Esters and ethers of 2,2,4,4-tetramethylcyclobutane-1,3-diol as aroma chemicals

Abstract

The present invention relates to the use of a compound of general formula (I), its stereoisomers or a mixture of its stereoisomers as an aromatic chemical. 1 is C1-C4 alkyl or -(C=O)-R 3 , R 2 is hydrogen, C1-C4 alkyl or -(C=O)-R 4 , and R 3 and R 4 The invention relates to an aromatic chemical composition comprising at least one compound of the general formula (I), its stereoisomers or mixtures of its stereoisomers, and a method for preparing a perfuming ready-to-use composition, which comprises incorporating at least one compound of the general formula (I), its stereoisomers or mixtures of its stereoisomers into the ready-to-use composition. The invention further relates to specific ethers and specific esters of the compound of the general formula (I), and methods for preparing the same.

Description

[0001] The present invention relates to the use of esters and ethers of 2,2,4,4-tetramethylcyclobutane-1,3-diol as aromachemicals, aromachemical compositions comprising at least one ester or ether of 2,2,4,4-tetramethylcyclobutane-1,3-diol, and methods for preparing perfuming ready-to-use compositions, which comprise incorporating at least one ester or ether of 2,2,4,4-tetramethylcyclobutane-1,3-diol into the ready-to-use compositions. The present invention further relates to specific ethers and specific esters of 2,2,4,4-tetramethylcyclobutane-1,3-diol and methods for preparing them. Background of the Invention

[0003] Aroma chemicals, especially fragrances, are of great importance, inter alia, in the field of cosmetics as well as cleaning and laundry compositions. Fragrances of natural origin are mostly expensive, are usually limited in their availability, and are also subject to variations in their content, purity, etc., due to fluctuating environmental conditions. To avoid these undesirable factors, it is therefore of great interest to produce synthetic substances which have organoleptic properties similar to those of the more expensive natural fragrances or which have new and interesting organoleptic characteristics.

[0004] Despite the large number of synthetic aromachemicals (fragrances and fragrances) already available, new components are still needed in order to be able to meet the large number of properties required for extremely diverse fields of application. These include, first of all, organoleptic properties, i.e. the compounds should have favorable odor (olfactory) or taste properties. In addition, however, aromachemicals should also have other positive secondary properties, for example, an efficient preparation method, the possibility of providing better sensory characteristics due to synergistic effects with other fragrances, higher stability under certain application conditions, higher extensibility, higher durability, etc.

[0005] However, since even small changes in chemical structure produce large changes in sensory properties such as odor and taste, targeted research on having specific sensory properties such as a specific odor is extremely difficult. Therefore, in most cases, research on new fragrances and flavors is difficult and laborious, and it is not even known whether a substance with the desired odor and / or taste will actually be found.

[0006] DE 1114811 describes a process for the preparation of diesters by reacting aliphatic carboxylic acids or benzoic acid with 2,2,4,4-tetramethylcyclobutane-1,3-diol, 2,4-dimethyl-2,4-diethylcyclobutane-1,3-diol or 2,2,4,4-tetraethylcyclobutane-1,3-diol, and the use of the esters as lubricants, plasticizers, heat transfer oils and hydraulic fluids.

[0007] DE 1142695 describes the plasticization of cellulose esters using diesters obtainable from aliphatic carboxylic acids or benzoic acid and 2,2,4,4-tetramethylcyclobutane-1,3-diol, 2,4-dimethyl-2,4-diethylcyclobutane-1,3-diol or 2,2,4,4-tetraethylcyclobutane-1,3-diol as plasticizers.

[0008] No. 3,043,791 describes the use of diesters obtainable from (C1-C4)carboxylic acids and 2,2,4,4-tetramethylcyclobutane-1,3-diol, 2,4-dimethyl-2,4-diethylcyclobutane-1,3-diol or 2,2,4,4-tetraethylcyclobutane-1,3-diol as plasticizers for polyvinyl chloride and plastic compositions comprising polyvinyl chloride and the diesters.

[0009] No. 3,062,852 describes diesters obtainable from aliphatic carboxylic acids and 2,2,4,4-tetra-(C1-C4)alkylcyclobutane-1,3-diol, and the use of said diesters as synthetic lubricants.

[0010] US 3,227,764 describes a process for separating 2,2,4,4-tetra-(C1-C4)alkylcyclobutane-1,3-diol, in particular 2,2,4,4-tetramethylcyclobutane-1,3-diol, into its cis- and trans-isomers, wherein the diol is reacted with a (C1-C9)carboxylic acid to give the corresponding diester, which can then be separated into the individual cis- and trans-isomers due to their different melting temperatures and converted back into the corresponding cis- and trans-isomers of 2,2,4,4-tetramethylcyclobutane-1,3-diol.

[0011] The use of esters and ethers of 2,2,4,4-tetramethylcyclobutane-1,3-diol as aroma chemicals has hitherto not been described in the prior art. SUMMARY OF THE INVENTION

[0013] The object of the present invention is to provide substances which exhibit pleasant organoleptic properties and can be advantageously used as aromachemicals. Another object of the present invention is to provide substances which can be used as aromachemicals in ready-to-use compositions. In particular, strongly odoriferous substances with a pleasant odor are sought. Furthermore, these aromachemicals should be combinable with other aromachemicals, allowing the creation of new advantageous sensory profiles. In addition, these aromachemicals should be obtainable from readily available raw materials, allowing their rapid and economical production, and should not present toxicological concerns.

[0014] Surprisingly, it has been found that these and other objects are achieved by esters and ethers of 2,2,4,4-tetramethylcyclobutane-1,3-diol.

[0015] Therefore, the first aspect of the present invention relates to the use of a compound of formula (I), its stereoisomers or a mixture of its stereoisomers as an aroma chemical:

[0016]

[0017] in:

[0018] R 1 is C1-C4 alkyl or -(C=O)-R 3 ,

[0019] R 2 is hydrogen, C1-C4 alkyl or -(C=O)-R 4 ,and

[0020] R 3 and R 4 are independently selected from hydrogen and C1-C4 alkyl.

[0021] The use according to the invention also includes, for example, in the group R 1 and / or group R 2 The invention also relates to the use of mixtures of two or more compounds of the general formula (I) which differ from one another in certain aspects.

[0022] The present invention further relates to an aromachemical composition comprising at least one compound of formula (I) as defined above, its stereoisomers or mixtures of stereoisomers, and at least one other compound selected from other aromachemicals different from compound (I) and non-aromachemical carriers.

[0023] It has further been found that the compounds of general formula (I) generally display a pleasant and characteristic odor and can be used to prepare perfuming ready-to-use compositions. In addition, they can advantageously be combined with other aroma chemicals different from compound (I) to produce new fragrance characteristics.

[0024] Therefore, the present invention further relates to a process for preparing a perfuming ready-to-use composition, which comprises incorporating into the ready-to-use composition at least one compound of formula (I), its stereoisomers or its mixture of stereoisomers, and the use of a compound of formula (I), its stereoisomers or its mixture of stereoisomers as defined above for improving the flavor profile of a perfuming ready-to-use composition.

[0025] Among the group of compounds of formula (I), ether compounds of formula (Ia) and ester compounds of formula (Ib) are not described in the art.

[0026] Therefore, the present invention also relates to novel compounds of the general formula (Ia), their stereoisomers or mixtures of their stereoisomers and processes for their preparation:

[0027]

[0028] in:

[0029] R 1a is a C2-C4 alkyl group and

[0030] R 2a It is hydrogen or C2-C4 alkyl.

[0031] Furthermore, the present invention relates to novel compounds of the general formula (Ib), their stereoisomers or mixtures of their stereoisomers and processes for their preparation:

[0032]

[0033] in:

[0034] R 1b -(C=O)-R 3 ,

[0035] R 2b is hydrogen or -(C=O)-R 4 ,and

[0036] R 3 and R 4 are independently selected from hydrogen and C1-C4 alkyl, provided that if present, R 3 and R 4 are different.

[0037] The compounds of formula (I), their stereoisomers or mixtures of their stereoisomers have advantageous organoleptic properties, in particular a pleasant odor. Therefore, they can be advantageously used as aroma chemicals, for example, in perfume compositions, cosmetic compositions, body care compositions, oral and dental hygiene products, hygiene articles, cleaning compositions, fabric detergent compositions, dishwashing compositions, perfume dispenser compositions, pharmaceutical compositions, crop protection compositions and other ready-to-use compositions.

[0038] By virtue of their physical properties, the compounds of formula (I), their stereoisomers or mixtures of their stereoisomers have particularly good, essentially universal solvent properties for other aromatics and other conventional ingredients in perfuming ready-to-use compositions, such as, in particular, perfume compositions. Therefore, the compounds of formula (I), their stereoisomers or mixtures of their stereoisomers are advantageously combined with other aroma chemicals, in particular allowing the creation of perfume compositions having novel advantageous sensory characteristics.

[0039] In addition, the compound of formula (I), its stereoisomer or its mixture of stereoisomers can be prepared in good yield and purity by a single step or two step synthesis, starting from the readily available and inexpensive 2,2,4,4-tetramethylcyclobutane-1,3-diol, respectively. Therefore, the compound of formula (I), its stereoisomer or its mixture of stereoisomers can be prepared on a large scale and in a simple and cost-effective manner.

[0040] Additionally, the compounds of formula (I), their stereoisomers or mixtures of their stereoisomers may have low or no toxicity since they are derived from 2,2,4,4-tetramethylcyclobutane-1,3-diol, for which no carcinogenic or toxic effects have been demonstrated. DETAILED DESCRIPTION OF THE INVENTION

[0042] In the context of the present invention, the expression "C1-C4-alkyl" refers to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutylene and tert-butyl. Preferably, the expression "C1-C4-alkyl" refers to methyl, ethyl, n-propyl and isopropyl, in particular methyl and ethyl.

[0043] The term "aromachemicals" denotes substances which are used to obtain a sensory impression, more precisely an olfactory or fragrance impression, in particular an aroma or fragrance impression. These aromachemicals are therefore suitable for use in "aromachemical compositions" and / or "ready-to-use perfuming compositions". Thus, as used herein, the term "aromachemical composition" refers to a composition which primarily evokes an odor impression. Likewise, as used herein, the term "ready-to-use perfuming composition" refers to a ready-to-use composition which primarily evokes an odor impression.

[0044] The term "olfaction" denotes an odor impression without any positive or negative judgment, whereas the term "aroma" (also called "fragrance" or "fragrance") relates to an odor impression that is generally perceived as pleasant. Odors give rise to taste impressions.

[0045] The term "strong-smelling substances" refers to substances or aroma chemicals which exhibit a strong odor impression. A strong odor impression is to be understood as meaning those properties of aroma chemicals which allow a surprising perception even at very low concentrations in the air space. The intensity can be determined with the aid of a threshold determination. The threshold is the concentration of the substance in the relevant air space at which the odor impression is still perceptible by a representative test panel, although it no longer has to be defined. Perhaps the strongest odor classes of known substances, i.e. those with a very low odor threshold, are mercaptans, whose thresholds are usually in the ppb / m 3 within the range.

[0046] "Favourable sensory properties", "favourable organoleptic properties" or "pleasant odour" are pleasant impressions which describe the beauty and simplicity of the odour impression conveyed by the aromachemical. "Beauty" and "simplicity" are terms familiar to the person skilled in the art, the perfumer. Beauty generally refers to a pleasant sensory impression which is spontaneously produced, positively perceived. However, "good" is not necessarily synonymous with "sweet". "Good" can also be a musk or sandalwood odour. "Simple" generally refers to a spontaneously produced sensory impression which produces some specific reproduction of the same suggestion for the same experimental group. For example, a substance may have a spontaneous recollection of "apple": the odour is then simply "apple". If the apple odour is very pleasant because the odour is, for example, a recollection of sweet ripe apples, the odour is called "good". However, the odour of a generally sour apple can also be simple. If two reactions occur when smelling a substance, in the embodiment, a good and simple apple odour therefore occurs, the substance has particularly favourable sensory properties.

[0047] Depending on the spatial arrangement of the oxygen atom relative to the cyclobutane ring, the compounds of formula (I) may exist as individual cis-isomers (I-cis) or trans-isomers (I-trans) or as cis / trans isomer mixtures:

[0048]

[0049] Therefore, the present invention relates to the use of cis isomers, i.e. (I-cis), trans isomers, i.e. (I-trans), and cis / trans isomer mixtures thereof, i.e. (I-cis / trans). Therefore, if not otherwise specified, the expressions "compound I", "compound of formula I", etc. as used herein refer to pure cis isomers, pure trans isomers, and cis / trans isomer mixtures thereof, wherein the isomers are present in the same amount or contain an excess of one isomer.

[0050] The pure cis-isomers and pure trans-isomers of compound (I) and the cis / trans isomer mixtures have all favorable organoleptic properties. Therefore, the pure cis-isomers and pure trans-isomers of compound (I) and the cis / trans isomer mixtures are equally suitable as aroma chemicals. In addition, at least for some compounds (I), for example for the ester compound acetic acid (3-acetoxy-2,2,4,4-tetramethyl-cyclobutyl) ester, the organoleptic properties of the cis-isomer are not significantly different from those of the trans-isomer.

[0051] On the other hand, the basic aroma characteristics of the ether compounds of the general formula (I) are different from the aroma characteristics of the ester compounds of the general formula (I).

[0052] Therefore, a first embodiment of the present invention relates to the use of ether compounds of the general formula (I), wherein in formula (I):

[0053] R 1 is a C1-C4 alkyl group, and

[0054] R 2 It is hydrogen or C1-C4 alkyl.

[0055] Compounds (I) of the first embodiment include monoethers and diethers of 2,2,4,4-tetramethylcyclobutane-1,3-diol. Generally, monoethers of 2,2,4,4-tetramethylcyclobutane-1,3-diol exhibit less intense odor than the corresponding diethers of 2,2,4,4-tetramethylcyclobutane-1,3-diol.

[0056] Therefore, it is preferred to use diether compounds, that is, wherein in formula (I), R 1 and R 2 The compounds of the general formula (I) are independently selected from C1-C4 alkyl groups.

[0057] Furthermore, the synthesis of ether compounds of the general formula (I) in which the substituents attached to the oxygen atom are identical is generally simpler than the synthesis of ether compounds of the general formula (I) having different substituents on the oxygen atom.

[0058] Therefore, it is further preferred to use 1 and R 2 They are ether compounds of the same general formula (I).

[0059] Preferred examples of ether compounds of general formula (I) are:

[0060] 2,4-Dimethoxy-1,1,3,3-tetramethyl-cyclobutane,

[0061] 2,4-dimethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer,

[0062] 2,4-dimethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0063] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane,

[0064] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer,

[0065] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0066] 2,4-di-n-propoxy-1,1,3,3-tetramethyl-cyclobutane,

[0067] 2,4-di-n-propoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer,

[0068] 2,4-di-n-propoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0069] 2,4-diisopropoxy-1,1,3,3-tetramethyl-cyclobutane,

[0070] 2,4-diisopropoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer,

[0071] 2,4-diisopropoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0072] 2,4-di-n-butoxy-1,1,3,3-tetramethyl-cyclobutane,

[0073] 2,4-di-n-butoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer,

[0074] 2,4-di-n-butoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0075] 2,4-diisobutoxy-1,1,3,3-tetramethyl-cyclobutane,

[0076] 2,4-diisobutoxy-1,1,3,3-tetramethyl-cyclobutane, which is present essentially in the form of its cis isomer, and

[0077] 2,4-diisobutoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0078] 2,4-di-tert-butoxy-1,1,3,3-tetramethyl-cyclobutane,

[0079] 2,4-di-tert-butoxy-1,1,3,3-tetramethyl-cyclobutane, which is present essentially in the form of its cis isomer, and

[0080] 2,4-Di-tert-butoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer.

[0081] Despite the generally slightly less intense odor of the monoethers of 2,2,4,4-tetramethylcyclobutane-1,3-diol compared to the corresponding diethers of 2,2,4,4-tetramethylcyclobutane-1,3-diol, these monoethers still have characteristic aroma characteristics. The monoether derivatives of 2,2,4,4-tetramethylcyclobutane-1,3-diol according to the invention are therefore valuable compounds for use as aroma chemicals.

[0082] Therefore, another preferred embodiment of the present invention relates to the use of the compound of general formula (I), its stereoisomers or mixtures of its stereoisomers as aroma chemicals:

[0083]

[0084] in:

[0085] R 1 is a C1-C4 alkyl group and

[0086] R 2 For hydrogen.

[0087] Examples of preferred monoether compounds (I) of this embodiment are:

[0088] 3-Methoxy-2,2,4,4-tetramethyl-cyclobutanol,

[0089] 3-methoxy-2,2,4,4-tetramethyl-cyclobutanol, which exists essentially in the form of its cis isomer,

[0090] 3-methoxy-2,2,4,4-tetramethyl-cyclobutanol, which exists essentially in the form of its trans isomer,

[0091] 3-Ethoxy-2,2,4,4-tetramethyl-cyclobutanol,

[0092] 3-ethoxy-2,2,4,4-tetramethyl-cyclobutanol, which exists essentially in the form of its cis isomer,

[0093] 3-ethoxy-2,2,4,4-tetramethyl-cyclobutanol, which exists essentially in the form of its trans isomer,

[0094] 3-n-propoxy-2,2,4,4-tetramethyl-cyclobutanol,

[0095] 3-n-propoxy-2,2,4,4-tetramethyl-cyclobutanol, which exists essentially in the form of its cis isomer,

[0096] 3-n-propoxy-2,2,4,4-tetramethyl-cyclobutanol, which exists essentially in the form of its trans isomer,

[0097] 3-n-Butoxy-2,2,4,4-tetramethyl-cyclobutanol,

[0098] 3-n-butoxy-2,2,4,4-tetramethyl-cyclobutanol, which exists essentially in the form of its cis isomer,

[0099] 3-n-butoxy-2,2,4,4-tetramethyl-cyclobutanol, which exists essentially in the form of its trans isomer,

[0100] 3-tert-Butoxy-2,2,4,4-tetramethyl-cyclobutanol,

[0101] 3-tert-Butoxy-2,2,4,4-tetramethyl-cyclobutanol, which exists substantially in the form of its cis isomer, and 3-tert-Butoxy-2,2,4,4-tetramethyl-cyclobutanol, which exists substantially in the form of its trans isomer.

[0102] More preferably, an ether compound of the general formula (I) is used, wherein R 1 and R 2 It is a C1-C3 alkyl group.

[0103] Even more preferably, ether compounds of the general formula (I) are used, wherein R 1 and R 2 are identical and are selected from methyl, ethyl, n-propyl and isopropyl.

[0104] Particularly preferably, ether compounds of the general formula (I) are used, wherein R 1 and R 2 It is methyl or ethyl.

[0105] Particularly preferably, use is made of:

[0106] 2,4-Dimethoxy-1,1,3,3-tetramethyl-cyclobutane,

[0107] 2,4-dimethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer,

[0108] 2,4-dimethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0109] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane,

[0110] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer, and

[0111] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer.

[0112] A second embodiment of the present invention relates to the use of ester compounds of general formula (I), wherein in formula (I):

[0113] R 1 -(C=O)-R 3 ,

[0114] R 2 is hydrogen or -(C=O)-R 4 ,and

[0115] R 3 and R 4 As defined above.

[0116] Compounds (I) of the second embodiment include monoesters and diesters of 2,2,4,4-tetramethylcyclobutane-1,3-diol. Generally, monoesters of 2,2,4,4-tetramethylcyclobutane-1,3-diol exhibit less intense odor than the corresponding diesters of 2,2,4,4-tetramethylcyclobutane-1,3-diol.

[0117] Therefore, it is preferred to use diester compounds, that is, compounds of the general formula (I), wherein in formula (I):

[0118] R 1 -(C=O)-R 3 ,

[0119] R 2 -(C=O)-R 4 and

[0120] R 3 and R 4 As defined above,

[0121] Here, too, the synthesis of ester compounds of the general formula (I) in which the substituents attached to the oxygen atom are identical is generally simpler than the synthesis of ester compounds of the general formula (I) having different substituents on the oxygen atom.

[0122] Therefore, it is further preferred to use an ester compound of the general formula (I), wherein:

[0123] R 1 -(C=O)-R 3 ,

[0124] R 2 -(C=O)-R 4 ,and

[0125] R 3 and R 4 As defined above,

[0126] And the group R 3 and R 4 for the same.

[0127] It is further preferred to use an ester compound of the general formula (I) wherein R 3 and R 4 Selected from hydrogen and C1-C3 alkyl.

[0128] Preferred examples of ester compounds of general formula (I) are:

[0129] Formic acid (3-formyloxy-2,2,4,4-tetramethyl-cyclobutyl) ester,

[0130] Formic acid (3-formyloxy-2,2,4,4-tetramethyl-cyclobutyl) ester, which exists essentially in the form of its cis isomer,

[0131] Formic acid (3-formyloxy-2,2,4,4-tetramethyl-cyclobutyl) ester, which exists essentially in the form of its trans isomer,

[0132] Acetate (3-acetoxy-2,2,4,4-tetramethyl-cyclobutyl) ester,

[0133] (3-acetoxy-2,2,4,4-tetramethyl-cyclobutyl) acetate, which exists essentially in the form of its cis isomer,

[0134] (3-acetoxy-2,2,4,4-tetramethyl-cyclobutyl) acetate, which exists essentially in the form of its trans isomer,

[0135] Propionic acid (3-propionyloxy-2,2,4,4-tetramethyl-cyclobutyl) ester,

[0136] Propionic acid (3-propionyloxy-2,2,4,4-tetramethyl-cyclobutyl) ester, which exists essentially in the form of its cis isomer,

[0137] Propionic acid (3-propionyloxy-2,2,4,4-tetramethyl-cyclobutyl) ester, which exists essentially in the form of its trans isomer,

[0138] Isobutyric acid (3-isobutyryloxy-2,2,4,4-tetramethyl-cyclobutyl) ester,

[0139] Isobutyric acid (3-isobutyryloxy-2,2,4,4-tetramethyl-cyclobutyl) ester, which exists essentially in the form of its cis isomer, and isobutyric acid (3-isobutyryloxy-2,2,4,4-tetramethyl-cyclobutyl) ester, which exists essentially in the form of its trans isomer.

[0140] Even more preferably, ester compounds of the general formula (I) are used, wherein R 3 and R 4 are the same and are selected from hydrogen and C1-C3 alkyl.

[0141] Particularly preferred is the use of ester compounds of the general formula (I) wherein R3 and R 4 is selected from hydrogen, methyl or ethyl.

[0142] Particularly preferably, use is made of:

[0143] Acetate (3-acetoxy-2,2,4,4-tetramethyl-cyclobutyl) ester,

[0144] (3-acetoxy-2,2,4,4-tetramethyl-cyclobutyl) acetate, which exists substantially in the form of its cis isomer, and (3-acetoxy-2,2,4,4-tetramethyl-cyclobutyl) acetate, which exists substantially in the form of its trans isomer.

[0145] In a particular embodiment of the invention, the compounds of general formula (I) are present essentially in the form of their cis isomers.

[0146] In another particular embodiment of the invention, the compounds of general formula (I) are present essentially in the form of their trans isomers.

[0147] Another preferred embodiment of the present invention relates to the use of the compound of general formula (I), its stereoisomers or mixtures of its stereoisomers as aroma chemicals:

[0148]

[0149] in:

[0150] R 1 is a C1-C4 alkyl group and

[0151] R 2 -(C=O)-R 3 .

[0152] Regarding the groups C1-C4 alkyl and -(C=O)-R 3 The preferred and very preferred meanings of , preference is given to the discussion given above.

[0153] Particularly preferred compounds of this embodiment are:

[0154] Acetate (3-methoxy-2,2,4,4-tetramethyl-cyclobutyl) ester,

[0155] (3-methoxy-2,2,4,4-tetramethyl-cyclobutyl) acetate, which exists substantially in the form of its cis isomer, and (3-methoxy-2,2,4,4-tetramethyl-cyclobutyl) acetate, which exists substantially in the form of its trans isomer.

[0156] In this context, the term "substantially" means that the cis or trans isomer of the specific compound is present in an amount of at least 90% by weight, preferably at least 95% by weight, in particular at least 98% by weight, based on the total amount of cis and trans isomers.

[0157] Typically, compound (I) is produced as a cis / trans isomer mixture. Separation of cis and trans isomers may be difficult and laborious, or may not be completely achieved with reasonable effort.

[0158] Therefore, a preferred embodiment of the present invention relates to the use of compounds of general formula (I) as defined above and below, wherein the compounds of general formula (I) are present in the form of cis / trans isomer mixtures. In these mixtures, the two isomers may be present in the same amount or almost the same amount, for example in a cis / trans or trans / cis isomer ratio of 50:50 or 55:45, or one isomer, i.e. the cis or trans isomer, may be present in excess, for example one isomer may be present in a cis / trans or trans / cis isomer ratio of 60:40, 65:35, 70:30 or 75:25.

[0159] Furthermore, compound (I) can be used as an aroma chemical in a wide range of purities, as long as the impurities do not have a significant adverse effect on the aroma of compound (I). Therefore, according to the present invention, for use as an aroma chemical, the purity of compound (I) is not particularly limited. Preferably, compound (I) has a purity of at least 70%, particularly at least 90%, and especially at least 95%.

[0160] Due to its preparation process starting from 2,2,4,4-tetramethylcyclobutane-1,3-diol, the diether compound of the general formula (I) may contain a minor amount of the monoether compound (I-OH), and the diester compound of the general formula (I) may contain a minor amount of the monoester compound (II-OH):

[0161]

[0162] Where R 1 and R 3 has one of the meanings given above.

[0163] Preferably, the amount of monosubstituted compounds (I-OH) or (II-OH) that may be contained in the diether and diester compounds of the general formula (I) is less than 25% by weight, more preferably less than 10% by weight, even more preferably less than 5% by weight, in particular less than 1% by weight, based on the total amount of compound (I).

[0164] In a particularly preferred embodiment of the present invention, the diether and diester compounds of the general formula (I) contain no monosubstituted compounds (I-OH) or (II-OH), respectively.

[0165] Likewise, the monoether and monoester compounds of the general formula (I) may contain a minor amount of the corresponding disubstituted compounds. Preferably, the amount of disubstituted compounds of the general formula (I) contained in the monoether and monoester compounds of the general formula (I) is less than 25% by weight, more preferably less than 10% by weight, even more preferably less than 5% by weight, in particular less than 1% by weight, based on the total amount of compound (I).

[0166] In addition, the group R 1 and R 2 are different diether compounds of general formula (I) and wherein the group R 3 and R 4 The diester compounds of the general formula (I) (hereinafter referred to as asymmetrically substituted compounds) may contain a minor amount of symmetrically substituted compounds, i.e., compounds in which the radical R 1 and R 2 are diether compounds of the same general formula (I) and wherein the radical R 3 and R 4 The same diester compound of general formula (I). Typically, the amount of the symmetrically substituted compound that may be contained in the asymmetrically substituted compound of general formula (I) is less than 50% by weight, preferably less than 25% by weight, more preferably less than 10% by weight, even more preferably less than 5% by weight, and in particular less than 1% by weight, based on the total amount of compound (I).

[0167] In addition, the group R 1 is a C1-C4 alkyl group and R 2 -(C=O)-R 3 The ether-ester compounds of the general formula (I), also referred to below as mixed substitution compounds (I), may contain corresponding diether or diester compounds. In addition, depending on whether monoether or monoester compounds are used as starting materials, these mixed substitution compounds (I) may also contain minor amounts of corresponding monoether or monoester compounds. Preferably, the amount of these by-products that may be contained in the mixed substitution compounds of the general formula (I) is less than 50% by weight, more preferably less than 40% by weight, and in particular less than 30% by weight, based on the total amount of compound (I).

[0168] The above-mentioned preferred embodiments can be combined with each other as required.

[0169] Therefore, in a particularly preferred embodiment of the present invention, it relates to the use of compounds of the general formula (I) having a purity of at least 95% and in the form of a cis / trans isomer mixture.

[0170] The monoether compound of the general formula (I) can be effectively prepared by using an alkylating agent R in the presence of a base. 1 -X is prepared by alkylating 2,2,4,4-tetramethylcyclobutane-1,3-diol, wherein R 1has one of the meanings given above and X denotes a leaving group selected from halogen, such as Cl, Br, I, and sulfonate, such as tosylate, mesylate, triflate or perfluorobutanesulfonate.

[0171] Suitable bases are generally selected from inorganic bases and organic bases.

[0172] Suitable inorganic bases which can be used in the alkylation reaction are, for example, alkali metal carbonates, such as Li2CO3, Na2CO3, K2CO3 or Cs2CO3, alkali metal hydroxides, such as LiOH, NaOH or KOH, and hydrogen donors, such as NaH, LiAlH4 or NaBH4.

[0173] Suitable organic bases which can be used in the alkylation reaction are, for example, tertiary amines, such as trimethylamine, triethylamine, tripropylamine, ethyldiisopropylamine, etc., or basic N-heterocycles, such as morpholine, pyridine, lutidine, DMAP, DABCO, DBU or DBN.

[0174] The alkylation reaction is carried out under conventional alkylation reaction conditions well known to those skilled in the art.

[0175] Typically, 2,2,4,4-tetramethylcyclobutane-1,3-diol is reacted with a subequimolar or nearly equimolar amount, such as 0.7, 0.8, 0.9 or 0.95 equivalents of an alkylating agent R 1 -X is reacted to give a monosubstituted compound (I-OH), which is further subjected to a purification step to remove unwanted by-products or impurities, such as residual starting materials or the corresponding disubstituted compound.

[0176] In general, the purification step is carried out by using customary purification methods, such as crystallization, distillation or chromatography, such as column chromatography or high performance liquid chromatography.

[0177] The group R 1 and R 2 The preparation of the diether compound of the same general formula (I) is usually carried out by reacting 2,2,4,4-tetramethylcyclobutane-1,3-diol with at least 2 equivalents, for example 2.0, 2.1, 2.5 or 3.0 equivalents of an alkylating agent R 1 -X or R 2 -X reaction, where the group R 1 , R 2 and X have one of the meanings given above, the crude product obtained is subsequently subjected to a purification step as defined above. If only minor amounts of impurities and by-products are present in the crude product mixture, the purification step can also be carried out by means of a simple extractive workup.

[0178] The group R 1 and R 2The preparation of the various diether compounds of the general formula (I) is usually carried out by first reacting 2,2,4,4-tetramethylcyclobutane-1,3-diol with a sub-equimolar or nearly equimolar amount, for example 0.7, 0.8, 0.9 or 0.95 equivalents of an alkylating agent R 1 -X to obtain a monosubstituted compound (I-OH), which after a purification step is further reacted with a second alkylating agent R 2 -X reaction.

[0179] Generally speaking, the ester compound of general formula (I) is effectively prepared by reacting 2,2,4,4-tetramethylcyclobutane-1,3-diol with a carboxylic acid R 3 -COOH and optionally with a carboxylic acid R 4 -COOH (where R 3 and R 4 has one of the meanings given above) or its anhydride, or a carboxylic acid R 3 -COOH and / or R 4 It is prepared by reacting a mixture of -COOH and its anhydride. The reaction is usually carried out in the presence of an esterification catalyst or a base.

[0180] Suitable esterification catalysts which can be used in the reaction are well known to the skilled person. Suitable esterification catalysts are, for example, metal-based catalysts, such as iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts such as metal alkoxides; mineral acids, such as sulfuric acid, hydrochloric acid or phosphoric acid; or organic sulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid.

[0181] Suitable bases are, for example, organic bases as defined above.

[0182] Alternatively, the ester compound of general formula (I) can be prepared by reacting 2,2,4,4-tetramethylcyclobutane-1,3-diol with a compound of formula R in the presence of an organic base. 3 -(C=O)X' or R 4 -(C=O)X' acid halide reaction, wherein R 3 and R 4 has one of the meanings given above, and X' is halogen such as Cl, Br or I.

[0183] Suitable organic bases are as defined above.

[0184] The individual reaction conditions for preparing the ester compounds of the general formula (I) are well known to the skilled person.

[0185] To prepare the monoester compound of the general formula (I), 2,2,4,4-tetramethylcyclobutane-1,3-diol is usually reacted with a sub-equimolar or almost equimolar amount, for example 0.7, 0.8, 0.9 or 0.95 equivalent of a carboxylic acid R 3-COOH or its anhydride or a mixture of the carboxylic acid and its anhydride. Alternatively, 2,2,4,4-tetramethylcyclobutane-1,3-diol is usually reacted with the same amount of an acid halide R 3 -(C=O)X' is reacted in the presence of an organic base. The crude product obtained is subsequently subjected to a purification step as defined above.

[0186] To prepare the group R 3 and R 4 The same diester compound of general formula (I) is usually prepared by reacting 2,2,4,4-tetramethylcyclobutane-1,3-diol with at least 2 equivalents, for example 2.0, 2.1, 2.5 or 3.0 equivalents of carboxylic acid R 3 -COOH or R 4 -COOH, its anhydride or a mixture of the carboxylic acid and its anhydride. Alternatively, 2,2,4,4-tetramethylcyclobutane-1,3-diol is usually reacted with at least 2 equivalents of an acid halide R 3 -(C=O)X' or R 4 -(C=O)X' is reacted in the presence of an organic base. The crude product obtained is subsequently subjected to a purification step as defined above. If only minor amounts of impurities and by-products are present in the crude product mixture, the purification step can also be carried out by means of a simple extractive work-up.

[0187] The group R 3 and R 4 The preparation of the various diester compounds of the general formula (I) is usually carried out by first reacting 2,2,4,4-tetramethylcyclobutane-1,3-diol with a sub-equimolar or nearly equimolar amount, for example 0.7, 0.8, 0.9 or 0.95 equivalents of a carboxylic acid R 3 -COOH or its anhydride to obtain a monosubstituted compound (II-OH), which, after a purification step, is further reacted with a second carboxylic acid R 4 -COOH or its anhydride.

[0188] Alternatively, wherein the group R 3 and R 4 The preparation of different compounds (I) can also be carried out by first reacting 2,2,4,4-tetramethylcyclobutane-1,3-diol with a subequimolar or nearly equimolar amount, for example 0.7, 0.8, 0.9 or 0.95 equivalents of an acid halide R 3 -(C=O)X' is reacted in the presence of an organic base to obtain a monosubstituted compound (II-OH), which is further reacted with a second acid halide R after a purification step. 4 -(C=O)X' reaction.

[0189] The raw material 2,2,4,4-tetramethylcyclobutane-1,3-diol is a diol structural unit commonly used as a monomer for synthesizing polymer materials. Therefore, 2,2,4,4-tetramethylcyclobutane-1,3-diol is easily obtained from commercial sources. Alternatively, 2,2,4,4-tetramethylcyclobutane-1,3-diol can also be synthesized in large quantities by using methods well described in the art, for example, by dimerization of dimethyl ketene.

[0190] Composition:

[0191] The compounds of formula (I), their stereoisomers or mixtures of their stereoisomers can be used in a variety of compositions such as ready-to-use compositions. The olfactory properties, material properties (e.g. solubility in conventional solvents and compatibility with other conventional components of such compositions) and toxicological acceptability of the compounds of formula (I) emphasize that they are particularly suitable for the stated purposes of use and compositions.

[0192] Furthermore, the compounds of the general formula (I) exhibit advantageous secondary properties.

[0193] For example, the compounds of general formula (I) may provide better sensory characteristics due to synergistic effects with other fragrances, which means that they may provide an enhancing effect on other fragrances. Therefore, they are suitable as enhancers for other fragrances.

[0194] The boosting effect means that in fragrance formulations a substance strengthens and intensifies the overall impression of the mixture. In the mint range, for example, it is known that menthyl methyl ether intensifies the aroma or taste mixture of peppermint oil, especially in the top notes, producing a considerably more intense and more complex perception, although the ether itself as a pure substance does not exhibit a strong odor at all. In fragrance applications, as a pure substance, (Methyl dihydrojasmonate) exhibits only a slight jasmine scent and acts as an odor booster to enhance the spread, freshness and volume of perfume compositions. The boosting effect is particularly desirable in applications where top note properties are required, in which the odor impression is to be conveyed particularly quickly and intensely, such as in deodorants, air fresheners or in the taste zone in chewing gum.

[0195] To achieve this boosting effect, the compound of formula (I), its stereoisomers or mixtures of its stereoisomers are usually used in an amount of 0.1-20% by weight, preferably 0.5-5% by weight, in particular 0.6-3% by weight, based on the total weight of the fragrance mixture.

[0196] In addition, the compounds of formula (I), their stereoisomers or mixtures of their stereoisomers may have other positive effects on the compositions in which they are applied. For example, the compounds of formula (I), their stereoisomers or mixtures of their stereoisomers may enhance the overall properties of the composition, such as the stability, formulation stability, extensibility or durability of the composition.

[0197] Therefore, another embodiment of the present invention relates to the use of a compound of the general formula (I) or a mixture of two or more different compounds of the formula (I) or a stereoisomer thereof or a mixture of their stereoisomers as aromachemical in a ready-to-use composition.

[0198] As used herein, the term "ready-to-use composition" refers to a composition intended to be directly applied or used by an end user.

[0199] Generally speaking, the ready-to-use compositions in which the aromachemicals of the present invention, ie the compounds of general formula (I) as defined above, can be used are perfuming ready-to-use compositions.

[0200] Perfuming ready-to-use compositions in which the aromachemicals according to the invention, i.e. the compounds of general formula (I) as defined above, can be used are, for example, compositions for personal care, for home care, for industrial applications and for other applications, such as pharmaceutical compositions or crop protection compositions.

[0201] Preferably, the ready-to-use composition is selected from the group consisting of fragrance compositions, cosmetic compositions, body care compositions, oral and dental hygiene products, hygiene articles, cleaning compositions, fabric detergent compositions, dishwashing compositions, compositions for perfume dispensers, pharmaceutical compositions and crop protection compositions.

[0202] The fragrance composition may be chosen from fine perfumes, air fresheners in liquid form, in gel-like form or in a form applied to a solid carrier, aerosol sprays, scented cleansers, scented candles and scented oils, such as lamp oils or massage oils.

[0203] Examples of fine fragrances are perfume extracts, Eau de Parfums, Eau de Toilettes, Eau de Colognes, Eau de Solide, Extrait Parfum and the like.

[0204] The body care composition may be chosen from aftershaves, preshave products, splash colognes, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water type, such as skin creams and lotions, face creams and lotions, sunscreen creams and lotions, aftersun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions and self-tanning creams and lotions, powders, hydrogels, hair care products, such as hair sprays, hair gels, hair styling lotions, conditioners, shampoos and permanent and semi-permanent hair dyes, hair styling compositions, such as cold perms, and hair softening compositions, hair conditioners, hair milks and shampoos, deodorants and antiperspirants, such as underarm sprays, roll-ons, deodorant sticks and deodorant creams, decorative make-up, such as eyeliners, eye shadows, nail polishes, foundations, lipsticks and eyebrow tints.

[0205] Products for oral and dental hygiene may be selected from toothpaste, dental floss, mouthwash, breath freshener, dental foam, dental gel and dental strips.

[0206] The hygiene article may be selected from perfumes, insecticides, repellents, propellants, rust removers, perfumed freshening wipes, underarm pads, baby diapers, sanitary napkins, toilet paper, cosmetic wipes, handkerchiefs, dishwashing detergents and deodorants.

[0207] Cleaning compositions, such as solid surface cleaners, may be selected from perfumed acidic, alkaline and neutral cleaners, for example floor cleaners, window cleaners, bathroom and sanitary cleaners, scouring milks, solid and liquid toilet cleaners, powder and foam carpet cleaners, dishwashing detergents for manual and machine dishwashing, waxes and polishes such as furniture polishes, floor waxes, shoe polishes, disinfectants, surface disinfectants and sanitary cleaners, brake cleaners, pipe cleaners, limescale cleaners, grill and oven cleaners, algae and moss removers, mould release agents and facade cleaners.

[0208] The fabric detergent composition may be selected from liquid detergents, powdered detergents, laundry pre-treaters such as bleaches, soaking agents and stain removers, fabric softeners, detergent soaps, detergent tablets.

[0209] Food means raw, cooked or processed edible substances, ices, beverages or ingredients used or intended in whole or in part for human consumption, or chewing gums, gums, jellies and candies.

[0210] A food supplement is a product intended for ingestion that contains dietary ingredients intended to add additional nutritional value to food. A dietary ingredient may be one or any combination of the following: a vitamin, a mineral, an herb or other botanical, an amino acid, a dietary substance, a concentrate, a metabolite, a component or an extract that a person uses to supplement their diet by increasing dietary intake. Food supplements can be found in many forms, such as tablets, capsules, soft gels, gel capsules, liquids or powders.

[0211] Pharmaceutical compositions include compositions intended for use in the diagnosis, care, mitigation, treatment or prevention of disease, as well as preparations (other than foods) intended to affect the structure or any function of the body of man or other animals.

[0212] Crop protection compositions comprise compositions intended for the management of plant diseases, weeds and other pests (vertebrates and invertebrates) which damage crops and forests.

[0213] The composition of the present invention may further comprise one or more substances, such as preservatives, abrasives, anti-acne agents, agents for combating skin aging, antibacterial agents, slimming agents, anti-dandruff agents, anti-inflammatory agents, anti-irritants, agents for alleviating irritation, antimicrobial agents, antioxidants, astringents, antiperspirants, antibacterial agents, antistatic agents, adhesives, buffers, carrier materials, chelating agents, cell stimulants, cleansing agents, care agents, depilatories, surface active substances, deodorants, antiperspirants, emulsifiers, enzymes, essential oils, fibers, film formers, color fixatives, foam formers, foam stabilizers, substances for preventing foaming, foam boosters, fungicides, gelling agents, gel formers, hair care agents, hair fixatives, hair softeners, moisturizers, moisturizing substances, wetting substances, bleaching agents, enhancers, detergents, Fluorescent brightener, impregnating agent, stain repellent, friction reducer, lubricant, moisturizer, ointment, sunscreen, plasticizer, covering agent, polish, glitter, polymer, powder, protein, refatting agent, exfoliant, silicone, skin soothing agent, skin cleanser, skin care agent, skin healing agent, skin lightening agent, skin protectant, skin softener, cooling agent, skin cooling agent, warming agent, skin warming agent, stabilizer, UV absorber, UV filter, fabric softener, suspending agent, skin tanning agent, thickener, vitamin, oil, wax, fat, phospholipid, saturated fatty acid, mono- or polyunsaturated fatty acid, alpha-hydroxy acid, polyhydroxy fatty acid, liquefier, dye, color protection agent, pigment, preservative, polyol, surfactant, electrolyte, organic solvent or silicone derivative.

[0214] As mentioned above, it has further been found that compounds of general formula (I) generally display a pleasant and characteristic odor and can be used to prepare perfuming ready-to-use compositions and / or they can be advantageously combined with other aroma chemicals different from compound (I) to produce new fragrance profiles.

[0215] Therefore, a particular embodiment of the present invention relates to the use of a compound of formula (I) or a mixture of two or more different compounds of formula (I) or their stereoisomers or mixtures of their stereoisomers for improving the flavour profile of a perfuming ready-to-use composition.

[0216] The present invention further relates to an aromachemical composition comprising at least one compound of formula (I) as defined above, its stereoisomers or mixtures of stereoisomers, and at least one other compound selected from other aromachemicals different from compound (I) and non-aromachemical carriers.

[0217] This includes aroma chemical compositions comprising at least one compound of formula (I) as defined above, a stereoisomer thereof or a mixture of stereoisomers thereof and at least one other aroma chemical different from compound (I).

[0218] Further included are aromachemical compositions comprising at least one compound of formula (I) as defined above, a stereoisomer thereof or a mixture of stereoisomers thereof and at least one non-aromachemical carrier.

[0219] Also included are aromachemical compositions comprising at least one compound of formula (I) as defined above, its stereoisomers or mixtures of its stereoisomers, at least one other aromachemical different from compound (I) and at least one non-aromachemical carrier.

[0220] Preferably, the aromachemical composition comprises at least one compound of formula (I) as defined above, its stereoisomers or mixtures of its stereoisomers, at least one other aromachemical different from compound (I) and at least one non-aromachemical carrier.

[0221] The other aroma chemicals different from compound (I) can be, for example, one, preferably 2, 3, 4, 5, 6, 7, 8 other aroma chemicals selected from: geranyl acetate (acetate 3,7-dimethyl-2,6-octadien-1-yl) ester, α-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate (Phenirat 1 ), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), dihydrojasmonate (preferably having a cis isomer content of greater than 60% by weight) (Hedione 9 、Hedione HC 9 )、4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydro-cyclopenta[g]benzopyran (Galaxolid 3 ), tetrahydrolinalool (3,7-dimethyloctan-3-ol), ethyllinalool, benzyl salicylate, 2-methyl-3-(4-tert-butylphenyl) propanal (Lilial2 ), cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5-indenyl acetate and / or 4,7-methano-3a,4,5,6,7,7a-hexahydro-6-indenyl acetate (Herbaflorat 1 ), citronellol, citronellol acetate, tetrahydrogeraniol, vanillin, linalyl acetate, phenylethyl acetate (1-phenylethyl acetate), octahydro-2,3,8,8-tetramethyl-2-naphthone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene (Iso ESuper 3 ), ethyl salicylate, 4-tert-butyl cyclohexyl acetate (Oryclone 1 ), 2-tert-butyl cyclohexyl acetate (Agrumex HC 1 ), α-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-butene-2-one), n-α-methylionone, α-isomethylionone, coumarin, terpineol acetate, 2-phenylethanol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde (Lyral 3 ), α-amylcinnamaldehyde, ethylene brazilate, (E)- and / or (Z)-3-methylcyclopentadecan-5-enone (Muscenon 9 ), 15-pentadeca-11-ene lactone and / or 15-pentadeca-12-ene lactone (Globalide 1 ), 15-cyclopentadecanolide (Macrolide 1 )、1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl)ethanone (Tonalid 10 ), 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol (Florol 9 )、2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-butene-1-ol (Sandolen 1 ), cis-3-hexenyl acetate, trans-3-hexenyl acetate, trans-2 / cis-6-nonadienol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde (Vertocitral 1 )、2,4,4,7-Tetramethyloct-6-en-3-one (Claritone 1 )、2,6-dimethyl-5-heptene-1-aldehyde (Melonal 2 ), borneol, 3-(3-isopropylphenyl)butyraldehyde (Florhydral 2 ), 2-methyl-3-(3,4-methylenedioxyphenyl)propanal (Helional 3)、3-(4-ethylphenyl)-2,2-dimethylpropanal (Florazon 1 ), 7-methyl-2H-1,5-benzodioxine -3(4H)-ketone (Calone), 3,3,5-trimethylcyclohexyl acetate (preferably having a cis isomer content of 70% by weight or more) and 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol (Ambrinol S 1 ).

[0222] Where trade names are given above, these refer to the following sources:

[0223] 1 Symrise GmbH, a trading name in Germany;

[0224] 2 Givaudan AG, a trade name of Switzerland;

[0225] 3 International Flavors & Fragrances Inc., a trade name in the United States;

[0226] 5 Danisco Seillans SA, a French trading name;

[0227] 9 Firmenich SA, a trade name of Switzerland;

[0228] 10 PFW Aroma Chemicals BV is a trading name of the Netherlands.

[0229] Other aroma chemicals with which the compounds of formula (I) as defined above, their stereoisomers or mixtures of their stereoisomers can be combined, for example, to obtain the compositions according to the invention can be found, for example, in S. Arctander, own publication, Perfume and Flavor Chemicals, Volumes I and II, Montclair, NJ, 1969, or in K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th edition, Wiley-VCH, Weinheim 2001. In particular, mention may be made of:

[0230] Extracts of natural origin, for example essential oils, condensates, absolutes, resins, resinoids, incense, tinctures, for example ambergris tincture; balsam oil; angelica seed oil; angelica root oil; fennel essential oil; valerian oil; clove basil oil; tree moss absolute; laurel oil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birch oil; bitter almond oil; celery oil; thornleaf oil; balsam bean oil; juniper oil; calamus oil; camphor oil; cananga oil; cardamom oil; quinoa oil; cassia oil; cassia absolute; castoreum absolute; cedar leaf oil; cedarwood oil; rockrose oil; citronella oil; lemon oil; copaiba balsam; coriander oil; costus root oil; cumin oil; cedarwood oil; davana oil; dill fruit oil; dill seed oil; Eau de brouts absolute; oakmoss absolute moss absolute); elemi oil; tarragon oil; lemon eucalyptus oil; eucalyptus oil; anise oil; pine needle oil; geranium oil; geranium oil; grapefruit oil; guaiac wood oil; guyun balsam; guyun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; orris root absolute; orris root oil; jasmine absolute; chamomile oil; Roman chamomile oil; carrot seed oil; spearmint oil; coriander oil; labdanum oil; labdanum absolute Oil; Cistus resin; Lavender absolute; Lavender oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Lime oil distilled; Lime oil pressed; Lina oil; Litsea cubeba oil; Bay leaf oil; Mace oil; Marjoram oil; Orange oil; Cinnamon bark oil; Mimosa absolute; Musk seed oil; Musk tincture; Clary sage oil; Nutmeg oil; Myrrh absolute; Myrrh oil; Myrtle oil; Clove Leaf Oil; Clove Flower Oil; Neroli Oil; Frankincense Absolute; Frankincense Oil; Parsnip Root Oil; Neroli Absolute; Orange Oil; Oregano Oil; Palmarosa Oil; Patchouli Oil; Perilla Seed Oil; Peru Balsam Oil; Parsley Leaf Oil; Parsley Seed Oil; Petitgrain Oil; Peppermint Oil; Pimento Oil; Pine Oil; Peppermint Oil; Rose Absolute; Rosewood Oil; Rose Oil; Rosemary Oil; Dalmatian Sage Oil; Spanish Sage Oil; Sandalwood Wood oil; celery seed oil; spike lavender oil; star anise oil; styrax oil; marigold oil; fir needle oil; tea tree oil; turpentine oil; thyme oil; tolu balsam; tonka bean absolute; tuberose absolute; vanilla essence extract; violet leaf absolute; verbena oil; vetiver root oil; juniper berry oil; lees oil; wormwood oil; wintergreen oil; hyssop oil; civet absolute; cassia leaf oil; cassia oil and its fractions or components isolated therefrom;

[0231] Various aromatics from the hydrocarbon group, such as 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; afarnesene; limonene; longifolene; myrcene; ocimene; valencia orangene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane;

[0232] Aliphatic alcohols, for example hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenols; 1-octen-3-ol; a mixture of 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;

[0233] Aliphatic aldehydes and acetals thereof, for example hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal ; heptaldehyde diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; (E / Z)-1-(1-methoxypropoxy)-hex-3-ene; aliphatic ketones and their oximes, for example 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one;

[0234] Aliphatic sulfur-containing compounds, such as 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylmercaptohexyl acetate; 1-menthene-8-thiol;

[0235] Aliphatic nitriles, for example 2-nonenenitrile; 2-undecenenitrile; 2-tridecenenitrile; 3,12-tridecadienenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile;

[0236] Esters of aliphatic carboxylic acids, for example (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate Esters; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octanoate; methyl 2-nonanoate; allyl 2-isopentyloxyacetate; methyl 3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl crotonate;

[0237] Acyclic terpene alcohols, for example geraniol; nerol; linalool; lavandinol; nerolidol; farnesol; tetrahydrolinalool; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octadien-3-ol; 2,6-dimethyl-2,5,7-octadien-1-ol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid enols and 3-methyl-2-butenoates; acyclic Terpene aldehydes and ketones, for example geranyl aldehyde; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl- and diethyl acetals of geranyl aldehyde, neral, 7-hydroxy-3,7-dimethyloctanal; cyclic terpene alcohols, for example menthol; isopulegol; alpha-terpene alcohols; terpene-4-ol; menth-8-ol; menth-1-ol; menth-7-ol; borneol; isoborneol; oxylinalool; nopol; cedrol; ambroxanol; vetiverol; guaiacol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid enols and 3-methyl-2-butenoates;

[0238] Cyclic terpene aldehydes and ketones, for example menthone; isomenthone; 8-mercaptoisomenth-3-one; carvone; camphor; fenchone; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethylionone; α-irone; α-damascone; β-damascone; β-damascenone; δ-damascone; γ-damascone; 1-(2,4,4-trimethyl-2-cyclohexene- 1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-naphthone-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; nootkatone; dihydronootkatone; 4,6,8-megatrien-3-one; α-sweet orange aldehyde; β-sweet orange aldehyde; acetylated cedarwood oil (methyl cedarone);

[0239] Cyclic alcohols, such as 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isoborneolcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[0240] Alicyclic alcohols, such as α-3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butene-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butene-1-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butene-1-ol; -(2,2,3-trimethyl-3-cyclopent-1-yl)pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;

[0241] Cyclic and alicyclic ethers, for example eucalyptol; methyl cedar ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclododecane; α-cedar oxide; 3a,6,6,9a-tetramethyldodecahydronaphthalene[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphthalene[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo-[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-diene alkyl;

[0242] Cyclic and macrocyclic ketones, for example 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentenone; 3-methyl-5-cyclopentenone; 3-methyl 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecene-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecene-1-one; 7-cyclohexadecene-1-one; (7 / 8)-cyclohexadecene-1-one; 9-cycloheptadecan-1-one; cyclopentadecanone; cyclohexadecanone;

[0243] Cycloaliphatic aldehydes, for example 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde;

[0244] Alicyclic ketones, for example 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthyl ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienone; tert-butyl(2,4-dimethyl-3-cyclohexen-1-yl)ketone;

[0245] Esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-amylcyclohexyl acetate; 4-tert-amylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; octahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; octahydro-2,5,5,8a-tetramethyl-2 -naphthyl ester; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methano-octahydro-5 or 6-indenyl acetate;

[0246] Esters of cycloaliphatic alcohols, for example 1-cyclohexylethyl crotonate;

[0247] Esters of cycloaliphatic carboxylic acids, for example allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; cis- and trans-methyl dihydrojasmonate; cis- and trans-methyl jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-acetate;

[0248] Aromatic aliphatic alcohols, for example benzyl alcohol; 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;

[0249] Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, for example benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; α-trichloromethylbenzyl acetate; α,α-dimethylphenylethyl acetate; α,α-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;

[0250] Aromatic aliphatic ethers, such as 2-phenylethyl methyl ether; 2-phenylethyl isopentyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; solanum nigrum aldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-di Alkane; 4,4a,5,9b-tetrahydroindenyl[1,2-d]-m-diol 4,4a,5,9b-tetrahydro-2,4-dimethylindenyl[1,2-d]-m-di Britain.

[0251] Aromatic and aromatic aliphatic aldehydes, for example benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; solanum nigrum aldehyde; 4-methylbenzaldehyde; 4-methylphenyl-acetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)-propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)-propanal; 3-(4-tert-butylphenyl)propanal; meat Cinnamaldehyde; α-butylcinnamaldehyde; α-amylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal;

[0252] Aromatic and araliphatic ketones, for example acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)-ethanone; 2-benzofuranyl-ethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanylmethanone; 6-tert-butyl-1,1-dimethyl-4-indanylmethanone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; 5′,6′,7′,8′-tetrahydro-3′,5′,5′,6′,8′,8′-hexamethyl-2-naphthylacetonone;

[0253] Aromatic and araliphatic carboxylic acids and their esters; for example benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isopentyl salicylate; hexyl salicylate; cyclohexyl salicylate; 3-hexenyl cis-salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; 3-phenyltriethylglycerol; ethyl 3-methyl-3-phenylglycerol;

[0254] Nitrogen-containing aromatic compounds, for example 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 3-methyl-5-phenyl-2-pentenenitrile; 3-methyl-5-phenylvaleronitrile; methyl anthranilate; methyl N-methyl anthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

[0255] Phenols, phenyl ethers and phenyl esters, for example estragole; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenol acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-tolyl phenylacetate;

[0256] Heterocyclic compounds, for example 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;

[0257] Lactones, such as 1,4-octanolactone; 3-methyl-1,4-octanolactone; 1,4-nonanolactone; 1,4-decanolactone; 8-decene-1,4-lactone; 1,4-undecanolactone; 1,4-dodecanolactone; 1,5-decanolactone; 1,5-dodecanolactone; 4-methyl-1,4-decanolactone; 1,15-pentadecanolactone; cis- and trans-11-pentadecan-1,15-lactone; cis- and trans- -12-pentadecadecene-1,15-lactone; 1,16-hexadecane lactone; 9-hexadecene-1,16-lactone; 10-oxa-1,16-hexadecane lactone; 11-oxa-1,16-hexadecane lactone; 12-oxa-1,16-hexadecane lactone; 1,12-dodecane dioic acid ethylene ester; 1,13-tridecanedioic acid ethylene ester; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin.

[0258] At least one non-aromatic chemical carrier can be a compound, a compound mixture or other additive that has no or no significant sensory properties. Generally, if present in the aromachemical composition of the present invention, at least one non-aromatic chemical carrier is a compound, a compound mixture or other additive that has no or no significant sensory properties. The non-aromatic chemical carrier is used to dilute and / or fix the aromachemical contained in the aromachemical composition, that is, the compound of formula (I), and optionally one or more other aromachemicals different from compound (I).

[0259] Suitable carrier materials may be liquid or oily carrier materials as well as waxy or solid carrier materials.

[0260] Suitable liquid or oily carrier materials are selected, for example, from water, alcohols, such as methanol or ethanol, aliphatic diols and polyols having a melting temperature of below 20° C., such as ethylene glycol, glycerol, diglycerol, propylene glycol or dipropylene glycol and 1,2-butylene glycol, cyclic siloxanes, such as hexamethylcyclotrisiloxane or decamethylcyclopentasiloxane, diethylene glycol monomethyl ether, diethyl phthalate, isopropyl myristate, triethyl citrate, benzyl benzoate, vegetable oils, such as fractionated coconut oil or fatty alcohol esters having a melting temperature of below 20° C., such as myristyl acetate or myristyl lactate, glycerol esters having a melting temperature of below 20° C., and fatty acid alkyl esters having a melting temperature of below 20° C., such as isopropyl myristate.

[0261] Suitable waxy or solid carrier materials are selected, for example, from fatty alcohols having a melting temperature below 20° C., such as myristyl alcohol, stearyl alcohol or cetyl alcohol, polyols having a melting temperature above 20° C., esters of fatty acids and fatty alcohols having a melting temperature above 20° C., such as lanolin, beeswax, carnauba wax, candelilla wax or Japan wax, waxes prepared from petroleum, such as hard paraffin, water-insoluble porous minerals, such as silica gel, silicates, such as talc, microporous crystalline aluminosilicates (zeolites), clay minerals, such as bentonites, or phosphates, such as sodium tripolyphosphate, paper, cardboard, wood, textile composites or nonwoven materials made of natural and / or synthetic fibers.

[0262] Suitable carrier materials are also selected, for example, from water-soluble polymers, such as polyacrylates or quaternized polyvinylpyrrolidones, or water-alcohol soluble polymers, such as special thermoplastic polyesters and polyamides. The polymer carrier material can be in various forms, for example in the form of gels, pastes, solid particles such as microcapsules or friable coatings.

[0263] Preferably, the aromachemical composition is chosen from the perfuming ready-to-use compositions as defined above.

[0264] In general, the total amount of at least one compound of formula (I), its stereoisomers or mixtures of its stereoisomers in the aromachemical composition of the invention is usually suitable for the specific intended use or intended application and can therefore vary within wide limits. Usually, standard commercial amounts commonly used in perfumes are used.

[0265] Therefore, the total amount of at least one compound of formula (I), its stereoisomers or mixtures of stereoisomers in the composition is 0.001-99.9% by weight, preferably 0.01-90% by weight, more preferably 0.05-80% by weight, even more preferably 0.1-60% by weight, in particular 0.1-40% by weight, based on the total weight of the composition.

[0266] In one embodiment of the present invention, the total amount of at least one compound of formula (I), its stereoisomers or mixtures of its stereoisomers in the composition is 0.001-5% by weight, preferably 0.01-2% by weight, based on the total weight of the composition.

[0267] Another embodiment of the present invention relates to a composition comprising at least one compound of formula (I), a stereoisomer thereof or a mixture of stereoisomers thereof and at least one component selected from the group consisting of surfactants, emollients and solvents.

[0268] One embodiment of the present invention relates to a composition comprising at least one compound of formula (I), a stereoisomer thereof or a mixture of stereoisomers thereof and at least one solvent.

[0269] In the context of the present invention, a "solvent" is used to dilute a compound of formula (I), its stereoisomers or a mixture of its stereoisomers as defined above. Some solvents have at the same time immobilizing properties.

[0270] One or more solvents can be present in the composition at 0.01-99 wt % based on the composition. In one embodiment of the invention, the composition comprises 0.1-90 wt % based on the composition, preferably 0.5-80 wt % solvent. The amount of solvent can be selected depending on the composition. In one embodiment of the invention, the composition comprises 0.05-10 wt % based on the composition, preferably 0.1-5 wt %, more preferably 0.2-3 wt %. In one embodiment of the invention, the composition comprises 20-70 wt % based on the composition, preferably 25-50 wt % solvent.

[0271] Preferred solvents are ethanol, dipropylene glycol (DPG), propylene glycol, 1,2-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethyl phthalate (DEP), isopropyl myristate (IPM), triethyl citrate (TEC) and benzyl benzoate (BB).

[0272] Particularly preferred solvents are selected from ethanol, propylene glycol, dipropylene glycol, triethyl citrate, benzyl benzoate and isopropyl myristate.

[0273] In a preferred embodiment of the present invention, the solvent is selected from ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, triethyl citrate and isopropyl myristate.

[0274] According to another aspect, the compound of formula (I), its stereoisomers or mixtures of its stereoisomers are suitable for use in surfactant-containing compounds. Due to their characteristic fragrance profile, the compound of formula (I), its stereoisomers or mixtures of its stereoisomers are particularly useful for perfuming surfactant-containing compositions such as detergents (particularly laundry detergents and multi-purpose detergents).

[0275] One embodiment of the present invention therefore relates to a composition comprising at least one compound of formula (I), a stereoisomer thereof or a mixture of its stereoisomers and at least one surfactant.

[0276] The surfactant may be selected from anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants. Surfactant-containing compositions, such as shower gels, bubble baths, shampoos, etc., preferably comprise at least one anionic surfactant.

[0277] The composition of the invention generally comprises a surfactant in an amount of 0-40% by weight, preferably 0-20% by weight, more preferably 0.1-15% by weight, in particular 0.1-10% by weight, based on the total weight of the composition. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, optionally partially oxidized alkyl (alkenyl) oligoglycosides or glucuronic acid derivatives, fatty acid-N-alkylglucamides, hydrolyzed proteins (in particular wheat-based plant products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution, although they preferably have a narrow range homolog distribution.

[0278] Zwitterionic surfactants are surfactants that contain at least one quaternary ammonium group and at least one -COO (-) or -SO3 (-)Particularly suitable zwitterionic surfactants are so-called betaines, for example N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinates, N-amidopropyl-N,N-dimethylammonium glycinates, for example cocoamidopropyldimethylammonium glycinates, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines containing 8 to 18 carbon atoms in the alkyl or acyl radical, and cocoamidoethylhydroxyethylcarboxymethylglycinate. Particular preference is given to fatty acid amides known under the CTFA name Cocamidopropyl Betaine.

[0279] Amphoteric surfactants are also particularly suitable as cosurfactants. 18 The present invention relates to a surface-active compound which contains at least one free amino group and at least one -COOH- or -SO3H- group in the molecule in addition to an alkyl or acyl group and is capable of forming an inner salt. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, which contain about 8 to 18 carbon atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-coconut alkylaminopropionate, cocoacylaminoethylaminopropionate and acylsarcosine.

[0280] Anionic surfactants are characterized by a water-soluble anionic group, such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic group. Skin-safe anionic surfactants are known in large quantities to practitioners from relevant textbooks and are commercially available. They are, in particular, alkyl sulfates, alkyl ether sulfates, alkyl ether carboxylates, acyl thiocyanates, acyl sarcosinates, linear C-containing anionic surfactants in the form of alkali metal, ammonium or alkanolammonium salts. 12 -C8 alkyl or acyl acyltaurines, and sulfosuccinates and acylglutamates in the form of alkali metal or ammonium salts.

[0281] Particularly suitable cationic surfactants are quaternary ammonium compounds, preferably ammonium halides, more especially chlorides and bromides, for example alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. In addition, readily biodegradable quaternary ester compounds, for example dialkylammonium methosulfates and methylhydroxyalkyldialkanoyloxyalkylammonium methosulfates sold under the name Stepantex and The corresponding products of the ester series can be used as cationic surfactants. "Esterquats" are generally understood to be quaternized fatty acid triethanolamine ester salts. They can provide a certain softness to the composition. They are known substances prepared by relevant methods of organic chemistry. Other cationic surfactants suitable according to the invention are quaternized hydrolyzed proteins.

[0282] One embodiment of the present invention relates to a composition comprising at least one compound of formula (I), a stereoisomer thereof or a mixture of its stereoisomers and at least one oil component.

[0283] The oil component is generally present in a total amount of 0.1-80, preferably 0.5-70, more preferably 1-60, even more preferably 1-50%, particularly 1-40%, more particularly 5-25%, especially 5-15% by weight based on the composition.

[0284] The oil component can be chosen, for example, from Guerbet alcohols based on fatty alcohols containing 6 to 18, preferably 8 to 10, carbon atoms, and other esters, for example myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate Esters, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate, and C 18 -C 38 Alkyl-hydroxycarboxylic acid with linear or branched C6-C 22 Esters of fatty alcohols, more particularly dioctyl malate, esters of linear and / or branched fatty acids with polyols (for example propylene glycol, dimer diol or trimer triol), based on C6-C 10 Triglycerides of fatty acids, based on C6-C 18 Liquid mixture of mono-, di- and triglycerides of fatty acids, C6-C 22Esters of fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, esters of dicarboxylic acids with polyols containing 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C 22 Fatty alcohol carbonates, for example dicaprylyl carbonate (Cetiol@CC), Guerbet carbonates based on fatty alcohols containing 6 to 18, preferably 8 to 10 carbon atoms, benzoic acid and linear and / or branched C6-C 22 Esters of alcohols (e.g. TN), a linear or branched, symmetrical or asymmetrical dialkyl ether containing 6 to 22 carbon atoms in each alkyl group, for example dioctyl ether ( OE), ring-opening products of epoxidized fatty acid esters with polyols and hydrocarbons, or mixtures thereof.

[0285] Preparation method:

[0286] Another embodiment of the invention relates to a process for the preparation of a perfuming ready-to-use composition, comprising incorporating into the ready-to-use composition at least one compound of formula (I), its stereoisomers or its mixture of stereoisomers as defined above.

[0287] The method comprises incorporating at least one compound of formula (I), its stereoisomer or a mixture of its stereoisomers into a ready-to-use composition having no or insignificant sensory properties to provide the ready-to-use composition with a special smell and / or a special fragrance. In addition, the method also comprises improving the smell and / or fragrance of a ready-to-use composition that already has significant sensory properties by incorporating at least one compound of formula (I), its stereoisomer or a mixture of its stereoisomers into the ready-to-use composition.

[0288] Preferred ready-to-use compositions are those mentioned above.

[0289] The total amount of at least one compound of formula (I), its stereoisomer or mixture of its stereoisomers incorporated into the ready-to-use composition is highly dependent on the intended use or intended application and can therefore vary over wide ranges. Typical amounts of at least one compound of formula (I), its stereoisomer or mixture of its stereoisomers incorporated into the ready-to-use composition are those defined above for the composition.

[0290] The compounds of formula (I) used according to the invention, their stereoisomers or mixtures of their stereoisomers, compositions obtainable by the above process of the invention and aromachemical compositions of the invention containing them may also be in the form of microcapsules, spray-dried forms, inclusion compounds or extruded products. The properties can be further optimized by so-called "coating" with materials suitable for a more targeted release of the fragrance, for which waxy synthetic substances, such as polyvinyl alcohol, are preferably used.

[0291] Microencapsulation can be carried out, for example, by means of capsule materials such as polyurethanes or soft gelatin through so-called coagulation methods. Spray-dried aromatic oils can be prepared, for example, by spray-drying an emulsion or dispersion comprising a compound of formula (I), a stereoisomer thereof, or a mixture of its stereoisomers, wherein the carrier material that can be used is modified starch, protein, cyclodextrin, and vegetable gum. Inclusion complexes can be prepared, for example, by introducing a dispersion of a fragrance composition and a cyclodextrin or urea derivative into a suitable solvent such as water. Compounds of formula (I), a stereoisomer thereof, or a mixture of its stereoisomers can be melted with a suitable waxy substance and solidified subsequently, optionally extruded in a suitable solvent such as isopropanol and prepared.

[0292] Another embodiment of the present invention relates to compounds of the general formula (Ia), their stereoisomers or mixtures of their stereoisomers:

[0293]

[0294] in:

[0295] R 1a is a C2-C4 alkyl group, and

[0296] R 2a It is hydrogen or C2-C4 alkyl.

[0297] A preferred embodiment of the present invention relates to diether compounds of the general formula (Ia), wherein R 1a and R 2a The compounds of the general formula (Ia) are independently selected from C2-C4 alkyl groups.

[0298] It is further preferred that the group R 1a and R 2a They are diether compounds of the same general formula (Ia).

[0299] Preferred examples of compounds of general formula (Ia) are:

[0300] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane,

[0301] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer,

[0302] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0303] 2,4-di-n-propoxy-1,1,3,3-tetramethyl-cyclobutane,

[0304] 2,4-di-n-propoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer,

[0305] 2,4-di-n-propoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0306] 2,4-diisopropoxy-1,1,3,3-tetramethyl-cyclobutane,

[0307] 2,4-diisopropoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer,

[0308] 2,4-diisopropoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0309] 2,4-di-n-butoxy-1,1,3,3-tetramethyl-cyclobutane,

[0310] 2,4-di-n-butoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer,

[0311] 2,4-di-n-butoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer,

[0312] 2,4-diisobutoxy-1,1,3,3-tetramethyl-cyclobutane,

[0313] 2,4-diisobutoxy-1,1,3,3-tetramethyl-cyclobutane, which is present essentially in the form of its cis isomer, and

[0314] 2,4-Diisobutoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer.

[0315] More preferably, the compounds of formula (Ia) wherein the group R 1a and R 2a Selected from ethyl, n-propyl and isopropyl.

[0316] Even more preferred are compounds of formula (Ia) in which the radical R 1a and R 2a are the same and are selected from ethyl, n-propyl and isopropyl.

[0317] Particularly preferred compounds (1.a) are:

[0318] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane,

[0319] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its cis isomer, and

[0320] 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane, which exists essentially in the form of its trans isomer.

[0321] The compounds of the general formula (Ia) may be present in the form of a cis / trans isomer mixture or may be present substantially in the form of its cis isomer or its trans isomer, respectively.

[0322] With regard to the expressions "cis / trans isomer mixture" and "substantially present", reference is made to the remarks given above in connection with the compounds of the general formula (I).

[0323] Preferably, the compound of formula (Ia) is present in the form of a cis / trans isomer mixture.

[0324] Compounds of general formula (Ia) can be prepared as described for compounds of general formula (I).

[0325] Therefore, the present invention also relates to a process for preparing a compound of formula (Ia) as defined above, its stereoisomers or a mixture of its stereoisomers, which comprises:

[0326] (i) 2,2,4,4-tetramethylcyclobutane-1,3-diol is reacted with an alkylating agent R 1a -X and optionally an alkylating agent R 2a -X in the presence of a base to give a crude product mixture, wherein R 1a and R 2a has one of the meanings given above, and X represents a leaving group selected from halogen, such as Cl, Br, I, and sulfonate, such as tosylate, mesylate, triflate or perfluorobutanesulfonate, and

[0327] (ii) subjecting the crude product mixture obtained in step (i) to a purification step.

[0328] The alkylation reaction in step (i) is carried out under conventional alkylation reaction conditions well known to those skilled in the art.

[0329] Suitable bases which may be used in the alkylation reaction are as defined above.

[0330] To prepare the monoether compound of the general formula (Ia), 2,2,4,4-tetramethylcyclobutane-1,3-diol is usually reacted with a subequimolar or nearly equimolar amount, for example 0.7, 0.8, 0.9 or 0.95 equivalents of an alkylating agent R 1a -X to give a monosubstituted compound (Ia-OH):

[0331]

[0332] Where R 1a has one of the meanings given above,

[0333] It is further subjected to a purification step as defined above in order to remove unwanted by-products or impurities, such as residual starting materials or the corresponding disubstituted compound.

[0334] Group R 1a and R 2a The preparation of the diether compound of the same general formula (Ia) is usually carried out by reacting 2,2,4,4-tetramethylcyclobutane-1,3-diol with at least 2 equivalents, for example 2.0, 2.1, 2.5 or 3.0 equivalents of an alkylating agent R 1a -X or R 2a -X reaction, where the group R 1a , R 2a and X has one of the meanings given above and the crude product obtained is subsequently subjected to a purification step as defined above.

[0335] The group R 1a and R 2a The preparation of the various diether compounds of the general formula (I) is usually carried out by first reacting 2,2,4,4-tetramethylcyclobutane-1,3-diol with a sub-equimolar or nearly equimolar amount, for example 0.7, 0.8, 0.9 or 0.95 equivalents of an alkylating agent R 1 -X to obtain a monosubstituted compound (I.-a-OH), which, after a purification step, is further reacted with a second alkylating agent R 2a -X reaction.

[0336] Generally speaking, the starting material 2,2,4,4-tetramethylcyclobutane-1,3-diol is used as a cis / trans isomer mixture. Therefore, compound Ia is usually obtained as a cis / trans isomer mixture.

[0337] In step (ii) of the process for preparing the compound of formula (Ia), the crude product mixture obtained in step (i) is subjected to a purification step to remove unwanted by-products or impurities, such as residual monosubstituted compounds (Ia-OH), and to separate cis / trans isomers if necessary.

[0338] Generally speaking, the purification in step (ii) can be carried out by using conventional purification methods, such as crystallization, distillation or chromatography, such as column chromatography or high performance liquid chromatography. If only minor amounts of impurities and by-products are present in the crude product mixture, the purification step can also be carried out by means of simple extraction post-treatment. If necessary, cis / trans isomers can be separated by fractional crystallization, column chromatography or high performance liquid chromatography. Alternatively, cis / trans isomers can also be separated by using methods such as US 3,227,764.

[0339] Another embodiment of the present invention relates to compounds of the general formula (Ib), their stereoisomers or mixtures of their stereoisomers:

[0340]

[0341] in:

[0342] R 1b -(C=O)-R 3 ,

[0343] R 2b is hydrogen or -(C=O)-R 4 ,and

[0344] R 3 and R 4 are independently selected from hydrogen and C1-C4 alkyl, provided that if present, R 3 and R 4 are different.

[0345] A preferred embodiment of the present invention relates to diether compounds of the general formula (Ib), wherein R 2b -(C=O)-R 4 A compound of the general formula (Ib).

[0346] Further preferred are compounds of general formula (Ib) wherein R 3 and R 4 is selected from hydrogen and C1-C3 alkyl, in particular selected from hydrogen, methyl and ethyl.

[0347] Compounds of general formula (Ib) can be prepared as described for the ester compounds of general formula (I).

[0348] Therefore, the present invention also relates to a process for preparing a compound of formula (Ib) as defined above, its stereoisomers or a mixture of its stereoisomers, which comprises:

[0349] (i) 2,2,4,4-tetramethylcyclobutane-1,3-diol and carboxylic acid R 3 -COOH or its anhydride or with acid halide R 3-(C=O)X' in the presence of an organic base and optionally with a carboxylic acid R 4 -COOH or its anhydride, or with an acid halide R 4 -(C=O)X' reaction to obtain a crude product mixture, wherein R 3 and R 4 has one of the meanings given above, and X' represents halogen, for example Cl, Br or I, and (ii) subjecting the crude product mixture obtained in step (i) to a purification step. Example

[0350] analyze:

[0351] The purity of the product was determined by gas chromatography (area %):

[0352] For esters:

[0353] GC system: Agilent 7890B;

[0354] GC column: CP-SIL 13 (50 m (length), 0.32 mm (ID), 1.2 μm (membrane));

[0355] Temperature program: from 120°C to 200°C at 3° / min, from 200°C to 250°C at 20° / min.

[0356] For ether:

[0357] GC system: Agilent 6890N;

[0358] GC column: DB1 (30 m (length), 0.25 mm (ID), 0.25 μm (membrane));

[0359] Temperature program: injection at 10°C, 50°C to 120°C at 3° / min, 120°C to 200°C at 20° / min.

[0360] 1. Preparation Example

[0361] 1.1 Preparation of formic acid (3-formyloxy-2,2,4,4-tetramethyl-cyclobutyl) ester

[0362] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol 144.21 10g 0.069 Formic acid 46.03 22.3g 0.485 Acetic anhydride 102.09 42.5g 0.416 N,N'-Dimethylaminopyridine 122.17 0.17g 0.001 Tetrahydrofuran 70mL

[0363] At 0 ℃, formic acid is slowly added to acetic anhydride. At 55 ℃, the mixture is stirred for 2 hours. Then the mixture is cooled to 0 ℃ and 20mL THF is added, at this temperature, a solution of alcohol in 50mL THF is slowly added. After the addition, DMAP is added to the mixture. The reaction is stirred at room temperature for 3.5 hours, and complete conversion is observed by GC. 60mL toluene is added to the mixture and the organic phase is washed 3 times with 30mL water. The organic phase is dried with sodium sulfate, and the solvent is removed in a laboratory evaporator to obtain 9.7g of a crude product containing 96% di-formic acid ester (according to GC area %). The crude product is purified by silica gel chromatography. The corresponding di-formic acid ester is obtained with a purity of 99.2% (GC area %). NMR shows that the product exists as a cis:trans isomer of a ratio of 55:45.

[0364] Product characterization:

[0365] GC: 99.2% purity (GC area %)

[0366] 13 C-NMR:

[0367]

[0368]

[0369] 1.2 Preparation of (3-acetoxy-2,2,4,4-tetramethyl-cyclobutyl) acetate

[0370] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol 144.21 75g 0.520 Acetic anhydride 102.09 146g 1.430 N,N'-Dimethylaminopyridine 122.17 1.906g 0.016 Tetrahydrofuran 350mL

[0371] DMAP was added to a THF solution of the diol under RF. The mixture was set to reflux (53° C.) and acetic anhydride (2.25 eq.) was slowly added at this temperature. After 2 hours, 99% diol conversion was observed. However, about 15% monoacetate was found in the mixture, for which 0.5 eq. of acetic anhydride was added to the reaction. After 3 hours, 97% conversion to diacetate was observed by GC under reflux. The reaction was cooled to room temperature and slowly quenched with 150 mL of water, 300 mL of ethyl acetate and 200 mL of water were added. The organic phase was separated and washed with NaHCO3 and brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 102.2 g of a crude product containing>97% diacetate (according to GC area %) was obtained. The product was purified by distillation. The corresponding diacetate was obtained with a purity of 99.6% (GC area %). NMR indicated the product existed as cis:trans isomers in a ratio of 55:45.

[0372] Product characterization:

[0373] GC: 99.6% purity (GC area %)

[0374] 13 C-NMR:

[0375]

[0376]

[0377] 1.3 Preparation of propionic acid (3-propionyloxy-2,2,4,4-tetramethyl-cyclobutyl) ester

[0378] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol 144.21 8g 0.055 Propionyl chloride 92.52 12.83g 0.139 N,N'-Dimethylaminopyridine 122.17 0.120g 0.001 Triethylamine 101.19 14g 0.139 Hexane 100mL

[0379] A solution of alcohol, triethylamine and DMAP in hexane (50 mL) was cooled to 0° C. At this temperature, propionyl chloride was slowly added. The reaction was stirred at room temperature for 1 hour, 50 mL of hexane was added, and the reaction was stirred at reflux (67° C.) for 1 hour. After this time, complete conversion was observed by GC. The reaction was cooled to room temperature and slowly quenched with 30 mL of water, 50 mL of hexane was added, and the organic phase was washed with NaHCO3 and brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 13 g of a crude product containing 64% dipropionate (according to GC area %) and 25% monopropionate (GC area %) was obtained. The product was purified by silica gel chromatography. The corresponding dipropionate was obtained with a purity of 94% (GC area %). NMR showed that the product existed as a cis:trans isomer in a ratio of 1:1.

[0380] Product characterization:

[0381] GC: 94% purity (GC area %)

[0382] 13 C-NMR:

[0383]

[0384]

[0385] 1.4 Preparation of 2,2-dimethylpropanoic acid [3-(2,2-dimethylpropionyloxy)-2,2,4,4-tetramethyl-cyclobutyl] ester

[0386] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol 144.21 50g 0.347 Pivaloyl chloride 120.58 156.754g 1.3 N,N'-Dimethylaminopyridine 122.17 2.118g 0.017 Triethylamine 101.19 87.710g 0.867 THF 250mL

[0387] The solution of alcohol, triethylamine and DMAP in THF is cooled to 0 ℃. At this temperature, pivaloyl chloride (2.5) is slowly added. The reaction is stirred at room temperature for 0.5 hour, and stirred for 4 hours under reflux. After this time, 96% conversion is observed, but only 49% dipivalate is detected by GC, and the rest are mono-derivatives. Therefore, 1.25 equivalents of pivaloyl chloride are further added, and the reaction is stirred for 21 hours under RF. The reaction is cooled to room temperature and quenched slowly with 200mL water, 200mL ethyl acetate is added and organic phase is washed with NaHCO3 and saline solution. The organic extract is combined and dried over sodium sulfate. After the solvent is evaporated under reduced pressure, 110.8g of crude product comprising 88% dipivalate (according to GC area %) and 11% monopivalate (GC area %) is obtained. The product is purified by distillation. The corresponding dipivalate is obtained with a purity of 99.8% (GC area %). NMR indicated the product existed as cis:trans isomers in a ratio of 55:45.

[0388] Product characterization:

[0389] GC: 99.8% purity (GC area %)

[0390] 13 C-NMR:

[0391]

[0392]

[0393] 1.5 2-Methylpropionic acid [3-(2-methylpropionyloxy)-2,2,4,4-tetramethyl-cyclobutyl] ester

[0394] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol 144.21 10g 0.069 Isobutyric anhydride 158.19 24.68g 0.156 N,N'-Dimethylaminopyridine 122.17 0.254g 0.03 Tetrahydrofuran 50mL

[0395] DMAP was added to a THF solution of diol under RF. The mixture was set to reflux (60°C) and isobutyric anhydride (2.25 equivalents) was slowly added at this temperature. After 2.5 hours, 99% diol conversion was observed. However, about 8% monoisobutyrate was found in the mixture. The reaction was cooled to room temperature and slowly quenched with 20mL water, 50mL ethyl acetate. The organic phase was separated and washed with NaHCO3 and brine solution. The organic extracts were combined and dried over sodium sulfate. After the solvent was evaporated under reduced pressure, 19.6g of a crude product containing>91% diisobutyrate (according to GC area %) was obtained. The product was purified by distillation. The corresponding diisobutyrate was obtained with a purity of 97.4% (GC area %). NMR showed that the product existed as a cis:trans isomer with a ratio of 55:45.

[0396] Product characterization:

[0397] GC: 97.4% purity (GC area %)

[0398] 13 C-NMR:

[0399]

[0400]

[0401] 1.6 Preparation of butyric acid (3-butyryloxy-2,2,4,4-tetramethyl-cyclobutyl) ester

[0402] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol 144.21 10g 0.069 Butyric anhydride 158.19 24.68g 0.156 N,N'-Dimethylaminopyridine 122.17 0.254g 0.03 Tetrahydrofuran 50mL

[0403] DMAP was added to a THF solution of the diol under RF. The mixture was set to reflux (60° C.) and n-butyric anhydride (2.25 equivalents) was slowly added at this temperature. After 2.5 hours, 99% diol conversion was observed. However, about 10% mono-n-butyrate was found in the mixture. The reaction was cooled to room temperature and slowly quenched with 20 mL of water, 50 mL of ethyl acetate. The organic phase was separated and washed with NaHCO3 and brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 18.8 g of a crude product containing>88% di-n-butyrate (according to GC area %) was obtained. The product was purified by distillation. The corresponding di-n-butyrate was obtained with a purity of 99.7% (GC area %). NMR showed that the product existed as a cis:trans isomer in a ratio of 55:45.

[0404] Product characterization:

[0405] GC: 99.7% purity (GC area %)

[0406] 13 C-NMR:

[0407]

[0408]

[0409] 1.7 Preparation of 2,4-dimethoxy-1,1,3,3-tetramethyl-cyclobutane

[0410] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol 144.21 30g 0.208 Methyl iodide 141.94 73.82g 0.520 Sodium hydride 23.99 12.476g 0.520 Tetrahydrofuran 300mL

[0411] At 0°C, a solution of caged diol in 150 mL THF was added to a dispersion of sodium hydride (2.5 equivalents) in 150 mL THF. The mixture was stirred at 0°C for 1 hour. After this time, 2.5 equivalents of methyl iodide were slowly added at RT. After the addition, the mixture was stirred at 40°C for 21 hours. At this time, the reaction was slowly quenched with 150 mL of water. The organic phase was extracted 3 times with 150 mL of MTBE. The organic extracts were combined and washed with 150 mL of NH3 solution and 150 mL of saline solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 18.8 g of a crude product with 54% dimethyl ether (according to GC area %), the rest being monomethylated alcohol (30%) and unreacted caged diol (10%) was obtained. The dimethyl ether product was purified by silica gel chromatography. The corresponding dimethyl ether was obtained with a purity of 99.8% (GC area %). NMR indicated that the product existed as cis:trans isomers in a ratio of 4:1.

[0412] Product characterization:

[0413] GC: 99.8% purity (GC area %)

[0414] 13 C-NMR:

[0415]

[0416]

[0417] 1.8 Preparation of 3-methoxy-2,2,4,4-tetramethyl-cyclobutanol

[0418] During the purification of 2,4-dimethoxy-1,1,3,3-tetramethyl-cyclobutane in Example 1.7, two isomers of the corresponding monomethyl ether were separated. 1.4 g of the high trans isomer of 3-methoxy-2,2,4,4-tetramethyl-cyclobutanol (high trans) were obtained in a purity of 94% (94% trans, GC area%, RT: 20.70 min). NMR confirmed the presence of a high content of the trans isomer.

[0419] Characterization of the product (high trans):

[0420] GC: 94% purity (94% trans (by GC area %); RT: 20.70 min)

[0421] 13 C-NMR:

[0422]

[0423] number of atoms <![CDATA[Measured 13 C displacement (multiple times)]]> <![CDATA[Calculated 13 C displacement (multiple times)]]> C1 88.73(d) 88.75(d) C2 / C4 40.65(s) 40.64(s) C3 79.53(d) 79.50(d) C7 58.53(q) 58.52(q) C8 / C9 22.59(q) 22.60(q) C10 / C11 23.14(q) 23.17(q)

[0424] 0.5 g of the high cis isomer of 3-methoxy-2,2,4,4-tetramethyl-cyclobutanol was well separated with a purity of 98% (98% cis, GC area%, RT: 20.30 min). GC confirmed the presence of the high cis isomer compared to the cis / trans isomer mixture of 3-methoxy-2,2,4,4-tetramethyl-cyclobutanol.

[0425] Characterization of the product (high cis):

[0426] GC: 98% purity (98% cis (by GC area %); RT: 20.30 min).

[0427] 1.9 Preparation of 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane

[0428] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol 144.21 20g 0.139 Ethyl iodide 155.97 82.25g 0.527 Sodium hydride 23.99 12.65g 0.527 Tetrahydrofuran 200mL

[0429] At 0°C, to a dispersion of 7.65g sodium hydride (2.3 equivalents) in 100mL THF, a solution of caged diol in 150mL THF was slowly added. The mixture was stirred for 1 hour at 0°C. After this time, 2.3 equivalents of ethyl iodide (49.75g) were slowly added at RT. After the addition, the mixture was stirred for 21 hours at 40°C. At this point, about 90% alcohol conversion was observed. However, only 35% diethyl ether was detected, and the rest (56%) were monoether derivatives. Therefore, the reaction was cooled to 0°C and 5g sodium hydride was added. After 15 minutes at this temperature, 32.5g ethyl iodide was slowly added. The mixture was stirred at 40°C during 22 hours. The reaction was then slowly quenched with 100mL water. The organic phase was extracted 3 times with 100mL MTBE. The organic extracts were combined and washed with 100mL NH3 solution and 100mL brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 22.8 g of a crude product with 61.5% diethyl ether (according to GC area %), the remainder being monoethylated alcohol (29%) and unreacted caged diol was obtained. The product was purified by silica gel chromatography. The corresponding diethyl ether was obtained with a purity of 99.8% (GC area %). NMR showed that the product existed as a cis:trans isomer in a ratio of 3:1.

[0430] Product characterization:

[0431] GC: 99.8% purity (GC area %)

[0432] 13 C-NMR:

[0433]

[0434]

[0435] 1.10 Preparation of 3-ethoxy-2,2,4,4-tetramethyl-cyclobutanol

[0436] During the purification of 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane of Example 1.9, 2.9 g of monoethyl ether (3-ethoxy-2,2,4,4-tetramethyl-cyclobutanol) was also isolated with a purity of 79% (GC area %), the remainder being 20.5% of the diethyl ether derivative (2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane). NMR information indicated a trans:cis ratio of 55:45 for 3-ethoxy-2,2,4,4-tetramethyl-cyclobutanol, and a cis / trans ratio of 3:1 for 2,4-diethoxy-1,1,3,3-tetramethyl-cyclobutane.

[0437] Product characterization:

[0438] GC: 79% purity (GC area %)

[0439] 13 C-NMR:

[0440]

[0441]

[0442]

[0443] 1.11 Preparation of 2,4-di-n-propoxy-1,1,3,3-tetramethyl-cyclobutane

[0444] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol 144.21 10g 0.069 1-Iodopropane 169.99 27.11g 0.159 Sodium hydride 23.99 3.83g 0.159 Tetrahydrofuran 105mL

[0445] At 0°C, to a dispersion of 3.83g sodium hydride (2.3 equivalents) in 75mL THF, a solution of caged diol in 30mL THF was slowly added. The mixture was stirred for 30 minutes at 0°C. After this time, 2.3 equivalents of 1-iodopropane (27.11g) were slowly added at RT. After the addition, the mixture was stirred for 4 hours at 50°C. About 80% alcohol conversion was observed at this time. However, only 12% di-n-propyl ether was detected, and the rest (about 65%) were monoether derivatives. Therefore, the reaction was cooled to 0°C and 1.67g sodium hydride was added. After 30 minutes at this temperature, 11.8g 1-iodopropane was slowly added. The mixture was stirred at 50°C during 18 hours. The reaction was then slowly quenched with 50mL water. The organic phase was extracted 3 times with 50mL MTBE. The organic extracts were combined and washed with 50mL NH3 solution and 30mL brine solution. The organic extracts are combined and dried over sodium sulfate. After the solvent is evaporated under reduced pressure, the crude product contains 22% di-n-propyl ether (according to GC area %), and the rest are mono-n-propylated alcohol (67%) and unreacted caged diol. The product is purified by silica gel chromatography. The corresponding di-n-propyl ether (0.7 g) is obtained with a purity of 99.4% (GC area %). NMR shows that the product exists as a cis:trans isomer with a ratio of 85:15.

[0446] Product characterization:

[0447] GC: 99.4% purity (GC area %)

[0448] 13 C-NMR:

[0449]

[0450]

[0451]

[0452] 1.12 Preparation of 3-propoxy-2,2,4,4-tetramethyl-cyclobutanol

[0453] During the purification of 2,4-di-n-propoxy-1,1,3,3-tetramethyl-cyclobutane of Example 1.11, 0.6 g of mono-n-propyl ether (3-propoxy-2,2,4,4-tetramethyl-cyclobutanol) was also isolated with a purity of 99% (GC area %). NMR indicated a 3:2 trans:cis ratio.

[0454] Product characterization:

[0455] GC: 99% purity (GC area %)

[0456] 13 C-NMR:

[0457]

[0458]

[0459] 1.13 Preparation of 2,4-di-n-butoxy-1,1,3,3-tetramethyl-cyclobutane

[0460]

[0461]

[0462] At 0 ℃, to the dispersion of 3.83g sodium hydride (2.3 equivalents) in 75mL THF, a solution of caged diol in 30mL THF was slowly added. The mixture was stirred for 30 minutes at 0 ℃. After this time, 2.3 equivalents of 1-iodobutane (29.35g) were slowly added at RT. After the addition, the mixture was stirred for 22 hours at 50 ℃. At this time, about 75% alcohol conversion was observed. However, only 12% di-n-butyl ether was detected, and the rest (about 65%) were monoether derivatives (according to GC area %). Then the reaction was slowly quenched with 50mL water. The organic phase was extracted 3 times with 50mL MTBE. The organic extracts were combined and washed with 50mL NH3 solution and 30mL saline solution. The organic extracts were combined and dried with sodium sulfate. After the solvent was evaporated under reduced pressure, the crude product was purified by silica gel chromatography. The corresponding di-n-butyl ether (1.6 g) was provided in 96% (GC area %) purity. NMR indicated that the product existed as cis:trans isomers in a ratio of 85:15.

[0463] Product characterization:

[0464] GC: 96% purity (GC area %)

[0465] 13 C-NMR:

[0466]

[0467] number of atoms <![CDATA[Measured 13 C displacement (multiple times)]]> C1 / C3 84.99 / 86.84(d) C2 / C4 42.37 / 40.86(s) C5 / C8 / C6 / C7 15.72(cis) / 23.60(trans) / 30.91(cis)(q) C9 / C13 72.66 / 70.18(t) C10 / C14 32.10 / 32.18(t) C11 / C15 19.44 / 19.41(t) C12 / C16 14.04 / 13.97(q)

[0468] 1.14 Preparation of 3-Butoxy-2,2,4,4-tetramethyl-cyclobutanol

[0469] During the purification of 2,4-di-n-butoxy-1,1,3,3-tetramethyl-cyclobutane in Example 1.13, 2 g of mono-n-butyl ether (3-butoxy-2,2,4,4-tetramethyl-cyclobutanol) were also isolated with a purity of 99% (GC area %). NMR indicated a 60:40 cis / trans ratio.

[0470] Product characterization:

[0471] GC: GC: 99% purity (GC area %)

[0472] 13 C-NMR:

[0473]

[0474] number of atoms <![CDATA[Measured 13 C displacement (multiple times)]]> C1 79.74 / 78.37(d) C2 / C4 42.76 / 40.87(s) C3 86.74(trans) / 85.02(cis)(d) C5 / C6 / C7 / C8 29.87(cis) / 22.84(trans) / 23.13(trans) / 15.33(cis)(q) C11 70.55 / 70.31(t) C12 32.12 / 32.09(t) C13 19.44(t) C14 14.03(q)

[0475] 1.15 Preparation of 2,4-di-tert-butoxy-1,1,3,3-tetramethyl-cyclobutane

[0476]

[0477] 10 g of caged diol was dissolved in 140 mL of methyl tert-butyl ether (MTBE) and 10 g of molecular sieve 4A was added. At 25 ° C, sulfuric acid was slowly added to the dispersion. The reaction was stirred at 40 ° C for 6 hours. Thereafter, about 90% diol conversion was observed. The molecular sieve was filtered and 50 mL of NaHCO3 was slowly added to the reaction. After phase separation, the aqueous phase was extracted twice with 30 mL of MTBE. The organic extracts were combined, washed with 50 mL of NaHCO3 and dried with sodium sulfate. After evaporating the solvent under reduced pressure, the crude product was purified by silica gel chromatography. The corresponding 2,4-di-tert-butoxy-1,1,3,3-tetramethyl-cyclobutane (0.9 g) was obtained with a purity of 90% (GC area %). NMR showed that the product existed as a cis:trans isomer in a ratio of 2:1.

[0478] Product characterization:

[0479] GC: GC: 90% purity (GC area %)

[0480] 13 C-NMR:

[0481]

[0482] number of atoms <![CDATA[Measured 13 C displacement (multiple times)]]> C1 / C3 78.27(d) C2 / C4 43.63 / 41.36(s) C5 / C6 / C7 / C8 29.83(cis) / 23.29(trans) / 16.71(cis)(q) C11 71.69 / 71.35(s) C12 / C13 / C14 / C15 / C16 / C17 / C18 28.74(q)

[0483] 1.16 Preparation of 3-tert-butoxy-2,2,4,4-tetramethyl-cyclobutanol

[0484] During the purification of 2,4-di-tert-butoxy-1,1,3,3-tetramethyl-cyclobutane in Example 1.15, 1.1 g of mono-tert-butyl ether (3-tert-butoxy-2,2,4,4-tetramethyl-cyclobutanol) was also isolated with a purity of 90% (GC area %). NMR indicated a 3:2 trans:cis ratio.

[0485] Product characterization:

[0486] GC: GC: 90% purity (GC area %)

[0487] 13 C-NMR:

[0488]

[0489]

[0490]

[0491] 1.17 Preparation of (3-acetoxy-2,2,4,4-tetramethyl-cyclobutyl) acetate having a 9:1 cis / trans isomer ratio

[0492] 68.5 g of the pure diacetate sample prepared in Example 1.2 was set in a refrigerator for two minutes and observed how crystallization began. Therefore, the sample was kept in a freezer for 30 minutes. At this time, the sample was completely solid. Thereafter, the sample was kept at RT and observed how the crystals slowly became liquid. 10 mL of this binary mixture was partially filtered and the two parts were analyzed by GC. The liquid portion contained a cis:trans mixture of 52:48 (according to GC area %). However, the crystals were a 9:1 cis:trans mixture (according to GC area % and NMR).

[0493] Product characterization:

[0494] GC: 9:1 cis / trans isomer mixture

[0495] 13 C-NMR:

[0496]

[0497] number of atoms <![CDATA[Measured 13 C displacement (multiple times)]]> <![CDATA[Calculated 13 C displacement (multiple times)]]> C1 / C3 79.70(d) 80.54(d) C2 / C4 41.11(s) 39.60(s) C5 / C6 / C7 / C8 28.55 / 16.61(q) 22.53(q) C11 / C14 170.91(d) 170.72(s) C13 / C16 20.71(q) 20.61(q)

[0498] 1.18 Preparation of (3-hydroxy-2,2,4,4-tetramethyl-cyclobutyl) acetate

[0499] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol 144.21 10g 0.069 Acetic anhydride 102.09 7.08g 0.069 N,N'-Dimethylaminopyridine 122.17 0.254g 0.002 Tetrahydrofuran 50mL

[0500] DMAP was added to the THF solution of the diol under RF. The mixture was set to 40°C and acetic anhydride (1 equivalent) was slowly added at this temperature. After 3 hours, the reaction was cooled to room temperature and slowly quenched with 50 mL of water, 50 mL of ethyl acetate. The organic phase was separated and washed with NaHCO and brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 7.2 g of a crude product containing 17.4% cage diol, 46.7% monoacetate and 35.7% diacetate (according to GC area %) was obtained. The product was purified by silica gel chromatography. The corresponding monoacetate was obtained as a cis:trans isomer mixture (GC analysis) in a ratio of 1:1 with a purity of 99% (GC area %).

[0501] 1.19 Preparation of (3-formyloxy-2,2,4,4-tetramethyl-cyclobutyl) acetate

[0502] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol monoacetate 186.25 7g 0.025 Formic acid 46.03 7.98g 0.173 Acetic anhydride 102.09 15.17g 0.149 N,N'-Dimethylaminopyridine 122.17 0.061g 0.0005 Tetrahydrofuran 40mL

[0503] At 0 ℃, formic acid is slowly added to acetic anhydride.At 55 ℃, the mixture is stirred for 2 hours.Then the mixture is cooled to 0 ℃ and 20mL THF is added, at this temperature, a solution of crude monoacetic ester derivative (prepared as described above) in 20mL THF is slowly added.After the addition, DMAP is added to the mixture.The reaction is stirred at room temperature for 3.5 hours.50mL toluene is added to the mixture, and the organic phase is washed three times with 50mL water.The organic phase is dried with sodium sulfate, and the solvent is removed in a laboratory evaporator to obtain 6.8g of a crude product comprising 19.12% monoformate, 43% monoacetate-monoformate and 33% diacetate (according to GC area %).The crude product is purified by silica gel chromatography.The corresponding monoacetate-monoformate is separated with 28% monoformate and 18% diacetate (according to GC area %) with a purity of 52% (GC area %).All compounds have an approximately 1:1 cis / trans ratio (according to GC area %).

[0504] 1.20 Preparation of (3-methoxy-2,2,4,4-tetramethyl-cyclobutyl) acetate

[0505] Compound MW Mass / Volume Number of moles 2,2,4,4-Tetramethyl-cyclobutane-1,3-diol monomethyl ether 158.24 7g 0.033 Acetic anhydride 102.09 3.387g 0.033 N,N'-Dimethylaminopyridine 122.17 0.244g 0.002 Tetrahydrofuran 50mL

[0506] 122 mg of DMAP were added to a solution of the monomethyl ether derivative of 2,2,4,4-tetramethyl-cyclobutane-1,3-diol in THF at RT. The monomethyl ether derivative used as starting material was prepared as described above with 1.3 equivalents of MeI. The starting material obtained after this reaction had a content of about 50% of the monomethyl ether derivative and was used in the synthesis without further purification.

[0507] The mixture was set to 40°C and acetic anhydride (1 equivalent) was slowly added at this temperature. After 5 hours, incomplete conversion of the alcohol was observed and 122 mg of DMAP was added to the mixture. The reaction was stirred at 40°C for 4 hours longer. Thereafter, the reaction was cooled to room temperature and slowly quenched with 50 mL of water, 50 mL of ethyl acetate. The organic phase was separated and washed with NaHCO3 and brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 5.6 g of a crude product containing 32% of a mixed ether-ester derivative, the remainder being methyl ether (21%) and diacetate (30%) (according to GC area %) was obtained. The product was purified by silica gel chromatography. The corresponding monomethyl ether-monoacetate was obtained with a purity of 72% (GC area %) as a cis:trans isomer mixture in the ratio 1:1, the remainder being dimethyl ether. NMR also confirmed the product distribution.

[0508] 2. Olfactory test

[0509] To test the odor quality and intensity of the compounds (I) of the present invention, a perfume bar test was performed.

[0510] For this purpose, absorbent paper strips are dipped into a solution comprising a 1-10% by weight ethanolic solution of the compound (I) to be tested. After evaporation of the solvent (approximately 30 seconds), the fragrance impression is assessed olfactorily by an experienced perfumer.

[0511] The aroma test results are summarized in Table 1.

[0512] Table 1: Fragrance test results

[0513]

[0514]

[0515]

[0516]

Claims

1. Use of a compound of formula (I), its stereoisomers or a mixture of its stereoisomers as an aroma chemical for non-diagnostic and non-therapeutic purposes: in: R 1 and R 2 are the same and are C1-C4 alkyl or R 1 -(C=O)-R 3 And R 2 -(C=O)-R 4 , where R 3 and R 4 are the same and are hydrogen or C1-C3 alkyl; or R 1 is a C1-C4 alkyl group and R 2 is hydrogen, or R 1 -(C=O)-R 3 , where R 3 is methyl, and R 2 is hydrogen, methyl or -(C=O)-R 4 , where R 4 For hydrogen.

2. The use according to claim 1, wherein in formula (I), R 1 is a C1-C4 alkyl group, and R 2 is a C1-C4 alkyl group, Where R 1 and R 2 for the same.

3. The use according to claim 2, wherein the compound of formula (I) has the following characteristics c): c) R 1 and R 2 are the same and are all C1-C3 alkyl.

4. The use according to claim 2, wherein the compound of formula (I) has the following characteristics d): d) R 1 and R 2 All are methyl or all are ethyl.

5. The use according to claim 1, wherein in formula (I), R 1 is a C1-C4 alkyl group, and R 2 For hydrogen.

6. The use according to claim 1, wherein in formula (I), R 1 -(C=O)-R 3 , where R 3 is a methyl group, and R 2 is hydrogen or -(C=O)-R 4 , where R 4 For hydrogen.

7. The use according to claim 6, wherein R 2 -(C=O)-R 4 .

8. The use according to claim 1, wherein in formula (I), R 1 -(C=O)-R 3 , where R 3 is a methyl group, and R 2 It is methyl.

9. Use according to any of the preceding claims in a composition selected from the group consisting of perfumery compositions, cosmetic compositions, body care compositions, hygiene products, cleaning compositions, compositions for perfume dispensers, pharmaceutical compositions and crop protection compositions.

10. The use according to claim 9, wherein the hygiene article is a product for oral and dental hygiene and the cleaning composition is selected from the group consisting of a fabric detergent composition and a dishwashing composition.

11. A fragrance chemical composition comprising at least one compound of formula (I) according to any one of claims 1 to 8, its stereoisomers or mixtures of its stereoisomers, and at least one other fragrance chemical different from compound (I) and optionally at least one non-fragrance chemical carrier; the fragrance chemical composition being selected from perfume compositions, cosmetic compositions, body care compositions, hygiene products, cleaning compositions, compositions for perfume dispensers, pharmaceutical compositions and crop protection compositions, Wherein the at least one other aroma chemical different from compound (I) is selected from: Geranyl acetate (acetate 3,7-dimethyl-2,6-octadien-1-yl), α-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate (Phenirat), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), dihydrojasmonate (Hedione, Hedione HC), 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydro-cyclopenta[g]benzopyran (Galaxolid), tetrahydrolinalool (3,7-dimethyloctan-3-ol), ethyllinalool, benzyl salicylate, 2-methyl-3-(4-tert-butylphenyl)propanal (Lilial), cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5-indenyl acetate and / or 4,7-methano-3a,4,5,6,7,7a-hexahydro-6-indenyl acetate (Herbaflorat), citronellol, citronellol acetate, tetrahydrogeraniol, vanillin, linalyl acetate, phenylethyl acetate (1-phenylethyl acetate), octahydro-2,3,8,8-tetramethyl-2-naphthone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene (Iso E Super), ethyl salicylate, 4-tert-butylcyclohexyl acetate (Oryclone), 2-tert-butylcyclohexyl acetate (Agrumex HC), α-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one), n-α-methylionone, α-isomethylionone, coumarin, terpinyl acetate, 2-phenylethanol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde (Lyral), α-amylcinnamaldehyde, ethylene brazilate, (E)- and / or (Z)-3-methylcyclopentadecan-5-enone (Muscenon), 15-pentadecan-11-enolactone and / or 15-pentadecan-12-enolactone (Globalide), 15-cyclopentadecanolactone (Macrolide), 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl -2-naphthyl)ethanone (Tonalid), 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol (Florol), 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (Sandolen), cis-3-hexenyl acetate, trans-3-hexenyl acetate, trans-2 / cis-6-nonadienol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde (Vertocitral), 2,4,4,7-tetramethyloct-6-en-3-one (Claritone), 2,6-dimethyl-5-heptene-1-al (Melonal), borneol, 3-(3-isopropylphenyl)butyraldehyde (Florhydral), 2-methyl-3-(3,4-methylenedioxyphenyl) propionaldehyde (Helional), 3-(4-ethylphenyl)-2,2-dimethylpropionaldehyde (Florazon), 7-methyl-2H-1,5-benzodioxine, -3(4H)-one (Calone), 3,3,5-trimethylcyclohexyl acetate and 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol (Ambrinol S), ambergris tincture; tantalum oil; angelica seed oil; angelica root oil; fennel essential oil; valerian oil; clove basil oil; tree moss absolute; laurel oil; artemisia oil; benzoin resin; bergamot oil; beeswax absolute; birch oil; bitter almond oil; celery oil; thorn leaf oil; balsam bean oil; juniper oil; calamus oil; camphor oil; cananga oil; cardamom oil; quinoa oil; cassia oil; cassia absolute; castoreum absolute; cedar leaf oil; cedarwood oil; rockrose oil; citronella oil; lemon oil; copaiba balsam; coriander oil; costus root oil; cumin oil; cedarwood oil; davana Oil; Dill Fruit Oil; Dill Seed Oil; Eau De Toilette Absolute; Oakmoss Absolute; Elemi Oil; Tarragon Oil; Lemon Eucalyptus Oil; Eucalyptus Oil; Anise Oil; Pine Needle Oil; Grenache Oil; Grenache Resin; Geranium Oil; Grapefruit Oil; Guaiac Wood Oil; Guyun Balsam; Guyun Balsam Oil; Helichrysum Absolute; Helichrysum Oil; Ginger Oil; Iris Root Absolute; Iris Root Oil; Jasmine Absolute; Chamomile Ripened Oil; Roman Chamomile Oil; Carrot Seed Oil; Spearmint Oil; Coriander Oil; Cistus Oil; Cistus Absolute; Cistus Resin; Lavender Absolute; Lavender Oil; Lavender Absolute; Lavender Oil; Lemongrass Oil ; Lovage Oil; Lime Oil Distilled; Lime Oil Pressed; Lina Oil; Litsea Cubeba Oil; Bay Leaf Oil; Mace Oil; Marjoram Oil; Mandarin Oil; Cinnamon Bark Oil; Mimosa Absolute; Musk Seed Oil; Musk Tincture; Clary Sage Oil; Nutmeg Oil; Myrrh Absolute; Myrrh Oil; Myrtle Oil; Clove Leaf Oil; Clove Flower Oil; Neroli Oil; Frankincense Absolute; Frankincense Oil; Parsnip Root Oil; Neroli Absolute; Orange Oil; Oregano Oil; Palmarosa Oil; Patchouli Oil; Perilla Seed Oil; Peru Balsam Oil; Parsley Leaf Oil; Parsley Seed Oil; Petitgrain Oil; Menthol Oil; Pepper Oil; Pimento Oil; Pine oil; mint oil; rose absolute; rosewood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil; star anise oil; styrax oil; marigold oil; fir needle oil; tea tree oil; turpentine; thyme oil; tolu balsam; tonka bean absolute; tuberose absolute; vanilla essence extract; violet leaf absolute; verbena oil; vetiver root oil; juniper berry oil; lees oil; wormwood oil; wintergreen oil; hyssop oil; civet absolute; cassia leaf oil; cassia bark oil and its fractions or components isolated therefrom; Various aromatics from the hydrocarbon group selected from 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; afarnesene; limonene; longifolene; myrcene; ocimene; valencia orangene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane; an aliphatic alcohol selected from the group consisting of hexanol, octanol, 3-octanol, 2,6-dimethylheptanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, (E)-2-hexenol, (E)- and (Z)-3-hexenols, 1-octen-3-ol, a mixture of 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol, (E,Z)-2,6-nonadienol, 3,7-dimethyl-7-methoxyoctan-2-ol, 9-decenol, 10-undecenol, and 4-methyl-3-decen-5-ol; Aliphatic aldehydes and acetals thereof, selected from hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal; heptanal diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; (E / Z)-1-(1-methoxypropoxy)-hex-3-ene; Aliphatic ketones and oximes thereof selected from 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one; an aliphatic sulfur-containing compound selected from the group consisting of 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylmercaptohexyl acetate; and 1-menthene-8-thiol; an aliphatic nitrile selected from the group consisting of 2-nonenenitrile; 2-undecenenitrile; 2-tridecenenitrile; 3,12-tridecadienenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile; Esters of aliphatic carboxylic acids selected from the group consisting of (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate Esters; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octanoate; methyl 2-nonanoate; allyl 2-isopentyloxyacetate; methyl 3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl crotonate; Acyclic terpene alcohols selected from geraniol; nerol; linalool; lavandinol; nerolidol; farnesol; tetrahydrolinalool; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octadien-3-ol; 2,6-dimethyl-2,5,7-octadien-1-ol; and formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid enols and 3-methyl-2-butenoates thereof; Acyclic terpene aldehydes and ketones selected from geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; geranylacetone; and dimethyl- and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal; Cyclic terpene alcohols selected from menthol; isopulegol; α-terpene alcohols; terpene-4-ol; menth-8-ol; menth-1-ol; menth-7-ol; borneol; isoborneol; oxylinalool; nopol; cedrol; ambroxol; vetiverol; guaiacol; and formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid enols and 3-methyl-2-butenoates thereof; Cyclic terpene aldehydes and ketones selected from the group consisting of menthone; isomenthone; 8-mercaptoisomenth-3-one; carvone; camphor; fenchone; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethylionone; α-irone; α-damascone; β-damascone; β-damascone; δ-damascone; γ-damascone; 1-(2,4,4-trimethyl-2-cyclohexene)-1-ol -1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-naphthone-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; nootkatone; dihydronootkatone; 4,6,8-megatrien-3-one; α-sweet orange aldehyde; β-sweet orange aldehyde; acetylated cedarwood oil (methyl cedarone); Cyclic alcohol selected from 4-tert-butyl cyclohexanol; 3,3,5-trimethyl cyclohexanol; 3-isoborneol cyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; Alicyclic alcohols selected from α-3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butene-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butene-1-ol; 3-methyl-5 -(2,2,3-trimethyl-3-cyclopent-1-yl)pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol; Cyclic and alicyclic ethers selected from eucalyptol; methyl cedar ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclododecane; α-epoxycedane; 3a,6,6,9a-tetramethyldodecahydronaphthalene[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphthalene[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo-[10.1.0]tridec-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-diene alkyl; Cyclic and macrocyclic ketones selected from 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentenone; 3-methyl-5-cyclopentenone; 3-methyl 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecene-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecene-1-one; 7-cyclohexadecene-1-one; (7 / 8)-cyclohexadecene-1-one; 9-cycloheptadecan-1-one; cyclopentadecanone; cyclohexadecanone; Alicyclic aldehydes selected from 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde; Alicyclic ketones selected from 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthyl ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienone; tert-butyl (2,4-dimethyl-3-cyclohexen-1-yl) ketone; An ester of a cyclic alcohol selected from 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-amylcyclohexyl acetate; 4-tert-amylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; octahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; octahydro-2,5,5,8a-tetramethyl- 2-naphthyl ester; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methano-octahydro-5 or 6-indenyl acetate; Esters of alicyclic alcohols selected from 1-cyclohexylethyl crotonate; Esters of cycloaliphatic carboxylic acids selected from allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; cis- and trans-methyl dihydrojasmonate; cis- and trans-methyl jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-acetate; Aromatic aliphatic alcohols selected from benzyl alcohol; 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol; Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids selected from the group consisting of benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; α-trichloromethylbenzyl acetate; α,α-dimethylphenylethyl acetate; α,α-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; Aromatic aliphatic ethers selected from 2-phenylethyl methyl ether; 2-phenylethyl isopentyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; solanum nigrum aldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-di Alkane; 4,4a,5,9b-tetrahydroindenyl[1,2-d]-m-diol 4,4a,5,9b-tetrahydro-2,4-dimethylindenyl[1,2-d]-m-di Britain; Aromatic and aromatic aliphatic aldehydes selected from benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; solanum nigrum aldehyde; 4-methylbenzaldehyde; 4-methylphenyl-acetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)-propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)-propanal; 3-(4-tert-butylphenyl)propanal; meat Cinnamaldehyde; α-butylcinnamaldehyde; α-amylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal; Aromatic and aromatic aliphatic ketones selected from acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)ethanone; 2-benzofuranyl-ethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanylmethanone; 6-tert-butyl-1,1-dimethyl-4-indanylmethanone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; 5′,6′,7′,8′-tetrahydro-3′,5′,5′,6′,8′,8′-hexamethyl-2-naphthylacetonone; Aromatic and aromatic aliphatic carboxylic acids and esters thereof; selected from benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isopentyl salicylate; hexyl salicylate; cyclohexyl salicylate; 3-hexenyl cis-salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; 3-phenyltriethylglycerol; ethyl 3-methyl-3-phenylglycerol; A nitrogen-containing aromatic compound selected from the group consisting of 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 3-methyl-5-phenyl-2-pentenenitrile; 3-methyl-5-phenylvaleronitrile; methyl anthranilate; methyl N-methyl anthranilate; a Schiff base of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine; Phenol, phenyl ether and phenyl ester selected from estragole; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenol acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-tolyl phenylacetate; A heterocyclic compound selected from 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one; Lactones selected from 1,4-octanolactone; 3-methyl-1,4-octanolactone; 1,4-nonanolactone; 1,4-decanolactone; 8-decene-1,4-lactone; 1,4-undecanolactone; 1,4-dodecanolactone; 1,5-decanolactone; 1,5-dodecanolactone; 4-methyl-1,4-decanolactone; 1,15-pentadecanolactone; cis- and trans-11-pentadecanolactone; cis- and trans-11-pentadecanolactone; -12-pentadecen-1,15-lactone; 1,16-hexadecane lactone; 9-hexadecene-1,16-lactone; 10-oxa-1,16-hexadecane lactone; 11-oxa-1,16-hexadecane lactone; 12-oxa-1,16-hexadecane lactone; 1,12-dodecane dioic acid ethylene ester; 1,13-tridecanedioic acid ethylene ester; coumarin; 2,3-dihydrocoumarin; and octahydrocoumarin; The non-aromatic chemical carrier is selected from water, methanol, ethanol, ethylene glycol, glycerin, diglycerin, propylene glycol, dipropylene glycol, 1,2-butylene glycol, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, diethylene glycol monomethyl ether, diethyl phthalate, isopropyl myristate, triethyl citrate, benzyl benzoate, vegetable oil, myristyl acetate, myristyl lactate, myristyl alcohol, stearyl alcohol, cetyl alcohol, lanolin, beeswax, carnauba wax, candelilla wax, Japan wax, hard paraffin, silica gel, silicates, talc, microporous crystalline aluminosilicate (zeolite), bentonite, and sodium tripolyphosphate.

12. A fragrance chemical composition according to claim 11, wherein the hygiene article is a product for oral and dental hygiene, and the cleaning composition is selected from a fabric detergent composition and a dishwashing composition.

13. Use of a compound of formula (I), its stereoisomers or mixtures of its stereoisomers according to any one of claims 1 to 8 for improving the flavour profile of a perfuming ready-to-use composition.

14. A compound of the general formula (Ia), a stereoisomer thereof or a mixture of stereoisomers thereof: in: R 1a is a C2-C4 alkyl group, and R 2a is a C2-C4 alkyl group, Where R 1a and R 2a are the same.

15. A compound according to claim 14, wherein R 1a and R 2a All are ethyl or all are n-propyl or all are n-butyl.

16. A compound of the general formula (Ib), a stereoisomer thereof or a mixture of stereoisomers thereof: in: R 1b -(C=O)-R 3 , R 2b -(C=O)-R 4 , R 3 is a methyl group, and R 4 For hydrogen.

17. A process for preparing a compound of formula (Ia) according to any one of claims 14 to 15, a stereoisomer thereof or a mixture of stereoisomers thereof, comprising: (i) 2,2,4,4-tetramethylcyclobutane-1,3-diol is reacted with an alkylating agent R 1a -X and optionally an alkylating agent R 2a -X in the presence of a base to give a crude product mixture, wherein R 1a and R 2a has one of the meanings given above, and X represents a leaving group selected from halogen and sulfonate, and (ii) subjecting the crude product mixture obtained in step (i) to a purification step.

18. The process according to claim 17, wherein the halogen is Cl, Br or I, and the sulfonate is tosylate, mesylate, triflate or perfluorobutanesulfonate.

19. A process for preparing a compound of formula (Ib) according to claim 16, a stereoisomer thereof or a mixture of stereoisomers thereof, comprising: (i) 2,2,4,4-tetramethylcyclobutane-1,3-diol and carboxylic acid R 3 -COOH or its anhydride, or with an acid halide R 3 -(C=O)X' in the presence of an organic base and optionally with a carboxylic acid R 4 -COOH or its anhydride, or with an acid halide R 4 -(C=O)X' reaction to obtain a crude product mixture, wherein R 3 and R 4 has one of the meanings given above, and X' represents a halogen, (ii) subjecting the crude product mixture obtained in step (i) to a purification step.

20. The method according to claim 19, wherein the halogen is Cl, Br or I.

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