超声条件下低共熔溶剂中的Biginelli反应

在超声辅助下和低共熔溶剂中,使用氯化锌催化Biginelli反应合成了9个3,4-二氢嘧啶-2（1H）-酮衍生物(4a~4i),其结构经¹H NMR和IR确证。以4a的合成为例,研究了超声时间、催化剂种类及用量、反应温度和原料摩尔比对反应的影响。结果表明：在最佳反应条件[氯化胆碱/尿素为溶剂,氯化锌作催化剂,n(苯甲醛)/n(乙酰乙酸乙酯)/n(尿素)=1.0/0.9/1.0,于90 ℃反应20 min]下,4a产率最高可达86.3%。     

深共融溶剂促进的亨利-傅克烷基化串联反应（英文）

在氯化锌和氯化胆碱组成的深共融溶剂中,以芳香醛、硝基甲烷和N-取代苯胺为原料,建立了一种绿色的亨利-傅克烷基化串联反应方法.在该方法中,醛先与硝基甲烷发生Henry反应,其产物再与富电子芳烃进行Friedel-Crafts烷基化反应.该一锅法串联反应不需要额外添加催化剂,在温和条件下就能以较高产率快速地合成一系列目标产物.深共熔溶剂(氯化锌和氯化胆碱)廉价,且可循环使用,从而降低了合成成本.     

5,7-二甲氧基香豆素合成方法的改进

以间苯三酚为原料,选甲醇进行甲基化反应制备3,5-二甲氧基苯酚,以丙炔酸乙酯经Pechmann环化反应制备了白柠檬素(5,7-二甲氧基香豆素)。考察了甲基化反应、环化反应的影响因素,结果表明n(间苯三酚)∶n(甲醇)=1∶15,干燥氯化氢为催化剂,75℃反应7h,甲基化收率为82%;n(丙炔酸乙酯)∶n(3,5-二甲氧基苯酚)∶n(无水氯化锌)=1∶3∶1,环化温度为100℃,N2保护下反应2h,环化反应收率为88%,两步反应总收率达73%。目标产物用红外、质谱、核磁分析手段进行了表征和分析。     

2-氯烟酸的合成

以3-氰基吡啶(2)为原料,经氧化、氯化和水解反应合成了2-氯烟酸(1),总收率75.1%,其结构经IR和MS表征.最点考察了影响氧化反应的因素,最佳氧化反应条件为: 2 410 mmol,n(H2O2) ∶ n(2)＝1.2 ∶ 1.0,在钨酸盐催化下于70 ℃反应8 h,收率92.2%.     

氯化胆碱/草酸型低共熔溶剂氧化脱除模拟油硫化物

通过氯化胆碱和草酸在100℃下搅拌,合成了氯化胆碱/草酸型低共熔溶剂。以氯化胆碱/草酸为催化剂、过氧化氢为氧化剂、咪唑氟硼酸盐离子液体为萃取剂氧化萃取一体法脱除模拟油中的二苯并噻吩(DBT)。考察了反应温度、反应时间、氧化剂加入量、萃取剂类型、硫化物类型等因素对脱硫效率的影响。结果表明,当以咪唑氟硼酸盐为萃取剂,n(H2O2)/n(S)=8、反应温度30℃、反应80 min时,二苯并噻吩的脱除率可以达到95%。催化剂重复使用5次后,脱硫率仍然保持在90%。     

2-[5-(3-羟基苯甲酰氨基)-1,3,4-噻二唑]基乙酸乙酯的合成

以丙二酸二乙酯为起始原料,经选择性皂化、酸化、氯化、环合和酰胺化反应合成了2-[5-(3-羟基苯甲酰氨基)-1,3,4-噻二唑]基乙酸乙酯(1),总收率37.2%,其结构经1H NMR,13C NMR,IR和LC-MS(ESI)确证。采用正交实验法[L_9(3~4)]优化了酰胺化反应的条件。结果表明:在最优反应条件{n[2-(5-氨基-[1,3,4]-噻二唑)基乙酸乙酯]∶n(三乙胺)∶n(间羟基苯甲酰氯)=1∶2∶3,于20℃反应8 h}下,1收率75.5%。     

基于复合氯化剂CuCl_2·5/3NaCl·5/2Al_2O_3的1-氯-2-芳基乙炔的合成

直接使用CuCl2氯化芳基乙炔的反应通常存在着选择性差(有取代氯化和多种加成氯化的产物生成)、副产物多和分离困难等问题.描述了一种复合氯化剂(CuCl2·无机盐·载体)的制备以及基于该氯化剂取代氯化芳基乙炔的有效方法.首先通过一系列对比实验获得了CuCl2、载体和无机盐添加物的最佳配比.在此基础上考察了溶剂、复合氯化剂用量、反应温度诸因素对取代氯化反应的影响,提出了最佳反应条件:复合氯化剂为CuCl2·5/3Na Cl·5/2Al2O3,芳基乙炔与氯化剂的物质的量比为1∶3,溶剂为CH2Cl2,反应温度为35℃.在优化条件下,高产率(72%~99%)地合成了一系列1-氯-2-芳基乙炔目标产物1a~1n,并对这些化合物进行了表征.该方法反应条件温和、产率高、选择性好,并且适用于芳环上带有各种基团的底物.     

NH_4Cl焙烧氯化Pr_2O_3及其动力学研究

研究了NH_4Cl(s)焙烧氯化Pr_2O_3(s)制备PrCl_3(s)的热力学可行性、反应过程、适宜条件和动力学.结果表明:NH_4Cl(s)焙烧氯化Pr_2O_3(s)制备PrCl_3(s)在热力学上是可行的;氯化反应的过程为NH_4Cl(s)先与Pr_2O_3(s)生成2NH_4Cl·PrCl_3(s),然后NH_4Cl·PrCl_3(s)渐渐分解为PrCl_3(s);氯化反应的起始温度为457.35 K,497 K时反应进行完全;T≥643 K时PrCl_3(s)开始水解为Pr OCl(s);氯化焙烧温度理论上应控制在T≤643 K.制备PrCl_3(s)的适宜条件为n(NH_4Cl)∶n(Pr_2O_3)=12∶1、T=(623±10)K和t=40 min,氯化率为100%;氯化反应动力学符合Bagdasarrym模型,反应进度遵从Erofeev方程,氯化反应的表观活化能48.246 k J·mol~(-1),频率因子A_0为2.28×10~3,反应过程限制环节是界面化学反应控制.     

七水合三氯化铈-碘化钠催化氨基苯硫酚与高位阻α,β-不饱和酮的迈克尔加成反应

对七水合三氯化铈-碘化钠(CeCl3·7H2O-NaI)化邻氨基苯硫酚、对氯邻氨基苯硫酚、间氨基苯硫酚、对氨基苯硫酚和对甲基苯硫酚与α,β-不饱和酮(1a~1o)的迈克尔加成反应进行了系统研究.结果表明,CeCl3·7H2O-NaI-SiO2复合催化剂能有效催化邻氨基苯硫酚及对氯邻氨基苯硫酚与α,β-不饱和酮(1a~1o)的迈克尔加成反应.在优化的反应条件下,即n(CeCl3·7H2O)∶n(NaI)∶n(α,β-不饱和酮)=1∶2∶2,m(CeCl3·7H2O)∶m(SiO2)=1∶1.6,三氯甲烷作溶剂,反应温度为回流温度,反应时间为2 h,反应可达到中等产率(43.1%~58.8%).催化剂重复使用4次基本稳定.此外,提出了可能的催化机理.     

酞菁氯化铟的固相合成及光敏性能

以尿素、邻苯二甲酸酐、钼酸铵和四水合三氯化铟为原料, 乙酸钠为催化剂, 采用固相法合成酞菁氯化铟, 并用元素分析、UV-Vis、IR和XRD进行了表征. 考察了反应物配比、催化剂、反应温度和时间对产率的影响, 寻找出最佳制备条件为n(尿素)∶n(邻苯二甲酸酐)∶n(三氯化铟)=14∶4.5∶1, 以乙酸钠为催化剂, 130 ℃下恒温0.5 h, 在220 ℃下反应4 h后, 用88％(质量分数)浓硫酸提纯. 研究了酞菁氯化铟光敏电阻薄膜的光敏性能, 结果表明, 当用0.2 g酞菁氯化铟和0.6 g PVB制备光敏电阻薄膜时, 分散介质丁酮-环己酮的最佳用量为36 mL, 其电阻灵敏度保持在1.50×10⁸以上, 积分灵敏度保持在30 μA/(lx·V)以上. 研究结果表明, 酞菁氯化铟光敏电阻薄膜具有很好的光敏性能.     

Choline chloride–ZnCl2: Recyclable and efficient deep eutectic solvent for the [2+3] cycloaddition reaction of organic nitriles with sodium azide

Herein we report first time choline chloride–zinc chloride based deep eutectic solvent is a green and efficient reaction medium for the [2+3] cycloaddition reaction of organic nitriles with sodium azide to afford the corresponding 5-substituted 1H-tetrazoles. The present method provides an environment-friendly route, short reaction times with excellent yields, safe process, and simple workup which make this method an attractive and useful contribution to the existing conventional processes for the synthesis of 5-substituted 1H-tetrazoles.     

离子色谱法测定饲料中氯化胆碱和三甲胺的含量

建立了离子色谱法测定饲料中氯化胆碱含量及鉴别饲料中氯化胆碱及掺假物三甲胺的方法。选用IonPac CS12阳离子交换色谱柱(250 mm×4 mm i.d.)和8.5 mmol/L H2SO4淋洗液,抑制型电导检测,在16 min内分离测定了包括胆碱和三甲胺在内的8种阳离子。胆碱和三甲胺的最小检出限分别为0.1 mg/L和0.05 mg/L。方法回收率为99.25%~102.5%。该方法具有灵敏度高、选择性强、操作简单等优点。     

Assessment of the In Vivo Release and Biocompatibility of Novel Vesicles Containing Zinc in Rats

This paper is focused on the in vivo release and biocompatibility evaluation in rats of some novel systems entrapping zinc chloride in lipid vesicles. The particles were prepared by zinc chloride immobilization inside lipid vesicles made using phosphatidylcholine, stabilized with 0.5% chitosan solution, and dialyzed for 10 h to achieve a neutral pH. The submicrometric systems were physico-chemically characterized. White Wistar rats, assigned into four groups of six animals each, were treated orally with a single dose, as follows: Group I (control): deionized water 0.3 mL/100 g body weight; Group II (Zn): 2 mg/kg body weight (kbw) zinc chloride; Group III (LV-Zn): 2 mg/kbw zinc chloride in vesicles; Group IV (LVC-Zn): 2 mg/kbw zinc chloride in vesicles stabilized with chitosan. Haematological, biochemical, and immune parameters were assessed after 24 h and 7 days, and then liver fragments were collected for histopathological examination. The use of zinc submicrometric particles—especially those stabilized with chitosan—showed a delayed zinc release in rats. No substantial changes to blood parameters, plasma biochemical tests, serum complement activity, or peripheral neutrophils phagocytic capacity were noted; moreover, the tested substances did not induce liver architectural disturbances. The obtained systems provided a delayed release of zinc, and showed good biocompatibility in rats.     

毛细管电泳电导法快速检测饲料添加剂氯化胆碱

采用毛细管电泳电导法对饲料添加剂氯化胆碱进行了测定.实验优化了缓冲介质、分离电压、毛细管长度和内径等参数.结果表明:在优化条件下,氯化胆碱在4 min左右可以实现分离检测,线性范围在41.8～1.20 μg/mL,检出限为0.8 μg/mL;迁移时间和峰面积的相对标准偏差分别为0.6%、2.1%;样品加标回收率为97%～105%.将该法用于粉剂和饲料中氯化胆碱的检测,取得了满意的结果.     

Studies of phase equilibria in the systems ZnCl2-AgCl and ZnBr2-AgBr

Phase equilibria in the systems zinc chloride - silver chloride and zinc bromide - silver bromide were investigated by differential scanning calorimetry, electric conductivity measurements and X-ray diffraction methods. No intermediate compounds were found. Solubility of components in the solid-state is negligible. Both systems are of the eutectic type. The eutectic temperatures in the ZnCl₂-AgCl system and in the ZnBr₂-AgBr system are 504 K and 551 K, respectively, and the compositions of the eutectic point are 53.5 mol% AgCl and 59.4 mol% AgBr, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Henry’s constant of carbon dioxide-aqueous deep eutectic solvent (choline chloride/ethylene glycol,choline chloride/glycerol,choline chloride/malonic acid) systems

In this study, we present a new set of Henry’s constant data for the system carbon dioxide-aqueous deep eutectic solvent (DES) (20 to 80 wt% DES) at T = (303.15, 308.15, and 313.15) K. The DESs used were choline chloride-based: ethaline (choline chloride/ethylene glycol), glyceline (choline chloride/glycerol), and maline (choline chloride/malonic acid). A differential Henry’s coefficient model was used to describe the behaviour of Henry’s constant, and correlate it with temperature and concentration of DES in the aqueous DES solution. The correlation was found satisfactory such that the proposed model can be used in engineering calculations with reasonable accuracy.     

A Facile Approach to Regioselective 1-O-Deacylation of Peracylated Glycopyranoses

The regioselective 1-O-deacylation of peracylated glycopyranoses 1a-d with zinc chloride and zinc oxide in THE/MeOH gave the corresponding tetra-O-acylglycopyranoses 2a-d in good yields.     

Synthesis and characterization of zinc chloride containing poly(acrylic acid) hydrogel by gamma irradiation

In this study, the characterization of zinc chloride incorporated into a poly(acrylic acid) (PAAc) hydrogel prepared by gamma-ray irradiation was investigated. Zinc chloride powder with different concentrations was dissolved in the PAAc solution, and it was crosslinked with gamma-ray irradiation. The effects of various parameters such as zinc ion concentration and irradiation doses on characteristics of the hydrogel formed were investigated in detail for obtaining an antibacterial wound dressing.In addition, the gel content, pH-sensitive (pH 4 or 7) swelling ratio, and UV–vis absorption spectra of the zinc particles in the hydrogels were characterized. Moreover, antibacterial properties of these new materials against Staphylococcus aureus and Escherichia coli strains were observed on solid growth media. The antibacterial tests indicated that the zinc chloride containing PAAc hydrogels have good antibacterial activity.     

镍离子对中磷镍基体氯化胆碱无氰浸金表面的改善

本文通过加入氯化镍解决了作者实验室之前开发的新型氯化胆碱（ChCl）无氰浸金液不适用于中磷镍基底上的问题. 氯化镍的加入不会对镀速产生明显影响,500 mg·L^-1的六水合氯化镍可以有效缓解浸金液对镍基底的过度腐蚀,并能改善镀金层的表面质量. 改良后的氯化胆碱体系镀液对中磷镍基底有良好的适用性,同时对所用的添加剂镍离子具有较高的承载能力（六水合氯化镍2000 mg·L^-1）,因此该镀液体系具备了应用于工业生产的潜力.