DE2447169A1 - 7-Acyl-hexahydro-azulenes - perfume components and inters for pharmaceuticals and cosmetics e.g. guaiazulene - Google Patents

7-Acyl-hexahydro-azulenes - perfume components and inters for pharmaceuticals and cosmetics e.g. guaiazulene

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DE2447169A1
DE2447169A1 DE19742447169 DE2447169A DE2447169A1 DE 2447169 A1 DE2447169 A1 DE 2447169A1 DE 19742447169 DE19742447169 DE 19742447169 DE 2447169 A DE2447169 A DE 2447169A DE 2447169 A1 DE2447169 A1 DE 2447169A1
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guaiazulene
hexahydroazulenes
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cosmetics
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Werner Dr Hoffmann
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BASF SE
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    • C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
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    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
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    • 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
    • C07C45/65—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C07C45/66—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
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    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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    • 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
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    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
    • C07C2602/30—Azulenes; Hydrogenated azulenes

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Abstract

Hexahydroazulenes of formula (I) are new (R1 = H or opt. branched satd. 1-4C hydrocarbyl; R2, R3. R4 and R5 = opt. branched 1-4C hydrocarbyl, 5-8C cycloalkyl or phenyl; or R1 + R2 or R4 + R5 can be 3-6C alkylene). (I) are perfume ingredients with a woody note and key inters. for new and known azulene derivs. e.g. for guaiazulene which has known applications in pharmaceuticals and cosmetics.

Description

Hexahydroazulene und ein Verfahren zu ihrer Herstellung Die Erfindung betrifft substituierte 7-Alkanoyl- oder 7-Cycloalkanoyl-hexahydroazulene und ein Verfahren zu ihrer Herstellunge Speziell betrifft sie Hexahydroazulene der allgemeinen Formel 1 in der R1 für Wasserstoff oder einen geradkettigen oder verzweigten gesättigten Kohlenwasserstoffrest mit 1 bis 4 C-Atomen steht, R2, R3, R4 und R5 Wasserstoff, einen geradkettigen oder verzweigten Kohlenwasserstoffrest mit 1 bis 4 C-Atomen, vorzugsweise Methyl, Cycloalkyl mit 5 bis 8 C-Atomen oder Phenyl bedeuten und darüber hinaus R1 und R2 sowie R4 und R5 jeweils zusammen eine Alkylengruppe mit 3 bis 6 C-Atomen bedeuten können.Hexahydroazulenes and a process for their preparation The invention relates to substituted 7-alkanoyl- or 7-cycloalkanoyl-hexahydroazulenes and a process for their preparation. Specifically, it relates to hexahydroazulenes of the general formula 1 in which R1 is hydrogen or a straight-chain or branched saturated hydrocarbon radical with 1 to 4 carbon atoms, R2, R3, R4 and R5 are hydrogen, a straight-chain or branched hydrocarbon radical with 1 to 4 carbon atoms, preferably methyl, cycloalkyl with 5 to 8 denote carbon atoms or phenyl and, in addition, R1 and R2 and R4 and R5 together can each denote an alkylene group having 3 to 6 carbon atoms.

Die neuen Hexahydroazulene eignen sich als Riechstoffkomponente zur Erzielung holzartiger Geruchseffekte. Darüber hinaus stellen sie eine Schlüsselverbindung für die Herstellung zahlreicher bekannter und neuer Azulenderivate dar. Beispielsweise läßt sich aus 1,4-Dimethyl-7^acyl-2,3,4,5,8,10-hexahydroazulen (Ia) durch einfache Grignardmethylierung und anschließende Dehydratisierung und Dehydrierung der bekannte in der Kamille vorkommende Naturstoff Guaiazulen (IV) herstellen. Guaiazulen findet vielfach in der Heilmittel- und Kosmetikindustrie Verwendung. cH O OH e CH5 H5 115 Dehydra~ v 01%OH5 N{HC7 CH5MgCl cH,MpC1 mX 3 Dehydrie--CHD W s Dehydrfe-Cf OH3 3 Ia III IV Das bei dieser Synthese auftretende neue Zwischenprodukt III ist ein Sesquiterpen mit wertvollen RiechstoffeigenschaftenO Es riecht harzig, Richtung Fichtenholz und gleichzeitig leicht blumige Gegenstand der Erfindung ist ferner ein Verfahren zur Herstellung der neuen Hexahydroazulene der Formel I, das dadurch gekennzeichnet ist, daß man eine Verbindung der allgemeinen Formel II in der R1 bis R5 die oben angegebene Bedeutung haben, gegebenenfalls in einem unter den Reaktionsbedingungen inerten Lösungsmittel in Gegenwart eines Dehydratisierungskatalysators auf Temperaturen von 100 bis 500°C, vorzugsweise 150 bis 250 0C, erhitzt.The new hexahydroazulenes are suitable as a fragrance component to achieve wood-like odor effects. In addition, they represent a key compound for the production of numerous known and new azulene derivatives. For example, 1,4-dimethyl-7 ^ acyl-2,3,4,5,8,10-hexahydroazulene (Ia) can be obtained by simple Grignard methylation and subsequent dehydration and dehydration of the well-known natural substance guaiazulene (IV) found in chamomile. Guaiazulene is widely used in the medicinal and cosmetic industries. cH O OH e CH5 H5 115 dehydration 01% OH5 N {HC7 CH5MgCl cH, MpC1 mX 3 dehydration - CHD W s Dehydrfe-Cf OH3 3 Ia III IV The new intermediate III occurring in this synthesis is a sesquiterpene with valuable odorant propertiesO It smells resinous, towards spruce wood and at the same time slightly flowery. The invention furthermore relates to a process for the preparation of the new hexahydroazulenes of the formula I, which is characterized in that a compound of the general formula II in which R1 to R5 have the meaning given above, optionally heated to temperatures of 100 to 500.degree. C., preferably 150 to 250.degree. C., in a solvent which is inert under the reaction conditions in the presence of a dehydration catalyst.

Es war überraschend, daß die Verbindungen der Formel II unter den erfindungsgemäßen Reaktionsbedingungen nicht, wie erwartet werden konnte, lineare Kondensationsprodukte liefern, sondern in glatter Reaktion zu einem 1-Acyl-Siebenring cyclisieren.It was surprising that the compounds of formula II among the The reaction conditions according to the invention are not, as could be expected, linear Provide condensation products, but in smooth reaction to form a 1-acyl seven-membered ring cyclize.

Die als Ausgangsstoffe für das erfindungsgemäße Verfahren benötigten Verbindungen der Formel II sind neue Stoffe. Sie können beispielsweise auf die aus dem folgenden Reaktionsschema wiedergegebene Weise aus bekannten Vorprodukten hergestellt werden. 4 R4 R R C2H2 R C2H2 "i 2B1 1 R2 R1 RIR2 R1 VI 0 VII V VI 4 R4 R'OOCCH,-COR R5 /\ II ~ >/ sR2 R ~ 7 - > II VIII Bevorzugte Ausgangsverbindungen der Formel II und daher auch bevorzugte Hexahydroazulene der Formel 1 sind solche, in denen R1 für Methyl, Äthyl, Isopropyl, Phenyl R2, R3, R4 und R5 fUr Methyl, Athyl oder R1 und R2 bzw. R4 und R5 zusammen für Propylen-(1,3) oder Butylen-(1,3) stehen.The compounds of the formula II required as starting materials for the process according to the invention are new substances. For example, they can be prepared from known precursors in the manner shown in the following reaction scheme. 4th R4 RR C2H2 R C2H2 "i 2B1 1 R2 R1 RIR2 R1 VI 0 VII V VI 4 R4 R'OOCCH, -COR R5 / \ II ~> / sR2 R ~ 7 -> II VIII Preferred starting compounds of the formula II and therefore also preferred hexahydroazulenes of the formula 1 are those in which R1 is methyl, ethyl, isopropyl, phenyl, R2, R3, R4 and R5 are methyl, ethyl or R1 and R2 or R4 and R5 together are propylene - (1,3) or butylene- (1,3) stand.

Genannt seien beispielsweise: 1-(2'-Oxobutan-4'-yl)-2-methyl-5-(1"-oxobutan-3"-yl)-cyclopent-1-en, 1-(2'-Oxobutan-4'-yl)-5-(1"-oxobutan-3"-yl)-cyclopent-1-en, 1-(2'-Oxobutan-4'-yl)-2-phenyl-5-(1"-oxobutan-3"-yl)-cyclopent-1-en, 1-(2'-Oxobutan-4'-yl)-2-methyl-5-(2"-formyl-cyclohex-1"-en-1"-yl)-cyclopent-1-en und 1-(2'-Oxobutan-4'-yl)-2,3-(propylen-1",3")-5-(1'''-oxobutan-3'''-yl)-cyclopent-1-en (besser: 5-(1'-Oxobutan-3'-yl)-6-(2''-oxobutan-4'-yl-bicyclo[3.3.0]oct-6-en).Examples include: 1- (2'-Oxobutan-4'-yl) -2-methyl-5- (1 "-oxobutan-3" -yl) -cyclopent-1-en, 1- (2'-Oxobutan-4'-yl) -5- (1 "-oxobutan-3" -yl) -cyclopent-1-ene, 1- (2'-Oxobutan-4'-yl) -2- phenyl-5- (1 "-oxobutan-3" -yl) -cyclopent-1-en, 1- (2'-Oxobutan-4'-yl) -2-methyl-5- (2 "-formyl-cyclohex-1" -en-1 "-yl) -cyclopent-1-en and 1- (2'-oxobutan-4'-yl) -2,3- (propylene-1 ", 3") - 5- (1 "'- oxobutan-3"' - yl) -cyclopent-1 -en (better: 5- (1'-Oxobutan-3'-yl) -6- (2 '' - oxobutan-4'-yl-bicyclo [3.3.0] oct-6-en).

Als unter den Reaktionsbedingungen inerte Lösungsmittel können erfindungsgemäß Kohlenwasserstoffe, wie Dekalin, Tetralin, Naphthalin, Paraffinöl, Xylol, Toluol, hochsiedende Ather wie Dibutylether sowie Siliconöl, N-Methylpyrrolidon, Dimethylformamid und Dimethylsulfoxid verwendet werden.According to the invention, solvents which are inert under the reaction conditions can be used Hydrocarbons such as decalin, tetralin, naphthalene, paraffin oil, xylene, toluene, high-boiling ethers such as dibutyl ether and silicone oil, N-methylpyrrolidone, dimethylformamide and dimethyl sulfoxide can be used.

Als Dehydratisierungskatalysatoren kommen die üblicherweise für Wasserabspaltungen unter Ringschluß verwendeten Mittel in Betracht. Es können neutral reagierende Katalysatoren, wie die Oxide von Zink, Aluminium Thorium, Wolfram (blaues Wolframoxid) und Titan, aber auch saure Katalysatoren, wie Kieselgel, Borsäure, Phosphorsäure, Schwefelsäure oder deren Salze sowie Salze, wie Piperidinacetat, in Betracht. Bevorzugt werden Metalloxide, wie ZnO, Th02, WO3, TiO2 und Al203 insbesondere aktiviertes ZnO. Bezüglich weiterer Einzelheiten über die Dehydratisierungskatalysatoren und deren Herstellung verweisen wir auf Houben-Weyl, "Methoden der organischen Chemie", Band 4/2, Seiten 209 bis 218.The dehydration catalysts that are usually used are those for dehydration means used under ring closure into consideration. It can be neutral reactive catalysts, such as the oxides of zinc, aluminum, thorium, tungsten (blue Tungsten oxide) and titanium, but also acidic catalysts such as silica gel, boric acid, Phosphoric acid, sulfuric acid or their salts and salts such as piperidine acetate, into consideration. Metal oxides such as ZnO, ThO2, WO3, TiO2 and Al203 are particularly preferred activated ZnO. For more details on the dehydration catalysts and their production, we refer to Houben-Weyl, "Methods of Organic Chemistry", Volume 4/2, pages 209 to 218.

Zur Durchführung des erfindungsgemäßen Verfahrens fügt man entweder zu der Verbindung der Formel II oder deren Lösung in einem inerten Lösungsmittel den Katalysator in Form von Pulver, Körnern oder Kristallen und erhitzt das Ganze auf die Reaktionstemperatur, oder aber man führt die Verbindung der Formel II bei der Reaktionstemperatur kontinuierlich über einen geeigneten Festbettkatalysator. Je nach der Art der Durchführung des Verfahrens ist die Reaktionstemperatur höher oder niedriger.To carry out the process according to the invention, either to the compound of the formula II or its solution in an inert solvent the catalyst in the form of powder, grains or crystals and heats the whole thing on the reaction temperature, or the compound of formula II is added the reaction temperature continuously over a suitable fixed bed catalyst. Depending on how the process is carried out, the reaction temperature is higher or lower.

Wird die Verbindung der Formel II in Gegenwart von einem inerten Lösungsmittel und einem suspendierten oder gelösten Katalysator erhitzt, so sind Terl,peraturen von 100 bis 5000C, vorzugsweise von 150 bis 2500C, notwendig. Führt man dagegen die Verbindung der Formel II kontinuierlich über einen Festbettkontakt, so sind vorzugsweise Temperaturen von 170 bis 2700C notwendig.If the compound of formula II is used in the presence of an inert solvent and a suspended or dissolved catalyst heated, so are Terl, temperatures from 100 to 5000C, preferably from 150 to 2500C, necessary. If you lead against it the compound of formula II continuously via a fixed bed contact so are preferably temperatures of 170 to 2700C are necessary.

Die Lösungsmittel verwendet man im allgemeinen in einem Volumenverhältnis von 1 : 1 bis 10 : 1.The solvents are generally used in a volume ratio from 1: 1 to 10: 1.

Die Isolierung der erfindungsgemäßen Verbindungen erfolgt im allgemeinen durch einfache Destillation des Reaktionsansatzes.The compounds according to the invention are generally isolated by simple distillation of the reaction mixture.

Das erfindungsgemäße Verfahren eröffnet einen neuen Weg zu in der Heilmittel- und Kosmetikindustrie verwendbaren Verbindungen der Azulenreihe. Die neuen Hexahydroazulene zeichnen sich durch ungewöhnliche Duftstoffeigenschaften aus und sind wertvolle Zwischenprodukte £r zahlreiche neue und bekannte Azulenderivase, Die folgenden Beispiele sollen das Verfahren erlautern.The inventive method opens up a new way to in the Compounds of the azulene series that can be used in the medicinal and cosmetic industries. the new hexahydroazulenes are characterized by unusual fragrance properties and are valuable intermediates for numerous new and well-known azulene derivatives, the the following examples are intended to explain the procedure.

Beispiel 1 22 g (0,1 Mol) 1-(2'-Oxo-butan-4'-yl)-2-methyl-5-(1"-oxo-butan-3"-yl)-cyclopent-1-en werden in 100 ml Dekalin gelöst und mit 10 g Zinkoxid aktiviert (Bayer Leverkusen Nr. 045046) versetzt.example 1 22 g (0.1 mol) of 1- (2'-oxo-butan-4'-yl) -2-methyl-5- (1 "-oxo-butan-3" -yl) -cyclopent-1-ene become dissolved in 100 ml of decalin and treated with 10 g of activated zinc oxide (Bayer Leverkusen No. 045046).

Unter kräftigem Rühren wird dann auf 1900C erhitzt und durch gaschromatographische Analyse der Reaktionsverlauf registriert.The mixture is then heated to 1900C while stirring vigorously and by gas chromatography Analysis of the reaction course registered.

Nach einer Stunde ist kein Ausgangsmaterial mehr nachweisbar.After one hour, no more starting material can be detected.

Man filtriert vom Zinkoxid ab und unterwirft das Filtrat einer fraktionierten Destillation, wobei 17 g 1,4-Dimethyl-7-acetyl-2,3,4,5,8,10-hexahydroazulen erhalten werden. Die Ausbeute beträgt 83 % der Theorie.The zinc oxide is filtered off and the filtrate is subjected to a fractionated one Distillation to give 17 g of 1,4-dimethyl-7-acetyl-2,3,4,5,8,10-hexahydroazulene will. The yield is 83% of theory.

Kp0,01 =92 bis 95°C; nD25 = 1,5192; Geruch: holzig (kiefernholzartig).Bp 0.01 = 92 to 95 ° C; nD25 = 1.5192; Odor: woody (like pine).

Beispiele 2 bis 7 22 g (0,1 Mol) 1-(2'-Oxo-butan-4'-yl)-2-methyl-5-(1"-oxo-butan-3"-yl)-cyclopent-1-en werden in 100 ml Dekalin gelöst und mit jeweils 10 g des in der folgenden Tabelle angegebenen Katalysators versetzt. Anschließend wird unter kräftigem Rühren auf 190°C erhitzt und durch gaschromatographische Analyse der Reaktionsverlauf registriert. Nachdem kein Ausgangsmaterial mehr nachweisbar war, wurde der Katalysator abfiltriert und das Filtrat fraktioniert destilliert. In der folgenden Tabelle sind die Reaktionszeit sowie die Ausbeuten an 1,4-Dimethyl-7-acetyl-2,3,4,5,8, 10-hexahydroazulen angegeben. Beispiel Katalysator Reaktionszeit Ausbeute Stunden (% der Theorie) 2 Zinkoxid-Rotsiegel 4 78 3 ZnO-Merck-reinst 4 78 4 TiO2 7 73 5 ThO2 7 75 x) 6 WO3 2 38 xx) 7 r-A1203 6 73 x) - noch 10 % Ausgangsmaterial im Reaktionsgemisch xx) = Bildung eines Nebenprodukts, dessen Struktur noch nicht ermittelt werden konnte, Beispiel 8 22 g (0,1 Mol) 1-(2'-Oxo-butan-4'-yl)-2-methyl-5-(1"-oxo-butan 3"-yl)-cyclopent-1-en werden in 150 ml Xylol gelöst, mit 0,85 g (0,01 Mol) Piperidin und 0,7 g (0,012 Mol) Eisessig versetzt und in einer für Wasserauskreisprozesse geeigneten Apparatur 7 Stunden-zum Sieden erhitzt. Anschließend läßt man abkühlen, wäscht mehrmals mit Wasser und unterwirft die organische Phase einer fraktionierten Destillation. 1,4-Dimethyl-7-acetyl-2,3, 4, 5,8,10-hexahydroazulen wird dabei mit ca. 36%iger Ausbeute erhalten.Examples 2 to 7 22 g (0.1 mol) 1- (2'-oxo-butan-4'-yl) -2-methyl-5- (1 "-oxo-butan-3" -yl) -cyclopent- 1-enes are dissolved in 100 ml of decalin and each time 10 g of the catalyst given in the table below are added. The mixture is then heated to 190 ° C. with vigorous stirring and the course of the reaction is recorded by gas chromatographic analysis. When the starting material was no longer detectable, the catalyst was filtered off and the filtrate was fractionally distilled. The following table shows the reaction time and the yields of 1,4-dimethyl-7-acetyl-2,3,4,5,8,10-hexahydroazulene. Example catalyst reaction time yield Hours (% of theory) 2 Zinc Oxide Red Seal 4 78 3 ZnO-Merck-pure 4 78 4 TiO2 7 73 5 ThO2 7 75 x) 6 WO3 2 38 xx) 7 r-A1203 6 73 x) - still 10% starting material in the reaction mixture xx) = formation of a by-product, the structure of which has not yet been determined, Example 8 22 g (0.1 mol) 1- (2'-oxo-butan-4'-yl) - 2-methyl-5- (1 "-oxo-butane 3" -yl) -cyclopent-1-en are dissolved in 150 ml of xylene, with 0.85 g (0.01 mol) of piperidine and 0.7 g (0.012 Mol) glacial acetic acid and heated to boiling for 7 hours in an apparatus suitable for water removal processes. It is then allowed to cool, washed several times with water and the organic phase is subjected to fractional distillation. 1,4-Dimethyl-7-acetyl-2,3, 4, 5,8,10-hexahydroazulene is obtained in about 36% yield.

Beispiel 9 44 g (0,2 Mol) 1-(2'-Oxo-butan-4'-yl)-2-methyl-5-(1"-oxo-butan-3"-yl)-cyclopent-1-en werden mit 10 g Zinkoxid-aktiviert (Bayer Leverkusen Nr. 045046) versetzt und unter Rühren 30 Minuten auf 220 bis 2300C erhitzt. Man filtriert nach Abkühlen vom Zinkoxid ab und unterwirft das Filtrat einer fraktionierten Destillation, wobei 1,4-Dimethyl-7-acetyl-2,3,4,5,8,10-hexahydroazulen in zeiger Ausbeute isoliert wird. Example 9 44 g (0.2 mol) 1- (2'-Oxo-butan-4'-yl) -2-methyl-5- (1 "-oxo-butan-3" -yl) -cyclopent-1- en are mixed with 10 g of activated zinc oxide (Bayer Leverkusen No. 045046) and under Stirring heated to 220 to 2300C for 30 minutes. After cooling, the zinc oxide is filtered off and subjects the filtrate to fractional distillation, 1,4-dimethyl-7-acetyl-2,3,4,5,8,10-hexahydroazulene is isolated in low yield.

Beispiel 10 40 g (0,15 Mol) 1-(2'-Oxo-butan-4'-yl)-2-methyl-5-(2"-formyl cyclopentan-1"-yl)-cyclopent-1-en werden in 100 ml Tetralin gelöst, mit 10 g Zinkoxid-aktiviert (Bayer Leverkusen Nr.Example 10 40 g (0.15 mol) of 1- (2'-oxo-butan-4'-yl) -2-methyl-5- (2 "-formyl cyclopentan-1" -yl) -cyclopent-1-en are in 100 ml of tetralin dissolved, activated with 10 g of zinc oxide (Bayer Leverkusen No.

045046) versetzt und unter kräftigem Rühren eine Stunde auf 2000C erhitzt. Man filtriert anschließend vom Zinkoxid ab und unterwirft das Filtrat einer fraktionierten Destillation, wobei 25 g 1-Methyl-4,5- (propylen-1 3' )-7-acetyl-2,3,4,5,8,10-hexahydroazulen erhalten werden. Die Ausbeute beträgt 67 % der Theorie.045046) and set at 2000C for one hour while stirring vigorously heated. The zinc oxide is then filtered off and the filtrate is subjected to a fractional distillation, wherein 25 g of 1-methyl-4,5- (propylene-1 3 ') -7-acetyl-2,3,4,5,8,10-hexahydroazulene can be obtained. The yield is 67% of theory.

Kp0,01 =96 bis 98°C; nD25 = 1,5319; Geruch: balsamig, holzig, erdig.Bp 0.01 = 96 to 98 ° C; nD25 = 1.5319; Smell: balsamic, woody, earthy.

Beispiel 11 50 g (0,2 Mol) 1-(2'-Oxo-butan-4'-yl)-2,3-(propylen-1",3" (1"'-oxo-butan-3"'-yl)-cyclopent-1-en werden in 50 ml Tetralin gelöst und mit 20 g Zinkoxid-aktiviert (Bayer Leverkusen Nr.Example 11 50 g (0.2 mole) 1- (2'-oxo-butan-4'-yl) -2,3- (propylene-1 ", 3" (1 "'- oxo-butan-3"' - yl ) -cyclopent-1-en are dissolved in 50 ml of tetralin and activated with 20 g of zinc oxide (Bayer Leverkusen No.

045046) versetzt. Unter kräftigem Rühren wird eine Stunde auf 2050C erhitzt, anschließend abfiltriert und das Filtrat einer fraktionierten Destillation unterworfen. Man erhält 27 g 1,2-(Propylen-1',3')-4-methyl-7-acetyl-2,3,4,5,8,10-hexahydroazulen.045046) offset. While stirring vigorously, it is set to 2050C for one hour heated, then filtered off and the filtrate a fractional distillation subject. 27 g of 1,2- (propylene-1 ', 3') -4-methyl-7-acetyl-2,3,4,5,8,10-hexahydroazulene are obtained.

Das entspricht einer Ausbeute von 58 % der Theorie.This corresponds to a yield of 58% of theory.

Kp0,1 = 102 bis 1050C; nD25 = 1,5285; Geruch: würzig-holzig.Bp 0.1 = 102 to 1050C; nD25 = 1.5285; Smell: spicy and woody.

Claims (3)

Patentansprüche Claims 1o Hexahydroazulene der allgemeinen Formel I in der R1 für Wasserstoff oder einen geradkettigen oder verzweigten gesättigten Kohlenwasserstoffrest mit 1 bis 4 C-Atomen steht, R22 R3, R4 und R5 Wasserstoff, einen geradkettigen oder verzweigten Kohlenwasserstoffrest mit 1 bis 4 C-Atomen, cycloalkyl mit 5 bis 8 C-Atomen oder Phenyl bedeuten und darüber hinaus R1 und R2 sowie R4 und R5 jeweils zusammen eine Alkylengruppe mit 3 bis 6 C-Atomen bedeuten können.1o hexahydroazulenes of the general formula I. in which R1 is hydrogen or a straight-chain or branched saturated hydrocarbon radical with 1 to 4 carbon atoms, R22, R3, R4 and R5 are hydrogen, a straight-chain or branched hydrocarbon radical with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or phenyl and, in addition, R1 and R2 and also R4 and R5 together can each denote an alkylene group having 3 to 6 carbon atoms. 2. Verfahren zur Herstellung der Hexahydroazulene der allgemeinen Formel I in der R1 für Wasserstoff oder einen geradkettigen oder verzweigten gesättigten Kohlenwasserstoffrest mit 1 bis 4 C-Atomen steht R29 R3, R4 und R5 Wasserstoff, einen geradkettigen oder verzweigten Kohlenwasserstoffrest mit 1 bis 4 C-Atomen, Cycloalkyl mit 5 bis 8 C-Atomen oder Phenyl bedeuten und daruber hinaus R1 und R2 sowie R4 und R5 jeweils zusammen eine Alkylengruppe mit 3 bis 6 C-Atomen bedeuten können, dadurch gekennzeichnet, daß man eine Verbindung der allgemeinen Formel II in der R1 bis R5 die oben angegebene Bedeutung haben, gegebenenfalls in einem unter den Reaktionsbedingungen inerten Lösungsmittel in Gegenwart eines Dehydratisierungskatalysators auf Temperaturen von 100 bis 5000C erhitzt.2. Process for the preparation of the hexahydroazulenes of the general formula I. in which R1 is hydrogen or a straight-chain or branched saturated hydrocarbon radical with 1 to 4 carbon atoms, R29, R3, R4 and R5 are hydrogen, a straight-chain or branched hydrocarbon radical with 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or Phenyl and, in addition, R1 and R2 and R4 and R5 together can each denote an alkylene group having 3 to 6 carbon atoms, characterized in that a compound of the general formula II in which R1 to R5 have the meaning given above, optionally heated to temperatures of 100 to 5000C in a solvent which is inert under the reaction conditions in the presence of a dehydration catalyst. 3. 1,4-Dimethyl-7-acetyl-2,3,4,5,8,10-hexahydroazulen.3. 1,4-Dimethyl-7-acetyl-2,3,4,5,8,10-hexahydroazulene.
DE2447169A 1974-10-03 1974-10-03 Process for the preparation of hexahydroazulenes and new hexahydroazulenes Expired DE2447169C2 (en)

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Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Chem. Abstracts, 81, 1974, Referat 136316n *
Chemistry and Industry, 68, 1956, S. 576-577 *
March, J.: Advanced Organic Chemistry, McGraw-Hill, 1968, S. 684 *
Tetrahedron Letters, 36, 1974, S. 3239-3240 *

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