GB1570928A

GB1570928A - Pesticidal cyclopropane carboxylic acid esters

Info

Publication number: GB1570928A
Application number: GB6501/77A
Authority: GB
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1976-02-17
Filing date: 1977-02-16
Publication date: 1980-07-09
Also published as: FR2341554B1; NL7701321A; DE2706184A1; OA05647A; FR2341554A1; JPS6113459B2; IL51466A0; JPS52100455A; IT1076892B; IL51466A

Description

(54) NOVEL PESTICIDAL CYCLOPROPANE CARBOXYLIC ACID ESTERS (71) We, CIBA-GEIGY AG, a body corporate organised according to the laws of Switzerland, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particulary described in and by the following statement:- The present invention relates to cyclopropane carboxylic acid esters, to - processes for producing them and to their use in combating pests.

The cyclopropane carboxylic acid esters have the formula

wherein R, represents hydrogen or methyl, R2 represents hydrogen, methyl, cyano or ethynyl, X represents hydrogen, halogen or methyl, and n represents the number 1 or 2.

By halogen are meant fluorine, chlorine, bromine and/or iodine, especially however chlorine.

Preferred on account of their action are compounds of the formula I wherein R, represents hydrogen or methyl, R2 represents hydrogen, cyano or ethynyl, X represents hydrogen, fluorine, chlorine or methyl, and n represents the number 1.

The compounds of the formula I can be produced by methods known per se, for example as follows:

(1) CH3 R1 \C/ R2 acid / binding /-7 -C H = CH - CH - CH - C - Z + HO- CH 3 0t agent I-- IIQflt' (X)n (11) (Ill)

(2) CH3 \ R1 0 R2 acid- /-7 II CH=CH-CH- CH-C-OH+Z-0 "0 agent (X)n (rev) (7 (3) CH3 R1 O R2 -H20 ACH = CH - CH - CH - COH 9 HO - CH t t binding binding (X)n (it) (lit) agent In the formulae II to V, the symbols R" R2, X and n have the meanings given for the formula I, and Z represents a halogen atom, especially chlorine or bromine.

Suitable acid-binding agents for the processes 1 and 2 are, in particular, tertiary amines e.g. trialkylamines and pyridine, also hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline-earth metals, and alkali metal alcoholates e.g. potassium-t.butylate and sodium methylate. The waterbinding agent used for the process 3 can be, for example, dicyclohexylcarbodiimide. The processes 1, 2 and 3 are generally performed at a reaction temperature of between -10 and 100"C, usually between 20 and 80"C, at normal or elevated pressure and preferably in an inert solvent or diluent. Suitable solvents or diluents are, e.g., ethers and ethereal compounds e.g. diethyl ether, dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; amides e.g. N,Ndialkylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, particularly benzene, toluene, xylene, chloroform and chlorobenzene; nitriles e.g. acetonitrile; dimethylsulphoxide and ketones e.g. acetone and methyl ethyl ketone. The process 2 can also be performed in an aqueous solution.

The starting materials of the formulae II to V are known or can be produced by methods analogous to known methods.

The compounds of the formula I can be obtained as mixtures of various optically active compounds and cis/trans isomers, unless the starting materials used to produce the said compounds are homogeneous optically active compounds or cis/trans isomers. The different stable isomeric mixtures can be separated by known methods into the homogeneous isomers. It is to be understood that the compounds of the formula I according to the invention include both the individual isomers and mixtures thereof.

The compounds of the formula I are suitable for combating animal and plant pests. Accordingly the invention provides a method of combating animal or plant pests at a locus which method comprises applying to the locus a compound of the formula I. The compounds of the formula I are suitable in particular for combating insects and representatives of the order Acarina. The compounds of the formula I can be used, for example, against insects of the families: Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabacidae. Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae; and also against acarids of the families Tetranychidae and Dermanyssidae.

The compounds of the formula I are especially suitable for combating insects which damage plants, particularly insects which damage plants by eating, in crops of ornamental plants and useful plants, especially in cotton crops (e.g. against Spodoptera littoralis and Heliothis vlrescens) and in crops of vegetables (e.g. against Leptinotarsa demcelineata and Myzus persicae). The active substances of the formula I also exhibit a very favourable action against flies, such as Musca domestica, and against mosquito larvae.

The acaricidal and insecticidal action can be substantially broadened and adapted to suit given circumstances by the addition of other insecticides and/or acaricides. Suitable additives are, e.g.: organic phosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, other pyrethrin-like compounds, as well as carbamates and chlorinated hydrocarbons.

Compounds of the formula I are combined particularly advantageously also with substances which have a synergistic or intensifying effect on pyrethroids.

Examples of such compounds are, inter alia, piperonylbutoxide, propinyl ethers and propinyl phosphonates, 2 - (3,4 - methylenedioxyphenoxy) - 3,6,9trioxaundecane (Sesamex or Sesoxane), S,S,S - tributylphosphorotrithioates and 1,2 - methylenedioxy - 4 - (2 - octylsulphony) - propyl) - benzene.

The compounds of the formula I can be used on their own or in composition form together with a solid extender and/or other additive. Suitable additives can be solid or liquid and they correspond to the substances common in formulation practice, such as natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers. The invention provides a solid pesticidal composition which comprises, as active ingredient, a compound of the formula I together with a solid extender and optionally a surface active agent. The invention further provides a liquid pesticidal composition comprising the active ingredient together with a liquid diluent and a surface active agent.

The compositions according to the invention may be produced in a manner known per se e.g. by the intimate mixing and/or grinding of active substances of the formula I with suitable extenders, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms: solid preparations: dusts, scattering agents, granulates (coated granulates, impregnated granulates and homogeneous granulates); liquid preparations: a) water-dispersible concentrates of active substance:-- wettable powders, pastes or emulsions; b) solutions.

The content of active substance in the described compositions is generally between 0.1 and 95%.

The active substances of the formula I can be formulated for example asfollows: Dusts: The following substances are used to produce a) a 5% dust and b) a 2% dust: a) 5 parts of active substance, 95 parts of talcum; b) 2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.

The active substances are mixed and ground with the extenders.

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

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

Wettable powder: The following constituents are used to produce a) a 40%, b) and c) a 25%, and d) a 10% wettable powder: a) 40 parts of active substance, 5 parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid; b) 25 parts of active substance, 4.5 parts of calcium lignin sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl-naphthalene sulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin; c) 25 parts of active substance, 2.5 parts of isooctylphenoxy - polyoxyethylene - ethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin; d) 10 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

The active substance is intimately mixed in suitable mixers with the additives, and the mixture is then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of the desired concentration.

Emulsifiable concentrates: The following substances are used to produce a) a 10%, b) a 25%, and c) a 50% emulsifiable concentrate: a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylaryl - sulphonate calcium salt, 40 parts of dimethylformamide, 43.2 parts of xylene; b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of alkylarylsulphonate/fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene; c) 50 parts of active substance, 4.2 parts of tributylphenol - polyglycol ether, 5.8 parts of calcium-dodecylbenzenesulphonate, 20 parts of cyclohexanone, 20 parts of xylene.

Emulsions of the desired concentration can be prepared from these concentrates by dilution with water.

Spray: The following constituents are used to produce a) a 5% spray and b) a 95% spray: a) 5 parts of active substance, 1 part of epichlorohydrin, 94 parts of ligroin (boiling limits 1600--1900C); b) 95 parts of active substance, 5 parts of epichlorohydrin.

The invention is further illustrated by the following Examples.

Example 1.

Production of2,2 - dimethyl - 3 - (2' - phenylvinyl) - cyclopropane - carboxylic acid 3" - phenoxy - a - cyanobenzyl ester 17g of thionyl chloride is added dropwise to 22 g of 2,2 - dimethyl - 3 - (2' phenylvinyl) - cyclopropanecarboxylic acid in 300 ml of hexane. The reaction mixture is refluxed for 4 hours. The 2,2 - dimethyl - 3 - (2' - phenylvinyl) cyclopropanecarboxylic acid chloride obtained after distilling off the hexane is added dropwise at a temperature of 5--10"C, with stirring, to a mixture of 300 ml of methyl ethyl ketone, 23 g of 3 - phenoxy - a - cyanobenzyl alcohol and 10 ml of pyridine. After being stirred for one hour and then being left to stand for 12 hours at room temperature, the reaction mixture is washed successively with 100 ml of benzene diluted with water, 3% hydrochloric acid, water, 3% sodium carbonate and water and subsequently dried over sodium sulphate. The oily crude product obtained after removal of the solvent by distillation is chromatographically purified with ether/hexane (1:6) as eluant. There is obtained the compound of the formula

as a colourless oil having a refractive index of n20= 1.5695. (mixture of isomers) refractive index of the pure cis compound: n20= = 1.5710. The following compounds are obtained analogously:

Physical X' X" X"' X"" XV R1 R2 data H H Cl H H CH3 H nD220=1.5927 H CH3 H H H CH3 CN nD220=1.5816 H CH3 H H H CH3 H nD220=1.5885 H H CH3 H H CH3 CN nD220=1.5807 H H CH3 H H CH3 H nD220=1.5879 Cl H H H H CH3 H nD220=1.5933 Cl H H H H CH3 CN nD220=1.5877 H H CH3 H H CH3 CH3 nD220=1.5811 H Cl Cl H H CH3 H nD200 = 1 1.5999 Cl H H H Cl CH3 H nD200= = 1.5942 Cl H H H Cl CH3 CN nD200=1 1.5839 H Cl Cl H H CH3 CN nD200=1.5890 H Cl Cl H H CH3 -C#CH nD200=1.5958 H H CH3 H H CH3 -C#CH nD200=1.5838 H H Cl H H CH3 -C#CH nD200=1.5958 H H F H H CH3 H nD200=1.5793 H H F H H CH3 CN nD200=1 1.5740 H H F H H CH3 -C#CH nD200=1.5752 H H Cl H H CH3 H nD200=1.5930 (trans isomer) H H Cl H H CH3 CN m.p.: 100-103 C H H H H H CH3 H nD200=1.5889 (trans isomer) H H H H H CH3 -C=CH nD200=1.5882 H H Cl H H CH3 -CN nD200=1.5907 H H CH3 H H CH3 -CH nD200=1.5816 H H H H H H -CN nD200=1.5918 Example 2.

A) Insecticidal stomach-poison action Tobacco and potato plants were sprayed with a 0.05% aqueous activesubstance emulsion (obtained from a 10% emulsifiable concentrate).

After drying of the coating, caterpillars of Spodoptera littoralis in the L3-stage and of Heliothis virescens in the L3-stage were placed on the tobacco and potato plants. The test was carried out at 24 C with 60% relative humidity.

Compounds according to Example I exhibited in the above test a good insecticidal stomach poison action against Spodoptera littoralis and Heliothis virescens caterpillars.

B) Insecticidal contact action One day before application of the active-substance emulsion, broad beans (Vicia faba) grown in pots were infested with about 200 bean aphids (Aphis fabae) per plant. The spray emulsion at a concentration of 1000 ppm (prepared from a 25% wettable powder) was applied by means of a compressed-air sprayer to the leaves infested with aphids. An evaluation was made 24 hours after application.

Compounds according to Example I exhibited in the above test a good contact action against Aphis fabae.

Example 3.

Acaricidal action Phaseolus vulgaris (bush beans) were infested, 12 hours before the test for acaricidal action, with an infested piece of leaf from a mass culture of Tetranychus urticae. The transferred mobile stages were sprayed with the emulsified test preparations from a chromatography-sprayer in a manner ensuring no overflow of the spray liquor. An assessment was made after 2 to 7 days, by examination under a binocular microscope, of the living and of the dead larvae, adults and eggs. The treated plants were kept during the "holding time" in greenhouse compartments at 25"C.

Compounds according to Example I exhibited a good action in the above test against adults, larvae and eggs of Tetranychus urticae.

Claims

WHAT WE CLAIM IS:

1. A compound of the formula

wherein R, represents hydrogen or methyl, R2 represents hydrogen, methyl, cyano or ethynyl, X represents hydrogen, halogen or methyl, and n represents the number I or 2.

2. A compound according to claim 1, wherein R, represents hydrogen or methyl, R2 represents hydrogen, cyano or ethynyl, X represents hydrogen, fluorine, chlorine or methyl, and n represents the number 1.

3. The compound of the formula

4. The compound of the formula

5. The compound of the formula

6. The compound of the formula

7. The compound of the formula

8. The compound of the formula

9. The compound of the formula

10. The compound of the formula

I I. The compound of the formula

12. The compound of the formula

13. A process for preparing a compound as claimed in claim I, which process. comprises reacting a compound of formula

(wherein R1, X and n are as defined in claim 1 and Z represents halogen), with a compound of the formula

(wherein R2 is as defined in claim 1) in the presence of an acid-binding agent.

14. A process for preparing a compound as claimed in claim 1 substantially as described herein.

15. A process for preparing a compound as claimed in claim 1 substantially as described with reference to Example 1.

16. A compound according to claim 1 prepared by the process claimed in any one of claims 13 to 15.

17. A pesticidal composition which comprises, as active ingredient, a compound as claimed in any one of claims 1 to 5, 7 and 9 together with a solid extender and/or other additive.

18. A solid pesticidal composition which composition comprises, as active ingredient, a compound as claimed in any one of claims 1 to 5, 7 and 9 together with a solid extender, and optionally a surface active agent.

19. A liquid pesticidal composition which composition comprises, as active ingredient, a compound as claimed in any one of claims 1 to 5, 7 and 9 together with a liquid diluent and a surface active agent.

20. A pesticidal composition containing a compound as claimed in claim 1 in the form of a dust, granulate, wettable powder, emulsifiable concentrate or spray specifically described herein.

21. A method of combating animal or plant pests at a locus which method comprises applying to the locus a compound as claimed in any one of claims 1 to 5, 7 and 9.

22. A method according to claim 21 wherein the pests are of the class insecta or of the order Acarina.

23. A pesticidal composition which comprises, as active ingredient, a - compound as claimed in any one of claims 6, 8 and 10 to 12 together with a solid extender and/or other additive.

24. A solid pesticidal composition which composition comprises, as active ingredient, a compound as claimed in any one of claims 6, 8 and 10 to 12 together with a solid extender, and optionally a surface active agent.

25. A liquid pesticidal composition which composition comprises, as active ingredient, a compound as claimed in any one of claims 6, 8 and 10 to 12 together with a liquid diluent and a surface active agent.

26. A method of combating animal or plant pests at a locus which method comprises applying to the locus a compound as claimed in any one of claims 6, 8 and 10 to 12.

27. A method according to claim 26 wherein the pests are of the class Insecta or of the order Acarina.