Month: December 2022

Roy, Sutapa published the artcileSynthesis, characterization and 3-D molecular modeling of some oxovanadium(IV) complexes involving O₂N₂ donor core, SDS of cas: 4551-69-3, the publication is Journal of Pharmacy and Chemistry (2014), 8(4), 9-13, database is CAplus.

In view of the wide application of vanadium complexes, oxovanadium(IV) complexes involving pyrazolone-based aroylhydrazone and 8-hydroxyquinoline were synthesized and characterized by different physicochem. studies such as elemental anal., molar conductance, magnetic measurements, IR, TGA, ESR, mass and electronic spectral studies. The overall exptl. data based from all the studies presented suggests the complexes under present investigation are [VO(L)(8-hq)(H₂O)], where LH- pyrazolone-based aroylhydrazone and 8-hqH = 8-hydroxyquinoline, involving a monobasic didentate (O,N) donor ligand. An octahedral structure with axial oxo groups are proposed for these complexes.

Journal of Pharmacy and 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, SDS of cas: 4551-69-3.

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

Makisumi, Yasuo published the artcileAzaindolizine compounds. X. Synthesis of 5,7-disubstituted pyrazolo[1,5-a]pyrimidines, Safety of 3-Acetamidopyrazole, the publication is Chemical & Pharmaceutical Bulletin (1962), 612-20, database is CAplus.

cf. CA 57, 16606b. The title compounds (I) were prepared in general by condensing AcCH₂CO₂Et (II), CH₂Ac₂ (III), NCCH₂CO₂Et (IV), and CH₂(CO₂Et)₂ (V) separately with 5-amino-pyrazole (VI), its 1-Ph derivative (VII), its 4-EtO₂C derivative (VIII), and its 4-NC. derivative (IX). II kept overnight at room temperature with VI, VII, or VIII in the absence of solvent gave the corresponding 5-EtO₂CCH:CMeNH derivatives (X-XII) of pyrazole, m. 102°, 80-1°, and 175-6°, resp. On the other hand, refluxing II with VI or VIII 2-2.5 hrs. in AcOH gave the cyclized compounds (Ia, R = H and EtO₂C), m. 298-9° and 218-20°, resp., whereas refluxing II 4 hrs. with VII in AcOH gave the different cyclized compound (XIII), m. 188-9°. Ia (R = H and EtO₂C) and XIII were formed also by refluxing X-XII 2-3 hrs. with AcOH. Ia (R = EtO₂C) was also formed by refluxing XI 10 hrs. with Na in EtOH, and Ia (R = H) was prepared by refluxing VI 3 hrs. with II in EtOH containing anhydrous ZnCl₂. Hydrolysis of 0.5 g. Ia (R = EtO₂C) by heating 2 hrs. on a steam bath with 10% NaOH yielded 0.45 g. corresponding free acid, m. 296-7° (decomposition), and this (0.5 g.) was successfully decarboxylated by refluxing 3 hrs. with 40% H₂SO₄ to yield 0.32 g. Ia (R = H). Also, 0.94 g. IX refluxed 2.5 hrs. with II in AcOH yielded 1.5 g. Ia (R = cyano), m. 313° (decomposition), and this (0.5 g.) hydrolyzed and decarboxylated by refluxing 4 hrs. with 40% H₂SO₄ also yielded 0.4 g. Ia (R = H). Refluxing III (in place of II) with VI or VIII 10-12 hrs. in EtOH containing 3 drops piperidine, removing the solvent, and purifying the residue by Al₂O₃ chromatography gave, resp., Ib (R = H), m. 40-40.5°, and Ib (R = EtO₂C), m. 107-7.5°. The latter, like Ia (R = EtO₂C) was hydrolyzed to the corresponding free acid, m. 178-9°, which was decarboxylated either by heating 20 min. at 200° without solvent or by refluxing with 40% H₂SO₄ to give Ib (R = H), formed likewise by refluxing the ester, Ib (R = EtO₂C), itself with 40% H₂SO₄. Use of IV (in place of II or III) with VI or VIII in EtOH containing Na gave, resp., Ic (R = H), m. 306° (decomposition), and Ic (R = EtO₂C), m. 236-7°, which was hydrolyzed to the free acid, m. 296° (decomposition), and this was decarboxylated by heating in vacuo at 260-70° to give Ic (R = H). However, heating IV with VI 2 hrs. at 160-70° in the absence of solvent gave the noncyclized 5-(2-cyanoacetamido)-pyrazole (XVI), m. 211-12° (decomposition), and this was cyclized to Ic (R = H) by heating 5 hrs. on a steam bath in AcOH. Finally, V (in place of II) with VI or VIII in EtOH containing Na gave, resp., Id (R = H), m. 239-40° (decomposition), and Id (R = EtO₂C), m. 186-7° (decomposition), which also was hydrolyzed to the corresponding acid, m. 229° (decomposition), and this heated 5 min. at 235° was not only decarboxylated but also decomposed to give 5-acetamidopyrazole (XV), m. 223-4°, identical with the product obtained by refluxing VI 1 hr. with AcOH. However, heating VI 15 min. on a steam bath with Ac₂O gave 1-acetyl-5-acetamidopyrazole, m. 190.5-1.5°, which was readily converted to XV by heating with H₂O. In support of the structures, ultraviolet absorption curves were shown for Ia (R = H, EtO₂C, and CN), X-XII, Ic (R = H), Id (R = H), XIV, and XV, and both infrared and ultraviolet absorption data were reported for most of the compounds The infrared spectra of I showed that the 5- or 7-HO groups were mainly in the lactam form, whereas the 5- or 7-H₂N groups kept the amino form in neutral medium, thus showing analogy with pyrimidine derivatives

Chemical & Pharmaceutical Bulletin published new progress about 3553-12-6. 3553-12-6 belongs to pyrazoles-derivatives, auxiliary class Pyrazole,Amine,Amide, name is 3-Acetamidopyrazole, and the molecular formula is C5H7N3O, Safety of 3-Acetamidopyrazole.

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

Lugovkin, B. P. published the artcileSynthesis of 3-indolyl(1-aryl-3-methylpyrazol-5-on-4-yl)methanephosphonates, Formula: C10H9ClN2O, the publication is Zhurnal Obshchei Khimii (1973), 43(6), 1261-3, database is CAplus.

Indole-3-carboxaldehyde reacted with 1-aryl-3-methyl-5-pyrazolones to form the 4-indoleninylpyrazolone analogs which with (RO)2PHO in the presence of RONa catalyst gave title compounds I (Ar = Ph, p-tolyl, o-, p-ClC6H4; (R = Me, Et).

Zhurnal Obshchei Khimii 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 C10H9ClN2O, Formula: C10H9ClN2O.

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

Ludington, Jennifer L. published the artcileVirtual Fragment Preparation for Computational Fragment-Based Drug Design, Category: pyrazoles-derivatives, the publication is Methods in Molecular Biology (New York, NY, United States) (2015), 31-41, database is CAplus and MEDLINE.

Fragment-based drug design (FBDD) has become an important component of the drug discovery process. The use of fragments can accelerate both the search for a hit mol. and the development of that hit into a lead mol. for clin. testing. In addition to exptl. methodologies for FBDD such as NMR and X-ray Crystallog. screens, computational techniques are playing an increasingly important role. The success of the computational simulations is due in large part to how the database of virtual fragments is prepared In order to prepare the fragments appropriately it is necessary to understand how FBDD differs from other approaches and the issues inherent in building up mols. from smaller fragment pieces. The ultimate goal of these calculations is to link two or more simulated fragments into a mol. that has an exptl. binding affinity consistent with the additive predicted binding affinities of the virtual fragments. Computationally predicting binding affinities is a complex process, with many opportunities for introducing error. Therefore, care should be taken with the fragment preparation procedure to avoid introducing addnl. inaccuracies.This chapter is focused on the preparation process used to create a virtual fragment database. Several key issues of fragment preparation which affect the accuracy of binding affinity predictions are discussed. The first issue is the selection of the two-dimensional at. structure of the virtual fragment. Although the particular usage of the fragment can affect this choice (i.e., whether the fragment will be used for calibration, binding site characterization, hit identification, or lead optimization), general factors such as synthetic accessibility, size, and flexibility are major considerations in selecting the 2D structure. Other aspects of preparing the virtual fragments for simulation are the generation of three-dimensional conformations and the assignment of the associated at. point charges.

Methods in Molecular Biology (New York, NY, United States) published new progress about 930-36-9. 930-36-9 belongs to pyrazoles-derivatives, auxiliary class Pyrazole, name is 1-Methylpyrazole, and the molecular formula is C4H6N2, Category: pyrazoles-derivatives.

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

Huppatz, John L. published the artcileSystemic fungicides. The synthesis of pyrazolo[1,5-a]pyrimidine analogs of carboxin, SDS of cas: 23286-70-6, the publication is Australian Journal of Chemistry (1985), 38(1), 221-30, database is CAplus.

Pyrazolo[1,5-a]pyrimidines I (R = H, Me, HO, Cl, Me₂N; R¹ = H, Me, Pr, HO, Cl) and II (R² = H, Br; R³ = CONHPh, CO₂Et, CO₂H, NO₂), structural analogs of the systemic fungicide carboxin, were prepared A common intermediate incorporating structural features desirable for fungicidal activity, pyrazole-4-carboxamide III, was used to prepare pyrazolo[1,5-a]pyrimidines variously substituted in positions 5 and 7 of the ring system. Bromination of I (R = R¹ = H) occurred preferentially in the Ph ring and II (R² = Br; R³ = CO₂Et) was prepared by bromination of II (R² = H; R³ = CO₂Et) (IV). Attempted nitration of the ester IV resulted in displacement of the ethoxycarbonyl substituent by a nitro group. The simplest pyrazolo[1,5-a]pyrimidine I (R = R¹ = H) showed a high level of fungicidal activity in fungal growth assays of Basidiomycete species, but compounds substituted in the pyrimidine ring were inactive.

Australian Journal of Chemistry published new progress about 23286-70-6. 23286-70-6 belongs to pyrazoles-derivatives, auxiliary class Pyrazole,Amine,Ester, name is Ethyl 5-amino-3-methyl-1H-pyrazole-4-carboxylate, and the molecular formula is C7H11N3O2, SDS of cas: 23286-70-6.

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

Graubaum, Heinz published the artcileAcyl migrations on 3(5)-aminopyrazole, Recommanded Product: 3-Acetamidopyrazole, the publication is Journal fuer Praktische Chemie/Chemiker-Zeitung (1993), 335(7), 585-8, database is CAplus.

3-Aminopyrazole forms 3 isomeric monoacylation products [I–III, R = Me, Et, Ph, 4-Me₂CHC₆H₄, 4-ClC₆H₄], 4 diacylation products and 3 triacylation products by reaction with RNCO. Acetamides IV [R¹ = RNHCO, R = Me, Et, Ph; R¹ = C(:NH)OR², R² = 4-MeOC₆H₄, 4-MeC₆H₄, 4-ClC₆H₄] were obtained from 3-acetylaminopyrazole and RNCO or R²OCN. Acyl migrations are observed depending on the reaction temperature and the structure of the acyl residue.

Journal fuer Praktische Chemie/Chemiker-Zeitung published new progress about 3553-12-6. 3553-12-6 belongs to pyrazoles-derivatives, auxiliary class Pyrazole,Amine,Amide, name is 3-Acetamidopyrazole, and the molecular formula is C5H7N3O, Recommanded Product: 3-Acetamidopyrazole.

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

Finar, I. L. published the artcilePreparation and properties of some bipyrazolyls, Application of 1,5-Diphenyl-1H-pyrazole-3-carboxylic acid, the publication is Journal of the Chemical Society (1955), 1205-8, database is CAplus.

The synthesis of 5,5′-dimethyl-1,1′-diphenyl-(I) and 1,1′,5,5′-tetraphenyl-3,3′-bipyrazolyl (II) was repeated, and the 3,5′-isomer (III) of the latter was isolated. Evidence was given for the orientations of these two isomers, and some 4,4′-disubstituted derivatives of I, II, and III were prepared (CO₂Et)₂ (IV) (36.5 g.) and 29 g. dry Me₂CO were added during 25 min. to NaOMe (from 12.5 g. Na) under Et₂O at 0°, the mixture was stirred for 2 days to give 21-38% octane-2,4,5,7-tetraone (V), yellow needles, m. 120-1° (from MeOH). IV (36.5 g.) and 1/2 of 16 g. PhCOMe were similarly treated, the other 1/2 added 4 hrs. later, and the mixture stirred 3 days to give 62-74% 1,6-diphenylhexane-1,3,4,6-tetraone (VI), yellow needles, m. 177-9°. V (3.4 g.) was heated with 4.3 g. PhNHNH₂ in HOAc for 1 hr. to give 3.4 g. I, buff needles, m. 141-2°. VI (47.2 g.) was similarly treated 3-4 hrs. with 34.6 g. PhNHNH₂ to give 35.2 g. II, m. 233°. The filtrate was diluted with H₂O and then crystallized to yield 12.2 g. III, white needles, m. 135-6°. VI (58.8 g.) in HOAc was treated during 2.75 hrs. with 21.6 g. PhNHNH₂ in HOAc, heated for a further 1.25 hrs., and set aside for 2 days to give after fractional crystallization unchanged starting material, II, and 3-(α-benzoylacetyl)-1,5-diphenylpyrazole (VII), yellow needles, m. 164-6.5°. VII on oxidation with alk. KMnO₄ yielded 1,5-diphenylpyrazole-3-carboxylic acid (VIII), m. 185-6°. VII (2.9 g.) and 0.97 g. PhNHNH₂ in HOAc heated 1 hr., and kept at room temperature overnight gave 2.4 g. II and 1 g. III. The infrared spectra of II and III were complex and similar. In general, the lowering of the symmetry as in III increases the number of bands. III in the 1600-650 cm.^-1 region had 25 strong bands. Bischler’s method [Ber. 25, 3143(1892)] of preparing VIII was modified as follows: MeCOCH₂CO₂Et (30 g.) was refluxed 6 hrs. with 5.4 g. Na wire under Et₂O, then 46 g. BzCH₂Br in Et₂O was added to maintain gentle reflux, then refluxed 2 hrs., and set aside overnight to give 56 g. AcCH(CH₂Bz)CO₂Et (IX) as a red oil. IX (12.4 g.) in EtOH was treated in the cold with 4.65 g. PhN₂Cl, and then 16.4 g. NaOAc in H₂O, the mixture set aside 24 hrs. in ice, and the oil which separated heated 15 min. with 6 g. NaOH in a little H₂O to give 6.7 g. VIII. I in CHCl₃ was treated with Br at room temperature to yield 4,4′-dibromo-5,5′-dimethyl-1,1′-diphenyl-3,3′-bipyrazolyl, rods, m. 159-60°. 4,4′-Dibromo-1,1′,5,5′-tetraphenyl-3,3′-bipyrazolyl, plates, m. 272-3°. 4,4′-Dibromo-1,1′,3′,5-tetraphenyl-3,5′-bipyrazolyl, white rosettes, m. 200-1°. II (13.2 g.) in HOAc and 26 cc. concentrated HCl was heated 2 hrs. with 2.4 g. paraformaldehyde to give the 4,4′-bis(chloromethyl) derivative, white needles, (6.2 g.), m. 274-6°. I (3.14 g.) in HOAc was heated 0.5 hrs. with 6.37 g. HgAc₂ to yield 4.8 g. 4,4′-bis(acetoxymercuri) compound (X), white needles, m. 204-4.5° (aqueous HOAc). II (4.38 g.) similarly treated yielded after 5 hrs. refluxing 7.6 g. 4,4′-bis(acetoxymercuri)-1,1′,5,5′-tetraphenyl-3,3′-bipyrazolyl (XI), white powder, m. 271.5°. The mercuri compounds when treated with HOAc and Br at room temperature gave the corresponding 4,4′-di-Br compounds X refluxed with dilute HCl gave I; however, XI had to be refluxed for some time with HOAc containing concentrated HCl before II could be obtained.

Journal of the Chemical Society 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, Application of 1,5-Diphenyl-1H-pyrazole-3-carboxylic acid.

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

Feid-Allah, Hassan M. published the artcileTrisubstituted pyrazoles of possible antidiabetic and antibacterial activity, Related Products of pyrazoles-derivatives, the publication is Pharmazie (1981), 36(11), 754-6, database is CAplus.

Condensation of benzalacetone and dibenzalacetone with 4-H₂NSO₂C₆H₄NHNH₂ (I) and 2-pyridylhydrazine led to the corresponding hydrazones. These were readily cyclized to pyrazolines on heating with HCl. The reaction of substituted benzalacetophenones with I and 2-pyridylhydrazine gave the pyrazoline derivatives directly. Oxidation of the pyrazolines with Br-H₂O afforded the pyrazoles. Reaction of epoxy-p-methoxybenzalacetophenone with I gave a hydroxapyrazoline which oxidized to the hydroxypyrazole with Br-H₂O. Condensation of acylhydrazines with substituted benzalacetophenones afforded the corresponding acylhydrazones.

Pharmazie published new progress about 71203-35-5. 71203-35-5 belongs to pyrazoles-derivatives, auxiliary class GPCR/G Protein,Ras, name is 4-(5-(4-Methoxyphenyl)-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)benzenesulfonamide, and the molecular formula is C22H21N3O3S, Related Products of pyrazoles-derivatives.

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

De Mendoza Sans, Javier published the artcileSynthesis of N-non-substituted 3(5)-hydrazino pyrazoles, Quality Control of 3553-12-6, the publication is Revista de la Real Academia de Ciencias Exactas, Fisicas y Naturales de Madrid (1971), 65(4), 739-839, database is CAplus.

A thesis with 68 references (5)-Amino-4-(ethoxycarbonyl)pyrazole (I) was hydrolyzed and decarboxylated to give 80% 3(5)-amino-pyrazole. I was diazotized and reduced to the corresponding hydrazine. Similarly I was diazotized and coupled to β-naphthol in base to give the asym-triazine (II).

Revista de la Real Academia de Ciencias Exactas, Fisicas y Naturales de Madrid published new progress about 3553-12-6. 3553-12-6 belongs to pyrazoles-derivatives, auxiliary class Pyrazole,Amine,Amide, name is 3-Acetamidopyrazole, and the molecular formula is C5H7N3O, Quality Control of 3553-12-6.

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