Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters

Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.     

Modified Coumarins. 9. Synthesis of Amino-Acid Derivatives of 3-(2,3,5-Trimethyl-7-oxofuro[3,2-g]chromen-6-yl)propanoic Acid

Furocoumarins modified by amino acids were prepared by condensation of the N-hydroxysuccinimide ester of 3-(2,3,5-trimethyl-7-oxofuro[3,2-g]chromen-6-yl)propanoic acid with amino acids.     

Synthesis of alkenes from tertiary esters utilizing the triphenylphosphine-iodine system

The treatment of tertiary esters with triphenylphosphine and iodine under mild conditions gives the most stable alkene in good yield. Formates, acetates and trifluoroacetates were studied.     

Dynamic mechanical thermal analysis transitions of partially and fully substituted cellulose fatty esters

The main transitions of cellulose fatty esters with different degrees of substitution (DSs) were investigated with dynamic mechanical thermal analysis. Two distinct main relaxations were observed in partially substituted cellulose esters (PSCEs). They were attributed to the glass‐transition temperature and to the chain local motion of the aliphatic substituents. The temperatures of both transitions decreased when DS or the number of carbon atoms (n) of the acyl substituent increased. Conversely, all the transitions of fully substituted cellulose esters occurred within a narrow temperature range, and they did not vary significantly with n. This phenomenon was explained by the formation of a crystalline phase of the fatty substituents. The presence of few residual OH groups in PSCEs was responsible for a large increase in the storage bending modulus, and it eliminated the effect of n on damping. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 281–288, 2003     

Electrochemically induced processes in the formation of phosphorus acid derivatives. 2. The role of polymerization processes in the electrosynthesis of the esters of phosphorus acids from white phosphorus

The mechanism of the electrosynthesis of phosphate esters from white phosphorus was investigated. It was shown that the reaction takes place by two paths, i.e., monomeric (with the participation of dissolved phosphorus) and polymeric (with the participation of phosphorus on the surface of an emulsion drop). It was established that in an alcohol solution of tetraethylammonium iodide the main part of the final product is formed through an intermediate polymeric compound. It was noticed that by studying the dynamics of the accumulation of the dissolved product during electrolysis it is possible to trace the mechanism of reaction of the phosphorus at the individual stages of the process.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420028 Kazan'. V. I. Ul'yanov-Lenin Kazan' State University, 420028 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1328–1333, June, 1992.     

液晶研究（Ⅰ）──4＇－酰基－4－羟基－1，1＇－联苯酯类液晶的合成与性质

以４＇－羟基联苯为原料合成了８种新型４＇－酰基－４－羟基联苯酯类化合物．除化合物５＿ｈ外，均为新的近晶相液晶化合物．它们具有较宽的相变温度范围和较高的热稳定性．用偏光显微镜和差热分析仪研究了它们的相行为，讨论了分子结构对液晶相行为的影响．     

Characterization of Ultrathin Films of Cellulose Esters

The adsorption of cellulose acetate (CA), cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) from solutions prepared in acetone onto silicon wafers led to ultrathin films, which were characterized by ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The polysaccharides films were characterized in the air just after their formation and after annealing at temperatures higher than their glass transition temperature or melt temperature. The films thickness close to 2 nm and surface roughness did not vary significantly upon annealing. AFM images revealed the presence of small clumps dispersed on a homogeneous layer, which covered completely the Si wafers. Such topographic details were also observed after annealing. However, upon annealing the films surfaces changed from hydrophilic to hydrophobic, evidencing molecular re-orientation at the solid–air interface. The adhesion of bovine serum albumin (BSA) and lipase onto the cellulose esters films was quantified in order to evaluate the possibility of applying such films as selective support for biomolecules.     

Enzymatic synthesis of neopentylpolyol esters in organic media

Utilization of lipases for synthesis of esters of hydrophilic polyols has been investigated. The choice of a suitable solvent is crucial in this type of reaction. An interesting case is fatty acid esters from neopentylpolyols, such as trimethylolpropane, which are of great interest as high temperature lubricants. Enzymatic synthesis of trimethylolpropane tricaprylate was studied as an alternative to chemical manufacturing. Triester production occurred only if the water produced by esterification was continuously removed from the medium. In these condition, kinetics of appearance and transformation of mono-, di- and triesters were determined in order to define optimal conditions.     

Some Conversions of Thiazoline Carboxylic Acid Esters

We have carried out solvolysis of the previously described ethyl esters of 3-methyl(aryl)-4-methyl-2-thioxothiazoline-5-carboxylic acids, leading to the corresponding acids without breaking down the heterocycle. We synthesized a series of novel esters from the latter by treatment with dimethyl sulfate or reactive halides. Of these, only in the case of the ethyl ester of 3,4-dimethyl-2-thioxothiazoline-5-carboxylic acid did we obtain the hydrazinolysis product (the hydrazide), from which we synthesized novel hydrazones by treatment with aldehydes and ketones.     

烯胺酮与烯胺酯的交叉缩合反应及自缩合反应的区域选择性研究

烯胺酮与烯胺酯以(3C+3C)缩合反应形成多取代芳环化合物,具有区域选择性。用波谱和 X-射线衍射技术确定了产物的结构,讨论了反应机理。