DE875512C - Process for the cleavage of unsaturated ketones - Google Patents

Process for the cleavage of unsaturated ketones

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Publication number
DE875512C
DE875512C DEF5939A DEF0005939A DE875512C DE 875512 C DE875512 C DE 875512C DE F5939 A DEF5939 A DE F5939A DE F0005939 A DEF0005939 A DE F0005939A DE 875512 C DE875512 C DE 875512C
Authority
DE
Germany
Prior art keywords
cleavage
water
unsaturated ketones
unsaturated
acids
Prior art date
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
Application number
DEF5939A
Other languages
German (de)
Inventor
Josef Dr Binapfl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to DEF5939A priority Critical patent/DE875512C/en
Application granted granted Critical
Publication of DE875512C publication Critical patent/DE875512C/en
Expired legal-status Critical Current

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Classifications

    • 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
    • C07C45/54—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 compounds containing doubly bound oxygen atoms, e.g. esters
    • 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
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton

Description

Verfahren zur Spaltung von ungesättigten Ketonen Es wurde gefunden, daß ungesättigte Betone, die in Nachbarstellung zur Carbonylgruppe eine Äthylenbindung enthalten, durch Erhitzen in Gegenwart von Wasser, gegebenenfalls unter Zusatz von Säuren, aufgespalten werden können. Die Aufspaltung des Betonmoleküls erfolgt unter Aufnahme von Wasser durch die Äthylenbindung. Dabei tritt der Wasserstoff des Wassers an das der Carbonylgruppe des Betons benachbarte Iiohlenstoffatom der Äthylenbindung unter Bildung eines gesättigten Betons, während der Sauerstoff des Wassers von dem anderen Iiohlenstoffatom der Äthylenbindung unter Bildung einer Carbonylgruppe aufgenommen wird, so daß als zweites Spaltstück ein beton bzw. ein Aldehyd entsteht.Process for the cleavage of unsaturated ketones It has been found that unsaturated concretes that have an ethylene bond in the vicinity of the carbonyl group contained, by heating in the presence of water, optionally with the addition of Acids, can be broken down. The splitting of the concrete molecule takes place under Absorption of water through the ethylene bond. The hydrogen of the water enters the process to the ethylene bond atom adjacent to the carbonyl group of the concrete forming a saturated concrete, while the oxygen of the water from that other Iiohlenstoffatom of the ethylene bond added to form a carbonyl group so that the second split piece is a concrete or an aldehyde.

Unter den ungesättigten Betonen, die nach dem vorliegenden Verfahren aufgespalten werden können, seien z. B. genannt: Benzalaceton, Dibenzalaceton, o-, m- oder p-Chlorbenzalaceton, p-Nitrobenzalaceton, a-Methyl-a'-benzalaceton, Benzalcyclohexanon, p-Methyl-benzalcyclohexanon, Benzalacetophenon, i-Oxoi, 3-diphenyl-2-butylen und i-Cyclohexylidencyclohexanon-2.Among the unsaturated concretes produced by the present method can be split, such as B. named: Benzalacetone, Dibenzalacetone, o-, m- or p-chlorobenzalacetone, p-nitrobenzalacetone, a-methyl-a'-benzalacetone, benzalcyclohexanone, p-methyl-benzalcyclohexanone, benzalacetophenone, i-Oxoi, 3-diphenyl-2-butylene and i-Cyclohexylidenecyclohexanone-2.

Die Spaltungsbedingungen hängen im einzelnen von der besonderen Natur des ungesättigten ILetons ab und sind von Fall zu Fall leicht durch einfachen Versuch zu ermitteln. In der Regel ist es erforderlich, die Erhitzung in Gegenwart von Wasser unter Druck vorzunehmen. Durch Zusatz von Säuren, insbesondere schwachen Säuren, z. B. Borsäure, Adipinsäure oder Benzoesäure, kann die Spaltung gefördert werden. Beispiel i 89o g (= 5 Mol) i-Cyclohexylidencyclohexanon-2 werden mit 396 g Wasser (= 22 11o1) in einem Druckgefäß unter Rühren 3 Stunden auf 295 bis 300° erhitzt. Dabei stellt sich ein Druck von etwa 96 bis zoo atü ein. Nach dem Erkalten wird das nicht verbrauchte Wasser (35o g) von dem nicht wäßrigen Reaktionsprodukt abgetrennt, dessen Destillation im Vakuum 340 g Cyclohexanon liefert. Als Rückstand verbleiben 469 g unverändertes i-Cyclohexylidencyclohexanon-2 sowie 75 g eines höher siedenden Reaktionsproduktes..The splitting conditions depend in detail on the particular nature of the unsaturated ILetons and can be easily obtained from case to case by a simple experiment to investigate. Usually it is necessary to do the heating in the presence of water to do under pressure. By adding acids, especially weak acids, z. B. boric acid, adipic acid or benzoic acid, the cleavage can be promoted. Example i 89o g (= 5 mol) of i-cyclohexylidenecyclohexanone-2 are mixed with 396 g of water (= 22 11o1) in a pressure vessel with stirring for 3 hours at 295 to 300 ° heated. A pressure of around 96 to zoo atmospheres is established. After it has cooled down the unused water (35o g) separated from the non-aqueous reaction product, whose distillation in vacuo yields 340 g of cyclohexanone. Remain as residue 469 g of unchanged i-cyclohexylidenecyclohexanone-2 and 75 g of a higher-boiling one Reaction product ..

Setzt man dem eaktionsgemisch o,2 °/o Benzoesäure, Adipinsäure oder Borsäure zu, so erhält man nach 3 Stunden eine Ausbeute von 358 g Cyclohexanon.If one sets the reaction mixture o, 2% o benzoic acid, adipic acid or Boric acid, a yield of 358 g of cyclohexanone is obtained after 3 hours.

Beispiel 2 167 g (= 0,75 Mol) i-Oxo-z, 3-diphenyl-2-butylen werden mit 135 g Wasser (= 7,5 Mol) im Druckgefäß unter Rühren 3 Stunden auf etwa 3oo° erhitzt. Dabei stellt sich ein Drück von 78 bis 92 atü ein. Das nicht verbrauchte Wasser (zoo g) wird nach dem Erkalten vom nicht wäßrigen Reaktionsprodukt abgetrennt, dessen Destillation 135 g Acetophenon liefert. Als Rückstand verbleiben 25 g eines dickflüssigen Produktes, das noch unverändertes Ausgangsmaterial enthält.Example 2 167 g (= 0.75 mol) of i-oxo-z, 3-diphenyl-2-butylene are heated with 135 g of water (= 7.5 mol) in a pressure vessel with stirring for 3 hours at about 300 °. The pressure is between 78 and 92 atmospheres. The unused water (zoo g) is separated from the non-aqueous reaction product after cooling, the distillation of which yields 135 g of acetophenone. The residue left is 25 g of a viscous product which still contains unchanged starting material.

Claims (1)

PATENTANSPRUCH: Verfahren zur Spaltung von ungesättigten Ketonen, die in Nachbarstellung zur Carbonylgruppe eine Äthylenbindung enthalten, dadurch gekennzeichnet, daß man die Ketone mit Wasser, vorzugsweise unter Druck und vorteilhaft in Gegenwart von Säuren, insbesondere schwachen Säuren, erhitzt.PATENT CLAIM: Process for the cleavage of unsaturated ketones, which contain an ethylene bond adjacent to the carbonyl group, thereby characterized in that the ketones with water, preferably under pressure and advantageously heated in the presence of acids, especially weak acids.
DEF5939A 1951-04-01 1951-04-01 Process for the cleavage of unsaturated ketones Expired DE875512C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEF5939A DE875512C (en) 1951-04-01 1951-04-01 Process for the cleavage of unsaturated ketones

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF5939A DE875512C (en) 1951-04-01 1951-04-01 Process for the cleavage of unsaturated ketones

Publications (1)

Publication Number Publication Date
DE875512C true DE875512C (en) 1953-05-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
DEF5939A Expired DE875512C (en) 1951-04-01 1951-04-01 Process for the cleavage of unsaturated ketones

Country Status (1)

Country Link
DE (1) DE875512C (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE927688C (en) * 1953-01-23 1955-05-16 Basf Ag Process for the production of cyclohexanone
DE932966C (en) * 1952-05-06 1955-09-12 Hoechst Ag Process for the cleavage of cyclohexenylcyclohexanone
DE1193040B (en) * 1960-03-10 1965-05-20 Inventa A G Fuer Forschung Process for the production of cyclohexanone
WO1988005771A1 (en) * 1987-02-04 1988-08-11 Mallinckrodt, Inc. Hydrolysis of activated olefinic ketones and aldehydes
US4871881A (en) * 1987-02-04 1989-10-03 Mallinckrodt, Inc. Hydrolysis of activated olefinic ketones and aldehydes
US4927805A (en) * 1987-02-04 1990-05-22 Mallinckrodt, Inc. Hydrolysis of curcumin
WO1994003420A1 (en) * 1992-08-05 1994-02-17 Exxon Chemical Patents Inc. Aquathermolytic cleavage of unsaturated ketones

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE932966C (en) * 1952-05-06 1955-09-12 Hoechst Ag Process for the cleavage of cyclohexenylcyclohexanone
DE927688C (en) * 1953-01-23 1955-05-16 Basf Ag Process for the production of cyclohexanone
DE1193040B (en) * 1960-03-10 1965-05-20 Inventa A G Fuer Forschung Process for the production of cyclohexanone
WO1988005771A1 (en) * 1987-02-04 1988-08-11 Mallinckrodt, Inc. Hydrolysis of activated olefinic ketones and aldehydes
GR880100035A (en) * 1987-02-04 1988-12-16 Mallinckrodt Inc Hydrolysis of activated olefinic ketones and aldehydes related application
US4810824A (en) * 1987-02-04 1989-03-07 Mallinckrodt, Inc. Hydrolysis of activated olefinic ketones and aldehydes
US4871881A (en) * 1987-02-04 1989-10-03 Mallinckrodt, Inc. Hydrolysis of activated olefinic ketones and aldehydes
US4927805A (en) * 1987-02-04 1990-05-22 Mallinckrodt, Inc. Hydrolysis of curcumin
EP0606934A1 (en) * 1987-02-04 1994-07-20 FRIES & FRIES, INC. Hydrolysis of activated olefins
WO1994003420A1 (en) * 1992-08-05 1994-02-17 Exxon Chemical Patents Inc. Aquathermolytic cleavage of unsaturated ketones

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