EP1078028A1 - Utilization of monocyclic aldehydes as odoriferous agents - Google Patents

Utilization of monocyclic aldehydes as odoriferous agents

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Publication number
EP1078028A1
EP1078028A1 EP99920865A EP99920865A EP1078028A1 EP 1078028 A1 EP1078028 A1 EP 1078028A1 EP 99920865 A EP99920865 A EP 99920865A EP 99920865 A EP99920865 A EP 99920865A EP 1078028 A1 EP1078028 A1 EP 1078028A1
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EP
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Prior art keywords
hydroformylation
cho
aldehydes
methyl
monocyclic
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Granted
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EP99920865A
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German (de)
French (fr)
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EP1078028B1 (en
Inventor
Thomas Markert
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Kao Corp SA
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Cognis Deutschland GmbH and Co KG
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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
    • C11B9/0003—Compounds of unspecified constitution defined by the chemical reaction for their preparation
    • 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
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms

Definitions

  • the invention relates to the use of special monocyclic aldehydes which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) enes as fragrances.
  • Cyclooct (adi) enes here means both cyclooctadienes and cyclooctenes, that is to say Cg monocycles with one or two CbC double bonds.
  • (di) methyl-substituted it is meant that the bicyclic system carries either one or two methyl groups as substituents.
  • fragrance industry has a constant need for new fragrances with interesting fragrances to complement the range of naturally available fragrances and make the necessary adjustments to changing fashionable tastes as well as the ever-increasing need for odor-improving products for everyday needs such as To be able to cover cosmetics and cleaning agents.
  • a fragrance booster is to be understood as a substance that is able to give the olfactory impressions of the components of a multi-substance system, i.e. a mixture of two or more fragrances to intensify sustainably.
  • the invention relates to the use of monocyclic aldehydes, which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) enes, as fragrances.
  • Another object of the invention is the use of monocyclic aldehydes, which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) enes, as a fragrance booster.
  • monocyclic aldehydes which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) enes, as a fragrance booster.
  • the compounds (3a), (3b) and (3c) described in more detail below are particularly preferred.
  • aldehydes to be used according to the invention are advantageously prepared by hydroformylation of (di) methyl-substituted cyclooct (adi) enes.
  • the latter compounds have a cyclooctane system as a common backbone.
  • Hydroformylation is a reaction known to the person skilled in the art, which was discovered in 1938 by von Roelen. Alkenes with carbon monoxide and hydrogen are converted into aldehydes. The reaction is also known as oxo synthesis.
  • the hydroformylation can be carried out partially or completely. Partial hydroformylation maintains one olefinic double bond per molecule of the starting compound, while only the other is hydroformylated; full hydroformylation introduces two CHO groups into the molecule. However, if (di) methyl-substituted cyclooctenes are used as starting materials, only complete hydroformylation is of course possible, since only one olefinic double bond is present per molecule of the starting compound.
  • the odor profile of the hydroformylation products according to the invention is original and new.
  • perfume compositions they enhance harmony and charisma as well as adhesion, whereby the dosage is adjusted to the desired fragrance, taking into account the other components of the composition.
  • Fragrances do not allow any conclusions to be drawn about the properties in the broadest sense of "structurally analogous" compounds - in the present case, for example, cyclooctanaldehyde (1) - or their mixtures with one another, because neither the mechanism of fragrance perception nor the influence of the chemical structure on fragrance perception have been adequately researched So it cannot normally be predicted whether a changed structure or special mixing ratios of known odoriferous substances will lead to a change in the olfactory properties and whether this change should be assessed positively or negatively.
  • the hydroformylation products according to the invention are particularly suitable for modifying and enhancing known compositions.
  • their extraordinary olfactory strength should be emphasized, which generally contributes to the refinement of compositions.
  • hydroformylation products according to the invention round off and harmonize the olfactory notes of a wide range of known compositions, but without dominating in an unpleasant manner.
  • the compounds (3a), (3b) and (3c) - compare the structural formulas below - are particularly suitable for use according to the invention as a fragrance and / or fragrance booster. Accordingly, the use of compounds (3a), (3b) and (3c) is particularly advantageous, for example, in room scents. In addition, it has been shown that the compounds (3a), (3b) and (3c) can be used with particular advantages in cleaning agents for strengthening citrus scents. CHO CHO ⁇ ⁇ CHO
  • the compounds (3 a), (3 b) and (3 c) can be prepared, for example, by hydroformylation of the corresponding (di) methyl-substituted cyclooctene or cyclooctadiene systems.
  • the usable proportions of the hydroformylation products according to the invention in fragrance compositions range from 0.001 to 70% by weight, based on the mixture as a whole.
  • the hydroformylation products according to the invention and compositions of this type can be used both for the perfuming of cosmetic preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants and in exudate perfumery.
  • perfuming technical products as well as washing and cleaning agents, fabric softeners, textile treatment agents or tobacco.
  • the compositions are metered into them in an olfactory effective amount, in particular in a concentration in the range from 0.05 to 2% by weight, based on the entire product.
  • these values should not 7

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

Abstract

The invention relates to the utilization of monocyclic aldehydes as odoriferous agents, obtained by partial or total hydroformylation of (di)methyl-substituted cyclooct(adi)enes. Said compounds are also characterized by good adhesive strength and propagating ability. Furthermore, said compounds also act as odor boosters.

Description

"Verwendung von monocyclischen Aldehyden als Riechstoffe" "Use of monocyclic aldehydes as fragrances"
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft die Verwendung spezieller monocyclischer Aldehyde, die erhältlich sind durch partielle oder vollständige Hydroformylierung von (Di)methyl-substituierten Cyclooct(adi)enen als Riechstoffe. Unter "Cyclooct(adi)enen" sind dabei sowohl Cyclooctadiene als auch Cyclooctene zu verstehen, also Cg-Monocyclen mit einer oder zwei C=C-Doppelbindungen. Unter "(Di)methyl-substituiert" ist zu verstehen, daß das bicyclische System entweder ein oder zwei Methylgruppen als Substituenten trägt.The invention relates to the use of special monocyclic aldehydes which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) enes as fragrances. “Cyclooct (adi) enes” here means both cyclooctadienes and cyclooctenes, that is to say Cg monocycles with one or two CbC double bonds. By "(di) methyl-substituted" it is meant that the bicyclic system carries either one or two methyl groups as substituents.
Stand der TechnikState of the art
Die Hydroformylierung cyclischer Diene ist literaturbekannt. So beschreibt beispielsweise A. Spencer in Journal of Organometallic Chemistry 1977, 124, Seilen 85 - 91 die Hydroformylierung von unter anderem 1,3- und 1,5- Cyclooctadien in Gegenwart spezieller Rhodiumkatalysatoren. Aus JP 58/21638 ist ein Herstellungsverfahren für Dialdehyde bekannt, bei dem nicht-konjugierte Diolefine in einem nicht mit Wasser mischbaren Lösungsmittel in Gegenwart eines Rhodium-Katalysators mit Wasserstoff und Kohlenmonoxyd umgesetzt werden. Aus US 3 985 769 ist Cyclooctanaldehyd (1), der gemäß als Rohstoff für dieThe hydroformylation of cyclic dienes is known from the literature. For example, A. Spencer in Journal of Organometallic Chemistry 1977, 124, ropes 85-91 describes the hydroformylation of 1,3- and 1,5-cyclooctadiene, among others, in the presence of special rhodium catalysts. JP 58/21638 discloses a production process for dialdehydes in which non-conjugated diolefins are reacted with hydrogen and carbon monoxide in a water-immiscible solvent in the presence of a rhodium catalyst. From US 3 985 769 cyclooctanaldehyde (1), which according to as a raw material for the
.CHO.CHO
(1) Herstellung davon abgeleiteter Acetale mit Dufteigenschaften beschrieben wird, hinsichtlich seiner geruchlichen Eigenschaften, die als „intensiv grün" beschrieben werden, bekannt.(1) Production of acetals derived therefrom with fragrance properties is described, with regard to its olfactory properties, which are described as "intensely green".
Viele natürliche Riechstoffe stehen gemessen am Bedarf in völlig unzureichender Menge zur Verfügung. Es ist daher klar, daß die Riechstoffindustrie einen ständigen Bedarf an neuen Riechstoffen mit interessanten Duftnoten hat, um die Palette der natürlich verfügbaren Riechstoffe zu ergänzen und die notwendigen Anpassungen an wechselnde modische Geschmacksrichtungen vornehmen sowie den ständig steigenden Bedarf ans geruchsverbessernden für Produkte des täglichen Bedarfs wie Kosmetika und Reinigungsmittel decken zu können.Many natural fragrances are available in completely inadequate amounts, measured by demand. It is therefore clear that the fragrance industry has a constant need for new fragrances with interesting fragrances to complement the range of naturally available fragrances and make the necessary adjustments to changing fashionable tastes as well as the ever-increasing need for odor-improving products for everyday needs such as To be able to cover cosmetics and cleaning agents.
Darüberhinaus besteht generell ein ständiger Bedarf an synthetischen Riechstoffen, die sich günstig und mit gleichbleibender Qualität herstellen lassen und erwünschte olfaktorische Eigenschafen haben, das heißt angenehme, möglichst naturnahe und qualitativ neuartige Geruchsprofile von ausreichender Intensität besitzen und in der Lage sind, den Duft von kosmetischen und Verbrauchs gutem vorteilhaft zu beeinflussen. Es besteht daher Bedarf an Verbindungen, die charakteristische neue Geruchsprofile bei gleichzeitig hoher Haftfestigkeit, Geruchsintensität und Strahlkraft haben.In addition, there is generally a constant need for synthetic fragrances that can be produced cheaply and with consistent quality and have desired olfactory properties, that is, pleasant, natural and qualitatively novel odor profiles of sufficient intensity and able to smell cosmetic and To influence consumption good advantageous. There is therefore a need for compounds which have characteristic new odor profiles with high adhesive strength, odor intensity and radiance.
Beschreibung der ErfindungDescription of the invention
Überraschenderweise wurde gefunden, daß Aldehyde, die erhältlich sind durch partielle oder vollständige Hydroformylierung von (Di)methyl-substituierten Cyclooct(adi)enen über bemerkenswerte Geruchseigenschaften verfügen. Über ihre spezielle Geruchscharakteristik hinaus, die durch eine große Bandbreite mit komplexen Schattierungen gekennzeichnet ist, zeichnen sich die Verbindungen 3It has surprisingly been found that aldehydes which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adienes) have remarkable odor properties. In addition to their special olfactory characteristics, which are characterized by a wide range with complex shades, the connections stand out 3
durch gute Haftfestigkeit und Strahlkraft aus. Darüber hinaus eignen sie sich in ausgezeichneter Weise als Duft-Booster. Unter einem Duft-Booster ist dabei eine Substanz zu verstehen, die in der Lage ist, die geruchlichen Eindrücke der Komponenten eines Mehrstoff- Systems, d.h. einer Mischung zweier oder mehrerer Riechstoffe, nachhaltig zu intensivieren.with good adhesive strength and radiance. In addition, they are excellent as fragrance boosters. A fragrance booster is to be understood as a substance that is able to give the olfactory impressions of the components of a multi-substance system, i.e. a mixture of two or more fragrances to intensify sustainably.
Gegenstand der Erfindung ist die Verwendung von monocyclischen Aldehyden, die erhältlich sind durch partielle oder vollständige Hydroformylierung von (Di)methyl-substituierten Cyclooct(adi)enen, als Riechstoffe.The invention relates to the use of monocyclic aldehydes, which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) enes, as fragrances.
Ein weiterer Gegenstand der Erfindung ist die Verwendung von monocyclischen Aldehyden, die erhältlich sind durch partielle oder vollständige Hydroformylierung von (Di)methyl-substituierten Cyclooct(adi)enen, als Duft-Booster. Hinsichtlich dieser Verwendung sind die unten näher beschriebenen Verbindungen (3a), (3b) und (3c) besonders bevorzugt.Another object of the invention is the use of monocyclic aldehydes, which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) enes, as a fragrance booster. With regard to this use, the compounds (3a), (3b) and (3c) described in more detail below are particularly preferred.
Die Herstellung der erfindungsgemäß einzusetzenden Aldehyde geschieht vorteilhaft durch Hydroformylierung von (Di)methyl-substituierten Cyclooct(adi)enen. Die letztgenannten Verbindungen weisen als gemeinsames Grundgerüst ein Cyclooctan-System auf. Das Grundgerüst - jedoch ohne die Angabe von Methylgruppen und C=C-Doppelbindungen wird durch die folgende Formel (2) veranschaulicht:The aldehydes to be used according to the invention are advantageously prepared by hydroformylation of (di) methyl-substituted cyclooct (adi) enes. The latter compounds have a cyclooctane system as a common backbone. The basic structure - but without the specification of methyl groups and C = C double bonds is illustrated by the following formula (2):
(2) 4(2) 4
Dieses System (2) enthält ein oder zwei Methylgruppen und ein oder zwei C=C- Doppelbindungen. Sofern zwei C=C-Doppelbindungen vorliegen gilt, daß diese nicht unmittelbar benachbart sind.This system (2) contains one or two methyl groups and one or two C = C double bonds. If there are two C = C double bonds, it applies that these are not immediately adjacent.
Bei der Hydroformylierung handelt es sich um eine dem Fachmann bekannte Reaktion, die bereits 1938 durch von Roelen entdeckt wurde. Dabei werden Alkene mit Kohlenmonoxyd und Wasserstoff in Aldehyde überführt. Die Reaktion ist auch als Oxo- Synthese bekannt.Hydroformylation is a reaction known to the person skilled in the art, which was discovered in 1938 by von Roelen. Alkenes with carbon monoxide and hydrogen are converted into aldehydes. The reaction is also known as oxo synthesis.
Sofern im Rahmen der vorliegenden Erfindung als Ausgangsstoffe (Di)methyl- substituierte Cyclooctadiene eingesetzt werden, kann die Hydroformylierung partiell oder vollständig durchgeführt werden. Bei der partiellen Hydroformylierung bleibt eine olefinische Doppelbindung pro Molekül der Ausgangsverbindung erhalten, während nur die andere hydroformyliert wird, bei der vollständigen Hydroformylierung werden zwei CHO-Gruppen in das Molekül eingeführt. Sofern jedoch als Ausgangsstoffe (Di)methyl-substituierte Cyclooctene eingesetzt werden, ist selbstverständlich lediglich die vollständige Hydroformylierung möglich, da nur eine olefinische Doppelbindung pro Molekül der Ausgangsverbindung vorhanden ist.If (di) methyl-substituted cyclooctadienes are used as starting materials in the context of the present invention, the hydroformylation can be carried out partially or completely. Partial hydroformylation maintains one olefinic double bond per molecule of the starting compound, while only the other is hydroformylated; full hydroformylation introduces two CHO groups into the molecule. However, if (di) methyl-substituted cyclooctenes are used as starting materials, only complete hydroformylation is of course possible, since only one olefinic double bond is present per molecule of the starting compound.
Das Geruchsprofil der erfindungsgemäßen Hydroformylierungsprodukte ist originell und neuartig. In Parfüm-Kompositionen verstärken sie die Harmonie und Ausstrahlung sowie auch die Haftung, wobei die Dosierung unter Berücksichtigung der übrigen Bestandteile der Komposition auf die jeweils angestrebte Duftnote abgestimmt wird.The odor profile of the hydroformylation products according to the invention is original and new. In perfume compositions, they enhance harmony and charisma as well as adhesion, whereby the dosage is adjusted to the desired fragrance, taking into account the other components of the composition.
Daß die erfindungsgemäßen Hydroformylierungsprodukte interessante parfümistische Noten aufweisen, war nicht vorhersehbar und ist eine Bestätigung für die allgemeine Erfahrung, daß die olfaktorischen Eigenschaften bekannter 5The fact that the hydroformylation products according to the invention have interesting perfume notes was not predictable and is a confirmation of the general experience that the olfactory properties are better known 5
Riechstoffe keinen zwingenden Rückschluß auf die Eigenschaften im weitesten Sinne "strukturanaloger" Verbindungen - im vorliegenden Fall etwa Cyclooctanaldehyd (1) - oder deren Mischungen untereinander zulassen, weil weder der Mechanismus der Duftwahrnehmung noch der Einfluß der chemischen Struktur auf die Duftwahrnehmung hinreichend erforscht sind, somit also normalerweise nicht vorhergesehen werden kann, ob ein geänderter Aufbau oder spezielle Mischungsverhältnisse bekannter Riechstoffe überhaupt zur Änderung der olfaktorischen Eigenschaften führt und ob diese Änderung positiv oder negativ zu beurteilen ist.Fragrances do not allow any conclusions to be drawn about the properties in the broadest sense of "structurally analogous" compounds - in the present case, for example, cyclooctanaldehyde (1) - or their mixtures with one another, because neither the mechanism of fragrance perception nor the influence of the chemical structure on fragrance perception have been adequately researched So it cannot normally be predicted whether a changed structure or special mixing ratios of known odoriferous substances will lead to a change in the olfactory properties and whether this change should be assessed positively or negatively.
Die erfindungsgemäßen Hydroformylierungsprodukte eigenen sich aufgrund ihrer Geruchsprofile insbesondere auch zur Modifizierung und Verstärkung bekannter Kompositionen. Hervorgehoben werden soll insbesondere ihre außerordentliche Geruchsstärke, die ganz allgemein zur Veredlung von Kompositionen beiträgt.Because of their odor profiles, the hydroformylation products according to the invention are particularly suitable for modifying and enhancing known compositions. In particular, their extraordinary olfactory strength should be emphasized, which generally contributes to the refinement of compositions.
Bemerkenswert ist ferner die Art und Weise, wie die erfindungsgemäßen Hydroformylierungsprodukte die Geruchsnoten einer breiten Palette bekannter Kompositionen abrunden und harmonisieren, ohne jedoch in unangenehmer Weise zu dominieren.Also noteworthy is the way in which the hydroformylation products according to the invention round off and harmonize the olfactory notes of a wide range of known compositions, but without dominating in an unpleasant manner.
In ganz besonderer Weise eignet sich die Verbindungen (3a), (3b) und (3c) - vergleiche hierzu die untenstehenden Strukturformeln - für die erfindungsgemäße Verwendung als Riechstoff und/oder Duft-Booster. Dementsprechend ist der Einsatz der Verbindungen (3a), (3b) und (3c) beispielsweise in Raumbeduftern besonders vorteilhaft. Darüber hinaus hat sich gezeigt, daß die Verbindungen (3a), (3b) und (3c) mit besonderen Vorteilen in Reinigungsmitteln zur Verstärkung von Zitrusdüften eingesetzt werden können. CHO CHO \ Λ CHOThe compounds (3a), (3b) and (3c) - compare the structural formulas below - are particularly suitable for use according to the invention as a fragrance and / or fragrance booster. Accordingly, the use of compounds (3a), (3b) and (3c) is particularly advantageous, for example, in room scents. In addition, it has been shown that the compounds (3a), (3b) and (3c) can be used with particular advantages in cleaning agents for strengthening citrus scents. CHO CHO \ Λ CHO
OHCOHC
(3a) (3b) (3c)(3a) (3b) (3c)
Die Verbindungen (3 a), (3 b) und (3 c) lassen sich beispielsweise durch Hydroformylierung der entsprechenden (Di)methyl-substituierten Cycloocten- bzw. Cyclooctadien-Systeme herstellen.The compounds (3 a), (3 b) and (3 c) can be prepared, for example, by hydroformylation of the corresponding (di) methyl-substituted cyclooctene or cyclooctadiene systems.
(3b) fällt dabei in der Regel in Form eines (E,Z)-Gemisches an, d.h. die C=C- Doppelbindung kann sowohl E- als auch Z-konfiguriert sein, wobei in aller Regel ein Gemisch vorliegen wird, in dem die Z-Konfiguration überwiegt. Es kann jedoch auch gewünscht sein, die E- bzw. Z-konfigurierte Form in Reinsubstanz einzusetzen.(3b) is usually obtained in the form of an (E, Z) mixture, i.e. the C = C double bond can be either E- or Z-configured, as a rule there will be a mixture in which the Z-configuration predominates. However, it may also be desirable to use the E or Z configured form in pure substance.
Die einsetzbaren Anteile der erfindungsgemäßen Hydroformylierungsprodukte in Riechstoffkompositionen bewegen sich von 0,001 bis 70 Gew.-%, bezogen auf die gesamte Mischung. Die erfindungsgemäßen Hydroformylierungsprodukte sowie Kompositionen dieser Art können sowohl zur Parfümierung kosmetischer Präparate wie Lotionen, Cremes, Shampoos, Seifen, Salben, Puder, Aerosole, Zahnpasten, Mundwässer, Deodorantien als auch in der Extraitparfümerie verwendet werden. Ebenso besteht eine Einsatzmöglichkeit zur Parfümierung technischer Produkte sowie Wasch- und Reinigungsmittel, Weichspüler, Textilbehandlungsmittel oder Tabak. Zur Parfümierung dieser verschiedener Produkte werden diesen die Kompositionen in einer olfaktorisch wirksamen Menge, insbesondere in einer Konzentration im Bereich von 0,05 bis 2 Gew.-%, bezogen auf das gesamte Produkt, zudosiert. Diese Werte sollen jedoch keine 7The usable proportions of the hydroformylation products according to the invention in fragrance compositions range from 0.001 to 70% by weight, based on the mixture as a whole. The hydroformylation products according to the invention and compositions of this type can be used both for the perfuming of cosmetic preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants and in exudate perfumery. There is also an application for perfuming technical products as well as washing and cleaning agents, fabric softeners, textile treatment agents or tobacco. To perfume these various products, the compositions are metered into them in an olfactory effective amount, in particular in a concentration in the range from 0.05 to 2% by weight, based on the entire product. However, these values should not 7
Grenzwerte darstellen, da der erfahrene Parfiimeur auch mit geringeren Konzentrationen Effekte erzielen oder aber mit noch höheren Dosierungen neuartige Komplexe aufbauen kann.Show limit values, since the experienced perfumer can achieve effects with lower concentrations or build new types of complexes with even higher doses.
Die vorliegenden Beispiele sollen den Gegenstand der Erfindung erläutern und sind nicht einschränkend aufzufassen. The present examples are intended to explain the subject matter of the invention and are not to be interpreted as restrictive.
B e i s p i e l eB e i s p i e l e
1. Herstellung von 2,6-Dimethyl-l-Formyl-cyclooctan (3a)1. Preparation of 2,6-dimethyl-l-formyl-cyclooctane (3a)
CHO CHO
(3a)(3a)
2 mol (272,46 g) l,5-Dimethyl-l,5-cyclooctadien (Hersteller: Fa. Shell; gaschromatographisch bestimmte Reinheit: 75%) wurden mit 1,7 mmol (1 ,175 g) eines Rhodium-Katalysators der Formel Rh(CO)Cl(PPh3)2 und 19 mmol (5 g) Triphenylphosphin zusammen in einem Autoklaven vorgelegt und ohne Lösungsmittel unter starker Durchmischung mit einer 1 : 1 Mischung Wasserstoff/Kohlenmonoxid bei einem Druck von 60 kg/cm^ bei 100 °C für 5 Stunden zur Reaktion gebracht. Zur Aufarbeitung wurde der Reaktorinhalt filtriert und über eine 20 cm Vigreux-Kolonne destilliert.2 mol (272.46 g) l, 5-dimethyl-l, 5-cyclooctadiene (manufacturer: Shell; purity determined by gas chromatography: 75%) were mixed with 1.7 mmol (1, 175 g) of a rhodium catalyst Formula Rh (CO) Cl (PPh3) 2 and 19 mmol (5 g) triphenylphosphine presented together in an autoclave and without solvent with thorough mixing with a 1: 1 mixture of hydrogen / carbon monoxide at a pressure of 60 kg / cm ^ at 100 ° C reacted for 5 hours. For working up, the reactor contents were filtered and distilled through a 20 cm Vigreux column.
Die anschließende Fraktionierung erfolgte an einer Drehbandkolonne. Es wurden 82 g Monoaldehyd (3a) erhalten (Siedepunkt: 65 °C/ 16 mbar), daneben 35,4 g Dialdehyd (Siedepunkt: 105 °C/ 16 mbar).The subsequent fractionation was carried out on a rotating column. 82 g of monoaldehyde (3a) were obtained (boiling point: 65 ° C / 16 mbar), in addition 35.4 g of dialdehyde (boiling point: 105 ° C / 16 mbar).
Geruchsbeschreibung von (3 a): minzig, holzig, Gurke-Dill-Note 9Description of the smell of (3 a): minty, woody, cucumber-dill note 9
2. Herstellung von 2,6-DimethyI-5-Formyl-cyclooct-l-en (3b)2. Preparation of 2,6-dimethyl-5-formyl-cyclooct-1-ene (3b)
CHOCHO
(3b)(3b)
2 mol (272,46 g) l,5-Dimethyl-l,5-cyclooctadien (Hersteller: Fa. Aldrich; gaschromatographisch bestimmte Reinheit: 76%) wurden mit 1,7 mmol (1,175 g) eines Rhodium-Katalysators der Formel Rh(CO)Cl(PPh3)2 und 19 mmol (5 g) Triphenylphosphin zusammen in einem Autoklaven vorgelegt und ohne Lösungsmittel unter starker Durchmischung mit einer 1 : 1 Mischung Wasserstoff/Kohlenmonoxid bei einem Druck von 60 kg/cm^ bei 100 °C für 5 Stunden zur Reaktion gebracht. Zur Aufarbeitung wurde der Reaktorinhalt filtriert und über eine 20 cm Vigreux-Kolonne destilliert.2 mol (272.46 g) l, 5-dimethyl-l, 5-cyclooctadiene (manufacturer: Aldrich; purity determined by gas chromatography: 76%) were mixed with 1.7 mmol (1.175 g) of a rhodium catalyst of the formula Rh (CO) Cl (PPh3) 2 and 19 mmol (5 g) triphenylphosphine together in an autoclave and without solvent with vigorous mixing with a 1: 1 mixture of hydrogen / carbon monoxide at a pressure of 60 kg / cm ^ at 100 ° C for Reacted for 5 hours. For working up, the reactor contents were filtered and distilled through a 20 cm Vigreux column.
Die Fraktionierung in Edukt und Monoaldehyd erfolgte an einer Drehbandkolonne. Es wurden 132 g Produkt (3b) erhalten (Siedepunkt: 58 °C/ 16 mbar).The fractionation into starting material and monoaldehyde was carried out on a rotating column. 132 g of product (3b) were obtained (boiling point: 58 ° C./16 mbar).
Geruchsbeschreibung: technischDescription of smell: technical
3. Herstellung von 2,6-Dimethyl-l,5-Di-FormyI-cyclooctan (3c)3. Preparation of 2,6-dimethyl-1,5-di-formyl-cyclooctane (3c)
CHOCHO
OHCOHC
(3c) 10(3c) 10
2 mol (272,46 g) l,5-Dimethyl-l,5-cyclooctadien (Hersteller: Fa. Shell; gaschromatographisch bestimmte Reinheit: 98%) wurden mit 1,7 mmol (1,175 g) eines Rhodium-Katalysators der Formel Rh(CO)Cl(PPh3)2 und 19 mmol (5 g) Triphenylphosphin zusammen in einem Autoklaven vorgelegt und ohne Lösungsmittel unter starker Durchmischung mit einer 1 : 1 Mischung Wasserstoff/Kohlenmonoxid bei einem Druck von 60 kg/cm^ bei 100 °C für 5 Stunden zur Reaktion gebracht. Zur Aufarbeitung wurde der Reaktorinhalt filtriert und über eine 20 cm Vigreux-Kolonne destilliert.2 mol (272.46 g) l, 5-dimethyl-l, 5-cyclooctadiene (manufacturer: Shell; purity determined by gas chromatography: 98%) were mixed with 1.7 mmol (1.175 g) of a rhodium catalyst of the formula Rh (CO) Cl (PPh3) 2 and 19 mmol (5 g) triphenylphosphine placed together in an autoclave and without solvent with thorough mixing with a 1: 1 mixture of hydrogen / carbon monoxide at a pressure of 60 kg / cm ^ at 100 ° C for Reacted for 5 hours. For working up, the reactor contents were filtered and distilled through a 20 cm Vigreux column.
Die anschließende Fraktionierung erfolgte an einer Drehbandkolonne. Es wurden 29 g eines Gemisches von 2,6-Dimethyl- 1 ,5-Di-Formyl-cyclooctan und 2,5- Dimethyl-l,4-Di-Formyl-cyclooctan erhalten (Siedepunkt: 105 °C/ 16 mbar).The subsequent fractionation was carried out on a rotating column. 29 g of a mixture of 2,6-dimethyl-1,5-di-formyl-cyclooctane and 2,5-dimethyl-1,4-di-formyl-cyclooctane were obtained (boiling point: 105 ° C./16 mbar).
Geruchsbeschreibung: grün, Kartoffel-Note Description of smell: green, potato note

Claims

1111
Patentansprücheclaims
1. Verwendung von monocyclischen Aldehyden, die erhältlich sind durch partielle oder vollständige Hydroformylierung von (Di)methyl-substituierten Cyclooct(adi)enen als Riechstoffe.1. Use of monocyclic aldehydes which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) enes as fragrances.
2. Verwendung der monocyclischen Aldehyde der nachstehenden Strukturformeln2. Use of the monocyclic aldehydes of the structural formulas below
CHO CHO CHOCHO CHO CHO
OHCOHC
als Riechstoffe.as fragrances.
3. Verwendung von monocyclischen Aldehyden, die erhältlich sind durch partielle oder vollständige Hydroformylierung von (Di)methyl-substituierten Cyclooct(adi)enen, als Duft-Booster.3. Use of monocyclic aldehydes, which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) enes, as a fragrance booster.
3. Verwendung der monocyclischen Aldehyde der nachstehenden Strukturformeln3. Use of the monocyclic aldehydes of the structural formulas below
CHO CHO CHOCHO CHO CHO
OHCOHC
als Duft-Booster. 12as a fragrance booster. 12
5. Verwendung von monocyclischen Aldehyden, die erhältlich sind durch partielle oder vollständige Hydroformylierung von (Di)methyl-substituierten Cyclooct(adi)enen, in kosmetischen Präparaten, technischen Produkten oder der alkoholischen Parfümerie.5. Use of monocyclic aldehydes, which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) enes, in cosmetic preparations, technical products or alcoholic perfumery.
6. Verwendung der monocyclischen Aldehyde der nachstehenden Strukturformeln6. Use of the monocyclic aldehydes of the structural formulas below
CHO CHO CHOCHO CHO CHO
OHCOHC
in kosmetischen Präparaten, technischen Produkten oder der alkoholischen Parfümerie. in cosmetic preparations, technical products or alcoholic perfumery.
EP99920865A 1998-04-17 1999-04-08 Utilization of monocyclic aldehydes as odoriferous agents Expired - Lifetime EP1078028B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19817043 1998-04-17
DE19817043A DE19817043A1 (en) 1998-04-17 1998-04-17 Monocyclic aldehydes obtained by hydroformylation of (di)-methyl-cyclooct(adi)enes used as perfumes or perfume boosters
PCT/EP1999/003207 WO1999054430A1 (en) 1998-04-17 1999-04-08 Utilization of monocyclic aldehydes as odoriferous agents

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EP1078028A1 true EP1078028A1 (en) 2001-02-28
EP1078028B1 EP1078028B1 (en) 2005-08-03

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EP (1) EP1078028B1 (en)
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WO (1) WO1999054430A1 (en)

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US6271193B1 (en) 2000-10-11 2001-08-07 International Flavors & Fragrances Inc. Carbon containing functional group substituted 4,5,6,7-tetrahydro-polyalkylated-4-indanes, isomers thereof, processes for preparing same and uses thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985769A (en) * 1974-11-15 1976-10-12 Universal Oil Products Company Acetal derivatives of cyclooctyl carboxaldehydes
US3984478A (en) 1975-05-27 1976-10-05 Universal Oil Products Company Hydroformylation process
DE2849742B2 (en) * 1978-11-16 1980-10-16 Henkel Kgaa, 4000 Duesseldorf Process for the production of aldehydes and use of the process products as fragrances
US4306085A (en) * 1979-07-05 1981-12-15 Shell Oil Company Hydroformylation process using resin-ligand-metal catalyst
JPS5821638A (en) 1981-07-31 1983-02-08 Mitsubishi Petrochem Co Ltd Preparation of dialdehydes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9954430A1 *

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ES2246569T3 (en) 2006-02-16
US6541446B1 (en) 2003-04-01
IL139026A0 (en) 2001-11-25
WO1999054430A1 (en) 1999-10-28
DE19817043A1 (en) 1999-10-21
EP1078028B1 (en) 2005-08-03
DE59912360D1 (en) 2005-09-08
JP2002512301A (en) 2002-04-23

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