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EP2861552A1 - Procédé de production de cétones macrocycliques - Google Patents

Procédé de production de cétones macrocycliques

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Publication number
EP2861552A1
EP2861552A1 EP13729318.9A EP13729318A EP2861552A1 EP 2861552 A1 EP2861552 A1 EP 2861552A1 EP 13729318 A EP13729318 A EP 13729318A EP 2861552 A1 EP2861552 A1 EP 2861552A1
Authority
EP
European Patent Office
Prior art keywords
metathesis reaction
reaction
compounds
metathesis
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP13729318.9A
Other languages
German (de)
English (en)
Inventor
Richard Dehn
Joaquim Henrique Teles
Michael Limbach
Stephan Deuerlein
Manuel Danz
Ralf Pelzer
Daniel Schneider
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP13729318.9A priority Critical patent/EP2861552A1/fr
Publication of EP2861552A1 publication Critical patent/EP2861552A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
    • C07C49/547—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings to a seven- to twelve-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered

Definitions

  • 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.
  • 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.
  • 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.
  • Cyclododecanone is an important intermediate for the production of lauryl lactam, dodecanedicarboxylic acid and derived polyamides.
  • 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,
  • 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.
  • 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.
  • 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.
  • 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) 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.
  • 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.
  • 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.
  • the 1, 5,9-cyclododecatriene is prepared by trimerization of butadiene.
  • 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%.
  • 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.
  • the 1, 5,9-cyclododecatriene-containing composition is subjected to oxidation with nitrous oxide.
  • 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.
  • 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.
  • 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.
  • the nitrous oxide is used in the form of a gas mixture obtained as the exhaust gas of another method, such as.
  • 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.
  • 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
  • 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.
  • an oxidation product which contains the following components:
  • 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.
  • 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.
  • 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.
  • 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.
  • the further compound may have at least one functional group.
  • the carbon chain of the further compound is interrupted by one or more nonadjacent keto groups.
  • the further compound has no further functional group in addition to at least one C-C double bond.
  • 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.
  • 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.
  • a starting material 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.
  • 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.
  • the composition of the product of the metathesis reaction can be controlled. So z.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a homogeneous catalyst which comprises at least one ruthenium-alkylidene complex, preferably a ruthenium-alkylidene complex which additionally has at least one N-heterocyclic carbene as ligand.
  • 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.
  • 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.
  • arylalkyl or "aralkyl” have at least one unsubstituted or substituted aryl group as defined below.
  • 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.
  • cycloalkyl denotes a cycloaliphatic radical having preferably 3 to 10, particularly preferably 5 to 8, carbon atoms.
  • cycloalkyl groups are in particular cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • 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.
  • 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.
  • 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.
  • heteroaryl 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.
  • 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.
  • 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.
  • R c is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • heterocycloalkyl groups are in particular pyrrolidinyl, piperidinyl,
  • 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,
  • X 1 , X 2 may be the same or different.
  • X 1 and X 2 are the same.
  • 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.
  • X 1 and X 2 are independently selected from fluorine, chlorine, bromine, iodine, cyano, thiocyano, methyl, ethyl, phenyl, phenyloxy, methyloxy or ethyloxy.
  • 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.
  • 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.
  • 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.
  • m is 0.
  • 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.
  • n is 0 and L 1 and L 2 are independently selected from pyridine or pyridine derivatives.
  • 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.
  • 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) -.
  • R 3A and R 4A are joined together and together form a divalent organic
  • Q is a divalent organic group having 1 to 40 carbon atoms.
  • 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.
  • 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.
  • 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
  • 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)
  • X 1 and X 2 are identical or different and denote an anionic ligand
  • 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
  • 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
  • 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 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 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,
  • 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,
  • 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.
  • 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;
  • n 0, 1 or 2;
  • Ruthenium alkylidene complexes suitable as metathesis catalysts are also the so-called “Grubbs" catalysts of the first generation, eg of the formula
  • 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-tritri
  • step b) at least one ruthenium-alkylidene complex which is selected from the formula F, G or H as a homogeneous catalyst is used
  • a heterogeneous catalyst which comprises a compound of tungsten or of rhenium on an inorganic carrier material.
  • the compound of tungsten or rhenium is selected from WO3, Re2Ü7 and Ch ReOs.
  • 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)
  • 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.
  • 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.
  • the separation of the reaction mixture obtained in step b) preferably comprises the removal of the solvent (component v)), preferably by distillation.
  • the metathesis reaction reaction mixture comprises at least one cyclic compound having at least 16 carbon atoms.
  • the metathesis reaction reaction mixture comprises at least one cyclic compound selected from compounds having 12 or 16 or 20 or 24 carbon atoms.
  • 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
  • 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.
  • 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.
  • 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).
  • 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.
  • the odoriferous substances according to the invention 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.
  • 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.
  • 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production de liaisons cycliques comportant au moins huit atomes de carbone et au moins un groupe cétone, les liaisons cycliques obtenues selon ce procédé, et leur utilisation, en particulier en tant que substance odorante ou pour la préparation d'une substance odorante.
EP13729318.9A 2012-06-13 2013-06-12 Procédé de production de cétones macrocycliques Withdrawn EP2861552A1 (fr)

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PCT/EP2013/062077 WO2013186238A1 (fr) 2012-06-13 2013-06-12 Procédé de production de cétones macrocycliques
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