DE3814975A1 - Process for the preparation of arylhaloacetic acid derivatives - Google Patents

Process for the preparation of arylhaloacetic acid derivatives

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Publication number
DE3814975A1
DE3814975A1 DE19883814975 DE3814975A DE3814975A1 DE 3814975 A1 DE3814975 A1 DE 3814975A1 DE 19883814975 DE19883814975 DE 19883814975 DE 3814975 A DE3814975 A DE 3814975A DE 3814975 A1 DE3814975 A1 DE 3814975A1
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acid
group
preparation
positions
aryl
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DE19883814975
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German (de)
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Mieczyslaw Makosza
Krzysztof Wojciechowski
Krzysztof Sienkiewicz
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • 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
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines

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

Abstract

The invention relates to a process for the preparation of arylhaloacetic acid derivatives of the general formula ArCHXCOR in which Ar denotes an aromatic or heteroaromatic group which contains a nitro group in positions 2 or 4 and which can be substituted in the other positions, X denotes chlorine or bromine and R denotes a hydroxyl group, amino group or alkoxy group, the process consisting in reacting nitro derivatives of arenes or heteroarenes with esters of dichloroacetic acid, bromochloroacetic acid or dibromoacetic acid in the presence of a base.

Description

Die Erfindung betrifft eine Verfahren zur Herstellung von Arylhalogenessigsäurederivaten, die sich zur Herstellung von Pflanzenschutzmitteln und pharmazeutischen Substan­ zen eignen.The invention relates to a method for producing Arylhaloacetic acid derivatives that are used in the manufacture of pesticides and pharmaceutical substances are suitable.

Sie entsprechen der allgemeinen Formel ArCHXCOR, worin Ar eine aromatische oder heteroaromatische Gruppe wie Phenyl, Naphthyl, Pyridyl, Thienyl, Pyrryl, Indolyl, Chinolyl, die in der 2- oder 4-Stellung eine Nitrogruppe enthält und in den anderen Stellungen Substituenten wie Halogenatome, insbesondere Fluor oder Chlor, oder Alkoxy-, Aryloxy-, Alkyl- oder Arylthio-, Amino- oder Aminoacyl-, Ester- und Cyanogruppen enthalten kann. X bedeutet Chlor- oder Bromatome und R bedeutet eine Hydroxygruppe, Aminogruppe oder Alkoxygruppe, enthaltend 1 bis 4 Kohlenstoffatome. They correspond to the general formula ArCHXCOR, in which Ar is an aromatic or heteroaromatic group such as Phenyl, naphthyl, pyridyl, thienyl, pyrryl, indolyl, Quinolyl, which is a nitro group in the 2- or 4-position contains and in the other positions substituents such as Halogen atoms, especially fluorine or chlorine, or Alkoxy, aryloxy, alkyl or arylthio, amino or May contain aminoacyl, ester and cyano groups. X means chlorine or bromine atoms and R means one Containing hydroxyl group, amino group or alkoxy group 1 to 4 carbon atoms.  

Bevorzugt werden C1-C4-Alkoxy-, insbesondere Methoxy- und Ethoxy-, C6-C12-Aryloxy-, C1-C4-Alkyl- oder C6-C12- Arylthio-, Amino- oder Amino-C1-C4-Acyl-, C1-C4-Ester- oder Cyanogruppen als Substituenten für die Positionen 3, 5 und 6, gegebenenfalls auch für die Positionen 2 oder 4, eingesetzt.Preferred are C 1 -C 4 alkoxy, especially methoxy and ethoxy, C 6 -C 12 aryloxy, C 1 -C 4 alkyl or C 6 -C 12 arylthio, amino or amino C 1 -C 4 acyl, C 1 -C 4 ester or cyano groups are used as substituents for positions 3, 5 and 6, optionally also for positions 2 or 4.

Derivate von Arylhalogenessigsäuren haben bei der Her­ stellung von Pflanzenschutzmitteln und pharamzeutischen Verbindungen, insbesondere als Zwischenprodukte von halbsynthetischen Antibiotika aus der Gruppe der Peni­ cilline und Cephalosporine, Bedeutung gefunden.Derivatives of aryl haloacetic acids have been used in the manufacture provision of pesticides and pharmaceuticals Compounds, especially as intermediates from semi-synthetic antibiotics from the peni group cilline and cephalosporins, found meaning.

Nach den bekannten Verfahren werden Arylhalogenessig­ säuren, die den Gegenstand der vorliegenden Erfindung bilden, durch Halogenierung der entsprechenden Aryl- oder Hereoarylessigsäuren oder von deren Derivaten unter Verwendung von Chlor und Brom hergestellt.According to the known methods, aryl halo are vinegar acids that are the subject of the present invention form by halogenation of the corresponding aryl or Hereoarylacetic acids or their derivatives made using chlorine and bromine.

Das erfindungsgemäße Verfahren zur Herstellung von Aryl­ halogenessigsäurederivaten besteht in der Kondensation von Estern von Dichloressigsäure, Bromchloressigsäure oder Dibromessigsäure mit aromatischen oder heteroaroma­ tischen Nitroverbindungen der obengenannten Art, die in Gegenwart von basischen Mitteln,wie Alkoxiden, Hydri­ den, Amiden oder Hydroxiden von Alkalimetallen in apro­ tischen Lösungsmitteln, wie Dimethylformamid, Dimehthyl­ sulfoxid, Tetramethylharnstoff, N-Methylpyrrolidon, Tetrahydrofuran oder flüssigem Ammoniak durchgeführt wird. The process according to the invention for the production of aryl Halogen acetic acid derivatives consist of condensation of esters of dichloroacetic acid, bromochloroacetic acid or dibromoacetic acid with aromatic or heteroaroma tables nitro compounds of the type mentioned above, which in Presence of basic agents such as alkoxides, hydri the, amides or hydroxides of alkali metals in apro table solvents, such as dimethylformamide, dimethyl sulfoxide, tetramethylurea, N-methylpyrrolidone, Tetrahydrofuran or liquid ammonia performed becomes.  

Die Kondensationsreaktion wird in einem Temperaturbe­ reich von -50°C bis +20°C vorgenommen. Die bei der Kon­ densationsreaktion gebildeten Ester der allgemeinen Formel ArCHXCOR, worin Ar und X die vorher angegebenen Bedeutungen haben und worin R einen Niedrigalkoxysubsti­ tuenten, insbesondere mit bis zu 4 C-Atomen, bedeutet, werden in einer Mischung von Essigsäure und konzentrier­ ter Salzsäure unter Ausbildung der entsprechenden Aryl­ chloressigsäuren hydrolysiert. Bei der in flüssigem Ammoniak durchgeführten Kondensationsreaktion erhält man die Produkte als Amide der entsprechenden Arylhalogen­ essigsäuren der allgemeinen Form ArCHXCONH2, worin Ar und X die vor angegebenen Bedeutungen haben.The condensation reaction is carried out in a temperature range from -50 ° C to + 20 ° C. The esters of the general formula ArCHXCOR formed in the condensation reaction, in which Ar and X have the meanings given above and in which R is a lower alkoxy substituent, in particular having up to 4 carbon atoms, are dissolved in a mixture of acetic acid and concentrated hydrochloric acid Formation of the corresponding aryl chloroacetic acids hydrolyzed. In the condensation reaction carried out in liquid ammonia, the products are obtained as amides of the corresponding aryl haloacetic acids of the general form ArCHXCONH 2 , in which Ar and X have the meanings given above.

Die nachfolgenden Beispiele beschreiben das erfindungs­ gemäße Verfahren, ohne dieses in seinem Umfang zu beschränken.The following examples describe the invention proper procedures, without this to its extent restrict.

Beispiel 1example 1 Ethyl-4-nitrophenyl-α-chloroacetatEthyl 4-nitrophenyl- α- chloroacetate

Zu einer gerührten Mischung von Kalium-t-butoxid (24,7 g) in Dimethylformamid (125 ml) gibt man tropfen­ weise eine Mischung von Nitrobenzol (12,3 g) und Ethyl­ dichloroacetat (15,7 g), wobei man die Temperatur auf -15°C bis -20°C hält. Nach Beendigung der Zugabe, die 15 Minuten dauerte, wird die Mischung bei dieser Tempe­ ratur weitere 30 Minuten gerührt und dann in 5%ige Salzsäure gegossen und anschließend mit Ethylacetat (3 × 100 ml) extrahiert. Das Extrakt wird mit gesättig­ ter wäßriger Ammoniumchloridlösung gewaschen, über Magnesiumsulfat getrocknet und das Produkt wird durch Destillation unter vermindertem Druck gereinigt. Die Ausbeute an reinem, destilliertem Ethyl-4-nitrophenyl-α- chloroacetat beträgt 18,3 g und damit 75%. Der Siede­ punkt ist 154°C bis 150°C/1,5 mmHg.A mixture of nitrobenzene (12.3 g) and ethyl dichloroacetate (15.7 g) is added dropwise to a stirred mixture of potassium t-butoxide (24.7 g) in dimethylformamide (125 ml), the temperature being reduced holds at -15 ° C to -20 ° C. After the addition, which lasted 15 minutes, the mixture is stirred at this temperature for a further 30 minutes and then poured into 5% hydrochloric acid and then extracted with ethyl acetate (3 × 100 ml). The extract is washed with saturated aqueous ammonium chloride solution, dried over magnesium sulfate and the product is purified by distillation under reduced pressure. The yield of pure, distilled ethyl 4-nitrophenyl- α -chloroacetate is 18.3 g and thus 75%. The boiling point is 154 ° C to 150 ° C / 1.5 mmHg.

Beispiel 2Example 2 Ethyl-5-chloro-2-nitrophenyl-α-chloroacetatEthyl 5-chloro-2-nitrophenyl- α- chloroacetate

Nach dem in Beispiel 1 beschriebenen Verfahren erhält man aus 4-Chlornitrobenzol (15,8 g), Ethyldichloroacetat (15,7 g) und Kalium-t-butoxid (25 g) Ethyl-5-chlor-2- nitrophenyl-α-chloroacetat in einer Menge von 17,3 g, entsprechend 62%, mit einem Siedepunkt von 167°C bis 169°C/1,2 mmHg. According to the process described in Example 1, 4-chloronitrobenzene (15.8 g), ethyl dichloroacetate (15.7 g) and potassium t-butoxide (25 g) gave ethyl 5-chloro-2-nitrophenyl- α- chloroacetate in an amount of 17.3 g, corresponding to 62%, with a boiling point of 167 ° C to 169 ° C / 1.2 mmHg.

Beispiel 3Example 3 4-Nitrophenyl-α-chloroacetamid4-nitrophenyl- α- chloroacetamide

Zu einer Suspension von Natriummethoxid (14 g) in flüs­ sigem Ammoniak (200 ml) wird eine Lösung von Nitrobenzol (12,3 g) und Ethyldichloroacetat (15,7 g) in Tetrahydro­ furan tropfenweise zugegeben. Die Umsetzung wird weitere 1,5 Stunden durchgeführt und dann gibt man Ammonium­ chlorid (20 g) hinzu und dampft das Ammoniak ab. Der Rückstand wird mit Wasser (100 ml) gewaschen und mit Ethylacetat (3 × 100 ml) extrahiert. Das Extrakt wird mit Magnesiumsulfat getrocknet, das Lösungsmittel abge­ dampft und der Rückstand durch Umkristallisation aus Tetrachlorkohlenstoff gereinigt. Die Ausbeute an 4- Nitrophenyl-α-chloroacetamid 9 g, entsprechend 42%; der Schmelzpunkt beträgt 80°C bis 82°C.A solution of nitrobenzene (12.3 g) and ethyl dichloroacetate (15.7 g) in tetrahydro furan is added dropwise to a suspension of sodium methoxide (14 g) in liquid ammonia (200 ml). The reaction is carried out for a further 1.5 hours and then ammonium chloride (20 g) is added and the ammonia is evaporated off. The residue is washed with water (100 ml) and extracted with ethyl acetate (3 × 100 ml). The extract is dried with magnesium sulfate, the solvent is evaporated off and the residue is purified by recrystallization from carbon tetrachloride. The yield of 4-nitrophenyl- α- chloroacetamide 9 g, corresponding to 42%; the melting point is 80 ° C to 82 ° C.

Beispiel 4Example 4 Ethyl-2-(3-nitro-6-methoxypyridyl)-α-chloroacetatEthyl 2- (3-nitro-6-methoxypyridyl) - α- chloroacetate

Eine Lösung aus 2-Methoxy-5-nitropyridin (3,1 g) und Ethyldichloroacetat (3,4 g) in Dimethylformamid (10 ml) wird tropfenweise zu einer Lösung von Kalium-t-butoxid (5,5 g) in Dimethylformamid (20 ml) gegeben und die Temperatur dabei auf -5°C bis -10°C gehalten. Die Umset­ zung wird weitere 5 Minuten durchgeführt und dann wird die Mischung zu 5%iger Salzsäure gegossen. Das Produkt wird mit Ethylacetat (3 × 50 ml) extrahiert und das Extrakt wird getrocknet und das Lösungsmittel abge­ dampft. Das Produkt wird durch Säulenchromatografie über Kieselgel unter Verwendung von Hexan/Ethylacetat (4 : 1) als Eluiermittel gereinigt. Man erhält 4,6 g Ethyl-2-(3- nitro-6-methoxypyridyl)-α-chloroacetat in Form eines dicken Öls, entsprechend einer Ausbeute von 84%.A solution of 2-methoxy-5-nitropyridine (3.1 g) and ethyl dichloroacetate (3.4 g) in dimethylformamide (10 ml) is added dropwise to a solution of potassium t-butoxide (5.5 g) in dimethylformamide ( 20 ml) and the temperature kept at -5 ° C to -10 ° C. The reaction is carried out for a further 5 minutes and then the mixture is poured into 5% hydrochloric acid. The product is extracted with ethyl acetate (3 × 50 ml) and the extract is dried and the solvent is evaporated off. The product is purified by column chromatography on silica gel using hexane / ethyl acetate (4: 1) as the eluent. 4.6 g of ethyl 2- (3-nitro-6-methoxypyridyl) α- chloroacetate are obtained in the form of a thick oil, corresponding to a yield of 84%.

Claims (5)

1. Verfahren zur Herstellung von Arylhalogenessig­ säurederivaten der allgemeinen Formel ArCHXCOR, worin Ar eine aromatische oder heteroaromatische Gruppe bedeutet, die in den Stellungen 2 oder 4 eine Nitrogruppe enthält und in den anderen Stel­ lungen substituiert sein kann, X für Chlor oder Brom steht und R eine Hydroxygruppe, Aminogruppe oder Alkoxygruppe bedeutet, dadurch gekennzeichnet, daß man Nitroderivate von Arenen oder Heteroarenen mit Estern von Dichloressigsäure, Bromchloressig­ säure oder Dibromessigsäure in Gegenwart einer Base umsetzt.1. A process for the preparation of aryl haloacetic acid derivatives of the general formula ArCHXCOR, in which Ar is an aromatic or heteroaromatic group which contains a nitro group in positions 2 or 4 and which can be substituted in the other positions, X represents chlorine or bromine and R represents a hydroxyl group, amino group or alkoxy group, characterized in that nitroderivatives of arenes or heteroarenes are reacted with esters of dichloroacetic acid, bromochloroacetic acid or dibromoacetic acid in the presence of a base. 2. Verfahren zur Herstellung von Arylhalogenessig­ säurederivaten der allgemeinen Formel ArCHXCOR nach Anspruch 1, worin Ar eine aromatische oder hetero­ aromatische Gruppe wie Phenyl, Naphthyl, Pyridyl, Thienyl, Pyrryl, Indolyl, Chinolyl, enthaltend in den Stellungen 2 oder 4 eine Nitrogruppe, und in den anderen Stellungen Substituenten wie Halogen­ atome, insbesondere Fluor oder Chlor, oder Alkoxy-, Aryloxy-, Alkyl- oder Arylthio-, Amino- oder Amino­ acyl-, Ester- oder Cyanogruppen enthalten kann, X Chlor- oder Bromatome bedeutet und R eine Hydroxy­ gruppe, Aminogruppe oder Niedrigalkoxygruppe, ent­ haltend 1 bis 4 Kohlenstoffatome, bedeutet, dadurch gekennzeichnet, daß man Nitroderivate von Arenen oder Heteroarenen, wie Pyridin, Pyrrol, Thiophen, Indol oder Chinolin, mit niedrigen Estern von Dichloressigsäure, Bromchloressigsäure oder Di­ bromessigsäure, in Gegenwart eines basischen Mittels in einem aprotischen Lösungsmittel kon­ densiert und anschließend das Produkt aus der Reaktionsmischung in an sich bekannter Weise isoliert.2. Process for the preparation of aryl haloacetic acid acid derivatives of the general formula ArCHXCOR Claim 1, wherein Ar is an aromatic or hetero aromatic group such as phenyl, naphthyl, pyridyl, Thienyl, pyrryl, indolyl, quinolyl, containing in positions 2 or 4 a nitro group, and in the other positions are substituents such as halogen atoms, especially fluorine or chlorine, or alkoxy, Aryloxy, alkyl or arylthio, amino or amino can contain acyl, ester or cyano groups, X Chlorine or bromine atoms and R is a hydroxy group, amino group or lower alkoxy group, ent holding 1 to 4 carbon atoms, means thereby characterized in that nitroderivate of arenes or heteroarenes, such as pyridine, pyrrole, thiophene,  Indole or quinoline, with low esters of Dichloroacetic acid, bromochloroacetic acid or di bromoacetic acid, in the presence of a basic By means of an aprotic solvent densified and then the product from the Reaction mixture in a manner known per se isolated. 3. Verfahren zur Herstellung von Arylhalogenessigsäure der allgemeinen Formel ArCHXCOR, worin Ar, R und X die in Anspruch 1 angegebenen Bedeutungen haben, dadurch gekennzeichnet, daß man Nitroderivate von Arenen oder Heteroarenen, wie Pyridin, Pyrrol, Thiophen, Indol oder Chinolin, mit Niedrigestern von Dichloressigsäure, Bromchloressigsäure und Dibromessigsäure in Gegenwart von basischen Mitteln, wie Hydroxiden, Hydriden, Amiden, oder Alkoxiden von Alkalimetallen oder Mischungen von solchen Verbindungen kondensiert.3. Process for the preparation of aryl haloacetic acid of the general formula ArCHXCOR, wherein Ar, R and X has the meanings given in claim 1, characterized in that nitroderivatives of Arenes or heteroarenes, such as pyridine, pyrrole, Thiophene, indole or quinoline, with lower esters of dichloroacetic acid, bromochloroacetic acid and Dibromoacetic acid in the presence of basic Agents such as hydroxides, hydrides, amides, or Alkoxides of alkali metals or mixtures of such compounds condensed. 4. Verfahren zur Herstellung von Arylhalogenessig­ säurederivaten gemäß Ansprüchen 1 und 2, wobei die Kondensationsreaktion in solchen Lösungsmitteln, wie Dimethylformamid, Dimethylsulfoxid, Tetrame­ thylharnstoff, Tetrahydrofuran, N-Methylpyrrolidon oder flüssigem Ammoniak oder Mischungen solcher Lösungsmittel durchgeführt wird. 4. Process for the preparation of aryl haloacetic acid acid derivatives according to claims 1 and 2, wherein the Condensation reaction in such solvents, such as dimethylformamide, dimethyl sulfoxide, tetrame ethyl urea, tetrahydrofuran, N-methylpyrrolidone or liquid ammonia or mixtures thereof Solvent is carried out.   5. Verfahren zur Herstellung von Arylhalogenessig­ säuren gemäß Ansprüchen 1, 2 und 3, wobei die Kondensationsreaktion in flüssigem Ammoniak unter Ausbildung von Amiden von Arylhalogenessigsäuren der allgemeinen Formel ArCHXCONH2, worin Ar und X die in Anspruch 1 angegebenen Bedeutungen haben, durchgeführt wird.5. A process for the preparation of arylhaloacetic acids according to claims 1, 2 and 3, wherein the condensation reaction in liquid ammonia to form amides of arylhaloacetic acids of the general formula ArCHXCONH 2 , in which Ar and X have the meanings given in claim 1, is carried out.
DE19883814975 1987-05-12 1988-05-03 Process for the preparation of arylhaloacetic acid derivatives Withdrawn DE3814975A1 (en)

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PL26564587A PL148350B2 (en) 1987-05-12 1987-05-12 Method of obtaining arylochloroacetic esters

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PL148350B2 (en) 1989-10-31

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