DE2003333A1 - Preparations for combating insects and arachnids and their stages of development - Google Patents

Description

Dr. F. Zumatein Sr. - Dr. E. Aesmann 2 G 0 ^ ^ ^ ^ Dr. R. Koenigsberger - Dipl. Phys. R. Holzbauer * ", ^w ^ ^ ° ^ Dr. F. Zumetein jun. 5a- 297 8 *

Patent to w fl It 8 Munich 2, Bräuhausstrasse 4 / III

Preparations for the control of insects and arachnids and their stages of development

The present invention relates to new agents and methods for controlling insects, arachnids and their stages of development using substituted 3-hydroxy-triazene as active ingredients.

Insecticidal and acaricidal active ingredients that have gained economic importance either belong to the class of phosphorus compounds, the carbamic acid ester or the halogenated hydrocarbons. On the one hand, such connections are mostly opposite Toxic to plants and / or warm-blooded animals; on the other hand, pests show signs of resistance. This is why it is necessary to develop new agents containing active ingredients with low toxicity and those against insects and arachnids are not resistant.

From the group of the triazenes, a large number of compounds are available as herbicidal active ingredients [British Patent No. 1.130.469] and as agents for protecting organic materials of all kinds from insect caused damage [British Patent No. 941,489]. These are l-phenyl-3,3-dialkyl-triazenes but which have no insecticidal and acaricidal properties.

It has now been found that agents which l-phenyl-3-hydroxy-triazenes Contained as active ingredients, they are excellent for combating insects, arachnids and their stages of development suitable. These active ingredients are in the usual use concentrations Not toxic to plants and warm-blooded animals. Particularly noteworthy is. the inhibiting influence of these active ingredients on development processes in insects and arachnids.

009841/1904

BATH ORIGINAL

The active ingredients contained in the agents according to the invention correspond to formula I:

N-N (D

In this formula:

R ^ hydrogen, halogen, nitro, a lower alkyl radical, a lower alkyl or alkynyl radical bonded to the nucleus via oxygen or sulfur, a haloalkyl radical, a Alkanoyloxy or alkanoylamino radical, the phenyl radical or a halogenated phenyl radical,

R2 and R ~ independently of one another are hydrogen, halogen, a lower one Alkyl or haloalkyl radical, a lower alkyl radical bonded to the nucleus via oxygen or sulfur and

R / is an alkyl radical with 1 to 8 carbon atoms, an alkenyl radical with 3 or 4 carbon atoms, the benzyl radical, a halogenated benzyl radical, a haloalkyl radical, the Phenyl radical or a halogenated phenyl radical.

Among the lower alkyl radicals represented by R ,, R2 and R ^, which can optionally be bonded to the core via oxygen or sulfur are normal or branched alkyl radicals with 1 to 4 carbon atoms, especially the methyl or ethyl radical to understand. The alkanoyl radical of an alkanoyloxy or alkanoylamino group has 2 to 5, especially 2, carbon atoms. The haloalkyl radicals R-, and R, come through one or more times Fluorine or chlorine substituted alkyl radicals with 1 to 4, especially 1 or 2 carbon atoms are possible. As lower alkynyl radicals R, " those bonded to the nucleus via oxygen or sulfur come those with 3 or 4 carbon atoms, especially the propargyl radical in question.

Some of the 3-hydroxy-triazenes covered by the formula I are known from publications as complexing agents. Indian Chem. Soc. 43, (1906) 289-290, ibid. 38, (1961) 771-775, ibid. .36, (1959) 563-566] became known. The new connections will be

009841/190 *

Known processes (loc. Cit.) by reacting an R, -substituted Hydroxylamines obtained with an aryldiazonium compound. Another production method consists in the conversion of an aryl hydrazine with a nitroso compound [M. Elkins et L. Hunter, J. Chem. Soc. 1938, 1346 ff].

The active ingredients contained in the agents according to the invention of formula I have a good feed poison, contact poison and long-term action, and they are also outstandingly suitable for combating sucking insects, for example to control the following eating and sucking insects: insects of the Muscidae family, Stornoxidae and Culicidae, such as the polyvalent-resistant and normally sensitive housefly (Musca domestica), calf stings (Stomoxys calcitrans) and mosquitoes (e.g. Aedes aegypti, Culex fatigans, Anopheles stephensi), of the families Curculionidae, Bruchididae, Dermestidae, Tenebrionidae, Chrysomelidae, Tineidae, e.g. grain beetles (Sitophilus granarius), bean beetle (Bruchidius obtectus), bacon beetle (Dennestes vulpinus), meal beetle (Tenebrio molitor), Colorado beetle (Leptinotarsa decemlineata), clothes moth (Tineola biselliella), of the families Pyralidae, e.g. flour moth caterpillars, Blattidae, e.g. cockroaches (Phyllodromia germanica, Periplaneta americana, Blatta orientalis), the family Locustidae, e.g. locusts (Logusta inigratoria), the families Noctuidae and Yponomeutidae, e.g. Prodenia litura, oak moth (Tortrix viridana), apple tree moth (Yponomeuta malinella) etc.

Furthermore, the new agents can be used to control the larval and adult stages of arachnids, e.g. the families letranychidae, Arachnidae, Ixodidae, Argasidae and to kill insect and arachnid eggs.

Particularly important for the control of insects and arachnids and their stages of development have those agents that contain one or more of the following active ingredients:

No connection

1 l-Phenyl-3-hydroxy-3-methyl-triazene m.p. 64-66 ^C C

2 1- (A'-ChlorphonylO-S-hydroxy-S-methyl-triazene mp 145-147 ^C C

3 1- (4 ¹ - · chlorophenyl) -3-hydroxy ~ 3-ethyl-triazene m.p. 109-11O ^C C

009841/1904

No connection

4 1- (4 ¹ -chlorophenyl) -S-hydroxy-1-isopropyl-triazene mp 133-134 ° C

5 l- (4'-Chlorophenyl) -S-hydroxy-Sn-propyl-triazene mp 95- 96 ⁰ C

6 L- (4'-Chlorophenyl) -S-hydroxy-S-n-butyl-triazene, mp 71-73 ° C

7 1- (4 ¹ -chlorophenyl) -3-hydroxy-3-n-amyl-triazene OeI

8 1- (4'-Chlorophenyl) -S-hydroxy-S-n-octyl-triazene OeI

9 1- (4'-Chlorophenyl) -3-hydroxy-3-allyl-triazene OeI

10 1- (4'-bromophenyl) -3-hydroxy-3-methyl-triazene m.p. 147-15O ° C

11 1- (4'-bromophenyl) -3-hydroxy-3-ethyl-triazene, mp 112-113 ⁰ C.

12 l- (4'-Bromophenyl) -3-hydroxy-3-isopropyl-triazene, mp 136-138 ° C

13 1- (3'-bromophenyl) -3-hydroxy-3-methyl-triazene, mp 77- 80 ⁰ C

14 1- (3'-bromophenyl) -3-hydroxy-3-ethyl-triazene mp 68- 71 ⁰ C

15 1- (4'-chlorophenyl) ^ -yyy

triazene OeI

16 1- (4'-Chlorophenyl) -3-hydroxy-3-phenyl-triazene m.p. 145-146 ° C

17 1- (4'-Chlorophenyl) -3-hydroxy-3-benzyl-triazene m.p. 149-151 ° C

18 L- (4'-methylphenyl) -3-hydroxy-3-methyl-triazene mp 113-115 ° C

19 l- (4'-methylphenyl) -3-hydroxy-3-ethyl-triazene mp 80- 82 ⁰ C

20 1- (4'-methylphenyl) -3-hydroxy-3-n-propyl-triazene m.p. 54-55 ° C

21 l- (2 ', 4'-dichlorophenyl) -S-yyy

triazene mp 90-100 ⁰ C.

22 l- (3 ', 4'-dichlorophenyl) -S-yyy

triazene m.p. 153-154 ° C

23 1- (3 ', 4'-dichlorophenyl) -S-yyy

triazene m.p. 97-99 ° C

24 1- (2 '-Hethyl-4 ¹ -chlorophenyl) -S-yyy
triazene OeI

25 1- (2'-Methyl-4 ¹ -chlorophenyl) -3-hydroxy-3-isopropyl-triazene · Mp 50-54 ° C

26 1- (2'-methyl-5'-chlorophenyl) -Syyy

triazene mp 82- 84 ⁰ C

27 1- (2'-methyl-5'-chlorophenyl) -3-hydroxy-3-isopropyl-triazene OeI

28 l- (4'-chloromethyl-phenyl) -3-hydroxy-3-ethyltriazene OeI

29 l- (3'-trifluoromethylphenyl) -3-hydroxy-3-methyl-

triazene mp 90- 92 ⁰ C

30 l- (3 '-TrifluomiGthylphenyl) -3-hydroxy-3-ethyl-

triazene m.p. 35-36 ° C

31 l- (4'-methoxyphenyl) -3-hydroxy-3-methyl-triazene m.p. 99-102 ° C

32 l- (2 ^l -Mechy.lthiophenyl) -3-hydroxy-3-ethyl-triazene OeI

0098A1 / 1904

No connection

33 l- (4'-Acetoxyphenyl) -3-hydroxy-3-ethyl-triazene OeI

34 l- (4'-propargyloxyphenyl) -3-hydroxy-3-methyl-

triazene mp 112-113 ⁰ C.

35 1- (4 ¹ -propargyloxyphenyl) -S-hydroxy-S-isopropyl-

triazene m.p. 113-115 ° C

36 1- (4'-acetaminophenyl) -3-hydroxy-3-methyl-

triazene m.p. 200-2O5 ° C

37 1- (4 ¹ -acetaminophenyl) -Sy

triazene m.p. 185-188 ° C

38 1- (4 ¹ -acetaminophenyl) -S-yyppy

triazene mp 178-18O ⁰ C

39 1,3-Diphenyl-3-hydroxy-triazene OeI

40 l- (4'-biphenylyl) -3-hydroxy-3-ethyl-triazene, mp 149-151 ⁰ C.

41 1- (2 ', 4'-dichlorophenyl) -S-hydroxy-S-isopropyl-

triazene m.p. 50-52 ° C

The active ingredient content of the agents according to the invention varies from 0.01 to 80% by weight, depending on whether it is directly applicable Work-up forms or so-called active ingredient concentrates. In addition, these agents can also contain other insecticides, for example from the group of phosphoric acid esters, phosphoric acid half-esters or half-amides, in particular the phosphoric acid esters of heterocyclic compounds, from the group of carbamic acid esters, in particular the heterocyclic carbamic acid esters and from the group of chlorinated hydrocarbons, furthermore Acaricides, for example from the series of benzilic acid esters, phosphoric acid esters, sulfonic acid derivatives, etc. contain.

Lure and bait substances can also be incorporated. Furthermore, the new agents can also contain active ingredients which have bactericidal, fungicidal or nematicidal properties, thereby broadening the biological effectiveness of the means according to the invention achieved; will.

The use concentrations of the active ingredients of the formula I are between 0.01 and 1% by weight, preferably between 0.01 and 0.5% by weight. The application rates are essentially of

009841/1904

BATH ORIGINAL

the object to be treated, for example for the field, For horticulture and fruit growing, the quantities are between 0.5 and 3 kg of active ingredient per ha, for soil treatment between 2 and 10 kg of active ingredient per ha.

As can be seen from the experiments described below, when the new means are used, the development processes are both inhibited by insects as well as arachnids. The larval development of hatched animals can either be inhibited or prevented or adult animals are no longer reproductive or viable. With treated vibes, e.g. the Akarinae comes normal oviposition · the hatching rate of larvae from these eggs is either zero or greatly reduced.

Experiments with larvae of Aedes aegypti (mosquito)

The active ingredient is pre-dissolved in a little acetone and the solution

3 is made up to 150 cm with stale tap water. These The solution is poured into 1 liter beakers and charged with 20 freshly hatched larvae of Aedes aegypti per glass. As feed Serves dog biscuits grated in water. The duration of the experiment is 12 days. In the daily check, the behavior becomes of the living larvae and the number of dead larvae are determined. To determine the number of hatched mosquitoes, the cup is used with Copper gases covered. Table I below shows the number of dead larvae in percent after 12 days at various concentrations of active ingredient compiled.

Table I.

links

X killed animals at an active ingredient concentration of

0.05%

0.01%

0.005%

l-phenyl-3-methyl-3-hydroxy-triazene 100% 1- (2'-methyl-5'-chloro-phenyl) -3-isopropyl-3-hydroxy-triazene 100%

l- (2'-methyl-5 ^1- chlorophenyl) -3-hydroxy-3-ynethyl-triazene 100%

1- (4'-chloro-phenyl) -3-hydroxy-3-ethyl-triazene 100%

009841/1904

100%

100%

40%

100%

100%

75%

100%

links % discounted
Act
0.05% killed animal
ffconcentra
0.01% I.
e at a ι
tion of
0.005% l- (3 ', 4 ^l -dichlorophenyl) -3-ethyl-3-
hydroxy triazene 100% 100% 100% 1- (4'-chlorophenyl) -3-methyl-3-
hydroxy triazene 100% - - 1- (4 * -chlorophenyl) -3-isopropyl-3-
hydroxy triazene 100% - - 1- (2 ¹ , 4'-dichlorophenyl) -3-isopropyl-
3-hydroxy-triazene 100% 50% - 1- (2 ¹ -methyl-4 ¹ -chlorophenyl) -3-
methyl-3-hydroxy-triazene 100% 25% - l- (2 ', 4'-dichlorophenyl) -3-hydroxy-
3-methyl-triazene 100% 100% 95% 1- (3 ', 4'-dichlorophenyl) -3-hydroxy-
3-methyl-triazene 100% 100% - 1- (2'-methyl-4 ^1- chlorophenyl) -3-
hydroxy-3-isopropyl triazene 100% 80% - 1- (4'-propargyloxyphenyl) -3-
hydroxy-3-methyl-triazene 100% 30% 1- (4 ^1- propargyloxy-phenyl) -3-
hydroxy-3-isopropyl triazene 100% 90% - methyl-triazene (US patent
3,162,571) Q " 0 0

Experiments with Musca domestica (housefly)

An acetone solution of the active ingredient is mixed with 50 g of flyworm substrate (bran, alfa mixture, 10% yeast suspension). After the acetone has been completely removed, 25 freshly hatched fly maggots are placed on this substrate. The animals are kept at 25 ^C and 65% relative humidity. The flies that have hatched are paid for 12 days after the start of the experiment. The mortality of the larvae is given in percent in Table II below.

009841/1904

Table II

links % killed
jarven at
the active substance-
concentration
O, 057o 1-phenyl-3-methyl-3-hydroxy-triazene 787o 1- (2'-methyl-5'-chlorophenyl) -3-hydroxy-3-methy1-
triazene 987o 1- (4'-chloro-phenyl) -3-hydroxy-3-ethyl-triazene 1007o 1- (3 ', 4'-dichlorophenyl) -3-ethyl-3-hydroxy-triazene 147. 1- (4'-Chlorophenyl) -3-methyl-3-hydroxy-triazene 707o 1- (4 ¹ -chlorophenyl) -S-isopropyl-S-hydroxy-triazene 100% l- (2'-methyl-4 ^1- chlorophenyl) -3-methyl-3-hydroxy-
triazene 647o 1- (2 ', 4'-dichloro-phenyl) -S-hydroxy-S-methyl-triazene 527o 1 - (3 ', 4'-dichloropheny]) - 3-hydroxy-3-methyl-triazene 807o 1- (2'-methyl-4 ¹ -chlorophenyl) -S-hydroxy-S-isopropyl-
triazene 747o l- (4'-propargyloxyphenyl) -3-hydroxy-3-methyl-
triazene 927o l- (4'-propargyloxyphenyl) -3-hydroxy-3-isopropyl-
triazene 867o

Effect on ticks (Boophilus microplus) and their stages of development

For the following experiment, 10 adult ticks from different strains mature to lay (Table III, 1st column) were immersed for 3 minutes in an aqueous emulsion of 1- (4'-chlorophenyl) -3-hydroxy-. 3-ethyl-triazene (for concentrations see 2nd column) submerged. The composition of the emulsion can be found under the following work-up forms. Then, the ticks at 27 ° C and 8O7 are re- _r

009841/1904

lative humidity kept. The eggs are laid on the 5th, 10th and 15th day determined using the oviposition of the control experiment as a reference. (Data in 3rd column). The eggs are under equal Conditions held for another 20 days. The hatching rate, based on that of the control (data in 4th column), is then determined.

Table III

Boophilus Active ingredient Egg laying Hatch rate Tick strains concentration normal in % Yeerongpilly 0.05 normal 0 Hanrahan 0.05 normal 0 Las Guerisas I 0.05 normal 0 Biarra 0.05 normal 0 control untreated 100

Experiments with larvae of Leptinotarsa decemlineata (Colorado beetle)

Potato plants 20 cm high are treated with a 0.025% strength Active ingredient solution (water: acetone = 1: 1) treated and after drying of the spray coating occupied with 20 larvae in the 3rd molting stage. The larvae are treated daily to fresh, similarly Potato plants moved, with the number of dead animals being determined at the same time.

Table IV

link 2 3 number 5 Dead 7th Larvae after X 9 10 11th 12th Days total 0 0 4th 0 6th 1 8th 4th 1 4th 4th 13th 19th 1- (4'-chlorophenyl) -3-
hydroxy-3-ethyl
triazene 0
Q ( 0 0 0
/1 0 C)
4th 3 0 0 0 0 2 0 1- (4'-chlorophenyl) -3,3-
dimethyl triazene fCollec
tion Czech.Chem. Commun.
30, Mon. 11, 3956-61
(1965)] 0
41 0
90 0 0

Try different stages of development of Musea domestica (Housefly)

1 kg of fermented larval substrate, consisting of bran, alfa flour and yeast, is mixed with 50 ml of a 1.5% active ingredient solution and, after the acetone has evaporated, placed in a large breeding cage. Furthermore, fly food consisting of sugar, milk and egg powder is placed in this cage. The cage is then populated with 25 4-day-old male and female fly and the larval substrate with 20 1-day, 20 2-day and 20 3-day fly maggots. The flies lay the eggs in the larval substrate. The culture is kept at 30 ^° C. for 4 days; Under these conditions and during this period of time, the newly laid eggs developed up to the pupal stage, and pupation of the added larvae occurred correspondingly earlier.

The pupae are then isolated from the larval substrate by flushing out and placed in a fly cage for determination of the hatching rate Spread out on damp filter paper. This determination is made 12 days after the start of the experiment at a point in time when it is out more than 50% of the pupae in the control experiment had hatched adults.

The following table shows the number of pupae obtained, the adults hatched from them and the percentage mortality, based on the control.

approach n-dolls n-flies
12 days
according to ver
search start % Mortality be
moved on n-
Flying the Kon
troll l- (4'-chloro-phenyl) -3-
hydroxy-3-ethyl-triazene
control 36
1520 3
350 99.7%

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Effect on arachnids: a)

Ovicidal effect on eggs of the red spider mite (Tetranychus urticae)

To test the ovicidal effect, bean leaves covered with spider mite eggs are coated with aqueous emulsions of the test Treated active ingredients. The emulsions are made from a 10 70igen emulsifiable Concentrate (see under preparation forms).

The eggs of phosphoric ester-resistant spider mites were used for the experiments. The following table shows the concentration of the active substance and the percent hatch rate after 7 days. In the control experiment, the hatching rate was 1007o. .

Table VI

Active ingredient Conc
tration
in % Hatch rate
in% after 7
Days l- (4'-chlorophenyl) -3-hydroxy-3-ethyl-
triazene 0.1
0.05 0
5

Effect on the development cycle of spider mites (Tetranychus urticae)

With 10 female spider mites (A) and 10 deutonymphs (B) each occupied bean leaves are coated with a watery active ingredient emulsion, obtained from a 10% emulsifiable concentrate (see work-up trays), sprayed. To determine the number of A and B eggs laid daily are the animals from the 3rd day after Test start daily on fresh, treated with the same emulsion Bean leaves implemented. The eggs are counted daily and placed on the leaves at 24 ° C and 50 to 60% relative humidity held. The hatching rate is determined after 8 days.

In Table VII is 1. the active ingredient concentration, 2. the Number of treated females (A) and from treated deutonymphs emerged females (B) deposited per day and animal

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BATH ORIGINAL

Eggs and 3. the hatching rate from these eggs as a percentage.

Table VII

Conc Number of per B. Slip B. Active ingredient tration Day and woman rate in % 11 X. 1. KV tJ l » \ J Λ- J- chen deposited 32 16 ten eggs A. 21 A. 11th 1- (4 ¹ -chlorophenyl) -3-hydroxy- 0.1 3-ethyl-triazene 19th 17th 1- (4'-chlorophenyl) -3-hydroxy- 0.1 3-isopropyl-triazene 12th 9

The agents according to the invention are produced in and of themselves known way by intimate mixing and grinding of active ingredients of the general formula I with suitable carriers, optionally with the addition of dispersion materials which are inert towards the active ingredients or solvents. The active ingredients can be used as dusts, scattering agents, granules (such as coating granules, impregnation granules and homogeneous granules), wettable powders, pastes, digestible concentrates, solutions or aerosols are present and used will.

For the production of dusts, grit and granulates the active ingredients are mixed with solid carriers. Carriers can include e.g. kaolin, talc, bolus, loess, chalk, limestone, Lime grit, ataclay, dolomite, diatonic earth, precipitated silica, Alkaline earth silicates, sodium and potassium aluminum silicates (feldspars and mica), calcium and magnesium sulfates, magnesium oxide, ground plastics, fertilizers such as ammonium phosphates, ammonium nitrate, urea, ground vegetable products such as cereal flour, Tree bark flour, wood flour, nutshell flour, cellulose powder, residues from plant extractions, activated charcoal, etc., each can be used alone or as mixtures with one another.

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BATH ORIGINAL

The grain size of the carrier substances is for dust practical up to approx. 0.1 mm, for grit approx. 0.075 to 0.2 mm and for granules 0.2 mm or more.

The active ingredient concentrates in the solid preparation forms are usually 0.5 to 80? _o .

These mixtures can also contain additives stabilizing the active substance and / or nonionic, anionic and cationic active substances Substances are added that, for example, improve the adhesive strength of the active ingredients on plants and parts of plants (adhesive and Adhesives) and / or ensure better wettability (wetting agents) and dispersibility (dispersants). As an adhesive For example, the following are possible: olein-lime mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), Hydroxyäthylglykoläther of mono- and dialkylphenols with 5 to Aethylenoxydresten per molecule and 8 to 9 carbon atoms in the Alkyl radical, lignosulfonic acids, their alkali and alkaline earth salts, Polyethylene glycol ether (Carbowaxe), fatty alcohol polyethylene glycol ether with 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol part, condensation products of ethylene oxide / propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea-formaldehyde and latex products.

Active ingredient concentrates dispersible in water, i.e. wettable powders (wettable powder), pastes and emulsifiable concentrates Represent means that can be diluted with water to any desired concentration. They consist of active ingredient, carrier, optionally additives stabilizing the active ingredient, surface-active Substances and antifoam agents and optionally solvents. The active ingredient concentration in these agents is 5 to 80%.

The wettable powders and pastes are obtained by mixing the active ingredients with dispersants and in powder form Carriers mixed and ground in suitable devices until homogeneous. Examples of carrier materials are those mentioned above for the solid preparation forms in question. In some cases it is advantageous to use mixtures of different carriers. As dispersants, both

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BATH ORIGINAL

For example, the following are used: condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, and alkali metal, ammonium and alkaline earth metal salts of ligninsulfonic acid, further alkylarylsulfonates, such as alkali metal sulfonates, alkali metal sulfonates and alkaline earth metal salts sulfated hexadecanols, heptadecanols, octadecanols and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salt of oleoyl methyl tauride, ditertiary acetylene glycols, dialkyldilauryl ammonium chloride and fatty acid alkali metal and alkaline earth metal chloride.

Silicones can be used as antifoam agents.

The active ingredients are made with the additives listed above so mixed, ground, sifted and that happens with the wettable powders the solid part has a grain size of 0.02 to 0.04 mm and does not exceed 0.003 mm for the pastes. For the production of emulsifiable concentrates and pastes, dispersants, as listed in the previous sections, organic solvents and water used. Come as a solvent for example the following are possible: alcohols, benzene, xylenes, toluene, dimethyl sulfoxide and in the range from 120 to 350.degree boiling mineral oil fractions. The solvents must be practically odorless, non-phytotoxic, inert to the active ingredients and must not be easily flammable.

The agents according to the invention can also be used in the form of solutions be applied. For this purpose, the active ingredient or several active ingredients of the general formula I are used in suitable organic Solvents, solvent mixtures or water. Aliphatic and aromatic solvents can be used as organic solvents Hydrocarbons, their chlorinated derivatives, alkylnaphthalenes, can be used alone or as a mixture with one another. The solutions should contain the active ingredients in a concentration range of 1 to 20% included.

The agents according to the invention described can be Mix in other biocidal active substances or agents. In addition to the compounds mentioned above, the new agents can also be used for the general

009841/1904

Formula I contain e.g. insecticides, fungicides, bactericides, fungistatic agents, bacteriostatic agents or nematocides to broaden the spectrum of activity. The agents according to the invention can also still contain plant fertilizers, trace elements, etc.

The following embodiments of agents according to the invention serve to illustrate the present invention; Unless otherwise expressly noted, "parts" mean parts by weight.

009841/1904

Dust

For the production of a) 10% and b) 5% dusting agent the following substances are used:

a) 10 parts of 1- (A'-chlorophenyl) -S-hydroxy-S-ethyl-triazene

5 parts of highly disperse silica, 85 parts of talc;

b) 5 parts of 1-phenyl-3-hydroxy-3-methyl-triazene, 1.2 parts of spindle oil

AO parts of carbonate of lime
53.8 parts of talc.

The active ingredients are mixed and ground with the carrier substances. The dusts obtained are used, for example, to combat used by cockroaches and ants, etc. in the house, but also for plant protection.

Wettable powder

To produce a) and b) 50%, c) 25% and d) The following ingredients are used for 10 70 wettable powders:

a) 50 parts of 1- (A ¹ -chlorophenyl) -S-hydroxy-S-ethyl-triazene

5 parts naphthalene sulfonic acid-benzenesulfonic acid-formaldehyde-

hyd condensate
5 parts of sodium dibutylnaphthylsulfonate

5 parts of champagne chalk
20 parts of silica

15 parts of kaolin;

b) 50 parts of 1- (2'-methyl-5 '-chlorphenyl) ^ -hydroxy ^ -isopropyl

triazene
5 parts of sodium dibutylnaphthylsulfonate

10 parts calcium lignosulfonate
1 part: Champagne-chalk-hydroxyethyl cellulose mixture

(1: 1)

20 parts of silica
IA parts of kaolin;

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c) 25 parts of 1- (2'-methyl-5'-chlorophenyl) -3 ~ hydroxy-3-methyl-

triazene
5 parts of lignosulfonic acid calcium salt

2 parts of sodium dibutylnaphthylsulfonate 68 parts of kaolin;

d) 10 parts of 1- (4'-chlorophenyl) -3-hydroxy-3-ethyl-triazene

3 parts mixture of the sodium salts of saturated Fettal

alcohol sulfates

5 parts of naphthalene sulfonic acid-formaldehyde condensate 82 parts of kaolin;

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on mills and rollers. You get wettable powders, which can be mixed with water to form suspensions allow to dilute the desired concentration. Such suspensions are mainly used in crop protection to control eaters and sucking insect use.

The following substances are used to produce a 40% paste used:

40 parts of 1- (4'-chlorophenyl) -3-hydroxy-3-ethyl-triazene

5 parts of lignosulfonic acid calcium salt 10 parts of ethylene glycol

0.5 parts of carboxymethyl cellulose, 44.5 parts of water.

The active ingredient is mixed with the additives in a suitable way Devices intimately mixed and ground. A paste is obtained from which, by diluting with water, suspensions of any desired Let concentration be established. These suspensions are suitable for combating insects in crop protection,

Emulsifiable concentrate

For the production of 10 70 emulsifiable concentrates will:

009841/1904

a) 10 parts of 1- (4 * -chlorophenyl) -3-hydroxy-3-ethyl-triazene 55 parts of xylene

32 parts of dimethylformamide

3 parts of a combination emulsifier (alkylaryl-polyethylene glycol-alkylarylsulfonate-calcium salt, or

b) 10 parts of l- (3 ', A ¹ -dichlorophenyl) -3-ethyl-3-hydroxy-triazene 54 parts of methylcellosolve - polyethylene glycol 30 parts of a mixture of aromatic hydrocarbons with a

Boiling range 180 to 220 °

6 parts of a combination emulsifier (alkylaryl polyethylene glycol-alkylarylsulfonate-calcium salt)

mixed together. These concentrates can be mixed with water to form emulsions be diluted to concentrations suitable for plant and stored product protection.

Sprays

For the production of a) 2 70% and b) 5% spray will:

a) 2 parts of 1- (4'-chlorophenyl) -3-methyl-3-hydroxy-triazene 10 parts of xylene

88 parts petrol;

b) 5 parts of 1- (4'-chlorophenyl) -3-isopropyl-3-hydroxy-tria2ene 95 parts of ethyl cellosolve

mixed together. The solutions are sprayed with pressure syringes, and are especially used to combat flies and mosquitoes in apartments, warehouses and slaughterhouses.

009841/1904

ORIGINAL INSPECTEO

Claims (2)

Claims in the R | Hydrogen, halogen, nitro, a lower alkyl radical, a lower alkyl or alkynyl radical bonded to the core via oxygen or sulfur, a haloalkyl radical, an alkanoyloxy or alkanoylamino radical, the phenyl radical or a halogenated phenyl radical, Rn and R3 independently of one another are hydrogen, halogen, a lower alkyl or haloalkyl radical, one via oxygen or sulfur bonded to the core lower alkyl radical, and R / an alkyl radical with 1 to 8 carbon atoms, an alkenyl radical with 3 or 4 carbon atoms, the benzyl radical, denote a halogenated benzyl radical, a haloalkyl radical, the phenyl radical or a halogenated phenyl radical, contains together with distribution agents and / or carriers. 2. Means 'happy' ss claim 1, characterized in that it contains a triazene of formula I as active ingredient ^H | 2 ^ 0H (D In the R | Hydrogen, halogen, the methyl or ethyl radical, the Methoxy, propargyloxy, trifluoromethyl, the chloromethyl radical, the acetyloxy or acetylamino radical, or the phenylresc, 009841/1904 R «and Rq independently of one another are hydrogen, halogen, the methyl or methylchio radical, and R is an alkyl radical with 1 to 8 carbon atoms, the allyl radical, the phenyl radical, the benzyl radical or the chloroethyl radical . their stages of development, rf'T-mr-rirhna * the use of Active ingredients ili ι Γη «Η I I ill Λ11 in in Ii 1 or of means that 0098A1 / 1904 Pr / avt / 12/18/69 ORIGINAL INSPECTED