Usui, Yoshiro published the artcileFungicides. XII. Synthesis and antifungal activity of halogen-substituted phenylpyrazolone derivatives, HPLC of Formula: 14580-22-4, the publication is Yakugaku Zasshi (1967), 87(1), 38-42, database is CAplus and MEDLINE.
cf. CA 64: 14181e. A mixture of 1.5 g. I (X = 2,4,5-tri-Cl) and 0.9 g. Et acetoacetate is added to a mixture of 5 ml. AcOH and 5 ml. H2O, the whole heated 2 hrs., and 35 ml. H2O added to give 81% II, yellow needles, m. 58-60° (EtOH). I (0.02 mole) is heated in a mixture of 25 ml. AcOH and 10 ml. H2O with 0.02 mole Et acetoacetate for 2 hrs., the mixture evaporated in vacuo, the residue heated 5 hrs. with 25 ml. AcOH, evaporated in vacuo, and H2O added to the residue to give the following III (X, m.p., and % yield given): 2,3-di-Cl, 174-5°, 18; 2,6-di-Cl (red), 206°, 46; 2,4,5-tri-Cl (yellow), 199°, 81; 2,6-di-Br (yellow), 200-1°, 49. I (0.02 mole) and 0.02 mole Ac2O are added to 30 ml. C6H6, the whole boiled 3 hrs., cooled, and the precipitate recrystallized (C6H6) to give the following IV (X, m.p., and % yield given): 2-Cl, 118°, 62; 3-Cl, 131-2°, 62; 2,3-di-Cl, 136°, 73; 2,5-di-Cl, 159°, 97; 2,6-di-Cl, 153-5°, 93; 3,4-di-Cl, 168-71°, 77; 2,4,6-tri-Cl, 158°, 95.5; 2,6-di-Br, 158-61°, 58; 4-I, 159°, 74. PCl3 (1 mole) is dropped into a mixture of 1 mole each of IV and Et acetoacetate, the whole warmed 1.5 hrs. and poured into iced H2O, and the precipitate recrystallized from EtOH to give the following V (X, m.p., and % yield given): 2-Cl, 183-5°, 53; 3-Cl, 183°, 45; 4-Cl, 219-21°, 89; 2,3-di-Cl, 231-2°, 60; 2,6-di-Cl, 211-13°, 67; 3,4-di-Cl, yellow 208-9°, 76; 2,4,5-tri-Cl, yellow, 178-80°, 49; 2,4,6-tri-Cl, 193-4°, 49; 2,6-di-Br, 223-4°, 6.2; 4-I (brown), 214-16°, 37. Na (2.3 g.) is added to 40 ml. EtOH, boiled 17 hrs. with 6.2 g. Et cyanoacetate (VI) and 7.1 g. 4-chlorophenylhydrazine, and the mixture evaporated in vacuo. To the residue is added 120 ml. H2O, washed with Et2O, the residual aqueous solution neutralized with AcOH, and the solid recrystallized from MeOH to give 2.3 g. 1-(4-chlorophenyl)-3-aminopyrazolin-5-one, dark yellow needles, m. 169°. The use of Et cyclohexanone-2-carboxylate instead of VI in the above reaction gives 70% 2-(4-chlorophenyl)-4,5,6,7-tetrahydro-3-indazolinone, m. 186-7° (EtOH). Similarly prepared is 1-(4-chlorophenyl)-4,5,6,7-tetrahydro-3-indazolinone, m. 217-19° (EtOH). The relation between the structure of these compounds and their antifungal activity was examined using Corticium sasakii. It was found that antifungal activity tended to become weaker in the order phenylhydrazines > β-acetylphenylhydrazines > phenylhydrazones > phenylpyrazolones, and with the increasing number of halogens substituted.
Yakugaku Zasshi published new progress about 14580-22-4. 14580-22-4 belongs to pyrazoles-derivatives, auxiliary class Organic Pigment, name is 1-(2-Chlorophenyl)-3-methyl-5-pyrazolone, and the molecular formula is C6H13I, HPLC of Formula: 14580-22-4.
Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics