DE946807C - Process for the simultaneous production of phenol and acetone - Google Patents

Process for the simultaneous production of phenol and acetone

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Publication number
DE946807C
DE946807C DES26716A DES0026716A DE946807C DE 946807 C DE946807 C DE 946807C DE S26716 A DES26716 A DE S26716A DE S0026716 A DES0026716 A DE S0026716A DE 946807 C DE946807 C DE 946807C
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Germany
Prior art keywords
parts
phenol
acetone
cumene
hydroperoxide
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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DES26716A
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German (de)
Inventor
Igor Scriabine
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Rhone Poulenc SA
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Rhone Poulenc SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/04—Phenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
    • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
    • C07C409/08—Compounds containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
    • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
    • C07C409/08—Compounds containing six-membered aromatic rings
    • C07C409/10—Cumene hydroperoxide
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/08—Acetone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/10—Methyl-ethyl ketone

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur gleichzeitigen Herstellung von Phenol und Aceton Die Erfindung betrifft ein Verfahren zur Herstellung von Phenol aus Cumolhydroperoxyd.Process for the simultaneous production of phenol and acetone Die The invention relates to a process for the production of phenol from cumene hydroperoxide.

Es ist bekannt, daB die alkylaromatischen Hydroperoxyde in Phenole und Carbonylverbindungen, und zwar in Ketone oder Aldehyde, zersetzt werden können, je nach dem Alkylsubstituenten des aromatischen Ringes.It is known that the alkyl aromatic hydroperoxides form phenols and carbonyl compounds can be decomposed into ketones or aldehydes, depending on the alkyl substituent on the aromatic ring.

Nach älteren Veröffentlichungen wird die Spaltung in Gegenwart von Katalysatoren mit saurer Reaktion bewirkt. Hock und Lang [vgl. Berichte der Deutschen Chemischen Gesellschaft 77, S. 257 (I944)] benutzten zu diesem Zweck Schwefelsäure. Sie beschreiben insbesondere die Spaltung von Cumolhydroperoxyd in Phenol und Aceton und die Spaltung von Diphenylmethan-hydroperoxyd in Phenol und Benzaldehyd durch Erhitzen in zo° Joiger Schwefelsäure. Weiterhin wird die Spaltung von Tetralinhydroperoxyd zu o-Oxyphenylbuttersäure (unter Bildung von Oxyphenylbutyraldehyd als Zwischenprodukt) in alkoholischer Lösung mittels konzentrierter Schwefelsäure beschrieben. Wieland und Maier [vgl. Berichte der Deutschen Chemischen Gesellschaft 64, S. I205 (193I)] stellten fest, daB bei Behandlung von Triphenylmethyl-hydroperoxyd mit Benzoylcblorid im organischen Medium die Spaltung in Phenol und Benzophenon hervorgerufen wird.According to older publications, the cleavage occurs in the presence of Catalysts with acidic reaction causes. Hock and Lang [cf. Reports from the Germans Chemischen Gesellschaft 77, p. 257 (1944)] used sulfuric acid for this purpose. In particular, they describe the cleavage of cumene hydroperoxide into phenol and acetone and the cleavage of diphenylmethane hydroperoxide into phenol and benzaldehyde Heat in zo ° Joiger sulfuric acid. Furthermore, the cleavage of tetralin hydroperoxide to o-oxyphenylbutyric acid (with formation of oxyphenylbutyraldehyde as an intermediate) described in alcoholic solution using concentrated sulfuric acid. Wieland and Maier [cf. Reports of the German Chemical Society 64, p. I205 (193I)] found that when triphenylmethyl hydroperoxide was treated with Benzoyl chloride in the organic medium the cleavage into phenol and benzophenone is caused.

Es wurde nun gefunden, daß die Spaltung von Cumolhydroperoxyd in Phenol und Aceton in guter Ausbeute erfolgt, wenn man es in Gegenwart von Schwefel, Phosphor oder Arsen ah Katalysatoren erhitzt. Von diesen Elementen ergeben Schwefel oder Phosphor gute Resultate. Arsen ergibt weniger gute Resultate.It has now been found that the cleavage of cumene hydroperoxide in phenol and acetone in good yield when taken in the presence of sulfur, phosphorus or arsenic ah catalysts heated. Of these elements result in sulfur or Phosphorus good results. Arsenic gives less good results.

Die "erfindungsgemäß verwendeten nicht sauren Katalysatoren üben auf die Apparatur keinerlei.korTodierende Wirkung aus. Weiterhin können sie in keinem Fall als Kondensationsmittel für die Reaktionsprodukte, z. B. Phenol und Aceton, wirken, was die Bildung von unerwünschten harzigen Produkten ausschließt.The "non-acidic catalysts used according to the invention exert the apparatus does not have any corrosive effect. Furthermore, they cannot in any Case as a condensing agent for the reaction products, e.g. B. phenol and acetone, act, which excludes the formation of undesirable resinous products.

Das Cumolhydroperoxyd wird nach bekannten Methoden durch Oxydation von Cumol nach Hock und Lang (vgl. die obige Literaturstelle), gegebenenfalls unter Druck und in der Hitze, hergestellt.The cumene hydroperoxide is oxidized according to known methods of cumene according to Hock and Lang (cf. the above reference), if necessary under Pressure and in the heat.

Zur Spaltung wird das Cumolhydroperoxyd entweder in wäßriger Suspension oder in Lösung in einem organischen Lösungsmittel, z. B. Cumol, verwendet. Wenn man mit dem isolierten Hydroperoxyd arbeiten will, so kann man die Abtrennung aus den Lösungen in bekannter Weise entweder durch Abdestillieren des Cumols oder durch Extraktion des Hydroperoxyds mit konzentrierter Natronlauge bewirken.For cleavage, the cumene hydroperoxide is either in an aqueous suspension or in solution in an organic solvent, e.g. B. cumene is used. if if you want to work with the isolated hydroperoxide, you can do the separation the solutions in a known manner either by distilling off the cumene or by Effect extraction of the hydroperoxide with concentrated sodium hydroxide solution.

Der Katalysator wird fest oder in Suspension (gegebenenfalls in Lösung im Falle von Phosphor oder Schwefel) in einer Flüssigkeit verwendet, welche dieselbe wie das Lösungsmittel für das Ciunolhydroperoxyd sein kann. Man arbeitet vorteilhaft bei einer solchen Temperatur, so daß das während der Umsetzung gebildete Aceton entweicht, z. B. bei der Siedetemperatur des Lösungsmittels, die man durch das Vakuum, unter dem die Apparatur gehalten wird, regulieren kann. Die exotherme Spaltung läuft im allgemeinen schnell an und wird durch das Sieden unter Rückfluß des Lösungsmittels reguliert. Wenn die Umsetzung beendet ist, destilliert man das Lösungsmittel und das Phenol ab.The catalyst becomes solid or in suspension (optionally in solution in the case of phosphorus or sulfur) in a liquid used which the same how the solvent for the Ciunolhydroperoxyd can be. One works well at such a temperature that the acetone formed during the reaction escapes, e.g. B. at the boiling point of the solvent, which is achieved by the vacuum, under which the apparatus is held, can regulate. The exothermic cleavage is in progress generally increases rapidly and is caused by refluxing the solvent regulated. When the reaction has ended, the solvent is distilled off and the phenol off.

Die folgenden Beispiele sollen die Erfindung näher erläutern. Die Teile bedeuten Gewichtsmengen. Beispiel 1 Man bringt 26o Teile Äthylbenzol, das 3,5 Teile Schwefel enthält, unter 253 mm Quecksilbersäule zum Sieden (98°). Andererseits stellt man eine Lösung von 369 Teilen Cumolhydroperoxyd in 998 Teilen Äthylbenzol her und gießt ioo Teile dieser Lösung in das siedende Äthylbenzol. Nach 8 Minuten kommt die Reaktion in Gang, und das gebildete Aceton destilliert ab. Man gießt innerhalb von 25 Minuten den Rest der Lösung des Cumolhydroperoxyds ein, wonach man das Sieden unter Rückfluß noch 25 Minuten aufrecht erhält, dann destilliert man. Man gewinnt iio Teile Aceton (Ausbeute 8o °% der Theorie und 194 Teile Phenol (Ausbeute 85 °/a der Theorie).The following examples are intended to explain the invention in more detail. the Parts mean amounts by weight. Example 1 Bringing 26o parts of ethylbenzene, the Contains 3.5 parts of sulfur, below 253 mm of mercury to boil (98 °). on the other hand a solution of 369 parts of cumene hydroperoxide in 998 parts of ethylbenzene is produced and pour 100 parts of this solution into the boiling ethylbenzene. After 8 minutes the reaction starts and the acetone formed distills off. One pours inside from 25 minutes the remainder of the solution of cumene hydroperoxide, after which the boiling maintained under reflux for a further 25 minutes, then distilled. One wins 100 parts of acetone (yield 80% of theory and 194 parts of phenol (yield 85 ° / a theory).

Beispiel 2 Man oxydiert Cumol nach Hock und Lang (vgl. obige Literaturstelle) in der Weise, daß man eine Lösung von 5oo Teilen Cumolhydroperoxyd in 930 Teilen Cumol erhält. Man gießt ioo Teile dieser Lösung in Cumol, das unter 21o mm Quecksilbersäule zum Sieden erhitzt -wird (io8 bis iio°) und das 2,5 Teile Schwefel enthält. Die Reaktion kommt innerhalb von 15 Minuten in Gang. Man gießt dann innerhalb von 21 Minuten den Rest der Hydroperoxydlösurig zu und erhitzt noch 40 Minuten. Das gesamte Hydroperoxyd wird zersetzt.EXAMPLE 2 Cumene is oxidized according to Hock and Lang (cf. above reference) in such a way that a solution of 500 parts of cumene hydroperoxide in 930 parts of cumene is obtained. 100 parts of this solution are poured into cumene, which is heated to boiling under 210 mm of mercury (10 8 to 10 °) and which contains 2.5 parts of sulfur. The reaction starts within 15 minutes. The remainder of the hydroperoxide solution is then poured in over the course of 21 minutes and the mixture is heated for a further 40 minutes. All of the hydroperoxide is broken down.

Man erhält 143 Teile Aceton und 232,6 Teile Phenol. Beispiel 3 Man arbeitet wie im vorhergehenden Beispiel mit denselben Mengen, jedoch verwendet man statt 2 5 Teilen Schwefel 5 Teile weißen Phosphor. Man e hält 132,5 Teile Aceton und 215,1 Teile Phenol.143 parts of acetone and 232.6 parts of phenol are obtained. EXAMPLE 3 The same amounts are used as in the previous example, but instead of 2 5 parts of sulfur, 5 parts of white phosphorus are used. 132.5 parts of acetone and 215.1 parts of phenol are kept.

r Beispiel 4 Man arbeitet wie in Beispiel 2, j edoch mit 1o45 Teilen einer Lösung aus 366 Teilen Cumolhydroperoxyd in Cumol in Gegenwart von 1o Teilen feinverteiltem Arsen. Man gewinnt 85 Teile Aceton und 16o,6 Teile Phenol.Example 4 You work as in Example 2, but with 1045 parts a solution of 366 parts of cumene hydroperoxide in cumene in the presence of 10 parts finely divided arsenic. 85 parts of acetone and 16o.6 parts of phenol are obtained.

Claims (1)

PATENTANSPRUCH: Verfahren zur gleichzeitigen Herstellung von Phenol und Aceton durch Spaltung -von Cumolhydroperoxyd, dadurch gekennzeichnet, daß man Cumolhydroperoxyd in Gegenwart von Schwefel, Phosphor oder Arsen als Katalysator erhitzt. In Betracht gezogene Druckschriften: Italienische Patentschrift Nr. 450 422. Claim: Process for the simultaneous production of phenol and acetone by cleavage of cumene hydroperoxide, characterized in that cumene hydroperoxide is heated in the presence of sulfur, phosphorus or arsenic as a catalyst. References considered: Italian patent specification No. 450 422.
DES26716A 1951-01-10 1952-01-06 Process for the simultaneous production of phenol and acetone Expired DE946807C (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR946807X 1951-01-10

Publications (1)

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DE946807C true DE946807C (en) 1956-08-09

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DES26716A Expired DE946807C (en) 1951-01-10 1952-01-06 Process for the simultaneous production of phenol and acetone

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