DE10163579A1 - Process for the oxidation of organic compounds, e.g. for production of esters from ethers, uses a liquid multi-phase ruthenium catalyst system and an oxygen atom donor and is carried out using an aqueous phase of neutral or alkaline pH - Google Patents

Abstract

A process for the oxidation of organic compounds using a liquid multi-phase catalyst system comprising at least one ruthenium-containing compound and an oxygen atom donor, is characterized in that the oxidation is carried out using an aqueous phase pH of at least 7.0.

Description

The invention relates to a process for the oxidation of organic compounds Use of a liquid, multi-phase catalyst system, the catalyst system has at least one ruthenium-containing compound and an oxygen atom donor and the aqueous phase of the reaction mixture during the entire reaction period a pH of greater than or equal to 7.0.

The selective oxidation of organic compounds under mild reaction conditions has great importance in the production of fine chemicals used in food and Fragrance sector, for agrochemicals and in the pharmaceutical industry as Basic building blocks can be used.

In the production of these basic building blocks, the turnover and the selectivity of the Oxidation in the foreground. As a mild oxidizing agent for the production of esters, Lactones, ketones and carboxylic acids are e.g. B. hydrogen peroxide, chlorates, nitrates, Bromates and hypochlorites are known, which are often associated with in the liquid phase a suitable catalyst can be used.

• - trans-[RuCl₂(dppp)₂], wobei dppp = 1,3-Bis(diphenylphosphino)propan
  (C. W. Jung, P. E. Garrou, P. R. Hoffman, K. G. Caulton, Inorg. Chem., 1984, 23, 726), ferner
• - RuO₂ × H₂O
  (Fa. Acros Organics N. V., 2440 Geel/Belgien),
• - Tetrapropylammoniumperruthenat (TPAP, [n-Pr₄N][RuO₄])
  (W. P. Griffith, S. V. Ley, G. P. Whitcombe, A. D. White, J. Chem. Soc., Chem. Comm. 1987, 1625),
• - cis-[RuCl₂(phen)], wobei phen = 1,10-Phenanthrolin
  (F. P. Dwyer, H. A,. Goodwin, E. C. Gyarfas, Aust. J. Chem., 1963, 16, 42) sowie
• - [RuCl₂(dppp)₂] PF₆
  (M. Bressan, P. Rigo, Inorg. Chem., 1975, 14, 2286),
• - Ruthenium-Porphyrin-Systeme, Rutheniumdiamintetraessigsäure, Rutheniumdioxid, Rutheniumtrichlorid
  (M. Bressan, A Morvillo, J. Chem. Soc., Chem. Commun., 1989, 421).

For extremely mild oxidation at room temperature, the use of ruthenium catalysts is state of the art. These are used in combination with an oxygen atom donor. Various suitable ruthenium catalysts for the oxidation of organic compounds are described in the literature. For the use of [RuCl ₂ (dmso) ₄ ] as catalyst, 0.05 mmol [RuCl ₂ (dmso) ₄ ] are dissolved in 2 cm ³ methylene chloride and 0.2 mmol NaOCl (1 molar) is added to this with stirring ( E. Alessio, G. Mestroni, G. Nardin, WM Attia, M. Calligaris, G. Sava, S. Zorzet, Inorg. Chem., 1988, 27, 4099). In addition, other starting compounds are suitable, such as. B.

• - trans- [RuCl ₂ (dppp) ₂ ], where dppp = 1,3-bis (diphenylphosphino) propane
  (CW Jung, PE Garrou, PR Hoffman, KG Caulton, Inorg. Chem., 1984, 23, 726), further
• - RuO ₂ × H ₂ O
  (Acros Organics NV, 2440 Geel / Belgium),
• Tetrapropylammonium perruthenate (TPAP, [n-Pr ₄ N] [RuO ₄ ])
  (WP Griffith, SV Ley, GP Whitcombe, AD White, J. Chem. Soc., Chem. Comm. 1987, 1625),
• - cis- [RuCl ₂ (phen)], where phen = 1,10-phenanthroline
  (FP Dwyer, H.A. Goodwin, EC Gyarfas, Aust. J. Chem., 1963, 16, 42) and
• - [RuCl ₂ (dppp) ₂ ] PF ₆
  (M. Bressan, P. Rigo, Inorg. Chem., 1975, 14, 2286),
• - Ruthenium-porphyrin systems, rutheniumdiamine tetraacetic acid, ruthenium dioxide, ruthenium trichloride
  (M. Bressan, A Morvillo, J. Chem. Soc., Chem. Commun., 1989, 421).

The reactive lithium hypochlorite is primarily used as an oxygen atom donor, however iodosobenzene (PhIO), hydrogen peroxide or persulfates are also used (M. Bressan, A Morvillo, J. Chem. Soc., Chem. Commun., 1989, 421; M. Bressan, A. Morvillo, G. Romanello, Inorg. Chem., 1990, 29, 2976). Small amounts (0.2 mol%) are required for this Ruthenium catalyst based on the amount of organic to be oxidized Connection needed. Disadvantages of this method are the very long reaction times and the associated low sales per hour. For example, sales are included Tetrahydropyran at 3-4% after one hour, although as an oxygen atom donor that is very efficiently known lithium hypochlorite is used. Furthermore, the Reaction mixture lithium hypochlorite are added at regular intervals. Other results published in the literature either require very high results Amounts of the ruthenium catalyst (A.B. Smith, R.M. Scarborough, Synth. Commun., 1980, 10, 205) or an up to 9-fold excess of an oxygen atom donor, such as. B. Hypochlorite (G. Balavoine, C. Eskenazi, F. Meunier, J. Mol. Catal., 1985, 30, 125).

It was therefore the object of the present invention to provide a process for the oxidation of organic compounds using a liquid, multi-phase To provide catalyst system, the catalyst system containing at least one ruthenium Compound and has an oxygen atom donor, in which a high conversion of oxidizing organic compound and a high selectivity of the oxidation is achieved, wherein the content of the ruthenium-containing catalyst system is preferably kept low and a short response time is achieved.

Surprisingly, the task was solved in that the oxidation a pH value greater than or equal to 7.0 is carried out. Because of the oxidation carried out during the entire reaction period in the neutral to alkaline pH range significantly higher sales can be achieved. Although the catalyst systems for one Selective oxidation of organic compounds has not been known for a long time recognized that with this reaction the adherence to a certain range of the pH value is essential. The solution to the task was all the more surprising, especially since showed that for each reaction system consisting of a catalyst system to be oxidized organic compound, oxygen atom donor and selected solvent, an optimal pH range exists.

The present invention therefore relates to a method according to claim 1 for Oxidation of organic compounds using a liquid, multi-phase Catalyst system, the catalyst system containing at least one containing ruthenium Compound and has an oxygen atom donor, which is characterized in that the oxidation is at a pH of the aqueous phase greater than or equal to 7.0 is carried out.

In addition, the present invention relates to the use of the Claims 1 to 21 prepared oxidation products, which are alcohols, Aldehydes, ketones, carboxylic acids, esters and / or lactones.

The process according to the invention has the advantage that the conversion of those to be oxidized organic compound is significantly higher than the reaction conditions of the process according to the state of the art. In contrast to conventional methods, this is obtained desired oxidation product with the same selectivity but in a much higher Yield. Thus it is possible to compare the reaction time of the oxidation with the To shorten processes according to the prior art significantly. It is favorable that of that previously required reactive lithium hypochlorite for this purpose and after that prior art slower sodium hypochlorite can be transferred. The Use of sodium hypochlorite not only offers price advantages, the accruing Co-product, in this case sodium chloride, can be used for other purposes such as B. the Electrolysis, continue to be used. In contrast to the methods according to the state of the Technology can in the method according to the invention from a regular addition of Oxygen atom donors are ignored during the oxidation.

The inventive method for the oxidation of organic compounds under Use of a liquid, multi-phase catalyst system, the catalyst system has at least one compound containing ruthenium and an oxygen atom donor, is characterized by the fact that the oxidation is greater at a pH of the aqueous phase or 7.0 is carried out. The oxidation is preferably carried out at a pH of aqueous phase from 7.3 to 11.0, in particular from 8.5 to 10.5 and very particularly preferably carried out from 9.0 to 10.0. With cyclic output connections it can be advantageous to the pH in the neutral to weakly alkaline range move, d. H. from 7.5 to 8.5 to exclude ring splitting.

By maintaining the pH range according to the invention, a higher conversion is achieved high selectivity with respect to the organic compound to be oxidized. Another The advantage of the process according to the invention is the significantly higher yields desired reaction product compared to the prior art. This results in, that the economic viability of the method according to the invention is clear compared to the state technology can be improved.

• - [RuCl₂(dmso)₄], wobei dmso = Dimethylsulfoxid, ferner
• - trans-[RuCl₂(dppp)₂], wobei dppp = 1,3-Bis(diphenylphosphino)propan,
• - RuO₂ × H₂O,
• - Tetrapropylammoniumperruthenat (TPAP, [n-Pr₄N][RuO₄]),
• - cis-[RuCl₂(phen)₂], wobei phen = 1,10-Phenanthrolin sowie
• - [RuCl₂(dpPP)₂] PF₆,
• - Ruthenium-Porphyrin-Systeme,
• - Rutheniumdiamintetraessigsäure,
• - Rutheniumdioxid,
• - Rutheniumtrichlorid,
• - Ruthenium-Phenanthrolin-Systeme,
• - Ruthenium-Phosphin-Systeme oder
• - Rutheniumsysteme auf Aktivkohle.

According to the invention, at least one compound containing ruthenium is required for the preparation of the catalyst system. For this purpose, the ruthenium-containing compound is preferably dissolved in an organic solvent. An aqueous solution of at least one oxygen atom donor is added to this solution with stirring. This results in a catalyst system which consists of at least one aqueous and one organic phase and optionally one or more solid phases. The following compounds containing ruthenium are preferred, some of which have already been described in the prior art:

• - [RuCl ₂ (dmso) ₄ ], where dmso = dimethyl sulfoxide, further
• - trans- [RuCl ₂ (dppp) ₂ ], where dppp = 1,3-bis (diphenylphosphino) propane,
• - RuO ₂ × H ₂ O,
• Tetrapropylammonium perruthenate (TPAP, [n-Pr ₄ N] [RuO ₄ ]),
• - cis- [RuCl ₂ (phen) ₂ ], where phen = 1,10-phenanthroline as well
• - [RuCl ₂ (dpPP) ₂ ] PF ₆ ,
• - ruthenium porphyrin systems,
• - ruthenium diamine tetraacetic acid,
• - ruthenium dioxide,
• - ruthenium trichloride,
• - ruthenium-phenanthroline systems,
• - Ruthenium-phosphine systems or
• - Ruthenium systems on activated carbon.

According to the inventive method, the compound to be oxidized, which in a organic solvent can be dissolved with the multi-phase catalyst system implemented. It may be advantageous to add further oxygen atom donors to the reaction mixture, z. B. in the form of an aqueous solution. Because the catalyst system already consists of at least one organic and an aqueous phase, one is obtained Reaction mixture which also has at least these two phases.

The amount of the ruthenium-containing compound of the catalyst system based on the oxidizing organic compound is preferably at most 2.5 mol%, in particular from 0.2 to 1 mol% and very particularly preferably from 0.25 to 0.7 mol%. By the Use of suitable promoters can increase the amount of ruthenium-containing compound halved further. Suitable promoters are all types of inorganic Bromide salts such as As potassium bromide, and pyridine oxides. The molar ratio of Promoter for the ruthenium-containing compound of the catalyst system is preferably from 1:20 to 20: 1, in particular from 1: 5 to 15: 1, particularly preferably from 1: 1 to 12: 1.

When carrying out the oxidation by the process according to the invention, it can be advantageous that at the beginning of the reaction from 1.0 to 10.0 equivalents, preferably from 1.1 to 3.0 equivalents and particularly preferably from 1.5 to 2.5 equivalents of Oxygen atom donors based on the amount of organic compound to be oxidized be used. This means that at the start of the reaction there is a maximum of ten times Amount, e.g. B. when using hydrogen peroxide, but preferably at most triple the amount of the theoretically necessary oxygen atom donor in the Reaction mixture is located. For example, this means for the oxidation of 1 mol n-propyl ether, that preferably at most 3 mol of a one-oxygen atom donor, such as. B. NaOCl, are necessary while maximum for the oxidation of 1,4-diethoxybutane 6 mol NaOCl required. It may be advantageous to continue during the oxidation Add oxygen atom donor.

Both for the production of the catalyst system and for the oxidation preferably used aqueous solutions of oxygen atom donors that are capable formally deliver one or more oxygen atoms. It can be the case Oxygen atom donor in the catalyst system and that added to the reaction mixture act on the same substance or different substances. It is therefore possible that Oxidation can also be carried out with a combination of different oxygen atom donors. For example, chlorates, bromates, persulfates, iodosobenzene, Hypochlorites, peroxides, perchlorates or perbrornates can be used. The Oxygen atom donors, such as. B. chlorates, bromates, nitrates, perchlorates or perbromates stand out by a very mild oxidation. Inputs are particularly preferred Oxygen atom donors, such as. B. hydrogen peroxide and hypochlorites, in particular Alkali compounds of hypochlorite and very particularly preferably lithium hypochlorite, Sodium hypochlorite and / or potassium hypochlorite. The oxidation process can be designed continuously, especially when using hydrogen peroxide, because as a by-product only water is formed, which is separated from the aqueous phase can be removed from the system.

In a special embodiment of the method according to the invention, it is possible to Oxidation in the presence of an oxygen-containing gas such. B. air in combination with to carry out an oxygen atom donor. For this it is necessary that with the help of Oxygen atom donors the ruthenium-containing compound already from a low to the higher oxidation state of the ruthenium has been transferred.

In the process according to the invention, organic starting materials for the oxidation can be used Compounds selected from propane, propene, propanol, acrolein, butane, butene, butanol, Butanal, isobutane, isobutene, isobutanol, isobutanal, tetralin, decalin, ethylbenzene, cumene, Butylbenzene, cyclohexylbenzene, cyclododecylbenzene, cyclohexane, cyclohexanol, Cyclohexene, cyclooctane, cyclooctanol, cyclooctene, cyclodecane, cyclodecanol, cyclodecene, Cyclododecane, cyclododecanol, cyclododecene, cyclopentadecane, cyclopentadecanol, Cyclopentadecene, dicyclododecyl ether, aminocyclododecane, trimethylcyclohexane, Trimethylcyclohexanol, trivinylcyclohexane, isophorone, toluene, anisole and anisole derivatives, ortho-xylene, meta-xylene, para-xylene, xylene derivatives, adamantane, camphor and its derivatives or picoline or a mixture of these compounds can be used. It can also be alcohols be used. The oxidation of compounds is particularly preferably selected from the group of substituted or unsubstituted ethers, substituted or unsubstituted cyclic ethers, substituted or unsubstituted 1,4-dioxacycloalkanes in particular substituted or unsubstituted 1,2: 4,5-di-O-isopropylidene-β-D-fructopyranose and / or substituted or unsubstituted pinacolone. When using gaseous starting materials in the inventive methods are either dissolved in a solvent or converted to the liquid phase state by means of increased pressure, since oxidation is preferred is carried out in the liquid phase.

The organic phase of the reaction mixture preferably has in addition to that to be oxidized organic compound also an organic solvent. The solvent of the Ruthenium-containing compound for the catalyst system can both with the solvent the reaction mixture may be identical as well as different. As solvents come alkanes substituted and unsubstituted by organic compounds to be oxidized, halogenated alkanes, substituted and unsubstituted alicycles, halogenated alicycles, substituted and unsubstituted aromatics, halogenated aromatics, substituted and unsubstituted ethers and esters, substituted and unsubstituted cyclic ethers and esters, substituted and unsubstituted nitrile compounds and carboxylic acids. Methylene chloride, chloroform, carbon tetrachloride, ethyl acetate, Butyl acetate, butyl butyrate, benzene, toluene, methyl tertiary butyl ether (MTBE), acetone, Acetonitrile, trifluorotoluene and acetic acid. The organic compound to be oxidized can be in certain cases, e.g. B. in the oxidation of ethers, even as an organic solvent serve so that you can work here without an additional organic solvent and is oxidized in bulk.

It can be advantageous for the oxidation if the pH of the aqueous phase during the entire reaction time with a maximum fluctuation range of ± 0.5 constant is held. The pH value is preferably maintained during the entire reaction with a suitable device, such as. B. a commercially available pH meter (from Metrohm) with a Glass electrode, monitored. In a particularly preferred procedure, the pH Value recorded and if necessary by coupling the pH meter to a Dosing device (e.g. Dosimat from Metrohm) regulated. The dosing device gives an acid, preferably a mineral acid, such as. B. hydrochloric acid, or a base, such as. B. Add aqueous sodium hydroxide solution. It can as well be advantageous to use an organic acid to regulate the pH. This can be particularly advantageous if an organic acid is used as the acid, which is also the target product of the oxidation, since this acid is used in the processing of the Product does not have to be separated. The pH value is maintained at this embodiment of the method according to the invention thus by metering Acid and / or base by means of a metering device. The addition of acid and / or Base may be based on experience and not as described above by monitoring the current pH value. Such an addition can continuously or at regular or irregular intervals with which Provided that the pH does not exceed the desired range and in particular does not decrease to a value less than 7.0.

In certain cases it is possible to use buffer systems whose areas of application are alkaline. Buffer systems consist of a weak acid, e.g. B. formic acid, acetic acid, carbonic acid, phosphoric acid and the alkali salt of the corresponding base, as also described in the Römpp chemistry dictionary (CD-ROM version 2.0). Examples of preferred buffer systems are:
Potassium dihydrogen phosphate / sodium hydrogen phosphate (so-called Sørensen buffer, pH: 7.2)
Sodium bicarbonate / sodium carbonate (pH: 9.5)
Barbital / barbital sodium (so-called Laurell buffer, pH: 9)
The use of a buffer system has the advantage, provided that the buffer system can intercept the pH changes, that monitoring by means of a pH meter and metering in of acid and / or base can be dispensed with. For 1 mmol of organic compound to be oxidized, preference is given to using from 0.3 to 2 cm ³ , in particular from 0.5 to 1.5 cm ³ , particularly preferably from 0.8 to 1.2 cm ^{3, of} a buffer solution such as that used, for B. is also sold by the companies Aldrich or Fluka ready for use. It may be advantageous to use a combination of a buffer system and a pH-controlled or pH-independent metering device for an acid and / or base. In a particular embodiment of the process according to the invention, the oxidation takes place at a temperature of 0 to 80 ° C, preferably at a temperature of 10 to 50 ° C, in particular from 15 to 30 ° C and very particularly preferably at a room temperature of 23 ° C ± 1 ° C. The oxidation is preferably carried out at a pressure less than 10 bar, in particular at less than or equal to 5 bar and very particularly preferably at an ambient pressure of 1 bar.

The use of phase transfer reagents, such as. B. crown ethers or organic Ammonium salts can be advantageous in some cases, as this results in a higher Yield can be achieved.

The compound containing ruthenium can easily be removed from the reaction after the end of the reaction Reaction mixture can be recycled, as these at pH values above 10.0, in particular but from 10.0 to 11.0 passes quantitatively into the aqueous phase. At a Lowering the pH of the aqueous phase to less than 7.0, in particular at a pH of 5.5 to 6.5 can the ruthenium-containing compound quantitatively in the organic phase be transferred.

This can be said about the recycling of the compound containing ruthenium Make use of. It may be advantageous to first use the pH of the aqueous phase to increase a base, for example to adjust a pH of 10.0 to 11.0. Now can replace the organic phase containing the desired oxidation product become, d. H. a new organic phase is added. This organic phase can besides an organic solvent also contain the organic compound to be oxidized. In a specific embodiment of the method according to the invention, this can organic phase consist only of the organic compound to be oxidized, d. H. it will in this case the oxidation is carried out in bulk. Then the pH of the aqueous phase using an acid, for example to a pH of 5.5 to 6.5, lowered and the aqueous phase are replaced, because under these conditions the ruthenium-containing compound passes completely into the organic phase. After that, a alkaline pH set and the catalyst system can thus be used for another Oxidation can be used. The process can not only, as already mentioned, at Hydrogen peroxide as an oxygen atom donor can be designed continuously, but this is generally possible because the ruthenium-containing compound of the catalyst system depends on adjusted pH value optionally transferred quantitatively into the organic or aqueous phase can be.

The desired oxidation product can e.g. B. by means of a conventional thermal Separation processes such as B. distillation, rectification separated from the organic solvent become. If the reaction is carried out in bulk, i. H. the starting material of the oxidation also used as an organic solvent and there is another one dispenses with organic solvent, the oxidation product can be separated off directly be isolated.

Basically, all types of batch reactors are suitable as reactors, but there is also one continuous driving style possible. The use of a ceramic membrane reactor, As described in EP 1 088 587 can be advantageous in some cases. Here will the ruthenium-containing compound is held in place by a membrane while the others Reaction partners can move freely in the reactor. This can help the recycling process the compound containing ruthenium can be simplified.

The process of this invention can be used to prepare substituted or unsubstituted Esters from substituted or unsubstituted ethers, from substituted or unsubstituted Lactones from substituted or unsubstituted cyclic ethers, from substituted or unsubstituted dioxacycloalkane anions or of substituted or unsubstituted Lactides from substituted or unsubstituted dioxacycloalkanes can be used. Preferred is the use of the method for the production of substituted or unsubstituted 1,2: 4,5-di-O-isopropylidene-β-D-erythro-2,3-hexadiulo-2,6-pyranose substituted or unsubstituted 1,2: 4,5-di-O-isopropylidene-β-D-fructopyranose, from substituted or unsubstituted trimethylpyruvic acid from substituted or unsubstituted pinacolon. The use of the method for is particularly preferred Preparation of 1,3-dioxacyclotridecan-2-one from 1,3-dioxacyclotridecan, from 1,8- Dioxacycloheptadecan-9-one from 1,8-dioxacycloheptadecan, from 1,7-dioxacycloheptadecan-8- on from 1,7-dioxacycloheptadecane, from 1-oxacyclohexadecane-2,13-dione 1-oxacyclohexadecan-5-one, from hexadecen-16-olide from 1-oxacycloheptadecen, from 1,4-dioxacycloheptadecane-5,17-dione from 1,4-dioxacycloheptadecane, from 1,4-dioxacyclohexadecane-5,16- dione from 1,4-dioxacyclohexadecane, from hexadecan-16-olide from 1-oxacycloheptadecane, from Pentadecan-15-olide from 1-oxacyclohexadecane or from pentadecen-15-olide 1-Oxacyclohexadecen, since the resulting oxidation products in turn as starting compounds for the production of fragrances or musk products are suitable.

The aforementioned starting compounds can in the course of the invention Process selectively in high yields to alcohols, aldehydes, ketones, carboxylic acids, Esters or lactones are oxidized.

The following examples are intended to illustrate the invention without restricting its scope.

The precursors of all ruthenium-containing catalyst systems were according to the on page 1 and 2 listed literature produced.

example 1 Production of the ruthenium-containing catalyst system I

0.05 mmol [RuCl ₂ (dmso) ₄ ] was dissolved in 2 cm ³ methylene chloride. 0.2 mmol of NaOCl (1 molar, aqueous solution) was rapidly added to this mixture at room temperature with vigorous stirring.

Example 2 Production of the ruthenium-containing catalyst system II

0.05 mmol [RuCl ₂ (dppp) ₂ ] was dissolved in 2 cm ³ methylene chloride. 0.2 mmol of KOCl (1-molar, aqueous solution) was rapidly added to this mixture at room temperature with vigorous stirring.

Example 3 Production of the ruthenium-containing catalyst system III

0.05 mmol TPAP was dissolved in 2 cm ³ methylene chloride. 0.2 mmol of NaOCl (1 molar, aqueous solution) was rapidly added to this mixture at room temperature with vigorous stirring.

Example 4 Production of the ruthenium-containing catalyst system IV

0.05 mmol [RuCl2 (dmso) 4] was dissolved in 2 cm ^{3 of} ethyl acetate. 0.2 mmol of NaOCl (1 molar, aqueous solution) was rapidly added to this mixture at room temperature with vigorous stirring.

Example 5 Production of the ruthenium-containing catalyst system V

0.05 mmol RuO ₂ × H ₂ O were dissolved in 2 cm ³ ethyl acetate. A 1.0 mmol hydrogen peroxide solution (concentration 30%) was quickly added to this mixture at room temperature with vigorous stirring.

Example 6 Carrying out the experiments not according to the invention

5 mmol of the compound to be oxidized were, according to Table 1, with a ruthenium-containing catalyst system and with 10 mmol of oxygen atom donor (when using hydrogen peroxide: 50 mmol) as a 1-molar aqueous solution at a room temperature of 23 ° C. and a pressure of 1 bar in 2 cm ³ solvents reacted in a laboratory stirred tank reactor. The catalyst system was made according to IV. The amount of the mixture of the catalyst system which corresponds to a content of 0.4125 mmol of compound containing ruthenium was used. At the start of the reaction, the pH of the aqueous phase of the reaction mixture was determined. After a reaction time of 5 hours, a sample was taken, the content of the oxidation product by means of a GC analysis (GC-9A with FI detector and integrator C-R3A Chromatopac - both from Shimadzu; capillary column SE 30, 25 m length, 2 mm Macherey &Nagel; carrier gas: 2 bar nitrogen) and the yield was calculated. Also after 5 hours, the pH of the aqueous phase is determined using a pH meter (from Metrohm).

Example 7 Carrying out the experiments according to the invention

The procedure was analogous to Example 6, but the pH was adjusted with a Fluctuation range of a maximum of ± 0.5 by adding 1 molar hydrochloric acid or adding 1 molar sodium hydroxide solution kept constant. In experiment No. 7 the pH was of 9.5 during the entire reaction time using the buffer system Sodium bicarbonate / sodium carbonate kept constant.

The experiments were carried out with different starting compounds, catalyst systems, oxygen atom donors and organic solvents. For comparison, the test was carried out both according to the prior art and according to this invention. Table 1 illustrates the results of Examples 6 and 7 after a reaction time of 5 hours.


Table 2 List of chemicals used

The table shows that the process is carried out at a constant pH gives significantly higher yield of the desired oxidation product after 5 hours.

Claims (27)

1. A process for the oxidation of organic compounds using a liquid, multi-phase catalyst system, the catalyst system having at least one ruthenium-containing compound and an oxygen atom donor, characterized in that the oxidation is carried out at a pH of the aqueous phase greater than or equal to 7.0 , 2. The method according to claim 1, characterized, that the amount of the ruthenium-containing compound of the catalyst system based on the organic compound to be oxidized is at most 2.5 mol%. 3. The method according to claim 1 or 2, characterized, that the oxidation is carried out at a pH of 7.3 to 11.0. 4. The method according to at least one of claims 1 to 3, characterized, that the pH value has a maximum during the entire reaction time Fluctuation range of ± 0.5 is kept constant. 5. The method according to at least one of claims 1 to 4, characterized, that the pH value is maintained by adding acid and / or base by means of a metering device. 6. The method according to at least one of claims 1 to 5, characterized, that the pH value is maintained by means of a buffer system. 7. The method according to at least one of claims 1 to 6, characterized, that the organic phase in addition to the compound to be oxidized has organic solvent. 8. The method according to at least one of claims 1 to 7, characterized, that as the oxygen atom donor chlorates, bromates, nitrates, persulfates, iodosobenzene, Hypochlorites, peroxides, perchlorates or perbromates can be used. 9. The method according to at least one of claims 1 to 8, characterized, that the oxidation is carried out with a one-oxygen atom donor. 10. The method according to claim 9, characterized, that the one-oxygen atom donor is hydrogen peroxide. 11. The method according to claim 9, characterized, that the one-oxygen atom donor is a hypochlorite. 12. The method according to claim 11, characterized, that the hypochlorite is an alkali compound. 13. The method according to at least one of claims 1 to 12, characterized, that based on the organic compound to be oxidized at the beginning of the reaction a maximum of 10 equivalents of the oxygen atom donor can be used. 14. The method according to at least one of claims 1 to 13, characterized, that the oxidation is carried out in the presence of an oxygen-containing gas. 15. The method according to at least one of claims 1 to 14, characterized, that the oxidation is carried out at a temperature of 0 to 80 ° C. 16. The method according to at least one of claims 1 to 15, characterized, that the oxidation is carried out at a pressure of less than 10 bar. 17. The method according to at least one of claims 1 to 16, characterized, that a promoter with a molar ratio to the ruthenium-containing compound of Catalyst system from 1:20 to 20: 1 is used. 18. The method according to at least one of claims 1 to 17, characterized, that an organic compound selected from propane, propene, propanol, acrolein, Butane, butene, butanol, butanal, isobutane, isobutene, isobutanol, isobutanal, tetralin, Decalin, ethylbenzene, cumene, butylbenzene, cyclohexylbenzene, cyclododecylbenzene, Cyclohexane, cyclohexanol, cyclohexene, cyclooctane, cyclooctanol, cyclooctene, Cyclodecane, cyclodecanol, cyclodecene, cyclododecane, cyclododecanol, cyclododecene, Cyclopentadecane, cyclopentadecanol, cyclopentadecene, dicyclododecyl ether, Aminocyclododecane, trimethylcyclohexane, trimethylcyclohexanol, trivinylcyclohexane, Isophorone, toluene, anisole and anisole derivatives, ortho-xylene, meta-xylene, para-xylene, Xylene derivatives, adamantane, camphor and its derivatives or picoline or a mixture of these compounds is oxidized. 19. The method according to at least one of claims 1 to 17, characterized, that an organic compound selected from the group of substituted or unsubstituted ethers, substituted or unsubstituted cyclic ethers, substituted or unsubstituted 1,4-dioxacycloalkanes, substituted or unsubstituted 1,2: 4,5-di-O-isopropylidene-β-D-fructopyranose and / or substituted or unsubstituted pinacolone is oxidized. 20. The method according to at least one of claims 1 to 19, characterized, that the ruthenium-containing compound of the catalyst system after the end of the reaction is recycled. 21. The method according to claim 20, characterized, that the compound containing ruthenium quantitatively into the aqueous phase passes over the reaction mixture, the organic phase is exchanged, the ruthenium-containing compound by lowering the pH in the organic phase is transferred back, then the aqueous phase is replaced and finally a pH value greater than or equal to 7.0 is set. 22. Use of the method according to at least one of claims 1 to 21 for Production of substituted or unsubstituted esters from substituted or unsubstituted ethers. 23. Use of the method according to at least one of claims 1 to 21 for Production of substituted or unsubstituted lactones from substituted or unsubstituted cyclic ethers. 24. Use of the method according to at least one of claims 1 to 21 for Production of substituted or unsubstituted dioxacycloalkane anions or of substituted or unsubstituted lactides from substituted or unsubstituted Dioxacycloalkanen. 25. Use of the method according to at least one of claims 1 to 21 for the production of
1,3-dioxacyclotridecan-2-one from 1,3-dioxacyclotridecan, from
1,8-dioxacycloheptadecan-9-one from 1,8-dioxacycloheptadecan, from
1,7-dioxacycloheptadecan-8-one from 1,7-dioxacycloheptadecan, from
1-oxacyclohexadecan-2, 13-dione from 1-oxacyclohexadecan-5-one, from
Hexadecen-16-olide from 1-oxacycloheptadecen, from
1,4-dioxacycloheptadecan-5,17-dione from 1,4-dioxacycloheptadecane, by
1,4-dioxacyclohexadecane-5,16-dione from 1,4-dioxacyclohexadecane, by
Hexadecan- 16-olide from 1-oxacycloheptadecane, from
Pentadecan-15-olide from 1-oxacyclohexadecane or from
Pentadecen-15-olide from 1-oxacyclohexadecen. 26. Use of the method according to at least one of claims 1 to 21 for Preparation of substituted or unsubstituted 1,2: 4,5-di-O-isopropylidene-β-D- erythro-2,3-hexadiulo-2,6-pyranose from substituted or unsubstituted 1,2: 4,5-di-O- isopropylidene-β-D-fructopyranose. 27. Use of the method according to at least one of claims 1 to 21 for Manufacture of substituted or unsubstituted trimethylpyruvic acid from substituted or unsubstituted pinacolone.