相转移催化法合成苯甲醚新工艺

通过相转移催化法合成苯甲醚新工艺,苯酚钠与一氯甲烷在相转移催化剂催化下合成了苯甲醚。最佳的反应条件为：苯酚与氢氧化钠摩尔比为1：1～2,苯酚与-氯甲烷摩尔为1：1．2～3,反应温度70～80℃,压力1．0～2．0MPa,反应时间4～8h,相转移催化剂的用量为苯酚重量的0．01％,苯甲醚的收率可达95％以上。     

苯乙醇和茴香醚在含Fe蚕沙基生物碳材料的储香与释放性能研究

选用桑蚕废弃物蚕沙为碳源,利用ZnCl₂和FeCl₂作为活化剂,通过一步合成法获得一种Fe掺杂高石墨化多孔生物炭材料Fe/Z-ASE,并测定香精化合物分子苯乙醇和茴香醚在Fe/Z-ASE上的吸附和缓释动力学行为,然后再通过量子化学计算分析苯乙醇、茴香醚与Fe/Z-ASE的作用关系以及苯乙醇、茴香醚分子间作用力。结果发现:蚕沙多孔炭Fe/Z-ASE孔隙结构发达,表面石墨化碳含量高,Fe元素分布均匀,其BET比表面积为950.9 m²/g且中孔占60%以上,是一种表面疏水并呈现弱极性的多级孔生物炭材料;在苯乙醇和茴香醚的扩散和控释过程中,茴香醚具有比苯乙醇更高的吸附量(510 mg/g)和扩散动力学常数(1.7×10^-2min^-1),而且在不同初始茴香醚吸附量下(150～500 mg/g)其都能获得较好的控释效果。随后通过密度泛函DFT模拟计算可知,茴香醚和苯乙醇都是弱碱,能与Fe/Z-ASE材料上的弱酸性吸附位(Fe-C)产生相互作用,而且由于茴香醚的碱性更弱,所以与Fe/Z-A...     

Investigation into the potential of a novel superacid catalyst for the catalytic upgrading of pyrolytic bio-oil

Treatment of zirconium oxide with sulphate ions forms a highly acidic, or superacidic catalyst; sulphated zirconia. This catalyst has been found previously to be highly applicable to a range of reactions including acylation alkylation, isomerization, cracking and dehydration at temperatures in the range 150–200°C. These relatively low-temperature reactions offer potential in the field of bio-oil catalytic upgrading. Here zeolite catalysts have been used predominantly, but with associated problems due to the high reaction temperatures related with their use. The paper describes the processes involved in optimization of a process for the catalytic upgrading of a bio-oil produced by slow pyrolysis of pine wood. Copyright © 2002 John Wiley & Sons, Ltd.     

载溴树脂作为3—甲基茴香醚的溴化剂

制备了一种新型的溴化试剂－载溴阴离子交换树脂。在间甲基茴香醚的溴化中，这种溴化剂有良好的选择性及稳定性，产物４－溴－３－甲基茴香醚的产率高达８９．２％。     

对丙烯基茴香醚的直接电氧化活化

采用循环伏安法（CV（、恒电位电解法和计时电流法研究了对丙烯基茴香醚（p-PA）在乙腈-水混合溶液中的直接电氧化行为,考察了水的含量、扫描速度、温度、反应底物浓度、电解电位、电极等因素对p-PA中C═C电氧化活化的影响。实验结果表明,p-PA在乙腈-水混合溶液中的电氧化过程是不可逆的,且该过程受扩散步骤控制,扩散系数D=2.53×10^-6cm²·s^-1。通过GC-MS检测,p-PA直接电氧化的主要产物为对甲氧基苯甲醛（p-MBA）。在一室型无隔膜电解槽中,以石墨棒为工作电极,25℃下,乙腈-水混合溶液中水的含量为20%时,反应底物几乎全部转化,p-MBA的产率可达93%。     

Aggregation pheromone system of adult gregarious desert locust schistocerca gregaria (forskal)

Six electrophysiologically active aromatic compounds, viz., anisole, benzaldehyde, veratrole, guaiacol, phenylacetonitrile, and phenol, were identified in the volatiles of older-adult male desert locust. Young adults and females of all age groups produced none or only trace quantities of these compounds. Comparison of the aggregation responses of young and older adults to the crude, older-adult, volatile extract and different synthetic blends of the six compounds showed that the aggregation pheromone system of the adult gregarious locust consists of phenylacetonitrile, guaiacol, phenol, and benzaldehyde. Like the crude volatile extract of older males, neither the synthetic blend of the six compounds nor the adult pheromone blend evoked any significant aggregation responses from nymphs. These results confirm our previous report of sexual differentiation in the production of adult aggregation pheromone in the desert locust and of the evidence of two distinct aggregation pheromone systems in the two stages of the insect.     

合成苯甲醚的新工艺

以碳酸二甲酯代替硫酸二甲酯作甲基化剂，在ＮａＸ 型分子筛催化剂上与苯酚发生气相反应合成苯甲醚；并自制了相应的小试装置，获得这一新工艺的最佳反应条件：苯酚与碳酸二甲酯物质的量比为１∶１，反应温度为２８０ ℃，平均停留时间为６ ｓ，苯甲醚的收率可达８４－３％ 。     

亚硝酸钠/盐酸催化氧气氧化碘化芳烃、醚、酚化合物

以廉价易得的盐酸/亚硝酸钠为催化剂,碘为碘化试剂,通过分子氧,氧化碘化芳烃、醚、酚的活泼芳香底物,发展了温和条件下高效碘化方法。以苯甲醚为模型底物,系统考察了影响反应的因素,确定的最佳反应条件为:20℃氧气条件下,1,2-二氯乙烷(DCE)为溶剂,n(苯甲醚)∶n(碘)∶n(亚硝酸钠)∶n(HC l)=1∶0.515∶0.05∶0.1。该方法碘原子经济性好,催化剂廉价易得,反应时间大为缩短,选择性好、转化率高,副产物仅为水,容易处理,绿色环保、易于工业化;通过反应机理验证实验,提出了可能的催化循环机理。     

催化氧化制备对甲氧基苯甲醛氧化液的气相色谱分析

建立了用气相色谱法分析测定对甲基苯甲醚氧化产物的方法,选用SE-30毛细管柱,以对甲基苯甲醛为内标物,在选定的条件下利用归一化法和内标法分析测定了对甲基苯甲醚、对甲氧基苯甲醛以及副产物2-溴-4-甲基苯甲醚和乙酸-4-甲氧基苄酯的含量.结果表明,各组分回收率为98.0%～103.8%,归一化法的相对标准偏差≤2.00%;内标法测定对甲基苯甲醚和目标产物对甲氧基苯甲醛的相对标准偏差≤1.00%.     

Aromatic chlorination of toluene and of anisole using clay-supported iron(III) chloride and m-chloroperbenzoic acid. A biomimetic approach

In the presence of meta-chloroperbenzoic acid, clay-supported ferric chloride is an efficient aromatic chlorinating agent for toluene and anisole. Influence of various experimental factors such as the nature of the solvent, the peracid or the metallic cation were investigated. These reactions represent a laboratory equivalent to biological halogenations through oxidation of halide ions by peroxidases in the presence of hydrogen peroxide.