DE3041152A1 - Synergistic pesticidal, esp. insecticidal, compsn. - contg. 2-propargyl:oxy benzothiazole or benzoxazole deriv. - Google Patents

Abstract

Pesticidal compsn. comprises at least one cpd. effective against arthropods (esp. carbamates, carboxylates, phosphorus cpds. or halogenated hydrocarbons) and as synergist at least one cpd. of formula (I). In (I), R1 to R4 are each H, halo, alkyl or alkoxy (opt. substd. by halo), nitro, cyano, alkylcarbonyl or alkoxycarbonyl, or two of them together form a benzo ring; X is oxygen or sulphur. (I) are new cpds. provided than when X is sulphur then R3 is not nitro. The compsns. are useful for control of mites, spiders and esp. insects in agriculture, forestry, protection of stored materials and for hygienic applications. They have excellent residual activity on clay and wood and are stable on white-washed surfaces. (I) are more effective synergists than piperonyl butoxide and can be used with a wider range of pesticides.

Description

2-propargyloxy-benzazoles, their preparation, 2-propargyl-

Pesticides containing oxy-benzazole, their production and Use The present invention relates to new mixtures of synergistic acting 2-propargyloxy-benzazoles and other active ingredients containing these mixtures Pesticides, their manufacture and use to control Arthropods, especially of insects, mites and arachnids, and new 2-propargyloxy-benzazoles and their manufacture.

Insecticidal and acaricidal active ingredients or groups of active ingredients of the most varied Kind are already known, e.g .: A) Carbamic acid esters, such as N-methyl-0- (2-iso-propoxyphenyl) -carbamic acid esters (Propoxur), N-methyl-0- (2,3-dihydro-2,2-dimethyl-7-benzofuranyl) carbamic acid ester (Carbofuran), N-methyl-0- (2,3-dimethylmethylenedioxy-phenyl) -carbamic acid ester (Bendiocarb) and N-methyl-0- (1 -methyl-thio-ethylidene-amino) -carbamic acid ester (methomyl), B) Carboxylic acid esters, such as the naturally occurring pyrethroids as well as synthetic ones Pyrethroids, such as 3- (2-methyl-1-propenyl) -2,2-dimethyl-cyclo- propanecarboxylic acid 3,4,5,6-tetrahydro-phthalimidomethyl ester (Tetramethrin), 3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropane-carboxylic acid 3-phenoxybenzyl ester (Permethrin), l-R-cis -3- (2,2-dibromovinyl) -2,2-dimethyl-cyclopropane-carboxylic acid µC-S-cyano-3-phenoxy-benzyl ester (Decamethrin) and 3- (2,2-dichlorovinyl) -2,2-dimethyl-cyclopropanecarboxylic acid pentafluorobenzyl ester and other carboxylic acid esters such as acetic acid (1- (3,4-dichlorophenyl) -2,2,2-trichloroethyl ester) (Penfenate), C) phosphoric acid esters, such as .3. 0,0-dimethyl-0- (2,2-dichloro-vinyl) phosphoric acid ester (DDVP) and 0,0-dimethyl-S- (N-methyl-aminocarbonylmethyl) -thiol phosphoric acid ester (Omethoate), and d) halogenated hydrocarbons such as γ-1,2,3,4,5,6-hexachlorocyclohexane (Lindane), DDT and methoxychlor.

Next are synergistic mixtures of carbamic acid esters, such as e.g. N-methyl-O- (2-iso-propoxyphenyl) -carbamic acid esters or of phosphoric acid esters, e.g., 0,0-diethyl-0- (2-isopropyl-4-methylpyrimidin (6) yl) -thionophosphoric acid ester or of natural or synthetic pyrethroids with piperonyl ethers, e.g.

(2- (2-Butoxy-ethoxy) -ethoxy) -4,5-methylenedioxy-2-propyltoluene are known (cf. Bull. Org. Mond. SanteiBull. Wld.

Hlth Org. 1966, 35, 691-708; Schrader, G .: The development of new insecticides Phosphoric acid ester 1963, p. 158).

But what is the effectiveness of these synergistic combinations of active ingredients not satisfying. A certain has practical significance so far only obtained α (2- (2-butoxyethoxy) ethoxy) -4,5-methyl-endioxy-2-propyl-toluene.

It has now been found that the new active ingredient combinations of 2-propargyloxy-benzazoles of the formula I. in which R ', R ",, R"' R and R "" independently represent hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, nitro, cyano, alkylcarbonyl or alkoxycarbonyl or two of the radicals R ' until R '"together form a benzo radical and X stands for oxygen or sulfur, and active ingredients which are effective against arthropods, it being possible for these active ingredients to be present individually or as a mixture, a particularly high effect against arthropods, preferably against insects, mites and arachnids, in particular against insects.

Active ingredient combinations of 2-propargyloxybenzazoles are preferred here of formula (I) and A) carbamic acid esters and / or B) carboxylic acid esters including the natural and synthetic pyrethroids and / or C) phosphorus compounds, in particular phosphoric acid and phosphonic acid esters and / or D) halogenated hydrocarbons.

The present invention thus relates to new mixtures of the synergistic acting 2-propargyloxy-benzazoles of the formula I and others effective against arthropods Active ingredients, in particular insecticides, and pesticides containing these mixtures, in particular insecticidal agents, their manufacture, as well as the use of the new Mixtures and pesticides for combating arthropods, preferably of insects, mites and arachnids, in particular insects.

The synergistic effect of the compounds of the general formula I extends practically to all classes of compounds which are effective against arthropods. It is preferably of interest for the following active ingredients: A) Carbamic acid esters of the formula II in which R1 stands for an optionally substituted carbocyclic or heterocyclic aromatic radical or for an optionally substituted oxime radical, R2 stands for C1-C4-alkyl and R3 stands for hydrogen, C1-C4-alkyl or for the radical Z, where Z stands for the radical -Co-R4, where 4 R is halogen, C1-C4-alkyl, C1-C4-alkoxy, C3-C5-alkenoxy, C3-C5-alkynoxy, C1-04-alkylthio, C1-C4-alkylamino, di- C1-C4-alkyl-amino, C1-C4-alkylhydroxylamino, for optionally by halogen, nitro, cyano, trifluoromethyl, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylenedioxy, C1-C4-alkylthio, C1 -C4-alkoxycarbonyl-substituted phenoxy, phenylthio or phenylamino, for 2,3-dihydroxy-2,2-dimethyl-7-benzofuranyl or for the remainder where R5 is hydrogen, C1-C4-alkyl or di-C1-C4-alkylamino-carbonyl and R6 is C1-C4-alkyl, C1-C4-alkylthio, cyano-C1-C4-alkylthio, C1-C4- Alkylthio-C1 -C4-alkyl, or the two radicals R5 and R6 together represent C2-C8-alkanediyl optionally interrupted by oxygen, sulfur, SO or SO2, in which Z also represents the radical -Sn (O) m-R7 where n is 1 or 2 and m is zero, 1 or 2 and R7 is optionally halogen-substituted C1-C4-alkyl, C3-C5-alkenyl, C3-C5-alkynyl or C3-C6-cycloalkyl, optionally phenyl, benzyl or phenylethyl substituted by halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, C1-C4-alkyl or C1-C4-alkoxy, or for the remainder R8 stands for C1-C4-alkyl, C3-C5-alkenyl, C3-C5-alkynyl, C3-C6-cycloalkyl or benzyl and R9 for C1-C4-alkyl, C3-C5-alkenyl, C3-C5-alkynyl , C3-C6-cycloalkyl, benzyl, phenylethyl, halocarbonyl, formyl, C1-C4-alkyl-carbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkoxyphenoxycarbonyl, C3-C5-alkynoxycarbonyl, C3-C5 -Alkenoxy-carbonyl, C1-C5-alkylthiocarbonyl, C1-C4-alkyl-amino-carbonyl, C1-C4-alkyl-hydroxylamino-carbonyl, C1-C10-alkylphenoxy-carbonyl di-C1 di-C1-C4-alkyl-amino -carbonyl, phenylthiocarbonyl, phenoxycarbonyl, 2,3-dihydro-2,2-dimethyl-7-benzofuranyloxycarbonyl, for phenylsulfenyl, phenylsulfinyl, optionally substituted by halogen, cyano, nitro, trifluoromethyl, C1-C10-alkyl or C1-C4-alkoxy , Phenylsulfonyl or phenyl, or represents the remainder where R10 has the meaning given above for R5 and R11 has the meaning given above for R6, furthermore in the remainder the radicals R8 and R9 together represent a hydrocarbon chain with 3 to 8 carbon atoms, optionally interrupted by oxygen or sulfur, and in which R7 can also represent the same radical to which the radical -Sn (O) m-R7 is bonded.

Carbamic acid esters of the formula (II), in which R1 optionally denotes C1-C4-alkyl, C2-C4-alkenyl, C1-C4-alkoxy, C1-C4-alkoxymethyl, C1-C4-alkylthio, are very particularly preferred as active ingredient components , C1-C4-alkylthio-methyl, C1-C4-alkylamino, di- (C1-C4-alkyl) -amino, di- (C3-C4-alkenyl) -amino, halogen, dioxolanyl, methylenedioxy and / or by the rest -NwCH-M (CH3) 2 substituted radicals from the series phenyl, naphthyl, 2,3-dihydro-7-benzofuranyl, pyrazolyl or pyrimidinyl, or in which R1 represents an alkylidene amino radical of the formula IIa stands in which R12 and R13 have the meanings given above for R5 and R6, respectively.

Examples of the carbamic acid esters of the formula (II) are: 2-methyl-phenyl-, 2-ethyl-phenyl-, 2-iso-propyl-phenyl-, 2-sec-butyl-phenyl-, 2-methoxyphenyl-, 2-ethoxyphenyl-, 2-iso-propoxyphenyl-, 4-methyl-phenyl-, 4-ethyl-phenyl-, 4-n-propyl-phenyl-, 4-methoxyphenyl, 4-ethoxyphenyl, 4-n-propoxyphenyl, 3,4,5-trimethylphenyl, 3.5 Di methyl-4-methylthio-phenyl-, 3-methyl-4-dimethylaminophenyl-, 2-ethylthiomethyl-phenyl-, 1-naphthyl-, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl, 2,3- (dimethyl-methylenedioxy) -phenyl-, 2- (4,5-dimethyl-1,3-dioxolan-2-yl) -phenyl-, 1-methylthio-ethylidene-amino-, 2-methylthio-2-methylpropylidene-amino-, 1- (2-cyano-ethylthio) -ethylideneamino- and 1 -Methylthiomethyl-2, 2-dimethyl-propylideneamino-N-methyl-carbamic acid ester, 2-iso-propoxyphenyl-N-methyl-carbamic acid ester as a particularly preferred compound is called.

The synergistic effect of the compound of the formula (I) is more preferably shown in the case of B) carboxylic acid esters of the formula III in which R14 stands for an open-chain or cyclic alkyl radical which is optionally substituted by halogen, alkyl, cycloalkyl, by alkenyl optionally substituted by halogen and / or alkoxy, by phenyl or styryl, which is optionally substituted by halogen, optionally halogen-substituted radicals in the series Alkyl, alkoxy, alkylenedioxy and / or alkylthio substituted. are, by spirocyclically linked, optionally halogen-substituted cycloalk (en) yl, which is optionally benzannellated, in which R15 is also hydrogen, alkyl, haloalkyl, alkenyl, alkynyl or cyano, and R16 is an optionally substituted alkyl or aryl radical or represents a heterocycle, or together with R15 and the carbon atom to which both radicals are bonded, forms a cyclopentenone ring.

Carboxylic acid esters of the formula (III), in which 14 is the remainder, are very particularly preferred as active ingredient components in which R17 represents hydrogen, methyl, fluorine, chlorine or bromine and R18 represents methyl, fluorine, chlorine, bromine, C 1 -C 2 fluoroalkyl or C1-C2 chlorofluoroalkyl or is optionally substituted by halogen and / or optionally halogen-substituted Radicals of the series C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio and / or C1-C2-alkylenedioxy is substituted phenyl and in which both radicals R17 and R18 are C2-C5-alkanediyl (alkylene); or in which R14 for the rest where R19 is phenyl optionally substituted by halogen and / or by optionally halogen-substituted radicals from the series C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C1-C2-alkylenedioxy and R20 is isopropyl or Cyclopropyl; or in which R14 for one of the radicals or methyl, in which R15 also represents hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, cyano or ethynyl and R16 represents optionally halogen and / or an optionally halogen-substituted radical from the series C1-C4-alkyl , C2-C4-alkenyl, C1-C4-alkoxy, C2-C4-alkenoxy, C1-C4-alkylthio, C1-C2-alkylenedioxy, phenoxy and / or benzyl-substituted radicals phenyl, furyl or tetrahydrophthalimido.

The naturally occurring pyrethroids are also particularly preferred.

Examples of the carboxylic acid esters of the formula (III) are: Acetic acid (2,2,2-trichloro-1- (3,4-dichlorophenyl) ethyl) ester, 2,2-dimethyl-3- (2-methyl-propen-1-yl) -cyclopropanecarboxylic acid (3 , 4,5,6-tetrahydro-phthalimido-methyl) ester, 2,2-Dimethyl-3- (2,2-dichloro-vinyl) -cyclopropanecarboxylic acid - (3-phenoxy-benzyl) -ester, 2,2-Dimethyl-3- (2,2-dichloro-vinyl) -cyclopropane-carboxylic acid- (g -cyano-4-fluoro-3-phenoxy-benzyl) -ester, 2, 2-dimethyl-3- (2, 2-dichlorovinyl) -cyclopropanecarboxylic acid (pentafluorobenzyl) -ester, 2,2-dimethyl-3- (2,2-dibromo-vinyl) -cyclopropanecarboxylic acid-! oi-cyano-3-phenoxy-benzyl) ester, 3-methyl-2- (4-chloro-phenyl) -butanoic acid- (<-cyano-3-phenoxybenzyl) -ester and 2,2-dimethyl-3- (2,2-dichloro-vinyl) -cyclopropanecarboxylic acid- (d -cyano-3-phenoxy-benzyl) ester.

Furthermore, the synergistic effect of the compounds of the general formula (I) is shown preferably in the case of C) phosphorus compounds, in particular phosphoric acid and phosphonic acid esters of the general formula IV in which X 'each represents 0 or S and Y' represents 0, S, -NH- or a direct bond between the central P atom and R23 and R21 and R22 are identical or different and represent optionally substituted alkyl or Aryl, R23 represents hydrogen, optionally substituted alkyl, aryl, heteroaryl, aralkyl, alkenyl, dioxanyl or an oxime radical or represents the same radical to which it is bonded.

Phosphoric and phosphonic esters of the formula (IV), in which R21 and R22 are identical or different and are C1-C4-alkyl or phenyl, R23 is alkyl with 1 to 4 carbon atoms, which may optionally be replaced by halogen, hydroxyl, are particularly preferred. Cyano, optionally halogen-substituted phenyl, carbamoyl, alkylsulfonyl, alkylsulfinyl, alkylcarbonyl, alkoxy, alkylmercapto, alkoxycarbonyl, alkylaminocarbonyl, the latter with up to 6 carbon atoms in each case, is substituted for alkenyl with up to 4 carbon atoms, which is optionally substituted by halogen, optionally halogen-substituted Phenyl or C1-C4-alkoxycarbonyl is substituted, or for the remainder of the general formula IV a where R24 and R25 have the meaning given above for R5 or R6, or represent cyano or phenyl, R23 furthermore represents dioxanyl which is substituted by the same radical to which R23 is bonded, or R23 represents the same radical to which it is bonded, or R23 represents phenyl which is optionally substituted by methyl, nitro, cyano, halogen and / or methylthio; R23 also particularly preferably represents heteroaromatic radicals optionally substituted by C1-C4-alkoxy, C1-C4-alkylthiomethyl, C1-C4-alkyl and / or halogen, such as pyridinyl, quinolinyl, quinoxalinyl, pyrimidinyl or benzo-1,2,4- triazinyl.

The following may be mentioned by way of example: O, O-dimethyl or O, O-diethyl-0- (2,2-dichloro- respectively.

2,2-dibromovinyl) phosphoric acid ester, O, O-diethyl-O- (4-nitro-phenyl) -thionophosphoric acid ester, O, O-dimethyl-0- (3-methyl-4-methylthio-phenyl) -thionophosphoric acid ester, 0,0-dimethyl-0- (3-methyl-4-nitro-phenyl) -thionophosphoric acid ester, 0-ethyl-S-n-propyl-0- (2 4-dichloro-phenyl) -thionophosphoric acid ester, O-ethyl-S-n-propyl-0- (4-methylthio-phenyl) -thionophosphoric acid ester, 0,0-dimethyl-S- (4-oxo-1,2,3-benzotriazin (3) yl-methyl) -thionothiolphosphoric acid ester, O-methyl-0- (2-iso-propyl-6-methoxy-pyrimidin (4) yl) -thionomethanephosphonic acid ester, 0,0-Diethyl-0- (2-iso-propyl-6-methyl-pyrimidin (a) yl) -thionophosphoric acid ester, 0,0-diethyl-O- (3-chloro-4-methyl-coumarin (7) yl ) thionophosphoric acid ester, 0,0-Dimethyl-2,2,2-trichloro-1-hydroxy-ethane-phosphonic acid ester, O, O-dimethyl-S- (methylaminocarbonyl-methyl) -thionophosphoric acid ester.

The synergistic effect of the compounds of the formula (I) is evident also preferably with halogenated hydrocarbons, such as g -1,2,3,4,5,6-hexachlorocyclohexane and 1,1,1-trichloro-2,2-bis (4-chloro-phenyl) -ethane.

A good overview of carbamates that can be used according to the invention, Carboxylic acid esters and phosphorus compounds also supplies "Plant protection and pest control", edited by K.H. Büchel, Thieme Verlag Stuttgart, 1977) The for the invention Combinations of active ingredients as synergists too. using 2-propargyloxybenzazole are defined by formula (I).

In formula I, R ', R ", R"', R "" are preferably independent of one another for hydrogen, halogen, for C1-C4-alkyl optionally substituted by halogen or C1-C4-alkoxy, for nitro, cyano, for C2 ~ 4-alkylcarbonyl or C24-alkoxycarbonyl or two of the radicals R 'to R "" together form benzo and X represents oxygen or Sulfur.

The present invention further relates to new 2-propargyloxy-benzazoles of the formula V in which R ', R "and R'"'independently represent hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, nitro, cyano, alkylcarbonyl or alkoxycarbonyl or the radicals R' and R "together represent a benzo radical and R "'represents hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, cyano, alkylcarbonyl or alkoxycarbonyl or the radical R'" together with one of the radicals R "or R""forms a benzo radical and X is oxygen or sulfur and in which R "'can still stand for nitro when X stands for oxygen.

In formula V, R ', R ", R', R" "are preferably independent of one another for hydrogen, halogen, for C1 -C4 -alkyl which is optionally substituted by halogen or C1-C4-alkoxy, for cyano, for C 2-4 -alkylcarbonyl or C 2-4 -alkoxycarbonyl or two of the radicals R 'to R "" together form benzo and X represents oxygen or Sulfur.

Alkyl and alkoxy, R 'to R "" contain preferably 1 to 4, in particular 1 or 2 carbon atoms, where methyl, ethyl, n- and i-propyl and n-, i-, sec.- and t-butyl, methoxy, ethoxy, n- and i-propoxy and n-, i-, sec- and t-butoxy be. Alkylcarbonyl and alkoxycarbonyl R 'to R1111 contain 2 to 4, preferably 2 or 3 carbon atoms, being methoxy-, ethoxy- and n- and i-propoxycarbonyl as well as methyl, ethyl and n- and i-propylcarbonyl may be mentioned.

Halogen as R 'to R "" and as a substituent of alkyl and alkoxy R 'to R "" stands for fluorine, chlorine, iodine and bromine, preferably for chlorine and bromine, especially for chlorine.

Halosubstituted alkyl and alkoxy R 'to R "" preferably contain 1 to 5, in particular 1 to 3 halogen atoms, preferably chlorine or fluorine atoms.

Compounds of the formulas I and V in are of particular interest which R 'to R "" independently represent hydrogen, halogen, C1 4 -alkyl or C1-4-alkoxy or two of the radicals R 'to R "" together form a benzo radical and X is oxygen or sulfur.

In particular, in the formulas I and V R ', R ", R' and R't" are independent each other for hydrogen, chlorine or methyl and X for oxygen or sulfur.

Examples of the compounds of the formula (I) and (V) include: 2-propargyloxy-benzoxazole and 2-propargyloxy-benzothiazole, 5-chloro-2-propargyloxy-benzoxazole and 5-chloro-2-propargyloxy-benzothiazole, 6-chloro-2-propargyloxy-benzoxazole and 6-chloro-2-propargyloxy-benzthiazole, 5,7-dichloro-2-propargyloxy-benzoxazole and 5,7-dichloro-2-propargyloxy-benzothiazole, 5-methyl-2-propargyloxy-benzoxazole and 5-methyl-2-propargyloxy-benzothiazole.

Unless otherwise stated in the description, contain alkyl radicals or the alkyl parts of radicals containing alkyl groups, preferably 1 to 6, especially especially 1 to 4 carbon atoms and are straight-chain or branched, methyl, ethyl, n- and i-propyl being mentioned as examples.

Alkenyl and alkynyl groups preferably contain 2 to 6, in particular 2 to 4 carbon atoms and preferably 1 or 2 in particular 1 double or triple bonds.

Aryl groups are preferably naphthyl and phenyl, especially phenyl.

Heterocyclic groups preferably contain 5 to 7, in particular 5 or 6 ring members and can have one or more heteroatoms, preferably 1 to 3, in particular 1 or 2 heteroatoms, such as nitrogen, oxygen and / or sulfur contain.

Halogen represents fluorine, chlorine, bromine and iodine, preferably fluorine, Chlorine and bromine, especially for chlorine and fluorine.

Multiply substituted radicals preferably contain 1 to 5, in particular 1 to 3 identical or different substituents.

The compounds of the formulas (I) and (V) can be found in the literature described processes are prepared in a known manner (see. Japanese patent application 54 020 137).

The 2-halobenzazoles to be used for this are known and / or obtainable according to known processes (cf. German Disclosure document 1 670 706, German Auslegeschrift 1 210 617 and British Patent 966 496).

The compounds of the formula (I) or formula (V) are obtained by adding 2-halobenzazoles of the formula VI in which Hal stands for halogen and R 'to R ″ ″ have the meaning given above, reacted with propargyl alcohol in the presence of a base and, if appropriate, in the presence of a solvent.

All inert organic solvents can be used as diluents in question. These preferably include aliphatic and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, benzene, toluene and xylene; Ethers, such as diethyl ether, Dibutyl ether, glycol dimethyl ether, tetrahydrofuran and dioxane; Amides such as dimethylformamide and alcohols such as methanol, ethanol and i-propanol and excess propargyl alcohol.

All customary acid binders can be used as acid binders. These preferably include alkali and alkaline earth metal hydroxides, such as KOH, NaOH, Mg and Ca hydroxide; Alkali carbonates, such as Na2C03 and K2C03; Alkali alcoholates, such as sodium methylate, potassium ethylate and potassium t-butylate; Alkali metals, their amides and hydrides.

The reaction temperatures can be varied within a relatively wide range will. In general, the temperature is between about -20 and about 1000.degree. C., preferably between about 0 ° and 80 ° C.

When carrying out the process, 1 mole of 2-halobenzazole is used of the formula VI preferably 1 to 1.5 mol, in particular 1.1 to 1.2 mol or

Equivalents of the acid binder.

Per mole of 2-halobenzazole of the formula VI is preferably at least 1 mole of propargyl alcohol used.

Propargyl alcohol can also be used in a larger excess without any disadvantage be used.

The reaction temperatures are expediently at low temperatures put together between approx. -20 to + 200C and then slowly while stirring warmed up.

The products can be worked up and isolated by customary methods be done, for example, by shaking with water and one with water practical Separate immiscible organic solvents such as methylene chloride the organic phase, washing, with water, drying, filtering and concentration or

complete distillation of the filtrate.

As already mentioned, the new active ingredient combinations show the according to the invention usable 2-propargyloxybenzenes of the formula (I) with active ingredients such as carbamic acid esters, Carboxylic acid esters, phosphoric and phosphonic acid esters and halogenated hydrocarbons an excellent increase in effectiveness compared to the individual active ingredients or compared to their sum.

Surprisingly, the pesticidal effect is that of the invention Combinations of active ingredients are much higher than the effects of the individual components or the sum of the effects of the individual components. It is also much higher than the effect of active ingredient combinations with the well-known synergist piperonyl butoxide.

In addition, show the 2-propargyloxy-benzazoles which can be used according to the invention excellent synergistic effectiveness not only for one class of active ingredients, but in the case of active ingredients from a wide variety of chemical substance groups.

The weight ratios of the synergists and active ingredients can be in can be varied over a relatively wide range. Generally they are called synergists compounds of the formula (I) used with the other active ingredients in the ratio 0.1: 10 to 10: 0.1, preferably 0.2 to 5 to 5 to 0.2, in particular 0.5: 1.0 to 1.0: 1.0 used.

The active ingredient combinations according to the invention do not have just one quick knock-down effect, but also cause the lasting killing of the animal pests, preferably insects and mites, especially insects, those in agriculture, forests, in store and material protection as well as in the hygiene sector occurrence. They are against normally sensitive and resistant species as well as against all or individual stages of development are effective.

The pests mentioned above include: From the order of the Isopoda e.g. Oniscus asellus, Porcellio scaber.

From the order of the Thysanura e.g. Lepisma saccharina.

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

From the order of the Dermaptera, e.g. Forficula auricularia.

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

From the order of the Anoplura, e.g. Pediculus humanus corporis, Haematopinus spp., Linograthus spp.

From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.

From the order of the Heteroptera e.g. Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera, e.g. Myzus spp. and Psylla spp.

From the order of the Lepidoptera, e.g. Ephestia kuehniella and Galleria mellonella.

From the order of the Coleoptera, e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bejulus, Oryzaephilus surinamensis, Sitophilus spp., Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp. and Tenebrio molitor.

From the order of the Hymenoptera, e.g. Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp.r Calliphora erythrocephala, Lucilia spp.r Chrysomyia spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp. and Tabanus spp.

From the order of the Siphonaptera, e.g. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnida, e.g. Scorpio maurus, Latrodectus mactans.

From the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.

The active ingredient combinations can be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, Foams, pastes, soluble powders, aerosols, suspension-emulsion concentrates, impregnated with active ingredients Natural and synthetic materials, finest encapsulation in polymer materials, furthermore in formulations with burning charges, such as smoking cartridges, cans, coils, etc., as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by. Mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents.

In the case of using water as an extender, e.g. organic solvents can be used as auxiliary solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. 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, like dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers are meant liquids which are at normal temperature and are gaseous under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers: natural Ground rock, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as highly dispersed silica, Alumina and silicates; as solid carriers for granules: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well synthetic granules made from inorganic and organic flours and granules made of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-producing agents: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, Alkyl sulfonates; as dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Combination of active ingredients, preferably between 0.5 and 90%.

The active ingredient combinations according to the invention are used in the form of their commercially available formulations and / or those from these formulations prepared application forms.

The total active ingredient content from the commercially available formulations Prepared application forms can vary within wide limits. The active ingredient concentration the use forms can range from 0.0001 to 100% by weight of active ingredient combination, preferably between 0.01 and 10 wt .-%.

They are used in a customary manner adapted to the use forms Way.

When used against hygiene and storage pests stand out the active ingredient combinations due to an excellent residual effect on wood and Clay as well as good alkali stability on limed substrates.

The following examples show active ingredients and 2-propargyloxy-benzazoles which can be used according to the invention, with the aid of their combination as an example of a synergistic effect: I. 3 examples of active ingredients which can be used according to the invention Propoxur) (carbofuran) (bendiocarb) (Methomyl) E) Pyrethrins of natural origin as a 25% extract (Tetramethrin) (Permethrin) (Decamethrin) (Penfenate) (γ-hexachlorocyclohexane) (DDVP) (omethoate) II. Examples of synergists which can be used according to the invention Standard synergist: 6) Piperonyl butoxide (known) Test examples: LT100 test Test animals: Musca domestica, Weymanns strain, (resistant to carbamic acid esters and p-esters) Solvent: Acetone Solutions are prepared from the active ingredients, synergists and mixtures of active ingredients and synergists 2.5 ml of it pipetted into Petri dishes on filter paper with a diameter of 9.5 cm. The filter paper soaks up the solutions. The Petri dishes remain open until the solvent has completely evaporated. Then 25 test animals are placed in the Petri dishes and covered with a glass lid.

The condition of the animals will be continuous for up to 6 hours and thereafter checked after 24, 48 and 72 hours.

The time required for a 100% knock-down effect is determined is required. If the LT100 is not reached after hours, the% rate will be the Knocked down test animals were found.

Concentrations of the active ingredients, synergists and mixtures and their Effect can be seen in the table below.

Active ingredient + synergist no. Concentrations in% LT1 00. after minutes, Code book - active ingredient + synergist. or% according to minutes stabe A) - 1.0 - 360 '= 0% B) - 1.0 - 360 '= 70% C) - 1.0 - 360' = 35% D) - 1.0 - 360 '= 80% E) - 0.2 - 90 'F) - 0.04 - 360' = 90% G) - 0.04 - 105 'H) - 0.0016 - 60' I) - 0.0016 - 105 ' J) - 1.0 - 360 '= 70% K) 0.04 - 210' L) - 0.008 - 150 'M) - 0.04 - 360' = 45% - 1) - 0.04 360 '= 60% 2) - 1.0 360' = 90% 3) - 1.0 360 '= 5% - 4) - 1.0 360' = 0% - 5) - 0.04 360 '= 60% - 6) - 1.0 360' = 0%.

(Standard) A + 6 1.0 + 1.0 360 'A + 1 0.008 + 0.008 150' A + 2 0.04 + 0.04 120 'A + 3 0.04 + 0.04 120' A + 4 0.04 + 0.04 210 'A + 5 0.04 + 0.04 90' Active ingredient + Synergist no. Concentrate in% LT100 according to Mi code book - active ingredient + synergist slot, or% after minutes B + 6 0.04 + 0.04 360 '= 50% B + 1 0.008 + 0.008 120' B + 2 0.008. + 0.008 210 'B + 3 0.04 + 0.04 105' B + 4 0.04 + 0.04 150 'B + 5 0.008 + 0.008 120 'C + 6 0.2 + 0.2 360' = 80% C + 1 0.04 + 0.04 105 'C + 2 0.04 + 0.04 90 'C + 3 0.2 + 0.2 120' C + 4 0.2 + 0.2 210 'C + 5 0.04 + 0.04 90' D + 6 0.2 + 0.2 210 'D + 2 0.2 + 0.2 90' D + 3 0.2 + 0.2 150 'D + 4 0.2 + 0.2 180' D + 5 0.04 + 0.04 210 '+ + 6 0.2 + 0.2 45' E + 1 0.2 + 0.2 45 'E + 4 0.2 + 0.2 45' E + 5 0.2 + 0.2 45 'F + 6 0.04 + 0.04 120' F + 1 0.04 + 0.04 105 'F + 2 0.04 + 0.04 75' F + 4 0.04 + 0.04 120 'r + 5 0.04 + 0.04 90' G + 6 0.04 + 0.04 901 G + 1 0.04 + 0.04 75 'G + 2 0.04 + 0.04 75' G + 4 0.04 + 0.04 90 'G + 5 0.04 + 0.04 75' H + 6 0.0016 + 0.0016 60 'H + 3 0.0016 + 0.0016 45' H + 4 0.0016 + 0.0016 45 'I + 6 0.0016 + 0.0016 360 '= 95% I + 1 0.0016 + 0.0016 75' I + 2 0.0016 + 0.0016 105 'I + 3 0.0016 + 0.0016 105 I + 4 0.0016 + 0.0016 105 'I + 5 0.0016 + 0.0016 90' Active ingredient + Synergist no. Concentrations in% LT100 according to Minu-Kennbuch- active ingredient + synergist th, or% after several minutes J + 6 1.0 + 1.0 360 '= 95% J + 1 0.04 + 0.04 120r J + 3 0.2 + 0.2 240 J + 4 0.04 + 0.04 360 'J + 5 0.04 + 0.04 210' K + 6 0.04 + 0.04 150 K + 1 0.04 + 0.04 90 'K + 2 0.04 + 0.04 120 K + 4 0.04 + 0.04 105' K + 5 0.04 + 0.04 90 'L + 6 0.008 + 0.008 105 L + 1 0.008 + 0.008 90 L + 3 0.008 + 0t008 90 L + 4 0.008 + 0.008 90 L + 5 0.008 + 0.008 90 'M + 6 0.04 + 0.04 360' = 90% M + 1 0.04 + 0.04 180 M + 2 0.04 + 0.04 240 M + 3 0.04 + 0.04 150 The manufacture of the Synergists of the formulas I and V which can be used according to the invention are carried out in a known manner Manner according to methods known from the literature and should be illustrated by the following examples are: (All percentages in the description are weight *, unless otherwise is specified): Example 1: 3.4 g (0.11 mol) of 80% sodium hydride are added to 75 ml of propargyl alcohol at room temperature (20 + 50C); then will at 250C (16.7 g) (0.1 mol) 2-chloro-5-methylbenzazole was added dropwise and the reaction mixture is stirred at this temperature for 15-20 hours. Excess propargyl alcohol is distilled off under reduced pressure; the residue is then washed with water and methylene chloride shaken, the organic phase separated, washed with water, dried, filtered and the filtrate is concentrated. The 2-propargyloxy-5-methylbenzthiazole obtained has a melting point of 550C.

The compounds of the following examples can be prepared analogously to Example 1 getting produced.

At- R 'R "Rtlt R" "X Melting point (OC) game or boiling point no. (OC / Torr) 2 H H H H 0 132/10 3 H Cl H H 0 72 4 H Cl H Cl 0 91 5 H H H H S 53 6 H H Cl H 0 148/3

Claims (10)

Claims 1. Pesticides which contain at least one active substance against arthropods, preferably from the group of carbamic acid esters, carboxylic acid esters, phosphorus compounds or halogenated hydrocarbons, and at least one synergist, characterized in that the synergist is a 2-propargyloxy-benzazole of the formula I. in which R ', R ", R' and R""independently represent hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, nitro, cyano, alkylcarbonyl or alkoxycarbonyl or two of the radicals R 'to R "" together form a benzo radical and X stands for oxygen or sulfur. 2. Pesticides according to claim 1, in which the 2-propargyloxy-benzazole of the formula I R ', R ", R'" and R "" independently. from each other for hydrogen, halogen, for optionally by Halogen substituted C1-C4-alkyl or alkoxy, for nitro, cyano, for C2 4-alkylcarbonyl or C 4-alkoxycarbonyl or two of the radicals R 'to R ″ ″ together form a benzo radical and X is Oxygen or sulfur. 3. Pesticide according to claim 1, in which in the 2-propargyloxy-benzazole of the formula I R ', R ", R"' and R "" independently of one another stand for hydrogen, halogen, C1-C4-alkyl or C1-4-alkoxy or two of the radicals R 'to R "together form a benzo radical and X stands for oxygen or sulfur. 4. Pesticide according to claim 1, in which in the 2-propargyloxy-benzazole of the formula I R ', R ", R"' and R "" independently of one another are hydrogen, chlorine or methyl and X is oxygen or sulfur. 5. Process for the manufacture of pesticides, thereby characterized in that at least one substance effective against arthropods and at least a propargyloxy-benzazole of formula 1 with inert extenders, carriers and diluents, Fillers, propellants, surface-active substances and / or formulation auxiliaries mixes. 6. Use of the compounds of the formula I as synergists in pesticides, especially in insecticides and acaricides. 7. 2-propargyloxy-benzazoles of the formula V in which R ', R "and R""independently represent hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, nitro, cyano, alkylcarbonyl or alkoxycarbonyl or the radicals R' and R" together form a benzo radical and R "'represents hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, cyano, alkylcarbonyl or alkoxycarbonyl or the radical R"' together with one of the radicals R "or R""forms a benzo radical and X represents oxygen or Is sulfur, and in which R "'can still stand for nitro when X stands for oxygen. 8. 2-propargyloxy-benzazole according to claim 7, in which R ', R ", R', R ″ ″ independently of one another for hydrogen, halogen, for optionally by halogen substituted C1-C4-alkyl or C1-C4-alkoxy, for cyano, for C2 4-alkylcarbonyl or C2 -alkoxycarbonyl or two of the radicals R 'to R "" together form benzo and X is oxygen or sulfur. 9. 2-propargyloxy-benzazole according to claim 7, in which R ', R ", R "'and R" "independently of one another represent hydrogen, chlorine or methyl and X represents Oxygen or sulfur. 10. Process for the preparation of 2-propargyloxybenzazoles of the formula V in which R ',, R "and R""independently represent hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, nitro, cyano, alkylcarbonyl or alkoxycarbonyl, or the radicals R' and REI together form a benzo radical and R "'represents hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, cyano, alkylcarbonyl or alkoxycarbonyl or the radical R"' together with one of the radicals R "or Rilt? forms a benzo radical and X stands for oxygen or sulfur, and in which R "'can also stand for nitro when X stands for oxygen, characterized in that 2-halobenzazoles of the formula VI in which Hal stands for halogen and R ', R ", R"' and R "" and X have the meaning given above, is reacted with propargyl alcohol in the presence of a base and optionally in the presence of a solvent.