Paired electrooxidation IV. Decarboxylation of sodium gluconate to D-arabinose

A paired electrooxidative method has been developed to synthesize D-arabinose in a divided cell. D-arabinose is a material which has an important role in the production of vitamin B2 and DNA. Sodium gluconate was directly oxidized at the anode and indirectly oxidized in the catholyte by bubbling oxygen which was reduced to H₂O₂ and OH free radicals. In the catholyte, indirect oxidation of sodium gluconate was mediated by Fe³⁺ and OH free radicals. The optimal current efficiencies for D-arabinose production in the anolyte and catholyte were found to be 88.37% and 39.12%, respectively, and the total current efficiency of the paired electrooxidation was 127.49%. The paired electrosynthesis of D-arabinose is more economical in terms of power consumption than electrosynthesis that employ a single anode or cathode as the working electrode. The influence of cathodic/anodic CV and I/E curves, redox mediators and the amount of charge passed were also examined.     

氨基酸脱羧反应研究进展

氨基酸脱羧是重要的生物质资源转化途径,通过氨基酸脱羧反应能够得到胺及胺的衍生物。该文综述了氨基酸脱羧基的不同方法,包括酶脱羧、化学催化脱羧、热脱羧和光电化学脱羧方法。重点阐述了使用化学催化剂脱羧的研究进展,对均相催化剂和非均相催化剂催化脱羧的催化途径以及机理进行了详细的介绍。中国目前已经成为氨基酸的生产与消费大国,氨基酸工业在食品与饲料等领域的发展已经趋于成熟,但是对氨基酸下游产品的工业化仍然缺少配套的技术与经验。为了应对氨基酸工业核心技术的垄断问题,开发新型高效催化剂与更加高效的工艺路线的研究显得尤为重要。     

Carbon-coated Ni-Co alloy catalysts: preparation and performance for in-situ aqueous phase hydrodeoxygenation of methyl palmitate to hydrocarbons using methanol as the hydrogen donor

Carbon-coated Ni, Co and Ni-Co alloy catalysts were prepared by the carbonization of the metal doped resorcinol-formaldehyde resins synthesized by the one-pot extended Stöber method. It was found that the introduction of Co remarkably reduced the carbon microsphere size. The metallic Ni, Co, and Ni-Co alloy particles (mainly 10–12 nm) were uniformly distributed in carbon microspheres. A charge transfer from Ni to Co appeared in the Ni-Co alloy. Compared with those of metallic Ni and Co, the d-band center of the Ni-Co alloy shifted away from and toward the Fermi level, respectively. In the in-situ aqueous phase hydrodeoxygenation of methyl palmitate with methanol as the hydrogen donor at 330 °C, the decarbonylation/decarboxylation pathway dominated on all catalysts. The Ni-Co@C catalysts gave higher activity than the Ni@C and Co@C catalysts, and the yields of n-pentadecane and n-C₆–n-C₁₆ reached 71.6% and 92.6%, respectively. The excellent performance of Ni-Co@C is attributed to the electronic interactions between Ni and Co and the small carbon microspheres. Due to the confinement effect of carbon, the metal particles showed high resistance to sintering under harsh hydrothermal conditions. Catalyst deactivation is due to the carbonaceous deposition, and the regeneration with CO₂ recovered the catalyst reactivity.     

四氟苯菊酯的合成

以四氯对苯二甲氰为原料,经过氟化、水解、脱羧、酰氯化、还原5步反应合成四氟苄醇,再与二氯菊酰氯缩合得四氟苯菊酯。反应总收率在39％以上,含量达93％。     

Thermal behaviour of partially neutralised ethylene-maleic acid copolymer

As part of continuing studies on the cure of candidate polymers for waterborne coatings, the thermal behaviour of partially neutralised ethylene-maleic acid copolymer, EMA, has been examined. Films of EMA neutralised with a variety of bases were heated at 250°C. For this copolymer, as for poly(acrylic acid) at the same temperature, reflectance infrared spectroscopy has shown that heating led initially to anhydride formation. In the unneutralised state, or with the divalent ions calcium, magnesium, cobalt or zinc, further heating led to little or no further reaction. By contrast, the presence of univalent metal ions lithium, sodium and potassium caused a second reaction to occur, namely decarboxylation to yield keto crosslinks. This second reaction, however, did not occur to the extent that it does with poly(acrylic acid) under identical conditions. Possible reasons for this are discussed. Unlike poly(acrylic acid), EMA when partially neutralised was found not to form continuous films on the tin-plate substrate.     

Molecular Simulation of Naphthenic Acid Removal on Acidic Catalyst II. Experimental results of catalytic decarboxylation over acidic catalysts

The energy barriers of thermal decarboxylation reactions of petroleum acids and catalytic decar-boxylation reactions of Brnsted acid and Lewis acid were analyzed using molecular simulation technology. Compared with thermal decarboxylation reactions of petroleum acids, the decarboxylation reactions by acid catalysts were easier to occur. The decarboxylaton effect by Lewis acid was better than Brnsted acid. The mechanisms of catalytic decarboxylation over acid catalyst were also verified by experiments on a...     

Direct Decarboxylative Alkynylation of α,α‐Difluoroarylacetic Acids under Transition Metal‐Free Conditions

An efficient and generally applicable protocol for decarboxylative coupling of α,α‐difluoroarylacetic acids with ethynylbenziodoxolone (EBX) reagents has been developed, affording α,α‐difluoromethylated alkynes bearing various functional groups in moderate to excellent yields. Remarkably, this potassium persulfate (K₂S₂O₈)‐promoted reaction employs water as solvent under transition metal‐free conditions, thus providing a green synthetic approach to α,α‐difluoromethylated alkynes.

     

Copper(II)/Silver(I)‐Catalyzed Sequential Alkynylation and Annulation of Aliphatic Amides with Alkynyl Carboxylic Acids: Efficient Synthesis of Pyrrolidones

A highly efficient protocol for the synthesis of pyrrolidones by the copper‐catalyzed alkynylation/annulation of aliphatic amides with alkynyl carboxylic acids is discussed in this paper. A broad range of easily accessible alkynyl carboxylic acids were introduced at the β‐methyl group of aliphatic amides with the assistance of an 8‐aminoquinolyl auxiliary group via decarboxylation to achieve the subsequent cyclic C N bond formation within one hour. High selectivity of β‐methyl groups over methylene groups was observed, and the extension of this catalytic system to the activation of methylene C H bonds failed. The substrates with two different groups at the α‐position of the aliphatic amides lead to the formation of diastereoisomers which is determined by ¹H NMR spectroscopy. The initially produced products with Z‐configurations can be easily transformed to the corresponding products with E‐configurations by the treatment with dilute p‐toluenesulfonic acid after the reaction. This catalytic tandem decarboxylative cyclization provides a new opportunity for the direct functionalization of sp³ C H bonds.