Crystalline modifications of prothioconazole

Abstract

There is disclosed a crystalline DMSO solvate of prothioconazole as well as amorphous prothioconazole. Methods for making these solid forms, microbicidal compositions comprising them and uses thereof are also disclosed.

What is claimed is: 
     
         1 . A crystalline solvate of prothioconazole with dimethylsulfoxide (DMSO). 
     
     
         2 . The crystalline solvate according to  claim 1 , wherein the solvate is a 1:1 solvate. 
     
     
         3 . The crystalline solvate according to  claim 1 , wherein the solvate is characterized by a desolvation peak in the range of 104.0° C.-109.0° C., as determined by differential scanning calorimetry (DSC). 
     
     
         4 . The crystalline solvate according to  claim 1 , wherein the solvate is characterized by an FT-IR absorption spectrum having at least one absorption band selected from among the following values (expressed as cm −1 ): (a) 712, (b) 859, (c) 1007, (d) 1401, and (e) 3259. 
     
     
         5 . The crystalline solvate according to  claim 4 , wherein the FT-IR absorption spectrum of the solvate has at least two absorption bands selected from the values recited in  claim 4 . 
     
     
         6 . The crystalline solvate according to  claim 4 , wherein the FT-IR absorption spectrum of the solvate has one or more additional FT-IR absorption bands having a value selected from among the following (expressed as cm −1 ): 644.6, 688.8, 781.5, 928.1, 1021.0, 1073.0, 1100.0, 1146.0, 1235.0, 1277.0, 1304.0, 1320.0, 1347.0, 1549.0, and 3137.0. 
     
     
         7 . The crystalline solvate according to  claim 1 , characterized by an X-ray powder diffraction (XRD) with at least one 20 value selected from 7.5, 10.15, 15.45, 16.75, 22.75, 24.85, 31.35, and 34.6. 
     
     
         8 . The crystalline solvate according to  claim 7 , wherein the XRD of the solvate has at least two of the 2θ values recited in  claim 7 . 
     
     
         9 . The crystalline solvate according to  claim 7 , wherein the XRD of the solvate has at least one additional 2θ value selected from the following: 15.95, 18.15, 19.40, 21.30, and 24.25. 
     
     
         10 . A method for preparing a crystalline solvate of prothioconazole with DMSO comprising:
 dissolving prothioconazole in DMSO;   providing a condition suitable for crystallization of prothioconazole DMSO solvate; and   isolating crystals of said solvate.   
     
     
         11 . The method according to  claim 10 , wherein said dissolving prothioconazole in DMSO is conducted with heating. 
     
     
         12 . The method according to  claim 10  wherein said condition is cooling. 
     
     
         13 . The method according to  claim 10  comprising:
 mixing prothioconazole and DMSO, 
 heating the mixture, 
 cooling the mixture, and 
 isolating crystals of said solvate from the cooled mixture. 
 
     
     
         14 . The method according to  claim 13 , wherein said heating is conducted during or after said mixing. 
     
     
         15 . The method according to  claim 13 , wherein said heating is conducted at a temperature of at least 50° C. 
     
     
         16 . The method according to  claim 13 , wherein the heating temperature is maintained for at least 30 minutes. 
     
     
         17 . The method according to  claim 12 , wherein said cooling comprises cooling the mixture to 40° C. or lower. 
     
     
         18 . The method according to  claim 12 , wherein said cooling is conducted at a rate of about 0.5 to 2.0° C./min. 
     
     
         19 . The method according to  claim 12 , wherein one or more secondary solvents are added to the cooled mixture. 
     
     
         20 . The method according to  claim 19 , wherein said one or more secondary solvents are selected from cyclohexane and a combination of cyclohexane and water. 
     
     
         21 . The method according to  claim 19 , wherein the mixture is further cooled. 
     
     
         22 . The method according to  claim 21 , wherein said further cooling is to a temperature in the range of 5 to 15° C. 
     
     
         23 . The method according to  claim 10 , wherein said isolating comprises filtering the crystals. 
     
     
         24 . A microbiocidal composition comprising crystalline prothioconazole DMSO solvate and one or more extenders and/or surfactants. 
     
     
         25 . A method for controlling unwanted microorganisms comprising applying an effective amount of crystalline prothioconazole DMSO solvate or a composition comprising thereof to one or both of the microorganisms and their habitat.