Rearrangement of alpha-alkynols

Abstract

The present invention relates to the formation of alpha-beta unsaturated ketones from alpha-alkynols by a Rupe re-arrangement using a phyllosilicate clay, particularly a clay from the smectite group as catalyst.

Description

[0001] REARRANGEMENT OF ALPHA-ALKYNOLS

[0002] Technical Field

[0003] The present invention relates to the formation of alpha, beta unsaturated ketones from alpha-alkynols.

[0004] Background of the invention

[0005] Alpha-beta unsaturated ketones are an important class in chemistry, particularly in the field of fragrances. An important synthetic route for such compounds is based on Rupe rearrangement which uses alpha alkynols.

[0006] The Rupe arrangement is known to be catalysed by certain transition metal complexes and Lewis acids.

[0007] WO 2015 / 144832 A1 discloses a Rupe rearrangement of 1-ethynyl-3,3- dimethylcyclohexan-1-ol to 1-(5,5-dimethylcyclohex-1-en-1-yl)ethan-1-one or 1- (3,3-dimethylcyclohex-1-en-1-yl)ethan-1-one, respectively, in the presence of a gold (I) complex. Gold complexes are, however, very expensive.

[0008] EP3 475 401 B1 discloses the formation of 1-(cyclododeca-1 ,5,9-trien-1 - yl)ethan-1-one from 1-ethynylcyclododeca-4,8-dien-1-ol in the presence of formic acid.

[0009] DE 198 48 305 C1 discloses the rearrangement of propargyl alcohol derivatives into alpha, beta-unsaturated ketones with an acidic cation-exchange resin. Ion exchange resins, however, are rather expensive.

[0010] Furthermore, Rupe rearrangement is observed to occur in the presence of zeolites as exemplified for example by G. Sartori et al., Tetrahedron, Vol- 52, no. 24, 8287-9296, 1996 or N. Mameda et al., Applied Catalysis A: General 505 (2015) 213-216. Zeolites, however, are rather expensive. Summary of the invention

[0011] Therefore, the problem to be solved by the present invention is to offer a synthesis of alpha, beta unsaturated ketone from alpha-alkynols by using a cheap catalyst which is available in large quantities.

[0012] Surprisingly, it has been found that the process according to claim 1 offers a solution to this problem.

[0013] Particularly, it has been found that a phyllosilicate clay, particularly a clay selected from the smectite group, preferably a montmorillonite-based clay, more preferably in the form of bentonite, offers a suitable catalyst for the rearrangement of the compound of formula (II) to formula (I) in a very high yield at high conversion and therefore high selectivity.

[0014] The use of a phyllosilicate clay, particularly a montmorillonite-based clay as catalyst is very advantageous as the clay is globally available at very high volume in a constant quality and at high purity and relatively low price. Furthermore, it has been shown that the clay can be easily disposed and handled without any problems. As the catalyst is a mineral and exhibits a high chemical inertness, the use of this catalyst results in a low ecological impact and is, therefore, very advantageous and sustainable.

[0015] Further aspects of the invention are subject of further independent claims. Particularly preferred embodiments are subject of dependent claims.

[0016] Detailed description of the invention

[0017] In a first aspect the present invention relates to a process of producing a compound of the formula (I) by a rearrangement reaction of a compound of the formula (II) characterized in that said rearrangement reaction is catalyzed by a phyllosilicate clay, particularly by a clay from the smectite group; and wherein

[0018] R1and R2and R3, independently from each other, either represents H, a

[0019] C1-1 o-alkyl group or a Ce-12-aryl group; and

[0020] R4and R5either, independently from each other, represents a Ci- -alkyl group which, optionally, comprises at least one carbon-carbon double bond or a Ce-12-aryl group; or form together a C2-2o-alkylene group, particularly a Cs-9-alkylene group, which, optionally, comprises at least one carbon-carbon double bond; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration; and any double bond having dotted line ( - ) represents independently from each other either a single carbon-carbon bond or a carbon-carbon double bond; with the proviso that the compound of the formula (I) does not comprise two cumulated carbon-carbon double bonds and that at least one of the double bond having dotted line ( - ) represents a carbon-carbon double bond.

[0021] For sake of clarity, some terms used in the present document are defined as follows:

[0022] In the present document, a “Cx-y-alkyl” group is an alkyl group comprising x to y carbon atoms, i.e. , for example, a Ci-3-alkyl group is an alkyl group comprising 1 to 3 carbon atoms. The alkyl group can be linear or branched. For example -CH(CH3)-CH2-CH3 is considered as a C4-alkyl group. A “Cx-y aryl” group is an aryl group comprising x to y carbon atoms. An aryl group designates the normal meaning in the art, i.e. , an aromatic hydrocarbyl group such as phenyl, pyridine, biphenyl, anthryl or naphthyl group optionally substituted. Non-limiting examples of the optional substituent of the aryl group may include a C1-4 alkyl or alkoxy group, a hydroxy group or a halogen atom.

[0023] A “Cx-y alkylene” group is an alkylene group comprising x to y carbon atoms. An alkylene is a substituent which, formally, is obtained from an alkane by removal of 2 H atoms and forms a carbon-carbon bond with each of the two rests of the molecule the alkylene group is bound to. For example, a Ci-3-alkylene group is an alkylene group comprising 1 to 3 carbon atoms. The alkylene group can be linear or branched. For example, -CH2-CH2-CH2- and -CH(CH3)-CH2- and -C(CH2- CH3)- and -C(CH3)2- are all considered to be Cs-alkylene groups.

[0024] In case identical labels for symbols or groups are present in several formulae, in the present document, the definition of said group or symbol made in the context of one specific formula applies also to other formulae which comprises the same said label.

[0025] The term “independently from each other” in this document means, in the context of substituents, moieties, or groups, that identically designated substituents, moieties, or groups can occur simultaneously with a different meaning in the same molecule.

[0026] Any single dotted line in any formulae represents the bond by which said substituent is bound to the rest of a molecule.

[0027] Any double bond having dotted line ( - ) represents independently from each other either a single carbon-carbon bond or a carbon-carbon double bond with the proviso that the respective formula does not comprise two cumulated carbon-carbon double bonds and that at least one of the double bond having dotted line ( - ) represents a carbon-carbon double bond.

[0028] In other words, when two such double bonds having dotted line ( - ) are adjacent to each other, exactly one of these double bonds having dotted lines ( - ) represents a carbon-carbon double bond and the other represents a carbon-carbon single bond to assure that none of the formulas in this document comprises an allene structure

[0029] In other words, for example, a representation of the formula is a shorted version of the following two formulas

[0030] Any wavy line in any formula of this document represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E-configuration.

[0031] The compound of the formula (II) is the starting product to produce

[0032] Compound of the formula (II) is an alpha-alkynol. The tertiary hydroxy group and the carbon-carbon triple bond in its alpha position are key elements of the structure of the compound of the formula (II).

[0033] It is preferred that R1represents H. It is furthermore preferred that R2or R3represents CH3.

[0034] It is particularly preferred that that R2= R3= CH3.

[0035] Compound of the formula (II)

[0036] In one of the preferred embodiments, the compound of the formula (II) is a linear compound. In this embodiment, R4and R5are particularly selected so that they independently from each other represent a C1-1 o-alkyl group or a Ce-12-aryl group. Furthermore, in this embodiment R4can also represent H.

[0037] The Ci- -alkyl group of R4can comprise at least one carbon-carbon double bond. It is, however, preferred that the Ci-w-alkyl group of R4does not comprise any carbon-carbon double bonds.

[0038] It is preferred that in this embodiment the compound of the formula (I) is selected from the group consisting of the compounds of formula

[0039] In another of the preferred embodiments, the compound of the formula (II) is a cyclic compound. In this embodiment, R4and R5are particularly selected so that they form together a C2-2o-alkylene group, particularly a Cs-9-alkylene group, which, optionally, comprises at least one carbon-carbon double bond.

[0040] Therefore, in this embodiment a cyclic compound having a ring size of preferably 6 to 12 carbon atoms is formed. It is particularly preferred that the alkylene group formed by R4and R5is a Cs-alkylene or a C39 -alkylene group, i.e. that a cyclic compound having a ring size of 6 or 12 carbon atoms is formed.

[0041] Particularly, the alkylene group formed by R4and R5is C2-alkylene group, i.e. a cyclic compound having a ring size of 5 carbon atoms is formed. Preferably, in this embodiment, the compound of the formula (II) is a compound of the formula (II-B1 ) or (II-B2) or (II-B3) or ( I I-B4), particularly of the formula (II-B1 a) or (ll-B2a) or (ll-B3a) or (ll-B4a), more preferably of the formula (II-B1 b) or (I l-B2b) or (I l-B3b) or (I l-B4b):

[0042]

[0043] R1and R2and R3, independently from each other, either represents H, a Ci- -alkyl group or a Ce-12-aryl group; and

[0044] R6represents is a Ci -1 o-alkyl group, preferably a methyl or an ethyl or an iso- propyl or a sec-butyl group.

[0045] Clay

[0046] The compound of the formula (I) is produced by a rearrangement reaction of the compound of the formula (II) by a phyllosilicate clay, particularly a clay from the smectite group. Phyllosilicates, also called sheet silicates. The basic structure of the phyllosilicates is based on interconnected six member rings of SiCU'4tetrahedra that extend outward in infinite sheets. Three out of the 4 oxygens from each tetrahedra are shared with other tetrahedra.

[0047] The major clay groups are kaolins, smectite, illites, chlorites and hormites. Smectites include the individual minerals sodium montmorillonite, calcium montmorillonite, nontronite, saponite, and hectorite. Bentonite is a rock in which montmorillonite is particular dominant mineral. These clays are globally available in vast quantities at a very low price.

[0048] Clays are used particularly for purification of hydrocarbons, particularly of benzene, toluene, xylene and other petrochemical liquids.

[0049] For the present invention it is preferred that the clay is a montmorillonitebased clay, particularly bentonite.

[0050] It has been found that particularly acid treated clays from the smectite group, preferably montmorillonite-based clay, particularly bentonite, are advantageously used as catalyst for the above process.

[0051] For example, the acid treatment can be performed as disclosed in US 2,671 ,058 or US 6,762,144.

[0052] The acid treatment of the clays is performed particularly by treatment with sulfuric acid.

[0053] Non-limiting examples of suitable clays may include F-20X, F20-XLM, F- 21X, F-24X, F-22, F-118FF sold by EP Minerals, Fulcat-22F and Fulcat-22B sold by Byk, K-5, K10, K-10-S300, K-20, K-21 , K-30, K-41 sold by Clariant, as well as clays as commercialized under the trademark TONSIL® by Sud-Chemie.

[0054] The process of producing the compound of the formula (I) by a rearrangement reaction of the compound of the formula (I) can be performed neat or in the presence of a solvent.

[0055] It is preferred that the rearrangement reaction is performed in a presence of an organic solvent, preferably an organic solvent selected from the group consisting of ethers, aromatic hydrocarbons, hydrogenated aromatic hydrocarbons, alcohols, and esters, particularly selected from the group consisting of tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF), cyclopentyl methyl ether (CPME), 1 ,4-dioxane, toluene, chlorobenzene, n-butanol and n-butylacetate, preferably 2-methyltetrahydrofuran. It has been shown that the rearrangement reaction is preferably performed in a presence of water, more preferably in the presence of water and an organic solvent, preferably an organic solvent selected from the group consisting of ethers, aromatic hydrocarbons, hydrogenated aromatic hydrocarbons, alcohols, and esters, particularly selected from the group consisting of tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF), cyclopentyl methyl ether (CPME), 1 ,4-dioxane, toluene, chlorobenzene, n-butanol and n-butylacetate, preferably 2-methyltetrahydrofuran.

[0056] It has been observed that the presence of water accelerates the rearrangement reaction.

[0057] It is preferred that the weight ratio amount of water to organic solvent is between 100: 1 and 100:20, preferably between 100:1 and 100:5.

[0058] The weight ratio of the clay : compound of the formula (II) is in the range of 100:0.5 to 100:60, preferably 100:2 to 100:50, more preferably 100:4 to 100:30, most preferably 100:5 to 100:20.

[0059] Furthermore, the rearrangement reaction is performed at a temperature of between 40 and 140°C. At temperatures above this range, a decrease in yield and selectivity is expected.

[0060] Preferably, the rearrangement reaction is performed at a temperature of between 60 and 90 °C.

[0061] The person skilled in the art is well able to select suitable heating apparatus to provide heat to the rearrangement reaction. Non-limiting examples include aluminium heating blocks, jacketed laboratory reactors, oil bath, and heat induction.

[0062] It is, furthermore, preferred that the rearrangement reaction is performed in a presence of an acid, preferably an acid with a pKa of more than 1 .5, preferably of between 1 .5 and 5.0. Particularly carboxylic acids such as Ci-io-monocarboxylic acids or C2- -dicarboxylic acids or Cs-12-tricarboxylic acid, such as particularly formic acetic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, fumaric acid or citric acid.

[0063] Most preferred acids are ammonium hydrogen sulfate, metal hydrogen sulfate, phosphoric acid or citric acid; more preferred in the presence of a metal hydrogen sulfate or citric acid.

[0064] Compound of the formula (I)

[0065] The process of rearrangement of compound of the formula (II) leads to the formation of the compound of the formula (I).

[0066] Typically, in the rearrangement reaction also other products are formed. However, compared to the use of other catalysts, the present process is very advantageous in that it yields the desired product of formula (I) in high conversion, and high yield at a very high selectivity.

[0067] In one embodiment, the compound of the formula (I) is a compound of the compound of the formula (II) is a compound of the formula

[0068] Preferably, the compound of the formula (I) is a compound of the formula (I-A1 ) and the compound of the formula (II) is a compound of the formula (II-A1 )

[0069] In a preferred embodiment, the compound of the formula (I) is a compound of the formula (I-B1 a) and the compound of the formula (II) is a compound of the formula (I I-B1 a) wherein R1represents H, a Ci-8-alkyl group or a Ce-12-aryl group, preferably H.

[0070] It is very preferred that the compound of the formula (I) is the compound of the formula (I-B1 b) and the compound of the formula (II) is the compound of the formula (ll-B1 b)

[0071] In another embodiment, the compound of the formula (I) is a compound of the formula (l-B2a) and the compound of the formula (II) is a compound of the formula (I l-B2a) wherein R1represents H, a Ci-8-alkyl group or a Ce-12-aryl group, preferably H, and R6represents is a Ci -1 o-alkyl group, preferably a methyl or an ethyl or an / so-propyl or a sec-butyl group.

[0072] Preferably the compound of the formula (I) is the compound of the formula (l-B2b) and the compound of the formula (II) is the compound of the formula (I l-B2b)

[0073] In another preferred embodiment, the compound of the formula (I) is a compound of the formula (I-B3), preferably a compound of the formula (l-B3a), and the compound of the formula (II) is a compound of the formula (II-B3), preferably a compound of the formula ( I l-B3a), wherein R1represents H, a Ci -8-alkyl group or a Ce-12-aryl group, preferably H.

[0074] Accordingly, it is very much preferred that the compound of the formula (I) is 1 -((1 Z,5E,9E)-cyclododeca-1 , 5, 9-trien-1 -yl)ethan-1 -one (l-B3aa) and the compound of the formula (II) is (4E,8E)-1-ethynylcyclododeca-4,8-dien-1-ol (ll-B3b).

[0075]

[0076] In another embodiment, the compound of the formula (I) is a compound of the formula ( I-B4) and the compound of the formula (II) is a compound of the formula (I I-B4) wherein R1, R2and R3, independently from each other, represent H, a C1-8- alkyl group or a Ce-12-aryl group, preferably H.

[0077] Preferably the compound of the formula (I) is the compound of the formula

[0078] (l-B4b) and the compound of the formula (II) is the compound of the formula (II-

[0079] B4b)

[0080] (l-B4b)

[0081] (ll-B4b).

[0082] It has been surprisingly found that compounds of the formula (I) can be produced from the respective compound of formula (II) in a high yield at very high conversion and selectivity. The process is also very advantageous as it uses a catalyst which is based on naturally occurring materials and is easy to dispose. Hence, the above process provides an excellent advantage in view of both high sustainability and low cost.

[0083] Therefore, in a further aspect, the invention relates to a composition which comprises a) a compound of the formula (II) b) a phyllosilicate clay, particularly a clay selected from the smectite group; c) optionally water d) optionally an organic solvent, preferably an organic solvent selected from the group consisting of ethers, aromatic hydrocarbons, hydrogenated aromatic hydrocarbons, alcohols, and esters, particularly selected from the group consisting of tetrahydrofuran (THF), 2- methyltetrahydrofuran (MeTHF), cyclopentyl methyl ether (CPME), 1 ,4- dioxane, toluene, chlorobenzene, n-butanol and n-butylacetate, preferably 2-methyltetrahydrofuran; e) optionally an acid, preferably an acid with a pKa of more than 1 .5, preferably of between 1 .5 and 5.0, most preferably in the presence of ammonium hydrogen sulfate, metal hydrogen sulfate, phosphoric acid or citric acid, more preferred in the presence of a metal hydrogen sulfate or citric acid;

[0084] The ingredients of this composition, particularly compound of the formula (II) , and the clay, as well its preferred embodiments, ratios and ranges have been discussion already in great detail above in this document.

[0085] In an embodiment, the composition comprises a) a compound of the formula (II) b) a phyllosilicate clay, particularly a clay selected from the smectite group; c) an organic solvent selected from the group consisting of tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF), cyclopentyl methyl ether (CPME), 1 ,4-dioxane, toluene, chlorobenzene, n-butanol and n- butylacetate, preferably 2-methyltetrahydrofuran; d) optionally an acid, preferably an acid with a pKa of more than 1 .5, preferably of between 1 .5 and 5.0, most preferably in the presence of ammonium hydrogen sulfate, metal hydrogen sulfate, phosphoric acid or citric acid, more preferred in the presence of a metal hydrogen sulfate or citric acid; e) optionally water; wherein

[0086] R1and R2and R3, independently from each other, either represents H, a Ci- -alkyl group or a Ce-12-aryl group; and R4and R5either, independently from each other, represents a Ci -1 o-alkyl group which, optionally, comprises at least one carbon-carbon double bond or a Ce-12-aryl group; or form together a C2-2o-alkylene group, particularly a C3-9-alkylene group, which, optionally, comprises at least one carbon-carbon double bond.

[0087] The compound of the formula (I) has olfactory properties.

[0088] Hence, in another aspect, the invention relates to a method of producing a perfumery composition, comprising the steps i) preparing a compound of the formula (I) by a process as described above in great detail ii) admixing the compound of the formula (I) to a perfumery carrier and a perfumery base, preferably to an alcohol, particularly a glycol, preferably dipropylene glycol, or ethanol, in a weight ratio of compound of the formula (I) : alcohol in the range of 1 : 10 to 1 : 10'000, preferably 1 :50 to 1 :5'000.

[0089] It is particularly preferred that the amount of the perfumery composition comprises 0.05 % to 20 % by weight, of the compound (I) based on the weight of the perfumery composition into which they are incorporated. In the case of perfumed consumer product, typical concentrations are in the order of 0.01% to 10% by weight, of the compound of the formula (I) based on the weight of the consumer product into which they are incorporated.

[0090] Furthermore, any other ingredients and additives which are typically used in the field of fragrance and perfumery industries are used, can be added to said perfumery composition.

[0091] It is preferred that perfumery composition is a perfume, a fabric care product, a body-care product, a cosmetic preparation, a skin-care product, an air care product or a home care product.

[0092] It is further preferred that the perfumery composition is a fine perfume, a splash or eau de parfum, a cologne, a shave or after-shave lotion, a liquid or solid detergent optionally in the form of a pod or tablet, a laundry sheet, a soluble laundry sheet, a fabric softener, a liquid or solid scent booster, a dryer sheet, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtaincare product, a shampoo, a leave-on or rinse-off hair conditioner, a coloring preparation, a color-care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair spray, skin cream or lotion, a vanishing cream, a deodorant or antiperspirant, a hair remover, a tanning or sun or after sun product, a nail product, a skin cleansing, a makeup, a perfumed soap, a shower or bath mousse, oil or gel, a foot / hand care product, a hygiene product, an air freshener, a “ready to use” powdered air freshener, a mold remover, a furnisher care, a wipe, a dish detergent or hard-surface detergent, a leather care product, a car care product.

[0093] Examples

[0094] The following examples are provided to further illustrate the compositions and effects of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way.

[0095] General procedure for producing compound of the formula (I)

[0096] 522 g clay as specified in table 1 in 900 g 2-methyltetrahydrofuran (Me- THF), saturated with water was stirred at room temperature (23°C). Then 607.97 g NaHSCU, has been added at room temperature with a good stirring. Then the reaction mixture has been heated to reflux of the solvent (80°C). Then 12.7 mol of the alpha-alkynol of the respective formula (II) given in table 1 in 527.90 g Me-THF saturated with water was added to the mixture and stirred at this temperature for another 90 minutes. After further vigorous stirring at reflux for 21 .5 hours a sample of the reaction mixture has taken been analysed.

[0097] After cooling to room temperature, 1426 g of water and 2145 g of toluene have been added to the reaction mixture which then has been filtrated. The two phases have been separated and the organic phase has been washed with aqueous NaOH solution (10%). After removal of the of the solvent the respective product of rearrangement has been distilled and characterized. Details of product obtained reported in table 1 .

[0098]

[0099] 1relative to compound of formula (II)

[0100] Characterization:

[0101] Examples 1 and 2: 13C-NMR (150.91 MHz, CDCI3): 23.7; 25.8; 26.7; 26.9; 29.4; 29.7; 30.1 ; 128.0; 129.4; 130.3; 131.0; 142.8; 143.6; 200.20.

[0102] 1H-NMR (600.15 MHz, CDCI3): 1.93-2.00 (m,2H; 2.03-2.09 (m,2H); 2.15-2.25 (m,4H); 2.31 (s,3H); 2.33-2.45 (m,4H); 5.24(mc,1 H); 5.31-5.38 (m,1 H); 5.45

[0103] Major Minor

[0104] Major :13C-NMR (125 MHz, CDCI3): 19.09; 23.17; 25.26; 29.19; 32.78; 36.36; 137.30; 149.81 ; 199.99.1H-NMR (600.15 MHz, CDCI3): 1.24 (s, 6H); 1.47-1.53 (m, 2H); 1.64-1.74 (m, 2H);

[0105] 2.13 (s, 3H); 2.33-2.45 (m,3H); 6.71 (s, 3H).

[0106] Minor:13C-NMR (125 MHz, CDCI3): 19.3; 24.16; 25.4; 28.1 ; 28.6; 34.3; 138.8; 139.9; 200.2. MHz, CDCI3): 0.94 (s, 6H); 1.53-1.65 (m, 2H); 1.84 (s, 2H); 1.95- 4 (s, 3H); 6.65-6.74 (m, 1 H). MHz, CDCI3): 12.32; 19.07; 22.30; 22.43; 22.54; 26.69; 27.56; .67; 142.46; 207.41. z, CDCI3): 0.94 (t, J = 8.0Hz, 3H); 1.09 (d, J=6.8 Hz, 3H); 1.34- 5-1.74 (m, 4H); 1.90-1.96 (m, 4H); 2.13 (s, 3H); 2.13-2.24 (m, Hz, CDCI3): 23.0; 26.8; 30.5; 34.0; 144.2; 145.7; 196.2. z, CDCI3): 6.72-6.68 (m, 1 H); 2.58-2.45 (m, 4H); 2.28 (s, 3H); , z, 2H).

[0107] In a further experimental series, the clays of experiments 1 using the compound of formula (ll-B3b) as compound of the formula (II) have been replaced by different zeolites (in the same amount). The results have been summarized in table 2.

[0108] (Il-B3b)

[0109] Table 2:1relative to compound of formula (II)

[0110] 2zeolite types:

[0111] Mordenite Type: CBV21A, CBV 10A

[0112] Y-Type (Linde): CBV 600, CBV 780

[0113] Beta-type: HSZ 940HOA, CP 814C, CP 814E

Claims

Claims1 . A process of producing a compound of the formula (I)characterized in that said rearrangement reaction is catalyzed by a phyllosilicate clay, particularly by a clay from the smectite group and whereinR1and R2and R3, independently from each other, either represents H, a C1-1 o-alkyl group or a Ce-12-aryl group; and R4and R5either, independently from each other, represents a Ci- -alkyl group which, optionally, comprises at least one carbon-carbon double bond or a Ce-12-aryl group; or form together a C2-2o-alkylene group, particularly a Cs-9-alkylene group, which, optionally, comprises at least one carbon-carbon double bond; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the Econfiguration; and any double bond having dotted line ( - ) represents independently from each other either a single carbon-carbon bond or a carbon-carbon double bond;with the proviso that the compound of the formula (I) does not comprise two cumulated carbon-carbon double bonds and that at least one of the double bond having dotted line ( - ) represents a carbon-carbon double bond.

2. The process according to claim 1 , characterized in that R1represents H.

3. The process according to claim 1 or 2, characterized in that R2= R3= CH3.

4. The process according to any of the preceding claims characterized in that the compound of the formula (I) is a compound of the formula (I-B1 ) and the compound of the formula (II) is a compound of the formula (II-B1 )wherein R1represents H, a Ci-s-alkyl group or a Ce-12-aryl group, preferably H.

5. The process according to any of the preceding claims characterized in that the compound of the formula (I) is a compound of the formula (l-B), preferably a compound of the formula (I-B3), and the compound of the formula (II) is a compound of the formula (II-B3), preferably a compound of the formula (II-B3),wherein R1represents H, a Ci-8-alkyl group or a Ce-12-aryl group, preferably H.

6. The process according to any of the preceding claims characterized in that the compound of the formula (I) is 1-((1Z,5E,9E)-cyclododeca-1 ,5,9-trien-1 - yl)ethan-1 -one and the compound of the formula (II) is (4E,8E)-1 - ethynylcyclododeca-4,8-dien-1 -ol.

7. The process according to any of the preceding claims characterized in that the clay is a montmorillonite-based clay, particularly in the form of bentonite.

8. The process to any of the preceding claims characterized in that the clay is an acid treated clay.

9. The process according to any of the preceding claims characterized in that the weight ratio of the clay : compound of the formula (II) is in the range of100:0.5 to 100:60, preferably 100:2 to 100:50, more preferably 100:4 to 100:30, most preferably 100:5 to 100:20.

10. The process according to any of the preceding claims characterized in that the rearrangement reaction is performed in a presence of an organic solvent, preferably an organic solvent selected from the group consisting of ethers, aromatic hydrocarbons, hydrogenated aromatic hydrocarbons, alcohols, and esters, particularly selected from the group consisting of tetrahydrofuran (THF), 2-methyltetrahydrofuran (MeTHF), cyclopentyl methyl ether (CPME),1 ,4-dioxane, toluene, chlorobenzene, n-butanol and n-butylacetate, preferably 2-methyltetrahydrofuran.11 . The process according to any of the preceding claims characterized in that the rearrangement reaction is performed in a presence of water, more preferably in the presence of water and an organic solvent, preferably an organic solvent selected from the group consisting of ethers, aromatic hydrocarbons, hydrogenated aromatic hydrocarbons, alcohols, and esters, particularly selected from the group consisting of tetrahydrofuran (THF), 2- methyltetrahydrofuran (MeTHF), cyclopentyl methyl ether (CPME), 1 ,4- dioxane, toluene, chlorobenzene, n-butanol and n-butylacetate, preferably 2- methyltetrahydrofuran.

12. The process according to any of the preceding claims characterized in that the rearrangement reaction is performed at a temperature of between 40 and 140°C, preferably between 60 and 90 °C.

13. The process according to any of the preceding claims characterized in that the rearrangement reaction is performed in a presence of an acid, preferably an acid with a pKa of more than 1 .5, preferably of between 1 .5 and 5.0, most preferably in the presence of ammonium hydrogen sulfate, metal hydrogen sulfate, phosphoric acid or citric acid, more preferred in the presence of a metal hydrogen sulfate or citric acid.

14. Composition comprising a) a compound of the formula (II)b) a phyllosilicate clay, particularly a clay selected from the smectite group; c) optionally water d) optionally an organic solvent, preferably an organic solvent selected from the group consisting of ethers, aromatic hydrocarbons, hydrogenated aromatic hydrocarbons, alcohols, and esters, particularly selected from the group consisting of tetrahydrofuran (THF), 2- methyltetrahydrofuran (MeTHF), cyclopentyl methyl ether (CPME), 1 ,4- dioxane, toluene, chlorobenzene, n-butanol and n-butylacetate, preferably 2-methyltetrahydrofuran. e) optionally an acid, preferably an acid with a pKa of more than 1 .5, preferably of between 1 .5 and 5.0, most preferably in the presence of ammonium hydrogen sulfate, metal hydrogen sulfate, phosphoric acid or citric acid, more preferred in the presence of a metal hydrogen sulfate or citric acid; whereinR1and R2and R3, independently from each other, either represents H, aCM o-alkyl group or a Ce-12-aryl group; andR4and R5either, independently from each other, represents a Ci- -alkyl group which, optionally, comprises at least one carbon-carbon double bond or a Ce-12-aryl group; or form together a C2-2o-alkylene group, particularly a Cs-9-alkylene group, which, optionally, comprises at least one carbon-carbon double bond.

15. Method of producing a perfumery composition, comprising the stepsi) preparing a compound of the formula (I) by a process according to any of the preceding claims 1 to 13ii) admixing the compound of the formula (I) to a perfumery carrier and a perfumery base, preferably to an alcohol, particularly a glycol, preferably dipropylene glycol, or ethanol, in a weight ratio of compound of the formula (I) : alcohol in the range of 1 : 10 to 1 : 10'000, preferably 1 :50 to 1 :5'000.

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