Tetrahydropyrido[3,4-b]pyrazine scaffolds from pentafluoropyridine

[reaction: see text] Representative polyfunctional tetrahydropyrido[3,4-b]pyrazine scaffolds have been synthesized very readily by a one-pot annelation reaction of pentafluoropyridine with appropriate diamines. The trifluorinated pyridopyrazine products react sequentially with various nucleophiles to give poly-substituted tetrahydropyridopyrazines, demonstrating the potential of the polyfluorinated ring fused pyridine system as a scaffold for the synthesis of previously inaccessible poly-substituted pyridopyrazine derivatives. This general approach has special relevance to the development of new chemical entities for the life science industries and particularly in the drug discovery arena, in which low molecular weight, polyfunctional heterocyclic derivatives are playing an increasingly important role.     

Carbohydrates as Multifunctional Chiral Scaffolds in Combinatorial Synthesis

Four orthogonally stable protecting groups and a selectively cleavable anchor that are stable under basic conditions are required in order that carbohydrates can be employed as chiral polyfunctional scaffolds in combinatorial solid-phase syntheses of high diversity. The schematic representation shows the combinatorial synthesis with a carbohydrate scaffold (SG=protecting group, A=anchor, P=polymer carrier), which proceeds by sequential selective deprotection, functionalization, washing of the solid phase, and cleavage of the anchor.     

Three‐Dimensional Metal–Fullerene Frameworks

Hexakis‐substituted [60]fullerene adducts with icosahedral symmetry provide an unprecedented scaffold for the spatial arrangement of twelve functional groups with high geometric precision. This unique molecular symmetry identifies such polyfunctional organic building blocks as potential highly connective linkers for coordination polymer and metal–organic framework synthesis. Hereby, the linker exhibits a higher connectivity than the metal ions and with the main connectivity based on the ligand, this can create a new type of inversely cross‐linked framework. Two hexakis adducts bearing either twelve glycolic acid or 3‐hydroxypropionic acid side chains attached to its malonate units were incorporated as organic connectivity centers in the first fullerene‐containing three‐dimensional frameworks by coordination with Zn²⁺.     

Synthesis of a Novel Polyfunctional Anionic Macroinitiator from a Polyfunctional 1,1‐Diphenylethylene Agent

Summary: A polyfunctional 1,1‐diphenylethylene (DPE) agent was prepared by ring‐opening metathesis polymerization of a DPE‐functionalized norbornene monomer. Its reaction with sec‐butyllithium gave a novel polyfunctional anionic macroinitiator with one 1,1‐diarylalkyllithium initiation functionality per repeating unit. The significant applicability of this polyfunctional anionic macroinitiator was demonstrated by its excellent initiation efficiencies in anionic polymerization and a preparation of a graft copolymer with well‐controlled long and dense diblock grafts.

Preparation of a polyfunctional anionic macroinitiator based on ROMP and DPE chemistry.     

Synthesis and properties of strongly basic acrylate polyfunctional anion-exchange resin for uranium extraction

Some studies on the synthesis of strongly basic acrylate polyfunctional anion-exchange resins designed for the extraction of uranium from uranium ore leaching solutions were performed. The alkylation reaction conditions providing the synthesis of a polyfunctional anion-exchange resin with 55% of strongly basic groups were determined. Its sorption properties were studied using model solutions. The capacity of the alkylated polyfunctional anion-exchange resin with respect to uranium was shown to be highly competitive with foreign analogues using the comparative analysis of its ion-exchange characteristics with the parameters of known ion-exchange resins.     

聚合物强化辐射交联研究进展

本文综述卫应用含有多个Ｃ＝Ｃ不饱和基团的多官能团单体来强化辐射交联聚合物的研究进展，对强化交联的反应机理、多官能团单体的强化交联行为、强化交联的影响因素及强化交联的研究表征方法进行了介绍。     

Synthesis of new polyfunctional 2-pyrrolidinones from methyl 2-(carboethoxyhydroxymethyl)acrylate

The synthesis of new polyfunctional 2-pyrrolidinone derivatives from methyl 2-(carboethoxyhydroxymethyl)acrylate is described. These alkenes present an extremely high reactivity upon Michael addition with primary amines leading to a simple, mild, and efficient route to the preparation of new polyfunctional pyrrolidinones.     

Electrophilic and Nucleophilic Addition of Alkanethiols to 2-Vinyloxyethylmethacrylate

Under acid- or base-catalyzed conditions, thiols add regio- and chemos-electively either to vinyloxy or methacrylate group of vinyloxyalkyl-methacrylates to give polyfunctional methacrylates or polyfunctional vinyl ethers, respectively.     

Enhanced radiation crosslinking of carboxymethylated chitosan in the presence of acids or polyfunctional monomers

Carboxymethylated chitosan (CMCt) hydrogels were synthesized by γ-ray radiation-induced crosslinking in the presence of acids or polyfunctional monomers. Compared with that of CMCt hydrogels synthesized without additives, the gel fraction was improved and the gelation dose was decreased obviously after incorporating acids or polyfunctional monomers into CMCt hydrogels. The diffusion behavior of water in the CMCt gels prepared at different conditions was Fickian diffusion, and the swelling of the CMCt gels displayed characteristic pH sensitivity, which was analyzed by fluorescence molecular probes. Preliminary mechanism of radiation-induced crosslinking of CMCt in the presence of acids or polyfunctional monomers was discussed based on the FTIR and sol-gel analysis. Furthermore, it was found that CMCt hydrogels were hydrodegradable with high temperature (>60 °C), and incorporating polyfunctional monomers into the CMCt hydrogels also could improve the thermal stability of the CMCt hydrogels obviously.     

Nazarov Reagent: New Role for the [4+2] Domino Benzannulation Reaction to Construct Polysubstituted Benzenes

A new role for the Nazarov reagent was revealed in the [4+2] benzannulation reaction, and delivered a series of polyfunctional benzenes in high yields under mild conditions. This metal‐free process not only expanded the application of the Nazarov reagent in organic synthesis, but also provided a new, efficient way to construct polyfunctional benzenes.     

Preparation of highly functionalized arylmagnesium reagents by the addition of magnesium phenylselenide to arynes

The described polyfunctional arylmagnesium reagents, resulting from the highly regioselective addition of magnesium phenylselenide to functionalized arynes, can be trapped by a range of electrophiles, yielding polyfunctional selenoethers in 45-85% yields. Furthermore, these Grignard reagents can be used in Negishi cross-coupling reactions with iodoarenes after transmetalation to the corresponding arylzinc compounds, furnishing functionalized biaryl products in 55-73% yields.     

Neue Tetrazyklische,polyfunktionelle diterpenoide aus euphorbia myrsinites L. röntgenstrukturanalyse und stereochimie des 14-desoxo-14β-hydroxymyrsinols

Two groups of new polyfunctional diterpenes were isolated from E. myrsinites L.: the hitherto unknown irritant and cocarcinogenic esters M₂ and M′₂ of the tetracyclic, polyfunctional diterpene ingenol and six non-irritant mixtures of esters M₁, M₃ – M₅, M₇, and M₈ of a new polyfunctional diterpene called myrsinol. Their structures and stereochemistry were established.     

Preparation of polyfunctional arylmagnesium reagents bearing a triazene moiety. A new carbazole synthesis

[reaction: see text] The reaction of iodo- or bromo-substituted aryltriazenes with i-PrMgCl.LiCl generates the corresponding magnesiated derivatives which react with various electrophiles (acid chlorides, 3-iodoenones, allylic halides, aldehydes) affording polyfunctional triazenes. They can be readily converted to the corresponding polyfunctional aryl iodides. This new synthetic strategy was applied to prepare functionalized carbazoles.     

New polyfunctional magnesium reagents for organic synthesis

The iodine-magnesium exchange reaction allows the preparation of polyfunctional aryl, heteroaryl, or alkenyl magnesium reagents at low temperature. These reagents display the typical reactivity of Grignard compounds and undergo various copper-catalyzed reactions such as allylation or 1,4-addition. Using this halogen-metal exchange reaction, it was possible to generate polyfunctional magnesium reagents on the solid phase.     

Radiation crosslinking of polyamide 610

In the present paper the gel formation of polyamide 610 by γ-ray irradiation in the presence of polyfunctional monomer and γ-crystal nucleating agent under vacuum or air atmosphere had been studied. It was found that the gel formation was dependent on the content of polyfunctional monomer and nucleating agent. However, there was very little difference between gel contents irradiated under vacuum and air atmosphere. The results showed that the crosslinking by γ-irradiation enhanced the mechanical properties of PA610 especially at high temperature in the presence of polyfunctional monomer and γ-crystal nucleating agent. The mechanism of radiation crosslinking and scission was discussed according to the composition and quantity of gas released from three kinds of PA during irradiation.     

Flash photolysis and antioxidant activity

The photo-chemical behaviour of a number of mono- and polyfunctional commercial phenolic antioxidants has been examined using kinetic micro-second flash photolysis. The technique provides useful information on the relationship between antioxidant structure and the efficiency of phenoxy radical production. The kinetics of decay of the phenoxy radicals are also found to be dependent on structure. Mono-functional antioxidants give phenoxy radicals which decay by a second-order process whereas polyfunctional antioxidants give phenoxy radicals that decay by a first-order process. In the former case dimerisation to give bisphenolic coupling products is observed whereas, with the latter, this process is sterically inhibited. The value of flash photolysis as a probe for studying antioxidant activity is discussed.     

聚己内酯/聚酯丙烯酸酯共混物的辐射交联及其形状记忆行为

研究了聚酯丙烯酸酯 (PEA)类多官能团物质与聚己内酯 (PCL)共混物的辐射交联效应 .分别考察了多官能团PEA的用量、官能团数目、辐射交联剂量等因素对聚己内酯的辐射交联规律、动态力学性能、形状记忆行为等性能的影响 .结果表明 ,PCL PEA共混物的辐射交联规律不再遵从Charlesby Pinner关系式 ,而是符合陈欣方 刘克静 唐敖庆关系式 .多官能团PEA的加入可以显著提高PCL辐射交联的效率 ;相同剂量时 ,官能团数目越多、用量越大的样品 ,生成的凝胶含量越多 ,强化辐射交联效应越大 .DMA分析表明 ,PCL强化辐照交联后的弹性模量和耐热性能显著提高 .强化交联PCL在其熔点以上都呈现出高弹态平台 ,可以实现形状记忆 .且交联度较高 ,形状记忆恢复速率较快 .     

Minor compounds of the oleoroesin of the Kamchatka,Japanese, and Siberian larches

The polyfunctional compounds of the oleoresins of three species of larch have been studied. Larixol diacetate, 3β-hydroxyepimanool, and 15-oxopimara-4(14)-enoic 13-hydroxy-7-oxoabicta-8(14)-enoic, 3β-hydroxysandaracopimaric, and 8,15-dihydroxyabietic acids have been isolated for the first time. The investigation performed has shown that the oleoresins of the larch contain polyfunctional compounds of various structural types. Depending on the species, their composition changes, and this fact can be used in the chemotaxonomy of larches.     

Divergent synthetic routes to biologically relevant types of compounds: chiral polyfunctional γ-lactams and amino acids

Divergent and versatile synthetic routes leading to the title compounds are described. They start from a common chiral precursor derived from (−)-(S)-verbenone and afford polyfunctional γ-lactams and γ- and ε-amino acids. The cyclobutane moiety in these molecules acts as a chiral and polyfunctional platform providing stereogenic centres with unambiguous absolute configuration that control the chirality of the newly produced asymmetric carbons. Furthermore, it affords functional groups and carbon chains suitable not only to create the basic skeleton of the desired products but additional functional groups. These features confer on these derivatives a great versatility for further uses in the development of new drugs and as synthetic building blocks.     

Microwave‐enhanced Efficient Synthesis of Some Polyfunctional Pyridazines

Microwave‐enhanced highly efficient protocol for the synthesis of polyfunctional pyridazines beginning from 3,6‐dichloropyridazine in environmentally benign ionic liquids have been developed. The products obtained were 3‐amino‐6‐chloropyridazine, 3,6‐diaminopyridazine, and 3‐chloro‐6‐methoxypyridazine. These derivatives were then be converted to a variety of polyfunctional pyridazine derivatives. The ionic liquids used were 1‐n‐butyl‐3‐methylimidazolium hydroxide/tetrafluoroborate/hexafluorophosphate and 1,3‐di‐n‐butylimidazolium hydroxide. This powerful strategy is less time‐consuming green methodology. The ionic liquid employed may be recovered and recycled.