Mixed ligand chelate extraction of lanthanides with 1-phenyl-3-methyl-4-octanoyl-5-pyrazolone systems

The equilibrium extraction behavior for a series of representative trivalent lanthanide ions, Pr, Eu, and Yb, using chloroform solutions containing 1-phenyl-3-methyl-4-octanoyl-5-pyrazolone (HPMOP), either alone or combined with 1,10-phenanthroline (phen), trioctylphosphine oxide (TOPO) or methyltrioctylaromonium chloride (R₃R'NCl), is studied. The results demonstrate that these lanthanides are extracted as LnP₃, or in the presence of phen or TOPO. as LnP₃ · phen or LnP₃ · TOPO, or in the presence of R₃R'NCl, as R₃R'NLnP₄. The effects of phen, TOPO, and R₃R—NCl on the extraction of lanthanide ions with HPMOP are more pronounced than their effects with 8-quinolinol or 5,7-dibromo-8-quinolinol.     

Synthesis of 1-phenyl-3-methyl-4-alkyl-4-[N-methylbutyro(capro)lactyl]-5-pyrazolones

The corresponding hydrazones, which on heating are cyclized to give 1-phenyl-3-methyl-4-alkyl-(benzyl)-4-(2-oxopyrrolidinomethyl)- and 1-phenyl-3-methyl-4-alkyl(benzyl)-4-(N-methylcaprolactyl)pyrazolones, are formed in the reaction of alkyl(benzyl) (2-oxopyrrolidinomethyl)- and alkyl-(benzyl) (N-methylcaprolactyl)acetoacetic esters with phenylhydrazine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1546–1548, November, 1976.     

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.     

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.     

Synthesis of 3-phenyl- and 3-phenyl-1-methylimidazo [5, 1-b] benzoxazoles

Reduction of 2-benzoylbenzoxazole oxime gives 2-(-aminobenzyl) benzoxazole, converted to the formyl or acetyl derivative by treatment with, respectively, ethyl formate or acetic anhydride. Thiourea derivatives are obtained by treating 2-(-aminobenzyl) benzoxazole with arylisothiocyanates. Heating the above formyl or acetyl derivative with phosphorus oxychloride converts them to 3-phenyl- and 3-phenyl-1-methylimidazo [5, 1-b]-benzoxazole, which are representative members of a new tricyclic system. It did not prove possible to cyclize 1-[-(benzoxazolyl-2) benzyl]-3-phenylthiourea.     

三组分一锅法合成3-甲基-1-苯基-4-芳基-4,11-二氢-4H-吡唑并[4',5':3,2]吡啶并[5,6-c]香豆素

以芳醛、4-羟基香豆素和3-甲基-1-苯基-5-氨基吡唑为原料,用少量冰醋酸作溶剂,三组分一锅法合成一系列吡唑并[4',5':3,2]吡啶并[5,6-c]香豆素衍生物,该反应产率高(79%～94%)、操作简单、后处理方便.产物的结构经红外光谱、核磁共振氢谱、元素分析及单晶X射线分析证实.     

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.     

4-Chloro-5-methyl-3-diphenylphosphino-1-phenyl-1,2,3,6-tetrahydrophosphinine as a bidentate P-ligand in a cis chelate Pt(II) complex

Double deoxygenation of a 3-phosphinoxido-1,2,3,6-tetrahydrophosphine oxide (2) led to bisphosphine 3-2 with an inverted ring P atom. The reaction of bidentate P-ligand 3-2 with dichlorodibenzonitrilo platinum(II) yielded the mixture of a novel cis chelate complex (7 = PtCl₂(3-2)) and a cis bis(3-diphenylphosphino-1,2,3,6-tetrahydrophosphininyl) complex (8 = PtCl₂(η¹-5)₂) containing two units of monodentate P-ligand 5.     

Mixed-ligand chelate extraction of trivalent lanthanides and actinides with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 and dihexyl-N,N-diethylcarbamoylmethyl phosphonate

Mixed-ligand chelate extraction of trivalent lanthanides such as La, Eu and Lu and a trivalent actinide, Am into xylene with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) and dihexyl-N,N-diethylcarbamoylmethylphosphonate (CMP) has been studied by tracertechniques. These trivalent metal ions are found to be extracted from 0.01 mol/dm³ chloroacetate buffer solutions as M(PMBP)₃·HPMBP type self adducts with HPMBP alone and in the presence of CMP as M(PMBP)₃·CMP (where M=La, Eu, Lu and Am) into the organic phase. The equilibrium constants of the above species are deduced by non-linear regression analysis. The synergistic constants of trivalent lanthanides do not increase monotonically with atomic number but have a maximum at Eu and that of Am was found to lie between that of La and Eu.     

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.     

Reaction of 4,5-diamino-3-methyl-1-phenylpyrazole with 3-dimethylaminopropiophenones. Synthesis of new 4-aryl-6-methyl-8-phenyl-2,3-dihydropyrazolo[3,4-b]diazepines and 4-aryl-8-methyl-6-phenyl-2,3-dihydropyrazolo[4,3-b]diazepines

New 4-Aryl-6-methyl-8-phenyl-2,3-dihydropyrazolo[3,4-b]diazepines and 4-aryl-8-methyl-6-phenyl-2,3-dihydropyrazolo[4,3-b]diazepines were obtained from the reaction of 4,5-diamino-3-methyl-1-phenylpyrazole 1 with one equivalent of the 3-dimethylaminopropiophenones 2 in absolute ethanol. The structures of 4-aryl-6-methyl-8-phenyl-2,3-dihydropyrazolo[3,4-b]diazepines 3 and 4-aryl-8-methyl-6-phenyl-2,3-dihydropyrazolo[4,3-b]diazepines 4 were determined by detailed nmr measurements.     

三组分一锅法合成3-甲基-1-苯基-4-芳基-4,11-二氢-4H-吡唑并[4’,5’∶3,2]吡啶并[5,6-c]香豆素

以芳醛、4-羟基香豆素和3-甲基-1-苯基-5-氨基吡唑为原料,用少量冰醋酸作溶剂,三组分一锅法合成一系列吡唑并[4′,5′∶3,2]吡啶并[5,6-c]香豆素衍生物,该反应产率高(79％～94％)、操作简单、后处理方便.产物的结构经红外光谱、核磁共振氢谱、元素分析及单晶X射线分析证实.     

Preparation of 3(5)-phenyl-1-hydroxypyrazole 2-oxide and 4-methyl-3(5)-phenyl-1-hydroxypyrazole 2-oxide

Nitrosation of acrylophenone oxime or of methacrylophenone oxime with n-butyl nitrite in the presence of pyridine and copper(II) sulfate gives the copper complexes of the title compounds. The free 1-hydroxypyrazole 2 -oxides are isolated by treating the copper complexes with dilute sodium hydroxide, filtration, and acidification of the basic filtrates. The title compounds are the first examples of 1-hydroxypyrazole 2 -oxides in which the C3(5) ring position is unsubstituted.