Method for producing 2,4,6-substituted triazines

Field of the invention

[0001] The invention relates to a method for producing 2,4,6-substituted triazines according to general formula (I) under sustainable and more eco-friendly conditions. The invention also relates to a 2,4,6-substituted triazine according to formula (V). Furthermore, the present invention relates to fragrance compositions comprising the 2,4,6-substituted triazine according to formula (V). Moreover, the invention relates to the use of the 2,4,6-substituted triazine according to formula (V) for absorbing UV rays, preferably in cosmetics, particularly in creams and household applications, more particular in sunscreens.

Prior art

[0002] 2,4,6-substituted triazines are known in the prior art. A famous 2,4,6 substituted triazine is 2,4-Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-metho xy-phenyl)-1 ,3,5- triazine, which is an oil-soluble organic compound that is added to sunscreens to efficiently absorb UV rays. 2,4-Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-metho xyphenyl)-1,3,5- triazine, corresponding to [6,6'-(6-(4-Methoxyphenyl)-1,3,5-triazine-2,4-diyl)bis(3-((2 - ethylhexyl)oxy)phenol)], is also referred to as Bemotrizinol or Tinosorb S.

[0003] The preparation of 2,4,6-substituted triazines is also known from the prior art. In particular, an established three-step preparation from Bemotrizinol known starts from cyanuric chloride and 4-Bromoanisole. In the first step, 4-Bromoanisole and cyanuric chloride are reacted in a Grignard reaction to obtain the monosubstituted product, 6-(4-Methoxyphenyl)- 2,4-dichloro-1,3,5-triazine. In a second step, 6-(4-Methoxyphenyl)-2,4-dichloro-1,3,5-triazine and Benzene-1,3-diol (resorcinol) are reacted in a Friedel-Crafts acylation in the presence of AICI3 to obtain the corresponding trisubstituted product, 2,4-Bis(2,4-dihydroxy-phenyl)-6-(4- methoxyphenyl)-1,3,5-triazine. In a third and last step, the trisubstituted product reacts with 3- Bromomethylheptane under basic conditions (e.g. in the presence of NaOH) to finally obtain Bemotrizinol (scheme 1).

total yield of less than 57%

Scheme 1.

[0004] Although the synthesis of Bemotrizinol has been approved in the practice, implementation on a commercial scale has some drawbacks. First of all, the use of Grignard reagents as known from organometallic compounds bear high risks in terms of working safety, in particular as the reactive intermediates might react heavily with water, i.e. these substances require special handling and are not cheap and therefore, not suitable for upscaling. Moreover, use of Grignard reagents as well as use of stoichiometric amounts of AICI3 in the second step (Friedel-Crafts acylation) and use of alkyl halides in the third step lead to significant amounts of halogenated waste. Hence, known methods to prepare 2,4,6-substituted triazines, e.g. Bemotrizinol, are dubious in terms of working safety, and moreover, in terms of environmental sustainability. Moreover, it was found that the intermediate reaction steps of the prior art synthesis of Bemotrizinol show only low selectivity. Furthermore, due to the low solubility of the bis-resorcinyl triazine intermediate (diopat) in conventional solvents high boiling polar solvents like methylcellosolve are needed, further decreasing the overall sustainability of the entire synthesis. Accordingly, the state of the art process is not efficient and sustainable.

[0005] However, the quest for 2,4,6-substituted triazines and in particular of 2,4,6-substituted triazines with ability to efficiently absorb UV rays is very high.

[0006] Moreover, in terms of sustainability and eco-friendliness, there is an increasing demand for reactions for the preparation of the valuable Bemotrizinol leading to reduced amounts of halogenated waste and further for less use of organometallic reagents. Accordingly, another aim of the present invention is to provide for a more green and less toxic preparation process of Bemotrizinol and other new valuable 2,4,6-substituted triazines as efficient UV absorbers.

[0007] In addition, it is an aim of the present invention to provide for a facilitated process with less synthetic steps, which avoids tedious chromatography, and which allows for a considerable reduction in wastes and costs. Furthermore, it is desired to provide for a new process which allows for upscaling at an industrial scale.

[0008] The primary objective of the present invention is thus to provide an improved method for producing 2,4,6-substituted triazines according to general formula (I) under sustainable and more eco-friendly conditions. Moreover, it is an object of the present invention to provide a new method for producing a new 2,4,6-substituted triazine. A further objective is to provide a new 2,4,6-substituted triazine as such applicable as an efficient absorber for UV rays, preferably in cosmetics such as sunscreens.

[0009] The inventors have now surprisingly found a new method for producing 2,4,6- substituted triazines applicable for implementation on a commercial scale avoiding the use of Grignard reagents and causing lower amounts of halogenated waste.

Summary of the invention

[0010] In a first aspect, the present invention relates to a method for producing 2,4,6- substituted triazines according to general formula (I):

Formula (I) wherein X represents an alkyl group or an aromatic group, preferably wherein X represents a methoxyphenyl group; and

- wherein Y and Z represent a cyclohexenone ether; or

- wherein Y and Z represent a resorcinol monoether;

- wherein, in case Y and Z represent a cyclohexenone ether, the compound according to general formula (I) is obtained by reaction of said cyclohexenone ether with a 2,4,6-substituted triazine under basic conditions and preferably in the presence of a strong base, more preferred in the presence of a non-nucleophilic base, even more preferred in the presence of a non- nucleophilic Li-amide base and most preferred in the presence of lithium diisopropylamide (LDA); or

- wherein, in case Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said resorcinol monoether in an electrophilic aromatic substitution with a 2,4,6-substituted triazine; or

- wherein, in case Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said resorcinol monoether with the 2,4,6- substituted triazine, followed by a photo-induced rearrangement.

[0011] All reactions specified above are based on the reaction of a 2,4,6-substituted triazine with an ether (monoether) substituted six-membered cyclic carbon-based compound.

[0012] Preferably, X represents an alkyl group or an aromatic group. Said functional groups can either be substituted with further functional groups or can be unsubstituted.

[0013] In a preferred embodiment of the invention, wherein, in case Y and Z represent a cyclohexenone ether or a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said cyclohexenone ether or said resorcinol ether with a 2,4,6- substituted triazine according to general formula (II):

Formula (II)

- wherein R1 represents hydrogen or wherein R1 comprises or represents an alkyl group or an aromatic group, preferably wherein R1 represents a methoxyphenyl group; and

- wherein R2 represents a halogen atom; and

- wherein R3 represents a halogen atom.

[0014] Preferably, R1 represents an alkyl group or an aromatic group. Said functional groups can either be substituted with further functional groups or can be unsubstituted.

[0015] In a preferred variant, wherein, in case Y and Z represent a cyclohexenone ether or a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said cyclohexenone ether or said resorcinol ether with a 2,4,6-substituted triazine, wherein the 2,4,6-substituted triazine is 2,4-Dichloro-6-(4-methoxyphenyl) triazine. [0016] In a preferred variant, the cyclohexenone ether is a compound according to general formula (III):

Formula (III)

- wherein R4 represents a branched or linear alkyl group.

[0017] In a preferred variant, the resorcinol monoether is a compound according to general formula (IV):

Formula (IV)

- wherein R5 represents a branched or linear alkyl group.

[0018] In a particularly preferred variant, in case Y and Z represent a cyclohexenone ether, the compound according to general formula (I) is obtained by reaction of said cyclohexenone ether with a 2,4,6-substituted triazine under basic conditions as specified herein, wherein the cyclohexenone ether is 3-(2-ethylhexoxy)cyclohex-2-en-1-one and wherein the 2,4,6- substituted triazine is 2,4-Dichloro-6-(4-methoxyphenyl) triazine.

[0019] In another particularly preferred variant, wherein, in case Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said resorcinol monoether in an electrophilic aromatic substitution with a 2,4,6-substituted triazine, wherein the 2,4,6-substituted triazine is 2,4-Dichloro-6-(4-methoxyphenyl) triazine and wherein said resorcinol monoether is 3-(2-ethylhexoxy)-phenol.

[0020] According to a further preferred variant, wherein, in case Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said resorcinol monoether with a 2,4,6-substituted triazine, followed by a photo-induced rearrangement, wherein said resorcinol monoether is 3-(2-ethylhexoxy)-phenol and wherein the 2,4,6-substituted triazine is 2,4-Dichloro-6-(4-methoxyphenyl) triazine. [0021] In an alternative embodiment, wherein Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained by oxidative aromatization from the compound according to general formula (I), wherein Y and Z represent a cyclohexenone.

[0022] In a further alternative of the invention, the 2,4-Dichloro-6-(4-methoxyphenyl) triazine is obtained from a reaction of 2,4,6-trichlortriazine and methoxybenzene in presence of at least one catalyst.

[0023] According to an embodiment of the invention, the at least one catalyst is a solution containing a Lewis acid, preferably AICI3, TiCL, FeCh, Fe , FeBrs, FeFs, Sc(OTf)3, BF3, TiCL, TfOH, methanesulfonic or trifluoromethanesulfonic acid or one of Montmorillonit KSF, Zeolith- Hp or Nation. Preferably, the catalyst is a solution containing a Lewis acid selected from the group consisting of AICI3, FeCh, TiCL, (i.e. chloride containing Lewis acids), TfOH, Nation, or a mixture of the aforementioned substances. Most preferred the catalyst is selected from the group consisting of AICI3, FeCh, TiCU (i.e. chloride containing Lewis acids), and Nation.

[0024] According to a preferred embodiment the catalyst used in the Friedel Craft reactions is a chloride containing Lewis acid, preferably AlCh, FeCh, or TiCL, and most preferred FeCh.

[0025] Preferably, the at least one catalyst is used in sub-stoichiometric amount.

[0026] In a second aspect, the present invention relates to a 2,4,6-substituted triazine according to the formula (V):

Formula (V)

[0027] In a preferred variant, the compound according to the formula (V) is present in the form of: a pure optically active enantiomer; a racemic mixture of the enantiomers; or an optically active mixture of various enantiomers.

[0028] In a further aspect, the present invention relates to a fragrance composition comprising at least the compound according to the formula (V) and optionally at least one further fragrance substance.

[0029] In a further aspect, the present invention relates to the use of a compound according to the invention or the use of a fragrance composition comprising a compound according to the invention as an odorant or fragrance compound or for improving the fixation of a fragrance compound or a composition comprising a fragrance compound or for the preparation of a perfumed product.

[0030] In addition, the present invention relates to the use of a compound according to the invention for the preparation of a cosmetic composition or homecare composition.

[0031] Moreover, in a fourth aspect, the present invention relates to a cosmetic composition or homecare composition comprising at least the compound according to the formula (V), preferably a sunscreen formulation or product.

[0032] In a preferred variant of the invention, the cosmetic composition or homecare composition is a cream.

[0033] More preferably, the cosmetic composition is a sunscreen.

[0034] In a further aspect, the present invention relates to a perfumed product comprising a compound according to the invention or the fragrance composition comprising a compound according to formula (I).

[0035] In yet another aspect, the present invention relates to a perfumed product comprising a compound according to the invention or the fragrance composition comprising a compound according to the invention in an effective amount, and a carrier or substrate.

[0036] Finally, the present invention relates to a perfumed product as defined comprising a compound according to the invention or the fragrance composition comprising a compound according to the invention, wherein the perfumed product is a perfume oil, perfume base, formulation for personal hygiene, cleaning agent or air freshener. According to present invention, this covers all household applications, e.g. laundry detergent, fabric softener and further applications as mentioned in the formulation section (see formulation examples below).

[0037] The inventors have now established a method for producing 2,4,6-substituted triazines without any Grignard reagents and with significantly reduced amounts of halogenated waste. [0038] Moreover, the present invention provides for a more green and less toxic preparation process (reduced salt freight, reduction of toxic reactants and solvents) of Bemotrizinol and other new valuable 2,4,6-substituted triazines as efficient UV absorbers.

[0039] In addition, the present invention to provides for a facilitated process with less synthetic steps, which avoids tedious chromatography, and which allows for a considerable reduction in wastes and costs. Furthermore, the new process according to the present invention allows for upscaling at an industrial scale.

Detailed description of the invention

[0040] In accordance with the invention, the above-mentioned object is achieved by a method for producing 2,4,6-substituted triazines according to general formula (I):

Formula (I) wherein X represents an alkyl group or an aromatic group, and preferably wherein X represents a methoxyphenyl group; and

- wherein Y and Z represent a cyclohexenone ether; or

- wherein Y and Z represent a resorcinol monoether;

- wherein, in case Y and Z represent a cyclohexenone ether, the compound according to general formula (I) is obtained by reaction of said cyclohexenone ether with a 2,4,6-substituted triazine under basic conditions, preferably in the presence of a strong base, more preferred in the presence of a non-nucleophilic base, even more preferred in the presence of a non- nucleophilic Li-amide base and most preferred in the presence of lithium diisopropylamide (LDA); or

- wherein, in case Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said resorcinol monoether in an electrophilic aromatic substitution with a 2,4,6-substituted triazine; or

- wherein, in case Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said resorcinol monoether with the 2,4,6- substituted triazine, followed by a photo-induced rearrangement. [0041] Preferably, X represents an alkyl group or an aromatic group. Said functional groups can either be substituted with further functional groups or can be unsubstituted.

[0042] Preferably, in case Y and Z represent a cyclohexenone ether, the reaction is performed under basic conditions, i.e. in the presence of a base, and preferably in the presence of a strong base, more preferred in the presence of a non-nucleophilic base, even more preferred in the presence of a non-nucleophilic Li-amide base such as lithium diisopropylamide (LDA) (see Example 1).

[0043] Alternatively, instead of LDA other strong bases such as lithium bis(trimethylsilyl)amide (LiHMDS), or potassium tert-butoxide (KOt-Bu) can be advantageously used.

[0044] Preferably the base is a strong base with a pKa of 20 or higher, further preferred a pKa of 25 or higher, more preferred a pKa of 30 or higher and most preferred a pKa of 35 or higher.

[0045] Even more preferred the basic conditions of the reaction of cyclohexenone ether with a 2,4,6-substituted triazine are established by providing a non-nucleophilic base. The use of such non-nucleophilic bases allows for the efficient reduction of unwanted side-reactions. Examples of such bases are for example: 1 ,8-Bis(dimethylamino)naphthalene, 2-tert-Butyl- 1 , 1 ,3,3-tetramethylguanidine, 2 , 6- Di-tert-buty I py rid ine, 1 ,5-Diazabicyclo(4.3.0)non-5-ene (DBN), 1 ,8-Diazabicyclo(5.4.0)undec-7-ene (DBU), Lithium bis(trimethylsilyl)amide (LiHMDS or Li(HMDS)), Lithium diisopropylamide (LDA), Lithium tert-butoxide, Lithium tetramethylpiperidide (LiTMP or harpoon base), 2,4-Lutidine, 2,6-Lutidine, 3,5-Lutidine, N,N- Diisopropylethylamine (DI PEA, DIEA, or i-P^Net), Neopentyllithium, P4-t-Bu, Phosphazene, Potassium bis(trimethylsilyl)amide (KHMDS), Potassium tert-butoxide, Sodium bis(trimethylsilyl)amide, Sodium tert-butoxide (NaOtBu), 1 ,1 ,3,3-Tetramethylguanidine, 2,2,6,6-Tetramethylpiperidine (TMP, HTMP, or TMPH), 2,4,6-Tri-tert-butylpyrimidine, Triisopropylamine, 2,4,6-Trimethylpyridine, or mixtures thereof.

[0046] These bases are sterically hindered organic bases that are poor nucleophiles which are typically bulky, such that protons can attach to the basic center, but alkylation and complexation is inhibited.

[0047] Even more preferred, the basic conditions of the reaction of cyclohexenone ether with a 2,4,6-substituted triazine are established by providing a non-nucleophilic Li-amide base such as Lithium bis(trimethylsilyl)amide (LiHMDS or Li(HMDS)), Lithium diisopropylamide (LDA), Lithium tetramethylpiperidide (LiTMP or harpoon base), and mixtures thereof. For these bases best results were achieved in terms of selectivity and yield.

[0048] It was found that nucleophilic bases such as n-butyllithium (n-BuLi) or sodium amide (NaNH2) did not provide the desired product. [0049] According to a preferred variant of the present invention according to the first aspect, X represents an alkyl group or an aromatic group. Preferably, X represents a methoxyphenyl group. In this case the resulting compounds exhibit pronounced UV absorbing properties. Thus, in a preferred variant the present invention relates to a method for producing 2,4,6- substituted triazines according to general formula (la):

Formula (la)

- wherein Y and Z represent a cyclohexenone ether; or

- wherein Y and Z represent a resorcinol monoether;

[0050] According to the present invention, 2,4,6-substituted triazines according to general formula (I) are available by multiple routes, in each case without use of Grignard reagents and with significantly reduced amounts of halogenated waste, hence under more eco-friendly conditions.

[0051] In case Y and Z represent a cyclohexenone ether, the compound according to general formula (I) is obtained in a first variant by reaction of said cyclohexenone ether with a 2,4,6- substituted triazine under basic conditions, preferably in the presence of a strong base, more preferred in the presence of a non-nucleophilic base, even more preferred in the presence of a non-nucleophilic Li-amide base, as specified above, such as lithium diisopropylamide (LDA).

[0052] Preferably, the cyclohexenone ether is present as its enolate, which could be obtained by reaction with a strong base, more preferred in the presence of a non-nucleophilic base, even more preferred in the presence of a non-nucleophilic Li-amide base such as Lithium diisopropylamide (LDA). Hence, in a preferred embodiment of the invention, the cyclohexenone enolate and the 2,4,6-substituted triazine react in a nucleophilic aromatic substitution.

[0053] The use of the enolate form avoids the use of halide-containing precursors thereby making the process greener and more sustainable by avoiding halide wastes. In addition, high selectivity can be achieved.

[0054] Thus, according to the present invention, 2,4,6-substituted triazine are obtainable without any Grignard reagents and moreover, with significantly reduced amounts of halogenated waste.

[0055] In case Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained in a second variant by reaction of said resorcinol monoether in an electrophilic aromatic substitution with a 2,4,6-substituted triazine.

[0056] The reaction of said resorcinol monoether in an electrophilic aromatic substitution with a 2,4,6-substituted triazine is a Friedel-Crafts acylation which is catalyzed by a Lewis acid.

[0057] Hence, the reaction of a resorcinol monoether with a 2,4,6-substituted triazine does not need any Grignard reagents. Thus, according to the present invention, 2,4,6-substituted triazine are obtainable without any Grignard reagents and moreover, with significantly reduced amounts of halogenated waste.

[0058] In case Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained in a third variant by reaction of said resorcinol monoether with the 2,4,6- substituted triazine, followed by a photo-induced rearrangement.

[0059] First, the deprotonated resorcinol monoether reacts with the 2,4,6-substituted triazine in a nucleophilic aromatic substitution to obtain an O-bridged intermediate, followed by a photoinduced rearrangement of the O-bridged intermediate to obtain the compound according to general formula (I).

[0060] Preferably, the photo-induced rearrangement is a Photo-Fries rearrangement.

[0061] Hence, Grignard reagents are not needed. Thus, according to the present invention, 2,4,6- substituted triazines are obtainable without any Grignard reagents and moreover, with significantly reduced amounts of halogenated waste.

[0062] In a preferred variant of the invention, wherein, in case Y and Z represent a cyclohexenone ether or a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said cyclohexenone ether or said resorcinol ether with a 2,4,6- substituted triazine according to general formula (II):

Formula (II)

- wherein R1 represents hydrogen or wherein R1 comprises or represents an alkyl group or an aromatic group, preferably wherein R1 represents a methoxyphenyl group; and

- wherein R2 represents a halogen atom; and

- wherein R3 represents a halogen atom.

[0063] Preferably, R1 represents an alkyl group or an aromatic group. Said functional groups can either be substituted with further functional groups or can be unsubstituted.

[0064] According to a preferred variant of the present invention, R1 represents a group comprising an alkyl group or an aromatic group. Preferably, R1 represents a methoxyphenyl group. In this case the resulting compounds exhibit pronounced UV absorbing properties. Thus, in a preferred variant the present invention relates to a method by reacting said cyclohexenone ether or said resorcinol ether with a 2,4,6-substituted triazine according to general formula (Ila):

Formula (Ila)

- wherein R2 represents a halogen atom; and

- wherein R3 represents a halogen atom.

[0065] Preferably, R2 is selected from the group consisting of chloride, bromide, iodide, even more preferred chloride. [0066] Preferably, R3 is selected from the group consisting of chloride, bromide, iodide, even more preferred chloride.

[0067] According to another preferred variant of the present invention R2 is different from R3.

[0068] According to an alternative, and more preferred variant, R2 represents the same functional group as R3 (R2 = R3).

[0069] According to a particularly preferred embodiment, the 2,4,6-substituted triazine according to general formula (II) or (Ila) is 2,4-Dichloro-6-(4-methoxyphenyl) triazine.

[0070] The 2,4,6-substituted triazine according to general formula (II) is an excellent starting material for the preparation of 2,4,6-substituted triazine according to general formula (I) as the compound according to general formula (II) has a high reactivity due to the substituents R2, R3 and moreover, the compound according to general formula (II) enables the preparation of 2,4,6-substituted triazine according to general formula (I) in a very eco-friendly manner, particularly without use of Grignard reagents.

[0071] According to a preferred embodiment the compound of formula (II) or (Ila), and more specifically the 2,4,6-substituted triazine according to general formula (II) or (Ila) is prepared by replacing the Grignard reaction of cyanuric chloride according to the state of the art by a Friedel-Crafts acylation of anisole, which takes place under considerably milder conditions. Thereby, preferably, a Lewis acid acting as catalyst such as AICI3 is added preferably in sub- stoichiometric to stoichiometric amounts. Other suitable catalysts are TiCL, FeCh, Fe , FeBra, FeFa, Sc(OTf)3, BF3, TiCL, TfOH, methanesulfonic or trifluoromethanesulfonic acid or one of Montmorillonit KSF, Zeolith-Hp or Nation. Preferably, the catalyst is a solution containing a Lewis acid selected from the group consisting of AICI3, FeCh, TiCL, (i.e. chloride containing Lewis acids), TfOH, Nation, or a mixture of the aforementioned substances. Most preferred the catalyst is selected from the group consisting of AICI3, FeCh, TiCL (i.e. chloride containing Lewis acids), Nation.

[0072] According to a preferred embodiment the catalyst used in the Friedel Craft reactions is a chloride containing Lewis acid, preferably AICI3, FeCh, or TiCL, and most preferred FeCh.

[0073] It was found, that the above-mentioned Lewis acids result in excellent formations of the 2,4,6-substituted triazine according to general formula (II) or (Ila). The reactions could successfully be performed at room temperature in conventional solvents such as CH2CI2, toluene, acetonitrile (MeCN) or 1 ,2-dichlorobenzene (DCB). For AICI3 best results were achieved when used in stoichiometric amounts. However, also sub-stoichiometric amounts lead to the desired product.

[0074] In an embodiment of the invention, wherein, in case Y and Z represent a cyclohexenone ether or a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said cyclohexenone ether or said resorcinol ether with a 2,4,6- substituted triazine, wherein the 2,4,6-substituted triazine is 2,4-Dichloro-6-(4-methoxyphenyl) triazine as specified above.

[0075] 2,4-Dichloro-6-(4-methoxyphenyl) triazine is a highly reactive compound suitable for the preparation of 2,4,6-substituted triazine according to general formula (I) in a very eco- friendly manner, particularly without use of Grignard reagents. Further-more, 2,4-Dichloro-6- (4-methoxyphenyl) triazine is nontoxic and easily prepared.

[0076] In another embodiment of the invention, the cyclohexenone ether is a compound according to general formula (III):

Formula (III)

- wherein R4 represents a branched or linear alkyl group.

[0077] According to a preferred variant of the present invention, R4 represents a linear or a branched 01-012 alkyl group, preferably a linear or a branched 04-010 alkyl group and even more preferred a linear or a branched 06-010 alkyl group. Most preferred R4 is a 08 alkyl group.

[0078] According to a most preferred variant R4 is an isooctyl group. Therefore, according to a most preferred embodiment the cyclohexenone ether is a compound according to general formula (Illa):

[0079] According to a particularly preferred embodiment, the cyclohexenone ether according to general formula (III) or (Illa) is 3-(2-ethylhexoxy)cyclohex-2-en-1-one.

[0080] The cyclohexenone ether according to general formula (III) is an excellent starting material for the preparation of 2,4,6-substituted triazine according to general formula (I) as it is easily available, nontoxic and furthermore enables the preparation of 2,4,6-substituted triazines according to general formula (I) in a very eco-friendly manner.

[0081] Compounds according to general formula (III) could be obtained from 1 ,3- cyclohexanedione and the corresponding alcohols (see Example 1).

[0082] In a yet another variant of the invention, the resorcinol monoether is a compound according to general formula (IV):

Formula (IV)

- wherein R5 represents a branched or linear alkyl group.

[0083] According to a preferred variant of the present invention, R5 represents a linear or a branched C1-C12 alkyl group, preferably a linear or a branched C4-C10 alkyl group and even more preferred a linear or a branched C6-C10 alkyl group. Most preferred R5 is a C8 alkyl group.

[0084] According to a most preferred variant R5 is an isooctyl group. Therefore, according to a most preferred embodiment the resorcinol monoether is a compound according to general formula (IVa):

[0085] According to a particularly preferred embodiment, the resorcinol monoether according to general formula (IV) or (IVa) is 3-(2-ethylhexoxy)phenol.

[0086] The resorcinol monoether according to general formula (IV) is an excellent starting material for the preparation of 2,4,6-substituted triazines according to general formula (I) as it is easily available, nontoxic and furthermore enables the preparation of 2,4,6-substituted triazines according to general formula (I) in a very eco-friendly manner.

[0087] 3-(2-Ethylhexoxy)phenol could be obtained from 1 ,3-cyclohexanedione and isooctanol, followed by oxidative aromatization.

[0088] In a preferred variant, wherein Y and Z represent a cyclohexenone ether, the compound according to general formula (I) is obtained by reaction of said cyclo-hexenone ether with a 2,4,6-substituted triazine under basic conditions (preferably in the presence of a strong base, more preferred in the presence of a non-nucleophilic base, even more preferred in the presence of a non-nucleophilic Li-amide base and most preferred in the presence of lithium diisopropylamide (LDA)), wherein the cyclohexenone ether is 3-(2- ethylhexoxy)cyclohex-2-en-1-one and wherein the 2,4,6-substituted triazine is 2,4-Dichloro-6- (4-methoxyphenyl) triazine.

[0089] Both, 3-(2-ethylhexoxy)cyclohex-2-en-1-one and 2,4-Dichloro-6-(4-methoxy-phenyl) triazine (or the corresponding bromide or iodide compounds) are excellent starting materials for the preparation of 2,4,6-substituted triazine according to general formula (I) and even better in combination. 2,4-Dichloro-6-(4-methoxyphenyl) triazine is a highly reactive compound suitable for the preparation of 2,4,6-substituted triazine according to general formula (I) in a very eco-friendly manner. Furthermore, 2,4-Dichloro-6-(4-methoxyphenyl) triazine is nontoxic and easily prepared. Also, 3-(2-ethylhexoxy)-cyclohex-2-en-1-one is easily available, nontoxic and furthermore enables the preparation of 2,4,6-substituted triazines according to general formula (I) in a very eco-friendly manner, particularly without use of Grignard reagents.

[0090] Preferably, the cyclohexenone ether, 3-(2-ethylhexoxy)cyclohex-2-en-1-one, is present as its enolate, which could be obtained by reaction with a strong base (preferably in the presence of a non-nucleophilic base, even more preferred in the presence of a non- nucleophilic Li-amide base) such as Lithium diisopropylamide (LDA). Hence, in a preferred embodiment of the invention, the corresponding enolate from 3-(2-ethylhexoxy)cyclohex-2-en- 1-one and the 2,4,6-substituted triazine, 2,4-Dichloro-6-(4-methoxyphenyl) triazine, react in a nucleophilic aromatic substitution without use of any Grignard reagents and furthermore with reduced amounts of halogenated waste, hence under eco-friendly reaction conditions. This route is favorable, on the one hand, because it avoids the intermediate poorly soluble diopate and, on the other hand, bypasses the less selective monoetherification of resorcinol.

[0091] Thus, preferably, in case Y and Z represent a cyclohexenone ether, the reaction is performed under basic conditions, i.e. in the presence of a base, and preferably in the presence of a strong base, more preferred in the presence of a non-nucleophilic base, even more preferred in the presence of a non-nucleophilic Li-amide base such as lithium diisopropylamide (LDA) (see Example 1).

[0092] Alternatively, instead of LDA other strong bases such as lithium bis(trimethylsilyl)amide (LiHMDS), or potassium tert-butoxide (KOt-Bu) can be advantageously used. [0093] The 2,4,6-substituted triazine thus obtained is 6,6'-(6-(4-Methoxyphenyl)-1 ,3,5- triazine-2,4-diyl)bis(3-((2-ethylhexyl)oxy)cyclohex-2-en-1-o ne), corresponding to the 2,4,6- substituted triazine according to the formula (V).

[0094] Compounds according to general formula (III) could be obtained from 1 ,3- cyclohexanedione and the corresponding alcohols as described above. 3-(2- Ethylhexoxy)cyclohex-2-en-1-one thus could be obtained from 1 ,3-cyclohexanedione and isooctanol. The reaction preferably takes place in the presence of a strong acid such as methane sulfonic acid (MSA). Alternatively, p-Toluenesulfonic acid (PTSA or pTsOH) or tosylic acid (TsOH) can be used instead of MSA. Also other strong acids (preferably sulfonic acids) can be used for this purpose. Said acids preferably have a pKa value of -1 or less.

[0095] In another preferred variant, wherein Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said resorcinol monoether in an electrophilic aromatic substitution with a 2,4,6-substituted triazine, wherein the 2,4,6- substituted triazine is preferably 2,4-Dichloro-6-(4-methoxyphenyl) triazine and wherein said resorcinol monoether is preferably 3-(2-ethylhexoxy)phenol.

[0096] The reaction of 3-(2-ethylhexoxy)phenol with 2,4-Dichloro-6-(4-methoxyphenyl) triazine (or the corresponding bromide or iodide compounds) in an electrophilic aromatic substitution is a Friedel-Crafts acylation which is catalyzed by a Lewis acid, preferably by AlCh. Preferably, the Lewis acid is added in sub-stoichiometric amounts. Other suitable catalysts are TiCL, FeCh, Fe , FeBra, FeFa, Sc(OTf)3, BF3, TiCL, TfOH, methanesulfonic or trifluoromethanesulfonic acid or one of Montmorillonit KSF, Zeolith-Hp or Nation. Preferably, the catalyst is a solution containing a Lewis acid selected from the group consisting of AICI3, FeCh, TiCL, (i.e. chloride containing Lewis acids), TfOH, Nation, or a mixture of the aforementioned substances. Most preferred the catalyst is selected from the group consisting of AICI3, FeCh, TiCU (i.e. chloride containing Lewis acids), Nation.

[0097] According to a preferred embodiment the catalyst used in the Friedel Craft reactions is a chloride containing Lewis acid, preferably AlCh, FeCh, or TiCL, and most preferred FeCh.

[0098] Hence, the reaction of the resorcinol monoether 3-(2-ethylhexoxy)phenol with the 2,4,6-substituted triazine 2,4-Dichloro-6-(4-methoxyphenyl) triazine in a Friedel-Crafts reaction does not need any Grignard reagents. Thus, according to the present invention, 2,4,6- substituted triazines according to general formula (I) are obtainable without any Grignard reagents and moreover, with significantly reduced amounts of halogenated waste. Furthermore, 3-(2-ethylhexoxy)phenol is easily available and nontoxic. Moreover, 2,4- Dichloro-6-(4-methoxyphenyl) triazine is nontoxic and easily available.

[0099] The final 2,4,6-substituted triazine thus obtained is 6,6'-(6-(4-Methoxyphenyl)-1 ,3,5- triazine-2,4-diyl)bis(3-((2-ethylhexyl)oxy)phenol), also referred to as Bemotrizinol. [0100] Hence, the method according to the invention enables an eco-friendly preparation of Bemotrizinol, which is widely used as compound, capable to absorb UV rays.

[0101] In another embodiment of the invention, wherein, Y and Z represent a resorcinol monoether, the compound according to general formula (I) is obtained by reaction of said resorcinol monoether with a 2,4,6-substituted triazine, followed by a photo-induced rearrangement, wherein said resorcinol monoether is 3-(2-ethylhexoxy)phenol and wherein the 2,4,6-substituted triazine is 2,4-Dichloro-6-(4-methoxyphenyl) triazine.

[0102] The final 2,4,6-substituted triazine thus obtained is 6,6'-(6-(4-Methoxyphenyl)-1 ,3,5- triazine-2,4-diyl)bis(3-((2-ethylhexyl)oxy)phenol), also referred to as Bemotrizinol.

[0103] Hence, the method according to the invention enables a further route to obtain Bemotrizinol in an eco-friendly manner.

[0104] Based on this, two further routes to Bemotrizinol are possible: on the one hand, Friedel-Crafts acylation with 2,4-dichloro-6-(4-methoxyphenyl)triazine, and on the other hand, nucleophilic aromatic substitution with the same, resulting in an O-brominated intermediate, which is subsequently rearranged to BEMT in a Photo-FrieB rearrangement.

[0105] In an embodiment of the invention, the compound according to general formula (I), wherein Y and Z represent a resorcinol monoether is obtained by oxidative aromatization from the compound according to general formula (I), wherein Y and Z represent a cyclohexenone.

[0106] Thus, a compound according to general formula (I), wherein Y and Z represent a cyclohexenone is a suitable starting material for producing different compounds according to general formula (I), namely wherein Y and Z represent a resorcinol monoether. Moreover, oxidative aromatization is an eco-friendly and nontoxic method for producing the compound according to general formula (I) as no by-products or waste are generated.

[0107] According to the invention, in case the 2,4,6-substituted triazine thus obtained is 6,6'- (6-(4-Methoxyphenyl)-1 ,3,5-triazine-2,4-diyl)bis(3-((2-ethylhexyl)oxy)phenol), also referred to as Bemotrizinol, said Bemotrizinol is obtained by oxidative aromatization of 6,6'-(6-(4- Methoxyphenyl)-1 ,3,5-triazine-2,4-diyl)bis(3-((2-ethyl-hexyl)oxy)-cyclohex-2 -en-1-one), corresponding to the 2,4,6-substituted triazine according to the formula (V).

[0108] In an embodiment of the invention, the 2,4-Dichloro-6-(4-methoxyphenyl) triazine is obtained from a reaction of 2,4,6-trichlor triazine and methoxybenzene in presence of at least one catalyst.

[0109] The Friedel-Crafts reaction of 2,4,6-trichlor triazine, also referred to as cyanuric chloride and methoxybenzene does not require any Grignard reagents and is therefore more eco-friendly. [0110] Preferably, the at least one catalyst is a solution containing a Lewis acid, preferably AICI3, TiCL, FeCh, Fe , FeBra FeFa, Sc(OTf)3 or trifluoromethanesulfonic acid or one of Montmorillonit KSF, Zeolith-Hp or Nation. Preferably, the catalyst is a solution containing a Lewis acid selected from the group consisting of AICI3, FeCh, TiCL, (i.e. chloride containing Lewis acids), TfOH, Nation, or a mixture of the aforementioned substances. Most preferred the catalyst is selected from the group consisting of AICI3, FeCh, TiCL (i.e. chloride containing Lewis acids), Nation.

[0111] According to a preferred embodiment the catalyst used in the Friedel Craft reactions is a chloride containing Lewis acid, preferably AICI3, FeCh, or TiCL, and most preferred FeCh.

[0112] In order to reduce halogenated waste, the at least one catalyst is used in sub- stoichiometric amount.

[0113] Whenever reference is made in the present description to a compound of general formula (I), this is deemed to refer to all stereoisomers, in particular to all enantiomers, indifferently to the isomerically pure stereoisomers or mixtures of any of their stereoisomers. For economic reasons it is preferred to use the compounds as mixtures of their stereoisomers, in particular mixtures of their enantiomers

[0114] The compounds of general formula (I) are thus present in the form of:

(a) a pure optically active enantiomer;

(b) a racemic mixture of the enantiomers; or

(c) an optically active mixture of various enantiomers.

[0115] In a second aspect, the present invention relates to a 2,4,6-substituted triazine according to the formula (V):

Formula (V) [0116] The 2,4,6-substituted triazine according to the formula (V) could be obtained from 3- (2-ethylhexoxy)cyclohex-2-en-1-one and 2,4-Dichloro-6-(4-methoxy-phenyl) triazine as described above.

[0117] It was surprisingly found, that the substance according to formula (V), which is also denoted as Tetrahydro-BEMT (BEMT for Bemotrizinol), shows excellent UV absorbing properties, thus being an efficient new UV filter.

[0118] Accordingly, in a further variant the present invention also relates to the use of the compound according to general formula (V) for the preparation of a broad variety of consumer products (preferably sunscreens) and more specifically for use as an UV absorber and for the preparation of UV absorbing products. Additionally, the present invention also relates to these products as such, i.e. to consumer products (preferably sunscreens) and UV absorbers comprising the compound according to general formula (V).

[0119] Preferably, the cyclohexenone ether, 3-(2-ethylhexoxy)cyclohex-2-en-1-one, is present as its enolate, which could be obtained by reaction with a strong base, more preferred in the presence of a non-nucleophilic base, even more preferred in the presence of a non- nucleophilic Li-amide base such as Lithium diisopropylamide (LDA). Other suitable strong bases are specified above. Hence, in a preferred embodiment of the invention, the corresponding enolate from 3-(2-ethylhexoxy)cyclohex-2-en-1-one and the 2,4,6-substituted triazine, 2,4-Dichloro-6-(4-methoxyphenyl) triazine, react in a nucleophilic aromatic substitution with reduced amounts of halogenated waste, hence under eco-friendly reaction conditions.

[0120] Subsequently, the compounds according to general formula (V) can be transferred to Bemotrizinol via oxidative aromatization. This can be done electrochemically using gold electrodes.

[0121] A summary of the reactions according to the present invention is shown below (scheme 2):

OR x

Tetrahydro-BEMT Bemotrizinol (BEMT)

1,3-Cyclohexandion R = isooctyl R = isooctyl

Cyclohexenone monoether Resorcinol monoether

Scheme 2.

[0122] As shown above, the cyclohexenone monoether can also be oxidized to the resorcinol monoether prior to attachment to the triazine core. The resorcinol monoether can either be attached to 2,4-dichloro-6-(4-methoxyphenyl)triazine in a Friedel-Crafts acylation, leading directly to BMT. Alternatively, the resorcinol monoether and the triazine can be connected via a nucleophilic substitution to obtain an O-arylated intermediate. Potentially, this could be converted to BMT in a Photo-FrieB rearrangement.

[0123] Whenever reference is made in the present description to the 2,4,6-substituted triazine according to the formula (V), this is deemed to refer to all stereoisomers, in particular to all enantiomers, indifferently to the isomerically pure stereoisomers or mixtures of any of their stereoisomers. For economic reasons it is preferred to use the compounds as mixtures of their stereoisomers, in particular mixtures of their enantiomers.

[0124] Therefore, the present invention also discloses a mixture of any of the above compounds and/or a mixture of any of the above stereoisomers as well as the use of such compounds and/or mixtures in the meaning of the present application.

[0125] Generally, in the context of the present invention, the term "compounds of formula (I)" means both, the individual compounds of formula (I) (as well as their isomeric forms) and all mixtures of the compounds (and isomeric forms) of formula (I) in any mixing ratio. That is to say, statements in the following description concerning "compounds of formula (I)" apply both, to a single compound of formula (I), a single isomeric form and to mixtures consisting of or comprising compounds of formula (I) and their isomeric forms in any mixing ratio. Therefore, the present invention relates to the compounds according to the invention as such individually or also mixtures of the compounds according to the invention. The same applies for the 2,4,6- substituted triazine according to the formula (V).

[0126] The compounds of general formula (I) according to the invention can either be used as individual substances or in mixtures with at least one other known fragrance substance selected from an extensive range of natural and synthetic substances available in a large number of fragrance mixtures and/or in admixture with one or more ingredients or excipients conventionally used in conjunction with odorants in fragrance compositions, for example carrier materials and other auxiliary agents commonly used in the art. The same applies for the 2,4,6- substituted triazine according to the formula (V).

[0127] Therefore, in a further aspect, the present invention refers to a fragrance composition comprising at least one compound according to the invention and at least one further fragrance substance. In particular, present invention refers to a fragrance composition comprising at least the 2,4,6-substituted triazine according to the formula (V).

[0128] The following specified fragrance substances can be used, either as individual substances or in mixtures with at least one, two, three or even more fragrance substances, in a large number of fragrance mixtures, selected from an extensive range of natural and synthetic substances. [0129] Fragrance substances which are advantageously suitable for combining are listed for example in S. Arctander, Perfume and Flavor Materials, volumes I and II, Montclair, N.J. 1969, private publication, and/or in H. Surburg, J. Panten, Common Fragrance and Flavor Materials, 6 ^th edition, Wiley-VCH, Weinheim 2016. The following list comprises examples of known odorant substances which are advantageously suitable for combining with the inventive compounds and mixtures thereof: extracts of natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures such as for example: ambergris tincture; amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; tree moss absolute; bay oil; artemisia oil; benzoin resin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; buchu leaf oil; cabreuva oil; cade oil; calamus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassie absolute; castoreum absolute cedar leaf oil; cedarwood oil; cistus oil; citronella oil; lemon oil; copaiba balsam; copaiba balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill weed oil; dill seed oil; eau de brouts absolute; oak moss absolute; elemi oil; tarragon oil; eucalyptus citriodora oil; eucalyptus oil; fennel oil; pine-needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; iris root absolute; iris root oil; jasmine absolute; calamus oil; blue camomile oil; Roman camomile oil; carrot seed oil; cascarilla oil; pine-needle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavandin absolute; lavandin oil; lavender absolute; lavender oil; lemongrass oil; lovage oil; distilled lime oil; pressed lime oil; linaloe oil; Litsea cubeba oil; bay leaf oil; mace oil; marjoram oil; mandarin oil; massoia bark oil; mimosa absolute; ambrette oil; musk tincture; muscatel sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove bud oil; neroli oil; olibanum absolute; olibanum oil; opopanax oil; orange blossom absolute; orange oil; origanum oil; palmarosa oil; patchouli oil; perilla oil; Peru balsam oil; parsley leaf oil; parsley seed oil; petitgrain oil; peppermint oil; pepper oil; pimento oil; pine oil; pennyroyal oil; rose absolute; rosewood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil; star anise oil; styrax oil; tagetes oil; fir needle oil; tea tree oil; turpentine oil; thyme oil; Tolu balsam; tonka absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper berry oil; cognac oil; wormwood oil; Wintergreen oil; ylang oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil, and fractions thereof or constituents isolated therefrom; individual fragrance substances from the group comprising hydrocarbons, such as for example: 3-carene; alpha-pinene; beta-pinene; alpha-terpinene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; famesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1 ,3,5-undecatriene; styrene; diphenylmethane; aliphatic alcohols, such as for example: hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2- methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixtures of 3,4,5,6,6-pentamethyl-3,4-hepten-2-ol and 3,5,6,6-tetramethyl-4- methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; aliphatic aldehydes and the acetals thereof, such as for example: hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)- 2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-unde-cenal; (E)-4-decenal; 2- dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal; heptanal diethylacetal; 1 ,1-dimethoxy-2,2,5-trimethyl-4-hexene; citro-nellyloxyacetaldehyde; 1-(1- methoxypropoxy)-(E/Z)-3-hexene; aliphatic ketones and the oximes thereof, such as for example: 2-heptanone; 2-octanone; 3- octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2, 4,4,7- tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one; aliphatic sulphur-containing compounds, such as for example: 3-methylthio-hexanol; 3- methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercapto-hexyl butyrate; 3-acetylthiohexyl acetate; 1-menthen-8-thiol; aliphatic nitriles, such as for example: 2-nonenoic acid nitrile; 2-undecenoic acid nitrile; 2- tridecenoic acid nitrile; 3,12-tridecadienoic acid nitrile; 3,7-dimethyl-2,6-octadienoic acid nitrile;

3.7-dimethyl-6-octenoic acid nitrile; esters of aliphatic carboxylic acids, such as for example: (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl-isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl-2-methyl pentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl-(E,Z)- 2,4-decadienoate; methyl-2-octinate; methyl-2-noninate; allyl-2-isoamyloxyacetate; me-thyl-

3.7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl-crotonate; acyclic terpene alcohols, such as for example: citronellol; geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6- dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6- dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1 ,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and the formates, ace-tates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2- butenoates thereof; acyclic terpene aldehydes and ketones, such as for example: geranial; neral; citronellal; 7- hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6, 10-tri-methyl-9-undecenal; geranyl acetone; and the dimethyl and diethyl acetals of gera-nial, neral, 7-hydroxy-3,7- dimethyloctanal; cyclic terpene alcohols, such as for example: menthol; isopulegol; alpha-terpineol; terpinenol- 4; menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol; guaiol; and the formates, acetates, propio-nates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2- butenoates thereof; cyclic terpene aldehydes and ketones, such as for example: menthone; isomenthone; 8- mercaptomenthan-3-one; carvone; camphor; fenchone; alpha-ionone; beta-ionone; alpha-n- methyl ionone; beta-n-methyl ionone; alpha-isomethyl ionone; beta-isomethyl ionone; alphairone; alpha-damascone; beta-damascone; beta-damascenone; delta-damascone; gamma- damascone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one; 1 ,3,4,6,7,8a-hexahydro- 1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1- cyclohexen-1-yl)-2-butenal; nootkatone; dihydrono-otkatone; 4,6,8-megastigmatrien-3-one; alpha-sinensal; beta-sinensal; acetylated cedarwood oil (methylcedryl ketone); cyclic alcohols, such as for example: 4-tert-butylcyclohexanol; 3,3,5-trimethyl-cyclo-hexanol;

3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4- methyltetrahydro-2H-pyran-4-ol; cycloaliphatic alcohols, such as for example: alpha-3, 3-trimethylcyclohexylmethanol; 1-(4- isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)buta-nol; 2-methyl-

4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trime-thyl-3-cyclopent-1-yl)- 2-buten-1-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pen-tan-2-ol; 3-methyl-5-(2,2,3- trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4- penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol; cyclic and cycloaliphatic ethers, such as for example: cineole; cedryl methyl ether; cyclododecyl methyl ether; 1,1 -dimethoxycyclododecane; (ethoxymethoxy)-cyclododecane; alpha-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydro-naphtho[2,1-b]furan; 3a-ethyl- 6,6,9a-trimethyldodeca-hydronaphtho[2,1-b]furan; 1 ,5,9-trimethyl-13- oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-

5-(1-methylpropyl)-1 ,3-dioxane; cyclic and macrocyclic ketones, such as for example: 4-tert-butylcyclohexanone; 2,2,5- trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclo-pentanone; 2- hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3- methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5- cyclopentadecenone; 3-methylcyclopentadecanone; 4-(1-ethoxyvinyl)-3, 3,5,5- tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one; 6,7- dihydro-1 ,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecen-1-one; 9-cycloheptadecen- 1-one; cyclopentadecanone; cyclohexadecanone; cycloaliphatic aldehydes such as for example: 2,4-dimethyl-3-cyclohexene carbaldehyde; 2- methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3- cyclohexene carbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclo-hexene carbaldehyde; cycloaliphatic ketones, such as for example: 1-(3,3-dimethyl-cyclohexyl)-4-penten-1-one; 2,2- dimethyl-1-(2,4-dimethyl-3-cyclohexene-1-yl)-1 -propanone; 1-(5,5-dimethyl-1-cyclohexen-1- yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1 ,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl-(2,4-dimethyl-3- cyclohexen-1-yl)ketone; esters of cyclic alcohols, such as for example: 2-tert-butylcyclohexyl acetate; 4-tert- butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5- trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclo-pentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2, 5,5, 8a-tetramethyl-2- naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or6-indenyl acetate; 4,7-methano- 3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl isobutyrate; 4,7-methanoocta-hydro-5- or 6-indenyl acetate; esters of cycloaliphatic alcohols, such as for example: 1 -cyclohexylethyl crotonate; esters of cycloaliphatic carboxylic acids such as for example: allyl-3-cyclohexyl propionate; allylcyclohexyl oxyacetate; cis- and trans-methyl dihydrojasmonate; cis- and trans-methyl jasmonate; methyl-2-hexyl-3-oxocyclopentane carboxylate; ethyl-2-ethyl-6,6-dimethyl-2- cyclohexene carboxylate; ethyl-2,3,6,6-tetramethyl-2-cyclo-hexene carboxylate; ethyl-2- methyl-1,3-dioxolane 2-acetate; araliphatic alcohols, such as for example: benzyl alcohol; 1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3- phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1 ,1-di-methyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phe-nylpropanol; 2-methyl-5- phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-pro-pen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol; esters of araliphatic alcohols and aliphatic carboxylic acids, such as for example: benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2- phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; alpha-trichloromethylbenzyl acetate; alpha, alpha-dimethylphenylethyl acetate; alpha, alpha-dimethylphenyl-ethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4- methoxybenzyl acetate; araliphatic ethers such as for example: 2-phenyl ethyl methyl ether; 2- phenyl ethyl isoamyl ether; 2-phenyl ethyl 1 -ethoxyethyl ether; phenylacetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal; hydratropaldehyde dimethylacetal; phenylacet-aldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4, 4a, 5,9b- tetrahydro-indeno[1 ,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1 ,2-d]-m-dioxin; aromatic and araliphatic aldehydes, such as for example: benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropaldehyde; 4-methylbenz-aldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3- (4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert- butylphenyl)propanal; cinnamaldehyde; alpha-butylcinnamaldehyde; alpha- amylcinnamaldehyde; alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4- methoxybenzaldehyde; 4-hydroxy-3-methoxybenzalde-hyde; 4-hydroxy-3- ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dim-ethoxybenzaldehyde; 2- methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methy-lenedioxyphenyl)propanal; aromatic and araliphatic ketones, such as for example: acetophenone; 4-methyl- acetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2- butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl)ethanone; 2- benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1 ,1 , 2, 3, 3,6- hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-1 , 1-dimethyl-4-indanyl methyl ketone; 1-[2,3- dihydro-1 ,1 ,2,6-tetramethyl-3-(1-methylethyl)-1 H-5-indenyl]-ethanone; 5',6',7',8'-tetrahydro- 3',5',5',6',8',8'-hexamethyl-2-acetonaphthone; aromatic and araliphatic carboxylic acids and the esters thereof, such as for example: benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methylphenyl acetate; ethylphenyl acetate; geranylphenyl acetate; phenylethylphenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxy acetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl- 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl-3-phenyl glycidate; ethyl-3-methyl-3-phenyl glycidate; nitrogenous aromatic compounds, such as for example: 2,4,6-trinitro-1 ,3-dimethyl-5-tert- butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butyl aceto-phenone; cinnamonitrile; 3-methyl-5- phenyl-2-pentenoic acid nitrile; 3-methyl-5-phenylpentanoic acid nitrile; methyl anthranilate; methyl-N-methyl anthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7- dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexene carbaldehyde 6-isopropyl quinoline; 6-isobutyl quinoline; 6-sec-butyl quinoline; 2-(3- phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-iso-propylpyrazine; 2-isobutyl-3- methoxypyrazine; phenols, phenyl ethers and phenyl esters, such as for example: estragole; anethole; eugenol; eugenyl methyl ether; isoeugenol; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthyl isobutyl ether; 1 ,4- dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1- propenyl) phenol; p-cresyl phenyl acetate; heterocyclic compounds, such as for example: 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2- ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3- hydroxy-4H-pyran-4-one; lactones, such as for example 1 ,4-octanolide; 3-methyl-1 ,4-octanolide; 1 ,4-nonanolide; 1 ,4- decanolide; 8-decen-1 , 4-olide; 1 ,4-undecanolide; 1 ,4-dodecan-olide; 1 ,5-deca-nolide; 1 ,5- dodecanolide; 4-methyl-1 ,4-decanolide; 1 ,15-penta-decanolide; cis- and trans-11- pentadecen- 1 ,15-olide; cis- and trans- 12-pentadecen-1 , 15-olide; 1 ,16-hexa-decanolide; 9- hexadecen-1 , 16-olide; 10-oxa-1 ,16-hexadecanolide; 11-oxa-1 ,16-hexa-decanolide; 12-oxa- 1 ,16-hexadecanolide; ethylene 1 ,12-dodecanedioate; ethylene 1 ,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin; and mixtures of the above substances.

[0130] Fragrance compounds according to the invention and fragrance compositions which comprise or contain the at least one compound according to the invention may be used for perfuming applications in liquid form, undiluted or diluted with a solvent. Solvents suitable for this purpose are for example ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1 ,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, triacetin, vegetable oils, etc.

[0131] Moreover, the fragrance compounds according to the invention or fragrance compositions which comprise or contain the compounds according to the invention may be adsorbed on a carrier which ensures both a fine distribution of the fragrance substances in the final product and controlled release upon use. Such carriers may be porous inorganic materials such as sodium sulphate, silica gels, zeolites, gypsums, clays, clay granules, aerated concrete etc., or organic materials such as woods, cellulose-based substances, sugars, dextrins (for example maltodextrin), or plastics such as PVC, polyvinyl acetates or polyurethanes.

[0132] Fragrance compounds according to the invention and fragrance compositions which comprise or contain the compound(s) according to the invention indicated by formula (I) and in particular by formula (V) may also be microencapsulated, spray-dried, be provided as inclusion complexes or as extrusion products (i.e. products according to the invention).

[0133] Optionally, the properties of the fragrance compounds or compositions modified in such a way may be further optimized with regard to a more targeted fragrance release by “coating” with suitable materials, for which purpose waxy plastics, such as for example polyvinyl alcohol, are preferably used. The resultant products are in turn products according to the invention.

[0134] The fragrance compounds according to the invention or fragrance compositions according to the invention may be encapsulated, for example, by coacervation methods with the assistance of capsule materials made, for example, from poly-urethane-type substances or soft gelatine.

[0135] Spray-dried fragrance formulations based on fragrance compounds according to the invention and fragrance compositions which comprise or contain the compound(s) according to the invention may be produced for example by spray-drying an emulsion or dispersion comprising or containing the fragrance compound or composition, wherein modified starches, proteins, dextrin and vegetable gums may be used as carriers. Inclusion complexes may be produced for example by introducing dispersions of the fragrance compound or composition and cyclodextrins or urea derivatives into a suitable solvent, for example water.

[0136] Extrusion products may be produced by melting the fragrance compound or compositions with a suitable waxy substance and extruding with subsequent solidification, optionally in a suitable solvent, for example isopropanol.

[0137] In another aspect, the present invention thus relates to the use of a compound according to general formula (I), in particular to the 2,4,6-substituted triazine according to the formula (V) or a fragrance composition comprising or containing a compound according to the invention as an efficient odorant or fragrance compound. The comments made above apply correspondingly to preferred compounds and mixtures.

[0138] The present invention also relates to the use of compounds according to the invention, in particular compounds according to general formula (I) as well as the 2,4,6-substituted triazine according to the formula (V) or a fragrance composition comprising or containing at least a compound according to the invention for improving the fixation of a fragrance compound while making simultaneous use of the compound or of the composition comprising or containing the compound according to the invention as a fragrance substance and for preparing perfumed products. With regard to the preferred choice of compounds and mixtures according to the invention, the comments made above of course apply correspondingly.

[0139] Therefore, the present invention relates to the use of said compounds and compositions for improving the fixation of a fragrance compound or for the preparation of a perfumed product.

[0140] The compounds or compositions which comprise or contain a compound according to the invention may be incorporated into products which are perfumed or are intended to be perfumed, in particular formulations serving for personal hygiene such as perfume oils, perfume bases, formulations for personal hygiene, cleaning agents or air fresheners.

[0141] Thus, in another aspect, the present invention also refers to perfumed products comprising or containing a compound according to formula (I) as well as a 2,4,6-substituted triazine according to the formula (V) or a fragrance composition comprising or containing at least one compound according to the invention.

[0142] In accordance with a preferred variant, the perfumed products according to the invention comprising or containing the compound or a fragrance composition which comprises or contains a compound according to the invention are produced by incorporating the compound or composition which comprises or contains a compound according to the invention, in pure form without a solvent, as a solution or in the form of a mixture with a solid or liquid carrier and optionally other auxiliaries and/or stabilizers to form a base preparation serving for personal hygiene such as cleaning agents and the like. [0143] The present invention therefore also provides a perfumed product comprising or containing a compound of general formula (I) as well as a 2,4,6-substituted triazine according to the formula (V) or a fragrance composition which comprises or contains at least a compound according to the invention in an effective amount in combination with a carrier or substrate.

[0144] Moreover, the present invention relates to a cosmetic composition or homecare composition comprising at least the 2,4,6-substituted triazine according to the formula (V).

[0145] The 2,4,6-substituted triazine according to the formula (V) is capable to absorb UV rays.

[0146] Hence, in a preferred embodiment, the cosmetic composition or homecare composition is a cream, preferably a sunscreen.

[0147] Accordingly, present invention further relates to the use of 2,4,6-substituted triazine according to the formula (V) for absorbing UV rays, preferably in cosmetic compounds, particularly in sunscreens.

Examples

[0148] The following compounds were prepared according to the methods indicated below. The structure determination by means of spectroscopy, was carried out by known techniques.

[0149] As indicated above, all compounds disclosed herein as well as all formulas generally should encompass both, the pure stereoisomers, in particular enantiomers, and mixtures of the stereoisomers, in particular mixtures of the enantiomers. Also, all intermediates obtained from the process can occur in different isomeric forms, and, thus, should encompass both the pure stereoisomers and mixtures of the stereo-isomers.

[0150] Example 1 : Preparation of 6,6'-(6-(4-Methoxyphenyl)-1,3,5-triazine-2,4- diyl)bis(3-((2-ethylhexyl)oxy)cyclohex-2-en-1-one) (corresponding to formula (V)) - Cyclohexenone Route

[0151] Step 1 : Preparation of 3-((2-Ethylhexyl)oxy)cyclohex-2-en-1-one (cyclohexenone monoether according to formula (Illa))

[0152] Methane sulfonic acid (MSA) (87 pL, 129 mg, 1.34 mmol, 0.03 equiv) was added to a stirred solution of cyclohexane- 1 , 3-dione (5.00 g, 44.6 mmol, 1.00 equiv) and 2-ethyl-1- hexanol (10.5 mL, 8.71 g, 66.9 mmol, 1.00 equiv) in toluene (50 mL) (acid catalyzed etherification, scheme 3). The mixture was heated to 111 °C for 20 h. After cooling to room temperature, the solution was neutralized with aqueous Na2COs solution. The organic layer was separated, washed with water and brine dried over sodium sulfate. The solvent was removed under reduced pressure. The crude product was purified via vacuum distillation: removal of residual isooctanol at 450 mbar / 80°C, then distillation of the resulting product at 10 mbar / 200°C. The title compound was obtained as a pale yellow oil (6.90 g, 30.8 mmol, 69%). The desired isooctyloxy cyclohexenone was obtained in a maximum yield of approx. 70% and the reaction could be scaled up to a multigram scale.

Synthesis 3-isooctyloxy cyclohexenone via an acid-catalyzed condensation.

Scheme 3.

[0153] Alternatively, p-Toluenesulfonic acid (PTSA or pTsOH) or tosylic acid (TsOH) can be used instead of MSA. Alto other strong acids (preferably sulfonic acids) can be used for this purpose. Said acids preferably have a pKa value of -1 or less. However, the use of MSA is preferred as it allows for an efficient etherification and is a cheap reactant and allows for a high selectivity.

¹ H NMR (500 MHz, CDCI ₃ ) 5 5.35 (s, 1 H), 3.75 - 3.66 (m, 2H), 2.40 (t, J = 6.3 Hz, 2H), 2.34 (dd, J = 7.3, 6.0 Hz, 2H), 1.97 (p, J = 6.5 Hz, 2H), 1.70 - 1.61 (m, 2H), 1.40 (tdd, J = 7.5, 6.1 , 3.8 Hz, 2H), 1.36 - 1.21 (m, 5H), 0.89 (td, J = 7.1 , 3.0 Hz, 6H).

¹³ C NMR (126 MHz, CDCI3) 6 200.0, 178.4, 102.8, 71.2, 38.9, 36.9, 30.5, 29.2, 29.1 , 23.9, 23.1 , 21.4, 14.2, 11.1.

FAB-MS m/z (%): 224 (39), 181 (66), 131 (71), 113 (86), 112 (30), 100 (18), 84 (26), 71 (42), 70 (30), 69 (100), 57 (43).

HRMS-FAB (m/z): [M + H] ⁺ calcd. for Ci ₄ H ₂ 4O ₂ , 224.1771 ; found, 224.1770.

IR (ATR, v) = 2955 (m), 2928 (m), 2871 (w), 2860 (w), 1727 (vw), 1652 (vs), 1602 (vs), 1458 (m), 1428 (w), 1400 (w), 1368 (s), 1349 (m), 1326 (m), 1310 (w), 1237 (m), 1217 (vs), 1181 (vs), 1133 (s), 1058 (w), 1003 (m), 958 (m), 931 (w), 905 (w), 863 (m), 823 (m), 772 (w), 759 (w), 728 (w), 662 (w), 606 (w), 535 (w), 460 (w), 446 (w), 425 (w), 384 (w) cm" ¹ .

[0154] Step 2: Preparation of 6,6'-(6-(4-Methoxyphenyl)-1 ,3,5-triazine-2,4-diyl)bis(3-((2- ethylhexyl)-oxy)cyclohex-2-en-1-one)

[0155] With the cyclohexenone monoether at hand, two possible routes. The cyclohexenone monoether can either be oxidized to the 3-isooctyloxy phenol building block (resorcinol monoether) or attached to the triazine core prior to oxidation of the entire system.

[0156] According to the latter, initially, 3-isooctyloxy cyclohexenone was treated with LDA and subsequently, 2,4-dichloro-6-(4-methoxyphenyl)triazine was added. [0157] Therefore, a 2M solution of LDA in THF (2.44 mL, 523 mg, 4.88 mmol, 2.50 equiv) was added to a solution of 3-((2-ethylhexyl)oxy)cyclohex-2-en-1-one (876 mg, 3.90 mmol, 2.00 equiv) in anhydrous THF at -78 °C under argon atmosphere. The solution was stirred for 30 min. Subsequently, the cooling was removed and 2,4-dichloro-6-(4-methoxyphenyl)-1 ,3,5- triazine (500 mg, 1.95 mmol, 1.00 equiv) dissolved in anhydrous THF (10 ml) was added dropwise to the reaction mixture and the resulting yellow solution was stirred for 15 to 16 h at 60 °C to 65 °C. The solvent was removed under reduced pressure, and the residue was purified via flash column chromatography (SiC>2, CH/EtOAc 20:1). The final product 6,6'-(6-(4- Methoxyphenyl)-1 ,3,5-triazine-2,4-diyl)bis(3-((2-ethylhexyl)oxy)cyclohex-2-e n-1-one) (also termed tetrahydro-Bemotrizinol or tetrahydro- BEMT) was isolated as a yellow resin (350 mg, 554 pmol, 28%) (scheme 4).

OMe

28%

Reaction of 2-chloro-4,6-diphenyltriazine with a Li-enolate derived from 3-isooctyl oxy cyclohexenone, R = isooctyl.

Scheme 4.

[0158] Alternatively, instead of LDA other strong bases and preferably non-nucleophilic bases, even more preferred non-nucleophilic Li-amide bases such as lithium bis(trimethylsilyl)amide (LiHMDS) can be advantageously used.

¹ H-NMR (500 MHz, CDCI ₃ ) 6 [ppm] = 8.45 (d, J = 9.0 Hz, 2H), 6.96 (d, J = 9.0 Hz, 2H), 5.50 (s, 2H), 3.91-3.86 (m, 1 H), 3.89 (s, 3H), 3.86-3.70 (m, 4H), 2.83 (t, J = 8.4 Hz, 1 H), 2.73- 2.62 (m, 1 H), 2.61-2.53 (m, 2H), 2.45 (td, J = 8.4, 3.0 Hz, 1 H), 2.40 (t, J = 6.3 Hz, 1 H), 2.37-2.27 (m, 2H), 1.98 (p, J = 6.5 Hz, 1 H), 1.75-1.60 (m, 2H), 1.48-1.21 (m, 16H), 0.97-0.77 (m, 12H). Minor signals at 15.28 (s), 13.59 (s).

¹³ C-NMR (126 MHz, CDCI3) <5 [ppm] = 195.5, 179.4, 178.1 , 172.9, 164.4, 131.8, 126.6, 114.3, 102.7, 71.6, 55.7, 55.3, 38.9, 30.5, 29.1 , 28.1 , 26.2, 23.9, 23.1 , 14.2, 11.1.

IR (ATR) v [cm- ¹ ] = 2956 (w), 2928 (w), 2871 (w), 2859 (w), 1728 (vw), 1655 (w), 1636 (w), 1604 (s), 1579 (m), 1503 (vs), 1462 (vs), 1402 (vs), 1375 (vs), 1327 (vs), 1312 (vs), 1281 (s), 1255 (vs), 1222 (vs), 1184 (vs), 1166 (vs), 1123 (s), 1113 (s), 1064 (s), 1028 (s), 1006 (s), 975 (m), 965 (m), 935 (m), 909 (m), 851 (s), 820 (s), 813 (s), 792 (m), 732 (s), 680 (m), 666 (m), 636 (m), 591 (s), 511 (m), 456 (w). FAB-MS m/z (%): 630 (14), 629 (27), 628 (51), 627 (14), 446 (33), 445 (48), 444 (100), 443 (70), 373 (18), 334 (11), 333 (14), 332 (44), 331 (29), 330 (37), 261 (10), 220 (29), 136 (13), 134 (33).

HRMS-FAB (m/z): [M + H] ⁺ calcd. for C23H22O2N3, 371.1707; found, 372.1707.

[0159] Example 2: Preparation of 6,6'-(6-(4-Methoxyphenyl)-1,3,5-triazine-2,4- diyl)bis(3-((2-ethylhexyl)oxy)phenol) - Electrochemical oxidation to Bemotrizinol

[0160] General remarks: Cyclic voltammetry measurements were performed to assess the redox potential of both the cyclohexenone and 6,6'-(6-(4-Methoxyphenyl)-1 ,3,5-triazine-2,4- diyl)bis(3-((2-ethylhexyl)-oxy)cyclohex-2-en-1-one). Every maximum corresponds to an oxidation process occurring at the indicated voltage. The incline of the curve towards higher voltage is due to oxidation of the solvent. As no minima occur during the reverse cycle, the oxidation process is irreversible. Upon repeated cycles, passivation of the electrodes is observed, decreasing the intensity over multiple cycles. Highest intensity was obtained using glassy carbon electrode, however, most pronounced passivation after the first cycle was observed. In case of the platinum electrode, the intensity of the oxidation is lower, and a second oxidative process arises. For both peaks, passivation was observed after one cycle. Almost no passivation occurred when gold electrodes were used.

[0161] The cyclic voltammetry results for 6,6'-(6-(4-Methoxyphenyl)-1 ,3,5-triazine-2,4- diyl)bis(3-((2-ethylhexyl)-oxy)cyclohex-2-en-1-one) showed significantly different redox behavior for different electrode materials. For glassy carbon, the overall intensity is quite low compared to the spectra of cyclohexenone. Additionally, a strong passivation was observed after the first cycle. For gold, the overall intensity was also relatively low, and no distinct oxidation peak occurred. In the case of a platinum electrode, a significant maximum at 1.8 V with a relatively highest intensity of up to 30 mA/cm2 was present. After the first cycle, the intensity was reduced due to passivation, however, remaining constant over the following cycles.

[0162] Cyclic voltammograms (CVs): Cyclic voltammetry measurements were carried out on a Gamry 600+ and a Gamry 3000 potentiostat (Gamry Instruments) using a Teflon cell and an MSR electrode rotator (Pine Research) equipped with a disc electrode (Pt, Au or glassy carbon, 0.5 mm dia.) and a platinum wire counter electrode. The potentials were normalized to a Ag/AgCI (KCI saturated in H2O) reference electrode (Meisenberger GmbH). A 0.1 M BU4NBF4 electrolyte was used for all electrochemical experiments. Before each measurement, the solution was purged with argon. Cyclic voltammetry experiments were carried out at ambient temperature. The potential window ranged from 0.05 to 1.6 V vs Ag/AgCI. Measurements were performed sequentially at scan rates of 200, 100, 50, 25, and 200 mV s’ ¹ , with three cyclic voltammograms per scan rate were recorded under argon atmosphere using a GAMRY INSTRUMENT Interface 1010B potentiostat. All the electrochemical oxidations were performed in an I KA ElectraSyn 2.0 equipped with electrodes (each 0.8 x 3.0 cm ² ). Electrodes were purchased from I KA and used as received. Reference electrodes were filled with fresh 3 M aqueous KCI solution.

[0163] In a 10 mL ElectraSyn vial, 6,6'-(6-(4-Methoxyphenyl)-1 , 3, 5-triazine-2,4-diyl)bis(3-((2- ethylhexyl)-oxy)cyclohex-2-en-1-one) (1.0 eq.) and B114NBF4 (20.0 eq.) were dissolved in anhydrous DCM (7 mL). The solution was electrolyzed under a constant current of 2.0 V for 4.2 F/mol using a platinum anode and a graphite cathode. After completion of the electrolysis, the solvent was removed under reduced pressure and the residue was purified via flash column chromatography. 6,6'-(6-(4-Methoxyphenyl)-1 ,3,5-triazine-2,4-diyl)bis(3-((2- ethylhexyl)oxy)phenol), Bemotrizinol, was isolated as a yellow resin.

[0164] Example 3: Preparation of 6,6’-(6-(4-Methoxyphenyl)-1,3,5-triazine-2,4- diyl)bis(3-((2-ethylhexyl)oxy)phenol) - Bemotrizinol via the compounds according to general formula (V) and via oxidative aromatization

[0165] In a 10 mL ElectraSyn vial, 6,6’-(6-(4-Methoxyphenyl)-1 , 3, 5-triazine-2,4-diyl)bis(3-((2- ethylhexyl)oxy)cyclohex-2-en-1-one) (Tetrahydro-BMT, THBMT, see Example 1) (20.0 mg,

31.7 pmol, 1.00 equiv), BU4NBF4 (208 mg, 633 pmol, 20.0 equiv), were dissolved in anhydrous CH2CI2 (7 mL). The solution was electrolyzed under a constant voltage of 2.0 V for 4.2 F/mol using a platinum anode and a graphite cathode. After completion of the electrolysis, the solvent was removed under reduced pressure, and the residue was purified via flash chromatography (SiC>2, CH/EtOAc 20:1). 1 was isolated as a yellow resin (2.00 mg, 3.19 pmol, 10%).

F? _f (SiO ₂ , CH/EtOAc, 4:1) = 0.70.

¹ H-NMR (500 MHz, CDCI3) 5 [ppm] = 13.40 (s, 2H), 8.53 - 7.86 (m, 4H), 6.93 (d, J = 8.9 Hz, 2H), 6.49 (dd, J = 8.9, 2.5 Hz, 2H), 6.42 (d, J = 2.5 Hz, 2H), 3.88 (dd, J = 5.9, 2.1 Hz, 4H), 3.85 (s, 3H), 1.76 (h, J = 6.2 Hz, 2H), 1.60 - 1.39 (m, 6H), 1.39 - 1.31 (m, 2H), 1.00 - 0.90 (m, 12H).

¹³ C-NMR (126 MHz, CDCI3) 5 [ppm] = 170.0 (2C, C _q , CN), 167.4 (C _q , CN), 165.5 (2C, C _q ),

164.7 (2C, C _q ), 163.9 (C _q ), 131.2 (2C, C _q ), 130.6 (2C, CH _Ar ), 126.6 (C _q ), 114.3 (2C, CH _Ar ), 110.1 , 108.5 (2C, CH _Ar ), 101.8 (2C, CH _Ar ), 70.9 (2C, CH ₂ ), 55.5 (CH ₃ ), 39.3 (2C, CH), 30.6 (2C, CH ₂ ), 29.2 (2C, CH ₂ ), 23.9 (2C, CH ₂ ), 23.2 (2C, CH ₂ ), 14.2 (2C, CH ₃ ), 11.2 (2C, CH ₃ ).

IR (ATR) v [cm- ¹ ] = 2956 (w), 2924 (m), 2868 (w), 2859 (w), 1628 (m), 1585 (vs), 1530 (vs), 1502 (vs), 1451 (s), 1439 (s), 1422 (s), 1414 (s), 1390 (m), 1370 (vs), 1353 (vs), 1319 (m), 1306 (m), 1249 (vs), 1232 (vs), 1186 (vs), 1170 (vs), 1159 (vs), 1119 (s), 1099 (vs), 1050 (m), 1020 (vs), 973 (m), 851 (w), 832 (vs), 796 (vs), 747 (m), 718 (m), 642 (m), 629 (m), 622 (s), 596 (vs), 510 (m), 462 (m), 411 (w).

FAB-MS m/z (%): 630 (14), 629 (27), 628 (51), 627 (14), 446 (33), 445 (48), 444 (100), 443 (70), 373 (18), 334 (11), 333 (14), 332 (44), 331 (29), 330 (37), 261 (10), 220 (29), 136 (13), 134 (33). HRMS-FAB (m/z): [M + H] ⁺ calcd. for C38H50O5N3, 628.3745; found, 628.3747.

[0166] Example 4: Preparation of 6,6’-(6-(4-Methoxyphenyl)-1,3,5-triazine-2,4- diyl)bis(3-((2-ethylhexyl)oxy)phenol) - Resorcinol Route

[0167] Step 1 : Preparation of 1-Bromo-3-((2-ethylhexyl)oxy)benzene

Scheme 5.

[0168] To a solution of 3-bromophenol (4.00 g, 23.1 mmol, 1.00 equiv) and isooctyl bromide (5.36 g, 27.7 mmol, 1.20 equiv) in DMF (100 mL) was added potassium carbonate (4.79 g, 34.7 mmol, 1.50 equiv) and the mixture was stirred at 110 °C for 12 h. After cooling to r.t., water (40 mL) was added, and the mixture was extracted with ethyl acetate (50 mL). The combined organic layers were dried over Na2SO4. The solvent was removed under reduced pressure, and the residue was purified via flash chromatography (SiC>2, CH/EE 40:1). 1-Bromo- 3-((2-ethylhexyl)oxy)benzene was obtained as a pale-yellow oil (5.32 g, 18.7 mmol, 81%).

[0169] Alternatively, the reaction was conducted using other halide reagents such as the corresponding chloride compounds (e.g. isooctyl chloride).

Rf (SiO ₂ , CH/EtOAc, 4:1) = 0.81.

¹ H NMR (400 MHz, CDCI ₃ ) <5 [ppm] = 7.13 (t, J = 8.3 Hz, 1 H), 7.08 - 7.03 (m, 2H), 6.83 (ddd, J = 8.2, 2.4, 1.2 Hz, 1 H), 3.87 - 3.76 (m, 2H, CH ₂ ), 1.71 (hept, J = 6.1 Hz, 1H, CH), 1.55 - 1.36 (m, 4H), 1.35 - 1.26 (m, 5H), 0.97 - 0.84 (m, 6H, CH ₃ ).

¹³ C NMR (100 MHz, CDCI3) 5 [ppm] = 160.4 (C _q , C ¹ ), 130.6 (CH _Ar ), 123.6 (CH _Ar ), 122.9 (C _q , C ³ ), 117.9 (CH _Ar ), 113.7 (CH _Ar ), 70.9 (CH ₂ ), 39.5 (CH), 30.6 (CH ₂ ), 29.2 (CH ₂ ), 24.0 (CH ₂ ), 23.2 (CH ₂ ), 14.2 (CH ₃ ), 11.2 (CH ₃ ).

IR (ATR) v [cm- ¹ ] = 2958 (s), 2925 (s), 2871 (m), 2859 (m), 1588 (vs), 1572 (vs), 1465 (vs), 1434 (m), 1424 (m), 1381 (m), 1323 (m), 1302 (m), 1283 (vs), 1242 (vs), 1227 (vs), 1166 (w), 1156 (m), 1119 (w), 1089 (m), 1064 (s), 1031 (vs), 1016 (vs), 992 (vs), 973 (m), 929 (m), 860 (vs), 837 (s), 764 (vs), 728 (m), 680 (vs), 603 (w), 601 (w), 441 (m).

FAB-MS m/z (%): 287 (61), 286 (65), 285 (100) [M + 2 H] ⁺ , 284 (56), 283 (49), 187 (19), 185 (19), 175 (54), 174 (26), 173 (54), 172 (22), 154 (29), 89 (78), 87 (33).

HRMS-FAB (m/z): [M + H] ⁺ calcd. for Ci ₄ H ₂ iOi ⁷⁹ Bri, 284.0770; found, 284.0772. [0170] Step 2: Preparation of 3-((2-Ethylhexyl)oxy)phenol

Scheme 6.

[0171] 1-Bromo-3-((2-ethylhexyl)oxy)benzene (700 mg, 2.45 mmol, I .OO equiv), Pchdbas (45 mg, 49.1 pmol, 0.02 equiv), XPhos (94 mg, 196 pmol, 0.08 equiv) and KOH (303 mg, 5.40 mmol, 2.20 equiv) were dissolved in a 4: 1 mixture of 1 ,4-dioxane and water (5 mL) under an argon atmosphere. The mixture was heated to 100 °C for 20 h. After cooling to room temperature, the solution was neutralized with 1 M HCI. The mixture was extracted with EtOAc, and the combined organic layers were dried over Na2SO4. The solvent was removed under reduced pressure and the residue was purified via flash chromatography (SiCh, CHCh). 3-((2- Ethylhexyl)oxy)phenol was obtained as a red oil (408 mg, 1.84 mmol, 75%).

F? _f (SiO ₂ , CH/EtOAc, 4:1) = 0.52.

¹ H NMR (400 MHz, CDCh) 5 [ppm] = 7.16 - 7.07 (m, 1 H, CH _Ar ), 6.53 - 6.45 (m, 1 H, CH _Ar ), 6.44 - 6.35 (m, 2H, CH _Ar ), 4.66 (s, 1 H), 3.81 (dd, J = 5.7, 1.3 Hz, 2H), 1.71 (hept, J = 6.2 Hz, 1 H), 1.50 - 1.35 (m, 2H), 1.35 - 1.29 (m, 4H), 0.99 - 0.85 (m, 6H).

¹³ C NMR (100 MHz, CDCh) 6 [ppm] = 161.0 (C _q ), 156.7 (C _q ), 130.2 (CH _Ar ), 107.5 (CH _Ar ), 107.3 (CH _Ar ), 102.2 (CH _Ar ), 70.6(CH ₂ ), 39.5 (CH), 30.7(CH ₂ ), 29.2 (CH ₂ ), 24.0 (CH ₂ ), 23.2 (CH ₂ ), 14.2(CH ₃ ), 11.2 (CH ₃ ).

IR (ATR) v [cm ¹ ] = 3376 (w), 2958 (m), 2927 (s), 2871 (m), 2860 (m), 1591 (vs), 1530 (m), 1494 (vs), 1458 (vs), 1371 (m), 1353 (s), 1327 (m), 1306 (m), 1282 (s), 1251 (s), 1232 (s), 1171 (vs), 1145 (vs), 1101 (s), 1028 (s), 1021 (s), 994 (m), 977 (m), 960 (m), 832 (vs), 796 (s), 765 (s), 728 (m), 684 (s), 642 (m), 629 (m), 622 (m), 596 (s), 528 (m), 511 (m), 460 (m).

FAB-MS m/z (%): 222 (27), 111 (18), 110 (100).

HRMS-FAB (m/z): [M + H] ⁺ calcd. for Ci ₄ H ₂ 2O ₂ , 222.1614; found, 222.1616.

[0172] Step 3: Preparation of Bemotrizinol (Friedel Crafts Acylation)

[0173] 2,4-Dichloro-6-(4-methoxyphenyl)-1 ,3,5-triazine (1.00 equiv) was dissolved in dichloromethane (10 ml). AlCh (2.30 equiv) and 3-((2-ethylhexyl)oxy)phenol (2.00 equiv) were added and the solution was stirred at 40 °C for 18 h. Subsequently, water was added to the mixture. The phases were separated, and the organic phase was washed with water (3x) and dried over Na2SO4. The solvent was removed under reduced pressure and the residue was purified via flash chromatography (SiO2, CH/EtOAc 20:1). Bemotrizinol was isolated as a yellow resin.

[0174] Example 5: Preparation of 3-((2-Ethylhexyl)oxy)phenol from resorcinol - acid catalyzed

[0175] Alternatively, resorcinol was dissolved in toluene. Isooctanol and p-toluene sulfonic acid monohydrate were added, and the solution was heated to 110 °C for 24 h. 3-((2- Ethylhexyl)oxy)phenol was obtained as a red oil.

[0176] Example 6: Preparation of 2,4-Dichloro-6-(4-methoxyphenyl)-1,3,5-triazine

[0177] Grignard Route:

[0178] Magnesium turnings (729 mg, 30.0 mmol, 1.00 equiv) was suspended in anhydrous THF (60 mL). 4-Bromoanisole (5.61 g, 3.75 mL, 30.0 mmol, 1.00 equiv) dissolved in anhydrous THF (100 mL) was added dropwise to the mixture while heating to 60 °C. The solution was stirred for 1.5 h. Subsequently, the mixture was added dropwise to a solution of cyanuric chloride (5.53 g, 30.0 mmol, 1.00 equiv) in anhydrous THF (100 mL) at 0 °C over 30 min. The solvent was removed under reduced pressure and the residue was washed with isopropanol and recrystallized from a mixture of toluene and hexane (1 :1). 2,4-Dichloro-6-(4- methoxyphenyl)-1 ,3,5-triazine was obtained as an off-white solid (4.40 g, 17.2 mmol, 57%).

[0179] Friedel Crafts Acylation Route:

[0180] Cyanuric chloride (100 mg, 542 pmol, 1.00 equiv) was dissolved in dichloromethane or chlorobenzene (10 ml). Nation beads (40 mg) and anisole (59 pL, 58.6 mg, 542 pmol, 1.00 equiv) were added and the solution was stirred at r.t. for 18 h (scheme 5). The solvent was removed under reduced pressure and the residue was washed with isopropanol and recrystallized from a mixture of toluene and hexane (1 :1). 2,4-Dichloro-6-(4-methoxyphenyl)- 1 ,3,5-triazine was obtained as an off-white solid (42 mg, 164 pmol, 30%).

[0181] The advantage of this route compared to the standard-Grignard-route is a considerable reduction in hazard potential. In addition, Nation is a solid catalyst allowing for facilitated handling.

[0182] According to an alternative route the triazine was obtained by dissolving cyanuric chloride (100 mg, 542 pmol, 1.00 equiv) in dichloromethane (10 ml). FeCh (99 mg, 1.25 mmol, 1.10 equiv) and anisole (59 pL, 58.6 mg, 542 pmol, 1.00 equiv) were added and the solution was stirred at r.t. for 18 h. Subsequently, water was added to the mixture. The phases were separated, and the organic phase was washed with water (3x) and dried over Na2SO4. The solvent was removed under reduced pressure and the residue was washed with isopropanol and recrystallized from a mixture of toluene and hexane (1 :1). 2,4-Dichloro-6-(4- methoxyphenyl)-1 ,3,5-triazine was obtained as an off-white solid (96 mg, 375 pmol, 69%).

[0183] The advantage of this route compared to the standard-Grignard-route is a considerable reduction in hazard potential. In addition, this approach allows for a significant increase in yield, reaching nearly 70%.

Scheme 7.

[0184] Based on this new route it was possible to considerably increase the yield. Accordingly, this route is more efficient compared to the standard Grignard-route and avoid all the disadvantages related to the use of Grignard reagents as specified above. Moreover, based on the Friedel Crafts Acylation Route it is possible to avoid the use of bromanisole (see scheme 1) by using the cheaper anisole educt (methoxybenzene).

[0185] It was found that other suitable catalysts are: AICI3 in CH2CI2 (10% yield), AICI3 in toluene (21 %), TiCU (23%). The formation of 2,4-dichloro-6-(4-methoxyphenyl)-1 ,3,5-triazine could also be observed for the following catalysts: FeFs, FeBrs, Feb, Sc(OTf)3, TfOH, Zeolithe- H, Mont. KSF.

F?r (SiO ₂ , CH/EtOAc, 4:1) = 0.66.

¹ H NMR (400 MHz, CDCI3) <5 [ppm] = 8.40 (dd, J = 8.9, 3.0 Hz, 2H), 6.96 (dd, J = 9.1 , 2.2 Hz, 2H), 3.89 (s, 3H).

¹³ C NMR (100 MHz, CDCI3) <5 [ppm] = 174.2 (C _q , C ^p ), 171.7 (2C, C _q ), 165.3 (C _q , COMe), 132.3 (2C, CH _Ar ), 125.1 (C _q , CN), 114.5(2C, CH _Ar ), 55.7 (CH ₃ ).

IR (ATR) v [cm- ¹ ] = 2975 (w), 2936 (w), 2901 (w), 2844 (w), 1604 (w), 1577 (w), 1514 (s), 1476 (vs), 1455 (s), 1442 (s), 1418 (m), 1388 (s), 1332 (w), 1317 (m), 1302 (m), 1256 (vs), 1244 (vs), 1180 (s), 1167 (s), 1152 (s), 1108 (s), 1016 (s), 975 (m), 902 (m), 844 (vs), 813 (s), 795 (vs), 776 (vs), 670 (s), 635 (m), 589 (vs), 547 (s), 510 (vs), 482 (s), 469 (s), 395 (m).

FAB-MS m/z (%): 259 (10), 258 (8), 257 (70), 256 (12), 255 [M + H] ⁺ (100), 159 (43), 133 (21), 118 (7), 103 (8), 90 (26), 89 (5), 87 (18), 69 (5), 63 (5).

HRMS-FAB (m/z): [M + H] ⁺ calcd. for CioH ₇ OiN ₃ ³⁵ Cl2, 254.9961 ; found, 254.9962. [0186] Example 7: Oxidative and electrochemically driven aromatization of cyclohexenone ether - 3-((2-Ethylhexyl)oxy)phenol via oxidative aromatization

[0187] Using stochiometric methods full conversion to the resorcinol monoether was achieved using iodine or IBX (scheme 8). Catalytic methods or photocatalytic methods did not lead to the desired reaction.

[0188] The conversion using electrochemistry was successful for the reaction depicted below (see Example 2).

Oxidative aromatization of cyclohexenone monoethers.

Scheme 8.

[0189] 3-((2-Ethylhexyl)oxy)cyclohex-2-en-1-one (135 mg, 602 p mol, I .OO equiv) was dissolved in water (10 mL). Iodine (183 mg, 722 pmol, 1.20 equiv) was added and the solution was stirred at r.t. for 24 h. After 24 h, GC/MS indicated complete conversion. Subsequently, the solution was extracted with DCM (3x) and the combined organic extracts were dried over Na2SC>4. The solvent was removed under reduced pressure. 3-((2-Ethylhexyl)oxy)phenol was obtained as a red oil (10 mg, 45 pmol, 7%).

[0190] Example 8: Formulation examples

[0191] In the following formulation examples the following five perfume oils PFO1 , PFO2, PFO3, PFO4 or PFO5 were each used as fragrance.

[0192] Table 1 : Composition of perfume oil 1 ; PO1) amounts in %o by weight)

[0193] Table 2: Composition of perfume oil 2; PO2 (amounts in %o by weight)

[0194] Table 3: Composition of perfume oil 3; PO3 (amounts in %o by weight)

[0195] Table 4: Composition of perfume oil 4; PO4 (amounts in %o by weight)

[0196] Table 5: Composition of perfume oil 5; PO5 (amounts in %o by weight)

[0197] The above perfume oils PO1 , PO2, PO3, PO4 or PO5 were incorporated into the formulations presented below.

[0198] Cosmetic formulations (compositions) (amounts in % by weight for all formulations).

[0199] Table 6: Sunscreen Oil Spray with Ethanol, expected SPF 30, UVA/UVB balanced

[0200] Table 7: Urban Sun Spray, o/w emulsion, expected SPF 50+ [0201] Table 8: Sunscreen Spray (O/W), expected SPF 30* (cold manufacturing process)

0202] Table 9: UV protection water spray, SPF 50

0203] Table 10: Sunscreen Spray, *SPF 50+, very water resistant**

[0204] Table 11 : Sunscreen Lotion (O/W), expected SPF 50* (cold/cold manufacturing process) 05] Table 12: Beach Time Lotion, SPF 30 206] Table 13: Anti-Sweat Sunscreen Lotion

207] Table 14: Sun protection milk (w/o) 208] Table 15: Protecting Watery Mousse, expected SPF 30* 209] Table 16: Full protection emulsion, expected SPF 50 210] Table 17: Whitening emulsion, expected SPF 50plus* 211] Table 18: Sunscreen Fluid for acne-prone Skin, expected SPF 30 212] Table 19: No More Shine Fluid, expected SPF50 213] Table 20: Light Sunscreen Fluid, expected SPF 50 214] Table 21 : Refreshing Gel Sunscreen, expected SPF 30, UVA/UVB balanced 215] Table 22: Sun protection balm, SPF 40

216] Table 23: Anti-Pollution Hair Care, SPF 15 217] Table 24: Perfect Hand emulsion, expected SPF 15, UVA/UVB balanced 218] Table 25: Tinted Sunscreen cream against hyperpigmentation 219] Table 26: BB Cream Dark Tone, expected SPF-20 220] Table 27: Daily Well Aging, SPF 30, UVA/UVB balanced, w/o Octocrylene 222] Table 29: Daily Tattoo Care, expected SPF 10, UVA/UVB balanced 223] Table 30: Sensitive Day Care Cream, expected SPF 15 224] Table 31 : Cream, expected SPF 15, UVA/UVB 225] Table 32: Air freshener (A/F spray water based)

Colorless liquid, pH neutral

0226] Table 33: All-purpose cleaner

Colorless liquid, pH 7

0227] Table 34: All-purpose cleaner

Colorless liquid, pH 7

0228] Table 35: All-purpose cleaner, alkaline

Colorless liquid, pH 9

0229] Table 36: Cleaner, liquid, citric acid

Liquid of low viscosity, pH 2

0230] Table 37: Cleaner, liquid, citric acid

Liquid of low viscosity, pH 2

0231] Table 38: Detergent liquid light duty Liquid, pH 7.3

0232] Table 39: Detergent liquid light duty

Liquid, pH 7.3

0233] Table 40: Dishwash liquid manual

Colorless liquid, pH 8.5

0234] Table 41 : Fabric softener

Liquid, pH 3

0235] Table 42: Fabric softener concentrate, encapsulated

White liquid, pH 2.5

0236] Table 43: Fabric softener concentrate, encapsulated White liquid, pH 2.5

0237] Table 44: Hand soap, liquid

Slightly colored liquid, pH 6

0238] Table 45: Rim block gel

Colorless paste/gel, pH = 4.5

0239] Table 46: Scent Lotion with capsules

White emulsion, pH neutral

0240] Table 47: Cleaner, liquid, lactic acid

Colorless liquid, pH 2,0

0241] Table 48: Cleaner, liquid, citric acid

Liquid, pH 2