EP3359516A1

EP3359516A1 - Use of novel mixtures of (e/z) cyclopentadecenone isomers, the production and use thereof as flavoring substance

Info

Publication number: EP3359516A1
Application number: EP16778043.6A
Authority: EP
Inventors: Frauke THRUN; Joaquim Henrique Teles; Albert Werner; Ralf Pelzer
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2015-10-08
Filing date: 2016-10-07
Publication date: 2018-08-15
Also published as: JP2018538237A; BR112018006730A2; CN108137460A; WO2017060440A1; MX2018004300A; US20180290959A1

Abstract

The present invention relates to a novel mixtures of cyclopentadecenone isomers, to the production and use thereof as a flavoring substance, in particular as an odoriferous substance, and to flavoring substance mixtures and products containing said mixtures.

Description

The present invention relates to novel mixtures of (E / Z) -cyclopentadecenone isomers, their preparation and their use as a flavoring agent, in particular as an odoriferous substance, the invention relates to novel mixtures of (E / Z) -cyclopentadecenone isomers, their preparation and their use as flavoring agents. and flavor compositions and agents containing these mixtures.

Background of the invention

There is a continuing need in the perfume industry for new fragrances that are useful as fragrance compositions or perfumed articles.

In particular, there is a need for musk-like fragrances and perfume compositions. By this is meant a smell that is similar to the naturally occurring musk fragrance.

Trans- and c / s-cyclopentadec-8-enone are already mentioned in US 5,936,100 and in Fürstner, A. et al, Synthesis 1997, 792. The compounds were prepared from heptadeca-1, 16-dienone by means of a ruthenium-catalyzed ring-closing alkene metathesis produced. EP-A-1 264 594 mentions the use of cis- and iran-cyclopentedec-7-enone as admixture in a formulation for inhibiting melanin synthesis. EP-A 216 185 mentions that the compounds of the c / s-7- and 8-cyclopentadecen-1 -ones starting from c / s-16-oxabicyclo- [13.1.0] -hexadec-8-ene via an acid or Lewis acid-catalyzed Meerwein rearrangement can be prepared, but without providing experimental evidence. Furthermore, the usefulness of the two compounds is postulated as perfume. However, the actual olfactory properties of the 7- or 8-cyclopentadecenones have not yet been described in the literature. The Cu-catalyzed oxidative decarbonylation is known and widely published, examples are: a) Tetrahedron Lett. 1969, 12, 985; US3496197; b) Tetrahedron Lett. 1995, 36, 4641, c) Org. Lett. 2011, 13, 2630, d) Bioorg. Med. Chem. Lett. 2013, 23, 5949, e) Chin. Chem. Lett. 2014, 25, 771. The oxidation of cyclohexadeca-1, 9-diene with N ₂ O is also known from the prior art (WO 2012/084673). The main product (E / Z) -cyclohexadec-8-enone and by-products are various cyclopentadecenylcarbaldehydes. A distillative Separation of the mixture of cyclohexadec-8-enone and cyclopentadecenylcarbaldehyde is possible only with a high yield loss of cyclohexadec-8-enone. However, a separation of the mixture of cyclohexadec-8-enone and cyclopentadecenylcarbaldehyde must be carried out, since otherwise cyclohexadec-8-enone is associated with a false note.

The object of the present invention is to provide novel musky fragrances.

Summary of the invention

Surprisingly, the above object was achieved in particular by providing the macrocyclic keto compounds defined in the claims and a process for their preparation and isolation. In particular, it has been found that the cyclic aldehydes, which are formed as by-products in the oxidation of cyclohexadeca-1, 9-diene with nitrous oxide, can be subjected to a Cu-catalyzed, oxidative decarbonylation. From the resulting reaction effluent, cyclohexadec-8-enone can be separated from the resulting cyclopentadec-8-enone by distillation without significant losses in yield; in addition, a mixture consisting essentially of (E / Z) -cyclopentadec-8-ene can be distilled off. enone (ratio eg 1: 1) and (E / Z) cyclopentadec-7-enone (ratio 1: 1), wherein the ratio of cyclopentadec-8-enone and cyclopentadec-7-enone is 10: 1, with valuable olfactory Isolate properties.

Surprisingly, it has been found that the cyclopentadecenones I-IV smell very well olfactorily from the Cu-catalyzed, oxidative decarbonylation of cyclopentadecenylcarbaldehyde XI. The cyclopentadecenones L-IV thus extend the repertoire of the fragrance industry, especially the musk-like fragrances. The compounds are characterized by a green, aldehydic, harsh, gaseous, sweet, powdery, after dried fruit and smelling of musk smell. The cyclopentadec-8-enones occur as a (E / Z) mixture in the ratio 1: 1 in the Cu-catalyzed, oxidative decarbonylation. As by-products, the (E / Z) cyclopentadec-7-enones were also obtained.

Detailed Description of the Invention a) General Definitions: An "aroma chemical" is a generic term for compounds that can be used as "fragrance" and / or as "flavor".

For the purposes of the present invention, "perfume" is to be understood as meaning natural or synthetic substances with an inherent odor.

For the purposes of the present invention, the term "flavoring agent" is to be understood as natural or synthetic substances with a natural taste. The "smell" or "olfactory perception" in the sense of the present invention is the interpretation of the sensory excitations delivered by the chemoreceptors of the nose or other olfactory organs to the brain of a living being. The smell can therefore be a sensory perception of the nose of fragrances, which takes place when inhaled. The air serves as a smell carrier.

For the purposes of the present invention, the term "fragrance" is to be understood as meaning a fragrant odor. The same applies to a "perfume" according to the invention.

For the purposes of the present invention, a "perfume" is a mixture of fragrances and carriers, in particular an alcohol.

For the purposes of the present invention, a "perfume composition" is a perfume which contains different amounts of harmoniously matched individual components. The properties of the individual components are used to create a new overall picture in the combination, with the characteristics of the ingredients fading into the background, but without being suppressed.

For the purposes of the present invention, a "perfume oil" is a concentrated mixture of several fragrances, which are e.g. used in alcoholic solutions for perfuming various products.

For the purposes of the present invention, a "fragrance theme" is the predominant fragrance note in a fragrance composition. For the purposes of the present invention, the "top note" is the first phase of the perfume course of a perfume. It plays the crucial role in the first impression, when opening the bottle and when applying the perfume to the skin. The task of the top note is interest to awaken the perfume in general and to attract attention. Therefore, an exceptional character is often more important than a sophisticated harmony. The top note is naturally determined by volatile odoriferous substances. "Modification" in the context of the present invention means to provide the basic theme of a fragrance composition with additional or different chords and odor nuances.

"Chords" arise in the context of the present invention by the combination of different fragrances, which thus unite to form new odors. The number of fragrances used can range from two to a hundred different.

An "organoleptically / sensory effective amount" in the context of the present invention is the amount of a fragrance sufficient to stimulate a sensory organ or stimulating a sensory receptor.

(E / Z) is (E and / or Z) and basically denotes, unless stated otherwise, mixtures comprising both the stereoisomeric E configuration and the corresponding Z configuration, but also the stereoisomerically pure E and Z forms of one Connection. b) specific embodiments of the invention

The present invention relates in particular to the following subjects:

1 . Process for the preparation of at least one macrocyclic, in particular mononuclear, macrocyclic keto compound of general formula X.

(X) where A is a cycloaliphatic hydrocarbon radical having m ring carbon atoms, where m is an integer from 13 to 17, such as 13, 14, 15, 16 or 17, in particular 15, and optionally n C = C double bonds where n is an integer value of 1, 2 or 3, in particular 1 wherein a) at least one cycloaliphatic carbaldehyde compound of the formula XI

(XI)

wherein A has the meanings given above, oxidatively decarbonylated; wherein reacting the compound of formula XI in the presence of, preferably a catalytic amount of a preferably homogeneous Cu (II) catalyst and molecular pure oxygen, lean air or preferably air, in particular dried, filtered ambient air, and optionally

b) isolating at least one compound of formula X from the reaction mixture;

This gives the target compound of formula X in stereoisomerically pure form or in the form of stereoisomer mixtures containing at least 2, in particular 2, 3 or 4, stereoisomeric forms of such keto compounds; or wherein mixtures of substances are obtained containing at least 2, e.g. 2, 3, or 4, in particular 2 or 3, such keto compounds in each stereoisomerically pure form or as a stereoisomer mixture. In particular, compounds are preferably obtained in which, in the case of n = 1, the keto group and the ring C =C double bond have 4 to 7 ring carbon atoms removed from one another. Substance mixtures, if n is not 0, may also include constitutional isomers. If n is 2 or 3 then the double bonds are not cumulated.

Process according to embodiment 1, wherein the oxidative decarbonylation additionally takes place in the presence of a particular organic base.

The base used in the process according to the invention is, for example, selected from diazabicycloalkanes, such as. Diazabicyclooctane (DABCO), diazabicycelloundecene (DBU), diazabicyclononane (DBN) tertiary amines such as trimethylamine, triethylamine, triisopropylamine, diisopropylethylamine or tripropylamine, N, N-dimethylpiperazine, / V-methylpyridine, / V-methylpyrrolidone, quinuclidine and the like , Preferably DBU is used. Method according to one of the preceding embodiments, wherein the oxidative decarbonylation takes place in the absence or in the presence of a solvent, such as in the presence of an organic solvent, in particular an organic solvent, wherein the catalyst is dissolved.

Non-limiting examples of organic solvents include: polar, aprotic solvents such as dimethylformamide (DMF), hexamethylphosphoramide (HMPA), dimethylsulfoxide (DMSO), tetramethylurea and dimethylacetamide, and mixtures thereof. Other suitable organic solvents which can be used alone or in combination with the above aprotic organic solvents are alcohols, such as methanol, ethanol, propanol or butanols, such as ie / f-butanol and tetrahydrofuran, dioxane or benzene. Preferably DMF is used.

In an alternative embodiment, the reaction takes place essentially without addition of solvent, preferably in a solvent-free reaction mixture. The mixture of reactants and catalyst may be preferably heated thereto, e.g. to a temperature of 30 to 70 or 40 to 60 ° C.

Process according to one of the preceding embodiments, wherein the catalyst is formed by adding to a Cu (II) salt, in particular a bidentate ligand, preferably diamine ligands.

The Cu (II) salt used according to the invention is selected, for example, from Cu (II) acetate, formate, sulfate, chloride or nitrate. Preferably, Cu (OAc) _{2 is} used.

Suitable complex ligands are in particular bidentate Cu complexing amine ligands, such as Λ /, Λ /, Λ / ', Λ /' - tetramethylethylenediamine (TMEDA), 1, 10-phenanthroline and 2,2-bipyridyl. Preferably, TMEDA is used.

Method according to one of the preceding embodiments, wherein the oxidative decarbonylation at a temperature in the range of 10 to 70, in particular 30 to 60 ^° C, over a period of 0.1 to 40, in particular 0.1 to 30 h, preferably 2 to 7 h, especially 3 to 5 h, such as about 4 h, and at a pressure of 0.1 to 10, in particular 1 to 2 atm is performed. A performance of the method in a vacuum, such as at a negative pressure in the range of 0.001 to 0.99 bar, or in particular 0.01 to 0.5 or 0.1 to 0.25 bar is also conceivable. Method according to one of the preceding embodiments, wherein in the compounds of the formula X and XI m is 15 and / or n is 1, in particular m is 15 and n is 1.

Process according to one of the preceding embodiments, wherein (E / Z) - cyclopentadec-8-enyl-1-carbaldehyde or a substance mixture containing this compound, such as e.g. a mixture of (E / Z) -cyclopentadec-8-enyl- and (E / Z) -cyclopentadec-7-enyl-1-carbaldehyde.

A process according to embodiment 7, wherein at least one compound selected from (E / Z) -cyclopentadec-8-en-1-one and (E / Z) -cyclopentadec-7-en-1-one is obtained.

Process according to embodiment 8, wherein at least one compound is selected from compounds of the following formulas I, II, III and IV

(8E =) - <_Vdopentadec (7E =) - <_Vdopentadec (8Z) -Q / dopentadec (7Z) -cyclopentadec-8-en-1-one 7-en-1-one 8-en-1- on 7-en-1-on

I II III IV

receives, in particular a mixture substantially, (ie at least 80% or 90% (ie area%) of the compounds I and III or a mixture substantially (ie at least 80% or 90% (area%) of the Compounds I, II and III or from the compounds I, II and III and optionally IV.

Method according to one of the preceding embodiments, wherein a reaction product is used in step a), which is obtained from the dinitrogen monoxide oxidation of a cycloaliphatic compound of formula XII

(XII) wherein A 'is a cycloaliphatic hydrocarbon radical having m + 1 ring carbon atoms, wherein m is an integer value of 13 to 17, such as 13, 14, 15, 16 or 17, in particular 15, and optionally n + 1 C = C Having double bonds, and wherein n is an integer value of 1, 2 or 3, in particular 1, method of embodiment 10, wherein in the compound of formula XII m is 15 and n is 1. Process according to embodiment 1 1, wherein the compound of formula XII is cyclohexadeca-1,9-diene.

A process for preparing globanone ((E / Z) -cyclohexadec-8-en-1-one) comprising: a) oxidizing cyclohexadeca-1,9-diene with dinitrogen monoxide to obtain a reaction mixture comprising a mixture comprising ( E / Z) -cyclohexadec-8-en-1-one (globanone) and at least one cyclopentadecenylcarbaldehyde compound, especially selected from (E / Z) -cyclopentadec-8-enylcarbaldehydes; optionally separating unreacted cyclohexadeca-1, 9-diene, e.g. distillatively, and then optionally recycled to the process, step a);

b) subjecting the reaction mixture of step a) to an oxidative decarbonylation reaction according to any one of embodiments 1 to 5; and

c) separates globanone from the cyclopentadecenones formed thereby, in particular the cyclopentadecenones I, II, III and / or IV formed therefrom or mixtures thereof.

The oxidative decarbonylation can be carried out in the presence or absence of a solvent.

Process according to embodiment 13, wherein the separation in step c) is carried out by distillation.

A substance or mixture of substances comprising at least one macrocydic keto compound of the above general formula X.

A composition according to embodiment 15 comprising substantially (ie at least 80% or 90% (FI .-%) at least two compounds selected from (E / Z) cyclopentadec-8-en-1-one and (E / Z) Cyclopentadec-7-en-1-one. A composition according to embodiment 16, comprising substantially (ie at least 80% or 90% (FI .-%) at least two compounds selected from compounds of the following formulas I, III and the regioisomers thereof, such as the formula II

(8E-O-clopentadec-7E-O-clopentadec-8Z-cyclopentadec-8-en-1-one 7-en-1-one 8-en-1-one

II III

or comprising substantially (i.e., at least 80% or 90% (FI .-%) of at least two compounds selected from compounds of the following Formulas I and III and the regioisomers thereof, such as Formulas II and IV

(8E) -Q dopentadec (7E-C-clopentadec-8Z) -Q dopentadec (7Z) -Q dopentadec-8-en-1-one 7-en-1-one 8-en-1-one 7 -en-1-one

I II III IV Use of at least one substance or substance mixture according to one of embodiments 15 to 17 as an aroma chemical, in particular as a fragrance. Use according to embodiment 18 in compositions selected from perfumes, detergents and cleaners, cosmetics, personal care products, hygiene articles, foods, food supplements, fragrance dispensers, fragrances, pharmaceuticals and crop protection agents. Use according to any of embodiments 18 and 19 of a mixture, essentially containing (E) -cyclopentadec-8-en-1-one (I) and (Z) -cyclopentadec-8-en-1-one (III). 21. Use according to embodiment 20, wherein the molar ratio of (I) to (III) ranges from about 1: 1 to about 10: 1, especially 1: 1 to 5: 1. 22. Use according to any of embodiments 18 to 21 for production a musk note in a fragrance composition.

23. Use according to embodiment 22, for imparting, modifying and / or enhancing a musk fragrance in a fragrance composition by admixing a sensory effective amount of at least one substance or a mixture according to the

Definition in one of the embodiments 15 to 17.

24. A fragrance composition comprising at least one substance or a mixture of substances as defined in one of the embodiments 15 to 17 or produced by one of the processes according to the embodiments 1 to 12.

25. Composition according to embodiment 21, containing the substance or mixture of substances in a proportion by weight of 0.01 to 99.9 wt .-%, 1 to 80 wt .-%, 2 to 50 wt .-%, 3 to 25 or 5 to 15 wt .-% based on the total weight of the composition.

26. Composition comprising at least one substance or a mixture of substances as defined in one of embodiments 15 to 17 or produced by one of the processes according to embodiments 1 to 12.

27. A composition according to embodiment 26, comprising the substance or the mixture of substances in a weight fraction of 0.01 to 99.9 wt .-%, 1 to 80 wt .-%, 2 to 50 wt .-%, 3 to 25 or 5 to 15 wt .-%, based on the total weight of the composition. 28. Composition according to embodiment 26 or 27, selected from perfumes, detergents and cleaners, cosmetics, personal care products, hygiene articles, foods, food supplements, fragrance dispensers, fragrances, pharmaceutical agents and crop protection agents.

Further embodiments of the invention

fragrance compositions According to a further aspect, the fragrances used according to the invention are used in particular for the purpose of more efficient handling and metering, also as perfume mixtures with diluents or solvents. Here, the proportion of fragrances, based on the sum of fragrances and solvents, in wt .-% is given.

Solvent:

For the purposes of the present invention, a "solvent" serves to dilute the fragrances or fragrance compositions according to the invention to be used without having their own odoriferous properties. Some solvents also have fixing properties.

The compound of the formula X according to the invention or an above-defined mixture of several compounds / isomers of the formula X can be admixed to form 0.1 to 99% by weight of a diluent or solvent. Preferably, at least 40 wt .-% solutions, more preferably at least 50 wt .-% solutions, further preferably at least 60 wt .-% solutions, more preferably at least 70 wt .-% solutions, more preferably at least 80 wt. -% solutions, more preferably at least 90 wt .-% solutions, preferably in olfactorily acceptable solvents.

Preferred olfactorily acceptable solvents are ethanol, isopropanol, dipropylene glycol (DPG), propylene glycol, 1,2-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethyl phthalate (DEP), isopropyl myristate (IPM), triethyl citrate (TEC), benzyl benzoate (BB) and benzyl acetate. Again preferred are ethanol, diethyl phthalate, propylene glycol, dipropylene glycol, triethyl citrate, benzyl benzoate and isopropyl myristate.

For the purposes of the present invention, a "fragrance composition" is a mixture which, in addition to a compound of the formula X according to the invention or a substance mixture of a plurality of compounds / isomers of the formula X as defined above, comprises at least one further fragrance. In particular, such a fragrance composition may be a perfume composition (a perfume oil).

Fragrance compositions according to the invention contain, based on the total amount of the perfume composition, for example an amount of a compound of the formula X according to the invention or of a substance mixture of several compounds / isomers of the formula X defined above of from 0.01 to 65% by weight, preferably of about 0, From 1 to about 50 weight percent, preferably from about 0.5 to about 30 weight percent, and more preferably from about 0.5 to about 25 weight percent. The Weight ratio of inventive compound / compounds of formula X to the total amount of other fragrances is for example in the range of 1: 1000 to 1: 0.5, preferably in the range of 1: 700 to 1: 1, particularly preferably in the range of 1: 500 to 1:10.

Fragrance compositions according to the invention contain, based on the total amount of the fragrance composition, e.g. an amount of compound (s) according to the invention of formula X of from 0.01 to 65% by weight and preferably from about 0.1 to about 50% by weight, preferably from about 0.5 to about 30% by weight and more preferably from about 0.5 to about 25 weight percent. The weight ratio of inventive compound (s) of the formula X to the total amount of other (different) fragrances is e.g. in the range of 1: 1000 to 1: 0.5, preferably in the range of 1: 700 to 1: 1, particularly preferably in the range of 1: 500 to 1:10.

The above information on the content of compounds of the formula X apply mutatis mutandis to the preferred compounds of formulas I, II, III and IV, especially for mixtures of the compounds of formulas I, II, III and IV. Further fragrances:

Fragrance compositions according to the invention contain, in addition to the compound (s) of the formula X according to the invention (in particular of the formulas I, II and III) at least one further fragrance, preferably 2, 3, 4, 5, 6, 7, 8 or more further fragrances, wherein further Fragrances eg are selected under:

Alpha-hexyl cinnamic aldehyde, 2-phenoxyethyl isobutyrate (phenate- ¹ ), dihydromyrcenol (2,6-dimethyl-7-octene-2-ol), methyl dihydrojasmonate (preferably containing more than 60% by weight of c / s isomers) (Hedione ⁹ , Hedione HC ⁹ ), 4,6,6,7,8,8-hexamethyl-1, 3,4,6,7,8-hexahydro-cyclopenta [g] benzopyran (Galaxolid ³ ), tetrahydrolinalool (3 , 7-dimethyloctan-3-ol), ethyllinalool, benzylsalicylate, 2-methyl-3- (4-he / f-butylphenyl) propanal (Lilial ² ), cinnamyl alcohol, 4,7-methano-3a, 4,5,6 , 7,7a-hexahydro-5-indenyl acetate and / or 4,7-methano-3a, 4,5,6,7,7a-hexahydro-6-indenyl acetate (Herbaflorate ¹ ), citronellol, citronellyl acetate, tetrahydrogeraniol, vanillin, Lina ethyl acetate, styrolyl acetate (1-phenylethyl acetate), octahydro-2,3,8,8-tetramethyl-2-acetonaphthone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2, 3,8,8-tetramethylnaphthalene (Iso E Super ³ ), hexylsaturate, 4-he / f-butylcyclohexyl acetate (Oryclone ¹ ), 2-he / f-butylcyclohexylacetate (Agrumex HC ¹ ), alphalonone (4- ( 2,2,6-trimethyl-2-cyclo witch n-1-yl) -3-buten-2-one), n-alpha-methylionone, alpha Isomethylionone, coumarin, terpinyl acetate, 2-phenylethyl alcohol, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexenecarboxaldehyde (Lyral ³ ), alpha-amylcinnamaldehyde, ethylene brassylate, (E) - and / or (Z) -3-methylcyclopentadec 5-enone (Muscenon ⁹ ), 15-pentadec-1 1 -enolide and / or 15-pentadec-12-enolide (Globalide ¹ ), 15-cyclopentadecanolide (Macrolide ¹ ), 1 - (5,6,7, 8 Tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthalenyl) ethanone (Tonalid ¹⁰ ), 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol (Florol ⁹ ), 2-ethyl -4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol (Sandols ¹ ), c / ^' s-3-hexenyl acetate, irans-3-hexenyl acetate, frans-2, -c / s-6-nonadienol, 2,4-dimethyl-3-cyclohexene-carboxaldehyde (Vertocitral ¹ ), 2,4,4,7-tetramethyl-oct-6-en-3-one (Claritone ¹ ), 2,6-dimethyl-5-hepten-1-al (melonal ² ), borneol, 3- (3-isopropylphenyl) butanal (florhydral ² ), 2-methyl-3- (3,4-methylenedioxyphenyl ) propanal (Helional ³ ), 3- (4-ethylphenyl) -2,2-dimethylpropanal (Florazon ¹ ), 7-methyl-2H-1, 5-benzodioxepin 3 (4H) -one (Calone ¹⁹⁵¹⁵ ), 3,3,5-trimethylcyclohexyl acetate (preferably containing 70% by weight of c / s isomers) or more and 2,5,5-trimethyl-1, 2,3,4,4a, 5,6,7-octahydronaphthalen-2-ol (Ambrinol S ¹ ). The above-mentioned fragrances are therefore preferably combined in the context of the present invention with mixtures according to the invention.

If trade names are given above, these refer to the following sources:

¹ trade name Symrise GmbH, Germany;

² trade name Givaudan AG, Switzerland;

3 Trade name International Flavors & Fragrances Inc., USA;

5 Trade name Danisco Seillans S.A., France;

⁹ trade name Firmenich SA, Switzerland;

¹⁰ Trade name PFW Aroma Chemicals BV, The Netherlands. Further fragrances, with which (E / Z) -cyclopentadec-7/8-enone can be combined, for example, into a fragrance composition, can be found, for example, in S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, NJ, 1969 , Self-published or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4rd. Ed., Wiley-VCH, Weinheim 2001. Specifically, may be mentioned:

Extracts of natural raw materials such as essential oils, concretes, absolues, resines, resinoids, balsams, tinctures such as e.g.

ambergris tincture; Amyrisöl; Angelica seed oil; Angelica root oil; anise oil; Valerian oil; Basil oil; Tree moss absolute; Bay oil; Mugwort oil; Benzoeresin; Bergamotteol; Beeswax absolute; Birch tar oil; Bitter almond oil; Savory oil; Buccoblätteröl; Cabreuvaöl; cade oil; calamus; camphor oil; Cananga oil; cardamom; Cascarillaöl; cassia; Cassie absolute; Castoreum- absolute; Cedernblätteröl; cedarwood; cistus; citronella; lemon; copaiba balsam; Copava balsam oil; 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 oil; Grapefruit oil; guaiac wood; gurjun balsam; gurjun balsam oil; Helichrysum absolute; Lysine oil; Ginger oil; Iris root absolute; Orris root oil; Jasmine absolute; calamus; Chamomile oil blue; Camomile oil Roman; Carrot seed oil; Kaskarillaöl; Pine needle oil; spearmint; Caraway oil; labdanum; Labdanum absolute; Labdanumresin; Lavandin absolute; lavender oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Distilled lime oil; Pressed lime oil; Linaloe oil; Litsea cubeba oil; Bay leaf oil; Macisöl; Marjoram oil; Mandarin oil; Massoirindenöl; Mosaic absolute; Musk kernel 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; Palmarose 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; Sage oil Dalmatian; Sage oil spanish; sandalwood; Celery seed oil; Spikla- vendelöl; star anise; Styraxöl; tagetes; Pine needle oil; Tea-tree-oil; turpentine; Thyme oil; Tolu; Tonka absolute; Tuberose absolute; Vanilla extract; Violet leaf absolute; Vegetable oil; 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 from the group of hydrocarbons, such as 3-carene; alpha-pinene; beta-pinene; alpha-terpinene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene; Cedars; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E, Z) -1, 3,5-undecatriene; Styrene; diphenylmethane; the aliphatic alcohols such as 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; Mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methylene-heptan-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 acetals such as 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; (E / Z) -1- (1-methoxypropoxy) -3-hexene; the aliphatic ketones and their oximes such as 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 as 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-Menthene-8-thiol; the aliphatic nitriles such as 2-nonenitrile; 2-Undecensäurenitril; 2-Tridecensäurenitril; 3,12-Tridecadiensäurenitril; 3,7-dimethyl-2,6-octadiensäurenitril; 3,7-dimethyl-6-octenoic acid nitrile; the ester of aliphatic carboxylic acids such as (E) - and (Z) -3-hexenylformate; Ethyl acetate to acetate; isoamyl; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E) - 2-hexenyl acetate; (E) - and (Z) -3-hexenylacetate; 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; (E / Z) -ethyl-2,4-decadienoate; Methyl-2-octinat; Methyl 2-noninate; Allyl-2-isoamyloxyacetat; Methyl-3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl crotonate; the acyclic terpene alcohols such as geraniol; nerol; linalool; Lavadulol; nerolidol; Fernsol; tetrahydrolinalool; 2,6-dimethyl-7-octene-2-ol; 2,6-dimethyl octane-2-ol; 2-methyl-6-methylene-7-octene-2-ol; 2,6-dimethyl-5,7-octadiene-2-ol; 2,6-dimethyl-3,5-octadiene-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; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates; the acyclic terpene aldehydes and ketones such as geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,1-trimethyl-9-undecenal; Geranylacetone; and the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal; the cyclic terpene alcohols such as menthol; isopulegol; alpha-terpineol; Terpinene-4-ol; Menthane-8-ol; Menthan-1-ol; Menthane-7-ol; borneol; soborneol; linalool; monopoly; cedrol; ambrinol; Vetyverol; guaiol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates; the cyclic terpene aldehydes and ketones such as menthone; menthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchon; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethylionone; alpha-lron; al-Damascon; beta-damascone; beta-damascenone; delta-damascone; gamma-damascone; 1 - (2,4,4-trimethyl-2-cyclohexene-1-yl) -2-butene-1-one; 1, 3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalene-8- (5H) -one; 2-methyl-4- (2,6,6-trimethyl-1-cyclohexene-1-yl) -2-butene-al; nootkatone; Dihydronootkaton; 4,6,8-Mega stigma triene-3-one; alpha-sinensal; beta-sinensal; acetylated cedarwood oil (methyl cedryl ketone); the cyclic alcohols such as 4-ie / f-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2, Z5, E9-cyclododecatriene-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; the 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-butene-1-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) -2-butene-1-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl) -pentan-2-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 3,3-dimethyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 1 - (2,2,6-trimethylcyclohexyl) pentan-3-ol; 1 - (2,2,6-trimethylcyclohexyl) hexan-3-ol; the cyclic and cycloaliphatic ethers such as cineole; cedryl methyl ether; Cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (Ethoxymethoxy) cyclododecane; alpha-Cedrenepoxid; 3a, 6,6,9a-tetramethyldodecahydronaphtho [2,1-b] furan; 3a-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-cyclohexene-1-yl) -5-methyl-5- (1-methylpropyl) -1,3-dioxane; the cyclic and macrocyclic ketones such as 4-ie f-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; c / s-3-methylpent-2-en-1-yl-cyclopent-2-en-1-one; 3-methyl-2-pentyl-2-cyclopentene-1 -οη; decenon 3-methyl-4-cyclo-penta; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone; 4 IU / f-pentylcyclohexanone; Cyclohexadec-5-en-1 -one; 6,7-dihydro-1,1,3,3,3-pentamethyl-4 (5H) -indanone; 8-cyclohexa-decene-1-o; 7-cyclohexadecen-1-one; (7/8) cyclohexadecen-1-one; 9-cyclohepta-decene-1-one; cyclopentadecanone; cyclohexadecanone; the cycloaliphatic aldehydes such as 2,4-dimethyl-3-cyclohexene carbaldehyde; 2-methyl-4- (2,2,6-trimethylcyclohexene-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 1- (3,3-dimethylcyclohexyl) -4-penten-1-one; 2,2-dimethyl-1 - (2,4-dimethyl-3-cyclohexene-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-cyclododecatrienyl ketone; ie / f-butyl (2,4-dimethyl-3-cyclohexene-1-yl) ketone; the ester of cyclic alcohols such as 2-ie f-butylcyclohexyl acetate; 4-ie f-butylcyclohexyl acetate;

2-ie / f-pentylcyclohexyl acetate; 4 IU / f-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-hexa-hydro-5, and 6-indenyl acetate, respectively; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, and 6-indenylpropionate, respectively; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate; 4,7-methanoctahydro-5, or 6-indenyl acetate; the ester of cycloaliphatic alcohols, e.g. 1-cyclohexylethyl crotonate; the ester of cycloaliphatic carboxylic acids, e.g. Allyl 3-cyclohexylpropionate; Allylcyclohexy-loxyacetate; cis and iran methyldihydrojasmonate; egg and iran methyl jasmonate; Methyl 2-hexyl-3-oxocyclopentanecarboxylate; Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; Ethyl 2,3,6,6-tetramethyl-2-cyclohexene carboxylate; Ethyl 2-methyl-1,3-dioxolane-2-acetate; the araliphatic alcohols such as e.g. 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-phenyl-pentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl; 1 - (4-isopropyl-phenyl) -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-trichloromethylbenzylacetate; alpha, alpha-dimethylphenylethyl acetate; alpha, alpha-dimethyl-phenylethyl butyrate; cinnamyl; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; the araliphatic ethers such as 2-phenylethyl methyl ether; 2-Phenylethylisoamylether; 2-phenylethyl-1-ethoxyethyl ether; phenylacetaldehyde; Phenylacetaldehyde diethyl acetal; 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-dimethyl-indeno [1,2-d] -m-dioxin; the aromatic and araliphatic aldehydes such as 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-hexy-f-butylphenyl) propanal; 2-methyl-3- (4-isobutylphenyl) -propanal; 3- (4-IE / f-butylphenyl) -propanal; cinnamic aldehyde; alpha-Butylzimtaldehyd; 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; the aromatic and araliphatic ketones such as acetophenone; 4 methyl acetophenone; 4-methoxyacetophenone; 4 IU / f-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) -1 H-5-indenyl] ethanone; 8'-hexamethyl-2-acetonaphthone, 5 ', 6', 7 ', 8'-tetrahydro-3', 5 ', 5', 6 ', 8'; the aromatic and araliphatic carboxylic acids and their esters such as benzoic acid; phenylacetic acid; methylbenzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; Methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; Methylcinnmat; ethylcinnamate; Benzyl; Phenylethylcinnamat; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl; hexyl salicylate; cyclohexyl; c / s-3-hexenyl salicylate; benzyl; phenylethyl; Methyl-2,4-dihydroxy-3,6-dimethylbenzoate; Ethyl 3-phenylglycidate; Ethyl-3-methyl-3-phenylglycidate; the nitrogen-containing aromatic compounds such as 2,4,6-trinitro-1,3-dimethyl-5-iert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-IE / f-butylacetophenone; cinnamic acid; 3-methyl-5-phenyl-2-pentenoic acid nitrile; 3-methyl-5-phenylpentansäurenitril; methyl anthranilate; Methyl / V-methyl anthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-he / f-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexene carbaldehyde; 6-isopropylquinoline; 6-lsobutylchinolin; 6-sec-butylquinoline; 2- (3-phenylpropyl) pyridine; indole; skatol; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine; the phenols, phenyl ethers and phenyl esters such as estragole; anethole; eugenol; Eugenylmethyl ether; isoeugenol; Isoeugenylmethylether; thymol; carvacrol; diphenyl ether; beta-naphthylmethyl ether; beta-Naphthylethylether; beta-Naphthylisobutylether; 1, 4-dimethoxybenzene; Eugenylacetat; 2-methoxy-4-methyl phenol; 2-ethoxy-5- (1-propenyl) -phenol; p-Kresylphenylacetat; 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-decene-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 iran-1-pentadecene-1, 15-olide; cis-and iran-12-pentadecene-1, 15-olide; 1, 16-hexadecanolide; 9-hexadecene-1, 16-olide; 10-oxa-1, 16-hexadecanolide; 1 1 -Oxa-1, 16-hexadecanolide; 12-oxa-1,16-hexadecanolide; Ethylene-1,12-dodecanedioate; Ethylene-1,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; Octahydrocoumarin.

c2) perfume-containing articles

Inventive (E / Z) -cyclopentadec-7/8-enone or perfume compositions according to the invention can be incorporated in a number of products or applied to such products.

Fragrances according to the invention can be used in the production of perfumed articles. The olfactory properties as well as the material properties (such as solubility in common solvents and compatibility with common other constituents of such products) as well as the toxicological harmlessness of the fragrances according to the invention underline their particular suitability for the stated purposes. The positive properties contribute to the fact that the fragrances used according to the invention and the perfume compositions according to the invention are particularly preferably used in perfumery products, personal care products, hygiene articles, textile detergents and in cleaners for solid surfaces. The perfumed article is selected, for example, from perfumery products, personal care products, hygiene articles, laundry detergents and solid surface cleaners. Preferred perfumed articles according to the invention are furthermore selected from: perfumery products selected from perfume extracts, Eau de Parfums, Eau de Toilettes, Eau de Colognes, Eau de Solide, Extrait Perfume, air fresheners in liquid, gel or solid-carrier form, aerosol sprays , Fragrance cleaners and oils;

Personal care products selected from among shampoos, pre-shave products, splash colognes, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving creams, bath oils, oil-in-water, water-in-oil and cosmetic emulsions Water-in-oil-in-water type such as Skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products such as Hair sprays, hair gels, hair setting lotions, hair lotions, hair shampoo, permanent and semi-permanent hair dyes, hair styling agents such as cold waving and hair straightening, hair lotions, hair creams and lotions, deodorants and antiperspirants such as hair wipes. Underarm sprays, roll-ons, deodorants, deodorants, decorative cosmetics, e.g. Eye shadows, nail polishes, make-ups, lipsticks, mascara, toothpaste, dental floss;

Sanitary articles selected from among candles, lamp oils, incense sticks, insecticides, repellents, fuels, rust removers, scented towelettes, underarm pads, baby diapers, sanitary napkins, toilet paper, facial tissues, handkerchiefs, douche machines;

Solid surface cleaners selected from perfumed acidic, alkaline and neutral detergents, e.g. Floor cleaners, window glass cleaners, dishwashing detergents, bath and sanitary cleaners, scouring creams, solid and liquid toilet cleaners, powder and foam carpet cleaners, waxes and polishes such as furniture polishes, floor waxes, shoe creams, disinfectants, surface disinfectants and sanitary cleaners, brake cleaners, pipe cleaners, descaler, Grill and oven cleaners, algae and moss removers, mold removers, facade cleaners;

Laundry detergents selected from among liquid detergents, powdered detergents, laundry pre-treatment agents such as bleaches, soaking and stain removers, laundry conditioners, laundry soaps, washing tablets. According to a further aspect, the fragrances used according to the invention and the fragrance substance compositions according to the invention are suitable for use in surfactant-containing perfumed articles. Namely sought - especially for the perfuming of surfactant-containing formulations such as detergents (especially dishwashing detergents and all-purpose cleaners) - often fragrances and / or fragrance compositions with a Rosenkopfno- te and pronounced naturalness.

According to a further aspect, fragrances and fragrance compositions according to the invention can be used rosily as agents for providing (a) hair or (b) textile fibers with the odor note.

The fragrances and fragrance compositions according to the invention to be used according to the invention are therefore particularly suitable for use in surfactant-containing perfumed articles. It is preferred if the perfumed article is one of the following:

an acidic, alkaline or neutral detergent especially selected from the group consisting of all-purpose cleaners, floor cleaners, window glass cleaners, dishwashing detergents, bath and sanitary cleaners, scouring cream, solid and liquid toilet cleaners, powder and foam carpet cleaners, liquid detergents, powdered Washing mitts, laundry pretreatment agents such as bleaches, soak and stain removers, fabric softeners, laundry soaps, washing tablets, disinfectants, surface disinfectants,

an air freshener in a liquid, gelatinous or solid support form or as an aerosol spray,

a wax or a polish selected in particular from the group consisting of furniture polishes, floor waxes and shoe creams, or

a personal care product selected in particular from the group consisting of shower gels and shampoos shaving soaps, shaving foams, bath oils, oil-in-water, water-in-oil and water-in-oil-in-water cosmetic emulsions Types such as skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products such as hair sprays, hair gels, firm hair lotions, hair conditioners, permanent and semipermanent hair dyes, hair styling agents such as cold waves and hair straighteners, hair lotions, hair creams and lotions, deodorants and antiperspirants such as underarm sprays, rollons, Deosticks, Deocremes, decorative cosmetics. Ingredients with which fragrances or fragrance compositions according to the invention can preferably be combined are, for example: preservatives, abrasives, anti-acne agents, anti-aging agents, antibacterial agents, anti-cellulite agents, anti-dandruff agents, anti-inflammatory agents, anti-irritants, anti-irritants Agents, antimicrobial agents, antioxidants, astringents, perspiration inhibitors, antiseptics, antistatic agents, binders, buffers, carrier materials, chelating agents, cell stimulants, cleansing agents, skin care agents, depilatory agents, surface-active substances, deodorants, antiperspirants, emollients, emulsifiers, enzymes, essential oils, fibers, film formers, fixatives, foaming agents, foam stabilizers, foaming inhibitors, foam boosters, fungicides, gelling agents, gelling agents, hair care products, hair styling agents, hair straighteners moisturizing agents, moisturizing substances, moisturizing substances, bleaching agents, restorers, stain removers, optically brightening agents, impregnating agents, soil repellents, friction reducing agents, lubricants, moisturizers, ointments, opacifying agents, plasticizing agents, covering agents , Polishes, brighteners, polymers, powders, proteins, lubricating agents, abrasives, silicones, skin soothing agents, skin cleansing agents, skin care agents, skin healing agents, skin lightening agents, skin protecting agents, skin softening agents, cooling agents, skin cooling agents, warming agents, skin warming agents , Stabilizers, UV-absorbing agents, UV filters, detergents, fabric softeners, suspending agents, skin tanning agents, thickeners, vitamins, oils, waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, α-hydroxy acids, P olyhydroxyfatty acids, plasticizers, dyes, color protectants, pigments, anti-corrosives, flavors, flavorings, fragrances, polyols, surfactants, electrolytes, organic solvents or silicone derivatives.

According to a further aspect, the fragrances are used in the preparation of the perfumed articles in liquid form, neat or diluted with a solvent or in the form of a fragrance composition. Suitable solvents for this purpose include, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc. For the solvents mentioned, these, in the case of the presence of their own olfactory properties , are to be assigned exclusively to the component "solvents" and not to the "fragrances". The fragrances and / or fragrance compositions contained in the perfumed articles according to the invention can in one embodiment be absorbed on a carrier which is suitable both for a fine distribution of the fragrance or the fragrance composition in the Product as well as providing controlled release during use. Such carriers may be porous inorganic materials such as light sulfate, silica gels, zeolites, gypsum, clays, clay granules, aerated concrete, etc., or organic materials such as wood and cellulose based materials.

The fragrances used in accordance with the invention and the fragrance substance compositions according to the invention can also be microencapsulated, spray-dried, present as inclusion complexes or as extruded products and added in this form to the product or article to be perfumed. The properties can be further optimized by so-called "coating" with suitable materials with a view to a more targeted release of fragrance, to which end preferably wax-like plastics, such as e.g. Polyvinyl alcohol can be used.

The microencapsulation can be achieved, for example, by the so-called coacervation method with the aid of capsule materials, e.g. made of polyurethane-like substances or soft gelatin. The spray-dried perfume oils can be prepared, for example, by spray-drying an emulsion or dispersion containing the perfume oil, wherein starches, proteins, dextrin and vegetable gums modified as carriers can be used. Inclusion complexes may be e.g. by incorporating dispersions of fragrance compositions and cyclodextrins or urea derivatives into a suitable solvent, e.g. Water. Extrusion products can be prepared by fusing fragrances and fragrance compositions according to the invention with a suitable waxy substance and by extrusion followed by solidification, optionally in a suitable solvent, e.g. Isopropanol. c3) Preparation of fragrances according to the invention

The macrocyclic ketones of the formula X according to the invention are prepared starting from the corresponding carbaldehydes of the formula XI,

(XI) wherein A is a cycloaliphatic hydrocarbon radical having m ring carbon atoms, wherein m is an integer value of 13 to 17, and optionally n has C = C double bonds, where n is an integer value of 1, 2 or 3. The carbaldehydes in turn, for example, starting from the corresponding cycloaliphatic compounds of the formula XII

(XII) where A 'is a cycloaliphatic hydrocarbon radical having m + 1 ring carbon atoms, m being an integer from 13 to 17, and optionally having n + 1 C = C double bonds, and n being an integer value of 1, 2 or 3 and is accessible by dinitrogen monoxide oxidation. i) Synthesis of carbaldehyde (XI) by N ₂ O oxidation

Such as. described in PCT / EP2015 / 072544 of the Applicant.

Starting from the corresponding aliphatic carbocycle, in particular a cyclic mono- or polyunsaturated olefin XII (ie compared to the cyclic radical A in the product of formula X, the starting compound XII contains an additional C = C double bond and an additional ring carbon atom) are compounds of formula XI Dinitrogen monoxide oxidation accessible, as described for example in WO 2012/084673. Example of a suitable starting compound (which can be used both in stereoisomerically pure form or in the form of stereoisomer) for the preparation of compounds of formula XI wherein A is ₅ radical of a monounsaturated C is cyclohexanone deca-1, 9- which is either commercially available or can be prepared according to Example 2 of EP-A-1 288 181.

In particular, a cyclic olefin is oxidized by reaction with dinitrogen monoxide. Nitrous oxide can be used in pure or optionally in admixture with other gaseous substances under reaction conditions, such as carbon dioxide for dilution. It can be carried out for the reaction of the cyclic olefin with dinitrogen monoxide in the substance or in the presence of at least one suitable solvent or diluent. Preferably, the reaction takes place in substance. Substantially all common solvents and / or diluents are suitable here, but with the proviso that they have neither a CC double bond nor a C-C triple bond nor an aldehyde group. Examples of suitable solvents include: cyclic alkanes, for example cyclohexane, cyclopentane, cyclooctane, cyclododecane or saturated aliphatic or aromatic, optionally alkyl-substituted hydrocarbons. The temperature in the reaction is, for example, at 140 to 350 ° C, in particular at 180 to 320 ° C or at 200 to 300 ° C. It is also possible to carry out the reaction at two or more temperatures or in two or more temperature ranges which are each within the limits specified above. Temperature changes in the course of the reaction can be carried out continuously or discontinuously. In particular, however, the reaction temperature is substantially constant. The reaction can also be carried out preferably adiabatically, so that the temperature rises in the reactor.

The pressure in the reaction of the cyclic olefin with dinitrogen monoxide is in particular higher than the autogenous pressure of the educt or product mixture at the selected reaction temperature or the selected reaction temperatures. The pressure is e.g. at 1 to 1000 bar, e.g. at 40 to 300 bar or at 50 to 200 bar.

It is possible to carry out the reaction of the cyclic olefin with dinitrogen monoxide at two or more pressures or in two or more pressure ranges, each within the limits given above. Pressure changes in the course of the reaction can be carried out continuously or discontinuously. In particular, however, pressure during the reaction is essentially constant.

There are no particular restrictions on the reactors that can be used for the implementation (on a laboratory or production scale). In particular, the reaction can be carried out in batch mode or in continuous mode. Consequently, for example, at least one CSTR (Continuous Stirred Tank Reactor) with at least one internal and / or at least one external heat exchanger, at least one tube reactor, at least one tube bundle reactor or at least one loop reactor can be used as reactors. It is also possible to design at least one of these reactors in such a way that it has at least two different zones. Such zones may be, for example, in reaction conditions such as, for example, the temperature or the pressure and / or in the geometry. differentiation of the zone such as volume or cross section. If the reaction is carried out in two or more reactors, two or more identical reactor types or at least two different reactor types can be used. In particular, the reaction with dinitrogen monoxide is carried out in a single reactor. For example, the reaction can be carried out in a continuous mode or in batch mode.

The residence time of the reaction mixture in the reactor is generally in the range of 0.1 to 40 hours, preferably in the range of 0.1 to 30 hours, more preferably in the range of 2 to 7 hours.

In the feed, the molar ratio of nitrous oxide and the cyclic olefin is generally in the range of 0.01 to 30, e.g. in the range of 0.03 to 10, more preferably in the range of 0.05 to 1, and most preferably in the range of 0.08 to 0.2. Since dinitrogen monoxide is preferably used in excess, only part of the olefin XII (e.g., cyclohexadeca-1, 9-diene) is reacted. Unreacted olefin (e.g., cyclohexadeca-1, 9-diene) is separated by distillation from the reaction product and recycled to the reaction. The unreacted olefin (e.g., cyclohexadeca-1,9-diene) as the top product and the reaction product as the bottom product of the column are precipitated. The distillation is hereby e.g. at 20 mbar head pressure and e.g. 210 ° C sump temperature instead. The differential pressure across the column is e.g. 18 mbar. The column is e.g. equipped with a structured fabric packing of the type Montz A3. The package height is e.g. 4 m and the feed is e.g. at 2 m. From the resulting bottom product, the compound XI is then isolated by distillation as a minor component.

The desired reaction product XI is formed as a minor component, so that the reaction mixture must be suitably purified.

In a further variant of the invention, however, no further purification takes place but the direct reaction of the reaction mixture to give the desired ketone of the formula X. However, additional purification can also be carried out.

In the case of a purification, this can be carried out, for example, by distillation (in particular by fractional distillation, preferably at reduced pressure) or by chromatography. Suitable purification methods are familiar to the person skilled in the art. The cleaning can be done, for example, batchwise or continuously. For example, distillation by means of a distillation column can be used with packings known to those skilled in the art. The optimum distillation conditions can be determined by the skilled person without undue burden. The distillation can be carried out in particular under reduced pressure, for example at a pressure <1000 mbar, <500 mbar, <300 mbar, <100 mbar or <10 mbar. The distillation column used may have several, such as at least 20, at least 25 or at least 30 theoretical, such as up to 70 separation stages. The reflux ratio may be, for example, in the range of about 5 to 100 and at least 20, at least 25 or at least 30, and is in particular about 100 for a particularly advantageous fractionation.

For example, column chromatography may also be carried out in place of or subsequent to a distillative purification. For this purpose, column media and eluents known to the person skilled in the art are used. The optimum chromatography conditions, such as column geometry and speed of the mobile phase, can be determined by the skilled person without undue burden.

Examples of suitable column materials are polar adsorbents such. As iron oxide Fe ₂ 0 ₃ , alumina, carbohydrates or silica gel with or without additives such. As fluorescent indicators or gypsum.

Examples of suitable eluents are: aliphatic or aromatic eluents, such as, for example, alkanes or cycloalkanes, for example pentane, petroleum ether, hexane, heptane, toluene or the corresponding cyclic compounds; aliphatic ethers, esters or, such as Et ₂ 0, MTBE, EtOAc, acetone or mixtures of such eluents such. Hexane / MTBE, hexane / EtOAc, pentane / Et ₂ 0, petroleum ether / Et ₂ 0.

A desired carbaldehyde of the formula X, or mixtures thereof, in pure form or in a purity of more than 20, e.g. more than 30, more than 40, more than 50, more than 60, more than 70 or more than 80 wt .-% isolate. The carbaldehyde of the formula XI can be isolated in stereoisomerically pure form, or in particular as a mixture of two or more stereoisomers, in particular if the radical A has a C =C double bond.

In particular, iran-Cyclopentadec-8-enyl-1 -carbaldehyde in this way and / or c / ^{'s-Cyclopentadec-8-enyl-1} -carbaldehyde accessible. ii) Synthesis of the cyclic ketone (X) by oxidative decarbonylation Starting from the corresponding cyclic carbaldehyde of the general formula (XI) (purified or obtainable as reaction mixture, as described above), the oxidative decarbonylation is carried out on the basis of the Cu (II) -based decarbonylations known from the prior art (cf. eg a) Tetrahedron Lett. 1969, 72, 985; US3496197; b) Tetrahedron Lett. 1995, 36, 4641, c) Org. Lett. 2011, 73, 2630, d) Bioorg. Med. Chem. Lett. 2013, 23, 5949, e) Chin. Chem. Lett. 2014, 25, 771).

Specific, nonlimiting example of a suitable starting compound (which can be used both in stereoisomerically pure form or in the form of stereoisomer) for the preparation of compounds of formula X wherein A is ₅ radical of a monounsaturated C are Cyclopentadec-8-enyl and -7-enylcarbaldehyde.

According to the invention, the catalytic reaction of the cyclic carbaldehydes with the molecular oxygen is optionally carried out in the presence of at least one suitable solvent or diluent.

Oxygen can be used as pure oxygen or preferably as part of ambient air or lean air in the process.

Suitable solvents include: polar, aprotic solvents such as dimethylformamide (DMF), hexamethylphosphoramide (HMPA), dimethylsulfoxide (DMSO), tetramethylurea and dimethylacetamide, and mixtures thereof. Other suitable organic solvents which can be used alone or in combination with the above aprotic organic solvents are alkanols such as, for example, methanol, ethanol, propanol, isopropanol or butanols, such as ie / f-butanol and tetrahydrofuran, dioxane or benzene.

The catalytic reaction of the cyclic carbaldehydes can also be carried out in the absence of a solvent or diluent.

The catalyst used is Cu (II) -based, in particular homogeneous catalysts. These are preferably formed in situ in the reaction mixture by adding to a Cu (II) salt, in particular a bidentate ligand, preferably diamine ligands.

The Cu (II) salt used according to the invention is selected, for example, from Cu (II) acetate, formate, sulfate, chloride or nitrate. Preferably, Cu (OAc) _{2 is} used. Suitable complexing ligands are in particular bidentate copper complexing amine ligands such as Λ /, Λ /, Λ / ', Λ /' - tetramethylethylenediamine (TMEDA), 1, 10-phenanthroline and 2,2'-bipyridine. Preferably, TMEDA is used.

Complex ligand and Cu (II) salt are used in approximately equimolar ratio. The molar proportion of complex is about 0.1 to 10, in particular 1 to 5, preferably about 2.5 mol%, based on the carbaldehyde (XI) used. In particular, the decarbonylation is additionally carried out in the presence of an organic base. The base used in the process according to the invention, for example, is selected from diazabicycloalkanes, such as. For example, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazobicyclononane (DBN), tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine or tripropylamine, Ν, Ν-dimethylpiperazine, N-methylpyridine, N-methylpyrrolidone, quinuclidine and the like. Preferably DBU is used. The base is used in a proportion of 0.1-1 equiv, 0.2-0.8 equiv or more preferably 0.4-0.6 equiv based on the carbaldehydes of the formula (XI) used

The temperature of the reaction is, depending on the reactants and solvent used, e.g. at 20 to 100 ° C, in particular at 30 to 80 ° C, especially at 40 to 60 ° C. It is also possible to carry out the reaction at two or more temperatures or in two or more temperature ranges which are each within the limits specified above. Temperature changes in the course of the reaction can be carried out continuously or discontinuously. In particular, the reaction temperature is essentially constant.

The pressure during the reaction of the carbaldehydes (XI) with oxygen is in particular at ambient pressure or approximately in the region of the autogenous pressure of the educt or product mixture at the selected reaction temperature or the selected reaction temperatures. The pressure is e.g. at 0.1 to 5 bar, e.g. at 0.1 to 3 bar, preferably about 1 bar.

It is possible to carry out the reaction at two or more pressures or in two or more pressure ranges, each within the limits specified above. Pressure changes in the course of the reaction can be carried out continuously or discontinuously. In particular, however, pressure during the reaction is essentially constant. In particular, the reaction can be carried out in batch mode or in continuous mode.

There are no particular limitations with regard to the reaction vessels which can be used for the implementation (on a laboratory or production scale). In the case of using a reactor, for example, conventional stirred reactors, CSTR (Continuous Stirred Tank Reactor), each with or without internal and / or external heat exchanger, a tubular reactor, a tube bundle reactor or a loop reactor can be used. It is also possible to design the reactors so that they have at least two different zones. Such zones may differ, for example, in reaction conditions such as, for example, the temperature or the pressure and / or in the geometry of the zone, for example the volume or the cross section. If the reaction is carried out in two or more reactors, two or more identical reactor types or at least two different reactor types can be used. In particular, however, the reaction is carried out in a single reactor, in particular a stirred reactor.

The residence time of the reaction mixture in the reactor is generally in the range of 0.1 to 40 hours, preferably in the range of 0.1 to 30 hours, more preferably in the range of 0.1 to 25 hours, in particular 1 to 4 hours.

In particular, the reaction can be carried out as follows:

A reaction mixture consisting of an excess of (E / Z) -cyclohexadec-8-enone and an amount of cyclopentadec-8-enylcarbaldehyde present in deficit is optionally dissolved in DMF. To the mixture are added as the base diazabicycloundecene (DBU, 0.5 to 1, 5, for example, 0.6 eq based on carbaldehyde (XI)) added. Through the mixture, an air stream was passed continuously. The bidentate complex ligand TMEDA (1 to 5 mol%, such as 2 mol% based on carbaldehyde (XI)) and Cu (OAc) ₂ (1 to 5 mol%, 2 mol%) are dissolved in DMF. Alternatively, a Cu-TMEDA mixture may also be prepared without adding a solvent. The Cu-TMEDA mixture, with or without DMF, is then added dropwise continuously or in a batch of the reaction solution. The reaction was stirred at 40 to 60, such as 50 ° C for 10 to 30 hours, such as 20 hours. Then EtOAc and water are added. The aqueous phase is adjusted to pH 4, for example, by means of acetic acid or 98% strength H ₂ SO ₄ . The organic phase is extracted. Subsequently, the aqueous phase is optionally again washed with E- tOAc. The combined organic phases are dried, filtered and concentrated in vacuo. The residue is then processed further if necessary. For example, a fractional distillation is carried out. The cyclopentadecenones X of the invention can thereby be separated from unreacted cyclohexadec-8-enone. If appropriate, the cyclopentadecenones X can subsequently be separated by column chromatography from low-boiling components which have not been separated off by distillation. For example, silica gel is suitable as the stationary phase and the mobile phase is a mixture of cyclohexane: EtOAc, for example by elution using a step gradient 100: 1/30: 1/20: 1. The product is eluted at about 80: 1.

The invention will now be explained in more detail with reference to the following nonlimiting embodiments:

Experimental part

methods:

Gas chromatography (GC)

Separation column: CP-Wax 52CB 25m x 0.32mm x 1, 2μηΊ, 1ml / min N ₂

Conditions: 90 ° -5min-107min-240 ° -30min Inj / Det 2007250 ° (Method A)

Conditions: 80 ° -37min-250 ° - Inj / Det 2007250 ° (Method B) (Example 2 only)

Sample volume: 0.2 ml GC / MS

Separation column: CP-Wax 52 CB (1 .2 μηι film thickness), split ratio 10: 1

Conditions: 80 ° -3min-240 ° -30min 0.2μΙ

MS conditions: 25-785 amu, 70 eV

GC / IR

Detector: MCT / A wavelength 650 - 4000 cm ^"1

Cell / transfer temperature 250 ° C

Scan 6

Resolution 8

column A glass column with frit bottom was used. The column was packed to 2/3 with suspended silica gel F ₂₅ 4. The solvent mixture was forced through the column at an overpressure of 0.2-0.4 bar. Unless defined otherwise, "(E / Z) -C-cyclopentadec-8-enone" is understood to mean a mixture consisting of (E / Z) -cyclopentadec-8-enone (I) and / or (III) and their regioisomers (II ) and / or (IV).

Example 1: Preparation of a cyclohexadecenone / cyclopentadone mixture according to the invention

(EZ) -cyclohexa (BZ) -cyclopentadec-8- (EZ) -cyclohexa (BZ) -cyclopentadec-8-enone-enylcarbaldehyde dec-8-enone-dec-8-enone

and regioisomers

(XI) (X)

100 g of a mixture consisting of 81% (E / Z) -Cyclohexadec-8-enone (Globanon ^®) and 5.9% Cyclopentadec-8-enylcarbaldehyd (for example prepared according to the PCT / EP2015 / 072 544 of the applicant) was dissolved in 300 ml DMF , To the mixture was added 2.3 g of diazabicycloundecene (DBU, 15.2 mmol, 0.6 eq). Through the mixture, an air stream was passed continuously. TM EDA (120 mg, 0.5 mmol, 2 mol%) and Cu (OAc) ₂ (90 mg, 0.5 mmol, 2 mol%) were dissolved in 30 ml of DMF. The Cu-TMEDA mixture was added dropwise via a syringe pump continuously for 6 h or in a batch of the reaction solution. The reaction was stirred at 50 ° C for 20 h. Subsequently, 300 ml of EtOAc were added and 200 ml of water. The aq. Phase is adjusted by means of 98% H ₂ S0 ₄ to pH 4. The organic phase was extracted. The aqueous phase was then washed once more with EtOAc (2 × 100 ml). The united org. Phases were dried over Na ₂ S0 ₄ , filtered off and concentrated in vacuo. The turnover of the carbaldehydes was> 95%. The selectivity of the cyclopentadecenones was 95%. Cyclohexadec-8-enone was not attacked. The residue was purified by fractional distillation in a rotary column column with a number of stages of 20 at 1 mbar top pressure and 125-129 ° C head and 170-180 ° C bottom temperature worked up. The reflux ratio was 75. The cyclopentadec-7/8-enone was separated from cyclohexadec-8-enone (yield 85%). The cyclopentadec-7/8 enones were separated by column chromatography after the addition of low boilers which could not be separated in the distillation (silica gel, eluent cyclohexane: EtOAc 100: 1, 30: 1, 20: 1) that 1 g of a colorless oil with a purity of 84% (3.7 mmol) could be obtained.

Proportion: (E) -cyclopentadec-8-enone (I) = 54%

(Z) cyclopentadec-8-enone (III) = 30%

Regioisomer of (I) = 0.45%

¹ H NMR (500 MHz, CDCl _3, 25 ° C): σ = 5.3 (m, 2H), 2.5-2.3 (m, 4H), 2.1 -1 .9 (m, 4H), 1.7-1.55 (m, 4H), 1 .45-1 .10 (m, 12H) (of the mixture) of iran-cyclopentadec-8-enone I

¹³ C-NMR (125 MHz, CDCl ₃ , 25 ° C): σ = 21 1 .98 (C = 0), 130.99 (C = C), 41.49 (2xCH ₂ ), 31.80 (2xCH ₂ ), 28.26 (2xCH ₂ ), 28.21 (2xCH ₂ ), 26.84 (2xCH ₂ ), 26.83 (2xCH ₂ ), 22.91 (2xCH ₂ ). c / s-cyclopentadec-8-enone III

¹³ C-NMR (125 MHz, CDCl ₃ , 25 ° C): σ = 21 1 .93 (C = 0), 130.44 (C = C), 41.57 (2xCH ₂ ), 31.80 (2xCH ₂ ), 28.48 (2xCH ₂ ), 27.68 (2xCH ₂ ), 25.74 (2xCH ₂ ), 23.16 (2xCH ₂ ).

MS m / z = 222, 204, 179, 165, 152, 135, 125, 11 1, 98, 81, 67, 55, 41. iran-cyclopentadec-8-enone I

IR (ATR) u [cm ^-1 ] = 3022, 2934, 2864, 1724, 1449, 1356, 1 121, 969. c / ^' s cyclopentadec-8-enone III

IR (ATR) u [crrf ¹ ] = 301 1, 2935, 2866, 1723, 1456, 1354, 716.

In the GC, another compound was found in the mixture, whose mass and IR spectrum for irans-cyclopentadecenone II speaks. The proportion was 0.45% For a spectroscopic evaluation of the compound, however, not enough material was available. By GC / MS-IR the compound could be identified: frans-cyclopentadecenone II

IR (ATR) υ [cm ^-1 ] = 3020, 2934, 2864, 1723, 1449, 1353, 969.

In addition, it was possible to identify compound IV from a further reaction mixture (prepared according to applicant's PCT / EP2015 / 072544, synthesis route 2 or example 5 there by means of GC / MS-IR): c / ^' s-cyclopentadecenone IV

IR (ATR) υ [cm ^-1 ] = 3012, 2936, 2866, 1723, 1457, 1353, 714.

Example 2 Olfactory Evaluation of a Cyclohexadecenone / Cyclopentadecenone Mixture According to the Invention Odor Test: Green, aldehydic, harsh, gaseous, to musk (84% cyclopentadec-8-enone)

Example 3: Preparation of a cyclohexadecenone / cyclopentadecenone mixture according to the invention

970 g of a mixture of (E / Z) -cyclohexadec-8-enone (globanone, 84%) and cyclopent-8-enylcarbaldehyde (XI, 1.5%, 0.52 mol) were dissolved in 944 g of DMF. To the solution was added 47.3 g of DBU (0.31 mol, 0.6 eq) and heated to 50 ° C. An air stream was continuously passed through the solution. 4.7 g of Cu (AcO) ₂ (25.9 mmol, 5 mol%) and 3.01 g of TMEDA (25.9 mmol, 5 mol%) dissolved in 150 ml of DMF were added dropwise to the solution by means of a syringe pump over a period of 6 h. The solution was stirred in total for 20 h at 50 ° C. Subsequently, 500 ml of water and 8 ml of 98% H ₂ S0 ₄ (pH 5) were added and 500 ml of EtOAc. The phases were stirred vigorously for 10 minutes and separated. Thereafter, the aq. Phase again extracted with 500 ml EtOAc. The united org. Phases were with sat. NaHC0 ₃ solution, dried over Na ₂ S0 ₄ , filtered off and concentrated. 969 g of a dark brown residue comprising globanone (83%), (E / Z) cyclopentadec-8 enone (I, III, 11.5%) and regioisomers of I and III (0.3%). This was purified by distillation.

Example 4 Pure Purification (E / Z) -Cyclopentadec-8-enone (I, III) and its Regioisomers:

First, the reaction product from Example 3 (969 g of (E / Z) cyclopentadec-8-enone and its regioisomers (1.8%)) was separated by short path evaporation at 240 ° C in heat transfer oil of the evaporator surfaces and 5 mbar of high boilers. Subsequently, the distillate was separated from the low boilers by means of batch distillation. The theoretical number of stages of the fabric packs used Sulzer DX was 50. It was worked at a top pressure of 10 mbar with a differential pressure across the column of 8 mbar. For the separation of the (E / Z) -cyclopentadec-7/8-enone, the reflux ratio was 50. The cyclopentadec-7/8-enone were fractionally distilled. After separation, the reflux ratio for the distillation of the cyclohexadec-8-enone was reduced to 20. The bottom temperature rose during the distillation of 204 to 220 ° C. The head temperature rose from 160 to 175 ° C.

By means of fractional distillation, the purity of (E / Z) -cyclopentadec-8-enone and its regioisomers s.o. from 1 1 .7% to 94-98% (FI .-%). The ratio of trans to cis-cyclopentadec-8-enone was 4: 1 (CHF 3) and 2: 1 (CHF 4).

Example 5 Olfactory Classification of the 98% Cyclopentadecenone Sample Samples "Fr 3" and "Fr.4" from Example 4

Intensity 4

Musk 6

Sweet, powdery 4

Dried fruit 2

Example 6: Preparation of a cyclohexadecenone / cyclopentadecenone mixture according to the invention in the absence of a solvent

400 g of a mixture consisting of 81% (E / Z) -cyclohexadec-8-enone and 5.9% cyclopentadec-8-enylcarbaldehyde (prepared, for example, according to the Applicant's PCT / EP2015 / 072544) were mixed with 18.5 g of diazabicycloundecene (DBU, 121 .8 mmol, 0.6 eq), 0.6 g of TMEDA (5.1 mmol, 2.5 mol%) and 0.92 g of Cu (OAc) ₂ (5.1 mmol, 2.5 mol%). The reaction mixture was heated to 50 ° C and through the mixture was continuously a stream of air (100 Nl / h) gelei- tet. The mixture was stirred for 4 h. Then, 200 ml of EtOAc, 200 ml of water and 43.4 g of AcOH were added at room temperature, and the mixture was stirred for 5 minutes. The phases were separated and the aqueous phase was extracted once more with 200 ml EtOAc. The combined organic phases were dried over Na ₂ S0 ₄ , filtered and concentrated. The sales of carbohydrates was 97%. The selectivity of cyclopentadecenone was 85%. The loss of cyclohexadec-8-enone was only 0.2%.

Reference is expressly made to the disclosure of the references mentioned herein.

Claims

claims Process for the preparation of a macrocyclic keto compound of the general formula

wherein A is a cycloaliphatic hydrocarbon radical having m ring carbon atoms, wherein m is an integer value of 13 to 17, and optionally n C = C double bonds, where n is an integer value of 1, 2 or 3, wherein a ) a cycloaliphatic carbaldehyde compound of the formula XI

wherein A has the meanings given above, is oxidatively decarbonylated; reacting the compound of formula XI in the presence of a Cu (II) catalyst and molecular oxygen; and optionally b) isolating at least one compound of the formula X from the reaction mixture.

The process of claim 1 wherein the catalyst is formed in situ by adding a ligand to a Cu (II) salt. Method according to one of the preceding claims, wherein in the compounds of the formula X and XI m is 15 and / or n is 1.

Process according to one of the preceding claims, wherein (E / Z) cyclopentadec-8-enyl-1-carbaldehyde or a mixture of (E / Z) -cyclopentadec-8-enyl and (E / Z) -cyclopentadec-7 enyl-1-carbaldehyde or a substance mixture containing this compound.

Process according to claim 4, wherein at least one compound chosen from (E / Z) -cyclopentadec-8-en-1-one and its regioisomers are obtained.

A process as claimed in claim 5, wherein at least one compound is selected from compounds of the following formulas I and III and regioisomers thereof, in particular of the formulas II and IV

(8E) -cyclopentadec (7E) -cyclopentadec (8Z) -cyclopentadec (7Z) -cyclopentadec-8-en-1-one 7-en-1-one 8-en-1-one 7-ene-1 -one

I II III IV

receives.

Process according to one of the preceding claims, wherein a reaction product which is obtained from the dinitrogen monoxide oxidation of a cycloaliphatic compound of the formula XII is used in stage a)

(XII) where A 'is a cycloaliphatic hydrocarbon radical having m + 1 ring carbon atoms, m being an integer from 13 to 17, and optionally n + 1 C = C double bonds, and wherein n is an integer value of 1, 2 or 3.

The process of claim 7, wherein in the compound of formula XII, m is 15 and n is 1.

The process of claim 8 wherein the compound of formula XII is cyclohexadeca-1,9-diene.

10. A process for the preparation of Globanon ((E / Z) -cyclohexadec-8-en-1-one), wherein

Cyclohexadeca-1, 9-diene with dinitrogen monoxide oxidized to obtain a reaction mixture which comprises a mixture comprising globanone and at least one cyclopentadecenyl-carbaldehyde compound, in particular selected from (E / Z) -cyclopentadec-8-enyl-1-carbaldehydes contains; optionally separating unreacted cyclohexadeca-1, 9-diene;

subjecting the reaction mixture of step a) to an oxidative decarbonylation reaction according to any one of claims 1 to 2; and

Globanon of the resulting cyclopentadecenones, in particular the resulting cyclopentadecenones I and III and optionally the regio- isomers II and / or IV or mixtures thereof.

1 1. Method according to one of the preceding claims, wherein the oxidative decarbonylation takes place in the presence or absence of a solvent.

13. A mixture according to claim 12, comprising at least two compounds selected from (E / Z) -cyclopentadec-8-en-1-one and their regioisomers.

14. A composition according to claim 13, comprising at least two compounds selected from compounds of the following formulas I and III and optionally regioisomers thereof, in particular of the formula II:

or comprising at least two compounds selected from compounds of the following formulas I and III and optionally regioisomers thereof, such as in particular of the formulas II and IV

(8-C-Clopentadec-7-C-clopentadec-8Z-C-clopentadec-7Z-C-clopentadec-8-en-1-one 7-en-1-one 8-en-1-one 7 -en-1-one

I II III IV

15. Use of at least one substance or mixture according to any one of claims 1 1 to 14 as Aromachemikalie, in particular as a fragrance.

Use according to claim 15 of a mixture, essentially containing (E) - cyclopentadec-8-en-1-one (I) and (Z) -cyclopentadec-8-en-1-one (III).

17. Use according to claim 16, wherein the molar ratio of (I) to (III) is in the range of about 1: 1 to about 5: 1

18. Use according to any one of claims 15 to 17 for producing a musk note in a fragrance composition.

19. A fragrance composition comprising at least one substance or a mixture of substances as defined in any one of claims 12 to 14 or prepared by one of the processes according to claims 1 to 11. 20. Composition comprising at least one substance or a mixture of substances as defined in any of claims 12 to 14 or prepared by one of the processes according to claims 1 to 11.