Cyclopropanated sandalwood-type compounds

Abstract

The present invention is in the field of fragrance and relates to novel fragrance compounds according to general formula (I) derived from campholenic aldehyde, which have a sandalwood-like odor note and improved acid stability. Furthermore, the present invention also relates to fragrance compositions containing one or more of the compounds of the present invention. Furthermore, the present invention relates to the use of these compounds or fragrance compositions as odorants or for improving the fixation of fragrance compounds or fragrance compositions, as well as for preparing perfumed products. Additionally, the present invention also refers to the use of said compounds or compositions for preparing perfumed products, as well as for the perfumed products themselves.

Description

[Technical field]

[0001] The present invention is in the field of fragrance and relates to novel fragrance compounds according to general formula (I) derived from campholenic aldehyde, with a sandalwood-like odor note and improved stability to acidic conditions. Moreover, the present invention also relates to fragrance compositions comprising one or more of the compounds of the present invention. Furthermore, the present invention relates to the use of these compounds or fragrance compositions as odorants or for improving the fixation of fragrance compounds or fragrance compositions, as well as for the preparation of perfumed products. In addition, the present invention therefore also refers to the use of said compounds or compositions for the preparation of perfumed products, as well as said perfumed products themselves. [ka] [Background technology]

[0002] Sandalwood is one of the oldest known fragrance materials, and one of the most popular fragrance materials still used in the perfume industry. It was originally produced in India, Ceylon, and Indonesia by extraction from the sandalwood tree. To meet high demand, and in light of the worldwide decline of natural sources of sandalwood oil, numerous synthetically produced fragrances with comparable odor characteristics have been produced in the past.

[0003] α-Campholenic aldehyde (2,2,3-trimethyl-3-cyclopenteneacetaldehyde, C 10 H 16 O) often serves as the starting material for these so-called "camphole sandalwood" aroma chemicals.

[0004] For example, DE 3441902 C1 discloses β,γ-unsaturated 2,2,3-trimethylcyclopent-3-enyl compounds obtained by reduction with sodium borohydride of aldol condensation products of campholenic aldehyde and aliphatic aldehydes, and their use as odorants, especially when combined with the corresponding α,β-unsaturated alcohols. These compounds were found to exhibit woody, animal-like and soft fruit-like odors.

[0005] It has further been found that sandalwood odor is sensitive to slight structural changes, for example the persistence of the fragrance can be increased by cyclopropanation.

[0006] For example, EP0801049B1 describes novel odorants derived from campholenic aldehyde, the molecule of which contains at least one cyclopropane ring and a saturated or unsaturated side chain containing one double bond at the α,β or β,γ positions, respectively. The resulting molecules exhibit various woody odor profiles, most of which give a sandalwood odor, but some are also woody / kunroku-like depending on the cyclopropanation. Furthermore, it has been found that [1-methyl-2-[(1,2,2-trimethyl-3-bicyclo[3.1.0]hexanyl)methyl]cyclo-propyl]methanol (also known as Javanol®, Givaudan) and in particular one of its specific diastereomers, have a natural, strong and persistent sandalwood odor.

[0007] WO 2017 / 024126 A1 refers to a process for cyclopropanation of substituted alkenes using dihalomethanes for the preparation of flavour or fragrance ingredients and discusses the efficient preparation of said fragrance material [1-methyl-2-[(1,2,2-trimethyl-3-bi-cyclo[3.1.0]hexanyl)methyl]cyclopropyl]methanol (Javanol®, Givaudan).

[0008] However, the search for synthetic substances with a sandalwood-like odor is still in progress, and furthermore, new fragrance compounds with comparable secondary olfactory properties, preferably superior to those of natural sandalwood oil, such as, for example, high persistence, low odor threshold, high efficacy, i.e. odor intensity and substantivity, as well as sufficient chemical stability, are all sought after.

[0009] In particular, sufficient chemical stability is required to ensure the stability of the fragrance material in the product formulation, and thus the stability of the perfumed product itself, as well as to ensure high product quality with a consistent odor (i.e., high odor stability). Decomposition of the fragrance material can cause undesirable off-odor notes, changes in color, etc. It is further known that certain fragrance materials are not stable over the entire pH range, especially in acidic environments, making it difficult to incorporate certain fragrances into acidic formulations, such as toilet cleaner formulations, limiting their applicability. Since the human skin surface exhibits an average acidic pH value below 5, not only can these fragrance compounds be incorporated into acidic product formulations, but also their use as odorants or in fragrance compositions themselves be challenging. Thus, fragrance materials should not react with the skin or decompose, resulting in changes in the olfactory and secondary properties of the fragrance material, etc.

[0010] However, it has been found that Javanol® (Givaudan) is not chemically stable under acidic conditions.

[0011] It is therefore a primary object of the present invention to provide new sandalwood fragrance compounds which simultaneously exhibit high olfactory properties closely resembling those of natural sandalwood oil and which simultaneously exhibit improved fixation / substantiation whilst exhibiting high chemical stability, especially in acidic environments.

[0012] It has now surprisingly been found that new α-camholenic aldehyde based compounds according to general formula (I) containing at least one cyclopropane substituent possess a pronounced natural, balanced and intense sandalwood oil odor as well as high chemical stability and enhanced substantivity in acidic environments, thus providing excellent fragrance materials suitable for a wide range of applications. Summary of the Invention

[0013] In a first aspect, the present invention provides a compound of general formula (I): [ka] or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said stereoisomers, where R represents H or an alkyl group, preferably H or a methyl group; and where, at the dotted line, independently, there is either a single bond, a C=C double bond, or a cyclopropane ring; The compound contains at least one cyclopropane ring.

[0014] In a second aspect, the present invention relates to a fragrance composition comprising at least one compound according to the invention and at least one further fragrance substance.

[0015] In a third aspect, the present invention relates to the use of a compound according to the invention as an odorant or fragrance compound or for improving the fixation of a fragrance compound or a composition comprising a fragrance compound or for the preparation of a perfumed product, or the use of a composition comprising a compound according to the invention.

[0016] In another aspect, the present invention relates to a perfumed product comprising a compound according to the present invention or a fragrance composition comprising a compound according to the present invention.

[0017] In yet another aspect, the present invention relates to a perfumed product comprising a compound according to the present invention or a fragrance composition comprising an effective amount of a compound according to the present invention and a carrier or support.

[0018] Finally, the present invention relates to a perfumed product as defined comprising a compound according to the invention or a fragrance composition comprising a compound according to the invention, said perfumed product being a perfume oil, a perfume base, a preparation for personal hygiene, a cleaning agent or an air freshener.

[0019] The inventors have now demonstrated that new cyclopropanated compounds according to general formula (I), comprising at least one cyclopropane functionalization, more particularly preferably comprising one or two cyclopropane functionalization(s), have a pronounced sandalwood-like odor with woody, leafy, floral and fruity notes, with a significantly lower odor threshold and high persistence. Furthermore, the compounds according to the invention show improved chemical stability under acidic conditions (and at elevated temperatures), making it possible to provide efficient fragrances or fragrance ingredients suitable for various applications, in particular for the incorporation of fragrance ingredients into acidic formulations. [Brief description of the drawings]

[0020] [Figure 1] FIG. 1 shows a comparison of the chemical stability of the compound of the present invention of general formula (I) and commercially available [1-methyl-2-[(1,2,2-trimethyl-3-bi-cyclo[3.1.0]hexanyl)methyl]cyclopropyl]methanol (Javanol®, Givaudan) under acidic conditions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] According to the present invention, the above object is achieved by the preparation of compounds of general formula (I): [ka] or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said stereoisomers, where R represents a hydrogen atom (H) or an alkyl group, preferably R represents H or a methyl (CH) group; and where at the dotted line there is independently either a single bond, a C=C double bond, or a cyclopropane ring; The compound contains at least one cyclopropane ring.

[0022] The compounds of general formula (I) have outstanding, balanced and characteristic odor characteristics similar to those of natural sandalwood oil with remarkable persistence as well as woody, floral, leafy and fruity notes. The fruity and leafy aspects are not observed in state-of-the-art sandalwood fragrances, resulting in a more complex and natural odor characteristic. The odor characteristics of natural sandalwood oil are the result of a large number of different odor notes reminiscent of santalol, cedarwood oil or linden oil, or sweet, balsamic, slightly amber, savory or animal notes, or milky notes reminiscent of freshly cooked milk. However, commercial sandalwood fragrances are generally described as having a rather deep, warm woody scent with soft, creamy and sweet notes, and are less complex than natural sandalwood oil. None of the currently available synthetic fragrance materials from the Santalaceae family exhibit the refreshing nuances found in the materials of the present invention. Based on the additional fruity and leafy nuances, the presently developed compounds have enhanced secondary properties and complex, balanced odor profiles, making them suitable for use as alternative fragrance materials with more natural odor profiles that add leafy and fruity undertones that can be advantageously incorporated into a wide range of formulations to create even fresher, more vibrant scents. Thus, the present invention provides a unique and previously unobserved combination of leafy and fruity notes with woody sandalwood.

[0023] Moreover, the compounds described herein have high olfactory intensity even when used at low concentrations.In addition, the outstanding chemical stability, especially under acidic conditions (and at high temperatures), as well as their high persistence, are advantages of the compounds according to the present invention.Therefore, these compounds are highly suitable for use as fragrances or in fragrance mixtures, and in preparations that contain these fragrances or fragrance mixtures.

[0024] Surprisingly, it was found that the position of the functionalization within the butyl chain mainly influences the chemical stability of the product: the best stability and at the same time the best olfactory properties (persistence, intensity, threshold) were found for substances in which the cyclopropane functionalization(s) are located in the position as shown in general formula (I).

[0025] Thereby, the butyl chain C1-C4 in general formula (I) is defined as a chain of four carbons. In general formula (I), the butyl chain is an n-butyl chain -CH2-CH2-CH2-CH2- which is connected to the cyclopentane ring at one of the two terminal carbon atoms and to a hydroxyl group (-OH group) at the other terminal carbon atom (i.e. the carbon atom designated C1).

[0026] In general formula (I), R represents either H or an alkyl group.

[0027] Preferably, the alkyl group is selected from the group consisting of methyl or higher linear or branched alkyl chains, such as ethyl, propyl, n-butyl, or isobutyl. More preferably, the alkyl group is either H or methyl, as these further result in compounds with enhanced strength and chemical stability as well as a natural and intense sandalwood fragrance. These compounds exhibit increased chemical stability and the most balanced and natural sandalwood-like odor characteristics with leafy and fruity notes.

[0028] Thus, in a preferred variant, the compound of general formula (I) comprises as substituent R a methyl group at the C2 position linked to a butyl chain C1-C4.

[0029] Surprisingly, these compounds have been further found to exhibit a natural sandalwood-like odor and to be chemically stable in acidic environments over a wide temperature range, particularly at or near room temperature (RTP).

[0030] However, the best combination of olfactory properties (odor profile, substantivity and intensity / odor detection threshold) and chemical stability was achieved with the embodiment of formula (I), where R represents a hydrogen residue (H). Due to the exceptionally low threshold, exceptionally efficient fragrance materials can be provided according to the invention.

[0031] Thus, in yet another further preferred variant, the compounds of general formula (I) contain as substituent R a hydrogen residue at the C2 position attached to a butyl chain C1-C4.

[0032] Regardless of the above (i.e., R), in general formula (I), there is either a C-C single bond, a C=C double bond, or a cyclopropane ring, independently of each other, at the butyl chain C1-C4 and / or at the dotted line position in the cyclopentane ring. The dotted line is the most concise way to express these options in the structural formula. The meaning is also clear to those skilled in the art, and the embodiment can be identified from the examples.

[0033] However, the compounds of general formula (I) contain at least one cyclopropane ring which provides enhanced persistence and even more pronounced sandalwood-like odor characteristics along with fruity and leafy notes and high chemical stability under acidic conditions.

[0034] However, preferably, the compounds of general formula (I) contain two cyclopropane rings at both positions shown by the dotted lines, i.e., both positions shown by the dotted lines can represent functionalization of the cyclopropane, allowing for increased persistence and high intensity while ensuring a high olfactory profile with a fresh scent.

[0035] Thus, in a preferred variant, the present invention relates to a first aspect, more specifically to compounds of general formula (II): [ka] or a mixture of said compounds, or a stereoisomer of said compounds, or a mixture of said stereoisomers, wherein R represents H or an alkyl group, preferably R represents H or a methyl group.

[0036] Thereby, the substituent R can have the functionality shown above.However, the best olfactory effect and stability have been achieved for compounds in which R represents either H or methyl.It has further been found that R should preferably represent a hydrogen atom, which further results in a sandalwood-like odor characteristic with fresh, leafy and fruity notes.Therefore, a further particularly preferred embodiment of the present invention relates to compounds of formula (I) in which R represents a hydrogen atom.

[0037] It has been found that compounds exhibiting two cyclopropane functions provide exceptionally high chemical stability in acidic environments as well as excellent odor detection thresholds (abbreviated below as "ODT" values). Furthermore, the inventors may demonstrate that these molecules exhibit predominantly sandalwood, woody, leafy, floral, fruity, and creamy odor notes as well as intense odor characteristics with high persistence. Thus, a particularly preferred embodiment of the present invention describes compounds of general formula (II) in which the molecule is dicyclopropanated, i.e., there is a cyclopropane functionalization at the dotted positions in the cyclopentane ring as well as at the butyl chains C1-C4 of general formula (I).

[0038] In another preferred variant, the compound according to general formula (I) is monocyclopropanated, i.e., the compound according to general formula (I) contains only one cyclopropane ring at one of the dotted positions, either at the distal end of the molecule in the bulky cyclopentane portion, or at a proximal position in the C1-C4 butyl chain of the molecule, in which case there is either a C-C single bond or a C=C double bond at each other dotted position not representing cyclopropanation.

[0039] However, in a preferred variant, the monocyclopropanated compounds of the invention contain a C=C double bond at the other dotted position shown in the molecule.

[0040] Thus, in a preferred variant, the present invention refers to compounds according to general formula (I) in which there is a C=C double bond in the C1-C4 butyl chain at the dotted position, while there is a cyclopropane ring in the cyclopentane moiety at the dotted position.

[0041] Thus, in a preferred variant of the invention, the compound according to the first aspect is more particularly of general formula (III): [ka] or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said stereoisomers, is described, wherein R represents H or an alkyl group, preferably R represents H or a methyl group.

[0042] Thereby, the substituent R can have the functionality indicated above. However, the best olfactory effect and stability is achieved when R represents either H or a methyl group, with R=H being preferred. For compounds according to general formula (III) in which R represents a hydrogen residue, the resulting odor profile is more intense and exhibits more fresh, leafy and fruity notes, resulting in a more complex and pleasant scent. In addition, lower ODT values ​​are observed for these compounds, which allows to achieve more efficient fragrance materials.

[0043] Furthermore, these compounds have been found to possess sandalwood-like, woody, leafy and fruity odor characteristics with high odor intensity and persistence, while at the same time exhibiting high chemical stability under acidic conditions.

[0044] In an alternative variant of the present invention, the compound of general formula (I) comprises a cyclopropane ring at the dotted position in the C1-C4 butyl chain and a C=C double bond at the dotted position in the cyclopentane moiety.

[0045] Thus, an alternative variant of the present invention relates to the first aspect, more specifically to compounds of general formula (IV): [ka] or a stereoisomer of said compound, or a mixture of said stereoisomers, wherein R represents H or an alkyl group, preferably R represents H or a methyl group.

[0046] Thereby, the substituent R can have the functionality indicated above. However, the best olfactory effect and stability was achieved when R represents either H or a methyl group. In comparison with the compounds of general formula (III), for the compounds of general formula (IV) the best primary and secondary olfactory properties were observed when R represents a hydrogen residue.

[0047] These compounds have also been found to exhibit excellent primary and secondary fragrance properties in terms of olfactory profile and chemical stability in acidic environments.

[0048] Consequently, in a preferred variant, the compound of general formula (I) (a) a cyclopropane ring, and (b) at least two functional groups selected from the group consisting of double bonds, while the compounds contain at least one cyclopropane functional group according to formula (II), (III) or (IV), respectively.

[0049] An alternative variant of the present invention is, for example, a compound of general formula (V): [ka] or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said stereoisomers, in which R represents H or an alkyl group, preferably R represents H or a methyl group.

[0050] Thereby, the substituent R can have the functionality indicated above. However, the best olfactory effect and stability is achieved when R represents either H or a methyl group, more preferably H. Comparable to the compounds of general formula (III) and (IV), for the compounds of general formula (V) the best primary and secondary olfactory properties are observed when R represents a hydrogen residue.

[0051] Furthermore, it has been found that monofunctionalized compounds exhibiting at least one cyclopropane functionality exhibit exceptional olfactory and secondary properties. Compounds according to formula (V) above exhibit an intense odor that can be described as cedarwood, sandalwood, and creamy.

[0052] In another alternative embodiment of the present invention, monocyclopropanated compounds exhibit cyclopropane functionality within the bulky cyclopentane moiety and similarly exhibit superior odor characteristics.

[0053] Campholenic aldehyde (Campholenic aldehyde) may contain chiral centers and therefore may exist as an isomerically pure form or in a mixture of stereoisomers, in particular in enantiomers as a specific isomeric functional group of α-pinene used as starting material for its preparation. This means that compounds derived from campholenic aldehyde (Campholenic aldehyde) may also occur in various stereoisomeric forms. Consequently, whenever a reference is made in this description to a compound of general formula (I), this is considered to refer to all stereoisomers, in particular all enantiomers, without distinction to isomerically pure stereoisomers or any mixture of these stereoisomers. For economic reasons, it is preferred to use the compound as a mixture of stereoisomers, in particular as a mixture of enantiomers. The same is true for the monofunctionalized compounds of general formulas (II), (III) and (IV) as well as general formula (V).

[0054] The compounds of general formula (I) and the compounds according to formulae (II), (III) and (IV) as well as (V) are therefore (a) Pure optically active enantiomers; (b) a racemic mixture of enantiomers; or (c) Optically active mixtures of different enantiomers It exists in the form:

[0055] Thus, the present invention also discloses any mixture of the above compounds and / or any mixture of the above stereoisomers, as well as the use of such compounds and / or mixtures within the contemplation of the present application.

[0056] Further in this context, the present invention also discloses the single isomeric forms of the compounds according to general formula (I), more specifically according to general formulas (II), (III), (IV) and / or (V). Exemplary single isomeric forms of the compounds according to general formula (II) are shown below: [ka]

[0057] Similarly, single isomeric structures can be derived for compounds of general formulae (I), (III) and (IV), as well as for compound (V).

[0058] In general, in the context of the present invention, the term "compounds of formula (I)" refers to both the individual compounds of formula (I) (as well as their isomeric forms) and mixtures of compounds of formula (I) (as well as their isomeric forms) in any mixing ratio. In other words, references in the following description to "compounds of formula (I)" apply to single compounds of formula (I), single isomeric forms as well as mixtures of compounds of formula (I) and their isomeric forms in any mixing ratio. The same definition applies to compounds of formula (II), (III) and / or (IV) and / or (V). Thus, the present invention relates to compounds according to the present invention, such as, for example, individual compounds according to the present invention as well as mixtures of compounds.

[0059] In addition, additional chiral centers may be present at the positions of the chain branches, i.e. at the positions of the C atoms shown as C2 and C3 in general formulae (I)-(V).Furthermore, with reference to general formula (I), and in particular to formulae (III) or (IV) and the C=C double bonds contained therein, the compounds optionally exist in the form of geometric isomers, i.e. in the Z configuration and / or the E configuration.

[0060] The compounds of general formula (I) unexpectedly have an intense and balanced odor profile (main characteristic) that closely resembles the complex natural woody odor profile of sandalwood with fresh, leafy and fruity notes, particularly the strong and balanced sandalwood odor profile, while at the same time exhibiting high chemical stability under acidic conditions.In particular, the new alcohols of general formula (I) and more specifically the alcohols of general formulas (II), (III) and (IV) as well as the monofunctionalized compounds of general formula (V) exhibit an intense, natural sandalwood-like, woody, leafy and fruity odor profile combined with a surprisingly high persistence.

[0061] In particular, the compounds of general formula (II) exhibit a natural and intense sandalwood odor note with fresh, leafy and fruity characteristics. Moreover, these compounds exhibit extremely high intensity and high chemical stability in acidic environments. Therefore, the compounds of general formula (II) are of particular interest for use as fragrance compounds and for the preparation of perfumed products, especially in acidic formulations.

[0062] Among the novel compounds of general formula (I), those compounds with cyclopropane functionalization at both positions shown by the dotted line, i.e. compounds according to general formula (II), have a particularly intense sandalwood-like odor note with low ODT values, high persistence and high chemical stability under acidic conditions, which are superior to commercial cyclopropanated sandalwood-type fragrances, such as Javanol® (Givaudan). As a result, these compounds exhibit excellent primary and secondary properties required to provide a superior fragrance. This fact may seem surprising considering the similarities that exist between the molecular structures of the novel compounds of general formula (I), especially those of general formula (II), and the compounds of the prior art, but the odor of the compounds is highly sensitive to structural variations.

[0063] Therefore, these dicyclopropanated compounds are particularly preferred within the scope of the present invention as indicated above.

[0064] A direct comparison of the corresponding ODT values ​​of the dicyclopropanated compounds according to general formula (I), more specifically according to general formula (II), where R represents either a hydrogen atom (compound 3b) or a methyl group (compound 3a), with Javanol® (Givaudan) shows that the compounds of the present invention exhibit comparable or even better threshold values ​​compared to the commercial sandalwood fragrance (see Table 1).

[0065] The odor detection threshold is defined as the lowest concentration of a particular odor compound (gaseous, sensory active substance) that can be perceived under standard conditions and therefore reliably distinguished from a blank reference. In general, lower ODT values ​​are preferred, since less of the corresponding fragrance compound is needed to achieve an intense odor impression, and therefore less of it can be used overall in perfumery. However, predictions referring to the ODT of a substance, i.e., a fragrance material, are difficult to make, since the threshold depends on various factors, such as, for example, concentration, solubility, partition coefficient between air and the olfactory active substance, vapor pressure, etc. The ODT was measured using an olfactometer TO8 and a panel of at least four experts according to the DIN standard EN13725.

[0066] Surprisingly, it has been found that the compounds of general formula (I), and more particularly of general formula (II), give off a natural and complex sandalwood-like odor at high concentration / intensity. Particularly preferred in view of their outstanding intensity are the compounds according to general formula (II) in which R represents a hydrogen atom (compound 3b).

[0067] Compared with the commercially available dicyclopropanated sandalwood fragrance Javanol® (Givaudan), compound 3b is distinguished by its high intensity, since it exhibits a substantially lower threshold value by a factor of about 6.5. Thus, less compound is needed to achieve a relatively intense, natural woody and sandalwood-like odor note. As a result, the compounds of the present invention are more efficient as fragrance materials.

[0068] [Table 1]

[0069] Therefore, according to Table 1, the present compound 3b according to general formula (II) is the most preferred compound in view of its exceptional ODT value and high persistence.

[0070] The compounds of general formula (I) according to the present invention as well as the compounds of general formulas (II)-(V) can be used as individual substances or in admixture with at least one other known odorant selected from the wide range of natural and synthetic substances available in numerous fragrance mixtures, and / or in admixture with one or more ingredients or excipients conventionally used in conjunction with odorant substances in fragrance compositions, such as carrier substances and other adjuvants commonly used in the art.

[0071] The olfactory properties of the novel compounds according to general formula (I), more specifically general formulas (II), (III) and (IV), as well as the monofunctionalized compounds of general formula (V), are in harmony with a large number of natural or synthetic odoriferous substances. They can therefore be advantageously used in the preparation of odoriferous compositions comprising at least one compound according to the invention and at least one further odoriferous substance, in particular in view of their high persistence and low threshold, in order to create long-lasting and intense odoriferous compositions with interesting, natural, novel and original odoriferous notes. In particular, the presently described compounds can be advantageously used to add fresher notes with leafy and fruity characteristics to various formulations, resulting in a fresher, brighter and more balanced odor profile compared to commercially available sandalwood-based products, which are rather raw and rich. In addition, the present compounds allow the formulation of natural acidic components, such as citrus oil-like essential oils, with a pH of about 5-5.8 due to their enhanced chemical stability under acidic conditions.

[0072] Therefore, in a second aspect, the present invention refers to a fragrance composition comprising at least one compound according to the invention and at least one further fragrance substance.

[0073] The fragrance materials identified below can be used as individual materials or in mixtures with at least one, two, three or more fragrance materials in a large number of fragrance mixtures selected from a wide range of natural and synthetic materials.

[0074] Fragrance substances which are advantageously suitable for combination are described, for example, in S. Arctander, Perfume and Flavor Materials, volumes I and II, Montclair, NJ 1969, private publication, and / or H. Surburg, J. Panten, Common Fragrance and Flavor Materials, vol. 6, pp. 1111-1115, 1997, and / or H. Surburg, J. Panten, Common Fragrance and Flavor Materials, vol. 6, pp. 1111-1115, 1997. th edition, Wiley-VCH, Weinheim, 2016. The following list contains examples of known odorants which are advantageously suitable for combination with the compounds of the invention and their mixtures: Extracts of natural materials such as essential oils, concretes, absolutes, resins, resinous substances, balsams and tinctures, for example; ambergris tincture;amyris oil;angelica seed oil;angelica root oil;anise oil;valerian oil;basil oil;flower sour absolute;bay oil;artemisia anguicida oil;benzoin resin;bergamot oil;beeswax absolute;birch tar oil;bitter almond oil;savory oil;bucco leaf oil;cabreuva oil;cade oil;shoyub oil;camphor oil;cananga oil;cardamom oil;cascarilla oil;cassia oil;cassi absolute;castorium absolute;cedarwood oil;cedarwood oil;cistus oil;citronella oil;lemon oil;copaiba balsam;copaiba balsam oil;coriander oil;costus root oil;cumin oil;cypress oil;davana oil;dillwood oil;dill seed oil;eau de blues brouts) absolute;oakmoss absolute;elemi oil;tarragon oil;eucalyptus lemon oil;eucalyptus oil;fennel oil;pine needle oil;galbanum oil;galbanum resin;geranium oil;grapefruit oil;guaiacwood oil;gluyun balsam;gluyun balsam oil;helichrysum absolute;helichrysum oil;ginger oil;iris root absolute;iris root oil;jasmine absolute;calamus oil;blue chamomile oil;roman chamomile oil;carrot seed oil;cascarilla oil;pine needle oil;spearmint oil;caraway oil;labdanum oil;labdanum absolute;labdanum resin;lavandin absolute;lavandin oil;lavender absolute;lavender oil;lemongrass oil;robe sage oil;distilled lime oil;pressed lime oil;linaloe oil;liquid cubeba oil;bay leaf oil;massis oil;marjoram oil;mandarin oil;massoia bark oil;mimosa absolute;ambrette oil;must tincture;muscat sage oil;nutmeg oil;myrrh absolute;myrrh oil;myrtle oil;clove leaf oil;clove bud oil;neroli oil;olibanum absolute;olibanum oil;opopanax oil;orange flower absolute;orange oil;oregano oil;palmarosa oil;patchouli oil;perilla oil;peruviana balsam oil;parsley leaf oil;parsley seed oil;petitgrain oil;peppermint oil;pepper oil;pimento oil;pine oil;pennyroyal oil;rose absolute;rosewood oil;rose oil;rosemary oil;sage oil dalmatian;Sage oil Spanish;Sandalwood oil;Celery seed oil;Spike lavender oil;Star anise oil;Styrax oil;Tagetes oil;Fir needle oil;Tea tree oil;Turpentine oil;Thyme oil;Tru balsam;Tonka absolute;Tuberose absolute;Vanilla extract;Violet leaf absolute;Verbena oil;Vetiver oil;Juniper berry oil;Cognac oil;Wormwood oil;Wintergreen oil;Yellow oil;Hyssop oil;Civet absolute;Cinnamon leaf oil;Cinnamon bark oil;and fractions thereof or components isolated therefrom; For example, 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valence; (E,Z)-1,3,5-undecatriene; styrene; and hydrocarbons such as diphenylmethane; Aliphatic alcohols such as, for example, hexanol, octanol, 3-octanol, 2,6-dimethylheptanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, (E)-2-hexenol, (E)- and (Z)-3-hexenol, 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 their acetals, such as, 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, heptanal diethyl acetal, 1,1-dimethoxy-2,2,5-trimethyl-4-hexene, citronellyloxyacetaldehyde, and 1-(1-methoxy-propoxy)-(E / Z)-3-hexene; Aliphatic ketones and their oximes, such as, 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, and 6-methyl-5-hepten-2-one; Aliphatic sulfur-containing compounds such as, for example, 3-methylthio-hexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol; Aliphatic nitriles such as, for example, 2-nonenoic acid nitrile; 2-undecenoic acid nitrile; 2-tridecenoic acid nitrile; 3,12-tridecadienoic acid nitrile; 3,7-dimethyl-2,6-octadienoic acid nitrile; and 3,7-dimethyl-6-octenoic acid nitrile; 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; (E)- and (Z)-3-hexenyl isobutyrate; Esters of aliphatic carboxylic acids such as hexyl crotonate;ethyl isovalerate;ethyl 2-methyl pentanoate;ethyl hexanoate;allyl hexanoate;ethyl heptanoate;allyl heptanoate;ethyl octanoate;(E,Z)-2,4-decadienoate;methyl 2-octynoate;methyl 2-nonynoate;allyl 2-isoamyloxyacetate;methyl 3,7-dimethyl-2,6-octadienoate;4-methyl-2-pentyl crotonate; For example, citronellol; geraniol; nerol; linalool; ravadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 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-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and acyclic terpene alcohols such as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglates and 3-methyl-2-butanoates; acyclic terpene aldehydes and ketones such as geranial, neral, citronellal, 7-hydroxy-3,7-dimethyloctanal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9-undecenal, geranyl acetone, and the dimethyl and diethyl acetals of geranial, neral, and 7-hydroxy-3,7-dimethyloctanal; For example, menthol; isopulegol; alpha-terpineol; terpinenol-4; menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambulinol; vetiverol; guaiol; and cyclic terpene alcohols such as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglates and 3-methyl-2-butanoates; For example, menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethyl-ionone; α-iron; α-damascone; β-damascone; β-damascenone; δ-damascenone; γ-damascone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one; 1,3,4 ,6,7,8a-Hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one;2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal;Nootkatone;Dihydronootkatone;4,6,8-Megastigmatrien-3-one;α-Sinensal;β-Sinensal;Cyclic terpene aldehydes and ketones such as acetylated cedarwood oil (methyl cedryl ketone); For example, cyclic alcohols such as 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; For example, 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-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5-(2,2,3-trimethyl alicyclic alcohols such as 1-(2,2,6-trimethylcyclohexyl)pentan-3-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 such as, for example, cineole; cedryl methyl ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclo-dodecane; α-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydro-naphtho[2,1b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1b]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-dioxane; 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-cyclopentadecenone; 3-methyl-5-cyclo Pentadecenone;3-Methylcyclopentadecanone;4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone;4-tert-pentylcyclohexanone;5-Cyclohexadecen-1-one;6,7-Dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone;8-Cyclohexadecen-1-one;9-Cycloheptadecen-1-one;Cyclopentadecanone;Cyclocyclic and macrocyclic ketones such as cyclohexadecanone; For example, alicyclic aldehydes such as 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde; Alicyclic ketones such as 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-naphthalenyl methyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; and tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl) ketone. For example, 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentyl-cyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decadoro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl acetate Esters of cyclic alcohols such as 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-methanooctahydro-5- or 6-indenyl acetate; For example, esters of alicyclic alcohols such as 1-cyclohexylethyl crotonate; Esters of alicyclic carboxylic acids such as, for example, allyl 3-cyclohexyl propionate; allyl cyclohexyl oxyacetate; cis- and trans-methyl dihydrojasmonate; cis- and trans-methyl jasmonate; methyl-2-hexyl-3-oxocyclopentane carboxylate; ethyl-2-ethyl-6,6-dimethyl-2-cyclohexene carboxylate; ethyl-2,3,6,6-tetramethyl-2-cyclohexene carboxylate; 2-ethyl-2-methyl-1,3-dioxolane ethyl acetate; Aromatic aliphatic alcohols such as, for example, benzyl alcohol; 1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl alcohol; 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; and 1-(4-isopropylphenyl)ethanol. Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids such as, 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; and 4-methoxybenzyl acetate; Aromatic aliphatic ethers such as, for example, 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydratropic aldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxine; and 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxine. For example, benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropic aldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 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-butyl-phenyl)propanal; cinnamaldehyde; α-butyl Aromatic and araliphatic aldehydes such as 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methoxyphenyl)propanal; 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; Aromatic and araliphatic ketones such as, for example, acetophenone, 4-methyl-acetophenone, 4-methoxyacetophenone, 4-tert-butyl-2,6-dimethylacetophenone, 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone, 1-(2-naphthalenyl)ethanone, 2-benzofuranylethanone, (3-methyl-2-benzofuranyl)ethanone, benzophenone, 1,1,2,3,6-hexamethyl-5-indanyl methyl ketone, 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone, 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-acetonaphthone; Aromatic and araliphatic carboxylic acids and their esters, such as, for example, benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenyl acetate; ethyl phenyl acetate; geranyl phenyl acetate; phenylethyl phenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxy acetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl-2,4-dihydroxy-3,6-dimethylbenzoate; ethyl-3-phenyl glycidate; ethyl-3-methyl-3-phenyl glycidate; For example, nitrogen-containing aromatic compounds such as 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-pentenoic acid nitrile; 3-methyl-5-phenylpentanoic acid nitrile; methyl anthranilate; methyl anthranilate-N-methyl; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butyl-phenyl)propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine; Phenols, phenyl ethers and phenyl esters such as, for example, estragole; anethole; eugenol; eugenyl methyl ether; isoeugenol; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresylphenyl acetate; Heterocyclic compounds such as, 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; For example, 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 4-methyl-1,4-decanolide; 1,15-pentadecanolide; cis and trans-11-pentadecen-1,15-olide; cis and trans-12- Pentadecen-1,15-olide;1,16-hexadecanolide;9-hexadecanolide;10-oxa-1,16-hexadecanolide;11-oxa-1,16-hexadecanolide;12-oxa-1,16-hexadecanolide;Ethylene 1,12-dodecanedioate;Ethylene 1,13-tridecanedioate;Coumarin;2,3-dihydrocoumarin;Lactones such as octahydrocoumarin; As well as mixtures of the above substances Individual aroma substances from the group including

[0075] In such fragrance compositions, the compounds according to the invention clearly enhance the woody, sandalwood-like character of the final composition with a fresh olfactory note, while at the same time exhibiting a favorable influence on the overall fragrance balance by providing good persistence, fixation and substantivity.Thus, the presently described compounds according to the invention can be used as efficient and stable fragrance compounds.

[0076] It goes without saying that, although not absolutely necessary, it is preferred that the fragrance composition according to the invention contains a certain amount of a compound according to the invention, preferably according to general formula (II), which allows the olfactory perception of a woody, sandalwood-like odor note, but due to the low ODT values, only small amounts of the compound according to the invention are needed to achieve the desired odor profile.

[0077] Furthermore, due to their high chemical stability towards acidic conditions, it is possible to incorporate the compounds of the present invention as fragrance ingredients into a variety of fragrance compositions, regardless of the pH value of the overall formulation.

[0078] In the fragrance composition, the amount of the compound according to the present invention used is preferably in the range of 0.0001 to 90% by weight, more preferably 0.01 to 70% by weight, particularly preferably 0.1 to 50% by weight, based on the total amount of the fragrance composition.

[0079] The fragrance compounds according to the invention and fragrance compositions comprising or containing at least one compound according to the invention may be used for fragrance applications in liquid form, either undiluted or diluted with a solvent.Suitable solvents for this purpose are, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, triacetin, vegetable oils, etc.

[0080] Furthermore, the fragrance compounds according to the invention or fragrance compositions which contain or contain the compounds according to the invention may be adsorbed on carriers which ensure both a fine distribution of the fragrance substances in the final product and a controlled release during use. Such carriers may be porous inorganic materials such as, for example, sodium sulfate, silica gel, zeolites, gypsum, clay, clay granules, aerated concrete, etc., or organic materials such as, for example, wood, cellulosic substances, sugars, dextrins (for example, maltodextrin), or plastics such as, for example, PVC, polyvinyl acetate or polyurethane.

[0081] The fragrance compounds according to the present invention and fragrance compositions comprising or containing the compound(s) according to the present invention as represented by formulae (I)-(V) may also be microencapsulated, spray dried, provided as an inclusion complex or as an extruded product (i.e. a product according to the present invention).

[0082] Optionally, the properties of the fragrance compounds or fragrance compositions modified in such a way may be further optimized with regard to targeted additional fragrance release by "coating" with a suitable material, for which a wax plastic such as polyvinyl alcohol is preferably used, the resulting product is now the product according to the invention.

[0083] The fragrance compounds according to the invention or the fragrance compositions according to the invention may be encapsulated, for example, by a coacervation method utilizing an encapsulant made from a polyurethane type material or soft gelatin.

[0084] Spray-dried fragrance preparations based on the fragrance compounds according to the invention and fragrance compositions comprising or containing the fragrance compound(s) according to the invention may for example be produced by spray-drying emulsions or dispersions comprising or containing the fragrance compounds or fragrance compositions, modified starches, proteins, dextrins and vegetable gums may be used as carriers. Inclusion complexes may for example be produced by introducing a dispersion of the fragrance compounds or fragrance compositions and cyclodextrins or urea derivatives into a suitable solvent, for example water.

[0085] The extruded product may be produced by melting the fragrance compound or fragrance composition with a suitable waxy substance, optionally extruding with a suitable solvent, for example isopropanol, and then solidifying.

[0086] Due to the specific sandalwood fragrance with leafy and fruity notes of the compounds described herein in combination with outstanding secondary properties such as, for example, low ODT values ​​and high chemical stability, which are superior to sandalwood fragrance substances known from the prior art, fragrance compositions comprising or containing compounds according to general formula (I), preferably compounds according to general formula (II) or compounds according to the present invention, allow a balanced sandalwood odor note to be obtained in the resulting perfumed formulation / product even with the addition of low proportions of the (fragrance) compounds of the present invention, while at the same time ensuring enhanced fixation (persistence) and improved chemical stability in acidic environments / formulations.

[0087] In another aspect, the present invention therefore relates to the use of the compounds according to general formula (I) or of fragrance compositions comprising or containing the compounds according to the invention as efficient odorants or fragrance compounds. The above comments apply correspondingly to preferred compounds and mixtures.

[0088] Based on their outstanding primary and secondary olfactory properties, such as for example persistence, low odor threshold and high chemical stability, the present invention therefore also relates to the use of a compound according to general formula (I) or a fragrance composition comprising or containing at least one compound according to the present invention for improving the fixation of fragrance compounds, while simultaneously using the compound according to the present invention or a composition comprising or containing at least one compound according to the present invention as a fragrance material and for preparing a scented product. With regard to the preferred selection of the compounds and mixtures according to the present invention, the comments given above naturally apply correspondingly.

[0089] The present invention therefore relates to the use of said compounds and compositions for improving the fixation of fragrance compounds or for preparing perfumed products.

[0090] The compounds according to the invention or compositions comprising or containing the compounds according to the invention may be incorporated into products which are or are intended to be perfumed, in particular preparations which benefit personal hygiene such as perfume oils, fragrance bases, preparations for personal hygiene, cleaning agents or air fresheners.

[0091] Therefore, in another aspect, the present invention also refers to a perfumed product comprising or containing a compound according to the present invention and formula (I) or comprising or containing a fragrance composition comprising or containing at least one compound according to the present invention.

[0092] According to a preferred variant, the perfumed products according to the invention, which comprise or contain the compounds according to the invention or the fragrance compositions which comprise or contain the compounds according to the invention, are produced by incorporating the compounds according to the invention or the compositions which comprise or contain the compounds according to the invention in pure form free from solvents, as a solution or in the form of a mixture with a solid or liquid carrier and optionally other auxiliary agents and / or stabilizers to form a base preparation useful for personal hygiene, such as, for example, a cleaning agent.

[0093] The present invention therefore also provides a perfumed product comprising or containing a compound of general formula (I) (or formulas (II), (III) and / or (IV) and / or (V)) in an effective amount in combination with a carrier or support, or a fragrance composition comprising or containing at least a compound according to the invention.

[0094] By sensory effective amount is meant that the proportion of the substances of formula (I), (II), (III) and / or (IV) as well as the monofunctionalized compounds of general formula (V), in particular the compounds according to general formula (I), in the mixture is already sufficient to produce a pleasant and perceptible fragrant impression, in particular a sandalwood-like woody odor impression. This perceptible olfactory impression is generally achieved when at least 0.001% by weight of the compounds of formula (I), (II), (III) and / or (IV) and / or (V) are present in the final preparation / formulation.

[0095] In addition to their intense sensory properties, the compounds of formula (I) described herein possess additional beneficial secondary properties, such as high stability under certain application conditions, particularly in acidic media, which qualifies the compounds of the invention for use and processing in a wide range of applications.

[0096] Perfumed products according to the invention are also suitable for use in the preparation of perfumed products, such as acidic, alkaline and neutral cleaning agents, for example floor cleaners, window cleaners, dish washing detergents, bath and toilet cleaners, stain remover creams, solid and liquid toilet cleaners, powder and foam carpet cleaners, fabric deodorisers, ironing aids, liquid detergents, washing powders, laundry pre-treatment agents, for example bleaches, soaking and stain removers, laundry rinse conditioners, laundry soaps, laundry tablets, disinfectants, surface disinfectants, as well as air fresheners in liquid or gel form or applied to a solid carrier or in solid form, aerosol sprays, waxes and polishes, for example furniture polishes, floor waxes, shoe polishes, as well as body care products, for example 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, for example skin creams and lotions, face creams and lotions, sunscreen creams and sun lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, suntan creams and lotions, hair care products such as hair sprays, hair gels, strengthening hair lotions, hair rinses, permanent and semi-permanent hair dyes, hair shaping products such as cold wave agents and hair straighteners, hair tonics, hair creams and lotions, deodorants and antiperspirants such as underarm sprays, roll-ons, deodorant sticks, deodorant creams, and decorative cosmetic products, such as eye shadow, nail varnish, make-up products, lipstick, mascara, as well as lamp oil, incense, insecticides, insect repellents, and fuel, or oral and / or dental care products, such as toothpaste, tooth gel, tooth powder, mouthwash, chewing gum, and other oral care products, including for flavoring such products, for example, fragrance extracts, eau de parfum, eau de toilette, shaving lotions, eau de cologne, pre-shave products, splash cologne, and scented cooling wipes.

[0097] The product according to the invention may also be a semi-finished product comprising an effective amount of a compound of general formula (I) or a perfuming composition which contains or comprises at least a compound according to the invention.

[0098] The proportion in which the compound of general formula (I) or the fragrance composition containing or comprising at least the compound according to the invention is used may vary within wide limits, ranging from a few parts per thousand in mass-market products such as detergents to a few percent in alcoholic extracts such as perfumes. However, even small amounts of the fragrance composition containing or comprising the novel compound or at least the compound according to the invention efficiently provide a rich sandalwood or woody note to the perfumed preparation / product. Preferably, the fragrance composition containing or comprising the compound of general formula (I) or at least the compound according to the invention is used in an amount of 0.0001 to 90% by weight, preferably 0.01 to 70% by weight, particularly preferably 0.1 to 50% by weight, based on the total weight of the final (product) formulation.

[0099] However, due to the enhanced chemical stability towards acidic conditions of the compounds of the invention, the use of the compounds and compositions of the invention for the preparation of acidic based formulations and products, such as acidic perfume oils, fragrance bases, formulations for personal hygiene, such as shampoos, shower gels, face creams and lotions, sunscreen creams and lotions, cleaning agents or air fresheners in liquid or gel form, or those applied to solid carriers (i.e. formulations and products exhibiting an acidic pH value, thus a pH of less than 7) is preferred.

[0100] Finally, the invention therefore relates to a perfumed product, which is preferably a perfume oil, a perfume base, a preparation for personal hygiene, a cleaning agent or an air freshener.

[0101] Since such products often contain a large number of chemical components, it is also important that the fragrance compounds or corresponding fragrance compositions have low chemical reactivity to counteract unwanted interactions or decomposition of the components and / or fragrance materials.The use of the compounds according to the invention is therefore particularly advantageous since they have low reactivity and high stability, especially in acidic media, so that neither the compounds according to the invention nor the components of the perfumed product are adversely affected.In this context, particular emphasis should be placed on the low concentrations of fragrance compounds necessary to achieve the desired fragrance effect, thereby further avoiding adverse changes in the properties of the perfumed product or its further components.

[0102] In this context, it was surprisingly found that the modification of the molecules aimed at the rearrangement of the functionalization within the butyl chains C1-C4 results in an increase in chemical stability under acidic conditions and at high temperatures, while at the same time resulting in a more leafy, fruity, sandalwood-like odor that results in a fresher, more vivid and therefore more balanced aroma. In addition, excellent ODT values ​​could be achieved. In conclusion, these compounds are very well suited to the formulation of various acidic products that can be used at high temperatures without losing their olfactory properties and intensity.

[0103] Surprisingly, the compounds according to the present invention show a balanced and natural sandalwood-like odor profile, with woody and floral notes as well as leafy and fruity notes.Moreover, the compounds according to the present invention, which are suitable odor substances or fragrance compounds, have a high chemical and physical stability, persistence as well as a significantly low odor threshold.Therefore, another advantage of the compounds according to the present invention is their high odor intensity at relatively low concentrations.

[0104] Due to their high chemical stability, the compounds of the present invention have an extremely low tendency to react with other ingredients of the product formulation or other fragrances, so that the olfactory and / or chemical properties of the individual ingredients are not adversely affected. Such changes in odor properties often result, for example, from the decomposition of the fragrance due to insufficient stability, or from the formation of by-products due to the chemical interaction of the fragrance with other ingredients of the formulation / product with each other. EXAMPLES

[0105] The following compounds were prepared according to the methods shown below, following the general scheme starting from campholenic aldehyde (compound 1): [ka]

[0106] Based on commercially available campholenic aldehyde (compound 1), the corresponding 2,2,3-trimethylcyclopent-3-enyl derivative (compound 2, R=H, Me) was synthesized according to the process disclosed in DE 3441902 C1. Since a compound with a C=C double bond between the C2 and C3 C atoms was also formed initially, the synthesis disclosed therein was appropriately adapted to isolate a compound with a double bond between the C3 and C4 C atoms as shown in general formula (I). In a second step, the final product according to general formula (I) (compound 3, R=H, Me) was obtained based on the Simmons·Smith cyclopropanation and the methods described in WO 2017 / 024126 A1 and EP 0801049 B1.

[0107] Spectroscopic structure determination was carried out by known techniques.

[0108] As indicated above, all formulas as well as all compounds disclosed herein are intended to encompass both pure stereoisomers, particularly enantiomers, and mixtures of stereoisomers, particularly mixtures of enantiomers. Also, all intermediates obtained from the process may exist in various isomeric forms and therefore are intended to encompass both pure stereoisomers and mixtures of stereoisomers.

[0109] Example 1: Preparation of compound 3a

[0110] Step 1: Preparation of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-3-en-1-ol (compound 2a)

[0111] Compound 2a was prepared according to the method described in DE 3441902 C1.

[0112] Experimental data for 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-3-en-1-ol (compound 2a) 1 H-NMR(400MHz,CDCl3)δ5.61(dd,J=15.4,8.5Hz,2H),5.26-5.22(m,2H),5.1 6(dtd,J=15.3,8.8,1.0Hz,2H),3.59-3.53(m,2H),3.42-3.34(m,2H),2.45- 2.37(m,2H),2.31-2.22(m,2H),2.18-2.05(m,4H),1.63-1.60(m,6H),1.51- 1.40(m,2H),1.31-1.18(m,2H),0.97(s,6H),0.96-0.85(m,6H),0.77(s,6H). 13 C-NMR(101MHz,CDCl3)δ148.02,148.02,135.24,134.75,131.78,131.56,121.46,121.46,65.88,65.80,54.34,54.2 0,48.09,48.05,47.83,47.81,35.60,35.30,25.46,25.37,24.08,24.05,20.64,20.50,12.72,12.72,11.81,11.66. GC-MS:208,193,177,161,135,121,107,93,79,55,41,28.

[0113] Step 2: Preparation of 2-[2-(1,2,2-trimethyl-3-bicyclo[3.1.0]hexanyl)cycloprop-yl]butan-1-ol (compound 3a according to general formula (II))

[0114] Compound 3a was prepared according to the method described in WO2017 / 024126A1.

[0115] Experimental data for 2-[2-(1,2,2-trimethyl-3-bicyclo[3.1.0]hexanyl)cycloprop-yl]butan-1-ol (compound 3a) 1 H-NMR(400MHz,CDCl3)δ3.67-3.56(m,4H),1.78-1.62(m,2H),1.65-1.46(m,4H),1.50-1.39(m, 2H),1.03(s,3H),1.03(s,3H),0.98-0.93(m,2H),0.95(s,6H),0.94(t,J=7.8Hz,3H),0.94(s,3H ),0.92(t,J=7.8Hz,3H),0.92(s,3H),0.80-0.65(m,2H),0.61(dt,J=10.9,7.9Hz,1H),0.45-0. 40(m,1H),0.40-0.30(m,6H),0.30-0.22(m,2H),0.20-0.11(m,2H),0.11(dd,J=7.8,4.9Hz,2H). 13 C-NMR(101MHz,CDCl3)δ66.09,65.46,49.97,49.11,47.18,47.03,41.95,41.72,32.99,31.68,31.52,31.42,24.34,24.27,2 3.70,23.25,22.32,22.02,20.72,20.67,19.88,18.90,17.36,17.28,17.11,16.66,13.82,13.78,11.49,11.33,9.87,8.79. Odor description: Sandalwood, cedarwood, floral, fruity, creamy, soft, leafy

[0116] Additional step: isolation of 2-ethyl-4-(1,2,2-trimethyl-3-bicyclo[3.1.0]hexanyl)but-3-en-1-ol (by-product, corresponding to general formula (III))

[0117] The by-product 2-ethyl-4-(1,2,2-trimethyl-3-bicyclo[3.1.0]hexanyl)but-3-en-1-ol, a monocyclopropanated alcohol, was isolated via conventional methods such as column chromatography.

[0118] Experimental data for 2-ethyl-4-(1,2,2-trimethyl-3-bicyclo[3.1.0]hexanyl)but-3-en-1-ol (by-product) 1 H-NMR(400MHz,CDCl3)δ5.40(dd,J=15.2,7.3Hz,1H),5.09-5.01(m,1H),3.56-3.5 0(m,1H),3.39-3.31(m,1H),2.08(ddt,J=14.6,5.8,3.6Hz,1H),1.86-1.76(m,1H) ,1.67(tt,J=12.0,5.7Hz,2H),1.47-1.39(m,1H),1.27-1.16(m,1H),1.04(s,3H), 0.88(t,J=3.7Hz,6H),0.77(s,3H),0.45(q,J=3.5,2.7Hz,1H),0.07-0.04(m,1H). 13 C-NMR(101MHz, CDCl3)δ134.22,131.42,65.80,47.95,47.86,42.47,31.87,30.95,24.05,22.70,22.62,20.55,17.45,13.97,11.67. Scent description: Sandalwood, woody, leafy, fruity

[0119] Example 2: Preparation of compound 3b

[0120] Step 1: Preparation of 2-methyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-3-en-1-ol (compound 2b)

[0121] Compound 2b was prepared according to the method described in DE3441902C1.

[0122] Experimental data for 2-methyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-3-en-1-ol (compound 2b) 1H-NMR(600MHz,CDCl3)δ5.59(dddd,J=15.6,8.5,7.3,1.0Hz,2H),5.28(ddd,J=15. 3,7.9,1.0Hz,2H),5.25-5.23(m,2H),3.52-3.46(m,2H),3.41-3.36(m,2H),2.41-2 .33(m,4H),2.30-2.22(m,2H),2.14-2.06(m,2H),1.62-1.60(m,6H),1.01(d,J=6.8 Hz,3H),1.01(d,J=6.8Hz,3H),0.96(s,3H),0.96(s,3H),0.76(s,3H),0.75(s,3H). 13 C-NMR(151MHz,CDCl3)δ148.09,148.03,133.19,133.12,132.97,132.92,121.47,121.44,67.36,67.33,54.1 6,54.05,47.93,47.89,39.94,39.89,35.45,35.42,25.44,25.35,20.56,20.45,16.88,16.70,12.70,12.72. GC-MS:194,179,163,151,135,121,107,93,79,69,55,41,29.

[0123] Step 2: Preparation of 2-[2-(1,2,2-trimethyl-3-bicyclo[3.1.0]hexanyl)cyclo-propyl]propan-1-ol (compound 3b, corresponding to general formula (II))

[0124] Compound 3b was prepared according to the methods described in WO2017 / 021126A1 or EP0801049B1.

[0125] Experimental data for 2-[2-(1,2,2-trimethyl-3-bicyclo[3.1.0]hexanyl)cyclo-propyl]propan-1-ol (compound 3b) 1H-NMR(400MHz,CDCl3)δ3.65-3.54(m,2H),3.55-3.45(m,2H),1.65-1.49(m ,4H),1.07(d,J=6.7Hz,3H),1.03(s,3H),1.03(s,3H),0.97(s,3H),0.96-0. 95(m,3H),0.97-0.94(m,7H),0.94(s,3H),0.91(s,3H),0.51-0.43(m,2H),0 .42-0.31(m,4H),0.38-0.29(m,2H),0.29-0.04(m,4H),0.02--0.05(m,2H). 13 C-NMR(101MHz,CDCl3)δ68.72,68.70,49.80,49.71,41.78,41.72,40.97,40.64,32.96,32.06,31.82,31.66,31.61,2 3.66,23.31,22.28,22.03,21.28,20.69,20.23,17.34,17.30,17.15,16.70,16.45,16.18,13.86,13.74,10.19,8.97. GC-MS:222,207,181,154,121,107,93,81,67,55,41,29. Scent description: young leaves, floral, fruity, woody, creamy, sandalwood

[0126] Example 3: Preparation of 2-[2-(2,2,3-trimethylcyclopentyl)cyclopropyl]propan-1-ol (corresponding to general formula (V))

[0127] Step 1: Synthesis of 2-(2,2,3-trimethylcyclopentyl)acetaldehyde (reference: Helvetica Chimica Acta, 2006, 89(11), 2638-2653)

[0128] The first step of the preparation was the hydrogenation of 2-(2,2,3-trimethylcyclopent-3-en-1-yl)acetaldehyde (600.0 g, 253.3 mmol) in an autoclave using Pd / C (5%) catalyst (30 g) at 80° C. and 30 bar. Following complete consumption of hydrogen, the reaction mixture was filtered and evaporated (60° C. / 500-10 mbar) to give 555 g of crude product. Then, Kugelrohr distillation (85° C., 0.1 mbar) gave 498 g of the intermediate product, 82%.

[0129] Experimental data for 2-(2,2,3-trimethylcyclopentyl)acetaldehyde 1 H-NMR(600MHz,C6D6)δ9.40(dd,J=2.4,1.8Hz,1H),2.02-1.96(m,1H),1.76-1.71(m,2H),1.65-1.61(m,1H),1.61-1. 56(m,1H),1.32-1.28(m,1H),1.07-1.01(m,1H),0.97-0.92(m,1H),0.74(d,J=6.8Hz,3H),0.67(s,3H),0.29(s,3H). 13 C-NMR(101MHz,C6D6)δ201.03,45.41,44.74,44.71,41.27,30.36,28.27,25.36,14.57,14.01. GC-MS: 139, 97, 69, 41. Odor description: Fruity, sweet, aniseed

[0130] Step 2: Synthesis of 2-methyl-4-(2,2,3-trimethylcyclopentyl)but-2-enal

[0131] To a solution of 2-(2,2,3-trimethylcyclopentyl)acetaldehyde (168.11 g, 1.09 mol) in methanol (300 ml), commercially available 32% NaOH (15.12 mL, 163.47 mmol) was slowly added (exothermic) at temperatures ranging from 15 to 20 °C, followed by the addition of propanal (156.5 mL) (exothermic). The addition reaction was then maintained at room temperature (approximately 16 h). The reaction was then quenched with water (400 mL), the pH was neutralized with sulfuric acid, and methanol was removed by distillation under reduced pressure. The as-obtained crude compound was extracted using MTBE (300 mL × 3) and the combined organic layers were washed with ammonium chloride (300 mL) and saturated solutions of sodium chloride. The combined organic layers were further washed with water until the aqueous phase showed a neutral pH value, then dried under Na2SO4, filtered, and the MTBE was removed using a rotary evaporator to obtain 261.73 g of crude product. The crude product was distilled (R T =140~210℃, H T = 90-122 °C, vacuum = 5 mbar) to give 83.8 g of the title compound.

[0132] Experimental data for 2-methyl-4-(2,2,3-trimethylcyclopentyl)but-2-enal 1 H-NMR(400MHz,CDCl3)δ9.39(s,1H),6.53(tq,J=7.5,1.4Hz,1H),2.49-2.40(m,1H),2.13(ddd,J=14.4,10.5,7.6Hz,1H),1.8 8-1.72(m,2H),1.76(d,J=1.3Hz,3H),1.62-1.48(m,2H),1.29-1.17(m,2H),0.93(s,3H),0.86(d,J=6.8Hz,3H),0.59(s,3H). 13 C-NMR(101MHz, CDCl3)δ195.46,155.24,139.17,50.34,44.91,42.59,30.31,29.94,28.20,25.67,14.49,13.91,9.29. GC-MS:194,179,161,137,123,109,95,84,69,55,41,29.

[0133] Step 3: Synthesis of 2-methyl-4-(2,2,3-trimethylcyclopentyl)but-3-en-1-ol (synthesized according to literature: DE3441902)

[0134] According to the procedure disclosed in DE3441902, 2-methyl-4-(2,2,3-trimethylcyclopentyl)but-2-enal (42.2 g, 161.6 mmol) in methanol (80 mL) was heated to 60° C. and a pre-dissolved solution of NaBH4 (2.0 g, 51.7 mmol) in 15 mL of 1% NaOH was added slowly at 60° C. for 1 h, followed by another hour at room temperature. The reaction mixture was then evaporated (60° C. / 350-150 mbar) to remove the methanol and subsequently extracted using MTBE (100 mL×3). The organic layer was washed with saturated NaCl solution (100 mL), dried under Na2SO4, filtered and the MTBE was removed using a rotary evaporator (40 °C / 500-30 mbar) followed by Kugelrohr distillation (120 °C, 0.8 mbar) to give 30 g of product as a mixture of 2-methyl-4-(2,2,3-trimethylcyclopentyl)but-3-en-1-ol and 2-methyl-4-(2,2,3-trimethylcyclopentyl)but-2-en-1-ol (1:5). Subsequent Spaltroh distillation (R T =70~85℃, H T = 75-95 °C, vacuum = 1 mbar) to give 8% of the title compound.

[0135] Experimental data for 2-methyl-4-(2,2,3-trimethylcyclopentyl)but-3-en-1-ol CG-MS:196,181,163,111,95,81,69,55,41,29.

[0136] Synthesis of 2-[2-(2,2,3-trimethylcyclopentyl)cyclopropyl]propan-1-ol (synthesized according to literature: WO2017 / 024126)

[0137] A literature-based synthesis starting from 2-methyl-4-(2,2,3-trimethylcyclopentyl)but-3-en-1-ol (2.85 g, 14.5 mmol) gave 1.62 g of the title compound after purification by Kugelrohr distillation (122-130 °C, 22 mbar).

[0138] Experimental data for 2-[2-(2,2,3-trimethylcyclopentyl)cyclopropyl]propan-1-ol 1 H-NMR(600MHz,C6D6)δ3.45(dd,J=10.3,5.3Hz,1H),3.30(t,J=10.3Hz,1H),1.74-1.63(m,2H ),1.48-1.31(m,2H),1.21-1.13(m,1H),1.03(d,J=6.8Hz,3H),0.97(s,3H),0.85(d,J=6.8Hz, 3H),0.80-0.73(m,1H),0.69(s,3H),0.61(dt,J=10.9,8.8Hz,1H),0.31(ddt,J=9.4,8.1,4.8 Hz,1H),0.25(tt,J=9.4,4.7Hz,1H),0.16(dt,J=8.6,4.9Hz,1H),0.04(dt,J=8.1,4.9Hz,1H). 13 C-NMR(151MHz,C6D6)δ68.26,56.21,45.76,43.14,41.56,30.05,28.24,26.45,21.45,17.44,17.21,15.27,14.10,9.16. GC-MS:210,195,177,149,137,123,109,95,82,69,55,41,29. Odor description: Cedarwood, sandalwood, creamy.

[0139] Example 4: Comparison of chemical stability

[0140] Example 4 illustrates the chemical stability of the compounds of the present invention of general formula (I), and more specifically of general formula (II), under acidic conditions in comparison with commercially available [1-methyl-2-[(1,2,2-trimethyl-3-bi-cyclo[3.1.0]hexanyl)methyl]cyclopropyl]methanol (Javanol®, Givaudan).

[0141] To analyze the stability of the compounds of the present invention, different samples containing either compound 3a, compound 3b or Javanol® (Givaudan) were analyzed in a citric acid based cleaner having a pH of 2, i.e., stability studies were performed using a representative acid cleaner (pH=2) in which the corresponding fragrance compound was incorporated in an amount of 0.3% relative to the acid cleaner.

[0142] The stability was analyzed for each sample containing one of the aroma compounds as indicated above via solid phase microextraction (SPME) and coupled gas chromatography-mass spectrometry (GC-MS) by using a combination of polydimethylsiloxane and divinylbenzene as SPME fiber coating (PDMS / DVB fiber) and a polydimethylsiloxane-based DB1 column (100% polydimethylsiloxane) for gas chromatography. The stability was investigated for the different samples after 14 days of acid treatment at different storage temperatures (6°C, 22°C, 40°C and 50°C) compared to a freshly prepared sample used as a reference (see Figure 1).

[0143] The results of said comparison are shown in Figure 1. As can be seen, when tested under acidic conditions for 14 days, compounds 3a and 3b of the present invention show good acid stability over the entire temperature range. The best stability may be observed for samples tested under acidic conditions at a temperature of 22°C for 14 days, especially compound 3a at a temperature of 22°C, while Javanol® (Givaudan) appears to decompose rapidly even at moderate temperatures when treated in acidic medium, completely decomposing when treated under acidic conditions at 50°C for 14 days.

[0144] For example, a pH-balanced body wash product was also adjusted to a pH of approximately 5.5. When showering or washing, the water temperature is often set to about 40° C., and the fragrance components should not be decomposed in the body wash formulation or when using the body wash or other perfumed products. It is also known that human sweat generally has a mildly acidic to neutral pH level, usually with a pH value of about 4.5. Furthermore, the normal skin surface exhibits an average pH of less than 5. In addition, our skin is often exposed to high temperatures, such as from the sun (especially in summer). These are only some of the many situations in which fragrance compounds are exposed to acidic conditions and / or high temperatures. However, based on the above experiments, it can be concluded that the compounds of the present invention of general formula (I) should be expected to have a significantly higher stability in such products or on the skin compared to Javanol® (Givaudan), and provide a stable fragrance (especially under acidic conditions), since they do not result in unpleasant odors or changes in odor characteristics due to the decomposition of the fragrance or reaction with other ingredients of the formulation and the formation of by-products.

[0145] The increased stability can be explained based on the position of the cyclopropanation in the side chain of the molecule relative to the R group (which is either H or a methyl group in compounds 3a and 3b, respectively, see compounds of general formula (II)): in Javanol® (Givaudan), the cyclopropane ring is located between the C atoms shown as C2 and C3, while the cyclopropane ring in the butyl chain C1-C4 includes the C atoms shown as C3 and C4, see general formula (I) of the compounds of the present invention. However, in Javanol® (Givaudan), the C2 atom is already bonded to either of the methyl groups, which may cause instability of the molecule under acidic conditions and at high temperatures in relation to the relatively high ring strain of the cyclopropane ring, which may result in the decomposition of the fragrance. The instability of the molecule when exposed to high temperatures and acidic conditions may result in the loss of olfactory properties and may cause unpleasant odors due to decomposition products and / or interactions with other components of the formulation.

Claims

1. General formula (II): 【Chemistry 1】 wherein R represents H or an alkyl group, or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said isomers.

2. 2. A compound of general formula (II) according to claim 1, wherein R is H or a methyl group, or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said isomers.

3. 3. A compound of general formula (II) according to claim 1 or 2, wherein R represents a hydrogen atom, or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said isomers.

4. The compound is (a) pure optically active enantiomers; (b) a racemic mixture of said enantiomers; or (c) Optically active mixtures of the various enantiomers A compound represented by general formula (II) according to any one of claims 1 to 3, or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said isomers, which is present in the form of

5. A fragrance composition comprising at least one compound of general formula (II) according to any one of claims 1 to 4, or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said isomers, and at least one further fragrance substance.

6. Use of a compound of general formula (II) according to any one of claims 1 to 4, or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said isomers, or use of a fragrance composition according to claim 5 as an odorant or fragrance compound, or for improving the fixation of fragrance compounds, or for the preparation of a perfumed product.

7. A perfumed product comprising a compound of general formula (II) according to any one of claims 1 to 4, or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said isomers, or a fragrance composition according to claim 5.

8. A perfumed product comprising an effective amount of a compound of general formula (II) according to any one of claims 1 to 4, or a mixture of said compounds, or a stereoisomer of said compound, or a mixture of said isomers, or a fragrance composition according to claim 5, and a carrier or support.

9. 9. The perfumed product of claim 7 or claim 8, wherein the perfumed product is a perfume oil, a perfume base, a personal hygiene preparation, a cleaning product or an air freshener.

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