CA1152092A

CA1152092A - Pesticidal phenoxybenzyl cyclopropanecarboxylate derivatives

Info

Publication number: CA1152092A
Application number: CA000296685A
Authority: CA
Inventors: Jozef Drabek; Peter Ackermann; Saleem Farooq; Laurenz Gsell; Odd Kristiansen; Willy Meyer
Original assignee: Ciba Geigy Investments Ltd
Current assignee: Novartis AG
Priority date: 1977-02-11
Filing date: 1978-02-10
Publication date: 1983-08-16
Also published as: FR2380248B1; DE2805312A1; ES466862A1; EG13106A; TR20016A; IT1093705B; IT7820194A0; NL7801510A; BE863839A; GB1588212A; FR2380248A1; IL54009A0; JPS53105462A; MX5368E

Abstract

Abstract of the Disclosure Cyclopropanecarboxylic acid esters of the formula (I) wherein X1 and X2 represent methyl, fluorine, chlorine or bromine, X3 and X4 represent chlorine or bromine, and R1 represents hydrogen or ethyl, or X1 and X2 represent methyl or fluorine, with the proviso that X1 and X2 are not both fluorine, X3 and X4 represent chlorine or bromine, and R1 represents methyl, R2 represents hydrogen, methyl, cyano or ethynyl, and each of Y1 and Y2 represents hydrogen, halogen, methyl or trifluoromethyl, processes for their manufacture and their use in pest control.

Description

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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 I 1 IX4 Yl

2 I CH Cl\ / H C O IH ~ ~ Y2 (I) wherein Xl and X2 represent methyl, fluorine, chlorine or bromine, X3 and X4 represent chlorine or bromine, and Rl represents hydrogen or ethyl, or Xl and X2 represent methyl or fluorine, with one proviso that Xl and X2 are not both fluorine, X3 and X4 represent chlorine or bromine, and Rl represents methyl, R2 represents hydrogen, methyl, cyano or ethynyl, and each of Yl 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:
1 1X4 0 Yl

3 / \ 2 Y2 (II) (III) acid acceptor>

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Xl X4 O Yl X2 ,C CH C~-- CH-C-Z + Ho-CH~3-o~ 2 CH3 Rl (V) (IV) acid acceptor ~ I .

~ 1 X4 o Y
2 , ~ ~CH C -OH + HO-CH~-O~ 2 CH3 Rl (II) (V) hydrophilic age~t I

, 3 / \ 2 CH3 Rl (VI ) (V) -ROH

S ) ~C =C H -C H - C H - C -O -C H~O ~ bromi~

CH3. Rl (VII) (each of X3 and X4 is bromine) In the formulae II to VII, Rl, R2, Xl.to X4, Yl and Y2 are as defined in formula I.

~2~Z

In the formulae III and IV, ~ represents a halogen atom, especially a chlorine or bromine atom, and in formula VI
R represents Cl-C~alkyl, especially methyl or ethyl.
Suitable acid aCceptors for processes 1 and 2 are in par-ticular 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 exampIe potassium tert-butyl-ate and sodium methylate. As hydrophilic agent for process 3, dicyclohexylcarbodiimide can be used for example. Processes l to 5 are carried out at a reaction tetnperature between -10 and 120C, usua]ly between 20 and 80C, under normal or elevated pressure and preferably in an inert solvent or di-luent. Examples of suitable solvQnts or diluents are: ether and ethereal compounds, for example diethyl ether, dipropyl ether, dioxane, dimethoxy ethane and tetrahydrofurane; amides, such a~ N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xy-lenes, chloroform and chlorobenæene; nitriles, such as ace-tonitrile; dimethyl sulphoxide; and ketones, such as acetone and methyl ethyl ketone.
The starting materials of the formulae II to VII are known or they can be prepared by methods analogous to known ones.
The co~pounds of the formula I are in the form of a mixture of different optically active isomers if individual opti-cally active starting materials are not used in the reaction.
The di~ferent isomer mixtures can be separated into the in-dividual isomers by known methods. The compound of the for-mula I is to be understood as comprising both the indivi-dual isomers and the mixtures thereof.

~lS2(~92 ~he con~pounds of the formula I are suitable for controllin~
a variety of animal and plant pests. In particular, the com-pounds of the formula I are suitable or controllin~ insects, phyt~pathogenic mites and ticks, for example o the orders:
Lepidoptera, Coleootera, 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 plan~s, especial-ly insects which damage plants by eating, in ornamentals and crops of useful plants, especially in cotton plantations (e.g. Spodoptera littoralis and Heliothis virescens) and in vegetable crops (for example Leptinotarsa decemlineata and Myzu8 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 substan-tially bxoadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides. Examples of-suitable additives include: organic phosphorus compounds, nitrophenols and derivatives thereof, ~ormamidines, ureas, pyethroids, carbamates, and chlorinated hydrocarbons.
Compounds of the formula I are also combined with parti-cular advantage with substances which exert a synergistic or potentiating effect on pyrethroids. Examples of such com-pounds 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-tributylphosphorotrithioate, 1,2-Methy-lenedioxy-4(2-(octylsulphonyl)-propyl)-benzene.

,, 1 ~5~
The compounds o~ the formula I ~ay be used as pure acti-ve substance or together with suitable carriers and/or addi-tives~ Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in the art of fonnulation, for example natural or r~generated sub-stances, solvents, dispersants, wetting agents~ tackifiers, thickeners, binders and/or fertilisers.
The compositions of the present invention are manufac-tured in known manner by homogeneously mixing and/or grin-ding active substances of the foL~ula 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, impregllated 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 con-centrations 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 ~ormula I can, for example, be formulated as follows (throughout the pre-sent specification all parts and percenkages are by weight):

.

, llSZ(~Z

Dus~s The following substances are used to produce a) a 5% and b) a 2% dust:
a) S parts of active substance, parts of talc;
b) 2 parts of active substance, 1 part of highly disperse silicic acid, 97 parts of talc.
~ he active substances are mixed with the carriers and ground.

Granules The following substances are used to produce 5%
granules:
S parts of active substance 0.25 parts of epichlorohydrin, 0.25 parts o~ 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 mixt~re is dissolved in 6 parts of acetone; the poly-ethylene glycol and cetyl polyglycol ether are then added.
The resultant solution is sprayed on kaolin, and the ace-tone is qubsequently evaporated in vacuo.

115~(~92 W able powders_ The following constituents are used for the preparation o 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, 1 part of sodium dibutylnaphthalenesulphonate, 54 parts parts of silic~c 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 dibutylnaphthalenesulphonate, 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 ~ixture (1:1), 8~3 parts of sodium alumlnium silicate, 16,5 parts of kieselguhr, 46 parts of kaolin;
d) 10 parts of active substance, f 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

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The active substances are homogeneously mixed with the additive~ in suitable mixers and the mixture i~ then ground in appropriate mills and rollers. Wettable powders are ob-tained which can be diluted with water to give suspensions of the desired concentration.

Emulsiiable 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 alkylarylsulphonate calcium salt, parts of dimethyl formamide, 43~2 parts of xylene;
b) 25 parts of active substance, 2,5 parts of epoxidised vegetable oil, parts of alkylarylsulphonatetfatty alcohol polyglycol ether mixture, 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 cylcium dodecylbenzenesulphonate, parts of cyclohexanene, parts of xylene.
By diluting these concentrates with water it is possible to obtain emulsions of the required concentration.

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Sprays:
The ollowing ingredients are used to prepare a) a 5%
spray, and b) a 95% spray:
a) 5 parts of active substance, 1 part of epichlorohydrin, 94 parts of ligroin (boiling range 160-190C);
b) 95 parts of active substance, parts of epi.chlorohydrin.
The invention is further illustrated by the following Examples.

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Example 1 Preparation of ~-cyano-m-phenoxybenzyl 3-(2',2l-dichloro-1', 2'-dibromoethyl-2-methylcyclopropanecarboxylate . _ . . .

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 of Br2 at 20-30C. The carbon tetrachloride is then distilled off, yielding the compound of the formula Cl Br 0 CN
C~ ~CH-C-O-CH~-O~

with a refractive index of n40. 1.5776 (isomer mixture).
The following compounds are prepared in analogous manner:

CH3-C - CH-CH - CH-C00-CH ~ -0 ~ nD : 1.5675 ~ \ isomer mixture C~13 CH3 CH3 Br 3 , CH\ - CH - C00-CH ~ 0 ~ n40 : 1.5605 / \ isomer mixture ~S2~92 Cl Br Br CH ~ ~3 nD : 1 . 5 8 2 8 ' isomer mixture Cl- C - CH-CH ~ CH-COO-CH~-O~ nD :1,.5639 ~ ~ isomer mixture Example 2 Insecticidal stomach pois~n action .. . . ~

Cotton plants were sprayed with a 0.05% aqueous emulsion of active substance (obtained from a 10% emulsifiable concen-trate). After the spray coating had dried, the cotton plants were populated with Spodoptera li~toralis and Heliothis vi-rescens in the L3-stage. The text was carried out at 24C
and 60% relative humidity.
In this teqt, the compounds of Example 1 exhibited a good in-secticidal stomach poison action against Spodoptera and He-liothis larvae.

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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. Inf~sta-tion with Chilo suppressalis larvae (Ll-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 ac-tive 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 -Twe~ e hours before the tes~ 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 ato-miser in such a way that the spray broth did not run off. The number of living and dead larvae, adults and eggs was eva-luated under a stereoscopic microscope after 2 and 7 days ,. ~ . .... . . . . .. . .

~'1 5;~(~92 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 Eæample 1 acted against adults, larvae and eggs of Tetranychus urticae.

xample 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 1 to 2 minutes in 2 ml of an aqueous emulsion 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 co~ton wool to absorb the active substance emul-sion. Evaluatioh 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) Test were carried out with 20 OP-sensitive and 20 OP-resist-ant larvae using aqueous emulsions similar to those used in Test A. (The resistance refers to the tolerance towards dia-zinone). The compounds of Exampl-_ 1 acted in these tests against adults and larvae of Ehipicephalus bursa and OP-sen-sitive and OP-resistant larvae of Boophilus microplus.

.

llS~092 Action against Erysiphe graminis on Hordeum vulgare Barley plants about 8 cm in height were sprayed with a spray broth (0.05% of active ingredient~ prepared from a wettable powder of the active compound. 48 hours later, the treated plants were dusted with conidia of the fungus. The infected barley plants were stood in a greenhouse at about 22C and the fungus attack was evaluated after 10 days. In this test, the compounds of Example 1 acted against Erysiphe graminis.

.. . , , . . . . . . . . . . ~

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A cyclopropanecarboxylic acid ester of the formula (I) wherein X1 and X2 represent methyl, fluorine, chlorine or bromine, X3 and X4 represent chlorine or bromine, and R1 represents hydrogen or ethyl, or X1 and X2 represent methyl or fluorine, with the proviso that X1 and X2 are not both fluorine, X3 and X4 represent chlorine or bromine, and R1 represents methyl, R2 represents hydrogen, methyl, cyano or ethynyl, and each of Y1 and Y2 represents hydrogen, halogen, methyl or trifluoromethyl.

2. The compound as claimed in claim 1 of the formula

3. The compound as claimed in claim 1 of the formula

4. The compound as claimed in claim 1 of the formula

5. The compound as claimed in claim 1 of the formula

6. The compound as claimed in claim 1 of the formula

7. A process for the manufacture of a compound as claimed in claim 1, which comprises a) reacting a compound of the formula wherein R1 and X1 to X4 are as defined in claim 1 and Z represents a halogen atom, in the presence of an acid acceptor, with a compound of the formula wherein R2, Y1 and Y2 are as defined in claim 1, or b) if X3 and X4 represent bromine, brominating a compound of the formula wherein R1, R2, X1, X2, Y1 and Y2 are as defined in claim 1.

8. A method of controlling animal and plant pest at a locus, which comprises applying to the locus a pesticidally effective amount of a compound according to claim 1, 2 or 3.

9. A method of controlling animal and plant pest at a locus, which comprises applying to the locus a pesticidally effective amount of a compound according to claim 4, 5 or 6.

10. A method of controlling animal and plant pests of the order of Acarina at a locus which comprises applying to the locus a pesticidally effective amount of a compound according to claim 1, 2 or 3.

11. A method of controlling animal and plant pests of the order of Acarina at a locus which comprises applying to the locus a pesticidally effective amount of a compound according to claim 4, 5 or 6.