1-Polyfluoroalkoxyphenyl-4-substituted-5-halopyridazones-6 and herbicidal uses thereof

The present invention relates to new and valuable substituted pyridazones, a process for the manufacture thereof, their use as herbicides, and herbicides containing these compounds.
It is known to use 1-phenyl-4-amino-5-chloro (or bromo)-pyridazone-6 (German 1,105,232), 1-(3-trifluoromethylphenyl)-4-methoxy-5-chloropyridazone-6 (German 1,670,315), 1-(3-trifluoromethylphenyl)-4-dimethylamino-5-chloropyridazone-6 or 1-(3-trifluoromethylphenyl)-4-methylamino-5-chloropyridazone-6 (Swiss 482,684) as herbicides. However, they cause damage to some crop plants, particularly cotton, or have only a weak herbicidal action.
We have now found that substituted pyridazones of the formula ##STR1## where Hal denotes halogen (chloro, bromo), R.sup.1 denotes unsubstituted lower fluoroalkyl or lower fluoroalkyl substituted by chloro or bromo, and R denotes amino, alkylamino or dialkylamino having 1 to 3 carbon atoms per alkyl, the alkyl radicals being identical or different, R further denotes alkoxy of 1 to 3 carbon atoms, chloroacetamido, the radical CH.sub.3 COOCH.sub.2 -CO-NH- or trimethylenimino, cause less damage to crop plants, especially cotton, than the prior art active ingredients, and have a better herbicidal action.
The new compounds are prepared by reacting a pyridazone derivative of the formula ##STR2## where Hal and R.sup.1 have the above meanings, with ammonia; an alkylamine or dialkylamine of 1 to 3 carbon atoms per alkyl; trimethylamine; or an alcoholate of 1 to 3 carbon atoms, and the reaction product is if desired reacted with chloroacetyl chloride or acetylglycolic acid chloride.
The m-tetrafluoroethoxyphenylhydrazine required as precursor is obtained in conventional manner from the corresponding diazonium salt by reduction, and may be reacted, without isolation, with a 3-formyl-2,3-dihaloacrylic acid to give the corresponding pyridazone. A purer end product is, however, obtained when the m-tetrafluoroethoxyphenylhydrazine is isolated as the hydrochloride.

EXAMPLE 1
(a) 314 parts (by weight) of m-tetrafluoroethoxyaniline (W.A. Sheppard, J.Org.Chem., 29, 1, 1964) is diazotized with NaNO.sub.2 and H.sub.2 SO.sub.4 ; reduction to m-tetrafluoroethoxyphenylhydrazine is carried out with Na.sub.2 SO.sub.3, and subsequently m-tetrafluoroethoxyphenylhydrazine hydrochloride is precipitated out with concentrated hydrochloric acid. The hydrochloride is suspended in 6 liters of 1N HCl, 228 parts of mucochloric acid is added and the mixture kept for 3 hours at 90.degree. C. The 1-(m-tetrafluoroethoxyphenyl)-4,5-dichloropyridazone-6 which forms is suction filtered and recrystallized from cyclohexane.
Yield: 399 parts (74.5% of theory) Melting point: 74.degree. to 75.degree. C.
(b) A suspension of 18 parts (by weight) of 1-(m-tetrafluoroethoxyphenyl)-4,5-dichloropyridazone-6 in 100 parts of water and 50 parts of 40% (wt%) dimethylamine solution is heated for 30 minutes at 60.degree. to 70.degree. C. After the mixture has cooled, there is isolated 14 parts of 1-(m-tetrafluoroethoxyphenyl)-4-dimethylamino-5-chloropyridazone-6 having a melting point of 131.degree. to 132.degree. C (from cyclohexane).
(Active ingredient I)
EXAMPLE 2
10 parts of 1-(m-tetrafluoroethoxyphenyl)-4,5-dichloropyridazone-6 and 5 parts of 30% sodium methylate solution in methanol are refluxed for 10 minutes. After water has been added there is obtained 7 parts of 1-(m-tetrafluoroethoxyphenyl)-4-methoxy-5-chloropyridazone-6 having a melting point of 119.degree. to 120.degree. C (from cyclohexane/benzene).
(Active ingredient III)
EXAMPLE 3
A suspension of 10 parts of 1-(m-tetrafluoroethoxyphenyl)-4,5-dichloropyridazone-6 in 50 parts of water and 50 parts of 40% methylamine solution is stirred for 5 hours at 30.degree. C. Suction filtration gives 9 parts of 1-(m-tetrafluoroethoxyphenyl)-4-methylamino-5-chloropyridazone-6 having a melting point of 188.degree. to 189.degree. C (from ethanol).
(Active ingredient IV)
The following compounds were prepared analogously;
1-(m-tetrafluoroethoxyphenyl)-4,5-dibromopyridazone-6(m.p.: 63.degree. to 65.degree. C) was also used as starting material:
1-(m-tetrafluoroethoxyphenyl)-4-amino-5-chloropyridazone-6 m.p. 173.degree. to 174.degree. C.
1-(m-tetrafluoroethoxyphenyl)-4-amino-5-bromopyridazone-6 m.p. 178.degree. to 179.degree. C.
1-(m-tetrafluoroethoxyphenyl)-4-methylamino-5-bromopyridazone-6 m.p. 177.degree. to 178.degree. C.
1-(m-tetrafluoroethoxyphenyl)-4-dimethylamino-5-bromopyridazone-6 m.p. 112.degree. to 113.degree. C.
1-(m-tetrafluoroethoxyphenyl)-4-methoxy-5-bromopyridazone-6 m.p. 107.degree. to 108.degree. C.
__________________________________________________________________________ ##STR3##R.sup.1 R.sup.2 R.sup.3 M.p. (.degree. C)__________________________________________________________________________ ##STR4## Cl OCF.sub.2CHF.sub.2 97 ##STR5## Cl OCF.sub.2CHF.sub.2 79 ##STR6## Cl OCF.sub.2CHF.sub.2 106-107 ##STR7## Cl OCHF.sub.2 177-178 ##STR8## Cl OCHF.sub.2 162-163 ##STR9## Cl OCHF.sub.2 69-70 ##STR10## Cl OCHF.sub.2 124-125 ##STR11## Cl OCHF.sub.2 124-125OCH.sub.3 Cl OCHF.sub.2 161-162N(CH.sub.3).sub.2 Cl OCF.sub.2CHF.sub.2 126-127OCH.sub.3 Cl OCF.sub.2CHF.sub.2 111-112NHCH.sub.3 Cl OCF.sub.2CHF.sub.2 186-187N(CH.sub.3).sub.2 Cl OCF.sub.3 126-127N(CH.sub.3).sub.2 Br OCF.sub.3 136-137OCH.sub.3 Br OCF.sub.3 132-133OCH.sub.3 Cl OCF.sub.3 140-141NHCH.sub.3 Cl OCF.sub.3 143-144NHCH.sub.3 Br OCF.sub.3 137-138NH.sub.2 Br OCF.sub.3 172-173OCH.sub.3 Br OCHF.sub.2 143-144NH.sub.2 Br OCHF.sub.2 185-186N(CH.sub.3).sub.2 Br OCHF.sub.2 107-108NHCH.sub.3 Br OCHF.sub.2 156-157NHCOCH.sub.2 Cl Br OCHF.sub.2 121-122NHCOCH.sub.2 OCOCH.sub.3 Br OCHF.sub.2 90-91OCH.sub.3 Br OCF.sub.2CHFCl 135-136N(CH.sub.3).sub.2 Cl OCF.sub.2CHFCl 103-104N(CH.sub.3).sub.2 Br OCF.sub.2CHFCl 99-100NHCH.sub.3 Br OCF.sub.2CHFCl 191-192NH.sub.2 Cl OCF.sub.2CHFCl 173-174NHCH.sub.3 Cl OCF.sub.2CHFCl 193-194NH.sub.2 Br OCF.sub.2CHFCl 178-179N(CH.sub.3).sub.2 Cl OCF.sub.2CHFBr 85-86OCH.sub.3 Cl OCF.sub.2CHFBr 124-125NHCH.sub.3 Br OCF.sub.2CHFBr 183-184OCH.sub.3 Br OCF.sub.2CHFBr 144-145N(CH.sub.3).sub.2 Br OCF.sub.2CHFBr 87-88NHCH.sub.3 Cl OCF.sub.2CHFBr 186-187__________________________________________________________________________
Application of the herbicide may be effected for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage, aqueous, oily or other suspensions or dispersions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. 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 ingredients.
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, etc. 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, dimethyl sulfoxide, 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 silica gel, silicic acid, silicates, talc, kaolin, Attaclay, limestone, lime, 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.
There may be added to the compositions or individual active ingredients (if desired, immediately before use (tankmix)) oils of various types, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoams (e.g., silicones), growth regulators, antidotes and other herbicidally effective compounds such as
substituted anilines
substituted aryloxycarboxylic acids and salts, esters and
amides thereof,
substituted ethers
substituted arsonic acids and their salts, esters and amides
substituted benzimidazoles
substituted benzisothiazoles
substituted benzothiadiazinone dioxides substituted benzoxazines
substituted benzoxazinones
substituted benzothiadiazoles
substituted biurets
substituted quinolines
substituted carbamates
substituted aliphatic carboxylic acids and their salts, esters and amides
substituted aromatic carboxylic acids and their salts, esters and amides
substituted carbamoylalkylthiol- or -dithiophosphates
substituted quinazolines
substituted cycloalkylamidocarbothiolic acids and their salts, esters and amides
substituted cycloalkylcarbonamidothiazoles
substituted dicarboxylic acids and their salts, esters and amides
substituted dihydrobenzofuranyl sulfonates
substituted disulfides
substituted dipyridylium salts
substituted dithiocarbamates
substituted dithiophosphoric acids and their salts, esters and amides
substituted ureas
substituted hexahydro-1H-carbothioates
substituted hydantoins
substituted hydrazides
substituted hydrazonium salts
substituted isoxazole pyrimidones
substituted imidazoles
substituted isothiazole pyrimidones
substituted ketones
substituted dihydropyran diones
substituted naphthoquinones
substituted cyclohexane diones
substituted aliphatic nitriles
substituted aromatic nitriles
substituted oxadiazoles
substituted oxadiazinones
substituted oxadiazolidine diones
substituted oxadiazine diones
substituted phenols and their salts and esters
substituted phosphonic acids and their salts, esters and amides
substituted phosphonium chlorides
substituted phosphonalkyl glycines
substituted phosphites
substituted phosphoric acids and their salts, esters and amides
substituted piperidines
substituted pyrazoles
substituted pyrazole alkylcarboxylic acids and their salts,
esters and amides
substituted pyrazolium salts
substituted pyrazolium alkyl sulfates
substituted pyridazines
substituted pyridazones
substituted pyridine carboxylic acids and their salts, esters and amides
substituted pyridines
substituted pyridine carboxylates substituted pyridinones
substituted pyrimidines
substituted pyrimidones
substituted pyrrolidine carboxylic acid and its salts, esters and amides
substituted pyrrolidines
substituted pyrrolidones
substituted arylsulfonic acids and their salts, esters and amides
substituted styrenes
substituted tetrahydrooxadiazine diones
substituted tetrahydroxadiazole diones
substituted tetrahydromethanoindenes
substituted tetrahydroxadiazole thiones
substituted tetrahydrothiadiazine thiones
substituted tetrahydrothiadiazole diones
substituted thiocarboxylic acids and their salts, esters and amides
substituted thiol carbamates
substituted thioureas
substituted thiophosphoric acids and their salts, esters and amides
substituted triazines
substituted triazoles
substituted uracils, and
substituted uretidine diones.
The last-mentioned herbicidal compounds may also be applied before or after the active ingredients or compositions thereof according to the invention.
These agents may be added to the herbicides according to the invention in a ratio by weight of from 1:10 to 10:1. The same applies to oils, fungicides, nematocides, insecticides, bactericides, antidotes and growth regulators.
The amount used of the agents according to the invention may vary and depends in essence on the type of effect to be achieved; it is generally from 0.1 to 15 (and more), preferably from 0.2 to 6, kg per hectare of active ingredient. The agents according to the invention may be used once or several times before planting (with or without incorporation) or after planting, before sowing (with or without incorporation), and before (with or without incorporation), during or after emergence of the crop plants and unwanted plants.
The herbicides according to the invention may be employed in cereal crop such as
______________________________________Avena spp. SorghumTriticum spp. Zea maysHordeum spp. Panicum miliaceumSecale spp. Oryza spp.Saccharum offinicarumand in dicotyledon crops such asCruciferae, e.g. spp.Brassica spp. Raphanus spp.Sinapis spp. Lepidium spp.Compositae, e.g.Lactuca spp. Carthamus spp.Helianthus spp. Scorzonera spp.Malvaceae, e.g.Gossypium hirsutumLeguminosae, e.g.Medicago spp. Phaseclus spp.Trifolium spp. Arachis spp.Pisum spp. Glycine max.Chenopodiaceae, e.g.Beta vulgarisSpinacia spp.Solanaceae, e.g.Solanum spp. Capsicum annuumNicotiania spp.Linaceae, e.g.Linum spp.Umbelliferae, e.g.Petroselinum spp. Apium graveolensDaucus carotaRosaceae, e.g. FragariaCurcurbitaceae, e.g.Cucumis spp. Cucurbita spp.Liliaceae, e.g.Allium spp.Vitaceae, e.g.Vitis viniferaBromeliaceae, e.g.Ananas sativus.______________________________________
The new compositions have a strong herbicidal action and may therefore be used as weedkillers or for controlling the growth of unwanted plants. Whether the new active ingredients are used as total or selective agents depends in essence on the amount of ingredient used per unit area.
By weeds and unwanted plant growth are meant all monocotyledonous and dicotyledonous plants which grow in loci where they are not desired.
The agents according to the invention may therefore be used for controlling for instance
______________________________________Cynodon spp. Dactylis spp.Digitaria spp. Avena spp.Echinochloa spp. Bromus spp.Setaria spp. Uniola spp.Panicum spp. Poa spp.Alopecurus spp. Leptochloa spp.Lolium spp. Brachiaria spp.Sorghum spp. Eleusine spp.Agropyron spp. Cenchrus spp.Phalaris spp. Eragrostis spp.Apera spp. Phragmites communisetc.;Cyperaceae, such asCarex spp. Eleocharis spp.Cyperus spp. Scirpus spp.etc.;dicotyledonous weeds, such asMalvaceae, e.g.,Abutilon theoprasti Hibiscus spp.Sida spp. Malva spp.etc.;Compositae, such asAmbrosia spp. Centaurea spp.Lactuca spp. Tussilago spp.Senecio spp. Lapsana communisSonchus spp. Tagetes spp.Xanthium spp. Erigeron spp.Iva spp. Anthemis spp.Galinsoga spp. Matricaria spp.Taraxacum spp. Artemisia spp.Chrysanthemum spp. Bidens spp.Cirsium spp. etc.;Convolvulaceae, such asConvolvulus spp. Cuscuta spp.Ipomoea spp. Jaquemontia tamnifoliaetc.;Cruciferae, such asBarbarea vulgaris Arabidopsis thalianaBrassica spp. Descurainia spp.Capsella spp. Draba spp.Sisymbrium spp. Coronopus didymusThlaspispp. Lepidiumspp.Sinapis arvensis Raphanus spp.etc.;Geraniaceae, such asErodium spp. Geranium spp.etc.;Portulacaceae, such asPortulaca spp. etc.;Primulaceae, such asAnagallis arvensis Lysimachia spp.etc.;Rubiaceae, such asRichardia spp. Diodia spp.Galium spp. etc.;Scrophulariaceae, such asLinaria spp. Digitalis spp.Veronica spp. etc.;Solanaceae, such asPhysalis spp. Nicandra spp.Solanum spp. Datura spp.etc.;Urticaceae, such asUrtica spp.Violaceae, such asViola spp. etc.;Zygophyllaceae, such asTribulus terrestris etc.;Euphorbiaceae, such asMercurialis annua Euphorbia spp.Umbelliferae, such asDaucus carota Ammi majusAethusa cynapium etc.;Commelinaceae, such asCommelina spp. etc.;Labiatae, such asLamium spp. Galeopsis spp.etc.;Leguminosae, such asMedicago spp. Sesbania exaltataTrifolium spp. Cassia spp.Vicia spp. Lathyrus spp.etc.;Plantaginaceae, such asPlantago spp. etc.;Polygonaceae, such asPolygonum spp. Fagopyrum spp.Rumex spp. etc.;Aizoaceae, such asMollugo verticillata etc.;Amaranthaceae, such asAmaranthus spp. etc.;Boraginaceae, such asAmsinckia spp. Anchusa spp.Myostis spp. Lithospermum spp.etc.;Caryophyllaceae, such asStellaria spp. Silene spp.Spergula spp. Cerastium spp.Saponaria spp. Agrostemma githagoScleranthus annuus etc.;Chenopodiaceae, such asChenopodium spp. Atriplex spp.Kochia spp. Monolepsis nuttallianaSalsola Kali etc.;Lythraceae, such asCuphea spp. etc.;Oxalidaceae, such asOxalis spp.Ranunculaceae, such asRanunculus spp. Adonis spp.Delphinium spp. etc.;Papaveraceae, such asPapaver spp. Fumaria offinicalisetc.;Onagraceae, such asJussiaea spp. etc.;Rosaceae, such asAlchemillia spp. Potentilla spp.etc.;Potamogetonaceae, such asPotamogeton spp. etc.;Najadeceae, such asNajas spp. etc.;EquisetaceaeEquisetum spp. etc.;Marsileaceae, such asMarsilea quadrifolia etc.;Polypodiaceae,Pteridium aquilinumAlismataceae, such asAlisma spp. Sagittaria sagittifoliaetc.______________________________________
EXAMPLE 4
In the greenhouse, loamy sandy soil was filled into pots and sown with various seeds. The soil was then immediately treated with active ingredient I and, for comparison purposes, with prior art compound II 1-(m-trifluoromethylphenyl)-4-dimethylamino-5-chloropyridazone-(6), each substance being dispersed or emulsified in 500 liters of water per hectare. The application rate was 1 kg/ha (in the case of the crop plant) and 0.4 kg/ha (in the case of the unwanted plants). During the experiment the soil was kept thoroughly moist. After 4 to 5 weeks it was ascertained that active ingredient I had the same good crop tolerance as II, but a better herbicidal action.
The results are given below:
______________________________________Active ingredient I IIkg/ha 1 1______________________________________Crop plant:Triticum aestivum 0 0Active ingredient I IIkg/ha 0.4 0.4______________________________________Unwanted plants:Alopecurus myosuroides 90 80Echinochloa crus-galli 90 85______________________________________ 0 = no damage 100 = complete destruction
EXAMPLE 5
In the greenhouse, various plants were treated at a growth height of from 7 to 12 cm with active ingredient I and, for comparison, compound II, each substance being emulsified or dispersed in 500 liters of water per hectare. After 2 to 3 weeks it was ascertained that active ingredient I at 0.5 kg/ha had better crop tolerance than II, and at 0.4 kg/ha a stronger herbicidal action than II.
The results are given below:
______________________________________Active ingredient I IIkg/ha 0.5 0.5______________________________________Crop plant:Gossypium hirsutum 10 30Active ingredient I IIkg/ha 0.4 0.4______________________________________Unwanted plant:Echinochloa crus-galli 80 60______________________________________ 0 = no damage 100 = complete destruction
EXAMPLE 6
An agricultural plot was sown with various seeds. The plot was then immediately treated with 3 kg/ha of each of active ingredients I, III and IV, each being dispersed or emulsified in 500 liters of water per hectare.
After 4 to 5 weeks it was ascertained that active ingredients I, III and IV had a strong herbicidal action and were well tolerated by the crop plant.
The results are given below:
______________________________________Active ingredient I III IVkg/ha 3 3 3______________________________________Crop plant:Gossypium hirsutum 10 10 10Unwanted plants:Amaranthus retroflexus 100 100 100Chenopodium album 85 100 95Matricaria chamomilla 100 100 100Sinapis arvensis 90 100 100Stellaria media 80 100 90Thlaspi arvense 100 100 100Galium aparine -- 90 90Alopecurus myosuroides -- 90 90Echinochloa crus-galli -- 90 90______________________________________ 0 = no damage 100 = complete destruction
EXAMPLE 7
90 parts by weight of compound I is mixed with 10 parts by weight of N-methyl-.chi.-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
EXAMPLE 8
20 parts by weight of compound III 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 9
20 parts by weight of compound IV 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 uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
EXAMPLE 10
20 parts by weight of compound I 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 11
20 parts by weight of compound III is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-.chi.-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic 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 liquid is obtained containing 0.1% by weight of the active ingredient.
EXAMPLE 12
3 parts by weight of compound IV is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
EXAMPLE 13
30 parts by weight of compound I 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 14
In the greenhouse, loamy sandy soil was filled into pots and sown with the seeds of various test plants, separated by species. The soil was then immediately treated with the following active ingredients, each being dispersed or emulsified in 500 liters of water per hectare. The application rates were 0.25, 0.5, 1.0 and 2.0 kg/ha. During the experiment the soil in the pots was kept thoroughly moist.
______________________________________ ##STR12##Active ingredient R.sup.1 R.sup.2 R.sup.3______________________________________ ##STR13## Cl OCF.sub.2CHF.sub.2III OCH.sub.3 Cl OCF.sub.2CHF.sub.2IV ##STR14## Cl OCF.sub.2CHF.sub.2V OCH.sub.3 Cl CF.sub.3 (prior art)VI ##STR15## Cl CF.sub.3 (prior art)VII ##STR16## Cl H (prior art)VIII ##STR17## Br H (prior art)______________________________________
The action of the compounds on the various test plants after 4 to 5 weeks is apparent from the following table:
__________________________________________________________________________ Active ingredient and assessment Appli- cationTest rateplants kg/ha I III IV V VI VII VIII__________________________________________________________________________Gossypium 0.25 10 0 20 10 30 -- --hirsutum 0.5 10 0 20 10 30 30 70 1.0 15 0 20 20 30 80 70Echino- 2.0 20 0 20 20 80 95 90chloa 0.25 100 20 95 50 95 -- --crus-galli 0.5 100 90 100 90 95 50 50 1.0 100 100 100 95 95 60 80 2.0 -- -- -- -- -- 85 95Eleusine 0.25 80 60 90 30 95 -- --indica 0.5 100 85 95 80 95 -- -- 1.0 100 85 100 85 100 -- -- 2.0 -- -- -- -- -- -- --Setaria 0.25 100 90 100 80 100 -- --faberii 0.5 100 95 100 100 100 90 95 1.0 100 100 100 100 100 90 95 2.0 -- -- -- -- -- 95 100Cyperus 0.25 40 10 50 30 60 -- --esculentus 0.5 70 20 65 50 100 -- -- 1.0 90 50 70 -- 100 -- -- 2.0 -- -- -- -- -- -- --Ipomoea 0.25 55 30 50 30 60 -- --lacunosa 0.5 80 40 75 30 75 -- -- 1.0 85 50 95 40 85 -- -- 2.0 -- -- -- -- -- -- --Sida 0.25 90 30 50 30 60 -- --spinosa 0.5 95 40 75 30 75 -- -- 1.0 95 50 95 40 85 -- -- 2.0 -- -- -- -- -- -- --__________________________________________________________________________
These results may be summarized as follows.
Cotton clearly tolerates I, III and IV better than VI.
The action of I and IV on unwanted grasses is very good.
The action of I and IV on broadleaved unwanted species is the same as, or better than, that of VI.
Active ingredient V takes up an intermediate position with regard to compatibility in cotton. The action on unwanted plants was inferior to that of I and IV. The action of III on unwanted plants was similar to that of V, but its compatibility with cotton was excellent and better than that of V.
The action of the following compounds corresponds to that of I, III and IV:
______________________________________ ##STR18##R.sup.1 R.sup.2 R.sup.3______________________________________ ##STR19## Cl OCF.sub.2CHF.sub.2 ##STR20## Cl OCF.sub.2CHF.sub.2 ##STR21## Cl OCF.sub.2CHF.sub.2 ##STR22## Cl OCHF.sub.2 ##STR23## Cl OCHF.sub.2 ##STR24## Cl OCHF.sub.2 ##STR25## Cl OCHF.sub.2 ##STR26## Cl OCHF.sub.2OCH.sub.3 Cl OCHF.sub.2NH.sub.2 Cl OCF.sub.2 CHF.sub.2NH.sub.2 Br OCF.sub.2 CHF.sub.2______________________________________
EXAMPLE 15
Loamy sandy soil was filled into paraffined paper beakers having a volume of 170 cm.sup.3 ; the following test plants, separated by species, were sown shallow:
Latin name
Cyperus esculentus
Echinochloa crus galli
Eleusine indica
Euphorbia geniculata
Gossypium hirsutum
Ipomoea spp. usually I. lacunosa
Setaria faberii
Sida spinosa
The compounds were applied preemergence immediately after sowing. The seeds had not yet germinated; only the tubers of Cyperus esculentus had tips showing. The agents were suspended or emulsified in water as diluent and sprayed through atomizing nozzles. The soil was watered regularly during the experiment. The beakers were kept in the warm part of the greenhouse (18.degree. to 26.degree. C). The observation period was 4 weeks. Assessment was visual, employing a 0 to 100 scale on which 0 = no damage and 100 = complete destruction. The germinating cotton plants were also thinned out to 5 per vessel; the dry substance was determined herefrom after completion of the experiment.
Results
(1) The excellent herbicidal action of the new compounds 1-(m-tetrafluoroethoxyphenyl)-4-dimethylamino-5-chloropyridazone-6 (I) and 1-(m-tetrafluoroethoxyphenyl)-4-methylamino-5-chloropyridazone-6 (IV) was as good as that of analogous prior art compounds (Table 1).
(2) Of decisive importance is the superior tolerance in the crop plant cotton, which is particularly in evidence in a comparison of IV with VI, the prior art compound coming chemically closest to it (Table 1).
(a) Even at very high application rates the plants treated with IV yielded dry substance amounts which differed insignificantly from those of the untreated plants; by contrast, the two high application rates in the case of compound VI caused a significant drop in the amount of dry substance compared with the untreated plants.
(b) In a direct comparison of the two compounds IV and VI, no differences can be detected with any certainty at an application rate of 2.0 kg/ha, but there are indications that compound IV is better tolerated. The plants treated with IV at the highest application rate of 4.0 kg/ha showed however significantly improved growth, which thus proves the superior compatibility of this new substance with cotton.
(3) Some of the other new compounds of the same class had a similar, and sometimes a somewhat weaker, action on unwanted plants. The selectivity of 1-(m-difluoromethoxyphenyl)-4-dimethylamino-5-bromopyridazone-(6) (XI) in cotton was however excellent and far better than that of the comparative agents (Table 2).
Table 1 - Legend
+) 0 = no damage
100 = complete destruction
++) Duncan's new multiple range test, level 0.05%; values which have any letter(s) in common are not significantly different.
Table 1__________________________________________________________________________Weed control and tolerance in cotton (Gossypium hirsutum) of new m-phenylsubstituted pyridazonesBasic molecule ##STR27##Activeingredients Applica- % damage to unwanted plants.sup.+) Dry substance ofand substituents tion rate Echinochloa Euphorbia Ipomoea Setaria Sida young cotton plantsR.sup.1 R.sup.2 R.sup.3 kg/ha crus galli geniculata spp. faberii spinosa in g/vessel__________________________________________________________________________Control -- 0 0 0 0 0 1.15 ab.sup.++) ##STR28## Cl H (prior art) ##STR29## ##STR30## ##STR31## ##STR32## ##STR33## ##STR34## ##STR35## ##STR36## Cl CF.sub.3 (prior art) ##STR37## ##STR38## ##STR39## ##STR40## ##STR41## ##STR42## ##STR43## ##STR44## Cl CF.sub.3 (prior art) ##STR45## ##STR46## ##STR47## ##STR48## ##STR49## ##STR50## ##STR51## ##STR52## Cl OCF.sub.2 CHF.sub.2 ##STR53## ##STR54## ##STR55## ##STR56## ##STR57## ##STR58## ##STR59## ##STR60## Cl OCF.sub.2 CHF.sub.2 ##STR61## ##STR62## ##STR63## ##STR64## ##STR65## ##STR66## ##STR67##__________________________________________________________________________
Table 2__________________________________________________________________________Weed control and tolerance in cotton ( Gossypium hirsutum) of other newm-phenyl substituted pyridazones ##STR68##Active ingredients Applica- Test plants and % damageand substituents tion rate Gossypium Cyperus Echinochloa Eleusine Euphorbia Setaria SidaR.sup.1 R.sup.2 R.sup.3 kg/ha hirsutum esculentus crus galli indica geniculata faberii spinosa__________________________________________________________________________IXOCH.sub.3 Cl CF.sub.3 0.5 10 40 68.3 70 20 100 85 2.0 40 -- 97.7 -- 95 100 97.5(prior art) 4.0 -- -- 95.0 -- -- -- -- ##STR69## Cl CF.sub.3 0.5 2.0 4.0 17 32 30 62.5 68 93.8 97 95 96.7 95 95 92.5 100 -- 95 95 95 97 97 95XOCH.sub.3 Br OCHF.sub.2 0.5 10 30 20 25 30 -- 95 2.0 10 50 80 90 95 95 95 4.0 30 -- 92.5 95 -- 95 95 ##STR70## Br OCHF.sub.2 0.5 2.0 4.0 0 0 0 -- -- -- 40 90 90 80 95 95 90 95 -- 60 95 95 90 95 --XIIOCH.sub.3 Cl OCHF.sub.2 0.5 0 0 50 -- 25 55 90 2.0 5 0 95 -- 45 100 100 4.0 30 0 -- -- -- -- -- ##STR71## Cl OCHF.sub.2 0.5 2.0 4.0 5 40 40 10 10 10 50 100 10 -- -- -- 85 100 -- 100 100 -- 80 100__________________________________________________________________________ -- 0 = no damage 100 = complete destruction
EXAMPLE 16
Different crops call for varying periods of action of weedicides. For instance, in crops having a short vegetation period (e.g. vegetables) the agents employed should have short persistence, whereas in permanent crops (e.g. small fruit, grapes, hops) herbicides having long persistence are desirable. Even greater persistance is required of agents for removing unwanted plants from paths and ways, squares and playgrounds and the like, railroad track, industrial plants, etc. The persistence of the new compounds in the soil was investigated by means of a biotest.
Loamy sandy soil containing 1.5% humus was filled into paper beakers having a volume of 170 cm.sup.3 ; the surface of the soil was treated with the active ingredients and at the application rates given in Table 3. The agents was applied using water as diluent and through atomizing spray nozzles. The vessels were kept at a temperature of from 15.degree. to 30.degree. C for the duration of the experiment and cared for in accordance with the horticultural art. During the first two months following the application of the active ingredients the soil was regularly watered, the germinating plants were removed and the surface of the soil was broken up. The test plants employed to demonstrate persistence were Sinapis alba (white mustard) and Sorghum bicolor (milo grain corghum, Funk's hybrid variety). Both were sown separately after two months, and their growth was observed for 4 to 6 weeks. The damage was assessed visually on a 0 to 100 scale (0 = no influence on growth, 100 = plants destroyed).
The results are given in Table 3. The new compounds I and IV demonstrated considerable persistence in the soil.
There is thus justification in using these compounds not only in some agricultural crops, but also for the uses mentioned above, where greater persistence is desirable.
Table 3__________________________________________________________________________ Persistence of new m-phenyl substituted pyridazones ##STR72##Active ingredients Application Test plants and % damage; seeds sownand substituents rate two months after treatment of the soilR.sup.1 R.sup.2 R.sup.3 kg/ha Sinapis alba Sorghum bicolor__________________________________________________________________________VII ##STR73## ClH (prior art) 0.25 0.5 1.0 2.0 4.0 10 15 25 30 -- -- 10 20 30 38II ##STR74## ClCF.sub.3 (prior art) 0.25 0.5 1.0 2.0 4.0 30 45 95 98 -- -- 25 45 90 95VI ##STR75## ClCF.sub.3 (prior art) 0.25 0.5 1.0 2.0 4.0 78 85 98 98 -- -- 72 92 98 98 ##STR76## ClOCF.sub.2CHF.sub.2 0.25 0.5 1.0 2.0 4.0 32 42 75 95 -- -- 48 95 95 98IV ##STR77## ClOCF.sub.2CHF.sub.2 0.25 0.5 1.0 2.0 4.0 68 98 98 98 -- -- 75 82 88 98__________________________________________________________________________ 0 = no damage 100 = complete destruction
EXAMPLE 17
Postemergence action of m-phenyl substituted pyridazones
The herbicidal action of m-phenyl substituted pyridazone derivatives when applied prior to emergence of the unwanted plants has already been illustrated in the foregoing examples. In further experiments the effect of new compounds of this class when applied to the plant during growth (leaf treatment, postemergence treatment) was investigated. The test plants, separated by species, were grown from seed to a height of 3 to 10 cm in vessels (paraffined paper cups having a volume of 170 cm.sup.3) filled with loamy sandy oil. The plants were then treated with the active ingredients in the table below at the application rates mentioned therein. They were emulsified or suspended in water as carrier and sprayed onto the plants through atomizing nozzles. For the 4-week duration of the experiment the vessels were kept thoroughly moist in the greenhouse. The scale employed in the visual assessment was 0 to 100 (0 = no damage, 100 = complete destruction).
When applied postemergence the new compounds exhibited an exceptional action on unwanted plants. Their effects are similar when applied to the soil preemergence. They therefore offer the special advantage of a - for herbicides - very wide scope with regard to the time of application because of their leaf and residual action. In the case of herbaceous crop plants which are sensitive to these compounds when they are applied to the leaf, technical measures may be adopted in order to prevent direct contact of the spray liquor with the leaves (e.g. post-directed spray or layby treatment).
______________________________________List of test plants:Latin name Abbreviation in tables______________________________________Alopecurus myosuroides Alopec. myosur.Avena fatua Avena fatuaCyperus esculentus Cyperus escul.Cynodon dactylon Cynodon dactl.Echinochloa crus galli Echinochloa c.g.Ipomoea spp. Ipomoea spp.Sorghum halepense Sorghum hal.______________________________________
Table 4__________________________________________________________________________Weed Control afforded by some m-phenyl subtituted pyridazone derivativeswhen applied postemergence(leaf treatment)Basic molecule ##STR78## Appli-Active ingredients cation Test plants and % damageand substituents rates Alopec. Avena Cyperus Cynodon Echinochloa Ipomoea SorghumR.sup.1 R.sup.2 R.sup.3 kg/ha myosur. fatua escul. dactl. c.g. spp. hal.__________________________________________________________________________IX OCH.sub.3 ClCF.sub.3 1.0 90 80 95 50 90 40 90 (prior art) 2.0 90 90 95 50 90 60 90 4.0 90 90 -- -- -- -- --II ##STR79## ClCF.sub.3 (prior art) 1.0 2.0 4.0 80 90 90 30 65 70 95 95 -- 30 30 -- 100 100 100 40 40 -- 80 80 --VI ##STR80## ClCF.sub.3 (prior art) 1.0 2.0 4.0 100 100 100 85 85 85 95 95 -- 70 70 -- 100 100 100 45 45 -- 85 85 --IV ##STR81## ClOCF.sub.2CHF.sub.2 1.0 2.0 4.0 90 98 -- 87 95 -- 100 100 -- -- -- -- 98 98 -- -- -- -- 100 100 --XIV ##STR82## BrOCF.sub.3 1.0 2.0 4.0 100 100 100 80 90 90 -- -- -- -- -- -- 100 100 100 -- -- -- -- -- --XV ##STR83## ClOCF.sub.3 1.0 2.0 4.0 80 80 100 70 80 80 -- -- -- -- -- -- 98 98 98 -- -- -- -- -- --XVI ##STR84## BrOCF.sub.3 1.0 2.0 4.0 70 80 80 95 98 98 -- -- -- -- -- -- 100 100 100 -- -- -- -- -- --XVII OCH.sub.3 ClOCF.sub.2CHBrF 1.0 98 80 95 90 80 35 90 2.0 98 80 95 90 90 80 90 4.0 98 100 -- -- -- -- --XVIII ##STR85## BrOCHF.sub.2 1.0 2.0 4.0 98 98 98 0 90 95 -- 90 90 -- 95 95 -- 10 70 -- 90 95 --XIX ##STR86## ClOCF.sub.2CHBrF 1.0 2.0 4.0 98 100 100 70 80 80 95 95 -- 90 90 -- 80 80 -- 50 60 -- 90 90 --XX OCH.sub.3 ClOCF.sub.3 1.0 100 98 95 70 95 20 60 2.0 100 98 95 80 95 45 90 4.0 100 98 -- -- -- -- --XXI ##STR87## ClOCF.sub.3 1.0 2.0 4.0 90 90 90 60 60 80 -- -- -- -- -- -- 90 100 100 -- -- -- -- -- --XXII ##STR88## ClOCF.sub.2CHClF 1.0 2.0 4.0 80 90 90 80 80 80 -- -- -- -- -- -- 85 90 90 -- -- -- -- -- --XXIII ##STR89## BrOCF.sub.2CHClF 1.0 2.0 4.0 90 90 90 70 80 80 -- -- -- -- -- -- 90 100 100 -- -- -- -- -- --XXIV ##STR90## ClOCHF.sub.2 1.0 2.0 4.0 100 100 100 90 100 100 -- -- -- -- -- -- 90 100 100 -- -- -- -- -- --__________________________________________________________________________ 0 = no damage 100 = complete destruction

Number	Name	Date	Kind
3644355	Ebner et al.	Feb 1972
3697522	Reichender et al.	Oct 1972

1-Polyfluoroalkoxyphenyl-4-substituted-5-halopyridazones-6 and herbicidal uses thereof

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