DE3145927A1 - 4(5)-Methyl-5(4)-chloroimidazole and process for its preparation - Google Patents

4(5)-Methyl-5(4)-chloroimidazole and process for its preparation

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Publication number
DE3145927A1
DE3145927A1 DE19813145927 DE3145927A DE3145927A1 DE 3145927 A1 DE3145927 A1 DE 3145927A1 DE 19813145927 DE19813145927 DE 19813145927 DE 3145927 A DE3145927 A DE 3145927A DE 3145927 A1 DE3145927 A1 DE 3145927A1
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DE
Germany
Prior art keywords
methyl
preparation
chloroimidazole
chlorimidazole
methylimidazole
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.)
Withdrawn
Application number
DE19813145927
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German (de)
Inventor
Toni Dipl.-Chem. Dr. 6701 Meckenheim Dockner
Matthias Dipl.-Chem. 6700 Ludwigshafen Wetzler
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BASF SE
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BASF SE
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.)
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DE19813145927 priority Critical patent/DE3145927A1/en
Priority to CA000414770A priority patent/CA1181082A/en
Priority to JP19263782A priority patent/JPS5892665A/en
Priority to DE8282110343T priority patent/DE3268888D1/en
Priority to AT82110343T priority patent/ATE17722T1/en
Priority to EP82110343A priority patent/EP0081679B1/en
Priority to US06/441,803 priority patent/US4481211A/en
Publication of DE3145927A1 publication Critical patent/DE3145927A1/en
Priority to CA000458999A priority patent/CA1189517A/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/68—Halogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

4(5)-Methyl-5(4)-chloroimidazole and process for its preparation by reaction with chlorine with exposure to light or with a salt of hypochlorous acid.

Description

(5)-Methyl-5(4)-chlorimidazol und Verfahren zu seiner(5) -Methyl-5 (4) -chlorimidazole and method for its

Herstellung 4(5)-Methyl-5(4)-chlorimidazol ist ein neuer Stoff, der vornehmlich zur Herstellung hochwirksamer Mikrozide dienen kann, in denen er beispielsweise als Imidazoliumverbindung vorliegt.Manufacture 4 (5) -Methyl-5 (4) -chlorimidazole is a new substance that can mainly be used to produce highly effective microcides, in which he, for example is present as an imidazolium compound.

Eine typische solche lmidazoliumverbindung hat die Formel wobei R R1, R2, R3 i.a. kurzkettige (C1 bis C4)-Alkylreste oder ein Halogenatom und R4 einen vorzugsweise langkettigen (C8 bis C25) Alkylrest, oder einen aromatischen Rest (Aryl bzw. Arylalkyl) bedeuten.A typical such imidazolium compound has the formula where R R1, R2, R3 generally mean short-chain (C1 to C4) -alkyl radicals or a halogen atom and R4 is a preferably long-chain (C8 to C25) alkyl radical or an aromatic radical (aryl or arylalkyl).

Das zur Herstellung solcher Stoffe erforderliche Methylchlorimidazol gewinnt man vorteilhaft durch photocheirische Chlorierung von 4(5)-Methylimidazol. Auch durch Umsetzung von Methylimidazol mit unterchloriger Säure bzw. deren Salzen in wäßriger Lösung läßt sich Methylchlorimidazol gewinnen Die photochemische Chlorierung ist ein zur Herstellung chlorierter Kohlenwasserstoffe und ähnlicher Verbindungen gut eingeführtes Verfahren Sie verläuft im vorliegenden Falle zwischen z.B. 0 und 100°Cs eine ausreichende Reaktionsgeschwindigkeit erzielt man bei 20 bis 800C im Lichte z,B, einer Quecksilberhochdrucklampe. Gewöhnlich venfendet man ein chemisch indifferentes Lösungsmittel, insbesondere einen perhalogenierten Kohlenwasserstoff wie CC14O Im vorliegenden Falle fällt die chlorierte Verbindung als Hydrochlorid an, aus dem man in bekannter Weise die freie 3ase freisetzen kann Das Hydrochlorid ist in z.B. CCl4 unlöslich und läßt sich somit leicht gewinnen.The methylchlorimidazole required to manufacture such substances is advantageously obtained by photochemical chlorination of 4 (5) -methylimidazole. Also through implementation of methylimidazole with hypochlorous acid or their salts in aqueous solution, methylchlorimidazole can be obtained Photochemical chlorination is one used to produce chlorinated hydrocarbons and similar compounds well established procedure It proceeds in the present If, for example, between 0 and 100 ° Cs, a sufficient reaction rate is achieved one at 20 to 800C in the light z, B, a high pressure mercury lamp. Usually used a chemically inert solvent, especially a perhalogenated one Hydrocarbon such as CC14O In the present case, the chlorinated compound is precipitated as a hydrochloride, from which the free 3ase can be released in a known manner The hydrochloride is insoluble in e.g. CCl4 and can therefore be easily obtained.

Bemerkenswerterweise wird über die Chlorierung von Imidazolen bisher wenig berichtet. Zu dieser Feststellung konmen auch Schofield> Grimmett und Keene in "The Azoles", Cambridge University Press, Cambridge, G.B. (1976) S. 46.Remarkably, the chlorination of imidazoles has been discussed so far little reported. Schofield> Grimmett and Keene also came to this conclusion in "The Azoles", Cambridge University Press, Cambridge, G.B. (1976) p. 46.

Auch die vorgenannten berichten lediglich daß 2-Methyl-bzw 2-Ethylimidazol bei Einhaltung enger Bedingungen mit Hypochlorit die 4>5-Dichlorverbindungen liefern Das vorstehend erläuterte erfindungsgemäße Herstellverfahren ist daher besonders überraschend.The aforementioned also only report that 2-methyl- or 2-ethylimidazole if strict conditions are met with hypochlorite, the 4> 5-dichloro compounds The manufacturing process according to the invention explained above is therefore special surprised.

J beispiel 1 Diskontinuierliche Herstellung von 4(5)-Methyl-5(4)-chlorimidazol auf photochemischem Wege.J Example 1 Batch production of 4 (5) -methyl-5 (4) -chlorimidazole by photochemical means.

In einem mit einer Quecksilber-Hochdruck-Entladungslampe (Fabrikat Hanau, Typ 0150) ausgerüsteten Rührkolben werden 82 g (1 Mol) 4-Methylimidazol in 1000 ml Tetrachlorkohlenstoff gelöst und während 7 Stunden in diese Lösung bei 50 bis 600C insgesamt 76 g Chlor eingeleitet. Der dabei entstehende Niederschlag besteht aus den Hydrochloriden des Ausgangs- und des Endproduktes. Er wird abfiltriert und aus DMF umkristallisiert, in Wasser gelöst und mit NaHCO3 auf pH = 7 gebracht. Der hierbei entstehenae Niederschlag wird abfiltriert und getrocknet. Man gewinnt 36 g, das sind 31 % Ausbeute. Fp = 131 bis 131,8°C.In one with a high pressure mercury discharge lamp (make Hanau, type 0150) equipped stirred flasks are 82 g (1 mol) of 4-methylimidazole in Dissolve 1000 ml of carbon tetrachloride and immerse it in this solution for 7 hours at 50 initiated up to 600C a total of 76 g of chlorine. The resulting precipitate exists from the hydrochlorides of the starting and the end product. It is filtered off and recrystallized from DMF, dissolved in water and brought to pH = 7 with NaHCO3. Of the this precipitate is filtered off and dried. You win 36 g, that's 31% yield. Mp = 131-131.8 ° C.

Analyse: Errechnet: Gefunden: C 41,2% 41,2% n 4,2% 4,2 N 24,03% 24,1% Cl 0,47% 30,5% Beispiel 2 Kontinuierliche erstellung auf photochemischem Wege von h(5)-sTethyl-5(4)-chlorimidazol.Analysis: Calculated: Found: C 41.2% 41.2% n 4.2% 4.2 N 24.03% 24.1% Cl 0.47% 30.5% Example 2 Continuous production by photochemical means of h (5) -s-ethyl-5 (4) -chlorimidazole.

In einem gläsernen Rohrreaktor, der mit einer Quecksilberhochdrucklampe (Fabrikat Hanau, 2000W), Utmlzpumpe, Kühler und Abscheider ausgerüstet ist, werden bei einer Temperatur ° von 25 bis 35 C stündlich 2000 g einer Lösung, bestehend aus 200 g 4-Methylimidazol und 1800 g Chlorbenzol und 150 1 Chlor umgesetzt.In a glass tube reactor with a high-pressure mercury lamp (Make Hanau, 2000W), utility pump, cooler and separator at a temperature of 25 to 35 C per hour 2000 g of a solution consisting reacted from 200 g of 4-methylimidazole and 1800 g of chlorobenzene and 150 l of chlorine.

L J Der sich im Abscheider ansammelnde Niederschlag wird von Zeit zu Zeit entnommen, abfiltriert 9 in Wasser gelöst und mit NaHC03 das 4(5)-idethyl-5(4)-chlorimidazol ausgefällt.L J The precipitate that collects in the separator is removed from time to time, filtered off 9 dissolved in water and with NaHCO3 the 4 (5) -idethyl-5 (4) -chlorimidazole precipitated.

Aus insgesamt 10,6 kg 4-Methylimidazol erhält man 10,5 kg 4(5)-Methyl-5(4) chlorimidazolO Das sind 70 % Ausbeute.10.5 kg of 4 (5) -methyl-5 (4) are obtained from a total of 10.6 kg of 4-methylimidazole chlorimidazolO that's 70% yield.

Fp = 130 bis a320C.M.p. 130 to a320C.

Beispiel 3 Herstellung von 4(5)-Methyl-5(4)"chlorimidazol in wäßriger Lösung 200 g 4 Methylimidazol werden in 200 g Wasser gelöst; in diese Lösung werden bei OOC innerhalb von 30 Minuten 2 kg 13die wäßrige Bleichlauge (NaOCl) eingetragen und noch 30 Minuten nachgerührt Der Niederschlag wird abgesaugt und mit Eiswasser (150 ml) nachgewaschen anschließend bei 500 im Vakuum getrocknet. Ausbeute 142 gn entsprechend 47,2 der berechneten; Reinheit 95 %.Example 3 Preparation of 4 (5) -methyl-5 (4) "chloroimidazole in aqueous Solution 200 g of 4 methylimidazole are dissolved in 200 g of water; be in this solution at OOC, 2 kg of the aqueous bleaching liquor (NaOCl) were added within 30 minutes and stirred for a further 30 minutes. The precipitate is filtered off and washed with ice water (150 ml) rewashed then dried in vacuo at 500. Yield 142 gn corresponding to 47.2 of the calculated; Purity 95%.

Aus dem Filtrat und dem Waschwasser können durch Extraktion mit Chloroform noch einmal 42 g des Produktes gewonnen werden, so daß sich eine Gesamtausbeute von 184 g, das sind 60 ß der berechneten Ausbeute ergibt.The filtrate and the washing water can be extracted by chloroform Another 42 g of the product can be obtained, so that there is an overall yield of 184 g, which is 60 ß of the calculated yield.

Claims (3)

Patentansprüche 1 4(5)Methyl-5(4)-chlorimidazol.Claims 1 4 (5) methyl-5 (4) chlorimidazole. 2. Verfahren zur Herstellung von 4(5)-Methyl-5(4)-chlorimidazol, dadurch gekennzeichnet, daß man 4(5)=Methylimidazol der Einwirkung von Chlor unter Belichtung aussetzt.2. Process for the preparation of 4 (5) -Methyl-5 (4) -chlorimidazole, thereby characterized in that one 4 (5) = methylimidazole the action of chlorine under exposure suspends. 3 Verfahren zur Herstellung von 4(5)-Methyl-5(4)-chlorimidazol9 dadurch gekennzeichnet, daß man 4(5)-Methylchlorimidazol in vorzugsweise wäßriger Lösung mit einem Salz der unterchlorigen Säure behandelt.3 Process for the preparation of 4 (5) -Methyl-5 (4) -chlorimidazole9 thereby characterized in that 4 (5) -Methylchlorimidazol in preferably aqueous solution treated with a salt of hypochlorous acid.
DE19813145927 1981-11-20 1981-11-20 4(5)-Methyl-5(4)-chloroimidazole and process for its preparation Withdrawn DE3145927A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE19813145927 DE3145927A1 (en) 1981-11-20 1981-11-20 4(5)-Methyl-5(4)-chloroimidazole and process for its preparation
CA000414770A CA1181082A (en) 1981-11-20 1982-11-03 Substituted benzylimidazolium salts and microbicides containing these compounds
JP19263782A JPS5892665A (en) 1981-11-20 1982-11-04 Substituted benzylimidazolium salt and fungicide
DE8282110343T DE3268888D1 (en) 1981-11-20 1982-11-10 Substituted benzylimidazolium salts and microbicides containing them
AT82110343T ATE17722T1 (en) 1981-11-20 1982-11-10 SUBSTITUTED BENZYLIMIDAZOLIUM SALTS AND MICROBICIDES CONTAINING THEM.
EP82110343A EP0081679B1 (en) 1981-11-20 1982-11-10 Substituted benzylimidazolium salts and microbicides containing them
US06/441,803 US4481211A (en) 1981-11-20 1982-11-15 Microbiocidal substituted benzylimidazolium salts
CA000458999A CA1189517A (en) 1981-11-20 1984-07-16 Substituted benzylimidazolium salts and microbicides containing these compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19813145927 DE3145927A1 (en) 1981-11-20 1981-11-20 4(5)-Methyl-5(4)-chloroimidazole and process for its preparation

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DE3145927A1 true DE3145927A1 (en) 1983-06-01

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DE19813145927 Withdrawn DE3145927A1 (en) 1981-11-20 1981-11-20 4(5)-Methyl-5(4)-chloroimidazole and process for its preparation

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DE (1) DE3145927A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0614891A2 (en) * 1993-03-12 1994-09-14 Lonza Ag Optionally 2-substituted 5-chloroimidazoles
US5484939A (en) * 1993-03-12 1996-01-16 Lonza Ltd. 2-substituted 5-chlorimidazoles

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4993443B2 (en) * 2006-07-28 2012-08-08 日本エンバイロケミカルズ株式会社 Industrial disinfectant and disinfecting method using the same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0614891A2 (en) * 1993-03-12 1994-09-14 Lonza Ag Optionally 2-substituted 5-chloroimidazoles
EP0614890A2 (en) * 1993-03-12 1994-09-14 Lonza Ag Optionally 2-substituted 5-chloroimidazoles
EP0614890A3 (en) * 1993-03-12 1995-01-11 Lonza Ag Optionally 2-substituted 5-chloroimidazoles.
EP0614891A3 (en) * 1993-03-12 1995-05-03 Lonza Ag Optionally 2-substituted 5-chloroimidazoles.
US5484939A (en) * 1993-03-12 1996-01-16 Lonza Ltd. 2-substituted 5-chlorimidazoles
US5508425A (en) * 1993-03-12 1996-04-16 Lonza Ltd. Process for producing 2-substituted 5-chlorimidazoles
US5606072A (en) * 1993-03-12 1997-02-25 Lonza Ltd. Process for the production of 2-substituted 5-chlorimidazole-4-carbaldehyde

Also Published As

Publication number Publication date
JPH0375544B2 (en) 1991-12-02
JPS5892665A (en) 1983-06-02

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