LU83208A1 - NOVEL 4-SUBSTITUTED 2-INDANOLS, DERIVATIVE ESTERS THEREOF, INSECTICIDE COMPOSITION CONTAINING SUCH ESTERS, AND METHODS FOR CONTROLLING INSECTS USING THE SAME - Google Patents

Description

k / NEW 2-INDAN0LS4-SUBSTITUES, DERIVATIVE ESTERS, *

INSECTICIDE COMPOSITION CONTAINING THESE ESTERS AND METHOD FOR CONTROLLING INSECTS USING THE SAME

The present invention relates to novel 4-substituted 2-in-danols, esters derived therefrom, an insecticidal composition containing these esters and a method of controlling insects using this composition.

More particularly, the invention relates to new alcohols which are 4-substituted 2-indanols and esters, in particular cyclopropanecarboxylates, derived therefrom, these esters having insecticidal activity, as well as an insecticidal composition containing these esters and a 10 method of controlling insects using this composition.

Pyrethrins, which are natural extracts of chrysanthemum flowers, have long received attention as insecticides. Since the structures of these 15 compounds have been elucidated, efforts have been made to synthesize related compounds with increased insecticidal activity and better stability against air and light. Since the insecticidal activity of pyrethroids requires the presence in a molecule of an appropriate acid fragment and an appropriate alcohol fragment, new acid radicals and / or alcohols have been sought in the art. Notable advances in alcohol research have been the discovery of 5-benzy1-3-fury1-methyl alcohol and then 3-phenoxybenzyl alcohol which is more stable to light. Similarly, significant progress has been made in the research of pyrethroid acids. An example of the use of a new acid fragment 30 and d is 3- (2,2-dichloroetheny1] -2,2-dimethylcyclo-p-ropanecarboxylate 3-phenoxyphenylmethyl marketed as an insecticide under the common name of permethrin. 'a new alcohol fragment in the same compound.

2, 'tu The invention relates to novel 4-substituted 2-indanols and certain esters with high insecticidal activity derived therefrom.

In the present description, the qualifier 5 "lower" applied to an aliphatic hydrocarbon radical indicates that it contains 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The term "halogen" denotes bromine, chlorine or fluorine and the term "halo" denotes the corresponding radicals. The term "halo-10alkyl" denotes an alkyl radical having 1 to 3 carbon atoms substituted by one or more atoms The term "insecticide" is taken here in its broadest sense and includes compounds active against insects themselves, mites and other pests of dwellings, animals or crops belonging to the junction of arthropods Unless explicitly stated otherwise, these definitions apply to the present description and to the claims.

The new compounds of the invention correspond to the general formula: R1 25 where represents a phenyl radical which may be substituted by a halo or alkyl radical containing from 1 to 4 carbon atoms, and R2 represents a hydrogen atom or a 2,2,3,3-1etramethylcyclopropylcarbony1e radical, 30 1 - (4-chlorophenyl) -2-methylpropyl-1-carbonyl or a radi cal of formula: Λ °

C = CH —L-C- II

35 Z / <»

»I

3 where V and Z which are identical or different, represent a hydrogen atom or a halo, lower alkyl, lower perhaloalkyl, phinyl radical which may be substituted by a halo or alkyl radical containing from 5 1 to 4 carbon atoms, or phenylthio which may be substituted by a halogen or lower alkyl radical, provided that one of the symbols Y and Z is other than a hydrogen atom. The new alcohols (2-indanols) are the compounds where represents a hydrogen atom while in the 1D insecticide compounds R ^ is other than a hydrogen atom.

Particularly useful insecticides or acaricides of the invention are the cyclopropanecarboxylates in which one of the symbols Y and Z represents a halo radical such as chloro or brorno and the other, which is similar or different, represents a halo or perhaloalkyl radical such as trihalomethyl and R1 represents the phenyl radical.

The cyclopropanecarboxylates comprising the acid radical of formula (II] have cis and trans isomeric forms, that is to say that the carboxy radical and the vinyl radical substituted in positions 1 and 3 of the cyclopropane ring are cis or trans to each other. The preparation of these compounds generally results in a mixture of the cis and trans isomers here called cis, trans in which the ratio of the cis form to the trans form can vary within a wide range Compounds where Y is different from Z may also exist as E_ or Z ^ isomers or as mixtures of the isomers and T_ designated * _E, _Z, depending on the spatial relationship of the substituents on carbon a of the vinyl radical compared to those on car-box 3 of the vinyl radical.

In the field of cyclopropanecarboxylates, it is well known that there may be significant quantitative differences in the insecticidal activity of the cis and trans isomers. In general, for a given cyclopropanecarboxylate, the cis isomer is more active than the trans and η _ ±! L- (J) 0 <r ______ '"Z? _ Ο) 5ε ΓΟΓ T' owoairo rgr ^ 'îi ii'os Who-3 η U) homi ^ o [Ο] 0Ε '' ΗΠϋΝ 9ίΙ90 / εΓΓ3Γΐν Ζ, 4 kl (jl I <-: - (a)

OH XX-v> q ^ TDOS T

(3) (a) (ÜJ (§), - v _ffPCH z 52 [ÖM <0zu ΟΙ ^ H0ShZD / 0 ^ / h ° M i {0) HZ00 Hz00 O) (g) (v) (Q) 0z0zDsH fOl fPl XVe -—— 2- xÙ ^ J-7- V'HOOH 02

(QJ | ^ H ^ OO) ZHD rQ / "OS * H / JflH | ^ V

sHzDsOO ^: Ξχοοοχε saq aajgdajd anod apaacud un aaqsnxxq xouepux-z-xAuaqd-fr ς i ax quBUjaauoo sajdB-xo Biuaqos a-] -suoîibj. sanaxsnxd ap uoxq -uaAux.x ap εχοοοχθ xneaAnou sax jajedajd qnad uo • uoqq "-uaAUX.x ap ajpeo ax susp quawaxeSa quajqua sa3uBX§ui sjnax qa sanbtpuaABJ sasodiuoo sap sa jawox * ajpso ax susp quajqua saSuBxatu sjnax anb tsute sxanpxAxpux z qa 3 sajauuosx sax 'axqsxqujas uoôbj. aQ ’O / OOL · Ç 001/0 aP SUJUJB3 Βχ subp sxjdiuoa qsa suBjq / sxo qJoddBj ax sxanbsax susp qa sa§UBxaw sjnax anb xsuxb sanbxpuaAaj sasoduioa sap s u b j q qa sxo sajaux. saq aqoxSua qa g auaaouoo uoqquaAUx, x 'ajxgjquoa uoqqBoxpux qnes Z qa 11 sajauiosx sax aujaauoo XNB ao ua saxqBxqujas aqxAqqoB, p saauajaqqxp sap jaAjasqo quawaxeSa qnad uo * suBjq' sxo aSuBxaw ax anb qxqoB snxd quaujaxsS ^ 1 ή 5

NaBll l ÎOJ

(I) C.1K0I1 110 (g) 5 (J)

This preparation method (Method A3 is described in more detail in Example 1. Other methods include hydroboration / oxidation (Method B) and epoxidation / reduction (Method C) of a suitable indene such than compound H of the above scheme. These additional processes are respectively described in detail in Examples 2 and 3.

The insecticidal compounds com-15 carrying an acid radical of formula (II) can be prepared from alkanoa-tes of formula:

y X Y

î__x

V

20 '\ —COR

U 3 where Y and Z have the same definition as above; R represents a lower alkoxy radical such as methoxy or ethoxy or a 4-substituted 2-indanyloxy radical derived from an alcohol of formula (I); and X represents a chloro or bromo radical. Example 4 illustrates a process for preparing the intermediate alkanoa-tes of formula (III) according to which a lower alkyl 3,3-dimethyl-4-pentenoate is allowed to react with a compound of formula XC (Y3 CZ] where X , Y and Z have the same 3G definition as above.

The dehydrohalogenation of the compound of formula (III) followed if necessary by a hydrolysis of the ester and also if necessary by a halogenation of the carboxy radical formed, provides a compound of formula:

/ V IV

z 'COK

35 i * i 6 where R represents a lower alkoxy, hydroxy, halogeno radical or a 4-substituted 2-indanyloxy radical deriving from an alcohol of formula (I), and Y and Z have the same definition as above . The dehydrohalogenation reaction can comprise, as intermediates, one or more compounds corresponding to the formulas:

V

V * l ____ A- *. , - v \ / * y

10 A n) l <A, - COR '1- COR

VII

and it can be carried out in a single stage by elimination of two equivalents of halogenated hydracid, HX, to obtain directly a compound of formula (VI) or in several stages under conditions allowing the successive elimination of two equivalents of HX in separate reactions. If desired, these intermediates or their mixtures can be recovered. The compound of formula (IV) can then be transformed into the compound of formula (I) according to methods known in the art, for example in the case where R represents a lower alkoxy, hydroxy or halogeno radical, by esterification or transesterification with a 4-substituted 2-indanol of formula (I) (R 1 represents a hydrogen atom).

The following examples illustrate the preparation of the insecticidal compounds and of the new alcohols serving them as intermediates according to the general method described above. In the examples, unless otherwise indicated, when concentrating a liquid under reduced pressure, op uses a water pump.

Examples 1 to 3 illustrate the preparation of compounds of formula (I) in which represents a hydrogen atom.

35 EXAMPLE 1

Synthesis of 4-phenyl-2-indanol (Method A)

K

7 - Ί A - Prégaration_de_2; Jbromométhy 1) _bighény le

In reflux for 5 hours, a stirred solution of 58.9 g (0.319 mole] of 2-biphenylmethanol and 6 ml of concentrated sulfuric acid in 67 ml of 48% aqueous hydrobromic acid. Gn cools the reaction mixture at room temperature, pour into ice water and extract the mixture obtained with three 100 ml portions of ethyl ether. The combined extracts are washed with 50 ml of a saturated aqueous solution of sodium bicarbonate. then with 50 ml of water. The organic layer is dried over magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure to obtain 76.8 g of 2- (bromomethyl] biphenyl in the form of a residual oil. The nuclear magnetic resonance spectrum and the infrared spectrum are in agreement with the proposed structure.

B - Pr | B§ration_de (2-ghénylbenzyl) _malonate_de_diéthyle

A stirred mixture of 12.5 g (0.54 mole) of sodium hydride (25 g of a 50% dispersion in mineral oil) is placed under a nitrogen atmosphere and cooled to 0 ° C. 20 line) in 300 ml of dimethylformamide and 900 ml of benzene. 104.3 g (0.9 mole) of diethyl malonate are added dropwise to this mixture over 5 minutes and the mixture is stirred until there is no more evolution of hydrogen. Gn is then added at 0 ° C, 117 g (0.47 mole) of 2- (bromomethyl) biphenyl. When the addition is complete, the reaction mixture is stirred at 0 ° C for 30 minutes and then allowed to warm to room temperature with stirring for one hour. The reaction mixture is poured into 500 ml of water, the layers are separated and the aqueous layer is washed with two 250 ml portions of diethyl ether. The organic layer is combined with the portions of ether used for washing and the whole is washed with a portion of 500 ml of 5% aqueous hydrochloric acid, a portion of 500 ml of water, a portion of 300 ml. 35 of a saturated sodium bicarbonate solution and finally a 500 ml portion of water. The organic layer “f 1” 8 is dried with magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure * to obtain an oily residue. The oil is distilled under reduced pressure to obtain 149.0 g of diethyl (2-phenylbenzy1) malonate; E: 1 75-1 800C / 107-120 Pa. The nuclear magnetic resonance spectrum is in agreement with the proposed structure.

C - Preparation of 1 ^ acid_ (2-phenylbenzy 1] _ü) 5î9DÎ9y§

A stirred solution of 149.0 g (0.456 mole] of (2-phenylbenzyl] diethyl malonate and 56.1 g (1.0 mole] of potassium hydroxide) is heated at reflux for 3 hours. in 50 ml of water and 500 ml of ethanol, the reaction mixture is allowed to cool to room temperature and left to stand for 60 hours, the etha-nol is distilled off and the residue is suspended in 400 ml of water The mixture is extracted with a 250 ml portion of diethyl ether, the aqueous phase is separated and acidified with concentrated hydrochloric acid and then extracted with two 250 ml portions of diethyl ether The two extracts from the acidified aqueous phase are combined, dried over magnesium sulphate, filtered and the filtrate is concentrated under reduced pressure to obtain (2-phenylbenzyl] malonic acid in the form of a pale yellow oil. This oil is used directly in the next stage of the reaction sequence.

D - Preparation_of_12açid§_3: (2: biphenyl] _prgpignigue

A solution of 124.2 g (0.46 mole] of the oil of stage C of the present example in 500 ml of water is refluxed for 16 hours, the reaction mixture is cooled and the mixture is collected. produced by filtration to obtain, after recrystallization from a mixture of ethanol and water, 92.9 g of 3- (2-biphenyl] propionic acid. The nuclear magnetic resonance spectrum is in agreement with the proposed structure.

Theoretical analysis for C ^ H ^ 0 ^: C = 79.62; H = 6.24% found: C = 79.84; H = 5.98% * 9 E - Prégaration_de_la_4-9énén-1-indanone

A solution of 92.9 g (0.41 mole) of 3- (2-biphenyl) propionic acid in 100 ml of thionyl chloride is stirred at room temperature for 16 hours. The excess thionyl chloride is distilled off and then co-distilled with three 50 ml portions of benzene.

The residue is dissolved in 150 ml of benzene and the solution is added dropwise over 15 minutes at 10 ° C. to a stirred mixture of 71.0 g (0.53 mole) of aluminum chloride in 900 ml of benzene . When the addition is complete, the reaction mixture is stirred at 10 ° C for 110 minutes and then poured into 1000 ml of ice water and stirred until the ice melts. The aqueous phase is separated and extracted with two 100 ml portions of diethyl ether. The ethereal extracts and the organic phase are combined and washed with a 10% aqueous solution of sodium hydroxide and then with two portions of water. The combined extracts are dried with magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure to obtain 85.4 g of 4-phenyl-1-indanone in the form of a brown crystalline solid; Mp: 85-90 ° C. The product is used without further purification.

We recrystallize a sample for analysis.

The nuclear magnetic resonance spectrum is in agreement with the proposed structure.

Theoretical analysis for G: P = 86.50; H = 5.81% found: C = 86.63, H = 5.74% F - Prégaration_du_4-ghényl-1-indanol 30 To a stirred solution of 20.8 g (0.10 mole) of, 4- phenyl-1-indanone in 150 ml of ethanol, 2.0 g (0.06 mol) of sodium borohydride are added in portions. During the addition, the reaction temperature rises to 33 ° C. When the addition is complete, the reaction mixture is allowed to cool to room temperature and stirred for 16 hours. The reaction mixture is mixed with water and concentrated under reduced pressure.

* 1 ο

A precipitate is collected which forms during the concentration of the aqueous solution, it is dried and it is re-crystallized in a mixture of toluene and hexane to obtain 17.3 g of 4-phenyl-1-indanol; M: 80.5-81.5 ° C.

5 The nuclear magnetic resonance spectrum is in agreement with the proposed structure.

Theoretical analysis for C ^ H ^ O: C = 85.68; H = 6.71% found: C = 85.63; H = 6.70% G - Prégaration_du 7-ghény1 - 1 H-indene 10 The mixture is heated at reflux for one hour by collecting the water formed as a by-product in a Dean-Stark trap, a stirred solution of 16, 7 g CO, 08 mol) of 4-phenyl-1-indanol and 0.1 g of p-toluenesulfonic acid in 180 ml of benzene. The reaction mixture is washed with two 50 ml portions of a 5% aqueous solution of sodium bicarbonate and then with a 50 ml portion of water. The organic phase is dried with magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure while maintaining the temperature below 50 ° C to obtain 14.8 g of 7-phenyl-1H-indine. The nuclear magnetic resonance spectrum is in agreement with the proposed structure.

Theoretical analysis for C ^ 5 H ^ 2: C = 93.71, H = 6.29% found: C = 93.47 d H = 6.31% 25 H - Prégaration_de_la_4-ghény1-2-indanone

A stirred solution of 53.2 ml of formic acid and 10.5 ml of hydrogen peroxide at 30% is heated to 35 ° C. and 14.5 g (0.075 mol) of 7-phenyl are added dropwise. 1 H-indene which raises the temperature of the reaction mixture to 41 ° C. When the addition is complete, the reaction mixture is allowed to cool to ordinary temperature and is stirred for 16 hours. The reaction mixture is concentrated under reduced pressure to obtain a semi-solid residue which is subjected to steam distillation in the presence of dilute aqueous sulfuric acid. The distillate is filtered to obtain 1.84 g of 4-phenyl-2-indanone at M: 133-136 ° C. The spectrum of nuclear magnetic resonance and the infrared spectrum are in agreement with the proposed structure.

I - Prégaration_du_4-phenyl-2-indanol To a stirred mixture of 0.30 g (0.0014 mol) of 5 4-phenyl-2-indanone in 10 ml of ethanol, 0.03 g is added per portion (0 , 0008 mole) of sodium borohydride.

The yellow solution obtained is stirred at room temperature for 1.5 hours, then concentrated and 50 ml of water are added. The mixture is extracted with two 50 ml portions of diethyl ether. The extracts are combined, dried over sodium sulfate, filtered and the filtrate is concentrated under reduced pressure to obtain, after recrystallization from hexane, 0.13 g of 4-phenyl-2-indanol.

The nuclear magnetic resonance spectrum and the infrared spectrum are in agreement with the proposed structure.

EXAMPLE 2

Synthesis of 4-pheny1-2-indanol (Method B)

Under a dry argon atmosphere, a stirred solution of 32.9 g (0.391 mole) of 2,3-dimethyl-2-butene in 250 ml of tetrahydrofuran is cooled to between 0 and -5 ° C.

372.5 ml of a 1.05 M (0.391 mol) solution of borane in tetrahydrofuran are added over 30 minutes and the mixture is stirred for 3/4 hour. A solution of 1 B8.2 g (0.355 mole) of 7-phenyl-1H-indene (which can be prepared according to Example 1G) in 250 ml of tetrahy- is added over 30 minutes while continuously cooling. drofuran and the mixture is stirred for 1.5 hours.

The mixture is cooled to -15 ° C and 71 ml of water are added over 30 minutes. 30,213 ml of a 3 N aqueous solution of sodium hydroxide and 213 ml of a 30% aqueous solution of hydrogen peroxide are added successively dropwise, the mixture is stirred at 0 ° C. for 30 minutes and then it is filtered on a layer of diatomaceous earth. The aqueous phase is separated from the two phases of the filtrate and extracted with ethyl ether. The extracts are combined with the organic phase of the filtrate and the whole is washed with a saturated aqueous sodium chloride solution * 12, dried over anhydrous potassium carbonate and filtered. The filtrate is concentrated under reduced pressure to obtain 79.6 g of a yellow green oil and it is shown by gas chromatographic analysis that it contains 90% 4-phenyl-2-indanol and 8.4% of 4-pheny1-1 -indano 1.

The mixture is heated to reflux for 15-20 minutes, collecting an azeotrope of toluene and water in a Dean-Stark trap, a solution of 79.6 g of the oil and 0.1 g of acid. p-toluenesulfonic acid in 350 ml of toluene. The mixture is cooled, placed on a chromatography column packed with silica gel and eluted first with toluene and then with a 1/1 mixture of toluene and ethyl acetate. The appropriate fractions are combined and concentrated to give, after crystallization from toluene, 44.5 g of 4-phenyl-2-indanol; M: 71-73 ° C. The nuclear magnetic resonance spectrum is in agreement with the proposed structure.

EXAMPLE 3 Synthesis of 4-phenyl-2-indanol (Method C] A - Pregaration of 1,2,2 -oxyoxy-42Bhenylindane

A stirred solution of 47.5 g (0.234 mole] of m-chloroperbenzoic acid (85% pure) in 390 ml of chloroform is cooled to 0 ° C. A solution of 45 g (0.234 mole) is added dropwise ] of 7-phenyl-1H-indene (which can be prepared as in Example 1G] in 110 ml of chloroform. When the addition is complete, the mixture is stirred for 2.5 hours and then left to stand for 21 hours at 0 ° C. Keeping the temperature in the range of 0 to 5 ° C., 100 ml of a 10% aqueous sodium hydroxide solution are added dropwise while 50 ml is added. of a 10% aqueous solution of sodium sulfate. When the addition is complete, the mixture is stirred in two phases for 30 minutes. The organic phase is separated, washed first with an aqueous solution. diluted with sodium bicarbonate then with water, dried over 13 "* anhydrous sodium sulfate and filtered. The filtrate is concentrated under reduced pressure to obtain 47.7 g of 1,2-epoxy- • 4-pheny lindane in the form of a pale yellow oil having a purity of 97% according to the analysis by gas chromatography.

5 B - Prégaratign_du_4-ghényl-2-indanol

Under a dry argon atmosphere, a stirred solution of 9 g [0.067 mol) of aluminum chloride in 225 ml of anhydrous diethyl ether is cooled to 0 ° C. 9.4 g (0.245 mole) of lithium aluminum hydride is added in portions. The cooling bath is removed and the mixture is stirred for 15 minutes. Maintaining the temperature at 25 ° C., a solution of 47.7 g (0.229 mole) of 1,2-epoxy-4-phenylindane in 175 ml of anhydrous diethyl ether is added dropwise. When the addition is complete, the mixture is heated to reflux for 18 hours and then cooled to 0 ° C. Water and an aqueous solution of sodium hydroxide are added to decompose the excess lithium aluminum hydride and the mixture is filtered. The filter cake is washed with ethyl ether, the filtrate and the washing liquids are combined and dried over anhydrous sodium sulfate. The mixture is filtered and the filtrate is concentrated under reduced pressure to obtain an oil. The oil is subjected to chromatography on a column of silica gel, eluting with a 9B / 2 mixture of toluene and ethyl acetate and then a 90/10 mixture of toluene and ethyl acetate to obtain 62.1 g of 4-phenyl-2-indanol mp: 72-76 ° C. The nuclear magnetic resonance spectrum is in agreement with the proposed structure.

Example 4 illustrates the preparation of compounds of formula (III).

EXAMPLE 4

Synthesis of ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-1rifluoroheptanoate

A stirred solution of 44.6 g (0.267 mole) of ethyl 3,3-dimethyl-4-pentenoate, 100 g "* 14 (0.533 mole) is heated at reflux for 16 hours under a nitrogen atmosphere. 1.1, 1 -1rich 1orotrif1uoroétha πe, 0.27 g (0.0027 mole] of cuprous chloride and 6.2 g (0.134 mole] of ethanolamine in 270 ml of tertiary butyl alcohol.

The reaction mixture is cooled to the gold-5 temperature and extracted with three 100 ml portions of ethyl ether. A precipitate forms in the extracts and is separated by vacuum filtration. The filter cake is washed with two 25 ml portions of diethyl ether.

The ethereal extracts are combined with the washing liquids, and the whole is concentrated under reduced pressure to obtain an oily residue. The volatile components remaining in the residue are removed by additional treatment under reduced pressure with a vacuum pump. The residue is distilled under reduced pressure to obtain 78.3 g of ethyl 3,3-dimethyl-4,6,6-1rich 1oro-7,7,7-trifluoroheptanoate; E.: 85-87 ° C / 16-20 Pa. The nuclear magnetic resonance spectrum is in agreement with the assigned structure.

Examples 5 and 6 illustrate the preparation of lower alkyl esters of formula (IV). Example 5 illustrates a two-stage process passing through formula (VII]. Example B illustrates a one-step process single stage.

EXAMPLE 5 2 5 Synthesis of cis, trans-3- (2-chloro-3,3,3-trifluoro-1-propeny1] -2,2-dimethylcyclopropanecarboxylate methyl A - pregaration_du cis, trans-3 (2,2- dichloro-3,3,3-tri-Îiy5îT99? I99yïIz? £.? zdïII} Etb ^ l9y9i9BïZ99§DE95rbo> <yla'te_de_rnéthyl Cooled to -5 ° C a stirred solution of 37.0 g 30 (0.121 mol) of 3,3-dimethyl-4,6,6-1richloro-7,7,7-tri - methyl fluoroheptanoate, 50 ml of tertiary butyl alcohol, 50 ml of dimethylformamide and 50 ml of hexane under an argon atmosphere. A solution of 16.4 g (0.14 mole] of potassium tert-butoxide in 200 ml of tertiary butyl alcohol is added dropwise to the stirred solution at a rate such that the temperature of the reaction mixture is maintained between -3 and -5 ° C. When the addition is complete,

a a

1 5 the reaction mixture is stirred for 4 hours between -3 and -5 ° C and then poured into a solution of 8.0 g of ammonium chloride in 250 ml of water. The mixture is extracted with two 200 ml portions of diethyl ether.

5 The combined ethereal extracts are washed with two 200 ml portions of water. The ether layer is dried with sodium sulfate and filtered. The filtrate is evaporated under reduced pressure to obtain a residual oil. The oil is distilled under reduced pressure to obtain 19.8 g of oak, trans-3- (2,2-dichloro-3,3,3-trifluoropropyl) -2,2-dimethylcyclopropanecarboxylate j E. = 55 -57 ° C / 12 Pa. The infrared spectrum and the nuclear magnetic resonance spectrum are in agreement with the proposed structure.

15 Theoretical analysis for C.-H Cl F „0: C = 40.98 j H = 4.47% IU I O <£ Ο Δ.

found: C = 41.50 d H = 4.41% B - cis synthesis, trans-3- (2-chloro ~ 3,3,3-trifluqro-1-0rogenyl ^ -2,2-dimethylcycloproganecarboxylate_de_méthyl

Heated at 100 ° C for 4 hours, a stirred solution of 30.6 g (0.105 mol) of cis, trans-3 (2,2-dichloro-3,3,3-trifluoropropyl) -2,2-dimethylcyclopropanecarboxylate methyl and 17.6 g (0.116 mole) of 1,5-diazabicyclo Js. 4.0_ / undecene-5 in 100 ml of dimethy lf ormamide. The reaction mixture is cooled and poured into a solution of 37.2 ml of concentrated hydrochloric acid in 300 ml of water. The mixture is extracted with three 200 ml portions of diethyl ether. The combined ether extracts are washed with a saturated aqueous solution of sodium chloride. The ethereal layer is dried with sodium sulfate and filtered. The filtrate is evaporated under reduced pressure to obtain an oily residue. The oil is dissolved in hexane, treated with bleaching charcoal and filtered. The filtrate is evaporated under reduced pressure to obtain an oily residue. The oil is distilled under reduced pressure to obtain in three fractions 10.0 g of cis, trans-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2- 1 ί 1 6 methyl dimethylcyclopropanecarboxylate; E. == 40 ~ 60 ° C / 6.67 Pa. The infrared spectrum and the nuclear magnetic resonance spectrum are in agreement with the proposed structure. The nuclear magnetic resonance spectrum indicates that the existence of a 60/12 mixture of the ci s and trans isomers.

Theoretical analysis for CioHi2C1F3 ° 2: C = 46.80 d H = 4.71% found: C = 46.91; H = 4.79% EXEHPLE 6 10 Synthesis of cis, t ran s - 3 - (2 - ch 1 oro - 3,3,3 - tr if lu oro -1-propenyl) -2,2-dimethylcyclopropanecarboxylate ethyl To a stirred solution of 70.3 g (0.228 mole] of ethyl 3,3-dimethyl-4,6,6-trichloro-7,7.7-trifluoroheptanoate in 200 ml of distilled ethanol, dropwise added 15 at room temperature 500 ml of a solution of sodium ethylate in ethanol prepared from 11.5 g of metallic sodium (0.50 mol). When the addition is complete, the reaction mixture is stirred for one hour at room temperature, then allowed to stand for 10 hours, the cloudy reaction mixture is filtered and the filtrate is evaporated under reduced pressure to obtain a residue, the residue is suspended in 200 ml of water and the mixture with three 50 ml portions of diethyl ether, the combined extracts are dried with sodium sulfate and filtered, the filtrates are evaporated under reduced pressure to obtain as an oily residue 58.5 g of cis, ethyl trans-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate.

The nuclear magnetic resonance spectrum and the infrared spectrum are in agreement with the assigned structure and indicate that the product is an approximately equal mixture of the cis and trans isomers.

Examples 7 and 8 illustrate the preparation of the individual cis and trans isomers of free acids of formula (IV). 35 EXAMPLE 7

Synthesis of the trans isomer and of the mixture of the cis and trans isomers of 3- (2-chloro-3,3,3-trifluoro-1-propeny1) -2,? - dimethylcyclopropanecarboxylic acid 1 7 Λ 4 TO

Stirred with heating at reflux for 1Θ hours a solution of 16.2 g CO, 06 mol) of ci s, trans-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2 -ethyl dimethylcyclopropane-carboxylate in 94 ml CO, 078 mol) of a stock solution containing 3.34 g of sodium hydroxide, 94 ml of ethanol and 6 ml of water. The reaction mixture is concentrated under reduced pressure, 25 ml of water are added and the mixture is acidified to pH 1 with 6N hydrochloric acid. The acidified mixture is extracted with two 50 ml portions of diethyl ether . The combined extracts are dried with magnesium sulfate and filtered. The filtrate is evaporated under reduced pressure to obtain a residue. This residue is heated with 50 ml of hexane. The hot hexane is decanted from a tarry residue and cooled to obtain a solid precipitate which is collected by filtration and then dried to obtain 3.3 g of a solid at F. "97-103 ° vs. The mother liquor is concentrated to obtain a second fraction of solid weighing 0.8 g; M.p .: 96-103 ° C. The nuclear magnetic resonance spectrum of the two fractions indicates that the solids each consist of trans-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopro- acid panecarboxylic. The mother liquor is evaporated to obtain a residue. The residue is taken up in 50 ml of hexane and the solution is cooled in a freezer for 18 hrs-25 res. By filtration, a solid precipitate is collected which is dried to obtain 4.3 g of a solid; M.p .: 64-74 ° C.

The nuclear magnetic resonance spectrum indicates that the solid is a 50/50 mixture of the cis and trans isomers of 3- [2-chloro-3,3,3-trifluoro-1-propeny1) -2,2-30 dimethylcyclopropanecarboxylic.

EXAMPLE 8

Synthesis of the cis isomer and of the mixture of the cis and trans isomers of 3- [2-chloro-3,3,3-trifluoro-1-propeny1) - 2,2-dimethylcyclopropanecarboxylic acid 35 The mixture is heated to reflux for one hour a stirred solution of 90.0 g (0.35 mole) of cis, trans-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecar-boxylate ( about 90% of the cis-isomer, prepared $ 18 as in Example 5B), 5.4 ml of concentrated sulfuric acid and 13.8 ml of water in 138 ml of acetic acid. The reaction mixture is cooled and extracted with two 100 ml portions of ethyl ether. The combined extracts are dried with sodium sulfate, filtered and the filtrate is concentrated under reduced pressure to obtain a solid residue. The residue is digested with 300 ml of hexane, the hexane solution is decanted from a tarry dark residue and allowed to cool to room temperature.

. A solid precipitate is formed which is collected by filtration to obtain 42.4 g of a product identified by nuclear magnetic resonance spectroscopy as being cis-3- (2-chloro-3.3 acid). , 3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylic. No melting point is determined. Another melting point of the cis isomer of the acid prepared at a different time is 106-110 ° C. The filtrate is concentrated and cooled to obtain 5.1 g of a solid which is identified by nuclear magnetic resonance spectroscopy as being a 50/50 mixture of the cis and trans isomers of 3 - C 2 -chloro acid. -3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropane-carboxylic. The filtrate is cooled in dry ice to obtain an additional 8.1 g of a 50/50 mixture of the cis and trans isomers.

Examples 9 and 10 illustrate the preparation of acid halides of formula [IV).

EXAMPLE 9

Synthesis of trans-3- [2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarbonyl chloride To a stirred solution of 4.1 g [0.0173 mole) of a trans-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylic acid in 40 ml of toluene, at ordinary temperature, 1.7 g (0.022 mole) of pyridine then 2.6 g (0.022 mole) of thionyl chloride in 25 ml of toluene. When the addition is complete, the reaction mixture is stirred at ordinary temperature 1 g

GO

for 17 hours. The reaction mixture is filtered on diatomaceous earth and the filtrate is evaporated under reduced pressure to obtain 3, B g of trans-3 - (2-chloro-3,3,3-trifluoro-1-propenyl] chloride] - 2,2-dimethylcyclo-5 propanecarbonyls The infrared spectrum is in agreement with the assigned structure.

EXAMPLE 10

Synthesis of cis-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarbonyl chloride 10 A stirred solution of 10.0 g (0.04) is heated to 80 ° C. mole) of cis-3- (2-chloro-3,3,3-trifluoro-1-propeny1) -2,2-dimethylcyc1opropanecarboxylic acid in 100 ml of toluene. In 10 minutes, a solution of 10.5 g (0.00 mole) of oxa-15 lyl chloride in 5 ml of toluene is added to this solution at BO 0 ° C and the whole is heated to 80 ° C. for 26 hours. Toluene and excess oxalyl chloride are distilled off to obtain a residual oil which is distilled under reduced pressure with a Kugelrohr distillation system to obtain 8.2 g of cis-3- (2- chloro-3,3,3-trifluoro-1-propenyl) - 2.2- dimethylcyclopropanecarbonyl; E.: 05 ° C / 12 Pa. The nuclear magnetic resonance spectrum and the infrared spectrum are in agreement with the proposed structure.

Examples 11 and 12 illustrate the preparation of compounds of formula (I) where is other than a hydrogen atom.

EXAMPLE 11

Synthesis of ci s-3- (2-chloro-3,3,3-trifluoro-1-propény1) - 2.2- dimethylcyclopropanecarboxylaie of 4-phenyl-2 ~ indanyl 30 A stirred solution of 0.25 is cooled to 5 ° C. g <0.0012 mole) of 4-phenyl-2-indanol and 0.11 g (0.0014 mole) of pyridine in 10 ml of toluene and a solution of 0.20 g (0.0011 mole) is added in portions ) of cis chloride 3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclo-35 propanecarbonyl prepared as in Example 10 in 5 ml of toluene. When the addition is complete, shake

I J

1b reaction mixture at room temperature for two hours, the reaction mixture is filtered and the filtrate is concentrated under reduced pressure to obtain an oily residue. The oil is placed on a pad of 5 silica gel and the product is eluted with 50 ml of a 1/1 mixture of hexane and toluene. The eluate is concentrated under reduced pressure at 1 00-1 1 50C / 2.67 Pa with a Kugelrohr distillation system to obtain 0.12 g of cis-3- (2-chloro 3,3-trifluoro-1- propenyl) -2,2-dimethylcyclopropanecarboxy-. 4-pheny1-2-indanyl late. The nuclear magnetic resonance spectrum is in agreement with the proposed structure. Theoretical analysis for C .H „„ C1F 0: C = 66.2B; H = 5.10%

in / Z J Z

found: C = 65.76; H = 5.28% EXAMPLE 12 ^ 5 Synthesis of cis, trans-3- (2,2-dichloroethény1) -2,2-diméthy1-cyclopropanecarboxylate of 4-phenyl-2 ~ indanyl

Stirred at room temperature for 16 hours a solution of 0.64 g (0.003 mole) of 4-phenyl-2-indanol, 0.70 g (0.003 mole) of cis chloride, trans ~ 3 ~ (2.2 -dichloroethenyl) -2,2-dimethylcyclopropanecarbonyl and 0.24 g (0.003 mole) of pyridine in 20 ml of benzene and then mixed with 50 ml of water. The organic layer is separated and the aqueous layer is washed with 50 ml of diethyl ether. The combined organic layers are washed with 100 ml of dilute aqueous hydrochloric acid, then with 100 ml of a 10% aqueous solution of sodium hydroxide and finally with water. The organic layer is dried with magnesium sulphate, filtered and the filtrate is concentrated under reduced pressure to obtain an oily residue. The oil is subjected to column chromatography eluting with benzene. The appropriate fractions are combined to obtain 1.1 g of cis, trans-3- (2,2-dichloro-ethenyl) -2,2-dimethylcyclopropanecarboxylate of 4-phenyl-2-indanyl.

35 Theoretical analysis for C23H22C12 ° 2: C = 68> 83 5 H = 5 * 53% found: C = 68.59; H = 5.79% 1 D> 21 The invention also relates to a method according to which an insecticidal amount of a compound of formula (I) is applied to which is other than a hydrogen atom at the site for combating insects , i.e. to the 5 insects themselves or to the foliage or seeds of cultivated plants. The compounds are useful for controlling insects living in the home or attacking animals and crops and can be used as a technical product or composition. Typical compositions consist of a combination of the active ingredient and a vehicle or diluent suitable for agriculture, preferably with a surfactant and optionally with other active ingredients. Appropriate compositions are in the form of granules, powders or liquids and the form to be used is chosen according to the nature of the unwanted animal and environmental factors of the particular site of infestation. It is thus possible to use the compounds of the invention in the form of granules of various sizes, powders, lab-moist powders, emulsifiable concentrates, solutions, dispersions and compositions with controlled release and the like. The concentration of active ingredient in a typical composition can vary greatly depending on the particular agent used, the additives and vehicles, the other active ingredients and the mode of application desired. Taking these factors into account, the active ingredient of a typical composition may for example be suitably present at a concentration of about 0.01 to about 99.5% and preferably from 0.1 to 90 or 95 % relative to the weight of the composition. A vehicle suitable for agriculture can have a concentration of from about 99.5% to about 0.5% by weight in the composition. When compatible surfactants are used in a composition, they may be present at various concentrations suitably in the range of 1 to 30% by weight of the composition.

> 22

The composition can be used as it is or diluted to the desired use dilution with an appropriate diluent or vehicle to facilitate the dispersion of the active ingredient. The concentration of the active ingredient 5 in the dilution of use may be in the range of 0.01% to about 5% and preferably at most about 10% by weight.

Various variants of the spray, dust, or controlled or slow release compositions of a type known in the art can be made by substitution or addition of one or more insecticide compounds of the invention in compositions known in the art. 'art or obvious.

The insecticide compounds of the invention can be combined and applied with other compatible active agents such as nematocides, insecticides, acaricides, fungicides, plant growth regulators, herbicides, fertilizers and the like .

When applying the compounds of the invention alone or in combination with other agricultural chemicals, an effective insecticidal amount of active ingredient should be used. Although the application dose will vary greatly depending on the choice of compound, composition, mode of application, plant species to be protected, planting density and the like, a Application rate suitable for cultivated plants can be in the range of 0.005 to 3 kg / ha and preferably from 0.01 to about 1 kg / ha.

Examples 13 and 14 illustrate tests of the insecticidal activity of the insecticidal compounds of the invention. EXAMPLE 13

Initial contact activity

The test compounds are dissolved in 5 to 10 ml of acetone containing 0.25% acetylphenoxypolyethoxyethanol. This solution is dispersed in a solution consisting of 90% water, 9.75% acetone and 0.25% acetylphenoxy-polyethoxyethanol to obtain a solution containing 512 ppm by weight of active ingredient . Portions of this solution are diluted with an appropriate amount of water to obtain solutions having varying concentrations of active ingredient. The organisms and study techniques are as follows: to evaluate the activity against the Mexican weevil (Epilachna varivestis Muls.) And the southern caterpillar (Spodoptera eridania £ Cram.J), we spray leaves of pinto bean plants with solution 10 to be studied and infested with larvae at the third development interval after the leaves have dried.

To assess the activity against the pea aphid (tAcyrthosiphon pisum / HarrisY), the leaves of large bean plants are sprayed before infestation by adult cerons. To prevent insects from escaping from the test site, whole test plants or cut leaves are placed in sealed paper cups. The tests are transferred to a room at 80 ° C and 50% relative humidity for at least 48 hours. At the end of this period, dead and living insects are counted and the percentage of mortality is calculated. The results of these tests are collated in the table below. This table also shows for comparison the insecticidal efficacy in these tests of the commercial insecticide which is permethrin, (-) ci s, trans-3- (2,2-dichloroethenyl) - 2,2-dimethylcyclopropanecarboxylate 3-phenoxybenzyl.

The mortality values in parentheses correspond to a second series of tests.

The compound of Example 12 is more active than 30 permethrin against the Mexican rustling beetle and pea aphid, but less active than permethrin against the southern caterpillar. The compound of Example 11 has an activity greater than that of permethrin against the three insect species. Compared with permethrin, the compounds of exem-35 pies 11 and 12 exhibit remarkable activity against the pea aphid.

"? 24

INITIAL ACTIVITY BY CONTACT

: Percentage of mortality at the concentration indicated (ppm) ^ Compounds: --------------------------------- -----------: Mexican bruche: 16: Ö: 6.5: 3.2 - I ", * II ··"? · ·

Example 11 .............: -: -: 100: 100 10:::::

Example 12 .............: 100 (100): 85 (80): -: -

• · “I

• “· ·

Permethrin .............: 50 (55): 35 (25): -: -: Southern caterpillar 15; ~ ~ ~

Example 11 .............: -: -: 100: 80

Example 12 .............: 100: 85: 35: 10

Permethrin .............: -: -: 100: 60 (7) 20 ------------------------ ---: ----------: ----------: ----------: -----------: Aphid pea

Example 11 .............: -: -: 100: 100

Example 12 .............: 80 (100): 80 (70): -: - ^ Permethrin .............: 10 (30): :: EXAMPLE 14

Trial of local application

To study the insecticidal activity of the compounds of the invention, they are applied to insects in appropriate amounts in the form of a solution containing 5 mg / ml of toxic agent in acetone. The results of the tests are read 24 hours after the application of the solution of the toxic agent and the percentage of mortality is determined. A commercial insecticide, permethrin, (-) ci s, trans-3- (2,2- ft 25 Λ> dichloroviny1) -2, 2-dimethylcyclopropanecarboxylate 3-phenoxybenzyl is used as the comparison standard. To determine the relative activity with respect to the value 1.0 assigned to the permethrin, the DL_n of the compound studied is compared to that of the standard. Insects

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5 used include the southern caterpillar (Spodoptera eridania /Cram.y), the cabbage caterpillar (Trichoplusia ni Hubner), the Mexican bruche (Epilachna varivestis Muls.), The beet caterpillar (Spodoptera exigua ^ HubnerJ], the bug euphorbia (Qncopeltus faciatus allas /), tobacco moth (Heliothis virescens ^ Fabricius7), and caterpillar of corn cobs (Heliothis zea / Boddi bJ}. The results of these tests are given in the table below.

The above-mentioned insects are designated respectively in the table by the abbreviations CM, CC, BM, CB, PE, NT and CEM.

In these tests, the compound of Example 11 is generally greater than the permethrin while the compound of Example 12 is generally less than the permethrin. The compound of Example 11, the activity of which has not been studied with regard to the beet caterpillar, the tobacco moth and the cob of the corn cobs, is less active than the permethrin vis. -to the southern caterpillar and more active than the permethrin vis-à-vis the caterpillar of cabbage, Mexican weevil and the spurge bug. The compound of Example 12 is less active than the permethrin vis-à-vis the southern caterpillar, the cabbage caterpillar and the caterpillar of the corn cobs, more active than the permethrin vis-à-vis the Euphorbia bug and about as active as the permethrin against the Mexican weevil, the beet caterpillar and the tobacco moth.

"26 * t"

LOCAL APPLICATION TEST

: Relative activity against: 5 Compounds

: CM: CC: BM: CB: PE: NT: CEM

Permethrin ......... 1.01: 1.02: 1.03: -: 1, O4: -: 10 Example 11 ........: 0.55: 1.50: 3.31: -: 1.58: -: 'c' R '7' ο 'q' in 'λλ

Permethrin ........: 1.0: 1.0: 1.0: 1.0: 1.0: 1.0: 1.0

Example 12 ........: 0.47: 0.65: 1.04: 0.96: 1.68: 0.93: 0.72 1 5 1. LD = 18 ng / insect

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2. DLrn = 130 ng / insect 5 u 3. DL ^ = 17 ng / insect 4. DL = 700 ng / insect

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20 5. LD50 = 24 ng / insect 6. DL = 140 ng / insect

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7. LD50 = 21 ng / insect 8. DL ^ = 1300 ng / insect 9. OL = 640 ng / insect 25 10. DLcn = 750 ng / insect b u 11. DL = 270 ng / insect

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Claims (9)

1. New compounds characterized in that they correspond to the formula: 5 i— I1 10 where R> | represents a phenyl radical which can be substituted by a halo or alkyl radical and containing 1 to 4 carbon atoms and represents a hydrogen atom, a 2,2,3,3-1étraméthy1cyc1opropy1carbony1e, 4 -C 4- radical chlorophény1) -2-methylpropylcarbony 1 e or a radical of formula: Vch-A-1/20 where Y and Z which are identical or different represent a hydrogen atom or a halo, alkyl radical containing 1 to 4 carbon atoms, perhaloalkyl having 1 or 2 carbon atoms, phenyl which may be substituted with a halo or alkyl radical having 1 to 4 carbon atoms or phenylthio which may be substituted by a halo or alkyl radical having 1 to 4 carbon atoms, subject that one of the symbols Y and Z is other than a hydrogen atom. AT 2. Compounds according to claim 1, characterized in that R ^ represents a hydrogen atom. 3. Compounds according to claim 2, characterized in that represents a phenyl radical. . 4. Compounds according to claim 1, charac-35 ses in that represents a phenyl radical and R ^ represents a radical of formula: v, Λ ° Z / i "i 28 5. Compounds according to claim 4, characterized in that one of the symbols Y and Z represents a halo radical and the other represents a halo or per-haloalkyl radical. 5 G. Compounds according to Claim 5, characterized in that Y and Z each represent a halo radical. 7. Compounds according to claim 6, characterized in that Y and Z each represent a chloro radical. h 10 8. Compounds according to claim 5, characterized in that one of the symbols Y and Z represents a halo radical and the other represents a trifluoromethyl radical. 9. Compounds according to claim 8, characterized in that one of the symbols Y and Z represents a chloro radical and the other represents a trifluoromethyl radical. 10. Insecticide or acaricide composition characterized in that it contains an insecticide or acaricide amount of a compound according to any one of claims 1, 4, 5, B, 7, 8 or 9, in which is other than a hydrogen atom, mixed with at least one additional component chosen from compatible adjuvants, diluents and vehicles. 11. Method for combating insects or mites, characterized in that it consists in applying to insects or mites or to the sites where it is desired to carry out the control, 0.005 to 3 kg / ha of a compound according to one any of claims 1, 4, 5, 6, 7, 8 or 9 in which is other than a hydrogen atom. * 12. An insecticide or acaricide composition according to claim 10, characterized in that it contains from Ο., ΟΙ% to 99.5% by weight of a compound according to claim 1, the remainder consisting of an additional component according to claim 10.