Methyl-l-phenyl-2-pyrazolin-5-one

Substituted pyrazolin-5-ones have only three and -substituted pyrazolin-3-ones only two tautomers, since now the corresponding 19c and 19d structures are isomers. The calculations involved l-methylpyrazolin-5-one (PM3/6-3H-G, anions and cations), l-phenyl-3-methyl-2-pyrazolin-5-one (DFT, radical reactions) [97JPC(A)3769], and l-(2, 4 -dinitrophenyl)-3-methyl-2-pyrazolin-5-one [B3LYP/6-31G and the crystal structure (Section V,D,2)] (98NJC1421). 

Chiesa, C., Oefner, P. J., Zieske, L. R. and O Neill, R. A. Micellar electrokinetic chromatography of monosaccharides derivatized with l-phenyl-3-methyl-2-pyrazolin-5-one. J Capillary Electrvphor, 2,175, 1995. 

The stability of the pyrazolinone tautomers was related to their scale of aromaticity.Experimental values for the tautomerism of pyrazolinone derivatives were obtained by flash vacuum pyrolysis (FVP), which allowed the calculation of the effect of the temperature on the equilibrium between tautomers. The variation of Kj with the temperature was determined by H NMR in solution for the model compound l-phenyl-3-methyl-2-pyrazolin-5-one (Scheme 25), showing that at 0 K the only tautomers present are either the NH or the OH ones. Temperature and solvent effects on the prototropic equilibrium of the model compound in solution showed that... 

Presumably the linking group is >NCH—N<. Bisamides of l-(amino-phenyl)-2-pyrazolin-5-ones and of 3-amino-2-pyrazolin-5-ones have been used. l-(3-Aminophenyl)-3-methyl-2-pyrazolin-5-one reacts with many aldehydes and ketones to form polymers.964 Probably condensation occurs at C-4 and the amino group. The product of reaction of p-cresol with formaldehyde has been found to react with 1-(4-hydroxy -phenyl)-3-methyl-2-pyTazolin-5-one to give a polymer that must have the aromatic and pyrazolinone rings connected by ether linkages.1269... 

Only half-a-dozen of these compounds are known (Table XLI) and at least this number of methods of preparing them have been reported. Borsche and Manteuffel125 have found that 2-pyrazolin-4,5-diones are formed as the by-products when oc-ketoesters are treated with aryl-diazonium salts. The principal products are 4-arylazo-2-pyrazolin-5-ones. Nitric acid oxidation of 3-methyl-l-phenyl-2-pyrazolin-5-one forms the corresponding 4,5-dione.809 Wislicenus and Gtiz1842 heated 4 -bromo - 4 - nitro -1 - (4 - bromophenyl) - 3 - methyl - 2 -pyrazolin - 5 - one in water and obtained the analogous 4-oxo compound. Acid hydrolysis of rubazonic acids, which are 4-imino-2-pyrazolin-5-ones, leads to 2-pyrazolin-4,5-diones.424 809 Oxidation of 4,4 -bis(2-pyrazolin-5-ones) or of rubazonic acids with nitric acid809 forms the 4,5-diones. 

A comprehensive theoretical smdy of some pyrazolones has been presented. The predicted tautomeric equilibrium constants of these compounds were found to be in good agreement with existing experimental data, indicating that the oxo tautomers are present in aqueous solution whereas, in the main, the hydroxy tautomers predominate in the gas phase. It has been shown that, in solution, the most abundant tautomer of both l-(2, 4 -dinitrophenyl)-3-methyl-2-pyrazolin-5-one and its 1-phenyl derivative is dependent on the solvent used, while an NMR study of a number of l(2)//-dihydropyrazolo[3,4-fc]pyridin-6-ones has revealed that they all exist as 2//-tautomers both in solution and in the solid state. DFT and ab initio calculations have been carried out to investigate the stability of different tautomers of 2-hydroxy- and 2,3-dihydroxy-pyrazine in the gas phase and in different media. The data obtained indicated that 2-hydroxypyrazine is more stable than its 2-keto tautomer in the gas phase, whereas in solution the stability order is reversed. For 2,3-dihydroxypyrazine it appears that the intramolecular hydrogen-bonded hydroxyoxo and the a-diketo tautomers are the most stable species at all theoretical levels in the gas phase. Both spectroscopic and theoretical studies of the tautomerism of 2,1,3-benzothiadiazinone 2,2-dioxides and other related fused heterocyclic amides have predicted that the keto form (415) is the most abundant tautomer in the gas phase, whereas the NH hydroxy form (416) is the preferred tautomer in solution and in the solid state. 

Cyclocondensation of 3-methyl-l-(5-substituted-3-phenyl-lH-indol-2-ylcarbonyl)-5-(4fi)-pyrazolones with arylidene derivatives of malononitrile using a catalytic amount of triethylamine in refluxing ethanol affords heterocycle [ ]-fused 6-amino-4-aryl-5-cyano-4H-pyrans (14JHC303). Other fused 6-amino-4-aryl derivatives arise from the three-component reaction of benzaldehydes, active methylene compounds (malononitrile/ ethyl cyanoacetate) and 1,3-dicarbonyl compounds catalyzed by 1,8-diaz-abicyclo[5.4.0]undec-7-ene (DBU) in refluxing water (14JHC618). Similar pyrazole[f)]-fused derivatives are obtained from the reaction of benzaldehydes, malonitrile, and 3-substituted-2-pyrazolin-5-ones using sodium... 

Methyl-l -phenyl-2-pyrazolin-5 -one CDCI3 -186.4 -54.5 C- N and H- coupling constants 77JCS P2)1024 ... 

Pyrazblin-5-one, 3-alkyl-(l,2,4-thiadiazol-5-yl)-reactions, 6, 483 2-Pyrazolin-5-one, 3-amino-tautomerism, 5, 215 2-Pyrazolin-5-one, 4,4-diazido-rearrangement, 5, 720 2-Pyrazolin-5-one, 3-hydroxy-tautomerism, 5, 215 2-Pyrazolin-5-one, 3-methyl-1 -phenyl-reactions, 5, 252... 

Benzylidene-3-methyl-l phenyl-2-pyrazolin-5-one on treatment with 2,4-dinitrophenylhydrazine and hydroxylamine hydrochloride afforded the pyrazolo[3,4-dpyrazole (96) and the isoxazolo[3,4-cl-pyrazole (97), respectively.101... 

The organisms Pyricularia oryzae, which causes rice blast, and Helminthosporium oryzae, which causes brown leaf spot, can be controlled with complexes of the ligands 1-phenyl-3-methyl-4-nitroso-2-pyrazolin-5-one (36) and 3-methyl-4-nitroso-2-pyrazolin-5-one (37). The complexes were of the type ML Xj (L = 36, 37 X = C1-, Br, N03 ) or [ML2]Y2 (Y = C104 ). The former were assigned an octahedral or distorted octahedral structure and the latter are tetrahedral. The most active nickel complex was (38).92... 

The non-aromatic CH tautomers of pyrazolones have a malonic-like reactivity due to the fact that the hydrogen atoms of the CH2 group at position 4 are acidic because the conjugate anion (239) is fully delocalized. Figure 27 illustrates some classical reactions of 3-methyl-l-phenyl-2-pyrazolin-5-one (396) (64HC(20)l). 

C17H14N202 4-benzoyl-3-methyl-l-phenyl-2-pyrazolin-5-one 4551-69-3 492.65 43.178 2 30136 C17H20N2S promazine 58-40-2 479.65 411 1,2... 

Pyrazol-5-ones are widely used in medicine, color photography, analytical chemistry, and agriculture. The tautomeric equilibria between the CFI, OH, and NH forms in a series of 4-substituted-l-phenyl-3-methyl-pyrazolin-5-ones 100-102 have been studied using ab initio calculations at various levels of theory and comparison made with the experimental results obtained from C NMR measurements <2001JP0566>. The tautomerism of 4-acyl-2-phenyl-2-pyrazolidin-3-ones 103 and 104 was studied by C NMR spectroscopy <1999CHE748>. The tautomerism of... 

The photochemical products indicated that ( /Z)-isomerization, intramolecular cyclization, and solvent addition (acetonitrile) occurred. A density functional study of the radical reactions of 3-methyl-l-phenyl-2-pyrazolin-5-one was carried out <1997JPC3769>. 

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