DE2514088A1 - Pesticidal substd. diamino-benzene derivs - prepd. by reacting alkyl 4-(2-aminophenyl)-3-Thio-allophanoates with halogenated aldehydes - Google Patents

Abstract

Diaminobenzene derivs. of formula (I): (where R1 is 1-5 C alkyl, R2 is H, halogen, 1-3C alkyl or halo-substd. 1-3C alkyl, and R3 is H, halogen, 1-4C alkyl or 1-4C alkoxy), e.g. 1-(1-hydroxy-2,2,2-trichloroethylamino)-2-(3-ethoxycarbonyl-2-thi- oureido)-benzene, are new cpds. (I) are plant-protection agents useful for combating fungal diseases and spider mites on crop plants. They are rapidly taken up by plants, and exert a long-lasting-systemic effect. They can be used both curatively and prophylactically against phytopathogenic fungi. When used in combination with other fungicides or with insecticides, herbicides, fertilizers or other plant protection agents, (I) can give rise to desirable synergistic and stimulant effects.

Description

New compounds of diaminobenzene The invention relates to new compounds of 1,2-diaminobenzene having the formula where R1 is an alkyl group with 1 - 5 carbon atoms, R2 is rasserstoft, halogen, an alkyl or halogen-substituted alkyl group with 1 - 3 carbon atoms, R3 is hydrogen, halogen, an alkyl or alkoxy group with 1 - 4 carbon atoms, their production and their use as crop protection agents, in particular for combating fungal diseases and spider mites on cultivated plants.

The new compounds have been used as pesticides before known products have the advantage of being absorbed particularly quickly by the plants and the long, lasting "systemic" effectiveness, i.e. they are delivered through the roots and the leafy green is absorbed and passed on in the sap stream. This makes it possible diseases caused by pathogenic fungi, both preventive and curative to combat and also fresh shoot and leaf growth for a certain time Protect infestation. The same applies to combating spider mites through the new connections. Against these sucking pests are considered systemic acting agents in general compounds from the group of phosphoric acid and Thiophosphoric acid esters or esters of carbamic acid in use, over against those however, the compounds according to the invention have the advantage of insignificant toxicity to warm-blooded animals exhibit. The new compounds are also, particularly as fungicides, in combination with other known fungicides or with insecticides, herbicides, fertilizers or other crop protection agents can be used advantageously, with syne rgisie rende and stimulating effects can be observed.

The new compounds can be used in a known manner common solution, stretching, dispersing, wetting and adhesive agents as well as mineral or organic carriers for wettable powders, dusting agents, emulsion concentrates, Pastes, granules, aerosol sprays, etc. can be prepared.

Among the fungal diseases of economic importance associated with the described new compounds can be combated effectively and sustainably, include, for example, powdery mildew (Erysiphe graminis) in cereal crops, the parasitic stalk disease (Cercospo rella herpotrichoides), black-leggedness (Ophiobolus graminis) and the husk tan (Septoria nodorum), in vegetable cultivation of the Powdery mildew on cucumbers (Erysiphe cichoriacearum), apple scab (Venturia inaequalis = Fusicladium dentriticum), pear scab (Venturia pirina = Fusicladium pirinum), apple powdery mildew (Podosphaera leucotiicha) and the storage rot in pome fruit (Gloeosporium fructigenum), in growing ornamental plants outdoors and in greenhouses especially rose powdery mildew (Sphaerotheca pannosa) and powdery mildew (Erysiphacean).

The common one, for example, is one of the sensitive species of spider mite Spider mite (Tetranychus urticae = T. bimaculatus), the fruit tree spider mite (Panonychus ulmi) and linden spider mite (Tetranychus telarius). In fruit growing is the at the same time fungicidal and acaricidal effectiveness of a plant protection product in particular he wishes. In some cases the combination of the new compounds with already known fungicides, such as those from the group of the dithiocarbamates (Mancozeb, Maneb, Propineb) or the haloalkylthio derivatives of tetrahydrophthalimide and phthalimide (Captan, Captafol, Folpet) or the organotin compounds (Fentin acetate) may be beneficial.

Particularly suitable compounds have the formula with R1 = alkyl group with 1 to 5 carbon atoms and R3 = hydrogen, chlorine, methyl, methoxy, ethyl or ethoxy or with R1 = methyl or isopropyl or with R2 = - CHCl - CH3 The new compounds are produced by reacting compounds of the formula with aldehydes of the formula and hydrated forms, respectively.

Here, R1 denotes an alkyl group with 1 - 5 carbon atoms, R2 denotes hydrogen, Halogen, an alkyl or halogen-substituted alkyl group with 1-3 carbon atoms and R3 hydrogenJ halogen, an alkyl or alkoxy group with 1 - 4 carbon atoms.

The reaction can be carried out by direct implementation of the components, e.g. B.

done in the melt flow, or under dilution with a solvent. The aldehyde is expediently used in a smaller excess.

In most cases the reaction is exothermic.

The preparation of the compounds according to the invention and their use as a plant protection agent is based on the following examples, for example and explained in more detail.

Example 1 1 mole of N - (3-methoxycarbonyl-2-thioureido) -orthoaminobenzene (Melting point 185 OC is dissolved in 1.2 mol of anhydrous chloral with heating to 70 OC solved. The liquid mass solidifies after a few minutes. After about an hour If it remains at 70 ° C, it is cooled, chopped up, washed out with plenty of water> filtered, dried and crystallized the 1 - (1 -hydroxy- 2, 2,2-trichlor) - ethylamino- 2 - (3 -m ethoxycarbonyl-2-thioureideo) benzene from a petroleum ether benzene Mixture around.

Melting point of the colorless crystals 153 ° C. Yield of relatively pure Crude product 90-95% of theory.

Example 2 1 mole of powdered N- (3-ethoxycarbonyl-2-thioureido) orthoaminobenzene suspended in boiling petroleum spirit (boiling point 40-60 ° C), added dropwise Stir in 1 mol of anhydrous chloral within one hour and boil for 2 hours under reflux. After cooling, the almost pure 1- (1-hydroxy-2,2,2-trichloro) ethylamine-2- (3-ethoxycarbonyl-2-thioureido) benzene is sucked off existing precipitate and dries. Almost quantitative yield. Melting point of the light powder 124 - 125 C.

Example 3 1 mole of N- (3-isopropoxycarbonyl-2-thioureido) -orthoaminobenzene one dissolves in 20 times the amount by weight of chloroform, drips within one hour 1 mol of anhydrous chloral is added, refluxed for 2 hours, and the solvent is evaporated zm vacuum and the residue crystallized from n-hexane. The 1- (1-hydroxy-2,2,2-trichloro) ethylamino-2- (3-isopropoxycarbonyl-2-thioureido) benzene obtained melts at 128 ° C. Example 4 22.5 g of N- (3-methoxycarbonyl-2-thioureido) -orthoaminobenzene and 23.2 g of trichlorobutyraldehyde hydrate (butyrchloral hydrate) are mixed with addition of 20 ml of diethyl ether, gradually warmed to 70 ° C with evaporation of the ether, the melt that is initially formed solidifies again and lasts for 4 hours Temperature lets cool, crushed and washed with 50 ml of ether The yield is almost quantitative at 41 g. The resulting N- (3-methoxycarbonyl-2-thioureido) -N ' - (1-hydroxy-2, 2, 3 -trichlorobutyl) -diaminobenzene is quite pure and can, for example from diacetone alcohol be recrystallized. Melting point 177 C.

In an analogous manner, 3-alkoxycarbonyl-2-thioureido-orthoaminobenzenes can be reacted with other aliphatic aldehydes halogenated in α -position: R1 R3 aldehyde melting point 4a CH3 H dichloroacetaldehyde 135 OC 4b C2H5 H dichloroacetaldehyde 117 ° C 4c CH3 H tribromoacetaldehyde 4d C3117 (i) H tribromoacetaldehyde 97 ° C 4e CH3 K trichlorobutyraldehyde 177 ° C 4f C2H5 H trichlorotutyraldehyde 156 OC 3-alkoxycarbonyl-2-thioureido-orthoaminobenzenes substituted on the benzene ring are also in the manner listed at the beginning of the example with α-halogenated aldehydes to bring to reaction, which show the following, each obtained with 2,2-trichloroacetaldehyde reaction products: R1 R3 melting point 4g CH3 Cl 168 - 169 ° C 4h 02H5 C1 171 ° C R1 R3 melting point 4i CH3 OCH3 118 - 119 OC 4k CH3 OC H 119 - 120 OC 3 25 41 0 2H5 OC 2H5 123 4m CH3 CH3 158 ° C Example 5 A water-emulsifiable solution of the compound obtained according to Example 1 is prepared, consisting of 25% active ingredient, 15% of a nonionic emulsifier of the nonylphenol polyglycol ether type and 60% N-methylpyrrolidone as solvent. At an application rate and concentration that corresponds to 1 kg of active ingredient in 500 liters of water / hectare, one treats once infected with powdery mildew, summer wheat (variety "Kolibri") kept in mitschei pots in the greenhouse at 22 0 and 95% humidity in the stage of beginning shooting . The treated plants remain completely free of powdery mildew until the ears emerge, while the control plants show severe infestation after a few days, which leads to the death of most of the leaves.

Example 6 Provides by homogeneous grinding and mixing with talc a powder containing 35% by weight of the compound obtained in Example 2 here. Wheat grains that have been artificially treated with Fusarium culmorum (causative agent of a casserole disease) infected are treated in the usual way in a pickling drum with this Powder in an application rate of 200 g / 100 kg. The grains are placed in Mftscherlich vessels sown and also infected in the same way as a comparison series, but untreated wheat. At the emergence of the seeds one finds that from unpickled Wheat less than 50% of the plants emerge, of which again in the next 14 days about half of them die off due to the action of the Fusarium fungus. From the pickled Grains, on the other hand, emerge 95% and develop healthy plants. It seems that the young plants remain immune to fungal attack for several weeks, resulting in the systemic effectiveness of the remedy indicates and with the conventional means was previously unavailable.

Example 7 Winter wheat sown outdoors in September on several plots at the beginning of November with the causative agent of the strawberry disease, Cercosporella herpotrichoides, infected. Another artificial infection occurs in February. in June will be a Part of the infected parcels at the stage of shooting the grain with the after Example 1 obtained / XMittel in an application rate of 300 g of active ingredient and 500 l water / hectare sprayed. In July, when the wheat is in bloom, it is removed Samples from the trial plots and check the stalks for symptoms of Cercosporella infestation herpotrichoides. This shows that the control plots that were not sprayed show an infestation of 90 - 95%, the treated plots, however, only one those from 0 - 51o. The infected, untreated plots continue to be harvested to a storage of the grain of 75 - 85%, however with the treated plots only from 5 - 10%.

Example 8 Spring wheat of the variety "Janus" is in the beginning stage Blossom by spraying with a spore suspension of the pathogen causing brown spots of wheat (Septoria nodorum) artificially infected.

and prepared as in Example 5 A spray powder, consisting of 10% active substance according to Example 4h, 40% manganese-zinc-dithiocarbamate, 38% chalk, 10% calcium lignosulfonate and 2% sodium dodecylbenzenesulfonate will at an application rate of 3 kg / hectare in 500 1 water / hectare a) 6 days before the artificial Infection b) Sprayed onto the ears 8 days after the artificial infection.

When checking for symptoms of infestation at the time of yellow maturity, the result is following infestation picture: The untreated infected ears show an infestation of 70 - 95% of the ear surface. The infected and injected before infection Parcels show an infestation of 5 - 10%, whereby the discoloration by infestation only are very weak. The parcels sprayed after infection are 10 - 12% infested. The harvest gives the following yields: Not infected, untreated 44 dz / hectare infected, untreated 27 dz / hectare infected, treated before infection 42 quintals / hectare infected, treated after infection 40 quintals / hectare not infected, treats 49 dz / hectare.

The latter figure shows an unexpected stimulation of earnings.

Example 9 By homogeneously grinding 25 parts of the according to Example 4i produced compound, 63 parts of kaolin, 10 parts of calcium lignosulfonate and 2 parts of wetting agent of the sodium alkylnaphthalene sulfonate type are known in the art Make a wettable powder that can be suspended in water.

At an application rate of 300 g of active ingredient in 600 l of water / hectare will in the first half of June trial plots of winter barley (sowing in September of the previous year), which was sprayed in February with the pathogen of the strawberry disease (Cercosporella herpotrichoides) have been artificially infected. The plots remain Practically free of fungal attack until harvest, while those treated with no fungicides Storage damage to grain caused by strawberry disease in control areas show to an extent greater than 70%.

Example 10: Grown in the greenhouse and infected with rose powdery mildew (Sphaerotheca pannosa) are artificially infected polyantha hybrids at the time of the first Appearance of light-colored infestation coverings with an aqueous containing 0.1510 active substance Emulsion of the compound obtained according to Example 4g sprayed to runoff. The fungal growth is prevented by the spray, and the protective effect of the agent maintains several weeks ahead. The horticultural practice particularly welcomes that due to the possibility of liquid preparation in many organic solvents soluble compound which otherwise, ds h. with conventional means of a similar type of action on a spray powder basis, spray stains noted as an unpleasant side effect be avoided.

Example 11 Roses grown under glass (Polyantha Hybrid "Mother's Day"), those infected by spider mites (Tetranychus urticae) are sprayed dripping wet a 0.1% solution of the emulsion concentrate prepared according to Example 5. The adult spider mites are all killed within 5 to 8 hours. As a result of the systemic effect, the acaricidal effect lasts for at least 2 - 3 weeks, so that the pests that hatch from already existing eggs can still be found can be detected.

- patent claims -

Claims (9)

Claims 1. Compounds of 1,2-diaminobenzene with the formula where R1 is an alkyl group with 1-5 carbon atoms, R2 is hydrogen, halogen, an alkyl or halogen-substituted alkyl group with 1-3 carbon atoms, R3 is hydrogen, halogen, an alkyl or alkoxy group with 1-4 carbon atoms. 2. Compounds according to claim 1, having the formula where R1 is an alkyl group with 1-5 carbon atoms and R3 is hydrogen, chlorine, methyl, methoxy, ethyl or ethoxy. 3. A compound according to claim 1 having the formula where R1 is methyl or isopropyl. 4. A compound according to claim 1 having the formula where R2 is - CHCl - OH3. 3. Process for the preparation of compounds according to one or more of claims 1 to 4, characterized in that compounds of the general formula are used with aldehydes of the formula or hydrated forms thereof, in which R1 is an alkyl group with 1-5 C atoms, R2 is hydrogen, halogen, an alkyl or halogen-substituted alkyl group with 1-3 C atoms, R3 is hydrogen, halogen, an alkyl or alkoxy group with 1 - is 4 carbon atoms. 6. The method according to claim 5, d a d u r c h g e k e n n z e i c h n e t that the reaction is carried out at an elevated temperature. 7. Use of the compounds according to Claim 1, 2, 3 or 4 as crop protection agents. 8. Application of the compounds according to claim 1, 2> 3 or 4 for Combating fungal diseases on cultivated plants. 9. Use of the compounds according to Claim 1, 2, 3 or 4 for combating of spider mites on crops.