Aqueous compositions containing 6-undecanol esters

Abstract

The present invention relates to aqueous compositions comprising 6-undecanol esters and methods for producing 6-undecanol esters, as well as the use of 6-undecanol esters in cosmetic applications.

Description

[Technical Field]

[0001] The present invention relates to aqueous compositions containing 6-undecanol esters, methods for producing 6-undecanol esters, and the use of 6-undecanol esters in cosmetic applications.

[0002] prior art Cosmetic leave-on formulations, such as sunscreen formulations, primarily consist of emulsions with an aqueous phase and an oil phase. A wide variety of cosmetic oils are used in the oil phase. Traditionally, these have been petrochemical-based mineral oils or other low-cost mineral-oil-based products. However, modern formulations attempt to avoid petrochemical origins as much as possible in light of sustainability. Therefore, fatty acid-fatty alcohol esters or vegetable and animal fats and oils, as well as waxes, are often used. Suitable oils fall within the range of medium to heavy oils, with moderate to good spreading behavior and moderate to low polarity, possessing rather average application properties, such as viscosities in the range of 10-50 mPas at room temperature and surface tensions in the range of 26-32 mN / m. Apart from the cleansing and nourishing effects of such cosmetic formulations, which determine their intended use, various parameters are important, such as the highest possible dermatological compatibility, good refatting properties, an elegant appearance, ease of spreadability, optimal sensory impression, and shelf stability.

[0003] New solutions are being explored to further improve the CO2 footprint and provide solutions using ingredients of non-tropical origin. One promising option is to create cosmetic ingredients directly from CO2 as a starting material. This opens the door to a new level of sustainable ingredients for cosmetics, meeting consumer needs for truly sustainable cosmetics.

[0004] The object of the present invention was to provide superior cosmetic emollients.

[0005] Detailed Description of the Invention Surprisingly, it has been found that 6-undecanol esters have excellent properties for cosmetic applications.

[0006] It is an advantage of the present invention that compositions comprising at least one 6-undecanol ester have excellent sensory properties on surfaces such as skin and hair.

[0007] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester are substantially colorless.

[0008] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester are substantially odorless.

[0009] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester exhibit very good solubility for active substances.

[0010] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester exhibit very good spreadability on the skin.

[0011] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester have high hydrolytic stability, particularly at low pH and at high and low temperatures.

[0012] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester exhibit good moisturizing benefits.

[0013] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester exhibit good wetting properties.

[0014] Another advantage of the present invention is that the compositions comprising at least one 6-undecanol ester are based on highly renewable or even fully renewable raw materials.

[0015] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester can be carbon (CO2) neutral.

[0016] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester exhibit good solubilization performance for organic UV filters.

[0017] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester exhibit a favorable toxicological profile.

[0018] Another advantage of the present invention is that compositions containing at least one 6-undecanol ester exhibit less spreadability than comparable light emollients.

[0019] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester exhibit good pigment stabilization.

[0020] Another advantage of the present invention is that compositions comprising at least one 6-undecanol ester exhibit good freeze stability.

[0021] The present invention provides an aqueous composition comprising at least one 6-undecanol ester selected from 6-undecanol esters obtained by esterification of undecan-6-ol with one selected from the following: A) a monocarboxylic acid having 6 to 32, preferably 6 to 22, more preferably 8 to 22 carbon atoms, and B) Polyfunctional carboxylic acids, preferably tricarboxylic acids and dicarboxylic acids, having 2 to 44, preferably 3 to 38, more preferably 4 to 18 carbon atoms, more preferably dicarboxylic acids having 2 to 18, preferably 3 to 13, more preferably 4 to 11 carbon atoms.

[0022] The term "6-undecanol ester" is used in the context of the present invention as a synonym for "undec-6-yl ester".

[0023] The term "aqueous" in the context of the present invention means a composition comprising water in an amount of at least 2% by weight, preferably at least 10% by weight, more preferably at least 30% by weight, wherein the weight percentages are relative to the total composition.

[0024] In the context of the present invention, the term "polyfunctional carboxylic acid" should be understood to mean a carboxylic acid having more than one carboxyl group.

[0025] "pH" in the context of the present invention is defined as the value measured at 25°C for the corresponding substance after 5 minutes of stirring using a pH electrode calibrated according to ISO 4319 (1977).

[0026] Unless otherwise specified, all percentages (%) are expressed as mass percentages.

[0027] Any type of monocarboxylic acid can be used in the context of the present invention, for example saturated or unsaturated, linear or branched, substituted or unsubstituted monocarboxylic acids, such as caproic acid, cyclopentanecarboxylic acid, 2-methylpentanoic acid, heptanoic acid, cyclohexanecarboxylic acid, caprylic acid, 2-ethylhexanoic acid, sorbic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, capric acid, pelargonic acid, 2-propylheptanoic acid, isodecanoic acid, undecanoic acid, 11-undecylenic acid, 2-butyloctanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, ricinoleic acid, stearic acid, oleic acid, isostearic acid, 12-hydroxystearic acid, arachidic acid or behenic acid.

[0028] A preferred aqueous composition according to the present invention is characterized in that the monocarboxylic acid is selected from fatty acids, preferably natural fatty acids. Natural fatty acids can be produced based on naturally occurring vegetable or animal oils and preferably have 6 to 30 carbon atoms, particularly 8 to 22 carbon atoms. Natural fatty acids are generally unbranched and contain an even number of carbon atoms. The double bond has a cis configuration. Examples include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linoleic acid, eicosapentaenoic acid, docosahexaenoic acid, and arachidonic acid. More preferred aqueous compositions according to the invention are characterized in that the monocarboxylic acid is selected from hexanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, 11-undecylenic acid, myristic acid, palmitic acid, palmitoleic acid, ricinoleic acid, stearic acid, 12-hydroxystearic acid, isostearic acid, oleic acid and behenic acid.

[0029] Any kind of polyfunctional acid can be used in the context of the present invention, such as, for example, di- and tricarboxylic acids, dimer fatty acids as defined in EP-A-1 683 781, oxalic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, malic acid, tartaric acid, tartronic acid, maleic acid, citric acid, or even aromatic acids, such as phthalic acid, isophthalic acid or terephthalic acid.

[0030] Preferred aqueous compositions according to the invention are characterized in that the polyfunctional carboxylic acid is selected from aliphatic linear dicarboxylic acids, in particular oxalic acid, malonic acid, tartronic acid, succinic acid, maleic acid, tartaric acid, maleic acid, fumaric acid, sorbic acid, α-ketoglutaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid and brassylic acid.

[0031] The aqueous composition according to the present invention is preferably a formulation.In the context of the present invention, the term "formulation" should be understood to mean a composition that contains at least one additional component (other than water and ester) that is obvious to those skilled in the art to enable the formulation to fulfill its purpose according to its application.For example, it is clear that a pharmaceutical formulation must contain at least one therapeutically active ingredient to be considered a "medicine", while a cosmetic formulation usually contains a cosmetically acceptable carrier.The formulation according to the present invention can be, for example, a pharmaceutical formulation, a skin formulation, a personal care formulation, a cosmetic formulation, a household care formulation, a professional skin care formulation and a pet care formulation.

[0032] The aqueous composition according to the invention is preferably a cosmetic formulation.

[0033] Preferred formulations according to the invention contain, in addition to water and esters, the following groups: Emollients, emulsifier, Thickeners / viscosity modifiers / stabilizers / consistency improvers, UV protection filters, antioxidants, Wetting agents, solids and fillers, pigments, film-forming agents, pearlizing / opacifying additives, Deodorizing and antiperspirant active ingredients, insect repellents, Self-tanning agents, fragrance, Preservatives, propellant, conditioner, dye, Cosmetic active ingredients, Care additives, Superfatting agents, solvent, The composition further comprises at least one additional component selected from the following, wherein preferably comprises humectants, emollients, emulsifiers, stabilizers / consistency improvers, fragrances, preservatives, UV protection filters, pigments and cosmetic active ingredients, with humectants, UV protection filters and pigments being the most preferred.Substances that can be used as exemplary representatives of each group are known to those skilled in the art and are described, for example, in German application DE102008001788.4.This patent application is incorporated herein by reference and therefore constitutes part of the present disclosure.For further optional components and the amounts of these components used, explicit reference is made to relevant handbooks known to those skilled in the art, such as K. Schrader, "Grundlagen und Rezepturen der Kosmetika [Fundamentals and principles of cosmetics]", 2nd edition, pages 329 to 341, Huethig Buch Verlag Heidelberg.The amount of specific additives depends on the application.Typical guide formulations for each application are known prior art and are described, for example, in the brochures of manufacturers of specific base materials and active ingredients. These existing formulations can usually be adopted as is, but if necessary, simple experimentation for adaptation and optimization allows desired modifications to be made without complication.

[0034] Preferred humectants included in the formulations according to the invention are selected from the group consisting of glycerin, 1,2-propylene glycol, 1,3-propanediol, diglycerin, dipropylene glycol, xylitol, sorbitol, maltitol, 1,2-butylene glycol, 1,3-butylene glycol, 1,2-pentylene glycol, 1,2-hexylene glycol, lactic acid, creatine and urea.

[0035] The 6-undecanol esters contained in the compositions according to the invention can be prepared by methods known in the art. Advantageously, and therefore preferably according to the invention, the 6-undecanol esters contained in the compositions according to the invention are: (a) providing ethanol and / or lower alkanoic acids or salts of either thereof and contacting the ethanol and / or lower alkanoic acids or salts of either thereof with at least one microorganism capable of two-carbon chain extension to produce hexanoic acid and / or salts thereof and / or esters thereof; (b) contacting the hexanoic acid and / or its salts and / or its esters obtained in (a) with at least one ketonization catalyst under suitable reaction conditions to chemically ketonize the hexanoic acid and / or its salts and / or its esters to 6-undecanone; (c) contacting the 6-undecanone with at least one metal hydrogenation catalyst to catalytically hydrogenate the 6-undecanone to 6-undecanol; (d) 6-undecanol with the following: A) an acyl group donor that provides an acyl group of an acid selected from monocarboxylic acids having 6 to 32, preferably 6 to 22, more preferably 8 to 22 carbon atoms, and B) an acyl group donor that provides an acyl group of an acid selected from polyfunctional carboxylic acids having 2 to 44, preferably 3 to 38, more preferably 4 to 18 carbon atoms, preferably tricarboxylic acids and dicarboxylic acids, more preferably dicarboxylic acids having 2 to 18, preferably 3 to 13, more preferably 4 to 11 carbon atoms; and esterifying the compound with at least one selected from It is produced by a method for producing a 6-undecanol ester comprising the steps of:

[0036] The term "lower alkanoic acid" as used herein refers to an alkanoic acid containing fewer than 6 carbon atoms. Examples of lower alkanoic acids are acetic acid (acetate), propanoic acid (propanoate), butanoic acid (butanoate), or pentanoic acid (pentanoate). As used herein, the term "contacting" means bringing the microorganism into direct contact with ethanol and / or a lower alkanoic acid, such as acetate. In one example, ethanol is the carbon source, and the contacting in step (a) includes contacting the ethanol of step (a) with the microorganism. The contacting may be direct or indirect, and indirect contact may include, for example, a membrane separating the cells from the ethanol, and the cells and ethanol may be stored in two different compartments, for example.

[0037] The source of ethanol and / or lower alkanoic acids or any salt thereof provided in step (a) of the method according to the present invention can vary depending on availability. For example, the ethanol and / or lower alkanoic acids or any salt thereof can be a fermentation product of synthesis gas (syngas) or any carbohydrate known in the art. In particular, the carbon source for the microbial production of ethanol and / or lower alkanoic acids or any salt thereof can be selected from the group consisting of alcohols, aldehydes, glucose, sucrose, fructose, dextrose, lactose, xylose, pentoses, polyols, hexoses, ethanol, and synthesis gas. A mixture of sources can also be used as the carbon source.

[0038] Preferably, the carbon source is synthetic gas (syngas), which is preferably converted by at least one acetogenic microorganism to ethanol and / or lower alkanoic acids or salts of either.

[0039] With respect to sources of syngas comprising carbon dioxide and / or carbon monoxide, those skilled in the art will recognize that there are many possible sources for providing syngas comprising CO and / or CO as a carbon source. The syngas or source of syngas can be derived, for example, from steam reforming, partial oxidation, or electrochemical synthesis from water or CO. Indeed, it will be recognized that any gas or any mixture of gases capable of providing a sufficient amount of carbon to a microorganism such that ethanol and / or lower alkanoic acids, or salts of any thereof, are formed from a source of CO and / or CO as a carbon source for the microbial production of ethanol and / or lower alkanoic acids, or salts of any thereof, of the present invention can be used.

[0040] In general, for the acetogenic microorganisms of the present invention, the carbon source comprises at least 50% by weight, at least 70% by weight, in particular at least 90% by weight of CO2 and / or CO, where the percentages by weight relate to all carbon sources available to the cells according to any embodiment of the present invention.

[0041] Examples of gaseous carbon sources include exhaust gases such as syngas, flue gas, and refinery gas produced by yeast or Clostridium fermentation. These exhaust gases are formed from the gasification of cellulose-containing materials or coal. In one example, these exhaust gases are not necessarily produced as by-products of other processes, but can be produced specifically for use in the mixed culture of the present invention.

[0042] According to any embodiment of the present invention, the carbon source for the production of ethanol and / or lower alkanoic acids or salts thereof provided in step (a) of the method according to the present invention may be synthesis gas. Synthesis gas can be produced, for example, as a by-product of coal gasification. Thus, the microorganisms according to any embodiment of the present invention can convert waste materials into valuable resources.

[0043] In another example, syngas may be a by-product of the gasification of widely available, low-cost agricultural feedstocks.

[0044] There are many examples of feedstocks that can be converted to syngas, as almost any vegetation can be used for this purpose, particularly feedstocks selected from the group consisting of perennial grasses such as miscanthus, corn residues, processing waste such as sawdust, etc.

[0045] Generally, synthesis gas can be obtained mainly through pyrolysis, partial oxidation, and steam reforming in a dry biomass gasifier, and the main products of synthesis gas are CO, H, and CO. Syngas can also be the product of electrolysis of CO. Those skilled in the art will know the appropriate conditions for electrolyzing CO to produce syngas containing the desired amount of CO.

[0046] Typically, a portion of the synthesis gas obtained from the gasification process is first treated to optimize product yields and avoid tar formation. Cracking of the undesirable tar and CO in the synthesis gas can be achieved using lime and / or dolomite.

[0047] The overall efficiency of the method of the present invention, the productivity of ethanol and / or acetate, and / or the overall carbon capture may depend on the stoichiometry of CO, CO, and H in the continuous gas stream. The applied continuous gas stream may have a composition of CO and H. In particular, the concentration of CO in the continuous gas stream may range from about 10 to 50 wt%, particularly 3 wt%, and H may be 44 to 84 wt%, particularly 64 to 66.04 wt%. In another example, the continuous gas stream may also contain an inert gas such as N, where the N concentration is up to 50 wt%.

[0048] More specifically, a carbon source comprising CO and / or CO2 is contacted with the acetogenic microorganisms in a continuous gas stream. Even more specifically, the continuous gas stream comprises synthesis gas. These gases can be supplied, for example, using a nozzle opening into the aqueous medium, a frit, a membrane in a pipe that supplies the gas into the aqueous medium, etc.

[0049] Those skilled in the art will recognize that it may be necessary to monitor the composition and flow rates of the streams at such intervals. Control of the composition of the streams can be achieved by varying the ratio of the component streams to achieve the target or desired composition. The composition and flow rate of the combined stream can be monitored by any means known in the art. In one example, the system is adapted to continuously monitor the flow rates and compositions of at least two streams and combine them to produce a single combined substrate stream with a continuous gas stream of optimal composition, and has means for passing the optimized substrate stream to the fermentor.

[0050] According to any embodiment of the present invention, a reducing agent, such as hydrogen, can be provided along with the carbon source. In particular, this hydrogen can be provided when CO and / or CO are provided and / or used. In one example, the hydrogen gas is part of the synthesis gas present according to any embodiment of the present invention. In another example, additional hydrogen gas can be provided if the hydrogen gas in the synthesis gas is insufficient for the process of the present invention.

[0051] As used herein, the term "acetogenic microorganism" refers to a microorganism capable of carrying out the Wood-Ljungdahl pathway and thus converting CO, CO2, and / or hydrogen into lower alkanoic acids, such as acetate. Such microorganisms also include those that do not natively possess the Wood-Ljungdahl pathway but have acquired this trait as a result of genetic modification. Examples of such microorganisms include, but are not limited to, Escherichia coli cells. These microorganisms may also be known as carboxydotrophic bacteria. Currently, 21 different genera of acetogenic bacteria are known in the art (Drake et al., 2006), which may include Clostridium species (Drake & Kusel, 2005). These bacteria can use hydrogen as an energy source and carbon dioxide or carbon monoxide as a carbon source (Wood, 1991). Additionally, alcohols, aldehydes, carboxylic acids, and numerous hexoses can also be utilized as carbon sources (Drake et al., 2004). The reductive pathway that leads to the production of acetate is called the acetyl-CoA or Woodrungar pathway.

[0052] In particular, acetogenic microorganisms include Acetoanaerobium notera (ATCC 35199), Acetonema longum (DSM 6540), Acetobacterium carbinolicum (DSM 2925), Acetobacterium malicum (DSM 4132), Acetobacterium species no. 446 (Morinaga et al., 1990, J. Biotechnol., Vol. 14, pp. 187-194), Acetobacterium wieringae (DSM 1911), and Acetobacterium woodii (DSM 1030), Alkalibaculum bacchi (DSM 22112), Archaeoglobus fulgidus (DSM 4304), Blautia producta (DSM 2950, ​​formerly Ruminococcus productus, formerly Peptostreptococcus productus), Butyribacterium methylotrophicum (DSM 3468), Clostridium aceticum (DSM 1496), Clostridium autoethanogenum (DSM 10061, DSM 19630 and DSM 23693), Clostridium carboxidivorans (DSM 15243), Clostridium coskatii (ATCC no.PTA-10522, Clostridium drakei (ATCC BA-623), Clostridium formicoaceticum (DSM 92), Clostridium glycolicum (DSM 1288), Clostridium ljungdahlii (DSM 13528), Clostridium ljungdahlii C-01 (ATCC 55988), Clostridium ljungdahlii ERI-2 (ATCC 55380), Clostridium ljungdahlii O-52 (ATCC 55989), Clostridium mayombei (DSM 6539), Clostridium methoxybenzovorans (DSM 12182), Clostridium ragsdalei (DSM 15248), Clostridium scatologenes (DSM 757), Clostridium species ATCC 29797 (Schmidt et al., 1986, Chem. Eng. Commun., Vol. 45, pp. 61-73), Desulfotomaculum kuznetsovii (DSM 6115), Desulfotomaculum thermobezoicum subsp. thermosyntrophicum (Desulfotomaculum thermobezoicum subsp.thermosyntrophicum (DSM 14055), Eubacterium limosum (DSM 20543), Methanosarcina acetivorans C2A (DSM 2834), Moorella sp. HUC22-1 (Sakai et al., 2004, Biotechnol. Let., Vol. 29, pp. 1607-1612), Moorella thermoacetica (DSM 521, formerly Clostridium thermoaceticum), Moorella thermoautotrophica (DSM 1974), Oxobacter phenigii pfennigii (DSM 322), Sporomusa aerivorans (DSM 13326), Sporomusa ovata (DSM 2662), Sporomusa silvacetica (DSM 10669), Sporomusa sphaeroides (DSM 2875), Sporomusa termitida (DSM 4440) and Thermoanaerobacter kivui (DSM 2030, formerly Acetogenium kivui).

[0053] More preferably, the ATCC BAA-624 strain of Clostridium carboxidivorans is used, and even more preferably, the strains of Clostridium carboxidivorans labeled "P7" and "P11," as described, for example, in U.S. Patent Application Publication Nos. 2007 / 0275447 and 2008 / 0057554, are used.

[0054] Another particularly suitable bacterium is Clostridium ljungdahlii. In particular, strains selected from the group consisting of Clostridium ljungdahlii PETC, Clostridium ljungdahlii ERI2, Clostridium ljungdahlii COL, and Clostridium ljungdahlii O-52 can be used to convert synthesis gas to hexanoic acid via the corresponding C2 intermediate. These strains are described, for example, in WO 98 / 00558, WO 00 / 68407, ATCC 49587, ATCC 55988, and ATCC 55989.

[0055] Preferably, the production of hexanoic acid begins with synthesis gas-derived ethanol and / or lower alkanoic acids, or salts of either, and involves the use of an acetogenic bacterium in combination with a microorganism capable of carbon chain elongation. For example, Clostridium ljungdahlii may be used simultaneously with Clostridium kluyveri. In another example, a single acetogenic cell may possess the activity of both organisms. For example, the acetogenic bacterium may be C. carboxidivorans, which is capable of both the Woodlungal pathway and the carbon chain elongation pathway.

[0056] Preferably, the lower alkanoic acid or any salt thereof provided in step (a) of the process according to the present invention is selected from the group consisting of acetic acid and butanoic acid.

[0057] Preferably, the ethanol and / or lower alkanoic acid or any salt thereof provided in step (a) of the method according to the present invention is ethanol combined with at least one other carbon source selected from the group consisting of acetate, propanoate, butanoate (butyrate), and pentanoate. More preferably, the ethanol and / or lower alkanoic acid or any salt thereof provided in step (a) of the method according to the present invention is ethanol and acetate. Also preferably, the ethanol and / or lower alkanoic acid or any salt thereof provided in step (a) of the method according to the present invention is a combination of ethanol and butyric acid. However, it is also possible to advantageously use ethanol or acetate alone as the ethanol and / or lower alkanoic acid or any salt thereof provided in step (a) of the method according to the present invention.

[0058] The microorganism in step (a) of the method according to the present invention, which is capable of carbon chain elongation to produce hexanoic acid and / or its salts and / or its esters, can be any organism capable of carbon chain elongation, as described in Jeon et al. Biotechnol Biofuels (2016) 9: 129. Microorganisms present in step (a) of the present invention can also include microorganisms that are incapable of carbon chain elongation in the wild but have acquired this trait as a result of genetic recombination. Preferably, the microorganism in (a) is selected from the group consisting of Clostridium carboxidivorans and Clostridium kluyveri, with Clostridium kluyveri being most preferred.

[0059] The microorganisms in step (a) of the method of the present invention, capable of carrying out carbon chain elongation to produce hexanoic acid and / or its salts and / or its esters, can be cultured using any medium, substrate, conditions, and process commonly known in the art for culturing bacteria. This allows for the production of hexanoic acid and / or its salts and / or its esters by biotechnological methods. Depending on the microorganism used to produce hexanoic acid and / or its salts and / or its esters, the appropriate growth medium, pH, temperature, agitation rate, inoculation level, and / or aerobic, microaerobic, or anaerobic conditions will vary. Those skilled in the art will be aware of other conditions necessary to carry out step (a) of the method of the present invention. In particular, the conditions during step (a) of the method of the present invention in a vessel (e.g., a fermenter) can be varied depending on the microorganism used. Modifying the conditions to suit optimal microorganism function is within the knowledge of those skilled in the art.

[0060] Step (a) of the method according to the invention is preferably carried out in an aqueous medium having a pH of 5 to 8, more preferably 5.5 to 8, and most preferably 5.5 to 7. The pressure in step (a) of the method according to the invention is preferably 1 to 10 bar. The microorganisms may be contacted in step (a) of the method according to the invention at a temperature in the range of 20°C to 80°C. Preferably, the microorganisms are contacted at a temperature in the range of 35°C to about 42°C.

[0061] Preferably, for the growth of microorganisms and the production of hexanoic acid and / or its salts and / or its esters, the aqueous medium contains any nutrients, components, and / or supplements suitable for promoting the growth of microorganisms or the production of hexanoic acid and / or its salts and / or its esters. In particular, the aqueous medium may contain at least one of the following: a carbon source, a nitrogen source, such as an ammonium salt, yeast extract, or peptone; inorganic substances; salts; cofactors; buffers; vitamins; and any other components and / or extracts that may promote bacterial growth. The medium used should be suited to the requirements of the specific strain. Descriptions of media for various microorganisms are found, for example, in the "Manual of Methods for General Bacteriology." For example, LB medium can be used for E. coli, and ATCC 1754 medium can be used for C. ljungdahlii. During step (a) of the method according to the present invention, the microorganisms are incubated with the carbon source for a time sufficient to produce the desired product, for example, at least 1, 2, 4, 5, 10, or 20 hours.

[0062] Between step (a) and step (b) of the method according to the present invention, it may be advantageous to purify hexanoic acid and / or its salts and / or its esters. This purification step preferably comprises (a) extraction of hexanoic acid and / or its salts and / or its esters with at least one extractant selected from alkylphosphine oxides and trialkylamines. More preferably, the extractant comprises at least one alkylphosphine oxide and, optionally, at least one alkane containing at least 12 carbon atoms, or at least one trialkylamine and at least one alkane containing at least 12 carbon atoms. At the end of the purification step involving extraction, excess water can be removed from the aqueous medium, resulting in an extractant containing the extracted hexanoic acid and / or its salts and / or its esters. In particular, what remains at the end of the purification step involving extraction and removal of hexanoic acid and / or its salts and / or its esters may be a fermentation medium containing cells used in the production of hexanoic acid and / or its salts and / or its esters. In this case, these cells, together with the fermentation medium, can be recycled to step (a).

[0063] Step (b) of the process according to the present invention comprises contacting the hexanoic acid and / or its salts and / or its esters obtained in (b)(a) with at least one ketonization catalyst under suitable reaction conditions to chemically ketonize the hexanoic acid and / or its salts and / or its esters to 6-undecanone.

[0064] Any metal oxide catalyst or mixture thereof can be used in step (b) of the method of the present invention. Ketonization involves the reaction of hexanoic acid and / or its salts and / or its esters to produce 6-undecanone, with the elimination of one water and one carbon dioxide. The mechanism involved in the ketonization of hexanoic acid, which can form hexanoic anhydride ((CH3(CH2)4)COOCO(CH2)4CH3), is disclosed at least in Woo, Y., Ind. Eng. Chem. Res. 2017, 56: 872-880. The ketonization of hexanoic acid in the presence of various metal oxide catalysts is also shown in Wang, S.J., Phys. Chem. C 2017, 121, 18030-18046.

[0065] The ketonization catalyst used in step (b) of the process according to the present invention is preferably a heterogeneous catalyst for the efficient production of 6-undecanone from biologically produced hexanoic acid according to step (a). In particular, the ketonization catalyst is preferably a heteropolyacid (HPW). 12 O 40 ) catalyst, niobium oxide (Nb2O5) catalyst, titanium oxide (TiO2) catalyst, cerium oxide (CeO2) catalyst, zinc-chromium (Zn-Cr) mixed oxide catalyst, manganese oxide (MnO x ) catalyst, lanthanum oxide (La2O3) catalyst, magnesium oxide (MgO) catalyst, iron oxide (FeO, FeO2, Fe2O3, Fe3O4, Fe4O5, Fe5O6, Fe5O7), silicon-aluminum (Si y Al z O) A mixed oxide catalyst, any metal oxide catalyst or mixture thereof selected from the group consisting of aluminum oxide (Al2O3) catalyst and zirconia (ZrO2) catalyst. MnO x "x" in Si may be 1, 2 or 4. y Al z The "y" and "z" in O can refer to any number such that the ratio z / y is any number between 0 and 1.

[0066] An exemplary ketonization is carried out using a suitable heterogeneous metal hydride catalyst and appropriate reaction conditions, as disclosed in Pham TN, ACS Catal. 2013, 3: 2456-2473. The disclosed conditions may vary depending on the catalyst used for the effective yield of 6-undecanone. In yet another example, MnO and / or AlO catalysts can be used to ketonize hexanoic acid to 6-undecanone, based on the disclosure of Glinski, M. et al., Polish J. Chem. 2004, 78: 299-302. In a further example, NbO catalysts can be used to ketonize hexanoic acid to 6-undecanone, as disclosed in U.S. Pat. No. 6,265,618, particularly Example 3. Those skilled in the art will be able to identify suitable catalysts and appropriate conditions for producing 6-undecanone from hexanoic acid through simple trial and error based on the prior art. Orozco, LM et al ChemSusChem, 2016, 9(17): 2430-2442 and Orozco, LM et al Green Chemistry, 2017, 19(6): 1555-1569 also disclose other catalysts that can be used as ketonization catalysts in step (b) of the process according to the invention.

[0067] The metal oxide catalyst or mixture thereof is preferably a heteropoly acid (H3PW 12 O 40The catalyst is preferably selected from the group consisting of titanium oxide (TiO2), cerium oxide (CeO2), zinc-chromium (Zn-Cr) mixed oxide catalysts, manganese oxide (MnO2), lanthanum oxide (La2O3), magnesium oxide (MgO), iron oxides (FeO, FeO2, Fe2O3, Fe3O4, Fe4O5, Fe5O6, Fe5O7), silicon-aluminum (Si-Al) mixed oxide catalysts, and zirconia (ZrO2). Preferably, the ketonization catalyst in step (b) is a zirconia aerogel catalyst. This can be used in the ketonization of hexanoic acid and / or its salts and / or its esters, as disclosed in Woo, Y., Ind. Eng. Chem. Res. 2017, 56: 872-880. Lee, Y. et al. in Applied Catalysis A: General. 2015, 506: 288-293 disclose different ketonization catalysts and their effectiveness in the ketonization of hexanoic acid and / or its salts and / or its esters. Those skilled in the art can easily determine suitable ketonization catalysts and / or conditions for use in the ketonization of hexanoic acid and / or its salts and / or its esters using the method described by Lee, Y. et al.

[0068] In particular, suitable reaction conditions for step (b) include reaction temperatures of 100°C to 50°C, 100°C to 45°C, 100°C to 40°C, 100°C to 35°C, 100°C to 30°C, 100°C to 25°C, 100°C to 20°C, 150°C to 50°C, 150°C to 45°C, 150°C to 40°C, 150°C to 35°C, 150°C to 30°C, 150°C to 25°C, 150°C to 20°C, 200°C to 50°C, 200°C to 45°C, 200°C to 40°C, 200°C to 35°C, 200°C to 30°C, 200°C to 25°C, 250°C to 50°C, 250°C to 45°C, 250°C to 40°C, 250°C to 35°C, and 250°C to 300°C.

[0069] Preferably, (b) of the method according to the invention is carried out at a temperature between 150°C and 350°C.

[0070] Preferably, 6MgO / SiO2 catalyst is the ketonization catalyst in step (b) of the process according to the invention, and step (b) is carried out at a temperature between 150°C and 350°C, preferably between 200°C and 350°C.

[0071] Step (c) of the process according to the present invention provides a step of contacting the 6-undecanone obtained in step (b) with at least one metal hydrogenation catalyst to catalytically hydrogenate the 6-undecanone to 6-undecanol. 11 H 24 O) is the product of catalytic hydrogenation of 6-undecanone, where a hydrogen molecule is added to the carbon-oxygen double bond, ultimately giving 6-undecanol as the final product.

[0072] The metal hydrogenation catalyst in the process of the present invention may be a homogeneous catalyst or a heterogeneous catalyst. The homogeneous metal catalyst may be a metal complex known in the art. Preferably, the metal hydrogenation catalyst in step (c) of the process of the present invention is a heterogeneous catalyst. Some advantages of using a multiphase catalytic reaction using a solid catalyst include easy separation of the catalyst and the product, easy recovery, easy catalyst recycling, and relatively mild operating conditions. There are also clear economic and environmental incentives for using a heterogeneous catalyst. Preferably, the metal hydrogenation catalyst in step (c) of the process of the present invention is selected from the group consisting of ruthenium (Ru), rhenium (Re), nickel (Ni), iron (Fe), cobalt (Co), palladium (Pd), and platinum (Pt) catalysts. The metal hydrogenation catalyst in step (c) of the method according to the present invention is preferably selected from the group consisting of ruthenium (Ru), rhenium (Re), nickel (Ni), iron (Fe), cobalt (Co), and platinum (Pt). More preferably, the metal hydrogenation catalyst in step (c) of the method according to the present invention is selected from the group consisting of Ni, Pd, and Pt. In one example, the metal hydrogenation catalyst used in step (c) of the method according to the present invention is nickel nanoparticles as described in Alonso, F. Tetrahedron, 2008, 64: 1847-52. In another example, the iron(II) PNP pincer complex disclosed in Gorgas, N., Organometallics, 2014, 33 (23): 6905-6914 can be used as the metal hydrogenation catalyst in step (c) of the method according to the present invention.In yet another example, ruthenium (Ru)-catalyzed, rhenium (Re)-catalyzed, nickel (Ni)-catalyzed, iron (Fe), cobalt (Co), palladium (Pd)-catalyzed or platinum (Pt)-catalyzed magnetite nanoparticles disclosed in Tariq Shah M., et al., ACS Applied Materials & Interfaces, 2015: 7(12), 6480-9 can be used as the heterogeneous metal catalyst in step (c) of the method according to the present invention. In yet another example, a copper-phosphine complex disclosed in Chen, JX., Tetrahedron, 2000, 56: 2153-2166 is used as the homogeneous metal hydrogenation catalyst in step (c) of the method according to the present invention. In a further example, a heterogeneous Pt catalyst, particularly a Pt / Al2O3 catalyst disclosed in Journal of Molecular Catalysis A: Chemical, 2014, 388-389: 116-122, can be used in step (c) of the process according to the present invention. ChemSusChem, 2017: 10(11), 2527-2533 also discloses various heterogeneous catalysts, such as Pt / C, Ru / C, and Pd / C, that can be used in combination with or without an acid catalyst for the hydrogenation of 6-undecanone to 6-undecanol. Based on the above, a person skilled in the art can determine an appropriate hydrogenation catalyst to be used in step (c) of the process according to the present invention to obtain 6-undecanol from 6-undecanone. A person skilled in the art can easily determine an appropriate hydrogenation metal catalyst for efficiently producing 6-undecanol from the hydrogenation of 6-undecanone and adjust the conditions accordingly.

[0073] Step (d) of the process according to the invention involves the esterification of 6-undecanol with at least one acyl group donor.

[0074] Any type of acyl group donor can be used for the acyl group donors of group A) and group B); these can be, for example, the carboxylic acid itself, its anhydride, or a carboxylic acid ester, such as a methyl, ethyl ester and / or a glycerol ester. Overall, in step (d) of the process according to the invention, preference is given to the acyl group donors used in group A) and group B) that donate the acyl group contained in the 6-undecanol ester preferably contained in the composition according to the invention.

[0075] Preferably, according to the present invention, the acyl donors of group A) are selected from triglycerides, in particular natural fats and oils, more preferably from the group consisting of coconut fat, palm kernel oil, olive oil, palm oil, argan oil, castor oil, linseed oil, babassu oil, rapeseed oil, algae oil, sesame oil, soybean oil, avocado oil, jojoba oil, safflower oil, almond oil, cottonseed oil, shea butter, sunflower oil, cupua butter and oils with a high proportion of polyunsaturated fatty acids (PUFAS). Likewise, it is also possible to preferentially use sorbitan esters, monoglycerides and diglycerides with the chain length distribution and modifications described above.

[0076] In step (d) of the method according to the present invention, esterification can be carried out by classical esterification methods. Esterification can be carried out without a catalyst, with an enzyme catalyst, with an acid catalyst, or with a base catalyst. In step (d) of the method according to the present invention, esterification can be enzyme-catalyzed esterification, which is a preferred type of esterification. This can be carried out, for example, using at least one lipase. Preferably, the lipase used in the enzyme-catalyzed esterification in step (d) of the method according to the present invention is one that can be isolated from organisms of the fungal division and has at least 60%, preferably at least 80%, more preferably at least 90%, particularly preferably at least 95%, 98%, or 99% amino acid identity with those that can be isolated from organisms of the fungal division. By comparison with a reference sequence, the enzyme with amino acid identity preferably has an enzymatic activity of at least 50%, particularly at least 90%, in terms of propyl laurate units. Measurement of the activity of carboxylic acid ester hydrolases in propyl laurate units is measured at the optimum temperature for a given enzyme, where "optimum temperature" is understood to mean the temperature at which the enzyme has the highest activity. For example, for lipase A and B from Candida antarctica with accession number P41365, the optimum temperature is 60°C.

[0077] "Homology at the amino acid level" in the context of the present invention is understood here and below to mean "amino acid identity", which can be determined using known methods. Generally, special computer programs are used with algorithms that take into account specific requirements. A preferred method for determining identity first produces a maximum alignment between the sequences to be compared. Computer programs for determining identity include: - GAP (Deveroy, J. et al., Nucleic Acid Research 12 (1984), page 387, Genetics Computer Group University of Wisconsin, Medicine (WI) and - BLASTP, BLASTN and FASTA (Altschul, S. et al., Journal of Molecular Biology 215 (1990), pages 403-410 Examples of BLAST programs include, but are not limited to, the GCG program package of the National Center for Biotechnology Information (NCBI) and other sources (BLAST Handbook, Altschul S. et al., NCBI NLM NIH Bethesda ND 22894; Altschul S. et al., supra).

[0078] Those skilled in the art will be aware that various computer programs are available for calculating the similarity or identity between two nucleotide or amino acid sequences.For example, the identity percentage between two amino acid sequences can be determined by, for example, the algorithm developed by Needleman and Wunsch (J. Mol. Biol. (48): 444-453 (1970)), which is integrated into the GAP program of GCG software package (available at http: / / www.gcg.com), and uses either Blossom 62 matrix or PAM250 matrix, gap weight of 16, 14, 12, 10, 8, 6 or 4, and length weight of 1, 2, 3, 4, 5 or 6.Those skilled in the art will be aware that although the use of different parameters will produce slightly different results, the overall identity percentage between two amino acid sequences will not be significantly different.Usually, Blossom 62 matrix is ​​used with default settings (gap weight: 12, length weight: 1).

[0079] In the context of the present invention, 60% identity according to the above algorithm means 60% homology, and similarly for any identity greater than this.

[0080] Lipases which are particularly preferably used in the enzyme-catalyzed esterification of step (d) in the process according to the invention are lipases from Thermomyces lanuginosus with accession number O59952, lipases A and B from Candida antarctica with accession number P41365, and lipases from Mucor miehei with accession number P19515, lipases from Humicola species with accession number O59952, lipases from Rhizomucor javanicus with accession number S32492, lipases from Rhizopus oryzae with accession number P61872, and lipases from oryzae lipase, Candida rugosa lipase with accession numbers P20261, P32946, P32947, P3294, and P32949, Rhizopus niveus lipase with accession number P61871, Penicillium camemberti lipase with accession number P25234, Aspergillus niger lipase with accession numbers ABG73613, ABG73614, and ABG37906, and Penicillium cyclopium lipase with accession number P61869. The lipase is an enzyme selected from the group consisting of lipases derived from Saccharomyces cerevisiae (Saccharomyces cerevisiae), ...

[0081] Commercially available examples of carboxylic acid ester hydrolysates which may also be used in the enzymatically catalysed esterification of step (d) in the process according to the invention are Lipozyme TL IM, Novozym 435, Lipozyme IM 20, Lipase SP382, Lipase SP525, Lipase SP523 (all commercially available from Novozymes A / S, Bagsvaerd, Denmark), Chirazyme L2, Chirazyme L5, Chirazyme L8, Chirazyme L9 (all commercially available from Roche Molecular Biochemicals, Mannheim, Germany), CALB Immo Plus™ from Purolite, and Lipase M “Amano”, Lipase F-AP 15 “Amano”, Lipase AY “Amano”, Lipase N “Amano”, Lipase R “Amano”, Lipase A “Amano”, Lipase D “Amano”, Lipase G "Amano" (both are commercially available products manufactured by Amano Enzyme Co., Ltd., Japan).

[0082] The enzyme-catalyzed esterification of step (d) in the process according to the invention is preferably carried out at a reaction temperature in the range of from 20°C to 160°C, preferably from 25°C to 130°C, in particular from 30°C to 90°C.

[0083] The enzyme-catalyzed esterification of step (d) in the process according to the invention is preferably carried out at a pressure of less than 1 bar, preferably less than 0.5 bar, more preferably less than 0.05 bar.

[0084] In an alternative preferred embodiment, the enzyme-catalyzed esterification of step (d) of the process according to the invention is carried out at a pressure above 1 bar, preferably in the range of 2 bar to 10 bar. In this connection, it is preferred that the reaction mixture is supplied with an inert gas; these are preferably selected from the group comprising, preferably consisting of, nitrogen and argon.

[0085] The acid-catalyzed esterification in step (d) of the process according to the present invention can be carried out using, for example, a Brønsted acid or a Lewis acid. Examples include hydrochloric acid, sulfonic acids (e.g., methanesulfonic acid, p-toluenesulfonic acid, 10-camphorsulfonic acid), sulfuric acid, phosphoric acid, hypophosphorous acid, phosphonic acid, phosphorous acid, phosphinic acid, tin(II) salts such as tin oxide, zinc salts such as zinc oxide or zinc acetylacetonate, or zirconium salts. Polymer / resin-based catalysts such as sulfonated polystyrene or supported catalysts can also be used. The above-mentioned acids can also be used in combination. The base-catalyzed esterification in step (d) of the process according to the present invention can be carried out using, for example, alkali metal salts, alkaline earth metal salts, or ammonium salts, such as the respective hydroxides, oxides, phosphates, or carbonates. Furthermore, amines or alkali metal salts of alcohols or organic acids can be used as bases. The above-mentioned bases can also be used in combination. Temperatures of 30 to 260°C, preferably 100 to 200°C, are typically used in the acid- or base-catalyzed esterification of step (d) in the process according to the invention. Vacuum and / or a flow of inert gas such as nitrogen or argon may also be applied to assist the condensation of water.

[0086] The present invention further relates to a method for producing a compound comprising undecan-6-ol and: A) a monocarboxylic acid having 6 to 32, preferably 6 to 22, more preferably 8 to 22 carbon atoms, and B) Polyfunctional carboxylic acids having 2 to 44, preferably 3 to 38, more preferably 4 to 18 carbon atoms, preferably tricarboxylic acids and dicarboxylic acids, more preferably dicarboxylic acids having 2 to 18, preferably 3 to 13, more preferably 4 to 11 carbon atoms. 6-undecanol esters obtained by esterification with one selected from the group consisting of: or 6-undecanol esters obtained by the process according to the invention The present invention provides the use of at least one 6-undecanol ester selected from the group consisting of:

[0087] The present invention further provides the use of at least one 6-undecanol ester contained in an aqueous composition according to the invention or obtainable by a process according to the invention, for avoiding dryness of the skin.

[0088] The present invention further provides the use of at least one 6-undecanol ester contained in an aqueous composition according to the invention or obtainable by a process according to the invention for solubilizing active ingredients and UV protection filters, preferably UV protection filters, more preferably organic UV protection filters, in cosmetic formulations.

[0089] The present invention further provides the use of at least one 6-undecanol ester contained in an aqueous composition according to the invention or obtainable by a process according to the invention, for providing a good, non-greasy skin feel to a cosmetic formulation.

[0090] The present invention further provides the use of at least one 6-undecanol ester contained in an aqueous composition according to the invention or obtained by a process according to the invention, for reducing the ability of a cosmetic formulation to disperse on the skin or hair, which is beneficial for use in eye care or face care formulations.

[0091] The present invention further provides the use of at least one 6-undecanol ester contained in an aqueous composition according to the present invention or obtainable by a process according to the present invention for stabilizing a cosmetic formulation in the form of an emulsion, preferably at pH values ​​below pH 5 and / or at temperatures below 15°C.

[0092] The use according to the invention is a cosmetic application.

[0093] The examples presented below are intended to illustratively explain the present invention, and are not intended to limit the present invention to the embodiments specified in the examples. The scope of application of the present invention is clear from the entire specification and claims.

[0094] The following figures are some examples: [Brief explanation of the drawings]

[0095] [Figure 1] FIG. 1 shows an emulsion after repeated freeze / thaw cycles.

[0096] Working Example: Example 1: Synthesis of 6-dodecanol from ethanol and acetate Cultivation of Clostridium kluyveri and extraction of hexanoic acid The bacterium Clostridium kluyveri was cultured and biotransformed from ethanol and acetate to hexanoic acid. For in situ extraction of the produced hexanoic acid, a mixture of tetradecane and trioctylphosphine oxide (TOPO) was continuously passed through the culture. Both cultivation steps were carried out under anaerobic conditions in pressure-resistant glass bottles that could be hermetically closed with butyl rubber stoppers.

[0097] A preculture of Clostridium kluyveri was prepared in a 1000 mL pressure-resistant glass bottle in 250 mL of EvoDM45 medium (pH 5.5, 0.004 g / L Mg acetate, 0.164 g / L Na acetate, 0.016 g / L Ca acetate, 0.25 g / L K acetate, 0.107 mL / L H3PO4 (8.5%), 2.92 g / L NH4 acetate, 0.35 mg / L Co acetate, 1.245 mg / L Ni acetate, 20 μg / L d-biotin, 20 μg / L folic acid, 10 μg / L pyridoxine hydrochloride, 50 μg / L thiamine hydrochloride, 50 μg / L thiamine hydrochloride). The culture medium was incubated at 37°C, 150 rpm, and 1 L / h with a mixture of 25% CO2 and 75% N2 in an open water bath shaker containing 0.702 mg / L riboflavin, 50 μg / L nicotinic acid, 50 μg / L calcium pantothenate, 50 μg / L vitamin B12, 50 μg / L p-aminobenzoate, 50 μg / L lipoic acid, 0.702 mg / L (NH4)2Fe(SO4)2 x 4H2O, 1 mL / L 93.5 mM KCl acetate, 20 mL / L ethanol, and 0.37 g / L acetic acid. The culture medium was then cooled to 37°C, 150 rpm, and vented to the reactor headspace. The pH was maintained at 5.5 by automatic addition of 2.5 M NH3 solution. Fresh medium was added for 2.0 days. -1 The fermentation broth was continuously removed from the reactor through a 0.2 μm pore size KrosFlo® hollow fiber polyethersulfone membrane (Spectrumlabs, Rancho Dominguez, USA) to retain the cells in the reactor and maintain an OD 600nm was kept at about 1.5.

[0098] For the main culture, 150 ml of EvoDM39 medium (pH 5.8, 0.429 g / L Mg acetate, 0.164 g / L Na acetate, 0.016 g / L Ca acetate, 2.454 g / L K acetate, 0.107 mL / L H3PO4 (8.5%), 1.01 mL / L acetic acid, 0.35 mg / L Co acetate, 1.245 mg / L Ni acetate, 20 μg / L d-biotin, 20 μg / L folic acid, 10 μg / L pyridoxine hydrochloride, 50 μg / L thiamine hydrochloride, 50 μg / L riboflavin, 50 μg / L nicotinic acid, 50 μg / L Ca pantothenate, 50 μg / L vitamin B12, 50 μg / L p-aminobenzoate, 50 μg / L lipoic acid, 0.702 mg / L (NH4)2Fe(SO4)2 × 4H2O, 1 mL / L KS acetate (93.5 mM), 20 mL / L ethanol, 8.8 27.75 ml / L of NH3 solution (2.5 mol / L), 27.75 ml / L of acetic acid (144 g / L)) was inoculated into a 1000 ml bottle, and 100 ml of cell broth obtained from the preculture was added to reach an OD 600nm was set to 0.71.

[0099] The culture was carried out in an open water bath shaker at 37°C, 150 rpm, and a ventilation rate of 1 L / h using a mixture of 25% CO2 and 75% N2 for 65 h. The gas was vented into the headspace of the reactor. The pH was maintained at 5.8 by automatic addition of 2.5 M NH3 solution. Fresh medium was added every 0.5 d. -1 The reactor was continuously fed with a dilution rate of 0.05%. 600nm The fermentation broth was continuously removed from the reactor while maintaining the pH at about 0.5. An additional 120 g of a 6% (w / w) mixture of TOPO in tetradecane was added to the fermentation broth. This organic mixture was then continuously fed to the reactor, and the organic phase was also continuously removed from the reactor. -1 During the cultivation, 5 mL samples were taken from both the aqueous and organic phases and the OD 600nm, pH, and product formation were investigated. Product concentration measurements were performed by semi-quantitative 1H-NMR spectroscopy. Sodium trimethylsilylpropionate (T(M)SP) was used as an internal quantitative standard. During the main cultivation in the aqueous phase, steady-state concentrations of ethanol 8.18 g / L, acetate 3.20 g / L, butyrate 1.81 g / L, and hexanoate 0.81 g / L were reached. OD 600nm The K value remained stable at 0.5. In the organic phase, steady-state concentrations of ethanol 0.43 g / kg, acetate 0.08 g / kg, butyrate 1.13 g / kg, and hexanoate 8.09 g / kg were reached. After the experiment, the cells survived even when transferred to further culture. The partition coefficients K for substrate and product in the system of aqueous medium and 6% TOPO in tetradecane were D was calculated from the concentrations of both phases.

[0100]

number

[0101] K at steady state D was 0.05 for ethanol, 0.03 for acetic acid, 0.62 for butyric acid, and 9.99 for hexanoic acid.

[0102] Ketonization of hexanoic acid to 6-undecanone The ketonization was carried out in a heated continuous fluidized-bed reactor. The reactor was first charged with magnesium oxide on silica (50 wt %, 14.00 g) and heated to 330 °C for 1 h under an argon flow (54 mL / min). The temperature was then increased to 360 °C. A mixture of hexanoic acid in tetradecane (v / v: 3 / 1) was then continuously fed to the reactor at a rate of 3.3 mL / h. The gaseous effluent was collected in two cold traps cooled with water and a mixture of dry ice and isopropanol. The collected fractions were weighed and analyzed for composition by gas chromatography (GC). A total of 370.65 g of hexanoic acid was fed to the reactor, corresponding to a maximum theoretical yield of 271.70 g of 6-undecanone, as well as 28.75 g of water and 70.21 g of carbon dioxide as by-products. The amount of 6-undecanone obtained was 267.67 g, and the amount of water was 28.32 g. This corresponds to a mass recovery rate of 99% with a total conversion. This high productivity and selectivity were confirmed by conventional GC measurements, where only a trace amount of hexanoic acid was detected, and no by-products were detected.

[0103] Hydrogenation of 6-undecanone to 6-undecanol The hydrogenation reaction of 6-undecanone to 6-undecanol was carried out in a 300 ml autoclave reactor (PARR Instrument Company). The reactor was placed in an aluminum block, and the temperature was controlled by a thermocouple installed inside the reactor. Typically, 30 mg of solid catalyst and 170.3 mg, 1.0 mmol of substrate were added to a 4 ml glass vial containing an oven-dried magnetic stirrer. 2.0 ml of anhydrous toluene was used as the solvent, and the vial was fitted with a screw cap and a needle inserted into the septum. The vial was then placed in the reactor. The reactor was purged three times with 10 bar H2, after which the pressure was increased to 20 bar. The reactor was heated to the target temperature of 120 °C over 20 hours. After the reaction, the reactor was cooled to 5 °C using an ice bath, the gas phase was slowly released, and the remaining liquid was carefully separated from the solid catalyst and analyzed separately using an internal standard (100 μL of n-hexadecane).

[0104] Catalyst 3.0Co@γ-AlO showed 99% ketone conversion and 98% alcohol yield. The catalyst preparation method was as follows: 3 wt% Co@γ-AlO, ascorbic acid as the reducing agent, and glucose as the capping agent in HO were pyrolyzed at 800 °C for 2 h. The Co salt was cobalt(II) nitrate hexahydrate. In a typical synthesis, 149 mg, 0.51 mmol of Co(NO)2.6HO was dissolved in 20 mL of demineralized water, followed by the stepwise addition of 265 mg, 3.0 mmol of ascorbic acid and 92 mg, 1 mmol of D-(+)-glucose. The contents were stirred at 90 °C for 2–3 h. Next, 1.0 g of γ-AlO support was added, and the slurry was stirred at RT overnight. Excess water was removed by centrifugation and the solid was dried in an oven at 120°C for 10 hours and then pyrolyzed at 800°C for 2 hours under an argon atmosphere.

[0105] Example 2: Undec-6-yl hexanoate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and hexanoic acid (116.2 g / mol, 70.9 g, 0.61 mol, >98% (purified intermediate obtained in Example 1)) was heated to 160°C and stirred under the catalytic addition of 0.17 g of p-toluenesulfonic acid. The resulting water was continuously distilled off under a nitrogen stream in vacuum until the acid number reached less than 20 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered, washed with water and distilled in vacuum. A colorless to slightly yellow oil was obtained. Saponification number: 207 mg KOH / g. Purity (GC): >98%.

[0106] Example 3: Undec-6-yl laurate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and lauric acid (≥99% (Sigma-Aldrich) 200.3 g / mol, 116.2 g, 0.58 mol) was heated to 150°C and stirred under the catalytic addition of 1.1 g of p-toluenesulfonic acid. The resulting water was continuously distilled off under a nitrogen stream in vacuo until the acid number reached less than 20 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered, washed with water and distilled in vacuo. A colorless to slightly yellow oil was obtained. Saponification number: 158 mg KOH / g. Purity (GC): >98%.

[0107] Example 4: Undec-6-yl stearate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and stearic acid (≥92%, Palmac 90-18 (IOI), acid value 199 mg KOH / g, 284 g / mol, 156.2 g, 0.55 mol) was heated to 180°C and stirred with the addition of 0.26 g of tin(II) oxide as a catalyst. The resulting water was continuously distilled off under a stream of nitrogen in vacuo until the acid value reached less than 20 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered, bleached with H2O2 solution, and washed with water. After drying, a slightly yellowish wax was obtained. Acid value: <1 mg KOH / g; Saponification value: 129 mg KOH / g; Purity (GC): >95%

[0108] Example 5: Undec-6-ylcaprylate / Caprate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and caprylic / capric acid (Kortacid 0810 (Oleon), acid value 360 ​​mg KOH / g, 156 g / mol, 95.2 g, 0.61 mol) was heated and stirred at 160°C with the catalytic addition of 0.2 g of p-toluenesulfonic acid. The resulting water was continuously distilled off under a nitrogen stream in vacuo until the acid value reached less than 20 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered, washed with water and distilled in vacuo. A slightly yellowish oil was obtained. Saponification value: 181 mg KOH / g. Purity (GC): >97%.

[0109] Example 6: Undec-6-yl cocoate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and distilled coconut fatty acid (Wilfarin DC-0818 (Wilmar), acid value 270 mg KOH / g, 208 g / mol, 114.4 g, 0.55 mol) was heated and stirred at 160°C with the addition of 0.43 g of tin(II) oxide as a catalyst. The resulting water was continuously distilled off under a stream of nitrogen in vacuo until the acid value reached less than 20 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered, bleached with H2O2 solution, and washed with water. After drying, a yellowish oil was obtained. Acid value: 1 mg KOH / g; Saponification value: 156 mg KOH / g; Purity (GC): >95%

[0110] Example 7: Undec-6-yl 12-hydroxystearate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and 12-hydroxystearic acid (HCO Fatty Acid (Jayant), acid value 182 mg KOH / g, 308 g / mol, 169.4 g, 0.55 mol) was heated and stirred at 180°C with the addition of 0.27 g of tin(II) oxide as a catalyst. The resulting water was continuously distilled off under a stream of nitrogen in vacuo until the acid value reached less than 20 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered, bleached with H2O2 solution, and washed with water. After drying, a yellowish wax was obtained. Acid value: 1 mg KOH / g; Saponification value: 122 mg KOH / g; Purity (GC): >92%

[0111] Example 8: Undec-6-yl isostearate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and isostearic acid (PRISORINE 3503 (Croda), acid value 190 mg KOH / g, 295 g / mol, 162.3 g, 0.55 mol) was heated and stirred at 180°C with the addition of 0.13 g of tin(II) oxide as a catalyst. The resulting water was continuously distilled off under a stream of nitrogen in vacuo until the acid value reached less than 20 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered, bleached with H2O2 solution, and washed with water. After drying, a yellowish oil was obtained. Acid value: 2 mg KOH / g; Saponification value: 125 mg KOH / g; Purity (GC): >90%

[0112] Example 9: Undec-6-yl oleate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and oleic acid (Wilfarin OA 7075 (Wilmar), acid value 200 mg KOH / g, 281 g / mol, 154.6 g, 0.55 mol) was heated and stirred at 180°C with the addition of 0.25 g of tin(II) oxide as a catalyst. The resulting water was continuously distilled off under a stream of nitrogen in vacuo until the acid value reached less than 20 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered, bleached with H2O2 solution, and washed with water. After drying, a yellow oil was obtained. Acid value: 1 mg KOH / g; Saponification value: 128 mg KOH / g; Purity (GC): >92%

[0113] Example 10: Bis(undec-6-yl)malate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and D,L-malic acid (≥98% (Sigma-Aldrich), 134.1 g / mol, 37.5 g, 0.28 mol) was heated and stirred at 160°C under the catalytic addition of 0.14 g of p-toluenesulfonic acid. The resulting water was continuously distilled off under a stream of nitrogen in vacuo until the acid number reached less than 30 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered and washed with water. After drying, a yellowish oil was obtained. Acid number: 2 mg KOH / g; Saponification number: 255 mg KOH / g; Purity (GC): >90%

[0114] Example 11: Bis(undec-6-yl)succinate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and succinic acid (>99% (Sigma-Aldrich), 118.9 g / mol, 33.3 g, 0.28 mol) was heated and stirred at 180°C with the catalytic addition of 0.13 g of p-toluenesulfonic acid. The resulting water was continuously distilled off under a stream of nitrogen in vacuo until the acid number reached less than 30 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered and washed with water. After drying, a slightly yellowish wax was obtained. Acid number: 2 mg KOH / g; Saponification number: 262 mg KOH / g; Purity (GC): >90%

[0115] Example 12: Bis(undec-6-yl) sebacate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and sebacic acid (≥99% (Sigma-Aldrich), 202.3 g / mol, 56.6 g, 0.28 mol) was heated and stirred at 180°C under the catalytic addition of 0.8 g of p-toluenesulfonic acid. The resulting water was continuously distilled off under a stream of nitrogen in vacuo until the acid number reached less than 30 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered and washed with water. After drying, a yellowish wax was obtained. Acid number: 1 mg KOH / g; Saponification number: 223 mg KOH / g; Purity (GC): >90%

[0116] Example 13: Furan-2,5-dicarboxylic acid bis(undec-6-yl) ester A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and dimethylfuran-2,5-dicarboxylate (>99% (Sigma-Aldrich), 184.1 g / mol, 53.4 g, 0.29 mol) was heated and stirred at 150°C under the catalytic addition of 0.15 g of p-toluenesulfonic acid. The resulting methanol was continuously distilled off under vacuum until the acid value reached less than about 20 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered and washed with water. After drying, a yellowish oil was obtained. Acid value: 2 mg KOH / g; Saponification value: 260 mg KOH / g; Purity (GC): >85%

[0117] Example 14: Tris(undec-6-yl) citrate A mixture of undecan-6-ol (172.3 g / mol, 100.0 g, 0.58 mol) and citric acid (≥99% (Sigma-Aldrich), 192.1 g / mol, 34.6 g, 0.18 mol) was heated and stirred at 180°C with the catalytic addition of 0.13 g of p-toluenesulfonic acid. The resulting water was continuously distilled off under a stream of nitrogen in vacuo until the acid number reached approximately 30 mg KOH / g. The product was neutralized with potassium hydroxide solution, then filtered and washed with water. After drying, a yellowish wax was obtained. Acid number: 2 mg KOH / g; Saponification number: 260 mg KOH / g; Purity (GC): >85%

[0118] Example 15: Application test To demonstrate the advantageous properties of aqueous compositions containing 6-undecanol esters, the following W / O emulsions were prepared in a conventional manner. The aqueous phase was slowly added and incorporated into the oil phase. The mixture was then homogenized. TEGOSOFT DC (decyl cocoate) was used as a reference substrate in the comparative examples, but this is outside the scope of the present invention.

[0119] To evaluate freeze-thaw stability, the following body lotion formulations were subjected to two freeze-thaw cycles from room temperature to -15°C and back to room temperature. The freeze stability of the aqueous compositions was determined by visual inspection after the samples had reached room temperature again. The following terms were used to describe freeze stability: [Table 1]

[0120] The sensory properties of cosmetic emulsions are evaluated by a trained sensory panel. At least five people evaluate the sensory profile of the formulation without knowing the composition of the evaluated samples. The attributes described by the majority of panelists are reported in the table below; the numbers shown are percentages by weight.

[0121] [Table 2]

[0122] Figure 1 compares Formulation B containing Example 3 on the left with Formulation A containing decyl cocoate on the right after freeze-thaw cycling. The sensory results surprisingly revealed that the system containing the inventive example exhibited high absorption and slipperiness 5 minutes after absorption, but poor dispensing ability compared to the reference sample. After the freeze stability test, the inventive system showed no signs of instability, whereas the reference sample exhibited severe syneresis, which is unacceptable for a cosmetic formulation.

[0123] Example 16: Additional exemplary aqueous compositions containing 6-undecanol esters according to the present invention The following examples demonstrate the versatility of 6-undecanol esters in various cosmetic formulations and their compatibility with various other ingredients that are usually difficult to formulate, such as emulsifiers, stabilizers, preservatives, or active compounds such as UV-filters and antibacterial agents. The application of the present invention is not limited to the formulations shown. The examples were prepared according to common standard methods.

[0124] Table 3

[0125] Table 4

[0126] Table 5

[0127] Table 6

[0128] Table 7

[0129] Table 8

[0130] Table 9

[0131] Table 10

[0132] Table 11

[0133] Table 12

[0134] Table 13

[0135] Table 14

[0136] Table 15

[0137] Table 16

[0138] Table 17-1 Table 17-2

[0139] Table 18

[0140] Table 19

[0141] Table 20

[0142] Table 21

[0143] Table 22

[0144] Table 23

[0145] Table 24

[0146] Table 25

[0147] Table 26

[0148] Table 27

[0149] Table 28

[0150] Table 29

[0151] Table 30

Claims

1. undecan-6-ol and the following: A) a monocarboxylic acid having 6 to 32 carbon atoms, and B) Polyfunctional carboxylic acids having 2 to 44 carbon atoms 1. An aqueous composition comprising at least one 6-undecanol ester selected from 6-undecanol esters obtained by esterification of:

2. The aqueous composition of claim 1 , wherein the monocarboxylic acid is selected from fatty acids.

3. 3. The aqueous composition of claim 1, wherein the polyfunctional carboxylic acid is selected from aliphatic linear dicarboxylic acids.

4. The aqueous composition of claim 1 or 2, wherein the aqueous composition is a formulation.

5. The aqueous composition of claim 1 or 2, wherein the aqueous composition comprises at least one humectant.

6. A method for producing a 6-undecanol ester, comprising the steps of: (a) providing ethanol and / or a lower alkanoic acid or a salt thereof, and contacting the ethanol and / or the lower alkanoic acid or a salt thereof with at least one microorganism capable of two-carbon chain extension to produce hexanoic acid and / or a salt thereof and / or an ester thereof; (b) contacting the hexanoic acid and / or its salts and / or its esters obtained in (a) with at least one ketonization catalyst under suitable reaction conditions to chemically ketonize the hexanoic acid and / or its salts and / or its esters to 6-undecanone; (c) contacting the 6-undecanone with at least one metal hydrogenation catalyst to catalytically hydrogenate the 6-undecanone to 6-undecanol; (d) treating the 6-undecanol with the following: A) an acyl group donor that provides an acyl group of an acid selected from monocarboxylic acids having 6 to 32 carbon atoms; and B) an acyl group donor that provides an acyl group of an acid selected from polyfunctional carboxylic acids having 2 to 44 carbon atoms; and esterifying the compound with at least one selected from the group consisting of: A method comprising:

7. 7. The method of claim 6, wherein the microorganism in (a) is selected from the group consisting of Clostridium carboxydivorans and Clostridium kluyveri.

8. 8. The method according to claim 6, wherein the ketonization catalyst in (b) is a metal oxide catalyst or a mixture thereof.

9. 8. The method of claim 6 or 7, wherein step (b) is carried out at a temperature of from 150°C to 350°C.

10. 8. The method of claim 6 or 7, wherein the metal hydrogenation catalyst in step (c) is selected from the group consisting of ruthenium (Ru) catalysts, rhenium (Re) catalysts, nickel (Ni) catalysts, iron (Fe) catalysts, cobalt (Co) catalysts, palladium (Pd) catalysts and platinum (Pt) catalysts.

11. 8. The method of claim 6 or 7, wherein the lower alkanoic acid in step (a) is selected from the group consisting of acetic acid and butanoic acid.

12. 8. The method according to claim 6 or 7, wherein providing ethanol and / or lower alkanoic acids or any salts thereof in step (a) comprises synthesizing the ethanol and / or lower alkanoic acids or any salts thereof from synthesis gas.

13. 10. Use of at least one 6-undecanol ester contained in an aqueous composition according to claim 1 or obtained by the process according to claim 6 for the preparation of a cosmetic formulation.

14. Use of at least one 6-undecanol ester contained in an aqueous composition according to claim 1 or obtained by the method according to claim 6 to avoid dryness of the skin.

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