溴法合成乙基香兰素的工艺改进

采用正交实验的方法，在用对羟基苯甲醛溴化台成乙基香兰素的过程中对原料配比、反应温度及溶剂选择等影响产率的因素进行了研究，得出了提高产率的最佳条件。在溴化阶段用氯化溴代替溴素、用乙酸甲酯作助溶剂使-溴化物的产率提高了10%，达到91．3％；在乙氧基化步骤中用CuO作催化剂，用乙醇和DMF作反应溶剂使得最终产物的产率达到85．2％。     

Bromine addition and successive amine substitution of mesoporous ethylenesilica: Reaction, characterizations and arsenate adsorption

Bromination and subsequent ethylenediamine substitution of the CC double bond in mesoporous ethylenesilica were carried out to explore the characteristics of this periodic mesoporous organosilica. The structures of the products (BrPMO and EDA–BrPMO, respectively) were analysed by IR, Br K-edge EXAFS and NMR spectroscopies, as well as X-ray diffraction and nitrogen adsorption. We showed (1) that the formulae of the two products that formed were [CHBrSiO_1.5]_0.45[CHSiO_1.5]_0.55 and [NH₂CH₂CH₂NHCHSiO_1.5]_0.05 [CHBrSiO_1.5]_0.40[CHSiO_1.5]_0.55, respectively, (2) that the addition of Br₂ at room temperature occurred on the CC double bonds with disturbing the framework structure, (3) that IR absorption band of CC bonds that reacted with Br₂ is significantly different from that of inactive CC bond, (4) that the length of the C–Br bond was considerably longer than in conventional alkyl bromides, and (5) that a large proportion of the ν(C–Br) band remained at the same position in the IR absorption spectrum after the ethylenediamine (EDA) substitution, while a new ν(C–Br) absorption also appeared. The mechanisms of these reactions are discussed at both the micro and mesoscopic levels.

Arsenate adsorption on EDA–BrPMO, in which the EDA is directly bound to the “surface” of the mesopores, was compared with adsorption on EDA–Pr–PMO, which was prepared by the direct synthesis of 3-chloropropyl-functionalized mesoporous ethanesilica followed by the substitution of Cl with EDA. The strength of the adsorption, as measured with the distribution coefficient, was greater for the former adsorbent than the latter. The origin of this difference was attributed to the distance between amino group and the surface.     

4-溴-1-溴甲基-2-对氯苯基-5-三氟甲基吡咯-3-腈的合成

以2 对氯苯基1 甲基5 三氟甲基2 吡咯啉3 腈为原料,经三步反应合成了4 溴1溴甲基2 对氯苯基5 三氟甲基吡咯3 腈,合成总收率为29.8%。     

异丁烯残留量对丁基橡胶溴化的影响

溶液法制备丁基橡胶可以直接得到丁基橡胶胶液,为溴化节省工艺步骤。但由于丁基橡胶优异的气密性,使得胶液中未反应的异丁烯单体很难彻底脱除。采用顶空气相色谱建立了测定胶液中异丁烯质量浓度的方法,将含有不同质量浓度异丁烯的胶液溴化,探究了异丁烯残留量对丁基橡胶溴化的影响。结果表明,随着胶液中异丁烯质量浓度的增加,溴化丁基橡胶的含溴质量分数不断降低,且溴代仲位烯丙基结构与溴代伯位烯丙基结构的相对摩尔比值逐渐增大。     

Polyynes Production in a Solvent-Submerged Electric Arc Between Graphite Electrodes. III. Chemical Reactivity and Stability Toward Air, Ozone, and Light

Since polyynes are easily accessible with the submerged electric arc synthesis between graphite electrodes, the chemical behavior of polyynes solutions in different solvents has been explored. It has been found that surprisingly the polyynes solutions, with polyynes having up to 16 carbon atoms arranged in a chain, are stable in air over 1 week time in the dark. These solutions react relatively slowly with ozone while add rapidly and completely bromine. The polyynes solutions are instead quite easily photolyzed under the action of UV radiation both in air and under N₂. Two different light sources were used in the study: a low pressure mercury lamp emitting almost a monochromatic radiation at 254 nm and an high pressure mercury lamp emitting in a broad wavelength range in the ultraviolet. With the former monochromatic light source, it has been demonstrated the possibility to perform a selective photolysis of selected polyynes in a mixture of homologous series.     

Bromination of Aromatic Compounds using Bromine in a Microreactor

2,4,5‐Trifluorobromobenzene is a valuable intermediate with important application in the synthesis of biologically active peptides and fluorescent reagents. A continuous‐flow system has been successfully developed for the synthesis of 2,4,5‐trifluorobromobenzene in a microreactor using FeBr₃ as a catalyst, which is steadily generated in situ from the reaction of Br₂ and Fe. The procedure is efficient and easy‐to‐handle, and 2,4,5‐trifluorobromobenzene can be obtained within minutes in high yields.     

Analysis of aflatoxin M1 and M2 in commercial dairy products using high-performance liquid chromatography with a fluorescence detector

Aflatoxin M₁ (AFM₁) and M₂ (AFM₂) in commercial dairy products were analyzed by high-performance liquid chromatography (HPLC) with a fluorescence detector (FLD). To ensure an accurate analysis, two derivatization methods, bromination and aflatoxin–trifluoroacetic acid derivatization (ATD), were compared. The limits of detection (LODs) of the bromination method were 124.42–151.73 ng/kg, and the recovery rates were between 64 and 102%. The detection rates and concentration levels of AFM₁ were 6–74% and 14.48–270.94 ng/kg, respectively. AFM₁ was detected in 74% of milk powder samples and 36% of ice cream samples. The mean values of AFM₁ in milk powder and ice cream samples were 270.94 and 33.16 ng/kg, respectively. In the case of AFM₂, the detection rates were 2–10%, and the concentration levels were 20.62–55.67 ng/kg in milk and milk powder. Among milk and milk powder samples, ultra heat-treated (UHT) milk had lower AFM₁ contamination levels than pasteurized milk.     

2-溴苯酚合成工艺的优化研究

2-溴-4-叔丁基苯酚与甲苯的叔丁基转移反应可以形成重要的有机中间体2-溴苯酚。考察了催化剂及反应条件对叔丁基转移反应的影响,结果表明,三氯化铝及其与叔胺盐酸盐的复合盐对叔丁基转移反应的具有较好的催化活性,27AlNMR的分析表明催化活性中心可能是三氯化铝与水解产生的氯化氢反应形成的氯铝酸。进一步研究表明,氯化氢及溴化氢可提高三氯化铝的催化活性,降低三氯化铝的用量。优化后的工艺条件：在二氯甲烷溶剂中,4-叔丁基苯酚与溴素在0℃反应选择性形成2-溴-4-叔丁基苯酚,加入摩尔分数为30%的AlCl3及600%的甲苯,30℃“一锅法”反应制备2-溴苯酚,2-溴-4-叔丁基苯酚反应的转化率及选择性可达96.5%、99.6%。     

Haloform plasma modification of polyolefin surfaces

Polyolefin surfaces (polyethylene and polypropylene) were exposed to haloform (CHX₃) plasmas for introduction of monosort halogen groups. Bromoform and chloroform plasmas produced selectively C-Br (100 Br/100 C) and C-Cl (200 Cl/100 C) groups in high yields. The bromoform plasma showed 1-3 and the chloroform plasma 2-7 post-plasma introduced O-functionalities per 100 C. The polyolefin C-Br groups were grafted wet-chemically or by exposure to the vapour of amines, diols and glycols. Thus, spacer molecules could be covalently bonded to maximal 15 spacer molecules per 100 C for the smallest grafted molecules and 1.2 molecules/100 C for larger molecules as octaaminophenylene-POSS. After metal evaporation the end groups of these polymer-bonded spacer molecules formed also covalent bonds to the metal. Thus, flexible, hydrophobic and barrier elements were introduced into the polymer-metal interfaces for high-impact, high-durable and water-resistant metal-polymer composites as measured by means of peel strengths.     

Isotopic Effect on the Kinetics of the Belousov-Zhabotinsky Reaction

In this work we present results about the deuterium isotope effect on the global kinetics of a Belousov-Zhabotinsky reaction in batch conditions. A nonlinear dependence of the Induction Period upon the percentage of deuterated reactants was found. The isotopic effect on the bromination reaction of malonic acid was evaluated.