3-hydroxypropylesters as antioxidants and tocopherol boosters

Abstract

The present invention primarily relates to compounds of formula (I) and their use as a antioxidants and / or as antioxidant boosters.

Description

3-Hydroxypropylesters as antioxidants and tocopherol boostersThe present invention primarily relates to compounds of formula (I) and their use as antioxidants and / or antioxidant boosters. It is one of a series of inventions related to 3- Hydroxypropylesters and structurally related compounds co-filed by the same applicant and on the same date as PCT patent applications, which are titled “3-Hydroxypropylesters as antioxidants and tocopherol boosters”, “3-Hydroxypropylesters as solubility enhancers for lipophilic ingredients”, “3-Hydroxypropylesters as foam and viscosity modulating agents in surfactant containing formulations”, “3-Hydroxypropylesters as emulsifying agents”, “3- Hydroxypropylesters as antimicrobial agents”, and “Antimicrobial synergies”, whose content is incorporated herein by way of reference.Oxidation of lipids, primarily unsaturated fatty acids, in products of personal care, household, pharmaceutical or food is a key factor that needs to be controlled and prevented, because it affects the life of the product, the perception of the product by the consumer, the nutritional value of the product and the health of the consumer. Oxidation of unsaturated fatty acids by the action of atmospheric oxygen begins with free radical chain reactions, generating highly reactive peroxides and hydroperoxides. In turn, these peroxides and hydroperoxides react with substrates present in the matrix and result in carboxylic acids, aldehydes and ketones, among other, which alter the sensory properties of the productions and potentially compromise the consumer health. For this reason, antioxidants are widely used by the industry to prevent or delay the onset of oxidative breakdown.Various natural or synthetic substances have proven their effectiveness as antioxidants. Besides vitamin C (ascorbic acid) the most well-known include the different carotene derivatives (e.g. beta carotene, lycopene, luteine) and, particularly, vitamin E and its derivatives (tocopherol, tocopheryl acetate and tocopheryl palmitate). Another important group is constituted by the polyphenols, specifically the anthocyanins and isoflavones, which are contained, for example, in a variety of red fruits.Many antioxidants are known. However, it is needless to say that there is not one antioxidant, which fits all needs. Moreover, there is a general desire to replace existing substances by “green” alternatives. Hence, there is an ongoing demand for improving both the potential and the range of efficiency of such antioxidants, either by achieving a higher performance with the same amounts or, vice versa, by achieving the same performance with lower amounts.Moreover, when searching for antioxidants it must be taken into account that substances used in regulated sectors must be toxicologically acceptable, well tolerated by the user (e.g., by the user’s skin) and stable within the matrix forming the product. In addition, it is preferred that the antioxidant is odorless or at least has a pleasant smell, is cheap and readily available.However, there is no clear dependency between the chemical structure of a substance, on the one hand, and its antioxidative property, on the other hand, which makes the search for suitable substances difficult. Furthermore, there is no predictable relationship between antioxidative property, toxicological acceptability, tolerability and the stability of a substance.It is therefore an object of the present invention to provide a formulation, for example a personal care, household, pharmaceutical, or food formulation, comprising an antioxidant, whereby the formulation shows an increased antioxidant performance. Its antioxidant performance advantageously renders the formulation, for example a personal care, household, pharmaceutical or food formulation, stable against oxidation or renders the formulation, for example a personal care or pharmaceutical formulation, suitable to protect a human from oxidative damage, for example protect a human’s skin upon application of the formulation onto the skin.A further object of the present invention is to provide a substance, which enhances the antioxidative effect of an antioxidant and / or which enhances the antioxidative effect of a formulation upon application.Furthermore, it is an object of the present invention to provide a substance by which the amount of an antioxidant in formulation, for instance a personal care, household, pharmaceutical or food formulation, can be reduced.The above objects are achieved by the various aspects of the present invention as described herein.A first aspect of the present invention pertains to the use of at least one of compounds of formula (I) as an antioxidant and / or as an antioxidant booster.The compounds of formula (I) as described herein are defined as follows:whereinX is: • straight-chain C5 - C14, preferably Ce - C14, more preferably C7 - C13, yet more preferably Ca - C12, most preferably C9 - Cn, alkyl or alkenyl; or selected from the group consisting of:with R3being -OCH3, -OCH2CH3, or -O(CH2)2CH3, and wherein• R1is selected from the group consisting of -H and -OH, and R2is selected from the group consisting of -H, -CH2(OH), -CH(OH)-CH2(OH), and -CH(OH)-CH(OH)-CH2(OH);• R1is -OH and R2and the -OH group shown in formula (I) are joined together to form the following compound of formula (l-a):• R1and R2are joined together to form the following compound of formula (l-b):(l-b)When X is , R3(as defined above) can be on any one of the free carbon atoms of the benzyl ring, i.e. X can be selected from the group consisting of:A preferred use as an antioxidant and / or as an antioxidant booster involves a use for protecting unsaturated fatty acids from oxidation, wherein the fatty acids are preferably part of a plant oil.The term “antioxidant” as used herein refers to a substance or composition which significantly delays, prevents or inhibits oxidation. Antioxidants react with free radicals, reducing them to stable, unreactive products.According to a further aspect of the present invention, a formulation comprises:(i) at least one of compounds of formula (I) as defined herein,(ii) unsaturated fatty acids, preferably derived from, or included in, an oil, preferably a plant oil, and / or(iii) at least one further antioxidant that is different from compounds of formula (I) as defined herein.Whenever reference is made herein to the term “comprising” it is intended to cover both meanings “comprising” and “consisting of” as alternatives, unless the context dictates otherwise.Preferably, the formulation is selected from the group consisting of personal care, household, pharmaceutical, and food formulations.In another aspect of the present invention, a method of protecting an object from oxidation, comprises or consists of the following steps:(a) providing at least one of compounds of formula (I) as defined herein, or a formulation as defined herein,(b) providing an object to be protected from oxidation, and(c) applying the compound(s) or the formulation of step (a) to the object of step (b) in an amount sufficient to provide an antioxidative benefit.In a specific embodiment of the present invention, the object to be protected is a formulation containing unsaturated fatty acids. Preferably, the unsaturated fatty acids are derived from an oil, preferably plant oil. It is further preferred that the formulation is selected from the group consisting of personal care, household, pharmaceutical and food formulations.The term “antioxidative benefit” as used herein means a tangible increase of antioxidative performance due to addition of the compound(s) of formula (I). Thus, the increase of antioxidative performance can be determined by comparing the antioxidative performance in the presence of the compound(s) of formula (I) with the antioxidative performance in the absence of the compound(s) of formula (I). The antioxidative performance can be determined by means of assessing pressure change upon treatment with oxygen, optionally while heating (Oxipres), odor evaluation or analysing the acidic value, optionally after accelerated aging / heating. Preferably, the antioxidative performance is determined by one or more of Oxipres, odor evaluation and analysing the acidic value as described in the example section herein.The expression “an amount sufficient to provide an antioxidative benefit” as understood herein denotes an amount of the compound(s) of formula (I) that provides a tangible increase of antioxidative performance that can be attributed to the presence of the compound(s) of formula (I).Surprisingly, it has been found that the compounds of formula (I) have antioxidative properties and can boost the antioxidative potential of other antioxidants such as Tocopherol. Therefore, by adding a compound of formula (I) to a formulation, for example a personal care, household, pharmaceutical, or food formulation, the formulation shows an increased antioxidant performance as compared to a corresponding formulation lacking thecompound of formula (I). If the formulation comprises another antioxidant than a compound of formula (I), addition of the compounds of formula (I) may further increase the antioxidative capacity of the formulation. Alternatively, the compounds of formula (I) may replace a part of or all of the other antioxidant(s), yet maintain antioxidative properties. Hence, the compounds of formula (I) can reduce the amount of another antioxidant in formulation.With the improvement of the antioxidative effect, the shelf life of a formulation can be improved by incorporating the compound(s) of formula (I) as specified herein.In addition, the compounds of formula (I) as specified herein have the benefit to be liquid at room temperature or slightly above room temperature. Thus, their incorporation in semifinished products or final products is eased and their availability in said products is increased. Additionally, in an emulsion the compounds of formula (I) tend to remain in the oil phase and can develop their antioxidative potential directly where it is needed.The antioxidant performance brought about by the compound(s) of formula (I), optionally in admixture with another antioxidant, advantageously renders the formulation stable against oxidation and / or suitable to protect a human from oxidative damage, for example protect a human’s skin upon application of the formulation onto the skin. This means, the compounds of formula (I) are suitable to enhance the antioxidative effect of an antioxidant, to protect a formulation from (aut)oxidation and to enhance the antioxidative effect of a formulation upon application.In addition, the compounds of formula (I) are environmentally friendly and meet requirements for being integrated into personal care, including oral care, preparations and / or household preparations. In particular, the compounds of formula (I) are toxicologically and dermatologically acceptable, odorless, and non-ethoxylated (not skin permeable).Further aspects and embodiments of the present invention will arise from the description below, in particular from the examples, as well as from the attached patent claims.According to a preferred embodiment of the present invention, the compounds of formula (I) are those in which X is selected from the group consisting of:It is further preferred that in compounds of formula (I), R1and R2are all -H.Most preferred compounds of formula (I) include the following compounds of formula (l-a) to (l-e):The term “at least one” as used herein means one or a mixture of two, three, four or five, or even more different of the respective components following said term. For example, the phrase “at least one of the compounds of formula (I)” provides for any one of the compounds as well as all possible combinations of two, three, four or five, or even more different compounds of formula (I).Using the abbreviations shown in the above table as a placeholder for the respective compound, specific combinations of two of the particular preferred compounds of formulas (l-a) to (l-e) include the following:A+B, A+C, A+D, A+E, B+C, B+D, B+E, C+D, C+E and D+E.Specific combinations of three of the particular preferred compounds of formulas (l-a) to (I- e) include the following:A+B+C, A+B+D, A+B+E, A+C+D, A+C+E, A+D+E, B+C+D, B+C+E, B+D+E and C+D+E.Specific combinations of four of the particular preferred compounds of formulas (l-a) to (I- e) include the following:A+B+C+D, A+B+D+E, A+C+D+E and B+C+D+E.It is assumed that combinations of two, three, four or five, or even more compounds of formula (I), preferably combinations of two, three, four or five of the particular preferred compounds of formulas (l-a) to (l-e) is associated with an even further improved antioxidative potential.A preferred purpose or use of the compounds of formula (I) concerns the protection of unsaturated fatty acids from oxidation. To this end, the compounds of formula (I) may beadded to, or comprised in a formulation containing unsaturated fatty acids. The unsaturated fatty acids can be derived from, or included in, an oil, e.g., a plant oil.The oil may be part of a formulation, for example may form an oil phase and serve as a carrier in a topic formulation. The oil may include, or the oil phase may be formed by, oil components selected from the group consisting of plant oils, hydrocarbons, fatty alcohols, fatty acid esters, liquid UV filters, or mixtures of two or more of the aforesaid oil components.Plant oils or vegetable oils are oils extracted from seeds, or less often, from other parts of fruits. Like animal fats, plant oils are mixtures of triglycerides. Soybean oil, rapeseed oil and cocoa butter are examples of plant oils from seeds. Olive oil, palm oil and rice bran oil are examples of oils from other parts of fruits. In common usage, plant oil or vegetable oil may refer exclusively to vegetable fats which are liquid at room temperature or at 35 to 37 °C skin temperature. Vegetable oils are usually edible.The term “plant oils” also includes unsaturated plant oils. Unsaturated oils or vegetable oils can be transformed through partial or complete “hydrogenation” into oils of higher melting point. As each carbon-carbon double-bond is chemically reduced to a single bond, two hydrogen atoms each form single bonds with the two carbon atoms. The elimination of double bonds by adding hydrogen atoms is called saturation; as the degree of saturation increases, the oil progresses toward being fully hydrogenated. An oil may be hydrogenated to increase resistance to rancidity (oxidation) or to change its physical characteristics. As the degree of saturation increases, the oil's viscosity and melting point increase.In a preferred embodiment, the plant oil is selected from the group consisting of Persea Gratissima (Avocado Oil), Abies Alba Seed Oil, Acacia Victoriae Seed Oil, Actinidia Chinensis (Kiwi) Seed Oil, Amaranthus Hypochondriacus Seed Oil, Arachis Hypogaea (Peanut) Oil, Astrocaryum Murumuru Seed Butter, Astrocaryum Tucuma Seed Butter, Astrocaryum Tucuma Seed Oil, Astrocaryum Vulgare Fruit Oil, Astrocaryum Vulgare Kernel Oil, Avena Sativa (Oat) Kernel Oil, Brassica Alba Seed Oil, Brassica Campestris (Rapeseed) Seed Oil, Butyrospermum Parkii (Shea) Butter, Butyrospermum Parkii (Shea) Oil, Calendula Officinalis Seed Oil, Calophyllum Inophyllum Seed Oil, Calophyllum Tacamahaca Seed Oil, Camellia Oleifera Seed Oil, Camellia Reticulata Seed Oil, Camellia Sinensis Seed Oil, Cannabis Sativa Seed Oil, Cannabis Sativa Seed / Stem Oil, Canola Oil, Carthamus Tinctorius (Safflower) Seed Oil, Chlorella Vulgaris Oil, Citrullus Lanatus (Watermelon) Seed Oil, Citrus Aurantifolia (Lime) Seed Oil, Citrus Aurantium Dulcis(Orange) Seed Oil, Citrus Grandis (Grapefruit) Seed Oil, Cocos Nucifera (Coconut) Oil, Cocos Nucifera (Coconut) Seed Butter, Coffea Arabica (Coffee) Seed Oil, Chlorella Oil (biotech), Corylus Americana (Hazelnut) Seed Oil, Corylus Avellana (Hazelnut) Seed Oil, Cucumis Melo (Melon) Seed Oil, Cucumis Sativus (Cucumber) Seed Oil, Cucurbita Pepo (Pumpkin) Seed Oil, Elaeis Guineensis (Palm) Oil, Elaeis (Palm) Fruit Oil, Glycine Soja (Soybean) Oil, Gossypium Herbaceum (Cotton) Seed Oil, Gossypium Hirsutum (Cotton) Seed Oil, Helianthus Annuus (Sunflower) Seed Oil, Macadamia Integrifolia Seed Oil, Macadamia Ternifolia Seed Oil, Mangifera Indica (Mango) Seed Butter, Mangifera Indica (Mango) Seed Oil, Melissa Officinalis Seed Oil, Microalgae Oil, Moringa Oleifera Seed Oil, Moringa Peregrina Seed Oil, Oenothera Biennis (Evening Primrose) Oil, Olea Europaea (Olive) Fruit Oil, Olus Oil, Orbignya Oleifera Seed Oil, Orbignya Speciosa Kernel Oil, Oryza Sativa (Rice) Bran / Germ Oil, Oryza Sativa (Rice) Bran Oil, Oryza Sativa (Rice) Germ Oil, Oryza Sativa (Rice) Lipids, Oryza Sativa (Rice) Seed Oil, Papaver Somniferum Seed Oil, Passiflora Edulis Seed Oil, Persea Gratissima (Avocado) Butter, Persea Gratissima (Avocado) Oil, Prunus Amygdalus Dulcis (Sweet Almond) Oil, Prunus Armeniaca (Apricot) Kernel Oil, Prunus Persica (Peach) Kernel Oil, Punica Granatum Seed Oil, Pyrus Malus (Apple) Seed Oil, Ricinoleic / Caproic / Caprylic / Capric Triglyceride(s), Ricinus Communis (Castor) Seed Oil, Rosa Canina Fruit Oil, Rosa Moschata Seed Oil, Rubus Idaeus (Raspberry) Seed Oil, Sesamum Indicum (Sesame) Seed Butter, Soybean Glycerides, Theobroma Cacao (Cocoa) Seed Butter, Theobroma Grandiflorum Seed Butter, Triticum Vulgare (Wheat) Bran Lipids, Triticum Vulgare (Wheat) Germ Oil, Vitis Vinifera (Grape) Seed Oil, Zea Mays (Corn) Germ Oil, and Zea Mays (Corn) Oil, and mixtures of two or more of the aforesaid plant oils.Preferably, the plant oil is selected from the group consisting of Caprylic Capric Triglycerides, Helianthus Annuus (Sunflower) Seed Oil, Simmondsia Chinensis (Jojoba) Seed Oil, Olea Europaea (Olive) Fruit Oil, Argania spinosa kernel oil (Argan oil), Prunus Amygdalus Dulcis (Sweet Almond) Oil, Persea Gratissima (Avocado Oil), Butyrospermum Parkii (Shea) Butter, Cocos Nucifera (Coconut) Oil, Theobroma Cacao (Cocoa) Seed Butter, and mixtures of two or more of the aforesaid plant oils.The plant oil can be used either as a single component or in mixture with one or more further different plant oil(s) as specified above.If the compound(s) of formula (I) as defined herein is / are used in conjunction with at least one further antioxidant, it is preferred that the at least one further antioxidant is selected from the group consisting of dimethylmethoxy chromanol, hydroxyacetophenone, ascorbicacid and its salts, hydroxymethoxyphenyl decanone, beta-aspartyl arginine, uric acid, urea, hydroxypinacolone retinoate, vitamin A and vitamin A derivatives, butylhydroxytoluol (BHT), butylhydroxyanisol (BHA), hydroxyphenyl propam idobenzoic acid, ascorbyl palmitate, ascorbyl phosphate and salts thereof, carnosine, rutin, tocopherol, tocopheryl acetate, ubiquinone-10, dilauryl thiodipropionate, pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, triethyl citrate, diethylhexyl syringylidene malonate, lactobacillus ferment, lactobacillus filtrate, lactobacillus lysate, cannabinoids, cannabidiol and its extracts, cannabinol, hydroxyphenyl propam idobenzoic acid, green tea extract, Zingiber Officinalis root extract, tropolone, allantoin, o-cymen-5-ol, and mixtures of two or more of said antioxidants. More preferably, the at least one further antioxidant is selected from the group consisting tocopherols, preferably, wherein the at least one further antioxidant contains or consists of a-tocopherol. With the latter group, the compounds of formula (I) combine in an advantageous manner, resulting in a boosting effect of the antioxidative property of tocopherol.Preferably, the formulation comprises 0.0001 to 10,0 wt.-%, preferably 0.0005 to 8.0 wt.- %, more preferably 0.001 to 5.0 wt.-%, of the at least one further antioxidant, preferably tocopherol, based on the total weight of the formulation.In preferred embodiments, the at least one compound of formula (1) is used in an amount of 0.01 to 10 wt.-%, preferably 0.05 to 2.5 wt.-%, more preferably 0.1 to 1.0 wt.-%. For example, the at least one compound of formula (1) is added to, or comprised in, the formulation in an amount of 0.01 to 10 wt.-%, preferably 0.05 to 2.5 wt.-%, more preferably 0.1 to 1.0 wt.-%, based on the total weight of the formulation.Generally, the use of the compounds of formula (I) is not limited to specific types of formulation. Preferred formulations, however, are in the form selected from the group consisting of dispersions, water free oil formulations, liquid surfactant formulations, solid surfactant formulations, micellar waters, and aqueous based solutions. It is further preferred that the dispersion is an emulsion, in particular an O / W emulsion, a W / O emulsion, a multiple emulsion, a hydrodispersion gel, a balm, a multiple emulsion of the water-in-oil type (W / O / W) or of the oil-in-water type (O / W / O), a PIT emulsion, a pickering emulsion, a micro-emulsion, a liquid, a lotion, a suspension, a milk, an ointment, a paste, a gel, an oil based cream or a liposome based formulation. The aqueous based solution preferably includes aqueous, aqueous alcoholic and aqueous glycolic solutions.The formulation as described herein may be comprised in a product of personal care, household, pharmaceutical, and food.Preferably, the personal care product is selected from the group consisting of deodorant products, body care and cleansing products, intimate care and cleansing products, foot care and cleansing products, oral care and cleansing products, scalp care and cleansing products, and face care and cleansing products, more preferably wherein the personal care product is selected from the group consisting of deodorant sprays, deodorant sticks, deodorant creams, foot creams, bodylotions, body butters, concentrates, body washes, mouth washes, toothpastes, shampoos, hair conditioner, styling wax, styling gels, styling foams, styling creams, styling mousses, styling serums, styling pomades, intimate washes, cleansers, micellar water, toners, serums, moisturizers, eye creams, balms, soaps, facial masks, sunscreens, liquids for wet wipes, primers, concealers, foundations, rouges, bronzers, highlighters, eyebrow pencils, eyebrow creams, eyebrow waxes, eyebrow gels, eyebrow powders, eyeshadows, eyeliners, mascara, lipsticks, lip glosses, lip liners, lip balms, face powders, setting powders, setting sprays, and nail polishes.Preferably, the household product is selected from the group consisting of alcohol free glass cleaners, glass cleaners, all-purpose cleaners, all-purpose sprays, degreasers, carpet cleaners, wood cleaners, floor cleaners, laminate cleaners, vinyl cleaners, ceramic cleaners, cork cleaners, linoleum cleaners, porcelain cleaners, stone cleaners, concrete cleaners, parquet cleaners, high gloss floor cleaners, kitchen cleaners, fat solver cleaners, bathroom cleaners, toilet cleaners, chalk cleaners, automatic dish washes, hand dish wash fluids, antibacterial hand dish wash fluids, fabric softeners, liquid laundry detergents, powder laundry detergents, and hygiene wash detergents.Preferably, the pharmaceutical product is selected from the group consisting of deodorant sprays, deodorant sticks, deodorant creams, foot creams, body washes, mouth washes, toothpastes, shampoos, intimate washes, cleansers, serums, moisturizers, eye creams, balms, soaps, facial masks, sunscreens, and liquids for wet wipes.Optional constituents of formulations as described herein include on or more of the following: abrasives, anti-acne agents, agents against ageing of the skin, anti-cellulitis agents, anti-dandruff agents, anti-inflammatory agents, anti-microbial agents, irritationpreventing agents, irritation-inhibiting agents, antioxidants, astringents, odor absorbers, perspiration-inhibiting agents, antiseptic agents, anti-statics, binders, buffers, carrier materials, chelating agents, cell stimulants, cleansing agents, depilatory agents, surface-active substances, deodorizing agents, antiperspirants, softeners, emulsifiers, enzymes, enzyme inhibitors, essential oils, fibers, film-forming agents, fixatives, foam-forming agents, foam stabilizers, substances for preventing foaming, foam boosters, gelling agents, gelforming agents, hair care agents, hair-setting agents, hair-straightening agents, moisturedonating agents, moisturizing substances, moisture-retaining substances, bleaching agents, strengthening agents, stain-removing agents, optically brightening agents, impregnating agents, dirt-repellent agents, dyes, friction-reducing agents, lubricants, moisturizing creams, ointments, opacifying agents, plasticizing agents, covering agents, polish, preservatives, gloss agents, green and synthetic polymers, powders, proteins, reoiling agents, abrading agents, silicones, skin-soothing agents, skin-cleansing agents, skin care agents, skin-healing agents, skin-lightening agents, skin-protecting agents, skinsoftening agents, hair promotion agents, cooling agents, skin-cooling agents, warming agents, skin-warming agents, stabilizers, surfactants, UV-absorbing agents, UV filters, primary sun protection factors, secondary sun protection factors, detergents, fabric conditioning agents, suspending agents, skin-tanning agents, actives modulating skin or hair pigmentation, matrix-metalloproteinase inhibitors, skin moisturizing agents, glycosaminoglycan stimulators, TRPV1 antagonists, desquamating agents, anti-cellulite agents or fat enhancing agents, hair growth activators or inhibitors, thickeners, rheology additives, vitamins, oils, waxes, pearlizing waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, a-hydroxy acids, polyhydroxyfatty acids, liquefiers, dyestuffs, colour-protecting agents, pigments, anti-corrosives, fragrances or perfume oils, aromas, flavouring substances, odoriferous substances, polyols, electrolytes, organic solvents, and mixtures of two or more of the aforementioned substances.Preferred constituents of formulations as described herein include on or more of the following: agents against ageing of the skin, anti-microbial agents, (further) antioxidants, chelating agents, emulsifiers, surfactants, preservatives, green and synthetic polymers, skin-cooling agents, rheology additives, oils, fragrances, perfume oils, and polyols (different from the compounds of formula (I) and the optional antioxidant(s) as described herein).Examples of the aforementioned optional and preferred constituents as well as further constituents that can be included in the preparations as described herein can be found in paragraphs

[0284] to

[0351] of WO2022 / 122935.While the preceding description was primarily made on the basis of compounds of formula (I) and corresponding formulations, it is to be understood that this description is also made in conjunction with the various uses and methods of the invention, and that theembodiments, features and effects described in conjunction with the compounds of formula (I) and formulations are to be understood to be applicable to all (other) aspects of the invention.Moreover, the compounds of formula (I) are to be understood as preferred compounds of the present disclosure only, and the aspects, embodiments, features and effects described in conjunction with the compounds of formula (I) are to be understood to be correspondingly applicable to the compounds of formula (II). This means, for instance, that the compounds of formula (II) can be used for the purposes, in the methods or in the preparations, as described herein in place of the compounds of formula (I). It likewise means, for example, that in preferred compounds of formula (II), X is as defined in formula (I), or that preferred preparations may comprise the compounds of formula (II) in the same amount as described for the compounds of formula (I).The compounds of formula (II) are defined as follows: with n = 1-10wherein X is:• straight-chain C5 - C14, preferably Ce - C14, more preferably C7 - C13, yet more preferably Cs - Ci2, most preferably C9 - Cn, alkyl or alkenyl; or• selected from the group consisting of:with R3being -OCH3, -OCH2CH3, or -O(CH2)2CH3,wherein if n = 1 :• R1is selected from the group consisting of -H and -OH, and R2is selected from the group consisting of -H, -CH2(OH), -CH(OH)-CH2(OH), and -CH(OH)-CH(OH)- CH2(OH); or ® R1is -OH, and R2and the -OH group shown in formula (II) are joined together to form the following compound of formula (ll-a):• R1and R2are joined together to form the following compound of formula (ll-b):wherein if n = 2-10, R1is -OH, and R2= -H.When X is , R3(as defined above) can be on any one of the free carbon atoms of the benzyl ring, i.e. X can be selected from the group consisting of:Structures of particular interest are:The compounds of formulae (I) are accessible not only via precursors of petrochemical origin, but advantageously also in a sustainable and / or cost-efficient way from biobased starting materials comprising only non-fossil fuel-based carbon. Assessment of the biobased carbon in a material can be performed through standard test methods. Using radiocarbon and isotope ratio mass spectrometry analysis, the biobased content of materials can be determined. ASTM International, formally known as the American Society for Testing and Materials, has established a standard test method for assessing the biobased content of materials. The ASTM method is designated ASTM D6866. According to a preferred embodiment of the present invention, more than 50% of the carbon atoms contained in a compound of formula (I) are biobased, based on the total number of carbon atoms contained in said compound of formula (I). More preferably, more than 60%, 70%, 75%, 80%, 85%, or 90% of the carbon atoms contained in a compound of formula (I) are biobased, based on the total number of carbon atoms contained in said compound of formula (I). The same is true for compounds of formula (II).The present invention is further described with reference to the examples, which are merely illustrative for, but do not limit, the present invention, and with reference to the drawings, which show:Fig. 1 : influence of 0.5 wt-% 3-hydroxypropylesters on the time after which a pressure increase was observed (induction period) in sunflower oil, as compared to sunflower oil lacking respective 3-hydroxypropylesters.Fig. 2: influence of 0.5 wt-% 3-hydroxypropylesters on the acidic value of sunflower oil, as compared to sunflower oil lacking respective 3-hydroxypropylesters.Fig. 3: influence of 0.5 wt-% 3-hydroxypropylesters on the odor intensity of sunflower oil, as compared to sunflower oil lacking respective 3-hydroxypropylesters.Fig. 4: influence of 0.5 wt-% 3-hydroxypropylesters on the time after which a pressure increase was observed (induction period) in sunflower oil containing tocopherol, as compared to tocopherol containing sunflower oil lacking respective 3- hydroxypropylesters (denoted as “Sunflower oil”) and sunflower oil lacking both tocopherol and respective 3-hydroxypropylesters (denoted as “Sunflower oil wo Tocopherol”).Fig. 5: influence of 0.5 wt-% 3-hydroxypropylesters on the acidic value of sunflower oil containing tocopherol, as compared to tocopherol containing sunflower oil lacking respective 3-hydroxypropylesters (denoted as “Sunflower oil”) and sunflower oil lacking both tocopherol and respective 3-hydroxypropylesters (denoted as “Sunflower oil wo Tocopherol”).Fig. 6: influence of 0.5 wt-% 3-hydroxypropylesters on the odor intensity of sunflower oil containing tocopherol, as compared to tocopherol containing sunflower oil lacking respective 3-hydroxypropylesters (denoted as “Sunflower oil”) and sunflower oil lacking both tocopherol and respective 3-hydroxypropylesters (denoted as “Sunflower oil wo Tocopherol”).Examples:In the following, the inventors’ research on the influence of the compounds of formula (1) as defined herein on the antioxidative capacity is shown, using compounds of formula (1- a) to (1-e) and sunflower oil, optionally containing tocopherol, as exemplary compounds and formulation, respectively. To this end, sunflower oil with and without tocopherol was used as base formulations, and the compounds of formula (1 -a) to (1 -e) were added thereto.1. MaterialsThe compounds of formulae (I) and (II) can be obtained, for instance, by following the synthetic approaches described in Synthesis, 2003, (15), 2373-2377; Journal of the Korean Chemical Society, 2002, 46(5); Tetrahedron Letters, 2015, 56(15), 1973-1975; and JP2011207990A.2. Methods2.1 OxipresPrior to their evaluation, each sample was prepared by stirring for 15 minutes at ambient temperature (20 to 25°C) with a magnetic stirrer (250rpm). 15g samples was transferred to Oxipres, 15g remained as comparison sample and start value.The samples were treated for 48 h at 80°C with 5 bar oxygen, and the time until a pressure reduction is observed was noted. The pressure correlates with oxidation; hence, the initial pressure reduction is indicative for the start of oxidation. The time until the pressure begins to drop denotes the induction period (IP). The higher the IP, the later oxidation starts.Based on the determined values a so-called protection factor was calculated as follows:Protection Factor (PF) = IP (sample) I IP (reference)The reference sample differed from the (test) sample in that neither a 3-HPE nor tocopherol as a further antioxidant was included.After oxipres treatment, the samples were subjected to evaluation of its odor and acidic value:2.2 Odor evaluationThe application of plant oil as a natural raw material in cosmetics is beneficial to the human body, but, as described further above, plant oils often contain free fatty acids, especially unsaturated fatty acids, which are unstable to heat and oxygen, and may thereby cause oily rancidity. To evaluate antioxidative properties, the samples were thus evaluated by a minimum number of 5 panelists on a scale from 1 to 5 regarding unpleasant odor.1 = No unpleasant odor5 = Very strong unpleasant odor2.3 Acidic valueThe acidic value was determined by titration with potassium hydroxide (KOH) and is defined as the quantity of KOH required to neutralize the acidic constituents in 1gram of sample. The acidic value for an oil sample is indicative for the age of the oil. The higher the acidic value the more fat is oxidized.3. Results3.1 Antioxidant properties of 3-HydroxypropylesterThe results are graphically presented in Figs. 1 to 3. 3.2 Tocopherol boostingAll samples were prepared in the same manner as above, except that 0.1% alpha- Tocopherol was added to each sample (unless indicated otherwise).The results are also shown in Figs. 4 to 6.. Formulation examplesCosmetic formulations (compositions) - amounts are indicated as % by weight for all formulations.4.1 DEO a) Deodorant Sprayb) Deodorant Aerosolc) Deodorant Roll-ond) Antiperspirant / deodorant roll-one) Deodorant formulation in the form of a roll-on gel4.2 GEL a) Flash SOS Aloe Geleeb) After Shavec) After Sun Refreshing Geld) Men After Shave Fluide) Clear Beard Gel4.3 EMULSIONS a) Anti-Wrinkle Night Emulsionb) Essential Care Face& Body Creamc) Barrier repair creamd) Detox Face Primere) Eye Cream for Mature Skinf) Refreshing and Soothing After Sun Cream4.4 Leave on w / o a) Baby Erythema Cotton Creamb) Natural Anti-Stretch Mark Creamc) Weather Protection Creamd) Natural Night Cream Aloee) Cracked Heel Cream4.5 SUN CARE a) Sun protection milk (w / o)b) Anti-Pollution HairCare (SPF 15)c) BB Cream Dark Tone SPF-20 (Expected)d) Natural Tanning Sun Milk SPF 30e) UV protection water spray SPF 50f) Urban Sun Spray exp. SPF 50+g) Sunscreen Spray, *SPF 50+, Very Water Resistant4.6 WIPES a) Clear Anti Acne Wipeb) Intimate Wipes4.7 UP CARE a) Refreshing Lip Gloss4.8 MASKS a) Warming Mineral Maskb) Glow Dream Maskc) Detox Maskd) Illuminating Snow MASK with Glacier Water4.9 Concentrate & Solid formulations a) Energy Concentrateb) Natural Beauty Enhancer (Solid concentrate)c) Solid Body Oild) Beard Tamere) Night SERUMf) Eye contour serumg) Sensi-SCALP (Green Solid Shampoo)h) Beautifying UV Defender Stick SPF 30i) Advanced Lifting serumj) Illumination effect serumk) Hair Soap SHAMPOO BarI) All in one bar- Shampoo- body- beard

Claims

Claims:1 . Use of at least one of compounds of formula (I)wherein X is straight-chain C5 - C14, preferably Ce - C14, more preferably C7 - C13, yet more preferably Ca - C12, most preferably C9 - Cn, alkyl or alkenyl; orX is selected from the group consisting of:with R3being -OCH3, -OCH2CH3, or -O(CH2)2CH3, and whereinR1is selected from the group consisting of -H and -OH, and R2is selected from the group consisting of -H, -CH2(OH), -CH(OH)-CH2(OH), and -CH(OH)- CH(OH)-CH2(OH); orR1is -OH and R2and the -OH group shown in formula (I) are joined together to form the following compound of formula (l-a):orR1and R2are joined together to form the following compound of formula (l-b):(l-b) as an antioxidant and / or as an antioxidant booster.

2. Use of claim 1 , wherein X is selected from the group consisting of:, and3. Use of claim 1 or 2, wherein R1and R2are all -H.

4. Use of any of the previous claims, wherein the use as an antioxidant and / or as an antioxidant booster involves protecting unsaturated fatty acids from oxidation, wherein the fatty acids are preferably part of a plant oil.

5. Use of any of the previous claims, wherein the formulation is selected from the group consisting of personal care, household, pharmaceutical and food formulations.

6. Formulation selected from the group consisting of personal care, household, pharmaceutical, and food formulations, comprising(i) at least one of compounds of formula (I) as defined in any of claims 1 to 3,(ii) unsaturated fatty acids, preferably derived from, or included in, an oil, preferably a plant oil, and / or(iii) at least one further antioxidant that is different from compounds of formula (I) as defined in any of claims 1 to 3 .

7. Formulation of claim 6, wherein the plant oil is selected from the group consisting of Caprylic Capric Triglycerides, Melianthus Annuus (Sunflower) Seed Oil, Simmondsia Chinensis (Jojoba) Seed Oil, Olea Europaea (Olive) Fruit Oil, Argania spinosa kernel oil (Argan oil), Prunus Amygdalus Dulcis (Sweet Almond) Oil, Persea Gratissima (Avocado Oil), Butyrospermum Parkii (Shea) Butter, Cocos Nucifera (Coconut) Oil, Theobroma Cacao (Cocoa) Seed Butter, and mixtures of two or more of the aforesaid plant oils.

8. Formulation of claim 6 or 7, wherein the at least one further antioxidant is selected from the group consisting of dimethylmethoxy chromanol, hydroxyacetophenone, ascorbic acid and its salts, hydroxymethoxyphenyl decanone, beta-aspartyl arginine, uric acid, urea, hydroxypinacolone retinoate, vitamin A and vitamin A derivatives,butylhydroxytoluol (BHT), butylhydroxyanisol (BHA), hydroxyphenyl propam idobenzoic acid, ascorbyl palmitate, ascorbyl phosphate and salts thereof, carnosine, rutin, tocopherol, tocopheryl acetate, ubiquinone-10, dilauryl thiodipropionate, pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, triethyl citrate, diethylhexyl syringylidene malonate, lactobacillus ferment, lactobacillus filtrate, lactobacillus lysate, cannabinoids, cannabidiol and its extracts, cannabinol, hydroxyphenyl propam idobenzoic acid, green tea extract, Zingiber Officinalis root extract, tropolone, allantoin, o-cymen-5-ol, and mixtures of two or more of said antioxidants.

9. Formulation of claim 8, wherein the at least one further antioxidant is selected from the group consisting of tocopherols, preferably, wherein the at least one further antioxidant contains or consists of a-tocopherol.

10. Formulation of any of claims 6 to 9, comprising 0.0001 to 10,0 wt.-%, preferably 0.0005 to 8.0 wt.-% , more preferably 0.001 to 5.0 wt.-%, of the at least one further antioxidant, preferably tocopherol, based on the total weight of the formulation.1 1 . Formulation of any of claims 6 to 10, comprising 0.01 to 10 wt.-%, preferably 0.05 to 2.5 wt.-%, more preferably 0.1 to 1.0 wt.-%, of the one or more compound(s) of formula (I) based on the total weight of the formulation.

12. Formulation of any of claims 6 to 1 1 , wherein the formulation is in the form selected from the group consisting of dispersions, water free oil formulations, liquid surfactant formulations, solid surfactant formulations, and aqueous based solutions, wherein, preferably: the dispersion is preferably an emulsion, in particular an O / W emulsion, a W / O emulsion, a multiple emulsion, a hydrodispersion gel, a balm, a multiple emulsion of the water-in-oil type (W / O / W) or of the oil-in-water type (O / W / O), a PIT emulsion, a pickering emulsion, a micro-emulsion, a liquid, a lotion, a suspension, a milk, an ointment, a paste, a gel, an oil based cream or a liposome based formulation; and / orthe aqueous based solution includes aqueous, aqueous alcoholic and aqueous glycolic solutions.

13. Method of protecting an object from oxidation, comprising or consisting of:(a) providing at least one of compounds of formula (I) as defined in any of claims 1 to 3, or a formulation as defined in any of claims 6 to 12;(b) providing an object to be protected from oxidation, and(c) applying the compound(s), or the formulation of (a) to the object of (b) in an amount sufficient to provide an antioxidative benefit.

14. Method of claim 13, wherein the object to be protected is a formulation containing unsaturated fatty acids, wherein the unsaturated fatty acids are preferably derived from an oil, preferably plant oil, and wherein the formulation is preferably selected from the group consisting of personal care, household, pharmaceutical and food formulations.

15. Use of any of claims 1 to 5, wherein the formulation is as defined in any of claims 8

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