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WO1992000266A1 - Procede d'aldolisation de composes contenant des atomes d'hydrogene actifs - Google Patents

Procede d'aldolisation de composes contenant des atomes d'hydrogene actifs 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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WO
WIPO (PCT)
Prior art keywords
reaction
compounds
water
active hydrogen
hydrogen atoms
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.)
Ceased
Application number
PCT/EP1991/001140
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German (de)
English (en)
Inventor
Udo Hees
Wolfgang Breuer
Hans-Christian Raths
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1992000266A1 publication Critical patent/WO1992000266A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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.

Landscapes

  • 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

On peut soumettre des aldéhydes gras à une condensation d'aldol en présence d'hydroxydes à double couche contenant de l'eau de cristallisation après avoir éliminé l'eau de cristallisation et de réaction dans des conditions azéotropes.
PCT/EP1991/001140 1990-06-29 1991-06-20 Procede d'aldolisation de composes contenant des atomes d'hydrogene actifs Ceased WO1992000266A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904020838 DE4020838A1 (de) 1990-06-29 1990-06-29 Verfahren zur aldolisierung von verbindungen mit aktiven wasserstoffatomen
DEP4020838.9 1990-06-29

Publications (1)

Publication Number Publication Date
WO1992000266A1 true WO1992000266A1 (fr) 1992-01-09

Family

ID=6409397

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/001140 Ceased WO1992000266A1 (fr) 1990-06-29 1991-06-20 Procede d'aldolisation de composes contenant des atomes d'hydrogene actifs

Country Status (3)

Country Link
EP (1) EP0536193A1 (fr)
DE (1) DE4020838A1 (fr)
WO (1) WO1992000266A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0792862A1 (fr) * 1996-02-29 1997-09-03 Elf Atochem S.A. Procédé d'obtention de composés carbonyles beta hydroxy et/ou -beta insaturés
EP0792863A1 (fr) * 1996-02-29 1997-09-03 Elf Atochem S.A. Procédé d'obtention d'isophorone
EP0921110A1 (fr) * 1997-12-05 1999-06-09 Elf Atochem S.A. Utilisation de composés de structure de type hydrotalcite pour la préparation de composés carbonyles-bèta-hydroxy et/ou alpha-bèta insaturés

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1203243B (de) * 1961-12-22 1965-10-21 Exxon Research Engineering Co Verfahren zur Herstellung von alpha, beta-ungesaettigten Aldehyden und Ketonen
DE2705857A1 (de) * 1976-02-12 1977-08-25 Union Carbide Corp Katalysator und dessen verwendung fuer die durchfuehrung der aldol-kondensation
GB2048239A (en) * 1979-05-01 1980-12-10 Turner W F Production of unsaturated carbonyl compounds
US4316990A (en) * 1980-10-29 1982-02-23 Eastman Kodak Company Preparation of α,β-aldehydes by aldol condensation
EP0095783A2 (fr) * 1982-06-02 1983-12-07 Union Carbide Corporation Condensations aldoliques catalysées
US4528405A (en) * 1983-12-30 1985-07-09 Union Carbide Corporation Aldol condensation of enolizable aldehydes using a metal carboxylate catalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1203243B (de) * 1961-12-22 1965-10-21 Exxon Research Engineering Co Verfahren zur Herstellung von alpha, beta-ungesaettigten Aldehyden und Ketonen
DE2705857A1 (de) * 1976-02-12 1977-08-25 Union Carbide Corp Katalysator und dessen verwendung fuer die durchfuehrung der aldol-kondensation
GB2048239A (en) * 1979-05-01 1980-12-10 Turner W F Production of unsaturated carbonyl compounds
US4316990A (en) * 1980-10-29 1982-02-23 Eastman Kodak Company Preparation of α,β-aldehydes by aldol condensation
EP0095783A2 (fr) * 1982-06-02 1983-12-07 Union Carbide Corporation Condensations aldoliques catalysées
US4528405A (en) * 1983-12-30 1985-07-09 Union Carbide Corporation Aldol condensation of enolizable aldehydes using a metal carboxylate catalyst

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0792862A1 (fr) * 1996-02-29 1997-09-03 Elf Atochem S.A. Procédé d'obtention de composés carbonyles beta hydroxy et/ou -beta insaturés
EP0792863A1 (fr) * 1996-02-29 1997-09-03 Elf Atochem S.A. Procédé d'obtention d'isophorone
FR2745565A1 (fr) * 1996-02-29 1997-09-05 Atochem Elf Sa Procede d'obtention de composes carbonyles beta hydroxy et/ou alpha-beta insatures
FR2745566A1 (fr) * 1996-02-29 1997-09-05 Atochem Elf Sa Procede d'obtention d'isophorone
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
CN1065229C (zh) * 1996-02-29 2001-05-02 埃尔夫阿托化学有限公司 制备β－羟基和/或α,β－不饱和羰基化合物的方法
CN1065232C (zh) * 1996-02-29 2001-05-02 埃尔夫阿托化学有限公司 制备异佛尔酮(3,5,5－三甲基－2－环己烯－1－酮)的方法
US6271171B1 (en) 1996-02-29 2001-08-07 Elf Atochem S.A. Catalyst for obtaining β-hydroxy and/or α,β-unsaturated carbonyl compounds
EP0921110A1 (fr) * 1997-12-05 1999-06-09 Elf Atochem S.A. Utilisation de composés de structure de type hydrotalcite pour la préparation de composés carbonyles-bèta-hydroxy et/ou alpha-bèta insaturés
FR2772024A1 (fr) * 1997-12-05 1999-06-11 Atochem Elf Sa Utilisation de composes de structure de type hydrotalcite pour la preparation de composes carbonyles-beta-hydroxy et/ou alpha-beta-insatures
US6046366A (en) * 1997-12-05 2000-04-04 Elf Atochem S.A. Preparation of β-hydroxycarbonyl and/or α,β-unsaturated carbonyl compounds

Also Published As

Publication number Publication date
EP0536193A1 (fr) 1993-04-14
DE4020838A1 (de) 1992-01-02

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