DE2447169C2 - Process for the preparation of hexahydroazulenes and new hexahydroazulenes - Google Patents
Process for the preparation of hexahydroazulenes and new hexahydroazulenesInfo
- Publication number
- DE2447169C2 DE2447169C2 DE2447169A DE2447169A DE2447169C2 DE 2447169 C2 DE2447169 C2 DE 2447169C2 DE 2447169 A DE2447169 A DE 2447169A DE 2447169 A DE2447169 A DE 2447169A DE 2447169 C2 DE2447169 C2 DE 2447169C2
- Authority
- DE
- Germany
- Prior art keywords
- hexahydroazulenes
- new
- methyl
- reaction
- butan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
- C07C49/553—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—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
- C07C29/38—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
- C07C29/40—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 carbon-to-metal bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—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
- C07C29/38—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/05—Alcohols containing rings other than six-membered aromatic rings
- C07C33/16—Alcohols containing rings other than six-membered aromatic rings containing rings with more than six ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/06—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a five-membered rings
-
- 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
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
-
- 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
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- 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
- C07C45/65—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/647—Unsaturated compounds containing a keto groups being part of a ring having unsaturation outside the ring
- C07C49/653—Unsaturated compounds containing a keto groups being part of a ring having unsaturation outside the ring polycyclic
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- 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
Description
R' für Wasserstoff oder einen geradkettigen oder verzweigten gesättigten Kohlenwasserstoffrest mn i bis
4 C-Atomen steht
R2, RJ. R4 und R5 Wasserstoff, einen geradkettigen oder verzweigten iCohlenwasserstoffrest mit I bis 4 C-R 'represents hydrogen or a straight-chain or branched saturated hydrocarbon radical with 1 to 4 carbon atoms
R 2 , R J. R 4 and R 5 hydrogen, a straight-chain or branched hydrocarbon radical with I to 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,Atoms. Cycloalkyl with 5 to 8 carbon atoms or phenyl and more
R 1 and R 2 as well as R 4 and R 5 together can each denote an alkylene group with 3 to 6 carbon atoms,
dadurch gekennzeichnet, daß man eine Verbindung der allgemeinen Formel 11
H Ocharacterized in that a compound of the general formula 11
HO
ODOD
in der R1 bis R5 die oben angegebene Bedeutung haben, gegebenenfalls in einem unter den Reaktionsbedingungen inerten Lösungsmittel in Gegenwart eines Dehydratisierungskatalysaiors auf Temperaturen von 100 bis 5000C erhitzt.in which R 1 to R 5 have the meaning given above, optionally heated to temperatures of 100 to 500 ° C. in a solvent which is inert under the reaction conditions in the presence of a dehydration catalyst.
2. Hexahydroazulene der allgemeinen Formel I, gemäß Anspruch 1, ausgenommen 4-Methy!-7-acetyl-2.3.4.5.8.10-hexahydroazulen. 2. Hexahydroazulenes of the general formula I according to claim 1, with the exception of 4-Methy! -7-acetyl-2.3.4.5.8.10-hexahydroazulene.
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.
Die Erfindung betrifft ein neues Verfahren zur Herstellung von Hexahydroazulenen der allgemeinen Formel IThe invention relates to a new process for the preparation of hexahydroazulenes of the general formula I.
IlIl
R4 R 4
ω r'5 ω r ' 5
R1 R 1
in derin the
R' für Wasserstoff oder einen geradkettigen oder verzweigten gesättigten Kohlenwasserstoffrest mit 1 bisR 'represents hydrogen or a straight-chain or branched saturated hydrocarbon radical with 1 to
4 C-Atomen steht.
R-. RJ. R4 und R5 Wasserstoff, einen geradkettigen oder verzweigten Kohlenwasserstoffrest mit ! bis 4 C-Ato-4 carbon atoms.
R-. R J. R 4 and R 5 are hydrogen, a straight-chain or branched hydrocarbon radical with! up to 4 carbon atoms
men, 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.men, preferably methyl, cycloalkyl with 5 to 8 carbon atoms or phenyl and more
R 1 and R 2 and R 4 and R 5 together can each denote an alkylene group having 3 to 6 carbon atoms.
Weiterhin betrifft die Erfindung die neuen Verbindungen der allgemeinen Formel I, ausgenommen 4-Methyl-7-acetyl-2A4,5.8,10-hexyhydroazu!en. The invention also relates to the new compounds of the general formula I, with the exception of 4-methyl-7-acetyl-2A4,5.8,10-hexyhydroazene.
Aus Tetrahedron Letters, Band 36, Ϊ974, Seiten 3239—3240 ist das 4-Methyl-7-acetyl-23,4,5,8,10-hexyhydroazulen, also eine Verbindung der allgemeinen Formel I mit R1 = R2 =■- R4 = H und RJ = R5 = Methyl, bekannt, jedoch ist das dort beschriebene Verfahren zur Herstellung dieser Verbindung aus (l-Cyclopenten-l-ylmethylen)-triphenylphosphoran und Sorbinsäureethylester über ein Azulenderivat mit annelliertem Cyclopropanring offensichtlich durch die Verwendung schlecht zugänglicher und daher teurer Ausgangsverbindungen, teurer Reaktionshilfsstoffe, wie dem Triphenylphosphin und Methyllithium, sowie durch schlechte Ausbeuten technisch unattraktiv und auf die Herstellung dieses Individuums beschränkt.From Tetrahedron Letters, Volume 36, Ϊ974, pages 3239-3240 is 4-methyl-7-acetyl-23,4,5,8,10-hexyhydroazulene, ie a compound of the general formula I with R 1 = R 2 = ■ - R 4 = H and R J = R 5 = methyl, known, but the process described there for the preparation of this compound from (l-cyclopenten-l-ylmethylene) triphenylphosphorane and ethyl sorbate via an azulene derivative with an annellated cyclopropane ring is evident from the use poorly accessible and therefore expensive starting compounds, expensive reaction auxiliaries such as triphenylphosphine and methyllithium, and poor yields technically unattractive and limited to the production of this individual.
Die neuen Hexahydroazulene eignen sich als Riechstoffkomponenten zur Erzielung holzartiger Geruchseffekte. Darüber hinaus stellen sie Schlüsselverbindungen für die Herstellung zahlreicher bekannter und neuer Azulenderivate dar. Beispielsweise läßt sich aus M-Dimethyl-Z-acetyW.SAS.S.lO-hv.-xahydroazulen (Ia) durch einfache Grignardmethylierung und anschließende Dehydratisierung und Dehydrierung überraschenderweise in guten Ausbeuten der bekannte in der Kamille vorkommende Naturstoff Guaiazulen (IV) herstellen. Guaiazulen findet vielfach in der Heilmittel- und Kosmetikindustrie Verwendung.The new hexahydroazulenes are suitable as fragrance components to achieve woody odor effects. In addition, they provide key links for the production of numerous familiar and new ones Azulene derivatives. For example, M-dimethyl-Z-acetyW.SAS.S.10-hv.-xahydroazulene (Ia) can be passed through simple Grignard methylation and subsequent dehydration and dehydration surprisingly in produce good yields of the well-known natural product guaiazulene (IV) found in chamomile. Guaiazulene is widely used in the medicine and cosmetics industry.
OHOH
■CHj CH3MgCl1 ■ CHj CH 3 MgCl 1
H3C /^,H 3 C / ^,
(TU)(TU)
CH3 CH 3
CH3 CH 3
CH3 CH 3
Das bei dieser Synthese auftretende neue Zwischenprodukt 111 ist ein Sesquiterpen mit wertvollen Riechstoffeigenschaften. Es riecht harzig. Richtung Fichtenholz, und gleichzeitig leicht blumig.The new intermediate product 111 occurring in this synthesis is a sesquiterpene with valuable odorous properties. It smells resinous. Direction of spruce wood, and at the same time slightly flowery.
Es ist zwar aus Chemistry and Industry, Band 68 (1956). Seiten 576—77 bereits ein Verfahren zur Herstellung von Guaiazulen bekannt, jedoch hat dieses Verfahren mehr wissenschaftliche als technische Bedeutung. Es geh! aus von der wenig gebräuchlichen 2-Methyl-5-isopropyl-7-oxo-octandisäure (dort ]-Methyl-4-isopropyl-6-oxokorksäure genannt) und führt in 10 teilweise technisch sehr teuren und schwierig realisierbaren Reaktionsstufen wie einer Wolff-Kishner-Rediiktion. einer Dieckmann-Kondensation unter hoher Verdünnung, einer Michaeladdition mit Ethylcrotonat, einer Reduktion mit dem teuren Na[BHj], einer Umsetzung mit Polyphosphorsäurc sowie einer Reduktion mit LiAIH4 zu dem gewünschten Guaiazulen. Demgegenüber ermöglicht das erfindungsgemäße Verfahren eine Synthese von Guaiazulen ausgehend von technischen Großprodukten wie 2-Methyl-2-hepten-6-on (Va: Zwischenprodukt der technischen Vitamin-A-Synthese) oder Dehydrolinalool (VIa. Weltproduktion ca. 4 bis 5000 jato) in nur 8 bzw. 7 technisch üblichen Reaktionsschritten über die neuen Verbindungen l-(2'-Oxo-butan-4'-yl)-2-methyl-5-(l"-oxo-butan-3"-yl-cyclopent-l"-en (Ha) und das l,4-Dimethyl-7-aceiyl-2,3.4,5,8,10-hexahydroazulen (la). So erhält man aus Dihydrolinalool (VIa) durch Erhitzen auf ca. 200"C im Autoklaven in praktisch quantitativer Ausbeute l-Hydroxy-l-methyi-2-methylen-3-isopropfnyl-cyclopeniun (Vila), welches durch Carrol-Reaktion mit Acetessigester mit etwa 75%iger Ausbeute in l-Methyl-2-(2'-o\o-butan-4'-yl)-3-isopropenyl-l-cyclopenten (Villa) überführt und durch Hydroformylierung in Ausbeulen von ca. 86% zu der neuen Verbindung Ha umgesetzt werden kann. Die erfindungsgemäße Umsetzung von Ha zu la gelingt in Ausbeuten von über 80%. Auch die folgende Grignard-Methylierung zu dem neuen Alkohol III sowie die anschließende Dehydratisierung und Dehydrierung sind in der technischen Durchführung unproblematisch und führen in überraschend guten Ausbeuten zu Guaiazulen.It is from Chemistry and Industry, Volume 68 (1956). Pages 576-77 already disclose a process for the production of guaiazulene, but this process has more scientific than technical significance. It go! from the less common 2-methyl-5-isopropyl-7-oxo-octanedioic acid (called there-methyl-4-isopropyl-6-oxocorkic acid) and results in 10 reaction stages, some of which are technically very expensive and difficult to implement, such as a Wolff-Kishner -Reduction. a Dieckmann condensation under high dilution, a Michael addition with ethyl crotonate, a reduction with the expensive Na [BHj], a reaction with polyphosphoric acid and a reduction with LiAlH 4 to give the desired guaiazulene. In contrast, the process according to the invention enables guaiazulene to be synthesized starting from large technical products such as 2-methyl-2-hepten-6-one (Va: intermediate product of technical vitamin A synthesis) or dehydrolinalool (VIa. World production approx. 4 to 5000 tpd) in only 8 or 7 technically usual reaction steps via the new compounds l- (2'-oxo-butan-4'-yl) -2-methyl-5- (l "-oxo-butan-3" -yl-cyclopent- l "-en (Ha) and 1,4-dimethyl-7-aceiyl-2,3,4,5,8,10-hexahydroazulene (la). Dihydrolinalool (VIa) is thus obtained by heating to approx. 200" C. in the autoclave in practically quantitative yield l-hydroxy-l-methyi-2-methylene-3-isopropfnyl-cyclopeniun (Vila), which by Carrol reaction with acetoacetic ester with about 75% yield in l-methyl-2- (2 ' -o \ o-butan-4'-yl) -3-isopropenyl-1-cyclopentene (Villa) and can be converted to the new compound Ha by hydroformylation in bulges of about 86%. The inventive conversion of Ha to la succeeds in yields of over 80%. The subsequent Grignard methylation to give the new alcohol III and the subsequent dehydration and dehydrogenation are also unproblematic in technical implementation and lead to guaiazulene in surprisingly good yields.
Daß es gelang, den neuen Alkohol III in guten Ausbeuten in Guaia/.uler: zu überführen, ist überraschend, da die inChern. Abstracts 81, 1974, Referat 13 6316 η referierte Umsetzung von Guaiol(la) bei 350 C und Zink überIt is surprising that it was possible to convert the new alcohol III into guaia / .uler: in good yields the inChern. Abstracts 81, 1974, Referat 13 6316 η reported implementation of guaiol (la) at 350 C and zinc over
das Λ-Guaene (1 b) zu einem Gemisch aus S-Guaiazulen (2) und Se-Guaiazulen (3)
OHthe Λ-guaene (1 b) to a mixture of S-guaiazulene (2) and Se-guaiazulene (3)
OH
C-CH3 ^ C = CH3 C-CH 3 ^ C = CH 3
CH3 ->CH 3 ->
CH3 CH 3
■M:■ M:
(Ia)(Ia)
(Ib)(Ib)
CH3 CH 3
H3CH 3 C
(2)(2)
gemäß der entsprechenden Originalliteratur (Flavour Ind. 1974.5(7—8), Seite 186) nur mit Ausbeuten von etwa 1,5% verlief.according to the corresponding original literature (Flavor Ind. 1974.5 (7-8), page 186) only with yields of about 1.5% passed.
Es wurde gefunden, daß man die Hexahydroazulene 1 auf einem neuen bemerkenswerten Weg erhält, wenn man eine Verbindung der allgemeinen Forme! 11It has been found that the hexahydroazulenes 1 are obtained in a remarkable new way if to connect the general form! 11th
(H)(H)
R2 R 2
gegebenenfalls in einem unter den Reaktionsbedingungen inerten Lösungsmittel in Gegenwart eines Dehydratisiei ungskatalysators auf Temperaturen von 100 bis 500° C, vorzugsweise 150 bis 2500C, erhitzt.optionally in an inert solvent under the reaction conditions in the presence of a Dehydratisiei ungskatalysators to temperatures of 100 to 500 ° C, preferably 150 to 250 0 C, heated.
Es war überraschend, daß die Verbindungen der Forme! 11 unter den erfindungsgemäßen Reaktionsbedingungen nicht, wie erwartet werden konnte, lineare iCondensationsprodukte liefern, sondern in glatter Reaktion zu einem l-Acyl-Siebenringcyclisieren.It was surprising that the connections of the Form! 11 under the reaction conditions according to the invention do not, as could be expected, give linear condensation products, but rather in smooth reaction a seven-membered l-acyl cyclization.
Die als Ausgangsstolie für das erfindungsgemäße Verfahren benötigten Verbindungen der Formel H sind neue Stoffe. Sie können beispielsweise auf die aus dem folgenden Reaktionsscheina wiedergegebene Weise aus bekannten Vorprodukten hergestellt werden (siehe hierzu auch DE-OS 24 47 170)The compounds of the formula H required as starting materials for the process according to the invention are new fabrics. For example, you can do the following: known preliminary products are produced (see also DE-OS 24 47 170)
R'R '
C2H,C 2 H,
OHOH
ROOCCH2-COR^ROOCCH 2 -COR ^
Bevorzugte Ausgangsverbindungen der Formel Il und daher auch bevorzugte llexahydroazulene der Formel
I sind solche, in denen R1 für Methyl. Äthyl, Isopropyl. Phenyl R2, R', R4 und R'1 für Methyl. Äthyl oder R1 und
R2 bzw. R4 und R1* zusammen für Propylen-( 1,3) oder Butylen-( 1,3) steheii.
Genannt seien beispielsweise:Preferred starting compounds of the formula II and therefore also preferred llexahydroazulenes of the formula I are those in which R 1 is methyl. Ethyl, isopropyl. Phenyl R 2 , R ', R 4 and R' 1 for methyl. Ethyl or R 1 and R 2 or R 4 and R 1 * together stand for propylene- (1,3) or butylene- (1,3).
For example:
I -(2'-Oxobutan-4'-yl)-2-methyl-5-( 1 "-oxobutan-3"-yl)-c>clopent-1 -en.
1 -(2'-Oxobutan-4'-yl)-5-( I "-oxobutan-3"-yl)-cyclopen t-1 -en,
1 -(2'-Oxobutan-4'-yl) -2-pheny!-5-( 1 "-oxobutan-3"-y l)-eyclopcnt-1 -en.
l-(2'-Oxobutan-4'-yl)-2-methyl-5-(2"-formyi-cyclohex-l"-cn-l"-yl)-cyclopent-l-en und
1 -(2'-Oxobutan-4'-yl)-2J-(propy!en-1 ",3")-5-( 1 '"-oxobutan-3'"-yl)-cyclopent-1 -en
(besser: 5-(r-Oxobutan-3'-yl)-6-(2"-oxobutan-4'-yl-bicyclo[3.3.0]oci-6en).I - (2'-Oxobutan-4'-yl) -2-methyl-5- (1 "-oxobutan-3" -yl) -c> clopent-1-ene.
1 - (2'-Oxobutan-4'-yl) -5- (I "-oxobutan-3" -yl) -cyclopen t-1-en,
1 - (2'-Oxobutan-4'-yl) -2-pheny! -5- (1 "-oxobutan-3" -yl) -eyclopcnt-1-en.
1- (2'-Oxobutan-4'-yl) -2-methyl-5- (2 "-formyi-cyclohex-1" -cn-1 "-yl) -cyclopent-1-en and
1 - (2'-Oxobutan-4'-yl) -2J- (propy! En-1 ", 3") - 5- (1 '"-oxobutan-3'" -yl) -cyclopent-1-en
(better: 5- (r-Oxobutan-3'-yl) -6- (2 "-oxobutan-4'-yl-bicyclo [3.3.0] oci-6en).
AU unter den Reakiionsbedingungen inerte Lösungsmittel könncrs crfindungsgcmaG Kohlenwasserstoffe, wie Dekahydronaphthalin, Tetrahydronaphthalin. Naphthalin, Paraffinöl, Xylol, Toluol, hochsiedende Äther wie Dibutyläther sowie Siliconöl, N-Methylpyrrolidon, Dimethylformamid und Dimethylsulloxid verwendet werden.Solvents which are inert under the reaction conditions can be used to identify hydrocarbons such as Decahydronaphthalene, tetrahydronaphthalene. Naphthalene, paraffin oil, xylene, toluene, high-boiling ethers such as Dibutyl ether and silicone oil, N-methylpyrrolidone, dimethylformamide and dimethyl sulfide can be used.
Als De.iydratisierungskatalysatoren kommen die üblicherweise für Wass,../ paltungen unter Ringschluß verwendeten Mittel in Betracht. Es kommen neutral reagierende Katalysatoren, wie die Oxide von Zink. Aluminium, Thorium, Wolfram (blaues Wolframoxid) und Titan, aber auch saure Katalysatoren, wie Kiesclgel. Borsäure, Phosphorsäure, Schwefelsäure oder deren Salze sowie Salze, wie Piperidinacetat, in Betracht. Bevorzugt werden Metalloxide, wie ZnO, ThOj. WOj, TiOj und AIiOj. insbesondere aktiviertes ZnO. Bezüglich weiterer Einzelheiten über die Dehydratisierungsk.italysatoren und deren Herstellung verweisen wir auf Houben-Weyl. »Methoden der organischen Chemie«. Band 4/2, Seiten 209 bis 218.The dehydration catalysts usually used for water splitting with ring closure funds used into consideration. There are neutrally reacting 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 salts thereof and salts such as piperidine acetate are suitable. Preferred metal oxides such as ZnO, ThOj. WOj, TiOj and AIiOj. in particular activated ZnO. In terms of For further details on the dehydration analyzers and their manufacture, 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 Il 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 Il bei der Reaktionstemperatur kontinuierlich über einen geeigneten Festbettkatalysator. Je nach der Art der Durchführung des Verfahrens ist die Reaktionstemperatur höher oder niedriger. Wird die Verbindung der Formel II in Gegenwart von einem inerten Lösungsmittel und einem suspendierten oder gelösten Katalysator erhitzt, so sind Temperaturen von 100 bis 50O0C, 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.To carry out the process according to the invention, either the compound of the formula II or its solution in an inert solvent is added the catalyst in the form of powder. Grains or crystals and the whole thing is heated to the reaction temperature, or the compound of the formula II is passed continuously over a suitable fixed bed catalyst at the reaction temperature. Depending on how the process is carried out, the reaction temperature is higher or lower. If the compound of the formula II is heated in the presence of an inert solvent and a suspended or dissolved catalyst, temperatures of 100 to 50O 0 C, preferably from 150 to 250 0 C, are necessary. If, on the other hand, the compound of the formula II is passed continuously over a fixed bed contact, temperatures of 170 to 270 ° C. are preferably 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 of 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 approach.
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 für zahlreiche neue und bekannte Azulenderivate. The method according to the invention opens up a new route to be used in the medicinal products and cosmetics industry usable compounds of the azulene series. The new hexahydroazulenes are characterized by unusual Fragrance properties and are valuable intermediates for numerous new and well-known azulene derivatives.
Die folgenden Beispiele sollen das Verfahren erläutern.The following examples are intended to illustrate the process.
22g (0.1 Mol) l-(2'-O.\o-butiiri-4'-yH-2-methy!-5-(l"-oxo-butan-J"-yl)-cyclopenl-l-cn werden in 100 ml Dekahvdronaphthalin gelöst und mit aktiviertem IO g Zinkoxid versetzt. Unter kräftigem Rühren wird dann auf 190 C erhit/t und durch t:a<n.liromaiographisehe Analyse der Reaktionsverlauf registriert. Nach einer Stunde ist kein Ausgangsmaterial mehr nachweisbar. Man filtriert vom Zinkoxid ab und unterwirft das ('iltrat einer fraktionierten Destillation, wobei i7 y l.4-Dimethy!-7acetyl-2.3.4.5.8.l()-hexahydroa/ulen erhalten werden. Die Ausbeute betragt 8 JV-O der Theorie.22g (0.1 mol) l- (2'-O. \ O-butiiri-4'-yH-2-methy! -5- (l "-oxo-butan-I" -yl) -cyclopenl-l-cn in 100 ml Dekahvdronaphthalin dissolved and mixed with activated 10 g zinc oxide. Then stir vigorously 190 C and recorded by t: a <n.liromaiographisehe analysis of the course of the reaction. After an hour is no more starting material detectable. The zinc oxide is filtered off and the filtrate is subjected to a fractional distillation, i7 y 1.4-Dimethy! -7acetyl-2.3.4.5.8.l () - hexahydroa / ulen are obtained. the Yield is 8 JV-O of theory.
Kp. = 42bis45 C/0.01 mbar:/r" = l.-5l92;Geruch: hol/ig (kiefernhol/artig).Bp. = 42 to 45 C / 0.01 mbar: / r "= l.-5l92; smell: hol / ig (pine hol / like).
B e i s ρ i e I e 2 bis 7B e i s ρ i e I e 2 to 7
22g (0.1 Mol) l-(2'-Oxobutan-4-vl)-2-methyl-5-(l"-o\o-butan-3"-yl)-cvclopcnt-l-en werden in 100ml Dekahydronaphthalin gelöst und mit jeweils 10 g des in der folgenden Tabelle angegebenen Katalysators verset/i. Anschließend wird unter kräftigem Rühren auf 190 C erhitzt und durch gasehromatographische 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 M-Dimethyl^-acetyl^JAS.S.lO-hexahydroazulen angegeben.22 g (0.1 mol) of 1- (2'-oxobutane-4-vl) -2-methyl-5- (l "-o \ o-butan-3" -yl) -cvclopcnt-l-en are dissolved in 100 ml of decahydronaphthalene dissolved and mixed with 10 g of the catalyst given in the table below. The mixture is then heated to 190 ° C. with vigorous stirring and the gas chromatographic analysis of the Reaction progress registered. After no more starting material was detectable. became the catalyst filtered off and the filtrate fractionally distilled. The following table shows the response time as well as the Yields of M-dimethyl ^ -acetyl ^ JAS.S.lO-hexahydroazulene indicated.
Katalysatorcatalyst
Zinkoxid-RotsiegelZinc Oxide Red Seal
ZnO-Mcrck-reinstZnO-Mcrck-pure
TiO,TiO,
ThO2 ThO 2
WOjWOj
*) Noch 10% Ausgangsmateriul im Reaklionsgemisch.
**) Bildung eines Nebenprodukts.dessen Struktur noch mehl ermittelt werden konnte.*) 10% starting material left in the reaction mixture.
**) Formation of a by-product, the structure of which could still be determined.
22 g (0.1 Mol) l-(2'-Oxo-butan-4'-yI)-2-methyl-5-(l"-oxo-butan-3"-yl)-eyclopcnt-1-en werden in I50ml Xylol gelöst, mit 0.85 g(0.0l MuI) 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. l.4-Dimethyl-7-acetyl 2.3.4.5.8.10-hexahydroazulen wird dabei mit ca. 36%iger Ausbeute erhalten.22 g (0.1 mol) of 1- (2'-oxo-butan-4'-yI) -2-methyl-5- (l "-oxo-butan-3" -yl) -eyclopcnt-1-en are dissolved in 150 ml Xylene dissolved, treated with 0.85 g (0.0l MuI) of piperidine and 0.7 g (0.012 mol) of glacial acetic acid and in one for water removal processes suitable apparatus heated to boiling for 7 hours. Then it is allowed to cool and washed several times with water and subjects the organic phase to a fractional distillation. 1,4-Dimethyl-7-acetyl 2.3.4.5.8.10-hexahydroazulene is obtained with a yield of about 36%.
44g (0.2 Mol) l-(2'-Oxo-butan-4'-yl)-2-methyl-5-(l"-oxo-butan-3"-yl)-cyclopent-l-en werden mit lOg aktiviertem Zinkoxid versetzt und unter Rühren 30 Minuten isuf 220 bis 2300C erhitzt. Man filtriert nach Abkühlen vom Zinkoxid ab und unterwirft das Filtrat einer fraktionierten Destillation, wobei 1.4-Dimethyl-7-acetyl 23,4,5.8.10-hexahydroazulen in 62%iger Ausbeute isoliert wird.44g (0.2 mol) of 1- (2'-oxo-butan-4'-yl) -2-methyl-5- (l "-oxo-butan-3" -yl) -cyclopent-1-ene are activated with 10 g zinc oxide and heated 30 minutes with stirring Isuf 220 to 230 0 C. After cooling, the zinc oxide is filtered off and the filtrate is subjected to fractional distillation, 1,4-dimethyl-7-acetyl 23,4,5.8.10-hexahydroazulene being isolated in 62% yield.
Beispiel 10Example 10
40g (0.15 Mol) l-(2'-Oxo-butan-4'-yl)-2-mcthyl-5-(2"-formylcyL-lopentan-l"-yl)-cyclopent-l-en werden in 100 ml Tetralin gelöst, mit IO g aktiviertem Zinkoxid versetzt und unter kräftigem Rühren eine Stunde auf 200 C erhitzt. Man filtriert anschließend vom Zinkoxid ab und unterwirft das Filtrat einer fraktionierten Destillation, π wobei 25g l-Mcthyl-4,5-(propylcn-l', 3')-7-acetyl-2.3.4.5,8.10-hexahydroa/ulen erhalten werden. Die Ausbeute beträgt 67% der Theorie.40g (0.15 mol) of 1- (2'-oxo-butan-4'-yl) -2-methyl-5- (2 "-formylcyL-lopentan-l" -yl) -cyclopent-1-en are in 100 ml of tetralin dissolved, mixed with 10 g of activated zinc oxide and heated to 200 ° C. for one hour while stirring vigorously heated. The zinc oxide is then filtered off and the filtrate is subjected to fractional distillation, π 25 g of 1-methyl-4,5- (propylcn-1 ', 3') - 7-acetyl-2.3.4.5.8.10-hexahydroa / ulen are obtained. The yield is 67% of theory.
Kp. = 96bis98°C/0.01 mbar./in = 1.5319:Geruch: balsamig, holzig.erdig.Bp. = 96 to 98 ° C / 0.01 mbar./in = 1.5319: Smell: balsamic, woody, earthy.
CHOCHO
50g (0,2 Mol) l-(2'-Oxo-butan-4'-yl)-2,3-(propylen-l".3")-(r"-oxo-butan-3'"-yl)-cyclopent-l-en werden in 50 ml Tetrahydronaphthalin gelöst und mit 20 g aktiviertem Zinkoxid aktiviert versetzt. Unter kräftigem Rühren wird eine Stunde auf 205°C 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.! 0-hexahydroazulen. Das entspricht einer Ausbeute von 58% der Theorie.50g (0.2 mol) of l- (2'-oxo-butan-4'-yl) -2,3- (propylene-l ".3") - (r "-oxo-butan-3 '" - yl ) -cyclopent-l-en are used in 50 ml of tetrahydronaphthalene dissolved and mixed with 20 g of activated zinc oxide activated. While stirring vigorously is heated to 205 ° C for one hour, then filtered off and the filtrate from a fractional distillation subject. 27 g of 1,2- (propylene-1 '.3') - 4-methyl-7-acetyl-2,3.4.5,8.! 0-hexahydroazulene. Corresponding a yield of 58% of theory.
Kp.= 102bisl05°C/0.13mbar:ni' = l,5285:Geruch: würzig-holzig.Bp. = 102 bisl05 ° C / 0.13 mbar: ni '= 1.5285: smell: spicy-woody.
Claims (1)
O1. Process for the preparation of hexahydroazulenes of the general formula I.
O
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2447169A DE2447169C2 (en) | 1974-10-03 | 1974-10-03 | Process for the preparation of hexahydroazulenes and new hexahydroazulenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2447169A DE2447169C2 (en) | 1974-10-03 | 1974-10-03 | Process for the preparation of hexahydroazulenes and new hexahydroazulenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2447169A1 DE2447169A1 (en) | 1976-04-15 |
| DE2447169C2 true DE2447169C2 (en) | 1984-08-09 |
Family
ID=5927404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2447169A Expired DE2447169C2 (en) | 1974-10-03 | 1974-10-03 | Process for the preparation of hexahydroazulenes and new hexahydroazulenes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2447169C2 (en) |
-
1974
- 1974-10-03 DE DE2447169A patent/DE2447169C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2447169A1 (en) | 1976-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2718549C3 (en) | New fragrances | |
| DE2315640C3 (en) | Process for the preparation of unsaturated cycloaliphatic ketones and the resulting cycloaliphatic diketones and their enolates | |
| DE2455761C2 (en) | Use of hydrogenated methyl ionones and their derivatives as fragrances, processes for their preparation and new hydrogenated methyl ionone derivatives | |
| DE2353145C3 (en) | Process for the preparation of oxo compounds | |
| CH633508A5 (en) | METHOD FOR PRODUCING NEW CYCLOALIPHATIC SATURED AND UNSATURATED KETONES USED AS AROMA AND FRAGRANCES. | |
| DE2462724C3 (en) | Bicyclo [2,2,2] octane derivatives and processes for their preparation | |
| EP0400509A1 (en) | Process for the production of muscone, intermediates for this process and their preparation | |
| DE3346213C2 (en) | Fragrance mixture, process for their preparation and compositions containing them | |
| DE2252864A1 (en) | POLYCYCLIC COMPOUNDS | |
| DE2141309C3 (en) | ||
| EP0044413B1 (en) | 3,6-dimethyl-oct-1-in-3-ols and -oct-1-en-3-ols and derivatives thereof, their use as fragrances and process for preparing 3,6-dimethyl-octan-3-ol | |
| DE2447169C2 (en) | Process for the preparation of hexahydroazulenes and new hexahydroazulenes | |
| DE2333265A1 (en) | NEW NITRILE | |
| CH625494A5 (en) | ||
| DE2918107A1 (en) | TRICYCLO-ALPHA, BETA-UNSATATULATED-ALDEHYDE | |
| DE69812997T2 (en) | REACTION OF ALKENES WITH EPOXIES, THE PRODUCTS THEREOF AND THEIR USE AS A FRAGRANCE | |
| DE2359659A1 (en) | NEW FRAGRANCE COMPOUNDS | |
| EP0093425B1 (en) | Unsaturated cyclic ketones | |
| DE1443594A1 (en) | Process for the preparation of esters of vitamin A acid | |
| DE2416584A1 (en) | HEXAMETHYLTETRACOSANE DIOL DERIVATIVES AND PROCESS FOR THE PREPARATION | |
| DE2435981A1 (en) | PROCESS FOR PRODUCING ETHYLENE-LIKE COMPOUNDS AND COMPOUNDS PRODUCED BY THIS PROCESS | |
| EP0051260B1 (en) | Methyl-4-oxatricyclo (5.2.1.02,6)dec-8-en-3-on and methyl-4-oxatricyclo (5.2.1.02,6)decan-3-on, their preparation and their use as perfume articles | |
| DE2844155A1 (en) | 1,7-OCTADIEN-3-ON AND THE METHOD OF ITS MANUFACTURING | |
| DE3020298C2 (en) | Process for the preparation of 2,2,4,5,5-pentamethyl-3-formyl-3-pyrroline | |
| DE2730176A1 (en) | METHOD FOR PRODUCING ALDEHYDES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8110 | Request for examination paragraph 44 | ||
| D2 | Grant after examination | ||
| 8364 | No opposition during term of opposition | ||
| 8330 | Complete disclaimer |