GB2110689A - Herbicidal heterocyclic aminosulfonyl ureas and isoureas - Google Patents

Abstract

Novel aminosulfonyl urea derivatives which are 1-diazinyl- or 1- triazinyl-3-aminosulfonyl ureas, 1- diazinyl- or 1-triazinyl-2-alkyl-3- aminosulfonyl isoureas and their corresponding isothioureas can be made up into herbicidal compositions.

Description

SPECIFICATION Herbicidal sulfonamides The present invention relates to novel aminosulfonyl urea derivatives, their use as herbicides, agriculture compositions for facilitating such use and the preparation of the novel compounds and the compositions of the invention.

Various alkyl- and arylsulfonyl urea compounds have been reported to possess herbicidal activity.

Aminosulfonyl urea compounds have hitherto not been proposed for use as herbicides; many of them are known to have pharmacological, particularly hypoglycaemic activity. The novel aminosulfonyl urea compounds of the invention have valuable herbicidal properties. They are readily obtained from relatively cheap starting materials.

The present invention provides novel aminosulfonyl urea derivatives belonging to the group consisting of 1 -diazinyl- or 1-triazinyl-3-aminosulfonyl urea, 1 -diazinyl- or 1 -triazinyl-2-alkyl-3- aminosulfonyl isourea and their corresponding isothiourea, herein after designated compounds of the invention.

A preferred subgroup of the compounds of the invention are 1-diazinyl- or 1-triazinyi-3- aminosulfonyl urea.

The diazine and triazine substituent and the amino group of the aminosulfonyl substituent of the compounds of the invention may be unsubstituted or substituted by substituents acceptable in the agricultural art. The amino group of the aminosulfonyl substituent may thereby also form part of an heterocyclic ring.

Suitable di- or triazine substituents are i.a. unsubstituted, mono- or disubstituted hetero rings of the group 2-pyrimidinyl, 4-pyrimidinyl 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl; preferred hetero rings belong to the group consisting of 2-pyrimidinyl and 1 ,3,5-triazin-2-yl, particularly the latter.

A particular group of compounds of the invention are those of formula I

wherein R, and R2 are independently H, CN, C18-alkoxy-CO or an unsubstituted or substituted hydrocarbyl selected from the group consisting of C1-6-alkyl, C2a-alkenyl, C26-alkinyl, C37 cycloalkyl or phenyl, or R, and R2 form together with the nitrogen to which they are bound a saturated 5-to 7-membered hetero ring, X is a group G1 of the formula NR3-CO-NR4R5 or a group G2 of the formula N=C(AR6)-NR4R5, R3 is H or C1-5alkyl, R4 is 4-R,-6-R8-pyrimindin-2-yl, 2-R7-6-R8-pyrimidin-4-yl, 4-R7-6-R8-1 ,3,5-triazin-2-yl or 5-R7-6 R8-1 ,3,4-triazin-2-yl, R5 is H or C1-5-alkyl, R6 is H or C1-5alkyl, R7 and R8 are independently H, halogen, C1-8-alkyl, C1-5-haloalkyl, C1-5-alkoxy, C1-5alkylthio, C1-5-alkoxy-C1-5-alkyl, NH2, C15-alkyl-NH or di(C,~5-alkyl)N and AisOorS.

Suitable C~6-alkyl significances of R, and R2 are e.g. C1-5-alkyl, particularly C,~3-alkyl groups such as CH3, C2H5, n-C3Hg and i-C3H7.

Suitable C2~6-alkenyl or alkinyl significances of R, and R2 are e.g. C3~5-alkenyl or alkinyl having the double or triple bond in ss,#-position of the N to which they are bound.

Suitable C3-7-cycloalkyl significances of R, and R2 are e.g. cyclopentyl or cyclohexyl.

Suitable substituents of the hydrocarbyl significances R1 and R2 are e.g. halogen, cyano, CF3, NO2, phenyl, di-C1-3-alkylamino, acyl, OH or SH in free form or in etherified or esterified form and COOH in free form or in esterified form and, of the cyclic hydrocarbyl significances of R, and R2, also C1-5-alkyl and C1-5-haloalkyl.

Where the hydrocarbyl significances of R1 and/or R2 are substituted, they bear preferably 1 substituent. If this substituent is or contains C1-5-alkyl, such alkyl is, for example, CH3 or C2H5.

Where the hydrocarbyl significances of R, and/or R2 are substituted by acyl, such acyl is e.g. C25 alkanoyl such as acetyl, or benzoyl.

Where the hydrocarbyl significances of R, and/or R2 are substituted by OH or SH in etherified or by COOH in esterified form, such substituents are e.g. C1-5-alkoxy such as CH3O, t.C4HgS or phenoxy resp. C1-5-alkoxy-carbonyl, such as COOCH3 or COOC2H5, Where NR1R2 is a saturated 5 - to 7-membered heteroring this may contain one or 2 additional heteroatoms selected from the group consisting of 0, S or N, whereby eventual additional nitrogen atoms bear H, C1-5alkyl (e.g. CH3) or C,~5-acyl (e.g. formyl or alkanoyl such as acetyl). Suitable examples of such heterocyclic significances of NR,R2 are e.g. pyrrolidin-1 -yl, piperidin-1-yl, (thio) morpholino, 4-OH3-piperazin-1 -yl, perhydroazepin-1 -yl.

Suitable C,~5-alkyl significances of R3, R5 and R6 are e.g. O13-alkyl such as CH3.

Where R7 and/or R8 are or contain C,~5-alkyl such alkyl has, for example, 1 to 3 e.g. 1 or 2 Catoms.

Where R7 and/or R8 are C,~5-alkoxy-C,~5-alkyl, such group comprises preferably 2 to 4 C-atoms.

Where R7 and/or Ra are haloalkyl, such group is for example CF3 or CH2CI.

Where any of R1, R2 or X comprises halogen, the halogen is selected from F, Cl or Br.

Preferred compounds of formula I have one or more of the following features X is group G, R, is H or unbranched C,~3-alkyl, R2 is allyl, propinyl, unbranched C,~3-alkyl, 2-cyanoethyl, R3 is H, R4 is 4,6-dimethylpyrimidin-2-yl or 4-methoxy-6-methyl-1 ,3,5-triazin-2-yl, particularly the latter R5 is H.

Depending on the meaning of the substituents of the compounds of the invention, such compounds may comprise acid and/or basic functions. The compounds of the invention may consequently be in free form or in salt form, e.g. in alkalimetal salt form, ammonium salt form and acid addition salt form.

Any salt form of the compounds of the invention is preferably in the form of an agriculturally acceptable salt form.

The salt forms of the compounds of the invention can be prepared from the corresponding free form in conventional manner and vice versa.

The presentivention also provides processes for producing the compounds of the invention.

The 1-diazinyl-and 1-triazinyl-3-aminosulfonyl ures of the invention are obtained by urea condensation of the appropriate isocyanate or carbamate, or reactive derivative thereof with the corresponding amine (analogous to process a) hereinafter), or by reaction of the appropriate chlorosulfonyl urea with the corresponding amine (analogous to process b) hereinafter) or by oxydation of the corresponding isothiourea. The 1 -diazinyl- and 1 -triazinyl-2-alkyl-3-amino-sulfonyl isourea and isothiourea compounds of the invention are obtained by reaction of the appropriate N-aminosulfonyl carbonimidic acid, the corresponding dithio acid or an ester of such acids with the corresponding amine (as indicated for process c) hereinafter).

The compounds of formula I are accordingly obtained by the following processes, comprising a) obtaining a compound of formula la R1R2N-SO2G1 la wherein R1, R2 and G, are as defined above, by reacting under urea condensation reaction conditions a compound of formula II R,R,N--SO,,-NR,X, 11 wherein R, and R2 are as defined above, either Ra is H or C~5-alkyl and X, is H or a carbonyl containing functional reactive derivative of COOH or Ra and X, together are 0=0 with a compound of formula III RgX1NR4 Ill wherein R4 is as defined above and R9' and X1' have the significances given for R9 and X1 respectively with the proviso that either the compound of formula II or the compound of formula III is a reactive carbamic acid or an isocyanate, or b) obtaining a compound of formula Ib R1 R2N-S02-NH-CO-NR4R5 Ib wherein R1, R2, R4 and Ra are as defined above, by reacting a compound of formula IV CISO2-NH-CO-NR4R5 IV wherein R4 and R5 are as defined above, with an amine of formula V R,R2NH V wherein R, and R2 are as defined above, or c) obtaining a compound of formula Ic R1R2NSO2-N=C(AR6)-NR4R5 lc wherein R1, R2, R4, R5, R6 and A are as defined above, by reacting a compound of formula VI

wherein Rr, R2, A and R8 are as defined above, with a compound of formula VII HNR4R5 VII wherein R4 and R5 are as defined above, d) obtaining a compound of formula Ib (as defined above) by oxydation of a compound of formula Id, R1R2N502-N=C(SR6)-NR4R5 Id wherein R1, R2, R4, R5 and Re are as defined above.

Process a) can be carried out by conventional manner under conditions known for the synthesis of urea starting from a reactive carbamic acid derivative or an isocyanate. Suitable reactive carbamic acid derivatives of a compound of formula II and formula Ill are e.g. the corresponding carbamic acid esters such as the methyl or ethyl ester, or the corresponding acid halogenides, such as the carbamoyl chloride.

Examples of reactions involved when preparing the compounds of formula la according to process a) are given in the following equations 1 to 6.

Eq. 1: R1R2N-SO2-NR3-COAAlkyl+HNR4R # la( 2: R1R2N-S02-NR3-COCL+HNR4R5 o la 3 : R1R2N-SO2-N=C=O+HNR4R5 # la (R3=H)( 4: R,R,N-SO,-NHR,+AlkylOOC-NR,R, # la 5: R1R2N-SO2-NHR3+ClCO-NR4R5 < la 6: R1R2N-S02-NHR3+O=C=N-R4 e la (Ra=H) la=compound of formula la ()la (R3=H)=compound of formula la wherein R3=H.

The reactions represented by the above Equations 1 to 6 are conveniently carried out in an inert aprotic organic solvent such as acetone, ethyl acetate, methylene chloride, tetrahydrofuran or acetonitrile. They are conveniently effected at temperatures from ambient temperature up to reflux temperature, and at ambient pressure.

The reactions represented by Equations 1, 2, 4 and 5 are preferably effected in the presence of a base such as an alkali metal hydride, alcoholate, carbonate (e.g. NaH, K2CO3, Na2CO3) or an aromatic, aliphatic or heterocyclic amine (e.g. triethylamine, pyridine or piperidine).

Process b) can be carried out by conventional manner under conditions known for the synthesis of sulfonamides starting from the corresponding sulfonyl chlorides and amines. It is preferably effected in a solvent which is inert under the reaction conditions, e.g. an ether such as tetrahydrofuran.

In general, the reaction proceeds smoothly at room temperature, so that usually heating is not necessary. Process b) is particularly suitable for the synthesis of compounds of formula Ib, wherein R, and/or R2 is H. The compounds of formula IV which are novel (and also form part of the invention) are conveniently prepared in situ e.g. by reaction of C@SO2-N=C=O with the corresponding amine of formula VII.

Process c) can be carried out by conventional manner under conditions known for the synthesis of isourea or isothiourea from the corresponding carbonimidic or carbonimido dithioc acid or ester. The amines of formula VII are preferably used in anion form. Such anion can be obtained by reaction of a compound of formula VII with an alkali metal base, e.g. NaH. Process c) is preferably carried out in an inert aprotic solvent, e.g. an ether such as tetrahydrofuran, in dimethylformamide or dimethylacetamide.

In general, process c) can be effected at room temperature.

The oxydation of the compound of formula Id to compounds of formula Ib according to process d) may be effected by methods known in the art for the oxydation of isothiourea to the corresponding urea. Suitable oxydation agents are e.g. mercuric oxide/boron trifluoride etherate, mercuric chloride/calcium carbonate and peracids.

The compounds of formula Ib are preferably prepared according to process b).

The compounds of formula I may be recovered from the reaction mixture in which it is formed by working up by established procedures.

Insofar as the production of starting material is not described herein, these compounds are known, or may be produced and purified in accordance with known processes or in a manner analogous to processes described herein or to known processes.

The compounds of the invention are useful as herbicides, whereby herbicide as used herein means a compound which controls or modifies the growth of plants. By plants it is meant germinant seeds, emerging seedlings and established vegetation including underground portions.

The useful herbicidal activity of the compounds of the invention is indicated by i.a. the damage caused to both mono-cotyledoneous and dicotyledoneous weeds such as Lepidium sativum, Avena sativa, Agrostis Alba and Lolium perenne in tests by test dosages equivalent to an application rate of from 1.4 to 5.6 kg/ha after pre- or post-emergence application.In view of their herbicidal effect the compounds of the invention are indicated for use in combatting dicotyledoneous and grassy weeds, as confirmed by further evaluation with representative compounds with test dosages equivalent to an application rate of from 0.2 to 5.0 kg active ingredient, e.g. test dosages equivalent to a rate of 0.2, 1.0 and 5.0 kg active ingredient/ha, in dicotyledoneous weeds such as Ameranthus retroflexus, Capsella bursa-pastoris Chenopodium alba, Stellaria media, Senecio vulgaris, Galium aparine, Portulaca spp.

and Abutilon spp. and in grassy weeds such as Agropyron repens, Agrostis alba, Alopecurus myosuroides, Apera spica venti, A vena fatua, Echinochloa crus-galli, Lolium perenne, Sorghum halepense, Digitaria sanguinalis, Setaria italica, Leptochloa dubia and Panicum spp.

The compounds of the invention are relatively less toxic towards crops, e.g. grassy crops such as a small grain (wheat, barley, upland rice, paddy rice) or corn (maize) or against broad leaved crops such as soybean, cotton, carrot, sugar beet, potato, alfalfa, sunflower or flax than towards weeds. The compounds of the invention are therefore also indicated for use as selective herbicides in a crop locus.

Said selective herbicidal activity of the compounds of the invention is, for example, noted after pre-emergence application in a crop locus including a small grain crop, such as wheat or rice, corn, potato, soybean, sunflower and cotton.The selective herbicidal effect of the compounds of the invention is also noted after post-emergence application to a crop locus including i.a. corn, potato, soybean and small grain crops such as wheat and rice. This post-emergence selective herbicidal activity is particularly effective in corn, wheat, rice and soybean.

The present invention therefore also provides a method of combatting weeds in a locus, preferably in a crop locus as mentioned above, which comprises applying to the locus a herbicidally effective amount of a compound of the invention.

For general herbicidal as well as for selective herbicidal use of compounds of the invention, the amount to be applied to attain the desired effect will vary depending on the particular crop if employed for selective use and other standard variables such as the compound employed, mode of application, conditions of treatment and the like. The appropriate application rates can be determined by routine procedures by those skilled in the art, or by comparing the activity of the compounds of the invention with standards for which the application rate is known, e.g. in greenhouse tests. However, in general, satisfactory results are usually obtained when the compound is applied at a rate in the range of from about 0.1 to 5 kg/ha, preferably from about 0.2 to 2 kg/ha, more preferably from 0.5 to 1.0 kg/ha, the application being repeated as necessary.When used in a crop locus, the application rate should preferably not exceed 2 kg/ha.

The emergence time referred to above is with respect to the weeds. In the post-emergence selective use, the compounds of the invention may be applied pre-emergence the crops but it is generally preferred to effect the application post-emergence both the weeds and crop.

The compounds of the invention may be and preferably are employed as herbicidal compositions in association with herbicidally acceptable diluent(s). Suitable formulations contain 0.01% to 99% by weight of active ingredient, from 0 to 20% herbicidally acceptable surfactant and 1 to 99.99% solid or liquid diluent(s). Higher ratios of surfactant to active ingredient are sometimes desirable and are achieved by incorporation into the formulation or by tank mixing. Application forms of composition generally contain between 0.01 and 25% by weight of active ingredient. Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Concentrate forms of compositions intended to be diluted before use generally contain between 2 and 90%, preferably between 10 and 80% by weight of active ingredient.

Useful formulations of the compounds of the invention include dusts, granules, pellets, suspension concentrates, wettable powders, emulsifiable concentrates and the like. They are obtained by conventional manner, e.g. by mixing the compounds of the invention with the diluent(s). More specifically liquid compositions are obtained by mixing the ingredients, fine solid compositions by blending and, usually grinding, suspensions by wet milling and granules and pellets by spraying the active material onto preformed granular carriers or by agglomeration techniques.

Alternatively, the compounds of the invention may be used in microencapsulated form.

Herbicidally acceptable additives may be employed in the herbicidal compositions to improve the performance of the active ingredient and to reduce foaming, caking and corrosion.

Surfactant as used herein means a herbicidally acceptable material which imparts emulsifiabiiity, spreading, wetting, dispersibility or other surface-modifying properties. Examples of surfactants are sodium lignin sulphonate and lauryl sulphate.

Diluents as used herein mean a liquid or solid herbicidally acceptable material used to dilute a concentrated material to a usable or desirable strength. For dusts or granules it can be e.g. talc, kaolin or diatomaceous earth, for liquid concentrate forms, for example a hydrocarbon such as xylene or an alcohol such as isopropanol, and for liquid application forms i.a. water or diesel oil.

The compositions of this invention can also comprise other compounds having biological activity, e.g. compounds having similar or complementary herbicidal activity such as a phenoxy acetic acid or phenoxy propionic acid, for example mecoprop, or a urea, for example linuron or metoxuron, or ioxynil, or diclofopmethyl, or compounds having antidotal, fungicidal or insecticidal activity.

Specific Examples of herbicidal compositions will now be described.

Example A Wettable powder 25 Parts of a compound of the invention, e.g. the compound of Example 1 hereinafter given are mixed and milled with 25 parts of synthetic fine silica, 2 parts of sodium lauryl sulphate, 3 parts of sodium ligninsulphonate and 45 parts of finely divided kaolin until the mean particle size is about 5 micron. The resulting wettable powder is diluted with water before use to a spray liquor with the desired concentration.

Example B Emulsion concentrate 25 Parts of a compound of the invention, e.g. the compound of Example 1 hereinafter given, 65 parts of xylene and 10 parts of emulsifier (e.g. Atlox 4851 B a blend of Ca alkylarylsulphonate and a polyethoxylated triglyceride of Atlas Chemie GmbH) are thoroughly mixed until a homogeneous solution is obtained. The resulting emulsion concentrate is diluted with water before use.

Example C Granules 5 Kg of a compound of the invention, e.g. the compound of Example 1 hereinafter given, are dissolved in 15 1 methylene chloride. The solution is then added to 95 kg of granulated attapulgite (mesh size 24/28 mesh/inch) and thoroughly mixed. The solvent is then evaporated off under reduced pressure.

The invention is further illustrated by the following Examples wherein temperatures are in 00.

Final compounds Example 1 N-(Diethylaminosulfonyl)-N'-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl) urea (process b) To a suspension of 7 g (0.05 Mol) 2-methoxy-4-methyl-6-amino-triazine in 100 ml tetrahydrofuran cooled at --50, are added, slowly, 4.5 ml (0.05 Mol) chlorosulfonylisocyanate. One obtains a light yellowish solution which is stirred during 10 hours at room temperature.

To this solution are added dropwise, at ambient temperature, 8 g (0.11 Mol) diethylamine, dissolved in 10 ml tetrahydrofuran and the reaction mixture thereafter stirred during 3 hours at ambient temperature. The precipitate is sucked off, dissolved in CH2CI2, the solution washed with water, dried and evaporated to dryness. The residue is then chromatographed on silica gel with CH2CI2:acetone 90:10 as mobile phase and consequently crystallised from CH2CI2/diethylether/n- hexane to yield the title compound in the form of white crystals m.p. 143--50.

Example 2 N-[(2-Cyanoethyl)methylaminojsulfonyl-N'-(4-methoxy-6-rnethyl-1 ,3,5-triazin-2-yl)urea To a suspension of 56 g (0.4 mol) 2-methoxy-4-methyl-6-aminotriazine in 650 ml 1,2dimethoxy-ethane (suspension prepared under N2-atmosphere) are added, over a period of 35 minutes, at 50, a solution of 35 ml (0.4 mol) chlorosulfonylisocyanate in 10 ml of 1 ,2-dimethoxyethane.

The so obtained, light yellow solution is stirred during 1 + hours, under ice cooling, and then added dropwise, over a period of 1 T hours, at 2" to 50, to a solution of 69 g (0.82 mol) 3methylamino-propionitril in 1 50 ml 1 ,2-dimethoxyethane. The reaction mixture is stirred 1 hour under ice cooling and 2 hours at ambient temperature (240), then poured onto 8 litres of ice water and then 400 ml 2N HCI-solution are added thereto.

After thorough stirring during 45 minutes the white suspension is sucked off, washed with water, and dried under vacuum at 4000. The so obtained title compound has a m.p. of 134--1370.

Example 3 N-[(2-Chlornethyl)methylaminosulfonyl]-N'-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)urea Under careful exclusion of humidity (apparatus rinsed with dry N2) a solution of 4.4 ml (0.05 mol) chlorosulfonylisocyanate in 10 ml absolute 1,2-dimethoxyethane is added dropwise at 00, within 10 minutes, to a suspension of 7 g (0.05 mol) 2-methoxy-4-methyl-6-aminotriazine in 80 ml absolute 1 ,2-dimethoxyethane, while stirring. The stirring is continued one more hour at 0 until a light yellow solution is formed.The solution is, at 00, added to a slurry of 13.3 g (0.102 mol) Z-chloro-N- methylethylamino-hydrochloride in 50 ml absolute 1,2-dimethoxyethane and to this reaction mixture (still at C=) are added dropwise, within 30 minutes, 10.3 g (0.102 mol) triethylamine in 30 ml absolute 1 ,2-di-methoxy-ethane. The mixture is then stirred during 4 hours at ambient temperature and the solvent then evaporated under water jet vacuum. The solid residue is dissolved in 200 ml of water, and acidified up to pH 3 with HCl solution. The acid solution is extracted 3 times with 100 mL CH2Cl2 and the combined CH2Ci2 solutions are washed with water (3 times 50 ml). The solution is dried, the solvent evaporated and the residue chromatographed on a silica gel column using diethylether/acetone 9:1 as eluent.The title compound is obtained in the form of colourless crystals which can be recrystallized from toluene, m.p. 1300.

Example 4 Following the procedure of one of the Examples 1 to 3, employing chlorosulfonylisocyanate and appropriate amines of formula VII and V, the following compounds of formula Ib are obtained, wherein R4 is 4-methoxy-6-methyi-l ,3,5-triazin-2-yl, R5 is H and R,R2N is 4.1 C2H5-NH ; white crystals ; m.p. 126-9 (decomp.) 4.2 anilino; white, amorphous; m.p. 146-8 (decomp.) 4.3 O-chloroanilino; white, amorphous, m.p. 65-85 (decomp.) 4.4 NH2 4.5 CH3NH 4.6 (CH3)2N ; m.p. 80-182 4.7 C2Hs(CH3)N; m.p. 159610 4.8 n-C3H7NH 4.9 i-C3H7NH 4.10 cyclopentyl-NH 4.11 cyclopentyl-N(CH3) ; m.p. 91-92 4.12 cyclohexyl-NH 4.13 cyclohexyl-N(CH3) ; m.p. 168-72 4.14 allyl-NH ; m.p. 112-14 4.15 allyl-N(CH3) ; m.p. 129-30 4.16 2-propinyl-NH 4.17 C6H5N(CH3); m.p. 151 0 4.18 C6HsN(C2Hs) 4.19 C6HsCH2NH 4.20 C6H5CH2N(C2H5) 4.21 HO-CH2CH2N(CH3) ; m.p. 120-123 4.22 CH3O-CH2CH2N(CH3) 4.23 9CH3OCH2CH2)2N ; m.p. 97-9 4.24 CICH2CH2CH2NH; m.p. 1530 4.25 NC-NH 4.26 NC-CH2N(CH3) ; m.p. 128-30 4.27 NC-CH2CH2N(CH2CH2OH) 4.28 C2H5OOC-CH2-NH ; m.p. 133-4 4.29 C2H5OOC-CH2-N(CH3) ; m.p. 109-12 4.30 (CH3)2NCH2CH2-NH 4.31 pyrrolidino ; m.p. 168-70 4.32 piperidino ; m.p. 152-154 4.33 morpholino; m.p. 177-9 (decomp.) 4.34 4-methyl-1 -piperazinyl 4.35 perhydroazepin-1-yl 4.36 N(i-C3H7)2; m.p. 141-4 4.37 N(#-C3H7)2 ; m.p. 132-4 4.38 N(n-C4Hg)2; m.p. 130-1 0 4.39 N(CH3)CH2-C#CH; m.p. 159-161 4.40 NH-CH2CH2OCH3 ; m.p. 132-5 4.41 N(C2H5)CH2CH2CN ; m.p. 149510 4.42 N(#-C3H7)CH2CH2CN ; m.p. 126-8 4.43 N(i-C3H7)CH2CH2CN; m.p. 157-9 4.44 NH-(O-ON-phenyl); m.p. 980 4.45 NH-(p.Cl-phenyl) ; m.p. 176 4.46 N(CH3)CH2CH2C6H5 ; m.p. 100 4.47 N9C6H5)CH2C6H5 ; m.p. 154 4.48 N(CH3)CH2C6H5 ; m.p. 149

4.51 NH-CH2CH2CN ; m.p. 142 (decomp.) 4.52 N(cyclopropyl)CH2CH2CN ; m.p. 108-112 (decomp.) 4.53 N(cyclopentyl)CH2CH2CN ; m.p. 149-51

4.58 N(CH2CH2CN)2; m.p. 151-4

4.60 N(CH3)CH2-CHCl-CN(amorphous) 4.61 NH-CH2CH2(OCH3)2 ; m.p. 135-8 4.62 NH-(CH2)3OCH3 4.63 N(CH3)CH2CH2COOCH3 ; m.p. 81-84 4.64 N(CH3)CH2CH2COCH3 4.65 NH-CH(COOCH3)2 ; m.p. 129-31 4.66 NH-C(CH3)=CH-COOCH3 4.67 N(CH3)CH2COCH3 4.68 NH-CH2CH2-N(CH3)2 4.69 N(CH3)CH2CH2-N(CH3)2 4.70 NH-(o.COOC2H5-phenyl) ; m.p. 145 4.71 NH-(o.OCH3-phenyl) ; m.p. 166 4.72 NH-(o.NH2-phenyl0 ; m.p. 135 4.73 N(phenyl)CH2CH2CN; m.p. 1160 4.74 NH-(m, CF3-phenyl) ; m.p. 160 4.75 1 ,3-thiazolidin-3-yl; m.p. 1360 4.76 thiomorpholino; m.p. 1600 4.77 NH-t.C4Hg; m.p. 2000 (decomp.) 4.78 NH-COOC2H5 4.79 N(CH3)COOC2H5 4.80 NH-C(CH3)=CH-CN 4.81 N(C2H5)CH2CH2Cl ; m.p. 90

4.83 N(CH3)CH2CH2CH2Cl ; m.p. 241

Rf. 0.65 (in ethylacetate on silica gel) 4.85 N(@C3H7)CH2CH2Cl ; m.p. 132 4.86 NH-CH(C2H5)-CH2Cl 4.87 N(CH2C6Hs)CH2CH2CI 4.88 N(CH2CH2Cl)2 4.89 N(CH3)CH2-CHCl-CH2Cl 4.90 N(CH3)CH2-CH=CHCl 4.91 N(CH3)CH2-CCl=CH2 4.92 N(CH3)CH2-CH=CCI2 4.93 NH-CH2CH2SCH2 4.94 N(CH3)CH2CH2SCH3 4.95 NH(2-CH3S-C6H4) 4.96 N(CH3)-CH2CH2S-C6H5 Example 5 Following the procedure of one of the Examples 1 to 3 employing chlorosulfonylisocyanate and the appropriats amines of formula VII and V, the following compounds of formula Ib are obtained, wherein R, and R2 are C2Hs, R5 is H and R4 is 5.1 4,6-dimethylpyrimidin-2-yl 5.2 4-chloro-6-methylpyrimidin-2-yl 5.3 2,4-dimethylpyrimidin-6-yl 5.4 4-chloro-2-methylthio-pyrimidin-6-yl 5.5 3,4-dimethyl-1,2,5-triazin-6-yl 5.6 4,6-dichloropyrimidin-2-yl 5.7 2,4-dichloro-1,3,5-triazin-6-yl 5.8 2-chloro-4-methoxy- 1,3,5-triazin-6-yl 5.9 2-amino-4-chloro-1,3,5-triazin-6-yl 5.10 2-chloro-4-methylamino-1 ,3,5-triazin-6-yl 5.11 2-chloro-4-dimethylamino-1,3,5-triazin-6-yl 5.12 2-chloro-4-diethylamino-1,3,5-triazin-6-yl (m.p. 149-52 ).

Example 6 Following the procedure of one of the Examples 1 to 3, employing the chlorosulfonylisocyanate and the appropriate amines of formula VII and V the following compounds of formula Ib are obtained wherein R4 is 4,6-dimethylpyrimidine, Ra is H and NR,R2 is 6.1 N(CH3)CH2CH2CN ; m.p. 161-2 6.2 N(CH3)2 ; m.p. 204-206 6.3 1 ,3-thiazolidin-3-yl; m.p. 1 570 6.4 NH-(o.CN-phenyl) ; m.p. 1310 6.5 N(CH3)CH2CH2OC6Hs; m.p. 1360 6.6 NH-t.C4Hg; m.p. 151 0 6.7 NH2; m.p. 1800 6.8 N(CH3)CH2CH2C6H5 ; m.p. 135 6.9 NH-CH2CH2OCH3 ; m.p. 128-30 6.10 NH-(m.CN-phenyl) ; m.p. 1490 6.11 NH-(p.CN-phenyl) ; m.p. 1710 6.12 NH-(o.CF3-phenyl) ; m.p. 80 6.13 NH-(m.OF3-phenyl); m.p. 1490 6.14 NH-(o.OH-phenyl) ; m.p. 1260 6.15 NH-(o.CH3O-phenyl) ; m.p. 165 6.16 NH-(o.NO2-phenyl) ; m.p. 149 6.17 NH-(o.COOC,H,-phenyl); m.p. 1480 6.18 N(C6H5)CH2CH2CN ; m.p. 161 6.19 NHCH2CH2-S-t.C4H3 ; m.p. 50 6.20 N(CH3)CH2CH2SCH3 6.21 NH(2-CH3S-C6H4) 6.22 N(CH3)CH2CH2SC6Hs.

Example 7 Methyl N-(piperidinosulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamimidothioate (process c) A suspension of 2.43 g (0.81 mol) NaH in oil (80% by weight) is suspended in 150 ml dimethylformamide and this added to 11.2 g (0.08 Mol) 2-amino-4-methoxy-6-methyl-1,3,5-triazine.

The reaction mixture is stirred during 3 hours at room temperature, until the H2 development is no longer observed. This solution is added dropwise, at 20 to 300, to a solution of 21.5 g (0.08 Mol) N piperidinosulfonyl-carbonimidodithioic acid dimethyl ester in 50 m 1 ml dimethylformamide. The reaction mixture is stirred during 2 hours at room temperature, poured onto 2 1 ice water, sucked off and the basic mother liquor adjusted to pH 2-3 with an aqueous, 10% HCI solution, sucked off after 15 minutes stirring and washed with water. The crystalline precipitate is dissolved in CH2C12, the solution shaken with water, dried with Na2SO4 evaporated to dryness and the residue recrystallised from CH2CI2/hexane fraction to give the title compound in the form of white crystals, m.p. 173-174 .

Example 8 Following the procedure of Example 7, but employing appropriate compounds of formula VI and of formula VII the following compounds of formula Ic are obtained, wherein NR4Rs is 4-CH30-6-CH3- 1 ,3,5-triazin-2-ylamine and NR,R2 and AR6 are 8.1 N(CH3)2 and SCH3 resp. (m.p., 171-173 ; white crystals) 8.2 piperidino and OCH2H5 resp. (m.p. 138-140 ; white crystals from CH2CI2/diethyl- ether/hexane fraction) 8.3 N(CH3)cyclohexyl and SCH3 resp.

8.4 morpholino and SCH3 resp.

8.5 N(CH3)cyclopentyl and SCH3 resp.

8.6 N(n-C3H72 and SCH3 resp.

8.7 pyrrolidino and SCH3 resp.

8.8 N(CH2CH20CH3)2 and SCH3 resp.

8.9 N(CH3)C2H5 and SCH3 resp.

8.10 N(CH3)CH2CH2C6Hs and SCH3 resp.

8.11 N(C6Hs)CH2C6Hs and SCH3 resp.

8.12 N(CH3)C6Hs and SCH3 resp.

8.13 N(CH3)CH2C6Hs and SCH3 resp.

8.14 N(i-C3H7)2 and SCH3 resp.

8.15 N(CH3)CH2CH2CN and SCH3 resp.

Example 9 Analogous to the procedure of Example 7 is obtained methyl N(dimethylaminosulfonyl)-N'-(4,6- dimethylpyrimidin-2-yl)carbamimidothioate.

Example 10 N-(Piperidinosulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea (process d) A suspension of 6 g (0.0279 Mol) HgO in 60 ml of a 15% by weight solution of water in tetrahydrofuran is added dropwise at 20-30 , to 4.5 ml (0.0353 Mol) BF3. O(C2Hs)2. The reaction is slightly exothermic. To this suspension are added, dropwise, after 30 minutes' stirring at room temperature, 6.1 g (0.017 Mol) N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-pipridinosulfonyl carbamimidothioic acid methyl ester. The reaction is slightly exothermic. The reaction mixture is stirred during 2 hours at room temperature, whereby its colour gradually changes from red to beige and sucked off. The crystals are washed with water and hereafter with CH2CI2.The white crystals are then dissolved in 0.1 N NaOH solution, the solution filtered, acidified with a 2N HCI solution and extracted with CH2CI2. The CH2Ci2 solution is dried with Na2SO4 and evaporated to dryness. The residue is purified with the aid of column chromatography and recrystallised from CH2CI2/diethylether/hexane fraction to give the title compound in the form of white crystals (m.p. 152-154 ).

Example 11 Following the procedure of Example 10, but employing the appropriate compounds of formula Ic as starting material, the following compounds of formula Ib are obtained, wherein R4 is 4-CH30-6-CH31,3,5-triazin-2-yl, R5 is H and NR,R2 is 11.1 N(CH3)2 (m.p. 172-175 white crystals; starting from Example 8.1) 11.2 N(CH3)CH2CH2CN; m.p. 129-31 (from Ex. 8.15) 11.3 N(CH3)cyclohexyl; m.p. 168-72 (from Ex. 8.3) 11.4 morpholino; m.p. 176-9 (from Ex. 8.4) 11.5 N(CH3)cyclopentyl; m.p. 91920 (from Ex. 8.5) 11.6 N(n-C3H7)2; m.p. 132-40 (from Ex. 8.6) 11.7 pyrrolidino; m.p. 168-70 (from Ex. 8.7) 11.8 N(CH2CH2OCH3)2; m.p. 97-9 (from Ex. 8.8) 11.9 N(CH3)C2H5 ; m.p. 159-61 (from Ex. 8.9) 11.10 N(CH3)CH2CH2C6H5 ; m.p. 100 (from Ex. 8.10) 11.11 N9C6H5)CH2C6H5 ; m.p. 154 (from ex. 8.11) 11.12 N(CH3)C6Hs; m.p. 1510 (from Ex. 8.12) 11.13 N(CH3)CH2C6Hs; m.p. 1490 (from Ex. 8.13) 11.14 N(i-C3H,)2; m.p. 141--40 (from Ex. 8.14).

Example 12 Following the procedure of Example 10, starting from the compound of Example 9, the corresponding compound of formula Ibis obtained, wherein 12.1 NR1R2 is N(CH3)2, R4 is 4,6-dimethylpyrimidin-2-yl and R5 is H (m.p. 204--60).

Example 13 The oxydation of the compound of Example 8.1 to the compound of Example 11.1 is advantageously effected as follows: To a solution of 102 g of the compound of Example 8.1 in 700 ml CH2CI2 are added dropwise, with stirring 355 g of a 15% solution of H202 in acetic acid, at ambient temperature.

The reaction mixture is stirred overnight at ambient temperature, poured onto 2 litres ice water and the separated CH2CI2-phase shuttled twice with 500 ml conc. NaHSO3 solution, three times with water, dried and concentrated by evaporation to give the compound of Example 11.1 in the form of white crystals (m.p. 172--750).

Intermediates Example 14 N-chlorosulfonyl-N'-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl urea) To a suspension of 3.5 g (0.025 Mol) 2-methoxy-4-methyl-6-aminotriazine in 35 ml tetrahydrofuran, cooled at --200, is slowly added a solution of 2.3 ml (0.026 Mol) chiorosulfonylisocyanate in 1 5 ml tetrahydrofuran. The reaction mixture is then stirred during 2 hours and the temperature allowed to rise up to 00. The title compound precipitates from the resulting yellow solution in the form of white needles, which are sucked off and washed with diethylether. The needles decompose at about 1600.

Example 15 N-( Piperidinosulfonyl)carboni midothithioic acid dimethyl ester To a solution of 32.8 g (0.2 Mol) piperidinosulfonamide in 150 ml dimethylformamide, are added, under vigorous stirring, 12 ml of a solution prepared from 1 6 g (0.4 Mol) NaOH in 20 ml water. The sodium salt of the sulfonamide precipitates thereby. After the addition of 6.6 mi (0.11 Mol) CS2 reaction temperature rises slightly (necessitating a slight ice cooling) and the reaction mixture first becomes deep orange-red and ca. 1 0 minutes thereafter yellow-orange. Then 6 ml of the above NaOH solution and 3.5 ml (0.055 Mol) CS2 are added and this operation repeated after 10 minutes.

The reaction mixture is stirred during 1 5 minutes and to the so prepared yellowish suspension are added, dropwise, and at 25--300, 56.7 g (0.4 Mol) CH31. After ca. 10--15 minutes a yellow solution is formed which is stirred 1 5 hours at room temperature. The precipitated crystals are sucked off at 00.

Additional substance is obtained from the mother liquor by column chromatography. The crystals are suspended in CH2CI2, shaken with H2O, dried with Na2SO4, evaporated to dryness and the residue recrystallised from CH2Ci2-hexane fraction. The title compound is obtained in the form of white crystals m.p. 88--900.

Example 16 N-(Piperidinosulfonyl)carbonimidic acid diethyl ester A mixture of 6.5 g (0.04 Mol) piperidino-sulfonamide and 11.5 g (0.06 Mol) C(OC2Hs)4 is heated, with stirring to 1300 and kept at this temperature during 2 hours 4.2 ml C2H5OH are then distilled off and the excess C(OC2Hs)4 thereafter distilled off under reduced pressure. The residue, a dark oil, is purified by column chromatography to yield the title compound in the form of an oil, which crystallises; m.p. 44--460.

Test results Example 17 Weed control-pre-emergence treatment Seed pots (7 cm diameter) are filled with a mixture of peat culture substrate and sand. The exposed surface of the peat culture substrate and same mixture is sprayed with a test liquid of a test compound (e.g. formulated in accordance with Example B) and seeds of Lepidium sativum, Agrostis a.lba,Avena sativa and Lolium perenne are sown in each pot, whereby theAvena sativa and Lolium perenne seeds are, after sowing covered with a thin layer (0.5 cm) of peat culture substrate/sand mixture. The pots are kept for 21 days at room temperature with 14 to 1 7 hours light (daylight or its equivalent) per day.

Determination of the herbicidal effect of the particular herbicide is made after the 21 day period.

The determination involves a visuai evaluation of the degree and quality of damage to the various seed plants.

The compounds of formula I of the above Example 1 to 13 are applied in the above manner at dosages equivalent to 1.4 and 5.6 kg of active agent/hectare.

Herbicidal activity is observed, that is to say, significant damage to the test plants is observed.

Example 18 Weed control-post-emergence treatment A procedure similar to that employed in Example 1 7 is followed with the exception that the test compounds (herbicides) are applied when the plants are at the 2 4 leaf stage, the sowing of the plant seeds being staggered to ensure that the plants reach the 2 4 leaf stage at about the same time.

Again the compounds are applied in the above manner at dosages corresponding to 1.4 kg/ha and 5.6 kg/ha. The determination of the herbicidal effect is made 21 days after application of the test compounds and involves an analogous evaluation as described in Example 17. Herbicidal activity is observed.

Example 19 Field trials The useful herbicidal activity of the compounds of the invention is confirmed by a further evaluation against various grassy and dicotyledonous weeds in various crops with application rates of 0.3, 0.6, 1.0, 1.2, 2.0. Valuable herbicidal activity is i.a. observed with the compounds of Examples 1, 2,4.1,4.6, 4.7, 4.37,4.41 and 4.42, particularly against dicotyledonous weeds. The post-emergence activity is in general more pronounced than the pre-em activity.

Claims (12)

Claims

1. Novel aminosulfonyl urea derivatives belonging to the group consisting of 1-diazinyl- or 1triazinyl-3-aminosulfonyl urea, 1 -diazinyl- or 1 -triazinyl-2-alkyl-3-aminosulfonyl isourea and their corresponding isothiourea.

2. A compound of Claim 1 of formula I

wherein R, and R2 are independently H, CN, C1~6-alkoxy-CO or an unsubstituted or substituted hydrocarbyl selected from the group consisting of C,~6-alkyl, C2~6-alkenyl, C2~6-alkinyl, C3~7-cycloalkyl or phenyl, or R, and R2 form together with the nitrogen to which they are bound a saturated 5- to 7-membered heteroring, X is a group G1 of the formula NR3-OO-NR4R5 or a group G2 of the formula N=C(AR6)-NR4R5, R3 is H or C,~5-alkyl, R4 is 4-R7-6-R8-pyrimidin-2-yl, 2-R7-6-R8-pyrimidin-4-yl, 4-R7-6-R8-1,3,5-triazin-2-yl or 5-R7-6 R8-1,3,4-triazin-2-yl, Ra is H or C,~5-alkyl, R8 is H or C,~5-alkyl, R7 and R6 are independently H, halogen, C,~5-alkyl, C,~5-haloalkyl, C,~5-alkoxy, C,~5-alkylthio, C1-5-alkoxy-C1-5-alkyl, NH2, C1-5-alkyl-NH or di(C1-5-alkyl)N and A is O or S.

3. A compound of Claim 2 wherein X is (4,6-dimethylpyrimidin-2-yl)-NH-CO-NH or is (4methoxy-6-methyl-1,3,5-triazin-2-yl)-NH-CO-NH.

4. A compound of Claim 3 wherein R, is H or unbranched C1~3-alkyl and R2 is unbranched O'13 alkyl, 2-cyanoethyl, allyl or propinyl.

5. Processes for the production of compounds of Claim 1, comprising a) obtaining 1-diazinyl- and 1-triazinyl-3-aminosulfonyl urea by urea condensation of the appropriate isocyanate or carbamate, or reactive derivative thereof with the corresponding amine, b) obtaining 1-diazinyl- and 1-triazinyl-3-aminosulfonyl urea by reaction of the appropriate chlorosulfonyi urea with the corresponding amine, c) obtaining 1-diazinyi- and 1 -triazinyl-2-alkyl-3-amino-sulfonyl isourea and isothiourea by reaction of the appropriate N-aminosulfonyl carbonimidic acid or dithio acid or an ester of such acids with the corresponding amine, d) obtaining 1-diazinyl- and 1-trlazinyl-3-aminosulfonyl urea by oxydation of the corresponding isothiourea.

6. Processes according to Claim 5 for the production of a compound of formula I as defined in Claim 2, comprising a) obtaining a compound of formula la R1R2N-SO2G, wherein R1, R2 and G, are as defined in Claim 2 by reacting under urea condensation reaction conditions a compound of formula II R1R2N-SO2-NR9X1 II wherein R, and R2 are as defined in Claim 2, either R9 is H or C1-5-alkyl, and X, is H or a carbonyl containing functional reactive derivative of COOH or R9 and X, together are 0=0 with a compound of formula Ill R9'x(NR4 III wherein R4 is as defined in Claim 2 and R9' and X, have the significances given for Ra and X, respectively, with the proviso that either the compound of formula II or the compound of formula Ill is a reactive carbamic acid or an isocyanate, or b) obtaining a compound of formula Ib R1 R2N-S02-NH-CO-NR4R5 Ib wherein R1, R2, R4 and Re are as defined in Claim 2, by reacting a compound of formula IV CISO2-NH-CO-NH4R5 IV wherein R4 and R6 are as defined in Claim 2, with an amine of formula V R,R2NH V wherein R, and R2 are as defined in Claim 2, or c) obtaining a compound of formula Ic R1 R2NSO2-N=C(AR6)-NR4R5 Ic wherein R1' R2, R4, R5, R6 and A are as defined in Claim 2, by reacting a compound of formula VI

wherein R1, R2, A and R6 are as defined in Claim 2, with a compound of formula VII HNR4R5 VII wherein R4 and R5 are as defined in Claim 2, d) obtaining a compound of formula Ib, as defined in this claim, by oxydation of a compound of formula Id, R1R2NSO2-N=C(SR8)-NR4R5 Id wherein R1, R2, R4, R5 and R6 are as defined in Claim 2.

7. A herbicide comprising a compound claimed in any one of Claims 1 to 4 and an agriculturally acceptable diluent.

8. The use of a compound claimed in any one of Claims 1 to 4 as herbicide.

9. A compound as claimed in Claim 2, substantially as hereinbefore described with reference to the accompanying Examples.

10. A process as claimed in Claim 5, substantially as hereinbefore described with reference to the accompanying Examples.

11. A compound as defined in Claim 1, whenever obtained by a process claimed in Claim 10.

12. A compound of formula IV as defined in Claim 6.