WO1992000266A1 - Method for the aldolization of compounds with active hydrogen atoms - Google Patents

Method for the aldolization of compounds with active hydrogen atoms Download PDF

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Publication number
WO1992000266A1
WO1992000266A1 PCT/EP1991/001140 EP9101140W WO9200266A1 WO 1992000266 A1 WO1992000266 A1 WO 1992000266A1 EP 9101140 W EP9101140 W EP 9101140W WO 9200266 A1 WO9200266 A1 WO 9200266A1
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reaction
compounds
water
active hydrogen
hydrogen atoms
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PCT/EP1991/001140
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German (de)
French (fr)
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Udo Hees
Wolfgang Breuer
Hans-Christian Raths
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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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts

Definitions

  • the invention relates to a process for the aldolization of compounds with active hydrogen atoms in the presence of double layer hydroxides.
  • the aldolization of fatty aldehydes is a long-known technical process for the production of alpha, beta-unsaturated, higher molecular weight aldehydes which hydrogenate to the corresponding alcohols and as raw materials, for. B. can be used for the production of surfactants [Actes Congr. Moon., Soc. Int. Etude Corporation Gras, 13th Vol. Sect.C, 45-50, 1976].
  • the aldol condensation is carried out in the presence of basic catalysts, which can be both homogeneous and heterogeneous in nature.
  • the object of the invention was therefore an improved
  • the invention relates to a process for the aldolization of compounds with active hydrogen atoms, characterized in that the reaction is carried out in the presence of double-layer hydroxides containing water of crystallization under azeotropic conditions.
  • the invention is based on the knowledge that water-crystal, ie. H. Non-calcined double-layer hydroxides are suitable as catalysts for the aldol condensation if the crystal water is separated off together with the reaction water released during the condensation in the presence of an entrainer via a water separator.
  • Suitable compounds with active hydrogen atoms which are suitable for aldol condensation are ketones, such as, for example, acetone or methyl ethyl ketone, but especially fatty aldehydes of the formula (I), -CHO (I)
  • R represents a saturated or unsaturated hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.
  • Fatty aldehydes are known chemical compounds which are accessible by the usual methods of preparative organic chemistry.
  • a process for their preparation consists, for example, of oxidizing fatty alcohols in the presence of 4-methoxy-2,2,6,6-tetramethylpiperidin-1-yloxyl (TEMPO) [J.Am.Chem.
  • Typical examples of fatty aldehydes which can be subjected to aldol condensation in the sense of the invention are hexanal, decanal, dodecanal, hexadecanal or octadecanal. Saturated fatty aldehydes having 8 to 16 carbon atoms are preferably used. As usual in fat chemistry, the fatty aldehydes can also be present as technical mixtures, such as those found in B. in the oxidation of fatty alcohols based on natural raw materials. Technical aldehyde fractions which are accessible via the hydroformylation of olefins are also suitable.
  • Double-layer hydroxides are to be understood as cationic layer compounds which are structurally derived from brucite [Mg (0H) 2] and crystallize in a layer structure with the metal ions in octahedral gaps between two layers of densely packed hydroxide ions, of which only every second layer of the octahedron gaps are occupied [Chimia, 24, 99 (1970)]. Chemically they are mixed basic hydroxy salts of di- and trivalent metal cations and follow the formula (II), [H II ⁇ _ x MlII ⁇ (0H) 2 A y • m H 2 0 (II)
  • M * l stands for at least one divalent metal cation
  • M 111 for at least one trivalent metal cation
  • A for the equivalent of an anion of a mono- or polybasic acid
  • Possible divalent metal ions M 11 are cations selected from the group formed by Mg 2+ , Ca 2+ , Mn2 + , Zn 2+ and Cu 2+ ;
  • Examples of trivalent metal ions M 111 are cations selected from the group formed by Al3 + f Fe3 + and Cr3 + .
  • Anions selected from the group formed by carbonate, carboxylate, chloride, nitrate, sulfate or phosphate are considered for A as the equivalent for the anion of a mono- or polybasic acid.
  • Typical examples of double-vision hydroxides which can be used as catalysts for the aldol condensation in the process according to the invention are, for example
  • hydrotalcite of the formula (III) is used as the double-layer hydroxide
  • hydrophobic double-layer hydroxides in particular hydrophobic hydrotalcite
  • hydrophobic double-layer hydroxides are used as catalysts in the aldol condensation.
  • the preparation of the hydrophobic double-layer hydroxides can, for. B. by reaction of natural or synthetic double-layer hydroxides, in particular hydrotalcite, in the presence or absence of solvents with C 2 -C 22 mono- or dicarboxylic acids, in particular lauric acid.
  • Hydrotalcite is a known chemical compound which is found both as a natural mineral and synthetically by the relevant methods of preparative inorganic chemistry [DE-A-1592 126; DE-B-3306822; DE-A-3346 943] is accessible.
  • Optimal conditions for the aldol condensation are temperatures of 100 to 150, in particular 120 to 130 ° C.
  • the reaction is usually carried out over a period of 1 to 10, in particular 3 to 7 hours.
  • reaction mixture After completion of the reaction, the reaction mixture is cooled and the catalyst z. B. separated by filtration. After drying, it can be returned to the aldolization.
  • the alpha, beta-unsaturated aldehydes obtained in the aldol condensation can be hydrogenated to the branched alcohols by methods known per se and then used as raw materials for the production of surface-active agents or lubricants.
  • Example 1 was repeated with 3 g of hydrotalcite which had previously been calcined at 500 ° C. for 12 h. 80 g of a colorless, clear liquid were obtained, the gas chromatographically determined content of aldol condensate being 61% by weight.
  • Example 1 Aldol condensation from Decanal.
  • Example 1 was repeated using 87 g (0.54 mol) of decanal.
  • 77 g of a colorless, clear liquid were obtained, the gas chromatographically determined content of aldol condensate being 69% by weight.
  • Example 1 Aldol condensation of hexadecanal.
  • Example 1 was repeated using 115 g (0.54 mol) of hexadecanal and 4.5 g of hydrotalcite. 100 g of a colorless pasty liquid were obtained, the gas chromatographically determined content of aldol condensate being 62% by weight.
  • Example 1 was repeated using 3 g of the hydrotalcite from Example 4 which had been hydrophobicized with lauric acid. Within 4.5 hours, 89 g of a colorless, clear liquid were obtained, the gas chromatographically determined content of aldol condensate being 68% by weight.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

In the method described, fatty aldehydes can be subjected to an aldol condensation in the presence of double-layer hydroxides containing water of crystallization if the water of crystallization and water of reaction are removed under azeotropic conditions.

Description

Verfahren zur Aldolisierunq von Verbindungen mit aktiven Wasserstoffatomen Process for the aldolization of compounds with active hydrogen atoms
Die Erfindung betrifft ein Verfahren zur Aldolisierung von Ver¬ bindungen mit aktiven Wasserstoffatomen in Gegenwart von Doppelschichthydroxiden.The invention relates to a process for the aldolization of compounds with active hydrogen atoms in the presence of double layer hydroxides.
Die Aldolisierung von Fettaldehyden stellt ein lange bekanntes technisches Verfahren zur Herstellung von alpha,beta-ungesättig- ten, höhermolekularen Aldehyden dar, die zu den entsprechenden Al¬ koholen hydriert und als Rohstoffe z. B. für die Herstellung von Tensiden dienen können [Actes Congr. Mond., Soc. Int. Etüde Corps Gras, 13th Vol. Sect.C, 45-50, 1976]. Die Aldolkondensation wird in Gegenwart basischer Katalysatoren durchgeführt, die sowohl ho¬ mogener als auch heterogener Natur sein können.The aldolization of fatty aldehydes is a long-known technical process for the production of alpha, beta-unsaturated, higher molecular weight aldehydes which hydrogenate to the corresponding alcohols and as raw materials, for. B. can be used for the production of surfactants [Actes Congr. Moon., Soc. Int. Etude Corps Gras, 13th Vol. Sect.C, 45-50, 1976]. The aldol condensation is carried out in the presence of basic catalysts, which can be both homogeneous and heterogeneous in nature.
Für eine technische Durchführung der Reaktion hat sich der Einsatz von Katalysatoren bewährt, die im Reaktionsprodukt unlöslich sind und somit nach Beendigung der Aldolisierung problemlos abgetrennt und gegebenenfalls wiederverwendet werden können. Als besonders effektiv hat sich hierbei die Verwendung von Hydrotalcit, einem Doppelsehichthydroxid mit Brucitstruktur, erwiesen [Bull.Soc.Che . Jpn. 61, 1008 (1988); J.Catal., 94. 547 (1985); EP-A-0 095 783]. Katalysatoren dieses Strukturtyps enthalten jedoch erhebliche Mengen Kristallwasser. Vor einer Verwendung als Katalysatoren in der Aldolkondensation müssen die Doppelschichthydroxide aktiviert werden. Dazu ist es erforderlich, sie zu calcinieren, d. h. einer Temperaturbehandlung bei 400 bis 600°C auszusetzen. Hierbei wird das zwischen den Schichten adsorbierte Kristallwasser ausgetrieben und - insbesondere im oberen Temperaturbereich - weitere Wassermo¬ leküle aus dem Hydroxidgerüst abgespalten. Enthält das Doppel¬ schichthydroxid Carbonationen, kann weiterhin Kohlendioxid freige¬ setzt werden. Der notwendige Calcinierungsprozeß ist mit einem hohen Aufwand an Zeit und Energie verbunden und beeinträchtigt daher die Wirtschaftl chkeit derartiger Verfahren.The use of catalysts which are insoluble in the reaction product and which can therefore be separated off and, if appropriate, reused after the end of the aldolization, has proven useful for carrying out the reaction industrially. The use of hydrotalcite, a double-layer hydroxide with a brucite structure, has proven to be particularly effective [Bull.Soc.Che. Jpn. 61: 1008 (1988); J. Catal., 94, 547 (1985); EP-A-0 095 783]. However, catalysts of this type of structure contain considerable amounts of water of crystallization. The double-layer hydroxides must be activated before they can be used as catalysts in aldol condensation become. This requires calcining them, ie exposing them to a temperature treatment at 400 to 600 ° C. Here, the crystal water adsorbed between the layers is driven out and - especially in the upper temperature range - further water molecules are cleaved from the hydroxide structure. If the double-layer hydroxide contains carbonate ions, carbon dioxide can still be released. The necessary calcination process is associated with a high expenditure of time and energy and therefore affects the economic viability of such processes.
Die Aufgabe der Erfindung bestand somit darin, ein verbessertesThe object of the invention was therefore an improved
Verfahren zur Aldolisierung von Verbindungen mit aktiven Wasser¬ stoffato en zur Verfügung zu stellen.To provide methods for the aldolization of compounds with active hydrogen atoms.
Gegenstand der Erfindung ist ein Verfahren zur Aldolisierung von Verbindungen mit aktiven Wasserstoffatomen, dadurch gekennzeich¬ net, daß die Reaktion in Gegenwart von kristallwasserhaltigen Doppelschichthydroxiden unter azeotropen Bedingungen durchgeführt wird.The invention relates to a process for the aldolization of compounds with active hydrogen atoms, characterized in that the reaction is carried out in the presence of double-layer hydroxides containing water of crystallization under azeotropic conditions.
Die Erfindung beruht auf der Erkenntnis, daß kristallwasserhal¬ tige, d. h. nicht-calcinierte Doppelschichthydroxide als Katalysa¬ toren für die Aldolkondensation geeignet sind, wenn das Kristall- wasser zusammen mit dem bei der Kondensation freiwerdenden Reak¬ tionswasser in Gegenwart eines Schleppmittels über einen Wasserab¬ scheider abgetrennt wird.The invention is based on the knowledge that water-crystal, ie. H. Non-calcined double-layer hydroxides are suitable as catalysts for the aldol condensation if the crystal water is separated off together with the reaction water released during the condensation in the presence of an entrainer via a water separator.
Als Verbindungen mit aktiven Wasserstoffatomen, die für eine Al¬ dolkondensation geeignet sind, kommen Ketone, wie z.B. Aceton oder Methylethylketon, insbesondere jedoch Fettaldehyde der Formel (I), -CHO (I )Suitable compounds with active hydrogen atoms which are suitable for aldol condensation are ketones, such as, for example, acetone or methyl ethyl ketone, but especially fatty aldehydes of the formula (I), -CHO (I)
in der R für einen gesättigten oder ungesättigten Kohlenwasser¬ stoffrest mit 6 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Dop¬ pelbindungen steht, in Betracht.in which R represents a saturated or unsaturated hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.
Fettaldehyde stellen bekannte chemische Verbindungen dar, die nach den gängigen Methoden der präparativen organischen Chemie zugäng¬ lich sind. Ein Verfahren zu ihrer Herstellung besteht beispiels¬ weise darin, Fettalkohole in Gegenwart von 4-Methoxy-2,2,6,6- tetramethylpiperidin-1-yloxyl (TEMPO) zu oxidieren [J.Am.Chem.Fatty aldehydes are known chemical compounds which are accessible by the usual methods of preparative organic chemistry. A process for their preparation consists, for example, of oxidizing fatty alcohols in the presence of 4-methoxy-2,2,6,6-tetramethylpiperidin-1-yloxyl (TEMPO) [J.Am.Chem.
Soc, 109. 3786 (1987)]. Typische Beispiele für Fettaldehyde, die im Sinne der Erfindung einer Aldolkondensation unterworfen werden können, sind Hexanal, Decanal, Dodecanal, Hexadecanal oder Octade- canal. Vorzugsweise werden gesättigte Fettaldehyde mit 8 bis 16 Kohlenstoffatomen eingesetzt. Wie in der Fettchemie üblich, können die Fettaldehyde auch als technische Gemische vorliegen, wie sie z. B. bei der Oxidation von Fettalkoholen auf der Basis natür¬ licher Rohstoffe anfallen. Gleichfalls geeignet sind technische Aldehydfraktionen, die über die Hydrofor ylierung von Olefinen zu¬ gänglich sind.Soc, 109, 3786 (1987)]. Typical examples of fatty aldehydes which can be subjected to aldol condensation in the sense of the invention are hexanal, decanal, dodecanal, hexadecanal or octadecanal. Saturated fatty aldehydes having 8 to 16 carbon atoms are preferably used. As usual in fat chemistry, the fatty aldehydes can also be present as technical mixtures, such as those found in B. in the oxidation of fatty alcohols based on natural raw materials. Technical aldehyde fractions which are accessible via the hydroformylation of olefins are also suitable.
Unter Doppelschichthydroxiden sind kationische Schichtverbindungen zu verstehen, die sich strukturell vom Brucit [Mg(0H)2] ableiten und in einer Schichtstruktur mit den Metallionen in Oktaederlücken zwischen zwei Schichten aus dichtgepackten Hydroxidionen kristal¬ lisieren, von denen jedoch nur jede zweite Schicht der Oktaeder¬ lücken besetzt ist [Chimia, 24, 99 (1970)]. Chemisch stellen sie gemischte basische Hydroxysalze zwei- und dreiwertiger Metallkat¬ ionen dar und folgen der Formel (II), [HIIι_xMlIIχ(0H)2 Ay • m H20 (II)Double-layer hydroxides are to be understood as cationic layer compounds which are structurally derived from brucite [Mg (0H) 2] and crystallize in a layer structure with the metal ions in octahedral gaps between two layers of densely packed hydroxide ions, of which only every second layer of the octahedron gaps are occupied [Chimia, 24, 99 (1970)]. Chemically they are mixed basic hydroxy salts of di- and trivalent metal cations and follow the formula (II), [H II ι_ x MlII χ (0H) 2 A y • m H 2 0 (II)
in derin the
M*l für mindestens ein zweiwertiges Metallkation, M111 für mindestens ein dreiwertiges Metallkation, A für das Äquivalent eines Anions einer ein- oder mehrbasigen Säure stehtM * l stands for at least one divalent metal cation, M 111 for at least one trivalent metal cation, A for the equivalent of an anion of a mono- or polybasic acid
und die Beziehungen 0,17 <. x <.0,5, 0,17 < y < 0,5 und 0 <_ m 1 gelten.and the relationships 0.17 <. x <.0.5, 0.17 <y <0.5 and 0 <_ m 1 apply.
Als zweiwertige Metallionen M11 kommen Kationen ausgewählt aus der Gruppe, die von Mg2+, Ca2+, Mn2+, Zn2+ und Cu2+ gebildet wird, in Betracht; Beispiele für dreiwertige Metallionen M111 sind Kationen ausgewählt aus der Gruppe, die von Al3+ f Fe3+ und Cr3+ gebildet wird. Für A als Äquivalent für das Anion einer ein- oder mehrbasi¬ gen Säuren kommen Anionen ausgewählt aus der Gruppe, die von Car- bonat, Carboxylat, Chlorid, Nitrat, Sulfat oder Phosphat gebildet wird, in Betracht. Typische Beispiele für Doppelsehichthydroxide, die im Sinne des erfindungsgemäßen Verfahrens als Katalysatoren für die Aldolkondensation eingesetzt werden können, sind bei¬ spielsweisePossible divalent metal ions M 11 are cations selected from the group formed by Mg 2+ , Ca 2+ , Mn2 + , Zn 2+ and Cu 2+ ; Examples of trivalent metal ions M 111 are cations selected from the group formed by Al3 + f Fe3 + and Cr3 + . Anions selected from the group formed by carbonate, carboxylate, chloride, nitrate, sulfate or phosphate are considered for A as the equivalent for the anion of a mono- or polybasic acid. Typical examples of double-vision hydroxides which can be used as catalysts for the aldol condensation in the process according to the invention are, for example
- Pyroaurit [Mg6Fe2(0H)i6]C03 • 4,5 H20,Pyroaurite [Mg 6 Fe 2 (0H) i6] C03 • 4.5 H 2 0,
- Magaldrat [ gι0Al5(0H)3i](S04)2 • H20 oder- Magaldrat [gι 0 Al5 (0H) 3i] (S04) 2 • H 2 0 or
- Zn/Al-Phasen des Typs [Zn6Al2(0H)16]C03 • H20.- Zn / Al phases of the type [Zn 6 Al 2 (0H) 16 ] C03 • H 2 0.
In einer besonderen Ausführungsform der Erfindung wird als Doppelschichthydroxid Hydrotalcit der Formel (III)In a particular embodiment of the invention, hydrotalcite of the formula (III) is used as the double-layer hydroxide
[Mg6Al2(0H)16]C03 • 4 H20 (III) eingesetzt.[Mg6Al 2 (0H) 16 ] C03 • 4 H 2 0 (III) used.
In einer bevorzugten Ausführungsform der Erfindung werden hydro- phobierte Doppelschichthydroxide, insbesondere hydrophobierter Hydrotalcit als Katalysator in die Aldolkondensation eingesetzt. Die Herstellung der hydrophobierten Doppelschichthydroxide kann z. B. durch Umsetzung von natürlichen oder synthetischen Doppel¬ schichthydroxiden, insbesondere Hydrotalcit, in Gegenwart oder Ab¬ wesenheit von Lösemitteln mit C2-C22-Mono- oder Dicarbonsäuren, insbesondere Laurinsäure erfolgen.In a preferred embodiment of the invention, hydrophobic double-layer hydroxides, in particular hydrophobic hydrotalcite, are used as catalysts in the aldol condensation. The preparation of the hydrophobic double-layer hydroxides can, for. B. by reaction of natural or synthetic double-layer hydroxides, in particular hydrotalcite, in the presence or absence of solvents with C 2 -C 22 mono- or dicarboxylic acids, in particular lauric acid.
Hydrotalcit stellt eine bekannte chemische Verbindung dar, die so¬ wohl als natürliches Mineral gefunden wird, als auch auf syntheti¬ schem Wege nach den einschlägigen Methoden der präparativen anor¬ ganischen Chemie [DE-A-1592 126; DE-B-3306822; DE-A-3346 943] zugänglich ist.Hydrotalcite is a known chemical compound which is found both as a natural mineral and synthetically by the relevant methods of preparative inorganic chemistry [DE-A-1592 126; DE-B-3306822; DE-A-3346 943] is accessible.
Zur Durchführung der Aldolkondensation ist es vorteilhaft, den Fettaldehyd im Schleppmittel zu lösen oder zu emulgieren und mit dem Doppelschichthydroxid zu versetzen. Als optimal hat es sich erwiesen, die Reaktion in Gegenwart von 0,1 bis 5, vorzugsweise 1 bis 3 Gew.-% eines kristallwasserhaltigen Doppelschichthydroxids, bezogen auf die Verbindungen mit aktiven Wasserstoffatomen, durch¬ zuführen, wobei als Schleppmittel Benzol, Toluol oder Xylol in Be¬ tracht kommen.To carry out the aldol condensation, it is advantageous to dissolve or emulsify the fatty aldehyde in the entrainer and to add the double-layer hydroxide. It has proven to be optimal to carry out the reaction in the presence of 0.1 to 5, preferably 1 to 3,% by weight of a double-layer hydroxide containing water of crystallization, based on the compounds having active hydrogen atoms, benzene, toluene or xylene being the entrainer come into consideration.
Da es im Sinne des erfindungsgemäßen Verfahrens erforderlich ist, Kristall- und Kondensationswasser während der Reaktion über einen Wasserabscheider aus der Reaktionsmischung zu entfernen, ist es sinnvoll, die Aldolisierung oberhalb des Siedepunktes des Wassers durchzuführen, während die Reaktionstemperatur nach oben hin durch den Siedepunkt des Schleppmittels begrenzt wird. Optimale Bedin¬ gungen für die Aldolkondensation stellen Temperaturen von 100 bis 150, insbesondere 120 bis 130°C dar.Since it is necessary in the sense of the method according to the invention to remove water of crystallization and condensation from the reaction mixture during the reaction by means of a water separator, it makes sense to carry out the aldolization above the boiling point of the water while the reaction temperature is increasing the boiling point of the entrainer is limited. Optimal conditions for the aldol condensation are temperatures of 100 to 150, in particular 120 to 130 ° C.
Mit dem Ende der Wasserabscheidung ist die Aldolisierung abge¬ schlossen. Üblicherweise wird die Reaktion über einen Zeitraum von 1 bis 10, insbesondere 3 bis 7 Stunden durchgeführt.With the end of the water separation, the aldolization is completed. The reaction is usually carried out over a period of 1 to 10, in particular 3 to 7 hours.
Nach Abschluß der Reaktion wird die Reaktionsmischung abgekühlt und der Katalysator z. B. durch Filtration abgetrennt. Nach Trock¬ nung kann er in die Aldolisierung zurückgeführt werden.After completion of the reaction, the reaction mixture is cooled and the catalyst z. B. separated by filtration. After drying, it can be returned to the aldolization.
Die bei der Aldolkondensation erhaltenen alpha,beta-ungesättigten Aldehyde können nach an sich bekannten Verfahren zu den verzweig¬ ten AIkohlen hydriert werden und dann als Rohstoffe zu Herstellung von oberflächenaktiven Mitteln oder Schmierstoffen dienen.The alpha, beta-unsaturated aldehydes obtained in the aldol condensation can be hydrogenated to the branched alcohols by methods known per se and then used as raw materials for the production of surface-active agents or lubricants.
Die folgenden Beispiele sollen den Gegenstand der Erfindung ver¬ deutlichen, ohne ihn darauf einzuschränken. The following examples are intended to clarify the subject matter of the invention without restricting it.
BeispieleExamples
Beispiel 1:Example 1:
Aldolkondensation von Dodecanal. In einem 500 ml-Dreihalskolben mit Rührer, Innenthermometer, Intensivkühler und Wasserabscheider wurden 100 g (0,54 Mol) Dodecanal in 100 ml Toluol vorgelegt und mit 3 g Hydrotalcit versetzt. Die Reaktionsmischung wurde unter Stickstoff 6 Stunden auf 120°C erhitzt und Kristall- und Konden¬ sationswasser über den Wasserabscheider gemeinsam abgetrennt. Nach dem Abkühlen wurde der Katalysator abfiltriert und das Toluol mit Hilfe eines Rotationsverdampfers abdestilliert. Es wurden 89 g ei¬ ner farblosen klaren Flüssigkeit erhalten, deren gaschromatogra¬ phisch bestimmter Gehalt an Aldolkondensat 64 Gew.-% betrug.Aldol condensation of dodecanal. 100 g (0.54 mol) of dodecanal in 100 ml of toluene were placed in a 500 ml three-necked flask equipped with a stirrer, internal thermometer, intensive cooler and water separator, and 3 g of hydrotalcite were added. The reaction mixture was heated to 120 ° C. under nitrogen for 6 hours and crystal and condensation water were separated off together using the water separator. After cooling, the catalyst was filtered off and the toluene was distilled off using a rotary evaporator. 89 g of a colorless, clear liquid were obtained, the gas chromatographically determined content of aldol condensate being 64% by weight.
Verqleichsbeispiel 1;Comparative Example 1;
Beispiel 1 wurde mit 3 g Hydrotalcit wiederholt, der zuvor 12 h bei 500°C calciniert worden war. Es wurden 80 g einer farblosen klaren Flüssigkeit erhalten, deren gaschromatographisch bestimmter Gehalt an Aldolkondensat 61 Gew.-% betrug. Example 1 was repeated with 3 g of hydrotalcite which had previously been calcined at 500 ° C. for 12 h. 80 g of a colorless, clear liquid were obtained, the gas chromatographically determined content of aldol condensate being 61% by weight.
Beispiel 2;Example 2;
Aldolkondensation von Decanal. Beispiel 1 wurde unter Einsatz von 87 g (0,54 Mol) Decanal wiederholt. Es wurden 77 g einer farblosen klaren Flüssigkeit erhalten, deren gaschromatographisch bestimmter Gehalt an Aldolkondensat 69 Gew.-% betrug.Aldol condensation from Decanal. Example 1 was repeated using 87 g (0.54 mol) of decanal. 77 g of a colorless, clear liquid were obtained, the gas chromatographically determined content of aldol condensate being 69% by weight.
Beispiel 3:Example 3:
Aldolkondensation von Hexadecanal. Beispiel 1 wurde unter Einsatz von 115 g (0,54 Mol) Hexadecanal und 4,5 g Hydrotalcit wiederholt. Es wurden 100 g einer farblosen pastösen Flüssigkeit erhalten, de¬ ren gaschromatographisch bestimmter Gehalt an Aldolkondensat 62 Gew.-% betrug.Aldol condensation of hexadecanal. Example 1 was repeated using 115 g (0.54 mol) of hexadecanal and 4.5 g of hydrotalcite. 100 g of a colorless pasty liquid were obtained, the gas chromatographically determined content of aldol condensate being 62% by weight.
Beispiel 4:Example 4:
Herstellung von hydrophobiertem Hydrotalcit. 50 g Hydrotalcit wur¬ den in 250 ml Isopropylalkohol suspendiert und bei Raumtemperatur innerhalb von 30 min mit 33,2 g Laurinsäure (Molverhältnis Hydro¬ talcit : Laurinsäure = 1 : 2) in 200 ml Isopropylalkohol versetzt. Während des Erhitzens auf Rückflußtemperatur setzte eine Kohlendi- oxidentwicklung ein. Nach beendeter Gasentwicklung ließ man noch 1 bis 2 Stunden nachreagieren, abkühlen und filtrierte die Suspen¬ sion. Der Filterkuchen wurde mit Isopropylalkohol gewaschen und bei 105°C und 100 hPa im Trockenschrank bis zur Gewichtskonstanz getrocknet. Die Ausbeute bezogen auf die Einsatzmenge an Hydrotalcit betrug 56,4 %. Beispiel 5;Production of hydrophobic hydrotalcite. 50 g of hydrotalcite were suspended in 250 ml of isopropyl alcohol and 33.2 g of lauric acid (molar ratio of hydro talcite: lauric acid = 1: 2) in 200 ml of isopropyl alcohol were added at room temperature within 30 min. Carbon dioxide evolution started while heating to reflux temperature. After the evolution of gas had ended, the mixture was left to react for a further 1 to 2 hours, cooled and the suspension was filtered. The filter cake was washed with isopropyl alcohol and dried at 105 ° C. and 100 hPa in a drying cabinet to constant weight. The yield based on the amount of hydrotalcite used was 56.4%. Example 5;
Beispiel 1 wurde unter Einsatz von 3 g des mit Laurinsäure hydro- phobierten Hydrotalcits aus Beispiel 4 wiederholt. Innerhalb von 4,5 Stunden wurden 89 g einer farblosen klaren Flüssigkeit erhal¬ ten, deren gaschromatographisch bestimmter Gehalt an Aldolkon¬ densat 68 Gew.-% betrug. Example 1 was repeated using 3 g of the hydrotalcite from Example 4 which had been hydrophobicized with lauric acid. Within 4.5 hours, 89 g of a colorless, clear liquid were obtained, the gas chromatographically determined content of aldol condensate being 68% by weight.

Claims

Patentansprüche Claims
1. Verfahren zur Aldolisierung von Verbindungen mit aktiven Was¬ serstoffatomen, dadurch gekennzeichnet, daß die Reaktion in Gegenwart von kristallwasserhaltigen Doppelschichthydroxiden unter azeotropen Bedingungen durchgeführt wird.1. A process for the aldolization of compounds with active hydrogen atoms, characterized in that the reaction is carried out in the presence of double layer hydroxides containing water of crystallization under azeotropic conditions.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Verbindungen mit aktiven Wasserstoffatomen Fettaldehyde der Formel (I),2. The method according to claim 1, characterized in that as compounds with active hydrogen atoms fatty aldehydes of formula (I),
R-CHO (I)R-CHO (I)
in der R für einen gesättigten oder ungesättigten Kohlenwas¬ serStoffrest mit 6 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen steht, eingesetzt werden.in which R represents a saturated or unsaturated hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.
3. Verfahren nach mindestens einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die kristallwasserhaltigen Doppelschicht¬ hydroxide der Formel (II),3. The method according to at least one of claims 1 and 2, characterized in that the water-containing double layer hydroxides of the formula (II),
[«IIl-χHIIIχ(0H)2]Ay • m H^ (II)[« II l-χH III χ (0H) 2 ] A y • m H ^ (II)
folgen, in derfollow in the
M11 für mindestens ein zweiwertiges Metallkation,M 11 for at least one divalent metal cation,
MIII -für- mindestens ein dreiwertiges Metallkation,MIII -for- at least one trivalent metal cation,
A für das Äquivalent eines Anions einer ein- oder mehrbasi- gen Säure stehtA stands for the equivalent of an anion of a mono- or polybasic acid
und die Beziehungen 0,17 < x < 0,5, 0,17 <. y , 0,5 und 0 <_ m <, 1 gelten. and the relationships 0.17 <x <0.5, 0.17 <. y , 0.5 and 0 <_ m < , 1 apply.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß M11 ein Kation ausgewählt aus der Gruppe, die von Mg2+, Ca2+, Mn2+, Zn2+ und Cu + gebildet wird, darstellt.4. The method according to claim 3, characterized in that M 11 is a cation selected from the group consisting of Mg 2+ , Ca 2+ , Mn 2+ , Zn 2+ and Cu + .
5. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß M111 ein Kation ausgewählt aus der Gruppe, die von Al3+, Fe3+ und Cr3+ gebildet wird, darstellt.5. The method according to claim 3, characterized in that M 111 is a cation selected from the group consisting of Al3 + , Fe3 + and Cr3 + .
6. Verfahren nach mindestens einem der Ansprüche 3 bis 5, dadurch gekennzeichnet, daß als kristallwasserhaltiges Doppelschicht- hydroxid Hydrotalcit der Formel (III)6. The method according to at least one of claims 3 to 5, characterized in that hydrotalcite of the formula (III) as double layer hydroxide containing water of crystallization
[Mg6Al2(0H)ι6]C03 • 4 H20 (III)[Mg6Al 2 (0H) ι 6 ] C0 3 • 4 H 2 0 (III)
eingesetzt wird.is used.
7. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß A ein Anion ausgewählt aus der Gruppe, die von Carbonat, Carboxylat, Chlorid, Nitrat, Sulfat oder Phosphat gebildet wird, dar¬ stellt.7. The method according to claim 3, characterized in that A represents an anion selected from the group consisting of carbonate, carboxylate, chloride, nitrate, sulfate or phosphate.
8. Verfahren nach mindestens einem der Ansprüche 1, 3 und 6, da¬ durch gekennzeichnet, daß als kristallwasserhaltiges Doppel- schichthydroxid ein mit Mono- oder Dicarbonsäuren modifizier¬ ter Hydrotalcit eingesetzt wird.8. The method according to at least one of claims 1, 3 and 6, da¬ characterized in that a hydrotalcite modified with mono- or dicarboxylic acids is used as the double layer hydroxide containing water of crystallization.
9. Verfahren nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Reaktion in Gegenwart von 0,1 bis 5 Gew.-% eines kristallwaserhaltigen Doppelschichthydroxids, be¬ zogen auf die Verbindungen mit aktiven Wasserstoffatomen, durchgeführt wird. 9. The method according to at least one of claims 1 to 8, characterized in that the reaction in the presence of 0.1 to 5 wt .-% of a crystal water-containing double layer hydroxide, based on the compounds with active hydrogen atoms, is carried out.
10. Verfahren nach mindestens einem der Ansprüche 1 bis 9, da¬ durch gekennzeichnet, daß die Reaktion bei einer Temperatur von 100 bis 150°C durchgeführt wird.10. The method according to at least one of claims 1 to 9, da¬ characterized in that the reaction is carried out at a temperature of 100 to 150 ° C.
11. Verfahren nach mindestens einem der Ansprüche 1 bis 10, da¬ durch gekennzeichnet, daß die Reaktion über einen Zeitraum von 1 bis 10 Stunden durchgeführt wird. 11. The method according to at least one of claims 1 to 10, da¬ characterized in that the reaction is carried out over a period of 1 to 10 hours.
PCT/EP1991/001140 1990-06-29 1991-06-20 Method for the aldolization of compounds with active hydrogen atoms WO1992000266A1 (en)

Applications Claiming Priority (2)

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DEP4020838.9 1990-06-29
DE19904020838 DE4020838A1 (en) 1990-06-29 1990-06-29 Aldol condensn. of active hydrogen cpds. esp. fatty aldehyde - in presence of hydrated double layer hydroxide catalyst under azeotropic conditions, giving intermediates for surfactants and lubricants

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EP0792862A1 (en) * 1996-02-29 1997-09-03 Elf Atochem S.A. Process for obtaining beta hydroxy and/or beta unsaturated carbonyl compounds
EP0921110A1 (en) * 1997-12-05 1999-06-09 Elf Atochem S.A. Use of compounds having hydrotalcite structure for the preparation of beta-hydroxy and/or alpha-beta unsaturated carbonyl compounds

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EP0792863A1 (en) * 1996-02-29 1997-09-03 Elf Atochem S.A. Process for producing isophorone
EP0792862A1 (en) * 1996-02-29 1997-09-03 Elf Atochem S.A. Process for obtaining beta hydroxy and/or beta unsaturated carbonyl compounds
FR2745565A1 (en) * 1996-02-29 1997-09-05 Atochem Elf Sa PROCESS FOR OBTAINING CARBONYL COMPOUNDS BETA HYDROXY AND / OR ALPHA-BETA UNSATURATED
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US5849957A (en) * 1996-02-29 1998-12-15 Elf Atochem S.A. Process for obtaining isophorone
US5936131A (en) * 1996-02-29 1999-08-10 Elf Atochem S,A Process for obtaining β-hydroxy and/or α,β-unsaturated carbonyl compounds
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