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EP1791804A1 - 2-alkylidene- and 2-(alkyl-1-ene)-cyclopentanone as perfumes - Google Patents

2-alkylidene- and 2-(alkyl-1-ene)-cyclopentanone as perfumes

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Publication number
EP1791804A1
EP1791804A1 EP05784683A EP05784683A EP1791804A1 EP 1791804 A1 EP1791804 A1 EP 1791804A1 EP 05784683 A EP05784683 A EP 05784683A EP 05784683 A EP05784683 A EP 05784683A EP 1791804 A1 EP1791804 A1 EP 1791804A1
Authority
EP
European Patent Office
Prior art keywords
formula
mixture
acetic acid
compound
oxo
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Withdrawn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
EP05784683A
Other languages
German (de)
French (fr)
Inventor
Marcus Eh
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.)
Symrise AG
Original Assignee
Symrise AG
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
Application filed by Symrise AG filed Critical Symrise AG
Publication of EP1791804A1 publication Critical patent/EP1791804A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

Definitions

  • the invention relates to novel 2-alkylidene and 2- (alkyl-1-ene) cyclopentanones, their use as fragrances and perfumed products and fragrance mixtures containing the compounds of the invention, and to a process for their preparation.
  • fragrance industry there is a sustained interest in the development of new fragrances, thus enabling the creation of new perfume oils for both alcoholic and functional perfumery.
  • Compounds with a floral odor are indispensable components in the perfume industry.
  • a special class of these flowery fragrances are compounds with floral-jasmine-like notes. Structurally, compounds with flowery-jasmine-like notes are sometimes characterized by a cyclopentanone ring which is substituted in the ⁇ -position by an alkyl or alkylene radical and in the ⁇ -position by a methylacetate radical.
  • Methyldihydrojasmonat (II) is characterized by a warm, floral Jasminnote, coupled with the fresh floral softness of a lemon.
  • Methyl jasmonate (IM), which is a volatile component of jasmine oil, has a strong flowery-herbaceous, sweet odor reminiscent of jasmine absolute.
  • a weak fruity odor reminiscent of jasmine is found for the cyclopentyl compound (IV).
  • B n-butyl as a pure alkyl group without heteroatoms and R 2 is an unbranched or branched Ci to C 4 alkyl group. It is stated that the compounds of the formula (V) can be used as intermediates for the synthesis of the compounds (II-IV) described above.
  • the object of the present invention to provide jasmine fragrances whose odor profile differs from that of the above-described compounds (II-IV).
  • the jasmine fragrances to be indicated should have original odor aspects in order to expand the range of raw materials available for the composition of perfumes.
  • R 1 is H or methyl
  • R is a branched or unbranched C 1 to C 5 alkyl group
  • meandering lines indicate the E isomer, the Z isomer and the E / Z isomer mixtures, respectively.
  • C 1 to C 5 alkyl group it is possible in particular to use: methyl, ethyl, n-propyl, / so-propyl, n-butyl, sec-butyl, isobutyl, n-pentyl, and the like Pentyl and 3-methylbutyl.
  • the alkyl radicals ethyl, n-propyl, / so-propyl, n-butyl, sec-butyl, isobutyl and n-pentyl and particularly preferably the alkyl radicals ethyl, n-propyl, n-butyl and n-butyl are preferred. pentyl.
  • Another object of the invention are compounds of formula (Ia) and (Ib), wherein
  • R 1 is H or methyl
  • R 2 is a branched or unbranched C 1 to C 5 alkyl group, wherein
  • the compounds of the formula (Ia) and (Ib) to be used according to the invention can be present in the form of a pure optically active enantiomer, an optically active mixture of different enantiomers or any other mixture of the stereoisomers encompassed by the formula I.
  • the compounds of the formula (Ia) and (Ib) which are to be used according to the invention have perfumistically interesting jasmine-like odor notes and, moreover, are distinguished by the desired interesting legotenes.
  • the compounds of the formula (Ia) and (Ib) in addition to the intense Jasminnote have very beautiful fruity and lactone aspects. This is surprising since the odor of the compound (IV) which contains an endocyclic ⁇ , ⁇ -unsaturated double bond is only remotely pronounced of jasmine, whereas the compounds of the formula (Ia) have an exocyclic ⁇ , ⁇ - unsaturated double bond as described have a very intense Jasmingeruch.
  • the compounds of formula (Ia) have a strong radiant jasmine odor with fruity and citrus aspects, and the compounds of formula (Ib) have a softer, less radiant jasmine odor, with lactone aspects.
  • the present invention also relates to mixtures each comprising at least one compound of the formula (Ia) and a compound of the formula (Ib), wherein the proportion of (Ia) is preferably greater than the proportion of (Ib).
  • the jasmine flower-like odor of the compounds of the formula (Ia) with the jasmine-lactone odor of the compounds of the formula (Ib) in a unique manner to an unmistakable, complex Jasmingeruch.
  • the substituents R 1 , R 2 may have the same or different meaning in the formula (Ia) as in the formula (Ib).
  • the invention also relates to the use of a mixture according to the invention as a fragrance.
  • the invention according to a related aspect relates to a method for producing, enhancing or modifying a jasmine smell in a mixture, comprising the following steps: Providing a compound of the invention or a mixture according to the invention,
  • composition of other ingredients with an amount of the inventive compound or mixture sufficient to (a) produce a jasmine smell in the resulting total mixture, (b) to enhance an existing jasmine odor in the composition of other ingredients, or (c) an existing one Jasmingeruch in the composition of other ingredients to modify.
  • the present invention also relates to a fragrance mixture with jasmine smell comprising
  • R 1 is H or methyl
  • R is a branched or unbranched C 1 to C 5 alkyl group and wherein the substituents R 1 and R 2 in the formula (Ia) have the same or different meaning as in the formula (Ib).
  • the invention also relates to perfumed products comprising a perfume mixture according to the invention and a carrier or a substrate which is in direct contact with the perfume mixture.
  • the perfumed product may advantageously be selected from the group consisting of alcoholic perfumes, personal care products and cleaning or care products to be used in the household.
  • the compounds of the formula (Ia) and (Ib) according to the invention can be used as individual substances or in the form of mixtures (see also above) in a large number of perfume mixtures and perfumed products.
  • the compounds of the invention of the above formulas can be combined with other fragrances to novel perfume compositions.
  • jasmine notes which are absolutely pronounced of jasmine and are paired with fruity and lactone accents can often be achieved even at lower doses, the overall impression of odor being remarkably harmonized, the aura perceptibly increased and the fixation, d. H. the adhesion of the perfume composition, are significantly enhanced.
  • fragrances with which the jasmine fragrances of the formula (I) according to the invention can advantageously be combined can be found, for example, in K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 3 rd . Ed., Wiley-VCH, Weinheim 1997.
  • Angelica seed oil Angelica root oil; anise oil; Valerian oil; Basil oil; Tree moss -
  • calamus camphor oil
  • Cananga oil cardamom; Cascarillaöl; cassia; Cassie absolute; Beaver-absolue; Cedemenseöl; Cedemholzöl; cistus;
  • citronella lemon; copaiba balsam; Copaivabalsamöl; Coriander oil;
  • Orris root oil Jasmine absolute; calamus; Chamomile oil blue; Camomile oil Roman; Carrot seed oil; Kaskarillaöl; Kiefemadelöl; spearmint; Seed oil;
  • Parsley leaf oil Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil;
  • fragrances from the group of hydrocarbons such as 3-carene; ⁇ -pinene; beta-pinene; ⁇ -terpinene; ⁇ -terpinene; p-cymene; bisabolene; camphene; Caryophyllene; cedrene; Famesen; limonene; longifolene; myrcene; ocimene; valencene; (E 1 Z) -1, 3,5-undecatriene;
  • the aliphatic alcohols such. Hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyl-octanol; (E) -2-hexenol; (E) - and (Z) -3-hexenol; 1-octene-3-ol; Mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E, Z) -2,6-Nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; the aliphatic aldehydes and their 1, 4-dioxacycloalkene-2-ones such.
  • the aliphatic ketones and their oximes e.g. 2-heptanone; 2-octanone; 3- Octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; the aliphatic sulfur-containing compounds, e.g. 3-methylthiohexanol; 3-Methylthiohexylacetat; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;
  • the aliphatic nitriles such as 2-nonenitrile; 2-Tridecen Textrenitril; 2,12-tridecenoic acid nitrile; 3,7-dimethyl-2,6-octadienklarenitril; 3,7-dimethyl-6-octenitrile; the aliphatic carboxylic acids and their esters such as (E) - and (Z) -3-hexenyl formate; ethylacetoacetate; isoamyl; hexyl acetate; 3,5,5-trimethyl-hexyl acetate; 3-methyl-2-butenyl acetate; (E) -2-hexenyl acetate; (E) - and (Z) -3-hexenylacetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; Butyl butyrate, isoamyl;
  • acyclic terpene alcohols e.g. citronellol; geraniol; nerol; linalool; Lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octene-2-ol; 2,6-dimethyl octane-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadiene-2-ol; 2,6-dimethyl-3,5-octadiene-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1, 5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-1-ol; as well as their formates, acetates, propionates, isobutyrate
  • geranial e.g. geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranyl acetone; and the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal;
  • the cyclic terpene alcohols e.g. Menthol; isopulegol; alpha-terpineol; Terpinenol-4; Menthane-8-ol; Menthane-1-ol; Menthane-7-ol; borneol; Isobomeol; linalool; monopoly; cedrol; ambrinol; Vetyverol; guaiol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates;
  • Menthol isopulegol
  • alpha-terpineol Terpinenol-4
  • Menthane-8-ol Menthane-1-ol
  • Menthane-7-ol borneol
  • Isobomeol linalool
  • monopoly cedrol
  • the cyclic terpene aldehydes and ketones such as menthone; menthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchon; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethyl-ionone; alpha-lron; alpha-damascone; beta-damascone; beta- damascenone; delta-damascone; gamma-damascone; 1 - (2,4,4-trin-ethyl-2-cyclohexene-1-yl) -2-butene-1-one; 1.SA ⁇ X ⁇ a-hexahydro-i, 1,5,5-tetrannethyl-2H-2,4a-methanonaphthalene-8 (5H) -one; nootkatone; Dihydronootkaton;
  • cyclic alcohols e.g. 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; S-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2, Z5, E9-cyclododecatriene-1-ol; 2-isobutyl-4-methyl tetrahydro-2H-pyran-4-ol;
  • cycloaliphatic alcohols such as alpha.SS-trimethylcyclohexylmethanol; 2-methyl-4- (2 J 2,3-trimethyl-3-cyclopent-1-yl) butanol; 2-methyl-4- (2 J 2,3-trimethyl-cyclopent-3-1-yl) -2-buten-1-ol; 2-ethyl-4- (2 J 2,3-trimethyl-3-cyclopent-1-yl) -2-buten-1-ol; 3-methyl-5- (2 J 2,3-trimethyl-3-cyclopent-1-yl) pentan-2-ol; 3-methyl-5- (2 J 2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 3 J 3-dimethyl-5- (2 J 2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 1 - (2,2,6-trimethylcyclohexyl) pentan-3-ol; 1 - (2,2,6-trimethylcyclohexyl)
  • cyclic and cycloaliphatic ethers e.g. cineol; cedryl methyl ether; cyclododecyl; (Ethoxymethoxy) cyclododecane; alpha-Cedrenepoxid; Sa.e.beta.-tetramethyldodecahydronaphthop, 1-b] furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho [2, 1 -bjfuran; 1, 5,9-trimethyl-13-oxabicyclo [10.1.0] trideca-4,8-diene; rose oxide; 2- (2,4-dimethyl-3-cyclohexene-1-yl) -5-methyl-5- (1-methylpropyl) -1,3-dioxane;
  • cyclic ketones such as 4-tert-butylcyclohexanone; 2 J 2,5-trimethyl-5- pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopentene-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopentene-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; S-methylcyclopentadecanone; 4- (1-ethoxyvinyl) -3,3,5,5-tetra methylcyclohexanone; 4-tert.-pentylcyclohexanone; 5-cyclohexadecen-i-one; 6,7-dihydro-1,1- J 2,3 J 3-pentamethyl-4 (5H) -indanone; 5-cyclohexadecene-
  • 1,2,3A5A7,8- ⁇ ( ⁇ ahydro-2-naphthalenylmethylketone; methyl ⁇ e.iO-trimethyl ⁇ S. ⁇ cyclododecatrienyl ketone; tert-butyl (2,4-dimethyl-3-cyclohexen-1-yl) ketone;
  • ester of cyclic alcohols e.g. 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate;
  • esters of cycloaliphatic carboxylic acids such as.
  • allyl-3-cyclohexylpropionate Allylcyclohexyloxyacetat; methyldihydrojasmonate; methyl jasmonate; Methyl 2-hexyl-3-oxocyclopentanecarboxylate; Ethyl ⁇ -ethyl- ⁇ , ⁇ -dimethylcyclohexenecarboxylate; Ethyl ⁇ SAE-tetramethyl ⁇ -cyclohexencarboxylat; Ethyl 2-methyl-1,3-dioxolane-2-acetate;
  • aromatic hydrocarbons such as Styrene and diphenylmethane
  • the araliphatic alcohols such as benzyl alcohol; 1-phenylethyl; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3- (3-methylphenyl) propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1, 1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propene-1-ol; 4-methoxybenzyl; 1 - (4-isopropylphenyl) ethanol; the ester of araliphatic alcohols and aliphatic carboxylic acids such as; benzyl acetate; benzylpropionate; benzyl isobutyrate;
  • aromatic and araliphatic ketones such as e.g. acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4- (4-hydroxyphenyl) -2-butanone; 1- (2-naphthalenyl) ethanone; benzophenone; I, I, ⁇ , ⁇ -hexamethyl-S-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1 - [2,3-dihydro-1, 1, 2,6-tetramethyl-3- (1-methylethyl) -1H-5-indenyl] ethanone; S'.e'y'. ⁇ '-tetrahydro-S'.S'.S'.e'. ⁇ '. ⁇ '-hexamethyl-acetonaphthone;
  • aromatic and araliphatic carboxylic acids and their esters such as benzoic acid; phenylacetic acid; methylbenzoate; ethyl benzoate; hexyl benzoate; Benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; Phenylethyl phenylacetate; Methylcinnmat; ethylcinnamate; Benzyl; Phenylethylcinnamat; cinnamyl cinnamate; AIIyI phenoxyacetate; methyl salicylate; isoamyl; hexyl salicylate; cyclohexyl; Cis-3-hexenyl salicylate; benzyl; phenylethyl; Methyl-2,4-dihydroxy-3,6-dinnethylbenzoat; Ethyl 3-phenylglycidate; E
  • the nitrogen-containing aromatic compounds such as e.g. 2,4,6-trinitro-i, 3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert.-butylacetophenone; cinnamic acid; 5-phenyl-3-methyl-2-penten Aciditril; 5-phenyl-3-methylpentanitrile; methyl anthranilate; Methyl N-methylanthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexene carbaldehyde; 6
  • the phenols, phenyl ethers and phenyl esters e.g. estragole; anethole; eugenol; Eugenylmethylether; isoeugenol; Isoeugenylmethylether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-Naphthylethylether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; Eugenylacetat; 2-methoxy-4-methylphenol; 2-ethoxy-5- (1-propenyl) phenol; p-Kresylphenylacetat;
  • heterocyclic compounds such as e.g. 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;
  • the lactones such as 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1, 5-dodecanolide; 1.15 pentadecanolide; cis- and trans-11-pentadecene-1,15-olide; cis- and trans-12-pentadecene-1, 15-olide; 1, 16-hexadecanolide; 9-hexadecene-1, 16-olide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1, 16-hexadecanolide; Ethylene-1,12-dodecanedioate; Ethylene-1,13-tridecandi
  • Perfume oils containing the compounds of the above formulas according to the invention can be used in perfumed form in liquid form, neat or diluted with a solvent.
  • Suitable solvents for this are, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc.
  • Perfume oils containing the compounds according to the invention can be absorbed on a carrier which ensures both a fine distribution of the odoriferous substances in the product and a controlled release during use.
  • a carrier may be porous inorganic materials such as light sulfate, silica gels, zeolites, gypsum, clays, clay granules, aerated concrete, etc., or organic materials such as woods and cellulosic based materials.
  • Perfume oils containing the compounds of the invention may also be microencapsulated, spray dried, present as inclusion complexes or as extrusion products and added in this form to the product to be perfumed.
  • the properties of the perfume oils modified in this way can be further optimized by so-called “coating” with suitable materials with a view to a more targeted release of fragrance, to which end waxy plastics such as polyvinyl alcohol are preferably used.
  • the microencapsulation of the perfume oils can be carried out, for example, by the so-called coacervation process with the aid of capsule materials, for example of polyurethane-like substances or soft gelatin.
  • the spray-dried perfume oils can be prepared, for example, by spray-drying a perfume oil-containing emulsion or dispersion, it being possible to use as starches modified starches, proteins, dextrin and vegetable gums.
  • Inclusion complexes may be prepared, for example, by incorporating dispersions of the perfume oil and cyclodextrins or urea derivatives into a suitable solvent, eg, water.
  • Extrusions- Products can be made by fusing the perfume oils with a suitable waxy substance and by extrusion with subsequent solidification, if appropriate in a suitable solvent, for example isopropanol.
  • the total amount of the compounds or mixtures according to the invention to be used according to the invention is preferably 0.05 to 50% by weight, preferably 0.5 to 20% by weight, based on the total perfume oil.
  • Perfume oils containing the compounds according to the invention can be used in concentrated form, in solutions or in modified form described above for the production of, for example, perfume extracts, Eau de perfumes, Eau de Toilettes, shaving waters, Eau de Colognes, Pre-shave Products, splash colognes and perfumed refreshing wipes and the perfuming of acidic, alkaline and neutral detergents, such as 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, powder detergents, laundry pretreatment agents such as bleaches, soak and stain removers, fabric softeners, laundry soaps, washing tablets, disinfectants, surface disinfectants and air fresheners in liquid, gel or solid support form, aerosol sprays, Waxes and polishes such as furniture polishes, floor waxes, shoe polishes and personal care products such as solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams
  • the invention also relates to a process for preparing mixtures according to the invention which comprise a compound of the formula (Ia) and a compound of the formula (Ib), comprising the following steps:
  • Compounds of the formula (Ib) can be obtained by chromatographic or distillative separation of a mixture according to the invention.
  • the compounds of the formula (Ia) and (Ib) to be used according to the invention as jasmine fragrances can be prepared by methods well known to the person skilled in the art.
  • the preferred Baylis-Hillman reaction of cyclopentenone with an aliphatic aldehyde for preparing the alcohol of the formula (VI) is preferably carried out according to the instructions of YMA Yamada and S. Ikegami, Tetrahedron Lett., 41, 2165 (2000), ie in the presence of rac-1, 1 '- bi-2-naphthol and tributylphosphine.
  • the Johnson-Claisen 3.3 sigmatropic rearrangement of the alcohol of formula (VI) is preferably carried out in toluene and in the presence of catalytic amounts of propionic acid, preferably according to the instructions of S.E. Drewes et al., Synth. Comm, 20, 1437 (1990) (Scheme 1).
  • a further aspect of the present invention relates to a process for the preparation of a compound of the formula (Ib) which comprises the following step: isomerizing a mixture of the compounds of the formulas (Ia) and (Ib) (or else the
  • a polar aprotic solvent such as dimethylformamide (DMF) or N-methyl-2- pyrrolidinone (NMP) or a polar protic solvent such as methanol, ethanol or tert-butanol.
  • DMF dimethylformamide
  • NMP N-methyl-2- pyrrolidinone
  • a polar protic solvent such as methanol, ethanol or tert-butanol.
  • the z. B. obtained after the Johnson-Claisen-3.3-sigmatropic rearrangement mixture of the compounds of formulas (Ia) and (Ib) with potassium butoxide-finished in DMF and then at z. B. 0 ° C quenched with 20% acetic acid, according to the procedure in EP 203 528.
  • reaction solution is diluted with hexane (1 ml / mmol cyclopentenone) and then washed each 1x with saturated NH 4 Cl solution, saturated NaHCO 3 solution and saturated NaCl solution, the organic phase is dried over Na 2 SO 4 and after filtration, the solvent is removed on a rotary evaporator.
  • Odor strong, radiant jasmine note, with fruity aspects
  • the odor of the isomeric mixture as shown in the table above is described as follows: strong, radiant and soft jasmine note with fruity aspects.
  • Odor of the isomer mixture strong, soft jasmine note, with a nice fruity note.
  • Odor of the isomer mixture jasmine, intense green note.
  • Odor of the isomer mixture soft jasmine note paired with fruity banana note.
  • the mixture is stirred for 4 hours at room temperature, before cooling to 0 ° C and 20% aqueous acetic acid (0.35 ml / mmol [2-alkylidene-3-oxo-cyclopentyl] - acetic acid methyl ester) rapidly added. After stirring for 15 minutes, add a little water and then extract three times with ether. The combined organic phases are each washed once each with 10% NaHCO 3 solution and water, dried over Na 2 SO 4 , filtered off and concentrated by rotary evaporation. The crude product obtained is purified by flash chromatography on silica gel.
  • the 1 H-NMR and 13 C-NMR spectra of the isomer mixture correspond to the sum of the spectra of the individual isomers from Example 7.
  • Odor of the isomer mixture soft jasmine note with lactone aspects.
  • the 1 H-NMR and 13 C-NMR spectra of the isomer mixture correspond to the 1 H-NMR and 13 C-NMR spectra of the isomer mixture from Example 8, with the difference that the intensities are shifted.
  • Odor of the isomer mixture soft jasmine note, with beautiful lactonigen aspects.
  • perfume oil can be used for the perfuming of various cosmetic products, in particular for bubble bath and shampoo.
  • DPG dipropylene glycol
  • IPM isopropyl myristate
  • the valuable character of [2-hex- (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester / [2 - ((E / Z) -hex-1-enyl) -3-oxo is particularly important -cyclopentyl] -acetic acid methyl ester in the ratio - 5: 1 by.

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Abstract

The invention relates to the use of a compound of formula (Ia) or (Ib) as a jasmine perfume. In each of the formulae (Ia) and (Ib), R<sup

Description

2-Alkyliden- und 2-(Alkyl-1-en)-cyclopentanone als Riechstoffe 2-Alkylidene and 2- (alkyl-1-ene) cyclopentanones as fragrances
Die Erfindung betrifft neue 2-Alkyliden- und 2-(Alkyl-1-en)-cyclopentanone, ihre Verwendung als Riechstoffe sowie parfümierte Produkte und Riechstoffmischungen enthaltend die erfindungsgemäßen Verbindungen, sowie ein Verfahren zu ihrer Herstellung.The invention relates to novel 2-alkylidene and 2- (alkyl-1-ene) cyclopentanones, their use as fragrances and perfumed products and fragrance mixtures containing the compounds of the invention, and to a process for their preparation.
In der Riechstoffindustrie besteht ein nachhaltiges Interesse an der Entwicklung von neuen Riechstoffen, um somit die Kreation von neuen Parfümölen für die alkoholische, wie auch funktionelle Parfümerie zu ermöglichen. Verbindungen mit blumigen Geruch sind hierbei unverzichtbare Komponenten in der Duftstoff¬ industrie. Eine besondere Klasse dieser blumigen Riechstoffe sind Verbindungen mit blumig-jasminartigen Noten. Strukturell zeichnen sich Verbindungen mit blumig-jasminartigen Noten in manchen Fällen durch einen Cyclopentanon-Ring aus, der in α-Position durch einen Alkyl- oder Alkylen-Rest und in ß-Position durch einen Methylacetat Rest substituiert ist. Die zwei wichtigsten Vertreter dieser Klasse von Riechstoffen sind die natürlich vorkommenden 3-Oxo-2-pentyl- cyclopentyl-essigsäuremethylester (II) (Methyldihydrojasmonat, Hedione®, Firmenich S.A.) und 3-Oxo-2-(pent-2-enyl)-cyclopentyl-essigsäuremethylester (IM) (Methyljasmonate). Ein weiterer Vertreter dieser Substanzklasse ist 3-Oxo-2- pentyl-cyclopent-1-enyl-essigsäuremethylester (IV), diese Verbindung wird aber weniger als Riechstoff, sondern vielmehr als Vorprodukt für die Synthese von 3- Oxo^-pentyl-cyclopentyl-essigsäuremethylester (II) eingesetzt.In the fragrance industry, there is a sustained interest in the development of new fragrances, thus enabling the creation of new perfume oils for both alcoholic and functional perfumery. Compounds with a floral odor are indispensable components in the perfume industry. A special class of these flowery fragrances are compounds with floral-jasmine-like notes. Structurally, compounds with flowery-jasmine-like notes are sometimes characterized by a cyclopentanone ring which is substituted in the α-position by an alkyl or alkylene radical and in the β-position by a methylacetate radical. The two most important members of this class of scents are the naturally occurring 3-oxo-2-pentyl cyclopentyl-methyl acetate (II) (methyldihydrojasmonate, Hedione ®, Firmenich SA) and 3-oxo-2- (pent-2-enyl) -cyclopentyl-acetic acid methyl ester (IM) (methyl jasmonate). Another representative of this class of substances is 3-oxo-2-pentyl-cyclopent-1-enyl-acetic acid methyl ester (IV), but this compound is less as a fragrance, but rather as a precursor for the synthesis of 3-oxo ^ -pentyl-cyclopentyl- Acetic acid methyl ester (II) used.
Methyldihydrojasmonat (II) zeichnet sich durch eine warme, blumige Jasminnote, gepaart mit der frischen blumigen Weichheit einer Zitrone aus. Methyljasmonat (IM), welches ein flüchtiger Bestandteil des Jasminöls ist, besitzt einen starken blumig-krautigen, süßen Geruch, der an Jasmin absolute erinnert. Demgegenüber steht ein schwacher fruchtiger Geruch, der nicht an Jasmin erinnert, für die Cyclopentylverbindung (IV).Methyldihydrojasmonat (II) is characterized by a warm, floral Jasminnote, coupled with the fresh floral softness of a lemon. Methyl jasmonate (IM), which is a volatile component of jasmine oil, has a strong flowery-herbaceous, sweet odor reminiscent of jasmine absolute. On the other hand, a weak fruity odor reminiscent of jasmine is found for the cyclopentyl compound (IV).
Aus S. Shicheng et al., Youji Huaxue, 1986, 20, 453 ist [2-Pentyliden-3-oxo- cyclopentyl]-essigsäuremethylester bekannt, welcher als Zwischenprodukt erhalten wird, und für die weitere Synthese zu Methyldihydrojasmonat der obigen Formel Il und Methyldihydroneojasmonat benutzt wird.S. Shicheng et al., Youji Huaxue, 1986, 20, 453 discloses [2-pentylidene-3-oxo-cyclopentyl] -acetic acid methyl ester, which is obtained as an intermediate, and for the further synthesis to methyl dihydrojasmonate of the above formula II and II Methyldihydroneojasmonat is used.
In WO 2004/043895 wird ein Prozess zur Synthese von Alkylidencyclopentanon- Derivaten (V) beschrieben.In WO 2004/043895 a process for the synthesis of Alkylidencyclopentanon- derivatives (V) is described.
Hierbei repräsentiert G eine C=O oder C(OR)2 Gruppe, R1 z. B. n-Butyl als reine Alkylgruppe ohne Heteroatome und R2 eine unverzweigte oder verzweigte Ci bis C4 Alkylgruppe. Es wird ausgeführt, dass die Verbindungen der Formel (V) als Zwischenprodukte für die Synthese der oben beschriebenen Verbindungen (Il - IV) eingesetzt werden können. Here G represents a C = O or C (OR) 2 group, R 1 z. B. n-butyl as a pure alkyl group without heteroatoms and R 2 is an unbranched or branched Ci to C 4 alkyl group. It is stated that the compounds of the formula (V) can be used as intermediates for the synthesis of the compounds (II-IV) described above.
Die Auswahl an blumig-jasminigen Riechstoffen, die dem Parfümeur für die Kreation von Parfümölen zur Verfügung stehen, ist sehr begrenzt.The range of floral-jasmine fragrances available to the perfumer for the creation of perfume oils is very limited.
Es war deshalb die Aufgabe der vorliegenden Erfindung, Jasmin-Riechstoffe anzugeben, deren Geruchsprofil sich von dem der oben beschriebenen Verbindungen (Il - IV) unterscheidet. Vorteilhafterweise sollten dabei die anzugebenden Jasmin-Riechstoffe originelle geruchliche Aspekte aufweisen, um so die für die Komposition von Parfüms zur Verfügung stehende Rohstoffpalette zu erweitern.It was therefore the object of the present invention to provide jasmine fragrances whose odor profile differs from that of the above-described compounds (II-IV). Advantageously, the jasmine fragrances to be indicated should have original odor aspects in order to expand the range of raw materials available for the composition of perfumes.
Erfindungsgemäß wird diese Aufgabe gelöst durch die Verwendung einer Verbindung der Formel (Ia) oder (Ib):According to the invention, this object is achieved by the use of a compound of the formula (Ia) or (Ib):
wobei in jeder der Formeln (Ia) und (Ib)wherein in each of the formulas (Ia) and (Ib)
R1 H oder Methyl undR 1 is H or methyl and
R eine verzweigte oder unverzweigte d- bis C5-Alkylgruppe ist,R is a branched or unbranched C 1 to C 5 alkyl group,
als (Jasmin-)Riechstoff. - A -as (jasmine) fragrance. - A -
In den Formeln (Ia) und (Ib) kennzeichnen geschlängelte Linien jeweils das E- Isomer, das Z-Isomer und die E/Z-Isomerenmischungen.In the formulas (Ia) and (Ib), meandering lines indicate the E isomer, the Z isomer and the E / Z isomer mixtures, respectively.
Als verzweigte oder unverzweigte d- bis C5-Alkylgruppe kann insbesondere eingesetzt werden: Methyl, Ethyl, n-Propyl, /so-Propyl, n-Butyl, se/c.-Butyl, iso- Butyl, n-Pentyl, /so-Pentyl und 3-Methylbutyl. Bevorzugt sind insoweit jedoch die Alkylreste Ethyl, n-Propyl, /so-Propyl, n-Butyl, sek.-Butyl, iso-Butyl und n-Pentyl und besonders bevorzugt die Alkylreste Ethyl, n-Propyl, n-Butyl und n-Pentyl.As branched or unbranched C 1 to C 5 alkyl group it is possible in particular to use: methyl, ethyl, n-propyl, / so-propyl, n-butyl, sec-butyl, isobutyl, n-pentyl, and the like Pentyl and 3-methylbutyl. However, the alkyl radicals ethyl, n-propyl, / so-propyl, n-butyl, sec-butyl, isobutyl and n-pentyl and particularly preferably the alkyl radicals ethyl, n-propyl, n-butyl and n-butyl are preferred. pentyl.
Ein weiterer Gegenstand der Erfindung sind Verbindungen der Formel (Ia) und (Ib), wobeiAnother object of the invention are compounds of formula (Ia) and (Ib), wherein
R1 H oder Methyl ist undR 1 is H or methyl and
R2 eine verzweigte oder unverzweigte Ci bis C5 Alkylgruppe ist, wobeiR 2 is a branched or unbranched C 1 to C 5 alkyl group, wherein
die bereits aus WO 2004/043895 bekannte Verbindung der Formel (Ia) mit R1 = H und R2 = n-Propyl ausgenommen ist.the already known from WO 2004/043895 compound of formula (Ia) with R 1 = H and R 2 = n-propyl is excluded.
Die erfindungsgemäß zu verwendenden Verbindungen der Formel (Ia) und (Ib) können in Form eines reinen optisch aktiven Enantiomers, einer optisch aktiven Mischung verschiedener Enantiomere oder einer sonstigen beliebigen Mischung der von der Formel I umfassten Stereoisomere vorliegen.The compounds of the formula (Ia) and (Ib) to be used according to the invention can be present in the form of a pure optically active enantiomer, an optically active mixture of different enantiomers or any other mixture of the stereoisomers encompassed by the formula I.
Die erfindungsgemäß zu verwendenden Verbindungen der Formel (Ia) und (Ib) besitzen parfümistisch interessante jasminartige Geruchsnoten und zeichnen sich überdies durch die gewünschten interessanten Beinoten aus. Überraschenderweise besitzen die Verbindungen der Formel (Ia) und (Ib) neben der intensiven Jasminnote sehr schöne fruchtige und lactonige Aspekte. Dies ist überraschend, denn der Geruch der Verbindung (IV), welche eine endocyclische α,ß-ungesättigte Doppelbindung enthält, erinnert nur entfernt an Jasmin, wohingegen die Verbindungen der Formel (Ia) mit einer exocyclischen α,ß- ungesättigten Doppelbindung wie beschrieben einen sehr intensiven Jasmingeruch aufweisen.The compounds of the formula (Ia) and (Ib) which are to be used according to the invention have perfumistically interesting jasmine-like odor notes and, moreover, are distinguished by the desired interesting legotenes. Surprisingly, the compounds of the formula (Ia) and (Ib) in addition to the intense Jasminnote have very beautiful fruity and lactone aspects. This is surprising since the odor of the compound (IV) which contains an endocyclic α, β-unsaturated double bond is only remotely reminiscent of jasmine, whereas the compounds of the formula (Ia) have an exocyclic α, β- unsaturated double bond as described have a very intense Jasmingeruch.
Sensorisch besonders wertvoll sind erfindungsgemäß zu verwendende Verbindungen der Formeln (Ia) und (Ib), wobei R1 = H ist und R2 vorzugsweise Ethyl, n-Propyl, n-Butyl oder n-Pentyl ist, besonders bevorzugt ist R1 = H und R2 = n-Propyl und n-Butyl.Of particular sensory value according to the invention are compounds of the formulas (Ia) and (Ib) to be used, where R 1 = H and R 2 is preferably ethyl, n-propyl, n-butyl or n-pentyl, R 1 = H being particularly preferred and R 2 = n-propyl and n-butyl.
Die Verbindungen der Formel (Ia) besitzen einen starken strahlenden Jasmin- Geruch mit fruchtigen und citrischen Aspekten, und die Verbindungen der Formel (Ib) besitzen einen weicheren, nichts so strahlenden Jasmin-Geruch, mit lactonigen Aspekten.The compounds of formula (Ia) have a strong radiant jasmine odor with fruity and citrus aspects, and the compounds of formula (Ib) have a softer, less radiant jasmine odor, with lactone aspects.
Gemäß einem weiteren Aspekt betrifft die vorliegende Erfindung auch Mischungen, die jeweils zumindest eine Verbindung der Formel (Ia) und eine Verbindung der Formel (Ib) umfassen, wobei der Anteil an (Ia) vorzugsweise größer ist als der Anteil an (Ib). In diesen Mischungen paart sich der an Jasminblüten erinnernde Geruch der Verbindungen der Formel (Ia), mit dem jasminig-lactonigen Geruch der Verbindungen der Formel (Ib) in einzigartiger Weise zu einem unverwechselbaren, komplexen Jasmingeruch. Die Substituenten R1, R2 können in der Formel (Ia) die gleiche oder eine andere Bedeutung haben als in Formel (Ib). Wie weiter unten noch anhand des Syntheseweges gemäß Schema I näher erläutert wird, lassen sich die Mischungen umfassend eine Verbindung der Formel (Ia) und eine Verbindung der Formel (Ib), wobei die Substituenten in (Ia) und (Ib) identisch sind, in besonders wirtschaftlicher Weise synthetisieren.According to a further aspect, the present invention also relates to mixtures each comprising at least one compound of the formula (Ia) and a compound of the formula (Ib), wherein the proportion of (Ia) is preferably greater than the proportion of (Ib). In these mixtures, the jasmine flower-like odor of the compounds of the formula (Ia), with the jasmine-lactone odor of the compounds of the formula (Ib) in a unique manner to an unmistakable, complex Jasmingeruch. The substituents R 1 , R 2 may have the same or different meaning in the formula (Ia) as in the formula (Ib). As will be explained in more detail below with reference to the synthesis route according to Scheme I, the mixtures comprising a compound of formula (Ia) and a compound of formula (Ib) wherein the substituents in (Ia) and (Ib) are identical, in synthesize particularly economically.
Die Erfindung betrifft auch die Verwendung einer erfindungsgemäßen Mischung als Riechstoff.The invention also relates to the use of a mixture according to the invention as a fragrance.
Des Weiteren betrifft die Erfindung gemäß einem verwandten Aspekt ein Verfahren zum Erzeugen, Verstärken oder Modifizieren eines Jasmingeruchs in einer Mischung, mit folgenden Schritten: Bereitstellen einer erfindungsgemäßen Verbindung oder einer erfindungsgemäßen Mischung,Furthermore, the invention according to a related aspect relates to a method for producing, enhancing or modifying a jasmine smell in a mixture, comprising the following steps: Providing a compound of the invention or a mixture according to the invention,
Bereitstellen einer Komposition sonstiger Bestandteile undProviding a composition of other ingredients and
Vermischen der Komposition sonstiger Bestandteile mit einer Menge der erfindungsgemäßen Verbindung oder der erfindungsgemäßen Mischung, die ausreicht, (a) in der resultierenden Gesamtmischung einen Jasmingeruch zu erzeugen, (b) einen vorhandenen Jasmingeruch in der Komposition sonstiger Bestandteile zu verstärken oder (c) einen vorhandenen Jasmingeruch in der Komposition sonstiger Bestandteile zu modifizieren.Mixing the composition of other ingredients with an amount of the inventive compound or mixture sufficient to (a) produce a jasmine smell in the resulting total mixture, (b) to enhance an existing jasmine odor in the composition of other ingredients, or (c) an existing one Jasmingeruch in the composition of other ingredients to modify.
Die vorliegende Erfindung betrifft auch eine Riechstoffmischung mit Jasmingeruch, umfassendThe present invention also relates to a fragrance mixture with jasmine smell comprising
(i) eine sensorisch wirksame Menge einer Verbindung der Formel (Ia) oder (Ib) oder einer Mischung unterschiedlicher Verbindungen der Formel (Ia) oder (Ib)(i) a sensorially effective amount of a compound of the formula (Ia) or (Ib) or of a mixture of different compounds of the formula (Ia) or (Ib)
wobei in jeder der Formeln (Ia) und (Ib)wherein in each of the formulas (Ia) and (Ib)
R1 H oder Methyl undR 1 is H or methyl and
R eine verzweigte oder unverzweigte d- bis C5-Alkylgruppe ist und wobei die Substituenten R1 und R2 in der Formel (Ia) die gleiche oder eine andere Bedeutung haben als in der Formel (Ib).R is a branched or unbranched C 1 to C 5 alkyl group and wherein the substituents R 1 and R 2 in the formula (Ia) have the same or different meaning as in the formula (Ib).
sowiesuch as
(ii) gegebenenfalls einen oder mehrere weitere übliche Bestandteile, wie Lösungsmittel, weitere Riechstoffe oder dergleichen.(ii) optionally one or more other conventional ingredients such as solvents, other fragrances or the like.
Die Erfindung betrifft auch parfümierte Produkte, umfassend eine erfindungsgemäße Riechstoffmischung sowie einen Träger oder ein Substrat, der bzw. das in direktem Kontakt mit der Riechstoffmischung steht. Das parfümierte Produkt kann dabei vorteilhafterweise ausgewählt sein aus der Gruppe bestehend aus alkoholischen Parfüms, Körperpflegeprodukten und im Haushalt zu verwendende Reinigungs- oder Pflegeprodukten.The invention also relates to perfumed products comprising a perfume mixture according to the invention and a carrier or a substrate which is in direct contact with the perfume mixture. The perfumed product may advantageously be selected from the group consisting of alcoholic perfumes, personal care products and cleaning or care products to be used in the household.
Die erfindungsgemäßen Verbindungen der Formel (Ia) und (Ib) können als Einzelstoffe oder in Form von Mischungen (siehe dazu auch oben) in einer Vielzahl von Riechstoffmischungen und parfümierten Produkten eingesetzt werden. Besonders vorteilhaft lassen sich die erfindungsgemäßen Verbindungen der oben angegebenen Formeln mit anderen Riechstoffen zu neuartigen Parfümkompositionen kombinieren.The compounds of the formula (Ia) and (Ib) according to the invention can be used as individual substances or in the form of mixtures (see also above) in a large number of perfume mixtures and perfumed products. Particularly advantageously, the compounds of the invention of the above formulas can be combined with other fragrances to novel perfume compositions.
Durch die Verwendung der erfindungsgemäßen Verbindungen der oben angegebenen Formeln lassen sich häufig bereits in geringerer Dosierung in den resultierenden Parfümkompositionen Jasminnoten erreichen, die an Jasmin absolute erinnern und mit fruchtigen und lactonigen Akzenten gepaart sind, wobei der geruchliche Gesamteindruck auffallend harmonisiert, die Ausstrahlung wahrnehmbar erhöht und die Fixierung, d. h. das Haftvermögen der Parfümkomposition, deutlich verstärkt sind.By using the compounds according to the invention of the formulas given above, jasmine notes which are absolutely reminiscent of jasmine and are paired with fruity and lactone accents can often be achieved even at lower doses, the overall impression of odor being remarkably harmonized, the aura perceptibly increased and the fixation, d. H. the adhesion of the perfume composition, are significantly enhanced.
Beispiele für Riechstoffe, mit denen die erfindungsgemäßen Jasmin-Riechstoffe der Formel (I) vorteilhaft kombiniert werden können, finden sich z.B. in K. Bauer, D. Garbe und H. Surburg, Common Fragrance and Flavor Materials, 3rd. Ed., Wiley-VCH, Weinheim 1997.Examples of fragrances with which the jasmine fragrances of the formula (I) according to the invention can advantageously be combined can be found, for example, in K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 3 rd . Ed., Wiley-VCH, Weinheim 1997.
Im einzelnen seien genannt:Specifically, may be mentioned:
Extrakte aus natürlichen Rohstoffen wie Etherische öle, Concretes, Absolues, Resine, Resinoide, Balsame, Tinkturen wie z. B. Ambratinktur; Amyrisöl;Extracts from natural raw materials such as essential oils, concretes, absolues, resines, resinoids, balsams, tinctures such. B. amber tincture; Amyrisöl;
Angelicasamenöl; Angel icawurzelöl; Anisöl; Baldrianöl; Basilikumöl; Baummoos -Angelica seed oil; Angelica root oil; anise oil; Valerian oil; Basil oil; Tree moss -
Absolue; Bayöl; Beifußöl; Benzoeresin; Bergamotteöl; Bienenwachs-Absolue;absolute; Bay oil; Mugwort oil; Benzoeresin; Bergamot oil; Beeswax absolute;
Birkenteeröl; Bittermandelöl; Bohnenkrautöl; Buccoblätteröl; Cabreuvaöl; Cadeöl;birch tar; Bitter almond oil; Savory oil; Buccoblätteröl; Cabreuvaöl; cade oil;
Calmusöl; Campheröl; Canangaöl; Cardamomenöl; Cascarillaöl; Cassiaöl; Cassie-Absolue; Castoreum-absolue; Cedemblätteröl; Cedemholzöl; Cistusöl;calamus; camphor oil; Cananga oil; cardamom; Cascarillaöl; cassia; Cassie absolute; Beaver-absolue; Cedemblätteröl; Cedemholzöl; cistus;
Citronellöl; Citronenöl; Copaivabalsam; Copaivabalsamöl; Corianderöl;citronella; lemon; copaiba balsam; Copaivabalsamöl; Coriander oil;
Costuswurzelöl; Cuminöl; Cypressenöl; Davanaöl; Dillkrautöl; Dillsamenöl; Eau de brouts-Absolue; Eichenmoos-Absolue; Elemiöl; Estragonöl; Eucalyptus- citriodora-öl; Eucalyptusöl; Fenchelöl ; Fichtennadelöl; Galbanumöl; Galbanumresin; Geraniumöl; Grapefruitöl; Guajakholzöl; Gurjunbalsam;costus root; Cuminöl; Cypress oil; Davanaöl; Dill herb oil; Dill seed oil; Eau de Brouts absolute; Oak moss absolute; elemi; Tarragon oil; Eucalyptus citriodora oil; eucalyptus oil; Fennel oil; Pine needle oil; galbanum; Galbanumresin; geranium; Grapefruit oil; guaiac wood; gurjun balsam;
Gurjunbalsamöl; Helichrysum-Absolue; Helichrysumöl; Ingweröl; Iriswurzel-gurjun balsam oil; Helichrysum absolute; Helichrysumöl; Ginger oil; Iriswurzel-
Absolue; Iriswurzelöl; Jasmin-Absolue; Kalmusöl; Kamillenöl blau; Kamillenöl römisch; Karottensamenöl; Kaskarillaöl; Kiefemadelöl; Krauseminzöl; Kümmelöl;absolute; Orris root oil; Jasmine absolute; calamus; Chamomile oil blue; Camomile oil Roman; Carrot seed oil; Kaskarillaöl; Kiefemadelöl; spearmint; Seed oil;
Labdanumöl; Labdanum-Absolue; Labdanumresin; Lavandin-Absolue; Lavandinöl ; Lavendel-Absolue; Lavendelöl; Lemongrasöl; Liebstocköl; Limetteöl destilliert; Limetteöl gepreßt; Linaloeöl; Litsea-cubeba-öl; Lorbeerblätteröl;labdanum; Labdanum absolute; Labdanumresin; Lavandin absolute; Lavandin oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Distilled lime oil; Pressed lime oil; linaloe; Litsea cubeba oil; Bay leaf oil;
Macisöl; Majoranöl; Mandarinenöl; Massoirindenöl; Mimosa-Absolue;Macisöl; Marjoram oil; Mandarin oil; Massoirindenöl; Mimosa absolute;
Moschuskömeröl; Moschustinktur; Muskateller-Salbei-Öl; Muskatnußöl; Myrrhen-Moschuskömeröl; musk tincture; Clary sage oil; nutmeg; Myrrhen-
Absolue; Myrrhenöl; Myrtenöl; Nelkenblätteröl; Nelkenblütenöl; Neroliöl; Olibanum-Absolue; Olibanumöl; Opopanaxöl; Orangenblüten-Absolue;absolute; Myrrh oil; myrtle; Clove leaf oil; Clove flower oil; neroli; Olibanum absolute; olibanum; Opopanaxöl; Orange blossom absolute;
Orangenöl; Origanumöl; Palmarosaöl; Patchouliöl; Perillaöl; Perubalsamöl;Orange oil; oregano; Palmarosa oil; patchouli oil; perilla oil; Peruvian balsam oil;
Petersilienblätteröl; Petersiliensamenöl; Petitgrainöl; Pfefferminzöl; Pfefferöl;Parsley leaf oil; Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil;
Pimentöl; Pineöl; Poleyöl; Rosen-Absolue; Rosenholzöl; Rosenöl; Rosmarinöl;chilli; pine oil; Poleyöl, Rose absolute; Rosewood oil; Rose oil; Rosemary oil;
Salbeiöl dalmatinisch; Salbeiöl spanisch; Sandelholzöl; Selleriesamenöl; Spiklavendelöl; Sternanisöl; Styraxöl; Tagetesöl; Tannennadelöl; Tea-tree-öl;Sage oil Dalmatian; Sage oil spanish; sandalwood; Celery seed oil; spike lavender oil; star anise; Styraxöl; tagetes; Pine needle oil; Tea-tree-oil;
Terpentinöl; Thymianöl; Tolubalsam; Tonka-Absolue; Tuberosen-Absolue; Vanilleextrakt; Veilchenblätter-Absolue; Verbenaöl; Vetiveröl; Wacholderbeeröl; Weinhefenöl; Wermutöl; Wintergrünöl; Ylangöl; Ysopöl; Zibet-Absolue; Zimtblätteröl; Zimtrindenöl; sowie Fraktionen davon, bzw. daraus isolierten Inhaltsstoffen;turpentine; Thyme oil; Tolu; Tonka absolute; Tuberose absolute; Vanilla extract; Violet leaf absolute; verbena; vetiver; Juniper berry oil; Wine yeast oil; Wormwood oil; Wintergreen oil; ylang oil; hyssop oil; Civet absolute; cinnamon leaf; cinnamon bark oil; and fractions thereof, or ingredients isolated therefrom;
Einzel-Riechstoffe aus der Gruppe der Kohlenwasserstoffe, wie z.B. 3-Caren; α- Pinen; ß-Pinen; α-Terpinen; γ-Terpinen; p-Cymol; Bisabolen; Camphen; Cary- ophyllen; Cedren; Famesen; Limonen; Longifolen; Myrcen; Ocimen; Valencen; (E1Z)-1 ,3,5-Undecatrien;Individual fragrances from the group of hydrocarbons, such as 3-carene; α-pinene; beta-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; Caryophyllene; cedrene; Famesen; limonene; longifolene; myrcene; ocimene; valencene; (E 1 Z) -1, 3,5-undecatriene;
der aliphatischen Alkohole wie z. B. Hexanol; Octanol; 3-Octanol; 2,6-Dimethyl- heptanol; 2-Methylheptanol, 2-Methyloctanol; (E)-2-Hexenol; (E)- und (Z)-3-Hexe- nol; 1-Octen-3-ol; Gemisch von 3,4,5,6, 6-Pentamethyl-3/4-hepten-2-ol und 3,5,6,6-Tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-Nonadienol; 3,7-Dimethyl- 7-methoxyoctan-2-ol; 9-Decenol; 10-Undecenol; 4-Methyl-3-decen-5-ol; der aliphatischen Aldehyde und deren 1 ,4-Dioxacycloalken-2-one wie z. B. Hexanal; Heptanal; Octanal; Nonanal; Decanal; Undecanal; Dodecanal; Tridecanal; 2- Methyloctanal; 2-Methyl nonanal; (E)-2-Hexenal; (Z)-4-Heptenal; 2,6-Dimethyl-5- heptenal; 10-Undecenal; (E)-4-Decenal; 2-Dodecenal; 2,6,10-Trimethyl-5,9- undecadienal; Heptanaldiethylacetal; 1 , 1 -Dimethoxy-2,2,5-trimethyl-4-hexen; Citronellyloxyacetaldehyd;the aliphatic alcohols such. Hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyl-octanol; (E) -2-hexenol; (E) - and (Z) -3-hexenol; 1-octene-3-ol; Mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E, Z) -2,6-Nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; the aliphatic aldehydes and their 1, 4-dioxacycloalkene-2-ones such. Hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyl octanal; 2-methyl nonanal; (E) -2-hexenal; (Z) -4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E) -4-decenal; 2-dodecenal; 2,6,10-trimethyl-5,9-undecadienal; Heptanaldiethylacetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde;
der aliphatischen Ketone und deren Oxime wie z.B. 2-Heptanon; 2-Octanon; 3- Octanon; 2-Nonanon; 5-Methyl-3-heptanon; 5-Methyl-3-heptanonoxim; 2,4,4,7- Tetramethyl-6-octen-3-on; der aliphatischen schwefelhaltigen Verbindungen wie z.B. 3-Methylthiohexanol; 3-Methylthiohexylacetat; 3-Mercaptohexanol; 3- Mercaptohexylacetat; 3-Mercaptohexylbutyrat; 3-Acetylthiohexylacetat; 1-Menthen-8-thiol;the aliphatic ketones and their oximes, e.g. 2-heptanone; 2-octanone; 3- Octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; the aliphatic sulfur-containing compounds, e.g. 3-methylthiohexanol; 3-Methylthiohexylacetat; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;
der aliphatischen Nitrile wie z.B. 2-Nonensäurenitril; 2-Tridecensäurenitril; 2,12- Tridecensäurenitril; 3,7-Dimethyl-2,6-octadiensäurenitril; 3,7-Dimethyl-6-octen- säurenitril; der aliphatischen Carbonsäuren und deren Ester wie z.B. (E)- und (Z)-3- Hexenylformiat; Ethylacetoacetat; Isoamylacetat; Hexylacetat; 3,5,5-Trimethyl- hexylacetat; 3-Methyl-2-butenylacetat; (E)-2-Hexenylacetat; (E)- und (Z)-3- Hexenylacetat; Octylacetat; 3-Octylacetat; 1-Octen-3-ylacetat; Ethylbutyrat; Butylbutyrat, ; Isoamylbutyrat; Hexylbutyrat; (E)- und (Z)-3-Hexenylisobutyrat; Hexylcrotonat; Ethylisovalerianat; Ethyl-2-methylpentanoat; Ethylhexanoat; Allylhexanoat; Ethylheptanoat; Allylheptanoat; Ethyloctanoat; Ethyl-(E,Z)-2,4- decadienoat; Methyl-2-octinat; Methyl-2-noninat; Allyl-2-isoamyloxyacetat; Methyl-3,7-dimethyl-2,6-octadienoat;the aliphatic nitriles such as 2-nonenitrile; 2-Tridecensäurenitril; 2,12-tridecenoic acid nitrile; 3,7-dimethyl-2,6-octadiensäurenitril; 3,7-dimethyl-6-octenitrile; the aliphatic carboxylic acids and their esters such as (E) - and (Z) -3-hexenyl formate; ethylacetoacetate; isoamyl; hexyl acetate; 3,5,5-trimethyl-hexyl acetate; 3-methyl-2-butenyl acetate; (E) -2-hexenyl acetate; (E) - and (Z) -3-hexenylacetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; Butyl butyrate, isoamyl; hexyl butyrate; (E) - and (Z) -3-hexenyl isobutyrate; hexyl crotonate; Ethylisovalerianat; Ethyl 2-methylpentanoate; ethylhexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; Ethyl (E, Z) -2,4-decadienoate; Methyl-2-octinat; Methyl-2-noninat; Allyl-2-isoamyloxyacetat; Methyl-3,7-dimethyl-2,6-octadienoate;
der acyclischen Terpenalkohole wie z.B. Citronellol; Geraniol; Nerol; Linalool; Lavadulol; Nerolidol; Famesol; Tetrahydrolinalool; Tetrahydrogeraniol; 2,6- Dimethyl-7-octen-2-ol; 2,6-Dimethyloctan-2-ol; 2-Methyl-6-methylen-7-octen-2-ol; 2,6-Dimethyl-5,7-octadien-2-ol; 2,6-Dimethyl-3,5-octadien-2-ol; 3,7-Dimethyl-4,6- octadien-3-ol; 3,7-Dimethyl-1 ,5,7-octatrien-3-ol 2,6-Dimethyl-2,5,7-octatrien-1 -ol; sowie deren Formiate, Acetate, Propionate, Isobutyrate, Butyrate, Isovalerianate, Pentanoate, Hexanoate, Crotonate, Tiglinate, 3-Methyl-2-butenoate;the acyclic terpene alcohols, e.g. citronellol; geraniol; nerol; linalool; Lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octene-2-ol; 2,6-dimethyl octane-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadiene-2-ol; 2,6-dimethyl-3,5-octadiene-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1, 5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-1-ol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates;
der acyclischen Terpenaldehyde und -ketone wie z.B. Geranial; Neral; Citronellal; 7-Hydroxy-3,7-dimethyloctanal; 7-Methoxy-3,7-dimethyloctanal; 2,6, 10-Trimethyl- 9-undecenal; Geranylaceton; sowie die Dimethyl- und Diethylacetale von Geranial, Neral, 7-Hydroxy-3,7-dimethyloctanal;the acyclic terpene aldehydes and ketones, e.g. geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranyl acetone; and the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal;
der cyclischen Terpenalkohole wie z.B. Menthol; Isopulegol; alpha-Terpineol; Terpinenol-4; Menthan-8-ol; Menthan-1-ol; Menthan-7-ol; Borneol; Isobomeol; Linalooloxid; Nopol; Cedrol; Ambrinol; Vetiverol; Guajol; sowie deren Formiate, Acetate, Propionate, Isobutyrate, Butyrate, Isovalerianate, Pentanoate, Hexanoate, Crotonate, Tiglinate, 3-Methyl-2-butenoate;the cyclic terpene alcohols, e.g. Menthol; isopulegol; alpha-terpineol; Terpinenol-4; Menthane-8-ol; Menthane-1-ol; Menthane-7-ol; borneol; Isobomeol; linalool; monopoly; cedrol; ambrinol; Vetyverol; guaiol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates;
der cyclischen Terpenaldehyde und -ketone wie z.B. Menthon; Isomenthon; 8- Mercaptomenthan-3-on; Carvon; Campher; Fenchon; alpha-lonon; beta-lonon; alpha-n-Methylionon; beta-n-Methylionon; alpha-lsomethylionon; beta- Isomethylionon; alpha-lron; alpha-Damascon; beta-Damascon; beta- Damascenon; delta-Damascon; gamma-Damascon; 1 -(2,4,4-Trinnethyl-2- cyclohexen-1 -yl)-2-buten-1 -on; 1.SAβXδa-Hexahydro-i , 1 ,5,5-tetrannethyl-2H- 2,4a-methanonaphthalen-8(5H)-on; Nootkaton; Dihydronootkaton; alpha- Sinensal; beta-Sinensal; Acetyliertes Cedemholzöl (Methylcedrylketon);the cyclic terpene aldehydes and ketones such as menthone; menthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchon; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethyl-ionone; alpha-lron; alpha-damascone; beta-damascone; beta- damascenone; delta-damascone; gamma-damascone; 1 - (2,4,4-trin-ethyl-2-cyclohexene-1-yl) -2-butene-1-one; 1.SAβXδa-hexahydro-i, 1,5,5-tetrannethyl-2H-2,4a-methanonaphthalene-8 (5H) -one; nootkatone; Dihydronootkaton; alpha-Sinensal; beta-sinensal; Acetylated cedar wood oil (methyl cedryl ketone);
der cyclischen Alkohole wie z.B. 4-tert.-Butylcyclohexanol ; 3,3,5-Trimethylcyclo- hexanol; S-Isocamphylcyclohexanol; 2,6,9-Trimethyl-Z2,Z5,E9-cyclododecatrien- 1 -ol; 2-lsobutyl-4-methyltetrahydro-2H-pyran-4-ol;the cyclic alcohols, e.g. 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; S-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2, Z5, E9-cyclododecatriene-1-ol; 2-isobutyl-4-methyl tetrahydro-2H-pyran-4-ol;
der cycloaliphatischen Alkohole wie z.B. alpha.S.S-Trimethylcyclohexylmethanol; 2-Methyl-4-(2J2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-Methyl-4-(2J2,3-trimethyl- 3-cyclopent-1 -yl)-2-buten-1 -ol; 2-Ethyl-4-(2J2,3-trimethyl-3-cyclopent-1 -yl)-2- buten-1 -ol; 3-Methyl-5-(2J2,3-trimethyl-3-cyclopent-1 -yl)-pentan-2-ol; 3-Methyl-5- (2J2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3J3-Dimethyl-5-(2J2,3-trimethyl-3- cyclopent-1 -yl)-4-penten-2-ol; 1 -(2,2,6-Trimethylcyclohexyl)pentan-3-ol; 1 -(2,2,6- Trimethylcyclohexyl)hexan-3-ol;the cycloaliphatic alcohols such as alpha.SS-trimethylcyclohexylmethanol; 2-methyl-4- (2 J 2,3-trimethyl-3-cyclopent-1-yl) butanol; 2-methyl-4- (2 J 2,3-trimethyl-cyclopent-3-1-yl) -2-buten-1-ol; 2-ethyl-4- (2 J 2,3-trimethyl-3-cyclopent-1-yl) -2-buten-1-ol; 3-methyl-5- (2 J 2,3-trimethyl-3-cyclopent-1-yl) pentan-2-ol; 3-methyl-5- (2 J 2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 3 J 3-dimethyl-5- (2 J 2,3-trimethyl-3-cyclopent-1-yl) -4-penten-2-ol; 1 - (2,2,6-trimethylcyclohexyl) pentan-3-ol; 1 - (2,2,6-trimethylcyclohexyl) hexan-3-ol;
der cyclischen und cycloaliphatischen Ether wie z.B. Cineol; Cedrylmethylether; Cyclododecylmethylether; (Ethoxymethoxy)cyclododecan; alpha-Cedrenepoxid; Sa.e.β.θa-Tetramethyldodecahydronaphthop, 1 -b]furan; 3a-Ethyl-6,6,9a- trimethyldodecahydronaphtho[2, 1 -bjfuran; 1 ,5,9-Trimethyl-13- oxabicyclo[10.1.0]trideca-4,8-dien; Rosenoxid; 2-(2,4-Dimethyl-3-cyclohexen-1- yl)-5-methyl-5-(1 -methylpropyl)-1 ,3-dioxan;the cyclic and cycloaliphatic ethers, e.g. cineol; cedryl methyl ether; cyclododecyl; (Ethoxymethoxy) cyclododecane; alpha-Cedrenepoxid; Sa.e.beta.-tetramethyldodecahydronaphthop, 1-b] furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho [2, 1 -bjfuran; 1, 5,9-trimethyl-13-oxabicyclo [10.1.0] trideca-4,8-diene; rose oxide; 2- (2,4-dimethyl-3-cyclohexene-1-yl) -5-methyl-5- (1-methylpropyl) -1,3-dioxane;
der cyclischen Ketone wie z.B. 4-tert.-Butylcyclohexanon; 2J2,5-Trimethyl-5- pentylcyclopentanon; 2-Heptylcyclopentanon; 2-Pentylcyclopentanon; 2-Hydroxy- 3-methyl-2-cyclopenten-1 -on; 3-Methyl-cis-2-penten-1 -yl-2-cyclopenten-1 -on; 3- Methyl-2-pentyl-2-cyclopenten-1 -on; 3-Methyl-4-cyclopentadecenon; 3-Methyl-5- cyclopentadecenon; S-Methylcyclopentadecanon; 4-(1-Ethoxyvinyl)-3,3,5,5-tetra- methylcyclohexanon; 4-tert.-Pentylcyclohexanon; 5-Cyclohexadecen-i-on; 6,7- Dihydro-1 , 1 J2,3J3-pentamethyl-4(5H)-indanon; 5-Cyclohexadecen-i -on; 8-Cyclo- hexadecen-1-on; 9-Cycloheptadecen-i-on; Cyclopentadecanon; der cycloaliphatischen Aldehyde wie z.B. 2,4-Dimethyl-3-cyclohexencarbaldehyd; 2-Methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-Hydroxy-4-methyl- pentyl)-3-cyclohexencarbaldehyd; 4-(4-Methyl-3-penten-1-yl)-3-cyclohexen- carbaldehyd;the cyclic ketones such as 4-tert-butylcyclohexanone; 2 J 2,5-trimethyl-5- pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopentene-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopentene-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; S-methylcyclopentadecanone; 4- (1-ethoxyvinyl) -3,3,5,5-tetra methylcyclohexanone; 4-tert.-pentylcyclohexanone; 5-cyclohexadecen-i-one; 6,7-dihydro-1,1- J 2,3 J 3-pentamethyl-4 (5H) -indanone; 5-cyclohexadecene-i -one; 8-cyclohexadecen-1-one; 9-cycloheptadecen-i-one; cyclopentadecanone; the cycloaliphatic aldehydes such as 2,4-dimethyl-3-cyclohexene carbaldehyde; 2-methyl-4- (2,2,6-trimethyl-cyclohexen-1-yl) -2-butenal; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene carbaldehyde; 4- (4-methyl-3-penten-1-yl) -3-cyclohexene carbaldehyde;
der cycloaliphatischen Ketone wie z. B. 1-(3,3-Dimethylcyclohexyl)-4-penten-1-on; 1 -(5,5-Dimethyl-1 -cyclohexen-1 -yl)-4-penten-1 -on; 2,3,8,8-Tetramethyl-the cycloaliphatic ketones such. B. 1- (3,3-dimethylcyclohexyl) -4-penten-1-one; 1 - (5,5-dimethyl-1-cyclohexene-1-yl) -4-penten-1-one; 2,3,8,8-tetramethyl
1,2,3A5A7,8-θ(Λahydro-2-naphtalenylmethylketon; Methyl^e.iO-trimethyl^S.Θ- cyclododecatrienylketon; tert. -Butyl-(2,4-dimethyl-3-cyclohexen-1 -yl)keton;1,2,3A5A7,8-θ (Λahydro-2-naphthalenylmethylketone; methyl ^ e.iO-trimethyl ^ S.Θcyclododecatrienyl ketone; tert-butyl (2,4-dimethyl-3-cyclohexen-1-yl) ketone;
der Ester cyclischer Alkohole wie z.B. 2-tert-Butylcyclohexylacetat; 4-tert Butyl- cyclohexylacetat; 2-tert-Pentylcyclohexylacetat; 4-tert-Pentylcyclohexylacetat;the ester of cyclic alcohols, e.g. 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate;
Decahydro-2-naphthylacetat; 3-Pentyltetrahydro-2H-pyran-4-ylacetat;Decahydro-2-naphthyl acetate; 3-pentyltetrahydro-2H-pyran-4-yl acetate;
Decahydro^S.S.δa-tetramethyl^-naphthylacetat; 4,7-Methano-3aJ4J5,6J7J7a- hexahydro-5, bzw. 6-indenylacetat; 4,7-Methano-3a,4,5,6,7,7a-hexahydro-5, bzw. 6-indenylpropionat; 4,7-Methano-3aJ4J5J6J7,7a-hexahydro-5J bzw. 6-indenylisobutyrat; 4,7-Methanooctahydro-5, bzw. 6-indenylacetat;Decahydro ^ SSδa-tetramethyl ^ naphthyl acetate; 4,7-methano-3a J 4 J 5.6 J 7 J 7-hexahydro-5 or 6-indenyl acetate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, and 6-indenylpropionate, respectively; 4,7-methano-3a J 4 J 5 J 6 J 7,7a-hexahydro-5 J or 6-indenyl isobutyrate; 4,7-Methanooctahydro-5, or 6-indenyl acetate;
der Ester cycloaliphatischer Carbonsäuren wie z. B. Allyl-3-cyclohexylpropionat; Allylcyclohexyloxyacetat; Methyldihydrojasmonat; Methyljasmonat; Methyl-2- hexyl-3-oxocyclopentancarboxylat; Ethyl^-ethyl-β.β-dimethyl^-cyclohexencarb- oxylat; Ethyl^SAe-tetramethyl^-cyclohexencarboxylat; Ethyl-2-methyl-1 ,3- dioxolan-2-acetat;the esters of cycloaliphatic carboxylic acids such as. For example, allyl-3-cyclohexylpropionate; Allylcyclohexyloxyacetat; methyldihydrojasmonate; methyl jasmonate; Methyl 2-hexyl-3-oxocyclopentanecarboxylate; Ethyl ^ -ethyl-β, β-dimethylcyclohexenecarboxylate; Ethyl ^ SAE-tetramethyl ^ -cyclohexencarboxylat; Ethyl 2-methyl-1,3-dioxolane-2-acetate;
der aromatischen Kohlenwasserstoffe wie z. B. Styrol und Diphenylmethan;the aromatic hydrocarbons such. Styrene and diphenylmethane;
der araliphatischen Alkohole wie z.B. Benzylalkohol; 1-Phenylethylalkohol; 2- Phenylethylalkohol; 3-Phenylpropanol; 2-Phenylpropanol; 2-Phenoxyethanol; 2,2- Dimethyl-3-phenylpropanol; 2,2-Dimethyl-3-(3-methylphenyl)propanol; 1 , 1 -Di- methyl-2-phenylethylalkohol; 1 ,1-Dimethyl-3-phenylpropanol; 1-Ethyl-1-methyl-3- phenylpropanol; 2-Methyl-5-phenylpentanol; 3-Methyl-5-phenylpentanol; 3- Phenyl-2-propen-1 -ol; 4-Methoxybenzylalkohol; 1 -(4-lsopropylphenyl)ethanol; der Ester von araliphatischen Alkoholen und aliphatischen Carbonsäuren wie z.B.; Benzylacetat; Benzylpropionat; Benzylisobutyrat; Benzylisovalerianat; 2-Phenylethylacetat; 2-Phenylethylpropionat; 2-Phenylethylisobutyrat; 2-Phenyl- ethylisovalerianat; 1 -Phenylethylacetat; alpha-Trichlormethyl benzylacetat; alpha, alpha-Dimethylphenylethylacetat; alpha, alpha-Dimethylphenylethylbutyrat; Cinnamylacetat; 2-Phenoxyethylisobutyrat; 4-Methoxybenzylacetat; der aralipha¬ tischen Ether wie z.B. 2-Phenylethylmethylether; 2-Phenylethylisoamylether; 2-Phenylethyl-1 -ethoxyethylether; Phenylacetaldehyddimethylacetal; Phenylacet- aldehyddiethylacetal; Hydratropaaldehyddimethylacetal; Phenylacetaldehydgly- cerinacetal; 2,4J6-Trimethyl-4-phenyl-1 J3-dioxane; 4,4a,5,9b-Tetrahydro- indeno[1 ,2-d]-m-dioxin; 4,4a,5,9b-Tetrahydro-2,4-dimethylindeno[1 ,2-d]-m-dioxin;the araliphatic alcohols such as benzyl alcohol; 1-phenylethyl; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3- (3-methylphenyl) propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1, 1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propene-1-ol; 4-methoxybenzyl; 1 - (4-isopropylphenyl) ethanol; the ester of araliphatic alcohols and aliphatic carboxylic acids such as; benzyl acetate; benzylpropionate; benzyl isobutyrate; Benzylisovalerianat; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-Phenylethylisobutyrat; 2-phenylethyl isovalerate; 1-phenylethyl acetate; alpha-trichloromethylbenzylacetate; alpha, alpha-dimethylphenylethyl acetate; alpha, alpha-dimethylphenylethyl butyrate; cinnamyl; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; the araliphatic ether such as 2-phenylethyl methyl ether; 2-Phenylethylisoamylether; 2-phenylethyl-1-ethoxyethyl ether; phenylacetaldehyde; Phenylacetaldehyde diethyl acetal; Hydratropaaldehyddimethylacetal; Phenylacetaldehyde glycerin acetal; 2,4 J 6-trimethyl-4-phenyl-1 J 3-dioxane; 4,4a, 5,9b-tetrahydro-indeno [1,2-d] -m-dioxin; 4,4a, 5,9b-tetrahydro-2,4-dimethylindo [1,2-d] -m-dioxin;
der aromatischen und araliphatischen Aldehyde wie z. B. Benzaldehyd; Phenylacetaldehyd; 3-Phenylpropanal; Hydratropaaldehyd; 4-the aromatic and araliphatic aldehydes such. B. benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; Hydratropaaldehyd; 4
Methylbenzaldehyd; 4-Methylphenylacetaldehyd; 3-(4-Ethylphenyl)-2,2- dimethylpropanal; 2-Methyl-3-(4-isopropylphenyl)propanal; 2-Methyl-3-(4-tert- butylphenyl)propanal; 3-(4-tert.-Butylphenyl)propanal; Zimtaldehyd; alpha- Butylzimtaldehyd; alpha-Amylzimtaldehyd; alpha-Hexylzimtaldehyd; 3-Methyl-5- phenylpentanal; 4-Methoxybenzaldehyd; 4-Hydroxy-3-methoxybenzaldehyd; 4- Hydroxy-3-ethoxybenzaldehyd; 3,4-Methylendioxybenzaldehyd; 3,4- Dimethoxybenzaldehyd; 2-Methyl-3-(4-methoxyphenyl)propanal; 2-Methyl-3-(4- methylendioxyphenyl)propanal;methylbenzaldehyde; 4-methylphenylacetaldehyde; 3- (4-ethylphenyl) -2,2-dimethylpropanal; 2-methyl-3- (4-isopropylphenyl) propanal; 2-methyl-3- (4-tert-butylphenyl) propanal; 3- (4-tert-butylphenyl) propanal; cinnamic aldehyde; alpha-butylcinnamaldehyde; alpha-amyl cinnamic aldehyde; alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-Hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3- (4-methoxyphenyl) propanal; 2-methyl-3- (4-methylenedioxyphenyl) propanal;
der aromatischen und araliphatischen Ketone wie z.B. Acetophenon; 4-Methyl- acetophenon; 4-Methoxyacetophenon; 4-tert.-Butyl-2,6-dimethylacetophenon; 4- Phenyl-2-butanon; 4-(4-Hydroxyphenyl)-2-butanon; 1 -(2-Naphthalenyl)ethanon; Benzophenon; I .I^ΛS.β-Hexamethyl-S-indanylmethylketon; 6-tert.-Butyl-1,1- dimethyl-4-indanylmethylketon; 1 -[2,3-dihydro-1 , 1 ,2,6-tetramethyl-3-(1 -methyl- ethyl)-1 H-5-indenyl]ethanon; S'.e'y'.δ'-Tetrahydro-S'.S'.S'.e'.β'.δ'-hexamethyl^- acetonaphthon;the aromatic and araliphatic ketones such as e.g. acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4- (4-hydroxyphenyl) -2-butanone; 1- (2-naphthalenyl) ethanone; benzophenone; I, I, β, β-hexamethyl-S-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1 - [2,3-dihydro-1, 1, 2,6-tetramethyl-3- (1-methylethyl) -1H-5-indenyl] ethanone; S'.e'y'.δ'-tetrahydro-S'.S'.S'.e'.β'.δ'-hexamethyl-acetonaphthone;
der aromatischen und araliphatischen Carbonsäuren und deren Ester wie z.B. Benzoesäure; Phenylessigsäure; Methylbenzoat; Ethylbenzoat; Hexylbenzoat; Benzyl-benzoat; Methylphenylacetat; Ethylphenylacetat; Geranylphenylacetat; Phenylethyl-phenylacetat; Methylcinnmat; Ethylcinnamat; Benzylcinnamat; Phenylethylcinnamat; Cinnamylcinnamat; AIIyI phenoxyacetat; Methylsalicylat; Isoamylsalicylat; Hexylsalicylat; Cyclohexylsalicylat; Cis-3-Hexenylsalicylat; Benzylsalicylat; Phenylethylsalicylat; Methyl-2,4-dihydroxy-3,6-dinnethylbenzoat; Ethyl-3-phenylglycidat; Ethyl-3-methyl-3-phenylglycidat;the aromatic and araliphatic carboxylic acids and their esters such as benzoic acid; phenylacetic acid; methylbenzoate; ethyl benzoate; hexyl benzoate; Benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; Phenylethyl phenylacetate; Methylcinnmat; ethylcinnamate; Benzyl; Phenylethylcinnamat; cinnamyl cinnamate; AIIyI phenoxyacetate; methyl salicylate; isoamyl; hexyl salicylate; cyclohexyl; Cis-3-hexenyl salicylate; benzyl; phenylethyl; Methyl-2,4-dihydroxy-3,6-dinnethylbenzoat; Ethyl 3-phenylglycidate; Ethyl-3-methyl-3-phenylglycidate;
der stickstoffhaltigen aromatischen Verbindungen wie z.B. 2,4,6-Trinitro-i ,3- dimethyl-5-tert.-butylbenzol; 3,5-Dinitro-2,6-dimethyl-4-tert.-butylacetophenon; Zimtsäurenitril; 5-Phenyl-3-methyl-2-pentensäurenitril; 5-Phenyl-3-methylpentan- säurenitril; Methylanthranilat; Methy-N-methylanthranilat; Schiffsche Basen von Methylanthranilat mit 7-Hydroxy-3,7-dimethyloctanal, 2-Methyl-3-(4-tert.-butyl- phenyl)propanal oder 2,4-Dimethyl-3-cyclohexencarbaldehyd; 6-the nitrogen-containing aromatic compounds such as e.g. 2,4,6-trinitro-i, 3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert.-butylacetophenone; cinnamic acid; 5-phenyl-3-methyl-2-pentensäurenitril; 5-phenyl-3-methylpentanitrile; methyl anthranilate; Methyl N-methylanthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexene carbaldehyde; 6
Isopropylchinolin; 6-lsobutylchinolin; 6-sec-Butylchinolin; Indol; Skatol; 2- Methoxy-3-isopropylpyrazin; 2-lsobutyl-3-methoxypyrazin;Isopropyl; 6-lsobutylchinolin; 6-sec-butylquinoline; indole; skatol; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;
der Phenole, Phenylether und Phenylester wie z.B. Estragol; Anethol; Eugenol; Eugenylmethylether; Isoeugenol; Isoeugenylmethylether; Thymol; Carvacrol; Diphenylether; beta-Naphthylmethylether; beta-Naphthylethylether; beta- Naphthylisobutylether; 1,4-Dimethoxybenzol; Eugenylacetat; 2-Methoxy-4- methylphenol; 2-Ethoxy-5-(1 -propenyl)phenol; p-Kresylphenylacetat;the phenols, phenyl ethers and phenyl esters, e.g. estragole; anethole; eugenol; Eugenylmethylether; isoeugenol; Isoeugenylmethylether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-Naphthylethylether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; Eugenylacetat; 2-methoxy-4-methylphenol; 2-ethoxy-5- (1-propenyl) phenol; p-Kresylphenylacetat;
der heterocyclischen Verbindungen wie z.B. 2,5-Dimethyl-4-hydroxy-2H-furan-3- on; 2-Ethyl-4-hydroxy-5-methyl-2H-furan-3-on; 3-Hydroxy-2-methyl-4H-pyran-4- on; 2-Ethyl-3-hydroxy-4H-pyran-4-on;the heterocyclic compounds such as e.g. 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;
der Lactone wie z.B. 1,4-Octanolid; 3-Methyl-1,4-octanolid; 1,4-Nonanolid; 1,4- Decanolid; 8-Decen-1,4-olid; 1 ,4-Undecanolid; 1,4-Dodecanolid; 1,5-Decanolid; 1 ,5-Dodecanolid; 1,15-Pentadecanolid; eis- und trans-11-Pentadecen-1,15-olid; eis- und trans-12-Pentadecen-1 ,15-olid; 1 ,16-Hexadecanolid; 9-Hexadecen-1 ,16- olid; 10-Oxa-1,16-hexadecanolid; 11-Oxa-1 ,16-hexadecanolid; 12-Oxa-1 ,16- hexadecanolid; Ethylen-1,12-dodecandioat; Ethylen-1,13-tridecandioat; Cumarin; 2,3-Dihydrocumarin; Octahydrocumarin. Parfümöle, welche die erfindungsgemäßen Verbindungen der oben genannten Formeln enthalten, können in flüssiger Form, unverdünnt oder mit einem Lösungsmittel verdünnt für Parfümierungen eingesetzt werden. Geeignete Lösungsmittel hierfür sind z.B. Ethanol, Isopropanol, Diethylen- glycolmonoethylether, Glycerin, Propylenglycol, 1,2-Butylenglycol, Dipropylen- glycol, Diethylphthalat, Triethylcitrat, Isopropylmyristat usw.the lactones such as 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1, 5-dodecanolide; 1.15 pentadecanolide; cis- and trans-11-pentadecene-1,15-olide; cis- and trans-12-pentadecene-1, 15-olide; 1, 16-hexadecanolide; 9-hexadecene-1, 16-olide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1, 16-hexadecanolide; Ethylene-1,12-dodecanedioate; Ethylene-1,13-tridecandioat; coumarin; 2,3-dihydrocoumarin; Octahydrocoumarin. Perfume oils containing the compounds of the above formulas according to the invention can be used in perfumed form in liquid form, neat or diluted with a solvent. Suitable solvents for this are, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc.
Parfümöle, welche die erfindungsgemäßen Verbindungen enthalten, können an einem Trägerstoff absorbiert sein, der sowohl für eine feine Verteilung der Riech¬ stoffe im Produkt als auch für eine kontrollierte Freisetzung bei der Anwendung sorgt. Derartige Träger können poröse anorganische Materialien wie Leichtsulfat, Kieselgele, Zeolithe, Gipse, Tone, Tongranulate, Gasbeton usw. oder organische Materialien wie Hölzer und Cellulose-basierende Stoffe sein.Perfume oils containing the compounds according to the invention can be absorbed on a carrier which ensures both a fine distribution of the odoriferous substances in the product and a 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 woods and cellulosic based materials.
Parfümöle, welche die erfindungsgemäßen Verbindungen enthalten, können auch mikroverkapselt, sprühgetrocknet, als Einschluss-Komplexe oder als Extrusions-Produkte vorliegen und in dieser Form dem zu parfümierenden Produkt hinzugefügt werden.Perfume oils containing the compounds of the invention may also be microencapsulated, spray dried, present as inclusion complexes or as extrusion products and added in this form to the product to be perfumed.
Gegebenenfalls können die Eigenschaften der derart modifizierten Parfümöle durch sog. „Coaten" mit geeigneten Materialien im Hinblick auf eine gezieltere Duftfreisetzung weiter optimiert werden, wozu vorzugsweise wachsartige Kunststoffe wie z.B. Polyvinylalkohol verwendet werden.Optionally, the properties of the perfume oils modified in this way can be further optimized by so-called "coating" with suitable materials with a view to a more targeted release of fragrance, to which end waxy plastics such as polyvinyl alcohol are preferably used.
Die Mikroverkapselung der Parfümöle kann beispielsweise durch das sogenannte Koazervationsverfahren mit Hilfe von Kapselmaterialien z.B. aus Polyurethan-artigen Stoffen oder Weichgelatine, erfolgen. Die sprühgetrockneten Parfümöle können beispielsweise durch Sprühtrocknung einer das Parfümöl enthaltenden Emulsion, bzw. Dispersion hergestellt werden, wobei als Trägerstoffe modifizierte Stärken, Proteine, Dextrin und pflanzliche Gummen verwendet werden können. Einschluss-Komplexe können z.B. durch Eintragen von Dispersionen von dem Parfümöl und Cyclodextrinen oder Harnstoffderivaten in ein geeignetes Lösungsmittel, z.B. Wasser, hergestellt werden. Extrusions- Produkte können durch Verschmelzen der Parfümöle mit einem geeigneten wachsartigen Stoff und durch Extrusion mit nachfolgender Erstarrung, ggf. in einem geeigneten Lösungsmittel, z.B. Isopropanol, erfolgen.The microencapsulation of the perfume oils can be carried out, for example, by the so-called coacervation process with the aid of capsule materials, for example of polyurethane-like substances or soft gelatin. The spray-dried perfume oils can be prepared, for example, by spray-drying a perfume oil-containing emulsion or dispersion, it being possible to use as starches modified starches, proteins, dextrin and vegetable gums. Inclusion complexes may be prepared, for example, by incorporating dispersions of the perfume oil and cyclodextrins or urea derivatives into a suitable solvent, eg, water. Extrusions- Products can be made by fusing the perfume oils with a suitable waxy substance and by extrusion with subsequent solidification, if appropriate in a suitable solvent, for example isopropanol.
In Parfümkompositionen beträgt die eingesetzte Gesamtmenge der erfindungsgemäß zu verwendenden Verbindungen bzw. erfindungsgemäßen Mischungen vorzugsweise 0,05 bis 50 Gew.-%, vorzugsweise 0,5 bis 20 Gew.-%, bezogen auf das gesamte Parfümöl.In perfume compositions, the total amount of the compounds or mixtures according to the invention to be used according to the invention is preferably 0.05 to 50% by weight, preferably 0.5 to 20% by weight, based on the total perfume oil.
Parfümöle, die die erfindungsgemäßen Verbindungen enthalten, können in konzentrierter Form, in Lösungen oder in oben beschriebener modifizierter Form verwendet werden für die Herstellung von z.B. Parfüm-Extraits, Eau de Parfüms, Eau de Toilettes, Rasierwässer, Eau de Colognes, Pre-shave-Produkte, Splash- Colognes und parfümierten Erfrischungstüchern sowie die Parfümierung von sauren, alkalischen und neutralen Reinigungsmitteln, wie z.B. Fußbodenreinigern, Fensterglasreinigern, Geschirrspülmittel, Bad- und Sanitär- reinigem, Scheuermilch, festen und flüssigen WC-Reinigern, pulver- und schaumförmigen Teppichreinigern, flüssigen Waschmitteln, pulverförmigen Waschmitteln, Wäschevorbehandlungsmitteln wie Bleichmittel, Einweichmittel und Fleckenentfernern, Wäscheweichspülem, Waschseifen, Waschtabletten, Desinfektionsmitteln, Oberflächendesinfektionsmitteln sowie von Luftverbesserem in flüssiger, gelartiger oder auf einem festen Träger aufgebrachter Form, Aerosolsprays, Wachsen und Polituren wie Möbelpolituren, Fußbodenwachsen, Schuhcremes sowie Körperpflegemitteln wie z.B. festen und flüssigen Seifen, Duschgelen, Shampoos, Rasierseifen, Rasierschäumen, Badeölen, kosmetischen Emulsionen vom öl-in-Wasser-, vom Wasser-in-öl- und vom Wasser-in-öl-in-Wasser-Typ wie z.B. Hautcremes- und -lotionen, Gesichtscremes und -lotionen, Sonnenschutzcremes-und -lotionen, After-sun- cremes und -lotionen, Handcremes und -lotionen, Fußcremes und -lotionen, Enthaarungscremes und -lotionen, After-shave-Cremes und -lotionen, Bräunungscremes und -lotionen, Haarpflegeprodukten wie z.B. Haarsprays, Haargelen, festigen Haarlotionen, Haarspülungen, permanenten und semipermanenten Haarfärbemitteln, Haarverformungsmitteln wie kaltwellen und Haarglättungsmitteln, Haarwässern, Haarcremes und -lotionen, Deodorantien und Antiperspirantien wie z.B. Achselsprays, Roll-ons, Deosticks, Deocremes, Produkten der dekorativen Kosmetik wie z.B. Lidschatten, Nagellacke, Make-ups, Lippenstifte, Mascara sowie von Kerzen, Lampenölen, Räucherstäbchen, Insektiziden, Repellenten und Treibstoffen.Perfume oils containing the compounds according to the invention can be used in concentrated form, in solutions or in modified form described above for the production of, for example, perfume extracts, Eau de Parfums, Eau de Toilettes, shaving waters, Eau de Colognes, Pre-shave Products, splash colognes and perfumed refreshing wipes and the perfuming of acidic, alkaline and neutral detergents, such as 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, powder detergents, laundry pretreatment agents such as bleaches, soak and stain removers, fabric softeners, laundry soaps, washing tablets, disinfectants, surface disinfectants and air fresheners in liquid, gel or solid support form, aerosol sprays, Waxes and polishes such as furniture polishes, floor waxes, shoe polishes and personal care products such as solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of oil-in-water, water-in-oil and 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, 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, roll-ons, deodorants, deodorants, decorative cosmetics, such as eyeshadows, nail polishes, make-ups, lipsticks, mascara and candles, lamp oils, incense sticks, insecticides , Repellents and fuels.
Die Erfindung betrifft auch ein Verfahren zur Herstellung erfindungsgemäßer Mischungen, die eine Verbindung der Formel (Ia) und eine Verbindung der Formel (Ib) umfassen, mit folgenden Schritten:The invention also relates to a process for preparing mixtures according to the invention which comprise a compound of the formula (Ia) and a compound of the formula (Ib), comprising the following steps:
Bereitstellen eines Alkohols der Formel (VI), z. B. durch Baylis-Hillman Reaktion von Cyclopentenon mit einem aliphatischen AldehydProviding an alcohol of formula (VI), e.g. By Baylis-Hillman reaction of cyclopentenone with an aliphatic aldehyde
und anschließendand subsequently
Johnson-Claisen 3.3-sigmatrope Umlagerung des Alkohols (VI) zu der erfindungsgemäßen Mischung umfassend eine Verbindung der Formel (Ia) und eine Verbindung der Formel (Ib), üblicherweise in Gegenwart vonJohnson-Claisen 3.3-sigmatropic rearrangement of the alcohol (VI) to the mixture according to the invention comprising a compound of the formula (Ia) and a compound of the formula (Ib), usually in the presence of
Trimethylorthoacetat und katalytischen Mengen Propionsäure.Trimethyl orthoacetate and catalytic amounts of propionic acid.
Verbindungen der Formel (Ia) können unter Verwendung der Vorschrift aus WO 2004/043895 hergestellt werden oder durch chromatographische oder destillative Trennung einer erfindungsgemäßen Mischung erhalten werden.Compounds of formula (Ia) can be prepared using the procedure of WO 2004/043895 or obtained by chromatographic or distillative separation of a mixture according to the invention.
Verbindungen der Formel (Ib) können durch chromatographische oder destillative Trennung einer erfindungsgemäßen Mischung erhalten werden. Die erfindungsgemäß als Jasmin-Riechstoffe zu verwendenden Verbindungen der Formel (Ia) und (Ib), können nach dem Fachmann wohlvertrauten Methoden hergestellt werden. Die zur Herstellung des Alkohols der Formel (VI) bevorzugte Baylis-Hillman-Reaktion von Cyclopentenon mit einem aliphatischen Aldehyd wird vorzugsweise nach der Vorschrift aus Y.M.A. Yamada and S. Ikegami, Tetrahedron Lett., 41, 2165 (2000) durchgeführt, d. h. in Gegenwart von rac-1 ,1 '- Bi-2-naphthol und Tributylphosphin.Compounds of the formula (Ib) can be obtained by chromatographic or distillative separation of a mixture according to the invention. The compounds of the formula (Ia) and (Ib) to be used according to the invention as jasmine fragrances can be prepared by methods well known to the person skilled in the art. The preferred Baylis-Hillman reaction of cyclopentenone with an aliphatic aldehyde for preparing the alcohol of the formula (VI) is preferably carried out according to the instructions of YMA Yamada and S. Ikegami, Tetrahedron Lett., 41, 2165 (2000), ie in the presence of rac-1, 1 '- bi-2-naphthol and tributylphosphine.
Die Johnson-Claisen-3.3-sigmatrope Umlagerung des Alkohols der Formel (VI) wird vorzugsweise in Toluol und in Gegenwart katalytischer Mengen Propionsäure durchgeführt, vorzugsweise nach der Vorschrift von S.E. Drewes et al., Synth. Comm, 20, 1437 (1990) (Schema 1).The Johnson-Claisen 3.3 sigmatropic rearrangement of the alcohol of formula (VI) is preferably carried out in toluene and in the presence of catalytic amounts of propionic acid, preferably according to the instructions of S.E. Drewes et al., Synth. Comm, 20, 1437 (1990) (Scheme 1).
Schema 1Scheme 1
Ein weiterer Aspekt der vorliegenden Erfindung betrifft ein Verfahren zur Herstellung einer Verbindung der Formel (Ib) mit folgendem Schritt: Isomerisieren einer Mischung der Verbindungen der Formeln (Ia) und (Ib) (oder auch derA further aspect of the present invention relates to a process for the preparation of a compound of the formula (Ib) which comprises the following step: isomerizing a mixture of the compounds of the formulas (Ia) and (Ib) (or else the
Verbindung der Formel (Ia) allein), wobei R1, R2 die oben genanntenCompound of the formula (Ia) alone), where R 1 , R 2 are those mentioned above
Bedeutungen haben, in Gegenwart einer Alkoholat-Base wie z.B.Have meanings in the presence of an alkoxide base such as e.g.
Natriummethylat, Natriumethylat oder Kalium-fert-butanolat in einem polaren aprotischen Lösungsmittel wie z.B. Dimethylformamid (DMF) oder N-Methyl-2- pyrrolidinon (NMP) oder einem polaren protischen Lösungsmittel wie z.B. Methanol, Ethanol oder fert-Butanol.Sodium methylate, sodium ethylate or potassium tert-butoxide in a polar aprotic solvent such as dimethylformamide (DMF) or N-methyl-2- pyrrolidinone (NMP) or a polar protic solvent such as methanol, ethanol or tert-butanol.
Vorzugsweise wird die z. B. nach der Johnson-Claisen-3.3-sigmatropen Umlagerung erhaltene Mischung der Verbindungen der Formeln (Ia) und (Ib) mit Kalium-fert-butanolat in DMF umgesetzt und anschließend bei z. B. 0° C mit 20 %iger Essigsäure gequencht, entsprechend der Vorgehensweise in EP 203 528.Preferably, the z. B. obtained after the Johnson-Claisen-3.3-sigmatropic rearrangement mixture of the compounds of formulas (Ia) and (Ib) with potassium butoxide-finished in DMF and then at z. B. 0 ° C quenched with 20% acetic acid, according to the procedure in EP 203 528.
Die folgenden, nicht limitierenden Beispiele erläutern die Erfindung. The following non-limiting examples illustrate the invention.
A. Baylis-Hillman-Reaktion von Cyclopentenon mit aliphatischen Aldehyden:A. Baylis-Hillman reaction of cyclopentenone with aliphatic aldehydes:
Allgemeine Vorschrift zur Baylis-Hillman-Reaktion von Cyclopentenon mit aliphatischen Aldehyden (vgl. die nachfolgenden Beispiele 1-6):General procedure for the Baylis-Hillman reaction of cyclopentenone with aliphatic aldehydes (see Examples 1-6 below):
Eine Lösung aus Cyclopentenon (1.0 Moläquivalente), einem aliphatischen Aldehyd (1.50 Moläquivalente), rac-1 ,1 '-Bi-2-naphthol (0.1 Moläquivalente) und nBu3P (0.2 Moläquivalente) in THF (2.0 ml/mmol Cyclopentenon) wird bei Raumtemperatur unter N2 über einen Zeitraum von 1 -5 Stunden gerührt. Nach beendeter Reaktion wird die Reaktionslösung mit Hexan (1 ml/mmol Cyclopentenon) verdünnt und anschließend je 1x mit gesättigter NH4CI-Lösung, gesättigter NaHCO3-Lösung und gesättigter NaCI-Lösung gewaschen, die organische Phase wird über Na2SO4 getrocknet und nach Filtration wird das Lösungsmittel am Rotationsverdampfer entfernt. Das Rohprodukt wird flashchromatographisch an Kieselgel (Cyclohexan/EtOAc = 2:1) gereinigt.A solution of cyclopentenone (1.0 molar equivalents), an aliphatic aldehyde (1:50 molar equivalents), rac-1, 1 '-Bi-2-naphthol (0.1 mole equivalents) and nBu 3 P (0.2 molar equivalents) in THF (2.0 ml / mmol cyclopentenone) is stirred at room temperature under N 2 for a period of 1-5 hours. After completion of the reaction, the reaction solution is diluted with hexane (1 ml / mmol cyclopentenone) and then washed each 1x with saturated NH 4 Cl solution, saturated NaHCO 3 solution and saturated NaCl solution, the organic phase is dried over Na 2 SO 4 and after filtration, the solvent is removed on a rotary evaporator. The crude product is flash-chromatographed on silica gel (cyclohexane / EtOAc = 2: 1).
Beispiel 1 :Example 1 :
2-(1-Hydroxy-hexyl)-cyclopent-2-enon (Verbindung der Formel (VI) mit R1 = H und R2 = n-Butyl): Wurde analog der allgemeinen Vorschrift zur Baylis-Hillman- Reaktion hergestellt, wobei als Ausgangsaldehyd n-Hexanal eingesetzt wurde.2- (1-Hydroxy-hexyl) -cyclopent-2-enone (compound of formula (VI) where R 1 = H and R 2 = n-butyl): Prepared analogously to the general procedure for the Baylis-Hillman reaction, wherein was used as the starting aldehyde n-hexanal.
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.91 (t, J = 6.9 Hz, 3H), 1.18-1.42 (m, 6H), 1.50-1.66 (m, 2H), 2.35-2.39 (m, 2H), 2.53-2.57 (m, 2H), 3.16 (s, 1OH), 4.36 (ddd, J = 7.8, 6.4, 1.3 Hz, 1 H), 7.42 (td, J = 2.8, 1.3 Hz, 1 H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.91 (t, J = 6.9 Hz, 3H), 1.18-1.42 (m, 6H), 1.50-1.66 (m, 2H), 2.35-2.39 (m, 2H), 2.53-2.57 (m, 2H), 3.16 (s, 1OH), 4.36 (ddd, J = 7.8, 6.4, 1.3 Hz, 1 H), 7.42 (td, J = 2.8, 1.3 Hz, 1 H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 14.0 (q), 22.6 (t), 25.1 (t), 26.6 (t), 31.6 (t), 35.3 (t), 35.8 (t), 67.5 (d), 148.1 (s), 158.1 (d), 210.0 (s). Beispiel 2: 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 14.0 (q), 22.6 (t), 25.1 (t), 26.6 (t), 31.6 (t), 35.3 (t), 35.8 (t ), 67.5 (d), 148.1 (s), 158.1 (d), 210.0 (s). Example 2:
2-(1-Hydroxy-pentyl)-cyclopent-2-enon (Verbindung der Formel (VI) mit R1 = H und R2 = n-Propyl): Wurde analog der allgemeinen Vorschrift zur Baylis-Hillman Reaktion hergestellt, wobei als Ausgangsaldehyd n-Pentanal eingesetzt wurde.2- (1-Hydroxy-pentyl) -cyclopent-2-enone (compound of formula (VI) where R 1 = H and R 2 = n-propyl): Was prepared analogously to the general procedure for Baylis-Hillman reaction, wherein Starting aldehyde n-pentanal was used.
Die 1H-NMR und 13C-NMR Spektren entsprechen denen aus WO 2004/043895 und werden somit an dieser Stelle nicht mehr angegeben.The 1 H-NMR and 13 C-NMR spectra correspond to those from WO 2004/043895 and are thus not specified here.
Beispiel 3:Example 3:
2-(1-Hydroxy-heptyl)-cyclopent-2-enon (Verbindung der Formel (VI) mit R1 = H und R2 = n-Pentyl): Wurde analog der allgemeinen Vorschrift zur Baylis-Hillman Reaktion hergestellt, wobei als Ausgangsaldehyd n-Heptanal eingesetzt wurde.2- (1-Hydroxy-heptyl) -cyclopent-2-enone (compound of formula (VI) where R 1 = H and R 2 = n-pentyl): Was prepared analogously to the general procedure for Baylis-Hillman reaction, wherein Starting aldehyde n-heptanal was used.
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.98 (t, J = 6.9 Hz, 3H), 1.24-1.38 (m, 8H), 1.59-1.73 (m, 2H), 2.43-2.47 (m, 2H), 2.60-2.64 (m, 2H), 3.93 (s, 1OH), 4.44 (ddd, J = 7.8, 5.5, 1.3 Hz, 1H), 7.46 (td, J = 2.7, 1.2 Hz, 1H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.98 (t, J = 6.9 Hz, 3H), 1.24-1.38 (m, 8H), 1.59-1.73 (m, 2H), 2.43-2.47 (m, 2H), 2.60-2.64 (m, 2H), 3.93 (s, 1OH), 4.44 (ddd, J = 7.8, 5.5, 1.3 Hz, 1H), 7.46 (td, J = 2.7, 1.2 Hz, 1H ).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 14.1 (q), 22.6 (t), 25.4 (t), 26.6 (t), 29.1 (t), 31.8 (t), 35.2 (t), 35.8 (t), 67.8 (d), 147.8 (s), 157.9 (d), 210.1 (s). 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 14.1 (q), 22.6 (t), 25.4 (t), 26.6 (t), 29.1 (t), 31.8 (t), 35.2 (t ), 35.8 (t), 67.8 (d), 147.8 (s), 157.9 (d), 210.1 (s).
Beispiel 4:Example 4:
2-(1-Hydroxy-butyl)-cyclopent-2-enon (Verbindung der Formel (VI) mit R1 = H und R2 = Ethyl): Wurde analog der allgemeinen Vorschrift zur Baylis-Hillman Reaktion hergestellt, wobei als Ausgangsaldehyd n-Butanal eingesetzt wurde.2- (1-hydroxy-butyl) -cyclopent-2-enone (compound of formula (VI) where R 1 = H and R 2 = ethyl): Was prepared analogously to the general procedure for Baylis-Hillman reaction, wherein as the starting aldehyde n Butanal was used.
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.93 (t, J = 7.4 Hz, 3H), 1.29-1.52 (m, 2H), 1.61 (dddd, J = 13.6, 9.5, 7.8, 5.1 Hz, 1H), 1.66 (dddd, J = 13.6, 9.5, 6.6, 5.1 Hz, 1 H), 2.41-2.44 (m, 2H), 2.60-2.64 (m, 2H), 3.18 (s, 1OH), 4.43 (ddd, J = 7.8, 5.1 1.3 Hz, 1H), 7.51 (td, J = 2.7, 1.3 Hz, 1H). 13C-NMR (100 MHz, CDCI3): δ (ppm) = 13.9 (q), 18.6 (t), 26.6 (t), 35.3 (t), 38.0 (t), 67.1 (d), 148.2 (s), 158.3 (d), 209.9 (s). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.93 (t, J = 7.4 Hz, 3H), 1.29-1.52 (m, 2H), 1.61 (dddd, J = 13.6, 9.5, 7.8, 5.1 Hz, 1H), 1.66 (dddd, J = 13.6, 9.5, 6.6, 5.1 Hz, 1H), 2.41-2.44 (m, 2H), 2.60-2.64 (m, 2H), 3.18 (s, 1OH), 4.43 (ddd, J = 7.8, 5.1 1.3 Hz, 1H), 7.51 (td, J = 2.7, 1.3 Hz, 1H). 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 13.9 (q), 18.6 (t), 26.6 (t), 35.3 (t), 38.0 (t), 67.1 (d), 148.2 (s ), 158.3 (d), 209.9 (s).
Beispiel 5:Example 5:
2-(1-Hydroxy-2-methyl-propyl)-cyclopent-2-enon (Verbindung der Formel (VI) mit R1 und R2 = Methyl): Wurde analog der allgemeinen Vorschrift zur Baylis-Hillman Reaktion hergestellt, wobei als Ausgangsaldehyd /so-Butyraldehyd eingesetzt wurde.2- (1-hydroxy-2-methyl-propyl) -cyclopent-2-enone (compound of formula (VI) with R 1 and R 2 = methyl): Was prepared analogously to the general procedure for Baylis-Hillman reaction, wherein Starting aldehyde / so-butyraldehyde was used.
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.89 (d, J = 6.9 Hz, 3H), 0.91 (d, J = 6.9 Hz, 3H), 1.95 (oct, J = 6.9 Hz, 1H), 2.43-2.46 (m, 2H), 2.62-2.66 (m, 2H), 3.07 (s, 10H), 4.20 (dd, J = 6.0, 1.3 Hz, 1 H), 7.49 (td, J = 2.8, 1.3 Hz, 1 H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.89 (d, J = 6.9 Hz, 3H), 0.91 (d, J = 6.9 Hz, 3H), 1.95 (oct, J = 6.9 Hz, 1H), 2.43-2.46 (m, 2H), 2.62-2.66 (m, 2H), 3.07 (s, 10H), 4.20 (dd, J = 6.0, 1.3 Hz, 1H), 7.49 (td, J = 2.8 , 1.3 Hz, 1 H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 17.1 (q), 19.0 (q), 26.6 (t), 32.8 (d), 35.3 (t), 73.0 (d), 146.7 (s), 159.4 (d), 210.1 (s). 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 17.1 (q), 19.0 (q), 26.6 (t), 32.8 (d), 35.3 (t), 73.0 (d), 146.7 (s ), 159.4 (d), 210.1 (s).
Beispiel 6:Example 6:
2-(1-Hydroxy-3-methyl-butyl)-cyclopent-2-enon (Verbindung der Formel (VI) mit R1 = H und R2 = /so-Propyl): Wurde analog der allgemeinen Vorschrift zur Baylis- Hillman Reaktion hergestellt, wobei als Ausgangsaldehyd /so-Valeraldehyd eingesetzt wurde.2- (1-hydroxy-3-methyl-butyl) -cyclopent-2-enone (compound of formula (VI) where R 1 = H and R 2 = / so-propyl): Was analogous to the general procedure for Baylis Hillman Reaction prepared using as starting aldehyde / so-valeraldehyde.
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.93 (d, J = 6.7 Hz, 3H), 0.94 (d, J = 6.7 Hz, 3H), 1.45 (ddd, J = 13.7, 8.7, 4.5 Hz, 1H), 1.59 (ddd, J = 13.7, 9.2, 5.3 Hz, 1 H), 1.80 (dsepd, J = 8.7, 6.7, 5.3 Hz, 1 H), 2.42-2.45 (m, 2H), 2.59-2.64 (m, 2H), 3.40 (s, 1OH), 4.51 (ddd, J = 9.2, 4.5, 1.2 Hz, 1 H), 7.49 (td, J = 2.7, 1.2 Hz, 1 H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.93 (d, J = 6.7 Hz, 3H), 0.94 (d, J = 6.7 Hz, 3H), 1.45 (ddd, J = 13.7, 8.7 , 4.5 Hz, 1H), 1.59 (ddd, J = 13.7, 9.2, 5.3 Hz, 1 H), 1.80 (dsepd, J = 8.7, 6.7, 5.3 Hz, 1 H), 2.42-2.45 (m, 2H), 2.59-2.64 (m, 2H), 3.40 (s, 1OH), 4.51 (ddd, J = 9.2, 4.5, 1.2 Hz, 1 H), 7.49 (td, J = 2.7, 1.2 Hz, 1 H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 21.8 (q), 23.3 (q), 24.4 (d), 26.6 (t), 35.3 (t), 44.8 (t), 65.5 (d), 148.5 (s), 158.0 (d), 210.0 (s). B. Johnson-Claisen-Umlagerung: 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 21.8 (q), 23.3 (q), 24.4 (d), 26.6 (t), 35.3 (t), 44.8 (t), 65.5 (i.e. ), 148.5 (s), 158.0 (d), 210.0 (s). B. Johnson-Claisen Rearrangement:
Allgemeine Vorschrift zur Johnson-Claisen Umlagerung von 2-(1-Hydroxy-alkyl)- cyclopent-2-enon mit Trimethylorthoacetat (vgl. die nachfolgenden Beispiele 7- 12):General procedure for the Johnson-Claisen rearrangement of 2- (1-hydroxy-alkyl) -cyclopent-2-enone with trimethyl orthoacetate (see Examples 7-12 below):
Eine Lösung aus 2-(1-Hydroxy-alkyl)-cyclopent-2-enon (1.0 Moläquivalente), Trimethylorthoacetat (3.6 Moläquivalente) und Propionsäure (0.05 Moläquivalente) wird in Toluol (1.0 ml/mmol 2-(1-Hydroxy-alkyl)-cyclopent-2- enon) zum Rückfluss erhitzt und ein Azeotrop aus Methanol und Toluol wird abdestilliert. Der Rückstand wird in Ether (1 ml/mmol 2-(1-Hydroxy-alkyl)- cyclopent-2-enon) aufgenommen und je 1x mit 1 M NaOH, gesättigter NaHCO3- Lösung und gesättigter NaCI-Lösung gewaschen, getrocknet, abfiltriert und einrotiert. Das Rohprodukt wird durch fraktionierte Destillation im Vakuum gereinigt.A solution of 2- (1-hydroxy-alkyl) -cyclopent-2-enone (1.0 molar equivalents), trimethyl orthoacetate (3.6 molar equivalents) and propionic acid (0.05 molar equivalents) is dissolved in toluene (1.0 ml / mmol 2- (1-hydroxy-alkyl ) -cyclopent-2-enone) is heated to reflux and an azeotrope of methanol and toluene is distilled off. The residue is taken up in ether (1 ml / mmol 2- (1-hydroxyalkyl) cyclopent-2-enone) and washed once each with 1 M NaOH, saturated NaHCO 3 solution and saturated NaCl solution, dried, filtered off and rotated. The crude product is purified by fractional distillation in vacuo.
Beispiel 7:Example 7:
[2-Hex-(E/Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester (Verbindung der Formel (Ia) mit R1 = H und R2 = n-Buty\y[2-((E/Z)-Hex-1-enyl)-3-oxo-cyclopentyl]- essigsäuremethylester (Verbindung der Formel (Ib) mit R1 = H und R2 = n-Butyl): Wurde analog der allgemeinen Vorschrift zur Johnson-Claisen Umlagerung, ausgehend von 2-(1-Hydroxy-hexyl)-cyclopent-2-enon, hergestellt. Man erhält ein E/Z Isomerengemisch von [2-Hex-(E/Z)-yliden-3-oxo-cyclopentyl]- essigsäuremethylester und [2-((E/Z)-Hex-1 -enyl)-3-oxo-cyclopentyl]- essigsäuremethylester im Verhältnis 5.0-6.0:1. Das folgende GC gibt die Isomerenverhältnisse des durch Destillation gereinigten Produktes an: GC (DB-I):[2-Hex (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester (Compound of the formula (Ia) where R 1 = H and R 2 = n-butyl \ y [2 - ((E / Z ) -Hex-1-enyl) -3-oxo-cyclopentyl] - acetic acid methyl ester (compound of formula (Ib) with R 1 = H and R 2 = n-butyl): Was analogous to the general procedure for Johnson-Claisen rearrangement, starting of 2- (1-hydroxy-hexyl) -cyclopent-2-enone, to give an E / Z isomer mixture of [2-hex- (E / Z) -ylidene-3-oxocyclopentyl] -acetic acid methyl ester and [ 2 - ((E / Z) -hex-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester in the ratio 5.0-6.0: 1 The following GC indicates the isomer ratios of the product purified by distillation: GC (DB-I):
Index Area % VerbindungIndex Area% connection
1694 2.91 [2-(Z)-Hex-1 -enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1694 2.91 [2- (Z) -hex-1-enyl-3-oxo-cyclopentyl] -acetic acid methyl ester
1712 11.14 [2-(E)-Hex-1-enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1712 11.14 [2- (E) -hex-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1730 36.47 [2-Hex-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1730 36.47 [2-Hex- (Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
1768 42.50 [2-Hex-(E)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1768 42.50 [2-Hex (E) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
Die einzelnen Isomere konnten durch präparative HPLC (Säule: GROM Saphir 110 Si, 5μm, 150x20 mm; Eluent: Heptan/MTBE = 9:1; Flussrate: 45 ml/min; Druck: 108 bar) getrennt, analysiert, spektroskopisch vermessen und geruchlich evaluiert werden.The individual isomers were separated by preparative HPLC (column: GROM sapphire 110 Si, 5 μm, 150 × 20 mm, eluent: heptane / MTBE = 9: 1, flow rate: 45 ml / min, pressure: 108 bar), analyzed, measured spectroscopically and odorless be evaluated.
[2-(Z)-Hex-1-enyl)-3-oxo-cyclopentyl]-essigsäuremethylester:[2- (Z) -hex-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester:
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.89 (t, J = 6.9 Hz, 3H), 1.22-1.40 (m, 4H), 1.48-1.61 (m, 1 H), 1.97-2.10 (m, 1 H), 2.17-2.37 (m, 5H), 2.39-2.48 (m, 1H), 2.55- 2.63 (m, 1 H), 2.81 (t, J = 9.8 Hz, 1 H), 3.68 (s, 3H), 5.08 (ddt, J = 10.7, 9.1 , 1.6 Hz, 1 H), 5.76 (dtd, J = 10.7, 7.4, 0.8 Hz, 1H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.89 (t, J = 6.9 Hz, 3H), 1.22-1.40 (m, 4H), 1.48-1.61 (m, 1H), 1.97- 2.10 (m, 1H), 2.17-2.37 (m, 5H), 2.39-2.48 (m, 1H), 2.55-2.63 (m, 1H), 2.81 (t, J = 9.8 Hz, 1H), 3.68 (s, 3H), 5.08 (ddt, J = 10.7, 9.1, 1.6Hz, 1H), 5.76 (dtd, J = 10.7, 7.4, 0.8Hz, 1H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 16.8 (q), 22.9 (t), 29.4 (2t), 33.6 (t), 39.9 (2t), 41.9 (d), 52.5 (q), 56.7 (d), 123.8 (d), 136.4 (d), 174.2 (s), 217.3. 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 16.8 (q), 22.9 (t), 29.4 (2t), 33.6 (t), 39.9 (2t), 41.9 (d), 52.5 (q ), 56.7 (d), 123.8 (d), 136.4 (d), 174.2 (s), 217.3.
Geruch: schwach jasminig, mit lactonigen AspektenOdor: weak jasmine, with lactone-like aspects
[2-(E)-Hex-1-enyl)-3-oxo-cyclopentyl]-essigsäuremethylester: 1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.90 (t, J = 6.9 Hz, 3H), 1.28-1.40 (m, 4H), 1.48-1.61 (m, 1H), 2.14-2.66 (m, 7H), 3.62-3.74 (m, 1H), 3.69 (s, 3H), 5.20 (ddt, J = 15.3, 7.6, 1.5 Hz, 1 H), 5.55 (dtd, J = 15.3, 6.5, 0.5 Hz, 1H).[2- (E) -hex-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester: 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.90 (t, J = 6.9 Hz, 3H), 1.28-1.40 (m, 4H), 1.48-1.61 (m, 1H), 2.14-2.66 (m, 7H), 3.62-3.74 (m, 1H), 3.69 (s, 3H), 5.20 (ddt, J = 15.3, 7.6, 1.5Hz, 1H), 5.55 (dtd, J = 15.3, 6.5, 0.5 Hz, 1H).
Geruch: weiche Jasminnoten mit lactonigen AspektenOdor: soft jasmine notes with lactone-like aspects
[2-Hex-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester[2-Hex (Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.88 (t, J = 6.9 Hz, 3H), 1.24-1.34 (m, 4H), 1.35-1.43 (m, 2H), 1.52-1.62 (m, 1 H), 2.14-2.43 (m, 5H), 2.61 (dd, J = 15.4, 5.9 Hz, 1 H), 2.64-2.72 (m, 1 H), 3.10-3.19 (m, J = 1H), 3.70 (s, 3H), 5.90 (td, J = 7.6, 2.3 Hz, 1H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.88 (t, J = 6.9 Hz, 3H), 1.24-1.34 (m, 4H), 1.35-1.43 (m, 2H), 1.52-1.62 (m, 1H), 2.14-2.43 (m, 5H), 2.61 (dd, J = 15.4, 5.9Hz, 1H), 2.64-2.72 (m, 1H), 3.10-3.19 (m, J = 1H ), 3.70 (s, 3H), 5.90 (td, J = 7.6, 2.3 Hz, 1H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 14.0 (q), 22.2 (t), 26.9 (t), 27.6 (t), 29.0 (t), 31.4 (t), 38.2 (t), 39.3 (t), 39.6 (d), 51.6 (q), 137.7 (s), 141.6 (d), 172.5 (s), 207.6 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 14.0 (q), 22.2 (t), 26.9 (t), 27.6 (t), 29.0 (t), 31.4 (t), 38.2 (t ), 39.3 (t), 39.6 (d), 51.6 (q), 137.7 (s), 141.6 (d), 172.5 (s), 207.6
(S).(S).
Geruch: stark Jasmin ig, mit citrischen AspektenOdor: strong jasmine, with citrusy aspects
[2-Hex-(E)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester[2-hex (E) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.88 (t, J = 6.9 Hz, 3H), 1.27-1.34 (m, 4H), 1.42-1.51 (m, 2H), 1.86 (dddd, J = 13.4, 8.4, 3.0, 1.8 Hz 1H), 2.05 (ddddd, J = 13.4, 11.4, 8.8, 7.8, 0.9 Hz, 1H), 2.18 (qd, J = 7.7, 0.9 Hz, 2H), 2.32 (dddd, J = 18.7, 8.8, 3.1, 0.4 Hz, 1 H), 2.38 (dd, J = 15.6, 10.2 Hz, 1 H), 2.39 (dddd, J = 18.7, 9.9, 2.5, 0.6 Hz, 1H), 2.47 (ddd, J = 15.6, 4.8, 0.8 Hz, 1 H), 3.39-3.48 (m, 1H), 3.71 (s, 3H), 6.59 (td, J = 7.7, 2.0 Hz, 1H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.88 (t, J = 6.9 Hz, 3H), 1.27-1.34 (m, 4H), 1.42-1.51 (m, 2H), 1.86 (dddd , J = 13.4, 8.4, 3.0, 1.8 Hz 1H), 2.05 (ddddd, J = 13.4, 11.4, 8.8, 7.8, 0.9 Hz, 1H), 2.18 (qd, J = 7.7, 0.9 Hz, 2H), 2.32 ( dddd, J = 18.7, 8.8, 3.1, 0.4 Hz, 1 H), 2.38 (dd, J = 15.6, 10.2 Hz, 1 H), 2.39 (dddd, J = 18.7, 9.9, 2.5, 0.6 Hz, 1H), 2.47 (ddd, J = 15.6, 4.8, 0.8 Hz, 1H), 3.39-3.48 (m, 1H), 3.71 (s, 3H), 6.59 (td, J = 7.7, 2.0 Hz, 1H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 13.9 (q), 22.5 (t), 25.2 (t), 28.3 (t), 29.2 (t), 31.6 (t), 34.9 (d), 35.8 (t), 38.6 (t), 51.7 (q), 138.4 (d), 139.7 (s), 172.3 (s), 206.3 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 13.9 (q), 22.5 (t), 25.2 (t), 28.3 (t), 29.2 (t), 31.6 (t), 34.9 (i.e. ), 35.8 (t), 38.6 (t), 51.7 (q), 138.4 (d), 139.7 (s), 172.3 (s), 206.3
(S).(S).
Geruch: starke, strahlende Jasminnote, mit fruchtigen Aspekten Der Geruch der Isomerenmischung, wie oben in der Tabelle gezeigt, wird wie folgt beschrieben: starke, strahlende und weiche Jasminnote mit fruchtigen Aspekten.Odor: strong, radiant jasmine note, with fruity aspects The odor of the isomeric mixture as shown in the table above is described as follows: strong, radiant and soft jasmine note with fruity aspects.
Beispiel 8:Example 8:
[2-Pent-(E/Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester (Verbindung der Formel (Ia) mit R1 = H und R2 = n-Pτopy\)/[2-((E/Z)-Pent-1-enyl)-3-oxo- cyclopentylj-essigsäuremethylester (Verbindung der Formel (Ib) mit R1 = H und R2 = n-Propyl): Wurde analog der allgemeinen Vorschrift zur Johnson-Claisen Umlagerung, ausgehend von 2-(1-Hydroxy-pentyl)-cyclopent-2-enon, hergestellt. Man erhält ein E/Z Isomerengemisch von [2-Pent-(E/Z)-yliden-3-oxo-cyclopentyl]- essigsäuremethylester und [2-((E/Z)-Pent-1 -enyl)-3-oxo-cyclopentyl]- essigsäuremethylester im Verhältnis 5.0-6.0:1. Das folgende GC gibt die Isomerenverhältnisse des durch Destillation gereinigten Produktes an:[2-Pent- (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester (compound of the formula (Ia) where R 1 = H and R 2 = n-p-popy \) / [2 - ((E / Z) -Pent-1-enyl) -3-oxo-cyclopentylj-acetic acid methyl ester (compound of formula (Ib) with R 1 = H and R 2 = n-propyl): Was analogous to the general procedure for Johnson-Claisen rearrangement, starting of 2- (1-hydroxy-pentyl) -cyclopent-2-enone. An E / Z isomer mixture of [2-pent (E / Z) -ylidene-3-oxocyclopentyl] -acetic acid methyl ester and [2 - ((E / Z) -pent-1-enyl) -3-oxo is obtained -cyclopentyl] -acetic acid methyl ester in the ratio 5.0-6.0: 1. The following GC indicates the isomer ratios of the product purified by distillation:
GC (DB-I):GC (DB-I):
Index Area % VerbindungIndex Area% connection
1602 3.15 [2-(Z)-Pent-1 -enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1602 3.15 [2- (Z) -pent-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1617 10.64 [2-(E)-Pent-1 -enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1617 10.64 [2- (E) -pent-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1637 44.08 [2-Pent-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1637 44.08 [2-Pent- (Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
1675 38.06 [2-Pent-(E)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1675 38.06 [2-Pent- (E) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
Die 1H-NMR und 13C-NMR Spektren der beiden Hauptkomponenten [2-Pent-(Z)- yliden-3-oxo-cyclopentyl]-essigsäuremethylester und [2-Pent-(E)-yliden-3-oxo- cyclopentyl]-essigsäuremethylester entsprechen denen aus WO 2004/043895 und werden somit an dieser Stelle nicht mehr angegeben. 1 H-NMR and 13 C-NMR spectra of the two main components [2-pent- (Z) - ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester and [2-pent- (E) -ylidene-3-oxo] cyclopentyl] -acetic acid methyl ester correspond to those from WO 2004/043895 and are therefore not specified here at this point.
Geruch der Isomerenmischung: starke, weiche Jasminnote, mit schöner Fruchtnote.Odor of the isomer mixture: strong, soft jasmine note, with a nice fruity note.
Beispiel 9:Example 9:
[2-Hept-(E/Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester (Verbindung der Formel (Ia) mit R1 = H und R2 = n-Penty\)/[2-((E/Z)-Hept-1-enyl)-3-oxo- cyclopentylj-essigsäuremethylester (Verbindung der Formel (Ib) mit R1 = H und R2 = n-Butyl): Wurde analog der allgemeinen Vorschrift zur Johnson-Claisen Umlagerung, ausgehend von 2-(1-Hydroxy-heptyl)-cyclopent-2-enon, hergestellt. Man erhält ein E/Z Isomerengemisch von [2-Hept-(E/Z)-yliden-3-oxo-cyclopentyl]- essigsäuremethylester und [2-((E/Z)-Hept-1 -enyl)-3-oxo-cyclopentyl]- essigsäuremethylester im Verhältnis 5-7:1 , Das folgende GC gibt die Isomerenverhältnisse des durch Destillation gereinigten Produktes an:[2-hept- (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester (compound of formula (Ia) where R 1 = H and R 2 = n-penty \) / [2 - ((E / Z) -Hept-1-enyl) -3-oxo-cyclopentylj-acetic acid methyl ester (compound of formula (Ib) with R 1 = H and R 2 = n-butyl): Was analogous to the general procedure for Johnson-Claisen rearrangement, starting of 2- (1-hydroxyheptyl) cyclopent-2-enone. An E / Z isomer mixture of [2-hept- (E / Z) -ylidene-3-oxocyclopentyl] -acetic acid methyl ester and [2 - ((E / Z) -hept-1-enyl) -3-oxo is obtained -cyclopentyl] -acetic acid methyl ester in the ratio 5-7: 1, The following GC indicates the isomer ratios of the product purified by distillation:
GC (DB-I):GC (DB-I):
Index Area % VerbindungIndex Area% connection
1791 3.29 [2-(Z)-Hept-1 -enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1791 3.29 [2- (Z) -Hept-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1813 9.67 [2-(E)-Hept-1 -enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1813 9.67 [2- (E) -Hept-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1833 24.40 [2-Hept-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1833 24.40 [2-Hept- (Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
1874 60.01 [2-Hept-(E)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester Die 1H-NMR und 13C-NMR Spektren der beiden Hauptkomponenten [2-Hept-(Z)- yliden-3-oxo-cyclopentyl]-essigsäuremethylester und [2-Hept-(E)-yliden-3-oxo- cyclopentylj-essigsäuremethylester werden an dieser Stelle angegeben.1874 60.01 [2-Hept- (E) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester The 1 H-NMR and 13 C-NMR spectra of the two main components [2-hept- (Z) - ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester and [2-hept- (E) -ylidene-3-oxocyclopentylj Acetic acid methyl ester are given at this point.
[2-Hept-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester:[2-hept-(Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester:
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.88 (t, J = 6.9 Hz, 3H), 1.23-1.36 (m, 6H), 1.40-1.50 (m, 2H), 1.52-1.62 (m, 1H), 2.25-2.50 (m, 5H), 2.61 (dd, J = 15.5, 4.1 Hz, 1 H), 2.64-2.72 (m, 1 H), 3.10-3.20 (m, J = 1H), 3.70 (s, 3H), 5.90 (td, J = 7.5, 2.3 Hz, 1H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.88 (t, J = 6.9 Hz, 3H), 1.23-1.36 (m, 6H), 1.40-1.50 (m, 2H), 1.52-1.62 (m, 1H), 2.25-2.50 (m, 5H), 2.61 (dd, J = 15.5, 4.1 Hz, 1H), 2.64-2.72 (m, 1H), 3.10-3.20 (m, J = 1H) , 3.70 (s, 3H), 5.90 (td, J = 7.5, 2.3 Hz, 1H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 14.1 (q), 22.6 (t), 26.7 (t), 27.7 (t), 28.9 (t), 29.2 (t), 31.6 (t), 38.3 (t), 38.7 (t), 39.4 (d), 51.7 (q), 137.8 (s), 141.7 (d), 172.5 (S), 207.6 (S). 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 14.1 (q), 22.6 (t), 26.7 (t), 27.7 (t), 28.9 (t), 29.2 (t), 31.6 (t ), 38.3 (t), 38.7 (t), 39.4 (d), 51.7 (q), 137.8 (s), 141.7 (d), 172.5 (S), 207.6 (S).
[2-Hept-(E)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester:[2-hept-(E) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester:
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.89 (t, J = 6.9 Hz, 3H), 1.23-1.36 (m, 6H), 1.40-1.50 (m, 2H), 1.86 (dddd, J = 13.3, 8.3, 3.1, 1.9 Hz 1H), 2.05 (ddddd, J = 13.3, 11.5, 8.7, 7.9, 0.8 Hz, 1H), 2.18 (qd, J = 7.7, 0.8 Hz, 2H), 2.25-2.43 (m, 3H), 2.47 (ddd, J = 15.6, 4.8, 0.8 Hz, 1H), 3.39-3.48 (m, 1H), 3.71 (s, 3H), 6.59 (td, J = 7.7, 2.0 Hz, 1 H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.89 (t, J = 6.9 Hz, 3H), 1.23-1.36 (m, 6H), 1.40-1.50 (m, 2H), 1.86 (dddd , J = 13.3, 8.3, 3.1, 1.9 Hz 1H), 2.05 (ddddd, J = 13.3, 11.5, 8.7, 7.9, 0.8 Hz, 1H), 2.18 (qd, J = 7.7, 0.8 Hz, 2H), 2.25- 2.43 (m, 3H), 2.47 (ddd, J = 15.6, 4.8, 0.8 Hz, 1H), 3.39-3.48 (m, 1H), 3.71 (s, 3H), 6.59 (td, J = 7.7, 2.0 Hz, 1 H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 14.1 (q), 22.5 (t), 25.2 (t), 28.6 (t), 29.1 (t), 29.2 (t), 31.6 (t), 34.9 (t), 35.8 (d), 38.6 (t), 51.7 (q), 138.4 (d), 139.7 (s), 172.3 (S), 206.3 (S). 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 14.1 (q), 22.5 (t), 25.2 (t), 28.6 (t), 29.1 (t), 29.2 (t), 31.6 (t ), 34.9 (t), 35.8 (d), 38.6 (t), 51.7 (q), 138.4 (d), 139.7 (s), 172.3 (S), 206.3 (S).
Geruch der Isomerenmischung: Jasminig, intensive Grünnote.Odor of the isomer mixture: jasmine, intense green note.
Beispiel 10:Example 10:
[2-But-(E/Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester (Verbindung der Formel (Ia) mit R1 = H und R2 = Ethy\)/[2-((E/Z)-But-1-enyl)-3-oxo-cyclopentyl]- essigsäuremethylester (Verbindung der Formel (Ib) mit R1 = H und R2 = Ethyl): Wurde analog der allgemeinen Vorschrift zur Johnson-Claisen Umlagerung, ausgehend von 2-(1-Hydroxy-butyl)-cyclopent-2-enon, hergestellt. Man erhält ein E/Z Isomerengemisch von [2-But-(E/Z)-yliden-3-oxo-cyclopentyl]- essigsäuremethylester und [2-((E/Z)-But-1 -enyl)-3-oxo-cyclopentyl]- essigsäuremethylester im Verhältnis 5.0-6.0:1. Das folgende GC gibt die Isomerenverhältnisse des durch Destillation gereinigten Produktes an:[2-But- (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester (compound of formula (Ia) where R 1 = H and R 2 = ethyl \) / [2 - ((E / Z) -but-1-enyl) -3-oxo-cyclopentyl] - Acetic acid methyl ester (compound of formula (Ib) with R 1 = H and R 2 = ethyl): Was prepared analogously to the general procedure for Johnson-Claisen rearrangement, starting from 2- (1-hydroxy-butyl) -cyclopent-2-enone , An E / Z isomer mixture of [2-but- (E / Z) -ylidene-3-oxocyclopentyl] -acetic acid methyl ester and [2 - ((E / Z) -but-1-enyl) -3-oxo is obtained -cyclopentyl] -acetic acid methyl ester in the ratio 5.0-6.0: 1. The following GC indicates the isomer ratios of the product purified by distillation:
GC (DB-I):GC (DB-I):
Index Area % VerbindungIndex Area% connection
1510 2.00 [2-(Z)-But-1 -enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1510 2.00 g of [2- (Z) -but-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1522 12.10 [2-(E)-But-1 -enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1522 12.10 [2- (E) -but-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1540 55.21 [2-But-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1540 55.21 [2-But- (Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
1575 24.60 [2-But-(E)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1575 24.60 [2-But- (E) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
Die 1H-NMR und 13C-NMR Spektren der beiden Hauptkomponenten [2-But-(Z)- yliden-3-oxo-cyclopentyl]-essigsäuremethylester und [2-But-(E)-yliden-3-oxo- cyclopentylj-essigsäuremethylester werden an dieser Stelle angegeben.The 1 H-NMR and 13 C-NMR spectra of the two main components [2-but- (Z) - ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester and [2-but- (E) -ylidene-3-oxocyclopentylj Acetic acid methyl ester are given at this point.
[2-But-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester:[2-but-(Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester:
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.92 (t, J = 7.3 Hz, 3H), 1.42 (sexd, J = 7.3, 1.1 Hz, 2H), 1.52-1.62 (m, 1 H), 2.26-2.50 (m, 5H), 2.61 (dd, J = 15.6, 6.0 Hz, 1H), 2.64-2.72 (m, 1 H), 3.09-3.19 (m, 1 H), 3.70 (s, 3H), 5.90 (td, J = 7.5, 2.2 Hz, 1H). 13C-NMR (100 MHz, CDCI3): δ (ppm) = 13.7 (q), 22.5 (t), 26.6 (t), 29.6 (t), 38.2 (t), 38.7 (d), 39.3 (t), 51.6 (q), 138.0 (s), 141.3 (d), 172.5 (s), 207.6 (s). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.92 (t, J = 7.3 Hz, 3H), 1.42 (sexd, J = 7.3, 1.1 Hz, 2H), 1.52-1.62 (m, 1 H), 2.26-2.50 (m, 5H), 2.61 (dd, J = 15.6, 6.0 Hz, 1H), 2.64-2.72 (m, 1H), 3.09-3.19 (m, 1H), 3.70 (s, 3H), 5.90 (td, J = 7.5, 2.2 Hz, 1H). 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 13.7 (q), 22.5 (t), 26.6 (t), 29.6 (t), 38.2 (t), 38.7 (d), 39.3 (t ), 51.6 (q), 138.0 (s), 141.3 (d), 172.5 (s), 207.6 (s).
[2-But-(E)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester:[2-but-(E) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester:
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.95 (t, J = 7.4 Hz, 3H), 1.50 (sexd, J = 7.4, 1.2 Hz, 2H), 1.86 (dddd, J = 13.5, 8.6, 3.1 , 1.8 Hz 1H), 2.05 (ddddd, J = 13.5, 11.4, 8.8, 7.8, 0.9 Hz, 1H), 2.18 (qd, J = 7.5, 0.7 Hz, 2H), 2.28-2.44 (m, 2H), 2.39 (dd, J = 15.6, 10.2 Hz, 1 H), 2.47 (dd, J = 15.6, 4.7 Hz, 1H), 3.40-3.48 (m, 1H), 3.71 (s, 3H), 6.59 (td, J = 7.7, 2.0 Hz, 1H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.95 (t, J = 7.4 Hz, 3H), 1.50 (sexd, J = 7.4, 1.2 Hz, 2H), 1.86 (dddd, J = 13.5 , 8.6, 3.1, 1.8 Hz 1H), 2.05 (ddddd, J = 13.5, 11.4, 8.8, 7.8, 0.9 Hz, 1H), 2.18 (qd, J = 7.5, 0.7 Hz, 2H), 2.28-2.44 (m, 2H), 2.39 (dd, J = 15.6, 10.2 Hz, 1H), 2.47 (dd, J = 15.6, 4.7 Hz, 1H), 3.40-3.48 (m, 1H), 3.71 (s, 3H), 6.59 ( td, J = 7.7, 2.0 Hz, 1H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 13.9 (q), 21.9 (t), 25.2 (t), 31.2 (t), 34.9 (d), 35.8 (t), 38.6 (t), 51.7 (q), 138.0 (d), 139.9 (s), 172.3 (s), 206.3 (s). 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 13.9 (q), 21.9 (t), 25.2 (t), 31.2 (t), 34.9 (d), 35.8 (t), 38.6 (t ), 51.7 (q), 138.0 (d), 139.9 (s), 172.3 (s), 206.3 (s).
Geruch der Isomerenmischung: weiche Jasminnote gepaart mit fruchtiger Bananennote.Odor of the isomer mixture: soft jasmine note paired with fruity banana note.
Beispiel 11 :Example 11:
P-ft-Methyl-prop-ζE/Zj-ylidenejS-oxo-cyclopentyll-essigsäuremethylester (Verbindung der Formel (Ia) mit R1 und R2 = Methy\)/cis/trans-[2-(2-Methyl- propenyl)-3-oxo-cyclopentyl]-essigsäuremethylester (Verbindung der Formel (Ib) mit R1 und R2 = Methyl): Wurde analog der allgemeinen Vorschrift zur Johnson- Claisen Umlagerung, ausgehend von 2-(1-Hydroxy-2-methyl-propyl)-cyclopent-2- enon, hergestellt. Man erhält ein E/Z Isomerengemisch von [2-(2-Methyl-prop- (E/Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester und c/s/ϊrans-[2-(Methyl- propenyl)-3-oxo-cyclopentyl]-essigsäuremethylester im Verhältnis 1 :1-2 bis . Das folgende GC gibt die Isomerenverhältnisse des durch Destillation gereinigten Produktes an: GC (DB-I):Methyl p-methyl-prop-1-ylidene-5-oxo-cyclopentylacetate (compound of the formula (Ia) in which R 1 and R 2 = methyl) / cis / trans- [2- (2-methyl-propenyl ) -3-oxo-cyclopentyl] -acetic acid methyl ester (compound of formula (Ib) with R 1 and R 2 = methyl): Was prepared analogously to the general procedure for Johnson-Claisen rearrangement, starting from 2- (1-hydroxy-2-methyl -propyl) -cyclopent-2-enone. An E / Z mixture of isomers of [2- (2-methyl-prop- (E / Z) -ylidene-3-oxocyclopentyl] -acetic acid methyl ester and c / s / trans [2- (methyl-propenyl) -] is obtained. Methyl 3-oxo-cyclopentyl] acetate in the ratio 1: 1-2 to The following GC indicates the isomer ratios of the product purified by distillation: GC (DB-I):
Index Area % VerbindungIndex Area% connection
1471 12.19 [2-(2-Methyl-prop-(Z)-ylidene)-3-oxo-cyclopentyl]- essigsäuremethylester1471 12.19 [2- (2-Methyl-prop- (Z) -ylidene) -3-oxo-cyclopentyl] -acetic acid methyl ester
1506 42.31 frans-[2-(2-Methyl-propenyl)-3-oxo-cyclopentyl]- essigsäuremethylester1506 42.31 frans- [2- (2-methyl-propenyl) -3-oxo-cyclopentyl] - acetic acid methyl ester
1516 33.27 [2-(2-Methyl-prop-(E)-ylidene)-3-oxo-cyclopentyl]- essigsäuremethylester1516 33.27 [2- (2-Methyl-prop- (E) -ylidene) -3-oxo-cyclopentyl] -acetic acid methyl ester
1523 8.99 c/s-[2-(2-Methyl-propenyl)-3-oxo-cyclopentyl]- essigsäuremethylester1523 8.99 c / s- [2- (2-Methyl-propenyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
Die 1H-NMR und 13C-NMR Spektren der beiden Hauptkomponenten trans-[2-(2- Methyl-propenyl)-3-oxo-cyclopentyl]-essigsäuremethylester und [2-(2-Methyl- prop-(E)-ylidene)-3-oxo-cyclopentyl]-essigsäuremethylester werden an dieser Stelle angegeben.The 1 H-NMR and 13 C-NMR spectra of the two main components trans- [2- (2-methyl-propenyl) -3-oxo-cyclopentyl] -acetic acid methyl ester and [2- (2-methyl-prop- (E) - ylidene) -3-oxo-cyclopentyl] -acetic acid methyl esters are given here.
frans-[2-(2-Methyl-propenyl)-3-oxo-cyclopentyl]-essigsäuremethylester:frans- [2- (2-methyl-propenyl) -3-oxo-cyclopentyl] -acetic acid methyl ester:
1H-NMR (400 MHz, CDCI3): δ (ppm) = 1.65 (d, J = 1.4 Hz, 3H), 1.78 (d, J = 1.4 Hz, 3H), 2.16-2.46 (m, 5H), 2.50-2.64 (m, 2H), 2.71 (ddd, J = 11.0, 9.0, 1.2 Hz, 1 H), 3.67 (s, 3H), 4.88 (dsep, J = 9.0, 1.4 Hz, 1 H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 1.65 (d, J = 1.4 Hz, 3H), 1.78 (d, J = 1.4 Hz, 3H), 2.16-2.46 (m, 5H), 2.50-2.64 (m, 2H), 2.71 (ddd, J = 11.0, 9.0, 1.2Hz, 1H), 3.67 (s, 3H), 4.88 (dsep, J = 9.0, 1.4Hz, 1H).
13C-NMR (100 MHz, CDCI3): 18.4 (q), 25.9 (q), 27.3 (t), 37.7 (t), 38.3 (t), 40.8 (d), 51.5 (q), 55.4 (d), 119.4 (d), 138.3 (s), 172.6 (s), 217.8 (s). 13 C-NMR (100 MHz, CDCl 3 ): 18.4 (q), 25.9 (q), 27.3 (t), 37.7 (t), 38.3 (t), 40.8 (d), 51.5 (q), 55.4 (i.e. ), 119.4 (d), 138.3 (s), 172.6 (s), 217.8 (s).
[2-(2-Methyl-prop-(E)-ylidene)-3-oxo-cyclopentyl]-essigsäuremethylester: 1H-NMR (400 MHz, CDCI3): δ (ppm) = 1.04 (d, J = 6.5 Hz, 3H), 1.05 (d, J = 6.5 Hz, 3H), 1.86 (dddd, J = 13.3, 8.6, 2.9, 1.8 Hz, 1H), 2.05 (dddd, J = 13.3, 11.3, 8.6, 7.5, Hz, 1 H), 2.16-2.46 (m, 5H), 3.43-3.50 (m, 1H), 3.71 (s, 3H), 6.39 (dd, J = 10.7, 1.9 Hz, 1H).[2- (2-methyl-prop- (E) -ylidene) -3-oxo-cyclopentyl] -acetic acid methyl ester: 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 1.04 (d, J = 6.5 Hz, 3H), 1.05 (d, J = 6.5 Hz, 3H), 1.86 (dddd, J = 13.3, 8.6 , 2.9, 1.8 Hz, 1H), 2.05 (dddd, J = 13.3, 11.3, 8.6, 7.5, Hz, 1H), 2.16-2.46 (m, 5H), 3.43-3.50 (m, 1H), 3.71 (s , 3H), 6.39 (dd, J = 10.7, 1.9 Hz, 1H).
13C-NMR (100 MHz, CDCI3): 22.1 (q), 22.2 (q), 25.2 (t), 28.7 (d), 34.8 (d), 35.7 (t), 39.1 (t), 51.7 (q), 137.3 (s), 144.2 (d), 172.3 (s), 206.9 (s). 13 C-NMR (100 MHz, CDCl 3 ): 22.1 (q), 22.2 (q), 25.2 (t), 28.7 (d), 34.8 (d), 35.7 (t), 39.1 (t), 51.7 (q ), 137.3 (s), 144.2 (d), 172.3 (s), 206.9 (s).
Geruch der Isomerenmischung: Jasminig, buttrigOdor of the isomer mixture: jasmine, buttery
Beispiel 12:Example 12:
ß-ß-Methyl-but-fE/Zj-ylidenj-S-oxo-cyclopentyll-essigsäuremethylester (Verbindung der Formel (Ia) mit R1 = H und R2 = iso-Propy\)/[2-((E/Z)-3-Methyl- but-1-enyl)-3-oxo-cyclopentyl]-essigsäuremethylester (Verbindung der Formel (Ib) mit R1 = H und R2 = /so-Propyl): Wurde analog der allgemeinen Vorschrift zur Johnson-Claisen Umlagerung, ausgehend von 2-(1 -Hydroxy-3-methyl-butyl)- cyclopent-2-enon, hergestellt. Man erhält ein E/Z Isomerengemisch von [2-(3- Methyl-but-(E/Z)-yliden)-3-oxo-cyclopentyl]-essigsäuremethylester und [2-((E/Z)- 3-Methyl-but-1-enyl)-3-oxo-cyclopentyl]-essigsäuremethylester im Verhältnis 5- 7:1. Das folgende GC gibt die Isomerenverhältnisse des durch Destillation gereinigten Produktes an:methyl β-β-methylbut-fE / Zi-ylidene-S-oxo-cyclopentylacetate (compound of the formula (Ia) where R 1 = H and R 2 = isopropyl) / [2 - ((E / Z) -3-Methyl-but-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester (compound of the formula (Ib) where R 1 = H and R 2 = / so-propyl): Was analogous to the general rule to Johnson-Claisen rearrangement prepared from 2- (1-hydroxy-3-methyl-butyl) cyclopent-2-enone. An E / Z isomer mixture of [2- (3-methylbut-1-yl) (E / Z) -ylidene) -3-oxo-cyclopentyl] -acetic acid methyl ester and [2 - ((E / Z) -methyl- but-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester in the ratio 5-7: 1. The following GC indicates the isomer ratios of the product purified by distillation:
GC (DB-I):GC (DB-I):
Index Area % VerbindungIndex Area% connection
1510 Z3Ϊ [2-((Z)-3-Methyl-but-1-enyl)-3-oxo-cyclopentyl]- essigsäuremethylester1510 Z3Ϊ [2 - ((Z) -3-methylbut-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1522 11.02 [2-((E)-3-Methyl-but-1 -enyl)-3-oxo-cyclopentyl]- essigsäuremethylester 1540 49.72 [2-(3-Methyl-but-(Z)-yliden)-3-oxo-cyclopentyl]- essigsäuremethylester1522 11.02 [2 - ((E) -3-Methylbut-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester 1540 49.72 [2- (3-Methylbut- (Z) -ylidene) -3-oxo-cyclopentyl] -acetic acid methyl ester
1575 34.34 [2-(3-Methyl-but-(E)-yliden)-3-oxo-cyclopentyl]- essigsäuremethylester1575 34.34 [2- (3-Methyl-but- (E) -ylidene) -3-oxo-cyclopentyl] - acetic acid methyl ester
Die 1H-NMR und 13C-NMR Spektren der beiden Hauptkomponenten [2-(3-Methyl- but-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester und [2-(3-Methyl-but-(E)- yliden-3-oxo-cyclopentyl]-essigsäuremethylester werden an dieser Stelle angegeben.The 1 H-NMR and 13 C-NMR spectra of the two main components [2- (3-methyl-but- (Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester and [2- (3-methyl-but- ( E) - ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester are given here.
[2-(3-Methyl-but-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester:[2- (3-methyl-but- (Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester:
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.90 (d, J = 6.7 Hz, 3H), 0.92 (d, J = 6.7 Hz, 3H), 1.53-1.63 (m, 1 H), 1.68 (sep, J = 6.7 Hz, 1 H), 2.25-2.51 (m, 5H), 2.53- 2.67 (m, 2H), 3.12-3.20 (m, 1H), 3.70 (s, 3H), 5.93 (td, J = 7.6, 2.3 Hz, 1 H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.90 (d, J = 6.7 Hz, 3H), 0.92 (d, J = 6.7 Hz, 3H), 1.53-1.63 (m, 1H) , 1.68 (sep, J = 6.7 Hz, 1H), 2.25-2.51 (m, 5H), 2.53-2.67 (m, 2H), 3.12-3.20 (m, 1H), 3.70 (s, 3H), 5.93 ( td, J = 7.6, 2.3 Hz, 1 H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 22.2 (q), 22.3 (q), 26.6 (t), 28.8 (d), 36.3 (t), 38.2 (t), 38.7 (d), 39.4 (t), 51.6 (q), 138.4 (s), 140.4 (d), 172.5 (s), 207.6 (s). 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 22.2 (q), 22.3 (q), 26.6 (t), 28.8 (d), 36.3 (t), 38.2 (t), 38.7 (i.e. ), 39.4 (t), 51.6 (q), 138.4 (s), 140.4 (d), 172.5 (s), 207.6 (s).
[2-(3-Methyl-but-(E)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester:[2- (3-methyl-but- (E) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester:
1H-NMR (400 MHz, CDCI3): δ (ppm) = 0.93 (d, J = 6.7 Hz, 3H), 0.96 (d, J = 6.7 Hz, 3H), 1.78 (sep, J = 6.7 Hz, 1 H), 1.87 (dddd, J = 13.3, 8.6, 3.1 , 1.7 Hz 1H), 2.03 (ddddd, J = 13.3, 11.3, 8.6, 7.7, 0.7 Hz, 1 H), 2.05-2.11 (m, 2H), 2.28-2.44 (m, 2H), 2.39 (dd, J = 15.5, 10.4 Hz, 1H), 2.47 (dd, J = 15.5, 4.6 Hz, 1 H), 3.39- 3.47 (m, 1H), 3.71 (s, 3H), 6.61 (ddd, J = 8.3, 7.2, 2.0 Hz, 1H). 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 0.93 (d, J = 6.7 Hz, 3H), 0.96 (d, J = 6.7 Hz, 3H), 1.78 (sep, J = 6.7 Hz, 1 H), 1.87 (dddd, J = 13.3, 8.6, 3.1, 1.7 Hz 1H), 2.03 (ddddd, J = 13.3, 11.3, 8.6, 7.7, 0.7 Hz, 1H), 2.05-2.11 (m, 2H) , 2.28-2.44 (m, 2H), 2.39 (dd, J = 15.5, 10.4 Hz, 1H), 2.47 (dd, J = 15.5, 4.6 Hz, 1H), 3.39- 3.47 (m, 1H), 3.71 ( s, 3H), 6.61 (ddd, J = 8.3, 7.2, 2.0 Hz, 1H).
13C-NMR (100 MHz, CDCI3): δ (ppm) = 22.3 (q), 22.7 (q), 25.2 (t), 28.3 (d), 34.9 (d), 35.7 (t), 38.1 (t), 38.4 (t), 51.7 (q), 137.2 (d), 140.4 (s), 172.3 (s), 206.3 (s). Geruch der Isomerenmischung: Jasminig, mit fruchtiger Bananennote. 13 C-NMR (100 MHz, CDCl 3 ): δ (ppm) = 22.3 (q), 22.7 (q), 25.2 (t), 28.3 (d), 34.9 (d), 35.7 (t), 38.1 (t ), 38.4 (t), 51.7 (q), 137.2 (d), 140.4 (s), 172.3 (s), 206.3 (s). Smell of the isomer mixture: Jasmine, with a fruity banana note.
C. Dekonjugation von Verbindungen gemäß Formel (Ia):C. Deconjugation of Compounds According to Formula (Ia):
Allgemeine Vorschrift zur Dekonjugation der [2-Alkyliden-3-oxo-cyclopentyl]- essigsäuremethylester der Formel (Ia) mit Kalium-fert-butanolat in DMF (vgl. die nachfolgenden Beispiele 13-14):General procedure for the deconjugation of [2-alkylidene-3-oxocyclopentyl] -acetic acid methyl esters of the formula (Ia) with potassium tert-butoxide in DMF (see Examples 13-14 below):
Zu einer auf 15°C abgekühlten Lösung aus Kalium-fert-butanolat (1.5 Moläquivalente) in DMF (1 ml/mmol Kalium-fert-butanolat), tropft man [2- Alkyliden-3-oxo-cyclopentyl]-essigsäuremethylester (1.0 Moläquivalente), gelöst in DMF (0.5 ml/mmol [2-Alkyliden-3-oxo-cyclopentyl]-essigsäuremethylester). Man lässt 4 Stunden bei Raumtemperatur rühren, bevor man auf 0°C abkühlt und 20%ige wässrige Essigsäure (0.35 ml/mmol [2-Alkyliden-3-oxo-cyclopentyl]- essigsäuremethylester) zügig zugibt. Nach 15-minütigem rühren gibt man etwas Wasser hinzu und extrahiert anschließend dreimal mit Ether. Die vereinigten organischen Phasen werden noch je 1x mit 10%iger NaHCO3-Lösung und Wasser gewaschen, über Na2SO4 getrocknet, abfiltriert und einrotiert. Das erhaltene Rohprodukt wird flashchromatographisch an Kieselgel gereinigt.To a cooled to 15 ° C solution of potassium tert-butoxide (1.5 molar equivalents) in DMF (1 ml / mmol potassium-but-butoxide-ready), is added dropwise [2-alkylidene-3-oxo-cyclopentyl] -acetic acid methyl ester (1.0 molar equivalents ) dissolved in DMF (0.5 ml / mmol [2-alkylidene-3-oxocyclopentyl] -acetic acid methyl ester). The mixture is stirred for 4 hours at room temperature, before cooling to 0 ° C and 20% aqueous acetic acid (0.35 ml / mmol [2-alkylidene-3-oxo-cyclopentyl] - acetic acid methyl ester) rapidly added. After stirring for 15 minutes, add a little water and then extract three times with ether. The combined organic phases are each washed once each with 10% NaHCO 3 solution and water, dried over Na 2 SO 4 , filtered off and concentrated by rotary evaporation. The crude product obtained is purified by flash chromatography on silica gel.
Beispiel 13:Example 13:
[2-Hex-(E/Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester (Verbindung der Formel (Ia) mit R1 = H und R2 = n-Buty\y[2-((E/Z)-Hex-1-enyl)-3-oxo-cyclopentyl]- essigsäuremethylester (Verbindung der Formel (Ib) mit R1 = H und R2 = n-Butyl):[2-Hex (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester (Compound of the formula (Ia) where R 1 = H and R 2 = n-butyl \ y [2 - ((E / Z ) -Hex-1-enyl) -3-oxo-cyclopentyl] - acetic acid methyl ester (compound of formula (Ib) with R 1 = H and R 2 = n-butyl):
Vorgehen gemäß der allgemeinen Vorschrift zur Dekonjugation. Ausgehend von einem ca. 5.0-6.0:1 Gemisch von [2-Hex-(E/Z)-yliden-3-oxo-cyclopentyl]- essigsäuremethylester und [2-((E/Z)-Hex-1 -enyl)-3-oxo-cyclopentyl]- essigsäuremethylester wurde isomerisiert. Man erhielt ein E/Z-Isomerengemisch von [2-Hex-(E/Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester und [2-((E/Z)- Hex-1-enyl)-3-oxo-cyclopentyl]-essigsäuremethylester im Verhältnis 1 :4-6. Das folgende GC gibt die Isomerenverhältnisse des durch Flashchromatographie (Cyclohexan/EtOAc = 10:1) gereinigten Produktes an:Procedure according to the general deconjugation procedure. Starting from a ca. 5.0-6.0: 1 mixture of [2-hex (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester and [2 - ((E / Z) -hex-1-enyl) 3-oxo-cyclopentyl] - acetic acid methyl ester was isomerized. An E / Z isomer mixture of [2-hex (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester and [2 - ((E / Z) -hex-1-enyl) -3- oxo-cyclopentyl] -acetic acid methyl ester in the ratio 1: 4-6. The the following GC indicates the isomer ratios of the product purified by flash chromatography (cyclohexane / EtOAc = 10: 1):
GC (DB-I):GC (DB-I):
Index Area % VerbindungIndex Area% connection
1694 7,88 [2-(Z)-Hex-1 -enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1694 7,88 [2- (Z) -hex-1-enyl-3-oxo-cyclopentyl] -acetic acid methyl ester
1712 70,77 [2-(E)-Hex-1 -enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1712 70,77 [2- (E) -hex-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1730 4,57 [2-Hex-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1730 4,57 [2-Hex- (Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
1768 13,27 [2-Hex-(E)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1768 13,27 [2-Hex- (E) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
Die 1H-NMR und 13C-NMR Spektren der Isomerenmischung entsprechen der Summe der Spektren der einzelnen Isomere aus Beispiel 7.The 1 H-NMR and 13 C-NMR spectra of the isomer mixture correspond to the sum of the spectra of the individual isomers from Example 7.
Geruch der Isomerenmischung: weiche Jasminnote mit lactonigen Aspekten.Odor of the isomer mixture: soft jasmine note with lactone aspects.
Beispiel 14:Example 14:
[2-Pent-(E/Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester (Verbindung der Formel (Ia) mit R1 = H und R2 = n-Propy\)/[2-((E/Z)-Pent-1-enyl)-3-oxo- cyclopentylj-essigsäuremethylester (Verbindung der Formel (Ib) mit R1 = H und R2 = n-Propyl):[2-Pent- (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester (compound of the formula (Ia) where R 1 = H and R 2 = n-propy) / [2 - ((E / Z) -pent-1-enyl) -3-oxo-cyclopentylj-acetic acid methyl ester (compound of the formula (Ib) where R 1 = H and R 2 = n-propyl):
Vorgehen gemäß der allgemeinen Vorschrift zur Dekonjugation. Ausgehend von einem ca. 5.0-6.0:1 Gemisch von [2-Pent-(E/Z)-yliden-3-oxo-cyclopentyl]- essigsäuremethylester und [2-((E/Z)-Pent-1-enyl)-3-oxo-cyclopentyl]- essigsäuremethylester wurde isomerisiert. Man erhielt ein E/Z-Isomerengemisch von [2-Pent-(E/Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester und [2-((E/Z)- Pent-1-enyl)-3-oxo-cyclopentyl]-essigsäuremethylester im Verhältnis 1 :5-6. Das folgende GC gibt die Isomerenverhältnisse des durch Flashchromatographie (Cyclohexan/EtOAc = 10:1) gereinigten Produktes an:Procedure according to the general deconjugation procedure. Starting from a ca. 5.0-6.0: 1 mixture of [2-pent (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester and [2 - ((E / Z) -pent-1-enyl) 3-oxo-cyclopentyl] - acetic acid methyl ester was isomerized. An E / Z isomer mixture was obtained of [2-pent (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester and [2 - ((E / Z) -pent-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester in proportion 1: 5-6. The following GC indicates the isomer ratios of the product purified by flash chromatography (cyclohexane / EtOAc = 10: 1):
Index Area % VerbindungIndex Area% connection
1602 6.45 [2-(Z)-Pent-1 -enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1602 6.45 [2- (Z) -pent-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1617 75.11 [2-(E)-Pent-1-enyl)-3-oxo-cyclopentyl]-essigsäuremethylester1617 75.11 [2- (E) -pent-1-enyl) -3-oxo-cyclopentyl] -acetic acid methyl ester
1637 3.25 [2-Pent-(Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1637 3.25 [2-Pent- (Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
1675 11.99 [2-Pent-(E)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester1675 11.99 [2-Pent- (E) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester
Die 1H-NMR und 13C-NMR Spektren der Isomerenmischung entsprechen den 1H- NMR und 13C-NMR Spektren der Isomerenmischung aus Beispiel 8, mit dem Unterschied, dass die Intensitäten verschoben sind.The 1 H-NMR and 13 C-NMR spectra of the isomer mixture correspond to the 1 H-NMR and 13 C-NMR spectra of the isomer mixture from Example 8, with the difference that the intensities are shifted.
Geruch der Isomerenmischung: weiche Jasminnote, mit schönen lactonigen Aspekten.Odor of the isomer mixture: soft jasmine note, with beautiful lactonigen aspects.
D. Parfümölkompositionen/Anwendungen:D. Perfume Oil Compositions / Applications:
Beispiel 15:Example 15:
Das nachfolgend angegebene Parfümöl kann zur Parfümierung diverser kosmetischer Produkte, insbesondere für Schaumbad und Shampoo verwendet werden. Zusammensetzung:The following perfume oil can be used for the perfuming of various cosmetic products, in particular for bubble bath and shampoo. Composition:
DPG = Dipropylenglycol; IPM = IsopropylmyristatDPG = dipropylene glycol; IPM = isopropyl myristate
Der Zusatz vonThe addition of
a) 55 Gewichtsteilen [2-Hex-(E/Z)-yliden-3-oxo-cyclopentyl]- essigsäuremethylester/[2-((E/Z)-Hex-1-enyl)-3-oxo-cyclopentyl]- essigsäuremethylester im Verhältnis - 5:1 führt zu einer deutlich wahrnehmbaren Harmonisierung der blumigen Herznote. Darüber hinaus verleiht die natürliche weiche Jasminnote der vorliegenden Komposition eine hervorragende Strahlung und gesteigerte Haftung. Hierbei setzt sich besonders der wertvolle Charakter von [2-Hex- (E/Z)-yliden-3-oxo-cyclopentyl]-essigsäuremethylester/[2-((E/Z)-Hex- 1-enyl)-3-oxo-cyclopentyl]-essigsäuremethylester im Verhältnis - 5:1 durch. a) 55 parts by weight of [2-hex (E / Z) -ylidene-3-oxocyclopentyl] -acetic acid methyl ester / [2 - ((E / Z) -hex-1-enyl) -3-oxocyclopentyl] - Acetic acid methyl ester in a ratio of 5: 1 leads to a clearly perceptible harmonization of the floral heart note. In addition, the natural soft jasmine note of the present composition gives excellent radiation and adhesion. Here, the valuable character of [2-hex- (E / Z) -ylidene-3-oxo-cyclopentyl] -acetic acid methyl ester / [2 - ((E / Z) -hex-1-enyl) -3-oxo is particularly important -cyclopentyl] -acetic acid methyl ester in the ratio - 5: 1 by.

Claims

Patentansprüche claims
1. Verwendung einer Verbindung der Formel (Ia) oder (Ib):1. Use of a compound of the formula (Ia) or (Ib):
wobei in jeder der Formeln (Ia) und (Ib)wherein in each of the formulas (Ia) and (Ib)
R1 H oder Methyl undR 1 is H or methyl and
R2 eine verzweigte oder unverzweigte d- bis C5-Alkylgruppe ist,R 2 is a branched or unbranched C 1 to C 5 alkyl group,
als Riechstoff.as a fragrance.
2. Verbindung der Formel (Ia) oder (Ib):2. Compound of the formula (Ia) or (Ib):
wobei in jeder der Formeln (Ia) und (Ib)wherein in each of the formulas (Ia) and (Ib)
R1 H oder Methyl undR 1 is H or methyl and
R2 eine verzweigte oder unverzweigte d- bis C5-Alkylgruppe ist, mit der Maßgabe, dass in Formel (Ia) nicht gleichzeitig R1 = H und R2 = n-Propyl ist.R 2 is a branched or unbranched C 1 to C 5 alkyl group, with the proviso that in formula (Ia) not simultaneously R 1 = H and R 2 = n-propyl.
3. Mischung umfassend zumindest jeweils eine Verbindung der Formel (Ia) und der Formel (Ib):3. Mixture comprising at least in each case a compound of the formula (Ia) and of the formula (Ib):
wobei in jeder der Formeln (Ia) und (Ib)wherein in each of the formulas (Ia) and (Ib)
R1 H oder Methyl undR 1 is H or methyl and
R2 eine verzweigte oder unverzweigte d- bis C5-Alkylgruppe ist undR 2 is a branched or unbranched C 1 to C 5 alkyl group and
wobei die Substituenten R1 und R2 in der Formel (Ia) die gleiche oder eine andere Bedeutung haben als in der Formel (Ib).wherein the substituents R 1 and R 2 in the formula (Ia) have the same or different meaning as in the formula (Ib).
4. Verwendung nach Anspruch 1 , Verbindung nach Anspruch 2 oder Mischung nach Anspruch 3, wobei4. Use according to claim 1, compound according to claim 2 or mixture according to claim 3, wherein
R1 H undR 1 H and
R2 Ethyl, n-Propyl, n-Pentyl oder n-Butyl ist.R 2 is ethyl, n-propyl, n-pentyl or n-butyl.
5. Riechstoffmischung mit Jasmingeruch, umfassend5. Fragrance mixture with jasmine smell, comprising
(i) eine sensorisch wirksame Menge einer Verbindung der Formel (Ia) oder (Ib) oder einer Mischung unterschiedlicher Verbindungen der Formel (Ia) oder (Ib) (i) a sensorially effective amount of a compound of the formula (Ia) or (Ib) or of a mixture of different compounds of the formula (Ia) or (Ib)
wobei in jeder der Formeln (Ia) und (Ib)wherein in each of the formulas (Ia) and (Ib)
R1 H oder Methyl undR 1 is H or methyl and
R2 eine verzweigte oder unverzweigte d- bis C5-Alkylgruppe istR 2 is a branched or unbranched C 1 to C 5 alkyl group
und wobei die Substituenten R1 und R2 in der Formel (Ia) die gleiche oder eine andere Bedeutung haben als in der Formel (Ib)and wherein the substituents R 1 and R 2 in the formula (Ia) have the same or different meaning than in the formula (Ib)
sowiesuch as
(ii) gegebenenfalls einen oder mehrere weitere übliche Bestandteile.(ii) optionally one or more other conventional ingredients.
6. Parfümiertes Produkt, umfassend6. Perfumed product comprising
- eine Riechstoffmischung nach Anspruch 5 sowie- A fragrance mixture according to claim 5 and
einen Träger oder ein Substrat, der bzw. das in direktem Kontakt mit der Riechstoffmischung steht.a support or substrate that is in direct contact with the perfume mixture.
7. Verfahren zur Herstellung einer Mischung nach Anspruch 3, mit folgenden Schritten:7. A process for the preparation of a mixture according to claim 3, comprising the following steps:
Bereitstellen eines Alkohols der Formel (VI) Providing an alcohol of the formula (VI)
und anschließendand subsequently
Johnson-Claisen 3.3-sigmatrope Umlagerung des Alkohols (VI) zu der Mischung.Johnson-Claisen 3.3-sigmatropic rearrangement of the alcohol (VI) to the mixture.
8. Verfahren zum Erzeugen, Verstärken oder Modifizieren eines Jasmingeruchs in einer Mischung, mit folgenden Schritten8. A method of producing, enhancing or modifying a jasmine odor in a mixture, comprising the steps of
Bereitstellen einer Verbindung nach Anspruch 2 oder einer Mischung nach Anspruch 3,Providing a compound according to claim 2 or a mixture according to claim 3,
Bereitstellen einer Komposition sonstiger Bestandteile undProviding a composition of other ingredients and
- Vermischen der Komposition sonstiger Bestandteile mit einer Menge der Verbindung oder der Mischung, die ausreicht, (a) in der resultierenden Gesamtmischung einen Jasmingeruch zu erzeugen, (b) einen vorhandenen Jasmingeruch in der Komposition sonstiger Bestandteile zu verstärken oder (c) einen vorhandenen Jasmingeruch in der Komposition sonstiger Bestandteile zu modifizieren.Mixing the composition of other ingredients with an amount of the compound or mixture sufficient to (a) produce a jasmine smell in the resulting total mixture, (b) to fortify an existing jasmine smell in the composition of other ingredients, or (c) an existing jasmine smell to modify in the composition of other components.
9. Verfahren zur Herstellung einer Verbindung in der Formel (Ib)9. Process for the preparation of a compound in the formula (Ib)
lgendem Schritt: a step:
Isomerisieren einer Verbindung der Formel (Ia)Isomerizing a compound of the formula (Ia)
oder einer Mischung der Verbindungen der Formeln (Ia) und (Ib),or a mixture of the compounds of the formulas (Ia) and (Ib),
wobei in jeder der Formeln (Ib) und (Ib)wherein in each of the formulas (Ib) and (Ib)
R1 H oder Methyl undR 1 is H or methyl and
R2 eine verzweigte oder unverzweigte d- bis C5-Alkylgruppe ist,R 2 is a branched or unbranched C 1 to C 5 alkyl group,
in Gegenwart einer Alkoholat-Base in einem polaren aprotischen oder polaren protischen Lösungsmittel. in the presence of an alkoxide base in a polar aprotic or polar protic solvent.
EP05784683A 2004-09-14 2005-09-13 2-alkylidene- and 2-(alkyl-1-ene)-cyclopentanone as perfumes Withdrawn EP1791804A1 (en)

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KR102072378B1 (en) * 2018-09-12 2020-02-03 부산대학교 산학협력단 New compounds having PPAR-γ activity, and medical use thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL179368C (en) * 1976-07-16 1986-09-01 Roure Bertrand Dupont Sa PROCESS FOR PREPARING OXOCYCLOPENTYL AND OXOCYCLOHEXYL COMPOUNDS.
DE3673071D1 (en) * 1985-05-31 1990-09-06 Givaudan & Cie Sa CYCLOPENTE DERIVATIVES AND THEIR USE AS A FRAGRANCE.
US5667995A (en) * 1994-12-12 1997-09-16 Firmenich Sa Process for the preparation of cyclic ketones
EP1562888A1 (en) * 2002-11-11 2005-08-17 Firmenich Sa A process for the preparation of alkylidenecyclopentanone derivatives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006030010A1 *

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