生物柴油及1,3-丙二醇联产工艺产业化进展

生物柴油作为可再生的清洁能源,已在美国、欧盟等多个国家和地区推行使用.在生物柴油的生产过程中,最高可得到约10%的副产物甘油,副产物甘油的去向将成为生物柴油大规模产业化发展所面临的严峻问题.1,3-丙二醇是一种重要的化工原料,作为合成新型聚酯PTT的原料,1,3-丙二醇已引起人们的广泛关注.以生物柴油副产物甘油为原料耦合生产1,3-丙二醇,不仅解决了生物柴油副产物甘油的出路问题,同时降低了1,3-丙二醇的生产成本.本文详细介绍了生物柴油及1,3-丙二醇生产技术及联产工艺的研究进展,并对其应用前景进行了展望.     

生物柴油及1,3-丙二醇联产工艺产业化进展

生物柴油作为可再生的清洁能源,已在美国、欧盟等多个国家和地区推行使用。在生物柴油的生产过程中,最高可得到约10%的副产物甘油,副产物甘油的去向将成为生物柴油大规模产业化发展所面临的严峻问题。1,3-丙二醇是一种重要的化工原料,作为合成新型聚酯PTT的原料,1,3-丙二醇已引起人们的广泛关注。以生物柴油副产物甘油为原料耦合生产1,3-丙二醇,不仅解决了生物柴油副产物甘油的出路问题,同时降低了1,3-丙二醇的生产成本。本文详细介绍了生物柴油及1,3-丙二醇生产技术及联产工艺的研究进展,并对其应用前景进行了展望。     

甘油催化氢解制备精细化学品的研究进展

随着生物柴油产业的快速发展,作为副产物的甘油大量过剩,因而有效利用甘油既能促进生物柴油产业的良性发展,又能节约大量石油资源。通过甘油催化氢解的方式来制备高附加值化学品丙二醇、乙二醇和丙醇等是甘油转化研究中最有潜在应用价值的路径之一,甘油氢解反应易于实现连续化生产,且目标产物附加值高、选择性高,因而具有良好的经济效益。本文首先简要介绍了甘油化学,深入探讨了甘油的氢解机理,然后重点综述了甘油氢解制备1, 2-丙二醇、1, 3-丙二醇、乙二醇和丙醇高效催化剂的研究进展,并对甘油氢解未来的研究方向和发展趋势作了进一步展望。     

甘油催化氢解的研究与应用

近年来由于生物柴油产业的快速发展,甘油作为其生产过程中的副产品大量生成,合理利用这些过剩的甘油将有助于增加整个生物柴油产业的经济效益。本文对近年来利用甘油为原料催化氢解合成二元醇（1,2-丙二醇、1,3-丙二醇和乙二醇）的研究进展进行了综述,介绍了甘油催化氢解的研究背景,着重讨论了甘油催化氢解生成二元醇的反应机理（包括脱水-加氢机理、脱氢-加氢机理和螯合机理）和甘油催化氢解在生产二元醇上的应用,并对甘油催化氢解的发展前景做了展望。     

甘油催化氢解制备1,2-丙二醇催化剂研究进展

综述了近年来通过生物柴油生产过程中的副产物甘油催化氢解制备高附加值1,2-丙二醇的催化剂研究新进展.对各类催化剂的研究工作做了简要的总结,并对研究热点做出展望.     

生物基甘油氢解合成1,3-丙二醇催化剂的研究进展

1,3-丙二醇（1,3-PDO）作为聚酯单体原料有广阔的市场空间,在化妆品和医药等领域也被广泛应用.由生物基甘油选择氢解一步法合成1,3-PDO工艺被认为是一条绿色环保和高经济性的技术路线.我们在这里主要介绍了甘油氢解制备1,3-PDO催化剂的研究进展,对催化剂类型、催化剂的合成方法和工艺条件进行了归类总结;分析了多种催化剂体系的甘油氢解反应机理,指出了该反应工业化过程中存在的一些问题,并展望了今后的研究发展方向.     

甘油在微生物代谢合成及生物催化中的应用

生物柴油是一种可再生能源,因其可替代石油来源的柴油而日益受到重视。随着生物柴油工业的蓬勃发展,其制备过程中的主要副产物甘油出现明显的产能过剩。作为一种廉价的清洁资源,甘油的深度开发和利用既是发展生物柴油工业的关键,也符合绿色化学的发展要求。近年来,甘油不仅作为重要的起始原料用于一些高附加值化学品的制备,而且因其独特的理化性质和易降解、生物相容性好等特性,在生物催化和绿色溶剂领域的应用研究日趋活跃。本文主要综述了甘油在工业微生物发酵、生物合成和绿色溶剂领域的研究进展,并就其应用中存在的一些问题,如甘油原料品质和微生物利用效率等进行分析,同时展望了甘油在生物催化领域的应用前景。     

生物法PTT纤维及原料研究进展

生物质材料在许多领域显现出广阔的应用前景。PTT纤维作为生物质纤维新品种,以其优良的性能、环保和可持续发展成为业内研究的新热点。系统介绍了国内外生物法1,3-丙二醇研究进展及生产概况,指出微生物法的能耗优势和技术瓶颈;详细综述了生物法PTT纤维制备、结构及性能等方面的研究进展,阐明了发展生物法纤维及其制品的有利形势。随着生物法1,3-丙二醇制备技术的日臻完善,长期制约PTT纤维发展的原料成本进一步降低,生物法PTT纤维的高速发展值得期待。     

丙烯醇反马氏水合制备1,3-丙二醇

1,3-丙二醇具有很高的经济价值，是合成纤维聚对苯二甲酸丙二酯的重要原料。基于甘油甲酸介入法获得的丙烯醇作为平台分子，通过丙烯醇与TiCl4-NaBH4反应，首次实现常温常压下1,3-丙二醇的制备, 为1,3-丙二醇的合成提供了一条新的路径。在最优条件下，1,3-丙二醇的产率68.73%，推测反应机理为：TiCl4和NaBH4发生反应，生成中间体 “BH3”，进而实现了丙烯醇反马氏水合制备1,3-丙二醇。     

亚临界条件下地沟油制备生物柴油副产物中有机氯化物的定性检测及来源分析

该文介绍了一种生物柴油副产物粗甘油和拔出轻组分中有机氯化物的气相色谱-质谱（GC-MS）定性检测方法。样品来自于亚临界条件下地沟油与甲醇的酯交换反应，总氯含量较高。在GC-MS分析之前采用正己烷萃取脱除样品中的脂肪酸甲酯和游离脂肪酸等脂溶性干扰组分，对参考标准样品3-氯代甘油和2-氯代甘油以及样品的脱脂水相部分进行苯硼酸衍生化、正己烷萃取、浓缩等处理，经正己烷复溶后进行GC-MS分析。结果表明，生物柴油副产物中的有机氯化物主要为3-氯代甘油和2-氯代甘油。参考已有文献的研究结果和生物柴油制备工艺对有机氯化物的来源进行了讨论，推断原料地沟油中存在的大量无机氯盐是导致产生3-氯代甘油和2-氯代甘油的主要原因。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.