Oxidative halogenation of substituted pyrroles with cu(II). Part I. Bromination of some 3-acetylpyrroles

3-Acetylpyrroles are brominated with copper(II) bromide. The reaction afforded almost quantitatively only nuclear monobromination. Evidence for the structures of final compounds was by mass spectrometry, ¹H-nuclear magnetic resonance, ir, and elemental analysis.     

Oxidative halogenation of substituted pyrroles with cu(II). Part II. Bromination of some ethyl 3-pyrrolecarboxylates and corresponding acids

Ethyl 3-pyrrolecarboxylates and their corresponding acids are brominated with copper(II) bromide. The reaction afforded at 0°, with high-yield nuclear monobromination.     

Oxidative halogenation of substituted pyrroles with Cu(II). Part IV. Bromination of 2-(2′-hydroxybenzoyl)pyrrole. A new synthesis of bioactive analogs of monodeoxypyoluteorin

The selective bromination with copper(II) bromide of the pyrrole ring in 2-(2′-hydroxybenzoyl)pyrrole II in the heterogeneous phase is described giving in almost quantitative yield the 4,5-dibromo derivative VI. The subsequent introduction of halogen into the phenol moiety was observed when the reaction was performed in the homogeneous phase with an excess of halogenating agent. The pentabromo derivative IX , a compound very active against Staphylococcus aureus (mic = 17 nmoles per dm^?3), was obtained by exhaustive bromination of the title compound. Poor yields of chloro derivatives of II were obtained by reaction of the parent compound with copper(II) chloride.     

Poly(ethylene sulfide). III. Oxidative degradation

Injection-molded poly(ethylene sulfide) containing polyamines and zinc salts as thermal stabilizers has excellent physical properties at room temperature, but discolors rapidly on air aging at 150°C, with embrittlement and general deterioration of properties. Degradative breakdown under these conditions is preponderantly thermo-oxidative in nature. The site of the polymer's thermo-oxidative instability was sought in oxidation experiments involving the resin as well as model compounds for the polymer's organic structure. Identification studies were carried out on the oxidation products of 3,6-dithiaoctane (a model compound). Rate of oxygen consumption by the model compound was measured by a pressure-bomb technique and by a volumetric method. Oxidation of the model compound was found to proceed indefinitely as long as the supply of oxygen was replenished. Rate of oxidation was nonaccelerating and independent of oxygen pressure within the range 1.7–3 atm O₂. The gaseous products of the oxidation of unstabilized (no polyamine) resin were found to be identical to the products from the oxidation of the model compound. A mechanism has been proposed taking into account the products isolated and identified, and the nonaccelerating nature of the oxidation. The poly(ethylene sulfide) structure is able to decompose hydroperoxides via formation of sulfoxides, preventing the acceleration of the oxidation reaction. While effecting this radical deactivation, the polymer chains are cleaved, with a resultant loss in molecular weight and physical properties. Some success has been met in the use of inorganic or metallo-organic additives as antioxidants. Among these are dithiocarbamate salts and selenocyanates. The effectiveness of these compounds has been demonstrated in the polymer, and a suggested rationale for stabilization is given.     

Electrochemical oxidation of 2,4,5-triaryl-substituted pyrroles. II. Oxidative dimerization of 4,5-diphenyl-2-mesitylylpyrrole

2,4,5-Triaryl-substituted pyrroles lead, upon chemical or electrochemical oxidation, to an intermediate β-β'-dimer, which, in the course of the reaction, undergoes further oxidation to a tetracyclic derivative. To improve the selectivity towards the uncyclized dimer the oxidation of a triarylpyrrole in which the ortho positions of the phenyl group in position 2 are hindered by the presence of methyl groups was attempted. The cyclization was hindered, but an α-β'-dimer was obtained as the major product. An unexspected isomeric α-β'-dimer, in which the mesitylyl group is shifted into the β position of the pyrrole ring which undergoes the oxidation, was obtained in minor amounts. Electroanalytical data indicate that the process goes through the formation of a monomeric radical cation, followed by a slow chemical reaction.     

Bromination of sydnones. II Bromination of 3-(2-aminophenyl)sydnone and related compounds

Bromination of 3-(2-aminophenyl)sydnone 2 under a variety of conditions is reported. The products obtained are interrelated by a series of subsequent reactions. One major product is the bromoaryl compound 8, the first example of bromination on the aryl rather than sydnone ring when the two are in competition. Surprisingly, bromoaminosydnone 9, prepared from its nitro analogue, was not among the products obtained by direct bromination of 2.     

Bromination of sydnones. III. Bromination of 3-(2-substituted-phenyl)sydnones and subsequent side chain modification

Bromination of the sydnone ring of several ortho-substituted N-arylsydnones is reported. Subsequent side-chain modification generally can be achieved without concomitant removal of the 4-bromo protective group.     

Electrochemical oxidation of substituted pyrroles. III. Anodic oxidation of 2,5-diphenyl-3-acetylpyrrole

The electrochemical oxidation of 2,5-diphenyl-3-acetylpyrrole (I) is described. The cyclic derivative 1,6a-dihydro-2,5,6a-triphenyl-3,4-diacetylbenzo[g]pyrrolo[3,2-e]indole (II) was obtained in very good yield. However, when water was present in the reaction medium, a different derivative, 4-acetyl-2-hydroxy-2,5-diphenyl-3-(4′-acetyl-2′,5′-diphenyl-3′-yl)-2H-pyrrole (III) , was obtained as the main product. 2,2′,5,5′-Tetraphenyl-4,4′-diacetyl-3,3′-dipyrryl (IV) , a potentially useful intermediate for the synthesis of condensed pyrroles, was synthesized by zinc reduction of III.     

Oxidative Dehydrogenation of Cu(II) Complexes with N-Aryl-N-2-hydroxybenzyl- and N-Aryl-N-2-hydroxynaphthylmethyleneamine Derivatives

The reactions of Cu²⁺, Co²⁺, and Ni²⁺ ions with N-phenyl-N-2-hydroxybenzyl- and N-phenyl-N-2-hydroxynaphthylmethyleneamine derivatives (HL ⁿ , n = 1–8) produced from the derivatives of aniline and aromatic -hydroxyaldehydes are studied. Among the ions studied, only Cu²⁺ forms stable complexes Cu(L ⁿ )₂ · 2H₂O. The structures of the synthesized compounds are studied by IR, UV, and EPR spectroscopies and differential thermal analysis. The magnetic moments of the Cu(L ⁿ )₂ · 2H₂O complexes are very small and range within 0.43–1.19 _B, depending on the ligand structure, which indicates a strong antiferromagnetic interaction between the Cu²⁺ ions. The temperature dependence of the magnetic susceptibility measured for the Cu(L³)₂ · 2H₂O complex (where HL³ is N-4-methoxyphenyl-N-2-hydroxybenzylamine) is closest to the theoretical curve calculated for the binuclear Cu(II) complexes connected by the intermolecular exchange interaction. The Cu(II) complexes with HL ⁿ are shown to undergo oxidative dehydrogenation to form the corresponding metal salicyl-aldiminates. This reaction can occur on heating in the absence of oxygen and is accompanied by the Cu²⁺ Cu⁺ transition.     

Polymerization of 3,4-dihydro-2H-carboxyaldehyde (acrolein dimer). Part II. Copolymerization with isocyanates

Copolymers of 3,4-dihydro-2H-pyran-2-carboxyaldehyde (acrolein dimer) with phenyl isocyanate were obtained under several conditions. Infrared and NMR analyses showed that the isocyanate always reacted with acrolein dimer forming urethane linkages, not block units of isocyanate. An alternating copolymer was obtained from the copolymerization in the presence of anionic catalysts such as butyllithium at room temperature, irrespective of the monomer ratios employed. The isocyanate content in the copolymer prepared with an Al(C₂H₅)₂Cl catalyst was increased by elevating polymerization temperature. The copolymerizability of aldehydes with the isocyanate depends upon the polarity of aldehyde group.     

Polythiolated complexes. Part 2(1). Palladium(II) and platinum(II) derivatives of polyfluorophenylthiolates

Summary The preparation and characterization of the new thiolate complexes [M(SR)₂(SEt₂)₂] (M=Pt, R=C₆F₅ orp-C₆HF₄) and [M(SR)₂]_n (M=Pd, R=C₆F₅,p-C₆HF₄ orp-C₆H₄F; M=Pt, R=p-C₆H₄F) is discussed. The tendency to form polymeric, rather than monomeric species, varies as follows: Pd>Pt; C₆H₄F>C₆HF₄> C₆F₅. [Pt(SC₆F₅)₂(SEt₂)₂] has atrans square planar coordination.     

2,2’─呋喃联吡咯型联体杂环化合物的合成

在强极性的醇酸体系中，利用Knorr－Paal反应制得了呋喃联吡咯系的13个新化合物，并进行了红外光谱、质谱、核磁共振谱及元素分析测定。     

Determination of Cu(III) and Cu(II) + Cu(III) in superconducting copper ceramics

Summary Copper(III) and total copper in superconducting Y-Ba-Cu oxide and related compounds can be determinated by two successive iodimetric titrations after the sample has been dissolved under Ar in HCl/KI medium. First, the iodine equivalent to copper(III) ist titrated with Na₂S₂O₃ solution at pH 4.8, copper(II) being masked with EDTA. The total copper is then determined in the same solution by demasking with acid and iodide, followed by iodimetric titration. The method is both accurate and reproducible. The relative standard deviations for 1.074% copper(III) and 23.37% total copper are 0.8% and 0.3%, respectively.     

Use of Complexation TLC to Investigate Selected Monosulfides. Part I. Silica Impregnated with Cu(II), Co(II), Ni(II), Mn(II), Al(III), Cr(III), and Fe(III) Cations as Stationary Phase

JPC – Journal of Planar Chromatography – Modern TLC - This paper focuses on the use of complexation liquid chromatography (in its TLC mode) to investigate eleven monosulfides. In the...     

Facile synthesis of N-aryl pyrroles via Cu(II)-mediated cross coupling of electron deficient pyrroles and arylboronic acids

N-Arylation of electron-deficient pyrroles has been achieved by cross-coupling with arylboronic acids at room temperature in the presence of stoichiometric amounts of copper(II) acetate. The generality of this reaction has been established with variously substituted pyrroles as well as boronic acids. A key intermediate in the synthesis of a matrix metalloprotease inhibitor has been achieved using this methodology.     

EPR Study of some Copper(II) Coordination Compounds with substituted Biguanides. III

Copper(II) coordination compounds with p-chlorphenylbiguanide of the type: [Cu(Cl-PhBig)₂]X₂ and [Cu(Cl–PhBig)X₂] with X =Cl^?, Br^? NO₃, OH^?, NCS^?, NCO^?, N₃, have been studied by EPR spectroscopy using polycrytalline powders and solutions in DMF. The parameters of the EPR spectra have been used to estimate molecular orbital coefficient, in these compounds and to discuss details of the chemical bonding.     

Gold(III)-catalyzed halogenation of aromatic boronates with N-halosuccinimides

Aromatic boronates bearing halogen substituents in the aromatic ring can be synthesized by AuCl(3)-catalyzed halogenations with N-halosuccinimides.     

Oxidative condensation reactions of (diethylenetriamine)cobalt(III) complexes with substituted bis(pyridin-2-yl)methane ligands

The synthesis and characterisation of Co(III) complexes derived from a condensation reaction with a central or terminal nitrogen of a dien ligand and the -carbon of a range of substituted bis(pyridin-2-yl)methane ligands are described. Aerial oxidation of bpm {bis(pyridin-2-yl)methane with Co(II)/dien or direct reaction with Co(dien)Cl₃ provided in low yield a single C–N condensation product 1 (at the primary terminal NH₂) after the pyridyl –CH₂– is formally oxidised to –CH⁺–. The methyl substituted ligand bpe {1,1-bis(pyridin-2-yl)ethane} behaves likewise, except both terminal (prim) and central (sec) amines condense to yield isomeric products 2 and 3. Two of these three materials have been characterised by single crystal X-ray crystallography. The corresponding reactions for the bis(pyridyl) ligand bpk {bis(pyridin-2-yl)ketone} provided C–N condensation products without the requirement for oxidation at the -C center; two carbinolamine complexes in different geometrical configurations resulted, mer-anti-[Co(dienbpc)Cl]ZnCl₄, 5, and unsym-fac-[Co(dienbpc)Cl]ZnCl₄, 6, {dienbpc=[2-(2-aminoethylamino)-ethylamino]-di-pyridin-2-yl-methanol}. In addition, a novel complex, [Co(bpk)(bpd-OH)Cl]ZnCl₄, 4, in which one bidentate N, N-bonded bpk ligand and one tridentate N, O, N-bonded bpd (the diol from bpk+OH⁻) were coordinated, was obtained via the Co(II)/O₂ synthetic route. When the bpc ligand (bpc=bis(pyridin-2-yl)methanol) was employed directly as a reagent along with dien, no condensation reactions were observed, but rather a single isomeric complex [Co(dien)(bpc)]Cl.ZnCl₄, 7, in which the ligand bpc acted as a N,N,O-bonded tridentate ligand rather than as a N,N-bidentate ligand was isolated. ¹³C, 1D and 2D ¹H NMR studies are reported for all the complexes; they establish the structures unambiguously.     

Poly(amine ester) dendrimer with naphthyl units as a fluorescent chemosensor for Al(III), Cu(II), and Zn(II).

A poly(amine ester) dendrimer with naphthyl units (G1N6) has been synthesized as a fluorescent chemosensor for metal ions. We investigated the metal-ion recognition of G1N6 by adding each of Ag(+), Al(3+), Ba(2+), Ca(2+), Cd(2+), Co(2+), Cu(2+), Fe(3+), Mg(2+), Ni(2+), and Zn(2+) in acetonitrile solution. Large changes were observed in the fluorescence spectra of G1N6 upon the addition of Al(3+), Cu(2+), and Zn(2+).