DE4013734A1 - Herbicidal compsns. contg. 3-phenyl-pyridazine derivs. - active against mono- and dicotyledonous weeds in e.g. cereal, onion, tomato or peanut crops - Google Patents

Abstract

Herbicidal compsn. comprises at least one 3-phenyl-pyridazine deriv. of formula (I) or a salt of (I). R1, R2 = OH, halo, CN, NO2, amino (opt. substd. by 1-4C alkyl), 1-10C alkyl (opt. substd. by one or more OH, halo or CN), 1-10C alkoxy, 5-7C cycloalkyl, 5-7C cycloalkoxy, phenyl, phenoxy, 1-4C alkylthio or 1-4C alkylsulphonyl; n,m = 0-3; m+n = 1-5; R3 = OH, OCOZR4 or OCONR4R5; R4,R5 = 1-5C opt. unsatd. alkyl (opt. more substd. by phenyl), phenyl or 5-7C cycloalkyl; Z = O, S or a bond; X = halo. USE - The compsns. are useful against mono- and dicotyledonous weeds, e.g. Arthemis arversis, lapsana communes, Setazia glauca or Stellaria medico, in grain, peanut, tomato or onion crops.

Description

The invention relates to a herbicidal composition comprising at least a substituted phenylpyridazine derivative.

Herbicidally active 3-arylpyridazines are known from JP-A 84/2 12 479, which in the 5-position on the pyridazine ring are an alkyl or dialkyl or have alkylalkoxy or dialkylalkoxyamino groups.

JP-A 81/1 13 767 also contains substituted aryl-4 (O-acyl) -6-halogenopyridazines known with fungicidal activity.

It has now surprisingly been found that such Substituted phenylpyridazine derivatives described in JP-A 81/1 13 767 excellent herbicidal activity exhibit.

The invention accordingly relates to herbicidal compositions by the content of at least one compound of formula

in the R₁ and R₂ each independently of the other hydroxyl, halogen, cyano, nitro, amino, which may optionally be substituted by alkyl with 1-4 C atoms, straight-chain or branched alkyl with 1-10 C atoms, optionally by hydroxy , Halogen or cyano can be substituted one or more times, alkoxy with 1-10 C atoms, cycloalkyl with 5-7 C atoms, cycloalkoxy with 5-7 C atoms, phenyl, phenoxy, straight-chain or branched alkylthio or alkylsulfonyl with 1-4 carbon atoms mean
n and m each independently represent the numbers 0, 1, 2 or 3, where n + m denotes the numbers 1 to 5,
R₃ is the radicals hydroxy, -OC (O) ZR₄ or -OC (O) NR₄R₅, wherein
R₄ is a straight-chain or branched, saturated or unsaturated alkyl radical with 1-15 C atoms which can optionally be substituted by a phenyl radical or a phenyl radical or a cycloalkyl radical with 5-7 C atoms,
R₅ is a straight-chain or branched, saturated or unsaturated alkyl radical with 1-15 C atoms which can optionally be substituted by a phenyl radical or a phenyl radical or a cycloalkyl radical with 5-7 C atoms,
Z is a single bond, oxygen or sulfur and
X is halogen or their physiologically acceptable salts.

In formula I, R₁ and R₂ are independently hydroxy, a cyano group, a nitro group, an amino group, which are optionally substituted by alkyl with 1-4 carbon atoms can be, such as a methylamino, ethylamino, propylamino, Butylamino, a dimethylamino, diethylamino, methylethylamino residue or the like. or a halogen atom, for example a chlorine, bromine or fluorine atom. R₁ and R₂ can independently from each other a straight-chain or branched alkyl radical with 1-10 C atoms, for example a methyl, Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl radical or their branched analogs, such as an i-propyl, mean i-butyl, t-butyl or the like. These alkyl residues can be one or more times by hydroxy, cyano or halogen, for example chlorine, bromine or fluorine. Examples of such radicals are cyanoalkyl radicals, such as the cyanomethyl radical, Hydroxyalkyl radicals, such as the hydroxyethyl radical or Haloalkyl radicals, such as the chloromethyl radical, the bromomethyl radical or the trifluoromethyl radical. Furthermore, R₁ and R₂ can independently an alkoxy radical with 1-10 C atoms in the alkyl chain, for example a methoxy, an ethoxy, a Propoxy, a butoxy group and the like, or a cycloalkyl group with 5-7 carbon atoms, such as a cyclopentyl, cyclohexyl or Cycloheptyl radical, or a phenyl radical or a phenoxy radical mean. R₁ and R₂ can also each be an alkylthio group with 1-4 C atoms in the alkyl chain, such as a methylthio, Ethylthio, propylthio or butylthio, or one Alkylsulfonyl radical with 1-4 C atoms, for example one Methylsulfonylrest mean.  

n and m each represent the numbers 0, 1, 2 or 3, where n + m the numbers 1 to 5 means.

Preferred are those compounds in which R₁ and R₂ each a halogen atom, for example chlorine, bromine or fluorine and n + m the numbers 1 or 2 or an alkyl radical with 1-4 C atoms which may be replaced one or more times by halogen, is preferably substituted by chlorine or fluorine and n + m the numbers 1 or 2, or an alkoxy radical with 1-4 C atoms in the alkyl chain or a cyclohexyl radical.

Particularly preferred are those compounds in which R₁ and R₂ a halogen atom, for example chlorine or fluorine, where n + m 1 or 2, or a trifluoromethyl radical, where n + m is the number 1 is mean.

R₃ is hydroxy or the radical -OC (O) ZR₄, or the radical -OC (O) NR₄R₅, where R₄ is a straight-chain or branched one saturated or unsaturated alkyl radical with 1-15 C atoms, for example a methyl, ethyl, propyl or butyl, Pentyl, heptyl, decyl, dodecyl, pentadecyl, or their means branched analogs, optionally by a Phenyl radical can be substituted. Furthermore, R₄ can Phenyl radical or a cycloalkyl radical with 5-7 C atoms, mean, for example, the cyclohexyl radical. R₅ means one straight-chain or branched, saturated or unsaturated Alkyl radical with 1-15 C atoms, for example a methyl, Ethyl, propyl or butyl, pentyl, heptyl, decyl, dodecyl, Pentadecylrest, or their branched analogs, the may optionally be substituted by phenyl. Furthermore, R₅ can be a phenyl radical or a cycloalkyl radical with 5-7 C atoms mean, for example, the cyclohexyl radical. The R₄ and R₅ may be the same or different. Prefers are those compounds in which R₃ is the radical -OC (O) ZR₄ means, where R₄ and Z has the meaning given above. X represents halogen, preferably chlorine or bromine.

The compounds of formula I can be prepared in the  one

• a) a correspondingly substituted 3-phenyl-pyridazinone-6 of formula II in which R₁, R₂, n and m have the meaning given above and Y is hydrogen or chlorine with phosphorus oxyhalide and, if Y is hydrogen, additionally with phosphorus or PCl₃ or PCl₅ and a halogenating agent to give the corresponding dihalo compound of the formula III in which X has the meaning given above,
• b) if appropriate in the presence of a diluent and in the presence of a base, to give the corresponding 3-phenyl-4-hydroxy-6-halogenopyridazine of the formula IV, in which X has the meaning given above, whereupon one
• c) optionally this compound of the formula IV in the presence of an organic diluent and in the presence of a base, for example sodium hydroxide, potassium hydroxide, or triethylamine with a corresponding acid halide of the formula V or Va in which R₄, R₅ and Z have the meaning given above,
  to the compounds of formula I, in which R₃ is not hydroxy and not halogen, is implemented.

However, you can also in step a) of the corresponding 3-Aryl-6-halopyridazine compound.

If R₁ or R₂ is a nitro group, this can optionally also before carrying out reaction step c) by nitriding the corresponding 3-aryl-4-hydroxy-6-halogenopyridazine compound introduce. But it is also possible Already in step a) the correspondingly substituted pyridazinone-6 to use.

The substituted 3-phenylpyridazinones-6 required as starting compounds are known from the corresponding acetophenone by reaction with glyoxylic acid and Hydrazine or from the corresponding benzoylacrylic acid Reaction with a lower aliphatic alcohol in the presence a catalyst and subsequent reaction with hydrazine or from the corresponding benzoylacrylic acid by esterification with a lower aliphatic alcohol in the presence of a Esterification catalyst and subsequent implementation with Hydrazine or by implementing the appropriate Obtained benzoylacrylic acids with NH₃ and hydrazine.

The preparation of the compound of formula II in which Y Cl means, according to Weissberger A., Taylor E. C. (Hersg.), The Chemistry of Heterocyclic Compounds Vol. 28, p. 32 done. The conversion to the dihalogen compounds takes place in the presence of phosphorus oxyhalide and if Y is H, additionally by reacting with phosphorus or PCl₃ or PCl₅ and one Halogenating agent. The dihalogen compounds are then optionally in the presence of a Diluent, for example a dioxane / water mixture Tetrahydrofuran u. Like. And in the presence of a base for example an alkali hydroxide such as sodium hydroxide solution, potassium hydroxide solution implemented to the compounds of formula IV.  

The optional subsequent acylation step by reaction with an acid halide of the formula V or Va in the presence of an organic diluent, for example in aqueous acetone, toluene or benzene u. the like and in the presence of a base. Inorganic bases come as bases, for example sodium hydroxide, potassium hydroxide, or organic Bases, such as triethylamine in question.

The preparation of the amine salts of the hydroxy compounds Formula I in which R₃ = OH, conveniently takes place directly in a suitable formulation agent with the addition of a Wetting agent. So z. B. a 50% preparation of Triethylamine salt of the compound of formula I, R₁ = 4-Cl, R₃ = H, R₃ = OH, X = Cl, prepared by the hydroxy compound (Substance 1.3526 g, 0.0146 mol) in a glycerol (4.445 g) -Rapidnetzer-Linz (0.500 g) mixture and then suspended slow triethylamine (1.527 g, 0.01509 mol, 3.2% excess) dripped. Then it was gently warmed for 2 hours Temperature was brought from 40 ° C to 60 ° C.

The result was a homogeneous, 50% ready-to-use mixture of the triethylamine salt.

The agents according to the invention are suitable for combating dicotyledons but also monocotyledon weeds in crops such as Cereals, corn, peanuts, cabbages, chickpeas, tomatoes and onions.  

They are particularly suitable for combating
Amaranthus retoflexus
Anthemis arvensis
Centaurea arvensis
Chenopodium ficifolium
Echinochloa crus-galli
Galium aparine
Mercurialis annua
Lapsana communis
Panicum millaceum
Setaria glauca
Solanum americanum
Solanum nigrum
Stellaria media
in the cultures mentioned above.

The agents according to the invention can be formulated in the usual way be, for example as solutions, wettable powders, Emulsion concentrates, emulsions, suspensions, dispersions, Dusts, granules and the like Like. And then contain if necessary the usual formulation aids such as extenders, i.e. liquid solvents, solid or liquid carriers, optionally using surfactants, ie emulsifiers and / or dispersing and / or wetting agents, grinding aids, Halftmittel and the like. In the case of using water as Extenders can e.g. B. also organic solvents Auxiliary solvents can be used. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene and other alkyl benzenes or alkyl naphthalenes, chlorinated Aromatics or chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, cycloaliphatic 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, strong polar solvents such as dimethylformamide or dimethyl sulfoxide, as well as water.  

Wettable powders are evenly dispersible in water Preparations which, in addition to the or inert substances still wetting agents z. E.g .: polyoxethylated Alkylphenols, polyoxethylated oleyl or stearyl amines, Alkyl or alkylphenylosulfonates and dispersants e.g. B .: Na oleyl methyl tauride, lignin sulfonates, or Contain condensation products of aryl sulfonates with formaldehyde can.

Emulsifiable concentrates can be dissolved, for example of the active ingredient in an organic solvent with addition be produced by one or more emulsifiers. As Emulsifiers come, for example, non-ionic and ionogenic Surfactants, such as polyoxyethylene sorbitan tall oil esters, polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ether, Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and Arylalkyl sulfonates, as well as protein hydrolysis in question.

Dusts are finely ground by grinding the active ingredient distributed solid materials, such as natural rock flours, e.g. B .: Kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic products such as highly disperse Silicic acid, aluminum oxide and silicates.

Broken materials, for example, are suitable as carriers for granules or fractionated natural rocks like calcite, Marble, pumice, spialite, dolomite, and synthetic granules from inorganic or organic flours, as well as granules organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Adhesives and thickeners, such as carboxymethyl cellulose, methyl cellulose, natural and synthetic powdery, granular and latex-shaped Polymers are used, such as gum arabic, polyvinyl alcohol, Polyvinyl acetate.

Dyes, such as inorganic pigments, e.g. E.g .: iron oxide, Titanium oxide, terracyan blue and organic dyes, such as Alizarin, phthalocyanine dyes are used.  

The formulations generally contain between 0.1-95% by weight Active ingredient, preferably between 0.5 and 90 wt .-%.

The active ingredients as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, Powders and granules can be applied. The application happens in the usual way, for example by pouring, spraying, Spraying, dusting, scattering and. the like

With the external conditions such as temperature, humidity and. a. the required application rate of the inventive varies Means. It can move within wide limits and is generally between 0.2 and 10 kg / ha of active ingredients preferably 0.3-1.5 kg / ha.

example 1 Preparation of the starting compound 3- (4'-fluorophenyl) pyridazinone-6 a) From p-fluoroacetophenone with glyoxylic acid and hydrazine

4'-fluoroacetophenone (138.1 g, 1 mol) and glyoxylic acid monohydrate (27.5 g, 0.3 mol) were mixed and mixed for 1.75 hours at 105 ° C touched. Then it was cooled to 60 ° C, between water (500 ml) and inhibisol (400 ml), the pH of which aqueous phase was brought to pH 9 with NH₄OH solution. Then the separated layers were mutually alternate again Inhibisol (200 ml) or very dilute NH₄OH solution (pH 9, 400 ml) and the combined aqueous portions (pH approx. 8.5) with hydrazine hydrate (16.5 g), under 4 hours Boiled under reflux, concentrated (400 ml distillate), to 0 ° C cooled, the resulting crystals isolated, with water washed and dried to constant weight. It became 3- (4'-fluorophenyl) pyridazinone-6 (48.0 g, 0.2524 mol, 84.5% of theory) obtained with mp = 264-269 ° C. From a DMF-ethanol blend recrystallized the product had a mp. = 268-270 ° C.

b) From (4'-fluorobenzoyl) aryl acid

(4′-fluorobenzoyl) aryl acid (582 g, 2.998 mol with mp = 134-137 ° C) was dissolved in ethanol (3300 ml), p-toluenesulfonic acid (23 g) and sulfuric acid (conc. 4 ml) were added and the mixture then refluxed for 18 hours. The mineral acid was then by adding anhydrous sodium bicarbonate neutralized. It was then removed from the inorganic salts filtered, to the mechanically stirred solution of the esterification product a hydrazine solution (6 mol hydrazine, 700 ml water) added and the mixture at reflux temperature for 3 hours brought. A solid product separates that isolates, washed with water and moistened with diluted Hydrochloric acid (700 ml HCl conc., 1600 ml water) mixed and 2 hours was brought to reflux temperature. It was chilled the resulting solid product is isolated, washed with water and dried to constant weight. One got 3- (4′-  Fluorophenyl) pyridazinone-6 in the form of a yellowish solid product (390 g, 2.0508 mol, 68.4% of theory) with mp = 266-269 ° C.

By recrystallization from dioxane an almost colorless Obtain the product as it sublimes into broad crystals from approx. 170 ° C and melts at 269-270.5 ° C.

c) From (4′-fluorobenzoyl) alanine

3- (4'-fluorobenzoyl) acrylic acid (9.7 g, 0.04996 mol) were added in 50 ml of concentrated aqueous ammonia solution dissolved and the solution left open for a few days.

The mixture was initially neutralized by adding hydrochloric acid (conc., 30 ml), then another 20 ml of concentrated hydrochloric acid and then Hydrazine hydrochloride (4.1 g, 0.06 mol) was added, followed by the mixture was refluxed for 8 hours. After cooling the separated solid product was isolated with water washed and dried to constant weight. 3- (4'-Fluorophenyl) pyridazinone-6 was obtained with mp = 265-267 ° C, 8.9 g, 0.04680 mol. Corresponding to a 93.7% yield d. Th.

Example 2 (Vgg. No. 68) 3- (4'-fluorophenyl) -4,6-dichloropyridazine

3- (4'-fluorophenyl) pyridazinone-6 (190 g, 0.9991 mol) was with red phosphorus (40 g, 1.291 mol) was mixed, followed by 1300 ml Added phosphorus oxychloride. The suspension was then in Bring to 90 ° over an hour and then a medium one Blown chlorine stream into the solution. The temperature of the reaction mixture rose to 100 ° C and was at this temperature held. Chlorination was carried out for 4 hours, then the dissolved ones were distributed Gases by introducing a medium stream of nitrogen, distilled 800 ml of phosphorus oxychloride in a water jet vacuum and then decomposed on ice, the resulting acid neutralized with concentrated ammonia. It resulted 235.2 g (0.9676 mol) of 3- (4'-fluorophenyl) -4,6-dichloropyridazine in the form of a solid product, corresponding to a 96.9% Raw yield. The product shows recrystallized from ethanol and cyclohexane a melting point of 124-127 ° C.  

Example 3 (Vgg. No. 56) 3- (4'-fluorophenyl) -4-hydroxy-6-chloropyridazine

3- (4′-fluorophenyl) -4,6-dichloropyridazine (145.84 g, 0.600 mol) was dissolved in dioxane (800 ml) at 60 ° C, water (300) added and heated the solution to reflux. Within half Hour then sodium hydroxide solution (48 g NaOH solid, in 300 ml water dissolved) added dropwise and kept under reflux for a further 5 hours. Then the residue was brought to dryness in vacuo dissolved in hot water (5 l), of insoluble components filtered and adjusted to pH 1 with concentrated hydrochloric acid. The resulting solid was isolated, washed with water and for further cleaning in dilute ammonia (8 l water, pH 9-10) dissolved. Then, by carefully adding Hydrochloric acid small amounts of 3- (4′-fluorophenyl) -4-chloropyridazinone-6 selectively precipitated, separated (by filtration) and then the main amount is precipitated (up to pH 1). The received Solid product was isolated, washed with water and used for Weight constant dried. There were 91.0 g, 0.4051 mol 3- (4'-fluorophenyl) -4-hydroxy-6-chloropyridazine with mp = 254-260 ° C (Z.P.) obtained, corresponding to a 67.5% yield d. Th.

Example 4 (Vgg. No. 64) 3- (4'-fluorophenyl) -6-chloro-4- (octylthiocarbonyloxy) pyridazine

3- (4'-fluorophenyl) -4-hydroxy-6-chloropyridazine (22.5 g, 0.1 mol) were suspended in 80 ml acetone. Then the solution of 4 g (0.1 mol) of sodium hydroxide in 80 ml of water and the initially cloudy solution was heated to 60 ° C. For now clear Solution became octylthiochloroformic acid ester (20.97 g, 0.1 mol) all at once. The solution warmed up through the Reaction process and an emulsion formed. It was Maintained at reflux for 3/4 hours and the pH dropped to 6 set to 9 with 25% sodium hydroxide solution. The heavier organic layer of the resulting two-phase mixture  separated and freed from the volatile components in vacuo. The crude ester obtained (brown oil, 36.7 g, 95% crude yield) was purified on a silica gel column, the above compound in the form of a yellow oil (n = 1.5567, 30.4 g, 79% of theory Th.) Was obtained.

Example 5 (Vgg. No. 57) 3- (4'-fluorophenyl-4- (propylthiolcarbonyloxy) -6-chloropyridazine

3- (4'-fluorophenyl) -4-hydroxy-6-chloropyridazine (22.4 g, 0.1 mol) was suspended in benzene (2000 ml) by stirring, triethylamine (10.1 g, 0.1 mol) added and the mixture 3.5 hours stirred at room temperature. Then was Propylthiolchlorocarbonic acid ester (13.86 g, 0.09999 mol) added dropwise within 10 minutes. There was slight warming and the reaction mixture was without for a further 3 hours Heat input stirred. From the deposited triethylamine hydrochloride was filtered and the benzene phase with 2 100 ml portions of water, then very dilute hydrochloric acid, then very dilute sodium hydroxide solution and then again water washed. Then the organic phase was over sodium sulfate dried, fined with charcoal and the solvent in Vacuum, at the end in an oil pump vacuum at a bath temperature of 90 ° C sold completely. There remain 27.0 g (0.08263 mol) 3- (4'-fluorophenyl) -4- (propylthiolcarbonyloxy) -6-chloropyridazine in the form of a yellow oil, corresponding to an 82.9% Yield d. Th.  

Example 6 (Vgg. No. 143) 3- (4'-Bromophenyl) -4- (2,2-dimethylpropyloxycarbonyloxy) -6-chlorine pyridazine

3- (4'-bromophenyl) -4-hydroxy-6-chloropyridazine (obtained analogously Examples 1-3) (8.57 g, 0.03 mol) were in benzene (90 ml) suspended and triethylamine (3.19 g) added. It kicked a visible change in the solid. It was 30 minutes stirred and then a solution of 2,2-dimethylpropyl chloroformate (4.38 g, 0.0291 mol) in 20 ml of benzene in Dropped 30 minutes. The mixture warmed slightly. To 20 ml of water was added for 3 hours, vigorously for 5 minutes stirred and then the benzene phase separated over Dried sodium sulfate and the solvent in vacuo away. The remaining residue solidified and became recrystallized twice from diisopropyl ether. It was 3- (4′- Bromophenyl) -4- (2,2-dimethylpropyloxycarbonyloxy) -6-chloropyridazine in the form of colorless crystal prisms with mp = 113.5-115.5 ° C obtained (6.7 g, 0.01676 mol, 57.6% of theory).

Example 7 (Vgg. No. 19) 3- (4'-chlorophenyl) -4,6-dibromopyridazine

3- (4′-chlorophenyl) -4-hydroxy-6-chloropyridazine (compound 1, 24.1 g, 0.09997 mol) were placed in the reaction flask, one Solution of phosphorus oxybromide (85.8 g, 0.3 mol) in toluene (150 ml) added whereupon the reaction mixture at 1 hour Room temperature was stirred. Then 3 hours became heated slightly reflux, releasing hydrogen bromide gas has been. It was broken down on ice, making a batter Reaction product was obtained when rubbing with Petroleum ether froze. The product was still good with water washed, isolated and dried to constant weight. It 30.0 g (0.0861 mol, 86.1% of theory) of 3- (4'-chlorophenyl) -4,6-dibromopyridazine with mp = 160-162 ° C receive. Recrystallized from an ethanol-dioxane mixture (20 + 3) shows the sample mp = 163-165 ° C.  

Example 8 (Vgg. No. 16) 3- (4'-chlorophenyl) -4-hydroxy-6-bromopyridazine

3- (4'-chlorophenyl) -4,6-dibromopyridazine (52.2 g, 0.1498 mol) was dissolved hot in dioxane (300 ml) and under gentle reflux a solution of 12 g (0.3 mol) of sodium hydroxide solution in 50 ml of water within added dropwise of 10 minutes. It was another 4.5 hours kept under reflux, the dioxane evaporated in vacuo and the solid residue dissolved in 1 liter of hot water (95 ° C). With help Animal charcoal was hot filtered from a little solid product (tarry) and the hydrolysis product is precipitated with hydrochloric acid. The isolated The product (solid) became suction-moist in 1 l of water slurried whereupon the pH of the suspension at 65 ° C with ammonia was brought down to 9-10. Most of the product went into solution, the insoluble parts were isolated and treated again with ammonia. The combined filtrates were then acidified with hydrochloric acid, the resulting 3- (4′- Chlorphenyl) -4-hydroxy-6-bromopyridazine isolated, washed with water and dried to constant weight, 27.5 g, 0.09631 mol, 64.3% of theory Th., Mp = 262-264 ° C.

Example 9 (Vgg. No. 17) 3- (4'-Chlorophenyl) -4- (butylthiocarbonyloxy) -6-bromopyridazine

3- (4'-chlorophenyl) -4-hydroxy-6-bromopyridazine (14.2 g, 0.0497 mol) were suspended in 100 ml of benzene, triethylamine (5.5 g, 0.0543 mol) was added and the mixture to complete the Reaction stirred for 3.5 hours at room temperature. Then was S-butylthiochlorocarbonic acid ester (7.85 g, 0.05162 mol) within dropped into the mixture for 5 minutes and the reaction mixture stirred for a further 3 hours without the addition of heat. From the retired Triethylamine hydrochloride was filtered and the benzene solution in succession with 150 ml portions of water, very strongly diluted hydrochloric acid, very strongly diluted sodium hydroxide solution, then washed again water and dried over sodium sulfate. The solvent was then in vacuo towards the end completely removed in an oil pump vacuum (0.2 Torr, 90 ° C bath temperature).  The initially oily S-butylthiocarbonate of 3- (4'-chlorophenyl) -4-hydroxy-6-chloropyridazine, 17.5 g, 0.04356 mol, 87.6% of theory Th., Froze when standing for a long time and pointed redissolved from hexane mp = 68-71 ° C.

Example 10 3- (3'-Nitro-4'-chlorophenyl) -4-hydroxy-6-chloropyridazine (Vbg. No. 138)

3- (4'-chlorophenyl) -4-hydroxy-6-chloropyridazine (12 g, 0.04978 mol) was within 15 minutes at a temperature of 0-5 ° C entered in chilled highly concentrated nitric acid. The mixture was stirred at 0 ° C. for a further 30 minutes and then the reaction mixture stirred in ice water. The resulting yellow Solid product was isolated, washed with water and with NH₄OH / HCl fell over. After drying, 11 g, 0.0385 mol of 3- (3'-nitro-4'-chlorophenyl) -4-hydroxy-6-chloropyridazine with mp: Obtained 204-209 ° C, corresponding to a 77.25% raw yield. The sample was shown by TLC analysis (SiO₂ / 10% ethanol-chloroform) as largely uniform. Recrystallized from ethanol the compound melts at 208-211 ° C.

3- (3'-nitro-4'-chlorophenyl) -4-butylthiocarbonyloxy) -6-chloropyridazine- (Vgg. No. 88)

3- (3'-nitro-4-chlorophenyl) -4-hydroxy-6-chloropyridazine (14.3 g, 0.05 mol) were in benzene according to the usual method Butylthiochloroformic acid ester (7.88 g) with triethylamine (5.05 g) implemented as a hydrochloric acid binder. There were 3- (3'-nitro-4'- chlorphenyl) -4- (butylthiocarbonyloxy) -6-chloropyridazine in the form of a light brown oil. 17.0 g, 0.04226 mol, 84.55% of theory Th., N = 1.6073.  

Examples

Example 1

20 parts of compound No. 9 are melted and in liquid Condition with 20 parts of precipitated, ground silica, 50 parts of diatomaceous earth, 3 parts of the sodium salt of diisobutyl naphthalenesulfonic acid and 7 parts Na lignin sulfonate intimately mixed and ground in a planetary ball mill for 1 hour. Man receives a wettable powder that is easily dispersed in water and therefore suitable for the production of a biologically active spray mixture is.

Example B

40 parts of compound No. 57, a light brown oil with 40 parts of precipitated, ground silica, 10 parts of diatomaceous earth, 4 parts of chalk, 3 parts of the sodium salt of diisobutyl naphthalenesulfonic acid and 3 parts Na-N-oleoyl-N-methyl tauride intimately mixed and ground in a planetary ball mill for 1 hour. A wettable powder is obtained which is easily dispersed in water and therefore for the production of a biologically active Spray liquor is suitable.

Example C

10 parts of compound no. 19 are precipitated with 10 parts, ground silica, 70 parts of Attaclay, 2 parts of the Na salt diisobutyl naphthalenesulfonic acid, 1 part Na-N-oleoyl-N-methyl tauride and 7 parts of Na lignin sulfonate intimately mixed and ground in a planetary ball mill for 1 hour. A wettable powder is obtained which is easily dispersed in water and therefore for the production of a biologically active spray mixture suitable is.

Example D

50 parts of compound no. 36 are precipitated with 45 parts, ground silica, 2 parts of the sodium salt of diisobutyl naphthalenesulfonic acid and 3 parts Na-N-oleoyl-N-methyl tauride intimately mixed and in a planetary ball mill for 1 hour  grind. You get a wettable powder that is easily in water dispersed and therefore for the production of a biologically active Spray liquor is suitable.

Example E

40 parts of compound no. 64 are felled with 45 parts, ground silica, 9 parts finely ground chalk, 3 parts of the sodium salt of diisobutyl naphthalenesulfonic acid and 3 parts Na-N-Oleoyl-N-methyltauride intimately mixed and in one Mill the planetary ball mill for 1 hour. You get one Spray powder that is easily dispersed in water and therefore for Production of a biologically active spray mixture is suitable.

Example F

25 parts of compound no.53 become 65 parts of Solvesso 100 (aromatic solvent consisting mainly of trimethylbenzenes) dissolved and 10 parts of an emulsifier mixture, consisting of calcium dodecylbenzenesulfonate and a polyoxyethylene sorbitan tall oil ester admitted. You get an emulsifiable Concentrate that is used to produce a biologically active Spray liquor is suitable.

Example G

60 parts of compound No. 52 are mixed in a mixture of 20 parts Xylene and 10 parts of butyrolactone dissolved and 10 parts an emulsifier mixture consisting of calcium dodecylbenzenesulfonate and a polyoxyethylene sorbitan tall oil ester. An emulsifiable concentrate is obtained which is suitable for production a biologically active spray mixture.

Example H

40 parts of compound No. 64 are mixed in a mixture of 30 parts Solvesso 100 and 20 parts of cyclohexanone dissolved and 10 parts an emulsifier mixture consisting of calcium dodecylbenzenesulfonate and added a polyethoxylated castor oil.  An emulsifiable concentrate is obtained which is suitable for production a biologically active spray mixture.

Example I

10 parts of compound no. 221 become Solvesso in 80 parts 100 dissolved and 10 parts of an emulsifier mixture consisting of Calcium dodecylbenzenesulfonate and a polyethoxylated Nonylphenol added. An emulsifiable concentrate is obtained, which is used to produce a biologically active spray mixture is suitable.

Example J Herbicidal Effect

The application of a certain amount of active ingredient (see respective Test batches were post-emergence (3-5 leaf stage of the test plants).

The tests were evaluated according to the rating scheme of Table 1.

The experiments were optically rated 2-3 times (scale 1-9). The values shown are average values of all assessments.

The codes of the test plants used in the following are in Table 2 broken down.  

Table 1

EWRC scale 1-9

Table 2

Codes of the test plants used

Standard: 6-chloro-3-phenylpyridazin-4yl-5-octylthiocarbonate
AS: active substance
a) Nopon [oil additive]

Example K

The connection given in this example exceeds in the above Try the standard presented.

Similar activity profiles were ensured for analogue compounds.

Example L

Similar values were achieved for analog connections.  

Example M

Similar values were achieved for analog connections.

Example N

Herbicidal activity against Solanum americanum (SOLAM) = American nightshade

Example O

Herbicidal activity against millet-like grasses

In all cases, connection 64 will use the values of the standard surpassed.

Example P

Example Q

Example R

Example S

Example T

Example U

Claims (5)

1. Herbicidal agent, characterized by the content of at least one compound of the formula in which R₁ and R₂ each independently of the other hydroxyl, halogen, cyano, nitro, amino, which can optionally be substituted by alkyl with 1-4 C atoms, straight-chain or branched alkyl with 1-10 C atoms, which optionally can be substituted one or more times by hydroxyl, halogen or cyano, straight-chain or branched alkoxy with 1-10 C atoms, cycloalkyl with 5-7 C atoms, cycloalkoxy with 5-7 C atoms, phenyl, phenoxy, alkylthio or alkylsulfonyl with 1-4 carbon atoms mean
n and m independently of one another each represent the numbers 0, 1, 2 or 3, where n + m denotes the numbers 1 to 5, R₃ denotes the radicals hydroxy, -OC (O) ZR₄ or -OC (O) NR₄R₅, where
R₄ is a straight-chain or branched saturated or unsaturated alkyl radical with 1-15 C atoms, which can optionally be substituted by a phenyl radical or a phenyl radical or a cycloalkyl radical with 5-7 C atoms,
R₅ is a straight-chain or branched saturated or unsaturated alkyl radical with 1-15 C atoms, which can optionally be substituted by a phenyl radical or a phenyl radical or a cycloalkyl radical with 5-7 C atoms,
Z is a single bond, oxygen or sulfur and
X is halogen or their physiologically acceptable salts. 2. Herbicidal composition according to claim 1, characterized by the Content of at least one compound of formula I, according to Claim 1, in which R₁ and R₂ independently of one another  Residues halogen, straight-chain or branched alkyl with 1-4 C atoms, optionally one or more times Halogen can be substituted, or straight-chain or are branched alkoxy with 1-4 carbon atoms and n + m is 1 or 2, or a cyclohexyl radical means, where n + m is the number 1, R₃ the rest -OC (O) ZR₄ means, wherein R₄ and Z that specified in claim 1 Has meaning, and X means chlorine and bromine and their plant physiologically compatible acid addition salts. 3. Herbicidal composition according to claim 1, characterized by the Content of at least one compound of formula I in the R₁ and R₂ independently of one another chlorine or fluorine and n + m the numbers 1 or 2 or trifluoromethyl, and n + m the Number 1 mean R₃ the rest -OC (O) ZR₄, where R₄ and Z are the has the meaning given in claim 1, and X is chlorine or Bromine means. 4. A method for controlling weeds, characterized in that that compounds of formula I in which R₁, R₂, R₃, X, n and m have the meaning given in claim 1 affects weeds or their habitat. 5. Process for the preparation of herbicidal compositions, thereby characterized in that compounds of the formula I in which R₁, R₂, R₃, X, n and m are those specified in claim 1 Have meaning with extenders and / or surfactants Means mixed.