CS199515B2 - Insecticide and acaricide - 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

Vynález.- with new ^one insektícidiní ·· · · and acaricidal, synergistic combinations of substances účinnýoití · composed · - of the partial-known and benzodinxoift · · · · z · other. known pesticidal, in particular insecticidally-active compounds.

It is already known; That benzodoxole derivatives, for example .alpha.,. Alpha. -Dimethyl {3,4- (1,4-methylenediocarbonylethylaminoethoxy) tri- and .alpha.-ethylene-N, N-methylenedioyphthyl) acetonitrile, are used as intermediates in the preparation , pharmaceutical preparations (see DOS No. 2 · 215496 and J. org. Chem. 1972, pp. 977-982).

The following insecticidally active substances or groups of substances are also known:

A. carbamates such as

2-isopropoxyxyanyl-N-mercurylcarbamate, 3,4,5-trimethylphenyl-N-methylcarbamate,

1-naphthyl N-methylcarbamate, d, 3-dihydr2-2,2 d'i ⁱ met7yl 7-bonzofuranyl-

-N-methylcarbamate,

2- (1,3-dioxolan-2-ylphenyl) -N-methylcarbamate a

2-methylpyrrolidin-1-yl-4-oxo-4-yl-N-methylcarbamate;

B. esters of alkoxy acids, such as

X

2,3; 4,5-tetrahydrophthaimidimidylchrysanthemate and '(5-benzyl-3-furyl) ethyl-5'-dimethyl-5' - (2-methylpropenyl · ·) cyclopropanecarboxylate;

C. phosphoric acid such as, for example,

O (O-Dimethyl-O (phosphoryl) phenyl) ester.

Also known are synergistic mixtures of carbamates, for example 2-isopropoxyphenyl-N-methylcarbamate, or phosphoric acid esters, for example G, O-diethyl-10- (B-isopropyl-methylpyridin-6-ylmethyl) phosphorothiate or of natural or synthetic pyrethroids with piperonyl ethers. such as [3- (2-butoxyethox-ylethoxy) -1H-methylenedioxy-2-propyltoluene (see Bull: Org. 1966, 35, 35, 691-708); · G. · Scraper; Die Entiwicklung · Neueninisiizide · · Phosphor.sau-reester · 1963, pp. 158; W: Per-metal, Die Insektizide, 1966, pp. 516-524. However, some practical applications have so far been achieved with essentially only α-ω (ω-hutoxy-ethoxy) ethoxy-4,5¾. ma | end í χ j Ž Ž Ž Ž Ž pi pi pi pi pi pi pi 1 1

It has now been found that a new active ingredient combination consisting of the benzodioxole derivatives of the general formula I,

(I) in which

R represents a hydrogen, chlorine or bromine atom, a nitro group, a straight or branched alkyl group having 1 to 6 carbon atoms or a straight or branched alkenyl group having 2 to 6 carbon atoms,

R 1 represents a hydrogen atom or a straight or branched (C 1 -C 3) alkyl group;

R2 represents a straight or branched alkyl or alkenyl group containing up to 6 carbon atoms, a C3-8 cycloalkyl group, a benzyl group or a hydrogen atom when R represents a nitro group, an alkyl or alkenyl group as defined above, or

R 1 and R 2 together form an alkylene radical having 2 to 8 carbon atoms, and

A. carbamates; and / or

B. carboxylic acid esters, including natural and synthetic pyrethroids, or

C. phosphoric acid esters exhibit particularly high insecticidal and acaricidal activity.

The synergistic effect of the compounds of the formula I is advantageously manifested in the following groups of active substances:

A. for carbamates of formula II,

R ⁴ · O \ II

N — C — O — R3, /

R5 (Π) in which

R3 represents an aryl group, a heterocyclic radical or an oxime radical,

R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and

R ⁵ represents an alkyl group, an alkylcarbonyl group. Having 1 to 6 carbon atoms in the alkyl moiety, which may be optionally substituted by hydroxy or methylthio, or • represents a radical of formula ku, in particular trichloromethyl and. trifluoromethyl, aryl, especially phenyl, optionally substituted, preferably with cyano, halogen, especially chlorine, methyl, trihalomethyl, trifluoromethylmercapto or nitro, further represents methoxycarbonyl or a radical of formula

R4

I _W _SO2 —N—. ,:

wherein W represents an alkyl group, a haloalkyl group, an alkylamino group, a dialkylamino group or an aryl radical optionally substituted, preferably by a halogen atom, a trihalomethyl group, a cyano group, a methyl group or a nitro group.

Particularly preferred are those carbamates of formula (II) above wherein:. R 3 represents a phenyl or naphthyl group which may be. optionally substituted with alkyl, alkenyl. alkoxy or alkyl-mercapto groups containing from 1 to 5 carbon atoms, dialkyl. amino- or dlalkenylamino groups containing not more than 3 carbon atoms in each alkyl or alkenyl moiety, or halogen atoms, in particular chlorine, furthermore a dioxolanyl group, or a radical of the formula --N = CH - N (C _1-4 alkyl) 2.

Further particularly preferred are those carbamates of formula (II) above wherein:

R 3 represents a 2,3-dihydrobenzofuranyl, benzodioxole, benzothieinyl or pyrimidinyl or pyrazole moiety which may be substituted by C 1 -C 4 alkyl groups, especially methyl groups, or C 1 -C 4 dialkylamino groups in each alkyl moiety.

Other particularly preferred compounds carbamates jissouty · · the above-mentioned general ¹ formula II wherein · · R3 represents an oxime radical of formula IIa.

R ⁶ '- O - N = C,

R7. (Ha.) Where

R 6 and R ⁷ may be the same or different and each represent an alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkylmercapto-, alkoxycarbonyl, carboxamide or alkylmercaptoalkyl group containing not more than 5 in each case. . carbon atoms, cyano, aryl, -S-Y where

Y represents an optionally halogenated aliphatic radical having 1 to 4 carbon atoms

the phenyl or an optionally substituted heterocyclic radical or an alkyl group substituted with a heterocyclic radical, or both together form an optionally C1 -C4 -alkyl substituted dioxolanyl or dithiolanyl radical.

B. For carboxylic acid esters of formula III,

О И »II

R8_C — O — CH — R10, (ΠΙ) in which

R ⁸ represents an alkyl, aralkyl, aryl or cycloalkyl group which may be optionally substituted,

R ^fl . represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group or a cyano group, and

R 10 represents an aryl radical or a heterocyclic radical, or together with R ⁹ forms an optionally substituted cyclopentenone ring.

Particularly preferred are the carboxylic acid esters of the above formula (III) in which:

R 8 represents an alkyl group having 1 to 6 carbon atoms, optionally substituted by a phenyl radical, which is itself optionally halogenated, cyclopropyl, optionally substituted by an alkyl, alkenyl, haloalkyl or haloalkenyl group containing up to 6 carbon atoms in each case or phenyl an optionally substituted halogen. ·

Preferred are the carboxylic acid esters of formula (III) in which:.

R 9 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl and up to 3 halogen atoms, cyano or ethenyl.

Further particularly preferred are the carboxylic acid esters of the general formula III in which

R 10 represents a phenyl group optionally substituted by a C 1 -C 4 alkyl group, a halogen atom, in particular a fluorine or chlorine atom, an optionally halogenated or methyl-substituted phenoxy group or an optionally substituted benzyl group, a furanyl, tetrahydrophthalimide or benzodioxole radical which may be optionally substituted halogens, especially chlorine, with alkyl or alkenyl groups containing up to 4 carbon atoms or benzyl groups, or further a cyclopentenone radical optionally substituted by an alkyl group. C 1 -C 4, furfuryl or C 1 -C 5 alkenyl. my carbon.

Natural pyrethroids are also particularly preferred.

C. For phosphoric acid esters of formula IV,

X X — R12 ···. wz

RH — X — P,. \ '

X — R13 <

. (! V) in which each symbol X is independently an oxygen or sulfur atom,

Y represents an oxygen atom, a sulfur atom, an —NH— group or a direct bond between central tertiary phosphorus and the remainder of each of RU and R12, which may be the same or different, is an alkyl or aryl group, and

R 13 represents an alkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkenyl group, a dioxanyl group, an oxime radical or the same radical to which it is attached.

Especially preferred are the phosphoric acid esters of the above general formula (IV) in which:

R ¹¹ and R 1 ^2, which may be identical or different, represent an alkyl group of _R having 1 to 4 carbon atoms or phenyl, and

R 13 is C 1 -C 4 alkyl optionally substituted by halogen, hydroxyl, cyano, optionally substituted halogen, carboxylic acid amide, sulfonylalkyl, sulfoxyalkyl, carbonylalkyl, alkoxy, alkylmercapto, alkoxycarbonyl, alkenyl having up to 4 carbon atoms, optionally substituted by halogen, optionally substituted by halogen or optionally substituted by phenyl or alkoxycarbonyl, further by an oxime radical of formula (IIa), R8

Z = O-N = C, (IIa) where

R ⁶ and R ⁷ are as defined above, in particular are cyano or phenyl, or R 13 represents, a dioxanyl group substituted with the same radical to which R 13 is attached, or R 13 represents the same radical to which it is attached or further represents phenyl, optionally substituted by methyl, nitro, cyano, haloalkyl, methylmercapto, and further preferably R ¹³ represents a heteroaromatic radical such as pyridine, quinoline, quinoxaline, pyrimidine, or the like. dtazinone or benzo-1,2,4-triazine, which are optionally substituted with C 1 -C 4 alkyl or halogen atoms.

The insecticidal and / or acaricidal effect of the active compound combinations according to the invention is surprisingly much higher than the effect of the individual components or the sum of the effect of the individual components. Furthermore, the effect of the active compound combinations according to the invention is considerably higher than that of the already known combination of 2-isopropoxyphenyl N-methylcarbamate and piperonyl butoxide. In addition, the synergistically active compounds of the benzodioxole series used in the present invention exhibit excellent synergistic activity not only in combination with a single group of active substances but also in combination with active substances belonging to a variety of chemical groups.

The synergistic mixtures containing the benzodioxole derivatives according to the invention thus represent a true enrichment of the prior art.

The synergistically active substances used in the combinations according to the invention are generally defined by the above formula I. In this formula, the alkyl group represented by R in particular 1 to 4 carbon atoms and alkenyl groups in the meaning of the symbol is particularly propenyl group, isopropenyl or -allylová, Alkylovou-, the radical R ¹ is in particular a methyl -group. Or alkyl. The alkenynyl group R @ 2 preferably contains up to 4 carbon atoms. The alkylene radical R @ 1 and R @ 2 together preferably contains 2 to 5 carbon atoms.

Examples of the benzodioxole derivatives of formula (I) used in the context of the invention include: .alpha.-methyl-, .alpha.-ethyl, .alpha.-propyl, .alpha.-propyl, .beta.-butyl, .alpha.-isobutyl. butyl-, α-tert-butyl, α-allyl ·, α-benzyl ·,,, α-dimethyl-, α-methyl-α-ethyl-, "methyl · -on-propyl, α-methyl-α-isopropyl , α, α-ethylene, α, α-trimethylene-, - α, α-tetramethylene-, α-cyclopropyl- and α-cyclohexyl- (3,4-methylenedioxyphenylacetonitrile), and in position 6 each time with chlorine, bromine , methyl, ethyl, n-propyl, isopropyl, tert-butyl, allyl, propenyl, isopropenyl or nitro-substituted-derivatives, and 6-nitro-, 6-methyl-, 6-ethyl-, 6-n-propyl-, 6-isopropyl-, 6-tert-butyl-, 6-allyl-,

6-propenyl- or Q-isoprooenyl- (3,4-methyleydoxyphenyl) acetonitrile.

These compounds are partially novel, but can be prepared by methods known in the literature [see, for example, DOS No. 2,215,496 and 2,335,347, British Patent No. 1109,527 to J. of Arn. Chem. Soc. 64 (1942), pp. 2486-2487 and J. of Org. Chem. 1972, pp. 977-982).

Said novel compounds can be prepared by the addition of a hydrogen atom, a halogen atom, or a 3,4-methylenedioxybenzaldehyde in the case of a hydrogen atom. redukuje- to piperoyy Saϊkobol ^{^,} which is converted to the corresponding halide, which is reacted with cyanide to 3,4-mθthyleydSoxyfeyylecetόyi.toil [see von Braun, Wirg Ber. dt. Chem. Ges. 68, 110 (1927)}. These compounds can then be used according to conventional literature procedures [tz Dehmtow, New Synthetic Methods Vol. 1, 19 (1975); Makosza et al., Chimie-et Industrie (Paris) 93, 537 (1965); Makosza, Pure Appl. Chem. 43, 439 (1975); Ma-kosza, Jonczyk, Org. Son. 55, 91 (1978)) and acylated to give compounds of formula (V) below. Compounds of formula (V) may then be halogenated, such as sulfuryl chloride or bromine, or nitrated, for example, with concentrated sulfuric acid and nitric acid.

The following reaction scheme illustrates the course of the above reaction:

198515

It is also possible. 11- (14) (1960); Weisse, Ber. Dt. Chem. Ges. 43, 2605 (1910)] and then proceed as described above. However, this method, or the consequence of the problems, leads to the poor production of the product.

In case that

a) R represents an n-propyl group, the synthesis is carried out in hashiloglyphenyl, safrole. ihydrióaa-frol. 6-Chloromethyldidihydrosafrol = 3 &apos; a compound of interest;

b) r represents an allyl group, the synthesis proceeds in the following steps:

safrol. 6-Chloroethylmethyl-6-cyanomethyl-methylbenzamide - the desired phthalic acid;

c) R represents a propenyl group, the synthesis proceeds in the following steps:

isosafrol. - 6-chloromethylisosafrole. 6-cyanomethylsafrole - the title compound; additional isomerisation of the alkyl derivative referred to in paragraph b) is more preferred;

d) r represents a tert-butyl group, the synthesis proceeds in the following steps:

4-tert-Butyloxy-choline-3,4-m-ethylenedioxyl-tert-butylene *. β-Chloromethyl-3,4-methylenedioxy - etc.butylbenzene-6-cyanomethyl-3 ', 4- ^, methylthioxy-tert-butylbenzene - the desired compound. In an analogous manner, the toluenes and ethylbenzenes of the present invention can be prepared from 4-methyl- or 4-ethylpyrocatechem. (See U.S. Patent Nos. 2,485,020 and 2,485,680, which is 6-6-membered).

Individual. Stage from above. of the process described above are 'known' or carried out in a manner known per se. For example, it is possible to use a chlorine-thiophthalic acid which always serves as a stripper. U.S. Pat. No. 2,485,600 and 2,485,680 are hereby incorporated by reference.

To carbamates. (group A) of the general formula II as used herein. According to the invention, 2-methoxyphenyl is 2-methylphenyl. 2- (4-Ethylphenyl) -2,4-propylphenyl- (2-methylphenyl) -2,4-propylphenyl- (4-ethylphenyl) -4,4-ethylphenyl. p-propylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-nitropoxyphenyl. 3,4,5-Trifluorophenyl-, 1- (4-methylphenyl) -2,3-dihydro-2,2-dimethylamino-γ-benzofuranyl- 2- (1,3-oxo-alpha-4-ylethyl) - optionally 2 2-Dimethyl-1,3-benzodioxole-4-yl-N-methylcarbamate and 6-methyl-N-methyl-N-acetyl-, 6-methyl-1H-trifluoromethylthio, -N-methyl- N-methyl-N-methyl-N-methyl-N-methyl-thiothiocarbamate.

These. the compounds they prepare. their use. are known (see, for example, US Patents Nos. 3,009,855, 2,903,478 and 3,111,539).

To the esters of carbocylic acid (B). of the general formula (III) used, if appropriate, as further components in the mixtures according to the invention are:

[1- ^(3,4 - <^ ί ^ ι ^ l ^^ l ^ i ^ iif <^ i ^ '^ i) -2 ^and 12.2 -' ^^ l ^ '^^ íéfi 01ié' t ^^^ j ^^ l] -.

acetic acid ester,

2,3, ^4, 5 - etrahyóroftaiimióó · ^ Chřýááíithemáf and Meth.

1- (5-Benzyl-3-furyl) methyl 1-2,2-dimethyl-3- (2-methylpropenyl) cyclopropanecarboxylate.

The above-mentioned compounds are known and for the most part generally commercial preparations [see R. Wegler "Chemie der Pflanzenschutz- und Schadlingsbekamfungsmittel", Vol. 1, pp. 87-118, Heidelberg (1970)].

The phosphoric acid esters (group C. of the formula IV, optionally used as further components in the mixtures according to the invention) include:

Phosphoric acid Ο, dl-dimethyl or O, O-diethyl-O- (2,2-dichloro- or 2,2-dibromvinyl) ester.

The compounds of formula IV are known and can conveniently be prepared by methods known in the literature (see, for example, U.S. Patent No. 2,965,073, DAS No. 1,167,324 and Belgian Patent No. 633,478).

As mentioned above, the novel combinations of the benzodioxole derivatives of the formula I according to the invention with carbamates, carboxylic acid esters and phosphoric acid esters show an excellent increase in activity over the individual active substances or, as the case may be, the sum of the effects of the individual substances.

The relative proportions by weight of the individual groups of active substances can be varied within relatively wide limits. Generally, the benzodioxole derivatives are combined with the other active ingredients in a ratio of 0.1: 10 to 10: 0.1. Mass ratios ranging from 0.5: 1.0 to 3.0: 1.0 have proven to be particularly suitable.

The active ingredient combination according to the invention not only causes a knockdown effect, but also kills all or at least the individual developmental stages of pests from the animal kingdom, in particular insects, in the long term. These pests include pests occurring in agriculture and forestry, pests of stocks and materials, as well as 1 pests in the field of hygiene. The above mentioned pests include:

from the order of the Isopods, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber;

from the class of the Diplopoda, for example, the Blaniulus guttulatus; from the class of the centipedes (Chilopoda), for example, Geophllus carpophagus, Scutiger and spec.

from the class of the Millipede (Symphyla), for example, Scutigerella immaculata;

from the order of the Thysanura, for example Lepisma saccharina;

from the order of the Collembola, for example Onychiurus armatus;

from the order Orthoptera eg.

Common cockroach (Blatta orientalls), American cockroach (Periplaneta americana),

Leucophaea maderae, Domestic Russian (Blattella germanica),. Cricket (Acheta domesticus), Gryllotalpa spec., Locusta migratorla migratorioiděs,

Melanopus differentialis, locust moss (Schistocerca gregaria); from the order of the Dermaptera, for example Forficula auricularia;

from the order of the Isoptera, for example Reticúlitermes spec.

from the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spec., Pediculus humanus corporls, Haematopinus Spec., Linognathus spec .;

from the order of the Mallophaga, for example, Trichodectes spec., Damalinea spec .;

from the order of the Thysanoptera, for example, Hercinothrips f emoralis, Thrips tabaci;

from the order of the Heteroptera, for example, Eurygaster spec., Dysdercus intermedius, Piesma quadrata, Gimex lectularius, Rhodnius prolixus, Triatoma spec .;

from the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gošsypii, Brevicoryne brassicae, Currant apis (Cryptomyzus) fabae), apple aphid (Doralis pomi), bloom aphid (Eriosoma lanigerum), aphid [Hyalopterus arundinls], Macrosiphum avenae, Myzus spec. , Euscelis bilobatus, Nephotetttlx cincticeps,

Lecanium corni, Saissetia oleae,

Laodelphax striatellus,

Nilaparvata lugens,

Aonidiella auraniii, Aspidiotus hederae, Pseudococcus spec., Psylla spec.

from the order of the butterflies (Lepidoptera), for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Llthocolletis blancardella, Hyponomeuta padella, Plutella maculipennis (Euproctis chrysorrhoea), moth (Lymantria spec.),

Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spec., Euxoa spec.

Feltia spec.,

Earias insulana, Hellothis spec., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura,

Spodoptera spec., Trichoplusia ni, Carpocapsa pomonella, white (Pieris spec.), Chilo spec., Corn moth (Pyrausta nubilalis), moth moth (Ephestia kuhniella), wax moth (Galleria mellonella), carpet moth (Cacoecia podana),

Capua reticulana,

Choristoneura fumiferana,

Clysia ambiguella, Homona magnanima, Tortrlx viridana;

from the order of the beetles (Coleoptera), for example, Anobium puctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica potato, Mandelinka, Mandelinka Cress (Phaedon 'cochleariae),

Diabrotica spec. (Psylliodes chrysocephala)

Epilachna varivestis, Atomaria spec., Oryzaephilus surinamensis, Anthonomus spec., Sitophilus spec., Otiorrhynchus sulcatus,

Gosmopolites sordidus, Ceuthorrhynchus assimilis,

Hypera, Dermestes spec.

Trogoderma spec., Anthrenus spec., Attagenus spec., Lyctus spec., Meligethes aeneus, Ptinus spec., Gibbium psylloides, the darkling beetle (Tribolium spec.), the darkling beetle (Tenebrio molltor), the black beetle (AgrioteS spec.), Conoderus spec., the common chafer (Melolontha melolonthá), summer chafer (Amphimallon solstitialis), Costelytra zealandica;

from the order of the Hymenoptera, for example Diprion spec., Hoplocampa spec., Lasius spec., Monomorium pharaonis, Hornet (Vespa spec.);

from the order of the Diptera, for example, the mosquito (Aedes spec.), anofeles (Anopheles spec.), mosquito (Culex spec.), fruit fly (Drosophila melanogaster), fly [Musea spec.], sunflower (Fannia spec.), buzzer Common buzzard (Calliphora erythrocephala), Buzzard (Lucilia spec.), Chrysomyia spec., Cuterebra spec., Hamster (Gastrophilus spec.), Hyppobosca spec., Thistle (Stomoxys spec.), Hamster (Oestrus spec.), Hypoderma spec. .), Horsefly [Tabanus spec.), Tannia spec., Garden Flycatcher (Bibio hortulanus), Barley Fly (Osclnella frit), Phorbia spec., Pegomyia hyoscyamij, Common Propeller (Ceratitis capitata), Dacus oleae, Marsh Marsh (Tipula paludosa);

from the order of the Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spec.

from the order of the Aarachnida, for example, Scorpio maurus, Latrodectus mactans;

from the order of the Acarina mites, for example Acarus broad, Argas spec., Ornithodoros spec., Dermanyssus galllnae, Eriophyes ribis, Boylus spec. (Rhipicephalus spec.), Drinker (Amblyomma spec.), Hyalomma spec., Tick (Ixodes spec.), Spurge (Psoroptes spec.), Scab (Chorioptes spec.), Sarcoptes spec., Mite (Tarsonemus spec.), Spider mite currant (Bryobia praeltiosa), spider mite (Panonychus spec.), spider mite (Tetranychus spec.).

The active ingredients may be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, concentrates based on suspensions and emulsions, seed dressing powders, natural and synthetic substances impregnated with active substances, small particles coated with polymeric substances and suntan substances for seeds, as well as compositions with flammable additives such as smoke cartridges, smoke cans, smoke spirals, etc., as well as formulations of active substance concentrates for diffusion cold or hot fog.

These compositions are prepared in a known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Basically suitable liquid solvents are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol, as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulfoxide, and water. By liquefied gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice, seplolite and dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells , corn sticks and tobacco stalks. Suitable emulsifiers and / or foaming agents are non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain coloring agents such as organic pigments such as iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes and metallic azphthalocyanine dyes as well as trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient.

The active compounds according to the invention can be used in the form of commercial preparations and / or in dosage forms prepared from these preparations.

The active ingredient content of the dosage forms prepared from the commercial preparations can vary within wide limits. The concentration of the active ingredient in the dosage forms may range from 0.0000001 to 100% by weight, preferably from 10 to 10% by weight.

The application is carried out in a conventional manner adapted to the application form used.

When used against hygiene pests and against storage pests, the active compounds according to the invention exhibit an excellent residual effect on wood and clay and good stability to alkali on lime substrates.

The following examples illustrate the properties of the benzodioxole derivatives used in the context of the invention in combination with the following known active ingredients:

AND)

O-CONHCl 3

Qi ^- lil

I) (CH 3 Q) 2.2-Q 1 H 1 = CCl 2

J) ryoethers in the form of 25% pyrethre extract

«)

о

CH 2 CH 2 CH. iX (CtybCsCH-CH. CHy

For comparative purposes, the formula is also used, the use of which as a feature of # pipeooyyl.butoxide below is known:

-CH4CW ^ Cf ^

- <dz

(l)

In the tables of the individual examples below, known active substances and known synergists are denoted by the aforementioned capital letters, whereas synergists recruited in the sense of the invention are denoted by numbers corresponding to the examples of their preparation. ,

Example 1 A-d A

LT10-test

Experimental insects:

female flies (Musea doqes- _; tica, Weymanns strain), - resistant to esters of taophoic acid.

Solvent: acet (nt

Solutions are prepared from the active ingredients, synergists and mixtures of active ingredients and synergists. 2.5 ml of a 9.5 cm diameter circular filter paper, laid in Petri, was pipetted from each solution. the solution is soaked in the filter paper and the Betri dish is collected; it is left open for a long time until the solvent is completely evaporated. 25 specimens of the test insect are then placed in the Petri spray and the bowl is covered with a glass candle.

The condition of the test insects was continuously maintained for 6 hours, and the time required to achieve the MOp / o-chrome effect (knock-out e-ffect) was determined. If the PO: 6 hours - ye.d ¢ o8ys. LXioo, the amount of paralyzed specimens of experimental insects in% is found.

The concentrations of the active substances, the synergists and the mixtures and the effects obtained are shown in the following tables.

TABLE

LTioo-test for female flies (Musea domestica, Weymanns strain) resistant to phosphoric acid esters

Active substance / synergist Concentration in% LTioo in minutes or hours AND 1.0 360 = 0% (B) 1.0 360 = 0 θ / o C 1.0 360 = 0% D 1.0 360 = 20 o / o E 1.0 360 = 10% F 1.0 360 = 30o / ₀ G 1.0 360 = 20% H 0.04 360 = 95% J 0.04 360 = 90% TO 0.04 120 min. L 1.0 360 = 0 θ / ο Active substance / synergist Concentration in% LT10 - in minutes or hours 1 0.2 210 min. 2 1.0 360- = -95 -θ / o 3 1.0 360 - - 80 «/ o 4 1.0 360 = 90% 35 0.2 360 37 1.0 360 38 1.0 360 = 80% 39 1.0 360 = 0 o / o 40 1.0 360 = - - - - OO 45 1.0 360 = 25/0 46 1.0 360 = 20 o / o Active substance + synergist Concentration in ° / o, active ingredient + synergist LT10 in minutes or - in hours A + L. (known) 0.2 + 0.2 360 = 85 o / o A +4 0.008 + 0.008 360 A + 40 0.04 + 0.04 240 A + 2 0.04 + 0.04 150 A + 3 0.04 + 0.04 150 A + 38 0.008 - + 0.008 360 = 90O / o A + 1 0.008 + 0.008 240 A + 45 · 0.008 + 0.008 360 B + L (known) 1.0 + 1.0 0.04 + 0.04 360 = -90 «/ o B + 4 360 = 90% B + 2 - 0.2 + 0.2 240 B + 3 0.2 + 0.2 360 B + 38 0.04 - + 0.04 360 - = 85 o / o B +1 0.2 + 0.2 240 B + 37 0.04 + 0.04 360 B + 39 0.04 + 0.04 360 = 90 o / o B + 46 0.2 + - 0.2 240 B + 45 0.04 + 0.04. 360 C + L (known) 1.0 - + 1.0 360 = 40O / O C + 38 0.2 + 0.2 6h = 90 o / o C + 1 0.2 + 0.2 180 C + 46 1.0 + - 1.0 360 C + 45 0.2 + 0.2 360 = 95 o / o

Active ingredient + synergist Concentration in ° / o, LT10 in minutes. Active ingredient + synergist or in hours

D + L (known) 0.2 + 0.2 360 = 75 ° / ο D + 4 o; oo8 4- 0.008 360 D + 2 0.008 + 0.008 240 D + 35 0.008 0.008 180 D + 3 0.04 + 0.04 180 D + 38 0.008 + 0.008 240 D + 1 0.008 0.008 150 D + 37 0.008 + 0.008 210 D 4- 39 Q, 008 + 0.008 240 D + 46 0.008 + 0.008 360 D + 45 0.008 + 0.008 210 Ё + L (known) 0.2 4- 0.2 360 E + 4 0.2 4 ~ 0.2 240 E + 2 0.2 4- 0.2 360 E + 35 0.04 '4- 0.04 360 E 4- 3 0,2, 4- 0.2 210 ° / o E 4- 38 · 0.04 4- 0.04 360 = 95 E -Н 1 0.2 4- 0.2 150 O / o E 4- 37 0.04 4- 0.04 360 = 90 E 4- 46 0.2 4- 0.2 240 F 4- L (known) 0.2 4- 0.2 360 = 70 o / o F 4- 4 0.008 4- 0.008 360 F Ψ 2 0.008 4- 0.008 360 F 4- 35 0.008 + 0.008 210 F 4- 3 0.04 4- 0.04 180 F 4- 38 0.008 4- 0.008 180 F 4- 1 0.008 4- 0.008 360 F 4- 37 0.008 4- 0.008 180 F + 46 0.008 4- 0.008 360 F 4- 45 0.008 4- 0.008 240 G 4- L (known) 1.0 4- 1.0 360 = 70 O / o G 4- 4 0.04 4- 0.04 360 = 85 %: G + 2 0.04 4- 0.04 360 G 4- 35 · 0.04 4- 0,04 · Э60 = 95 o / o G 4- 3 0.2 4- 0.2 360 o / o G 4- 38 0.2 4- 0.2 360 = 90 G 4- 1 0.04 4- 0.04 360 G 4- 46 0.2 4- 0.2 360 G 4- 45 0.04 4- 0.04 360 H 4- 4 0.04 4- 0.04 90 H 4- 35 0.04 4- 0.04 105 H 4- 38 0.04 4- 0.04 105 H 4- 37 0.04 + 0.04 180 H 4- 39 0.04 4- 0.04 150 J 4- ' 4 0.04 4- ' 0.04 105 J 4- 35 0.04 + 0.04 180 J 4- 38 0.04 + 0.04 240 AND 4- 39 0.04 + 0.04 150 J 4- 37 0.04 4- 0.04 180 к + L (known) 0.04 4- 0.04 90 к 4- 4 0.04 4- 0.04 45 к 4- 38 0.04 + 0.04 60 к + 37 0.04 + 0.04 60 к 4 ~ 39 0.04 4- 0.04 60

195515

Active ingredient + synergist Concentration in%, LTioe in minutes active ingredient + synergist or in hours

AND 1.0 360 = 3S0 = 0% 0% 5 0.2 AND 4- 5 0.008 4- 0.008 360 7 1.0 300 = 0% AND 4- 7 0.04 4- 0.04 240 8 0.2 360 0% AND + 8 0.04 + 0.04 360 10 1.0 360 0% AND 4- 10 0.04 4- Q, Q4 360 11 1.0 360 ад- 0% AND 4- 11 0.04 4- 0.04 360 12 1.0 360 SS 0 o / o AND 4- 12 0.04 4- 0.04 360 13 1.0 360 Я » 25 o / o AND 4- 13 0.04 + 0.04 360 14 1.0 360 = 0% AND + 14 0.04 + 0.04 360 15 Dec 1.0 360 PS 0 o / o AND + 15 Dec 0.04 + 0.04 360 16 1.0 360 ад 5 o / o AND + 16 0.04 + 0, Q4 360 17 1.0 360 = 0 «/ o AND 4- 17 0.04 4- 0.04 240 18 1.0 300 ад 0 o / o AND 4- 18 0.04 4 0.04 360 ад 0 o / o 19 Dec 1.0 360 ад 0% AND 4- 19 Dec 0.04 + 0.04 240 20 May 1.0 36® set 0% AND 4- 20 May 0.008 4- 0.008 íao 21 1.0 360 = 0% AND 4- 21 0.008 + 0.008 180 22nd 1.0 360 ад 40 o / o AND 4- 22nd 0.008 4- 0.008 210 23 1.0 360 ад 5 o / o AND 4- 23 0.04 4- 0.04 150 24 1.0 300 3S% AND 4- 24 0.008 4- 0.008 180 25 1.0 360 = ж Q% AND 4- 25 0.04 + 0.04 120 26 1.0 360 ад 0% AND + 26 0.04 4- 0.04 150 27 Mar: 1.0 360 - 0 ° / o AND 4- 27 Mar: 0.04 4- 0.04 150 28 1.0 360 ад 0 o / o AND + 28 0.04 4- 0.04 180 29 1.0 260 ss » 0 o / o AND 4- 29 0.04 4- 0.04 180 30 1.0 360 X » 0 o / o AND + 30 0.04 + ' 0.04 180 31 1.0 360 ад 20 o / o AND 4- 31 0.04 + 0.04 120 32 1.0 360 ад 20 o / o AND 4- 32 0.008 4- 0.008 360 33 1.0 360 = 0 o / o AND 4- 33 0.04 0.04 180 34 1.0 360 5 » 0% AND 4- 34 0.04 + ‘ 0.04 150 41 1.0 360 ад 0 o / o AND 4- 41 0.04 + 0.04 210 43 1.0 360 3 0% AND 4- 43 0.2 4- 0.2 360 . = 70 O / o 44 1.0 360 = 0 o / o AND 4- 44 0.04 T 0.04 210

Active substance + synergist

Concentration in%, active substance + synergist

LT100. in minutes or hours

47 1.0 360 '= 0% A + 47 0.04 + 0.04 360 48 1.0 360 · = 0% A + 48 0.04 + 0.04 240 49 1.0 360 = 0% A + 49 0.04 + · 0.04 360 50 1.0 360 = 0% A + 50 0.2 + 0.2 360 51 1.0 360 = 0% A + 51 0.2 + 0.2 360 = 70% 52 1.0 360 = 0% A + 52 0.04 + 0.04 360 53 1.0 360 '= 0% A + 53 0.2 + 0.2 240 54 1.0 360 = 0% A + 54 0.2 + 0.2 360 55 1.0 360 = 0% A + 55 . 0.2 + 0.2 360 = 95% 58 1.0 360 = 0% A + 58 0.2 + 0.2 360 = 80% A + L 0.2 + 0.2 360 = 80%

Example Β

LT10-test

Experimental insects:

Blatella germanica 99 (Russian) - normally sensitive,

Blatella germanica 99 (Russian) - resistant,

Tribolium confusum,

Derméstes peruvianus (skin-beetle), larvae of Attagenus piceus (dark skin-beetle), larvae of Ornithodoros moubata.

Solvent: acetone.

Solutions are prepared from the active ingredients, synergists and mixtures of active ingredients and synergists.

From each solution, 2.5 ml was then pipetted onto a 9.5 cm diameter circular filter paper placed in a Petri dish. The solution is soaked in the filter paper and the Petri cream is left open until the solvent is completely evaporated. 25 specimens of test insects are then placed in a Petri spray and the bowl is covered with a glass lid.

The condition of the test insects is continuously monitored. for 6 hours and then again after · 24, 28 and 72 hours to determine the time required to achieve a 100% knocktdown effect. If LT100 is not reached after 72 hours, the amount of paralyzed specimens is determined. insects in%.

The concentration of the active ingredients of the synergists and mixtures and the effects achieved are shown in the following table.

TABLE

LTioo-test with various pests

Active substance Synergist Pest Concentration in% LTioo in minutes or hours active substance synergist AND Blattella germ. 22nd (normally sensitive) 0.008 24 ”= 80 o / o AND Blattella germ. 22nd (resistant) 0.008 24 ”= 60% 4 Blattella germ. 22nd (normally · sensitive) 1.0 24 ”· = 0 o / o A + 4 Blattella germ. 22nd (normally sensitive) 0.008 + 0.008 60 min. A + 4 Blattella germ. 22nd (resistant) 0.008 + 0.04 6 ^h AND Tribollum confusum 0.2 72 ”= 50« / o 4 Tribollum confusum 0.2 72 ”= 0 o / ₀ AND 4 Tribolium confusum 0.04 + 0.04 72 ”= 90 o / o AND Dermestes peruvianus 0.04 72 ”ø 0 o / o 4 T Dermestes peruvianus 0.2 72 ”= 0 O / o JLi (known) Dermestes peruvianus 0.2 72 ”= 0 o / o A + L (known) Dermestes peruvianus 0.04 + 0.04 72 ”= 20O / o A + 4 Dermestes peruvianus 0.04 + 0.04 24 ” AND larvae of Attagenus piceus 0.2 72 ”= · 0% 4 τ larvae of Attagenus piceus 0.2 72 ”= 0 o / o 1j (.known) larvae of Attagenus piceus 0.2 72 ”· = 0 0/0 A + L (known) larvae of Attagenus piceus 0.2 + 0.2 72 ”= 0 O / o A + 4 larvae of Attagenus piceus 0.2 Λ + 0.2 24 ” AND' r larvae Ornithodoros moubata 0.008 72 ”· = 80% ij (known) larvae Ornithodoros moubata 1.0 72 ”= 0 o / o A + L (known) larvae Ornithodoros moubata 0.008 + 0.008 72 ” 2 larvae Ornithodoros moubata 1.0 72 ”= 0 o / o A + 2 larvae Ornithodoros moubata 0.008 + 0.008 24 ” ‘3 larvae Ornithodoros moubata 1.0 . 72 ”= 80 o / o A + 3 larvae Ornithodoros moubata 0.008 + 0.008 24 ” ‘38 larvae Ornithodoros moubata 1.0 72 ”= 0 · 0/0 A + 38 larvae Ornithodoros moubata 0.008 + 0.008 120 min. 1 larvae Ornithodoros moubata 1.0 72 ”= 0 o / o A + 1 larvae Ornithodoros moubata 0.008 + 0.008 150 45 larvae Ornithodoros moubata 1.0 72 ”= 0 Oo A + 45 larvae Ornithodoros · moubata 0.008 + · 0.008 105 min.

Example С

Test of effectiveness in aerosol application

Experimental insects:

male and female flies (Musea domestica; Weymanns strain) resistant to phosphoric acid esters.

Solvent: acetone.

To prepare a suitable active agent, the active agents are dissolved in a solvent.

A wire cage with about 25 specimens of experimental insects is suspended in the center of a gas-tight 1 m ³ glass chamber. After closing the chamber, 2 ml of the active agent are sprayed into the chamber. The condition of the test insects is continuously visually inspected from outside the chamber through the glass walls and the time required for 100% knock-down effect is determined. After 60 minutes, the test insects are removed from the test chamber, stored in a drug-free atmosphere and rechecked after 24 hours.

The following table shows the active substances, the amounts of active substances used and the times at which the 100% paralyzing effect was observed, as well as the percentage of test animals killed after 24 hours.

TABLE

Efficacy test for aerosol application on housefly (Musea domestica; strain Weymanns) Active substance Synergíst Concentration in the active substance mg / m ³ air synergist LTioo in minutes % of dead animals after 24 hours females: AND 5 60 = 32% 40 К 5 42 min. 13 sec. 95 L 10 60 = 0% 0 37 10 60 = 0% 0 AND L 5 5 60 = 0% 5 AND 37 5 5 60 = 68% 90 К 37 5 5 30 min. 10 sec. 100 ALIGN! samečkové: AND 10 60 = 0% 0 L 10 60 = 0% 0 4 10 60 = 0% 0 3 10 60 = 0% 0 1 10 60 = 0% 0 37 10 60 = 0% 0 AND L 10 + 10 60 = 0% 0 AND 3 10 + 10 60 = 33% 90 AND 1 5 + 5 60 = 93% 70 AND 1 10 + 2,5 45 min. 23 sec. 100 ALIGN! AND 37 10 + 10 60 = 70% 100 ALIGN! AND 37  10 + 2,5 60 = 63% 90 AND 4 10 + 10 60 = 73% 10

The following are non-limiting examples of the preparation of the compounds of Formula I of the present invention.

Examples 1 - 58

Alkylation of 3,4-methylenedioxyphenylacetonitrile to a suspension of 1.1 mol of potassium butoxide in 1500 ml of toluene is added dropwise at a temperature of up to 30 ° C under gentle cooling.

1.0 mol of 3,4-methylenedioxyphenylacetonitrile or 3,4-methylenedioxyphenyl-.alpha.-alkylacetonitrile, stirred at 40 DEG-50 DEG C. for 30 minutes, then added dropwise with cooling at 50 DEG C., 1 mol of alkyl halide, the reaction mixture is stirred at reflux for 3 hours, cooled, water is added, the organic phase is washed neutral, dried over sodium sulphate, the solvent is evaporated and the residue is distilled under vacuum.

By this procedure the compounds summarized in the following overview are prepared.

R ¹

AND

-CN

2.

Example Number starting halide R1 R2 yield (% of theory) the boiling point (° C) 1 CH3J H CH3 66 138/400 Pa 2 C2H5-Br H C2H5 76 147–149 / 533 Pa 3 n-C3H7-Br H n-C3H7 75 156/400 Pa 4 ISSO-C3H7 — Br H ISSO-C3H7 78 133 / 267—400 Pa 5 CH 2 = CH-CH ₂ Br H - -CH 2 - CH = CH 2 76 146/400 Pa 6 O-C 1 H 2 ^OCt H 73 206/400 Pa 7 H 46 134 / 133—267. ' Bye X) 8 2 CH ₃ J CH3 CH3 85 134/533 Pa 9 C 2 H 5 -Br + CH 3 ’CH3 C2H5 70 138/400 Pa Alkylation 6-alkyl-3,4-methylenedioxyphenyl- to give compounds summarized in follow of acetonitriles in accordance with the 1a) whose overview:

pi -C-CN i .5 g

example number starting halide Ri R2 R3 yield (O / o theory) the boiling point (° C) 10 CH3J H CH3 n-C3H7 71 125 / 1.3 Pa 11 CzHsBr H C2H5 n-C3H7 65 132 / 1.3 Pa 12 n-C3H7Br H n-C3H7 n-C3H7 68 ' 168/400 Pa 13 iso-C3H7Br H ISSO-C3H7 n-C 3 H 7 50 162/400 Pa 14 CH 2 = CH — CH 2 Br H CH2 = CH-CH2 n-C3H7 74 160/400 Pa 15 Dec - H H t-C4H9 68 138 / 1.3. Bye 16 CH3J H CHs tert-C 6 H 8 46 104 17 C2r3Br H C2H5 tert - C 4 H 9 52 94 18 n-CsHzBr H n-C3H7 tert - C4Ha 19 Dec lso-C3H7Br H ISSO-C3H7 tert-C 1 H 10 20 May - H H CH3 21 CH3J H CH3 CHs 22nd CzHsBr H C2H5 CHs 23 n-C3H7Br H n-C3H7 CH3 24 iso-C3H7Br H ISSO-C3H7 CH3 25 - H H C 10 CH 2 CH 2 61 110-112 / 1,3,3 Bye 26 CHsJ H CHs CH 2 CH = CH 2 27 Mar: CzHsBr H CzHs CH2CH = CH2 28 n-C3H7Br H 11-C3H7 CH 2 CH = CH 2 29 iso-C3H7Br H ISSO-C3H7 CH2CH = CH2 140 / 13.3 Pa 30 - H H —CH = CH — CH3 31 CH3J H CH3 —CH = CH — CH3 32 C2H5Br H C2H5 —CH = CH — CH3 33 n-C3H7Br H n-CsH7 —CH = CH — CH3 34 iso-C 3 H 7 Br H 1SO-C3H7 —CH = CH — CH3

1b) Procedure using a phase transfer catalyst

To a mixture of 1000 ml of a 50% sodium hydroxide solution, 1.0 mol of 3,4-methylenedioxyphenylacetoniltril and 10 g of a phase transfer catalyst (e.g. triethylbenzylammonium chloride) at 40 to 50 ° C is added dropwise 1.0 mol of dihalocalalkane or alkyl halide or dialkyl sulfate, the mixture was stirred at 90 ° C for 2 hours, then cooled, poured into 1500 ml of ice water, the resulting mixture was extracted with methylene chloride, the extract was washed neutral, dried, the solvent was evaporated and the residue subjected to distillation.

Examples of this procedure are summarized below.

example number alkylating agent yield (% of theory) boiling point (° C) 35 Br — СЙ2 — CH2 — Br 19 Dec 130/400 Pa 36 Gl _{СЙ2--CH2-CH2-CH2} - Cl 58 155/400 Pa 37 (C2H5O) 2SO? 34 148/533 Pa

Halogenation of 3,4-methylenedioxyphenyl-.alpha.-alkylacetonitrile

2a) Sulfuryl chloride glorination

Dissolve 0.11 mol of sulfuryl chloride at room temperature with 0.1 mol of Beta-methylenedioxyphenyl-.alpha.-alkyloxyacetonitrile, dissolved in 100 ml. then with sodium ^bicarbonate: sodium carbonate and again with water until neutral reactive. It is dried over calcium chloride, the solvent is evaporated and the residue is subjected to distillation or crystallization, or is purified by melting, i.e. by prolonged heating under reduced pressure to a medium temperature, to remove the last residual volatiles.

The compounds thus prepared are summarized as follows:

přtód čfsilo Ri R ² yield (% of theory) Boiling Point (° C) or melting point ^(U C) 37 H Сйз 61 152/533 Pa ‘38 H С2Й5 91 158/533 Pa 39 H П-СЗЙ7 74 165/533 PŠ 40 H ISSO-C3H7 81 163/533 Fri 41 СЙз ’ СНз 83 162-165 / 533 'Pa 42 -СЙ! 2 — СЙ2-СН2-СЙ2- 70 86 43 H СЙ2— С6Й5 87 84 44 СИз С2Й5 72 150/533 Pa

2b) Bromination

To a solution of 0.1 mol of 3,4-triethylenedioxyphenyl-.alpha.-alkylacetonitrile in 150 ml of glacial acetic acid, a solution of .105 mol of bromine in 10 ml of glacial acetic acid is added dropwise at room temperature, stirred for 4 hours at room temperature. ^The mixture was extracted with methylene chloride, the extract was washed with sodium bicarbonate solution and then with water, dried over anhydrous calcium chloride, the solvent was evaporated and the residue was distilled or recrystallized.

The compounds prepared in this way are summarized below.

)

2 ·

example number R1 R2 (° / o theory) the boiling point (° C) 45 H CH3 55 158/533 Pa 46 H C2H5 54 158–160 / 400 Pa 47 H n-C3H7 45 160–164 / 533 Pa 48 H ISSO-C3H7 71 160/533 Pa 49 СНз CH3 58 156/533 Pa

3) Nltrace

Κ 0.1 mol of 3,4-methylenedioxyphenyl-α-alk-ylacetonitrile in 100 ml of glacial acetic acid is added dropwise at a temperature of 20 to 30 ° C with a mixture of 12 ml of concentrated sulfuric acid and 10 ml of nitric acid. After stirring at room temperature for 3 hours, it was poured into ice water. Further processing may be carried out by: (a) aspirating the precipitate and drying after washing to neutral, or (b) removing the precipitated product with methylene chloride, washing the organic phase first with an acidic solution. sodium carbonate and then neutral to water, dried, the solvent evaporated and the oily residue either distilled or triturated with ether, the solid yellow precipitate was filtered off with suction and dried.

The products prepared in this way are summarized in the following overview.

Example R ¹ Number

R2 physical data yield [melting point [° C]; [% of theory] refractive index; ....., boiling point (° C)]

50 H CH3 nD20 = 1.5890 68 51 H H 114 85 52 H C2H5 nD 20 = 1.5757 60 53 H n-C3H7 196/533 Pa 81 54 H ISSO-C3H7 ‘'72 77 55 CH3 CH3 126 74 56 —CH2 — CH2 — CH2 — CH2— 81 96 57 H 161 87 58 H —CH2 — CH = CH2 104 54

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Claims (1)

OBJECT OF THE INVENTION An insecticidal and acaricidal composition comprising as active substances carbamates and / or carboxylic acid esters, including natural and synthetic pyrethroles, and / or phosphoric acid esters, characterized in that it contains a derivative as a synergistic additive. benzodioxole of the general formula I, (I) in which: R represents a hydrogen, chlorine or bromine atom, a nitro group, a straight or branched alkyl group having 1 to 6 carbon atoms or a straight or branched alkenyl group having 2 to 6 carbon atoms, R 1 represents an atom. hydrogen or a straight or branched (C 1 -C 3) alkyl group; and R2 represents a straight or branched alkyl or alkenyl group containing up to 6 carbon atoms, a cycloalkyl group having from 3 to 8 carbon atoms. a benzyl group or a hydrogen atom when R is a nitro group, an alkyl or alkenyl group as defined above, or R 1 and R ² together form an alkylene radical having 2 to 8 carbon atoms, the weight ratio of the benzodioxole derivative to the active ingredients being between 0.1: 10 and 10: 0.1.