6,7-二羟基香豆素的研制

以苯醌和醋酐为原料,通过酰化反应制备了中间体1,2,4-三乙酰氧基苯,再与苹果酸发生环合反应制得6,7-二羟基香豆素。     

Copper‐Catalyzed Selective Oxidative Acylation of Secondary Anilines with Ethyl Glyoxalate: Domino Synthesis of Indoline‐2,3‐diones

A novel, easy and useful copper‐catalyzed selective acylation of secondary anilines with ethyl glyoxalate has been developed, and the corresponding indoline‐2,3‐dione derivatives were prepared. The procedure comprises the sequential intermolecular copper‐catalyzed selective oxidative ortho‐site aromatic acylation of the NH group in secondary anilines and intramolecular nucleophilic attack of the NH group to the ester. The inexpensive, easy and efficient method should provide a new strategy for synthesis of dicarbonyl compounds.     

Mild Palladium‐Catalyzed Oxidative Direct ortho‐C?H Acylation of Anilides under Aqueous Conditions

Palladium‐catalyzed cross‐dehydrogenative coupling between anilides and aromatic aldehydes was achieved under aqueous conditions. A wide variety of the desired benzophenone derivatives was isolated in good to excellent yield. The reaction rate acceleration effect of acid and detergent has been demonstrated. Mechanistic insight has been obtained from quantum chemical calculations.     

季铵盐类氯铝酸离子液体的表征及其催化苯与苯酐的酰基化反应

制备了多种季铵盐离子液体,考察了不同阴阳离子的离子液体对苯与苯酐酰基化合成邻苯甲酰苯甲酸(BBA)反应的催化性能.采用FTIR、紫外吸收光谱与Hammett酸强度函数联用的方法对离子液体进行表征,并借助量化计算分析反应路径.实验结果表明,不同阴离子的Et3NHCl离子液体催化活性的高低顺序为:Et3NHCl-2.5Al...     

Microwave‐Assisted One‐Step Synthesis of Acetophenones via Palladium‐Catalyzed Regioselective Arylation of Vinyloxytrimethylsilane

The regiochemistry of the palladium‐mediated arylation (Heck arylation) of enol ethers is sensitive to the structure of the enol ether, the arylating agent and the catalytic system. In this study, an effective and practical method was successfully developed for the synthesis of acetophenones with high regioselectivity under palladium‐catalyzed conditions. A variety of acetophenones was readily prepared from aryl iodides in good to excellent yields under microwave irradiation in a single step. The key feature of our new protocol is the use of vinyloxytrimethylsilane as a highly regioselective acylation reagent.     

磷钨酸铋非均相催化合成乙酸环己酯

以乙酸酐与环己醇为原料,磷钨酸铋为催化剂,合成乙酸环己酯,考察了催化剂用量、反应时间、醇酐摩尔比对乙酸环己酯产率的影响。结果表明,磷钨酸铋催化活性良好,当乙酸酐的加入量为0.1 mol,醇酐摩尔比为1.2时,使用0.9 g催化剂,反应30 min后,乙酸环己酯收率可达到93.8%,且催化剂重复使用5次仍保持良好活性。产品经折光率和红外光谱进行了表征。     

酰基稳态化花色苷的制备及其热降解特性和抗氧化活性

食品级的肉桂酸甲酯为酰基供体,运用减压酶法,催化其与矢车菊素-3-O-葡萄糖苷（C3G）发生酰化反应,具有绿色安全、高效且酰化产物单一等优点。对酰化产物进行分离,并进行热稳定性和抗氧化性等性质的测定。结果表明：酰化转化率为80%;利用半制备高效液相色谱仪对酰化后的产物进行分离纯化,纯化后的酰化C3G纯度达98.3%;经质谱分析可知,酰化后产物为矢车菊素-3-(6-肉桂酰)-葡萄糖苷（C3(6C)G）。酰基化修饰使花色苷的脂溶性、热稳定性得到了明显改善。采用1,1-二苯基-2-三硝基苯肼（1,1-diphenyl-2-picrylhydrazyl,DPPH）自由基清除、2,2-氨基-二(3-乙基-苯并噻唑啉-6-磺酸)（2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid,ABTS）阳离子自由基清除、铁离子还原/抗氧化能力法（ferric reducing and antioxidant power,FRAP）、羟自由基清除体外实验测定不同浓度下C3G、C3(6C)G和VC的抗氧化能力。与相同浓度的VC相比,除了在ABTS阳离子自由基清...     

6-2-氨丙基-2,3-二氢苯并呋喃的合成

以3-甲氧基苯甲醛为原料,经亨利反应、还原硝基和双键、氨基保护、傅-克酰基化、脱甲基、环合、羰基还原等反应,合成目的产物6-2-氨丙基-2,3-二氢苯并呋喃。并对硝基和双键的还原反应、傅-克酰基化和脱甲基反应的工艺条件进行了优化,得出较佳工艺条件:(1)化合物Ⅱ的还原反应:反应温度40℃,氢气压力4.0 MPa,Raney-Ni用量为化合物Ⅱ质量的8%,产物收率为78.6%;(2)合成化合物Ⅵ的反应:反应温度45℃,n(氯乙酰氯)/n(化合物Ⅳ)=1.4,反应时间6 h,产物收率为68.8%。     

Mechanical,Thermal, and Electrical Properties of Epoxy Matrix Composites Reinforced With Polyamide-Grafted-MWCNT/poly(azo-pyridine-benzophenone-imide)/Polyaniline Nanofibers

Friedel-Crafts acylation and in situ polymerization were adopted to graft polyamide on multi-walled carbon nanotube (MWCNT) surface to form MWCNT-PA using γ-Phenyl-?-caprolactone. Via electrospinning, MWCNT-PA/PAPBI and MWCNT-PA/PAPBI/PANI nanofibers were prepared using MWCNT-PA, poly(azo-pyridine-benzophenone-imide) (PAPBI) and polyaniline (PANI) and DGEBA as matrix. Compared with 3 wt% MWCNT-PA/PAPBI nanofibers (20.2 GPa), tensile modulus for film reinforced with 3 wt% MWCNT-PA/PAPBI/PANI nanofibers (27.6 GPa) was considerably increased. Thermal stability of MWCNT-PA/PAPBI/PANI nanofibers reinforced epoxy was higher with T₁₀ 633–654°C and T_g 283–291°C relative to DGEBAMWCNT-PA/PAPBI system. The filler loading also increased the electrical conductivity of DGEBA/MWCNT-PA/PAPBI/PANI from 3.44 to 6.01 S cm^?1.     

盐酸丁咯地尔的合成研究

以4-氯丁酸甲酯为起始原料,与吡咯烷缩合反应后,经水解、酰化、傅克烷基化、成盐得到目标化合物盐酸丁咯地尔。目标化合物的结构经红外光谱、1H-NMR和MS确证。该合成方法具有原料易得,合成路线短,操作简单,生产成本低廉的优点,总收率由文献报道的70%提高到75.7%,更适合工业化生产。