Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/608—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a ring other than a six-membered aromatic ring in the acid moiety
• • 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
  • C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
• • 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
  • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing 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
  • C11B9/0053—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms both rings being six-membered

Definitions

• the present invention relates to new ⁇ , ⁇ -unsaturated esters and to their use.
• R is a straight or branched C 3 -C 4 alkenyl residue having the double bond in position 2 or a C alkylcycloalkyl residue , i.e. allyl, methallyl, crotyl or methylcyclopropyl residue, and
• X is either a residue of formula A
• R , R 3 are independently hydrogen, methyl or ethyl
• one or more hydrogen atoms in the ring system A may be substituted by (R) y , R 4 is a straight or branched C ⁇ -C hydrocarbon residue,
• y is an integer of 1 to 4,
• k is 0 or an integer of 1,2 or 3,
• R 5 or R6 are independently hydrogen or a straight or branched C ⁇ -C 3 hydrocarbon residue being at any position of the ring system B, and the sum of the carbon atoms of R 5 and R 6 is 3 or less,
• n 0 or an integer of 1 or 2
• n 0 or an integer of 1 or 2
• R , R are independently hydrogen or methyl one or more hydrogen atoms in the ring system A may be substituted by (R) y , R 4 is ' a straight or branched C ⁇ -C 4 hydrocarbon residue,
• y is an integer of 1 to 4,
• k stands for 0 or 1.
• R 1 is C alkylcycloalkyl (such as methyl- cyclopropyl) or a C 4 alkenyl residue (such as crotyl) having the double bond in position 2,
• X is a residue of formula (A)
• R 2 and R are independently hydrogen or methyl
• one or more hydrogen atoms in the ring system A may be substituted by (R) y , R 4 is a straight or branched C ⁇ -C hydrocarbon residue, y is an integer of 1 to 4,
• k 0 or 1.
• the new ⁇ , ⁇ -unsaturated esters of formula I, wherein X is a residue of formula A, may be prepared according to procedures known in the art as shown in scheme 1.
• the starting ketones (a) may be converted by a Knoevenagel reaction well known in the art to compounds (b) .
• the ⁇ , ⁇ - unsaturated diesters may be reduced by metal hydrides or hydrogen to (c) and then saponified to (d) .
• the new ⁇ , ⁇ -unsaturated esters of formula I wherein X is a residue of formula B can be prepared from the corresponding bicyclic ketones according to the process illustrated in scheme 3.
• the , ⁇ -unsaturated esters wherein X is a residue of formula B, are generally obtained as mixtures of cis/trans-isomers.
• the double bond is either in position 1 or 2.
• compositions comprising a compound according to the present invention possess fruity organolepic characteristics.
• organoleptic characteristics make the new compounds well suited for different functional perfumery applications, as well as for imparting unique green galbanum and fruity notes to fine perfumery products.
• the compounds of the invention show outstanding diffusion and/or high substantivity, the latter meaning persistence of odor.
• the high diffusion and substantivity is well perceived on fabrics washed with a detergent or treated with a softener comprising one or more of the new , ⁇ -unsaturated esters.
• the typical fresh green odor is already perceived very strongly on the wet fabric and later also on the dry material.
• the new compounds are excellent fragrances for use in any field of fine and functional perfumery, such as perfumes, household products, laundry products, body care products and cosmetics.
• Fragrance or flavor compositions comprising a compound according to the present invention may optionally be combined with numerous organoleptic ingredients of natural and/or synthetic origin.
• the range of the natural fragrances and flavors includes in addition to readily volatile, also moderately and only slightly volatile components.
• the synthetic organoleptic ingredients embrace representatives from practically all classes of organoleptic substances. The following list comprises examples of known organoleptic ingredients which may be combined with the compounds of the invention:
• tree moss absolute basil oil, tropical fruit oils (such as bergamot oil, mandarin oil, etc.), astix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, wormwood oil, lavender oil, rose oil, jasmin oil, ylang-ylang oil, etc.;
• alcohols farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol, (Z) -hex-3-en-l-ol, menthol, -terpineol, etc.;
• aldehydes citral, ⁇ -hexyl cinnamaldehyde, Lilial, methylionone, verbenone, nootkatone, geranylacetone, etc.;
• 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, etc.;
• lactones ⁇ -undecalactone, ⁇ -decalactone, pentadecanolide, 12-oxahexadecanolide, etc.;
• novel compounds of the invention harmonize particularly well with floral notes (lily of the valley, rose, iris, jasmine, ylang-ylang, narcissus notes, etc.) as well as with woody, chypre and animalic notes, tobacco like an patchouli compositions, etc.
• the percentage in which the compounds of the invention are used in a composition may vary within wide limits ranging from a few parts per thousand in mass market products (e.g. cleaning compositions, deodorant, etc.) up to a few percents in alcoholic extracts for fine perfumery.
• the compounds of formula I provide fragrance compositions with green-galbanum and intense fresh green-fruity notes and a remarkable increase of the volume (strength, diffusivity) and of the duration (substantivity) of the odor.
• the organoleptic characteristic of compounds according to the present invention make the new compounds well suited for imparting an intense pineapple and galbanum flavor into food and beverage products.
• Odor fruity, green, rosy, galbanone
• MS(EI) 250 (M + , 2), 209 (6), 193 (56), 163 (16), 152 (22), 135 (57), 107 (76), 105 (40), 981 (46), 81 (40), 79 (100), 67 (58) .
• IR (ATR) 2940s, 2863m, 1719vs, 1450m, 1365m, 1273m, 1237m, 1157s, 1121s, 986m, 931m cm -1 .
• MS(EI) 250 (M + , 1), 235 (1), 193 (58), 163 (18), 153 (18), 147 (20), 135 (63), 107 (77), 105 (37), 91 (53), 81 (43), 79 100), 77 (42), 67 (70).
• GCMS(EI) isomer 1: 220 (M + , 12), 179 (17), 161 (18), 133 (100), 91 (70), 79 (15), 67 (22); Isomer 2: 220 (M + , 5), 179 (40), 161 (26), 135 (54), 133 (100), 91 (68), 79 (49), 67 (59); Isomer 3: 220 (M + , 7), 179 (44), 161 (29), 133 (100), 91 (65), 79 (47), 67 (53); Isomer 4: 220 (M + , 17), 179 (50), 163 (44), 161 (40), 133 (100), 91 (62), 81 (46), 79 (51), 67 (68). IR (ATR): 2923sm, 2853m, 1711vs, 1647m, 1447m, 1234vs, 1061s, 989m, 928m cm "1 .
• 2-cyclohexyl-acrylic acid allyl ester reinforces the fresh and clean aspect. It provides richness and volume and increases the diffusivity of this Fougere fragrance. It enhances the sparkling effect of the green hesperidic and agrestic top notes and harmonizes with the floral, musky, ambery and woody middle and dry-down notes.
• the green-galbanum note of 2-cyclohexyl-acrylic acid allyl ester gives a fresh and clean effect in the fragrance and enhances the lavandine aspect in this composition.
• 2- Cyclohexyl-acrylic acid allyl ester blends nicely with agrestic, hesperidic and fruity notes.

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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)
• Cosmetics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (6)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

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Citations (1)

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• 2000
  • 2000-08-25 EP EP00810759A patent/EP1182190A1/en not_active Withdrawn
• 2001
  • 2001-08-20 AT AT01960027T patent/ATE281426T1/de not_active IP Right Cessation
  • 2001-08-20 DE DE60106941T patent/DE60106941T2/de not_active Expired - Lifetime
  • 2001-08-20 AU AU2001281641A patent/AU2001281641A1/en not_active Abandoned
  • 2001-08-20 ES ES01960027T patent/ES2231532T3/es not_active Expired - Lifetime
  • 2001-08-20 JP JP2002521183A patent/JP2004506047A/ja not_active Withdrawn
  • 2001-08-20 US US10/362,550 patent/US20040023839A1/en not_active Abandoned
  • 2001-08-20 EP EP01960027A patent/EP1311470B1/en not_active Expired - Lifetime
  • 2001-08-20 WO PCT/CH2001/000507 patent/WO2002016307A1/en not_active Ceased

Patent Citations (1)

Non-Patent Citations (3)

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