EP1078027B1 - Utilization of bicyclic aldehydes as odoriferous agents - Google Patents
Utilization of bicyclic aldehydes as odoriferous agents Download PDFInfo
- Publication number
- EP1078027B1 EP1078027B1 EP99920864A EP99920864A EP1078027B1 EP 1078027 B1 EP1078027 B1 EP 1078027B1 EP 99920864 A EP99920864 A EP 99920864A EP 99920864 A EP99920864 A EP 99920864A EP 1078027 B1 EP1078027 B1 EP 1078027B1
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- EP
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- Prior art keywords
- bicyclo
- hydroformylation
- oct
- fragrance
- aldehydes
- Prior art date
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- Expired - Lifetime
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- -1 bicyclic aldehydes Chemical class 0.000 title claims description 10
- 238000007037 hydroformylation reaction Methods 0.000 claims description 21
- 239000003205 fragrance Substances 0.000 claims description 20
- 239000002537 cosmetic Substances 0.000 claims description 5
- 239000002304 perfume Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims 2
- 239000000203 mixture Substances 0.000 description 12
- LHOQCEAXPLQECM-UHFFFAOYSA-N 1,2,3,3a,4,5,6,6a-octahydropentalene-1-carbaldehyde Chemical compound C1CCC2C(C=O)CCC21 LHOQCEAXPLQECM-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- IGGUWVNICWZJQU-UHFFFAOYSA-N cyclooctanecarbaldehyde Chemical compound O=CC1CCCCCCC1 IGGUWVNICWZJQU-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- KEHFJHPSOFFXBO-SFYZADRCSA-N (3ar,6ar)-1,2,3,3a,4,6a-hexahydropentalene Chemical compound C1C=C[C@@H]2CCC[C@@H]21 KEHFJHPSOFFXBO-SFYZADRCSA-N 0.000 description 1
- WGGHTQJCLFQFTA-UHFFFAOYSA-N 1,2,3,3a,4,5-hexahydropentalene Chemical compound C1CC=C2CCCC21 WGGHTQJCLFQFTA-UHFFFAOYSA-N 0.000 description 1
- ABIPLJQFLRXYES-UHFFFAOYSA-N 1,2,3,3a-tetrahydropentalene Chemical compound C1=CC=C2CCCC21 ABIPLJQFLRXYES-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- ZAOKSGRIAGOZJA-UHFFFAOYSA-N O=CC1CC(CCC2)C2C1 Chemical compound O=CC1CC(CCC2)C2C1 ZAOKSGRIAGOZJA-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002324 mouth wash Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
- C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
- C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms
-
- 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
Definitions
- the invention relates to the use of special bicyclic aldehydes which are obtainable by partial or complete hydroformylation of - optionally (di) methyl-substituted - bicyclo [3.3.0] oct (adi) enes as Fragrances. Under "Bicyclo [3.3.0] oct (adi) enen” there are both Bicyclo [3.3.0] octadiene as well as Bicyclo [3.3.0] octene. Under "(Di) methyl-substituted” is understood to mean that the bicyclic system is either a or can carry two methyl groups as substituents.
- the invention relates to the use of bicyclic aldehydes which are obtainable by partial or complete hydroformylation of - optionally (di) methyl-substituted - bicyclo [3.3.0] oct (adi) enen, as Fragrances.
- Another object of the invention is the use of bicyclic Aldehydes which are obtainable by partial or complete hydroformylation of - optionally (di) methyl-substituted - bicyclo [3.3.0] oct (adi) enes, as Fragrance boosters.
- 3-formyl-bicyclo [3.3.0] is octane particularly preferred.
- aldehydes to be used according to the invention are advantageously prepared by hydroformylation of - optionally (di) methyl-substituted - bicyclo [3.3.0] oct (adi) enes.
- the latter compounds have a bicyclic system as a common framework.
- hydroformylation is known to the person skilled in the art Reaction discovered by von Roelen in 1938. This alkenes converted to aldehydes with carbon monoxide and hydrogen. The reaction is too known as oxo synthesis.
- the odor profile of the hydroformylation products according to the invention is original and new.
- perfume compositions they reinforce the harmony and Radiance as well as liability, taking the dosage below Consideration of the other components of the composition on each desired fragrance is coordinated.
- hydroformylation products according to the invention are suitable on the basis of their Odor profiles in particular for the modification and reinforcement of known ones Compositions.
- their extraordinary should be emphasized Strength of smell, which generally contributes to the refinement of compositions.
- (3) 2-Formyl-bicyclo [3.3.0] octane ( 3 ) is particularly suitable for use according to the invention as a fragrance and / or fragrance booster. Accordingly, the use of (3) 2-formyl-bicyclo [3.3.0] octane, for example in room fragrances, is particularly advantageous. In addition, it has been shown that ( 3 ) can be used with particular advantages in cleaning agents for strengthening citrus scents.
- 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 entire mix.
- the hydroformylation products according to the invention as well Compositions of this type can be used for both perfuming cosmetic Preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, Toothpastes, mouthwashes, deodorants as well as in exquisite perfumery be used.
- perfuming cosmetic Preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, Toothpastes, mouthwashes, deodorants as well as in vibrant perfumery be used.
- perfuming technical products as well as washing and cleaning agents, fabric softener, Textile treatment agents or tobacco.
Description
Die Erfindung betrifft die Verwendung spezieller bicyclischer Aldehyde, die erhältlich sind durch partielle oder vollständige Hydroformylierung von - gegebenenfalls (Di)methyl-substituierten - Bicyclo[3.3.0]oct(adi)enen als Riechstoffe. Unter "Bicyclo[3.3.0]oct(adi)enen" sind dabei sowohl Bicyclo[3.3.0]octadiene als auch Bicyclo[3.3.0]octene zu verstehen. Unter "(Di)methyl-substituiert" ist zu verstehen, daß das bicyclische System entweder ein oder zwei Methylgruppen als Substituenten tragen kann.The invention relates to the use of special bicyclic aldehydes which are obtainable by partial or complete hydroformylation of - optionally (di) methyl-substituted - bicyclo [3.3.0] oct (adi) enes as Fragrances. Under "Bicyclo [3.3.0] oct (adi) enen" there are both Bicyclo [3.3.0] octadiene as well as Bicyclo [3.3.0] octene. Under "(Di) methyl-substituted" is understood to mean that the bicyclic system is either a or can carry 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
Herstellung davon abgeleiteter Acetale mit Dufteigenschaften beschrieben wird,
hinsichtlich seiner geruchlichen Eigenschaften, die als "intensiv grün" beschrieben
werden. bekannt.
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 geruchsverbessemden für Produkte des täglichen Bedarfs wie Kosmetika und Reinigungsmittel decken zu können.Many natural odoriferous substances are completely inadequate when measured against the demand Amount available. It is therefore clear that the fragrance industry is one has a constant need for new fragrances with interesting fragrance notes in order to To complement the range of naturally available fragrances and the necessary ones Make adjustments to changing fashionable flavors as well the constantly increasing need for odor-improving products of the daily needs such as 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 Verbrauchsgütern 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, which can be produced cheaply and with consistent quality and desired have olfactory properties, that is to say pleasant and as natural as possible possess qualitatively new odor profiles of sufficient intensity and in which Are able to take advantage of the scent of cosmetic and consumer goods influence. There is therefore a need for connections that are characteristic new Odor profiles with high adhesive strength, odor intensity and Have radiance.
Überraschenderweise wurde gefunden, daß spezielle bicyclische Aldehyde, die erhältlich sind durch partielle oder vollständige Hydroformylierung von - gegebenenfalls (Di)methyl-substituierten - Bicyclo[3.3.0]oct(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 was found that special bicyclic aldehydes, the are obtainable by partial or complete hydroformylation of - optionally (di) methyl-substituted - bicyclo [3.3.0] oct (adi) enes via have remarkable odor properties. About your special Odor characteristics beyond that by a wide range with complex Shades is marked. the connections are characterized by good ones Adhesion and radiance. They are also suitable in excellent as a fragrance booster. There is one under a fragrance booster To understand substance that is able to understand the olfactory impressions of the Components of a multi-component system, i.e. a mixture of two or more Fragrances to intensify sustainably.
Gegenstand der Erfindung ist die Verwendung von bicyclischen Aldehyden, die erhältlich sind durch partielle oder vollständige Hydroformylierung von - gegebenenfalls (Di)methyl-substituierten - Bicyclo[3.3.0]oct(adi)enen, als Riechstoffe.The invention relates to the use of bicyclic aldehydes which are obtainable by partial or complete hydroformylation of - optionally (di) methyl-substituted - bicyclo [3.3.0] oct (adi) enen, as Fragrances.
Ein weiterer Gegenstand der Erfindung ist die Verwendung von bicyclischen Aldehyden, die erhältlich sind durch partielle oder vollständige Hydroformylierung von - gegebenenfalls (Di)methyl-substituierten - Bicyclo[3.3.0]oct(adi)enen, als Duft-Booster. Hinsichtlich dieser Verwendung ist 3-Formyl-Bicyclo[3.3.0]octan besonders bevorzugt.Another object of the invention is the use of bicyclic Aldehydes which are obtainable by partial or complete hydroformylation of - optionally (di) methyl-substituted - bicyclo [3.3.0] oct (adi) enes, as Fragrance boosters. With regard to this use, 3-formyl-bicyclo [3.3.0] is octane particularly preferred.
Die Herstellung der erfindungsgemäß einzusetzenden Aldehyde geschieht
vorteilhaft durch Hydroformylierung von - gegebenenfalls (Di)methylsubstituierten
- Bicyclo[3.3.0]oct(adi)enen. Die letztgenannten Verbindungen
weisen als gemeinsames Grundgerüst ein bicyclisches System auf. Das
Grundgerüst - jedoch ohne die Angabe der (optionalen) Methylgruppen und der
C=C-Doppelbindungen wird durch die folgende Formel (2) veranschaulicht:
Dieses System (2) enthält ein oder zwei C=C-Doppelbindungen. Sofern zwei C=C-Doppelbindungen vorliegen gilt, daß diese nicht unmittelbar benachbart sind. Optional können ein oder zwei Methylgruppen vorhanden sein.This system (2) contains one or two C = C double bonds. If two C = C double bonds it applies that these are not immediately adjacent. One or two methyl groups can optionally be present.
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 the person skilled in the art Reaction discovered by von Roelen in 1938. This alkenes converted to aldehydes with carbon monoxide and hydrogen. The reaction is too known as oxo synthesis.
Sofern im Rahmen der vorliegenden Erfindung als Ausgangsstoffe - gegebenenfalls (Di)methyl-substituierten - Bicyclo[3.3.0]oct(adi)enen 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 Verbindungen Verbindungen mit nur einer C=C-Doppelbindung pro Molekül eingesetzt werden, ist selbstverständlich lediglich die vollständige Hydroformylierung möglich.If in the context of the present invention as starting materials - optionally used (di) methyl-substituted - bicyclo [3.3.0] oct (adi) enes the hydroformylation can be carried out partially or completely become. Partial hydroformylation leaves an olefinic one Obtained double bond per molecule of the starting compound, while only that others will be hydroformylated during the complete hydroformylation two CHO groups introduced into the molecule. Unless, however, as starting materials Compounds Compounds with only one C = C double bond per molecule used, of course, is only the complete one Hydroformylation possible.
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 reinforce the harmony and Radiance as well as liability, taking the dosage below Consideration of the other components of the composition on each desired fragrance is coordinated.
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 according to the invention are interesting show perfume notes was unpredictable and is a confirmation for general experience that the olfactory properties are better known Odoriferous substances do not make a compelling conclusion about the properties in the broadest The meaning of "structurally analogous" connections - in the present case, for example Allow cyclooctanaldehyde (1) - or their mixtures with one another, because neither the mechanism of fragrance perception nor the influence of chemical ones Structure on the scent perception are sufficiently researched, therefore can usually not be predicted whether a modified structure or special mixing ratios of known odoriferous substances to change at all of the olfactory properties and whether this change is positive or negative is to be assessed.
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 on the basis of their Odor profiles in particular for the modification and reinforcement of known ones Compositions. In particular, their extraordinary should be emphasized Strength of smell, 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 inventive Hydroformylation products the olfactory notes of a wide range of well-known Round off and harmonize compositions without, however, in an unpleasant way to dominate.
In ganz besonderer Weise eignet sich (3)2-Formyl-Bicyclo[3.3.0]octan (3) für die
erfindungsgemäße Verwendung als Riechstoff und/oder Duft-Booster.
Dementsprechend ist der Einsatz von (3)2-Formyl-Bicyclo[3.3.0]octan
beispielsweise in Raumbeduftem besonders vorteilhaft. Darüber hinaus hat sich
gezeigt, daß (3) mit besonderen Vorteilen in Reinigungsmitteln zur Verstärkung
von Zitrusdüften eingesetzt werden kann.
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% by weight, based on the entire mix. The hydroformylation products according to the invention as well Compositions of this type can be used for both perfuming cosmetic Preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, Toothpastes, mouthwashes, deodorants as well as in exquisite perfumery be used. There is also an application for perfuming technical products as well as washing and cleaning agents, fabric softener, Textile treatment agents or tobacco. To perfume these different Products will give these compositions an olfactory effect Amount, in particular in a concentration in the range from 0.05 to 2% by weight, based on the entire product, metered. However, these values should not Limit values represent, since the experienced perfumer also with lower Concentrations achieve effects or with even higher doses can build new complexes.
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.
2 mol (216 g) cis-Bicyclo[3.3.0]oct-2-en (Hersteller: Fa. Wiley; gaschromatographisch bestimmte Reinheit: 99%) 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 (216 g) of cis-bicyclo [3.3.0] oct-2-ene (manufacturer: Wiley; purity determined by gas chromatography: 99%) 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) 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 2 at 100 ° C 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 (3)2-Formyl-Bicyclo[3.3.0]octan (3)erfolgte an einer Drehbandkolonne. Es wurden 132 g (3)2-Formyl-Bicyclo[3.3.0]octan erhalten (Siedepunkt: 97 °C/ 20 mbar).The fractionation into starting material and (3) 2-formyl-bicyclo [3.3.0] octane ( 3 ) was carried out on a rotating band column. 132 g (3) 2-formyl-bicyclo [3.3.0] octane were obtained (boiling point: 97 ° C./20 mbar).
Geruchsbeschreibung: grün, krautigDescription of smell: green, herbaceous
Claims (6)
- Use of bicyclic aldehydes which can be obtained by partial or complete hydroformylation of - optionally (dimethyl-substituted-bicyclo[3.3.0]oct(adi)enes as perfumes.
- Use of (3)2-formyl-bicyclo[3.3.0]octane as perfume.
- Use of bicyclic aldehydes which can be obtained by partial or complete hydroformylation of - optionally (di)methyl-substituted- bicyclo[3.3.0]oct(adi)enes as fragrance boosters.
- Use of (3)2-formyl-bicyclo[3.3.0]octane as fragrance booster.
- Use of bicyclic aldehydes which can be obtained by partial or complete hydroformylation of - optionally (di)methyl-substituted-bicyclo[3.3.0]oct(adi)enes in cosmetic preparations, industrial products or alcoholic perfumery.
- Use of (3)2-formyl-bicyclo[3.3.0]octane in cosmetic preparations, industrial products or alcoholic perfumery.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19817042A DE19817042A1 (en) | 1998-04-17 | 1998-04-17 | Bicyclic aldehydes obtained by hydroformylation of bicyclo(3.3.0)oct(adi)enes used as perfumes or perfume boosters |
| DE19817042 | 1998-04-17 | ||
| PCT/EP1999/003206 WO1999054429A1 (en) | 1998-04-17 | 1999-04-08 | Utilization of bicyclic aldehydes as odoriferous agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1078027A1 EP1078027A1 (en) | 2001-02-28 |
| EP1078027B1 true EP1078027B1 (en) | 2004-12-22 |
Family
ID=7864829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99920864A Expired - Lifetime EP1078027B1 (en) | 1998-04-17 | 1999-04-08 | Utilization of bicyclic aldehydes as odoriferous agents |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6537963B1 (en) |
| EP (1) | EP1078027B1 (en) |
| JP (1) | JP2002512300A (en) |
| DE (2) | DE19817042A1 (en) |
| ES (1) | ES2233044T3 (en) |
| IL (1) | IL139025A (en) |
| WO (1) | WO1999054429A1 (en) |
Families Citing this family (3)
| 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 |
| FR2981070B1 (en) | 2011-10-11 | 2014-01-10 | V Mane Fils | NOVEL CYCLOALCANIC ALDEHYDES, PROCESS FOR THEIR PREPARATION AND USE IN PERFUMERY |
| KR20210077676A (en) | 2018-09-11 | 2021-06-25 | 에너자이저 브랜즈, 엘엘씨 | Hearing aid battery with slotted grommets |
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 |
| 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 |
| DE2849720A1 (en) | 1978-11-16 | 1980-05-29 | Henkel Kgaa | NEW ALDEHYDE, THEIR PRODUCTION AND THEIR USE AS A FRAGRANCE |
| US4524017A (en) | 1981-02-28 | 1985-06-18 | Nippon Petrochemicals Co., Ltd. | Derivatives of norbornanes having hydrocarbon side chains and perfume compositions containing the same |
| JPS5821638A (en) | 1981-07-31 | 1983-02-08 | Mitsubishi Petrochem Co Ltd | Preparation of dialdehydes |
-
1998
- 1998-04-17 DE DE19817042A patent/DE19817042A1/en not_active Withdrawn
-
1999
- 1999-04-08 WO PCT/EP1999/003206 patent/WO1999054429A1/en active IP Right Grant
- 1999-04-08 IL IL13902599A patent/IL139025A/en not_active IP Right Cessation
- 1999-04-08 JP JP2000544762A patent/JP2002512300A/en active Pending
- 1999-04-08 US US09/673,376 patent/US6537963B1/en not_active Expired - Fee Related
- 1999-04-08 ES ES99920864T patent/ES2233044T3/en not_active Expired - Lifetime
- 1999-04-08 DE DE59911332T patent/DE59911332D1/en not_active Expired - Fee Related
- 1999-04-08 EP EP99920864A patent/EP1078027B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ES2233044T3 (en) | 2005-06-01 |
| WO1999054429A1 (en) | 1999-10-28 |
| JP2002512300A (en) | 2002-04-23 |
| DE59911332D1 (en) | 2005-01-27 |
| US6537963B1 (en) | 2003-03-25 |
| IL139025A (en) | 2004-02-08 |
| IL139025A0 (en) | 2001-11-25 |
| EP1078027A1 (en) | 2001-02-28 |
| DE19817042A1 (en) | 1999-10-21 |
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