DE10322635A1 - Non-allergenic perfumes or perfume formers, having floral notes and useful e.g. in cosmetic or domestic products, comprising alpha-terpene alcohol, aldehyde or ester compounds - Google Patents

Abstract

The use of alpha-terpene alcohol, aldehyde or ester compounds (I) is claimed as non-allergenic perfumes or perfume formers. The use of alpha-terpene compounds of formula (I) is claimed as non-allergenic perfumes or perfume formers. n : 0 or 1; R1, R2 : H or together form an additional bond; R3, R4 : H or together form an additional bond; R5 : CH 2OH, CHO or CH 2OCOR6; R6 : H, optionally unsaturated 1-10C alkyl, benzyl, phenyl, phenethyl, anthranyl, cinnamyl or salicyl. Independent claims are included for: (a) the use of (I) as perfumes or perfume formers (not necessarily non-allergenic), provided that if n= 0 and R3= R4= H, then R5= CHO or CH 2OCOR6 (proviso (1); (b) perfumes comprising one or more compounds (I') selected from (E,Z)-, (Z,E)- or (Z,Z)-alpha-farnesol, (E,E)-, (E,Z)-, (Z,E)- or (Z,Z)-alpha-farnesal, (E)- or (Z)-dihydro-alpha-farnesol and/or (E)- or (Z)-dihydro-alpha-farnesal; (c) perfume compositions (preferably, but not necessarily, non-allergenic) comprising a sensorially active amount of two perfumes and/or perfume formers (other than configurational isomers), at least one of which is a compound (I), provided that either (a) proviso (1) applies or (b) if the mixture additionally contains a beta -terpene (II) corresponding to (I), then the weight ratio of (I) to (II) is more than 100:1 (preferably more than 1000:1); and (d) the production of perfume or aroma compositions, involving addition of (I) to a starting compound mixture to modify its sensorial properties, provided that either (a) proviso (1) applies or (b) the starting and final compositions are non-allergenic. [Image].

Description

wobei R den weiteren Verlauf der Kohlenstoffkette symbolisiert) als (nicht-allergene) Riechstoffe und/oder Riechstoffbildner sowie neue α-terpenoide-Riechstoffe, nämlich (a) (E,Z)-α-Farnesol, (Z,E)-α-Farnesol, (Z,Z)-α-Farnesol und Mischungen bestehend aus zwei oder drei der letztgenannten Verbindungen, (b) (E,E)-α-Farnesal, (E,Z)-α-Farnesol, (Z,E)-α-Farnesal, (Z,Z)-α-Farnesal und Mischungen bestehend aus zwei bis vier dieser Verbindungen, (c) (E)-Dihydro-α-Farnesol, (Z)-Dihydro-α-Farnesol und Mischungen bestehend aus diesen Verbindungen sowie (d) (E)-Dihydro-α-Farnesal, (Z)-Dihydro-α-Farnesal und Mischungen bestehend aus diesen Verbindungen.The invention relates to the use of certain α-terpenes (compounds with a terminal group

where R symbolizes the further course of the carbon chain) as (non-allergenic) fragrances and / or fragrance formers and new α-terpenoid fragrances, namely (a) (E, Z) -α-farnesol, (Z, E) -α- Farnesol, (Z, Z) -α-Farnesol and mixtures consisting of two or three of the latter compounds, (b) (E, E) -α-Farnesal, (E, Z) -α-Farnesol, (Z, E) -α-Farnesal, (Z, Z) -α-Farnesal and mixtures consisting of two to four of these compounds, (c) (E) -Dihydro-α-Farnesol, (Z) -Dihydro-α-Farnesol and mixtures consisting of these compounds and (d) (E) -dihydro-α-farnesal, (Z) -dihydro-α-farnesal and mixtures consisting of these compounds.

Further Aspects of the invention relate to fragrance compositions containing certain α-terpenes contain.

The Finally, invention relates also methods for creating, modifying or amplifying sensory Properties of a (possibly non-allergenic) starting material or -stoffgemisches.

In The fragrance industry has a constant need for new fragrances with improved product properties. When developing new ones Fragrance substances are not the only important sensory properties, but also the harmlessness of the substances to humans and the environment must be at its best Dimensions invoice be worn. Among the properties of a (new) fragrance fulfill needs to face each other Knowing successfully / other fragrances therefore count in addition to stronger and / or interesting new smell properties, a better price / performance ratio and / or a higher one stability in if possible many different applications, especially an improved one toxicological, ecotoxicological and dermatological safety. From a dermatological point of view In particular, the new fragrance must not cause any skin-irritating, sensitizing and / or photosensitizing, especially no allergenic or allergy-promoting Have properties.

During the last decade has been used by dermatologists as part of epidemiological Studies increasingly observed that various commercially important fragrances can cause allergenic contact dermatitis (J.D.Johansen T.Menné, Contact Dermatitis Vol. 32, p.18-23 (1995); W. Larsen et al., American Journal of Contact Dermatitis Vol 7 (2), p.77-83 (1996); W. Larsen et al., Contact Dermatitis Vol. 44, p.344-346 (2001); P.J. Frosch, Contact Dermatitis Vol. 47, p.78-85 (2002)). The as dermatological Fragrances recognized as being of concern - including a number owned by terpenes - were then by the IFRA (International Fragrance Association), based on their more or less strong contact allergenic risk potential grouped into 2 subcategories. Subcategory 1 contains fragrances, in which very often allergenic reactions have been observed. These include amyl cinnamaldehyde (Chemical Abstract registry number, abbreviation CARN: 122-40-7), amyl cinnamon alcohol (CARN: 101-85-9), benzyl alcohol (CARN: 100-51-6), benzyl salicylate (CARN: 118-58-1), cinnamon alcohol (CARN: 104-54-1), cinnamaldehyde (CARN: 104-55-2), citral (a mixture of isomers consisting of neral and geranial, CARN: 5392-40-5), coumarin (CARN: 91-64-5), eugenol (CARN: 97-53-0), geraniol (CARN: 106-24-1), hydroxycitronellal (CARN. 107-75-5), Lyral (CARN: 31906-04-4) and isoeugenol (CARN 97-54-1). Subcategory 2 includes Fragrance substances whose allergenic potential is less common, however still observed in a significantly high number of subjects has been. Which includes Anise alcohol (CARN: 105-13-5), benzyl benzoate (CARN: 120-51-4), benzyl cinnamate (CARN: 103-41-3), Citronellol (CARN: 106-22-9), Farnesol (CARN: 4602-84-0; Mixture of isomers consisting of (Z, Z) -farnesol, (E, Z) -farnesol, (Z, E) -farnesol and (E, E) -farnesol), Hexyl cinnamaldehyde (CARN: 101-86-0), lilial (CARN: 80-54-6), d-limonene (CARN: 5989-27-5), Linalool (CARN: (78-70-6), methylheptin carbonate (CARN: 111-12-6) and γ-methyl ionone (CARN: 127-51-5).

For that The permissible use concentrations were assigned to two subcategories so severely limited in different product categories that only by using replacement products with comparable sensory Characteristics of the original Odor impression can be achieved.

considered you get closer to the substance lists, one observes that among those classified as contact allergens Fragrance substances also various acyclic mono- and sesquiterpenes like citral (a mixture of isomers consisting of the fragrances neral and geranial), geraniol, hydroxycitronellal, citronellol or farnesol with predominantly floral odor characteristics.

• – Die Mechanismen der Riechstoffwahrnehmung sind nicht ausreichend bekannt.
• – Die Zusammenhänge zwischen Riechstoffwahrnehmung einerseits und der chemischen Struktur des Riechstoffes andererseits sind nicht hinreichend erforscht.
• – Es gibt keinen vorhersehbaren Zusammenhang zwischen den Geruchscharakteristika, der toxikologischen Unbedenklichkeit und dem allergieauslösendem Potential einer Substanz.
• – Auch aus der chemischen Struktur eines Stoffes ist in der Regel ihr allergenes Potential nicht zu erkennen.

Especially with these - but also with other - frequently used fragrances, there is a very high need for substitutes and substitutes. The search for suitable odoriferous substances is made more difficult for the person skilled in the art, for example, by the following facts:

• - The mechanisms of fragrance perception are not well known.
• - The relationships between fragrance perception on the one hand and the chemical structure of the fragrance on the other hand have not been sufficiently researched.
• - There is no foreseeable relationship between the odor characteristics, the toxicological safety and the allergy-causing potential of a substance.
• - As a rule, their allergenic potential cannot be recognized from the chemical structure of a substance.

The Success in the search for suitable fragrances and aromas therefore depends to a considerable extent from the intuition of the seeker.

The present invention was primary the task under consideration of those described above general framework non-allergenic odorants or fragrance formers specify. Those with floral odor properties were preferred (see the corresponding task below).

die als – vorteilhafterweise nicht-allergene – Riechstoffe und/oder Riechstoffbildner verwendet werden können, wobei in Formel I
n 0 oder 1,
R1 und R2 jeweils H oder zusammen eine weitere chemische Bindung,
R3 und R4 jeweils H oder zusammen eine weitere chemische Bindung und
R5 CH₂OH, CHO oder CH₂OCOR6 mit
R6 H oder unverzweigter oder verzweigter, gesättigter oder ungesättigter Alkylrest mit 1-10 Kohlenstoffatomen, ein Benzyl-, ein Phenyl-, ein Phenylethyl-, ein Anthranyl-, ein Cinnamyl- oder ein Salicylrest, sind.According to the invention, the object is achieved by specifying compounds of the formula I

which can be used as - advantageously non-allergenic - fragrances and / or fragrance formers, wherein in formula I
n 0 or 1,
R1 and R2 are each H or together a further chemical bond,
R3 and R4 are each H or together a further chemical bond and
R5 CH ₂ OH, CHO or CH ₂ OCOR6 with
R6 is H or unbranched or branched, saturated or unsaturated alkyl radical having 1-10 carbon atoms, a benzyl, a phenyl, a phenylethyl, an anthranyl, a cinnamyl or a salicyl radical.

The chosen in Formula I. Presentation is that of a constitutional formula, which all potential Configurations.

wobei R den weiteren Verlauf der Kohlenstoffkette symbolisiert) allergen sind. Ebenfalls besonders überraschend war, dass innerhalb der Gruppe der α-Terpene der Formel I eine Vielzahl von Substanzen enthalten sind, die interessante und bis dato nicht bekannte Geruchseigenschaften aufweisen, obgleich die natürlich vorkommenden Terpene sowie eine Vielzahl synthetischer Strukturanaloga vor allem im Hinblick auf deren potentielle Verwendung als Riech- und Aromastoffe bereits seit Beginn dieses Jahrhunderts intensiv bearbeitet wurden.The invention is based on the results of our own investigations, in which it surprisingly turned out that the structurally closely related compounds (α-terpenes) of the general formula I listed as examples in Table 1 are non-allergenic fragrances. This is particularly surprising since many of the β-terpenes corresponding to the compounds of the formula (compounds with a terminal group,

where R symbolizes the further course of the carbon chain) are allergenic. It was also particularly surprising that the group of α-terpenes of the formula I contains a large number of substances which have interesting and hitherto unknown odor properties, although the naturally occurring terpenes and a large number of synthetic structural analogs, especially with regard to their potential Use as fragrance and aroma substances have been intensively worked on since the beginning of this century.

The "β-terpene corresponding to a compound of formula I" is a substance which has the same configuration as the respective α-terpene, with the difference that the double bond in the α-terpene within the carbon chain (in the formula I left) is shifted by one carbon atom into the interior of the molecule

Under "non-allergenic" connections of general formula I are chemical within the scope of this text To understand substances that are listed in the toxicological Test method to prove the allergenic effectiveness of chemical substances are not allergenic in any laboratory animal Cause reaction. The investigations on which this application is based were carried out using the so-called LLNA test ("Local Lymph Node Assay"), with with the allergenic potential of chemical substances high sensitivity can be detected.

The "Local Lymph Node Assay "(LLNA) introduces a new generation of predictive test systems for recording the sensitizing / allergenic potential of chemicals In contrast to biphasic test protocols (induction / challenge) the LLNA represents a monophasic scheme (induction). It is oriented address the immunopathogenetic mechanisms of sensitization and enables for the first time the measurement of chemical-induced lymph node cell proliferation an objective assessment of the test reactions in vivo. 1992 was the LLNA in the guidelines of the OECD (Organization for Economic Cooperation and Development) for the immunotoxicological risk analysis of new chemicals was started. As a result, can Test chemicals are characterized as potential allergens, provided that they trigger positive reactions in this test.

In the LLNA tests carried out on alpha-terpenes according to the invention of the general formula 1, CBA / Ca mice were treated on three successive days with the substance to be tested on the dorsal surfaces of both ears. 5 days after the first local treatment, the mice received an iv injection with 20 pCi ³ H-methyl-thymidine. 5 hours later, the locally draining lymph nodes of the ears were removed, pooled for each group, and lymph node single cell suspensions were made. These were incubated in the presence of trichloroacetate overnight at 4 ° C. The following day, the ³ H-methyl-thymidine incorporation was measured using a scintillation counter as a measure of the lymph node cell proliferation. The evaluation of the test reaction was carried out via the index from the ³ H-methyl-thymidine incorporation of the test group divided by the ³ H-methyl-thymidine incorporation of the vehicle-treated control group. The measure for the allergenic reaction of a chemical substance is the stimulation index, which was determined in each case at 3 concentrations of the substances to be tested, namely at 100%, 50% and 10% concentration. The stimulation index is calculated from the ratio of the ³ H-methyl-thymidine incorporation in lymph node cells of test group animals and the ³ H-methyl-thymidine incorporation in lymph node cells of control group animals (negative control), with the stimulation index (quotient : Test group animals / negative control) was determined for each test concentration. The allergenic reaction of a substance was considered to have been proven if the incorporation of ³ H-methyl-thymidine was increased by at least a factor of 3 compared to the negative control at at least one of the 3 test concentrations.

For the connections Formula I was stimulated at all test concentrations Index <3 determined, which clearly proves that, in contrast to the As allergens, known beta-structure analogues are not allergenic Possess potential.

In Table 1 (Appendix) shows some of the structural formulas the α-terpenoid compounds according to formula I listed. On the one hand, these are known substances, but the vast majority Some were not previously known as fragrances and the other for new connections.

Surprisingly have the compounds of formula I (especially those in Table 1 listed) floral fragrance notes, making it in a variety of applications possible is, instead of the corresponding (allergenic) β-terpenes the respective α-terpenes use. The property of the compounds of formula I, non-allergenic being is a clear advantage over the allergenic, corresponding β-terpenes.

German Offenlegungsschrift 2,060,898 does disclose α-citronellol (rhodinol) as a fragrance and the use of mixtures of α-citronellol and β-citronellol with a content of at least 10 % β-citronellol for the production of compositions with valuable fragrance properties, but it does not indicate from this that (a) α-citronellol is non-allergenic or (b) β-citronellol could be replaced by α-citronellol.

It should be pointed out that when the compounds of the formula I with R5 = CH ₂ OCOR6 (ester) are used according to the invention - regardless of the intrinsic odor of the particular compound - the desired fragrance note will only arise in individual cases after hydrolysis of the ester during use. The ester can thus itself act as a fragrance or else as a fragrance former (fragrance precursor), which is only converted into the actual fragrance (alcohol, ie compound of the formula I with R5 = CH ₂ OH) by hydrolysis.

Some Compounds of formula I are chiral. For commercial reasons it’s regularly beneficial for them, to use a mixture of the respective R and S enantiomers. Especially is advantageous in many cases the use of racemates of the respective enantiomeric pairs, since these are particularly easily accessible synthetically. The pure enantiomers (R or S) or non-racemic mixtures of the enantiomers but also for the purposes of the invention suitable.

Closely connected with the above primary The task is the task according to the invention, alternative connections specify which can be used as fragrances.

Accordingly, the invention also relates to compounds of the formula I which can be used as fragrances and / or fragrance formers, the structural variables n and R1-R6 in formula I having the meaning given above, but with the proviso that if n = 0 with R3 and R4 = H: R5 = CHO or CH ₂ OCOR6. In other words, the substance α-citronellol, which is already known as a fragrance, is excluded.

Though became namely α-Citronellol (Rhodinol) as a fragrance in German Offenlegungsschrift 2 060 898 (see above). But there are none Evidence that other α-terpenes can be used as fragrances and / or fragrance formers.

Especially use according to the invention is preferred a compound of formula I as a (non-allergenic) fragrance in a (fragrance) mixture (e.g. perfume or perfume oil), the mixture optionally contains a β-terpene corresponding to the compound of the formula I, with provided that in this case the mass ratio the compound of formula I to the corresponding β-terpene> 100: 1, preferably> 1000: 1, particularly preferably> 1: 10000 is.

by virtue of the possibility of α-terpenes can be displayed in high purity instead of the corresponding β-terpenes the respective α-terpenes of formula I used as a fragrance and so the β-terpene content low being held. This is particularly from an allergological point of view advantageous.

Acyclic terpenes can be prepared by various synthetic routes (see, for example, review articles by H. Boelens, "Acyclic Monoterpenes Alcohols with a 2,6-Dimethyloctane Sceleton"; in "Fragrance Chemistry, The Science of the Sense and Smell" p. 123-163 , Ed.ETTheimer, Academic Press Inc. Orlando, New York, London, Tokyo 1982). Depending on the chosen synthetic route, mixtures of isomers can also be formed. For the synthesis of the compounds of the formula I (α-terpenes) according to the invention, a synthetic route must therefore be chosen in which, in addition to the α-terpenes, no or only minimal amounts of the dermatologically questionable, corresponding β-terpenes such as, for. B. (β-) Citral, (β-) Geraniol, (β-) Citronellol or (β-) Farnesol arise. Preferably, the synthetic route is chosen so that the corresponding β-terpenes such as. B. β-citral, β-geraniol, β-citronellol, or β-farnesol or the individual isomers forming them in the end product in relation to the respective α-terpenes of <1: 100, preferably <1: 1000, particularly preferably < 1: 10000 are included. Terpene qualities such as B. according to the in DE 2060898 or EP1142859 The synthetic routes described are therefore not suitable or only suitable to a limited extent for the use according to the invention as a fragrance since they contain comparatively high proportions of the corresponding β-terpenes.

A suitable starting material for the synthesis of highly pure compounds of the formula I (α-terpenes) is 6-methyl-6-hepten-2-one (cf. 1 ). Starting from 6-methyl-6-hepten-2-one, the α-terpenes can be prepared in analogy to known processes for the commercially used β-terpenes (with regard to the production processes for citronellol, nerol, geraniol, neral, geranial, Farnesol starting from 5-methyl-6-hepten-2-one see also review article by H. Boelens et al.)

On Another aspect of the invention relates - as mentioned - to new fragrances selected from of group (a) consisting of: (E, Z) -α-farnesol, (Z, E) -α-farnesol, (Z, Z) -α-farnesol and mixtures consisting of two or three of these compounds. The isomers of α-farnesol mentioned were not yet known in pure form and increased as (non-allergenic) fragrances the possibilities the perfumers. Other new fragrances are (b) (E, E) -α-farnesal, (E, Z) -α-farnesal, (Z, E) -α-farnesal, (Z, Z) -α-farnesal and mixtures consisting of two to four of these compounds, (c) (E) -dihydro-α-farnesol, (Z) -dihydro-α-Farnesol and mixtures consisting of these compounds and (d) (E) -dihydro-α-farnesal, (Z) -Dihydro-α-farnesal and mixtures consisting of these connections. All isomers of α-farnesal, of dihydro-α-farnesol and the dihydro-α-farnesal as well as any mixtures are new and thus increase as (non-allergenic) Fragrances also significantly increase the possibilities of perfumers. The under (a), (b), (c) and (d) in any combination with each other again represent fragrances, which is also part of the invention. Preferred configurations the invention can also be found in the claims.

The invention also relates to a fragrance composition which comprises at least one sensor-effective amount of two, preferably three, more preferably five, again preferably eight mutually non-configuration-isomeric fragrances and / or fragrance formers, at least one of these fragrance substances and / or fragrance formers being a compound of Formula I is (with the meanings of the structural variables n and R1-R6 mentioned), again with the proviso that if n = 0 with R3 and R4 = H the following applies: R5 = CHO or CH ₂ OCOR6 (α-citronellol is excluded ).

There the olfactory properties of an α-terpene of Formula I regularly those of the corresponding β-terpene are similar or even exceed them qualitatively and / or quantitatively, is the use of α-terpenes in many fragrance compositions instead of their corresponding β-terpenes easily possible what given the non-allergenic Properties of the α-terpenes to be used according to the invention are regularly desirable is (see above).

The Compounds of the formula I have an effect here - in comparison with a basic composition without compounds of formula I - regularly one Shift in the overall smell impression towards more flowery effects different nuances.

If a mixture in which a compound of formula I is used (e.g. a fragrance composition), one to the compound of formula I corresponding β-terpene contains and the mass ratio of the Compound of formula I to the corresponding β-terpene> 100: 1, preferably> 1000: 1, particularly preferred 10000: 1, the α-terpene can also α-citronellol his.

The Advantage of a big one mass ratio of α-terpenes of the formula I for the corresponding β-terpenes is that then by the latter, if (as often) allergenic properties have the allergenic potential of a mixture of substances at most, slightly elevated becomes.

The Use concentration of the α-terpenes of formula I in mixtures and in particular fragrance compositions (like perfume oils) e.g. B. for the fine perfumery, for washing and cleaning agents as well as for cosmetic or pharmaceutical end products are preferably in the range between 0.001 and 99% by weight and preferably in the range between 0.01 and 50 wt .-%, each based on the total mass the mixture.

Especially a fragrance composition according to the invention is preferred, which is characterized by being (overall) non-allergenic is. Those skilled in the art can easily find such fragrance compositions under Establish exclusion of known allergenic components.

The fragrance substance composition according to the invention preferably contains compounds of the formula I for which R3 and R4 together represent a further chemical bond, since these substances are particularly suitable for replacing the β-terpenes corresponding to them. Preferred component of the substance composition according to the invention with the compounds of formula I are the fragrance components mentioned below, the non-allergenic fragrance components being of course particularly preferred:
Extracts from natural raw materials such as essential oils, concretes, absolute, resins, resinoids, balms, tinctures such as B.
ambergris tincture; Amyrisöl; Angelica seed oil; Angelica root oil; anise oil; Valerian oil; Basil oil; Tree moss absolute; Bay oil; Mugwort oil; Benzoeresin; Bergamot oil; Beeswax absolute; birch tar; Bitter almond oil; Savory oil; Buccoblätteröl; Cabreuvaöl; cade oil; calamus; camphor oil; Cananga oil; cardamom; Cascaril laöl; cassia; Cassie absolute; Beaver-absolue; Cedernblätteröl; cedarwood; cistus; citronella; lemon; copaiba balsam; Copaivabalsamöl; Coriander oil; costus root; Cuminöl; Cypress oil; Davanaöl; Dill herb oil; Dill seed oil; Eau de brouts absolute; Oak moss absolute; elemi; Tarragon oil; Eucalyptus citriodora oil; eucalyptus oil; Fennel oil; Pine needle oil; galbanum; Galbanumresin; geranium; Grapefruit oil; guaiac wood; gurjun balsam; gurjun balsam oil; Helichrysum absolute; Helichrysumöl; Ginger oil; Iris root absolute; Orris root oil; Jasmine absolute; calamus; Chamomile oil blue; Roman chamomile oil; Carrot seed oil; Kaskarillaöl; Pine needle oil; spearmint; Seed oil; labdanum; Labdanum absolute; Labdanumresin; Lavandin absolute; lavender oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Distilled lime oil; Lime oil pressed; linaloe; Litsea cubeba oil; Bay leaf oil; Macisöl; Marjoram oil; Mandarin oil; Massoiarindenöl; Mimosa absolute; Musk seed oil; musk tincture; Clary sage oil; nutmeg; Myrrh absolute; Myrrh oil; myrtle; Clove leaf oil; Clove flower oil; neroli; Olibanum absolute; olibanum; Opopanaxöl; Orange blossom absolute; Orange oil; oregano; Palmarosa oil; patchouli oil; perilla oil; Peruvian balsam oil; Parsley leaf oil; Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil; chilli; pine oil; Poleyöl; Rose absolute; Rosewood oil; Rose oil; Rosemary oil; Dalmatian sage oil; Sage oil spanish; sandalwood; Celery seed oil; spike lavender oil; star anise; Styraxöl; tagetes; Pine needle oil; Tea-tree oil; turpentine; Thyme oil; Tolu; Tonka absolute; Tuberose absolute; Vanilla extract; Violet leaf absolute; verbena; vetiver; Juniper berry oil; Wine yeast oil; Wormwood oil; Wintergreen oil; ylang oil; hyssop oil; Civet absolute; cinnamon leaf; Cinnamon bark oil and fractions thereof, or ingredients isolated therefrom;
Individual fragrances (fragrance components) from the group
of hydrocarbons, such as B. 3-carene; alpha-pinene; beta-pinene; alpha-terpinene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; Lime (allergenic !; note when using); longifolene; myrcene; ocimene; valencene; (E, Z) -1,3,5-undecatriene; styrene; diphenylmethane;
the aliphatic alcohols such. B. hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E) -2-hexenol; (E) - and (Z) -3-hexenol; 1-octene-3-ol; 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-methoxyoctane-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;
the aliphatic aldehydes and their acetates such. B. Hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methyl nonanal; (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; Heptanaldiethylacetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; 1- (1-methoxypropoxy) - (E / Z) -3-hexene;
the aliphatic ketones and their oximes such. B. 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;
the aliphatic sulfur-containing compounds such. B. 3-methylthiohexanol; 3-Methylthiohexylacetat; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;
aliphatic nitriles such as 2-nonenenitrile; 2-Undecensäurenitril; 2-Tridecensäurenitril; 3,12-Tridecadiensäurenitril; 3,7-dimethyl-2,6-octadiensäurenitril; 3,7-dimethyl-6-octensäurenitril;
the ester of aliphatic carboxylic acids such as (E) - and (Z) -3-hexenyl formate; ethylacetoacetate; isoamyl; 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; hexyl butyrate; (E) - and (Z) -3-hexenyl isobutyrate; hexyl crotonate; Ethylisovalerianat; Ethyl 2-methylpentanoate; ethylhexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; Ethyl (E, Z) -2,4-decadienoate; Methyl-2-octinat; Methyl-2-noninat; Allyl-2-isoamyloxyacetat; Methyl-3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentylcrotonat;
the acyclic terpene alcohols such as B. Citronellol (allergenic); Geraniol (allergenic); nerol; Linalool (allergenic); Lavadulol; nerolidol; Farnesol (allergenic); tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octene-2-ol; 2,6-dimethyl octane-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadiene-2-ol; 2,6-dimethyl-3,5-octadiene-2-ol; 3,7-dimethyl-4,6-octadiene-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-1-ol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerianates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoate;
the acyclic terpene aldehydes and ketones such as B. Geranial (allergenic); Neral (allergenic); Citronellal (allergenic); 7-hydroxy-3,7-dimethyloctanal (= hydroxycitronellal; allergenic); 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranyl acetone; as well as the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal;
the cyclic terpene alcohols such as B. menthol; isopulegol; alpha-terpineol; Terpinenol-4; Menthane-8-ol; Menthane-1-ol; Menthane-7-ol; borneol; soborneol; linalool; monopoly; cedrol; ambrinol; Vetyverol; guaiol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerianates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoate;
the cyclic terpene aldehydes and ketones such. B. Menthon; menthone; 8-mercaptomenthan-3-one; Car of; camphor; fenchon; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethylionone; alpha-irone; alpha-damascone; beta-damascone; beta-damascenone; delta-damascone; gamma-damascone; 1- (2,4,4-trimethyl-cyclohexen-2-1-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; Dihydronootkaton; 4,6,8-Mega stigma triene-3-one; alpha-sinensal; beta-sinensal; acetylated cedarwood oil (methyl cedryl ketone);
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-methyl tetrahydro-2H-pyran-4-ol;
cycloaliphatic alcohols such as alpha, 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-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 cycloaliphatic ethers such as cineol; cedryl methyl ether; cyclododecyl; 1,1-Dimethoxycyclododecan; (Ethoxymethoxy) cyclododecane; alpha-Cedrenepoxid; 3a, 6,6,9a-tetramethyl-dodecahydronaphtho [2,1-b] furan; 3α-ethyl-6,6,9a-trimethyldodecahydronaphtho [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-dioxane;
cyclic and macrocyclic ketones such as 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-cyclopentadecenone; 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) -indanon; 8-cyclohexadecen-1-one; 9-cycloheptadecen-1-one; cyclopentadecanone; cyclohexadecanone;
cycloaliphatic 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-cyclohexene carbaldehyde; 4- (4-methyl-3-penten-1-yl) -3-cyclohexene carbaldehyde;
the cycloaliphatic ketones such as. B. 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-naphtalenylmethylketon; Methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienylketon; tert-butyl (2,4-dimethyl-3-cyclohexen-1-yl) ketone;
the ester of cyclic alcohols such as 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5-Trimethylcyclohexylacetat; Decahydro-2-naphthyl acetate; 2-Cyclopentylcyclopentylcrotonat; 3-pentyltetrahydro-2H-pyran-4-yl acetate; Decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 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-indenylpropionate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, or 6-indenyl isobutyrate; 4,7-methanooctahydro-5 or 6-indenyl acetate;
the ester of cycloaliphatic alcohols such as 1-cyclohexylethyl crotonate; the ester of cycloaliphatic carboxylic acids such as. B. allyl-3-cyclohexylpropionate; Allylcyclohexyloxyacetat; 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-dioxolan-2-acetate;
araliphatic alcohols such as benzyl alcohol (allergenic); 1-phenylethyl; 2-phenylethyl; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3- (3-methylphenyl) propanol; 1,1-dimethyl-2-phenylethyl; 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; 1- (4-isopropylphenyl) ethanol;
the ester of araliphatic alcohols and aliphatic carboxylic acids such as benzyl acetate; benzylpropionate; benzyl isobutyrate; Benzylisovalerianat; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-Phenylethylisobutyrat; 2-Phenylethylisovalerianat; 1-phenylethyl acetate; alpha-Trichlormethylbenzylacetat; alpha, alpha-Dimethylphenylethylacetat; alpha, alpha-Dimethylphenylethylbutyrat; cinnamyl; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;
the araliphatic ether such as 2-phenylethyl methyl ether; 2-Phenylethylisoamylether; 2-phenylethyl-1-ethoxyethyl ether; phenylacetaldehyde; phenylacetaldehyde; Hydratropaaldehyddimethylacetal; Phenylacetaldehydglycerinacetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a, 5,9b-tetrahydroindeno [1,2-d] -m-dioxin; 4,4a, 5,9b-tetrahydro-2,4-dimethylindeno [1,2-d] -m-dioxin;
the aromatic and araliphatic aldehydes such as. B. Benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; Hydratropaaldehyd; 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-butylphenyl) propanal; Cinnamaldehyde (allergenic); alpha-Butylzimtal dehyd; alpha-amyl cinnamic aldehyde; alpha-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 araliphatic ketones such as acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4- (4-hydroxyphenyl) -2-butanone; 1- (2-naphthalenyl) ethanone; 2-Benzofuranylethanon; (3-methyl-2-benzofuranyl) ethanone; benzophenone; 1,1,2,3,3,6-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 benzoic acid; phenylacetic acid; methylbenzoate; ethyl benzoate; hexyl benzoate; Benzyl benzoate (allergenic); methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; Phenylethyl phenylacetate; Methylcinnmat; ethylcinnamate; Benzyl; Phenylethylcinnamat; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl; hexyl salicylate; cyclohexyl; Cis-3-hexenyl salicylate; benzyl; phenylethyl; Methyl-2,4-dihydroxy-3,6-dimethylbenzoate; Ethyl 3-phenylglycidate; Ethyl-3-methyl-3-phenylglycidate;
nitrogenous aromatic compounds such as 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert.-butylacetophenone; cinnamic acid; 3-methyl-5-phenyl-2-pentensäurenitril; 3-methyl-5-phenylpentansäurenitril; methyl anthranilate; Methyl N-methylanthranilate; Schiff bases of methylanthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-Isopropyl; 6-Isobutylchinolin; 6-sec.-butylquinoline; 2- (3-phenylpropyl) pyridine; indole; skatol; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;
of phenols, phenyl ethers and phenyl esters such as, for example, estragole; anethole; Eugenol (allergenic); Eugenylmethylether; Isoeugenol (allergenic); Isoeugenylmethylether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-Naphthylethylether; beta-Naphthylisobutylether; 1,4-dimethoxybenzene; Eugenylacetat; 2-methoxy-4-methyl phenol; 2-ethoxy-5- (1-propenyl) phenol; p-Kresylphenylacetat;
the heterocyclic compounds such as 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;
the lactones such as 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-hexadecene-1,16-olide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; Ethylene-1,12-dodecanedioate; Ethylene-1,13-tridecandioat; Coumarin (allergenic); 2,3-dihydrocoumarin; Octahydrocoumarin.

Of these fragrance components several in different proportions in the fragrance compositions according to the invention, e.g. Perfume oils included his. Mixtures according to the invention (Fragrance compositions; perfume oils) can in perfumed Products such as Household products, personal care and perfumery products, be used.

Especially preferred perfumed Products are e.g. alcoholic perfumes, washing powder, fabric softener, Laundry cloths, surface cleaners, Toilet cleaner, detergent, All-purpose cleaner, disinfectant, polishes, glass cleaner, Dishwashing liquid, Air fresheners, shampoos, conditioners, hair colors, deodorants, Antiperspirants, solid and liquid Soaps, body lotions, Skin creams and waxes.

• a) Bereitstellen eines (vorzugsweise nicht-allergenen) Ausgangsstoffes oder -stoffgemisches,
• b) Bereitstellen einer Verbindung der Formel I, wobei in Formel I die Strukturvariablen n sowie R1–R6 die oben genannten Bedeutungen haben,
• c) Kombinieren des (vorzugsweise nicht-allergenen) Ausgangsstoffes oder -stoffgemisches mit einer sensorisch wirksamen Menge der Verbindung der Formel I, so dass die resultierende Riechstoff- oder Aromakomposition sensorische Eigenschaften besitzt, die gegenüber denen des Ausgangsstoffes oder -stoffgemisches (in vorbestimmter Weise, d.h. gezielt) modifiziert sind.

Another aspect of the invention relates to a method for producing a (preferably non-allergenic) fragrance or aroma composition (with a predetermined fragrance or aroma characteristic, comprising the following steps:

• a) provision of a (preferably non-allergenic) starting material or mixture,
• b) providing a compound of the formula I, the structure variables n and R1-R6 in formula I having the meanings mentioned above,
• c) combining the (preferably non-allergenic) starting material or mixture with a sensorially effective amount of the compound of the formula I, so that the resulting fragrance or aroma composition has sensory properties which are compared to those of the starting material or mixture (in a predetermined manner, modified).

In the event that an allergenic fragrance or aroma composition is generated with the described method, the condition applies that in the case of n = 0 with R3 and R4 = H: R5 = CHO or CH ₂ OCOR6.

In the processes, a starting material mixture, which is preferred, is preferably provided under a) example includes one or more fragrances that do not fall under the formula I, and whose respective name is advantageously contained in the above list of fragrance components. Non-allergenic fragrance components are particularly advantageous.

Preferably a compound of formula I is provided in step b), in which R3 and R4 together represent another chemical bond.

If through steps a) –c) and possibly further steps of a method according to the invention or aroma composition is made which is one of the compound of formula I contains corresponding β-terpene the concentrations of those used in the respective steps Connections advantageously chosen so that the mass ratio of the Compound of formula I to the corresponding β-terpene in the generated Fragrance or aroma composition> 100 : 1, preferably> 1000 : 1, again preferably 1: 10000.

1 is a simplified scheme for the synthesis of α-terpenes from 6-methyl-6-hepten-2-one.

Claims (10)

Use of a compound of formula I.

as a non-allergenic fragrance and / or fragrance generator, wherein in formula I n 0 or 1, R1 and R2 each H or together a further chemical bond, R3 and R4 each H or together a further chemical bond and R5 CH ₂ OH, CHO or CH ₂ OCOR6 with R6 H or unbranched or branched, saturated or unsaturated alkyl radical having 1-10 carbon atoms, a benzyl, a phenyl, a phenylethyl, an anthranyl, a cinnamyl or a salicyl radical. Use of a compound of formula I.

as a fragrance and / or fragrance generator, wherein in formula I n 0 or 1, R1 and R2 each H or together a further chemical bond, R3 and R4 each H or together a further chemical bond and R5 CH ₂ OH, CHO or CH ₂ OCOR6 with R6 H or unbranched or branched, saturated or unsaturated alkyl radical having 1-10 carbon atoms, a benzyl, a phenyl, a phenylethyl, an anthranyl, a cinnamyl or a salicyl radical, with the proviso that in the case from n = 0 with R3 and R4 = H: R5 = CHO or CH ₂ OCOR6. Use according to claim 1 or 2 in a mixture, wherein the mixture is optionally one to the compound of formula I corresponding β-terpene contains with the proviso that in this case the mass ratio of the compound of formula I to the corresponding β-terpene is> 100: 1, preferably> 1000: 1. Fragrance selected from the group consisting of out: (E, Z) -α-farnesol, (Z, E) -α-farnesol, (Z, Z) -α-farnesol, (E, E) -α-farnesal, (E, Z) -α-farnesal, (Z, E) -α-farnesal, (Z, Z) -α-farnesal, (E) -dihydro-α-farnesol, (Z) -dihydro-α-farnesol, (E) -dihydro-α-farnesal, (Z) -dihydro-α-farnesal and mixtures consisting of two, three or more of these compounds. Fragrance composition, comprising at least one sensor-effective amount of two mutually non-configuration-isomeric fragrances and / or fragrance formers, at least one of these fragrance substances and / or fragrance formers being a compound of the formula I,

where in formula I n 0 or 1, R1 and R2 each H or together a further chemical bond, R3 and R4 each H or together another chemical bond and R5 CH ₂ OH, CHO or CH ₂ OCOR6 with R6 H or unbranched or branched , saturated or unsaturated alkyl radical having 1-10 carbon atoms, a benzyl, a phenyl, a phenylethyl, an anthranyl, a cinnamyl or a salicyl radical, with the proviso that in the case of n = 0 with R3 and R4 = H applies: R5 = CHO or CH ₂ OCOR6. Fragrance composition, comprising at least one sensor-effective amount of two mutually non-configuration-isomeric fragrances and / or fragrance formers, at least one of these fragrance substances and / or fragrance formers being a compound of the formula I,

where in formula I n 0 or 1, R1 and R2 each H or together a further chemical bond, R3 and R4 each H or together another chemical bond and R5 CH ₂ OH, CHO or CH ₂ OCOR6 with R6 H or unbranched or branched , saturated or unsaturated alkyl radical having 1-10 carbon atoms, a benzyl, a phenyl, a phenylethyl, an anthranyl, a cinnamyl or a salicyl radical, with the proviso that when the mixture is added to the compound of the Formula I contains corresponding β-terpene, the mass ratio of the compound of formula I to the corresponding β-terpene is> 100: 1, preferably> 1000: 1. Fragrance composition according to claim 5 or 6, characterized characterized that it is non-allergenic. A method for producing a fragrance or aroma composition, comprising the following steps: a) providing a starting material or mixture of substances, b) providing a compound of formula I,

where in formula I n 0 or 1, R1 and R2 each H or together a further chemical bond, R3 and R4 each H or together another chemical bond and R5 CH ₂ OH, CHO or CH ₂ OCOR6 with R6 H or unbranched or branched , saturated or unsaturated alkyl radical having 1-10 carbon atoms, a benzyl, a phenyl, a phenylethyl, an anthranyl, a cinnamyl or a salicyl radical, with the proviso that in the case of n = 0 with R3 and R4 = H applies: R5 = CHO or CH ₂ OCOR6, c) combining the starting material or mixture with a sensorially effective amount of the compound of the formula I, so that the resulting fragrance or aroma composition has sensory properties that are comparable to those of the starting material or mixture of substances are modified. A method for producing a non-allergenic fragrance or aroma composition, comprising the following steps a) providing a non-allergenic starting material or mixture, b) providing a compound of formula I,

where in formula I n 0 or 1, R1 and R2 each H or together a further chemical bond, R3 and R4 each H or together another chemical bond and R5 CH ₂ OH, CHO or CH ₂ OCOR6 with R6 H or unbranched or branched , saturated or unsaturated alkyl radical with 1-10 carbon atoms, a benzyl, a phenyl, a phenylethyl, an anthranyl, a cinnamyl or a salicyl radical, c) combining the non-allergenic starting material or mixture of substances with a sensory effective amount of the compound of formula I, so that the resulting fragrance or aroma composition has sensory properties that are modified compared to those of the starting material or mixture. A method according to claim 8 or 9, with the proviso that if the fragrance or aroma composition generated by steps a) -c) and possibly further steps contains a β-terpene corresponding to the compound of formula I, the concentrations of the in the respective steps used compounds are chosen so that the mass ratio of the compound of formula I to the corresponding β-Ter pen in the fragrance or aroma composition produced is> 100: 1, preferably> 1000: 1.