EP1791804A1 - 2-alkylidene-cyclopentanones et 2-(alkyl-1-ene)-cyclopentanones comme parfums - Google Patents

2-alkylidene-cyclopentanones et 2-(alkyl-1-ene)-cyclopentanones comme parfums

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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
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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Withdrawn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
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German (de)
English (en)
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
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Symrise AG
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Publication date
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Publication of EP1791804A1 publication Critical patent/EP1791804A1/fr
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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne l'utilisation, comme parfum jasmin, d'un composé de formules (Ia) ou (Ib) dans lesquelles R1 représente H ou méthyle et R2 représente un groupe alkyle C1 à C5 ramifié ou linéaire.
EP05784683A 2004-09-14 2005-09-13 2-alkylidene-cyclopentanones et 2-(alkyl-1-ene)-cyclopentanones comme parfums Withdrawn EP1791804A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004044250A DE102004044250A1 (de) 2004-09-14 2004-09-14 2-Alkyliden- und 2-(Alkyl-1-en)-cyclopentanone als Riechstoffe
PCT/EP2005/054551 WO2006030010A1 (fr) 2004-09-14 2005-09-13 2-alkylidene-cyclopentanones et 2-(alkyl-1-ene)-cyclopentanones comme parfums

Publications (1)

Publication Number Publication Date
EP1791804A1 true EP1791804A1 (fr) 2007-06-06

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EP05784683A Withdrawn EP1791804A1 (fr) 2004-09-14 2005-09-13 2-alkylidene-cyclopentanones et 2-(alkyl-1-ene)-cyclopentanones comme parfums

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EP (1) EP1791804A1 (fr)
DE (1) DE102004044250A1 (fr)
WO (1) WO2006030010A1 (fr)

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KR102072378B1 (ko) * 2018-09-12 2020-02-03 부산대학교 산학협력단 PPAR-γ 활성을 갖는 신규 화합물 및 이의 의학적 용도

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Publication number Priority date Publication date Assignee Title
NL179368C (nl) * 1976-07-16 1986-09-01 Roure Bertrand Dupont Sa Werkwijze voor het bereiden van oxocyclopentyl- en oxocyclohexylverbindingen.
DE3673071D1 (de) * 1985-05-31 1990-09-06 Givaudan & Cie Sa Cyclopentenderivate und ihre anwendung als riechstoffe.
US5667995A (en) * 1994-12-12 1997-09-16 Firmenich Sa Process for the preparation of cyclic ketones
WO2004043895A1 (fr) * 2002-11-11 2004-05-27 Firmenich Sa Procédé de preparation de dérivés d'alkylidènecyclopentanone

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Title
See references of WO2006030010A1 *

Also Published As

Publication number Publication date
WO2006030010A1 (fr) 2006-03-23
DE102004044250A1 (de) 2006-03-16

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