DE19923121A1 - Hydrogen peroxide oxidation of primary alcohols to give aldehydes and carboxylic acids uses a catalyst containing a manganese salt, a 1,4,7-tri-(1-20C alkyl)-1,4,7-triazacyclononane and a co-ligand - Google Patents

Hydrogen peroxide oxidation of primary alcohols to give aldehydes and carboxylic acids uses a catalyst containing a manganese salt, a 1,4,7-tri-(1-20C alkyl)-1,4,7-triazacyclononane and a co-ligand

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DE19923121A1
DE19923121A1 DE1999123121 DE19923121A DE19923121A1 DE 19923121 A1 DE19923121 A1 DE 19923121A1 DE 1999123121 DE1999123121 DE 1999123121 DE 19923121 A DE19923121 A DE 19923121A DE 19923121 A1 DE19923121 A1 DE 19923121A1
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acid
alkyl
tatacn
hydrogen peroxide
tri
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Thomas Barth
Joaquim Henrique Teles
Albrecht Berkessel
Christoph Sklorz
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium

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Abstract

H2O2 oxidation of mono- or poly-hydric alcohols is effected using a catalyst comprising: (a) an Mn salt; (b) 1,4,7-tri-(1-20C alkyl)-1,4,7-triazacyclononanes (TATACN); and (c) co-ligands comprising organic compounds containing \-2 OH or carboxyl groups, tosylglycine, 2-sulfobenzoic acid or 1,2-diaminocyclohexane. H2O2 oxidation of mono- or poly-hydric alcohols is effected using a catalyst comprising (a) an Mn salt; (b) 1,4,7-tri-(1-20C alkyl)-1,4,7-triazacyclononanes (TATACN); and (c) co-ligands comprising organic compounds containing \-2 OH or carboxyl groups, tosylglycine, 2-sulfobenzoic acid or 1,2-diaminocyclohexane. AnMnXm (I) A = alkali(ne earth) metal cation; X = an anion; and m = greater than 0 and n \- 0 such that (I) is electro-neutral An Independent claim is also included for the catalyst system..

Description

Die Erfindung betrifft ein Verfahren zur Oxidation primärer ein- oder mehrwertiger Alkohole zu Aldehyden und/oder Carbonsäuren. Aldehyde und Carbonsäuren sind wichtige Bausteine für organische Synthesen.The invention relates to a process for the oxidation of primary or polyhydric alcohols to aldehydes and / or carboxylic acids. Aldehydes and Carboxylic acids are important building blocks for organic synthesis.

Bei der Oxidation von Alkoholen mit Salpetersäure werden stöchiometrische Mengen an Nebenprodukten wie Lachgas erhalten, die entsorgt oder weiter verwertet werden müssen.The oxidation of alcohols with nitric acid becomes stoichiometric Amounts of by-products such as laughing gas are received or disposed of must be recycled.

In jüngerer Zeit wurde daher die Verwendung von Mangan enthaltenden Katalysatoren für Oxidationsreaktionen vorgeschlagen. In WO 98/39098 ist beispielsweise ein Verfahren zur Oxidation von Alkoholen wie 3,4- Dimethoxybenzylalkohol zu Aldehyden unter Verwendung von [Mn(Bcyclam)]Cl2 beschrieben. Auch andere spezielle heterocyclische Liganden können eingesetzt werden. Die Aldehyde werden jedoch nur in geringen Ausbeuten erhalten. Zudem werden keine Säuren gebildet.Recently, the use of manganese-containing catalysts for oxidation reactions has been proposed. WO 98/39098, for example, describes a process for the oxidation of alcohols such as 3,4-dimethoxybenzyl alcohol to aldehydes using [Mn (Bcyclam)] Cl 2 . Other special heterocyclic ligands can also be used. However, the aldehydes are only obtained in low yields. In addition, no acids are formed.

In der EP-A-0 798 311 ist ein Verfahren zum Abbau von Stärke, insbesondere teilchenförmiger Stärke beschrieben, bei dem mit Wasserstoffperoxid in Gegenwart eines Katalysators umgesetzt wird. Als Katalysator können dabei beispielsweise Mangankomplexe mit 1,4,7-Trimethyl-1,4,7-triazacyclononan (TMTACN) als Liganden eingesetzt werden. EP-A-0 798 311 describes a process for the degradation of starch, in particular described particulate starch, in which with hydrogen peroxide in Is implemented in the presence of a catalyst. Can act as a catalyst for example manganese complexes with 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN) can be used as ligands.  

In Tetrahedron Letters 1998, 39, Seiten 4909 bis 4912 ist die Oxidation von Kohlenwasserstoffen oder Cyclohexanol mit Oxidationsmitteln wie Peressigsäure oder Wasserstoffperoxid/Essigsäure-Gemischen beschrieben. Dabei wird in Gegenwart von [(Mn(TNTACN))2O3](PF6)2-Komplexen als Katalysator gearbeitet.Tetrahedron Letters 1998, 39, pages 4909 to 4912 describes the oxidation of hydrocarbons or cyclohexanol with oxidizing agents such as peracetic acid or hydrogen peroxide / acetic acid mixtures. The catalyst is used in the presence of [(Mn (TNTACN)) 2 O 3 ] (PF 6 ) 2 complexes.

Aufgabe der vorliegenden Erfindung ist die Bereitstellung eines Verfahrens zur Oxidation primärer Alkohole zu Aldehyden und Carbonsäuren, bei dem mit Wasserstoffperoxid als Oxidationsmittel gearbeitet werden kann und das die Produkte in hoher Ausbeute liefert.The object of the present invention is to provide a method for Oxidation of primary alcohols to aldehydes and carboxylic acids Hydrogen peroxide can be worked as an oxidizing agent and that Delivers products in high yield.

Die Aufgabe wird erfindungsgemäß gelöst durch ein Verfahren zur Oxidation primärer ein- oder mehrwertiger Alkohole mit Wasserstoffperoxid in Gegenwart eines Katalysators, bei dem ein Katalysator­ system eingesetzt wird aus
The object is achieved according to the invention by a process for the oxidation of primary mono- or polyhydric alcohols with hydrogen peroxide in the presence of a catalyst, in which a catalyst system is used

a) Mangansalzen der allgemeinen Formel (I)
a) Manganese salts of the general formula (I)

AnMnXm (I)
A n MnX m (I)

mit
A Kation aus der Gruppe der Alkali- und Erdalkalimetalle,
X Anion,
m < 0,
n ≧ 0,
wobei m und n so gewählt sind, daß die Elektroneutralitätsbedingung erfüllt ist,
With
A cation from the group of alkali and alkaline earth metals,
X anion,
m <0,
n ≧ 0,
where m and n are chosen so that the electroneutrality condition is fulfilled,

b) 1,4,7-Tri(C1-20-alkyl)-1,4,7-triazacyclononanen (TATACN) und
b) 1,4,7-tri (C 1-20 alkyl) -1,4,7-triazacyclononanes (TATACN) and

c) Coliganden, die ausgewählt sind aus organischen Verbindungen, die mindestens 2 Hydroxyl- oder Carboxylgruppen aufweisen, oder Tosylglycin, 2-Sulfobenzoesäure oder 1,2-Diaminocyclohexan.c) Coligands which are selected from organic compounds which have at least 2 hydroxyl or carboxyl groups, or Tosylglycine, 2-sulfobenzoic acid or 1,2-diaminocyclohexane.

Es wurde erfindungsgemäß gefunden, daß unter Einsatz des vorstehenden Katalysatorsystems die Oxidation primärer Alkohole mit Wasserstoffperoxid in hohen Ausbeuten gelingt. Wasserstoffperoxid ist dabei technisch erhältlich. Mangan ist ein kostengünstiges Übergangsmetall. Da der Katalysator zudem in sehr geringen Konzentrationen verwendet werden kann, kann die Oxidation kostengünstig durchgeführt werden.It has been found according to the invention that using the above Oxidation of primary alcohols with hydrogen peroxide in the catalyst system high yields succeed. Hydrogen peroxide is technically available. Manganese is an inexpensive transition metal. Since the catalyst is also in very low concentrations can be used, the oxidation be carried out inexpensively.

Im Katalysatorsystem können die Komponenten (a) und (b) auch in Form von [(TATACN)Mn(O-C1-20-Alkyl)3]X oder [(TATACN)Mn(µ-O)3Mn (TATACN)]X vorliegen. Hierbei sind somit die Komponenten (a) und (b) kombiniert. Die Kombination kann jedoch auch in situ erfolgen. Der Alkylrest ist vorzugsweise ein C1-6-Alkylrest, insbesondere Methylrest.In the catalyst system, components (a) and (b) can also be in the form of [(TATACN) Mn (OC 1-20 alkyl) 3 ] X or [(TATACN) Mn (µ-O) 3 Mn (TATACN)] X available. Components (a) and (b) are thus combined. However, the combination can also take place in situ. The alkyl radical is preferably a C 1-6 alkyl radical, in particular methyl radical.

Als Komponente (a) werden Mangansalze der vorstehenden allgemeinen Formel eingesetzt. Für n = 0 entsprechen die Salze der Formel MnXm. Die Alkali- und Erdalkalimetalle sind vorzugsweise Natrium oder Kalium. X kann ein beliebig gewähltes Anion sein, wie beispielsweise RO-, F-, Cl-, Br-, I-, NCS-, N3-, RCOO-, RSO3-, RSO4-, OH-, O2 2-, HOO-, SH-, CN-, OCN-, NO3-, ClO4-, PF6-, SO4 2-, OAc-, BPh4-, oder F3CSO3-, R steht für C1-C20-Alkyl, -Cycloalkyl, -Aryl oder -Benzyl. Beispiele für solche Salze sind Mangan(II)sulfat, Mangan(II)acetat, Mangan­ (III)chlorid oder Kaliumhexachloromanganat(IV). Manganese salts of the above general formula are used as component (a). For n = 0, the salts correspond to the formula MnX m . The alkali and alkaline earth metals are preferably sodium or potassium. X can be any anion selected, such as RO, F, Cl, Br, I, NCS, N 3 , RCOO, RSO 3 , RSO 4 , OH, O 2 2 , HOO-, SH-, CN-, OCN-, NO 3 -, ClO 4 -, PF 6 -, SO 4 2 -, OAc-, BPh 4 -, or F 3 CSO 3 -, R stands for C 1 - C 20 alkyl, cycloalkyl, aryl or benzyl. Examples of such salts are manganese (II) sulfate, manganese (II) acetate, manganese (III) chloride or potassium hexachloromanganate (IV).

Als Komponente (b) wird TATACN eingesetzt. Dabei weist der Alkylrest vorzugsweise 1 bis 12, besonders bevorzugt 1 bis 6, insbesondere 1 oder 2 C- Atome auf. Insbesondere wird 1,4,-Trimethyl-1,4,7-triazacyclononan (TMTACN) eingesetzt.TATACN is used as component (b). The alkyl residue preferably 1 to 12, particularly preferably 1 to 6, in particular 1 or 2 C- Atoms on. In particular, 1,4-trimethyl-1,4,7-triazacyclononane (TMTACN) used.

Der Coligand (c) kann ausgewählt sein aus Verbindungen der allgemeinen Formel (II)
The coligand (c) can be selected from compounds of the general formula (II)

R6R7C(OH)-L-C(OH)R4R5 (II)
R 6 R 7 C (OH) -LC (OH) R 4 R 5 (II)

mit
L gegebenenfalls substituierter, gesättigter oder ungesättigter, gegebenenfalls cyclischer C1-20 Kohlenwassrstoffrest,
R4 bis R6 unabhängig C1-12-Alkyl, wobei R4 und R6 zusammen einen C1-9- Alkylenrest bilden können, oder R4, R5 und/oder R6, R7 gemeinsam doppelt gebundener Sauerstoff.With
L optionally substituted, saturated or unsaturated, optionally cyclic C 1-20 hydrocarbon residue,
R 4 to R 6 are independently C 1-12 alkyl, where R 4 and R 6 together can form a C 1-9 alkylene radical, or R 4 , R 5 and / or R 6 , R 7 together double-bonded oxygen.

Bevorzugt ist der Coligand (c) ausgewählt aus Dicarbonsäuren und Ascorbinsäure, wobei der pKa 1-Wert < 7 ist (bestimmt in Wasser bei 25°C), deren Alkalisalzen oder Gemischen davon.The coligand (c) is preferably selected from dicarboxylic acids and ascorbic acid, the pK a 1 value being <7 (determined in water at 25 ° C.), their alkali metal salts or mixtures thereof.

Vorzugsweise ist der Coligand (c) ausgewählt aus Oxalsäure, Ascorbinsäure, Dihydroxyfumarsäure, Weinsäure, Maleinsäure, Quadratsäure, deren Alkalisalzen und Gemischen davon oder ähnlichen Verbindungen. Besonders bevorzugt sind Gemische von Oxalsäure/Natriumoxalat und Ascorbinsäure/Natriumascorbat oder die reinen Komponenten. Statt der Alkalimetallsalze der Säuren können auch die Dicarbonsäuren in situ mit Basen wie Alkalimetallhydroxiden umgesetzt werden. The coligand (c) is preferably selected from oxalic acid, ascorbic acid, Dihydroxyfumaric acid, tartaric acid, maleic acid, squaric acid, their alkali salts and mixtures thereof or similar compounds. Are particularly preferred Mixtures of oxalic acid / sodium oxalate and ascorbic acid / sodium ascorbate or the pure components. Instead of the alkali metal salts of the acids, the Dicarboxylic acids are reacted in situ with bases such as alkali metal hydroxides.  

Die Umsetzung kann lösungsmittelfrei oder in einem Lösungsmittel durchgeführt werden. Als Lösungsmittel können dabei die Alkohole selbst im Überschuß eingesetzt werden. Auch der Einsatz von Wasser oder anderen Lösungsmitteln wie Acetonitril, Aceton oder halogenierten Kohlenwasserstoffen ist möglich.The reaction can be carried out without solvent or in a solvent become. The alcohols themselves can be used as solvents in excess be used. The use of water or other solvents such as acetonitrile, acetone or halogenated hydrocarbons is possible.

Der primäre Alkohol kann aus einer Vielzahl organischer primärer ein- oder mehrwertiger Alkohole ausgewählt werden. Vorzugsweise handelt es sich um einen ein- oder zweiwertigen Alkohol.The primary alcohol can be a variety of organic primary ones polyhydric alcohols can be selected. It is preferably a monohydric or dihydric alcohol.

Die primären Alkohole können beispielsweise der allgemeinen Formel R'-CH2OH entsprechen, wobei R' ein geradkettiger oder verzweigter Alkyl-, Aryl-, substituierter Alkyl- oder substituierter Aryl-Rest ist, der vorzugsweise 1 bis 20, besonders bevorzugt 1 bis 10 C-Atome aufweist.The primary alcohols can correspond, for example, to the general formula R'-CH 2 OH, where R 'is a straight-chain or branched alkyl, aryl, substituted alkyl or substituted aryl radical, which is preferably 1 to 20, particularly preferably 1 to 10 C atoms.

Beispiele geeigneter derartiger Alkohole sind Methanol, Ethanol, Propanol, Butanol, Pentanol, Hexanol, Heptanol, Octanol, Nonanol, Decanol, Undecanol, usw. bis Eicosanol oder entsprechende verzweigte Isomere, Allylalkohol, Benzylalkohol, Prenol, Isoprenol, Geraniol, Nerol, Phytol, Retinol, 2- Phenylethanol.Examples of suitable alcohols of this type are methanol, ethanol, propanol, Butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, etc. to eicosanol or corresponding branched isomers, allyl alcohol, Benzyl alcohol, prenol, isoprenol, geraniol, nerol, phytol, retinol, 2- Phenylethanol.

Erfindungsgemäß einsetzbare Diole können beispielsweise der allgemeinen Formel HOH2C-Y-CH2OH entsprechen, wobei Y ein geradkettiger oder verzweigter Alkylen-, Arylen-, substituierter Alkylen- oder substituierter Arylen- Rest ist, der vorzugsweise 1 bis 20, besonders bevorzugt 1 bis 10 C-Atome aufweist. Beispiele bevorzugter Diole sind 1,2-Ethandiol, 1,3-Propandiol, 1,4- Butandiol, 1,5-Pentandiol, 1,6-Hexandiol, 1,7-Heptandiol, 1,8-Octandiol, 1,9- Nonandiol, 1,10-Decandiol, 1,11-Undecandiol usw. bis 1,20-Eicosandiol oder deren verzweigte Isomere, But-2-en-1,4-diol, But-2-in-1,4-diol, Hexin-1,6-diol, Hexadiin-1,6-diol, Cyclohexandimethanol.Diols which can be used according to the invention can, for example, correspond to the general formula HOH 2 CY-CH 2 OH, where Y is a straight-chain or branched alkylene, arylene, substituted alkylene or substituted arylene radical, which is preferably 1 to 20, particularly preferably 1 to 10 C atoms. Examples of preferred diols are 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, 1,11-undecanediol etc. to 1,20-eicosanediol or their branched isomers, but-2-ene-1,4-diol, but-2-in-1,4-diol, Hexin-1,6-diol, hexadiene-1,6-diol, cyclohexanedimethanol.

Mehrwertige Alkohole sind beispielsweise Glycerin, Trimethylolethan, Trimethylolpropan, Pentaerythrit, Sorbit. Polyhydric alcohols are, for example, glycerol, trimethylolethane, Trimethylolpropane, pentaerythritol, sorbitol.  

Die Umsetzung wird vorzugsweise bei einer Temperatur im Bereich von -50 bis 100°C, besonders bevorzugt -30 bis 80°C, insbesondere -10 bis 60°C durchgeführt.The reaction is preferably carried out at a temperature in the range from -50 to 100 ° C, particularly preferably -30 to 80 ° C, in particular -10 to 60 ° C carried out.

Der Druck beträgt dabei vorzugsweise 1 bis 200 bar, besonders bevorzugt 1 bis 100 bar, insbesondere etwa Normaldruck.The pressure is preferably 1 to 200 bar, particularly preferably 1 to 100 bar, especially about normal pressure.

Die eingesetzte Menge an Wasserstoffperoxid kann in weiten Bereichen frei gewählt werden.The amount of hydrogen peroxide used can be free in a wide range to get voted.

Die Erfindung wird nachstehend durch Beispiele näher erläutert.The invention is explained in more detail below by examples.

BeispieleExamples Beispiel 1example 1 ButtersäureButyric acid

In einem im Wasserbad gekühlten Kolben wurden 3 ml Acetonitril, 2 × 10-5 mol TMTACN (0,5 mol-%), 1,5 × 10-5 mol Mangansulfat (0,375 mol-%), 1,6 × 10-4 mol Natriumascorbat, 4 × 10-5 mol Ascorbinsäure und 4 mmol 1-Butanol vereinigt. Hierzu gab man 1 ml 30%ige Wasserstoffperoxid-Lösung. Nach 18 Stunden (79% Butanol-Umsatz) erhielt man (GC-Fl.-%) 69% Buttersäure (Selektivität: 87%) und 3,5% 1-Butanal (Selektivität: 4%).In a flask cooled in a water bath, 3 ml of acetonitrile, 2 × 10 -5 mol TMTACN (0.5 mol%), 1.5 × 10 -5 mol manganese sulfate (0.375 mol%), 1.6 × 10 -4 mol sodium ascorbate, 4 × 10 -5 mol ascorbic acid and 4 mmol 1-butanol combined. 1 ml of 30% hydrogen peroxide solution was added. After 18 hours (79% butanol conversion), 69% butyric acid (selectivity: 87%) and 3.5% 1-butanal (selectivity: 4%) were obtained (GC area%).

Bei einem identischen Ansatz mit 2 ml 30%iger Wasserstoffperoxid-Lösung und einer Reaktionszeit von drei Stunden bei 0°C erhielt man ein Verhältnis von Buttersäure zu 1-Butanal von 1,17 : 1.In an identical batch with 2 ml of 30% hydrogen peroxide solution and A reaction time of three hours at 0 ° C gave a ratio of Butyric acid to 1-butanal of 1.17: 1.

Beispiel 2Example 2 CaprylsäureCaprylic acid

In einem im Wasserbad gekühlten Kolben wurden 1,5 ml Acetonitril, 1 × 10-5 mol TMTACN (0,5 mol-%), 0,75 × 10-5 mol Mangansulfat (0,375 mol-%), 1,2 × 10-4 mol Natriumascorbat, 2 × 10-5 mol Ascorbinsäure und 2 mmol 1-Octanol vereinigt. Hierzu gab man 1 ml 30%ige Wasserstoffperoxid-Lösung. Nach 18 Stunden (45% Octanol-Umsatz) erhielt man (GC-Fl.-%) ein Verhältnis von Caprylsäure zu 1- Octanal von 1 : 13.1.5 ml of acetonitrile, 1 × 10 -5 mol of TMTACN (0.5 mol%), 0.75 × 10 -5 mol of manganese sulfate (0.375 mol%), 1.2 × 10 were placed in a flask cooled in a water bath -4 mol sodium ascorbate, 2 × 10 -5 mol ascorbic acid and 2 mmol 1-octanol combined. 1 ml of 30% hydrogen peroxide solution was added. After 18 hours (45% octanol conversion), a ratio of caprylic acid to 1-octanal of 1:13 was obtained (GC area%).

Claims (10)

1. Verfahren zur Oxidation primärer ein- oder mehrwertiger Alkohole mit Wasserstoffperoxid in Gegenwart eines Katalysators, dadurch gekennzeichnet, daß ein Katalysatorsystem eingesetzt wird aus
  • a) Mangansalzen der allgemeinen Formel (I)
    AnMnXm (I)
    mit
    A Kation aus der Gruppe der Alkali- und Erdalkalimetalle,
    X Anion,
    m < 0,
    n ≧ 0,
    wobei m und n so gewählt sind, daß die Elektroneutralitätsbedingung erfüllt ist,
  • b) 1,4,7-Tri(C1-20-alkyl)-1,4,7-triazacyclononanen (TATACN) und
  • c) Coliganden, die ausgewählt sind aus organischen Verbindungen, die mindestens 2 Hydroxyl- oder Carboxylgruppen aufweisen, oder Tosylglycin, 2-Sulfobenzoesäure oder 1,2-Diaminocyclohexan.
1. A process for the oxidation of primary mono- or polyhydric alcohols with hydrogen peroxide in the presence of a catalyst, characterized in that a catalyst system is used
  • a) Manganese salts of the general formula (I)
    A n MnX m (I)
    With
    A cation from the group of alkali and alkaline earth metals,
    X anion,
    m <0,
    n ≧ 0,
    where m and n are chosen so that the electroneutrality condition is fulfilled,
  • b) 1,4,7-tri (C 1-20 alkyl) -1,4,7-triazacyclononanes (TATACN) and
  • c) Coligands which are selected from organic compounds which have at least 2 hydroxyl or carboxyl groups, or tosylglycine, 2-sulfobenzoic acid or 1,2-diaminocyclohexane.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß im Katalysatorsystem die Komponenten (a) und (b) in Form von [(TATACN)Mn(O-C1-20-Alkyl)3]X oder [(TATACN)Mn(µ-O)3Mn (TATACN)]X vorliegen.2. The method according to claim 1, characterized in that in the catalyst system components (a) and (b) in the form of [(TATACN) Mn (OC 1-20 alkyl) 3 ] X or [(TATACN) Mn (µ- O) 3 Mn (TATACN)] X are present. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Coligand (c) ausgewählt ist aus Verbindungen der allgemeinen Formel (II)
R6R7C(OH)-L-C(OH)R4R5 (II)
mit
L gegebenenfalls substituierter, gesättigter oder ungesättigter, gegebenenfalls cyclischer C1-20 Kohlenwasserstoffrest,
R4 bis R6 unabhängig C1-12-Alkyl, wobei R4 und R6 zusammen einen C1-9- Alkylenrest bilden können, oder R4, R5 und/oder R6, R7 gemeinsam doppelt gebundener Sauerstoff.3. The method according to claim 1 or 2, characterized in that the coligand (c) is selected from compounds of the general formula (II)
R 6 R 7 C (OH) -LC (OH) R 4 R 5 (II)
With
L optionally substituted, saturated or unsaturated, optionally cyclic C 1-20 hydrocarbon radical,
R 4 to R 6 are independently C 1-12 alkyl, where R 4 and R 6 together can form a C 1-9 alkylene radical, or R 4 , R 5 and / or R 6 , R 7 together double-bonded oxygen. 4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Coligand (c) ausgewählt ist aus Dicarbonsäuren mit pKa 1 < 7 und Ascorbinsäure, deren Alkalisalzen oder Gemischen davon.4. The method according to claim 1 or 2, characterized in that the coligand (c) is selected from dicarboxylic acids with pK a 1 <7 and ascorbic acid, its alkali metal salts or mixtures thereof. 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß der Coligand (c) ausgewählt ist aus Oxalsäure, Ascorbinsäure, Dihydroxyfumarsäure, Wein­ säure, Maleinsäure, Quadratsäure, deren Alkalisalzen und Gemischen davon. 5. The method according to claim 4, characterized in that the coligand (c) is selected from oxalic acid, ascorbic acid, dihydroxy fumaric acid, wine acid, maleic acid, squaric acid, their alkali salts and mixtures thereof.   6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Komponente (b) 1,4,7-Trimethyl-1,4,7-triazacyclononan (TMTACN) ist.6. The method according to any one of claims 1 to 5, characterized in that the Component (b) is 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN). 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der primäre Alkohol ein ein- oder zweiwertiger Alkohol ist.7. The method according to any one of claims 1 to 6, characterized in that the primary alcohol is a monohydric or dihydric alcohol. 8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der primäre Alkohol zu Aldehyden, Carbonsäuren oder Gemischen davon oxidiert wird.8. The method according to any one of claims 1 to 7, characterized in that the primary alcohol oxidized to aldehydes, carboxylic acids or mixtures thereof becomes. 9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es bei einer Temperatur im Bereich von -50 bis 100°C und einem Druck im Bereich von 1 bis 200 bar durchgeführt wird.9. The method according to any one of claims 1 to 8, characterized in that it at a temperature in the range of -50 to 100 ° C and a pressure in Range from 1 to 200 bar is carried out. 10. Katalysatorsystem, wie es in einem der Ansprüche 1 bis 6 definiert ist.10. A catalyst system as defined in any one of claims 1 to 6.
DE1999123121 1999-05-19 1999-05-19 Hydrogen peroxide oxidation of primary alcohols to give aldehydes and carboxylic acids uses a catalyst containing a manganese salt, a 1,4,7-tri-(1-20C alkyl)-1,4,7-triazacyclononane and a co-ligand Withdrawn DE19923121A1 (en)

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DE10024617A DE10024617A1 (en) 1999-05-19 2000-05-18 Production of carboxylic acid and/or aldehydes comprises oxidation in the presence of a catalyst comprising a manganese salt, 1,4,7-tri(1-20C alkyl)-1,4,7-triazacyclononane and co-ligands

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US8975423B2 (en) 2010-02-02 2015-03-10 Hexion Inc. Epoxidation process
US9102640B2 (en) 2010-02-02 2015-08-11 Evonik Degussa Gmbh Process for the manufacture of a 1,2-epoxide and a device for carrying out said process
US9145378B2 (en) 2010-02-02 2015-09-29 Hexion Inc. Manufacture of an epoxyethyl ethers or glycidyl ethers
US9174955B2 (en) 2010-02-02 2015-11-03 Hexion Inc. Manufacture of an epoxyethyl carboxylate or glycidyl carboxylate
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US8946470B2 (en) 2010-07-21 2015-02-03 Catexel Limited Method for the oxidation of unsaturated organic compounds
US9024048B2 (en) 2011-06-22 2015-05-05 Evonik Degussa Gmbh Apparatus and methods to preserve catalyst activity in an epoxidation process

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