EP0000390B1 - Derivatives of 2-(2,2-dihalogenvinyl)-3,3-dimethyl-cyclopropane carboxylic acid and process for preparing them - Google Patents

Derivatives of 2-(2,2-dihalogenvinyl)-3,3-dimethyl-cyclopropane carboxylic acid and process for preparing them Download PDF

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EP0000390B1
EP0000390B1 EP78100347A EP78100347A EP0000390B1 EP 0000390 B1 EP0000390 B1 EP 0000390B1 EP 78100347 A EP78100347 A EP 78100347A EP 78100347 A EP78100347 A EP 78100347A EP 0000390 B1 EP0000390 B1 EP 0000390B1
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dimethyl
general formula
compounds
preparation
acid
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French (fr)
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EP0000390A1 (en
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Dieter Dr. Arlt
Manfred Dr Jautelat
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Bayer 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/12—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals containing only hydrogen and carbon atoms
    • 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
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2

Definitions

  • the present invention relates to new derivatives of 2- (2,2-dihalovinyl) -3,3-dimethylcyclopropane carboxylic acid, a process for their preparation and intermediates for their preparation.
  • the cyclopropanecarboxylic acid derivatives of the general formula (I) serve as intermediates for the preparation of the known cyclopropanecarboxylic acids on which they are based, which in turn are intermediates for the preparation of known insecticides.
  • the cyclopropanecarboxylic acids are obtained by hydrolyzing the compounds of the general formula (I) acidic or alkaline under suitable conditions (Houben-Weyl, Methods of Organic Chemistry, Volume VIII, p. 432 (1952) and Methodicum Chimicum, Volume 5, p. 572 (1975)).
  • cyclopropanecarboxylic acid derivatives of the general formula (1) represents a decisive improvement in the process for the preparation of cyclopropanecarboxylic acids, starting from the corresponding cyclopropanecarboxylic acid nitrile.
  • the step of cyclopropanecarboxylic acid nitrile which is difficult to saponify in low yield and in low yield is thereby avoided .
  • the use of the new substances according to the invention leads to a process which has the decisive advantage that the synthesis of the insecticidally active 2- (2,2-dihalovinyl) -3,3-dimethylcyclopropanecarboxylic acid esters such as 2- (2,2-dichlorovinyl) ) -3,3-dimethylcyclopropanecarboxylic acid-3-phenoxy-benzyl ester is easier and possible in better yields than from the corresponding nitriles.
  • Atoms such as ethylene or trimethylene are furthermore the rest of the formula (b), where R 5 is hydrogen, alkyl radicals having 1 to 4 carbon atoms and R 6 is hydrogen, alkyl radicals having 1 to 4 carbon atoms, aryl such as Phenyl, hydroxyl, alkoxy radicals with 1 to 4 carbon atoms or amino and R 5 and R 8 also represent parts of a ring such as tetramethylene, pentamethylene or ⁇ CH 2 ⁇ CH 2 ⁇ O ⁇ CH 2 ⁇ CH 2 -, furthermore for the rest of the formula (c), where R 7 is hydrogen, alkyl radicals having 1 to 4 carbon atoms, aryl such as phenyl, alkylamino having 1 to 4 carbon atoms, dialkylamino having 2 to 8 carbon atoms, hydroxyl, alkoxy radicals 1 to 4 carbon atoms and R 8 is hydrogen and alkyl radicals having 1 to 4 carbon atoms and R 9 is hydrogen, alkyl radicals having
  • the individual reaction stages can be combined in one process in such a way that the purification and isolation of the pure intermediates can be dispensed with.
  • Y has the meaning given above, optionally in the presence of a diluent with tetrahalomethane in the presence of a catalyst.
  • tetrahalomethanes are carbon tetrachloride, bromotrichloromethane or tetrabromomethane.
  • Preferred compounds of general formula (III) are those which lead to the preferred compounds of formula (11).
  • the addition of the tetrahalomethanes to the compounds of the formula (III) is carried out in the temperature range from 50 to 120 ° C., preferably 70 to 100 ° C., using catalysts such as dibenzoyl peroxide, azobisisobutyronitrile, copper or iron salts.
  • inert organic solvents such as hydrocarbons, ethers, nitriles, esters, ketones are suitable as diluents.
  • the process for the preparation of the 2 (2,2-dihalovinyl) -3,3-dimethylcyclopropanecarboxylic acid derivatives according to the invention is carried out by the action of at least two moles of base on the compounds of the formula II and gives the compounds of the invention with cyclization and ⁇ -elimination. Cyclization and ⁇ -elimination can be carried out either sequentially or simultaneously.
  • Bases include tertiary amines, for example pyridine, triethylamine, dimethylaniline, benzyldimethylamine, N-methylpiperidine, 1,8-diazabicyclo (5,4,0) -undecene, alkali metal alkolates, for example sodium methylate, sodium ethylate, potassium t-butoxide and also alkali metal hydroxides such as Sodium hydroxide or potassium hydroxide and alkali and alkaline earth carbonates.
  • tertiary amines for example pyridine, triethylamine, dimethylaniline, benzyldimethylamine, N-methylpiperidine, 1,8-diazabicyclo (5,4,0) -undecene
  • alkali metal alkolates for example sodium methylate, sodium ethylate, potassium t-butoxide and also alkali metal hydroxides such as Sodium hydroxide or potassium hydroxide and alkali and alkaline
  • Suitable diluents are alcohols such as methanol, ethanol or t-butanol, ethers such as dioxane or diethyl ether, and polar solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide or hexamethylphosphoric triamide.
  • reaction temperatures can be varied within a wide range. Generally one works between room temperature and 120 ° C, preferably between 40 ° and 80 ° C.
  • Y represents the oxazoline radical of the general formula IV in which
  • R 12 ⁇ R 15 independently of one another represent hydrogen, alkyl, aralkyl, aryl or together with the adjacent C atoms can form a carbocyclic ring are new.
  • R 12 ⁇ R 15 have the meaning given above, if appropriate at temperatures of 150-200 ° C in the presence of a catalyst and a diluent.
  • R 12 ⁇ R 15 de oxazoline radical of the general formula IV independently of one another are hydrogen, alkyl having 1-4 C atoms, aralkyl having 7-9 C atoms or phenyl, possibly by halogen, alkoxy or Phe noxy is substituted, where R 12 and R 13 or / and R 14 and R 15 can form an alkylene chain with 4-6 C atoms and R 12 with R 14 or R 15 can form an alkylene chain with 3-4 C atoms .
  • the present invention is illustrated by the following examples.
  • the formation of the residue Y i.e. the carboxylic acid derivative group, starting from 4-cyano-3,3-dimethyl-1-or 3,3-dimethyl-4-pentenoic acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

Die vorliegende Erfindung betrifft neue Derivate der 2-(2,2-Dihalogenvinyl)-3,3-dimethylcyclo- propancarbonsäure, ein Verfahren zu ihrer Herstellung und Zwischenprodukte zu ihrer Herstellung.The present invention relates to new derivatives of 2- (2,2-dihalovinyl) -3,3-dimethylcyclopropane carboxylic acid, a process for their preparation and intermediates for their preparation.

Die Herstellung von 2-(2,2-Dichlorvinyl)-3,3-dimethylcyclopropancarbonsäure durch Umsetzung von 1,1-Dichlor-4-methyl-1,3-pentadien mit Diazoessigester und nachfolgender Hydrolyse ist bereits bekannt (Farkas et al, Collect. Czechosl. Chem. Commun. 24, 2250 (1959)). Dieses Verfahren weist jedoch eine Reihe von Nachteilen auf. So ist die Handhabung großer Mengen Diazoessigester, der sich explosionsartig zersetzen kann, in der Technik mit großen Risiken behaftet. Auch aus physiologischer Sicht ist die Verwendung von Diazoverbindungen problematisch.The preparation of 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylic acid by reacting 1,1-dichloro-4-methyl-1,3-pentadiene with diazoacetic ester and subsequent hydrolysis is already known (Farkas et al, Collect Czechosl. Chem. Commun. 24, 2250 (1959)). However, this method has a number of disadvantages. The handling of large amounts of diazoacetic ester, which can explode explosively, is associated with great risks in technology. The use of diazo compounds is also problematic from a physiological point of view.

Es ist ferner vorgeschlagen worden, anstelle der Carbonsäure 1-Cyano-2-(2,2-dichlorvinyl)-3,3-dimethyl-cyclopropan als Zwischenstufe zur Herstellung der insektizid wirksamen Carbonsäureester zu verwenden. Dieses Nitril läßt sich durch Wasserabspaltung aus dem entsprechenden Aldoxim (vgl. Deutsche Offenlegungsschrift 2 621 832) oder durch basenkatalysierten Ringschluß aus 3-Brom-1-cyano-2,2-dimethyl-5,5,5-trichlor-pentan (vgl. deutsche Offenlegungsschrift 2 261 831) herstellen. Die Verfahren leiden jedoch unter dem Mangel, daß 1-Cyano-2-(2,2-dichlorvinyl)-3,3-dimethyl- cyclopropan selbst unter drastischen Bedingungen nur in geringen Ausbeuten zur entsprechenden Carbonsäure verseift werden kann.It has also been proposed to use 1-cyano-2- (2,2-dichlorovinyl) -3,3-dimethyl-cyclopropane instead of the carboxylic acid as an intermediate for the preparation of the insecticidally active carboxylic acid esters. This nitrile can be eliminated from the corresponding aldoxime (cf. German Offenlegungsschrift 2,621,832) or by base-catalyzed ring closure from 3-bromo-1-cyano-2,2-dimethyl-5,5,5-trichloropentane (cf. German Offenlegungsschrift 2 261 831). However, the processes suffer from the defect that 1-cyano-2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane can only be saponified to give the corresponding carboxylic acid in low yields even under drastic conditions.

Aus DE-OS 2 639 777 sind 2-(ßß-disubstituiertes Vinyl)-3,3-dimethylcyclopropancarbonsäure- amid sowie -N-alkylamide bekannt. Sie werden in einem mehrstufigen Verfahren aus den entsprechenden 2-Acetyl-3,3-dimethylcyclopropancarbonsäureamiden erhalten. Dieses Verfahren ist technisch aufwendig.From DE-OS 2 639 777 2- (β-disubstituted vinyl) -3,3-dimethylcyclopropanecarboxamide and -N-alkylamides are known. They are obtained in a multi-stage process from the corresponding 2-acetyl-3,3-dimethylcyclopropanecarboxamides. This process is technically complex.

Es werden nun die neuen Derivate der 2-(2,2-Dihalogenvinyl)-3,3-dimethylcyclopropancarbon- säure der allgemeinen Formel (I)

Figure imgb0001
in welcher

  • Hai unabhängig voneinander für Halogen steht und
  • Y für ein C-Atom steht, das ausschließlich sowohl einfach als auch doppelt an Sauerstoff oder Schwefel und/oder Stickstoff gebunden ist, wobei mindestens eine Bindung durch Stickstoff besetzt ist, und Y nicht für den Carbonamidrest, steht,
The new derivatives of 2- (2,2-dihalogenvinyl) -3,3-dimethylcyclopropanecarboxylic acid of the general formula (I)
Figure imgb0001
 in which
  • Shark independently represents halogen and
  • Y stands for a C atom which is exclusively bound both single and double to oxygen or sulfur and / or nitrogen, at least one bond being occupied by nitrogen, and Y does not represent the carbonamide radical,

gefunden.found.

Es wurde ferner gefunden, daß die neuen Derivate der 2-(2,2-Dihalogenvinyl)-3,3-dimethylcyclo- propancarbonsäure der allgemeinen Formel (I) hergestellt werden können, indem man eine Verbindung der allgemeinen Formel (11)

Figure imgb0002
in welcher

  • Hal und Y die oben angegebene Bedeutung haben,
  • in Gegenwart eines Verdünnungsmittels mit einer Base behandelt.
It has also been found that the new derivatives of 2- (2,2-dihalovinyl) -3,3-dimethylcyclopropane carboxylic acid of the general formula (I) can be prepared by using a compound of the general formula (11)
Figure imgb0002
 in which
  • Hal and Y have the meaning given above,
  • treated with a base in the presence of a diluent.

Die Cyclopropancarbonsäurederivate der allgemeinen Formel (I) dienen als Zwischenprodukte zur Herstellung der ihnen zugrundeliegenden bekannten Cyclopropancarbonsäuren, die ihrerseits Zwischenprodukte zur Herstellung bekannter Insektizide sind. Die Cyclopropancarbonsäuren werden erhalten, indem man die Verbindungen der allgemeinen Formel (I) sauer oder alkalisch unter geeigneten Bedingungen hydrolysiert (Houben-Weyl, Methoden der organischen Chemie, Band VIII, S. 432 (1952) und Methodicum Chimicum, Band 5, S. 572 (1975)).The cyclopropanecarboxylic acid derivatives of the general formula (I) serve as intermediates for the preparation of the known cyclopropanecarboxylic acids on which they are based, which in turn are intermediates for the preparation of known insecticides. The cyclopropanecarboxylic acids are obtained by hydrolyzing the compounds of the general formula (I) acidic or alkaline under suitable conditions (Houben-Weyl, Methods of Organic Chemistry, Volume VIII, p. 432 (1952) and Methodicum Chimicum, Volume 5, p. 572 (1975)).

Die Verwendung der Cyclopropancarbonsäurederivate der allgemeinen Formel (1) stellt eine entscheidende Verbesserung des Verfahrens zur Herstellung von Cyclopropancarbonsäuren, ausgehend vom entsprechenden Cyclopropancarbonsäurenitril, dar. Es wird dabei die Stufe des nur schwer und in geringer Ausbeute zur Cyclopropancarbonsäure oder zu deren Derivaten zu verseifenden Cyclopropancarbonsäurenitrils umgangen.The use of the cyclopropanecarboxylic acid derivatives of the general formula (1) represents a decisive improvement in the process for the preparation of cyclopropanecarboxylic acids, starting from the corresponding cyclopropanecarboxylic acid nitrile. The step of cyclopropanecarboxylic acid nitrile which is difficult to saponify in low yield and in low yield is thereby avoided .

Es ist als ausgesprochen überraschend zu bezeichnen, daß die Umwandlung der Cyangruppe in funktionelle Carbonsäurederivate auf der Stufe des 4-Cyano-3,3-dimethyl-1-butens, des Ausgangsproduktes zur Herstellung der Verbindungen der Formel (I), sehr viel leichter und besser möglich ist als auf der Stufe des 1-Cyano-2-(2,2-dichlorvinyl)-3,3-dimethylcyclopropans. Die Verwendung der erfindungsgemäßen neuen Stoffe führt zu einem Verfahren, das den entscheidenden Vorteil aufweist, daß die Synthese der insektizid wirksamen 2-(2,2-Dihalogenvinyl)-3,3-dimethylcyclopropancarbon- säureester wie beispielsweise 2-(2,2-Dichlorvinyl)-3,3-dimethylcyclopropancarbonsäure-3-phenoxy- benzylester einfacher und in besseren Ausbeuten möglich ist als aus den entsprechenden Nitrilen.It is extremely surprising that the conversion of the cyano group into functional carboxylic acid derivatives at the 4-cyano-3,3-dimethyl-1-butene stage, the starting product for the preparation of the compounds of the formula (I), is much easier and better possible than at the 1-cyano-2- stage (2,2-dichlorovinyl) -3,3-dimethylcyclopropane. The use of the new substances according to the invention leads to a process which has the decisive advantage that the synthesis of the insecticidally active 2- (2,2-dihalovinyl) -3,3-dimethylcyclopropanecarboxylic acid esters such as 2- (2,2-dichlorovinyl) ) -3,3-dimethylcyclopropanecarboxylic acid-3-phenoxy-benzyl ester is easier and possible in better yields than from the corresponding nitriles.

Die Ausgangsstoffe zur Herstellung der Cyclopropancarbonsäurederivate der Formel (I) sind neu, sie sind durch die Formel (II) allgemein definiert. In der Formel (II) steht Hal bevorzugt für Chlor oder Brom und Y bevorzugt für einen der folgenden Reste a bis d:

Figure imgb0003
wobei

  • R3, R4 unabhängig voneinander für Wasserstoff, Alkyl, Aryl oder Acyl stehen, oder gemeinsam mit den angrenzenden Atomen einen Heterocyclus bilden können, ferner für
    Figure imgb0004
    wobei
  • R5, R6 unabhängig voneinander für Wasserstoff, Aryl, Hydroxy, Alkoxy oder Amino stehen, oder gemeinsam mit dem angrenzenden N-Atom einen Heterocyclus bilden können, ferner für
    Figure imgb0005
    wobei
  • R7 für Wasserstoff, Alkyl, Aryl, Amino, Alkylamino, Dialkylamino, hydroxyl, Alkoxy steht und
  • R8, R9 unabhängig voneinander für Wasserstoff, Alkyl, Aryl, Arylamino, Dialkylamino oder Hydroxyl stehen oder gemeinsam zwei der Reste R7, R8 und R9 mit den angrenzenden Atomen einen Heterocyclus bilden können, ferner für
    Figure imgb0006
    wobei
  • R10 für Alkyl steht und
  • R11 für Wasserstoff, Alkyl, Aryl, Hydroxyl, Alkoxy oder Amino steht oder R10 und R" gemeinsam mit den angrenzenden Atomen einen Heterocyclus bilden können.
The starting materials for the preparation of the cyclopropanecarboxylic acid derivatives of the formula (I) are new, they are generally defined by the formula (II). In the formula (II), Hal preferably represents chlorine or bromine and Y preferably represents one of the following radicals a to d:
Figure imgb0003
 in which
  • R 3 , R 4 independently of one another represent hydrogen, alkyl, aryl or acyl, or together with the adjacent atoms can form a heterocycle, furthermore for
    Figure imgb0004
     in which
  • R 5 , R 6 independently of one another represent hydrogen, aryl, hydroxy, alkoxy or amino, or together with the adjacent N atom can form a heterocycle, furthermore for
    Figure imgb0005
     in which
  • R 7 represents hydrogen, alkyl, aryl, amino, alkylamino, dialkylamino, hydroxyl, alkoxy and
  • R 8 , R 9 independently of one another represent hydrogen, alkyl, aryl, arylamino, dialkylamino or hydroxyl or together two of the radicals R 7 , R 8 and R 9 can form a heterocycle with the adjacent atoms, furthermore for
    Figure imgb0006
     in which
  • R 10 represents alkyl and
  • R 11 represents hydrogen, alkyl, aryl, hydroxyl, alkoxy or amino or R 10 and R "together with the adjacent atoms can form a heterocycle.

Besonders bevorzugt sind Ausgangsverbindungen der allgemeinen Formel (II), in der Y für den Rest der Formel (a) steht, wobei R3 für Alkylreste mit 1 bis 4 C-Atomen, Aryl wie Phenyl, oder Acyl mit 1 bis 7 C-Atomen steht und R4 für Wasserstoff, Alkylreste mit 1 bis 4 C-Atomen, Aryl wie Phenyl oder Acylreste mit 1 bis 7 C-Atomen steht und R3 und R4 gemeinsam für einen Alkylenrest mit 2 bis 5 C-Atomen wie Ethylen oder Trimethylen stehen, ferner für den Rest der Formel (b) steht, wobei R5 für Wasserstoff, Alkylreste mit 1 bis 4 C-Atomen steht und R6 für Wasserstoff, Alkylreste mit 1 bis 4 C-Atomen, Aryl wie Phenyl, Hydroxyl, Alkoxyreste mit 1 bis 4 C-Atomen oder Amino steht und R5 und R8 auch für Teile eines Ringes wie Tetramethylen, Pentamethylen oder ―CH2―CH2―O―CH2―CH2- stehen, ferner für den Rest der Formel (c) steht, wobei R7 für Wasserstoff, Alkylreste mit 1 bis 4 C-Atomen, Aryl wie Phenyl, Alkylamino mit 1 bis 4 C-Atomen, Dialkylamino mit 2 bis 8 C-Atomen, Hydroxyl, Alkoxyreste mit 1 bis 4 C-Atomen steht und R8 für Wasserstoff und Alkylreste mit 1 bis 4 C-Atomen steht und R9 für Wasserstoff, Alkylreste mit 1 bis 4 C-Atomen, Aryl wie Phenyl, Amino, Alkylamino mit 1 bis 4 C-Atomen, Dialkylamino mit 2 bis 8 C-Atomen oder Hydroxyl steht und R7 und R8 gemeinsam für einen Alkylenrest mit 2 bis 5 C-Atomen wie Ethylen oder Trimethylen stehen und R8 und R9 auch für Teile eines Ringes wie Tetramethylen, Pentamethylen oder ―CH2―CH2―O―CH2―CH2― stehen, ferner für den Rest der Formel (d) steht, wobei R10 für Alkylreste mit 1 bis 4 C-Atomen steht, R11 für Wasserstoff, Alkylreste mit 1 bis 4 C-Atomen, Aryl wie Phenyl, Hydroxyl, Alkoxyresten mit 1 bis 4 C-Atomen oder Amino steht.Starting compounds of the general formula (II) in which Y represents the rest of the formula (a) are particularly preferred, where R 3 is alkyl radicals having 1 to 4 carbon atoms, aryl such as phenyl, or acyl having 1 to 7 carbon atoms R 4 represents hydrogen, alkyl radicals having 1 to 4 carbon atoms, aryl such as phenyl or acyl radicals having 1 to 7 carbon atoms and R 3 and R 4 together represent an alkylene radical having 2 to 5 carbon atoms. Atoms such as ethylene or trimethylene are furthermore the rest of the formula (b), where R 5 is hydrogen, alkyl radicals having 1 to 4 carbon atoms and R 6 is hydrogen, alkyl radicals having 1 to 4 carbon atoms, aryl such as Phenyl, hydroxyl, alkoxy radicals with 1 to 4 carbon atoms or amino and R 5 and R 8 also represent parts of a ring such as tetramethylene, pentamethylene or ―CH 2 ―CH 2 ―O ― CH 2 ―CH 2 -, furthermore for the rest of the formula (c), where R 7 is hydrogen, alkyl radicals having 1 to 4 carbon atoms, aryl such as phenyl, alkylamino having 1 to 4 carbon atoms, dialkylamino having 2 to 8 carbon atoms, hydroxyl, alkoxy radicals 1 to 4 carbon atoms and R 8 is hydrogen and alkyl radicals having 1 to 4 carbon atoms and R 9 is hydrogen, alkyl radicals having 1 to 4 carbon atoms, aryl such as phenyl, amino, alkylamino having 1 to 4 carbon atoms Atoms, dialkylamino with 2 to 8 carbon atoms or hydroxyl and R 7 and R 8 together represent an alkylene radical with 2 to 5 carbon atoms such as ethylene or trimethylene and R 8 and R 9 also represent parts of a ring such as tetramethylene, pentamethylene or ―CH 2 ―CH 2 ―O ― CH 2 ―CH 2 -, furthermore stands for the rest of the formula (d), where R 10 represents alkyl radicals having 1 to 4 carbon atoms R 11 represents hydrogen, alkyl radicals having 1 to 4 carbon atoms, aryl such as phenyl, hydroxyl, alkoxy radicals having 1 to 4 carbon atoms or amino.

Nach einer besonderen Ausführungsform dieser Erfindung lassen sich die einzelnen Reaktionsstufen in einem Verfahren so zusammenfassen, daß auf die Reinigung und Isolierung der reinen Zwischenprodukte verzichtet werden kann.According to a particular embodiment of this invention, the individual reaction stages can be combined in one process in such a way that the purification and isolation of the pure intermediates can be dispensed with.

Als Beispiele für Ausgangsverbindungen der allgemeinen Formel (II), die besonders vorteilhaft zur Herstellung der Cyclopropancarbonsäurederivate verwendet werden können, seien genannt:

  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexansäure-imid-ethylester
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexansäure-methylimidmethylester
  • 2-(2',2'-Dimethyl-3',5',5',5'-tetrachlorpentyl)oxazolin
  • 2-(2',2'-Dimethyl-3',5',5',5'-tetrabrompentyl)oxazolin
  • 2-(2',2'-Dimethyl-3',5',5',5'-tetrachlorpentyl-5,6-dihydro-4H-1,3-oxazin
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexanhydroximsäure-O-methylethylester
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexanthiocarbonsäureamid
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexanthiocarbonsäure-N-tert.-butylamid
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexanthiocarbonsäure-N-ethylamid
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexansäure-amidin
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexansäure-N-methyl-N'-phenylamidin
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexansäure-amidoxim
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexansäure-amidrazon
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexanthiocarbonsäure-N-methylhydrazonid-S-methylester
  • 3,3-Dimethyl-4,6,6,6-tetrachlorhexan-S-methyl-thiohydroxamsäure.
Examples of starting compounds of the general formula (II) which can be used particularly advantageously for the preparation of the cyclopropanecarboxylic acid derivatives are:
  • 3,3-Dimethyl-4,6,6,6-tetrachlorohexanoic acid imide ethyl ester
  • 3,3-Dimethyl-4,6,6,6-tetrachlorohexanoic acid methylimidemethyl ester
  • 2- (2 ', 2'-dimethyl-3', 5 ', 5', 5'-tetrachloropentyl) oxazoline
  • 2- (2 ', 2'-Dimethyl-3', 5 ', 5', 5'-tetrabrompentyl) oxazoline
  • 2- (2 ', 2'-Dimethyl-3', 5 ', 5', 5'-tetrachloropentyl-5,6-dihydro-4H-1,3-oxazine
  • 3,3-Dimethyl-4,6,6,6-tetrachlorohexane hydroximic acid-O-methylethyl ester
  • 3,3-dimethyl-4,6,6,6-tetrachlorohexanthiocarboxamide
  • 3,3-Dimethyl-4,6,6,6-tetrachlorohexanthiocarboxylic acid N-tert-butylamide
  • 3,3-Dimethyl-4,6,6,6-tetrachlorohexanthiocarboxylic acid N-ethylamide
  • 3,3-Dimethyl-4,6,6,6-tetrachlorohexanoic acid amidine
  • 3,3-Dimethyl-4,6,6,6-tetrachlorohexanoic acid-N-methyl-N'-phenylamidine
  • 3,3-Dimethyl-4,6,6,6-tetrachlorohexanoic acid amidoxime
  • 3,3-Dimethyl-4,6,6,6-tetrachlorohexanoic acid amidrazone
  • 3,3-Dimethyl-4,6,6,6-tetrachlorohexanthiocarboxylic acid N-methylhydrazonide-S-methyl ester
  • 3,3-dimethyl-4,6,6,6-tetrachlorohexane-S-methyl-thiohydroxamic acid.

Wie bereits erwähnt, sind die Ausgangsverbindungen der allgemeinen Formel (11) neu. Sie können jedoch erhalten werden, indem man Verbindungen der Formel (III)

Figure imgb0007
in welcherAs already mentioned, the starting compounds of the general formula (11) are new. However, they can be obtained by using compounds of the formula (III)
Figure imgb0007
 in which

Y die oben angegebene Bedeutung hat, gegebenenfalls in Anwesenheit eines Verdünnungsmittels mit Tetrahalogenmethan in Gegenwart eines Katalysators umsetzt.Y has the meaning given above, optionally in the presence of a diluent with tetrahalomethane in the presence of a catalyst.

Dabei kann der Reaktionsablauf durch folgendes Formel-schema wiedergegeben werden:

Figure imgb0008
The course of the reaction can be represented by the following formula:
Figure imgb0008

Besonders bevorzugte Tetrahalogenmethane sind Tetrachlorkohlenstoff, Bromtrichlormethan oder Tetrabrommethan.Particularly preferred tetrahalomethanes are carbon tetrachloride, bromotrichloromethane or tetrabromomethane.

Bevorzugte Verbindung der allgemeinen Formel (III) sind diejenigen, die zu den bevorzugten Verbindungen der Formel (11) führen.Preferred compounds of general formula (III) are those which lead to the preferred compounds of formula (11).

Die Addition der Tetrahalogenmethane an die Verbindungen der Formel (III) wird in Temperaturbereich von 50 bis 120°C, vorzugsweise 70 bis 100°C, unter Verwendung von Katalysatoren wie Dibenzoylperoxid, Azobisisobuttersäurenitril, Kupfer- oder Eisensalzen durchgeführt.The addition of the tetrahalomethanes to the compounds of the formula (III) is carried out in the temperature range from 50 to 120 ° C., preferably 70 to 100 ° C., using catalysts such as dibenzoyl peroxide, azobisisobutyronitrile, copper or iron salts.

Als Verdünnungsmittel eignen sich alle inerten organischen Lösungsmittel wie Kohlenwasserstoffe, Ether, Nitrile, Ester, Ketone, Bevorzugt werden jedoch die auch als Ausgangsstoffe verwendbaren Tetrahalogenmethane verwendet.All inert organic solvents such as hydrocarbons, ethers, nitriles, esters, ketones are suitable as diluents. However, preference is given to using the tetrahalomethanes which can also be used as starting materials.

Die Ausgangsverbindungen der allgemeinen Formel III sind zum Teil neu. Sie können erhalten werden, indem man

  • a) die Nitrilgruppe von 4-Cyano-3,3-dimethyl-1-buten in an sich bekannter Weise in den Rest Y der Verbindungen der allgemeinen Formel 111 überführt (vgl. Houben Weyl, Methoden der Organischen Chemie Band VIII und Methodicum Chimicum, Band 6, 1974, Thieme Verlag Stuttgart) oder
  • b) den Carboxylrest der 3,3-Dimethyl-4-pentensäure in an sich bekannter Weise in den Rest Y der Verbindungen der allgemeinen Formel III überführt (vgl. Houben Weyl, Methoden der Organischen Chemie Band VIII und Methodicum Chimicum, Band 6, 1974, Thieme Verlag Stuttgart).
Some of the starting compounds of the general formula III are new. You can get one by one
  • a) the nitrile group of 4-cyano-3,3-dimethyl-1-butene is converted into the radical Y of the compounds of the general formula 111 in a manner known per se (cf. Houben Weyl, Methods of Organic Chemistry Volume VIII and Methodicum Chimicum, Volume 6, 1974, Thieme Verlag Stuttgart) or
  • b) the carboxyl radical of 3,3-dimethyl-4-pentenoic acid is converted into the radical Y of the compounds of the general formula III in a manner known per se (cf. Houben Weyl, Methods of Organic Chemistry Volume VIII and Methodicum Chimicum, Volume 6, 1974 , Thieme Verlag Stuttgart).

Das Verfahren zur Herstellung der erfinungsgemäßen 2(2,2-Dihalogenvinyl)-3,3-dimethylcyclo- propancarbonsäurederivate wird durch Einwirkung von wenigstens zwei Mol Base auf die Verbindungen der Formel II durchgeführt und ergibt unter Cyclisierung und ß-Eliminierung die erfindungsgemäßen Verbindungen. Dabei können Cyclisierung und ß-Eliminierung sowohl nacheinander als auch gleichzeitig erfolgen.The process for the preparation of the 2 (2,2-dihalovinyl) -3,3-dimethylcyclopropanecarboxylic acid derivatives according to the invention is carried out by the action of at least two moles of base on the compounds of the formula II and gives the compounds of the invention with cyclization and β-elimination. Cyclization and β-elimination can be carried out either sequentially or simultaneously.

Als Basen kommen tertiäre Amine, beispielsweise Pyridin, Triäthylamin, Dimethylanilin, Benzyldimethylamin, N-Methylpiperidin, 1,8-Diazabicyclo(5,4,0)-undecen, Alkalimetallalkolate, beispielsweise Natriummethylat, Natriumäthylat, Kalium-t-butylat und ebenso Alkalihydroxide wie Natriumhydroxid oder Kaliumhydroxid sowie Alkali- und Erdalkalicarbonate.Bases include tertiary amines, for example pyridine, triethylamine, dimethylaniline, benzyldimethylamine, N-methylpiperidine, 1,8-diazabicyclo (5,4,0) -undecene, alkali metal alkolates, for example sodium methylate, sodium ethylate, potassium t-butoxide and also alkali metal hydroxides such as Sodium hydroxide or potassium hydroxide and alkali and alkaline earth carbonates.

Als Verdünnungsmittel eignen sich Alkohole wie Methanol, Äthanol oder t-Butanol, Äther wie Dioxan oder Diäthyläther, und polare Lösungsmittel wie Acetonitril, Dimethylformamid, Dimethylsulfoxid oder Hexamethylphosphorsäuretriamid.Suitable diluents are alcohols such as methanol, ethanol or t-butanol, ethers such as dioxane or diethyl ether, and polar solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide or hexamethylphosphoric triamide.

Die Reaktionstemperaturen können in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man zwischen Raumtemperatur und 120°C, bevorzugt zwischen 40° und 80°C.The reaction temperatures can be varied within a wide range. Generally one works between room temperature and 120 ° C, preferably between 40 ° and 80 ° C.

Verbindungen der allgemeinen Formel III

Figure imgb0009
in welcherCompounds of the general formula III
Figure imgb0009
 in which

Y für den Oxazolinrest der allgemeinen Formel IV steht

Figure imgb0010
in welcherY represents the oxazoline radical of the general formula IV
Figure imgb0010
 in which

R12―R15 unabhängig voneinander für Wasserstoff, Alkyl, Aralkyl, Aryl stehen oder gemeinsam mit den angrenzenden C-Atomen einen carbocylischen Ring bilden können sind neu.R 12 ―R 15 independently of one another represent hydrogen, alkyl, aralkyl, aryl or together with the adjacent C atoms can form a carbocyclic ring are new.

Man erhält sie, indem man 4-Cyano-3,3-dimethyl-1-buten der Formel V

Figure imgb0011
mit 2-Amino-alkanolen der allgemeinen Formel VI
Figure imgb0012
in welcherThey are obtained by using 4-cyano-3,3-dimethyl-1-butene of the formula V
Figure imgb0011
 with 2-amino-alkanols of the general formula VI
Figure imgb0012
 in which

R12―R15 die oben angegebene Bedeutung haben, bei Temperaturen von 150-200°C gegebenenfalls in Gegenwart eines Katalysators sowie eines Verdünnungsmittels umsetzt.R 12 ―R 15 have the meaning given above, if appropriate at temperatures of 150-200 ° C in the presence of a catalyst and a diluent.

Bevorzugt sind solche der neuen Verbindungen der allgemeinen Formel III in denen die Reste R12―R15 de Oxazolinrestes der allgemeinen Formel IV unabhängig voneinander für Wasserstoff, Alkyl mit 1-4 C-Atomen, Aralkyl mit 7-9 C-Atomen oder Phenyl, das ggf. durch Halogen, Alkoxy oder Phenoxy substituiert ist stehen, wobei R12 und R13 oder/sowie R14 und R15 eine Alkylenkette mit 4-6 C-Atomen bilden können und R12 mit R14 oder R15 eine Alkylenkette mit 3-4 C-Atomen bilden kann.Preferred are those of the new compounds of the general formula III in which the radicals R 12 ―R 15 de oxazoline radical of the general formula IV independently of one another are hydrogen, alkyl having 1-4 C atoms, aralkyl having 7-9 C atoms or phenyl, possibly by halogen, alkoxy or Phe noxy is substituted, where R 12 and R 13 or / and R 14 and R 15 can form an alkylene chain with 4-6 C atoms and R 12 with R 14 or R 15 can form an alkylene chain with 3-4 C atoms .

Als Beispiele seien im einzelnen genannt:

  • 2-(2,2-Dimethyl-3-buten-1-yl)-2-oxazolin,
  • 2-(2,2-Dimethyl-3-buten-1-yl)-4,4-dimethyl-2-oxazolin
  • 2-(2,2-Dimethyl-3-buten-1 -yl)-5,5-dimethyl-2-oxazolin
  • 2-(2,2-Dimethyl-3-buten-1 -yl)-4,4,5,5-tetramethyl-2-oxazolin
  • 2-(2,2-Dimethyl-3-buten-1 -yl)-5-benzyl-2-oxazolin
  • 2-(2,2-Dimethyl-3-buten-1-yl)-4,4-tetramethylen-2-oxazolin
  • 2-(2,2-Dimethyl-3-buten-1 -yl)-4,5-tetramethylen-2-oxazolin
  • 2-(2,2-Dimethyl-3-buten-1 -yl)-4-phenyl-2-oxazolin
  • 2-(2,2-Dimethyl-3-buten-1-yl)-5-phenyl-2-oxazolin
  • 2-(2,2-Dimethyl-3-buten-1-yl)-5-(m-phenoxyphenyl)-2-oxazolin
The following are examples:
  • 2- (2,2-dimethyl-3-buten-1-yl) -2-oxazoline,
  • 2- (2,2-dimethyl-3-buten-1-yl) -4,4-dimethyl-2-oxazoline
  • 2- (2,2-dimethyl-3-buten-1-yl) -5,5-dimethyl-2-oxazoline
  • 2- (2,2-dimethyl-3-buten-1-yl) -4,4,5,5-tetramethyl-2-oxazoline
  • 2- (2,2-dimethyl-3-buten-1-yl) -5-benzyl-2-oxazoline
  • 2- (2,2-dimethyl-3-buten-1-yl) -4,4-tetramethylene-2-oxazoline
  • 2- (2,2-dimethyl-3-buten-1-yl) -4,5-tetramethylene-2-oxazoline
  • 2- (2,2-dimethyl-3-buten-1-yl) -4-phenyl-2-oxazoline
  • 2- (2,2-dimethyl-3-buten-1-yl) -5-phenyl-2-oxazoline
  • 2- (2,2-Dimethyl-3-buten-1-yl) -5- (m-phenoxyphenyl) -2-oxazoline

Das Verfahren zur Herstellung der neuen Verbindungen der Formel III wird analog dem in Angew. Chem. Band 88, Seite 321 (1976) beschriebenen Verfahren durchgeführt. Als Katalysatoren werden dabei bevorzugt verwendet:

  • Cadmiumacetate, Zinkacetat, Manganacetat, Zinkchlorid, Kupfer-(II)-chlorid, Cobaltacetat oder Lithiumchlorid.
The process for the preparation of the new compounds of formula III is analogous to that in Angew. Chem. Volume 88, page 321 (1976). The following are preferably used as catalysts:
  • Cadmium acetate, zinc acetate, manganese acetate, zinc chloride, copper (II) chloride, cobalt acetate or lithium chloride.

Die vorliegende Erfindung wird durch die folgenden Beispiele erläutert. Dabei wird unter .1 eines jeden Beispiels die Bildung des Restes Y, d.h. der Carbonsäurederivatgruppe, ausgehend von 4-Cyano-3,3-dimethyl-1-oder 3,3-Dimethyl-4-pentensäure, beschrieben.The present invention is illustrated by the following examples. The formation of the residue Y, i.e. the carboxylic acid derivative group, starting from 4-cyano-3,3-dimethyl-1-or 3,3-dimethyl-4-pentenoic acid.

Unter .2 eines jeden Beispiels wird die Addition des Tetrahalogenmethans an die Doppelbindung des Ausgangsstoffes, der gemäß den unter .1 beschriebenen Verfahren erhalten wird, beschrieben.Under .2 of each example, the addition of the tetrahalomethane to the double bond of the starting material, which is obtained according to the processes described under .1, is described.

Unter .3 eines jeden Beispiels wird schließlich die Ringbindung und β-Eliminierung aus den gemäß .2 erhaltenen Produkten beschrieben.Finally, under .3 of each example the ring binding and β-elimination from the products obtained according to .2 are described.

Beispiel 1example 1 Herstellung von 2-(2'-(2,2-Dichlorvinyl)-3',3'-dimethylcyclopropyl)-oxazolinPreparation of 2- (2 '- (2,2-dichlorovinyl) -3', 3'-dimethylcyclopropyl) oxazoline

  • 1.1 10,9 g (0,1 Mol) 4-Cyano-3,3-dimethyl-1-buten werden mit 6,7 g (0,11 Mol) Aminoethanol unter Katalyse von Cadmiumacetat bis zum Ende der NH3-Entwicklung auf 150 bis 160°C erhitzt. Nach dem Erkalten wird das Reaktionsgemisch in Tetrachlorkohlenstoff aufgenommen.1.1 10.9 g (0.1 mol) of 4-cyano-3,3-dimethyl-1-butene are mixed with 6.7 g (0.11 mol) of aminoethanol with catalysis of cadmium acetate until the end of the NH 3 evolution Heated from 150 to 160 ° C. After cooling, the reaction mixture is taken up in carbon tetrachloride.
  • 1.2 Diese Lösung des 2-(2',2'-Dimethyl-3'-butenyl)-oxazolins in CC14 wird unter Zusatz von 0,5 g Dibenzoylperoxid 15 Stunden unter Rückfluß erhitzt. Das Lösungsmittel wird im Vakuum abgezogen und der Rückstand in 100 ml DMSO gelöst.1.2 This solution of 2- (2 ', 2'-dimethyl-3'-butenyl) oxazoline in CC1 4 is heated under reflux for 15 hours with the addition of 0.5 g of dibenzoyl peroxide. The solvent is removed in vacuo and the residue is dissolved in 100 ml of DMSO.
  • 1.3 Nach Zusatz von 24 g (0,21 Mol) Kalium-t-butylat erhitzt man 1 Stunde auf 70°C. Die Lösung wird mit Methylenchlorid verdünnt und mit Wasser mehrfach ausgeschüttelt. Nach Trocknen und Abziehen des Lösungsmittels im Vakuum erhält man 2-(2',2'-Dichlorvinyl)-3',3'-dimethyl- cyclopropyl)-oxazolin vom Kp1mm 86 bis 88°C.1.3 After adding 24 g (0.21 mol) of potassium t-butoxide, the mixture is heated at 70 ° C. for 1 hour. The solution is diluted with methylene chloride and shaken out several times with water. After drying and evaporation of the solvent in vacuo, 2- (2 ', 2'-dichlorovinyl) -3', 3'-dimethyl-cyclopropyl) -oxazoline, bp 1mm 86 to 88 ° C.
Beispiel 2Example 2 Herstellung von 2-(2,2-Dimethylvinyl)-3,3-dimethylcyclopropanthiocarbonsäure-N-t-butylamidPreparation of 2- (2,2-dimethylvinyl) -3,3-dimethylcyclopropanthiocarboxylic acid-N-t-butylamide

  • 2.1 9,15 g (10 mmoi) 3,3-Dimethyl-4-pentensäure-N-tert.-butylamid vom Fp. 73 bis 75°C (s. Beispiel 3a) werden mit 5 g Phosphorpentasulfid in 100 ml Pyridin 1 Stunde unter Rückfluß erhitzt. Die Lösung wird filtriert und Pyridin im Vakuum abdestilliert. Der Rückstand wird in Tetrachlorkohlenstoff aufgenommen.2.1 9.15 g (10 mmoi) of 3,3-dimethyl-4-pentenoic acid-N-tert-butylamide of mp 73 to 75 ° C. (see Example 3a) are mixed with 5 g of phosphorus pentasulfide in 100 ml of pyridine for 1 hour heated under reflux. The solution is filtered and pyridine is distilled off in vacuo. The residue is taken up in carbon tetrachloride.
  • 2.2 Diese Lösung wird bei sukzessiver Zugabe von 0,5 g Dibenzoylperoxid 12 Stunden unter Rückfluß erhitzt. Tetrachlorkohlenstoff wird im Vakuum abgezogen und der Rückstand in 100 ml tert.-Butanol gelöst.2.2 This solution is heated under reflux for 12 hours with the successive addition of 0.5 g of dibenzoyl peroxide. Carbon tetrachloride is removed in vacuo and the residue is dissolved in 100 ml of tert-butanol.
  • 2.3 Unter Zusatz von 17 g (0,15 Mol) Kalium-t-butylat erhitzt man die Lösung 2 Stunden unter Rückfluß. Nach dem Erkalten verdünnt man das Reaktionsgemisch mit Methylenchlorid und schüttelt mit Wasser gut aus. Die organische Phase wird getrocknet und im Vakuum abgezogen. Zurück bleibt 2-(2,2-Dimethylvinyl)-3,3-dimethyl-cyclopropan-thiocarbonsäure-N-t-butylamid.2.3 With the addition of 17 g (0.15 mol) of potassium t-butoxide, the solution is heated under reflux for 2 hours. After cooling, the reaction mixture is diluted with methylene chloride and shaken well with water. The organic phase is dried and removed in vacuo. This leaves 2- (2,2-dimethylvinyl) -3,3-dimethyl-cyclopropane-thiocarboxylic acid-N-t-butylamide.
Beispiel 3Example 3 Herstellung von 2-(2,2-Dichlorvinyl)-3,3-dimethylcyclopropancarbonsäure-amidoximPreparation of 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylic acid amidoxime

  • 3.1 4 g (0,12 Mol) Hydroxylamin in 100 ml n-Butanol werden mit 10,9 g (0,1 Mol) 4-Cyano-3,3-dimethyl-1-buten 48 Stunden bei 40°C gerührt. Dann wird n-Butanol im Vakuum abdestilliert und der Rückstand in Tetrachlorkohlenstoff gelöst.3.1 4 g (0.12 mol) of hydroxylamine in 100 ml of n-butanol are stirred with 10.9 g (0.1 mol) of 4-cyano-3,3-dimethyl-1-butene at 40 ° C. for 48 hours. Then n-butanol is distilled off in vacuo and the residue is dissolved in carbon tetrachloride.
  • 3.2 Diese Lösung wird unter periodischem Zusatz von insgesamt 0,5 g Dibenzoylperoxid 12 Stunden unter Rückfluß erhitzt. Dann wird das Lösungsmittel abgezogen und der Rückstand in Ethanol aufgenommen.3.2 This solution is refluxed for 12 hours with the periodic addition of a total of 0.5 g of dibenzoyl peroxide. The solvent is then stripped off and the residue is taken up in ethanol.
  • 3.3 Die ethanolische Lösung wird nach Zusatz von 0,3 Mol Natriumethylat 3 Stunden unter Rückfluß erhitzt. Dann wird die Lösung im Vakuum eingeengt, mit Ether verdünnt und mit Wasser gut ausgeschüttelt. Nach dem Trocknen und Abdampfen des Ethers erhält man 2-(2,2-Dichlorvinyl)-3,3-dimethylcyclopropancarbonsäure-amidoxim.3.3 After the addition of 0.3 mol of sodium ethylate, the ethanolic solution is heated under reflux for 3 hours. Then the solution is concentrated in vacuo, diluted with ether and well with water shaken out. After drying and evaporating the ether, 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylic acid amidoxime is obtained.
Beispiel 4Example 4 Herstellung von 2-(2,2-Dichlorvinyl)-3,3-dimethyl-cyclopropancarbonhydroxamsäurePreparation of 2- (2,2-dichlorovinyl) -3,3-dimethyl-cyclopropanecarbonhydroxamic acid

  • 4.1 12,8 g (0,1 Mol) 3,3-Dimethyl-4-pentensäure (J.Org. Chem. 27, 3602 (1962)) werden durch Kochen mit 50 ml Ethanol unter Zusatz einer Spur p-Toluolsulfonsäure in 8 Stunden azeotrop verestert. Dann wird eine Lösung von 3,3 g Hydroxylamin in 20 ml Ethanol sowie 0,01 Mol Natriumethylat zugegeben und 24 Stunden bei RT gerührt. Die Lösung wird mit verd. Salzsäure neutralisiert und im Vakuum eingeengt. Mit Tetrachlorkohlenstoff extrahiert man den Rückstand.4.1 12.8 g (0.1 mol) of 3,3-dimethyl-4-pentenoic acid (J.Org. Chem. 27, 3602 (1962)) are boiled in 8 with 50 ml of ethanol with the addition of a trace of p-toluenesulfonic acid Hours esterified azeotropically. A solution of 3.3 g of hydroxylamine in 20 ml of ethanol and 0.01 mol of sodium ethylate is then added and the mixture is stirred at RT for 24 hours. The solution is neutralized with dilute hydrochloric acid and concentrated in vacuo. The residue is extracted with carbon tetrachloride.
  • 4.2 Diese Lösung wird bei sukzessiver Zugabe von 0,5 g Benzoylperoxid 15 Stunden am Rückflußerhitzt. Dann wird das Lösungsmittel abgezogen und der Rückstand in Ethanol gelöst.4.2 This solution is refluxed for 15 hours with the successive addition of 0.5 g of benzoyl peroxide. The solvent is then stripped off and the residue is dissolved in ethanol.
  • 4.3 Man gibt 0,3 Mol Natriumethylat zu dieser Lösung und erhitzt 4 Stunden unter Rückfluß. Dann engt man im Vakuum ein, stellt mit verdünnter Salzsäure sauer und extrahiert mit Ether. Die Etherlösung wird nach Waschen mit Wasser getrocknet und einrotiert. Zurück bleibt 2-(2,2-Dichlorvinyl)-3,3-dimethylcyclopropanhydroxamsäure.4.3 0.3 mol of sodium ethylate is added to this solution and the mixture is heated under reflux for 4 hours. The mixture is then concentrated in vacuo, acidified with dilute hydrochloric acid and extracted with ether. After washing with water, the ether solution is dried and evaporated. What remains is 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanhydroxamic acid.

Claims (6)

1. Derivatives of 2-(2,2-dihaiogenovinyl)-3,3-dimethylcyclopropanecarboxylic acid of the general formula I
Figure imgb0027
in which
the Hal's independently of one another represent halogen and
Y represents a C-atom which is exclusively linked both by a single bond and by a double bond to oxygen or sulphur and/or nitrogen, at least one bond being taken up by nitrogen and Y does not represent the carboxylic amide radical.
2. A process for the preparation of the derivatives of 2-(2,2-dihalogenovinyl)-3,3-dimethylcyclopropanecarboxylic acid of the general formula I according to claim 1, characterised in that a compound of the general formula II
Figure imgb0028
in which
Hal and Y have the meaning indicated above, is treated with a base in the presence of a diluent.
3. Compounds of the general formula II according to claim 2 when they are used in the process according to claim 2.
4. A process for the preparation of the compounds II according to claim 3, characterised in that compounds of the formula III
Figure imgb0029
in which
Y has the meaning indicated in claim 1, are reacted with tetrahalogenomethane optionally in the presence of a diluent and in the presence of a catalyst.
5. Compounds of the general formula III
Figure imgb0030
in which
Y represents the oxazoline radical of the general formula IV
Figure imgb0031
in which
R12―R15, independently of one another represent hydrogen, alkyl, aralkyl, aryl or together with the adjacent C-atoms can form a carbocyclic ring, when they are used in the process according to claim 4 for the preparation of the compounds according to claim 3.
6. A process for the preparation of the compounds of the general formula III according to claim 5, characterised in that 4-cyano-3,3-dimethyl-1-butene of the formula V
Figure imgb0032
is reacted with 2-amino-alkanoles of the general formula VI
Figure imgb0033
in which
R12-R15 have the meaning indicated above, at temperatures of 150 to 200°C optionally in the presence of a catalyst and a diluent.
EP78100347A 1977-07-16 1978-07-11 Derivatives of 2-(2,2-dihalogenvinyl)-3,3-dimethyl-cyclopropane carboxylic acid and process for preparing them Expired EP0000390B1 (en)

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NZ185635A (en) * 1976-11-18 1980-04-28 Ici Ltd Preparation of 3-dihalovinyl-2,2-dimethylcyclopropane carboxylic acid derivatives
DE2732213A1 (en) * 1977-07-16 1979-01-25 Bayer Ag DERIVATIVES OF THE CYCLOPROPANCARBONIC ACID DERIVATIVES, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS INTERMEDIATE PRODUCTS IN THE MANUFACTURING OF INSECTICIDES

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DE2861156D1 (en) 1981-12-24
DE2732213A1 (en) 1979-01-25
IL55132A0 (en) 1978-09-29
BR7804547A (en) 1979-03-06
JPS5419941A (en) 1979-02-15
DK317778A (en) 1979-01-17
IT7825713A0 (en) 1978-07-14
EP0000390A1 (en) 1979-01-24
US4216162A (en) 1980-08-05

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