EP0862911A2 - Use of macrocyclic lactones as fragrances - Google Patents

Use of macrocyclic lactones as fragrances Download PDF

Info

Publication number
EP0862911A2
EP0862911A2 EP98102945A EP98102945A EP0862911A2 EP 0862911 A2 EP0862911 A2 EP 0862911A2 EP 98102945 A EP98102945 A EP 98102945A EP 98102945 A EP98102945 A EP 98102945A EP 0862911 A2 EP0862911 A2 EP 0862911A2
Authority
EP
European Patent Office
Prior art keywords
tetradecen
olid
methyl
fragrances
macrocyclic lactones
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98102945A
Other languages
German (de)
French (fr)
Other versions
EP0862911A3 (en
Inventor
Heinz-Jürgen Dr. Bertram
Oskar Dr. Koch
Peter Wörner
Horst Dr. Surburg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Symrise AG
Original Assignee
Haarmann and Reimer GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haarmann and Reimer GmbH filed Critical Haarmann and Reimer GmbH
Publication of EP0862911A2 publication Critical patent/EP0862911A2/en
Publication of EP0862911A3 publication Critical patent/EP0862911A3/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0069—Heterocyclic compounds
    • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
    • C11B9/0084—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing more than six atoms
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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

Definitions

  • the invention relates to the use of macrocyclic lactones as Fragrances.
  • 15-pentadecanolide of the formula is a component of angelica root oil and has a delicate musky smell and the ability to act as a fixative. It has therefore been intensively concerned with the production of such macrocyclic lactones.
  • Another method involves adding hydrogen peroxide or alkyl peroxide 13-Oxabicyclo [10.4.0] hexadec-1 (12) en in the presence of sulfuric acid. Thermal or UV-initiated cleavage of the resulting 12-hydroperoxy-13-oxabicyclo [10.4.0] hexadecane (III) leads to 15-pentadecanolide (I) and to 15-pentadecenolides, which too I can be hydrogenated (DE-AS 2 026 056).
  • the 12-oxo-15-pentadecanolide reduced in the presence of Raney nickel to 12-hydroxy-15-pentadecanolide, this then for example in the presence of phosphoric acid to the corresponding 15-Pentadec-11- and -12-enolids dehydrated and these products in the presence hydrogenated a nickel catalyst to I.
  • Lactones II and thus III can be produced in different ways. This is how they are produced by a metathesis reaction on nickel catalysts (p. Inoue et al; Nippon Kagaku Kaishi (1985), 425), by Claisen rearrangement (D.W. Knight et al., J. Chem. Soc., Perkin Trans. I (1986), 161; R. L. Funk et al. Tetrahedron 42 (1986), 2831) and thermal or photochemical fragmentation of peroxides (DE-OS 20 26 056) or other derivatives (DE-OS 41 15 182).
  • lactones II and III are particularly advantageous if this is done easily prepared 12-hydroperoxy-13-oxabicyclo [10.3.0] pentadecane or 12-hydroperoxy-14-methyl-oxabicyclo [10.30] pentadecane with the addition of copper (II) - and Iron (II) salts based on one of S.L. Schreiber et al. (J. Amer. Chem. Soc. 102 (1980), 6163) fragmented for the synthesis of recifeiolide.
  • fragrances listed can be used individually or in a mixture because of their excellent olfactory properties in a wide range of Fragrance compositions are used. It has been shown that through skillful mixing of these compounds with other ingredients can be reinforced. Another important characteristic of these connections is their suitability for "rounding" when mixed with other ingredients and to cause "intensity of the initial smell" of fragrance compositions.
  • “Rounding” refers to a property of a fragrance composition that is expresses that when combining the individual components a harmonious Odor impression arises and none of the individual fragrance components from the Bouquet of composition stands out.
  • the term "intensity of the initial smell” refers to the first impression that a fragrance composition gives, ie on the characterization of the initial smell.
  • Lactones II and III allow the formulation of new and interesting compositions. Amounts of 8-15% by weight Lactone, based on composition, are preferred.
  • compositions can be used to perfume Cosmetics such as creams, lotions, aerosols, toilet soaps, technical articles, Detergents, fabric softeners, disinfectants and textile treatment agents to serve.
  • perfume Cosmetics such as creams, lotions, aerosols, toilet soaps, technical articles, Detergents, fabric softeners, disinfectants and textile treatment agents to serve.
  • a solution of 114 g of copper (II) acetate in 2,250 g of water is placed in a 6 liter three-necked flask and a suspension of 150 g of IV in 500 g (MTBE) is added with stirring.
  • a solution of 172 g of iron (II) sulfate in 760 g of water is then metered in at RT within 15 min, the mixture is stirred for a further 30 min after the addition and the pH is adjusted to 1 with 550 g of 2N hydrochloric acid x 1,500 g MTBE extracted, the org.
  • Phase washed neutral with bicarbonate and distilled, after which 107 g of cyclotetradecenolide IIa are present as a mixture of isomers.
  • this sweet oriental composition receives an enhanced base note through a musky impression, which can best be characterized with nitro musk.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Fats And Perfumes (AREA)
  • Pyrane Compounds (AREA)
  • Cosmetics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

Use macrocyclic lactones of formula (I) and/or (II) as perfumes is claimed. R = H or Me; and the dotted line indicates an additional bond in the 11- 12- position.

Description

Die Erfindung betrifft die Verwendung von macrocyclischen Lactonen als Riechstoffe.The invention relates to the use of macrocyclic lactones as Fragrances.

Moschus ist bekanntlich selten und teuer. Deshalb sind Duftstoffe mit moschusähnlichem Geruch, die besser zugänglich sind, begehrte Komponenten für die Duftstoffindustrie. 15-Pentadecanolid der Formel

Figure 00010001
ist Bestandteil des Angelicawurzelöls und besitzt einen zarten moschusartigen Geruch und die Fähigkeit, als Fixativ zu wirken. Man hat sich deswegen schon intensiv mit der Herstellung solcher makrocyclischen Lactone befaßt. Die heute wichtigsten Synthesen gehen von 13-Oxabicyclo[10.4.0]hexadec-1(12)en aus, das z.B. durch radikalische Addition von Allylalkohol an Cyclododecanon und säurekatalysierte Dehydratisierung des resultierenden 2-(γ-Hydroxypropyl)-cyclododecanons hergestellt werden kann (DE-AS 21 36 496).It is well known that musk is rare and expensive. That is why fragrances with a musky smell, which are more accessible, are sought-after components for the fragrance industry. 15-pentadecanolide of the formula
Figure 00010001
is a component of angelica root oil and has a delicate musky smell and the ability to act as a fixative. It has therefore been intensively concerned with the production of such macrocyclic lactones. The most important syntheses today are based on 13-oxabicyclo [10.4.0] hexadec-1 (12) en, which can be prepared, for example, by radical addition of allyl alcohol to cyclododecanone and acid-catalyzed dehydration of the resulting 2- (γ-hydroxypropyl) cyclododecanone ( DE-AS 21 36 496).

Nach einem anderen Verfahren addiert man Wasserstoffperoxid oder Alkylperoxid an 13-Oxabicyclo[10.4.0]hexadec-1(12)en in Gegenwart von Schwefelsäure. Thermische oder UV-initiierte Spaltung des entstandenen 12-Hydroperoxy-13-oxabicyclo[10.4.0]hexadecans (III) führt zu 15-Pentadecanolid (I) und zu 15-Pentadecenoliden, die zu I hydriert werden können (DE-AS 2 026 056).Another method involves adding hydrogen peroxide or alkyl peroxide 13-Oxabicyclo [10.4.0] hexadec-1 (12) en in the presence of sulfuric acid. Thermal or UV-initiated cleavage of the resulting 12-hydroperoxy-13-oxabicyclo [10.4.0] hexadecane (III) leads to 15-pentadecanolide (I) and to 15-pentadecenolides, which too I can be hydrogenated (DE-AS 2 026 056).

Gemäß dem russischen Urheberschein 1 133 274 wird das 12-Oxo-15-pentadecanolid in Gegenwart von Raney-Nickel zum 12-Hydroxy-15-pentadecanolid reduziert, dieses anschließend beispielsweise in Gegenwart von Phosphorsäure zu den entsprechenden 15-Pentadec-11- und -12-enoliden dehydratisiert und diese Produkte in Gegenwart eines Nickelkatalysators zu I hydriert. According to the Russian copyright certificate 1 133 274, the 12-oxo-15-pentadecanolide reduced in the presence of Raney nickel to 12-hydroxy-15-pentadecanolide, this then for example in the presence of phosphoric acid to the corresponding 15-Pentadec-11- and -12-enolids dehydrated and these products in the presence hydrogenated a nickel catalyst to I.

Überraschenderweise wurde nun festgestellt, daß sowohl Tetradecenolide, deren C=C-Doppelbindungen in 11- oder 12-Position stehen, als auch die entsprechend gesättigten Verbindungen wertvolle organoleptische Eigenschaften besitzen.Surprisingly, it has now been found that both tetradecenolides, their C = C double bonds are in the 11- or 12-position, as well as the corresponding saturated compounds have valuable organoleptic properties.

Gegenstand der Erfindung ist also die Verwendung von Verbindungen der Formeln

Figure 00020001
worin

R
für Wasserstoff oder Methyl steht und die gestrichelten Linien eine zusätzliche Bindung in 11- oder 12-Position bedeuten,
als Riechstoffe.The invention therefore relates to the use of compounds of the formulas
Figure 00020001
wherein
R
represents hydrogen or methyl and the dashed lines mean an additional bond in the 11- or 12-position,
as fragrances.

Lactone II und damit auch III können auf verschiedenen Wegen hergestellt werden. So gelingt ihre Herstellung durch Metathesereaktion an Nickel-Katalysatoren (S. Inoue et al; Nippon Kagaku Kaishi (1985), 425), durch Claisen-Umlagerung (D. W. Knight et al., J. Chem. Soc., Perkin Trans. I (1986), 161; R. L. Funk et al. Tetrahedron 42 (1986), 2831) und thermische oder photochemische Fragmentierung von Peroxiden (DE-OS 20 26 056) oder anderen Derivaten (DE-OS 41 15 182).Lactones II and thus III can be produced in different ways. This is how they are produced by a metathesis reaction on nickel catalysts (p. Inoue et al; Nippon Kagaku Kaishi (1985), 425), by Claisen rearrangement (D.W. Knight et al., J. Chem. Soc., Perkin Trans. I (1986), 161; R. L. Funk et al. Tetrahedron 42 (1986), 2831) and thermal or photochemical fragmentation of peroxides (DE-OS 20 26 056) or other derivatives (DE-OS 41 15 182).

Besonders vorteilhaft gelingt die Herstellung der Lactone II bzw. III, wenn man das leicht herstellbare 12-Hydroperoxy-13-oxabicyclo[10.3.0]pentadecan bzw. 12-Hydroperoxy-14-methyl-oxabicyclo[10.30]pentadecan unter Zusatz von Kupfer-(II)- und Eisen-(II)-salzen in Anlehnung an ein von S. L. Schreiber et al. (J. Amer. Chem. Soc. 102 (1980), 6163) zur Synthese von Recifeiolide angegebenes Verfahren fragmentiert.The production of lactones II and III is particularly advantageous if this is done easily prepared 12-hydroperoxy-13-oxabicyclo [10.3.0] pentadecane or 12-hydroperoxy-14-methyl-oxabicyclo [10.30] pentadecane with the addition of copper (II) - and Iron (II) salts based on one of S.L. Schreiber et al. (J. Amer. Chem. Soc. 102 (1980), 6163) fragmented for the synthesis of recifeiolide.

Sowohl für die ungesättigten als auch für die gesättigten Lactone sind die hervorragenden olfaktorischen Eigenschaften bisher nicht erkannt worden. Zwar wird Lacton III (R=H) in der Literatur mit einem sandelartigen Geruch beschrieben (Helv. Chim. Acta 78, 440 (1995)), aber die von uns hergestellte Ware besitzt einen ausgesprochen weichen, lang anhaftenden Moschus- und Nitromoschus-Charakter. Unser Befund gilt im gleichen Maß auch für die isomeren Verbindungen der Lactone II.The outstanding olfactory properties have not been recognized for either the unsaturated or the saturated lactones. Lactone III (R = H) is described in the literature with a sandal-like odor (Helv. Chim. Acta 78 , 440 (1995)), but the goods we manufacture have a very soft, long-lasting musk and nitro musk character . Our findings apply equally to the isomeric compounds of lactones II.

Die erfindungsgemäß zu verwendenden makrocyclischen Lactone sind im einzelnen:

  • cis-Tetradecen-(11)-olid-(14,1)
  • trans-Tetradecen-(11)-olid-(14,1)
  • cis-Tetradecen-(12)-olid-(14,1)
  • trans-Tetradecen-(12)-olid-(14,1)
  • cis-14-Methyl-tetradecen-(11)-olid-(14,1)
  • trans-14-Methyl-tetradecen-(11)-olid-(14,1)
  • cis-14-Methyl-tetradecen-(12)-olid-(14,1)
  • trans-14-Methyl-tetradecen-(12)-olid-(14,1)
  • Tetradecanolid-(14,1)
  • 14-Methyl-tetradecanolid-(14,1).
    • The macrocyclic lactones to be used according to the invention are in detail:
  • cis-tetradecen- (11) -olid- (14.1)
  • trans-tetradecen- (11) -olid- (14.1)
  • cis-tetradecen- (12) -olid- (14.1)
  • trans-tetradecen- (12) -olid- (14.1)
  • cis-14-methyl-tetradecen- (11) -olid- (14.1)
  • trans-14-methyl-tetradecen- (11) -olid- (14.1)
  • cis-14-methyl-tetradecen- (12) -olid- (14.1)
  • trans-14-methyl-tetradecen- (12) -olid- (14.1)
  • Tetradecanolide- (14.1)
  • 14-methyl-tetradecanolide- (14.1).

    • Die aufgezählten Riechstoffe können einzeln wie auch im Gemisch wegen ihrer hervorragenden olfaktorischen Eigenschaften in einer breiten Palette von Riechstoffkompositionen verwendet werden. Es hat sich gezeigt, daß durch geschicktes Mischen dieser Verbindungen mit anderen Ingredienzien Riechstoffnoten verstärkt werden können. Ein weiteres wichtiges Charakteristikum dieser Verbindungen ist ihre Eignung, beim Mischen mit anderen Ingredienzien "Abrundung" und "Intensität des Anfangsgeruches" von Riechstoffkompositionen zu bewirken. "Abrundung" bezieht sich auf eine Eigenschaft einer Riechstoffkomposition, die sich darin äußert, daß beim Zusammengeben der einzelnen Komponenten ein harmonischer Geruchseindruck entsteht und keine der einzelnen Riechstoffkomponenten aus dem Bouquet der Komposition herausragt. Der Begriff "Intensität des Anfangsgeruchs" bezieht sich auf den ersten Eindruck, den eine Riechstoffkomposition erweckt, also auf die Charakterisierung des Anfangsgeruchs. Bekanntlich ist es eine der wesentlichen Aufgaben der Kompositionsarbeit, "Abrundung" und "Intensität des Anfangsgeruchs" besonders ausgewogen zu gestalten. Die Lactone II und III gestatten die Formulierung neuartiger interessanter Kompositionen. Mengen von 8-15 Gew.-% Lacton, bezogen auf Komposition, sind bevorzugt.The fragrances listed can be used individually or in a mixture because of their excellent olfactory properties in a wide range of Fragrance compositions are used. It has been shown that through skillful mixing of these compounds with other ingredients can be reinforced. Another important characteristic of these connections is their suitability for "rounding" when mixed with other ingredients and to cause "intensity of the initial smell" of fragrance compositions. "Rounding" refers to a property of a fragrance composition that is expresses that when combining the individual components a harmonious Odor impression arises and none of the individual fragrance components from the Bouquet of composition stands out. The term "intensity of the initial smell" refers to the first impression that a fragrance composition gives, ie on the characterization of the initial smell. As is well known, it is one of the essential tasks of composition work, "rounding off" and "intensity of Initial smell "particularly balanced. Lactones II and III allow the formulation of new and interesting compositions. Amounts of 8-15% by weight Lactone, based on composition, are preferred.

    Außer in der Feinparfümerie können derartige Kompositionen zur Parfümierung von Kosmetika wie Cremes, Lotionen, Aerosolen, Toilettenseifen, technischen Artikeln, Waschmitteln, Weichspülern, Desinfektionsmitteln und Textilbehandlungsmitteln dienen. Für diesen Zweck sind 1-5 Gew.-%, bezogen auf zu parfümierendes Substrat, bevorzugt. Except in the fine perfumery, such compositions can be used to perfume Cosmetics such as creams, lotions, aerosols, toilet soaps, technical articles, Detergents, fabric softeners, disinfectants and textile treatment agents to serve. For this purpose, 1-5% by weight, based on the substrate to be perfumed, prefers.

    BeispieleExamples 1. Herstellung des Hydroperoxids 1. Preparation of the hydroperoxide

    Figure 00050001
    Figure 00050001

    In einem 2-Ltr.-Dreihalskolben werden 880 g Essigsäure vorgelegt und bei 0°C 154 g des Enolethers V zugegeben. Man dosiert dann innerhalb von 30 min eine Mischung aus 147 g 30-proz. Perhydrol und 36 g halbkonz. Schwefelsäure, rührt bei der angegebenen Temperatur noch 15 min nach und filtriert das ausgefallene Produkt ab. Es wird mit 250 ml 50-proz. Essigsäure sowie mit 5 x 400 ml Wasser neutralgewaschen. Man suspendiert das weiße Kristallisat in 500 g Methyl-t.-butylether (MTBE), trennt die sich absetzende Wasserphase ab und erhält 150 g des Hydroperoxids IV.880 g of acetic acid are placed in a 2 liter three-necked flask and 154 g of enol ether V are added at 0.degree. A mixture of 147 g of 30 percent is then metered in within 30 minutes. Perhydrol and 36 g semi-concentrated. Sulfuric acid, stirring at the specified temperature for a further 15 min and filtering off the precipitated product. It is 50 percent with 250 ml. Acetic acid and washed neutral with 5 x 400 ml of water. The white crystals are suspended in 500 g of methyl t-butyl ether (MTBE), the water phase which separates out is separated off and 150 g of the hydroperoxide IV are obtained .

    2. Herstellung des Cyclotetradecenolids 2. Preparation of the cyclotetradecenolide

    Figure 00050002
    Figure 00050002

    In einem 6-Ltr.-Dreihalskolben wird eine Lösung von 114 g Kupfer-(II)-acetat in 2.250 g Wasser vorgelegt und unter Rühren eine Suspension von 150 g von IV in 500 g (MTBE) zugegeben. Man dosiert dann bei RT innerhalb von 15 min eine Lösung von 172 g Eisen-(II)-sulfat in 760 g Wasser, rührt noch 30 min nach Zugabe und stellt mit 550 g 2 N Salzsäure auf pH 1. Anschließend wird das Produkt mit 3 x 1.500 g MTBE extrahiert, die org. Phase mit Bicarbonat neutral gewaschen und destilliert, wonach 107 g des Cyclotetradecenolids IIa als Isomerengemisch vorliegen. A solution of 114 g of copper (II) acetate in 2,250 g of water is placed in a 6 liter three-necked flask and a suspension of 150 g of IV in 500 g (MTBE) is added with stirring. A solution of 172 g of iron (II) sulfate in 760 g of water is then metered in at RT within 15 min, the mixture is stirred for a further 30 min after the addition and the pH is adjusted to 1 with 550 g of 2N hydrochloric acid x 1,500 g MTBE extracted, the org. Phase washed neutral with bicarbonate and distilled, after which 107 g of cyclotetradecenolide IIa are present as a mixture of isomers.

    3. Herstellung des Cyclotetradecanolids 3. Preparation of the cyclotetradecanolide

    Figure 00060001
    Figure 00060001

    52 g des ungesättigten Lactons IIa werden in isopropanolischer Lösung unter Zusatz von Pd/C Katalysator bei 40°C hydriert. Nach Abfiltrieren des Katalysators entfernt man das Lösungsmittel, destilliert den verbleibenden Rückstand und erhält 42 g des Cyclotetradecanolids IIIa.52 g of the unsaturated lactone IIa are hydrogenated in isopropanolic solution with the addition of Pd / C catalyst at 40 ° C. After filtering off the catalyst, the solvent is removed, the remaining residue is distilled and 42 g of cyclotetradecanolide IIIa are obtained .

    4. Präparation eines Parfümöls 4. Preparation of a perfume oil

    IngredienzienIngredients Menge in gQuantity in g BergamottölBergamot oil 100100 VertocitralVertocitral 22nd Hexenylsalicylat, cis-3Hexenyl salicylate, cis-3 1313 ProfarnesolProfarnesol 1010th IsoananatIsoananate 55 HexähydroiraldeinHexahydroiraldein 2525th HedionHedion 200200 IndolIndole 55 LinaloolLinalool 150150 Mandarinenöl, ital.Mandarin oil, Italian. 5050 Octalacton, gammaOctalactone, gamma 55 PhenoxanolPhenoxanol 5050 RosaphenRosaphen 100100 BoisanolBoisanol 100100 SandolenSandolen 3030th CumarinCoumarin 1010th VanillinVanillin 1010th Verbindung IIIaCompound IIIa 135135 Summetotal 1.0001,000

    Durch Zugabe von 8-15 % der Substanz IIIa erhält diese süß-orientalische Komposition eine verstärkte Fondnote durch einen Moschuseindruck, der am besten mit Nitromoschus zu charakterisieren ist.With the addition of 8-15% of substance IIIa , this sweet oriental composition receives an enhanced base note through a musky impression, which can best be characterized with nitro musk.

    Claims (1)

    Verwendung von Verbindungen der Formeln
    Figure 00070001
    worin
    R
    für Wasserstoff oder Methyl steht und die gestrichelten Linien eine zusätzliche Bindung in 11- oder 12-Position bedeuten,
    als Riechstoffe.    Use of compounds of the formulas
    Figure 00070001
    wherein
    R
    represents hydrogen or methyl and the dashed lines mean an additional bond in the 11- or 12-position,
    as fragrances.
    EP98102945A 1997-03-05 1998-02-20 Use of macrocyclic lactones as fragrances Withdrawn EP0862911A3 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19708924A DE19708924A1 (en) 1997-03-05 1997-03-05 Use of macrocyclic lactones as fragrances
    DE19708924 1997-03-05

    Publications (2)

    Publication Number Publication Date
    EP0862911A2 true EP0862911A2 (en) 1998-09-09
    EP0862911A3 EP0862911A3 (en) 2000-04-26

    Family

    ID=7822284

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP98102945A Withdrawn EP0862911A3 (en) 1997-03-05 1998-02-20 Use of macrocyclic lactones as fragrances

    Country Status (4)

    Country Link
    US (1) US6008185A (en)
    EP (1) EP0862911A3 (en)
    JP (1) JPH10251684A (en)
    DE (1) DE19708924A1 (en)

    Cited By (8)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1375491A1 (en) * 2002-06-19 2004-01-02 Symrise GmbH & Co. KG Process for the preparation of 11(12)-pentadecen-15-olides
    WO2005014569A1 (en) * 2003-07-17 2005-02-17 Akzo Nobel N.V. 1,2,4,-trioxepanes as precursors for lactones
    WO2005113533A1 (en) * 2004-05-13 2005-12-01 Symrise Gmbh & Co. Kg Process for preparing unsaturated lactones
    WO2010082684A1 (en) * 2009-01-13 2010-07-22 Kao Corporation Fragrance composition
    EP2540712A1 (en) 2011-06-30 2013-01-02 Basf Se Process for the preparation of cyclic enolethers
    EP2540713A1 (en) 2011-06-30 2013-01-02 Basf Se Macrocyclic lactones
    US8410293B2 (en) 2011-06-30 2013-04-02 Basf Se Process for the preparation of cyclic enol ethers
    US8648031B2 (en) 2011-06-30 2014-02-11 Basf Se Macrocyclic lactones

    Families Citing this family (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE10113963A1 (en) * 2001-03-22 2002-09-26 Haarmann & Reimer Gmbh Process for the preparation of 15-pentadecanolide
    GB2423986A (en) * 2004-12-24 2006-09-13 Givaudan Sa Fragrance Compound
    JP5474360B2 (en) * 2009-01-13 2014-04-16 花王株式会社 New macrocyclic lactone

    Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE2034737A1 (en) * 1969-07-17 1971-03-11 Research Corp , New York, N Y (VStA) Process for the preparation of macrocyclic compounds
    US3890353A (en) * 1969-05-29 1975-06-17 Firmenich & Cie Process for preparing lactones
    EP0424787A2 (en) * 1989-10-27 1991-05-02 Firmenich Sa Use of unsaturated macrocyclic ketones as perfuming ingredients
    WO1997032948A1 (en) * 1996-03-08 1997-09-12 Firmenich S.A. Fragrant macrocyclic lactones

    Family Cites Families (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    BE786518A (en) * 1971-07-21 1973-01-22 Haarmann & Reimer Gmbh OXA-BICYCLO-ALCENES PREPARATION PROCESS
    JPS5125033B2 (en) * 1971-08-18 1976-07-28
    JPH0710234B2 (en) * 1986-08-05 1995-02-08 株式会社ジャパンエナジー Method for producing lactone
    DE4115182A1 (en) * 1991-05-09 1992-11-12 Haarmann & Reimer Gmbh NEW DERIVATIVES OF CYCLIC LACTONES, METHOD FOR THE PRODUCTION THEREOF AND METHOD FOR THE PRODUCTION OF 15-PENTADECANOLIDE AND ITS HOMOLOGOS

    Patent Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3890353A (en) * 1969-05-29 1975-06-17 Firmenich & Cie Process for preparing lactones
    DE2034737A1 (en) * 1969-07-17 1971-03-11 Research Corp , New York, N Y (VStA) Process for the preparation of macrocyclic compounds
    EP0424787A2 (en) * 1989-10-27 1991-05-02 Firmenich Sa Use of unsaturated macrocyclic ketones as perfuming ingredients
    WO1997032948A1 (en) * 1996-03-08 1997-09-12 Firmenich S.A. Fragrant macrocyclic lactones

    Non-Patent Citations (5)

    * Cited by examiner, † Cited by third party
    Title
    CAMERON A G ET AL: "MODEL STUDIES ON THE SYNTHESIS OF MEDIUM-SIZED AND LARGE CARBOCYCLES USING THE IRELAND ENOLATE CLAISEN REARRANGEMENT" JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1,GB,CHEMICAL SOCIETY. LETCHWORTH,1. Januar 1986 (1986-01-01), Seiten 161-167, XP000673911 ISSN: 0300-922X *
    DATABASE WPI Section Ch, Derwent Publications Ltd., London, GB; Class D23, AN 1973-51241U XP002131861 & JP 48 028488 A (SODA AROMATIC KK) *
    DATABASE WPI Section Ch, Week 198813 Derwent Publications Ltd., London, GB; Class B03, AN 1988-088332 XP002131862 & JP 63 039594 A (NIPPON MINING CO), 20. Februar 1988 (1988-02-20) *
    FEY H.; OTTE I.: 'Wörterbuch der Kosmetik', 1985, WISSENSCHAFTLICHE VERLAGSGESELLSCHAFT, STUTTGART *
    FUNK ET AL: "claisen-rearrangement-mediated ring contraction of macrocyclic lactones" TETRAHEDRON, Bd. 42, 1986, Seiten 2831-28446, XP002131860 CHEMICAL SOCIETY. LETCHWORTH.; GB *

    Cited By (15)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1375491A1 (en) * 2002-06-19 2004-01-02 Symrise GmbH & Co. KG Process for the preparation of 11(12)-pentadecen-15-olides
    EP1690860A1 (en) * 2002-06-19 2006-08-16 Symrise GmbH & Co. KG Process for the preparation of 11(12)-pentadecen-15-olides and of 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane
    US7183420B2 (en) 2002-06-19 2007-02-27 Symrise Gmbh & Co. Kg Method for the preparation of 11(12)-pentadecen-15-olides
    WO2005014569A1 (en) * 2003-07-17 2005-02-17 Akzo Nobel N.V. 1,2,4,-trioxepanes as precursors for lactones
    WO2005113533A1 (en) * 2004-05-13 2005-12-01 Symrise Gmbh & Co. Kg Process for preparing unsaturated lactones
    US8383834B2 (en) 2004-05-13 2013-02-26 Symrise Ag Process for preparing unsaturated lactones
    US8338361B2 (en) 2009-01-13 2012-12-25 Kao Corporation Fragrance composition
    WO2010082684A1 (en) * 2009-01-13 2010-07-22 Kao Corporation Fragrance composition
    EP2540712A1 (en) 2011-06-30 2013-01-02 Basf Se Process for the preparation of cyclic enolethers
    EP2540713A1 (en) 2011-06-30 2013-01-02 Basf Se Macrocyclic lactones
    WO2013000846A1 (en) 2011-06-30 2013-01-03 Basf Se Method for producing cyclic enol ethers
    WO2013000842A1 (en) 2011-06-30 2013-01-03 Basf Se Macrocyclic lactones
    US8410293B2 (en) 2011-06-30 2013-04-02 Basf Se Process for the preparation of cyclic enol ethers
    US8648031B2 (en) 2011-06-30 2014-02-11 Basf Se Macrocyclic lactones
    EP2813496A1 (en) 2011-06-30 2014-12-17 Basf Se Macrocyclic lactones

    Also Published As

    Publication number Publication date
    DE19708924A1 (en) 1998-09-10
    JPH10251684A (en) 1998-09-22
    US6008185A (en) 1999-12-28
    EP0862911A3 (en) 2000-04-26

    Similar Documents

    Publication Publication Date Title
    DE69905136T2 (en) ESTER WITH A MUSK SMELL AND THEIR APPLICATION IN PERFUME
    DE602004005890T2 (en) MUSK ODOR SUBSTANCES
    DE60013353T2 (en) Use of substituted acetaldehydes having a cyclic substituent as perfume ingredients
    EP2474301A1 (en) Perfume mixtures containing Cyclopent-2-Enyl-ethyl acetate
    EP0862911A2 (en) Use of macrocyclic lactones as fragrances
    DE2455761C2 (en) Use of hydrogenated methyl ionones and their derivatives as fragrances, processes for their preparation and new hydrogenated methyl ionone derivatives
    DE69028755T2 (en) Use of unsaturated macrocyclic ketones and perfume ingredients
    DE60315776T2 (en) Spiro compounds as perfumes
    DE60009394T2 (en) Cyclopentylalkylnitriles and the use of cyclopentylalkyl derivatives as perfumes
    DE69314121T2 (en) Use of a cyclopentadecenone as a perfume ingredient
    DE2910579C2 (en)
    DE60125670T2 (en) Use of unsaturated esters as fragrances
    DE2756772C2 (en)
    DE2812288C2 (en)
    US4572796A (en) 1,1,4,7-Tetramethyl-3-indanone, product produced thereby and organoleptic uses thereof
    DE69523404T2 (en) USE OF DIHYDROBENZOFURANONES AS PERFUME INGREDIENTS
    DE69812997T2 (en) REACTION OF ALKENES WITH EPOXIES, THE PRODUCTS THEREOF AND THEIR USE AS A FRAGRANCE
    DE602005002304T2 (en) Use of 3- (methoxymethyl) -2-pentylcyclopenta derivatives in perfume compositions
    DE602004001076T2 (en) fragrance compounds
    DE60217236T2 (en) Use of tertiary alcohols or their esters as perfume
    EP0908439B1 (en) Use of substituted 5-phenyl-pentanols as flavour and perfume
    DE60209664T2 (en) Perfume composition containing 3- (3-hexenyl) -2-cyclopentenone
    EP0105157B1 (en) Spirolactones containing perfume compositions
    EP0768294A1 (en) Process for preparing 2,4,4,7-tetramethyl-oct-6-en-3-on and its use as perfume
    DE69803429T2 (en) Nitriles and aldehydes derived from 3-isopropenyl-1,2-dimethyl-1-cyclopentanol and their use in perfumery

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A2

    Designated state(s): CH DE FR GB IT LI NL

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A3

    Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    RIC1 Information provided on ipc code assigned before grant

    Free format text: 7A 61K 7/46 A, 7C 11D 3/50 B, 7C 07D 313/00 B, 7C 11B 9/00 B

    17P Request for examination filed

    Effective date: 20001026

    AKX Designation fees paid

    Free format text: CH DE FR GB IT LI NL

    17Q First examination report despatched

    Effective date: 20030805

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: SYMRISE GMBH & CO. KG

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

    18D Application deemed to be withdrawn

    Effective date: 20031216