N-(3-吡啶基甲基)氮杂环化合物的合成

以3 氯甲基吡啶盐酸盐和含氮杂环化合物四氢吡咯、哌啶、吗啉、哌嗪及咔唑为原料,通过N 烷基化反应,合成了6个N (3 吡啶基甲基)氮杂环化合物。3 氯甲基吡啶盐酸盐分别与四氢吡咯、哌啶、吗啉在二甲亚砜中于50℃下反应3h,后在室温下反应16h,得到N (3 吡啶基甲基)四氢吡咯、N (3 吡啶基甲基)哌啶及N (3 吡啶基甲基)吗啉,收率分别为87 1%、85 5%和73 1%;3 氯甲基吡啶盐酸盐与无水哌嗪以不同的投料比〔n(3 氯甲基吡啶盐酸盐)∶n(无水哌嗪)=1∶2 67和3∶1),分别在甲醇中于50℃下反应8h和10h,得到N (3 吡啶基甲基)哌嗪和N,N′ 二(3 吡啶基甲基)哌嗪,收率分别为82 4%和61 3%;3 氯甲基吡啶盐酸盐与咔唑在N,N 二甲基甲酰胺中于室温下反应12h,得到9 (3 吡啶基甲基)咔唑,收率93 7%。用1HNMR和13CNMR对产品进行了表征,证明了合成方法的可靠性。     

Selective aminolysis of mixed esters of cellulose

Aminolysis of cellulose esters was investigated. Of the amines tested (pyrrolidine, n-butylamine, sec-butylamine, 2,2-dimethylpropylamine, piperidine, cyclohexylamine, morpholine), pyrrolidine was the most reactive. The rate of aminolysis by pyrrolidine was approximately the same in dioxane as in dimethyl sulfoxide (DMSO). Using pyrrolidine in DMSO, the relative order of reactivity of the cellulose esters studied was acetate > butyrate ? phenylpropionate. With two mixed esters, cellulose acetate 2-phenylpropionate and cellulose acetate polystyrene carboxylate, deacetylation could be achieved with high specificity. Pyrrolidine in DMSO may also be used to perform a controlled deacetylation of cellulose triacetate in a homogeneous solution down to a degree of substitution of about 0.05. The aminolysis conditions did not cause any degradation of the cellulose chains.     

Efficient and Selective Synthesis of E‐Vinylamines via Tungsten(0)‐Catalyzed Hydroamination of Terminal Alkynes

The hydroamination of terminal alkynes (RCCH=phenylacetylene, 4‐methylphenylacetylene, 4‐fluorophenylacetylene, 1‐hexyne, methyl 2‐propynyl ether, prop‐2‐yn‐1‐ol) with secondary amines (piperidine, pyrrolidine, morpholine, piperazine, methylpiperazine, 4‐methylpiperidine and 3‐methylpiperidine) was achieved in high yield (up to 99%), regioselectivity (only anti‐Markovnikov product) and stereoselectivity (only E‐isomers) within a maximum of 5 h in reactions catalyzed by the tungsten tetracarbonyl complex cis‐[W(CO)₄(piperidine)₂] at 90 °C without any additional solvent.

     

CO2 Absorption into Aqueous Solutions of Monoethanolamine,Methyldiethanolamine, Piperazine and their Blends

The removal of carbon dioxide from industrial gases, e.g. in thermal power stations to meet the discharge limits for CO₂ in flue gases, is usually achieved with a reactive absorption technique using aqueous solutions of alkanolamines. From the absorption performance point of view, primary and secondary amines are preferred. However, in case the costs of the solvent regeneration are also taken into account, tertiary amines are much more attractive. In order to combine the specific advantages of tertiary and primary/secondary alkanolamines, both types of solvents are mixed. In this paper, mixtures of monoethanolamine and methyldiethanolamine with piperazine as absorption activator are experimentally compared with respect to CO₂ removal performances at 25 °C. The absorption process in a special packed column has also been simulated with the use of published data on reaction kinetics, physicochemical properties (densities, viscosities, diffusivities, Henry coefficients) of the CO₂‐amines systems, including experimentally determined hydrodynamic and mass transfer characteristics of the CO₂ scrubber.     

Durability of adhesives based on different epoxy/aliphatic amine networks

The mechanical and adhesives properties of epoxy formulations based on diglycidyl ether of bisphenol A cured with various aliphatic amines were evaluated in the glass state. Impact tests were used to determine the impact energy. The adhesive properties have been evaluated in terms single lap shear using steel adherends. Its durability in water at ambient temperature (24 °C) and at 80 °C has also been analyzed. The fracture mechanisms were determined by optical microscopy. It was observed a strong participation of the cohesive fracture mechanisms in all epoxy system studied. The 1-(2-aminoethyl)piperazine epoxy adhesive and piperidine epoxy adhesive presents the best adhesive strength and the largest impact energy. The durability in water causes less damage to piperidine epoxy networks. This behavior appears to be associated with the lower water uptake tendency of homopolymerised resins due to its lower hydroxyl group concentration.     

Michael addition polymerizations of trifunctional amines with diacrylamides

With the aim to get a clear understanding of this category of polymerizations, the Michael addition polymerizations of trifunctional amines, i.e. 4-aminomethyl piperidine (AMPD), N-methyl ethylenediamine (MEDA), and 1-(2-aminoethyl) piperazine (AEPZ), with an equimolar diacrylamide, N,N′-methylene diacrylamide (MDA), were investigated. Similar to the polymerizations of these amines with an equimolar diacrylate, novel linear poly(amido amine)s containing secondary and tertiary amines in the backbones are obtained from these polymerizations as reflected by ¹³C NMR (INVGATE). In situ monitoring the polymerization processes using NMR shows that the reactivity sequence of three types amines in the trifunctional amines is 2° amine (original)>1° amine?2° amine (formed), and the 2° amine (formed) is kept out of the reaction. But these results are different from those reported for the polymerizations of the similar amines with an equimolar divinyl sulfone and some diacrylates. The molecular weights and properties of poly(amindo amine)s obtained were characterized by GPC, DSC and TGA, respectively.     

Role of Amines in Adhesion of Polybutadiene to Glass Substrates I. Reactions of Amines During Peroxide Curing of Polybutadiene

An attempt to elucidate the role of amines in general, and of 3-aminopropyltriethoxysilane in particular, has been made through a study of the title subject by several different approaches. This paper describes the interactions of amines during curing of the rubber phase. When aromatic or cyclic amines were added, maximum stress at break and minimum swelling ratios were observed when the number of alkoxide radicals generated was equal to the number of hydrogen atoms on the nitrogen of the amines. The order of reactivity was thus no amine > aniline > piperazine > m-phenylenediamine. The greatest effect of aliphatic amines also occurred when the concentration of primary amino groups was equal to the concentration of peroxide; but the behavior was complex and dependent on the backing against which samples were molded. The higher rigidity and reinforcement of the polybutadiene in the presence of low concentrations of amines was attributed to formation of chemical bonds between the amines and the polybutadiene.     

A simple and versatile protocol for the preparation of functionalized heterocycles utilizing 4-benzoyl-5-phenylamino-2,3-dihydrothiophene-2,3-dione

The reaction of ethyl benzoylpyruvate with phenyl isothiocyanate in alkaline medium yields 4-benzoyl-5-phenylamino-2,3-dihydrothiophene-2,3-dione (1). Reaction of the intermediate 1 with primary aromatic amines such as aniline derivatives, benzidine and secondary aliphatic amines, namely diethylamine, piperidine, morpholine and piperazine afforded the corresponding thiophene 2a–2g and amide 3a–3d derivatives. Compound 1 reacts with N,N′- and N,O-dinucleophiles such as 1,2-diaminoalkanes, 2-aminoethanol, 1-aminoguanidine, guanidine, urea, 1,2-phenylenediamine and 2-amino-4-methylphenol to form the heterocylic compounds 4–10.     

Atom transfer radical polymerization by [RuCl<Subscript>2</Subscript>(PPh<Subscript>3</Subscript>)<Subscript>2</Subscript>(amine)] catalysts: Cyclic amines as tuner of reactivity

Atom transfer radical polymerizations (ATRP) of styrene (St) and methyl methacrylate (MMA) mediated by [RuCl₂(PPh₃)₂(amine)] complexes, with amine = pyrrolidine (1), piperidine (2), or perhydroazepine (3), were investigated as a function of time, temperature, and concentrations of monomers and 2-bromoisobutyrate as initiator. The plots of ln([M]₀/[M]) vs. time and molecular weights vs. monomer conversion were linear and the dispersity indexes decreased with increasing monomer conversions. The complexes 1, 2, and 3 were able to mediate the polymerizations with acceptable rate and level of control. Differences in the rate and control of polymerization were observed in the order 3 > 2 > 1 for both monomers. The activities were discussed considering the steric hindrance and electronic characteristics of the amines as ancillary ligands in the metal centres, considering studies by cyclic voltammetry and NMR.     

Synthesis of 2H‐Thiopyrans by Rhodium(II) Acetate‐Catalyzed Reaction of 4‐Amino‐2,5‐dihydro‐3‐thiophenecarbonitriles with α‐Diazocarbonyl Compounds. Part 1

4‐Amino‐2,5‐dihydro‐3‐thiophenecarbonitriles 1 reacted with dimethyl diazomalonate in the presence of rhodium(II) acetate to give regioselectively 4‐cyano‐2H‐thio‐pyrans 2 (C ₂— S insertion), and 5‐cyano‐2H‐thiopyrans (C ₅— S insertion) were not isolated. Similar insertion was also observed in the reaction of 1 with methyl diazoacetoacetate and ethyl diazobenzoylacetate. The starting compounds 1 were synthesized by the reaction of tetrahydro‐4‐oxo‐3‐thiophene‐carbonitrile with morpholine, piperidine, and pyrrolidine in the presence of formic acid in ethanol.     

One pot catalytic NO2 reduction,ring hydrogenation,and N-alkylation from nitroarenes to generate alicyclic amines using Ru/C-NaNO2

A report to produce alicyclic amines and subsequent N-alkylation with alcohols using Ru/C-NaNO₂ catalyzed facile transformation of nitrobenzene was investigated. Effects of solvent, temperature, pressure, reaction time, and molar-ratio of substrate/catalyst on product composition were also studied. These mechanistic studies explain that nitrobenzene undergoes hydrogenation reaction in the following order; –NO₂ reduction to –NH₂, aromatic ring-hydrogenation to alicyclic, and from the reaction of alcohol to give N-alkylated amines. This investigation shed lights on possible application to polyurethane chemistry since these amines are used as important precursors for diisocyanates.     

Tetrazolverbindungen. 5. Synthese und Umaminierung von Enaminoketonen der Tetrazolreihe

Tetrazole Compounds. 5. Synthesis and Transamination of Enamino Ketones of the Tetrazole Series Tetrazole-5-acetaldehyde enamines 5 react with aliphatic and aromatic carboxylic acid chlorides in the presence of an auxiliary base (e.g. pyridine or triethylamine) to give tetrazolylsubstituted enamino ketones 6 . The latter can be modified by acid-catalyzed transamination with secondary aliphatic amines (e.g. diethylamine, pyrrolidine, piperidine, morpholine, hexamethylene imine) yielding 5-(1-acyl-2-dialkylamino-vinyl)-1-aryl-1 H-tetrazoles 7 . The analogue transamination of 6 with primary alkyl, aralkyl, and aryl amines results in corresponding secondary enamino ketones 8 , which exist in solution as an equilibrium mixture of the Z and E form. Acylation of secondary tetrazole-5-acetaldehyde enamines 9 does not lead to 8 , but to the isomeric N-acyl derivatives 10 . – Characteristic ¹H-n.m.r., u.v., and i.r. spectroscopic data of the novel products are reported.     

Novel thin-film composite nanofiltration membranes fabricated via the incorporation of ssDNA for highly efficient desalination

In this work, the biomacromolecule, single-stranded deoxyribonucleic acid (ssDNA) was innovatively incorporated into the polyamide layer to tailor the permeate flux and antifouling performance of the nanofiltration (NF) membranes. With active amines groups, the ssDNA was as the aqueous phase monomers along with piperazine (PIP), and reacted with trimesoyl chloride on polyethersulfone substrate to fabricate thin-film composite (TFC) NF membranes. The NF membrane prepared under optimal ratio of ssDNA/PIP had a pure water permeability of 75.8 L m⁻² h⁻¹ (improved 58% compared to PIP NF membrane) and Na₂SO₄ rejection of 98.0% at 6.0 bar. The rejections for different inorganic salts were the order: Na₂SO₄ (98.0%) > MgSO₄ (89.2%) > MgCl₂ (72.8%) > NaCl (23.0%). Furthermore, the TFC NF membranes showed good antifouling performance in long-term running with 300 ppm bovine serum albumin and humic acid solution. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 47102.     

手性化合物和杂环酮的法沃尔斯基重排

法沃尔斯基重排反应在精细有机合成方面比如在含杂原子的脂环酮的合成中，尤其是在制新药方面，仍然有着开发与应用的价值和前景。     

Electrokinetic decontamination of heavy metals in construction materials: contribution of the different parameters to the global efficiency

To discriminate between the relative weights of each factor involved in the global process of an electrokinetic treatment for remediation, mortar and brick contaminated with Cs, Sr, Co, Cd and Cu were submitted to electrokinetic treatments with different enhancing electrolytes (distilled water, Na₂-EDTA, oxalic acid and citric acid), and the efficiency was analysed in function of the parameters involved in the process. The data obtained in this research, a matrix including 40 cases, have been correlated for the decontamination percentage in function of the key variables of the treatment, and the best correlation found, able to explain a variance of the 78.5% of the data, was a non linear exponential grow regression. An order in the weight of the contributions has been established that, from bigger to smaller contribution, is: constants of chelation equilibriums > precipitation as hydroxide constants > zeta potential > conductivity of the catholyte > pH catholyte > diffusion coefficient > pH of the material.     

Amino-salicylaldimine–palladium(II) complexes: New and efficient catalysts for Suzuki and Heck reactions

A series of amino-salicylaldimine–palladium(II) complexes bearing 5-methyl-3-(R-1-ylmethyl)-salicylaldimine ligands (R = morpholine, piperidine, pyrrolidine, 4-methylpiperazin, diisopropylamine) have been prepared and characterized by IR, ¹H NMR and elemental analysis. Crystal structure details of complex 2b have been confirmed by X-ray structure analysis. The obtained Pd(II) complexes were found to be effective catalysts for the Suzuki and Heck cross-coupling reactions which could be carried out in the undried solvent under air.     

The Condensation of 2-Aminofluorene with α, ω-Dibromoalkanes

N, N′-(2-fluorenyl) derivatives of piperazine, azetidine, pyrrolidine, piperidine and hexamethyleneimine are formed in the condensation of 2-aminofluorene with α,ω-dibromoalkanes in the presence of calcium hydroxide or sodium ethoxide. The same products have been prepared also by other routes.     

Synthesis and characterization of comb-shaped poly(amido amine)-g-PEO via Michael addition polymerization

Linear pH-sensitive poly(amido amine)s were synthesized via Michael addition polymerization of N-aminoethyl piperazine (AEPZ) or 4-aminomethyl piperidine (AMPD) with 1,12-dodecylene diacrylamide (DDA). Successive Michael addition reaction of acryl-terminated poly(ethylene oxide) (A-PEO) with the secondary amine of linear poly(DDA-AEPZ) that has one secondary amine in every repeating unit afforded PEO-grafted poly(amido amine). Variation of grafting degree could be obtained conveniently via tuning the feed molar ratio of acryl/secondary amine. When this ratio equals to 1.2, all the secondary amines on the backbone of poly(DDA-AEPZ) (or poly(DDA-AMPD)) were consumed and the comb-shaped polymers were formed. The amphiphilic comb-shaped poly(DDA-AEPZ)-g-PEO was molecularly dissolved in water at pH 2.0 (w/v=0.25%), and micelles were formed when pH value of aqueous solution was adjusted to 6.5. ¹H NMR data verify the formation of micelles due to the disappearance of signals attributed to poly(DDA-AEPZ). The formation of micelles can be confirmed further by TEM photos, they show that all the particles are approximately spherical and their number-average diameter is around 95 nm.     

Direct Amide Synthesis from Alcohols and Amines by Phosphine‐Free Ruthenium Catalyst Systems

Amides are synthesized directly from alcohols and amines in high yields using an in situ generated catalyst from easily available ruthenium complexes such as the (p‐cymene)ruthenium dichloride dimer, [Ru(p‐cymeme)Cl₂]₂, or the (benzene)ruthenium dichloride dimer, [Ru(benzene)Cl₂]₂, an N‐heterocyclic carbene (NHC) ligand, and a nitrogen containing L‐type ligand such as acetonitrile. The phosphine‐free catalyst systems showed improved or comparable activity compared to previous phosphine‐based catalytic systems. The in situ generated catalyst from [Ru(benzene)Cl₂]₂, an NHC ligand, and acetonitrile showed excellent activity toward reactions with cyclic secondary amines such as piperidine and morpholine.     

1H-咪唑并[4,5-c]喹啉衍生物的合成

以1-(2-甲基丙基)-4-氯-1H-咪唑并[4,5-c]喹啉(Ⅰ)为原料与哌啶反应合成了1-(2-甲基丙基)-4-[哌啶-1-基]-1H-咪唑并[4,5-c]喹啉(Ⅱ),当用甲苯为溶剂,n(Ⅰ)∶n(哌啶)∶n(K2CO3)=1∶2∶0.3时,Ⅱ的收率为88.5%;Ⅰ与三倍过量的吗啉反应合成1-(2-甲基丙基)-4-[吗啉-4-基]-1H-咪唑并[4,5-c]喹啉(Ⅲ),收率86.5%;Ⅰ与三倍过量的哌嗪在体积分数50%的1,4-二氧六环水溶液中反应合成1-(2-甲基丙基)-4-[哌嗪-1-基]-1H-咪唑并[4,5-c]喹啉(Ⅳ),收率59%。Ⅱ、Ⅲ、Ⅳ的合成工艺均较简单。