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101.
Herein we report the synthetic strategy towards the pyran core of macrolactin 3 via Sharpless epoxidation, titanium(IV) mediated regioselective ring-opening reaction of epoxyallyl alcohol/epoxy alcohol and oxa-Michael addition as the key steps. 相似文献
102.
The synthesis and copolymerization of 4-hydroxybenzylglycolide: experimental and theoretical aspects
《Mendeleev Communications》2021,31(5):701-703
Based on tyrosine, 4-hydroxybenzylglycolide was synthesized. Its study in ring-opening copolymerization with lactides in view of the ability of the phenolic hydroxy group to initiate polymerization was performed experimentally and with DFT modeling. 相似文献
103.
The reaction of esterification of benzoic acid with benzyl chloride was chosen as a model reaction to study the esterification by SN2 promoted by tertiary amine as deprotonating agent. The use of ionic liquid (IL) 1,3-dimethylimidazolium methanesulfonate [MMIm][OMs] as reaction medium has proven to give quantitative yield of the ester, but interestingly the reaction does occur even in solvent-free conditions, where the acid + the amine form a liquid system (a protic IL) in situ. This last methodology was extended to several carboxylic acids in conditions of atom economy (i.e., without excess of any reagent), giving moderately good yields of esters (54–78%) recovered by weight in pure form. 相似文献
104.
Rongyi Zhang Qigang Li Dr. Qiqiang Xie Prof. Dr. Chuanfa Ni Prof. Dr. Jinbo Hu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(71):17773-17779
The ring-opening difluoromethylation-halogenation of cyclic (thio)ethers is reported through a simple strategy relying on carbon-chalcogen bond activation with difluorocarbene. The reaction proceeds through in situ protonation of the previously little-known difluoromethylene oxonium or sulfonium ylide intermediate followed by ring-opening with halide ion to afford halogenated acyclic difluoromethyl (thio)ethers that can then be employed for further elaboration. TMSCF2X (X=Br, Cl) are unique reagents to achieve this synthetic purpose, which serve as both the difluorocarbene source and the halide ion source. 相似文献
105.
Dynamical Bifurcation in Gas‐Phase XH− + CH3Y SN2 Reactions: The Role of Energy Flow and Redistribution in Avoiding the Minimum Energy Path 下载免费PDF全文
Yaicel G. Proenza Prof. Miguel A. F. de Souza Prof. Ricardo L. Longo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(45):16220-16229
The gas‐phase reactions of XH? (X=O, S) + CH3Y (Y=F, Cl, Br) span nearly the whole range of SN2 pathways, and show an intrinsic reaction coordinate (IRC) (minimum energy path) with a deep well owing to the CH3XH???Y? (or CH3S????HF) hydrogen‐bonded postreaction complex. MP2 quasiclassical‐type direct dynamics starting at the [HX???CH3???Y]? transition‐state (TS) structure reveal distinct mechanistic behaviors. Trajectories that yield the separated CH3XH+Y? (or CH3S?+HF) products directly are non‐IRC, whereas those that sample the CH3XH???Y? (or CH3S????HF) complex are IRC. The IRCIRC/non‐IRC ratios of 90:10, 40:60, 25:75, 2:98, 0:100, and 0:100 are obtained for (X, Y)=(S, F), (O, F), (S, Cl), (S, Br), (O, Cl), and (O, Br), respectively. The properties of the energy profiles after the TS cannot provide a rationalization of these results. Analysis of the energy flow in dynamics shows that the trajectories cross a dynamical bifurcation, and that the inability to follow the minimum energy path arises from long vibration periods of the X?C???Y bending mode. The partition of the available energy to the products into vibrational, rotational, and translational energies reveals that if the vibrational contribution is more than 80 %, non‐IRC behavior dominates, unless the relative fraction of the rotational and translational components is similar, in which case a richer dynamical mechanism is shown, with an IRC/non‐IRC ratio that correlates to this relative fraction. 相似文献
106.
107.
Daniel D. Stöbener Dorian Donath Marie Weinhart 《Journal of polymer science. Part A, Polymer chemistry》2018,56(21):2496-2504
Low-molecular weight linear poly(glycidyl ether)s are typically synthesized via the “classical,” oxy-anionic ring-opening polymerization (ROP) of glycidyl ether monomers at elevated temperatures. To reduce reaction times, a fast process was developed to synthesize oligo(glycidyl ether)s (OGEs) in bulk at a gram-scale utilizing microwave heating. Well-defined thermoresponsive copolymers comprising glycidyl methyl ether and ethyl glycidyl ether with molecular weights of up to 3 kDa were synthesized via microwave-assisted ROP with reaction times of approximately 10 min. The fast reaction kinetics were attributed to the rapid and uniform heating and high temperatures reached during the reaction. Consequently, no significant microwave-specific acceleration of the oxy-anionic ROP was observed. The temperature-triggered phase transition of the OGEs in aqueous solution revealed cloud point temperatures that are highly dependent on the OGE molecular weight, concentration, and comonomer composition, which extends previously reported data. Furthermore, oligo(glycidyl ether) acrylates (OGEAs) with reactive, functional end groups were directly accessible via in situ quenching of the anionic, microwave-assisted ROP with acrylic acid chloride. The obtained thermoresponsive OGEA macromonomers represent a promising material for the functionalization of surfaces via radical grafting methods to obtain functional, thermoresponsive coatings with potential application in cell culture. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2496–2504 相似文献
108.
Muhammad Imran ul‐haq Rajesh A. Shenoi Donald E. Brooks Jayachandran N. Kizhakkedathu 《Journal of polymer science. Part A, Polymer chemistry》2013,51(12):2614-2621
Hyperbranched polyglycerols (HPGs) are globular structures with a large number of functionalizable hydroxyl groups and have excellent in vitro and in vivo biocompatibility profiles comparable to polyethylene glycol. This work introduces a facile method for the synthesis of medium molecular weights (Mws) (50–300 kDa) HPGs, which has been difficult to synthesize with low polydispersity, with the assistance of solvents by ring opening polymerization. The influence of different solvents (1,4‐dioxane, tetrahydropyran (THP), ethylene glycol diethyl ether (EGDE) and decane), solvent to glycidol ratio, concentration of glycidol and the time of polymerization on Mw and polydispersity of HPGs has been studied. The Mw and polydispersity of HPGs are significantly affected by the nature of the polymerization phase (homogeneous or heterogeneous) and chemical structure of the solvent. The differences in the solvation of the potassium cations and change in the nucleophilicity of the alkoxide anion in various solvents may be responsible for the changes in Mw and PDI of the HPG. The Mw of the HPG decreases in the order 1,4‐dioxane > THP > EGDE >decane. The microstructure, solution and thermal properties of the HPG do not depend on the nature of solvent. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2614–2621 相似文献
109.
110.
Efficient Synthesis of Cyclic Block Copolymers by Rotaxane Protocol by Linear/Cyclic Topology Transformation 下载免费PDF全文
Stephanie Valentina Dr. Takahiro Ogawa Dr. Kazuko Nakazono Dr. Daisuke Aoki Prof. Dr. Toshikazu Takata 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(26):8759-8762
High‐yielding synthesis of cyclic block copolymer (CBC) using the rotaxane protocol by linear‐cyclic polymer topology transformation was first demonstrated. Initial complexation of OH‐terminated sec‐ammonium salt and a crown ether was followed by the successive living ring‐opening polymerizations of two lactones to a linear block copolymer having a rotaxane structure by the final capping of the propagation end. CBC was obtained in a high yield by an exploitation of the mechanical linkage through the translational movement of the rotaxane component to transform polymer structure from linear to cyclic. Furthermore, the change of the polymer topology was translated into a macroscopic change in crystallinity of the block copolymer. 相似文献