EP0000390B1 - Dérivés de l'acide 2-(2,2-Halogénovinyle)-3,3-diméthylcyclopropane-carboxylique et procédé pour la préparation - Google Patents

Dérivés de l'acide 2-(2,2-Halogénovinyle)-3,3-diméthylcyclopropane-carboxylique et procédé pour la préparation Download PDF

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Publication number
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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EP
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Prior art keywords
dimethyl
general formula
compounds
preparation
acid
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EP78100347A
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German (de)
English (en)
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EP0000390A1 (fr
Inventor
Dieter Dr. Arlt
Manfred Dr Jautelat
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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
    • 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.

Landscapes

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

Claims (6)

1. Dérivés de l'acide 2-(2,2-dihalogénovinyl)-3,3-diméthylcyclopropanecarboxylique de formule générale 1
Figure imgb0020
dans laquelle
Hal représente chacun indépendamment un halogène, et
Y représente un atome de carbone qui est exclusivement relié par une liaison simple ou également une liaison double à l'oxygène ou au soufre et/ou à l'azote, au moins une liaison étant occupée par l'azote, et Y n'est pas le reste carboxamide.
2. Procédé pour la préparation des dérivés de l'acide 2-(2,2-dihalogénovinyl)-3,3-diméthylcyclo- propanecarboxylique de formule générale 1 selon la revendication 1, caractérisé en ce que l'on traite un composé de formule générale
Figure imgb0021
dans laquelle
Hal et Y sont tels que définis ci-dessus par une base en présence d'un agent diluant.
3. Composés de formule générale II selon la revendication 2.
4. Procédé pour la préparation des composés II selon la revendication 3, caractérisé en ce que l'on fait réagir des composés de formule III
Figure imgb0022
dans laquelle Y est tel que défini ci-dessus avec un tétrahalogénométhane, éventuellement en présence d'un agent diluant, en présence d'un catalyseur.
5. Composés de formule générale III
Figure imgb0023
dans laquelle Y représente un reste oxazoline de formule générale (IV)
Figure imgb0024
dans laquelle
R12 à R15 représentent indépendamment l'un de l'autre l'hydrogène ou un groupe alkyle, arylalkyle, aryle ou peuvent former ensemble avec les atomes de carbone qui les limitent un noyau carboxylique, si on les utilise dans le procédé selon la revendication 4, pour la préparation des composés selon la revendication 3.
6. Procédé pour la préparation des composés de formule générale III selon la revendication 5, caractérisé en ce que l'on fait réagir le 4-cyano-3,3-diméthyl-1-butène de formule (V)
Figure imgb0025
avec des 2-aminoalcanols de formule générale (VI)
Figure imgb0026
dans laquelle
R12―R15 sont tels que définis ci-dessus, à des températures de 150 à 200°C, éventuellement en présence d'un catalyseur ainsi que d'un agent diluant.
EP78100347A 1977-07-16 1978-07-11 Dérivés de l'acide 2-(2,2-Halogénovinyle)-3,3-diméthylcyclopropane-carboxylique et procédé pour la préparation Expired EP0000390B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2732213 1977-07-16
DE19772732213 DE2732213A1 (de) 1977-07-16 1977-07-16 Derivate der cyclopropancarbonsaeurederivate, verfahren zu ihrer herstellung und ihre verwendung als zwischenprodukte zur herstellung von insektiziden

Publications (2)

Publication Number Publication Date
EP0000390A1 EP0000390A1 (fr) 1979-01-24
EP0000390B1 true EP0000390B1 (fr) 1981-10-14

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EP78100347A Expired EP0000390B1 (fr) 1977-07-16 1978-07-11 Dérivés de l'acide 2-(2,2-Halogénovinyle)-3,3-diméthylcyclopropane-carboxylique et procédé pour la préparation

Country Status (8)

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US (1) US4216162A (fr)
EP (1) EP0000390B1 (fr)
JP (1) JPS5419941A (fr)
BR (1) BR7804547A (fr)
DE (2) DE2732213A1 (fr)
DK (1) DK317778A (fr)
IL (1) IL55132A0 (fr)
IT (1) IT7825713A0 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2732213A1 (de) * 1977-07-16 1979-01-25 Bayer Ag Derivate der cyclopropancarbonsaeurederivate, verfahren zu ihrer herstellung und ihre verwendung als zwischenprodukte zur herstellung von insektiziden
DE2923777A1 (de) * 1979-06-12 1980-12-18 Bayer Ag Verfahren zur herstellung von 2-cyano-3,3-dimethyl-cyclopropan-1- carbonsaeureestern sowie zwischenprodukte zu seiner durchfuehrung
DE2937815A1 (de) 1979-09-19 1981-04-02 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von 3,3-dimethyl-pent-4-en-saeureamiden
FR2535315A1 (fr) * 1982-11-02 1984-05-04 Roussel Uclaf Nouveaux derives de l'acide cyclopropane carboxylique comportant un groupement alcoylthio carbonyle et un atome d'halogene, leur preparation, leur application a la lutte contre les parasites des vegetaux, des animaux et des locaux et les compositions les renfermant
US5227494A (en) * 1988-09-14 1993-07-13 Schering Corporation Process for preparing oxazoline compounds
EP0555340B1 (fr) * 1990-10-25 1994-12-07 Schering Corporation Procede de preparation de florfenicol, de ses analogues et de ses intermediaires d'oxazoline
DE4401099A1 (de) * 1994-01-17 1995-07-20 Bayer Ag Substituierte Oxazoline
AU1454995A (en) * 1994-01-17 1995-08-01 Bayer Aktiengesellschaft Azatrioxaspiroalkenes as parasiticides
US10913649B2 (en) * 2017-09-01 2021-02-09 Eaton Intelligent Power Limited Fluid nozzle with one or more sensors

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3201466A (en) * 1963-03-08 1965-08-17 Gulf Oil Corp Substituted cyclopropanecarboxanilide herbicides
FR1437448A (fr) * 1965-01-27 1966-05-06 Rhone Poulenc Sa Acides méthylène-2 cycloalcane-carboxyliques et leurs dérivés
US3484485A (en) * 1967-06-20 1969-12-16 Herbert Schwartz Cyclopropanecarboxanilides
US3753679A (en) * 1968-05-03 1973-08-21 Exxon Research Engineering Co Herbicidal s-aryl arylamides as herbicides
US3919227A (en) * 1969-06-12 1975-11-11 Du Pont Copolymers or cyclopropenes with polymerizable ethylenic compounds
US4012430A (en) * 1972-05-16 1977-03-15 Shell Oil Company Process for the preparation of cyclopropane derivatives
JPS5417877B2 (fr) * 1972-07-28 1979-07-03
AU507776B2 (en) * 1975-05-16 1980-02-28 Imperial Chemical Industries Limited Carboxylic acids, oximes and nitriles
GB1572183A (en) * 1975-09-05 1980-07-23 Wellcome Found Cyclopropane carboxylic acid ester synthesis and intermediates therefor
NZ185635A (en) * 1976-11-18 1980-04-28 Ici Ltd Preparation of 3-dihalovinyl-2,2-dimethylcyclopropane carboxylic acid derivatives
DE2732213A1 (de) * 1977-07-16 1979-01-25 Bayer Ag Derivate der cyclopropancarbonsaeurederivate, verfahren zu ihrer herstellung und ihre verwendung als zwischenprodukte zur herstellung von insektiziden

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

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