GB1588212A

GB1588212A - Cyclopropanecarboxylic acid esters

Info

Publication number: GB1588212A
Application number: GB5514/78A
Authority: GB
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1977-02-11
Filing date: 1978-02-10
Publication date: 1981-04-15
Also published as: FR2380248B1; EG13106A; NL7801510A; CA1152092A; TR20016A; JPS53105462A; BE863839A; MX5368E; IT7820194A0; ES466862A1; IT1093705B; IL54009A0; FR2380248A1; DE2805312A1

Description

(54) NEW CYCLOPROPANECARBOXYLIC ACID ESTERS (71) We, CIBA-GEIGY AG, a Swiss body corporate, 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 particularly described in and by the following statement :- The present invention relates to cyclopropanecarboxylic acid esters, to a process for their manufacture and to their use in pest control.

The cyclopropanecarboxylic acid esters have the formula

wherein X, and X2 both represent methyl, fluorine, chlorine or bromine X, and X, both represent chlorine or bromine, and R, represents hydrogen or ethyl, or X, and X2 both represent methfl or nuorine, X, and X4 both represent chTorine or bromine, and R, represents methyl, R2 represents hydrogen, methyl, cyano or ethynyl, and each of Y, and Y2 represents hydrogen, halogen, methyl or trifluoromethyl.

The compounds of the formuta I are prepared by methods which are known per se, for example as follows : PATENTS ACT, 1949 SPECIFICATION NO 1588212 In pursuance of Section 8 of the Patents Act, 1949, the Specification has been amended in the followingmanner: Page 1, line 17, after trifluoromethyl delete full stop insert comma Page 1, after line 17, page 7, after line 28, insert with the proviso that when R, represents methyl, X1 and X2 both represent fluorine and Y, and Y2 each represent hydrogen chlorine or methyl, R2 represents methyl.

Page 7, line 28, after fluorine delete full stop insert comma THE PATENT OFFICE 20 January 1983 Bas 94482/1 (54) NEW CYCLOPROPANECARBOXYLIC ACID ESTERS (71) We, CIBA-GEIGY AG, a Swiss body corporate, 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 particularly described in and by the following statement :- The present invention relates to cyclopropanecarboxylic acid esters, to a process for their manufacture and to their use in pest control.

The cyclopropanecarboxylic acid esters have the formula

wherein X, and X, both represent methyl, fluorine, chlorine or bromine X, and X4 both represent chlorine or bromine, and R, represents hydrogen or ethyl, or X, and X2 both represent methyl or fluorine, X3 and X4 both represent chlorine or bromine, and R, represents methyl, R2 represents hydrogen, methyl, cyano or ethynyl, and each of Y, and Y2 represents hydrogen, halogen, methyl or trifluoromethyl.

The compounds of the formula I are prepared by methods which are known per se, for example as follows :

y V l \/2 t~ Y2 1) X2-C-HC-CH-CH-C-OH + Z-CH-O.-, S 3"c% % R 2 2 Cl3 1 (ici) (") OH) acid acpeptior. j Xl X4 O Yl 2) X2-C-CH-CH-CH-C-Z + HO-CH \ -0 \/ X3/C\ R2 Y2 CH3 R1 (V) (IV) acid acceptor 0 y X1 X4 O Y1 3) X-C-CH-CH-CH-C-OH + HO-CH i O 2 X \C/R y C R t. 'y 3/\ 2"2 CH3 1 (II) (V) hydrophilic agent p I 4) X2-C-CH-CH-CH-C-OR + HO-CHo Y X -C R 2 CH3 R1 (VI) (V) () -ROH ''I N 1 5) \ : =CH-CH-CH-C-0-CH- < )-0-f) bromination < z I-cr I CH3 R1 (Vil) (each of X3 and X4 is bromine) In the formulae II to VII, R"R2, X"to X4, Y1 and Y2 are as defined in formula 1.

In the formulae III and IV, Z represents a halogen atom, especially a chlorine or bromine atom, and in formula VI R represents C,-C, alkyl, especially methyl or ethyl.

Suitable acid acceptors for processes I and 2 are in particular tertiary amines, such as trialkylamine and pyridine, and also hydroxides, oxides carbonates and bicarbonates of alkali metals and alkaline earth metals, and in addition alkali metal alcoholates, for example potassium tert-butylate and sodium methylate. As hydrophilic agent for process 3, dicyclohexylcarbodiimide can be used for example. Processes I to 5 are carried out at a reaction temperature between-10 and 120 C, usually between 20 and 80 C, under normal or elevated pressure and preferably in an inert solvent or diluent. Examples of suitable solvents or diluents are: ether and ethereal compounds, for example diethyl ether, dipropyl ether, dioxane, dimethoxy ethane and tetrahydrofurane ; amides, such as N, N-dialkylated carboxamides : aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xylenes, chloroform and chlorobenzene ; nitriles, such as acetonitrile ; dimethyl sulphoxide ; and ketones, such as acetone and methyl ethyl ketone.

The starting materials of the formulae II to Vll are known or can be prepared by methods analogous to known ones. Thus, for example, appropriate starting materials of the formulae 11 and IV can be prepared by chlorination or bromination of a compound of the formula :

wherein R2 is hydroxyl or a halogen atom and X represents chlorine or bromine.

The compounds of the formula I are in the form of a mixture of different optically active isomers if individual optically active starting materials are not used in the reaction. The different isomer mixtures can be separated into the individual isomers by known methods. The compound of the formula I is to be understood as comprising both the individual isomers and the mixtures thereof.

The compounds of the formula I are suitable for controlling a variety of animal and plant pests. In particular, the compounds of the formula I are suitable for controlling insects phytopathogenic mites and ticks, for example of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.

In particular, the compounds of the formula I are suitable for controlling insects which are harmful to plants, especially insects which damage plants by eating, in ornamentals and crops of useful plants, especially in cotton plantations (e. g. Spodoptera littorals and Heliothis virescens) and in vegetable crops (for example Leptinotarsa decemlineata and Myzus persicae).

The active compounds of the formula I also have a very good action against flies, for example Musca domestica and mosquito larvae.

The insecticidal and/or acaricidal action can be substantially broadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides. Examples of suitable additives include: organic phosphorus compound) nitrophenols and derivatives thereof, formamidines, ureas, pyethoids, carbamates, and chlorinated hydrocarbons.

Compounds of the formula I are also combine with particular advantage with substances which exert a synergistic or potentiating effect on pyrethoids. Examples of such compounds include : piperonyl butoxide, propynyl ether, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2- (3, 4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamex or Sesoxane), S, S, S-tributylphos- phorotrithioate, 1, 2-methylenedioxy-4 (2- (octylsulphonyl)-propyl)- benzene.

The compounds of the formula I may be used as pure active substance or together with suitable carriers and/or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in the art of formulation, for example natural or regenerated substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders and/or fertilisers.

The compositions of the present invention are manufactured in known manner by homogeneously mixing and/or grinding active substances of the formula I with the suitable carriers, with or without the addition of dispersants or solvents which are inert to the active substances.

The compounds of the formula I may be processed to the following formulations: Solid formulations : Dusts, tracking powders and granules (coated granules, impregnated granules and homogeneous granules).

Liquid formulations : a) active substances which are dispersable in water wettable powders, pastes and emulsions ; b) solutions.

The content of active substance in the above described compositions is generally between 0. 1% and 95%, though concentrations of up to 99.5'/' or even pure active substance can also be used if the compositions are applied from an aircraft or other appropriate application devices.

The compounds (active substances) of the formula I can, for example, be formulated as follows (throughout the present specification all parts and percentages are by weight): Dusts The following substances are used to produce a) a 5'/', and b) a 2% dust: a) 5 parts of active substance.

95 parts of talc ; b) 2 parts of active substance, I part of highly disperse silicic acid, 97 parts of talc.

The active substances are mixed with the carriers and ground.

Granules The following substances are used to produce 5% granules : 5 parts of active substance 0. 25 parts of epichlorohydrin, 0.25 parts 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 the mixture is dissolved in 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The resultant solution is sprayed on kaolin, and the acetone is subsequently evaporated in vacuo.

Wettable powders.

The following constituents are used for the preparation of a) a 40%, b) and c) a 25%, and d) a 10% wettable powder: a) 40 parts of active substance, 5 parts of sodium ligninsulphonate, part of sodium dibutyinaphthalenesulphonate, 54 parts parts of silic acid. b) 25 parts of active substance, 4.5 parts of calcium ligninsulphonate, 1. 9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1 : 1), 1. 5 parts of sodium dibutylnaphthalenesulphcnate, 19. 1 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 substances are homogeneously mixed with the additives in suitable mixers and the mixture is then ground in appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of the desired concentration.

Emulsifrable concentrates : The following substances are used to produce a) a 10 ", b) a 25 ,, and c) a oni, emulsifiable concentrate: a) l0 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 alkylarylsulphonate calcium salt, 40 parts of dimethyl formamide, 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 dimethyl formamide, 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 cyclohexanene, 20 parts of xylene.

By diluting these concentrates with water it is possible to obtain emulsions of the required concentration.

Sprays : The following ingredients are used to prepare a) a 5% spray, and b) a 95% spray: a) 5 parts of active substance, part of epichlorohydrin, 94 parts of ligroin (boiling range 160 -190 C) ; b) 95 parts of active substance, 5 parts of epichlorohydrin.

The invention is further illustrated by the following Examples.

EXAMPLE I Preparation of a-cyano-m-phenoxybenzyl - (1', 2'-dichloro-l'. 2'-dibromoethyl-2- methylcyclopropanecabo, rylate 12 g of -cyano-m-phenoxybenzyl 3- (2', 2'-dichloro-vinyl)-2, 2-dimethylcyclopropanecarboxylate are dissolved in 100 ml of carbon tetrachloride. To this solution are added dropwise 4.77 g ouf bru at 20 -30 C. The carbon tetrachloride is then distilled off, yielding the compound of the formula

with a refractive index of n40 : 1. 5776 (isomer mixture).

The following compounds are prepared in analogous manner:

CH Br CH--C-CH-CH-CH-COO-CH-f-O-ji"D'1. 5675 Br isomer mixture CH3 CH3 CH3Br CH -H-CH-CH-COO-CH nD 1. 5605 Br C/ isomer mixture CH3 CH3 Cl Br Cl-H-CH-CH-COOCH n 40 : 1. 5828 BU CL 'isomer mixture CHEZ C1 Br Cl-H-CH CH-COO-CH-----O D Br C CN '.,. ir \ isomer mixture CH3 C2H5 EXAMPLE 2.

Insecticidal stomach poison action Cotton plants were sprayed with a 0. OS ; a aqueous emulsion of active substance (obtained from a 10% emulsifiable concentrate). After the spray coating had dried, the cotton plants were populated with Spodoptera littoralis and Heliothis virescens in the L3-stage. The test was carried out at 24 C and 60% relative humidity.

In this test, the compounds of Example I exhibited a good insecticidal stomach poison action against Spodoptera and Hetiothis larvae.

EXAMPLE 3 Action against Chilo suppressalis Rice seedlings of the variety Caloro were transplanted into plastic pots (6 plants per pot) having a diameter of 17 cm at the top and reared to a height of about 60 cm. Infestation with Chilo suppressalis larvae (L,-stage, 3 to 4 mm in length) took place two days after the addition of active substance in granule form (rate of application : 8 kg of active ingredient per hectare) to the paddy water. Evaluation of the insecticidal action was made 10 days after addition of the granules. In this test, the compounds of Example 1 acted against Chilo suppressalis.

EXAMPLE 4.

Acaricidal action Twelve hours before the test for acaricidal action, Phaseolus vulgaris plants were populated with an infested piece of leaf from a mass culture of Tetranychus urticae. The mobile stages which had migrated to the plants were sprayed with the emulsified test preparations from a chromatography atomiser in such a way that the spray broth did not run off. The number of living and dead larvae, adults and eggs was evaluated under a stereoscopic microscope after 2 and 7 days and the result expressed in percentage values. During the test run, the plants stood in greenhouse compartments at 25 C.

In this test, the compounds of Example I acted against adults, larvae and eggs of Tetranychus urticae.

EXAMPLE 5 Action against ticks A) Rhipicephalus bursa Five adult ticks and 50 tick larvae were counted into each of a number of test tubes and immersed for I to 2 minutes in 2 mi of an aqueous mulsion containing a concentration of 100, 10, 1 or 0. 1 ppm of test substance. Each test tube was then sealed with a cotton-wool plug and placed on its head to enable the cotton wool to absorb the active substance mulsion. Evaluation of the action against adults was made after 2 weeks and of that against larvae after 2 days. Each test was repeated twice.

B) Boophilus microplus (larvae) Tests were carried out with 20 OP-sensitive and 20 OP-resistant larvae using aqueous mulsions similar to those used in Test A. (The resistance refers to the tolerance towards diazinone). The compounds of Example I acted in these tests against adults and larvae of Rhipicephalus bursa and OP-sensitive and OP-resistant larvae of Boophilus microplus.

Claims

WHAT WE CLAIM IS :- 1. A compound of the formula

wherein each of Y, and Y2, which may be the same or different, represents hydrogen, halogen, methyl or trifluoromethyl, R2 represents hydrogen, methyl, cyano or ethynyl, X, and X, both represent chlorine or bromine, and either R, represents hydrogen or ethyl, and X, and X, both represent methyl, fluorine, chlorine or bromine, or R, represents methyl, and X, and X2 both represent methyl or fluorine.
2. The compound of the formula
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. A process for preparing a compound as claimed in claim 1, which process comprises reacting a compound of the formula

(wherein R, and X, to X, are as defined in claim I and Z represents a halogen atom), in the presence of an acid acceptor with a compound of the formula

wherein R,, Y, and Y, are as defined in claim 1.
8. A process for preparing a compound as claimed in claim I wherein X, and X4 represent bromine, which process comprises brominating a compound of the formula

wherein R,, X"X,, Y, and Y2 are as defined in claim 1.
9. A process for preparing a compound as claimed in claim I substantially as described herein.
10. A process for preparing a compound as claimed in claim I substantially as described in Example 1.
1 I. A compound according to claim I prepared by the process claimed in any one of claims 7 to 10.
12. A pesticidal composition which contains, as active ingredient, a compound as claimed in any one of claims I to 6 together with a suitable carrier and/or other ingredient.
13. A composition according to claim 12 which contains the active ingredient together with a solid extender and optionally a surface active agent or together with a liquid diluent and a surface active agent.
14. 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 I to 6.
15. A method according to claim 14 wherein the pests are insects or prepresentatives of the order Acarina.
16. A compound according to claim I wherein each of Y, and Y2 which may be the same or different, represents hydrogen or halogen and R, is hydrogen or methyl.
17. A pesticidal composition which contains, as active ingredient, a compound as claimed in claim 16 together with a suitable carrier and/or other ingredient.
18. A composition according to claim 17 which contains the active ingredient together with a solid extender and optionally a surface active agent or together with a liquid diluent and a surface active agent.
19. A method of combating animal or plant pests at a locus, which method comprises applying to the locus a compound as claimed in claim 16.
20. A method according to claim 19 wherein the pests are insects or representatives of the order Acarina.