EP1078028B1 - Utilization of monocyclic aldehydes as odoriferous agents - Google Patents
Utilization of monocyclic aldehydes as odoriferous agents Download PDFInfo
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- EP1078028B1 EP1078028B1 EP99920865A EP99920865A EP1078028B1 EP 1078028 B1 EP1078028 B1 EP 1078028B1 EP 99920865 A EP99920865 A EP 99920865A EP 99920865 A EP99920865 A EP 99920865A EP 1078028 B1 EP1078028 B1 EP 1078028B1
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- hydroformylation
- aldehydes
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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
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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
- C11B9/0026—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 specific monocyclic aldehydes which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) s as fragrances.
- (di) methyl-substituted is meant that the bicyclic system carries either one or two methyl groups as substituents.
- 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 obtainable by partial or complete hydroformylation of (di) methyl-substituted Cyclooct (adi) enes, as a fragrance booster.
- monocyclic Aldehydes obtainable by partial or complete hydroformylation of (di) methyl-substituted Cyclooct (adi) enes, as a fragrance booster.
- 3a), (3b) described in more detail below and (3c) particularly preferred.
- the preparation of the aldehydes to be used according to the invention is advantageously carried out by hydroformylation of (di) methyl-substituted cyclooct (adi) s.
- the latter compounds have as common backbone on a cyclooctane system.
- hydroformylation is known to one skilled in the art Reaction that was discovered in 1938 by von Roelen. These are alkenes converted into aldehydes with carbon monoxide and hydrogen. The reaction is too known as oxo synthesis.
- methyl-substituted Cyclooctadienes can be used in hydroformylation be carried out partially or completely. In the partial Hydroformylation remains an olefinic double bond per molecule of Starting compound while only the other hydroformylieil, at In complete hydroformylation, two CHO groups are incorporated into the molecule introduced. If, however, as starting materials (di) methyl-substituted cyclooctenes Of course, only the complete one is used Hydroformylation possible because only one olefinic double bond per molecule the starting compound is present.
- the odor profile of the hydroformylation products of the invention is original and novel.
- perfume compositions they enhance harmony and harmony Radiation as well as the adhesion, whereby the dosage under Consideration of the remaining components of the composition on each desired scent is matched.
- the hydroformylation products according to the invention are suitable because of their Odor profiles especially for modifying and amplifying known Compositions. Emphasized in particular is their extraordinary Odor strength, which generally contributes to the refinement of compositions.
- the compounds (3a), (3b) and (3c) - compare the structural formulas below - for the inventive use as a fragrance and / or fragrance booster. Accordingly, the use of the compounds (3a), (3b) and (3c), for example, in Griffinbeduftern particularly advantageous. In addition, it has been found that the compounds (3a), (3b) and (3c) can be used with particular advantages in cleaning agents for strengthening citrus diets.
- the compounds (3a), (3b) and (3c) can be, for example, by Hydroformylation of the corresponding (di) methyl-substituted cyclooctene or produce cyclooctadiene systems.
- the usable proportions of the hydroformylation products according to the invention in Fragrance compositions range from 0.001 to 70 wt .-%, based on the entire mix.
- the hydroformylation products according to the invention and Compositions of this kind can be used both for perfuming cosmetic Preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, Toothpastes, mouthwashes, deodorants as well as in extract perfumery be used.
- perfuming cosmetic Preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, Toothpastes, mouthwashes, deodorants as well as in extract perfumery be used.
- perfuming technical products as well as detergents and cleaners, fabric softeners, Textile treatment or tobacco.
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- 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)
Description
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 C8-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 specific monocyclic aldehydes which are obtainable by partial or complete hydroformylation of (di) methyl-substituted cyclooct (adi) s as fragrances. "Cyclooct (adi) enes" are to be understood as meaning both cyclooctadienes and cyclooctenes, ie C 8 monocycles having one or two C =C double bonds. By "(di) methyl-substituted" is meant that the bicyclic system carries either one or two methyl groups as substituents.
Die Hydroformylierung cyclischer Diene ist literaturbekannt. So beschreibt beispielsweise A. Spencer in Journal of Organometallic Chemistry 1977, 124, Seiten 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 die The hydroformylation of cyclic dienes is known from the literature. For example, A. Spencer in Journal of Organometallic Chemistry 1977, 124, pages 85-91 describes the hydroformylation of, inter alia, 1,3- and 1,5-cyclooctadiene in the presence of specific rhodium catalysts. JP 58/21638 discloses a preparation process for dialdehydes in which non-conjugated diolefins are reacted in a water-immiscible solvent in the presence of a rhodium catalyst with hydrogen and carbon monoxide. From US 3,985,769 cyclooctanaldehyde (1), according to as raw material for the
Herstellung davon abgeleiteter Acetale mit Dufteigenschaften beschrieben wird, hinsichtlich seiner geruchlichen Eigenschaften, die als "intensiv grün" beschrieben werden, bekannt.Preparation of derived acetals with fragrance properties is described in terms of its odor properties, described as "intense green" become known.
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 completely inadequate in terms of demand Quantity available. It is therefore clear that the fragrance industry a Constant need for new fragrances with interesting scents has to the Range of naturally available fragrances to complete and the necessary Make adjustments to changing fashionable tastes as well the ever-increasing need for odor-improving products for the daily necessities such as cosmetics and cleaning products.
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 natumahe und qualitativ neuartige Geruchsprofile von ausreichender Intensität besitzen und in der Lage sind, den Duft von kosmetischen und Verbrauchsgütern vorteilhaft zu beeinflussen. Es besteht daher Bedarf an Verbindungen, die charakteristische neue Geruchsprofile bei gleichzeitig hoher Haftfestigkeit, Geruchsintensität und Strahlkraft haben.Moreover, there is generally a continuing need for synthetic fragrances, which can be produced cheaply and with consistent quality and desired have olfactory properties, that is pleasant, as near as possible and possess qualitatively new smell profiles of sufficient intensity and in the Are able to favor the fragrance of cosmetic and consumer goods too influence. There is therefore a need for compounds that are characteristic new Odor profiles with simultaneously high adhesive strength, odor intensity and Have radiance.
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 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.Surprisingly, it has been found that aldehydes obtainable by partial or complete hydroformylation of (di) methyl-substituted Cyclooct (adi) enes have remarkable odor properties. About their special odor characteristic, which comes with a large bandwidth characterized by complex shades, the connections stand out due to good adhesion and radiance. In addition, they are suitable in Excellent way as a fragrance booster. Under a fragrance booster is one To understand substance that is capable of the odorous impressions of the Components of a multi-fuel system, i. 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 obtainable by partial or complete hydroformylation of (di) methyl-substituted Cyclooct (adi) enes, as a fragrance booster. Regarding this use are the compounds (3a), (3b) described in more detail below and (3c) 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 preparation of the aldehydes to be used according to the invention is advantageously carried out by hydroformylation of (di) methyl-substituted cyclooct (adi) s. The latter compounds have as common backbone on a cyclooctane system. The backbone - but without the indication of methyl groups and C = C double bonds is illustrated by the following formula (2):
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 two C = C double bonds are present that this 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.The hydroformylation is known to one skilled in the art Reaction that was discovered in 1938 by von Roelen. These are alkenes converted into aldehydes with carbon monoxide and hydrogen. The reaction is too 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 hydroformylieil 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 in the context of the present invention as starting materials (di) methyl-substituted Cyclooctadienes can be used in hydroformylation be carried out partially or completely. In the partial Hydroformylation remains an olefinic double bond per molecule of Starting compound while only the other hydroformylieil, at In complete hydroformylation, two CHO groups are incorporated into the molecule introduced. If, however, as starting materials (di) methyl-substituted cyclooctenes Of course, only the complete one is used Hydroformylation possible because only one olefinic double bond per molecule the starting compound is present.
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 of the invention is original and novel. In perfume compositions they enhance harmony and harmony Radiation as well as the adhesion, whereby the dosage under Consideration of the remaining components of the composition on each desired scent is matched.
Daß die erfindungsgemäßen Hydroformylierungsprodukte interessante parfümistische Noten aufweisen, war nicht vorhersehbar und ist eine Bestätigung für die allgemeine Erfahrung, daß die olfaktorischen Eigenschaften bekannter 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.That the hydroformylation products of the invention interesting have perfumistic marks, was unpredictable and is a confirmation for the general experience that the olfactory properties are better known Fragrances no compelling conclusion on the properties in the widest Meaning "structurally analogous" compounds - in the present case, for example Cyclooctanaldehyde (1) - or allow their mixtures with each other, because neither the mechanism of the smell perception nor the influence of the chemical Structure are sufficiently researched on the fragrance perception, thus therefore usually can not be foreseen, whether a modified construction or special mixing ratios of known fragrances at all to change the olfactory properties and whether this change is positive or negative to judge.
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.The hydroformylation products according to the invention are suitable because of their Odor profiles especially for modifying and amplifying known Compositions. Emphasized in particular is their extraordinary Odor strength, 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 invention Hydroformylation known the odor notes of a wide range Round off and harmonize compositions without, however, in an unpleasant way to dominate.
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 Zitrusditften eingesetzt werden können. In a very special way, the compounds (3a), (3b) and (3c) - compare the structural formulas below - for the inventive use as a fragrance and / or fragrance booster. Accordingly, the use of the compounds (3a), (3b) and (3c), for example, in Raumbeduftern particularly advantageous. In addition, it has been found that the compounds (3a), (3b) and (3c) can be used with particular advantages in cleaning agents for strengthening citrus diets.
Die Verbindungen (3a), (3b) und (3c) lassen sich beispielsweise durch Hydroformylierung der entsprechenden (Di)methyl-substituierten Cycloocten- bzw. Cyclooctadien-Systeme herstellen.The compounds (3a), (3b) and (3c) can be, for example, by Hydroformylation of the corresponding (di) methyl-substituted cyclooctene or produce 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) usually occurs in the form of an (E, Z) mixture, i. the C = C double bond can be both E- and Z-configured, and usually there will be a mixture in which the Z configuration predominates. It can however, also be desired, the E- or Z-configured form in pure substance use.
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 Grenzwerte darstellen, da der erfahrene Parfümeur auch mit geringeren Konzentrationen Effekte erzielen oder aber mit noch höheren Dosierungen neuartige Komplexe aufbauen kann.The usable proportions of the hydroformylation products according to the invention in Fragrance compositions range from 0.001 to 70 wt .-%, based on the entire mix. The hydroformylation products according to the invention and Compositions of this kind can be used both for perfuming cosmetic Preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, Toothpastes, mouthwashes, deodorants as well as in extract perfumery be used. Likewise, there is a possible use for perfuming technical products as well as detergents and cleaners, fabric softeners, Textile treatment or tobacco. To perfume this different Products become these the compositions in an olfaktisch effective Amount, in particular in a concentration in the range of 0.05 to 2 wt .-%, based on the entire product, added. However, these values should not be Limit values represent, since the experienced perfumer with less Concentrations achieve effects or with even higher dosages can build novel complexes.
Die vorliegenden Beispiele sollen den Gegenstand der Erfindung erläutern und sind nicht einschränkend aufzufassen. The present examples are intended to illustrate the subject matter of the invention and are not meant to be limiting.
2 mol (272,46 g) 1,5-Dimethyl-1,5-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/cm2 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) of 1,5-dimethyl-1,5-cyclooctadiene (manufacturer: Shell Co., purity determined by gas chromatography: 75%) were mixed with 1.7 mmol (1.175 g) of a rhodium catalyst of the formula Rh (CO) Cl (PPh 3 ) 2 and 19 mmol (5 g) of 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 2 at 100 ° C. reacted for 5 hours. For workup, 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 band column. There were 82 g of monoaldehyde (3a) were obtained (boiling point: 65 ° C / 16 mbar), next to 35.4 g Dialdehyde (boiling point: 105 ° C / 16 mbar).
Geruchsbeschreibung von (3a): minzig, holzig, Gurke-Dill-Note Odor description of (3a): minty, woody, cucumber-dill note
2 mol (272,46 g) 1,5-Dimethyl-1,5-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/cm2 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) of 1,5-dimethyl-1,5-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 (PPh 3 ) 2 and 19 mmol (5 g) of 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 2 at 100 ° C. reacted for 5 hours. For workup, 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 in educt and monoaldehyde was carried out on a rotating column. There were obtained 132 g of product (3b) (boiling point: 58 ° C / 16 mbar).
Geruchsbeschreibung: technischOdor description: technical
2 mol (272,46 g) 1,5-Dimethyl-1,5-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/cm2 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) of 1,5-dimethyl-1,5-cyclooctadiene (manufacturer: Shell Co., 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 (PPh 3 ) 2 and 19 mmol (5 g) of 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 2 at 100 ° C. reacted for 5 hours. For workup, 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-1,4-Di-Formyl-cyclooctan erhalten (Siedepunkt: 105 °C/16 mbar).The subsequent fractionation was carried out on a rotating band column. There were 29 g of a mixture of 2,6-dimethyl-1,5-di-formyl-cyclooctane and 2,5-dimethyl-1,4-di-formyl-cyclooctane obtained (boiling point: 105 ° C / 16 mbar).
Geruchsbeschreibung: grün, Kartoffel-NoteOdor description: green, potato note
Claims (6)
- Use of monocyclic aldehydes which can be obtained by partial or complete hydroformylation of (di)methyl-substituted cyclooct(adi)enes as odorous substances.
- Use of monocyclic aldehydes which can be obtained by partial or complete hydroformylation of (di)methyl-substituted cyclooct(adi)enes as fragrance boosters.
- Use of monocyclic aldehydes which can be obtained by partial or complete hydroformylation of(di)methyl-substituted cyclooet(adi)enes in cosmetic preparations, industrial products or alcoholic perfumery.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
DE19817043 | 1998-04-17 | ||
PCT/EP1999/003207 WO1999054430A1 (en) | 1998-04-17 | 1999-04-08 | Utilization of monocyclic aldehydes as odoriferous agents |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1078028A1 EP1078028A1 (en) | 2001-02-28 |
EP1078028B1 true EP1078028B1 (en) | 2005-08-03 |
Family
ID=7864830
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99920865A Expired - Lifetime EP1078028B1 (en) | 1998-04-17 | 1999-04-08 | Utilization of monocyclic aldehydes as odoriferous agents |
Country Status (7)
Country | Link |
---|---|
US (1) | US6541446B1 (en) |
EP (1) | EP1078028B1 (en) |
JP (1) | JP2002512301A (en) |
DE (2) | DE19817043A1 (en) |
ES (1) | ES2246569T3 (en) |
IL (1) | IL139026A0 (en) |
WO (1) | WO1999054430A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Family Cites Families (5)
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 |
-
1998
- 1998-04-17 DE DE19817043A patent/DE19817043A1/en not_active Withdrawn
-
1999
- 1999-04-08 WO PCT/EP1999/003207 patent/WO1999054430A1/en active IP Right Grant
- 1999-04-08 DE DE59912360T patent/DE59912360D1/en not_active Expired - Fee Related
- 1999-04-08 EP EP99920865A patent/EP1078028B1/en not_active Expired - Lifetime
- 1999-04-08 US US09/673,391 patent/US6541446B1/en not_active Expired - Fee Related
- 1999-04-08 ES ES99920865T patent/ES2246569T3/en not_active Expired - Lifetime
- 1999-04-08 JP JP2000544763A patent/JP2002512301A/en active Pending
- 1999-04-08 IL IL13902699A patent/IL139026A0/en unknown
Also Published As
Publication number | Publication date |
---|---|
IL139026A0 (en) | 2001-11-25 |
DE19817043A1 (en) | 1999-10-21 |
US6541446B1 (en) | 2003-04-01 |
JP2002512301A (en) | 2002-04-23 |
DE59912360D1 (en) | 2005-09-08 |
EP1078028A1 (en) | 2001-02-28 |
ES2246569T3 (en) | 2006-02-16 |
WO1999054430A1 (en) | 1999-10-28 |
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