WO1993002997A1 - Method of preparing cyclopentanones - Google Patents

Method of preparing cyclopentanones Download PDF

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WO1993002997A1
WO1993002997A1 PCT/EP1992/001630 EP9201630W WO9302997A1 WO 1993002997 A1 WO1993002997 A1 WO 1993002997A1 EP 9201630 W EP9201630 W EP 9201630W WO 9302997 A1 WO9302997 A1 WO 9302997A1
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catalyst
ruthenium
cyclopentanones
carbon monoxide
inert solvent
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PCT/EP1992/001630
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German (de)
French (fr)
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Peter Eilbracht
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Henkel Kommanditgesellschaft Auf Aktien
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    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters

Definitions

  • the invention relates to a one-stage process for the preparation of cyclopentanones by rearrangement of corresponding bisallyl, allyl vinyl ether or 4-pentenals in an inert solvent in the presence of carbon monoxide and a ruthenium catalyst at elevated temperature.
  • hydroacylation Reactions of olefins with aldehydes to ketones in the presence of certain metal catalysts are known under the name hydroacylation.
  • the intramolecular variant of this reaction in particular the rearrangement of 4-pentenals to the corresponding cyclopentanones, has particularly aroused the interest of various research groups. This latter cyclizing hydroacylation is referred to below as the CHA reaction.
  • Sakai et al. have resorted to the CHA response in prostaglandin synthesis; however, they required equimolar amounts of tin chloride or tris (triphenylphosphine) rhodium I chloride ("Wilkinson's catalyst”) [Tetrahedron Lett. 1971, 1287].
  • the 4-pentenals required to carry out the CHA reaction can be prepared from allyl vinyl ethers by thermal Claisen rearrangement.
  • Boeckman, Jr. et al. Obtained 3,3-dimethyl-4-pentenal by heating (3-methyl) -2-butenyl vinyl ether to about 150 ° C. for 24 hours [J.Am.Chem.Soc. 1982 (104) 1033].
  • the prior art described thus opens up the possibility of producing cyclopentanones in a two-stage process, the first step of which is a thermal Claisen rearrangement of allyl vinyl ethers or a ruthenium-catalyzed Claisen rearrangement of bisallyl ethers and the second step of the reaction of the 4- Pentenale consists of a rhodium-catalyzed CHA reaction.
  • Cyclopentanones are interesting raw materials for further organic syntheses. There is therefore a constant need for methods that facilitate preparative access to these substances. In particular, the task was to develop a method by which cyclopentanones in a one-step process directly accessible from bisallyl ethers or allyl vinyl ethers.
  • cyclopentanones with up to four alkyl radicals each having 1 to 3 carbon atoms, in which one carbon atom bears at least one hydrogen atom in the ⁇ position to the carbonyl group can be prepared in one step in an intramolecular reaction, that one rearranges corresponding bisallyl ether, allyl vinyl ether or 4-pentenals in an inert solvent in the presence of carbon monoxide and a ruthenium catalyst at elevated temperature.
  • the subject of the invention is therefore a process for the preparation of cyclopentanones with up to four alkyl radicals each having 1 to 3 carbon atoms, in which a carbon atom in the ⁇ -position to the carbonyl group carries at least one hydrogen atom, by rearrangement of corresponding bisallyl ether, allyl vinyl ether or 4-pentenals in an inert solvent in the presence of carbon monoxide or a gas containing carbon monoxide and a ruthenium catalyst at elevated temperature.
  • the process according to the invention has the advantage that the isomerization of bisallyl ethers to allyl vinyl ethers, its rearrangement to 4-pentenals and finally its further rearrangement to the desired cyclopentanones is effected in one step in an intramolecular hydroacylation and is carried out in a simple one-pot reaction can.
  • cyclopentanones IV can be prepared in this way from bisallyl ethers (I), allyl vinyl ethers (II), 4-pentenals III or mixtures of these starting materials.
  • Soluble ruthenium complexes are preferably used as catalysts in the process according to the invention. Ruthenium 0 1 or ruthenium II complexes containing phosphine ligand are particularly suitable. In a particularly preferred embodiment of the invention, tris (triphenylphosphine) ruthenium II dichloride, (PPh 3 ) 3 RuCl 2 is used as catalyst.
  • the concentration of the catalyst in the reaction mixture is not subject to any particular restrictions, but 0.5 to 20% by weight, based on the starting material to be rearranged, is preferred. It is particularly advantageous to adjust the concentration of the catalyst in the reaction mixture to values in the range from 5 to 10% by weight.
  • the catalyst can be reused several times in the course of the process according to the invention without having to accept losses in terms of the yield. It has been shown that the recovered catalyst complex as RuCl 2 (CO) 2 (PPh 3 ) 2 [Wilkinson et al., J. Inorg. Nucl. Chem. 1966 [28] 945] is obtained. This is also catalytically active and can - if desired several times - be used in the process according to the invention.
  • the intramolecular hydroacylation is preferably carried out in the process according to the invention at temperatures of 180 to 250 ° C. Higher temperatures do not result in a significant increase in yield and at most involve the risk of decomposition of the starting materials or intermediate products. Reaction temperatures in the range from 190 to 220 ° C. have proven to be particularly favorable.
  • the rearrangement according to the invention is carried out at carbon monoxide pressures of 5 to 100 bar, preferably at 10 to 60 bar.
  • the process according to the invention is carried out in an inert solvent.
  • Aliphatic, cycloaliphatic or aromatic hydrocarbons for example, are suitable for this purpose and, if desired, can also carry halogen substituents.
  • solvents which are free of halogens and / or aromatic groups are particularly preferred for reasons of increased safety for personnel and the environment.
  • aliphatic and cycloaliphatic hydrocarbons that are liquid at room temperature, for example cyclohexane or octane.
  • the solvent is used in an anhydrous and air-free form.
  • the starting material, solvent and catalyst are in a pressure reactor, e.g. an autoclave, and this mixture is brought into contact with carbon monoxide.
  • the reaction mixture is stirred at elevated temperature, reaction times of the order of 5 to 20 hours being generally chosen. After the reaction is worked up in the usual manner.
  • RuCl 2 (PPh 3 ) 3 according to Wilkinson et al. (J. Inorg. Nucl. Chem.
  • n-octane Merck, 99% (treated with P 2 O 10 , degassed according to the "freezing and thawing" method under evacuation or argon atmosphere)
  • (3-methyl-2-butenyl) alkyl ether represented by Reuter and Salomon (J.
  • the mixture was allowed to cool, the yellowish-colored reaction mixture was decanted from precipitated acicular crystals and washed with pentane.
  • the decanted solution and the pentane phase were placed on a silica gel column, the n-octane was removed by washing with 200 ml of n-pentane, and the crude product was then eluted with 200 ml of diethyl ether.
  • the ether was removed on a rotary evaporator at 35 ° C./200 Torr and the residue was distilled in a Kugelrohr distillation apparatus at 70 ° C. 60 Torr.
  • the colorless crystals obtained by decanting [105 mg / 0.14 mmol; Mp 290-316 ° C] were spectroscopically identified as RuCl 2 (CO) 2 (PPh 3 ) 2 (IR, NMR, MS).
  • Example 2 Analogously to Example 2, the reaction was carried out at a CO pressure of 50 bar and a reaction time of 18 hours: 90 mg (0.141 mmol) dodecacarbonyltriruthemium, Ru 3 (CO) 12 , 950 mg (8.47 mmol) (3-methyl-2 -butenyl) vinyl ether, 25 ml n-octane.
  • the crude product was first worked up by distillation at 45 ° C./760 torr (spherical tube), the solvent being obtained in a mixture with 3,3-dimethylbutene. Chromatography of the residue on silica gel with n-pentane eluted successively with n-octane and then the orange-red dodecacarbonyltriruthenium. By concentrating the eluate and drying in an oil pump vacuum, 40.6 mg (45%) of the catalyst were recovered. The more polar fractions of the chromatography were eluted with 200 ml of diethyl ether, the ether was removed on a rotary evaporator and the residue was distilled in a Kugelrohr distillation apparatus.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention concerns a method of preparing cyclopentanones containing up to four alkyl groups, each with 1 to 3 C-atoms, a C-atom in the β-position with respect to the carbonyl group having at least one hydrogen atom. Such compounds can be prepared in a single step by an intramolecular rearrangement reaction in which appropriate bis-allyl ethers, allyl, vinyl ethers or 4-pentenals are heated at elevated temperatures in an inert solvent in the presence of carbon monoxide and a ruthenium catalyst.

Description

"Verfahren zur Herstellung von Cyclopentanonen"  "Process for the preparation of cyclopentanones"
Die Erfindung betrifft ein einstufiges Verfahren zur Herstellung von Cyclopentanonen durch Umlagerung entsprechender Bisallyl-, Allyl-vinyl-ether oder 4-Pentenale in einem inerten Lösungsmittel in Gegenwart von Kohlen- monoxid und eines Ruthenium-Katalysators bei erhöhter Temperatur. The invention relates to a one-stage process for the preparation of cyclopentanones by rearrangement of corresponding bisallyl, allyl vinyl ether or 4-pentenals in an inert solvent in the presence of carbon monoxide and a ruthenium catalyst at elevated temperature.
Umsetzungen von Olefinen mit Aldehyden zu Ketonen in Gegenwart bestimmter Metall-Katalysatoren sind unter der Bezeichnung Hydroacylierung bekannt. Die intramolekulare Variante dieser Reaktion, insbesondere die Umlagerung von 4-Pentenalen zu den entsprechenden Cyclopentanonen, hat in besonderem Maße das Interesse verschiedener Forschungsgruppen geweckt. Diese letztgenannte cyclisierende Hydroacylierung wird im folgenden als CHA-Reaktion bezeichnet. Reactions of olefins with aldehydes to ketones in the presence of certain metal catalysts are known under the name hydroacylation. The intramolecular variant of this reaction, in particular the rearrangement of 4-pentenals to the corresponding cyclopentanones, has particularly aroused the interest of various research groups. This latter cyclizing hydroacylation is referred to below as the CHA reaction.
Sakai et al. haben auf die CHA-Reaktion im Zuge von Prostaglandinsynthesen zurückgegriffen; allerdings benötigten sie äquimolare Mengen von Zinnchlorid bzw. Tris(triphenylphosphin)rhodiumIchlorid ("Wilkinson-Katalysator") [Tetrahedron Lett. 1971, 1287]. Sakai et al. have resorted to the CHA response in prostaglandin synthesis; however, they required equimolar amounts of tin chloride or tris (triphenylphosphine) rhodium I chloride ("Wilkinson's catalyst") [Tetrahedron Lett. 1971, 1287].
Später haben Larock et al. die CHA-Reaktion eingehender untersucht und gefunden, daß die in situ aus dimerem Bis(cycloocten)rhodiumIdichlorid und Trisarylphosphinen hergestellten RhodiumI-Komplexe dabei die effektivsten Katalysatoren darstellen. Darüber hinaus fanden sie, daß die Ausbeuten der CHA-Reaktion erheblich gemindert werden, wenn 4-Pentenal in bestimmten Positionen, insbesondere in 2- und 5-Stellung substituiert ist [J.Am.Chem.Soc. 1980 (102) 190 und US-Patent 4288613]. Later Larock et al. the CHA reaction was investigated in more detail and found that the rhodium I complexes prepared in situ from dimeric bis (cyclooctene) rhodium I dichloride and trisarylphosphines are the most effective catalysts. In addition, they found that the yields of the CHA reaction are considerably reduced if 4-pentenal is substituted in certain positions, in particular in the 2- and 5-positions [J.Am.Chem.Soc. 1980 (102) 190 and U.S. Patent 4,288,613].
Vor kurzem haben Bosnich et al. gezeigt, daß mit in situ hergestellten RhodiumI-Katalysatoren, die bidentate Phosphin-Liganden wie "diphos" ent halten, die CHA-Reaktion auch bei substituierten 4-Pentenalen unter milden Bedingungen und hohen Ausbeuten verläuft [Organometallics 1988, 936]. Recently, Bosnich et al. showed that with rhodium I catalysts prepared in situ, the bidentate phosphine ligands such as "diphos" ent consider that the CHA reaction proceeds even under substituted 4-pentenals under mild conditions and high yields [Organometallics 1988, 936].
Die zur Durchführung der CHA-Reaktion erforderlichen 4-Pentenale lassen sich durch thermische Claisen-Umlagerung aus Allylvinylethern herstellen. So haben beispielsweise Boeckman, Jr. et al. 3,3-Dimethyl-4-pentenal durch 24-stündiges Erhitzen von (3-Methyl)-2-butenyl-vinylether auf etwa 150 °C erhalten [J.Am.Chem.Soc. 1982 (104) 1033]. The 4-pentenals required to carry out the CHA reaction can be prepared from allyl vinyl ethers by thermal Claisen rearrangement. For example, Boeckman, Jr. et al. Obtained 3,3-dimethyl-4-pentenal by heating (3-methyl) -2-butenyl vinyl ether to about 150 ° C. for 24 hours [J.Am.Chem.Soc. 1982 (104) 1033].
Zur Herstellung ungesättigter Ketone und Aldehyde durch Claisen-Umlagerung von Bisally-ethern sowie zur intermolekularen Hydroacylierung von Olefinen sind auch spezielle Ruthenium-Katalysatoren herangezogen worden. Special ruthenium catalysts have also been used for the production of unsaturated ketones and aldehydes by Claisen rearrangement of bisallyl ethers and for the intermolecular hydroacylation of olefins.
So berichten R.G.Salomon et al., daß Tris(triphenylphosphin)rutheniumll- dichlorid die Umlagerung unsymmetrischer Bisallylether zu ungesättigten Ketone und Aldehyden katalysiert [J.Org.Chem. 1977 (42) 3360]. R.G. Salomon et al. Report that tris (triphenylphosphine) ruthenium III dichloride catalyzes the rearrangement of unsymmetrical bisallyl ethers to unsaturated ketones and aldehydes [J.Org.Chem. 1977 (42) 3360].
Y.Watanabe et al. fanden, daß der Phosphinligand-freie Ruthenium0-Komplex Dodecacarbonyltriruthenium, ein orangeroter Feststoff, die intermolekulare Hydroacylierung von Olefinen mit Aldehyden zu unsymmetrischen Ketonen katalysiert. Als Aldehyde wurden dabei ausschließlich aromatische Aldehyde oder Formaldehyd eingesetzt, also Aldehyde, die in α-Stellung keinen Wasserstoff enthalten [Tetr. Lett. 1987 (28) 6229]. Y. Watanabe et al. found that the phosphine ligand-free ruthenium 0 complex dodecacarbonyltriruthenium, an orange-red solid, catalyzes the intermolecular hydroacylation of olefins with aldehydes to give asymmetric ketones. Only aromatic aldehydes or formaldehyde, ie aldehydes which contain no hydrogen in the α position, were used as aldehydes [Tetr. Lett. 1987 (28) 6229].
Der beschriebene Stand der Technik eröffnet somit die Möglichkeit, Cyclopentanone in einem zweistufigen Verfahren herzustellen, dessen erster Schritt in einer thermischen Claisen-Umlagerung von Allylvinylethern oder einer Ruthenium-katalysierten Claisen-Umlagerung von Bisallylethern und dessen zweiter Schritt in der Umsetzung der dabei erhaltenen 4-Pentenale in einer Rhodiuml-katalysierten CHA-Reaktion besteht. The prior art described thus opens up the possibility of producing cyclopentanones in a two-stage process, the first step of which is a thermal Claisen rearrangement of allyl vinyl ethers or a ruthenium-catalyzed Claisen rearrangement of bisallyl ethers and the second step of the reaction of the 4- Pentenale consists of a rhodium-catalyzed CHA reaction.
Cyclopentanone sind interessante Rohstoffe für weitere organische Synthesen. Es besteht daher ein ständiger Bedarf nach Methoden, die den präparativen Zugang zu diesen Substanzen erleichtern. Insbesondere bestand die Aufgabe, ein Verfahren zu entwickeln, nach dem Cyclopentanone in einem einstufigen Verfahren direkt aus Bisallylethern bzw. Allyl-vinyl- ethern zugänglich sind. Cyclopentanones are interesting raw materials for further organic syntheses. There is therefore a constant need for methods that facilitate preparative access to these substances. In particular, the task was to develop a method by which cyclopentanones in a one-step process directly accessible from bisallyl ethers or allyl vinyl ethers.
Es wurde nun gefunden, daß sich Cyclopentanone mit bis zu vier Alkylresten mit je 1 bis 3 C-Atomen, bei denen ein C-Atom in ß-Stellung zur Carbonylgruppe mindestens ein Wasserstoffatom trägt, in einem Schritt in einer intramolekularen Reaktion dadurch herstellen lassen, daß man entsprechende Bisallylether, Allyl-vinyl-ether oder 4-Pentenale in einem inerten Solvens in Gegenwart von Kohlenmonoxid und einem Ruthenium-Katalysator bei erhöhter Temperatur umlagert. It has now been found that cyclopentanones with up to four alkyl radicals each having 1 to 3 carbon atoms, in which one carbon atom bears at least one hydrogen atom in the β position to the carbonyl group, can be prepared in one step in an intramolecular reaction, that one rearranges corresponding bisallyl ether, allyl vinyl ether or 4-pentenals in an inert solvent in the presence of carbon monoxide and a ruthenium catalyst at elevated temperature.
Erfindungsgegenstand ist daher ein Verfahren zur Herstellung von Cyclopentanonen mit bis zu vier Alkylresten mit je 1 bi s 3 C-Atomen , bei denen ein C-Atom in ß-Stellung zur Carbonylgruppe mindestens ein Wasserstoffatom trägt, durch Umlagerung entsprechender Bisallyl-ether, Allyl-vinylether oder 4-Pentenale in einem inerten Solvens in Gegenwart von Kohlenmonoxid oder einem kohlenmonoxid-haltigen Gas und eines Ruthenium-Katalysators bei erhöhter Temperatur. The subject of the invention is therefore a process for the preparation of cyclopentanones with up to four alkyl radicals each having 1 to 3 carbon atoms, in which a carbon atom in the β-position to the carbonyl group carries at least one hydrogen atom, by rearrangement of corresponding bisallyl ether, allyl vinyl ether or 4-pentenals in an inert solvent in the presence of carbon monoxide or a gas containing carbon monoxide and a ruthenium catalyst at elevated temperature.
Das erfindungsgemäße Verfahren hat den Vorteil, daß in einem Schritt die Isomerisierung von Bisallylethern zu Allyl-vinyl-ethern, dessen Umlagerung zu 4-Pentenalen und schließlich dessen weitere Umlagerung zu den gewünschten Cyclopentanonen in einer intramolekularen Hydroacylierung bewirkt wird und in einer einfachen Eintopfreaktion durchgeführt werden kann. Infolgedessen lassen sich entsprechend Schema 1 Cyclopentanone IV auf diese Weise aus Bisallylethern (I), Allyl-vinyl-ethern (II), 4-Pentenalen III oder Gemischen dieser Edukte herstellen. The process according to the invention has the advantage that the isomerization of bisallyl ethers to allyl vinyl ethers, its rearrangement to 4-pentenals and finally its further rearrangement to the desired cyclopentanones is effected in one step in an intramolecular hydroacylation and is carried out in a simple one-pot reaction can. As a result, according to Scheme 1, cyclopentanones IV can be prepared in this way from bisallyl ethers (I), allyl vinyl ethers (II), 4-pentenals III or mixtures of these starting materials.
Figure imgf000006_0001
Figure imgf000006_0001
Schema 1: Dabei bedeuten 0 bis 4 der Reste R1 bis R7 Alkylgruppen mit jeweils 1 bis 3 C-Atomen und die anderen Wasserstoff; der Alkylidenrest =CHR11 ist so definiert, daß er bei einer Absättigung der Doppelbindung in den Alkylrest R1 übergeht. Bevorzugt werden in dem erfindungsgemäßen Verfahren lösliche Ruthenium- Komplexe als Katalysatoren eingesetzt. Ganz besonders eignen sich dabei phosphinligandhaltige Ruthenium01 oder RutheniumII-Komplexe. In einer besonders bevorzugten Ausführungsform der Erfindung wird als Katalysator Tris(triphenylphosphin)rutheniumIIdichlorid, (PPh3)3RuCl2 eingesetzt. Scheme 1: 0 to 4 of the radicals R 1 to R 7 are alkyl groups each having 1 to 3 carbon atoms and the other are hydrogen; the alkylidene radical = CHR 11 is defined such that it changes into the alkyl radical R 1 when the double bond is saturated. Soluble ruthenium complexes are preferably used as catalysts in the process according to the invention. Ruthenium 0 1 or ruthenium II complexes containing phosphine ligand are particularly suitable. In a particularly preferred embodiment of the invention, tris (triphenylphosphine) ruthenium II dichloride, (PPh 3 ) 3 RuCl 2 is used as catalyst.
Die Konzentration des Katalysators in der Reaktionsmischung unterliegt keinen besonderen Einschränkungen, jedoch werden 0,5 bis 20 Gew.-% - bezogen auf das umzulagernde Edukt - bevorzugt. Dabei ist es von besonderem Vorteil, die Konzentration des Katalysators in der Reaktionsmischung auf Werte im Bereich von 5 bis 10 Gew.-% einzustellen. The concentration of the catalyst in the reaction mixture is not subject to any particular restrictions, but 0.5 to 20% by weight, based on the starting material to be rearranged, is preferred. It is particularly advantageous to adjust the concentration of the catalyst in the reaction mixture to values in the range from 5 to 10% by weight.
Der Katalysator kann im Zuge des erfindungsgemäßen Verfahrens mehrfach wiederverwendet werden, ohne daß Einbußen in bezug auf die Ausbeute hingenommen werden müssen. Es hat sich gezeigt, daß der zurückgewonnene Katalysatorkomplex als RuCl2(CO)2(PPh3)2 [Wilkinson et al., J. Inorg. Nucl. Chem. 1966 [28] 945] anfällt. Dieser ist ebenfalls katalytisch aktiv und kann - gewünschtenfalls mehrfach - im erfindungsgemäßen Verfahren eingesetzt werden. The catalyst can be reused several times in the course of the process according to the invention without having to accept losses in terms of the yield. It has been shown that the recovered catalyst complex as RuCl 2 (CO) 2 (PPh 3 ) 2 [Wilkinson et al., J. Inorg. Nucl. Chem. 1966 [28] 945] is obtained. This is also catalytically active and can - if desired several times - be used in the process according to the invention.
Die intramolekulare Hydroacylierung wird im erfindungsgemäßen Verfahren vorzugsweise bei Temperaturen von 180 bis 250 °C durchgeführt. Höhere Temperaturen ergeben keine signifikante Ausbeutesteigerung und bergen allenfalls die Gefahr einer Zersetzung der Ausgangsmaterialien bzw. Zwischenprodukte. Als besonders günstig haben sich Reaktionstemperaturen im Bereich von 190 bis 220 °C erwiesen. The intramolecular hydroacylation is preferably carried out in the process according to the invention at temperatures of 180 to 250 ° C. Higher temperatures do not result in a significant increase in yield and at most involve the risk of decomposition of the starting materials or intermediate products. Reaction temperatures in the range from 190 to 220 ° C. have proven to be particularly favorable.
Die erfindungsgemäße Umlagerung wird bei Kohlenmonoxid-Drucken von 5 bis 100 bar, vorzugsweise bei 10 bis 60 bar durchgeführt. The rearrangement according to the invention is carried out at carbon monoxide pressures of 5 to 100 bar, preferably at 10 to 60 bar.
Das erfindungsgemäße Verfahren wird in einem inerten Solvens durchgeführt. Dazu eignen sich z.B. aliphatische, cycloaliphatische oder aromatische Kohlenwasserstoffe, die gewünschtenfalls auch Halogensubstituenten tragen können. Aus Gründen erhöhter Sicherheit für Personal und Umwelt werden jedoch Lösungsmittel, die frei von Halogenen und/oder aromatischen Gruppen sind, besonders bevorzugt. Aus praktischen Gründen kommen dabei vor allem aliphatische und cycloaliphatische Kohlenwasserstoffe in betracht, die bei Raumtemperatur flüssig sind, z.B. Cyclohexan oder Octan. Um optimale Ausbeuten zu erreichen und eine Desaktivierung des Katalysators zu vermeiden, wird das Solvens in wasser- und luftfreier Form eingesetzt. The process according to the invention is carried out in an inert solvent. Aliphatic, cycloaliphatic or aromatic hydrocarbons, for example, are suitable for this purpose and, if desired, can also carry halogen substituents. However, solvents which are free of halogens and / or aromatic groups are particularly preferred for reasons of increased safety for personnel and the environment. For practical reasons, above all aliphatic and cycloaliphatic hydrocarbons that are liquid at room temperature, for example cyclohexane or octane. In order to achieve optimum yields and to avoid deactivation of the catalyst, the solvent is used in an anhydrous and air-free form.
Im Zuge des erfindungsgemäßen Verfahrens werden Edukt, Solvens und Katalysator in einem Druckreaktor, z.B. einem Autoklaven, vorgelegt und diese Mischung mit Kohlenmonoxid in Kontakt gebracht. Die Reaktionsmischung wird bei erhöhter Temperatur gerührt, wobei in der Regel Reaktionszeiten in der Größenordnung von 5 bis 20 Stunden gewählt werden. Nach beendeter Reaktion wird in üblicher Weise aufgearbeitet. In the course of the process according to the invention, the starting material, solvent and catalyst are in a pressure reactor, e.g. an autoclave, and this mixture is brought into contact with carbon monoxide. The reaction mixture is stirred at elevated temperature, reaction times of the order of 5 to 20 hours being generally chosen. After the reaction is worked up in the usual manner.
Die folgenden Beispiele dienen der Erläuterung der Erfindung und sind nicht einschränkend zu verstehen. The following examples serve to illustrate the invention and are not to be understood as restrictive.
B e i s p i e l e B e i s p i e l e
1. Verwendete Substanzen 1. Substances used
Ru3(CO)12: Fa. Aldrich Ru 3 (CO) 12 : Aldrich
RuCl2(PPh3)3: dargestellt nach Wilkinson et al. (J. Inorg. Nucl. Chem.RuCl 2 (PPh 3 ) 3 : according to Wilkinson et al. (J. Inorg. Nucl. Chem.
1966 [28] 945) 1966 [28] 945)
CO: Fa. Messer-Griesheim, 99,0 %  CO: Messrs. Griesheim, 99.0%
n-Octan: Fa. Merck, 99 % (Behandelt mit P2O10, Entgast nach der Methode des "Einfrierens und Auftauens" unter Evakuieren bzw. Argonatmosphäre)n-octane: Merck, 99% (treated with P 2 O 10 , degassed according to the "freezing and thawing" method under evacuation or argon atmosphere)
PPh3: Fa. Riedel-de Haen PPh 3 : Riedel-de Haen
(3-Methyl-2-butenyl)alkylether: dargestellt nach Reuter und Salomon (J. (3-methyl-2-butenyl) alkyl ether: represented by Reuter and Salomon (J.
Org. Chem. 1977 [42] 3360) Org. Chem. 1977 [42] 3360)
(3-Methyl-2-butenyl)vinylether: dargestellt nach Boeckmann und Ko (J. Am. (3-methyl-2-butenyl) vinyl ether: represented by Boeckmann and Ko (J. Am.
Chem. Soc. 1982 [104] 1033) Chem. Soc. 1982 [104] 1033)
3,3-Dimethyl-4-pentenal: dargestellt nach Boeckmann und Ko (J. Am. Chem. 3,3-Dimethyl-4-pentenal: represented according to Boeckmann and Ko (J. Am. Chem.
Soc. 1982 [104] 1033) Soc. 1982 [104] 1033)
2. Versuchsbeschreibungen 2. Test descriptions
Beispiel 1 example 1
In einem 50-ml-Laborautoklaven wurden unter Argon 190 mg (0,198 mmol) Tris(triphenylphosphin)ruthenium(II)dichlorid, (PPh3)3RuCl2, vorgelegt und mit einem Gemisch von 500 mg (3,96 mmol) 3-Methyl-2-butenylallylether in 20 ml wasser- und sauerstofffreiem n-Octan versetzt. Nach dreimaligem Aufpressen und Entspannen von jeweils 10 bar Kohlenmonoxid wurde ein Druck von 60 bar Kohlenmonoxid aufgegeben und das Reaktionsgemisch 16 Stunden auf 200 °C erhitzt. Zur Aufarbeitung ließ man abkühlen, dekantierte das gelblich gefärbte Reaktionsgemisch von ausgefallenen nadeiförmigen Kristallen und wusch diese mit Pentan. Die dekantierte Lösung und die Pentanphase gab man auf eine Kieselgelsäule, entfernte durch Waschen mit 200 ml n-Pentan das n-Octan und eluierte dann das Rohprodukt mit 200 ml Di- ethylether. Der Ether wurde am Rotationsverdampfer bei 35 °C/200 Torr entfernt und der Rückstand in einer Kugelrohrdestillationsapparatur bei 70 °C/60 Torr destilliert. Die durch Dekantieren erhaltenen farblosen Kristalle [105 mg/0, 14 mMol; Schmp. 290-316 °C] wurden spektroskopisch als RuCl2(CO)2(PPh3)2 identifiziert (IR, NMR, MS). 190 mg (0.198 mmol) of tris (triphenylphosphine) ruthenium (II) dichloride, (PPh 3 ) 3 RuCl 2 , were placed in a 50 ml laboratory autoclave under argon and mixed with a mixture of 500 mg (3.96 mmol) 3- Methyl 2-butenyl allyl ether in 20 ml of anhydrous and oxygen-free n-octane. After pressing and releasing 10 bar of carbon monoxide three times, a pressure of 60 bar of carbon monoxide was applied and the reaction mixture was heated to 200 ° C. for 16 hours. For working up, the mixture was allowed to cool, the yellowish-colored reaction mixture was decanted from precipitated acicular crystals and washed with pentane. The decanted solution and the pentane phase were placed on a silica gel column, the n-octane was removed by washing with 200 ml of n-pentane, and the crude product was then eluted with 200 ml of diethyl ether. The ether was removed on a rotary evaporator at 35 ° C./200 Torr and the residue was distilled in a Kugelrohr distillation apparatus at 70 ° C. 60 Torr. The colorless crystals obtained by decanting [105 mg / 0.14 mmol; Mp 290-316 ° C] were spectroscopically identified as RuCl 2 (CO) 2 (PPh 3 ) 2 (IR, NMR, MS).
Ausbeute: 230 mg 2,2,3-Trimethylcyclopentanon (46 % der Theorie). Beispiel 2 Yield: 230 mg of 2,2,3-trimethylcyclopentanone (46% of theory). Example 2
Analog zu Beispiel 1 wurden umgesetzt: 406 mg (0,423 mmol) (PPh3)3RuCl2. 950 mg (8,47 mmol) (3-Methyl-2-butenyl)-vinylether, 20 ml n-Octan. Aufarbeitung: wie Beispiel 1. The following were implemented analogously to Example 1: 406 mg (0.423 mmol) (PPh 3 ) 3 RuCl 2 . 950 mg (8.47 mmol) (3-methyl-2-butenyl) vinyl ether, 20 ml n-octane. Refurbishment: as example 1.
Ausbeute: 693 mg (6,18 mmol) 3,3-Dimethylcyclopentanon, das sind 73% der Theorie.  Yield: 693 mg (6.18 mmol) of 3,3-dimethylcyclopentanone, that is 73% of theory.
Beispiel 3 Example 3
Analog zu Beispiel 2 wurden bei einem CO-Druck von 50 bar und einer Reaktionszeit von 18 Stunden umgesetzt: 90 mg (0,141 mmol) Dodecacarbonyltriruthemium, Ru3(CO)12, 950 mg (8,47 mmol) (3-Methyl-2-butenyl)-vinylether, 25 ml n-Octan. Analogously to Example 2, the reaction was carried out at a CO pressure of 50 bar and a reaction time of 18 hours: 90 mg (0.141 mmol) dodecacarbonyltriruthemium, Ru 3 (CO) 12 , 950 mg (8.47 mmol) (3-methyl-2 -butenyl) vinyl ether, 25 ml n-octane.
Die Aufarbeitung des Rohproduktes erfolgte zunächst durch Destillation bei 45 °C/760 Torr (Kugelrohr), wobei das Solvens im Gemisch mit 3,3-Dimethylbuten erhalten wurde. Durch Chromatographie des Rückstandes an Kieselgel mit n-Pentan wurden nacheinander n-Octan und dann das orangerote Dodecacarbonyltriruthenium eluiert werden. Durch Einengen des Eluats und Trocknen im Ölpumpenvakuum wurden 40,6 mg (45%) des Katalysators zurückgewonnen. Die polareren Fraktionen der Chromatographie wurden mit 200 ml Diethylether eluiert, der Ether am Rotationsverdampfer abgezogen und der Rückstand in einer Kugelrohrdestillationsapparatur destilliert.  The crude product was first worked up by distillation at 45 ° C./760 torr (spherical tube), the solvent being obtained in a mixture with 3,3-dimethylbutene. Chromatography of the residue on silica gel with n-pentane eluted successively with n-octane and then the orange-red dodecacarbonyltriruthenium. By concentrating the eluate and drying in an oil pump vacuum, 40.6 mg (45%) of the catalyst were recovered. The more polar fractions of the chromatography were eluted with 200 ml of diethyl ether, the ether was removed on a rotary evaporator and the residue was distilled in a Kugelrohr distillation apparatus.
Ausbeute: 135 mg (1,2 mmol) 3,3-Dimethylcyclopentanon, das sind 30% der Theorie.  Yield: 135 mg (1.2 mmol) of 3,3-dimethylcyclopentanone, that is 30% of theory.
Beispiel 4 Example 4
Die in Beispiel 3 beschriebene Umsetzung wurde wiederholt, wobei dem Reaktionsgemisch zusätzlich 540 mg (0,846 mmol) Triphenylphosphin zugesetzt worden waren. Aufarbeitung wie Beispiel 1.  The reaction described in Example 3 was repeated, 540 mg (0.846 mmol) of triphenylphosphine being additionally added to the reaction mixture. Refurbishment as example 1.
Ausbeute: 202 mg 3,3-Dimethylcyclopentanon (45 % der Theorie). Yield: 202 mg of 3,3-dimethylcyclopentanone (45% of theory).
Beispiel 5 Example 5
Analog zu Beispiel 1 wurden in einem 75-ml-Autoklaven umgesetzt: 428 mg Analogously to Example 1, the following were implemented in a 75 ml autoclave: 428 mg
(0,45 mol) (PPh3)3RuCl2, 1,0 g (8,9 mmol) 3,3-Dimethyl-4-pentenal, 25 ml n-Octan. Aufarbeitung: wie Beispiel 1. (0.45 mol) (PPh 3 ) 3 RuCl 2 , 1.0 g (8.9 mmol) 3,3-dimethyl-4-pentenal, 25 ml n-octane. Refurbishment: as example 1.
Ausbeute: 665 mg (5,9 mmol) 3,3-Dimethylcyclopentanon, das sind 67 % der Yield: 665 mg (5.9 mmol) of 3,3-dimethylcyclopentanone, that is 67% of the
Theorie. Theory.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Verfahren zur Herstellung von Cyclopentanonen mit bis zu vier Alkylresten mit je 1 bis 3 C-Atomen, bei denen ein C-Atom in ß-Stellung zur Carbonylgruppe mindestens ein Wasserstoffatom trägt, durch Umlagerung entsprechender Bisallyl-ether, Allyl-vinylether oder 4-Pentenale in einem inerten Solvens in Gegenwart von Kohlenmonoxid oder einem kohlenmonoxid-haltigen Gas und eines Ruthenium-Katalysators bei erhöhter Temperatur. 1. A process for the preparation of cyclopentanones with up to four alkyl radicals each having 1 to 3 carbon atoms, in which one carbon atom in the β-position to the carbonyl group carries at least one hydrogen atom, by rearrangement of corresponding bisallyl ether, allyl vinyl ether or 4 -Pentenals in an inert solvent in the presence of carbon monoxide or a gas containing carbon monoxide and a ruthenium catalyst at elevated temperature.
2. Verfahren nach Anspruch 1, wobei als Katalysator ein löslicher Ruthenium-Komplex eingesetzt wird. 2. The method according to claim 1, wherein a soluble ruthenium complex is used as catalyst.
3. Verfahren nach Anspruch 1 oder 2, wobei als Katalysator ein phosphin- ligandhaltiger Ruthenium0- oder RutheniumII-Komplex eingesetzt wird. 3. The method of claim 1 or 2, wherein a ruthenium 0 or ruthenium II complex containing phosphine ligand is used as catalyst.
4. Verfahren nach einem der Ansprüche 1 bis 3, wobei als Katalysator RuCl2(PPh3)3 eingesetzt wird. 4. The method according to any one of claims 1 to 3, wherein RuCl 2 (PPh 3 ) 3 is used as catalyst.
5. Verfahren nach einem der Ansprüche 1 bis 4, wobei der Katalysator in einer Menge von 0,5 bis 20 Gew.-% - bezogen auf das umzulagernde Edukt - eingesetzt wird. 5. The method according to any one of claims 1 to 4, wherein the catalyst is used in an amount of 0.5 to 20 wt .-% - based on the starting material to be rearranged.
6. Verfahren nach einem der Ansprüche 1 bis 5, wobei die Umlagerung bei Temperaturen im Bereich von 180 bis 250 °C , vorzugsweise im Bereich von 190 bis 220 °C durchgeführt wird. 6. The method according to any one of claims 1 to 5, wherein the rearrangement is carried out at temperatures in the range from 180 to 250 ° C, preferably in the range from 190 to 220 ° C.
7. Verfahren nach einem der Ansprüche 1 bis 6, wobei ein Kohlenmonoxiddruck 5 bis 100 bar, vorzugsweise von 10 bis 60 bar, eingestellt wird. 7. The method according to any one of claims 1 to 6, wherein a carbon monoxide pressure 5 to 100 bar, preferably from 10 to 60 bar, is set.
8. Verfahren nach einem der Ansprüche 1 bis 7, wobei ein inertes Solvens eingesetzt wird, das ausgewählt ist aus der Gruppe der aliphatischen, cycloaliphatischen oder aromatischen Kohlenwasserstoffe. 8. The method according to any one of claims 1 to 7, wherein an inert solvent is used, which is selected from the group of aliphatic, cycloaliphatic or aromatic hydrocarbons.
9. Verfahren nach einem der Ansprüche 1 bis 8, wobei als inertes Solvens ein bei Raumtemperatur flüssiger aliphatischer Kohlenwasserstoff eingesetzt wird. 9. The method according to any one of claims 1 to 8, wherein an aliphatic hydrocarbon which is liquid at room temperature is used as the inert solvent.
10. Verwendung der nach einem der Ansprüche 1 bis 9 hergestellten Cyclopentanone für organische Synthesen. 10. Use of the cyclopentanones prepared according to one of claims 1 to 9 for organic syntheses.
PCT/EP1992/001630 1991-07-26 1992-07-17 Method of preparing cyclopentanones WO1993002997A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190607A (en) * 1978-09-29 1980-02-26 Carter-Wallace, Inc. Method for the preparation of 2,3-dimethyl-pent-4en-aldehyde
US4288613A (en) * 1979-12-03 1981-09-08 Iowa State University Research Foundation, Inc. Cyclopentanone synthesis

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190607A (en) * 1978-09-29 1980-02-26 Carter-Wallace, Inc. Method for the preparation of 2,3-dimethyl-pent-4en-aldehyde
US4288613A (en) * 1979-12-03 1981-09-08 Iowa State University Research Foundation, Inc. Cyclopentanone synthesis

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF ORGANIC CHEMISTRY. Bd. 42, Nr. 21, 1977, EASTON US Seiten 3360 - 3364 J.M. REUTER ET AL. 'Ruthenium(II) catalyzed rearrangement of diallyl ethers. A synthesis of gamma, delta - unsaturated aldehydes and ketones.' in der Anmeldung erwähnt *
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. Bd. 102, Nr. 1, 1980, GASTON, PA US Seiten 190 - 197 R.C. LAROCK ET AL. 'A convenient synthesis of cyclopentanones via Rhodium(I) catalyzed intramolecular hydroacylation of unsaturated aldehydes.' in der Anmeldung erwähnt *

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