Method for producing oxacyclohexane or oxacyclopentane derivatives

Abstract

The present invention relates to the field of organic synthesis, and more particularly to a process for the preparation of cycloethers of formula (I), comprising the cyclization of compounds of formula (II) in the presence of a heterogeneous acidic catalyst.

Description

[Technical Field]

[0001] Technical field The present invention relates to the field of organic synthesis, and more particularly to a method for producing a cycloether of formula (I), comprising the cyclization of a compound of formula (II) carried out in the presence of a heterogeneous acidic catalyst.

[0002] background Cycloether derivatives represent highly desirable skeletons and can be used as is, or as key intermediates useful in producing more complex compounds, particularly in different fields such as fragrances, cosmetics, pharmaceuticals, or agrochemicals. Relevant cycloether derivatives in the fragrance industry include, for example, Cetalox® (3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; manufactured by Firmenich SA, Geneva, Switzerland) or Ambrox® ((3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; manufactured by Firmenich SA, Geneva, Switzerland), which are major components of natural ambergris. These fragrance components represent some of the most sought-after components in the fragrance industry. Several alternative methods have been developed for producing Cetalox® or Ambrox®, in particular, a method involving the cyclization of 2-(5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol as the final step. It has been disclosed that cyclization under acidic conditions results in low yield or low selectivity due to isomerization of the double bond of the starting material or the formation of undesirable diastereoisomers.

[0003] On the other hand, today there is a need to promote sustainable processes that use recyclable catalysts, such as heterogeneous catalysts. The cyclization reaction of 2-(5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol in the presence of a heterogeneous catalyst for the production of Cetalox® or Ambrox® has not been reported to date.

[0004] Accordingly, there still remains a need to develop a sustainable cyclization process in the presence of a small amount of a heterogeneous catalyst while improving conversion and selectivity.

[0005] The present invention makes it possible to solve the above problems by using a heterogeneous acid catalyst for producing the cycloether of formula (I). To the best of the inventors' knowledge, the conditions of the present invention have not been reported in the prior art.

[0006] Summary of the Invention The present invention relates to a novel method that enables production of a cycloether of formula (I) by cyclizing a compound of formula (II) in the presence of a small amount of a heterogeneous acid catalyst, which has neither been reported nor suggested in the prior art.

[0007] Accordingly, a first object of the present invention is the following formula (I)

Chemical structure

[0008] The second object of the present invention is, a) at least 95% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, b) at most 5% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan The composition contains [the specified substance], and the percentage is relative to the total weight of the composition.

[0009] Description of the Invention Surprisingly, it was discovered that compound (I) can be produced in high yield and with high selectivity by cyclizing compound (II) in the presence of a small amount of heterogeneous acidic catalyst. The method of the present invention makes it possible to limit and even prevent double bond isomerization at more stable positions, i.e., terminal double bond isomerization, while maintaining and improving the formation of desired isomers, i.e., limiting the formation of undesirable diastereoisomers.

[0010] Therefore, the first object of the present invention is the following formula (I) [ka] [wherein m is 1 or 2; R 1 is a hydrogen atom or C 1~3 Represents an alkyl group; Each R 2 , R 3 , R 4 Each C separately and independently contains a hydrogen atom or one or two functional groups selected from ether, ester, carbonyl, amine, amide, or alcohol groups. 1~18 Does it represent an alkyl group? R 1 and R 2 Together, C optionally contains one or two functional groups selected from ether, ester, carbonyl, amine, amide, or alcohol groups. 2~11 Represents an alkanediyl group and / or R 2 and R 3 Together, C 1~11 Represents an alkanediyl group and / or R 3 and R 4 Together, C 4~9 Represents an alkanediyl group and / or R 1 and R 4 Together, C 2~9 Represents an alkanediyl group; R 5 is a hydrogen atom or C 1~3 A method for producing a cycloether of an alkyl group in the form of one of its stereoisomers or a mixture thereof, wherein the following formula (II) [ka] [In the formula, m, R 1 , R 2 , R 3 , R 4 and R 5The method comprises cyclizing a compound [having the same meaning as defined] in the form of one of its stereoisomers or a mixture thereof, in the presence of a heterogeneous acidic catalyst.

[0011] For clarity, the expression "one of its stereoisomers or a mixture thereof," or similar expressions, means in the ordinary sense understood by those skilled in the art, that is, the compounds referenced in this invention may be pure enantiomers or mixtures of enantiomers. In other words, the compounds referenced in this invention may have at least one stereocenter which may have two different stereochemistrys (e.g., R or S), for example, R 2 The group may contain at least one stereocenter. The compound may be in the form of a pure enantiomer or a mixture of enantiomers. The compounds referenced in this invention may be in the form of a pure diastereoisomer or, if the compound has two or more stereocenters, a mixture of diastereoisomers. The compound may be in the form of a racemic or scalemic form. Thus, the compound may be a single stereoisomer, or it may contain various stereoisomers, or it may be in the form of a composition comprising them.

[0012] The term "arbitrarily" is understood to mean that the group may or may not contain a specific functional group.

[0013] The terms "alkyl" and "alkanediyl" are understood to include linear, branched, cyclic, or alicyclic alkyl and alkanediyl groups.

[0014] The phrase "...optionally comprising one or two functional groups selected from ether, ester, carbonyl, amine, amide, or alcohol groups" is understood to mean that these groups can be substituted for hydrogen atoms of the alkyl group and thus bonded laterally to the alkyl group, or substituted for carbon atoms of the alkyl group (where chemically possible) and thus inserted into the alkyl chain. For example, the -CH2-CH2-CHOH-CH2- group represents a C4 alkyl group containing an alcohol group (hydrogen atom substitution), the -CH2-CH2-COO-CH2-CH2-OCO-CH2-CH2- group represents a C6 alkyl group containing two ester groups (carbon atom substitution / insertion into the alkyl chain), and similarly, the -CH2-CH2-O-CH2-CH2-O-CH2-CH2- group represents a C6 alkyl group containing two ether groups.

[0015] "...R" 1 and R 2 Together, ...C 2~11 Represents an alkanediyl group and / or R 2 and R 3 Together, C 1~11 Represents an alkanediyl group and / or R 3 and R 4 Together, they represent ... and / or R 1 and R 4 It is understood that the above groups can form a (poly)cyclic alkyl group by the expression "together, ..." or similar. In other words, compound (II) may be acyclic, monocyclic, bicyclic, or tricyclic, and compound (I) may be monocyclic, bicyclic, tricyclic, or tetracyclic. For example, R 2 and R 3 , and R 3 and R 4 However, when combined, the compound of formula (II) contains a bicyclic part such as decalin. For example, R 2 , R 3 and R 4 When combined, they represent Arcantril.

[0016] According to a particular embodiment, the compound of formula (II) is a compound of formula (II) and formula (II') [ka] [In the formula, m, R 1 , R 2 , R 3 , R 4 and R 5 The compound of formula (II) may be in the form of a composition containing the compound of formula (II) as defined above. In particular, the compound of formula (II) may be in the form of a composition containing the compound of formula (II) and the compound of formula (II'). In particular, the compound of formula (II) may be in the form of a composition containing at least 50% of the compound of formula (II) and up to 50% of the compound of formula (II'), where the percentages are relative to the total weight of the composition. In particular, the compound of formula (II) may be in the form of a composition containing at least 60% of the compound of formula (II) and up to 40% of the compound of formula (II'). In particular, the compound of formula (II) may be in the form of a composition containing at least 70% of the compound of formula (II) and up to 30% of the compound of formula (II'). In particular, the compound of formula (II) may be in the form of a composition containing at least 80% of the compound of formula (II) and up to 20% of the compound of formula (II'). In particular, the compound of formula (II) may be in the form of a composition containing at least 90% of the compound of formula (II) and up to 10% of the compound of formula (II'). In particular, the compound of formula (II) may be in the form of a composition containing at least 95% of the compound of formula (II) and up to 5% of the compound of formula (II'). In particular, the compound of formula (II) may be in the form of a composition containing at least 98% of the compound of formula (II) and up to 2% of the compound of formula (II'). In particular, the compound of formula (II) may be in the form of a composition containing at least 99% of the compound of formula (II) and up to 1% of the compound of formula (II'). In particular, the compound of formula (II) may be in the form of a composition containing at least 99.5% of the compound of formula (II) and up to 0.5% of the compound of formula (II'). More specifically, the compound of formula (II) does not contain the compound of formula (II').

[0017] According to any embodiment of the present invention, the heterogeneous acidic catalyst may be amorphous or crystalline, and in particular crystalline.

[0018] According to certain embodiments of the present invention, the heterogeneous acidic catalyst may be an acidic resin. Non-limiting examples of suitable acidic resins include A-15 Dry, A-35 Dry, and A-36 Dry, which are sold by Dupont.

[0019] According to any embodiment of the present invention, the heterogeneous acidic catalyst comprises silicon, tin, zirconium, hafnium, or titanium, and a second metal selected from the group consisting of aluminum, boron, iron, or mixtures thereof. In particular, the heterogeneous acidic catalyst may be an aluminosilicate catalyst. In particular, the aluminosilicate catalyst may be a zeolite or clay.

[0020] According to any embodiment of the present invention, commercially available clay may contain water. This water can be partially or completely removed before use. Those skilled in the art are familiar with methods for removing water, such as azeotropic distillation, vacuum removal, or heating under a nitrogen stream.

[0021] According to any embodiment of the present invention, the clay may be a naturally occurring material. In particular, the clay is an acid-treated clay. Non-limiting examples of suitable clays include F-20X, F20-XLM, F-21X, F-24X, F-22, F-118FF, currently sold by EP Minerals; Fulcat-22F and Fulcat-22B, sold by Byk; and K-5, K-10-S300, K-20, K-21, K-30, and K-41, sold by Clariant.

[0022] According to any embodiment of the present invention, the zeolite is a large-pore zeolite.

[0023] The term "large-pore zeolite" means, in the common sense in the art, a 12-membered ring zeolite having a pore size that falls within the range of 6.0 angstroms to 7.5 angstroms.

[0024] According to any embodiment of the present invention, the zeolite has FAU, BEA, and MOR topologies. In particular, the zeolite has a FAU topology.

[0025] According to any embodiment of the present invention, the silicon:aluminum ratio is in the range of 2.5:1 to 300:1. In particular, the silicon:aluminum ratio is in the range of 5:1 to 150:1. In particular, the silicon:aluminum ratio is in the range of 10:1 to 150:1. More specifically, the silicon:aluminum ratio is in the range of 10:1 to 70:1.

[0026] According to any embodiment of the present invention, the zeolite is used in its protonated form. The latter is supplied directly by the manufacturer and can be used as is, or can be obtained by calcining an ammonium exchanger as needed. In particular, the zeolite may be pre-activated before the reaction. Pre-activation may be carried out by heating the zeolite at a temperature between 300°C and 600°C for at least one hour.

[0027] Non-specific examples of suitable zeolites include CBV720, CBV760, and CBV780, currently sold by Zeolyst Corporation.

[0028] Heterogeneous acidic catalysts can be added to the reaction medium of the method of the present invention to form the cycloether of formula (I) at a wide range of concentrations. As a non-limiting example, heterogeneous acidic catalyst concentrations can range from 0.5% to 20% by weight relative to the total amount of cycloether of formula (I). In particular, the heterogeneous acidic catalyst concentration can be between 1% and 15% by weight. More specifically, the heterogeneous acidic catalyst concentration can be between 3% and 10% by weight. Needless to say, this method will also function with greater amounts of catalyst. However, the optimal concentration of the heterogeneous acidic catalyst will depend, as those skilled in the art will know, on the properties of the latter, the properties of the substrate, the temperature, and the desired reaction time.

[0029] Heterogeneous acidic catalysts are commercially available compounds or can be manufactured by several methods, such as those reported in U.S. Patent No. 20040141911, U.S. Patent No. 6054113, U.S. Patent No. 4840930, U.S. Patent No. 2470872 and European Patent No. 0398636.

[0030] According to any one embodiment of the present invention, the method of the present invention for producing the cycloether of formula (I) is carried out at a temperature between 0°C and 150°C. In particular, the temperature is in the range of 30°C to 70°C. Of course, those skilled in the art may also select a preferred temperature depending on the melting and boiling points of the starting materials and the final product, as well as the desired reaction time, conversion rate, or selectivity.

[0031] The method of the present invention for producing the cycloether of formula (I) may be carried out in or without a solvent. Where a solvent is required or used for practical reasons, any existing solvent of this type of reaction may be used for the purposes of the present invention. A non-limiting example is C 6~12Examples of solvents include aromatic solvents such as xylene, toluene, 1,3-diisopropylbenzene, cumenepsoidcumene, anisole, or chlorobenzene or mixtures thereof; hydrocarbon solvents such as cyclohexane, heptane, or mixtures thereof; nitrile solvents such as acetonitrile; ester solvents such as ethyl acetate; or ether solvents such as tetrahydrofuran, diethyl ether, methyltetrahydrofuran, or mixtures thereof. The choice of solvent depends on the properties of the substrate and / or catalyst, and those skilled in the art can successfully select the most suitable solvent in each case to optimize the reaction.

[0032] The present invention's method for producing the cycloether of formula (I) can be carried out under batch or continuous conditions.

[0033] The present invention's method for producing the cycloether of formula (I) can be carried out under atmospheric pressure or slight reduced pressure.

[0034] According to any one embodiment of the present invention, the cycloether of formula (I) is a polycyclic compound. The term “polycyclic compound” is understood to mean that the compound of formula (I) contains at least two rings, for example, the cycloether of formula (I) is a bicyclic compound. In particular, the cycloether of formula (I) may be a bicyclic, tricyclic, tetracyclic, or pentacyclic compound. More specifically, the cycloether of formula (I) may be a condensed bicyclic, tricyclic, or tetracyclic compound.

[0035] According to any one of the above embodiments of the present invention, the cycloether of formula (I) is C9~C 20 It is a compound.

[0036] According to any one of the above embodiments of the present invention, R 1 is a hydrogen atom or C 1~3 They may be linear or branched alkyl groups. In particular, R 1 R may be a hydrogen atom, a methyl group, or an ethyl group. In particular, 1may be a hydrogen atom or a methyl group. More specifically, R 1 may be a hydrogen atom.

[0037] According to any one of the embodiments of the present invention, m may be 1. In other words, the compound of formula (I) is a tetrahydrofuran derivative.

[0038] According to any one of the embodiments of the present invention, R 2 and R 3 together may represent a C 1~11 alkanediyl group. In particular, R 2 and R 3 together may represent a linear or branched alkanediyl group of C 1~11 .

[0039] According to any one of the embodiments of the present invention, the cyclic ether is a compound of the following formula

Chemical Formula

[0040] According to any one of the embodiments of the present invention, the compound of formula (II) is a compound of the following formula

Chemical Formula

[0041] According to certain embodiments, compound (III) may be a tricyclic compound, and the compound of formula (IV) may be a bicyclic compound. Said compound of formula (IV) may be synthetic or natural.

[0042] According to any one of the embodiments of the present invention, R 6 and R 7 may each independently, separately from each other, represent a hydrogen atom or C optionally containing one or two functional groups selected from ether, ester, carbonyl, amine, amide or alcohol groups 1~9 alkyl group, or R 6 and R 7 together represent C 3~9 a linear or branched alkanediyl group. In particular, R 6 and R 7 may each independently, separately from each other, represent an optionally substituted C containing one or two functional groups selected from ether, ester, carbonyl, amine, amide or alcohol groups 1~6 alkyl group, and R 6 and R 7 together may represent C 3~8 a linear or branched alkanediyl group. In particular, R6 and R 7 Each C is separately and independently of the others, and is optionally substituted with one or two functional groups selected from a hydrogen atom or an ether, ester, carbonyl, amine, amide, or alcohol group. 1~4 It may also represent an alkyl group, R 6 and R 7 Together, C 3~8 It may represent a linear or branched alkanediyl group.

[0043] According to any one embodiment of the present invention, the above R 6 The group is a hydrogen atom or C 1~3 It may also represent an alkyl group. In particular, R 6 The group may represent a hydrogen atom or a methyl group. More specifically, R 6 The base may represent a hydrogen atom.

[0044] According to any one embodiment of the present invention, the above R 7 The group is a hydrogen atom or C 1~3 It may also represent an alkyl group. In particular, R 7 The group may represent a hydrogen atom or a methyl group. More specifically, R 7 The base may represent a hydrogen atom.

[0045] According to any one embodiment of the present invention, the above R 6 and R 7 Together, C 3~6 It may represent a linear or branched alkanediyl group, or more preferably a C6 branched alkanediyl group.

[0046] According to any one embodiment of the present invention, n may be 1.

[0047] According to any one embodiment of the present invention, the cycloether is the following formula [ka] [In the formula, R 8This has the same meaning as defined above, and each R 9 and R 10 They are independent of each other, C 1~3 The compound may be in the form of one or a mixture thereof of stereoisomers of a linear or branched alkyl group.

[0048] According to any one embodiment of the present invention, the compound of formula (II) is the following formula [ka] [In the formula, R 8 This has the same meaning as defined above, and each R 9 and R 10 They are independent of each other, C 1~3 A compound in the form of one of its stereoisomers or a mixture thereof, representing a linear or branched alkyl group.

[0049] According to any one embodiment of the present invention, R 8 C 1~3 It may also be a linear alkyl group. In particular, R 8 R may be a methyl group or an ethyl group. More specifically, 8 It may be a methyl group.

[0050] According to any one embodiment of the present invention, R 9 R may be a methyl group or an ethyl group. More specifically, 9 It may be a methyl group.

[0051] According to any one embodiment of the present invention, R 10 R may be a methyl group or an ethyl group. More specifically, 10 It may be a methyl group.

[0052] According to certain embodiments of the present invention, the compound of formula (II) may be 2-(5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol, and the corresponding cycloether of formula (I) may be 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, which has four stereocenters and is in the configuration of R or S, or a mixture thereof. In other words, 2-(5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol may be in the form of a substantially pure stereoisomer or a mixture of stereoisomers. According to certain embodiments of the present invention, the compound of formula (II), (IV), or (VI) may be 2-(5,5,8a-trimethyl-2-methylenedecahydronaphthalen-1-yl)ethane-1-ol in the form of a mixture of stereoisomers containing at least 50% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalen-1-yl)ethane-1-ol. More specifically, the compound of formula (II), (IV), or (VI) may be 2-(5,5,8a-trimethyl-2-methylenedecahydronaphthalen-1-yl)ethane-1-ol in the form of a mixture of stereoisomers containing at least 75% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalen-1-yl)ethane-1-ol. According to certain embodiments of the present invention, the compound of formula (II), (IV), or (VI) may be 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol. For clarity, the expression "1SR,4aSR,8aRS" means an equimolar mixture of 1S,4aS,8aR and 1R,4aR,8aS. According to certain embodiments of the present invention, the compound of formula (II), (IV), or (VI) may be 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol.

[0053] According to certain embodiments of the present invention, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 50% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 50% 2-((1SR,4aSR,8aSR)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 60% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 40% 2-((1SR,4aSR,8aSR)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 70% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 30% 2-((1SR,4aSR,8aSR)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 80% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 20% 2-((1SR,4aSR,8aSR)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol.In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 90% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 10% 2-((1SR,4aSR,8aSR)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 95% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 5% 2-((1SR,4aSR,8aSR)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 98% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 2% 2-((1SR,4aSR,8aSR)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 99% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 1% 2-((1SR,4aSR,8aSR)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol.More specifically, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 99.5% 2-((1SR,4aSR,8aSR)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 0.5% 2-((1SR,4aSR,8aSR)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol.

[0054] According to certain embodiments of the present invention, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 50% 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 50% 2-((1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 60% 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 40% 2-((1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 70% 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 30% 2-((1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 80% 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 20% 2-((1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 90% 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 10% 2-((1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol.In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 95% 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 5% 2-((1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 98% 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 2% 2-((1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. In particular, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 99% 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 1% 2-((1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol. More specifically, the compound of formula (II), (IV), or (VI) may be in the form of a composition comprising at least 99.5% 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and up to 0.5% 2-((1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol.

[0055] According to any embodiment of the present invention, the method of the present invention is stereoselective. In other words, dehydration cyclization of 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol provides (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.

[0056] According to a particular embodiment of the present invention, the compound of formula (I) may be 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan in the form of a mixture of stereoisomers containing at least 50% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. More specifically, the compound of formula (I) may be 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan in the form of a mixture of stereoisomers containing at least 75% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. According to a particular embodiment of the present invention, the compound of formula (I) may be (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. For clarity, the expression "3aRS,5aSR,9aSR,9bRS" means an equimolar mixture of 3aR,5aS,9aS,9bR and 3aS,5aR,9aR,9bS. According to a particular embodiment of the present invention, the compound of formula (I) may be (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.

[0057] According to certain embodiments of the present invention, the compound of formula (I) may be in the form of a composition comprising at least 95% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 5% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition comprising at least 96% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 4% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing at least 97% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 3% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing at least 98% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 2% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing at least 99% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 1% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing at least 99.3% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.7% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.In particular, the compound of formula (I) may be in the form of a composition containing at least 99.4% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.6% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. More specifically, the compound of formula (I) may be in the form of a composition containing at least 99.5% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.5% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.

[0058] According to certain embodiments of the present invention, the compound of formula (I) may be in the form of a composition comprising at least 95% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 5% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition comprising at least 96% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 4% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing at least 97% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 3% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing at least 98% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 2% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing at least 99% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 1% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing at least 99.3% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.7% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.In particular, the compound of formula (I) may be in the form of a composition containing at least 99.4% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.6% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1]furan. More specifically, the compound of formula (I) may be in the form of a composition containing at least 99.5% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.5% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.

[0059] According to certain embodiments of the present invention, the compound of formula (I) may be in the form of a composition comprising 95% to 99.99% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 5% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing 96% to 99.99% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 4% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing 97% to 99.99% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 3% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing 98% to 99.99% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 2% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing 99% to 99.99% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 1% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing 99.3% to 99.99% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 0.7% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.In particular, the compound of formula (I) may be in the form of a composition containing 99.3% to 99.9% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.1% to 0.7% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing 99.4% to 99.9% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.1% to 0.6% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing 99.5% to 99.9% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.1% to 0.5% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compound of formula (I) may be in the form of a composition containing 99.5% to 99.8% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.2% to 0.5% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.

[0060] Unless otherwise specified, percentages (%) refer to the weight percentage of the composition.

[0061] The compounds of formulas (II), (IV), and (VI) can be produced by several methods known in the art, for example, in the case of 2-(5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol, which can be obtained as reported in the Australian Journal of Chemistry, 1989, 497. The compounds of formulas (II), (IV), or (VI) may be produced in vitro by fermentation using enzymes prepared by purified recombinant enzymes, or by fermentation using host cells such as microbial cells that have been genetically engineered to convert an inexpensive carbon source (such as sugar) into the desired compound of formula (II), (IV), or (VI), or in particular, into 2-(5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethyl in the form of one of its stereoisomers or a mixture thereof. 2-(5,5,8a-trimethyl-2-methylenedecahydronaphthalen-1-yl)ethyl acetate can be converted to 2-(5,5,8a-trimethyl-2-methylenedecahydronaphthalen-1-yl)ethane-1-ol using chemical or enzymatic conditions known in the art. The advantage of using compounds of formula (II), (IV), or (VI) obtained by fermentation is evident, as it allows easy access to starting materials with a high enantiomer excess.

[0062] According to any one of the above embodiments of the method of the present invention, the method further comprises a step of contacting farnesyl pyrophosphate with at least one enzyme to produce a compound of formula (II), (IV), or (VI), in particular 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol.

[0063] Another subject of the present invention is a composition comprising at least 95% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 5% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the composition of the present invention may comprise at least 96% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 4% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain at least 97% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 3% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain at least 98% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 2% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain at least 99% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 1% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain at least 99.3% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.7% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.In particular, the compositions of the present invention may contain at least 99.4% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.6% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. More specifically, the compositions of the present invention may contain at least 99.5% (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.5% (3aSR,5aSR,9aSR,9bRS)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.

[0064] According to certain embodiments of the present invention, the composition of the present invention may contain at least 95% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 5% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the composition of the present invention may contain at least 96% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 4% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain at least 97% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 3% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain at least 98% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 2% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain at least 99% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 1% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain at least 99.3% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.7% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.In particular, the compositions of the present invention may contain at least 99.4% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.6% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. More specifically, the compositions of the present invention may contain at least 99.5% (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and up to 0.5% (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.

[0065] According to certain embodiments of the present invention, the composition of the present invention may contain 95% to 99.99% of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 5% of (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the composition of the present invention may contain 96% to 99.99% of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 4% of (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the composition of the present invention may contain 97% to 99.99% of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 3% of (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the composition of the present invention may contain 98% to 99.99% of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 2% of (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain 99% to 99.99% of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 1% of (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain 99.3% to 99.99% of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.01% to 0.7% of (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.In particular, the composition of the present invention may contain 99.3% to 99.9% of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.1% to 0.7% of (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the composition of the present invention may contain 99.4% to 99.9% of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.1% to 0.6% of (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain 99.5% to 99.9% of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.1% to 0.5% of (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. In particular, the compositions of the present invention may contain 99.5% to 99.8% of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan and 0.2% to 0.5% of (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan.

[0066] The compositions of the present invention described above can be used, for example, as fragrance components to impart amber-like fragrance notes. Therefore, another subject of the present invention is the use of the compositions of the present invention as defined above as fragrance components. In other words, the present invention relates to a method or process for imparting, enhancing, improving or modifying the olfactory properties of a fragranced composition or a fragranced article or surface, the method comprising adding an effective amount of the composition of the present invention to the composition or article, for example, to impart its typical notes. It is understood that the final pleasurable effect may depend on the precise dosage and the sensory stimulation properties of the composition of the present invention, but in any case, the addition of the composition of the present invention will impart its typical feel to the final product in the form of notes, textures or appearances depending on the dosage.

[0067] It should also be understood herein that "use of the composition of the present invention" means the use of any composition containing the composition of the present invention that can be advantageously used in the fragrance industry.

[0068] The above-mentioned compositions, which can actually be advantageously used as fragrance components, are also subject to the present invention.

[0069] Therefore, another subject of the present invention is, i) As a fragrance component, at least the composition of the present invention as defined above, ii) At least one component selected from the group consisting of fragrance carriers and fragrance bases, iii) Optionally, at least one fragrance enhancer This is a fragrance composition containing [a specific ingredient].

[0070] In this specification, "fragrance carrier" means a material that is substantially neutral from the standpoint of fragrance, that is, a material that does not significantly alter the sensory stimulation properties of the fragrance components. The carrier may be a liquid or a solid.

[0071] Examples of liquid carriers include, but are not limited, emulsions, i.e., solvents and surfactants, or solvents commonly used in fragrances. A detailed description of the properties and types of solvents commonly used in fragrances cannot be exhaustive. However, examples of solvents include, but are limited, but include, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, but are, solvents of natural origin such as glycerol or various vegetable oils, such as palm oil, sunflower oil or linseed oil. In the case of a composition containing both a fragrance carrier and a fragrance base, suitable fragrance carriers other than those previously specified may also be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins, e.g., those known by the trademark Isopar® (manufactured by Exxon Chemical), or glycol ethers and glycol ether esters, e.g., those known by the trademark Dowanol® (manufactured by Dow Chemical Company), or hydrogenated castor oil, e.g., those known by the trademark Cremophor® RH 40 (manufactured by BASF).

[0072] A solid carrier refers to a material that can chemically or physically bond a fragrance composition or several elements of a fragrance composition. Generally, such solid carriers are used to stabilize a composition or to control the evaporation rate of a composition or several of its components. Solid carriers are currently used in the art, and those skilled in the art know how to achieve the desired effect. However, non-limiting examples of solid carriers include absorbent gums or polymers or inorganic materials, such as porous polymers, cyclodextrins, dextrins, maltodextrins, woody materials, organic or inorganic gels, clays, gypsum talc, or zeolites.

[0073] Other non-limiting examples of solid carriers include encapsulation materials. Examples of such materials include wall-forming and plasticizing materials, such as glucose syrup, natural or modified starch, hydrophilic colloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins or pectin, plant gums, such as gum arabic, urea, sodium chloride, sodium sulfate, zeolite, sodium carbonate, sodium bicarbonate, clay, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, carbohydrates, sugars, such as sucrose, monosaccharides, disaccharides, trisaccharides and polysaccharides, and derivatives, such as chitosan, starch, cellulose, carboxymethylmethylcellulose. Methylcellulose, hydroxyethylcellulose, ethylcellulose, propylcellulose, polyols / sugar alcohols, e.g., sorbitol, maltitol, xylitol, erythritol, and isomalt, polyethylene glycol (PEG), polyvinylpyrrolidine (PVP), polyvinyl alcohol, acrylamide, acrylates, polyacrylic acid and related products, maleic anhydride copolymers, amine-functional polymers, vinyl ethers, styrene, polystyrene sulfonates, vinyl acids, ethylene glycol-propylene glycol block copolymers, vegetable gums, acacia gum, pectin, xanthan gum, alginates, carrageenan, citric acid or any water-soluble solid acid, fatty alcohols or fatty acids and mixtures thereof, or references, e.g., H. Scherz, Hydrokolloide: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitaet, Behr's Verlag GmbH & Co., Hamburg, This may include materials cited in 1996. Encapsulation is a method well known to those skilled in the art and can be carried out by using techniques such as spray drying, agglomeration or further extrusion, or by coating encapsulation including coacervation and composite coacervation techniques.

[0074] As non-limiting examples of solid supports, we can cite core-shell capsules containing aminoplasts, polyamides, polyesters, polyureas, or polyurethane-type resins or mixtures thereof (all of the above resins are well known to those skilled in the art) using techniques such as polymerization, interfacial polymerization, coacervation, or phase separation processes induced by these (all of the above techniques are described in the art), optionally in the presence of polymer stabilizers or cationic copolymers.

[0075] The resins can be produced by polycondensation of aldehydes (e.g., formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid, or glycolaldehyde, and mixtures thereof) with amines, such as urea, benzoguanamine, glycolyl, melamine, methylolmelamine, methylated methylolmelamine, guanazole, and mixtures thereof. Alternatively, pre-formed alkylolated polyamines of resins, such as those commercially available under the trademarks Urac® (manufactured by Cytec Technology Corp.), Cymel® (manufactured by Cytec Technology Corp.), Urecoll®, or Luracoll® (manufactured by BASF), may be used.

[0076] Other resins are produced by polycondensation of polyisocyanates such as hexamethylene diisocyanate trimers, isophorone diisocyanate or xylylene diisocyanate trimers, or hexamethylene diisocyanate biuret, or xylylene diisocyanate and trimethylolpropane trimers (known as the trademark Takenate®, manufactured by Mitsui Chemicals) with polyols such as glycerol.

[0077] Some influential literature on the encapsulation of fragrances by polycondensation of amino resins, i.e., melamine-based resins, with aldehydes includes papers by K. Dietrich et al., Acta Polymerica, 1989, Vol. 40, pp. 243, 325, and 683, and 1990, Vol. 41, p. 91. Such papers already describe various parameters that affect the production of such core-shell microcapsules according to prior art methods, which are further detailed and illustrated in the patent literature. U.S. Patent No. 4,396,670 by Wiggins Teape Group Limited is a suitable early example of the latter. Since then, many other authors have enriched the literature in this field, and it would be impossible to cover all developments published here, but a general understanding of encapsulation techniques is of great importance. More recent and relevant publications disclosing the appropriate use of such microcapsules are represented, for example, by the article by K. Bruyninckx and M. Dusserier, ACS Sustainable Chemistry & Engineering, 2019, Vol. 7, pp. 8041–8054.

[0078] As used herein, "fragrance base" means a composition containing at least one fragrance-enhancing component.

[0079] The above-mentioned fragrance-adding auxiliary component is not (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan. Furthermore, “fragrance-adding auxiliary component” as used herein means a compound used in a fragrance preparation or composition for the primary purpose of imparting a pleasurable effect, i.e., imparting or modulating a scent. In other words, such auxiliary components that should be considered fragrance-adding components should be recognized by those skilled in the art not merely as having a scent, but as being able to impart or modify the scent of a composition in a positive or pleasant way. Fragrance-adding auxiliary components may impart additional benefits other than modulating or imparting a scent, such as long-lasting effect, blooming, odor neutralization, antimicrobial effect, antiviral effect, microbial stability, or pest control.

[0080] The properties and types of fragrance-enhancing components present in the base are not guaranteed to be described in more detail herein, and these are not exhaustive in any case. Those skilled in the art can select them based on their general knowledge and according to the intended use or application and the desired sensory stimulation effect. Generally speaking, these fragrance-enhancing components belong to various chemical classes such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen-containing or sulfur-containing heterocyclic compounds, and essential oils, and these fragrance-enhancing components may be of natural or synthetic origin.

[0081] In particular, fragrance-enhancing ingredients commonly used in fragrance formulations, for example, - Aldehyde components: decanal, dodecanal, 2-methyl-undecinal, 10-undecenal, octanal, nonanal and / or nonenal, - Aromatic herbal components: Eucalyptus oil, camphor, eucalyptol, 5-methyltricyclo[6.2.1.0~2,7~]undecane-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4,4-dimethyl-1,3-oxatian, 2,2,7 / 8,9 / 10-tetramethylspiro[5.5]undecane-8-en-1-one, menthol and / or alpha-pinene, - Balsamic components: Coumarin, ethyl vanillin and / or vanillin, - Citrus components: Dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpene, limonene, 1-p-menthen-8-yl acetate and / or 1,4(8)-p-mentadiene, - Floral components: Methyl dihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, beta-ionone, methyl 2-(methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-butene-2- (1E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-penten-3-one, 1-(2,6,6-trimethyl-1,3-cyclohexadiene-1-yl)-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (2E)-1-[2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl) (Lu)-2-buten-1-one, 2,5-dimethyl-2-indanmethanol, 2,6,6-trimethyl-3-cyclohexen-1-carboxylate, 3-(4,4-dimethyl-1-cyclohexen-1-yl)propanal, 3-(3,3 / 1,1-dimethyl-5-indanyl)propanal, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, berzyl acetate, geraniol, p-ment-1-en-8- All, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, high cis-dihydrojasmonate methyl, 3-methyl-5-phenyl-1-pentanol, verzyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-p-menthanol, propyl(S)-2-(1,1-dimethylpropoxy)propanoate, 2-methoxynaphthalene, 2,2,2-Trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, amyl cinnamaldehyde, 8-decene-5-olido, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, berzyl isobutyrate and / or mixture of methyl ionone isomers, - Fruit components: γ-Undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxatian, 4-decanolide, ethyl 2-methylpentanoate, hexyl acetate, ethyl 2-methylbutyrate, γ-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-ethyl acetate, diethyl 1,4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, 1-[3,3-dimethylcyclohexyl]ethyl[3-ethyl-2-oxyranyl]acetate and / or diethyl 1,4-cyclohexanedicarboxylate, - Green ingredients: 2-methyl-3-hexanone(E)-oxime, 2,4-dimethyl-3-cyclohexen-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styraryl acetate, allyl(2-methylbutoxy) acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-1-ol and / or 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, - Musk components: 1,4-dioxa-5,17-cycloheptadecanedione, (Z)-4-cyclopentadecene-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecene-2-one, 1-oxa-13-cyclohexadecene-2-one, (9Z)-9-cycloheptadecene-1-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, 3-methyl-5-cyclo Pentadecene-1-one, 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]isochromene, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate, oxacyclohexadecane-2-one and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate, - Woody components: 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4'-dimethylspiro[oxiran-2,9'-tricyclo[6.2.1.0 2,7 Undeca[4]ene, (1-ethoxyethoxy)cyclododecane, 2,2,9,11-tetramethylspiro[5.5]undeca-8-ene-1-ylacetate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone, patchouli oil, terpene fraction of patchouli oil, Clearwood (registered trademark) (Manufacturer: Firmenich) SA), (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methylcedyl ketone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, 1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalene-2-yl)ethane-1-one and / or isobornyl acetate, - Other ingredients (e.g., amber, powdery spicy, or watery): may include heliotropin, anisaldehyde, eugenol, cinnamic aldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4,4]nonane and / or 3-(3-isopropyl-1-phenyl)butanal.

[0082] The fragrance base according to the present invention is not limited to the above-mentioned fragrance-adding auxiliary components, and many other such auxiliary components are listed in reference to the book *Perfume and Flavor Chemicals*, 1969, Montclair, New Jersey, USA, or its latest edition, or other papers of similar nature, as well as the extensive patent literature in the field of fragrances. It is also understood that the above-mentioned auxiliary components may be compounds known to release various types of fragrance compounds, also known as properfumes or profragrances, in a controlled manner. Non-limiting examples of suitable professional fragrances include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, trans-3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 3-(dodecylsulfonyl)-1-(2,6,6-trimethylcyclohexa-3-en-1-yl)butan-1-one, linear polysiloxane copolymer of (3-mercaptopropyl)(methyl)dimethoxysilane, and 1-[6-ethyl-2,6-dimethyl-3-cyclohexen-1-yl]-2-butane n-1-one, 2-(dodecylthio)octane-4-one, 2-(dodecylsulfonyl)octane-4-one, 4-oxooctane-2-yldodecanoate, 2-phenylethyloxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yloxo(phenyl)acetate, (Z)-hexa-3-en-1-yloxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-ylhexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl)succinate, (2E,6Z)-2,6-nonadienylhexadecanoate, (2E,6Z)-2,6-nonadien-1-yltetradecanoate, (2E,6Z)-2,6-Nonadiene-1-yldodecanoate, (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-Methoxy-4-(3-methyl-4-phenethoxybuta-3-en-1-yl)benzene, (3-methyl-4-phenethoxybuta-3-en-1-yl)benzene, 1-(((Z)-hexa-3-en-1-yl)oxy)-2-methylundeca-1-ene, (2-((2-methylundeca-1-en-1-yl)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undeca-1-ene, 1-Me Toxy-4-(1-phenethoxypropa-1-en-2-yl)benzene, 1-methyl-4-(1-phenethoxypropa-1-en-2-yl)benzene, 2-(1-phenethoxypropa-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,7-dimethylocta-6-en-1-yl)oxy)propa-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene , (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-methoxy-4-(1-phenethoxypropane-1-en-2-yl)benzene, (2-((2-methyl-4-(2,6,6-trimethylcyclohexa-1-en-1-yl)buta-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(2-methyl-3-phenethoxyaryl)benzene, (2-((2-isopropyl-5-methylcyclohexylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl-2-((2-pentylcyclopentyl Examples include 2-methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 2-ethoxy-1-((2-methoxy-2-phenylvinyl)oxy)-4-methylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)benzaldehyde, 1-isopropyl-2-((2-methoxy-2-phenylvinyl)oxy)-4-methylbenzene, 4-((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde, or mixtures thereof.

[0083] "Fragrance auxiliary agents" as used herein means ingredients that can impart additional benefits such as color, specific lightfastness, and chemical stability. A detailed description of the properties and types of auxiliary agents commonly used in fragrance compositions cannot be exhaustive, but it should be noted that the above ingredients are well known to those skilled in the art. Specific, non-limiting examples include: viscosifiers (e.g., surfactants, thickeners, gelling agents and / or rheological modifiers), stabilizers (e.g., preservatives, antioxidants, heat / light and / or buffering or chelating agents, e.g., BHT), colorants (e.g., dyes and / or pigments), preservatives (e.g., antimicrobial or bactericidal or antifungal or anti-irritant agents), abrasives, skin coolants, fixatives, insecticides, ointments, vitamins and mixtures thereof. A “fixative,” also called a “modifier,” is understood herein to be an agent having the ability to influence, over time, the manner in which the odor of a composition incorporating the modifier, particularly its evaporation rate and intensity, can be perceived by an observer or user, compared to the same perception in the absence of the modifier. In particular, this modifier allows for an extension of the time over which the fragrance is perceived.Non-limiting examples of suitable modifiers include methyl glucoside polyols, ethyl glucoside polyols, propyl glucoside polyols, isocetyl alcohol, PPG-3 myristyl ether, neopentyl glycol diethylhexanoate, sucrose laurate, sucrose dilaurate, sucrose myristate, sucrose palmitate, sucrose stearate, sucrose distearate, sucrose tristearate, sodium hyaluronate disaccharide, sodium hyaluronate, propylene glycol propyl ether; dicetyl ether; polyglycerin-4 ether Examples include: Isoceteth-5; Isoceteth-7, Isoceteth-10; Isoceteth-12; Isoceteth-15; Isoceteth-20; Isoceteth-25; Isoceteth-30; Disodium lauroamphodipropionate; Hexaethylene glycol monododecyl ether; and mixtures thereof; Neopentyl glycol diisononanoate; Cetearyl ethyl hexanoate; Panthenol ethyl ether, DL-Panthenol, N-Hexadecyl n-nonanoate, n-Octadecyl n-nonanoate, ProFragrance, Cyclodextrin, Encapsulation, and combinations thereof. Up to 20% by weight of the fragrance composition of the modifier may be incorporated into the fragranced consumer product.

[0084] Those skilled in the art will understand that by mixing the above-mentioned components of a fragrance composition, not only by applying standard knowledge in the art but also by trial and error, it is possible to perfectly design a formulation that is optimal for the desired effect.

[0085] The present invention comprises a composition and at least one fragrance carrier, as well as a fragrance composition comprising the composition of the present invention, at least one fragrance carrier, at least one fragrance base, and optionally at least one fragrance auxiliary agent.

[0086] For clarity, it is understood that any mixture obtained directly from chemical synthesis, such as an unrefined reaction medium in which the compositions of the present invention may be included as a starting, intermediate, or final product, cannot be considered a fragranced composition according to the present invention unless the mixture provides the compositions of the present invention in a form suitable for fragrance. Therefore, unless otherwise specified, unrefined reaction mixtures are generally excluded from the present invention.

[0087] The compositions of the present invention can also be advantageously used in all fields of modern fragrances, i.e., perfumes or functional fragrances, to positively impart or alter the scent of consumer products to which the compositions of the present invention are added. Accordingly, another subject of the present invention is a scented consumer product comprising the compositions of the present invention as defined above as a fragrance component.

[0088] The compositions of the present invention can be added as is or as part of the fragrance composition of the present invention.

[0089] To clarify, “Fragrant consumer product” means a consumer product that provides at least a pleasant fragrance effect to the surface or space to which it is applied (e.g., skin, hair, textiles, or household surfaces). In other words, a fragrance consumer product according to the present invention is a fragrance consumer product comprising a functional formulation, as well as optionally additional beneficial agents corresponding to the desired consumer product, and an olfactory effective amount of at least one compound of the present invention. To clarify, the above fragrance consumer product is a non-edible product.

[0090] The nature and types of ingredients in flavored consumer products are not guaranteed to be described in more detail herein (and will not be exhaustive in any case), and those skilled in the art can select them based on general knowledge and in accordance with the nature of the product and the desired effect.

[0091] Examples of suitable scented consumer products include: fragrances, e.g., fine perfumes, splashes or eau de parfums, colognes or shave or aftershave lotions; fabric care products, e.g., liquid or solid detergents (optionally in pod or tablet form), fabric softeners, liquid or solid fragrance enhancers, dryer sheets, fabric refreshers, ironing water, paper, bleach, carpet cleaners, curtain care products; body care products, e.g., hair care products (e.g., shampoos, leave-on or rinse-off hair conditioners, coloring preparations or hairsprays, color care products, hair shaping products, dental care products), disinfectants, intimate care products; cosmetic preparations (e.g., skin creams or lotions, vanishing creams or deodorants); Other products include antiperspirants (e.g., sprays or roll-ons), depilators, sunscreens or after-sun products, nail products, skin cleansers, and makeup; or skincare products (e.g., soaps, shower or bath mousses, oils or gels, or hygiene products or foot / hand care products); air care products, e.g., air fresheners or "ready-to-use" powdered air fresheners that can be used in home spaces (rooms, refrigerators, cupboards, shoes or cars) and / or public spaces (halls, hotels, shopping malls, etc.); or home care products, e.g., mold removers, furniture care products, wipes, dish soap or hard surface cleaners (e.g., floors, bathtubs, sanitary or window cleaning); leather care products; and car care products, e.g., polishes, waxes or plastic cleaners.

[0092] Some of the above-mentioned flavored consumer products may act as aggressive mediators for the compositions of the present invention and therefore may need to be protected from premature degradation, for example, by encapsulation or by chemically binding them with another suitable chemical substance. This is suitable for releasing the compositions of the present invention by a suitable external stimulus such as enzymes, light, heat, or a change in pH.

[0093] Typical methods for carrying out the method of the present invention are reported in the following examples herein. [Examples]

[0094] The present invention will be further described in detail by the following embodiments, where abbreviations have their usual meanings in the art and temperatures are given in degrees Celsius (°C). Gas chromatography was prepared using an Agilent 7890 A series with an HP5 column (30 m × 0.25 mm ID, 0.25 μm film), with tetradecane used as the internal standard.

[0095] [Example 1] (Typical experimental procedure for pre-activation of zeolite catalysts) In the case of zeolite, pre-activation before testing involves placing 10g of the material in its raw state at 10°C for 10 minutes. -1 This was carried out by placing the samples in a muffle furnace (static air) heated to 550°C for 3 hours. Since this process is essential for converting the ammonium form of the samples to their proton form, pre-activation by calcination was systematically applied to all zeolites for comparison.

[0096] [Example 2] (Production of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan by cyclization of 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol) 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol (compound of formula (II), 5 g, 21.16 mmol) and toluene (95 g, 1.03 mol) were placed in a 100 ml round-bottom flask and heated to 40°C with mechanical stirring. Once the desired reaction temperature was reached, 250 mg (5 wt% relative to the starting materials) of a solid acid catalyst containing either acid-treated clay, acid zeolite, or acid resin was added, and the mixture was left standing with stirring for up to 22 hours. Table I shows the desired (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan (compound of formula (I)), its isomer (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan (corresponding to compound A), and the isomer of the starting material 2-[(1S,4aS,8aS)- We report the yields of 2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydro-1-naphthalenyl]ethanol and 2-((4aS,8aS)-2,5,5,8a-tetramethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-1-yl)ethane-1-ol (corresponding to compound (II') and compound B, respectively). [Table 1-1] [Table 1-2]

[0097] The method of the present invention makes it possible to obtain compounds of formula (I) with very selective results, with little to no formation of undesirable compounds such as (3aS,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan (compound A), 2-[(1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydro-1-naphthalenyl]ethanol (compound of formula (II')) and 2-((4aS,8aS)-2,5,5,8a-tetramethyl-3,4,4a,5,6,7,8,8a-octahydronaphthalen-1-yl)ethane-1-ol (compound B). In the cyclization of the compound of formula (II) in the presence of a homogeneous catalyst as reported in the prior art (Table 1, entries 15 and 16), a larger amount of isomerization products, namely the compound of formula (II') and compound B, is supplied. However, in the cyclization of compound B (Table 1, entry 17) or the compound of formula (II') (Table 1, entry 19) in the presence of a heterogeneous catalyst, the compound of formula (I) is either not supplied or only a trace amount is supplied.

[0098] [Example 3] (Preparation of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan by cyclization of 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol using different solvents) Experiment 2 was repeated using CBV780, but with different solvents as summarized in Table 2. [Table 2]

[0099] [Example 4] (Production of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan by cyclization of 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol) 50 g of 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and 450 g of toluene were placed in a reactor and heated to 40°C. Once the desired temperature was reached, 2.5 g of CBV780 was added, and the reaction mixture was left to stand with stirring for 12 hours to obtain 97.7 GC% of the desired (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan product.

[0100] [Example 5] (Production of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan by cyclization of 22-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol) 50 g of 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and 115 g of toluene were placed in a reactor and heated to 50°C. Once the desired temperature was reached, 2.5 g of CBV780 was added, and the reaction mixture was left to stand with stirring for 12 hours to obtain 94.3 GC% of the desired (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan product.

[0101] [Example 6] (Production of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan by cyclization of 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol) 50 g of 2-((1S,4aS,8aS)-5,5,8a-trimethyl-2-methylenedecahydronaphthalene-1-yl)ethane-1-ol and 200 g of toluene were packed into a reactor and heated to 50°C. Once the desired temperature was reached, 2.5 g of F-24X was added, and the reaction was allowed to stand with stirring for 12 hours to obtain 88 GC% of the desired (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan product.

Claims

1. The following formula 【Chemistry 1】 [wherein n is 0 or 1; Each R6 and R7 separately and independently represents a C1-9 alkyl group optionally containing a hydrogen atom or one or two functional groups selected from ether, ester, carbonyl, amine, amide, or alcohol groups; R6 and R7 together represent a C3-10 linear or branched alkanediyl group; and A method for producing a cycloether of [R8 represents a hydrogen atom or a C1-3 linear or branched alkyl group] in the form of one of its stereoisomers or a mixture thereof, wherein the following formula 【Chemistry 2】 [wherein n is 0 or 1; Each R6 and R7 separately and independently represents a C1-9 alkyl group optionally containing a hydrogen atom or one or two functional groups selected from ether, ester, carbonyl, amine, amide, or alcohol groups; R6 and R7 together represent a C3-10 linear or branched alkanediyl group; and A method comprising cyclizing a compound in which R8 represents a hydrogen atom or a C1-3 linear or branched alkyl group in the form of one of its stereoisomers or a mixture thereof, in the presence of a heterogeneous acidic catalyst.

2. The method according to claim 1, wherein the heterogeneous acidic catalyst is crystalline or amorphous.

3. The method according to claim 1 or 2, wherein the heterogeneous acidic catalyst comprises silicon, tin, zirconium, hafnium, or titanium, and a second metal selected from the group consisting of aluminum, boron, iron, or mixtures thereof.

4. The method according to claim 1 or 2, wherein the heterogeneous acidic catalyst is an aluminosilicate catalyst.

5. The method according to claim 4, wherein the aluminosilicate catalyst is a zeolite or clay.

6. The method according to claim 5, wherein the clay is acid-treated clay.

7. The method according to claim 5, wherein the zeolite is a large-pore zeolite.

8. The method according to claim 7, wherein the zeolite has a FAU, BEA, or MOR topology.

9. The method according to claim 7, wherein the silicon:aluminum ratio is in the range of 2.5:1 to 300:

1.

10. The cycloether mentioned above is given by the following formula 【Transformation 3】 [In the formula, R ８ This has the same meaning as defined above, and each R ９ and R １０ They are independent of each other, C １～３ The method according to claim 1, wherein the compound is in the form of one of the stereoisomers of a linear or branched alkyl group or a mixture thereof.

11. The compound of formula (IV) above is the following formula 【Chemistry 4】 [In the formula, R ８ This has the same meaning as defined above, and each R ９ and R １０ They are independent of each other, C １～３ The method according to claim 1, wherein the compound is in the form of one of the stereoisomers of a linear or branched alkyl group or a mixture thereof.

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