NZ732847B2 - Novel crystal forms of the monosodium salt of foramsulfuron - Google Patents

Abstract

The present invention relates to a novel crystal form of the monosodium salt of foramsulfuron (formula (I)), a method for producing said crystal form, the use therof in agrochemical preparations as well as certain compositions, mixtures and/or agrochemical preparations containing said crystal form. The invention also relates to a novel monomethanol solvate of the monosodium salt of foramsulfuron. The invention also relates to a novel monomethanol solvate of the monosodium salt of foramsulfuron.

Description

James & Wells Ref: 307010NZ Novel crystal forms of the monosodium salt of foramsulfuron The present invention relates to a novel crystal form of the dium salt of foramsulfuron, a method for preparing this l form, use thereof in agrochemical ations and also particular compositions , mixtures or agrochemical formulations comprising this crystal form, and also a novel thanol solvate of the monosodium salt of foramsulfuron.

Foramsulfuron of formula (I) below and the monosodium salt thereof are known from EP 0 757 679 A1.

H C N O 3 3 O O O N S CH O N N N O 3 H H Foramsulfuron of formula (I) and certain salts of this compound are known herbicidal active ingredients, see "The Pesticide Manual", 16th edition, The British Crop Protection l and the Royal Society of Chemistry, 2012.

It is also known that foramsulfuron of formula (I) and salts thereof may be used in ation with other herbicidal active ingredients and/or with safeners, described in EP 0 790 771 A1 or EP 1 104 239 A1 for example.

Foramsulfuron has the empirical formula C17H20N6O7S, CAS number 1731594 and IUPAC name 1- (4,6-dimethoxypyrimidinyl)[2-(dimethylcarbamoyl)formamidophenylsulphonyl]urea, and is also referred to below as N-[(4,6-dimethoxypyridinyl)aminocarbonyl]dimethylaminocarbonyl formylaminobenzenesulphonamide.

The compound of formula (I) and the monosodium salt thereof can be prepared by the s described in EP 0 757 679 A1 and US 6,500,952 B1.

James & Wells Ref: 307010NZ EP 1 902 618 A1 bes methods for preparing sulphonamide salts.

Only one l form of the monosodium salt of foramsulfuron has been known to date, which is referred to after as l form A. This crystal form A corresponds to a semi-methanol solvate.

The crystal lattice of a solid can be made up of l chemical components. If one of these is a liquid (e.g. a solvent), these are termed solvates.

The occurrence of active ingredients in various crystalline modifications orphs) is of great icance both for the development of production processes and for the development of formulations (agrochemical formulations). For instance, the different crystalline modifications of a chemical compound differ not only in appearance (crystal habit) and hardness, but also in numerous further physicochemical properties. Differences in terms of stability, filterability, solubility, hygroscopicity, melting point, solid density and flowability can exert a strong influence on the quality and the efficacy of plant ent compositions. It has not been possible to date to t the occurrence and number of crystalline cations, including the physicochemical properties thereof. In particular, the thermodynamic stability and also the different behaviour after administration to living organisms cannot be predicted.

The above embodiments, referring to polymorphs, are applicable analogously to pseudopolymorphs.

The known crystal form A has some disadvantageous properties which are briefly described below.

Crystal form A may have a disadvantageous effect on the stability or storability of compositions (e.g. agrochemical formulations) comprising crystal form A. This may be the case because, for example, the chemical stability of crystal form A in certain compositions is not sufficient and/or further constituents (e.g. other active ingredients) of these compositions are negatively nced in terms of their chemical stability by l form A, and their content in the composition decreases with time. It may also occur that a composition (e.g. agrochemical formulation) comprising crystal form A is unstable over a long (storage) period, and the physical properties of the composition changes, for example, the viscosity or flowability of the composition changes in an undesirable manner.

It is also known that sulphonylurea herbicides are subjected to chemical degradation reactions in the presence of particular auxiliaries, such as alcoholic ts, particularly methanol, which leads to a decrease in the active ingredient content of the sulphonylurea herbicide over long storage periods, which is undesirable. This al degradation also occurs in compositions (such as mixtures or formulations) comprising foramsulfuron and salts thereof in combination with other sulphonylurea herbicides or salts thereof, for example, in itions described in EP 1 104 239 A1. This applies in particular to readily James & Wells Ref: 307010NZ chemically degradable / ysable sulphonylurea herbicides such as lfuron, iodosulfuron-methyl and respective salts thereof such as iodosulfuron-sodium or iodosulfuron-methyl-sodium.

In some cases, furthermore, the technical handling of the known crystal form A is difficult. For instance, according to the preparation method described in EP 0 757 679 A1, this crystal form A occurs in the form of flocculent and poorly filterable aggregates.

The object of the invention, therefore, is to remedy one, several or all of the disadvantage(s) mentioned above in connection with the known crystal form A or to improve the disadvantageous properties mentioned above in connection with the known crystal form A.

This object is achieved in accordance with the invention by a novel crystal form of the monosodium salt of the compound of formula (I) having the empirical formula C17H19N6O7SNa, which is referred to hereinafter as crystal form B.

Therefore, the invention ily s to the dium salt of foramsulfuron in crystalline form (crystal form B), characterized in that the X-ray powder diffractogram of this salt using Cu Kα radiation at 25°C has at least 3 of the following 2Θ (2 theta) values: 2Θ (2 theta) values in ° This ive crystal form B is characterized in that it has an X-ray powder diffractogram having the 2Θ (2 theta) reflections ed in Table 1. The X-ray powder diffractogram of crystal form B is also shown in Figure 2. The most intensive and characteristic 2Θ (2 theta) signals in the X-ray powder dif- fractogram of crystal form B are at 6.2, 6.4, 14.4, 14.6, 14.7, 18.4, 19.2, 20.1, 23.2, and 24.7° (in each case ± 0.2°).

James & Wells Ref: 307010NZ The inventive crystal form B is characterized in that the X-ray powder diffractogram of this salt using Cu Kα radiation at 25°C has at least 4, preferably at least 5, preferably at least 6, more preferably at least 7, ularly preferably at least 8 and especially preferably all of the most intensive 2Θ (2 theta) signals specified above.

The inventive crystal form B is preferably terized in that the X-ray powder diffractogram of this salt using Cu Kα radiation at 25°C additionally has at least two, four, six, eight, ten, twelve or more, preferably at least 15, 20, 23, 25, 27, 30, 33, 35, 38, 40, 42, 44, 46, 48, 50 or more, preferably all of the following 2Θ (2 theta) values: James & Wells Ref: NZ The inventive crystal form B, unlike crystal form C bed below, is non-hygroscopic and has improved stability in formulations (agrochemical formulations).

The inventive crystal form B is better suited to the preparation of (storage) stable formulations and it is more compatible with other sulphonylurea herbicides and salts thereof, particularly with iodosulfuron and salts thereof, since sulphonylurea herbicides (in particular here iodosulfuron) and salts thereof have unsatisfactory ity, particularly unsatisfactory chemical stability, in mixtures with crystal form A.

James & Wells Ref: 307010NZ All X-ray powder diffractometry data stated in the present text refers to the following measurement parameters: Scan axis gonio Scan Mode transmission Start Position [°2theta] 2.0066 End Position [°2theta] 6 Anode material Cu Wavelength a1 [Å] 1.54060 Wavelength K-alpha2 [Å] 1.54443 Wavelength K-beta [Å] 5 K-A2 / K-A1 ratio 0.50000 Generator 40 mA, 40 kV Incident Beam romator ng X-ray mirror Spinning yes 2Θ (2 theta) values ± 0.2° Furthermore, in the context of the present invention, the crystalline form referred to below as crystal form C was found. It takes the form of the monomethanol solvate of the monosodium salt of the compound of formula (I). Crystal form C may be obtained, for example, when crystal form A is stored over a long time period with methanol, which changes crystal form A into crystal form C. Crystal form C is described in further detail below.

Crystal forms A, B and C are characterized by ent X-ray powder diffractograms. In Table 1 below, the respective most intensive characteristic 2Θ (2 theta) reflections are stated, while Table 3 further below shows all 2Θ (2 theta) reflections.

Table 1: Characteristic reflections – X-ray diffractometry of crystal forms A, B and C (as defined above) James & Wells Ref: 307010NZ Peak maximum [2 theta], data in ° Crystal form A Crystal form B Crystal form C 7.4 6.2 9.1 8.7 6.4 9.1 9.0 14.4 9.7 9.2 14.6 12.6 9.3 14.7 16.2 .7 18.4 18.5 23.3 19.2 24.1 23.3 20.1 24.3 23.6 23.2 24.6 26.0 24.7 If the 2Θ (2 theta) reflections of the X-ray powder diffractogram specified in the present text for a given crystalline form have the same value twice (for example the 2Θ peak maximum at 23.3° in the case of l form A), this takes the form of two closely spaced peaks. Due to rounding of the measurement value of the respective peak maximum to one decimal place, two peaks with the same value can arise, but which actually take the form of two peaks in the X-ray powder diffractogram.

The X-ray powder diffractogram of crystal form A is shown in Figure 1.

The X-ray powder ctogram of crystal form B is shown in Figure 2.

The X-ray powder diffractogram of crystal form C is shown in Figure 3.

The inventive monosodium salt of ulfuron in crystalline form is particularly preferably characterized in that the X-ray powder diffractogram using Cu Kα radiation at 25°C corresponds essentially to the spectrum shown in Figure 2.

Crystal forms A, B and C are terized by Raman spectra. In Table 2 below, the most intensive, characteristic bands are given in each case.

All Raman spectroscopy data given in the present text refer to the following measurement parameters, in which the position of the band maxima of the wave number are in each case stated in cm-1: Instrument Bruker Raman RFS 100/S Number of scans 64 James & Wells Ref: 307010NZ Resolution 2 - 4 cm-1 Laser power 50 mW Laser wavelength 1064 nm Inventive crystal form B is preferably characterized in that the Raman spectrum thereof has at least the following bands: Band maximum [cm-1] The Raman spectrum of crystal form B according to the invention preferably has at least ten of the bands specified in Table 4 below, ably 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65 or more, preferably all of the bands specified in Table 4 below.

Table 2: Characteristic bands of the Raman spectra of l forms A, B and C (as defined above) Band maximum [cm-1] Crystal form A Crystal form B Crystal form C 2941 2959 3090 1700 2915 2943 1320 1686 2919 1250 1587 1593 990 1526 1576 697 694 691 362 345 156 103 133 122 James & Wells Ref: 307010NZ The Raman spectrum of crystal form A is shown in Figure 4.

The Raman spectrum of crystal form B is shown in Figure 5.

The Raman spectrum of crystal form C is shown in Figure 6.

The Raman spectrum of inventive crystal form B ably corresponds essentially to the spectrum shown in Figure 5.

Table 3: X-ray diffractometry of crystal forms A, B and C (as defined above) Peak maximum [2 theta] Crystal form A Crystal form B Crystal form C .6 6.2 9.1 .9 6.4 9.1 7.4 10.3 9.7 7.6 10.5 12.0 7.9 11.1 12.6 8.4 11.3 14.8 8.7 11.4 15.7 9.0 12.0 16.2 9.2 12.1 16.3 9.3 12.4 17.8 11.1 12.6 18.0 11.6 12.9 18.2 11.8 13.6 18.5 13.2 14.0 19.0 13.4 14.4 19.5 13.9 14.6 19.9 14.5 14.7 20.1 14.8 15.0 20.9 .3 15.1 21.1 .5 15.4 21.7 .7 16.0 22.1 16.1 16.2 22.6 James & Wells Ref: 307010NZ Peak maximum [2 theta] l form A Crystal form B Crystal form C 16.7 17.0 23.5 17.0 17.2 23.8 17.3 18.2 24.1 18.1 18.4 24.3 19.0 18.8 24.5 19.2 19.2 24.6 19.7 20.1 25.1 .7 20.3 25.6 .9 20.6 25.8 21.3 20.8 26.5 22.3 21.2 26.8 22.6 21.6 27.1 22.8 22.7 28.8 23.3 23.2 29.2 23.3 23.7 29.7 23.6 24.6 30.0 24.5 24.7 30.5 24.8 25.4 30.8 .1 25.9 31.3 26.0 26.2 31.7 26.8 26.9 31.9 27.6 27.1 32.0 28.2 27.7 33.1 28.7 28.3 33.2 29.1 29.0 33.5 .1 30.2 34.2 .7 30.5 34.4 32.0 30.7 34.9 33.0 31.0 35.4 34.4 31.2 35.8 37.0 31.9 36.2 37.4 32.5 36.6 32.6 37.2 James & Wells Ref: NZ Peak maximum [2 theta] Crystal form A Crystal form B Crystal form C 33.7 37.7 Table 4: Raman spectroscopy bands of crystal forms A, B and C (as defined above) Band maximum [cm-1] Crystal form A Crystal form B Crystal form C 3114 3338 3302 3.097 3.100 3.090 3.072 3.061 3.030 3.032 3.035 3.016 2.941 3.018 2.999 2.890 2.959 2.943 2.878 2.915 2.919 2.842 2.865 2.870 2.798 2.810 2.839 1.700 1.686 2.812 1.691 1.654 1.693 1.653 1.628 1.628 1.639 1.604 1.617 1.604 1.587 1.607 1.537 1.526 1.593 1.513 1.478 1.576 1.449 1.451 1.533 James & Wells Ref: 307010NZ Band m [cm-1] Crystal form A Crystal form B Crystal form C 1.404 1.421 1.517 1.382 1.393 1.480 1.320 1.372 1.449 1.267 1.304 1.415 1.250 1.262 1.404 1.218 1.244 1.384 1.196 1.216 1.372 1.160 1.206 1.303 1.150 1.175 1.261 1.120 1.142 1.243 1.101 1.112 1.215 1.053 1.092 1.207 1.004 1.064 1.168 990 1.048 1.148 936 1.031 1.137 926 1.022 1.111 896 1.002 1.092 760 983 1.074 744 938 1.048 697 925 1.031 684 910 1.015 642 904 1.002 598 882 984 555 864 940 534 823 924 500 812 908 446 786 895 424 763 883 362 735 837 310 713 826 294 694 788 263 688 761 215 649 739 James & Wells Ref: 307010NZ Band maximum [cm-1] Crystal form A Crystal form B Crystal form C 159 623 710 103 614 691 85 594 649 580 620 555 593 512 581 464 517 445 469 421 431 394 394 356 370 345 347 254 333 218 283 186 266 147 242 133 156 98 122 84 82 In a further aspect, the present invention s to a composition comprising inventive crystal form B in a total amount of at least 5% by weight, wherein this total amount is ably at least 10, 15, 20, 25, , 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95% by weight or more, based in each case on the total weight of monosodium salt of foramsulfuron present in the composition.

Such a composition according to the invention is preferably characterized in that the composition comprises ive crystal form B in a total amount of at least 10% by weight, preferably 15% by weight or more, based in each case on the total amount of monosodium salt of foramsulfuron present in the composition.

A preferred ition according to the invention is thereby characterized in that it is present in solid form at 25°C and 1013 mbar, James & Wells Ref: 307010NZ and/or the content of monosodium salt of foramsulfuron is 80% by weight or more, preferably 85% by weight or more, preferably 90% by weight or more, particularly preferably 95% by weight or more, based in each case on the total weight of the ition.

A preferred composition according to the invention is characterized in that the composition comprises inventive crystal form B in a total amount of at least 25% by weight, preferably 40% by weight or more, based in each case on the total amount of monosodium salt of foramsulfuron present in the composition, the t of monosodium salt of foramsulfuron is 80% by weight or more, preferably 85% by weight or more, based in each case on the total weight of the composition.

A particularly preferred composition according to the invention is characterized in that the composition comprises inventive crystal form B in a total amount of at least 50% by weight, ably 60% by weight or more, based in each case on the total amount of monosodium salt of foramsulfuron present in the composition, the content of monosodium salt of foramsulfuron is 85% by weight or more, preferably 90% by weight or more, based in each case on the total weight of the composition.

An especially preferred composition according to the ion is characterized in that the composition comprises inventive crystal form B in a total amount of at least 70% by weight, preferably 80% by weight or more, based in each case on the total amount of monosodium salt of foramsulfuron present in the composition, the content of monosodium salt of foramsulfuron is 85% by weight or more, preferably 90% by weight or more, based in each case on the total weight of the composition.

An especially preferred composition according to the invention is characterized in that the composition comprises ive l form B in a total amount of at least 80% by , preferably 85% by weight or more, based in each case on the total amount of monosodium salt of foramsulfuron present in the composition, James & Wells Ref: 307010NZ the content of monosodium salt of foramsulfuron is 90% by weight or more, preferably 95% by weight or more, based in each case on the total weight of the composition.

One of the most particularly preferred configurations is a composition ing to the invention terized in that the composition comprises inventive crystal form B in a total amount of at least 90% by weight, preferably 95% by weight or more, based in each case on the total amount of monosodium salt of foramsulfuron present in the ition, the content of monosodium salt of foramsulfuron is 90% by weight or more, preferably 95% by weight or more, based in each case on the total weight of the ition.

In a r aspect, the present invention relates to the use of crystal form B according to the invention or a composition according to the invention as defined above for preparing agrochemical formulations, preferably for preparing herbicidally active agrochemical formulations.

In a further aspect, the present invention relates to the monomethanol solvate of the monosodium salt of foramsulfuron in crystalline form (crystal form C), characterized in that the X-ray powder ctogram of this salt using Cu Kα radiation at 25°C has at least 3 of the following 2Θ (2 theta) values: 2Θ (2 theta) values in ° The X-ray diffractogram of ive crystal form C using Cu Kα radiation at 25°C preferably has at least 4, preferably at least 6, preferably at least 8, more preferably all of the 2Θ (2 theta) values men- tioned above.

James & Wells Ref: 307010NZ The X-ray powder diffractogram of inventive crystal form C using Cu Kα radiation at 25°C more preferably additionally has at least two, four, six, eight, ten, twelve or more, ably at least 15, 20, 23, , 27, 30, 33, 35, 38, 40, 42, 44, 46, 48, 50 or more, preferably all of the following 2Θ (2 theta) values: James & Wells Ref: NZ Inventive crystal form C is preferably characterized in that the Raman spectrum thereof has at least the following bands: Band maximum [cm-1] James & Wells Ref: 307010NZ The Raman spectrum of crystal form C according to the ion preferably has at least ten of the bands specified in Table 4, preferably 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65 or more, preferably all of the bands specified in Table 4.

The Raman spectrum of inventive crystal form C preferably ponds essentially to the spectrum shown in Figure 6.

The present invention r relates to a composition comprising crystal form C in a total amount of at least 5% by weight, wherein this total amount is preferably at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95% by weight or more, based in each case on the total amount of monosodium salt of foramsulfuron present in the composition.

The present invention ably relates to a composition comprising crystal form C (as d above), wherein the composition is present in solid form at 25°C and 1013 mbar, and/or the content of monosodium salt of foramsulfuron is 80% by weight or more, wherein the content of monosodium salt of foramsulfuron is preferably 85% by weight or more, preferably 90% by weight or more, particularly preferably 95% by weight or more, based in each case on the total weight of the composition.

Inventive crystal form B can be prepared by the method described below.

The invention further relates to a method for preparing crystal form B comprising the steps of (a) suspending a monosodium salt of foramsulfuron (preferably of crystal form A), of crystal form C, or a mixture of these substances in a diluent or t mixture, wherein the diluent or diluent mixture used in step (a) is selected from the group consisting of alcohols having 3 to 6 carbon atoms, in this case preferably primary alcohols having 3 to 6 carbon atoms, and ketones having 3 to 6 carbon atoms, and mixtures thereof, or comprises at least 20% by weight thereof, preferably at least 30% by weight, more preferably at least 40% by , even more preferably at least 50% by weight thereof.

Crystal form B according to the invention can be obtained if the t or diluent e used in the method described above comprises 20% by weight or more of alcohols having 3 to 6 carbon atoms and/or ketones having 3 to 6 carbon atoms.

James & Wells Ref: 307010NZ It is able if the diluent or diluent mixture used in the method described above comprises 60% by weight or more of alcohols having 3 to 6 carbon atoms and/or ketones having 3 to 6 carbon atoms, since readily filterable crystals are obtained in this manner, which is of considerable advantage in process engineering terms.

The invention therefore relates particularly to a method for preparing crystal form B comprising the steps of (a) suspending a monosodium salt of foramsulfuron (preferably of crystal form A), of l form C, or a mixture of these substances in a diluent or diluent mixture, wherein the diluent or diluent mixture used in step (a) is selected from the group ting of alcohols having 3 to 6 carbon atoms, in this case ably primary alcohols having 3 to 6 carbon atoms, and s having 3 to 6 carbon atoms, and es thereof, or comprises at least 60% by weight thereof.

The invention further relates to a method for preparing crystal form B comprising the steps of (a) suspending foramsulfuron in a diluent or t mixture, (b) reacting foramsulfuron with a base containing sodium, preferably an organic base, in this case preferably sodium methoxide and/or sodium ethoxide, wherein the diluent or t mixture used in step (a) is selected from the group consisting of alcohols having 3 to 6 carbon atoms, in this case ably primary ls having 3 to 6 carbon atoms, and ketones having 3 to 6 carbon atoms, and mixtures thereof, or comprises at least 20% by weight thereof, preferably at least 30% by weight, more preferably at least 40% by weight, even more preferably at least 50% by weight thereof.

The invention relates particularly to a method for preparing crystal form B comprising the steps of (a) suspending foramsulfuron in a diluent or diluent e, (b) reacting foramsulfuron with an organic base containing sodium, preferably sodium methoxide and/or sodium de, wherein the diluent or t mixture used in step (a) is selected from the group consisting of alcohols having 3 to 6 carbon atoms, in this case preferably primary alcohols having 3 to 6 carbon atoms, and ketones having 3 to 6 carbon atoms, and mixtures thereof, or comprises at least 60% by weight thereof.

In this case, sodium methoxide in methanol and/or sodium ethoxide in ethanol is preferably used as organic base containing sodium in step (b).

James & Wells Ref: 307010NZ The methods according to the invention for preparing crystal form B are preferably conducted in a manner such that the diluent or diluent mixture used in step (a) is selected from the group consisting of alcohols having 3 to 6 carbon atoms, in this case preferably primary alcohols having 3 to 6 carbon atoms, and ketones having 3 to 6 carbon atoms, and mixtures thereof, or comprises at least 60% by weight thereof, preferably 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, particularly preferably 95% by weight or more thereof.

The methods according to the invention for preparing crystal form B are preferably conducted in a manner such that the t or diluent mixture used in step (a) is selected from the group consisting of 1- butanol, acetone, methyl isobutyl ketone, and es thereof, or comprises 60% by weight or more thereof (preferably 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, particularly preferably 95% by weight or more thereof).

The methods ing to the invention for preparing crystal form B are carried out preferably at temperatures of at least 0°C. The methods according to the invention for preparing crystal form B are preferably carried out at temperatures in the range of 0 to 150°C, preferably at temperatures in the range of to 130°C.

The s according to the invention for preparing crystal form B are preferably carried out at temperatures of at least 25°C, preferably of at least 30°C, preferably of at least 40°C. The methods ing to the invention for ing crystal form B are ably carried out at temperatures in the range of 40 to 150°C, preferably at atures in the range of 45 to 130°C, particularly preferably in the range of 50 to 120°C.

In particularly preferred methods according to the invention for preparing crystal form B, acetone is used as a diluent or the diluent in step (a). In this case, the methods according to the invention for the preparation are preferably carried out at atures in the range of 0 to 65°C, preferably in the range of 25 to 56°C.

In further particularly preferred methods according to the invention for preparing crystal form B, acetone is used as a diluent or the diluent in step (a). In this case, the methods according to the invention for the preparation are preferably carried out at temperatures in the range of 40 to 65°C, preferably in the range of 45 to 56°C, particularly preferably in the range of 50 to 56°C.

The methods ing to the invention for preparing l form B are preferably carried out in a manner such that the ratio by weight of the total amount of ulfuron, crystal form A and crystal form C, to the total amount of diluent or diluent mixture used in step (a) is less than 2:1. The ratio by weight of the total amount of foramsulfuron, monosodium salts of ulfuron (preferably crystal form A) and of crystal form C, to the total amount of t or diluent mixture used in step (a) is James & Wells Ref: NZ preferably in the range of 3: 1 to 1: 20, preferably in the range of 2: 1 to 1: 15, more ably in the range of 1: 1 to 1: 10. In many cases, this ratio by weight is preferably in the range of 2: 3 to 1: 8, and particularly in the range of 1: 2 to 1: 5.

The method according to the invention for preparing inventive crystal form B preferably comprises further steps, preferably a cooling of the resulting mixture containing crystal form B. In this case, the g preferably takes place over a period of at least 15 s, preferably of at least 30 minutes.

Here, the g more preferably takes place over a period of at least 60 minutes, even more ably of at least 120 minutes, and particularly preferably of at least 180 minutes.

The method according to the invention for preparing inventive crystal form B preferably comprises further steps, preferably filtration of the resulting mixture containing crystal form B, and/or isolation of crystal form B, and/or drying of crystal form B.

In the context of the method according to the invention for preparing inventive crystal form B, it is red if the starting material used, preferably crystal form A and/or crystal form C, is at most sparingly dissolved in the diluent, and in particular – in contrast to recrystallization processes – is not completely dissolved, but rather a solid–solid conversion of the starting material into crystal form B takes place, i.e. a conversion of solid substances.

The invention further relates to a mixture comprising (i) monosodium salt of foramsulfuron and/or a e thereof, ably comprising crystal form A, crystal form B, crystal form C, or a mixture comprising two or all of these crystal forms, and (ii) a diluent or diluent mixture selected from the group consisting of alcohols having 3 to 6 carbon atoms, in this case ably primary alcohols having 3 to 6 carbon atoms, and ketones having 3 to 6 carbon atoms, and mixtures thereof, or comprises at least 20% by weight thereof, ably at least % by , more preferably at least 40% by weight, even more preferably at least 50% by weight thereof.

The invention relates particularly to a mixture comprising (i) monosodium salt of foramsulfuron and/or a solvate f, preferably comprising crystal form A, crystal form B, crystal form C, or a mixture comprising two or all of these crystal forms, and James & Wells Ref: 307010NZ (ii) a diluent or diluent mixture ed from the group consisting of alcohols having 3 to 6 carbon atoms, in this case preferably primary ls having 3 to 6 carbon atoms, and ketones having 3 to 6 carbon atoms, and mixtures thereof, or comprises at least 60% by weight f, and preferably 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, particularly preferably 95% by weight or more thereof.

The diluent or diluent mixture is preferably such a mixture according to the invention selected from the group consisting of 1-butanol, acetone, methyl isobutyl ketone, and mixtures thereof, or it comprises at least 60% by weight f (preferably 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, ularly preferably 95% by weight or more thereof).

The ratio by weight of the total amount of constituent (a), monosodium salt of foramsulfuron, to the total amount of constituent (b), diluent or diluent mixture in a mixture according to the invention, preferably corresponds to the weight ratios specified above (as preferred), based in each case on the total weight of the mixture which are stated in connection with the preparation method of inventive crystal form B.

Inventive crystal form B can be employed as such or in the form of agrochemical formulations (formulations) with other pesticidally active ingredients, such as, for example, icides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, for example as ed formulation or as tank mixes. The combination formulations can be prepared on the basis of the ations mentioned hereinafter, while taking t of the physical properties and stabilities of the active ingredients to be combined. Inventive crystal form B can be formulated in s ways, in which in general ary formulation auxiliaries in the pesticide field are used and/or other (agrochemical) active ingredients.

The invention therefore relates in a further aspect to an agrochemical formulation comprising (a) a herbicidally effective amount of crystal form B, and one or more further constituents ed from the group consisting of the following constituents (bi ), (b-ii) and (b-iii): (b-i) formulation auxiliaries customary in the pesticide field, (b-ii) further agrochemical active ingredients, (b-iii) crystal form C.

James & Wells Ref: 307010NZ A ation according to the invention preferably comprises one or more safeners (here preferably isoxadifen, isoxadifen-ethyl and/or cyprosulfamide) as constituent (b-ii) and/or one or more further herbicidal active ients.

The further herbicidal active ients are preferably selected from the herbicidal active ingredients mentioned in "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Society of Chemistry, 2012. In this case, the preferred herbicidal active ingredients are the herbicidal active ingredients mentioned in EP 0 790 771 A1 or EP 1 104 239 A1, particularly other ALS inhibitors (acetolactate synthase inhibitors), in turn ably thiencarbazone-methyl and salts thereof and/or other sulphonylurea herbicides, in turn ably amidosulfuron, mesosulfuron, mesosulfuron-methyl, iodosulfuron, iodosulfuron-methyl, and respective salts thereof such as lfuron-sodium or iodosulfuron-methyl-sodium (the particular advantages with t to the (stability) improvement in combination with other sulphonylurea herbicides has already been stated earlier).

In addition, the agrochemical formulations (formulations) mentioned ally comprise the respective ary stickers, wetters, dispersants, emulsifiers, penetrants, preservatives, eeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity. Examples of ation auxiliaries are described, inter alia, in "Chemistry and Technology of Agrochemical Formulations", ed. D. A. Knowles, Kluwer Academic Publishers (1998).

Potential useful formulations for inventive agrochemical formulations comprising crystal form B according to the invention e: wettable powders (WP), soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oilmiscible solutions, e sions (CS), dusting products (DP), seed-dressing products, granules for scattering and soil application, es (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.

It has also been found that is advantageous, in particular agrochemical formulations according to the invention such as some oil dispersions (OD), to use a mixture of inventive crystal form B and ive crystal form C. Such agrochemical formulations according to the invention are in this case based preferably on formulations such as are described in US 2002/0016263 A1 or US 2005/0032647 A1.

Such agrochemical formulations comprising a mixture of inventive crystal form B and inventive crystal form C showed, with respect to ise identical formulations which ned only crystal form B, further improved properties, for e, a further improved storage stability, particularly in this case with respect to flowability and viscosity of the formulation.

James & Wells Ref: 307010NZ In such agrochemical formulations according to the invention, the ratio by weight of the total amount of crystal form B to the total amount of crystal form C is preferably in the range of 20: 1 to 1: 10, preferably in the range of 10: 1 to 1: 5, more preferably in the range of 10: 1 to 1: 3 and particularly preferably in the range from 5: 1 to 1: 1, based in each case on the total weight of the agrochemical formulation according to the ion.

These individual formulation types are known in principle and are described, for e, in: Winnacker-Küchler, "Chemische Technologie" [Chemical Technology], volume 7, C. Hanser Verlag Munich, 4th ed. 1986; Wade van burg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd.

London.

The formulation auxiliaries required, such as inert materials, surfactants, solvents and further ves, are se known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd ed., Darland Books, Caldwell N.J.; H.v. Olphen, duction to Clay Colloid Chemistry", 2nd ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide", 2nd ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; eldt, "Grenzflächenaktive Äthylenoxidaddukte" [Interface-active Ethylene Oxide Adducts], Wiss.

Verlagsgesellschaft, Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie" [Chemical Technology], volume 7, C. Hanser Verlag Munich, 4th ed. 1986. le powders are preparations which can be dispersed uniformly in water and, in addition to the active ingredient, apart from a diluent or inert substance, also se surfactants of the ionic and/or nonionic type ng agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulphates, alkanesulphonates, alkylbenzenesulphonates, sodium lignosulphonate, sodium 2,2'-dinaphthylmethane- 6,6'-disulphonate, sodium dibutylnaphthalenesulphonate or else sodium methyltaurate. To produce the wettable powders, the herbicidally active ingredients are finely ground, for example in customary apparatus such as hammer mills, blower mills and air-jet mills, and simultaneously or subsequently mixed with the formulation auxiliaries.

Emulsifiable concentrates are produced by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene, or else vely high-boiling aromatics or hydrocarbons or mixtures of the organic ts, with addition of one or more ionic and/or nonionic tants (emulsifiers). Examples of emulsifiers which may be used are: calcium alkylarylsulphonates such as m dodecylbenzenesulphonate, or nonionic emulsifiers such as fatty acid polyglycol esters, James & Wells Ref: 307010NZ alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or yethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.

Dustable s are obtained by grinding the active ingredient with finely distributed solid substances, for example talc, l clays such as , bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates may be water- or sed. They may be prepared, for example, by wetgrinding by means of commercial bead mills and optional addition of surfactants as have, for example, already been listed above for the other formulation types.

Emulsions, for example oil-in-water emulsions (EW), can be produced, for e, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and optionally surfactants as already listed above, for example, for the other formulation types.

Granules can be prepared either by spraying the active ingredient onto adsorptive granular inert material or by applying active ient concentrates to the surface of carriers, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium rylate or else mineral oils. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer es - if desired as a mixture with fertilizers.

Water-dispersible granules are produced generally by the customary processes such as spray-drying, fluidized bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material.

For the production of pan granules, fluidized bed granules, extruder granules and spray granules, see, for e, processes in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E.

Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff.; 's Chemical Engineer's Handbook", 5th ed., McGraw-Hill, New York 1973, pp. 8-57.

Preferred agrochemical formulations according to the invention are those in which the inventive crystal form B is present in solid form. These are, for e, granules, encapsulated granules, tablets, waterdispersible granules, water-dispersible s, water-dispersible powders, dust formulations, formulations in which the active ingredient is t in dispersed form, such as, for example: suspension concentrates (SC), sed suspension concentrates, suspo-emulsions or suspension concentrates.

Particularly preferred agrochemical formulations ing to the invention comprising inventive crystal form B are those in which the agrochemical formulation is present in a form selected from the group consisting of wettable powders (WP), water-soluble powders (SP), suspension concentrates (SC), oil James & Wells Ref: 307010NZ dispersions (OD), capsule suspensions (CS), dusting products (DP), granules for scattering and soil application , granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), soluble granules (SG), ULV formulations, microcapsules and waxes.

For further s regarding the ation of crop protection compositions, see, for example, G.C.

Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

The agrochemical formulations according to the invention generally comprise 0.1 to 99% by weight, particularly 0.1 to 95% by weight of inventive crystal form B, based on the total weight of the agrochemical formulation, wherein the total amount of inventive crystal form B may be varied depending on the formulations.

In wettable powders, the total amount of inventive crystal form B is typically 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation constituents.

In emulsifiable concentrates, the total amount of inventive crystal form B may be about 1 to 90% and preferably 5 to 80% by weight. Formulations in the form of dusts generally comprise a total amount of ive crystal form B of 1 to 30% by weight, preferably 5 to 20% by weight. In water-dispersible granules, the total amount of inventive crystal form B is for example in the range of 1 and 95% by , in the range of 10 and 80% by , based on the total weight of the agrochemical formulation.

The present invention therefore also provides a method for controlling harmful plants and/or for regulating the growth of , characterized in that an effective amount - of crystal form B, - a composition comprising l form B, as d above, - an agrochemical formulation according to the invention, as defined above, is d to the plants, seeds of plants, the soil in which or on which the plants grow or the area under ation.

It has also been found that crystal form B according to the invention, mixtures according to the invention, compositions ing to the invention and formulations according to the invention, defined in each case in the t of the present invention, are suitable for controlling harmful plants or for regulating James & Wells Ref: NZ the growth of plants. Controlling of l plants or regulating the growth of plants is effected advantageously in particular crop plants. In this case, preferred crop plants are in particular oilseed rape, soya bean, cotton, sugar beet and true grasses, in particular here corn, barley, wheat, rye, oats, triticale, millet, rice, wherein corn is ularly preferred. In a preferred configuration, the crop plants, particularly the crop plants ied as preferred, are transgenic plants.

In addition, application to turf areas, for example golf s, is also possible.

Examples: The invention is elucidated by the examples which follow. Unless stated otherwise, all data refer to the weight.

The symbol ">" means "greater than" and the symbol "< " means "less than".

Example 1: Preparation of crystal form A 1000 g of N-[(4,6-dimethoxypyridinyl)aminocarbonyl]dimethylaminocarbonylformylaminobenzenesulphonamide were lly charged in 4750 g of cold 5°C MeOH (6000 mL).

To this were added 32 g of seed crystals of crystal form A (according to EP 0 757 679 A1) and the mixture cooled to 0°C over 20 minutes. After reaching a temperature of 0°C, 418 g (440 mL) of 30% sodium methoxide solution were metered in 2 hours, such that an internal temperature of 5°C was not exceeded.

The resulting very pasty mixture was then divided between two coolable 4 L frits and filtered under suction. After about 2 hours, the filtration was te and each frit was washed with 500 mL.

In total, 2220 g of moist product were obtained, which were then dried at 65°C at a pressure < 100 mbar.

The drying takes 44 h in total. The drying is terminated at a residual methanol content of 1.5% by weight. 1012 g of a 97% strength product were obtained.

Example 2: Variation of temperature in the preparation of crystal form A in methanol.

In separate containers, 20 g of N-[(4,6-dimethoxypyridinyl)aminocarbonyl]dimethylaminocarbonylformylaminobenzenesulphonamide were each initially charged in 100 g MeOH.

In each case, 1 g of seed crystals of crystal form A was added and one equivalent of NaOMe as a 30% olic solution was added at the temperature stated in each case over a period of 2 hours. The post reaction time was 3 hours in each case.

James & Wells Ref: 307010NZ To isolate the respective product, the respective mixture was heated or cooled to 20°C and then filtered.

After drying at 65°C at a pressure < 100 mbar, the residual t of ol in each product was determined.

Experiment T in °C Filtration time in s MeOH content in % by No. weight 1 0 150 0.53 2 15 50 1.49 3 35 4 2.83 4 50 5 5.19 Example 3: Storage of the methanol-moist crystal form A and conversion thereof into crystal form In separate containers, 5 g each of crystal form A were each stirred with 20 g of MeOH and subsequently filtered off.

At 20°C, 30°C and 35°C, the moistened products were stored for one week and a sample taken daily.

These s were dried at 65°C and 100 mbar and the respective methanol content subsequently determined.

Already after 2 days (35°C), 3 days (30°C) and 7 days (20°C), crystal form A had converted practically completely into crystal form C (MeOH content about 6.4% by weight).

Example 4: Preparation of crystal form B from crystal form A 1000 g of N-[(4,6-dimethoxypyridinyl)aminocarbonyl]dimethylaminocarbonylformylaminobenzenesulphonamide Na salt (crystal form A) were suspended in 3000 g of acetone and heated under reflux for 2 hours. After cooling to 20°C, the suspension was filtered. The filtration took 60 minutes.

The moist product thus obtained was then dried ght at 70°C and a pressure < 100 mbar. 9230 g of a 98.6% strength product were obtained. The MeOH content in this product was < 0.1% by , and the e content < 0.05% by weight.

Example 5: Preparation of crystal form B from crystal form C James & Wells Ref: 307010NZ 100 g of N-[(4,6-dimethoxypyridinyl)aminocarbonyl]dimethylaminocarbonylformylaminobenzenesulphonamide Na salt (crystal form C; MeOH content about 6.4%) were suspended in 300 g of acetone and heated under reflux for 2 hours. After g to 20°C, the suspension was ed. The filtration took a few seconds.

The moist product was dried overnight at 70°C and a pressure < 100 mbar. 92 g of a 99.2% strength product were obtained. The methanol content in this product was below the detection limit, and the acetone content was 0.026% by weight.

Example 6: Preparation of crystal form B from foramsulfuron and sodium methoxide 100 g of N-[(4,6-dimethoxypyridinyl)aminocarbonyl]dimethylaminocarbonylformyl-aminobenzenesulphonamide were suspended in 300 g of acetone and treated with one equivalent of NaOMe as a 30% methanolic solution (40.21 g) at 40°C over 1 hour. uently, the resulting mixture was heated under reflux for 2 hours. After cooling to 20°C, the suspension was filtered. The filtration took ca. 30 seconds.

The moist product was dried ght at 70°C and a pressure < 100 mbar. 104 g of a 98.4% strength product were obtained. The ol content in the product obtained was 0.006% by weight and the acetone content was 0.048% by weight.

Example 7: Preparation of crystal form B from foramsulfuron and sodium ethoxide 100 g of N-[(4,6-dimethoxypyridinyl)aminocarbonyl]dimethylaminocarbonylformylaminobenzenesulphonamide were suspended in 400 g of acetone and treated with one equivalent of NaOEt as a 21% ethanolic solution (73.1 g) under reflux over 1 hour. The mixture was subsequently heated r under reflux for 2 hours. After cooling to 20°C, the suspension was filtered. The filtration took ca. 60 seconds.

The moist product was dried overnight at 70°C and a pressure < 100 mbar. 102 g of a 98.6% strength product were obtained. The ethanol t in the product obtained was 0.0105% by weight and the acetone content was 0.024% by weight.

Example 8: Stability test of crystal form B in ol g of l form B (MeOH content < 0.01%) were suspended in 100 g of methanol and stirred for 7 days at 30°C. The product was filtered and then dried overnight at 70°C and a pressure < 100 mbar.

James & Wells Ref: 307010NZ 9.1 g of a 99.4% strength product were obtained. The methanol content in the product obtained was 0.004% by weight and the acetone content was 0.0003% by weight.

Example 9: Investigation of the chemical storage stability of crystal forms A and B Crystal forms A and B were each incorporated separately in an otherwise identical formulation in the form of oil dispersions (OD) and stored under the same conditions.

The oil dispersions were stored under the following storage ions and were ed with respect to the chemical degradation of crystal form A or B: Storage for two weeks at 40°C (specified below as 2W 40°C) Storage for four weeks at 40°C (specified below as 4W 40°C) Storage for two weeks at 54°C (specified below as 2W 54°C) In this manner, storage over a longer time period at a correspondingly lower temperature is also simulated.

The crystal forms were incorporated in three different formulations in the form of oil dispersions (OD), where these ations, in addition to the agrochemical active ingredients specified below, comprised customary formulation constituents such as emulsifiers, thickeners and diluents, and also in some cases pH regulators and/or ers.

In addition to 3.05% by weight of crystal form A or B, formulation OD1 comprised as further active ingredients 0.1% by weight iodosulfuron-methyl-sodium (a sulphonylurea herbicide) and 2.91% by weight isoxadifen-ethyl (a safener).

In addition to 3.21% by weight of l form A or B, ation OD2 comprised as further active ients 1.02% by weight thiencarbazone-methyl and 1.53% by weight cyprosulfamide (a safener).

In addition to 3.21% by weight of crystal form A or B, formulation OD3 comprised as r active ingredients 0.11% by weight iodosulfuron-methyl-sodium (a sulphonylurea herbicide), 1.02% by weight thiencarbazone-methyl and 1.53% by weight cyprosulfamide (a r).

Table 9-1: Chemical stability of crystal forms A and B in formulation OD 1 Crystal form Degradation in % 4W 40°C 2W 54°C Crystal form A 3.4 7.7 James & Wells Ref: 307010NZ Crystal form B 1.5 3.4 Table 9-2: Chemical stability of crystal forms A and B in formulation OD 2 Crystal form Degradation in % 2W 40°C 2W 54°C l form A 1.8 8.6 l form B 0.6 1.8 Table 9-3: Chemical stability of crystal forms A and B in formulation OD 3 Crystal form Degradation in % Hardness 2W 54°C (40°C) Crystal form A 2.1 4.8 Crystal form B 0.3 1.4 Example 10: Preparation of crystal form B from foramsulfuron and sodium methoxide 100 g of N-[(4,6-dimethoxypyridinyl)aminocarbonyl]dimethylaminocarbonylformylaminobenzenesulphonamide were suspended in 300 g of an acetone/methanol mixture (80:20 parts by weight) and d with one lent of NaOMe as a 30% methanolic on at 30°C over 2 hours. Subsequently , the mixture was stirred at 30°C for another 2 hours. After g to 20°C, the suspension was filtered. The filtration took 50 seconds.

The moist t was dried overnight at 70°C and a pressure < 100 mbar. 102 g of a 98.6% strength product were obtained. The methanol content in the product obtained was 0.03% by weight and the acetone content was 0.014% by weight.

Example 11: Preparation of crystal form B from foramsulfuron and sodium methoxide 100 g of N-[(4,6-dimethoxypyridinyl)aminocarbonyl]dimethylaminocarbonylformylaminobenzenesulphonamide were suspended in a mixture of 150 g of acetone and 100 g of methanol and heated to 30°C. To this were added at the same time 38.6 g of NaOMe as a 30% methanolic solution over two hours. Stirring was continued at 30°C for one hour. The temperature was then increased to 40°C, and after 1 hour at this temperature a further hour at 45°C.

James & Wells Ref: 307010NZ After cooling to 20°C, the suspension was filtered and the filter cake was washed with 100 g of acetone.

The moist product was dried ght at 70°C and a pressure < 100 mbar.

The methanol content in the product obtained was 0.10% by weight and the acetone content was 0.13% by weight.

Example 12: Sorption/desorption curve of l form B Sorption and tion curves of crystal form B were measured isothermically at 25°C.

The sorption curve gives the water uptake at increasing relative humidity and the desorption curve gives the drying behaviour on moisture reduction.

Relative humidity Sorption (% by Desorption (% by weight) weight) .0% 0.100 0.846 .0% 0.201 1.227 .0% 0.313 1.495 40.0% 0.444 1.760 50.0% 0.566 2.086 60.0% 0.684 2.269 70.0% 0.864 2.485 80.0% 1.085 3.016 90.0% 2.335 5.151 The result of the investigation shows that crystal form B is not copic.

Example 13: Investigation of the copicity of crystal forms A, B and C 100 mg each of crystal forms A, B and C were separately filled into small glass vials with snap-on caps.

These three glass vials with snap-on caps were placed unsealed in a glass beaker of which the bottom was covered with a small amount of water. The glass beaker was then sealed with a reversible sealing film and stored for one week at 25°C. After this storage , the water content of the respective sample was determined by Karl Fischer titration. The water content of the sample of crystal form B was 0.4% by weight, and the water content of the samples of crystal forms A and C was 15.7 and 21.3% by weight.

James & Wells Ref: NZ The samples of crystal forms A and C were hygroscopic and after storage were very ductile and sticky whereas the sample of crystal form B was still crystalline and powdery.

Claims (20)

Claims

1. Monosodium salt of foramsulfuron in crystalline form, wherein the X-ray powder diffractogram of the salt using Cu Kα radiation at 25°C has all of the following 2Θ (2 theta) values: 2Θ (2 theta) values in °

2. Monosodium salt of foramsulfuron according to Claim 1, wherein the X-ray powder diffractogram of the salt using Cu Kα ion at 25°C has at least 4 of the 2Θ (2 theta) values specified in Claim 1.

3. Monosodium salt of foramsulfuron ing to Claim 1 or 2, wherein the X-ray powder diffractogram of the salt using Cu Kα radiation at 25°C has at least 6 of the 2Θ (2 theta) values specified in Claim 1.

4. Monosodium salt of foramsulfuron according to any one of Claims 1 to 3, wherein the X-ray powder diffractogram of the salt using Cu Kα radiation at 25°C has at least 8 of the 2Θ (2 theta) values specified in Claim 1.

5. Monosodium salt of foramsulfuron according to any one of Claims 1 to 4, wherein the X-ray powder diffractogram of the salt using Cu Kα radiation at 25°C in on has at least two, four, six, eight, ten, twelve or more of the following 2Θ (2 theta) values:

6. Monosodium salt of foramsulfuron according to any one of Claims 1 to 5, wherein the Raman spectrum thereof has at least the following bands: Band maximum [cm-1]

7. Composition comprising the monosodium salt of foramsulfuron according to any one of Claims 1 to 6 in a total amount of at least 5% by , based on the total amount of monosodium salt of foramsulfuron present in the composition.

8. Composition according to Claim 7, wherein the composition is present in solid form at 25°C and 1013 mbar, and/or the content of dium salt of foramsulfuron is about 80% by weight or more, based on the total weight of the composition.

9. Use of the monosodium salt of foramsulfuron according to any one of Claims 1 to 6 or of a composition according to Claim 7 or 8 for preparing an emical formulation.

10. Method for preparing the monosodium salt of foramsulfuron in crystalline form according to any one of Claims 1 to 6, comprising the steps of: (a) suspending a monosodium salt of foramsulfuron, the monomethanol solvate of the monosodium salt of foramsulfuron, or a e of these 2 forms, in a diluent or diluent e, wherein the X-ray powder diffractogram of the monomethanol solvate of the monosodium salt of foramsulfuron using Cu Kα radiation at 25°C has at least 3 of the following 2Θ (2 theta) values: 2Θ (2 theta) values in ° wherein the diluent or diluent mixture used in step (a) is selected from the group consisting of alcohols having 3 to 6 carbon atoms, and ketones having 3 to 6 carbon atoms, and mixtures f, or comprises at least 20% by weight of alcohols having 3 to 6 carbon atoms and/or ketones having 3 to 6 carbon atoms.

11. Method for preparing the monosodium salt of foramsulfuron in crystalline form according to any one of Claims 1 to 6, comprising the steps of: (a) suspending foramsulfuron in a diluent or diluent mixture, (b) reacting foramsulfuron with a base containing sodium, n the diluent or diluent mixture used in step (a) is ed from the group consisting of ls having 3 to 6 carbon atoms, and ketones having 3 to 6 carbon atoms, and mixtures thereof, or comprises at least 20% by weight of alcohols having 3 to 6 carbon atoms and/or ketones having 3 to 6 carbon atoms.

12. Method according to Claim 10 or 11, wherein the alcohol is a primary l having 3 to 6 carbon atoms.

13. Method according to Claim 11, wherein the base containing sodium is an organic base.

14. Method according to Claim 13, wherein the organic base is sodium methoxide or sodium ethoxide.

15. Method according to any one of Claims 10 to 14, wherein the method is carried out at a temperature of at least 0°C.

16. Method according to any one of Claims 10 to 15, wherein the ratio by weight of the total amount of foramsulfuron, monosodium salt of foramsulfuron, and monomethanol e of the monosodium salt of foramsulfuron as defined in Claim 10, to the total amount of diluent or diluent mixture used in step (a) is less than about 2:1.

17. Mixture comprising: (i) the monosodium salt of foramsulfuron according to any one of Claims 1 to 6 or a mixture of the monosodium salt of foramulsufuron according to any one of Claims 1 to 6 and a monomethanol solvate thereof as defined in Claim 10, and (ii) a t or diluent mixture selected from the group consisting of alcohols having 3 to 6 carbon atoms, and ketones having 3 to 6 carbon atoms, and mixtures thereof, or comprises at least 20% by weight of alcohols having 3 to 6 carbon atoms and/or ketones having 3 to 6 carbon atoms.

18. Mixture according to Claim 17, wherein the alcohol is a primary alcohol having 3 to 6 carbon atoms.

19. Agrochemical ation comprising (a) a idally effective amount of the monosodium salt of foramsulfuron in crystalline form according to any one of Claims 1 to 6, and one or more further constituents ed from the group consisting of the following constituents (b-i), (b-ii) and (b-iii): (b-i) formulation auxiliaries ary in the pesticide field, (b-ii) further agrochemical active ingredients, (b-iii) the monomethanol e of the monosodium salt of foramsulfuron as defined in Claim

20. Method for controlling harmful plants or for regulating the growth of plants, wherein an effective amount - of the monosodium salt of foramsulfuron according to any one of Claims 1 to 6, - a composition according to Claim 7 or 8, or - an agrochemical formulation according to Claim 19, is d to the plants, seeds of plants, the soil in which or on which the plants grow or the area under cultivation. WO 96613 -