Polymorphs and amorphous forms of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile
The present invention relates to novel crystalline polymorphs, solvate pseudomorphs and amorphous form of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoroethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (fipronil). The present invention also provides methods for preparing the novel polymorphs, pseudomorphs and amorphous form, as well as insecticidal or pesticidal compositions comprising same, and methods of use thereof as pesticidal agents.
1. A toluene hemi solvate (FS-T) pseudomorph of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile exhibiting at least one of the following characteristics:
(a) an X-ray powder diffraction pattern having characteristic peaks expressed in degrees 2θ(+/−0.20° θ) at about 7.2, 9.3, 12.5, 17.6, 19.15, 20.85, 28.1, 30.05, and 33.40;
(b) an infrared (IR) spectrum having characteristic peaks at about 694.6, 733.2, 3328.4 and 3409.5 cm −1 .
2. The toluene hemisolvate pseudomorph according to claim 1 , wherein the toluene hemisolvate pseudomorph exhibits an X-ray powder diffraction pattern having characteristic peaks expressed in degrees 2θ (+/−0.20° θ) at about 7.2, 9.3, 12.5, 15.1, 17.6, 18.65, 14.15, 20.85, 25.95, 28.1, 30.05, and 33.40.
3. The toluene hemisolvate pseudomorph according to claim 1 , wherein the toluene hemisolvate pseudomorph exhibits an X-ray powder diffraction pattern substantially as shown in FIG. 10 .
4. The toluene hemisolvate pseudomorph according to claim 1 , wherein the toluene hemisolvate pseudomorph exhibits an infrared (IR) spectrum at the 3000 cm −1 range substantially as shown in FIG. 11 .
5. A process for the preparation of a compound which is a toluene hemi solvate (FS-T) pseudomorph of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile according to claim 1 , the process comprising the steps of crystallizing said compound from toluene; and isolating the resulting crystals.
6. The process according to claim 5 , comprising the steps of:
a) preparing a solution of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile in toluene;
b) cooling the solution so as to form crystals of said compound; and
c) isolating the crystals.
7. The process according to claim 6 , wherein step a) is conducted with heat.
8. The process according to claim 6 , wherein the solution obtained after step a) is cooled to a temperature of about 0° C. to about room temperature.
9. A pesticidal composition comprising an acceptable adjuvant and a pesticidally effective amount of a
toluene hemi solvate (FS-T) pseudomorph of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazol-3-carbonitrile according to claim 1 .
10. The pesticidal composition according to claim 9 for use in veterinary medicine, agriculture, treating fields or crops, household pest control, or roach, ant or termite control.
11. The pesticidal composition according to claim 9 , in a form suitable for percutaneous administration or topical administration.
12. The pesticidal composition according to claim 9 , in a form suitable for a spray, pest bait, granules, a gel or a solution.
13. A method for controlling pests at a locus, said method comprising applying to said locus a pesticidally effective amount of a composition according to claim 9 .