NL8204635A - SULPHONAMIDES WITH HERBICIDE ACTION. - Google Patents

Description

* i *. t

Sulphonamides with herbicidal action.

The invention relates to new amino sulfonylurea derivatives, their use as herbicides, agricultural preparations to facilitate such use and the preparation of the new compounds and the compositions of the invention.

Many alkyl and arylsulfonylureas have been reported to have a herbicidal action. However, aminosulfonyl urea compounds have not hitherto been proposed for use as herbicides; many are known to have a pharmacological, especially hypoglycaemic, action. The new aainosulfonylureas of the invention have valuable herbicidal properties. They were easily obtained from relatively inexpensive starting materials.

The present invention provides novel amino sulfonyl urea derivatives which belong to the group consisting of 1-diazinyl or 1-triazinyl-3-aminosulfonyl urea, 1-diazinyl or 1-triazinyl-2-alkyl-3-aminosulfonyl isoureas their corresponding isothiourea derivatives, hereinafter referred to as compounds 20 of the invention.

A recommended subset of the compounds of the invention are 1-diazinyl "or 1-triazinyl-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 field. The amino group of the aminosulfonyl substituent may also form part of a heterocyclic ring.

Suitable di- or triazine substituents include unsubstituted, mono or disubstituted hetero-8204635-2-rings of the group 2-pyrimidinyl, U-pyrimidinyl, 1,3,5-triazin-2-yl and 1,2 k Triazin-3-yl * recommended hetero rings belong to the group consisting of 2-pyrimidinyl and 1,3,5-triazin-2-yl, especially the latter.

A particular group of compounds according to the invention are those of the formula

»1V T

N - SO X * * 2 in which R 1 and R 2, independently of one another, is a hydrogen atom, a cyano group, a C 1-6 alkoxy-CO group or an unsubstituted or substituted hydrocarbon group selected from alkyl of 1-6 carbon atoms, alkenyl of 2-6 carbon atoms, alkinyl with 2-6 carbon atoms, cycloalkyl with 3 "7 carbon atoms or phenyl, or wherein R 1 and R 2 together with the nitrogen atom to which they bond form a saturated heterocyclic 5" to 7 "ring, X a group of formula NR ^ -CO-NR ^ R ^ represents whether a group G ,, of formula N = C (AR ^) - NR ^ R ^, R ^ represents a hydrogen atom or an alkyl group with 1-5 carbon atoms, R ^ a kR ^ -6-Rg-pyrimidin-2-yl-, 2-R ^ -6-Rg-pyrimidin-U-yl-, 4-R ^ -6-Rq-1,3,5 "triazine -2-yl- or 5-R ^ -6-Rg-1jSj ^ -triazine-R-yl group, R_ represents a hydrogen atom or 5 represents an alkyl group with 1-5 carbon atoms, Rg represents a hydrogen atom or an alkyl group with 1-5 carbon atoms independently, R ^ and Rg is a hydrogen or halogen 2 5 atom, an alkyl group with 1 to 5 carbon atoms, a haloalkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, an alkylthio group with 1 to 5 carbon atoms, a C 1-6 alkoxy-C 1 alkyl group, an NHO group , a C 1 -alkyl-NH-1-5 1-5 d 1-5 or -di (C 1-6 alkyl) N group and A = 0 or S.

3Q Suitable meanings of an alkyl group with 1-6 carbon atoms for R1 and R1 are, for example, alkyl groups with 1-5 carbon atoms, in particular alkyl groups with 3.Ts 1-3 carbon atoms, such as methyl, ethyl, n.propyl - and iso-propyl group.

Suitable alkenyl or alkinyl groups with 2-6 carbon 8204635 ι - 3 - * ........ 4 atoms for and Rg are, for example, alkenyl and alkinyl groups with 3 * 5 carbon atoms having a double or triple bond at the 6, γ position of the nitrogen atom to which they are attached.

Suitable meanings of cycloalkyl groups with 3 * 7 carbon atoms for R 1 and R 8 are, for example, a cyclopentyl or cyclohexyl group.

Suitable substituents of the hydrocarbon * meanings and Rg are, for example, halogen, cyano, trifluoromethyl, nitro, phenyl, di-C 1-6 alkylamino, acyl, hydroxyl or SH in free form or in an etherified or esterified form and the carboxyl group in free form or in esterified form and, from the cyclic hydrocarbon meanings of R 1 and R 5, also alkyl groups of 1-5 carbon atoms and haloalkyl groups of 1-5 carbon atoms.

When the hydrocarbon groups for R1 and / or Rg are substituted, they preferably contain a substituent.

If this substituent is or contains an alkyl group with 1 to 5 carbon atoms, such an alkyl group is, for example, the methyl or ethyl group.

When the hydrocarbon groups for R 1 and / or R 6 are substituted by acyl, such an acyl group is, for example, an alkanoyl group with 2-5 carbon atoms, such as an acetyl or benzoyl group.

When the hydrocarbon groups for R. and / or R are substituted by ether or SH in etherified or by C00H in esterified form, such substituents are, for example, alkoxy groups with 1-5 carbon atoms, such as the methoxy group, tC ^ H ^ S group or phenoxy group resp. an alkoxy, carbonyl group, such as a C00CH3 or C00CgH5 group.

If NR ^ g gives a saturated heterocyclic 5- to 7 "ring ^ ee ^ i it can contain 1 or 2 extra hetero atoms selected from the group consisting of 0, S or N, with any additional nitrogen atoms hydrogen, alkyl having 1 -5 carbon atoms (e.g., methyl) or acyl of 1-5 carbon atoms (e.g., 8204 6 35

Jp; * + - Including formyl or alkanoyl, such as acetyl). Suitable examples of such heterocyclic groups of formula NR ^ Rg are, for example, pyrrolidin-1-yl, piperidin-1-yl, (thio) morpholino, U-CHg-piperazin-1-yl and perhydroazepine-1-5 yl.

Suitable alkyl groups with 1-5 carbon atoms for Rg, Rjj and Rg are, for example, alkyl groups with 1-3 carbon atoms, such as the methyl group.

If R 1 and / or R 8 are or contain alkyl groups of 1-5 carbon atoms, such an alkyl group contains, for example, 1-3 carbon atoms, for example 1 or 2 carbon atoms.

When R 1 and / or R 5 represent an alkoxy-C 1 -alkyl group, such a group preferably contains 2-b carbon atoms.

When R 1 and / or R 5 give a haloalkyl group, such a group is preferably a trifluoromethyl or chloromethyl group.

If R, Rg or X contain halogen, this is fluorine, chlorine or bromine.

Recommended compounds of formula 1 have one or more of the following characteristics: X represents a group G1, R1 represents a hydrogen atom or a straight chain alkyl group with 1 to 3 carbon atoms, R is eqallyl, propinyl, straight chain

d I

alkyl group with 1-3 carbon atoms or a 2-cyanoethyl group, Rg represents a hydrogen atom, R ^ represents a U, 6-dimethyl-pyrimidin-2-yl or U-methoxy-6-methyl-1,3,5 " triazin-2-yl, especially the last group, spring and R 2 is a hydrogen atom.

Depending on the meanings of the substituents of the compounds of the invention, such compounds may contain acidic and / or basic functions. The compounds according to the invention can therefore be present as much in free form as in salt form, for example in an alkali metal salt form, ammonium salt form and acid addition salt form.

An optional salt form of the compounds according to 3204635-1; "T -..-". iJSfe-Λ v-j ··.

The invention is preferably in the form of a salt form acceptable for agricultural purposes.

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

The invention also provides methods of preparing the compounds of the invention.

The 1-diazinyl and 1-triazinyl-3 "aminosulfonyl urea derivatives of the invention can be rained by 10 urea condensation of the appropriate isocyanate or carbamate, or a reactive derivative thereof with the corresponding amine (analogous to process a) described below), or by reaction of the appropriate chlorosulfonylurea with the corresponding amine (analogous to process b) described below) or by oxidation of the corresponding isothiourea. The 1-diazinyl and 1-triazinyl-2-alkyl-3-amino-sulfonylisourea and isothiourea compounds of the invention can be obtained by reacting the appropriate N-aminosulfonylcarbonimidic acid, the corresponding dithioic acid or an ester of such acids with the corresponding amine (as indicated for the following method c)}.

The compounds of formula I are therefore obtained according to the following methods, which include: a) preparing a compound of formula 25 R ^ N-SOgG ^ Ia in which R ^, Rg and G1 have the previously defined meanings, by reaction under urea condensation reaction conditions of a compound of formula R ^ gN-SOg-NR ^, ii wherein R1 and Rg have the meanings defined above and either R9 contains a hydrogen atom or an elkyl group containing t-5 carbon atoms and X ^ contains a hydrogen atom or a carbonyl group, represent a functional reactive derivative of C00H, or wherein Rp and together form a C0 group, with a compound of formula 8204635

f V

- 6 - ψ; Ν] \ πι, where R ^ has a previously defined "meaning and R ^ and have the meanings indicated for R ^ and respectively, provided that the bond of formula II or the compound of the formula III is a reactive carbamic acid or an isocyanate, or b) preparing a compound of formula R1R2N-SO2-NH "C0" NR ^ R5 Ib, wherein R ^, R ^, R ^ and R ^ have the meanings defined above 10 by reacting a compound of formula

ClSOg-NH-CO-HR ^ Rj IV, wherein R ^ and R ^ have the previously defined meanings, with an amine of formula R ^ NH V, wherein R1 and R ^ have the previously defined meanings, or c) preparing of a compound of formula R1 R2NSO2-N = C (ARg) -NR ^ R Ic, wherein R ^, R ^, R ^, R ^, Rg and A have the meanings defined above, by reaction of a compound 20 ib i -so -K y 6 n 12 2 'ab6 in which R4, Rg, A and Rg have the meanings defined above, with a compound of formula 25 Hrur5 VII, wherein R4 and R8. have the previously defined meanings, d) preparing a compound of formula Ib (as defined above) by oxidation of a compound of formula R 2 NSOg-N-CtSRgJ-NRj ^ 1d, wherein R1, R2, R ^, R ^ and Rg have the meanings defined above.

Process a) can be carried out in a conventional manner, under conditions known for the synthesis of urea starting from a reactive carbamic acid derivative or an 8204635-7 isocyanate. Suitable reactive carbamic acid derivatives of a compound of formula II and formula III are, for example, the corresponding esters of carbamic acid, such as the methyl or ethyl ester, or the corresponding acid halides, such as the carbamoyl chloride.

Examples of the respective reactions in preparing the compounds of formula Ia according to method a) are given in the following equations I-VI.

Cf. 1: R1R2N-SO2-BR3-C0AAlkyl + HNR ^ - * Ia * 1 ^ 10 2: R, R „H-S0„ -inL-C0Cl + "* Ia 1 2 2 3 /« \

3: R ^ gN-SOg-H-OO + "- * · Ia (R3» H) ^ V

k: R1R2N-S02-HHR3 + alkylOOC-NR ^ y— * · Ia 5 ï R1R2H-S02- »HR3 + CICO-NR ^ —► Ia 6: R ^ R2H-S02-HHR3 + 0« CNR ^ —► IaiR ^ H) ^ Ia * compound of formula Ia ^ 2 ^ Ia (R3 * H) * compound of formula Ia, wherein R3eH.

The reactions represented by the above equations I-VI are suitably carried out in an inert, aprotic, organic solvent such as acetone, ethyl acetate, methylene chloride, tetrahydrofuran or acetonitrile. They are suitably run at temperatures from room temperature to the reflux temperature and at normal pressure.

The reactions represented by equations 1,2, U and 5 are preferably in the presence of a base, such as an alkali hydride, alcoholate, carbonate (eg

NaH, K2CO3, Na2CO3) or an aromatic, aliphatic or heterocyclic amine (e.g. triethylamine, pyridine or piperidine).

Process b) can be carried out in a conventional manner under the conditions known for the synthesis of sulfonamides starting from the corresponding sulfonyl chlorides and amides. The reaction preferably proceeds,.

is inert in a solvent bath under the reaction conditions, for example an ether such as tetrahydrofuran.

In general, the reaction proceeds easily at 8204635 1 - 8 - • ♦ room temperature, so that usually no heating is required. Process h) is particularly suitable for the synthesis of compounds of formula Ib wherein and / or represent a hydrogen atom. The compounds of formula IV which are new (and also part of the invention) are conveniently prepared in situ, for example, by reaction of 0130 -11 = 0 = 0 with the corresponding amine of formula VII.

Process c) may be carried out in a conventional manner, under the conditions known for the synthesis of isourea or isothiourea from the corresponding carbonimidine or carbonimidodithioic acid or ester. The amines of formula VII are preferably used in anionic form.

Such an anion can be obtained by reacting a compound of formula VII with an alkali metal base, for example, NaH. Method c) / preferably in an inert, aprotic solvent, for example an ether, such as tetrahydrofuran, in. dimethylformamide or dimethylacet amide.

In general, method c can be performed at room temperature.

The oxidation of the compounds of formula Id to compounds of formula Ib according to method d) can be carried out according to methods known in the art for the oxidation of isothiourea to the corresponding urea. Examples of suitable oxidizing agents are mercuric oxide-boron trifluoride etherate, mercuric chloride calcium carbonate and peracids.

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

The compounds of formula I can be recovered by customizing the reaction mixture in which they are formed in a customary manner.

Insofar as the preparation of the starting material is not described herein, these compounds are known, or may be by known methods or in a manner consistent with methods described herein or with known 8204635

% A

Processes are obtained and purified.

The compounds of the invention are useful as herbicides, wherein the term herbicide used herein refers to a compound that fights or controls plant growth. Planting refers to germinating seeds, emerging seedlings and established vegetation, including the parts underground.

The useful herbicidal action of the compounds of the invention is indicated, inter alia, by the damage caused by both single-seed and dicotyledonous weeds, such as Lepidium sativum. Avena sativa, Agrostis Alba and

Loliiaa perenne in trials at test dosages equivalent to an application rate of 1.5-5.5 kg / ha when applied as much as before hatching. In view of their herbicidal activity, the compounds of the invention are indicated for use in controlling dicotyledonous and grassy weeds, as confirmed by further studies with representative compounds at test dosages equivalent to an administration amount of 0.2-5.0 kg of active ingredients, for example study dosages equivalent to an amount of 0.2; 1.9 and 5.0 kg of active ingredient per hectare, for dicotyledonous weeds, such as Amaranthus retroflexus. Capsella bursa-pastoris Chenopodium alba. Stellaria media.

Senecio vulgaris. Galium aparine. Portulaca spp. and Abutilon 25 spp. and grassy weeds, such as Agropyron repens

Agrostis alba. Alopecurus myosuroides. Apera spica venti.

Avena fatua. Echinochloa crus-galli. Lolium perenne. Sorghum halepense. Digitaria sanquinalis. Setaria italics. Leptochloa dubia and Panicum spp.

The compounds according to the invention are relatively less toxic to crops, for example grass-like crops, such as small cereals (wheat, barley barley, overhead rice, paddy rice) or grain (corn) or against broad-leaved crops, such as soybeans, cotton, carrots, sugar beets , potatoes, 35 alfalfa, sunflowers or flax, then against weeds. The 8204635 w * - 10 compounds of the invention are therefore also indicated for use as selective herbicides in a crop region.

This selective herbicidal action of the compounds according to the invention is observed, for example, after the. // use for hatching in an area of crops, including small cereal crops such as wheat or rice, corn, potatoes, soybeans, sunflowers and cotton. The selective herbicidal activity of the compounds of the invention is also noted after post-application use in an area of crops including corn, potatoes, soybeans and small grain crops such as wheat and rice. This selective hatching herbicidal activity is particularly effective with corn, wheat, rice and soybeans.

Thus, the present invention also provides a method of controlling weeds in an area, preferably an area of crops as described above, which comprises applying a herbicidally effective amount of one or a number of compounds of the invention in this area.

For general herbicidal as well as for selective herbicidal use of compounds of the invention, the amount to be used to obtain the desired effect will vary depending on the particular crop, if used for selective application, and other standard variables, such as the compound used, mode of administration, treatment conditions, etc. The appropriate amounts to be used can be determined according to routine methods by those skilled in the art, or by comparing the action of the compounds of the invention with standard compounds for which the amount to be used is known, for example, by tests in greenhouses, however, are generally found, however, satisfactory results are usually obtained when the compound is used in an amount ranging from about 0.1 to 5 kg / ha, preferably from about 0.2 to 2 kg / ha ha, in 8204635: '' '· !! ΡΙ ^ ............. ... ,,, 1 m' * - 11 - especially from 0.5 to 1.0 kg / ha, which application can be repeated if necessary. When applied in an area with crops, the amount to be applied will preferably not exceed 2 kg / ha.

5 The aforementioned time for infestation is related to the weed species. When used selectively after hatching, the compounds of the invention may be administered before hatching, but it is generally recommended to use them after hatching both the weeds and the crops.

The compounds of the invention can and are preferably used as preparations with a herbicidal action, if desired together with herbicidally effective diluent (s). Suitable formulations contain 0.01-15.99% by weight of active ingredient, 0-20% herbicidally acceptable surfactant and 1-99% 99% solid or liquid diluent (s). Higher ratios of surfactant to active ingredient are sometimes desired and are obtained by incorporation into the composition or by mixing in a tank. The use forms of the preparation generally contain between 0.01 and 25% by weight of active ingredient. Lower or higher levels of active ingredient may of course be present depending on the intended purpose and the physical properties of the compound. Concentrated forms of the composition, which are intended to be diluted before use, generally contain between 2 and 90 wt.%, Preferably between 10 and 80 wt.%. %, active ingredient.

Useful preparations of the compounds according to the invention include powders, granules, pellets, concentrated suspensions, wettable powders, emulsifiable concentrates, etc. They are obtained in a customary manner, for example by mixing the compounds according to the invention with one or more thinners. More particularly, the liquid preparations are obtained by mixing the ingredients 8204635 ψ - 12 - fine solid preparations by mixing and usually comminuting, suspensions by moist grinding and capsules and pellets by the active material pre-formed, granular carriers for spraying or by agglomeration methods.

It is also possible to use the compounds according to the invention in a microencapsulated form.

In the herbicidal formulations, herbicidally acceptable additives may be used to enhance the action of the active ingredient and reduce foaming, cake formation and corrosion.

A surfactant used herein is a herbicidally acceptable material that contributes or imparts emulsifiability, dispersion, wetting, dispersibility, or other surface modifying properties.

Examples of surfactants are sodium lignin sulfonate and lauryl sulfate.

Diluents to be used herein are a liquid or solid herbicidally acceptable material used to dilute a concentrated material to a useful or desired strength. For powders or granules, it may be, for example, talc, kaolin or diatomaceous earth, for liquid, concentrated forms, for example, a hydrocarbon, such as xylene or an alcohol, such as isopropanol, and for liquid forms of application, inter alia, water or diesel oil.

The compositions of the invention may also contain other compounds with a biological activity, for example compounds with corresponding or complementary herbicidal activity, such as phenoxy-acetic acid or phenoxypropionic acid, for example mecoprop, or a urea derivative, for example linuron or metoxuron, or ioxynil, or diclofop- methyl, or compounds with antidotal, fungicidal or insecticidal activity.

Specific examples of herbicidal formulations will be described below.

Example A: wettable powder.

For example, 25 parts of a compound of the invention 3204635-13 - the compound of Example 1 below, were mixed and comminuted with 25 parts of synthetic fine silica, 2 parts of sodium lauryl sulfate, 3 parts of sodium lignin sulfate, and 45 parts of finely divided kaolin, 5 until the average particle size was about 5 microns.

Dilute the resulting wettable powder for use as a spray liquid at the desired concentration with water.

Example B: Concentrated emulsion 25 parts of a compound of the invention, for example the compound of Example 1 below, 65 parts of xylene and 10 parts of emulsifier (for example ATLOX 4851 B, a mixture of calcium alkylarylsulfonate and a polyethoxylated triglyceride from Atlas Chemie GmbH ) were mixed well until a homogeneous solution was obtained. The concentrated emulsion obtained was diluted with water before use. Example C: Granules 5 kg of a compound according to the invention, for example the compound of Example 1, 20 below, were dissolved in 15 l of methylene chloride. This solution was then added to 95 kg of attapulgite granules (mesh dimensions 24/28 mesh / inch) and mixed well. The solvent was then distilled off under reduced pressure.

In the following examples, the temperatures are given in ° C.

Example 1: N- (diethylaminosulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea (method b)

To a suspension of 7 g (0.05 mol) of 2-methoxy-U-30 methyl-6-amino-triazine in 100 ml of tetrahydrofuran, which is at -5 ° C

was cooled, 4.5 ml (0.05 mol) of chlorosulfonyl isocyanate were slowly added. A slightly yellowish solution was obtained, which was stirred at room temperature for 10 hours.

At room temperature, 8 g (0.11 mole) of diethylamine dissolved in 10 ml of tetrahydrofuran were added dropwise to this solution and the reaction mixture was then stirred at 8204635 m - 1 - room temperature for 3 hours. The precipitate was sucked off, dissolved in CH 2 Cl 2, the solution washed with water, dried and evaporated. Thereafter, the residue was chromatographed on silica gel with a mixture of CH 2 Cl 2 and acetone (90:10) as the mobile phase and finally crystallized from a mixture of CH 2 Cl 2, diethyl ether and n-hexane to give the title compound as white crystals with a melting point of 143-1.5 ° C were obtained.

Example 2: 10 N- (2-cyanoethyl) -methyl-amino-sulfonyl-N '- (U-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea.

To a suspension of 56 g (0.10 mole) of 2-methoxy-k-methyl-6-aininotriazine in 650 µl 1,2-dimethoxyethane (suspension prepared in a nitrogen atmosphere) was added for 15 minutes and at at a temperature of 5 ° C add a solution of 35 ml (0.1 mole) of chlorosulfonyl isocyanate in 10 ml of 1,2-dimethoxyethane.

The pale yellow solution thus obtained was stirred under cool ice for 1.5 hours and then dripped to a solution of 69 g (0.82 mol) for 1.5 hours and at a temperature between 2 and 5 ° C. ) 3-methylamino-propionitrile in 150 ml 1,2-dimethoxyethane. The reaction mixture was then stirred under ice-cooling for 1 hour and at room temperature (2h ° C) for 2 hours, then poured onto 8 l of ice water and then 100 ml of 2N hydrochloric acid were added thereto.

After stirring well for 5 min, the white suspension was filtered off, washed with water and dried under reduced pressure at 50 ° C. The title compound thus obtained has a melting point of 13-137 ° C.

Example 3: N- / (2-chloroethyl) -methylaminosulfonyl-7-N1 - (i + - methoxy-6-methyl-1,3,5-triazin-2-yl) urea_

With careful exclusion of moisture (the device was purged with dry nitrogen), a solution of 35 ml (0.05 mol) of chlorosulfonyl isocyanate in 10 ml of absolute 9204635 - 15 -

1.2-dimethoxyethane within 10 min and at a temperature of 0 ° C, added with stirring to a suspension of 7 g (0.05 nol) 2-methoxy-1-methyl-6-aminotriazine in 80 ml absolute 1,2-dimethoxyethane . Stirring was continued for 1 hour at 0 ° C

5 until a light yellow solution was formed. This solution was added to a suspension of 13.3 g (0.102 mol) at 0 ° C. 2-Chloro-N-methylethylamino.hydrochloride in 50 ml of absolute 1,2-dimethoxyethane and 10.3 g (0.102 mol) of triethylamine in 30 ml of absolute 1.2- within this mixture (flask at 0 ° C) within 30 min. dimethoxyethane is added dropwise. The mixture was then stirred at room temperature for k hours and the solvent was then distilled off from a water pot under reduced pressure. The resulting solid residue was dissolved in 200 ml of water and acidified with hydrochloric acid to pH 3 · 15. The acidic solution was extracted three times with 100 ml of CH 2 and the combined OH 2 solutions were washed with water (three times with 50 ml). The solution was dried, the solvent was evaporated and the residue was chromatographed on a column of silica gel, using a mixture of diethyl ether 20 and acetone (9: 1) as eluent. The title compound was obtained in the form of colorless crystals which can be recrystallized from toluene. Melting point: 130 ° C.

Example fr: 25 Following the procedure of any one of Examples 1-3, using chlorosulfonyl isocyanate and suitable amines of formulas VII and V, the following compounds of formula Ib were obtained, wherein an h-methoxy-6-methyl-1, Represents 3,5 "triazin-2-yl group, R 1 represents hydrogen and 30" U 1 C 8 H 2 -HH; white crystals; m.p. 126-129 ° (dec.) U.2 anilino; white, amorphous; m.p. 1U6-1U8 ° (dec.) U, 3 O-chloroanilino; white, amorphous, m.p. 65 ~ 85 ° (dec.) U.U HHg 35 ch3hh 8204635-16-1 + 6 (CH3) 2N; m.p. 180-182 ° 1 + .7 C 2 H 5 (CH 3) N; m.p. 159 ", 161 °

1 + .8 n-C ^ ^ HH k.9 i-C H ^ ÏH

5 1+. Cyclopentyl-NH

1+. 11 cyclopentyl-N (CH3); m.p. 91 "92 °

1+. 12 cyclohexyl-NH

1 + .13 cyclohexyl-N (CH3); m.p. 168-172 ° 1 + .11 + allyl-NH; m.p. 112-111 + ° 10 1 + .15 allyl-N (CH); m.p. 129-130 °

1+. 16 2-propinyl-NH

U.17 C6H5N (CH3); m.p. 151 ° 1 + .18 c6h5n (c2h5)

1 + .19 CgH ^ HgNH

1 + 20 C6H5CH2N (C2H5) 1 + .21 HO-CH2CH2N (CH3); m.p. 120-123 ° 1 + .22 CH30-CH2CH2N (CH3) 1 + .23 (C130CH2CH2) 2N; m.p. 91-99 ° 1 + .2¾ C1CH2CH2CH2NH; m.p. 153 °

20 1 + .25 NC-NH

U.26 NC-CH2N (CH3); m.p. 128-130 ° 1 + .27 IC-CH2CH2li (CH2CH2OH) 1 + .28 C_H_Q0C-CH-NH; m.p .: 133-13 ^ d p d U.29 C2H500C-CH2-N (CH3); m.p. 109-112 ° 25 + 3o (ch3) 2nch2ch2-hh U.31 pyrrolidino; m.p. 168-170 ° it.32 piperidino; m.p. 152-151 + ° 1 + .33 morpholino; m.p. 17179 ° (dec.) I + .3I + 1 + -methyl-1-piperazinyl 30 1 + .35 perhydroazepin-1-yl 1 + .36 N (i-C3H7) 2; m.p. ll + 1-ll + l + ° 1 + .37 Ν (η-03Η?) 2; m.p. 132-131 + ° 1 + .38 Ιί (η-0 ^ Η9) 2; m.p. 130-131 ° 1 + .39 N (CH3) CH2-CSCH; m.p. 159 ° 161 ° 35 + 1 + O HH-CH2CH2OCH3; m.p. 132-135 ° 8204635 .......... ——'—-—: ........... ::::: ....... ..... ...................., ΐ ^ ριίΐρΐιΛιΐιι ^. ».; :: ........

- 17 - "" S? kM N (C 2 H 5) CH 2 CH 2 CNi m.p. 9-151 ° k.k2 N (nC3H7) CH2CN; m.p. 126-128 ° 1 * N3 N (i-CH) CH CH CN; m.p. 157 * 159 ° 3 7 2 2 U.UU NH- (O-CN-phenyl); m.p. 98 ° U.U5 NH- (p.Cl-phenyl); m.p. 176 ° U.U6 N (CH3) CH2CH2C6H5; m.p. 100 ° 1 * 7 N (C6H5) CH2C6H5; m.p. 15 ° J »M N (CH 3) CH 2 C 6 H 5; m.p. 1, 90 k.k9 N (CH_) CH m.p. 131-133

3 v CN

U.50 n (ch3) Xcn

If.51 NH-CHgCHgCN; m.p. 1 ^ 2 ° (dec.) 4.52 N (cyclopropyl) CH 2 CH 2 CN; m.p. 108-112 ° (dec.) 4.53 H (cyclopentyl) CH2CH2CNi m.p. 149-151 °

CH

4.5¾ N (CH3) -CH2-CH-CN

^ 55 N (CH3) A / CN; m.p. 16M66 ° ^ 56 h (ch3) X / cn

¾.57 N {CH3) / X CN

^ 58 N (CH2CH2CN) 2; m.p. 151-15 ° C 59 N (CH 3) ^ CN i m.p. 13¾-136 ° ¾.60 N (CH3) CH2-CHCl-CN (amorphous) ¾.61 NH-CH2CH2 (OCH3) 2; m.p. 135-138 ° C 62 nh- (ch 2) 3 OCH 3 ¾ 63 N (CH 3) CH 2 CH 2 COOCH 3; m.p. 81-8¾ ° ¾.6¾ n (ch3) ch2ch2coch3 ^ 65 NH-CH (C00CH3) 2; m.p. 129-131 ° ¾.66 NH-C (CH3) »CH-C00CH3 ¾.67 n (ch3) ch2coch3 ¾.6β NH-CH2CH2-N (CH3) 2 h.69 n (ch3) ch2ch2-n (ch3) 2 8204635-18 - U.70 RH- (o.COOCgH-phenyl); m.p. 1U50 U.71 NH- (o.OCH 3 ~ phenyl); m.p. 166 ° h, 72 RH- (o.NHg-phenyl); m.p. 135 ° U.73 N (phenyl) CH2 CH2 CN; m.p. 116 ° b, 7 ^ NH-imiCF-phenyl); m.p. 160 ° b.75 1,3-thiazolidin-3 "yl; m.p. 136 ° C. thiomorpholino; m.p. 1600 b.YY NH-tC ^; m.p. 200 ° (dec.) U.78 nh-cooc2h5 b.79 N (CH3) COOC2ï5

U.80 NH-C (CH 3) = CH-CN

1 * .81 N (COH) C 1 -CH 2 Cl; m.p. 90 ° <:) d d Λ Cl; m.p. 11U ° J • Cl U.83 N (CH3) CH2CH2CH2Cl; m.p. 2U1 ° A ci U.8 ^ NH-CH2; Rf. 0.65 (in ethyl acetate, op

Cl silica gel) fc.85 Nd.C ^ JCHgCHgCl; m.p. 132 ° b.86 m-ch (c2h5) -ch2ci 1 + .87 N (CH2C6H5) CH2CH2C1 U.88 n (ch2ch2ci) 2 U.89 N (CH3) CH2-CHC1-CH2C1 u.90 N (CH3) CH2 “CH = CHC1 lt.91 N (CH3) CH2-CC1 = CH2 k.92 N (CH3) CH2-CH = CC12 U.93 NH-CH2CH2SCH3 b.9b N (CH3) CH2CH2SCH3 k.95 NH (2-CH3S -CgHlt) b.96 N (CH3) -CH2CH2S-C6H5

Example 5

According to the method of any of Examples 1-3j using chlorosulfonyl isocyanate and a suitable amine of formula VII or V, the following 8204635 ---------: ......... '* ................... ·' ·: "........ ~ · '· ...... * ·' ·" -: - 19 - bonds of the formula Ib obtained, in which R 1 and the ethyl group represent a hydrogen atom and R 1 is 5.1 U. 6-dimethylpyrimidin-2-yl 5.2 U-chloro-6-methylpyrimidin ** 2 -yl 5 5.3 2, U-dimethylpyrimidin-6-yl 5.U U-chloro-2-methylthio-pyrimidin-6-yl 5 * 5 3 ^ dimethyl-1,2-yl-triazin-6-yl 5.6 U, 6 -dichloropyrimidin-2-yl 5.7 2 ^ U "dichloro-1 ^ 3> 5" triria-6-yl 10 5.8 2-chloro * ^ - methoxy-1 ^ 3> 5 * triazin-6-yl 5 * 9 2- amino-U-chloro-1,3,5 ”triazin-6-yl 5 * 10 2-chloro-1» -methyl-amino-1> 3> 5 “triazin-6-yl 5 *.” 11 2-chloro-U -dimethylamino-1, 3> 5 "triazin-6-yl 5.12 2-chloro-U-diethylamino-1 ^, 3> 5" triazin-6-yl 15 (snq? t. 1U9-1520)

Example 6

Following the procedure of any one of Examples 1-3, using the chlorosulfonyl isocyanate and the appropriate amines of formulas VII and V, the following compounds were obtained with formula Tb, wherein R 1 represents a U, 6-dimethylpyrimidine group, R ^ represents a hydrogen atom and MR ^ R2 * 6.1 N (CH3) CH2CH2CN; m.p. 16I-1620 6.2 NiCH2; amp * 20U-2060 6.3 1 ^ 3 “thiazolidin-3-yl” mp. 157 ° 25 6.V NH- (o.CN-phenyl); m.p. 131 ° 6.5 N (CH2) CHgCHgOCgH ^; m.p. 136 ° 6.6 NH-t. C ^; m.p. 151 ° 6.7 NH2; m.p. 180 ° 6.8 N (CH.) CH CH-C 1 H-; m.p. 135 ° 32 205 30 6.9 HH-CH 2 CH 2 OCH 3; m.p. 128-130 ° 6.10 NH- (m.CN-phenyl); m.p. 19 ° 6.11 NH- (p.CN-phenyl); m.p. 171 ° 6.12 NH- (o.CF3-phenyl); m.p. 80 ° 6.13 NH- (m.CF3-phenyl); m.p. 1U90 35 6.1U HH (o.OH-phenyl) i m.p. 126 ° 8204635-20 - 6.15 ΝΗ- (o.CH2-phenyl); m.p. 165 ° 6.16 NH- (o.enyl); m.p. 1U90 6.17 NH- (0.COOC ^ H ^ -phenyl); m.p. 1U8 ° 6.18 N (C / .H_) CH_CH_CN; m.p. 161 ° O 5 2 2 5 6.19 NHCHgCH2 -S-t.CjjH ^; m.p. 50 ° 6.20 N (CH3) CH2CH2SCH3 6.21 NH (2 ~ CH3S “CgH ^) 6.22 n (ch3) ch2ch2sc6h5

Example 7: methyl Hipiperidinosulfonyli-N '- - - methoxy-ö-methyl-1,3,5-triazin-2-yl) carbamimidothioate (method c)

A suspension of 2.0 g (0.81 mol) of sodium hydride in oil (80% by volume) was suspended in 150 ml of diraethylformamide and this suspension was added to 11.2 g (0.08 mol) of 2- amino "U-methoxy-6-methyl" 1,3,5 "triazine. The reaction mixture was stirred at room temperature for 3 hours until no hydrogen evolution could be observed. This solution was then added dropwise to a solution of 21.5 g (0.08 mol of the dimethyl ester of N-piperidinosulfonylcarbonimidodithioic acid in 50 ml of dimethylformamide) at a temperature between 20 and 30 ° C. stirred at room temperature for hours, poured onto 2 l of ice water, aspirated and the pH of the basic mother liquor was adjusted between 2 and 3 with an aqueous 10% hydrochloric acid solution. After 15 min.

25 was aspirated, stirred there. washed with water. The crystalline precipitate was dissolved in CH 2 Cl 2, the solution was shaken with water, dried over sodium sulfate, evaporated to dryness, and the residue was recrystallized from a mixture of C 2 Cl 2 and hexane to give the title compound as white crystals. with a melting point of 173-17 ° C.

Example 8

Following the procedure of Example 7, however, using suitable compounds of formula VI and of formula VII, the following compounds of formula Ic 8204635-21 were obtained, in which RH 1 R 3 a -CH 2 O-6-CH 3 -1,3,5 "triazin-2-yl-amine group and NR ^ Rg and ARg are: 8.1 NiCH ^ Jg and SCH ^, respectively. m.p. 171 "173 °; white crystals).

8.2 piperidino and OCgH ^. resp. m.p. 138-11 * 0 ° white crystals from CHgClg / diethyl ether / hexane fraction).

8.3 N (CH ^) cyclohexyl and SCH ^ resp.

8.1 »morpholino and SCH ^ resp.

8.5 N (CH_) cyclopentyl and SCH. resp.

8.7 pyrrolidino and SCH ^ resp.

8.8 M (CH2CH20CH3) 2 and SCa3, respectively.

8.9 H (CH3) C2H5 and SCH3, respectively.

8.10 N (CH3) CH2CH2C6H5 and SCH3, respectively.

8.11 N {CgH ^) CHgCgHj and SCH3, respectively.

8.12 (CH3) C6H5 and SCH3, respectively.

3.13 N (CH3) CH2C6H5 and SCH3, respectively.

8.1 * »N (i-C3H ^) 2« ï SCH3 resp.

8.15 N (CH3) CH2CH2CN and SCH3, respectively.

Example 9

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

Example 10: N- (piperidinosulfonyl) -N '- (1'-methoxy-6-methyl-1,3,5 ”triazin-2-yl) urea (method d).

A suspension of 6 g (0.0279 mol) of HgO in 60 ml of a 15 ml solution of water in tetrahydrofuran is added dropwise to U, 5 ml (0.0353 mol) of BF3 at a temperature between 20 and 30 ° C. .0 (C2H5) 2. The reaction is weakly exothermic. To this suspension, after stirring at room temperature for 30 min, 6.1 g (0.017 mol) of the methyl ester of N- (1'-methoxy-6-methyl-1,3,5 ”triazin-2-yl) - N'-piperidinosulfonyl carbamidothioic acid 35 was added. The reaction is again slightly exothermic. The reaction mixture is stirred at room temperature for 2 hours, the color of which gradually changes from red to beige and is then aspirated. The crystals are washed with water and then with CH2 Cl2. Then the white crystals are dissolved in a 0.1 N sodium hydroxide solution, the solution is filtered, acidified with a 2N hydrochloric acid solution and extracted with CHgClg. The CHgCl 2 solution is dried over sodium sulfate and evaporated to dryness. The residue is purified by column chromatography and recrystallized from a mixture of CH 2 Cl 2, diethyl ether and a hexane fraction to give the title compound as white crystals (melting point 152 DEG-15 DEG C.).

Example 11

Following the method of Example 10, however, using the appropriate compounds of formula Ic as starting material, the following compounds of formula Ib were obtained, wherein a -CH-O-ö-CH--1,3,5-triazine - represents 2-yl group, R 1 represents a hydrogen atom and NR 2 = 11.1 (mp 172-175 °, white crystals, starting from example 8.1).

11.2 N (CH2) CHgCHgCN; m.p. 129, 131 ° of example 8.15).

11.3 N (CH2) cyclohexyl; m.p. 168-172 ° (from example 8.3).

11.U morpholino; m.p. 176-179 ° (from Example 8.k) 11.5 N (CH2) cyclopentyl; m.p. 91 “92 ° (from example 8.5) 11.6 Νίη-Ο ^ Η, ^; m.p. 132-13 ° (of Example 8.6) 11.7 pyrrolidino; m.p. 168-170 ° (from Example 8.7) 11.8 N (CHgCH2 OCH2) g; m.p. 97 ° 99 ° (from example 8.8) 11.9 NÉCH ^ JCgHj ,; m.p. 159 ”161 ° (from Example 8.9) 11.10 N (CH2) CHgCHgC; m.p. 100 ° (from example 8.10) 11.11 NiCgHjJCHgCgHj .; m.p. 15 ^ (of Example 8.11) 11.12 N'CH ^ JCgH ^; m.p. 151 ° (from example 8.12) 8204635-11-23 N (CH3) CH2CgH5i m.p. Ik9 ° (from example 8.13) 11.1¾ Sd ^ C ^ Sjj ^ i saq? T. 11 »1-1M ° (from example 8.1¾) Example 12

According to the procedure of Example 10, starting from the compound of Example 9, the corresponding compound of formula Ib is obtained, in which 12.1 NB ^ Rg represents a -NiCH ^ Jg group, represents a, 6-dimethylpyrimidin-2-yl group and R ^ represents a hydrogen atom (mp .: 20U-206 ° C).

10 Example 13

The oxidation of the compound of Example 8.1 to the compound of Example 11.1 is conveniently carried out as follows

To a solution of 102 g of the compound of Example 8.1 in 700 ml of CH 2 Cl 2 is added dropwise, with stirring, 355 g of a 15% strength solution of hydrogen peroxide in acetic acid, at room temperature.

The reaction mixture is stirred at room temperature overnight, poured onto 2 l of ice-cream and the separated 20 CHgClg phase is twice with 500 ml of a concentrated

Shake NaHSO 2 solution and three times with water, dry and concentrate by evaporation to give the compound of Example 11.1 in the form of white crystals (mp: 172-175 ° C).

25 Intermediates

Example 1U: N-chlorosulfonyl-N '- (U-methoxy-6-methyl-1,3,5-triazin-2-yl urea).

To a suspension of 3.5 g of 30 (0.025 mol) 2-methoxy-U-methyl-6-aminotriazine in 35 ml of tetrahydrofuran cooled to -20 ° C, a solution of 2.3 ml (0.026 mol) of chlorosulfonyl isocyanate in 15 is slowly added. ml of tetrahydrofuran added. The reaction mixture is then stirred for 2 hours and the temperature is allowed to rise to 0 ° C. The title compound precipitates from the resulting yellow solution in the 8204635-2k form of needles, which are aspirated and washed with diethyl ether. The needles decompose at about 160 ° C.

Example 15: 5 The dimethyl ester of N- (piperidinosulfonyl) carbonimidodithioic acid.

To a solution of 32.8 g (0.2 mole) of piperidino-sulfonamide in 150 ml of dimethylformamide, 12 ml of a solution prepared from 16 g (0.10 mole) of sodium hydroxide in 20 ml of water are added with vigorous stirring. The precipitate of the sulfonamide precipitates. After adding 6.6 ml (0.11 mol) of sulfur carbon, the temperature rises little (making it necessary to cool a little with ice) and the reaction mixture turns deep orange-red first and after 10 min.

15 yellow orange. Then 6 ml of the aforementioned sodium hydroxide solution and 3.5 ral (0.055 raol) of carbon sulfur are added and this procedure is repeated after 10 min.

The reaction mixture is stirred for 15 minutes and 56.7 g (0mol) of methyl iodide are added dropwise to the yellowish suspension thus obtained at 25 ° C. After about 10-15 rain, a yellow solution is obtained, which is stirred at room temperature for 15 hours. The precipitated crystals are aspirated at 0 ° C. An additional fraction is obtained by column chromatography from the mother liquor. The crystals are suspended in CH 2 Cl 2, shaken with water, dried over sodium sulfate, evaporated to dryness and the residue is recrystallized from a mixture of CH 2 Cl 2 and hexane.

The title compound is obtained in the form of white crystals with a melting point of 88-90 ° C.

Example 16;

The diethyl ester of N- (piperidinosulfonyl) carbonimidic acid ________________

A mixture of 6.5 g (0.0U mole) of piperidino-sulfonamide and 11.5 g (0.06 mole) of CfOC 3 H 3) was heated at 130 ° C with stirring and kept at this temperature for 2 hours .

8204635 - 25 -

Then, 1.2 ml of ethanol was distilled off, and then excess C (OCgH2) 2 was distilled off under reduced pressure. The resulting residue, a dark oil, is purified by column chromatography, whereby the title compound is obtained in the form of an oil which crystallizes, melting point: kk-U6 ° C.

Study results Example 17:

Weed control - Treatment before hatching. _

Seed pots (with a diameter of 7 cm) were filled with a mixture of a peat culture substrate and sand. The exposed surface of this mixture was sprayed with a test liquid of a test compound (eg processed according to example B) and seeds of Lepidium sativum. Agrostis alba. Avena sativa and Lolium perenne were sown in each pot, the Avena sativa and Lolium perenne seeds being covered after sowing with a thin layer (0.5 cm) of peat culture substrate and sand. The 20 pots were kept at room temperature for 21 days with 1k-17 hours of exposure (daylight or corresponding light) per day. The herbicidal activity of the special herbicide was determined after a period of 21 days. This assay included a visual assessment of the degree and quality of damage inflicted on different plants.

The compounds of formula I of the above examples 1-13 were used in the manner described above in dosages equivalent to 1 and 5.6 kg of active agent per hectare.

Herbicidal activity was observed, that is to say that considerable damage was found to the plants to be tested.

Example 18:

Weed control - post hatching treatment. A procedure analogous to that used in Example 8204635-26-17 was followed, except that the compounds to be tested (herbicides) were applied when the plants were at the 2-k leaves stage, with the sowing of the plant seeds being performed that it was ensured that the plants reached the stage of 2-h leaves at about the same time.

The compounds were again used in dosages corresponding to 1.1 Kg per hectare and 5 * 6 Kg per hectare as described above. The determination of the herbicidal activity was performed 21 days after the application of the compounds to be tested and this entailed a similar evaluation as described in example "17-. A herbicidal activity was observed. Example 19: 15 Studies on the field

The useful herbicidal activity of the compounds of the invention has been confirmed by a further study on different grassy and dicotyledonous weeds in different crops at application rates of 0.3; 0.6; 1.0; 1.2 and 2.0. The recommended herbicidal activity was observed, inter alia, with the compounds of Examples 1,2, k.1, U.6, U.7, k.37 »U.U1 and k.k2t in particular against dicotyledonous weeds. The effect after hatching is. . ...

m generally clearer than before hatching.

8204535

Claims (7)

New aminosulfonylurea derivatives belonging to the group consisting of 1-diazinyl or 1-triazinyl-3 * amino-sulfonylurea, 1-diazinyl or 1-triazinyl-2-alkyl-3-aminosulfonyl-isourea and their corresponding isothiourea derivatives. 2. Compounds according to claim 1 of formula 'N - SO.XI p 2 2 1Q in which and Rg, independently of one another, is a hydrogen atom, a cyano group, C 1-8 alkoxy-CO group or an unsubstituted or substituted alkyl group with 1- 6 carbon atoms, alkenyl group with 2-6 carbon atoms, alkinyl group with 2-6 carbon atoms, cycloalkyl group with 3-7 carbon atoms and / or phenyl group represent, or wherein R 1 and R 8 together with the nitrogen atom to which they are attached a saturated , heterocyclic 5 ”to 7-ring forms, X represents a group of formula NR ^ -CO-NR ^ R ^ or a group Gg of formula N * C (ARg) -NR ^ R ^, a hydrogen atom or an alkyl group with 1-5 carbon atoms, 2Q Rj ^ is a 1 * -R ^ * 6 "RQ-pyrimidin-2-yl-, 2-R ^ -6-Rg-pyrimidin-U-yl-, UR ^ -6-Rg -1,3,5 "triazin-2-yl- or 5" R ^ ~ 6 "Rg-1,3, ^" triazin-2-yl group, R ^ represents a hydrogen atom or an alkyl group of 1-5 carbon atoms , Rg represents a hydrogen atom or an alkyl group with 1-5 carbon atoms, Rg and Rg, independently v an 2 £. each other, a hydrogen or halogen atom, an alkyl group with 1-5 carbon atoms, a haloalkyl group with 1-5 carbon atoms, an alkoxy group with 1-5 carbon atoms, an alkyl-thio group with 1-5 carbon atoms, an alkoxy-C 1-6 alkyl group, a lfflg group, an alkyl-NH group and / or a diiC 1 -alkylN growth group and A 0 or S. Compounds according to claim 2, wherein X is a (b, 6-dimethylpyrimidin-2-yl) -NH-CO-NH group or a (U-methoxy-6-methyl-1,3,5 "triazine-2- yl) -NH-CO-HH group. k. Compounds according to claim 3, wherein R 1 represents a 8204635-28 hydrogen atom or a straight-chain alkyl group with 1-3 carbon atoms and a straight-chain alkyl group with 1-3 carbon atoms, a 2-cyanoethyl group, an allyl group or a propinyl group. Methods for preparing compounds according to claim 1, characterized in that a) 1-diazinyl and 1-triazinyl-3-aminosulfonyl urea is prepared by urea condensation of the appropriate isocyanate or carbamate, or a reactive derivative thereof, with the corresponding amine, b) 1-diazinyl and 1-triazinyl-3-aminosulfonyl urea, by reacting the appropriate chlorosulfonyl urea with the corresponding amine, c) 1-diazinyl and 1-triazinyl-2-alkyl-3-aminosulfonyl - 15 isourea and isothiourea obtained by reaction of the appropriate R-aminosulfonylcarbonimidic acid or dithioic acid, or an ester of such acids, with the corresponding amine, d) 1-diazinyl-1-triazinyl-3-aminosulfonylurea prepared by oxidation of the corresponding isothiourea . Processes according to claim 5 for preparing a compound of the formula I as defined in claim 2, characterized in that a) a compound of the formula R 1 R 2 N "SO 2 G 1 Ia 25 is prepared, wherein R 1, R 2, and G.] de meanings defined in claim 2 have, under urea condensation reaction conditions, a compound of formula r1r2h-so2-nr9x1 II wherein R1 and R2 have the meanings defined in claim 2, either R1 is a hydrogen atom or an alkyl group of 1-5 carbon atoms and a hydrogen atom or a carbonyl group-containing functional, reactive derivative of C00H, or R9 and X ^ together form a C = O group ^ flates react with a compound of formula 35 in 8204635-29 wherein R ^ has a meaning defined in claim 2 and R'g and X'1 have meanings given respectively Rl and Xl, provided that the compound of formula II or the compound of formula III has a reactive carbamic acid or an isocyanate or b) a compound of formula r1r2h-so2-hh-co-hr ^ r5 Ib, wherein Rp R2, Rl and Rl have the meanings defined in claim 2, prepared by a compound of formula 10 ciso2-nh- co-nHj4r5 IV, wherein R ^ and R ^ have the meanings defined in claim 2, to react with an amine of formula vyra v wherein R ^ and Rg have the meanings defined in claim 2, or c) a compound of formula h1r2nso2-n «c (ar6) -hrur5 Ic, wherein Rp R2, R ^, R ^, Rg and A have the meanings defined in claim 2, prepared by a compound of formula / AR, R1R H-SO-HC ° VI Xar6 wherein Rp Rg, A and R ^ have the meanings defined in claim 2, to react with a compound of formula HHRi ^ VII wherein and have the meanings defined in claim 2, or d) a compound of formula Ib , as defined in this claim, prepared by a compound of formula R1RgNSOg-H ^ C (SRg) -HR ^ R ^ 1d wherein Rp R2, R ^, R ^ and Rg oxidize the meanings defined in claim 2. // 25 7 · A herbicidal formulation comprising one or an 8204635-30 number of compounds according to any one of claims 1-U and optionally an agricultural diluent acceptable. 8. A method of controlling weeds, characterized in that one or more compounds according to claims 1-U are used as a herbicide. 9. Methods as described in the description and / or examples. 10. Compounds of formula IV as defined in claim 6. ---- b * 8204635