GB2110689A - Herbicidal heterocyclic aminosulfonyl ureas and isoureas - Google Patents

Herbicidal heterocyclic aminosulfonyl ureas and isoureas Download PDF

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GB2110689A
GB2110689A GB08234220A GB8234220A GB2110689A GB 2110689 A GB2110689 A GB 2110689A GB 08234220 A GB08234220 A GB 08234220A GB 8234220 A GB8234220 A GB 8234220A GB 2110689 A GB2110689 A GB 2110689A
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Werner Trueb
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Sandoz KK
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Sandoz KK
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D239/00Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32One oxygen, sulfur or nitrogen atom
    • C07D239/42One nitrogen atom
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40Nitrogen atoms
    • C07D251/48Two nitrogen atoms
    • C07D251/50Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D295/00Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2.] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2.] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/26Sulfur atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D417/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D521/00Heterocyclic compounds containing unspecified hetero rings

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 <img class="EMIRef" id="027123213-00010001" />

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 <img class="EMIRef" id="027123213-00030001" />

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 <img class="EMIRef" id="027123213-00070001" />

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 <img class="EMIRef" id="027123213-00070002" />

4.58 N(CH2CH2CN)2; m.p. 151-4 <img class="EMIRef" id="027123213-00070003" />

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 <img class="EMIRef" id="027123213-00070004" />

4.83 N(CH3)CH2CH2CH2Cl ; m.p. 241 <img class="EMIRef" id="027123213-00070005" />

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)cyc