Method for producing cyclic dienes

Abstract

The present invention relates to the field of organic synthesis, more specifically to a method for preparing a compound of formula (I), which comprises reacting a compound of formula (II) with a base having a boiling point higher than that of the compound of formula (I). Furthermore, the compound of formula (I) and the compound of formula (II) are also part of the present invention.

Description

[Technical field]

[0001] The present invention relates to the field of organic synthesis, more specifically to a method for preparing a compound of formula (I), which comprises reacting a compound of formula (II) with a base having a boiling point higher than that of the compound of formula (I). Furthermore, the compound of formula (I) and the compound of formula (II) are also part of the present invention.

[0002] Background technology Conjugated cyclic derivatives represent highly desirable scaffolds that can be used as such or as important intermediates useful for the preparation of more complex compounds in various fields, such as fragrance, cosmetics, pharmaceuticals or agrochemicals, among others. Important conjugated cyclic derivatives in the fragrance industry are, for example, 1-(2,6,6-trimethyl-1-cyclohexa-1,3-dienyl)but-2-en-1-one or ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate, which are especially appreciated for their floral odor. These perfuming ingredients represent some of the most sought-after ingredients in the fragrance industry. Methods known in the art for the preparation of these compounds, such as elimination processes, result in mixtures of several positional isomers, also known as α, β and γ isomers, which cannot be separated.

[0003] Therefore, there remains a need to develop highly selective, preferably catalytic, processes that afford conjugated cyclic derivatives in high yields.

[0004] The present invention makes it possible to solve the above problems by using a base having a boiling point higher than that of the compound of formula (I) for the preparation of the conjugated dienes of formula (I), i.e. the β-isomers. To the best of the inventors' knowledge, the conditions of the present invention have never been reported in the prior art.

[0005] Summary of the Invention The present invention relates to novel processes that allow the preparation of compounds of formula (I) while limiting or even preventing the formation of other regioisomers, using methodology not reported or suggested in the prior art.

[0006] A first subject of the invention is therefore a compound of formula (I) [ka] [In the formula, n is an integer from 0 to 13; R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 represents an alkenyl group; or R 4 and R 5 Together, C 3-6 forms a cycloalkyl group; X is C(O)R 6 Group, COOR 6 group, CN group or C=NR 6 is a group, R 6 is a hydrogen atom, C 1-6 Alkyl group or C 2-6 A method for preparing a compound of formula (II) [ka] [In the formula, n, X, R 1 , R 2 , R 3 , R 4 and R 5 has the same meaning as defined in formula (I), R 7 is a hydrogen atom, C 2-6 Alkenyl group, C 1-6 an alkyl group optionally substituted with one or more halogen atoms, or 6-10 Aryl groups, including hydroxy groups, C 1-6 Alkyl group, C 2-6 Alkenyl group, C 1-6and optionally substituted with one or more of an alkoxy group and / or a halogen atom] with a base having a boiling point higher than that of the compound of formula (I).

[0007] Another subject of the invention is a compound of formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 represents an alkenyl group; or R 4 and R 5 Together, C 3-6 forms a cycloalkyl group; X is C(O)R 6 Group, COOR 6 group, CN group or C=NR 6 is a group, R 6 is a hydrogen atom, C 1-6 Alkyl group or C 2-6 represents an alkenyl group, R 7 is a hydrogen atom, C 2-6 Alkenyl group, C 1-6 an alkyl group optionally substituted with one or more halogen atoms, or 6-10 Aryl groups, including hydroxy groups, C 1-6 Alkyl group, C 2-6 Alkenyl group, C 1-6 wherein R represents an integer from 1 to 10, and R represents an integer from 1 to 10, and R represents an integer from 1 to 10, and R represents an integer from 1 to 10, and R represents an integer from 1 to 10, with the proviso that 4-(but-2-enoyl)-3,5,5-trimethylcyclohex-2-en-1-yl acetate and ethyl 4-acetoxy-2,6,6-trimethylcyclohex-2-ene-1-carboxylate are excluded.

[0008] A further subject of the invention is a compound of formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 represents an alkenyl group; or R 4 and R 5 Together, C 3-6 forms a cycloalkyl group; X is C(O)R 6 Group, COOR 6 group, CN group or C=NR 6 is a group, R 6 is a hydrogen atom, C 1-6 Alkyl group or C 2-6 represents an alkenyl group], with the proviso that ethyl 2-ethyl-6,6-dimethylcyclohexa-1,3-diene-1-carboxylate, methyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate, ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate, 1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)ethan-1-one and 1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one are excluded.

[0009] Description of the invention Surprisingly, it has now been discovered that compounds of formula (I) can be advantageously prepared by reacting compounds of formula (II) with a base having a boiling point higher than that of the compound of formula (I). This unprecedented process allows the production of compounds of formula (I) with high selectivity towards the β isomer, while limiting or even preventing the formation of the α and / or γ isomers.

[0010] A first subject of the invention is therefore a compound of formula (I) [ka] [In the formula, n is an integer from 0 to 13; R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 represents an alkenyl group; or R 4 and R 5 Together, C 3-6 forms a cycloalkyl group; X is C(O)R 6 Group, COOR 6 group, CN group or C=NR 6 is a group, R 6 is a hydrogen atom, C 1-6 Alkyl group or C 2-6 A method for preparing a compound of formula (II) [ka] [In the formula, n, X, R 1 , R 2 , R 3 , R 4 and R 5 has the same meaning as defined in formula (I), R 7 is a hydrogen atom, C 2-6 Alkenyl group, C 1-6 an alkyl group optionally substituted with one or more halogen atoms, or 6-10 Aryl groups, including hydroxy groups, C 1-6 Alkyl group, C 2-6 Alkenyl group, C 1-6 and optionally substituted with one or more of an alkoxy group and / or a halogen atom] with a base having a boiling point higher than that of the compound of formula (I).

[0011] For clarity, expressions such as "any one stereoisomer of the compound or a mixture thereof" have the usual meaning as understood by a person skilled in the art, i.e., the compounds mentioned in the present invention may be a pure enantiomer or a mixture of enantiomers. In other words, the compounds mentioned in the present invention may have at least one stereocenter, which may have two different configurations (e.g., R or S), e.g., R 1 The group may have at least one stereocenter. The compound may be in the form of a pure enantiomer or in the form of a mixture of enantiomers. The compounds mentioned in the present invention may furthermore be in the form of a pure diastereomer or in the form of a mixture of diastereomers, if the compound has two or more stereocenters or at least one double bond. The compound may be in racemic or scalene form. Thus, the compound may be in the form of a stereoisomer or in the form of a composition of matter that comprises or consists of various stereoisomers.

[0012] According to any one of the above embodiments of the present invention, the compound may be in the form of its E or Z isomer or a mixture thereof, for example, the present invention includes a composition of matter consisting of one or more compounds of formula (I) and (II) having the same chemical structure but differing in the arrangement of double bonds. In particular, compound (I) and compound (II) may be in the form of a mixture consisting of E and Z isomers.

[0013] The term "optionally" is understood to mean that a group may be substituted or unsubstituted. The term "one or more" is understood to include 1 to 7, preferably 1 to 5, preferably 1 to 3 functional groups, more preferably 1 or 2 functional groups.

[0014] The terms "alkyl" and "alkenyl" are understood to include both branched and straight chain alkyl and alkenyl groups.

[0015] The term "alkenyl" is understood to include 1, 2 or 3 olefinic double bonds, preferably 1 or 2 olefinic double bonds.

[0016] "C 3-6 The term "cycloalkyl" refers to a group containing 3 to 6 carbon atoms, 4 and R 5 It is understood that the radical is a saturated ring containing the carbon atom to which it is attached.

[0017] The term "aryl" is understood to include any group that contains at least one aromatic group, such as a phenyl, indenyl, indanyl, tetrahydronaphthalenyl or naphthalenyl group.

[0018] The term "CN group" is understood to be a nitrile group, ie a -C≡N group.

[0019] According to any embodiment of the present invention, n may be an integer from 0 to 10, particularly an integer from 0 to 8, particularly an integer from 0 to 6, and especially an integer from 0 to 4. In particular, n may be 0, 1 or 2. Even more particularly, n may be 1.

[0020] According to any embodiment of the present invention, R 2 is a hydrogen atom, C 1-4 Alkyl group or C 2-4 In particular, R 2 is a hydrogen atom or C 1-3 R may be an alkyl group. 2 may be a hydrogen atom, a methyl group or an ethyl group. Even more particularly, R 2 may be a hydrogen atom.

[0021] According to any embodiment of the present invention, R 3 is a hydrogen atom, C 1-4 Alkyl group or C 2-4 In particular, R 3 is a hydrogen atom or C 1-3R may be an alkyl group. 3 may be a hydrogen atom, a methyl group or an ethyl group. Even more particularly, R 3 may be a hydrogen atom.

[0022] According to any embodiment of the present invention, the compound of formula (I) has the formula [ka] [In the formula, n, R 1 , R 4 and R 5 has the same meaning as defined above] in the form of any one of the stereoisomers or mixtures thereof.

[0023] According to any embodiment of the present invention, the compound of formula (II) has the formula [ka] [In the formula, n, X, R 1 , R 4 , R 5 and R 7 has the same meaning as defined above.

[0024] According to any embodiment of the present invention, R 1 is a hydrogen atom, C 1-4 Alkyl group or C 2-4 In particular, R 1 is a hydrogen atom or C 1-3 R may be an alkyl group. 1 may be a hydrogen atom, a methyl group or an ethyl group. Even more particularly, R 1 may be a methyl or ethyl group.

[0025] According to any embodiment of the present invention, R 4 is a hydrogen atom, C 1-4 Alkyl group or C 2-4 In particular, R4 is a hydrogen atom or C 1-3 R may be an alkyl group. 4 may be a hydrogen atom, a methyl group or an ethyl group. Even more particularly, R 4 may be a methyl or ethyl group.

[0026] According to any embodiment of the present invention, R 5 is a hydrogen atom, C 1-4 Alkyl group or C 2-4 In particular, R 5 is a hydrogen atom or C 1-3 R may be an alkyl group. 5 may be a hydrogen atom, a methyl group or an ethyl group. Even more particularly, R 5 may be a methyl or ethyl group.

[0027] According to any embodiment of the present invention, R 4 and R 5 Together, C 3-5 It is possible to form a cycloalkyl group. In particular, R 4 and R 5 can be taken together to form a C3 cycloalkyl group.

[0028] According to any embodiment of the present invention, R 6 is a hydrogen atom, C 1-4 Alkyl group or C 2-4 In particular, R 6 is a hydrogen atom, C 1-3 Alkyl group or C 2-3 R may be an alkenyl group. 6 may be a hydrogen atom, a methyl group, an ethyl group or a prop-1-en-1-yl group. Even more particularly, R 6 may be a methyl or ethyl group.

[0029] According to any embodiment of the present invention, X is C(O)R 6 Group or COOR 6 R may be a 6has the same meaning as defined above.

[0030] According to any embodiment of the present invention, R 7 is a hydrogen atom, C 2-4 Alkenyl group, C 1-4 an alkyl group optionally substituted with one, two or three halogen atoms, or a phenyl group optionally substituted with a hydroxy group, C 1-6 Alkyl group, C 2-6 Alkenyl group, C 1-6 It may be optionally substituted with one or more alkoxy groups and / or halogen atoms. In particular, R 7 is a hydrogen atom, C 2-4 Alkenyl group, C 1-4 an alkyl group optionally substituted with one, two or three halogen atoms, or a phenyl group optionally substituted with a hydroxy group, C 1-4 Alkyl group, C 2-4 Alkenyl group, C 1-4 It may be optionally substituted with one or more alkoxy groups and / or halogen atoms. In particular, R 7 is a hydrogen atom, C 2-3 Alkenyl group, C 1-3 an alkyl group optionally substituted with one, two or three halogen atoms, or a phenyl group optionally substituted with a hydroxy group, C 1-3 Alkyl group, C 2-3 Alkenyl group, C 1-3 It may be optionally substituted with one or more alkoxy groups and / or halogen atoms. In particular, R 7 may be a methyl group, an ethyl group, a propyl group, an isopropyl group or a phenyl group. Even more particularly, R 7 may be a methyl group.

[0031] Non-limiting examples of suitable compounds of formula (I) include 1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one, 2-methyl-1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one, 1-(6-ethyl-2,6-dimethylcyclohexa-1,3-dien-1-yl)-2-methylbut-2-ene, -1-one, 1-(6-ethyl-2,6-dimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one, 1-(5-methylspiro[2.5]octa-4,6-dien-4-yl)but-2-en-1-one, 1-(5-methylspiro[2.5]octa-4,6-dien-4-yl)ethan-1-one, 1-(2,6,6-trimethylcyclohexa-1,3-dien-1 1-(6-ethyl-2,6-dimethylcyclohexa-1,3-dien-1-yl)ethan-1-one, 1-(6-ethyl-2,6-dimethylcyclohexa-1,3-dien-1-yl)ethan-1-one, methyl or ethyl 6-ethyl-2,6-dimethylcyclohexa-1,3-diene-1-carboxylate, methyl or ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate, 1-(2,5,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one, methyl or ethyl 2-ethyl-6,6-dimethylcyclohexa-1,3-diene-1-carboxylate, methyl or ethyl 2,5,6-trimethylcyclohexa-1,3-diene-1-carboxylate, methyl or ethyl 5-methylspiro[2.5]octa-4,6-diene-4-carboxylate.

[0032] Non-limiting examples of suitable compounds of formula (II) include 4-acetyl-3,5,5-trimethylcyclohex-2-en-1-yl acetate, 4-(but-2-enoyl)-3,5,5-trimethylcyclohex-2-en-1-yl acetate, 3,5,5-trimethyl-4-(2-methylbut-2-enoyl)cyclohex-2-en-1-yl acetate, 5-ethyl-3,5-dimethyl-4-(2-methylbut-2-enoyl)cyclohex-2-en-1-yl acetate, and 5-ethyl-3,5-dimethyl-4-(2-methylbut-2-enoyl)cyclohex-2-en-1-yl acetate. Acetate, 4-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 8-(but-2-enoyl)-7-methylspiro[2.5]oct-6-en-5-yl acetate, 4-acetyl-3,5,5-trimethylcyclohex-2-en-1-yl acetate, 4-acetyl-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 8-acetyl-7-methylspiro[2.5]oct-6-en-5-yl acetate methyl or ethyl 7-acetoxy-5-methylspiro[2.5]oct-5-ene-4-carboxylate; methyl or ethyl 4-acetoxy-2,6,6-trimethylcyclohex-2-ene-1-carboxylate; methyl or ethyl 4-acetoxy-6-ethyl-2,6-dimethylcyclohex-2-ene-1-carboxylate; methyl or ethyl 4-acetoxy-2,5,6-trimethylcyclohex-2-ene-1-carboxylate; carboxylate, 4-(but-2-enoyl)-3,5,5-trimethylcyclohex-2-en-1-yl acetate, 4-(but-2-enoyl)-3,5,6-trimethylcyclohex-2-en-1-yl acetate, methyl or ethyl 4-acetoxy-2-ethyl-6,6-dimethylcyclohex-2-ene-1-carboxylate, methyl or ethyl 7-acetoxy-5-methylspiro[2.5]oct-5-ene-4-carboxylate.

[0033] According to any embodiment of the present invention, the base has a boiling point at least 5° C. higher than the boiling point of the compound of formula (I). In particular, the base has a boiling point at least 10° C., 15° C., or even 20° C. higher than the boiling point of the compound of formula (I).

[0034] According to any embodiment of the invention, the base is a metal carboxylate, metal bicarbonate or metal carbonate.

[0035] According to any embodiment of the present invention, the metal carbonate is represented by the formula M p CO3(III) wherein M is an alkali metal or an alkaline earth metal and p is 1 or 2; with the proviso that when M is an alkaline earth metal, p is 1, and when M is an alkali metal, p is 2.

[0036] According to any embodiment of the present invention, the metal bicarbonate is represented by the formula M(HOCO2) q (IV) wherein M is an alkali metal or an alkaline earth metal and q is 1 or 2; with the proviso that when M is an alkaline earth metal, q is 2, and when M is an alkali metal, q is 1.

[0037] According to any embodiment of the present invention, the metal carboxylate is represented by the formula (RCOO) r M (V) [In the formula, R is a hydrogen atom or C 1-18 M is an alkali metal or an alkaline earth metal, and r is 1 or 2; provided that when M is an alkali metal, r is 1, and when M is an alkaline earth metal, r is 2.

[0038] "...hydrocarbon group..." is understood to mean that said group consists of hydrogen and carbon atoms and may be in the form of an aliphatic hydrocarbon, i.e. linear or branched saturated hydrocarbon (e.g. alkyl group), linear or branched unsaturated hydrocarbon (e.g. alkenyl or alkynyl group), saturated cyclic hydrocarbon (e.g. cycloalkyl) or unsaturated cyclic hydrocarbon (e.g. cycloalkenyl or cycloalkynyl group), aromatic hydrocarbon, i.e. aryl group, or mixtures of said types of groups, e.g. a particular group may contain linear alkyl, branched alkenyl (e.g. having one or more carbon-carbon double bonds), (poly)cycloalkyl and aryl moieties, unless a specific limitation to only one type is mentioned. Similarly, in all embodiments of the present invention, when a group is referred to as being in the form of more than one type of topology (e.g., linear, cyclic or branched) and / or being saturated or unsaturated (e.g., alkyl, aromatic or alkenyl), it also means the group can have any one of said topologies or contain moieties that are saturated or unsaturated, as explained above. Similarly, in all embodiments of the present invention, when a group is referred to as being in the form of one type of saturated or unsaturated (e.g., alkyl), it means that the group can be in any type of topology (e.g., linear, cyclic or branched) or have several moieties with various topologies.

[0039] According to any embodiment of the present invention, M may be selected from the group of magnesium, calcium, potassium, sodium and lithium, and is preferably potassium.

[0040] According to any embodiment of the present invention, the process of the present invention is carried out in the presence of a metal carboxylate.

[0041] According to any embodiment of the present invention, R is a hydrogen atom or C 1-15 In particular, R is a hydrogen atom, a phenyl group, a C1-15 Alkyl group or C 2-15 In particular, R can be a hydrogen atom, a phenyl group, a C 1-10 Alkyl group or C 2-10 In particular, R can be a hydrogen atom, a phenyl group, a C 1-8 Alkyl group or C 2-8 In particular, R is a hydrogen atom, a phenyl group or a C 1-6 In particular, R may be a hydrogen atom, a phenyl group or a C 1-3 It may be an alkyl group. Even more particularly, R may be a methyl group.

[0042] Non-limiting examples of suitable metal carbonates include potassium carbonate, magnesium carbonate, calcium carbonate, sodium carbonate or lithium carbonate.

[0043] Non-limiting examples of suitable metal bicarbonates include potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, sodium bicarbonate or lithium bicarbonate.

[0044] Non-limiting examples of suitable metal carboxylates include potassium acetate, magnesium acetate, sodium acetate, calcium acetate, lithium acetate, potassium benzoate, magnesium benzoate, sodium benzoate, calcium benzoate, lithium benzoate, potassium propionate, magnesium propionate, sodium propionate, calcium propionate, lithium propionate, potassium octanoate, magnesium octanoate, sodium octanoate, calcium octanoate, lithium octanoate, potassium 2-ethylhexanoate, magnesium 2-ethylhexanoate, sodium 2-ethylhexanoate, calcium 2-ethylhexanoate, or lithium 2-ethylhexanoate.

[0045] To form the compound of formula (I), the metal bicarbonate or metal carbonate can be added to the reaction medium of the process of the invention in a wide range of concentrations. As non-limiting examples, metal bicarbonate or metal carbonate concentration values ​​can be mentioned ranging from 1 mol % to 10 equivalents relative to the total amount of the compound of formula (II). In particular, the metal bicarbonate or metal carbonate concentration can be from 1 mol % to 5 equivalents. In particular, the metal bicarbonate or metal carbonate concentration can be from 1.2 mol % to 2 equivalents. It goes without saying that the process also works with more metal bicarbonate or metal carbonate. However, the optimum concentration of the metal bicarbonate or metal carbonate depends, as known by the skilled person, on the nature of the metal bicarbonate or metal carbonate, the nature of the compound of formula (II), the temperature and the desired reaction time.

[0046] According to any embodiment of the present invention, the process of the present invention is carried out in the presence of a catalytic amount of a metal carboxylate.

[0047] To form the compound of formula (I), the metal carboxylate can be added to the reaction medium of the process of the invention in a wide range of concentrations. As non-limiting examples, metal carboxylate concentration values ​​can be mentioned in the range of 0.1 mol% to 100 mol% with respect to the total amount of the compound of formula (II). In particular, the metal carboxylate concentration can be 1 mol% to 50 mol%. In particular, the metal carboxylate concentration can be 2 mol% to 20 mol%. Even more particularly, the metal carboxylate concentration can be 5 mol% to 15 mol%. It goes without saying that the process also works with more metal carboxylates. However, the optimum concentration of the metal carboxylate depends on the nature of the metal carboxylate, the nature of the compound of formula (II), the temperature and the desired reaction time, as known to the skilled person.

[0048] The formation of a compound of formula (I) by the process of the present invention may be carried out under batch, semi-continuous, or continuous conditions.

[0049] According to any embodiment of the present invention, a compound of formula (I) and optionally of formula R 7Relatively volatile compounds produced during the process of the invention, such as carboxylic acids of COOH, are removed continuously during the process, for example by distillation at atmospheric or reduced pressure.

[0050] The process of the present invention can be carried out under an inert atmosphere such as nitrogen or argon. The process of the present invention can be carried out under atmospheric pressure or under a slight vacuum. In particular, the process of the present invention can be carried out at a pressure of 100 Pa to 10000 Pa (1 to 100 mbars), in particular 3000 Pa to 5000 Pa (30 to 50 mbars). A person skilled in the art is fully capable of adjusting the pressure depending on the compounds of formulae (II) and (I) and the solvent.

[0051] The formation of the compound of formula (I) by the method of the present invention can be carried out in the presence or absence of a solvent. If a solvent is necessary or used for practical reasons, any solvent customary in such reaction types can be used for the purposes of the present invention, in particular at least one aprotic dipolar solvent. Non-limiting examples include 2-pyrrolidone, N-methylpyrrolidone, N-octylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, hexamethylphosphoramide or mixtures thereof. The choice of solvent depends on the nature of the compound of formula (II) and / or the base, and the skilled person is fully capable of choosing the most suitable solvent in each case to optimize the reaction.

[0052] According to any one of the embodiments of the present invention, the formation of the compound of formula (I) by the method of the present invention is carried out at a temperature of 80° C. to 250° C. In particular, the temperature ranges from 100° C. to 200° C. The skilled person can also select the preferred temperature depending on the melting and boiling points of the starting and final products and the desired reaction time or conversion rate.

[0053] The compounds of formula (I) and (II) are generally novel compounds and have many advantages as described above and illustrated in the examples.

[0054] Another subject of the invention is therefore a compound of formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 represents an alkenyl group; or R 4 and R 5 Together, C 3-6 forms a cycloalkyl group; X is C(O)R 6 Group, COOR 6 group, CN group or C=NR 6 is a group, R 6 is a hydrogen atom, C 1-6 Alkyl group or C 2-6 represents an alkenyl group, R 7 is a hydrogen atom, C 2-6 Alkenyl group, C 1-6 an alkyl group optionally substituted with one or more halogen atoms, or 6-10 Aryl groups, including hydroxy groups, C 1-6 Alkyl group, C 2-6 Alkenyl group, C 1-6 wherein R represents an integer from 1 to 10, and R represents an integer from 1 to 10, and R represents an integer from 1 to 10, and R represents an integer from 1 to 10, and R represents an integer from 1 to 10, with the proviso that 4-(but-2-enoyl)-3,5,5-trimethylcyclohex-2-en-1-yl acetate and ethyl 4-acetoxy-2,6,6-trimethylcyclohex-2-ene-1-carboxylate are excluded.

[0055] According to any embodiment of the present invention, the compound of formula (II) is 4-acetyl-3,5,5-trimethylcyclohex-2-en-1-yl acetate, 3,5,5-trimethyl-4-(2-methylbut-2-enoyl)cyclohex-2-en-1-yl acetate, 5-ethyl-3,5-dimethyl-4-(2-methylbut-2-enoyl)cyclohex-2-en-1-yl acetate, 4-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 8-(but-2-enoyl)-7-methyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 9-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 10-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 11-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 12-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 13-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 14-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 15-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 16-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 17-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 18-(but-2-enoyl)-5-ethyl-3,5-dimethylcyclohex-2- -Methylspiro[2.5]oct-6-en-5-yl acetate, 4-acetyl-3,5,5-trimethylcyclohex-2-en-1-yl acetate, 4-acetyl-5-ethyl-3,5-dimethylcyclohex-2-en-1-yl acetate, 8-acetyl-7-methylspiro[2.5]oct-6-en-5-yl acetate, methyl 7-acetoxy-5-methylspiro[2.5]oct-5-ene-4-carboxylate, ethyl 7-acetoxy-5-methylspiro[2.5]oct-5-ene-4-carboxylate, Methyl 4-acetoxy-2,6,6-trimethylcyclohex-2-ene-1-carboxylate, methyl 4-acetoxy-6-ethyl-2,6-dimethylcyclohex-2-ene-1-carboxylate, ethyl 4-acetoxy-6-ethyl-2,6-dimethylcyclohex-2-ene-1-carboxylate, 4-(but-2-enoyl)-3,5,6-trimethylcyclohex-2-en-1-yl acetate, methyl 4-acetoxy-2-ethyl-6,6-dimethylcyclohex-2-ene-1-carboxylate, ethyl 4- It can be selected from the group consisting of acetoxy-2-ethyl-6,6-dimethylcyclohex-2-ene-1-carboxylate, methyl 4-acetoxy-2,5,6-trimethylcyclohex-2-ene-1-carboxylate, ethyl 4-acetoxy-2,5,6-trimethylcyclohex-2-ene-1-carboxylate, methyl 7-acetoxy-5-methylspiro[2.5]oct-5-ene-4-carboxylate and ethyl 7-acetoxy-5-methylspiro[2.5]oct-5-ene-4-carboxylate.

[0056] Another subject of the invention is a compound of formula [ka] [In the formula, R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, C 1-6 Alkyl group or C 2-6 represents an alkenyl group; or R 4 and R 5 Together, C 3-6 forms a cycloalkyl group; X is C(O)R 6 Group, COOR 6 group, CN group or C=NR 6 is a group, R 6 is a hydrogen atom, C 1-6 Alkyl group or C 2-6 represents an alkenyl group], with the proviso that ethyl 2-ethyl-6,6-dimethylcyclohexa-1,3-diene-1-carboxylate, methyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate, ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate, 1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)ethan-1-one and 1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one are excluded.

[0057] According to any embodiment of the present invention, the compound of formula (I) is 2-methyl-1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one, 1-(6-ethyl-2,6-dimethylcyclohexa-1,3-dien-1-yl)-2-methylbut-2-en-1-one, 1-(6-ethyl-2,6-dimethylcyclohexa-1,3-dien-1-yl)-2-methylbut-2-en-1-one, 1-yl)but-2-en-1-one, 1-(5-methylspiro[2.5]octa-4,6-dien-4-yl)but-2-en-1-one, 1-(5-methylspiro[2.5]octa-4,6-dien-4-yl)ethan-1-one, 1-(6-ethyl-2,6-dimethylcyclohexa-1,3-dien-1-yl)ethan-1-one, methyl 6-ethyl-2,6-dimethyl cyclohexa-1,3-diene-1-carboxylate, ethyl 6-ethyl-2,6-dimethylcyclohexa-1,3-diene-1-carboxylate, 1-(2,5,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one, methyl 2-ethyl-6,6-dimethylcyclohexa-1,3-diene-1-carboxylate, ethyl 5-methylspiro[2.5]octa-4,6-diene-4-carboxylate, methyl 5-methylspiro[2.5]octa-4,6-diene-4-carboxylate, methyl 2,5,6-trimethylcyclohexa-1,3-diene-1-carboxylate and ethyl 2,5,6-trimethylcyclohexa-1,3-diene-1-carboxylate.

[0058] Said compound of formula (I) can be used as a perfuming ingredient, for example to impart an amber-type odor note. Therefore, another subject of the present invention is the use of the compound of formula (I) of the present invention as defined above, as a perfuming ingredient. In other words, the present invention relates to a method or a method for imparting, enhancing, improving or modulating the odor properties of a perfuming composition or a perfumed article or surface, which method comprises adding to said composition or article an effective amount of the substance composition of the present invention, for example to impart its typical note. The final hedonic effect may depend on the exact dosage and the organoleptic properties of the substance composition of the present invention, but it is understood that in any case, the addition of the compound of formula (I) of the present invention imparts its typical touch to the final product in the form of a note, touch or aspect depending on the dosage.

[0059] "Use of the compound of formula (I) of the present invention" should also be understood herein as the use of any composition that contains the compound of formula (I) of the present invention and that can be advantageously used in the perfumery industry.

[0060] Said compositions, which in fact can be advantageously used as perfuming ingredients, are also the subject of the present invention.

[0061] Another subject of the invention is therefore i) at least one compound of formula (I) as defined above as a perfuming ingredient, ii) at least one ingredient selected from the group consisting of a perfume carrier and a perfume base; iii) optionally at least one flavor adjuvant; The fragrance composition comprises:

[0062] By "perfume carrier" is meant herein a material that is substantially neutral from the perfume point of view, i.e. does not significantly alter the organoleptic properties of the perfuming ingredients. Said carrier may be liquid or solid.

[0063] The liquid carrier may be, as a non-limiting example, an emulsifying system, i.e., a solvent and surfactant system, or a solvent commonly used in perfumery. The nature and type of solvents commonly used in perfumery cannot be described in full detail. However, as a non-limiting example, it may be the most commonly used solvents such as butylene glycol or propylene glycol, glycerin, dipropylene glycol and its monoethers, 1,2,3-propanetriyl triacetate, dimethyl glutarate, dimethyl adipate, 1,3-diacetyloxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, Abalyn® (rosin resin, available from Eastman), benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanol, triethyl citrate or mixtures thereof, or naturally occurring solvents such as glycerin, or various vegetable oils such as palm oil, sunflower oil, linseed oil. For compositions containing both a fragrance carrier and a fragrance base, suitable fragrance carriers other than those defined above may include ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar® (supplied by Exxon Chemical), or glycol ethers and glycol ether esters such as those known under the trademark Dowanol® (supplied by Dow Chemical Company), or hydrogenated castor oil such as those known under the trademark Cremophor® RH 40 (supplied by BASF).

[0064] Solid carrier means a material that can be chemically or physically bound to perfume composition or some of the components of perfume composition.Generally, such solid carrier is used to stabilize composition or control the evaporation rate of composition or some of the components.Solid carrier is currently used in the art, and the skilled person knows how to obtain the desired effect.However, non-limiting examples of solid carrier can include absorbent gum or polymer or inorganic material, such as porous polymer, cyclodextrin, dextrin, maltodextrin, wood-based material, organic or inorganic gel, clay, gypsum, talc or zeolite.

[0065] Other non-limiting examples of solid carriers can include encapsulating materials. Examples of such materials include wall-forming and plasticizing materials such as glucose syrup, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins or pectins, vegetable gums such as gum acacia (gum arabic), urea, sodium chloride, sodium sulfate, zeolites, sodium carbonate, sodium bicarbonate, clays, 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, carboxymethyl methylcellulose, ... Cellulose, hydroxyethyl cellulose, ethyl cellulose, propyl cellulose, polyols / sugar alcohols such as sorbitol, maltitol, xylitol, erythritol and isomalt, polyethylene glycol (PEG), polyvinylpyrrolidine (PVP), polyvinyl alcohol, acrylamides, acrylates, polyacrylic acid and related structures, maleic anhydride copolymers, amine functional polymers, vinyl ethers, styrene, polystyrene sulfonate, vinyl acid, ethylene glycol-propylene glycol block copolymers, vegetable gums, acacia gum, pectin, xanthan, alginates, carrageenan, citric acid or any water soluble solid acid, fatty alcohols or fatty acids and mixtures thereof, or even H. These may include materials cited in references such as Scherz, Hydrokolloides: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitaet, Behr's Verlag GmbH & Co., Hamburg, 1996.Encapsulation is a process well known to those skilled in the art and can be carried out using techniques such as spray drying, agglomeration or even extrusion; or it can consist of coating encapsulation, including coacervation and complex coacervation techniques.

[0066] Non-limiting examples of solid carriers include core-shell capsules comprising aminoplast, polyamide, polyester, polyurea or polyurethane type resins or mixtures thereof (all of which are well known to those skilled in the art) using techniques such as phase separation processes induced by polymerization, interfacial polymerization, coacervation, or all of which are described in the prior art, optionally in the presence of polymeric stabilizers or cationic copolymers.

[0067] The resins can be prepared by polycondensation of aldehydes (e.g. formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid or glycolaldehyde and mixtures thereof) with amines such as urea, benzoguanamine, glycouril, melamine, methylolmelamine, methylated methylolmelamine, guanazole and mixtures thereof. Alternatively, preformed resins, alkylolated polyamines, such as those commercially available under the trademarks Urac® (supplied by Cytec Technology Corp.), Cymel® (supplied by Cytec Technology Corp.), Urecoll® or Luracoll® (supplied by BASF) can be used.

[0068] Other resins are produced by polycondensation of polyols such as glycerin with polyisocyanates such as the trimer of hexamethylene diisocyanate, the trimer of isophorone diisocyanate or xylylene diisocyanate, the biuret of hexamethylene diisocyanate or the trimethylolpropane adduct of the trimer of xylylene diisocyanate (known under the trade name Takenate®, supplier: Mitsui Chemicals, Inc.), of which the trimethylolpropane adduct of the trimer of xylylene diisocyanate and the biuret of hexamethylene diisocyanate are preferred.

[0069] Some of the seminal publications related to the encapsulation of perfumes by polycondensation of amino resins, i.e. melamine-based resins with aldehydes, include articles such as Acta Polymerica, Vol. 40, pages 243, 325 and 683, 1989, and Vol. 41, page 91, 1990, published by K. Dietrich et al., which already describe the various parameters that affect the production of such core-shell microcapsules according to the methods of the prior art, which are further detailed and illustrated in the patent literature. U.S. Patent No. 4,396,670 by Wiggins Teape Group Limited is a good early example of the latter. Since then, many other authors have enriched the literature in this field, and although it is impossible to cover all the published developments here, a general knowledge in encapsulation technology is very important. A more recent relevant publication disclosing suitable uses of such microcapsules is, for example, the article by K. Bruyninckx and M. Dusselier in ACS Sustainable Chemistry & Engineering, 2019, vol. 7, pages 8041-8054.

[0070] As meant herein, a "perfume base" is a composition that includes at least one perfuming co-ingredient.

[0071] The perfuming co-ingredient is not a compound of formula (I). Moreover, the term "perfuming co-ingredient" as used herein means a compound used in a perfuming preparation or composition to provide a hedonic effect, i.e., a compound used primarily to provide or modulate an odor. In other words, such a co-ingredient must be recognized by those skilled in the art as being capable of providing or modulating the odor of a composition in a positive or pleasant manner, rather than merely having an odor, in order to be considered perfuming. Perfuming co-ingredients can provide additional benefits other than modulating or providing an odor, such as persistence, blooming, malodor neutralization, antimicrobial effect, antiviral effect, microbial stability, or pest control.

[0072] A more detailed description herein of the nature and type of perfuming co-ingredients present in the base is not warranted, but in any case is not exhaustive, and the skilled person can select them on the basis of his / her common knowledge, depending on the intended use or application and the desired sensory effect.In general terms, these perfuming co-ingredients belong to various chemical classes, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, thiols, terpene hydrocarbons, nitrogen- or sulfur-containing heterocyclic compounds and essential oils, and said perfuming co-ingredients may be of natural or synthetic origin.

[0073] Mention may in particular be made of perfuming co-ingredients commonly used in perfume formulations, such as: - aldehyde compounds: decanal, dodecanal, 2-methylundecanal, 10-undecenal, octanal, nonanal and / or nonenal; - Aromatic Herbal Ingredients: Eucalyptus Oil, Camphor, Eucalyptol, 5-Methyltricyclo[6.2.1.0~2,7~]undec-4-one, 1-Methoxy-3-Hexanethiol, 2-Ethyl-4,4-dimethyl-1,3-oxathiane, 2,2,7 / 8,9 / 10-Tetramethylspiro[5.5]undec-8-en-1-one, Menthol and / or α-Pinene; - Balsamic ingredients: coumarin, ethyl vanillin and / or vanillin; - Citrus Ingredients: Dihydromyrcenol, Citral, Orange Oil, Linalyl Acetate, Citronellyl Nitrile, Orange Terpenes, Limonene, 1-p-Menthen-8-yl Acetate and / or 1,4(8)-p-Menthadiene; - Floral ingredients: Methyl dihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexylcinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, β-ionone, methyl 2-(methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, (1E )-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-penten-3-one, 1-(2,6,6-trimethyl-1,3-cyclohexadien-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)-2- Buten-1-one, 2,5-dimethyl-2-indanmethanol, 2,6,6-trimethyl-3-cyclohexene-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, vergyl acetate, geraniol, p-mentha-1-en-8-ol , 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, cis-high methyl dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, vergyl proprionate, 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, amylcinnamaldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, vergyl isobutyrate and / or a mixture of methyl ionone isomers;, - fruity ingredients: gamma-undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxathiane, 4-decanolide, ethyl 2-methylpentanoate, hexyl acetate, ethyl 2-methylbutanoate, gamma-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, diethyl 1,4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, 1-[3,3-dimethylcyclohexyl]ethyl[3-ethyl-2-oxiranyl]acetate and / or diethyl 1,4-cyclohexanedicarboxylate; - Green ingredients: 2-methyl-3-hexanone (E)-oxime, 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styrallyl 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 ingredients: 1,4-dioxa-5,17-cycloheptadecanedione, (Z)-4-cyclopentadecen-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecen-2-one, 1-oxa-13-cyclohexadecen-2-one, (9Z)-9-cycloheptadecen-1-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, 3-methyl-5-cyclohexyl lopentadecen-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, oxacyclohexadecan-2-one and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate; - Woody ingredients: 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[oxirane-2,9'-tricyclo[6.2.1.0 2,7 ]undec[4]ene, (1-ethoxyethoxy)cyclododecane, 2,2,9,11-tetramethylspiro[5.5]undec-8-en-1-yl acetate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone, patchouli oil, terpene fraction of patchouli oil, Clearwood® (supplied by 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, methyl cedryl 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-octahydronaphthalen-2-yl)ethan-1-one and / or isobornyl acetate; - other ingredients (e.g. amber, powdery-spicy or watery): dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan and any of its stereoisomers, heliotropin, anisaldehyde, eugenol, cinnamaldehyde, 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.

[0074] The perfume base according to the present invention is not limited to the above-mentioned perfuming co-ingredients, and many others of these co-ingredients are in any case listed in references such as the document Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, by S. Arctander, or its newer versions, or other works of similar nature and the abundant patent literature in the perfumery field.It is also understood that said co-ingredients may be compounds known to release in a controlled manner various types of perfuming compounds, also known as pro-perfumes or pro-fragrances. Non-limiting examples of suitable propurfumes 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-trimethylcyclohex-3-en-1-yl)butan-1-one, linear polysiloxane copolymers of (3-mercaptopropyl)(methyl)dimethoxysilane, 1-[6-ethyl-2,6-dimethyl-3-cyclohexen-1-yl]-2-butanone, and the like. Ten-1-one, 2-(dodecylthio)octan-4-one, 2-(dodecylsulfonyl)octan-4-one, 4-oxooctane-2-yl dodecanoate, 2-phenylethyloxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yloxo(phenyl)acetate, (Z)-hex-3-en-1-yloxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl)succinate, (2E,6Z)-2,6-nonadienyl hexadecanoate, (2E,6Z)-2,6-nonadien-1-yl tetradecanoate, (2E,6Z)-2,6-Nonadien-1-yl dodecanoate, (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene, (3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-(((Z)-hex-3-en-1-yl)oxy)-2-methylundec-1-ene, (2-((2-methylundec-1-en-1-yl)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undec-1-ene, 1-methyl 1-phenethoxy-4-(1-phenethoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenethoxyprop-1-en-2-yl)benzene, 2-(1-phenethoxyprop-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1-yl)oxy)prop-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-phenethoxyprop-1-en-2-yl)benzene, (2-((2-methyl-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(2-methyl-3-phenethoxyallyl)benzene, (2-((2-isopropyl-5-methylcyclohexylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl-2-((2-pentylcyclopentylidene ) methoxy) benzene, 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.

[0075] By "perfume adjuvant" is meant herein an ingredient that may impart further additional benefits such as color, specific lightfastness, chemical stability, etc. The nature and type of adjuvants commonly used in perfumed compositions cannot be described in exhaustive detail, but it must be mentioned that such ingredients are well known to those skilled in the art. Specific non-limiting examples include viscosity agents (e.g. surfactants, thickeners, gelling agents and / or rheology modifiers), stabilizers (e.g. preservatives, antioxidants, heat / light and / or buffers or chelating agents, e.g. BHT), colorants (e.g. dyes and / or pigments), preservatives (e.g. antibacterial or antimicrobial or antifungal or antiirritant agents), abrasives, skin cooling agents, fixatives, insect repellents, ointments, vitamins and mixtures thereof. A "fixative", also called a "modulator", is understood herein to be an agent capable of influencing the manner in which the odor of a composition incorporating said modulator, in particular the evaporation rate and intensity, can be perceived over time by the observer or user, compared to the same perception in the absence of said modulator. In particular, a modulator makes it possible to extend the time for which the fragrance is perceived.Non-limiting examples of suitable modulators include methyl glucoside polyol; ethyl glucoside polyol; propyl glucoside polyol; isocetyl alcohol; PPG-3 myristyl ether; neopentyl glycol diethylhexanoate; sucrose laurate; sucrose dilaurate, sucrose myristate, sucrose palmitate, sucrose stearate, sucrose distearate, sucrose tristearate, hyaluronic acid disaccharide sodium salt, sodium hyaluronate, propylene glycol propyl ether; dicetyl ether; polyglycol Serine-4 ether; isocetyl-5; isocetyl-7, isocetyl-10; isocetyl-12; isocetyl-15; isocetyl-20; isocetyl-25; isocetyl-30; disodium lauroamphodipropionate; hexaethylene glycol monododecyl ether; and mixtures thereof; neopentyl glycol diisononanoate; cetearyl ethylhexanoate; panthenol ethyl ether, DL-panthenol, n-hexadecyl n-nonanoate, noctadecyl n-nonanoate, profragrance, cyclodextrin, encapsulants, and combinations thereof. Up to 20% by weight of the modulator, based on the total weight of the fragrance composition, can be incorporated into the perfumed consumer product.

[0076] It is understood that a person skilled in the art is entirely capable of designing the optimal formulation for obtaining the desired effect by mixing the above-mentioned components of the perfuming composition not only by applying standard knowledge in the art but also by trial and error method.

[0077] The composition of the present invention, which comprises a compound of formula (I) of the present invention and at least one fragrance carrier, constitutes a particular embodiment of the present invention, and also comprises a fragrance composition comprising the substance composition of the present invention, at least one fragrance carrier, at least one fragrance base, and optionally at least one fragrance adjuvant.

[0078] For the sake of clarity, it is also understood that mixtures obtained directly from chemical synthesis, which may contain the compound of formula (I) of the invention as a starting material, intermediate or final product, such as reaction media without appropriate purification, cannot be considered as perfuming compositions according to the invention, unless said mixture provides the compound of formula (I) of the invention in a form suitable for perfumery.Unless otherwise stated, unpurified reaction mixtures are generally excluded from the present invention.

[0079] The compounds of formula (I) of the invention can also be advantageously used in the field of modern perfumery, i.e. in all fields of fine perfumery or functional perfumery, to positively impart or modulate the odor of consumer products to which they are added. Another subject of the invention therefore also relates to perfumed consumer products, which contain, as perfuming ingredient, the composition of matter according to the invention as defined above.

[0080] The compounds of formula (I) of the present invention can be added as such or as part of the perfuming composition of the present invention.

[0081] For the sake of clarity, "perfumed consumer product" is intended to refer to a consumer product that delivers at least a pleasant fragrance effect to the surface or space to which it is applied (e.g., skin, hair, textile or domestic surface).In other words, the perfumed consumer product according to the present invention is a perfumed consumer product that comprises a functional compound, optionally additional benefit agents according to the desired consumer product, and an olfactory effective amount of at least one compound according to the present invention.For the sake of clarity, the perfumed consumer product is a non-edible product.

[0082] A more detailed description herein of the nature and type of ingredients of the perfumed consumer product is not warranted, but in any case is not exhaustive, and the skilled person can select them on the basis of his common knowledge and depending on the nature of the product and the desired effect.

[0083] Non-limiting examples of suitable perfumed consumer products include perfumes, such as fine perfumes, splash perfumes or eau de parfums, colognes, shave or aftershave lotions; fabric care products, such as liquid or solid detergents, optionally in pod or tablet form, fabric softeners, liquid or solid scent boosters, dryer sheets, fabric refreshers, ironing waters, paper, bleach, carpet cleaners, curtain care products; body care products, such as hair care products (e.g. shampoos, leave-on or rinse-off hair conditioners, coloring preparations or hairsprays, color care products, hair styling products, dental care products), disinfectants, intimate care products; cosmetics (e.g. skin creams or lotions, vanishing creams or deodorants or antiperspirants (e.g. sprays or roll-ons), depilatories, tanning or after-sun products, nail products, skin cleansers, cosmetics); or skin care products (e.g. soaps, shower mousses, shower oils or gels or bath mousses, bath oils or gels, or hygiene or foot / hand care products); air care products, such as air fresheners or "ready-to-use" powdered air fresheners that can be used in domestic spaces (rooms, refrigerators, cupboards, shoes or cars) and / or in public spaces (hall, hotel, mall, etc.); or home care products, such as mould removers, furniture care products, wipes, dishwashing detergents or hard surface (e.g. floor, bathroom, hygiene or window cleaner) detergents; leather care products; car care products, such as polishes, waxes or plastic cleaners.

[0084] Some of the above mentioned perfumed consumer products may be aggressive media for the substance composition of the present invention, which may require protection against premature degradation, for example by encapsulation or by chemically binding the compound of formula (I) of the present invention with another chemical suitable for releasing it upon an appropriate external stimulus, such as an enzyme, light, heat or a change in pH.

[0085] Typical methods for carrying out the method of the invention are reported in the following examples.

[0086] Working Example The invention will now be described in more detail by the following examples, in which abbreviations have their usual meaning in the art and temperatures are given in degrees Celsius (°C). Solvents were conventionally dried and distilled under an argon atmosphere. NMR spectra were recorded on a Bruker AV 300, AV 400, or AV 500 MHz spectrometer at 20°C. Chemical shifts were expressed as the solvent signals (chloroform, δ H = 7.26 ppm, δ C = 77.0 ppm. Signal assignments are 1 H, 1 H-COSY, -NOESY, 13 C. 1 Confirmation was performed by recording H-HSQC and -HMBC experiments. Gas chromatography was performed on an Agilent 7890 A series equipped with an HP5 column (30 m × 0.25 mm id, 0.25 μm film) and tetradecane was used as the internal standard.

[0087] Example 1 Preparation of 1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)ethan-1-one by the process of the present invention In a 1 L glass reactor equipped with a mechanical stirrer, a packed column and a reflux condenser, 60 g (0.61 mol) of potassium acetate, 250 g of 2-pyrrolidone and 250 g (1.11 mol) of 4-acetyl-3,5,5-trimethylcyclohex-2-en-1-yl acetate were added. The reaction mixture was stirred and then heated to 135° C. while gradually reducing the internal pressure to 40 mbar. The formed product was continuously distilled into the flask together with acetic acid over a period of 4 hours. The reaction mixture was then heated to 155° C. while reducing the pressure to 25 mbar. The distillate was then set aside and neutralized with aqueous soda and then washed with water. The resulting crude oil (188 g) was fractionally distilled at 65-80 °C / 5 mbar to obtain 169 g (92% yield) of 1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)ethan-1-one. Analysis of this fraction by GC chromatography showed that it was 97% 1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)ethan-1-one, 1.8% 1-(6,6-dimethyl-2-methylenecyclohex-3-en-1-yl)ethan-1-one, and 0.2% 1-(2,6,6-trimethylcyclohexa-2,4-dien-1-yl)ethan-1-one.

[0088] [ka]

[0089] Example 2 Preparation of ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate by the process of the present invention In a 1 L glass reactor equipped with a mechanical stirrer, a packed column and a reflux condenser, 50 g (0.50 mol) of potassium acetate, 200 g of 2-pyrrolidone and 300 g (1.18 mol) of ethyl 4-acetoxy-2,6,6-trimethylcyclohex-2-ene-1-carboxylate were added. The reaction mixture was stirred and then heated to 155 °C while gradually reducing the internal pressure to 50 mbar. The formed product was continuously distilled into the flask together with acetic acid over 4 hours. The reaction material was then heated to 165 °C while reducing the pressure to 25 mbar. The distillate was then set aside and neutralized with aqueous soda, followed by washing with water. The resulting crude oil (228 g) was fractionally distilled at 65-80 °C / 3 mbar to give 199 g (88% yield) of ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate. Analysis of this fraction by GC chromatography revealed that it was 97.2% ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate, 1.0% ethyl 6,6-dimethyl-2-methylenecyclohex-3-ene-1-carboxylate, and 1.0% ethyl 2,6,6-trimethylcyclohexa-2,4-diene-1-carboxylate.

[0090] [ka]

[0091] Example 3 Preparation of methyl 2-ethyl-6,6-dimethylcyclohexa-1,3-diene-1-carboxylate by the process of the present invention In a 1 L glass reactor equipped with a mechanical stirrer, a packed column and a reflux condenser, 50 g (0.50 mol) of potassium acetate, 200 g of 2-pyrrolidone and 300 g (1.18 mol) of methyl 4-acetoxy-2-ethyl-6,6-dimethylcyclohex-2-ene-1-carboxylate were added. The reaction mixture was stirred and then heated to 155 °C while gradually reducing the internal pressure to 50 mbar. The formed product was continuously distilled into the flask together with acetic acid over 4 hours. The reaction material was then heated to 165 °C while reducing the pressure to 25 mbar. The distillate was then set aside and neutralized with aqueous soda, followed by washing with water. The resulting crude oil (231 g) was fractionally distilled at 65-80 °C / 3 mbar to give 202 g of methyl 2-ethyl-6,6-dimethylcyclohex-1,3-diene-1-carboxylate (89.5% yield). Analysis of this fraction by GC chromatography showed that it was 98.5% methyl 2-ethyl-6,6-dimethylcyclohexa-1,3-diene-1-carboxylate, 0.3% methyl 2-ethylidene-6,6-dimethylcyclohex-3-ene-1-carboxylate, and 0.9% methyl 2-ethyl-6,6-dimethylcyclohexa-2,4-diene-1-carboxylate.

[0092] [ka]

[0093] Example 4 Preparation of ethyl 2,5,6-trimethylcyclohexa-1,3-diene-1-carboxylate by the process of the present invention In a 1 L glass reactor equipped with a mechanical stirrer, a packed column and a reflux condenser, 50 g (0.50 mol) of potassium acetate, 200 g of 2-pyrrolidone and 300 g (1.18 mol) of ethyl 4-acetoxy-2,5,6-trimethylcyclohex-2-ene-1-carboxylate were added. The reaction mixture was stirred and then heated to 155 °C while gradually reducing the internal pressure to 50 mbar. The formed product was continuously distilled into the flask together with acetic acid over 4 hours. The reaction material was then heated to 165 °C while reducing the pressure to 25 mbar. The distillate was then set aside and neutralized with aqueous soda, followed by washing with water. The resulting crude oil (223 g) was fractionally distilled at 65-80 °C / 3 mbar to give 194 g (85% yield) of 2,5,6-trimethylcyclohexa-1,3-diene-1-carboxylate. Analysis of this fraction by GC chromatography revealed that it was 98% 2,5,6-trimethylcyclohexa-1,3-diene-1-carboxylate (a cis + trans mixture of 44:56), 0.5% ethyl 5,6-dimethyl-2-methylenecyclohex-3-ene-1-carboxylate, and 1.0% ethyl 2,5,6-trimethylcyclohexa-2,4-diene-1-carboxylate.

[0094] Ethyl (5SR,6RS)-2,5,6-trimethylcyclohexa-1,3-diene-1-carboxylate (trans isomer): [ka]

[0095] Ethyl (5RS,6RS)-2,5,6-trimethylcyclohexa-1,3-diene-1-carboxylate (cis isomer): [ka]

Claims

1. Formula (I) 【Chemical 1】 [In the formula, n is an integer from 0 to 13; R １ , R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom, C １－６ Alkyl group or C ２－６ represents an alkenyl group; or R ４ and R ５ Together, C ３－６ forming a cycloalkyl group; X is C(O)R ６ Group, COOR ６ group, a CN group or a C═NR ６ group, and R ６ is a hydrogen atom, C １－６ Alkyl group or C ２－６ represents an alkenyl group], the method comprising the steps of: 【Chemistry 2】 [In the formula, n, X, R １ , R ２ , R ３ , R ４ and R ５ has the same meaning as defined in formula (I), and R ７ is a hydrogen atom, C ２－６ Alkenyl group, C １－６ an alkyl group optionally substituted with one or more halogen atoms, or C ６－１０ An aryl group, including a hydroxy group, C １－６ Alkyl group, C ２－６ Alkenyl group, C １－６ wherein R represents an integer from 1 to 3 and R represents an integer from 1 to 3, optionally substituted with one or more of an alkoxy group and / or a halogen atom, with a base having a boiling point higher than that of the compound of formula (I).

2. 2. The method of claim 1, wherein the base is a metal carboxylate, metal bicarbonate, or metal carbonate.

3. The metal carbonate is represented by the formula M ｐ CO ３ (III) wherein M is an alkali metal or alkaline earth metal, and p is 1 or 2; provided that when M is an alkaline earth metal, p is 1, and when M is an alkali metal, p is 2.

4. The metal bicarbonate is represented by the formula M(HOCO ２ ) ｑ (IV) wherein M is an alkali metal or alkaline earth metal, and q is 1 or 2; provided that when M is an alkaline earth metal, q is 2, and when M is an alkali metal, q is 1.

5. The metal carboxylate is represented by the formula (RCOO) ｒ M (V) wherein R is a hydrogen atom or C １－１８ 3. The method of claim 2, wherein M is a hydrocarbon group; M is an alkali metal or an alkaline earth metal; and r is 1 or 2; provided that when M is an alkali metal, r is 1, and when M is an alkaline earth metal, r is 2.

6. R is a hydrogen atom, a phenyl group, or C １－１０ Alkyl group or C ２－１０ is an alkenyl group, and preferably R is a hydrogen atom, a phenyl group or C １－６ Preferably, R is a hydrogen atom, a phenyl group, or a C １－３ The method of claim 5, wherein the group is an alkyl group.

7. 7. A process according to any one of claims 3 to 6, wherein M is selected from the group of magnesium, calcium, potassium, sodium and lithium, preferably potassium.

8. 6. The process of claim 5, wherein said process is carried out in the presence of a catalytic amount of said metal carboxylate.

9. 3. The method according to claim 1 or 2, wherein n is an integer from 0 to 4, preferably n is 1.

10. X is C(O)R ６ , or COOR ６ represents a group, and R ６ is a hydrogen atom, C １－３ Alkyl group or C ２－３ 3. The method of claim 1 or 2, wherein the alkyl group represents an alkenyl group.

11. R ２ and R ３ are each independently a hydrogen atom; R ４ and R ５ are each independently a hydrogen atom or C １－３ is an alkyl group; R １ is a hydrogen atom or C １－３ is an alkyl group, preferably R １ is a methyl group or an ethyl group, and R ７ 3. The method of claim 1, wherein is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a phenyl group.

12. 3. The process according to claim 1 or 2, wherein the compound of formula (I) is removed continuously during the process.

13. 3. The process according to claim 1 or 2, wherein the process is carried out in the presence of at least one aprotic dipolar solvent.

14. formula 【Chemistry 3】 [In the formula, R １ , R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom, C １－６ Alkyl group or C ２－６ represents an alkenyl group; or R ４ and R ５ Together, C ３－６ forming a cycloalkyl group; X is C(O)R ６ Group, COOR ６ group, a CN group or a C═NR ６ group, and R ６ is a hydrogen atom, C １－６ Alkyl group or C ２－６ represents an alkenyl group, R ７ is a hydrogen atom, C ２－６ Alkenyl group, C １－６ an alkyl group optionally substituted with one or more halogen atoms, or C ６－１０ An aryl group, including a hydroxy group, C １－６ Alkyl group, C ２－６ Alkenyl group, C １－６ wherein R represents an integer of 1 to 3, and R represents an integer of 1 to 3, optionally substituted with one or more of an alkoxy group and / or a halogen atom, with the proviso that 4-(but-2-enoyl)-3,5,5-trimethylcyclohex-2-en-1-yl acetate and ethyl 4-acetoxy-2,6,6-trimethylcyclohex-2-ene-1-carboxylate are excluded.

15. formula 【Chemistry 4】 [In the formula, R １ , R ２ , R ３ , R ４ and R ５ are each independently a hydrogen atom, C １－６ Alkyl group or C ２－６ represents an alkenyl group; or R ４ and R ５ Together, C ３－６ forming a cycloalkyl group; X is C(O)R ６ Group, COOR ６ group, a CN group or a C═NR ６ group, and R ６ is a hydrogen atom, C １－６ Alkyl group or C ２－６ represents an alkenyl group], with the proviso that ethyl 2-ethyl-6,6-dimethylcyclohexa-1,3-diene-1-carboxylate, methyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate, ethyl 2,6,6-trimethylcyclohexa-1,3-diene-1-carboxylate, 1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)ethan-1-one and 1-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)but-2-en-1-one are excluded.

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