DE2145418A1 - Arylazo-thiocarbonic acid amide derivs - with acaricidal fungitoxic and bacteriotoxic props - Google Patents

Abstract

Title derivs. of formula (I) (where X is Cl, Br, CH3 or CF3, n is 0, 1, 2 or 3, and R and R' are 1-4C alkyl or NRR' is a 5- or 6-membered ring which can also contain O as a ring member) which are partic. useful for combatting rice disease, are prepd. by treating a cpd. of formula (II) with an oxidising agent at 5-100 degrees C.

Description

Arylazo-thiocarboxylic acid dialkylamides The present invention relates to new arylazothiocarboxylic acid dialkylamides, which have acaricidal and fungicidal properties own and a process for their preparation.

It is already known that various arylazo compounds have acaricidal properties such. B.

Arylazosulfide and arylazo-su] fone. These connections are satisfactory but not in their effect, mainly because they are practically exclusively on eggs and spider mite larvae are not effective against adult forms. Hence they can at best in a mixture with other acaricidally active compounds in practice can be used (Japanese Auslegeschrift 15618/63, Japanese Auslegeschrift 15645/65).

It has now been found that the new arylazo-thiocarboxylic acid dialkylamides of the formula (I) in which X stands for chlorine or bromine, a methyl or trifluoromethyl group, n stands for an integer from 0 to 5 and R and R 'stand for alkyl groups with up to 4 carbon atoms, where R and R' also together with the nitrogen atom one Can form 5- or 6-membered ring, which can also contain an oxygen atom as a ring member, have strong acaricidal and fungicidal properties.

The compounds according to the invention act in contrast to those mentioned above also against adult stages of spider mites, and also against a number of them phytopathogenic fungi.

The active ingredients according to the invention are therefore a valuable asset of technology.

It has been found that they can be prepared by oxidizing 1-aryl-4,4-dialkyl-thiosemicarbazides of the formula II with suitable oxidizing agents. In formula II, the symbols R, R ', X and n have the same meaning as in formula I.

The arylazo-thiocarboxylic acid dialkylamides according to the invention are through the aforementioned formula (I) is clearly defined.

In this formula, X preferably represents chlorine, n represents O, 1 or 2, R and R 'stand for alkyl with 1 to 4 carbon atoms. Furthermore, R and R 'stand together with the nitrogen atom for a preferably unsubstituted heterocyclic one A radical with 4 to 5 methylene groups, one of which can be replaced by oxygen. As examples of the substances that can be used according to the invention, the following may be mentioned in detail: Phenylazo-thiocarboxylic acid dimethylamide phenylazo-thiocarboxylic acid diethylamide phenylazo-thiocarboxylic acid dipropylamide Phenylazo-thiocarboxylic acid diisopropylamide Phenylazo-thiocarboxylic acid dibutylamide Phenylazo-thiocarboxylic acid diisobutylamide Phenylazo-thiocarboxylic acid di-sec. -butylamide Phenylazo-thiocarboxylic acid-N-methyl-N-butyl-amide Phenylazo-thiocarboxylic acid-pyrrolidide Phenylazo-thiocarboxylic acid piperidide Phenylazo-thiocarboxylic acid-morpholide 4-chloro-phenylazo-thiocarboxylic acid-dimethylamide 2-chloro-phenylazo-thiocarboxylic acid dimethylamide 3-chloro-phenylazo-thiocarboxylic acid dimethylamide 2,4-dichloro-phenylazo-thiocarboxylic acid dimethyl amide 3,4-dichloro-phenylazo-thiocarboxylic acid dimethylamide 2,3-dichloro-phenylazo-thiocarboxylic acid dimethylamide 2,3,6-trichloro-phenylazo-thiocarboxylic acid dimethylamide 2,4,6-Trichlorophenylazo-thiocarboxylic acid dimethylamide 4-Bromo-phenylazo-thiocarboxylic acid dimethylamide 4-methyl-phenylazo-thiocarboxylic acid dimethylamide 3-chloro-4-methyl-phenylazo-thiocarboxylic acid dimethylamide 3-Trifluoromethyl-phenylazo-thiocarboxylic acid-dimethylamide 4-Trifluoromethyl-phenylazo-thiocarboxylic acid-dimethylamide 3-chloro-4-trifluoromethyl-phenylazo-thiocarboxylic acid dimethylamide The preliminary products of the formula II are largely known (cf.

Belgian patent 735 562). As far as they are not yet in detail are described, they water completely analogous to the procedure specified there manufacture0 To carry out the oxidation of the 1-aryl-4,4-dialkyl-thiosemicarbazide (II) The compounds of the formula (1) according to the invention are various oxidizing agents useful, e.g.

Hydrogen peroxide, alkali or ammonium peroxodisulphates, mercury (II) oxide, Alkali chromates, chromium trioxide, ammoniacal silver oxide, iron (III) chloride, potassium hexacyanoferrate (III), Lead (TV) oxide, bloi (IV) acetate or quinones, among others. The reaction takes place in the organic or organic-aqueous medium, e.g. in alcohols, ketones, dioxane, Carboxylic acids (formic acid, acetic acid) or their mixtures with water or else in hydrocarbons, e.g. carbon tetrachloride, benzene and the like, or in a two-phase system from water and these solvents. The reaction temperature can be within wide limits vary. It is preferable to work in the temperature range from -5 to 100 ° C, e.g. at 20 to 70 ° C.

The reaction batches are worked up in the customary manner Evaporation of the solutions or precipitation of the reaction products with water.

The active ingredients according to the invention have a strong acaricidal effect, so that they are suitable for use as pesticides.

The mites (Acari) include the spider mites (Tetranychidae) like the bean (Tetranyhus telarius = Tetranychus althaeae or Tetratlychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = I'anonychus ulmi), gall mites, e.g. the currant mite (Eriophyes ribis) and tarsonemids, for example the shoot tip mite (llemitarsonemus la-tus) and cyclamen mite (Tarsonemus pallidus); and finally ticks such as the Lederzeoke (Ornithodorus moubata).

They also have deterrent properties against rodents, so that they are also used as a means of protecting organic materials against rodent damage can be.

The active ingredients according to the invention also have a strongly fungitoxic and bacteriotoxic effects. They damage crops in the control concentrations of fungi and bacteria are not necessary. For the-Ben reasons they are used as pesticides to combat fungi and Suitable for bacteria.

Fungitoxic agents in crop protection are used for control of Archimyoetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti.

The active ingredients according to the invention have a very broad spectrum of activity and can be used against parasitic fungi and bacteria that live above ground Affect plant parts or attack the plants from the ground, as well as seed-borne Pathogens The active ingredients according to the invention have above all in the Proven to combat rice diseases. So they showed an excellent effect against the fungi Piricularia'oryzae and Pellicularia sasakii, on the basis of which they can be used to combat these two diseases together. That means a substantial advance, since so far against these two Pile means different chemical constitution were required. Surprisingly show the active ingredients do not only have a protective effect, but also a curative and systemic effect.

The systemic WiikUlli against rice diseases can also be done by application the compounds of the invention for irrigation water can be achieved.

However, the compounds of the invention also act against others Fungi that attack rice or other crops, such as Cochliobolus miyabeanus, Mycosphaerella musicola, Cercospora personata, Botrytis cinerea, Alternaria species, Verticillium alboatrum, Phialophora cinerescens and Fusarium species, as well as against the bacterium Xanthomonas oryzae.

The active ingredients according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These are made in a known manner, e.g. B. by mixing the active ingredients liquefied liquids under pressure with extenders, i.e. liquid solvents Gases and / or solid carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants.

In the case of the use of water as an extender, z. Belly organic solvents can be used as auxiliary solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers such fluids meant which at normal Temperature and are gaseous under normal pressure. e.g.

Aerosol propellants such as halogenated hydrocarbons, e.g., freon; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite, or diatomaceous earth, and synthetic rock flour, such as finely divided silica, aluminum oxide and silicates; as emulsifier: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g., alkylaryl polyglycol ethers, alkyl sulfates, alkyl sulfates, and aryl sulfonates; as dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be mixed in the formulations with other known active ingredients.

The formulations generally contain between X, 1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90 9 '.

The active ingredients can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable Concentrates, emulsions, suspensions, wettable powders, pastes, soluble powders, dusts and granules can be used. It is used in the usual way, e.g. by spraying, atomizing, atomizing, dusting, scattering, smoking, gasifying, Pouring, pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can be vanilated in larger areas l @ general lie cle between 0.0001 and 10% * preferably between 0.01 and 1%.

The active ingredients can also be used with good results in the IJltra-Low-Volume-Procedure (ULV) used where possible, formulations up to 95% or even to apply the 100% active ingredient alone.

Example A: Tetranychus test / resistant solvent: 3 parts by weight DMF emulsifier: 1 part by weight of alkylaryl polyglycol ether Active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent that contains the specified amount of emulsifier and dilutes the Concentrate with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which have a height of about 10 to 30 cm, sprayed dripping wet. These bean plants are strong with all stages of development of the bean spider mite (Tetranychus urticae) infested.

After the times indicated, the effectiveness of the active ingredient preparation determined by counting the dead animals. The degree of destruction thus obtained becomes given in%.

100% means that all spider mites have been killed, 0% means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 1 below: Table 1 (plant-damaging mites) Tetranychus urticae / resistant Active ingredients Active ingredient concentration degree of destruction in tration in% 9/0 after 2 days i 5 C, H50 \, I P-0 - N02 0.1 65 C2H5 - (known) 5 0 CH3ONI? rt PS-CH2-C-NH-CH3 0.1 70 CHo / (known) 5 (CH3 2 0.1 100 S. Cl-O-N = NCN (CH3) 2 0.1 100 Example B: Piricularia and Pellicularia test Solvent: 1.9 parts by weight DMF dispersant: 0.1 part by weight alkyl aryl polyglycol ether water: 98 parts by weight water The amount of active ingredient required for the desired concentration of active ingredient in the spray liquid is mixed with the specified amount the solvent and the dispersant and dilute the concentrate with the specified amount of water.

The spray liquid is used to spray 2 x 30 approximately 2 - 4 weeks old Rice plants to dripping wet. The plants remain in one until they dry out Greenhouse at temperatures from 22 to 240C and a relative humidity of about 70 96. After that, one part of the plants is coated with an aqueous suspension from 100,000 to 200,000 spores / ml of Piricularia oryzae inoculated and in one Room set up at 24 to 260C and 100% relative humidity. The other Part of the plants is made with a culture of Pellicularia grown on malt agar sasakii and placed at 28 to 300C and 100 96 relative humidity.

5 to 8 days after the inoculation, the infestation is present in all the inoculation with Piricularia oryzae leaves as a percentage of the untreated, but also determined inoculated control plants. In those with Peliicularia sasakii infected plants, the infestation will occur on the leaf sheaths after the same time also determined in relation to the untreated but infected control. 0 9 'means no infestation, 100% means that the infestation is just as high as in the control plants.

Active ingredients, active ingredient concentrations and results are based on the following Table 2 shows.

Table 2 Piricularia (a) and Pellicularia (b) tests Infestation in 9 'of the infestation of the Active ingredient untreated control an active ingredient concentration (in 9 ') from a) 0.05 a) 0.025 b) 0.05 b) 0.025 CH2-NH-CS-S protectiv 25 100 100 ZN CH2-NH-CS-S curative 100 Known t'Ziheb " S protectiv 0 0 9 N = NCN (CH3) 2 curative 33 5 protectiv. 0 0 -N = NCN (C2Hg2 cur? Ativ 25 5 9N = NCN (C3H7) 2 protectiv 0 0 S. -N = NCN (CH) 2 protectiv 0 100 25 3 5 C1 protectiv 0 0 25 Example C: Mycelium growth test Nutrient medium used: 20 parts by weight of agar-agar 200 parts by weight of potato decoction 5 parts by weight of malt 15 parts by weight of dextrose 5 parts by weight of peptone 2 parts by weight of Na2HP04 0.3 parts by weight of Ca (NO3) 2 ratio of solvent mixture to nutrient medium: 2 parts by weight of solvent mixture 100 Part by weight of agar medium Composition of solvent mixture 0.19 part by weight of DMF 0.01 part by weight of emulsifier alkyl aryl polyglycol ether 1.80 part by weight of water 2. - parts by weight of solvent mixture The amount of active substance required for the desired concentration of active substance in the culture medium is mixed with the specified amount of the solvent mixture. The concentrate is mixed thoroughly with the liquid nutrient medium, cooled to 420C, in the specified proportions and poured into Petri dishes with a diameter of 9 cm. Furthermore, control plates are set up without adding any preparation.

If the culture medium is cold and solid, the plates are filled with the in inoculated and with the mushroom species indicated in the table about 21 0C incubated.

The evaluation is carried out after 4 to 10 days, depending on the rate of growth of the fungi. During the evaluation, the radial mycelial growth on the treated culture media is compared with the growth on the control culture media. The rating of the fungal growth is done with the following key figures: 0 no fungal growth 1 very strong growth inhibition 2 medium growth inhibition 3 weak growth inhibition 4 growth equal to the untreated control active ingredients, active ingredient concentrations and results are shown in Table 3 below: Table 3: Mycelium growth test fungi and bacteria aezbJo 0 0 II 1 seuonrroytx-e) l mnLrajJo r MI r mnyTxoaZo3 snrxaqedm IO r 1 I. snlnqoFlqo oD Oa) cd 0) cd H cdcd 4 ro mnr - Fcyxah 0) 0 0) 0 HP 0 0 0) +> cd 0 0) Active ingredients concentrate 0 cd H 0 H 1 H 0) 0) cd slooFsnm HN cd 0) H cd 0 0 o H 0 to 0 »H Cf» 10 t cd> 0) r u0 O><cdo T PLC BFJBlnoFllaa Zn known n I 3 1 4 4 4 4 strasasau I r I 0 roydos-Fy6 aezro o - / \ N = NC1N (CH3 2 0 - - 0 1 - 1 0 ll Fi h p 5 rna, A4 N: O zz O r F (F: or ç = 0 3 0 - - 1 - Cl cd F: 5 4) N F9 = 1 1 0 2 - 1 - cm s s NN n N aJ - ~ t C \ .l S tD M t æ II vvvv uz uz Q v ç v uz = v vg y Z z O x> = v ul, -v uz = v uz = u 11 w æ z | Z | ffi æ w II », z; z; Nz; 1 o cq ct 11 11 11 11 Æ> 3 x v Example 1: 25 g (0.22 mol) of 30% strength hydrogen peroxide are gradually added dropwise to a suspension of 39 g (0.2 mol) of 1-phenyl-4,4-dimethyl-thiosemicarbazide in 150 ml of glacial acetic acid, starting at room temperature. The temperature is kept below 30 ° C. by external cooling. After the addition is complete, the mixture is stirred for a further 2 hours at 30 ° C. and the reaction product is then precipitated by adding 500 ml of water. This is filtered off with suction, washed well with water and dried.

Yield: 28.6 g (74 9 'of theory) phenylazo-thiocarboxylic acid dimethylamide F: 740C (after recrystallization from white spirit). RRR 'F 0C C2H5 C2H5 C2H5 45-47 C3H7 C3H7 oil ONR '= NO 57-58 9 CH3 CH3 93-95 CH3 - CH3 93-95 Table (continued) RRR 'F (oc Cl o CH3 CH3 69-70 Clc 9 CH3 CH3 82-83

Claims (6)

Claims: 1) Arylazo-thiocarboxylic acid dialkylamides of the formula I, in which X stands for chlorine, bromine, a methyl or rifluoromethyl group, n stands for an integer from 0 to 3 and R and R 'stand for alkyl groups having 1 to 4 carbon atoms, where R and R' also together with the nitrogen atom 5- or 6 "membered ring, which can also contain an oxygen as a ring member. 2) Process for the preparation of arylazo-thiocarboxylic acid dialkylamides of the formula I according to Claim 1, characterized in that 1-aryl-4,4-dialkyl-thiosemicarbazides of the formula in which X, n, R and R 'have the meaning given above, is reacted with suitable oxidizing agents, optionally in the presence of solvents or diluents, at temperatures between 5 and 1000C. 3) Means for combating mites and phytopathogenic fungi, marked by a content of arylazothiocarboxylic acid dialkylamides of the formula I according to claim 1. 4) methods of combating mites and phytopathogenic fungi, characterized in that arylazo-thiocarboxylic acid dialkylamides of the formula I according to claim 1 act on mites and phytopathogenic fungi or their habitat leaves. 5) Use of arylazo-thiocarboxylic acid dialkylamides of the formula I according to claim 1 for combating mites and phytopathogenic fungi. 6) process for the preparation of an acaricidal and fungicidal agent, characterized in that arylazothiocarboxylic acid dialkylamides of the formula I. according to claim 1 mixed with extenders and / or surface-active agents.