PT89574A - Herbicidal sulphonyl:urea salt prepn. - from alkali(ne earth) hydroxide and soln. of sulphonyl:urea in halogenated hydrocarbon solvent - Google Patents

Abstract

Prepn of herbicidal sulphonylurea salts of formula (I) (J-S02-N(-)-C0-NR-B)m M(m+) (I) where M = Li, Na, K, Mg or Ca; R = H or alkyl; J = opt. substd. homocyclic gp or heterocyclic gp; B = opt. substd. heterocyclic gp with C and N ring atoms; and m = 1 or 2; comprising contacting a soln of the corresp sulphonylurea (II) in a water-immiscible halogenated hydrocarbon solvent with the corresp. alkali(ne earth) metal hydroxide and separating the salt, pref. by evapn of the solvent. Prepn. of a soln. of (I) comprises contacting the corresp. (II) with an alkali(ne earth) base in a water-immiscible aprotic solvent.

Description

BACKGROUND OF THE INVENTION BACKGROUND OF THE INVENTION BACKGROUND OF THE INVENTION BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for the preparation of a sulfonylurea,

U.S. Patents Nos. 4,599,412 and 4,659,823 relate to the preparation of sulfonylurea salts using a large number of methods, including the reaction of corresponding N-protonated sulfonylureas with a solution of an alkali metal or alkaline earth metal salt having an anion sufficiently basic (for example, hydroxide) or via ion exchange. These methods provide a sulfonylurea salt having a purity of approximately 70%, according to elemental analyzes. This process uses water or miscible solvents with water (for example, methanol or tetrahydrofuran) and consequently a less pure salt contaminated with water is obtained, whereby molecular sieves should be used. The quantum stability of these products contaminated with water does not often correspond to commercial requirements.

SUMMARY OF THE INVENTION The present invention relates to a novel process for the preparation of herbicidal salts of sulfonylurea and of general formula

(D

J-S-N-C-N-B

IIθ I

Wherein M represents a lithium, sodium, potassium, magnesium or calcium atom; R represents a hydrogen atom or an alkyl group; J represents an optionally substituted heterocyclic or homocyclic group; B represents an optionally substituted heterocyclic group of which the cyclic skeleton contains carbon atoms and at least one nitrogen atom; and m is the integer 1 or 2; which comprises treating a sulfonylurea solution in a non-water miscible halogenated hydrocarbon solvent with an appropriate alkali metal or alkaline earth metal hydroxide. The resulting salts are then separated by evaporation of the solvent.

Alternatively, the salts of formula

The solution is partitioned directly into a water-miscible, non-hydroxylic solvent to give a stable liquid solution containing 5 to 40% of the active ingredient,

It is understood that when in the above-mentioned general formula I, R represents a hydrogen atom, the salt prepared consists, if need be, of two equilibrium forms of deprotected species as can be seen in Scheme I. (II) J-S-N-C-N-B 11 Θ | (1: 1)

The non-limiting aspects of the processes according to the present invention providing preferred salts due to their more intense herbicidal action or greater stability are processes for the preparation of salts of the above-mentioned general formula in which R represents a hydrogen atom or a CH3; 0 represents a group of formula

-4-

J-14 J-15-5- *

in which Q represents an oxygen or sulfur atom or an S (O) group, (O) 2 or C (O); R 1 represents a fluorine, chlorine or bromine atom, a nitro group, cyclopropyl, C1 -C3 alkyl, C1 -C3 alkoxy, C1 -C3 alkoxy, C1 -C3 alkoxy, C1 -C3 alkoxy, C2-3 alkoxy, C2-3 alkoxy or CH2 CN, or a group of formula (C 1 -C 6) alkyl,

wherein Ra represents a C1-3 alkyl group optionally substituted with a halogen atom or a C1-2 alkoxy or CN group, cyclopropylmethoxy group, C1-6 alkoxy group, allyl or propargyl; R 2 represents a hydrogen atom or a C 1 -C 3 alkyl group or C 2 -C 20 alkoxy, R c represents a C 1-6 alkyl group; R j represents a C1 -C12 alkyl or C1 -C10 cycloalkyl group; R & represents a hydrogen atom or a C1-4 alkyl group; Rf has a C1-3 alkyl, halo-C1-4 alkyl, allyl or propargyl group; R6 represents a C1-4 alkyl, haloalkyl or C3-5 cycloalkyl; n is zero or the integer 1 or 2 and L represents a group

L-3 L-4

L-5

L-6

L-7

L-8

L-9 L-10

L-11 -7 '

S - = -

L-26 L-27 L-28 N-Ν '" (I.e.

R Ο " R e and R »are each hydrogen atom or a CU grupo; group; R. is a hydrogen atom or a CH3 or CH3 CH3 group; R- | R 3 is hydrogen, CH 3, CH 2 CH 3, OCH 3, OCH 2 CH 3, SCH 3 or SCH 2 CH 3; and R m represents a hydrogen atom or a CH 3 group; R 2 represents an atom of hydrogen, fluorine, chlorine or bromine or a group NO 2, CN, C 1 -C 4 alkyl, CF 3, C 1 -C 12 H 2, halogen, C 2-32 alkoxy or C 1-6 alkyl; R 3 represents a NO 2, CO 2 CH 3, CO 2 CH 2 CH 3, S (O) 2 N (CH 3) 2, S (O) 2 CH 3 or S (O) 2 CH 2 CH 3 group; C 3, ,alkenyl, C 3 alco ,alkenyl, C ^ alco alcoalkoxy, C ^ alco alcoalkoxy, C ^ 2 ,alkyl, C 3 alquilo alcoalkoxy, C 3 alquilo alcoalkoxy, C _ alquilo alquiloalkyl, C _ alquilo alquiloalkyl, C ^ alquilo alquiloalkyl, C ^ alquilo alquiloalkyl, C ^ alquilo alquiloalkyl, C ^ alquilo alquiloalkyl, C ^ alquilo alquiloalkyl, C ^ alquilo alquiloalkyl, ) 2 NR d R e, S (O) n R f, C (O) R g or L wherein

R ', R', R ', R', R ', R' ', and L have the meaning defined above;

R5 represents a fluorine, chlorine or bromine atom, a C1-6 alkyl group, halo-C1-4 alkyl, halo-C1-4 alkoxy, C1-4 alkoxy or C1-4 alkyl or a (O) n R f, C (O) R g or L wherein Ra, Rfe, Rc, Rd 'R', R ', Rg, and Rt The meaning defined above;

R6 represents a hydrogen, fluorine, chlorine or bromine atom or a CH3 group;

Ry represents a fluorine, chlorine or bromine atom, a C _ alquilo gr alkyl group, a C alco alco alco alkoxy or a C₂ al hal alkoxy or a group of the formula C 0 0 C C 0 N NR ampRc, S 0] 2 NR d R e, S (O) n R f, C (O) R or L wherein R 1, R 2, R c> Rd, R e> R f, R g, n or L has the meanings defined herein;

R6 represents a hydrogen, fluorine or chlorine atom or a CH3 or OCH3 group;

R 2 represents a hydrogen atom or an alkyl group; R 1 represents a fluorine, chlorine or bromine atom, a hydrogen atom, C (O) NR b R c, S (O) 2 NR d R e, S (O) R 2, R 2, R 3, nRf, C (O) Rg or L wherein Ra 'Rb' Rcs Rd 'Re' Rf 'Rg' n or L has the meaning -10 defined above;

R11 represents a hydrogen, chlorine, fluorine or bromine atom or a C1-3 alkyl or C1-3 alkoxy group; R 2 represents a hydrogen atom or an alkyl group; R 2 represents a hydrogen atom or a CH 3 group; R 4 represents a hydrogen atom or a C 1-6 alkyl, halogen-C 1-4 alkoxy, C 2-4 alkoxy or C 4-8 cycloalkyl-C 1-4 alkyl; R 1g represents a hydrogen, fluorine, chlorine or bromine atom or a CF 1, OCH 2, or SCH 2 group; and B represents a group of the formula wherein X represents a chlorine atom or a CggCHCH₂ OC group; Y represents a C1-3 alkyl group; (C1 -C3) alkoxy, C1 -C2 H, OCH2 CF3, NHCH3 or N (CH3) 2, and Z represents a nitrogen atom or a Cd group, with the proviso that (1) Z represents a CH group and Y represents a C when X represents a chlorine atom; and â € ‡ â € ‡ â € ‡ â € ‡ â € ‡ â € ‡ â € ‡ â € ‡ â € ‡ / (2) Z represents a CH group when X or Y represents a Câ,

In the definitions cited above the term " alkyl " used individually or in compound words such as " alkyl-thio " or " halogenoalkyl " means a straight or branched chain alkyl group such as, for example, a methyl, ethyl, n-propyl, isopropyl or different butyl isomers, the term " alkoxy " means a methoxy, ethoxy, n-propyloxy, isopropyloxy group and the different isomers: butyloxy. The term " alkenyl " means a straight or branched chain alkene such as, for example, a vinyl, 1-propenyl, 2-propenyl or 3-propenyl group, the term " alkylthio " means a methylthio, ethylthio group and the various butylthio and propylthio isomers, the term " cycloalkyl " means a cyclopropyl cyclobutyl or cyclopentyl group. The term " cycloalkyl-alkyl " means a cyclopropylmethyl group, more specifically from cyclopropylpropylo to cyclopentylmethyl, the term " halogen " individually or in compound words such as " halogenoalkyl " means a Stomo of fluoro, chloro, bromo or iodo. Moreover, when used in the words

(compounds such as " halogenoalkyl " this alkyl group may be partially or fully substituted with the same or different halogen atoms. Examples of halogenalkyl groups include CH 2 CH 2 F, CF 2 CF 3 or CH 2 CHF 3 groups, the term quot; halogen-alkenyl " is in a difference similar to that of " halogenoalkyl " cited above. The total number of carbon atoms in a substituted group is indicated by the suffix C 1 -C 6 wherein i and j represent numbers For example, a C1-3 alkylthio group should designate from a methylthio group to propylthio, alkoxy-C1-2 alkoxy group may represent a C2-C20 alkoxy group; to designate various isomers of a substituted alkoxy group with a second alkoxy group containing a total of 3 carbon atoms, examples of which include the alkoxy-C1-4 alkyl group, C1-6 alkoxy- C2 may designate the group CH20CH3 and a group alkoxy-alkyl may designate the various isomers of an alkyl group substituted with an alkoxy group having 4 carbon atoms in the total such as, for example, a group CH 2 OCH 2 CH 2 CH 3, CH 2 CH 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 3, CH 2 CH 2 CH 2 CH 2 CH 3, CH (CH 2 CH 3) and (ch3) 2och3.

Especially preferred processes

Especially preferred processes for reasons of higher yield or more intense herbicidal action or greater chemical stability of the salts prepared are the processes according to the present invention which enable the isolated salt or a liquid solution to be prepared to be prepared; 1-N-methyl-7-carbonyl-17-2- (4-methoxyphenyl) -3- (5-methyl-1H-tetrazol-1-yl) -benzenesulfonamide, (Compound 1) 2. N-7 / N- (4,6-Dimethoxy-1,3,5-triazin-2 (5-methyl-1H-tetrazol-1-yl) -benzenesulfonamide. chloro-6-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate (Compound 2) chloro-6-methoxy-2-pyrimidinyl) -amino] carbonyl] amino] sulfonyl} benzoate. 1,3,5-triazin-2-yl) -N-methylaniline carbonyl 17-amino-7-sulfonyl benzoate, (Compound 3) 6. 2- (N- 4-methoxy-6-methyl-1,3,5-triazol-1-yl) -N-methylamino] carbonyl] amino] sulfonyl] benzoate, (4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] sulfonyl] -N, N-dimethyl] -3-pyridinecarboxamide (Compound 4). [(4,6-dimethoxy-2 piperidin-1-yl) amino] carbonyl] amino] sulfonyl] - N, α-dimethyl-3-pyridinecarboxamide.

A liquid composition containing the preferred salt shown in 5,

A liquid composition containing the preferred salt shown in 6.

2- (2-Chloroethoxy) -N-CCC ('(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] benzenesulfonamide, (Compound 5)

2- (2-Chloroethoxy) -N - ((((4-methoxy-6-methyl-1,3,5-triazin-2-yl] amino) carbonyl) benzenesulfonamide gives,

3 - (((((((4-Methoxy > 6-methyl-1,3,5-triazin-2-yl) aminocarbonyl)) - amino] )) -2-thiophenecarboxylate (Compound 6)

3 - ((((((4-Methoxy-6-methyl-1,3,5-triazin-2-yl) amino) carbonyl]) amino)) > sulfonyl) ) -2-thiophenecarboxylate,

2 - [[[2 - [(2,6-Dimethoxy-2-pyridyl) amino] amino] carbonyl] amino] sulfonyl] methyl] benzoate, Compound 7],

16. To a solution of methyl 2- (7 '' - (4,6-dimethoxy-2-pyrimidinyl) amino) carbonyl] amino] sulfonyl} (Compound 8) The title compound was prepared as a white solid.1H NMR (DMSO-d6) δ 18. 2-Chloro-N-methyl-2- (3-methyl-2-pyrimidyl) amino] carbonyl] amino] sulfonylbenzoate. methoxy-6-methyl-1,3,5-triazin-2-yl} -amino] carbonylamino] benzenesulfonamide (Compound 9) 20. 2-Chloro- 2-yl] amino] carbonyl] -benzenesulfonamide The title compound is prepared from 2 - [(4-methoxy- methoxy-6-methyl-1,3,5-triaza-2-yl} amino] carbonyl] amino] sulfonyl} benzoate (Compound 10) (4-methoxy-6-methyl-1,3,5-triazol-2-yl) aminocarbonylamino] sulfonyl] benzoate.

2- [77 (4-Ethoxy-6'-methylamino-1,3,5-

-triazin-2-yl) amino] carbonyl] amino] sulfonamide. -benzoate. [Compound 11] 24. 2- [7-Ethoxy-6-methylamino-1,3,5-triazin-2-yl) amino] carbonyl] amino] -sulfonyl] (4,6-dimethoxy-2-pyridyl) amino] carbonyl] amino] -sulfonyl} -1-methyl-1 H -pyrazole- 1-methyl-1 H -pyrazolo [4,3-d] pyrimidinyl} amino] carbonyl] amino] -5-methylimidazo [1,2- 4-Methoxy-6-methyl-1,3,5-triazol-2-yl) -N-amino-7-carbonyl] -2- - [2-methoxyT-ethoxy] -benzenesulfonamide, (Compound 13). 2- [7-N- [4-methoxy-6-methyl-1,3,5-triazol- A solution containing the preferred salt shown in 10 and wherein the solvent used is triethiolphosphate. A liquid solution containing the preferred salt shown in 10 and wherein the solvent used is triethyl phosphate. liquid solution containing the preferred salt shown at 10. and wherein the solvent used is 1-methyl-2-pyrrolidine, 31. A solution liquor 1a presented in 29 or 30 directly prepared by a process with a single phase which allows to prepare the salt in the aprotic organic solvent,

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel process for the preparation of sulfonylurea salts which are used in liquid and anion compositions which are readily dispersible with improved chemical stability and biological action. These solutions are miscible with water, obtaining true solutions that are usable as herbicides during pre-emergence or during post-emergence.

Part of this novel process uses water-immiscible halogenated hydrocarbons as the solvent in which the heterogeneous reaction takes place between the sulfonylurea and the metal hydroxide. This process provides products in the form of very pure salts (purity greater than 96%, according to elemental analysis). The dispersible liquid or anhydrous solutions of the salts prepared by the process according to the present invention exhibit excellent stability during storage, which makes them suitable for commercialization,

An alternative process employs a water-miscible solvent in which a homogeneous reaction takes place between the sulfonylurea and the metal hydroxide. This process is provided in the very pure liquid solutions (96%) of salts according to the present invention. These solutions exhibit excellent stability during storage and are readily miscible with water. Examples of water-soluble solvents are triethylphosphate, 1-methyl-2-pyrrolidine, diacetone alcohol, dimethylsulfoxide and dimethylformamide.

Free sulfonylureas whose salts are prepared by this process may in turn be prepared by conventional methods. See, for example, U.S. Patents 4,127,405; 4 310 346; 4 370 480; 4 383 113; 4 394 506; 4,398,939; 4,420,325; 4,435,261; 4,441,910; 4 548 638; 4,452,628; 4,456,469; 4,481,029; 4,494,979; 4 544 401; 4,547,215; 4,586,950; 4,643,759; 4,655,817 and 4,569,369; European Patent Applications Nos. 44,209 published January 20, 1982, 44,808 published January 27, 1982, 79,683 published May 25, 1983, 83,975 issued July 20, 1983, 85 476 published August 10, 1983, 9 925 issued December 7, 1983, 155,767 published September 25, 1985, 162,723 published November 27, 1985, 165,753 issued December 27, 1985 and 204 513 published December 10, 1986; and the South African Patent Applications Nos. 82/5042, 81/4874, 82/5045 and 82/5671 whose contents are referred to by the present invention by way of reference.

A part of the present invention relates to a novel process for the preparation of a sulfonylurea salt consisting of mixing the sulfonylurea and a controlled amount of an alkali metal or alkaline earth metal hydroxide in a halogenated hydrocarbon solvent.

The heterogeneous suspension is stirred for 16 hours prior to filtration and evaporation of the solvent to give the salt. The heterogeneous reaction according to the present invention is outlined in Equation 1,

Equation 1

0 II II + ΜΧη _ > I + HX- |

J-S-N-C-N-BIII,

In which B, J, R and M are as defined above and MX-j represents the alkali metal or alkaline earth metal salt is used as the base.

Usable bases include alkali or alkaline earth metal hydroxides, methoxides and carbonates, among which sodium hydroxide is preferred because of its low cost and the low cost,

their ability to provide products that are easily characterized. This base may be used as is commercially available, i.e. in aggregates or powders; however, it is preferred to use the powder because it reacts more effectively because of having a larger contact surface during the heterogeneous reaction.

In this process the base stoichiometry is important. For example, although the process may be carried out using 1.0 to 1.3 equivalents of sodium hydroxide for each equivalent of technical grade sulphonylurea, i.e., at about 95% purity, it is preferred to use 1.1 to 1.2 equivalents of the base, because it allows obtaining a more stable product. Even more preferred is the use of 1.15 to 1.20 equivalents of the base because it has been found to allow the best product to be obtained which solution in the triethyl phosphate is most stable when subjected to mock polishing tests. the results of the aging assays of various 2- (N-methyl-4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N-methylamino] (compound 3) prepared by addition of insufficient or excess amounts of sodium hydride.

Compound 3 sodium chloride recovery frame, 1 week after its preparation in triethyl Stoichiometry of NaOH phosphate, at 55 ° C, 0.5 eq. 45% 0.9 eq. 79% 1.1 eq. 92% 1.2 eq. 100 * 1.5 eq, 96%

The data presented: in Table 1 thus indicate about 1.15 to 1.20 equivalents and the optimum amount of base. It is believed that to annul the acidic contaminants in the technical grade sulfonylurea, it is necessary to use only a small excess of base, about 0.15 equivalent. The use of an immunity less than 1.15 equivalents does not allow complete formation of the sulfonylurea salt and to give a solution of the initial sulfonylurea and its salt in the liquid solution. The starting sulfonylurea decomposes rapidly during the simulated aging test. Any excess base of greater than 1.15-1.20 equivalents can react with the sodium salt of Compound 3 and decrease the chemical yield of the sodium salt of the sulfonylurea.

Solvents suitable for use in this process include:

methylene chloride, chloroform, triethylchloroethanes or other halogenated hydrocarbon solvents with the proviso that they can be imbibed with water. Among these solvents, methylene chloride and chloroform are most preferred because of their low cost and because they exhibit low boiling points which facilitate elimination of the solvent after the reaction. It is not essential that these solvents are used prior to using them in the reaction when its water content and less than 0.02% by weight. When water-containing solvents are used, the solvent should be dried by stirring with hydrogen carbonate and anhydrous sodium. Ethanol used in the proportion of 0.75% as a preservative in chloroform is not detrimental to the process because in the final phase there is an evaporation which efficiently eliminates ethanol and chloroform.

When using solvents with boiling points

A greater than about 30 DEG C., the reaction may be carried out at ambient temperature or at a high tem- perature between 30 DEG and 50 DEG C. When chloroform or methylene chloride is used at ambient temperature and preferred. When the solvent is fluorotrichloromethane, an ice bath should be used to prevent evaporation of the solvent. The amount of solvent used in the reaction is not a critical factor. In general, 10 to 40 parts by weight of the solvent are used in this reaction for each part of the sulfonylurea. When methylene chloride or chloroform is used as the solvent, it is preferred to use 20 parts by weight to provide an efficient reaction allowing the complete formation of sulfonylurea salt. -23-

The time required to complete this type of reaction depends on the sulfonylurea species and the base. When a metal methoxide is used as the base, the reaction generally takes 4 to 10 hours to complete. When a metal hydroxide is used as the base, the reaction time is higher, i.e. 10 to 16 hours. Among all alternatives it is preferred to use sodium hydroxide and a reaction time of from 14 to 16 hours,

Depending on the sulfonylurea species and the solvent, the reaction mixture may be dissolved during the reaction. When the salt dissolves in the solvent the solution is filtered and the filtrate is evaporated at ambient temperature to 250 ° C under reduced pressure (20 to 30 mm Hg) to provide the salt under reduced pressure. the shape of a solid. When the salt does not dissolve in the solvent, the solids are filtered and the solid retained on the filter is washed with fresh solvent (about 10 parts of solvent in each case for each part of the sulfonylurea used at the start of the reaction) The addition of an excising agent to the optional reaction mixture,

Those skilled in the art readily select an appropriate excising agent, for example, between alkali metal sulfates, chlorides and carbonates, with alkali metal sulfates being preferred. The amount of excising agent is not critical but: generally one part by weight is used for each sulphonylurea otter. The addition of the desiccating agent may occur at any time during the reaction. Upon completion of the reaction the excising agent can be easily removed by filtration. When the sulfonylurea salt is not soluble in the solvent, the addition of a desiccating agent should be avoided as it would require a phase to remove the sulfonylurea salt from the extinguishing agent after completion of the reaction.

The sulfonylurea salts thus prepared are almost always very Fiyroscopic. These salts should be dried under vacuum at a pressure of 1 to 30 mm Hg and at room temperature and then stored in a desiccator.

The dried salts may be dissolved in water miscible organic solvents such as triethylphosphate, 1-methyl-2-pyrrolidinone, diacetone alcohol and dimethylsulfoxide. The concentration may range from 5 to 30% by weight. Among these solvents, triethylphosphate and 1-methylpyrrolidinone are preferred since they provide liquid compositions exhibiting the highest chemical stability in the simulated aging assays. A solution containing the sodium salt of compound 3 in the amount of 20 % in 1-methyl-2-pyrrolidinone undergoes a decomposition of less than 2% after 1 week at a temperature of 55 DEG C. The solution of an equal amount of the same salt in triethylphosphate and also very stable from the chemical point of view, undergoing a 2% decomposition after three weeks at 55 ° C,

As described above, an alternative process is to prepare a very pure and stable salt of the sulfonylurea directly in an aqueous solvent for solutions which are used in agriculture, this prevents the need to separate the sulfonylurea salt and add it afterwards the one! Do not use water.

For example, the addition of a hydroxide such as sodium hydroxide or potassium hydroxide to a suspension of a compound of formula I in triethyl phosphate gives a stable, water-soluble solution which contains a salt of the compound of formula I in triethylphosphate,

Suitable salts and solvents are those mentioned above. In general, stable solutions may contain between 5 and 40%,

Typical reaction temperatures are from 0 DEG to 60 DEG C., preferably by working at ambient temperature. The reaction time may vary from 1 hour to 2 days, it is preferred that the reaction is continued for 1 day. should be dried prior to use. In general such drying is to use 4A molecular sieves for 24 hours.

The aforesaid liquid solutions, prepared either using a 2-phase process or directly in the above-mentioned process prior to a single phase, are known to all salts of the general formula. However, such liquid solutions are stable over long periods when R represents an alkyl group,

The organic solvents which are used to prepare these solutions may be used as commercially available if their water content is less than 0.5%. Otherwise, it is preferred to dry the solvents using conventional methods. Many of the solvents may be dried over anhydrous magnesium sulfate and then filtered to remove the desiccant. The anhydrous solvent should then be kept in sterile containers or on molecular sieves. is applied to the dimethylsulphoride which is to be dried using a conventional method, for example, distillation under reduced pressure, in the presence of sodium hydroxide in pellets and stored on molecular sieves; 4A,

These liquid solutions can tolerate the presence of small amounts of hydroxy acids, for example as much as 2% of 1-propanol, without significantly reducing their stability. A water content of 0.5% in these liquid compositions, for example, does not diminish their chemical stability, the anhydrous salt itself is very stable from the chemical point of view. In the Simulated Aging Test, which is described below, the anhydrous salt did not change in a detectable ratio. In the preparation of dispersible anhydrous solutions an anhydrous salt can be used and this salt can be used directly as a herbicide in the ore- or oost-emergency,

Both the isolated salts and their liquid solutions are fully water soluble and form true clear solutions when mixed with water in a spray tank in commercial concentrations of 100 to 10,000 pom.

The aqueous solutions of these salts can be stored in a spray tank for at least 100 hours without significant reduction of stability, the pH of the water should preferably be between 7, 8 and 8, Q, since the weakly alkaline water dissolves the sulfonylurea salt faster and more efficiently than the acidic or neutral water. EXPERIMENTAL TESTS '

Simulated Aging Assay The simulated aging assay consists of heating a sample of the solution at a temperature of 55 ° C for a period of time, generally between 1 and 3 weeks. After this time, the amount of active ingredient remaining per dose HPLC (high performance liquid chromatography). The 1 week period in this accelerated aging test corresponds to storage at room temperature for one year.

High Resolution Liquid Chromatography

High performance liquid chromatography (HPLC) was used to determine the amount of the sulfonylurea salt of the isolated products and the samples subjected to the simulated aging test. A mixture of acetonitrile and water buffered to pH2.2. One of two columns was used as the stationary phase: Du Pont Zorbax * Sil ODS 4.15 cm and Uhatman ODS 3RAC II, 10 cm.

Once the eluent was buffered at d2.2, the sulfonylurea salts were reprotonated in the column until the starting materials were obtained. As the free salt of the free sulfonylurea salt was not differentiated in these conditions, the utility of the HPLC was confined to the control of the decomposition. Conversion of the free sulfonylurea to its salt was confirmed by the determination of the melting point and nuclear magnetic resonance spectroscopy.

Differential Scanning Calorimetry (DSC)

In the experimental descriptions DSC stands for differential scanning calorimetry and is used to determine the melting points of the isolated sulfonylurea salts.

Nuclear Magnetic Resonance Spectroscopy

Nuclear magnetic resonance (NMR) spectra were determined using a Yarian EM390 spectrometer. Chemical shifts are expressed in parts per million for " low field " in relation to tetramethylsilane: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet and d coupling constant. -29 COMPOUNDS 1-16

Compound 1

Compound 2

Compound 3

Compound 4

3 0

COMPOUNDS OF 1-16 (cont,)

COgCHg

Compound 8

S02 NH

NH

-31 COMPOUNDS 1-16 (eont.)

Compound 9

Compound 10

OCH,

Compound 11

Compound 12

* 32 * * * 32 * *

Compound 13

Compound 14

Compound 15

Examples

The following examples illustrate the process according to the present invention.

Example 1

Preparation of 2- [6-N- (4-methoxy > [methyl-1,3,5-triazin-2-yl) -N-methylamino] carbonyl] -amino] -sulfonyl-1 > -benzoate (compound 3). To a stirred suspension of 20 g (48.5 mmol) of Compound 3 prepared by a conventional procedure, with a purity of 95.7%, and 30 g of sodium carbonate in 400 g of chloride of methylene chloride was added 2.23 g (55.7 mmol) of sodium hydroxide in powder. The solution was stirred for 16 hours at room temperature, at 20-25 ° C, after which it was filtered A clear yellow solution was obtained which was evaporated under reduced pressure using a rotary evaporator. 20 g of the sodium salt of Compound 1 were obtained as a pale yellow solid with a purity of 99 ° F. 184 ° C (DSC) HPLC using 43% acetonitrile as the eluent was reacted as described in Example 3 and gave a retention time (RL of 7 minutes, NMR (CDCl3): 8.20-8.05 (m, 1H), 7.47 (M, 6H), 3.25 (s, 3H), and 2.3 (s, 3H);

Example 2

Preparation of the sodium salt of ethyl 2 - [[[(4-chloro-6-methoxy-2-pyridinyl) -1amino] carbonyl] amino] sulfonyl] benzoate (Compound 2 }.

To a stirred solution of 50 g (0.12 mole) of Compound 9 prepared by conventional methods in 1500 g of methylene chloride was added 5.31 g (0.133 mole) of sodium hydroxide in powder. The suspension was stirred for 20 hours at room temperature at 20 DEG to 25 DEG C. The cloudy suspension was then filtered and the solid contained in the filter was removed, which was further washed twice with methylene chloride The salt was identified as the sodium salt of Compound 2. MP, 205øC (DSC) HPLC using 45% acetonitrile as eluent gave a R of 13 minutes similar to the retention time of NMR (DMSO-d6): 8.99 (s, 1H), 8.13-8.00 (m, IR), 7.65-7.40 (m, 3H), 6.45 (s, 1H), 4.30 (q, 2H, J = 7 Hz), 3.88 (s, 3H), 1.27 (t, 3H, J = 7 Hz),

Method B

I

A stirred solution of (2.4 mmol) of Compound 2 in 50 g of chloroform was reacted with 0.1 g (2.5 mmol) of sodium hydroxide. The suspension was then stirred for 16 hours at room temperature. The slightly cloudy solution was filtered, yielding a clear solution which was filtered. evaporated in a rotary evaporator under reduced pressure to give the salt as a yellow solid. The salt obtained by this method exhibited the same NMR spectrum as that obtained by Method A,

Exemolo 3

Preparation of the lithium salt of Compound 2,

Determinations by DSC showed that the lithium salt melted at 143øC, NMR (DMSO-d6): 9.12 (s, 1H ), 8.13-8.00 (m, 1H), 7.67-7.33 [m, 3H); 6.58 (s, 1H); 4.25 (t, 2H, J = 7Hz); 3.87 (s, 3H); 1.25 (q, 3H, J = 7Hz),

Example 4

Preparation of the lithium salt of 2,3-dihydro-N - [[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N-methylamino] benzo [B] thiophene-7-sulfonic acid] Compound 14),

According to the technique described in the. Example 1, 0.5 g (1.13 mmol) of Compound 3, prepared by standard methods, lithium carbonate Ig, 0.052 g (1.24 mmol) of lithium fiidroxide monohydrate and 50 g of methylene chloride to provide 0.5 g (yield 99%) of the lithium salt of Compound 14, mp, 1250 ° C (with decomposition by DSC). HPLC using acetonitrile at 30 ° C as eluent gave a Biol of 6 , 7 minutes, similar to the retention time of the initial sulfonylurea.

Example 5

Preparation of the sodium salt of Compound 14,

Using the general technique described in Method A of Example 2, 0.5 g (1.13 mmol) of Compound 14, 0.05 g (1.25 mmol) of sodium hydroxide and 50 g of methylene chloride were used to afford 0.52 g (99% yield) of the sodium salt of Compound 3. MP 238 ° C (with decomposition, DSC), NMR (DMSO-d6): 8.20-8.03 (m, 1H), 7.85 (M, 20), 3.87 (s, 301, 3.55-3.40 (m, 1H), 3.28 (s, 30), 2.90-2.50 , 20), 2.32 (s, 30), 1.33 (d, 30, J = 6Hz)

Example 6

Preparation of N - [- N-4-methoxy-6-methyl-1, 3,5-triazin-2-yl] -N-methylamino] -carbonyl] -K ', N'-dimethyl -1,2-benzenedisulfonamide (Compound 15),

Using the technique described in Method A of Example 2, 0.283 g (0.6 mmol) of Compound 4, prepared by conventional methods, were used, 0.288 g (0.7 mmol) of sodium hydroxide and 28 g of methylene chloride to provide 0.83 mmol (100 mmol) of sodium salt of Comnote 15, mp, 160øC (decomposed by DSC), NMR (CDCl3): 8.60- 8.40 (m, 1H), 7.85-7.55 (m, 3H), 3.87 (s, 3H), 3.47 (s, 3H), 2.9 (s, 6H); , 39 (s, 3H)

Example 7

Preparation of Compound 15 Salt

Using the technique described in Method A of Example 2, 0.25 g (0.56 mmol of Compound 4, 0.027 g (0.64 mmol) of lithium hydroxide (monohydrate) and 32 g of methylene chloride were used to give 0.26 g (0.57 mmol, 100% yield) of the lithium salt of Compound 15, mp, 130øC (decomposed by DSC) .1 H NMR (CDCl3): 8.45-8.31 (m, 1H (S, 3 H), 2.84 (s, 6H), 2.25 (s, 3H), 3.95 (s,

Example 8

Preparation of N - [[N-4,6-dimethoxy-1,3,5-triazol-2-yl) -N-methylamino] carbonyl] -2- (5- -1H-tetrazol-1-yl) -benzenesulfonamide (Compound 1),

Using the technique described in Example 1, 16.87 g (38.7 mmol) of the Formula 5 was prepared by conventional techniques, 36 g of sodium carbonate, 1.79 g (44.7 mmol) of sodium hydroxide and 480 g of methylene chloride to provide 17.8 g (38.7 mmol, 100% yield) of the sodium salt of Compound 16. NMR (CHCl3): 8.4-8.13 (m, 1H); 7.70-7.40 (m, 2H), 7.25-7.00 (m, 1H), 3.85 (s, 6H), 3.19 (s, 3H), 2.32 (s, 3H) ,

Example 9

Preparation of the. lithium of Compound 1,

Using the technique described in Example 1, 0.5 g (1.1 mmol) of Compound 5, 0.053 g (1.26 mmol) of lithium hydroxyde monohydrate and 5% of methylene chloride were used to obtain 0.45 g 1.02 mmol, yield 89%) of Compound 16 salt. NMR (CDCl3): 8.55-8.20 (m, 1H), 7.90-7.50 (m, 7.15 (m, 1H), 3.90 (s, 6H), 3.43 (s, 3H), 2.50 (s, 3R).

Example 10

Preparation of 2 - [[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -N, Ν-dimethyl-3- trimethylcarboxamide (Compound 41,

By the procedure described in Example 1, 5 g (12.2 mmol) of Compound 4, prepared by standard methods, 5 g of sodium carbonate, 0.56 g (13.4 mmol) of sodium hydroxide and 150 g of methylene chloride, the sodium salt of Compound 4 was quantitatively obtained. mp 200 ° C (with decomposition by DSC) .1 H-NMR (CDCl3): 8.40-8.27 (m, 1H); , 97 (s, 1H), 7.63-7.47 (m, 1H), 7.40-7.17 (m, 1H), 5.54 (s, 1H), 3.77 (s, 6H). , 10 (S, 3H), 2.81 (s, 3H), -40-

Example ΤΙ

Preparation of methyl 2 - [[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfophthyl] benzoate Compound 10),

Using Method A of Example 2, the sodium salt of Formula 1 was quantitated by reacting 5 g (13.1 mmol) of Compound 10, prepared by conventional methods, 0.157 g (14.3 mmol) of sodium hydroxide and 150 g of methylene chloride. Mp 1950 ° C (DSC). NMR (DMSO-d 6): 9.18 (s, 1 H); 8.20-8.07 (m, 1H); 7.70-7.43 (m, 3H); 3.87 (s, 3H), 3.80 (s, 3H), 2.31 (s, 3H),

Example 12

Preparation of the lithium salt of Compound 1Q

Using the technique described in Example 1, the lithium salt of Compound 10 was quantitated by reacting 3 g (7.9 mmol) of Compound 10, 3 g of lithium carbonate, 0.36 g (8.6 mmol) of lithium hydroxide monohydrate and methyl chloride and η o.

NMR (DMSOd 6): 9.60 (s, 1H), 8.15-7.96 (m, 1H), 7.78-7.37 (m, 3H), 3.90 (s, 3H), 3.76 (s, 3H), 2.32 [s, 3H] Example 13 Preparation of 3 - [[[[(4-Methoxy-6-methyl-1,3,5-triazin-2 methyl] amino] carbonyl] amino] sulfonyl} -2-thiophene carboxylate (Compound 61

Using Method A of Example 2, the sodium salt of Compound 6 was prepared quantitatively by reacting 5 g (12.9 mmol) of Compound 6 prepared in a conventional manner, 0.57 g (14.2 mmol) (DMSO-d6): 7.87 (d, 1H, J = 5 Hz), 7.7 (d, 1H) (S, 3H), 2.35 (s, 3R), 3.83 (s, 3H), 2.35 (s, 3H)

Direct Preparation of Sulphonylurea Salt Solutions Example 14

Preparation of a liquid solution of. 2- [2 - [[[N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N-methylamino] carbonyl] -amino] sulfonyl] benzoate (Compound 3) To a stirred suspension of 10 g (24.2 mmol) of Compound 3 as a free acid and with a degree of nrness of 95.7% in 55 g of triethyl phosphate, pre-dried on soft sieves 4A for 24 hours, 1.25 g (31.25 mmol) of powdered sodium hydroxide was added. Using a magnetic stirrer the heterogeneous mixture was stirred in a closed flask overnight. 24 hours and then filtered to give a clear yellow solution containing 14.4% of the active ingredient This solution was water miscible in any preparation,

Example 15 2 - [[[N - (4-methoxy-6-methyl-1,3,5-triazet-2-yl) -N-methylamino] carbonyl] amino] sulfonyl] benzoate of methyl (Comoosto 3),

The procedure described in Example 14 was repeated using 1.0 g (25 mmol) of sodium hydroxide. A semisynthetic product was obtained.

Example 16

Using a procedure similar to that described in Example 14, the lithium salt of Compound 3 was prepared in a solution of triethyl phosphate, by reacting 0.74 g (31.25 mmol) of anhydrous 1-thiohydroxide instead of hydroxide The resulting yellow solution contained 14.55% of Compound 3,

Example 17

The procedure described in Example 16 was repeated using 21 g of 1-methyl-2-pyrrolidone instead of triethyl phosphate as solvent. The product contained 30.1% of Compound 3 as 1Tion salt.

Example 18

The orocesso described in Ex. 14 was repeated using a mixed solvent consisting of 35 g of triethylphosphate and 8 g of 1-methyl-2-pyrrolidone. The product contained 17.6% of Compound 3,

The salts prepared by the oocysts 1 to 13 were dissolved in either the triethyl phosphate or the 1-methyl-2-pyrrolidone or the mixtures of these solvents to give solutions containing 1 to 40% of the active ingredient and water soluble in all ratios,

Generally, the Ittio salts were more soluble than the sodium salts. Also 1-methyl-2-pyrrolidone dissolved at least 25% more of the salt than triethylphosphate.

These solutions dissolved almost instantaneously in stirred water after dilution prior to spray application. Conventional compositions of the above-mentioned compounds took some time to dissolve or disperse in water.

Claims (32)

-44 1. A process for the preparation of sulfonylurea salts having herbicidal activity of general formula - wherein M represents a lithium, sodium, potassium, magnesium or calcium atom; R represents a hydrogen atom or an alkyl group; J represents an optionally substituted heterocyclic or homocyclic group; B represents an optionally substituted heterocyclic group the cyclic skeleton of which contains carbon atoms and at least one nitrogen atom; and m is the integer 1 or 2; characterized in that a solution of the corresponding sulphonylurea is contacted with a hydrocarbon solvent, which is immiscible with water, with the corresponding alkali metal or alkaline earth metal hydroxide, and the resulting sulphonylurea salt is separated. 2. A process according to claim 1, wherein the resulting salt is removed by evaporation. 3. A process for the preparation of solutions containing sulphonylurea salts of the general formula I mentioned above, characterized in that the corresponding sulfonylurea is contacted with an alkaline or alkaline-earth base in a water miscible aprotic solvent. 4. A process according to claim 3 for the preparation of compounds of general formula I in which R 1 represents a hydrogen atom or a CH 2 group; J represents a group of formula -4- Jnlfi Jt-1? -47 wherein Q represents an oxygen or sulfur atom or an S (O), S (O) 2 or C (O) group; represents a fluorine, chlorine or bromine atom, a NO2 / cyclopropylalkyl group, halogeno-C1-3 alkyl, halogeno-C2-3 alkenyl, alkoxy-halo-C1-3 alkoxy, C2-3 alkoxy- (O) NR, R ', S (O), -NR, R, S (O) R', and quot; 2 a o c 2 d. and in which R represents a C1-3 alkyl group optionally substituted with one halogen atom or a C1-2 alkoxy or CN group, cyclopropylmethyl, allyl or propargyl; R3 represents a hydrogen atom or a C1-3 alkyl or C1-2 alkoxy group; Rc represents a C1-2 alkyl group; R 2 represents a C 1-12 alkoxy, allyl or cyclopropyl group; R6 represents a hydrogen atom or a C1-2 alkyl group; Rf represents a C1-3 alkyl, halo-C1-3 alkyl, allyl or propargyl group;  € ƒâ € ƒâ € ƒR8 represents a C1-4 alkyl, halo-C1-4 alkyl or C3-8 cycloalkyl; n is zero or the integer 1 or 2 and L represents a group J N-N-N 1, -5 Ld & 1 L-1 L-1 L-12 L-12 L-1 L-1 L = 1 L L-15 XV - / O - (I.e. L = ia) · Lr2Q LJJ L = 2 LnlB L = 22 ° C-24 ° C. / X L-25 or a group of general formula L-28 or L-29 wherein R3 and R4 each represent a hydrogen atom or a CH3 group; R 1 represents a hydrogen atom or a CH 3 or CH 2 CH 2 group; R 2 represents a hydrogen atom or a CH 3, CH 2, CH 2, OCH 3, OCH 2 CH 3, SCH 3 or CH 2 Cl 3 group; and R 2 represents a hydrogen atom or a CH 3 group; R3 represents a hydrogen, fluorine, chlorine or bromine group or a CN, CN, C1-3 alkyl, CF3, C1-6 alkoxy, halo-C1-3 alkoxy or C1-4 alkylthio group; -6- R 3 represents a NO 2 group, CC > 2 CH 3, CO 2 CH 2 CH 3, s (O) 2 N (CH 3) 2, S (O) 2 CH 3 or S (O) 2 CH 2 CH 3; represents a hydrogen, fluorine, chlorine or bromine atom, a C1-4 alkyl, halo-C1-3 alkyl, C2-3 haloalkenyl, C1-3 alkoxy, NO2 or SO2 -C1-3 alkyl or a group of formula in which R 1, R 2, R 3, R 4, R 5, R 6, R 5, R 5, R 5, R 5, R 5, R 5, R 5, wherein R1 represents a fluorine, chlorine or bromine atom, a C1-3 alkyl group, halogeno-C1-3 alkyl, halogeno-C2-3 alkenyl, C2-2 alkoxy, N02 or (O) NR 1, R 2, R 3, R 4, S (O) R 2, R 2, R 3, Wherein R1, R2, R3, R4, R4, R4 and R4 are as defined above; R3 represents a fluorine, chlorine or bromine atom, a C1-3 alkyl group, a C1-3 alkoxy or a halogen-C2-3 alkyl or a group of the general formula C02Ra 'G (O) NRkRc' (O) n Rf 'C (O) R g or L, wherein R & Rfa, Rc, Rd, Rq, Rf, Rg, n or L are as defined above; R 2 represents a hydrogen, fluorine or chlorine atom or a CH 3 or CH 3 group; R6 represents a hydrogen atom or a C1-3 alkyl group, R4 represents a fluorine, chlorine or bromine atom, a C1-3 alkyl, C2-3 haloalkenyl, C1-4 alkoxy, OCF2 H or NO2 group or a (0) nRf, C (O) R or L, wherein Ra, Rfa, Rc, Rd, R, Rf, R, n, or L have the meaning defined above; R representa represents a hydrogen, chlorine, fluorine or bromine atom or a C _ alquilo alquilo alkyl or C alco alco alco alkoxy group represents a hydrogen atom or a C 1-2 alquilo alquilo alkyl group; R² represents a hydrogen atom or a CH 2 group; R3 represents a hydrogen atom or a C1-6 alkyl, halo-C1-4 alkyl, C1-4 alkoxy-C1-8 alkyl or cycloalkyl C1-6 alkyl; R3 represents a hydrogen, fluorine, chlorine or bromine or a CH3, OCH3 or SCH2 group; and B represents a group of formula X Y in which X represents a chlorine atom or a group CH 2, OCH 2, C 2 H 2 or COCH 2 H; Y represents an alkyl group 2, alkoxy, 0 ± 2, 0 CF 2 H, OCH 2 CF 3, NHCH 3, or N (CH 3) 2; and Z represents a nitrogen atom or a CH group, with the proviso that (1) Z represents a CH group and Y represents a C1-2 alkoxy group when X represents a chlorine atom; and (2) Z represents a CH group when X and Y each represent a C H H H H group, wherein the starting materials are suitably substituted. 5. A process according to claim 1 for the preparation of the sodium salt of 2- [N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) - N-methylamino-carbonyl] amino] sulfonyl] benzoate, characterized in that correspondingly substituted starting compounds are used. i 6. A process according to claim 3 for the preparation of the sodium salt of N- [N- (4,6-dimethoxy-1,3,5-triazin-2-yl) -N-methyl- amino-carbonyl] -2- (5-methyl-1H-tetrazol-1-yl) -benzenesulfonamide, characterized in that correspondingly substituted starting compounds are used. 7. A process according to claim 3 for the preparation of the lithium salt of 2 - [(4-chloro-6-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] / -benzoate, characterized in that correspondingly substituted starting compounds are used. 8. A process according to claim 3 for the preparation of the sodium salt of 2 - [(4-chloro-6-methoxy-2-pyrimidinyl) -5Î ± -amino-carbonylamino] y-sulfonyl-benzoate, characterized in that the starting compounds are suitably substituted. A process according to claim 3 for the preparation of the lithium salt of 2- (N-methoxy-6-methyl-1,3,5-triazol-2-yl) -N- methylamino-carbonyl and amino-sulfonyl y-benzoate, characterized in that correspondingly substituted starting compounds are used. I A process according to claim 3 for the preparation of the sodium salt of 2- (7-methoxy-6-methyl-1,3,5-triazol-2-yl) -N-methylamino-carbonyl and amino-sulfonyl y-benzoate, characterized in that correspondingly substituted starting compounds are used. 11. A process as claimed in claim 3 for the preparation of the lithium salt of 2- [2- (4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl and amino-sulfonyl and N, N -dimethyl-3-pyridinecarboxamide, characterized in that correspondingly substituted starting compounds are used. 12. A process as claimed in claim 3 for the preparation of the sodium salt of 2- [2- (4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -N-N-dimethyl-5-pyridinecarboxamide, characterized in that correspondingly substituted starting compounds are used. A process according to claim 3 for the preparation of 2- (2-chloroethoxy) -N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -amino] -carbonyl] -benzenesulfonamide, characterized in that correspondingly substituted starting compounds are used. 14. A process according to claim 3 for the preparation of the sodium salt of 2- (2-chloroethoxy) -N - [(4-methoxy-6-methyl-1,3 , 5-triazin-2-yl) -amino] carbonyl} -benzenesulfonamide, characterized in that correspondingly substituted starting compounds are used. A process according to claim 3 for the preparation of the lithium salt of 3 - [[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) -amino] carbonyl] amino} sulfonyl} -2-thiophene carboxylate, characterized in that correspondingly substituted starting compounds are used. 16. A process according to claim 3 for the preparation of the sodium salt of 3 - [(4-methoxy-6-methyl-1,3,5-triazin-2-yl ) -amino] carbonyl} -amino} sulfonyl} -2-thiophene carboxylate, characterized in that the corresponding starting compounds are used. 17. A process according to claim 3 for the preparation of the lithium salt of 2 - [[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methylbenzoate, characterized in that correspondingly substituted starting compounds are used. 18. A process according to claim 3, for the preparation of the sodium salt of 2-77777 " (4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methylbenzoate, characterized in that correspondingly substituted starting compounds are used. 19. A process according to claim 3, for the preparation of the lithium salt of 2-777 " (4,6-dimethyl-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate, characterized in that correspondingly substituted starting compounds are used. 20. A process as claimed in claim 3 for the preparation of the sodium salt of 2 - [[(4,6-dimethyl-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate methyl, characterized in that correspondingly substituted starting compounds are used. 21. A process according to claim 3 for the preparation of the lithium salt of 2-chloro-N- [4 '- (4-methoxy-6-methyl-1,3,5-triazin-2 -yl) amino] carbonyl] -7-amino-benzenesulfonamide, characterized in that correspondingly substituted starting compounds are used. 22. A process according to claim 3 for the preparation of the sodium salt of 2-oxo-4 - [(4-methoxy-6-methyl-1,3,5-triazin-2- yl) amino] carbonyl] benzenesulfonamide, which is characterized in that correspondingly substituted starting compounds are used. 23. A process according to claim 3 for the preparation of 2- [7 - (4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] y-carbonyl and amino-sulfonyl y-benzoate, characterized in that correspondingly substituted starting compounds are used. 24. A process according to claim 3 for the preparation of the sodium salt of 2 - [(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] y-carbonyl and amino-sulfonyl y-benzoate, characterized in that correspondingly substituted starting compounds are used. 25. A process according to claim 3 for the preparation of the lithium salt of 2 - [(4-ethoxy-6-methylamino-1,3,5-triazin-2-yl) - amino-γ-carbonyl and γ-amino sulfonyl y-benzoate, characterized in that correspondingly substituted starting compounds are used. A process according to claim 3 for the preparation of the sodium salt of 2 - [(4-ethoxy-6-methylamino-1,3,5-triazol-2-yl) amino] -carbonyl-amino-sulfonyl-benzoate, characterized in that correspondingly substituted starting compounds are used. 27. A process as claimed in claim 3 for the preparation of the lithium salt of 5 - [(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] -amino and sulfonyl lithium methyl-1H-4-pyrazole-2-carboxylate, characterized in that correspondingly substituted starting compounds are used. 28. A process as claimed in claim 3 for the preparation of the sodium salt of 5 - [[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl-1H-4-pyrazolecarboxylate, characterized in that correspondingly substituted starting compounds are used. 29. A process as claimed in claim 3 for the preparation of the lithium salt of 2- (N- (4-methoxy-6-methyl-1,3,5-triazin- -yl) -N-amino-carbonyl] -2- (2-methoxy-ethoxy) -benzenesulfonamide, which comprises starting compounds of the formula (I). A process according to claim 3 for the preparation of the sodium salt of 2- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N-amino- carbonyl and 2- (2-methoxyethoxy) y-benzenesulfonamide, which comprises starting compounds which are suitably substituted. \ 31. A process according to claim 9, wherein triethylphosphate is used as the solvent. 32. A process according to claim 10, wherein the 1-methyl-2-pyrrolidine is used as the solvent,