Tag: M.W=250-300

Fusco, Raffaello published the artcileFormazyls. III. A new method of synthesis of pyrazoles. Application to the synthesis of 3-arylazopyrazoles and 3-aminopyrazoles, Recommanded Product: 1,5-Diphenyl-1H-pyrazole-3-carboxylic acid, the publication is Gazzetta Chimica Italiana (1948), 332-41, database is CAplus.

cf. C.A. 42, 1232d. Compounds of the ArN:NC(Hal):NNHAr type studied in the previous work show the properties of both formazyls and hydrazonic halides because of the C(Hal):NNHîŒ?group common to the 2 classes. In the present work their behavior as hydrazonic halides was examined by an investigation of their cyclization to pyrazolic and other heterocyclic systems according to methods of synthesis alrady developed by F. and collaborators. This offered the possibility of preparing pyrazoles with arylazo groups in the 3-position, which have not been described, and which should be reducible to NH₂ derivatives PhN:NCCl:NNHPh (I) was used as a starting compound In general I was found to be more reactive than the hydrazonic halides previously studied, probably because of the great mobility of the Cl atom in such a central position. However, this reactivity does not result in high yields, but in darkening, evolution of gas, isonitrile odor, formation of resins, and general difficulty in isolating the desired products. Of the various methylenic agents studied, β-ketonic acid nitriles and β-diketones gave the best results. A suspension of 2.58 g. (0.01 mol) I in 20 cc. anhydrous MeOH, poured into 0.01 mol AHcCNaCN in 20 cc. anhydrous MeOH at 0° (spontaneous heating, evolution of gas, darkening, and precipitation of NaCl), allowed to stand ice-cold 20 h., and the precipitate washed with MeOH and water and purified by MeOH, yields 0.2-0.3 g. of 1-phenyl-3-phenylazo-4-cyano-5-methylpyrazole, PhN.N:C(N:NPh).C(CN):CMe, yellow, m. 130°, not hydrolyzed by prolonged heating in alc. KOH at 100°. Under the same conditions from I and BzCHNaCN, with final purification by glacial AcOH, is obtained 0.5 g. 1,5-diphenyl-3-phenylazo-4-cyanopyrazole, lustrous orange-yellow, m. 204-5°. A suspension of 2.58 g. I in anhydrous MeOH, poured into an equimol. weight of AcCHNaCOCH₂OPh in anhydrous MeOH at 0° (energetic reaction), allowed to stand cold, and the precipitate purified by EtOH, yields 0.2 g. 1-phenyl-3-phenylazo-4-acetyl-5-(phenoxymethyl)pyrazole, peach, m. 168°. When heated with p-O₂NC₆H₄NHNH₂ (II) in 50% AcOH, it forms the p-nitrophenylhydrazone, C₃₀H₂₅O₃N₇, orange-red, m. 218-19°. In the same way, 2.58 g. I and Ac₂CH₂ yield, after purification by MeOH, 0.3-0.5 g. of 1-phenyl-3-phenylazo-4-acetyl-5-methylpyrazole (III), orange-yellow, m. 179°. With II in 50% AcOH, III gives a p-nitrophenylhydrazone, C₂₄H₂₁O₂N₇, orange-red, m. 222°; with semicarbazide, a semicarbazone, C₁₉H₁₉ON₇, yellow, m. 193-4°. III (0.5 g.) and 50 cc. 40% HNO₃, refluxed 30 min. (the mixture turns yellow, nitrous vapors are evolved, and a little resin is formed), cooled to 0°, the product washed with water, macerated with aqueous Na₂CO₃, the yellow solution decolorized, filtered, acidified with HCl, and the precipitate purified by dilute MeOH, yield 1-(p-nitrophenyl)-3-phenylazo-5-methyl-4-pyrazolecarboxylic acid, light brown-yellow, m. 205°. Hot III (0.5 g.) in 20 cc. 80% AcOH, treated with excess powd. Zn, the solution, when decolorized, dried in vacuo, the residue taken up in MeOH, filtered hot, cooled, and the precipitate purified rapidly by MeOH (the product tends to oxidize rapidly), yields 1-phenyl-3-phenylhydrazino-4-acetyl-5-methylpyrazole, m. approx. 170° (difficult to purify because of its great tendency to oxidize to III). III (2 g.) in 200 cc. MeOH, 1 g. Raney Ni, and several drops aqueous NaOH, treated with H under 3 atm. pressure until hydrogenation is complete (about 4 h.), filtered, acidified (Congo red) with concentrated HCl, concentrated to a small volume, distilled to dryness in vacuo, the residue taken up in 20 cc. water, water added successively until all the solid dissolves and then seps., filtered, and the residue purified by MeOH, yield 0.6 g. of 1-phenyl-3-amino-4-acetyl-5-methylpyrazole (IV), m. 195-6°. The aqueous solution, treated with NaOAc, increases the yield to a total of 0.7-0.8 g. Treatment of the aqueous solution with NaOH and steam distillation yield approx. 0.6 g. of PhNH₂. IV is the 1st 3-aminopyrazole reported. It gives a p-nitrophenylhydrazone, C₁₈H₁₈O₂N₆, orange-red (from AcOH), m. 256° (decomposition). IV (0.05 g.) in 4 cc. 10% HCl and a small excess of solid NaNO₂, kept ice-cold until clear and poured into excess alk. 2-naphthol, precipitates a dark red compound IV (0.1 g.) in 5 cc. 10% HCl, diazotized with NaNO₂, the excess HNO₂ eliminated with urea, 5 cc. concentrated HCl and a trace of CuCl added (N is evolved), boiled to complete the reaction, allowed to stand, and the precipitate purified by MeOH, yields 1-phenyl-3-chloro-4-acetyl-5-methylpyrazole, m. 67°. All these experiments show the well-defined aromaticity of 3-amino derivatives (V) of pyrazole and point to the existence of the IV form in the possible tautomeric equilibrium: IV â‡?PhN.NH.C(:NH).CAc:CMe. Another method of preparing V more easily was studied, viz., by the action of diazo compounds on substituted malonic acids to form the corresponding formazyl ketones or aldehydes, according to the general reaction: RCOCH₂CH-(CO₂H)₂ + 2ArN₂X â†?RCOCH₂C(:NNHAr)N:NAr (VI) + HX + CO₂, and cyclization by mineral acids to the pyrazoles having the arylazo chain in the 3-position: VI H₂O â†?ArN.N:C(N:NAr).CH:CR. However, all attempts to couple diazo compounds with (formylmethyl)- and acetonylmalonic acids gave only intractable pitches. But an aqueous suspension of 2.7 g. BzCH₂CH(CO₂H)₂ in 18 cc., neutralized with NaHCO₃, 12 g. NaOAc added, heated until dissolved, cooled to 0°, PhN₂Cl (from 1.1 g. PhNH₂, 4.8 cc. concentrated HCl, 20 cc. water, and 0.85 g. NaNO₂) added, kept several hrs. at 0°, and the precipitate purified by dilute AcOH and EtOH, yields N,N’-diphenyl-C-phenacylformazan, BzCH₂C(:NNHPh)N:NPh (VII), red, m. 110°. HCl, added to the mother liquor from the precipitation of VII, filtered, and the residue purified by EtOH and dried at 150°, yields PhN.CPh:CH.C(CO₂H):N, m. 185° [cf. Ber. 20, 2185(1887)]. All attempts to cyclize VII under various conditions led to uncrystallizable pitches. Hence the method based on the use of formazyl halides remains the only one for the preparation of V.

Gazzetta Chimica Italiana published new progress about 13599-22-9. 13599-22-9 belongs to pyrazoles-derivatives, auxiliary class Pyrazole,Carboxylic acid,Benzene, name is 1,5-Diphenyl-1H-pyrazole-3-carboxylic acid, and the molecular formula is C16H12N2O2, Recommanded Product: 1,5-Diphenyl-1H-pyrazole-3-carboxylic acid.

Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics

Idemudia, Omoruyi G. published the artcileMetal complexes of new bioactive pyrazolone phenylhydrazones; crystal structure of 4-acetyl-3-methyl-1-phenyl-2-pyrazoline-5-one phenylhydrazone Ampp-Ph, Recommanded Product: 4-Benzoyl-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, the publication is International Journal of Molecular Sciences (2016), 17(5), 687/1-687/24, database is CAplus and MEDLINE.

The condensation reaction of phenylhydrazine and dinitrophenylhydrazine with 4-acetyl and 4-benzoyl pyrazolone precipitated air-stable acetyldinitrophenylhydrazone Ampp-Dh, benzoylphenylhydrazone Bmpp-Ph and benzoyldinitrophenylhydrazone Bmpp-Dh in their keto imine form; a study inspired by the burning interest for the development of new bioactive materials with novel properties that may become alternative therapeutic agents. Elemental anal., FTIR, 1H, and 13C NMR, and mass spectroscopy have been used to justify their proposed chem. structures, which were in agreement with the single crystal structure of Bmpp-Dh earlier reported according to X-ray crystallog. The single crystal structure of 4-acetyl-3-methyl-1-phenyl-pyrazoline-5-one phenylhydrazone Ampp-Ph, which crystallizes in a triclinic crystal system with a P-1 (Number 2) space group is presented. Octahedral Mn(II), Ni(II), Co(II), and Cu(II) complexes of these resp. ligands with two mols. each of the bidentate Schiff base, coordinating to the metal ion through the azomethine nitrogen C=N and the keto oxygen C=O, which were afforded by the reaction of aqueous solutions of the corresponding metal salts with the ligands are also reported. Their identity and proposed structures were according to elemental anal., FTIR spectroscopy, UV-VIS spectrophotometry (electronic spectra) and Bohr magnetic moments, as well as thermogravimetric anal. (TGA) results. A look at the antibacterial and antioxidant activities of synthesized compounds using the methods of the disk diffusion against some selected bacterial isolates and 1,1-diphenyl-2-picryl-hydrazil (DPPH) resp., showed biol. activities in relation to employed standard medicinal drugs.

International Journal of Molecular Sciences published new progress about 4551-69-3. 4551-69-3 belongs to pyrazoles-derivatives, auxiliary class Benzenes, name is 4-Benzoyl-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, and the molecular formula is C17H14N2O2, Recommanded Product: 4-Benzoyl-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one.

Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics

Idemudia, Omoruyi G. published the artcileSynthesis and characterization of bioactive acylpyrazolone sulfanilamides and their transition metal complexes: single crystal structure of 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one sulfanilamide, COA of Formula: C17H14N2O2, the publication is Bioinorganic Chemistry and Applications (2015), 1-15, database is CAplus and MEDLINE.

Two Schiff base ligands Ampp-Sn (1) and Bmpp-Sn (2), afforded by a condensation reaction between sulfanilamide and the resp. acylpyrazolone carbonyl precursors, their Mn(II), Co(II), Ni(II), and Cu(II) complexes prepared by the reaction of ligands and corresponding metal salts in aqueous solutions, were synthesized and then characterized by both anal. and spectroscopic methods, in a view to developing new improved bioactive materials with novel properties. From elemental anal., spectroscopic and TGA results, transition metal complexes, with octahedral geometry having two mols. of the bidentate keto-imine ligand each, are proposed. The single crystal structure of Bmpp-Sn according to x-ray crystallog. showed a keto-imine tautomer type of Schiff base, having three intramol. bonds, one short N2···H2···O3 hydrogen bond of 1.90 Å and two long C13···H13···O2 and C32···H32···O3 hydrogen bonds of 2.48 Å. A moderate to low biol. activities were exhibited by synthesized compounds when compared with standard antimicrobial agents on screening the synthesized compounds against Staphylococcus aureus, Bacillus pumilus, Proteus vulgaris, and Aeromonas hydrophila for antibacterial activity and against free radical 1,1-diphenyl-2-picryl-hydrazyl (DPPH) for antioxidant activity.

Bioinorganic Chemistry and Applications published new progress about 4551-69-3. 4551-69-3 belongs to pyrazoles-derivatives, auxiliary class Benzenes, name is 4-Benzoyl-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, and the molecular formula is C17H14N2O2, COA of Formula: C17H14N2O2.

Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics

Idemudia, Omoruyi G. published the artcileCrystal structure of 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one sulfadiazine dimethylformamide monosolvate, C₃₀H₂₉N₇O₄S, Name: 4-Benzoyl-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, the publication is Zeitschrift fuer Kristallographie – New Crystal Structures (2014), 229(4), 455-457, database is CAplus.

The crystal and mol. structure of a 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one Schiff base with sulfadiazine is presented. In the asym. unit the title compound occurs together with 1 DMF solvent mol. There are 2 notable intramol. H bonds, both with O1, namely N3-H3···O1 and C12-H12···O1 that hold the phenylpyrazolone backbone essentially planar together with extended resonance. The least square plane through the atoms N1-N3, O1, C1-C3, C5, and C11-C16 has a r.m.s. of 0.0671 Å. Adjacent mols. are held together at the sulfadiazine group with 2 short N4-H4···N6 H bonds with lengths of 2.062(19) Å which in terms of graph-set anal. can be described by means of a R²₂(8) descriptor on the unary level. There are a large number of π···π ring interactions. The 2 shortest interactions occur with the Ph ring C31-C36 which has 2 π···π ring interactions; 1 with an adjacent pyrazole ring N1, N2, C1-C3, and 1 with the Ph ring C11-C16. The centroid to centroid distances are 4.2512(8) and 4.2530(9) Å, resp. The crystal contains the solvent DMF positionally disordered in a 0.82:0.18 ratio. Crystallog. data are given.

Zeitschrift fuer Kristallographie – New Crystal Structures published new progress about 4551-69-3. 4551-69-3 belongs to pyrazoles-derivatives, auxiliary class Benzenes, name is 4-Benzoyl-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, and the molecular formula is C17H14N2O2, Name: 4-Benzoyl-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one.

Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics

Valecha, Sheela M. published the artcileSynthesis and characterization of manganese (II), cobalt (II), nickel (II), copper (II) and zinc (II) mixed ligand complexes with [(1-phenyl-3-methyl-5-hydroxopyrazol-4-yl) phenylimino]2′,3′ dimethylaniline and 2-hydroxy-1-naphthaldehyde, Application In Synthesis of 4551-69-3, the publication is Acta Chimica Pharmaceutica & Indica (2015), 5(1), 16-21, database is CAplus.

Mixed ligand complexes of the type [MLL′] where M = Mn (II), Co (II), Ni (II), Cu (II), Zn (II) HL = [(1-phenyl-3-methyl-5-hydroxopyrazol-4-yl)phenylimino]2,3-dimethylaniline; (HPMPZP)dma. HL′= 2-hydroxy-1-naphaldehyde; (HNA), have been synthesized and characterized on the basis of elemental anal., conductivity measurements, magnetic, electronic and infra red spectral studies. The complexes confirm to 1:1:1 stoichiometry and are non electrolytes. The schiff base HL act as a monovalent bidentate ligand co-ordinating through azomethine nitrogen and phenolic oxygen. On the basis of electronic spectra, IR spectra and magnetic moment measurements; six coordinated octahedral structures have been proposed for the complexes. Thermal studies revealed the presence of two coordinated water mols. The shiff base and mixed ligand complexes have been tested for their antibacterial activity against the Escherichia coli, Bacillus substilis, staphylococcus aureus.

Acta Chimica Pharmaceutica & Indica published new progress about 4551-69-3. 4551-69-3 belongs to pyrazoles-derivatives, auxiliary class Benzenes, name is 4-Benzoyl-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, and the molecular formula is C24H12, Application In Synthesis of 4551-69-3.

Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics

Venturella, Pietro published the artcileReactivity of the flavanone nucleus. II. Effect of substituents on the reaction with phenylhydrazine, Computed Properties of 13599-22-9, the publication is Annali di Chimica (Rome, Italy) (1961), 759-68, database is CAplus.

cf. CA 55, 15467b. Substituents in the flavanone nucleus do not particularly affect the conversion of their phenylhydrazones into pyrazoline derivatives The possibility to isolate the intermediate phenylhydrazones depends on the nature and the position of the substituents. The appropriate flavanone (0.5 g.) in 10 cc. 95% EtOH refluxed 1 hr. with 0.3 g. PhNHNH₂, kept some time, and diluted with H₂O gave the corresponding phenylhydrazone. In this manner were prepared the following compounds: 2-(p-methoxyphenyl)flavanone phenylhydrazone (I); 2-[3,4-(CH₂O₂)C₆H₃] analog (II) of I, m. 127-8°; 2-(3,4-methyl-enedioxyphenyl)-5,6,8-trimethoxyflavanone phenylhydrazone (III) (without EtOH), m. 129-31°; 2-Ph analog of III; 2-phenyl-6-methoxyflavanone phenylhydrazone (IV); and the 5,6-di-MeO analog of IV, needles, m. 118-20°. The appropriate flavanone (0.5 g.) and excess PhNHNH₂ heated a few min. in a test tube over a free flame, cooled, dissolved in AcOH, and poured into H₂O gave the corresponding 3,5-diarylpyrazoline (V). The appropriate flavanone (0.5 g.) in 5 cc. AcOH refluxed 1 hr. with 0.3 g. PhNHNH₂, cooled, and diluted with H₂O gave the corresponding V. The appropriate chalcone (0.2 g.) and PhNHNH₂ heated a few min. in a test tube over a free flame, dissolved in AcOH, and poured into H₂O gave the corresponding V. The appropriate phenylhydrazone refluxed 1 hr. with AcOH gave the corresponding V. The appropriate V refluxed with Ac₂O and NaOAc gave the corresponding acetate which fluoresces in EtOH intensely blue-green. By these methods were prepared the following V and their acetates (3- and 5-aryl group, crystal form, and m.p., and m.p. of acetate given): o-HOC₆H₄, p-MeOC₆H₄ (Va), needles, 168-9°, 132-3°; o-HOC₆H₄, 3,4-(CH₂O₂)C₆H₃ (VI), needles, 145-6°, 116-17°; 2,3,5,6-HO(MeO)₃C₆H, 3,4-(CH₂O₂)C₆H₃ (VIa), needles, 185-6°, 195-6°, 2,3,5,6-HO(MeO)₃C₆H, Ph (VII), yellow-green plates, 193-4°, 132-3°; 2,5-HO(MeO)C₆H₃, Ph (VIII), needles, 150-1°, 114-15°; 2,5,6-HO(MeO)₂C₆H₂, Ph (IX), yellow plates, 147-8°, 147°, VII or VIII or IX (1 g.) in 30 cc. refluxing 5% aqueous NaOH treated gradually with 6.5 g. KMnO₄ in 70 cc. H₂O, refluxed 3 hrs., and worked up gave 1,5-diphenyl-3-pyrazolecarboxylic acid, m. 183-5° (EtOH). Va or VI, or Via oxidized similarly with 8 g. KMnO₄ in 100 cc. H₂O gave 1-phenyl-3,5-pyrazoledicarboxylic acid, platelets, m. 265-6° (H₂O). The ultraviolet absorption spectra of the various pyrazolines, and II, III, and V, and the infrared absorption spectra of VI and its acetate are recorded.

Annali di Chimica (Rome, Italy) published new progress about 13599-22-9. 13599-22-9 belongs to pyrazoles-derivatives, auxiliary class Pyrazole,Carboxylic acid,Benzene, name is 1,5-Diphenyl-1H-pyrazole-3-carboxylic acid, and the molecular formula is C12H10O4S, Computed Properties of 13599-22-9.

Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics

Liu, Deng-Feng published the artcileRing-opening copolymerization of epoxides and anhydrides using manganese(III) asymmetrical Schiff base complexes as catalysts, Formula: C17H14N2O2, the publication is RSC Advances (2015), 5(5), 3854-3859, database is CAplus.

Based on a series of asym. Schiff base H₂Lⁿ (n = 1-4) ligands with different electronic and steric effects, a series of [Mn(Lⁿ)Cl] complexes were obtained and shown to be effective catalysts in cyclohexene oxide and maleic anhydride, cyclohexene oxide and phthalic anhydride, styrene oxide and maleic anhydride or styrene oxide and phthalic anhydride ring-opening copolymerizations Through the structure design, the input of the electron-withdrawing Br substituent para to the phenoxide group of the complexes is quite beneficial to the improved activities. Moreover, both steric and electronic effects of a suitable MeO substituent at the ortho position of the phenoxide group have much more influence on the formation of alternating ring-opening copolymers than that of selected reaction conditions.

RSC Advances published new progress about 4551-69-3. 4551-69-3 belongs to pyrazoles-derivatives, auxiliary class Benzenes, name is 4-Benzoyl-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, and the molecular formula is C17H14N2O2, Formula: C17H14N2O2.

Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics

Liu, Deng-Feng published the artcileRing-opening copolymerization of epoxide and dianhydride in the presence of manganese(III) asymmetrical bis-Schiff base catalysts, Related Products of pyrazoles-derivatives, the publication is Canadian Journal of Chemistry (2014), 92(11), 1098-1105, database is CAplus.

Based on a series of asym. bis-Schiff base H₂Lⁿ (n = 1-4) ligands with different electronic and steric effects, a series of [Mn(Lⁿ)Cl] complexes 1-4 are obtained and shown to be effective catalysts in ring-opening copolymerization of epoxides and dianhydrides. Through the structure design, the input of electron-withdrawing bromine substituent para to the phenoxide group of the complexes is considerately beneficial to the improved activities. Moreover, steric and electronic effects of the suitable MeO substituent at the ortho orientation on the phenoxide group may both play a role in the formation of alternating ring-opening copolymers under the identical reaction conditions. In three cocatalysts tested, n-Bu₄NBr is pos. to monomer conversion and chain growth of polymer.

Canadian Journal of Chemistry published new progress about 4551-69-3. 4551-69-3 belongs to pyrazoles-derivatives, auxiliary class Benzenes, name is 4-Benzoyl-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, and the molecular formula is C17H14N2O2, Related Products of pyrazoles-derivatives.

Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics

Cusmano, Sigismondo published the artcileTransformation of 3-isoxazolecarboxylic acids into pyrazole derivatives. IV, HPLC of Formula: 13599-22-9, the publication is Gazzetta Chimica Italiana (1940), 227-35, database is CAplus.

cf. C. A. 34, 7903.8. The transformation of 3-isoxazolecarboxylic acids into pyrazolonimines by fusion with PhNHNH₂ may proceed by decarboxylation followed by ring closure of the resulting cyano ketone phenylhydrazone. To test this hypothesis the fusion was repeated in the presence of Natur Kupfer C (I) (or ordinary reduced Cu) so that, at the lower decarboxylation temperatures it might be possible to isolate the phenylhydrazone prior to ring closure and so shed some light on the mechanism of the reaction. A mixture of 1 g. of 5-phenyl-3-isoxazolecarboxylic acid (II), 1 g. I and 1 g. PhNHNH₂ in 20 cc. alc. was boiled for a few min. over a free flame, filtered, alkalinized with Na₂CO₃, extracted free from PhNHNH₂ with ether, acidified with dilute H₂SO₄, and extracted with ether. The residue from the evaporated extract gave 1,5-diphenyl-3-pyrazolecarboxylic acid (III), m. 185° (Et ester, m. 98°), decarboxylated by fusion to give 1,5-diphenylpyrazole, m. 55°, and identical with the known acid prepared by the action of PhNHNH₂ on BzCH₂COCO₂H. A similar transformation of 5-methyl-3-isoxazolecarboxylic acid (IV) gave 1-phenyl-5-methyl-3-pyrazolecarboxylic acid, m. 136° (Me ester, m. 55°), decarboxylated to 1-phenyl-5-methylpyrazole, transformed into the known picrate, m. 98°. In these transformations alc. can be replaced by other solvents. In the absence of I or in the presence of PhNH₂ instead of PhNHNH₂ the isoxazolecarboxylic acid is recovered unchanged.

Gazzetta Chimica Italiana published new progress about 13599-22-9. 13599-22-9 belongs to pyrazoles-derivatives, auxiliary class Pyrazole,Carboxylic acid,Benzene, name is 1,5-Diphenyl-1H-pyrazole-3-carboxylic acid, and the molecular formula is C16H12N2O2, HPLC of Formula: 13599-22-9.

Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics

D’Alcontres, G. Stagno published the artcileHydrogenation of isoxazoles with Raney nickel, Quality Control of 13599-22-9, the publication is Gazzetta Chimica Italiana (1950), 441-55, database is CAplus.

The object of the work was to ascertain whether 4-isoxazolines are capable of existence and whether it is possible to prepare them by hydrogenation of isoxazole (I) and its derivatives by a reaction analogous to that of the formation of pyrazolines from pyrazoles [Ber. 26, 100(1893)]. Under the conditions used by Claisen with I derivatives, the ring is opened with formation of the isomeric imino ketones, NH:CRCHR’COR” (IA) (cf. Ber. 24, 3912(1891)), so a less drastic method had first of all to be derived. To this end, Raney Ni (II) in neutral alc. or aqueous media at room temperature and atm. pressure (according to the nature of the I derivative) was tested as a catalyst. In all cases, hydrogenation progressed smoothly, but in no case was a cyclic isoxazoline isolated, and, on addition of 1 H mol., opening of the nucleus occurred, with formation of IA. The experiments confirm the instability of the cyclic system of 4-isoxazolines, which are probably incapable of existence, or at least it is probably impossible to synthesize them by hydrogenation of the I nucleus (Panizzi, C.A. 40, 7190.1). I (2 g.) in 20 cc. alc. and 1.5 g. II, hydrogenated and filtered, give a liquid which has the odor of NH₃, is alk. to litmus, gives a blood-red color with FeCl₃, and reduces warm NH₃AgNO₃. This reaction liquid (15 cc., i.e., 0.5 the total) and p-O₂NC₆H₄NHNH₂ (III), allowed to stand 1 hr., filtered, and the residue (1.54 g.) purified by dilute EtOH and animal charcoal, yields 1-(p-nitrophenyl)pyrazole (IV), m. 168.5-9°, insoluble in aqueous alkalies and gives no color with them. The other half of the reaction liquor gives no precipitate with H₂NCONHNH₂.HCl and NaOAc, even after several days. 1-Phenylpyrazole (2 g.), poured very slowly into ice-cold fuming HNO₃ (much heat is evolved), allowed to stand, poured into ice water, and the precipitate (3.1 g.) purified by EtOH, yields IV. Dimethylisoxazole (5 g.) in 50 cc. alc. and 2.5 g. II, hydrogenated, filtered, slowly evaporated, and the sirupy residue allowed to stand in vacuo until crystallized, yields MeC(:NH)CH₂Ac (V), m. 43° (from EtOH) [cf. Ber. 24, 3915(1881); Bull. soc. chim. 7, 779(1892)]. V (0.5 g.) in dilute AcOH and III in AcOH give a precipitate of 1-(p-nitrophenyl)-3,5-dimethylpyrazole (VI), light yellow, m. 99.5-100° (from dilute EtOH). VI (0.35 g.) in 10 cc. dilute H₂SO₄, distilled, part of the distillate treated with III, and the precipitate purified by EtOH, yields VI. Another part of the distillate and KOH distilled, and the distillate treated with III, give a p-nitrophenylhydrazone, m. 148.5°. The mother liquor gives the reaction of AcOH. The distillation residue, treated with H₂SO₄, and made alk., evolves NH₃. Diphenylisoxazole (1.5 g.) in 80 cc. alc. and 3 g. II, hydrogenated (with FeCl₃ the reaction liquor turns dark green, then red) and evaporated, yields dibenzoylmethaneimide, PhC(:NH)CH₂Bz (VII), m. 97° (from alc.), soluble in acids and reprecipitated by aqueous alkali carbonates. VII (0.5 g.) in 20 cc. dilute H₂SO₄, refluxed 30 min., half of the liquid saturated with (NH₄)₂SO₄, extracted with Et₂O, the extract dried, and the residue purified by EtOH, yields the compound C₁₅H₁₂O₂, m. 77-8°; FeCl₃ turns its alc. solutions violet-red. The other half of the liquid, extracted with Et₂O, and the residue treated with concentrated KOH, evolves NH₃. VII (0.2 g.) in dilute AcOH and PhHNNH₂ (VIII), heated to boiling and allowed to stand, yield 1,3,5-triphenylpyrazole, m. 137-8° (from Et₂O) [cf. Ber. 21, 1206(1888); Ann. 308, 252(1889)]. O.N:CMe.CH:CCO₂Na (4 g.) in 40 cc. water and 2 g. II, hydrogenated, filtered, and the green filtrate kept in vacuo, leaves a sirupy residue (IX) whose aqueous solutions are alk. to litmus, turn blood-red with FeCl₃, and with KOH evolve NH₃. Aqueous IX and III give 1-(p-nitrophenyl)-3-methyl-5-pyrazolecarboxylic acid, m. 231° (from EtOH) (cf. Musante and Berretti, C.A. 44, 4905a). VIII (2 cc.), 7 cc. water, 0.3 cc. glacial AcOH, and 0.3 g. IX, heated and allowed to stand yield 1-phenyl-3-methyl-5-carboxypyrazole, m. 189-90° (from hot water), decompose 200-10°, with evolution of CO₂ and formation of 1-phenyl-3-methylpyrazole. VIII (1 g.) in 25 cc. dilute H₂SO₄, boiled, saturated with (NH₄)₂SO₄, extracted with Et₂O, and the extract evaporated yields the compound C₅H₆O₄ (IX), m. 98° (from C₆H₆). IX (0.1 g.) in boiling aqueous KOH evolves Me₂CO, and the distillate gives with III a p-nitrophenylhydrazone, yellow, m. 148°. The distillation residue, acidified with AcOH, and aqueous CaCl₂ added, precipitates Ca oxalate (X). O.N:C(CO₂Na).CH:CMe (3.5 g.) in 40 cc. water and 2 g. II, hydrogenated, and the filtered product evaporated, gives a green sirupy product, which with III yields 1-(p-nitrophenyl)-3-methyl-5-pyrazolecarboxylic acid (XI), m. 231° (from EtOH), turns intense red with FeCl₃; with KOH its aqueous solutions evolve NH₃; boiling in dilute H₂SO₄ and extraction with Et₂O yields a compound m. 98°. O.N:C(CO₂Et).CH:CHMe (5 g.) in 40 cc. alc. and 2 g. II, hydrogenated (the mixture turns brown, is alk., and gives with FeCl₃ a cherry-red solution), and the filtered product allowed to evaporate, yields a compound (XII), C₇H₁₁O₃N, m. 109-10° (from EtOH), soluble in dilute aqueous alkalies; in boiling aqueous KOH it evolves NH₃ and Me₂CO, and the residue contains X. XII and III in dilute AcOH precipitate a compound which, purified by dilute EtOH and animal charcoal, yields Et 1-(p-nitrophenyl)-3-methyl-5-pyrazolecarboxylate (XIII), yellowish, m. 78-9°. Alc. XIII (0.5 g.) and 0.4 g. KOH in 4 cc. water, refluxed 75 min., evaporated, the residue taken up in water, filtered, the filtrate acidified with HCl, and the precipitate purified by EtOH and animal charcoal, yield XI. O.N:CPh.C(CO₂Na):CMe (1.2 g.) in 25 cc. water and 1 g. II, hydrogenated (the product is alk. and turns red with FeCl₃), and evaporated, leaves a sirup (XIV), which with HCl evolves CO₂. XIV and KOH evolve NH₃; distillation (odor of BzMe) and treatment of the distillate with III in AcOH gives p-O₂NC₆H₄NHN:CPhMe. The mother liquor, saturated with (NH₄)₂SO₄, extracted with Et₂O, and the extract evaporated, leaves HCO₂H. Aqueous XIV and dilute H₂SO₄ (1:1), allowed to stand until no more CO₂ is evolved, saturated with NH₃, extracted with Et₂O, and the extract evaporated, leave a yellow acidic oil (XV) which reduces NH₃-AgNO₃. XV, exactly neutralized with dilute NaOH, and aqueous PhNH₂.HCl added, yields BzCH₂CH:NPh, m. 140-1° (from EtOH) [cf. Ber. 20, 2192(1887)]. O.N:C(CO₂Na).CH:CPh (2 g.) in 30 cc. water and 1 g. II, hydrogenated, the reaction liquor (alk. to litmus and turns orange-red with FeCl₃) acidified with dilute H₂SO₄, filtered (the filtrate has the odor of NH₃), and the residue purified by C₆H₆, yield PhC(:NH)CH₂COCO₂H (XVI), m. 161° (decomposition) (Mumm and Münchmeyer, C.A. 5, 703). XVI (0.48 g.) in dilute AcOH and VIII in AcOH give a precipitate of diphenylpyrazolecarboxylic acid (XVII), m. 185° (from C₆H₆) [cf. Ber. 20, 2186(1887)]. XVII, heated until no more CO₂ is evolved, then at 250°, the yellow oil allowed to solidify in vacuo, dissolved in aqueous HCl, and water added, precipitates a compound, C₁₅H₁₂N₂ (XIX), m. 55-6°. XIX in dilute H₂SO₄, refluxed 1 hr., allowed to stand, filtered, and the residue purified by boiling water, yields a compound, C₁₀H₈O₄.2H₂O (XX), m. 156-8° (decomposition to BzMe); its aqueous solutions are acid to litmus; its solutions in concentrated H₂SO₄ are purple-red (decolorized by dilution with water). Na salt, precipitates with aqueous FeSO₄ a dark blue compound and, fused with resorcinol, gives a dark red product. The mother liquor from XX and aqueous KOH evolve NH₃. O.N:CMe.C(CO₂Na):CPh (3.1 g.) in 20 cc. water and 1.5 g. II, hydrogenated, the liquid (yellow, alk., and turns intense red with FeCl₃), acidified with dilute HCl, evaporated, and the residue purified by boiling EtOH, yield a compound C₁₁H₁₁O₃N (XXI), m. 89-90°. XXI in dilute H₂SO₄, distilled, and the distillate allowed to stand, yields a compound, C₁₀H₁₀O₂, m. 60-1°, soluble in aqueous alk. carbonates, with FeCl₃ turns Bordeaux red. Treatment of the mother liquor with aqueous KOH yields NH₃. XXI in dilute AcOH and VIII in AcOH give 1-(p-nitrophenyl)-3-methyl-5-phenylpyrazole, m. 100-1° (from MeOH) (Reilly, et al., C.A. 26, 452).

Gazzetta Chimica Italiana published new progress about 13599-22-9. 13599-22-9 belongs to pyrazoles-derivatives, auxiliary class Pyrazole,Carboxylic acid,Benzene, name is 1,5-Diphenyl-1H-pyrazole-3-carboxylic acid, and the molecular formula is C16H12N2O2, Quality Control of 13599-22-9.

Referemce:
https://en.wikipedia.org/wiki/Pyrazole,
Pyrazoles – an overview | ScienceDirect Topics