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
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
  • C07C47/277—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
  • C07C49/175—Saturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
  • C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/003—Esters of saturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/56—Crotonic acid esters; Vinyl acetic acid esters
• • 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
  • C07C69/67—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 saturated acids
  • C07C69/675—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 saturated acids of saturated hydroxy-carboxylic acids
• • 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
  • C07C69/67—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 saturated acids
  • C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0007—Aliphatic compounds
  • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
  • C11B9/0019—Aliphatic compounds containing oxygen as the only heteroatom carbocylic acids; Salts or esters thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

• This invention relates to novel compounds having musk characteristics, their manufacture and their use in fragrance compositions.
• Helvetolide ® (4-(3,3- dimethyl-1-cyclohexyl)-2,2-dimethyl-3-oxapentyl propionate, trademark of Firmenich SA, Switzerland).
• the present invention refers in a first aspect to a compound of formula I
• R 1 and R 3 are independently hydrogen, methyl, or ethyl
• R 2 is hydrogen, methyl, ethyl, methylene, or ethylidene
• R 4 is Ci to C 4 alkyl, for example methyl, ethyl, /-propyl, n-propyl, cyclopropyl, sec- butyl, n-butyl, te/f-butyl, or cyclobutyl; or
• 30075 PCT 19.11.2003 CS R 4 is vinyl or a linear, branched or cyclic C 3 to C 4 alkenyl, for example propen-1-yl, propen-2-yl, prop-2-en-1-yl, cyclobut-1-en-1-yl, butenyl, e.g.
• X is carbonyl or a divalent radical -(CMe 2 )- ;
• Y is oxygen or a divalent radical -(CH 2 )- ;
• the bond between C-2 and R 2 is a single bond, and the bond between C-2 and C-3 together with the dotted line represents a double bond; or the bond between C-2 and C-3 is a single bond, and the bond between C-2 and R 2 together with the dotted line represents a double bond; or the bond between C-2 and R 2 is a single bond and the bond between C-2 and C-3 is a single bond.
• the compounds according to the present invention comprise one or more chiral centres and as such may exist as a mixture of stereoisomers, or they may be resolved as isomerically pure forms. Resolving stereoisomers adds to the complexity of manufacture and purification of these compounds and so it is preferred to use the compounds as mixtures of their stereoisomers simply for economic reasons. However, if it is desired to prepare individual stereoisomers, this may be achieved according to methodology known in the art, e.g. preparative HPLC and GC or by stereoselective syntheses.
• Preferred compounds are unsaturated aliphatic carbonyl compounds of formula I, i.e. compounds of formula I wherein the bond between C-2 and R 2 is a single bond, and the bond between C-2 and C-3 together with the dotted line represents a double bond; or the bond between C-2 and C-3 is a single bond, and the bond between C-2 and R 2 together with the dotted line represents a double bond, e.g.
• R 1 and R 2 are independently hydrogen or methyl
• R 4 is Ci to C alkyl, for example methyl, ethyl, / ' -propyl, n-propyl, cyclopropyl, sec- butyl, n-butyl, -erf-butyl, or cyclobutyl; or R 4 is vinyl or a linear, branched or cyclic C 3 to C alkenyl, for example propen-1-yl, propen-2-yl, prop-2-en-1-yl, cycloprop-1-en-1-yl, cycloprop-2-en-1-yl, cyclobut-2-en-1- yl, butenyl, e.g. but-1-en-1-yl, or butadiene.
• the present invention refers in a further aspect to compound of formula I wherein the bond between C-2 and R 2 is a single bond, and C-2 and C-3 together with the dotted line represents a double bond, enriched in one of the double bond isomers, i.e. (E)- or (Z)-configurated double bond.
• enriched is used herein for a compound having an isomeric purity of over 1:1 in favour of the selected double bond isomer.
• Compounds are preferred having a purity of about 55:45 or greater, e.g. about 70:30.
• the compounds according to the present invention may be used alone or in combination with known odourant molecules selected from the extensive range of natural and synthetic molecules currently available, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and/or in admixture with one or more ingredients or excipients conventionally used in conjunction with odourants in fragrance compositions, for example carrier materials, and other auxiliary agents commonly used in the art.
• oils and extracts e.g. castoreum, costus root oil, oak moss absolute, geranium oil, jasmine absolute, patchouli oil, rose oil, sandalwood oil or ylang-ylang oil;
• alkohols e.g. citronellol, EbanolTM, eugenol, geraniol, Super MuguetTM, linalool, phenylethyl alcohol, SandaloreTM, terpineol or TimberolTM.
• ketones e.g. ⁇ -amylcinnamaldehyde, GeorgywoodTM, hydroxycitronellal, Iso E Super ® , Isoraldeine ® , Hedione ® , maltol, methyl cedryl ketone, methylionone or vanillin;
• esters and lactones e.g. benzyl acetate, cedryl actetate, ⁇ -decalactone, Helvetolide 18 ⁇ -undecalactone or vetivenyl acetate.
• heterocycles e.g. isobutylchinoline.
• the compounds of formula I are especially well suited for use in fresh musky accords, woody-spicy or floral-hesperidic compositions as is more specifically illustrated in the Example.
• the compounds of the present invention may be used in a broad range of fragrance applications, e.g. in any field of fine and functional perfumery, such as perfumes, household products, laundry products, body care products and cosmetics.
• the compounds can be employed in wide ranging amounts depending upon the specific application and on the nature and quantity of other odourant ingredients that may be, for example, from about 0.001 to about 20 weight percent.
• compounds of the present invention may be employed in a fabric softener in an amount of about 0.001 to 0.05 weight percent.
• compounds of the present invention may be used in an alcoholic solution in amounts of about 0.1 to 20 weight percent, more preferably between about 0.1 and 5 weight percent.
• these values should not be limiting on the present invention, since the experienced perfumer may also achieve effects or may create novel accords with lower or higher concentrations.
• the compounds of the present invention may be employed into the fragrance application simply by direct mixing the fragrance composition with the fragrance application, or they may, in an earlier step be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, precursors, film formers, absorbents such as for example by using carbon or zeolites, cyclic oligosaccharides and mixtures thereof, or they may be chemically bound to substrates which are adapted to release the fragrance molecule upon application of an exogenous stimulus such as light, enzyme, or the like, and then mixed with the application.
• an entrapment material for example, polymers, capsules, microcapsules and nanocapsules, liposomes, precursors, film formers, absorbents such as for example by using carbon or zeolites, cyclic oligosaccharides and mixtures thereof, or they may be chemically bound to substrates which are adapted to release the fragrance molecule upon application of an exogenous stimulus such as light
• the invention additionally provides a method of manufacturing a fragrance application, comprising the incorporation of a compound of formula I as a fragrance ingredient, either by directly admixing the compound of formula I to the application or by admixing a fragrance composition comprising a compound of formula I, which may then be mixed to a fragrance application, using conventional techniques and methods.
• fragment application means any product, such as fine perfumery, e.g. perfume and Eau de Toilette; household products, e.g. detergents for dishwasher, surface cleaner; laundry products, e.g. softener, bleach, detergent; body care products, e.g. shampoo, shower gel; and cosmetics, e.g. deodorant, vanishing creme, comprising an odourant.
• fine perfumery e.g. perfume and Eau de Toilette
• household products e.g. detergents for dishwasher, surface cleaner
• laundry products e.g. softener, bleach, detergent
• body care products e.g. shampoo, shower gel
• cosmetics e.g. deodorant, vanishing creme
• Compounds of formula I wherein X is carbonyl and Y is a divalent radical -(CH 2 )-, i.e. oxo esters, may be prepared by esterification of an appropriately substituted allylic alcohol with an appropriately substituted oxo carboxylic acid, e.g. laevulinic acid.
• Compounds of formula I wherein X is a divalent radical -(CMe 2 )- and Y is a divalent radical -(CH 2 )-, i.e. oxa ketones, may be prepared by etherification of an appropriately substituted allylic alcohol with isobutylene oxide, subsequent oxidation to the aldehyde, followed by Wittig-Horner-Emmons reaction under conditions known to the skilled person and selective hydrogenation of the formed double bond. The resulting compounds may be further hydrogenated in a known manner to give further compounds of formula I.
• the aforementioned substituted allylic alcohol starting material is accessible by reduction of an aldol-condensation product, as known in the art.
• Example 1 (2"E/Z. Acetic acid 2 , -methyl-2'-(1".2”.4"-trimethylnent-2"-enyloxy.Dropyl ester
• Odour description musky, sweet, fruity, floral.
• Odour description intense musky, slightly floral, fruity, rosy.
• Odour description intense musky, fruity-floral undertones, sweet.
• Odour description strong musky with fruit-green nuances, floral.
• Odour description musky, sweet, green, fruity.
• Example 10 .2'E/Z.-6-Methyl-6-.1'.2'.4'-trimethylpent-2'-enyloxy.heptan-3-one
• reaction mixture was stirred at room temp, for 1 d, with a further portion of PCC (4.30 g, 20.0 mmol) being added after the first 5 h, and then filtered by suction over a pad of Celite ® .
• Odour description musky, sweet, green, grapefruit.
• Odour description musky, sweet, fruity, powdery, anisic.
• Example 15 .2'E.-4-Oxopentanoic acid 1'.4'.4'-trimethylpent-2'-enyl ester
• Odour description fresh, musky, slightly metallic, pear, ambrette seed oil.
• Linalool synthetic 30.00 16. [1-Methyl-2-(1 ,2,2-trimethylbicyclo[3.1.0]hex- 3-ylmethyl)cyclopropyl]methanol (JavanolTM) 1.00
• the (2"E/Z)-cyclopropanecarboxylic acid 2'-methyl-2'-(1 ",2",4"-trimethylpent-2"-enyl- oxy)propyl ester conveys to this fragrance a very pleasant, sensual musk tonality. It adds volume, sweetness and warmth to the composition. In addition it provides fixative properties to the fragrance; yet, the musk characteristics are present from the top note impressions till the dry down of this perfume.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (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)

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• 2003
  • 2003-11-24 AU AU2003280275A patent/AU2003280275A1/en not_active Abandoned
  • 2003-11-24 MX MXPA05005487A patent/MXPA05005487A/es active IP Right Grant
  • 2003-11-24 JP JP2004570666A patent/JP4518957B2/ja not_active Expired - Lifetime
  • 2003-11-24 ES ES03770840T patent/ES2274282T3/es not_active Expired - Lifetime
  • 2003-11-24 US US10/535,974 patent/US7384906B2/en not_active Expired - Lifetime
  • 2003-11-24 DE DE60309200T patent/DE60309200T2/de not_active Expired - Lifetime
  • 2003-11-24 AT AT03770840T patent/ATE342880T1/de not_active IP Right Cessation
  • 2003-11-24 WO PCT/CH2003/000773 patent/WO2004050595A1/en not_active Ceased
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