DE3148889C2 - - Google Patents

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Publication number
DE3148889C2
DE3148889C2 DE3148889A DE3148889A DE3148889C2 DE 3148889 C2 DE3148889 C2 DE 3148889C2 DE 3148889 A DE3148889 A DE 3148889A DE 3148889 A DE3148889 A DE 3148889A DE 3148889 C2 DE3148889 C2 DE 3148889C2
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DE
Germany
Prior art keywords
chlorine
bromine
butyl
hal
substituted
Prior art date
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Expired
Application number
DE3148889A
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German (de)
Other versions
DE3148889A1 (en
Inventor
Michael Dipl.-Chem. Dr. 6700 Ludwigshafen De Thomas
Heinz Dipl.-Chem. Dr. 6710 Frankenthal De Eilingsfeld
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BASF SE
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BASF SE
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Priority to DE19813148889 priority Critical patent/DE3148889A1/en
Publication of DE3148889A1 publication Critical patent/DE3148889A1/en
Application granted granted Critical
Publication of DE3148889C2 publication Critical patent/DE3148889C2/de
Granted legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/45—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
    • C07C205/46—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group the carbon skeleton containing carbon atoms of quinone rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/56—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/44—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing doubly-bound oxygen atoms bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/02—Quinones with monocyclic quinoid structure
    • C07C50/06—Quinones with monocyclic quinoid structure with unsaturation outside the quinoid structure
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/24—Quinones containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
    • C07C50/28—Quinones containing groups having oxygen atoms singly bound to carbon atoms with monocyclic quinoid structure
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
    • C07C50/30—Quinones containing groups having oxygen atoms singly bound to carbon atoms with polycyclic non-condensed quinoid structure
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C66/00—Quinone carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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

Description

Die Erfindung betrifft ein Verfahren gemäß Patentanspruch 1.The invention relates to a method according to claim 1.

Als Lösungsmittel für die Umsetzungen eignen sich beispiels­ weise Ameisensäure, Essigsäure oder Propionsäure und insbe­ sondere Chlorbenzol, Dichlorbenzole, Nitrobenzol, Dichlor­ methan, Trichlormethan, Dichlorethan, Trichlorethane, Trichlorethylen oder Tetrachlorethylen.Examples of suitable solvents for the reactions are wise formic acid, acetic acid or propionic acid and esp special chlorobenzene, dichlorobenzenes, nitrobenzene, dichloro methane, trichloromethane, dichloroethane, trichloroethane, Trichlorethylene or tetrachlorethylene.

Als Chlorierungsmittel können z. B. Chlor oder Sulfuryl­ chlorid verwendet werden.As a chlorinating agent, e.g. B. chlorine or sulfuryl chloride can be used.

Als Katalysatoren können z. B. einzeln oder in Mischungen N,N-Dimethylformamid, Lewis-Säuren, wie Eisentrichlorid, Aluminiumtrichlorid oder Titantetrachlorid, und Radikal­ bildner wie Benzoylperoxid oder Azoisobutyronitril zuge­ setzt werden. Auch eine Katalyse durch Licht ist möglich.As catalysts such. B. individually or in mixtures N, N-dimethylformamide, Lewis acids, such as iron trichloride, Aluminum trichloride or titanium tetrachloride, and radical formers such as benzoyl peroxide or azoisobutyronitrile be set. Catalysis by light is also possible.

Das erfindungsgemäße Verfahren wird zweckmäßigerweise so durchgeführt, daß man die Verbindung der Formel II und die Katalysatoren im Lösungsmittel oder Lösungsmittelgemisch vorgelegt und dann bei Temperaturen von ungefähr 50 bis 150°C das Chlorierungsmittel zugibt.The method according to the invention is expediently so carried out that the compound of formula II and Catalysts in the solvent or solvent mixture submitted and then at temperatures of about 50 to 150 ° C. the chlorinating agent adds.

Bevorzugt als Ausgangsmaterial sind Verbindungen der Formel II, in denen n=0 bedeutet.Compounds of the formula II in which n = 0 are preferred as the starting material.

Bevorzugte Lösungsmittel sind Trichlorethane, bevorzugte Temperaturen liegen zwischen 70 und 90°C, und das bevor­ zugte Chlorierungsmittel ist Sulfurylchlorid. Vorzugs­ weise verwendet man pro zu ersetzendes Wasserstoffatom 1 bis 1,3 Mol des Chlorierungsmittels.Preferred solvents are trichloroethanes, preferred Temperatures are between 70 and 90 ° C, before that The chlorinating agent used is sulfuryl chloride. Preferential one uses wisely for each hydrogen atom to be replaced 1 to 1.3 moles of the chlorinating agent.

Als Katalysatoren werden vorzugsweise N,N-Dimethylformamid und Eisentrichlorid eingesetzt. N, N-dimethylformamide are preferably used as catalysts and iron trichloride used.  

Einzelheiten der Reaktionsführung können den Beispielen entnommen werden, in denen sich Angaben über Teile und Prozente, sofern nicht anders vermerkt, auf das Gewicht beziehen.Details of the reaction procedure can be found in the examples are taken, in which information about parts and Unless otherwise noted, percentages are by weight Respectively.

Überraschenderweise können nach dem erfindungsgemäßen Ver­ fahren Verbindungen der Formel II selektiv im Chinonring ohne Kernchlorierung des Ringes A in eine Stufe chloriert werden.Surprisingly, according to the Ver drive compounds of formula II selectively in the quinone ring Chlorinated in one step without core chlorination of ring A. will.

Es ist bekannt 2,3,6-Trichlor-5-phenylbenzochinon-1,4 aus 2-Phenylbenzochinon-1,4 durch stufenweise Chlorwasserstoff- Anlagerung und anschließende Oxidation herzustellen [z. B. J. G. Wilson, Aust. J. Chem. 25, 2383 (1972)], jedoch ist dieses dreistufige Verfahren wegen der schlechten Ausbeute von insgesamt ca. 15% technisch nicht brauchbar. Nach dem erfindungsgemäßen Verfahren kann z. B. 2,3,6-Trichlor-5- phenylbenzochinon-1,4 einstufig in 80%iger Ausbeute aus 2-Phenylbenzochinon-1,4 hergestellt werden.It is known from 2,3,6-trichloro-5-phenylbenzoquinone-1,4 2-phenylbenzoquinone-1,4 by stepwise hydrogen chloride To produce attachment and subsequent oxidation [z. B. J.G. Wilson, Aust. J. Chem. 25, 2383 (1972)], however this three-step process because of poor yield of a total of approx. 15% cannot be used technically. After this inventive method can, for. B. 2,3,6-trichloro-5- phenylbenzoquinone-1,4 in one step in 80% yield 2-phenylbenzoquinone-1,4 can be produced.

Spezielle Chinone können, wie in der US-Def. Publ. T 9 17 001 beschrieben ist, in wäßrigem Eisessig chloriert werden; man erhält jedoch bei Einsatz von Verbindungen der Formel II keine einheitlichen Produkte.Special quinones can, as in US Def. Publ. T 9 17 001 is chlorinated in aqueous glacial acetic acid; one however, when compounds of the formula are used II no uniform products.

Die Halogenchinone der allgemeinen Formel I sind wertvolle Redoxkatalysatoren sowie Vorprodukte für Wirk- und Farbstoffe.The haloquinones of the general formula I are valuable redox catalysts and intermediate products for active substances and dyes.

Die Erfindung betrifft weiterhin neue Verbindungen der all­ gemeinen Formel IV gemäß Patentanspruch 2. The invention further relates to new compounds of all general formula IV according to claim 2.  

Beispiel 1Example 1

Zu 36,8 Teilen 2-Phenylbenzochinon-1,4, 140 Teilen 1,1,2- Trichlorethan, 0,2 Teilen Eisentrichlorid und 1 Teil N,N- Dimethylformamid tropft man bei 70-80°C 90 Teile Sulfuryl­ chlorid innerhalb von 1 Stunde zu und rührt noch ca. 2 Stunden bei gleicher Temperatur nach. Die abgekühlte Reaktions­ mischung wird zweimal mit je 200 Teilen Wasser gewaschen, über Calciumchlorid getrocknet und unter vermindertem Druck eingeengt. Der ölige Rückstand wird aus ca. 40 Teilen Alkohol umkristallisiert. Man erhält 47 Teile 2,3,6- Trichlor-5-phenylbenzochinon-1,4 vom Schmelzpunkt 106-108°C.To 36.8 parts of 1,4-phenylbenzoquinone, 140 parts of 1,1,2- Trichloroethane, 0.2 part iron trichloride and 1 part N, N- Dimethylformamide is added dropwise at 70-80 ° C 90 parts of sulfuryl chloride within 1 hour and stir for about 2 hours at the same temperature. The cooled reaction mixture is washed twice with 200 parts of water, Dried over calcium chloride and under reduced Pressure reduced. The oily residue becomes approx. 40 parts Alcohol recrystallized. 47 parts 2, 3, 6 Trichloro-5-phenylbenzoquinone-1,4 with a melting point of 106-108 ° C.

Analog zu dem beschriebenen Verfahren erhält man auch die in der folgenden Tabelle gekennzeichneten Verbindungen: Analogously to the process described, the Connections marked in the following table:  

Claims (2)

1. Verfahren zur Herstellung von arylsubstituierten Halogenchinonen der allgemeinen Formel I in der Hal Chlor oder Brom bedeutet und der Ring A ein- oder zweifach durch Fluor, Chlor, Brom, Cyan, Nitro, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tert.-Butyl, Trifluormethyl, Chlormethyl, 2-Chlorethyl, Methoxymethyl, 2-Methoxyethyl, 2-Cyanoethyl, Methylmercapto, Methylsulfonyl, Phenyl, Hydroxycarbonyl, Methoxycarbonyl, Ethoxycarbonyl, Hydroxysulfonyl, Methoxysulfonyl oder Ethoxysulfonyl substituiert sein kann, dadurch gekennzeichnet, daß man Verbindungen der Formel II in der Hal die oben genannte Bedeutung hat und n 0 oder 1 sein kann,
mit einem Chlorierungsmittel in unter den Reaktionsbedingungen nicht halogenierbaren Lösungsmitteln bei erhöhter Temperatur umsetzt.1. Process for the preparation of aryl-substituted haloquinones of the general formula I in which Hal is chlorine or bromine and ring A is mono- or disubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, trifluoromethyl, chloromethyl , 2-chloroethyl, methoxymethyl, 2-methoxyethyl, 2-cyanoethyl, methylmercapto, methylsulfonyl, phenyl, hydroxycarbonyl, methoxycarbonyl, ethoxycarbonyl, hydroxysulfonyl, methoxysulfonyl or ethoxysulfonyl can be substituted, characterized in that compounds of the formula II in which Hal has the meaning given above and n can be 0 or 1,
reacted with a chlorinating agent in solvents which cannot be halogenated under the reaction conditions at elevated temperature. 2. Arylsubstituierte Halogendinone der allgemeinen Formel in der Hal Chlor oder Brom ist und der Ring A ein- oder zweifach durch Fluor, Chlor, Brom, Cyan, Nitro, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, tert.-Butyl, Trifluormethyl, Chlormethyl, 2-Chlorethyl, Methoxymethyl, 2-Methoxyethyl, 2-Cyanomethyl, Methyl­ mercapto, Methylsulfonyl, Phenyl, Hydroxycarbonyl, Methoxycarbonyl, Ethoxycarbonyl, Hydroxysulfonyl, Methoxy­ sulfonyl oder Ethoxysulfonyl substituiert ist.2. Aryl-substituted halodinones of the general formula in which Hal is chlorine or bromine and ring A is mono- or disubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, trifluoromethyl, chloromethyl , 2-chloroethyl, methoxymethyl, 2-methoxyethyl, 2-cyanomethyl, methyl mercapto, methylsulfonyl, phenyl, hydroxycarbonyl, methoxycarbonyl, ethoxycarbonyl, hydroxysulfonyl, methoxy sulfonyl or ethoxysulfonyl.
DE19813148889 1981-12-10 1981-12-10 Process for the preparation of aryl-substituted haloquinones, and novel haloquinones Granted DE3148889A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19813148889 DE3148889A1 (en) 1981-12-10 1981-12-10 Process for the preparation of aryl-substituted haloquinones, and novel haloquinones

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19813148889 DE3148889A1 (en) 1981-12-10 1981-12-10 Process for the preparation of aryl-substituted haloquinones, and novel haloquinones

Publications (2)

Publication Number Publication Date
DE3148889A1 DE3148889A1 (en) 1983-06-23
DE3148889C2 true DE3148889C2 (en) 1989-11-16

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Publication number Priority date Publication date Assignee Title
GB9211110D0 (en) * 1992-05-26 1992-07-08 Ici Plc Compound

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