DE2144170C3 - Process for the preparation of optionally alkyl-substituted 3-hydroxycyclohexen <2) -ones - Google Patents

Process for the preparation of optionally alkyl-substituted 3-hydroxycyclohexen <2) -ones

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Publication number
DE2144170C3
DE2144170C3 DE19712144170 DE2144170A DE2144170C3 DE 2144170 C3 DE2144170 C3 DE 2144170C3 DE 19712144170 DE19712144170 DE 19712144170 DE 2144170 A DE2144170 A DE 2144170A DE 2144170 C3 DE2144170 C3 DE 2144170C3
Authority
DE
Germany
Prior art keywords
preparation
ones
substituted
hydroxycyclohexen
optionally alkyl
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
DE19712144170
Other languages
German (de)
Other versions
DE2144170B2 (en
DE2144170A1 (en
Inventor
Faisal Dipl.-Chem. Dr. Abo Dagga
Martin Dipl.-Chem. Dr. Cherubim
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.)
Wintershall Dea Deutschland AG
Original Assignee
Deutsche Texaco 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 Deutsche Texaco AG filed Critical Deutsche Texaco AG
Priority to DE19712144170 priority Critical patent/DE2144170C3/en
Priority to GB3868072A priority patent/GB1398535A/en
Priority to IT2860972A priority patent/IT964354B/en
Priority to CA150,594A priority patent/CA1006539A/en
Priority to NL7211822A priority patent/NL7211822A/xx
Priority to BE788317D priority patent/BE788317A/en
Priority to JP8784472A priority patent/JPS4834859A/ja
Priority to FR7231178A priority patent/FR2151105B3/fr
Publication of DE2144170A1 publication Critical patent/DE2144170A1/en
Publication of DE2144170B2 publication Critical patent/DE2144170B2/en
Application granted granted Critical
Publication of DE2144170C3 publication Critical patent/DE2144170C3/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
    • C07C45/61—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
    • C07C45/64—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 introduction of functional groups containing oxygen only in singly bound form
    • 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
    • C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
    • C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
    • 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
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
    • 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

Description

in der Ri und R2 jeweils H oder Alkylgruppen mit 1—5 C-Atomen, vorzugsweise 1—3 C-Atomen, bedeuten, mit 30—300 g Wasser und 0,05—2,0 Mol einer starken Mineralsäure je Mol des cyanäthylierten Ketons bei einer Temperatur von etwa 20 bis 150° C umgesetzt werden.in which Ri and R2 each have H or alkyl groups 1-5 carbon atoms, preferably 1-3 carbon atoms, with 30-300 g water and 0.05-2.0 mol a strong mineral acid per mole of the cyanoethylated ketone at a temperature of about 20 to 150 ° C are implemented.

2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als starke Mineralsäure Schwefelsäure oder Phosphorsäure eingesetzt wird.2. The method according to claim 1, characterized in that the strong mineral acid is sulfuric acid or phosphoric acid is used.

3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Umsetzung bei etwa 50 bis etwa 1500C vorgenommen wird.3. The method of claim 1 or 2, characterized in that the reaction is carried out at about 50 to about 150 0 C.

Es ist bekannt, daß sich reaktionsfähige CH2-Gruppen in Gegenwart basischer Katalysatoren wie Pyridin, quartärer Ammoniumhydroxyd-Verbindungen oder Alkali, an aktivierte C = C-Doppelverbindungen addieren lassen.It is known that reactive CH 2 groups can be added to activated C =C double compounds in the presence of basic catalysts such as pyridine, quaternary ammonium hydroxide compounds or alkali.

Diese sogenannte Michael-Addition wurde bereits zur Cyanäthylierung von Ketonen verwendet, vgl. z. B. US-Patentschrift 23 86 736. Zur Herstellung insbesondere Λ-monocyanäthylierter Ketone kann man nach dem in der US-Patentschrift 28 50 519 beschriebenen Verfahren auch Ketone mit Acrylsäurenitril in Gegenwart von primären Aminen oder deren Salzen in einem pH-Bereich von 5—12 umsetzen. Alle diese cyanäthylierten Ke .one lassen sich durch nachfolgende alkalische oder saure Verseifung ihrer Nitrilgruppen in die entsprechenden Carbonsäuren oder deren Derivate umwandeln.This so-called Michael addition has already been used for the cyanoethylation of ketones, cf. B. US Pat. No. 2,386,736. For the preparation of, in particular, Λ-monocyanethylated ketones, according to the process described in US Pat. No. 2,850,519 also includes ketones with acrylonitrile in the presence of primary amines or their salts in a pH range of 5-12. All of these cyanoethylated Ke .one can be converted into the .one by subsequent alkaline or acidic saponification of their nitrile groups convert corresponding carboxylic acids or their derivatives.

Überraschenderweise wurde nun gefunden, daß man in saurem Medium unter bestimmten Bedingungen aus monocyanäthylierten aliphatischen Ketonen, zweckmäßig unter Rückflußbedingungen, cyclische Ketone erhält.Surprisingly, it has now been found that under certain conditions in an acidic medium monocyanethylated aliphatic ketones, expediently under reflux conditions, cyclic ketones receives.

Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von ggf. alkylsubstituierten 3-Hydroxy-cyclohexen-(2)-onen, dadurch gekennzeichnet, daß monocyanäthylierte Ketone der allgemeinen FormelThe invention therefore relates to a process for the preparation of optionally alkyl-substituted 3-hydroxy-cyclohexen (2) -ones, characterized in that monocyanethylated ketones of the general formula

R, CH,R, CH,

Il οIl ο

C CH2 CH2 C CH 2 CH 2

R1 R 1

ten, mit 30—300 g Wasser und 0,05—2,0 Mol einer starken Mineralsäure je Mol des monocyanäthylierten Ketons bei einer Temperatur von etwa 20 bis etwa 150" C umgesetzt werden.th, with 30-300 g of water and 0.05-2.0 moles of one strong mineral acid per mole of the monocyanethylated ketone at a temperature of about 20 to about 150 "C are implemented.

Als starke Mineralsäuren sind Phosphorsäure und besonders Schwefelsäure geeignetPhosphoric acid and especially sulfuric acid are suitable as strong mineral acids

Die Umsetzung kann so vorgenommen werden, daß das monocyanäthylierte Keton in Wasser gelöst und die starke Mineralsäure zugetropft wird.The reaction can be carried out in such a way that the monocyanethylated ketone is dissolved in water and the strong mineral acid is added dropwise.

Die Temperaturen liegen vorzugsweise im Bereich von etwa 50 bis etwa 150° C.The temperatures are preferably in the range from about 50 to about 150 ° C.

Die Umsetzung kann über eine Zeitdauer von 0,1 — 10 Stunden erfolgen. Bevorzugt sind Reaktionszeiten von 0,1 —1 Stunde.The reaction can take place over a period of 0.1-10 hours. Reaction times of 0.1-1 hour.

Die Zusammensetzung und Struktur der erfindungsgemäßen Verbindungen wurde durch CHN-Bestimmungen, Nachweis der funktionellen Gruppen, durch chemische Analyse, durch Aufnahme der UV-, IR-, NMR- und Massenspektren sowie durch Molekularge-Wichtsbestimmungen sichergestellt. Die erfindungsgemäß hergestellten Verbindungen können als Zwischenprodukte für organische Synthesen, vor allem für die Herstellung von Resorcin-Derivaten, beispielsweise von 2,6-Dialkylresorcinen verwendet werden. Derartige Resorcin-Derivate können als Ausgangsstoffe für die Herstellung von Phenol- und Epoxidharzen oder als Oxydations-Inhibitoren sowie als Modifizierungsmittel und Härter verwendet werden. Außerdem eignen sie sich als Alterungsschutzmittel für Schmieröle, Elastome-The composition and structure of the compounds according to the invention was determined by CHN, Detection of the functional groups, by chemical analysis, by recording the UV, IR, NMR and mass spectra as well as molecular weight determinations ensured. According to the invention Compounds produced can be used as intermediates for organic syntheses, especially for the Production of resorcinol derivatives, for example of 2,6-dialkylresorcines, can be used. Such Resorcinol derivatives can be used as starting materials for the production of phenolic and epoxy resins or as Oxidation inhibitors as well as modifiers and hardeners can be used. They are also suitable as an anti-aging agent for lubricating oils, elastomer

jo re und Plastomere; sie können als Additive eingesetzt werden und sind wirksame Bakterizide.jo re and plastomers; they can be used as additives are and are effective bactericides.

Die Herstellung der Resorcin-Derivate aus den erfindungsgemäß hergestellten 2,6-Dialkyl-3-hydroxycyclohexenonen kann nach bekannten Verfahren durch Erhitzen mit Essigsäureanhydrid und konzentrierter Schwefelsäure vorgenommen werden.The preparation of the resorcinol derivatives from the 2,6-dialkyl-3-hydroxycyclohexenones prepared according to the invention can by known methods by heating with acetic anhydride and concentrated Sulfuric acid can be made.

Das folgende Beispiel soll die Erfindung näher erläutern.The following example is intended to explain the invention in more detail.

Beispielexample

2,6-Dimethyl-3-hydroxy-cyclohexen-(2)-on2,6-dimethyl-3-hydroxy-cyclohexen (2) -one

64 g 2-Mono-(j3-cyanäthyl)-pentanon-(3) (0,46 Mol) wurden zusammen mit 36 g Wasser vorgelegt und innerhalb von ca. 5 Minuten tropfenweise mit 70,5 ml konzentrierter Schwefelsäure versetzt. Dabei stieg die Temperatur bis 130°C. Anschließend wurde noch weitere 5 Minuten bei Rückflußtemperatur gekocht.64 g of 2-mono- (j3-cyanoethyl) -pentanone- (3) (0.46 mol) were presented together with 36 g of water and 70.5 ml of concentrated sulfuric acid were added dropwise over a period of approx. 5 minutes. The Temperature up to 130 ° C. The mixture was then boiled for a further 5 minutes at reflux temperature.

Das Reaktionsgemisch wurde in 600 ml Eiswasser gegossen, wobei sich Kristalle abschieden, welche abgenutscht und aus Wasser umkristallisiert wurden (54 g = 83% der Theorie). Der Schmelzpunkt betrug 115 —1170C. Die Kristalle waren luftfeuchtigkeitsempfindlich. The reaction mixture was poured into 600 ml of ice water, crystals separating out, which were suction filtered and recrystallized from water (54 g = 83% of theory). The melting point was 115 -117 0 C. The crystals were air-sensitive to moisture.

CHN-BestimmungCHN determination

CNCN

Molekulargewicht Molecular weight

in welcher Ri und R2 jeweils H oder Alkylgruppen mit Berechnet 68,54 8,63% 140in which Ri and R 2 each have H or alkyl groups with Calculated 68.54 8.63% 140

1—5 C-Atomen, vorzugsweise 1—3 C-Atomen, bedeu- 65 Gefunden 68,9 8,5% 1451-5 carbon atoms, preferably 1-3 carbon atoms, mean 65 found 68.9 8.5% 145

Claims (1)

Patentansprüche:Patent claims: 1. Verfahren zur Herstellung von ggf. alkylsubstituierten 3-Hydroxy-cycIohexen-(2)-onen, dadurch gekennzeichnet, daß monocyanäthylierte Ketone der allgemeinen Formel1. A process for the preparation of optionally alkyl-substituted 3-hydroxy-cycIohexen- (2) -ones, characterized in that monocyanethylated General formula ketones R1-CH1-C-C-CH1-CH1-CNR 1 -CH 1 -CC-CH 1 -CH 1 -CN ' Il I'Il I O R2 O R 2
DE19712144170 1971-09-03 1971-09-03 Process for the preparation of optionally alkyl-substituted 3-hydroxycyclohexen <2) -ones Expired DE2144170C3 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE19712144170 DE2144170C3 (en) 1971-09-03 1971-09-03 Process for the preparation of optionally alkyl-substituted 3-hydroxycyclohexen <2) -ones
GB3868072A GB1398535A (en) 1971-09-03 1972-08-18 Process for the production of substituted cyclohexen-2-ones
IT2860972A IT964354B (en) 1971-09-03 1972-08-29 PROCEDURE FOR MANUFACTURING CICLOESEN 2 ONI REPLACED
NL7211822A NL7211822A (en) 1971-09-03 1972-08-30
CA150,594A CA1006539A (en) 1971-09-03 1972-08-30 Process for production of substituted cyclohexene-2-ones
BE788317D BE788317A (en) 1971-09-03 1972-09-01 PROCESS FOR PREPARING SUBSTITUTED CYCLOHEXENE-2-ONES
JP8784472A JPS4834859A (en) 1971-09-03 1972-09-01
FR7231178A FR2151105B3 (en) 1971-09-03 1972-09-01

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19712144170 DE2144170C3 (en) 1971-09-03 1971-09-03 Process for the preparation of optionally alkyl-substituted 3-hydroxycyclohexen <2) -ones

Publications (3)

Publication Number Publication Date
DE2144170A1 DE2144170A1 (en) 1973-03-08
DE2144170B2 DE2144170B2 (en) 1979-09-20
DE2144170C3 true DE2144170C3 (en) 1980-06-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
DE19712144170 Expired DE2144170C3 (en) 1971-09-03 1971-09-03 Process for the preparation of optionally alkyl-substituted 3-hydroxycyclohexen <2) -ones

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5492942A (en) * 1977-12-28 1979-07-23 Mitsui Petrochem Ind Ltd Production of 3-amino-2-cyclohexenone
US4175135A (en) * 1978-07-18 1979-11-20 Union Carbide Corporation Method of controlling acarina ectoparasites on warmblooded animals by orally administering to the animal an ectoparasitically effective amount of a 2-aryl-1,3-cyclohexanedione compound, and alkali metal salts, ammonium salts and enol esters thereof

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Publication number Publication date
DE2144170B2 (en) 1979-09-20
DE2144170A1 (en) 1973-03-08

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