EP0000478B1 - Procédé de préparation d'acyloines - Google Patents

Procédé de préparation d'acyloines Download PDF

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Publication number
EP0000478B1
EP0000478B1 EP78100262A EP78100262A EP0000478B1 EP 0000478 B1 EP0000478 B1 EP 0000478B1 EP 78100262 A EP78100262 A EP 78100262A EP 78100262 A EP78100262 A EP 78100262A EP 0000478 B1 EP0000478 B1 EP 0000478B1
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EP
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Prior art keywords
carbon atoms
catalyst
mol
thiazolium
methyl
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EP78100262A
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German (de)
English (en)
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EP0000478A1 (fr
Inventor
Horst-Jürgen Dr. Krause
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/17—Saturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups

Definitions

  • the invention relates to a process for the preparation of acyloin by condensing aldehydes in the presence of thiazolium salts.
  • the known processes have the disadvantage that the thiazolium salts used as catalysts can only be removed from the reaction mixture using very complex methods. If it is not possible to completely free the crude reaction product from the thiazolium salt, the subsequent distillation gives rise to unpleasant-smelling decomposition products, some of which pass over with the distillate and severely impair the quality of the acyloins obtained.
  • Another disadvantage is that the low molecular weight thiazolium salts can only be recovered from the wash water with great difficulty in pure form after working up the reaction mixture.
  • the object of the invention was therefore to find a process for the preparation of acyloin in which the disadvantages described do not occur.
  • a catalyst should be found which can be prepared from easily accessible components and can be removed in a simple manner from the reaction mixture of the acyloin condensation.
  • R3 represents a straight-chain or branched alkyl radical having 1 to 18 carbon atoms, a cycloalkyl radical having 3 to 18 carbon atoms, an arylalkyl radical having 7 to 18 carbon atoms or the group in which n is an integer from 2 to 4.
  • hydrocarbon radicals of the aforementioned aldehydes can also contain substituents, for example hydroxyl groups, ester or ether groups, as long as it is ensured that these substituents do not interfere with the acyloin condensation.
  • the thiazoles are generally allowed to act on the crosslinked chloromethyl polystyrenes in an inert solvent or in water.
  • Aprotic solvents such as e.g. Dimethylformamide, acetonitrile. Dioxane or tetrahydrofuran in question.
  • Excess thiazole can also be used as a solvent. It has proven to be expedient in any case to work with a stoichiometric excess of the thiazole in order to achieve a virtually complete conversion of the chloromethyl groups of the polystyrene resin.
  • the polymer catalyst containing thiazolium groups is filtered off, extracted with an inert solvent, for example ether or alcohol, and finally dried.
  • Inorganic and organic bases are suitable as co-catalysts, for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium acetate, potassium acetate, disodium hydrogen phosphate, triethylamine, triethanolamine, N-methylpyrrolidine or basic ion exchangers.
  • the amount of catalyst used is not critical. In general, the method according to the invention is used. those amounts of the catalyst resin carried out, which - based on the aldehyde to be reacted - contain 0.1 to 20 mol%, preferably 0.5 to 5 mol% of quaternary thiazolium groups. However, amounts which correspond to less than one mol% are sufficient to carry out the process.
  • the amount of base used is also not critical. In general, an amount which is equimolar to the thiazolium salt groups contained in the catalyst is used. However, it is preferred to work with 2 to 5 times the molar amount. When working in aqueous or aqueous-alcoholic solutions, the amount of base must be measured so that a pH of about 7.3 to about 8.5 is maintained.
  • the aldehydes to be reacted are optionally dissolved in a solvent, with the catalyst suspended therein, stirred at room temperature or at elevated temperature until the desired degree of conversion is reached.
  • the reaction temperature should not significantly exceed 100 ° C.
  • polar solvents such as water, methanol, ethanol, isopropanol, dioxane, tetrahydrofuran, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric acid triamide and pyridine and mixtures of these solvents, in particular water / ethanol mixtures, are suitable.
  • the catalyst is separated off from the reaction mixture by filtration. After distilling off the solvent which may be present, the liquid portions of the reaction mixture are worked up by the methods customary in organic chemistry, such as fractional distillation and recrystallization.
  • the separated catalyst can be reused after washing with a solvent and drying.
  • the thiazolium group-containing catalyst resin is used in the base form.
  • This procedure can be used as a cocatalyst without an additional base.
  • the base or OH form of the catalyst can be obtained very easily by treating the salt form of the thiazolium group-containing resin with an aqueous solution of a base such as sodium hydrogen carbonate until chloride ions are no longer present in the resin.
  • the products accessible via the process according to the invention are valuable fragrance and aroma substances; they are also valuable intermediates for organic synthesis.
  • the process according to the invention has the advantage over the known procedures that the catalyst used can be removed quantitatively from the reaction mixture in an extremely simple manner, namely by filtering. Any reduction in the quality of the acyloins produced by decomposition products which arise when the catalyst is distilled off is thereby avoided.
  • caprylaldehyde 25.6 g (0.2 mol) of caprylaldehyde were dissolved in 100 ml of water / ethanol mixture as in Example 4. 9.5 g (0.01 mol) of thiazolium salt catalyst in the CI form according to Example 1 were stirred into the solution. After adding 1 g of disodium hydrogen phosphate in 5 ml of water, the pH of the solution was adjusted to 7.4. The mixture was heated to 60 ° C under nitrogen and held at this temperature for 7 1/4 hours. The reaction mixture was worked up as described in Example 2. According to gas chromatographic determination, the crude reaction product contained 75% by weight of capryloin, 19.2% by weight of caprylaldehyde, 2.6% by weight of acetal and 3.2% by weight of aldol.
  • An ion exchange column made of glass (inner diameter 1 cm; length 60 cm), which was provided with a glass jacket and a glass frit, was charged with 20 g of the thiazolium salt catalyst in the OH form according to Example 8.
  • the column was filled with caprylic aldehyde under nitrogen.
  • the column contents were heated to 80 ° C by passing hot glycerin through the liquid jacket.
  • Fresh caprylic aldehyde was added at the top of the column under nitrogen from a dropping funnel to the same extent as the reaction product was drawn off via a glass tap at the bottom of the column. An average residence time of 2 hours was set for the reaction product.
  • the reaction product drawn off at the foot of the exchange column consisted of 90% by weight of capryloin, the rest was unreacted caprylaldehyde.
  • the resin containing 5- (2'-hydroxyethyl) -4-methyl-1,3-thiazolium groups contained 8.61% by weight of ionic chlorine; the total chlorine content was 9.33% by weight.
  • the resin catalyst thus obtained contained 7.17% by weight of ionic chlorine; the total chlorine content was 7.68% by weight.
  • the catalyst was filtered off from the resulting reaction mixture.
  • the unreacted acetaldehyde was distilled off in a water pump vacuum.
  • 1912 g of acetoin of bp 37 to 39 ° C./16 mbar (64% of theory) were obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (4)

1. Procédé de fabrication d'acyloïnes de formule:
Figure imgb0009
dans laquelle R1 et R2 sont identiques ou différents et représentent des radicaux alcoyle à chaîna droite ou ramifiée ayant 1 à 18 atomes de carbone, des radicaux cycloalcoyle ayant 3 à 18 atomes de carbone, des radicaux arylalcoyle ayant 7 à 18 atomes de carbone, ou bien R, et R2 représentent ensemble un radical alcoylène ayant 2 à 4 atomes de carbone, par condensation des aldéhydes correspondantes en présence de catalyseurs et de bases, caractérisé en ce qu'en tant que catalyseurs on utilise des produits de réaction de thiazols de formule:
Figure imgb0010
dans laquelle R3 représente de l'hydrogène ou un radical alcoyle ayant 1 à 5 atomes de carbone et R4 représente de l'hydrogène, un radical alcoyle ayant 1 à 5 atomes de carbone ou un groupe hydroxy- alcoyle ayant 2 à 4 atomes de carbone, et d'un chlorométhylpolystyrène réticulé.
2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise des quantités de résine catalyseur qui - par rapport à l'aldéhyde que l'on fait réagir - contiennent 0,1 à 20 moles %, de préférence 0,5 à 5 moles % de groupes thiazolium quaternaires.
3. Procédé selon les revendications 1 et 2, caractérisé en ce qu'on utilise comme catalyseur un produit de réaction de 5-(2'-hydroxyéthyl)-4-méthyl-1,3-thiazol et d'un chlorométhyl-polystyrène réticulé.
4. Procédé selon les revendications 1 à 3, caractérisé en ce qu'on utilise la résine catalyseur contenant des groupes thiazolium sous la forme de base.
EP78100262A 1977-07-20 1978-06-28 Procédé de préparation d'acyloines Expired EP0000478B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2732714 1977-07-20
DE2732714A DE2732714C2 (de) 1977-07-20 1977-07-20 Verfahren zur Herstellung von Acyloinen

Publications (2)

Publication Number Publication Date
EP0000478A1 EP0000478A1 (fr) 1979-02-07
EP0000478B1 true EP0000478B1 (fr) 1981-11-25

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Family Applications (1)

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EP78100262A Expired EP0000478B1 (fr) 1977-07-20 1978-06-28 Procédé de préparation d'acyloines

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EP (1) EP0000478B1 (fr)
JP (1) JPS5422310A (fr)
DE (1) DE2732714C2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998010160A1 (fr) 1996-09-04 1998-03-12 The Dow Chemical Company Revetement pour plancher, mur ou plafond
JP2008222596A (ja) * 2007-03-09 2008-09-25 Asahi Kasei Chemicals Corp シス二重結合含有ジカルボン酸誘導体の製造方法
CN104744615B (zh) * 2013-12-25 2017-05-24 浙江衢州万能达科技有限公司 一种全氟季铵型强碱性阴离子交换树脂的制备方法
CN106397151B (zh) * 2016-08-31 2019-06-11 濮阳天源生物科技有限公司 一种偶姻类化合物的制备方法

Also Published As

Publication number Publication date
DE2732714C2 (de) 1985-08-14
DE2732714A1 (de) 1979-02-08
JPS6223733B2 (fr) 1987-05-25
JPS5422310A (en) 1979-02-20
EP0000478A1 (fr) 1979-02-07

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