TW593258B - Process for the preparation of 2,3,5-trimethyl-p-benzoquinone - Google Patents

Abstract

Process for the preparation of 2,3,5-trimethyl-p-benzoquinone by oxidising 2,3,5-trimethylphenol or 2,3,6-trimethylphenol with oxygen or an oxygen-containing gas mixture in the presence of a catalyst system consisting of a copper halide and a transition metal halide from the group iron, chromium, manganese, cobalt, nickel, zinc or a rare earth halide, in a two-phase reaction medium, at elevated temperature.

Description

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593258 A7 _ B7 V. Description of the Invention (1) The present invention relates to a novel method for preparing 2,3,5-trimethyl-p-benzoquinone. Oxidation of phenols with oxygen in the presence of two-phase liquid reaction media of copper chloride and other catalyst mixtures of transition metal halides or rare earth element halides of the iron, chromium, manganese, cobalt, nickel or zinc group. , 3,5-trimethylphenol and 2,3,6-trimethylphenol can be used as reactants in this reaction. 2,3,5-trimethyl-p-benzoquinone is an intermediate, which is especially used for the preparation of α-tocopherol (vitamin E). A method for oxidizing trimethylphenol to 2,3,5-trimethyl-p-benzoquinone is known. The use of inorganic oxides, including potassium permanganate, potassium dioxide, and lead oxide, has been disclosed in previously known methods requiring the use of stoichiometric oxidants. The use of these expensive oxidants results in high chemical consumption and production of Corresponding to waste gas contaminated by reduced metals and must be regenerated or discarded at high cost. Catalytic methods are also known in which the oxidation of trimethylphenol is carried out using an oxygen-containing gas as an oxidant in the presence of a metal catalyst. These methods are converted for commercial applications, such as the use of cobalt-salene complex catalysts. The service life of the media is very short, complicated and expensive, because it requires adding a small amount of fresh catalyst and discarding or expensively treating a large amount of metal-contaminated exhaust gas. For example, in EP 0 6 5 9 7 2 7, it reveals that the compound bond The tetrazine [1 4] annulene of the heavy metal ion that is bound is used as an oxygen-containing catalyst. This catalyst is destroyed during oxidation and cannot be recovered, so it is not suitable for commercial use. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ~ " Γ. --- 装 —— — ----— Order · —------- (Please read the back first (Notes to fill out this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) In this regard, US 3 7 9 6 7 3 2 discloses the use of copper chloride as a catalyst for the reaction, in which the operation is in the presence of an inert solvent such as DMF In the homogeneous phase, which causes the problem of catalyst treatment, which can only be solved technically at high cost. In JP 17585/1978, it was revealed that the use of a catalyst system containing copper ions and halogen ions can improve the yield. The disadvantage of this method is that in addition to high yield, the space-time production quota is very low and a large amount of water is needed to extract the catalyst and remove water in order to The catalyst is recovered, and the residual water in the catalyst has a negative effect on the performance of the catalyst. In JP 93931/1975, halogens or halogenated compounds were added during the recovery process in order to maintain catalyst activity, but these compounds were used up quickly in the case of the reaction and must therefore be replenished regularly, which is expensive and leads to a significant increase in process technology projects Cost of production. One possible method to avoid the problem of catalyst recovery while maintaining catalyst activity is to disclose in RU-2 0 3 9 037, which reveals that triphenylphenol and structurally related compounds are passed through oxygen or containing in the presence of heterogeneous catalysts. Oxygen gas oxidizes. The disadvantage of this method has proven to be the expensive preparation of heterogeneous catalysts, which is derived from the application of monovalent copper chloride to the hydroxide as a carrier in the presence of a defined amount of phosphoric acid, in the presence of chloride and alkali metal chloride. aluminum. According to EP 0127 888, an aqueous solution of Li (Cu C 1 3) in the presence of a high excess of a corresponding lithium halide is used as an oxidation catalyst, but it has been found that, in addition to high yield, this method is converted into a commercial application and Disadvantage, because a large amount of expensive lithium halide is required, it must be Γ, --K -------- r --- ^ --------- (Please read the precautions on the back before (Fill in this page) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -5-Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 593258 A7 B7 V. Description of the invention (3) It must be prepared expensively Composite copper (II) catalyst, and at least equivalent catalyst based on trimethylphenol must be used to achieve good yield. EP 0 167 153 discloses the use of an aqueous catalyst solution containing Li (C u C 1 3) or a corresponding copper (I I) complex in the presence of an excess of the corresponding lithium halide. EP 0 294 584 also discloses the contact between copper (II) chloride and lithium chloride in a two-phase reaction medium containing a mixture of water and aromatic hydrocarbons and a low-carbon aliphatic alcohol containing from 1 to 4 carbon atoms. In the presence of a medium, a method for preparing 2,3,5-trimethyl-p-benzoquinone using a complex organic solvent mixture must be subjected to distillation treatment after the reaction, which is disadvantageous from a commercial point of view. EP 0 369 824 discloses another variation of oxidation in a two-phase reaction system, the catalyst of which is composed of copper (II) halide and nitrogen-containing compounds, preferably hydroxylamine, oxime or amine or the corresponding ammonium salt. The composition of the meta-system proves that the disadvantage of the nitrogen-containing catalyst component is that it can be decomposed and cannot be recovered in the case of oxidation, thus increasing the high cost. EP 0 475 272 discloses the use of a catalyst containing copper (II) halide and alkaline earth metal halides in a two-phase solvent system containing water and saturated aliphatic alcohols from 5 to 10 carbon atoms, in an oxygen-containing gas In the presence of oxidation, in this method, the active catalyst is formed on the spot from copper (II) salts and alkaline earth metal additives, and compared with the reaction temperature used, the organic solvent system has a sufficiently high flash point, but in order to achieve good For conversion and yield, a stoichiometric catalyst must be added. Revealed in EP 〇3 8 7 820 Contains from 12 to this paper size Applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -6- f, ----- installation ----- r --- Order --------- · (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593258 A7 B7 V. Description of Invention (4) 1 8 Reactions in aliphatic alcohols with carbon atoms also allow oxidation at temperatures below the flash point of organic solvents, but this method is not commercially attractive because of the 2,3,5-trimethyl-p-benzoquinone reaction And the separation is very complicated, which is due to the relatively high melting point and boiling point of alcohols. The object of the present invention is to provide a novel method for the preparation of 2'3,5-trimethyl-p-benzoquinone, in order to solve the problem of preventing the use of material costs, handling costs and safety aspects disclosed in the prior art in the same situation. This translates into many problems on a commercial scale. The purpose of the present invention is, in particular, to meet the following requirements of the method: a) Use of inexpensive materials that are freely available on the market and can produce active catalysts on the spot under given reaction conditions The catalyst system is different from the catalysts described previously. In some cases, it must be prepared in the separation method step before the actual oxidation reaction or the catalyst system is used up in the oxidation process. B) The catalyst system used It is highly active and has a long service life at the same time. It can be recovered after the reaction and can be reused again without special measures. c) Use a reaction system composed of different phases that are immiscible at room temperature. One phase contains the catalyst in dissolved or suspended form, and the other phase contains dissolved substances in the reactants and products formed during the reaction. The reactant / product phase is separated from the catalyst phase after the reaction and thus the product can be separated in a simple method and with high yield, and the catalyst phase can be recovered at low cost. Oxygen is used in a two-phase reaction medium at high temperature in the presence of a catalyst containing at least one copper halide with oxygen or a gas mixture containing oxygen. This paper is sized to Chinese National Standard (CNS) A4 (210 X 297) (Mm) Z '" " ί ----------- r --- order --------- (Please read the notes on the back before filling this page) Ministry of Economy Printed by the Intellectual Property Bureau employee consumer cooperative 593258 Α7 Β7 V. Description of the invention (5) Conversion of trimethylphenol to achieve this purpose. This method is characterized by the presence of water and lipids containing 5 to 10 carbon atoms. Group alcohols or reaction media containing aliphatic alcohols and aromatic hydrocarbons containing from 1 to 4 carbon atoms, halogenated in copper-containing halides and other transition metals from the iron, chromium, manganese, cobalt, nickel, zinc group In the presence of a catalyst of a rare earth element halide, the reaction is carried out at a temperature from 20 to 120 ° C. During the reaction, the organic phase containing a trimethylphenol substrate and a suitable solvent which is insoluble or slightly soluble in water at room temperature can be brought into contact with the aqueous phase containing the catalyst system, and the reaction mixture thus prepared can be brought into contact with oxygen. Contact the gas, and when the reaction is completed, the organic product phase is separated from the aqueous catalyst phase which is still active in order to separate the 2,3,5-trimethyl-p-benzoquinone product. The results were unexpected, because in aqueous systems of copper halides and transition metal halides or rare-earth element halides, it is necessary to take into account the formation of partially dissolved or, in some cases, oligomeric or polymeric hydrolysates. The oxidation in the study showed no selective catalytic activity. It has been found that in the case of the present invention, if a binary catalyst system containing copper halides on the one hand and transition metal halides or rare earth element halides on the other hand is used, even when the aqueous catalyst phase is reused, there is no or only A negligible catalyst deactivation occurs, and from a commercial point of view, it can be oxidized to 2,3,5-trimethyl-p-benzenesulfonate in a novel and economical manner at the same time. Even when the catalyst phase is reused, the yield of 2,3,5-trimethyl-p-benzoquinone can reach more than 90%, using selective transition metal halides such as C r C 1 3, F e C 1 3 or Z n C 1 2 and make Γ .----------- r ------------ (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -8-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593258 A7 ___ B7 V. Description of the invention (6) For example, expensive L i C A comparison can further provide economic advantages. The oxidant used in the method according to the present invention is pure form or diluted form of oxygen such as air, based on 1 liter of the reaction mixture, usually supplying gaseous oxygen from 10 to 150 NL per hour, suitable for the present invention. The copper salts that can be listed include but are not limited to Cu C 1 2 and Cu B 2 or corresponding Cu (I) salts such as CuC 1 or CuB r, especially CuCl 2 and CuCl. Copper chloride is more preferably used (II). Transition metal halides suitable for use in the scope of the present invention are the chlorides of transition metals, particularly suitable are the halides of Group IV elements, such as Ci :, Mn, Fe, Co, Ni and Zn elements and rare earths Ce halide. Suitable for mixing with water as the reaction medium are branched and straight chain aliphatic C 5 -C! 〇 Alcohols such as 1-pentyl alcohol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1 —Decanol, 2-ethylhexanol or cyclohexanol. Also suitable for mixing with water and aromatic hydrocarbons as reaction medium are branched and straight chain aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol and tertiary butanol . Aromatic hydrocarbons which are preferably used are aromatic compounds containing from 6 to 8 carbon atoms, especially benzene, toluene, xylene or halo substituents such as chlorobenzene. The preparation of the aqueous catalyst phase is carried out by simply mixing an aqueous solution of the ingredients or dissolving the solid salt compound in water, which makes this method significantly easier. The molar ratio of copper halide to trimethylphenol can be changed within a wide range, and usually copper salt / trimethylphenol = from 0 · 1 to 10, it is more suitable to apply Chinese National Standard (CNS) A4 from this paper scale Specifications (210 X 297 mm) -9-, >-r ^ ------- III l · --- order --IIII I-- line (please read the precautions on the back before filling this page ) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593258 A7 B7 V. Description of Invention (7) 0.2 to 3. The transition metal halide can be used in an amount of 0.1 to 1 fold based on trimethylphenol, preferably 0.2 to 5 times the molecular weight. In the case of using a copper (II) salt, the copper halide is The concentration in the aqueous catalyst phase can be varied from 1 to 70% by weight, preferably from 5 to 30% by weight. Transition metal halides or rare earth halides are more preferably used from 5 to 80. Concentration by weight. Copper salts known in the art can be used as an additional activator for the reaction system, for example, copper (I) chloride or a corresponding hydroxide is most advantageous. Phase transfer catalysts can be provided as required from a two-phase mixture produced, for example, using water and solvents that are immiscible or only limitedly soluble in water. Considered as phase transfer catalysts are conventional products known per se, such as tetraalkylammonium halides , Benzyltrialkylammonium halide or hydrogen sulfate and corresponding scale salts and polyethylene glycol compounds, this novel method is usually carried out at normal pressure and at a temperature from 20 to 120 ° C This method can also be performed under reduced pressure. The operation under reduced pressure is particularly suitable in the case of gas mixtures containing oxygen, and the steps can be performed continuously or discontinuously. In order to carry out the reaction, trimethylphenol is dissolved in the organic component of the solvent system, and is added to the aqueous phase containing the catalyst under metering. In a different specific embodiment, a portion of the organic is The solvent is placed in a container with an aqueous phase, and a trimethylphenol solution is added under metering. In another variation of the reaction step of the present invention, the reaction is performed in batches, all the ingredients are placed in a container, stirred and metered in Oxygen-containing gas. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 10- f * -------- r --- ^ --------- (Please read the back first Note: Please fill in this page again) 593258 A7 B7 V. Description of the invention (8) The concentration of trimethylphenol in the organic phase can be changed within a large concentration range. The concentration of trimethylphenol is usually adjusted from 5 to 80. %, Preferably from 10 to (Please read the notes on the back before filling out this page) 50%. The volume ratio of water to organic solvents can be varied from 10: 1 to 1:10, and more preferably from 3: 1 to 1: 5. The reaction temperature can be varied within a large temperature interval, and it is preferred to carry out the reaction from 20 to 120 ° C. In a particularly preferred embodiment, the reaction is carried out from 40 to 90 ° C. The 2,3,5-trimethyl-paraquinone reaction product can be isolated in a conventional manner, such as by vacuum and steam distillation. The method according to the present invention can be simply carried out and the reaction product can be supplied in good yield and high purity.

A J & W DB-5 capillary column with a length of 30 meters, an inner diameter of 0.32 mm, and a membrane thickness of 1 micron was used to measure the yield on a HP 5890 or HP 6 890 gas chromatograph. Fourteen carbon was used. As an internal standard, the reference material used is TMQ, which is purified by distillation and repeated crystallization. Printed by Jasco's system equipped with UV 9 75 uV detector, PU 9 80 pump, and AS 9 50 automatic sampler, the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics uses a PLC column to measure. From GL Sciences Inc. 2lntersil-〇DS3V-5 μ, 250 x 4.6 mm inner diameter, using the above TMQ reference material as an internal standard. The following examples are provided to illustrate the present invention in more detail. TMP stands for trimethylphenol. -11-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593258 Α7 _________ Β7 5. Invention Description (9) TMQ Representative 2, 3, 5 -Trimethyl-p-benzenes. EXAMPLES Example 1: 2.98 grams (18.4 millimoles) of FeC3 and 0.91 grams (9.2 millimoles) of CuCl were dissolved in a 100 ml three-necked flask of water (Cu C 1: F e C 1 3 molar ratio = 0. 5), the catalyst concentration of the binary salt mixture in the water phase is 1 3. 5 weight%, and 2.5 g of TMP (= 18 · 4 mmol) Ear) A solution in 25 ml of hexanol was added to the aqueous catalyst phase and stirred vigorously. The TP concentration in the organic phase was 11% by weight. The reaction mixture was heated to 60 ° C and oxygen was added through the frit. The progress of the reaction was monitored by a gas chromatograph. When the reaction was completed, a TMQ yield of 82.2% was obtained. Examples 2 to 6: Similar to Example 1, the ingredients were placed in a 100 ml three-necked flask, and the ratio of TMP: CuCl2: FeCls was 1: 0.75.75: 1. 5, all tested in the aqueous binary catalyst The concentration is 39.4% by weight. TMP-alcohol solution is first added to the used catalyst phase, and then the mixture is adjusted to the temperature indicated, and oxygen is started to pass in. By changing the reaction temperature and reaction time, After the reaction was completed, the following was obtained. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) * -------- r --- Order --------- (Please read the precautions on the back first (Fill in this page again) 593258 A7 B7 V. Description of Invention (10)

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Add copper chloride (; [I) (66 mmol) and chromium (III) chloride (132 mmol) to the glass reactor as an aqueous solution (catalyst concentration in the aqueous phase: 39 · 0 weight %), Add 40 ml of 1-hexanol • and heat the mixture to 65 t: and then dropwise add 12 g of 2,3'6-trimethylphenol (88 mmol) in 20 ml of 1-hexane The solution in alcohol lasted 3 hours. Stir (900 rpm) and add oxygen through the glass frit. When the addition is complete, continue stirring at 80 ° C for another 2 hours and pass in oxygen. Monitor the progress of the reaction via HPLC. After the reaction was completed, the liquid phase was separated, the organic phase was washed twice with water, and the TMQ production was measured by a gas chromatograph using an internal standard. The combined aqueous phase was concentrated to the original volume in a rotary evaporator and transferred to As a catalyst solution in a glass reactor, this step was repeated several times. Table 3 Example 13 / Number of repetitions of the round method TMQ yield (%) 1 1 92.0 2 2 94.2 3 3 94.3 4 4 9 3.8 * 5 5 93.7 6 6 92.3 7 7 94.3 (CNS) A4 specification (210 X 297 mm) -16- -------------- install ----- r --- order ---------. (Please read the precautions on the back before filling this page) 593258 A7 B7 V. Description of the invention (14) Example 1 4 to 17 7 Copper (III) chloride (1 each alcohol amount shown by the catalyst in the water phase) Incorporate 12 grams of 2, the indicated amount of each alcohol rpm), and monitor the organic phase with water TMQ output by Η PLC according to the table under the temperature. &Quot;) (6 3 2 millimoles) Concentration: 3 9. Heat the mixture in a solution of 3, 6-trimethylamine for the duration of the reaction time indicated by the addition of oxygen to the glass frit. When washed twice, use 6 millimoles) and chromium chloride (addition of glass in the form of an aqueous solution. Wt%). ), Add the temperature indicated in Table 4 to the indicated temperature, and then add the phenol (88 mmol) dropwise in Table 4 for 3 hours, stirring (900 gas, when the addition is complete, continue stirring at the instruction. Pass in oxygen, and after the reaction is completed, the liquid phase is separated, and the internal standard is measured by gas chromatography (please read the precautions on the back before filling this page). Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -17- 593258 A7 B7 V. Invention Description (15) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

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Claims (1)

593258 Male tongue 豕 A8 B8 C8 D8 6. Application scope 1 · A method for preparing 2,3,5-trimethyl-p-benzoquinone, which is at high temperature in a two-phase reaction medium, containing Trimethylphenol is oxidized with oxygen or a gas mixture containing oxygen in the presence of at least one copper halide catalyst, which is characterized by the presence of water and aliphatic alcohols containing 5 to 10 carbon atoms or water and In the reaction medium of aliphatic alcohols and aromatic hydrocarbons of 1 to 4 carbon atoms, in copper-containing halides and other transition metal halides or rare-earth element halides from the iron, chromium, manganese, cobalt, nickel, zinc group In the presence of a catalyst, the reaction is performed at a temperature from 20 to 120 ° C. 2. A method for preparing 2,3,5-trimethyl-p-benzoquinone according to item 1 of the scope of the patent application, which is characterized in that it contains water and an aliphatic alcohol containing from 1 to 4 carbon atoms and toluene or benzene. The mixture is carried out in the reaction medium. 3. The method for preparing 2,3,5-trimethyl-p-benzoquinone according to item 1 of the scope of the patent application, which is characterized in the presence of water and 1-hexanol, 1-heptanol, 2-ethylhexanol Or in the reaction medium of 1-octanol. 4. The method for preparing 2,3,5-trimethyl-p-benzoquinone according to item 1 of the scope of the patent application, which is characterized by using chromium (III) chloride, manganese (II) or cobalt (II) as a transition Metal halide. ----- l · ---- r)-install -------- order --------- line offering (please read the precautions on the back before filling this page) economy The Ministry of Intellectual Property Bureau's Employee Cooperative Cooperative printed 3 I and Γν 2 for preparing chlorine for use. The law of halogenated quinone is based on the benzoin roots. I soil 5 bases are three crops I Ί · 19- This paper size is applicable to China National Standard (CNS) A4 (210 X 297) Li) Notice of the amendment to the Chinese specification of the patent application No. 89121128 J Min® filed in April 91 Application 9 October 89 E No. 89121128 \ Category (the above columns are filled by the Office) A4 :: C4 || Patent specification 593258 Chinese 2, 3, 5-trimethyl phenyl hydrazone production method invention new name English Process for the preparation of 2,3,5-tr i methy1-p-benzoqu i none Name Nationality ⑴ 雷福 • Martha Maassen, Ralf 0 Steven Riel Kriil, Steffen (3 Miao Mage Jager, Barbara Inventor living, domicile ⑴ Germany 0 Germany 那 Germany Hanerelier Hof Road 22 Lehrhofer Strasse 22, DE-63457 Hanau Germany (2) Friedrich-Holderlin-Weg 23, DE-67346 Speyer, Germany (3) 11 Anhatten, Fryger District, Laos An Huttenrain 11, D-63579 Freigericht, G ermany (3 German binding name (name) (1) Degussa Akt i engese11schaft, Tigusa company, Ministry of Economic Affairs, Intellectual Property and Finance, 4th Bureau, Consumer Cooperatives, Printing Line, Nationality Applicant's Residence, Residence (Office) Name of Representative ⑴ 徳 Guo⑴ 徳 Germany Düsseldorf Bennigsenplatz 1, DE-40474 Dusseldorf, Germany ⑴Matters Schiefer Schaffer, Matthias Wufugang • Boer Weber, Wolfgang This paper is applicable to Chinese national standards (CNS) A4 specification (210X297 mm) 593258 Application date 9 October 89 E Case No. 89121128 Category (the above sheds are filled by this bureau) A4 C4 Printed by the Ministry of Economy ’s Smart Finance / $ Bureau Employee Consumer Cooperative Patent Specification Invention I. Name New Chinese English Name W) Klaus Husmacher Huthmacher, Klaus Nationality M) Germany One Invention 2-, Creation A Μ) 18, Lachingen Road, Gelnhausen, Germany Larchenweg 18, D-63584 Gelnhausen, Germany Name of residence and residence (name) Nationality III. Applicant's residence and residence (office) Representative Name This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)