CS269385B1 - 3- [2,2-Dichloro-ethenyl] -2,2-dimethyl-cyclopropanecarboxylic acid ester with bicyclic alcohols as biologically active substances and process for their preparation - Google Patents

Abstract

The subject of the solution are new biologically active substances of the general formula I, where the symbol R denotes group Ha or group II b. Their pesticidal effects were tested, for example, on insects, mites. Another part is a method of preparing substances of the general formula I, consisting in the reaction of 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid with bicyclic alcohols or in the presence of an equimolar amount of dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine at a temperature of 10 to 20 °C.

Description

The invention relates to 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid ester with bicyclic alcohols as biologically active substances and to a process for their preparation.

The substances which are the subject of the invention are an example of another new type of pesticide, in the molecule of which, in addition to the classical pyrethroid component, a component representing a bioanalog of juvenile insect hormone is also present.

The present invention relates to esters of 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid with bicyclic alcohols of the general formula I ^C1 '' OCH-CH-CH-COOR ^C1Z ch | ^c gh ₃ (i) »where the symbol R denotes the group Ha

(II a), or group II b

-o-ch ₂ -ch ₂ -c (ch ₃ ) ₂ oc ₂ h ₅ (II b),

A process for the preparation of 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid ester with bicyclic alcohols of the formula I is characterized in that 3- (2,2-dichloroethenyl) -2,2-dimethylc. cyclopropanecarboxylic acid with a bicyclic alcohol selected from the group consisting of a compound of formula II and ck ₃

C ^h 2- / Q \ -O- ^C H2 ~ ^C = CH-CO ° ^C 2 ^H 5 (II a),

or II o

-o-ch ₂ -ch ₂ -c (ch ₃ ) ₂ -oc ₂ h ₅ (II b), in the presence of an equimolar amount of dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine at 10 to 20 ° C.

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

Example 1

0.1 g (0.5 mmol) of 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid, 0.18 g (0.55 mmol) of 2- [4- (3-ethoxycarbonyl-2-methyl- 2-propen-1-yloxy / benzyl] cyclohexanol, 0.1 g (0.5 mmol) of dicyclohexylcarbodiimide and 0.005 g (0.05 mmol) of N, N-dimethylaminopyridine were stirred in 5 ml of anhydrous diethyl ether at 15 to 20 ° C for 2 hours. Then, the reaction mixture was diluted with diethyl ether, filtered, and the filtrate was washed successively with 5% aqueous hydrochloric acid solution, saturated brine.

CS 269 385 Bl

The residue of the washed ether layer was separated by column chromatography on silica gel with 8 wt. % water (eluent: petroleum ether containing up to 20% by volume of diethyl ether).

0.17 g (66%) of 2- [4- (3-ethoxycarbonyl-2-methyl-2-propen-1-yloxy) 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid ester was obtained. benzyl] cyclohexynol. ·

IR / CC1 _4, 5% /: 1723.1710 / C = 0 Oester. /, 1665/0 C = C /, 1614,1585,1515 / Aromatics 0 /, 1389.1377 / jgCH-j / cm ^-1.

¹³ C-NMR / 200MHz /: 14.26 / _{CH3 CH2} /, 15.65 / CH · ^ * /, 24.67 / CHqJ /, 25.44 / ICH ₂ /, // 27.9 CH ₃ / C ₂ ^ // 27.90 / ^ /, 14.89 and 28.38 // CH _3/2 cJ /, 31.88 and 32.40 / CH ^ CH /, 34.9Ο / _α ζ) /. 37.44 / ζ) -CH ₂ /, 42.38 / OH /, 55.72 / Q /, 59.76 / CH ₃ CH ₂ /, 71.68 / OCH ₂ /,

114.59 / /, 115.57 / = CH- /, 12O.42 / C1 ₂ C = /, 124.98 / C1 ₂ C =

CH 2, 129.94 / /, 132.97 / ₁ 152.97 / CH ₂ -C = / _t 156.50 / (CjC-O),

166.48 / COO /, 17O.O5 / COO /

Example 2

In the same manner, 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid ester with 2- [4- (3-ethoxy-3-methylbutoxy) benzyl] cyclohexanol was prepared.

IR spectrum (CCl ₄ , 5%): 1723 (0 CO ester.), 1614, 1584, 1516 (0 aromatics), 1391.1380, 1366 (<T _S CH ₃ ) cm ^-1 .

¹³ C-NMR spectrum (200 MHz): 16.07 (CH ₃ CH ₂ 0), 24.52 (¾)), 25.03 (CH ₂ Cl 2), 26.05 ((CH ₃ ) ₂

C-0), 27.08 _{((CH3) 2-C),} and ^about 14.92 2Θ.4Ό () 29.87 (), 32.06 (^), 32.12 and 32.28 (CH-CH), 37.73 (0¾).

^ó · ^ó n

39.18 (CH ₂ C-), 43.78 (<J _CH ), 56.48 (OCH ₂ CH ₃ ), 64., 16 (0 (¾¾)),

73.38 (C (CH ₃ ) ₂ O), 76.85 (Q), 114.13 (gH 2 O). 12O.43 (= CC1 ₂ ),

125.O8 (CH = CCl ₂ ), 129.49 (° @ ~ .O), 131.92 (^ Q) ^), 157.16 ((q £ ^- °) »17O.17 (OCO).

Biological efficacy has been tested, for example, on insects and mites. For example, ester of 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropane carboxylate with 2- ^ 4- (3-ethcxykarbonyl-2-methyl-2-propen-l-yloxy) benzylJcyklohexanolem exhibited even at a concentration of ⁴ vol 1O .% strong insecticidal effect in Tetranychus urticae.

The biological activity of 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid ester with 2- ^ 4- (3-ethoxy-2-methylbutoxy) benzyl] cyclohexanol was tested on Tenebrio molitor, the morphogenesis of which was suppressed already at a concentration of 5.10 " ² mg.

Claims (1)

P 6 E D MÉ T OF THE INVENTION A ester of 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid with bicyclic alcohols of general formula I (I), Clx ₍ Cl / C = CH-CH-CH-COOH AND CH ₃ CH ₃ where the symbol H denotes a group of formula IIa CH, i · 3 OCH 2 CH-COOC-H, 2 2 5 (Ha), or a group of formula Hb OH as biologically active substances. Process for the preparation of compounds according to point 1 of general formula I, characterized in that 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid is reacted with a bicyclic alcohol selected from the group comprising a compound of formula Ha (Ha), or Hb -och, ch ₂ -c (ch ₃ ) ₂ -oc ₂ h ₅ (Hb), in the presence of an equimolar amount of dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine at 10 to 20 ° C.