CA1223591A - N-arylsulfonyl-n'-triazinylureas and n-arylsulfonyl- n'-pyrimidinylureas - Google Patents

Abstract

N-Arylsulfonyl-N'-triazinylureas and N-arylsulfonyl-N'-pyrimidinylureas Abstract of the Disclosure N-Arylsulfonyl-N'-triazinylureas and N-arylsulfonyl-N'-pyrimidinyl-ureas of the general formula

Description

~Z355~

N-Arylsulfonyl-N'-trlazinylureas and N-arylsulfonyl-N'-pyrimidinylureas The present invention relates to novel N-arylsulfonyl-N'-triazinyl-ureas and N-arylsulfonyl-N'-pyrimldinylureas with herbicidal and plant growth regulating properties, to the preparation thereof, to compositions containing them as active ingredients, and to methods of using them for controlling weeds, preferably selectively, in crops of useful plants, or for regulating and inhibiting plant growth. The invention further relates to novel aminopyrimidines and aminotriazines prepared as intermediates.

The invention relates to N-arylsulfonyl-N'-triaziDylureas and N-arylsulfonyl-N'-pyrimidinylureas of the general formula I

OSSIFY
X-SOz-NH-~
18 No wherein X it 8 radical of the formula - or \ / R

Y it Cl-C3alkyl~ Cl-C3haloalkyl~ Cl-C3alkoxy, I 3haloalkoxy, Schick alkoxyalkyl, Cl-C3alkylthio, halogen or -NRI6Rl7, Z is oxygen or sulfur, E is nitrogen or the methane bridge -SHEA, W it chlorine or bromide, .

~23~

R1 is hydrogen, halogen, cyan, vitro, C~-C4haloalkyl, C1-C4alkyl, Cl-C4alkoxy, -CRY, -~R7R8, -S(O)m-C1-CI,alkyl or -S02R9, R2 it hydrogen, fluorine, chlorine, bromide, vitro, trifler-methyl, -NR20R2l, methyl, ethyl, methoxy, ethics or -s(o)m-Cl-C4alkYl, R3 is hydrogen, fluorine chlorine, bromide, amino, nicker or methoxy, I is hydrogen, C1-C4alkyl, C3-Csalkenyloxy, C3-C~alkynyloxy, C1-C4haloalkyl~ C1-Csalkylthio, phonics, benzyloxy, -NR10RIl, or is C1-Csalkoxy which is unsubstltuted or substituted by 1 to 3 halogen atoms or C1-C3alkoxy, R7 is hydrogen, methoxy, ethics, C1-C4alkyl or -CRY, R8 is hydrogen or C1-C4alkyl, I is an -0-R1 3 or -NR1~R1s group, R13 is C1-C4alkyl which is unsubstituted or substituted by 1 to 3 halogen atoms, or is phenol or Bunnell, Rl8 is hydrogen, C1-C3alkyl or C1-C3alkoxy and m is 0, 1 or 2, and I has the same meaning as R2; Us has the same meaning as R1;
R1 D, R11, Rl4 and R20 have the same meaning as R7; and R12, R15, Rl6, Rl7 and R21 have the same meaning as R8;
and to the salts thereof.

Ureas, treasons and pyrimidines with herbicidal properties are generally known in the art. Arylsulfamoylheterocyclylaminocarbamoyl compounds with he}bicidal and plant growth regulating properties have recently been described, for example in European patent publications 9 419, 30 141 and 84 020.

In the above definitions, alkyd denotes straight chain or branched alkyd, e.g. methyl, ethyl, n-propyl, isopropyl, or the four bottle isomers.

Alkoxy denotes methoxy, ethics, n-propyloxy, isopropyloxy, the four battleax isomers, n-amyloxy, isoamyloxy, 2-amyloxy or 3-amyloxy, with methoxy, ethics or isopropyloxy being preferred.

Alkylthlo is e.g. methylthio, ethylthio, n-propyl~hio, isopropyl-trio, n-butylthio or n-pentylthio, with methylthio and ethylthio being preferred.

Alkenyl radicals are e.g. vinyl, ally, isopropenyl, l-propenyl, buttonhole, buttonhole, buttonhole, l-isobutenyl, 2-isobutenyl, l-pentenyl, 2-pentenyl, 3-pentenyl and 4-pentenyl 3 with vinyl, ally or 4-pentenyl being preferred.

Alkylsulfinyl is e.g. methylsulfinyl, ethylsulfinyl, n-propyl-sulfinyl sod n-butylsulfinyl, with methylsulfinyl and ethylsulfinyl being preferred.

Alkylsulfonyl is e.g. methylsulfonyl, ethylsulfonyl or n-propyl-sulfonyl, with methylsulfonyl and ethylsulfonyl busing preferred.

In the definitions, halogen by itself and as moiety of haloalkoxy is fluorine, chlorine and bromide, with fluorine and chlorine being preferred.

In the definitions of the above symbols, alkynyl radicals are normally propargyl, buttonhole, buttonhole and pentynyl isomers, with propargyl, buttonhole or buttonhole being preferred.

The invention also comprises the salts which the compounds of formula I are able to form with amine, alkali metal bases and alkaline earth metal bases, or with qua ternary 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 amine are primary, secondary and tertiary aliphat~c and aromatic amine such a methyl amine, ethyl-amine, propylamine, isopropyl amine, the four butylamine isomers, ~35~3~

dimethylamine, diethylamine, diethanolamine, dlpropylamine, dyes-propylamine, di-n-butylamine, pyrrolidine, piperidlne, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine~
pardon, quinoline and isoqulnoline. Preferred amine are ethyl-amine, propylamine, diethylamine or triethylamine, with isopropyl-amine and diethanolamine being most preferred.

Examples of qua ternary ammonium bases are, in general, the cations of haloammonium salts, e.g. the tetramethylammonlum cation, the trimethylbenzylammonium cation, the triethylben~ylammonium cation the tetraethylammonium cation, the trimethylethylammonium cation, and also the ammonium cation.

Among the compounds of formula I of the present invention, those compounds are preferred wherein either a) X is the unsubstltuted or substituted phenol radical or b) Y is a radical containing not more than 2 carbon atoms or c) Z is oxygen or d) E is the methane bride -OH= or e) W is bromide or f) R3 and R4 are hydrogen or g) Al 8 it hydrogen or methyl.

By combining a number of preferred features, the following further preferred group of compounds of formula I is obtained, wherein X is the unsubstituted or substituted phenol radical, Y it a radical containing not more than 2 carbon atoms, Z is oxygen and R3 and Al 8 are hydrogen.

Furthermore, within this group, those compounds are preferred wherein R2 is hydrogen.

A particularly interesting subgroup of compounds of formula I
comprises those compounds wherein X it the un6ubstituted or subset-tuned phenol nucleus, Y is a radical containing not more than ~235~

2 carbon atoms, Z is oxygen, is the methane group, W is bromide and Rl8 it hydrogen, and Al is hydrogen, halogen, vitro, C1-C4-haloalkyl, Cl-C4alkoxy, Cl-C4alkyl, us -Cl-C4alkyl, -SOzN(CH3)z, -SOzOCH2CF3 or -COREY, R2 is hydrogen, fluorine, chlorine, vitro, amino, trifluoromethyl, methyl, methoxy, ethics or us -Cluck-alkyd, R6 it hydrogen, methyl, C3-C5alkenylo~y, C3-Csalkynyloxy, Cl-C3alkylthio, dimethylamino, methyl amino, amino, or is Clucks-alkoxy which is unsubstituted or substituted by 1 to 3 halogen atoms or Cl-C3alkoxy, and m is O, 1 or 2.

Preferred individual compound are:

N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-difluoroobromomethoxy-6-methylpyrimidin-2-yl)urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(difluorobrromomethoxy-4-methylpyrimidin-2-yl)urea and N-(2-nitrophenylsulfonyl)-N'-(4-difluorobromomethooxy-6-methyl-pyrimidin-2-yl)urea.

The preparation of the compounds of formula I it carried out in an inert organic solvent.

In accordance with a first process, the compounds of formula I are obtained by reacting an arylsulfonamide of formula II

X - SO - NH2 (II) wherein X is as defined for formula I, with an N-tria~inylcarbamate or N-pyrimidinylcarbamate of formula III

OSSIFY

wherein Rl8, E, W, Y and Z are as defined for formula I, in the presence of a base.

I, I

In accordance with a second process, compounds of formula I are obtained by reacting an arylsulfonylisocyanate or arylsulfonyliso-thiocyanate of formula IV

X - SO - N - C a Z ( IV) wherein X and Z are as defined for formula I, with an amino-pyrimidine or aminotria~ine of formula V

OSSIFY
X -I YE (V) ~18\N3~
my wherein Rl8, E, W and Y are as defined for formula I, in the absence or presence of a base.

In accordance with a further process, compounds of formula I, wherein Rl8 it hydrogen, are obtained by reacting an arylsulfonamide of the above formula II with an lsocyanate or isothiocyanate of formula VI

OSSIFY
ZcC~N-~ (VI) No wherein E, W, Y and Z are as defined for formula I, in the absence or presence of a base.

Finally, the compounds of formula I can also be obtained by reacting an N-arylsulfonylcarbamate of formula VII

X-SO2-NH-~-O-~ (VII) US

wherein X and Z are as defined for formula I, with an amino-pyrimidine or aminotriazine of the above formula V.

If desired, the resultant ureas of formula I can be converted into addition salts with amine, alkali metal hydroxides or alkalis earth metal hydroxides or with qua ternary ammonium bases This is accomplished e.g. by reaction with the equimolar amount of base and by evaporating off the solvent.

It is convenient to carry out these reactions for obtaining come pounds of formula I in aprotic, inert organic solvents such as ethylene chloride, tetrahydrofuran, acetonitrile, Dixon, Tulane.

The reaction temperatures are preferably in the range from -20C
to +120C. The coupling reactions are normally slightly exothermic and can be carried out with advantage 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.

The bases employed may be organic bases, e.g. amine such as triethylamine, quinuclidine, pardon etc., or inorganic bases, e.g. hydrides such as sodium hydrides or calcium hydrides hydroxides such as sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate or potassium carbonate, or bicarbonates such as potassium bicarbonate or sodium bicarbonate.

The final products of formula I can be isolated by concentrating and/or evaporating off the solvent and purified by recrystallizing or triturating the solid residue in solvents in which they are not readily soluble, e.g. an ether, an aromatic hydrocarbon or a chlorinated hydrocarbon.

The compounds of formula I are stable compounds and no precautionary measures are required for handling them.

I

The intermediates of formulae II, IV and VII are known or can be prepared by methods analogous to known ones.

The intermediates of formula V are novel. They have been specially developed for the synthesis of compounds of formula I and therefore constitute a further object of the present invention.

The compounds of formula V are obtained by reacting an amino-pyrimidine or aminotriszine of formula VIII

OH
Ho (VIII) 18 so wherein I, Rl8 and Y are as defined for formula I, with Delaware-bromochloromethane or difluorodibromomethane, in the presence of a base.

The process for the preparation of compounds of formula V it advantageously carried out in an inert, polar solvent or solvent mixture. Suitable solvents are ethers such as dictions, tetrahydro-Furman, ethylene glycol dim ethyl ether, diethylene glycol dim ethyl ether; alcohols such as methanol, ethanol; kittens such as acetone, ethyl methyl kitten; dimethylformamide; acetonitrile or dim ethyl sulfoxide. Particularly suitable bases are sodium hydrides calcium hydrlde, potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate. In suitable cases, the base may be added in the form of an aqueous solution.

The starting materials of formula VIII are known or can be prepared by methods analogous to known ones.

The intermediates of formulae III and VI are likewise novel. They can be prepared from the intermediates of formula V by methods analogous to known ones.

PA

When used at low rates of application, the compounds of formula I
have good selective growth inhibiting and selective herbicldal properties which make them most suitable for use in crops of useful plants, preferably in sugar cane, cotton, soybeans, maize and rice, and most preferably in cereals. 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 trays-locatable, 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 formula I are effective even when used at very low rates of application.

The compounds of formula I have in addition pronounced growth regulating properties which can take the form of an increase in yield of cultivated plants or harvest produce. Moreover, many compounds of formula I have a plant growth inhibiting action which is dependent on the concentrations in which the compounds are applied. The growth of both monocots and divots is inhibited.

Thus, for example, the compounds of formula I selectively inhibit the growth of leguminous which are frequently planted as cover crops in tropical regions, so that, while isle 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, 80 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.

Inhibition of the vegetative growth of monocots, e.g. grasses or also cultivated plants such as cereals, is sometimes desirable and advantageous. Such a growth inhibition is of economic interest, inter alias in respect of grasses, as the frequency of cutting in flower gardens, parks, sports fields and road shoulders can thereby be reduced. Of importance too is the inhibition of the growth of herbaceous and igneous plants on road shoulders and near trays-mission lines, or generally in areas in which strong growth is undesirable.

The use of growth regulators for inhibiting the growth in height of cereal it also important, as shortening the stalks diminishes or completely eliminates the danger of lodging before harvesting. In addition, growth regulators are able to bring about a strengthening of the stalks in crops of cereals and this too counteracts lodging.

Further, the compounds of formula I are suitable for preventing stored potatoes from seeding. During winter storage, potatoes often develop sprouts which result in shrinkage, weight loss, and rot.

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 formula I, and also to methods of controlling weeds pro- and post emergence and of inhibiting the growth of monocots and divots, especially grasses, tropical cover crops and tobacco plant suckers.

The compounds of formula I are used in unmodified form or, pro-fireball, as compositions together with the adjutants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, directly spray able or dilatable solutions, dilute emulsions, wettable powders, soluble so 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, atomizing, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjutant, 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 (~urfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. zillion mixtures or substituted naphthalenes, phthalates such a dibutyl phthalate or ductile phthalate, aliphatic hydrocarbons such as cyclone or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monthly ether, kittens such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dim ethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidlsed 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 cold or highly dispersed absorbent polymers. Suitable granulated adsorb-live 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 pulverized plant residues.

~35~

Depending on the nature of the compound of formula I to be for-mutated, suitable surface-active compounds are non ionic, cat ionic 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 salt, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Cluck), e.g. the sodium or potassium salts of oleic or Starkey 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 alit methyltaurin salts.

More frequently, however, so-called synthetic surfactant~ are used, especially fatty sulfonates, fatty sulfates, sulfonated benæimid-azalea derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstitued or sub3ti-tuned ammonium salts and contain a Cg-C22alkyl radical which also includes the alkyd moiety of azalea radicals, e.g. the sodium or calcium Walt 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 adduces. The cellophane-ted 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 in-ethanol amine salts of dodecylbenzenesulfonic acid, dibutylnaph-thalenesulfonic acid, or of a naphthalenesulfonic acid/formalde-Hyde condensation product.

I

Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduce 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 10 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the allcyl moiety o f the alkylphenols.

Further suitable non ionic surfactants are the water-soluble adduces of polyethylene oxide with polypropylene glycol, ethylenediamino-polypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyd chain, which adduces contain I 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 nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/-polyethylene oxide adduces, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid ester of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cat ionic surfactants are preferably quatsrnary ammonium salts which contain, as N-substituent, at least one Cg-C2zalkyl radical and, as further substituents, unsubstituted or halogenated lower allcyl, bouncily or hydroxy-lower alkyd radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stroll-trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

23~

The surfactants customarily employed in the art of formulation are described e.g. in the following publications:

"McCutcheon's Detergents and Emulsifiers Annual", MY Publishing Corp., Rouged, New Jersey, 1981; H. Statue, "Tensid-Taschenbuch"
(Handbook of Surfactants),2nd Edition, C. Hanson Verlag, Munich &
Vienna, 1981; M. and J. Ash, "Encyclopedia of Surfactants", Vol.
I-III, Chemical Publishing Co., New York, 1980-81.

The herbicidal compositions usually contain 0.1 to 95 %, preferably 0.1 to 80 %, of a compound of formula I, 1 to 99.9 %, of a solid or liquid Advent, and 0 to 25 %, pro-fireball 0.1 to 25 %, of a ~urfactant.

Preferred formulations are composed in particular of the following constituents (% percentage by weight):

Emulsifiable concentrates active ingredient to 20 %, preferably 5 to 10 %
~urfactant:5 to 30 %, preferably 10 to 20 %
liquid courier to 94 %, preferably 70 to 85 %

Dusts active ingredient to 10 %, preferably 0.1 to 1 %
solid corollary to 90 %, preferably 99.9 to 99 %

Suspension concentrates active ingredient to 75 %, preferably 10 to 50 %
whetter Jo 25 %, prcfèrably 88 to 30 %
surfactant:1 to 40 %, preferably 2 to 30 %

Wettable powders active ingredient to 90 %, preferably 1 to 80 %
surfactant:0.5 to 20 %, preferably 1 to 15 %
solid courier to 95 %, preferably 15 to 90 %

Granulates active ingredient: 0.5 to 30 %, preferably 3 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %.

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 %
of active ingredient. The rates of application are normally from 0.01 to 10 kg aye, preferably from 0.025 to 5 kg aye.

The compositions may also contain further ingredients such as stabilizers, anti foams, viscosity regulators, binders, tackifiers, as well as fertilizers and other compounds for obtaining special effects.

Preparatory Examples xample Pi: No MethoxYcarbonylphenylsulfonyl)-N'-(4-difluoro-bromomethoxy-6-methoxypyrimidin-2-~l)urea a) 7.1 g of 2-amino-4-hydroxy-6-methoxypyrimidine, 7.3 g of potassium carbonate and 20.8 g of dlbromodifluoromethane are shaken for 10 hours at 80C in 50 ml of dimethylformamide in a bomb tube.
The dimethylformamide is removed by evaporation and the residue is token up in ethyl acetate/water. The organic phase is separated and the residue is purified by chromatography over silica gel eluded with toluenelethyl acetate (9:1), affording 2-amino-4-difluoro-bromomethoxy-6-methoxyprimidine as a colorless oil which is further processed direct.

b) 1.3 g of2-amino-4-difluorobromomethoxy-6-methoxypyrimidinee and 1.16 g of 2-methoxycarbonylphenylsulfonylisocyanate are stirred for lo hours at room temperature in 20 ml of ethylene chloride and the reaction mixture is then concentrated by evaporation. The residue it chromatographed over silica gel eluded with ethyl acetate/hexane 35;~

lo affording 1.4 g of N-(2-methoxycarbonylphenylsulfonyl)~N'-(4-difluorobromomethoxy-6-methoxypyrimidln-2-yl)urfee with a molting point of 144-145C.

The intermediates and final products listed in the following Tables are obtained in analogous manner.

Table 1:
OSSIFY
No 18 N=.
y Cc~p~und _ _ _ _ - mop. lC]
Lyle H By SHEA OH 112-113 1.02 H Of SHEA OH
1.03 H By OUCH OH oil 1.04 H Of OUCH OH
1.05 H By OOZE 5 OH
1.06 H Of OOZE OH
1.07 H By CH20CH3 OH
1.08 H Of CHzOCH3 OH
Lowe H By Of OH
l.10 H Of Of OH
lull H By N(CH3)2 OH
1.12 H Of No SHEA OH
1.13 SHEA By OUCH OH
1.14 SHEA Of OUCH OH
1.15 H By OUCH N
1.16 H Of OUCH N
1.17 H By SHEA N
1.18 H Of Cud N __ _ _ I

Table 2:
OSSIFY
SENECA NO
R2 I`_ _ _ Coup. Al R2 y Z W E m.p.[C]
_ _ COUCH H SHEA O By OH 164-165 COUCH H OUCH O By OH 144-145 COUCH H OUCH O Of OH
COUCH H SHEA O Of OH
COUCH H Shea 5 O By OH
COUCH H C2Hs O Of OH
COUCH H OH 2 F O By OH
COUCH H CHEF O Of OH
COUCH H N(CH3)2 O Of OH
COUCH H N(CH3)z O By OH
COOK H Osseous O By OH
COUCH H Osseous O Of OH
COUCH H OUCH O By N
Cook H SHEA O By N
COUCH H SHEA O Of N
COUCH H OUCH O Of N
khakis H OUCH O By OH

I

Table I (continuation) Kelp. Al R2 Z W Z mop. C]
2.18 Khakis H SHEA O By OH
2.19 Couch H SHEA O Of OH
2.20 GooG2Hs H OUCH O Of OH
2.21 Of H OUCH O Of OH
2. 22 Of H SHEA O Of OH
2.23 Of H SHEA O By OH
2.24 Of H OUCH O By OH
2. 25 OUCH H SHEA O By OH
2.26 OUCH H OUCH O By OH
2.27 OUCH 3 H OUCH O Of OH
2.28 OUCH H SHEA O Of OH
2.29 OX ohs H SHEA O Of OH
2.30 Osseous H OUCH O Of OH
2.31 Osseous H OUCH O By OH
2.32 Osseous H SHEA O By OH
2.33 NO H SHEA O By OH 159- 160 2.34 NO H OUCH O By OH
2.35 NO H OUCH O Of OH
2.36 NO H SHEA O Of OH
2.37 SYNCH H SHEA O Of OH
2.38 SYNCH) 2 H OUCH O Of OH
2.39 SYNCH) 2 H OUCH O By C3 aye Table 2: (continuation) Coup. Al R2 _ Z W Z
2.40 SYNCH H SHEA O By OH
2.41 SWISH H SHEA O By OH
2~42 SWISH H OUCH O By OH
2.43 SWISH H OUCH O C1 OH
2.44 SWISH H SHEA O Of OH
2.45 SHEA H SHEA O Of OH
2.46 SHEA H OUCH O Of OH
2.47 SHEA H OUCH O By OH
2.48 SHEA H SHEA O By OH
2.49 By H SHEA O By OH
2.50 By H OUCH O By OH
2.51 By H OUCH O Of OH
2.52 By H SHEA O Of OH
2.53 -(CH2)z-CF3 H SHEA O Of OH
2.54 -(CHECKOFF H OUCH O Of OH
2.55 -(CHECKOFF H OUCH O By OH
2.56 -(CHECKOFF H SHEA O By OH
2.57 CF3 H OUCH O Of OH
2.58 CF3 H SHEA O Of OH
2.59 CF3 H SHEA O By OH
2.60 CF3 H OUCH O By OH
2.61 F H OUCH O By OH
2 . 62 F H SHEA O By CUB

35~

Table 2: (continuation) Co~p.Rl R2 Z W Z
. __ _ _ _ 2.63 F H SHEA O Of OH
2.64 F H OUCH O Of OH
SHEA H OUCH O Of OH

SHEA H SHEA O By OH
SHEA H OUCH O By OH
2.69 Shekel H OUCH O By OH
2.70 Shekel H SHEA O By OH
2.71 Shekel H SHEA O Of OH
2.72 Shekel H OUCH O Of OH
2.73 Sicken H OUCH O Of OH
2.74 Sicken H SHEA O Of OH
2.75 Sicken H SHEA O By OH
2.76 Sicken H OUCH O By OH
2.77 Ozone H OUCH O By OH
2.78 Ozone H SHEA O By OH
2.79 Ozone H SHEA O Of OH
2.80 Ozone H SHEA O Of OH

Formulation Examples Example Fly Fo~lulation Examples for compounds of formula I

(percentages are by weight) a) Wettable powders a) b) c) compound of formula I 20 % 50 % 0.5 %
sodium lignosulfonate 5 % 5 % 5 %
sodium laurylsulfate 3 %
sodium diisobutylnaphthalenesulfonate - 6 % 6 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 % 2 %
highly dispersed silicic acid % 27 % 27 %
kaolin 67 % - -sodium chloride - 59~5 %
The active ingredient is thoroughly mixed with the adjutants 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.

b) Emulsifiable concentrate a) b) compound of formula I 10 % 1 %
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide % 3 %
calcium dodecylbenzenesulfonate 3 % 3 %
castor oil polyglycol ether (36 moles of ethylene oxide % 4 %
cyclohexanone 30 % 10 %
zillion mixture 50 % 79 %
Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

c) Dusts a) b) -compound of formula I 0.1 % 1 %
talcum 99.9 %
kaolin 99 %

Dusts which are ready for use are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.

d) Extrude granulate a) b) compound of formula I 10 % 1 %
sodium lignosulfonate 2 % 2 %
carboxymethylcellulose 1 % 1 %
kaolin 87 % 96 %

The active ingredient is mixed and ground with the Advents, and the mixture is subsequently moistened with water. The mixture it extruded and then dried in a stream of air.

e) Coated granulate compound of formula I 3 %
polyethylene glycol (Malta. 200) 3 %
kaolin 94 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-tusty coated granulates are obtained in this manner.

f) Suspension concentrate a) b) compound of formula I 40 % 5 %
ethylene glycol 10 % 10 %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 % 1 %
sodium lignosulfonate 10 % 5 %
carboxymethylcellulose 1 % 1 %
37 aqueous formaldehyde solution 0.2 % 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 0.8 %
water 32 % 77 %
The finely ground active ingredient is intimately mixed with the adjutants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

g) Salt solution compound of formula I 5 %
isopropyl amine 1 %
octylphenol polyethylene glycol ether (78 moles of ethylene oxide) 3 %
water 91 %
Biological Examples Example By: Reemergence herbicidal action Plastic pots are filled with expanded vermiculite (density:
0.135 g~cm3, water-absorbing capacity: 0.565 l/l). After the non-adsorptive vermiculite has been saturated with an aqueous emulsion in deionized water which contains the test compound in a concentra-lion of 70.8 Pam, seeds of the following plants are sown on the surface: Nasturtium officin~lis, Agro~tis tennis, Digit aria sanguinalis and Styler media. The pots are then kept in a climatic chamber at 20C, an illumination of about 20 flux and a relative humidity of 70 %. During the germinating phase of 4 to so 5 days, the pots are covered with light permeable material and watered with deionized water to increase the local humidity. After the Thea day, 0.5 % of a commercial liquid fertilizer (Greenest, ox 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).

Reemergence action:

Concentration of the test compound emulsion: 70.8 Pam _ _ . . ... . .. ..... .
Test plant Nasturtium Styler Agrostis Digit aria complained 2 1 2 2 Example By: Growth inhibition of tropical leguminous cover crops The test plants (Phosphocarpus pulsators and Centrosema pubescent) are reared until fully grown and then cut back to a height of 15 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 lug artificial light for 14 hours per day, at day tempera-lures of 27C and night temperatures of 21C. The test is evaluated 4 weeks after application by assessing and weighing the new growth compared with controls and by determining the phytotoxicity.

~35~

In this test a marked reduction in new growth of the plants treated with compounds of formula I is observed (less than 20 % of the new growth of untreated control plants).

Example By: Growth regulation of soybeans Soybeans of the "Hark" variety are sown in plastic containers in an earth/pea Sand mixture (6:3:1). The containers are put into a climatic chamber and the plants develop to the 5-6 trefoil loaf stage after about 5 weeks by optimum control of temperature, light, fertilizer addition, and watering. The plants are then sprayed with an aqueous mixture of a compound of formula I until thoroughly wetted. The concentration corresponds to up to 100 g aye. per Hector. Evaluation is made about 5 weeks after application.
Compared with untreated control, the compounds of formula I
markedly increase the number and weight of the harvested Salk on the leading shoot.

Example By: Growth inhibition of cereals Summer barley (Hordeum ~ulgare) and summer rye (Scale) are sown in sterilized soil in plastic pots 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 formula I. The concentration corresponds to up to 100 g of active ingredient per Hector. 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 formula I it reduced (~0~90 % of the controls) and that the diameter of the stalks has in some cases increased.

Example By: Growth inhibition of grasses Seeds of the grasses Lolium porn, Poe pretenses, Fistic ovine, Dactyls glomerate sod Sundown dactyl on 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 l day after the last cut are sprayed with an aqueous spray mixture of a compound of ~Z35~

formula I. The concentration of test compound corresponds to a rate of application of up Jo 100 g aye. per Hector. 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 (23)

What is claimed is:

1. An N-arylsulfonyl-N'-triazinylurea or N-arylsulfonyl-N'-pyrimidinylurea of the general formula I

(I) wherein X is a radical of the formula , Y is C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C2-C3-alkoxyalkyl, C1-C3alkylthio, halogen or -NR16R17, Z is oxygen or sulfur, E is nitrogen or the methine bridge -CH=, W is chlorine or bromine, R1 is hydrogen, halogen, cyano, nitro, C1-C4haloalkyl, C1-C4alkyl, C1-C4alkoxy, -CO-R6, -NR7R8, -S(O)m-C1-C4alkyl or -SO2R9, Ra is hydrogen, fluorine, chlorine, bromine, nitro, trifluoro-methyl, -NR20R21, methyl, ethyl, methoxy, ethoxy or -S(O)m-C1-C4alkyl, R3 is hydrogen, fluorine, chlorine, bromine, amino, nitro or methoxy, R6 is hydrogen, C1-C4alkyl, C3-C5alkenyloxy, C3-C5alkynyloxy, C1-C4haloalkyl, C1-C5alkylthio, phenoxy, benzyloxy, -NR10R11, or is C1-C5alkoxy which is unsubstituted or substituted by 1 to 3 halogen atoms or C1-C3alkoxy, R7 is hydrogen, methoxy, ethoxy, C1-C4alkyl or -CO-R12, R8 is hydrogen or C1-C4alkyl, R9 is an -O-R13 or -NR14R15 group, R13 is C1-C4alkyl which is unsubstituted or substituted by 1 to 3 halogen atoms, or is phenyl or benzyl, R18 is hydrogen, C1-C3alkyl or C1-C3alkoxy and m is 0, 1 or 2, and R4 has the same meaning as R2; R5 has the same meaning as R1;
R10, R11, R14 and R20 have the same meaning as R7; and R12, R15, R16, R17 and R21 have the same meaning as R8;
or a salt thereof.

2. A compound according to claim 1, wherein X is the unsubstituted or substituted phenyl radical.

3. A compound according to claim 1, wherein Y is a radical containing not more than 2 carbon atoms.

4. A compound according to claim 1, wherein Z is oxygen.

5. A compound according to claim 1, wherein E is the methine bridge =CH-.

6. A compound according to claim 1, wherein W is bromine.

7. A compound according to claim 1, wherein R3 and R4 are hydrogen.

8. A compound according to claim 1, wherein R19 is hydrogen or methyl.

9. A compound according to claim 1, wherein X is the unsubstituted or substituted phenyl radical, Y is a radical containing not more than 2 carbon atoms, Z is oxygen and R3 and R18 are hydrogen.

10. A compound according to claim 9, wherein R2 is hydrogen.

11. A compound according to claim 1, wherein X is the unsubstituted or substituted phenyl nucleus, Y is a radical containing not more than 2 carbon atoms, Z is oxygen, E is a methine group =CH-, W is bromine and R18 is hydrogen, and R1 is hydrogen, halogen, nitro, C1-C4haloalkyl, C1-C4alkoxy, C1-C4alkyl, -S(O)m-C1-C4alkyl, -SO2N(CH3)2, -SO2-OCH2CF3 or -CO-R6, RZ is hydrogen, fluorine, chlorine, nitro, amino, trifluoromethyl, methyl, methoxy, ethoxy or -S(O)m-C1-C4alkyl, R6 is hydrogen, methyl, C3-C5alkenyloxy, C3-C5alkynyloxy, C1-C3alkylthio, dimethylamino, methylamino, amino, or is C1-C5alkoxy which is unsubstituted or substituted by 1 to 3 halogen atoms or C1-C3alkoxy, and m is 0, 1 or 2.

12. N-(2-Methoxycarbonylphenylsulfonyl)-N'-(4-difluorobromo-methoxy-6-methylpyrimidin-2-yl)urea according to claim 1.

13. N-(2-Methoxycarbonylphenylsulfonyl)-N'-(4-difluorobromo-methoxy-6-methoxypyrimidin-2-yl)urea according to claim 1.

14. N-(2-Nitrophenylsulfonyl)-N'-(4-difluorobromomethoxy-6-methyl-pyrimidin-2-yl)urea according to claim 1.

15. A process for the preparation of a compound of formula I
according to claim 1, which process comprises a) reacting an arylsulfonamide of formula II

X - SO2 - NH2 (II) wherein X is as defined for formula I, with an N-triazinylcarbamate or N-pyridmidinylcarbamate of formula III

(III) wherein R18, E, W, Y and Z are as defined for formula I, in the presence of a base, or b) reacting an arylsulfonylisocyanate or arylsulfonylisothiocyanate of formula IV

X - SO2 - N = C = Z (IV) wherein X and Z are as defined for formula I, with an amino-pyrimidine or aminotriazine of formula V

(V) wherein R18, E, W and Y are as defined for formula I, in the absence or presence of a base, or c) for the preparation of a compound of formula I according to claim 1, wherein R18 is hydrogen, reacting an arylsulfonamide of the above formula II with an isocyanate or isothiocyanate of formula VI

(VI) wherein E, W, Y and Z are as defined for formula I, in the absence or presence of a base, or d) reacting an N-arylsulfonylcarbamate of formula VII

(VII) wherein X and Z are as defined for formula I, with an amino-pyrimidine or aminotriazine of the above formula V, and, if desired, converting the resultant compound of formula I into a salt by reacting a sulfonylurea of formula I with an amine, an alkali metal hydroxide or an alkaline earth metal hydroxide or with a quaternary ammonium base.

16. A method of controlling undesired plant growth, which method comprises applying to the plants or to the locus thereof an effec-tive amount of an N-arylsulfonyl-N'-triazinylurea or N-arylsulfonyl-N'-pyrimidinylurea of formula I according to claim 1, or of a composition containing such a compound.

17. A method of regulating plant growth, which method comprises applying to the plant or to the locus thereof an effective amount of an N-arylsulfonyl-N'-triazinylurea or N-arylsulfonyl-N'-pyrimidinyl-urea of formula I according to claim 1, or of a composition contain-ing such a compound.

18. A method of regulating the growth of cultivated plants for increasing yield, which method comprises applying to the plants or to the locus thereof an effective amount of an N-arylsulfonyl-N'-triazinylurea or N-arylsulfonyl-N'-pyrimidinylurea of formula I
according to claim 1, or of a composition containing such a compound.

19. A method according to claim 16 of selectively controlling weeds pre- or postemergence in corps of useful plants.

20. A method according to claim 19 of controlling perennial weeds in crops of useful plants.

21. A method according to claim 17 of suppressing plant growth beyond the 2-leaf stage, which method comprises applying the active ingredient premergence.

22. A method according to claim 19, wherein the crops are cereals.

23. A herbicidal composition which contains as active ingredient a compound of formula I according to claim 1, together with a carrier and/or inert adjutants.