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
  • C11B9/0038—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing more than six carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/13—Monohydroxylic alcohols containing saturated rings
  • C07C31/133—Monohydroxylic alcohols containing saturated rings monocyclic
• • 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
  • C07C33/16—Alcohols containing rings other than six-membered aromatic rings containing rings with more than six ring members
• • 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
  • C07C45/004—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with organometalhalides
• • 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
  • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
  • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
  • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
  • C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
• • 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
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/29—Saturated compounds containing keto groups bound to rings
  • C07C49/307—Saturated compounds containing keto groups bound to rings to a seven- to twelve-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
  • C07C49/547—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings to a seven- to twelve-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
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered

Definitions

• This invention relates to substituted cyclooctenes having agrestic, natural, and floral, green, woody odour notes, their manufacture, and to fragrance compositions containing them.
• odour notes imparted by cyclooct-4-en aldehyde (1 ) may be interesting in their own right, in the fragrance industry, there is always an ongoing demand for new compounds that enhance or improve on odour notes, or impart ' new odour notes.
• the invention refers to the use of a compound of formula I as fragrance,
• X is carbonyl, or -(CHOH)- ;
• R is methyl or ethyl, or linear or branched C 3 to C 5 alkyl, such as /-propyl, r/-propyl, n- butyl, sec-butyl, terf-butyl, /.-pentyl, sec-pentyl, and .ert-pentyl; or
• R is vinyl, or linear or branched C 3 to C 5 alkenyl, such as propen-1-yl, propen-2-yl, allyl, but-1-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, and pentenyl; and the dotted line represents one optional double bond.
• the compounds according to the present invention may contain 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 of formula I are 1-cyclooct-3-enylethanone, 1-cyclooct-3- enylpropan-1 -one, 1 -cyclooct-3-enyl-2-methylpropan-1 -one, 1 -cyclooct-3-enylpropan-1 - ol, 1-cyclooct-4-enylethanone, 1 -cyclooct-2-enylethanone, 1-cyclooct-2-enylethanol, 1- cyclooct-1-enylethanone, 1-cyclooctylpropanone, 1-cyclooctyl-2-methylpropanone, and 1-cyclooctyl-2-methylpropanol.
• one optional double bond refers to compounds of formula I wherein the bond between C-1 and C-2 together with the dotted line represents a double bond, and the bonds between C-2 and C-3, C-3 and C- 4, and C-4 and C-5 represent each a single bond; or the bond between C-2 and C-3 together with the dotted line represents a double bond, and the bonds between C-1 and C-2, C-3 and C-4, and C-4 and C-5 represent each a single bond; or the bond between C-3 and C-4 together with the dotted line represents a double bond, and the bonds between C-1 and C-2, C-2 and C-3, and C-4 and C-5 represent each a single bond; or the bond between C-4 and C-5 together with the dotted line represents a double bond, and the bonds between C-1 and C-2, C-2 and C-3, and C-3 and C-4 represent each a single bond; or the bonds between C-1 and C-2, C-2 and C-3, and C-3 and C-4 represent each a single bond; or the bonds between C-1 and C-2, C-2 and
• 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 products 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.
• known odourant molecules selected from the extensive range of natural products 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.
• alcohols farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol, (Z)-hex-3-en-1-ol, menthol, ⁇ -terpineol.
• aldehydes citral, -hexyl cinnamaldehyde, Lilial, methylionone, verbenone, nootkatone, geranylacetone.
• esters allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, decyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethyl acetoacetate, cis-3-hexenyl isobutyrate, cis-3-hexenyl salicylate, linalyl acetate, methyl dihydrojasmonate, styralyl propionate, vetiveryl acetate, benzyl acetate, geranyl acetate.
• lactones ⁇ -undecalactone, ⁇ -decalactone, pentadecanolide, 12-oxahexadecanolide.
• acetals Viridine (phenylacetaldehyde dimethylacetal). other components often used in perfumery: indole, p-mentha-8-thiol-3-one, methyleugenol, eugenol, anethol.
• the present invention refers in a further aspect to a fragrance composition
• a fragrance composition comprising a mixture of A) a compound of formula Ic; and B) at least one compound selected from a compound of formula la, a compound of formula lb, and a compound of formula Id
• mixtures comprising a compound of formula la, a compound of formula Ic, and a compound of formula Id.
• 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.
• 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 of the application.
• compounds 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 regarded as limiting 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 compound of the present invention or the fragrance composition comprising the compound with the fragrance application. Alternatively, they may be added in an entrapped form, by being in a previous step entrapped with an entrapment material, for example polymers, capsules, microcapsules and nanocapsules, liposomes, precursors, film formers, absorbents, for example by using carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and then mixed with the application.
• an entrapment material for example polymers, capsules, microcapsules and nanocapsules, liposomes, precursors, film formers, absorbents, for example by using carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and then mixed with the application.
• 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 into 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
• X is carbonyl, or -(CHOH)- ; and R is methyl or ethyl, or linear or branched C 3 to C 5 alkyl, such as /-propyl, n-propyl, n- butyl, sec-butyl, terf-butyl, n-pentyl, sec-pentyl, and terf-pentyl; or R is vinyl or linear or branched C 3 to C s alkenyl, such as propen-1-yl, propen-2-yl, allyl, but-1-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, and pentenyl; and the dotted line represents one optional double bond; provided that when X is carbonyl and one of the bonds between C-1 and C-2, C-2 and C-3, and C-3 and C-4 together with the dotted line is a double bond, R is not methyl or ethyl; when X is carbony
• a double bond isomeric mixture of compounds of formula I i.e. a mixture of substituted cyclooct-1-enes, -3-enes and -4-enes, may be prepared by addition of an alkanoic acid chloride to cyclooctene followed by dehydrochlorination of the resulting chloro-cyclootyl alkanone under conditions known to the person skilled in the art.
• Example 1 1-cvclooct-3-enylethanone
• Odour description agrestic, armoise, wormwood, thujone, natural.
• Example 2 Obtained according to the experimental procedure of Example 1 from cyclooctene (150 g, 1.36 mol), propionic anhydride (354 g, 2.72 mol) and zinc bromide (30.6 g, 0.14 mol) in 27% yield. Boiling point 60°C/80 mbar.
• Odour description fruity, banana, tagete.
• Example 2 Obtained according to the synthetic procedure of Example 1 from cyclooctene (150 g, 1.36 mol), isobutyric anhydride (430.3 g, 2.72 mol) and zinc bromide (30.6 g, 0.14 mol) in 33% yield. Boiling point 85°C/80 mbar).
• 1-cyclooct-3-enylpropan-1-one (84.0 g, 0.5 mol) was slowly added to a solution of sodium borohydride (11.9 g, 0.3 mol) in ethanol (330 ml) at 0°C (ice bath), and stirring was continued at room temperature for 4 h.
• the reaction mixture was poured into ice- cold 2N HCI (500 ml) and extracted with MTBE (2 x 200ml).
• Odour description cassie, mimosa, green, moss, natural, forest, fatty
• Odour description green leaves, thuja oil, armoise, fruity.
• Odour description green, thuja oil, wormwood, fruity.
• Odour description fruity, sweet, anisic, minty, terpineol, camphoraceous.
• Odour description agrestic, camphoraceous, armoise, thujone-like, earthy, woody.
• Odour description floral, woody, rosy, fruity.
• Example 12 A fragrance composition for a soap :

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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)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2003
  • 2003-10-08 WO PCT/CH2003/000660 patent/WO2004035017A1/en not_active Ceased
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