CS268082B1 - Biologically active esters with pyrethroid component in molecule and method of their preparation - Google Patents

Abstract

Leading Stem Solutions Are New Biologically active esters with a pyrethroid component in the molecule of formula I, wherein the symbol R1 denotes an alkyl group with a straight line with a branched chain with a maximum of 4. \ t carbon atoms, R represents Ia or Ib and X are halogen (chloro) bromine). Their posticidal effects were for example on insects and mites. Method of preparation of general substances of formula (I), consists in the reaction of a hydroxybenzoate of formula II wherein the symbol R, R is as defined above the presence of 4-dimethylaminopyridine a dicyclohexylcargodllmide at temperature 10 to 20 ° C or with chloride or anhydride organic acids in the presence of of anhydrous pyridine at 20 to 60 ° C.

Description

The invention relates to biologically active esters with a pyrethroid component in the molecule and to a process for their preparation.

The present invention relates to biologically active esters with a pyrethroid component in the molecule of general formula I wherein the symbol R denotes a straight-chain or branched alkyl group with a maximum of 4 ato where halogen denotes the symbol X (chlorine, bromine).

A process for the preparation of biologically active esters with a pyrethroid component in a molecule of formula I is characterized in that a hydroxy compound of formula II is reacted.

wherein X, R is as defined above with an organic acid of formula III wherein X is as defined above in the presence of 4-dimethylaminopyridine and dicyclohexylcarbodiimide at 10 to 20 ° C or with an organic acid chloride or anhydride in the presence of anhydrous pyridine at 20 up to 60 ° C.

In the following, the invention is further elucidated by means of exemplary embodiments without being limited thereto.

Example

0.12 g (0.55 mmol) of 1- (2,2-dimethyl-6-chromenyl) -1-propanol, 0.1 g (0.5 mmol) of 3- (2,2-dichloroethenyl) -2, 2-Dimethylcyclopropanecarboxylic acid, 0.1 g (0.5 mmol) of dicyclohexylcarbodiimide and 0.005 g (0.05 mmol) of β, β-dimethylaminopyridine were stirred in 5 ml of anhydrous diethyl ether at 15 to 20 ° C for 2 hours. Everything was left to stand overnight at the same temperature. Then, the reaction mixture was diluted with diethyl ether, filtered, and the filtrate was washed successively with 5% aqueous hydrochloric acid solution, saturated brine. The ether layer was dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was then separated by column chromatography on silica gel with 8 wt. % water (eluent: petroether containing up to 20% by volume of diethyl ether). 0.13 g (65%) of 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid 1- (2,2-dimethyl-6-chromenyl) propyl ester was obtained. IR analysis (CCl 3, 5%): 1726.1712 (CO ester.), 1616.1493 (arom.), 1650.1641 (CC), 1614 (CC conc.), 1390.1378 1378 ( _a CH ₃ ) cm- ¹ . MS analysis: 408/10/12 / M ⁺ /, (Cl-CGG) 393/5/7 {C ^ H ^ Cl ^), 201 (C ₁₄ H ₁₇ O), 185 (C ₁₃ H ₁₃ O ), 144 (C ₁₀ H ₁₀ O).

In the same manner was prepared 1- (E- (2-bromo-3-l.dimethyl ethoxypropoxy / -phenyl propyl 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropane acid. IR analysis (UCI ₄ ^ ) = 1727.1710 (EI, analysis: 327 / § (M ⁺ -G ₈ iI ₉ 0 ₂ Cl ₂ ).

The biological effects were tested on the mite Tetranychus urticae, where it was found to affect its ogenesis and hatchability. For example, for 1 "(2,2-dimethyl-6-chromenyl) propyl ether of 3- (2,2-dichloroethenyl)" 2,2-dimethylcyclopropanecarboxylic acid at con-

concentration of 10% by volume in acetone and contact application of 5 .mu.l to the bean leaves loaded 12 mites in 96 hours. After 7 days, 3 of them were dead. For 3- (4-bromo-1,1-dimethyl-3-ethoxypropoxy) phenyl] propyl ester of 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid at a concentration of 10% by volume, 13 mites did not charge any For comparison, 12 mites were placed on leaves treated with acetone only on 26 eggs, from which nymphs hatched after 7 days.

Claims (2)

OBJECT OF THE INVENTION Biologically active esters with a pyrethroid component in a molecule of general formula I ^x X ₂ C-CH-CH-CH-COOCH (R ¹ ) R ² (I) In (ch ₃ ) ₂ where the symbol R ¹ denotes a straight-chain or branched alkyl group with a maximum of 4 carbon atoms R ² denotes the group fOT J ^H 3 or the group _ ^ 0 ^ -οΟ (ΟΗ ₃ ) ₂ CHBrCH ₂ 0R ¹ zl X is halogen. 2. A process for the preparation of biologically active esters with a pyrethroid component in a molecule of the formula I as claimed in claim 1, which comprises reacting a hydroxy compound of the formula II. ' R ¹ -CH-OH (II) R ² 'wherein the symbol R ¹ , R ² has the meaning given above with an organic acid of general formula III (III) wherein the symbol X has the above meaning x ₂ c-ch-ch-ch-cooh ^K C (CH ₃ ) _{2 has the} meaning given above in the presence of 4-dimethylaminopyridine and dicyclohexylcarbodiimide at 10 to 20 ° C or with an organic acid chloride or anhydride in the presence of anhydrous pyridine at 20 to 60 ° C.