoholates.

[0168] As mentioned previously, it is particularly advantageous if the catalyst is recycled after esterification and / or transesterification.

[0169] According to this particular embodiment of the method of the invention, the temperature can vary within a wide range. In particular, according to synthetic route (B), the second process step is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst at a temperature in the range of 20° C. to 150° C., in particular in the range of 50° C. to 140° C., preferably in the range of 70° C. to 130° C., more preferably in the range of 80° C. to 125° C., even more preferably in the range of 100° C. to 120° C.

[0170] Furthermore, the amount of catalyst can also be varied according to this particular embodiment: the catalyst can thus be used in an amount in the range of 0.01% to 30% by weight, in particular in the range of 0.05% to 15% by weight, preferably in the range of 0.1% to 15% by weight and more preferably in the range of 0.2% to 10% by weight, based on the total amount of starting compounds.

[0171] According to this particular embodiment of the invention, if, according to synthetic route (B), the second process step is carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst, the pressure can vary in a wide range: in particular, the second process step can be carried out in the presence of a metal-containing and / or metal-based acidic or basic catalyst at a pressure in the range from 0.0001 bar to 10 bar, in particular in the range from 0.001 bar to 5 bar, preferably in the range from 0.01 bar to 2 bar, more preferably in the range from 0.05 bar to 1 bar, even more preferably at a pressure of about 1 bar.

[0172] In this particular embodiment of the process of the invention, according to synthetic route (B), in the second process step, a compound of general formula (IX) R 1 -OR 5 (IX) are simultaneously formed. Where: Radical R 1 represents C1-C4-alkyl, in particular methyl or ethyl, preferably ethyl, Radical R 5are each independently the same or different and are hydrogen or a radical R as defined above. 3 Represents.

[0173] In this context, it is specifically contemplated that the compound of general formula (IX) is recovered during or after the reaction, in particular during the reaction, preferably by distillation.

[0174] In the process according to the invention, according to the first and second aspects of the invention, in particular fatty acids or derivatives thereof, in particular esters or anhydrides, can be used for functionalization or esterification or transesterification.

[0175] According to the invention, fatty acids, preferably C5-C 34 -fatty acids, more preferably C8-C 34 - The group of fatty acids is: caprylic, pelargonic, capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, margaric, stearic, nonadecanoic, arachidic, heneicosanoic, behenic, lignoceric, cerotic, montanic, melissic, racemic, gedic, undecylic, myristoleic, palmitic, margaric, petroselinic, oleic, elaidic, vaccenic, gadolic, cetrilic, erucic, nervonic. It is specifically contemplated that the fatty acids are selected from the group consisting of linoleic acid, linolenic acid, calendulic acid, punic acid, eleosteaic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, docosadienoic acid, docosatetraenoic acid, docosapentaenoic acid, wellosahexaenoic acid, and tetracosahexaenoic acid, and mixtures thereof.

[0176] According to a particular embodiment of the invention, fatty acids, particularly in the free form or in the form of their esters or anhydrides, preferably C5-C 34 -Fatty acids, preferably C8-C 34It is preferred that the fatty acids are selected from the group consisting of myristic acid, pentadecanoic acid, palmitoleic acid, cetrilic acid, oleic acid, gadoleic acid, cetrilic acid, erucic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, docosatetraenoic acid, docosapentaenoic acid, docosahexaenoic acid, docosahexaenoic acid, preferably from the group consisting of eicosapentaenoic acid and docosahexaenoic acid, and mixtures thereof.

[0177] According to a further particular embodiment, fatty acids, particularly in the free form or in the form of their esters or anhydrides, preferably C5-C 34 -Fatty acids, preferably C8-C 34 It is preferred that the fatty acids are selected from the group of fatty acids based on and / or present in fish oil, in particular the group consisting of eicosapentaenoic acid, docosadienoic acid, docosatetraenoic acid, docosapentaenoic acid, docosahexaenoic acid and tetracosahexaenoic acid, and mixtures thereof, preferably eicosapentaenoic acid, docosahexaenoic acid, as well as mixtures thereof.

[0178] Within the scope of the inventive process according to the two aforementioned aspects of the invention, one or more optionally functionalized, preferably optionally functionalized with fatty acids, more preferably optionally C5-C 34 - functionalized with a fatty acid, more preferably optionally C8-C 34 It is preferred that fatty acid-functionalized 3-oxobutyric acid polyol esters (III″), in particular 3-oxobutyric acid polyglycerol esters, are obtained.

[0179] In particular, in the inventive process according to the first aspect of the invention, it is preferred to obtain, as reaction product, one or more 3-oxobutyric acid polyol esters (III), in particular three oxobutyric acid polyglycerol esters.

[0180] Furthermore, in the process of the invention according to the first or second aspect of the invention, it is also possible to use, as the reaction product, one or more functionalized, in particular functionalized with fatty acids, preferably C5-C34 - functionalized with fatty acids, more preferably C8-C 34 It is preferred that fatty acid-functionalized 3-oxobutyric acid polyol esters (III'), in particular 3-oxobutyric acid polyglycerol esters, are obtained.

[0181] Furthermore, the present invention relates, according to a third aspect of the present invention, to a reaction product obtained according to the process of the present invention. In particular, the reaction product is at least one or more optionally functionalized, in particular optionally functionalized with a fatty acid, preferably optionally C5-C 34 - functionalized with a fatty acid, more preferably optionally C8-C 34 - Polyol esters of 3-oxobutyric acid (beta-oxobutyric acid or 3-oxobutanoic acid) functionalized with fatty acids, in particular polyglycerol esters, or mixtures thereof.

[0182] In particular, the reaction products, in particular (chemical) products or product mixtures obtained according to the process of the invention are optionally functionalized with one or more, preferably optionally functionalized with fatty acids, preferably optionally functionalized with C5-C 34 - functionalized with fatty acids, in particular optionally C8-C 34 - 3-oxobutyric acid polyol esters functionalized with fatty acids (III"), in particular of the general formula (IIIa") (R 6 O) m -(X)-(OR 6 ) n (IIIa") It is preferred to have an oxobutyric acid polyglycerol ester of the formula: In this general formula (IIIa"), X denotes an organic radical, particularly preferably a saturated organic radical, which in particular contains 4 to 21 carbon atoms and optionally contains 1 to 9 oxygen atoms and is preferably selected from alkyl radicals or (poly)alkyl ether radicals, in particular (poly)alkylene glycol radicals, preferably C4-C21-alkyl radicals or C4-C21-(poly)alkyl ether radicals, in particular C4-C21-(poly)alkylene glycol radicals, The variables m and n are each independently an integer between 1 and 10; Radical R 6 are each independently the same or different hydrogen, CH3-C(O)-CH2-C(O)- or a radical R 3 denotes the radical R 3 The type may be linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)-, provided that at least one radical R 6 , preferably at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , preferably at least two radicals R 6 represents CH3-C(O)-CH2-C(O)-; In particular, the group R 6 O- may be present in any position of the radical X, and preferably at least one group R 6 O- is the terminal end.

[0183] According to a particular embodiment of the invention, the reaction product is optionally functionalized with one or more, preferably optionally functionalized with a fatty acid, more preferably optionally functionalized with a C5-C 34 - functionalized with fatty acids, particularly preferably C8-C 34 - general formula (IIIb") functionalized with a fatty acid R 6 O-CH2-CH(OR 6 )-CH2-[O-CH2-CH(OR 6 )-CH2] q -OR 6 (IIIb") It is preferable that the polyglycerol 3-oxobutyrate is ester of 3-oxobutyric acid. Here, in the general formula (IIIb"), the variable q represents an integer from 0 to 6, in particular from 0 to 4, preferably 0 or 1, more preferably 1, Radical R 6 are each independently the same or different hydrogen, CH3-C(O)-CH2-C(O)- or a radical R 3 represents the radical R 3 The type may be linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)-, provided that at least one radical R 6 , preferably at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , preferably at least two radicals R 6 represents CH3-C(O)-CH2-C(O)-.

[0184] According to yet another particular embodiment of the present invention, the reaction product is optionally functionalized with one or more, preferably optionally functionalized with a fatty acid, more preferably optionally functionalized with a C5-C 34 - functionalized with fatty acids, particularly preferably C8-C 34 - functionalized with a fatty acid of general formula (IIIc") R 6 O-CH2-CH(OR 6 )-CH2-O-CH2-CH(OR 6 )-CH2-OR 6 (IIIc") It is preferred to have a 3-oxobutyric acid polyglycerol ester of the formula: Here, in the general formula (IIIc"), the radical R 6 are each independently the same or different hydrogen, CH3-C(O)-CH2-C(O)- or a radical R 3 represents the radical R 3 The type may be linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C33 -alkyl)-C(O)-, provided that at least one radical R 6 , preferably at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , preferably at least two radicals R 6 represents CH3-C(O)-CH2-C(O)-.

[0185] According to an alternative particular embodiment of the present invention, the reaction product has one or more optionally functionalized, preferably optionally functionalized with fatty acids, more preferably optionally functionalized with C5-C34-fatty acids, particularly preferably optionally functionalized with C8-C34-fatty acids, of the general formula (IIId") R 6 O-CH2-CH(OR 6 )-CH2-OR 6 (IIId") It is preferred to have a 3-oxobutyric acid polyglycerol ester of the formula: In the general formula (IIId"), the radical R 6 are each independently the same or different hydrogen, CH3-C(O)-CH2-C(O)- or a radical R 3 represents the radical R 3 The type may be linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)-, provided that at least one radical R 6 , preferably at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , preferably at least two radicals R 6 represents CH3-C(O)-CH2-C(O)-.

[0186] According to a particular embodiment of the invention, it is preferred that the reaction product comprises in particular a mixture of at least two different optionally functionalized, preferably optionally functionalized with fatty acids, more preferably optionally functionalized with C5-C34-fatty acids, particularly preferably optionally functionalized with C8-C34-fatty acids, 3-oxobutyric acid polyol esters (III"), in particular 3-oxobutyric acid polyglycerol esters as defined above.

[0187] According to another particular embodiment of the invention, the reaction product is optionally functionalized with at least three different, preferably optionally functionalized with fatty acids, more preferably optionally functionalized with C5-C 34 - functionalized with fatty acids, particularly preferably C8-C 34 It is particularly preferred to comprise a mixture of 3-oxobutyric acid polyol esters (III″) functionalized with fatty acids, in particular the 3-oxobutyric acid polyglycerol esters defined above.

[0188] If no functionalization or esterification or transesterification is carried out, one or more 3-oxobutyric acid polyol esters, in particular 3-oxobutyric acid polyglycerol esters, are obtained as reaction products (i.e. (chemical) products or product mixtures).

[0189] In particular, the reaction product (i.e. (chemical) product or product mixture) obtained according to the process of the invention or the reaction product of the invention has the general formula (IIIa) (R 2 O) m -(X)-(OR 2 ) n (IIIa) It is preferred that the 3-oxobutyric acid polyol ester (III) comprises one or more of the following 3-oxobutyric acid polyol esters, in particular the 3-oxobutyric acid polyglycerol esters: Here, in the general formula (IIIa), X especially contains from 4 to 21 carbon atoms, optionally from 1 to 9 oxygen atoms, and is preferably selected from alkyl radicals or (poly)alkyl ether radicals, in particular (poly)alkylene glycol radicals, more preferably C4-C 21 -Alkyl radical or C4-C 21 -(Poly)alkyl ether radicals, especially C4-C 21 - represents an organic radical, particularly preferably a saturated organic radical, selected from (poly)alkylene glycol radicals, the variables m and n each independently represent an integer from 1 to 10; · Radika R 2 are each independently the same or different and represent hydrogen or CH3-C(O)-CH2-(O)-, provided that at least one radical R 2 , in particular at least two radicals R 2 provided that does not represent hydrogen; In particular, the group R 2 O- may be present in any position of the radical X, and preferably at least one group R 2 O- is the terminal end.

[0190] In particular, the reaction product has the general formula (IIIb) R 2 O-CH2-CH(OR 2 )-CH2-[O-CH2-CH(OR 2 )-CH2] p -OR 2 (IIIb) It is preferred that the polyglycerol esters comprise one or more 3-oxobutyric acid polyglycerol esters of Here, in the general formula (IIIb), the variable p represents an integer from 1 to 6, in particular from 1 to 4, preferably 1 or 2, more preferably 1, Radical R 2 are each independently the same or different and represent hydrogen or CH3-C(O)-CH2-C(O)-, provided that at least one radical R 2 , in particular at least two radicals R2 provided that does not represent hydrogen.

[0191] According to a particular embodiment of the invention, the reaction product has the general formula (IIIc) R 2 O-CH2-CH(OR 2 )-CH2-O-CH2-CH(OR 2 )-CH2-OR 2 (IIIc) It is preferred that the polyglycerol esters comprise one or more 3-oxobutyric acid polyglycerol esters of Here, in the general formula "(IIIc), the radical R 2 are each independently the same or different and represent hydrogen or CH3-C(O)-CH2-C(O)-, provided that at least one radical R 2 , in particular at least two radicals R 2 provided that does not represent hydrogen.

[0192] Alternatively, the reaction product obtained according to the process of the present invention or the reaction product of the present invention (i.e. the (chemical) product or product mixture) may be represented by the general formula (IIId) R 2 O-CH2-CH(OR 2 )-CH2-OR 2 (IIId) It is preferred that the glycerol ester of 3-oxobutyric acid is one or more of the following: In general formula (IIId), the radical R 2 are each independently the same or different and represent hydrogen or CH3-C(O)-CH2-C(O)-, provided that at least one radical R 2 , in particular at least two radicals R 2 provided that does not represent hydrogen.

[0193] According to a particular embodiment, the reaction product preferably comprises a mixture of at least two different 3-oxobutyric acid polyol esters (III), in particular 3-oxobutyric acid polyglycerol esters, as defined above.

[0194] In particular, it is preferred that said mixtures have a weight ratio of monoglyceride esters / di-glyceride esters and higher in the range of 15-70 / 30-85, especially in the range of 20-65 / 35-80.

[0195] According to a further particular embodiment, the reaction product preferably comprises a mixture of at least three different 3-oxobutyric acid polyol esters (III), in particular 3-oxobutyric acid polyglycerol esters, as defined above.

[0196] In particular, it is preferred that said mixtures have a weight ratio of monoglyceride esters / diglyceride esters / tri- and higher glyceride esters within the range of 15-50 / 35-60 / 1-35, especially within the range of 20-45 / 40-55 / 3-30.

[0197] When functionalization of esterification and transesterification is carried out, the reaction product (i.e., (chemical) product or product mixture) is functionalized with one or more fatty acids, in particular with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 The resulting product is a fatty acid-functionalized 3-oxobutyric acid polyol ester, in particular a 3-oxobutyric acid polyglycerol ester.

[0198] In particular, the reaction products (i.e. (chemical) products or product mixtures) obtained according to the process of the invention are functionalized with one or more fatty acids, in particular functionalized with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 - general formula (IIIa') functionalized with a fatty acid (R 6 O) m -(X)-(OR 6 ) n (IIIa") It is preferred to have an oxobutyric acid polyglycerol ester of the formula: Here, in this general formula (IIIa"), X contains in particular 4 to 21 carbon atoms and optionally 1 to 9 oxygen atoms and is preferably selected from alkyl radicals or (poly)alkyl ether radicals, in particular (poly)alkylene glycol radicals, preferably C4-C 21 -Alkyl radical or C4-C 21 -(Poly)alkyl ether radicals, especially C4-C 21 - represents an organic radical, particularly preferably a saturated organic radical, selected from (poly)alkylene glycol radicals, The variables m and n are each independently an integer between 1 and 10; Radical R 6 are each independently the same or different hydrogen, CH3-C(O)-CH2-C(O)- or a radical R 3 denotes the radical R 3 The type may be linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)-, provided that there are at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , preferably at least two radicals R 6 represents CH3-C(O)-CH2-C(O)- and at least one radical R 6 , preferably at least two radicals R 6 is as defined above; In particular, the group R 6 O- may be present in any position of the radical X, and preferably at least one group R 6 O- is the terminal end.

[0199] In particular, in the general formula (IIIa′), the radical R 6are each independently of one another, identical or different, and represent CH3-C(O)-CH2-C(O)- or a radical R3 as defined above, provided that at least one radical R 6 , in particular at least two radicals R 6 represents CH3-C(O)-CH2-C(O)- and at least one radical R 6 is a radical R as defined above. 3 The condition is that

[0200] In particular, in the general formula (IIIa′), the radical R 6 are each independently the same or different and preferably do not represent hydrogen.

[0201] In particular, the reaction product is functionalized with one or more fatty acids, in particular with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 - general formula (IIIb") functionalized with a fatty acid R 6 O-CH2-CH(OR 6 )-CH2-[O-CH2-CH(OR 6 )-CH2] q -OR 6 (IIIb") It is preferable that the polyglycerol 3-oxobutyrate is ester of 3-oxobutyric acid. Here, in the general formula (IIIb"), the variable q represents an integer from 0 to 6, in particular from 0 to 4, preferably 0 or 1, more preferably 1, Radical R 6 are each independently of one another the same or different hydrogen, CH3-C(O)-CH2-C(O)- or a radical R as defined above. 3 with at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , preferably at least two radicals R 6represents CH3-C(O)-CH2-C(O)- and at least one radical R 6 , preferably at least two radicals R 6 is a radical R as defined above 3 The condition is that

[0202] In particular, in the general formula (IIIb'), the radical R 6 are independent of each other, identical or different, and are CH3-C(O)-CH2-C(O)- or a radical R as defined above. 3 with the proviso that at least one radical R6, in particular at least two radicals R6, represent CH3-C(O)-CH2-C(O)- and at least one radical R 6 is a radical R as defined above 3 The condition is that the

[0203] In particular, in the general formula (IIIb'), the radical R 6 are each independently the same or different and preferably do not represent hydrogen.

[0204] According to a particular embodiment of the invention, the reaction product is functionalized with one or more fatty acids, in particular with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 - functionalized with a fatty acid of general formula (IIIb1') R 6 O-CH2-CH(OR 6 )-CH2-[O-CH2-CH(OR 6 )-CH2] p -OR 6 (IIIb1') It is preferred that the 3-oxobutyric acid polyglycerol ester of Here, in the general formula (IIIb1′), the variable p represents an integer from 1 to 6, in particular from 1 to 4, preferably 1 or 2, more preferably 1, Radical R 6are each independently the same or different and are hydrogen, CH3-C(O)-CH2-C(O)- or a radical R as defined above. 3 with the proviso that there are at least two radicals R 6 does not represent hydrogen, and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 , in particular at least two radicals R 6 is a radical R as defined above 3 The condition is that

[0205] In particular, in the general formula (IIIb1′), the radical R 6 are each independently the same or different and are CH3-(O)-CH2-C(O)- or a radical R as defined above. 3 with the proviso that there is at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)-, and at least one radical R 6 is a radical R as defined above 3 The condition is that

[0206] In particular, in the general formula (IIIb1′), the radical R 6 are each independently the same or different and preferably do not represent hydrogen.

[0207] According to another particular embodiment of the invention, the reaction product is functionalized with one or more fatty acids, in particular with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 - functionalized with a fatty acid of general formula (IIIc') R 6 O-CH2-CH(OR 6 )-CH2-O-CH2-CH(OR 6 )-CH2-OR6 (IIIc') It is preferred that the 3-oxobutyric acid polyglycerol ester of In the general formula (IIIc'), the radical R 6 are each independently the same or different and are hydrogen, CH3-(O)-CH2-C(O)- or a radical R as defined above. 3 with the proviso that at least two radicals R6 do not represent hydrogen and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)-, and at least one radical R 6 , at least two radicals R 6 is a radical R as defined above 3 The condition is that

[0208] In particular, in the general formula (IIIc'), the radicals R6 are each independently identical or different and are CH3-(O)-CH2-C(O)- or a radical R as defined above. 3 with the proviso that there is at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 is a radical R as defined above 3 The condition is that

[0209] In particular, in the general formula (IIIc'), the radical R 6 are each independently the same or different and preferably do not represent hydrogen.

[0210] According to an alternative embodiment of the invention, the reaction product is functionalized with one or more fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 - functionalized with a fatty acid of general formula (IIId') R 6 O-CH2-CH(OR 6 )-CH2-OR 6 (IIId') It is preferred that the 3-oxobutyric acid polyglycerol ester of In the general formula (IIId'), the radical R 6 are independent of each other, identical or different, and are hydrogen, CH3-(O)-CH2-C(O)- or the radical R 3 represents the radical R 3 are of type linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)-, provided that there are at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 , in particular at least two radicals R 6 is a radical R as defined above 3 The condition is that

[0211] In particular, in the general formula (IIId'), the radical R 6 are each independently the same or different and are CH3-(O)-CH2-C(O)- or a radical R as defined above. 3 with the proviso that there is at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 is a radical R as defined above 3 The condition is that

[0212] In particular, in the general formula (IIId'), the radical R6 are each independently the same or different and preferably do not represent hydrogen.

[0213] According to a particular embodiment, the reaction product is functionalized with at least two different fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 It is preferred that the 3-oxobutyric acid polyol esters (III') functionalized with fatty acids comprise a mixture of 3-oxobutyric acid polyglycerol esters as defined above.

[0214] According to a further particular embodiment, the reaction product is functionalized with at least three different fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 It is particularly preferred that the 3-oxobutyric acid polyol esters (III′) are functionalized with fatty acids, in particular mixtures of the 3-oxobutyric acid polyglycerol esters defined above.

[0215] The object of the present invention is also to provide an optionally functionalized, preferably optionally functionalized with a fatty acid, more preferably optionally C5-C 34 - functionalized with fatty acids, particularly preferably C8-C 34 - 3-oxobutyric acid polyol esters (III '') functionalized with fatty acids, in particular of the general formula (IIIa '') (R 6 O) m -(X)-(OR 6 ) n (IIIa") It is a 3-oxobutyric acid polyglycerol ester of the formula: Here, in the general formula (IIIa"), X has 4 to 12 carbon atoms and optionally 1 to 9 oxygen atoms, and is preferably selected from an alkyl radical or a (poly)alkyl ether radical, in particular a (poly)alkylene glycol radical, more preferably a C4-C 21-Alkyl radical or C4-C 21 -(Poly)alkyl ether radicals, especially C4-C 21 - represents an organic radical, particularly preferably a saturated organic radical, selected from (poly)alkylene glycol radicals, The variables m and n are independent of each other and represent integers between 1 and 10. Radical R 6 are each independently the same or different and are hydrogen, CH3-(O)-CH2-C(O)- or a radical R 3 represents the radical R 3 The type may be linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, provided that at least one radical R 6 , in particular at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)-; In particular, the group R 6 O- may be present in any position of the radical X, and preferably at least one group R 6 O- is the terminal end.

[0216] A further object of the present invention is also the optionally functionalized 3-oxobutyric acid polyol esters (III"), in particular as described above, Optionally functionalized, preferably optionally functionalized with a fatty acid, preferably optionally C5-C 34 - functionalized with fatty acids, in particular optionally C8-C 34 - 3-oxobutyric acid polyglycerol esters functionalized with fatty acids have the general formula (IIIb") R 6 O-CH2-CH(OR 6 )-CH2-[O-CH2-CH(OR 6 )-CH2] q -OR 6(IIIb") Corresponds to. Here, in the general formula (IIIb"), the variable q represents an integer from 0 to 6, in particular from 0 to 4, preferably 0 or 1, more preferably 1, Radical R 6 are each independently the same or different and are hydrogen, CH3-(O)-CH2-C(O)- or a radical R 3 represents the radical R 3 represents a radical of the type linear (straight-chain) or branched, saturated or mono- or polyunsaturated (C1-C33-alkyl)-C(O)-, in particular (C4-C33-alkyl)-C(O)-, preferably (C1-C33-alkyl)-C(O)-, with the proviso that there are at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)-.

[0217] Again, another object of the present invention is the optionally functionalized 3-oxobutyric polyol esters (III″), in particular as shown above, Optionally functionalized, preferably optionally functionalized with a fatty acid, preferably optionally C5-C 34 - functionalized with fatty acids, in particular optionally C8-C 34 - 3-oxobutyric acid polyol esters functionalized with fatty acids have the general formula (IIIb1") R 6 O-CH2-CH(OR 6 )-CH2-[O-CH2-CH(OR 6 )-CH2] p -OR 6 (IIIb1") Corresponds to. Here, in the general formula (IIIb1"), the variable p represents an integer from 1 to 6, in particular from 1 to 4, preferably 1 or 2, more preferably 1, Radical R 6are each independently the same or different and are hydrogen, CH3-(O)-CH2-C(O)- or a radical R 3 represents the radical R 3 The type may be linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C-C 33 -alkyl)-C(O)-, provided that there are at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)-.

[0218] A further object of the present invention is also the optionally functionalized 3-oxobutyric acid polyol esters (III″), in particular as described above, Optionally functionalized, preferably optionally functionalized with a fatty acid, preferably optionally C5-C 34 - functionalized with fatty acids, in particular optionally C8-C 34 - 3-oxobutyric acid polyglycerol esters functionalized with fatty acids have the general formula (IIIc") R 6 O-CH2-CH(OR 6 )-CH2-O-CH2-CH(OR 6 )-CH2-OR 6 (IIIc") Corresponds to. Here, in general formula (IIIc"), Radical R 6 are each independently the same or different and are hydrogen, CH3-(O)-CH2-C(O)- or a radical R 3 represents the radical R 3 The type may be linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C33 -alkyl)-C(O)-, provided that at least one radical R 6 , in particular at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)-.

[0219] Again, another object of the invention is also the optionally functionalized 3-oxobutyric polyol esters (III″), in particular as explained above, Optionally functionalized, preferably optionally functionalized with a fatty acid, preferably optionally C5-C 34 - functionalized with fatty acids, in particular optionally C8-C 34 - 3-oxobutyric acid polyglycerol esters functionalized with fatty acids have the general formula (IIId") R 6 O-CH2-CH(OR 6 )-CH2-OR 6 (IIId") Corresponding to, In the general formula (IIId"), the radical R 6 are each independently the same or different and are hydrogen, CH3-(O)-CH2-C(O)- or a radical R 3 represents the radical R 3 The type may be linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)-, provided that at least one radical R 6 , in particular at least two radicals R 6 does not represent hydrogen and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)-.

[0220] A further object of the present invention according to this aspect of the invention, according to a particular embodiment, is to provide a glycerol-containing glycerol complex comprising at least two different optionally functionalized, preferably optionally functionalized with fatty acids, more preferably optionally C5-C 34 - functionalized with fatty acids, particularly preferably C8-C 34 - 3-oxobutyric acid polyol esters (III") functionalized with fatty acids, in particular mixtures comprising the 3-oxobutyric acid polyglycerol esters defined above.

[0221] Again, another object of the invention according to this aspect of the invention is, according to a particular embodiment, to provide at least three different optionally functionalized, preferably optionally functionalized with fatty acids, more preferably optionally C5-C 34 - functionalized with fatty acids, particularly preferably C8-C 34 - 3-oxobutyric acid polyol esters (III") functionalized with fatty acids, in particular mixtures comprising the 3-oxobutyric acid polyglycerol esters defined above.

[0222] According to a further embodiment, the subject of the present invention is also 3-oxobutyric acid polyol esters (III) of general formula (IIIa), in particular of general formula (IIIa) (R 2 O) m -(X)-(OR 2 ) n (IIIa) It is a 3-oxobutyric acid polyglycerol ester of Here, in the general formula (IIIa), X in particular contains from 4 to 21 carbon atoms, optionally containing from 1 to 9 oxygen atoms, and is preferably selected from alkyl radicals or (poly)alkyl ether radicals, in particular (poly)alkylene glycols, more preferably C4-C 21 -Alkyl radical or C4-C 21 -(Poly)alkyl ether radicals, especially C4-C 21 - represents an organic radical, a saturated organic radical selected from the group consisting of (poly)alkylene glycol radicals, The variables m and n are each independent of the other and represent integers from 1 to 10; Radical R 2 are each independently the same or different and represent hydrogen or CH3-(O)-CH2-C(O)-, provided that at least one radical R 2 , in particular at least two radicals R 2 does not represent hydrogen; In particular, the group R 2 O- may be present in any position of the radical X, and preferably at least one group R 2 O- is the terminal end.

[0223] According to this embodiment, another object of the invention is the 3-oxobutyric acid polyol esters (III) as particularly described above, The 3-oxobutyric acid polyglycerol ester is represented by the general formula (IIIb) R 2 O-CH2-CH(OR 2 )-CH2-[O-CH2-CH(OR 2 )-CH2] p -OR 2 (IIIb) Corresponding to, Here, in the general formula (IIIb), the variable p represents an integer from 1 to 6, in particular from 1 to 4, preferably 1 or 2, more preferably 1, Radical R 2 are each independently the same or different and represent hydrogen or CH3-(O)-CH2-C(O)-, provided that at least one radical R 2 , in particular at least two radicals R 2 provided that does not represent hydrogen.

[0224] According to this embodiment, yet another subject of the invention are 3-oxobutyric acid polyol esters (III) as especially described above, The 3-oxobutyric acid polyglycerol ester has the general formula (IIIc) R 2 O-CH2-CH(OR2 )-CH2-O-CH2-CH(OR 2 )-CH2-OR 2 (IIIc) Corresponding to, In the general formula (IIIc), the radicals R2 are each independently of one another, identical or different, and represent hydrogen or CH3-(O)-CH2-C(O)-, provided that at least one radical R 2 , in particular at least two radicals R 2 does not represent hydrogen.

[0225] According to this embodiment, a further embodiment of the present invention is a compound represented by the general formula (IIId) R 2 O-CH2-CH(OR 2 )-CH2-OR 2 (IIId) It is the glycerol 3-oxobutyrate. In general formula (IIId), the radicals R2 are each independently of one another, identical or different, and represent hydrogen or CH3-(O)-CH2-C(O)-, provided that at least one radical R 2 , in particular at least two radicals R 2 does not represent hydrogen.

[0226] Another object of the invention according to this aspect of the invention according to further particular embodiments is a mixture comprising at least two different 3-oxobutyric acid polyol esters (III), in particular 3-oxobutyric acid polyglycerol esters as defined above.

[0227] In particular, it is preferred that the mixture has a weight ratio of monoglyceride esters / di- and higher glyceride esters within the range of 15-70 / 30-85, especially within the range of 20-65 / 35-80.

[0228] Yet another object of the invention according to this aspect of the invention according to further particular embodiments is a mixture comprising at least three different 3-oxobutyric acid polyol esters (III), in particular 3-oxobutyric acid polyglycerol esters as defined above, as specifically defined.

[0229] In particular, it is preferred that the mixture has a weight ratio of monoglyceride esters / diglyceride esters / tri- and higher glyceride esters within the range of 15-50 / 35-60 / 1-35, especially within the range of 20-45 / 40-55 / 3-30.

[0230] According to a further alternative embodiment, also an object of the present invention is to provide a functionalized, in particular functionalized with a fatty acid, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 - 3-oxobutyric acid polyol esters (III') functionalized with fatty acids, in particular of the general formula (IIIa') (R 6 O) m -(X)-(OR 6 ) n (IIIa) is a 3-oxobutyric acid polyglycerol ester of Here, in the general formula (IIIa'), X in particular contains from 4 to 21 carbon atoms, optionally containing from 1 to 9 oxygen atoms, and is preferably selected from alkyl radicals or (poly)alkyl ether radicals, in particular (poly)alkylene glycols, more preferably C4-C 21 -Alkyl radical or C4-C 21 -(Poly)alkyl ether radicals, especially C4-C 21 - represents an organic radical, in particular a saturated organic radical, selected from (poly)alkylene glycol radicals, The variables m and n are each independent of the other and represent integers from 1 to 10; Radical R 6 are independent of each other and may be the same or different, and are hydrogen, the radical CH3-(O)-CH2-C(O)- or the radical R3 represents the radical R 3 are of type linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)-, provided that there are at least two radicals R 6 does not represent hydrogen, and at least one radical R 6 , at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 , at least two radicals R 6 is a radical R as defined above 3 Provided that it represents; In particular, the group R 6 O- may be present in any position of the radical X, and preferably at least one group R 6 O- is the terminal end.

[0231] In particular, in the general formula (IIIa′), the radical R 6 are each independently identical or different and are CH3-(O)-CH2-C(O)- or a radical R as defined above. 3 with the proviso that there is at least one radical R 6 , at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 is a radical R as defined above 3 The condition is that

[0232] In this particular embodiment, in the general formula (IIIa′), the radical R 6 are each independently of one another, identical or different, and advantageously do not represent hydrogen.

[0233] According to this particular embodiment, another object of the invention is the functionalized 3-oxobutyric polyol ester (III'), in particular as explained above, Functionalized, in particular functionalized with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 - fatty acid-functionalized 3-oxobutyric acid polyglycerol esters of the general formula (IIIb') R 6 O-CH2-CH(OR 6 )-CH2-[O-CH2-CH(OR 6 )-CH2] q -OR 6 (IIIb') corresponds to Here, in the general formula (IIIb'), the variable q represents an integer from 0 to 6, in particular from 0 to 4, preferably 0 or 1, more preferably 1, Radical R 6 are independent of each other and may be the same or different and are hydrogen, CH3-(O)-CH2-C(O)- or the radical R 3 with at least two radicals R 6 does not represent hydrogen, and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R6, in particular at least two radicals R 6 is a radical R as defined above 3 The condition is that

[0234] In particular, in the general formula (IIIb'), the radical R 6 are each independently identical or different and are CH3-(O)-CH2-C(O)- or a radical R as defined above. 3 with the proviso that at least one radical R 6 , in particular at least two radicals R 6represents CH3-(O)-CH2-C(O)- and at least one radical R 6 is a radical R as defined above 3 The condition is that

[0235] In this particular embodiment, in the general formula (IIIb′), the radical R 6 are each independently the same or different, and preferably do not represent hydrogen.

[0236] According to this particular embodiment, yet another object of the invention is the functionalized 3-oxobutyric acid polyol ester (III'), in particular as explained above, Functionalized, in particular functionalized with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 - fatty acid-functionalized 3-oxobutyric acid polyglycerol esters of the general formula (IIIb1') R 6 O-CH2-CH(OR 6 )-CH2-[O-CH2-CH(OR 6 )-CH2] p -OR 6 (IIIb1') corresponds to Here, in the general formula (IIIb1′), the variable p represents an integer from 1 to 6, in particular from 1 to 4, preferably 1 or 2, more preferably 1, Radical R 6 are independent of each other, identical or different, and are hydrogen, CH3-(O)-CH2-C(O)- or the radical R 3 with the proviso that there are at least two radicals R 6 does not represent hydrogen, and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 , in particular at least two radicals R 6is a radical R as defined above 3 The condition is that

[0237] In particular, in the general formula (IIIb1′), the radical R 6 are each independently identical or different and represent CH3-(O)-CH2-C(O)- or a radical R3 as defined above, provided that at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 is a radical R as defined above 3 The condition is that

[0238] In this particular embodiment, in the general formula (IIIb1′), the radical R 6 are each independently the same or different, and preferably do not represent hydrogen.

[0239] According to this particular embodiment, another object of the invention is the functionalized 3-oxobutyric acid polyol ester (III'), in particular as explained above, Functionalized, in particular functionalized with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 The 3-oxobutyric acid polyol esters functionalized with fatty acids have the general formula (IIIc') R 6 O-CH2-CH(OR 6 )-CH2-O-CH2-CH(OR 6 )-CH2-OR 6 (IIIc') corresponds to In the general formula (IIIc'), the radical R 6 are each independently the same or different and are hydrogen, CH3-(O)-CH2-C(O)- or a radical R as defined above. 3with at least two radicals R 6 does not represent hydrogen, and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 , in particular at least two radicals R 6 is a radical R as defined above 3 The condition is that

[0240] In particular, in the general formula (IIIc'), the radical R 6 are each independently identical or different and are CH3-(O)-CH2-C(O)- or a radical R as defined above. 3 with the proviso that there is at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 is a radical R as defined above 3 The condition is that

[0241] In this particular embodiment, in the general formula (IIIc′), the radical R 6 are each independently the same or different, and preferably do not represent hydrogen.

[0242] According to this particular embodiment, yet another object of the invention is the functionalized 3-oxobutyric acid polyol ester (III'), in particular as explained above, Functionalized, in particular functionalized with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 The 3-oxobutyric acid polyglycerol esters functionalized with fatty acids have the general formula (IIId') R 6 O-CH2-CH(OR 6 )-CH2-OR 6 (IIId') corresponds to In the general formula (IIId'), the radical R 6 are independent of each other, identical or different, and are hydrogen, CH3-(O)-CH2-C(O)- or the radical R 3 represents the radical R 3 The type may be linear (straight chain) or branched, saturated or mono- or polyunsaturated (C1-C 33 -alkyl)-C(O)-, especially (C4-C 33 -alkyl)-C(O)-, preferably (C7-C 33 -alkyl)-C(O)-, provided that there are at least two radicals R 6 does not represent hydrogen, and at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 , in particular at least two radicals R 6 is a radical R as defined above 3 The condition is that

[0243] In particular, in the general formula (IIId'), the radical R 6 are each independently the same or different and are CH3-(O)-CH2-C(O)- or a radical R as defined above. 3 with the proviso that there is at least one radical R 6 , in particular at least two radicals R 6 represents CH3-(O)-CH2-C(O)- and at least one radical R 6 is a radical R as defined above 3 The condition is that

[0244] In particular, in the general formula (IIId'), the radical R 6 are each independently the same or different, and preferably do not represent hydrogen.

[0245] A further object of the invention according to this aspect of the invention is, according to a further particular embodiment, to provide at least two different functionalized, in particular functionalized with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 - fatty acid functionalized 3-oxobutyric acid polyol esters (III'), in particular mixtures comprising 3-oxobutyric acid polyglycerol esters as defined above.

[0246] Another object of the invention according to this aspect of the invention is, according to another particular embodiment, to provide at least three different functionalized, in particular functionalized with fatty acids, preferably C5-C 34 - functionalized with fatty acids, more preferably C8-C 34 - fatty acid functionalized 3-oxobutyric acid polyol esters (III'), in particular mixtures comprising 3-oxobutyric acid polyglycerol esters as defined above.

[0247] The Applicant has surprisingly found that the reaction products obtainable by the process of the invention or the reaction products of the invention as defined above and / or the 3-oxobutyric acid polyol esters obtainable by the process of the invention, in particular the 3-oxobutyric acid polyglycerol esters of the invention as defined above, are particularly optimal as precursors or metabolites of acetoacetate (acetoacetic acid) and ultimately 3-hydroxybutyric acid or its salts, since this precursor or metabolite is, on the one hand, physiologically converted to acetoacetate, in particular in the gastrointestinal tract, and ultimately to 3-hydroxybutyric acid or its salts, and, on the other hand, at the same time has good physiological compatibility or tolerance, in particular in terms of non-toxicity and acceptable organoleptic properties. In particular, the sustained release of the physiologically active substance (i.e. acetoacetate and ultimately 3-hydroxybutyric acid) in the gastrointestinal tract is advantageous in the medical field, since the active substance 3-hydroxybutyric acid is available for a longer period of time, thereby enabling ketosis therapy. 3-Oxobutyric acid polyol esters have a stronger delay effect or onset of action than 3-hydroxybutyric acid polyol esters, which means that the time required to release the active ingredient in the corresponding treatment is longer compared to the use of 3-hydroxybutyric acid polyol esters.

[0248] Furthermore, the reaction products obtainable according to the process of the invention or the inventive reaction products as defined above and / or the 3-oxobutyric acid polyol esters, in particular the 3-oxobutyric acid polyglycerol esters or in particular the 3-oxobutyric acid polyol esters as defined above, in particular the 3-oxobutyric acid polyglycerol esters obtainable by the process of the invention are easily accessible or available on a large scale in the required pharmaceutical or pharmacological quality on a synthetic basis, even on a commercial scale.

[0249] The reaction products obtainable according to the process of the invention or the reaction products of the invention as defined above and / or the 3-oxobutyric acid polyol esters, in particular the 3-oxobutyric acid polyglycerol esters obtainable according to the production process of the invention or the 3-oxobutyric acid polyol esters of the invention as defined above, in particular the 3-oxobutyric acid polyglycerol esters, thereby represent an efficient pharmacological drug target for the ketotherapy of the human or animal body in the field of lipometabolic diseases such as glucose transporter deficiency (GLUT1 deficiency), VL-FAOD, etc.

[0250] The remaining aspects of the invention are described in more detail below.

[0251] Likewise, the present invention relates, according to a fourth aspect, to a reaction product obtainable by the process of the invention or to a reaction product of the invention as defined above, respectively, and / or to one or more 3-oxobutyric acid polyol esters obtainable by the process of the invention and / or to a pharmaceutical composition comprising one or more 3-oxobutyric acid polyol esters of the invention, respectively, as defined above, in particular to a drug or medicament comprising a reaction product obtainable according to the process of the invention or to a reaction product of the invention as defined above.

[0252] In particular, according to this aspect of the invention, the present invention relates to a pharmaceutical composition for the preventive and / or therapeutic treatment or for use in the preventive and / or therapeutic treatment of diseases of the human or animal body, which is particularly relevant for the treatment of disorders of energy metabolism, in particular keto metabolism such as craniocerebral trauma, stroke, hypoxia, cardiovascular diseases such as myocardial infarction, refeeding syndrome, anorexia, epilepsy, dementia, neurodegenerative diseases such as Alzheimer's disease, Parkinson's disease, multiple sclerosis, amyotrophic lateral sclerosis, glucose tolerance, cardiovascular diseases such as osteoporosis, ... transporter deficiency (GLUT1 deficiency), lipid metabolism disorders such as VL-FAOD, mitochondrial diseases such as mitochondrial thiolase deficiency and Huntington's disease, cancers such as T-cell lymphoma, astrocytoma and glioblastoma, HIV, rheumatic diseases such as rheumatoid arthritis and urinary tract arthritis, gastrointestinal diseases such as chronic inflammatory bowel disease, particularly ulcerative colitis and Crohn's disease, lysosomal storage diseases such as sphingolipidosis, particularly Niemann-Pick disease, diabetes mellitus, and the effects or side effects of chemotherapy.

[0253] Also in this case, according to a fifth aspect of the invention, a further subject of the invention is a method for treating diseases of the human or animal body, respectively, in particular diseases associated with disturbances in energy metabolism, in particular cardiovascular diseases such as craniocerebral trauma, stroke, hypoxia, myocardial infarction, neurodegenerative diseases such as refeeding syndrome, anorexia, epilepsy, dementia, keto body metabolism such as Alzheimer's disease, Parkinson's disease, multiple sclerosis and amyotrophic lateral sclerosis, lipid metabolism disorders such as glucose transporter deficiency (FLUT1 deficiency), mitochondrial disorders such as VL-FAOD and mitochondrial thiolase deficiency, Huntington's disease, cancers such as T-cell lymphoma, astrocytoma and glioblastoma, HIV, rheumatoid arthritis and urinary a reaction product obtainable according to the process of the invention or a reaction product of the invention, respectively, and / or one or more 3-oxobutyric acid polyol esters obtainable according to the process of the invention and / or one or more 3-oxobutyric acid polyol esters of the invention as defined above, for or for use in the preventive and / or therapeutic treatment, in particular of rheumatic diseases such as inflammatory bowel diseases, such as ulcerative colitis and Crohn's disease, diseases of the gastrointestinal tract, such as chronic inflammatory bowel diseases, in particular ulcerative colitis and Crohn's disease, sphingolipidoses, in particular Niemann-Pick disease, diabetes mellitus, liosomal storage diseases and diseases related to the effects or side effects of chemotherapy.

[0254] Likewise, according to a sixth aspect of the invention, a further subject of the invention is a method for treating diseases of the human or animal body, respectively, in particular diseases associated with disturbances in the energy metabolism, in particular cardiovascular diseases such as craniocerebral trauma, stroke, hypoxia, myocardial infarction, neurodegenerative diseases such as refeeding syndrome, anorexia, epilepsy, dementia, keto body metabolism such as Alzheimer's disease, Parkinson's disease, multiple sclerosis and amyotrophic lateral sclerosis, lipid metabolism diseases such as glucose transporter deficiency (FLUT1 deficiency), mitochondrial disorders such as VL-FAOD and mitochondrial thiolase deficiency, Huntington's disease, cancers such as T-cell lymphoma, astrocytoma and glioblastoma, HIV, rheumatoid arthritis and urinary arthritis. and / or the use of one or more 3-oxobutyric acid polyol esters of the invention obtained according to the production process of the invention and / or one or more 3-oxobutyric acid polyol esters of the invention as defined above for or in the preventive and / or therapeutic treatment, particularly of rheumatic diseases such as inflammatory bowel diseases, in particular ulcerative colitis and Crohn's disease, diseases of the gastrointestinal tract, such as sphingolipidoses, in particular Niemann-Pick disease, diabetes mellitus, lyosomal storage diseases and diseases related to the effects or side effects of chemotherapy.

[0255] Likewise, a further subject of the present invention is, according to a seventh aspect of the invention, the use of a reaction product obtainable by the production process of the invention or of the reaction product of the invention as defined above, respectively, for the manufacture of a medicament for the prophylactic and / or therapeutic treatment or for the prophylactic and / or therapeutic treatment of a catabolic metabolic condition, such as hunger, diet or low-carbohydrate nutrition, or for its application, and / or the use of one or more 3-oxobutyric acid polyol esters obtainable by the production process of the invention and / or one or more 3-oxobutyric acid polyol esters of the invention as defined above, respectively.

[0256] Likewise - according to an eighth aspect of the invention - a further subject of the invention is a food product and / or food product comprising a reaction product, respectively obtainable by the process of the invention or a reaction product of the invention as defined above, and / or one or more 3-oxobutyric acid polyol esters, respectively obtainable by the process of the invention and / or one or more 3-oxobutyric acid polyol esters as defined above.

[0257] According to certain embodiments, the food and / or food products are preferably essentially dietary supplements, functional foods, novel foods, food additives, food supplements, nutraceuticals, power snacks, appetite suppressants or strength and / or endurance sports supplements.

[0258] Finally, yet another subject of the invention, according to a ninth aspect, is the use of a reaction product obtainable by the inventive production process as defined above or the use of an inventive reaction product as defined above, and / or the use of one or more 3-oxobutyric acid polyol esters obtainable according to the inventive production process and / or the use of one or more inventive 3-oxobutyric acid polyol esters, respectively defined above, in food and / or food products.

[0259] According to this aspect of the invention, the food and / or food product is preferably, in particular, a dietary supplement, a functional food, a novel food, a food additive, a food supplement, a nutraceutical, a power snack, an appetite suppressant or a strength and / or endurance sports supplement.

[0260] Further embodiments, modifications and variations of the invention can be readily discerned or effected by those skilled in the art upon reading the specification, without departing from the scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0261] The present invention is illustrated by the following examples, which are not intended to limit the invention in any way, but are intended only to illustrate exemplary and non-limiting implementations and configurations of the invention. EXAMPLES

[0262] Abbreviations used PG(2) = diglycerol: HO-CH2-CH(OH)-CH2-O-CH2-CH(OH)-CH2-OH PG(3) = Polyglycerol: HO-CH2-CH(OH)-CH2-[O-CH2-CH(OH)-CH2]2-OH

[0263] Production example The process of the present invention is illustrated by the following examples: General reaction schemes are shown and explained in the general description section.

[0264] Preparation of 3-oxobutyric acid diglycerol ester mixture 25 g of 3-oxobutyric acid ethyl ester (ethyl acetoacetate or acetoacetate) and 6.54 g of diglycerol are placed in a 100 mL multi-neck flask equipped with a dephlegmator (partial condenser) and a distillation bridge.

[0265] At a temperature of 50° C., 0.35 g of immobilized enzyme (CALB lipase on a polymeric support derived from Candida antarctica, e.g. Novozym® 435) is added. The reaction mixture is stirred for 24 hours at 50° C. Then, the enzyme is filtered off and the excess 3-oxobutyric acid ethyl ester is distilled off under vacuum.

[0266] The reaction product obtained is 3-oxobutyric acid diglycerol ester, which after analytical analysis has the following composition: 45% 3-oxobutyric acid mono-diglycerol ester, 48% 3-oxobutyric acid di-diglycerol ester, 7% 3-oxobutyric acid tri-diglycerol ester. Characterization is carried out by GC, GPC and GC-MS.

[0267] During purification, reactants and reaction by-products are removed to obtain a pure mixture. One part of the mixture is separated by chromatography to obtain various diglycerol esters as pure substances (i.e., pure 3-oxobutyric acid mono-diglycerol ester, pure 3-oxobutyric acid di-diglycerol ester and pure 3-oxobutyric acid tri-diglycerol ester). Another part of the mixture is subjected to separation by fractional distillation.

[0268] Further preparation of 3-oxobutyric acid diglycerol ester mixture 106 g of 3-oxobutyric acid ethyl ester (ethyl acetoacetate or acetoacetic ester) and 29 g of diglycerol are placed in a 250 mL multi-neck flask equipped with a dephlegmator (partial condenser) and a distillation bridge.

[0269] At a temperature of 100° C., 1.4 g of a 30% methanolic NaOMe solution is added with stirring. The ethanol formed during the reaction is continuously distilled off. After a reaction time of 5 hours, the reaction mixture is cooled and washed with NaCl solution. The crude ester mixture is then dried and the excess ethyl 3-oxobutyrate is distilled off under vacuum.

[0270] The reaction product is 3-oxobutyric acid diglycerol ester with the following composition: 26% 3-oxobutyric acid mono-diglycerol ester, 51% 3-oxobutyric acid di-diglycerol ester, 22% 3-oxobutyric acid tri-diglycerol ester, 1% 3-oxobutyric acid tetra-diglycerol ester. Characterization is performed by GC, GPC, GC-MS.

[0271] During purification, reactants and reaction by-products are removed to obtain a pure mixture. One part of the mixture is separated by chromatography to obtain various diglycerol esters as pure substances (i.e., pure 3-oxobutyric acid mono-diglycerol ester, pure 3-oxobutyric acid di-diglycerol ester, and pure 3-oxobutyric acid tri-diglycerol ester, etc.). Another part of the mixture is subjected to separation by fractional distillation.

[0272] Further preparation of 3-oxobutyric acid diglycerol ester mixture The aforementioned experiments are repeated (using enzyme and NaOMe as catalyst), respectively, but with different polyols (i.e., glycerol, polyglycerol PG(3) and 1,2-pentanediol). Comparable results are obtained. Purification and fractionation are carried out in the same way.

[0273] Other production examples Various polyol components based on polyhydric alcohols (polyols) are enzymatically reacted with 3-oxobutyric acid ethyl ester (ethyl acetoacetate or acetoacetic ester).

[0274] The polyalcohols chosen are 1,2-pentanediol and diglycerol PG (2). Each polyol is reacted with an immobilized enzyme (CALB lipase on a polymeric support derived from Candida antarctica, e.g. Novozym® 435 from Sigma-Aldrich or Novozym® 435 from Merck) at 70°C for 24 hours (in each case 1% by weight of enzyme and 40% molar excess of 3-oxobutyric acid ethyl ester). The aforementioned polyols 1,2-pentanediol and diglycerol PG (2) are efficiently converted into the desired products by the aforementioned enzymes (Novozym® 435), respectively. Comparable results are obtained as in the previous experiments. Purification and separation or fractionation are carried out in the same way.

[0275] The experiment is repeated using sodium methylate (NaOMe) as catalyst instead of the enzyme and at temperatures between 100 and 120 °C. Comparable results are obtained. Purification and separation or fractionation are carried out in the same way.

[0276] These esters are an efficient product family for therapeutic applications, especially since 3-oxobutyric acid PG(2) esters have only a slightly bitter taste. Therefore, the aforementioned experiments using the enzyme and diglycerol PG(2) as the polyalcohol will be carried out on a larger scale (2-4 kg).

[0277] First, the stoichiometric reaction conditions of the previous experiment are applied on a 2 kg scale (40 mol% excess of 3-oxobutyric acid ethyl ester, 1 wt% enzyme). After 15 h, a portion of the reaction mixture (about 200 g) is removed for further testing. This is the mono- / di-PG(2) ester mixture. Then, about 1 kg more 3-oxobutyric acid ethyl ester is added. The aim is to produce the complete ester. After about 20-30 h, it is seen that a constant content of di-PG(2) ester is obtained. The mono-PG(2) ester portion decreases and the tri-PG(2) ester portion increases. Further analysis (GPC) shows that tetra-PG(2) ester is also formed.

[0278] After distillation of the excess 3-oxobutyric acid ethyl ester, the first (low boiling) mono / di-PG(2)-ester mixture obtained has a slightly bitter taste, whereas the higher (high boiling) di- / tri- / tetra-PG(3)-ester mixture has a slightly stronger bitter taste, although both mixtures are organoleptically acceptable and interchangeable.

[0279] After further purification by removal of residual starting compounds and reaction by-products, a pure mixture is obtained with significantly improved organoleptic properties.

[0280] Functionalization experiments 1. Anhydrous production A 2,000 mL multi-neck flask equipped with a dephlegmator (partial condenser) and a distillation bridge is charged with 860 g of heptanoic acid and 445 g of acetic anhydride are added under stirring at 90 °C. The reaction mixture is stirred under reflux at 130 °C for 6 hours. The resulting acetic acid and excess acetic anhydride are then distilled off under vacuum. A heptanoic acid / heptanoic anhydride mixture is obtained with the following composition: 15% heptanoic acid, 85% heptanoic anhydride. Characterization is carried out using GC, GPC and GC-MS. 2. sensualization In a 100 mL multi-neck flask equipped with a dephlegmator (partial condenser) and a distillation bridge, 25 g of heptanoic anhydride and 5 g of the 3-oxobutyric acid mono-, di-, tri-, tetra-diglycerol mixture prepared according to the invention are provided. The reaction mixture is stirred at 70° C. for 24 hours. The excess heptanoic anhydride and the resulting heptanoic acid are then distilled off by short-path distillation. A 3-oxobutyric acid-heptanoic acid-diglycerol ester mixture is obtained.

[0281] Equivalent functionalization experiments were also carried out with fatty acids and alternative fatty acid anhydrides as well as alternative fatty acid esters (in each case with eicosapentaenoic / docosahexaenoic acid mixtures and their anhydrides and esters as well as with oleic acid and its anhydrides and esters), leading in each case to similar results (i.e. esterification of the free OH groups), as confirmed by the corresponding analyses.

[0282] The experiments show that the intended functionalization by reaction with carboxylic anhydrides leads to the desired products (i.e. esterification of the free OH groups), as confirmed by appropriate analyses.

[0283] Further synthesis of functionalized 3-oxobutyric acid polyol esters As polyols, 1,2-pentanediol and diglycerol PG (2) are used. The respective polyol is first reacted with fatty acids, or fatty acid anhydrides, or even fatty acid esters (in each case eicosapentaenoic acid and docosahexaenoic acid and their anhydrides and esters) at temperatures of 100-120 ° C using sodium methanolate (NaOMe) as catalyst; the corresponding fatty acid esterified polyol results, which is then further reacted in the second process step with 3-oxobutyric acid ethyl ester. The corresponding 3-oxobutyric acid / fatty acid polyol ester mixture is obtained. Equivalent results can be obtained by the reverse procedure (i.e., first reaction of the polyol with 3-oxobutyric acid ethyl ester, followed by further reaction with the abovementioned fatty acids or their alternative anhydrides and esters).

[0284] Physiological application test: In vitro digestion test Digestion experiments (fractionation or cleavage experiments) of 3-BHB-PG(2)-ester mixtures Cleavage experiments have demonstrated that 3-oxobutyric acid PG(2) esters or mixtures thereof (including reaction by-products) produced according to the present invention are cleaved in the human gastrointestinal tract.

[0285] The starting mixture used is, on the one hand, a purified mixture of 3-oxobutyric acid mono-, di-, tri- and tetra-diglycerol esters obtained by the process of the invention, and, on the other hand, a purified mixture of functionalized 3-oxobutyric acid mono-, di- and tri-diglycerol esters obtained by the process of the invention.

[0286] For amputation experiments under near-body conditions, two mediums are investigated: FaSSGF to simulate the stomach FaSSIF to simulate the intestinal tract Both media are manufactured by Biorelevant®, UK. In addition, in some experiments, porcine pancreas (Panzytrat® 40,000, Fa. Allergan) is added.

[0287] The results of cleavage experiments in FaSSGF or FaSSIF medium with and without Panzytrat® (both at 35° C. for 24 hours) show that the samples hydrolyze under FaSSGF conditions with and without Panzytrat®. This is mainly due to the low pH of the medium (pH=1.6). Under FaSSIF conditions, a lower conversion is achieved with Panzytrat®.

[0288] The experiments prove that the starting mixture according to the invention is a suitable physiological precursor to the keto bodies acetoacetate and ultimately 3-hydroxybutyric acid for use in the corresponding keto therapy.

[0289] Further digestion experiments (cleavage experiments) of the 3-oxobutyric acid-PG(2)-ester mixture of the present invention Opening experiment using pancreatin 2 g of the mixture prepared as described above based on 3-oxobutyric acid mono-diglycerol ester, 3-oxobutyric acid di-diglycerol ester, 3-oxobutyric acid tri-diglycerol ester and 3-oxobutyric acid tetra-diglycerol ester are dissolved in 50 g of water and 0.5 g (1% by weight) of pancreatin are added. Pancreatin is used in the form of the commercial product "Panzytrat® 40,000" from Allergan. The entire mixture is stirred on a hot plate at 50° C. and the course of the reaction is measured and monitored by continuously recording the acid value over time. During the observation period, the acid value increases (cleavage of the 3-oxobutyric acid diglycerol ester mixture). The conversion / time course of the aqueous cleavage of the mixture of esters according to the invention with pancreatin indicates the desired decomposition of the educt mixture into free acids, including an increase in the acid value over time. This is confirmed by appropriate analyses. This experiment also proves that the starting mixture (educt mixture) according to the invention is a suitable physiological precursor of the keto body acetoacetate and thus of 3-hydroxybutyric acid for the corresponding keto therapy. This test is repeated and verified on the basis of the individual esters in pure form. Comparable results are obtained: 3-oxobutyric acid mono-diglycerol ester, 3-oxobutyric acid di-diglycerol ester, 3-oxobutyric acid tri-diglycerol ester, 3-oxobutyric acid tetra-diglycerol ester are all cleaved by pancreatin.

[0290] Further digestion experiments (cleavage experiments) of further 3-oxobutyric acid polyol ester mixtures according to the invention Additionally, other polyol ester mixtures of 3-oxobutyric acid prepared according to the present invention have been subjected to digestion testing in the appropriate manner as described above with similar results.

[0291] The cleavage experiments described above prove that polyol esters of 3-oxobutyric acid, in particular polyglycerol esters, are efficient precursors or metabolites of the keto bodies acetoacetate and ultimately 3-hydroxybutyric acid for use in the corresponding keto therapy, and are available in a more physiologically acceptable or physiologically compatible form, particularly with regard to their intended effects.

Claims

1. General formula (IIIc") R ６ O-CH ２ -CH(OR ６ )-CH ２ -O-CH ２ -CH(OR ６ )-CH ２ -OR ６ (IIIc") 3-oxobutyric acid polyglycerol ester corresponding to In the general formula (IIIc"), the radical R ６ are each independently the same or different, and each represents hydrogen, CH ３ —C(O)—CH ２ -C(O)- or a radical R ３ wherein the radical R ３ represents a heptanoic acid radical, an eicosapentaenoic acid radical, a docosahexaenoic acid radical, an oleic acid radical, or a combination thereof, provided that at least one radical R ６ does not represent hydrogen, and at least one radical R ６ But, CH ３ —C(O)—CH ２ 3-Oxobutyric acid polyglycerol ester, characterized in that it represents --C(O)--.

2. General formula (IIIc) R ２ O-CH ２ -CH(OR ２ )-CH ２ -O-CH ２ -CH(OR ２ )-CH ２ -OR ２ (IIIc) 3-oxobutyric acid polyglycerol ester corresponding to In the general formula (IIIc), the radical R ２ are each independently the same or different, and each represents hydrogen or CH ３ —C(O)—CH ２ represents —C(O)—, provided that at least one radical R ２ 2. The polyglycerol 3-oxobutyrate ester according to claim 1, characterized in that: does not represent hydrogen.

3. General formula (IIIc') R ６ O-CH ２ -CH(OR ６ )-CH ２ -O-CH ２ -CH(OR ６ )-CH ２ -OR ６ (IIIc') 3-oxobutyric acid polyglycerol ester corresponding to In the general formula (IIIc′), the radical R ６ are each independently the same or different, and each represents hydrogen, CH ３ —C(O)—CH ２ -C(O)- or a radical R ３ wherein the radical R ３ represents a heptanoic acid radical, an eicosapentaenoic acid radical, a docosahexaenoic acid radical, an oleic acid radical, or a combination thereof, provided that at least two radicals R ６ does not represent hydrogen, and at least one radical R ６ But, CH ３ —C(O)—CH ２ represents —C(O)— and at least one radical R ６ is the radical R ３ 2. The polyglycerol 3-oxobutyrate according to claim 1, characterized in that it has the formula:

4. A mixture comprising at least two different 3-oxobutyric acid polyglycerol esters according to claim 1.

5. A pharmaceutical composition comprising one or more 3-oxobutyric acid polyglycerol esters according to claim 1 or a mixture according to claim 4.

6. 6. The pharmaceutical composition according to claim 5, which is a medicine or drug.

7. Use of at least one 3-oxobutyric acid polyglycerol ester according to claim 1 or a mixture according to claim 4 for the production of a drug or medicinal product for the prevention and treatment of diseases of the human or animal body.

8. The use according to claim 7, characterized in that the disease is selected from among diseases associated with disorders of energy metabolism or diseases associated with disorders of keto body metabolism.

9. The use according to claim 7 or 8, characterized in that the disease is selected from the group consisting of craniocerebral trauma, stroke, hypoxia, cardiovascular disease, myocardial infarction, refeeding syndrome, anorexia, epilepsy, neurodegenerative disease, dementia, Alzheimer's disease, Parkinson's disease, multiple sclerosis, amyotrophic lateral sclerosis, lipid metabolism disease, glucose transporter deficiency (GLUT1 deficiency), long-chain fatty acid metabolism disorder (VL-FAOD), mitochondrial disease, mitochondrial thiolase deficiency, Huntington's disease, cancer, T-cell lymphoma, astrocytoma, glioblastoma, AIDS (HIV), rheumatic disease, rheumatoid arthritis, urinary arthritis, gastrointestinal disease, chronic inflammatory bowel disease, ulcerative colitis, Crohn's disease, lysosomal storage disease, sphingolipidosis, Niemann-Pick disease, diabetes, and effects and side effects of chemotherapy.

10. A food or food product comprising at least one 3-oxobutyric acid polyglycerol ester according to claim 1 or a mixture according to claim 4.

11. 11. The food or food product according to claim 10, characterized in that it is selected from the group consisting of nutritional supplements, functional foods, novel foods, food additives, food supplements, diet foods, power snacks, appetite suppressants, strength sports supplements and endurance sports supplements.

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