US 4,643,760 AGrant
Herbicidal Sulfonylureas
Issue Date:1987-02-17
•20 Claims
Abstract
Substituted N-arylsulfonyl-N'-pyrimidinylureas and N-arylsulfonyl-N'-triazinylureas of the general formula ##STR1## wherein R.sup.1 is a ##STR2## R.sup.2 is hydrogen, halogen, nitro, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy or --COOR.sup.9, and the salts of these compounds with amines, alkali metal bases or alkaline earth metal bases, have good pre- and postemergence selective herbicidal and growth regulating properties. R.sup.3 is hydrogen, C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy, R.sup.4 and R.sup.5 are each independently of the other hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 haloalkylthio, C.sub.2 -C.sub.4 alkoxyalkyl, C.sub.3 -C.sub.6 -cycloalkyl or --NR.sup.10 R.sup.11, R.sup.6 is hydrogen or C.sub.1 -C.sub.3 alkyl, R.sup.7 is hydrogen or methyl, R.sup.8 is C.sub.4 -C.sub.6 cycloalkanonyl which is unsubstituted or substituted by C.sub.1 -C.sub.3 alkyl or halogen; C.sub.3 -C.sub.6 cycloalkyl which is unsubstituted or substituted by one or more identical or different members selected from the group consisting of C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, halogen or cyano; or is C.sub.5 -C.sub.6 cycloalkenyl which is unsubstituted or substituted by C.sub.1 -C.sub.3 alkyl, halogen or cyano, R.sup.9 is C.sub.1 -C.sub.3 alkyl or allyl, R.sup.10 and R.sup.11 are each independently of the other hydrogen or C.sub.1 -C.sub.4 alkyl, n is 0 or 1, X is sulfur or oxygen, and E and Z are each independently of the other nitrogen or the methine bridge, with the proviso that R.sup.8 is only unsubstituted or substituted C.sub.3 -C.sub.6 cycloalkyl if at the same time Z is nitrogen,
Metadata
Assignee
- Ciba-Geigy Corporation
Inventors
- Willy Meyer
- Werner Fory
Application Information
Application Number:US 6769055
Filing Date:1984-11-30
Priority Date:1983-12-08
Art Unit:122
Classifications
IPC:
C07D40112C07D23946A01N 4736
Field of Search:
54471331;320;321;332;323;32492
Patent Drawings
This patent does not have any drawings.
Description
The present invention relates to novel substituted N-arylsulonyl-N'-pyrimidinylureas and N-arylsulfonyl-N'-triazinylureas with herbicidal and plant growth regulating properties, to the preparation thereof, to compositions containing them, and to the use thereof for controlling weeds, in particular selectively, in crops of useful plants, or for regulating plant growth. The invention further relates to novel substituted arylsulfonylureas obtained as intermediates.
Specifically, the present invention relates to substituted N-arylsulfonyl-N'-pyrimidinylureas and N-arylsulfonyl-N'-triazinylureas of the formula I ##STR3## wherein R.sup.1 is a ##STR4## R.sup.2 is hydrogen, halogen, nitro, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 -alkoxy or --COOR.sup.9,
R.sup.3 is hydrogen, C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy,
R.sup.4 and R.sup.5 are each independently of the other hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 haloalkylthio, C.sub.2 -C.sub.4 alkoxyalkyl, C.sub.3 -C.sub.6 cycloalkyl or --NR.sup.10 R.sup.11,
R.sup.6 is hydrogen or C.sub.1 -C.sub.3 alkyl,
R.sup.7 is hydrogen or methyl,
R.sup.8 is C.sub.4 -C.sub.6 cycloalkanoyl which is unsubstituted or substituted by C.sub.1 -C.sub.3 alkyl or halogen; C.sub.3 -C.sub.6 cycloalkyl which is unsubstituted or substituted by one or more identical or different members selected from the group consisting of C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, halogen or cyano; or is C.sub.5 -C.sub.6 cycloalkenyl which is unsubstituted or substituted by C.sub.1 -C.sub.3 alkyl, halogen or cyano,
R.sup.9 is C.sub.1 -C.sub.3 alkyl or allyl,
R.sup.10 and R.sup.11 are each independently of the other hydrogen or C.sub.1 -C.sub.4 alkyl,
n is 0 or 1,
X is sulfur or oxygen, and
E and Z are each independently of the other nitrogen or the methine bridge, with the proviso that R.sup.8 is only unsubstituted or substituted C.sub.3 -C.sub.6 cycloalkyl if at the same time Z is nitrogen,
and to the salts thereof.
Herbicidally active ureas, triazines and pyrimidines are generally known. Recently, sulfonylureas with herbicidal and plant growth regulating properties have been described in European patent applications 35893, 44211, 44807, 85028 and 94790.
In the definititions of formula I, alkyl denotes straight chain or branched alkyl, e.g. methyl, ethyl, n-propyl or isopropyl.
Alkoxy denotes methoxy, ethoxy, n-propoxy or isopropoxy, with methoxy, ethoxy or isopropoxy being preferred.
Alkylthio is e.g. methylthio, ethylthio, n-propylthio or isopropylthio, with methylthio and ethylthio being preferred.
Halogen by itself or as moiety of haloalkoxy, haloalkyl or haloalkylthio is fluorine, chlorine and bromine, with fluorine and chlorine being preferred.
Alkoxyalkyl is e.g. methoxymethyl, ethoxymethyl, methoxyethyl and ethoxyethyl.
The carbocyclic radicals represented by R.sup.8 within the scope of this invention are for example the following radicals: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-oxocyclobutyl, 3-oxocyclobutyl, 2-oxocyclopentyl, 3-oxocyclopentyl, 2-oxocyclohexyl, 3-oxocyclohexyl, 4-oxocyclohexyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, or 3-cyclohexenyl. Preferred carbocyclic radicals are cycloalkyl radicals, in particular cyclopentyl and cyclohexyl.
The carbocyclic radicals R.sup.8 can be attached to the oxygen atom direct or through a further carbon atom. The direct bond is preferred, i.e. n is 0.
Haloalkyl as moiety of another substituent such as haloalkoxy or haloalkylthio is normally chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, 1,1,2-trifluoro-2-chloroethyl, 2,2,2-trifluoro-1,1-dichloroethyl, pentachloroethyl, 3,3,3-trifluoropropyl, 2,3-dichloropropyl, 1,1,2,3,3,3-hexafluoropropyl, with fluoromethyl, chloromethyl, difluoromethyl and trifluoromethyl being preferred.
The invention also comprises the salts which the compounds of formula I are able to form with amines, alkali metal bases and alkaline earth metal bases, or with quaternary ammonium bases. Preferred salt-forming alkali metal hydroxides and alkaline earth metal hydroxides are the hydroxides of lithium, sodium, potassium, magnesium or calcium, most preferably those of sodium or potassium.
Examples of suitable salt-forming amines are primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, propylamine, isopropylamine, the four butylamine isomers, dimethylamine, diethylamine, diethanolamine, dipropylamine, diisopropylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and isoquinoline. Preferred amines are ethylamine, propylamine, diethylamine or triethylamine, with isopropylamine, diethanolamine and 1,4-diazabicyclo[2.2.2]octane being most preferred.
Examples of quaternary ammonium bases are, in general, the cations of haloammonium salts, e.g. the tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzylammonium cation. The tetraethylammonium cation, the trimethylethylammonium cation, and also the ammonium cation.
Among the compounds of formula I, those compounds are preferred in which Z is nitrogen and in which either
(a) X is oxygen or
(b) R.sup.2 is hydrogen or
(c) R.sup.3 is hydrogen or
(d) R.sup.4 and R.sup.5 are each independently halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, di(C.sub.1 -C.sub.3)alkylamino or C.sub.1 -C.sub.3 haloalkoxy, and together contain not more than 4 carbon atoms,
(e) R.sup.1 is --O--R.sup.8 or
(f) R.sup.1 is --O--CHR.sup.7 -cyclopropyl.
Among the compounds of the subgroup (e), those compounds are particularly preferred in which R.sup.8 is C.sub.3 -C.sub.6 cycloalkyl, in particular cyclopentyl or cyclohexyl.
Further preferred subgroups of compounds of formula I are those in which X is oxygen, R.sup.2 and R.sup.3 are hydrogen, R.sup.4 and R.sup.5 are each independently of the other halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, di(C.sub.1 -C.sub.3)alkylamino or C.sub.1 -C.sub.3 haloalkoxy, and together contain not more than 4 carbon atoms, Z is nitrogen and R.sup.1 is a --O--R.sup.8 radical; and 4 carbon atoms, Z is nitrogen and R.sup.1 is a --O--R.sup.8 radical; and especially those in which X is oxygen and Z is nitrogen, R.sup.2 and R.sup.3 are hydrogen, R.sup.4 and R.sup.5 are each independently of the other C.sup.1 -C.sub.3 -alkyl, halogen, C.sub.1 -C.sub.3 alkoxy, di(C.sub.1 14 C.sub.3)alkylamino or C.sub.1 -C.sub.3 haloalkoxy, and together contain not more than 4 carbon atoms, and R.sup.1 is C.sub.3 -C.sub.6 -cycloalkoxy, preferably cyclopenyl or cyclohexyloxy.
Preferred individual compounds of formula I are:
N-(2-cyclopentyloxypyridin-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triaz in-2-yl)urea and
N-(2-cyclopropylmethoxypyridin-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-t riazin-2-yl)urea.
The preparation of the compounds of formula I is generally carried out by the following methods.
A first process for the preparation of the compounds of formula I comprises reacting a substituted arylsulfonamide of the formula II ##STR5## wherein R.sup.1, R.sup.2 and Z are as defined for formula I, with an N-pyrimidinylcarbamate or N-triazinylcarbamate of the formula III ##STR6## wherein E, R.sup.3, R.sup.4, R.sup.5 and X are as defined for formula I and R is phenyl, alkyl or substituted phenyl, in the presence of a base.
A second process for obtaining the compounds of formula I comprises reacting a substituted N-arylsulfonylcarbamate of the formula IV, ##STR7## wherein R.sup.1, R.sup.2, X and Z are as defined for formula I, and R is phenyl, alkyl or substituted phenyl, with an aminopyrimidine or aminotriazine of the formula V ##STR8## wherein E, R.sup.3, R.sup.4 and R.sup.5 are as defined for formula I.
Finally, the compounds of formula I may also be obtained by reacting a sulfonylisocyanate of the formula VI ##STR9## wherein R.sup.1, R.sup.2, X and Z are as defined for formula I, with an aminopyridimine or aminotriazine of the formula V above.
If desired, the ureas of formula I so obtained can be converted into addition salts with amines, alkali metal hydroxides or alkaline earth metal hydroxides, or with quaternary ammonium bases. This conversion is carried out e.g. by reacting the compounds of formula I with the equimolar amount of a base and removing the solvent by evaporation.
It is convenient to carry out these reactions for obtaining compounds of formula I in aprotic, inert organic solvents. Examples of such solvents are: benzene, toluene, xylene or cyclohexane; chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, or chlorobenzene; ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane; nitriles such as acetonitrile or propionitrile; amides such as dimethylformamide, diethylformamide or N-methylpyrrolidinone.
The reaction temperatures are preferably in the range from -20.degree. to +120.degree. C. The coupling reactions are normally slightly exothermic and can be carried out at room temperature. To shorten the reaction time or also to initiate the reaction it is expedient to heat the reaction mixture briefly to boiling point. The reaction times can also be shortened by addition of a few drops of a base or isocyanate as catalyst. Preferred bases are tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicylo[4,3,0]-non-5-ene or 1,8-diazabicyclo[5,4,0]undec-7-ene. However, the bases employed may also be inorganic bases, e.g. hydrides such as sodium hydride or calcium hydride, hydroxides such as sodium hydroxide or potassium hydroxide, carbonates such as sodium or potassium carbonate, or bicarbonates such as potassium or sodium bicarbonate.
The final products of formula I can be isolated by concentrating the reaction mixture and/or removing the solvent by evaporation, and by recrystallisation or by triturating the solid residue in a solvent in which it is poorly soluble, such as an ether, an aromatic hydrocarbon or a chlorinated hydrocarbon.
The intermediates of formula II, IV and VI, in which Z is the methine group, are known from published EP application 94790 and can be prepared by methods which are known per se.
The intermediates of the formulae II, IV and VI, in which Z is nitrogen, are novel and have been specially developed for the synthesis of the compounds of formula I. They therefore constitute an object of the present invention.
The novel intermediates of the formula II, in which Z is nitrogen, are prepared by procedures which are known per se. Thus, for example, the compounds of the subformula IIa ##STR10## wherein R.sup.1 and R.sup.2 are as defined for formula II, are obtained by reacting a halopyridinylsulfonamide of the formula VII ##STR11## wherein R.sub.2 is as defined for formula I and Hal is halogen, preferably fluorine or chlorine, with an alcohol of the formula VIII ##STR12## wherein n, R.sup.6, R.sup.7 and R.sup.8 are as defined for formula I, in the presence of a base and in a polar aprotic solvent.
The novel compounds of the formula IIa are also obtained by diazotising amines of the formula IX ##STR13## wherein R.sup.1 and R.sup.2 are as defined for formula I, and replacing the diazo group with sulfur dioxide in the presence of a catalyst such as copper chloride, in hydrochloric acid or acetic acid, and reacting the resultant pyridinylsulfonyl chloride of the formula X ##STR14## wherein R.sup.1 and R.sup.2 are as defined for formula I, with ammonium hydroxide solution. The appropriate starting amines are known or they can be obtained by known procedures.
Likewise, the novel compounds of formula IIa can be obtained by converting a pyridinylsulfonic acid of the formula XI, ##STR15## wherein R.sup.1 and R.sup.2 are as defined for formula I, by treatment with a chlorinating agent such as PCl.sub.5, POCl.sub.3, COCl.sub.2 or SOCl.sub.2, to give the corresponding pyridinylsulfonyl chloride of the formula X, and reacting this chloride with ammonium hydroxide solution.
The compounds of formula IIa can also be obtained by converting a benzyl thioether of the formula XII ##STR16## wherein R.sup.1 and R.sup.2 are as defined for formula I, by treatment with chlorine, and reacting the resultant pyridinylsulfonyl chloride of the formula X with ammonium hydroxide solution.
The pyridinylsulfonyl isocyanates of the formula VI, which are also novel, can be obtained by phosgenating the sulfonamides of the formula IIa, in the presence of butylisocyanate, in a chlorinated hydrocarbon as solvent, at reflux temperature. Similar reactions are described in "Neuere Methoden der praparativen organischen Chemie", Band. VI, 211-229, Verlag Chemie, Weinheim, 1970.
The isothiocyanates of the formula VI are obtained by treating the sulfonamides of formula II with carbon disulfide and potassium hydroxide and subsequently phosgenating the dipotassium salt. Such processes are described in Arch. Pharm. 299, 174 (1966).
The N-arylsulfonylcarbamates of the formula IV are obtained by reacting the sulfonamides of the formula IIa with a carbonate in the presence of a base. Similar processes are described in Japanese patent specification 61 169.
The starting aminopyrimidines and aminotriazines of the formula V, as well as corresponding carbamates of the formula III, have either long been known or are described in European patent application 70 804, or they can be prepared by known methods from compounds disclosed therein.
The final products can be isolated by concentrating the reaction mixture and/or evaporating off the solvent, and purified by recrystallising or triturating the solid residue in solvents in which they are not readily soluble, e.g. in an ether, an aromatic hydrocarbon or a chlorinated hydrocarbon.
The compounds of formula I are stable compounds, and no protective measures are required for handling them.
The compounds of the formula VII, XIII, IX, X, XI and XII are known or can be prepared by procedures analogous to known ones.
When used at low rates of application, the compounds of formula I have good selective growth inhibiting and selective herbicidal properties which make them most suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, maize and rice. In some cases damage is also caused to weeds which have only been controlled up to now with total herbicides.
The mode of action of these compounds is unusual. Many are translocatable, i.e. they are absorbed by the plant and transported to other parts of it where they then exert their action. Thus, for example, it is possible to damage perennial weeds to the roots by surface treatment. Compared with other herbicides and growth regulators, the novel compounds of the formula I are effective even when used at very low rates of application.
The compounds of formula I have in addition pronounced growth-regulating, especially growth-inhibiting, properties. The growth of both monocots and dicots is inhibited. Thus, for example, the compounds of formula I selectively inhibit the growth of legumiosae which are frequently planted as cover crops in tropical regions, so that, while soil erosion between cultivated plants is prevented, the cover crops cannot compete with the cultivated plants.
Inhibition of the vegetative growth of many cultivated plants permits more plants to be sown in a crop area, so that a higher yield may be obtained per unit of area. A further mechanism of yield increase using growth regulators resides in the fact that nutrients are able increasingly to promote flower formation and fruiting, whereas vegetative growth is inhibited.
At higher rates of application, all tested plants are so severely damaged in their development that they die.
The invention also relates to herbicidal and growth-regulating compositions which contain a novel compound of the formula I, and also to methods of controlling weeds pre- and postemergence and of inhibiting the growth of monocots and dicots, especially grasses, tropical cover crops and tobacco plant suckers.
The compounds of the formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of applications, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions containing the compound (active ingredient) of the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts or higher fatty acids (C.sub.10 -C.sub.22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C.sub.8 -C.sub.22 alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethylanolamine salts of dodecylbenzene sulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, caster oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C.sub.8 -C.sub.22 alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described e.g. in the following publications:
"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., 1981; H. Stache, "Tensid-Taschenbuch", 2nd Edition, C. Hanser Verlag, Munich & Vienna, 1981; M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81.
The pesticidal compositions usually contain 0.1 to 95%, preferably 0.1 to 80%, of a compound of the formula I, 1 to 99.9%, of a solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%, of a surfactant.
Preferred formulations are composed in particular of the following constituents (%=percentage by weight):
Whereas commercial products will be preferably formulated as concentrates, the end user will normally employ dilute formulations. The formulations can be diluted to a concentration as low as 0.001% The rates of application are normally from 0.01 to 10 kg a.i./ha, preferably from 0.025 to 5 kg a.i./ha.
The compositions may also contain further ingredients such as stabilisers, antifoams, viscosity regulators, binders, tackifiers, as well as fertilisers and other compounds for obtaining special effects.
The invention is illustrated by the following Examples.
EXAMPLE P1
N-(2-Cyclopentyloxypyridin-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triaz in-2-yl)urea (compound 5.1)
(a) 2-Cyclopentyloxypyridin-3-ylsulfonamide 10.9 g of a 55% dispersion of sodium hydride are suspended in 40 ml of dimethylformamide and then 13.6 ml of cyclopentanol are added dropwise. Then a solution of 19.24 g of 2-chloropyridin-3-ylsulfonamide in 40 ml of dimethylformamide is added dropwise and the reaction mixture is stirred for 2 hours at 35.degree.-40.degree. C. and then taken up in a mixture of 250 ml of ethyl acetate, 250 ml of ice-water and 125 ml of 1N hydrochloric acid. After extraction with 3.times.100 ml of ethyl acetate the combined organic phases are washed with 4.times.100 ml of water. The organic solution is washed and dried, affording an oily residue which crystallises after trituration with 50 ml of ether to give 19.64 g of 2-cyclopentyloxypyridin-3-ylsulfonamide with a melting point of 134.degree.-135.degree. C.
(b) To a mixture of 4.84 g of 2-cyclopentyloxypyridin-3-ylsulfonamide and 3.13 ml of 1,8-diazabicyclo[5.4.0]undec-7-ene in 50 ml of absolute dioxan are added 5.46 g of N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)phenylcarbamate at 20.degree. to 25.degree. C. The mixture is stirred for 1/2 hour, the precipitate is isolated and the filtrate is concentrated by evaporation. The residue is triturated with 10 ml of 2N hydrochloric acid and the crystals so obtained are isolated, washed with ether and water and dried, affording 7.79 g of N-(2-cyclopentyloxypyridin-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-tria zin-2-yl)urea with a melting point of 170.degree.-172.degree. C.
EXAMPLE P2
N-(2-Cyclopropylmethyoxypyridin-3-ylsulfonyl)-N'-(4-methoxy-6-methy 1-1,3,5-triazin-2-yl)urea (compound 5.60)
(a) 2-Cyclopropylmethoxypyridin-3-ylsulfonamide
11.99 g of a 55% dispersion of sodium hydride are suspended in 40 ml of dimethylformamide and 13.04 ml of cyclopropylmethanol are added dropwise at 10.degree. C. under a nitrogen atmosphere. The mixture is stirred for 15 minutes and then a solution of 21.16 g of 2-chloropyridin-3-ylsulfonamide in 40 ml of dimethylformamide is added dropwise. The reaction mixture is stirred for 30 minutes at 35.degree.-40.degree. C. and then taken up in a mixture of 275 ml of ethyl acetate, 275 ml of ice-water and 137.5 ml of 2N hydrochloric acid. The organic phase is separated and the aqueous phase is extracted with 3.times.100 ml of ethyl acetate. The combined organic phases are washed with 4.times.100 ml of water, dried, concentrated by evaporation and the residue is triturated with ether/hexane (2:1). The crystals so obtained are isolated and dried, affording 22.25 g of 2-cyclopropylmethoxypyridin-3-ylsulfonamide with a melting point of 121.degree.-122.degree. C.
(b) 4.56 g of 2-cyclopropylmethoxypyridin-3-ylsulfonamide and 3.13 ml of 1,8-diazabicyclo[5.4.0]undec-7-ene are suspended in 50 ml of dioxan and to this suspension are added 5.46 g of N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)phenylcarbamate. The mixture is stirred for 20 minutes and concentrated by evaporation. The residue is triturated with 10 ml of 2N hydrochloric acid and the precipitated solid is isolated and washed with water and ether, affording 6.90 g of N-(2-cyclopropylmethoxypyridin-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5- triazin-2-yl)urea with a melting point of 165.degree.-167.degree. C.
The compounds and intermediates listed in the following tables are obtained in an analogous manner.
FORMULATION EXAMPLES
EXAMPLE F1
Formulation Examples for compounds of formula I (percentages are by weight)
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
Dusts which are ready for use are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill.
The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
BIOLOGICAL EXAMPLES
EXAMPLE B1
Preemergence herbicidal action
Plastic pots are filled with expanded vermiculite (density: 0.135 g/cm.sup.3, water-absorbing capacity: 0.565 l/l). After the non-adsorptive vermiculite has been saturated with an aqueous emulsion in deionised water which contains the test compound in a concentration of 70.8 ppm, seeds of the following plants are sown on the surface: Nasturtium officinalis, Agrostis tenuis, Stellaria media and Digitaria sanguinalis. The pots are then kept in a climatic chamber at 20.degree. C., an illumination of about 20 klux and a relative humidity of 70%. During the germinating phase of 4 to 6 days, the pots are covered with lightpermeable material and watered with deionised water to increase the local humidity. After the 5th day, 0.5% of a commercial liquid fertiliser (Greenzit.RTM., ex Ciba-Geigy) is added to the water. The test is evaluated 12 days after sowing and the action on the plants is assessed according to the following rating:
1: plants have not emerged or are totally withered
2-3: very pronounced action
4-6: medium action
7-8: weak action
9: no action (as untreated controls).
Preemergence action
Concentration of the test compound emulsion: 70.8 ppm
EXAMPLE B2
Growth inhibition of tropical cover crops
The test plants (Centrosema plumieri and Centrosema pubescens) are reared until fully grown and then cut back to a height of 60 cm. The plants are sprayed 7 days later with an aqueous emulsion of the test compound. The test plants are kept at 70% relative humidity and 6000 lux artificial light for 14 hours per day, at day temperatures of 27.degree. C. and night temperatures of 21.degree. C. The test is evaluated 4 weeks after application by assessing and weighing the new growth compared with controls and by determining the phytotoxicity.
In this test a marked reduction in new growth of the plants treated with compounds of the formula I is observed (less than 20% of the new growth of untreated control plants), without damage being caused to the test plants.
EXAMPLE B3
Growth regulation of soybeans
Soybeans of the "Hark" variety are sown in plastic containers in an earth/peat/sand mixture (6:3:1). The containers are put into a climatic chamber and the plants develop to the 5-6 trefoil leaf stage after about 5 weeks by optimum control of temperature, light, fertiliser addition, and watering. The plants are then sprayed with an aqueous mixture of a compound of the formula I until thoroughly wetted. The rate of application corresponds to 100 g a.i. per hectare. Evaluation is made about 5 weeks after application. Compared with untreated controls, the compounds of the formula I markedly increase the number and weight of the harvested siliques on the leading shoot.
EXAMPLE B4
Growth inhibition of cereals
Summar barley (Hordeum vulgare) and summer rye (Secale) are sown in sterilised soil in plastic beakers in a greenhouse and watered as required. The cereal shoots are treated about 21 days after sowing with an aqueous spray mixture of a compound of the formula I. The concetration corresponds to 100 g of active ingredient per hectare. Evaluation of the growth of the cereals is made 21 days after application. A comparison with untreated controls shows that the growth of cereal plants treated with compounds of the formula I is significantly reduced (60-90% of the controls) and that the diameter of the stalks has in some cases increased.
EXAMPLE B5
Growth inhibition of grasses
Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina, Dactylis glomerate and Cynodon dactylon are sown in plastic dishes filled with an earth/peat/sand mixture (6:3:1), in a greenhouse, and watered as required. The emergent grasses are cut back weekly to a height of 4 cm, and about 50 days after sowing and 1 day after the last cut are sprayed with an aqueous spray mixture of a compound of the formula I. The concentration of test compound corresponds to a rate of application of up to 100 g a.i. per hectare. The growth of the grasses is evaluated 21 days after application. The compounds of formula I effect a reduction in new growth in the range of 10-30% in comparison with untreated controls.
Claims
What is claimed is:
1. A N-arylsulfonyl-N'-pyrimidinylurea of the formula I ##STR23## wherein R.sup.1 is a ##STR24## R.sup.2 is hydrogen, halogen, nitro, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy or --COOR.sup.9, R.sup.3 is hydrogen, C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy, R.sup.4 and R.sup.5 are each independently of the other hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 haloalkylthio, C.sub.2 -C.sub.4 alkoxyalkyl, C.sub.3 -C.sub.6 -cycloalkyl or --NR.sup.10 R.sup.11, R.sup.6 is hydrogen or C.sub.1 -C.sub.3 alkyl, R.sup.7 is hydrogen or methyl, R.sup.8 is C.sub.4 -C.sub.6 cycloalkanonyl which is unsubstituted or substituted by C.sub.1 -C.sub.3 alkyl or halogen; C.sub.3 -C.sub.6 cycloalkyl which is unsubstituted or substituted by one or more identical or different members selected from the group consisting of C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, halogen or cyano; or is C.sub.5 -C.sub.6 cycloalkenyl which is unsubstituted or substituted by C.sub.1 -C.sub.3 alkyl, halogen or cyano, R.sup.9 is C.sub.1 -C.sub.3 alkyl or allyl, R.sup.10 and R.sup.11 are each independently of the other hydrogen or C.sub.1 -C.sub.4 -alkyl, n is 0 or 1, X is sulfur or oxygen, and E is methane and Z is nitrogen or the methine bridge, with the proviso that R.sup.8 is only unsubstituted or substituted C.sub.3 -C.sub.6 cycloalkyl if at the same time Z is nitrogen, or a salt thereof.
2. A compound according to claim 1, wherein Z is nitrogen.
3. A compound according to claim 2, wherein X is oxygen.
4. A compound according to claim 2, wherein R.sup.2 is hydrogen.
5. A compound according to claim 2, wherein R.sup.3 is hydrogen.
6. A compound according to claim 2, wherein R.sup.1 is --O--R.sup.8.
7. A compound according to claim 2, wherein R.sup.1 is --O--CHR.sup.7 -cyclopropyl.
8. A compound according to claim 6, wherein R.sup.8 is C.sub.3 -C.sub.6 cycloalkyl.
9. A compound according to claim 2, wherein R.sup.4 and R.sup.5 are each independently halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, di(C.sub.1 -C.sub.3)alkylamino or C.sub.1 -C.sub.3 haloalkoxy, and together contain not more than 4 carbon atoms.
10. A compound according to claim 2, wherein X is oxygen, R.sup.2 and R.sup.3 is hydrogen, R.sup.4 and R.sup.5 are each independently of the other halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, di(C.sub.1 -C.sub.3)alkylamino or C.sub.1 -C.sub.3 haloalkoxy, and together contain not more than 4 carbon atoms, Z is nitrogen and R.sup.1 is an --O--R.sup.8 radical.
11. A compound according to claim 2, wherein X is oxygen and Z is nitrogen, R.sup.2 and R.sup.3 are hydrogen, R.sup.4 and R.sup.5 are each independently of the other C.sub.1 -C.sub.3 alkyl, halogen, C.sub.1 -C.sub.3 alkoxy, di(C.sub.1 -C.sub.3)alkylamino or C.sub.1 -C.sub.3 haloalkoxy, and together contain not more than 4 carbon atoms, and R.sup.1 is C.sub.3 -C.sub.6 cycloalkoxy.
12. A herbicidal and plant growth inhibiting composition which contains at least one substituted N-arylsulfonyl-N'-pyrimidinylurea of claim 1, together with carriers and/or other adjuvants.
13. A method of controlling undesired plant growth, which comprises applying of an effective amount of a compound of claim 1, or of a composition containing such a compound to the plant or the locus thereof.
14. A method of inhibiting plant growth, which comprises applying of an effective amount of a compound of claim 1, or of a composition containing such a compound to the plant or the locus thereof.
15. A method of influencing plant growth for increasing yield, which comprises applying of an effective amount of a compound of claim 1, or of a composition containing such a compound to the plant or the locus thereof.
16. A method of selectively controlling weeds pre- or postemergence in crops of useful plants, which method comprises applying of an effective amount of a compound as claimed in claim 13, or of a composition containing such a compound to the plant or the locus thereof.
17. A method of inhibiting plant growth beyond the 2-leaf stage preemergence, which method comprises applying of an effective amount of a compound as claimed in claim 14, or of a composition containing such a compound to the plant or the locus thereof.
18. N-(2-cyclopentyloxypyridin-3-ylsulfonyl) -N'-(4,6-dimethoxypyrimidin-2-yl)urea.
19. A compound according to claim 6, wherein R.sup.8 is cyclopentyl or cyclohexyl.
20. A compound according to claim 2, wherein X is oxygen and Z is nitrogen, R.sup.2 and R.sup.3 are hydrogen, R.sup.4 and R.sup.5 are each independently of the other C.sub.1 -C.sub.3 alkyl, halogen, C.sub.1 -C.sub.3 alkoxy, di(C.sub.1 -C.sub.3)alkylamino or C.sub.1 -C.sub.3 haloalkoxy, and together contain not more than 4 carbon atoms, and R.sup.1 is cyclopentyloxy or cyclohexyloxy.