HU179923B - Insecticide and acaricide compositions with synergetic activity containing benzodioxolane derivatives and known carbamate derivatives as active substances - Google Patents

Abstract

Insecticidal and acaricidal compsn. contains as active ingredients a benzodioxole deriv. of formula (I) (R H, halo, alkyl, alkenyl or NO2; R2=alkyl or H; R2 = aralkyl, alkyl, alkenyl, cycloalkyl, or H when R is not H or halo, R1+R2 can also together be alkylene), plus >=1 of carbamates, carboxylic acid esters (including natural or synthetic pyrethrins) and phosphoric acid esters. The wt. ratio (I): other active ingredient is 0.1-10-10:0.1, and compsns. can contain usual diluents and/or surfactants. (I) are synergists for the other pesticides being more active than piperonyl butoxide and effective for a wide range of insecticides. The compsns. are useful in agriculture, forestry, hygiene and protection of stored goods.

Description

The present invention relates to synergistic insecticidal and acaricidal compositions containing the benzodioxolane derivatives of formula I and the carbamate derivatives of formula II as active ingredients.

In the formula (I):

R is hydrogen, (1-4C) alkyl, halogen;

R ¹ is hydrogen or C 1-4 alkyl;

R ² is hydrogen or C 1-4 alkyl; and

R ¹ and R ^{2 taken} together may be C 1-4 alkylene.

In the formula (II):

R ³ is naphthyl, dioxolanylphenyl, phenyl substituted up to three times with C 1-4 alkyl, C 1 -C 4 alkyl mono- or di-substituted with 2,3-dihydrobenzofuranyl or benzodioxolanyl, or C 1-4 alkoxy substituted with phenyl; ; and

R ⁴ is C 1-4 alkyl.

The formulations of the present invention contain the active ingredient in a concentration of 0.1 to 95% by weight with solid carriers, preferably natural or artificial rock flour, and / or liquid diluents, preferably organic solvents such as halogenated hydrocarbons, lower dialkylformamides or dimethylsulfoxide. optionally surfactants, preferably emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, and protein hydrolysates or dispersants. such as lignin, sulphite impurities or methylcellulose.

The synergistic compositions of the present invention have very strong insecticidal and acaricidal activity.

Benzodioxolane derivatives such as α, α-dimethyl- (3,4-methylenedioxyphenyl) acetonitrile and α, α-ethylene- (3,4-methylenedioxyphenyl) are known to acetonitrile can be used as an intermediate for the preparation of medicaments (German Patent Publication No. 2,215,496 and J. Org. Chem. 1972, 977-82). Also known are carbamate-type insecticides, such as 2-isopropoxyphenyl-N-methylcarbamate, 3,4,5-trimethylphenyl-N-methylcarbamate, 1-naphthyl-N-methylcarbamate. , 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-N-methylcarbamate, and 2- [1,3-dioxolan-2-yl20-phenyl] -N-methylcarbamate.

Synergistic compositions containing carbamate derivatives such as 2-isopropoxyphenyl-N-methylcarbamate as active ingredient are also known [Bull. Org. Health. Org. 35, 691-708 (1966), Die 25 Insecticide 1966, 516-524], however, the efficacy of these synergistic drug combinations is not satisfactory.

The synergistic effect of the compositions of the present invention is advantageously observed when, in addition to the benzodioxolane derivatives of formula (I), R, R ¹ and R ^{2 are} present as the active ingredient of the compositions.

-1179923 Designation as defined above - contain - a (II) carbamate of the formula: - in formula (II), R ³ and R ⁴ are as defined above.

Preferably, the carbamate derivatives of formula (II) having the formula (II):

R ³ is phenyl or naphthyl optionally substituted with C 1-4 alkyl; and R ⁴ is as defined above.

Also very preferred are the carbamate derivatives of formula (II) wherein, in the formula (II):

R ³ is 2,3-dihydrobenzofuranyl or benzodioxolanyl optionally substituted with C 1-4 alkyl, preferably methyl; and

R ⁴ is as defined above.

Surprisingly, the insecticidal and / or acaricidal activity of the compositions containing the active compound combinations according to the invention is significantly greater than the effect of the individual components or the sum of the effects of the components. In addition, the effect of the compositions comprising the active compound combinations of the present invention is significantly greater than that of the active compound combination of the already known 2-isopropoxyphenyl-N-methylcarbamate and piperonyl butoxide. The synergistic compositions containing the benzodioxolane derivatives of the present invention exhibit excellent synergistic effects not only with one class of active ingredient but also with a broad range of chemical classes.

The synergistic compositions containing the benzodioxolane derivatives of the present invention thus provide a valuable enrichment of the range of insecticidal and acaricidal compositions.

The compounds which can be used as synergistic components in the compositions comprising the combinations of the invention are defined by formula (I).

Preferred substituents in formula (I) are: R is hydrogen, chloro or bromo, C 1-4 alkyl;

R ¹ is hydrogen or C 1-3 alkyl, especially methyl;

R ² is C 1-4 alkyl or hydrogen when R is C 1-4 alkyl; and

R ¹ and R ^{2 taken} together may be C 1-4 alkylene.

Examples of benzodioxolane derivatives of the formula I for use in the compositions of the invention include the following: α-methyl, α-ethyl, α-η-propyl, α-isopropyl, α-η-butyl, α- isobutyl, α-sec-butyl, α-tert-butyl, α, α-dimethyl, α-methyl-α-ethyl, α-methylan-propyl, α-methyl-α-isopropyl- (3,4-methylenedioxyphenyl) acetonitrile and derivatives thereof at the 6-position substituted by chlorine or bromine, methyl, ethyl, η-propyl, isopropyl, tert-butyl and 6-methyl, 6-ethyl, 6-n-propyl, 6-isopropyl, 6-tert-butyl (3,4-methylenedioxyphenyl) acetonitrile.

The listed compounds are partly novel but can be prepared by methods known in the art [German Patent Nos. 2,215,496 and 2,335,347, British Patent No. 1,109,527, J. Am. Chem. Soc. 64, 24 862,487 (1942), J. Org. Chem. 1972, 977-982].

The novel compounds of formula (I) of the present invention wherein R 5 is hydrogen or halo may be prepared by reducing 3,4-methylenedioxybenzaldehyde to piperonyl alcohol and converting it to the corresponding halide derivative. which is reacted with a cyanide compound to give 3,410-methylenedioxyphenylacetonitrile [Braun, Wirz, Bér. dt. Chem. Ges. 60,110 (1927)]. This compound is then prepared by a known method (Dehmlov, 1975, New Synthetic Methods 1, 19, Makosa, Pure Appl. Chem. 43, 439 (1975), Makosa et al., Chimie et In15 dustrie 93, 537 (1965), Paris). , Makosa, Jonczyk, Org.

Syn. 55, 91 (1976)] compounds of the general formula (III) - alkylation - in formula (III), ^R1 and ^R2 are as defined above. The alkylated compounds can then be halogenated, for example with sulfonyl chloride or with bromine. The reaction scheme is illustrated in Scheme a).

Alternatively, 3,4-methylenedioxybenzaldehyde can be halogenated (Dallacker, Liebigs Ann. Chem. 633, 14 (1960), Weisse, Bér. dt. Chem. Ges. 43, 2605-25 (1910)] and the halogenated derivative is reacted as described above. However, this method, or this order, yields the end product in poor yield.

Where:

a) R is n-propyl and R ¹ and R ² are as defined above, the synthesis is carried out by the following steps: safrole-dihydrosafrol-6- (chloromethyl) -dihydrosafrol -> 6- (cyanomethyl) -dihydrosafrol-1-desired compound;

b) R is a tert-butyl group and R ¹ and R ² are the same as described above: 4-tert-butylpyrocatechin - 3,4-methylenedioxytert-butylbenzene 6- (chloromethyl) -3,4-methyl) -3,4-methylenedioxy-tert-butylbenzene 6- (cyanomethyl) -3,4-methylenedioxy-tert-butylbenzene * the desired compound. The toluene and ethylbenzene derivatives of the present invention can be prepared analogously from 4-methyl and 4-ethylpyrocatechin (U.S. Patent Nos. 2,485,600 and 2,485,680 for the preparation of the chloromethyl compound). .

Each step of the described synthesis steps is known or can be carried out according to known methods. For example, 6- (chloromethyl) intermediates may be prepared according to U.S. Patent Nos. 2,485,600 and 2,485,680.

Among the carbamate derivatives of the formula (II) used in the compositions of the invention, the following compounds are mentioned: 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, 4-methylphenyl, 4-ethylphenyl, 4-n-propylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl -, 4-n-propoxyphenyl, 3,4,5-trimethylphenyl, 1-naphthyl, 2,3-dihydro-2,2-dimethyl-6-benzofuranyl, 2- (1,3) dioxolan-2-yl-phenyl) and 2,2-dimethyl-1,3-benzodioxolan-4-yl-N-methylcarbamate.

These compounds are known in the art for their preparation and use (U.S. Patent Nos. 3,009,855, 2,903,478 and 3,111,539).

As mentioned above, the active ingredient 65 of the present invention is a combination of formula (I)

A benzodioxolane derivative of -2179923, wherein R, R ¹ and R ^{2 in} formula (I) are as defined above, and a carbamate derivative of formula (II), in which R ³ and R ⁴ are as defined above Formulations containing an excellent increase in the effect of each component or the sum of the effects of the components.

The weight ratio of the components in the compositions of the invention may vary within a relatively wide range. The benzodioxolane derivatives of formula (I), wherein R, R ¹ and R ^{2 in} formula (I) are as defined above, and the carbamate derivatives of formula (II), wherein R ³ and R ^{4 in} formula (II) in a ratio of from 0.1: 10 to 10: 0.1, particularly preferably from 0.5: 1.0 to 3.0: 1.0. The compositions containing the active compound combinations according to the invention not only have a rapid pest control effect, but also exterminate pests, in particular insects, in various stages of development. These pests include those found in agriculture, forests and stored products as well as those found in material and health protection.

The compounds of the present invention may be used, for example, against the following pests:

From the order of the Isopoda, such as Oniscus asellus, Armadillidium vulgare, Porcellio scaber,

From the order of the Diplopoda, for example, Baniulus guttulatus,

From the order of Chilopoda, for example, Gephilus carpophagus, Scutigera spec.,

From the order of the Symphyla, such as Scutigerella immaculata,

From the order of Thysanura, such as Lepisma saccharina,

From the order of Collembola, for example, Onychiurus armatus, 35

From the order of Orthoptera, e.g., Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spec., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria, 40

From the order of the Dermaptera, such as Forficula auricularia,

From the order of the Isoptera, for example Reticulitermes spec.,

From the order of Anaplura, for example, Phylloxera vastatrix, Pemphigus spec., Pediculus humanus corporis, Haema-topinus spec., Linognathus spec.,

From the order of Mallophaga, for example, Teichodectes spec. Demalinea spec.,

From the order of Thysanoptera, such as Hercinothrips femoralis, Thrips tabaci,

From the order of Heteroptera, e.g., Eurygaster spec., Dysdercus intermedius, Piesma quadrat, Cimex lectularius, Rhodnius prolixus, Triatoma spec.

From the order of Homoptera, for example, Aleurodes brassicae, Bemesia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiph. ., Euscelis billobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax stritellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spec., Pxylla spec.,

From the order of Lepidoptera, such as Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata,

Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spec., Bucculatrix thurberiella, Phyllocnistic citrella, Agrotis spec., Euxoa spec., Feltia spec., Earias insulans, Heliothis, Heliothis. Panolis flammea, Prodenia litura, Spdoptera spec., Trichoplusia ni, Carpocapsa pomonella, Pieris spep., Chilo spec., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoeeia 10 podana, Capua reticulans, Choristoneura fumiferana, Clysia viridana,

Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acenthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Laptinotarsa decemlineata, Phaedon cochleeriae, Diabotica spec., Psylliodes ch. , Sitophilus spec., Otiorrhyn20 chus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spec., Trogoderma spec., Anthrenus spec., Attagenus spec., Lyctus spec., Meligethes aeneus, Ptinusole, Miptus holol. , Tribolium spec., Tenebrio molitor, 25 Agriotes spec. ,, Gonoderus spec., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica

From the order of Hymenoptera, e.g. Diprion spec., Hoplocampa spec., Lasius spec., Menomorium pharonis, Vespa spec.,

From the order of Diptera, for example, Aedes spec., Anopheles spec., Culex spec., Drosophila melanogaster, Musca spec., Fannia spec., Calliphora erythrocephala, Lucilia spec., Chrysomyia spec., Cuterebra spec., Gastrophilus spec., Hyppobosca spec. , Stomoxys spec., Oestrud spec., Hypoderma spec., Tabanus spec., Tannia spec., Bibio hortulanus, Oscinella frit, Phorbia spec., Pegomyia hyoscyami, Geratitis capitata, Dacus oleae, Tipula paludosa,

From the order of the Siphonaptera, e.g., Xenopsylla sheopis, Ceratohyllus spec.,

From the order of the Arachnia, such as Scorpio maurus, Latrodectus mactans,

From the order of Acarina, e.g., Acerus siro, Argas spec., Ornithodoros spec., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spec., Rhipicephalus spec., Amblyomma spec., Hyalomma spec., Ixodes spec., Psoroptes spec. spec., Sarcoptes spec., Tarsonemus spec., Brybia praetiosa, Panonychus spec., Tetranychus spec.

The active compounds of the present invention are formulated into conventional formulations such as solutions, emulsions, sprays, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, natural suspensions, emulsifiers, capsules, seed coatings, combustible compositions such as smoking cartridges, cans, spirals, and 60 ultra-low volume (ULV) cold and warm fog formulations.

These formulations may be prepared in a known manner, for example, by avoiding the active ingredients with fillers, for example, liquid solvents, other liquefied gases and / or solids.

-3179923 with carriers, optionally with the addition of surfactants such as emulsifiers or dispersants and / or foaming agents. When water is used as a solvent, auxiliary solvents such as organic solvents may be used.

Suitable liquid solvents include: aromatic hydrocarbons such as xylene, toluene, benzene or alkylnaphthalenes: chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffins such as petroleum fractions; alcohols, such as butanol or glycol, and ethers or esters of these alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; highly polar solvents such as dimethylformamide, dimethylsulfoxide and water. By liquefied gas fillers or carriers are meant liquids which are gaseous at room temperature, such as aerosol propellants such as hydrogen halides such as freon and butane, propane, nitrogen and carbon dioxide. Solid carriers include natural rock meals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock meals such as highly dispersed silica, alumina, and silicates. Solid carriers for granules include crushed or fractionated natural rocks such as chelate, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic or organic rock flour, and granules of organic materials such as sawdust, coconut shells and tobacco stalks. Emulsifiers and / or foaming agents include nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl poly (glycol ether). Dispersing agents include, for example, lignin, sulphite impurities and methyl cellulose, for example, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and protein hydrolysates.

The compositions may also contain adhesives such as carboxymethylcellulose, natural and synthetic powder, lump or latex-like polymers, acacia, polyvinyl alcohol, polyvinyl acetate.

Pesticides consist of an active ingredient and an additive. Active ingredients can also be referred to as "active substances", which are mixtures of chemical products and actually act as plant protection agents. Additives determine the physical properties of the mixtures which make the active ingredient suitable for use as insecticides and acaricides.

In addition, inorganic pigments such as iron oxide, titanium oxide, ferrocyan, and organic dyes such as alizarin, azo-metal phthalocyanine inks, and printing elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc may also be used.

The compositions of the invention generally contain from 0.1 to 95 sú1y%, preferably from 0.5 to 90 weight ⁰ / drug.

The active compounds of the invention may be used in the form of their commercially available formulations or as ready-to-use formulations prepared from these formulations.

Ready-to-use formulations of commercially available formulations have a wide range of active ingredient concentrations ranging from 0.000,000 to 1 to 95% by weight, preferably 0.01 to 10% by weight.

When used in health and storage stock, the active ingredients are distinguished by their excellent residual action on wood and clay and their alkaline stability on calcined surfaces.

Preparation examples

1. Preparation of a dusting agent

To prepare a convenient formulation of the active compound, 1 part by weight of the active ingredient of formula (A 1), (A ₂ ), (A ₃ ), (A ₅ ) or (A ₆ ), 1 part by weight of 1-4, 39, 45 or 46 is compared. The synergist of Example 1 and 98 parts by weight of natural rock flour and the mixture are ground to a powder. The resulting composition is pulverized to the insect-infested portion of the plants at the required concentration.

2. Production of dispersible powder (dispersible powder)

20 parts by weight of the active ingredient of formula (Aj), (A ₃ ) or (A ₄ ) and 20 parts by weight of the synergist of Examples 1-4, 35, 37 or 39 are mixed with 1 part by weight of dibutylnaphthalene sulfonate. , 4 parts by weight of lignin sulfonate, 8 parts by weight of highly dispersed silica and 47 parts by weight of natural rock meal, and the mixture is ground to a powder. Before use, the wettable powder is mixed with water so that the resulting mixture contains the required amount of the active ingredient.

3. Preparation of a spray formulation

To prepare a suitable spray formulation, 2 parts by weight of the active ingredient of formula A, 0.5 parts by weight of the active compounds of Examples 1-4, 35, 37-40, 45 or 46 are dissolved in 25 parts by weight of methylene chloride and the resulting solution is sprayed and then in a 50:50 ratio

57.5 parts by weight of difluorodichloromethane 11/12 are added.

4. Preparation of an oily spray

For the preparation of an oily spray, 1 part by weight of the active ingredient of formula (A 1), (A ₂ ), (A ₃ ), (A ₄ ), (A ₅ ) or (A ₆ ) and 1 part by weight of 1-4, 35, 37. , 45 or 46 is dissolved in 10 parts by weight of n-propanol, 98 parts by weight of petroleum are added and the resulting mixture is stirred until a homogeneous solution is obtained. The resulting oil spray can be sprayed on insects in homes.

The following examples illustrate the effect of formulations containing benzodioxolane derivatives of the invention and known active compounds. Known carbamate-type active compounds of the known formulas are represented by formulas (A ₁ ) to (A ₆ ).

the effect of formulations containing the known piperonyl butoxide synergist (compound of formula (K)) is also shown for comparison purposes.

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Example A)

LT _{] 00} test

Experimental animals: female Musca domestica resistant to phosphoric ester derivatives: strain: Weymanns.

Solvent: Aceton.

Solutions of the active compounds, synergists and the active synergist mixture are prepared from which

Pipette 2.5 ml into Petri dishes on 9.5 cm diameter filter paper discs. The filter paper absorbs the solutions. Allow the Petri dishes to remain open until the solvent has completely evaporated. 25 experimental animals were then placed in each Petri dish and covered with a glass lid.

The condition of the experimental animals is examined for a maximum of 6 hours. The time required for a 100% destructive effect is determined. If the LT ₁₀₀ is not reached after 6 hours, the percent mortality is determined.

Table I summarizes the concentrations and activity of the active substances, synergists and mixtures:

Table I

LT ₁₀₀ test against phosphoric acid ester resistant female Musca domestica (strain: Weymanns)

Active substance v. synergistic formula v. example number Concentration (%) LT ₁₀₀ (min), respectively. death rate (%) THE, 1.0 360 = 0% a ₂ 1.0 360 = 0% ₃ 1.0 360 = 0% ₄ 1.0 360 = 20% A5 1.0 360 = 10% THE* 1.0 360 = 30% K 1.0 360 = 0% First 0.2 210 0.04 360 = 35% Second 1.0 360 = 95% Third 1.0 360 = 80% 4th 1.0 360 = 90% 35th 0.2 360 1.0 180 0.04 360 = 10% 37th 1.0 360 38th 1.0 360 = 80% 39th 1.0 360 = 0% 40th 1.0 360 = 0% 45th 1.0 360 = 25% 46th 1.0 360 = 20% 41st 1.0 360 = 10% 20th 1.0 360 = 10% 21st 1.0 360 = 90% 0.2 360 = 20%

atoauyag + synergistic diet v. example number Concentration of active ingredient + synergist (%) LT _lt , (min) and degree of death (° / o) Aj + K (known) 0.2 p 0.2 360 = 85% J + 4 0.008 +0.008 360 J + 40 0.04 + 0.04 240 J + 2 0.04 + 0.04 150

Active ingredient + synergistic formula v. example number Concentration of active ingredient + synergist (%) LTi "(minutes) and degree of death (%) A] + 3 0.04 + 0.04 150 A, + 38 0.008 + 0.008 360 = 90% J + 45 0.008 +0.008 360 Aj + 35 0.04 ± 0.2 90 ' 0.008 + 0.04 240 ' 0.2 + 0.04 105 ' 0.04 + 0.008 360 ' 0.008 + 0.08 180 ' 0.04 + 0.004 360 ' Aj + 1 0.008 + 0.04 150 ' 0.2 + 0.04 105 ' 0.008 + 0.08 150 ' 0.04 + 0.004 360 ' The! +37 0.2 + 1.0 60 ' 0.2 + 0.04 150 ' 0.04 + 0.4 60 ' 0.0084 to 0.8 150 ' 0.2 + 0.02 105 ' J + 41 0.2 + 1.0 120 ' 0.2 + 0.04 180 ' 0.04 + 0.4 180 ' 0.008 +0.8 240 ' 0.2 + 0.02 360 ' J + 20 0.2 + 1.0 90 ' 0.008 +0.04 360 ' 0.2 + 0.04 150 ' 0.04 + 0.4 105 ' 0.008 +0.8 150 ' 0.2 + 0.02 180 ' J + 21 0.4 ± 0.2 90 ' 0.04 +0.008 150 ' 0.008 +0.08 150 ' 0.2 + 0.02 105 ' ₂ + K (known) 1.0 + 1.0 == S 360 »U% ₂ +4 0.04 + 0.04 360 = 90% A ₂ + ₂ 0.2 ± 0.2 240 The ₂ +3 0.2 ± 0.2 360 The ₂ +38 0.04 + 0.04 360 = 85% a ₂ + i 0.2 ± 0.2 240 A ₂ +37 0.04 + 0.04 360 A ₂ +39 0.04 + 0.04 360 = 90% A ₂ +46 0.2 ± 0.2 240 A ₂ +45 0.04 + 0.04 360 ₃ + K (known) 1.0 + 1.0 360 = 40% The ₃ +38 0.2 ± 0.2 6 ^hours = 90% a ₃ + i 0.2 ± 0.2 180 The ₃ +46 1.0 + 1.0 360 The ₃ +45 0.2 ± 0.2 360 = 95% ₄ + K (known) 0.2 ± 0.2 360 = 75% The ₄ +4 0.008 + 0.008 360 A ₄ + 2 0.008 +0.008 240 The ₄ +35 0.008 +0.008 180 The ₄ +3 0.04 + 0.04 180 The ₄ +38 0.008 +0.008 240 The ₄ + l 0.008 + 0.008 150 A ₄ +37 0.008 +0.008 210 A ₄ +39 '0.008 +0.008 240 A ₄ +46 0.008 +0.008 360 The ₄ +45 0.008 +0.008 210 The ₅ + K (known) 0.2 ± 0.2 360

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Active ingredient + synergistic formula v. example number Concentration of active ingredient + synergist (%) LTuo (min) and degree of death (%) ₅ +4 0.2 ± 0.2 240 The ₅ + 2 0.2 ± 0.2 360 A _s + 35 0.04 + 0.04 360 The ₅ +3 0.2 ± 0.2 210 The ₅ +38 0.04 + 0.04 360 = 95% a ₅ + i 0.2 ± 0.2 150 A ₅ +37 0.04 + 0.04 360 = 90% A ₅ +46 0.2 ± 0.2 240 The ₆ + K (known) 0.2 ± 0.2 360 = 70% ₆ +4 0.008 +0.008 360 A ₆ % 2 0.008 +0.008 360 The ₆ +3 0.04 + 0.04 180 ₆ +38 0.008 +0.008 180 Ag + 46 0.008 +0.008 360 A ₆ +45 0.008 +0.008 240 ₆ +35 0.008 +0.04 180 ' 0.2 + 0.04 105 ' 0.2 + 0.02 150 ' 0.04 + 0.004 210 ' a ₆ + i 0.008 + 0.04 240 ' 0.2 + 0.04 120 ' 0.04 + 0.008 150 ' 0.008 +0.08 150 ' 0.2 + 0.02 150 ' 0.04 + 0.004 180 ' A ₆ +37 0.2 + 1.0 75 ' 0.04 ± 0.2 90 ' 0.008 + 0.04 150 ' 0.2 + 0.04 105 ' 0.04 + 0.4 90 ' 0.008 +0.8 120 ' 0.008 +0.4 150 ' 0.2 + 0.02 150 ' 0.04 + 0.004 210 ' As + 41 0.2 + 1.0 150 ' 0.04 ± 0.2 180 ' 0.2 + 0.04 240 ' 0.04 + 0.4 105 ' 0.008 +0.8 360 ' 0.008 +0.4 360 ' 0.2 + 0.02 360 ' ₆ +20 0.2 + 1.0 150 ' 0.04 ± 0.2 105 '

Active ingredient 4-synergistic formula v. example number Concentration of active substance + synergist (° / ₀ ) LTioo (minutes) and degree of death (%) 0.2 + 0.04 150 ' 0.04 + 0.4 120 ' 0.008 + 0.08 180 ' 0.008 + 0.8 210 ' 0.008 +0.4 210 ' 0.2 + 0.02 180 ' 0.04 + 0.004 360 ' ₆ +21 0.2 + 1.0 75 ' 0.04 ± 0.2 90 ' 0.008 + 0.04 180 ' 0.2 + 0.04 120 ' 0.04 + 0.4 105 ' 0.008 + 0.08 180 ' 0.008 + 0.8 210 ' 0.2 + 0.02 150 '

Example B ₂₅ LT ₁₀₀ Assay

Experimental animals: Blattella germanica Q $ (normally sensitive), Blattella germanica 9 $ (resistant), Tribolium confusum, Dermetes peruvianus, Attagenus 30 piceus larvae, Ornithodoros moubata larvae.

Solvent: acetone.

Solutions of the active compounds, synergists and the active synergist mixture are prepared from which

2.5 ml are pipetted into Petri dishes on 9.5 cm diameter filter paper 35 discs. The filter paper absorbs the solutions. Allow the Petri dishes to remain open until the solvent has completely evaporated. 25 experimental animals were then placed in each Petri dish and covered with a glass lid.

The condition of the experimental animals was monitored continuously for a maximum of 6 hours and then for 24, 48 and 72 hours. The time required for a 100% destructive effect is determined. If the LT ₁₀₀ is not reached after 72 hours, the death rate is determined as%.

II. The following table summarizes the concentrations and effects of the active substances, synergists and mixtures:

II. spreadsheet

LT ₁₀₀ test against various pests

Active substance + synergist example v. formula number Malware Concentration of active ingredient + synergist (%) LT _II0 (minutes or hours) or degree of death (%) A1 Blattella germ. $$ norm. sensitive.) 0,008 ^24h = 80% THE] Blattella germ. 9 5 (resistant) 0,008 ^24h = 60% 4 Blattella germ. 9 9 (normal sensitivity) 1.0 24 ^hours = 0% I + 4 Blattella germ. 9 9 (normal sensitivity) 0.008 +0.008 60 ' J + 4 Blattella germ. 9 9 (resistant) 0.008 +0.004 6 ^h Ai Tribolium confusum 0.2 72 ^h = 50% 4 Tribolium confusum 0.2 72 ^hours = 0% J + 4 Tribolium confusum 0.04 + 0.04 72 ^h = 90% Aj Dermestes peruvianus 0.04 72 ^hours = 0%

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Example of active ingredient-synergist v. formula number Malware Concentration of active ingredient + synergist (%) LT ₁₀₀ (minutes or hours) and degree of death (° / ₀ ) 4 Dermestes peruvianus 0.2 72 ^hours = 0% K (known) Dermestes peruvianus 0.2 72 ^hours = 0% The [+ K (known) Dermestes peruvianus 0.04 + 0.04 72 ^h = 20% The + 4 Dermestes peruvianus 0.04 + 0.04 24 ^hrs A ₍ Attagenus picues larvae 0.2 72 ^hours = 0% 4 Attagenus picues larvae 0.2 72 ^hours = 0% K Attagenus picues larvae 0.2 72 ^hours = 0% (known) ? T + K Attagenus picues larvae 0.2 ± 0.2 ^H = 72% O J + 4 Attagenus picues larvae 0.2 ± 0.2 24 ^hrs Ai Ornithodoros moubata larvae 0,008 72 ^h = 80% K (known) Omithodoros moubata larvae 1.0 72 ^hours = 0% Aj + K (known) Ornithodoros moubata larvae 0.008 +0.008 72 ^h 2 Ornithodoros moubata larvae 1.0 72 ^hours = 0% J + 2 Ornithodoros moubata larvae 0.008 +0.008 24 ^hrs 3 Ornithodoros moubata larvae 1.0 72 ^h = 8O% Aj4 3 ~ Ornithodoros moubata larvae 0.008 +0.008 24 ^hrs 38 Ornithodoros moubata larvae 1.0 72 ^hours = 0% A ₁ + 38 Ornithodoros moubata larvae 0.008 +0.008 120 ' 1 Ornithodoros moubata larvae 1.0 72 ^hours = 0% Aj + 1 Ornithodoros moubata larvae 0.008 +0.008 150 ' 45 Ornithodoros moubata larvae 1.0 72 ^hours = 0% J + 45 Ornithodoros moubata larvae 0.008 +0.008 105 '

Example C)

Aerosol test

Experimental animals: Phosphoric ester-resistant male Musca domestica: strain: Weymanns.

Solvent: acetone.

The active compounds are dissolved in the solvent to form a suitable formulation. A wire cage was placed in the center of a 1 m ³ gas impermeable glass chamber in which about 25 experimental animals were placed. The chamber is then sealed again and sputtered III. Table 45

Aerosol test with phosphoric acid ester resistant male Musca domestica (strain: Weymanns)

Active ingredient ++ Synergist Concentration (mg / m ⁸ air) active ingredient + + synergistically LT ". (minute) Death rate (%) within 24 hours 50 Ai 10 60 = 0% 0 K 10 60 = 0% 0 4 10 60 = 0% 0 55 3 10 60 = 0% 0 1 10 60 = 0% 0 37 10 60 = 0% 0 Aj + K 10 + 10 60 = 0% 0 J + 3 10 + 10 60 = 33% 90 60 J + 1 5 + 5 60 = 93% 70 Aj + 1 10 + 2.5 45 '23 100 Ai + 37 10 + 10 60 = 70% 100 J + 37 10 + 2.5 60 = 63% 90 J + 4 10 + 10 60 = 73% 10 65

2 ml of the active ingredient were added. The condition of the experimental animals is constantly monitored through the glass wall and the time required for 100% destruction is determined. After 60 minutes, the experimental animals are removed from the glass chamber, transferred to a drug-free atmosphere and re-examined after 24 hours.

In III. Table 4 summarizes the concentrations of the active compounds, synergists, mixtures thereof, the time required for 100% killing, and the percentage of animals killed 24 hours later.

Production examples

Alkylation of 3,4- (methylenedioxy) phenylacetonitrile

1. (a) To a suspension of 1.1 moles of potassium tert-butylate in 1500 ml of toluene are added dropwise 1.0 moles of 3,4-methylenedioxyphenylacetonitrile and 3,4- (1.5 g) at 25-30 ° C with gentle cooling. methylenedioxy) phenyl-a-alkyl-acetonitrile. The reaction mixture is stirred at 40-50 ° C for 30 minutes and then 1.1 moles of alkyl halide are added dropwise with cooling at 50 ° C. The reaction mixture was refluxed for 3 hours, cooled, water was added, the phases were separated, the organic phase was washed neutral, dried over sodium sulfate, evaporated and the solvent was distilled off.

Final product obtained by the above procedure, the products of general formula represented by the preparation of compounds of formula (I), (Id): - wherein ^R1 and ^R2 are as IV. The yield, yield, boiling point of the resulting compound and starting halide starting material are shown in Table IV. table:

-7179923

ARC. Table II: Products of Formula Id

Starting halide R ¹ R ^a Yield (%) Boiling point (° C / mbar) 1. ch ₃ i H -ch ₃ 66 138 / 4.0 2. C ₂ H ₅ Br H -c ₂ h ₅ 76 147-149 / 5.33 3. nC ₃ H ₇ Br H nC ₃ H ₇ 75 156 / 4.0 4. iso-C ₃ H ₇ Br H iso-C ₃ H ₇ 78 133 / 30.66 5. CH ₂ = CH-CH ₂ Br H —Ch ₂ —ch = ch ₂ 76 146 / 4.0 6. C ₆ H ₅ —CH ₂ Cl H —Ch ₂ —c ₆ h ₅ 73 206 / 4.0 7. C ₅ H _n Br H -C ₆ H _n 46 134 / 1.33 to 2.67 8. 2 CH ₃ I -ch ₃ -ch ₈ 85 134 / 5.33 9. C ₂ H ₅ Br + CH ₃ I -CHj -c ₂ h ₅ 70 138 / 4.0

In a manner analogous to that described in Example 1a, the 6-alkyl-3,4- (methylenedioxy) phenylacetonitrile derivatives can be alkylated.

Table V summarizes the yields of the compounds of formula (I) wherein R, R ¹ and R ² 20 are as defined in Table V, the boiling point of the resulting compound and the starting halide required for its preparation. compound.

Table V Products of Formula I

Starting halide R ¹ R ' R Yield (%) Melting point (° C) Boiling point CC / mbar) 10. ch _b i H CH _S nC _g H ₇ 71 125 / 0.013 11. C ₂ H ₅ Br H —C ₂ h ₅ nC _g H ₇ 71 125 / 0.013 12. nC _g H ₇ Br H nC _g H ₇ nC _g H ₇ 68 168 / 4.0 13. iso-C _g H ₇ Br H iso-C ₃ H ₇ nC ₃ H ₇ 50 162 / 4.0 14. CH ₂ = CH-CH ₂ Br H CH _g = CH-CH ₂ - nC ₃ H ₇ 74 160 / 4.0 15th - H H terc-C ₄ H ₉ 68 138 / 0,013 16. CH _g I H -CH _g terc-C ₄ H ₉ 46 104 17. C ₂ H ₅ Br H -c ₂ h ₅ terc-C ₄ H ₉ 52 94 18. nC ₃ H ₇ Br H nC _g H ₇ terc-C ₄ H ₉ 49 106 124 / 0.01 19. iso-C ₃ H ₇ Br H iso-C _g H ₇ terc-C ₄ H ₉ 49 132 / 0.01 20th - H H —CH _S. 62 51 145/3 21. CH ₃ I H —CH _g -ch ₃ 74 143/3 22. C ₂ H ₅ Br H -c ₂ h ₅ -ch ₃ 79 138/1 23. nC ₃ H ₇ Br H nC _g H ₇ CH, 68 150/2 24. iso-C _g H ₇ Br H iso ^- C ₃ H ₇ -ch ₃ 71 143/2 25th - H H —Ch ₂ —ch = ch ₂ 61 110-112 / .13 26. CH ₈ I H -CH _g —Ch ₂ —ch = ch ₂ 63 125 / 0.1 27. C ₂ H ₅ Br H -C ₂ H ₅ —Ch ₂ —ch = ch ₂ 76 124 / 0.2 28. nC ₃ H ₇ Br H nC _g H ₇ —Ch ₂ —ch = ch ₂ 60 124 / 0.15 29. iso-C ₃ H ₇ Br H iso-C ₈ H ₇ —Ch ₂ —ch = ch ₂ 140 / 0.13 30th - H H —CH = CH — CH _g 78 89 134 / 0.1 31. CH ₃ I H -CH _g -CH = CHG 69 125 / 0.1 32. C ₂ H ₅ Br H -c ₂ h ₅ -CH = CH-CH ₃ 64 141 / 0.7 33. nC _g H ₇ Br H nC ₈ H ₇ -CH = CHG 66 149 / 0.7 34. iso-C ₃ H ₇ Br H iso-C ₃ H ₇ -CH = CH-CH _S 67 130 / 0.1

1. b) Alkylation by phase transfer catalyst process

40-50 per 1000 ml of a 5% sodium hydroxide solution, 1.0 mole of 3,4-methylenedioxyphenylacetonitrile and 10 g of a phase transfer catalyst (e.g. triethylbenzylammonium chloride) 1.0 mole of dihaloalkane or alkyl halide or 65 dialkyl sulfate is added dropwise at 0 ° C. After stirring for 2 hours at 90 ° C, the reaction mixture was cooled, poured into 1500 ml of ice water, extracted with methylene chloride, washed to neutral, the solvent was evaporated and the final product was distilled.

VI. The following table summarizes the alkylating agents,% yield and boiling point of the final product obtained.

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VI. Compounds of formula (Id)

alkylating agents R., R. Yield (% j Boiling point ('C / ikbar) 35. Br— € H ₂ —CH ₂ Br —Ch ₂ —ch ₂ - 19 130 / 4.0 36. Cl-CH ₂ -CH ₂ -CH ₂ -Cl -CHj-CH 2 CHj- 58 155 / 4.0

Halogenation of 2,3,4- (methylenedioxy) phenyl-α-alkylacetonitrile derivatives

(a) Chlorination with sulfonyl chloride

To a solution of 0.1 mol of 3,4-methylenedioxyphenylacetonitrile in 100 ml of methylene chloride was added dropwise 0.11 mol of sulfonyl chloride at room temperature. The reaction mixture was stirred at reflux for 2 hours and then cooled with water; washed with sodium bicarbonate solution and then with water, neutralized, dried over calcium chloride, the solvent was evaporated and the final product was distilled or filtered off.

VII. summarized the general képleffi blonder compounds representative of the compounds of formula (I) (W) table - where R * and R ² in jeleötése

VII. as well as yields and identification data.

VII. Table Tfera (Ia)

Rí Rí Yield: (7o) melting point Space 37. H CHg 61 152 / 5.33 38. HC ₂ H ₅ 91 158 / 5.33 39. H nC ₃ H ₇ 74 165 / 5.33 40. H iso-C ₃ H ₇ 81 163 / 5.33 41. —CHg - CH ₃ 83 162-165 / 5.33 42. —CH ₂ —CH ₂ —CH ₂ —CH ₂ - 70 83 43. H —CH ₂ —C ₆ H ₅ 87 84 44. -CH _g - -C ₂ H ₅ 72 150 / 5.33

(b) Bromination with bromine

A solution of 0.105 mol of bromine in 10 ml of glacial acetic acid was added dropwise at room temperature to a solution of 0.1 mol of 3,4-methylenedioxyphenyl-α-alkylacetonitrile in 150 ml of glacial acetic acid. After stirring at room temperature for 4 hours, the reaction mixture was poured into water, extracted with methylene chloride, washed with sodium bicarbonate solution and water, neutralized, dried over calcium chloride, the solvent was evaporated and the final product was recrystallized.

VIII. Table I summarizes compounds of formula (Ib) which represent a more limited set of compounds of formula (I) - wherein R ¹ and R ² are

VIII. - as well as the yield% and boiling points.

3. Nitration of 3,4- (Methylenedioxy) phenyl-α-alkylacetonitrile

To a solution of 0.1 mol of 3,4-methylenedioxyphenyl-α-alkylacetonitrile in 100 ml of glacial acetic acid was added dropwise a mixture of 12 ml of concentrated sulfuric acid and 10 ml of nitric acid under gentle cooling at 20-30 ° C. The reaction mixture was stirred at room temperature for 3 hours and then poured into ice water. The reaction mixture may be worked up by either (a) suctioning off the precipitate, washing to neutral and drying, or (b)

IX. Table II: Products of general formula Ic

VIII. Table II (Products of Formula Ib)

R ¹ Ri mining, % Boiling point, ° C / mbar 45th H -ch ₃ 55 158 / 5.33 60 46th H -c ₂ h ₅ 54 158-160 / 4.00 47th H n C ₃ H ₇ 45 160-164 / 5.33 48th H iso-C ₃ H ₇ 71 160 / 5.33 49th -CH _a -ch ₃ 58 156 / 5.33 65

R ' Ri Yield% Identification data (melting point, ° C, refractive index, boiling point, ° C) 50. H -ch ₃ 68 n "= 1.5890 51. H H 85 114 52. H c ₂ h ₃ 60 n "= 1.5757 53. H n-C ₃ H ₇ 81 196 / 5.33 mbar 54. H iso-C ₃ H ₇ 77 72 55 -CH -ch ₃ 74 126 56-CH, CH, CH, CH, - 96 81 57. H —Ch ₂ —c ₆ h ₅ 87 161 58. H —CH ₂ € H = CH ₂ 54 104

-9179923 was dissolved in methylene chloride, washed neutral with sodium bicarbonate solution and water, dried, evaporated to remove impurities from the residual oil, or the residual oil was mixed with petroleum ether, filtered off with a solid yellow precipitate and dried.

IX. Table I summarizes compounds of formula (Ic) which represent a more limited set of compounds of formula (I) - wherein R ¹ and R ² are as defined in Table IX. - as well as the yield and identification data.

Claims (1)

Patent claims Insecticidal and acaricidal compositions having a synergistic effect, characterized in that they contain from 0.1 to 50% by weight, as active ingredient, of a benzodioxolane derivative of the formula (I) - in the formula (I): R is hydrogen, (1-4C) alkyl or halogen; R ¹ is hydrogen or C 1-4 alkyl; R ² is hydrogen or C 1-4 alkyl; and R ¹ and R ² together may form a C 1 -C 4 alkylene group - and a carbamate derivative of formula II - in formula II: R ³ is naphthyl, dioxolanylphenyl, phenyl substituted up to three times with C 1-4 alkyl, C 1 -C 4 alkyl singly or twice substituted with 2,3-dihydrobenzofuranyl or benzodioxolanyl, or substituted with C 1-4 alkoxy; and R ⁴ is C 1 -C 4 alkyl, containing from 0.1: 10 to 10: 0.1 weight percent solids, preferably natural or artificial rock flour, and / or liquid diluents, preferably organic solvents such as optionally halogenated hydrocarbons; dialkylformamides or dimethylsulfoxide and optionally surfactants, preferably emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, alkylsulfonates, alkylsulfates, aryls. sulfonates as well as protein hydrolysates and / or dispersants such as lignin, sulfite impurities or methyl cellulose.