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EP3359516A1 - Utilisation de nouveaux mélanges d'isomères (e/z) de cyclopentadécénone, leur préparation et leur utilisation comme arôme - Google Patents

Utilisation de nouveaux mélanges d'isomères (e/z) de cyclopentadécénone, leur préparation et leur utilisation comme arôme

Info

Publication number
EP3359516A1
EP3359516A1 EP16778043.6A EP16778043A EP3359516A1 EP 3359516 A1 EP3359516 A1 EP 3359516A1 EP 16778043 A EP16778043 A EP 16778043A EP 3359516 A1 EP3359516 A1 EP 3359516A1
Authority
EP
European Patent Office
Prior art keywords
cyclopentadec
mixture
compound
oil
formula
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.)
Withdrawn
Application number
EP16778043.6A
Other languages
German (de)
English (en)
Inventor
Frauke THRUN
Joaquim Henrique Teles
Albert Werner
Ralf Pelzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from EP15188870.8A external-priority patent/EP3153494A1/fr
Application filed by BASF SE filed Critical BASF SE
Publication of EP3359516A1 publication Critical patent/EP3359516A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/607—Unsaturated compounds containing a keto groups being part of a ring of a seven-to twelve-membered ring
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0038—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing more than six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • 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 novel mixtures of (E / Z) -cyclopentadecenone isomers, their preparation and their use as a flavoring agent, in particular as an odoriferous substance, the invention relates to novel mixtures of (E / Z) -cyclopentadecenone isomers, their preparation and their use as flavoring agents. and flavor compositions and agents containing these mixtures.
  • musk-like fragrances and perfume compositions By this is meant a smell that is similar to the naturally occurring musk fragrance.
  • EP-A 216 185 mentions that the compounds of the c / s-7- and 8-cyclopentadecen-1 -ones starting from c / s-16-oxabicyclo- [13.1.0] -hexadec-8-ene via an acid or Lewis acid-catalyzed Meerwein rearrangement can be prepared, but without providing experimental evidence. Furthermore, the usefulness of the two compounds is postulated as perfume. However, the actual olfactory properties of the 7- or 8-cyclopentadecenones have not yet been described in the literature. The Cu-catalyzed oxidative decarbonylation is known and widely published, examples are: a) Tetrahedron Lett.
  • the object of the present invention is to provide novel musky fragrances.
  • the above object was achieved in particular by providing the macrocyclic keto compounds defined in the claims and a process for their preparation and isolation.
  • the cyclic aldehydes which are formed as by-products in the oxidation of cyclohexadeca-1, 9-diene with nitrous oxide, can be subjected to a Cu-catalyzed, oxidative decarbonylation.
  • cyclohexadec-8-enone can be separated from the resulting cyclopentadec-8-enone by distillation without significant losses in yield; in addition, a mixture consisting essentially of (E / Z) -cyclopentadec-8-ene can be distilled off.
  • enone ratio eg 1: 1
  • E / Z cyclopentadec-7-enone
  • ratio 1: 1 wherein the ratio of cyclopentadec-8-enone and cyclopentadec-7-enone is 10: 1, with valuable olfactory Isolate properties.
  • the cyclopentadecenones I-IV smell very well olfactorily from the Cu-catalyzed, oxidative decarbonylation of cyclopentadecenylcarbaldehyde XI.
  • the cyclopentadecenones L-IV thus extend the repertoire of the fragrance industry, especially the musk-like fragrances.
  • the compounds are characterized by a green, aldehydic, harsh, gaseous, sweet, powdery, after dried fruit and smelling of musk smell.
  • the cyclopentadec-8-enones occur as a (E / Z) mixture in the ratio 1: 1 in the Cu-catalyzed, oxidative decarbonylation.
  • the (E / Z) cyclopentadec-7-enones were also obtained.
  • perfume is to be understood as meaning natural or synthetic substances with an inherent odor.
  • the term "flavoring agent” is to be understood as natural or synthetic substances with a natural taste.
  • the "smell” or “olfactory perception” in the sense of the present invention is the interpretation of the sensory excitations delivered by the chemoreceptors of the nose or other olfactory organs to the brain of a living being.
  • the smell can therefore be a sensory perception of the nose of fragrances, which takes place when inhaled.
  • the air serves as a smell carrier.
  • fragment is to be understood as meaning a fragrant odor.
  • perfume a fragrant odor
  • a "perfume” is a mixture of fragrances and carriers, in particular an alcohol.
  • a "perfume composition” is a perfume which contains different amounts of harmoniously matched individual components. The properties of the individual components are used to create a new overall picture in the combination, with the characteristics of the ingredients fading into the background, but without being suppressed.
  • a "perfume oil” is a concentrated mixture of several fragrances, which are e.g. used in alcoholic solutions for perfuming various products.
  • a "fragrance theme” is the predominant fragrance note in a fragrance composition.
  • the “top note” is the first phase of the perfume course of a perfume. It plays the crucial role in the first impression, when opening the bottle and when applying the perfume to the skin. The task of the top note is interest to awaken the perfume in general and to attract attention. Therefore, an exceptional character is often more important than a sophisticated harmony. The top note is naturally determined by volatile odoriferous substances. "Modification" in the context of the present invention means to provide the basic theme of a fragrance composition with additional or different chords and odor nuances.
  • “Chords” arise in the context of the present invention by the combination of different fragrances, which thus unite to form new odors.
  • the number of fragrances used can range from two to a hundred different.
  • An "organoleptically / sensory effective amount" in the context of the present invention is the amount of a fragrance sufficient to stimulate a sensory organ or stimulating a sensory receptor.
  • (E / Z) is (E and / or Z) and basically denotes, unless stated otherwise, mixtures comprising both the stereoisomeric E configuration and the corresponding Z configuration, but also the stereoisomerically pure E and Z forms of one Connection. b) specific embodiments of the invention
  • the present invention relates in particular to the following subjects:
  • A has the meanings given above, oxidatively decarbonylated; wherein reacting the compound of formula XI in the presence of, preferably a catalytic amount of a preferably homogeneous Cu (II) catalyst and molecular pure oxygen, lean air or preferably air, in particular dried, filtered ambient air, and optionally
  • the base used in the process according to the invention is, for example, selected from diazabicycloalkanes, such as. Diazabicyclooctane (DABCO), diazabicycelloundecene (DBU), diazabicyclononane (DBN) tertiary amines such as trimethylamine, triethylamine, triisopropylamine, diisopropylethylamine or tripropylamine, N, N-dimethylpiperazine, / V-methylpyridine, / V-methylpyrrolidone, quinuclidine and the like , Preferably DBU is used.
  • a solvent such as in the presence of an organic solvent, in particular an organic solvent, wherein the catalyst is dissolved.
  • Non-limiting examples of organic solvents include: polar, aprotic solvents such as dimethylformamide (DMF), hexamethylphosphoramide (HMPA), dimethylsulfoxide (DMSO), tetramethylurea and dimethylacetamide, and mixtures thereof.
  • aprotic solvents such as dimethylformamide (DMF), hexamethylphosphoramide (HMPA), dimethylsulfoxide (DMSO), tetramethylurea and dimethylacetamide, and mixtures thereof.
  • Other suitable organic solvents which can be used alone or in combination with the above aprotic organic solvents are alcohols, such as methanol, ethanol, propanol or butanols, such as ie / f-butanol and tetrahydrofuran, dioxane or benzene.
  • DMF is used.
  • the reaction takes place essentially without addition of solvent, preferably in a solvent-free reaction mixture.
  • the mixture of reactants and catalyst may be preferably heated thereto, e.g. to a temperature of 30 to 70 or 40 to 60 ° C.
  • the catalyst is formed by adding to a Cu (II) salt, in particular a bidentate ligand, preferably diamine ligands.
  • the Cu (II) salt used according to the invention is selected, for example, from Cu (II) acetate, formate, sulfate, chloride or nitrate.
  • Cu (OAc) 2 is used.
  • Suitable complex ligands are in particular bidentate Cu complexing amine ligands, such as ⁇ /, ⁇ /, ⁇ / ', ⁇ /' - tetramethylethylenediamine (TMEDA), 1, 10-phenanthroline and 2,2-bipyridyl.
  • TMEDA is used.
  • Method according to one of the preceding embodiments wherein the oxidative decarbonylation at a temperature in the range of 10 to 70, in particular 30 to 60 ° C, over a period of 0.1 to 40, in particular 0.1 to 30 h, preferably 2 to 7 h, especially 3 to 5 h, such as about 4 h, and at a pressure of 0.1 to 10, in particular 1 to 2 atm is performed.
  • a performance of the method in a vacuum, such as at a negative pressure in the range of 0.001 to 0.99 bar, or in particular 0.01 to 0.5 or 0.1 to 0.25 bar is also conceivable.
  • Method according to one of the preceding embodiments wherein in the compounds of the formula X and XI m is 15 and / or n is 1, in particular m is 15 and n is 1.
  • step a a reaction product is used in step a), which is obtained from the dinitrogen monoxide oxidation of a cycloaliphatic compound of formula XII
  • Process according to embodiment 1 wherein the compound of formula XII is cyclohexadeca-1,9-diene.
  • a process for preparing globanone ((E / Z) -cyclohexadec-8-en-1-one) comprising: a) oxidizing cyclohexadeca-1,9-diene with dinitrogen monoxide to obtain a reaction mixture comprising a mixture comprising ( E / Z) -cyclohexadec-8-en-1-one (globanone) and at least one cyclopentadecenylcarbaldehyde compound, especially selected from (E / Z) -cyclopentadec-8-enylcarbaldehydes; optionally separating unreacted cyclohexadeca-1, 9-diene, e.g. distillatively, and then optionally recycled to the process, step a);
  • step b) subjecting the reaction mixture of step a) to an oxidative decarbonylation reaction according to any one of embodiments 1 to 5;
  • c) separates globanone from the cyclopentadecenones formed thereby, in particular the cyclopentadecenones I, II, III and / or IV formed therefrom or mixtures thereof.
  • the oxidative decarbonylation can be carried out in the presence or absence of a solvent.
  • a substance or mixture of substances comprising at least one macrocydic keto compound of the above general formula X.
  • a composition according to embodiment 15 comprising substantially (ie at least 80% or 90% (FI .-%) at least two compounds selected from (E / Z) cyclopentadec-8-en-1-one and (E / Z) Cyclopentadec-7-en-1-one.
  • a composition according to embodiment 16 comprising substantially (ie at least 80% or 90% (FI .-%) at least two compounds selected from compounds of the following formulas I, III and the regioisomers thereof, such as the formula II
  • I II III IV Use of at least one substance or substance mixture according to one of embodiments 15 to 17 as an aroma chemical, in particular as a fragrance.
  • 21. Use according to embodiment 20, wherein the molar ratio of (I) to (III) ranges from about 1: 1 to about 10: 1, especially 1: 1 to 5: 1. 22.
  • a fragrance composition comprising at least one substance or a mixture of substances as defined in one of the embodiments 15 to 17 or produced by one of the processes according to the embodiments 1 to 12.
  • composition according to embodiment 21, containing the substance or mixture of substances in a proportion by weight of 0.01 to 99.9 wt .-%, 1 to 80 wt .-%, 2 to 50 wt .-%, 3 to 25 or 5 to 15 wt .-% based on the total weight of the composition.
  • composition comprising at least one substance or a mixture of substances as defined in one of embodiments 15 to 17 or produced by one of the processes according to embodiments 1 to 12.
  • composition according to embodiment 26 comprising the substance or the mixture of substances in a weight fraction of 0.01 to 99.9 wt .-%, 1 to 80 wt .-%, 2 to 50 wt .-%, 3 to 25 or 5 to 15 wt .-%, based on the total weight of the composition.
  • Composition according to embodiment 26 or 27, selected from perfumes, detergents and cleaners, cosmetics, personal care products, hygiene articles, foods, food supplements, fragrance dispensers, fragrances, pharmaceutical agents and crop protection agents.
  • fragrances used according to the invention are used in particular for the purpose of more efficient handling and metering, also as perfume mixtures with diluents or solvents.
  • proportion of fragrances, based on the sum of fragrances and solvents, in wt .-% is given.
  • a “solvent” serves to dilute the fragrances or fragrance compositions according to the invention to be used without having their own odoriferous properties. Some solvents also have fixing properties.
  • the compound of the formula X according to the invention or an above-defined mixture of several compounds / isomers of the formula X can be admixed to form 0.1 to 99% by weight of a diluent or solvent.
  • a diluent or solvent Preferably, at least 40 wt .-% solutions, more preferably at least 50 wt .-% solutions, further preferably at least 60 wt .-% solutions, more preferably at least 70 wt .-% solutions, more preferably at least 80 wt. -% solutions, more preferably at least 90 wt .-% solutions, preferably in olfactorily acceptable solvents.
  • Preferred olfactorily acceptable solvents are ethanol, isopropanol, dipropylene glycol (DPG), propylene glycol, 1,2-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethyl phthalate (DEP), isopropyl myristate (IPM), triethyl citrate (TEC), benzyl benzoate (BB) and benzyl acetate.
  • DPG dipropylene glycol
  • PDP diethyl phthalate
  • IPM isopropyl myristate
  • TEC triethyl citrate
  • BB benzyl benzoate
  • BB benzyl acetate
  • a “fragrance composition” is a mixture which, in addition to a compound of the formula X according to the invention or a substance mixture of a plurality of compounds / isomers of the formula X as defined above, comprises at least one further fragrance.
  • a fragrance composition may be a perfume composition (a perfume oil).
  • Fragrance compositions according to the invention contain, based on the total amount of the perfume composition, for example an amount of a compound of the formula X according to the invention or of a substance mixture of several compounds / isomers of the formula X defined above of from 0.01 to 65% by weight, preferably of about 0, From 1 to about 50 weight percent, preferably from about 0.5 to about 30 weight percent, and more preferably from about 0.5 to about 25 weight percent.
  • the Weight ratio of inventive compound / compounds of formula X to the total amount of other fragrances is for example in the range of 1: 1000 to 1: 0.5, preferably in the range of 1: 700 to 1: 1, particularly preferably in the range of 1: 500 to 1:10.
  • Fragrance compositions according to the invention contain, based on the total amount of the fragrance composition, e.g. an amount of compound (s) according to the invention of formula X of from 0.01 to 65% by weight and preferably from about 0.1 to about 50% by weight, preferably from about 0.5 to about 30% by weight and more preferably from about 0.5 to about 25 weight percent.
  • the weight ratio of inventive compound (s) of the formula X to the total amount of other (different) fragrances is e.g. in the range of 1: 1000 to 1: 0.5, preferably in the range of 1: 700 to 1: 1, particularly preferably in the range of 1: 500 to 1:10.
  • Fragrance compositions according to the invention contain, in addition to the compound (s) of the formula X according to the invention (in particular of the formulas I, II and III) at least one further fragrance, preferably 2, 3, 4, 5, 6, 7, 8 or more further fragrances, wherein further Fragrances eg are selected under:
  • fragrances with which (E / Z) -cyclopentadec-7/8-enone can be combined, for example, into a fragrance composition, can be found, for example, in S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, NJ, 1969 , Self-published or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4rd. Ed., Wiley-VCH, Weinheim 2001. Specifically, may be mentioned:
  • Extracts of natural raw materials such as essential oils, concretes, absolues, resines, resinoids, balsams, tinctures such as e.g.
  • ambergris tincture Amyrisöl; Angelica seed oil; Angelica root oil; anise oil; Valerian oil; Basil oil; Tree moss absolute; Bay oil; Mugwort oil; Benzoeresin; Bergamotteol; Beeswax absolute; Birch tar oil; Bitter almond oil; Savory oil; Buccorightöl; Cabreuvaöl; cade oil; calamus; camphor oil; Cananga oil; cardamom; Cascarillaöl; cassia; Cassie absolute; Castoreum- absolute; Cedern diligentöl; cedarwood; cistus; citronella; lemon; copaiba balsam; Copava balsam oil; Coriander oil; costus root; Cuminöl; Cypress oil; Davanaöl; Dill herb oil; Dill seed oil; Eau de Brouts absolute; Oak moss absolute; elemi; Tarragon oil; Eucalyptus citriodora oil; eucalyptus oil; Fenne
  • fragrances from the group of hydrocarbons such as 3-carene; alpha-pinene; beta-pinene; alpha-terpinene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene; Cedars; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E, Z) -1, 3,5-undecatriene; Styrene; diphenylmethane; the aliphatic alcohols such as hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E) -2-hexenol; (E) - and (Z) -3-hexenol; 1-octen-3-ol; Mixture of 3,4,5,6,6-penta
  • 1-cyclohexylethyl crotonate the ester of cycloaliphatic carboxylic acids, e.g. Allyl 3-cyclohexylpropionate; Allylcyclohexy-loxyacetate; cis and iran methyldihydrojasmonate; egg and iran methyl jasmonate; Methyl 2-hexyl-3-oxocyclopentanecarboxylate; Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; Ethyl 2,3,6,6-tetramethyl-2-cyclohexene carboxylate; Ethyl 2-methyl-1,3-dioxolane-2-acetate; the araliphatic alcohols such as e.g.
  • benzyl alcohol 1-phenylethyl alcohol, 2-phenylethyl alcohol, 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3- (3-methylphenyl) -propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1, 1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol;
  • Inventive (E / Z) -cyclopentadec-7/8-enone or perfume compositions according to the invention can be incorporated in a number of products or applied to such products.
  • Fragrances according to the invention can be used in the production of perfumed articles.
  • the olfactory properties as well as the material properties (such as solubility in common solvents and compatibility with common other constituents of such products) as well as the toxicological harmlessness of the fragrances according to the invention underline their particular suitability for the stated purposes.
  • the positive properties contribute to the fact that the fragrances used according to the invention and the perfume compositions according to the invention are particularly preferably used in perfumery products, personal care products, hygiene articles, textile detergents and in cleaners for solid surfaces.
  • the perfumed article is selected, for example, from perfumery products, personal care products, hygiene articles, laundry detergents and solid surface cleaners.
  • Preferred perfumed articles according to the invention are furthermore selected from: perfumery products selected from perfume extracts, Eau de perfume extracts, Eau de Toilettes, Eau de Colognes, Eau de Solide, Extrait Perfume, air fresheners in liquid, gel or solid-carrier form, aerosol sprays , Fragrance cleaners and oils;
  • Personal care products selected from among shampoos, pre-shave products, splash colognes, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving creams, bath oils, oil-in-water, water-in-oil and cosmetic emulsions
  • Water-in-oil-in-water type such as Skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products such as Hair sprays, hair gels, hair setting lotions, hair lotions, hair shampoo, permanent and semi-permanent hair dyes, hair styling agents such as cold waving and hair straightening, hair lotions, hair creams and lotions, deodorants and antiperspirants such as hair wipes.
  • Sanitary articles selected from among candles, lamp oils, incense sticks, insecticides, repellents, fuels, rust removers, scented towelettes, underarm pads, baby diapers, sanitary napkins, toilet paper, facial tissues, handkerchiefs, douche machines;
  • Solid surface cleaners selected from perfumed acidic, alkaline and neutral detergents, e.g. Floor cleaners, window glass cleaners, dishwashing detergents, bath and sanitary cleaners, scouring creams, solid and liquid toilet cleaners, powder and foam carpet cleaners, waxes and polishes such as furniture polishes, floor waxes, shoe creams, disinfectants, surface disinfectants and sanitary cleaners, brake cleaners, pipe cleaners, descaler, Grill and oven cleaners, algae and moss removers, mold removers, facade cleaners;
  • Laundry detergents selected from among liquid detergents, powdered detergents, laundry pre-treatment agents such as bleaches, soaking and stain removers, laundry conditioners, laundry soaps, washing tablets.
  • the fragrances used according to the invention and the fragrance substance compositions according to the invention are suitable for use in surfactant-containing perfumed articles. Namely sought - especially for the perfuming of surfactant-containing formulations such as detergents (especially dishwashing detergents and all-purpose cleaners) - often fragrances and / or fragrance compositions with a Rosenkopfno- te and pronounced naturalness.
  • fragrances and fragrance compositions according to the invention can be used rosily as agents for providing (a) hair or (b) textile fibers with the odor note.
  • fragrances and fragrance compositions according to the invention to be used according to the invention are therefore particularly suitable for use in surfactant-containing perfumed articles. It is preferred if the perfumed article is one of the following:
  • an acidic, alkaline or neutral detergent especially selected from the group consisting of all-purpose cleaners, floor cleaners, window glass cleaners, dishwashing detergents, bath and sanitary cleaners, scouring cream, solid and liquid toilet cleaners, powder and foam carpet cleaners, liquid detergents, powdered Washing mitts, laundry pretreatment agents such as bleaches, soak and stain removers, fabric softeners, laundry soaps, washing tablets, disinfectants, surface disinfectants,
  • an air freshener in a liquid, gelatinous or solid support form or as an aerosol spray in a liquid, gelatinous or solid support form or as an aerosol spray
  • a wax or a polish selected in particular from the group consisting of furniture polishes, floor waxes and shoe creams, or
  • a personal care product selected in particular from the group consisting of shower gels and shampoos shaving soaps, shaving foams, bath oils, oil-in-water, water-in-oil and water-in-oil-in-water cosmetic emulsions Types such as skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products such as hair sprays, hair gels, firm hair lotions, hair conditioners, permanent and semipermanent hair dyes, hair styling agents such as cold waves and hair straighteners, hair lotions, hair creams and lotions, deodorants and antiperspirants such as underarm sprays, rollons, Deosticks, Deocremes, decorative cosmetics.
  • fragrances or fragrance compositions according to the invention are, for example: preservatives, abrasives, anti-acne agents, anti-aging agents, antibacterial agents, anti-cellulite agents, anti-dandruff agents, anti-inflammatory agents, anti-irritants, anti-irritants Agents, antimicrobial agents, antioxidants, astringents, perspiration inhibitors, antiseptics, antistatic agents, binders, buffers, carrier materials, chelating agents, cell stimulants, cleansing agents, skin care agents, depilatory agents, surface-active substances, deodorants, antiperspirants, emollients, emulsifiers, enzymes, essential oils, fibers, film formers, fixatives, foaming agents, foam stabilizers, foaming inhibitors, foam boosters, fungicides, gelling agents, gelling agents, hair care products, hair styling agents, hair straighteners moisturizing agents, moisturizing substances, moisturizing substances, bleaching agents, restore
  • the fragrances are used in the preparation of the perfumed articles in liquid form, neat or diluted with a solvent or in the form of a fragrance composition.
  • suitable solvents for this purpose include, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc.
  • solvents mentioned these, in the case of the presence of their own olfactory properties , are to be assigned exclusively to the component "solvents" and not to the "fragrances”.
  • the fragrances and / or fragrance compositions contained in the perfumed articles according to the invention can in one embodiment be absorbed on a carrier which is suitable both for a fine distribution of the fragrance or the fragrance composition in the Product as well as providing controlled release during use.
  • a carrier which is suitable both for a fine distribution of the fragrance or the fragrance composition in the Product as well as providing controlled release during use.
  • Such carriers may be porous inorganic materials such as light sulfate, silica gels, zeolites, gypsum, clays, clay granules, aerated concrete, etc., or organic materials such as wood and cellulose based materials.
  • fragrances used in accordance with the invention and the fragrance substance compositions according to the invention can also be microencapsulated, spray-dried, present as inclusion complexes or as extruded products and added in this form to the product or article to be perfumed.
  • the properties can be further optimized by so-called “coating” with suitable materials with a view to a more targeted release of fragrance, to which end preferably wax-like plastics, such as e.g. Polyvinyl alcohol can be used.
  • the microencapsulation can be achieved, for example, by the so-called coacervation method with the aid of capsule materials, e.g. made of polyurethane-like substances or soft gelatin.
  • the spray-dried perfume oils can be prepared, for example, by spray-drying an emulsion or dispersion containing the perfume oil, wherein starches, proteins, dextrin and vegetable gums modified as carriers can be used.
  • Inclusion complexes may be e.g. by incorporating dispersions of fragrance compositions and cyclodextrins or urea derivatives into a suitable solvent, e.g. Water.
  • Extrusion products can be prepared by fusing fragrances and fragrance compositions according to the invention with a suitable waxy substance and by extrusion followed by solidification, optionally in a suitable solvent, e.g. Isopropanol. c3) Preparation of fragrances according to the invention
  • the macrocyclic ketones of the formula X according to the invention are prepared starting from the corresponding carbaldehydes of the formula XI,
  • the carbaldehydes in turn, for example, starting from the corresponding cycloaliphatic compounds of the formula XII
  • Example of a suitable starting compound (which can be used both in stereoisomerically pure form or in the form of stereoisomer) for the preparation of compounds of formula XI wherein A is 5 radical of a monounsaturated C is cyclohexanone deca-1, 9- which is either commercially available or can be prepared according to Example 2 of EP-A-1 288 181.
  • a cyclic olefin is oxidized by reaction with dinitrogen monoxide.
  • Nitrous oxide can be used in pure or optionally in admixture with other gaseous substances under reaction conditions, such as carbon dioxide for dilution. It can be carried out for the reaction of the cyclic olefin with dinitrogen monoxide in the substance or in the presence of at least one suitable solvent or diluent. Preferably, the reaction takes place in substance.
  • Substantially all common solvents and / or diluents are suitable here, but with the proviso that they have neither a CC double bond nor a C-C triple bond nor an aldehyde group.
  • Suitable solvents include: cyclic alkanes, for example cyclohexane, cyclopentane, cyclooctane, cyclododecane or saturated aliphatic or aromatic, optionally alkyl-substituted hydrocarbons.
  • the temperature in the reaction is, for example, at 140 to 350 ° C, in particular at 180 to 320 ° C or at 200 to 300 ° C. It is also possible to carry out the reaction at two or more temperatures or in two or more temperature ranges which are each within the limits specified above. Temperature changes in the course of the reaction can be carried out continuously or discontinuously. In particular, however, the reaction temperature is substantially constant.
  • the reaction can also be carried out preferably adiabatically, so that the temperature rises in the reactor.
  • the pressure in the reaction of the cyclic olefin with dinitrogen monoxide is in particular higher than the autogenous pressure of the educt or product mixture at the selected reaction temperature or the selected reaction temperatures.
  • the pressure is e.g. at 1 to 1000 bar, e.g. at 40 to 300 bar or at 50 to 200 bar.
  • the reaction can be carried out in batch mode or in continuous mode. Consequently, for example, at least one CSTR (Continuous Stirred Tank Reactor) with at least one internal and / or at least one external heat exchanger, at least one tube reactor, at least one tube bundle reactor or at least one loop reactor can be used as reactors. It is also possible to design at least one of these reactors in such a way that it has at least two different zones. Such zones may be, for example, in reaction conditions such as, for example, the temperature or the pressure and / or in the geometry. differentiation of the zone such as volume or cross section.
  • CSTR Continuous Stirred Tank Reactor
  • reaction is carried out in two or more reactors, two or more identical reactor types or at least two different reactor types can be used.
  • the reaction with dinitrogen monoxide is carried out in a single reactor.
  • the reaction can be carried out in a continuous mode or in batch mode.
  • the residence time of the reaction mixture in the reactor is generally in the range of 0.1 to 40 hours, preferably in the range of 0.1 to 30 hours, more preferably in the range of 2 to 7 hours.
  • the molar ratio of nitrous oxide and the cyclic olefin is generally in the range of 0.01 to 30, e.g. in the range of 0.03 to 10, more preferably in the range of 0.05 to 1, and most preferably in the range of 0.08 to 0.2. Since dinitrogen monoxide is preferably used in excess, only part of the olefin XII (e.g., cyclohexadeca-1, 9-diene) is reacted. Unreacted olefin (e.g., cyclohexadeca-1, 9-diene) is separated by distillation from the reaction product and recycled to the reaction.
  • olefin XII e.g., cyclohexadeca-1, 9-diene
  • the unreacted olefin (e.g., cyclohexadeca-1,9-diene) as the top product and the reaction product as the bottom product of the column are precipitated.
  • the distillation is hereby e.g. at 20 mbar head pressure and e.g. 210 ° C sump temperature instead.
  • the differential pressure across the column is e.g. 18 mbar.
  • the column is e.g. equipped with a structured fabric packing of the type Montz A3.
  • the package height is e.g. 4 m and the feed is e.g. at 2 m.
  • the compound XI is then isolated by distillation as a minor component.
  • the desired reaction product XI is formed as a minor component, so that the reaction mixture must be suitably purified.
  • a purification this can be carried out, for example, by distillation (in particular by fractional distillation, preferably at reduced pressure) or by chromatography.
  • Suitable purification methods are familiar to the person skilled in the art.
  • the cleaning can be done, for example, batchwise or continuously.
  • distillation by means of a distillation column can be used with packings known to those skilled in the art.
  • the optimum distillation conditions can be determined by the skilled person without undue burden.
  • the distillation can be carried out in particular under reduced pressure, for example at a pressure ⁇ 1000 mbar, ⁇ 500 mbar, ⁇ 300 mbar, ⁇ 100 mbar or ⁇ 10 mbar.
  • the distillation column used may have several, such as at least 20, at least 25 or at least 30 theoretical, such as up to 70 separation stages.
  • the reflux ratio may be, for example, in the range of about 5 to 100 and at least 20, at least 25 or at least 30, and is in particular about 100 for a particularly advantageous fractionation.
  • column chromatography may also be carried out in place of or subsequent to a distillative purification.
  • column media and eluents known to the person skilled in the art are used.
  • the optimum chromatography conditions, such as column geometry and speed of the mobile phase, can be determined by the skilled person without undue burden.
  • Suitable column materials are polar adsorbents such. As iron oxide Fe 2 0 3 , alumina, carbohydrates or silica gel with or without additives such. As fluorescent indicators or gypsum.
  • eluents examples include: aliphatic or aromatic eluents, such as, for example, alkanes or cycloalkanes, for example pentane, petroleum ether, hexane, heptane, toluene or the corresponding cyclic compounds; aliphatic ethers, esters or, such as Et 2 0, MTBE, EtOAc, acetone or mixtures of such eluents such. Hexane / MTBE, hexane / EtOAc, pentane / Et 2 0, petroleum ether / Et 2 0.
  • alkanes or cycloalkanes for example pentane, petroleum ether, hexane, heptane, toluene or the corresponding cyclic compounds
  • a suitable starting compound which can be used both in stereoisomerically pure form or in the form of stereoisomer for the preparation of compounds of formula X wherein A is 5 radical of a monounsaturated C are Cyclopentadec-8-enyl and -7-enylcarbaldehyde.
  • the catalytic reaction of the cyclic carbaldehydes with the molecular oxygen is optionally carried out in the presence of at least one suitable solvent or diluent.
  • Oxygen can be used as pure oxygen or preferably as part of ambient air or lean air in the process.
  • Suitable solvents include: polar, aprotic solvents such as dimethylformamide (DMF), hexamethylphosphoramide (HMPA), dimethylsulfoxide (DMSO), tetramethylurea and dimethylacetamide, and mixtures thereof.
  • aprotic organic solvents such as dimethylformamide (DMF), hexamethylphosphoramide (HMPA), dimethylsulfoxide (DMSO), tetramethylurea and dimethylacetamide, and mixtures thereof.
  • Other suitable organic solvents which can be used alone or in combination with the above aprotic organic solvents are alkanols such as, for example, methanol, ethanol, propanol, isopropanol or butanols, such as ie / f-butanol and tetrahydrofuran, dioxane or benzene.
  • the catalytic reaction of the cyclic carbaldehydes can also be carried out in the absence of a solvent or diluent.
  • the catalyst used is Cu (II) -based, in particular homogeneous catalysts. These are preferably formed in situ in the reaction mixture by adding to a Cu (II) salt, in particular a bidentate ligand, preferably diamine ligands.
  • the Cu (II) salt used according to the invention is selected, for example, from Cu (II) acetate, formate, sulfate, chloride or nitrate.
  • Cu (OAc) 2 is used.
  • Suitable complexing ligands are in particular bidentate copper complexing amine ligands such as ⁇ /, ⁇ /, ⁇ / ', ⁇ /' - tetramethylethylenediamine (TMEDA), 1, 10-phenanthroline and 2,2'-bipyridine.
  • TMEDA is used.
  • Complex ligand and Cu (II) salt are used in approximately equimolar ratio.
  • the molar proportion of complex is about 0.1 to 10, in particular 1 to 5, preferably about 2.5 mol%, based on the carbaldehyde (XI) used.
  • the decarbonylation is additionally carried out in the presence of an organic base.
  • the base used in the process according to the invention for example, is selected from diazabicycloalkanes, such as.
  • DBU diazabicyclooctane
  • DBU diazabicycloundecene
  • DBN diazobicyclononane
  • tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine or tripropylamine, ⁇ , ⁇ -dimethylpiperazine, N-methylpyridine, N-methylpyrrolidone, quinuclidine and the like.
  • DBU is used.
  • the base is used in a proportion of 0.1-1 equiv, 0.2-0.8 equiv or more preferably 0.4-0.6 equiv based on the carbaldehydes of the formula (XI) used
  • the temperature of the reaction is, depending on the reactants and solvent used, e.g. at 20 to 100 ° C, in particular at 30 to 80 ° C, especially at 40 to 60 ° C. It is also possible to carry out the reaction at two or more temperatures or in two or more temperature ranges which are each within the limits specified above. Temperature changes in the course of the reaction can be carried out continuously or discontinuously. In particular, the reaction temperature is essentially constant.
  • the pressure during the reaction of the carbaldehydes (XI) with oxygen is in particular at ambient pressure or approximately in the region of the autogenous pressure of the educt or product mixture at the selected reaction temperature or the selected reaction temperatures.
  • the pressure is e.g. at 0.1 to 5 bar, e.g. at 0.1 to 3 bar, preferably about 1 bar.
  • reaction vessels which can be used for the implementation (on a laboratory or production scale).
  • a reactor for example, conventional stirred reactors, CSTR (Continuous Stirred Tank Reactor), each with or without internal and / or external heat exchanger, a tubular reactor, a tube bundle reactor or a loop reactor can be used.
  • CSTR Continuous Stirred Tank Reactor
  • a tubular reactor a tube bundle reactor or a loop reactor
  • the reactors so that they have at least two different zones. Such zones may differ, for example, in reaction conditions such as, for example, the temperature or the pressure and / or in the geometry of the zone, for example the volume or the cross section.
  • two or more identical reactor types or at least two different reactor types can be used. In particular, however, the reaction is carried out in a single reactor, in particular a stirred reactor.
  • the residence time of the reaction mixture in the reactor is generally in the range of 0.1 to 40 hours, preferably in the range of 0.1 to 30 hours, more preferably in the range of 0.1 to 25 hours, in particular 1 to 4 hours.
  • reaction can be carried out as follows:
  • a reaction mixture consisting of an excess of (E / Z) -cyclohexadec-8-enone and an amount of cyclopentadec-8-enylcarbaldehyde present in deficit is optionally dissolved in DMF.
  • DBU diazabicycloundecene
  • XI carbaldehyde
  • a Cu-TMEDA mixture may also be prepared without adding a solvent.
  • the Cu-TMEDA mixture, with or without DMF, is then added dropwise continuously or in a batch of the reaction solution.
  • the reaction was stirred at 40 to 60, such as 50 ° C for 10 to 30 hours, such as 20 hours.
  • EtOAc and water are added.
  • the aqueous phase is adjusted to pH 4, for example, by means of acetic acid or 98% strength H 2 SO 4 .
  • the organic phase is extracted. Subsequently, the aqueous phase is optionally again washed with E- tOAc.
  • the combined organic phases are dried, filtered and concentrated in vacuo. The residue is then processed further if necessary. For example, a fractional distillation is carried out.
  • the cyclopentadecenones X of the invention can thereby be separated from unreacted cyclohexadec-8-enone. If appropriate, the cyclopentadecenones X can subsequently be separated by column chromatography from low-boiling components which have not been separated off by distillation.
  • silica gel is suitable as the stationary phase and the mobile phase is a mixture of cyclohexane: EtOAc, for example by elution using a step gradient 100: 1/30: 1/20: 1. The product is eluted at about 80: 1.
  • (E / Z) -C-cyclopentadec-8-enone is understood to mean a mixture consisting of (E / Z) -cyclopentadec-8-enone (I) and / or (III) and their regioisomers (II ) and / or (IV).
  • Example 1 Preparation of a cyclohexadecenone / cyclopentadone mixture according to the invention
  • TM EDA 120 mg, 0.5 mmol, 2 mol%) and Cu (OAc) 2 (90 mg, 0.5 mmol, 2 mol%) were dissolved in 30 ml of DMF.
  • the Cu-TMEDA mixture was added dropwise via a syringe pump continuously for 6 h or in a batch of the reaction solution. The reaction was stirred at 50 ° C for 20 h. Subsequently, 300 ml of EtOAc were added and 200 ml of water. The aq. Phase is adjusted by means of 98% H 2 S0 4 to pH 4. The organic phase was extracted. The aqueous phase was then washed once more with EtOAc (2 ⁇ 100 ml). The united org.
  • Phases were dried over Na 2 S0 4 , filtered off and concentrated in vacuo.
  • the turnover of the carbaldehydes was> 95%.
  • the selectivity of the cyclopentadecenones was 95%.
  • Cyclohexadec-8-enone was not attacked.
  • the residue was purified by fractional distillation in a rotary column column with a number of stages of 20 at 1 mbar top pressure and 125-129 ° C head and 170-180 ° C bottom temperature worked up.
  • the reflux ratio was 75.
  • the cyclopentadec-7/8-enone was separated from cyclohexadec-8-enone (yield 85%).
  • the cyclopentadec-7/8 enones were separated by column chromatography after the addition of low boilers which could not be separated in the distillation (silica gel, eluent cyclohexane: EtOAc 100: 1, 30: 1, 20: 1) that 1 g of a colorless oil with a purity of 84% (3.7 mmol) could be obtained.
  • IR (ATR) u [crrf 1 ] 301 1, 2935, 2866, 1723, 1456, 1354, 716.
  • IR (ATR) ⁇ [cm -1 ] 3020, 2934, 2864, 1723, 1449, 1353, 969.
  • IR (ATR) ⁇ [cm -1 ] 3012, 2936, 2866, 1723, 1457, 1353, 714.
  • Example 3 Preparation of a cyclohexadecenone / cyclopentadecenone mixture according to the invention
  • the reaction product from Example 3 (969 g of (E / Z) cyclopentadec-8-enone and its regioisomers (1.8%)) was separated by short path evaporation at 240 ° C in heat transfer oil of the evaporator surfaces and 5 mbar of high boilers. Subsequently, the distillate was separated from the low boilers by means of batch distillation. The theoretical number of stages of the fabric packs used Sulzer DX was 50. It was worked at a top pressure of 10 mbar with a differential pressure across the column of 8 mbar. For the separation of the (E / Z) -cyclopentadec-7/8-enone, the reflux ratio was 50.
  • the cyclopentadec-7/8-enone were fractionally distilled. After separation, the reflux ratio for the distillation of the cyclohexadec-8-enone was reduced to 20. The bottom temperature rose during the distillation of 204 to 220 ° C. The head temperature rose from 160 to 175 ° C.
  • Example 6 Preparation of a cyclohexadecenone / cyclopentadecenone mixture according to the invention in the absence of a solvent
  • the reaction mixture was heated to 50 ° C and through the mixture was continuously a stream of air (100 Nl / h) gelei- tet. The mixture was stirred for 4 h. Then, 200 ml of EtOAc, 200 ml of water and 43.4 g of AcOH were added at room temperature, and the mixture was stirred for 5 minutes. The phases were separated and the aqueous phase was extracted once more with 200 ml EtOAc. The combined organic phases were dried over Na 2 S0 4 , filtered and concentrated. The sales of carbohydrates was 97%. The selectivity of cyclopentadecenone was 85%. The loss of cyclohexadec-8-enone was only 0.2%.

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Abstract

Nouveaux mélanges d'isomères de cyclopentadécénone, leur préparation et leur utilisation comme arôme, en particulier en tant que substance odorante; compositions de substances aromatiques, et produits contenant ces mélanges.
EP16778043.6A 2015-10-08 2016-10-07 Utilisation de nouveaux mélanges d'isomères (e/z) de cyclopentadécénone, leur préparation et leur utilisation comme arôme Withdrawn EP3359516A1 (fr)

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EP15188870.8A EP3153494A1 (fr) 2015-10-08 2015-10-08 Utilisation de nouveaux melanges d'isomeres (e/z) de cyclopentadecanone, et son utilisation comme arome
EP16155621 2016-02-15
PCT/EP2016/074021 WO2017060440A1 (fr) 2015-10-08 2016-10-07 Utilisation de nouveaux mélanges d'isomères (e/z) de cyclopentadécénone, leur préparation et leur utilisation comme arôme

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EP3178788A1 (fr) 2015-12-08 2017-06-14 Basf Se Matériau zéolitique à base d'étain présentant une structure bea
ES2899827T3 (es) 2015-12-08 2022-03-14 Basf Se Material zeolítico que contiene estaño y que tiene una estructura de marco BEA
EP3411357A1 (fr) 2016-02-01 2018-12-12 Basf Se Procédé de production lactames c4-c15
BR112018016789A2 (pt) 2016-02-19 2018-12-26 Basf Se processo para preparação biocatalítica e preparação de um composto
BR112018074538B1 (pt) 2016-05-31 2022-09-13 Basf Se Composto, método para preparar compostos, uso de compostos, composição de substância aromatizante e/ou fragrância, produto perfumado ou aromatizado, e, método para perfumar um produto
MY191494A (en) 2016-06-29 2022-06-28 Basf Se Process for the preparation of alpha, beta unsaturated aldehydes by oxidation of alcohols in the presence of a liquid phase
CN109415311B (zh) 2016-07-08 2021-07-23 巴斯夫欧洲公司 制备有机砜的方法
CA3056168A1 (fr) 2017-03-21 2018-09-27 Basf Se Procede de fabrication d'un composant de protection contre la corrosion pour un fluide antigel

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US3496197A (en) * 1969-03-05 1970-02-17 Upjohn Co Oxidation of aldehydes to ketones employing copper ions as catalysts
DE2934678A1 (de) * 1979-08-28 1981-03-12 Haarmann & Reimer Gmbh, 3450 Holzminden Cyclopentadecen-8-on-1, verfahren zu seiner herstellung und seine verwendung als riechstoff
US5936100A (en) * 1996-12-16 1999-08-10 Studiengesellschaft Kohle Mbh Synthesis of functionalized macrocycles by ring closing metathesis
US7485668B2 (en) * 2005-04-14 2009-02-03 International Flavors & Fragrances Inc. Cyclopropanated macrocyclic ketones and lactones
CN102365256A (zh) * 2009-01-28 2012-02-29 巴斯夫欧洲公司 制备纯环十二酮的方法
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