丁基羟基茴香醚的合成

对苯二酚在树脂催化作用下与甲醇反应生成对羟基苯甲醚,产物不经分离即与甲基叔丁基醚反应得到了丁基羟基茴香醚（BHA）,实验表明,用甲苯作溶剂可提高对羟基苯甲醚的产率,用甲苯与丁酮的混合溶剂能显提高BHA的选择性。     

The Effect of Aromatic Ethers on the Trimerisation of Ethylene using a Chromium Catalyst and Aryloxy Ligands

A catalyst system consisting of a chromium source, a 2,6‐disubstituted phenol and an aromatic ether solvent, on activation with triethylaluminium, is active and selective for the trimerisation of ethylene to form 1‐hexene. The aromatic ether appears to play a role as both solvent and reagent and is pivotal in ensuring both the good activity of the system as well as selectivity to the desired product, 1‐hexene.     

碘催化苯甲醚的苯甲酰化反应

在碘催化作用下,以苯甲醚和苯甲酰氯为原料,通过Friedel-Crafts酰基化反应合成对甲氧基二苯甲酮。考察了原料物质的量比、催化剂用量以及反应温度和时间等因素对产品收率的影响。确定的适宜工艺条件为: 苯甲醚0.1 mol,苯甲醚与苯甲酰氯的物质的量比为1.0∶1.5,催化剂质量为1. 5 g,反应温度140 ℃,反应时间为4. 0 h ,产物收率达59.0%。     

Hb沸石催化合成对甲氧基苯乙酮及其反应物与产物的竞争吸附

研究了无溶剂条件下,Hb沸石催化苯甲醚(AN)与乙酸酐(AA)的多相Friedel-Crafts酰化反应选择性生成对甲氧基苯乙酮(P-MOAP),探讨了反应物摩尔比、催化剂用量和反应温度对产品收率的影响. 在AN 0.1 mol,AN/AA摩尔比1:1.5,催化剂用量1.0 g,反应温度95℃,反应时间4 h的条件下,最终产品收率为73.25%. 利用Langmuir- Hinshelwood机理研究了该反应的动力学,结果表明,反应物和产物的竞争吸附是由于吸附平衡常数不同. 催化剂对产物P-MOAP的吸附远大于反应物,且提高反应温度,产物的吸附平衡常数降低.     

Storage and release properties of pheneylethanol and anisole flavor on Fe-based silkworm excrement biocarbon

The silkworm waste from the silkworm was selected as the carbon source, and ZnCl₂ and FeCl₂ were used as activators to obtain a Fe-doped highly graphitized porous biochar material Fe/Z-ASE through a one-step synthesis method. The fabricated Fe/Z-ASE was tested for the adsorption and sustained-release kinetics of pheneylethanol and anisole while their mutual interaction and intermolecular interactions were evaluated by quantum chemical calculation. The silkworm feces exhibited a well-developed pore structure, high surface graphitized carbon content, high BET surface area (950.9 m²/g), more than 60% mesopores and uniform distribution of Fe. Fe/Z-ASE exhibited hydrophobic surface and weak polarity, while anisole realized higher adsorption capacity (510 mg/g) and diffusion rate of 1.7×10^-2 min^-1 than that of phenylethanol under variable anisole adsorption amounts (150—510 mg/g). Density functional simulations suggested anisole and phenylethanol as weak bases and hence interacted with the weakly acidic adsorption sites (Fe-C) on the Fe/Z-ASE, while the relatively higher basicity of anisole endorsed it stronger interaction with Fe/Z-ASE. Molecular dynamics analysis showed strong hydrogen bonding between pheneylethanol molecules while no such interaction existed among anisole molecules, which hindered the desorption of pheneylethanol molecules under high initial adsorption capacity as compared to those of anisole.     

过渡金属修饰的磷钨酸盐催化剂在Friedel-Crafts乙酰化反应中的应用

制备了过渡金属修饰的磷钨酸盐(M_xH_(3-2x)PW_(12)O_(40),M=Co,Cu,Zn,Ni)催化剂,用BET,ICP,XRD,FTIR,NH_3-TPD等技术对其性能进行了表征,并考察了该系列催化剂在芳香类化合物的Friedel-Crafts乙酰化反应中的活性。实验结果表明,多孔性M_xH_(3-2x)PW_(12)O_(40)保持了磷钨酸的Keggin结构和酸强度,酸量明显大于磷钨酸。在茴香醚乙酰化反应中,M_xH_(3-2x)PW_(12)O_(40)(除Co_(1.5)PW_(12)O_(40)外)的催化活性和选择性明显高于磷钨酸和Cs_(2.5)H_(0.5)PW_(12)O_(40),其中Co_(0.5)H_2PW_(12)O_(40)的催化活性最高。以Co_(0.5)H_2PW_(12)O_(40)为催化剂合成对甲氧基苯乙酮(p-MOPA)时,P-MOPA收率和选择性分别达到84.36%和96.78%。Co_(0.5)H_2PW_(12)O_(40)用于苯衍生物、噻吩及其衍生物的乙酰化反应时电呈现较好的催化活性和选择性,其中,2-乙酰噻吩的收率和选择性分别达到86.93%和99%以上。     

碘催化合成对甲氧基苯乙酮

以碘为催化剂,由苯甲醚与乙酸酐进行酰基化反应合成对甲氧基苯乙酮。考察了反应物摩尔比、催化剂用量、反应温度及反应时间对产物收率的影响,确定了最佳反应条件为：苯甲醚为0.1mol,苯甲醚与乙酸酐的摩尔比为1：1.5,催化剂的最佳质量为1g,反应时间为1.5h,反应温度100℃,产品收率达到52.9％。比较了不同种类催化剂对苯甲醚与乙酸酐酰化反应的催化效果。结果表明,碘的催化效率远高于杂多酸及沸石分子筛,是高效酰化反应的催化剂。初步探讨了反应机理。     

茴香醚在葡萄糖基多孔碳材料上缓释机理

选择葡萄糖为碳源制备了一种多孔碳材料,对材料进行孔隙结构表征,研究材料孔隙结构对茴香醚脱附扩散机制的影响。应用重量法测定茴香醚在不同吸附剂上的脱附动力学曲线,建立扩散系数D_e估算模型,然后计算出茴香醚在吸附剂上的扩散系数D_e（t）-q（t）关系曲线,根据扩散系数值的大小划分扩散机理区域,讨论吸附剂的孔隙结构对茴香醚在吸附剂材料上扩散机制的影响。研究结果表明,所制备样品的比表面积可达1133～3153 m²·g⁻¹,茴香醚在吸附剂上的吸附量可达到1050 mg·g⁻¹;茴香醚香料分子在3种材料上的脱附扩散都经历了一般扩散、Knudsen扩散和表面扩散。吸附剂的孔隙结构对茴香醚香料分子在材料上的脱附扩散机制有影响,其微孔比例越高,茴香醚分子在此吸附剂上以表面扩散机制进行脱附所占比例越高。茴香醚分子在3种吸附剂上的脱附均以Knudsen扩散和表面扩散为主,约占78%～83%。本研究成果对于指导香料物质缓释材料的制备具有实际指导和借鉴意义。     

高效液相色谱法测定辛伐他汀中的抗氧化剂叔丁基羟基茴香醚

建立了测定辛伐他汀中抗氧化剂叔丁基羟基茴香醚(BHA)含量的高效液相色谱方法.采用C18色谱柱(Supelcosil C18, 4.6 mm i.d.×33 mm,3 μm);流动相A为乙腈,流动相B为0.1 %磷酸水溶液;洗脱梯度为0～3 min 65 % B,3～3.5 min 65 %～45 % B,3.5～8.5 min 45 %～10 % B,8.5～9.5 min 10 % B,9.5～10 min 10 %～65 % B,10～11.9 min 65 % B,12 min stop.检测波长为292 nm,流速为3.0 mL·min-1,柱温为35 ℃.结果BHA与辛伐他汀及各杂质分离良好,BHA在0.1～0.9 μg·mL-1范围内峰面积与浓度呈良好的线性关系(r=0.9998),最低检出量为0.4 ng,回收率为99.3 %,相对标准偏差为1.0 %.该方法简便、快速、准确,可用于辛伐他汀中微量BHA的含量测定.