Classifications

• • 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-dimethylcyclopropanecarboxylic acid, a process for their preparation and their use as intermediates for the production of insecticides such as 2- (2,2-dichlorovinyl) -3 , 3-dimethylcyclopropanecarboxylic acid 3-phenoxybenzyl ester and new intermediates for their production.
• 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 I 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-dimethylcyclopropane caffonic acid esters such as 2- (2,2-dichlorovinyl) ) -3,3-dimethylcyclopropanecarboxylic acid 3-phenoxy-benzyl ester is simpler and possible in better yields than from the corresponding nitriles.
• R 1 is hydrogen, alkyl radicals having 1-4 C atoms or aryl such as phenyl or tolyl
• R 2 is hydrogen, alkyl radicals having 1-4 C atoms, aryl residues such as phenyl or tolyl, hydroxyl, alkoxy residues with 1-4 C atoms, amino, alkylamino with 1-4 C atoms, dialkylamino with 2-8 C atoms, acyl residues with 1-7 C atoms, Alkoxycarbonyl with 2-5 C-atanes, or aminocarbonyl and R 1 and R 2 together also represent parts of a ring such as tetramethylene, pentamethylene or -CH2-CH2-0-CH2-CH2-, furthermore stands for the rest of the formula b , where R represents alkyl radicals with 1-4 C atoms, aryl such as phenyl, or acyl with 1-7
• 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.
• the 3,3-dimethyl-4-pentenoic acid amide produced by partial hydrolysis from the 4-cyano-3,3-dimethyl-1-butene, is taken up in carbon tetrachloride and after addition of dibenzoyl peroxide by heating in the adduct 3 , 3-Dimethyl-4,6,6,6-tetrachlorohexane amide.
• the starting compounds of the general formula II are new. However, they can be obtained by using compounds of the formula III in which 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 II.
• 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.
• tetrahalomethanes which can also be used as starting materials are preferably used.
• 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 mol of base on the compounds of the formula II and gives the compounds according to the invention with cyclization and ⁇ -elimination. Cyclization and ⁇ -elimination can be carried out either sequentially or simultaneously.
• Bases are 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.
• 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.
• 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.
• R 12 -R 15 of the 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, which is optionally substituted by halogen, alkoxy or phenoxy, 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 Can form 3-4 carbon atoms.
• the present invention is illustrated by the following examples. Under .1 of each example, the. Formation of the residue Y, i.e. the carboxylic acid derivative group, starting from 4-cyano-3,3-dimethyl-1-butene or 3,3-dimethyl-4-pentenoic acid.

Landscapes

• 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)

Applications Claiming Priority (2)

Publications (2)

Family

ID=6014088

Family Applications (1)

Country Status (8)

Families Citing this family (9)

Citations (3)

Family Cites Families (8)

• 1977
  • 1977-07-16 DE DE19772732213 patent/DE2732213A1/de not_active Withdrawn
• 1978
  • 1978-06-28 US US05/920,031 patent/US4216162A/en not_active Expired - Lifetime
  • 1978-07-11 EP EP78100347A patent/EP0000390B1/fr not_active Expired
  • 1978-07-11 DE DE7878100347T patent/DE2861156D1/de not_active Expired
  • 1978-07-13 IL IL55132A patent/IL55132A0/xx unknown
  • 1978-07-14 IT IT7825713A patent/IT7825713A0/it unknown
  • 1978-07-14 BR BR7804547A patent/BR7804547A/pt unknown
  • 1978-07-14 JP JP8526478A patent/JPS5419941A/ja active Pending
  • 1978-07-14 DK DK783177A patent/DK317778A/da unknown

Patent Citations (3)

Also Published As

Similar Documents

Legal Events