EP0000924A1 - Heterocyclic phenyl ethers and process for their preparation - Google Patents

Heterocyclic phenyl ethers and process for their preparation Download PDF

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Publication number
EP0000924A1
EP0000924A1 EP78100686A EP78100686A EP0000924A1 EP 0000924 A1 EP0000924 A1 EP 0000924A1 EP 78100686 A EP78100686 A EP 78100686A EP 78100686 A EP78100686 A EP 78100686A EP 0000924 A1 EP0000924 A1 EP 0000924A1
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Prior art keywords
methyl
compounds
formula
benzthiazol
benzoxazol
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EP0000924B1 (en
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Reinhard Dr. Handte
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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 in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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 in position 2
    • C07D235/26—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2

Definitions

  • the compounds of formula II can be prepared by known methods e.g. from the corresponding 2-mercapto or 2-0xo compounds by halogenation or else from the 2-amino compounds by diazotization and subsequent Sandmeyer reaction (see CA 59, 396j; Am. Chem. J. 21 (1899) , 111).
  • the compounds of the formula IV can be prepared by the process (a) by using 2 mol or more of the compound II per 1 mol of the compound III.
  • reaction temperatures are between 80 ° and 250 ° C, preferably 90 ° to 150 ° C, optionally at the boiling point of the solvent used.
  • compound IV is increasingly formed as an undesirable by-product per se. However, this converts back to I above 80 ° with further III (see variant b)).
  • the reaction can also be carried out at temperatures above the boiling point in a closed vessel under autogenous pressure; this is necessary if the solvent used boils below 80 °.
  • Polar aprotic solvents e.g.
  • Acid amides such as dimethylformamide, dimmthylacetamide, diethylacetamide, N-methylpyrrolidone and hexamethylphosphoric triamide, also dimethyl sulfoxide; Nitriles such as acetonitrile or propionitrile, ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone.
  • Nitriles such as acetonitrile or propionitrile, ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone.
  • aliphatic alcohols and aromatic hydrocarbons such as toluene or xylene can also be used.
  • Suitable basic compounds are the customary organic and inorganic bases such as, for example, tertiary amines such as pyridine, triethylamine, alcoholates such as Na, K methylate, -Ethylate, -butylate, but especially inorganic bases such as potassium or sodium hydroxide or the corresponding carbonates. They are used at least in stoichiometric, but preferably at least equimolar amounts or in an excess of 10-20% more. Larger excesses are possible, but offer no advantage and lead to an increased salt load.
  • the molar ratio of reactants II: III and IV: III can be varied within wide limits.
  • the compound III can be used in a double molar amount or more based on II.
  • Working with approximately equimolar amounts has the additional advantage that the reaction products can be processed without further purification.
  • the production process (a) is generally carried out by first heating the compound of the formula III with the basic compound in a suitable solvent to the reaction temperature, at least partially forming the salt of the compound III. Then the compound of formula II, optionally dissolved in the same solvent, is added and the mixture is stirred at elevated temperature until the reaction has ended.
  • the salt (mono salt) of compound III can also be completely prepared first and reacted with II. It is also possible to add the reactants in a different order.
  • the required reaction time depends on the reaction temperature, on the solvent and on the ratio II: III and decreases with increasing temperature and increasing excess of III. The reaction is usually complete after 30 minutes to 50 hours.
  • the production process (b) is carried out analogously to (a) by using a compound of the formula IV instead of a compound II, which in turn can be obtained from II and III.
  • the bases used here are used to prepare the salts of the compounds III, which in turn react with the bisethers of the formula IV to give the compounds (salts) of the formula I.
  • Both reactions are expediently carried out under protective gas.
  • protective gas are useful, for example, N 21 Ar, C0 2, preferably N 2.
  • the reaction mixture is acidified, the salt formed is filtered off and, if appropriate after washing with water, the solvent is distilled off.
  • excess III its removal is taken up in a water-immiscible solvent - for example in hot xylene - and washed several times with a little hot water, the organic phase is dried and the solvent is distilled off.
  • Other processing methods are described in the examples.
  • Processes (a) and (b) can advantageously also be applied to the reaction of 2-halogeno, in particular 2-chloro-benzothiazole, with hydroquinone.
  • the compounds of formula I are precursors for active biocides, e.g. for herbicides, in particular for those as proposed in German patent application P 26 40 730.7.
  • reaction with 2-halogenopropionic acid derivatives such as esters and amides in known selective herbicides from the compounds of formula I.
  • 2-halogenopropionic acid derivatives such as esters and amides in known selective herbicides from the compounds of formula I.
  • 2-halogenopropionic acid derivatives such as esters and amides in known selective herbicides from the compounds of formula I.
  • 4- (6'-chlorobenzthiazolyl-2'-oxy) phenol and 2-bromopropionic acid ethyl ester in the presence of potassium carbonate the 2- [4 '- (6 "-chlorobenzthiazolyl-2" -oxy) -phenoxy] -propionic acid- ethyl ester.
  • the invention therefore also relates to the use of compounds of the formula I for the preparation of biocides.
  • the salt content is filtered off and the filtrate is stirred into about 2 l of ice water.
  • the pH is adjusted to 2 with 10% sulfuric acid and the light precipitate is filtered off with suction, washed neutral with water and dried. After drying it is taken up in hot xylene and repeatedly with hot water to remove excess hydroquinone washed. Cooling the xylene phase and suctioning off the precipitate provides 106.8 g (81.7% of theory) of 4- (5'-chlorobenzoxazolyl-2'-oxy) phenol with an mp of 179.5 ° -181 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Heterocyclische Phenyläther der Formel I <IMAGE> in der R gleiche oder verschiedene Reste aus der Gruppe Halogen, CF3, NO2, CN, (C1-C4)Alkyl, (C1-C4)Alkoxy, (C1-C4)Alkylthio, A O, S oder N-(C1-C4)alkyl und n 0 bis 3 bedeuten mit der Einschränkung, dass für n = 0 und A = S die freie OH-Gruppe nicht in p-Stellung zur Ätherbindung steht, sowie ein Verfahren zu ihrer Herstellung.Heterocyclic phenyl ethers of the formula I <IMAGE> in which R is identical or different radicals from the group halogen, CF3, NO2, CN, (C1-C4) alkyl, (C1-C4) alkoxy, (C1-C4) alkylthio, AO, S or N- (C1-C4) alkyl and n 0 to 3 mean with the restriction that for n = 0 and A = S the free OH group is not in the p-position to the ether bond, and a process for their preparation.

Description

Aus J.Che.Soc. 1965, 954-73 ist die Verbindung 4-(Benzthiazolyl-2'-oxo)-phenol und ihre Herstellung aus 2-Chlor-benzthiazol und Hydrochinon in siedendem Aethanol in Gegenwart von metallischem Natrium bekannt. Über eine praktische Verwendung dieser Verbindung werden dort keine Angaben gemacht.From J.Che.Soc. 1965, 954-73 the compound 4- (benzthiazolyl-2'-oxo) -phenol and its preparation from 2-chloro-benzothiazole and hydroquinone in boiling ethanol in the presence of metallic sodium is known. No information is given on the practical use of this connection.

Gegenstand der vorliegenden Erfindung sind heterocyclische Phenyläther der allgemeinen Formel I

Figure imgb0001
in der

  • R gleiche oder verschiedene Reste aus der Gruppe Halogen, CF3, NO2, CN, (C1-C4)Alkyl, (C1-C4)Alkoxy, (C1-C4)Alkyl- thio,
  • A 0, S oder N-(C1-C4)alkyl und
  • n 0 bis 3 bedeuten

mit der Einschränkung, daß für n = 0 und A = S die freie OH-Gruppe nicht in p-Stellung zur Ätherbindung steht.The present invention relates to heterocyclic phenyl ethers of the general formula I.
Figure imgb0001
 in the
  • R are identical or different radicals from the group halogen, CF 3 , NO 2 , CN, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) alkylthio,
  • A 0, S or N- (C 1 -C 4 ) alkyl and
  • n is 0 to 3

with the restriction that for n = 0 and A = S the free OH group is not in the p-position to the ether bond.

Bevorzugt unter den Verbindungen der Formel I sind solche, in denen n = 0 - 2 ist, für n ≠ 0 insbesondere solche, in denen R Reste aus der Gruppe Halogen, CF3, N02, Methyl bedeutet, wobei als Halogen Fluor, Chlor und/oder Brom bevorzugt ist. Ist A = N-Alkyl, so ist N-Methyl bevorzugt.Preferred among the compounds of the formula I are those in which n = 0-2, for n ≠ 0 in particular those in which R is radicals from the group halogen, CF 3 , N0 2 , methyl, fluorine and chlorine being the halogen and / or bromine is preferred. If A = N-alkyl, N-methyl is preferred.

Gegenstand der Erfindung ist ferner ein Verfahren zur Herstellung der Verbindungen der Formell, das dadurch gekennzeichnet ist, daß man

  • a) Verbindungen der Formel II
    Figure imgb0002
    in der Hal für Halogen, vorzugsweise Cl oder Br steht, oder
  • b) Vmrbindungen der Formel IV
    Figure imgb0003
    mit Verbindungen der Formel III
    Figure imgb0004
    in Gegenwart basischer Verbindungen umsetzt.
The invention further relates to a process for the preparation of compounds of the formula, which is characterized in that
  • a) Compounds of formula II
    Figure imgb0002
     in which Hal represents halogen, preferably Cl or Br, or
  • b) compounds of the formula IV
    Figure imgb0003
     with compounds of formula III
    Figure imgb0004
     in the presence of basic compounds.

Die Verbindungen der Formel II lassen sich nach bekannten Verfahren z.B. aus den entsprechenden 2-Mercapto- bzw. 2-0xo-Verbindungen durch Halogenierung oder auch aus den 2-Amino-Verbindungen durch Diazotierung und anschließende Sandmeyer-Reaktion herstellen (s. z.B. C.A. 59, 396j; Am. Chem. J. 21 (1899), 111).The compounds of formula II can be prepared by known methods e.g. from the corresponding 2-mercapto or 2-0xo compounds by halogenation or else from the 2-amino compounds by diazotization and subsequent Sandmeyer reaction (see CA 59, 396j; Am. Chem. J. 21 (1899) , 111).

Die Verbindungen der Formel IV lassen sich nach dem Verfahren (a) durch Einsatz von 2 Mol oder mehr der Verbindung II auf 1 Mol der Verbindung III herstellen.The compounds of the formula IV can be prepared by the process (a) by using 2 mol or more of the compound II per 1 mol of the compound III.

Als Verbindungen der Formel II sind verwendbar die 2-Halogenverbindungen entsprechend substituierter Benzthiazole, Benzoxazole und 1-Alkyl-benzimidazole. Beispiele hierfür sind:

  • 2-Chlor-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2-Chlor-6-fluor-benzthiazol, -benzoxazol, 1-methyl-benzimidazol,
  • 2,6-Dichlor-benzthiazol, -benzoxazol, -1-butyl-benzimidazol,
  • 2,5-Dichlor-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2-Chlor-5-methyl-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2-Chlor-6-methyl-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2-Chlor-6-äthyl-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2-Chlor-6-nitro-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2,5-Dichlor-6-nitro-benzthiazol, -benzoxazol, -1-methylbenzimidazol,
  • 2-Chlor-5-methoxy-benzthiazol, -benzoxazol, -1-methylbenzimidazol,
  • 2-Chlor-6-methoxy-benzthiazol, -benzoxazol, -1-methylbenzimidazol,
  • 2-Chlor-6-methylthio-benzthiazol, -benzoxazol, -1-methylbenzimidazol,
  • 2,5,6-Trichlor-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2-Chlor-5-brom-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2-Chlor-6-brom-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2-Chlor-5,6-dibrom-benzthiazol, -benzoxazol, -1-methylbenzimidazol,
  • 2-Chlor-5-trifluormethyl-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2-Chlor-6-trifluormethyl-benzthiazol, -benzoxazol, -1-methyl-benzimidazol,
  • 2-Chlor-6-cyano-benzthiazol, -benzoxazol, -1-methyl-benzimidazol, sowie die entsprechenden 2-Bromderivate.
The compounds of the formula II which can be used are the 2-halogeno compounds correspondingly substituted benzothiazoles, benzoxazoles and 1-alkylbenzimidazoles. Examples for this are:
  • 2-chloro-benzothiazole, -benzoxazole, -1-methyl-benzimidazole,
  • 2-chloro-6-fluoro-benzothiazole, -benzoxazole, 1-methyl-benzimidazole,
  • 2,6-dichlorobenzthiazole, -benzoxazole, -1-butyl-benzimidazole,
  • 2,5-dichlorobenzthiazole, benzoxazole, -1-methylbenzimidazole,
  • 2-chloro-5-methyl-benzothiazole, -benzoxazole, -1-methyl-benzimidazole,
  • 2-chloro-6-methyl-benzothiazole, -benzoxazole, -1-methyl-benzimidazole,
  • 2-chloro-6-ethyl-benzothiazole, -benzoxazole, -1-methyl-benzimidazole,
  • 2-chloro-6-nitro-benzothiazole, -benzoxazole, -1-methyl-benzimidazole,
  • 2,5-dichloro-6-nitro-benzothiazole, -benzoxazole, -1-methylbenzimidazole,
  • 2-chloro-5-methoxy-benzothiazole, -benzoxazole, -1-methylbenzimidazole,
  • 2-chloro-6-methoxy-benzothiazole, -benzoxazole, -1-methylbenzimidazole,
  • 2-chloro-6-methylthio-benzothiazole, -benzoxazole, -1-methylbenzimidazole,
  • 2,5,6-trichlorobenzthiazole, benzoxazole, -1-methylbenzimidazole,
  • 2-chloro-5-bromo-benzothiazole, -benzoxazole, -1-methyl-benzimidazole,
  • 2-chloro-6-bromo-benzothiazole, -benzoxazole, -1-methyl-benzimidazole,
  • 2-chloro-5,6-dibromo-benzothiazole, -benzoxazole, -1-methylbenzimidazole,
  • 2-chloro-5-trifluoromethyl-benzothiazole, -benzoxazole, -1-methyl-benzimidazole,
  • 2-chloro-6-trifluoromethyl-benzothiazole, -benzoxazole, -1-methyl-benzimidazole,
  • 2-chloro-6-cyano-benzothiazole, -benzoxazole, -1-methyl-benzimidazole, and the corresponding 2-bromo derivatives.

Die Reaktionstemperaturen liegen zwischen 80° und 250°C, vorzugsweise 90° bis 150°C, gegebenenfalls beim Siedepunkt des verwendeten Lösungsmittels. Bei Temperaturen < 80° entsteht bei der Variante a) in zunehmendem Maße die Verbindung IV als an sich unerwünschtes Nebenprodukt. Dieses setzt sich jedoch oberhalb 80° mit weiterem III wieder zu I um (siehe Variante b)). Auch kann man die Reaktion bei Temperaturen oberhalb der Siedetemperatur im geschlossenen Gefäß unter Eigendruck durchführen; dies ist erforderlich, wenn das verwendete Lösungsmittel unterhalb 80° siedet. Man verwendet vorzugsweise polare aprotische Lösungsmittel, z.B. Säureamide wie Dimethylformamid, Dimmthylacetamid, Diäthylacetamid, N-Methylpyrrolidon und Hexamethylphosphorsäuretriamid, ferner Dimethylsulfoxid; Nitrile wie Acetonitril oder Propionitril, Ketone wie Aceton, Methyläthylketon oder Methylisobutylketon. Aber auch alipahtische Alkohole und aromatische Kohlenwasserstoffe wie Toluol oder Xylol sind verwendbar.The reaction temperatures are between 80 ° and 250 ° C, preferably 90 ° to 150 ° C, optionally at the boiling point of the solvent used. At temperatures <80 ° in variant a) compound IV is increasingly formed as an undesirable by-product per se. However, this converts back to I above 80 ° with further III (see variant b)). The reaction can also be carried out at temperatures above the boiling point in a closed vessel under autogenous pressure; this is necessary if the solvent used boils below 80 °. Polar aprotic solvents, e.g. Acid amides such as dimethylformamide, dimmthylacetamide, diethylacetamide, N-methylpyrrolidone and hexamethylphosphoric triamide, also dimethyl sulfoxide; Nitriles such as acetonitrile or propionitrile, ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone. However, aliphatic alcohols and aromatic hydrocarbons such as toluene or xylene can also be used.

Als basische Verbindungen eignen sich die üblichen organischen und anorganischen Basen wie z.B. tertiäre Amine wie Pyridin, Triäthylamin, Alkoholate wie Na-, K-Methylat, -Aethylat, -Butylat, insbesondere jedoch anorganische Basen wie Kalium- oder Natriumhydroxid oder die entsprechenden Carbonate. Sie werden mindestens in stöchiometrischen, vorzugsweise jedoch mindestens äquimolaren Mengen bzw. einem Überschuß von 10 - 20 % darüber eingesetzt. Größere Überschüsse sind möglich, bieten jedoch keinen Vorteil und führen zu einer erhöhten Salzbelastung.Suitable basic compounds are the customary organic and inorganic bases such as, for example, tertiary amines such as pyridine, triethylamine, alcoholates such as Na, K methylate, -Ethylate, -butylate, but especially inorganic bases such as potassium or sodium hydroxide or the corresponding carbonates. They are used at least in stoichiometric, but preferably at least equimolar amounts or in an excess of 10-20% more. Larger excesses are possible, but offer no advantage and lead to an increased salt load.

Das Molverhältnis der Reaktanten II : III bzw. IV : III läßt sich in weiten Grenzen variieren. So kann die Verbindung III in doppelt molarer Menge oder mehr bezogen auf II eingesetzt werden. Da jedoch die Entfernung von nicht umgesetztem III zusätzliche Operationen erfordert, die auch zu Ausbeuteverlusten führen können, arbeitet man bevorzugt mit etwa äquimolaren Mengen bzw. einem Überschuß von 5 bis 10 % der Verbindung III. Das Arbeiten mit etwa äquimolaren Mengen hat den zusätzlichen Vorteil, daß die Reaktionsprodukte ohne weitere Reinigung weiterverarbeitet werden können.The molar ratio of reactants II: III and IV: III can be varied within wide limits. Thus, the compound III can be used in a double molar amount or more based on II. However, since the removal of unreacted III requires additional operations which can also lead to losses in yield, it is preferred to work with approximately equimolar amounts or an excess of 5 to 10% of compound III. Working with approximately equimolar amounts has the additional advantage that the reaction products can be processed without further purification.

Das Herstellungsverfahren (a) wird im allgemeinen so durchgeführt, daß man die Verbindung der Formel III mit der basischen Verbindung in einem geeigneten Lösungsmittel zunächst auf Reaktionstemperatur erwärmt, wobei zumindest teilweise das Salz der Verbindung III gebildet wird. Dann gibt man die Verbindung der Formel II, gegebenenfalls gelöst in dem gleichen Lösungsmittel, zu und rührt so lange bei erhöhter Temperatur, bis die Umsetzung beendet ist. Man kann aber auch zunächst das Salz (Monosalz) der Verbindung III vollständig herstellen und dieses mit II umsetzen. Auch ist die Zugabe der Reaktionspartner in anderer Reihenfolge möglich. Die erforderliche Reaktionszeit hängt von der Reaktionstemperatur, vom Lösungsmittel und vom Verhältnis II : III ab und wird geringer mit wachsender Temperatur und wachsendem Überschuß an III. Gewöhnlich ist die Umsetzung nach 30 Minuten bis 50 Stunden beendet.The production process (a) is generally carried out by first heating the compound of the formula III with the basic compound in a suitable solvent to the reaction temperature, at least partially forming the salt of the compound III. Then the compound of formula II, optionally dissolved in the same solvent, is added and the mixture is stirred at elevated temperature until the reaction has ended. However, the salt (mono salt) of compound III can also be completely prepared first and reacted with II. It is also possible to add the reactants in a different order. The required reaction time depends on the reaction temperature, on the solvent and on the ratio II: III and decreases with increasing temperature and increasing excess of III. The reaction is usually complete after 30 minutes to 50 hours.

Das Herstellungsverfahren (b) wird analog (a) durchgeführt, indem statt einer Verbindung II eine Verbindung der Formel IV eingesetzt wird, die wiederum aus II und III erhalten werden kann. Die verwendeten Basen dienen hier zur Herstellung der Salze der Verbindungen III, die sich ihrerseits mit den Bisäthern der Formel IV zu den Verbindungen (Salzen) der Formel I umsetzen.The production process (b) is carried out analogously to (a) by using a compound of the formula IV instead of a compound II, which in turn can be obtained from II and III. The bases used here are used to prepare the salts of the compounds III, which in turn react with the bisethers of the formula IV to give the compounds (salts) of the formula I.

Beide Reaktionen werden zweckmäßig unter Schutzgas durchgeführt. Als solche sind verwendbar z.B. N21 Ar, C02, bevorzugt ist N2.Both reactions are expediently carried out under protective gas. As such, are useful, for example, N 21 Ar, C0 2, preferably N 2.

Nach beendeter Reaktion wird das Reaktionsgemisch angesäuert, von gebildetem Salz abfiltriert und - gegebenenfalls nach einer Wasserwäsche - das Lösungsmittel abdestilliert. Bei Arbeiten mit Überschuß an III wird zu seiner Entfernung in einem mit Wasser nicht mischbaren Lösungsmittel - beispielsweise in heißem Xylol - aufgenommen und mit wenig heißem Wasser mehrmals gewaschen, die organische Phase getrocknet und das Lösungsmittel abdestilliert. Andere Aufarbeitungsmethoden sind in den Beispielen beschrieben.When the reaction has ended, the reaction mixture is acidified, the salt formed is filtered off and, if appropriate after washing with water, the solvent is distilled off. When working with excess III, its removal is taken up in a water-immiscible solvent - for example in hot xylene - and washed several times with a little hot water, the organic phase is dried and the solvent is distilled off. Other processing methods are described in the examples.

Eine weitere Reinigung der so erhaltenen Verbindungen der Formel I durch Umkristallisieren, Destillieren oder Umfällen ist möglich, doch sind die Produkte vielfach für die Weiterverarbeitung rein genug.Further purification of the compounds of formula I thus obtained by recrystallization, distillation or reprecipitation is possible, but the products are often pure enough for further processing.

Die Verfahren (a) und (b) lassen sich vorteilhaft auch auf die Umsetzung von 2-Halogen-, insbesondere 2-Chlor-benzthiazol mit Hydrochinon anwenden.Processes (a) and (b) can advantageously also be applied to the reaction of 2-halogeno, in particular 2-chloro-benzothiazole, with hydroquinone.

Die Verbindungen der Formel I sind Vorprodukte für wirksame Biozide, z.B. für Herbizide, insbesondere für solche, wie sie in der deutschen Patentanmeldung P 26 40 730.7 vorgeschlagen werden.The compounds of formula I are precursors for active biocides, e.g. for herbicides, in particular for those as proposed in German patent application P 26 40 730.7.

Gemäß dieser Anmeldung erhält man durch Umsetzung mit 2-Halogenpropionsäurederivaten wie Estern und Amiden in an sich bekannter Weise aus den Verbindungen der Formel I wertvolle Selektivherbizide. Beispielsweise entsteht aus 4-(6'-Chlorbenzthiazolyl-2'-oxy)-phenol und 2-Brompropionsäureäthylester in Gegenwart von Kaliumcarbonat der 2-[4'-(6"-Chlorbenzthiazolyl-2"-oxy)-phenoxy]-propionsäure- äthylester.According to this application, reaction with 2-halogenopropionic acid derivatives such as esters and amides in known selective herbicides from the compounds of formula I. For example, from 4- (6'-chlorobenzthiazolyl-2'-oxy) phenol and 2-bromopropionic acid ethyl ester in the presence of potassium carbonate the 2- [4 '- (6 "-chlorobenzthiazolyl-2" -oxy) -phenoxy] -propionic acid- ethyl ester.

Gegenstand der Erfindung ist daher auch die Verwendung von Verbindungen der Formel I zur Herstellung von Bioziden.The invention therefore also relates to the use of compounds of the formula I for the preparation of biocides.

Die folgenden Beispiele sollen die Herstellung der erfindungsgemäßen Verbindungen erläutert, ohne sie zu beschränken.The following examples are intended to illustrate the preparation of the compounds according to the invention without restricting them.

HERSTELLUNGSBEISPIELEMANUFACTURING EXAMPLES Beispiel 1:Example 1: 4-(6'-Chlorbenzthiazolyl-2'-oxy)-phenol4- (6'-chlorobenzthiazolyl-2'-oxy) phenol

Figure imgb0005
Figure imgb0005

12,1 g (0,11 Mol) Hydrochinon und 16,6 g (0,12 Mol) Kaliumcarbonat werden in 120 ml Dimethylacetamid 1,5 Stunden unter Stickstoffschutzgas bei 95° - 100°C gerührt Anschließend werden innerhalb von 30 Minuten 20,4 g (0,1 Mol) 2,6-Dichlorbenzthiazol, gelöst in 50 ml Dimethylacetamid, zugetropft Nach der Zugabe wird die Temperatur bei 95° - 100°C gehalten und der Reaktionsablauf dünnschichtchromatographisch verfolgt. Nach 6 Stunden Reaktionszeit beträgt der Umsatz ca. 90 - 95 %. Zur Vervollständigung der Reaktion wird die Temperatur insgesamt 16 Stunden beibehalten. Man filtriert vom Salzanteil ab und rührt das Filtrat in ca. 500 ml Eiswasser ein. Mit 10 %iger Schwefelsäure wird anschließend auf pH 2 eingestellt, der helle Niederschlag abgesaugt, mit Wasser neutral gewaschen und getrocknet.12.1 g (0.11 mol) of hydroquinone and 16.6 g (0.12 mol) of potassium carbonate are stirred in 120 ml of dimethylacetamide for 1.5 hours under a protective nitrogen gas at 95 ° -100 ° C. Then, within 20 minutes, 4 g (0.1 mol) of 2,6-dichlorobenzothiazole, dissolved in 50 ml of dimethylacetamide, are added dropwise. After the addition, the temperature is kept at 95 ° -100 ° C. and the course of the reaction is followed by thin-layer chromatography. After a reaction time of 6 hours, the conversion is approximately 90-95%. The temperature is maintained for a total of 16 hours to complete the reaction. The salt content is filtered off and the filtrate is stirred into about 500 ml of ice water. Then with 10% sulfuric acid The pH is adjusted to 2, the light precipitate is filtered off with suction, washed neutral with water and dried.

Nach dem Trocknen erhält man 27 g (97,2 % d.Th.) 4-(6'-Chlorbenzthiazolyl-2'-oxy)-phenol vom Fp. 174°C. Umkristallisieren aus Xylol ergibt ein Produkt mit Fp. 177° - 178°C.After drying, 27 g (97.2% of theory) of 4- (6'-chlorobenzthiazolyl-2'-oxy) phenol, mp. 174 ° C. Recrystallization from xylene gives a product with mp. 177 ° - 178 ° C.

Zu ähnlichen Ergebnissen gelangt man, wenn man bei sonst gleichen Reaktionsbedingungen an Stelle von Dimethylacetamid N-Methylpyrrolidon, Methyl-isobutylketon, Acetonitril, Methyl-äthylketon, Aceton oder Äthanol (mit Natriumäthylat anstatt K2C03 als Base) verwendet.Similar results are obtained if, under otherwise identical reaction conditions, N-methylpyrrolidone, methyl isobutyl ketone, acetonitrile, methyl ethyl ketone, acetone or ethanol (with sodium ethylate instead of K 2 CO 3 as the base) is used instead of dimethylacetamide.

Beispiel 2:Example 2: 4-(5'-Chlorbenzoxazolyl-2'-oxy)-phenol4- (5'-chlorobenzoxazolyl-2'-oxy) phenol

Figure imgb0006
Figure imgb0006

110 g (1 Mol) Hydrochinon und 82,8 g (0,6 Mol) Kaliumcarbonat werden in 600 ml Dimethylformamid 1 1/2 Stunden unter Stickstoffschutzgas bei 120°C gerührt. Innerhalb von 1 1/2 Stunden werden danach 94 g (0,5 Mol) 2,5-Dichlorbenzoxazol in 150 ml Dimethylformamid, gelöst bei 95°C, zugetropft. Nach der Zugabe wird die Temperatur beibehalten, 1/2 Stunde nach Zugabe ist die Reaktion beendet. Dünnschichtchromatographisch ist nur noch 5'-Chlorbenzoxazolyloxy-phenol und Hydrochinon, jedoch kein 2,5-Dichlorbenzoxazol mehr festzustellen. Der Salzanteil wird abfiltriert und das Filtrat in ca. 2 1 Eiswasser eingerührt. Mit 10 %iger Schwefelsäure wird auf pH 2 eingestellt und der helle Niederschlag abgesaugt, mit Wasser neutral gewaschen und getrocknet. Nach der Trocknung wird in heioßem Xylol aufgenommen und zur Entfernung von überschüssigem Hydrochinon mehrfach mit heißem Wasser gewaschen. Abkühlen der Xylolphase und Absaugen des Niederschlags liefert 106,8 g (81,7 % d.Th.) 4-(5'-Chlor- benzoxazolyl-2'-oxy)-phenol mit einem Fp. 179,5°-181°C.110 g (1 mol) of hydroquinone and 82.8 g (0.6 mol) of potassium carbonate are stirred in 600 ml of dimethylformamide at 120 ° C. for 1 1/2 hours under a protective nitrogen gas. 94 g (0.5 mol) of 2,5-dichlorobenzoxazole in 150 ml of dimethylformamide, dissolved at 95 ° C., are then added dropwise within 1 1/2 hours. The temperature is maintained after the addition and the reaction is complete 1/2 hour after the addition. Only 5'-chlorobenzoxazolyloxyphenol and hydroquinone can be determined by thin layer chromatography, but no more 2,5-dichlorobenzoxazole. The salt content is filtered off and the filtrate is stirred into about 2 l of ice water. The pH is adjusted to 2 with 10% sulfuric acid and the light precipitate is filtered off with suction, washed neutral with water and dried. After drying it is taken up in hot xylene and repeatedly with hot water to remove excess hydroquinone washed. Cooling the xylene phase and suctioning off the precipitate provides 106.8 g (81.7% of theory) of 4- (5'-chlorobenzoxazolyl-2'-oxy) phenol with an mp of 179.5 ° -181 ° C.

Beispiel 3:Example 3: 4-(5'-Chlorbenzthiazolyl-2'-oxy)-phenol4- (5'-chlorobenzthiazolyl-2'-oxy) phenol

Figure imgb0007
Figure imgb0007

22 g (0,2 Mol) Hydrochinon und 16,6 g (0,12 Mol) Kaliumcarbonat werden in 120 ml Dimethylformamid 1 Stunde bei 120°C unter Stickstoffschutzgas gerührt. Innerhalb von 1 Stunde werden 20,4 g (0,1 Mol) 2,5-Dichlorbenzthiazol, gelöst in 50 ml Dimethylsulfoxid, zugetropft. Nach der Zugabe wird die Temperatur 2 1/2 Stunden beibehalten. Dünnschichtchromatographisch ist danach nur noch 5'-Chlorbenzthiazolyloxy-phenol und Hydrochinon, jedoch kein 2,5-Dichlorbenzthiazol mehr festzustellen. Der Salzanteil wird abfiltriert und das Filtrat in ca. 500 ml Eiswasser eingerührt. Mit 10 %iger Schwefelsäure wird auf pH 2 eingestellt und der helle Niederschlag abgesaugt, mit Wasser neutral gewaschen und getrocknet. Nach dem Trocknen wird in heißem Xylol aufgenommen und mehrfach mit heißem Wasser zur Entfernung von überschüssigem Hydrochinon gewaschen. Abkühlen der Xylolphase und Absaugen liefert 23 g (82,7 ï d.Th.) 4-(5'-Chlorbenzthiazolyl-2'-oxy)-phenol, Fp. 188°-190°C.22 g (0.2 mol) of hydroquinone and 16.6 g (0.12 mol) of potassium carbonate are stirred in 120 ml of dimethylformamide at 120 ° C. for 1 hour under a protective nitrogen gas. 20.4 g (0.1 mol) of 2,5-dichlorobenzothiazole, dissolved in 50 ml of dimethyl sulfoxide, are added dropwise within 1 hour. After the addition, the temperature is maintained for 2 1/2 hours. According to thin layer chromatography, only 5'-chlorobenzthiazolyloxyphenol and hydroquinone can then be determined, but no more 2,5-dichlorobenzothiazole. The salt content is filtered off and the filtrate is stirred into about 500 ml of ice water. The pH is adjusted to 2 with 10% sulfuric acid and the light precipitate is filtered off with suction, washed neutral with water and dried. After drying, it is taken up in hot xylene and washed several times with hot water to remove excess hydroquinone. Cooling the xylene phase and filtering off with suction gives 23 g (82.7% of theory) of 4- (5'-chlorobenzthiazolyl-2'-oxy) phenol, mp. 188 ° -190 ° C.

Beispiel 4:Example 4: 4-(6'-Chlorbenzthiazolyl-2'-oxy)-phenol4- (6'-chlorobenzthiazolyl-2'-oxy) phenol

Figure imgb0008
Figure imgb0008

12,1 g (0,11 Mol) Hydrochinon und 16,6 g (0,12 Mol) Kaliumcarbonat werden in 150 ml Dimethylformamid 1 1/2 Stunden unter Stickstoffschutzgas bei 100°C gerührt. Nach der Zugabe von 44,5 g (0,1 Mol) Hydrochinon-1,4-bis-6'-chlor-benzthiazolyl-2'-äther wird die Temperatur beibehalten. Die Spaltung des Bisäthers wird dünnschichtchromatographisch verfolgt. Nach 8 Stunden ist die Reaktion beendet. Nach Abkühlen wird das Reaktionsgemisch in 500 ml Eiswasser eingerührt. Mit 10 %iger Schwefelsäure wird auf pH 2 eingestellt und der helle Niederschlag abgesaugt, mit Wasser neutral gewaschen und getrocknet.12.1 g (0.11 mol) of hydroquinone and 16.6 g (0.12 mol) of potassium carbonate are stirred in 150 ml of dimethylformamide at 100 ° C. for 1 1/2 hours under a protective nitrogen gas. After the addition of 44.5 g (0.1 mol) of hydroquinone-1,4-bis-6'-chloro-benzothiazolyl-2'-ether, the temperature is maintained. The cleavage of the bisether is followed by thin layer chromatography. The reaction is complete after 8 hours. After cooling, the reaction mixture is stirred into 500 ml of ice water. The pH is adjusted to 2 with 10% sulfuric acid and the light precipitate is filtered off with suction, washed neutral with water and dried.

Man erhält 50,4 g (91 % d.Th.) 4-(6'-Chlorbenzthiazolyl-2'- oxy)-phenol mit Fp. 175°C. Umkristallisieren aus Xylol ergibt ein Produkt mit Fp. 177° - 178°C.50.4 g (91% of theory) of 4- (6'-chlorobenzthiazolyl-2'-oxy) phenol with mp 175 ° C. are obtained. Recrystallization from xylene gives a product with mp. 177 ° - 178 ° C.

Gemäß den Verfahrensbeispielen 1 bis 4 erhält man ferner:

Figure imgb0009
Figure imgb0010
 According to process examples 1 to 4, the following are also obtained:
Figure imgb0009
Figure imgb0010

Claims (3)

1. Heterocyclische Phenyläther der Formel I
Figure imgb0011
in der R gleiche oder verschiedene Reste aus der Gruppe Halogen, CF3, N022 CN, (C1-C4)Alkyl, (C1-C4)Alkoxy, (C1-C4)Alkylthio, A 0, S oder N-(C1-C4)alkyl und n 0 bis 3 bedeuten
mit der Einschränkung, daß für n = 0 und A = S die freie OH-Gruppe nicht in p-Stellung zur Aetherbindung steht.1. Heterocyclic phenyl ether of the formula I.
Figure imgb0011
 in the R are identical or different radicals from the group halogen, CF 3 , NO 22 CN, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) alkylthio, A 0, S or N- (C 1 -C 4 ) alkyl and n is 0 to 3
with the restriction that for n = 0 and A = S the free OH group is not in the p-position to the ether bond. 2. Verfahren zur Herstellung von Verbindungen der Formel I, dadurch gekennzeichnet, daß man a) Verbindungen der Formel II
Figure imgb0012
in der Hal für Halogen, vorzugsweise Cl oder Br steht, oder b) Verbindungen der Formel IV
Figure imgb0013
 mit Verbindungen der Formel III
Figure imgb0014
in Gegenwart basischer Verbindungen umsetzt. 2. A process for the preparation of compounds of formula I, characterized in that a) Compounds of formula II
Figure imgb0012
 in which Hal represents halogen, preferably Cl or Br, or b) compounds of the formula IV
Figure imgb0013
 with compounds of formula III
Figure imgb0014
 in the presence of basic compounds. 3. Verwendung von Verbindungen der Formel I zur Herstellung von Bioziden.3. Use of compounds of formula I for the production of biocides.
EP78100686A 1977-08-30 1978-08-17 Heterocyclic phenyl ethers and process for their preparation Expired EP0000924B1 (en)

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EP0123087A1 (en) * 1983-03-28 1984-10-31 CASSELLA Aktiengesellschaft Process for the preparation of heterocyclic phenyl ether

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DE2738963A1 (en) * 1977-08-30 1979-03-15 Hoechst Ag HETEROCYCLIC PHENYLAETHERS AND THE PROCESS FOR THEIR PRODUCTION
DE2914300A1 (en) * 1979-04-09 1980-11-13 Hoechst Ag HETEROCYCLIC PHENYL ETHERS AND HERBICIDES CONTAINING THEM
US4790868A (en) * 1986-03-17 1988-12-13 Ppg Industries, Inc. Herbicidally active substituted phenoxy or phenylthio benzoxazolone (or benzthiazolone) compounds
US4746351A (en) * 1986-05-12 1988-05-24 Ppg Industries, Inc. Herbicidally active substituted phenoxy benzoxazole (or benzothiazole)
US9617247B1 (en) * 2015-12-01 2017-04-11 Rotam Agrochem International Company Limited Form of halosulfuron-methyl, a process for its preparation and use of the same
US9629370B1 (en) * 2015-12-01 2017-04-25 Rotam Agrochem International Company Limited Synergistic herbicidal composition and use thereof

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US2541003A (en) * 1948-08-17 1951-02-06 American Cyanamid Co Process for reacting salts of phenols with halo-alkanoic acid compounds
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US3658835A (en) * 1966-08-22 1972-04-25 Eastman Kodak Co 1-phenyl-5-aryloxytetrazoles
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Publication number Priority date Publication date Assignee Title
WO1980002111A1 (en) * 1979-04-05 1980-10-16 Massachusetts Inst Technology Process and composition for treating disorders by administering lecithin
EP0123087A1 (en) * 1983-03-28 1984-10-31 CASSELLA Aktiengesellschaft Process for the preparation of heterocyclic phenyl ether

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