Process for the production of c6-c18 alkyl esters of 4-aminobenzoic acid

Abstract

A process for the production of a C6-18 alkyl ester of 4-aminobenzoic acid of formula (I), wherein the process comprises the step of reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a C6-18 alkyl ester of 4-aminobenzoic acid of formula (I) wherein R is a C6-18 alkyl group; and wherein the catalyst is a titanium catalyst, preferably a titanium alkoxide catalyst.

Description

[0001] DSM IP Assets B.V. 2024P00096WO

[0002] PROCESS FOR THE PRODUCTION OF C6-C18 ALKYL ESTERS OF 4-AMINOBENZOIC ACID

[0003] Field of the invention

[0004]

[0001] The present invention relates to a novel process for the preparation of C6-C18 hydrocarbyl esters of 4-aminobenzoic acid, compositions obtained in such a process and uses of the compositions so obtained.

[0005] Background of the invention

[0006]

[0002] Nowadays, there is a growing awareness among consumers that the finite nature of traditional resources requires a shift towards renewable sources so to ensure long-term availability for generations to come. Renewable sources have indeed several advantages, including higher sustainability and being a cleaner and “green” alternative to non-renewable resources.

[0007]

[0003] To serve their customers, pharmaceutical and cosmetic companies around the world are in search of more sustainable manners to produce their products and have an increased desire to manufacture their products from renewable resources.

[0008]

[0004] Esters of 4-aminobenzoic acid (also referred to as para-aminobenzoic acid, abbreviated as “PABA”) have found widespread applications in the preparation of active pharmaceutical and / or cosmetic ingredients. For example, the 2-ethylhexyl ester of para-aminobenzoic acid can be applied as a light stabilizer in sunscreen compositions or can serve as a precursor or an intermediate in the synthesis of certain UV filters such as ethylhexyl triazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP). Thus, esters of 4-aminobenzoic acid, in particular higher alkyl esters, are highly interesting compounds.

[0009]

[0005] There are many chemical processes for the preparation of esters of 4-aminobenzoic acid known in industry. However, traditionally these processes have not been very friendly to the environment.

[0010]

[0006] Traditionally esters of 4-aminobenzoic acid have been prepared in a two-step chemical synthesis starting from 4-nitrobenzoic acid. For example, Adams et al. describe in their article titled “Chemical constitution, physiological action and physical properties in a series of alkyl paraaminobenzoates”, published in J. Am Chem Soc vol. 48, June 1926, pages 1758-1770 a process wherein various esters of p-amino benzoic acid were made by condensing p-nitrobenzoyl chloride with alcohols and subsequently reducing the nitro esters with iron or by catalysis with platinum oxideplatinum black. However, such a process is not considered sustainable. For example p-Nitrobenzoic acid is a nitroaromatic compound, which can be toxic and persistent in the environment.

[0007] CN112321522A describes a preparation method for octyl triazone, comprising an esterification reaction on p-nitrobenzoic acid and isooctyl alcohol, a hydrogenation reaction in the presence of a catalyst, and a finishing step to obtain the octyl triazone.

[0011]

[0008] CN117384053A describes a method of manufacturing iso-octyl p-dimethylaminobenzoate. Isooctyl p-dimethylaminobenzoate comprises a so-called tertiary amine, which tertiary amine is bonded on one side to the benzoate ring and is further substituted with two methyl groups. CN117384053A describes preparation of such iso-octyl p-dimethylaminobenzoate by a multi-step method including a transesterification of ethyl p-aminobenzoate and isooctanol to prepare an intermediate and reacting the intermediate with formaldehyde and formic acid. In the examples a catalyst solution of isooctyl alcohoktitanate of 3:1 is applied. The method is carried out in one pot, without any isolation of any intermediate transesterification product. The tertiary amine product (iso-octyl p-dimethylaminobenzoate) was obtained in a yield of 92-95 % and purity of 98.3-98.5 %. CN117384053A does not specify how the ester starting material, ethyl para-aminobenzoate, is prepared and hence it is unclear whether the production of such ethyl para-aminobenzoate involved for example a reaction between p-nitrobenzoic acid and ethanol or not. From an industrial perspective, a multistep transesterification process such as described in CN117384053A is less desirable than a direct production of the desired product.

[0012]

[0009] Following the desire within the market for more sustainable products there is an increasing desire in the cosmetics industry to base ingredients as much as possible on sustainable resources, for example resources comprising a high degree of renewable carbon atoms.

[0013]

[0010] Methods for a sustainable microbial production of 4-aminobenzoic acid are already known. For example, WO2013103894, WO2016053649A1 and WO2017146241 describe different genetically modified micro-organisms capable of producing para-aminobenzoic acid. Such para-aminobenzoic acid would be considered completely renewable.

[0014]

[0011] The manufacture of esters of 4-aminobenzoic acid directly from such sustainable and / or environmental friendly 4-aminobenzoic acid would be desirable from an environmental, a cost and economical point of view. However, up to today, such a manufacture has been challenging.

[0015]

[0012] Whilst for example W02021010681 describes a SOCh - mediated process to manufacture a low alkyl ester such as methyl 4-aminobenzoate directly from para-aminobenzoic acid, the direct manufacture of higher alkyl esters of para-aminobenzoic acid, applying an alcohol component featuring more than five carbon atoms, have been proven to be more challenging. RU2428105 describes the sulfuric acid mediated esterification of 4-aminobenzoic acid with beta-cyclodextrin. This method, however, employs a large excess of the toxic solvent N,N-dimethylformamide and is thus not desirable for sustainable industrial manufacture.

[0013] In their article titled “Direct synthesis of long-chain alcohol esters of p-aminobenzoic acid”, published in the Journal of Henan Normal University (Natural Science), 2008 (vol. 36), pages 174-175 Liu et al. describe a sulfuric acid mediated esterification of 4-aminobenzoic acid with n- butanol, n-pentanol, n-heptanol and n-octanol. The article reports results obtained at a reaction time of 7 hours at reflux temperature. According to the article of Liu et al., the highest yield occurs when the molar ratio of concentrated sulfuric acid to p-aminobenzoic acid (PABA) is 1 :1. According to Liu et al. the yield is the highest when the ratio alcohol: PABA is 12.

[0016]

[0014] It would be an advancement in the art to provide a process for the manufacture of C6-C18 alkyl esters of 4-aminobenzoic acid, wherein the C6-C18 alkyl esters of 4-aminobenzoic acid are increasingly manufactured from renewable or otherwise sustainable resources. For example, it would be an advantage to provide a sunscreen composition comprising a UV filter with a maximum content of renewable carbon (either mass balanced renewable carbon or 100% renewable carbon).

[0017]

[0015] In addition or in the alternative it would be an advancement in the art to provide a process for the manufacture of C6-C18 alkyl esters of 4-aminobenzoic acid that is economic and / or provides products in high purity and / or in high yield. It is thus an objective of the present invention to provide a process for the direct synthesis of C6-C18 alkyl esters of 4-aminobenzoic acid that is economically attractive to industry.

[0018] Summary of the invention

[0019]

[0016] Advantageously a process for the manufacture of C6-C18 alkyl esters of 4-aminobenzoic acid, that is economic and / or provides products in high purity and / or in high yield, has now been found. In addition, this process advantageously allows for the so produced C6-C18 alkyl esters of 4-aminobenzoic acid to be at least partly manufactured from sustainable resources. Further the provided process allows for a direct synthesis of C6-C18 alkyl esters of 4-aminobenzoic acid that is economically attractive to industry.

[0020]

[0017] Accordingly, in a first aspect, the invention provides a process for the production of a Ce- alkyl ester of 4-aminobenzoic acid of formula (I), wherein the process comprises a step of reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a Ce-is alkyl ester of 4-aminobenzoic acid of formula (I)

[0021]

[0022] wherein R is a Ce-is alkyl group and wherein the catalyst is a titanium catalyst, preferably a titanium alkoxide catalyst.

[0023]

[0018] The above process can advantageously be used as part of a process for the preparation of certain UV filters such as ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP).

[0024]

[0019] Hence, in a second aspect, the invention provides a process for the production of a UV filter, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT) or ethylhexyl dimethyl PABA (EHDP),

[0025] wherein the process comprises the steps of:

[0026] a) reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a mono Ce-is alkyl ester of 4-aminobenzoic acid of formula (I)

[0027]

[0028] wherein Ris a Ce-is alkyl group; and

[0029] wherein the catalyst is a titanium catalyst, preferably a titanium alkoxide catalyst; and

[0030] b) converting the mono Ce-is alkyl ester of 4-aminobenzoic acid of formula (I) in one or more further reaction steps to a UV filter, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP).

[0031]

[0020] From an industrial perspective, direct esterification of benzoic acid is more desirable than a multi-step process involving initial ester formation followed by transesterification because it is more atom-economical, avoids the need for intermediate purification, and reduces waste and reaction time. However, direct esterification is more challenging than transesterification, for example from a reactivity and byproduct generation perspective. For example, in a transesterification the formed byproduct (such as ethanol in CN117384053A) may be easier to remove than any water formed in a direct esterification. Transesterification are therefore known to proceed more readily and under milder conditions than direct esterifications.

[0032]

[0021] As illustrated in the experimental section below, although the direct esterification process described in the article of Liu et al generates high yields, unfortunately the process as described by Liu et al also resulted in significant amounts of a secondary amine. Aromatic secondary amines are associated with a risk of genotoxicity and hence are undesired. Without wishing to be bound by any kind of theory, it is believed that the conditions as described by Liu et al promote the formation of such secondary amines of formula (IV) as a by-product.

[0033]

[0034] The process according to the invention advantageously allows one to reduce the production of such secondary amines of formula (IV) as a by-product.

[0035] In addition, the article of Liu et al is silent about the origin of the 4-aminobenzoic acid.

[0036]

[0022] In a third aspect, the invention therefore provides a composition comprising, essentially consisting of or consisting of:

[0037] a Ce-18 alkyl ester of 4-aminobenzoic acid of formula (I)

[0038]

[0039] and a secondary amine of formula (IV)

[0040]

[0041] wherein Ris a Ce-is alkyl group, and

[0042] wherein the molar ratio of Ce-is alkyl ester of 4-aminobenzoic acid of formula (I) to any secondary amines of formula (IV) is equal to or more than 25, more preferably equal to or more than 50, still more preferably equal to or more than 75, even more preferably equal to or more than 99, yet more preferably equal to or more than 500, yet still more preferably equal to or more than 800 and most preferably equal to or more than 900 or even equal to or more than 1000.

[0043] The invention also provides a composition comprising, consisting essentially of or consisting of : a Ce-18 alkyl ester of 4-aminobenzoic acid of formula (I)

[0044]

[0045] and a secondary amine of formula (IV)

[0046]

[0047] wherein the secondary amine of formula (IV) is present in the composition at a concentration of equal to or less than 1000 parts per million (ppm), more preferably equal to or less than 500 ppm, still more preferably equal to or less than 100 ppm, yet more preferably equal to or less than 50 ppm and most preferably equal to or less than 10 ppm, based on the total weight of the composition.

[0048] Preferably such Ce-is alkyl ester of 4-aminobenzoic acid and / or such compositions contain in the range from equal to or more than 1 wt% to equal to or less than 100 wt% of mass balanced renewable carbon, more preferably renewable carbon, most preferably microbial produced carbon, as calculated based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid, respectively based on the total weight of carbon present in such composition.

[0049] Preferably the Ce-is alkyl ester of 4-aminobenzoic acid and / or such compositions have a total content of biobased carbon in the range from equal to or more than 1wt% to equal to or less than 100 wt%, preferably as determined in accordance with ASTM-D6866, based on the total weight of carbon atoms of the Ce-is alkyl ester of 4-aminobenzoic acid and / or such compositions. More preferably the Ce-18 alkyl ester of 4-aminobenzoic acid and / or such compositions have a total content of biobased carbon of at least 1.0 wt.-%, more preferably of at least 10 wt.-%, even more preferably of at least 25 wt.-%, and most preferably of at least 35 wt.-%, preferably as determined in accordance with ASTM-D6866, based on the total weight of carbon atoms of the Ce-is alkyl ester of 4-aminobenzoic acid and / or such compositions.

[0050]

[0023] More preferably the 4-aminobenzoic acid of formula (II) and / or the hydroxy compound of formula (III) are derived partly or wholly from a mass balanced renewable, a renewable, or otherwise sustainable and / or environmental friendly source. More preferably both the 4-aminobenzoic acid of formula (II) and the hydroxy compound of formula (III) are derived partly or wholly from a mass balanced renewable, a renewable, or otherwise sustainable and / or environmental friendly source. More preferably both the 4-aminobenzoic acid of formula (II) and the hydroxy compound of formula (III) comprise solely renewable carbon or mass balanced renewable carbon. Such would advantageously allow the produced Ce-is alkyl ester of 4-aminobenzoic acid to be a compound that comprises 100% renewable carbon or mass balanced renewable carbon. Most preferably such renewable carbon is microbial produced carbon.

[0051]

[0024] Accordingly, in a fourth aspect, the invention provides a Ce-is alkyl ester of 4-aminobenzoic acid which contains equal to or more than 45 wt.%, more preferably 100 wt%, of mass balanced renewable carbon, more preferably renewable carbon, most preferably microbial produced carbon, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid. Such a Ce-18 alkyl ester of 4-aminobenzoic acid which contains 100 wt% of mass balanced renewable carbon, renewable carbon, respectively microbial produced carbon is herein also referred to as a 100% mass balanced renewable Ce-is alkyl ester of 4-aminobenzoic acid, respectively a 100% renewable Ce-is alkyl ester of 4-aminobenzoic acid, respectively a 100% microbial produced Cs-is alkyl ester of 4-aminobenzoic acid. Further preferences of such can be found below.

[0052]

[0025] More preferably the invention provides a Ce-is alkyl ester of 4-aminobenzoic acid which contains equal to or more than 45 wt.%, more preferably 100 wt%, of biobased carbon, preferably as determined in accordance with ASTM-D6866, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid.

[0026] Such a 100% mass balanced renewable, respectively 100% renewable, respectively 100% microbial, respectively 100% biobased, Ce-is alkyl ester of 4-aminobenzoic acid can advantageously be used to produce a UV filter with an increased percentage of respectively mass balanced renewable carbon, respectively renewable carbon, respectively microbial produced carbon, which in turn can be advantageously used to prepare a more sustainable suncare product.

[0053]

[0027] Accordingly, in a fifth aspect, the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three elements, such as substituents, derived from a Ce-is alkyl ester of 4-aminobenzoic acid, wherein 100% of the carbon present in the substituent is mass balanced renewable carbon, more preferably renewable carbon, most preferably microbial produced carbon.

[0054]

[0028] More preferably, the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three elements, such as substituents, derived from a Ce-is alkyl ester of 4-aminobenzoic acid, wherein 100% of the carbon present in the substituent is biobased carbon, preferably as determined in accordance with ASTM-D6866.

[0055]

[0029] Further, in a sixth aspect, the invention provides a cosmetic composition, preferably a suncare product, comprising such a UV filter compound. The invention further provides the use of such a UV filter to protect skin against UV radiation and / or to prevent solar damage and skin diseases.

[0056]

[0030] The above aspects of the invention can advantageously support industry in the so-called principles of green chemistry. By producing a more pure end-product, process waste streams can be minimized and the incorporation of resources into the final product can be maximized. The use of the catalyst increases reaction efficiency which can allow for the reduction of energy use and waste formation. The processes according to the invention allow for the use of mass balanced renewable or renewable starting compounds that can be used in a more environmental friendly production where less fossil-based chemical sysnthesis is required.

[0057]

[0031] Further details of the invention are provided below.

[0058] Detailed description of the invention

[0059] Definitions

[0060]

[0032] Unless defined otherwise or clearly indicated by context, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

[0061]

[0033] The articles “a” and “an” are used herein to refer to one or to more than one (i.e. to one or at least one) of the grammatical object of the article. By way of example, “an element” may mean one element or more than one element. When referring to a noun (e.g. a compound, an additive, etc.) in the singular, the plural is meant to be included. Thus, when referring to a specific entity, e.g. a "compound", this means "at least one" of that compound, e.g. "at least one compound", unless specified otherwise.

[0062]

[0034] Throughout the present specification and the accompanying claims, all transitional phrases such as ‘comprising,’ ‘including,’ ‘carrying,’ ‘having,’ ‘containing,’ ‘involving,’ ‘holding,’ ‘composed of, and variations such as "comprises", "comprise", "includes" and "include" are to be interpreted inclusively and to be understood to be open-ended, i.e. , to mean including but not limited to. That is, these words are intended to convey the possible inclusion of other elements or integers not specifically recited, where the context allows. Only the transitional phrases ‘consisting of and ‘consisting essentially of’ shall be closed or semi-closed transitional phrases, respectively.

[0063]

[0035] The term 'consisting essentially of as used herein means that the total amount of the listed ingredients ideally sums upto 100 wt. % (weight percent). It is however not excluded that small amount of impurities derived from the ingredients and / or the production process may be present.

[0064]

[0036] When referring to a compound of which several isomers exist (e.g. a D and an L enantiomer), the compound in principle includes all enantiomers, diastereomers and cis / trans isomers of that compound that may be used in the particular aspect of the invention; in particular when referring to such as compound, it includes the natural isomer(s).

[0065]

[0037] Unless explicitly indicated otherwise, the various embodiments of the invention described herein can be cross-combined.

[0066]

[0038] The term "cosmetic composition " or “cosmetic preparation” refers in the present document to a composition suitable for cosmetic purposes. Suitably a cosmetic composition is herein understood to be a composition for cosmetic, that is, non-therapeutic use. More preferably the term "cosmetic composition " or “cosmetic preparation” refers in the present document to a composition which is applied to the surface of a mammalian keratinous tissue. The terms "cosmetic composition " or “cosmetic preparation” can comprise or consist of those cosmetic compositions as defined under the heading "Kosmetika" in Rompp Lexikon Chemie, 10th edition 1997, Georg Thieme Verlag Stuttgart, New York as well as to cosmetic compositions as disclosed in A. Domsch, "Cosmetic Compositions", Verlag fur chemische Industrie (ed. H. Ziolkowsky), 4thedition, 1992. More preferably the "cosmetic composition " or “cosmetic preparation” is a cosmetic preparation, respectively a cosmetic composition, that can be topically applied to mammalian keratinous tissue such as e.g. human skin or hair (including eyelashes, the eyebrows, the nails or the lips), particularly human skin. Hence, the cosmetic composition is preferably a topical composition.

[0067]

[0039] By a topical composition is herein understood a composition for, preferably external, use on keratinous tissue such as the skin.

[0040] The term “keratinous tissue" as used in this document refers to tissue containing keratine, more preferably it means the skin (body, face, contour of the eyes, scalp), head hair, eyelashes, eyebrows, bodily hairs, nails and / or lips. Preferably, the keratinous tissue is the skin and hair.

[0068]

[0041] The term cosmetically acceptable carrier herein refers to all carriers and / or diluents conventionally used in cosmetic preparations. Preferably the cosmetically acceptable carrier comprises or consists of water, oil or a combination of water and oil.

[0069]

[0042] By an “active ingredient”, “active compound”, “active component”, “active agent” or simply “active” is herein understood a substance that has a certain activity. So-called “primary substances” are substances designed to achieve a specific intended effect in a cosmetic product.

[0070]

[0043] By an “excipient” is herein understood an inactive substance formulated alongside the active ingredient in a composition. Whilst the active ingredient provides the primary cosmetic effect or desired outcome, the excipient helps deliver, protect, and stabilize the active ingredient and / or improves the product's usability and acceptability.

[0071]

[0044] By a feedstock can conveniently be understood a raw material used to supply a process. Herein a renewable feedstock is understood to be a raw material derived from natural sources that can be naturally replaced over a relatively short time scale. More preferably, a renewable feedstock is understood to be a raw material that is not from a fossil origin, preferably that is not from coal, oil or natural gas. Examples of a renewable feedstock include sugars, wood, biomass and biobased feedstocks, including microbial produced feedstocks, etc. However a feedstock can also be renewable if it is produced using for example CO2captured from the atmosphere. A renewable feedstock is to be distinguished from non-renewable feedstocks. Non-renewable feedstocks are raw materials deriving from natural sources that are not naturally replaced (i.e. , that are depleted) on a human timescale or are naturally replaced only very slowly by natural processes. Examples of non-renewable feedstock are those of fossil origins, such as coal, oil, and natural gas.

[0072]

[0045] Preferably, said renewable feedstock is a biobased feedstock. In accordance with standard analysis method ASTM D6866, a material can be considered biobased if it contains carbon derived from renewable biological sources, such as: plants, forestry materials, animals, microbial organisms or biomass.

[0073]

[0046] More preferably, said renewable feedstock is a microbial produced feedstock. As defined herein a “microbial produced” feedstock or material is understood to be a feedstock, respectively material, produced by one or more species or strains of living organisms, preferably microbial organisms, such as strains of bacteria, yeast, fungus and other microbes. Herein “microbial", “microbial produced” and “microbially produced” can be considered as synonyms.

[0074]

[0047] Unfortunately most industrial facilities are currently still set up to use fossil-based feedstocks. The conversion of the infrastructure towards green alternatives is taking time. In addition, the industry is struggling with a limited availability of renewable resources. In order to allow for a gradual transition and progressive increase of renewable carbon content in their products, some industries are applying production methods using “mass-balanced renewable carbon”. "Mass-balanced renewable carbon" refers to a method for incorporating renewable carbon into chemical production processes in a controlled and verifiable way. The "mass balance" approach allows renewable carbon sources (such as for example microbially produced feedstocks, feedstocks derived from biomass or feedstocks produced from CO2captured from the atmosphere) to be blended with traditional fossil-based feedstocks in existing production facilities, enabling a gradual transition to renewable carbon without overhauling existing infrastructure.

[0075]

[0048] The term “mass balanced renewable material” is thus used herein for a material produced from mass balanced renewable feedstock, preferably wherein the feedstock is certified as a mass balanced renewable raw material. For example, a mass balanced renewable UV filter contains a certain amount of mass balanced renewable carbon, which is a certified mass balanced renewable carbon as defined herein.

[0076]

[0049] More preferably, the term “mass balance renewable” or “mass balanced renewable” is used herein with the same meaning as indicated in the white paper from “co. project mass balance” of The Ellen MacArthur Foundation having the title “Enabling A Circular Economy For Chemicals With The Mass Balance Approach” and the International Sustainability and Carbon Certification (ISCC) provisions, defining guidelines for the uses of mass balanced raw materials in the chemical industry.

[0077]

[0050] A “mass balanced renewable material” (for example a “mass balanced renewable UV filter” or a “mass balanced renewable ethylhexanol”, etc.) according to the present invention is therefore most preferably a “certified mass balanced renewable material” in accordance with the International Sustainability and Carbon Certification (ISCC) provisions. Such provisions can be found, for example in the “ISCC PLUS” documentation, Version 3.4, of the ISCC - International Sustainability and Carbon Certification (ISCC) of 1 September 2023, publishec by ISCC System GmbH.

[0078]

[0051] According to this definition, the expressions “total content of mass balanced renewable carbon” or “total content of certified mass balanced renewable carbon” indicate a “total content of mass balanced renewable carbon as certified by the International Sustainability and Carbon Certification”. This definition applies also to similar expressions.

[0079]

[0052] In all embodiments of the present invention, the content of “renewable carbon” as defined above is preferably measured by Carbon-14 (C-14 or 14 C) standard analysis (radiocarbon dating), in accordance with ASTM-D6866. Preferably, the “renewable carbon” according to the present invention can be a “biobased” carbon, wherein the term “biobased” is according to the definition given above.

[0080]

[0053] That is, preferably the “renewable carbon” in all embodiments of the invention is biobased carbon as determined according to ASTM test D6866, which test is suitably titled “Standard Test Methods for Determining the Biobased Content of Solid, Liquid and Gaseous samples using Radiocarbon Analysis’, method B. The ASTM test D6866 can therefore advantageously be used to distinguish renewable, biobased, carbon from non-renewable, non-biobased, carbon. The ASTM test D6866 was last updated in 2022 and referred to as ASTM D6866-22.

[0081]

[0054] As explained above, the ASTM test D6866 can use the fact that biobased materials contain carbon from recent biological sources, which includes a measurable amount of the radioactive isotope carbon-14 (“14C”), whilst fossil-based materials, being millions of years old, have no detectable14C due to its decay overtime.

[0082]

[0055] The UV filters and other products described herein are considered to be partly or fully “renewable” when at least one of its educts (for example a starting compound or reactant) is produced from renewable raw materials, respectively renewable feedstock. In this case, they contain an amount of renewable carbon (for example., “100% renewable carbon” deriving from 100% renewable raw materials). According to another embodiment, the UV filters and other products described herein are considered as “mass balanced renewable” when at least one of its educts (for example a starting compound or reactant) is produced from mass balanced renewable raw materials, respectively mass balanced renewable feedstock. In this case, they contain an amount of mass balanced renewable carbon (i.e. , deriving from mass balanced renewable raw materials).

[0083]

[0056] These definitions apply also to similar disclosures, such as to the expressions “mass balanced renewable or renewable ethyl hexanol” etc.

[0084]

[0057] In the present invention, the content of “renewable carbon” as defined above can for example be measured by Carbon-14 (C-14 or 14 C) standard analysis (radiocarbon dating), in accordance with ASTM-D6866. Preferably, the “renewable carbon” according to the present invention can be a “microbial produced” carbon, wherein the term “microbial produced” is according to the definition given above.

[0085]

[0058] In line with the above a microbial produced compound can suitably therefore be considered to a subcategory of a renewable compound and, in turn, a renewable compound can suitbaly be considered to be a 100% mass balanced renewable compound.

[0086]

[0059] In the present document, a “Cx-y-alkyl” group or a “Cx-Cy-alkyl group is an alkyl group comprising in the range from x to y carbon atoms. For example, a Ci-3-alkyl group is an alkyl group comprising 1 to 3 carbon atoms. The alkyl group can be linear or branched. For example -CH(CH3)-CH2-CH3 is considered as a C4-alkyl group.

[0087]

[0060] The skilled person is well aware of the meaning of the term “moiety”. According to the IUPAC Gold Book, a moiety is “part of a molecule”. For example, an ester moleclue RiCOORz may be said to comprise an alcohol moiety (R2O). In chemistry, the term moiety can conveniently be used to describe a distinct and identifiable part or component of a molecule, usually a functional group or a specific substructure.

[0088]

[0061] In case identical labels for symbols or groups are present in several formulae, in the present document, the definition of said group or symbol made in the context of one specific formula applies also to other formulae which comprises the same said label.

[0089]

[0062] By a secondary amine is herein understood a compound comprising a nitrogen atom wherein such nitrogen atom is bonded to two carbon atoms and one hydrogen atom, whereas such carbon atoms are not at the same time double bonded to an oxygen atom. Hence, the carbon atoms to which the nitrogen atom is bonded can be part of an alkyl or aryl group, but not a carbonyl group.

[0090]

[0063] Preferably the secondary amine is a secondary amine of formula (IV)

[0091]

[0092] wherein Ris a Ce-is alkyl group.

[0093] Production of the C6-18 alkyl ester of 4-aminobenzoic acid

[0094]

[0064] As indicated above, in a first aspect, the invention provides a process for the production of a Ce-18 alkyl ester of 4-aminobenzoic acid of formula (I), wherein the process comprises the step of reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a Ce-is alkyl ester of 4-aminobenzoic acid of formula (I)

[0095]

[0096] wherein Ris a Ce-is alkyl group; and

[0097] wherein the catalyst is a titanium catalyst, preferably a titanium alkoxide catalyst.

[0065] In this aspect and other aspects of the invention, R can be a non-cyclic linear or non-linear Cs-Cis alkyl group. More preferably R is a Cs-Cie alkyl group. Most preferably R is a non-cyclic linear or non-linear Cs-Cie alkyl group. Suitable examples for R include a linear or branched hexyl-, heptyl-, octyl-, nonyl-, decyl-, undecyl-, dodecyl-, tridecyl-, tetradecyl-, pentadecyl-, hexadecyl-, heptadecyl- and octadecyl- groups. More preferably R is a branched Ce-is alkyl group, still more preferably a branched Cs-16 alkyl group. Preferred examples for R include branched hexyl-, heptyl-, octyl-, nonyl-, decylundecyl-, dodecyl-, tridecyl-, tetradecyl-, pentadecyl-, hexadecyl-, heptadecyl- and octadecyl- groups. Of these, octyl-groups are most preferred. Still more preferred are mono-branched Ce-is alkyl groups, even more preferably mono-branched Cs-16 alkyl groups. Preferably the branches in such branched Ce-18 alkyl groups are C1-4 alkyl groups, most preferably methyl or ethyl. Hence, even more preferably R is chosen from the group consisting of methylpentyl-, methylhexyl-, methylheptyl-, methyloctyl-, methylnonyl-, methyldecyl-, methylundecyl-, methyldodecyl-, methyltridecyl-, methyltetradecyl-, methylpentadecyl-, methylhexadecyl-, methylheptadecyl-, ethylbutyl-, ethylpentyl- , ethylhexyl-, ethylheptyl-, ethyloctyl-, ethylnonyl-, ethyldecyl-, ethylundecyl-, ethyldodecyl-, ethyltridecyl-, ethyltetradecyl-, ethylpentdecyl- and ethylhexadecyl-. More preferably R is an octyl group. Still more preferably R is an ethylhexyl- group. Suitable examples of ethylhexyl- groups include 2-ethylhexyl- and 3-ethylhexyl-. Most preferably R is a 2-ethylhexyl-group.

[0098]

[0066] The hydroxy compound of formula (III) is preferably an alkanol, more preferably a Cs-16 alkanol. Preferred are non-cyclic, linear or non-linear Ce-is alkanols. More preferred are non-cyclic, linear or non-linear Cs-16 alkanols Suitable alkanols with formula (III) include hexanols, heptanols, octanols, nonanols, decanols, undecanols, dodecanols, tridecanols, tetradecanols, pentadecanols, hexadecanols, heptadecanols and octadecanols. Of these, octanols are most preferred. More preferably the hydroxy compound of formula (III) is a branched Ce-is alkanol, still more preferably a branched Cs-16 alkanol. Preferred examples for the hydroxy compound of formula (III) include branched hexanols, heptanols, octanols, nonanols, decanols, undecanols, dodecanols, tridecanols, tetradecanols, pentadecanols, hexadecanols, heptadecanols and octadecanols. Still more preferred are mono-branched Ce-is alkanols, even more preferably mono-branched Cs-16 alkanols. Preferably the branches in such branched Ce-is alkanols are C1-4 alkyl groups, most preferably methyl or ethyl. Hence, even more preferably the hydroxy compound of formula (III) is chosen from the group consisting of methylpentanol, methylhexanol, methylheptanol, methyloctanol, methylnonanol, methyldecanol, methylundecanol, methyldodecanol, methyltridecanol, methyltetradecanol, methylpentadecanol, methylhexadecanol, methylheptadecanol, ethylbutanol, ethylpentanol, ethylhexanol, ethylheptanol, ethyloctanol, ethylnonanol, ethyldecanol, ethylundecanol, ethyldodecanol, ethyltridecanol, ethyltetradecanol, ethylpentdecanol and ethylhexadecanol. More preferably the hydroxy compound of formula (III) is an octanol, most preferably an ethylhexanol. Suitable examples of ethylhexanols include 2-ethylhexanol and 3-ethylhexanol. Most preferably the hydroxy compound of formula (III) is 2-ethylhexanol.

[0099]

[0067] The reaction can be carried out at a wide range of temperatures. However, preferably the reaction is carried out at a temperature below the boiling temperature of the hydroxy compound of formula (III). More preferably the reaction is carried out at a temperature in the range from equal to or more than than 80°C, more preferably from equal to or more than 100°C, even more preferably from equal to or more than 120°C, still more preferably from equal to or more than 140°C, to equal to or less than 185°C, more preferably to equal to or less than 180°C, even more preferably to equal to or less than 175°C, yet more preferably to equal to or less than 170°C, still more preferably to equal to or less than 160°C. More preferred ranges include a temperature in the range from equal to or more than 100°C to equal to or less than 185°C, more preferably in the range from equal to or more than 120°C to equal to or less than 175°C, even more preferably in the range from equal to or more than 140°C to equal to or less than 160°C.

[0100]

[0068] The reaction can be carried out at a wide range of pressures. However, preferably the reaction is carried out at a pressure of more than 200 millibar (corresponding to about 0.02 MegaPascal), more preferably at a pressure of equal to or more than 400 millibar (corresponding to about 0.04 MegaPascal). Without wishing to be bound by any kind of theory it is believed that such a pressure allows for the best results. For practical and economic purposes, the reaction is preferably carried out at a pressure of less than 20 bar (corresponding to about 2 MegaPascal), more preferably at a pressure of equal to or less than 10 bar (corresponding to about 1 MegaPascal). More preferably the reaction is carried out at a pressure in the range from equal to or more than 400 millibar (corresponding to about 0.04 MegaPascal) to equal to or less than 4 bar (corresponding to about 0.4 MegaPascal), more preferably in the range from equal to or more than 400 millibar to equal to or less than 2 bar (corresponding to about 0.2 MegaPascal), most preferably in the range from equal to or more than 400 millibar to equal to or less than 1 bar (corresponding to about 0.1 MegaPascal). Most preferably the reaction is carried out at an ambient pressure of about 1 bar (corresponding to about 0.1 MegaPascal).

[0101]

[0069] The process can be a batch, semi-continuous or continuous process.

[0102]

[0070] Similar to other esterification reactions, during the reaction of the compound of formula (II) with the compound of formula (III), reaction water may be formed. As esterification is an equilibrium process, when water remains in the reaction mixture, it can shift the equilibrium back toward the reactants (the acid and alcohol), thus reducing the yield of the ester. It is therefore preferred to remove the reaction water during the process of the invention. The reaction water may be removed in any manner known to a person skilled in the art. The reaction water may be removed in a non-continuous or continuous manner and is preferably continuously removed during the reaction. Most preferably reaction water was, preferably continuously, removed by a flow of nitrogen. Alternatively reaction reaction water may be continuously or non-continuously removed by applying a reduced pressure, preferably a pressure of less than 1 bar, more preferably a pressure of equal to or less than 800 millibar. For example the reaction may be carried out by means of catalytic reactive distillation. Such a catalytic reactive distillation can be advantageous from an efficiency perspective.

[0103]

[0071] The reaction time may vary widely. In a batch or semi-continous process, preferably the reaction is carried out to completion, that is until such time as the compound of formula (II) is fully or nearly fully reacted away. Preferably the reaction is carried out for a period in the range from equal to or more than 15 minutes, more preferably from equal to or more than 30 minutes, yet more preferably from equal to or more than 1 hour, still more preferably from equal to or more than 4 hours, most preferably from equal to or more than 6 hours to equal to or less than 60 hours, more preferably to equal to or less than 48 hours, still more preferably to equal to or less than 36 hours, most preferably to equal to or less than 28 hours. Most preferably the reaction is carried out for a period in the range from equal to or more than 6 hours to equal to or less than 24 hours. In a continuous process, for example when the reaction is carried out via catalytic reactive distillation, the residence time may suitably be in the range from equal to or more than 10 minutes, more preferably equal to or more than 15 minutes, still more preferably equal to or more than 20 minutes to equal to or less than 6 hours, more preferably equal to or less than 4 hours, still more preferably equal to or less than 2 hours.

[0104]

[0072] The molar ratio of the hydroxy compound of formula (III) to the 4-aminobenzoic acid of formula (II) may be varied widely. However, preferably the hydroxy compound of formula (III) is present in a molar excess to the 4-aminobenzoic acid of formula (II). That is, preferably the reaction is carried out at a molar ratio of moles of the hydroxy compound of formula (III) to moles of the 4-aminobenzoic acid of formula (II) of equal to or more than 1. Thus, in the reaction preferably the hydroxy compound of formula (III) is applied in a molar surplus to the 4-aminobenzoic acid of formula (II), preferably a less than 10-fold molar surplus. Preferably the reaction is carried out at a molar ratio of the hydroxy compound of formula (III) to the 4-aminobenzoic acid of formula (II) in the range from equal to or more than 1 :1 to equal to or less than 10:1 , more preferably in the range from equal to or more than 2:1 to equal to or less than 6:1, most preferably in the range from equal to or more than 2.5:1 to 5:1.

[0105] Production of the UV filter

[0106]

[0073] In a second aspect, the invention provides a process for the production of a UV filter, preferably ethylhexyltriazone (EHT), iscotrizinol (DBT) or ethylhexyl dimethyl PABA (EHDP), wherein the process comprises the steps of:

[0107] a) reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a mono Ce- alkyl ester of 4-aminobenzoic acid of formula (I)

[0108]

[0109] wherein Ris a Ce-is alkyl group; and

[0110] wherein the catalyst is a titanium catalyst, preferably a titanium alkoxide catalyst; and

[0111] b) converting the mono Ce-is alkyl ester of 4-aminobenzoic acid of formula (I) in one or more further reaction steps to a UV filter, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP).

[0112]

[0074] Preferences for step a) are as described herein above and below.

[0113]

[0075] Step b) can conveniently be carried out in any manner known to a person skilled in the art.

[0114]

[0076] For example a Ce-is alkyl ester of 4-aminobenzoic acid, such as ethylhexyl p-a mi no benzoate, can be reacted with cyanuric chloride in multiple steps to synthesize ethylhexyltriazone (EHT), such as for example described in EP3674293.

[0115]

[0077] The ethylhexyl ester of 4-aminobenzoic acid, also referred to as ethylhexyl p-aminobenzoate, can also be used as one of the reactants in the preparation of diethylhexyl butamido triazone (iscotrizinol, DBT). For example WO2013156270 describes a process for the preparation of diethylhexyl butamido triazone of claims 1-4 which comprises:

[0116] a) reacting cyanuryl chloride with one equivalent of para-amino-benzoic acid to give a compound of formula (V):

[0117]

[0118] or a salt thereof;

[0119] b) reacting the compound obtained in a) with two equivalents of 2-ethylhexyl-4-aminobenzoate to give a compound of formula (VI):

[0120]

[0121] c) and reacting the compound obtained in b) with agents selected from halogenating agents, such as thionyl chloride, sulphuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, oxalyl chloride, phosgene, or mesyl or tosyl halides and a subsequent reaction with tertbutylamine to prepare diethylhexyl butamido triazone.

[0122]

[0078] Ethylhexyl dimethyl PABA (also often referred to as “Padimate O”) can be obtained from the 2-ethylhexyl ester of para-aminobenzoic acid (also referred to as 2-ethylhexyl-4-aminobenzoate) via methylation of the amino group of the 2-ethylhexyl-4-aminobenzoate. Preferably such a methylation would be carried out with the help of formaldehyde and / or formic acid. Such formaldehyde and / or formic acid preferably comprises equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, most preferably 100 wt% of mass balanced renewable carbon, more preferably renewable carbon, most preferably microbial produced carbon, based on the total weight of carbon present in such formaldehyde and / or formic acid.

[0123]

[0079] In one preferred embodiment the methylation is carried out with the help of formaldehyde and / or formic acid obtained from a biobased source. Such biobased formaldehyde and / or formic acid preferably comprises equal to or more than 30 wt%, more preferablyequal to or more than 45 wt%, most preferably 100 wt% of biobased carbon, preferably as determined according to ASTM test D6866, based on the total weight of carbon present in such formaldehyde and / or formic acid.

[0124] The catalyst

[0125]

[0080] The titanium catalyst is preferably a titanium alkoxide catalyst, and more preferably is a titanium (IV) alkoxide, wherein preferably the alkoxide substituent(s), each individually, comprise in the range from equal to or more than 3, more preferably equal to or more than 4, still more preferably equal to or more than 6, to equal to or less than 20, more preferably equal to or less than 18, still more preferably equal to or less than 16 carbon atoms.

[0126]

[0081] More preferably the substituents are the same and the titanium alkoxide catalyst is preferably a titanium (IV) alkoxide, wherein preferably each alkoxide substituent is the same substituent comprising in the range from equal to or more than 3, more preferably equal to or more than 4, still more preferably equal to or more than 6, to equal to or less than 20, more preferably equal to or less than 18, still more preferably equal to or less than 16 carbon atoms.

[0127]

[0082] Preferably the invention provides a process for the production of a Ce-is alkyl ester of 4-aminobenzoic acid of formula (I), wherein the process comprises the step of reacting the 4-aminobenzoic acid offormula (II) with an hydroxy compound of formula (III) inthe presence of a catalyst to generate a Ce-is alkyl ester of 4-aminobenzoic acid of formula (I)

[0128]

[0129] wherein Ris a Ce-is alkyl group,

[0130] and wherein the catalyst is chosen from the group consisting of titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) propoxide, titanium(IV) butoxide, titanium(IV) tert-butoxide, titanium(IV) oxycetylacetonate, titanium (triethanolaminato)isopropoxide, titanium(IV) bis(acetylacetonate) diisopropoxide, titanyl acetylacetonate. Further preferences for such a process are as described herein above and below.

[0131]

[0083] More preferred catalysts include titanium(IV)tetra-iso-propyloxide (Ti(OiPr)4), titanium(IV)tetrabutyloxide (Ti(OBu)4), and titanium(IV) 2-ethylhexyloxide (Ti(OEH)4). Even more preferably the titanium alkoxide catalyst is a titanium alkoxide catalyst with the formula Ti(OR)4, wherein R is a Ce-18 alkyl group. Preferences for the R group are as described herein before. Hence, more preferably R is a Cs-C alkyl group. Preferably the R group in the applied titanium alkoxide catalyst and the R group in the applied hydroxy compound offormula (III) are the same. Most preferably the titanium alkoxide catalyst is titanium(IV) tetraethylhexyloxide

[0132]

[0084] The molar ratio of the catalyst to the 4-aminobenzoic acid offormula (II) may be varied widely. However, preferably the molar ratio of moles catalyst to moles of the 4-aminobenzoic acid of formula (II) lies in the range from equal to or more than 0.0001 :1 to equal to or less than 1 :1 , more preferably in the range from equal to or more than 0.001 :1 to equal to or less than 0.5:1 , most preferably in the range from equal to or more than 0.005:1 to 0.1 :1. The 4-Aminobenzoic acid of formula (II)

[0133]

[0085] Para-aminobenzoic acid is herein also referred to as PABA or 4-aminobenzoic acid. The preferred IUPAC nomenclature for this compound is 4-aminobenzoic acid. 4-Aminobenzoic acid comprises an amino functional group and a carboxyl functional group attached across each other in “para” position to a benzene ring, as illustrated in formula (I).

[0134]

[0086] 4-Aminobenzoic acid traditionally used to be derived from a fossil source. For example by nitration of petroleum-derived toluene, followed by oxidation of 4-nitrotoluene to 4-nitrobenzoic acid and conversion of the 4-nitrobenzoic acid to 4-aminobenzoic acid. These reactions require high temperature conditions and a great deal of energy and are less sustainable.

[0135]

[0087] Preferably the 4-aminobenzoic acid in the process according to the invention comprises or consists of 4-aminobenzoic acid that has a total content of mass balanced renewable carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such 4-aminobenzoic acid. More preferably the 4-aminobenzoic acid in the process according to the invention comprises or consists of 4-aminobenzoic acid that has a total content of renewable carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such 4-aminobenzoic acid. Most preferably the 4-aminobenzoic acid in the process according to the invention comprises or consists of 4-aminobenzoic acid that has a total content of microbial produced carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such 4-aminobenzoic acid. A 4-aminobenzoic acid compound which contains 100 wt% of microbial produced carbon is herein also referred to as a 100% microbial 4-aminobenzoic acid.

[0136]

[0088] Most preferably the 4-aminobenzoic acid in the process according to the invention comprises or consists of 4-aminobenzoic acid that is microbially produced. A 4-aminobenzoic acid compound which is microbially produced is herein also referred to as microbial produced 4-aminobenzoic acid.

[0137]

[0089] Suitable processes for microbial production of 4-aminobenzoic acid include the processes of WO2013103894, WO2016053649A1 and WO2017146241 , which describe different genetically modified micro-organisms capable of producing para-aminobenzoic acid. Such para-aminobenzoic acid would be considered completely (100%) microbially produced.

[0138]

[0090] Preferably the process according to the invention therefore comprises a microbial production of 4-aminobenzoic acid, wherein a fermentable, preferably renewable, carbon containing substrate is, partly or fully, converted to p-a mi no benzoic acid by fermentation with the help of a microbial cell. The microbial cell may or may not be a recombinant microbial cell. Preferably the carbon containing substrate is a biomass, more preferably a biomass comprising or consisting of one or more saccharides. Suitable examples of such saccharides include mono-saccharides, di-saccharides, oligo- saccharides and poly-saccharides. Preferably the microbial cell is a bacterium, a cyanobacterium, an archaeon, or a fungus. More preferably the microbial cell is a E.Coli bacteria or a coryneform bacterium. Further preferences for the carbon containing substrate and the microbial cells are as described in WO2013103894, WO2016053649A1 and WO2017146241 , incorporated herein by reference.

[0139]

[0091] Hence, preferably the invention provides a process for the production of a Ce- alkyl ester of 4-aminobenzoic acid of formula (I), wherein the process comprises:

[0140] a step of partly or fully converting a fermentable carbon containing substrate, to 4-aminobenzoic acid of formula (II) by fermentation with the help of a microbial cell; and

[0141] a step of reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a Ce-is alkyl ester of 4-aminobenzoic acid of formula (I)

[0142]

[0143] wherein Ris a Ce-is alkyl group,

[0144] and wherein the catalyst is preferably a catalyst as described herein.

[0145]

[0092] In addition the invention provides a process for the production of a UV filter, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein the process comprises the steps of:

[0146] partly or fully converting a fermentable carbon containing substrate, to 4-aminobenzoic acid of formula (II) by fermentation with the help of a microbial cell; and

[0147] reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a mono Ce-is alkyl ester of 4-aminobenzoic acid of formula (I)

[0148]

[0149] wherein R is a Ce-is alkyl group; and wherein the catalyst is preferably a catalyst as described herein; and

[0150] converting the mono Ce-is alkyl ester of 4-aminobenzoic acid of formula (I) in one or more further reaction step to a UV filter, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT) or ethylhexyl dimethyl PABA (EHDP).

[0151] The hydroxy compound of formula (III)

[0152]

[0093] Hydroxy compounds of formula (III) traditionally used to be derived from a fossil source. For example, traditionally ethylhexanol is prepared via a reaction of fossil derived propene and carbon monoxide to form butanal, which butanal is subsequently then dimerized and reduced to ethylhexanol. Such hydroxy compounds are not desirable from a sustainability perspective.

[0153]

[0094] Preferably the hydroxy compound of formula (III) in the process according to the invention comprises or consists of a hydroxy compound of formula (III) that has a total content of mass balanced renewable carbon of equal to or more than 25 wt%, more preferably equal to or more than 45 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such hydroxy compound of formula (III). More preferably the hydroxy compound of formula (III) in the process according to the invention comprises or consists of a hydroxy compound of formula (III) that has a total content of renewable carbon of equal to or more than 25 wt%, more preferably equal to or more than 45 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such hydroxy compound of formula (III). Most preferably the hydroxy compound of formula (III) in the process according to the invention comprises or consists of a hydroxy compound of formula (III) that has a total content of microbial produced carbon of equal to or more than 25 wt%, more preferably equal to or more than 45 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such hydroxy compound of formula (III). A hydroxy compound of formula (III) which contains 100 wt% of microbial produced carbon is herein also referred to as a 100% microbial hydroxy compound of formula (III).

[0154]

[0095] In a preferred embodiment, the hydroxy compound of formula (III) is derived from a renewable resource, preferably a biomass. More preferably the hydroxy compound of formula (III) is a mass balanced renewable ethylhexanol, a renewable ethylhexanol or a microbial produced ethylhexanol. Advantageously, the hydroxy compounds of formula (III) can be produced via a reaction of renewable propene and renewable carbon monoxide to form butanal, which butanal can be subsequently dimerized and reduced to ethylhexanol. Recently, PERSTORP, a Swedish company, started to offer ethyl hexanol (EH) manufactured from propene and carbon monoxide (CO), both produced from renewable feedstocks, such as biomass. For example, carbon monoxide may be obtained by gasification of biomass, for example bio-waste or “compost”. The propene may for example be obtained from bio-naphta which in turn may be obtained from spent cooking oil. Another suitable source of renewable propene could be biomethane which can in turn be obtained from biomass, for example from the gasses obtained from are crop residues, municipal solid waste, animal manure, wastewater treatment plants. Such ethyl hexanol that is 100% produced from renewable sources is defined herein as “renewable ethyl hexanol”.

[0155]

[0096] Hence, preferably the process according to the invention further comprises a step of preparing a hydroxy compound of formula (III), wherein such hydroxy compound of formula (III) comprises a mass balanced renewable ethyl hexanol, and more preferably a fully renewable ethyl hexanol. Such renewable ethyl hexanol is preferably obtained by reaction of a renewable propene and and renewable carbon monoxide to form butanal, which butanal is subsequently then dimerized and reduced to ethylhexanol. The dimerization and reduction can suitably be carried out in a manner as known by the person skilled in the art.

[0156]

[0097] In another preferred embodiment the hydroxy compound of formula (III) in the process according to the invention comprises or consists of a hydroxy compound of formula (III) that is partially or wholly microbially produced. A hydroxy compound of formula (III) which is partially or wholly microbially produced is herein also referred to as microbial produced hydroxy compound of formula (III). For example, a carbon containing substrate can be, partly or fully, converted to butanol and / or ethanol by fermentation with the help of a microbial cell. The butanol and / or ethanol may subsequently be converted in one or more steps to ethylhexanol, for example via a Guerbet reaction. Such a Guerbet reaction may comprise a sequence of dehydrogenation(s), aldol condensation(s), and hydrogenation steps.

[0157]

[0098] The microbial cell may or may not be a recombinant microbial cell. Preferably the microbial cell is a bacterium, a cyanobacterium, an archaeon, or a fungus. Preferably the carbon containing substrate is a biomass, more preferably a biomass comprising or consisting of one or more saccharides. Suitable examples of such saccharides include mono-saccharides, di-saccharides, oligo-saccharides and polysaccharides.

[0158]

[0099] Preferably the hydroxy compound of formula (III) in the processes of the invention is a ethylhexanol that is derived from a renewable resource, preferably a biomass.

[0159]

[0100] Hence, the invention also provides a process for the production of a Ce-is alkyl ester of 4-aminobenzoic acid of formula (I), wherein the process comprises:

[0160] a step of providing a partly or wholly renewable, or mass balanced renewable, or microbial produced 4-aminobenzoic acid of formula (II), for example as described herein above; and a step of providing a partly or wholly renewable, or mass balanced renewable, or microbial produced hydroxy compound of formula (III), for example as described herein above; and a step of reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a Ce-is alkyl ester of 4-aminobenzoic acid of formula (I)

[0161]

[0162] wherein Ris a Ce-is alkyl group,

[0163] and wherein the catalyst is preferably a catalyst as described herein.

[0164]

[0101] In addition the invention provides a process for the production of a UV filter, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein the process comprises the steps of:

[0165] providing a partly or wholly renewable, or mass balanced renewable, or microbial produced 4- aminobenzoic acid of formula (II), for example as described herein above; and

[0166] providing a partly or wholly renewable, or mass balanced renewable, or microbial produced hydroxy compound of formula (III), for example as described herein above; and

[0167] reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a mono Ce-is alkyl ester of 4-aminobenzoic acid of formula (I)

[0168]

[0169] wherein R is a Ce-is alkyl group; and wherein the catalyst is preferably a catalyst as described herein; and

[0170] converting the mono Ce-is alkyl ester of 4-aminobenzoic acid of formula (I) in one or more further reaction step to a UV filter, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT) or ethylhexyl dimethyl PABA (EHDP). Ce-is alkyl ester of 4-aminobenzoic acid

[0171]

[0102] The invention advantageously allows one to produce a more pure Cs-is alkyl ester of 4-aminobenzoic acid of formula (I).

[0172]

[0103] Hence, the invention therefore provides a composition comprising, consisting essentially of, or consisting of :

[0173] a Ce-is alkyl ester of 4-aminobenzoic acid of formula (I)

[0174]

[0175] and a secondary amine of formula (IV)

[0176]

[0177] wherein Ris a Ce-is alkyl group, and

[0178] wherein the molar ratio of Ce-is alkyl ester of 4-aminobenzoic acid of formula (I) to any secondary amines of formula (IV) is equal to or more than 25, more preferably equal to or more than 50, still more preferably equal to or more than 75, even more preferably equal to or more than 99, yet more preferably equal to or more than 500, yet still more preferably equal to or more than 800 and most preferably equal to or more than 900. There is no upper limit for the molar ratio but due to limitations of measurement equipment, the molar ratio may be equal to or less than 1000000, equal to or less than 100000 or suitably equal to or less than 10000.

[0179] Most preferably the secondary amine of formula (IV) is present in the composition at a concentration of equal to or less than 1000 parts per million (ppm), more preferably equal to or less than 500 ppm, still more preferably equal to or less than 100 ppm, yet more preferably equal to or less than 50 ppm and most preferably equal to or less than 10 ppm, based on the total weight of the composition. There is no bottom limit but due to limitations of measurement equipment, the secondary amine of formula (IV) may be present in the composition at a concentration equal to or more than 0.1 ppm, or suitably equal to or more than 1 ppm, based on the total weight of the composition.

[0104] The Ce-18 alkyl ester of 4-aminobenzoic acid of formula (I) is herein also referred to as the (primary) “aminobenzoic ester”, “alkyl 4-aminobenzoate” or the (primary) “product of formula (I)”. The secondary amine of formula (IV) is herein also referred to as the (secondary) “N-alkylated aminobenzoic ester”.

[0180]

[0105] Preferences for the R group are as described above. Preferably R is an octyl group, more preferably an ethylhexylgroup, most preferably an 2-ethylhexyl group. Preferably the Ce-is alkyl ester of 4-aminobenzoic acid of formula (I) is an ethylhexyl ester of 4-aminobenzoic acid, also referred to as ethylhexyl 4-aminobenzoate. Hence, suitably the secondary amine of formula (IV) is an N-alkylated aminobenzoic ester, more suitably ethylhexyl 4-((ethylhexyl)amino) benzoate, as illustrated in formula (VII) below:

[0181]

[0182]

[0106] Preferably the 4-aminobenzoic acid of formula (II) and / or the hydroxy compound of formula (III) are derived partly or wholly from a mass balanced renewable, renewable, microbial produced or otherwise sustainable and / or environmental friendly source. More preferably both the 4-aminobenzoic acid of formula (II) and the hydroxy compound of formula (III) are derived partly or wholly from a mass balanced renewable, a renewable, microbial produced or otherwise sustainable and / or environmental friendly source.

[0183]

[0107] In one preferred embodiment both the 4-aminobenzoic acid of formula (II) and the hydroxy compound of formula (III) comprise solely microbial produced carbon. Such advantageously allows the produced Ce-is alkyl ester of 4-aminobenzoic acid to be a compound that comprises a only microbial produced carbon.

[0184]

[0108] However, given the availability of resources, another preferred embodiment is wherein:

[0185] -the 4-aminobenzoic acid of formula (II) is partly or wholly derived from a microbial produced feedstock and / or comprises solely microbial produced carbon; and

[0186] - the hydroxy compound of formula (III) is partly or wholly derived from a mass balanced renewable feedstock or a partly or wholly renewable feedstock and / or comprises solely mass balanced produced carbon or (100%) renewable carbon.

[0187]

[0109] In an additional embodiment, the invention provides a Ce-is alkyl ester of 4-aminobenzoic acid which contains a mixture of:

[0188] - microbial produced carbon; and - renewable carbon or mass balanced renewable carbon, wherein such renewable carbon or mass balanced renewable carbon is not microbial produced carbon.

[0189] The invention may thus suitably also provide a Ce-is alkyl ester of 4-aminobenzoic acid which contains, based on the total weight of carbon within the molecule:

[0190] - in the range from 5 wt% to 95% of microbial produced carbon; and

[0191] - in the range from 5 wt% to 95% of mass-balanced renewable or renewable carbon, wherein such renewable carbon or mass balanced renewable carbon is not microbial produced carbon.

[0192] In this embodiment the renewable carbon is preferably understood to be carbon that fully originates from a 100% renewable feedstock.

[0193]

[0110] The invention may suitably also provides a composition comprising:

[0194] - a Ce-18 alkyl ester of 4-aminobenzoic acid which contains equal to or more than 45 wt.%, even more preferably equal to or more than 60 wt%, more preferably 100 wt% of mass balanced renewable carbon, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid; and / or

[0195] - a Ce-18 alkyl ester of 4-aminobenzoic acid which contains equal to or more than 45 wt.%, even more preferably equal to or more than 60 wt%, more preferably 100 wt% of renewable carbon, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid; and / or

[0196] - a Ce-18 alkyl ester of 4-aminobenzoic acid which contains equal to or more than 45 wt.%, even more preferably equal to or more than 60 wt%, more preferably 100 wt% of microbial produced carbon, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid.

[0197]

[0111] Preferably the Ce-is alkyl ester of 4-aminobenzoic acid contains in the range from equal to or more than 1 wt% to equal to or less than 100 wt%, of mass balanced renewable carbon, more preferably of renewable carbon, most preferably of microbial produced carbon, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid. More preferably the Ce-is alkyl ester of 4-aminobenzoic acid compound comprises or consists of a Ce-is alkyl ester of 4-aminobenzoic acid which comprises in the range from equal to or more than 20 wt%, more preferably from equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, to equal to or less than 100 wt% of renewable carbon, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid. A Ce-is alkyl ester of 4-aminobenzoic acid which contains 100 wt% of renewable carbon is herein also referred to as a 100% renewable Ce-is alkyl ester of 4-aminobenzoic acid.

[0198]

[0112] The invention thus advantageously provides a Ce-is alkyl ester of 4-aminobenzoic acid that has a total content of mass balanced renewable carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid. More preferably the Ce-is alkyl ester of 4-aminobenzoic acid has a total content of renewable carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid. Most preferably the Ce-is alkyl ester of 4-aminobenzoic acid has a total content of microbial produced carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid. A Ce-is alkyl ester of 4-aminobenzoic acid which contains 100 wt% of microbial produced carbon is herein also referred to as a 100% microbial produced Cs-is alkyl ester of 4-aminobenzoic acid.

[0199]

[0113] Preferably the Ce-is alkyl ester of 4-aminobenzoic acid is ethylhexyl p-aminobenzoate. Hence preferably the invention provides a ethylhexyl p-aminobenzoate that has a total content of mass balanced renewable carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such ethylhexyl p-aminobenzoate. More preferably the ethylhexyl p-aminobenzoate has a total content of renewable carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such ethylhexyl p-aminobenzoate. Most preferably the ethylhexyl p-aminobenzoate has a total content of microbial produced carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such ethylhexyl p-aminobenzoate. A ethylhexyl p-aminobenzoate which contains 100 wt% of microbial produced carbon is herein also referred to as a 100% microbial ethylhexyl p-aminobenzoate.

[0200]

[0114] The invention therefore preferably provides a composition comprising:

[0201] a Cs-is alkyl ester of 4-aminobenzoic acid of formula (I)

[0202]

[0203] and a secondary amine of formula (IV)

[0204]

[0205] wherein Ris a ethylhexyl group, and

[0206] wherein the molar ratio of Ce-is alkyl ester of 4-aminobenzoic acid of formula (I) to any secondary amines of formula (IV) is equal to or more than 25, more preferably equal to or more than 50, still more preferably equal to or more than 75, even more preferably equal to or more than 99, yet more preferably equal to or more than 500 and most preferably equal to or more than 999.

[0207]

[0115] That is, preferably the invention also provides a composition comprising ethylhexyl 4-aminobenzoate and ethylhexyl 4-((ethylhexyl)amino) benzoate, wherein the molar ratio of ethylhexyl 4-aminobenzoate to ethylhexyl 4-((ethylhexyl)amino) benzoate is equal to or more than 25, more preferably equal to or more than 50, still more preferably equal to or more than 75, even more preferably equal to or more than 99, yet more preferably equal to or more than 500 and most preferably equal to or more than 999.

[0208] Most preferably the ethylhexyl 4-((ethylhexyl)amino) benzoate is present in such composition at a concentration of equal to or less than 1000 parts per million (ppm), more preferably equal to or less than 500 ppm, still more preferably equal to or less than 100 ppm, yet more preferably equal to or less than 50 ppm and most preferably equal to or less than 10 ppm, based on the total weight of the composition.

[0209] Preferably such composition comprises a partly or fully mass balanced renewable ethylhexyl ester of 4-aminobenzoic acid (also referred to as ethylhexyl 4-aminobenzoate) as described above. More preferably such composition comprises a partly or fully renewable ethylhexyl 4-aminobenzoate as described above. Most preferably such composition comprises a partly or fully microbial produced ethylhexyl 4-aminobenzoate as described above. Further preferences are as described above.

[0210] UV Filters

[0211]

[0116] The Ce-18 alkyl ester of 4-aminobenzoic acid as described herein can advantageously be used to produce a more pure UV filter and / or a UV filter with an increased percentage of mass balanced renewable carbon, an increased percentage of renewable carbon, or an increased percentage of microbial produced carbon, which in turn can be advantageously used to prepare a more sustainable suncare product.

[0117] Most preferably the Ce- alkyl ester of 4-a mi no benzoic acid is a renewable ethylhexyl ester of 4-aminobenzoic acid.

[0212]

[0118] Accordingly, the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three elements derived from a Ce-is alkyl ester of 4-aminobenzoicacid, wherein each such element has a total content of mass balanced renewable carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such element. Most preferably the Ce-is alkyl ester of 4-aminobenzoic acid is an ethylhexyl ester of 4-aminobenzoic acid.

[0213]

[0119] Preferably, the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three substituents derived from a Ce-is alkyl ester of 4-aminobenzoic acid, wherein each such substituent has a total content of mass balanced renewable carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such substituent. Most preferably the Ce-is alkyl ester of 4-aminobenzoic acid is an ethylhexyl ester of 4-aminobenzoic acid.

[0214]

[0120] More preferably, the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three elements derived from a Ce-is alkyl ester of 4-aminobenzoic acid, wherein each such element has a total content of renewable carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such element. Most preferably the Ce-is alkyl ester of 4-aminobenzoic acid is an ethylhexyl ester of 4-aminobenzoic acid.

[0215]

[0121] More preferably, the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three substituents derived from a Ce-is alkyl ester of 4-aminobenzoic acid, wherein each such substituent has a total content of renewable carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such substituent. Most preferably the Ce-is alkyl ester of 4-aminobenzoic acid is an ethylhexyl ester of 4-aminobenzoic acid.

[0122] More preferably, the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three elements derived from a Ce-is alkyl ester of 4-aminobenzoic acid, wherein each such element has a total content of microbial produced carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such element. Most preferably the Ce-is alkyl ester of 4-aminobenzoic acid is an ethylhexyl ester of 4-aminobenzoic acid.

[0216]

[0123] More preferably, the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three substituents derived from a Ce-is alkyl ester of 4-aminobenzoic acid, wherein each such substituent has a total content of microbial produced carbon of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such substituent. Most preferably the Ce-is alkyl ester of 4-aminobenzoic acid is an ethylhexyl ester of 4-aminobenzoic acid.

[0217]

[0124] In an especially preferred embodiment a UV filter compound is provided, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT) or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three substituents derived from a Ce-18 alkyl ester of 4-aminobenzoic acid, wherein 100% of the carbon present in the substituent is mass balanced renewable carbon, more preferably renewable carbon, most preferably microbial produced carbon.

[0218]

[0125] In an especially preferred embodiment the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT) or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three elements derived from a Ce-18 alkyl ester of 4-aminobenzoic acid, wherein 100% of the carbon present in the element is microbial produced carbon. In a further especially preferred embodiment the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT) or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three substituents derived from a Cs-is alkyl ester of 4-aminobenzoic acid, wherein 100% of the carbon present in the substituent is microbial produced carbon. Most preferably the Ce-is alkyl ester of 4-aminobenzoic acid is an ethylhexyl ester of 4-aminobenzoic acid.

[0219]

[0126] The mass balanced renewable carbon percentage, respectively renewable carbon percentage, respectively microbial produced carbon percentage, mentioned herein can suitably be calculated on the basis of the total weight of carbon present in the element, respectively substituent.

[0127] Even more preferably, the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three elements derived from a Ce-18 alkyl ester of 4-aminobenzoic acid, wherein each such element has a total biobased carbon content, preferably as determined according to ASTM test D6866, of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such element. Most preferably the Ce-is alkyl ester of 4-aminobenzoic acid is an ethylhexyl ester of 4-aminobenzoic acid.

[0220]

[0128] Also preferably, the invention provides a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three substituents derived from a Ce-is alkyl ester of 4-aminobenzoic acid, wherein each such substituent has a total biobased carbon content, preferably as determined according to ASTM test D6866, of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such substituent. Most preferably the Ce-is alkyl ester of 4-aminobenzoic acid is an ethylhexyl ester of 4-aminobenzoic acid.

[0221]

[0129] In a very preferred embodiment, the invention provides a UV filter compound, wherein this UV filter compound comprises one, two or three [4-(2-ethylhexyloxycarbonyl)anilino]-moieties, wherein each such [4-(2-ethylhexyloxycarbonyl)anilino]-moiety has a total biobased carbon content, preferably as determined according to ASTM test D6866, of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such [4-(2-ethylhexyloxycarbonyl)anilino]-moiety. More preferably such UV filter compound is a ethylhexyltriazone compound (EHT) or a diethylhexyl butamido triazone compound (iscotrizinol, DBT).

[0222]

[0130] Still more preferably, the invention provides a UV filter compound, wherein this UV filter compound comprises one, two or three [4-(2-ethylhexyloxycarbonyl)anilino]-moieties bound to a triazine moiety, wherein each such [4-(2-ethylhexyloxycarbonyl)anilino]-moiety has a total biobased carbon content, preferably as determined according to ASTM test D6866, of equal to or more than 30 wt%, more preferably equal to or more than 45 wt%, even more preferably equal to or more than 60 wt%, and most preferably 100 wt%, based on the total weight of carbon present in such [4-(2-ethylhexyloxycarbonyl)anilino]-moiety. More preferably such UV filter compound is a ethylhexyltriazone compound (EHT) or a diethylhexyl butamido triazone compound (iscotrizinol, DBT).

[0223]

[0131] For convenience, the [4-(2-ethylhexyloxycarbonyl)anilino]-moiety may also be referred to herein as a [4-[(2-ethylhexyloxycarbonyl)phenyl]amino]-moiety.

[0132] Preferably the element, respectively substituent, respectively moiety, is an ethylhexyl 4-aminobenzoate group. Such ethylhexyl 4-aminobenzoate group can become incorporated as an element or substituent or moiety in a UV filter as described herein above for the production of a UV filter.

[0224]

[0133] Given the availability of resources, another preferred embodiment is wherein a UV filter compound is provided, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT) or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises: - microbial produced carbon; and

[0225] - renewable carbon or mass balanced renewable carbon, wherein such renewable carbon or mass balanced renewable carbon is not microbial produced carbon.

[0226] The invention may thus suitably also provide a UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT) or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises, based on the total weight of carbon within the molecule:

[0227] - in the range from 5 wt% to 95% of microbial produced carbon; and / or

[0228] - in the range from 5 wt% to 95% of mass-balanced renewable or renewable carbon, wherein such renewable carbon or mass balanced renewable carbon is not microbial produced carbon.

[0229] In this embodiment the renewable carbon is preferably understood to be carbon that fully originates from a 100% renewable feedstock.

[0230] Such a UV filter compound has the advantage that it may allow for an an optimum use of available sustainable resources during its production, as explained in the sections above.

[0231] Fully biobased 2-Ethylhexyl 4-(dimethylamino)benzoate

[0232]

[0134] The invention advantageously also provides a process to prepare fully biobased 2-Ethylhexyl 4-(dimethylamino)benzoate. Such 2-Ethylhexyl 4-(dimethylamino)benzoate is herein also referred to as ethylhexyl dimethyl PABA (EHDP).

[0233]

[0135] As mentioned above, 2-Ethylhexyl 4-(dimethylamino)benzoate can be obtained from the 2-ethylhexyl ester of para-aminobenzoic acid (also referred to as 2-ethylhexyl-4-aminobenzoate) via methylation of the amino group of the 2-ethylhexyl-4-aminobenzoate. In one preferred embodiment such methylation is carried out with the help of formaldehyde and / or formic acid obtained from a biobased source. Such biobased formaldehyde and / or formic acid preferably comprises equal to or more than 30 wt%, more preferablyequal to or more than 45 wt%, most preferably 100 wt% of biobased carbon, preferably as determined according to ASTM test D6866, based on the total weight of carbon present in such formaldehyde and / or formic acid.

[0234]

[0136] Such biobased formaldehyde and / or formic acid can conveniently be obtained by the production of formic acid or formaldehyde from carbon dioxide, such as for example described in US20240228419A1 and WO2022223746, incorporated herein by reference. Alternatively such biobased formaldehyde and / or formic acid can conveniently be obtained by a method as described by Park et al. in their article titled “Biomass-formic acid-hydrogen conversion process: sustainable production of formic acid from biomass using greenhouse gas”, published in Green Chem., 2025, vol.

[0235] 27, pages 4750-4765.

[0236]

[0137] The invention therefore also provides a 2-Ethylhexyl 4-(dimethylamino)benzoate comprising in the range from equal to or more than 1 wt % to 100 wt%, more preferably in the range from equal to or more than 20 wt % to 100 wt%, even more preferably in the range from equal to or more than 50 wt % to 100 wt%, and most preferably 100 wt% biobased carbon, preferably as determined according to ASTM test D6866, based on the total weight of carbon present in such 2-Ethylhexyl 4-(dimethylamino)benzoate.

[0237]

[0138] In addition, the invention provides a volume comprising or consisting of 2-Ethylhexyl 4-(dimethylamino)benzoate molecules:

[0238] - wherein the total volume of 2-Ethylhexyl 4-(dimethylamino)benzoate molecules comprises equal to or more than 1 wt%, more preferably equal to or more than 2 wt%, still more preferably equal to or more than 5 wt%, even more preferably equal to or more than 10 wt%, yet more preferably equal to or more than 30 wt%, even still more preferably equal to or more than 50 wt%, and preferably equal to or less than 100 wt%, of renewable carbon, more preferably biobased carbon, preferably as determined according to ASTM test D6866, based on the total weight of carbon present in the total volume of 2-Ethylhexyl 4-(dimethylamino)benzoate molecules; and / or

[0239] - wherein each individual 2-Ethylhexyl 4-(dimethylamino)benzoate molecule comprises equal to or more than 1 wt%, more preferably equal to or more than 2 wt%, still more preferably equal to or more than 5 wt%, even more preferably equal to or more than 10 wt%, yet more preferably equal to or more than 30 wt%, even still more preferably equal to or more than 50 wt%, and preferably equal to or less than 100 wt%, of renewable carbon atoms, more preferably biobased carbon atoms, preferably as determined according to ASTM test D6866, based on the total weight of carbon atoms present in the individual 2-Ethylhexyl 4-(dimethylamino)benzoate molecule.

[0240]

[0139] In an especially preferred embodiment the invention provides a volume comprising or consisting of 2-Ethylhexyl 4-(dimethylamino)benzoate molecules:

[0241] - wherein the total volume of 2-Ethylhexyl 4-(dimethylamino)benzoate molecules comprises 100 wt%, of renewable carbon, more preferably biobased carbon, preferably as determined according to ASTM test D6866, based on the total weight of carbon present in the total volume of 2-Ethylhexyl 4-(dimethylamino)benzoate molecules; and / or

[0242] - wherein each individual 2-Ethylhexyl 4-(dimethylamino)benzoate molecule comprises 100 wt%, of renewable carbon atoms, more preferably biobased carbon atoms, preferably as determined according to ASTM test D6866, based on the total weight of carbon atoms present in the individual 2-Ethylhexyl 4-(dimethylamino)benzoate molecule.

[0243] Cosmetic composition

[0244]

[0140] The invention further provides a cosmetic composition comprising a UV filter compound as described herein. In addition, the invention provides the use of such a UV filter to protect skin against UV radiation and / or to prevent solar damage and skin diseases. Such cosmetic composition is preferably a skincare or suncare composition, most preferably a sunscreen composition.

[0245]

[0141] The invention also provides for the use of a composition comprising a Ce-is hydrocarbyl ester of 4-aminobenzoic acid as described herein or a UV filter compound as described herein for the preparation of such a cosmetic composition.

[0246]

[0142] In all embodiments of this invention, such cosmetic compositions, preferably skincare or sunscreen compositions, are intended for topical applications. That is, the cosmetic composition is preferably a topical composition.

[0247]

[0143] Preferably the cosmetic compositions of the invention comprise a physiologically acceptable medium, i.e., a medium compatible with keratinous substances, such as the skin, mucous membranes, and keratinous fibres. More preferably, the physiologically acceptable medium is a cosmetically acceptable carrier. That is, preferably the cosmetic composition comprises at least a UV filter as described herein and a cosmetically acceptable carrier.

[0248]

[0144] The exact amount of carrier will depend upon the actual level of the UV filters and any other optional ingredients, for example other active ingredients.

[0249]

[0145] In an embodiment, the cosmetic compositions according to the present invention can comprise from 50 to 99%, preferably from 60 to 98%, more preferably from 70 to 98%, such as in particular from 80 to 95% of a carrier, based on the total weight of the cosmetic composition.

[0250]

[0146] In an advantageous embodiment, the carrier consists furthermore of at least 30 wt.%, more preferably of at least 40 wt.%, most preferably of at least 45 wt.% of water, such as in particular of 50 to 90 wt.% of water.

[0251]

[0147] Preferably the cosmetic composition is a non-therapeutic composition.

[0252]

[0148] Examples of cosmpetic compositions include light protective preparations, anti-ageing preparations, preparations for the treatment of photo-ageing, body oils, body lotions, body gels, treatment creams, skin protection ointments, skin powders, moisturizing gels, moisturizing sprays, face and / or body moisturizers, skin-tanning preparations (i.e., compositions for the artificial / sunless tanning and / or browning of human skin), for example self-tanning creams as well as skin lightening preparations.

[0149] Preferably, the cosmetic composition is a sunscreen composition, more preferably a light-protective preparation (sun care products, sunscreens), such as a sun protection milk, skin protection lotion, sun protection cream, sun protection oil, sun block or tropical’s or day care creams with a SPF (sun protection factor). Of particular interest are sun protection creams, sun protection lotions and sun protection milks.

[0253]

[0150] The cosmetic compositions of the invention (including the carrier) may further comprise conventional adjuvants and additives, such as preservatives / antioxidants, fatty substances / oils, organic solvents, silicones, thickeners, softeners, emulsifiers, antifoaming agents, aesthetic components such as fragrances, surfactants, fillers, anionic, cationic, nonionic or amphoteric polymers or mixtures thereof, propellants, acidifying or basifying agents, dyes, colorings / colorants, abrasives, absorbents, chelating agents and / or sequestering agents, essential oils, skin sensates, astringents, pigments or any other ingredients usually formulated into such compositions.

[0254]

[0151] In accordance with the present invention, the cosmetic compositions according to the invention may also comprise further ingredients such as ingredients for skin lightening, tanning prevention, treatment of hyperpigmentation, preventing or reducing acne, wrinkles, lines, atrophy and / or inflammation, chelators and / or sequestrants, anti-cellulites and slimming (e.g., phytanic acid), firming, moisturizing and energizing, self-tanning, soothing agents, as well as agents to improve elasticity and skin barrier and carriers and / or excipients or diluents conventionally used in sunscreen compositions.

[0255]

[0152] If nothing else is stated, the excipients, additives, diluents, etc., mentioned in the following are suitable for cosmetic compositions, preferably sunscreen compositions, according to the present invention.

[0256]

[0153] The additional ingredients can either be added to the oily phase, the aqueous phase or separately as deemed appropriate. The mode of addition can easily be adapted by a person skilled in the art.

[0257]

[0154] Examples of cosmetic excipients, diluents, adjuvants, additives as well as active ingredients commonly used in the skin care industry which are suitable for use in the cosmetic compositions of the present invention are for example described in the International Cosmetic Ingredient Dictionary & Handbook by Personal Care Product Council 5 (http : / / www.personalcarecouncil.org / ), accessible by the online INFO BASE (http : / / online. personalcarecouncil.org / jsp / Home.jsp), without being limited thereto.

[0258]

[0155] The cosmetically active ingredients useful herein can in some instances provide more than one benefit or operate via more than one mode of action. Of course, one skilled in this art will take care to select the above mentioned optional additional ingredients, adjuvants, diluents and additives and / or their amounts such that the advantageous properties intrinsically associated with the combination in accordance with the invention are not, or not substantially, detrimentally affected by the envisaged addition or additions.

[0259]

[0156] Preferred cosmetic compositions in all embodiments of the present invention are emulsions containing an oily phase and an aqueous phase such as in particular an O / W, W / O, Si / W, W / Si, O / W / O, W / O / W multiple or a pickering emulsions. The amount of the oily phase (i.e. the phase containing all oils and fats) present in such emulsions is preferably at least 10 wt.-%, such as in the range from 10 to 60 wt.-%, preferably in the range from 15 to 50 wt.-%, most preferably in the range from 15 to 40 wt.-%, based on the total weight of the composition.

[0260]

[0157] According to one even more preferred embodiment, the cosmetic compositions according to the present invention as outlined herein are O / W emulsions comprising an oily phase dispersed in an aqueous phase in the presence of an O / W emulsifier.

[0261]

[0158] Hereinbelow the invention is illustrated by non-limiting examples. Examples

[0262] Instruments and Materials

[0263]

[0159] Analytical U-HPLC chromatograms were measured on a Waters Acquity Ultra Performance Liquid Chromatography (UPLC), equipped with an Acquity HSST3100 A 1.8pm 2.1 x50 mm2 analytical column and a PDA detector operating in the 200-400 nm wavelength range. H2O + 0.02 % TFA (A phase) and MeCN + 0.02 % TFA (B phase) were used as eluents, with a flow of 0.5 mL / min.

[0264]

[0160] Nuclear magnetic resonance spectra were recorded on a AVNeo400NB spectrometer equipped with 5 mm BBO BB-1 H probe head operating at 400 MHz for1H and 100 MHz for13C. Spectra were recorded in in DMSO-d6 and referenced to the residual solvent signal (1H: 2.50 ppm).

[0265] Examples 1 to 9

[0266]

[0161] Examples 1 to 9 were carried out in accordance with the following procedure unless mentioned otherwise in Table 2.

[0267]

[0162] To 73 millimol (mmol) 4-aminobenzoic acid and 321 mmol ethylhexanol (4.4 equiv.) was added 1.46 mmol (0.02 equivalent) titanium tetraethylhexyloxide (Ti(OEH)4), respectively titanium tetrabutyloxide ((Ti(OBu)4), The mixture was warmed to 152-156 °C (internal temperature) and was stirred at that temperature for 5.5 hours while reaction water was constantly removed with a stream of nitrogen. The reaction was subsequently cooled to 70 °C and the reaction mixture was filtered. The filter cake was rinsed with 5 milliliters (mL) toluene. Ethylhexanol and toluene were removed by distillation under reduced pressure, providing the compound of formula I as an orange oil. The HPLC purity was determined at 290 nm and was indicated in Table 3.

[0268]

[0163] According to the results in Table 3, Footnote b, as well as those in Tables 4-7, the HPLC area percentages at 290 nm can be used as a good approximation for the molar or weight percent ratios of the two compounds in the case of the compounds of formulas (I) and (IV). Based on this, it was considered that a determination of <0.1 %a corresponds to <0.1% wt and <0.1% mol. Abbreviations used in the examples

[0269] Abbreviations used in the examples are listed below in Table 1

[0270] Table 1: Abbreviations

[0271]

[0272] Table 2: Reaction conditions of examples 1 to 10

[0273]

[0274] amolar equivalents with respect to starting compound p-aminobenzoic acid (PABA);bqNMR yield after distillation 95%; qNMR assay after distillation 97%w (corrected for residual ethylhexanol);

[0275] cqNMR yield after distillation 96%; qNMR assay after distillation 98%w (corrected for residual ethylhexanol);

[0276] dSublimation of PABA. Table 3: Results of examples 1 to 10

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[0288]

[0289] bqNMR yield after distillation 95%; qNMR assay after distillation 97%w (corrected for residual ethylhexanol); as indicated above, the HPLC area percentages at 290 nm can be used as a good approximation for the molar or weight percent ratios of the two compounds in the case of the compounds of formulas (I) and (IV).

[0290] cqNMR yield after distillation 96%; qNMR assay after distillation 98%w (corrected for residual ethylhexanol);

[0291] dSublimation of PABA.

[0292] ebased on %area determined by HPLC at 290 nm, wherein

[0293] Conversion=%a product I (%a product + %aaminobenzoic acid);

[0294] fHPLC percentage primary product of formula (I), here ethylhexyl 4-aminobenzoate, based on %area at 290 nm, wherein percentage = %aPrimary product / sum of %a off all peaks at 290 nm;

[0295] 9HPLC percentage secondary amine of formula (IV), here ethylhexyl 4-((ethylhexyl)amino) benzoate, based on %area at 290 nm, wherein percentage = asecondary amine I sum of %a off all peaks at 290 nm;

[0296]

[0165] As explained above the ratio by % area as measured by HPLC corresponds to the ratio by % mol as determined by qNMR. It can thus be derived from the HPLC results in % area that the process of the invention allows for a composition to be produced wherein the molar ratio of Ce- alkyl ester of 4-aminobenzoic acid of formula (I) to secondary amine of formula (IV) was equal to or more than 870 and in some examples even equal to or more than 980.

[0297] Comparative example A - according to the article of Liu et al.

[0298]

[0166] In this experiment the process for preparation of n-octyl ester of p-aminobenzoic acid according to the process of Liu et al, Journal of Henan Normal University (Natural Science), 2008, vol. 36(5) pages 174-175 was mimicked.

[0299]

[0167] An n-octyl ester of p-aminobenzoic acid was prepared in line with the process of the examples of the article titled “Direct synthesis of long-chain alcohol esters of p-aminobenzoic acid”, published in the Journal of Henan Normal University (Natural Science), 2008 (vol. 36), pages 174-175 by Liu et al.. For these examples reaction time was 7 hours (h) and as temperature for the reaction reflux temperature was applied and the reaction was run at ambient pressure (about 1 bar).

[0300]

[0168] Hence, 2.5 g (18 mmol) 4-aminobenzoic acid were suspended in 28 g (220 mmol, about 12 equivents) n-octanol. 1.9 g H2SO4 95% (18 mmol) were added. The mixture was warmed to 150 °C external temperature and was stirred for 7 hours at ambient pressure. The reaction was monitored by U-HPLC chromatography at 290 nm and by quantitative NMR. The results are listed in Table 4 and Table 5 below. The NMR yield was moderate, and the process as described by Liu et al resulted also in the presence of significant amounts of a secondary amine of formula (IV), in this case an N-alkylated aminobenzoic ester of the n-octanol : n-octyl 4-(n-octyl)amino) benzoate of formula (VIII):

[0301]

[0302] Table 4: Results of comparative example A in % area as determined by HPLC at 290 nm

[0303]

[0304]

[0169] Based on the HPLC % area, the ratio between the octyl-4-aminobenzoate (primary product of formula (I)) and the N-alkylated aminobenzoic ester, i.e. octyl 4-(octyl) amino) benzoate (secondary amine of formula (IV)) after 7 hours was about 5.2.

[0305] Table 5: Results of comparative example A, in mol % derived from qNMR, based on moles of starting compound aminobenzoic acid

[0306]

[0307]

[0170] Based on the qNMR results, the molar ratio between the octyl-4-aminobenzoate (primary product of formula (I)) and the N-alkylated aminobenzoic ester, i.e. octyl 4-( octyl) amino) benzoate (secondary amine of formula (IV)) after 7 hours was about 6.

[0308] Comparative example B

[0309]

[0171] In a second comparative experiment, 2-ethylhexyl ester of p-aminobenzoic acid (ethylhexyl 4-amino benzoate) was prepared with a process similar to the process of Liu et al, as described in the article titled “Direct synthesis of long-chain alcohol esters of p-aminobenzoic acid”, published in the Journal of Henan Normal University (Natural Science), 2008 (vol. 36), pages 174-175. For these examples reaction time was 7 hours (h) and as temperature for the reaction reflux temperature was applied and the reaction was run at ambient pressure (about 1 bar, corresponding to about 0.1 MegaPascal).

[0310]

[0172] 2.5 g (18 mmol) 4-aminobenzoic acid were suspended in 28 g (220 mmol, about 12 equivents) 2-ethylhexanol. 1.9 g H2SO495% (18 mmol) were added. The mixture was warmed to 150 °C external temperature and was stirred for 7 hours. The reaction was monitored by U-HPLC chromatography at 290 nm. The results are listed in Table 6 below. Although high yields were obtained as desired, unfortunately also in this process significant amounts of an N-alkylated aminobenzoic ester, that is, a secondary amine of formula (IV) were formed. The N-alkylated aminobenzoic ester in this case was 2-ethylhexyl 4-(2-ethylhexyl)amino) benzoate as illustrated in formula (VI I) below.

[0311]

[0312] Table 6: Results of comparative example B in % area as determined by HPLC at 290 nm

[0313]

[0314]

[0173] Based on the HPLC % area, the ratio between the ethylhexyl-4-aminobenzoate (primary product of formula (I)) and the N-alkylated aminobenzoic ester, i.e. ethylhexyl 4-( ethylhexyl) amino) benzoate (secondary amine of formula (IV)) after 7 hours was about 17.

[0315] Table 7: Results of comparative example B, in mol % derived from gNMR, based on moles of starting compound aminobenzoic acid

[0316]

[0317]

[0174] Based on the qNMR results, the molar ratio between the octyl-4-aminobenzoate (primary product of formula (I)) and the N-alkylated aminobenzoic ester, i.e. octyl 4-( octyl) amino) benzoate (secondary amine of formula (IV)) after 7 hours was about 18.

[0318]

[0175] The results of comparative example A and comparative example B show that the percentage area as determined by HPLC at 290 nm serve as a good indication of percentage mol.

[0319]

[0176] According to the article of Liu et al., the highest yield occurs when the molar ratio of concentrated sulfuric acid to p-aminobenzoic acid (PABA) is about 1 :1. Further, according to Liu et al. the experimental results allegedly show that the reaction yield is the highest when the molar ratio of alcohol to PABA (alcohol:PABA) is 12. However, as illustrated by comparative example A and comparative example B above, NMR yields obtained are mere moderate (octanol) to moderately high (ethylhexanol). In addition, as illustrated above unfortunately the process as described by Liu et al resulted in significant amounts of secondary amines of formula (IV). Such aromatic secondary amines are associated with a risk of genotoxicity and hence are undesired in any cosmetic product.

[0320]

[0177] As illustrated by examples 1 to 9 above, advantageously the process according to the invention allows one to reach significantly higher yields. In addition a significantly higher purity was obtained via the process according to the invention and the presence of secondary amines of formula (IV) was minimized.

[0321] Comparative example C - Experiment without water removal

[0322]

[0178] This example was carried out without water removal. To 10 g (73 mmol) 4-aminobenzoic acid and 42 g ethylhexanol (320 mmol, 4.4 equivalents) was added 496 mg (1.458 mmol, 0.02 eq.) titanium tetrabutoxide. The mixture was warmed to 150-160 °. Conversion (%area at 290 nm) was ca. 19% after 1 h, 62% after 6 h and 65% after 8h.

[0323] This result illustrates the preference for the removal of the reaction water to allow sufficient conversion and high yields.

[0324] Comparative example D - Experiment using zinc chloride as catalyst

[0325]

[0179] In this example zinc chloride was applied as an alternative catalyst. To 5 g (37 mmol) 4-aminobenzoic acid and 21.4 g ethylhexanol (164 mmol, 4.5 equiv.) was added 248 mg (1.82 mmol, 0.05 eq.) zinc chloride. The mixture was warmed to 150 °. Conversion was <1% after 1 hour according to HPLC.

[0326] Comparative example E - Experiment using aluminium isopropoxide as catalyst

[0327]

[0180] In this example aluminium isopropoxide was applied as an alternative catalyst. To 10 g (73 mmol) 4-aminobenzoic acid and 42.0 g ethylhexanol (320 mmol, 4.5 equiv.) was added 298 mg (1.46 mmol, 0.02 eq.) aluminium isopropoxide. The mixture was warmed to 150-170 °. Conversion was 38% after 17 hours according to HPLC.

[0328] Comparative example F - Experiment using zinc oxide as catalyst

[0329]

[0181] In this example zinc oxide was applied as an alternative catalyst. To 10 g (73 mmol) 4-aminobenzoic acid and 42.0 g ethylhexanol (320 mmol, 4.5 equiv.) was added 119 mg (1.46 mmol, 0.02 eq.) zinc oxide. The mixture was warmed to 150-170 °. Conversion was 24% after 5 hours according to HPLC.

[0330] Comparative example G - Experiment using zinc acetate as catalyst

[0331]

[0182] In this example zinc acetate was applied as an alternative catalyst. To 10 g (73 mmol) 4-aminobenzoic acid and 42.0 g ethylhexanol (320 mmol, 4.5 equiv.) was added 320 mg (1.46 mmol, 0.02 eq.) zinc acetate. The mixture was warmed to 150-170 °. Conversion was 25% after 5 hours according to HPLC.

Claims

Claims1. A process for the production of a Ce-is alkyl ester of 4-aminobenzoic acid of formula (I), wherein the process comprises a step of reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a Ce-is alkyl ester of 4-aminobenzoic acid of formula (I)wherein Ris a Ce-is alkyl group,and wherein the catalyst is a titanium catalyst, preferably a titanium alkoxide catalyst.

2. A process for the production of a UV filter, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT), or ethylhexyl dimethyl PABA (EHDP), wherein the process comprises the steps of:a) reacting the 4-aminobenzoic acid of formula (II) with an hydroxy compound of formula (III) in the presence of a catalyst to generate a mono Ce-is alkyl ester of 4- aminobenzoic acid of formula (I)wherein Ris a Ce-is alkyl group; andwherein the catalyst is a titanium catalyst, preferably a titanium alkoxide catalyst; andb) converting the mono Ce-is alkyl ester of 4-aminobenzoic acid of formula (I) in one or more further reaction step to a UV filter, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT) or ethylhexyl dimethyl PABA (EHDP).

3. A process according to claim 1 or 2, wherein the 4-aminobenzoic acid comprises or consists of 4-aminobenzoic acid that comprises equal to or more than 45 wt% renewable carbon, more preferably 100 wt% renewable carbon, based on the total weight of carbon present in such 4-aminobenzoic acid.

4. A process according to any one of claims 1 to 3, which process further comprises a microbial production of 4-aminobenzoic acid, wherein a fermentable carbon substrate is, partly or fully, converted to p-aminobenzoic acid by fermentation with the help of a microbial cell.

5. A process according to any one of claim 1 or 4, wherein the hydroxy compound of formula (III) comprises or consists of a hydroxy compound of formula (III) that comprises equal to or more than 45 wt% renewable carbon, more preferably 100 wt% renewable carbon, based on the total weight of carbon present in such hydroxy compound of formula (III).

6. A process according to any one of claims 1 to 5, wherein R is a Cs-Cie alkyl group, more preferably an octyl group and most preferably an ethylhexyl group.

7. A process according to any one of claims 1 to 6, wherein the molar ratio of the hydroxy compound of formula (III) to the 4-aminobenzoic acid of formula (II) lies in the range from equal to or more than 1:1 to equal to or less than 10:1.

8. A process according to any one of claims 1 to 7, wherein the 4-aminobenzoic acid of formula (II) and the hydroxy compound of formula (III) are reacted at a temperature in the range from equal to or more than 140°C to equal to or less than 160°C.

9. A composition comprising:a Ce-18 alkyl ester of 4-aminobenzoic acid of formula (I)wherein Ris a Ce-is alkyl group, andwherein the molar ratio of Ce-is alkyl ester of 4-aminobenzoic acid of formula (I) to any secondary amines of formula (IV) is equal to or more than 25, more preferably equal to or more than 50, still more preferably equal to or more than 75 and most preferably equal to or more than 99; andwherein preferably the Ce-is alkyl ester of 4-aminobenzoic acid contains in the range from equal to or more than 1 wt%, more preferable from equal to or more than 45 wt%, to equal to or less than 100 wt% of renewable carbon, more preferably microbial produced carbon, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid.

10. A composition according to claim 9, wherein R is a Cs-C alkyl group, more preferably an octyl group and most preferably an ethylhexyl group11. A Cs-18 alkyl ester of 4-aminobenzoic acid, preferably ethylhexyl 4-aminobenzoate, which contains in the range from equal to or more than 1 wt%, more preferable from equal to or more than 45 wt%, to equal to or less than 100 wt% of renewable carbon, more preferably biobased carbon, preferably as determined according to ASTM test D6866, based on the total weight of carbon present in such Ce-is alkyl ester of 4- aminobenzoic acid.

12. A composition according to claim 9 or claim 10 or an Cs-is alkyl ester of 4- aminobenzoic acid according to claim 11, wherein the Cs-is alkyl ester of 4- aminobenzoic acid contains 100 wt% of renewable carbon, more preferably 100 wt% biobased carbon, preferably as determined according to ASTM test D6866, based on the total weight of carbon present in such Ce-is alkyl ester of 4-aminobenzoic acid,13. A UV filter compound, preferably ethylhexyltriazone (EHT), diethylhexyl butamido triazone (iscotrizinol, DBT) or ethylhexyl dimethyl PABA (EHDP), wherein this UV filter compound comprises one, two or three substituents derived from a Ce-is alkyl ester of 4-aminobenzoic acid, wherein 100% of the carbon present in the substituent is biobased carbon, as determined according to ASTM test D6866.

14. A volume comprising or consisting of 2-Ethylhexyl 4-(dimethylamino)benzoate molecules wherein the total volume of 2-Ethylhexyl 4-(dimethylamino)benzoate molecules comprises equal to or more than 1 wt%, more preferably equal to or more than 2 wt%, still more preferably equal to or more than 5 wt%, even more preferably equal to or more than 10 wt%, yet more preferably equal to or more than 30 wt%, even still more preferably equal to or more than 50 wt%, and preferably equal to or less than 100 wt%, of biobased carbon, as determined according to ASTM test D6866, based on the total weight of carbon present in the total volume of 2- Ethylhexyl 4-(dimethylamino)benzoate molecules15. A cosmetic composition comprising a UV filter compound according to claim 13 and / or a volume according to claim 14.

16. Use of a composition according to claim 9 or claim 10 or claim 12, a Ce-is hydrocarbyl ester of 4-aminobenzoic acid according to claim 11 or claim 12 or a UV filter compound according to claim 13 or a volume according to claim 14 for the preparation of a cosmetic composition.

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