WO1984000542A1 - 1-(1-methylthio -3-oxo-butyl) - 2,6, 6-trimethyl-cyclohexenes and utilization thereof as aroma or perfume - Google Patents

1-(1-methylthio -3-oxo-butyl) - 2,6, 6-trimethyl-cyclohexenes and utilization thereof as aroma or perfume Download PDF

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Publication number
WO1984000542A1
WO1984000542A1 PCT/EP1983/000202 EP8300202W WO8400542A1 WO 1984000542 A1 WO1984000542 A1 WO 1984000542A1 EP 8300202 W EP8300202 W EP 8300202W WO 8400542 A1 WO8400542 A1 WO 8400542A1
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Prior art keywords
aroma
methylthio
general formula
compound
oxo
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PCT/EP1983/000202
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German (de)
French (fr)
Inventor
Ernst-Joachim Brunke
Erich Klein
Willi Rojahn
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Dragoco Gerberding Co Gmbh
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Publication of WO1984000542A1 publication Critical patent/WO1984000542A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Abstract

The new thiomethyl ether 1a and 1b have the following formula and are used as aroma or perfume.

Description

1- (1-Methylthio-3-oxo-butyl)-2,6,6-trimethyl-cyclohexene und deren Verwendung als Riech- und Aroinastoff1- (1-Methylthio-3-oxo-butyl) -2,6,6-trimethyl-cyclohexenes and their use as a fragrance and aroma substance
BesehreibungDescription
Die Erfindung betrifft die Verbindungen der allgemeinen Formel - die Thiomethylether von. α-Jonon bzw. ß-Jonon - sowie deren Verwendung als Riech- oder Aromastoff.The invention relates to the compounds of the general formula - the thiomethyl ether of. α-Jonon or ß-Jonon - and their use as a fragrance or flavoring.
Figure imgf000003_0001
Figure imgf000003_0001
Jonone (A), Irone (B) und Damascone (C) sind als organolep tisch und olfaktorisch bedeutsame Verbindungen bekannt [Über sicht in: E. Theimer (ed.), Fragrance Chemistry, Academic Press, New York 1982], Ebenfalls bekannt sind einige schwefel haltige Derivate dieser Verbindungen. So beschreibt die Dt. Offenleg. 2 159 924 (22.6.72) die Verbindungen der allgemeinen Formel D, nämlich die Thiole und Thioacetate der Jonone und Irone. Die Verbindungen der Formel D (R=H) bewirken in MiJonone (A), Irone (B) and Damascone (C) are known to be organoleptically and olfactory important compounds [review in: E. Theimer (ed.), Fragrance Chemistry, Academic Press, New York 1982], are also known some sulfur-containing derivatives of these compounds. So describes the German. Disclosed 2,159,924 (6/22/72) the compounds of the general formula D, namely the thiols and thioacetates of Jonone and Irone. The compounds of the formula D (R = H) in Mi
Figure imgf000003_0002
schung mit α-Jonon einen typischen Himbeergeschmack, wobei alle hier verwendeten Einzelkomponenten in keiner Weise geruchlich an Himbeeren erinnern. Von den Thiomethyiethern 1a,bwar nichts bekannt.
Figure imgf000003_0002
a typical raspberry taste with α-Jonon, whereby all of the individual components used here are in no way reminiscent of raspberries. Nothing was known about Thiomethyiethern 1a, b.
In dem Dt. Patent 2 808 710 (Ausgabetag 18.9.1980) werden die in schwarzem Tabaköl gefundenen Verbindungen E beschrieben. Diese Thiomethylether der Damascone besitzen facettenreiche süß-heuartige Geruchs- und Geschmackseigenschaften, die anIn the German Patent 2 808 710 (date of issue September 18, 1980) describes the compounds E found in black tobacco oil. These thiomethyl ethers from Damascone have multifaceted sweet-hay-like smell and taste properties
Figure imgf000004_0001
Figure imgf000004_0001
Tee und trockene Früchte erinnern.Remember tea and dry fruits.
Wie wenig man auch bei chemisch nah verwandten Verbindungen aus der Struktur auf Geschmack oder Geruch schließen kann, zeigt das 8-Mercaptomenthon-3-on welches das Aroma von schwarzen Johannisbeeren hat (Helv. Chim. Acta 54, 1971, 1801 ff.; 1803),während der entsprechende aus der DE-OS 20 43 366, Beispiel 4, bekannte Methylthio ether in seiner Geruchswirkung an Pfefferminze, Geranium und Kümmel erinnert.How little one can conclude from the structure of taste or smell from chemically closely related compounds is shown by 8-mercaptomenthon-3-one, which has the aroma of black currants (Helv. Chim. Acta 54, 1971, 1801 ff .; 1803 ), while the corresponding methylthio ether known from DE-OS 20 43 366, Example 4, is reminiscent of peppermint, geranium and caraway in its olfactory effect.
Es war daher überraschend, daß die bisher nicht beschriebenenIt was therefore surprising that those not described so far
Verbindungen 1a,b ausgesprochen frische Geschmackseigenschaften in fruchtiger Richtung besitzen und sich somit vorteilhaft in zahlreiche unterschiedliche Aroma-Kompositionen fruchtigen Typs einarbeiten lassen, denen sie bereits bei Konzentrationen von 0,1 ppm eine natürlich wirkende Frische und Abrundung verleihen. Die Verbindungen la,b bewirken auf geschmacksschwachen Rauchtabaken bereits in Konzentrationen von 0.5 ppb frische, fruchtige Geschmacksaspekte. Die Verbindungen 1a,b können auch vorteilhaft in Parfüm-Kompositionen eingesetzt werden, denen sie bereits bei geringer Dosierung eine natürliche Aus strahlung verleihen.Compounds 1a, b have extremely fresh taste properties in the fruity direction and are therefore advantageous in numerous different aroma compositions of the fruity type let it work in, which gives it a natural freshness and roundness even at concentrations of 0.1 ppm. The compounds la, b produce fresh, fruity taste aspects on weak-tasting smoking tobacco in concentrations of 0.5 ppb. The compounds 1a, b can also be used advantageously in perfume compositions to which they give natural radiation even at low doses.
Figure imgf000005_0001
Figure imgf000005_0001
Die Darstellung der "Verbindungen 1a,b erfolgt in an sich bekannter Weise durch Umsetzung von α- oder ß-Jonon (2) mit Methylmercaptan in Gegenwart von organischen Basen, vorzugsweise Triethylamin, bei Temperaturen von 0 bis 20°C. Vorzugsweise wird ein Überschuß von Methylmercaptan verwendet. Die Isolierung und Reinigung der erhaltenen Verbindung erfolgt ebenfalls in an sich bekannter Weise, vorzugsweise durch Aufnehmen in ein geeignetes Lösungsmittel, Waschen und Abtreiben des Lösungsmittels, gegebenenfalls gefolgt von vorsichtiger Destillation. Es ist allerdings nicht unbedingt nötig, Wasser zuzugeben, also ein Zweiphasengemisch herzustellen, damit die organische Base größtenteils schon bei dieser Stufe entfernt werden kann. Die Entfernung mit Schwefelsäure, gegebenenfalls unter Kühlung in der nächsten Waschstufe genügt grundsätzlich.Compounds 1a, b are prepared in a manner known per se by reacting α- or β-ionone (2) with methyl mercaptan in the presence of organic bases, preferably triethylamine, at temperatures from 0 to 20 ° C. An excess is preferred The isolation and purification of the compound obtained is likewise carried out in a manner known per se, preferably by taking up in a suitable solvent, washing and stripping off the solvent, if appropriate followed by careful distillation, although it is not absolutely necessary to add water, ie to prepare a two-phase mixture so that most of the organic base can already be removed at this stage. Removal with sulfuric acid, if necessary with cooling in the next washing stage, is generally sufficient.
Die folgenden Beispiele erläutern die Erfindung: Beispiel 1The following examples illustrate the invention: example 1
Herstellung von 1 (1-Methylthio—3-oxo-butyl)-2,6,6-trimethyl cyclohexen-2 (1b)Preparation of 1 (1-methylthio-3-oxo-butyl) -2,6,6-trimethylcyclohexen-2 (1b)
Bei 10°C wurden 192 g (1 mol) α-Jonon (2b) und 20 ml Triethyl amin unter Rühren mit 57.6 g (1.2 mol) Methylmercaptan ver setzt. Nach 1 Stde. Rühren bei 10ºC wurde mit 0.2 l Wasser und 0.3 l Diethylether versetzt. Die organische Phase wurde mit 5 %iger Schwefelsäure und danach mit 1. Wasser und 2. ges. NaHCO3-Lsg. gewaschen. Das nach Einengen i. Vak. verblei bende Rohprodukt wurde über eine 60 cm Vigreux-Kolonne des tilliert. Man erhielt 185 g (77 %) 1b als farbloses Öl.At 10 ° C 192 g (1 mol) of α-Jonon (2b) and 20 ml of triethylamine were mixed with 57.6 g (1.2 mol) of methyl mercaptan while stirring. After stirring for 1 hour at 10 ° C, 0.2 l of water and 0.3 l of diethyl ether were added. The organic phase was washed with 5% sulfuric acid and then with 1st water and 2nd sat. NaHCO 3 solution. washed. After narrowing i. Vac. remaining raw product was distilled over a 60 cm Vigreux column. 185 g (77%) of 1b were obtained as a colorless oil.
Figure imgf000006_0001
1 H-NMR-Spektrum : Fig. 1 Massenspektrum : Fig. 2
Figure imgf000006_0001
1 H-NMR spectrum: FIG. 1 mass spectrum: FIG. 2
Beispiel 2Example 2
1-(1-Methylthio-3-oxo-butyl)-2,6,6-trimethyl-cyclohexen-1 (1a)1- (1-methylthio-3-oxo-butyl) -2,6,6-trimethyl-cyclohexene-1 (1a)
In Analogie zu Beispiel 1 wurden aus 192 g (1 mol) ß-Jonon (2a) nach Destillation 196 g (82 %) 1a erhalten.Analogously to Example 1, 196 g (82%) of 1a were obtained from 192 g (1 mol) of β-ionone (2a) after distillation.
Figure imgf000006_0002
1H-NMR-Spektrum : Fig. 3 Massenspektrum : Fig. 4 Beispiel 3 Geschmacksbewertung
Figure imgf000006_0002
1H-NMR spectrum: FIG. 3 mass spectrum: FIG. 4 Example 3 Taste Assessment
Die Verbindungen 1a und 1b wurden in einer Konzentration von 1 g/100 kg Zuckerlösung (10 %ig) von einem Testgremium sensorisch beurteilt.Compounds 1a and 1b were sensory-assessed in a concentration of 1 g / 100 kg sugar solution (10%) by a test panel.
1a: natürlich fruchtig, in Richtung Himbeere, Bromb Kirsche1a: naturally fruity, in the direction of raspberry, bromb cherry
1b: fruchtig, holzig.1b: fruity, woody.
Die Reizschwelle liegt jeweils bei ca. 0.1 g/100 kg Zucker lösung und die Erkennungsschwelle bei ca. 0. 3 g/100 kg Zuckerlösung. The irritation threshold is approx. 0.1 g / 100 kg sugar solution and the detection threshold is approx. 0.3 g / 100 kg sugar solution.
Figure imgf000008_0001
Die Mischung a ist ein typisches Himbeer-Aromakonzentrat. Der Geschmackseindruck in Zuckerlösung (1 g/100 kg 10/oiger Zucker Isg.) ist deutlich himbeerartig. Bei Austausch von ß-Jonon gegen die Verbindung 1b (Mischung b) wird der Geschmackseindruck natürlicher, voller und erinnert an Vollreife Himbeeren. Die Mischung c (Austausch von ß-Jonon gegen 1a) hat ein Him beeraroma mit Geschmacksaspekten die an Himbeerkerne erinnern.
Figure imgf000008_0001
Mixture a is a typical raspberry flavor concentrate. The taste impression in sugar solution (1 g / 100 kg 10% sugar Isg.) Is clearly raspberry-like. When ß-Jonon is replaced by compound 1b (mixture b), the taste impression becomes more natural, fuller and reminiscent of fully ripe raspberries. The mixture c (exchange of ß-Jonon for 1a) has a raspberry aroma with taste aspects that are reminiscent of raspberry seeds.
Figure imgf000009_0001
Die Mischung a entspricht dem Hauptteil des bulgarischen Rosenöls und besitzt einen starken Duftkomplex in Richtung "Rose". Bei einem Zusatz von 1b (Mischung b) werden wachsiggrüne Aspekte betont und der Geruchseindruck wird dem des bulgarischen Rosenöls ähnlicher. Die Mischung c wirkt gegenüber a harmonischer und mehr abgerundet.
Figure imgf000009_0001
Mixture a corresponds to the main part of Bulgarian rose oil and has a strong fragrance complex in the direction of "rose". When 1b (mixture b) is added, waxy green aspects are emphasized and the smell impression becomes more similar to that of Bulgarian rose oil. The mixture c appears more harmonious and more rounded than a.

Claims

PATENTANSPRÜCHE PATENT CLAIMS
1. 1 -(1-Methylthio-3-oxo-butyl)-2,6,6-trimethylcyclohexene der allgemeinen Formel 1, wobei die gestrichelte Linie eine Doppelbindung alternativ an C-1 oder C-2 bedeutet.1. 1 - (1-Methylthio-3-oxo-butyl) -2,6,6-trimethylcyclohexenes of the general formula 1, the dashed line meaning a double bond alternatively at C-1 or C-2.
Figure imgf000011_0001
Figure imgf000011_0001
2. Verfahren zur Herstellung der Verbindungen nach Anspruch 1, dadurch gekennzeichnet, daß man α-Jonon oder ß-Jonon in an sich bekannter Weise mit Methylmercaptan in Gegenwart von organischen Basen bei Temperaturen von 0 bis 20°C umsetzt.2. A process for the preparation of the compounds according to claim 1, characterized in that α-Jonon or ß-Jonon is reacted in a manner known per se with methyl mercaptan in the presence of organic bases at temperatures from 0 to 20 ° C.
3. Verwendung der Verbindung der allgemeinen Formel 1 als Riech- und Aromastoff, bzw. als Bestandteil von Riech- und Geschmackstoff-Kompositionen.3. Use of the compound of general formula 1 as a fragrance and aroma, or as a component of fragrance and flavor compositions.
4. Verfahren, um Aromakompositionen für Nahrungs- und Genußmittel, Tabakwaren sowie Tiernahrungsmittel oder Parfümkompositionen für kosmetische und technische Anwendung eine natürlich wirkende Frische und Abrundung zu verleihen, dadurch gekennzeichnet, daß man darin eine Verbindung der allgemeinen Formel 1, worin die gestrichelten Linien eine Doppelbindung alternativ zu4. A process for imparting a natural-looking freshness and rounding off to aroma compositions for foodstuffs and luxury foods, tobacco products and pet foods or perfume compositions for cosmetic and technical use, characterized in that a compound of the general formula 1 in which the dashed lines are double-bonded therein alternative to
C-1 oder C-2 bedeuten, in einer Menge von mindestens 0,5 ppb, bezogen auf Gesamtgewicht des erhaltenen Materials, einbringt. C-1 or C-2 mean, in an amount of at least 0.5 ppb, based on the total weight of the material obtained.
5. Künstliches ätherisches öl, dadurch gekennzeichnet, daß es eine Menge an Verbindung der Formel 1 gemäß Anspruch 1 aufweist, die ausreicht, um der Zusammensetzung einen organoleptischen Effekt mit natürlich wirkender Frische und Abrundung zu verleihen. 5. Artificial essential oil, characterized in that it has an amount of compound of formula 1 according to claim 1, which is sufficient to give the composition an organoleptic effect with a natural freshness and roundness.
PCT/EP1983/000202 1982-07-29 1983-07-29 1-(1-methylthio -3-oxo-butyl) - 2,6, 6-trimethyl-cyclohexenes and utilization thereof as aroma or perfume WO1984000542A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984003508A1 (en) * 1983-03-05 1984-09-13 Dragoco Gerberding Co Gmbh Methyl substituted 1- ad(3-methylthio)-1-oxo-butyl bd-cyclohexene, production process thereof and utilization as perfum and aromatic product
US7723286B2 (en) 2001-12-13 2010-05-25 Firmenich Sa Compounds for a controlled release of active molecules
WO2022084437A1 (en) * 2020-10-21 2022-04-28 Firmenich Sa Improved freshness imparting compositions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107881011B (en) * 2017-12-12 2021-02-26 江西中烟工业有限责任公司 Preparation method of composite fruit extract

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2159924A1 (en) * 1970-12-08 1972-06-22
DE2808710A1 (en) * 1977-03-03 1978-09-14 Int Flavors & Fragrances Inc SINGLE-SQUARE CLAMP ON 3-METHYLTHIO) BUTYRYL SQUARE CLAMP FOR -2,6,6-TRIMETHYLCYCLOHEXEN AND THE 1,3-CYCDOHEXADIENE ANALOGUE, PROCESS FOR THEIR PRODUCTION AND THEIR USE

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2159924A1 (en) * 1970-12-08 1972-06-22
DE2808710A1 (en) * 1977-03-03 1978-09-14 Int Flavors & Fragrances Inc SINGLE-SQUARE CLAMP ON 3-METHYLTHIO) BUTYRYL SQUARE CLAMP FOR -2,6,6-TRIMETHYLCYCLOHEXEN AND THE 1,3-CYCDOHEXADIENE ANALOGUE, PROCESS FOR THEIR PRODUCTION AND THEIR USE

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984003508A1 (en) * 1983-03-05 1984-09-13 Dragoco Gerberding Co Gmbh Methyl substituted 1- ad(3-methylthio)-1-oxo-butyl bd-cyclohexene, production process thereof and utilization as perfum and aromatic product
US7723286B2 (en) 2001-12-13 2010-05-25 Firmenich Sa Compounds for a controlled release of active molecules
WO2022084437A1 (en) * 2020-10-21 2022-04-28 Firmenich Sa Improved freshness imparting compositions

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DE3228289A1 (en) 1984-02-09

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