FR2462419A1 - NOVEL CYCLOPENTENONE CYCLOPROPANECARBOXYLATES, THEIR PRODUCTION AND THEIR USE AS INSECTICIDES - Google Patents

Abstract

CARBOXYL ESTER OF FORMULA I BELOW, IN WHICH X IS AN ATOM OF CHLORINE, BROMINE OR FLUORINE; INSECTICIDES CHARACTERIZED BY THE FACT THAT THEY CONTAIN THE CARBOXYL ESTER OF FORMULA I AS AN ACTIVE ELEMENT; AND PROCESS FOR THE PREPARATION OF THE CARBOXYL ESTER OF FORMULA I, CHARACTERIZED BY THE REACTION OF A CARBOXYLIC ACID OF FORMULA II, OR OF A REACTIVE DERIVATIVE OF THIS ACID, WITH AN ALCOHOL OR A REACTIVE DERIVATIVE OF THE SAME. OF FORMULA III, IN WHICH A IS A HYDROXYL GROUP OR A TOSYLOXY GROUP.

Description

the present invention relates to new carboxylic esters.

calves of formula (I) CH2

H H H

HC E C - CH2 -I X (1)

2 oc - C -C - C S 0o C \

CH3 CH3

in which X is a chlorine, bromine or fluorine atom, their production and insecticides of low toxicity and action

  which contain these esters as active ingredient.

Since a large number of infectious diseases are carried by insects, the extermination of these insects is a very effective means to prevent these diseases from spreading and the use of insecticides is the most effective measure to achieve this. . As a result, insecticides play a very big

  role in maintaining a high standard of living for the human race.

Many high quality insecticides have been invented to date to achieve this goal and are used in different

regions with good results. However, organo- insecticides

  chlorinated, such as BHC and DDT, and organophospho- insecticides

  phoreas have seen their scope of restriction significantly, by the fact that they have given birth to insects resistant to them and that they have raised difficulties of various kinds, including environmental pollution and the

toxicity to non-target organisms. With the new insecti-

  cides that have taken over from the precedents, this problem of insects

  resistant is becoming serious in different areas.

In view of these circumstances, the development of new insecticides

  calves and more efficient is eagerly desired. From this point devueg we can say the following about the essential properties for insecticides: naturally, a strong insecticidal activity and a marked effect of "knockdown", ie immobilization

  rapid insect, are necessary, but in addition it requires impe-

of an insecticide, at present, that it has low toxicity towards non-target organisms, such as mammals, that its persistence is zero and that it has little effect polluting the environment. Natural pyrethrin is

somewhat toxic to mammals and decomposes easily-

  ment under the action of external conditions, so that it has some of the above properties, essential for insecticides. But its insecticidal activity is relatively weak in comparison with organophosphates and carbamates; moreover, it is broken down too quickly to keep a residual effect and it is expensive L- "Advantages and Disadvantages of Pyrethrum"

  (J.3. Casida, Academic Press, New York and London, 1973) pp. 307 -

311J.

The inventors have done extensive research

dies to develop compounds that fill in the gaps

  natural pyrethrin and superior to insecticides

currently in use. Following this work, it was discovered that the compounds of formula (I) according to the invention have

the following characteristics: -

(1) A remarkably fast effect (knockdown effect) and a

strong insecticide activity.

  (2) Relatively low toxicity to mammals.

(3) Excellent insecticidal activity against insects

resistant to organophosphates and carbamates.

  (4) The possibility of producing them at relatively low cost.

This is how the authors came to the present information.

  vention. The compounds of the present invention fall, from a general point of view, within the framework of the Japanese patent application published before examination No. 47531/1974. However, in this request

patent, there is no particular description of the compounds

  and, all the more reason, there is no reference to physical properties, examples of synthesis, or insecticidal activity

compounds.

  The authors of the present invention were the first to discover that the compounds of formula (I) in question have a much higher knockdown effect than any other compound cited in the patent application relating to the present compounds. By

  Therefore, the invention is of great importance.

The compounds of the present invention are obtained by reacting a carboxylic acid of formula (II) H E x

HOC - C C - C = (II)

O / C

CH3 CH3

  in which X has the meaning given above, or a reactive derivative of this acid, with an alcohol or a reactive derivative thereof of formula (III) CH3

HC C - CH2 A (III)

wherein A is a hydroxyl group or a tosyloxy group, in the presence of an appropriate solvent, a reaction aid and a catalyst if necessary. The reactive derivative of the carboxylic acid of formula (II) considered here can 8trechaîsi for example among acid helogenides, acid anhydrides, lower alkyl esters, alkali metal salts and salts of tertiary organic bases. The reactive alcohol derivative of formula (III) may for example be a compound obtained

  replacing the hydroxyl group of the alcohol with a halo atom

gene or tosylozy group.

  The carboxylic esters of formula (I) have isomeric forms, namely geometric isomers (Cie and trans isomers) according to the steric configuration of the carboxylic acid part and optical isomers based on the asymmetric carbon atoms of the acid parts carboxylic and alcohol. It goes without saying that all these isomers also fall within the framework

of the present invention.

  We can summarize the process for the preparation of carboxyl esters.

  liques of the present invention by saying that the carboxylic ester of formula (I) is obtained by reaction of a carboxylic acid of formula (II)

H E H (

HO - C - a - / C - a = C (II)

O C

0H3 GH3

  in which x has the meaning given above, or a reactive derivative of this acid, with an alcohol or a reactive derivative thereof of formula (III) CH3

HC - C - CH2 A

P (III)

or

  wherein A is a hydroxyl group or a tosyloxy group.

  In addition, the aforementioned reactive derivative of the carboxylic acid is an acid halide (acid chloride or acid bromide) or an acid anhydride when A in formula (III) is a hydroxyl group, and it is an alkaline salt of the acid when A in formula (III) is a tosyloxy group. In other words:

Synthesis A: Reaction between alcohol and carboxylic halide.

  The ester of formula (I) sought is obtained by reacting an alcohol of formula (III ') CHC

HCEC -0CH2 OH

2 (III ')

0 -

with a carboxylic halide (chloride or bromide), preferably

  Reference to a carboxylic chloride, of formula (II)

H H H

Ho - C - 0 - - 0 (II)

O C

CH3 CH3

  in which X has the meaning given above, at a time

  temperature from -30- to 100 ° C. for 0.5 to 20 hours in an inert solvent (for example benzene, toluene, hexane, ether),

  in the presence of a base (for example pyridine, latriethylamine).

  The base is usually used in a proportion of 1.0 to 3.0 mol per 1 mol of the aleool of formula (III '). The proportion of the carboxylic halide of formula (II) used is 1.0

  at 1.5 mol per 1 mol of the alcohol of formula (III ').

  Synthesis B: Reaction between alcohol and carboxylic anhydride, The ester of formula (I) sought is obtained by reacting an alcohol of formula (III ') CH3

HC E C - CH2 OH

(III ')

with a carboxylic anhydride of formula (II)

H H H

g! II X HO - C - C - C = a _

"X

O / C

0 \ /

CH3 CH3

  in which X has the meaning given below temperature from -20 to 100 2C for 1 to 20 hours inert (for example benzene, toluene, 1 'in the presence of a base (for example pyridin The base is used for habit in a p to 3.0 moles per 1 mole of the alcohol of formula portion of the carboxylic anhydride of formula (II)

essus, at a time

in a hexane solvent, acetone)

e, trietbhylamine).

ratio of 1.0

(III '). The pro-

(II) used is

from 1.0 to 1.5 mol per 1 mol of the alcohol of formula (III ').

Synthesis C: Dehydration reaction between alcohol and carboxylic acid The ester of formula (I) sought is obtained by reacting an alcohol of formula (III ') CH3

HC _ C - CH2 - OH (II ')

with a carboxylic acid of formula (II)

H H H X

HOC - C - C - C = C (II)

È \ C X

CH 3CH3

  in which X has the meaning given above, at a time

  temperature from 0 to 150oC for 0.5 to 10 hours in an inert solvent (for example benzene, toluene, ether, acetone)

in the presence of a dehydrating agent (for example dicyclohexyl-

carbodiimide).

  The dehydrating agent is usually used in a proportion

- tion of 1.0 to 2.0 mol per 1 mol of the alcohol of formula (III ').

  The proportion of the carboxylic acid of formula (II) used

  is from 1.0 to 1.5 mol per 1 mol of the alcohol of formula (III ').

  Synthesis D: Reaction between alcohol tosylate and carboxylic acid salt The ester of formula (I) sought is obtained by reacting an alcohol tosylate of formula (III) CH3

HC - C- C2A (III)

in which A is a tosyloxy group, with an alkaline salt

2,462 4 1 9

  carboxylic acid represented by formula (IV)

H H H

  t t t z Mo - c - c - C = C (Iv) n% 1x

O C / X

0 /

CH3 YH3

  in which X has the meaning given above and M is a sodium or potassium atom, at a temperature of 02 to 150o0 for 0.5 to 10 hours in an inert solvent (for example the

benzene, toluene, acetone, dimethylformamide, sulfoxy-

dimethyl).

  The proportion of the alkali salt of carboxylic acid represented by formula (IV) is from 1.0 to 1.5 mol per 1 mol of the tosylate

of alcohol of formula (III).

  The carboxylic esters of formula (I), obtained by

above described processes, can be purified by chromatography

  writing or distillation if necessary.

  The present invention will be illustrated in detail by the following examples, but which should not be interpreted

as limiting the invention.

Example 1

  (+) - 2-methyl-3-2'- was dissolved in toluene (50 ml)

propynyl-cyclopent-2-en -4-on-l-1ol (3.0 g) and pyridine

  (2.4 g) and anhydride (+) - 2,2-dimethyl-3-cis- was added thereto

  2 ', 2' -dichlorovinylcyclopropane-carboxylic (8.0 g), then the mixture was stirred at 40 0 for 24 h. The reaction solution was poured into an aqueous hydrochloric acid solution and separated into the aqueous and toluene phases. The toluene phase has

been washed with a 5% aqueous solution of potassium carbonate-

  sium, then with an aqueous solution of sodium chloride and, by elimination of the solvent by evaporation, 6.6 g were obtained

  of a pale yellow oil. This oil was purified by chromato-

written on silica gel (developer solvent, mixture of

n-hexane / ethyl acetate) and 4.1 g of (+) - 2.2- were obtained

  dimethyl-3-cis-2 ', 2' -dichlorovinylcyclopropane-carboxylate 8-

  (+) - 2-methyl-3-2 '-propynyl-cyclopent-2-en-4-on-1-yl (compound A).

  Refractive index, 1.5310 (22.59C).

Example 2

(T +) - 2methyl-3-2'-propynyl-cyclopent-2-en-4-on-l-ol (3.0 g) was dissolved in dimethylformamide (50 ml)

  we added (+) - 2,2-dimethyl-3-trans-2 ', 2'-dichlorovinylcyclo-

  potassium propane carboxylate (2.5 g), then stirred at 6020 for 15 hours. The reaction solution was poured into an aqueous hydrochloric acid solution and extracted with ethyl acetate. The ethyl acetate phase was washed with a 5% aqueous solution of potassium carbonate, then with an aqueous solution of sodium chloride and, by elimination of the solvent by evaporation, 2.8 g of an oil were obtained Pale yellow. This oil was purified by chromatography on silica gel (developing solvent, mixture of n-hexane / ethyl acetate) and we obtained

  2.1 g of (+) - 2,2-dimethyl-3-trans-2 ', 2' -dichlorovinylcyclopropane-

  (+) - 2-methyl-3,2 '-propynyl-cyclopent-2-en-4-on-1- carboxylate

yle (compound B).

  Refractive index, 1.5282 (22.5 0).

Example 3

  (+) - 2-methyl-3-2'-pro- was dissolved in toluene (10 ml)

  pynyl-cyclopent-2-en-4-on-l-ol (320 mg) and pyridine (240m)

  and acid chloride (+) - 2.2- was added dropwise

  dimethyl-3-trans-2 ', 2' -difluorovinylcyclopropane-carboxylic acid, followed by stirring at room temperature for 5 hours. The

reaction solution was poured into an aqueous solution

of hydrochloric acid and separated into aqueous and toluene phases. The

toluene phase was washed with an aqueous solution of bicar-

sodium bonate, then with an aqueous solution of sodium chloride and, by elimination of the solvent by evaporation, 680 mg of a pale yellow oil were obtained. This oil was purified by chromatography on silica gel (developer solvent, mixture

  n-hexane / ethyl acetate) and 450 mg of (+) - 2.2- were obtained

  dimethyl-3-trans-2 ', 2' -difluorovinylcyclopropane-carboxylate

  (+) - 2-methyl-3-2'-propynyl-cyclopent-2-en-4-on-1-yl (compound 0).

9-

Refractive index, 1.4921 (25.020).

Example 4

  (+) - 2-methyl-3-2'-pro- was dissolved in toluene (10 ml)

  pynyl-cyclopent-2-en-4-on-l-ol (150 mg) and added acid (+) - 2, 2-dimethyl-3-cis-2 ', 2' -dibromovinylecyclopropane- carboxylice (300 mg) and dicyclohexylcarbodiimide (400 mg), then stirred

  at room temperature for 5 hours. The reaction solution

  It was poured into an aqueous solution of hydrochloric acid and separated into the aqueous and toluene phases. The toluene phase was washed with an aqueous solution of sodium bicarbonate, then

  with an aqueous solution of sodium chloride and, after eliminating

  tion of the solvent by evaporation, 410 mg of a pale yellow oil were obtained. This oil was purified by chromatography on silica gel (developing solvent, mixture of n-hexane / acetate

ethyl) and 320 mg of (+) - 2,2-dimethyl-3-cis-2 ', 2'- were obtained

  (+) - 2-methyl-3-2'-proljyrl- (dibromovinylcyclopropane-carboxylate)

cyclopent-2-en-4-on-1-yl (compound D).

  Refractive index, 1.5621 (22.520).

Example 5

(+) - 2-methyl-32'- was dissolved in toluene (10 ml)

  propynyl-cyclopent-24n-4-on-l-ol (150 mg) and pyridine (120

mg), then acid chloride (+) - was added dropwise

2, 2-dimethyl-3-cis-2, 2 '-dichlorovinylcyclopropane-carboxylic acid and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into a 5% aqueous hydrochloric acid solution and separated into the aqueous and toluene phases. The toluene phase was washed with an aqueous solution of sodium bicarbonate, then with an aqueous solution of sodium chloride and the solvent was removed by evaporation

  to give 320 mg of a pale yellow oil. This oil has been puri-

  checked by chromatography on silica gel (developing solvent, mixture of n-hexane / ethyl acetate) and 270 mg of (+) - 2,2dimethyl-3-cis-2 ', 2' -dichlorovinylcyclopropane-carboxyvlate were obtained.

of (+) - 2-methyl-3-2 '-propynyl-cyclopent-2-en-4-on-1-yl (ompos E).

  Refractive index, 1.5298 (24.090).

Example 6

(+) - 2-methyl-3-2'- was dissolved in toluene (30 ml)

propynyl-cyclopent-2-en-4-on-1-ol (1.50 g) and pyridine (1.20 g) and acid chloride (+) - 2 was added dropwise 2-dimethyl-3-cis trans-2 ', 2' -dichlorovinylcyclopropane-carboxylic and the solution was stirred at 2020 for 5 hours. The reaction solution was poured into an aqueous solution containing% hydrochloric acid and separated in aqueous and luene phases. The toluene phase was washed with an aqueous solution of sodium bicarbonate, then with an aqueous solution of sodium chloride and sacdhe on magnesium sulphate. The solvent has

was removed by evaporation and the residue was purified by chromium

matography on silica gel (developer solvent, mixture

  n-hexane / ethyl acetate) and 2.50 g of (+) - 2.2- were obtained

  dimethyl-3-cistrans-2 ', 2' -dichlorovinyl cyclopropane-carboxylate

  of (+) - 2-methyl-3-2 '-propynylcyclopent-2-en-4-on-1-yl (compound F).

Refractive index, 1.5290 (22.520).

The compounds of formula (I) according to the invention have a very rapid effect on insalubrious harmful insects such as flies, mosquitoes and cockroaches; in addition, they are very useful in the fight against insects harmful to agricultural crops, in particular plant hoppers, leaf hoppers, leucania caterpillars and harvest plots, diamondback moth (Plutella xvylostella), budworms, aphids, stem borers, as well as against insects harmful to stored cereals, especially the mite flour (Plodia interpunctella) and rice weevils (Sitophilus zeamais) and against parasitic lice and ticks animals. They

  are also useful for controlling other insect pests.

wheat. Furthermore, the compounds of the present invention not only have the effect of immobilizing the insects to death, but also a repellant effect, provoking a distancing reaction.

  insects with respect to their plant hosts.

The excellent properties of the carboxylic ester of formula

(I) are particularly remarkable with (+) - 2,2-dimethyl-

1 1

  (+) 2- 3-cis, trans-2 ', 2' -dichlorovinylcyclopropane-carboxylate

  methyl-3-2 '-propynyl-eyclopent-2-4n-4-on-1-yle, le (+) - 2,2-

dimethyl-3-trans-2 ', 2' -difluorovinyleyclopropane-carboxylate

(+) -2-methyl = 3-2'-propynyrl-cyclopent-2-4n.4-on-l-yle and the (+) -

2 2-dimethyl-3-cis-2 '2' -dibromovinylcyelopropane-carboxylate

  (+) -2-methyl-3-2 'propynyl-cyclopent-2n-4on-1-yl.

In practice, the compounds of the present invention may

  Can be used for various purposes in different forms of preparation.

tion.

In order to make the excellent pro-

  properties of the compounds of the present invention, some typical experimental examples are presented below. The compounds of formula (I) other than those of the examples also manifest

the same trend.

  Experimental Example 1 0.1 parts of each of the compounds of the invention and the reference compounds were dissolved in deodorized kerosene and made up to a total weight of 100 parts with kerosene, to obtain an oily spray of each of the compounds. . Ten adult female domestic cousins (Oulex iuions allens) and ten adult domestic flies (Muzca domestica) were released into a (70 cm) 3 glass chamber, in which they were sprayed

0.7 ml of this oily spray. Then we counted in function-

tion of the time elapsed the number of insects immobilized ("knocked-

  down ") and the value of TK50 (average knockdown time) was determined from the average knockdown ratio of three repetitive tests according to Finney's method. After 10 min, the experimental insects were collected and given gave 5% sugar water and then counted the dead and the living after

24 hours.

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009 C 009 <09 009 <009 <009 <OUf úL 0o6 LL Experimental example 2 An oily spray at 1% of each of the compounds of the invention and of the control compound was prepared using

  deodorized kerosene as solvent.

Ten adult German cockroaches (Blattella germanica) were released into a 10 cm diameter glass Petri boot, the inner wall of which was covered with a thin layer of petroleum jelly, and the boot was covered with nylon gauze. 50 mesh. Then 0.6 ml of the oily spray was sprayed 50 cm away from the box using a glass atomizer and the number of insects immobilized was counted after 5, 10

and 20 minutes.

  When preparing an insecticide and acaricide product from the compounds (I) of the invention, the compounds, as well as the conventional pyrethroids, can be formulated in any desired form of presentation, using the diluents used for the conventional insecticides and by applying the methods known in the art. The forms of presentation embrace by

example oily sprays, emulsified concentrates

wheat, dusting powders, aerosols, wet powders

  lables, granules, mosquito coils, heating and non-heating fumigants, baits in powder or solid form containing substances attracting insects and

  other forms chosen at will.

  Knockdown rate (%) Compound tested end to end after 5 min of 10 min of 20 min Compound A of the invention 93 100 100 Compound B of the invention 90 100 100 Compound C of the invention 100 100 100 Compound D of the invention 97 100 100 Compound E of the invention 100 100 100 Compound F of the invention 90 100 100 Allethrin 0 30 60 In addition, a more energetic insecticidal activity can be developed by mixing two or more of these compounds . Likewise, the insecticidal activity of the compounds of the invention can be enhanced by their mixture with synergistic substances of pyrethroids and other known products having a synergistic effect with llethrine and pyrethrin. The substances

  synergistic of pyrethroids are for example -L2- (2-butoxy-

  ethoxy) -ethoxyJ_4,5-methylene-dioxy-2-propyltoluene (eci-après

  called piperonyl butoxide), 1,2-methylene-dioxy-4 '2- (oc-

  tylsulfinyl) -propylJ-benzene (hereinafter called sulfoxide), 4- (3,4methylenedioxyphnyl) -5-methyl-1,3-dioxane (hereinafter

called sulfozanne), N- (2-ethylhexyl) -bicyclo2, 2, 17hepta-5-

  ene-2,3-dicarboximide (hereinafter called MGK-264), ether octa-

  ohlorodipropyl (hereinafter called S-421) and thiocyanoaretate

* isobornyl (hereinafter called Thanite).

  In general, carboxylic esters have poor resistance to light, heat and oxidation and it is therefore possible to obtain compositions whose effect is more stable by adding an appropriate amount of stabilizer to the stabilizers, Mention may be made, for example, of antioxidants and absorbents of the ultraviolet, in particular phenolic derivatives (for example BET, BHA), bisphenolic derivatives,

arylamines (e.g. phenyl-oe-naphthylamine, phenyl- -

  naphthylamine, condensation products of phenetidine and

  acetone) and benzophenonic compounds.

  In addition, universal compositions with excellent efficacy can be produced by mixing with other elements.

  active, for example allethrin, N- (chrysanthemoxymethyl) -

3,4,5,6-tetrahydrophthalamide (hereinafter called tetramethrin), the-

5-benzyl-3-furylmethyl ehrysanthemate (hereinafter called resme-

thrine), 3-phenoxybenzyl chrysanthemate (hereinafter called phenothrin), 5-propargylfurfuryle chrysanthemate,

  2-methyl-5-propargyl-3-furylmethyl chrysanthemate, the isomes

  res d-trans or d-cis, trans of these chrysanthemums, pyrethrum extracts, chrysanthemic esters d-trans or d-cis, trans

  d-allethrolone; 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclo-

3-phenoxybenzy propane-carboxylate, 2 ', 2' -dimethyl-3'L (2,2-

  dichlorovinyl) -cyclopropane-carboxylate (-cyano-3-phenoxybenmz

  2 ', 2', 3 ', 3' -tetramethylcyclopropane-carboxylate d 'c -cyano-3-

  phenoxybenzyl, u-cyano-3phenoxybenzyl 2- (4-chlorophenyl) -isovalerate and other cyclopropane-carboxylic esters cann

  organophosphate insecticides such as 0- (3-methyl-4-nitro-

phenyl) -0,0-dimethyl phosphorothioate (hereinafter called feni-

  trothion), O-0O-dimethyl 0-4-cyanophenylphosphorothioate (ci-

  after called Cyanophos), the 0- (2,2-dichlorovinyl) -phosphated '0,0-

dimethyl (hereinafter called Dichlorvos), Baycide, Vinyphate,

Malathion, Salithion, Papthion, Dipterex and Diazi-

no; carbamate insecticides like N-methylcarbamate c

  l-naphthyl, 3,4-dimethylphenyl N-methylcarbamate, N-

3-methylphenyl methylcarbamate, 2- N-methylcarbamate

  isopropoxyphenyl and S-methyl-N- (methylcarbamoyloxy) -thioaceto-

  imidate; N '- (2-methyl-4-chlorophenyl) -N, N-dimethylformamidine;

  2,3-bis (carbamoylthio) -2- (N, N-dimethylamino) hydrochloride -

  propane; other insecticides, microbial pesticides such as fungicides, nematocides, acaricides, growth regulators

plants, B.T. and B.M., composed of insect hormones, herbi-

  cides, fertilizers and other chemicals for agricultural use. We

can also expect a synergistic effect from such a mixture.

  The preparations considered above generally contain

0.01 to 80% by weight, preferably 0.05 to 60% by weight of the

  ment active (including other mixed elements). However, since the dose and the concentration of the active element depend on the form of presentation, the duration of application, the

application technique, application site, disease and-

  crops, we can conveniently increase or decrease them

  without taking into account the ranges indicated above.

The following are examples of preparations for

  the insecticides and acaricides of the invention.

Preparation example 1 0.2 parts of each of the compounds of the invention (A) to (F) are dissolved in kerosene and the solution is made up to parts with kerosene, to obtain a spray

oily of each compound.

  Preparation example 2 To 0.05 parts of the compound of the invention (A), 0.25 parts of piperonyl butoxide are added and the mixture is dissolved in kerosene and made up to 100 parts with kerosene to give

an oily spray. Preparation example 3 to 20 parts of each of the compounds of

  the invention (A) to (F), 15 parts of Sorpol 3005X (registered trademark of Toho Kagaku Co.) and 65 parts of xylene are added and the mixture is well stirred

  to form a solution. An emulsifying concentrate is thus obtained

ble of each compound.

  Example of reaction To 60 parts of each of the compounds of the invention (A) to (F), we add 10 parts of Sorpol 3005X (registered trademark of Toho Kagaku 0Co.) And 30 parts of xylene and the mixture is well stirred

  to form a solution. An emulsifying concentrate is thus obtained

ble of each compound.

  Example of variation To 10 parts of each of the compounds of the invention (B) and (D), 20 parts of S-421, 15 parts of Sorpol 3005X (see above) and 55 parts of xylene are added and the mixture is well agitated

  to form a solution. An emulsifying concentrate is thus obtained

ble of each compound.

  Preparation example 6 0.1 parts of the compound of the invention (C), 0.2 parts of

resmethrin, 7 parts of xylene and 7.7 parts of de-kerosene

  golden are well mixed to form a solution. The solution is loaded into an aerosol container. After attaching a valve to the container, 85 parts of a propellant (liquefied petroleum gas) is charged under pressure through the valve to

get an aerosol can.

  Preparation example 7 0.3 parts of the compound of the invention (E), 0.1 parts of d-cis, 3-phenoxybenzyl trans-chrysanthemate, 7 parts of exylene and 7.6 parts of deodorized kerosene are well mixed to form a solution. The solution is loaded into an aerosol container and an aerosol can is obtained by doing the same

as in preparation example 6.

  Preparation example 8 To 0.15 g of each of the compounds of the invention (C) and (E), 0.2 g of d-trans allethrin chrysanthemic ester and the

  mixture is dissolved in 20 ml of methanol. The solution is mixed

  uniformly, with stirring, with 99.65 g of a support for mosquito repellent coil containing Tabu powder, pyrethrum marc and wood powder in the ratio 3: 5: 1, then methanol is evaporated. 150 ml of water are added to the residue

and the mixture is well kneaded, put in the form of an anti-serpentine

  mosquito and dried. This gives a mosquito coil

of each compound.

  Preparation example 9 To 0.02 g of the compound of the invention (A), 0.05 g of dl-cis, 5-propargylfurfuryl trans-chrysanthemate and 0.1 g of BHT are added and the mixture is dissolved in an appropriate amount of chloroform. The solution is adsorbed uniformly in a

  sheet of filter paper 3.5 cm x 1.5 cm x 0.3 cm (thickness).

  A fibrous fumigant is thus obtained, intended to be heated on

a hot plate.

  Preparation example 10 To 20 parts of each of the compounds of the invention (B) and (D), we add 10 parts of fenitrothion (see above) and 5 pairs of Sorpol SM-200 (registered trademark of Toho Eagaku Co.) , then mix thoroughly. Then 65 parts are added to this mixture

  diatomaceous earth of 300 mesh by mixing it in a hammer.

A wettable powder of each compound is thus obtained.

  Preparation example 11 To 1 part of the compound of the invention (A), 2 parts of 3-methylphenyl N-methylcarbamate are added and the mixture is dissolved in 20 parts of acetone. Then the solution is well mixed with 97 parts of 300 mesh talc, being vigorously stirred in a mortar; the acetone is then removed by evaporation and a powder is obtained for sprinkling. Preparation example 12 To 3 parts of each of the compounds of the invention (A) and (B), 5 parts of Toyolignin eT (registered trademark of Toyo Spinning Co.) and 92 parts of Clay GeS (registered trademark of the Zieklite Mining Co.) and everything is well mixed with stirring

in a mortar.

  Then 10% of water is incorporated into the mixture which is granulated in a granulator and air dried. This gives a granule

of each compound.

Repair example 13 0.1 parts of the compound of the invention (D), 0.2 parts of the d-cis acid trans isomer of Fenothrin, 11.7 parts of deodorized kerosene and 1 part of Atmos 300 (emulsifier, registered trademark of Atlas Chemical Co.) are mixed, then the mixture is emulsified by the addition of 50 parts of pure water. The emulsion is then loaded into an aerosol container with 35 parts of a 3: 1 mixture of deodorized butane and deodorized propane;

  a water-based aerosol is thus obtained.

  The insecticidal effect of the esters of the present invention will now be illustrated in more detail by the examples.

of application that follow.

  Experimental example 3 ml of each of the oily sprays obtained in the preparation examples 1 and 2 were sprayed according to the

  Campbell lSoap and Sanitary Che- turntable method

micals, vol. 14, ne 6, 119 (1938) 3, using approximately 100 adult house flies (Musca domestica) per group. The

  adult house flies have been exposed to fog

ash for 10 min. The next day, we saw that more

  80% of the flies were killed in each case.

  Experimental example 4 The emulsifiable concentrate obtained in preparation example 3 was diluted 1/100 000 with water. 200 ml of the solution were placed in a 300 ml glass beaker, in which 30 larvae of northern domestic cousins (Culex pipiens pallens) were released at the last stage of growth. The following day, it was observed that more than 90% of the larvae had been killed in all

cases.

Experimental example 5

Insecticide activity, with regard to adult house flies

  tes (Musca domestica), of each aerosol obtained in Preparation Examples 6, 7 and 13 was checked by the aerosol test method (Soap and Chemical Specialties, Blue BOok, 1965), using a Peet chamber Grady (6 feet) 3. With all aerosols, more than 80% of the flies could be immobilized within minutes of spraying and more than 70% could be killed

flies in one day.

  Experimental example 6 About 50 adult female northern domestic cousins (Cule pipiens Pallens) were released into a glass chamber of

(70 cm) 3 in which a small fan was installed and turned

  battery-powered electric reader (diameter of the fins, 13cm).

  0.1 g of each of the mosquito coils obtained in Preparation Example 8 were ignited by one of their ends and placed in the middle of the bottom of the chamber. With all

  mosquito coils, we could observe within 20 minutes

  more than 90% of adults were immobilized and the slow

tomorrow more than 80% of adults had been killed.

  Experimental example 7 About 50 adult house flies (Musca domestica) were released in a glass chamber of (70 cm3) in which was installed and turned a small electric battery fan

(diameter of the fins, 13 cm).

the heating fumigant obtained in preparation example 9 was placed on a hot plate in the chamber, so that

give off vapors. Over 90% of adults were able to be immobilized

read within 20 minutes.

Experimental example 8 About 20 young rice plants were grown up to the 3-4 leaf stage in a 10 cm diameter flowerpot

and the powder obtained in preparation example II was spread

due at the rate of 3 kg / 10 ares by means of a shaker shaker

  Bell. Following the dusting, the pot was covered with a tzeil-

  metallic lily and 20 to 30 green hoppers of the adult rice leaf (Nephotettix cinctipces) were released there. The dead and the living were counted after 24 hours and it was found that the

mortality was over 80%.

  EXAMPLE EXAMPLE 9 liters of water were poured into a 14-liter polypropylene bucket and 1 g of each of the granules obtained in Preparation Example 12 was added thereto. After 1 minute, about 100 cousin larvae Northern domestic (Culex piUiens pallens) in the final stage of development were released into the water. The dead and the living were counted and it was found in all cases that more than 90% of the larvae had been killed in space

24 hours.

R E V E N D I

CAT I ON S

  1. Compound of formula: CH3 HC _ C - CH2 o0c O 0 Oil

0 0

H H H

I I I x

- C - C - C = C

\ / \ x / \

CH3 CH3

  in which X is a chlorine, bromine or fluorine atom.

  2. (+) - 2,2-dimethyl3-cis, trans, 2 ', 2'-dichlorovinylcyclopropane-

  (+) - 2-methyl-3-2'-propynyl-cyclopent2-en-4-on- carboxylate

l-yle.

  3. (+) - 2,2-dimethyl-3-trans-2 ', 2'-difluorovinylcyclopropane-

  (+) - 2-methyl-3-2'-propynyl-cyclopent-2-ên-4-on- carboxylate

l-yle.

15.4. (+) - 2,2-dimethyl-3-cis-2 ', 2'-dibromovinylcyclopropanecar-

  (+) - 2-methyl-3-2'-propynyl-cyclopent-2-en-4-on-l yl boxylate. 5. Process for preparing the compound according to claim 1, characterized in that a carboxylic acid of formula (II) is reacted, w w I I i X

HO - C - C - C - C = C -

He \ / x

0 C

/ \

CH3 CH3

(II) in which

  X has the meaning given in claim 1, or a derivative

reagent of this acid, with an alcohol of formula (III '), (I) CH3

C C - OCH2 OH

H C H 01-1 (III ')

  6. Insecticidal composition, characterized in that it comprises,

  as an active ingredient, an effective amount for insect

  ticides of the compound according to claim 1, and an inert excipient. L. Method for combating an insect, characterized in that it consists in applying to the insect an effective amount for purposes

insecticide of the compound according to claim 1.

  8. Use of the compound according to claim 1 as

than insecticide.