Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C33/05—Alcohols containing rings other than six-membered aromatic rings
  • C07C33/12—Alcohols containing rings other than six-membered aromatic rings containing five-membered rings
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/20—Synthetic spices, flavouring agents or condiments
  • A23L27/203—Alicyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
  • C07C49/537—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings to a five-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
  • C07C49/557—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings having unsaturation outside the rings
• • 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
  • 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
  • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
  • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
  • C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms
• • 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
  • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated

Definitions

• the present invention refers to a novel class of campholitic aldehyde derivatives and their use as odorants. This invention furthermore relates to a method of their production and to flavour and fragrance compositions comprising them.
• the present invention refers in one of its aspects to the use as flavour or fragrance of a compound of formula (I)
• R 4 is hydrogen and the bond between C-3 and C-4 is a single bond or the dotted line together with the bond between C-3 and C-4 represents a double bond; or R 4 is methylene, forming with C-3 and C-4 a cyclopropane ring;
• R 3 is hydrogen, C 1 , C 2 , C 3 , C 4 , C 5 , C 6 alkyl (e.g. methyl, ethyl, isobutyl), or C 2 , C 3 , C 4 , C 5 , C 6 alkenyl (e.g. vinyl, propenyl, 3-butenyl); and I) R 1 and R 2 together with the carbon atom to which they are attached form a carbonyl group; or
• R 1 is hydroxyl and R 2 is selected from C 1 , C 2 , C 3 alkyl (e.g. methyl, ethyl, n-propyl, isopropyl), and C 2 , C 3 , C 4 alkenyl (e.g. vinyl, isopropenyl, 4-pentenyl).
• the compounds of formula (I) may comprise several 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.
• stereoisomers it is desired to prepare individual stereoisomers, this may be achieved according to methods known in the art, e.g. preparative HPLC and GC, crystallization or by departing from chiral starting materials, e.g. starting from enantiomerically pure or enriched raw materials such as terpenoids, and/or by applying stereoselective synthesis.
• methods known in the art e.g. preparative HPLC and GC, crystallization or by departing from chiral starting materials, e.g. starting from enantiomerically pure or enriched raw materials such as terpenoids, and/or by applying stereoselective synthesis.
• Non-limiting examples are compounds of formula (I) wherein R 4 is hydrogen and the dotted line together with the bond between C-3 and C-4 represents a double bond.
• the compounds according to the present invention may be used alone or in combination with known fragrances selected from the extensive range of natural and synthetic molecules currently available, such as essential oils and extracts, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles.
• the compounds of formula (I) may be admixed with one or more ingredients or excipients conventionally used in conjunction with fragrances in fragrance adjations, for example, carrier materials, and other auxiliary agents, such as solvents (e.g. dipropyleneglycol (DPG), isopropylmyristate (IPM), triethylcitrate (TEC) and alcohol (e.g. ethanol)), commonly used in the art.
• solvents e.g. dipropyleneglycol (DPG), isopropylmyristate (IPM), triethylcitrate (TEC) and alcohol (e.g. ethanol)
• solvents e.g. dipropyleneglycol (DPG), isopropylmyristate (IPM), triethylcitrate (TEC) and alcohol (e.g. ethanol)
• solvents e.g. dipropyleneglycol (DPG), isopropylmyristate (IPM), trieth
• - essential oils and extracts e.g. oak moss absolute, basil oil, tropical fruit oils, such as bergamot oil and mandarin oil, mastic absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, wormwood oil, lavender oil, rose oil, jasmin oil, ylang- ylang oil and sandalwood oil.
• aldehydes and ketones e.g. citral, hydroxycitronellal, Lilial ® (3-(4-tert-butylphenyl)-2- methylpropanal), methylnonylacetaldehyde, anisaldehyde, allylionone, verbenone, nootkatone, geranylacetone, ⁇ -amylcinnamic aldehyde, GeorgywoodTM (1 -(1 ,2,8,8- tetramethyl-1 ,2,3,4,5,6,7,8-octahydronaphthalen-2-y!ethanone), hydroxycitronellal, lso E Super ® (1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2- yl)ethanone), Isoraldeine ® (4-(2,6,6-trimethyl-2-cyclohexenyl)-3-methyl-3-buten-2- one
• esters and lactones e.g. benzyl acetate, cedryl actetate, ⁇ -decalactone, Helvetolide ® (2-[1-(3,3-dimethylcyclohexyl)ethoxy]-2-methylpropan-1-ol propanoate), ⁇ - undecalactone, vetivenyl acetate, cinnamyl propionate, citronellyl acetate, decyl acetate, dimethylbenzylcarbinyl acetate, ethyl acetoacetate, ethyl acetylacetate, cis- 3-hexenyl isobutyrate, linalyl acetate and geranyl acetate.
• benzyl acetate cedryl actetate
• ⁇ -decalactone Helvetolide ® (2-[1-(3,3-dimethylcyclohexyl)ethoxy]-2-methylpropan-1-o
• - macrocycles e.g. Ambrettolide, Ethylene brassylate or Exaltolide ® (oxacyclohexadecan-2-one).
• heterocycles e.g. isobutylchinoline.
• the compounds of the present invention may be used in a broad range of fragranced 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 of formula (I) can be employed in widely varying amounts, depending upon the specific application and on the nature of the composition or application one intends to fragrance, for example the nature and quantity of co-ingredients, and the particular effect that the perfumer seeks.
• the proportion is typically from 0.001 to 20 weight percent of the application.
• compounds of the present invention may be employed in a fabric softener in an amount of from 0.001 to 0.05 weight percent.
• compounds of the present invention may be used in an alcoholic solution in amounts of from 0.1 to 30 weight percent, more preferably between 1 and 20 weight percent.
• these values are given only by way of example, since the experienced perfumer may also achieve effects or may create novel accords with lower or higher concentrations, e.g. up to about 50 weight percent based on the composition.
• the compounds of the present invention may be employed into a consumer product base by mixing a compound of formula (I), a mixture thereof or fragrance composition comprising it, with the consumer product base, and/or they may, in an earlier step, be entrapped with an entrapment material such as polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and/or they may be chemically bonded to substrates, which together with the substrate forms a precursor, which are adapted to release the compound of formula (I) upon application of an external stimulus such as light, enzyme, or the like, and then mixed with the consumer product base.
• an entrapment material such as polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and/or they may be chemically bonded to
• the invention additionally provides a method of manufacturing a fragrance application comprising the incorporation of a compound of formula (I) as fragrance ingredient, either by admixing the compound to the consumer product base or by admixing a composition comprising a compound of formula (I) or a precursor thereof, which may then be mixed to the consumer product base, using conventional techniques and methods.
• a method of manufacturing a fragrance application comprising the incorporation of a compound of formula (I) as fragrance ingredient, either by admixing the compound to the consumer product base or by admixing a composition comprising a compound of formula (I) or a precursor thereof, which may then be mixed to the consumer product base, using conventional techniques and methods.
• an organoleptically acceptable amount of a compound of formula (I) or a mixture thereof the organoleptic properties of the consumer product base will be improved, enhanced or modified.
• precursors is meant, in particular, reaction products of the aldehydes / ketones of formula (I), i.e. compounds of formula (I) wherein R 1 and R 2 together with the carbon atom to which they are attached form a carbonyl group, with a compound comprising at least one functional group selected from the group of primary amine, secondary amine, sulfhydryl (thiol), hydroxy! and carboxyl, in which a covalent bond is formed between at least one carbon atom of the compound of formula (I) and at least one of the hetero atoms of said compounds comprising at least one functional group selected from the group of N, S and O.
• the invention furthermore provides a method for improving, enhancing or modifying a consumer product base by means of the addition thereto of an olfactorily acceptable amount of a compound of formula (I), or a mixture thereof.
• the invention also provides a fragrance application comprising: a) as fragrance a compound of formula (I) or a mixture thereof; and b) a consumer product base.
• consumer product base is meant a formulation for use as a consumer product to fulfill specific actions, such as cleaning, softening, and caring or the like.
• examples of such products include fine perfumery, e.g. perfume and eau de toilette; fabric care, household products and personal care products such as laundry care detergents, rinse conditioner, personal cleansing products, detergent for dishwasher, surface cleaner; laundry products, e.g. softener, bleach, detergent; body care products, e.g. shampoo, shower gel; air care products and cosmetics, e.g. deodorant, and vanishing creme.
• fine perfumery e.g. perfume and eau de toilette
• fabric care, household products and personal care products such as laundry care detergents, rinse conditioner, personal cleansing products, detergent for dishwasher, surface cleaner
• laundry products e.g. softener, bleach, detergent
• body care products e.g. shampoo, shower gel
• air care products and cosmetics e.g. deodorant, and vanishing creme.
• R 4 is hydrogen and the bond between C-3 and C-4 is a single bond or the dotted line together with the bond between C-3 and C-4 represents a double bond; or R 4 is methylene, forming with C-3 and C-4 a cyclopropane ring;
• R 3 is hydrogen, C 1 , C 2 , C 3 , C 4 , C 5 , C 6 alkyl (e.g. methyl, ethyl, isobutyl), or C 2 , C 3 , C 4 , C 5 , C 6 alkenyl (e.g.
• R 1 and R 2 together with the carbon atom to which they are attached form a carbonyl group; or II) R 1 is hydroxyl and R 2 is selected from C 1 , C 2 , C 3 alkyl (methyl, ethyl, n-propyl, isopropyl), and C 2 , C 3 , C 4 alkenyl (e.g. vinyl, isopropenyl, 4-pentenyl); with the proviso that 2,2,3-trimethyl-cyclopent-3-enecarbaldehyde, 2,2,3- trimethylcyclopentanecarbaldehyde.and 1-(2,2,3-trimethylcyclopent-3-enyl)ethanol are excluded.
• the compounds of formula (I) may be prepared starting from the commercially-available ⁇ -campholenic aldehyde of any enantiomeric ratio (pure (R) or (S) or any mixture of both enantiomers, e.g. from about 9:1 to about 1 :9 (R/S)) via the corresponding quality of its lower homologue, ⁇ -campholytic aldehyde, described in the literature by Ch. Chapuis et al., Helvetica Chimica Acta 2006, 89, 2638-2653. The latter may be converted by reaction with Grignard reagents to the corresponding secondary alcohols, which in turn can be oxidised with pyridinium chlorochromate to the corresponding ketones.
• ⁇ -campholytic aldehyde can be hydrogenated, e.g. under palladium on-carbon catalysis, to obtain the corresponding saturated derivative, 2,2,3-trimethyl-cyclopentanecarbaldehyde, which can be submitted to the reaction described above in order to produce the corresponding saturated secondary or tertiary alcohols or the ketones.
• cyclopropanate a- campholytic aldehyde or an alcohol derived therefrom see above
• submit the product to the transformation described previously (i.e. Grignard reagent addition and oxidation of alcohols to the corresponding ketones) under conditions known to the person skilled in the art.
• Campholytic alcohol is obtainable from ⁇ -campholytic aldehyde, e.g. via sodium borohydride reduction.
• a solution of ⁇ -campholytic aldehyde (10 g, 72 mmol, 20.6% ee (R)) in 11 mL THF is added drop-wise into a cooled, mechanically stirred solution of ethylmagnesium bromide (40 mL, 87 mmol, 2.2 M in THF) at a rate allowing the mixture temperature to be kept between -10 0 C and 0 °C (ca. 20 min).
• the resulting solution is stirred for 2h while the temperature is allowed to warm to 0 0 C.
• the resulting heterogeneous mixture is quenched with 100 mL of 2M HCI.
• aqueous layer is extracted with MTBE and the combined organic layers are dried over MgSO 4 , then evaporated yielding 11.9 g of a yellow liquid (98 % yield).
• This material can be purified by distillation or chromatography, but was used directly in the next step.
• Odour description very natural, agrestic, patchouli, a bit earthy/mossy, fruity (fenchyl acetate-type), slightly green.
• Odour description earthy, slightly woody, fruity, agrestic, camphoraceous; +4h: earthy, humus, green; +24h: earthy, green, watery, mossy
• Odour description agrestic, camphoraceous, balsamic, fruity, pine.
• Example 2 Following the general procedure according to Example 1 , Example 2 or Example 3 the following compound was prepared from 2,2,3-trimethylcyclopentancarbaldehyde (dihydro-campholyte aldehyde).
• Odour description fruity apple, sparkling, interesting; +4h: fruity, like agrumex, herbaceous; +24h: weak, fruity apple, agrestic (agrumex).
• Odour description fruity, agrestic, floral; +4h: fruity, slightly agrestic, piney, floral; +24h: fruity, slightly agrestic, spicy, floral.
• Odour description Very natural, agrestic, patchouli, a bit earthy/mossy, fruity (fenchyl acetate-type), slightly green.
• Example 9 1-((3S)-1.2.2-trimethylbicvcloF3.1.0lhex-3-yl)ethanol; ca. 20%ee
• a drop of acetyl bromide (1 drop) was added to a mixture of activated (with 1 N HCI) zinc (19.6 g, 0.3 mol), cuprous bromide (1.5 g, 0.01 mol) and 1-((1S)-2,2,3- trimethylcyclopent-3-enyl)ethanol (ca. 20%ee, 15.4 g, 0.3 mol) in diethyl ether (50 ml). After 10 minutes stirring, dibromomethane (52.0 g, 0.3 mol) was added and stirring at reflux continued for 6 h.
• Odour description agrestic, minty, camphoraceous, woody, slightly patchouli.
• Example 10 Fouqere aromatic qreen-fruitv composition for a shower gel
• Labienoxime (2,4,4,7-tetramethyl-6,8-nonadiene-3-one-oxime) at 1% in IPM-TEC (isopropylmyristate - triethylcitrate mixture 90/10) 2 Linalool 160 Maltol isobutyrate at 10% in DPG 4
• This fougere fragrance with a spearmint leaf effect and fruity green undertones in the direction of apple provides a green-aromatic freshness to shower gel formulations, which is greatly enhanced by the patchouli character of 1-(2,2,3-trimethylcyclopent-3- en-1-yl)ethanol.
• Incorporation of this new odorant conveys a natural resinous-woody, balsamic character that enhances the fresh-aromatic theme of the composition without dominating the fragrance with its patchouli note.
• 1-(2,2,3-trimethylcyclopent-3-en-1- yl)ethanol also stresses the fresh eucalyptus and spearmint effect, but most importantly renders it the construction of a fougere theme possible without incorporation of oak moss. Without the woody-camphoraceous-earthy patchouli scent of 1 -(2,2,3- trimethylcyclopent-3-en-1-yl)ethanol with its slightly spicy accents and fruity-green facets that idea.
• Example 11 Fougere aromatic lavender composition for a masculine eau-de-coloqne
• AIIyI amyl glycolate 6 Ambrofix (dodecahydro-3a,6,6,9a-tetramethyl-naphtho-(2,1-b)-furan) 20 Anise oil 2
• Cyclohexal 80 Damascenone (1-(2,6,6-trimethylcyclohexa-1 ,3-dienyl)but-2-en-1-one) at 10% in dipropyleneglycol (DPG) 4
• Fennaldehyde (3-(4-methoxyphenyl)-2-methylpropanal) 10
• Fixolide (1-(3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)- ethanone) 120
• This composition presents a fresh cologne character with a particular emphasis on a true natural lavender effect.
• the lavender is blended with a rich woody ambery and powdery background, while the heart is a soft floral with watery connotations.
• 1-(2,2,3- trimethylcyclopent-3-enyl)prop-2-en-1-ol brings an agrestic patchouli character to the composition. It enhances also the crisp and natural feeling while improving the lift and freshness.

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• Chemical & Material Sciences (AREA)
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• Food Science & Technology (AREA)
• Polymers & Plastics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Fats And Perfumes (AREA)
• Cosmetics (AREA)
• Detergent Compositions (AREA)

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