Process for preparation of 2, 4, 6-substituted triazines

Abstract

The invention relates to a method for producing 2, 4, 6-substituted triazines of general formula (I) under sustainable and more environmentally friendly conditions. The invention also relates to 2, 4, 6-substituted triazines of formula (V). Furthermore, the present invention relates to aromatic compositions comprising 2, 4, 6-substituted triazines of formula (V). Furthermore, the present invention relates to the use of 2, 4, 6-substituted triazines of formula (V) for the absorption of ultraviolet rays, preferably in cosmetics, in particular in cream and domestic applications, more particularly in sunscreens.

Description

Technical Field

[0001] The present invention relates to a method for preparing 2,4,6-substituted triazines of general formula (I) under sustainable and more environmentally friendly conditions. The present invention also relates to 2,4,6-substituted triazines of formula (V). In addition, the present invention relates to a fragrance composition comprising 2,4,6-substituted triazines of formula (V). In addition, the present invention relates to the use of 2,4,6-substituted triazines of formula (V) for absorbing ultraviolet rays, preferably in cosmetics, in particular in creams and household applications, more particularly in sunscreens. Background Art

[0002] 2,4,6-substituted triazines are known in the art. One well-known 2,4,6-substituted triazine is 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxy-phenyl)-1,3,5-triazine, which is an oil-soluble organic compound added to sunscreens to effectively absorb UV rays. 2,4-bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-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 known as Bemotrizinol or Tinosorb S.

[0003] The preparation of 2,4,6-substituted triazines is also known in the prior art. Specifically, the three-step preparation of bemotriazine alcohol established is known to start from cyanuric chloride and 4-bromoanisole. In the first step, 4-bromoanisole and cyanuric chloride react in a Grignard reaction to obtain a monosubstituted product 6-(4-methoxyphenyl)-2,4-dichloro-1,3,5-triazine. In the second step, 6-(4-methoxyphenyl)-2,4-dichloro-1,3,5-triazine and benzene-1,3-diphenol (resorcinol) are reacted in the presence of AlCl3 in a Friedel-Crafts acylation to obtain the corresponding trisubstituted product 2,4-bis(2,4-dihydroxy-phenyl)-6-(4-methoxyphenyl)-1,3,5-triazine. In the third and final step, the trisubstituted product is reacted with 3-bromomethylheptane under basic conditions (eg in the presence of NaOH) to finally obtain bemotriazinol (Scheme 1).

[0004]

[0005] Although the synthesis of bemotriazine alcohol has been approved in practice, there are some disadvantages in the implementation of commercial scale. First, the use of Grignard reagents as known from organometallic compounds has high risks in terms of work safety, especially because reactive intermediates may react violently with water, i.e., these substances require special treatment and are not cheap, and are therefore not suitable for scale-up. In addition, the use of Grignard reagents and the use of stoichiometric amounts of AlCl3 (Friedel-Crafts acylation) in the second step and the use of alkyl halides in the third step lead to a large amount of halogenated waste. Therefore, the known methods for preparing 2,4,6-substituted triazines (such as bemotriazine alcohol) are questionable in terms of work safety and environmental sustainability. In addition, it is found that the intermediate reaction steps of the prior art synthesis of bemotriazine alcohol only show low selectivity. In addition, due to the low solubility of the diresorcinol-based triazine intermediate (diopat) in conventional solvents, high boiling point polar solvents such as methyl cellosolve are required, further reducing the overall sustainability of the entire synthesis. Therefore, the prior art methods are not effective and sustainable.

[0006] However, the demand for 2,4,6-substituted triazines, particularly 2,4,6-substituted triazines having the ability to effectively absorb ultraviolet rays, is very high.

[0007] Furthermore, in terms of sustainability and eco-friendliness, there is an increasing demand for reactions for the preparation of valuable bemotriazinol which result in a reduced amount of halogenated waste and also reduce the use of organometallic reagents. Therefore, another object of the present invention is to provide a greener and less toxic preparation process for bemotriazinol and other new valuable 2,4,6-substituted triazines as effective UV absorbers.

[0008] Furthermore, it is an object of the present invention to provide a convenient process with fewer synthesis steps, which avoids tedious chromatography and which allows a significant reduction of waste and costs. Furthermore, it is desirable to provide a new process that allows scale-up on an industrial scale.

[0009] Therefore, the main object of the present invention is to provide an improved process for preparing 2,4,6-substituted triazines of general formula (I) under sustainable and more environmentally friendly conditions. In addition, one object of the present invention is to provide a new process for preparing novel 2,4,6-substituted triazines. Another object is to provide a new 2,4,6-substituted triazine, which can be used as an effective absorber of ultraviolet rays, preferably in cosmetics such as sunscreens.

[0010] The present inventors have now surprisingly found a new process for producing 2,4,6-substituted triazines which is suitable for implementation on a commercial scale, avoids the use of Grignard reagents and produces lower amounts of halogenated waste. Summary of the invention

[0011] In a first aspect, the present invention relates to a process for preparing 2,4,6-substituted triazines of the general formula (I):

[0012]

[0013] wherein X represents an alkyl group or an aromatic group, preferably wherein X represents a methoxyphenyl group; and

[0014] - wherein Y and Z represent cyclohexenone ether;

[0015] or

[0016] - wherein Y and Z represent resorcinol monoether;

[0017] - wherein, in the case where Y and Z represent cyclohexenone ether, the compound of general formula (I) is obtained by reacting the cyclohexenone ether with a 2,4,6-substituted triazine under alkaline conditions and preferably in the presence of a strong base, more preferably in the presence of a non-nucleophilic base, even more preferably in the presence of a non-nucleophilic Li-amide base and most preferably in the presence of lithium diisopropylamide (LDA);

[0018] or

[0019] - wherein, in the case where Y and Z represent a resorcinol monoether, the compound of the general formula (I) is obtained by reaction of said resorcinol monoether with a 2,4,6-substituted triazine in an electrophilic aromatic substitution;

[0020] or

[0021] - wherein, when Y and Z represent resorcinol monoether, the compound of general formula (I) is obtained by reacting the resorcinol monoether with a 2,4,6-substituted triazine, followed by photoinduced rearrangement.

[0022] All reactions specified above are based on the reaction of 2,4,6-substituted triazines with ether (monoether) substituted six-membered cyclic carbon-based compounds.

[0023] Preferably, X represents an alkyl group or an aromatic group. The functional groups may be substituted by other functional groups or may be unsubstituted.

[0024] In a preferred embodiment of the present invention, where Y and Z represent cyclohexenone ether or resorcinol monoether, the compound of general formula (I) is obtained by reacting the cyclohexenone ether or the resorcinol ether with a 2,4,6-substituted triazine of general formula (II):

[0025]

[0026] - wherein R1 represents hydrogen or wherein R1 comprises or represents an alkyl or aromatic group, preferably wherein R1 represents methoxyphenyl; and

[0027] - wherein R2 represents a halogen atom; and

[0028] - wherein R3 represents a halogen atom.

[0029] Preferably, R1 represents an alkyl group or an aromatic group. The functional group may be substituted by other functional groups or may be unsubstituted.

[0030] In a preferred variant, where Y and Z represent cyclohexenone ether or resorcinol monoether, the compound of general formula (I) is obtained by reacting the cyclohexenone ether or the resorcinol ether with a 2,4,6-substituted triazine, wherein the 2,4,6-substituted triazine is 2,4-dichloro-6-(4-methoxyphenyl)triazine.

[0031] In a preferred variant, the cyclohexenone ether is a compound of the general formula (III):

[0032]

[0033] - wherein R4 represents a branched or straight chain alkyl group.

[0034] In a preferred variant, the resorcinol monoether is a compound of the general formula (IV):

[0035]

[0036] - wherein R5 represents a branched or straight chain alkyl group.

[0037] In a particularly preferred variant, in the case where Y and Z represent cyclohexenone ether, the compound of the general formula (I) is obtained by reaction of the cyclohexenone ether with a 2,4,6-substituted triazine under alkaline conditions, as specified herein, wherein the cyclohexenone ether is 3-(2-ethylhexyloxy)cyclohex-2-en-1-one and wherein the 2,4,6-substituted triazine is 2,4-dichloro-6-(4-methoxyphenyl)triazine.

[0038] In another particularly preferred variant, in which, in the case where Y and Z represent resorcinol monoether, the compound of the general formula (I) is obtained by reaction of the resorcinol monoether with a 2,4,6-substituted triazine in an electrophilic aromatic substitution, wherein the 2,4,6-substituted triazine is 2,4-dichloro-6-(4-methoxyphenyl)triazine, and wherein the resorcinol monoether is 3-(2-ethylhexyloxy)-phenol.

[0039] According to a further preferred variant, in which, in the case where Y and Z represent a resorcinol monoether, the compound of general formula (I) is obtained by reacting the resorcinol monoether with a 2,4,6-substituted triazine, followed by photoinduced rearrangement, wherein the resorcinol monoether is 3-(2-ethylhexyloxy)-phenol, and wherein the 2,4,6-substituted triazine is 2,4-dichloro-6-(4-methoxyphenyl)triazine.

[0040] In an alternative embodiment, the compound of the general formula (I), in which Y and Z represent resorcinol monoether, is obtained from the compound of the general formula (I), in which Y and Z represent cyclohexenone, by oxidative aromatization.

[0041] In another alternative of the present invention, the 2,4-dichloro-6-(4-methoxyphenyl)triazine is obtained by reacting 2,4,6-trichlorotriazine and methoxybenzene in the presence of at least one catalyst.

[0042] According to an embodiment of the present invention, the at least one catalyst is a solution containing a Lewis acid, and the Lewis acid is preferably AlCl3, TiCl4, FeCl3, FeI3, FeBr3, FeF3, Sc(OTf)3, BF3, TiCl4, TfOH, methanesulfonic acid or trifluoromethanesulfonic acid, or one of montmorillonite (Montmorillonit) KSF, Zeolith-Hβ or Nafion. Preferably, the catalyst is a solution containing a Lewis acid, and the Lewis acid is selected from AlCl3, FeCl3, TiCl4 (i.e., a Lewis acid containing chloride), TfOH, Nafion or a mixture of the above substances. The most preferred catalyst is selected from AlCl3, FeCl3, TiCl4 (i.e., a Lewis acid containing chloride) and Nafion.

[0043] According to a preferred embodiment, the catalyst used in the Friedel-Crafts reaction is a chloride-containing Lewis acid, preferably AlCl3, FeCl3 or TiCl4, most preferably FeCl3.

[0044] Preferably, the at least one catalyst is used in a substoichiometric amount.

[0045] In a second aspect, the present invention relates to 2,4,6-substituted triazines of formula (V):

[0046]

[0047] In a preferred variant, the compound of formula (V) is present in the form of:

[0048] Pure optically active enantiomers;

[0049] a racemic mixture of enantiomers; or

[0050] An optically active mixture of individual enantiomers.

[0051] In another aspect, the present invention relates to a fragrance composition comprising at least a compound of formula (V) and optionally at least one other fragrance substance.

[0052] In another aspect, the invention relates to the use of a compound according to the invention or a fragrance composition comprising a compound according to the invention as an odorant or fragrance compound or for improving the fixative of a fragrance compound or a composition comprising a fragrance compound or for preparing a perfumed product.

[0053] Furthermore, the invention relates to the use of the compounds according to the invention for preparing cosmetic or home care compositions.

[0054] Furthermore, in a fourth aspect, the present invention relates to a cosmetic composition or home care composition, preferably a sunscreen formulation or product, comprising at least a compound of formula (V).

[0055] In a preferred variant of the invention, the cosmetic or home care composition is a cream.

[0056] More preferably, the cosmetic composition is a sunscreen.

[0057] In another aspect, the invention relates to a perfumed product comprising a compound according to the invention or a fragrance composition comprising a compound of formula (I).

[0058] In another aspect, the invention relates to a perfuming product comprising an effective amount of a compound according to the invention or a fragrance composition comprising a compound according to the invention and a carrier or base.

[0059] Finally, the present invention relates to a perfumed product as defined, comprising a compound according to the invention or a fragrance composition comprising a compound according to the invention, wherein the perfumed product is a perfume oil, a perfume base, a personal hygiene preparation, a cleaning agent or an air freshener. According to the invention, this encompasses all household applications, such as laundry detergents, fabric softeners and other applications as mentioned in the formulation section (see the formulation examples below).

[0060] The present inventors have now established a process for producing 2,4,6-substituted triazines which does not use any Grignard reagent and in which the amount of halogenated waste is significantly reduced.

[0061] Furthermore, the present invention provides a greener and less toxic preparation process (reduced salt frequency, reduced toxic reactants and solvents) of bemotriazineol and other new valuable 2,4,6-substituted triazines as effective UV absorbers.

[0062] Furthermore, the present invention provides a convenient process with fewer synthesis steps, which avoids tedious chromatography and which allows a significant reduction of waste and costs. Furthermore, the new process according to the present invention allows for scale-up on an industrial scale. DETAILED DESCRIPTION

[0063] According to the present invention, the above object is achieved by a method for preparing a 2,4,6-substituted triazine of general formula (I):

[0064]

[0065] wherein X represents an alkyl or aromatic group, and preferably wherein X represents a methoxyphenyl group; and wherein Y and Z represent cyclohexenone ether;

[0066] or

[0067] - wherein Y and Z represent resorcinol monoether;

[0068] - wherein, in the case where Y and Z represent cyclohexenone ether, the compound of general formula (I) is obtained by reacting the cyclohexenone ether with a 2,4,6-substituted triazine under alkaline conditions, preferably in the presence of a strong base, more preferably in the presence of a non-nucleophilic base, even more preferably in the presence of a non-nucleophilic Li-amide base, most preferably in the presence of lithium diisopropylamide (LDA);

[0069] or

[0070] - wherein, in the case where Y and Z represent a resorcinol monoether, the compound of the general formula (I) is obtained by reaction of said resorcinol monoether with a 2,4,6-substituted triazine in an electrophilic aromatic substitution;

[0071] or

[0072] - wherein, when Y and Z represent resorcinol monoether, the compound of general formula (I) is obtained by reacting the resorcinol monoether with a 2,4,6-substituted triazine, followed by photoinduced rearrangement.

[0073] Preferably, X represents an alkyl group or an aromatic group. The functional groups may be substituted by other functional groups or may be unsubstituted.

[0074] Preferably, in the case where Y and Z represent cyclohexenone ether, the reaction is carried out under alkaline conditions, i.e. in the presence of a base, and preferably in the presence of a strong base, more preferably in the presence of a non-nucleophilic base, even more preferably in the presence of a non-nucleophilic Li-amide base such as lithium diisopropylamide (LDA) (see Example 1).

[0075] Alternatively, other strong bases such as lithium bis(trimethylsilyl)amide (LiHMDS) or potassium tert-butoxide (KOt-Bu) may be advantageously used instead of LDA.

[0076] Preferably, the base is a strong base with a pKa of 20 or higher, further preferably a pKa of 25 or higher, more preferably a pKa of 30 or higher and most preferably a pKa of 35 or higher.

[0077] Even more preferably, the alkaline conditions for the reaction of the cyclohexenone ether with the 2,4,6-substituted triazine are established by providing a non-nucleophilic base. The use of such a non-nucleophilic base allows for an effective reduction in 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-butylpyridine, 1,5-diazabicyclo(4.3.0)non-5-ene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), bis(trimethylsilyl)lithium amide (LiHMDS or Li(HMDS)), lithium diisopropylamide (LDA), lithium tert-butoxide, lithium tetramethylpiperidinium (LiTMP or harpoon base), 2,4-lutidine, 2,6 -lutidine, 3,5-lutidine, N,N-diisopropylethylamine (DIPEA, DIEA or i-Pr2Net), neopentyl lithium, 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 a mixture thereof.

[0078] These bases are sterically hindered organic bases that are weak nucleophiles that are generally bulky so that protons can attach to the basic center, but alkylation and complexation are inhibited.

[0079] Even more preferably, the basic conditions for the reaction of cyclohexenone ether with 2,4,6-substituted triazines are established by providing a non-nucleophilic Li-amide base such as lithium bis(trimethylsilyl)amide (LiHMDS or Li(HMDS)), lithium diisopropylamide (LDA), lithium tetramethylpiperidinium (LiTMP or harpoon base) and mixtures thereof. For these bases, the best results were achieved in terms of selectivity and yield.

[0080] It was found that nucleophilic bases such as n-butyllithium (n-BuLi) or sodium amide (NaNH2) failed to provide the desired product.

[0081] According to a preferred variant of the invention of the first aspect, X represents an alkyl or aromatic group. Preferably, X represents a methoxyphenyl group. In this case, the resulting compound exhibits significant UV absorption properties. Therefore, in a preferred variant, the present invention relates to a process for preparing a 2,4,6-substituted triazine of general formula (Ia):

[0082]

[0083] - wherein Y and Z represent cyclohexenone ether;

[0084] or

[0085] - wherein Y and Z represent resorcinol monoether;

[0086] According to the invention, 2,4,6-substituted triazines of the general formula (I) are obtainable by various routes, in each case without the use of Grignard reagents and with a significantly reduced amount of halogenated waste, thus under more environmentally friendly conditions.

[0087] In the case where Y and Z represent cyclohexenone ethers, the compounds of the general formula (I) are obtained in a first variant by reacting the cyclohexenone ethers with 2,4,6-substituted triazines under alkaline conditions, preferably in the presence of a strong base, more preferably in the presence of a non-nucleophilic base, even more preferably in the presence of a non-nucleophilic Li-amide base, as described above, for example in the presence of lithium diisopropylamide (LDA).

[0088] Preferably, the cyclohexenone ether is present as its enolate, which can be obtained by reaction with a strong base, more preferably in the presence of a non-nucleophilic base, even more preferably in the presence of a non-nucleophilic Li-amide base such as lithium diisopropylamide (LDA). Therefore, in a preferred embodiment of the present invention, the cyclohexenone enolate and the 2,4,6-substituted triazine are reacted in a nucleophilic aromatic substitution.

[0089] The use of the enolate form avoids the use of halide-containing precursors, thereby making the process greener and more sustainable by avoiding halide waste. In addition, high selectivities can be achieved.

[0090] Therefore, according to the present invention, 2,4,6-substituted triazines can be obtained without any Grignard reagent, and the amount of halogenated waste is significantly reduced.

[0091] In the case where Y and Z represent resorcinol monoethers, the compounds of the general formula (I) are obtained in a second variant by reaction of said resorcinol monoethers with 2,4,6-substituted triazines in an electrophilic aromatic substitution.

[0092] The reaction of the resorcinol monoether with a 2,4,6-substituted triazine in an electrophilic aromatic substitution is a Friedel-Crafts acylation catalyzed by a Lewis acid.

[0093] Therefore, the reaction of resorcinol monoether with 2,4,6-substituted triazine does not require any Grignard reagent. Therefore, according to the present invention, 2,4,6-substituted triazine can be obtained without any Grignard reagent, and the amount of halogenated waste is significantly reduced.

[0094] In the case where Y and Z represent resorcinol monoethers, the compounds of the general formula (I) are obtained in a third variant by reaction of said resorcinol monoethers with 2,4,6-substituted triazines followed by photoinduced rearrangement.

[0095] First, the deprotonated resorcinol monoether reacts with a 2,4,6-substituted triazine in a nucleophilic aromatic substitution to give an O-bridged intermediate, which is then subjected to a photoinduced rearrangement to give compounds of general formula (I).

[0096] Preferably, the light-induced rearrangement is a Photo-Fries rearrangement.

[0097] Therefore, no Grignard reagent is required. Therefore, according to the present invention, 2,4,6-substituted triazines can be obtained without any Grignard reagent, and the amount of halogenated waste is significantly reduced.

[0098] In a preferred variant of the invention, in which case Y and Z represent cyclohexenone ether or resorcinol monoether, the compound of general formula (I) is obtained by reaction of said cyclohexenone ether or said resorcinol ether with a 2,4,6-substituted triazine of general formula (II):

[0099]

[0100] - wherein R1 represents hydrogen or wherein R1 comprises or represents an alkyl or aromatic group, preferably wherein R1 represents methoxyphenyl; and

[0101] - wherein R2 represents a halogen atom; and

[0102] - wherein R3 represents a halogen atom.

[0103] Preferably, R1 represents an alkyl group or an aromatic group. The functional group may be substituted by other functional groups or may be unsubstituted.

[0104] According to a preferred variant of the invention, R1 represents a group comprising an alkyl group or an aromatic group. Preferably, R1 represents a methoxyphenyl group. In this case, the resulting compound exhibits significant UV absorption properties. Therefore, in a preferred variant, the present invention relates to a method for reacting the cyclohexenone ether or the resorcinol ether with a 2,4,6-substituted triazine of the general formula (IIa):

[0105]

[0106] - wherein R2 represents a halogen atom; and

[0107] - wherein R3 represents a halogen atom.

[0108] Preferably, R2 is selected from chlorine, bromine, iodine, even more preferably chlorine.

[0109] Preferably, R3 is selected from chlorine, bromine, iodine, even more preferably chlorine.

[0110] According to another preferred variant of the invention, R2 is different from R3.

[0111] According to an alternative and more preferred variant, R2 represents the same functional group as R3 (R2=R3).

[0112] According to a particularly preferred embodiment, the 2,4,6-substituted triazine of the general formula (II) or (IIa) is 2,4-dichloro-6-(4-methoxyphenyl)triazine.

[0113] The 2,4,6-substituted triazines of the general formula (II) are excellent starting materials for preparing the 2,4,6-substituted triazines of the general formula (I), since the compounds of the general formula (II) are highly reactive due to the substituents R2, R3, and furthermore, the compounds of the general formula (II) enable the preparation of the 2,4,6-substituted triazines of the general formula (I) in a very environmentally friendly manner, in particular without the use of Grignard reagents.

[0114] According to a preferred embodiment, the compound of formula (II) or (IIa), more specifically the 2,4,6-substituted triazine of general formula (II) or (IIa) is prepared by replacing the Grignard reaction of cyanuric chloride according to the prior art with Friedel-Crafts acylation of anisole, the Friedel-Crafts acylation occurring under fairly mild conditions. Therefore, preferably, a Lewis acid such as AlCl3 as a catalyst is preferably added in a substoichiometric to stoichiometric amount. Other suitable catalysts are TiCl4, FeCl3, FeI3, FeBr3, FeF3, Sc(OTf)3, BF3, TiCl4, TfOH, methanesulfonic acid or trifluoromethanesulfonic acid or one of montmorillonite KSF, Zeolith-Hβ or Nafion. Preferably, the catalyst is a solution containing a Lewis acid, the Lewis acid being selected from AlCl3, FeCl3, TiCl4 (i.e., a chloride-containing Lewis acid), TfOH, Nafion or a mixture of the above substances. The most preferred catalyst is selected from AlCl3, FeCl3, TiCl4 (ie, chloride-containing Lewis acids), and Nafion.

[0115] According to a preferred embodiment, the catalyst used in the Friedel-Crafts reaction is a chloride-containing Lewis acid, preferably AlCl3, FeCl3 or TiCl4, most preferably FeCl3.

[0116] It was found that the above Lewis acids achieve excellent formation of 2,4,6-substituted triazines of formula (II) or (IIa). The reaction can be successfully carried out at room temperature in conventional solvents such as CH2Cl2, toluene, acetonitrile (MeCN) or 1,2-dichlorobenzene (DCB). For AlCl3, the best results are achieved when used in stoichiometric amounts. However, substoichiometric amounts also produce the desired product.

[0117] In one embodiment of the present invention, where Y and Z represent cyclohexenone ether or resorcinol monoether, the compound of general formula (I) is obtained by reacting the cyclohexenone ether or the 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 described above.

[0118] 2,4-Dichloro-6-(4-methoxyphenyl)triazine is a highly reactive compound which is suitable for preparing 2,4,6-substituted triazines of the general formula (I) in a very environmentally friendly manner, in particular without using Grignard reagents. In addition, 2,4-dichloro-6-(4-methoxyphenyl)triazine is non-toxic and easy to prepare.

[0119] In another embodiment of the present invention, the cyclohexenone ether is a compound of formula (III):

[0120]

[0121] - wherein R4 represents a branched or straight chain alkyl group.

[0122] According to a preferred variant of the invention, R4 represents a linear or branched C1-C12 alkyl group, preferably a linear or branched C4-C10 alkyl group, even more preferably a linear or branched C6-C10 alkyl group. Most preferably R4 is a C8 alkyl group.

[0123] According to the most preferred variant, R4 is isooctyl. Therefore, according to the most preferred embodiment, the cyclohexenone ether is a compound of formula (IIIa):

[0124]

[0125] According to a particularly preferred embodiment, the cyclohexenone ether of the general formula (III) or (IIIa) is 3-(2-ethylhexyloxy)cyclohex-2-en-1-one.

[0126] Cyclohexenone ethers of the general formula (III) are excellent starting materials for preparing 2,4,6-substituted triazines of the general formula (I) since they are readily available, non-toxic and furthermore enable the preparation of 2,4,6-substituted triazines of the general formula (I) in a very environmentally friendly manner.

[0127] The compound of the general formula (III) can be obtained from 1,3-cyclohexanedione and the corresponding alcohol (see Example 1).

[0128] In yet another variant of the present invention, the resorcinol monoether is a compound of general formula (IV):

[0129]

[0130] - wherein R5 represents a branched or straight chain alkyl group.

[0131] According to a preferred variant of the invention, R5 represents a linear or branched C1-C12 alkyl group, preferably a linear or branched C4-C10 alkyl group, even more preferably a linear or branched C6-C10 alkyl group. Most preferably, R5 is a C8 alkyl group.

[0132] According to the most preferred variant, R5 is isooctyl. Therefore, according to the most preferred embodiment, the resorcinol monoether is a compound of general formula (IVa):

[0133]

[0134] According to a particularly preferred embodiment, the resorcinol monoether of the general formula (IV) or (IVa) is 3-(2-ethylhexyloxy)phenol.

[0135] Resorcinol monoethers of the general formula (IV) are excellent starting materials for preparing 2,4,6-substituted triazines of the general formula (I) since they are readily available, non-toxic and furthermore enable the preparation of 2,4,6-substituted triazines of the general formula (I) in a very environmentally friendly manner.

[0136] 3-(2-Ethylhexyloxy)phenol can be obtained from 1,3-cyclohexanedione and isooctyl alcohol by oxidative aromatization.

[0137] In a preferred variant, wherein Y and Z represent cyclohexenone ether, the compound of general formula (I) is obtained by reacting the cyclohexenone ether with a 2,4,6-substituted triazine under alkaline conditions (preferably in the presence of a strong base, more preferably in the presence of a non-nucleophilic base, even more preferably in the presence of a non-nucleophilic Li-amide base, most preferably in the presence of lithium diisopropylamide (LDA)), wherein the cyclohexenone ether is 3-(2-ethylhexyloxy)cyclohex-2-en-1-one, and wherein the 2,4,6-substituted triazine is 2,4-dichloro-6-(4-methoxyphenyl)triazine.

[0138] 3-(2-ethylhexyloxy)cyclohex-2-en-1-one and 2,4-dichloro-6-(4-methoxy-phenyl)triazine (or the corresponding bromide or iodide compounds) are both excellent starting materials for the preparation of 2,4,6-substituted triazines of general formula (I), and the combination of the two is even better. 2,4-dichloro-6-(4-methoxyphenyl)triazine is a highly reactive compound suitable for the preparation of 2,4,6-substituted triazines of general formula (I) in a very environmentally friendly manner. In addition, 2,4-dichloro-6-(4-methoxyphenyl)triazine is non-toxic and easy to prepare. In addition, 3-(2-ethylhexyloxy)-cyclohex-2-en-1-one is easily available, non-toxic, and in addition enables the preparation of 2,4,6-substituted triazines of general formula (I) in a very environmentally friendly manner, in particular without the use of Grignard reagents.

[0139] Preferably, the cyclohexenone ether 3-(2-ethylhexyloxy)cyclohex-2-en-1-one is present as its enolate, which can be obtained by reaction with a strong base (preferably in the presence of a non-nucleophilic base, even more preferably in the presence of a non-nucleophilic Li-amide base) such as lithium diisopropylamide (LDA). Therefore, in a preferred embodiment of the present invention, the corresponding enolate from 3-(2-ethylhexyloxy)cyclohex-2-en-1-one and the 2,4,6-substituted triazine, i.e. 2,4-dichloro-6-(4-methoxyphenyl)triazine, are reacted in a nucleophilic aromatic substitution without using any Grignard reagent and, moreover, with a reduced amount of halogenated waste and, therefore, under environmentally friendly reaction conditions. This route is advantageous, on the one hand, because it avoids the poorly soluble intermediate diopate and, on the other hand, bypasses the less selective monoetherification of resorcinol.

[0140] Therefore, preferably, when Y and Z represent cyclohexenone ether, the reaction is carried out under basic conditions, i.e. in the presence of a base, and preferably in the presence of a strong base, more preferably in the presence of a non-nucleophilic base, even more preferably in the presence of a non-nucleophilic Li-amide base such as lithium diisopropylamide (LDA) (see Example 1).

[0141] Alternatively, other strong bases such as lithium bis(trimethylsilyl)amide (LiHMDS) or potassium tert-butoxide (KOt-Bu) may be advantageously used instead of LDA.

[0142] 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-one), corresponding to the 2,4,6-substituted triazine of formula (V).

[0143] The compound of general formula (III) can be obtained from 1,3-cyclohexanedione and the corresponding alcohol as described above. Therefore, 3-(2-ethylhexyloxy)cyclohex-2-ene-1-one can be obtained from 1,3-cyclohexanedione and isooctyl alcohol. The reaction is preferably carried out in the presence of a strong acid such as methanesulfonic acid (MSA). Alternatively, p-toluenesulfonic acid (PTSA or pTsOH) or toluenesulfonic acid (TsOH) can be used instead of MSA. Other strong acids (preferably sulfonic acids) can also be used for this purpose. The acid preferably has a pKa value of -1 or less.

[0144] In another preferred variant, in which Y and Z represent resorcinol monoethers, the compound of the general formula (I) is obtained by reaction of the resorcinol monoether with a 2,4,6-substituted triazine in an electrophilic aromatic substitution, wherein the 2,4,6-substituted triazine is preferably 2,4-dichloro-6-(4-methoxyphenyl)triazine, and wherein the resorcinol monoether is preferably 3-(2-ethylhexyloxy)phenol.

[0145] The reaction of 3-(2-ethylhexyloxy)phenol with 2,4-dichloro-6-(4-methoxyphenyl)triazine (or the corresponding bromide or iodide) in electrophilic aromatic substitution is a Friedel-Crafts acylation catalyzed by a Lewis acid, preferably by AlCl3. Preferably, the Lewis acid is added in a substoichiometric amount. Other suitable catalysts are one of TiCl4, FeCl3, FeI3, FeBr3, FeF3, Sc(OTf)3, BF3, TiCl4, TfOH, methanesulfonic acid or trifluoromethanesulfonic acid or montmorillonite KSF, Zeolith-Hβ or Nafion. Preferably, the catalyst is a solution containing a Lewis acid, the Lewis acid being selected from AlCl3, FeCl3, TiCl4 (i.e., a chloride-containing Lewis acid), TfOH, Nafion or a mixture of the above substances. The most preferred catalyst is selected from AlCl3, FeCl3, TiCl4 (i.e., a chloride-containing Lewis acid), Nafion.

[0146] According to a preferred embodiment, the catalyst used in the Friedel-Crafts reaction is a chloride-containing Lewis acid, preferably AlCl3, FeCl3 or TiCl4, most preferably FeCl3.

[0147] Therefore, the reaction of resorcinol monoether 3-(2-ethylhexyloxy)phenol with 2,4,6-substituted triazine 2,4-dichloro-6-(4-methoxyphenyl)triazine in Friedel-Crafts reaction does not require any Grignard reagent. Therefore, according to the present invention, 2,4,6-substituted triazines of general formula (I) can be obtained without any Grignard reagent, and the amount of halogenated waste is significantly reduced. In addition, 3-(2-ethylhexyloxy)phenol is easily available and non-toxic. In addition, 2,4-dichloro-6-(4-methoxyphenyl)triazine is non-toxic and easily available.

[0148] 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 known as bemotriazinol.

[0149] Therefore, the method according to the present invention enables the preparation of bemotriazine alcohol, which is widely used as a compound capable of absorbing ultraviolet rays, in an environmentally friendly manner.

[0150] In another embodiment of the present invention, wherein Y and Z represent resorcinol monoether, the compound of general formula (I) is obtained by reacting the resorcinol monoether with a 2,4,6-substituted triazine, followed by photoinduced rearrangement, wherein the resorcinol monoether is 3-(2-ethylhexyloxy)phenol, and wherein the 2,4,6-substituted triazine is 2,4-dichloro-6-(4-methoxyphenyl)triazine.

[0151] 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 known as bemotriazinol.

[0152] The process according to the invention thus enables another way to obtain bemotriazine alcohol in an environmentally friendly manner.

[0153] Based on this, two other routes to bemotriazine alcohol 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 2,4-dichloro-6-(4-methoxyphenyl)triazine to give the O-brominated intermediate, which is subsequently rearranged to BEMT in a Photo-Frieβ rearrangement.

[0154] In one embodiment of the present invention, compounds of the general formula (I) in which Y and Z represent resorcinol monoethers are obtained by oxidative aromatization from compounds of the general formula (I) in which Y and Z represent cyclohexenone.

[0155] Therefore, compounds of general formula (I) wherein Y and Z represent cyclohexenone are suitable starting materials for preparing different compounds of general formula (I) wherein Y and Z represent resorcinol monoether. In addition, oxidative aromatization is an eco-friendly and non-toxic process for producing compounds of general formula (I) since no by-products or waste are generated.

[0156] According to the invention, in the case where 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 known as bemotriazinol), the bemotriazinol is obtained by oxidative aromatization 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 the 2,4,6-substituted triazine of formula (V)).

[0157] In one embodiment of the present invention, the 2,4-dichloro-6-(4-methoxyphenyl)triazine is obtained by reacting 2,4,6-trichlorotriazine and methoxybenzene in the presence of at least one catalyst.

[0158] The Friedel-Crafts reaction of 2,4,6-trichlorotriazine (also known as cyanuric chloride) and methoxybenzene does not require any Grignard reagent and is therefore more environmentally friendly.

[0159] Preferably, the at least one catalyst is a solution containing a Lewis acid, and the Lewis acid is preferably one of AlCl3, TiCl4, FeCl3, FeI3, FeBr3, FeF3, Sc(OTf)3 or trifluoromethanesulfonic acid or montmorillonite KSF, Zeolith-Hβ or Nafion. Preferably, the catalyst is a solution containing a Lewis acid, and the Lewis acid is selected from AlCl3, FeCl3, TiCl4 (i.e., a Lewis acid containing chloride), TfOH, Nafion or a mixture of the above substances. The most preferred catalyst is selected from AlCl3, FeCl3, TiCl4 (i.e., a Lewis acid containing chloride), Nafion.

[0160] According to a preferred embodiment, the catalyst used in the Friedel-Crafts reaction is a chloride-containing Lewis acid, preferably AlCl3, FeCl3 or TiCl4, most preferably FeCl3.

[0161] In order to reduce halogenated wastes, the at least one catalyst is used in a substoichiometric amount.

[0162] Whenever a compound of the general formula (I) is mentioned in the present description, this is taken to mean all stereoisomers, in particular all enantiomers, indiscriminately the isomerically pure stereoisomers or any mixture of stereoisomers thereof. For economic reasons, the compounds are preferably used as mixtures of their stereoisomers, in particular mixtures of their enantiomers.

[0163] Therefore, the compounds of general formula (I) exist in the following forms:

[0164] (a) pure optically active enantiomers;

[0165] (b) a racemic mixture of enantiomers; or

[0166] (c) An optically active mixture of individual enantiomers.

[0167] In a second aspect, the present invention relates to 2,4,6-substituted triazines of formula (V):

[0168]

[0169] The 2,4,6-substituted triazines of formula (V) can be obtained as described above from 3-(2-ethylhexyloxy)cyclohex-2-en-1-one and 2,4-dichloro-6-(4-methoxyphenyl)triazine.

[0170] Surprisingly it has been found that the substances according to formula (V), which are also denoted tetrahydro-BEMT (BEMT stands for bemotriazinol), show excellent UV-absorbing properties and are therefore effective novel UV filters.

[0171] Therefore, in another variant, the present invention also relates to the use of compounds of general formula (V) for the preparation of a wide range of consumer products (preferably sunscreens), more specifically as UV absorbers and for the preparation of UV absorbing products. In addition, the present invention also relates to these products themselves, i.e. to consumer products (preferably sunscreens) and UV absorbers comprising compounds of general formula (V).

[0172] Preferably, the cyclohexenone ether 3-(2-ethylhexyloxy)cyclohex-2-ene-1-one is present as its enolate, which can be obtained by reaction with a strong base, more preferably in the presence of a non-nucleophilic base, even more preferably in the presence of a non-nucleophilic Li-amide base such as lithium diisopropylamide (LDA). Other suitable strong bases are as described above. Therefore, in a preferred embodiment of the present invention, the corresponding enolate from 3-(2-ethylhexyloxy)cyclohex-2-ene-1-one and 2,4,6-substituted triazine, i.e., 2,4-dichloro-6-(4-methoxyphenyl)triazine, react in a nucleophilic aromatic substitution, and the amount of halogenated waste is reduced, so it is under environmentally friendly reaction conditions.

[0173] Subsequently, the compound of general formula (V) can be converted to bemotriazinol by oxidative aromatization. This can be accomplished electrochemically using a gold electrode.

[0174] An overview of the reaction according to the invention is shown below (Scheme 2):

[0175]

[0176] As shown above, cyclohexenone monoether can also be oxidized to resorcinol monoether before attachment to the triazine core. Resorcinol monoether can be attached to 2,4-dichloro-6-(4-methoxyphenyl)triazine in a Friedel-Crafts acylation to directly produce BMT. Alternatively, resorcinol monoether and triazine can be attached via nucleophilic substitution to obtain an O-arylated intermediate. Potentially, this can be converted to BMT in a photo-Fries rearrangement.

[0177] Whenever a 2,4,6-substituted triazine of formula (V) is mentioned in the present description, this is taken to mean all stereoisomers, in particular all enantiomers, indiscriminately the isomerically pure stereoisomers or any mixture of stereoisomers thereof. For economic reasons, the compounds are preferably used as mixtures of their stereoisomers, in particular mixtures of their enantiomers.

[0178] Therefore, the present invention also discloses mixtures of any of the above mentioned compounds and / or mixtures of any of the above mentioned stereoisomers and the use of such compounds and / or mixtures within the meaning of the present application.

[0179] Generally, in the context of the present invention, the term "compound of formula (I)" refers to individual compounds of formula (I) (and their isomeric forms) and all mixtures of compounds of formula (I) (and isomeric forms) in any mixing ratio. That is, the statements about "compound of formula (I)" in the following description apply not only to a single compound of formula (I), a single isomeric form, but also to a mixture of compounds of formula (I) and their isomeric forms composed of or containing compounds of formula (I) and their isomeric forms in any mixing ratio. Therefore, the present invention relates to individual compounds according to the present invention per se or also mixtures of compounds according to the present invention. The same applies to 2,4,6-substituted triazines of formula (V).

[0180] The compounds of general formula (I) according to the invention can be used as a single substance or mixed with at least one other known aromatic substance, the aromatic substance being selected from a wide range of natural and synthetic substances available in a large number of aromatic mixtures, and / or mixed with one or more ingredients or excipients (e.g. carrier materials and other auxiliaries commonly used in the art) commonly used in combination with flavor enhancers in aromatic compositions. The same applies to 2,4,6-substituted triazines of formula (V).

[0181] Therefore, in another aspect, the present invention relates to a fragrance composition comprising at least one compound according to the present invention and at least one other fragrance substance. In particular, the present invention relates to a fragrance composition comprising at least a 2,4,6-substituted triazine of formula (V).

[0182] The aroma substances specified below may be used as individual substances or in admixture with at least one, two, three or even more aroma substances selected from a large number of aroma mixtures of natural and synthetic substances.

[0183] Fragrance substances advantageously suitable for combination are listed, for example, in S. Arctander, Perfume and Flavor Materials, Volumes I and II, Montclair, NJ 1969, private publication and / or H. Surburg, J. Panten, Common Fragrance and Flavor Materials, 6th edition, Wiley-VCH, Weinheim 2016. The following list includes examples of known odorous substances advantageously suitable for combination with the compounds according to the invention and mixtures thereof:

[0184] Extracts of natural raw materials, for example essential oils, extracts, absolutes, resins, balsams, tinctures, for example ambergris tincture; balsam oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; moss absolute; laurel oil; artemisia oil; benzoin resin; bergamot oil; beeswax absolute; birch tar; bitter almond oil; savory oil; buchu leaf oil; balsam bean oil; juniper oil; calamus oil; camphor oil; ylang-ylang oil; cardamom oil; cassia oil; cinnamon oil; tin absolute; castoreum absolute; cedar leaf oil; cypress oil; labdanum oil; citronella oil; lemon oil; cupaba oil; cupaba balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill weed oil; dill seed oil; eau de coix brouts absolute; oakmoss absolute; elemi oil; tarragon oil; lemon eucalyptus oil; eucalyptus oil; anise oil; pine needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; gujun balsam; gujun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; orris root absolute; orris root oil; jasmine absolute; calamus oil; blue chamomile oil; Roman chamomile oil; carrot seed oil; cassia oil; pine needle oil; spearmint oil; Caraway oil; Cistus oil; Cistus absolute; Cistus resin; Lavender absolute; Lavandula oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Lime oil distilled; Lime oil pressed; Camphor oil; Litsea cubeba oil; Bay leaf oil; Nutmeg oil; Marjoram oil; Orange oil; Cinnamon bark oil; Mimosa absolute; Ambrette oil; Musk tincture; Musk sage oil; Nutmeg oil; Myrrh absolute; Myrrh oil; Myrtle Oil; Clove Leaf Oil; Clove Bud Oil; Neroli Oil; Frankincense Absolute; Frankincense Oil; Poppy Oil; Neroli Absolute; Orange Oil; Oregano Oil; Palmarosa Oil; Patchouli Oil; Perilla Oil; Peru Balsam Oil; Parsley Leaf Oil; Parsley Seed Oil; Orange Leaf Oil; Peppermint Oil; Peppermint Oil; Pine Oil; Peppermint 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; Marigold oil; Fir needle oil; Tea tree oil; Turpentine oil; Thyme oil; Tolu balsam; Tonka bean extract; Tuberose absolute; Vanilla extract; Violet leaf absolute; Verbena oil; Vetiver oil; Juniper berry oil; Cognac oil; Wormwood oil; Wintergreen oil; Ylang-ylang oil; Achyranthes oil; Civet absolute; Cinnamon leaf oil; Cinnamon bark oil and fractions thereof or components isolated therefrom;

[0185] Various aromatic substances selected from hydrocarbons, for example: 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane;

[0186] Aliphatic alcohols, for example: hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenols; 1-octen-3-ol; a mixture 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;

[0187] Aliphatic aldehydes and acetals thereof, 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-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal; heptaldehyde diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; 1-(1-methoxypropoxy)-(E / Z)-3-hexene;

[0188] Aliphatic ketones and their oximes, 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;

[0189] Aliphatic sulfur compounds, for example: 3-methylthio-hexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercapto-hexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;

[0190] Aliphatic nitriles, for example: 2-nonenenitrile; 2-undecenenitrile; 2-tridecenenitrile; 3,12-tridecadienenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile;

[0191] Esters of aliphatic carboxylic acids, 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; butyric acid hexyl ester; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octanoate; methyl 2-nonanoate; allyl 2-isopentyloxyacetate; methyl 3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl crotonate;

[0192] Acyclic terpene alcohols, 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 their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters and 3-methyl-2-butenoate esters;

[0193] Acyclic terpene aldehydes and ketones, for example: geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial, neral and 7-hydroxy-3,7-dimethyloctanal;

[0194] Cyclic terpene alcohols, for example: menthol; isopulegol; α-terpineol; terpinenol-4; menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; aminobenzyl alcohol; vetiverol; guaiacol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters and 3-methyl-2-butenoate esters;

[0195] Cyclic terpene aldehydes and ketones, for example: menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; α-ionone; β-ionone; α-N-methylionone; β-N-methylionone; α-isomethylionone; β-isomethylionone; α-irone; α-damascenone; β-damascenone; β-damascenone; δ-damascenone; γ-damascenone; 1-(2,4,4-trimethyl-2-cyclohexane)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1 Hexen-1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methylenenaphthalene-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; nootkatone; dihydronootkatone; 4,6,8-megatrien-3-one; α-sweet orange aldehyde; β-sweet orange aldehyde; acetylated cedarwood oil (methyl cedarwood ketone);

[0196] Cyclic alcohols, for example: 4-tert-butylcyclohexanol; 3,3,5-trimethyl-cyclohexanol; 3-isoborneol-cyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[0197] Alicyclic alcohols, for example: α-3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butene-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butene-1-ol; 3-methyl-5 -(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-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;

[0198] Cyclic and alicyclic ethers, for example: eucalyptol; cedryl methyl ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)-cyclododecane; α-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[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;

[0199] Cyclic ketones and macrocyclic ketones, for example: 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 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-cyclohexadecene-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecene-1-one; 9-cycloheptadecene-1-one; cyclopentadecanone; cyclohexadecanone;

[0200] Alicyclic aldehydes, for example: 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde;

[0201] Alicyclic ketones, for example: 1-(3,3-dimethyl-cyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-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-naphthylmethyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl) ketone;

[0202] Esters of cyclic alcohols, for example: 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-amylcyclohexyl acetate; 4-tert-amylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate Esters; 4,7-methylene-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl acetate; 4,7-methylene-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl propionate; 4,7-methylene-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl isobutyrate; 4,7-methyleneoctahydro-5- or 6-indenyl acetate;

[0203] Esters of alicyclic alcohols, for example: 1-cyclohexylethyl crotonate; Esters of alicyclic carboxylic acids, for example: allyl-3-cyclohexyl propionate; allylcyclohexyloxyacetate; cis- and trans-methyl dihydrojasmonate; cis- and trans-methyl jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolanecarboxylate;

[0204] Aromatic aliphatic alcohols, for example: benzyl alcohol; 1-phenylethanol; 2-phenylethanol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;

[0205] Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, 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; α-trichloromethylbenzyl acetate; α,α-dimethylphenylethyl acetate; α,α-dimethylphenyl-ethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; aromatic aliphatic ethers, for example: 2- Phenylethyl methyl ether; 2-phenylethyl isopentyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydrogenated rosin aldehyde dimethyl acetal; phenylacetaldehyde 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;

[0206] Aromatic and aromatic aliphatic aldehydes, for example: benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydrorobaraldehyde; 4-methylbenzaldehyde; 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; meat Cinnamaldehyde; α-butylcinnamaldehyde; α-amylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal;

[0207] Aromatic and araliphatic ketones, 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-naphthyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanylmethyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanylmethyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]-ethanone; 5′,6′,7′,8′-tetrahydro-3′,5′,5′,6′,8′,8′-hexamethyl-2-naphthylacetonone;

[0208] Aromatic and araliphatic carboxylic acids and their esters, for example: benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methylphenyl acetate; ethylphenyl acetate; geranylphenyl acetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isopentyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidate; ethyl 3-methyl-3-phenylglycidate;

[0209] Nitrogen-containing aromatic compounds, for example: 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 3-methyl-5-phenyl-2-pentenoic acid nitrile; 3-methyl-5-phenylvaleric 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-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

[0210] Phenols, phenyl ethers and phenyl esters, for example: estragole; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl phenylacetate;

[0211] Heterocyclic compounds, 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;

[0212] Lactones, such as 1,4-octanolactone; 3-methyl-1,4-octanolactone; 1,4-nonanolactone; 1,4-decanolactone; 8-decene-1,4-lactone; 1,4-undecalactone; 1,4-dodecane-lactone; 1,5-decanolactone; 1,5-dodecalactone; 4-methyl-1,4-decanolactone; 1,15-pentadecalactone; cis- and trans-11-pentadecadecene-1,15-lactone; cis- and trans- Formula-12-pentadecadecene-1,15-lactone; 1,16-hexadecane lactone; 9-hexadecene-1,16-lactone; 10-oxa-1,16-hexadecane lactone; 11-oxa-1,16-hexadecane lactone; 12-oxa-1,16-hexadecane lactone; 1,12-dodecane dioic acid ethylene ester; 1,13-tridecane dioic acid ethylene ester; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin;

[0213] and mixtures of the above substances.

[0214] The aroma compounds according to the invention and the aroma compositions comprising or containing at least one compound according to the invention can be used for perfuming applications in liquid form, either undiluted or diluted with solvents. Suitable solvents 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.

[0215] Furthermore, the aroma compound according to the invention or the aroma composition comprising or containing the compound according to the invention can be adsorbed on a carrier, which ensures a fine distribution of the aroma substance in the final product and a controlled release when used. Such a carrier can be a porous inorganic material, such as sodium sulfate, silica gel, zeolite, gypsum, clay, clay particles, aerated concrete, etc., or an organic material, such as wood, cellulose-based substances, sugars, dextrins (such as maltodextrin), or plastics, such as PVC, polyvinyl acetate or polyurethane.

[0216] The aroma compounds of the present invention and the aroma compositions comprising or containing the compounds of the present invention represented by formula (I), especially formula (V) can also be microencapsulated, spray-dried, provided as inclusion complexes or as extruded products (i.e. products according to the present invention).

[0217] Optionally, the properties of the aroma compound or composition modified in this way can be further optimized with regard to a more targeted aroma release by "coating" with a suitable material, for which purpose waxy plastics such as polyvinyl alcohol are preferably used. The resulting product is again a product according to the invention.

[0218] The aroma compound according to the invention or the aroma composition according to the invention can be encapsulated, for example, by a coacervation process with the aid of an encapsulating material, for example made of a polyurethane-type substance or soft gelatin.

[0219] Spray-dried aromatic preparations based on aromatic compounds according to the present invention and aromatic compositions comprising or containing compounds according to the present invention can be prepared, for example, by spray-drying an emulsion or dispersion comprising or containing the aromatic compound or composition, wherein modified starch, protein, dextrin and vegetable gum can be used as carriers. Inclusion complexes can be prepared, for example, by introducing a dispersion of the aromatic compound or composition and cyclodextrin or urea derivatives into a suitable solvent, for example water.

[0220] Extruded products may be prepared by melting the fragrance compound or composition with a suitable waxy substance and extruding followed by solidification, optionally in a suitable solvent such as isopropyl alcohol.

[0221] In another aspect, the present invention therefore relates to the use of compounds of the general formula (I), in particular 2,4,6-substituted triazines of the formula (V), or fragrance compositions comprising or containing the compounds according to the invention as effective odorants or fragrance compounds. The comments made above apply correspondingly to the preferred compounds and mixtures.

[0222] The invention also relates to the use of compounds according to the invention, in particular compounds of the general formula (I) and 2,4,6-substituted triazines of the formula (V), or fragrance compositions comprising or containing at least one compound according to the invention, for improving the fixation of fragrance compounds, and the use of compounds according to the invention or compositions comprising or containing compounds according to the invention as fragrance substances and for the preparation of perfumed products. With regard to the preferred selection of compounds and mixtures according to the invention, the comments made above of course apply accordingly.

[0223] The invention therefore relates to the use of said compounds and compositions for improving the fixation of aromatic compounds or for the preparation of perfumed products.

[0224] The compounds according to the invention or compositions comprising or containing the compounds according to the invention can be incorporated into perfumed or intended perfumed products, in particular preparations for personal hygiene, such as perfume oils, perfume bases, personal hygiene preparations, cleaning agents or air fresheners.

[0225] Therefore, in another aspect, the present invention also relates to a perfumed product comprising or containing a compound of formula (I) and a 2,4,6-substituted triazine of formula (V), or a fragrance composition comprising or containing at least one compound according to the invention.

[0226] According to a preferred variant, the perfuming product according to the invention comprising or containing a compound according to the invention or a fragrance composition comprising or containing a compound according to the invention is produced by incorporating the compound according to the invention or a composition comprising or containing a compound according to the invention in pure form without solvent in the form of a solution or in a mixture with a solid or liquid carrier and optionally other auxiliaries and / or stabilizers to form a base formulation for personal hygiene, such as a detergent or the like.

[0227] The invention therefore also provides a perfumed product comprising or containing a compound of formula (I) and a 2,4,6-substituted triazine of formula (V) or a fragrance composition comprising or containing an effective amount of at least one compound according to the invention and a carrier or matrix.

[0228] Furthermore, the present invention relates to a cosmetic or home care composition comprising at least a 2,4,6-substituted triazine of formula (V).

[0229] The 2,4,6-substituted triazine of formula (V) is capable of absorbing ultraviolet light.

[0230] Therefore, in a preferred embodiment, the cosmetic or home care composition is a cream, preferably a sunscreen.

[0231] The present invention therefore also relates to the use of 2,4,6-substituted triazines of the formula (V) for absorbing UV rays, preferably in cosmetic compositions, in particular in sunscreens.

[0232] Example

[0233] The following compounds were prepared according to the methods indicated below. Structural determination was performed by spectroscopy by known techniques.

[0234] As mentioned above, all compounds and all formulas disclosed herein are generally intended to encompass pure stereoisomers, especially enantiomers, as well as mixtures of stereoisomers, especially mixtures of enantiomers. In addition, all intermediates obtained from the process may exist in different isomeric forms and therefore should include pure stereoisomers and mixtures of stereoisomers.

[0235] Example 1: Route for preparing 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

[0236] Step 1: Preparation of 3-((2-ethylhexyl)oxy)cyclohex-2-en-1-one (cyclohexenone monoether of formula (IIIa))

[0237] Methanesulfonic acid (MSA) (87 μL, 129 mg, 1.34 mmol, 0.03 eq) was added to a stirred solution of cyclohexane-1,3-dione (5.00 g, 44.6 mmol, 1.00 eq) and 2-ethyl-1-hexanol (10.5 mL, 8.71 g, 66.9 mmol, 1.00 eq) in toluene (50 mL) (acid-catalyzed etherification, Scheme 3). The mixture was heated to 111 °C and maintained for 20 h. After cooling to room temperature, the solution was neutralized with aqueous Na2CO3. The organic layer was separated, washed with water and brine, and dried over sodium sulfate. The solvent was removed under reduced pressure. The crude product was purified by vacuum distillation: residual isooctyl alcohol was removed at 450 mbar / 80 °C, and the resulting product was then distilled at 10 mbar / 200 °C. The title compound was obtained as a light yellow oil (6.90 g, 30.8 mmol, 69%). The desired isooctyloxycyclohexenone is obtained in a maximum yield of about 70% and the reaction can be scaled up to multi-gram quantities.

[0238]

[0239] Alternatively, p-toluenesulfonic acid (PTSA or pTsOH) or toluenesulfonic acid (TsOH) may be used instead of MSA. In addition, other strong acids (preferably sulfonic acids) may also be used for this purpose. The acid preferably has a pKa value of -1 or less. However, the use of MSA is preferred because it allows efficient etherification and is a cheap reactant and allows high selectivity.

[0240] 1 H NMR (500MHz, CDCl3) δ5.35(s,1H),3.75–3.66(m,2H),2.40(t,J=6.3Hz,2H),2.34(dd,J=7.3,6.0Hz,2H),1.97(p,J =6.5Hz,2H),1.70–1.61(m,2H),1.40(tdd,J=7.5,6.1,3.8Hz,2H),1.36–1.21(m,5H),0.89(td,J=7.1,3.0Hz,6H).

[0241] 13 C NMR (126MHz, CDCl3) δ200.0,178.4,102.8,71.2,38.9,36.9,30.5,29.2,29.1,23.9,23.1,21.4,14.2,11.1.

[0242] 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).

[0243] HRMS-FAB(m / z):[M+H] + C 14 H 24 The calculated value of O2 is 224.1771; the measured value is 224.1770.

[0244]

[0245] 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)

[0246] Cyclohexenone monoether In the case at hand, there are two possible routes. The cyclohexenone monoether can be oxidized to the 3-isooctyloxyphenol building block (resorcinol monoether) or attached to the triazine core before the whole system is oxidized.

[0247] According to the latter, initially, 3-isooctyloxycyclohexenone is treated with LDA, followed by the addition of 2,4-dichloro-6-(4-methoxyphenyl)triazine.

[0248] Therefore, 2M LDA in THF (2.44 mL, 523 mg, 4.88 mmol, 2.50 equiv) was added to a dry THF solution of 3-((2-ethylhexyl)oxy)cyclohex-2-ene-1-one (876 mg, 3.90 mmol, 2.00 equiv) at -78 ° C under argon atmosphere. The solution was stirred for 30 minutes. 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 dry THF (10 mL) was added dropwise to the reaction mixture and the resulting yellow solution was stirred at 60 ° C to 65 ° C for 15 to 16 h. The solvent was removed under reduced pressure and the residue was purified by flash column chromatography (SiO2, 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-en-1-one) (also known as tetrahydro-bemotriazinol or tetrahydro-BEMT) was isolated as a yellow resin (350 mg, 554 μmol, 28%) (Scheme 4).

[0249]

[0250] Alternatively, other strong bases may advantageously be used instead of LDA, preferably non-nucleophilic bases, even more preferably non-nucleophilic Li-amide bases such as lithium bis(trimethylsilyl)amide (LiHMDS).

[0251] 1 H-NMR (500 MHz, CDCl3) δ [ppm] = 8.45 (d, J = 9.0 Hz,2H),6.96(d,J=9.0Hz,2H),5.50(s,2H),3.91–3.86(m,1H),3.89(s,3H),3.86–3.70(m,4H),2.83(t,J=8.4 Hz,1H),2.73–2.62(m,1H),2.61–2.53(m,2H),2.45(td,J=8.4,3.0 Hz,1H),2.40(t,J=6.3 Hz,1H),2.37–2.27(m,2H),1.98(p,J=6.5 Hz, 1H), 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).

[0252] 13 C-NMR(126 MHz, CDCl3)δ[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.

[0253]

[0254] 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).

[0255] HRMS-FAB(m / z):[M+H] + C 23 H 22 The calculated value of O2N3 is 371.1707; the measured value is 372.1707.

[0256] 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 Bemotriazine Alcohol

[0257] General remarks: Cyclic voltammetry measurements were performed to evaluate the redox potentials of cyclohexenone and 6,6'-(6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl)bis(3-((2-ethylhexyl)-oxy)cyclohex-2-en-1-one). Each maximum corresponds to an oxidation process occurring at the indicated voltage. The slope of the curve towards higher voltages is due to the oxidation of the solvent. Since no minima occur during the reverse cycle, the oxidation process is irreversible. Upon repeated cycling, a passivation of the electrode is observed, with a decrease in intensity over multiple cycles. The highest intensity was obtained using a glassy carbon electrode, however, the most pronounced passivation was observed after the first cycle. In the case of a platinum electrode, the oxidation intensity was lower and a second oxidation process appeared. For both peaks, passivation was observed after one cycle. Almost no passivation occurred when a gold electrode was used.

[0258] The cyclic voltammetry results of 6,6'-(6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl)bis(3-((2-ethylhexyl)-oxy)cyclohex-2-en-1-one) show significantly different redox behaviors for different electrode materials. For glassy carbon, the total intensity is quite low compared to the spectrum of cyclohexenone. In addition, a strong passivation is observed after the first cycle. For gold, the total intensity is also relatively low, and no obvious oxidation peak appears. In the case of the platinum electrode, there is a significant maximum at 1.8 V with a relatively highest intensity of up to 30 mA / cm2. After the first cycle, the intensity decreases due to passivation, however, it remains constant in subsequent cycles.

[0259] Cyclic Voltammetry measurements were performed on a Gamry 600+ and Gamry 3000 potentiostats (Gamry Instruments) using a Teflon cell and an MSR electrode rotator (Pine Research) equipped with a disk electrode (Pt, Au, or glassy carbon, 0.5 mm diameter) and a platinum wire counter electrode. The potentials were normalized to a Ag / AgCl (KCl saturated in H2O) reference electrode (Meisenberger GmbH). 0.1 M Bu4NBF4 electrolyte was used for all electrochemical experiments. Prior to each measurement, the solutions were purged with argon. Cyclic voltammetry experiments were performed at ambient temperature. The potential window ranged from 0.05 to 1.6 V vs Ag / AgCl. The potentials were measured at 200, 100, 50, 25, and 200 mV s -1 The scan rates were measured successively, where three cyclic voltammograms were recorded for each scan rate using a GAMRYINSTRUMENT Interface 1010B potentiostat under argon atmosphere. All electrochemical oxidations were performed on a 400 nm electrode (each 0.8 × 3.0 cm 2 ) was carried out in an IKA ElectraSyn 2.0 equipped with 100 μL of 20 μL of MgCl. The electrodes were purchased from IKA and used as received. The reference electrode was filled with fresh 3 M KCl aqueous solution.

[0260] 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 equiv) and Bu4NBF4 (20.0 equiv) were dissolved in anhydrous DCM (7 mL). The solution was electrolyzed at a constant current of 2.0 V using a platinum anode and a graphite cathode at 4.2 F / mol. After the electrolysis was complete, the solvent was removed under reduced pressure and the residue was purified by flash column chromatography. 6,6'-(6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl)bis(3-((2-ethylhexyl)oxy)phenol) i.e. bemotriazinol was isolated as a yellow resin.

[0261] Example 3: Preparation of 6,6'-(6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl)bis(3-((2-ethylhexyl)oxy)phenol)-bemotriazinol by oxidative aromatization of the compound of formula (V)

[0262] 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 μmol, 1.00 equiv), Bu4NBF4 (208 mg, 633 μmol, 20.0 equiv) were dissolved in anhydrous CH2Cl2 (7 mL). The solution 4.2 F / mol was electrolyzed at a constant voltage of 2.0 V using a platinum anode and a graphite cathode. After the electrolysis was complete, the solvent was removed under reduced pressure and the residue was purified by flash chromatography (SiO2, CH / EtOAc 20:1). 1 (2.00 mg, 3.19 μmol, 10%) was isolated as a yellow resin.

[0263] R f (SiO2, CH / EtOAc, 4:1) = 0.70.

[0264] 1 H-NMR (500MHz, CDCl3) δ [ppm] = 13.40 (s, 2H), 8.53–7.86 (m, 4H), 6.93 (d, J = 8.9Hz, 2H), 6.49 (dd, J = 8.9, 2.5Hz, 2H), 6.42 (d, J = 2.5 Hz, 2H), 3.88 (dd, J=5.9, 2.1Hz, 4H), 3.85 (s, 3H), 1.76 (h, J=6.2Hz, 2H), 1.60–1.39 (m, 6H), 1.39–1.31 (m, 2H), 1.00–0.90 (m, 12H).

[0265] 13 C-NMR (126MHz, CDCl3) δ [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,CH2),55.5(CH3),39.3(2C,CH),30.6(2C,CH2),29.2(2C,CH2),23.9(2C,CH2),23.2(2C,CH2),14.2(2C,CH3),11.2(2C,CH3).

[0266]

[0267] 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).

[0268] HRMS-FAB(m / z):[M+H] + C 38 H 50 O5N3 calculated value 628.3745; measured value 628.3747.

[0269] Example 4: Preparation of 6,6'-(6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl)bis(3-((2-ethylhexyl)oxy)phenol)-resorcinol route

[0270] Step 1: Preparation of 1-bromo-3-((2-ethylhexyl)oxy)benzene

[0271]

[0272] 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 room temperature, 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. The residue was purified by flash chromatography (SiO2, CH / EE 40:1). 1-bromo-3-((2-ethylhexyl)oxy)benzene (5.32 g, 18.7 mmol, 81%) was obtained as a light yellow oil.

[0273] Alternatively, the reaction is carried out using other halide reagents such as the corresponding chloride compounds (eg isooctyl chloride).

[0274] R f (SiO2, CH / EtOAc, 4:1) = 0.81.

[0275] 1 H NMR (400 MHz, CDCl3) δ [ppm] = 7.13 (t, J = 8.3 Hz, 1H), 7.08–7.03 (m, 2H), 6.83 (ddd, J = 8.2, 2.4, 1.2 Hz, 1H), 3.87–3.76 (m, 2H, CH2), 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,CH3).

[0276] 13 C NMR (100 MHz, CDCl3) δ [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(CH2),39.5(CH),30.6(CH2),29.2(CH2),24.0(CH2),23.2(CH2),14.2(CH3),11.2(CH3).

[0277]

[0278] 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).

[0279] HRMS-FAB(m / z):[M+H] + C 14 H 21 O1 79 Br1 calculated value: 284.0770; found value: 284.0772.

[0280] Step 2: Preparation of 3-((2-ethylhexyl)oxy)phenol

[0281]

[0282] 1-Bromo-3-((2-ethylhexyl)oxy)benzene (700 mg, 2.45 mmol, 1.00 equiv), Pd2dba3 (45 mg, 49.1 μmol, 0.02 equiv), XPhos (94 mg, 196 μmol, 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 argon atmosphere. The mixture was heated to 100 °C for 20 h. After cooling to room temperature, the solution was neutralized with 1 M HCl. 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 by flash chromatography (SiO2, CHCl3). 3-((2-ethylhexyl)oxy)phenol (408 mg, 1.84 mmol, 75%) was obtained as a red oil.

[0283] R f (SiO2, CH / EtOAc, 4:1) = 0.52.

[0284] 1 H NMR (400MHz, CDCl3) δ [ppm] = 7.16–7.07 (m, 1H, CH Ar ),6.53–6.45(m,1H,CH Ar ),6.44–6.35(m,2H,CH Ar), 4.66 (s, 1H), 3.81 (dd, J = 5.7, 1.3Hz, 2H), 1.71 (hept, J = 6.2Hz, 1H), 1.50–1.35 (m, 2H), 1.35–1.29 (m, 4H), 0.99–0.85 (m, 6H).

[0285] 13 C NMR (100MHz, CDCl3) δ [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(CH2),39.5(CH),30.7(CH2),29.2(CH2),24.0(CH2),23.2(CH2),14.2(CH3),11.2(CH3).

[0286]

[0287] FAB-MS m / z(%):222(27),111(18),110(100).

[0288] HRMS-FAB(m / z):[M+H] + C 14 H 22 O2 calculated value 222.1614; measured value 222.1616.

[0289] Step 3: Preparation of bemotriazine alcohol (Friedel-Crafts acylation)

[0290] 2,4-Dichloro-6-(4-methoxyphenyl)-1,3,5-triazine (1.00 equiv) was dissolved in dichloromethane (10 mL). AlCl3 (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 by flash chromatography (SiO2, CH / EtOAc 20:1). Bemotriazine alcohol was isolated as a yellow resin.

[0291] Example 5: Preparation of 3-((2-ethylhexyl)oxy)phenol from resorcinol - acid catalysis

[0292] Alternatively, resorcinol was dissolved in toluene. Isooctyl alcohol and p-toluenesulfonic acid monohydrate were added and the solution was heated to 110° C. for 24 hours. 3-((2-ethylhexyl)oxy)phenol was obtained as a red oil.

[0293] Example 6: Preparation of 2,4-dichloro-6-(4-methoxyphenyl)-1,3,5-triazine

[0294] Grignard pathway:

[0295] Magnesium chips (729mg, 30.0mmol, 1.00 equivalent) are suspended in anhydrous THF (60mL). 4-bromoanisole (5.61g, 3.75mL, 30.0mmol, 1.00 equivalent) dissolved in anhydrous THF (100mL) is added dropwise to the mixture while being heated to 60°C. The solution is stirred for 1.5h. Subsequently, the mixture is added dropwise to a solution of cyanuric chloride (5.53g, 30.0mmol, 1.00 equivalent) in anhydrous THF (100mL) at 0°C over 30min. The solvent is removed under reduced pressure, and the residue is washed with isopropanol and recrystallized with a mixture of toluene and hexane (1: 1). 2,4-dichloro-6-(4-methoxyphenyl)-1,3,5-triazine (4.40g, 17.2mmol, 57%) is obtained as an off-white solid.

[0296] Friedel-Crafts acylation pathway:

[0297] Cyanuric chloride (100 mg, 542 μmol, 1.00 equivalent) was dissolved in dichloromethane or chlorobenzene (10 mL). Nafion beads (40 mg) and anisole (59 μL, 58.6 mg, 542 μmol, 1.00 equivalent) were added, and the solution was stirred at room temperature for 18 hours (Scheme 5). The solvent was removed under reduced pressure, and the residue was washed with isopropanol and recrystallized with a mixture of toluene and hexane (1: 1). 2,4-dichloro-6-(4-methoxyphenyl)-1,3,5-triazine (42 mg, 164 μmol, 30%) was obtained as an off-white solid.

[0298] The advantage of this route is that the potential hazards are significantly reduced compared to the standard Grignard route. In addition, Nafion is a solid catalyst that allows for convenient handling.

[0299] According to the alternative approach, triazine is obtained by dissolving cyanuric chloride (100mg, 542μmol, 1.00 equivalent) in dichloromethane (10mL). FeCl3 (99mg, 1.25mmol, 1.10 equivalent) and anisole (59μL, 58.6mg, 542μmol, 1.00 equivalent) are added, and the solution is stirred at room temperature for 18h. Subsequently, water is added to the mixture. Each phase is separated, and the organic phase is washed with water (3x) and dried over Na2SO4. The solvent is removed under reduced pressure, and the residue is washed with isopropanol and recrystallized with a mixture of toluene and hexane (1: 1). 2,4-dichloro-6-(4-methoxyphenyl)-1,3,5-triazine (96mg, 375μmol, 69%) is obtained as an off-white solid.

[0300] The advantage of this approach is that the potential hazards are significantly reduced compared to the standard Grignard approach. In addition, this method allows a significant increase in yield, reaching nearly 70%.

[0301]

[0302] Based on this new approach, the yield can be significantly improved. Therefore, compared with the standard Grignard approach, this approach is more efficient and avoids all the disadvantages associated with the use of Grignard reagents as described above. In addition, based on the Friedel-Crafts acylation approach, the use of bromoanisole can be avoided by using the cheaper anisole reactant (methoxybenzene) (see Scheme 1).

[0303] Other suitable catalysts were found to be: AlCl3 in CH2Cl2 (10% yield), AlCl3 in toluene (21%), TiCl4 (23%). The formation of 2,4-dichloro-6-(4-methoxyphenyl)-1,3,5-triazine was also observed for the following catalysts: FeF3, FeBr3, FeI3, Sc(OTf)3, TfOH, Zeolithe-H, Mont.KSF.

[0304] R f (SiO2, CH / EtOAc, 4:1) = 0.66.

[0305] 1 H NMR (400 MHz, CDCl3) δ [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).

[0306] 13 C NMR (100MHz, CDCl3) δ [ppm] = 174.2 (C q ,C p ),171.7(2C,Cq ),165.3(C q ,COMe),132.3(2C,CH Ar ),125.1(C q ,CN),114.5(2C,CH Ar ),55.7(CH3).

[0307]

[0308] 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).

[0309] HRMS-FAB(m / z):[M+H] + C 10 H7O1N3 35 Cl2 calculated value 254.9961; found value 254.9962.

[0310] Example 7: Oxidation and electrochemically driven aromatization of cyclohexenone ethers - Oxidative aromatization of 3-((2-ethylhexyl)oxy)phenol

[0311] Using stoichiometric methods, complete conversion to resorcinol monoether was achieved using iodine or IBX (Scheme 8). Catalytic or photocatalytic methods did not achieve the desired reaction.

[0312] Conversion using electrochemistry was successful for the reaction described below (see Example 2).

[0313]

[0314] 3-((2-ethylhexyl)oxy)cyclohex-2-ene-1-one (135 mg, 602 μmol, 1.00 equiv) was dissolved in water (10 mL). Iodine (183 mg, 722 μmol, 1.20 equiv) was added, and the solution was stirred at room temperature 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 Na2SO4. The solvent was removed under reduced pressure. 3-((2-ethylhexyl)oxy)phenol (10 mg, 45 μmol, 7%) was obtained as a red oil.

[0315] Example 8: Formulation Example

[0316] In the following formulation examples, the following five kinds of fragrance oils PFO1, PFO2, PFO3, PFO4 or PFO5 were each used as a fragrance.

[0317] Table 1: Composition of fragrance oil 1; PO1 (amount in ‰ weight)

[0318]

[0319]

[0320]

[0321] Table 2: Composition of fragrance oil 2; PO2 (amount in ‰ weight)

[0322]

[0323]

[0324] Table 3: Composition of fragrance oil 3; PO3 (amount in ‰ weight)

[0325]

[0326]

[0327] Table 4: Composition of fragrance oil 4; PO4 (amount in ‰ weight)

[0328]

[0329]

[0330] Table 5: Composition of fragrance oil 5; PO5 (amount in ‰ weight)

[0331]

[0332]

[0333]

[0334] The above-mentioned perfume oils PO1, PO2, PO3, PO4 or PO5 were incorporated into the formulations given below. Cosmetic formulations (compositions) (amounts of all formulations are in % by weight).

[0335] Table 6: Sunscreen spray with ethanol, expected SPF30, UVA / UVB balance

[0336]

[0337]

[0338] Table 7: Urban sunscreen spray, o / w lotion, expected SPF50+

[0339]

[0340]

[0341] Table 8: Sunscreen spray (O / W), expected SPF30* (cold manufacturing process)

[0342]

[0343]

[0344] Table 9: UV protection water spray, SPF50

[0345]

[0346]

[0347]

[0348] Table 10: Sunscreen spray, *SPF 50+, very water resistant**

[0349]

[0350]

[0351] Table 11: Sunscreen lotion (O / W), expected SPF 50* (cold / cold manufacturing process)

[0352]

[0353]

[0354] Table 12: Beach Time Lotion, SPF 30

[0355]

[0356]

[0357] Table 13: Sweat-resistant sunscreen lotions

[0358]

[0359]

[0360] Table 14: Sunscreen lotion (w / o)

[0361]

[0362]

[0363] Table 15: Protective Water Mousse, Expected SPF 30*

[0364]

[0365]

[0366] Table 16: Full protection lotion, expected SPF 50

[0367]

[0368]

[0369] Table 17: Whitening lotion, expected SPF 50plus*

[0370]

[0371]

[0372] Table 18: Sunscreen lotions for acne-prone skin, intended SPF 30

[0373]

[0374]

[0375]

[0376] Table 19: No More Shine Fluid, expected SPF50

[0377]

[0378]

[0379]

[0380] Table 20: Lightweight sunscreen liquid, expected SPF 50

[0381]

[0382]

[0383] Table 21: Clear gel sunscreen, expected SPF 30, UVA / UVB balance

[0384]

[0385]

[0386] Table 22: Sunscreen, SPF 40

[0387]

[0388]

[0389] Table 23: Anti-Pollution Hair Treatment, SPF 15

[0390]

[0391]

[0392] Table 24: Perfect Hand Lotion, Expected SPF 15, UVA / UVB Balance

[0393]

[0394]

[0395]

[0396] Table 25: Tinted sunscreens for combating hyperpigmentation

[0397]

[0398]

[0399]

[0400] Table 26: BB Cream Dark Shades, Expected SPF-20

[0401]

[0402]

[0403]

[0404] Table 27: Daily Well Aging, SPF 30, UVA / UVB Balance, w / o Octocrylene

[0405]

[0406]

[0407] Table 28: Anti-wrinkle day cream, expected SPF 15

[0408]

[0409]

[0410]

[0411] Table 29: Daily tattoo care, expected SPF 10, UVA / UVB balance

[0412]

[0413]

[0414]

[0415] Table 30: Sensitive day cream, expected SPF 15

[0416]

[0417]

[0418] Table 31: Cream, expected SPF 15, UVA / UVB

[0419]

[0420]

[0421]

[0422] Table 32: Air Fresheners (A / F Spray Water-Based)

[0423]

[0424] Colorless liquid, pH neutral

[0425] Table 33: General Purpose Cleaners

[0426]

[0427] Colorless liquid, pH 7

[0428] Table 34: General Purpose Cleaners

[0429]

[0430] Colorless liquid, pH 7

[0431] Table 35: Alkaline general purpose cleaners

[0432]

[0433]

[0434] Colorless liquid, pH 9

[0435] Table 36: Cleaning agents, liquid, citric acid

[0436]

[0437] Low viscosity liquid, pH 2

[0438] Table 37: Cleaning agents, liquid, citric acid

[0439]

[0440]

[0441] Low viscosity liquid, pH 2

[0442] Table 38: Light Duty Detergents

[0443]

[0444] Liquid, pH 7.3

[0445] Table 39: Light Duty Detergents

[0446]

[0447]

[0448] Liquid, pH 7.3

[0449] Table 40: Dishwashing liquid

[0450]

[0451] Colorless liquid, pH 8.5

[0452] Table 41: Fabric Softeners

[0453]

[0454]

[0455] Liquid, pH 3

[0456] Table 42: Encapsulated Fabric Softener Concentrates

[0457]

[0458] White liquid, pH 2.5

[0459] Table 43: Encapsulated Fabric Softener Concentrates

[0460]

[0461]

[0462] White liquid, pH 2.5

[0463] Table 44: Hand Sanitizer, Liquid

[0464]

[0465] Slightly colored liquid, pH 6

[0466] Table 45: Rim block gel

[0467]

[0468] Colorless paste / gel, pH=4.5

[0469] Table 46: Scented Lotion with Capsules

[0470]

[0471] White emulsion, pH neutral

[0472] Table 47: Cleaning agents, liquid, lactic acid

[0473]

[0474] Colorless liquid, pH 2.0

[0475] Table 48: Cleaning agents, liquid, citric acid

[0476]

[0477] Liquid, pH 2

Claims

1. A method for preparing a 2,4,6-substituted triazine of general 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 cyclohexenone ether; or - wherein Y and Z represent resorcinol monoether; - wherein, when Y and Z represent cyclohexenone ether, the compound of general formula (I) is obtained by reacting the cyclohexenone ether with a 2,4,6-substituted triazine under alkaline conditions; or -in, In the case where Y and Z represent resorcinol monoethers, the compounds of the general formula (I) are obtained by reaction of said resorcinol monoethers with 2,4,6-substituted triazines in an electrophilic aromatic substitution; or - wherein, when Y and Z represent resorcinol monoether, the compound of general formula (I) is obtained by reacting the resorcinol monoether with a 2,4,6-substituted triazine, followed by photoinduced rearrangement.

2. The method according to claim 1, wherein: In the case where Y and Z represent cyclohexenone ether or resorcinol monoether, the compound of general formula (I) is obtained by reaction of said cyclohexenone ether or said resorcinol ether with a 2,4,6-substituted triazine of general formula (II): - wherein R1 represents hydrogen or wherein R1 comprises an alkyl or aromatic group, preferably wherein R1 represents methoxyphenyl; and - wherein R2 represents a halogen atom; and - wherein R3 represents a halogen atom.

3. The method according to claim 1, wherein: In the case where Y and Z represent cyclohexenone ether or resorcinol monoether, the compound of general formula (I) is obtained by reacting the cyclohexenone ether or the resorcinol ether with a 2,4,6-substituted triazine, wherein the 2,4,6-substituted triazine is 2,4-dichloro-6-(4-methoxyphenyl)triazine.

4. The method according to any one of the preceding claims 1 to 3, wherein the cyclohexenone ether is a compound of the general formula (III): - wherein R4 represents a branched or straight chain alkyl group.

5. The method according to any one of the preceding claims 1 to 4, wherein the resorcinol monoether is a compound of the general formula (IV): - wherein R5 represents a branched or straight chain alkyl group.

6. A method according to any one of the preceding claims, wherein: When Y and Z represent cyclohexenone ether, the compound of general formula (I) is obtained by reacting the cyclohexenone ether with a 2,4,6-substituted triazine under alkaline conditions, wherein the cyclohexenone ether is 3-(2-ethylhexyloxy)cyclohex-2-en-1-one, and wherein the 2,4,6-substituted triazine is 2,4-dichloro-6-(4-methoxyphenyl)triazine.

7. A method according to any one of the preceding claims, wherein: In the case where Y and Z represent resorcinol monoether, the compound of general formula (I) is obtained by reaction of the resorcinol monoether with a 2,4,6-substituted triazine in an electrophilic aromatic substitution, wherein the 2,4,6-substituted triazine is 2,4-dichloro-6-(4-methoxyphenyl)triazine, and wherein the resorcinol monoether is 3-(2-ethylhexyloxy)phenol.

8. A method according to any one of the preceding claims, wherein: In the case where Y and Z represent resorcinol monoether, the compound of general formula (I) is obtained by reacting the resorcinol monoether with a 2,4,6-substituted triazine, followed by photoinduced rearrangement, wherein the resorcinol monoether is 3-(2-ethylhexyloxy)phenol, and wherein the 2,4,6-substituted triazine is 2,4-dichloro-6-(4-methoxyphenyl)triazine.

9. A method according to any one of the preceding claims, wherein: Compounds of the general formula (I) in which Y and Z represent resorcinol monoethers are obtained by oxidative aromatization of compounds of the general formula (I) in which Y and Z represent cyclohexenone.

10. The process according to claim 3, wherein the 2,4-dichloro-6-(4-methoxyphenyl)triazine is obtained by reacting 2,4,6-trichlorotriazine and methoxybenzene in the presence of at least one catalyst.

11. The method according to claim 10, wherein the at least one catalyst is a solution containing a Lewis acid, wherein the Lewis acid is preferably one of AlCl3, TiCl4, FeCl3, FeBr3, FeF3, Sc(OTf)3 or trifluoromethanesulfonic acid or montmorillonite KSF, Zeolith-Hβ or Nafion.

12. The process according to claim 11, wherein the at least one catalyst is used in a substoichiometric amount.

13. 2,4,6-substituted triazines of formula (V):

14. The compound according to claim 13, wherein the compound is present in the form of: Pure optically active enantiomers; a racemic mixture of enantiomers; or An optically active mixture of individual enantiomers.

15. A fragrance composition comprising at least the compound according to claim 13 or claim 14 and optionally at least one other fragrance substance.

16. A cosmetic composition or a home care composition comprising at least the compound according to claim 13 or claim 14.

17. The cosmetic or home care composition according to claim 16, wherein the cosmetic or home care composition is a cream, preferably a sunscreen.

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