Preparation of allene ketones using ammonium (thio)sulfate or hydrogen (thio)sulfate

Abstract

The present invention relates to a method for producing allene ketones using a specific ammonium (thio)sulfate or hydrogen (thio)sulfate as a catalyst, which provides allene ketones in high yield and high selectivity.

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to the preparation of allene ketones.

[0002] [Background of the invention] The allene ketones of formula (I) are an important class of industrial chemicals and are central products in the synthesis of vitamins and fragrance ingredients, of particular importance. One viable synthetic route uses tertiary propargyl carbinol as the starting product.

[0003] U.S. Pat. No. 3,029,287 and G. Saucy et al. disclose in Helv. Chim. Acta 1967, 50(4), 1158-1167 disclose the condensation of tertiary propargyl alcohols with ketals or enol ethers in the presence of a strong acid, particularly sulfuric acid or phosphoric acid or p-toluenesulfonic acid, to form allene ketones.

[0004] US Pat. No. 6,380,437 discloses the condensation of a tertiary propargyl alcohol with a ketal or alkenyl alkyl ether in the presence of an aliphatic sulfonic acid or metal salt thereof to form an allene ketone.

[0005] U.S. Pat. No. 3,330,867 and WO 2017 / 131607 disclose that allene ketones can be isomerized using hydrogen to give unsaturated ketones.

[0006] The use of strong acids in the preparation of allene ketones is disadvantageous because the handling of these chemicals (strong acids) is dangerous, requires special protective measures, and requires special and corrosion-resistant materials in the equipment used in the manufacturing process.

[0007] [Summary of the Invention] Therefore, the problem solved by the present invention is to provide a process for preparing allene ketones of formula (I) in high yield in the absence of strong acids and corrosive conditions.

[0008] Surprisingly, it has been found that the method according to claim 1 and the mixture of reactants according to claim 15 make it possible to solve this problem.

[0009] It has been found that certain ammonium (thio)sulfates or hydrogen (thio)sulfates are particularly well suited as catalysts for the reaction.

[0010] Further aspects of the invention are the subject matter of further independent claims. Particularly preferred embodiments are the subject matter of the dependent claims. [Brief explanation of the drawings]

[0011] [Figure 1] 3,7-Dimethyloct-6-en-1-yn-3-ol (=dehydrolinalool, "DLL") was mixed with 4 equivalents of isopropenyl methyl ether ("IPM") in the presence of the corresponding ammonium catalyst in an amount as shown in Table 1 and stirred at 115°C for a reaction time as shown in Table 1. The corresponding product, i.e., 6,10-dimethylundeca-4,5,9-trien-2-one, was obtained in the yield and selectivity as shown in Table 1. [Figure 2] 3,7-Dimethyloct-6-en-1-yn-3-ol (=dehydrolinalool, "DLL") was mixed with 2.6 equivalents of butenyl methyl ether (a 53 / 37 / 10 mixture of 2-methoxybut-1-ene, (E)-2-methoxybut-2-ene, and (Z)-2-methoxybut-2-ene) in the presence of the corresponding ammonium catalyst in the amount shown in Table 2 and stirred at a temperature of 80-95 °C for the reaction time shown in Table 2. The corresponding products, i.e., 7,11-dimethyldodeca-5,6,10-trien-3-one (=DMDTO) and 3,6,10-trimethylundeca-4,5,9-trien-2-one (=TMUTO), were obtained with the conversion, yield, and selectivity shown in Table 2. [Figure 3] 3,7,11-Trimethyldodec-1-yn-3-ol was mixed with 2.6 equivalents of butenyl methyl ether (a mixture of 2-methoxybut-1-ene / (E)-2-methoxybut-2-ene / (Z)-2-methoxybut-2-ene = 53 / 37 / 10) in the presence of the corresponding ammonium catalyst in the amount shown in Table 3, and stirred at a temperature of 80-95 °C for the reaction time shown in Table 3. The corresponding products, i.e., 7,11,15-trimethylhexadeca-5,6-dien-3-one (TMHDO) and 3,6,10,14-tetramethylpentadeca-4,5-dien-2-one (TMPDO), were obtained with the conversion, yield, and selectivity shown in Table 3.

[0012] [Detailed Description of the Invention] In a first aspect, the present invention provides an allene ketone of formula (I): [ka] a compound of formula (II) and a compound of formula (IIIa) or (IIIb) [ka] and the formula [ka] in the presence of an ammonium catalyst, During the ceremony, R 1 represents a methyl group or an ethyl group, R 2 represents a saturated or unsaturated, linear or branched or cyclic hydrocarbyl group having 1 to 46 C atoms, R 3 represents a methyl group or an ethyl group, R 4 represents H or a methyl group or an ethyl group, R 5 is a linear or branched chain C 1~10represents an alkyl group, in particular a methyl or ethyl group, R 5’ and R 5’’ teeth, Either straight or branched chain C 1~10 represents an alkyl group, in particular a methyl or ethyl group, Or R 5’ and R 5’’ is a linear or branched chain C 1~10 together forming an alkylene group, in particular an ethylene or propylene group, and, R 6 and R 7 and R 8 and R 9 are independently H or straight or branched chain C 1~10 represents one of the alkyl groups, R 30 , R 31 , R 32 , R 33 and R 34 are independently H or straight or branched chain C 1~12 represents either an alkyl group or a cycloalkyl group, and, X = [HSO4] - or [HS2O3] - and Y=[SO4] 2- or [S2O3] 2- and The wavy line refers to a method of representing a carbon-carbon bond that is in either the Z or E configuration when connected to a carbon-carbon double bond.

[0013] For clarity, some terms used herein are defined as follows:

[0014] As used herein, "C x~y An "alkyl" group is an alkyl group containing x to y carbon atoms, i.e., for example, C 1~3An alkyl group is an alkyl group containing 1 to 3 carbon atoms. An alkyl group may be straight-chain or branched. For example, -CH(CH3)-CH2-CH3 is considered a C4 alkyl group.

[0015] In this specification, when the same designation for a symbol or group occurs in more than one formula, the definition of the group or symbol given in connection with a particular formula also applies to other formulas containing the same designation.

[0016] As used herein, the term "independently of each other" in the context of substituents, moieties, or groups means that similarly designated substituents, moieties, or groups can exist simultaneously in the same molecule while having different meanings.

[0017] The term "(thio)sulfuric acid" or "(thio)hydrogen sulfate" refers to sulfuric acid (=[SO4] 2- ) and thiosulfate (=[S2O3] 2- ), or hydrogen sulfate (=[HSO4] - ) and hydrogen thiosulfate (=[HS2O3] - ) respectively.

[0018] As used herein, any dotted line in a formula represents the bond by which a substituent is attached to the remainder of the molecule.

[0019] As used herein, all wavy lines, independent of one another, when connected to a carbon-carbon double bond, represent carbon-carbon bonds that are in either the Z or E configuration.

[0020] As will be explained in greater detail below, compounds of formula (II) can be converted to compounds of formula (IIIa) or (IIIb) in the presence of specific ammonium (thio)sulfate or hydrogen (thio)sulfate catalysts (= "Cat"). [ka] React with either

[0021] [Compound of formula (II)] The compounds of formula (II) are known to those skilled in the art.

[0022] R 1 represents a methyl group or an ethyl group, preferably a methyl group.

[0023] R 2 represents a saturated or unsaturated, linear or branched or cyclic hydrocarbyl group having 1 to 46 C atoms, preferably a methyl group.

[0024] In a preferred embodiment, R 2 are represented by the formulae (R2-I), (R2-II), (R2-III) and (R2-IV) [ka] represents a group selected from the group consisting of:

[0025] The dotted line represents the bond by which a substituent of formula (R2-I), (R2-II), (R2-III) or (R2-IV) is attached to the remainder of the compound of formula (I) or formula (II). [ka] All double bonds represented by, independently of one another, represent either a carbon-carbon single bond or a carbon-carbon double bond. All wavy lines represented, independently of one another, represent carbon-carbon bonds in either the Z or E configuration when connected to a carbon-carbon double bond.

[0026] In the above formula, n represents 1, 2, 3 or 4, in particular 1 or 2.

[0027] In one preferred embodiment, R 2 represents either a group of formula (R2-I) or a group of formula (R2-II).

[0028] In another preferred embodiment, R 2represents either a group of formula (R2-III) or a group of formula (R2-IV).

[0029] Compounds of formula (II) include 2-methylbut-3-yn-2-ol (= methylbutynol, "MBY"), 3-methylpent-1-yn-3-ol (= ethylbutynol, "EBY"), 3,5-dimethylhex-1-yn-3-ol, 3,7-dimethyloct-6-en-1-yn-3-ol (= dehydrolinalool, "DLL"), 3,7-dimethyloct-1-yn-3-ol, 3,7-dimethylnon-6-en-1-yn-3-ol (= ethyldehydrolinalool, "EDLL"), 3,7,11-trimethyldodec-1-yn-3-ol, 3,7,11-trimethyl Preferably, it is selected from the group consisting of dodec-6-en-1-yn-3-ol, 3,7,11-trimethyldodeca-6,10-dien-1-yn-3-ol (= dehydronerolidol, "DNL"), 3,7,11-trimethyldodeca-4,6,10-trien-1-yn-3-ol (= ethynylpseudoionol, "EPI"), 3-methyl-5-(2,6,6-trimethylcyclohex-1-en-1-yl)pent-1-yn-3-ol and 3-methyl-1-(2,6,6-trimethylcyclohex-1-en-1-yl)pent-1-en-4-yn-3-ol.

[0030] It is particularly preferred that the compound of formula (II) is selected from the group consisting of 2-methylbut-3-yn-2-ol (= methylbutynol, "MBY"), 3-methylpent-1-yn-3-ol (= ethylbutynol, "EBY"), 3,7-dimethyloct-6-en-1-yn-3-ol (= dehydrolinalool, "DLL"), 3,7-dimethylnon-6-en-1-yn-3-ol (= ethyldehydrolinalool, "EDLL"), 3,7,11-trimethyldodeca-6,10-dien-1-yn-3-ol (= dehydronerolidol, "DNL") and 3,7,11-trimethyldodec-1-yn-3-ol.

[0031] Even more preferably, the compound of formula (II) is 3,7-dimethyloct-6-en-1-yn-3-ol (=dehydrolinalool, "DLL") or 3,7,11-trimethyldodec-1-yn-3-ol.

[0032] [Compound of formula (IIIa)] The compounds of formula (IIIa) are known to those skilled in the art.

[0033] In formula (IIIa), R 3 represents a methyl group or an ethyl group, and R 4 represents H, a methyl group, or an ethyl group; R 5 is a linear or branched chain C 1~10 It represents an alkyl group, in particular a methyl or ethyl group.

[0034] Preferably, R 3 The group represents a methyl group.

[0035] Preferably, R 4 The group represents H.

[0036] Preferably, R 5 The group represents a methyl group.

[0037] The compound of formula (IIIa) is most preferably either isopropenyl methyl ether ("IPM") or isopropenyl ethyl ether ("IPE"), especially isopropenyl methyl ether ("IPM").

[0038] In the synthesis of compounds of formula (IIIa), mixtures of compounds of formula (IIIa) are also often used in the reaction with compounds of formula (II). For example, in the case of butenyl methyl ether, a mixture of 2-methoxybut-1-ene, (E)-2-methoxybut-2-ene and (Z)-2-methoxybut-2-ene prepared from methanol and methyl ethyl ketone is often used.

[0039] [Compound of formula (IIIb)] The compounds of formula (IIIb) are known to those skilled in the art.

[0040] In formula (IIIb), R 3 represents a methyl group or an ethyl group, and R 4 represents H or a methyl group or an ethyl group.

[0041] R 5’ and R 5’’ In one embodiment, each of C is either linear or branched. 1~10 represents an alkyl group, in particular a methyl or ethyl group. 5’ and R 5’’ is a linear or branched chain C 1~10 Together they form an alkylene group, in particular an ethylene or propylene group.

[0042] Preferably, R 3 The group represents a methyl group.

[0043] Preferably, R 4 The group represents H.

[0044] In one preferred embodiment, R 5’ =R 5’’ and especially R 5’ =R 5’’ = methyl or ethyl, more preferably R 5’ =R 5’’ =CH3.

[0045] In another preferred embodiment, R 5’ and R 5’’ together form an ethylene (CH2CH2) group or a propylene (CH2CH2CH2 or CH(CH3)CH2) group.

[0046] The compound of formula (IIIb) is most preferably either 2,2-dimethoxypropane, or 2,2-diethoxypropane, or 2,2-dimethyl-1,3-dioxolane, or 2,2,4-trimethyl-1,3-dioxolane, or 2,2-dimethyl-1,3-dioxane.

[0047] The compound of formula (IIIb) is most preferably either 2,2-dimethoxypropane or 2,2-diethoxypropane, especially 2,2-dimethoxypropane.

[0048] It is preferred to use compounds of formula (IIIa) rather than compounds of formula (IIIb).

[0049] [Ammonium (thio)sulfate or hydrogen (thio)sulfate] The reaction of a compound of formula (II) with a compound of formula (IIIa) or (IIIb) can be carried out by the reaction of the formula [ka] is carried out in the presence of an ammonium catalyst of During the ceremony, R 6 and R 7 and R 8 and R 9 are independently H or straight or branched chain C 1~10 represents one of the alkyl groups, R 30 , R 31 , R 32 , R 33 and R 34 are independently H or straight or branched chain C 1~12 represents either an alkyl group or a cycloalkyl group, and, X = [HSO4] - or [HS2O3] - and Y=[SO4] 2- or [S2O3] 2- is.

[0050] In other words, suitable ammonium catalysts for reacting compounds of formula (II) according to the present invention with compounds of formula (IIIa) or (IIIb) are ammonium compounds which are highly specific not only with regard to the choice of cation but also of anion.

[0051] R 6=R 7 =R 8 It is preferable that:

[0052] R 6 =R 7 =R 8 =R 9 It is more preferable that:

[0053] R 9 It is more preferred that =H.

[0054] Therefore, in one highly preferred embodiment, the cation is an inorganic ammonium cation, i.e., NH + is.

[0055] In another highly preferred embodiment, the cation is a protonated tertiary amine, particularly triethylammonium and tributylammonium, with triethylammonium being preferred.

[0056] In another highly preferred embodiment, the cation is pyridinium or at least one straight or branched chain C 1~12 It is a pyridinium substituted with an alkyl group or a cycloalkyl group.

[0057] R 30 , R 31 , R 32 , R 33 and R 34 preferably represent, independently of each other, either H or a methyl group.

[0058] In one of these preferred embodiments, R 30 , R 31 , R 32 , R 33 and R 34 One or two of the groups represent a methyl group. Particularly preferred in this embodiment are α-picolinium, β-picolinium and γ-picolinium.

[0059] Of these embodiments, pyridinium is the most preferred, i.e., R30 =R 31 =R 32 =R 33 =R 34 =H.

[0060] The anion of the ammonium catalyst is sulfate (=[SO4] 2- ) or thiosulfate (=[S2O3] 2- ) or hydrogen sulfate (=[HSO4] - ) or hydrogen thiosulfate (=[HS2O3] - )

[0061] It has been found that the reaction is preferably carried out when the molar ratio of the compound of formula (II) to the compound of formula (IIIa) or (IIIb) is in the range of 1:15 to 1:1.

[0062] When a compound of formula (IIIa) is used, the ratio is more preferably in the range of 1:5 to 1:2, even more preferably in the range of 1:3.5 to 1:2, most preferably in the range of 1:3 to 1:2, and particularly preferably in the range of 1:2.5 to 1:2.

[0063] When a compound of formula (IIIb) is used, the ratio is more preferably in the range of 1:10 to 1:2, even more preferably in the range of 1:8 to 1:3, and most preferably in the range of 1:8 to 1:5.

[0064] Furthermore, the amount of the ammonium catalyst is in the range of 0.01 to 1 mol%, preferably in the range of 0.02 to 0.6 mol%, more preferably in the range of 0.05 to 0.6 mol%, based on the amount of the compound of formula (II). In particular, a very small amount of the compound of formula (II), in the range of 0.01 to 0.1 mol%, preferably in the range of 0.01 to 0.05 mol%, is preferred. [ka] It was found that the ammonium catalyst of the formula (I) gave particularly high yields and showed high selectivity.

[0065] It has also been observed that when the ammonium catalyst is used at such low catalyst concentrations and the molecular weight of the compound of formula (II) is increased, the yield and selectivity are improved.

[0066] Furthermore, it has been found that extremely short reaction times, typically less than 3 hours, can be achieved even when the concentration of ammonium catalyst is less than 0.5 mol %.

[0067] Most preferably, the reaction is carried out at an ammonium catalyst concentration of 0.5 to 0.05 mol % for a reaction time of 60 to 110 minutes, or at an ammonium catalyst concentration of 0.1 to 0.01 mol % for a reaction time of 2 to 22 hours.

[0068] The reaction is preferably carried out at a temperature in the range of 70 to 170° C. In one embodiment, the temperature is preferably in the range of 110 to 160° C., most preferably in the range of 115 to 150° C. This temperature range is particularly suitable for isopropenyl methyl ether as the compound of formula (IIIa).

[0069] In another embodiment, the temperature is preferably in the range of 75 to 100° C., and most preferably in the range of 80 to 95° C. This temperature range is 3 =R 4 = methyl or ethyl, or R 3 Particularly preferred are compounds of formula (IIIa) either with .intg. ethyl, most particularly butenyl methyl ether as compound of formula (IIIa).

[0070] In one embodiment, the reaction is preferably carried out at a pressure in the range of 5 to 20 bara, more preferably in the range of 6 to 15 bara, which pressure range is particularly suitable for isopropenyl methyl ether as the compound of formula (IIIa).

[0071] In another embodiment, the reaction is preferably carried out at ambient pressure (1 bara), which is particularly suitable for butenyl methyl ether as the compound of formula (IIIa).

[0072] The reaction can be carried out without a solvent or in the presence of an organic solvent. Preferably, the reaction is carried out without a solvent.

[0073] Even when the reaction is carried out in the absence of an organic solvent, the starting materials, the compound of formula (II) and the compound of formula (IIIa) or (IIIb), and the ammonium catalyst may still be provided in an organic solvent. Thus, the organic solvent may be present in an amount of up to 10% by weight, preferably up to 5% by weight, and more preferably up to 3% by weight, based on the total weight of the reactant mixture.

[0074] If the reaction is carried out in an organic solvent, a polar aprotic organic solvent is preferred, for example an aliphatic ketone, such as acetone.

[0075] The above reaction has been found to provide compounds of formula (I) in high conversion, high yield and high selectivity.

[0076] In particular, it has been found that compounds of formula (I) selected from the group consisting of 6-methylhepta-4,5-dien-2-one, 6,10-dimethylundeca-4,5-dien-2-one, 6,10-dimethylundeca-4,5,9-trien-2-one, 6,10,14-trimethylpentadeca-4,5,9,13-tetraen-2-one, 6,10,14-trimethylpentadeca-4,5,9-trien-2-one, 6,10,14-trimethylpentadeca-4,5,13-trien-2-one and 6,10,14-trimethylpentadeca-4,5-dien-2-one can be preferably produced.

[0077] The mixture of reactants itself, with or without organic solvent, is also an object of the present invention.

[0078] Thus, in a further aspect, the present invention provides a method for producing a composition comprising: i) a compound of formula (II), [ka] ii) a compound of formula (IIIa) or (IIIb), [ka] and iii) Formula [ka] The present invention relates to a mixture of reactants containing an ammonium catalyst of the formula:

[0079] The compounds of formula (II) and formula (IIIa) or (IIIb), and the ammonium catalyst have already been fully described above.

[0080] The compound of formula (I) is isomerized in the presence of a base or an acid, preferably a base, to give a diene ketone of formula (IV) [ka] can be obtained.

[0081] Thus, in a further aspect, the present invention provides a diene ketone of formula (IV) [ka] A method for producing a) preparing a compound of formula (I) as already described in great detail above, Next, b) isomerizing the compound of formula (I) in the presence of a base or an acid, preferably a base, to give a diene ketone of formula (IV).

[0082] The isomerization of compounds of formula (I) to obtain compounds of formula (IV) is primarily known to those skilled in the art from, for example, U.S. Pat. No. 3,330,867 and WO 2017 / 131607, the contents of both of which are incorporated herein by reference in their entirety.

[0083] The base used in the isomerization step, i.e. step b), is preferably an alkali metal or alkaline earth metal hydroxide or carbonate or hydrogencarbonate, preferably a hydroxide, in particular KOH or NaOH.

[0084] In another preferred embodiment, the base is a basic ion exchange resin, preferably the basic anion exchange resins Amberlite® IRA 900, Dowex® MSA-1, Diaion® HPA25 or PA308, and Amberlyst® A260H, DOW XE-4, XE-8, XE-8 new model and XE-10, and equivalent resins with the same chemical structure and similar physicochemical properties.

[0085] The temperature in this isomerization step is preferably less than 30°C, particularly in the range of -10°C to 25°C, preferably 0°C to 10°C.

[0086] The isomerization step is 1~6 It is preferably carried out in an alcohol, particularly methanol, or in an aqueous medium.

[0087] Said process allows the preparation of compounds of formula (I) or (IV), respectively, in high yield and selectivity relative to compounds of formula (II). Hence, the present invention offers significant advantages over processes known to those skilled in the art.

[0088] [Example] The present invention is further illustrated by the following experiments.

[0089] [Experimental series 1] 3,7-Dimethyloct-6-en-1-yn-3-ol (=dehydrolinalool, "DLL") was mixed with 4 equivalents of isopropenyl methyl ether ("IPM") in the presence of the corresponding ammonium catalyst in an amount as shown in Table 1 and stirred at 115°C for a reaction time as shown in Table 1. The corresponding product, i.e., 6,10-dimethylundeca-4,5,9-trien-2-one, was obtained in the yield and selectivity as shown in Table 1 (see Figure 1).

[0090] [Table 1]

[0091] 6,10-dimethylundeca-4,5,9-trien-2-one from Table 1 was quantitatively isomerized to give 6,10-dimethylundeca-3,5,9-trien-2-one by a reaction as shown in Example 2 of WO 2011 / 131607.

[0092] [Experimental series 2] 3,7-Dimethyloct-6-en-1-yn-3-ol (=dehydrolinalool, "DLL") was mixed with 2.6 equivalents of butenyl methyl ether (a 53 / 37 / 10 mixture of 2-methoxybut-1-ene / (E)-2-methoxybut-2-ene / (Z)-2-methoxybut-2-ene) in the presence of the corresponding ammonium catalyst in the amount shown in Table 2 and stirred at a temperature of 80-95 °C for the reaction time shown in Table 2. The corresponding products, i.e., 7,11-dimethyldodeca-5,6,10-trien-3-one (=DMDTO) and 3,6,10-trimethylundeca-4,5,9-trien-2-one (=TMUTO), were obtained with the conversion, yield, and selectivity shown in Table 2 (see Figure 2).

[0093] [Table 2]

[0094] By the reaction as shown in Example 2 of WO 2011 / 131607, 3,6,10-trimethylundeca-4,5,9-trien-2-one and 7,11-dimethyldodeca-5,6,10-trien-3-one from Table 2 were quantitatively isomerized to give 3,6,10-trimethylundeca-3,5,9-trien-2-one and 7,11-dimethyldodeca-4,6,10-trien-3-one, respectively.

[0095] [Experimental series 3] 3,7,11-Trimethyldodec-1-yn-3-ol was mixed with 2.6 equivalents of butenyl methyl ether (a 53 / 37 / 10 mixture of 2-methoxybut-1-ene / (E)-2-methoxybut-2-ene / (Z)-2-methoxybut-2-ene) in the presence of the corresponding ammonium catalyst in the amount shown in Table 3, and the mixture was stirred at a temperature of 80-95°C for a reaction time shown in Table 3. The corresponding products, i.e., 7,11,15-trimethylhexadeca-5,6-dien-3-one (TMHDO) and 3,6,10,14-tetramethylpentadeca-4,5-dien-2-one (TMPDO), were obtained with the conversion, yield, and selectivity shown in Table 3 (see Figure 3).

[0096] [Table 3]

[0097] By the reaction shown in Example 2 of WO 2011 / 131607, 7,11,15-trimethylhexadeca-5,6-dien-3-one and 3,6,10,14-tetramethylpentadeca-4,5-dien-2-one from Table 3 were quantitatively isomerized to give 7,11,15-trimethylhexadeca-4,6-dien-3-one and 3,6,10,14-tetramethylpentadeca-3,5-dien-2-one, respectively.

Claims

1. Allene ketones of formula (I) 【Chemistry 1】 a compound of formula (II) and a compound of formula (IIIa) or (IIIb) 【Chemistry 2】 and the formula 【Transformation 3】 in the presence of an ammonium catalyst, During the ceremony, R １ represents a methyl group or an ethyl group, R ２ represents a saturated or unsaturated, linear or branched or cyclic hydrocarbyl group having 1 to 46 C atoms, R ３ represents a methyl group or an ethyl group, R ４ represents H or a methyl group or an ethyl group, R ５ is a straight or branched chain C １～１０ represents an alkyl group, R ５’ and R ５’’ teeth, Either straight or branched chain C １～１０ represents an alkyl group, or Or, R ５’ and R ５’’ is a linear or branched chain C １～１０ together form an alkylene group, and, R ３０ , R ３１ , R ３２ , R ３３ and R ３４ are independently H or straight or branched chain C １～１２ represents either an alkyl group or a cycloalkyl group, and, X = [HSO ４ ] － or [HS ２ O ３ ] － and A method for preparing an allene ketone of formula (I), wherein the wavy line represents a carbon-carbon bond that is in either the Z or E configuration when connected to a carbon-carbon double bond.

2. R １ 2. The method of claim 1, wherein represents a methyl group.

3. R ３０ , R ３１ , R ３２ , R ３３ and R ３４ 3. The method according to claim 1 or 2, characterized in that, independently of each other, represent either H or a methyl group.

4. R ３０ , R ３１ , R ３２ , R ３３ and R ３４ 4. The method according to claim 1, wherein one or two of the groups represent a methyl group.

5. R ３０ =R ３１ =R ３２ =R ３３ =R ３４ 4. The method according to claim 1, wherein: =H.

6. R ２ 6. The method according to claim 1, wherein: = a methyl group.

7. R ２ Formula (R2-I), (R2-II), (R2-III) and (R2-IV) 【Chemistry 4】 wherein the dotted line represents a bond by which a substituent of formula (R2-I), (R2-II), (R2-III) or (R2-IV) is attached to the remainder of the compound of formula (I) or formula (II); 【Transformation 5】 any double bond according to the formula: represents, independently of one another, either a carbon-carbon single bond or a carbon-carbon double bond; all wavy lines, independently of one another, when connected to a carbon-carbon double bond, represent carbon-carbon bonds that are in either the Z or E configuration; n represents 1, 2, 3 or 4. The method according to any one of claims 1 to 5, characterized in that the compound is selected from the group consisting of:

8. 8. The process according to any one of claims 1 to 7, characterized in that the molar ratio of the compound of formula (II) to the compound of formula (IIIa) or (IIIb) is in the range of 1:15 to 1:

1.

9. 9. The method according to any one of claims 1 to 8, characterized in that the amount of the ammonium catalyst ranges from 0.01 to 1 mol %, based on the amount of the compound of formula (II).

10. 10. The method according to any one of claims 1 to 9, characterized in that the compound of general formula (I) is selected from the group consisting of 6-methylhepta-4,5-dien-2-one, 6,10-dimethylundeca-4,5-dien-2-one, 6,10-dimethylundeca-4,5,9-trien-2-one, 6,10,14-trimethylpentadeca-4,5,9,13-tetraen-2-one, 6,10,14-trimethylpentadeca-4,5,9-trien-2-one, 6,10,14-trimethylpentadeca-4,5,13-trien-2-one and 6,10,14-trimethylpentadeca-4,5-dien-2-one.

11. Diene ketones of formula (IV) 【Transformation 6】 A method for producing a) preparing a compound of formula (I) according to any one of claims 1 to 10, Next, b) isomerizing the compound of formula (I) in the presence of a base or an acid to obtain the diene ketone of formula (IV).

12. i) a compound of formula (II), 【Transformation 7】 ii) a compound of formula (IIIa) or (IIIb), 【Transformation 8】 and iii) Formula 【Chemistry 9】 1. A reaction mixture comprising an ammonium catalyst of During the ceremony, R １ represents a methyl group or an ethyl group, R ２ represents a saturated or unsaturated, linear or branched or cyclic hydrocarbyl group having 1 to 46 C atoms, R ３ represents a methyl group or an ethyl group, R ４ represents H or a methyl group or an ethyl group, R ５ is a straight or branched chain C １～１０ represents an alkyl group, R ５’ and R ５’’ teeth, Either straight or branched chain C １～１０ represents an alkyl group, or Or, R ５’ and R ５’’ is a linear or branched chain C １～１０ together form an alkylene group, and, X = [HSO ４ ] － or [HS ２ O ３ ] － and Any wavy lines, independent of each other, represent carbon-carbon bonds that are in either the Z or E configuration when connected to a carbon-carbon double bond. Reaction mixture.

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