WO2011029743A1 - Lily of the valley-type fragrance compositions comprising 2,5,7,7-tetramethyloctanal - Google Patents

Lily of the valley-type fragrance compositions comprising 2,5,7,7-tetramethyloctanal Download PDF

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Publication number
WO2011029743A1
WO2011029743A1 PCT/EP2010/062662 EP2010062662W WO2011029743A1 WO 2011029743 A1 WO2011029743 A1 WO 2011029743A1 EP 2010062662 W EP2010062662 W EP 2010062662W WO 2011029743 A1 WO2011029743 A1 WO 2011029743A1
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methyl
fragrance
fragrance composition
total amount
composition according
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PCT/EP2010/062662
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French (fr)
Inventor
Wolfgang Krause
Ralf Pelzer
Jörg Botzem
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Basf Se
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Publication of WO2011029743A1 publication Critical patent/WO2011029743A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • 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
    • 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
    • C11B9/0069—Heterocyclic compounds
    • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
    • C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms

Definitions

  • the present invention relates to fragrance compositions of the lily of the valley-type comprising 2,5,7,7-tetramethyloctanal (Lyrisal®) and 2-isobutyl-4-methyl-tetrahydro- 2H-pyran-4-ol.
  • the present invention further relates to a method for producing a perfumed product or article as well as perfumed or aromatized articles comprising the fragrance compositions of the present invention.
  • Lily of the valley- or muguet-type fragrances are widely used and accepted in a large variety of consumer products such as for example detergents of all kind, washing soaps and hygiene and cosmetic products of all kinds.
  • Blends or mixtures of those lily of the valley- or muguet-type fragrances (hereinafter referred to as "fragrance compositions") often contain the synthetic compound 2-methyl-3-(4-tert.-butylphenyl)propanal of formula (I)
  • Lysmeral® also known under the tradenames Lysmeral® (BASF SE), Lilial® (Givaudan SA) and Lilestralis® (Innospec Inc.). Some of those product may also contain the meta- substituted isomer 2-methyl-3-(3-tert.-butylphenyl)propanal (CAS Registry Number 62518-65-4) of formula (II)
  • EP 0 252 378 discloses aliphatic aldehydes and their use as fragrance ingredients. Specifically, 2,5,7,7-tetramethyloctanal is described as a valuable fragrance ingredient with an intense lily-of-the-valley note. Furthermore, a method for the preparation of the abovementioned aldehydes is disclosed comprising base catalyzed condensation of the corresponding precursor aldehydes followed by catalytic hydrogenation.
  • EP 0 269 999 discloses the corresponding aliphatic alcohols and esters and their use as fragrance ingredients. Specifically, 2,5,7,7-tetramethyloctanol is described as a valuable fragrance ingredient with a flowery rose-like note. The document further discloses the preparation of 2,5,7,7-tetramethyloctanol by hydrogenation of the corresponding aldehyde 2,5,7,7-tetramethyloctanal.
  • EP 0 395 982 discloses beta, gamma-unsaturated nitriles, the preparation thereof and their use as scents. More specifically, 4,7,9,9-tetramethyl-dec-3-en-nitrile is disclosed as well as the preparation thereof by condensation of 2,5,7,7-tetramethyloctanal with cyanoacetic acid. The reaction product is described as having a waxy, floral and fresh fragrance note.
  • WO 2009/027957 discloses perfumes wherein the compound 2-methyl-3-(4-tert.- butylphenyl)propanal is replaced by other perfume raw materials in accordance with specific mass ratio replacement levels.
  • fragrances or fragrance compositions with similar, preferable exchangeable fragrance characteristics to those of known lily of the valley- or muguet-type fragrances, especially of para- or meta- substituted dihydrocinnamaldehyde derivatives such as for example the compounds of formula (I) and/or (II).
  • the fragrances or fragrance compositions should be readily accessible in technical quantities under economically favorable conditions.
  • fragrance composition comprising a) 2,5,7,7-tetramethyloctanal and
  • d) optionally one or more diluent(s).
  • fragrance compositions of the present invention comprising 2,5,7,7-tetramethyloctanal of formula (III)
  • fragrance compositions of the present invention comprise at least organoleptically active quantities of 2,5,7,7-tetramethyloctanal (CAS Registry Number 1 141 19-97-0) of formula (III)
  • the compound 2,5,7,7-tetramethyloctanal of formula (III) may, if desired, be used in optically active or diastereomerically enriched form or in another preferred embodiment in form of a racemic mixture of diastereomers.
  • 2,5,7,7-tetramethyloctanal of formula (III) may be synthesized in pure form, e.g. according to the route as described in EP 0 252 378 by base catalyzed condensation of 3,5,5- trimethylhexanal with propionic aldehyde and subsequent catalytic hydrogenation.
  • the compound 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) may advantageously be used in form of a mixture of the respective diastereomers (cis/trans) both either in optically active or preferably in racemic form.
  • 2-isobutyl-4-methyl- tetrahydro-2H-pyran-4-ol of formula (IV) is commercially available, e.g. under the trade names Florol® (Firmenich S.A.) and Florosa® (Givaudan S.A.) in form of dia- stereomeric mixtures and may be used as such.
  • the fragrance compositions of the present invention comprise diastereomers of 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) with at least 62% of the cis form.
  • the fragrance composi- tions of the present invention comprise diastereomers of 2-isobutyl-4-methyl- tetrahydro-2H-pyran-4-ol of formula (IV) having 65-95% of the cis form and 5-35% of the trans form, very preferred 70-80% cis form and 20-30% trans form.
  • fragrance compositions of the present invention may also optionally comprise as component or components c) one or more additional fragrance substance(s).
  • the fragrance compositions of the present invention may also optionally comprise as component or components d) one or more diluent(s).
  • the fragrance compositions of the present invention may also optionally comprise further constituents known to those of skill in the art as common ingredients in fragrance compositions.
  • fragrance compositions of the present invention can be combined advantageously can be found for example in S. Arctander, Perfume and Flavor Materials, Vol. I and 1 1 , Montclair, N.J., 1969, self- published, or in K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th Edition, Wiley-VCH, Weinheim 2001.
  • fragrance compositions of the present invention can be combined with one or more individual fragrance substances known to those of skill in the art as additional fragrance substance c) or o as an additional component to be combined or mixed with the fin- ished fragrance composition, comprising but not limited to, for example, fragrances selected from the following groups: of hydrocarbons, such as, for example, 3-carene; alpha-pinene; beta-pinene; alpha- terpinene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene;
  • phenylacetaldehyde 3-phenylpropanal; hydratropaldehyde; 3-(3-lsopropyl- phenyl)butanal, 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4- ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-
  • Preferred fragrance substances c) according to the present invention are those, selected from the group of fragrance compounds consisting of 7-hydroxy-3,7- dimethyloctanal; 4-isopropyl-cyclohexylmethanol; limonene; hexanol; octanol; 3- octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenol; 3,7-dimethyl-6-octenenitrile; 3,7-dimethyl-octanenitrile; (E)- and (Z)-3-hexenyl formate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; citronellol; gera- niol; nerol; linalool; lavandul
  • the fragrance compositions of the present invention comprise one or more, usually 1 to 20, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3 and most preferably 1 or 2 additional fragrance substances selected from the group of fragrance listed above, whereas the fragrance substances 7-hydroxy-3,7- dimethyloctanal and 4-isopropyl-cyclohexylmethanol are particularly preferred fragrance substances c) comprised by the fragrance compositions of the present inven- tion.
  • fragrance compositions of the present invention are those comprising 7-hydroxy-3,7-dimethyloctanal (Hydroxycitronellal, CAS Registry Number 107- 75-5) of formula (V) as additional fragrance substance c).
  • fragrance compositions of the present invention are those comprising 4-isopropyl-cyclohexylmethanol (4-(1 -methylethyl)-cyclohexanemethanol); CAS Registry Number 13828-37-0) of formula (VI)
  • fragrance substance c The compounds 7-hydroxy-3,7-dimethyloctanal of formula (V) and 4-isopropyl-cyclohexylmethanol of formula (VI) are known and commercially widely available e.g. as Mayol® (Firmenich SA), MeijiffTM (International Flavors & Fragrances Inc.) or may be synthesized by known methods. Further particularly preferred fragrance compositions of the present invention are those comprising 2,6-dimethylheptan-2-ol (CAS Registry Number 13254-34-7) of formula (VII) as additional fragrance substance c).
  • fragrance compositions of the present invention are those comprising 3,7-dimethyl-octan-1 ,7-diol (Hydroxycitronellol; CAS Registry Number 107- 74-4) of formula (VIII) as additional fragrance substance c).
  • fragrance compositions of the present invention are those comprising 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal; CAS Registry Number 30168-23-1 ) of formula (IX), as additional fragrance substance c).
  • the compound 4-(Octahydro-4,7-methano-5H- inden-5-yliden)butanal is commercially available as Dupical® (Givaudan).
  • fragrance compositions of the present invention are those comprising the compounds 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde of formula (X) and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde of formula (XI) (CAS Registry Number 31906-04-4 and 51414-25-6 respectively),
  • the compounds 4-(4-Hydroxy-4-methylpentyl)- 3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde are commercially available as a 70:30 mixture under tradenames Kovanol® (Takasago) or Lyral® (International Flavors & Fragrances Inc.).
  • fragrance compositions of the present invention comprise or (substantially) consist of the components
  • d) optionally one or more diluent(s).
  • fragrance compositions of the present invention comprise or (substantially) consist of the components
  • fragrance compositions of the present invention comprise or (substantially) consist of the components
  • d) optionally one or more diluent(s).
  • fragrance compositions of the present inven- tion comprise or (substantially) consist of the components
  • fragrance compositions of the present invention comprise or (substantially) consist of the components
  • d) optionally one or more diluent(s).
  • fragrance compositions of the present invention comprise or consist of the components a) 2,5,7,7-tetramethyloctanal of formula (III) and
  • d) optionally one or more diluent(s).
  • d) optionally one or more diluent(s).
  • d) optionally one or more diluent(s).
  • additional fragrance substances means one or more, usually 1 to 20, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3 and most preferably 1 or 2 additional fragrance substances selected from the group of fragrance substances c) listed above other than 7-hydroxy- 3,7-dimethyloctanal and 4-isopropyl-cyclohexylmethanol and 4-(Octahydro-4,7- methano-5H-inden-5-yliden)butanal and 2,6-dimethylheptan-2-ol and 3,7-dimethyl- octan-1 ,7-diol and 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 2-isobutyl-4- methyl-tetrahydro-2H-pyran-4-ol may generally be varied within a broad range.
  • the weight-based ratio of the total amount 2,5,7,7-tetramethyloctanal to the total amount of 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol in the finished fragrance com- position ranges from about 100:1 to about 1 :100, more preferably from 50:1 to 1 :50, more preferably from 30:1 to 1 :30, more preferably from 20:1 to 1 :20, more preferably from 10:1 to 1 :10 and most preferably from 5:1 to 1 :5.
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 2,6-dimethylheptan-2- ol may also generally be varied within a broad range.
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 2,6- dimethylheptan-2-ol in the finished fragrance composition ranges from about 50:1 to about 1 :50, more preferably from 20:1 to 1 :10, more preferably from 20:1 to 1 :1 , and most preferably from 10:1 to 1 :1.
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 3,7-dimethyl-octan- 1 ,7-diol may also generally be varied within a broad range.
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 3,7- dimethyl-octan-1 ,7-diol in the finished fragrance composition ranges from about 1 :30 to about 30:1 , more preferably from 10:1 to 1 :10, more preferably from 5:1 to 1 :5, and most preferably from 3:1 to 1 :3.
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 7-hydroxy- 3,7-dimethyloctanal may also generally be varied within a broad range.
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 7-hydroxy-3,7-dimethyloctanal in the finished fragrance composition ranges from about 30:1 to about 1 :30, more preferably from 10:1 to 1 :10, more preferably from 5:1 to 1 :5 and most preferably from 3:1 to 1 :3.
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-isopropyl- cyclohexylmethanol may also generally be varied within a broad range.
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-isopropyl-cyclohexylmethanol in the finished fragrance composition ranges from about 30:1 to about 1 :30, more preferably from 20:1 to 1 :10, more preferably from 15:1 to 1 :1 , more preferably from 10:1 to 1 :1 and most preferably from 5:1 to 1 :1.
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-(Octahydro- 4,7-methano-5H-inden-5-yliden)butanal may generally be varied within a broad range.
  • the weight-based ratio of the total amount 2,5,7,7-tetramethyloctanal to the total amount of 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal in the finished fragrance composition ranges from about 100:1 to about 1 :100, more preferably from 50:1 to 1 :50, more preferably from 30:1 to 1 :30, more preferably from 20:1 to 1 :20, more preferably from 10:1 to 1 :10 and most preferably from 5:1 to 1 :5.
  • the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3- cyclohexen-1 -carboxaldehyde may generally be varied within a broad range.
  • the weight-based ratio of the total amount 2,5,7,7-tetramethyloctanal to the total amount of 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4- Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde in the finished fragrance composition ranges from about 100:1 to about 1 :100, more preferably from 50:1 to 1 :50, more preferably from 30:1 to 1 :30, more preferably from 20:1 to 1 :20, more preferably from 10:1 to 1 :10 and most preferably from 5:1 to 1 :5.
  • the fragrance compositions according to the present invention comprise at least or- ganoleptically active quantities of the named ingredients 2,5,7,7-tetramethyloctanal and 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol and, if present, of the optional further fragrance substances 7-hydroxy-3,7-dimethyloctanal and/or 4-isopropyl- cyclohexylmethanol and, if present of the optional further fragrance substances, preferably 2,6-dimethylheptan-2-ol and/or 3,7-dimethyl-octan-1 ,7-diol.
  • or- ganoleptically active amount means an amount sufficient to stimulate an olfactorial impression in a human being, especially the olfactorial impression of a typical lily of the valley- or muguet-type scent.
  • fragrance substances of the present invention especially in the case of those comprising 2,5,7,7-tetramethyloctanal and 2-isobutyl-4-methyl-tetrahydro-2H- pyran-4-ol and 7-hydroxy-3,7-dimethyloctanal and 4-isopropyl-cyclohexylmethanol generally only minor amounts or concentrations are necessary to generate the desired lily of the valley- or muguet-type fragrance.
  • fragrance substances of the present invention especially in the case of those comprising 2, 5, 7, 7-tetramethyloctanal and 2-isobutyl-4-methyl- tetrahydro-2H-pyran-4-ol and 7-hydroxy-3,7-dimethyloctanal and 4-isopropyl- cyclohexylmethanol and 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal and 4- (4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 -carboxaldehyde also generally only minor amounts or concentrations are necessary to generate the desired substantive lily of the valley- or muguet-type fragrance.
  • fragrance substances of the present invention especially in the case of those comprising 2, 5, 7, 7-tetramethyloctanal and 2-isobutyl-4- methyl-tetrahydro-2H-pyran-4-ol and 4-(Octahydro-4,7-methano-5H-inden-5- yliden)butanal and optionally 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde also generally only minor amounts or concentrations are necessary to generate the desired substantive lily of the valley- or muguet-type fragrance.
  • compositions of the present invention comprise or consist of, based on the total amount of the finished composition, a total amount of 2, 5, 7, 7-tetramethyloctanal in the range from about 0,1 to 95 wt.%, preferably from about 0,1 to 90 wt.%, more preferably from 0,1 to 50 wt.%, more preferably from 0,1 to 30 wt.%, more preferably from 0,1 to 20 wt.%, more preferably from 0,1 to 15 wt.%, more preferably from 0,2 to 10 wt.%, even more preferably from 0,5 to 10 wt.% and most preferably in the range from 1 to 5 wt.%.
  • compositions of the present invention comprise or consist of, based on the total amount of the finished composition, a total amount of 2,5,7,7- tetramethyloctanal in the range from about 15 to 90 wt.%, preferably from about 30 to 80 wt.%, more preferably from 50 to 70 wt.%.
  • compositions of the present invention comprise or consist of, based on the total amount of the finished composition, a total amount of 2-isobutyl-4-methyl- tetrahydro-2H-pyran-4-ol in the range from about 0,1 to 95 wt.%, preferably from about 0,1 to 90 wt.%, more preferably from 1 to 90 wt.%, more preferably from 1 to 70 wt.%, more preferably from 5 to 50 wt.%, more preferably from 10 to 50 wt.%, even more preferably from 10 to 40 wt.% and most preferably in the range from 20 to 30 wt.%.
  • compositions of the present invention comprise or consist of, based on the total amount of the finished composition, a total amount of 2-isobutyl-4- methyl-tetrahydro-2H-pyran-4-ol in the range from about 5 to 80 wt.%, preferably from about 10 to 60 wt.%, more preferably from 15 to 45 wt.%.
  • compositions of the present invention comprising 7-hydroxy-3,7- dimethyloctanal comprise or consist of, based on the total amount of the finished com- position, a total amount of 7-hydroxy-3,7-dimethyloctanal in the range of up to 30 wt.%, preferably from 0,1 to 30 wt.%, more preferably from 0,5 to 25 wt.%, more preferably from 1 to 20 wt.%, even more preferably from 1 to 10 wt.% and most preferably in the range from 2 to 4 wt.%.
  • compositions of the present invention comprising 4-isopropyl- cyclohexylmethanol comprise or consist of, based on the total amount of the finished composition, a total amount of 4-isopropyl-cyclohexylmethanol in the range of up to 30 wt.%, preferably from 0,01 to 30 wt.%, more preferably from 0,1 to 20 wt.%, more preferably from 0,1 to 10 wt.%, even more preferably from 0,1 to 5 wt.% and most preferably in the range from 0,1 to 2,5 or even to 1 wt.%.
  • compositions of the present invention comprising 4-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3- cyclohexen-1 -carboxaldehyde comprise or consist of, based on the total amount of the finished composition, a total amount of 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde in the range of up to 30 wt.%, preferably from 0,01 to 30 wt.%, more preferably from 0,1 to 20 wt.%, more preferably from 0,1 to 10 wt.%, even more preferably from 0,1 to 5 wt.% and most preferably in the range from 0,1 to
  • compositions of the present invention comprising 4-(4- Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 -carboxaldehyde comprise or consist of, based on the total amount of the finished composition, a total amount of 4-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3- cyclohexen-1 -carboxaldehyde in the range of up to 10 wt.%, preferably from 0,01 to 8 wt.%, more preferably from 0,1 to 5 wt.%, more preferably from 0,1 to 2.5 wt.%.
  • the perfume compositions of the present invention do preferably not contain significant amounts of 2-methyl-3-(4-tert.-butylphenyl)propanal (the para-substituted compound of formula (I)).
  • the weight-based ratio of 2-methyl-3-(3-tert.- butylphenyl)propanal to 2-methyl-3-(4-tert.-butylphenyl)propanal, if present at all, in the finished perfume composition ranges from over 10000:1 or higher to 50:1 , preferably from 10000:1 to 100:1 .
  • the fragrance compositions of the present invention comprise, based on the total amount of the finished composition, a total amount of 2-methyl-3-(4-tert.-butylphenyl)propanal of 1 wt.% or less, preferably of 0,5 wt.% or less, more preferably of 0,1 wt.% or less, more preferably of 0,05 wt.% or less and most preferably of 0,01 wt.% or less.
  • the fragrance compositions of the present invention are substantially free of 2-methyl-3-(4- tert.-butylphenyl)propanal of formula (I), meaning that it comprises based on the total amount of the finished composition, a total amount of 2-methyl-3-(4-tert.-butylphenyl) propanal of 0,005 wt.% or less, preferably of 0,001 wt.% or less.
  • the fragrance compositions of the present invention may optionally comprise as component d) one or more diluent(s).
  • the expression "one or more diluent(s)" means that one diluent or a mixture of two or more diluents may be present in fragrance compositions.
  • fragrance means a substance known to those of skill in the art as a suiable solvent for perfume or fragrance compositions such as, e.g. an alcohol such as ethanol or isopropanol and/or a polyol or an ether derived thereof such as diethylene glycol monoethyl ether, glycerol, propylene glycol, 1 ,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, dialkyl esters of 1 ,2- cyclohexanedicarboxylic acid, especially 1 ,2-cyclohexanedicarboxylic acid diisononyl ester (Hexamoll® DINCH, BASF SE) or and the like.
  • an alcohol such as ethanol or isopropanol
  • a polyol or an ether derived thereof such as diethylene glycol monoethyl ether, glycerol, propylene glycol,
  • particularly preferred fragrance compositions according to the present invention comprise one or more diluents) d) selected from the group consisting of diethylene glycol monoethyl ether, glycerol, propylene glycol, 1 ,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate and dialkyl esters of 1 ,2-cyclohexanedicarboxylic acid, especially 1 ,2-cyclohexanedicarboxylic acid diisononyl ester.
  • diluents selected from the group consisting of diethylene glycol monoethyl ether, glycerol, propylene glycol, 1 ,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate and dialkyl esters of 1 ,2-cyclohexanedicarboxylic acid, especially 1
  • the components of the fragrance compositions according to the present invention namely 2,5,7,7-tetramethyloctanal and 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol and, if present, of the optional further fragrance substances 7-hydroxy-3,7- dimethyloctanal and/or 4-isopropyl-cyclohexylmethanol and, if present other optional further fragrance substances, preferably 2,6-dimethylheptan-2-ol and/or 3,7-dimethyl- octan-1 ,7-diol and/or 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal as well as the diluent(s), if present, may be blended or mixed by conventional techniques known to those of skill in the art.
  • Exemplary fragrance compositions according to the present invention may comprise, based on the total amount of the composition, e.g.:
  • Particularly preferred fragrance compositions according to the present invention may comprise, based on the total amount of the composition, e.g.
  • fragrance compositions of the present invention can also be combined with extracts of natural raw materials such as essential oils, concretes, absolutes, resins, resi- noids, balsams, tinctures and the like known to those of skill in the art, comprising but not limited to, for example:
  • Ambergris tincture amyris oil; angelica seed oil; angelica root oil; aniseed oil; valerian oil; basil oil; treemoss absolute; bay oil; mugwort oil; benzoin resin; bergamot oil;
  • the fragrance compositions of the present invention can also be combined with antioxidants (stabilizers) known to those of skill in the art, comprising but not limited to, for example: phenolic antioxidants such as sodium salicylate, 2,4-dihydroxybenzophenone, 2,6-di-t- butyl-p-cresol, butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4-methylphenol (BHT), 2,6-di-t-butyl-4-ethylphenol, stearyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, propyl 3,4,5-trihydroxybenzoate, hydroquinone, and catechol; bisphenolic antioxidants such as 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'- methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-
  • the fragrance compositions of the present invention may contain the usual amounts of fixatives known to those of skill in the art.
  • Preferred fixative for the use in the fragrance compositions of the present invention include but are not limited to sandalwood, ambra products, polycyclic, macrocyclic and alicyclic substances like Am- brox® (Firmenich SA), Galaxolide® (Int. Flavors & Fragrances Inc.), Tonalide, Exalto- lide® (Firmenich SA), Habanolide® (Firmenich SA) und Helvetolide® (Firmenich SA).
  • the fragrance compositions of the present invention can also comprise encapsulating substances like cyclodextrines; chelating and complexing agents like EDTA or citric acid.
  • the fragrance compositions of the present invention may advantageously used for em- parting and/or enhancing an odor or flavor of a product or article of all kind with a lily of the valley- or muguet-type note or with a syringa-type note, a magnolia-type note, a cyclamen-type note or a hyacinth-type note, preferably with a lily of the valley- or muguet-type note.
  • a further embodiment of the present invention therefore relates to a method for emparting and/or enhancing an odor or flavor of a product or article with a lily of the valley- or muguet-type note or with a syringa-type note, a magnolia-type note, a cyclamen-type note, a hyacinth-type note or a lilac-type note, preferably with a lily of the valley- or muguet-type note, comprising bringing into contact or mixing with or add- ing to said product or article an organoleptically active quantity of a fragrance composition according to the present invention whereas the term "organoleptically active quantity" has the meaning as defined above.
  • the fragrance compositions of the present invention may be used or applied in every suited form e.g. in pure form or in form of dilutions or mixtures as well as in microencapsulated form.
  • a further embodiment of the present invention relates to a method for producing a perfumed product or article comprising bringing into contact or mixing with or adding to said product or article an organoleptically active quantity of the fragrance composition according to the present invention.
  • the present invention relates to a perfumed or aromatized product or article comprising an organoleptically active quantity of the fragrance composition according to the present invention as hereinbefore described.
  • the perfumed or aromatized articles or products accessible by the present invention may be a perfumed or aromatized article of manufacture of all kind.
  • Preferred aromatized or perfumed articles or products comprise, but are not limited to, e.g. perfumes, detergents and washing soaps, both liquid and solid and toilet articles of all kinds.
  • Preferred perfumed or aromatized articles according to the present invention are selected from the group consisting of extracts, eaux de perfume, eaux de toilette, after-shave lotions, eaux de Co- logne, pre-shave products, splash colognes, perfumed refreshing tissues, acidic, alkaline and neutral cleaning products, textile fresheners, ironing aids, liquid detergents, powder detergents, fabric preconditioners, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants, air purifiers, aerosol sprays, waxes and polishes, body care products, hand creams and lotions, foot creams and lotions, depila- tory creams and lotions, after-shave creams and lotions, tanning creams and lotions, treatment cosmetic products, hair care products, deodorants and antiperspirants, decorative cosmetic products, candles, lamp oils, incense sticks, insecticides, repellents and propellants.
  • Fragrance composition 1 has an intense and harmonious lily of the valley note with slightly less power than fragrance characteristics of pure 2-methyl-3-(4-tert.- butylphenyl) propanal (Lysmeral®, BASF SE).
  • Fragrance composition 2 has an intense and harmonious lily of the valley note indistinguishable from the fragrance characteristics of pure 2-methyl-3-(4-tert.-butylphenyl) propanal (Lysmeral®, BASF SE).
  • Example 3 Fragrance Composition 3:
  • Fragrance composition 3 has an intense and harmonious lily of the valley note indistin- guishable from the fragrance characteristics of pure 2-methyl-3-(4-tert.-butylphenyl) propanal (Lysmeral®, BASF SE).
  • Fragrance composition 4 has an intense and harmonious lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Total 100 Fragrance composition 5 has an intense and harmonious lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Fragrance composition 6 has an intense and harmonious lily of the valley note very similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Fragrance composition 7 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Example 8 Fragrance Composition 8:
  • Fragrance composition 8 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Fragrance composition 9 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Example 10 Fragrance Composition 10:
  • Fragrance composition 10 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
  • Fragrance composition 1 1 has an intense and harmonious lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Fragrance composition 12 has an intense and harmonious lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Fragrance composition 13 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Example 14 Fragrance Composition 14:
  • Fragrance composition 14 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Fragrance composition 15 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Fragrance composition 16 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
  • Fragrance composition 17 has an intense and powerful lily of the valley note very similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE)
  • Total 100 Fragrance composition 18 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
  • Fragrance composition 19 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
  • Fragrance composition 20 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
  • Example 21 Fragrance Composition 21 :
  • Fragrance composition 21 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
  • Fragrance composition 22 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
  • Total 100 Fragrance composition 23 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
  • Fragrance composition 24 has an intense and powerful lily of the valley note very simi- lar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE)
  • Fragrance composition 25 has an intense and powerful lily of the valley note very similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE)
  • Example 26 Fragrance Composition 26:
  • Fragrance composition 26 has an intense and powerful lily of the valley note very simi- lar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE)

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Abstract

The present invention relates perfume compositions of the lily of the valley-type comprising 2,5,7,7-tetramethyloctanal and 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol. The present invention further relates to a method for producing a perfumed product or article as well as perfumed or aromatized articles comprising the fragrance compositions of the present invention.

Description

Lily of the Valley-type Fragrance Compositions comprising 2,5,7,7-tetramethyloctanal
The present invention relates to fragrance compositions of the lily of the valley-type comprising 2,5,7,7-tetramethyloctanal (Lyrisal®) and 2-isobutyl-4-methyl-tetrahydro- 2H-pyran-4-ol. The present invention further relates to a method for producing a perfumed product or article as well as perfumed or aromatized articles comprising the fragrance compositions of the present invention.
Lily of the valley- or muguet-type fragrances are widely used and accepted in a large variety of consumer products such as for example detergents of all kind, washing soaps and hygiene and cosmetic products of all kinds. Blends or mixtures of those lily of the valley- or muguet-type fragrances (hereinafter referred to as "fragrance compositions") often contain the synthetic compound 2-methyl-3-(4-tert.-butylphenyl)propanal of formula (I)
Figure imgf000002_0001
also known under the tradenames Lysmeral® (BASF SE), Lilial® (Givaudan SA) and Lilestralis® (Innospec Inc.). Some of those product may also contain the meta- substituted isomer 2-methyl-3-(3-tert.-butylphenyl)propanal (CAS Registry Number 62518-65-4) of formula (II)
Figure imgf000002_0002
Due to more recent results and concerns about the allergenic and toxicologic potential of para-substituted dihydrocinnamaldehyde derivatives such as, for example, the compound of formula (I), there is a constant need for safe alternatives with fragrance characteristics very similar to those already accepted and expected by the consumer. EP 0 252 378 discloses aliphatic aldehydes and their use as fragrance ingredients. Specifically, 2,5,7,7-tetramethyloctanal is described as a valuable fragrance ingredient with an intense lily-of-the-valley note. Furthermore, a method for the preparation of the abovementioned aldehydes is disclosed comprising base catalyzed condensation of the corresponding precursor aldehydes followed by catalytic hydrogenation. EP 0 269 999 discloses the corresponding aliphatic alcohols and esters and their use as fragrance ingredients. Specifically, 2,5,7,7-tetramethyloctanol is described as a valuable fragrance ingredient with a flowery rose-like note. The document further discloses the preparation of 2,5,7,7-tetramethyloctanol by hydrogenation of the corresponding aldehyde 2,5,7,7-tetramethyloctanal.
EP 0 395 982 discloses beta, gamma-unsaturated nitriles, the preparation thereof and their use as scents. More specifically, 4,7,9,9-tetramethyl-dec-3-en-nitrile is disclosed as well as the preparation thereof by condensation of 2,5,7,7-tetramethyloctanal with cyanoacetic acid. The reaction product is described as having a waxy, floral and fresh fragrance note.
WO 2009/027957 discloses perfumes wherein the compound 2-methyl-3-(4-tert.- butylphenyl)propanal is replaced by other perfume raw materials in accordance with specific mass ratio replacement levels.
It was an object of the present invention to provide suitable fragrances or fragrance compositions with similar, preferable exchangeable fragrance characteristics to those of known lily of the valley- or muguet-type fragrances, especially of para- or meta- substituted dihydrocinnamaldehyde derivatives such as for example the compounds of formula (I) and/or (II). The fragrances or fragrance compositions should be readily accessible in technical quantities under economically favorable conditions.
The problem was surprisingly solved by the provision of a fragrance composition comprising a) 2,5,7,7-tetramethyloctanal and
b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol and
c) optionally one or more additional fragrance substance(s) and
d) optionally one or more diluent(s).
It was surprisingly found that the fragrance compositions of the present invention comprising 2,5,7,7-tetramethyloctanal of formula (III)
Figure imgf000003_0001
and 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV)
Figure imgf000004_0001
are very well suited as replacements for the established lily of the valley- or muguet- type fragrances of the para- and meta-substituted dihydrocinnamaldehyde type, espe- cially of 2-methyl-3-(4-tert.-butylphenyl)propanal of formula (I).
It was furthermore found that the combination of the known fragrances 2,5,7,7- tetramethyloctanal and 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol results in an unexpected synergistic effect. It was surprisingly found that the readily available 2- isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol enhances the fragrance characteristics of 2,5,7,7-tetramethyloctanal so that only minor amount of 2,5,7,7-tetramethyloctanal of formula (III) are necessary to evoke an odour very similar to that of Lysmeral®.
The fragrance compositions of the present invention comprise at least organoleptically active quantities of 2,5,7,7-tetramethyloctanal (CAS Registry Number 1 141 19-97-0) of formula (III)
Figure imgf000004_0002
as component a) and at least organoleptically active quantities of 2-isobutyl-4-methyl- tetrahydro-2H-pyran-4-ol (CAS Registry Number 63500-71 -0) of formula (IV)
Figure imgf000004_0003
as component b).
For the purposes of the present invention the compound 2,5,7,7-tetramethyloctanal of formula (III) may, if desired, be used in optically active or diastereomerically enriched form or in another preferred embodiment in form of a racemic mixture of diastereomers. 2,5,7,7-tetramethyloctanal of formula (III) may be synthesized in pure form, e.g. according to the route as described in EP 0 252 378 by base catalyzed condensation of 3,5,5- trimethylhexanal with propionic aldehyde and subsequent catalytic hydrogenation. The compound 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) may advantageously be used in form of a mixture of the respective diastereomers (cis/trans) both either in optically active or preferably in racemic form. 2-isobutyl-4-methyl- tetrahydro-2H-pyran-4-ol of formula (IV) is commercially available, e.g. under the trade names Florol® (Firmenich S.A.) and Florosa® (Givaudan S.A.) in form of dia- stereomeric mixtures and may be used as such.
In a preferred embodiment the fragrance compositions of the present invention comprise diastereomers of 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) with at least 62% of the cis form. In a more preferred embodiment the fragrance composi- tions of the present invention comprise diastereomers of 2-isobutyl-4-methyl- tetrahydro-2H-pyran-4-ol of formula (IV) having 65-95% of the cis form and 5-35% of the trans form, very preferred 70-80% cis form and 20-30% trans form.
The fragrance compositions of the present invention may also optionally comprise as component or components c) one or more additional fragrance substance(s). The fragrance compositions of the present invention may also optionally comprise as component or components d) one or more diluent(s). Furthermore, the fragrance compositions of the present invention may also optionally comprise further constituents known to those of skill in the art as common ingredients in fragrance compositions.
Examples of additional fragrance substances c) with which the fragrance compositions of the present invention can be combined advantageously can be found for example in S. Arctander, Perfume and Flavor Materials, Vol. I and 1 1 , Montclair, N.J., 1969, self- published, or in K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th Edition, Wiley-VCH, Weinheim 2001.
The fragrance compositions of the present invention can be combined with one or more individual fragrance substances known to those of skill in the art as additional fragrance substance c) or o as an additional component to be combined or mixed with the fin- ished fragrance composition, comprising but not limited to, for example, fragrances selected from the following groups: of hydrocarbons, such as, for example, 3-carene; alpha-pinene; beta-pinene; alpha- terpinene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene;
cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1 ,3,5- undecatriene; styrene; diphenylmethane; of aliphatic alcohols, such as, for example, hexanol; octanol; 3-octanol; 2,6- dimethylheptanol; 2-methyl-2-heptanol, 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)- 3-hexenol; 1 -octen-3-ol; mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6- tetramethyl-4-methylene heptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7- methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; of aliphatic aldehydes and acetals thereof, such as, for example, hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2- methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9- undecadienal;heptanal diethyl acetal; 1 ,1 -dimethoxy-2,2,5-trimethyl-4-hexene; citro- nellyl oxyacetaldehyde; 1 -(1 -methoxypropoxy)-(E/Z)-3-hexene; of aliphatic ketones and oximes thereof, such as, for example, 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; 6-methyl-5-hepten-2-one; of aliphatic sulfur-containing compounds, such as, for example, 3-methylthiohexanol; 3- methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3- mercaptohexylbutyrate; 3-acetylthiohexyl acetate; l-menthene-8-thiol; of aliphatic nitriles, such as, for example, 2-nonenenitrile; 2-undecenenitrile; 2- tridecenenitrile; 3,12-tridecadienenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl- 6-octenenitrile; 3,7-dimethyl-octanenitrile; of esters of aliphatic carboxylic acids, such as, for example, (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1 -octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl is- ovalerate; ethyl-2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl hep- tanoate; allyl heptanoate; ethyl octanoate; ethyl-(E,Z)-2,4-decadienoate; methyl-2- octynoate; methyl-2-nonynoate; allyl-2-isoamyloxyacetate; methyl-3,7-dimethyl-2,6- octadienoate; 4-methyl-2-pentyl crotonate; of acyclic terpene alcohols, such as, for example, citronellol; geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7- octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl- 5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-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; and formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, croto- nates, tiglinates and 3-methyl-2-butenoat.es thereof; of acyclic terpene aldehydes and ketones, such as, for example, geranial; neral; citron- ellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9- undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial, neral, 7- hydroxy-3,7-dimethyloctanal; of cyclic terpene alcohols, such as, for example, menthol; isopulegol; alpha-terpineol; terpinenol-4; menthan-8-ol; menthan-1 -ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol; guaiol; and formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoat.es thereof; of cyclic terpene aldehydes and ketones, such as, for example, menthone; isomen- thone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; alpha-ionone; beta- ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta- isomethylionone; alpha-irone; alphadamascone; beta-damascone; beta-damascenone; deltadamascone; gamma-damascone; 1 -(2,4,4-trimethyl-2-cyclohexen-1 -yl)-2-buten-1 - one; 1 ,3,4,6,7,8a-hexahydro-1 ,1 ,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)- one; 2-methyl-4-(2,6,6-trimethyl-1 -cyclohexen-1 -yl)-2-butenal; nootkatone; dihydro- nootkatone; 4,6,8-megastigmatrien-3-one; alpha-sinensal; beta-sinensal; acetylated cedarwood oil (methyl cedryl ketone); of cyclic alcohols, such as, for example, 4-tert-butylcyclohexanol; 3,3,5- trimethylcyclohexanol; 3 -isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9- cyclododecatrien-1 -ol, 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol; of cycloaliphatic alcohols, such as, for example, alpha-3,3-trimethyl- cyclohexylmethanol; 1 -(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3- cyclopent-1 -yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1 -yl)-2-buten-1 -ol; 2- ethyl-4-(2,2,3-trimethyl-3-cyclopent-1 -yl)-2-buten-1 -ol; 3-methyl-5-(2,2,3-trimethyl-3- cyclopent-1 -yl)-pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1 -yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1 -yl)-4-penten-2-ol; 1 -(2,2,6-trimethyl- cyclohexyl)pentan-3-ol; 1 -(2,2,6-trimethylcyclohexyl)hexan-3-ol; 4-isopropyl- cyclohexylmethanol; of cyclic and cycloaliphatic ethers, such as, for example, cineol; cedryl methyl ether; cyclododecyl methylether; 1 ,1 -dimethoxycyclododecane; (ethoxymethoxy)cyclodo- decane; alpha-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1 - b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1 -b]furan; 1 ,5,9-trimethyl-13- oxabicyclo[10.1 .0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1 -yl)-5- methyl-5-(1 -methylpropyl)-1 ,3-dioxane; of cyclic and macrocyclic ketones, such as, for example, 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentan- one; 2-hydroxy-3-methyl-2-cyclopenten-1 -one; 3-methyl-cis-2-penten-1 -yl-2- cyclopenten-1 -one; 3-methyl-2-pentyl-2-cyclopenten-1 -one; 3-methyl-4- cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4-(1 -ethoxyvinyl )-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5- cyclohexadecen-1 -one; 6,7-dihydro-1 ,1 ,2,3,3-pentamethyl-4(5H)-indanone; 8- cyclohexadecen-1 -one; 9-cycloheptadecen-1 -one; cyclopentadecanone; cyclohexa- decanone; of cycloaliphatic aldehydes, such as, for example, 2,4-dimethyl-3-cyclohexenecarb- aldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4- methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1 -yl)-3-cyclohexene- carbaldehyde; of cycloaliphatic ketones, such as, for example, 1 -(3,3-dimethylcyclohexyl)-4-penten-1 - one; 2,2-dimethyl-1 -(2,4-dimethyl-3-cyclohexen-1 -yl)-1 -propanone; 1 -(5,5-dimethyl-1 - cyclohexen-1 -yl)-4-penten-1 -one; 2,3,8,8-tetramethyl-1 ,2, 3,4,5,6, 7,8-octahydro-2- naphthalenyl methyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl-(2,4-dimethyl-3-cyclohexen-1 -yl) ketone; of esters of cyclic alcohols such as, for example, 2-tert-butylcyclohexyl acetate; 4-tert- butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentyl- cyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a- tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate; 4,7-methano- 3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate; 4,7-methanooctahydro-5 or 6- indenyl acetate; of esters of cycloaliphatic alcohols such as, for example, 1 -cyclohexylethyl crotonate; of esters of cycloaliphatic carboxylic acids, such as, for example, allyl-3-cyclohexyl propionate; allyl cyclohexyloxyacetate; cis- and trans-methyl dihydrojasmonate; cis- and trans-methyl jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl-2- ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl-2,3,6,6-tetramethyl-2- cyclohexenecarboxylate; ethyl-2-methyl-1 ,3-dioxolane-2-acetate; of araliphatic alcohols, such as, for example, benzyl alcohol; 1 -phenylethyl alcohol; 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-propen-1 -ol; 4- methoxybenzylalcohol; 1 -(4-isopropylphenyl)ethanol; of esters of araliphatic alcohols and aliphatic carboxylic acids, such as, for example, benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1 -phenylethyl acetate; alpha-trichloromethylbenzyl acetate; alpha, alpha- dimethylphenylethyl acetate; alpha, alpha-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; of araliphatic ethers, such as, for example, 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl-1 -ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydratropaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1 ,3-dioxane; 4,4a,5,9b-tetrahydro- indeno[1 ,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1 ,2-d]-m-dioxin; of aromatic and araliphatic aldehydes, such as, for example, benzaldehyde;
phenylacetaldehyde; 3-phenylpropanal; hydratropaldehyde; 3-(3-lsopropyl- phenyl)butanal, 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4- ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-
3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; alpha- butylcinnamaldehyde; alpha-amylcinnamaldehyde; silvial; alpha-hexylcinnamaldehyde;
3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3- methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4- methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4- methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal; of aromatic and araliphatic ketones, such as, for example, acetophenone; 4- methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1 -(2-naphthalenyl)ethanone; 2- benzofuranyl ethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone;
1 ,1 ,2,3,3,6-hexamethyl-5-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)-1 H-5- indenyl]ethanone; 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-acetonaphthone; of aromatic and araliphatic carboxylic acids and esters thereof, such as, for example, benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; pheuylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; ben- zyl salicylate; phenylethyl salicylate; methyl-2,4-dihydroxy-3,6-dimethylbenzoate; ethyl- 3-phenylglycidate; ethyl-3-methyl-3-phenylglycidate; of nitrogen-containing aromatic compounds, such as, for example, 2,4,6-trinitro-1 ,3- dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cin- namonitrile; 3-methyl-5-phenyl-2-pentenenitrile; 3-methyl-5-phenyl pentanenitrile;
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-cyclohexenecarbaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec- butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3- isopropylpyrazine; 2-isobutyl-3-methoxypyrazine; of phenols, phenyl ethers and phenyl esters, such as, for example, estragole; anethole; eugenol; eugenyl, methyl ether; isoeugenol; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthyl isobutyl ether; 1 ,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2- ethoxy-5-(1 -propenyl)phenol; p-cresyl phenylacetate; of heterocyclic compounds, such as, for example, 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; of lactones, such as, for example, 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; 4-methyl-1 ,4-decanolide; 1 ,15-pentadecanolide; cis- and trans-1 1 -pentadecen-1 ,15-olide; cis- and trans-12-pentadecen-1 ,15-olide;1 ,16- hexadecanolide; 9-hexadecen-1 ,16-olide; 10-oxa-1 ,16-hexadecanolide; 1 1 -oxa-1 ,16- hexadecanolide; 12-oxa-1 ,16-hexadecanolide; ethylene-1 ,12-dodecanedioate; ethyl- ene-1 ,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin.
Preferred fragrance substances c) according to the present invention are those, selected from the group of fragrance compounds consisting of 7-hydroxy-3,7- dimethyloctanal; 4-isopropyl-cyclohexylmethanol; limonene; hexanol; octanol; 3- octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenol; 3,7-dimethyl-6-octenenitrile; 3,7-dimethyl-octanenitrile; (E)- and (Z)-3-hexenyl formate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; citronellol; gera- niol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-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; gera- nial; neral; citronellal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7- dimethyloctanal; menthol; isopulegol; alpha-terpineol; terpinenol-4; menthan-8-ol; men- than-1 -ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol; guaiol; and formates, acetates, propionates, isobutyrates, butyrates, isovaler- ates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoat.es thereof; menthone; carvone; camphor; fenchone; alpha-ionone; beta-ionone; alpha-n- methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethylionone; alpha-irone; alpha-damascone; beta-damascone; beta-damascenone; delta- damascone; gamma-damascone; 1 -(2,4,4-trimethyl-2-cyclohexen-1 -yl)-2-buten-1 -one; 1 ,3,4,6,7,8a-hexahydro-1 ,1 ,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one; 2- methyl-4-(2,6,6-trimethyl-1 -cyclohexen-1 -yl)-2-butenal; nootkatone; dihydro- nootkatone; 4,6,8-megastigmatrien-3-one; alpha-sinensal; beta-sinensal; acetylated cedarwood oil (methyl cedryl ketone); 4-tert-butylcyclohexanol; 3,3,5- trimethylcyclohexanol; 3 -isocamphylcyclohexanol; alpha-3,3-trimethyl- cyclohexylmethanol; 1 -(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3- cyclopent-1 -yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1 -yl)-2-buten-1 -ol; 2- ethyl-4-(2,2,3-trimethyl-3-cyclopent-1 -yl)-2-buten-1 -ol; 3-methyl-5-(2,2,3-trimethyl-3- cyclopent-1 -yl)-pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1 -yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1 -yl)-4-penten-2-ol; 1 -(2,2,6-trimethyl- cyclohexyl)pentan-3-ol; 1 -(2,2,6-trimethylcyclohexyl)hexan-3-ol; 4-tert- butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentan-one; 2-hydroxy-3-methyl-2-cyclopenten-1 -one; 3-methyl-cis-2- penten-1 -yl-2-cyclopenten-1 -one; 3-methyl-2-pentyl-2-cyclopenten-1 -one; 3-methyl-4- cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4-(1 -ethoxyvinyl )-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5- cyclohexadecen-1 -one; 6,7-dihydro-1 ,1 ,2,3,3-pentamethyl-4(5H)-indanone; 8- cyclohexadecen-1 -one; 9-cycloheptadecen-1 -one; cyclopentadecanone; cyclohexa- decanone; 2,4-dimethyl-3-cyclohexenecarb-aldehyde; 2-methyl-4-(2,2,6- trimethylcyclohexen-1 -yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3- cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1 -yl)-3-cyclohexene-carbaldehyde; 1 - (3,3-dimethylcyclohexyl)-4-penten-1 -one; 2,2-dimethyl-1 -(2,4-dimethyl-3-cyclohexen-1 - yl)-1 -propanone; 1 -(5,5-dimethyl-1 -cyclohexen-1 -yl)-4-penten-1 -one; 2,3,8,8- tetramethyl-1 ,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; methyl-2,6,10- trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl-(2,4-dimethyl-3-cyclohexen-1 -yl) ketone; 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert- pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentyl-cyclopentyl crotonate; 3- pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methano- 3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a- hexahydro-5 or 6-indenyl isobutyrate; 4,7-methanooctahydro-5 or 6-indenyl acetate; benzyl alcohol; 1 -phenylethyl alcohol; 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-propen-1 -ol; 4-methoxybenzylalcohol; 1 -(4- isopropylphenyl)ethanol; benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; benzaldehyde;
phenylacetaldehyde; 3-phenylpropanal; hydratropaldehyde; 4-methylbenzaldehyde; 4- methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4- isopropylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert- butylphenyl)propanal; cinnamaldehyde; alpha-butylcinnamaldehyde; alpha- amylcinnamaldehyde; alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4- methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3- ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal; acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6- dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1 -(2- naphthalenyl)ethanone; 2-benzofuranyl ethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1 ,1 ,2,3,3,6-hexamethyl-5-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)- 1 H-5-indenyl]ethanone; estragole; anethole; eugenol; iso-eugenol; thymol; 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; 4-methyl- 1 ,4-decanolide; 1 ,15-pentadecanolide; cis- and trans- 1 1 -pentadecen-1 ,15-olide; cis- and trans-12-pentadecen-1 ,15-olide;1 ,16-hexadecanolide; 9-hexadecen-1 ,16-olide; 10-oxa-1 ,16-hexadecanolide; 1 1 -oxa-1 ,16-hexadecanolide; 12-oxa-1 ,16- hexadecanolide; ethylene-1 ,12-dodecanedioate; ethylene-1 ,13-tridecanedioate; cou- marin; 2,3-dihydrocoumarin and octahydrocoumarin.
In a preferred embodiment the fragrance compositions of the present invention comprise one or more, usually 1 to 20, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3 and most preferably 1 or 2 additional fragrance substances selected from the group of fragrance listed above, whereas the fragrance substances 7-hydroxy-3,7- dimethyloctanal and 4-isopropyl-cyclohexylmethanol are particularly preferred fragrance substances c) comprised by the fragrance compositions of the present inven- tion.
Particularly preferred fragrance compositions of the present invention are those comprising 7-hydroxy-3,7-dimethyloctanal (Hydroxycitronellal, CAS Registry Number 107- 75-5) of formula (V)
Figure imgf000012_0001
as additional fragrance substance c).
Further particularly preferred fragrance compositions of the present invention are those comprising 4-isopropyl-cyclohexylmethanol (4-(1 -methylethyl)-cyclohexanemethanol); CAS Registry Number 13828-37-0) of formula (VI)
Figure imgf000013_0001
as additional fragrance substance c). The compounds 7-hydroxy-3,7-dimethyloctanal of formula (V) and 4-isopropyl-cyclohexylmethanol of formula (VI) are known and commercially widely available e.g. as Mayol® (Firmenich SA), Meijiff™ (International Flavors & Fragrances Inc.) or may be synthesized by known methods. Further particularly preferred fragrance compositions of the present invention are those comprising 2,6-dimethylheptan-2-ol (CAS Registry Number 13254-34-7) of formula (VII)
Figure imgf000013_0002
as additional fragrance substance c).
Further particularly preferred fragrance compositions of the present invention are those comprising 3,7-dimethyl-octan-1 ,7-diol (Hydroxycitronellol; CAS Registry Number 107- 74-4) of formula (VIII)
Figure imgf000013_0003
as additional fragrance substance c).
Further particularly preferred fragrance compositions of the present invention are those comprising 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal; CAS Registry Number 30168-23-1 ) of formula (IX),
Figure imgf000014_0001
as additional fragrance substance c). The compound 4-(Octahydro-4,7-methano-5H- inden-5-yliden)butanal is commercially available as Dupical® (Givaudan).
Further particularly preferred fragrance compositions of the present invention are those comprising the compounds 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde of formula (X) and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde of formula (XI) (CAS Registry Number 31906-04-4 and 51414-25-6 respectively),
Figure imgf000014_0002
Figure imgf000014_0003
as additional fragrance substance(s) c). The compounds 4-(4-Hydroxy-4-methylpentyl)- 3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde are commercially available as a 70:30 mixture under tradenames Kovanol® (Takasago) or Lyral® (International Flavors & Fragrances Inc.).
In a particularly preferred embodiment the fragrance compositions of the present invention comprise or substantially consist of or consist of the components
a) 2,5,7,7-tetramethyloctanal of formula (III) and
b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) and
c) 7-hydroxy-3,7-dimethyloctanal of formula (V) and/or 4-isopropyl- cyclohexylmethanol of formula (VI) and optionally one or more additional fragrance substance(s) and
d) optionally one or more diluent(s). In another preferred embodiment the fragrance compositions of the present invention comprise or (substantially) consist of the components
a) 2,5,7,7-tetramethyloctanal of formula (III) and b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) and
c) 7-hydroxy-3,7-dimethyloctanal of formula (V) and 4-isopropyl- cyclohexylmethanol of formula (VI) and optionally one or more additional fragrance substance(s) and
d) optionally one or more diluent(s).
In yet another more preferred embodiment the fragrance compositions of the present invention comprise or (substantially) consist of the components
a) 2,5,7,7-tetramethyloctanal of formula (III) and
b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) and
c) 7-hydroxy-3,7-dimethyloctanal of formula (V) and/or 2,6-dimethylheptan-2-ol of formula (VII) and optionally one or more additional fragrance substance(s) and d) optionally one or more diluent(s). In yet another even more preferred embodiment the fragrance compositions of the present invention comprise or (substantially) consist of the components
a) 2,5,7,7-tetramethyloctanal of formula (III) and
b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) and
c) 7-hydroxy-3,7-dimethyloctanal of formula (V) and/or 3,7-dimethyl-octan-1 ,7-diol of formula (VIII) and optionally one or more additional fragrance substance(s) and
d) optionally one or more diluent(s).
In yet another preferred embodiment the fragrance compositions of the present inven- tion comprise or (substantially) consist of the components
a) 2,5,7,7-tetramethyloctanal of formula (III) and
b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) and
c) 7-hydroxy-3,7-dimethyloctanal of formula (V) and 2,6-dimethylheptan-2-ol of formula (VII) and optionally one or more additional fragrance substance(s) and d) optionally one or more diluent(s).
In yet another even more preferred embodiment the fragrance compositions of the present invention comprise or (substantially) consist of the components
a) 2,5,7,7-tetramethyloctanal of formula (III) and
b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) and
c) 7-hydroxy-3,7-dimethyloctanal of formula (V) and 2,6-dimethylheptan-2-ol of formula (VII) and 3, 7-dimethyl-octan-1 ,7-diol of formula (VIII) and optionally one or more additional fragrance substance(s) and
d) optionally one or more diluent(s).
In yet another even more preferred embodiment the fragrance compositions of the present invention comprise or consist of the components a) 2,5,7,7-tetramethyloctanal of formula (III) and
b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) and
c) 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal of formula (IX) and optionally one or more additional fragrance substance(s) and
d) optionally one or more diluent(s).
In yet another even more preferred embodiment the fragrance compositions of the pre sent invention comprise or consist of the components
a) 2,5,7,7-tetramethyloctanal of formula (III) and
b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) and
c) 7-hydroxy-3,7-dimethyloctanal of formula (V) and 2,6-dimethylheptan-2-ol of formula (VII) and/or 3, 7-dimethyl-octan-1 ,7-diol of formula (VIII) and/or 4- (Octahydro-4,7-methano-5H-inden-5-yliden)butanal of formula (IX) and optionally one or more additional fragrance substance(s) and
d) optionally one or more diluent(s).
In yet another even more preferred embodiment the fragrance compositions of the pre sent invention comprise or consist of the components
a) 2,5,7,7-tetramethyloctanal of formula (III) and
b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) and
c) 7-hydroxy-3,7-dimethyloctanal of formula (V) and 2,6-dimethylheptan-2-ol of formula (VII) and/or 3, 7-dimethyl-octan-1 ,7-diol of formula (VIII) and/or 4- (Octahydro-4,7-methano-5H-inden-5-yliden)butanal of formula (IX) and/or 4-(4- Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde of formula (X) and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde of formula (XI) and optionally one or more additional fragrance substance(s) and
d) optionally one or more diluent(s).
In yet an especially preferred embodiment the fragrance compositions of the present invention comprise or consist of the components
a) 2,5,7,7-tetramethyloctanal of formula (III) and
b) 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol of formula (IV) and
c) 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal of formula (IX) and/or 4- (4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde of formula (X) d) optionally one or more diluents.
For the purposes of the above-mentioned preferred embodiments the term "additional fragrance substances" means one or more, usually 1 to 20, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3 and most preferably 1 or 2 additional fragrance substances selected from the group of fragrance substances c) listed above other than 7-hydroxy- 3,7-dimethyloctanal and 4-isopropyl-cyclohexylmethanol and 4-(Octahydro-4,7- methano-5H-inden-5-yliden)butanal and 2,6-dimethylheptan-2-ol and 3,7-dimethyl- octan-1 ,7-diol and 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde. In the fragrance compositions according to the present invention the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 2-isobutyl-4- methyl-tetrahydro-2H-pyran-4-ol may generally be varied within a broad range. Preferably the weight-based ratio of the total amount 2,5,7,7-tetramethyloctanal to the total amount of 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol in the finished fragrance com- position ranges from about 100:1 to about 1 :100, more preferably from 50:1 to 1 :50, more preferably from 30:1 to 1 :30, more preferably from 20:1 to 1 :20, more preferably from 10:1 to 1 :10 and most preferably from 5:1 to 1 :5.
In the preferred fragrance compositions according to the present invention comprising 2,6-dimethylheptan-2-ol as additional fragrance substance the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 2,6-dimethylheptan-2- ol may also generally be varied within a broad range. Preferably the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 2,6- dimethylheptan-2-ol in the finished fragrance composition ranges from about 50:1 to about 1 :50, more preferably from 20:1 to 1 :10, more preferably from 20:1 to 1 :1 , and most preferably from 10:1 to 1 :1.
In the preferred fragrance compositions according to the present invention comprising 3, 7-dimethyl-octan-1 ,7-diol as additional fragrance substance the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 3,7-dimethyl-octan- 1 ,7-diol may also generally be varied within a broad range. Preferably the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 3,7- dimethyl-octan-1 ,7-diol in the finished fragrance composition ranges from about 1 :30 to about 30:1 , more preferably from 10:1 to 1 :10, more preferably from 5:1 to 1 :5, and most preferably from 3:1 to 1 :3.
In the preferred fragrance compositions according to the present invention comprising 7-hydroxy-3,7-dimethyloctanal as additional fragrance substance c) the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 7-hydroxy- 3,7-dimethyloctanal may also generally be varied within a broad range. Preferably the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 7-hydroxy-3,7-dimethyloctanal in the finished fragrance composition ranges from about 30:1 to about 1 :30, more preferably from 10:1 to 1 :10, more preferably from 5:1 to 1 :5 and most preferably from 3:1 to 1 :3.
In the preferred fragrance compositions according to the present invention comprising 4-isopropyl-cyclohexylmethanol as additional fragrance substance c) the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-isopropyl- cyclohexylmethanol may also generally be varied within a broad range. Preferably the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-isopropyl-cyclohexylmethanol in the finished fragrance composition ranges from about 30:1 to about 1 :30, more preferably from 20:1 to 1 :10, more preferably from 15:1 to 1 :1 , more preferably from 10:1 to 1 :1 and most preferably from 5:1 to 1 :1.
In the fragrance compositions according to the present invention the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-(Octahydro- 4,7-methano-5H-inden-5-yliden)butanal may generally be varied within a broad range. Preferably the weight-based ratio of the total amount 2,5,7,7-tetramethyloctanal to the total amount of 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal in the finished fragrance composition ranges from about 100:1 to about 1 :100, more preferably from 50:1 to 1 :50, more preferably from 30:1 to 1 :30, more preferably from 20:1 to 1 :20, more preferably from 10:1 to 1 :10 and most preferably from 5:1 to 1 :5.
In the fragrance compositions according to the present invention the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3- cyclohexen-1 -carboxaldehyde may generally be varied within a broad range. Preferably the weight-based ratio of the total amount 2,5,7,7-tetramethyloctanal to the total amount of 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4- Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde in the finished fragrance composition ranges from about 100:1 to about 1 :100, more preferably from 50:1 to 1 :50, more preferably from 30:1 to 1 :30, more preferably from 20:1 to 1 :20, more preferably from 10:1 to 1 :10 and most preferably from 5:1 to 1 :5.
The fragrance compositions according to the present invention comprise at least or- ganoleptically active quantities of the named ingredients 2,5,7,7-tetramethyloctanal and 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol and, if present, of the optional further fragrance substances 7-hydroxy-3,7-dimethyloctanal and/or 4-isopropyl- cyclohexylmethanol and, if present of the optional further fragrance substances, preferably 2,6-dimethylheptan-2-ol and/or 3,7-dimethyl-octan-1 ,7-diol. The term "or- ganoleptically active amount" as used herein means an amount sufficient to stimulate an olfactorial impression in a human being, especially the olfactorial impression of a typical lily of the valley- or muguet-type scent.
In the case of the fragrance substances of the present invention, especially in the case of those comprising 2,5,7,7-tetramethyloctanal and 2-isobutyl-4-methyl-tetrahydro-2H- pyran-4-ol and 7-hydroxy-3,7-dimethyloctanal and 4-isopropyl-cyclohexylmethanol generally only minor amounts or concentrations are necessary to generate the desired lily of the valley- or muguet-type fragrance. In the case of the preferred fragrance substances of the present invention, especially in the case of those comprising 2, 5, 7, 7-tetramethyloctanal and 2-isobutyl-4-methyl- tetrahydro-2H-pyran-4-ol and 7-hydroxy-3,7-dimethyloctanal and 4-isopropyl- cyclohexylmethanol and 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal and 4- (4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 -carboxaldehyde also generally only minor amounts or concentrations are necessary to generate the desired substantive lily of the valley- or muguet-type fragrance.
In the case of the especially preferred fragrance substances of the present invention, especially in the case of those comprising 2, 5, 7, 7-tetramethyloctanal and 2-isobutyl-4- methyl-tetrahydro-2H-pyran-4-ol and 4-(Octahydro-4,7-methano-5H-inden-5- yliden)butanal and optionally 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde also generally only minor amounts or concentrations are necessary to generate the desired substantive lily of the valley- or muguet-type fragrance.
The absolute content of the named ingredients 2, 5, 7, 7-tetramethyloctanal and 2- isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol and, if present, of the optional further fragrance substances 7-hydroxy-3,7-dimethyloctanal and/or 4-isopropyl-cyclohexyl- methanol and, if present of the optional further fragrance substances, preferably 2,6- dimethylheptan-2-ol and/or 3,7-dimethyl-octan-1 ,7-diol and/or 4-(Octahydro-4,7- methano-5H-inden-5-yliden)butanal and 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde in the fragrance compositions of the present invention, based on the total amount of the fragrance composition, may be varied within broad ranges. Preferred compositions of the present invention comprise or consist of, based on the total amount of the finished composition, a total amount of 2, 5, 7, 7-tetramethyloctanal in the range from about 0,1 to 95 wt.%, preferably from about 0,1 to 90 wt.%, more preferably from 0,1 to 50 wt.%, more preferably from 0,1 to 30 wt.%, more preferably from 0,1 to 20 wt.%, more preferably from 0,1 to 15 wt.%, more preferably from 0,2 to 10 wt.%, even more preferably from 0,5 to 10 wt.% and most preferably in the range from 1 to 5 wt.%.
Further more preferred compositions of the present invention comprise or consist of, based on the total amount of the finished composition, a total amount of 2,5,7,7- tetramethyloctanal in the range from about 15 to 90 wt.%, preferably from about 30 to 80 wt.%, more preferably from 50 to 70 wt.%. Preferred compositions of the present invention comprise or consist of, based on the total amount of the finished composition, a total amount of 2-isobutyl-4-methyl- tetrahydro-2H-pyran-4-ol in the range from about 0,1 to 95 wt.%, preferably from about 0,1 to 90 wt.%, more preferably from 1 to 90 wt.%, more preferably from 1 to 70 wt.%, more preferably from 5 to 50 wt.%, more preferably from 10 to 50 wt.%, even more preferably from 10 to 40 wt.% and most preferably in the range from 20 to 30 wt.%.
Further more preferred compositions of the present invention comprise or consist of, based on the total amount of the finished composition, a total amount of 2-isobutyl-4- methyl-tetrahydro-2H-pyran-4-ol in the range from about 5 to 80 wt.%, preferably from about 10 to 60 wt.%, more preferably from 15 to 45 wt.%.
Those preferred compositions of the present invention comprising 7-hydroxy-3,7- dimethyloctanal comprise or consist of, based on the total amount of the finished com- position, a total amount of 7-hydroxy-3,7-dimethyloctanal in the range of up to 30 wt.%, preferably from 0,1 to 30 wt.%, more preferably from 0,5 to 25 wt.%, more preferably from 1 to 20 wt.%, even more preferably from 1 to 10 wt.% and most preferably in the range from 2 to 4 wt.%. Small amounts of 4-isopropyl-cyclohexylmethanol, if at all, may be necessary to optimize the desired lily of the valley- or muguet-type scent of the fragrance compositions of the present invention into direction of olfactorial identity with Lysmeral®.
Those preferred compositions of the present invention comprising 4-isopropyl- cyclohexylmethanol comprise or consist of, based on the total amount of the finished composition, a total amount of 4-isopropyl-cyclohexylmethanol in the range of up to 30 wt.%, preferably from 0,01 to 30 wt.%, more preferably from 0,1 to 20 wt.%, more preferably from 0,1 to 10 wt.%, even more preferably from 0,1 to 5 wt.% and most preferably in the range from 0,1 to 2,5 or even to 1 wt.%.
Small amounts of 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal, if at all, may be necessary to optimize the desired lily of the valley- or muguet-type scent of the fragrance compositions of the present invention into direction of identity with Lysmeral®. Those preferred compositions of the present invention comprising 4-(Octahydro-4,7- methano-5H-inden-5-yliden)butanal comprise or consist of, based on the total amount of the finished composition, a total amount of 4-(Octahydro-4,7-methano-5H-inden-5- yliden)butanal in the range of up to 30 wt.%, preferably from 0,01 to 30 wt.%, more preferably from 0,1 to 20 wt.%, more preferably from 0,1 to 10 wt.%, even more pref- erably from 0,1 to 5 wt.% and most preferably in the range from 0,1 to 2,5 or even to 1 wt.%. Those especially preferred compositions of the present invention comprising 4- (Octahydro-4,7-methano-5H-inden-5-yliden)butanal comprise or consist of, based on the total amount of the finished composition, a total amount of 4-(Octahydro-4,7- methano-5H-inden-5-yliden)butanal in the range of up to 5 wt.%, preferably from 0,01 to 3 wt.%, more preferably from 0,1 to 1 wt.%, more preferably from 0,1 to 0,8 wt.%.
Small amounts of 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde, if at all, may be neces- sary to optimize the desired lily of the valley- or muguet-type scent of the fragrance compositions of the present invention into direction of identity with Lysmeral®.
Those preferred compositions of the present invention comprising 4-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3- cyclohexen-1 -carboxaldehyde comprise or consist of, based on the total amount of the finished composition, a total amount of 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde in the range of up to 30 wt.%, preferably from 0,01 to 30 wt.%, more preferably from 0,1 to 20 wt.%, more preferably from 0,1 to 10 wt.%, even more preferably from 0,1 to 5 wt.% and most preferably in the range from 0,1 to 2,5 or even to 1 wt.%.
Those especially preferred compositions of the present invention comprising 4-(4- Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 -carboxaldehyde comprise or consist of, based on the total amount of the finished composition, a total amount of 4-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3- cyclohexen-1 -carboxaldehyde in the range of up to 10 wt.%, preferably from 0,01 to 8 wt.%, more preferably from 0,1 to 5 wt.%, more preferably from 0,1 to 2.5 wt.%. The perfume compositions of the present invention do preferably not contain significant amounts of 2-methyl-3-(4-tert.-butylphenyl)propanal (the para-substituted compound of formula (I)). Preferably the weight-based ratio of 2-methyl-3-(3-tert.- butylphenyl)propanal to 2-methyl-3-(4-tert.-butylphenyl)propanal, if present at all, in the finished perfume composition ranges from over 10000:1 or higher to 50:1 , preferably from 10000:1 to 100:1 .
In a particularly preferred embodiment the fragrance compositions of the present invention comprise, based on the total amount of the finished composition, a total amount of 2-methyl-3-(4-tert.-butylphenyl)propanal of 1 wt.% or less, preferably of 0,5 wt.% or less, more preferably of 0,1 wt.% or less, more preferably of 0,05 wt.% or less and most preferably of 0,01 wt.% or less. In a even more preferred embodiment the fragrance compositions of the present invention are substantially free of 2-methyl-3-(4- tert.-butylphenyl)propanal of formula (I), meaning that it comprises based on the total amount of the finished composition, a total amount of 2-methyl-3-(4-tert.-butylphenyl) propanal of 0,005 wt.% or less, preferably of 0,001 wt.% or less. The fragrance compositions of the present invention may optionally comprise as component d) one or more diluent(s). The expression "one or more diluent(s)" means that one diluent or a mixture of two or more diluents may be present in fragrance compositions. The term "diluent" means a substance known to those of skill in the art as a suiable solvent for perfume or fragrance compositions such as, e.g. an alcohol such as ethanol or isopropanol and/or a polyol or an ether derived thereof such as diethylene glycol monoethyl ether, glycerol, propylene glycol, 1 ,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, dialkyl esters of 1 ,2- cyclohexanedicarboxylic acid, especially 1 ,2-cyclohexanedicarboxylic acid diisononyl ester (Hexamoll® DINCH, BASF SE) or and the like. Therefore, particularly preferred fragrance compositions according to the present invention comprise one or more diluents) d) selected from the group consisting of diethylene glycol monoethyl ether, glycerol, propylene glycol, 1 ,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate and dialkyl esters of 1 ,2-cyclohexanedicarboxylic acid, especially 1 ,2-cyclohexanedicarboxylic acid diisononyl ester.
The components of the fragrance compositions according to the present invention, namely 2,5,7,7-tetramethyloctanal and 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol and, if present, of the optional further fragrance substances 7-hydroxy-3,7- dimethyloctanal and/or 4-isopropyl-cyclohexylmethanol and, if present other optional further fragrance substances, preferably 2,6-dimethylheptan-2-ol and/or 3,7-dimethyl- octan-1 ,7-diol and/or 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal as well as the diluent(s), if present, may be blended or mixed by conventional techniques known to those of skill in the art.
Exemplary fragrance compositions according to the present invention may comprise, based on the total amount of the composition, e.g.:
2,5,7,7-tetramethyloctanal: 10 - 90 wt.%
2-lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol: 10 - 90 wt.%
7-Hydroxy-3,7-dimethyloctanal: 0 - 10 wt.%
4-lsopropyl-cyclohexylmethanol: 0 - 1 wt.%
Diluent: 0 - 80 wt.% or more preferred
2,5,7,7-tetramethyloctanal: 10 - 50 wt.%
2-lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol: 10 - 70 wt.% 7-Hydroxy-3,7-dimethyloctanal: 1 - 5 wt.%
4-lsopropyl-cyclohexylmethanol: 0 - 1 wt.%
Diluent: 0 - 79 wt.% or even more preferred:
2,5,7,7-tetramethyloctanal: 20 - 70 wt.%
2-lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol: 20 - 70 wt.%
7-Hydroxy-3,7-dimethyloctanal: 2 - 7 wt.%
4-lsopropyl-cyclohexylmethanol: 0 - 1 wt.%
Diluent: 0 - 58 wt.%.
Particularly preferred fragrance compositions according to the present invention may comprise, based on the total amount of the composition, e.g.
2,5,7,7-tetramethyloctanal: 20- 70 wt.%
2_lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol: 20 - 70 wt.%
7-Hydroxy-3,7-dimethyloctanal: 1 - 5 wt.%
2.6- dimethylheptan-2-ol: 0 - 2 wt.%
3.7- dimethyl-octan-1 ,7-diol: 5 - 50 wt.%
4-lsopropyl-cyclohexylmethanol: 0 - 1 wt.%
Diluent: 0 - 54 wt.% or even more preferred
2,5,7,7-tetramethyloctanal: 30- 70 wt.%
2-lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol: 20 - 70 wt.%
7-Hydroxy-3,7-dimethyloctanal: 1 - 5 wt.%
2.6- dimethylheptan-2-ol: 0 - 1 wt.%
3.7- dimethyl-octan-1 ,7-diol: 5 - 25 wt.%
4-lsopropyl-cyclohexylmethanol: 0 - 1 wt.%
Diluent: 0 - 44 wt.% or even more preferred
2,5,7,7-tetramethyloctanal: 30 - 70 wt.%
2-lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol: 20 - 70 wt.%
7-Hydroxy-3,7-dimethyloctanal: 2 - 5 wt.%
2.6- dimethylheptan-2-ol: 0 - 1 wt.%
3.7- dimethyl-octan-1 ,7-diol: 5 - 20 wt.%
4-lsopropyl-cyclohexylmethanol: 0 - 43 wt.%
4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal: 0 - 5 wt.% Diluent: 0-43wt.% or even more preferred 2,5,7,7-tetramethyloctanal: 30-70 wt.%
2-lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol: 20 - 70 wt.% 7-Hydroxy-3,7-dimethyloctanal: 2-5 wt.%
2.6- dimethylheptan-2-ol: 0 - 1 wt.%
3.7- dimethyl-octan-1 ,7-diol: 5 -10 wt.% 4-lsopropyl-cyclohexylmethanol: 0 - 1 wt.%
4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal 0-5 wt.% Diluent: 0-43 wt.% or even more preferred
2,5,7,7-Tetramethyloctanal: 30 -70 wt.%
2-lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol: 30-50 wt.%
7-Hydroxy-3,7-dimethyloctanal: 2-5 wt.%
2,6-dimethylheptan-2-ol: 0 - 1 wt.% 3, 7-dimethyl-octan-1 ,7-diol: 5 -10 wt.%
4-lsopropyl-cyclohexylmethanol: 0 - 1 wt.%
4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal 0-3 wt.%
4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1- carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)- 3-cyclohexen-1 -carboxaldehyde: 0-10wt. %
Diluent: 0-33 wt.% or even more preferred 2,5,7,7-Tetramethyloctanal: 50 -70 wt.%
2- lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol: 10-30 wt.% 7-Hydroxy-3,7-dimethyloctanal: 2-5 wt.%
2.6- dimethylheptan-2-ol 0 - 1 wt.%
3.7- dimethyl-octan-1 ,7-diol 0-10 wt.% 4-lsopropyl-cyclohexylmethanol : 0 - 1 wt.%
4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal 0-5 wt.% 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1- carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-
3- cyclohexen-1 -carboxaldehyde: 0 - 5 wt. % Diluent: 0-38 wt.% or even more preferred
2,5,7,7-Tetramethyloctanal: 50 - 70 wt.%
2-lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol: 20 - 40 wt.%
4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal: 0 - 1 wt.%
4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 - carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)- 3-cyclohexen-1 -carboxaldehyde: 0 - 5 wt. %
Diluent: 0 - 15 wt.%
The fragrance compositions of the present invention can also be combined with extracts of natural raw materials such as essential oils, concretes, absolutes, resins, resi- noids, balsams, tinctures and the like known to those of skill in the art, comprising but not limited to, for example:
Ambergris tincture; amyris oil; angelica seed oil; angelica root oil; aniseed oil; valerian oil; basil oil; treemoss absolute; bay oil; mugwort oil; benzoin resin; bergamot oil;
beeswax absolute; birch tar oil; bitter almond oil; savory oil; buchu leaf oil; cabreuva oil; cade oil; calamus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassie absolute; castoreum absolute; cedar leaf oil; cedarwood oil; cistus oil; citronella oil; citrus oil; copaiba balsam; copaiba balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill weed oil; dill seed oil; eau de brouts absolute; oakmoss absolute; elemi oil; tarragon oil; eucalyptus citriodora oil; eucalyptus oil; fennel oil; spruce needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; iris root absolute; iris root oil; jasmine absolute; calamus oil; camomile blue oil; camomile Roman oil; carrot seed oil; cascarilla oil; pine needle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavandin absolute; lavandin oil; lavender absolute; lavender oil; lemongrass oil; lovage oil; distilled lime oil; pressed lime oil; linaloe oil; litsea cubeba oil; bayleaf oil; mace oil; marjoram oil; mandarin oil; massoi bark oil; mimosa absolute; musk seed oil; musk tincture; clary sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove flower oil; neroli oil; olibanum absolute; olibanum oil; opopanax oil; orange flower absolute; orange oil; origanum oil; palmarosa oil; patchouli oil; perilla oil; Peru balsam oil; parsley leaf oil; parsley seed oil; petitgrain oil; peppermint oil; pepper oil; pimento oil; pine oil; pennyroyal oil; rose absolute; rosewood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil; star anise oil; styrax oil; tagetes oil; fir needle oil; tea-tree oil; turpentine oil; thyme oil; tolu balsam; tonka absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper beny oil; cognac oil; wormwood oil; wintergreen oil; ylang-ylang oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil and fractions thereof, or ingredients isolated therefrom. The fragrance compositions of the present invention can also be combined with antioxidants (stabilizers) known to those of skill in the art, comprising but not limited to, for example: phenolic antioxidants such as sodium salicylate, 2,4-dihydroxybenzophenone, 2,6-di-t- butyl-p-cresol, butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4-methylphenol (BHT), 2,6-di-t-butyl-4-ethylphenol, stearyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, propyl 3,4,5-trihydroxybenzoate, hydroquinone, and catechol; bisphenolic antioxidants such as 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'- methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'- butylidenebis(3-methyl-6-t-butylphenol) 3,9-bis[1 ,1-dimethyl-2-[3-(3-t-butyl-4-hydroxy-5- methylphenyl)propionyloxy]ethyl]2,4,8,IO-tetraoxaspiro[5,5]undecane, and 4,4'-(2,3- dimethyltetramethylene)dipyrrocatechol; high-molecular phenolic antioxidants such as 1 ,1 ,3-tris(2-methyl-4-hydroxy-5-t- butylphenyl)butane, 1 ,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'- bis-(4'-hydroxy-3'-t-butylpheny1 )butyric acid]glycol ester, 1 ,3,5-tris(3',5'-di-t-butyl-4'- hydroxybenzyl)-s-triazine-2,4,6-(1 H,3H,5H)trione, and alpha-tocopherol; tocotrienols and their esters; alcoholic antioxidants such as erythorbic acid, sodium erythorbat and isopropyl citrate; as well as ascorbic acid and its esters, especially ascorbyl palmitate; and other anti-oxidants such as N-aspartylphenylalanin alkyl ester, eugenol oi- soeugenol, quercetin7,4-dimethoxy-5-hydroxy-flavone, gallic acid, chlorogenic acid, dihydro-norguajaretic acid (NDGA), caffeic acid.
Further, the fragrance compositions of the present invention may contain the usual amounts of fixatives known to those of skill in the art. Preferred fixative for the use in the fragrance compositions of the present invention include but are not limited to sandalwood, ambra products, polycyclic, macrocyclic and alicyclic substances like Am- brox® (Firmenich SA), Galaxolide® (Int. Flavors & Fragrances Inc.), Tonalide, Exalto- lide® (Firmenich SA), Habanolide® (Firmenich SA) und Helvetolide® (Firmenich SA).
The fragrance compositions of the present invention can also comprise encapsulating substances like cyclodextrines; chelating and complexing agents like EDTA or citric acid. The fragrance compositions of the present invention may advantageously used for em- parting and/or enhancing an odor or flavor of a product or article of all kind with a lily of the valley- or muguet-type note or with a syringa-type note, a magnolia-type note, a cyclamen-type note or a hyacinth-type note, preferably with a lily of the valley- or muguet-type note. A further embodiment of the present invention therefore relates to a method for emparting and/or enhancing an odor or flavor of a product or article with a lily of the valley- or muguet-type note or with a syringa-type note, a magnolia-type note, a cyclamen-type note, a hyacinth-type note or a lilac-type note, preferably with a lily of the valley- or muguet-type note, comprising bringing into contact or mixing with or add- ing to said product or article an organoleptically active quantity of a fragrance composition according to the present invention whereas the term "organoleptically active quantity" has the meaning as defined above. The fragrance compositions of the present invention may be used or applied in every suited form e.g. in pure form or in form of dilutions or mixtures as well as in microencapsulated form.
Therefore, a further embodiment of the present invention relates to a method for producing a perfumed product or article comprising bringing into contact or mixing with or adding to said product or article an organoleptically active quantity of the fragrance composition according to the present invention.
In yet a further embodiment the present invention relates to a perfumed or aromatized product or article comprising an organoleptically active quantity of the fragrance composition according to the present invention as hereinbefore described. The perfumed or aromatized articles or products accessible by the present invention may be a perfumed or aromatized article of manufacture of all kind. Preferred aromatized or perfumed articles or products comprise, but are not limited to, e.g. perfumes, detergents and washing soaps, both liquid and solid and toilet articles of all kinds. Preferred perfumed or aromatized articles according to the present invention are selected from the group consisting of extracts, eaux de parfum, eaux de toilette, after-shave lotions, eaux de Co- logne, pre-shave products, splash colognes, perfumed refreshing tissues, acidic, alkaline and neutral cleaning products, textile fresheners, ironing aids, liquid detergents, powder detergents, fabric preconditioners, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants, air purifiers, aerosol sprays, waxes and polishes, body care products, hand creams and lotions, foot creams and lotions, depila- tory creams and lotions, after-shave creams and lotions, tanning creams and lotions, treatment cosmetic products, hair care products, deodorants and antiperspirants, decorative cosmetic products, candles, lamp oils, incense sticks, insecticides, repellents and propellants.
The following examples illustrate the present invention without, however, limiting it in any way: Example 1 : Fragrance composition 1 :
Figure imgf000028_0001
Fragrance composition 1 has an intense and harmonious lily of the valley note with slightly less power than fragrance characteristics of pure 2-methyl-3-(4-tert.- butylphenyl) propanal (Lysmeral®, BASF SE).
Example 2: Fragrance composition 2:
Figure imgf000028_0002
Fragrance composition 2 has an intense and harmonious lily of the valley note indistinguishable from the fragrance characteristics of pure 2-methyl-3-(4-tert.-butylphenyl) propanal (Lysmeral®, BASF SE). Example 3: Fragrance Composition 3:
Figure imgf000029_0001
Fragrance composition 3 has an intense and harmonious lily of the valley note indistin- guishable from the fragrance characteristics of pure 2-methyl-3-(4-tert.-butylphenyl) propanal (Lysmeral®, BASF SE).
Example 4: Fragrance Composition 4:
Figure imgf000029_0002
Fragrance composition 4 has an intense and harmonious lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
Example 5: Fragrance Composition 5:
Component Parts by weight
(wt.-%)
2,5,7,7-Tetramethyoctanal 50
2-lsobutyl-4-methyltetrahydro-2H-pyran-4-ol 30
7-Hydroxy-3,7-dimethyloctanal 5
3,7-dimethyl-octan-1 ,7-diol 14
4-(Octahydro-4,7-methano-5H-inden-5- 1
yliden)butanal
Total 100 Fragrance composition 5 has an intense and harmonious lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
Example 6: Fragrance Composition 6:
Figure imgf000030_0001
Fragrance composition 6 has an intense and harmonious lily of the valley note very similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
Example 7: Fragrance Composition 7:
Figure imgf000030_0002
Fragrance composition 7 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact. Example 8: Fragrance Composition 8:
Figure imgf000031_0001
Fragrance composition 8 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
Example 9: Fragrance Composition 9:
Figure imgf000031_0002
Fragrance composition 9 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact. Example 10: Fragrance Composition 10:
Figure imgf000032_0001
Fragrance composition 10 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
Example 1 1 : Fragrance Composition 1 1 :
Figure imgf000032_0002
Fragrance composition 1 1 has an intense and harmonious lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
Example 12: Fragrance Composition 12:
Figure imgf000033_0001
Fragrance composition 12 has an intense and harmonious lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
Example 13: Fragrance Composition 13:
Figure imgf000033_0002
Fragrance composition 13 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact. Example 14: Fragrance Composition 14:
Figure imgf000034_0001
Fragrance composition 14 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
Example 15: Fragrance Composition
Figure imgf000034_0002
Fragrance composition 15 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact. Example 16: Fragrance Composition 16:
Figure imgf000035_0001
Fragrance composition 16 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with stronger impact.
Example 17: Fragrance Composition 17:
Figure imgf000035_0002
Fragrance composition 17 has an intense and powerful lily of the valley note very similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE)
Example 18: Fragrance Composition 18:
Component Parts by weight
(wt.-%)
2,5,7,7-Tetramethyoctanal 70
2-lsobutyl-4-methyltetrahydro-2H-pyran-4-ol 25
4-(Octahydro-4,7-methano-5H-inden-5- 1
yliden)butanal
Dipropylene glycol 4
Total 100 Fragrance composition 18 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
Example 19: Fragrance Composition 19:
Fragrance composition 19 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
Example 20: Fragrance Composition 20:
Figure imgf000036_0002
Fragrance composition 20 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact. Example 21 : Fragrance Composition 21 :
Figure imgf000037_0001
Fragrance composition 21 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
Example 22: Fragrance Composition
Figure imgf000037_0002
Fragrance composition 22 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
Example 23: Fragrance Composition 23:
Component Parts by weight
(wt.-%)
2,5,7,7-Tetramethyoctanal 86
4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen- 4
1 -carboxaldehyde and/or 3-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1 - carboxaldehyde
4-(Octahydro-4,7-methano-5H-inden-5- 0.5
yliden)butanal
Dipropylene glycol 9-6
Total 100 Fragrance composition 23 has an intense and powerful lily of the valley note similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) with slightly stronger impact.
Example 24: Fragrance Composition 24:
Figure imgf000038_0001
Fragrance composition 24 has an intense and powerful lily of the valley note very simi- lar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE)
Example 25: Fragrance Composition 25:
Figure imgf000038_0002
Fragrance composition 25 has an intense and powerful lily of the valley note very similar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE) Example 26: Fragrance Composition 26:
Figure imgf000039_0001
Fragrance composition 26 has an intense and powerful lily of the valley note very simi- lar to that of pure 2-methyl-3-(4-tert.-butylphenyl)propanal (Lysmeral®, BASF SE)

Claims

Claims:
A fragrance composition comprising a) 2,5,7,7-tetramethyloctanal and
b) 2-lsobutyl-4-methyl-tetrahydro-2H-pyran-4-ol and
c) optionally one or more additional fragrance substance(s) and
d) optionally one or more diluent(s).
A fragrance composition according to claim 1 , comprising 7-hydroxy-3,7- dimethyloctanal as additional fragrance substance c).
A fragrance composition according to claim 1 or 2, comprising 4-isopropyl- cyclohexylmethanol as additional fragrance substance c).
A fragrance composition according to any of claims 1 to 3, comprising 2,6- dimethylheptan-2-ol as additional fragrance substance c).
A fragrance composition according to any of claims 1 to 4, comprising 3,7- dimethyl-octan-1 ,7-diol as additional fragrance substance c).
A fragrance composition according to any of claims 1 to 5, comprising 4- (Octahydro-4,7-methano-5H-inden-5-yliden)butanal as additional fragrance substance c).
A fragrance composition according to any of claims 1 to 6, comprising 4-(4- Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4- Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde as additional fragrance substance(s) c).
A fragrance composition according to any of claims 1 to 7, wherein the fragrance composition comprises, based on the total amount of the composition, a total amount of 2,5,7,7-tetramethyloctanal in the range from 0,1 to 95 wt.%.
A fragrance composition according to any of claims 1 to 8, wherein the fragrance composition comprises, based on the total amount of the composition, a total amount of 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol in the range from 0,1 to 95 wt.%.
A fragrance composition according to any of claims 1 to 9, wherein the weight- based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol ranges from 1 :30 to 30:1 .
A fragrance composition according to any of claims 2 to 10, wherein the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 7-hydroxy-3,7-dimethyloctanal in the fragrance composition ranges from 30:1 to 1 :30.
A fragrance composition according to any of claim 3 to 1 1 , wherein the weight- based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-isopropyl-cyclohexylmethanol in the fragrance composition ranges from 30:1 to 1 :30.
A fragrance composition according to any of claims 4 to 12, wherein the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 2,6-dimethylheptan-2-ol ranges from 1 :50 to 50:1.
A fragrance composition according to any of claims 5 to 13, wherein the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 3,7-dimethyl-octan-1 ,7-diol ranges from 1 :30 to 30:1.
A fragrance composition according to any of claims 6 to 14, wherein the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-(Octahydro-4,7-methano-5H-inden-5-yliden)butanal ranges from 1 :50 to 50:1.
A fragrance composition according to any of claims 7 to 15, wherein the weight-based ratio of the total amount of 2,5,7,7-tetramethyloctanal to the total amount of 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde and/or 3-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1 -carboxaldehyde ranges from 1 :50 to 50:1.
A fragrance composition according to any of claims 1 to 16, wherein the fragrance composition comprises, based on the total amount of the composition, a total amount of 2-methyl-3-(4-tert.-butylphenyl)propanal of 1 wt.% or less.
18. A fragrance composition according to any of claims 1 to 17, wherein the fragrance composition is substantially free of 2-methyl-3-(4-tert.- butylphenyl)propanal.
19. A fragrance composition according to any of claims 1 to 18, wherein the fragrance composition comprises one or more diluent or diluents selected from the group consisting of diethylene glycol monoethyl ether, glycerol, propylene glycol, 1 ,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate and isopropyl myristate and dialkyl esters of 1 ,2-cyclohexanedicarboxylic acid, especially 1 ,2-cyclohexanedicarboxylic acid diisononyl ester.
20. A method for emparting and/or enhancing an odour or flavour of a product or article with a lily of the valley- or muguet-type note, a syringa-type note, a magnolia-type note, a cyclamen-type note, a hyacinth-type note or a lilac-type note comprising bringing into contact or mixing with or adding to said product or article an organoleptically active quantity of a fragrance composition according to any of claims 1 to 19.
A method for producing a perfumed product or article comprising bringing into contact or mixing with or adding to said product or article an organoleptically active quantity of the fragrance composition according to any of claim 1 to 19.
A perfumed or aromatized product or article comprising an organoleptically tive quantity of the fragrance composition according to any of claim 1 to 19.
A perfumed article or product according to claim 20, wherein the article or product is selected from the group consisting of perfume extracts, eaux de parfum, eaux de toilette, after-shave lotions, eaux de Cologne, pre-shave products, splash colognes, perfumed refreshing tissues, acidic, alkaline and neutral cleaning products, textile fresheners, ironing aids, liquid detergents, powder detergents, fabric preconditioners, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants, air purifiers, aerosol sprays, waxes and polishes, body care products, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, treatment cosmetic products, after-shave creams and lotions, tanning creams and lotions, hair care products, deodorants and antiperspirants, decorative cosmetic products, candles, lamp oils, incense sticks, insecticides, repellents and propellants.
PCT/EP2010/062662 2009-09-09 2010-08-31 Lily of the valley-type fragrance compositions comprising 2,5,7,7-tetramethyloctanal WO2011029743A1 (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103030538A (en) * 2011-10-07 2013-04-10 西姆莱斯有限公司 Fragrances with note of lily of the valley
US20130230476A1 (en) * 2010-11-10 2013-09-05 Basf Se Fragrance Compositions Comprising Special Mixtures of Diastereomers of 2-Isobutyl-4-Methyl-Tetrahydro-2H-Pyran-4-OL
JP2016518460A (en) * 2012-10-15 2016-06-23 ジボダン エス エー Organic compounds
WO2019122236A1 (en) 2017-12-21 2019-06-27 Firmenich Sa Method for identifying positive allosteric modulators for odorant receptors
CN110809622A (en) * 2017-06-19 2020-02-18 西姆莱斯有限公司 Novel ambergris and/or indole aromatic composition
WO2020127325A2 (en) 2018-12-19 2020-06-25 Firmenich Sa Use of volatile compounds to modulate the perception of floral muguet
WO2021069331A1 (en) * 2019-10-10 2021-04-15 Firmenich Sa Lily of the valley odorant

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0252378A1 (en) 1986-07-05 1988-01-13 BASF Aktiengesellschaft Aliphatic aldehydes, method for their production and their application as perfume agents
EP0269999A2 (en) 1986-12-03 1988-06-08 BASF Aktiengesellschaft Aliphatic alcohols and esters, their preparation and use as flavouring agents
US4963285A (en) * 1989-02-09 1990-10-16 International Flavors & Fragrances Inc. 2,4,4-irisubstituted tetrahydro pyranyl esters and organoleptic uses thereof
EP0395982A2 (en) 1989-04-29 1990-11-07 BASF Aktiengesellschaft Beta,gamma unsaturated nitriles, their preparation and their use as perfumes
US6297211B1 (en) * 1999-02-19 2001-10-02 Givaudan Roure (International) Sa Odorant compositions
WO2005110967A1 (en) * 2004-05-12 2005-11-24 Symrise Gmbh & Co. Kg 3-methylbenzyl-isobutyrat
WO2009027957A2 (en) 2008-12-16 2009-03-05 The Procter & Gamble Company Perfume systems

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0252378A1 (en) 1986-07-05 1988-01-13 BASF Aktiengesellschaft Aliphatic aldehydes, method for their production and their application as perfume agents
EP0269999A2 (en) 1986-12-03 1988-06-08 BASF Aktiengesellschaft Aliphatic alcohols and esters, their preparation and use as flavouring agents
US4963285A (en) * 1989-02-09 1990-10-16 International Flavors & Fragrances Inc. 2,4,4-irisubstituted tetrahydro pyranyl esters and organoleptic uses thereof
EP0395982A2 (en) 1989-04-29 1990-11-07 BASF Aktiengesellschaft Beta,gamma unsaturated nitriles, their preparation and their use as perfumes
US6297211B1 (en) * 1999-02-19 2001-10-02 Givaudan Roure (International) Sa Odorant compositions
WO2005110967A1 (en) * 2004-05-12 2005-11-24 Symrise Gmbh & Co. Kg 3-methylbenzyl-isobutyrat
WO2009027957A2 (en) 2008-12-16 2009-03-05 The Procter & Gamble Company Perfume systems

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
K. BAUER; D. GARBE; H. SURBURG: "Common Fragrance and Flavor Materials, 4th Edition,", 2001, WILEY-VCH
S. ARCTANDER: "Perfume and Flavor Materials", vol. I, II, 1969

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130230476A1 (en) * 2010-11-10 2013-09-05 Basf Se Fragrance Compositions Comprising Special Mixtures of Diastereomers of 2-Isobutyl-4-Methyl-Tetrahydro-2H-Pyran-4-OL
CN103030538A (en) * 2011-10-07 2013-04-10 西姆莱斯有限公司 Fragrances with note of lily of the valley
US20130090390A1 (en) * 2011-10-07 2013-04-11 Symrise Ag Fragrances with note of lily of the valley
JP2016518460A (en) * 2012-10-15 2016-06-23 ジボダン エス エー Organic compounds
CN110809622A (en) * 2017-06-19 2020-02-18 西姆莱斯有限公司 Novel ambergris and/or indole aromatic composition
WO2019122236A1 (en) 2017-12-21 2019-06-27 Firmenich Sa Method for identifying positive allosteric modulators for odorant receptors
WO2020127325A2 (en) 2018-12-19 2020-06-25 Firmenich Sa Use of volatile compounds to modulate the perception of floral muguet
WO2021069331A1 (en) * 2019-10-10 2021-04-15 Firmenich Sa Lily of the valley odorant

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