Methylation of 3-methyl- and 3-phenyl-4-arylhydrazonoisoxazol-5-ones with methyl iodide and dimethyl sulfate

Methylation of 3-methyl-4-arylhydrazonoisoxazol-5-ones with methyl iodide affords both 2,3-dimethyl-4-arylazoisoxazol-5-ones and 3-methyl-4-(N-methylarylhydrazono)isoxazol-5-ones but with dimethyl sulfate only the former products are formed. 3-Phenyl-4-arylhydrazonoisoxazol-5-ones behave in a similar way on methylation with methyl iodide and dimethyl sulfate.     

Mass spectral fragmentation pattern of 2,3-dimethyl- and 2-methyl-3-phenyl-4-arylazoisoxazol-5-ones

2,3-Dimethyl-4-arylazoisoxazol-5-ones and 2-methyl-3-phenyl-4-aryiazoisoxazol-5-ones undergo considerable fragmentation on electron impact. The base peaks in the mass spectra are at mass 56 and 118 respectively attributed to the N-methylacetonitrile cation and the N-methylbenzonitrile cation.     

Synthesis of 1,4-dihydro-4-methyl-1-phenyl-5H-1,3,4-benzotriazepin-5-ones

The synthesis of 1,4-dihydro-4-methyl-1-phenyl-5H-1,3,4-benzotriazepin-5-one ( 4a ) and its 8-chloro analog ( 4b ) is described. Attempted synthesis of the 2-methyl analog of 4a from 2-(phenylamino)benzoic acid 1-methylhydrazide ( 10 ) and triethyl orthoaeetate led only to the Schiff base intermediate, 2-(phenylamino)benzoic acid 2-(1-ethoxyethylidene)-1-methylhydrazide ( 11 ). Cyclization of 11 was attempted unsuccessfully with a variety of reagents. The intere?ting reaction products from the treatment of 11 with trifluoroacetic acid are described.     

Mass spectral fragmentation pattern of 3-methyl- and 3-phenyl-4-(N-methylarylhydrazono)isoxazol-5-ones

3-Methyl-4-(N-methylarylhydrazono)isoxazol-5-ones and 3-phenyl-4-(N-methylarylhydrazono)isoxazol-5-ones undergo considerable fragmentation on electron impact involving rupture of the isoxazolone ring and bonds in the N-methylarylhydrazono side chain.     

Solvent extraction of alkaline earth metals,and lithium with 1-phenyl-3-methyl-4-acylpyrazol-5-ones and trioctylphosphine oxide

The synergic extraction of magnesium, calcium, strongium, barium and lithium into cyclohexane or benzene containing 1-phenyl-3-methyl-4-acyl-pyrazol-5-one (HA) and tri-n-octylphosphine oxide (TOPO) was investigated as a function of pH, HA and TOPO concentration. The extracted species when the 4-benzoyl compound was used, were MA₂(TOPO)₂ (M = Mg, Ca, Sr), BaA₂(TOPO)₃ and LiA(TOPO)₂. When the 4-trifluoro-acetyl derivatives was used, the extracted species were the same except for SrA₂(TOPO)₃. Extraction constants for the synergic extractions were calculated.     

Reaction of 4-arylidene-3-methyl-1-phenyl-5-pyrazolones with amines

The reaction of primary and secondary amines with 4-arylidenepyrazolones gives the corresponding ammonium salts of 4,4-benzylidenebis-5-pyrazolone derivatives but not adducts on the exocyclic C=C bond as was previously believed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 905–908, July, 1988.     

Tautomerism of 1-phenyl-3-methyl-4-benzyl-5-pyrazolone

The tautomerism of 1-phenyl-3-methyl-4-benzyl-5-pyrazolone —a side product in the reaction of acetoacetic ester with benzaldehyde phenylhydrazone — was studied by IR and PMR spectroscopy, and its thermodynamic characteristics were determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 355–359, March, 1991.     

Synthesis and spectral behavior of 5-methyl-3-phenyl-1,3-oxazolidin-2-ones using NMR

Heterocyclic compounds of four 5-methyl-3-phenyl-1,3-oxazolidin-2-ones have been synthesized by the reaction of N-2-hydroxyethyl- or N-2-hydroxypropylanilines with phosgene in the presence of pyridine. From the spectral behavior, the title compounds are found to exist in the trans and cis forms.     

Anionic lanthanide complexes with 3-methyl-4-formyl-1-phenyl-5-pyrazolone

The coordination compounds Na[LnL₄] · 2H₂O and [NBu₄][LnL₄] (Ln = Nd, Sm, Eu, Tb; HL is 3-methyl-4-formyl-1-phenyl-5-pyrazolone) have been synthesized and studied by IR spectroscopy and thermogravimetry. According to X-ray diffraction data, the coordination polyhedra of lanthanides are shaped as square antiprisms and formed by the oxygen atoms of four deprotonated moieties of the enol form of 4-formyl-5-pyrazolone. In the complex Na[EuL₄] · 2H₂O, sodium cations are bonded to the two nitrogen atoms of pyrazole heterocycles, combining discrete complex anions into two interpenetrating three-dimensional frameworks. Polycrystalline samples of neodymium(III), samarium(III), and terbium(III) complexes manifest intense luminescence in the spectral regions that are typical for them.     

Extraction of group VIII elements with 1-phenyl-3-methyl-4-trifluoroacetyl-pyrazolone-5

The extraction of group VIII elements with 1-phenyl-3-methyl-4-trifluoracetyl-pyrazolone-5 from aqueous solutions in chloroform has been studied as a function of pH. Fe(III), Ni(II), Pd(II) and Rh(III) show partial extraction whereas Co(II) is extracted quantitatively. The effect of citrate, cyanide, fluoride, iodide, thiosulphate and thiourea on the extraction of metal ions has been investigated. Back-extraction studies were carried out to strip metal ions from organic phase into appropriate aqueous solutions. Based on these findings some useful analytical separations have been proposed and a few of their possible applications have been discussed.     

Formation and structure of 1-Amino-4-methyl-4-(4-methyl-5-phenyl-1H-pyrazol-3-ylamino)-3-phenyl-4,5-dihydro-1H-pyrazol-5-one

The title compound 3 was obtained during the rearrangement of isoxazol-5-yl hydrazine 1 to 1-aminopyrazolone 2 at 115°. X-ray analysis of the corresponding benzylidene derivative allowed us to achieve the structure assignment.     

Mass spectral fragmentation pattern of 3-methyl-4-arylaminomethyleneisoxazol-5-ones

The mass spectral fragmentation patterns of 3-methyl-4-arylaminomethyleneisoxazol-5-ones obtained by electron impact have been elucidated. The base peaks are due to the molecular ions. The main fragmentation routes involve loss of H, OH, H₂O, CO₂ and COOH from the molecular ions as well as rupture of the exocyclic CH-NH bond.     

Coordination compounds of some 3d metals with 3-methyl-1-phenyl-4-formylpyrazol-5-one

CuL₂ · 1.5H₂O and ML₂ · 2H₂O · 2EtOH (M = Co²⁺, Ni²⁺, Mn²⁺) coordination compounds were synthesized via the exchange reaction between the sodium salt of 3-methyl-1-phenyl-4-formylpyrazol-5-one (HL) and metal chlorides.The synthesized compounds were studied by thermogravimetry, magnetochemistry, and electron and IR spectroscopy. The complexes CuL₂ · 2Py and CoL₂ · 2Py · MeOH were obtained via recrystallization from a methanol-pyridine mixture, and their structures were studied by X-ray diffraction. Pyrazolone was found to be coordinated in the deprotonated enol form and to form six-membered chelate rings with a metal. The coordination polyhedron of a metal cation was found to be a square bipyramid (Cu²⁺) or an axially elongated octahedron (Co²⁺) with its vertices occupied by the oxygen atoms of 3-methyl-1-phenyl-4-formylpyrazol-5-one and the nitrogen atoms of pyridine.     

Synthesis of some 4-methyl- and 4-phenyl-3-hydroxycoumarins

Some 4-methyl- and 4-phenyl-3-hydroxycoumarins were synthesized by the reaction of phenols with -acetoxyacetyl- or -acetoxybenzoylacetic esters.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1595–1596, December, 1970.     

Synergistic complexes of uranyl ion with 1-phenyl-3-methyl-4-acetyl-pyrazolone-5 and some oxo-donors

Complexes of uranyl ion with 1-phenyl-3-methyl-4-acetyl-pyrazolone-5(PMAP) and various oxo-donors such as aliphatic sulphoxides [R₂SO, where R = i-C₅H₁₁(DISO), n-C₆H₁₃(DHSO), n-C₇H₁₅(DSSO), n-C₈H₁₇(DOSO), n-C₉H₁₉(DNSO), n-C_1OH₂₁(DDSO), n-C₁₁H₂₃(DUDSO) and n-C₄H₉(DBUSO)] tributylphosphate (TBP) and tri-n-octyl phosphine oxide (TOPO) have been synthesised and characterized. Analytical data establish that they have the stoichiometry UO₂(PMAP)₂X where X is the oxo-donor. The IR spectra of the sulphoxide complexes in the SO stretching region indicate that the ligands R₂SO are O-bonded. The methyl protons of the pyrazole ring and acetyl group in the PMAP ligand are equivalent giving rise to a single sharp peak in the PMR spectra, whereas in the synergistic complexes with the oxo-donors, two deshielded peaks of equal intensity are observed which indicate the non-equivalence of the methyl groups. The peak which is more deshielded has been ascribed to the methyl of the acetyl group. The higher deshielding of these methyl protons arises due to the transfer of electron density to the metal atom on complexation.     

Solvent extraction of gold(III) with 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5

A simple, rapid and selective separation procedure of gold based on its extraction with 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5 has been developed. The dependence of the distribution ratio of gold on the pH of aqueous solutions, concentration of hydrochloric, nitric and perchloric acids and the organic solvents has been investigated. Decontamination factors for a number of metal ions with respect to gold are reported. Excellent separation of gold is obtained from many elements including noble metals. Citrate, cyanide, iodide, thiosulfate and thiourea completely mask gold, whereas oxalate does not interfere. Solutions of 1 M HCl, 0.2 M KCN, and the buffer of pH 0.8 readily strip gold from the organic phase. Some useful analytical applications of this procedure are discussed.