Allgemeiner Zugang zu Polyaminen mit Ethan-1,2-diamin-Einheiten: Synthese von nicht natürlich vorkommenden homologen und isomeren N1,4-Di(4-cumaroyl)sperminen

█tl="American"█The synthesis of the three N,N′-di(4-coumaroyl)tetramines, i.e., of (E,E)-N-{3-[(2-aminoethyl)amino]propyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1a ), (E,E)-N-{4-[(2-aminoethyl)amino]butyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1b ), and (E,E)-N-{6-[(2-aminoethyl)amino]hexyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1c ), is described. It proceeds through stepwise construction of the symmetric polyamine backbone including protection and deprotection steps of the amino functions. Their behavior on TLC in comparison with that of 1,4-di(4-coumaroyl)spermine (=(E,E)-N-{4-[(3-aminopropyl)amino]butyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(propane-1,3-diyl)bis[prop-2-enamide]; 2 ) is discussed.     

A new synthesis of 1,3-difunctionalized 2-sulfonamidopropane derivatives via regioselective ring opening reactions of 2-(bromomethyl)-1-sulfonylaziridines by substituted arylsulfonamides

The novel functionalized N,N′-[2-(arylsulfonamido)propane-1,3-diyl]bis(N-allylarylsulfonamide) and N,N′-[2-(methylsulfonamido)propane-1,3-diyl]bis(N-benzylarylsulfonamide) derivatives have been prepared from 2-(bromomethyl)-1-sulfonylaziridines for the first time using substituted arylsulfonamides in the presence of sodium methoxide under catalyst-free condition in good yields.     

Bisthiourea: thermal and structural investigation

Bisthiourea derivatives 1,1′-(ethane-1,2-diyl)bis(3-phenylthiourea), 1,1′-(propane-1,3-diyl)bis(3-phenylthiourea), and 1,1′-(butane-1,4-diyl)bis(3-phenylthiourea) have been synthesized and characterized by IR, ¹H NMR, and ¹³C NMR. Suitable crystals of 1,1′-(propane-1,3-diyl)bis(3-phenylthiourea) were grown for single-crystal X-ray analysis and from the data it was observed that they organize into the P-1 space group. The thermal decomposition of these compounds has been studied by TG–DSC.     

Developments in transfer hydrogenations of aromatic ketones catalyzed by boron compounds

Boron complexes BL1 and BL2 were prepared from O-donor ligands, 2,2′-(1E,1′E)-(ethane-1,2-diylbis(azan-1-yl-1-ylidene))bis(methane-1-yl-1-ylidene)diphenol (L1) and 2,2′-(propane-1,3-diylbis(azan-1-yl-1-ylidene))bis(methane-1-yl-1-ylidene)diphenol (L2). The complexes were fully characterized by ¹H and ¹³C NMR, LC-MS/MS, TGA/DTA, UV-Vis, elemental analysis, SEM, and FTIR. The transfer hydrogenation of acetophenone derivatives was investigated by the boron complexes in the presence of isoPrOH, as the hydrogen source, under basic condition with NaOH. The results showed that the boron complexes were promising catalytic precursors for transfer hydrogenation of aromatic ketones in 0.1 M isoPrOH solution (up to 99%). Both steric and electronic factors of this class of molecules had a significant impact on the catalytic properties.     

Reaction of thiourea with formaldehyde and simplest aliphatic diamines

N,N′-Bis(hydroxymethyl)thiourea reacted with propane-1,3-diamine at a molar ratio of 2 : 1 to give 5,5′-propane-1,3-diylbis(1,3,5-triazinane-2-thione), whereas 1,3,5,7,11,13,15,17-octaazatricyclo[15.3.1.1^7,11]-docosane-4,14-dithione was obtained in the reaction with equimolar amounts of the reactants. Tricyclic product was also formed in the three-component condensation of thiourea with formaldehyde and propane-1,3-diamine at a ratio of 1 : 3 : 1. The reactions of N,N′-bis(hydroxymethyl)thiourea with ethane-1,2-diamine (2 : 1) and of thiourea with formaldehyde and butane-1,4-diamine (1 : 2 : 1) afforded 5,5′-(ethane-1,2-diyl)bis(1,3,5-triazinane-2-thione) and 5,5′-(butane-1,4-diyl)bis(1,3,5-triazinane-2-thione), respectively.     

选择性响应Cu~(2+)、Ag~+及阴离子的菲咯啉-水杨醛荧光探针

在乙酸酐中用2,9-二甲基-1,10-菲咯啉与水杨醛缩合反应得到2,2′-(1E,1′E)-2,2′-(1,10-菲咯啉-2,9-二基)双(乙烯-2,1-二基)双(2,1-亚苯基)二乙酸酯(探针1);再将其进一步水解得到2,2′-(1E,1′E)-2,2′-(1,10-菲咯啉-2,9-二基)双(乙烯-2,1-二基)二苯酚(探针2)。经1H NMR、13C NMR、IR、MS表征,探针化合物为大共轭结构,发光性能良好。两种探针分别表现出对Cu2+、Ag+不同的荧光猝灭作用,探针2还能识别阴离子F-和AcO-,具有双功能离子检测性能。光谱滴定、等温滴定量热及质谱等测定了配合物组成、作用常数及热力学参数,探针与金属离子的配合为放热反应,作用比为2∶1。     

选择性响应Cu2+、Ag+及阴离子的菲咯啉-水杨醛荧光探针

在乙酸酐中用2,9-二甲基-1,10-菲咯啉与水杨醛缩合反应得到2,2’-（1E,1’E）-2,2’-（1,10-菲咯啉-2,9-二基）双（乙烯-2,1-二基）双（2,1-亚苯基）二乙酸酯（探针1）;再将其进一步水解得到2,2’-（1E,1’E）-2,2’-（1,10-菲咯啉-2,9-二基）双（乙烯-2,1-二基）二苯酚（探针2）。经¹H NMR、¹³C NMR、IR、MS表征,探针化合物为大共轭结构,发光性能良好。两种探针分别表现出对Cu²⁺、Ag⁺不同的荧光猝灭作用,探针2还能识别阴离子F^-和AcO^-,具有双功能离子检测性能。光谱滴定、等温滴定量热及质谱等测定了配合物组成、作用常数及热力学参数,探针与金属离子的配合为放热反应,作用比为2：1。     

Complexes of Iron(III) and Chrom(III) Salen and Saloph Schiff Bases with Bridging 2,4,6-tris(4-nitrophenylimino-4′-formylphenoxy)-1,3,5-triazine

Four new trinuclear Fe(III) and Cr(III) complexes involving tetradenta Schiff bases N,N′-bis(salicylidene)ethylenediamine-(salenH₂) or bis(salicylidene)-o-phenylenediamine-(saloph H₂) with 2,4,6-tris(4-nitrophenylimino-4′-formylphenoxy)-1,3,5-triazine (TNPI-TRIPOD) have been synthesized and characterized by means of elemental analysis carrying out ¹H-NMR., IR spectroscopy, thermal analyses and magnetic susceptibility measurements. The complexes can also be characterized as high-spin distorted octahedral Fe(III) and Cr(III) bridged by nitro. The nitro play a role as bridges for weak anti-ferromagnetic intramolecular exchange.     

Tetradentate vs pentadentate coordination in copper(II) complexes of pyridylbis(aminophenol) ligands depends on nucleophilicity of phenol donors

The ligand binding preferences of a series of potentially pentadentate pyridylbis(aminophenol) ligands were explored. In addition to the previously reported ligands 2,2'-(2-methyl-2-(pyridin-2-yl)propane-1,3-diyl)bis(azanediyl)bis(methylene)diphenol (H(2)L(1)) and 6,6'-(2-methyl-2-(pyridin-2-yl)propane-1,3-diyl)bis(azanediyl)bis(methylene)bis(2,4-di-tert-butylphenol) (H(2)L(1-tBu)), four new ligands were synthesized: 6,6'-(2-methyl-2(pyridine-2-yl)propane-1,3-diyl)bis(azanediyl)bis(methylene)bis(2,4-dibromophenol) (H(2)L(1-Br)), 6,6'-(2-methyl-2(pyridine-2-yl)propane-1,3diyl)bis(azanediyl)bis(methylene)bis(2-methoxyphenol) (H(2)L(1-MeO)), 2,2'-(2-methyl-2(pyridine-2-yl)propane-1,3diyl)bis(azanediyl)bis(methylene)bis(4-nitrophenol) (H(2)L(1-NO2)), and 2,2'-(2-phenylpropane-1,3-diyl)bis(azanediyl)bis(methylene)diphenol (H(2)L(2)). These ligands, when combined with copper(II) salts and base, form either tricopper(II) species or monocopper(II) species depending on the nucleophilicity of the phenol groups in the ligands. All copper complexes were characterized by X-ray crystallography, cyclic voltammetry, and spectroscopic methods in solution. The ligands in trimeric complexes [{CuL(1)(CH(3)CN)}(2)Cu](ClO(4))(2) (1), [{CuL(1)Cl}(2)Cu] (1a), and [{CuL(2)(CH(3)CN)}(2)Cu](ClO(4))(2) (1b) and monomeric complex [CuL(1-tBu)(CH(3)OH)] (2) coordinate in a tetradentate mode via the amine N atoms and the phenolato O atoms. The pyridyl groups in 1, 1a, and 2 do not coordinate, but instead are involved in hydrogen bonding. Monomeric complexes [CuL(1-Br)] (3a), [CuL(1-NO2)] (3b), and [CuL(1-MeO)Na(CH(3)OH)(2)]ClO(4) (3c) have their ligands coordinated in a pentadentate mode via the amine N atoms, the phenolato O atoms, and the pyridyl N atom. The differences in tetradentate vs pentadentate coordination preferences of the ligands correlate to the nucleophilicity of the phenolate donor groups, and coincide with the electrochemical trends for these complexes.     

The water-soluble indolium-based fluorescence probes for detection of the extreme acidity or extreme alkalinity

In this work, 3,3′-(((1E,1′E)-(H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,1-dimethyl-1H-benzo[e]indole-3-ium-2,3-diyl))bis(propane-1-sulfonate) (1), 3,3’-(((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(3,3-dimethyl-3H-indole-1-ium-2,1-diyl))bis(propane-1-sulfonate) (2), 2,2’-((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,3,3-trimethyl-3H-indol-1-ium) iodide (3) and 2,2’-((1E,1′E)-(6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-diyl)bis(ethene-2,1-diyl))bis(1,1,3-trimethyl-1H-benzo[e]indol-3-ium) iodide (4) were designed and synthesized by ethylene bridging of the N-substituted indolium salts and the Tröger’s Base (TB) framework. The probes exhibited a longer absorption and emission wavelength and the emission wavelength of them in dichloromethane (DCM) was more than 600 nm, performed a red fluorescence. All of the probes could work on the extreme acidic and the extreme alkaline environments and showed a good liner response in the working pH range. Especially, 2 and 4 were soluble in water and manifested a good pH sensing in a water system. Also, ¹H NMR analysis illustrated how these dyes worked as the pH-sensitive fluorescence probes. In addition, they performed excellent reversibility, high selectivity and good photostability.     

Recyclization of ethyl 1-alkyl-5-benzoyl-6-methylsulfanyl-2-oxo-1,2-dihydropyridine-3-carboxylates into Bicyclic <Emphasis Type="Italic">N</Emphasis>-alkyl-5-benzoyl-2-oxo-1,2-dihydropyridine-3-carboxamide derivatives by the action of nitrogen-containing 1,4- and 1,5-binucleophiles

Reactions of ethyl 1-alkyl-5-benzoyl-6-methylsulfanyl-2-oxo-1,2-dihydropyridine-3-carboxylates with nitrogen-containing 1,4- and 1,5-binucleophiles (o-phenylenediamine, o-aminobenzenethiol, ethane-1,2-diamine, and propane-1,3-diamine) involved recyclization, leading to the formation of fused N-alkyl-5-benzoyl- 2-oxo-1,2-dihydropyridine-3-carboxamides, diethyl 6,6′-oxybis(1-alkyl-5-benzoyl-2-oxo-1,2-dihydropyridine-3-carboxylates), and diethyl 6,6′-[ethane-1,2-diyl(or propane-1,3-diyl)diimino]bis(1-alkyl-5-benzoyl-2-oxo-1,2-dihydropyridine-3-carboxylates), depending on the reactant ratio. The sequence of formation of intermediate recyclization products was determined.     

Synthesis,characterization, and immobilization of nickel(II) tetradentate Schiff-base complexes on clay as heterogeneous catalysts for the oxidation of cyclooctene

Nickel(II) tetradentate Schiff-base complexes of N,N′-(bis(pyridin-2-yl)formylidene)ethane-1,2-diamine (L1), N,N′-(bis(pyridin-2-yl)formylidene)cyclohexane-1,2-diamine (L2), N,N′-(bis(pyridin-2-yl)formylidene)benzene-1,2-diamine (L3), N,N′-(bis(pyridin-2-yl)formylidene)meso-stilben-1,2-diamine (L4), and N,N′-(bis(pyridin-2-yl)formylidene)propane-1,3-diamine (L5) were synthesized, characterized, and immobilized on sodium montmorillonite. The complexes were characterized by IR spectroscopy, diffuse reflectance spectra (DRS), and atomic absorption spectroscopy (AAS). IR and DRS data of the heterogeneous catalysts show that the Ni(II) complexes were physically entrapped within the sodium montmorillonite clay. The supported complexes show good catalytic activity for the epoxidation of cyclooctene using tert-butylhydroperoxide (TBHP) as oxygen source in acetonitrile. The Ni-catalyzed oxidation proceeds with 62.3% selectivity for epoxidation with 69% conversion for supported [Ni(L5)].     

Synthesis and antibacterial activity of new dimeric pyridinium chlorides based on 2,2-bis(hydroxymethyl)propane-1,3-diyl spacer

Russian Chemical Bulletin - New bispyridinium dichlorides based on 2,2-bis(hydroxymethyl)propane-1,3-diyl spacer were synthesized from pentaerythritol, 4-aminopyridine, and carboxylic acids. The...     

Synthesis and mesomorphic properties of esters derived from alkanediols

New alkane-α,ω-diyl esters, propane-1,3-diyl and butane-1,4-diyl bis[4-(4-alkoxybenzoyloxy)-3-bromobenzoates], were synthesized and were found to form nematic mesophase. The effects of the lateral substituent and the length of the central and terminal hydrocarbon chains on the mesomorphic properties of butane-1,4-diyl bis[4-(4-alkoxybenzoyloxy)-3-bromobenzoates] were studied. Structural factors responsible for mesogenic properties of these compounds were determined by conformation analysis.     

Facile access to arsenic-containing triacylglycerides

The previously unknown arsenic-containing triacylglycerides (AsTAGs) 3-((15-(dimethylarsinoyl)pentadecanoyl)oxy)propane-1,2-diyl dipalmitate 1 and 2-((15-(dimethylarsinoyl)pentadecanoyl)oxy)propane-1,3-diyl dipalmitate 2 have been synthesized. They will serve as model compounds in the search for naturally occurring AsTAGs, recently proposed natural constituents of fish oils.     

Multiblock copolymer synthesis via controlled radical polymerization in aqueous dispersions. Part 1: Synthesis of S-tert-alkyl-N,N-alkoxycarbonylalkyldithiocarbamates

In a novel two- or three-step synthetic route, S-(1,4-phenylenebis(propane-2,2-diyl)) bis(N-methyldithiocarbamate) is reacted at low temperature with various alkyl chloroformates to form various S-tert-alkyl-N,N-alkoxycarbonylmethyl-dithiocarbamate RAFT agents. Also an alternative and novel synthetic route towards S-(1,4-phenylenebis(propane-2,2-diyl)) bis(N-methyldithiocarbamate), is proposed.     

Synthesis,crystal structures,and catalytic properties of phenoxo-bridged dinuclear manganese(III) complexes with bis-Schiff bases

Two structurally similar centrosymmetric phenoxo-bridged dinuclear manganese(III) complexes, [Mn₂(L¹)₂(N₃)₂] (1) and [Mn₂(L²)₂(NCS)₂] (2), were prepared from the tetradentate bis-Schiff base ligands, N,N’-bis(salicylidene)propane-1,2-diamine (H₂L¹) and N,N’-bis(salicylidene)ethane-1,2-diamine (H₂L²), respectively, in the presence of pseudohalides. The complexes have been characterized by FTIR, elemental analyses, and molar conductivity. Structures of the complexes have been confirmed by single-crystal X-ray determination. The bis-Schiff base ligands coordinate with Mn through their phenolate oxygen and imino nitrogen. Each Mn is an octahedral. The complexes showed that they exhibit high activity in catalytic olefin oxidation.     

The synthesis and characterization of a new (<Emphasis Type="Italic">E,E</Emphasis>)-dioxime containing 13-membered dithiadiazamacrocyclic moieties and its mononuclear complexes

A new (E,E)-dioxime, (6Z,7Z)-15,16-dihydro-14H-dibenzo[b,h][1,10,4, 7]dithiadiazacyclotride-cine-6,7(5H,8H)-dionedioxime (H ₂ L) has been synthesized by reacting cyanogen-di-N-oxide (2) with 2,2′-[propane-1,3-diylbis(thio)]dianiline (1). Mononuclear complexes (4) and (5) of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with NiCl₂ · 6H₂O and CoCl₂ · 6H₂O, respectively. The BF ₂ ⁺ capped Ni(II) and Co(III) complexes (6) and (7) of the dioxime have been synthesized from (4) and (5). The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-n.m.r, i.r. and m.s. spectral data.     

Photosynthesis of dimeric cinnamaldehyde,eugenol, and safrole as antimicrobial agents

It has been reported that trans-cinnamaldehyde, eugenol and safrole inhibited bacteria and fungi growth in vivo mode. In order to improve their biological activity, dimeric cinnamaldehyde, eugenol and safrole have been photosynthesized. The photosynthesis compounds were 4,6-diphenyl-1,2-dioxane-3,5-dicarboxaldehyde, 4,4-(cyclobutone-1,3-diyl bis(methylene))bis(2-methoxyphenal), and 3,6-bis(benzo[d][1,3]dioxol-5-ylmethyl)-1,2-dioxane. These new dimeric compounds strongly inhibited Candida albicans growth more than the monomers.     

Synthesis of Star-Shaped Macromolecular Schiff Base Complexes Having Melamine Cores and Their Magnetic and Thermal Behaviors

Abstract

We aim to study magnetic and thermal behaviors of some melamine cored macromolecular Schiff base complexes. In this context, tripodal ligands were synthesized by reacting melamine with 4-carboxybenzaldehyde or 4-hydroxybenzaldehyde. Then, 16 new trinuclear Fe(III), Cr(III), Mn(III), and Al(III) complexes were synthesized by reacting the ligands [tris-(4-carboxybenzimino)-1,3,5-triazine) or tris-(4-hydroxybenzimino)-1,3,5-triazine)] with pentadentate Schiff bases N,N′-bis(1-hydroxy-2-benzyliden)-1,7-diamino-4-azaheptane or N,N′-bis(salicylidene)pyridine-2,6-diamine. Later, ligands and complexes were characterized by means of elemental analysis, infrared spectroscopy, ¹H NMR, liquid chromatography–mass spectrometry, thermal analyses, and magnetic susceptibility measurements. Finally, metal ratios of the prepared complexes were determined by using atomic adsorption spectrometry. The complexes were also characterized as distorted octahedral high-spin d ³ (S = 3 × 1/2) Cr(III), high-spin d ⁵ (S = 5 × 1/2) Fe(III), low-spin d ⁴ (S = 2 × 1/2) Mn(III), and diamagnetic Al(III) bridged by ?OH group of COO^? or OH group of phenol.