α-乙酰基二硫缩烯酮α碳原子的酰化反应

进行了α-乙酰基二硫缩烯酮与酰氯的酰化反应. 以干燥的二氯甲烷为溶剂, 在四氯化钛催化下, α-乙酰基环二硫缩烯酮(1)可与脂肪及芳酰氯(2)反应, 在化合物1的α-碳原子上发生酰化反应, 以较高的产率生成各种α-乙酰基-α-酰基二硫缩烯酮(3).     

Dehalogenation of o-dihalogen substituted arenes and α,α′-dihalogen substituted o-xylenes with lanthanum metal

It was found that lanthanum metal caused the dehalogenation of o-dihalogen substituted arenes and α,α′-dihalogen substituted o-xylenes to generate the corresponding benzynes and o-quinodimethanes. When o-dihalogen substituted arenes were allowed to react with lanthanum metal in the presence of dienes, the Diels-Alder products between benzyne and dienes were formed in moderate to good yields. Similarly, the Diels-Alder adducts of o-quinodimethane with dienophiles were obtained, in the reaction of α,α′-dibromo-o-xylenes with lanthanum metal in the presence of dienophiles.     

Synthesis of N-（α-Alkoxyalkyl）benzotriazoles Catalyzed by Acidic Ionic Liquid at Room Temperature

N-（α-Alkoxyalkyl）benzotriazoles were synthesized via the condensation of benzotriazole with various aldehydes and alcohols catalyzed by acidic ionic liquid [hmim]HSO4 at room temperature. The yield was up to 99%. This novel method was effective when triethoxymethane was utilized instead of alcohols. Moreover, acidic ionic liquid could be reused easily with no significant degradation of its catalytic activity.     

α-酮酯和α-酮酰胺的Henry反应

用三乙胺催化环状α-酮酯和α-酮酰胺同硝基甲烷的Henry反应, 首次合成了12个多官能团的β-硝基醇, 它们的结构用元素分析、红外光谱和核磁共振进行了表征. 这一反应速度较快, 室温下进行, 条件温和, 产率较好, 是合成多官能团硝基醇的有效方法.     

4—叔丁基—β—氯—α甲基肉桂醛的合成

从苯和叔丁醇出发，经过３步反应合成得标题化合物，总收率在６８％以上。     

Synthesis of novel silylated 1,2,4-triazin-5-ones

The reaction of various α-silyl-α-keto esters with thiosemicarbazide at 50 °C in ethyl acetate was found to give α-silyl-substituted thiosemicarbazone-acetic acid esters in good yield. These may then be converted to their corresponding silyl-substituted 1,2,4-triazin-5-ones by cyclization under basic conditions.     

Absolute stereochemistries and total synthesis of (+)-arisugacins A and B, potent, orally bioactive and selective inhibitors of acetylcholinesterase

In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins.     

稀土高氯酸盐-谷氨酸配合物[Pr2(L-α-Glu)2(ClO4)(H2O)7](ClO4)3•4H2O的低温热容和热化学研究

合成了一种稀土高氯酸盐-谷氨酸配合物. 经TG/DTG、化学和元素分析、FTIR及与相关文献对比, 确定其组成为[Pr₂(L-α-Glu)₂(ClO₄)(H₂O)₇](ClO₄)₃•4H₂O, 纯度为99.0%以上. 利用显微熔点仪分析发现其没有熔点. 在78～370 K温区, 用精密绝热量热仪测量其低温热容, 在285～306 K温区发现一明显吸热峰, 归结为固-固相变过程. 通过相变温区三次重复热容测量, 得到相变温度T_tr、相变焓Δ_trH_m和相变熵Δ_trS_m分别为(297.158±0.280) K, (12.338±0.016) kJ•mol^－1和(41.520±0.156) J•K^－1•mol^－1. 用最小二乘法将非相变温区的热容对温度进行拟合, 得到了热容随温度变化的两个多项式方程. 用此方程进行数值积分, 得到每隔5 K的舒平热容值和相对于273.15 K的热力学函数值. 根据TG/DTG结果, 推测了该配合物的热分解机理. 依据Hess定律, 选择1 mol•dm^－3盐酸为量热溶剂, 利用等温环境溶解-反应量热计, 测定了该配合物的标准摩尔生成焓为: Δ_fH_m⁰＝－(7223.1±2.4) kJ•mol^－1.     

金负载量对低温水煤气变换Au/α-Fe2O3催化剂结构和性能的影响

采用共沉淀法制备了低温水煤气变换Au/α-Fe2O3催化剂。通过正交实验优化催化剂的还原活化条件，考察了金负载量对催化剂性能的影响。采用BET、XRD、UV-VIS、XRF、H2-TPR和O2-TPO等表征手段对催化剂的结构进行分析，并与其催化性能进行关联。结果表明，（1）采用10%-H2/N2还原气将催化剂在150 ℃原位还原9 h，其催化活性最高；（2）金的最佳负载量为8.00%，此时在催化剂制备过程中金的流失量较少，金粒子较小，也有利于抑制催化剂在反应过程中烧结；（3）TPR-TPO结果表明，金的负载量为8.00%时，Au/α-Fe2O3催化剂具有较易被还原、不易被氧化的性质，从而显示出最高催化活性。（4）Au/α-Fe2O3催化剂中的金以单质金（Au0）形式存在；其高活性与Au0-Fe3O4间的协同作用有关。     

水介质中α,α-双(4-羟基香豆素-3-基)甲苯的洁净合成

在水介质中三乙基苄基氯化铵(TEBA)存在下, 芳醛与4-羟基香豆素反应为α,α-双(4-羟基香豆素-3-基)甲苯提供了一种快速、方便、高效和洁净的合成方法.