EP0000771B1 - 2,5,7-trimethyloctane-3-ol and 2,4-dimethylnonane-8-ol; processes for their preparation; their use as olfactory agents; olfactory compositions containing them, as well as the preparation of such olfactory compositions - Google Patents

2,5,7-trimethyloctane-3-ol and 2,4-dimethylnonane-8-ol; processes for their preparation; their use as olfactory agents; olfactory compositions containing them, as well as the preparation of such olfactory compositions Download PDF

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Publication number
EP0000771B1
EP0000771B1 EP19780100580 EP78100580A EP0000771B1 EP 0000771 B1 EP0000771 B1 EP 0000771B1 EP 19780100580 EP19780100580 EP 19780100580 EP 78100580 A EP78100580 A EP 78100580A EP 0000771 B1 EP0000771 B1 EP 0000771B1
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dimethyl
olfactory
preparation
methyl
trimethyl
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German (de)
French (fr)
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EP0000771A2 (en
EP0000771A3 (en
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Paul Albert Dr. Ochsner
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Givaudan SA
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L Givaudan and Co SA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0007—Aliphatic compounds
    • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
    • 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
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
    • 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
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
    • C07C33/03—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond in beta-position, e.g. allyl alcohol, methallyl alcohol
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/17—Saturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups

Definitions

  • the invention relates to new fragrances, namely compounds of the formula wherein R represents the 1-hydroxy-2-methyl-propyl or the 3-hydroxy-butyl radical.
  • Formula I accordingly comprises 2,5,7-trimethyloctan-3-01 (la) and 2,4-dimethyl-nonan-8-ol (Ib).
  • Chloride, bromide and iodide are suitable as halide; bromide and chloride are particularly suitable.
  • Raney nickel and palladium are expediently suitable as catalysts.
  • the octanone can also be reduced to alcohol using sodium borohydride or lithium aluminum hydride (L.F. Fieser & M. Fieser, Reagents for Organic Synthesis, John Wiley & Sons 1967, 582, 1049).
  • 1,4-octadienone it is expedient first to work at room temperature in order first to hydrogenate the double bonds, and then - for the purpose of hydrogenating the keto group - at elevated temperature.
  • This latter hydrogenation can e.g. at temperatures of 120-150 ° C, especially at about 140 ° C.
  • nonenol it is preferred to start with material prepared in situ, which is accessible, for example, by catalytic hydrogenation from 6,8-dimethyl-3-nonen-2-one using copper chromite.
  • the 3,5-nonadienone is also preferably hydrogenated using copper chromite.
  • the nonanone is expediently reduced to the alcohol Ib using sodium borohydride or lithium aluminum hydride.
  • the 2,4-dimethylpentyl halides required for process variant a) can be obtained by adding hydrogen halide to 2,4-dimethyl-1-pentene according to methods known per se - in the presence of a peroxide - or by replacing the primary alcoholic grouping of 2,4- Dimethylpentanol - also in a manner known per se by means of phosphorus halides - accessible.
  • 2,5,7-trimethyl-1,4-octadien-3-one is known, for example, from 2,4,7-trimethyl-7-octen-5-yn-4-ol by propargylic rearrangement Way with the help of a vanadium catalyst - possible.
  • Catalytic hydrogenation of the dienone obtained at room temperature - as described above - makes 2,5,7-trimethyl-3-octane p n accessible.
  • the 6,8-dimethyl-3-nonen-2-one is accessible, for example, by aldol condensation of 3,5-dimethylhexanal with acetone.
  • the alcohols I have special organoleptic properties which make them particularly suitable as fragrances.
  • the invention accordingly also relates to the use of I, in particular in the form of mixtures, as fragrances, and fragrance compositions which are characterized by a content of these alcohols I.
  • the compound la used as a fragrance according to the invention is distinguished by interesting fruity (apricot-like) smell nuances.
  • the alcohol Ib on the other hand, is characterized by a pleasantly floral, fruity, earthy green, mushroom note, whereby aldehydic secondary notes can be identified.
  • the compounds can accordingly serve, for example, for perfuming products such as cosmetics (soaps, mouthwashes, deodorants, shampoos, lotions, ointments, powders, etc.), detergents, etc., the compounds preferably not alone, but in the form of compositions other fragrances are used.
  • 2,5,7-trimethyi-octan-3-oi produces a velvety, rounded effect in bouquets of various directions, which can be much more important than the apricot-like odor.
  • 2,4, -dimethyl-nonan-8-ol which has an earthy, natural note, its addition in compositions achieves considerable reinforcement and a radiance that is particularly noticeable in rose and jasmine notes. Since the new compounds are also saturated alcohols, they are extremely stable in mixtures.
  • Compounds I are suitable as fragrances because of their high harmonic insertion capacity, in particular in combination with a number of natural fragrances, e.g. Galbanum oil, vetiver oil, patchouli oil, cedarwood oil, bergamot oil, spruce needle oil, petitgrain oil, tree moss, lemon oil, coriander oil, angelica seed oil, cardamom oil.
  • natural fragrances e.g. Galbanum oil, vetiver oil, patchouli oil, cedarwood oil, bergamot oil, spruce needle oil, petitgrain oil, tree moss, lemon oil, coriander oil, angelica seed oil, cardamom oil.
  • Compound la can also be used advantageously in mixtures with mastic oil, palmarosa oil, jasmine absolute, mandarin oil and hyssop oil, while compound Ib, on the other hand, produces desired effects with ylang-ylang oil.
  • the compounds Ia and Ib can accordingly be used in the production of compositions and - as the production above shows - using a wide range of known odoriferous substances, in particular for the production of compositions with fruity, floral, green, woody, chyper-like and cologne-like notes.
  • Alcohol Ib has a natural, mushroom-like odor that is reminiscent of damp forests. Because of this property, Ib, for example in jasmine or rose compositions, significantly enhances the desired natural character of the perfume. The radiance that the compound Ib gives to compositions is particularly valuable in the production of Compositions used in industrial perfumery, such as perfuming soaps and washing powders.
  • 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 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.
  • n D 20 1.4736
  • 64 g of the ketone are hydrogenated in a stirred autoclave in the presence of 6 g of copper chromite under a hydrogen pressure of 40 bar.
  • the temperature is first brought to 140 ° C.
  • the hydrogen absorption ceases (after 3 hours)
  • the mixture is heated to 170 ° C. and kept between 165 and 170 ° C. for 3 hours.
  • the catalyst is filtered off with suction and distilled.
  • 65 g of chemically pure 2,4-dimethyl-nonan-8-ol are obtained (yield: 85.4%).
  • This composition probably has the character of a lily of the valley and targets lilac; for the time being, however, it appears synthetic and somewhat aggressive. After adding 100 parts by weight of 2,5,7-trimethyl-octan-3-ol there is a velvety impression, the note now appears rounded and fruity.
  • this composition has a fruity character; the addition of 2,5,7-trimethyloctan-3-ol strengthens and improves the fruity note in the direction of apricots, the natural effect of ripe apricots is achieved.
  • the 100 parts by weight of 2,5,7-trimethyloctan-3-ol impart a natural, rounded character to the mixture, the typical note of the ripe melon is more recognizable.
  • This floral base is particularly suitable for perfuming soaps and washing powders. With a dosage of 1 to 1.5% by weight in soaps, the composition behaves like an extremely stable, powerful perfume. In washing powders, the optimal effect is obtained at a dosage of 0.1 to 0.3%; the floral note is particularly emphasized by the presence of 2,4-dimethyl-nonan-8-ol.
  • This composition represents an "ordinary" rose composition. If you now add 145 parts by weight of 2,4-dimethyl-nonan-8-ol, you get a base with much more volume, which looks more natural and especially on rose petals and on the "Rose de mai "(cross between Rosa centifolia and Rosa gallica).
  • This classic chypre base is clearly improved by adding 100 parts by weight of 2,4-dimethyl-nonan-8-ol, creating a floral and green shade and enhancing the (desired) smell of undergrowth.
  • the conventional lilac composition gets an earthy shade, which makes the otherwise “synthetic" smell more balanced, flowery, more natural.
  • the new alcohol has a rounded effect.
  • the composition with the new alcohol appears less “sharp”, but more powerful, it is much more suitable for perfumery.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)

Description

Die Erfindung betrifft neue Riechstoffe, nämlich Verbindungen der Formel

Figure imgb0001
worin R den 1-Hydroxy-2-methyl-propyl- oder den 3-Hydroxy-butylrest darstellt.The invention relates to new fragrances, namely compounds of the formula
Figure imgb0001
 wherein R represents the 1-hydroxy-2-methyl-propyl or the 3-hydroxy-butyl radical.

Die Formel I umfasst demzufolge das 2,5,7-Trimethyloctan-3-01 (la) und das 2,4-Dimethyl-nonan-8-ol (Ib).Formula I accordingly comprises 2,5,7-trimethyloctan-3-01 (la) and 2,4-dimethyl-nonan-8-ol (Ib).

Die Erfindung betrifft auch ein Verfahren zur Herstellung dieser neuen Alkohole. Es ist dadurch gekennzeichnet, dass man entweder

  • a) 3,5-Dimethylhexanal mit einem Isopropylmagnesiumhalogenid bzw. Isobutyraldehyd mit einem 2,4-Dimethylpentylmagnesiumhalogenid umsetzt, oder dass man
  • b) 2,5,7-Trimethy!-4-octen-3-o! bzw. 6,8-Dimethyl-3-nonen-2-ol oder 2,5,7-Trimethyl-1,4-octadien-3-on bzw. 6,8-Dimethyl-3,5-nonadien-2-on oder 2,5,7-Trimethyl-3-octanon bzw. 6,8-Dimethyl-2-nonanon hydriert.
The invention also relates to a process for the preparation of these new alcohols. It is characterized by either
  • a) reacting 3,5-dimethylhexanal with an isopropyl magnesium halide or isobutyraldehyde with a 2,4-dimethylpentyl magnesium halide, or that
  • b) 2,5,7-Trimethy! -4-octen-3-o! or 6,8-dimethyl-3-nonen-2-ol or 2,5,7-trimethyl-1,4-octadien-3-one or 6,8-dimethyl-3,5-nonadien-2-one or 2,5,7-trimethyl-3-octanone or 6,8-dimethyl-2-nonanone.

Die - ausschliesslich zu la führende - Umsetzung gemäss Verfahrensvariante a) kann nach den an sich bekannten Methoden der Grignardreaktion durchgeführt werden. Man arbeitet also zweckmässigerweise in Diäthyläther als Lösungsmittel und bei Temperaturen von 0-10°C.The - according to process variant a) - leading exclusively to la - can be carried out according to the Grignard reaction methods known per se. It is therefore convenient to work in diethyl ether as a solvent and at temperatures of 0-10 ° C.

Als Halogenid kommen Chlorid, Bromid und Jodid in Frage, besonders geeignet sind Bromid und Chlorid.Chloride, bromide and iodide are suitable as halide; bromide and chloride are particularly suitable.

Die Hydrierungen gemäss Verfahrensvariante b) werden zweckmässigerweise katalytisch durchgeführt.The hydrogenations according to process variant b) are advantageously carried out catalytically.

Im Falle des Octenols kommen als Katalysatoren zweckmässigerweise Raney-Nickel und Palladium in Frage.In the case of octenol, Raney nickel and palladium are expediently suitable as catalysts.

Bevorzugt ist Palladium auf Kohle.Palladium on carbon is preferred.

Man arbeitet zweckmässigerweise bei Raumtemperatur - doch kommen auch höhere oder niedrigere Temperaturen in Frage - und in Lösungsmitteln wie Aethylacetat, Aethanol, Aceton, etc.It is expedient to work at room temperature - but higher or lower temperatures are also possible - and in solvents such as ethyl acetate, ethanol, acetone, etc.

Im Falle des Octanons bzw. des 1,4-Octadienons kommen insbesondere Kupferchromit oder Nickel als Katalysatoren in Frage.In the case of octanone or 1,4-octadienone, copper chromite or nickel are particularly suitable as catalysts.

Das Octanon kann schliesslich auch mittels Natriumborhydrid oder Lithiumaluminiumhydrid zum Alkohol reduziert werden (L.F. Fieser & M. Fieser, Reagents for Organic Synthesis, John Wiley & Sons 1967, 582, 1049).Finally, the octanone can also be reduced to alcohol using sodium borohydride or lithium aluminum hydride (L.F. Fieser & M. Fieser, Reagents for Organic Synthesis, John Wiley & Sons 1967, 582, 1049).

Irri Falle des 1,4-Octadienons arbeitet man zweckmässigerweise zunächst bei Raumtemperatur, um zunächst die Doppelbindungen zu hydrieren, und hierauf - zwecks Hydrierung der Ketogruppe - bei erhöhter Temperatur. Diese letztere Hydrierung kann z.B. bei Temperaturen von 120-150°C, insbesondere bei ca. 140°C erfolgen.In the case of 1,4-octadienone, it is expedient first to work at room temperature in order first to hydrogenate the double bonds, and then - for the purpose of hydrogenating the keto group - at elevated temperature. This latter hydrogenation can e.g. at temperatures of 120-150 ° C, especially at about 140 ° C.

Im Falle des Nonenols geht man vorzugsweise von in situ hergestelltem Material aus, das beispielsweise durch katalytische Hydrierung aus 6,8-Dimethyl-3-nonen-2-on unter Verwendung von Kupferchromit zugäglich ist.In the case of the nonenol, it is preferred to start with material prepared in situ, which is accessible, for example, by catalytic hydrogenation from 6,8-dimethyl-3-nonen-2-one using copper chromite.

Auch das 3,5-Nonadienon wird vorzugsweise unter Verwendung von Kupferchromit hydriert.The 3,5-nonadienone is also preferably hydrogenated using copper chromite.

Das Nonanon wird zweckmässigerweise unter Verwendung von Natriumborhydrid oder Lithiumaluminiumhydrid zum Alkohol Ib reduziert.The nonanone is expediently reduced to the alcohol Ib using sodium borohydride or lithium aluminum hydride.

Die für die Verfahrensvariante a) benötigten 2,4-Dimethylpentylhalogenide sind durch Addition von Halogenwasserstoff an 2,4-Dimethyl-1-penten nach an sich bekannten Methoden - in Anwesenheit eines Peroxyds - oder durch Ersatz der primären alkoholischen Gruppierung von 2,4-Dimethylpentanol - ebenfalls in an sich bekannter Weise mittels Phosphorhalogeniden - zugänglich.The 2,4-dimethylpentyl halides required for process variant a) can be obtained by adding hydrogen halide to 2,4-dimethyl-1-pentene according to methods known per se - in the presence of a peroxide - or by replacing the primary alcoholic grouping of 2,4- Dimethylpentanol - also in a manner known per se by means of phosphorus halides - accessible.

Die Herstellung von 2,5,7-Trimethyl-1,4-octadien-3-on ist beispielsweise aus 2,4,7-Trimethyl-7- octen-5-in-4-ol durch propargylische Umlagerung - in an sich bekannter Weise unter Zuhilfenahme eines Vanadium-Katalysators - möglich. Durch katalytische Hydrierung des erhaltenen Dienons bei Zimmertemperatur - wie vorne beschrieben - ist 2,5,7-Trimethyl-3-octanpn zugänglich. Das 6,8-Dimethyl-3-nonen-2-on ist beispielsweise durch Aldolkondensation von 3,5-Dimethylhexanal mit Aceton zugänglich.The preparation of 2,5,7-trimethyl-1,4-octadien-3-one is known, for example, from 2,4,7-trimethyl-7-octen-5-yn-4-ol by propargylic rearrangement Way with the help of a vanadium catalyst - possible. Catalytic hydrogenation of the dienone obtained at room temperature - as described above - makes 2,5,7-trimethyl-3-octane p n accessible. The 6,8-dimethyl-3-nonen-2-one is accessible, for example, by aldol condensation of 3,5-dimethylhexanal with acetone.

Die Alkohole I weisen besondere organoleptische Eigenschaften auf, auf Grund derer sie sich vorzüglich als Riechstoffe eignen.The alcohols I have special organoleptic properties which make them particularly suitable as fragrances.

Die Erfindung betrifft demgemäss auch die Verwendung von I, insbesondere in Form von Gemischen, als Riechstoffe, und Riechstoffkompositionen, die durch einen Gehalt an diesen Alkoholen I gekennzeichnet sind.The invention accordingly also relates to the use of I, in particular in the form of mixtures, as fragrances, and fragrance compositions which are characterized by a content of these alcohols I.

Die erfindungsgemäss als Riechstoff verwendete Verbindung la zeichnet sich durch interessante fruchtige (aprikosenartige) Geruchsnuancen aus. Der Alkohol Ib zeichnet sich andererseits durch eine angenehm blumige, fruchtige, erdig-grüne, pilzige Note aus, wobei aldehydrische Nebennoten festgestellt werden können. Die Verbindungen können demgemäss beispielsweise zur Parfümierung von Produkten, wie Kosmetika (Seifen, Mundwässern, Desodorantien, Shampoos, Lotions, Salben, Pudern, etc.), Detergentien, etc. dienen, wobei die Verbindungen vorzugsweise nicht allein, sondern in Form von Kompositionen mit andern Riechstoffen eingesetzt werden.The compound la used as a fragrance according to the invention is distinguished by interesting fruity (apricot-like) smell nuances. The alcohol Ib, on the other hand, is characterized by a pleasantly floral, fruity, earthy green, mushroom note, whereby aldehydic secondary notes can be identified. The compounds can accordingly serve, for example, for perfuming products such as cosmetics (soaps, mouthwashes, deodorants, shampoos, lotions, ointments, powders, etc.), detergents, etc., the compounds preferably not alone, but in the form of compositions other fragrances are used.

Von grossem Vorteil ist die Tatsache, dass das 2,5,7-Trimethyi-octan-3-oi in Bouquets der verschiedensten Richtungen einen samtartigen, abrundenden Effekt bewirkt, der dabei noch wesentlich wichtiger sein kann als der aprikosenartige Eigengeruch. Mit dem 2,4,-Dimethyl-nonan-8-ol, das eine erdige, natürliche Note besitzt, erzielt man durch dessen Zusatz in Kompositionen eine erhebliche Verstärkung, und eine Strahlungskraft, die besonders in Rosen- und Jasminnoten zur Geltung kommt. Da es sich zudem bei den neuen Verbindungen um gesättigte Alkohole handelt, sind sie in Gemischen äusserst stabil.Of great advantage is the fact that 2,5,7-trimethyi-octan-3-oi produces a velvety, rounded effect in bouquets of various directions, which can be much more important than the apricot-like odor. With the 2,4, -dimethyl-nonan-8-ol, which has an earthy, natural note, its addition in compositions achieves considerable reinforcement and a radiance that is particularly noticeable in rose and jasmine notes. Since the new compounds are also saturated alcohols, they are extremely stable in mixtures.

Als Riechstoffe eignen sich die Verbindungen I auf Grund ihres hohen harmonischen Einfügungsvermögens, insbesondere in Kombination mit einer Reihe von natürlichen Riechstoffen, wie z.B. Galbanumöl, Vetiveröl, Patchouliöl, Zedernholzöl, Bergamotteöl, Fichtennadelöl, Petitgrainöl, Baummoos, Citronenöl, Corianderöl, Angelikasamenöl, Cardamomenöl.Compounds I are suitable as fragrances because of their high harmonic insertion capacity, in particular in combination with a number of natural fragrances, e.g. Galbanum oil, vetiver oil, patchouli oil, cedarwood oil, bergamot oil, spruce needle oil, petitgrain oil, tree moss, lemon oil, coriander oil, angelica seed oil, cardamom oil.

Die Verbindung la kann auch vorteilhaft in Mischungen mit Mastixöl, Palmarosaöl, Jasmin Absolut, Mandarinenöl und Ysopöl verwendet werden, während die Verbindung Ib andererseits mit Ylang-Ylangöl erwünschte Effekte bewirkt.Compound la can also be used advantageously in mixtures with mastic oil, palmarosa oil, jasmine absolute, mandarin oil and hyssop oil, while compound Ib, on the other hand, produces desired effects with ylang-ylang oil.

Dank ihrer Strahlungskraft und Natürlichkeit können beide Verbindungen vorteilhaft für die Herstellung von Kompositionen mit z.B. folgenden synthetischen Riechstoffen verwendet werden:

  • - mit Aldehyden, wie Hydroxycitronellal, n-Decanal, 2,4-Dimethyl-3-cyclohexenyl-1-carboxaldehyd, substituierten Zimtaldehyden, 3,5,6-Trimethyl-3-cyclohexen-1-carbox- aldehyd, p-tert.-Butyl-α-methylhydrozimtaldehyd, p-Isopropyl-a-methylhydrozimtaldehyd, p-Tolyl-acetaldehyd, α-Methyl-3,4-methylen-dioxy-hydrozimtaldehyd, 2,6-Dimethyl-5- heptenal, usw.
  • - mit Ketonen, wie 7-Acetyl-1,1,3,4,4,6-hexamethyltetrahydro-(1,2,3,4)-naphthalin, α-Jonon, Allyl-a-jonon, Ketonmoschus, p-Methylacetophenon, usw.
  • - mit Acetalen, wie 1-Phenyl-4-methyl-3,5-dioxaoctan, Phenyiacetaldehyddimethylacetal, usw.
  • - mit phenolischen Körpern, wie Eugenol, usw.
  • - mit Alkoholen, wie Phenyläthylalkohol, Linalool, Citronellol, cis-6-Nonenol, Zimtalkohol, Phenylpropyl-alkohol, Geraniol, Nerol, usw.
  • - mit Aethern, wie 1-Methylcyclododecan-1-yl-methyläther, 8α,12-Oxido-13,14,15,16-tetranorlabdan, usw.
  • - mit Estern, wie Benzylacetat, Aethyl-a-methylphenylglycidester, Linalylacetat, Vetivenylacetat, Linalylanthranilat, Methyldihydrojasmonat, Benzylsalicylat, 2-tert.-Butylcyclohexylacetat, Acetessigsäureäthylester, Dimethylbenzylmethylbutyrat, 5-[4- oder 5-(Acetoxymethyl)-1-cyclohexenyl]-2-methyl-2-penten, Hexenylsalicylat, Hexenylacetat, Benzylpropionat, Phenoxyäthylisobutyrat, p-Cresylphenylessigsäureester, Zimtformiat, Geranylacetat, Styrallylacetat, Phenyläthylformiat, usw.
  • - mit Lactonen, wie Cumarin, y-Undecalacton, y-Nonalacton, usw.
  • - mit schwefelhaltigen Verbindungen, wie p-Menthan-8-thiol-3-on, Sulfiden, usw.
  • - mit stickstoffhaltigen Verbindungen, wie Indol, 5-Methyl-3-heptanonoxim, Dimethylpyrazin, usw.
Thanks to their radiance and naturalness, both compounds can be used advantageously for the production of compositions with, for example, the following synthetic fragrances:
  • - With aldehydes, such as hydroxycitronellal, n-decanal, 2,4-dimethyl-3-cyclohexenyl-1-carboxaldehyde, substituted cinnamaldehydes, 3,5,6-trimethyl-3-cyclohexen-1-carboxaldehyde, p-tert. -Butyl-α-methylhydrocinnamaldehyde, p-isopropyl-a-methylhydrocinnamaldehyde, p-tolyl-acetaldehyde, α-methyl-3,4-methylene-dioxy-hydrocinnamaldehyde, 2,6-dimethyl-5-heptenal, etc.
  • with ketones, such as 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydro- (1,2,3,4) -naphthalene, α-ionone, allyl-a-ionone, ketone musk, p-methylacetophenone , etc.
  • with acetals such as 1-phenyl-4-methyl-3,5-dioxaoctane, phenyiacetaldehyde dimethyl acetal, etc.
  • - with phenolic bodies, such as eugenol, etc.
  • - With alcohols, such as phenylethyl alcohol, linalool, citronellol, cis-6-nonenol, cinnamon alcohol, phenylpropyl alcohol, geraniol, nerol, etc.
  • - With ethers such as 1-methylcyclododecan-1-yl methyl ether, 8α, 12-oxido-13,14,15,16-tetranorlabdan, etc.
  • with esters, such as benzyl acetate, ethyl-a-methylphenylglycide ester, linalyl acetate, vetivenyl acetate, linalylanthranilate, methyldihydrojasmonate, benzylsalicylate, 2-tert-butylcyclohexyl acetate, acetoacetic acid ethyl ester, dimethylbenzylmethyl-4-methylethyl-butyl-5-methyl-methyl-methyl-4-methyl-4-methyl-4-methyl-4-methyl-4-methyl-4-methyl-4 -2-methyl-2-pentene, hexenyl salicylate, hexenyl acetate, benzyl propionate, phenoxyethyl isobutyrate, p-cresylphenylacetic acid ester, cinnamon formate, geranyl acetate, styrallyl acetate, phenylethyl formate, etc.
  • with lactones, such as coumarin, y-undecalactone, y-nonalactone, etc.
  • - With sulfur-containing compounds, such as p-menthan-8-thiol-3-one, sulfides, etc.
  • with nitrogen-containing compounds such as indole, 5-methyl-3-heptanone oxime, dimethylpyrazine, etc.

Die Verbindungen la und Ib können demgemäss bei der Herstellung von Kompositionen und - wie obige Herstellung zeigt - unter Verwendung einer breiten Palette bekannter Riechstoffe, insbesondere zur Herstellung von Kompositionen mit fruchtigen, blumigen, grünen, holzigen, chyperartigen und cologneartigen Noten verwendet werden.The compounds Ia and Ib can accordingly be used in the production of compositions and - as the production above shows - using a wide range of known odoriferous substances, in particular for the production of compositions with fruity, floral, green, woody, chyper-like and cologne-like notes.

Die unter Verwendung von I hergestellten Riechstoffkompositionen bestechen insbesondere durch die ausserordentliche Strahlungskraft, Natürlichkeit und Lebhaftigkeit.The fragrance compositions produced using I impress in particular with their extraordinary radiance, naturalness and liveliness.

So vermag z.B. la blumig-fruchtige Parfüm-Kompositionen durch zusätzliche Strahlungskraft und Natürlichkeit zu bereichern und kommt damit den Tendenzen der modernen Parfümerie in willkommener Weise entgegen. Der Alkohol la hebt in frischen, citrusartigen, holzigen Kompositionen die Hesperidennote in vorteilhafter Weise und unterstreicht zugleich den Holzcharakter auf veredelnde Art. Allgemein kann festgestellt werden, dass la beispielsweise sehr gute Effekte in ausgeprägt femininen Parfüms zeigt, aber andererseits auch vorteilhaft in maskulinen Kompositionen verwendet wird. Es können unter Zuhilfenahme von la auch interessante Blumenkomplexe hergestellt werden und la lässt sich gut mit Edelholznoten kombinieren.For example, To enrich the floral-fruity perfume compositions with additional radiance and naturalness and thus meets the trends of modern perfumery in a welcome way. In fresh, citrus-like, woody compositions, the alcohol la lifts the Hesperid note in an advantageous manner and at the same time underlines the wood character in a refining way. In general, it can be stated that la shows very good effects in distinctly feminine perfumes, but on the other hand also advantageously used in masculine compositions becomes. Interesting flower complexes can also be produced with the help of la and la can be easily combined with precious wood notes.

Der Alkohol Ib weist einen natürlichen, pilzartigen, an feuchten Wald erinnernden Eigengeruch auf. Aufgrund dieser Eigenschaft erzielt man mittels Ib z.B. in Jasminoder Rosenkompositionen eine deutliche Verstärkung des erwünschten natürlichen Charakters des Parfums. Die Strahlungskraft, die die Verbindung Ib Kompositionen verleiht, ist besonders wertvoll bei der Herstellung von Kompositionen, die in der industriellen Parfümerie verwendet werden, wie z.B. beim Parfümieren von Seifen und Waschpulvern.Alcohol Ib has a natural, mushroom-like odor that is reminiscent of damp forests. Because of this property, Ib, for example in jasmine or rose compositions, significantly enhances the desired natural character of the perfume. The radiance that the compound Ib gives to compositions is particularly valuable in the production of Compositions used in industrial perfumery, such as perfuming soaps and washing powders.

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 Parfümbasen 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). In perfume bases or concentrates, the concentrations 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.

Bei niedrigen Dosierungen (z.B. 0,5-2%) von kann bereits eine deutliche Zunahme der Strahlungskraft festgestellt werden, ohne dass der Grundcharakter der Komposition wesentlich verändert wird. Bei höheren Dosierungen (z.B. 10-30%) tritt zusätzlich eine den olfaktischen Eigenschaften der verwendeten Verbindung entsprechende Modifizierung ein.At low dosages (e.g. 0.5-2%) of, a significant increase in radiance can already be determined without significantly changing the basic character of the composition. At higher doses (e.g. 10-30%), a modification corresponding to the olfactory properties of the compound used also occurs.

Beispiel 1example 1

In einen Rundkolben, der mit Rührer, Kühler, Thermometer und Tropftrichter versehen ist, gibt man 26,4 g (1,1 Grammatom) Magnesiumspäne und 100 ml trockenen Aether. Man gibt hierauf langsam eine Lösung von 86,4 g (1,1 Mol) Isopropylchlorid in 150 ml wasserfreiem Aether zu und hält das Gemisch bei Rückftusstemperatur. Die Umsetzung wird durch Zugabe von wenig Jod zum Magnesium in Gang gebrächt. Nach Beendigung der Zugabe des Isopropylchlorids hält man das Gemisch noch 1 Stunde bei Rückflusstemperatur. Man gibt nun langsam bei 5°C 128,2 g (1 Mol) 3,5-Dimethylhexanal, gelöst in 250 ml wasserfreiem Aether zu. Wiederum hält man das Gemisch - 3 Stunden - bei Rückflusstemperatur. Man kühlt hierauf auf 0°C ab und zersetzt das Reaktionsprodukt durch Zugabe von 340 ml eisgekühlter 10%iger Salzsäure. Die ätherische Lösung wird mittels Wasser neutral gewaschen, hierauf getrocknet und das Lösungsmittel abgedampft. Man erhält auf diese Weise 176 g (70%) Rohprodukt, dessen fraktionierte Destillation 121,4 g 2,5,7-Trimethyloctan-3-ol ergibt. Sdp. = 79°/5 mmHg, nD 20= 1,4362.26.4 g (1.1 gram atom) of magnesium shavings and 100 ml of dry ether are placed in a round bottom flask equipped with a stirrer, cooler, thermometer and dropping funnel. A solution of 86.4 g (1.1 mol) of isopropyl chloride in 150 ml of anhydrous ether is then slowly added and the mixture is kept at the reflux temperature. The reaction is started by adding a little iodine to the magnesium. After the addition of the isopropyl chloride has ended, the mixture is kept at the reflux temperature for 1 hour. 128.2 g (1 mol) of 3,5-dimethylhexanal, dissolved in 250 ml of anhydrous ether, are then slowly added at 5 ° C. Again, the mixture is held at the reflux temperature for 3 hours. The mixture is then cooled to 0 ° C. and the reaction product is decomposed by adding 340 ml of ice-cooled 10% hydrochloric acid. The ethereal solution is washed neutral with water, then dried and the solvent is evaporated off. 176 g (70%) of crude product are obtained in this way, the fractional distillation of which gives 121.4 g of 2,5,7-trimethyloctan-3-ol. Bp = 79 ° / 5 mmHg, n D 20 = 1.4362.

Beispiel 2Example 2

  • a) In einen Rundkolben, der mit Rührer, Kühler, Thermometer und Tropftrichter versehen ist, gibt man 26,4 g (1,1 Grammatom) Magnesiumspäne und 100 ml wasserfreien Aether. Man gibt nun langsam eine Lösung von 90,2 g (1,15 Mol) Isopropylchlorid in 150 ml Aether zu. Nach Beendigung der Zugabe hält man das Reaktionsgemisch noch 1 Stunde bei Rückflusstemperatur. Man gibt hierauf bei einer Temperatur von 10°C 126,2 g (1 Mol) 3,5-Dimethyl-2-hexenal, gelöst in 250 ml wasserfreiem Aether, zu. Man hält 3 Stunden bei Rückflusstemperatur, kühlt hierauf auf 0°C ab und zersetzt durch Zugabe von 370 ml 10%iger, eisgekühlter Salzsäure. Die ätherische Lösung wird durch Zugabe von Wasser neutral gewaschen, hierauf getrocknet und das Lösungsmittel abgedampft. Man erhält auf diese Weise 168 g Rohmaterial, dessen fraktionierte Destillation 123,7 g (72,6%) 2,5,7-Trimethyl-4- octen-3-ol geben. Sdp. = 78-79°/5 mmHg, nD 20= 1,4526.a) 26.4 g (1.1 gram atom) of magnesium shavings and 100 ml of anhydrous ether are added to a round bottom flask equipped with a stirrer, cooler, thermometer and dropping funnel. A solution of 90.2 g (1.15 mol) of isopropyl chloride in 150 ml of ether is now slowly added. After the addition has ended, the reaction mixture is kept at the reflux temperature for 1 hour. 126.2 g (1 mol) of 3,5-dimethyl-2-hexenal, dissolved in 250 ml of anhydrous ether, are then added at a temperature of 10 ° C. The mixture is kept at the reflux temperature for 3 hours, then cooled to 0 ° C. and decomposed by adding 370 ml of 10% ice-cooled hydrochloric acid. The ethereal solution is washed neutral by adding water, then dried and the solvent is evaporated off. This gives 168 g of raw material, the fractional distillation of which gives 123.7 g (72.6%) of 2,5,7-trimethyl-4-octen-3-ol. Bp = 78-79 ° / 5 mmHg, n D 20 = 1.4526.
  • b) 100 g des Octenols, gelöst in 200 ml Aethylacetat werden in Anwesenheit von 10 g 5%igem Palladium auf Kohle hydriert. Nach Aufnahme von 5,08 It Wasserstoff bei 20°C (die theoretische Menge beträgt 14,6 It) und bei Atmosphärendruck hört die Wasserstoffaufnahme auf. Man entfernt den Katalysator durch Filtration, verdampft das Lösungsmittel und beendigt die Hydrierung in einem Autoklaven in Anwesenheit von 1 g Raney-Nickel bei 100°C/10 Atm. Nach 2 Stunden lässt man Abkühlen, filtriert den Katalysator ab und destilliert das Produkt. Man erhält auf diese Weise 63 g 2,5,7-Trimethyl-octan-3-ol, Sdp. = 72°/5 mmHg, n20 = 1,4362, d4 20 = 0,8287. Die Ausbeute beträgt 62,5%.b) 100 g of the octenol, dissolved in 200 ml of ethyl acetate, are hydrogenated on carbon in the presence of 10 g of 5% palladium. After taking up 5.08 It hydrogen at 20 ° C (the theoretical amount is 14.6 It) and at atmospheric pressure the hydrogen absorption stops. The catalyst is removed by filtration, the solvent is evaporated and the hydrogenation is terminated in an autoclave in the presence of 1 g of Raney nickel at 100 ° C./10 atm. After 2 hours, the mixture is allowed to cool, the catalyst is filtered off and the product is distilled. This gives 63 g of 2,5,7-trimethyl-octan-3-ol, bp = 72 ° / 5 mmHg, n2 0 = 1.4362, d 4 20 = 0.8287. The yield is 62.5%.
Beispiel 3Example 3

In einen 2 1-Rundkolben, der mit Rührer, Kühler, Thermometer und Tropftrichter versehen ist, gibt man 400 ml wasserfreies Toluol und 200 g pulverförmiges Kaliumhydroxyd. Man kühlt auf -20°C und gibt nun bei einer Temperatur zwischen -20 und --10°C 66 g (1 Mol) 3-Methyl-3-buten-1-in [A.F. Thompson jun., N.A. Milas, Ida Rovno, J.Am.Chem.Soc. 63, (1941), 752-755] zu. Man hält das Gemisch 1 1/2 Stunden unter Rühren bei einer Temperatur von -10°C und gibt hierauf langsam bei 0°C 110 g (1,1 Mol) Methyl-isobutylketon zu. Man rührt nun 1 Stunde bei 0°C und lässt hierauf innert 2 Stunden unter Weiterrühren die Temperatur auf 20°C ansteigen. Das Reaktionsgemisch wird auf Eis gegeben; man extrahiert mit 500 ml Toluol, wäscht mit Sole bis zur Neutralität und dampft das Lösungsmittel ab. Man erhält 183 g Rohprodukt, dessen Destillation 129,5 g (78,4%) 2,4,7-Trimethyl-7-octen-5-in-4-ol ergeben. Sdp. 76-77°/5 mmHg, nD 20 = 1,4690, d4 20 = 0,8620.400 ml of anhydrous toluene and 200 g of powdered potassium hydroxide are added to a 2 1 round-bottom flask equipped with a stirrer, cooler, thermometer and dropping funnel. The mixture is cooled to -20 ° C. and 66 g (1 mol) of 3-methyl-3-buten-1-yne are added at a temperature between -20 and -10 ° C. [AF Thompson jun., NA Milas, Ida Rovno , J.Am.Chem.Soc. 63, (1941), 752-755]. The mixture is kept under stirring at a temperature of -10 ° C. for 1 1/2 hours and then 110 g (1.1 mol) of methyl isobutyl ketone are slowly added at 0 ° C. The mixture is then stirred at 0 ° C. for 1 hour and the temperature is then allowed to rise to 20 ° C. within 2 hours while stirring. The reaction mixture is poured onto ice; the mixture is extracted with 500 ml of toluene, washed with brine until neutral and the solvent is evaporated off. 183 g of crude product are obtained, the distillation of which gives 129.5 g (78.4%) of 2,4,7-trimethyl-7-octen-5-yn-4-ol. Bp 76-77 ° / 5 mmHg, n D 20 = 1.4690, d 4 20 = 0.8620.

b) In einen 2 1-Rundkolben, der mit Thermometer, Rührer und Kühler versehen ist, gibt man 880 g Paraffinoel. Man erhitzt dieses bei einem Druck von 0,1 mmHg zwecks Entgasen 1 Stunde auf 140°C.b) 880 g of paraffin are added to a 2 1 round-bottom flask equipped with a thermometer, stirrer and cooler. This is heated at a pressure of 0.1 mmHg for 1 hour to 140 ° C for degassing.

Nach Abkühlung auf 30°C gibt man 75 g Triphenylsilanol, 2 g Stearinsäure, 7,6 ml Triisopropylvanadat und 100 g des obigen Octeninols zu. Man erhitzt nun das Gemisch 2 Stunden auf 140°C, und zwar unter Stickstoffatmosphäre, und lässt wiederum auf 80°C abkühlen. Das gebildete" rohe Keton destilliert man bei einer Temperatur von 50-70°C ab. Die Destillation wird weitergeführt, bis eine Innentemperatur von 150°C und ein Vakuum von 1 mmHg erreicht ist. Man erhält auf diese Weise 71 g (71%) des rohen 2,5,7-Trimethyl-1,4-octadien-3-on (z + e), nD 20 = 1,4736. Die Konstanten des destillierten reinen Produkts sind die folgenden: Sdp. = 77°/5 mmHg, nD 20 = 1,4742, d4 20 = 0,8674.After cooling to 30 ° C., 75 g of triphenylsilanol, 2 g of stearic acid, 7.6 ml of triisopropyl vanadate and 100 g of the above octeninol are added. The mixture is now heated for 2 hours 140 ° C, namely under a nitrogen atmosphere, and in turn allows to cool to 80 ° C. The crude ketone formed is distilled off at a temperature of 50-70 ° C. The distillation is continued until an internal temperature of 150 ° C. and a vacuum of 1 mmHg is reached. 71 g (71%) are obtained in this way. of crude 2,5,7-trimethyl-1,4-octadien-3-one (z + e), n D 20 = 1.4736 The constants of the distilled pure product are the following: bp = 77 ° / 5 mmHg, n D 20 = 1.4742, d 4 20 = 0.8674.

c) 16,6 g des rohen Ketons werden in 250 ml Methanol bei Atmosphärendruck und 20°C in Anwesenheit von 3 g Raney-Nickel und 1 g Natriumcarbonat hydriert. Nach Aufnahme von 4,84 1 Wasserstoff (theoretische Menge: 7,5 1) hört die Wasserstoffaufnahme auf. Man filtriert den Katalysator ab, dampft das Methanol ab und gibt das Reaktionsprodukt - enthaltend 2,5,7-Trimethyl-3-octanon - in einen Autoklaven, zusammen mit 3 g Raney-Nickel und 1 g Natriumcarbonat. Nach 48 Stunden bei 140°C und 40 Atmosphären/Wasserstoffdruck ist die Hydrierung beendigt. Man gewinnt 14 g (67%) Rohprodukt, dessen Destillation 11,5 g 2,5,7-Trimethyl-octan-3-ol liefern. Sdp. = 72°/5 mmHg, no° = 1,4362, d4 20= 0,8287.c) 16.6 g of the crude ketone are hydrogenated in 250 ml of methanol at atmospheric pressure and 20 ° C. in the presence of 3 g of Raney nickel and 1 g of sodium carbonate. After taking in 4.84 l of hydrogen (theoretical amount: 7.5 l), the hydrogen uptake ceases. The catalyst is filtered off, the methanol is evaporated off and the reaction product - containing 2,5,7-trimethyl-3-octanone - is placed in an autoclave together with 3 g of Raney nickel and 1 g of sodium carbonate. The hydrogenation is complete after 48 hours at 140 ° C. and 40 atmospheres / hydrogen pressure. 14 g (67%) of crude product are obtained, the distillation of which yield 11.5 g of 2,5,7-trimethyl-octan-3-ol. Bp = 72 ° / 5 mmHg, no ° = 1.4362, d 4 20 = 0.8287.

Beispiel 4Example 4

  • a) In einen rostfreien Stahlautoklaven (300 ml Fassungsvermögen) gibt man 112 g 2,4-Dimethyl-2-pentenal und 5 g Kupferchromit. Man hält das Gemisch bei einem Druck von 25 Atmosphären Wasserstoff und einer Temperatur von 150°C. Nach 8 Stunden ist die theoretische Wasserstoffmenge aufgenommen, nämlich 50 1 (auf Atmosphärendruck berechnet). Man filtriert vom Katalysator ab und destilliert die erhaltenen 108 g Rohprodukt. Man erhält 90,7 g (78,3%) 2,4-Dimethylpentanol, Sdp. = 81°/34 mmHg, nD 20= 1,4232, d4 20= 0,8199.a) 112 g of 2,4-dimethyl-2-pentenal and 5 g of copper chromite are placed in a stainless steel autoclave (300 ml capacity). The mixture is kept at a pressure of 25 atmospheres of hydrogen and a temperature of 150 ° C. After 8 hours, the theoretical amount of hydrogen has been absorbed, namely 50 liters (calculated on atmospheric pressure). The catalyst is filtered off and the 108 g of crude product obtained are distilled. 90.7 g (78.3%) of 2,4-dimethylpentanol are obtained, bp = 81 ° / 34 mmHg, n D 20 = 1.4232, d 4 20 = 0.8199.
  • b) In einen Rundkolben, der mit Rührer, Thermometer, Kühler und Tropftrichter versehen ist, gibt man 116 g (1 Mol) des obigen Pentanols und 12 g wasserfreies Pyridin. Man gibt nun langsam unter Kühlung 110 g (0,4 Mol) Phosphortribromid zu. Während der Zugabe hält man die Temperatur unterhalb 60°C, hält aber nach der Zugabe das Gemisch noch 1 Stunde bei 60°C. Nach Abkühlung nimmt man das Gemisch in Aether auf, wäscht die ätherische Lösung mit Wasser, hierauf mit einer 8%igen Natriumbicarbonatlösung und dann nochmals mit Wasser bis zur neutralen Reaktion. Man trocknet über wasserfreiem Natriumsulfat und dampft das Lösungsmittel ab. Man erhält 206 g rohes Bromid, dessen Destillation 111,5 g (62,3%) 2,4-Dimethylpentyl-bromid (1) ergeben. Sdp. = 70°/40 mmHg, nD 20= 1,4495, d4 20= 1,1376.b) 116 g (1 mol) of the above pentanol and 12 g of anhydrous pyridine are added to a round-bottom flask equipped with a stirrer, thermometer, cooler and dropping funnel. 110 g (0.4 mol) of phosphorus tribromide are then slowly added with cooling. The temperature is kept below 60 ° C. during the addition, but the mixture is kept at 60 ° C. for 1 hour after the addition. After cooling, the mixture is taken up in ether, the ethereal solution is washed with water, then with an 8% sodium bicarbonate solution and then again with water until the reaction is neutral. It is dried over anhydrous sodium sulfate and the solvent is evaporated off. 206 g of crude bromide are obtained, the distillation of which gives 111.5 g (62.3%) of 2,4-dimethylpentyl bromide (1). Bp = 70 ° / 40 mmHg, n D 20 = 1.4495, d 4 20 = 1.1376.
  • c) In einen Rundkolben, der mit Rührer, Thermometer, Kühler und Tropftrichter versehen ist, gibt man 9 g Magnesiumspäne und 50 ml wasserfreien Aether. Man gibt nun langsam beim Siedepunkt des Aethers eine Lösung von 72,2 g des obigen Bromids in 100 ml wasserfreiem Aether zu. Man erhitzt eine halbe Stunde auf Rückflusstemperatur und kühlt hierauf auf 10°C ab. Man fügt nun bei einer Temperatur von 10°C eine Lösung von 27,6 g Isobutyraldehyd in 60 ml getrocknetem Aether zu. Man bringt das Gemisch 3 Stunden auf Rückflusstemperatur und kühlt hierauf wiederum ab. Durch Zugabe von 20%iger Ammoniumchloridlösung wird das Reaktionsgemisch zersetzt. Man nimmt in Aether auf, wäscht sukzessive mit einer 10%igen Weinsäurelösung, mit Wasser, mit 10%iger Natriumcarbonatlösung, und hierauf nochmals mit Wasser bis zum Neutralpunkt. Man trocknet über wasserfreiem Natriumsulfat und dampft das Lösungsmittel ab. Man gewinnt 56,6 g Rohmaterial, dessen Destillation 32 g (46,2%) 2,5,7-Trimethyl-octan-3-ol ergeben. Sdp. = 78°C/6 mmHg. nD 20= 1,4370, d4 20=0,8287.c) 9 g of magnesium shavings and 50 ml of anhydrous ether are added to a round bottom flask equipped with a stirrer, thermometer, cooler and dropping funnel. A solution of 72.2 g of the above bromide in 100 ml of anhydrous ether is then slowly added at the boiling point of the ether. The mixture is heated to the reflux temperature for half an hour and then cooled to 10 ° C. A solution of 27.6 g of isobutyraldehyde in 60 ml of dried ether is then added at a temperature of 10 ° C. The mixture is brought to the reflux temperature for 3 hours and then cooled again. The reaction mixture is decomposed by adding 20% ammonium chloride solution. It is taken up in ether, washed successively with a 10% tartaric acid solution, with water, with 10% sodium carbonate solution and then again with water to the neutral point. It is dried over anhydrous sodium sulfate and the solvent is evaporated off. 56.6 g of raw material are obtained, the distillation of which gives 32 g (46.2%) of 2,5,7-trimethyl-octan-3-ol. Bp = 78 ° C / 6 mmHg. n D 20 = 1.4370, d 4 20 = 0.8287.
Beispiel 5Example 5

In einen Rundkolben, der mit Rührer, Kühler, Thermometer und Tropftrichter versehen ist, gibt man 128 g 3,5-Dimethylhexanal und 58 g Aceton. Das Gemisch wird auf 80°C erhitzt. Bei dieser Temperatur werden unter Rühren 150 ml 1 n Natriumhydroxydlösung innerhalb einer Stunde zugetropft. Nach der Zugabe wird das Reaktionsgemisch noch 1/4 Stunde bei 80°C gehalten. Nach Erkalten wird in 200 ml Aether aufgenommen und mit Wasser bis zur Neutralität gewaschen. Nach dem Abdampfen des Lösungsmittels erhält man 147 g Rohprodukt, das durch Destillation fraktioniert wird. Die ersten Fraktionen (34 g) bestehen aus dem Ausgangsaldehyd (Sdp. 33°C/8 mmHg). Der zweite Teil (28 g) Des Destillats stellt das gewünschte Kondensationsprodukt 6,8-Dimethyl-3-nonen-2-on (Sdp. 88°C/6 mmHg) dar. Der dritte Teil (55 g) besteht aus dem Additionsprodukt 6,8-Dimethyl-4-hydroxynonan-2-on (Sdp. 106-108°C/6 mmHg), das wie folgt dehydratisiert wird:

  • 55 g 6,8-Dimethyl-4-hydroxy-nonan-2-on werden in einem Claisenkolben über 2 g Kaliumhydrogensulfat unter einem Vakuum von 18 mmHg bei 92-1 03°C destilliert. Das Destillat wird in 100 ml Aether aufgenommen, mit Natriumhydrogencarbonatlösung, hierauf mit Wasser gewaschen. Nach dem Abdampfen des Lösungsmittels erhält man 43 g Rohprodukt, die durch Destillation.40 g 6,8-Dimethyl-3-nonen-2-on (Sdp. 88°C/6 mmHg) ergeben. Totalausbeute: 71 g 6,8-Dimethyl-3-nonen-2- on (42% der Theorie).
128 g of 3,5-dimethylhexanal and 58 g of acetone are added to a round-bottomed flask equipped with a stirrer, cooler, thermometer and dropping funnel. The mixture is heated to 80 ° C. At this temperature, 150 ml of 1N sodium hydroxide solution are added dropwise within one hour with stirring. After the addition, the reaction mixture is kept at 80 ° C. for a further 1/4 hour. After cooling, it is taken up in 200 ml of ether and washed with water until neutral. After evaporation of the solvent, 147 g of crude product are obtained, which is fractionated by distillation. The first fractions (34 g) consist of the starting aldehyde (bp 33 ° C / 8 mmHg). The second part (28 g) of the distillate is the desired condensation product 6,8-dimethyl-3-nonen-2-one (bp. 88 ° C / 6 mmHg). The third part (55 g) consists of the addition product 6 , 8-Dimethyl-4-hydroxynonan-2-one (bp 106-108 ° C / 6 mmHg), which is dehydrated as follows:
  • 55 g of 6,8-dimethyl-4-hydroxy-nonan-2-one are distilled in a Clais flask over 2 g of potassium hydrogen sulfate under a vacuum of 18 mmHg at 92-1 03 ° C. The distillate is taken up in 100 ml of ether, washed with sodium hydrogen carbonate solution and then with water. After evaporation of the solvent, 43 g of crude product are obtained which, by distillation, give 40 g of 6,8-dimethyl-3-nonen-2-one (bp 88 ° C / 6 mmHg). Total yield: 71 g of 6,8-dimethyl-3-nonen-2-one (42% of theory).

64 g des Ketons werden in einem Rührautoklaven in Gegenwart von 6 g Kupferchromit unter 40 bar Wasserstoffdruck hydriert. Die Temperatur wird zunächst auf 140°C gebracht. Wenn die Wasserstoffabsorption nachlässt (nach 3 Stunden), wird auf 170°C erhitzt und 3 Stunden zwischen 165 und 170°C gehalten. Nach dem Abkühlen auf 25°C wird vom Katalysator abgenutscht und destilliert. Man erhält 65 g chemisch reines 2,4-Dimethyl-nonan-8-ol (Ausbeute: 85,4%).64 g of the ketone are hydrogenated in a stirred autoclave in the presence of 6 g of copper chromite under a hydrogen pressure of 40 bar. The temperature is first brought to 140 ° C. When the hydrogen absorption ceases (after 3 hours), the mixture is heated to 170 ° C. and kept between 165 and 170 ° C. for 3 hours. After cooling to 25 ° C., the catalyst is filtered off with suction and distilled. 65 g of chemically pure 2,4-dimethyl-nonan-8-ol are obtained (yield: 85.4%).

Beispiel 6Example 6

In einen 1 1-Stahlautoklaven, der mit einem Magnetrührer versehen ist (Autoclave Engineers, Inc.), gibt man 200 g frisch destilliertes 6,8-Dimethyl-3,5-nonadien-2-on und 2 g Kupferchromit. Man spült den Autoklaven mit Wasserstoff und setzt ihn zunächst unter einen Druck von 30 bar Wasserstoff. Man erhitzt nun rasch auf 100°C, hierauf langsam - innert 3 Stunden - auf 170°C. Der Druck wird alsdann auf 50 bar eingestellt, die Temperatur wird auf 200°C fixiert. Die theoretisch aufzunehmende Wasserstoffmenge beträgt 90 I. Man hält bei einem Druck von 50 bar und in einem Temperaturbereich zwischen 180-200°C. Nach 5 Stunden ist im Gemisch noch 7% ungesättigtes Material vorhanden. Man setzt die Hydrierung 6 weitere Stunden fort, um den Anteil an unhydriertem Produkt auf 0,2% herunterzudrücken. Das erhaltene Rohprodukt wird vom Katalysator abfiltriert und destilliert. Man erhält 171 g (Ausbeute 83%) chemisch reines 2,4-Dimethyl-nonan-8-ol vom Siedepunkt 91 °/6 mmHg, no = 1,4368; 136 g dieses Produktes werden als olfaktisch gut bezeichnet (Ausbeute 83% bzw. 65,7%).200 g of freshly distilled 6,8-dimethyl-3,5-nonadien-2-one and 2 g of copper chromite are placed in a 1 1 steel autoclave equipped with a magnetic stirrer (Autoclave Engineers, Inc.). The autoclave is flushed with hydrogen and first placed under a pressure of 30 bar of hydrogen. The mixture is then heated rapidly to 100 ° C, then slowly - within 3 hours - to 170 ° C. The pressure is then set to 50 bar and the temperature is fixed at 200 ° C. The theoretical amount of hydrogen to be absorbed is 90 I. It is kept at a pressure of 50 bar and in a temperature range between 180-200 ° C. After 5 hours there is still 7% unsaturated material in the mixture. The hydrogenation is continued for a further 6 hours in order to reduce the proportion of unhydrogenated product to 0.2%. The crude product obtained is filtered off from the catalyst and distilled. 171 g (yield 83%) of chemically pure 2,4-dimethyl-nonan-8-ol with a boiling point of 91 ° / 6 mmHg, no = 1.4368; 136 g of this product are said to be olfactively good (yield 83% and 65.7%).

Beispiel 7Example 7

Figure imgb0002
Figure imgb0002

Das Gemisch wirkt vorerst "synthetisch", nicht abgerundet, wenn man dazu 100 Gewichtsteile 2,5,7-Trimethyloctan-3-ol gibt, erhält man eine sehr angenehme, reichhaltige, ausserordentlich natürliche Parfumkomposition, in der der fruchtige Charakter dominiert.

Figure imgb0003
The mixture initially appears "synthetic", not rounded off, if you add 100 parts by weight of 2,5,7-trimethyloctan-3-ol, you get a very pleasant, rich, extraordinarily natural perfume composition in which the fruity character dominates.
Figure imgb0003

Diese Komposition hat wohl Maiglöckchencharakter und zielt in Richtung Flieder; sie wirkt aber vorerst synthetisch und etwas agressiv. Nach Zugabe von 100 Gewichtsteilen 2,5,7-Trimethyl-octan-3-ol herrscht ein samtartiger Eindruck vor, die Note wirkt nun abgerundet und fruchtig.

Figure imgb0004
This composition probably has the character of a lily of the valley and targets lilac; for the time being, however, it appears synthetic and somewhat aggressive. After adding 100 parts by weight of 2,5,7-trimethyl-octan-3-ol there is a velvety impression, the note now appears rounded and fruity.
Figure imgb0004

Wenn zu dieser Base 120 Gewichtsteile 2,5,7-Trimethyl-octan-3-ol gegeben werden, wird die grüne, agressive Note gedämpft, und es entsteht ein einheitlicher, abgerundeter, fruchtiger Geruch.

Figure imgb0005
If 120 parts by weight of 2,5,7-trimethyl-octan-3-ol are added to this base, the green, aggressive note is dampened and a uniform, rounded, fruity smell is produced.
Figure imgb0005

Die Anwesenheit von 2,5,7-Trimethyloctan-3-ol erteilt der Komposition einen angenehmen, abgerundeten Charakter, der ohne diesen Alkohol eindeutig fehlt.

Figure imgb0006
The presence of 2,5,7-trimethyloctan-3-ol gives the composition a pleasant, rounded character that is clearly lacking without this alcohol.
Figure imgb0006

Zugabe von 2,5,7-Trimethyl-3-octanol verstärkt die fruchtige Note der Komposition. Sie wirkt voller, kräftiger und erweckt einen abgerundeten, angenehmen Eindruck.

Figure imgb0007
Addition of 2,5,7-trimethyl-3-octanol increases the fruity note of the composition. It looks fuller, stronger and gives a rounded, pleasant impression.
Figure imgb0007

Auch ohne 2,5,7-Trimethyloctan-3-ol weist diese Komposition einen fruchtigen Charakter auf; der Zusatz an 2,5,7-Trimethyloctan-3-ol verstärkt und verbessert aber die fruchtige Note in Richtung Aprikosen, der natürliche Effekt von reifen Aprikosen wird erzielt.

Figure imgb0008
Even without 2,5,7-trimethyloctan-3-ol, this composition has a fruity character; the addition of 2,5,7-trimethyloctan-3-ol strengthens and improves the fruity note in the direction of apricots, the natural effect of ripe apricots is achieved.
Figure imgb0008

Die 100 Gewichtsteile 2,5,7-Trimethyloctan-3-ol vermitteln dem Gemisch einen natürlichen, abgerundeten Charakter, die typische Note der reifen Melone ist besser erkennbar.

Figure imgb0009
The 100 parts by weight of 2,5,7-trimethyloctan-3-ol impart a natural, rounded character to the mixture, the typical note of the ripe melon is more recognizable.
Figure imgb0009

Ohne Zusatz von 2,5,7-Trimethyloctan-3-ol wirkt die Mischung "spitzig" und agressiv; mit dem neuen Alkohol erhält man eine abgerundete, viel angenehmer wirkende Komposition, die sich für die, Parfümerie besonders gut eignet.

Figure imgb0010
Without the addition of 2,5,7-trimethyloctan-3-ol, the mixture appears "pointed" and aggressive; with the new alcohol you get a rounded, much more pleasant-looking composition that is particularly suitable for perfumery.
Figure imgb0010

Mit 185 Teilen 2,5,7-Trimethyloctan-3-ol erhält man eine Mischung mit einem originellen, den Salbeicharakter eindeutig betonenden Effekt, die Note ist in der modernen Parfümerie gesucht.

Figure imgb0011
With 185 parts of 2,5,7-trimethyloctan-3-ol, you get a mixture with an original effect that clearly emphasizes the character of the sage. The note is sought in modern perfumery.
Figure imgb0011

Wenn zu dieser klassischen Jasminbase 10C Gewichtsteile 2,4-Dimethyl-nonan-8-ol gegeben werden, entsteht eine Base, die nun nicht nur viel natürlicher wirkt, sondern auch einen abgerundeteren blumigen Charakter aufweist.If 10 parts by weight of 2,4-dimethyl-nonan-8-ol are added to this classic jasmine base, a base is created which not only looks much more natural, but also has a more rounded floral character.

Diese blumige Base eignet sich besonders gut für die Parfümierung von Seifen und Waschpulvern. Bei einer Dosierung von 1 bis 1,5% Gewichtsteilen in Seifen verhält sich die Komposition wie ein äusserst stabiles kräftiges Parfum. In Waschpulvern wird die optimale Wirkung bei einer Dosierung von 0,1 bis 0,3% erhalten; die blumige Note wird so durch die Anwesenheit von 2,4-Dimethyl-nonan-8-ol besonders hervorgehoben.

Figure imgb0012
This floral base is particularly suitable for perfuming soaps and washing powders. With a dosage of 1 to 1.5% by weight in soaps, the composition behaves like an extremely stable, powerful perfume. In washing powders, the optimal effect is obtained at a dosage of 0.1 to 0.3%; the floral note is particularly emphasized by the presence of 2,4-dimethyl-nonan-8-ol.
Figure imgb0012

Diese Komposition stellt eine "gewöhnliche" Rosenkomposition dar. Wenn man nun 145 Gewichtsteile 2,4-Dimethyl-nonan-8-ol zugibt, erhält man eine Base mit viel mehr Volumen, die natürlicher wirkt und besonders an Rosenblütenblätter und an die "Rose de mai" (Kreuzung zwischen Rosa centifolia und Rosa gallica) erinnert.

Figure imgb0013
This composition represents an "ordinary" rose composition. If you now add 145 parts by weight of 2,4-dimethyl-nonan-8-ol, you get a base with much more volume, which looks more natural and especially on rose petals and on the "Rose de mai "(cross between Rosa centifolia and Rosa gallica).
Figure imgb0013

Diese klassische Chypre-Base wird durch Zugabe von 100 Gewichtsteilen 2,4-Dimethyl-nonan-8-ol eindeutig verbessert, indem so eine blumige und grüne Nuance entsteht, und der (erwünschte) Geruch von Unterholz verstärkt wird.

Figure imgb0014
This classic chypre base is clearly improved by adding 100 parts by weight of 2,4-dimethyl-nonan-8-ol, creating a floral and green shade and enhancing the (desired) smell of undergrowth.
Figure imgb0014

Durch Zugabe von 100 Gewichtsteilen des neuen Alkohols erhält die konventionelle Flieder-Komposition eine erdige Nuance, welche den sonst "synthetisch" wirkenden Geruch ausgewogener, blumiger, natürlicher macht.

Figure imgb0015
By adding 100 parts by weight of the new alcohol, the conventional lilac composition gets an earthy shade, which makes the otherwise "synthetic" smell more balanced, flowery, more natural.
Figure imgb0015

In dieser Komposition bewirkt der neue Alkohol einen abrundenden Effekt. Die Komposition mit dem neuen Alkohol wirkt weniger "scharf", aber kräftiger, sie ist für die Parfümerie weit besser geeignet.

Figure imgb0016
In this composition, the new alcohol has a rounded effect. The composition with the new alcohol appears less "sharp", but more powerful, it is much more suitable for perfumery.
Figure imgb0016

Abwesenheit von 2,4-Dimethyl-8-nonanol in der Komposition erweckt wohl einen blumigen, aber "synthetischen", "chemischen" Eindruck. Der Zusatz von 2,5-Dimethyl-nonan-8-ol verleiht der Base einen erdigen, natürlichen Charakter.The absence of 2,4-dimethyl-8-nonanol in the composition gives a floral, but "synthetic", "chemical" impression. The addition of 2,5-dimethyl-nonan-8-ol gives the base an earthy, natural character.

Claims (3)

1. Process for the manufacture of compounds of the formula
Figure imgb0023
wherein R represents the 1-hydroxy-2-methyl-propyl residue of the 3-hydroxy-butyl residue, characterised by either
a) reacting 3,5-dimethylhexanal with an isopropylmagnesium halide or reacting isobutyraldehyde with a 2,4-dimethylpentylmagnesium halide, or
b) hydrogenating 2,5,7-trimethyl-4-octen-3-ol or 6,8-dimethyl-3-nonen-2-ol, or 2,5,7-trimethyl-1,4-octadien-3-one or 6,8-dimethyl-3,5-nonadien-2-one, or 2,5,7-trimethyl-3-octanone or 6,8-dimethyt-2-nonanone.
2. Odorant substance composition, characterised in that it contains a compound of the formula
Figure imgb0024
wherein R represents the 1-hydroxy-2-methyl-propyl residue or the 3-hydroxy-butyl residue.
3. Compounds of the formula
Figure imgb0025
wherein R represents the 1-hydroxy-2-methyl-propyl residue or the 3-hydroxy-butyl residue.
EP19780100580 1977-08-04 1978-08-02 2,5,7-trimethyloctane-3-ol and 2,4-dimethylnonane-8-ol; processes for their preparation; their use as olfactory agents; olfactory compositions containing them, as well as the preparation of such olfactory compositions Expired EP0000771B1 (en)

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