1-Substituted phenyl-pyridazone herbicides

Abstract

Substituted pyridazone derivatives having a good herbicidal action, herbicides containing these compounds as active ingredients, and a process for controlling the growth of unwanted plants with these compounds.

Description

The present invention relates to new and valuable pyridazones, herbicides containing these compounds as active ingredients, and a process for controlling the growth of unwanted plants with these compounds.

It has been disclosed to use 1-phenyl-4,5-dimethoxypyridazone-(6), 1-(m-trifluoromethylphenyl)-4,5-dimethoxypyridazone-(6) and 1-(m-tetrafluoroethoxyphenyl)-4-methylamino-5-chloropyridazone-(6) as herbicides (German Laid-Open Application DE-OS No. 2,526,643, Belgian 728,164, and German No. 1,197,676).

We have now found that substituted pyridazones of the formula ##STR1## where R and R.sup.1 denote lower alkoxy, preferably methoxy, R.sup.2 denotes difluoromethyl, fluoro, chloro, or X--R.sup.4, X denoting O or S and R.sup.4 denoting haloalkyl of 1 to 3 carbon atoms, e.g., --CHF.sub.2, --CF.sub.2 --CHF.sub.2, --CF.sub.2 CHF--CF.sub.3, --CF.sub.2 --CHFCl, --CF.sub.2 --CHFBr or CF.sub.3, and R.sup.3 denotes hydrogen when R.sup.2 is difluoromethyl or X--R.sup.4, or fluoro when R.sup.2 is fluoro or chloro, have a good herbicidal action.

The new compounds may be prepared by reacting 4,5-dihalo- or 4-alkoxy-5-halopyridazones of the formula ##STR2## where A denotes halogen (Cl, Br) or alkoxy (methoxy) and Hal denotes halogen (Cl, Br) and R.sup.2 and R.sup.3 have the above meanings, with an alcoholate of the formula R--R or R.sup.1 --B, R and R.sup.1 having the above meanings and B denoting Na or K, in the presence of an organic liquid.

The 4-alkoxy-5-halopyridazones and 4,5-dihalopyridazones required as starting products are either known or can be obtained in analogy to the processes disclosed in German No. 1,245,207, German No. 1,210,241 and German Laid-Open Application DE-OS No. 2,526,643; for instance, substituted hydrazines are prepared in conventional manner by reduction from the corresponding diazonium salt and are reacted, with or without being isolated as salts, with a 3-formyl-2,3-dihaloacrylic acid in known manner to give the corresponding pyridazone.

Purer products are obtained when the substituted hydrazines are isolated as salts, e.g., hydrochlorides, before the reaction to give the corresponding pyridazone.

When the 4,5-dialkoxypyridazones are prepared by reaction with an alcoholate, there are used for example 2 moles of alcoholate per mole of pyridazone when 4,5-dihalopyridazones are employed, and for example 1 mole of alcohoalte per mole of pyridazone when 4-alkoxy-5-halopyridazones are employed.

Suitable organic solvents are those which are inert to alcoholates between 100.degree. and 160.degree. C., e.g., toluene or xylene. The reaction may be carried out at from 100.degree. to 160.degree. C.

The intermediates have the following physical data:

______________________________________ ##STR3##R.sup.5 R.sup.6 R.sup.2 R.sup.3 m.p. (.degree.C.)______________________________________Cl Cl F F 196-197Cl Cl CHF.sub.2 H 118-119Br Br OCF.sub.2CHFCF.sub.3 H 72-74Cl Cl Cl F 200-202CH.sub.3 O Cl SCF.sub.3 H 129-131Cl Cl OCF.sub.2CHF.sub.2 H 74-75Cl Cl OCHF.sub.2 H 143-144Br Br OCF.sub.2CHFCl H 72-74Br Br OCF.sub.3 H 86-88Cl Cl OCF.sub.2CHFBr H 67-68______________________________________

EXAMPLE 1

7.2 parts (by weight) of 30% (by weight) sodium methylate solution is concentrated to dryness in vacuo and the residue is slurried in 250 parts of toluene. 10.8 parts of 1-(3-trifluoromethylthiophenyl)-4-methoxy-5-chloropyridazone-6 is added and the suspension is refluxed for 2 hours. After filtration has been carried out, the toluene is evaporated in vacuo. The residue is recrystallized from isopropanol. There is obtained 5.9 parts of 1-(3-trifluoromethylthiophenyl)-4,5-dimethoxypyridazone-6; m.p.: 93.degree.-95.degree. C.

EXAMPLE 2

39.6 parts of 30% sodium methylate solution is evaporated to dryness in vacuo and the residue is slurried in 500 parts of toluene. 36.6 parts of 1-(3-difluoromethoxyphenyl)-4,5-dichloropyridazone-6 is added and the whole refluxed for 2 hours. After filtration has been carried out, the toluene is evaporated in vacuo.

Yield: 28 parts of 1-(3-difluoromethoxyphenyl)-4,5-dimethoxypyridazone-6.

Melting point: 48.degree.-50.degree. C., after chromatography on SiO.sub.2 using a 7:3 mixture of toluene and acetone.

The following compounds are obtained analogously:

______________________________________ ##STR4## m.p.R R.sup.1 R.sup.2 R.sup.3 (.degree.C.) n.sub.D.sup.23______________________________________CH.sub.3 O CH.sub.3 O F F 136-138CH.sub.3 O CH.sub.3 O OCF.sub.2CHF.sub.2 H 81-83CH.sub.3 O CH.sub.3 O CHF.sub.2 H 52-55CH.sub.3 O CH.sub.3 O OCF.sub.2CHFCF.sub.3 H 58-60CH.sub.3 O CH.sub.3 O Cl F 148-149CH.sub.3 O CH.sub.3 O OCF.sub.3 H 84-85CH.sub.3 O CH.sub.3 O OCF.sub.2CHFCl H 64-65C.sub.2 H.sub.5 O C.sub.2 H.sub.5 O OCF.sub.2CHF.sub.2 H 1.5177CH.sub.3 O CH.sub.3 O OCF.sub.2CHFBr H 68-69______________________________________

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or tering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, talc, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

The new herbicidal pyridazones according to the invention may be mixed and applied with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable mixture components are anilides, diazines, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, biscarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, etc. Such combinations broaden the spectrum of action, and synergistic effects are at times achieved. A number of active ingredients which together with the new compounds give mixtures useful for various application are as are listed below by way of example.

______________________________________ ##STR5##R R.sup.1 R.sup.2______________________________________ ##STR6## NH.sub.2 Cl ##STR7## NH.sub.2 Br ##STR8## NH.sub.2 Cl ##STR9## ##STR10## Cl ##STR11## NHCH.sub.3 Cl ##STR12## NHCH.sub.3 Cl ##STR13## ##STR14## Cl______________________________________ ##STR15##R R.sup.1 R.sup. 2 R.sup.3______________________________________H i-C.sub.3 H.sub.7 H H or salts of this compoundH i-C.sub.3 H.sub.7 H CH.sub.3 or salts of this compoundCH.sub.2OCH.sub.3 i-C.sub.3 H.sub.7 H H ##STR16## or salts of this compound______________________________________ ##STR17##R R.sup.1 R.sup.2 R.sup.3 R.sup.4______________________________________H F.sub.3 C H C.sub.2 H.sub.5 C.sub.4 H.sub.9H F.sub.3 C H n-C.sub.3 H.sub.7 n-C.sub.3 H.sub.7H F.sub.3 C H CH.sub.2CH.sub.2 Cl n-C.sub.3 H.sub.7H SO.sub.2 NH.sub.2 H n-C.sub.3 H.sub.7 n-C.sub.3 H.sub.7H F.sub.3 C H n-C.sub.3 H.sub.7 ##STR18##H.sub.3 C H.sub.3 C H H CH(C.sub.2 H.sub.5).sub.2H F.sub.3 C NH.sub.2 n-C.sub.3 H.sub.7 n-C.sub.3 H.sub.7H H.sub.3 C H n-C.sub.3 H.sub.7 n-C.sub.3 H.sub.7______________________________________ ##STR19##R R.sup.1 R.sup.2______________________________________ ##STR20## H i-C.sub.3 H.sub.7 ##STR21## H CH(CH.sub.3)CCH ##STR22## H CH.sub.2CCCH.sub.2 Cl ##STR23## H i-C.sub.3 H.sub.7 ##STR24## H CH(CH.sub.3)CONHC.sub.2 H.sub.5 ##STR25## H NC(CH.sub.3).sub.2______________________________________ ##STR26##R R.sup.1 R.sup.2______________________________________ ##STR27## H CH.sub.3 ##STR28## H C.sub.2 H.sub.5 ##STR29## CH.sub.3 CH.sub.3 ##STR30## H C.sub.2 H.sub.5 ##STR31## H C.sub.2 H.sub.5______________________________________ ##STR32##R R.sup.1 R.sup.2______________________________________i-C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 CH.sub.2CClCCl.sub.2i-C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 CH.sub.2CClCHCln-C.sub.3 H.sub.7 n-C.sub.3 H.sub.7 C.sub.2 H.sub.5 ##STR33## C.sub.2 H.sub.5 C.sub.2 H.sub.5sec.-C.sub.4 H.sub.9 sec.-C.sub.4 H.sub.9 C.sub.2 H.sub.5n-C.sub.3 H.sub.7 n-C.sub.3 H.sub.7 n-C.sub.3 H.sub.7i-C.sub.4 H.sub.9 i-C.sub.4 H.sub.9 C.sub.2 H.sub.5 ##STR34## C.sub.2 H.sub.5 C.sub.2 H.sub.5i-C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 ##STR35##i-C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 ##STR36##______________________________________ ##STR37##______________________________________CH.sub.2CClCHClCH.sub.2CClCCl.sub.2______________________________________ ##STR38##R X Y R.sup.1______________________________________CH.sub.3 Cl Cl Na ##STR39## Cl H CH.sub.3 ##STR40## H H H, or salts of this compoundCl Cl Cl Na ##STR41## H CH.sub.3 CH.sub.3 ##STR42## H CH.sub.3 C.sub.2 H.sub.5C.sub.2 H.sub.5 Cl Cl Na ##STR43## H CH.sub.3 i-C.sub.3 H.sub.7 ##STR44## H CH.sub.3 CH.sub.3 ##STR45## H CH.sub.3 CH.sub.2CH(CH.sub.3).sub.2 ##STR46## H CH.sub.3 Na ##STR47## H CH.sub.3 CH.sub.3______________________________________ ##STR48##R R.sup.1 R.sup.2 R.sup.3 X______________________________________H tert.-C.sub.4 H.sub.9 H C.sub.2 H.sub.5 SCH.sub.3H i-C.sub.3 H.sub.7 H i-C.sub.3 H.sub.7 SCH.sub.3H i-C.sub.3 H.sub.7 H C.sub.2 H.sub.5 SCH.sub.3H CH.sub.3 H i-C.sub.3 H.sub.7 SCH.sub.3H i-C.sub.3 H.sub.7 H C.sub.2 H.sub.5 ClH i-C.sub.3 H.sub.7 H ##STR49## ClH C.sub.2 H.sub.5 H C.sub.2 H.sub.5 ClH C.sub.2 H.sub.5 H ##STR50## ClH i-C.sub.3 H.sub.7 H i-C.sub.3 H.sub.7 ClH i-C.sub.3 H.sub.7 H i-C.sub.3 H.sub.7 OCH.sub.3 ##STR51## H ##STR52## ClH C.sub.2 H.sub.5 H CH(CH.sub.3)CH.sub.2OCH.sub.3 ClH C.sub.2 H.sub.5 H CH(CH.sub.3)CCH Cl______________________________________ ##STR53##R R.sup.1 R.sup.2______________________________________CH.sub.3 CH.sub.3 CH(C.sub.6 H.sub.5).sub.2 ##STR54## H ##STR55##C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR56##HCCC(CH.sub.3).sub.2 H ##STR57## ##STR58## H CH.sub.3______________________________________ ##STR59##R R.sup.1 R.sup.2 R.sup.3______________________________________ ##STR60## H CH.sub.3 CH.sub.3 ##STR61## H CH.sub.3 H ##STR62## H CH.sub.3 CH.sub.3 ##STR63## H CH.sub.3 CH.sub.3 ##STR64## H CH.sub.3 OCH.sub.3 ##STR65## H CH.sub.3 OCH.sub.3 ##STR66## H CH.sub.3 OCH.sub.3 ##STR67## H CH.sub.3 OCH.sub.3 ##STR68## H CH.sub.3 CH.sub.3 ##STR69## H CH.sub.2CH(CH.sub.3).sub.2 ##STR70## CH.sub.3 H CH.sub.3 ##STR71## H CH.sub.3 CH.sub.3 ##STR72## H H ##STR73##______________________________________ ##STR74##R R.sup.1 R.sup.2 R.sup.3______________________________________NO.sub.2 CF.sub.3 H HCl CF.sub.3 H COOH, or salts or esters of this compoundCl Cl H ##STR75##H CF.sub.3 Cl OC.sub.2 H.sub.5______________________________________ ##STR76##R R.sup.1 R.sup.2______________________________________tert.-C.sub.4 H.sub.9 NH.sub.2 SCH.sub.3 ##STR77## NH.sub.2 CH.sub.3tert.-C.sub.4 H.sub.9 ##STR78## SCH.sub.3______________________________________ ##STR79##R R.sup.1 R.sup.2 R.sup.3______________________________________H CH.sub.3 Br ##STR80##H CH.sub.3 Cl tert.-C.sub.4 H.sub.9H CH.sub.3 Cl ##STR81##H (CH.sub.2).sub.3 ##STR82##H CH.sub.3 Br C.sub.3 H.sub.7 i______________________________________ ##STR83## R R.sup.1______________________________________ CH.sub.3 C.sub.2 H.sub.5 ##STR84## C.sub.2 H.sub.5 ##STR85## C.sub.2 H.sub.5______________________________________ ##STR86## ##STR87## #STR88## ##STR89##R R.sup.1 R.sup.2 R.sup.3______________________________________H n-C.sub.3 H.sub.7 CH.sub.2CHCH.sub.2 CH.sub.3Na n-C.sub.3 H.sub.7 CH.sub.2CHCH.sub.2 CH.sub.3______________________________________ ##STR90## or salts or esters of this compound ##STR91## ##STR92## ##STR93## ##STR94## ##STR95## or salts, esters or amides of this compound ##STR96## or salts, esters or amides of this compound ##STR97## or salts, esters or amides of this compound ##STR98## ##STR99## ##STR100## or salts of this compound ##STR101## ##STR102## or salts of this compound______________________________________ ##STR103##R.sup.1 R.sup.2 R.sup.3______________________________________ ##STR104## H H salts, esters, amides ##STR105## CH.sub.3 H " ##STR106## H H " ##STR107## CH.sub.3 H " ##STR108## H H " ##STR109## CH.sub.3 H "______________________________________ ##STR110##R.sup.1 R.sup.2 R.sup.3______________________________________ ##STR111## sec.C.sub.4 H.sub.9 H ##STR112## tert.C.sub.4 H.sub.9 H ##STR113## tert.C.sub.4 H.sub.9 CH.sub.3H CH.sub.3 H salts and estersH sec.C.sub.4 H.sub.9 H salts and estersH tert.C.sub.4 H.sub.9 H salts and estersH tert.C.sub.4 H.sub.9 CH.sub.3 salts and esters______________________________________ ##STR114##R.sup.1 R.sup.2 R.sup.3______________________________________ ##STR115## ##STR116## CH.sub.2 Cl ##STR117## ##STR118## CH.sub.2 Cl ##STR119## CH.sub.2CH.sub.2 OCH.sub.3 CH.sub.2 Cl ##STR120## CH.sub.2OCH.sub.3 CH.sub.2 Cl ##STR121## ##STR122## CH.sub.2 Cl ##STR123## CH.sub.2OC.sub.4 H.sub.9 n CH.sub.2 Cl ##STR124## ##STR125## CH.sub.2 Cl ##STR126## H ##STR127## ##STR128## H C.sub.2 H.sub.5 ##STR129## H C(CH.sub.3).sub.2C.sub.3 H.sub.7 ##STR130## H CH.sub.3______________________________________ ##STR131##X X.sub.1 R______________________________________Br Br H and saltsI I H and saltsBr Br ##STR132##______________________________________ ##STR133## and saltsX = NO.sub.2CN ##STR134## salts and esters ##STR135## ##STR136## ##STR137##______________________________________

EXAMPLE 3

Herbicidal action of the new compounds

The following experiments demonstrate the influence of various compounds according to the invention on the germination and growth of unwanted and crop plants. The series of experiments were carried out in the greenhouse and in the open.

I. Greenhouse exeriments

Plastic flowerpots having a volume of 300 cm.sup.3 were filled with a loamy sand containing about 1.5% humus. Seeds of the test plants given in Table 1 were sown shallow, and separated according to species. In the preemergence treatment, the active ingredients were then applied immediately to the surface of the soil. The active ingredients were suspended or emulsified in water as the vehicle and sprayed onto the surface of the soil by means of atomizing nozzles. After treatment, the vessels were lightly sprinkler-irrigated to stimulate germination and growth, and to activate the chemical compounds. The vessels were then covered with transparent plastic hoods until the plants had taken root. This cover ensured uniform germination of the test plants, to the extent that this was not impaired by the active ingredient.

For the postemergence treatment, the plants were first grown to a height of from 3 to 10 cm, depending on habit, before being treated. No hoods were placed on the pots. The plants were placed in either cooler (15.degree.-30.degree. C.) or warmer (25.degree.-40.degree. C.) parts of the greenhouse, depending on their temperature requirements. The experiments were run for from 4 to 6 weeks. During this period the plants were tended and their reaction to the individual treatments was assessed. The application rate of the compounds examined is given in kg/ha of active ingredient. For assessment, the 0 to 100 scale was used, 0 denoting no damage or normal emergence, and 100 denoting no emergence or complete destruction of at least the visible plant parts.

II. Experiments in the open

The experiments were carried out on small plots in a loamy sand (pH 5 to 6) containing from 1 to 1.5% humus. Treatment was preemergence, and was effected either immediately after sowing or at the latest 3 days later. The crop plants were sown in rows. The weed flora was made up of widely varying species and was natural. The compounds were applied, as an emulsion or suspension in water, with the aid of a motor-driven plot spray. Where no rain fell, sprinkling was carried out to ensure germination and growth of crop plants and weeds. All the experiments were run for several weeks or months. During this period, assessments on the 0 to 100 scale were made at various intervals.

Results

The new compounds exhibit a high degree of herbicidal activity (Tables 2, 3, 4, 5 and 6). Compared with prior art active ingredients, they offer advantages either with regard to their action on unwanted plants or they are much better tolerated by crop plants.

The compounds according to the invention are selective herbicidal active ingredients for the control of unwanted plants in agricultural and horticultural crops and forestry. They may also be used for removing plant growth on non-cropland, e.g., as total weedkillers on railroads, parking lots and in industrial plants. They may further be used for controlling or eliminating the growth of unwanted woody plants in aggregate and other fruit, nuts and grapes. Examples of crop plants are as follows:

______________________________________Botanical name Common name______________________________________Allium cepa onionsAnanas comosus pineappleArachis hypogaea peanuts (groundnuts)Asparagus officinalis asparagusAvena sativa oatsBeta vulgaris spp. altissima sugarbeetsBeta vulgaris spp. rapa fodder beetsBeta vulgaris spp. esculenta table beets, red beetsBrassica napus var. napus rapeBrassica napus var. napobrassicaBrassica napus var. rapa turnipsBrassica rapa var. silvestrisCamellia sinensis tea plantsCarthamus tinctorius safflowerCarya illinoinensis pecan treesCitrus limon lemonCitrus maxima grapefruitCitrus reticulataCitrus sinensis orange treesCoffea arabica (Coffea canephora, coffee plantsCoffea liberica)Cucumis melo melonsCucumis sativus cucumberCynodon dactylon Bermudagrass in turf and lawnsDaucus carota carrotsElacis guineensis oil palmsFragaria vesca strawberriesGlycine max soybeansGossypium hirsutum cotton(Gossypium arboreumGossypium herbaceumGossypium vitifolium)Helianthus annuus sunflowersHelianthus tuberosusHevea brasiliensis rubber plantsHordeum vulgare barleyHumulus lupulus hopsIpomoea batatas sweet potato Juglans regia walnut treesLactuca sativa lettuceLens culinaris lentilsLinum usitatissimum flaxLycopersicon lycopersicum tomatoMalus spp. apple treesManihot esculenta cassavaMedicago sativa alfalfa (lucerne)Mentha piperita peppermintMusa spp. banana plantsNicotiana tabacum (N. rustica) tobaccoOlea europaea olive treesOryza sativa ricePanicum miliaceumPhaseolus lunatus limabeansPhaseolus mungo mungbeansPhaseolus vulgaris snapbeans, green beans, dry beansPennisetum glaucumPetroselinum crispum parsleyspp. tuberosumPicea abies Norway spruceAbies alba firPinus spp. pine treesPisum sativum English peasPrunus avium cherry treesPrunus domestica plum treesPrunus dulcia almond treesPrunus persica peach treesPyrus communis pear treesRibes sylvestre redcurrantsRibes uva-crispaRicinus communisSaccharum officinarum sugar caneSecale cereale ryeSesamum indicum SesamiSolanum tuberosum Irish potatoesSorghum bicolor (s. vulgare) sorghumSorghum dochnaSpinacia oleracea spinachTheobroma cacao cacao plantsTrifolium pratense red cloverTriticum aestivum wheatVaccinium corymbosum blueberryVaccinium vitis-idaea cranberryVicia faba tick beansVigna sinensis (V. unguiculata) cow peasVitis vinifera grapesZea mays Indian corn, sweet corn, maize______________________________________

In the tables, pre- and postemergence use are documented. In addition to surface aplication, the agents may of course also be incorporated into the soil either before or after crop plants are sown, or after the crop plants have emerged.

Special applications such as post-directed or lay-by treatment are also possible. In this case, the spray is directed in such a manner that the leaves of sensitive crop plants are not touched; the agents are sprayed onto the soil beneath the crop plants, or the unwanted plants growing there.

In view of the wide variety of application methods, the agents according to the invention, or compositions containing them, may be used not only in the crop plants in the above tables, but also in a further large number of crop plants for eliminating unwanted plants. The application rates may vary from 0.1 to 15 kg/ha and more, depending on the object to be achieved.

TABLE 1______________________________________List of test plants AbbreviationBotanical name in tables Common name______________________________________Abutilon theophrasti Abutilon theo. velvet leafAlopecurus myosuroides Alepec. myos. slender foxtailAmaranthus retroflexus Amar. retr. redroot pigweedAvena fatua Avena fat. wild oatsChenopodium album Chenop. alb. lambsquarters (goosefoot)Chrysanthemum segetum Chrys. seg. corn marigoldIpomoea spp. Ipom. spp. morninggloryDatura stramonium Datura stram. jimsonweedEchinochloa crus galli Echin. c.g. barnyardgrassEuphorbia geniculata Euph. gen. South American member of the spurge familyGalium aparine Galium apar. catchweed bedstrawGlycine max Glyc. max soybeansGossypoum hirsutum Gossyp. hirs. cottonMatricaria spp. Matric. spp. chamomileOryza sativa Oryza sat. ricePolygonum persicaria Polyg. pers. ladysthumbPortulaca oleracea Port. oler. purslaneSida spinosa Sida pin. teaweed (prickly sida)Sinapis alba -- white mustardSolanum nigrum Solan. nigr. black nightshadeStellaria media -- chickweedVeronica spp. -- speedwell______________________________________ TABLE 2__________________________________________________________________________Herbicidal action and tolerance of active ingredients by crop plants;preemergence application in the greenhouse ##STR138##__________________________________________________________________________Com- Test plants and % damagepound Glyc. Gossyp. Oryza Abutilon Alopec. Amaranth. Chrys.no. R R.sup.1 R.sup.2 R.sup.3 kg/ha max hirs. sat. theo. myos. retr. seg.__________________________________________________________________________1 OCH.sub.3 OCH.sub.3 F F 1.0 0 -- 10 -- -- 98 902 OCH.sub.3 OCH.sub.3 CHF.sub.2 H 0.5 10 -- -- 100 70 30 -- 1.0 10 -- -- 100 100 100 --3 OCH.sub.3 OCH.sub.3 OCF.sub. 2CHFCF.sub.3 H 0.5 15 0 -- 100 70 100 -- 1.0 55 0 -- 100 98 100 -- Portulac. Euph. gen.4 OCH.sub.3 OCH.sub.3 OCHF.sub.2 H 0.5 -- 10 -- 100 90 40 100 1.0 -- 20 -- 100 95 75 100 Abutilon5 OCH.sub.3 OCH.sub.3 OCF.sub.2CHF.sub.2 H 0.5 -- 0 10 100 92 98 100 1.0 -- 5 20 100 95 98 100 2.0 -- 10 60 -- 95 95 100A OCH.sub.3 OCH.sub.3 H H 0.5 15 40 20 90 52 78 95prior 1.0 15 55 20 100 72 93 100art__________________________________________________________________________Com- Test plants and % damagepound Datura Ipom. Matric Sida Sinapsis Solan. Stellariano. R R.sup.1 R.sup.2 R.sup.3 kg/ha stram. spp. spp. spin. alba nigr. media__________________________________________________________________________1 OCH.sub.3 OCH.sub.3 F F 1.0 80 -- 100 70 90 98 --2 OCH.sub.3 OCH.sub.3 CHF.sub.2 H 0.5 95 100 100 100 -- 100 100 1.0 95 100 100 100 -- 100 1003 OCH.sub.3 OCH.sub.3 OCF.sub.2CHFCF.sub.3 H 0.5 75 100 100 100 -- 100 100 1.0 95 100 100 100 -- 100 1004 OCH.sub.3 OCH.sub.3 OCHF.sub.2 H 0.5 -- 65 100 70 -- 45 90 1.0 -- 65 100 95 -- 70 100 Echin.5 OCH.sub.3 OCH.sub.3 OCF.sub.2CHF.sub.2 H 0.5 95 85 100 98 55 98 100 1.0 95 90 100 98 80 98 100 2.0 -- 100 100 100 95 95 100A OCH.sub.3 OCH.sub.3 H H 0.5 89 66 100 53 98 92 94prior 1.0 94 100 100 69 98 98 98art__________________________________________________________________________ 0 = no damage 100 = plants destroyed TABLE 3__________________________________________________________________________Herbicidal action and tolerance of new active ingredientsby crop plants; preemergence application in the open ##STR139## Test plants and % damageCompound Gossyp. Amar. Chenop. Echin. Polyg.no. R R.sup.1 R.sup.2 R.sup.3 kg/ha hirs. retr. alb. c.g. pers.__________________________________________________________________________5 OCH.sub.3 OCH.sub.3 OCF.sub.2CHF.sub.2 H 1.0 1 67 84 51 30 2.0 11 93 95 78 70A OCH.sub.3 OCH.sub.3 H H 1.0 20 90 92 37 10prior art 2.0 55 100 99 68 56B prior art ##STR140## Cl OCF.sub.2CHF.sub.2 H 1.0 2.0 19 36 72 35 60 34 58 2 12__________________________________________________________________________ 0 = no damage 100 = nonemergence, or plants destroyed TABLE 4__________________________________________________________________________Herbicidal action of new active ingredients; postemergence applicationin the greenhouse ##STR141## Test plants and % damageCompound Avena Echin. Amar. Euph. Galium Port. Sida Veronicano. R R.sup.1 R.sup.2 R.sup.3 kg/ha fat. c.g. retr. gen. agar oler. spin. spp.__________________________________________________________________________5 OCH.sub.3 OCH.sub.3 OCF.sub.2CHF.sub.2 H 1.0 100 98 100 100 95 100 100 1003 OCH.sub.3 OCH.sub.3 OCF.sub.2CHFCF.sub.3 H 1.0 -- 100 100 -- 90 -- 100 --4 OCH.sub.3 OCH.sub.3 OCHF.sub.2 H 1.0 100 85 90 20 -- 100 100 1002 OCH.sub.3 OCH.sub.3 CHF.sub.2 H 1.0 -- 100 -- -- 80 -- 60 --6 OCH.sub.3 OCH.sub.3 SCF.sub.3 H 1.0 -- 80 -- -- 98 -- -- --A OCH.sub.3 OCH.sub.3 H H 1.0 80 70 75 22 60 100 80 100priorart__________________________________________________________________________ 0 = no damage 100 = plants destroyed TABLE 5__________________________________________________________________________Selective herbicidal action of the active ingredients;preemergence application in the greenhouse ##STR142## Test plants and % damage Gossyp- Eu- ium Abu- Echi- phor- Portu- Ses-Com- hirsut- tilon nochloa bia Ipo- laca bania Sidapound kg/ um theo- crus genic- moea oler- exal- Setaria spi-no R R.sub.1 R.sub.2 R.sub.3 ha cotton phrasti galli ulata spp. acea tata faberii nosa__________________________________________________________________________2 OCH.sub.3 OCH.sub.3 CHF.sub.2 H 0.25 0 -- 85 100 75 89 -- 70 95 0.5 10 92 85 -- 98 89 72 98 1003 OCH.sub.3 OCH.sub.3 OCF.sub.2CHFCF.sub.3 H 0.25 3 88 53 100 72 89 50 65 90 0.5 3 100 72 100 98 94 87 75 1005 OCH.sub.3 OCH.sub.3 OCF.sub.2CHF.sub.2 H 0.25 15 100 92 98 75 90 65 85 1006 OCH.sub.3 OCH.sub.3 SCF.sub.3 H 0.5 10 100 79 100 100 92 90 100 100C OCH.sub.3 OCH.sub.3 CF.sub.3 H 0.25 15 100 69 68 80 85 50 70 100priorart__________________________________________________________________________ TABLE 6__________________________________________________________________________Herbicidal action of the active ingredients; postemergenceapplication in the greenhouse ##STR143## Test plants and % damageCompound Centaurea Echinochloa Ipomoea Loliumno. R R.sub.1 R.sub.2 R.sub.3 cyanus crus galli spp. multiflorum__________________________________________________________________________7 OCH.sub.3 OCH.sub.3 OCF.sub.2CHFCl H 3.0 100 100 100 1008 OCH.sub.3 OCH.sub.3 OCF.sub.2CHFBr H 3.0 100 100 100 1009 OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 OCF.sub.2CHF.sub.2 H 3.0 -- 100 70 10010 OCH.sub.3 OCH.sub.3 OCF.sub.3 H 3.0 100 100 100 100__________________________________________________________________________

EXAMPLE 4

90 parts by weight of compound 1 is mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 5

20 parts by weight of compound 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 6

20 parts by weight of compound 3 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 7

20 parts by weight of compound 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210.degree. and 280.degree. C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 8

20 parts by weight of compound 2 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-.alpha.-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 9

3 parts by weight of compound 3 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 10

30 parts by weight of compound 4 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 11

40 parts by weight of compound 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt % of active ingredient.

EXAMPLE 12

20 parts of compound 2 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

Claims

1. A substituted pyridazone selected from the group consisting of 1-(3-tetrafluoroethoxyphenyl)-4,5-dimethoxypyridazone-6 and 1-(3-monobromotrifluoroethoxyphenyl)-4,5-dimethoxypyridazone.-6

2. A process for combating the growth of unwanted plants wherein the soil or the plants are treated with a substituted pyridazone selected from the group consisting of 1-(3-tetrafluoroethoxyphenyl)-4,5-dimethoxypyridazone-6 and 1-(3-monobromotrifluoroethoxyphenyl)-4,5-dimethoxypyridazone-6.