NZ225160A

NZ225160A - Sulphonylurea derivatives and herbicidal compositions

Info

Publication number: NZ225160A
Application number: NZ225160A
Authority: NZ
Inventors: Guy Borrod; Alain Gadras
Original assignee: Rhone Poulenc Agrochimie
Priority date: 1987-06-25
Filing date: 1988-06-24
Publication date: 1990-11-27
Also published as: EP0297000A3; MY103737A; AU608332B2; EP0297000A2; AU1839188A; FR2628427A2

Description

New Zealand Paient Spedficaiion for Paient Number £25160 22 5 1 6 0 WO DRAWINGS Priority Date(s): Complete Specification Filed;?^'.t^5L-cias«.- _.

Publication Date: P.O. Jourrva!, No: NEW ZEALAND Class Cont: .fr\.Q I )ASS/d£>/. .k>&.t7o^ £oP7.0^/3^" Class Cone ... c V. CQ.7p2g,.(/ PATENTS ACT 1953 ! .A!* ' PATENTS FORM NO. 5 COMPLETE SPECIFICATION PH 2687/2687A "SPLPgQNYLUREA-TYPE HERBICIDES, THEIR PREPARATION, PREPARATIONS CONTAINING TEEM. AND THEIR USE" WE, RHONE-POULENC AGROCHIKIE, A French Body Corporate of H-20 Rue Pierre B&izet, Lyon 9e, France, hereby declare the invention for Which ve pray that a patent inay be granted to us and the method by Which it is to be performed, to be particularly described in and by the following statement: -1- (followed by page la) 1 I ef 1 2 1 rs > . 0 f> ft i nA * •* ** -i^ The present invention relates to novel silicon-containing sulphonylureas having herbicidal activity, compositions containing them, processes for their preparation, and their use.

Sulphonylurea-type compounds for use as herbicides are mentioned in numerous earlier documents, including EP-A-0,030,139, EP-A-0,209,230 and EP-A-0,212,779.

The present invention seeks to provide compounds exhibiting herbicidal activity with the aim of providing 10 compounds exhibiting selective herbicidal activity with particular regard to cereals, maize, sugar beet, sunflower, rice, soya beans, cotton and oil seed rape.

These aims are partly or completely achieved by means of the compounds of the invention. 15 The present invention accordingly provides sulphonylureas of the general formula: L-S02-NH-C0-NR6-A (I) in which: L represents one of the groups of the formulae L-l to L-6 20 depicted below and A represents a group of the formula depicted below: , 2 2 5100 ^_SiRjR2R3 o 8 R9 L-3 ll^-^SiRlR2R3 L-3 R-7 v ^ ^2^3 (0) m L-2 A. Z^siRiVs 11 z L-A SiRjR^ f V XN / I 11 , C/s siRiR2R: 11 L-6 ! -</ x K (•A) wherein R^, R2 and R3, which are identical or different, each represents a C^-C^ alkyl radical or a C7~C^ aralkyl radical, especially benzyl; Ry, Rg and R^, which are identical or different, each represents a hydrogen or halogen atom, a C^-C^ alkyl radical which is optionally substituted by one or more halogen atoms or C^-C^ alkoxy or C^-C^ alkylthio radicals, a C-j-Cg 225160 cycloalkyl radical which is optionally substituted by one or more halogen atoms or C1-C4 alkoxy or alkylthio radicals, a C^-C4 alkoxy or C^-C4 alkylthio radical each of which is optionally substituted by one or more halogen atoms 5 or C1~C4 alkoxy or C^-C4 alkylthio radicals, a group R13-S(0)n~, in which n is 1 or 2 and represents a C^-C4 alkyl radical which is optionally substituted by one or more halogen atoms or C^-C4 alkoxy or C^-C4 alkylthio radicals, a group COOR14, in which R14 is a hydrogen atom, or a C^-C4 10 alkyl or C^-Cg cycloalkyl radical each of which is optionally substituted by one or more halogen atoms or C^-C4 alkoxy or C^-C4 alkylthio radicals, or a C^-Cg alkenyl radical which is optionally substituted by one or more halogen atoms; R1q and R^ are identical or different and are as hereinbefore defined for R^, with the exception of the halogen atom; m is 0 or 1; Z is the oxygen atom, the sulphur atom or a group =N~R^2 *n which R12 represents a C^-Cg alkyl, Cg-C1Q aryl or 20 aralkyl radical, preferably methyl; X is —CH= or -N=, preferably -N=; R4 and R5 are identical or different and each represents a ^1~C4 alkyl ra<3ical (preferably methyl) , a C^-C4 alkoxy <r> 22 5 1 6 0 radical (preferably methoxy), a C^-C^ alkylthio radical (preferably methylthio), a C^-C4 haloalkyl radical (preferably trifluoromethyl), a C^-C^ haloalkoxy radical (preferably di- or tri-fluoromethoxy), a C^-C4 haloalkylthio 5 radical (preferably trifluoromethylthio), a Cj-Cg alkoxyalkyl radical (preferably methoxymethyl), a C2-Cg ' alkoxyalkoxy radical (preferably raethoxyraethoxy), a alkylamino radical, a di(C^-C4 alkyl) amino radical or a halogen atom (preferably chlorine); and 10 Rg represents the hydrogen atom or a alkyl radical (preferably methyl) (advantageously, Rg is the hydrogen atom); and agriculturally acceptable salts thereof.

Suitable salts are known and include especially those which are formed with mineral bases, e.g. sodium hydroxide, 15 potassium hydroxide and alkylammonium hydroxides.

L preferably represents the group L-l.

R^, R2 and R^ preferably each represent the methyl radical. R^ and Rg, which are identical or different, preferably represent a halogen atom (preferably the chlorine atom), a 20 C^-C4 alkyl radical (preferably methyl), a C]_-C4 alkoxy radical (preferably methoxy), a C^-C4 haloalkoxy radical (preferably difluoromethoxy). Ci-C4 alkylthio, cj~c4 alkoxy, R13S02, R13 being a C1~C4 alkyl radical. :5100 o i^0 and Rj^» which are identical or different R^, Rg and Rg, which are identical or different, preferably represent a halogen atom, a hydrogen atom or a C^-C4 alkoxy radical; R^, Rg and Rg most preferably represent the hydrogen atom. • 5 R] each represent a hydrogen atom or a ^-C^j alkoxy radical; and R1q and most preferably represent the hydrogen atom.

According to a feature of the present invention the silicon-containing sulphonylureas of the formula (I) can 10 be obtained by reacting an aminopyrimidine or an aminotriazine of the formula A-NHRg/ wherein A is as hereinbefore defined, with a sulphonyl isocyanate of the formula (III) L-S02~NC0; the reaction is preferably carried out using a stoichiometric quantity of isocyanate, in an 15 inert solvent such as chloroform, acetonitrile, toluene, xylene or chloroben2ene, at a temperature from 20 to 100°C.

The sulphonyl isocyanate's of the formula (III) p can be obtained by reacting phosgene with a sulphonamide of the formula (IV) L-S02-NH2, preferably with an excess of 20 phosgene (1.5 to 15 moles), in the presence of an alkyl (preferably butyl) isocyanate in a proportion of 10 to 100% of the stoichiometry, and in the presence of a catalytic amount of a tertiary amine (for ex^B^e^-i^-diazabicyclo- 225160 [2.2.2]octane) in an inert solvent having a high boiling point, such as: xylene, chlorobenzene, dichlorobenzene or tetralin; the reaction is generally carried out at temperatures from 120 to 200°C.

When , Rg and Rg are other than the halogen atom, the sulphonamides of the formula (IV) can be obtained by reacting a compound of the formula (V) L-SiR^RjRg with sulphamoyl chloride ClSOjNE^/ in the presence of aluminium trichloride, as described for example in Journal of Chemical 10 Research (s) , 1982, pages 16-17, P. Babin et al.

The compounds of formula (V), which are ortho-di-(trialkylsilane)aryls, can be prepared by reacting a compound of the formula (VI) R-Hal, wherein R has one of the meanings of the group L, except that the group SiR^^Rg 15 is replaced by the Hal radical, Hal being a bromine or chlorine atom, with a silyl chloride, e.g. trimethylsilane chloride, in the presence of magnesium, as described for example in Journal of Organometallic Chemistry _84 (1975), pages 165-175, Bourgeois et al.

The compounds of the formulae A-NHRg and (VI) are obtained in a known manner. For the compounds of the formula A-NHRg reference is made for example to the document EP-A-0,209,230, columns 45 and 46.

According to a further feature of the present 225160 invention the silicon-containing sulphonylureas of the formula (I) can also be obtained by reacting a pyrimidinyl or triazinyl aryl carbamate of the formula (XII) Ph-O-CO-NR^-A, wherein A is as hereinbefore defined and Ph is an aryl ring, 5 preferably phenyl, with a sulphonamide of the formula (IV); the reaction is preferably carried out using a stoichiometric quantity of sulphonamide, in the presence of a tertiary amine (for example 1,8-diazabicyclo[5.4.0]undec-7-ene) in an inert solvent, such as chloroform, 10 acetonitrile, acetone, tetrahydrofuran or dioxan, at a temperature from 20 to 100°C.

The aryl carbamates of the formula (XII) can be obtained by reacting an aryl chloroformate, preferably phenyl chloroformate, with an amine of the formula A-MHR^, 15 wherein A is as hereinbefore defined, in the presence of an amine such as pyridine, in a polar aprotic solvent, such as tetrahydrofuran, preferably at room temperature.

Alternatively, the sulphonamides of the formula 20 (IV) can be obtained from N-tert-butylsulphonamides (VII) L-S02~NH-C(CHg)g, by treating them in an acid medium, such as hydrochloric acid in methanol or trifluoroacetic acid, at room temperature. 225160 obtained by reacting an organolithium compound, preferably n-butyl-lithium, with a sulphonamide of the formula (VIII) Q-SOj-NH-C(CHg)2, wherein Q has the same meaning as L except that the SiR^RjR^ group is replaced by the hydrogen atom, in 5 an ether-containing solvent and at -78°C to 20°C, following a process similar to the one described in Journal of Organic Chemistry, ^36 (1971), pages 1843-1845, J.G. Lombardino. The resulting dilithium intermediate is treated with a silyl chloride, e.g. trimethylsilyl chloride, for 1 to 5 hrs at 10 -30°C to 20°C to give (VII).

The sulphonamides of the formula (VIII) can be prepared from sulphonyl chlorides (IX) Q-S02-C1 and tert-butylamine, in accordance with the methods described in "The sulfonamides" H.K. Lewis and Co., London, 1950, F. 15 Hawking and J.S. Lawrence.

The sulphonyl chlorides (IX) can be obtained either by oxidizing a thiol or a sulphide of the formula (XI) Q-SH or Q-S-R15, R^5 being a C^-Cg alkyl, Cg-C10 aryl or C^-C^^ aralkyl group, with chlorine in the presence of 20 water and in a solvent, such as acetic acid, as described in Canadian Journal of Chemistry, 54 (1976) , pages 498-499, R.F. Langler, or from an amine of the formula (X) Q-NH2f by diazotizing it with sodium nitrite in hydrochloric acid, and then reacting the resulting diazonium salt with sulphur 25 dioxide in the presence of cupric chloride, in acetic acid, as described in Journal of Organic Chemistry, 25 (1960), 225160 page 1824, Yale, Sowinski. In the case where Q denotes L-4 and R1q and denote the hydrogen atom, the compound of the formula (IX) can be prepared from the sulphonic acid as described by A. Arcoria et al in the Journal of Organic 5 Chemistry, J39 (1974), pages 1689-1691.

In the formulae (II) to (XII), the various substituents have the same meanings as in formula (I).

The compounds of the formulae (III) to (V) are novel and constitute features of the invention. 10 The invention also relates to the use of the compounds of the formula (I) as herbicides.

The compounds of the formula (I) are generally used in the form of a herbicidal composition comprising one or more agriculturally acceptable excipients. 15 As a matter of fact, the compounds according to the invention are rarely used on their own for their practical application. Most frequently, these compounds are part of compositions. These compositions which can be used as herbicidal agents contain, as the active substance, a 20 compound according to the invention as described above in a mixture with solid or liquid excipients which are agriculturally acceptable and surfactants which are also agriculturally acceptable. Specific excipients which may be used are the customary inert excipients and the customary 22 5 1 6 0 surfactants.

The present invention accordingly provides a herbicidal composition which comprises a compound of general formula (I) or an agriculturally acceptable salt thereof in association with an agriculturally acceptable diluent or carrier and/or surface active agent.

These compositions may also contain a variety of other components such as, for example, protecting colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers and sequestering agents. More generally, the compounds used in the invention may be mixed with all solid or liquid additives corresponding to customary formulation techniques.

The application rates of the compounds used in the invention may be varied within a wide range, especially depending on the nature of the weeds to be destroyed and the degree of infestation of the crops with the weeds.

Generally, the compositions according to the invention usually contain about 0.05 to 95% (by weight) of a compound according to the invention, one or more solid or liquid excipients and, if appropriate, one or more surfactants.

In the present description, the expression "excipient" is taken to mean an organic or inorganic natural or synthetic substance with which the compound is mixed in 22 5 1 6 0 order to facilitate its application on the plant, on seeds or on the soil. Thus, this excipient is generally inert and it roust be agriculturally acceptable, in particular on the treated plant. The excipient may be solid (e.g. clays, 5 natural or synthetic silicates, silica, resins, waxes or solid fertilizers) or liquid (e.g. water and alcohols, especially butanol).

The surfactant may be an emulsifier, dispersing agent or ionic or non-ionic wetting agent, or a mixture of\ 10 these surfactants. Examples which may be mentioned are salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (especially 15 alkyl phenols or aryl phenols), salts of sulphosuccinic acid esters, taurine derivatives (especially alkyltaurides), phosphoric esters of polycondensates of ethylene oxide with alcohols or phenol, esters of fatty acids and polyols, or sulphate, sulphonate and phosphate derivatives of the above 20 compounds. Generally, the presence of at least one surfactant is indispensable if the compound and/or the inert excipient is/are not water-soluble, and the carrier agent of the application is water. 22 5 1 6 0 For their application, the compounds are thus generally present in the form of compositions. These compositions according to the invention are in a variety of forms, solid or liquid.

Solid compositions include powders for dusting (having a content of compound of up to 100%) and granules, especially those obtained by extrusion, by compression, by impregnating a granulated excipient, by granulation of a powder (the content of compound in these granules being 10 between 0.5 and 80%, for the latter cases).

Liquid compositions or compositions to give liquid compositions for application include flowables.

The flowables, which can be applied by spraying are prepared such that a stable fluid product which does not 15 settle is obtained (fine grinding), and they usually contain 10 to 75% of compound, 0.5 to 30% of surfactants, 0.1 to 30% of thixotropic agents, 0 to 30% of appropriate additives, such as antifoams, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as excipient, water or 20 an organic liquid in which the active substance is scarcely soluble or insoluble: certain organic solids or mineral salts may be dissolved in the excipient in order to prevent settling, or as antifreeze for the water.

In the following composition Examples "compound" 22 5 1 6 0 is a compound of general formula I.

By way of example, the following is a preparation of a flowable: Composition Example 1 - compound 500 g - polycondensate of ethylene oxide with tristyrylphenol phosphate 50 g - polycondensate of ethylene oxide with alkylphenol 50 g - sodium polycarboxylate 20 g - ethylene glycol 50 g organopolysiloxane oil (antifoam) 1 g - polysaccharide 1.5 g - water 316.5 g The wettable powders (or powders for spraying) are usually prepared in a manner such that they contain 20 to 90% of compound, and they usually contain 0 to 15% of a wetting agent, 3 to 10% of a dispersing agent, and, if this should be necessary, 0 to 15% of one or more stabilizers 20 and/or other additives, such as penetrating agents adhesives, or anti-caking agents or colorants, in addition to the solid excipient. 1 O ••fw G 22 5 1 6 By way of example, the following are various preparations of wettable powders: Composition Example 2 compound 50 % - calcium lignosulphonate (antiflocculant) 5 % Ws- .'■ib, • -fa ■ / ...' • ... \ n r^--. v '; 22 5 1 6 0 #£ • -15- f # - isopropylnaphthalenesulphonate (anionic wetting agent) 1 X - anti-caking silica 5 X -kaolin (filler) 39 Composition Example 3 - compound 80 X - sodium alkylnaphthalenesulphonate 2 . X - sodium Iignosulphonate 2 X - anti-caking silica 3 X 10 - kaolio 13 X Composition Example 4 - compound -50 X - sodium alkylnaphthalenesulphonate 2 X - low-viscosity methylcellulose 2 X 15 - diatomaceous earth 46 X S"\ i/ Composition Example 5 - compound 90 X - sodium dioctylsulphosuccinate 0.2 X - synthetic silica 9.8 X t Composition Example 6 - compound 400 g - sodium Iignosulphonate 50 g - sodium dibutylnaphthalenesulphonate 10 g - silica 540 g 25 Composition Example 7 - compound 250 g - isooctylphenoxy(polyoxyethylene)ethanol 25 g 22 5 1 6 0 mixture of equal parts by weight of Champagne chalk and hydroxyethylcellulose 17 g - sodium aluminosilicate 543 g kieselguhr 165 g Composition Example 8 - compound 100 g - mixture of sodium sulphate salts of saturated fatty acids 30 g condensation product of naphthalenesulphonic acid and formaldehyde 50 g - kaolin 820 g In order to obtain these powders for spraying or wettable powders, the active substances are mixed intimately, in appropriate mixers, with the additives, or 15 the porous filler is impregnated with the compound and ground in mills or other suitable grinders. Thus, powders for spraying are obtained, the wettability and the suspendability of which powders are advantageous; they can be suspended in water at any desired concentration. 20 The composition of dry flowables is substantially similar to that of wettable powders. They can be prepared by granulating the formulations described for the wettable powders, either by the moist way (the finely-divided compound being brought into contact with the inert filler 22 5 1 6 0 and with a small quantity of water, for example 1 to 20%, or of an aqueous solution of dispersant or binder, followed by drying and sieving), or the dry way (compressing followed by grinding and sieving).

The following formulation is an example of a dry flowable Composition Example 9 compound 800 g sodium alkylnaphthalenesulphonate 20 g - sodium methylenebis(naphthalenesulphonate) 80 g kaolin 100 g Instead of wettable powders, pastes may be produced. The conditions and methods of production and use of these pastes are similar to those of wettable powders or 15 powders for spraying.

As already mentioned, the dispersions and aqueous emulsions, for example the preparations which are obtained by diluting a wettable powder according to the invention, by means of water, are encompassed in the general scope of the 20 compositions which can be used in the present invention.

All these aqueous dispersions or emulsions or slurries can be applied to crops for weeding in any convenient way, mainly by spraying, at application rates I 22 5 1 6 0 which are generally of the order of 50 to 500 litres of slurry per hectare.

The granules to be deposited on the soil are usually prepared in a manner such that their dimensions are 5 between 0.1 and 2mra, and they can be produced by compressing or impregnating. Preferably, the granules contain 1 to 95% of compound and 0 to 50% of additives, such as stabilizers, slow-release agents, binders and solvents.

Following an example of the preparation of 10 granules, the following constituents are used Composition Example 10 - compound 50 g - propylene glycol 25 g linseed oil mixture 50 g - clay (particle size : 0.3 to 0.8 mm) 910 g The present invention also provides a method of controlling the growth of weeds at a locus which comprises the application to the locus of an effective amount of a compound of general formula (I) or an agriculturally 20 acceptable salt thereof.

The compounds and compositions according to the invention are generally applied to the vegetation and especially to the weeds to be eliminated when they have a green foliage. 225160 Alternatively, the invention provides a method of weeding which consists in applying an effective quantity of a compound of the formula (I) to the areas or places where it is desirable to prevent' growth or development of plants which have not yet emerged (pre-emergence treatment), for « the compounds suitable for this application. Likewise, a procedure may be followed such that the crop is sown either before or after the treatment.

In general, the active substance is applied at 10 application rates between 1 and 2,000 g/ha, preferably between 5 and 1,000 g/ha (generally 50 to 500 litres of slurry per hectare).

The following Examples illustrate the invention.

Example No. 1 Preparation of N-tert-butyl-2-(triethylsilyl)benzene-sulphonamide (product comes under formula VII). 30g (0.14 mole) of N-tert-butylbenzene-sulphonamide and 500ml of tetrahydrofuran are introduced in a three-neck round-bottom 1,000ml flask which is equipped 20 with two funnels, and through which argon is passed. 200ml of 1.6 N n-butyllithium (0.32 mole) are then introduced in one funnel. The tetrahydrofuran solution is cooled to -30°C, and the n-butyllithium is then added at this temperatu're. The solution is clear at the beginning 22 5 1 6 0 and turns yellow and eventually orange when the addition has ended. The mixture is allowed to warm to 0°C, maintained at 0°C for half an hour, and then cooled again to -20°C. In the second funnel, 50ml (0.3 mole) of triethylsilyl chloride 5 are introduced and added dropwise at 20°C to the previously formed salt. The mixture is allowed to come to room temperature and is then hydrolysed with 30ml of a 6 N hydrochloric acid solution. The solution is then washed to neutrality with 300ml of a saturated ammonium chloride 10 solution, dried over magnesium sulphate and concentrated. 38g of a solid in the form of a il 22 5 1 6 0 o o paste is obtained, which is recrysta 11ized from 70 ml of heptane. N-tert-butyltriethyl-2-(silyl)benzenesulphonamide is obtained in the form of a white powder, netting point 98.6°C.

Mass collected: 35 g. Yield: 76X TABLE (I) Compounds of the formula (VII) in which Rs/RlO and R1-j stand for the hydrogen atom, which are prepared in accordance with Example 1 O c Ex.

Preparation of 2-(triethyIsiIyI)benzenesuIphonamide (The product comes under the formula IV). 16.5 g (50 mmol) of N-tert-but'yl-2-(triethylsilyl)-benzenesulphonamide are dissolved in 80 ml of trifluoro-15 acetic acid in a one-neck round-bottom 250-ml flask. The ^ "■! jv :='"""r,-1 :«,. ,-..., \ JL-.W .J.,, ■ - -" I v - ^ 225160 mixture is maintained at room temperature for 2 h, with stirring.

The trifIuoroacetic acid is then removed in vacuo, and the resulting residue is taken up in 60 ml of heptane. 5 2-(Triethy IsilyI)benzenesulphonamide is obtained in the form of white crystals, melting point 8S.6°C.

Mass collected: 11.9 g. Yield: 88X table (ii) Compounds of the formula (IV) in which R0, R10 and 10 R1i represent the hydrogen atom, prepared according to E x amp Ie 11 e x . !g r o u p 1 1 siRiR2R3 1 R7 1 1 Rg 1 1 z 1 1 1 a iMe 11 i ng ' jpoint in °c 11 1 L-1 1 SlEt3 1 H h 1 85.6 12 1 L-1 1 SlMe3 i h h | - | - I 160.7 13 1 L-1 1 SiHe3 1 CI H 1 - 1 - 1 162 14 1 L-1 1 SlMe3 1 H CF3 | - | - 1 122 1 L-1 1 SlMe3 1 H OMe | - 1 - 1 82 16 1 L-1 I SiMe3 1 H CI 1 - 1 - I 80.8 17 ! L-1 1 SiMe3 1 H F | - | - 1 89 18 1 L-1 1 SlMe3 1 h SMe 1 - 1 - 1 144 19 1 L-1 1 SlMe3 1 h s02me 1 137.1 1 L-2 1 sime3 1 h - 1 - 1 o 1 127.1 21 1 L-2 I SiMe3 1 h - 1 - 1 1 1 231.7 22 1 L-4 I SiMe, - 1 s 1 - 1 124.3 Example 23.

Preparation of N-(4,6-dimethoxy-2-pyrimidinyI)amino-carbonyl-2-(tri ethyls ilyl)benzenesulphonamide. (The product 15 comes under the formula I). 22 5 1 6 0 ** tt - • -23- 1-97 g (7.26 mmol) of 2-1riethyIsUyI benzenesuI-phonamide and 2 g (7.26 mmol) of phenyl N-(4,6-dimethoxy-1,3-pyrimidin-2-yl)carbamate in 35 ml of dry acetonitrile are introduced in a 100-ml round-bottom flask. 1.1 g (7.26 mmol) of 1,8-diazabicycloC5.4.0]undec-7-ene, dissolved in 8 ml of acetonitrile, are added to the previous solution, at room temperature.

The temperature is raised by 3 to 4°C. The reaction mixture is allowed to stand for 4 h at room temperature, with stirring. 6 ml of a 10 X strength hydrochloric acid solution are then added.

A white precipitate which is formed rapidly is filtered off, washed with 15 ml of diisopropyl ether and then dried in vacuo.

N-(4,6-Dimethoxy-2-pyrimid inyl)aminocarbonyl-2-(triethylsilyl)benzenesulphonamide--is obtained in the form of a white powder, melting point 136.5°C.

Mass collected: 2.3 g. Yield: 701 TABLE (III) Compounds of the formula I in which Rg, R7, Rjq and R11 denotes the hydrogen atom, prepared in accordance with Example 23 -24r- LX .

Group SiW3 lR8 1 1 1 R9 1 1 1 Z 1 1 a R4 R5 X rte11 i ng point in 0 23 L-1 Sl£t3 i H 1 H - OMe OMe CH 136.5 24 L-1 SlMe3 1 H 1 H | - - OMe OMe CH 169,9 L-1 SlHe3 1 H 1 H I - - Me Me CH 19*0,4 26 L-1 Slhie3 1 H 1 H I - - OMe He N 166.1 27 L-1 SlMe3 1 H ! H' I - - OMe y.e CK 168.1 28 L-1 SlMe3 1 H 1 H | - - OHe OMe N 174.4 • 7S L-1 SiEt3 1 H 1 H | - - OHe Me N 169.2 L-1 Si Et3 ! H 1 H 1 - - He He CH 192 .6- 31 L-1 Si Et3 1 H 1 H - OHe Me^CH 156.3 32 L-1 SlMe3 1 H 1 CI | - - OHe OMe CH 179 33 L-1 SlHe3 1 H 1 CI I - - He Me CH 198 34 L-1 51He3 1 H 1 CI .

| - - OHe Me N 200 L-1 SiMe3 1 H 1 CI | - - OMe OMe N 202 36 L-1 SiMe^ 1 H Icf3 | - - Me Me CH 210 37 L-1 SlMe3 1 H Icf3 | - - OHe OHe CH 164 38 L-1 SlKe3 1 H Icf3 | - - OMe OMe N 160 39 L-1 SiKe3 1 K Icf3 | - - OMe Me N 177 40 L-1 SiKe3 1 H |cf3 | - - OMe Me CH 164 41 L-1 SiKe3 1 H 1 f 1 - - He Me CH 184 42 L-1 SiHe3 1 K 1 P | - - OMe OMe CH 157 43 L-1 Sl«e3 I H 1 f 1 - - OMe Me CH 188 44 L-1 SiHe3 1 H 1 f | - - OMe Me n 188.5 45 L-1 SlHe3 1 H 1 f | - - OMe OMe n 179 46 L-1 SlHe3 1 r 1 f | - - OMe CI CH 172 47 L-1 SlHe3 1 k 1 OHe i - - OMe OMe CH 130.1 48 L-1 SiHe, 1 H 1 SMe | - - Me Me CH 157.3 22 5 1 6 0 49 L-1 i SlMe3 1 H SHe I-I-I OMe I OMe CH 1 134 .3 50 L-1 1SlHe3 1 H SMe l-l-l OHe | He Ml 156 .5 51 L-1 1SlMe3 1 H S02Me l-l-l OHe | OMe CH | 109 .8 52 L-1 1SlMe3 1 H SOjMe l-l-l Me | Me CH 1 195 .8 53 L-1 1SlHe3 1 H S02Me l-l-l OHe | OHe N| 169 .8 54 L-1 1SlMe3 1 H S02Me l-l-l OHe 1 Me Nl 175 .5 55 L-2 |SlHe3 1 H - l-lol He | Me CH 1 179 • 56 L-2 1SlMe3 1 H - l-lol OHe 1 OMe CH | 165 57 L-2 1SlMe3 I H - l-lol OMe | • Me CH | 181 58 L-2 ISlMe3 1 H - l-lol OHe 1 Me N| 160 59 L-2 1SlMe3 I OMe - l-lol OMe 1 OMe CH I 156 .1 60 L-2 1SlMe3 1 H - l-lll OHe 1 He CH | 180 . 3 61 L-2 1SiMe3 1 H - l-lll Me 1 He CH I 62 L-2 ISIMe3 - i05) OMe 1 OMe Nl 159 .4 63 L- 2 1SlMe3 1 % - 0U)| OMe 1 OMe CH 1 150 .7 6 4 L-4 1 SIMe3- | - - i s T-1 OMe 1 OMe CH | 166 .9 65 L-4 ISlMe3 | - - lsl-1 Me 1 Me CH I 190 .2 66 L-4 1SlMe3 | - - lsl-1 OMe 1 He Nl 156 .3 67 L-4 I SlMe3 | - - lsl-1 OMe | OMe Nl 155 .3 68 L-4 1SiMe3 | - - lsl-1 OMe 1 CI CH 1 167 .1 Exampl e A - Herbicidal application as a pre-eme rgence treatment of plant species A certain number of seeds depending on the plant species and on the size of the seeds are sown in 7 x 7 x 5 8 cm pots containing light agricultural soil.

The pots are sprayed with slurry in an amount which corresponds to an application rate of 500 l/ha and which contains the active substance in the desired concentration.

Thus, treatment with the slurry is carried out on seeds which are not covered with soil (the expression 22 5 160 C slurry is used for generally describing water-diluted preparations which are applied to the plants).

The slurry used in this treatment is a solution or suspension of the active substance in an acetone/water mixture in the ratio 50/50, in the presence of 0.05 X by. weight of Cemulsol NP 10 (surfactant), comprising a polycondensate of ethylene oxide with an alkyl phenol (especially a polycondensate of ethylene oxide with nonylphenol) and 0.04 X by weight of T*een 20 (surfactant containing an oleate which is a polyoxyethylene derivative of sorbitol).

In the case of a suspension, it is obtained by mixing and grinding the ingredients in a grinder in a manner such tha tan average particIe size of less than 40 microns is achieved.

Various concentrations of active substance of the slurry have been used, corresponding to various rates of applied active substance. Results are given for the following application rates: Example Nos. 38, 39 at 250 g/ha Example Nos. 34 at 500 g/ha Examples Nos. 27, 28, 32, 33, 35, 36, 55, 56, 57, 58 at 1,000 g/ha.

After the treatment, the seeds are covered with a layer of soil of about 3 mm in thickness.

The pots are then placed in containers Into which the water for watering is poured, the pots are watered from beneath, and maintained for 24 days at room temperature at 22 5 1 6 0 70 X atmospheric humidity.

After 24 days, the number of living plants in the pots which have been treated with the slurry containing the active substance to be tested, are counted, and the number of living plants in a control pot treated in the ' same way but with a slurry which does not contain active substance, are counted. In this manner, the percentage of destroyed treated plants is determined by comparison with a non-treated control (first line of the results). A destruction percentage of 100 X means that complete destruction of the plant species in question has taken place, and a percentage of 0 X means that the number of living plants in the treated pot is identical to that in the control pot. Likewise, the percentage of reduced height of undestroyed or partially destroyed species is determined (second line of results).

The results obtained are presented after Example B. Example B: Herbicidal application as post-emergence treatment of plant spec ies.

A certain number of seeds, depending on the plant species and the size of the seeds, are sown in 7 x 7 x 8 cm pots containing light agricultural soil.

The seeds are then covered with a layer of soil of approximately 3 mm in thickness, and the 'seeds are allowed to germinate until a plantlet in a suitable stage is formed. For grasses, the stage where the second leaf is being formed is the treatment stage. For dicotyledon plants, the stage where the cotyledons are fully grown and the first true leaf is formed is the treatment stage.

The pots are then treated by spraying then with 5 slurry in an amount corresponding to an application rate* of 500 l/ha, and containing the active substance in the desiredconcentration.

The slurry has been prepared in the same way as in Example A.

Various concentrations of active substance of the slurry have been used which correspond to various rates of applied active substance. Results are given for the following application rates: Example Nos. 38, 39 at 250 g/ha, Example Nos. 34 at 500 g/ha Example Nos. 27, 28, 32, 33, 35, 36, 55, 56, 57, 58 at 1,000 g/ha The treated pots are then placed in containers into which the water for watering is poured, the pots are 20 watered from beneath, and maintained for 24 days at room temperature at 70 X atmospheric humidity.

After 24 days, the number of living plants in the pots which have been treated with the slurry containing the active substance to be tested are counted, and the 25 number of living plants in a control pot treated in the same way but with a slurry which does not contain active substance, are counted. In this manner, the percentage 22 5 1 6 0 of destroyed treated plants is determined by comparison with a non-treated control (first line of the results).

« A destruction percentage of 100 X means that complete destruction of the plant species in question has taken place, 5 and a percentage of 0 X neans that the number of living ' plants in the treated pot is identical to that in the control pot. Likewise, the percentage of reduced height of undestroyed - or partially destroyed species is determined (second line of results).

The plant species which have been used in Examples A and B are the following: Abbreviations Latin name English name ECH Echinochloa crusgall i barnyard grass LOL Lolium multiflorum Italian ryegrass CYP Cyperus esculentu's earth almond CEN Centaurea cyanus cornflower IPO I pomea purpurea common morning-glory SIN Sinapis alba mus tard ABU Abutilon theophrasti Indian mallow DAU Daucus carota carrot The results which have been obtained in the pre-emergence treatment (application method of Example A) are listed below: Iex ech lol cyp cen ipo sin abu dau 1 I 2 7 50 100 50 0 90 0 01 50 70 50 70 50 | |28 0 0 0 100 o 0 1 50 i |32 80 100 0 98 o | 40 | 134 100 100 100 0 80 o 0 1 70 0 50 40 | 135 100 100 100 100 100 90 | 136 100 100 70 0 40 50 138 98 so 0 60 60 0 0 60 0 139 100 100 80 0 80 o 70 155 0 70 70 0 70 156 80 100 100 0 98 70 157 80 98 80 80 40 80 80 158 50 100 80 100 80 0 Th e results obtained in the post-emergence treat ment (application method of Example B) are listed below .;uwr* «?><<•1 / f"l 22 5 7 © ^ 1 EX ECH LOL CYP1CEN IPO 1 SIN ABU DAU 1 127 0 95 0 1 0 0 | 100 0 50 | v,, 1 60 | 50 | 50 50 1 128 1 0 | 100 0 01 1 50 1 50 | 1 132 1 80 0 50 0 1 30 I 0 50 0 | 100 40 | 80 100 1 i Q 133 1 0 i 100 0 1 1 80 1 | 1 134 1 100 95 1 50 1 0 30 0 | 100 70 | 80 50 1 50 | 135 1 80 100 01 50 1 100|100 1 100 801 1 136 Oi C |100 1 I 80 70 40 1 0 60 1 50 1 138 1 70 60 91 60 1 100|100 1 0 30 1 1 139 1 70 50 70 01 301 100 1100 I 60 1 I 155 1 1 1 | 80 30 | 1 1 C • 156 1 100 70 01 60 1 100|100 I 40 1 1 157 1 80 80 01 201 70|100 70 | 0 30 1 1 158 90 100 1 100|100 1 c 1 1 1 1 1 1 1 1 The trials which have been carried out clearly show the advantageous properties of the compounds according to the invention, both for pre-emergenee treatments of the crops and for post-emergence treatments, both on mono cotyledon (grasses) and dicotyledon weed species. ?:j J-:^ 22UU>0

Claims

WHAT WE CLAIM IS: A sulphonylurea derivative of the formula; 'Va>i? L-SO~-NH-CO-NRc-A 2 6 (I) in which: L represents one of the groups of the formulae L-1 to L-6 depicted below, and A represents a group of the formula depicted below, P? %w__siRiR2R3 O 8 R9 L-1 llOs /SiR.R.R, L-2 Rj^ z 'SiRl&& L-3 10 SiFjP2R3 € V / I *11 L-5 L-4 -ft K< ».£>* < ' •> r ^ 11 L-6 lA) 225160 -33- wherein R^, R2 and , which are identical or different, each represents a C1-C4 alkyl radical or a aralkyl radical; R^, Rg and Rg, which are identical or different, each represents a hydrogen or halogen atom, a C^-C^ alkyl radical which is optionally substituted by one or more halogen atoms or alkoxy or alkylthio radicals, a C^-C^ cycloalkyl radical which is optionally substituted by one or more halogen atoms or alkoxy or alkylthio radicals, a C^-C^ alkoxy or alkylthio radical, each of which is optionally substituted by one or more halogen atoms or C^-C^ alkoxy or C^-C^ alkylthio radicals, a group R^2 s (0) n~ in which n is 1 or 2 and R^ represents a C^-C4 alkyl radical which is optionally substituted by one or more halogen atoms or C^-C4 alkoxy or C^-C4 alkylthio radicals, a group COOR14 in which R^4 is a hydrogen atom, or a C^-C4 alkyl or C^-C& cycloalkyl radical each of which is optionally substituted by one or more halogen atoms or alkoxy or C^-C4 alkylthio radicals, or a C^-C^ alkenyl radical which is optionally substituted by one or more halogen atoms; r^q and R^ are identical or different and are as hereinbefore defined for R^ with the exception of the halogen atom; 225160 -34- m is 0 or 1; Z is the oxygen atom, the sulphur atom or a group *n which R^2 is a C^-Cg alkyl, cg~cio aryl or C^-C^ aralkyl radical; X is -CH= or -N=; R4 and R5 are identical or different and each represents a C1~C4 alky1 radical, a C^-C4 alkoxy radical, a C^-C^ alkylthio radical, a C1~C4 haloalkyl radical, a C1~C4 haloalkoxy radical, a C^-C4 haloalkylthio radical, a C2-Cg alkoxyalkyl radical, a C2~Cg alkoxyalkoxy radical, a C^-C4 alkylamino radical, a di(C^-C4 alkyl)amino radical or a halogen atom; and Rg represents the hydrogen atom or a C^-C4 alkyl radical; and agriculturally acceptable salts thereof.
2. A compound according to claim 1 wherein the aryl radicals are phenyl, aralkyl radicals are benzyl, R12 represents methyl, X is -N=i R4 and R,., which are identical or different, each represents methyl, methoxy, methylthio, trifluoromethyl, di- or tri-fluoromethoxy, trifluoromethylthio, methoxymethyl, methoxymethoxy or chlorine, and Rg represents hydrogen or methyl.
3. A compound according to claim 1 or 2 wherein Rg is hydrogen.
4. A compound according to claim 1, 2 or 3 wherein L represents a group L-1.
5. A compound according to any one of the preceding claims wherein R1, R2 and R3 each represent the methyl radical. 225100 "»*r 1 -35-
6. A compound according to any one of claims 1, 3, 4 and 5 wherein R4 and Rg, which are identical or different, represent a halogen atom, a C^-C4 alkyl radical, a C^-C4 alkoxy radical, or a C^-C4 haloalkoxy radical.
7. A compound according to claim 6 wherein R4 and C~) Rg, which are identical or different, each represents chlorine, methyl, methoxy or difluoromethoxy.
8. A compound according to any one of the preceding claims, wherein R?, Rg and Rg which are identical or different, represent a halogen atom, a hydrogen atom or a Ci-C4 alkoxy radical.
9. A compound according to any one of claims 1 to 7 wherein R?, Rg and Rg represent hydrogen atoms.-
10. A compound according to any one of the preceding claims, wherein R^q and R^ which are identical or different, each represents a hydrogen atom or a C^-C4 alkoxy kL/ radical. r '
11. A compound according to any one of claims 1 to 9 wherein R^q and R^ represent hydrogen atoms.
^ 12. A compound according to.claim 1 hereinbefore identified in any one of Examples 23 to 68.
13. A process for the preparation of a sulphonylurea derivative according to any one of claims 1 to 12, which comprises reacting an aminopyridine or an aminotriazine of the formula A-NHR- wherein A is as defined in claim 1 with a 5 _ sulphonyl isocyanate of the formula (III) L-SOr^SQ-,,wherein 1<J o| 225160 -36- L is as defined in claim 1, and optionally converting a sulphonylurea derivative thus obtained into an agriculturally acceptable salt thereof.
14. A process according to claim 13 which is carried out using a stoichiometric quantity of the sulphonylisocyanate, in an inert solvent, at a temperature from 20° to 100°C.
15. A process for the preparation of a sulphonylurea derivative according to any one of claims 1 to 12, which comprises reacting a pyrimidinyl or triazinyl aryl carbamate of the formula (XII) Ph-O-CO- NRg-A, in which Ph is a Cg-Cjg aryl ring and A is as defined in claim 1, with a sulphonamide of the formula (IV) L-SO^-NI^ wherein L is as defined in claim 1, and optionally converting a sulphonylurea derivative thus obtained into an agriculturally acceptable salt thereof.
16. A process according to claim 15 which is carried out using a stoichiometric quantity of the sulphonamiAg^ in the presence of a tertiary amine in an inert solvent, at a o S temperature from 20 to 100 C. /r* ^ 7V °
17. A process according to claim 13 or 15 (p? substantially as hereinbefore described in any one of a°CTl99( Examples 23 to 68. i
18. A sulphonylurea derivative according to claim 1 when prepared by a process according to any one of claims 13 to 17.
19. A herbicidal composition which comprises a sulphonylurea derivative according to any one of claims 1 to 12 and 18 or an agriculturally acceptable salt thereof in association with an agriculturally acceptable diluent or carrier and/or surface active agent.
20. A composition according to claim 19, which comprises 0.05 to 95% by weight of the sulphonylurea derivative or agriculturally acceptable salt thereof.
21. A herbicidal composition according to claim 19 substantially as hereinbefore described.
22. A method of controlling the growth of weeds at a locus which comprises applying to the locus a sulphonylurea derivative according to any one of claims 1 to 12 and 18, or an agriculturally acceptable salt thereof.
23. A method according to claim 22 substantially as hereinbefore described. Tl H|| , ,| | , J**" By l^s/their authorised Agents. A. J. PARK & SON.