EP2861552A1

EP2861552A1 - Method for producing macrocyclic ketones

Info

Publication number: EP2861552A1
Application number: EP13729318.9A
Authority: EP
Inventors: Richard Dehn; Joaquim Henrique Teles; Michael Limbach; Stephan Deuerlein; Manuel Danz; Ralf Pelzer; Daniel Schneider
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2012-06-13
Filing date: 2013-06-12
Publication date: 2015-04-22
Also published as: JP2015525225A; MX2014015264A; US20130338402A1; JP6290195B2; CN104379547B; US8940940B2; WO2013186238A1; CN104379547A; MX356142B

Abstract

The invention relates to a method for producing cyclic compounds having at least eight carbon atoms and at least one keto group, the cyclic compounds obtained according to said method, and the use of said cyclic compounds, in particular as an aromatic substance or to provide an aromatic substance.

Description

Process for the preparation of macrocyclic ketones

BACKGROUND OF THE INVENTION The present invention relates to a process for producing cyclic compounds having at least eight carbon atoms and at least one keto group, the cyclic compounds obtained by this process and their use, especially as a fragrance or to provide a fragrance. STATE OF THE ART

There is a need for effective processes for preparing middle and especially large ring based cyclic compounds having at least one keto group. Medium rings usually have 8 to 1 1 carbon atoms, from 12 carbon atoms are called large rings, and compounds based on large rings are also referred to as macrocyclic compounds. Macrorocyclic ketones, lactones and epoxides, as well as other functionalized macrocycles, are sought-after aroma chemicals in the fragrance industry. Important representatives are z. Muskon (1), (E / Z) -8-cyclohexadecenone (2), cyclohexadecanone (3) or

9-hexadecene-16-olide (4).

The known processes for the preparation of cyclic ketones are usually associated with a considerable synthetic effort. For example, in Synthesis 1999, 10, 1707-1723, AS Williams reviews the synthesis of macrocyclic moieties. scatterbrained connections. Thereafter, for example, the preparation of Muskon (1) in a multistage synthesis starting from cyclododecanone by ring expansion.

DE 101 42 032 A1 describes the preparation of cycloalkadienes from cycloalka monoenes, cyclopolyenes, acyclic polyenes or mixtures thereof by metathesis reaction in the presence of a Re 207 y-Al 2 O 3 catalyst. Specifically, the preparation of 1, 9-cyclohexadecadiene from cyclooctene is described.

B. Mookherjee et al. Describe in J. Org. Chem. 36, 22 (1971), 3266-3270, the synthesis of racemic Muskon and cyclopentadecanone (Exalton) starting from 1, 9-cyclohexadecadiene. The synthesis involves a complex reaction sequence which includes, inter alia, an epoxidation and a rearrangement step.

EP 0 322537 A2 describes a process for the preparation of cyclic ketones by isomerization of epoxides in a polar solvent in the presence of alkali or alkaline earth halides.

US 5,936,100 describes the synthesis of functionalized macrocycles by ring-closing metathesis. Thus, for example, the synthesis of 9-hexadecene-16-olide (D) by ring-closing metathesis of 10-undecenyl 5-hexenyl ester. The Eduktdien is technically only poorly available.

Paul R. Story and P. Busch describe in "Modern methods for the synthesis of macrocyclic compounds", Adv. Org. Chem. 1972, 8, 67-95, various synthetic routes, inter alia, by ring expansion, ring reduction, 1, 2 -Cycloaddition, etc. The so-called "story synthesis" includes the formation and decomposition of corresponding peroxides, which is associated with correspondingly high synthetic and safety effort. The known processes for the preparation of cyclic compounds having at least eight, especially at least 12, ring carbon atoms are either multistage syntheses or are based on industrially difficultly available starting materials.

Cyclododecanone is an important intermediate for the production of lauryl lactam, dodecanedicarboxylic acid and derived polyamides. For the preparation of cyclododecanone 1, 5,9-cyclododecatriene an oxidation, especially an oxidation with N2O, be subjected to, is obtained as the main product cyclododeca-4,8-dienone, which then subjected to a selective hydrogenation to cyclododecanone becomes. Such methods are described, for example, in WO 2005/030690,

WO 2008/000754 and WO 2010/086314.

Surprisingly, it has now been found that starting from cyclododeca-4,8-dienone cyclic compounds having at least eight carbon atoms and at least one keto group can be prepared simply and effectively by metathesis reaction. In particular, it is possible to prepare a metathesis product which has a high proportion of macrocyclic ketones and diketones of the ring sizes Ci6, C20, C24 and higher homologs, each with four additional carbon atoms. This metathesis product is suitable, optionally after separation into fractions or substantially pure compounds, as a fragrance or to provide a fragrance. This process is also particularly advantageous since cyclododeca-4,8-dienone is available industrially in large quantities as an intermediate in the preparation of cycloiododecanone. In addition, only one synthesis step is required to obtain a product that can have a variety of interesting compounds. Thus, the metathesis products or fractions or substantially pure compounds thereof obtainable by the process according to the invention can also serve as valuable intermediates. They are suitable for further processing z. B. by hydrogenation, Baeyer-Villiger oxidation to macrocyclic lactones, synthetic building blocks of various specialty chemicals and fragrances, etc.

SUMMARY OF THE INVENTION

A first aspect of the invention is a process for preparing at least one cyclic compound having at least eight carbon atoms and at least one keto group, in which a) a cyclododeca-4,8-dienone-containing starting material is provided, and b) the starting material of an olefin Methathesis reaction in the presence of a

Transition metal catalyst undergoes.

Another object of the invention is a composition containing at least one cyclic compound having at least eight carbon atoms and at least one keto group and which is obtainable by the method described above and in the following. Another object of the invention is the use of at least one cyclic compound, which is obtainable by the method described above and below, as a fragrance or to provide a fragrance. Another object of the invention is a cosmetic composition, a consumer or commodity containing an organoleptically effective amount of at least one cyclic compound, which is obtainable by the method described above and in the following, as a fragrance. DESCRIPTION OF THE INVENTION

Step a)

In step a) of the process according to the invention, pure cyclododeca-4,8-dienone or a technically available cyclododeca-4,8-dienone-containing mixture can be used as cyclododeca-4,8-dienone-containing starting material.

Preferably, to provide the cyclododeca-4,8-dienone-containing starting material in step a) a 1, 5,9-cyclododecatriene-containing composition is used and subjected to oxidation to give an oxidation product, the cyclododeca-4.8 contains dienone.

1, 5,9-Cyclododecatriene can generally be used in the form of any possible isomer, for example, ice, trans, trans-1, 5,9-cyclododecatriene, cis, cis, trans-1, 5,9-cyclododecatriene, all-trans -1, 5,9-cyclododecatriene or all-cis-1, 5,9-cyclododecatriene. In step a) of the process according to the invention, it is also possible to use an isomer mixture which comprises at least two of the abovementioned isomers.

The 1,5,9-cyclododecatriene used in the process according to the invention can generally be obtained by all processes known to the person skilled in the art for its preparation. In a preferred embodiment, the 1, 5,9-cyclododecatriene is prepared by trimerization of butadiene.

1, 5,9-Cyclododecatrien, for example, by trimerization of pure

1, 3-butadiene, as described, for example, in T. Schiffer, G. Oenbrink, "Cyclododecatrienes, Cyclooctadienes, and 4-vinylcyclohexenes," in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition (2000), Electronic Release, Wiley VCH, pages 1 to 4, is described. In the context of this process, for example, in the case of trimerization in the presence of Ziegler catalysts, cis, trans, trans-1, 5,9- Cyclododecatriene, cis, cis, trans-1, 5,9-cyclododecatriene and all-trans-1, 5,9-cyclododecatriene, as described, for example, in H. Weber et al. "The formation of cis, trans, trans-1, 5,9-cyclododecatriene by means of titanium-containing catalysts" in Liebigs Ann. Chem. 681 (1965), pages 10 to 20. Cyclododecatriene can be prepared, for example, by trimerization of 1,3-butadiene using a titanium or nickel catalyst. This is described for example in DE 1283836.

A preferred titanium catalyst for the trimerization of butadiene is a titanium tetrachloride / ethylaluminum sesquichloride catalyst, as described, for. In H. Weber et al., Liebigs Ann. Chem. 681 (1965), pages 10 to 20.

A preferred nickel catalyst for the trimerization of butadiene is the bis-cyclooctadienyl nickel / ethoxydiethylaluminum catalyst described in DE 1283836.

The butadiene used for the trimerization preferably has a purity determined by gas chromatography of at least 99.5%. With particular preference, the 1,3-butadiene used contains no 1,2-butadiene and no 2-butyne within the scope of the accuracy of detection.

The mixtures obtained in the trimerization of butadiene preferably have at least 95 wt .-%, more preferably at least 96 wt .-%, in particular at least 97 wt .-% cis, trans, trans-1, 5,9-cyclododecatriene.

In a preferred embodiment, the 1, 5,9-cyclododecatriene-containing composition is subjected to oxidation with nitrous oxide. Such methods are described in WO 2005/030690, WO 2008/000754 and WO 2010/086314, to which reference is made in its entirety.

The nitrous oxide can be used in pure form or in the form of a gas mixture containing nitrous oxide. The term "gas mixture" in the context of the present invention refers to a mixture of two or more compounds which are in the gaseous state at ambient pressure and ambient temperature.

For the oxidation of the 1, 5,9-cyclododecatriene-containing composition in step a), the dinitrogen monoxide or the dinitrogen monoxide-containing gas mixture can be gas- shaped, in liquid form, in supercritical form or as a solution in a suitable solvent.

The oxidation of the 1, 5,9-cyclododecatriene-containing composition in step a) can be carried out in the presence or absence of a catalyst.

In a specific embodiment, the nitrous oxide is used in the form of a gas mixture obtained as the exhaust gas of another method, such as. In

WO 2006/032502, WO 2007/060160, WO 2008/071632, EP 08153953.8 and

EP 08153952.0. It can also be used a mixture of different exhaust gases. The dinitrogen monoxide is preferably used in the form of a gas mixture which is obtained as waste gas from an adipic acid plant, a dodecanedioic acid plant, a hydroxylamine plant and / or a nitric acid plant. If desired, the gas mixture containing dinitrogen monoxide may be subjected to a purification and / or concentration of the ISO content before it is used for the oxidation. A suitable purification process comprises, for example, the absorption of the gas mixture in an organic solvent or water, the desorption of the gas mixture from the loaded organic solvent or the charged water and the adjustment of the content of nitrogen oxides NOx in the gas mixture to at most 0.01 to 0.001 vol .-%, based on the total volume of the gas mixture. Such a method is described, for example, in DE 10 2004 046 167.8, to which reference is hereby made in its entirety.

The oxidation of the 1, 5,9-cyclododecatriene-containing composition with dinitrogen monoxide in step a) can be carried out without the addition of a solvent. If desired, the oxidation can also take place in the presence of a solvent which is inert under the reaction conditions. Essentially, all common solvents are suitable which have neither a C-C double bond nor a C-C triple bond nor an aldehyde group. These include z. As cyclic alkanes, for example cyclododecane or cyclododecanone or saturated aliphatic or aromatic, optionally alkyl-substituted hydrocarbons.

The temperature during the oxidation with dinitrogen monoxide is preferably from 140 to 350.degree. C., more preferably from 180 to 320.degree.

The pressure during the oxidation with dinitrogen monoxide is preferably higher than the autogenous pressure of the educt or product mixture at the selected reaction temperature or the selected reaction temperatures. The pressure is preferably 1 to 1000 bar, more preferably at 40 to 325 bar and in particular at 50 to

200 bar.

For oxidation with nitrous oxide, the molar ratio of nitrous oxide to 1,5,9-cyclododecatriene is generally in the range of 0.05 to 4, preferably in the range of 0.06 to 1, more preferably in the range of 0.07 to 0.5 and more preferably in the range of 0.1 to 0.4.

In the oxidation of the 1, 5,9-cyclododecatriene-containing composition with dinitrogen monoxide in step a), an oxidation product is obtained which contains the following components:

Cyclododeca-4,8-dienone,

optionally unreacted 1, 5,9-cyclododecatriene,

optionally at least one acyclic compound containing 12 carbon atoms which has at least one aldehyde group.

The oxidation product obtained in the oxidation of the 1, 5,9-cyclododecatriene-containing composition with dinitrogen monoxide in step a) can be subjected to separation to give a cyclododeca-4,8-dienone-enriched fraction and one of cyclododeca-4,8- dienon depleted fraction. The separation can be carried out by customary methods known to the person skilled in the art, preferably by distillation. A process for the distillative separation of such an oxidation product is described in detail in WO 2010/086314, which is incorporated herein by reference in its entirety.

In general, the preferred oxidation of cis, trans, trans-1, 5,9-cyclododecatriene with dinitrogen monoxide results in a cyclododeca-4,8-dienone isomer mixture containing at least two of the isomers cis, trans-cyclododeca-4,8 dienone, trans, cis -cyclododeca-4,8-dienone and trans, trans -cyclododeca-4,8-dienone. However, it is also possible to use further mixtures of isomers, as described, for. B. obtained by other oxidation methods.

Step b)

The metathesis reaction in step b) is preferably carried out at a temperature in the range from 0 to 200 ° C., particularly preferably from 10 to 150 ° C., in particular from 20 to 100 ° C.

The metathesis reaction can be in the liquid phase or in the gas phase. In a specific embodiment, in addition to cyclododeca-4,8-dienone, at least one further compound capable of participating in the metathesis reaction is used for the metathesis reaction in step b).

The further compound is generally selected from cyclododeca-4,8-dienone-different cyclic compounds having at least one C-C double bond. The further compound preferably has 1, 2 or 3 C-C double bonds.

If desired, the further compound may have at least one functional group. The carbon chain of the further compound is then preferably interrupted by one or more nonadjacent groups which are selected from -O-, -S-, -NR ^a -, -C (= 0) -, -S (= 0) - and / or or -S (= O) ₂ -, wherein R ^{a is} preferably hydrogen, alkyl, cycloalkyl or aryl. In a specific embodiment, the carbon chain of the further compound is interrupted by one or more nonadjacent keto groups. Particularly preferably, the further compound has no further functional group in addition to at least one C-C double bond.

In one possible embodiment, the metathesis reaction in step b) is additionally carried out in the presence of at least one cycloalkamonone or at least one cycloalkane polyene. Particularly preferably, the metathesis reaction is carried out in the presence of at least one cyclic oligobutadiene. In a specific embodiment, the metathesis reaction in step b) is carried out using, in addition to cyclododeca-4,8-dienone, at least one further compound which is capable of participating in the metathesis reaction and which is selected from 1,4-cyclooctadiene, 1,4,8- Cyclododecatriene and mixtures thereof. In a suitable embodiment, a starting material is used for the metathesis reaction in step b), which in addition to cyclododeca-4,8-dienone at least one further compound capable of participation in the metathesis reaction in an amount of 0.1 to 50 wt .-%, based to the total amount of cyclododeca-4,8-dienone and other compounds capable of participating in the metathesis reaction.

Specifically, for the metathesis reaction in step b), a starting material is used which contains at least one cycloalkamonone or at least one cycloalkapolyene in an amount of from 0.1 to 30% by weight, particularly preferably from 0.5 to 25% by weight, in particular from 1 to 20 wt .-%, based on the total amount of cyclododeca-4,8-dienone and cycloalcoholone or cycloalkapolyene.

More specifically, for the metathesis reaction in step b) a starting material is used, the 1, 4-cyclooctadiene and / or 1, 4,8-cyclododecatriene in an amount of 0.1 to 30 wt .-%, particularly preferably 0.5 to 25 Wt .-%, in particular 1 to 20 wt .-%, based on the total amount of cyclododeca-4,8-dienone and 1, 4-cyclooctadiene and / or 1, 4,8-cyclododecatriene contains. By adding appropriate compounds capable of participating in the metathesis reaction, the composition of the product of the metathesis reaction can be controlled. So z. As the use of suitable cyclic Oligobutadiene, such as 1, 4-cyclooctadiene and / or 1, 4,8-cyclododecatriene, to a higher proportion of monoketones in the product of the metathesis reaction.

The metathesis reaction in step b) is preferably carried out in the presence of a solvent which is inert under the reaction conditions. Suitable solvents are, for example, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, esters of aliphatic and aromatic carboxylic acids with alkanols and mixtures thereof. These include z. For example, n-pentane, n-hexane, n-heptane, n-octane, petroleum ether, ligroin, cyclopentane, cyclohexane, toluene, xylene, dichloromethane, chloroform, 1, 2-dichloroethane, ethyl acetate and mixtures thereof. It has been found that with increasing educt concentration in the reaction mixture used for metathesis increasingly cyclic compounds having a higher number of carbon atoms are formed. These are undesirable for use of the product of the metathesis reaction as a fragrance or to provide a fragrance.

Preferred for the metathesis reaction in step b) are cyclododeca-4,8-dienone and, if present, various cyclic compounds having at least one CC double bond, in a total concentration in the range from 0.01 to 1 mol / L, particularly preferably in one Total concentration in the range of 0.01 to 0.5 mol / L, used.

In principle, homogeneous and heterogeneous catalysts are suitable as metathesis catalysts. Preferably, the metathesis catalyst used in step b) comprises at least at least one transition metal of groups 6, 7 or 8 of the Periodic Table of the Elements, more preferably Mo, W, Re or Ru.

Suitable homogeneous metathesis catalysts for use in step b) of the inventive method z. As salts or complexes of tungsten or rhenium, z. For example, WCI6 or CH3Re (CO) 5 or metal-carbene complexes, which are preferably based on ruthenium or molybdenum. The catalysts based on Re, Mo or W are often used in combination with a co-catalyst, for. As an organometallic complex of a main group element, such as aluminum alkyls, Aluminiumalkylchloride or zinc alkyls. The catalysts based on Re, Mo or W are furthermore frequently used in combination with an activator, for example an oxygen-containing compound, such as ethanol or diethyl ether.

In a first preferred embodiment, in step b) a homogeneous catalyst is used which comprises at least one ruthenium-alkylidene complex, preferably a ruthenium-alkylidene complex which additionally has at least one N-heterocyclic carbene as ligand.

In the context of the present invention, the term "alkyl" includes straight-chain or branched alkyl. Alkyl is preferably C 1 -C 20 -alkyl, in particular C 1 -C 12 -alkyl and very particularly preferably C 1 -C 6 -alkyl. Examples of alkyl groups are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.

Substituted alkyl groups may have one or more (eg, 1, 2, 3, 4, 5 or more than 5) substituents depending on the length of the alkyl chain.

Aryl-substituted alkyl radicals ("arylalkyl" or "aralkyl") have at least one unsubstituted or substituted aryl group as defined below. each

Aryl group preferably has 6 to 14, preferably 6 to 10, carbon atoms, and the alkyl part in aralkyl preferably has 1 to 20, preferably 1 to 12 carbon atoms. Arylalkyl is, for example, phenyl-Ci-Cio-alkyl, preferably phenyl-Ci-C4-alkyl, for. Benzyl, 1-phenethyl, 2-phenethyl, 1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut-1 -yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl , 1 - (phenmeth) -eth-1-yl, 1 - (phen-methyl) -1 - (methyl) -eth-1-yl or 1 - (phen-methyl) -1 - (methyl) -prop-1-yl; preferably for benzyl and 2-phenethyl. In the context of the invention, "cycloalkyl" denotes a cycloaliphatic radical having preferably 3 to 10, particularly preferably 5 to 8, carbon atoms. Examples of cycloalkyl groups are in particular cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The term "aryl" in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals having usually 6 to 18, preferably 6 to 14, particularly preferably 6 to 10, carbon atoms. Examples of aryl are in particular phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, etc., and especially phenyl or naphthyl.

Substituted aryls may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the number and size of their ring systems. These are preferably selected independently from among alkyl, cycloalkyl and aryl. The alkyl, cycloalkyl and aryl substituents on the aryl may in turn be unsubstituted or substituted. Reference is made to the substituents previously mentioned for these groups. An example of substituted aryl is substituted phenyl, which generally carries 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents.

Substituted aryl is preferably aryl ("alkylaryl") substituted by at least one alkyl group. Each alkyl group usually has 1 to 20, preferably 1 to 12, carbon atoms, and the aryl part in alkaryl has 6 to 14, preferably 6 to 10, carbon atoms. Alkylaryl groups may have one or more (eg 1, 2, 3, 4, 5, 6, 7, 8, 9 or more than 9) alkyl substituents depending on the size of the aromatic ring system. The alkyl substituents may be unsubstituted or substituted. The previous information on unsubstituted and substituted alkyl is referred to in this regard. In a preferred embodiment, the alkylaryl groups have exclusively unsubstituted alkyl substituents. Alkylaryl is preferably phenyl which carries 1, 2, 3, 4 or 5, preferably 1, 2 or 3, particularly preferably 1 or 2, alkyl substituents having 1 to 12 carbon atoms.

The expression "heteroaryl" (hetaryl) in the context of the present invention encompasses heteroaromatic, mononuclear or polynuclear groups. These have in addition to the ring carbon atoms 1, 2, 3, 4 or more than 4 ring heteroatoms. The heteroatoms are preferably selected from oxygen, nitrogen, and sulfur. The hetaryl groups preferably have 5 to 18, z. B. 5, 6, 8, 9, 10, 1 1, 12, 13 or 14, ring atoms. The term "heterocycloalkyl" in the context of the present invention comprises non-aromatic, unsaturated or fully saturated, cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms. In the heterocycloalkyl groups 1, 2, 3, 4 or more than 4 of the ring carbon atoms are replaced by heteroatoms or heteroatom-containing groups over the corresponding cycloalkyl groups. The hetero atoms or heteroatom-containing groups are preferably selected from -O-, -S-, -NR ^C -, -C (= O) -, -S (= O) - and / or -S (= O) ₂ -. R ^c is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Examples of heterocycloalkyl groups are in particular pyrrolidinyl, piperidinyl,

2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, dihydro-2-yl, tetrahydrofuranyl, dihydrofuran-2-yl, tetrahydropyranyl,

1, 2-oxazolin-5-yl, 1, 3-oxazolin-2-yl and dioxanyl. Preferred is a method according to the invention, wherein the ruthenium-carbene complex is a compound d

(Xi) (X2) (

wherein each may be the same or different and each represents an anionic ligand, may be the same or different and each represents a neutral electron donor ligand, may be the same or different and each represents hydrogen or a Ci-C4o-carbon-containing radical, or two or more of the ligands or radicals selected from the group consisting of X ¹ , X ² , L ¹ , L ² , L ³ R ¹ and R ² are joined together and form a monocyclic or polycyclic ring system,

0 or 1 is and

0, 1 or 2 is.

X ¹ , X ² may be the same or different. In particular, X ¹ and X ^{2 are the} same. Preferably, X ¹ and X ^{2 are} independently selected from halogen, pseudo-halogen halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkyloxy, aryl or aryloxy. In particular, X ¹ and X ^{2 are} independently selected from fluorine, chlorine, bromine, iodine, cyano, thiocyano, methyl, ethyl, phenyl, phenyloxy, methyloxy or ethyloxy. Particularly preferably, X ¹ and X ^{2 are} both chlorine.

L ¹ , L ² , L ³ may be the same or different and each represents a neutral electron donor ligand. Preferred neutral electron donor ligands are described in WO 2010/021740, page 16, paragraph 0070, and page 17, paragraph 0075, the cited document being fully incorporated in the present disclosure. Particularly preferred neutral electron donor ligands are with two atoms of the 15th or 16th group of the Periodic Table of the Elements, in particular with two nitrogen atoms stabilized carbenes (so-called Arduengo carbenes), and ethers, thio-ethers, amines or nitrogen-containing heterocycles, in particular pyridine or pyridine - private.

R ¹ , R ² may be the same or different and each represents hydrogen or a Ci-C4o-carbon-containing radical, such as Ci-C2o-alkyl, C2-C2o-alkenyl, C ₂ -C ₂ o-alkynyl, C ₆ -C ₄ o-aryl, C ₇ -C ₄ o-alkylaryl, C ₇ -C ₄ o-arylalkyl, C ₅ -C ₄ o-hetaryl, C ₅ -C 20 heterocycloalkyl or a silyl radical having 3 to 24 carbon atoms. In this case, the carbon-containing radical may contain further heteroatoms selected from the group of elements consisting of F, Cl, Br, I, N, P, O and S and / or may be substituted by functional groups.

Two or more of the ligands or groups selected from the group consisting of X ^1, X ^2, L ^1, L ^2, L ^3, R ¹ and R ² may also be joined together to form a mo- nocyclisches or polycyclic ring system. Preferably, exactly one of the radicals L ¹ , L ² or L ^{3 is} bonded together with exactly one of the radicals R ¹ or R ² , and these together form a monocyclic or polycyclic ring system. N is preferably 0. Preferably, m is 0.

In a suitable embodiment, n is 0 and L ¹ and L ^{2 are} independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine and thioether. In particular, n is 0 and L ¹ and L ^{2 are} independently selected from pyridine or pyridine derivatives. In the process according to the invention, it is particularly preferable to use a ruthenium-carbene complex of the formula (A) in which the neutral electron donor ligand L ^{1 represents} a carbene of the formula (B),

wherein

X, Y may be identical or different, preferably the same, and in each case a heteroatom selected from the group of elements consisting of N, O, S and P, preferably N, mean, p is 0, if X is O or Is S, and p is 1 if X is N or P, 0 if Y is O or S, and p is 1 if Y is N or P,

Q ^2, Q ^3, Q ⁴ are each independently a divalent organic group having 1 to 40 carbon atoms, and in addition, two or more substi- tuenten on adjacent atoms within Q ^1, Q ^2, Q ³ and / or Q ⁴ are interconnected to form an additional monocyclic or polycyclic structure, w, x, y, z are independently 0 or 1, and

R ³ , R ^3A , R ⁴ , and R ^{4A may be the} same or different and each independently represent hydrogen or a Ci-C4o-carbon-containing radical.

R ^3, R ^3A; R ⁴ and R ^4A may be identical or different and each independently of one another denote hydrogen or a C 1 -C 4 -carbon-containing radical, such as, for example, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 5 -C 4 -oaryl Aryl, C7-C4o-alkylaryl, C7-C4o-arylalkyl, C2-C4o-heteroaromatic radical, saturated C3-C2o-heterocyclic radical or silyl radical having 3 to 24 carbon atoms, wherein the carbon-containing radical further heteroatoms selected from the group of elements consisting of F, Cl, Br, I, N, P, O and S may contain and / or be substituted with functional groups. In the carbenes of the formula (B), w, x, y and z are preferably all 0.

Q ¹ , Q ² , Q ³ , Q ⁴ are preferably each independently a divalent hydrocarbon group, a substituted divalent hydrocarbon group, a divalent heteroatom-containing hydrocarbon group, a substituted and heteroatom-containing divalent hydrocarbon group or - (CO) -.

Very particular preference is given to using in the process according to the invention a ruthenium-carbene complex of the formula (A) in which the neutral electron donor ligand L ^{1 is} a carbene of the formula (B) in which m is 0, w, x, y, z each equal to 0, p, q are each equal to 1,

X, Y is N, and

R ^3A and R ^4A are joined together and together form a divalent organic

Form Q with 1 to 40 carbon atoms.

An especially preferred ruthenium-carbene complex is the compound of general formula (C)

wherein X ¹ , X ² , L ² , L ³ , R ¹ , R ² , R ³ , R ⁴ and n have the meanings given above, and

Q is a divalent organic group having 1 to 40 carbon atoms.

In the ruthenium-carbene complex of the formula (C), the neutral electron donor ligand L ^{2 is} preferably phosphite, phosphinite, arsine, stibane, ether, amine, amide, imine, sulphoxide, carboxylate, nitrosyl, pyridine, substituted pyridine, Imidazole, substituted imidazole, pyrazine, thioether or pyrrolidone. Q is, for example, a divalent hydrocarbon group, a substituted divalent hydrocarbon group, a divalent heteroatom-containing hydrocarbon group or a substituted and heteroatom-containing divalent hydrocarbon group.

In the ruthenium-carbene complex of the formula (C) may be any combination of two or more of the groups X ^1, X ^2, L ^2, L ^3, R ¹ R ^2, R ³ and R ⁴ may be joined together to form cyclic structures, ,

Ruthenium alkylidene complexes useful as metathesis catalysts are further the second generation "Grubbs" catalysts, as disclosed, for example, in RH Grubbs, Handbook of Metathesis, Vol. 1, p. 128, Wiley-VCH, 2003. In these "Grubbs Second-generation catalysts are catalysts bearing N-heterocyclic carbene ligands alongside or in place of the phosphane ligands. An example of a suitable second generation "Grubbs" catalyst is

Cy = cyclohexyl,

Mes = 2,4,6-trimethylphenyl.

Such catalysts are also described in US 6,759,537, which is incorporated herein by reference.

Rutheniumalkylidenkomplexe suitable as metathesis catalysts continue to be the "Hoveyda Grubbs' -Katal catalysts

Such catalysts are also described in US Pat. No. 6,921,735, which is incorporated herein by reference.

Suitable metal complexes having a carbene ligand and methods for their preparation are also described in WO 99/00396, which is incorporated herein by reference.

Suitable ruthenium-alkylidene complexes which have an N-heterocyclic carbene as ligand and processes for their preparation are also described in WO 99/51344, which is hereby incorporated by reference in its entirety. These are, for example, compounds of the general formula (D)

(D)

wherein

X ¹ and X ^{2 are} identical or different and denote an anionic ligand,

X ³ and X ^{4 are the} same or different and are a chemical bond or are selected from -O-, -S-, -NR ^d -, -C (= 0) -, -S (= 0) - and / or -S (= O) ₂ -, where R ^{d is} hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,

R ^a and R ^{b are the} same or different, wherein R ^a and R ^b together with the carbon atom to which they are attached can form a cycle, and

R ^a and R ^b independently of one another represent hydrogen, in each case straight-chain or branched C 1 -C 6 -alkyl, C 2 -C 5 -alkenyl, C 2 -C 5 -alkynyl, C 5 -C -cycloalkyl, C 6 -C 30 -aryl or silyl, where d-Cso-alkyl, C 2 -C 30 -alkenyl, C 2 -C 30 -alkynyl, C 5 -C 8 -cycloalkyl, C 6 -C 30 -aryl or silyl radicals one or more or all of the hydrogen atoms independently of one another by an alkyl, Aryl, alkenyl, alkynyl, metallocenyl, halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio or / and sulfonyl group can be replaced, L ^{1 is} an N-heterocyclic carbene of the general formulas E.1 to E.8 and L ^{2 is} a neutral electron donor, in particular an N-heterocyclic carbene of the general formulas E.1 to E.4 or an amine, imine, phosphine, Phosphite, stibine, arsine, carbonyl compound, carboxyl compound, nitrile, alcohol, ether, thiol or thioether,

(E.1) (E.2) (E.3) (E.4)

(E.5) (E.6) (E.7) (E.8) where R ¹ , R ² , R ³ and R ⁴ in the formulas E.1, E.2, E.3, E.4 , E.5, E.6, E.7 and E.8 are identical or different and R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, in each case straight-chain or branched C ₁ -C 8 -alkyl, C ₂ -C ₅ o-alkenyl, C ₂ -C ₅ o-alkynyl, C ₅ -C ₈ -cycloalkyl, C ₆ -C ₃ o-aryl or silyl, where in the d-Cso-alkyl, d-dicarboxylic Alkenyl, d-do-alkynyl, Cs-Cs-cycloalkyl, C6-C3o-aryl or silyl radicals one or more of the hydrogen atoms independently by an alkyl, aryl, alkenyl, alkynyl, metallocenyl, halogen -, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio or / and sulfonyl group may be replaced, wherein at least one of the radicals R ³ and R ^{4 may} also be a halogen, nitro, nitroso, alkoxy, aryloxy, amido, carboxyl, carbonyl, thio-silyl or / and sulfonyl group. Suitable ruthenium-alkylidene complexes which have an N-heterocyclic carbene as ligand and processes for their preparation are also described in EP 1 022 282 A2, which is hereby incorporated by reference in its entirety. These are compounds of the general formula (E)

(E)

wherein X is an anionic ligand,

Y is a mono- to tridentate ligand containing a metal non-ionically bound to the ruthenium center,

R ^a and R ^b independently of one another represent hydrogen, in each case straight-chain or branched C 1 -C 6 -alkyl, C 2 -C 5 -alkenyl, C 2 -C 5 -alkynyl, C 5 -C -cycloalkyl, C 6 -C 30 -aryl or silyl, where Ci-Cso-alkyl, C2-Cso-alkenyl, C2-Cso-alkynyl, Cs-Cs-cycloalkyl, C6-C3o-aryl or silyl radicals one or more or all of

Hydrogen atoms independently of one another by an alkyl, aryl, alkenyl, alkynyl, metallocenyl, halogen, nitro, nitroso, hydroxyl, alkoxy, aryloxy, amino, amido, carboxyl, , Carbonyl, thio or / and sulfonyl group may be replaced,

L is an N-heterocyclic carbene of the general formulas E.1 to E.8,

(E.1) (E.2) (E.3) (E.4)

(E.5) (E.6) (E.7) (E.8) where R ¹ , R ² , R ³ and R ⁴ in the formulas E.1, E.2, E.3, E.4 , E.5, E.6, E.7 and E.8 are identical or different and R ¹ , R ² , R ³ and R ⁴ independently of one another are hydrogen, in each case straight-chain or branched C 1 -C 8 -alkyl,

C ₂ -C ₅ o-alkenyl, C ₂ -C ₅ o-alkynyl, C ₅ -C ₈ -cycloalkyl, C ₆ -C ₃ o-aryl or silyl, where in the d-Cso-alkyl-, d- do-alkenyl, d-do-alkynyl, Cs-Cs-cycloalkyl, C6-C30-aryl or silyl radicals, one or more of the hydrogen atoms independently of one another by an alkyl, aryl, alkenyl, alkynyl, metallocenyl Halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl,

Carbonyl, thio or / and sulfonyl group may be replaced, wherein at least one of R ³ and R ^{4 is} also a halogen, nitro, nitroso, alkoxy, aryloxy, amido, carboxyl, carbonyl, Thio, silyl or / and sulfonyl group can stand.

Suitable 5-fold coordinated metal complexes which have a carbene ligand and processes for their preparation are also described in WO 03/062253, which is incorporated herein by reference in its entirety. These are complexes containing a carbene ligand, a multidentate ligand, and at least one sterically hindered ligand.

Suitable Rutheniumalkylidenkomplexe and methods for their preparation are also z. As described in WO 2007/003135, which is incorporated herein by reference in its entirety.

Suitable Rutheniumalkylidenkomplexe and methods for their preparation are also z. As described in WO 2008/065187, which is incorporated herein by reference in its entirety.

WO 2009/097955, to which reference is made in its entirety, describes photoactivatable, latent catalysts of the general formula

Ru (NHC) _n (X ¹ ) m (L) ₀ P ⁺ + ((X ² ) -) p in which

NHC is an N-heterocyclic carbene,

n = 1 or 2;

X ^{1 represents} a Ci-Ci8 mono- or polyhalogenated carboxylic acid or trifluoromethanesulfonate;

X ² denotes a C 1 -C 18 -mono- or polyhalogenated carboxylic acid, trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate or hexafluoroantimonate;

m is 0, 1 or 2;

L = a C4-C18-carbonitrile or a C4-C18-carboxylic acid di-or -trinitrile; o = 6 - n - m or 5 - n - m is and

p = 2 - m.

Ruthenium alkylidene complexes suitable as metathesis catalysts are also the so-called "Grubbs" catalysts of the first generation, eg of the formula

Cy = cyclohexyl. Such catalysts are also described in US 5,969,170 and US 6,111,112, which is incorporated herein by reference.

In step b), the catalyst used is preferably at least one ruthenium-alkylidene complex which is selected from dichloro (3-methyl-2-butenylidene) bis (tricyclopentylphosphine) ruthenium (II), isopentenylidene (1,3-dimesitylimidazolidin-2-ylidene) - (tricyclohexylphosphine) ruthenium (II) dichloride, benzylidene bis (tricyclohexylphosphine) dichlorotruthenium, 1, 3-bis (2,4,6-trimethylphenyl) -2 (imidazolidinylidene) dichloro (phenylmethylene) (tricyclohexylphosphine ) ruthenium, dichloro (o-isopropoxyphenylmethylene) - (tricyclohexylphosphine) ruthenium (II), (1,3-bis- (2,4,6-trimethylphenyl) -2-imidazoli- dinylidene) dichloro (o-isopropoxyphenylmethylene) ruthenium, 1 , 3-bis (2-methylphenyl) -2-imidazolidinylidene] dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (II), dichloro [1,3-bis (2-methylphenyl) -2-imidazolidinylidene] (2-isopropoxyphenylmethylene) - ruthenium (II), dichloro [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] [3- (2-pyridinyl) propylidene] ruthenium (II), dichloro [1, 3-bis (2,4,6-trimet hylphenyl) -2-imidazolidin ylidene] (benzylidene) bis (3-bromopyridine) ruthenium (II), [1, 3-bis (2,6-di-i-propylphenyl) -4,5-dihydroimidazol-2-ylidene ] - [2-isopropoxy-5- (trifluoroacetamido) phenyl] methylene- ruthenium (II) dichloride, bis (tricyclohexylphosphine) -3-phenyl-1 H -inden-1-ylidene ruthenium (II) dichloride, bis (tricyclohexylphosphine) [(phenylthio) methylene] ruthenium (II) dichloride, bis (tricyclohexylphosphine ) [(Phenylthio) methylene] ruthenium (II) dichloride, 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene [2- (isopropoxy) -5- (N, N dimethylaminosulphonyl) phenyl] methylene ruthenium (II) dichloride, 1, 3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene [2- (isopropoxy) -5- (N, N-dimethylaminosulphonyl) phenyl] methylene ruthenium (II) dichloride, [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolinediylidene] - [2 - [[(4-methylphenyl) imino] methyl] -4-nitrophenolyl] - [3-phenyl-1H-inden-1-ylidene] ruthenium (II) chloride; [1, 3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] - [2 - [[(2-methylphenyl) imino] methyl] phenolyl] - [3-phenyl-1H-indene-1 - yliden] ruthenium (II) chloride, 3-phenyl-1H-inden-1-ylidene [bis (isobutylpropane)] ruthenium (II) dichloride, {[2- (isopropoxy) -5- (N, N-dimethylaminosulfonyl) phenyl ] methylene} (tricyclohexylphosphine) ruthenium dichloride, tricyclohexylphosphine [1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene] [(phenylthio) methylene] ruthenium (II) dichloride, tricyclohexylphosphine [ 1, 3-bis (2,4,6-trimethylphenyl) imidazol-2-ylidene] [3-phenyl-1H-inden-1-ylidene] ruthenium (II) dichloride, tricyclohexylphosphine [1,3-bis ( 2,4,6-trimethylphenyl) imidazol-2-ylidene] [2-thienylmethylene] ruthenium (II) dichloride, tricyclohexylphosphine [2,4-dihydro-2,4,5-triphenyl-3H-1, 2,4-triazole 3-ylidene] [2-thienylmethylene] ruthenium (II) dichloride, tricyclohexylphosphine ^, 5-dimethyl-1,3-bis (2,4,6-trimethylphenyl) imidazol-2-ylidene] [2-thienylmethylene] ruthenium (II) dichloride, tricyclohexylphosphine [3-phenyl-1 H-indene 1 -ylidene] - [1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene] ruthenium (II) dichloride, trifluoroacetato [4,5-dihydro-1, 3 bis (2,4,6-trimethylphenyl) imidazol-2-ylidene] tetra (2,2-dimethylpropanenitrile) ruthenium (II) trifluoroacetate, tri (isopropoxy) phosphine (3-phenyl-1H-inden-1-ylidene) [1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene] ruthenium (II) dichloride or tricyclohexylphosphine [3-phenyl-1H-inden-1-ylidene [1 , 3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene] ruthenium (II) dichloride.

In a specific embodiment, in step b), at least one ruthenium-alkylidene complex which is selected from the formula F, G or H as a homogeneous catalyst is used

Cy = cyclohexyl

Mes = 2,4,6-trimethylphenyl. Catalysts containing an indenylidene carbene (F) and their preparation are described in WO 2010/037550. Catalysts based on the phosphite-containing structures (G) are described in detail in WO 201 1/1 17571. A detailed description of the compounds of the general formula (H) can be found in US Pat

WO 99/00396. The disclosure of these documents is hereby incorporated by reference.

In a second preferred embodiment, in step b) a heterogeneous catalyst is used, which comprises a compound of tungsten or of rhenium on an inorganic carrier material. Preferably, the compound of tungsten or rhenium is selected from WO3, Re2Ü7 and Ch ReOs.

Step c)

The metathesis reaction mixture obtained in step b) contains the following components: i) at least one cyclic compound having at least eight carbon atoms and at least one keto group,

ii) optionally at least one product of the metathesis reaction other than i), especially cycloaliphatic olefins (unsaturated cyclic hydrocarbons)

iii) unreacted cyclododeca-4,8-dienone,

iv) optionally at least one unreacted cyclododeca-4,8-dienone cyclic or acyclic compound having at least one C-C double bond,

v) if present, the solvent used,

vi) the transition metal catalyst.

The reaction mixture obtained in step b) is preferably subjected to a separation of the metathesis reaction before it is used further, specifically for its further use as a fragrance or to provide a fragrance. Preferably, the separation of the reaction mixture obtained in step b) comprises the separation of the transition metal catalyst used (component vi)). If a heterogeneous transition metal catalyst is used for the reaction in step b), then its separation z. B. by filtration or distillation. In the distillative removal of a heterogeneous transition metal catalyst are preferably in a conventional, known to the expert device all volatile components separated. The distillative removal of a heterogeneous transition metal catalyst preferably takes place under elevated temperature and / or under reduced pressure. If a homogeneous transition metal catalyst is used for the reaction in step b), its removal is carried out, for example, by By distillation, extraction, chromatography or a combination of at least two of these methods.

If a solvent is used for the metathesis reaction in step b), the separation of the reaction mixture obtained in step b) preferably comprises the removal of the solvent (component v)), preferably by distillation.

Removal of the catalyst (vi) used and, if present, removal of the solvent (v) used give a reaction mixture containing the products of the metathesis reaction (component (i) and, if present, (ii)), which are not set educts (component (iii) and, if present, (iv)) and optionally further undesirable secondary components (impurities).

Preferably, the metathesis reaction reaction mixture comprises at least one cyclic compound having at least 16 carbon atoms.

Preferably, the metathesis reaction reaction mixture comprises at least one cyclic compound selected from compounds having 12 or 16 or 20 or 24 carbon atoms. Preferably, the reaction mixture of the metathesis reaction without transition metal catalyst and solvent to at least 5 wt .-%, preferably at least 15 wt .-%, of at least one of the compounds I to IV

Preferably, the reaction mixture of the metathesis reaction in step c) is subjected to a separation to obtain at least one fraction which is attached to at least one of the compounds.

subjected. This separation is preferably carried out after the separation of the catalyst (vi) used and, if present, separation of the solvent (v) used. It is also conceivable that when using a homogeneous catalyst, this is not separated before the distillation, but remains in the bottom of the distillation.

Preference is given to a reaction mixture which comprises at least one of the compounds I to IV as products of the metathesis reaction (i), if present further products of the metathesis reaction, unreacted starting materials (iii) and, if present, (iv) and optionally further undesired secondary components, subjected to separation according to customary methods known to the person skilled in the art. The reaction mixture is preferably subjected to a distillative separation. Suitable apparatus for distillative separation include distillation columns, such as tray columns, which may be equipped with bells, sieve plates, sieve trays, packings, random packings, valves, side draws, etc., evaporators, such as thin film evaporators, falling film evaporators, forced circulation evaporators, Sambay evaporators, etc. , and combinations of them.

The fraction depleted in at least one of the compounds I to IV is preferably recycled to the metathesis reaction in step b).

The compositions according to the invention and the compositions obtainable by the process according to the invention are particularly advantageously suitable as fragrance or to provide a fragrance. The compositions according to the invention can be diluted as desired for use as a fragrance with at least one solvent customary in this field of application. Examples which may be mentioned as suitable solvents are: ethanol, dipropylene glycol or its ethers, phthalates, propylene glycols, or carbonates of diols, preferably ethanol. Water is also suitable as a solvent for diluting the perfume compositions according to the invention and can advantageously be used together with suitable emulsifiers.

A preferred embodiment of the fragrances according to the invention is characterized in that they comprise at least one compound which is selected from compounds of the formulas (I), (II), (III), (IV) or mixtures which have two, three or four of these Contain connections.

Due to the structural and chemical similarity of the components, the odoriferous substances according to the invention have a high stability and durability and are distinguished by a pleasant musky odor. The fragrances according to the invention are suitable for incorporation into cosmetic compositions as well as consumer and consumer goods or agents as described in more detail below. A further aspect of the present invention therefore relates to cosmetic compositions, consumables or consumer goods, which comprise an organoleptically effective amount of the fragrances according to the invention, wherein the fragrances may be incorporated into or applied to said goods. An organoleptically effective amount is to be understood, as in the context of the entire present invention, in particular an amount which, when used properly, is sufficient to produce a scent impression on the user or consumer, especially the impression of a pleasant musk odor.

As cosmetic compositions, all the usual cosmetic compositions are suitable. These are preferably perfume, toilet water, deodorants, soap, shower gel, bath gel, creams, lotions, sunscreens, compositions for cleaning and care of hair such as hair shampoo, conditioner, hair gel, hair fixative in the form of liquids or foams and other hair cleansers or conditioners, compositions for decorative use on the human body, such as cosmetic sticks, e.g. Lipsticks, lip balms, concealers, blushers, eyeshadow sticks, lip contour pens, eye contour pens, eyebrow pencils, correction pens, sun protection pens, anti-acne pens and similar products, as well as nail polishes and other nail care products. The fragrances according to the invention are particularly suitable for use in perfumes, for. As Eau de Toilette, shower gels, bath gels and body deodorants.

They are also suitable for the flavoring of consumer goods, in which they are incorporated or on which they are applied and thereby give them a pleasant musky fragrance. Examples of consumer goods or consumer goods are: air-deodorants (air care), detergents or care products for textiles (especially detergents, fabric softeners), textile treatment agents such as ironing aids, cleaning agents, cleaning agents, care products for the treatment of surfaces, such as furniture, floors, kitchen equipment, glass and windows and screens, bleaching, toilet blocks, descaling agents, fertilizers, building materials, mold removers, disinfectants, car care products and the like. The metathesis products obtainable by the process according to the invention or

Fractions or substantially pure compounds thereof may also serve as valuable intermediates. They are suitable for further processing, eg. B. by hydrogenation, Baeyer-Villiger oxidation to macrocyclic lactones, synthetic building blocks of various specialty chemicals and fragrances, etc.

The following examples serve to illustrate the invention without limiting it in any way.

EXAMPLES

GC analysis:

Device: HP 5890 Series II

Column: HP5 15m x 0.32 μηι

Detector: Fl D detector

Injection: 0.5 μΙ_

Temperature program:

isothermal for 5 min at 60 ° C,

heat up to 300 ° C at 10 ° C / min,

Isothermal for 15 minutes,

heat up to 320 ° C at 10 ° C / min,

Isothermal for 18 minutes. Example 1 :

A solution of cyclododeca-4,8-dienone (0.87 g, 4.9 mmol, 1 eq.) In toluene (100 mL) was treated with the Ru catalyst of formula (F) (4.7 mg, 4.9 g pmol, 0.1 mol%) and brought to 60 ° C.

After 68 hours, the conversion of dienone was 44%. The determination of the compounds I, II, III and IV was carried out by gas chromatography, as described above. The selectivities are shown in Table 1.

Table 1

Example 2:

A solution of cyclododeca-4,8-dienone (4.35 g, 24.4 mmol, 1 eq.) In toluene (95 mL) is treated with Ru catalyst of formula A (23.3 mg, 24.5 pmol, 0 , 1 mol%) and on Brought to 60 ° C. After 68 hours, the conversion of dienone was 93%. The following selectivities were observed:

Table 2

Note: Mass selectivity is defined as the ratio in% of the mass of a product X present in the reaction product divided by the mass of the educt used.

Claims

Patent claims

Process for producing at least one cyclic compound having at least eight carbon atoms and at least one keto group, in which a) a cyclododeca-4,8-dienone-containing starting material is provided, and b) the starting material is subjected to an olefin metathesis reaction in the presence of a transition metal catalyst.

Process according to Claim 1, in which c) the reaction mixture obtained in step b) is subjected to a separation of the metathesis reaction.

Method according to one of the preceding claims, wherein a 1,5,9-cyclododecatriene-containing composition is used to provide the cyclododeca-4,8-dienone-containing starting material in step a).

The method according to claim 3, wherein the 1,5,9-cyclododecatriene-containing composition is subjected to oxidation, preferably with nitrous oxide.

5. The method according to any one of the preceding claims, wherein the metathesis reaction in step b) is carried out at a temperature in the range from 0 to 200 °C, preferably from 10 to 150 °C, in particular from 20 to 100 °C.

6. The method according to any one of the preceding claims, wherein the metathesis reaction in step b) is carried out in the presence of a solvent that is inert under the reaction conditions.

7. The method according to any one of the preceding claims, wherein the metathesis reaction in step b) is additionally carried out in the presence of at least one cyclic compound other than cyclododeca-4,8-dienone with at least one

C-C double bond is carried out.

8. The method according to claim 7, wherein the metathesis reaction in step b) is additionally carried out in the presence of at least one cyclic oligobutadiene.

9. The method according to any one of the preceding claims, wherein for the metathesis reaction in step b) cyclododeca-4,8-dienone and, if present, various cyclic compounds with at least one C-C double bond, in a total concentration in the range from 0.01 to 1 mol/L, preferably in a total concentration in the range from 0.01 to 0.5 mol/L.

Method according to one of the preceding claims, wherein the metathesis catalyst used in step b) comprises at least one transition metal from groups 6, 7 or 8 of the periodic table of the elements, preferably Mo, W, Re or Ru.

Process according to one of claims 1 to 10, wherein in step b) a homogeneous catalyst is used which comprises at least one ruthenium alkylidene complex, preferably a ruthenium alkylidene complex which additionally has at least one N-heterocyclic carbene as a ligand.

Process according to one of claims 1 to 10, wherein in step b) a heterogeneous catalyst is used which comprises a compound of tungsten or rhenium, preferably selected from WO3, Re2Ü7 and CI-ReC, on an inorganic support material.

Process according to one of the preceding claims, wherein the reaction mixture of the metathesis reaction without transition metal catalyst and solvent consists of at least 50% by weight of cyclic compounds which have one or two keto groups.

14. The method according to any one of the preceding claims, wherein the reaction mixture of the metathesis reaction comprises at least one cyclic compound which has at least 16 carbon atoms.

15. The method according to any one of the preceding claims, wherein the reaction mixture of the metathesis reaction comprises at least one cyclic compound selected from compounds with 12 or 16 or 20 or 24 carbon atoms.

16. The method according to any one of the preceding claims, wherein the reaction mixture of the metathesis reaction in step c) undergoes a separation to obtain at least one fraction which contains at least one of the compounds I to IV is enriched, and is subjected to at least one fraction which is depleted in at least one of the compounds I to IV.

17. The method according to claim 16, wherein the fraction depleted in at least one of the compounds I to IV is recycled into the metathesis reaction in step b).

18. The method according to any one of the preceding claims, wherein the product from step b) or step c) is subjected to at least one further reaction.

19. Composition containing at least one cyclic compound having at least eight carbon atoms and at least one keto group, obtainable by a process according to any one of claims 1 to 18.

20. Use of at least one cyclic compound, which is obtainable by a process according to one of claims 1 to 18, as a fragrance or to provide a fragrance.

21. Cosmetic composition, consumable or consumer good, which contains an organoleptically effective amount of at least one cyclic compound with at least eight carbon atoms and at least one keto group, obtainable by a process according to one of claims 1 to 18, as a fragrance.