The Increasing Value of Biomass: Moving From C6 Carbohydrates to Multifunctionalized Building Blocks via 5-(hydroxymethyl)furfural

Recent decades have been marked by enormous progress in the field of synthesis and chemistry of 5-(hydroxymethyl)furfural (HMF), an important platform chemical widely recognized as the “sleeping giant” of sustainable chemistry. This multifunctional furanic compound is viewed as a strong link for the transition from the current fossil-based industry to a sustainable one. However, the low chemical stability of HMF significantly undermines its synthetic potential. A possible solution to this problem is synthetic diversification of HMF by modifying it into more stable multifunctional building blocks for further synthetic purposes.     

Simple Synthesis of 7‐Formyl‐indole

A simple route to 7‐formyl‐indole (5) is described in which appropriately functionalized o‐nitrotoluenes (1) are converted to 7‐hydroxymethyl‐indole (4) using the Batcho–Leimgruber process. Condensation of 3‐methyl‐2‐nitrobenzyl alcohol (1a) with N,N‐dimethylformamide dimethyl acetal yields the enamine 2a, which upon catalytic hydrogenation affords 4 in 22% yield. When the hydroxyl function in 1 is protected with pivaloyl or tetrahydropyranyl group, the yields of 4 are increased to 39% and 48%, respectively. Finally, 4 is oxidized with pyridinium chlorochromate (PCC) to afford 5 in 86% yield.     

Synthesis of carborane-containing phosphates by catalytic phosphorylation

The catalytic phosphorylation ofo-carboranylmethanol with different phosphorus acid chlorides has been studied. This method makes it possible to obtain esters of phosphorus acids and esters of the corresponding phosphorus acid chlorides containing carboranylmethyl groups. The catalytic phosphorylation of 1,2-bis(hydroxymethyl)-o-carborane affords both acyclic and cyclic phosphate esters. The structure of the synthesizedo-carborano[1,2-e]-1,3,2-dioxaphosphepane was confirmed by X-ray diffraction analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 145–149, January, 1995.     

Synthesis and study of organic nitrates of the heterofunctional series 3. Synthesis and structure of tris(hydroxymethyl)aminomethane dinitrate benzoate hydronitrate

Tris(hydroxymethyl)aminomethane dinitrate benzoate hydronitrate, the first representative of mixed nitric and carboxylic esters of aminopolyatomic alcohols, was obtained by the reaction of a mixture of concentrated HNO₃ and Ac₂O with 4,4-bis(hydroxymethyl)-2-phenyl-2-oxazoline. X-ray structural analysis demonstrated that the title compound exists in the crystal as two independent molecules. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 505–509, March, 1999.     

An effective new access to ethyl 2-[(alkylamino)(cyano)methyl] acrylates: first synthesis of ethyl 3-cyano-2-(hydroxymethyl) acrylate

A regioselective coupling of ethyl 2-(bromomethyl)-3-cyanoacrylate and primary amines is described to give ethyl 2-[(alkylamino)(cyano)methyl] acrylates in good yields. Whereas the conversion of allyl bromide in the presence of TEAF leads to the first synthesis of ethyl 3-cyano-2-(hydroxymethyl) acrylate.     

乙醇或乙醇-水为新的溶剂体系沉淀聚合制备单分散聚合物微球

以三羟甲基丙烷三丙烯酸酯(TMPTA)作交联剂,, 苯乙烯 (St) 作共聚单体,, 偶氮二异丁腈(AIBN)作引发剂,, 在低毒性乙醇和乙醇-水混合物这一新的溶剂体系中沉淀聚合反应4 h制备了单分散交联微球. 通过提高交联剂用量、引发剂用量和改变反应介质中水的用量探讨了提高单体转化率的方法. 结果表明,, 提高引发剂用量和增加溶剂中水的用量都能有效提高单体转化率并制得粒径均匀的微球. 保持其他条件不变,, 在乙醇中使用2 wt% AIBN仅能得到79%的单体转化率,, 提高AIBN用量至6 wt%或在介质中增加水的用量至28 vol%,, 在制得单分散微球的同时单体转化率可以达到95%以上. 文中对微球的形成机理和提高单体转化率的方法给出了理论解释.     

Challenges in modelling and optimisation of stability constants in the study of Cu-(TAPS)x-(OH)y system by polarography

This work describes the application of polarography, a technique scarcely used for modelling and optimisation of stability constants, in the study of copper complexes with [(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)amino]-1-propanesulfonic acid (TAPS). Direct current polarography (DCP), using low total copper ion and large total ligand to total copper concentration, enabled the full characterization of Cu-(TAPS)_x-(OH)_y system, whose complexation occurs in the pH range of copper hydrolysis and Cu(OH)₂ precipitation. Cu-(TAPS)_x-(OH)_y system was studied by DCP and glass electrode potentiometry (GEP) in aqueous solution at fixed total ligand to total metal concentrations ratios and varied pH values (25.0 °C; I = 0.1 M, KNO₃). The predicted model, as well as the overall stability constants values, are (as log β): CuL⁺ = 4.2, CuL₂ = 7.8, CuL₂(OH)⁻ = 13.9 and CuL₂(OH)₂²⁻ = 18.94. GEP only allowed confirming the stability constants for CuL⁺ and CuL₂ and was used to determine the pKa of TAPS, 8.342.Finally, a briefly comparative analysis between TAPS and other structural related buffers was done. Evaluation based on log β_CuL versus pKa revealed that TES, TRIS, TAPS and AMPSO coordinated via amino and hydroxymethylgroups forming a five-membered chelate ring. For BIS-TRIS and TAPSO, and possibly DIPSO, one or more five-membered chelate rings involving additional hydroxyl groups are also likely formed.     

Microchip-based electrochromatography: designs and applications

Different techniques and methods of electrochromatography on “lab on a chip” devices are reviewed. Described approaches include open-channel microchip electrochromatography relying on C₈, C₁₈ and novel gold nanoparticle (GNP) coating of microchannel wall; packed-channel microchip electrochromatography with new ways of automated loading and unloading of conventional octadecylsilica beads; monolith-based microchip electrochromatography with tailored casting of stationary phase at the specific places of microfluidic network and novel photolitographically fabricated collocated monolithic structures. Specific issues related to the microchip electrochromatography, i.e. importance of high aspect ratio of the microchannels in the open-channel electrochromatography or approaches eliminating the wall effect in the monolith-based electrochromatography, are discussed. Various applications for environmental, pharmacological, genomic and proteomic analysis are described. The operation parameters of reviewed microsystems are summarized in easy-to-read tables.     

鱼心中新的4—羟基—2—羟甲基—2—十七烷基—1,5—戊内酯的研究

从鳙鱼（Ａｒｉｓｔｉｃｈｔｈｙｓｎｏｂｉｌｉｓ）的心脏肌肉中分离得到一种带长链的六环内酯化合物，熔点６２．３～６２．８℃，由１ＨＮＭＲ，１３ＣＮＭＲ，ＩＲ，ＭＳ等波谱数据推导其化学结构为４羟基２羟甲基２十七烷基１，５戊内酯，文献检索表明为新化合物。     

季戊四醇双缩醛的合成

以苯为溶剂，ＴｓＯＨ为催化剂合成了几种长直链的季戊四醇双缩醛。