Abstract:
What is described is a thermodynamically stable crystal modification of the herbidically active compound 2-({2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]phenyl}carbonyl)cyclohexan-1,3-dione (tembotrione). This thermodynamically stable crystal modification has particular advantages in the stability of suspension formulations.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is a Continuation of PCT/EP2008/006386, filed Aug. 2, 2008, which claims priority to European Application No. 07016606.1, filed Aug. 24, 2007. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    1. Field of the Invention 
         [0003]    The invention relates to the technical field of the crop protection agents. 
         [0004]    More specifically, it relates to a thermodynamically stable crystal modification of 2-({2-chloro-4-(methy Isulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]phenyl}carbonyl)cyclo-hexan-1,3-dione of the formula 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    (hereinbelow referred to as tembotrione), to processes for its preparation and to its use as herbicide. 
         [0005]    2. Description of Related Art 
         [0006]    It is known that some organic compounds can occur in only one crystal structure while others (so-called polymorphs) can occur in various crystal structures, see, for example, J. Bernstein, R. J. Davey, J. O. Henck, Angew. Chem. Int. Ed., 1999, 38, 3440-3461. Thus, EP 1 314 724 A1 discloses two crystal structures of the herbidically active compound sulcotrione. 
         [0007]    Tembotrione, which is known, for example, from WO 00/21924 (example No. 3 in table 1), has herbicidal properties and is suitable for preparing crop protection compositions used for weed control. However, it has been found that the tembotrione preparable in accordance with the disclosure of WO 00/21924 is not suitable for preparing user-friendly presentation forms. User-friendly presentation forms are, for example, suspension formulations in which tembotrione is present finely ground in solid form. In tests in practice, it has been found that, in suspension formulations, tembotrione preparable in accordance with the disclosure of WO 00/21924 leads to crystal growth and, as a consequence thereof, to agglomeration and precipitation, such that the suspension formulation becomes unusable. The crystal growth may occur spontaneously or over a relatively long period of time and is unpredictable. 
       SUMMARY OF THE INVENTION 
       [0008]    It was an object of the present invention to provide a modification of tembotrione which overcomes these disadvantages and which is suitable for preparing a suspension formulation which is storage-stable for a relatively long period of time. 
         [0009]    We have found a thermodynamically stable modification of tembotrione which crystallizes in an orthorhombic system and which does not have the abovementioned disadvantages and is thus suitable for preparing suspension formulations such as suspoconcentrates, suspoemulsiones and oil dispersions. 
         [0010]    Accordingly, the invention provides a modification of 2-({2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]phenyl}carbonyl)cyclohexan-1,3-dione (tembotrione) which crystallizes in an orthorhombic system. 
       DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT 
       [0011]    In the context of the present invention, it was found that tembotrione, in addition to the stable modification crystallizing in an orthorhombic system, also occurs in at least two metastable modifications. 
         [0012]    Hereinbelow, the terms “stable modification I”, “stable crystal modification I”, “thermodynamically stable modification I” and “thermodynamically stable crystal modification I” are to be understood as being equivalent. 
         [0013]    The stable modification has a melting point of 124.0° C., a characteristic Raman spectrum ( FIG. 1 ) and a characteristic infrared spectrum ( FIG. 1   a ). Hereinbelow, it is referred to as crystal modification I. 
         [0000]    The first metastable modification has a melting point of 123.9° C., a characteristic Raman spectrum ( FIG. 2 ) and a characteristic infrared spectrum ( FIG. 2   a ). Hereinbelow, it is referred to as crystal modification II. 
         [0014]    The second metastable modification has a melting point of 121.6° C., a characteristic Raman spectrum ( FIG. 3 ) and a characteristic infrared spectrum ( FIG. 3   a ). Hereinbelow, it is referred to as crystal modification III. 
         [0015]    The single-crystal structural analysis of the crystal modification I of tembotrione shows the characteristic bond angles and bond lengths for this crystal modification, which are stated in table 3. 
         [0016]    The single-crystal structural analysis of the crystal modification II of tembotrione shows the characteristic bond angles and bond lengths for this crystal modification, which are stated in table 4. 
         [0017]    The x-ray powder diffractometry of the crystal modification I of tembotrione shows peaks characteristic for this crystal modification, which are stated in table 5. 
         [0018]    The x-ray powder diffractometry of the crystal modification II of tembotrione shows peaks characteristic for this crystal modification, which are stated in table 6. 
         [0019]    Further crystallographic data of the crystal modifications I and II of tembotrione are stated in table 7. 
     
    
     
       DESCRIPTION OF THE FIGURES 
         [0020]      FIG. 1  shows the Raman spectrum of the crystal modification I of tembotrione. The values of the band maxima in wave numbers are listed in table 1. 
           [0021]      FIG. 1   a  shows the infrared spectrum of the crystal modification I of tembotrione. The values of the band maxima in wave numbers are listed in table 2. 
           [0022]      FIG. 2  shows the Raman spectrum of the crystal modification II of tembotrione. The values of the band maxima in wave numbers are listed in table 1. 
           [0023]      FIG. 2   a  shows the infrared spectrum of the crystal modification II of tembotrione. The values of the band maxima in wave numbers are listed in table 2. 
           [0024]      FIG. 3  shows the Raman spectrum of the crystal modification III of tembotrione. The values of the band maxima in wave numbers are listed in table 1. 
           [0025]      FIG. 3   a  shows the infrared spectrum of the crystal modification III of tembotrione. The values of the band maxima in wave numbers are listed in table 2. 
       
    
    
       [0026]      
         [0000]    
       
         
               
             
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Band maxima of the Raman spectra in [cm −1 ] 
               
             
          
           
               
                 Crystal modification I 
                 Crystal modification II 
                 Crystal modification III 
               
               
                   
               
             
          
           
               
                 91 
                 921 
                 94 
                 976 
                 85 
                 867 
               
               
                 130 
                 952 
                 146 
                 992 
                 92 
                 891 
               
               
                 171 
                 968 
                 181 
                 1015 
                 95 
                 899 
               
               
                 192 
                 1002 
                 203 
                 1055 
                 108 
                 927 
               
               
                 213 
                 1053 
                 215 
                 1072 
                 124 
                 957 
               
               
                 265 
                 1075 
                 253 
                 1123 
                 145 
                 977 
               
               
                 279 
                 1116 
                 292 
                 1144 
                 215 
                 1004 
               
               
                 291 
                 1141 
                 313 
                 1171 
                 269 
                 1008 
               
               
                 311 
                 1166 
                 334 
                 1196 
                 299 
                 1037 
               
               
                 363 
                 1176 
                 360 
                 1239 
                 315 
                 1050 
               
               
                 402 
                 1197 
                 378 
                 1255 
                 361 
                 1081 
               
               
                 431 
                 1272 
                 393 
                 1281 
                 371 
                 1112 
               
               
                 445 
                 1289 
                 416 
                 1315 
                 392 
                 1129 
               
               
                 460 
                 1300 
                 441 
                 1335 
                 434 
                 1144 
               
               
                 490 
                 1325 
                 481 
                 1356 
                 440 
                 1154 
               
               
                 507 
                 1337 
                 508 
                 1420 
                 449 
                 1188 
               
               
                 517 
                 1358 
                 535 
                 1435 
                 456 
                 1226 
               
               
                 540 
                 1377 
                 550 
                 1466 
                 474 
                 1238 
               
               
                 550 
                 1418 
                 571 
                 1487 
                 480 
                 1254 
               
               
                 599 
                 1461 
                 594 
                 1538 
                 493 
                 1279 
               
               
                 613 
                 1557 
                 626 
                 1554 
                 506 
                 1286 
               
               
                 655 
                 1587 
                 649 
                 1584 
                 513 
                 1326 
               
               
                 675 
                 1665 
                 672 
                 1610 
                 522 
                 1353 
               
               
                 687 
                 1679 
                 746 
                 1662 
                 539 
                 1410 
               
               
                 738 
                 2888 
                 782 
                 1681 
                 550 
                 1445 
               
               
                 775 
                 2925 
                 791 
                 2895 
                 557 
                 1453 
               
               
                 813 
                 2971 
                 807 
                 2908 
                 575 
                 1469 
               
               
                 836 
                 2978 
                 830 
                 2928 
                 579 
                 1487 
               
               
                 853 
                 3010 
                 845 
                 2971 
                 591 
                 1553 
               
               
                 883 
                 3075 
                 855 
                 3011 
                 604 
                 1583 
               
               
                   
                   
                 885 
                 3062 
                 625 
                 1610 
               
               
                   
                   
                 919 
                 3096 
                 653 
                 1637 
               
               
                   
                   
                 927 
                   
                 670 
                 1663 
               
               
                   
                   
                   
                   
                 684 
                 1684 
               
               
                   
                   
                   
                   
                 694 
                 1711 
               
               
                   
                   
                   
                   
                 707 
                 2838 
               
               
                   
                   
                   
                   
                 722 
                 2892 
               
               
                   
                   
                   
                   
                 750 
                 2937 
               
               
                   
                   
                   
                   
                 768 
                 2973 
               
               
                   
                   
                   
                   
                 805 
                 3020 
               
               
                   
                   
                   
                   
                 832 
                 3073 
               
               
                   
                   
                   
                   
                 850 
                 3099 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Band maxima of the infrared spectra in [cm −1 ] 
               
             
          
           
               
                 Crystal modification I 
                 Crystal modification II 
                 Crystal modification III 
               
               
                   
               
             
          
           
               
                 593 
                 1164 
                 555 
                 1033 
                 555 
                 1154 
               
               
                 612 
                 1196 
                 571 
                 1082 
                 585 
                 1190 
               
               
                 654 
                 1253 
                 592 
                 1116 
                 604 
                 1211 
               
               
                 686 
                 1282 
                 625 
                 1142 
                 611 
                 1226 
               
               
                 765 
                 1298 
                 645 
                 1194 
                 666 
                 1238 
               
               
                 777 
                 1336 
                 680 
                 1275 
                 678 
                 1273 
               
               
                 786 
                 1356 
                 743 
                 1299 
                 766 
                 1293 
               
               
                 813 
                 1386 
                 766 
                 1333 
                 778 
                 1309 
               
               
                 836 
                 1409 
                 777 
                 1353 
                 791 
                 1325 
               
               
                 853 
                 1417 
                 789 
                 1375 
                 804 
                 1350 
               
               
                 883 
                 1461 
                 804 
                 1400 
                 831 
                 1414 
               
               
                 921 
                 1553 
                 816 
                 1413 
                 851 
                 1467 
               
               
                 951 
                 1675 
                 828 
                 1464 
                 867 
                 1553 
               
               
                 966 
                 2897 
                 838 
                 1538 
                 927 
                 1584 
               
               
                 994 
                 2926 
                 853 
                 1580 
                 955 
                 1611 
               
               
                 1010 
                 2959 
                 883 
                 1591 
                 971 
                 1641 
               
               
                 1085 
                 3010 
                 918 
                 1660 
                 988 
                 1662 
               
               
                 1112 
                 3075 
                 927 
                 1695 
                 1016 
                 1696 
               
               
                 1138 
                   
                 956 
                 2929 
                 1034 
                 2901 
               
               
                   
                   
                 973 
                 2968 
                 1052 
                 2938 
               
               
                   
                   
                 991 
                 3023 
                 1081 
                 2972 
               
               
                   
                   
                 1001 
                 3098 
                 1119 
                 3023 
               
               
                   
                   
                 1012 
                   
                 1144 
                 3099 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Bond lengths [Å] and bond angles [°] of the crystal modification I 
               
             
          
           
               
                 Bond 
                 Å (°) 
                 Bond 
                 Å (°) 
               
               
                   
               
               
                 CL(1)—C(3) 
                 1.732(2) 
                 O(6)—C(17) 
                 1.305(3) 
               
               
                 S(1)—O(2) 
                 1.4377(17) 
                 C(9)—C(10) 
                 1.486(3) 
               
               
                 S(1)—O(1) 
                 1.439(2) 
                 C(11)—C(12) 
                 1.441(3) 
               
               
                 S(1)—C(7) 
                 1.755(3) 
                 C(12)—C(17) 
                 1.395(3) 
               
               
                 S(1)—C(1) 
                 1.784(2) 
                 C(12)—C(13) 
                 1.472(3) 
               
               
                 C(1)—C(6) 
                 1.391(3) 
                 C(13)—C(14) 
                 1.516(3) 
               
               
                 C(1)—C(2) 
                 1.405(3) 
                 C(14)—C(15) 
                 1.505(4) 
               
               
                 F(1)—C(10) 
                 1.328(3) 
                 C(15)—C(16) 
                 1.515(4) 
               
               
                 C(2)—C(3) 
                 1.400(3) 
                 C(16)—C(17) 
                 1.491(3) 
               
               
                 C(2)—C(8) 
                 1.511(3) 
                 O(3)—C(9)—C(10) 
                 107.7(2) 
               
               
                 F(2)—C(10) 
                 1.316(3) 
                 F(2)—C(10)—F(1) 
                 105.9(3) 
               
               
                 C(3)—C(4) 
                 1.390(3) 
                 F(2)—C(10)—F(3) 
                 106.8(2) 
               
               
                 O(3)—C(9) 
                 1.407(4) 
                 F(1)—C(10)—F(3) 
                 106.6(2) 
               
               
                 O(3)—C(8) 
                 1.427(3) 
                 F(2)—C(10)—C(9) 
                 114.6(2) 
               
               
                 F(3)—C(10) 
                 1.331(4) 
                 F(1)—C(10)—C(9) 
                 111.3(2) 
               
               
                 O(4)—C(11) 
                 1.245(3) 
                 F(3)—C(10)—C(9) 
                 111.2(3) 
               
               
                 C(4)—C(5) 
                 1.387(3) 
                 O(4)—C(11)—C(12) 
                 121.6(2) 
               
               
                 C(4)—C(11) 
                 1.502(3) 
                 O(4)—C(11)—C(4) 
                 115.24(19) 
               
               
                 O(5)—C(13) 
                 1.219(3) 
                 C(12)—C(11)—C(4) 
                 123.02(19) 
               
               
                 C(5)—C(6) 
                 1.387(3) 
                 C(17)—C(12)—C(11) 
                 117.8(2) 
               
               
                 O(2)—S(1)—O(1) 
                 117.41(13) 
                 C(17)—C(12)—C(13) 
                 119.7(2) 
               
               
                 O(2)—S(1)—C(7) 
                 109.36(14) 
                 C(11)—C(12)—C(13) 
                 122.49(19) 
               
               
                 O(1)—S(1)—C(7) 
                 108.37(12) 
                 O(5)—C(13)—C(12) 
                 122.2(2) 
               
               
                 O(2)—S(1)—C(1) 
                 109.85(10) 
                 O(5)—C(13)—C(14) 
                 120.4(2) 
               
               
                 O(1)—S(1)—C(1) 
                 107.25(11) 
                 C(12)—C(13)—C(14) 
                 117.2(2) 
               
               
                 C(7)—S(1)—C(1) 
                 103.72(12) 
                 C(15)—C(14)—C(13) 
                 114.9(2) 
               
               
                 C(6)—C(1)—C(2) 
                 121.89(19) 
                 C(14)—C(15)—C(16) 
                 110.0(2) 
               
               
                 C(6)—C(1)—S(1) 
                 114.88(16) 
                 C(17)—C(16)—C(15) 
                 111.2(2) 
               
               
                 C(2)—C(1)—S(1) 
                 123.15(16) 
                 O(6)—C(17)—C(12) 
                 122.0(2) 
               
               
                 C(3)—C(2)—C(1) 
                 116.25(19) 
                 O(6)—C(17)—C(16) 
                 115.4(2) 
               
               
                 C(3)—C(2)—C(8) 
                 118.4(2) 
                 C(12)—C(17)—C(16) 
                 122.6(2) 
               
               
                 C(1)—C(2)—C(8) 
                 125.3(2) 
               
               
                 C(4)—C(3)—C(2) 
                 122.7(2) 
               
               
                 C(4)—C(3)—Cl(1) 
                 116.81(16) 
               
               
                 C(2)—C(3)—Cl(1) 
                 120.43(17) 
               
               
                 C(9)—O(3)—C(8) 
                 112.98(19) 
               
               
                 C(5)—C(4)—C(3) 
                 119.1(2) 
               
               
                 C(5)—C(4)—C(11) 
                 119.83(19) 
               
               
                 C(3)—C(4)—C(11) 
                 120.7(2) 
               
               
                 C(6)—C(5)—C(4) 
                 120.1(2) 
               
               
                 C(5)—C(6)—C(1) 
                 119.8(2) 
               
               
                 O(3)—C(8)—C(2) 
                 111.96(18) 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Bond length [Å] and bond angles of the crystal modification II 
               
             
          
           
               
                 Bond 
                 Å (°) 
                 Bond 
                 Å (°) 
               
               
                   
               
               
                 Cl(1)—C(3) 
                 1.7352(16) 
                 C(9B)—C(10B) 
                 1.505(5) 
               
               
                 S(1)—O(1) 
                 1.4294(14) 
                 C(10B)—F(3B) 
                 1.323(5) 
               
               
                 S(1)—O(2) 
                 1.4297(16) 
                 C(10B)—F(1B) 
                 1.328(5) 
               
               
                 S(1)—C(7) 
                 1.743(3) 
                 C(10B)—F(2B) 
                  1.361(11) 
               
               
                 S(1)—C(1) 
                 1.7843(16) 
                 C(11)—C(12) 
                 1.444(2) 
               
               
                 C(1)—C(6) 
                 1.381(2) 
                 C(12)—C(13) 
                 1.390(2) 
               
               
                 C(1)—C(2) 
                 1.407(2) 
                 C(12)—C(17) 
                 1.469(2) 
               
               
                 C(2)—C(3) 
                 1.391(2) 
                 C(13)—C(14) 
                 1.480(2) 
               
               
                 C(2)—C(8) 
                 1.506(2) 
                 C(14)—C(15) 
                 1.510(3) 
               
               
                 C(3)—C(4) 
                 1.392(2) 
                 C(15)—C(16) 
                 1.506(3) 
               
               
                 O(4)—C(11) 
                 1.243(2) 
                 C(16)—C(17) 
                 1.512(2) 
               
               
                 C(4)—C(5) 
                 1.384(2) 
                 F(2A)—C(10A)—F(1A) 
                 106.2(6) 
               
               
                 C(4)—C(11) 
                 1.505(2) 
                 F(3A)—C(10A)—C(9A) 
                 114.0(9) 
               
               
                 O(5)—C(13) 
                 1.312(2) 
                 F(2A)—C(10A)—C(9A) 
                 112.2(5) 
               
               
                 C(5)—C(6) 
                 1.380(2) 
                 F(1A)—C(10A)—C(9A) 
                 113.8(5) 
               
               
                 O(6)—C(17) 
                 1.220(2) 
                 C(9B)—O(3B)—C(8) 
                 113.6(2) 
               
               
                 C(8)—O(3A) 
                 1.381(4) 
                 O(3B)—C(9B)—C(10B) 
                 112.3(3) 
               
               
                 C(8)—O(3B) 
                 1.495(3) 
                 F(3B)—C(10B)—F(1B) 
                 106.5(4) 
               
               
                 O(3A)—C(9A) 
                 1.396(5) 
                 F(3B)—C(10B)—F(2B) 
                 102.9(6) 
               
               
                 C(9A)—C(10A) 
                 1.491(8) 
                 F(1B)—C(10B)—F(2B) 
                 109.5(7) 
               
               
                 C(10A)—F(3A) 
                  1.267(16) 
                 F(3B)—C(10B)—C(9B) 
                 112.5(3) 
               
               
                 C(10A)—F(2A) 
                 1.330(8) 
                 F(1B)—C(10B)—C(9B) 
                 112.3(3) 
               
               
                 C(10A)—F(1A) 
                 1.340(7) 
                 F(2B)—C(10B)—C(9B) 
                 112.7(5) 
               
               
                 O(3B)—C(9B) 
                 1.406(4) 
                 O(4)—C(11)—C(12) 
                 122.17(15) 
               
               
                 O(1)—S(1)—O(2) 
                 117.29(10) 
                 O(4)—C(11)—C(4) 
                 116.88(14) 
               
               
                 O(1)—S(1)—C(7) 
                 109.74(15) 
                 C(12)—C(11)—C(4) 
                 120.93(14) 
               
               
                 O(2)—S(1)—C(7) 
                 107.43(18) 
                 C(13)—C(12)—C(11) 
                 118.64(14) 
               
               
                 O(1)—S(1)—C(1) 
                 111.12(8)  
                 C(13)—C(12)—C(17) 
                 119.17(14) 
               
               
                 O(2)—S(1)—C(1) 
                 107.13(8)  
                 C(11)—C(12)—C(17) 
                 122.10(14) 
               
               
                 C(7)—S(1)—C(1) 
                 103.11(11) 
                 O(5)—C(13)—C(12) 
                 122.28(15) 
               
               
                 C(6)—C(1)—C(2) 
                 121.53(15) 
                 O(5)—C(13)—C(14) 
                 114.49(15) 
               
               
                 C(6)—C(1)—S(1) 
                 115.28(13) 
                 C(12)—C(13)—C(14) 
                 123.23(15) 
               
               
                 C(2)—C(1)—S(1) 
                 123.08(12) 
                 C(13)—C(14)—C(15) 
                 111.94(15) 
               
               
                 C(3)—C(2)—C(1) 
                 116.11(14) 
                 C(16)—C(15)—C(14) 
                 110.06(16) 
               
               
                 C(3)—C(2)—C(8) 
                 120.47(14) 
                 C(15)—C(16)—C(17) 
                 113.94(15) 
               
               
                 C(1)—C(2)—C(8) 
                 123.42(14) 
                 O(6)—C(17)—C(12) 
                 122.32(14) 
               
               
                 C(2)—C(3)—C(4) 
                 122.82(15) 
                 O(6)—C(17)—C(16) 
                 119.85(15) 
               
               
                 C(2)—C(3)—Cl(1) 
                 120.15(12) 
                 C(12)—C(17)—C(16) 
                 117.72(14) 
               
               
                 C(4)—C(3)—Cl(1) 
                 117.03(12) 
               
               
                 C(5)—C(4)—C(3) 
                 119.20(15) 
               
               
                 C(5)—C(4)—C(11) 
                 119.03(14) 
               
               
                 C(3)—C(4)—C(11) 
                 121.76(14) 
               
               
                 C(6)—C(5)—C(4) 
                 119.46(15) 
               
               
                 C(5)—C(6)—C(1) 
                 120.70(16) 
               
               
                 O(3A)—C(8)—O(3B) 
                  30.21(15) 
               
               
                 O(3A)—C(8)—C(2) 
                 110.68(18) 
               
               
                 O(3B)—C(8)—C(2) 
                 104.49(15) 
               
               
                 C(8)—O(3A)—C(9A) 
                 116.4(3) 
               
               
                 O(3A)—C(9A)—C(10A) 
                 112.2(4) 
               
               
                 F(3A)—C(10A)—F(2A) 
                  110.4(11) 
               
               
                 F(3A)—C(10A)—F(1A) 
                  99.2(10) 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 5 
               
               
                   
               
               
                 X-ray powder diffractometry pattern of the crystal 
               
               
                 modification I of tembotrione [2θ] 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 7.3765 
                 20.8117 
                 26.6207 
                 32.4069 
               
               
                   
                 8.0674 
                 21.1093 
                 27.2879 
                 32.8121 
               
               
                   
                 10.7988 
                 21.5838 
                 27.4979 
                 33.1960 
               
               
                   
                 13.5030 
                 21.6983 
                 27.9884 
                 33.5965 
               
               
                   
                 14.7553 
                 23.5072 
                 28.2728 
                 34.4007 
               
               
                   
                 16.4462 
                 23.9969 
                 28.5989 
                 35.1147 
               
               
                   
                 16.6192 
                 24.3808 
                 29.0017 
                 35.7136 
               
               
                   
                 17.0512 
                 24.8173 
                 30.0318 
                 35.9960 
               
               
                   
                 17.1467 
                 25.0316 
                 30.2456 
                 36.4372 
               
               
                   
                 17.6444 
                 25.2513 
                 30.6058 
                 36.7974 
               
               
                   
                 17.7792 
                 25.5214 
                 30.7628 
               
               
                   
                 19.3008 
                 25.7119 
                 31.2971 
               
               
                   
                 20.4034 
                 25.9248 
                 31.6675 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 6 
               
               
                   
               
               
                 X-ray powder diffractometry pattern of the crystal 
               
               
                 modification II of tembotrione [2θ] 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 7.3765 
                 20.8117 
                 26.6207 
                 32.4069 
               
               
                   
                 8.0674 
                 21.1093 
                 27.2879 
                 32.8121 
               
               
                   
                 10.7988 
                 21.5838 
                 27.4979 
                 33.1960 
               
               
                   
                 13.5030 
                 21.6983 
                 27.9884 
                 33.5965 
               
               
                   
                 14.7553 
                 23.5072 
                 28.2728 
                 34.4007 
               
               
                   
                 16.4462 
                 23.9969 
                 28.5989 
                 35.1147 
               
               
                   
                 16.6192 
                 24.3808 
                 29.0017 
                 35.7136 
               
               
                   
                 17.0512 
                 24.8173 
                 30.0318 
                 35.9960 
               
               
                   
                 17.1467 
                 25.0316 
                 30.2456 
                 36.4372 
               
               
                   
                 17.6444 
                 25.2513 
                 30.6058 
                 36.7974 
               
               
                   
                 17.7792 
                 25.5214 
                 30.7628 
               
               
                   
                 19.3008 
                 25.7119 
                 31.2971 
               
               
                   
                 20.4034 
                 25.9248 
                 31.6675 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
             
               
               
               
             
               
               
               
               
               
             
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Crystallographic data 
               
             
          
           
               
                   
                 Crystal modification I 
                 Crystal modification II 
               
               
                   
                   
               
             
          
           
               
                 Symmetry type 
                 orthorhombic 
                 monocline 
               
               
                 Space group 
                 Pna2 1   
                 P2(1)/n 
               
             
          
           
               
                 Dimensions of the 
                 a = 31.1647(18) Å 
                             = 90° 
                 a = 15.8491(5) (18) Å 
                             = 90° 
               
               
                 unit cell 
                 b = 10.3522(6) Å 
                             = 90° 
                 b = 7.1164(2) Å 
                             = 95.721° 
               
               
                   
                 c = 5.5449(3) Å 
                             = 90° 
                 c = 16.1656(6) Å 
                             = 90° 
               
             
          
           
               
                 Volume of the unit cell 
                 1788.91(18) Å3 
                 1814.21(10) Å3 
               
               
                 Coordination number 
                 4 
                 4 
               
               
                 Density (calculated) 
                 1.637 Mg/m 3   
                 1.614 Mg/m 3   
               
               
                   
               
             
          
         
       
     
       DESCRIPTION OF THE INVENTION 
       [0027]    The melting points were determined by means of DSC (Pyris 1 from Perkin Elmer, heating rate 10 K min −1 ). For determining the Raman spectra, at least two spectra with 128 scans each were recorded for each batch by means of an RFS 100/S FT Raman from Bruker. The infrared spectra were recorded using an FT-IR spectrometer (from Bruker, Tensor 37), with in each case 64 scans. 
         [0028]    The solid density was determined by the SOP 5024 density determination method using an Ultrapyknometer 1000 T from Quanta-Chrome or determined from the single-crystal x-ray structure analysis (SCS). The single-crystal x-ray structure analysis (SCS) was carried out using an M18X—HF rotating anode with MoKα radiation from MACScience Co and a SMART-CCD-1000 detector from Bruker-AXS. The data were processed using the programs SAINT-NT V 5.0 (data reduction, Bruker-AXS) and SADABS (absorption correction, Bruker-AXS). The resolution of the structure and the refinement were carried out using SHELXTL NT Version V5.1. 
       Preparation 
       [0029]    Tembotrione can be prepared, for example, by the process mentioned in WO 00/21924. Depending on the nature of the solvent used in the final purification step and the temperatures used, tembotrione usually crystallizes as a mixture or in the form of one of the pure metastable crystal modifications II and III described here. 
         [0030]    In a general manner, the thermodynamically stable crystal modification I of tembotrione can be prepared by suspending and/or dissolving the crystal modifications II and III of tembotrione obtainable according to WO 00/21924 or mixtures thereof in a suitable solvent and treating it at temperatures of from 0° C. to 80° C. until it is converted quantitatively into the thermodynamically stable crystal modification I. 
         [0031]    Accordingly, the invention furthermore provides a process for preparing the thermodynamically stable crystal modification I of tembotrione wherein the crystal modifications II and III of tembotrione or mixtures thereof are suspended and/or dissolved in solvents and treated at temperatures of from 0° C. to 80° C. up to the quantitative conversion into the thermodynamically stable crystal modification I. 
         [0032]    Suitable solvents which may be employed in this process are, for example, lower alcohols, such as methanol, ethanol, 2-propanol, or ketones, such as acetone, 2-butanone, which may also be used as a mixture with water. Here, lower alcohols or ketones refer to compounds having one to ten carbon atoms, preferably one to five carbon atoms. Further suitable solvents are benzene, toluene and chlorobenzene. 
         [0033]    The conversion into the thermodynamically stable crystal modification I takes place at temperatures of below 100° C., preferably at temperatures of from 0° C. to 80° C., particularly preferably at temperatures of from 60° C. to 80° C., very particularly preferably at temperatures of from 50° C. to 80° C. The duration of the conversion depends on the temperature and the type of solvent. The duration of the conversion furthermore depends on whether seed crystals of the crystal modification I are used. In general, the conversion into the crystal modification I can be achieved directly, without the use of seed crystals, when the crystals of crystal modifications II and III or mixtures thereof are dissolved completely at elevated temperature when the solution is cooled to crystal at room temperature. Cooling to room temperature is preferably carried out using a cooling rate of less than 25° C., particularly preferably a cooling rate of less than 20° C. The conversion of a suspension of crystal modifications II and III or mixtures thereof can generally be effected without the use of seed crystals over a period of 14 days. If seed crystals of the crystal modification I are used in the conversion of a suspension, a duration of treatment of from 24 to 48 hours is generally sufficient for achieving a quantitative conversion of the crystals into the crystal modification I. 
         [0034]    The resulting crystals of the crystal modification I are finally separated off and dried at room temperature or elevated temperature to constant weight in order to remove the solvent. 
         [0035]    The stable crystal modification I can also be obtained by grinding under high pressure from the crystal modifications II and III or mixtures thereof. A suitable pressure is a pressure of at least 5 bar. 
         [0036]    By virtue of its stability, the crystal modification I is outstandingly suitable for preparing formulations, in particular suspension formulations, of crop protection agents. Accordingly, the invention also provides for crop protection compositions comprising the crystal modification I of tembotrione on its own or as a mixture with auxiliaries and carriers, and also as a mixture with other active compounds. The invention also includes mixtures of the crystal modification I of tembotrione with the crystal modifications II and III of tembotrione, for example those which occur at any point in the process according to the invention for the conversion of the crystal modifications II and III or mixtures thereof into the crystal modification I. Preference is given to an active compound quality comprising more than 20% by weight of the crystal modification I of tembotrione, particularly preferably comprising more than 90% by weight, very particularly preferably comprising more than 95% by weight and most preferably comprising more than 98% by weight. 
         [0037]    If appropriate tembotrione in the crystal modification I is mixed with one or more other herbicides. Such mixtures also benefit from the advantageous properties of the crystal modification I according to the invention. 
         [0038]    By virtue of its stability, the crystal modification I of tembotrione is in general suitable as starting material for the preparation of any tembotrione-comprising crop protection formulations, even if, after formulation, the tembotrione is no longer present in this form but, for example, in dissolved form. 
         [0039]    Accordingly, the invention also provides processes for preparing tembotrione-comprising crop protection formulations which use the crystal modification I of tembotrione, and also to tembotrione-comprising crop protection formulations obtained from the crystal modification I of tembotrione. By using the crystal modification I, the safety is increased for preparations of tembotrione and the risk of incorrect dosages is thus reduced. 
         [0040]    The crystal modification I of tembotrione can be converted in a known manner into the customary formulations, such as suspension concentrates, colloidal concentrates, dispersible concentrates, emulsifiable concentrates (emulsion concentrates), emulsion dressings, suspension dressings, granules, microgranules, suspoemulsiones, oil dispersions, water-soluble granules, water-soluble concentrates and water-dispersible granules, using suitable auxiliaries and carriers or solvents. Here, the active compound should be present in a concentration of from 0.5 to 90% by weight of the total mixture, i.e. in amounts which are sufficient to achieve the necessary dosage level. The formulations are prepared, for example, by extending the crystal modification I of tembotrione with solvents and/or carriers, if appropriate if the use of emulsifiers and/or dispersants, and/or other auxiliaries, such as, for example, penetrants. 
         [0041]    Application is effected in the customary manner by bringing the unwanted plants and/or their habitat into contact with the active compound or its formulation. 
         [0042]    Tembotrione in the crystal modification I has an outstanding herbicidal action against representatives of the group consisting both of the monocotyledonous and the dicotyledonous plants. Accordingly, the invention also provides the use of the crystal modification I of tembotrione for preparing a crop protection composition for treating weed infestation. 
         [0043]    Dicotyledonous plants of the genera:  Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datum, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.    
         [0044]    Monocotyledonous plants of the genera:  Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.    
         [0045]    By virtue of its good compatibility with crop plants, the crystal modification I according to the invention of tembotrione is suitable for controlling unwanted plants in crops of, for example, wheat, barley, oats, rye, rice, corn, sugar beet, sugar cane, cotton and soya beans, in particular in rice, corn and sugar cane. 
         [0046]    All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and recombinant methods or by combinations of these methods, including the transgenic plants and including the plant cultivars protectable or not protectable by plant breeders&#39; rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offsets and seeds. 
         [0047]    Treatment according to the invention of the plants and plant parts with the crystal modification I according to the invention of tembotrione is carried out directly or by allowing the compounds to act on their surroundings, environment or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on. 
         [0048]    The crystal modification I according to the invention of tembotrione can, as already discussed above, be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric materials. 
         [0049]    These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers. 
         [0050]    If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, or else water. 
         [0051]    Suitable solid carriers are: for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates, or else protein hydrolysates; suitable dispersants are: for example lignosulfite waste liquors and methylcellulose. 
         [0052]    Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or lattices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils. 
         [0053]    It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants such as alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. 
         [0054]    The formulations generally comprise between 0.1 and 95% by weight of active compound in the crystal modification I according to the invention, preferably between 0.5 and 90%. 
         [0055]    For controlling weeds, the crystal modification I according to the invention of tembotrione, as such or in their formulations, can also be used as mixtures with other agrochemically active compounds, for example known herbicides and/or substances which improve the compatibility with crop plants (“safeners”), finished formulations or tank mixes being possible. Also possible are thus mixtures with weedkillers comprising one or more known herbicides and a safener. 
         [0000]    Possible components for the mixtures are known herbicides, for example 
         [0056]    acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazon, benzfendizone, benzobicyclon, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone (-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D, 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (—P), diclofop (-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPIC, esprocarb, ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop (—P-ethyl), fentrazamide, flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (—P-butyl), fluazolate, flucarbazone (-sodium), flufenacet, flufenpyr, flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluoroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron, glufosinate (-ammonium), glyphosate (-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl, —P-methyl), hexazinone, imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet, mesosulfuron (-methyl, -sodium), mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-) metolachlor, metosulam, metoxuron, metribuzin, metsulfuron (-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmedipham, picolinafen, pinoxadene, piperophos, pretilachlor, primisulfuron (-methyl), profluazol, prometryn, propachlor, propanil, propaquizafop, propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrasulfotole, pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol, pyriftalid, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop (—P-ethyl, —P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron. 
         [0057]    Furthermore suitable for the mixtures are known safeners, for example AD-67, BAS-145138, benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, 2,4-D, DKA-24, dichlormid, dymron, fenclorim, fenchlorazol (-ethyl), flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), MCPA, mecoprop (—P), mefenpyr (-diethyl), MG-191, oxabetrinil, PPG-1292, R-29148. 
         [0058]    A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and soil improvers is also possible. 
         [0059]    The crystal modification I according to the invention of tembotrione can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is carried out in a customary manner, for example by watering, spraying, atomizing, broadcasting. 
         [0060]    The crystal modification I according to the invention of tembotrione can be applied both before and after emergence of the plants. They can also be incorporated into the soil prior to sowing. 
         [0061]    The application rate of active compound can vary within a relatively large range. It depends essentially on the nature of the desired effect. In general, the application rates are between 1 g and 1 kg of active compound per hectare of soil, preferably between 5 g and 500 g per ha. 
         [0062]    As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The term “parts” or “parts of plants” or “plant parts” has been explained above. Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are understood as meaning plants with specific properties (“traits”) which have been obtained by conventional cultivation, by mutagenesis or else by recombinant DNA techniques. These may be cultivars, biotypes or genotypes. 
         [0063]    Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive (“synergistic”) effects. Thus, for example, reduced application rates and/or widenings of the activity spectrum and/or an increase in the activity of the substances and compositions that can be used according to the invention also in combination with other agrochemical active compounds, better crop plant growth, increased tolerance of the crop plants to high or low temperatures, increased tolerance of the crop plants to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products which exceed the effects which were actually to be expected are possible. 
         [0064]    The preferred transgenic plants or plant cultivars (i.e. those obtained by genetic engineering) which are to be treated according to the invention include all plants which, in the genetic modification, received genetic material which imparted particularly advantageous useful properties (“traits”) to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such properties are a better defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), soya beans, potatoes, cotton, oilseed rape and also in particular corn and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to corn, soya beans, potatoes, cotton and oilseed rape. Traits that are emphasized are in particular increased defense of the plants against insects by toxins formed in the plants, in particular those formed in the plants by the genetic material from  Bacillus thuringiensis  (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (hereinbelow referred to as “Bt plants”). Traits which are also particularly emphasized are the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and the correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinothricin (for example the “PAT” gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of “Bt plants” which may be mentioned are corn varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example corn, cotton, soya beans), KnockOut® (for example corn), StarLink® (for example corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are corn varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosates, for example corn, cotton, soya bean), Liberty Link® (tolerance to phosphinothricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulfonylureas, for example corn). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example corn). Of course, these statements also apply to plant cultivars having these genetic traits or genetic traits still to be developed, which cultivars will be developed and/or marketed in the future. 
       Working Examples 
     Preparation of the Thermodynamically Stable Crystal Modification I 
       [0065]    At boiling point (56° C.) 2 g of tembotrione were dissolved completely in acetone and then slowly, i.e. at a cooling rate of less than 20° C./h, cooled to room temperature. The crystals are filtered off and dried at temperatures of &lt;60° C. 
       Preparation of the Metastable Crystal Modification II 
       [0066]    At boiling point (78° C.), 2 g of tembotrione were dissolved completely in ethanol. The clear solution was then slowly, i.e. at a cooling rate of less than 20° C./h, cooled to 7° C. The crystals are filtered off and dried at temperatures of &lt;60° C. 
       Preparation of the Metastable Crystal Modification III 
       [0067]    At boiling point (111° C.), 2 g of tembotrione were dissolved completely in toluene. The clear solution was then slowly, i.e. at a cooling rate of less than 20° C./h, cooled to 7° C. The crystals are filtered off and dried at temperatures of &lt;60° C. 
       Stability Test 
       [0068]    Compared to an oil dispersion of tembotrione of the crystal modification II, III or a mixture thereof, an oil dispersion of tembotrione of the crystal modification I shows no signs of agglomeration and precipitation even after several weeks of storage.