EP0000719A2 - 1,4-Epoxy-trimethyl-butenylidene-cyclohexanes (I), process for their preparation, use of (I) as fragrance and/or flavouring substance, fragrance and/or flavour compositions containing the cyclohexanes - Google Patents

1,4-Epoxy-trimethyl-butenylidene-cyclohexanes (I), process for their preparation, use of (I) as fragrance and/or flavouring substance, fragrance and/or flavour compositions containing the cyclohexanes Download PDF

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Publication number
EP0000719A2
EP0000719A2 EP7878100472A EP78100472A EP0000719A2 EP 0000719 A2 EP0000719 A2 EP 0000719A2 EP 7878100472 A EP7878100472 A EP 7878100472A EP 78100472 A EP78100472 A EP 78100472A EP 0000719 A2 EP0000719 A2 EP 0000719A2
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trans
formula
cis
trimethyl
compounds
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German (de)
French (fr)
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EP0000719A3 (en
EP0000719B1 (en
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Roman Kaiser
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Givaudan SA
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L Givaudan and Co SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
    • C07C45/305—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation with halogenochromate reagents, e.g. pyridinium chlorochromate
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/38—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
    • C07C47/46—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings containing hydroxy groups
    • 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
    • C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention relates to new fragrances and / or flavors. These are the compounds of the formula wherein R represents the 2-cis or the 2-trans-buten-1-ylidene radical.
  • the formula accordingly comprises the compounds of the formula -1,4-epoxy-1,3,3-trimethyl-2- (2-buten-1-ylidene) cyclohexane
  • the invention further relates to a process for the preparation of the compounds of formula I.
  • This process is characterized in that 1,3,3-trimethyl-2- (3-hydroxybutylidene) -6-cyclohexen-4-ol is heated in an acidic medium.
  • the acidic medium can be produced with the aid of mineral acids, such as sulfuric acid or hydrochloric acid, of acidic salts, such as bisulfates, for example KHS0 4 , or acidic earths, such as diatomaceous earth, for example Filtrol.
  • mineral acids such as sulfuric acid or hydrochloric acid
  • acidic salts such as bisulfates, for example KHS0 4
  • acidic earths such as diatomaceous earth, for example Filtrol.
  • Suitable organic acids such as medium to strong acids of this type, are also suitable. Examples include alkanesulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or picric acid.
  • the reaction temperature is not critical. It is expediently about 20-200 C, preferably 60-130 C. It is expediently higher when using weaker acids and lower when using stronger acids.
  • the reaction is preferably carried out with the aid of an.
  • Organic solvent in particular an aromatic solvent. Examples are benzene, toluene, Xylene, etc.
  • a mixture of Ia: Ib is obtained in an approximate ratio of 15:85. Traces of the cis / cis and trans / cis isomers can also be detected in the mixture.
  • the isomer mixture can be separated in a customary manner, for example by means of column chromatography or preparative gas chromatography. As can be seen below, the isomers do not differ fundamentally in their organoleptic properties, so that the - isomer mixture can be used for economic reasons.
  • the 1,3,3-trimethyl-2- (3-hydroxybutylidene) -6-cyclohexen-4-ol referred to below and in Example 1 as compound 14 is a new compound and likewise forms the subject of the invention. As shown there, it can be obtained from the known 2-hydroxy- ⁇ -ionone.
  • this 2-hydroxy-ß-ionone is advantageously reacted with an enol acylate in the presence of one of the acids specified above;
  • an enol acylate for example, dissolved in (an excess of) acetonenol acetate, mixed with a catalytic amount of p-toluenesulfonic acid and the reaction mixture kept at the reflux temperature for 1-2 hours.
  • the diacetate 13 obtained after working up can be converted directly into the diol 14 by treatment with a strong reducing agent, such as lithium aluminum hydride.
  • the compound 13 is new and also forms the subject of the present invention.
  • the compounds I have special organoleptic properties which make them particularly suitable as fragrances and / or flavors.
  • the invention accordingly also relates to the use of the compounds I, in particular in practically pure form or in the form of mixtures (with the exception of natural mixtures containing I) as fragrances and / or flavorings.
  • Practically pure I should be understood to mean in particular those I which are free of accompanying substances such as are present in addition to I in natural extracts.
  • Practically pure I in the sense of the present invention should be understood to mean, in particular, synthetically produced I.
  • the compounds I used according to the invention as fragrances and / or flavors - in particular Ib [because of its greater diffusion and intensity] - are distinguished by fresh, green, spicy, very natural-looking, with certain aspects of cassis buds and exotic fruits - such as mango, passion fruit , Guanabana - pronounced of smells.
  • the compounds can accordingly be used, for example, for perfuming or aromatizing products, such as cosmetics (soaps, ointments, powders, toothpastes, mouthwashes, deodorants, shampoos, lotions, etc.), detergents or foods, luxury foods and beverages, the compounds preferably not used alone, but in the form of compositions with other fragrances or flavors.
  • fragrance or flavoring compositions containing compounds I and their preparation taking place in a manner known per se (Addition of I to known fragrance or flavoring compositions or mixing of I with natural or synthetic compounds or mixtures suitable as a component of fragrance or flavoring compositions) likewise forms the subject of the invention.
  • fragrance compositions produced using compounds I are particularly spectacular due to their spectacular freshness and originality.
  • fragrances listed above can be used in a manner known to the perfumer, e.g. from W.A. Poucher, Perfumes, Cosmetics and Soaps 2, 7th edition, Chapman and Hall, London, 1974.
  • the concentration of the compounds I can vary within wide limits, depending on the intended use, for example between about 0.01 (detergents) and about 15% by weight (alcoholic solutions).
  • concentrations in perfume bases or concentrates can of course also be higher.
  • the perfume bases can be used in the usual way for perfuming Eaux de Cologne, Eaux de toilette, lotions, creams, shampoos, soaps and detergents, etc.
  • the compounds I can be used, for example, to produce or improve, enhance, increase or modify fruit or berry flavors in foods (yogurt, confectionery, etc.); be used in luxury foods (tea, etc.) and beverages (lemonades, etc.).
  • a suitable dosage includes, for example, the range from 0.1 ppm to 100 ppm, preferably from 1 ppm to 20 ppm in the finished product, i.e. the flavored food, luxury food or drink.
  • the compounds can be mixed in a conventional manner with the constituents used for flavoring compositions or added to such flavors.
  • the aromas used according to the invention are understood to mean flavoring compositions which can be diluted in a manner known per se or distributed in edible materials. They can be converted into the usual forms of use, such as solutions, pastes or powders, using methods known per se.
  • the products can be spray dried, vacuum dried or lyophilized.
  • Perfume composition (towards grapefruit, lemon peel)
  • Perfumery composition (masculine chypre note)
  • the two yoghurts were presented to the test panel (10 people) and sensory-assessed in comparison to a fresh mango fruit.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
  • Seasonings (AREA)

Abstract

1,4-Epoxy - trimethyl - butenyliden - cyclohexane der Formel <IMAGE> worin R den 2-cis- oder 2-trans-Buten-1-ylidenrest bedeutet. Verfahren und Mittel zu deren Herstellung durch Erhitzen von 1,3,3- Trimethyl -2- (3-hydroxybutyliden)- 6-cyclohexen -4- ol in saurem Medium. Verwendung von (I) als Riech- und/oder Geschmackstoffe, Riech- und/oder Geschmackstoff-Kompositionen mit einem Gehalt an den neuen Cyclohexanen und Herstellung der Kompositionen.1,4-epoxy - trimethyl - butenylidene - cyclohexane of the formula <IMAGE> in which R denotes the 2-cis or 2-trans-buten-1-ylidene radical. Process and agents for their preparation by heating 1,3,3-trimethyl -2- (3-hydroxybutylidene) - 6-cyclohexen -4-ol in an acid medium. Use of (I) as fragrances and / or flavorings, fragrance and / or flavoring compositions containing the new cyclohexanes and preparation of the compositions.

Description

Die Erfindung betrifft neue Riech- und/oder Geschmackstoffe. Es handelt sich dabei um die Verbindungen der Formel

Figure imgb0001
worin R den 2-cis- oder den 2-trans-Buten-1-ylidenrest bedeutet.The invention relates to new fragrances and / or flavors. These are the compounds of the formula
Figure imgb0001
 wherein R represents the 2-cis or the 2-trans-buten-1-ylidene radical.

Die Formel umfasst demgemäss die Verbindungen der Formel

Figure imgb0002
-1,4-Epoxy-1,3,3-trimethyl-2-(2-buten-1-yliden)-cyclohexanThe formula accordingly comprises the compounds of the formula
Figure imgb0002
 -1,4-epoxy-1,3,3-trimethyl-2- (2-buten-1-ylidene) cyclohexane

Die Formeln sollen ausserdem je beide der im Hinblick auf die vorhandene cis/trans-Isomerie (2'-Stellung) möglichen geometrischen .Isomeren umfassen.The formulas are also intended to encompass both of the geometric isomers possible with regard to the cis / trans isomerism (2 'position) present.

Die Erfindung betrifft ferner ein Verfahren zur Herstellung der Verbindungen der Formel I.The invention further relates to a process for the preparation of the compounds of formula I.

Dieses Verfahren ist dadurch gekennzeichnet, dass man 1,3,3-Trimethyl-2-(3-hydroxybutyliden)-6-cyclohexen-4-ol in saurem Medium erhitzt.This process is characterized in that 1,3,3-trimethyl-2- (3-hydroxybutylidene) -6-cyclohexen-4-ol is heated in an acidic medium.

Das saure Medium kann unter Zuhilfenahme von Mineralsäuren, wie Schwefelsäure oder Salzsäure, von sauren Salzen, wie Bisulfaten, beispielsweise KHS04, oder sauren Erden, wie Diatomeenerde, z.B. Filtrol, erzeugt werden. Aber auch geeignete organische Säuren, wie mittelstarke bis starke solcher Säuren kommen in Frage. Beispiele hierfür sind Alkansulfonsäuren, wie.Methansulfonsäure, p-Toluolsulfonsäure oder Pikrinsäure.The acidic medium can be produced with the aid of mineral acids, such as sulfuric acid or hydrochloric acid, of acidic salts, such as bisulfates, for example KHS0 4 , or acidic earths, such as diatomaceous earth, for example Filtrol. Suitable organic acids, such as medium to strong acids of this type, are also suitable. Examples include alkanesulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or picric acid.

Die Reaktiönstemperatur ist nicht kritisch. Sie beträgt zweckmässigerweise ca. 20-200 C, vorzugsweise 60-130 C. Sie liegt zweckmässigerweise höher bei Verwendung schwächerer Säuren und niedriger bei Verwendung stärkerer Säuren.The reaction temperature is not critical. It is expediently about 20-200 C, preferably 60-130 C. It is expediently higher when using weaker acids and lower when using stronger acids.

Die Umsetzung wird vorzugsweise unter Zuhilfenahme eines .organischen Lösungsmittels, insbesondere eines aromatischen Lösungsmittels, durchgeführt. Beispiele sind Benzol, Toluol, Xylol, etc.The reaction is preferably carried out with the aid of an. Organic solvent, in particular an aromatic solvent. Examples are benzene, toluene, Xylene, etc.

Nach dem erfindungsgemässen Verfahren fällt ein Gemisch von Ia:Ib im ungefähren Verhältnis 15:85 an. Im Gemisch können ferner Spuren des cis/cis - und des trans/cis-Isomeren nachgewiesen werden. Die Trennung des Isomerengemisches kann auf übliche Weise, z.B. mittels Säulenchromatographie oder präparativer Gaschromatographie erfolgen. Wie weiter unten ersichtlich, unterscheiden sich die Isomeren in ihren organoleptischen Eigenschaften nicht grundlegend, sodass aus wirtschaftlichen Gründen das-Iso- merengemisch verwendet werden kann.According to the method according to the invention, a mixture of Ia: Ib is obtained in an approximate ratio of 15:85. Traces of the cis / cis and trans / cis isomers can also be detected in the mixture. The isomer mixture can be separated in a customary manner, for example by means of column chromatography or preparative gas chromatography. As can be seen below, the isomers do not differ fundamentally in their organoleptic properties, so that the - isomer mixture can be used for economic reasons.

Das - weiter unten und im Beispiel 1 - als Verbindung 14 bezeichnete l,3,3-Trimethyl-2-(3-hydroxybutyliden)-6-cyclohexen-4-ol stellt eine neue Verbindung dar und bildet ebenfalls Gegenstand der Erfindung. Es kann - wie dort gezeigt - aus dem bekannten 2-Hydroxy-ß-ionon erhalten werden.The 1,3,3-trimethyl-2- (3-hydroxybutylidene) -6-cyclohexen-4-ol referred to below and in Example 1 as compound 14 is a new compound and likewise forms the subject of the invention. As shown there, it can be obtained from the known 2-hydroxy-β-ionone.

Zu diesem Zweck wird dieses 2-Hydroxy-ß-ionon zweckmässigerweise mit einem Enolacylat in Anwesenheit einer der oben angegebenen Säuren umgesetzt; also z.B. in (einem Ueberschuss von) Acetonenolacetat gelöst, mit einer katalytischen Menge p-Toluolsulfonsäure versetzt und das Reaktionsgemisch während 1-2 Stunden bei Rückflusstemperatur gehalten. Das nach Aufarbeitung erhaltene Diacetat 13 kann durch Behandlung mit einem starken Reduktionsmittel, wie Lithiumaluminiumhydrid, direkt in das Diol 14 übergeführt werden.

Figure imgb0003
For this purpose, this 2-hydroxy-ß-ionone is advantageously reacted with an enol acylate in the presence of one of the acids specified above; Thus, for example, dissolved in (an excess of) acetonenol acetate, mixed with a catalytic amount of p-toluenesulfonic acid and the reaction mixture kept at the reflux temperature for 1-2 hours. The diacetate 13 obtained after working up can be converted directly into the diol 14 by treatment with a strong reducing agent, such as lithium aluminum hydride.
Figure imgb0003

Die Verbindung 13 ist neu und bildet ebenfalls Gegenstand der vorliegenden Erfindung.The compound 13 is new and also forms the subject of the present invention.

Die Verbindungen I weisen besondere organoleptische Eigenschaften auf, auf Grund derer sie sich vorzüglich als Riech- und/oder Geschmackstoffe eignen.The compounds I have special organoleptic properties which make them particularly suitable as fragrances and / or flavors.

Die Erfindung betrifft demgemäss auch die Verwendung der Verbindungen I, insbesondere in praktisch reiner Form oder in Form von Gemischen (mit Ausnahme von natürlichen, I enthaltenden Gemischen) als Riech- und/oder Geschmackstoffe.The invention accordingly also relates to the use of the compounds I, in particular in practically pure form or in the form of mixtures (with the exception of natural mixtures containing I) as fragrances and / or flavorings.

Unter praktisch reinen I sollen insbesondere solche I verstanden werden, die frei von Begleitstoffen sind, wie sie neben I in natürlichen Extrakten vorliegen. Als praktisch reine I im Sinne der vorliegenden Erfindung sollen insbesondere synthetisch hergestellte I verstanden werden.Practically pure I should be understood to mean in particular those I which are free of accompanying substances such as are present in addition to I in natural extracts. Practically pure I in the sense of the present invention should be understood to mean, in particular, synthetically produced I.

Die natürlichen, I enthaltenden Gemische sollen darum ausgeschlossen sein, da im Zuge der vorliegenden Arbeiten gefunden wurde, dass Ia/Ib, und zwar im Verhältnis von 1:5 im Osmanthus absolue enthalten sind.The natural mixtures containing I should therefore be excluded, since it was found in the course of the present work that Ia / Ib, namely in a ratio of 1: 5, are contained in the osmanthus absolut.

Die erfindungsgemäss als Riech- und/oder Geschmackstoffe verwendeten Verbindungen I - insbesondere Ib [wegen seiner grösseren Diffusion und Intensität] - zeichnen sich durch frische, grüne, würzige, sehr natürlich wirkende, an gewisse Aspekte von Cassisknospen und exotische Früchte - wie Mango, Passionsfruchr, Guanabana - erinnernde Geruchsnuancen aus. Die Verbindungen können demgemäss beispielsweise zur Parfümierung bzw. Aromatisierung von Produkten, wie Kosmetika (Seifen, Salben, Pudern, Zahnpasten, Mundwässern, Desodorantien, Shampoos, Lotionen, etc.), Detergentien, bzw. Nahrungsmitteln, Genussmitteln und Getränken dienen, wobei die Verbindungen vorzugsweise nicht allein, sondern in Form von Kompositionen mit andern Riech- bzw. Geschmackstoffen eingesetzt werden. Solche Riech- bzw. Geschmackstoffkompositionen mit einem Gehalt an Verbindungen I und deren auf an sich bekannte Art erfolgende Herstellung (Zugabe von I zu bekannten Riech- bzw. Geschmackstoffkompositionen oder Vermischung von I mit als Bestandteil von Riech- bzw. Geschmackstoffkompositionen geeigneten natürlichen oder synthetischen.Verbindungen oder Gemischen) bildet ebenfalls Gegenstand der Erfindung.The compounds I used according to the invention as fragrances and / or flavors - in particular Ib [because of its greater diffusion and intensity] - are distinguished by fresh, green, spicy, very natural-looking, with certain aspects of cassis buds and exotic fruits - such as mango, passion fruit , Guanabana - reminiscent of smells. The compounds can accordingly be used, for example, for perfuming or aromatizing products, such as cosmetics (soaps, ointments, powders, toothpastes, mouthwashes, deodorants, shampoos, lotions, etc.), detergents or foods, luxury foods and beverages, the compounds preferably not used alone, but in the form of compositions with other fragrances or flavors. Such fragrance or flavoring compositions containing compounds I and their preparation taking place in a manner known per se (Addition of I to known fragrance or flavoring compositions or mixing of I with natural or synthetic compounds or mixtures suitable as a component of fragrance or flavoring compositions) likewise forms the subject of the invention.

Als Riechstoffe eignen sich die Verbindungen I, insbesondere Ib, auf Grund ihrer oben beschriebenen, originellen Noten, insbesondere in Kombination mit einer Reihe von natürlichen und synthetischen Riechstoffen wie z.B.

  • - Galbanumöl, Mastixöl, Vetiveröl, Patchouliöl, Sandelholzöl, Mandarinenöl,. Petitgrainöl, Ylang-Ylang-Oel, Basilikumöl, Baummoos absolue, Patchouliblätteröl, Cedernöl, Fichtenöl, Lorbeeröl, Costuswurzelöl, Calmusöl, Beifussöl, Kamillenöl, Wermutöl, Wurmsamen- öl, Selleriesamenöl, Angelikasamenöl, Sternanisöl, Thymianöl, Rosmarinöl, Lavendelöl, Lavandinöl, Aspik- öl, Salbeiöl, Neroliöl, Bergamottöl, Citronenöl, Orangenöl, Grapefruitöl, Geraniumöl, Benzoeresinoid, Melilotus absolue, Jasmin absolue, Rosenöl, Cananga- öl, Corianderöl, Cassie absolue, Narzissen absolue, Verveine absolue oder Oel, Veilchenblätter absolue, Tuberosen absolue usw.
  • - Aldehyden wie Hydroxycitronellal, Zyklamenaldehyd, p-tert.-Butyl-α-methylhydrozimtaldehyd, alpha-Hexylzimtaldehyd, 3,5-Dimethyl-cyclohex-3-en-1-yl-carbox- aldehyd, Citral, Citronellal, 2,6-Dimethyl-6=hepten-1-al, Isovaleraldehyd, trans-2-Hexenal, Sorbinaldehyd, trans-2-Octenal, n-Octanal, n-Nonanal, trans-2,-cis-6-Nonadienal, 2,4-Decadienal, Methylnonyl-acetaldehyd usw.
  • - Ketonen wie alpha-Ionon, beta-Ionon, Allylionon, Acetanisol, 4-(para-Hydroxyphenyl)-2-butanon, Campher, Menthon, Carvon, Pulegon usw
  • - Acetalen und Ketalen wie Phenylacetaldehyd-dimethylacetal, Phenylacetaldehyd-glycerinacetal, 2-Methyl-1,3-dioxolan-2-äthylacetat, Capronaldehyd-dimethylacetal usw.
  • - Aethern wie Eugenolmethyläther, Methyl-l-methylcyclododecyläther, Anethol, Estragolusw.
  • - Phenolkörpern wie Eugenol, Isoeugenol, Creosol usw.
  • - Alkoholen wie Butanol, cis-3-Hexanol, trans-2,cis-6-Nonadienol, cis-6-Noneol, Linalool, Geraniol, Nerol, Citronellol, Nerolidol, Farnesol, Benzylalkohol, Phenyläthylalkohol, Zimtalkohol usw.
  • - Estern wie Methyldihydrojasmonat, Linalylacetat, Geranylacetat, Cedrylacetat, Vetiverylacetat, Aethylisovalerat, Aethylcaproat, para-tert.-Butylcyclohexyl- acetat, ortho-tert.-Butylcyclohexylacetat, Myraldylacetat R (Givaudan), Benzylacetat, Benzylsalicylat, Styrallylacetat, Aethyl-a-methylphenylglycidat, Aethyl-trans-2-hexenoat, Aethyl-trans-2-octenoat usw.
  • - Lactone wie y-Undecalacton, y-Decalacton, y-Nonalacton, δ-Decalacton, S-Octalacton, Cumarin usw.
  • - Säuren wie Milchsäure, Buttersäure, a-Methylbuttersäure, trans-2-Hexensäure, trans-2-Octensäure usw.
  • - Moschus- und ambraartig riechenden Körpern wie Aethylen brassylat, 4-Acetyl-6-tert.-butyl-1,1-dimethylindan, 12-Oxahexadecanolid, 8a,12-Oxido-13,14,15,16-tetranor- labdan usw.
  • - schwefelhaltigen Verbindungen wie p-Menthan-8-thiol-3-on, Dimethylsulfid und anderen Sulfiden und Disulfiden usw.
  • - stickstoffhaltigen Verbindungen wie
    Figure imgb0004
    Indol, Isobutylchinolin, verschiedenen Pyrazinen, 5-Methyl-heptan-3-on-oxim usw.
Suitable fragrances are the compounds I, in particular Ib, on the basis of their original notes described above, in particular in combination with a number of natural and synthetic fragrances such as, for example
  • - Galbanum oil, mastic oil, vetiver oil, patchouli oil, sandalwood oil, mandarin oil ,. Petitgrain oil, ylang-ylang oil, basil oil, tree moss absolut, patchouli leaf oil, cedar oil, spruce oil, laurel oil, costus root oil, calamus oil, mugwort oil, wormwood oil, worm seed oil, celery seed oil, lavender oil, thyme oil, rosemary oil, rosemary oil - oil, sage oil, neroli oil, bergamot oil, lemon oil, orange oil, grapefruit oil, geranium oil, benzoeresinoid, melilotus absolue, jasmine absolut, rose oil, cananga oil, coriander oil, cassie absolue, daffodil absolue, verveine absolue or oil, violet leaves absolue, tuberose absolue .
  • Aldehydes such as hydroxycitronellal, cyclamen aldehyde, p-tert.-butyl-α-methylhydrocinnamaldehyde, alpha-hexyl cinnamaldehyde, 3,5-dimethyl-cyclohex-3-en-1-yl-carboxaldehyde, citral, citronellal, 2,6- Dimethyl-6 = hepten-1-al, isovaleraldehyde, trans-2-hexenal, sorbinaldehyde, trans-2-octenal, n-octanal, n-nonanal, trans-2, -cis-6-nonadienal, 2,4-decadienal , Methylnonyl acetaldehyde etc.
  • - Ketones such as alpha-ionone, beta-ionone, allylionone, acetanisole, 4- (para-hydroxyphenyl) -2-butanone, camphor, menthone, carvone, pulegon, etc
  • Acetals and ketals such as phenylacetaldehyde dimethyl acetal, phenylacetaldehyde glycerol acetal, 2-methyl-1,3-dioxolane-2-ethyl acetate, capronaldehyde dimethyl acetal etc.
  • - Ethers such as eugenol methyl ether, methyl l-methylcyclododecyl ether, anethole, estragol etc.
  • - Phenolic bodies such as eugenol, isoeugenol, creosol etc.
  • - Alcohols such as butanol, cis-3-hexanol, trans-2, cis-6-nonadienol, cis-6-noneol, linalool, geraniol, nerol, citronellol, nerolidol, farnesol, benzyl alcohol, phenylethyl alcohol, cinnamon alcohol, etc.
  • - Esters such as methyl dihydrojasmonate, linalyl acetate, geranyl acetate, cedrylacetate, vetiveryl acetate, ethyl isovalerate, ethyl caproate, para-tert.-butylcyclohexyl acetate, ortho-tert.-butylcyclohexyl acetate, myraldyl acetate R (Givaudan), benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate, benzyl acetate; , Ethyl trans-2-hexenoate, ethyl trans-2-octenoate etc.
  • - Lactones such as y-undecalactone, y-decalactone, y-nonalactone, δ-decalactone, S-octalactone, coumarin etc.
  • - Acids such as lactic acid, butyric acid, a-methylbutyric acid, trans-2-hexenoic acid, trans-2-octene acid, etc.
  • - Musky and amber-smelling bodies such as ethylene brassylate, 4-acetyl-6-tert-butyl-1,1-dimethylindane, 12-oxahexadecanolide, 8a, 12-oxido-13,14,15,16-tetranor-labdan, etc .
  • - Sulfur-containing compounds such as p-menthan-8-thiol-3-one, dimethyl sulfide and other sulfides and disulfides etc.
  • - nitrogenous compounds such as
    Figure imgb0004
    Indole, isobutylquinoline, various pyrazines, 5-methyl-heptan-3-one oxime, etc.

Die unter Verwendung von Verbindungen I hergestellter Riechstoffkompositionen, insbesondere vom Typ Chypre, Cologne, Muguet bzw. allgemein blumiger und holziger Richtung bestechen insbesondere durch ihre eindrückliche Frische und Originalität.The fragrance compositions produced using compounds I, in particular of the Chypre, Cologne, Muguet or generally floral and woody direction, are particularly impressive due to their impressive freshness and originality.

Bei der Herstellung solcher Kompositionen können die oben aufgeführten bekannten Riechstoffe nach (dem Parfumeur bekannter) Art und Weise verwendet werden, wie z.B. aus W.A. Poucher, Perfumes, Cosmetics and Soaps 2, 7. Auflage, Chapman und Hall, London, 1974 hervorgehend.In the preparation of such compositions, the known fragrances listed above can be used in a manner known to the perfumer, e.g. from W.A. Poucher, Perfumes, Cosmetics and Soaps 2, 7th edition, Chapman and Hall, London, 1974.

Es hat sich schliesslich gezeigt, dass die Verbindungen Ia/Ib auch bei der Rekonstitution einer Reihe von ätherischen Oelen oder Absolues, wie z.B. Mandarinenöl, Grapefruitöl, Cassis-Knospen absolue - in denen diese Verbindungen nie nachgewiesen wurden - verwendet werden können.Finally, it has been shown that the compounds Ia / Ib also in the reconstitution of a number of essential oils or absolute, such as e.g. Mandarin oil, grapefruit oil, cassis buds absolute - in which these compounds have never been proven - can be used.

Die Konzentration'der Verbindungen I kann je nach dem Verwendungszweck innerhalb weiter Grenzen variieren, bei.- spielsweise zwischen etwa 0,01 (Detergentien) und etwa 15 Gew.% (alkoholische Lösungen). In Parfumbasen bzw. Konzentraten können die Konzentrationen selbstverständlich auch höher liegen. Die Parfumbasen können in üblicher Weise zur-Parfümierung von Eaux de Cologne, Eaux de toilette, Lotionen, Cremes, Shampoos, Seifen und Detergentien, etc. verwendet werden.The concentration of the compounds I can vary within wide limits, depending on the intended use, for example between about 0.01 (detergents) and about 15% by weight (alcoholic solutions). The concentrations in perfume bases or concentrates can of course also be higher. The perfume bases can be used in the usual way for perfuming Eaux de Cologne, Eaux de toilette, lotions, creams, shampoos, soaps and detergents, etc.

Als Geschmackstoffe können die Verbindungen I beispielsweise zur Erzeugung bzw. Verbesserung, Verstärkung, Steigerung oder Modifizierung von Frucht- oder Beerenaromen in Nahrungsmitteln (Joghurt, Süsswaren, etc.); in Genussmitteln (Tee, etc.) und Getränken (Limonaden etc.) verwendet werden.As flavorings, the compounds I can be used, for example, to produce or improve, enhance, increase or modify fruit or berry flavors in foods (yogurt, confectionery, etc.); be used in luxury foods (tea, etc.) and beverages (lemonades, etc.).

Die ausgeprägten geschmacklichen Qualitäten von insbesondere praktisch reinen, insbesondere von synthetisch hergestellten Verbindungen I ermöglichen die Verwendung in geringen Konzentrationen. Eine geeignete Dosierung umfasst beispielsweise den Bereich von 0,1 ppm.- 100 ppm, vorzugsweise von 1 ppm - 20 ppm im Fertigprodukt, d.h. dem aromatisierten Nahrungsmittel, Genussmittel oder Getränk.The pronounced taste qualities of, in particular, practically pure, in particular of synthetically produced compounds I enable use in low concentrations. A suitable dosage includes, for example, the range from 0.1 ppm to 100 ppm, preferably from 1 ppm to 20 ppm in the finished product, i.e. the flavored food, luxury food or drink.

In der folgenden Tabelle sind einige Effekte 2usammengestellt, wie sie sich mit den AethernI erzielen lassen.

Figure imgb0005
The following table summarizes some of the effects 2 that can be achieved with AethernI.
Figure imgb0005

Die Verbindungen können auf übliche Weise mit den für Geschmackstoffkompositionen verwendeten Bestandteilen vermischt bzw. solchen Arömen zugesetzt werden. Unter den erfindungsgemäss verwendeten Aromen werden Geschmackstoffkompositionen verstanden, die sich auf an sich bekannte Art verdünnen bzw. in essbaren Materialien verteilen lassen. Sie können nach an sich bekannten Methoden in die üblichen Gebrauchsformen, wie Lösungen, Pasten oder Pulver übergeführt werden. Die Produkte können sprühgetrocknet, vakuumgetrocknet oder lyophilisiert werden.The compounds can be mixed in a conventional manner with the constituents used for flavoring compositions or added to such flavors. The aromas used according to the invention are understood to mean flavoring compositions which can be diluted in a manner known per se or distributed in edible materials. They can be converted into the usual forms of use, such as solutions, pastes or powders, using methods known per se. The products can be spray dried, vacuum dried or lyophilized.

Die bei der Herstellung solcher Aromen zweckmässigerweise verwendeten bekannten Aromastoffe sind entweder in der obigen Zusammenstellung bereits enthalten oder können leicht der Literatur entnommen werden, wie z.B. J. Merory, Food Flavorings, Composition, Manufacture and Use, Second Edition, The Avi Pbublishing Company, Inc., Westport, Conn. 1968, oder G. Fenaroli, Fenaroli's Handbook of Flavor Ingredients, Second Edition, Volume 2, CRC-Press, Inc. Cleveland, Ohio, 1975.The known flavoring substances expediently used in the production of such flavors are either already included in the above compilation or can easily be found in the literature, e.g. J. Merory, Food Flavors, Composition, Manufacture and Use, Second Edition, The Avi Publishing Company, Inc., Westport, Conn. 1968, or G. Fenaroli, Fenaroli's Handbook of Flavor Ingredients, Second Edition, Volume 2, CRC-Press, Inc. Cleveland, Ohio, 1975.

Für die Herstellung solcher üblicher Gebrauchsformen kommen beispielsweise folgende Trägermaterialien, Verdickungsmittel, Geschmackstoffverbesserer, Gewürze und Hilfsingredientien, etc. in Frage:

  • Gummi arabicum, Tragant, Salze oder Brauereihefe, Alginate, Carrageen oder ähnliche Absorbentien; Indole, Maltol, Gewürzoleoresine, Raucharomen; Gewürznelken, Natriumcitrat; Mononatriumglutamat, Dinatrium-inosin-5'-monophosphat (IMP), Dinatriumguanosin-5-phosphat (GMP); oder spezielle Aromastoffe, Wasser, Aethanol, Propylenglykol, Glycerin.
The following carrier materials, thickeners, flavor improvers, spices and auxiliary ingredients, etc. are suitable for the production of such customary forms of use:
  • Gum arabic, tragacanth, salts or brewer's yeast, alginates, carrageenan or similar absorbents; Indoles, maltol, spice oleoresins, smoke flavors; Cloves, sodium citrate; Monosodium glutamate, disodium inosine 5'-monophosphate (IMP), disodium guanosine 5-phosphate (GMP); or special flavorings, water, ethanol, propylene glycol, glycerin.

Beispiel 1example 1

Eine Lösung von 25,0 g (0,129 Mol) a-Safransäureäthylester 2 und 0,25 g Bengalrosa in 300 ml Aethanol wurde in einer Belichtungsapparatur aus Pyrexglas bei gleichzeitigem Durchperlen von reinem Sauerstoff während 2 Stunden belichtet. Als Lichtquelle diente ein zentralangeordneter, wassergekühlter Quecksilber-Hochdruckstrahler Typ TQ-150 der Firma. Hanau. Die mittlere Sauerstoffaufnahme betrug rund 30 ml/Minute. Der Reaktionsverlauf wurde auf gaschromatographischem Wege (Abnahme des Eduktes) verfolgt.

Figure imgb0006
Die so erhaltene äthanolische Lösung des 1,4-Epidioxy-1,3,3-trimethyl-2-äthoxycarbonyl-5-cyclohexens 3 wurde mit 0,3 g Platin-IV-oxyd versetzt und anschliessend bei Normaldruck bis zur Sättigung hydriert. Der Wasserstoffverbrauch betrug 4,95 1 in 1,5 Stunden (=̂77,5% der Theorie). Die Reaktionslösung wurde durch Filtration vom Katalysator befreit, eingeengt und die erhaltenen rohen 31 g Reaktionsprodukte an der 20-fachen Menge Kieselgel chromatographiert. Die Elution mit Aether ergab 14,0 g cis-2,5-Dihydroxy-2,6,6-trimethylcyclohexancar- bonsäureäthylester 4 vom Schmelzpunkt 92-940 (Ausbeute = 51%, Reinheit >98%).

  • IR: 3600,3450, 1720, 1333, 1142, 1031, 1025, 932, 891 cm-1 (als Lsg. in CHCl3);
  • NMR: 1,02+1,18 (je 3H,s); 1,23 (3H,s); 1,28 (3H,t, J~6, 8 Hz); 2,57 (lH,s); 3,90 (1H, m, Jax-ax ~8 Hz, Jax-eq ~4 Hz); 4,15 (2H,q, J~6, 8 Hz) δ ppm;
  • MS: 212 (M+-H2O, 13), 166 (34), 154 (15), 129 (100), 123 (25), 113 (15), 101 (68), 95 (24), 83 (43), 43 (90).
A solution of 25.0 g (0.129 mol) of ethyl a-saffronate 2 and 0.25 g of rose bengal in 300 ml of ethanol was exposed in a Pyrex glass exposure apparatus with simultaneous bubbling of pure oxygen for 2 hours. A centrally located, water-cooled high-pressure mercury lamp type TQ-150 from the company served as the light source. Hanau. The mean oxygen uptake was around 30 ml / minute. The course of the reaction was followed by gas chromatography (removal of the starting material).
Figure imgb0006
 The ethanolic solution of 1,4-epidioxy-1,3,3-trimethyl-2-ethoxycarbonyl-5-cyclohexene 3 thus obtained was treated with 0.3 g of platinum IV oxide and then hydrogenated to saturation at atmospheric pressure. The hydrogen consumption was 4.95 l in 1.5 hours (= ̂77.5% of theory). The reaction solution was freed from the catalyst by filtration and concentrated, and the crude 31 g of reaction products obtained were chromatographed on 20 times the amount of silica gel. Elution with ether gave 14.0 g of cis-2,5-dihydroxy-2,6,6-trimethylcyclohexancar- bonsäureäthylester 4 of melting point 92-94 0 (yield = 51%, purity> 98%).
  • IR: 3600.3450, 1720, 1333, 1142, 1031, 1025, 932, 891 cm -1 (as solution in CHCl 3 );
  • NMR: 1.02 + 1.18 (each 3H, s); 1.23 (3H, s); 1.28 (3H, t, J ~ 6.8 Hz); 2.57 (1H, s); 3.90 (1H, m, J ax-ax ~ 8 Hz, J ax-eq ~ 4 Hz); 4.15 (2H, q, J ~ 6.8 Hz) δ ppm;
  • MS: 212 (M + - H 2 O, 13), 166 (34), 154 (15), 129 (100), 123 (25), 113 (15), 101 (68), 95 (24), 83 (43), 43 (90).

34,9 g (0,152 Mol) des Dihydroxyesters 4 und 3,0 g p-Toluolsulfonsäure wurden in 250 ml Toluol gelöst und anschliessend während 2 Stunden bei gleichzeitiger Entfernung des Reaktionswassers bei der Rückflusstemperatur des Reaktionsgemisches gerührt. Die abgekühlte Reaktionslösung verdünnte man mit 200 ml Aether, wusch je dreimal mit Sodalösung una Wasser, trocknete mit Natriumsulfat und engte ein. Es resultierten 32, 0 g Rohprodukt, welche gemäss gaschromatographischer Analyse 83% bzw. 10% der 2-Hydroxy-α- und ß-cyclogeraniumsäureester 5 und 6 enthielten. Als Nebenprodukt entstand zu 7% der 2,5-Oxaester 7.

Figure imgb0007
Spektrale Daten:

  • 5 IR: 3460, 1730, 1336, 1151, 1049, 1039, 1029 cm-1;
  • NMR: 0,92+0,98 (je 3H,s); 1,25 (3H, t, J~6, 8 Hz); 1,62 (3H); 2,76 (1H) ; 4,0 (1H, m) ; 4,08 (2H, q, J~6, 8 Hz); 5,4 (m,lH) δ ppm;
  • MS: 212 (M+, 9) ; 194 (25), 166 (28), 141 (19), 139 (27), 123 (28), 121 (100), 113 (32), 107 (18), 95 (53), 43 (27)
  • 6 IR: 3460, 1720, 1280,. 1235, 1030 cm-1;
  • NMR: 1,12 (6H,2s) ; 1,30 (3H, t, J~6, 8 Hz); 1,67 (3H,s); 3,52 (1H, m 4,20 (2H, q, J~6, 8 Hz) δ ppm;
  • MS: 212 (M+, 6); 169 (69), 139 (55), 125 (42), 123 (81), 121 (42), 96 (63), 95 (68), 79 (40), 67 (35), 55 (43), 43 (100)
  • 7 IR: 1730, 1310, 1216, 1179, 1119, 1046, 1000, 871 cm-1;
  • NMR: 0,98+1,21 (6H,2s); 1,24 (3H, t, J~6, 8 Hz); 1,45 (3H,s); 2,29 (1H) ; 3,90 (1H, d, J~4 Hz); 4,11 (2H, q, J~6, 8 Hz) δ ppm
  • MS: 212 (M+, 15) , 197 (45), 167 (64), 154 (76), 139 (50), 130 (84), 121 (65), 109 (36) , 95 (52), 83 (44), 55 (39), 43 (100).
34.9 g (0.152 mol) of the dihydroxy ester 4 and 3.0 g of p-toluenesulfonic acid were dissolved in 250 ml of toluene and then stirred for 2 hours while removing the water of reaction in the R ückflusstemperatur the reaction mixture. The cooled reaction solution was diluted with 200 ml of ether, washed three times with sodium carbonate solution and water, dried with sodium sulfate and concentrated. The result was 32.0 g of crude product which, according to gas chromatographic analysis, contained 83% and 10% of the 2-hydroxy-α- and β-cyclogeranic acid esters 5 and 6, respectively. 7% of the 2,5-oxaester 7 was formed as a by-product
Figure imgb0007
 Spectral data:
  • 5 IR: 3460, 1730, 1336, 1151, 1049, 1039, 1029 cm -1 ;
  • NMR: 0.92 + 0.98 (3H, s each); 1.25 (3H, t, J ~ 6.8 Hz); 1.62 (3H); 2.76 (1H); 4.0 (1H, m); 4.08 (2H, q, J ~ 6.8 Hz); 5.4 (m, 1H) δ ppm;
  • MS: 212 (M + , 9); 194 (25), 166 (28), 141 (19), 139 (27), 123 (28), 121 (100), 113 (32), 107 (18), 95 (53), 43 (27)
  • 6 IR: 3460, 1720, 1280 ,. 1235, 1030 cm -1 ;
  • NMR: 1.12 (6H, 2s); 1.30 (3H, t, J ~ 6.8 Hz); 1.67 (3H, s); 3.52 (1H, m 4.20 (2H, q, J ~ 6.8 Hz) δ ppm;
  • MS: 212 (M + , 6); 169 (69), 139 (55), 125 (42), 123 (81), 121 (42), 96 (63), 95 (68), 79 (40), 67 (35), 55 (43), 43 (100)
  • 7 IR: 1730, 1310, 1216, 1179, 1119, 1046, 1000, 871 cm -1 ;
  • NMR: 0.98 + 1.21 (6H, 2s); 1.24 (3H, t, J ~ 6.8 Hz); 1.45 (3H, s); 2.29 (1H); 3.90 (1H, d, J ~ 4 Hz); 4.11 (2H, q, J ~ 6.8 Hz) δ ppm
  • MS: 212 (M + , 15), 197 (45), 167 (64), 154 (76), 139 (50), 130 (84), 121 (65), 109 (36), 95 (52), 83 (44), 55 (39), 43 (100).

Das obige Rohprodukt (32,0 g) - gelöst in 80 ml Tetrahydrofuran - liess man im Verlaufe von 30 Minuten zu einer Suspension von 4,60 g (0,12 Mol) Lithiumaluminiumhydrid in 300 ml wasserfreiem Tetrahydrofuran zutropfen. Man rührte das entstandene Gemisch während 16 Stunden bei Rückflusstemperatur. Das auf O° abgekühlte Reaktionsgemisch wurde vorsichtig mit Wasser, hierauf mit 2 N Salzsäurelösung versetzt, in 400 ml Aether aufgenommen und die ätherische Schicht mit Wasser gewaschen, getrocknet und eingeengt. Es verblieben 26,2 g Rohprodukt, welches gemäss gaschromatographischer Analyse 80% 2-Hydroxy-a-cyclogeraniol 8 enthielten.

Figure imgb0008
Eine aus Aether umkristallisierte Probe zeigte die folgenden spektroskopischen Daten:

  • IR: 3615, 3450, 1175, 1068, 1037, 1018, 955, 845 cm 1 (als Lsg. in CHC13);
  • NMR: 0,90+1,09 (je 3H,2s); 1,75 (3H); 3,80 (2H, d, J~4 Hz); 3,95 (lH,m); 5,50 (lH,m) δ ppm;
  • MS: 170 (M+, 1), 152 (83), 121 (80), 109 (36), 107 (52), 95 (47), 93 (34), 81 (79), 72 (59), 55 (42), 43 (100), 41 (51);
  • Smp. 103-104°.
The above crude product (32.0 g) - dissolved in 80 ml of tetrahydrofuran - was added dropwise over 30 minutes to a suspension of 4.60 g (0.12 mol) of lithium aluminum hydride in 300 ml of anhydrous tetrahydrofuran. The resulting mixture was stirred at reflux temperature for 16 hours. The reaction mixture, cooled to 0 °, was carefully mixed with water, then 2N hydrochloric acid solution, taken up in 400 ml of ether and the ethereal layer was washed with water, dried and concentrated. There remained 26.2 g of crude product which, according to gas chromatographic analysis, contained 80% 2-hydroxy-a-cyclogeraniol 8.
Figure imgb0008
 A sample recrystallized from ether showed the following spectroscopic data:
  • IR: 3615, 3450, 1175, 1068, 1037, 1018, 955, 845 cm 1 (as L see in CHC1 3 );
  • NMR: 0.90 + 1.09 (3H, 2s each); 1.75 (3H); 3.80 (2H, d, J ~ 4 Hz); 3.95 (1H, m); 5.50 (1H, m) δ ppm;
  • MS: 170 (M + , 1), 152 (83), 121 (80), 109 (36), 107 (52), 95 (47), 93 (34), 81 (79), 72 (59), 55 (42), 43 (100), 41 (51);
  • M.p. 103-104 °.

15,0 g (0',088 Mol) rohes 2-Hydroxy-a-cyclogeraniol 8 wurden in 60 ml Methylchlorid gelöst und im Verlaufe von 10 Minuten so zu einer Lösung von 19,0 g (0,088 Mol) Pyridiniumchlorochromat (E.J. Corey, J.W. Suggs, Tet. Lett. 31, 2647 [1975]) in 250 ml Methylchlorid zugetropft, dass die Reaktionstemperatur zwischen 20 und 25° blieb. Anschliessend rührte man noch während 20 Minuten bei Raumtemperatur, dekantierte die Reaktionslösung vom gebildeten Niederschlag ab, spülte den Niederschlag zweimal mit Methylenchlorid und wusch die kombinierten organischen Phasen mit Wasser, 2 N Salzsäure, Spektrale Daten:

  • 11 IR: 3450, 1670, 1620, 1256, 1051, 989, 905, 815 cm-1;
  • NMR: 0,96 (6H,2s); 1,58 (3H); 2,27 (3H, s); 2,54 (1H, d, J~10 Hz); 3,68 (lH,dxd, Jax-ax~7 Hz, J ax-eq~5 Hz); 5,44 (lH,m); 6,08 (1H, d, J~16 Hz); 6,68 (lH,dxd, J1~16 Hz), J2~10 Hz) δ ppm;
  • MS: 208 (M+, 1); 175 (51), 157 (10), 147 (19), 137 (26), 121 (43), 109 (13), 93 (51), 77 (14), 72 (21), 43 (100);
  • 12 IR: 3460, 1665, 1608, 1256, 1190, 1175, 1115, 1042, 1005 978 cm-1
  • NMR: 1,08+1,11 (je 3H,2s); 1,75 (3H); 2,29 (3H,s); 3,56 (lH,dxd, Jax-ax~7 Hz, Jax-eq~4, 6 Hz); 6,10 (1H, d, J~16, 5 Hz); 7,21 (1H, d, J~16, 5 Hz) δ ppm;
  • MS: 208 (M+, 2) , 193 (69), 175 (44), 157 (8), 149 (26), 147 (20), 121 (36), 105 (33), 83 (16), 81 (19), 79 (14), 43 (100).
15.0 g (0 ', 088 mol) of crude 2-hydroxy-a-cyclogeraniol 8 were dissolved in 60 ml of methyl chloride and in the course of 10 minutes to a solution of 19.0 g (0.088 mol) of pyridinium chlorochromate (EJ Corey, JW Suggs, Tet. Lett. 31, 2647 [1975]) was added dropwise in 250 ml of methyl chloride so that the reaction temperature remained between 20 and 25 °. The mixture was then stirred for a further 20 minutes at room temperature, the reaction solution was decanted from the precipitate formed, the precipitate was rinsed twice with methylene chloride and the combined organic phases were washed with water, 2N hydrochloric acid, Spectral data:
  • 11 IR: 3450, 1670, 1620, 1256, 1051, 989, 905, 815 cm -1 ;
  • NMR: 0.96 (6H, 2s); 1.58 (3H); 2.27 (3H, s); 2.54 (1H, d, J ~ 10 Hz); 3.68 (1 H , dxd, J ax-ax ~ 7 Hz, J ax-eq ~ 5 Hz); 5.44 (1H, m); 6.08 (1H, d, J ~ 16 Hz); 6.68 (1H, dxd, J 1 ~ 16 Hz), J 2 ~ 10 Hz) δ ppm;
  • MS: 208 (M + , 1); 175 (51), 157 (10), 147 (19), 137 (26), 121 (43), 109 (13), 93 (51), 77 (14), 72 (21), 43 (100);
  • 12 IR: 3460, 1665, 1608, 1256, 1190, 1175, 1115, 1042, 1005 978 cm -1
  • NMR: 1.08 + 1.11 (3H, 2s each); 1.75 (3H); 2.29 (3H, s); 3.56 (1H, dxd, J ax-ax ~ 7 Hz, J ax-eq ~ 4.6 Hz); 6.10 (1H, d, J ~ 16.5 Hz); 7.21 (1H, d, J ~ 16.5 Hz) δ ppm;
  • MS: 208 (M + , 2), 193 (69), 175 (44), 157 (8), 149 (26), 147 (20), 121 (36), 105 (33), 83 (16), 81 (19), 79 (14), 43 (100).

3,87 g der 2-Hydroxy-ionone 11 + 12 (1:5) wurden in 20 ml Acetonenolacetat gelöst und anschliessend in Gegenwart von 0,03 g p-Toluolsulfonsäure 2 Stunden bei Rückflusstemperatur gerührt. Das Reaktionsgemisch wurde abgekühlt, in 150 ml Aether aufgenommen, die ätherische Phase mit Bicarbonatlösung und Wasser gewaschen, getrocknet und eingeengt. Es verblieben 4,5 g des 4-Acetoxy-1, 3, 3-trimethyl-2-(3-acetoxy-2-butenyliden)-cyclohex-6-ens 13, welche wie folgt direkt zum Diol 14 weiterverarbeitet wurden:

Figure imgb0009
3.87 g of the 2-hydroxy-ionones 11 + 12 (1: 5) were dissolved in 20 ml of acetonenol acetate and then stirred for 2 hours at the reflux temperature in the presence of 0.03 g of p-toluenesulfonic acid. The reaction mixture was cooled, taken up in 150 ml of ether, the ethereal phase washed with bicarbonate solution and water, dried and concentrated. There remained 4.5 g of 4-acetoxy-1, 3, 3-trimethyl-2- (3-acetoxy-2-butenylidene) -cyclohex-6-ene 13, which were processed directly to diol 14 as follows:
Figure imgb0009

Eine Lösung von 3,9 g Diacetat 13 in 10 ml Aether liess man im Verlaufe von 10 Minuten zu einer Suspension von 1,06 g Lithiumaluminiumhydrid in 70 ml Aether zutropfen, rührte das Bicarbonatlösung und nochmals mit Wasser. Nach dem Trocknen und Einengen verblieben 11,9 g Rohprodukt, welche die beiden Hydroxyaldehyde

Figure imgb0010
im Verhältnis von 3:1 enthielten.A solution of 3.9 g of diacetate 13 in 10 ml of ether was allowed to A is added dropwise over 10 minutes to a suspension of 1.06 g lithium aluminum hydride in 70 ml of ether, stirring the Bicarbonate solution and again with water. After drying and concentrating, 11.9 g of crude product remained, which are the two hydroxyaldehydes
Figure imgb0010
 contained in a ratio of 3: 1.

Spektrale Daten:

  • 9 MS: 168 (M+,23), 150 (14), 137 (38), 121 (55), 107 (42), 97 (59), 95 (44), 79 (28), 72 (30), 55 (40), 43 (10);
  • 10 MS: 168 (M+, 16), 137 (100), 123 (15), 109 (31), 95 (11), 81 (46), 79 (14), 70 (78), 67 (31), 55 (13), 41 (21)
Spectral data:
  • 9 MS: 168 (M + , 23), 150 (14), 137 (38), 121 (55), 107 (42), 97 (59), 95 (44), 79 (28), 72 (30) , 55 (40), 43 (10);
  • 10 MS: 168 (M + , 16), 137 (100), 123 (15), 109 (31), 95 (11), 81 (46), 79 (14), 70 (78), 67 (31) , 55 (13), 41 (21)

11,9 g des rohen Aldehydgemisches 9/10 wurden in 120 ml Aceton gelöst, mit 23 ml 10%iger wässriger KOH-Lösung versetzt und anschliessend während 19 Stunden bei Rückflusstemperatur gerührt. Die Hälfte des Acetons wurde unter vermindertem Druck abdestilliert, das Konzentrat in 200 ml Aether aufgenommen und die ätherische Lösung mit konzentrierter Kochsalzlösung gewaschen. Nach Trocknen und Einengen verblieben 12,5 g Rohprodukt, welche gemäss gas hromatographischer Analyse zu rund 40% aus den 2-Hydroxy-β-iononen 11 und 12 im Verhältnis von 1:5 bestanden. Die säulenchromatographische Reinigung des Rohproduktes lieferte bei der Elution mit Hexan/Aether-= 1:1 4,2 g 92%iges Gemisch der 2-Hydroxy-ionone 11 und 12.

Figure imgb0011
Zur spektroskopischen Charakterisierung gelangten Proben, welche mit Hilfe von präparativer Gaschromatographie auf eine Reinheit von >95% gebracht wurden.
Reaktionsgemisch während einer Stunde bei
Figure imgb0012
kühlte hierauf auf Raumtemperatur, zersetzte den Uehereschuse an Lithiumaluminiumhydrid vorsichtig mit Wasser, wusch d;.e Aetherphase mit Wasser, t cocknete und engte ein. Die verbliebenen 2,7 g Diol 14 löst man zusammen mit 0,05 g
Figure imgb0013
sulfonsäure in 25 ml Benzol und rührte das Gemisch anschli send während einer Stunde bei Rückflusstemperatur,
Figure imgb0014
das abgekühlte Gemisch mit 50 ml Aether und wusch die etherphase mit Bicarbonatlösung und Wasser. Nach dem Trocknen und Einengen verblieben 2,3 g Rohprodukt, welche gemäss gaschromatographischer Analyse neben schwererflüchtigen Verbindungen zu rund 50% aus 1, 4-Epoxy-1, 3, 3-trimethyl-2-(2-buten-1-yliden)-cyclohexan la und lb (Verhältnis cis/trans = 15:85) bestand.11.9 g of the crude aldehyde mixture 9/10 were dissolved in 120 ml of acetone, mixed with 23 ml of 10% aqueous KOH solution and then stirred at reflux temperature for 19 hours. Half of the acetone was distilled off under reduced pressure, the concentrate was taken up in 200 ml of ether and the ethereal solution was washed with concentrated saline. After drying and concentration, 12.5 g of crude product remained, which according to gas chromatographic analysis consisted of around 40% of the 2-hydroxy-β-ionones 11 and 12 in a ratio of 1: 5. Column chromatographic purification of the crude product gave 4.2 g of 92% mixture of 2-hydroxy-ionones 11 and 12 on elution with hexane / ether = 1: 1.
Figure imgb0011
 For spectroscopic characterization, samples were obtained which were brought to a purity of> 95% using preparative gas chromatography.
Reaction mixture during one hour
Figure imgb0012
Thereupon cooled to room temperature, carefully decomposed the lithium aluminum hydride Uescheschuse with water, washed the ether phase with water, t cocknete and constricted. The remaining 2.7 g of diol 14 are dissolved together with 0.05 g
Figure imgb0013
sulfonic acid in 25 ml of benzene and then stirred the mixture for one hour at reflux temperature,
Figure imgb0014
the cooled mixture with 50 ml of ether and washed the ether phase with bicarbonate solution and water. After drying and concentration, 2.3 g of crude product remained, which, according to gas chromatographic analysis, contains around 50% of 1, 4-epoxy-1, 3, 3-trimethyl-2- (2-buten-1-ylidene) in addition to less volatile compounds. cyclohexane la and lb (ratio cis / trans = 15:85) existed.

Durch Kugelrohrdestillation des Rohproduktes erhielt man 0,95 g Produkt, welches zu über 92% aus dem Isomerengemisch bestand. Das Gemisch besitzt einen frischen, grünen, würzigen, sehr natürlich wirkenden Geruch, der an gewisse Aspekte von Tomatenblättern,Cassisknospen und exotischen Früchten erinnert.Kugelrohr distillation of the crude product gave 0.95 g of product, which consisted of over 92% of the isomer mixture. The mixture has a fresh, green, spicy, very natural smell that is reminiscent of certain aspects of tomato leaves, cassis buds and exotic fruits.

Zur spektroskopischen Charakterisierung gelangten Proben der einzelnen Isomeren, welche durch Chromatographie an der 40-fachen Menge Kieselgel (Hexan/Aether = 30:1) auf eine Reinheit von über 98% gebracht worden waren.For the spectroscopic characterization, samples of the individual isomers were obtained which had been brought to a purity of over 98% by chromatography on 40 times the amount of silica gel (hexane / ether = 30: 1).

Spektralen Daten:

  • la IR: 1410, 1183, 1118, 1019, 1002, 990, 961, 928, 878, 833, 770 cm-1;
  • NMR: 1,04+1,13 (je 3H,s); 1,75 (3H,s); 1,78 (3H, d, J~7 Hz); 3,93 (1H, d, J~4 Hz); 5,55 (1H, dxq, J3', 2' ~16 Hz, J3', CH3~7 Hz), ~5, 55 (1H, d, J~10 Hz), ~6, 3 (lH,dxd, J2', 3'~16 Hz, J2', 1'~10 Hz);
  • MS: 192 (M+, 24); 149 (16), 136 (22), 123 (45), 121 (35), 109 (49), 93 (26), 91 (32), 81 (44), 69 (86), 43 (100)
  • lb IR: 1421, 1235, 1195, 1117, 1021, 1003, 963, 872, 823 cm-1;
  • NMR: 1,28 (6H,2s); 1,50 (3H,s); 1,78 (3H, d, J~7 Hz); 3,89 (1H, d, J~4 Hz); 5,55 (lH,dxq, J3', 2' ~16 Hz; J3',CH3 ~7 Hz); 5,65 (1H, d, J1', 2' ~10 Hz); 6,30 (1H, dxd, J2', 3' ~16 Hz; J2', 1' ~10 Hz);
  • MS: 192 (M+, 24) , 149 (12), 136 (12), 123 (39), 121 (22), 109 (36), 93 (18), 91 (18), 81 (33), 69 (82), 43 (100).
Spectral data:
  • la IR: 1410, 1183, 1118, 1019, 1002, 990, 961, 928, 878, 833, 770 cm -1 ;
  • NMR: 1.04 + 1.13 (each 3H, s); 1.75 (3H, s); 1.78 (3H, d, J ~ 7 Hz); 3.93 (1H, d, J ~ 4 Hz); 5.55 (1H, dxq, J 3 ', 2' ~ 16 Hz, J 3 ' , CH 3 ~ 7 Hz ), ~ 5.55 (1H, d, J ~ 10 Hz), ~ 6, 3 (l H , d x d , J 2 ', 3' ~ 16 Hz, J 2 ', 1' ~ 10 Hz);
  • MS: 192 (M + , 24); 149 (16), 136 (22), 123 (45), 121 (35), 109 (49), 93 (26), 91 (32), 81 (44), 69 (86), 43 (100)
  • l b IR : 1421, 1 235 , 1195, 1117, 1 0 21, 1003 , 9 6 3 , 872 , 823 cm -1 ;
  • NMR: 1.28 (6H, 2s); 1.50 (3H, s); 1.78 (3H, d, J ~ 7 Hz); 3.89 (1H, d, J ~ 4 Hz); 5.55 (1H, dx q , J 3 ', 2' ~ 16 Hz; J 3 ', CH3 ~ 7 Hz); 5.65 (1H, d, J 1 ', 2' ~ 10 Hz); 6.30 (1H, dxd, J 2 ', 3' ~ 16 Hz; J 2 ', 1' ~ 10 Hz);
  • M S: 192 (M + , 24), 149 (12), 136 (12), 123 (39), 121 (22), 109 (36), 93 (18), 91 (18), 81 (33) , 69 (82), 43 (100).

Beispiel 2Example 2 Grün-BaseGreen base

Figure imgb0015
Figure imgb0015

Gibt man zu dieser konventionellen Grün-Base (Richtung Salbei) 200 Teile der neuen Verbindung I*, wird die Base in Richtung Tomatenblätter und Cassis-Knospen sehr angenehm abgerundet. Die neue Substanz fügt sich sehr harmonisch in den Komplex ein und verleiht ihm eine frische, würzige etwas trockene und viel weniger süsse Note.If 200 parts of the new compound I * are added to this conventional green base (towards sage), the base is rounded off very pleasantly in the direction of tomato leaves and cassis buds. The new substance blends harmoniously into the complex and gives it a fresh, spicy, slightly dry and much less sweet note.

* Unter "Verbindung I" wird in den Formulierungsbeispielen das im Beispiel 1 erhaltene Isomerengemisch verstanden. * "Compound I" in the formulation examples means the isomer mixture obtained in Example 1.

Beispiel 3Example 3 Parfumerie-Komposition (Richtung Grapefruit, Zitronenschale)Perfume composition (towards grapefruit, lemon peel)

Figure imgb0016
Figure imgb0016

Werden 100 Teile der neuen Verbindung I zu dieser Base mit schwarzem Johannisbeer-Charakter gegeben,.verschwindet die Cassis-Note zu Gunsten einer sehr angenehm frischen Note Richtung Grapefruit und Zitronenschale. Die Substanz verbindet sich, wie ersichtlich, sehr harmonisch mit schwefelhaltigen Verbindungen. Die neue Base erhält eine sehr natürliche Frische. Ueberraschenderweise wird dieser Frische-Effekt auch nach 24 Stunden noch sehr deutlich wahrgenommen.If 100 parts of the new compound I are added to this base with black currant character, the cassis note disappears in favor of a very pleasantly fresh note in the direction of grapefruit and lemon peel. As can be seen, the substance combines very harmoniously with sulfur-containing compounds. The new base gets a very natural freshness. Surprisingly, this freshness effect is still very clearly perceived even after 24 hours.

Beispiel 4Example 4 Parfumerie-Komposition (Grünnote)Perfume composition (green note)

Figure imgb0017
Figure imgb0017

Gibt man zu dieser Grün-Base 40 Teile der neuen Verbindung I, so wirkt die Komposition viel diffusiver, frischer, natürlicher. Die Grün-Note erhält einen fruchtigen Aspekt Richtung Cassis-Knospen. Der - für die Grünnote wesentliche - Komplex von Galbanumöl und Methyldihydrojasmonat wird durch Zugabe von I in äusserst vorteilhafter Weise unterstrichen.If you add 40 parts of the new compound I to this green base, the composition appears much more diffuse, fresher, more natural. The green note gets a fruity aspect towards cassis buds. The - essential for the green note - complex of galbanum oil and methyl dihydrojasmonate is emphasized in an extremely advantageous manner by adding I.

Beispiel 5Example 5 Parfümerie-Komposition (maskuline Chypre-Note)Perfumery composition (masculine chypre note)

Figure imgb0018
Figure imgb0018

'Versetzt man diese Komposition (Chypre-Charakter) mit 20 Teilen der neuen Verbindung I, so wirkt die gesamte Kom- position lebhafter, wirkt gleichzeitig abgerundeter, hat eindeutig mehr Charakter eines "fertigen" Cologne. Die neue Komposition eignet sich gut zur Herstellung eines maskulinen Herren-Cologne.'If you add 20 parts of the new compound I to this composition (chypre character), the entire composition appears livelier, at the same time appears rounded, has clearly more character of a "finished" cologne. The new composition is well suited for the production of a masculine men's cologne.

Beispiel 6Example 6 Parfümerie-Komposition (Muguet-Charakter)Perfumery composition (Muguet character)

Figure imgb0019
Figure imgb0019

Versetzt man diese konventionelle Muguet-Komposition mit 10 Teilen der neuen Verbindung I, so wird sofort eine eindeutige Verbesserung des Geruchseindrucks in Richtung der natürlichen Vorlage festgestellt.If this conventional Muguet composition is mixed with 10 parts of the new compound I, a clear improvement in the smell impression in the direction of the natural template is immediately noticed.

Gewisse Aspekte des taufrischen Maiglöckchens kommen nun sehr schön zur Geltung.Certain aspects of the dewy lily of the valley now come into their own.

Beispiel 7Example 7

1 Liter eines handelsüblichen Passionsfrucht-Saftes Wurde mit 0,35 g einer 0,1% igen alkoholischen Lösung des 1,4-Epoxy-1, 3, 3-trimethyl-2-(2-butenyliden)-cyclohexanes versetzt. Entsprechend versetzte man 1 Liter Passionsfrucht-Saft mit 0,35 g reinem Alkohol. Die beiden Früchtsäfte wurden einer Gruppe von 10 Testpersonen zur sensorischen Beurteilung vorgelegt. Die Mehrheit der Testpersonen (8) erklärte, dass in der zusätzlich aromatisierten Probe der angenehm süsse, exotisch wirkende Geruchsaspekt der Passionsfrucht eindeutig besser zur Geltung käme.1 liter of a commercially available passion fruit juice was mixed with 0.35 g of a 0.1% alcoholic solution of 1,4-epoxy-1, 3, 3-trimethyl-2- (2-butenylidene) cyclohexane. Accordingly, 1 liter of passion fruit juice was mixed with 0.35 g of pure alcohol. The two fruit juices were presented to a group of 10 test persons for sensory evaluation. The majority of the test persons (8) stated that the pleasantly sweet, exotic smell aspect of the passion fruit was clearly better used in the additionally flavored sample.

Beispiel 8Example 8

Analog dem vorgehenden Beispiel wurde 1 Liter Grapefruit-Saft mit 0,40 g einer 0,1%igen alkoholischen Lösung des 1,4- Epoxy-l,3,3-trimethyl-2-(2-butenyliden)-cyclohexanes versetzt. In diesem Falle wurde im Vergleich zur Blindprobe von der Mehrheit der Testpersonen (8) eine ausgeprägtere Holznote festgestellt, zudem wurde eine Assoziation an reife Grapefruit-Früchte äusserst positiv vermerkt.Analogous to the preceding example, 1 liter of grapefruit juice was mixed with 0.40 g of a 0.1% alcoholic solution of the 1,4-e poxy-l, 3,3-trimethyl-2- (2-butenylidene) -cyclohexanes added. In this case, the majority of the test persons (8) found a more pronounced wood note compared to the blind sample, and an association with ripe grapefruit fruits was noted extremely positively.

Beispiel 9Example 9

1 kg Yoghurt "nature" wurde mit 100 g Mango-Früchtpulpe und 80 g Saccharose versetzt. Zu 500 g dieses Mango-Yoghurts gab man 0,25 g einer O,1%igen alkoholischen Lösung des 1,4-Epoxy-1,3,3-trimethyl-2-(2-butenyliden)-cyclohexanes.1 kg of "nature" yoghurt was mixed with 100 g of mango fruit pulp and 80 g of sucrose. 0.25 g of an 0.1% alcoholic solution of 1,4-epoxy-1,3,3-trimethyl-2- (2-butenylidene) cyclohexane was added to 500 g of this mango yoghurt.

Die beiden Yoghurts wurden dem Testpanel (10 Personen) vorgelegt und im Vergleich zu einer frischen Mangofrucht sensorisch beurteilt.The two yoghurts were presented to the test panel (10 people) and sensory-assessed in comparison to a fresh mango fruit.

Die Mehrheit der Testpersonen (6) fand im zusätzlich mit I aromatisierten Yoghurt eindeutig wesentlich mehr Charakter der frischen Mango-Frucht.The majority of the test persons (6) found the yoghurt flavored with I clearly more character of the fresh mango fruit.

Claims (14)

1. Verfahren zur Herstellung der Verbindungen der Formel
Figure imgb0020
worin R den 2-cis- oder den 2-trans-Buten-1-ylidenrest bedeutet,
dadurch gekennzeichnet, dass man 1,3,3-Trimethyl-2-(3-hydroxybutyliden)-6-cyclohexen-4-ol in saurem Medium erhitzt.1. Process for the preparation of the compounds of the formula
Figure imgb0020
 where R is the 2-cis or the 2-trans-buten-1-ylidene radical,
characterized in that 1,3,3-trimethyl-2- (3-hydroxybutylidene) -6-cyclohexen-4-ol is heated in an acidic medium. 2. Riech- und/oder Geschmackstoffkompositionen, gekennzeichnet durch einen Gehalt an einer Verbindung der Formel
Figure imgb0021
worin R den 2-cis- oder den 2-trans-Buten-1-ylidenrest bedeutet,
in praktisch reiner Form oder in Form von Gemischen (mit Ausnahme der natürlichen, Verbindungen der Formel I enthaltenden Gemische). 2. R iech- and / or flavoring substance compositions, characterized by a content of a compound of formula
Figure imgb0021
 where R is the 2-cis or the 2-trans-buten-1-ylidene radical,
in practically pure form or in the form of mixtures (with the exception of the natural mixtures containing compounds of the formula I). 3. Riech- und/oder Geschmackstoffkompositionen nach Anspruch 2, gekennzeichnet durch einen Gehalt an einer synthetisch hergestellten Verbindung der Formel I.3. fragrance and / or flavoring compositions according to claim 2, characterized by a content of a synthetically produced compound of formula I. 4. Verfahren zur Herstellung von neuen Kompositionen gemäss Anspruch 2, dadurch gekennzeichnet, dass man bekannten Riech- und/oder Geschmackstoffkompositionen eine Verbindung der Formel
Figure imgb0022
worin R den 2-cis- oder den 2-trans-Buten-1-ylidenrest bedeutet,
in praktisch reiner Form oder in Form von Gemischen (mit Ausnahme der natürlichen, Verbindungen der Formel I enthaltenden Gemische) zusetzt, oder dass man eine Verbindung der Formel I in praktisch reiner Form oder in Form von Gemischen (mit Ausnahme der natürlichen, Verbindungen der Formel I enthaltenden Gemische) mit als Bestandteil von Riech- und/oder Geschmackstoffkompositionen geeigneten natürlichen oder synthetischen Verbindungen oder Gemischen vermischt.4. A process for the preparation of new compositions according to claim 2, characterized in that known fragrance and / or flavoring compositions are a compound of the formula
Figure imgb0022
 where R is the 2-cis or the 2-trans-buten-1-ylidene radical,
in practically pure form or in the form of mixtures (with the exception of the natural mixtures containing compounds of the formula I), or that a compound of the formula I in practically pure form or in the form of mixtures (with the exception of the natural compounds of the formula I containing mixtures) mixed with natural or synthetic compounds or mixtures suitable as a constituent of fragrance and / or flavoring compositions. 5. Verfahren zur Herstellung von neuen Kompositionen gemäss Anspruch 3, dadurch gekennzeichnet, dass man bekannten Riech- und/oder Geschmackstoffkompositionen eine synthetisch hergestellte Verbindung I zusetzt, oder dass man eine synthetisch hergestellte Verbindung der Formel I mit als Bestandteil von Riech- und/oder Geschmackstoffkompositionen geeigneten natürlichen oder synthetischen Verbindungen oder Gemischen vermischt.
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
den 2-cis- oder den 2-trans-Buten-
Figure imgb0028
bedeutet.5. A process for the preparation of new compositions according to claim 3, characterized in that known fragrance and / or flavoring compositions are added to a synthetically produced compound I, or in that a synthetically produced compound of the formula I is used as a component of odoriferous and / or Flavor compositions mixed suitable natural or synthetic compounds or mixtures.
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
the 2-cis or the 2-trans-butene
Figure imgb0028
means. 10. Praktisch reines cis/trans-1,4-Epoxy-1,3,3-trimethyl-2-(2-buten-1-yliden)-cyclohexan.10. Practically pure cis / trans-1,4-epoxy-1,3,3-trimethyl-2- (2-buten-1-ylidene) cyclohexane. 11. Praktisch reines trans/trans-1,4-Epoxy-1,3,3-trimethyl-
Figure imgb0029
1-yliden)-cyclohexan.11. Practically pure trans / trans-1,4-epoxy-1,3,3-trimethyl
Figure imgb0029
1-ylidene) cyclohexane. 12. Synthetisch hergestellte Verbindungen der Formel
Figure imgb0030
worin R den 2-cis- oder den 2-trans-Buten-1-ylidenrest bedeutet.12. Synthetically prepared compounds of the formula
Figure imgb0030
 wherein R represents the 2-cis or the 2-trans-buten-1-ylidene radical. 13. Synthetisch hergestelltes cis/trans-1, 4-Epoxy-1, 3, 3-trimethyl-2-(2-buten-1-yliden)-cyclohexan.13. Synthetically produced cis / trans-1,4-epoxy-1,3,3-trimethyl-2- (2-buten-1-ylidene) cyclohexane. 14. Synthetisch hergestelltes trans/trans-1,4-Epoxy-1, 3, 3-trimethyl-2-(2-buten-1-yliden)-cyclohexan.14. Synthetically produced trans / trans-1,4-epoxy-1,3,3-trimethyl-2- (2-buten-1-ylidene) cyclohexane. 15. 1,3,3-Trimethyl-2-(3-hydroxybutyliden)-6-cyclohexen-4-ol.15. 1,3,3-trimethyl-2- (3-hydroxybutylidene) -6-cyclohexen-4-ol. 16. 4-Acetoxy-1, 3, 3-trimethyl-2-(3-acetoxy-2-butenyliden)-cyclohex-6-en.16. 4-Acetoxy-1,3,3-trimethyl-2- (3-acetoxy-2-butenylidene) cyclohex-6-ene. 17. Verwendung von Verbindungen der Formel
Figure imgb0031
worin R den 2-cis- oder den 2-trans-Buten-1-ylidenrest bedeutet,
in praktisch reiner Form oder in Form von Gemischen (mit Ausnahme der natürlichen, Verbindungen der Formel I enthaltenden Gemische) als Riech- und/oder Geschmackstoffe.17. Use of compounds of the formula
Figure imgb0031
 where R is the 2-cis or the 2-trans-buten-1-ylidene radical,
in practically pure form or in the form of mixtures (with the exception of the natural mixtures containing compounds of the formula I) as fragrances and / or flavors. 18. Verwendung von synthetisch hergestellten Verbindungen der Formel
Figure imgb0032
worin R den 2-cis- oder den 2-trans-Buten-1-ylidenrest bedeutet,
als Riech- und/oder Geschmackstoffe.18. Use of synthetically produced compounds of the formula
Figure imgb0032
 where R is the 2-cis or the 2-trans-buten-1-ylidene radical,
as fragrances and / or flavors.
EP78100472A 1977-07-25 1978-07-21 1,4-epoxy-trimethyl-butenylidene-cyclohexanes (i), process for their preparation, use of (i) as fragrance and/or flavouring substance, fragrance and/or flavour compositions containing the cyclohexanes Expired EP0000719B1 (en)

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LU77834A LU77834A1 (en) 1977-07-25 1977-07-25 PROCESS FOR THE PRODUCTION OF NEW SMELLS AND / OR FLAVORS
LU77834 1977-07-25
CH5464/78 1978-05-19
CH546478 1978-05-19

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FR (1) FR2398751A1 (en)
GB (1) GB2002364B (en)
NL (1) NL7807609A (en)

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FR2707630A1 (en) * 1993-07-13 1995-01-20 Centre Nat Rech Scient Derived from cyclohexenemethanol, its preparation and its use in the synthesis of taxoids.

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FR2621912B1 (en) * 1987-10-16 1990-03-02 Oreal NOVEL NORBORNANE DERIVATIVES, THEIR PREPARATION PROCESS AND COSMETIC AND MEDICINAL COMPOSITIONS CONTAINING THEM
US6166371A (en) * 1999-04-30 2000-12-26 Beckman Coulter, Inc. Diffuse reflective light curtain system
JP6496806B2 (en) 2015-03-06 2019-04-10 三井化学株式会社 Cross-linked body and damping material

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0114612A2 (en) * 1983-01-20 1984-08-01 BASF Aktiengesellschaft Racemic and optically actif 3-hydroxy-alpha-cyclocitral, their acetals and optically actif 3-oxo-alpha-cyclocitralacetals, and also the preparation and use of these compounds
EP0114612A3 (en) * 1983-01-20 1986-02-19 Basf Aktiengesellschaft Racemic and optically actif 3-hydroxy-alpha-cyclocitral, their acetals and optically actif 3-oxo-alpha-cyclocitralacetals, and also the preparation and use of these compounds
FR2707630A1 (en) * 1993-07-13 1995-01-20 Centre Nat Rech Scient Derived from cyclohexenemethanol, its preparation and its use in the synthesis of taxoids.
WO1995002569A1 (en) * 1993-07-13 1995-01-26 Centre National De La Recherche Scientifique Cyclohexenemethanol derivative, preparation thereof and use thereof for taxoid synthesis

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US4225501A (en) 1980-09-30
JPS6159317B2 (en) 1986-12-16
DE2860714D1 (en) 1981-08-27
DE2832137A1 (en) 1979-02-08
JPS5424893A (en) 1979-02-24
EP0000719A3 (en) 1979-06-27
GB2002364A (en) 1979-02-21
FR2398751A1 (en) 1979-02-23
GB2002364B (en) 1982-02-17
NL7807609A (en) 1979-01-29
US4250062A (en) 1981-02-10
US4258071A (en) 1981-03-24
EP0000719B1 (en) 1981-05-20

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