Direct Use of Benzylic Alcohols for Gold(III)‐Catalyzed S‐Benzylation of Mercaptobenzoic Acids in Water

We demonstrate the gold(III)‐catalyzed direct substitution of benzylic alcohols in water. These atom economic and environmentally benign protocols afford S‐benzylated products in moderate to excellent yields. In contrast, common Lewis or Brønsted acids as catalyst, and organic solvents such as dichloromethane or toluene were ineffective for the S‐benzylation of mercaptobenzoic acids. Water can be an attractive tool for new transition metal‐catalyzed reactions. A Hammett study for the rate constants with various substituted alcohols shows a good correlation (R²=0.97) between the log(k_X/k_H) and the σ⁺ value of the respective substituents. From the slope negative ρ values of 2.35 are obtained, suggesting that there is a build‐up of positive charge in the transition state. Our catalytic system can be performed with the use of only 2 mol% of gold(III) catalyst without any other additives in water, and scaled up to 10 mmol scale (85% isolated yield). Notably, the present method can accomplish the S‐benzylation of unprotected mercaptobenzoic acids, which is chemoselective and leaves the carboxyl group intact. Furthermore, the direct substitution of allylic and propargylic alcohols also proceeded smoothly in good yields.

     

But‐2‐ene‐1,4‐diamine and But‐2‐ene‐1,4‐diol as Donors for Thermodynamically Favored Transaminase‐ and Alcohol Dehydrogenase‐Catalyzed Processes

Both cis‐ and trans‐but‐2‐ene‐1,4‐diamines have been prepared and efficiently applied as sacrificial cosubstrates in enzymatic transamination reactions. The best results were obtained with the cis‐diamine. The thermodynamic equilibrium of the stereoselective transamination process is shifted to the amine formation due to tautomerization of 5H‐pyrrole into 1H‐pyrrole, achieving high conversions (78–99%) and enantiomeric excess (up to >99%) by using a small excess of the amine donor. Furthermore, when the reaction proceeded, a strong coloration was observed due to polymerization of 1H‐pyrrole. A structurally related compound, cis‐but‐2‐ene‐1,4‐diol, has been utilized as cosubstrate in different alcohol dehydrogenase (ADH)‐mediated bioreductions. In this case, high conversions (91–99%) were observed due to a lactonization process. Both strategies are convenient from both synthetic and atom economy points of view in the production of valuable optically active products.

     

5-氨基-1-戊醇的制备

以1,5-戊二醇为起始原料,与30%盐酸氯代反应得到5-氯戊醇,再与氨气(氨水)氨基化,得目标产物5-氨基-1-戊醇。考察了原料配比、反应温度等因素的影响。结果表明:以过量1,5-戊二醇为原料,水做溶剂,氯化氢取代生成的5-氯戊醇转化率较高,套用收率在90%以上;5-氯戊醇在90℃,乙醇做溶剂,氨气过量20倍条件下,反应2 h,得到5-氨基-1-戊醇,收率73%,纯度99%。     

Synergistic Effect on Wettability of Mixtures of Amine Oxides,Alkylpolyglucosides, and Ethoxylated Fatty Alcohols

The mixture proportions of three surfactants, i.e. an alkylpolyglucoside (APG), an ethoxylated fatty alcohol, and an amine oxide (AO), were optimized by applying Response Surface Methodology in order to achieve the surfactant ratio that produces the highest wetting power. The synergistic effect of the binary samples of AO with the other surfactants was firstly verified. An improvement in this synergistic effect on wettability was found in the ternary mixture. In the experimental range analyzed, the surfactant concentration ratio that produced the highest wettability was a composition with 19.3 % APG, 30.1 % ethoxylated alcohol, and 50.6 % lauramine oxide.     

腰果酚/聚乙烯醇改性酚醛树脂的制备

以腰果酚、聚乙烯醇作为苯酚与甲醛缩聚的改性剂,研究了腰果酚和聚乙烯醇的用量,催化剂类型和用量等对其性能的影响。结果表明:改性酚醛树脂的最佳条件为:苯酚、腰果酚、聚乙烯醇、甲醛的最佳摩尔比为0.85:0.32:0.02:1,最佳的催化剂为苯磺酸,用量为4.5%。     

聚乙烯醇在石膏聚苯板外墙内保温体系中的应用

介绍适用于夏热冬冷地区的石膏聚苯板外墙内保温体系的特点、材料组成、产品配方、石膏以及外加剂的性能等。通过实验确定了聚乙烯醇粉末胶粘剂在石膏聚苯板外墙内保温体系中的作用。     

PVA纤维增强应变硬化水泥基材料韧性性能研究

水泥基材料抗拉强度低、韧性差是其易于开裂、导致结构耐久性低劣的主要原因之一。高模量聚乙烯醇(PVA)纤维可增强水泥基材料韧性,使其呈现准应变硬化和多缝开裂特征,从而改善结构耐久性。本文通过四点弯曲试验得出了不同加载速率和不同配比应变硬化水泥基复合材料(PVA-SHCC)的力-变形曲线并用CONSOFT软件计算断裂能。结果表明,硅灰使材料的抗压强度有所提高,但最大抗弯承载力和变形下降,断裂能随之降低;甲基纤维素使PVA-SHCC脆性增大;随着加载速率的降低,材料表现出更好的应变硬化性能,微裂缝条数增多。     

碳氢/有机硅/低碳醇三元系泡沫及抑制煤自燃的效果分析

泡沫灭火剂是常用的火灾扑救方法之一,但常规泡沫灭火剂存在半衰期短,析液、聚并迅速而影响灭火效能的问题,基于火灾化学和活性剂技术,提出碳氢表面活性剂SDS、有机硅表面活性剂LS-99和低碳醇的三元系泡沫体系,并系统探究碳氢/有机硅/低碳醇的复配配比。通过表面张力、发泡高度、稳泡系数的大量测试,发现LS-99的临界胶束浓度为0.0083%。LS-99和SDS二元系在降低表面张力、提升发泡高度和稳泡系数方面具有良好的协同增效作用。在此基础上引入适量浓度的能够延缓泡沫析液、聚并的异丁醇,设计出了性能优良的碳氢/有机硅/低碳醇泡沫灭火剂。LS-99、SDS和异丁醇的质量分数为0.1%时,测试结果表明SDS/LS-99/醇三元系泡沫的发泡倍数可达52.5倍,25%析液时间可达210 s,300 s时的稳泡系数高达0.958,半衰期远超常规泡沫。煤自燃的灭火抑制实验表明,SDS/LS-99/醇三元系泡沫作用下,煤自燃各反应阶段的活化能相较于空气氛围均增大,反应难度增强;最大失重速率下降,反应剧烈程度减弱。初期吸热阶段的吸热量为78.3 J/g,大于空气氛围下煤氧复合的吸热量,吸热增幅高达2.16倍。放热阶段的放热量为1765.4 J/g,相较于空气氛围放热降幅达到15.15%,表明SDS/LS-99/醇三元系泡沫对煤自燃具有良好的灭火效果。     

农林废弃物气化合成混合醇生命周期环境影响分析

生物质热化学气化合成混合醇技术具有工艺相对简单、产物的能源化工应用广泛等优点,为准确评价该技术的资源能源消耗、辨析合成燃料的环境性能,基于生命周期分析框架和ReCiPe2016中点评价方法,对农林废弃玉米秸秆和木屑经气化、催化合成混合醇工艺的清单和9种环境影响类型开展分析和比较。结果表明：农林业阶段均为环境影响的主要阶段,秸秆混合醇生命周期影响高于木屑混合醇。前者的臭氧层耗竭潜值、海洋和淡水富营养化潜值、全球变暖潜值均为木屑混合醇相应结果的9倍以上。废弃物原料高碳含量和高混合醇收率有利于降低资源消耗和环境影响。与石化汽油相比,秸秆和木屑混合醇的全球变暖和化石能源消耗潜值均降低40%以上。     

Kinetics,mechanism, and simulation of hydrogen transfer reaction of α, β-unsaturated aldehydes to allylic alcohols

Homogeneous hydrogen transfer reactions of methacrolein (MAL) and isopropanol to methallyl alcohol (MAA) were investigated in batch reactor (Conv. 89%, Select 93.1%) and tubular reactor (Conv. 88.1%, Select 95%) using aluminum isopropoxide (Al(OPrⁱ)₃) as catalyst. Kinetic experiments on hydrogen transfer reactions and reaction order were investigated in batch reactor and tubular reactor. Response surface methodology was applied to optimize the optimum reaction conditions of hydrogen transfer reaction. Purification process of MAA from product mixture after hydrogen transfer reaction was simulated with Aspen Plus software; theoretical stages, reflux ratio, and feed stage of distillation tower were optimized. Density functional theory was used to investigate viable reaction pathway and to probe the catalytic mechanism between reactants and catalyst, including dehydrogenation, coupling, and hydrogenation reaction. Microscopic mechanisms of hydrogen transfer reaction from MAA to MAL were acquired in detail and could be easily extended to other series of hydrogen transfer reaction.