NEW PESTICIDES

Abstract: New compounds of general formula (I) wherein R<2> stands for hydrogen or C1-4 alkyl; and R<3> represents C1-4 alkyl or C2-8 dialkylamino, or a group of general formula R<4>-(CH2)n- wherein n is an integral number 1 or 2; R<4> represents -COOR<5>, wherein R<5> is C1-4 alkyl or a group of general formula (II), and R<6> and R<7> stand for hydrogen or C1-4 alkoxy; or R<2> and R<3> together may form a group of formula -(CH2)2-O-(CH2)2- and salts thereof and a process for the preparation of the same. The compounds of general formula (I) exhibit useful pesticidal - particularly insecticidal, akaricidal and/or nematocidal - effect and the invention also relates to pesticidal compositions comprising as active ingredient at least one compound of general formula (I) or a salt thereof.

Description: NEW PESTICIDES This invention relates to new benzofurane derivatives, a process for the preparation thereof, pesticidal com¬ positions comprising the same and the use of the said compositions for combating pests - particularly insects - and for inhibiting the growth thereof. In the body of the specification and the set of claims the general symbols have the following definition: R stands for hydrogen or C\ , alkyl ; and -ι____,<•~ * _/> . represents C-, , alkyl or G-, Q άialkylamino or -L—'+ d— ^ a group of the general formula R'-CcZp. -, w e in n is an integral number 1 or 2 ; R represents -C00R"', wherein 15 R"' is C-, alkyl or a group -of -the general formula II, and * . ■ ° and R stands for hydrogen or C-, - alkozy; or 3 md together may form a groun of the Formula -C C:- 2 ) 2 -0-C -tr _ '"2 J 2 * 20 It is known that the 2,3*-dii_ydro-2,2-diπethyl-benao- fυrane-7-yl- ethyl-carbamate C German Federal Republic patent ZTo. 1 4-93 646) useful as a general soil desinfec- tant is a very topical compound. On rat the acute 25 toxicity amounts to L-D C = 8-10 rag/kg p.o. For this reason the use of this compound is authorized only on industrial scale application. It is the object of the present invention to provide a nev/ compounds which maintain the activity of the knov/n 30 derivatives but are less toxical. It has been found that the new compounds of the ge¬ neral Formula I and salts thereof exhibit outstanding pesticical - parti¬ cularly insecticidal, acaricidal and nematodical - effect either per se or incombinated with additives. 2he toxici- ty of the said new compounds is generally lower than that of chemically related known compounds. Uoreover the com¬ pounds of the general Formula I have a more simple struc¬ ture, are less expensive and can be more readily prepared than the knov/n derivatives having a satisfactory toxicity. According to the present invention there are provided new compounds of the general Formula I and salts thereof C herein R 2 and R are as stated above). Preferable representatives of the compounds of the general Formula I are the following derivatives : 2 , 3-dihyάro- , 2-dimethyl-7-benzofuranyl-lϊ-methyl-2T-C -!' - -morpholinyl-methyD-carbamate and salts thereof ; 2 , 3-dihydro- , 2-dimethyl-7-benzofuranyl-H-methyl-H-/C I ' - -isopropyl D— IT' — C B-carbethoxyethyD-amino-methyl/-carbamate and salts thereof ; 2 , 3-dihydro-2, 2-dimethyl-7-benzofuranyl-ϊT-methyl-ϊT-/C β -3 , 4- -dimethoxy-phenyl-ethyD-__mino-methyl/-carbanate and salts thereof ; 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-ϊT-methyl-π-/ l'T'- - l,l-dimethyl-hydrazino)-methyl/-carbamate and salts thereof. According to a further aspect of the present invention there if provided a process for the preparation of compounds of the general Formula I and salt3 thereof, v/hich comprises a) reacting a compound of the general Formula III with a reactive derivative of an acid of the general Formula IT; or b) reacting a compound of the general Formula 7 with a compound of the general Formula 71, 711 and/or VIII; C7I) or c) reacting a compound of the general Formula IX with and if desired converting the compound of the general Formula I into a salt thereof. According to method a) of the process of the present invention a compound of the general Formula III is reacted with a reactive derivative of an acid of the general For¬ mula 17. As reactive acid derivative an acid halide of the general Formula XI or an anhydride of the general Formula Cxil or an active ester - preferably an ester of the general Formula XIII - Cxiii) may be used. The reaction may be preferably carried out in the presence of an aprotic solvent C e.g. benzene or toluene) and a tertiary base. As tertiary base e.g. a trialkyl amine may be used. The reaction may be accomplished pre- ferably at a temperature between 10 °C and 30 °C. Method b) of the process of the present invention may be preferably carried out under the same reaction conditions as method a). According to method c) of the process of the present invention it is preferred to use as starting material a compound of the general Formula IX, v/hich is prepared by reacting 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-methyl- -carbamate with thionyl chloride and paraformaldehyde, preferably in the presence of an aprotic organic solvent. The 2,3-dihydro-2,2-dime hyl-7-bensofuranyl- e hyl-carba- ate may be prepared from benzofuranol of the Formula III by known methods, e.g. by reacting with methyl isocyanate. The reaction according to method c) may be preferably carried out in the presence of an aprotic organic solvent Ce.g. benzene) at a temperature between 10 °C and 40 °C. It is preferred to add a tertiary base to the reaction mixture.- The compounds of the general Formula I may be converte into the salts thereof. Salt formation may be carried out by using inorganic or organic acids. The salts also exhibit the insecticidal, acaricidal and nematocidal effect of the bases of the general Formula I. According to a further aspect of the present invention there are provided pesticides - particularly compositions suitable for combating insects, mites and ne atodes - comp¬ rising as active ingredient at least one compound of the general Formula I or a salt thereof. The present invention encompasses all formulations comprising a compound of the general Formula I or a salt thereof. This the present invention covers all compositions whic comprise a compound of the general Formula I or a salt thereof and a carrier and appear in this form on the market. The scope of protecting extends furtheron to ready- -for-use preparations prepared from the above compositions by aqueous dilution; the latter compositions may be di¬ rectly used in agriculture or in other environment where pests occur. The compositions of the present invention may be ex¬ cellently used for combating insects at any suitable stage of the growth of the insect. Thus the compositions are particularly suitable for combating house fly, granary weerils, flour beetle, plant louse, cabbage butterfly, plum beetle, Ilexican bean beetle, sunflower beetle, pea louse, etc. The compositions of the present invention are parti¬ cularly useful as soil desinfectant and in glasshouse. The field of application of the said compositions is still broadened by the systemic effect thereof. The compositions of the present invention generally comprise additives in addition to the active ingredients. The said additives may be biologically active components or inert carriers and auxiliary agents which facilitate transport and storing and furtheron synergists. As further active ingredient insecticidal, nematocidal or acaricidal compounds having a different chemical struc¬ ture or point of biological attack may be used. Thus fungicidal or plant growth regulating compounds or artifical fertilizers may be used. The auxiliary agents are selected on the basis of the form in which the composition is intended to be used. Thus suspension concentrates may comprise 1-60 % by weight of an active ingredient of the general Formula I or a salt thereof and 40_99 by weight of auxiliary agents suitable for the formation of a stable suspension concent¬ rate. As auxiliary agent 1-10 by v/eight of a surfactant may be used. As preferable representatives of the surfac¬ tants the following compounds may be mentioned: alkyl phenol ethoxylates, polyoxyethylene alkylethers, polyoxy- ethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, non-ionic adducts of calcium alkyl aryl sulfo- nate, ethoxylated esters and salts thereof, phosphatated esters and salts thereof, alkali and alkaline earth lignine sulfonates, condensation products of formaldehyde and sodium alkyl aryl sulfonates, adducts of cresol and formaldehyde, etc. According to a preferred embodiment of the present invention there are provided dispersible granules compris¬ ing as active ingredient 1-99 % by weight of a compound of the general Formula I or a salt thereof in admixture with 99-1 by weight of an additive suitable for the formation of dispersible granules. As auxiliary agent preferably 0.1-1 J ' by v/eight* of an anionic and/or non-ionic surfactant, particularly one or more of the following agents may be used: alkali salts of alkyl and aryl sulfonic acids; alkali salts of condensation products of alkyl aryl sulfonic acids and ormaldehyde, alkyl aryl polyglycol ethers; sulfatated higher alcohols, polyethylene oxides; sulfatated fatty alcohols; esters of fatty acids and polyglycols and various other commercially available surfactants. According to a further preferred embodiment of the present invention there are provided granular compositions comprising preferably 1-20 % by weight of a compound of the general Formula I or a salt thereof as active ingredients in admixture with 80-99 % by weight of an additive. For this purpose adhesives, colouring agents and/or carriers may be used. Suitable adhesives are the following compounds polyvinyl alcohol, polyvinyl pyrrolidone, sugar, lignine sulfonates, polysaccharides and/or natural oils. As carrier e.g. sand, ground minerals, agricultural waste materials and products prepared thereof Ce.g. furfurol bran) and other commercially available substances having large surface may be used. According to a still further preferably embodiment of the present invention there are provided emulsion con¬ centrates comprising preferably 10-50 " _ by weight of a compound of the general Formula I or a salt thereof in admixture v/ith 50-90 by weight of an additive suitable for the formation of a stable emulsion, when the emulsion concentrate is emulsified in or in the presence of water. As additive e.g. 1-20 % by weight of a tenside and/or 0.1-5 5 by weight of a stabilizing agent may be used and ' the mixture may be filled up to 100 "oj weight with an or¬ ganic solvent. As tenside a mixture of anionic and non-ionic tensides having a HL3 value of 8-14 may be advantageously used. Thus the following tensides may be preferably applied: calcium salts of alkyl ar l sulfonic acids; mono- and diesters of phosphoric acid; nonyl and tributyl phenol polyglycol ethers adducts of fatty alcohols and ethylene oxide; fatty acid polyglycol esters; ethylene oxide and propylene oxide block polymers, etc. The following solvents may be used preferably for this purpose: mixtures of aromatic solvents Ce.g. xylenes, cyclohexanol, butanol, methyl ethyl ketone, isopropanol, etc. ). The compositions of the present invention may also contain a stabilizer. For this purpose preferably compounds comprising an epoxide group Ce.g. epichloro hydrine or edenol - epodised soya oil -, etc.) may be used. The compositions of the present invention may also comprise a synergi3t v/hich enables the use of smaller amount of the active ingredient of the general Formula I in the composition. The said additives are particularly useful in compositions v/hich are applied onto the surface of the plant or sites being contacted v/ith warm-blooded living organisms rather than onto the soil. As synergist preferably piperonyl butoxide may be used. According to a still further aspect of the present invention there is provided a method for combating undesire insects, mites and/or nematodes which comprises contacting the said pests at any suitable stage of their growth with an effective amount of a compound of the general Formula I or a salt thereof or a composition comprising the same. The compositions of. the present invention are parti- cularly suitable as soil desinfectant or on the surface of the plants and may be successfully applied both in glass¬ house and under field conditions. Further details of the present invention are to be found in the following Examples without limiting the scope of protection to the said Examples. Example 1 104.7 g of 2,3-dihydro-2,2-dimethyl-7-oenzofuranyl- -methyl-xT-chloro ethyl-carbamate are dissolved in 600 ml of benzene. To the solution at room temperature and within an hour a solution of 37.7 g of morpholine, 43.8 g of tri- ethyl amine and 50 ml of benzene is added. The reaction mixture is stirred for 2 hours whereupon 200 ml of water are added. The solid material goes into solution. The orga¬ nic phase is separated, dried over sodium sulfate and the solvent is distilled off. Thus 120.1 g of 2,3-dihydro-2,2- -dimethyl-7-benzofuranyl-IT-methyl-2 : r-/ϊT , -morpholinyl-methyl/- -carbaiaate are obtained, m.p.: 90-91 °C. The product is purified through the hydrochloride, mp. : 92-96 °C. Analysis : for the Formula C-,.--E ^l^O^ calculated: C = 63.75 Z H = 7.50 % IT = 8.75 55 found: C = 63.36 % H = 7.51 ft IT = 8.3655. Example 2 40.5 g of 2,3-dihydro-2,2-dimethyl-benzofuranyI-I'T-methyl -IT-chloromethyl-carbamate are dissolved in 250 ml of benzene To the solution at room temperature within an hour a solu¬ tion of 10.1 g of isopropyl amine, 17.2 g of triethyl amine and 50 ml of benzene is added. The reaction mixture is stirred for 2 hours and worked up as described in Example 1. Thus 30.4 g of 2,3-dihydro-2,2-dimethyl-77benzofuranyl-17- -methyl-_-/isopropyl-__mino-methyl/-carbamate are obtained, p.: 73-76 °C. Analysis: for the Formula C J-,LO. H dt„-2? d_0 j-> . calculated : C = 65 .75 % Ξ = 8.22 % IT = 9.59 found : C = 66 .01 ~ O H = 8 .07 5$ IT = 9.68 Example 3 24.5 g of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-I7- -methyl-IT-chloromethyl-carbamate are dissolved in 100 ml of benzene whereupon at room temperature within an hour a solu¬ tion of 10.1 g of triethyl " amine, 23.8 g of lT-/β-carbethoxy- -ethyl/-isopropylamine and 50 ml of benzene is added. The reaction mixture is worked up according to -Example 1. Thus oily 2, -dihydro-2,2-dimethyl-7-benzofuranyl-IT-methyl-H- -/CIT'-isopropyl)-IT'-Cfi-carbethoxy-ethyl)-amino-methyl/- -carbamate are obtained. Analysis: for the Formula C 21 H 31 I 2 0c calculated: G = 64.37 ft H = 7.92 ft IT = 7.15 ft found: C = 63.90 ft H = 3.12 ft IT = 7.05 ft. Example 4 13-5 g of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-IT- -methyl-IT-/chloromethyl/-carbamate are dissolved in 100 ml of benzene, whereupon within an hour -a solution of 12.8 g of 3,4-dimethoxy-β-phenyl-ethyl amine and 30 ml of benzene is added. The reaction mixture is worked up as described in Example 1. Thus 15.4 g of oily 2,3-dihydro-2,2-dimethyl- -7-benzofuranyl-IT-methyl-I.-/ 3,4-Cdime hoxy)-phenylethy1/- -amino-methyl-carbamate are obtained. Analysis: for the Formula G 3 H 30" 7 2 0 5 calculated : C = 66.66 ft H = 7.25 ft IT = 6.76 ft •found : C = 67.00 ft .H = 6 .85 ft Ε = 6.23 ft • Example 5 53.8 g of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-].T- -methyl-T-chloromethyl-carba ate are dissolved in 250 ml of benzene. To the solution at room temperature within an hour a mixture of 15.25 g of 1,1-dimethyl-hydrazine, 25.25 g of triethyl amine and 50 ml of benzene is added. The suspen¬ sion thus formed is stirred for 2 hours and filtered. Thus 51 g of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-IT-methyl-ΪT- -/H'-C1,1'-dimethy1-hydrazino)-methyl/-carbamate hydro- chloride are obtained, mp.: 107-110 C. Analysis: for the Formula C-, --IL-^ClIgO-, calculated : C = 54.63 ft H = 7.28 ft IT = 12.75 ft Cl = 1 found : C = 53.61 ft H = 7.27 ft IT = 11.94 ft Gl = 1 Example 6 16.4 g of 2,3-dihydro-2,2-dimethyl-7-benzofuranol are dissolved in 50 ml of toluene whereupon 14.9 g of phosgene are introduced into the solution at a temperature of -5 C within an hour. As acid binding agent 5 IT sodium hydroxide solution is added at a temperature between -5 °C and 0 °C at a rate that during addition the pH value should not be higher than 7. After an hour the toluene phase if separated, washed neutral with water, dried over sodium sulfate and the solvent is distilled off. The residual 2,3-dihydro-2,2-dimethyl-7-benzofuranyl- -chloro-formic acid esther are dissolved in 100 ml benzene. To the solution is added a solution of 15.6 g IT- orpholino- methyl)-methylamine and 12 g triethyl amine in 50 ml benzene at a temperature between +5 C and +10 C within an hour. The reaction mixture is worked up as described in Example 1. Thus 25.1 g 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-IT-methyl -l-/IT'-Cmorpholinomethyl)/-carbamate melts at 92-95 °C and is identical with the product obtained according to Example Example 7 22.6 g 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-chloro- -formic acid ester are dissolved in 100 ml benzene. To the solution is added a solution of 29.3 g pentachloro benzene in 100 ml benzene. As acid binding agent 5 IT sodium hydroxid solution or triethylamine is added in an amount to adjust the pH to 7. The obtained benzene solution is washed neutral, and to the solution is added a solution of 14.3 g IT-Cmorpho- linomethyl)-methylamine and 11 g triethylamine in 50 ml ben¬ zene at a temperature of 20 C within an hour. After mixing for 3 hours the reaction mixture is worked up as described in Example 1. Thus 2,3-dihydro-2,2-dimethyl-7-benzofuranyl- -lT-methyl-lT- lT'-morpholinomethyl)-carba ate melts at 92-96 ° Example 8 13 g of 1T----Cmorpholinomethyl)-methylamine are dissolved in 100 ml toluene whereupon 14.9 g phosgene are introduced into the solution at a temperature between -5 °C and 0 °G. To the mixture containing T-methyl-T-C orpholinomethyl)- -amino-carbonyl chloride a mixture of 15 g of 2,3-dihydro- -2,2-dimethyl-7-benzofuranol, 10 g of triethylamine and 50 ml of benzene is added. The reaction mixture is worked up as described in Example 1. Thus 2,3-dihydro-2,2-di- methyl-7-benzofuranyl-27-methyl-IT-CIT'-morpholinomethyl)- -carbamate melts at 92-95 °C and is identical with the product obtained according to Example 1. Example 9 13 g of IT—C orpholinomethyl)-methylamine are dissolved in 100 ml of toluene. Into the solution 7 g of phosgene are introduced at a temperature between -5 G and 0 C within an hour. As acid binding agent 5 IT aqueous sodium hydroxide solution is added in an amount to adjust the pH to 7. After 2 hours the toluene phase is washed neutral with water and to the solution comprising bis-/lT-methyl-C_T-morpholino- methyl)/-urea a solution of 15.8 g of 2,3-dihydro-2,2-di- methyl-7-benzofuranol, 10.1 g of triethyl amine and 50 ml of v/ater is added at room temperature within an hour. The reaction mixture is washed neutral with water, the organic phase is separated, dried and the solvent is removed. The residue is dissolved in hydrochloric acid whereafter the salt is re-converted into the base alkalizing the solution Thus 22.7 g of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-lT- -methyl-lT-ClT'-mo__ * pholinomethyl)-carbamate are obtained. Mp.: 92-96 °C. Exam le 10 To a toluene solution of IT-methyl-IT-Cmorpholinomethyl)- -amino-carbonyl-chloride a solution of 29.3 g of pentachloro phenol, 11 g of triethylamine and 100 ml of benzene is added. After 2 hours to the solution containing the penta- chlorophenyl-IT-methyl-2T-Cmorpholinomethyl)-amino-carboxylate at room temperature within an hour a solution of 15.8 g of 2,3-dilιydro-2,2-dimethyl-7-benzofuranol, 11 g of triethyl amine and 50 ml of toluene is added at room temperature within an hour. The reaction mixture is stirred at room temperature for 2 hours, treated with water, washed neutral, the organic solvent phase is separated, dried over sodium sulfate evaporated. The residue is converted into the sulfat with the aid. of diluted s Ifuric acid. On making the solu- tion alkaline 123.1 g of 2,3-dihydro-2,2-dimethyl-7-benzo- uranyl-IT-metliyl-IT-CIT'-morpholinoιne"-hyl)-carbarαate precipi¬ tates, mp. : 92-95 °G. Examp -le 11 In a mixture of 7 g of ethylene glycol and 52.6 g of water 4 g of Atlox 4862 are dissolved whereupon 35 g of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-I7-metliyl-IT-CIT'- -morpholinomethyl)-carbamate are incorporated with the aid of a high shear strength desagglomerating stirrer Ultra Turax 15 IT; 15 m/sec). The suspension thus obtained is ground in a cooled attritor C200 ml) in the presence of 100 ml of silicoquarzite glass pearls diameter 2 mm) for 45 minutes at 750 r.p.m. To the ground material 2 g of Soitem 22 FL/2T are added whereupon the glass pearls are removed by sieving through a sieve Cmesh size 1.5 mm). To the suspension 0.2 g of Tensiofix 821 are added and in¬ corporated with the aid of a Turrax 15 IT desagglomerating stirrer v/ithin 5 minutes. To the product 0.2 g of Tensiofix LO 51 antifoam agent are added. The particle size of the active ingredient of the composition thus obtained is below 5 um 95 ft Cmeasured by ultrasonic moist sieving), the floating capacity amounts to 90 ft Caccording to GIPAC) and the flow value is 52 sec CFord Ho. 4 glass). Preparations having the following composition are prepared: Component Amount Cft by v/eight) Active ingredient 1-60 Anionic or non-ionic surfactant 1-7 Antifreezer 5-10 Antisedimentating agent 0.1-0.5 Antifoam agent 0.1-0.5 Water ad 100 " . Example 12 Dis-persible granule A mixture of 700 g of 2,3-dihydro-2,2-dimethyl-7-benzo- furanyl-IT-methyl-IT-Cπ'-morpholinomethyl)-carbamate, 50 g of Atlox 4862, 50 g of Aerosil 0TB, 10 g of Plasdon K 25 and 1,90 g of lactose is homogenized in a MTH K7-10 CPapen- meier) powder mixer for 2 minutes Cl 000 r.p.m.). The powder mixture is ground in an air-flow mill C-HRS-80) so that 90 ft of the particles should be smaller than IQ/um Cmeasured by ultrasonic moist sieving). 10 g of the powder mixture thus obtained are contacted in a household coffee-mill with 1.2 ml of water to form granules C stirring period 20 seconds). The granules thus obtained are dried in vacuo at 50 °c. The dried product is 3ievedCmesh size 0.1 and 1.0 mm). The floating capacity of the granules thus obtained amounts to 84 ft Cmeasured by the CIPAG method). Preparations having following composition are prepared: Components Amount ft by weight) Active ingredient 1-99 Synthetic silicic acid 0.1-2 Dispersing agent 0.1-10 Anionic and non-ionic surfactant 0.1-5 Adhesive macromolecule 0.2-2 Sugar ad 100.0 Example 13 Gran les 5 ft by v/eight of 2,3-dihydro-2,2-dimethyl-7-benzofura- nyl-IT-me hyl-2T-/IT'-Cisopropyl)-IT'-Cβ-carbethoxyethyl)-amino- -methyl/-carbamate are admixed with 10 ft by weight of dimeth formamide and ,85 ft by weight of furfurol bran Cparticle size 0.2-1 mm). The granules are of the following composition: Component Amount ft by v/eight) Active ingredient 1-20 Solvent 3-10 Carrier ad 100 Example 14 Ξ ulsifiable concentrate 25 ft by weight of 2,3-dihydro-2,2-dimethyl-7-benzo- furanyl-IT-methyl-N-Cisopropyl-aminomethyl)-carbamate are dissolved in 49 ft by weight of methyl ethyl ketone. To the solution 1 ft by weight of edenol epoxidized soya oil) and 25 ft by weight of a mixture of e ulaifiers are added. The emulsifier mixture consists of the following components: ATLOX-4857 3 15 ft by weight ATLOX-3400 B 10 ft by weight SHΞLISOL R 62.5 ft by weight Isopropanol 12.5 ft by weight Preparations having the following composition are prepared: Component Amount ft by v/eight) Active ingredient 10-50 Ionic and non-ionic surfactant 5-10 Stabilizer 0.5-1.5 Solvent ad 100.0 Example 15 From the compounds of the present invention a series of dilution is prepared in acetone; concentration 1, 0.2, 0.04, 0.008 and 0.0016 ft, respectively. The solutions thus obtained θ.5 ml) are poured dropv/ise onto Whatman ITo. 1. filter paper discs Cdiameter 90 mm) placed in Petri-dishes. After the solvent has evaporated 1-2 weeks' old bean beetle C canthoscalides obtectus) images are placed into the Petri-dishes. 3 replicates C10-15 insects each) are used for each concentration. The pesticidal effect of the test compounds is evaluated after 24 hours, on the basis of the percental ratio of the killed and paralysed individuals. The solvent control group shov/s no mortality. The results obtained are summarized in Table I. Active ingredient Concentration of active ingredient Cft) Example ITu ber 1 0.2 0.04 0.008 0.001 m o r t a 1 i t y ' 3 97 80 53 27 0 1 100 97 87 50 0 4 100 87 70 37 0 2 100 100 60 40 0 Dioxacarb 100 • 93 43 30 0 Carbofurar 100 100 100 93 0 Example 16 From the test compounds a series of dilution disclose in Example 15 is prepared whereupon 3-5 days' old house fl Clαusca domestica) images being under slight carbon dioxide narcosis are -placed onto the infected treated filter paper discs. Three replicates C10-15 flies each) are used for each concentration. The insecticidal activity of the test compounds and that of the referent compounds is evaluated after 24 hours on the basis of the percental ratio of the killed and paralyzed flies. In the solvent control grop there was no mortality. The results are summarized in Tabl II. Test compound Concentration of active ingredient Cft) Example ITumber 1 0.2 0.04 0.08 0.001 m o r li t y ft 3 97 70 40 33 0 1 100 80 43 40 30 4 100 83 37 20 0 2 90 67 30 10 0 Dioxacarb 100 90 17 10 0 Carbofuran 100 100 67 53 43 - 20 - xample 17 From the 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-IT- -raethyl-IT-CIT'-morpholinomethyl)-carbamate, dioxacarb and carbofuran series of dilutions are prepared in acetone: the active ingredient content of the solutions amounts to 40.5, 13.5, 4.5, 1.5, 0.5, 0.16 and 0.05 mg active ingredient per 3.5/ul, respectively. The solutions Cθ.5/ul are applied v/ith the aid of a Hamilton syringe onto the dorsal cuticulum of small iunerican flour-beetle CTribolium confu3um) of L. larva stage. The age of the larvae is determined on the basis of the average larva v/eight C= 1.81 + 0.37 mg/larva) /See Sokoloff 1972/. Two replicates are used for each concentration C10 individuals per replicate). The insecticidal effect of the test compounds is evaluated after ,96 hours on the basi of the percental ratio of killed larvae. The control treat ment carried out v/ith 0. /Ul pure acetone solution shows no mortality. The results obtained are summarized in Table III. Test compound Dose, Ug/larva 40.5 13.0 4.5 1.5 0.5 0.16 0.03 Compound of m o r t a 1 i t y ft Example 1 100 100 95 90 90 80 75 Dioxacarb 80 55 50 50 45 40 25 Carbofuran 100 100 100 100 100 70 30 Example 18 The acute toxicity data Cp.o.) of the test compounds are disclosed in Table 17. Test compound on male rats on female rats C mg/kg ) . 2,3-dihydro-2,2-dimethyl-7- -benzofuranyl-IT-methyl-IT- -/IT'-Cisopropyl)-IT'-Cβ-car- betoxyethyl)-aιnino-methyl/- -carba ate 23.26 31.84 2,3-dihydro-2,2-dimethyl-7- -benzofuranyl-IT-methyl-lT- -CIT'-morpholinomethyl)-car- bamate 50.00 50.00 Carbofuran 8-14 Example 19 _> Preparation of a .starting material To a solution of 88.3 g of 2,3-dihydro-2,2-dimethyl- -7-benzofuranyl-IT-methyl-carbamate and 700 ml of benzene 12.6 g of paraformaldehyde are added, v/hereupon 48.8 g of thionyl chloride are added dropv/ise within an hour. After 2 hours the solution is clarified, filtered and the solvent is evaporated. Thus 104.7 g of 2,3-dihydro-2,2-dimethyl-7- -benzofuranyl-IT-methyl-IT-chloromethyl-carbamate are obtained mp.: 115-118 °C. Analysis: for the Formula C-^H- j gClITO- j calculated: C = 57.88 ft H = 5.94 ft IT = 5.19 ft Cl = 13-1 found: C = 57.67 ft H = 6.17 ft IT = 5.22 ft Gl = 12.0 Example 20 Preparation of gran les 3 ft by weight of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl- -ϊT-methyl-IT-CIT'-morpholinomethyl)-car- bamate - 22 - 6 ft by weight of piperonyl butoxide 15 ft by weight of dimethyl formamide and 76 ft by v/eight of furfurol bran Cparticle size 0.2-1 mm) are admixed. Granules having the following composition are prepared Com onent Amount Cft by weight) Active ingredient 1-10 Piperonyl butoxide 2-20 Solvent 5-20 Carrier ad 100 Example 21 Emulsifiable concentrate 20 ft by weight of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl -IT-methyl-II-CIT'-morpholinomethyl)-carba mate 15 ft by weight of piperonyl butoxide 7 ft by weight of ATLOX 3276 FLIT and 58 ft by weight of xylene are admixed. The emulsifiable concentrate thus obtained has the following composition: Component Amount Cft by weight) Active ingredient 5-30 Piperonyl butoxide 10-30 Ionic and non-ionic surfactant 5-15 Solvent ad 100. Example 22 Determination of synergistic effect From the compound according to Example 1 a series of dilution is prepared in acetone; concentration: 0.6, 0.2, 0.067 and 0.022 ft by weight, respectively. From these solutions 0.5 ml each is poured dropwise onto Whatman Ho. 1. filter paper discs Cdiameter 90 mm) placed in Petri-dishes. The discs vere previously treated with 0.5 ml of a 0.04 ft piperonyl butoxide solution. After the evapo¬ ration of the acetone 3-5 days' old house fly C usca do¬ mestica) imagos being under slight carbon dioxide narcosis are placed onto the filter paper discs. The test is evaluat as described in Example 16. The results are summarized in Table 7. Test compound Concentration of active ingredient Cft) 0.6 0.2 0.067 0.022 m 0 r t a 1 i t y ft Compound accor¬ ding, to Example 1 100 100 78 32 Compound ' accor¬ * _ ding to Example 1 + piperonylbuto- xide 100 100 100 69 Carbofuran 100 100 100 71 Example 23 Deter ination of s;ystemic effect The granules prepared according to Example 13 Cactive ingredient content ft) are spread in an amount correspond ing to a dose of 15 kg/ha and 7.5 kg/ha, respectively, into flower pots filled with soil, whereupon seeds of broad bean C icia faba) are sown into the soil. T e plants are infected with plant louse CMegaure viciae) placed into lea isolator at a 2 weeks' age. Twenty insects are used for each isolator. The percental mortality is evaluated after 48 hours. The data obtained are summarized in Table 71. - 24 - Test compound Dose m o r t a l i t y ft Compound according to Example 13 100 38 CHIITUFUR 5 G 100 56 Untreated control 0 0

Claims: 3 3 AMENDED CLAIMS [received by the International Bureau on 23 April 1986 (23.04.86); original claims 1—24 replaced by new claims 1—24 (8 pages)] 1. Compounds of the general Formula I and salts thereOJ. wherein _2 stands for hydrogen or C, - alkyl; and represents 0-, _ . alkyl or C p _ Q dialkyla ino or ε group of the general Formula R'- CH p egral number 1 or 2*. _Vj - wherein . is an int 4. *-*• . ' represents -000? , wherein — -> is C-, ^ alkyl or a group of the general For¬ mula II, 20 <- Z and R and R _' stand for hydrogen or C-^ εlkoxy; or *5 and RR ttooggeetthheerr m mayy.. form a group of the Formula .;-C i;' -morpholinyl )-methyl-carbamate and salts thereof . 3. 2, 3-dihydro-2 , 2-dimethyl-7-benzofuranyl-II-methyl- -I- isopropylamino-methyl)-carbamate and salts thereof. 4. 2,3-dihydro-2,2-dimethyl-7-benzo ranyl-IT-methyl- -IT-/CH'-isopropyl)-H'-Cβ-carbetoxy-ethyl)-amino-methyl/- -carbamate and salts thereof. 5. 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-IT- ethyl- -IT-/C β -3,4-dimethoxy-phenyl-ethyl)-amino-methyl/-carba ate and salts thereof. 6. 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-IT-methyl- —17—/I7*— l,l-dimethyl-hydrazino)-methyl/-carbamate and salts thereof. 7. Process for the preparation of new benzofurane derivativ wherein R,2; stands for hydrogen or G^ A alkyl; and R- represents C-, * alkyl or C 2 _ 8 dialkylamino, or a group of the general Formula R - CHD - wherein n is an integral number 1 or 2; 4 5 r *eepresents -C00R , wherein ,5 is C, * alkyl or a group of the general Formula II, ClD and 6 7 R and R stand for hydrogen or C-, , alkoxy; or 2 3 l ~' R and R together may form a group of the _orπι:_,a -CCH 2 ) 2 -C- CH 2 )p-, with the proviso that R 2 and R3 together do not stand for methyl, and salts thereof, which comprises a) reacting a compound of the general Forπula III with a reactive derivative of an acid of the general Fo: la IV; or b) reacting a compound of the general .-orz la with a compound of the general Forπula Vi, VII anc/or VIII; or c) reacting a compound of the general Formula IX with an amine of the general Formula X and if desired converting the compound of the general For¬ mula I into a salt thereof. 8. Process according to method a) of Claim 7 which comprises using as reactive derivative of the acid of the general Formula IV an acid chloride of the general Formula XII or an urea of the general Formula XI or an active esther - preferably a compound of the gene¬ ral Formula XIII 9. Process according to method a) of Claim 7 v/hich comprises carrying out the reaction in an aprotic solvent - preferably benzene or toluene - in the presence of a tertiary base at a temperature between 10 and 30 C 10. Process according to method b) of Claim 7 v/hich comprises carrying out the reaction in an aprotic organic solτent - preferably benzene or toluene - in the presence of an acid binding agent - preferably a tertiary base. 11. Process according to method c ) of Claim 7 which comprises using in the reaction a compound of the general Formula IX prepared by reacting benzofuranol of the For¬ mula III with methyl isocyanate and reacting the 2,3-di- 36 hydro-2,2-dimethyl-7-benzofuranyl-methyl-carbamate thus obtained with thionyl chloride and paraformaldehyde, preferably in the presence of an aprotic organic solvent. 12. Process according to method c) of Claim 1 which comprises carrying out the reaction in the presence of an aprotic solvent, preferably in benzene, at a temperature between 10 and 40 °C, preferably in the presence of a tertiary base. 13. Pesticidal composition comprising as active ingre¬ C dient at least one compound of the general Formula I 0 v/herein stands for hydrogen or C\ 4 alkyl; and R' represents a group of is an integral number 1 or 2; 5 5 represents -C00R , wherein ~ , R is C-, / alkyl or a group of the general For¬ mula II ; or R2 and R3 together may form a group of the Formula -CCH 2 ) 2 -0-CCH 2 ) 2 - or a salt thereof. 14. Pesticidal composition according to Claim 13 in the form of a suspension concentrate comprising as active ingredient 1-60 ft by weight of a compound of the general Formula I or a salt thereof in admixture with suitable auxiliary agents and optionally further active ingredientC s . 15. Suspension concentrate according to Claim 14 coπp- rising 1-10 ft by weight of a surfactant as auxiliary agent. 16. Dispersible granular composition according to Claim 13 comprising as active ingredient 1-99 ft by weight of a com of the general Formula I or a salt thereof in admixture with suitable auxiliary agents and optionally further active in- gredientCs). 17. Dispersible granular composition according to Claim 16 comprising 0.1-10 ft by weight of an anionic and/or non- -ionic surfactant as auxiliary agent. 18. Granular composition according to Claim 13 comp- rising as active ingredient in an amount of 1-20 ft by v/eight a compound of the general Formula I or a salt thereof in admixture with 80-99 ft by v/eight of suitable auxiliary agents and optionally further active ingredientC s) and/or syner- gist s). 19. Granular composition according to Claim 18 comp¬ rising an adhesive, colouring agent and/or carrier as auxi¬ liary agent. 20. Granular composition according to Claim 18 comp¬ rising piperonyl butoxide as synergist. 21. Emulsifiable concentrate according to Claim 13 comprising as active ingredient in an amount of 10-50 ft by weight a compound of the general Formula I or a salt thereof in admixture with suitable auxiliary agents suitable to form a stable emulsion and optionally further active ingredientCs) and/or synergistCs). 22. Emulsifiable concentrate according to Claim 21 comprising as auxiliary agent 1-20 ft by weight of tenside and/or 0.1-5 ft by weight of a stabilizer and a solvent up to 100 ft by weight. 23. Emulsifiable concentrate according to Claim 21 comprising piperonyl butoxide as synergist. 24. llethod for combating insect pests and for in¬ hibiting the growth thereof v/hich comprises contacting the insects at optional growth stage with at least one compound of the general Formula I or a salt thereof or a composition comprising the same, preferably on a plant or in * he soil.

Inventors: DENES VALERIA, DETRE TAMAS, LANYI GYOERGY, NAGY LAJOS, PAP LASZLO, RADVANY ERZSEBET, SOMFAI EVA, SZEGOE ANDRAS, VISNYOVSZKY MARIA, DENES, VALERIA, DETRE, TAMAS, LANYI, GYOERGY, NAGY, LAJOS, PAP, LASZLO, RADVANY, ERZSEBET, SOMFAI, EVA, SZEGOE, ANDRAS, VISNYOVSZKY, MARIA
Applicants: CHINOIN GYOGYSZER ES VEGYESZET, CHINOIN GYOGYSZER ES VEGYESZETI TERMEKEK GYARA RT.
Application year: 1985
Main classification: C07D307
IPC codes: A01N47, A01P5, A01P7, C07D307