CS229644B2 - Herbicide - Google Patents

Description

The present invention relates to herbicidal compositions comprising esters of 2-phenylhydrazino-2-cyanoacrylic acid as active ingredients.

The 2'-phenylhydrazine-2-cyanoacrylic acid esters which contain an atom of chloro or a nitro group in the phenylocane are known from the literature (Farmaco Ed. Sci. 22 (1967), p. 58 $ str · 418) ·

These substances serve as intermediates, for example, for the diuretics prosynthase and antibacterial compounds. The herbicidal properties of these compounds are not known.

It has now been found that esters of 2'-phenylhydrazino-2-cyanoacrylic acid of general formula I

wherein R 1 is chlorine or bromine, 229 844 o R is chloro, bromo or iodo, R 1 is hydrogen, chloro or bromo, and 4 R is an alkyl group having 1 to 3 carbon atoms, have a surprisingly strong and selective herbicide. The present invention provides a herbicidal composition comprising, as active ingredient, at least one 2 * -phenylhydrazino-2-cyano-acrylic acid ester of the general formula I as defined above, in common with a solid or liquid carrier.

The 2'-phenoylhydrazino-2-cyanoacrylic acid esters of the formula I are obtained, for example, by substituting the substituted phenylhydrazines of the formula II

wherein R, R and R are each as defined above,

they are reacted with ethers substituted 2-cyano-acrylic acids of the formula III

R 5 is CO 4 R 4 (III) wherein R 4 is as defined above and R 4 is C 1 -C 4 alkoxy or N, R 1 -cycloalkyl-C 1-6 -alkylamino or hydroxy. It is expedient to operate at gentle conditions at temperatures from -25 to 70 ° 0, preferably at room temperature (20 ° 0) ·

Suitable solvents are those in which both reactants are soluble or partially soluble, in particular alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethers such as tetrahydrofuran, dioxane or mixtures of these solvents.

The 2 ' -phenylhydroxy-2-cyanoacrylic acid esters of formula (I) crystallize mostly from the reaction solution in pure form and can be isolated by filtration and gentle drying (below 50 [deg.] C.).

The 2-cyanacrylic acid esters of formula III are used in at least a molar amount, based on the substituted phenylhydroxy of formula II, preferably in a stoichiometric amount. When arbitrary phenylhydrazines of formula II are used with their mineral acid salts, such as hydrochlorides or sulphates, then it is expedient to release the substituent the phenylhydrazine of formula II by adding an equivalent amount of an alkali metal alkoxide or alkali metal acetate and then performing the reaction.

The phenyl hydrazines of formula II used are known or can be prepared according to known methods (Methoden der Organ. Chemie, Houben-Weyl, Vol. 10/2, p. 180 et seq.). The 2-cyanoacrylic acid esters of formula III used are known or can be prepared according to known methods (BOS 2 635 841 Chem. Ber. (1964) 22, 3397). In the following examples, parts by weight have kilograms per liter by volume. Production of 2'-phenylhydrazino-2-cyanoacrylic acid esters of formula (I) Example 1 148.1 parts by weight of 2,4,6-trichlorophenylhydrazine are added to the solution. 108.5 parts by weight of ethoxymethylene-2-cyanoacetic acid methyl ester in 1000 parts by volume of methanol · 187.4 parts by weight of methyl ester 2 * were isolated from the solution by suction and drying in a vacuum oven at 40 ° C for 3 hours. M.p. 174 DEG-175 DEG C. (Compound No. 1) (- (2,4,6-trichlorophenyl) hydrazino-2-cyanoacrylic acid). 229 944

H, 2.52; N, 13.11. Found: C, 40.9; H, 2.8; N, 12.9. 2

A suspension of 21.4 parts by weight of 2,4-dichloro-phenylhydrazine hydrochloride in 150 parts by volume of methanol was neutralized by adding about 18 parts by weight of 30% sodium ethoxide solution and after adding 15.5 parts by weight of ethoxymethylene-2-cyanoacetic acid methyl ester to the reaction mixture was stirred for 3 hours at 25 ° C and then heated under reflux for 15 minutes. 17.5 parts by weight of methyl 2 '- (2,4-dichlorophenyl) hydrazino-2-cyanoacrylic acid are isolated from the filtrate after evaporation of the methanol in vacuo and recrystallization from ethanol (at 0 ° C). mp 154-156 ° C (Compound No. 2) ·

H, 14.1; H, 14.69; Found: C, 46.0; H, 3.2; N, 14.8. 229 844

Correspondingly, the following 2 * -phenylhydrazino-2-cyanoacrylic acid esters of general formula 1 are prepared: R1 R1 R3 R3Cl3 Cl2H4ClCl6-Cl5ClCl. 6-C1 6 CBj Cl H 7 'Br Br 6-Br 8 Cl Cl 5-C1 melting point (° C) ^ 2H5 175 C2H5 166 í-C3H7 130 C & j 140 ch3 182 0¾ 195

The use as herbicides is, for example, in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreads, granulates by spraying, coating, impregnating, fogging, dusting, 229 M4 sprinkling or watering. The application forms are entirely intended for use. These planks each have the finest possible dispersion of the new active ingredients in the process. · For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, there are ladleheads in medium to high temperature mineral oil, such as kerosene or diesel engine oil. oils, etc., as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, xylene, paraffin, tetrahydronaphthalie, alkylated naphthalenes or their derivatives, for example methanol, ethanol, propanol, butanol, chloroform, tetrachloroethane, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., heavy polar solvents such as dimethylformamide, dimethylsulfoxide, H-methylpyrrolidone, water, and the like.

Aqueous use forms can be prepared from emulsion concentrates, pastes or 6wettable powders, oil dispersions by adding water. The production of emulsions, pastes or oil dispersions as such or dissolved in an oil or 229 844 solvent can be homogenized in water with wetting agents, adhesives, dispersants or emulsifiers. Concentrates consisting of the active ingredient, a wetting agent, an adhesive, a dispersant or an emulsifier and, optionally, a solvent or an oil which are suitable for dilution with water may also be produced.

The herbicides contain, for example, 5 to 95% by weight of active ingredient, in particular 10 to 80% by weight of active ingredient. Surfactants include: ligninsulfonic acid salts, naphthalenesulfonic acids, alkali metal phenolsulfonic acids, alkaline earth metals or ammonium or ammonium salts, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, alkaline earth alkali metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, sulfated fatty alcohols, salts of fatty acids with alkali and alkaline earth metals, solisulfated hexadecanols, heptadecanols, octadecanols, salts of sulphated glycol ether of fatty alcohol, condensation products of sulphonated naphthalene and naphthalene-formaldehyde condensate, naphthalene or naphthalenesulphonic acid naphthalene and phenol condensation products and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenolpolygol ethers, tri-butylphenylpolyglycycles, alkylarylpolyetherkools, isotridecyl alcohol, condenser ethylene oxide products with fatty alcohols, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulphite waste liquors and methylcellulose ·

Powders, dusts and dusts can be produced by mixing or grinding together the active ingredients with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be produced by binding the active ingredients to solid carriers. Solid carriers are, for example, mineral clays such as silicas, silicates, talc, kaolin, lime, ore, grit, clay, dolomite. diatomaceous earth, calcium sulphate and magnesium sulphate, magnesium oxide, milled plastic materials, such as ammonium sulphate, ammonium phosphate, mm ammonium nitrate, urea and plant products, as a mobile qjouka, tree bark flour, wood flour and ground nut shells, powdered cellulose and others solid carriers · Examples illustrating the composition and preparation of compositions The Example and 90 parts of Compound No. 1 are mixed with 10 parts by weight of N-methyl-α-pyrrolidone to give a seroconcentrate suitable for application in the form of small droplets. EXAMPLE b 10 parts by weight of Compound No. 2 are dissolved in a mixture consisting of 90 parts by weight of oxylene, 6 parts by weight of the dispersion product of 8 to 10 moles of ethylene oxide with 1 mol of N-monoethanolamide, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil · Example c ** '* »- -. and. 229,844 20 parts by weight of Compound # 2 are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the addition product of 7 moles of ethylene oxide in 1 mol of octylphenol and 5 parts by weight of the adduct of 40 moles of ethylene oxide with & mole of castor oil · Example d 20 parts by weight of Compound No. 1 were dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction boiling 210 to 280 ° C and 10 parts by weight of 40 moles ethylene oxide 1 mol of castor oil. For example, 80 parts by weight of active ingredient No. 1 are mixed with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 10 parts by weight of ligninsulfonic acid sodium salt from sulphite waste 22SM4 are extracted with 7 parts by weight of silica gel and the mixture obtained is grind the hammer mill. 5 parts by weight of Compound No. 2 are mixed thoroughly with 95 parts by weight of finely dispersed kaolin. A dust containing 5% by weight of active ingredient is obtained in this way. is mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 3 parts by weight of paraffin oil which has not been sprayed on top of this silica gel. In this way, an effective agent is obtained with good adhesion. EXAMPLE h 229 844 40 parts by weight of active ingredient No. 2 are thoroughly mixed with 10 parts of the sodium salt of the phenolsulfonic acid, urea and formaldehyde condensation product, 2 parts of silica gel and 48 parts of water. This gives a stable aqueous dispersion. An aqueous dispersion is obtained by dilution with water. Example 1 20 parts of active ingredient No. 1 are intimately mixed with 12 parts of calcium salt of dodecylbenzenesulfonic acid, 3 parts of polyglycol ether of fatty alcohol, 2 parts of sodium condensation product of phenolsulfonic acid, urea and formaldehyde and 68 parts of paraffinic mineral oil · In this way a stable oil dispersion is obtained ·

The effect of various representatives of the novel 2 ' -phenylhydrazino-2-cyanoacrylic acid esters on the growth of the desired and undesired plants was monitored by the following greenhouse experiments: asm

300 ml plastic pots filled with clay sandy soil containing about 1.5% humus as substrate were used as culture vessels. Seeds of test plants were seeded by species on the soil surface. The pre-emergence treatment of the application of the active substances on the soil surface was carried out immediately. The active ingredients were suspended or emulsified in water as a dispersing medium and applied by spraying with finely dispersed ticks. In this method of application, an amount of active ingredient which corresponds to 3 kg / kg of active ingredient / ha was used. Shortly before or after the application of the compositions, the containers are gently irrigated to achieve plant germination and growth. The containers are then covered with a transparent platinum film and covered until the plants begin to grow. This covering causes the germinated plants to germinate evenly, if they have not yet been affected by the active ingredients.

For post-emergence treatment, the test plants are always grown to 3 to 10 cm depending on the growth form, and then treated with 229 844.

directly sown and planted in the same vein or planted with allogenic plants and transplanted into test vessels only a few days prior to treatment. It should be noted that the peat used in the post-emergence application trials was enriched in peat. The same is true for Galium aparine. The applied amount for the post-emergence treatment is 5 kg of active ingredient / ha for the new compounds No. 1 and 3> 0 kg / active substances for Compound No. 1 as well as for Compound No. 2 ·

In general, the postemergence treatment does not cover plastic foils. The experiments are carried out in a greenhouse, with the warmer parts of the greenhouse (at 20 to 35 ° C) being chosen for thermophilic species of plants and those parts of the greenhouse chosen for plants with a milder climate. in which the temperature is 15 to 20 ° C. Experiment time 2 to 4 weeks · During this time the plants are treated and their responses to individual treatments are evaluated. The evaluation is based on a scale from 0 to 100. In this context, 0 means no damage to or no normal damage occurs at I * 228 844 and at least 100 means at least plants where at least overground parts are destroyed · Results of greenhouse trials show that active substances Nos. 1 and 2 have a good herbicidal effect when applied at a rate of 3.0 kg of active ingredient / ha for pre-emergence and post-emergence applications. kg of active substance / coughing very good against a wide range of undesirable crops · Certain crop plants tolerate treatment with this active substance with minimal temporary damage ·

If crop plants are somewhat more sensitive to the active ingredients of the present invention, a method of application wherein the herbicidal compositions by the sprayers are maintained so that the leaves of the sensitive crops remain as intact as possible while the spray is directed to the leaves while the spray is directed to the leaves. With regard to the versatility of the application methods, the herbicides of the invention can still be used in a much larger number of crop plants to remove undesired plant growth. The application rates are between 0.1 and 15 kg / ha or more. To enhance the efficiency spectrum and to achieve synergistic effects, the novel compounds of the invention can be mixed with numerous representatives of other herbicidally active or regulator growth groups and then applied together. For example, diazines, 4H-3,1-bensoxazine derivatives, benzothiadiazinones, 2, 6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones can be used as such as diazines, , benzofuran derivatives, cyclohexane-1,3-dione derivatives and others.

In addition, it is useful to mix the novel compounds alone or in combination with other herbicide agents with other plant protection agents to apply the compositions together, for example, to control pests or phytopathogenic bacteria or bacteria. Furthermore, the miscibility of mineral salt roots, which are used to eliminate nutritional deficiencies or to remove trace element deficiencies, is of importance. Mighty non-phytotoxic oils and oil concentrates are added.

Table 1

List of names of the tested plants abutilon (Abutilon theophrasti) Amaranth (Amaranthus spp.) Blue Knapweed (Cent aura and cyanus) White Goosefoot (Chenopodium album) Carrot (Daucus carota) Stinking Bedstraw (Galium aparine) Wormworm (Ipomoea spp.) Deadnettle (Lamium purpureum) ) rice (Oryza sativa)

Sida spinosa White mustard (Sinapis alba) Solanum nigrum wheat (Triticum aestivum)

Table 2,229,944

Selective herbicidal action of Compound No. 1 (cf. Example 1) in post-emergence application in the greenhouse of the experimental plant% of damage using 0.5 kg of the active substance per hectare

Daucus carota 10

Oryza sativa 10

Triticum aestivum 3

AbutiIon theophrasti 100

Amaranthus spec · 71

Chenopodium album 100

Galium aparine 70 * Lamium purpure um 100

Sida spinosa 90

Solanum nigrum 100

Table 3,229,944

Herbicidal efficacy of compounds of general yeast

the addition of the active substance per hectare of BHB * lb. iáloi &amp; Wilil No. 2 2 F F i c c r 3 F 6-Article OHj fl ch3 tested dew fcliSy aPiFeeVtó% ^ SkoWeHistory Sinapis alba 3 iQ kg / ha ilbričwiiriy 1 100 '3 ii, 0 kg / ha iloučeniny δ . 80 80 ..i -—. . .... ia-a <· - <=. ίιι »- ^ γ · --jra“ - »rf '·' · '- - ..... ·, ...: - .., 3 =, 1, -.

Postemergence experiment: 229,644 test plants% damage at application 3.00 kg / ha of Compound # 1 of Compound # 2 Centaurea cyanus 100 80 Galiua aparine 90 90 Ipoaoea spec · 100 80

Claims (1)

IN THE INVENTION 229 644 A herbicidal composition characterized in that the active ingredient comprises at least one ester of 2'-phenylhydrazino-2-cyanoacetic acid of general formula I wherein R is chloro, bromo or iodo, is hydrogen, chloro or bromo, and R 1 is an alkyl group having 1 to 3 carbon atoms, together with a solid or liquid carrier. 12, Leninova 21, Olomouc Price: 2,40 Kčs