EP0117371B1 - Verfahren zur Herstellung von Aminobenzoesäuren aus entsprechenden Nitrotoluolen - Google Patents

Verfahren zur Herstellung von Aminobenzoesäuren aus entsprechenden Nitrotoluolen Download PDF

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Publication number
EP0117371B1
EP0117371B1 EP83400366A EP83400366A EP0117371B1 EP 0117371 B1 EP0117371 B1 EP 0117371B1 EP 83400366 A EP83400366 A EP 83400366A EP 83400366 A EP83400366 A EP 83400366A EP 0117371 B1 EP0117371 B1 EP 0117371B1
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Prior art keywords
process according
acid
electrolyser
solution
stage
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EP83400366A
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English (en)
French (fr)
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EP0117371A1 (de
Inventor
Jacques Chaussard
Claude Lahitte
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Electricite de France SA
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Electricite de France SA
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Priority to EP83400366A priority Critical patent/EP0117371B1/de
Priority to DE8383400366T priority patent/DE3371232D1/de
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction

Definitions

  • the present invention relates to a new process for preparing aminobenzoic acids, and in particular para-aminobenzoic acid, by oxidation of nitrotoluenes, followed by electrochemical reduction of the nitrobenzoic acids obtained.
  • n represents an integer equal to 1, 2 or 3
  • the penetrating bond in the benzene cycle represents a possibility of substitution of the latter in ortho, meta and / or para position
  • the benzene cycle can also carry other substituents remaining unchanged during the reaction.
  • Aminobenzoic acids obtained according to the process of the present invention, are chemicals mainly used in the pharmaceutical industry and in the dye industry.
  • chromic acid is an expensive and particularly toxic reagent which is preferred to be replaced in industry by oxygen in the presence of a catalyst or by nitric acid.
  • Electrochemistry does not have these drawbacks: pure aminobenzoic acid sulfate can be recovered by simple filtration after electrolysis.
  • the present invention relates to a process for the preparation of aminobenzoic acids, of the type comprising a first step of oxidation of nitrotoluenes to nitrobenzoic acids, followed by a second step of electrochemical reduction of said nitrobenzoic acids, characterized in that the agent oxidant used for the implementation of the first step is a sulfochromic solution which is regenerated at the anode of an electrolyser simultaneously ensuring the electrochemical reduction of the second step, said second electrochemical reduction step being carried out in an electrolyser whose compartments anode and cathode are separated by a membrane.
  • nitrobenzoic acid optionally containing unprocessed nitrotoluene is recovered by filtration after cooling.
  • the reaction medium is extended with ice water to a chromium concentration of less than 2.5 atomograms per liter and a sulfuric acid concentration of less than 50% by weight, then filtered.
  • the sulfochromic solution used to ensure the oxidation of nitrotoluenes can, for example, advantageously consist of an aqueous solution of 3 to 20% by weight of chromic oxide and 10 to 95% by weight of sulfuric acid which may contain chromium sulfate, and possibly other additives.
  • the nitrobenzoic acid is introduced into the cathode compartment 19 of the electrolyser in the form of a suspension in sulfuric acid of concentration 5 to 40% by weight (optionally containing metal salts serving as catalysts) , while the "used" sulfochromic solution is introduced into the anode compartment s .
  • the electrochemical process can for example be advantageously implemented in an electrolysis cell whose electrodes are lead plates, and the diaphragm which separates them, a cation exchange membrane.
  • This membrane is chosen as a function of its chemical resistance and of its selectivity: it must resist the corrosive action of the sulfochromic mixture and be allowed to pass, under the action of an electric current, only by hydrogen ions.
  • a circulation of the anodic and cathodic solutions between the electrodes and the diaphragm makes it possible to create sufficient agitation in the vicinity of the electrodes for the good progress of the electrochemical reactions.
  • the temperature is maintained between 20 and 100 ° C and preferably between 50 and 80 ° C, the current density between 3 and 15 A / dm2.
  • the electrolysis voltage is generally between 3 and 5 V.
  • the amount of current theoretically necessary to reduce one mole of mono-nitrated product at the cathode makes it possible to manufacture, at the anode, a quantity of chromic acid corresponding to the oxidation of one mole of nitrotoluene (6 electrons are required for reduce a nitrated function and 6 electrons to oxidize a 'methyl function).
  • the catholyte After electrolysis, that is to say when the catholyte no longer contains nitrated product and when the chromic solution has reached the desired concentration, the catholyte is cooled and filtered. The precipitate is aminobenzoic acid in the form of sulfate. The filtrate is re-acidified with concentrated sulfuric acid to compensate for the departure of acid bound to the amine. He can again serve as a catholyte.
  • the anode solution will be used for further oxidation of nitrotoluene.
  • the solution is stirred at 80 ° C for 46 hours. After cooling, the organic products are filtered. The filtrate is dosed and contains 31% sulfuric acid, 2% chromium trioxide and 11.3% chromium sulphate.
  • the solid is suspended in 500 ml of water which is basified to pH 13 by progressive addition of sodium hydroxide. The mixture is filtered.
  • the precipitate containing 8.5 g of unprocessed nitrotoluene and 1.7 g of chromium hydroxide (from insufficient filtration) will be recycled in the following experiment.
  • the filtrate containing the sodium salt of nitrobenzoic acid is acidified to pH 1 and then filtered. 16.2 g of para-nitrobenzoic acid are thus recovered, which corresponds to a yield of 85% relative to the para-nitrotoluene consumed and 82% relative to the chromic acid consumed.
  • anode compartment circulates the sulfochromic solution used to oxidize the nitrotoluene.
  • the cathode solution is a suspension of the 16.2 g of nitrobenzoic acid previously obtained in 500 g of a solution which had already served as a catholyte in a previous experiment and containing 125 g of sulfuric acid and 15 g of titanyl sulfate .
  • the temperature is maintained at 60 ° C, the current density at 10 A / dm2.
  • the electrolysis voltage is close to 4 V.
  • the catholyte When twice the amount of electricity necessary for the reduction of nitrobenzoic acid has passed through the electrolyzer, the catholyte is cooled before filtering it.
  • para-aminobenzoic acid sulfate 14.8 g of para-aminobenzoic acid sulfate are thus obtained (mass yield 82%).
  • Para-aminobenzoic acid can be recovered by basifying an aqueous suspension of the sulfate at pH 4.
  • the titanium salt solution will be reused in subsequent reductions after adding 4 g of concentrated sulfuric acid.
  • the anodic solution contains 6.7% chromic acid and can be used for other oxidations (current efficiency 48%).
  • Example 1 The procedure is the same as in Example 1.
  • the chromic solution used is the regenerated solution in Example 1. 13 g of para-nitrotoluene are added thereto and the mixture of nitrotoluene and chromous hydroxide recovered at the end of the chemical reaction of Example 1.
  • nitrobenzoic acid 12.7 g of nitrobenzoic acid are obtained, which represents a yield of 80% relative to the nitrotoluene consumed and 81% relative to the chromic acid consumed.
  • the concentration of the chromic solution goes from 2.01% to 5.81%, ie a current yield of 40%.
  • reaction medium After reaction with 30.1 g of para-nitrotoluene for 10 hours at 95 ° C, the reaction medium is extended with 380 g of water and then filtered.
  • the chromic solution contains 0.3% chromic acid.
  • the yield is therefore 97% compared to nitrotoluene and 96% compared to chromic acid.
  • the concentration of the chromic solution goes from 0.3% to 5.3%, giving a current yield of 49%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Claims (12)

1. Verfahren zun Herstellen von Aminobezoesäuren, durch Oxidation von Nitrotoluolen zu Nitrobenzoesäuren in einer ersten Stufe und elektrochenischer Reduktion dieser Nitrobenzoesäuren in einer anschließenden zweiten Stufe, dadurch gekennzeichnet, daß das zur Durchführung der ersten Stufe benutzte Oxidationsmittel eine Chromschwefelsäurelösung ist, die an der Anode einer Elektrolysevorrichtung regeneriert wird, wobei gleichzeitig die elektrochemische Reduktion der zweiten Stufe sichergestellt wird, und daß die genannte zweite Stufe der elektrochemischen Reduktion in einer Elektrolysiervorrichtung ausgeführt wird, deren Anoden- und Kathodenkammern durch eine Membran getrennt sind.
2. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, daß
die Chromschwefelsäurelösung eine wässrige Lösung von 3 bis 20 Gew.-% Chromoxid und 10 bis 95 Gew.-% Schwefelsäure ist, die Chromsulfat und gegebenenfalls noch andere Zusätze enthalten kann.
3. Verfahren nach einem der Ansprüche 1 oder 2,
dadurch gekennzeichnet, daß
die Nitrobenzoesäure, das Produkt der Oxidation der ersten Stufe, nach der Umsetzung aus der Chromschwefelsäurelösung abgetrennt wird durch:
gegebenenfalls Verdünnen bis zu einer Chromkonzentration von weniger als 2,5 g-Atom/I und einer Schwefelsäurekonzentration von weniger als 50 Gew.-%, gefolgt von
einer Filtration, die die Abtrennung der festen Nitrobenzoesäure von der zu regenerierenden Chromschwefelsäure sicherstellt.
4. Verfahren nach einem der Ansprüche 1 bis 3,
dadurch gekennzeichnet, daß
die genannte Membran eine Kationenaustauschmembran ist.
5. Verfahren nach einem der Ansprüche 1 bis 4,
dadurch gekennzeichnet, daß
die Elektrode der Anodenkammer der Elektrolysevorrichtung eine Blei- oder Bleioxid-Anode ist.
6. Verfahren nach einem der Ansprüche 1 bis 5,
dadurch gekennzeichnet, daß
die Elekrolyse in der genannten Elektrolysevorrichtung bei einer Temperatur von 20 bis 100°C, vorzugsweise von 50 bis 80°C ausgeführt wird.
7. Verfahren nach einem der Ansprüche 1 bis 6,
dadurch gekennzeichnet, daß
die in die Kathodenkammer der Elektrolysevorrichtung eingeführte Flüssigkeit eine in der ersten Stufe erhaltene Suspension von Nitrobenzoesäure in einer wässrigen Schwefelsäurelösung ist, die Aminobenzoesäure und gegebenenfalls andere Zusätze enthalten kann.
8. Verfahren nach einem der Ansprüche 1 bis 7,
dadurch gekennzeichnet, daß
der Katholyt, der die Kathode der Elektrolysevorrichtung bespülende Elektrolyt, 5 bis 40 Gew.-% Schwefelsäure enthält.
9. Verfahren nach einem der Ansprüche 3 bis 8,
dadurch gekennzeichnet, daß
die in die Anodenkammer der Elektrolysevorrichtung eingeführte Flüssigkeit eine Chromschwefelsäurelösung ist, die bei der Abtrennung nach Anspruch 3 anfällt.
10. Verfahren nach einem der Ansprüche 1 bis 9,
dadurch gekennzeichnet, daß
der Anolyt, der die Anode bespülende Elektrolyt, nach der Elektrolyse zur Wiederverwendung in einer neuen Oxidationsstufe von Nitrotoluol konzentriert wird.
11. Verfahren nach einem der Ansprüche 1 bis 10,
dadurch gekennzeichnet, daß
die Aminobenzoesäure in Form des Sulfats der Aminobenzoesäure durch Filtration aus dem Katholyten extrahiert wird.
12. Verfahren nach Anspruch 11,
dadurch gekennzeichnet, daß
das Filtrat, das durch die Extraktion der Aminobenzoesaure aus dem Katholyten erhalten wird, zur Wiederverwendung als Katholyt, der in die Kathodenkammer der Elektrodenvorrichtung eingeleitet wird, mit Schwefelsäure und Nitrobenzoesäure versehen wird.
EP83400366A 1983-02-22 1983-02-22 Verfahren zur Herstellung von Aminobenzoesäuren aus entsprechenden Nitrotoluolen Expired EP0117371B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP83400366A EP0117371B1 (de) 1983-02-22 1983-02-22 Verfahren zur Herstellung von Aminobenzoesäuren aus entsprechenden Nitrotoluolen
DE8383400366T DE3371232D1 (en) 1983-02-22 1983-02-22 Process for the production of aminobenzoic acids from corresponding nitrotoluenes

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EP83400366A EP0117371B1 (de) 1983-02-22 1983-02-22 Verfahren zur Herstellung von Aminobenzoesäuren aus entsprechenden Nitrotoluolen

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EP0117371A1 EP0117371A1 (de) 1984-09-05
EP0117371B1 true EP0117371B1 (de) 1987-04-29

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Publication number Priority date Publication date Assignee Title
US5021132A (en) * 1990-08-07 1991-06-04 Sandoz Ltd. Electrochemical process for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and the salts thereof
US6168172B1 (en) 1993-07-19 2001-01-02 K-2 Corporation In-line roller skate
KR100540888B1 (ko) * 2002-02-26 2006-01-11 에스케이케미칼주식회사 피-아미노벤조산의 제조방법
CN111041516B (zh) * 2019-12-19 2021-06-25 湖南大学 抗高血压药替米沙坦中间体制备新方法
CN113774414B (zh) * 2020-06-08 2023-04-14 清华大学 制备对氨基苯甲酸的方法及系统
CN112251770B (zh) * 2020-10-14 2021-07-27 湖南大学 一种抗高血压药替米沙坦中间体电化学制备新方法

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FR2512844A1 (fr) * 1981-09-14 1983-03-18 Electricite De France Procede de preparation d'acides aminobenzoiques a partir des nitrotoluenes correspondants

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