CH602006A5 - Cyclopropane carboxylic esters - Google Patents

Abstract

Cyclopropane carboxylic esters are insecticides and acaricides

Description

  

  
 



   The present invention relates to a pesticide which, as an active component, is a compound of the formula
EMI1.1
 contains, where Xt and X2 are each fluorine, chlorine or bromine and Y is hydrogen, cyano or ethynyl.



   Because of their action of particular importance are compounds of the formula 1 in which X1 and X2 are identical and fluorine or chlorine and Y are hydrogen, cyano or ethynyl.



   The compounds of formula I are prepared according to methods known per se, for. B. manufactured as follows:
EMI1.2


<tb> <SEP> x <SEP> O <SEP> Y <SEP> acid bin
<tb> 1) <SEP> C = CH-CH <SEP> - <SEP> CH-C-Hal <SEP> + <SEP> HO-CH <SEP> 4 <SEP> O <SEP> <
<tb> <SEP> C = CH-CH <SEP> - <SEP> CH-C-Hal <SEP> +
<tb> <SEP> X2 <SEP> CH <SEP> U <SEP> U <SEP> Medium
<tb> <SEP> CH3 <SEP> (Itt)
<tb> <SEP> (11)
<tb> <SEP> xl <SEP> O <SEP> Y <SEP> acid bin
<tb> 2) <SEP> c = cH-CH-cH-c "-0H <SEP> + <SEP> Hal-CH <SEP> 2 <SEP> O <SEP> t <SEP> medium
<tb> <SEP> \ CH <SEP> IJ
<tb> <SEP> CH3 <SEP> (V)
<tb> <SEP> (Iv)
<tb> <SEP> X <SEP> O <SEP> Y <SEP> water binding
<tb> 3) <SEP> C-CH-CH <SEP> - <SEP> CH-C-OH <SEP> + <SEP> HO-CH <SEP> 1 <SEP> of the <SEP>
<tb> <SEP> x <SEP> CH <SEP> U <SEP> <<SEP> medium
<tb> <SEP> H20
<tb> <SEP> CH3 <SEP> (III)
<tb> <SEP> (1V)
<tb> In formulas II to V have <RTI

    ID = 1.2> XI, X2 and Y the meaning given for the formula I and Hal stands for a halogen atom, in particular for chlorine or bromine.



   Acid-binding agents for processes 1 and 2 are in particular tertiary amines such as trialkylamines and pyri dine, and also hydroxides, oxides, carbonates and bicarbonates of alkali and alkaline earth metals and alkali metal alcoholates such as. B. Potassium-t. butylate and sodium methylate into consideration. As a water-binding agent for the method 3, for. B. dicyclohexylcarbodiimide can be used. Processes 1 to 3 are carried out at a reaction temperature between -10 and 100 ° C., usually between 20 and 80 ° C., under normal or elevated pressure and preferably in an inert solvent in an inert solvent or diluent.



   Suitable solvents or diluents are, for. B.



  Ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; Amides such as N, N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylene, chloroform and chlorobenzene; Nitriles such as acetonitrile; Dimethyl sulfoxide and ketones such as acetone and methyl ethyl ketone. Process 2 can also be carried out in aqueous solution.



   The starting materials of the formulas II to IV are known or can be prepared analogously to known methods.



   The compounds of the formula I are in the form of mixtures of different optically active and cis-trans isomers if optically active or cis / trans isomeric starting materials were not used uniformly in the preparation. The various stable isomer mixtures can be separated into the uniform isomers by known methods. The term “compounds of the formula I” is understood to mean both the individual isomers and their mixtures. The compounds of the formula I are suitable for combating various animal and vegetable pests.



   In particular, however, they are suitable for controlling insects and representatives of the order Akarina. You can e.g. B. against insects of the families Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestymaline Tidae, Coccinellidae, Pyrrhocoridae, Tenebromionelidae, Coccinellidae, Lysidae, Chrysulidae, Crysulidae, Lysulidae, Lysulidae, Crysulidae, Chrysulidae, Crysulidae. Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae, as well as acarids of the families Tetranychidae and Dermanyssidae, are used.



   The compounds of the formula I are particularly suitable for combating plant-damaging insects, in particular plant-damaging feeding insects, in ornamental and useful plants, especially in cotton crops (e.g.



  against Spodoptera littoralis and Heliothis virescens) and vegetable crops (e.g. against Leptinotarsa decemlineata and Myzus persicae).



   The active ingredients of formula I also show a very beneficial effect against flies such as. B. Musca domestica and mosquito larvae.



   The acaricidal or insecticidal effect can be significantly broadened by adding other insecticides and / or acaricides and adapted to the given circumstances.



   Suitable additives are, for. B.



  org. Phosphorus compounds; Nitrophenols and their derivatives; Formamidine; Ureas; other pyrethrin-like compounds; as well as carbamates and chlorinated hydrocarbons.



   It is particularly advantageous to combine compounds of the formula I with substances which have a synergistic or reinforcing effect on pyrethroids.



  Examples of such compounds include: a. Piperonyl butoxide, propynyl ether and propynyl phosphonate, 2- (3,4-methylenedioxy.



     phenoxyS3,6,9-trioxaundecane (Sesamex or Sesoxane), S, S, S tributylphosphorotrithioate, 1,2-methylenedioxy 4- (2- (octylsulfinyl> propyl) benzene.



   The compounds of the formula I can be used alone or together with suitable carriers and / or additives. Suitable additives can be solid or liquid and correspond to the substances customary in formulation technology such as. B. natural or regenerated substances, solvents, dispersants, networks, adhesives, thickeners, binders and / or fertilizers.



   The agents according to the invention are produced in a manner known per se by intimately mixing and / or grinding active ingredients of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active ingredients. The active ingredients can be present and used in the following working-up forms;
Fixed forms of processing;

  Dusts, grit, granules (coated granules, impregnation granules and homogeneous granules);
Liquid working-up forms: a) Active substance concentrates dispersible in water: wettable powders, pastes, emulsions; b) Solutions
The content of active ingredient in the agents described above is between 0.1 and 95%, it should be mentioned that when applied from the aircraft or by means of other suitable application devices, concentrations of up to 99.5% or even pure active ingredient can be used.



   The active ingredients of the formula I can be formulated, for example, as follows (parts mean parts by weight): Dusts: The following substances are used to produce an a) 50% and b) 20 / own dust: a) 5 parts of active ingredient,
95 parts of talc; b) 2 parts of active ingredient,
1 part of highly dispersed silica,
97 parts of talc.



   The active ingredients are mixed and ground with the carrier substances.



  Granulate: The following substances are used to produce 50% granulate:
5 parts active ingredient,
0.25 parts epichlorohydrin,
0.25 part of cetyl polyglycol ether,
3.50 parts of polyethylene glycol,
91 parts of kaolin (grain size 0.3-0.8 mm).



   The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution obtained in this way is sprayed onto kaolin and the acetone is then evaporated in vacuo.



  Pointed powder: To produce a) 400 / above, b) and c) 25 / above d) 100 / o wettable powder, the following ingredients are used; a) 40 parts of active ingredient,
5 parts of lignin sulfonic acid sodium salt,
1 part dibutylnaphthalenesulfonic acid sodium salt,
54 parts of silica; b) 25 parts of active ingredient,
4.5 parts calcium lignosulfonate,
1.9 parts of champagne chalk / hydroxyalkyl cellulose mixture (1: 1),
1.5 parts of sodium dibutyl naphthalene sulfonate,
19.5 parts of silica,
19.5 parts of champagne chalk,
28.1 parts of kaolin; c) 25 parts of active ingredient,
2.5 parts of isooctylphenoxy-polyethylene-ethanol,
1.7 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1),
8.3 parts sodium aluminum silicate,
16.5 parts kieselguhr,
46 parts kaolin:

   d) 10 parts of active ingredient,
3 parts mixture of the sodium salts of saturated
Fatty alcohol sulfates,
5 parts of naphthalenesulfonic acid / formaldehyde condensate,
82 parts of kaolin.



   The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. Wettable powders are obtained which can be diluted with water and suspensions of any desired concentration.

 

  Emulsifiable concentrates; The following substances are used to produce a) 100% b) 25 above and c) 500 / above emulsifiable concentrate: a) 10 parts of active ingredient,
3.4 parts epoxidized vegetable oil,
3.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and
Alkylarylsulfonate calcium salt,
40 parts of dimethylformamide,
43.2 parts of xylene; b) 25 parts of active ingredient,
2.5 parts epoxidized vegetable oil,
10 parts of an alkylarylsulfonate / fatty alcohol poly glycol ether mixture,
5 parts of dimethylformamide,
57.5 parts of xylene; c) 50 parts of active ingredients,
4.2 parts of tributylphenol polyglycol ether
5.8 parts calcium dodecylbenzenesulfonate,
20 parts of cyclohexanone,
20 parts of xylene.



   Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.



  Spray: To produce a) 50% and b) 950 / above spray, the following ingredients are used: a) 5 parts of active ingredient,
1 part epichlorohydrin,
94 parts of gasoline (boiling point 160-190 C); b) 95 parts of active ingredient,
5 parts of epichlorohydrin.



  example 1
Production of 2-methyl-3- (ss, B-dichlorovinyl) -cyclopropa carboxylic acid (3-phenoxy-benzyl) ester
To a solution of 3.9 g of 2-methyl-3- (ss, ss-dichlorovinyl) -cyclopropankarbonsäure (bp: 102-104 "C / 0.07 Torr) in 15 ml of methyl ethyl ketone are stirred at 15-20 "C first 2.92 g of triethylamine and then 5.25 g of 3-phenoxybenzyl bromide were added dropwise. The reaction mixture is stirred for 5 hours at 70-80 ° C. and then poured into 100 ml of ice water. The crude product is extracted with ether, the ether solution obtained is washed with sodium bicarbonate solution and with water and dried over sodium sulfate.



   After distilling off the ether, the compound of the formula is obtained
EMI3.1
 as a colorless oil with a refraction of nD20 = 1, S739.



   The following connections are also established in the same way:
EMI3.2
 Xl X2 Y Physical data Cl Cl CN n20 = l 5702 FF CN now = 1.5403 FFH nn = 1.5424 FF -C = -CH n9 1.5402 Cl Cl -CECH nD = 1.5748 Example 2 A) Insecticidal food poison -Effect
Tobacco and potato bushes are sprayed with a 0.05% aqueous active substance emulsion (obtained from a 100% emulsifiable concentrate).



   After the topping had dried on, the tobacco and potato plants were populated with caterpillars of Spodoptera littoralis in the L3 stage and of Heliothis virescens in the L3 stage. The experiment was carried out at 24 ° C. and 60% relative humidity.



   In the above test, compounds according to Example 1 showed a positive action against Spodoptera littoralis and Heliothis virescens caterpillars.



  B) Insecticidal contact effect
One day before the application, broad beans (Vicia faba) grown in pots were infected with about 200 aphids (Aphis fabae) per plant. It was applied by means of a compressed air syringe to the leaves infected with lice with a spray mixture in a concentration of 1000 ppm (made from a 25% wettable powder).



   The rating took place 24 hours after the application. Compounds according to Example 1 showed good contact action against Aphis fabae in the above test.



  Example 3 Effect against acarina
Phascolus vulgaris (French beans) were covered with an infected piece of leaf from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal activity. The overflowing mobile stages were dusted with the emulsified test preparations from a chromatography atomizer so that the spray mixture did not run off. After two and seven days, larvae, adults and eggs were evaluated under the binocular for living and dead individuals and the result expressed as a percentage. During the holding time, the treated plants stood in greenhouse cabins at 25 ° C.

 

   Compounds according to Example 1 showed good activity in the above test against eggs, larvae and adults of Tetranychus urticae.



   PATENT CLAIM 1
A pesticide which, as the active component, is a compound of the formula
EMI3.3
 contains, where X1 and X2 are each fluorine, chlorine or bromine and Y is hydrogen, cyano or ethynyl.



   SUBCLAIMS
1. A means according to claim 1, which is the active component of the compound of the formula
EMI3.4
 contains.



   2. A means according to claim 1, which is the active component of the compound of the formula
EMI3.5
 contains.

** WARNING ** End of DESC field could overlap beginning of CLMS **.



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. Emulsions of any desired concentration can be prepared from such concentrates by dilution with water. Spray: To produce a) 50% and b) 950 / above spray, the following ingredients are used: a) 5 parts of active ingredient, 1 part epichlorohydrin, 94 parts of gasoline (boiling point 160-190 C); b) 95 parts of active ingredient, 5 parts of epichlorohydrin. example 1 Production of 2-methyl-3- (ss, B-dichlorovinyl) -cyclopropa carboxylic acid (3-phenoxy-benzyl) ester To a solution of 3.9 g of 2-methyl-3- (ss, ss-dichlorovinyl) -cyclopropankarbonsäure (bp: 102-104 "C / 0.07 Torr) in 15 ml of methyl ethyl ketone are stirred at 15-20 "C first 2.92 g of triethylamine and then 5.25 g of 3-phenoxybenzyl bromide were added dropwise. The reaction mixture is stirred for 5 hours at 70-80 ° C. and then poured into 100 ml of ice water. The crude product is extracted with ether, the ether solution obtained is washed with sodium bicarbonate solution and with water and dried over sodium sulfate. After distilling off the ether, the compound of the formula is obtained EMI3.1 as a colorless oil with a refraction of nD20 = 1, S739. The following connections are also established in the same way: EMI3.2 Xl X2 Y Physical data Cl Cl CN n20 = l 5702 FF CN now = 1.5403 FFH nn = 1.5424 FF -C = -CH n9 1.5402 Cl Cl -CECH nD = 1.5748 Example 2 A) Insecticidal food poison -Effect Tobacco and potato bushes are sprayed with a 0.05% aqueous active substance emulsion (obtained from a 100% emulsifiable concentrate). After the topping had dried on, the tobacco and potato plants were populated with caterpillars of Spodoptera littoralis in the L3 stage and of Heliothis virescens in the L3 stage. The experiment was carried out at 24 ° C. and 60% relative humidity. In the above test, compounds according to Example 1 showed a positive action against Spodoptera littoralis and Heliothis virescens caterpillars. B) Insecticidal contact effect One day before the application, broad beans (Vicia faba) grown in pots were infected with about 200 aphids (Aphis fabae) per plant. It was applied by means of a compressed air syringe to the leaves infected with lice with a spray mixture in a concentration of 1000 ppm (made from a 25% wettable powder). The rating took place 24 hours after the application. Compounds according to Example 1 showed good contact action against Aphis fabae in the above test. Example 3 Effect against acarina Phascolus vulgaris (French beans) were covered with an infected piece of leaf from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal activity. The overflowing mobile stages were dusted with the emulsified test preparations from a chromatography atomizer so that the spray mixture did not run off. After two and seven days, larvae, adults and eggs were evaluated under the binocular for living and dead individuals and the result expressed as a percentage. During the holding time, the treated plants stood in greenhouse cabins at 25 ° C. Compounds according to Example 1 showed good activity in the above test against eggs, larvae and adults of Tetranychus urticae. PATENT CLAIM 1 A pesticide which, as the active component, is a compound of the formula EMI3.3 contains, where X1 and X2 are each fluorine, chlorine or bromine and Y is hydrogen, cyano or ethynyl. SUBCLAIMS 1. A means according to claim 1, which is the active component of the compound of the formula EMI3.4 contains. 2. A means according to claim 1, which is the active component of the compound of the formula EMI3.5 contains. 3. A means according to claim 1, which as active Component the compound of the formula EMI4.1 contains. PATENT CLAIM 11 Use of an agent according to patent claim I for combating insects and representatives of the Akarina order.