Crystal Structure and Thermal Property of 4-(3-Chlorophenyl)-3-isopropyl-1-methyl-3,4-dihydroquinolin-2(1H)-one

The target compound(C_(19)H_(20)ClNO) was structurally determined by single-crystal X-ray diffraction. The crystal is in monoclinic system, space group P2_1/n with a = 9.2365(2), b = 12.1241(3), c = 14.9960(4) ?, β = 106.589(3)°, C_(19)H_(20)ClNO, M_r = 313.81, D_c = 1.295 g/cm~3, V = 1609.42(7) ?~3, Z = 4, F(000) = 664, μ(MoKa) = 2.097 mm~(-1), T = 200(10) K, 2813 independent reflections with 2533 observed ones(I 2σ(I)), R = 0.0389 and wR = 0.1057 with GOF = 1.043(R = 0.0423 and wR = 0.1083 for all data). The 3,4-dihydroquinolin-2(1 H)-one moiety maintains thermodynamically stable trans configuration. The decomposition mechanism of compound 3 is complex by thermal analysis.     

Stability constants of thorium(IV) complexes with aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl) methane ligands

Summary Stability constants of complexes of aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl) methane [ArBPyM] derivatives with thorium(IV) ions were determined by the potentiometric method at 30°C and an ionic strength of 0.1 mol·dm^–3 (KNO₃) in 75% (v/v) dioxane-water. The evaluation of the titration data indicated that four kinds of complexes ([ThL]²⁺, [ThLOH]⁺, [ThL ₂], and [ThL(OH)₂]^2–) were formed. The formation constants for all [ThL]²⁺ and [ThL ₂] complexes have been calculated to compare these values with those previously reported [1, 2] with Ln³⁺ and UO ₂ ²⁺ metal ions [2, 3]. The probable ligand-bonding sites of the complexes are proposed. In addition, the applicability of theHammett equation for the correlation of the stability constants of [Th(IV)-ArBPyM] complexes are discussed.

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Stabilitätskonstanten von Thorium(IV)-Komplexen mit Aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl)-methan-Liganden

Zusammenfassung Stabilitätskonstanten von Komplexen von Aryl-bis-(5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl)-methan — Derivaten [ArBPyM] mit Thorium(IV) — Ionen wurden bei 30°C und einer Ionenstärke von 0.1 mol-dm^–3 (KNO₃) in 75% (v/v) Dioxan-Wasser potentiometrisch bestimmt. Die Auswertung der Titrationskurven zeigte, daß vier verschiedene Komplexe vorlagen ([ThL]²⁺, [ThLOH]⁺, [ThL ₂] und [ThL(OH)₂]²⁺). Die Bildungskonstanten aller [ThL]²⁺- und [ThL ₂]-Komplexe wurden berechnet, um sie mit den früher für Ln³⁺- und UO ₂ ²⁺ -Ionen publizierten zu vergleichen. Potentielle Bindungsstellen der Komplexe für Liganden werden vorgeschlagen. Zusätzlich wird die Anwendbarkeit derHammet-Beziehung auf die Korrelation der Stabilitätskonstanten von [Th(IV)-ArBPyM] — Komplexen diskutiert.

     

Electrophilic substitution reactions in trispyrazolediyls,structure of tris(3-methyl-4-isopropyl-1,5-pyrazolediyl)

Halogenation, nitration, and sulfonation of previously obtained tris(1,5-pyrazolediyls) proceeds at position 4 of the pyrazole nucleus with the formation of symmetrical tris(4-substituted 1,5-pyrazolediyls) in quantitative yield. However, only a monoformyltrispyrazolediyl is obtained in the Vilsmeier reaction. An x-ray structural investigation has been carried out on the trispyrazolediyl nucleus of compound (1c).Moscow K. A. Timiryazev Academy of Agriculture, Moscow 127550. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 925–931, July, 1996. Original article submitted March 20, 1996.     

三-(4-吡唑基)苯基胺的合成及其晶体结构

以三苯胺为原料,通过改进的乌尔曼反应高效地合成了三-(4-吡唑基)苯基胺(1),其结构经X-射线单晶衍射仪,1H NMR,IR,MS和元素分析表征.1属于正交晶系,Pccn空间群,晶胞参数:a=23.394(7)A,b=34.021(9)A,c=11.719(3)A.分子问通过氢键和弱的π----π作用相互连接.     

Naphth[1,2-d]oxazole intermediates in the preparation of 3-hydroxy-4-(1-alkyl-3-methyl-5-hydroxy-4-pyrazolyl)-azo-1-naphthalenesulfonamide dyes

Acylation of 4-amino-3-hydroxy-1-naphthalenesulfonic acid ( 3 ) with benzoyl chloride in pyridine gave pyridinium 3-hydroxy-4-(N-benzoylamino)-1-naphthalenesulfonate ( 12 ) which was converted by thionyl chloride followed by diethylamine into N,N-diethyl-2-phenylnaphth[1,2-d]oxazole-5-sulfonamide ( 14 ). The naphthoxazole moiety was hydrolyzed with potassium hydroxide and the resulting N,N-diethyl-4-amino-3-hydroxy-1-naphthalenesulfonamide ( 11 ) coupled with 1-alkyl-3-methyl-5-pyrazolones. The 2-phenylnaphth[1,2-d]oxazole intermediates and various by-products were investigated.     

2－异丙基－1，3－二氢－4（1H）异喹啉酮及其衍生物的合成

异喹啉酮（1）与羟胺反应得异喹啉酮肟（2），再经Schroeter重排合成得到 4-氨基异喹啉的盐（3），进而经催化加氢还原生成其脱烷基产物6.另外 ，异喹啉 酮与NaN3反应合成得到苯并二氮杂Zhuo酮（4），4经还原可生成苯并二氮杂Zhuo（ 5），合成得到的5个新化合物的结构经元素分析、红外、^1H NMR及质谱等方法所 证实。     

Synthesis of 1,3-Bis[2-hydroxy-3-(3-methyl-5-oxo-2,5-dihydro-1-pyrazolyl)propyl)uracils

A reaction was studied of newly synthesized 1,3-bis(2-hydroxy-3-chloropropyl)uracil and 1,3-bis(2-hydroxy-3-chloropropyl)-6-methyluracil with hydrazine hydrate followed by treating the compounds formed with ethyl acetoacetate. The hydrazones obtained cyclized into pyrazolones in the presence of sodium methylate.     

Polymeric methylenebis(diphenylphosphine oxide) hydrogen triiodide

The conformation of the cationic part of the title compound, [{(C₆H₅)₂POH_0.5}₂CH₂]I₃ or dppmO₂H⁺·I₃^? (dppm is di­phenyl­phosphino­methane), is determined by hydrogen bonds between cations of monoprotonated [(C₆H₅)₂P(=O)]₂CH₂ (dppmO₂). Symmetric P=O?H?O=P bridging, with H atoms lying on centres of inversion, leads to chain‐like polymeric cations, (dppmO₂H⁺)_x, made up of H?OP(C₆H₅)₂—CH₂—(C₆H₅)₂PO? moieties. These are, in turn, cross‐connected by non‐classical C—H?I contacts between the (dppmO₂H⁺)_x methyl­ene‐group H atoms and the terminal I atoms of the triiodide anions, which display crystallographic inversion symmetry.