US 4,634,465 AGrant
Fused N-Phenylsulfonyl-N'-Pyrimidinylureas and N-Phenylsulfonyl-N'triazinylureas
Issue Date:1987-01-06
•13 Claims
Abstract
The invention relates to N-phenylsulfonyl-N'-pyrimidinylureas and N-phenylsulfonyl-N-triazinylureas of the general formula ##STR1## wherein Z is oxygen or sulfur, and to the salts of these compounds with amines, alkali metal bases or alkaline earth metal bases or with quaternary ammonium bases. These compounds have good pre- and postemergence selective herbicidal and growth regulating properties. E is nitrogen or .dbd.CH--, R.sub.1 is hydrogen, halogen, nitro, 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 alkoxycarbonyl, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkylsulfinyl, C.sub.1 -C.sub.4 alkylsulfonyl or C.sub.2 -C.sub.5 alkoxyalkoxy, R.sub.2 is hydrogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.3 alkoxy, R.sub.3 and R.sub.4, each independently of the other, are hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.1 -C.sub.4 alkylthio, halogen, C.sub.2 -C.sub.5 alkoxyalkyl, C.sub.2 -C.sub.5 alkoxyalkoxy or --NR.sub.5 R.sub.6, wherein R.sub.5 and R.sub.6 are hydrogen or C.sub.1 -C.sub.4 alkyl, and A is an unsubstituted or substituted bridge of 3 or 4 atoms which contains 1 or 2 oxygen, sulfur or nitrogen atoms and, together with the linking carbon atom, forms a non-aromatic 5- or 6-membered heterocyclic ring system, with the proviso that two oxygen atoms are separated by at least one carbon atom and that oxygen and sulfur atoms are only linked to each other if the sulfur atom takes the form of the --SO-- or --SO.sub.2 -- group;
Metadata
Assignee
- Ciba-Geigy Corporation
Inventors
- Josef Ehrenfreund
- Werner Fory
- Willy Meyer
- Werner Topfl
Application Information
Application Number:US 5120918
Filing Date:1983-07-08
Priority Date:1982-07-16
Art Unit:122
Classifications
IPC:
C07D41112A01N 4736
Field of Search:
54471321;332;325;209;21291
Patent Drawings
This patent does not have any drawings.
Description
The present invention relates to novel N-phenylsulfonyl-N'-pyrimidinylureas and N-phenylsulfonyl-N'-triazinylureas having herbicidal and growth regulating properties, to the production thereof, to compositions containing them, and to the use thereof for controlling weeds, in particular selectively, in crops of useful plants, or for regulating and inhibiting plant growth. The invention also relates to novel fused phenylsulfonylisocyanates, phenylsulfonylthioisocyanates, phenylsulfonylcarbamates, phenylsulfonamides and phenylsulfonyl chlorides.
The fused N-phenylsulfonyl-N'-pyrimidinylureas and N-phenylsulfonyl-N'-triazinylureas of this invention, and the salts thereof, have the general formula I ##STR2## wherein Z is oxygen or sulfur,
E is nitrogen or .dbd.CH--,
R.sub.1 is hydrogen, halogen, nitro, 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 alkoxycarbonyl, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkylsulfinyl, C.sub.1 -C.sub.4 alkylsulfonyl or C.sub.2 -C.sub.5 alkoxyalkoxy,
R.sub.2 is hydrogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.3 alkoxy,
R.sub.3 and R.sub.4, each independently of the other, are hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.1 -C.sub.4 alkylthio, halogen, C.sub.2 -C.sub.5 alkoxyalkyl, C.sub.2 -C.sub.5 alkoxyalkoxy or --NR.sub.5 R.sub.6, wherein R.sub.5 and R.sub.6 are hydrogen or C.sub.1 -C.sub.4 alkyl, and
A is an unsubstituted or substituted bridge of 3 or 4 atoms which contains 1 or 2 oxygen, sulfur or nitrogen atoms and, together with the linking carbon atom forms a non-aromatic 5- or 6-membered heterocyclic ring system, with the proviso that two oxygen atoms are separated by at least one carbon atom and that oxygen and sulfur atoms are only linked to each other if the sulfur atom takes the form of the --SO-- or --SO.sub.2 -- group.
Herbicidally active areas, triazines and pyrimidines are generally known in the art. Arylsulfamoyl-heterocyclyl-aminocarbamoyl compounds with herbicidal and plant growth-regulating action have recently been described e.g. in Netherlands patent specification 121 788, U.S. Pat. No. 4,127,405 and in European patent applications 44 807, 44 808 and 51 465.
In the above definitions, alkyl denotes straight-chain or branched alkyl, e.g. methyl, ethyl, n-propyl, isopropyl, or the four butyl isomers. Alkoxy denotes methoxy, ethoxy, n-propoxy, isopropoxy, the four butoxy isomers, n-amyloxy, isoamyloxy, 2-amyloxy or 3-amyloxy, with methoxy, ethoxy or isopropoxy being preferred.
Alkylthio is e.g. methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio or n-pentylthio, with methylthio and ethylthio being preferred.
Alkylsulfinyl is e.g. methylsulfinyl, ethylsulfinyl, n-propylsulfinyl and n-butylsulfinyl, with methylsulfinyl and ethylsulfinyl being preferred.
Alkylsulfonyl is e.g. methylsulfonyl, ethylsulfonyl or n-propylsulfonyl, with methylsulfonyl and ethylsulfonyl being preferred.
Halogen in the above definitions, as well as moiety of haloalkyl, haloalkoxy and haloalkylthio, is fluorine, chlorine and bromine, with fluorine and chlorine 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 and diethanolamine 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.
Examples of suitable substituents of the bridge A are: halogen, cyano, 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 alkylcarbonyl, C.sub.1 -C.sub.4 alkoxycarbonyl, C.sub.1 -C.sub.4 alkylthiocarbonyl, carbamoyl, C.sub.1 -C.sub.4 alkylaminocarbonyl, di(C.sub.1 -C.sub.4)alkylaminocarbonyl, C.sub.1 -C.sub.4 alkylsulfonyl, C.sub.3 -C.sub.5 alkenyl or C.sub.3 -C.sub.5 alkynyl.
Condensed heterocyclic non-aromatic saturated ring systems, in which the sulfur and carbon atoms contained as chain members may also be present in higher stages of oxidation, are formed by the phenyl ring and the fused bridge A. Accordingly, in addition to heterocyclic systems which contain an ether, thioether, acetyl or amino bridge, the present invention also encompasses those heterocyclic systems which contain lactone, lactam, sultone, sultine, sultam or acid anhydride functions or higher oxidation stages of thioether functions.
Typical representatives of the basic types of condensed saturated heterocyclic systems which are formed by the sulfonyl-substituted phenyl ring and the fused bridge A are: 2,3-dihydrobenzo[b]furan, benzodioxole, 2-(3H)-benzofuranone, chromane, dihydrocoumarin, benzodioxan, phthalide, dihydroisocoumarin, 3-isochromanone, indoline, 2,3-dihydrobenzothiophene, 1-oxo-2,3-dihydrobenzothiophene, 1,1-dioxo-2,3-dihydrobenzothiophene, 4-chromanone and 3-chromanone.
Preferred compounds of formula I are those in which either
(a) the substituents of the bridge A are halogen or C.sub.1 -C.sub.4 alkyl, or
(b) the bridge A contains at least one oxygen atom, or
(c) the bridge A contains only one heteroatom, or
(d) Z is oxygen, or
(e) R.sub.1 is hydrogen, halogen or C.sub.1 -C.sub.4 alkoxycarbonyl, or
(f) R.sub.2 is hydrogen, or
(g) R.sub.3 and R.sub.4, independently of each other, are C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, di(C.sub.1 -C.sub.4)alkylamino, C.sub.1 -C.sub.4 haloalkoxy or halogen, and together contain not more than 4 carbon atoms.
Further preferred subgroups comprise those compounds of formula I in which
the bridge A contains an oxygen atom as heteroatom and is unsubstituted or substituted by halogen or C.sub.1 -C.sub.4 alkyl, or
the bridge A contains at least one oxygen atom and is unsubstituted or substituted by halogen or C.sub.1 -C.sub.4 alkyl, or
the bridge A, together with the phenyl nucleus which carries it, forms a 3,4-dihydro-2-dioxo-1,2-benzoxathiine system and is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, or
Z is oxygen, R.sub.1 is hydrogen, halogen or C.sub.1 -C.sub.4 alkoxycarbonyl, R.sub.2 is hydrogen, and each of R.sub.3 and R.sub.4 independently of the other is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, di(C.sub.1 -C.sub.4)alkylamino, C.sub.1 -C.sub.4 haloalkoxy or halogen, and together contain not more than 4 carbon atoms.
Particularly preferred groups of compounds of formula I comprise those compounds in which
Z is oxygen, R.sub.1 is hydrogen, halogen or C.sub.1 -C.sub.4 alkoxycarbonyl, R.sub.2 is hydrogen, each of R.sub.3 and R.sub.4 independently of the other is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, di(C.sub.1 -C.sub.4)alkylamino, C.sub.1 -C.sub.4 haloalkoxy or halogen, and together contain not more than 4 carbon atoms, and the bridge A contains at least one oxygen atom and is unsubstituted or substituted by halogen or C.sub.1 -C.sub.4 alkyl,
or those in which
Z is oxygen, R.sub.1 is hydrogen, halogen or C.sub.1 -C.sub.4 alkoxycarbonyl, R.sub.2 is hydrogen, each of R.sub.3 and R.sub.4 independently of the other is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, di(C.sub.1 -C.sub.4)alkylamino, C.sub.1 -C.sub.4 haloalkoxy or halogen, and together contain not more than 4 carbon atoms, and the bridge A contains only one oxygen atom and is unsubstituted or substituted by halogen or C.sub.1 -C.sub.4 alkyl,
or those in which
Z is oxygen, R.sub.1 is hydrogen, halogen or C.sub.1 -C.sub.4 alkoxycarbonyl, R.sub.2 is hydrogen, each of R.sub.3 and R.sub.4 independently of the other is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, di(C.sub.1 -C.sub.4)alkylamino, C.sub.1 -C.sub.4 haloalkoxy or halogen, and together contain not more than 4 carbon atoms, and the bridge A, together with the phenyl nucleus which carries it, is a 3,4-dihydro-2,2-dioxo-1,2-benzoxathiine system and is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl.
Preferred individual compounds are:
N-chroman-8-ylsulfonyl-N'-(4-methoxy-6-methylpyrimidin-2-yl)urea,
N-(2,3-dihydro-2-methylbenzo[b]furan-7-ylsulfonyl)-N'-(4,6-dimethylpyrimidi n-2-yl)urea,
N-(2,3-dihydro-2-methylbenzo[b]furan-7-ylsulfonyl)-N'-(4-methoxy-6-methylpy rimidin-2-yl)urea.
The process for preparing the compounds of formula I is carried out in an inert organic solvent.
A first process for the preparation of the compounds of formula I comprises reacting a fused phenylsulfonamide of the formula II ##STR3## wherein R.sub.1 and A are as defined for formula I, with an N-pyrimidinylcarbamate or N-triazinylcarbamate of the formula III ##STR4## wherein E, R.sub.2, R.sub.3, R.sub.4 and Z 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 fused phenylsulfonylisocyanate or phenylsulfonylisothiocyanate of the formula IV ##STR5## wherein A, R.sub.1 and Z are as defined for formula I, with an aminopyridine or aminotriazine of the formula V ##STR6## wherein E, R.sub.2, R.sub.3 and R.sub.4 are as defined for formula I, optionally in the presence of a base.
Finally, the compounds of formula I may also be obtained by reacting a fused N-phenylsulfonylcarbamate of the formula VI ##STR7## wherein A, R.sub.1 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 above.
If desired, the ureas of formula I 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 dioxan; 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-diazabicyclo(4,3,0)-non-5-ene or 1,5-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, or bicarbonates such as potassium bicarbonate or sodium bicarbonate.
The final products 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 formulae II, IV and VI are novel and have been specially developed for the synthesis of compounds of the formula I. Accordingly, they constitute an object of the present invention.
The novel intermediates of the formula II can be prepared by different methods. For example, the compounds of formula II are obtained by diazotising anilines of formula VII ##STR8## wherein R.sub.1 and A 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 phenylsulfonyl chloride of the formula X ##STR9## wherein A and R.sub.1 are as defined for formula I, with ammonium hydroxide solution. The corresponding aniline derivatives employed as starting materials are known or they can be prepared by known methods.
Likewise, the compounds of formula II can be obtained by converting a phenylsulfonic acid of the formula VIII ##STR10## wherein R.sub.1 and A 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 the corresponding phenylsulfonyl chloride of the formula X, and reacting this chloride with ammonium hydroxide solution.
The compounds of formula II can also be obtained by treating a benzyl thioether of the formula IX ##STR11## wherein R.sub.1 and A are as defined for formula I, with chlorine, and reacting the resultant phenylsulfonyl chloride of the formula X with ammonium hydroxide solution. In specific cases, for example where an activated substitution position is available, a direct sulfochlorination of the phenyl nucleus is possible, giving the corresponding phenylsulfonyl chloride by reaction with an excess of chlorosulfuric acid. Correspondingly activated fused benzene derivatives are known.
The phenylsulfonylisocyanates of the formula IV, which are also novel, can be obtained by reacting the sulfonamides of the formula II with phosgene, in the presence of butylisocyanate, in a chlorinated hydrocarbon as solvent, at reflux temperature. Similar reactions are described in "Newer Methods of Preparative Organic Chemistry", Vol. VI, 223-241, Academic Press, New York and London.
The isothiocyanates of the formula IV are obtained by treating the sulfonamides of formula II with carbon disulfide and potassium hydroxide and by subsequent reaction of the dipotassium salt with phosgene. Such processes are described in Arch. Pharm. 299, 174 (1966).
The N-phenylsulfonylcarbamates of the formula VI are obtained by reacting the sulfonamides of the formula II with diphenyl carbonate in the presence of a base. Similar processes are described in Japanese patent specification No. 61 169.
The fused phenylsulfonyl chlorides of the formula X, which are also novel, have likewise been specially developed for the synthesis of the compounds of formula I. Accordingly, they also constitute an object of this invention.
The starting aminopyrimidines and aminotriazines of the formula V, as well as corresponding phenylcarbamamtes 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 compounds of formula I are stable compounds, and no protective measures are required for handling them.
When used in 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 in 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 leguminosae 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, whilst 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 application, 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 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 of 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 ammoniums 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 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, castor 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 "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ridgewood, N.J., 1979, and Sisley and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York, 1964.
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 or other active ingredients in order to obtain special effects .
PREPARATORY EXAMPLES
Example 1
(a) 5-Bromo-2,3-dihydro-2-methylbenzo[b]furan
With efficient stirring, 283 g. (1.77 moles) of bromine are added dropwise at 0.degree.-5.degree. C. to a mixture of 237 g (1.77 moles) of 2,3-dihydro-2-methylbenzo[b]furan, 148.7 g (1.77 moles) of sodium bicarbonate, 500 ml of methylene chloride and 500 ml of water. When the addition of bromine is complete, the mixture is stirred for another 1/2 hour at 20.degree.-25.degree. C. The organic phase is separated, dried over sodium sulfate, concentrated and fractionated in vacuo. Yield: 242 g (66% of theory) of 5-bromo-2,3-dihydro-2-methylbenzo[b]furan and 77 g (15% theory) of 5,7-dibromo-2,3-dihydro-2-methylbenzo[b]furan.
(b) 5-Bromo-2,3-dihydro-2-methyl-7-benzo[b]furanylsulfochloride
470 g (4.03 moles) of chlorosulfonic acid are added dropwise over 20 minutes at -7.degree. C. to a solution of 106 g (0.5 mole) of 5-bromo-2,3-dihydro-2-methylbenzo[b]furan in 300 ml of chloroform, and the mixture is then stirred for a further 15 minutes at 20.degree.-25.degree. C. The reaction mixture is taken up in ice/water, the organic phase is separated, and aqueous phase is extracted with two 500 ml portions of chloroform. The combined organic phases are washed with two 250 ml portions of water, dried over sodium sulfate, and concentrated, affording 101 g (65% of theory) of 5-bromo-2,3-dihydro-2-methyl-7-benzo[b]furanylsulfochloride.
(c) 5-Bromo-2,3-dihydro-2-methyl-7-sulfamoylbenzo[b]furan
The crude product obtained in (b) is dissolved in 200 ml of ethyl acetate and the solution is added dropwise at 20.degree.-25.degree. C. to 250 ml of 25% aqueous ammonia. The reaction mixture is stirred for an hour at the same temperature and the organic phase is then separated, treated with activated carbon, dried over sodium sulfate, and concentrated. The residue is crystallised, affording 75 g (80% of theory) of 5-bromo-2,3-dihydro-2-methyl-7-sulfamoylbenzo[b]furan with a melting point of 167.degree.-169.degree. C.
(d) 2,3-Dihydro-2-methyl-7-sulfamoylbenzo[b]furan
72.5 g (0.25 mole) of 5-bromo-2,3-dihydro-2-methyl-7-sulfamoylbenzo[b]furan are hydrogenated in the presence of 22.4 g (0.25 mole) of sodium acetate and 7.5 g of 5% palladium on carbon catalyst in 750 ml of methanol. The catalyst is removed, the solvent evaporated, and the residue crystallised from a mixture of water/ethanol, affording 42.3 g (79% of theory) of 2,3-dihydro-2-methyl-7-sulfamoylbenzo[b]furan with a melting point of 174.degree.-177.degree. C.
(e) N-(2,3-Dihydro-2-methylbenzo[b]furan-7-ylsulfonyl-N'-(4,6-dimethylpyrimidi n-2-yl)urea
3.9 g (0.025 mole) of 1,5-diazabicyclo(5,4,0)undec-5-ene are added to a solution of 5.2 g (0.025 mole) of 2,3-dihydro-2-methyl-7-sulfamoylbenzo[b]furan and 6 g (0.025 mole) of N-(4,6-dimethylpyrimidin-2-yl)phenylcarbamate in 50 ml of acetonitrile, and the mixture is stirred for 2 hours at 20.degree. to 25.degree. C. When the reaction is complete, the mixture is diluted with water and the product crystallises out. The precipitate is isolated, washed with water and hexane, and dried in vacuo over potassium hydroxide. Yield: 7 g (78% of theory) of N-(2,3-dihydro-2-methylbenzo[b]furan-7-ylsulfonyl)-N'-(4,6-dimethylpyrimid in-2-yl)urea with a melting point of 190.degree.-193.degree. C.
Example 2: 1,3-Benzodioxol-4-sulfonamide
(a) 1,3-Benzodioxol-4-sulfonyl chloride
7.5 g of 4-amino-1,3-benzodioxol are suspended in 23 ml of 36% hydrochloric acid. While cooling with ice, diazotisation is effected with a solution of 4.06 g of sodium nitrite in 8 ml of water. To the solution of the diazonium salt is added dropwise a mixture of 50 ml of glacial acetic acid, 5 ml of water, 15 g of sulfur dioxide and 2.3 g of copper (II) chloride hydrate. The temperature is kept constant at 40.degree. C. until the addition to the solution of the diazonium salt is complete. The reaction mixture is then cooled and diluted with 500 ml of ice/water. The crude 1,3-benzodioxol-4-sulfochloride is isolated and dried. Melting point: 121.degree.-124.degree. C.
(b) 1,3-Benzodioxol-4-sulfonamide
The 1,3-benzodioxol-4-sulfochloride obtained in (a) is dissolved in 20 ml of ethyl acetate and the solution is added dropwise at 20.degree.-25.degree. C. to 25 ml of 25% aqueous ammonia. This mixture is stirred for 1 hour at the same temperature. The organic phase is separated, dried and concentrated, affording 1,3-benzodioxol-4-sulfonamide.
Example 3: 2,3-Dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonylisocyanate
(a) N-(2,3-Dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonyl)-N'-methylurea
6.54 ml of 1,5-diazabicyclo(5,4,0)undec-5-ene are added to 9.9 g (0.0436 mole) of 2,3-dihydro-2,2-dimethyl-7-sulfamoylbenzo[b]furan (compound 1.4) in dioxan. While cooling with ice, 2.65 ml of methyl isocyanate are added dropwise. The reaction mixture is stirred for 2 hours at 20.degree. to 25.degree. C., then diluted with water, neutralised with 10 ml of 5% sodium carbonate solution, and filtered. Acidification of the filtrate yields 11.1 g (89.5% of theory) of N-(2,3-dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonyl)-N'-methylurea.
(b) 2,3-Dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonylisocyanate
8 g of N-(2,3-dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonyl)-N'-methylurea are dispersed in 400 ml of absolute chlorobenzene and the dispersion is saturated with phosgene at about 130.degree. C., whereupon a clear solution forms. The solvent is then destilled off in vacuo, with the exclusion of moisture, to give 2,3-dihydro-2,2-dimethylbenzo[b]furan-7-ylsulfonylisocyanate in the form of an oil, which can be used without further purification for obtaining the fused N-phenylsulfonyl-N'-pyrimidinylureas and N-phenylsulfonyl-N'-triazinylureas of the formula I.
The intermediates and final products listed in the following tables are obtained in corresponding manner.
The ring system numbers additionally listed in Table 1 refer only to the fused phenyl ring and are employed for the same substituent in the subsequent tables.
Example 4: 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 5: Preemergence herbicidal action
Plastic pots are filled with expanded vermiculite (density: 0.135 g/cm.sup.3, water-absorbing capacity: 0.565 1/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 lux and a relative humidity of 70%. During the germinating phase of 4 to 5 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.) 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:
Preemergence action:
Concentration of the test compound emulsion: 70.8 ppm
Example 6: Selective preemergence action in cotton
In a greenhouse, seeds of cotton and of the weeds associated with them are sown in flower pots of 12-15 cm diameter. Immediately afterwards the surface of the soil is treated with an aqueous dispersion or solution of the test compounds. Concentrations of 125 and 30 g/ha are employed. The pots are then kept in the greenhouse at a temperature of 22.degree. to 25.degree. C. and at 50 to 70% relative humidity. The test is evaluated 3 weeks later and the action is assessed in accordance with the rating indicated in Example 5.
Example 7: Postemergence herbicidal action (contact action)
A number of weeds and cultivated plants, both monocots and dicots, are sprayed postemergence, in the 4- to 6-leaf stage, with an aqueous dispersion of test compound at a rate of application of 0.5 kg a.i./ha, and then kept at 24.degree. to 26.degree. and 45 to 60% relative humidity. The test is evaluated 15 days after treatment using the same rating as in the preemergence test.
Preemergence action
Rate of application: 0.5 kg/ha
Example 8: 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.
Claims
What is claimed is:
1. A fused N-phenylsulfonyl-N'-pyrimidinylurea or N-phenylsulfonyl-N'-triazinylurea of the formula ##STR60## wherein Z is oxygen or sulfur, E is nitrogen or .dbd.CH--, R.sub.1 is hydrogen, halogen, nitro, 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 alkoxycarbonyl, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkylsulfinyl, C.sub.1 -C.sub.4 alkylsulfonyl or C.sub.2 -C.sub.5 alkoxyalkoxy, R.sub.2 is hydrogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.3 alkoxy, R.sub.3 and R.sub.4, each independently of the other, are hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.1 -C.sub.4 alkylthio, halogen, C.sub.2 -C.sub.5 alkoxyalkyl, C.sub.2 -C.sub.5 alkoxyalkoxy or --NR.sub.5 R.sub.6, wherein R.sub.5 and R.sub.6 are hydrogen or C.sub.1 -C.sub.4 alkyl, and the bridge A, together with the phenyl nucleus which carries it, forms a 3,4-dihydro-2,2-dioxo-1,2-benzoxathiine system which is substituted by C.sub.1 -C.sub.4 alkyl.
2. A compound according to claim 1, wherein Z is oxygen, R.sub.1 is hydrogen, halogen or C.sub.1 -C.sub.4 alkoxycarbonyl, R.sub.2 is hydrogen, each of R.sub.3 and R.sub.4 independently of the other is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, di(C.sub.1 -C.sub.4)alkylamino, C.sub.1 -C.sub.4 haloalkoxy or halogen, and together contain not more than 4 carbon atoms.
3. N-(3,4-Dihy dro-2,2-dioxo-3-methyl-1,2-benzoxathiin-8-sulfonyl)-N'-(4-methoxy-6-methyly pyrimidin-2-yl)-urea according to claim 1.
4. N-(3,4-dihydro-2,2-dioxo-3-methyl-1,2-benzoxathiin-8-yl sulfonyl)-N'-(4,6-dimethoxy pyrimidin-2-yl)urea.
5. N-(3,4-dihydro-2,2-dioxo-3-methyl-1,2-benzoxat hiin-8-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea.
6. N-(3,4-dihydro-2,2-dioxo-3-methyl-1,2-benzoxathiin-8-yl sulfonyl)-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)urea.
7. The compound of claim 1 wherein said 3,4-dihydro-2,2-dioxo-1,2-benzoxathiine system is substituted by a methyl group in the 3-position thereof.
8. A herbicidal and plant growth inhibiting composition which contains an effective amount at least one fused N-phenylsulfonyl-N'-pyrimidinylurea or N-phenylsulfonyl-N'-triazinylureas of the formula ##STR61## wherein Z is oxygen or sulfur, E is nitrogen or .dbd.CH--, R.sub.1 is hydrogen, halogen, nitro, 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 alkoxycarbonyl, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkylsulfinyl, C.sub.1 -C.sub.4 alkylsulfonyl or C.sub.2 -C.sub.5 alkoxyalkoxy, R.sub.2 is hydrogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.3 alkoxy, R.sub.3 and R.sub.4, each independently of the other, are hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.1 -C.sub.4 alkylthio, halogen, C.sub.2 -C.sub.5 alkoxyalkyl, C.sub.2 -C.sub.5 alkoxyalkoxy or --NR.sub.5 R.sub.6, wherein R.sub.5 and R.sub.6 are hydrogen or C.sub.1 -C.sub.4 alkyl, and the bridge A, together with phenyl nucleus which carries it, forms a 3,4-dihydro-2,2-dioxo-1,2-benzoxathiine system which is substituted by C.sub.1 -C.sub.4 alkyl, together with carriers and/or others adjuvants.
9. A method of controlling undesired plant growth, which comprises applying an effective amount of a composition of claim 8 to the plant or the locus thereof.
10. A method of inhibiting plant growth, which comprises applying an effective amount of a composition of claim 8 to the plant or the locus thereof.
11. A method of influencing plant growth for increasing yield, which comprises applying an effective amount of a composition of claim 8 to the plant or the locus thereof.
12. A method according to claim 9 for selectively controlling weeds pre- or postemergence in crops of useful plants.
13. A method for inhibiting plant growth beyond the 2-leaf stage which method comprises preemergence applying an effective amount of a composition of claim 8 to the locus of the plant.