EP0000719B1 - 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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EP0000719B1
EP0000719B1 EP78100472A EP78100472A EP0000719B1 EP 0000719 B1 EP0000719 B1 EP 0000719B1 EP 78100472 A EP78100472 A EP 78100472A EP 78100472 A EP78100472 A EP 78100472A EP 0000719 B1 EP0000719 B1 EP 0000719B1
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compounds
formula
trans
fragrance
trimethyl
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EP0000719A3 (en
EP0000719A2 (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 method for producing the compounds of the formula
  • This process is characterized in that 1,3,3-trimethyl-2- (3-hydroxybutylidene) -6-cyclohexen-4-ol is reacted in an acidic medium.
  • the acidic medium with the aid of 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. B. 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 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.
  • organic solvent in particular an aromatic solvent. Examples are benzene, toluene and xylene.
  • a mixture of la: 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 separation of the isomer mixture can be carried out in a conventional manner, e.g. B. by means of column chromatography or preparative gas chromatography. As can be seen further 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-trimethy) 2- (3 hydroxylbutylidene) -6-cyclohexen-4-ol referred to below and in Example 1 as compound 14 is a new compound. It can - as shown there - from the known 2-hydroxy-ß-ionon can be obtained.
  • this 2-hydroxy- ⁇ -ionone is advantageously reacted with an enol acylate in the presence of one of the acids specified above; so z. B. dissolved in (an excess of) acetonenol acetate, mixed with a catalytic amount of p-toluenesulfonic acid and the reaction mixture kept at 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.
  • Connection 13 is new.
  • 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 1) as fragrances and / or flavorings.
  • Practically pure 1 should in particular be understood to mean 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 flavorings - in particular Ib [because of its greater diffusion and intensity] - are distinguished by fresh, green, spicy, very natural-looking, certain aspects of cassis buds and exotic fruits - such as mango, passion fruit , Guanabana - reminiscent of smells.
  • the compounds can accordingly serve, for example, for perfuming or aromatizing products, such as cosmetics (soaps, salves, 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 with a content of compounds I and their preparation in a manner known per se (addition of I to known fragrance or flavoring compositions or mixing of I with natural or suitable components of fragrance or flavoring positions synthetic compounds or mixtures) also forms the subject of the invention.
  • fragrance compositions produced using compounds 1, in particular of the Chypre, Cologne, Muguet or generally floral and woody direction, are particularly spectacular due to their spectacular freshness and originality.
  • fragrances can be used in a manner known to the perfumer, such as, for example, B. 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, 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 1 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 0.1 ppm-100 ppm, preferably 1 ppm -20 ppm in the finished product, i. H. the flavored food, stimulant or drink.
  • the compounds can be mixed in a customary manner with the constituents used for flavoring compositions or added to such flavors.
  • the flavors used according to the invention are understood to mean flavoring compositions which can be diluted in a manner known per se or can be 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 evaluated in terms of their senses in comparison to a fresh mango fruit.
  • test persons (6) found significantly more character of the fresh mango fruit in the additionally flavored yoghurt.

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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)

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-I-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 FormelThe invention further relates to a method for producing the compounds of the formula

Dieses Verfahren ist dadurch gekennzeichnet, daß man 1,3,3-Trimethyl-2-(3-hydroxybutyliden)-6-cyclohexen-4-ol in saurem Medium zur Reaktion bringt.This process is characterized in that 1,3,3-trimethyl-2- (3-hydroxybutylidene) -6-cyclohexen-4-ol is reacted 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 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. B. 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 Reaktionstemperatur ist nicht kritisch. Sie beträgt zweckmäßigerweise 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 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 und Xylol.The reaction is preferably carried out with the aid of an organic solvent, in particular an aromatic solvent. Examples are benzene, toluene and xylene.

Nach dem erfindungsgemäßen Verfahren fällt ein Gemisch von la : 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 Isomerengemisch verwendet werden kann.In the process according to the invention, a mixture of la: 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 separation of the isomer mixture can be carried out in a conventional manner, e.g. B. by means of column chromatography or preparative gas chromatography. As can be seen further 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 1,3,3-Trimethy) 2-(3 hydro- xybutyliden)-6-cyclohexen-4-ol stellt eine neue Verbindung dar Es kann - wie dort gezeigt - aus dem bekannten 2-Hydroxy-ß-ionon erhalten werden.The 1,3,3-trimethy) 2- (3 hydroxylbutylidene) -6-cyclohexen-4-ol referred to below and in Example 1 as compound 14 is a new compound. It can - as shown there - from the known 2-hydroxy-ß-ionon can be obtained.

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 Überschuß 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-β-ionone is advantageously reacted with an enol acylate in the presence of one of the acids specified above; so z. B. dissolved in (an excess of) acetonenol acetate, mixed with a catalytic amount of p-toluenesulfonic acid and the reaction mixture kept at 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.Connection 13 is new.

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, 1 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 1) as fragrances and / or flavorings.

Unter praktisch reinen 1 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 1 should in particular be understood to mean 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 la/lb, 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 la / lb, namely in a ratio of 1: 5, is 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, Passionsfrucht, Guanabana - erinnernde Geruchsnuancen aus. Die Verbindungen können demgemäß beispielsweise zur Parfümierung bzw. Aromatisierung von Produkten, wie Kosmetika (Seifen, Saleben, 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 ändern 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. Geschmackstoffkorr.positionen geeigneten natürlichen oder synthetischen Verbindungen oder Gemischen) bildet ebenfalls Gegenstand der Erfindung.The compounds I used according to the invention as fragrances and / or flavorings - in particular Ib [because of its greater diffusion and intensity] - are distinguished by fresh, green, spicy, very natural-looking, certain aspects of cassis buds and exotic fruits - such as mango, passion fruit , Guanabana - reminiscent of smells. The compounds can accordingly serve, for example, for perfuming or aromatizing products, such as cosmetics (soaps, salves, 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 with a content of compounds I and their preparation in a manner known per se (addition of I to known fragrance or flavoring compositions or mixing of I with natural or suitable components of fragrance or flavoring positions synthetic compounds or mixtures) also 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-ÖI, Basilikumöl, Baummoos absolue, Patchouliblätteröl, Cedernöl, Fichtenöl, Lorbeeröl, Costuswurzelöl, Calmusöl, Beifußöl, Kamillenöl, Wermutöl, Wurmsamenöl, Selleriesamenöl, Angelikasamenöl, Sternanisöl, Thymianöl, Rosmarinöl, Lavendelöl, Lavandinöl, Aspiköl, Salbeiöl, Neroliöl, Bergamottöl, Citronenöl, Orangenöl, Grapefruitöl, Geraniumöl, Benzoeresinoid, Melilotus absolue, Jasmin absolue, Rosenöl, Canangaöl, Corianderöl, Cassie absolue, Narzissen absolue, Verveine absolue oder Öl, Veilchenblätter absolue, Tuberosen absolue usw.
  • - Aldehyden wie Hydroxycitronellal, Zyklamenaldehyd, p-tert.-Butyl-α-methylhydrozimtaldehyd, alpha-Hexylzimtaldehyd, 3,5-Dimethyl-cyclohex-3-en-1-yl-carboxaldehyd, 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-lonon, 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.
  • - Äthern wie Eugenolmethyläther, Methyl-1-methylcyclododecyläther, Anethol, Estragol usw.
  • - 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, Äthylisovalerat, Äthylcaproat, para-tert.-Butylcyclohexylacetat, ortho-tert.-Butylcyclohexylace- tat, MyraldylacetatR (Givaudan), Benzylacetat, Benzylsalicylat, Styrallylacetat, Äthyl-α-methylphenylglycidat, Äthyl-trans-2-hexenoat, Äthyl-trans-2-octenoat usw.
  • - Lactone wie y-Undecalacton, y-Decalacton, y-Nonalacton, ö-Decalacton, ö-Octalacton, Cumarin usw.
  • - Säuren wie Milchsäure, Buttersäure, α-Methylbuttersäure, trans-2-Hexensäure, trans-2-Octen- säure usw.
  • - Moschus- und ambraartig riechenden Körpern wie Äthylenbrassylat, 4-Acetyl-6-tert.-butyl-1,1-dimethylindan, 12-Oxahexadecanolid, 8α,12-Oxido-13,14,15,16-tetranorlabdan usw.
  • - schwefelhaltigen Verbindungen wie p-Menthan-8-thiol-3-on, Dimethylsulfid und anderen Sulfiden und Disulfiden usw.
  • - stickstoffhaltigen Verbindungen wie Methylanthranilat, 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, B.
  • - galbanum, Mastic, vetiver, patchouli, sandalwood, mandarin oil, petit grain oil, ylang-ylang oil, basil oil, tree moss absolue, Patchouliblätteröl, cedar oil, pine oil, bay oil, costus root, calamus, mugwort oil, chamomile oil, wormwood oil, worm seed oil, celery seed oil, angelica oil, Star anise oil, thyme oil, rosemary oil, lavender oil, lavandin oil, aspic oil, sage oil, neroli oil, bergamot oil, lemon oil, orange oil, grapefruit oil, geranium oil, benzoeresinoid, melilotus absolue, jasmine absolute, rose oil, cananga oil, coriander oil, cassie or absolute, oil daffodils , Violet leaves absolut, tuberoses absolut etc.
  • - 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 1-methylcyclododecyl ether, anethole, estragole 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 (givaudylate, benzyl ethyl acetate, benzyl ethyl acetate, benzyl acetate), , Ethyl trans-2-hexenoate, ethyl trans-2-octenoate etc.
  • - Lactones such as y-undecalactone, y-decalactone, y-nonalactone, ö-decalactone, ö-octalactone, coumarin etc.
  • - Acids such as lactic acid, butyric acid, α-methylbutyric acid, trans-2-hexenoic acid, trans-2-octenoic acid etc.
  • - musky and amber-smelling bodies such as ethylene brassylate, 4-acetyl-6-tert-butyl-1,1-dimethylindane, 12-oxahexadecanolide, 8α, 12-oxido-13,14,15,16-tetranorlabdan etc.
  • - Sulfur-containing compounds such as p-menthan-8-thiol-3-one, dimethyl sulfide and other sulfides and disulfides etc.
  • - nitrogenous compounds such as methyl anthranilate, indole, isobutylquinoline, various pyrazines, 5-methyl-heptan-3-one oxime, etc.

Die unter Verwendung von Verbindungen 1 hergestellten 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 1, 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 above-mentioned known fragrances can be used in a manner known to the perfumer, such as, for example, B. from W. A. Poucher, Perfumes, Cosmetics and Soaps 2, 7th edition, Chapman and Hall, London, 1974.

Es hat sich schließlich gezeigt, daß die Verbindungen la/lb auch bei der Rekonstitution einer Reihe von ätherischen Ölen oder Absolues, wie z. B. Mandarinenöl, Grapefruitöl, Cassis-Knospen absolue - in denen diese Verbindungen nie nachgewiesen wurden - verwendet werden können.It has finally been shown that the compounds la / lb also in the reconstitution of a number of essential oils or absolute, such as. B. mandarin oil, grapefruit oil, cassis buds absolute - in which these compounds have never been detected - can be used.

Die Konzentration der Verbindungen I kann je nach dem Verwendungszweck innerhalb weiter Grenzen variieren, beispielsweise 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.Depending on the intended use, the concentration of the compounds I can vary within wide limits, 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 1 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 1 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 0.1 ppm-100 ppm, preferably 1 ppm -20 ppm in the finished product, i. H. the flavored food, stimulant or drink.

In derfolgenden Tabelle sind einige Effekte zusammengestellt, wie sie sich mit den Äthern! rzielen lassen.

Figure imgb0004
The following table summarizes some effects of how they affect the ether! let it aim.
Figure imgb0004

Die Verbindungen können auf übliche Weise mit den für Geschmackstoffkompositionen verwendeten Bestandteilen vermischt bzw. solchen Aromen 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 customary manner with the constituents used for flavoring compositions or added to such flavors. The flavors used according to the invention are understood to mean flavoring compositions which can be diluted in a manner known per se or can be 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, such as e.g. BJ Merory, Food Flavors, Composition, Manufacture and Use, Second Edition, The Avi Pbublishing Company, Inc., Westport, Conn. 1968, or G. Fenaroli, Fenaroli's Handbook of Flavor Ingredients, Second Edition, Volume 2, CRC-Press, Inc. Cleveland, Ohio, 1975.

Spektrale Daten:Spectral data:

  • 5 IR: 3460,1730,1336,1151,1049,1039,1029 cm-1;5 IR: 3460.1730.1336.1151.1049.1039.1029 cm- 1 ;
  • NMR: 0,92+0,98 (je 3H,s); 1,25 (3H,t,J-6,8Hz); 1,62 (3H); 2,76 (1H); 4,0 (1H,m); 4,08 (2H,q,J~6,8 Hz); 5,4 (m,1 H) δppm;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) δppm;
  • MS: 212 (M+, 9); 194 (25), 166 (28), 141 (19), 139 (27), 123 (28), 121 (100), 113 (32), 107 (18), 95 (53), 43 (27)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;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 (1 H,m); 4,20 (2H,q,J~6,8 Hz) δppm;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) δppm;
  • 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)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;7 IR: 1730.1310.1216.1179.1119.1046.1000.871 cm -1 ;
  • NMR: 0,98+1,21 (6H,2s); 1,24 (3H,t,J-6,8Hz); 1,45 (3H,s); 2,29 (1H); 3,90 (1H,d,J-4Hz); 4,11 (2H,q,J~6,8 Hz) δppmNMR: 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-4Hz); 4.11 (2H, q, J ~ 6.8 Hz) δppm
  • 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).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 0° abgekühlte Reaktionsgemisch wurde vorsichtig mit Wasser, hierauf mit 2 N Salzsäurelösung versetzt, in 400 ml Äther aufgenommen und die ätherische Schicht mit Wasser gewaschen, getrocknet und eingeengt. Es verblieben 26,2 g Rohprodukt, welches gemäß gaschromatographischer Analyse 80% 2-Hydroxy-α-cyclogeraniol 8 enthielten.

Figure imgb0005
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 2 N 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-α-cyclogeraniol 8.
Figure imgb0005

Eine aus Äther umkristallisierte Probe zeigte die folgenden spektroskopischen Daten:

  • IR: 3615, 3450, 1175, 1068, 1037, 1018, 955, 845 cm-1 (als Lösung in CHCl3);
  • NMR: 0,90+1,09 (je 3H,2s); 1,75 (3H); 3,80 (2H,d,J -4 Hz); 3,95 (1 H,m); 5,50 (1 H,m) δppm;
  • 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°.
A sample recrystallized from ether showed the following spectroscopic data:
  • IR: 3615, 3450, 1175, 1068, 1037, 1018, 955, 845 cm -1 (as a solution in CHCl 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) δppm;
  • 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-α-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, Bicarbonatlösung nochmals mit Wasser. Nach dem Trocknen und Einengen verblieben 11,9 g Rohprodukt, welche die beiden Hydroxyaldehyde

Figure imgb0006
im Verhältnis von 3 : 1 enthielten.
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)
15.0 g (0.088 mol) of crude 2-hydroxy-α-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 again with water, 2N hydrochloric acid and bicarbonate solution with water. After drying and concentrating, 11.9 g of crude product remained, which are the two hydroxyaldehydes
Figure imgb0006
 contained in a ratio of 3: 1.
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)

Für die Herstellung solcher üblicher Gebrauchsformen kommen beispielsweise folgende Trägermaterialien, Verdickungsmittel, Geschmackstoffverbesserer, Gewürze und Hilfsingredientien 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, Äthanol, Propylenglykol, Glycerin.
The following carrier materials, thickeners, flavor enhancers, spices and auxiliary ingredients can be used to produce 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 1 - Example 1

Eine Lösung von 25,0 g (0,129 Mol) α-Safransäureäthylester 2 und 0,25 g Bengalrosa in 300 ml Äthanol 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 imgb0007
A solution of 25.0 g (0.129 mol) of ethyl α-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 arranged, water-cooled high-pressure mercury lamp type TQ-150 from Hanau served as the light source. 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 imgb0007

Die so erhaltene ähtanolische 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 4,951 in 1,5 Stunden (

Figure imgb0008
77,5% der Theorie). Die Reaktionslösung wurde durch Filtration vom Katalysator befreit, eingeengt und die erhaltenen rohen 31 g Reaktionsprodukte an der 20fachen Menge Kieselgel chromatographiert. Die Elution mit Äther ergab 14,0 g cis-2,5-Dihydroxy-2,6,6-trimethylcyclohexancarbonsäureäthylester 4 vom Schmelzpunkt 92-94° (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~6,8Hz); 2,57 (1H,s); 3,90 (1H,m,Jax-ax~8 Hz, Jax-eq -4 Hz); 4,15 (2H,q, J -6,8 Hz)δppm;
  • MS: 212 (M+-H2O, 13), 166(34), 154(15), 129(100), 123(25), 113(15), 101 (68), 95 (24), 83 (43),43 (90).
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 under normal pressure. The hydrogen consumption was 4.951 in 1.5 hours (
Figure imgb0008
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 ethyl cis-2,5-dihydroxy-2,6,6-trimethylcyclohexanecarboxylate 4 with a melting point of 92-94 ° (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) δppm;
  • MS: 212 (M + - H2O, 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 Äther, wusch je dreimal mit Sodalösung und 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-cyclogeranium-säureester 5 und 6 enthielten. Als Nebenprodukt entstand zu 7% der 2,5-Oxaester 7.

Figure imgb0009
Figure imgb0010
 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 at the reflux temperature of the reaction mixture for 2 hours while removing the water of reaction. 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-cyclogeranium acid esters 5 and 6, respectively. 7% of the 2,5-oxaester 7 was formed as a by-product.
Figure imgb0009
Figure imgb0010

11,9 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 Äther aufgenommen und die ätherische Lösung mit konzentrierter Kochsalzlösung gewaschen. Nach Trocknen und Einengen verblieben 12,5 g Rohprodukt, welche gemäß gaschromatographischer Analyse zu rund 40% aus den 2-Hydroxy-ß-iononen 11 und 12 im Verhältnis von 1 : 5 bestanden. Die säulenchromatographische Reinigung des Rohproduktes lieferte bei der Elution mit Hexan/Äther= 1 : 14,2 g 92%iges Gemisch der 2-Hydroxy-ionone 11 und 12.

Figure imgb0011
11.9 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-ß-ionones 11 and 12 in a ratio of 1: 5. Column chromatographic purification of the crude product gave elution with hexane / ether = 1: 14.2 g of a 92% mixture of 2-hydroxy-ionones 11 and 12.
Figure imgb0011

Zur spektroskopischen Charakterisierung gelangten Proben, welche mit Hilfe von präparativer Gaschromatographie auf eine Reinheit von > 95% gebracht wurden.
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-10Hz); 3,68 (lH,dxd, Jax-ax~7Hz, Jax-eq~5Hz); 5,44(1H,m): 6,08 (1H,d,J~16Hz); 6,68 (1H,dxd,J1~16Hz), J2~10Hz)δppm;
  • 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 (1H,dxd, Jax-ax~7 Hz, Jax-eq-4,6 Hz), 6,10 (1 H,d,J - 16,5 Hz); 7,21 (1 H,d,J~16,5 Hz) δppm;
  • 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).
For spectroscopic characterization, samples were obtained which were brought to a purity of> 95% using preparative gas chromatography.
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-10Hz); 3.68 (1H, dxd, J ax-ax ~ 7Hz, J ax-eq ~ 5Hz); 5.44 (1H, m): 6.08 (1H, d, J ~ 16Hz); 6.68 (1H, dxd, J 1 ~ 16Hz), J 2 ~ 10Hz) δppm;
  • 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 (j e 3H, 2 s ); 1.75 (3H); 2.29 (3H, s); 3.56 (1H, dxd, J ax-ax ~ 7 Hz, J ax - e q-4.6 Hz), 6.10 (1 H, d, J - 16.5 Hz); 7.21 (1H, d, J ~ 16.5 Hz) δppm;
  • 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 Acetonenolactat gelöst und anschließend in Gegenwart von 0,03 g p-Toluolsulfonsäure 2 Stunden bei Rückflußtemperatur gerührt. Das Reaktionsgemisch wurde abgekühlt, in 150 ml Äther aufgenommen, die ähterische 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 imgb0012
3.87 g of the 2-hydroxy-ionones 11 + 12 (1: 5) were dissolved in 20 ml of acetone olactate 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 imgb0012

Eine Lösung von 3,9 g Diacetat 13 in 10 ml Äther ließ man im Verlaufe von 10 Minuten zu einer Suspension von 1,06 g Lithiumaluminiumhydrid in 70 ml Äther zutropfen, rührte das Reaktionsgemisch während einer Stunde bei Rückflußtemperatur, kühlte hierauf auf Raumtemperatur, zersetzte den Überschuß an Lithiumaluminiumhydrid vorsichtig mit Wasser, wusch die Ätherphase mit Wasser, trocknete und engte ein. Die verbliebenen 2,7 g Diol 14 löst man zusammen mit 0,05 g p-Toluolsulfonsäure in 25 ml Benzol und rührte das Gemisch anschließend während einer Stunde bei Rückflußtemperatur, verdünnte das abgekühlte Gemisch mit 50 ml Äther und wusch die Ätherphase 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 1a a und 1b (Verhältnis cis/trans= 15 : 85) bestand.A solution of 3.9 g of diacetate 13 in 10 ml of ether was added dropwise to a suspension of 1.06 g of lithium aluminum hydride in 70 ml of ether in the course of 10 minutes, the reaction mixture was stirred for one hour at reflux temperature, then cooled to room temperature and decomposed the excess lithium aluminum hydride carefully with water, washed the ether phase with water, dried and concentrated. The remaining 2.7 g of diol 14 are dissolved together with 0.05 g of p-toluenesulfonic acid in 25 ml of benzene and the mixture is then stirred for one hour at reflux temperature, the cooled mixture is diluted with 50 ml of ether and the ether phase is washed 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 1a a and 1b (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 40fachen Menge Kieselgel (Hexan/Äther =30 : 1) auf eine Reinheit von über 98% gebracht worden waren.
Spektrale Daten:

  • 1a 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-7Hz); 3,93 (1H,d,J~4Hz); 5,55 (1H,dxq,J3',2' ~ 16 Hz, J3', CH3 ~ 7 Hz), ~5,55 (1H,d,J ~ 10 Hz), ~6,3 (1H,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)
  • 1b 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).
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).
Spectral data:
  • 1a 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-7Hz); 3.93 (1H, d, J ~ 4Hz); 5.55 (1H, dxq, J 3 ', 2' ~ 16 Hz, J 3 ' , CH 3 ~ 7 Hz), ~ 5.55 (1H, d, J ~ 10 Hz), ~ 6.3 (1H , dxd, 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)
  • 1b 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 (1H, dxq, J 3 ', 2' ~ 16 Hz; J 3 ', CH 3 ~ 7 Hz); 5.65 (1H, d, J1 ', 2' ~ 10 Hz); 6.30 (1H, dxd, J 2 ', 3' ~ 16 Hz; J 2 ', 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).

Beispiel 2Example 2 Grün-BaseGreen base

Figure imgb0013
Figure imgb0013

Gibt man zu dieser konventionellen Grünbase (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.

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

Figure imgb0014
Figure imgb0014

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 Rapefruit und Zitronenschale. Die Substanz verbindet sich, wie ersichtlich, sehr harmonisch mit schwefelhaltigen Verbindungen. Die neue Base erhält eine sehr natürliche Frische. Überraschenderweise 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 rapefruit 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.

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

Figure imgb0015
Figure imgb0015

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 imgb0016
Figure imgb0016

Versetzt man diese Komposition (Chypre-Charakter) mit 20 Teilen der neuen Verbindung I, so wirkt die gesamte Komposition 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 whole 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 imgb0017
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.
Figure imgb0017
 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 Fruchtsäfte 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-1,3,3-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.Analogously to the previous example, 0.40 g of a 0.1% alcoholic solution of 1,4-epoxy-1,3,3-trimethyl-2- (2-butenylidene) cyclohexane was added to 1 liter of grapefruit juice. In this case, the majority of the test persons (8) found a more pronounced wood note than 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-Fruchtpulpe und 80 g Saccharose versetzt. Zu 500 g dieses Mango-Yoghurts gab man J,25 g einer 0,1%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. To 500 g of this mango yoghurt was added J, 25 g of a 0.1% alcoholic solution of 1,4-epoxy-1,3,3-trimethyl-2- (2-butenylidene) cyclohexane.

Die beiden Yoghurts wurden dem Testpanel (10 Personen) vorgelegt und im Vergleich zu einer frischen Mangofruchtsensorisch beurteilt.The two yoghurts were presented to the test panel (10 people) and evaluated in terms of their senses in comparison to a fresh mango fruit.

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

Claims (10)

1. Compounds of the general formula
Figure imgb0021
wherein R represents the 2-cis- or the 2-trans-buten-1-ylidene group.
2. Cis/trans-1,4-epoxy-1,3,3-trimethyl-2-(2-buten-1-ylidene)-cyclohexane according to cleim 1 of the formula
Figure imgb0022
3. Trans/trans-1,4-epoxy-1,3,3-trimethyl-2-(2-buten-1-ylidene)-cyclohexane according to claim 1 of the formula
Figure imgb0023
4. Practically pure compounds of the general formula I according to claim 1.
5. Synthetically manufactured compounds of the general formula I according to claim 1.
6. A process for the manufacture of the compounds of formula I given in claim 1, which process comprises reacting 1,3,3-trimethyl-2-(3-hydroxy-butylidene)-6-cyclohexen-4-ol in acid medium.
7. Odorant and/or flavouring compositions which contain a compound of formula I given in claim 1 in practically pure form or in the form of mixtures, with the exception of natural mixtures containing compounds offormula I.
8. Odorant and/or flavouring compositions according to claim 7 which contain synthetically manufactured compounds of formula I.
9. The use of compounds of formula I given in claim 1 in practically pure form or in the form of mixtures, with the exception of natural mixtures containing compounds of formula I, as odorant and/or flavouring compositions.
10. The use according to claim 9 of compounds of formula I given in claim 1, characterized in that the compounds of formula I have been synthetically manufactured.
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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EP0168882A1 (en) * 1984-07-13 1986-01-22 The Procter & Gamble Company Oxa-fenchols and oxa-fenchyl amines useful for preparing high intensity sweeteners
EP0312412A1 (en) * 1987-10-16 1989-04-19 L'oreal Norbornane derivatives, method for their preparation and cosmetic and medicinal compositions containing them

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JPS591415A (en) * 1982-06-28 1984-01-06 Mochida Pharmaceut Co Ltd Remedy for circulatory disease
DE3470032D1 (en) * 1983-01-20 1988-04-28 Basf Ag 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
US4868901A (en) * 1987-10-13 1989-09-19 Sci-Agra, Inc. Reflected light detecting apparatus and method
FR2707630B1 (en) * 1993-07-13 1995-09-29 Centre Nat Rech Scient Derived from cyclohexenemethanol, its preparation and its use in the synthesis of taxoids.
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0168882A1 (en) * 1984-07-13 1986-01-22 The Procter & Gamble Company Oxa-fenchols and oxa-fenchyl amines useful for preparing high intensity sweeteners
EP0312412A1 (en) * 1987-10-16 1989-04-19 L'oreal Norbornane derivatives, method for their preparation and cosmetic and medicinal compositions containing them
FR2621912A1 (en) * 1987-10-16 1989-04-21 Oreal NOVEL NORBORNANE DERIVATIVES, PROCESS FOR THEIR PREPARATION AND COSMETIC AND MEDICAMENT COMPOSITIONS CONTAINING SAME
US5047575A (en) * 1987-10-16 1991-09-10 L'oreal Norbornene carboxylic acids and esters

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