WO1996025382A1 - Condensation products - Google Patents

Condensation products Download PDF

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Publication number
WO1996025382A1
WO1996025382A1 PCT/EP1996/000475 EP9600475W WO9625382A1 WO 1996025382 A1 WO1996025382 A1 WO 1996025382A1 EP 9600475 W EP9600475 W EP 9600475W WO 9625382 A1 WO9625382 A1 WO 9625382A1
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WIPO (PCT)
Prior art keywords
condensation product
isomers
fragrance
weight
product according
Prior art date
Application number
PCT/EP1996/000475
Other languages
German (de)
French (fr)
Inventor
Thomas Markert
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication date
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Publication of WO1996025382A1 publication Critical patent/WO1996025382A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration

Definitions

  • the invention relates to a condensation product of isononyl aldehyde and methyl ethyl ketone. It is characterized in that it contains at least 85% by weight of the isomers 3,6,8,8-tetramethylnon-3-en-2-one and 7,9,9-trimethy1-4-decen-3- one contains, these isomers being present in a weight ratio of 1:10 to 10: 1.
  • the condensation product has a characteristic odor profile (citrus / bergamot) and a high radiance.
  • the subject of the invention is therefore a condensation product of isononyl aldehyde and methyl ethyl ketone, which contains at least 85% by weight of the isomeric compounds 3,6,8,8-tetramethylnon-3-en-2-one and 7,9,9-trimethyl-4-decen- Contains 3-one, these isomers being present in a weight ratio of 1:10 to 10: 1.
  • the two isomers mentioned are present in a weight ratio of 1: 4 to 4: 1. In a further preferred embodiment, the proportion of the condensation product in the two isomers mentioned is at least 95% by weight.
  • the condensation product is prepared according to known synthetic methods of organic chemistry.
  • Commercially available 3,5,5-trimethylhexanal is used as the starting material, which is reacted with 2-butanone (methyl ethyl ketone) in a mixed aldol condensation in the presence of customary catalysts, the corresponding .alpha. ⁇ -unsaturated isomeric condensation products according to the invention are obtained.
  • the reaction is expediently carried out with an excess of 2-butanone.
  • catalysts are Sodium hydroxide, sodium methanolate, sodium amide, potassium tert-butoxide or heterogeneous catalysts such as potassium fluoride on aluminum oxide are possible.
  • the crude condensation product can then be processed by conventional methods, e.g. be purified by distillation.
  • the condensation product according to the invention has remarkable odor properties, such as are very sought after in the fragrance industry, namely citrus / bergamot-like with very complex shades and great charisma.
  • Another object of the invention is therefore the use of the condensation product as a fragrance.
  • German patent application DE 3245047 describes aliphatic alcohols and esters which have fruity and in particular pear-like fragrance notes or ambrette-woody, flowery and balm-like fragrance notes. Particular emphasis is placed on 5,7,7-trimethyloctyl propionate, whose fruity, pear-like note is particularly emphasized.
  • JP 90/282 339 A2 discloses ketones with an ionic odor profile. A large number of compounds are specifically disclosed, including the individual compounds 3,6,8,8-tetramethylnon-3-en-2-one and 7,9,9-trimethyl-4-decen-3-one. However, nothing is disclosed about the perfume properties of mixtures of these (individually isolated) compounds. In particular, JP 90/282 339 A2 does not give any indication that completely different odor profiles which differ from the ionone characteristics are accessible through targeted mixing of the individual substances disclosed.
  • the odor profile of the condensation product according to the invention is original and novel.
  • the condensation product enhances harmony and charisma as well as adhesion, the dosage being matched to the desired fragrance note, taking into account the other components of the composition.
  • condensation product according to the invention has fresh citrus / bergamot notes was not predictable and is therefore a further confirmation of the general experience that the olfactory properties of known fragrances do not allow any conclusions to be drawn about the properties of structurally related compounds or their mixtures with one another , because neither the mechanism of the fragrance perception nor the influence of the chemical structure on the fragrance perception have been sufficiently researched, so it cannot normally be predicted whether a changed The structure or special mixing ratios of known odoriferous substances leads to a change in the olfactory properties and whether these changes are assessed positively or negatively.
  • the condensation product according to the invention is also particularly suitable for modifying and reinforcing known compositions. It should be emphasized in particular its extraordinary olfactory strength, which generally contributes to the refinement of compositions.
  • the condensation product according to the invention can be used with numerous known fragrance ingredients, e.g. combine other fragrances of natural, synthetic or partially synthetic origin, essential oils and plant extracts.
  • the range of natural fragrances can include both volatile, medium and low volatile components and that of synthetic fragrances includes representatives from practically all classes of substances. Examples are:
  • Natural products such as tree moss absolute, basil oil, agricultural oils such as bergamot oil, mandarin oil, etc., mastic absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, wormwood oil, myrrh oil, olibanum oil
  • aldehydes such as citral, Helional R , ⁇ -hexylcinnamaldehyde, hydroxycitronellal, Lilial R [p-tert-butyl-methyldihydrocinnamaldehyde], methylnonyl acetaldehyde,
  • ketones such as allyl ionone, ⁇ -ionone, ⁇ -ionone, isoraldein, methyl ionone,
  • esters such as allylphenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethylbenzylcarbyl acetate, ethyl acetoacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasyl acetate, cyclohexyl acetate, vetyl hexyl acetate
  • Lactones such as T-undecalactone, l-0xaspiro [4.4] nonan-2-one, as well as various other components often used in perfumery such as ketone musk, indole, p-menthan-8-thiol-3-one, methyleugenol, ambroxan . Also noteworthy is the way in which the condensation product according to the invention rounds off and harmonizes the olfactory notes of a wide range of known compositions, but without dominating in an unpleasant manner.
  • the usable proportions of the condensation product according to the invention in fragrance compositions range from 1 to 70 percent by weight, based on the mixture as a whole.
  • the condensation product according to the invention and compositions of this type can be used both for perfuming cosmetic preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants and in alcoholic perfumery (eg Eaux de Cologne, Eaux de toilet, tincts) are used.
  • perfuming technical products such as detergents and cleaning agents, fabric softeners and textile treatment agents or tobacco.
  • compositions are added to them in an olfactory effective amount, in particular in a concentration of 0.05 to 2 percent by weight, based on the entire product.
  • these values are not intended to represent any limit values, since the experienced perfumer can achieve effects with even lower concentrations or build new types of complexes with even higher doses.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a condensation product of isononyl aldehyde and methylethyl ketone. It contains the isomers 3,6,8,8-tetramethylnon-3-en-2-one and 7,9,9-trimethyl-4-decen-3-one in a proportion of at least 85 wt.%, in which said isomers are in the ratio by weight of 1:10 to 10:1. This product is characterized by a citrus-bergamot aroma.

Description

Kondensationsprodukt Condensation product
Die Erfindung betrifft ein Kondensationsprodukt aus Isononylaldehyd und Methylethylketon. Es ist dadurch charakterisiert, daß es mindestens 85 Gew.-% an den isomeren 3,6,8,8-Tetramethylnon-3-en-2-on und 7,9,9-Trime- thy1-4-decen-3-on enthält, wobei diese Isomeren im GewichtsVerhältnis von 1:10 bis 10:1 vorliegen. Das Kondensationsprodukt weist ein charakteristi¬ sches Geruchsprofil (Citrus/Bergamotte) sowie eine hohe Strahlkraft auf.The invention relates to a condensation product of isononyl aldehyde and methyl ethyl ketone. It is characterized in that it contains at least 85% by weight of the isomers 3,6,8,8-tetramethylnon-3-en-2-one and 7,9,9-trimethy1-4-decen-3- one contains, these isomers being present in a weight ratio of 1:10 to 10: 1. The condensation product has a characteristic odor profile (citrus / bergamot) and a high radiance.
Viele natürliche Riechstoffe stehen gemessen am Bedarf in völlig unzurei¬ chender Menge zur Verfügung. Beispielsweise sind zur Gewinnung von 1 kg Rosenöl 5.000 kg Rosenblüten notwendig; die Folgen sind eine sehr stark limitierte WeltJahresproduktion sowie ein hoher Preis. 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 mo¬ dische Geschmacksrichtungen vornehmen sowie den ständig steigenden Bedarf an Geruchsverbesserern für Produkte des täglichen Bedarfs wie Kosmetika und Reinigungsmittel decken zu können.Many natural odoriferous substances are available in a completely inadequate amount, measured according to need. For example, 5,000 kg of rose petals are required to obtain 1 kg of rose oil; the consequences are a very limited world annual production and a high price. It is therefore clear that the fragrance industry has a constant need for new fragrances with interesting fragrance notes in order to supplement the range of naturally available fragrances and to make the necessary adaptations to changing fashionable tastes, as well as the constantly increasing need for odor improvers for everyday products To cover needs such as cosmetics and cleaning agents.
Darüber hinaus besteht generell ein ständiger Bedarf an synthetischen Riech¬ stoffen, die sich günstig und mit gleichbleibender Qualität herstellen lassen und erwünschte olfaktorische Eigenschaften haben, d.h. angenehme, möglichst naturnahe und qualitativ neuartige Geruchsprofile von ausrei¬ chender Intensität besitzen und in der Lage sind, den Duft von kosmeti¬ schen und Verbrauchsgütern vorteilhaft zu beeinflussen. Es wurde daher nach Verbindungen gesucht, die charakteristische neue Geruchsprofile bei gleichzeitig hoher Haftfestigkeit, Geruchsintensitat und Strahlkraft auf¬ weisen sollten. Es wurde nun gefunden, daß ein Kondensationsprodukt aus Isononylaldehyd (3,5,5-Trimethylhexanal) und Methylethylketon (2-Butanon), das die Iso¬ meren 3,6,8,8-Tetramethylnon-3-en-2-on und 7,9,9-Trimethyl-4-decen-3-on zu mindestens 85 Gew.-% enthält, und worin diese Isomeren im Gewichtsverhält¬ nis von 1:10 bis 10:1 vorliegen, diese Forderung in jeder Hinsicht ausge¬ zeichnet erfüllen und in vorteilhafter Weise als Riechstoffe mit ausgepräg¬ tem Citrus/Bergamotte-Geruchsprofil sowie guter Haftfestigkeit eingesetzt werden können.In addition, there is generally a constant need for synthetic fragrances which can be produced cheaply and with a constant quality and which have desired olfactory properties, ie which have pleasant, near-natural and qualitatively novel odor profiles of sufficient intensity and are able to do so To influence the fragrance of cosmetic and consumer goods advantageously. It was therefore sought for compounds which should have characteristic new odor profiles with high adhesive strength, odor intensity and radiance. It has now been found that a condensation product of isononyl aldehyde (3,5,5-trimethylhexanal) and methyl ethyl ketone (2-butanone), which isomers 3,6,8,8-tetramethylnon-3-en-2-one and Contains 7,9,9-trimethyl-4-decen-3-one to at least 85% by weight, and in which these isomers are present in a weight ratio of 1:10 to 10: 1, this requirement is excellent in every respect meet and can be used advantageously as fragrances with a pronounced citrus / bergamot odor profile and good adhesive strength.
Erfindungsgegenstand ist daher ein Kondensationsprodukt aus Isononylaldehyd und Methylethylketon, das mindestens 85 Gew.-% der isomeren Verbindungen 3,6,8,8-Tetramethylnon-3-en-2-on und 7,9,9-Trimethyl-4-decen-3-on enthält, wobei diese Isomeren im Gewichtsverhältnis von 1:10 bis 10:1 vorliegen.The subject of the invention is therefore a condensation product of isononyl aldehyde and methyl ethyl ketone, which contains at least 85% by weight of the isomeric compounds 3,6,8,8-tetramethylnon-3-en-2-one and 7,9,9-trimethyl-4-decen- Contains 3-one, these isomers being present in a weight ratio of 1:10 to 10: 1.
In einer bevorzugten Ausführungsform liegen die beiden genannten Isomeren im Gewichtsverhältnis von 1:4 bis 4:1 vor. In einer weiteren bevorzugten Ausführungsform beträgt der Anteil des Kondensationsproduktes an den bei¬ den genannten Isomeren mindestens 95 Gew.-%.In a preferred embodiment, the two isomers mentioned are present in a weight ratio of 1: 4 to 4: 1. In a further preferred embodiment, the proportion of the condensation product in the two isomers mentioned is at least 95% by weight.
Die Herstellung des Kondensationsproduktes erfolgt nach an sich bekannten Syntheseverfahren der organischen Chemie. Als Ausgangsmaterial dient kom¬ merziell erhältliches 3,5,5-Trimethylhexanal (Isononylaldehyd), das in Gegenwart üblicher Katalysatoren mit 2-Butanon (Methylethylketon) in einer gemischten Aldolkondensation umgesetzt wird, wobei über intermediäre Aldol- kondensationsprodukte unter Wasserabspaltung direkt die entsprechenden α,ß-ungesättigten erfindungsgemäßen isomeren Kondensationsprodukte erhal¬ ten werden. Zweckmäßigerweise führt man die Reaktion mit einem Überschuß an 2-Butanon durch. Als Katalysatoren kommen z.B. Natriumhydroxid, Natriu - methanolat, Natriumamid, Kaliu -tert.-butanolat oder heterogene Katalysa¬ toren wie Kaliumfluorid auf Aluminiumoxid in Frage.The condensation product is prepared according to known synthetic methods of organic chemistry. Commercially available 3,5,5-trimethylhexanal (isononyl aldehyde) is used as the starting material, which is reacted with 2-butanone (methyl ethyl ketone) in a mixed aldol condensation in the presence of customary catalysts, the corresponding .alpha. β-unsaturated isomeric condensation products according to the invention are obtained. The reaction is expediently carried out with an excess of 2-butanone. Examples of catalysts are Sodium hydroxide, sodium methanolate, sodium amide, potassium tert-butoxide or heterogeneous catalysts such as potassium fluoride on aluminum oxide are possible.
Das rohe Kondensationsprodukt kann anschließend nach üblichen Methoden, z.B. durch Dest llation gereinigt werden.The crude condensation product can then be processed by conventional methods, e.g. be purified by distillation.
Das erfindungsgemäße Kondensationsprodukt verfügt über bemerkenswerte Ge¬ ruchseigenschaften, wie sie in der Riechstoffindustrie sehr gesucht sind, nämlich Citrus-/Bergamotte-artig mit sehr komplexen Schattierungen und großer Ausstrahlung.The condensation product according to the invention has remarkable odor properties, such as are very sought after in the fragrance industry, namely citrus / bergamot-like with very complex shades and great charisma.
Ein weiterer Gegenstand der Erfindung ist daher die Verwendung des Konden¬ sationsproduktes als Riechstoff.Another object of the invention is therefore the use of the condensation product as a fragrance.
Die deutsche Patentanmeldung DE 3245047 beschreibt aliphatische Alkohole und Ester, die fruchtige und insbesondere birnenähnliche Duftnoten oder ambrette-holzige, blumige und balsamartige Duftnoten aufweisen. Besonders betont wird dabei 5,7,7-Trimethyloctylpropionat, dessen fruchtige, bir¬ nenähnliche Note besonders hervorgehoben wird.German patent application DE 3245047 describes aliphatic alcohols and esters which have fruity and in particular pear-like fragrance notes or ambrette-woody, flowery and balm-like fragrance notes. Particular emphasis is placed on 5,7,7-trimethyloctyl propionate, whose fruity, pear-like note is particularly emphasized.
Aus JP 90/282 339 A2 sind Ketone mit lonon-Geruchsprof l bekannt. Konkret offenbart sind dabei eine Vielzahl von Verbindungen, darunter unter an¬ derem die EinzelVerbindungen 3,6,8,8-Tetramethylnon-3-en-2-on und 7,9,9- Trimethyl-4-decen-3-on. Ober die parfümistisehen Eigenschaften von Mischun¬ gen dieser (einzeln isolierten) Verbindungen ist jedoch nichts offenbart. Insbesondere kann JP 90/282 339 A2 kein Hinweis darauf entnommen werden, daß durch gezielte Abmischung einzelner offenbarter Substanzen völlig an¬ dersartige und von der Iononcharakteristik abweichende Geruchsprofile zu¬ gänglich sind.JP 90/282 339 A2 discloses ketones with an ionic odor profile. A large number of compounds are specifically disclosed, including the individual compounds 3,6,8,8-tetramethylnon-3-en-2-one and 7,9,9-trimethyl-4-decen-3-one. However, nothing is disclosed about the perfume properties of mixtures of these (individually isolated) compounds. In particular, JP 90/282 339 A2 does not give any indication that completely different odor profiles which differ from the ionone characteristics are accessible through targeted mixing of the individual substances disclosed.
Das Geruchsprofil des erfindungsgemäßen Kondensationsproduktes ist ori¬ ginell und neuartig. In Parfüm-Kompositionen verstärkt das Kondensations¬ produkt 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 condensation product according to the invention is original and novel. In perfume compositions, the condensation product enhances harmony and charisma as well as adhesion, the dosage being matched to the desired fragrance note, taking into account the other components of the composition.
Daß das erfindungsgemäße Kondensationsprodukt frische Citrus-/Bergamotte- Noten aufweist, war nicht vorhersehbar und ist damit eine weitere Bestäti¬ gung für die allgemeine Erfahrung, daß die olfaktorischen Eigenschaften bekannter Riechstoffe keine zwingenden Rückschlüsse auf die Eigenschaften strukturverwandter Verbindungen oder deren Mischungen untereinander zulas¬ sen, 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 geänder- ter Aufbau oder spezielle Mischungsverhältnisse bekannter Riechstoffe über¬ haupt zur Änderung der olfaktorischen Eigenschaften führt und ob diese Änderungen positiv oder negativ beurteilt werden.The fact that the condensation product according to the invention has fresh citrus / bergamot notes was not predictable and is therefore a further confirmation of the general experience that the olfactory properties of known fragrances do not allow any conclusions to be drawn about the properties of structurally related compounds or their mixtures with one another , because neither the mechanism of the fragrance perception nor the influence of the chemical structure on the fragrance perception have been sufficiently researched, so it cannot normally be predicted whether a changed The structure or special mixing ratios of known odoriferous substances leads to a change in the olfactory properties and whether these changes are assessed positively or negatively.
Das erfindungsgemäße Kondensationsprodukt eignet sich aufgrund seines Ge¬ ruchsprofils insbesondere auch zur Modifizierung und Verstärkung bekannter Kompositionen. Hervorgehoben werden soll insbesondere seine außerordent¬ liche Geruchsstärke, die ganz allgemein zur Veredelung von Kompositionen beiträgt.Due to its olfactory profile, the condensation product according to the invention is also particularly suitable for modifying and reinforcing known compositions. It should be emphasized in particular its extraordinary olfactory strength, which generally contributes to the refinement of compositions.
Das erfindungsgemäße Kondensationsprodukt läßt sich mit zahlreichen be¬ kannten Riechstoffingredientien, z.B. anderen Riechstoffen natürlichen, synthetischen oder partial-synthetischen Ursprungs, etherischen Ölen und Pflanzenextrakten kombinieren. Die Palette der natürlichen Riechstoffe kann dabei sowohl leicht- als auch ittel- und schwerflüchtige Komponenten und diejenige der synthetischen Riechstoffe Vertreter aus praktisch allen Stoffklassen umfassen. Beispiele sind:The condensation product according to the invention can be used with numerous known fragrance ingredients, e.g. combine other fragrances of natural, synthetic or partially synthetic origin, essential oils and plant extracts. The range of natural fragrances can include both volatile, medium and low volatile components and that of synthetic fragrances includes representatives from practically all classes of substances. Examples are:
(a) Naturprodukte wie Baummoos-Absolue, Basilikumöl, Agrumenöle wie Berga- motteöl, Mandarinenöl, usw., Mastix-Absolue, Myrtenöl, Palmarosaöl, Patchouliöl, Petitgrainöl, Wermutöl.Myrrheöl, Olibanumöl(a) Natural products such as tree moss absolute, basil oil, agricultural oils such as bergamot oil, mandarin oil, etc., mastic absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, wormwood oil, myrrh oil, olibanum oil
(b) Alkohole wie Farnesol, Geraniol, Linalool, Nerol, Phenylethylalkohol, Rhodinol, Zimtalkohol, Sandalore [3-Methyl-5-(2.2.3-trimethylcyclo- pent-3-en-l-yl)pentan-2-ol], Sandela [3-Isocamphyl-(5)-cyclohexanol],(b) alcohols such as farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamon alcohol, Sandalore [3-methyl-5- (2.2.3-trimethylcyclopent-3-en-l-yl) pentan-2-ol] , Sandela [3-isocamphyl- (5) -cyclohexanol],
(c) Aldehyde wie Citral, HelionalR, α-Hexylzimtaldehyd, Hydroxycitronel- lal, LilialR [p-tert.-Butyl- -methyldihydrozimtaldehyd], Methylnonyl- acetaldehyd,(c) aldehydes such as citral, Helional R , α-hexylcinnamaldehyde, hydroxycitronellal, Lilial R [p-tert-butyl-methyldihydrocinnamaldehyde], methylnonyl acetaldehyde,
(d) Ketone wie Allylionon, α-Ionon, ß-Ionon, Isoraldein, Methylionon,(d) ketones such as allyl ionone, α-ionone, β-ionone, isoraldein, methyl ionone,
(e) Ester wie Allylphenoxyacetat, Benzylsalicylat, Cinnamylpropionat, Ci- tronellylacetat, Citronellylethoxylat, Decylacetat, Dimethylbenzyl- carbinylacetat, Ethylacetoacetat, Hexenylisobutyrat, Linalylacetat, Methyldihydrojasmonat, Vetiverylacetat, Cyclohexylsalicylat(e) esters such as allylphenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethylbenzylcarbyl acetate, ethyl acetoacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasyl acetate, cyclohexyl acetate, vetyl hexyl acetate
(f) Lactone wie T-Undecalacton, l-0xaspiro[4.4]nonan-2-on, sowie verschiedene weitere in der Parfümerie oft benutzte Komponenten wie Ketonmoschus, Indol, p-Menthan-8-thiol-3-on, Methyleugenol, Ambroxan. Bemerkenswert ist ferner die Art und Weise, wie das erfindungsgemäße Kon¬ densationsprodukt, die Geruchsnoten einer breiten Palette bekannter Kompo¬ sitionen abrundet und harmonisiert, ohne aber in unangenehmer Weise zu dominieren.(f) Lactones such as T-undecalactone, l-0xaspiro [4.4] nonan-2-one, as well as various other components often used in perfumery such as ketone musk, indole, p-menthan-8-thiol-3-one, methyleugenol, ambroxan . Also noteworthy is the way in which the condensation product according to the invention rounds off and harmonizes the olfactory notes of a wide range of known compositions, but without dominating in an unpleasant manner.
Die einsetzbaren Anteile des erfindungsgemäßen Kondensationsproduktes in Riechstoffkompositionen bewegen sich von 1 bis 70 Gewichtsprozent, bezogen auf die gesamte Mischung. Das erfindungsgemäße Kondensationsprodukt sowie Kompositionen dieser Art können sowohl zur Parfümierung kosmetischer Prä¬ parate wie Lotionen, Cremes, Shampoos, Seifen, Salben, Puder, Aerosole, Zahnpasten, Mundwässer, Desodorantien als auch in der alkoholischen Par¬ fümerie (z.B. Eaux de Cologne, Eaux de Toilette, Extraits) verwendet wer¬ den. Ebenso besteht eine Einsatzmöglichkeit zur Parfümierung technischer Produkte wie Wasch- und Reinigungsmittel, Weichspüler und Textilbehand- lungsmittel oder Tabak. Zur Parfümierung dieser verschiedenen Produkte werden diesen die Kompositionen in einer olfaktorisch wirksamen Menge, insbesondere in einer Konzentration von 0,05 bis 2 Gewichtsprozent, be¬ zogen auf das gesamte Produkt, zugesetzt. Diese Werte sollen jedoch keine Grenzwerte darstellen, da der erfahrene Parfümeur auch mit noch geringeren Konzentrationen Effekte erzielen oder aber mit noch höheren Dosierungen neuartige Komplexe aufbauen kann.The usable proportions of the condensation product according to the invention in fragrance compositions range from 1 to 70 percent by weight, based on the mixture as a whole. The condensation product according to the invention and compositions of this type can be used both for perfuming cosmetic preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants and in alcoholic perfumery (eg Eaux de Cologne, Eaux de toilet, extraits) are used. There is also an application for perfuming technical products such as detergents and cleaning agents, fabric softeners and textile treatment agents or tobacco. To perfume these various products, the compositions are added to them in an olfactory effective amount, in particular in a concentration of 0.05 to 2 percent by weight, based on the entire product. However, these values are not intended to represent any limit values, since the experienced perfumer can achieve effects with even lower concentrations or build new types of complexes with even higher doses.
Die folgenden Beispiele sollen den Gegenstand der Erfindung erläutern und sind nicht einschränkend aufzufassen. The following 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 eines Isoaerengeaisches enthaltend 3,6,8,8-Tetraβethyl- non-3-en-2-on (A) und 7,9,9-Trinιethyl-4-decen-3-on (B)1. Preparation of an isoerene mixture containing 3,6,8,8-tetraethyl-non-3-en-2-one (A) and 7,9,9-trin-ethyl-4-decen-3-one (B)
In einem 250-ml-Dreihalskolben wurden 42,6 g 3,5,5-Trimethylhexanal (Iso¬ nonylaldehyd) mit 108 g 2-Butanon (Methylethylketon) bei 20 °C unter Rühren und unter Stickstoffatmosphäre vermischt. Unter Rühren und Eiskühlung wur¬ den innerhalb von 30 Minuten über einen Tropftrichter 35 g einer Natrium- methanolatlösung (21 gew.-%ig in Methanol) kontinuierlich bei Innentempera¬ turen bis maximal 30 °C zudosiert. Anschließend wurde das Gemisch 7 Stun¬ den bei 90 °C unter Rückfluß gerührt bis aller Isononylaldehyd verbraucht war (Kontrolle durch Probenahme und gaschromatographische Analyse).In a 250 ml three-necked flask, 42.6 g of 3,5,5-trimethylhexanal (isononyl aldehyde) were mixed with 108 g of 2-butanone (methyl ethyl ketone) at 20 ° C. with stirring and under a nitrogen atmosphere. While stirring and cooling with ice, 35 g of a sodium methanolate solution (21% by weight in methanol) were metered in continuously at internal temperatures up to a maximum of 30 ° C. over a dropping funnel. The mixture was then stirred at 90 ° C. under reflux for 7 hours until all the isononylaldehyde had been consumed (control by sampling and gas chromatographic analysis).
Das Gemisch wurde anschließend mit 10 %iger Salzsäure neutralisiert, die organische Phase abgetrennt und mehrmals mit Wasser ausgewaschen, ge¬ trocknet, filtriert, eingeengt und an einer 20 cm Vigreux-Kolonne de¬ stilliert. Dabei wurden 59 g Rohprodukt isoliert, in denen Tetramethyl- nonenon (A) und Trimethyldecenon (B) im Verhältnis von 2:1 vorlagen (gaschromatographische Analyse). Nach Feindestillation wurden 32,5 g des Isomerengemisches erhalten (Siedepunkt: 45-47 °C / 0,01 mbar; gaschroma- tographisch bestimmte Reinheit: 98 %). Das IR-Spektru des gereinigten Isomerengemisches zeigte Absorptionsbanden bei 2952, 1700, 1674, 1630, 1364, 1200 und 981 cm"!. Geruchscharakteristik: grün, Myrcenylacetat, Ber- gamotte. The mixture was then neutralized with 10% hydrochloric acid, the organic phase separated and washed several times with water, dried, filtered, concentrated and distilled on a 20 cm Vigreux column. 59 g of crude product were isolated, in which tetramethyl-nonenone (A) and trimethyldecenone (B) were present in a ratio of 2: 1 (gas chromatographic analysis). After fine distillation, 32.5 g of the isomer mixture were obtained (boiling point: 45-47 ° C./0.01 mbar; purity determined by gas chromatography: 98%). The IR spectrum of the purified isomer mixture showed absorption bands at 2952, 1700, 1674, 1630, 1364, 1200 and 981 cm "!. Odor characteristics: green, myrcenyl acetate, bergoth.

Claims

P a t en t a n s p rü c h e P at en tansp rü che
1. Kondensationsprodukt aus Isononylaldehyd und Methylethylketon, dadurch gekennzeichnet, daß es mindestens 85 Gew.-% an den isomeren 3,6,8,8-Te- tramethylnon-3-en-2-on (A) und 7,9,9-Trimethyl-4-decen-3-on (B) ent¬ hält, wobei die Isomeren (A) und (B) im Gewichtsverhältnis von 1:10 bis 10:1 vorliegen.1. condensation product of isononyl aldehyde and methyl ethyl ketone, characterized in that it contains at least 85% by weight of the isomers 3,6,8,8-tetramethylnon-3-en-2-one (A) and 7.9.9 -Trimethyl-4-decen-3-one ent (B) ent, the isomers (A) and (B) being present in a weight ratio of 1:10 to 10: 1.
2. Verwendung des Kondensationsproduktes nach Anspruch 1 als Riechstoff mit Citrus-/Bergamotte-Geruchscharakteristik.2. Use of the condensation product according to claim 1 as a fragrance with citrus / bergamot odor characteristics.
3. Verwendung nach Anspruch 2 in kosmetischen Präparaten, technischen Produkten oder der alkoholischen Parfümerie.3. Use according to claim 2 in cosmetic preparations, technical products or alcoholic perfumery.
4. Riechstoffkompositionen mit einem Gehalt an dem Kondensationsprodukt nach Anspruch 1 in einer Menge von 1-70 Gew.-% (bezogen auf die ge¬ samte Komposition). 4. fragrance compositions containing the condensation product according to claim 1 in an amount of 1-70 wt .-% (based on the entire composition).
PCT/EP1996/000475 1995-02-15 1996-02-06 Condensation products WO1996025382A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02282339A (en) * 1989-04-25 1990-11-19 T Hasegawa Co Ltd Ketones and alcohols
DE4125765A1 (en) * 1991-08-03 1993-02-04 Henkel Kgaa TRIMETHYLHEXANAL DERIVATIVES, THEIR PRODUCTION AND USE

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02282339A (en) * 1989-04-25 1990-11-19 T Hasegawa Co Ltd Ketones and alcohols
DE4125765A1 (en) * 1991-08-03 1993-02-04 Henkel Kgaa TRIMETHYLHEXANAL DERIVATIVES, THEIR PRODUCTION AND USE

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 114, no. 19, 13 May 1991, Columbus, Ohio, US; abstract no. 184803, TAKAGI K ET AL: "Preparation of aliphatic ketones and alcohols as odorous substances" *

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