2—甲氧基—5—乙酰氨基—N,N—二烯丙基苯胺的合成研究

本文以烯丙醇为合成３－溴丙烯,并以此作烷化剂合成２－甲氧基－５－乙酰氨基－Ｎ,Ｎ－二烯丙基苯胺。探讨优化了反应条件,该路线具有操作简单、反应快、产率高的特点。     

2,4,6—三溴苯胺的合成

通过选用合适的催化剂ＭｇＢｒ２,用Ｂｒ２的ＨＢｒ水溶液溴化苯胺氢溴酸盐水溶液,一步制得９９％以上纯度的２,４,６－三溴苯胺,收率９８％左右。     

N-烯丙基-邻卤苯胺类衍生物的合成

以邻卤苯胺为原料先对氨基进行酰化,然后采用成本低廉的NaOH作碱;或在K2CO3和相转移催化剂TBAB存在下,与烯丙基溴反应制备N-烯丙基对甲苯磺酰邻卤苯胺(3a,3b)和N-烯丙基乙酰邻卤苯胺(3c,3d)。该类化合物可作为合成2,3-二氢吲哚衍生物的重要中间体。反应条件温和、操作简单,且产物收率高,其结构经IR和1H NMR分析得到确证。     

甲代烯丙基磺酸钠的合成

以Na2SO3和甲基丙烯氯为原料合成了甲代烯丙基磺酸钠,研究了反应温度、反应时间、反应物摩尔比等因素对结果的影响。确定了合成目标产物的最佳反应条件为:甲基丙烯氯0.5mol,Na2SO3与甲基丙烯氯的摩尔比为1.05~1.10∶1,甲基丙烯氯滴加到Na2SO3溶液中,65°C下反应90min,在此最佳反应条件下,产品收率超过74%。     

在微乳体系中合成N,N-二乙基苯胺

在常压下向苯胺/十六烷基三甲基溴化铵/正丁醇/水微乳体系中滴加溴乙烷合成N,N-二乙基苯胺。研究了各种因素对目的产物产率的影响,其优化工艺条件为反应温度50℃,反应时间5小时,溴乙烷与苯胺的摩尔比为1.75∶1,氢氧化钠加入量为4.0g。N,N-二乙基苯胺产率可达70.1%。     

苯胺连续合成二苯胺动力学研究

对苯胺在DH－1催化剂合成二苯胺的反应规律进行了研究。归结出反应动力学方程式为r=[CBA/(CBA KDCD/KBA)]^2K;反应温度与反应速度常数的关系为K＝K0e^-E/RT;反应温度与相对吸附常数的关系为Z=Z0e^-Q/RT。实验结果表明：苯胺在DH－1催化剂活性中心上缩合脱氨反应为反应速度控制步骤。在实验温度范围内,该动力学方程的计算值与实验值绝对误差小于3．0％,该动力学方程式可以作为工业装置设计的依据。     

烯丙基醚的合成技术研究

介绍了几种多元醇烯丙基醚的不同合成方法,并将各种方法及产物性能进行了对比,结果表明,用烯丙醇与环氧乙（丙）烷开环反应合成二元醇单烯丙基醚,工艺简单,反应时间短,收率高,产物性能好,成本低,生产过程无废液排放。     

N-乙基间甲氧基苯胺的合成

以Cu／Zn／Ni混合氧化物为催化剂，常压气相催化合成N—乙基间甲氧基苯胺。转化率为90％，选择性为94％，反应温度：230℃—240℃，醇胺比为1：1．2，反应空速：0．75h-1。     

N-氰乙基苯胺的合成研究

报导了以三氯化铝为催化剂、低温条件下合成N-氰乙基苯胺的新工艺。以苯胺和丙烯腈为原料，加入少量对苯二酚，在水介质中75℃～80℃回流24小时合成标题化合物，收率96％，纯度96％。其收率随三氯化铝用量的增加而提高，在7％时达到最高；反应温度超过80℃时收率有所降低，当苯胺与丙烯腈的摩尔比为1：1．1时标题化合物的收率最高。     

N-甲基对硝基苯胺合成工艺研究

本文以对氯硝基苯、二乙醇胺和N-甲基甲酰胺(NMF)为原料合成了N-甲基对硝基苯胺,优化了工艺路线。用红外、核磁、气相色谱等方法对产物进行了表征。     

关于二氟马来酸苯胺盐的合成试验研究

了解二氟马来酸苯胺盐的合成试验,首选需要对五氟苯酚进行氧化,把五氟苯酚在过氧乙酸中进行充分氧化,然后在苯胺的作用下,就能得到二氟马来酸苯胺盐,总收率在40%。本文主要阐述了合成二氟马来酸苯胺盐的原料配比、反应的时间以及温度对产物收率的影响等。     

烯丙硫醇的合成研究

研究了以烯丙基溴和硫脲为原料,在相转移催化剂四丁基溴化铵的作用下,以水作溶剂,制得5-烯丙基异硫脲盐,并在氢氧化钠水溶液中水解,酸化,制得了重要的含硫香料烯丙硫醇。用气相色谱和红外光谱对其含量和结构进行了分析。     

2-(4-卤代苯甲酰基)苯胺的合成研究

研究了重要的有机中间体2-(4-卤代苯甲酰基)苯胺的通用合成路线,是以邻苯二甲酸酐为原料,与卤代苯(分别为氟苯、氯苯和溴苯)进行付-克反应得到羧酸;羧酸经酰氯化、酰胺化,制得邻苯甲酰基苯甲酰胺衍生物,然后再经过霍夫曼降解合成了标题化合物。对主要步骤反应条件进行了优化,得出比较合理的条件为:付-克反应,催化剂:AlCl3,配料比:1:2.2:6.4(苯酐:AlCl3:卤代苯);同时使用卤代苯既作反应试剂,又作溶剂,未反应的卤代苯回收套用,使收率基本定量;酰胺化反应氨气流量:10mLmin-1,使反应得以室温进行,无需制冷;四步反应总收率可达70%。     

氟氯苯胺的合成研究现状

氟氯苯胺是一种很有发展前途的医药合成中间体。综述了氟氯苯胺的几种合成方法,总结了以对硝基氯苯、邻二氯苯、邻氯苯胺、对硝基苯胺等为原料合成氟氯苯胺的方法,并对合成路线进行分析、比较,指出邻二氯苯为原料的合成路线工业生产可行。     

Preparation and characterization of pyrrole/aniline copolymer nanofibrils using the template‐synthesis method

Copolymer nanofibrils composed of pyrrole and aniline had been prepared by synthesizing the desired polymer within the pores of microporous anodic aluminum oxide (AAO) template membrane. To analyze their structure and properties, FTIR spectra were taken and thermogravimetric analysis (TGA) was applied. Also, the copolymer nanofibrils were photographed under scanning electron microscopy (SEM) and transmission electron microscopy (TEM) for microstructure analysis, and the conductivities were obtained by the four‐probe method. The result of SEM and TEM revealed that the obtained copolymer nanofibrils had uniform and well‐aligned array, and their diameter and length can be controlled by changing the aspect ratios of the AAO membrane. The result of IR spectrometry and TGA indicated that both polypyrrole and polyaniline were involved in the copolymer. The obtained nanofibrils were identified to be copolymer rather than composite. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3002–3007, 2001     

Investigation on the microstructure and the electric property of poly(propylene)/chlorinated poly(propylene)/poly(aniline) composites

The article presents results of studies on composites made from poly(propylene) (PP) modified with poly(aniline) (PANI) doped with dodecylbenzene sulfonic acid (DBSA) and chlorinated poly(propylene) (CPP). The volume resistivity of PP/CPP/PANI composites was detected, and the results show that the volume resistivity decreases with increasing CPP content, and there exists a minimum volume resistivity. Effects of CPP on the microstructure and crystalline structure of the PP/CPP/PANI composites and the relationship between the effects and the electric property were carefully analyzed by scanning electron microscope (SEM) and wide angle X‐ray diffraction (WAXD). The method that the specimens of SEM are polished is appropriate to investigate the morphology of conducting polymer composites. The obtained results illuminate that the area of conducting parts and insulating parts obtained from the digital analysis of the SEM image is obviously influenced by the CPP content, the parameters of the lamellar‐like structure are immediately related to CPP content and denote the dispersion of PANI‐DBSA, and the percent crystallinity and mean crystal size of PP are directly correlated with the CPP content. The increasing area of conducting parts, the increasement of layer distance, the decreasement of size and layer number of the lamellar‐like structure of PANI‐DBSA, and the increasement of the percent crystallinity and mean crystal size of PP are beneficial to the improvement of the conductive property of PP/CPP/PANI composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

催化加氢法绿色合成3,4-二氯苯胺关键技术研究

催化加氢还原法存在的技术难题是如何抑制脱卤现象,本研究选用特殊的脱卤抑制剂来抑制脱卤,使催化加氢还原法具有了操作环境温和、产品质量好、反应选择性高、无污染以及后处理容易等特点。这种3,4-二氯苯胺的绿色合成工艺使成本降低、环保效益好,对增强企业的竞争能力有一定意义。     

NMR investigation of aniline oligomers produced in the oxidation of aniline in alkaline medium

The chloroform‐soluble products of aniline or (¹⁵N)aniline oxidation in alkaline medium were analysed using one‐ and two‐dimensional ¹H NMR, ¹³C NMR and ¹⁵N NMR spectroscopy. Among the products, two were found to be prominent, namely a carbonyl‐containing semiquinonoid and a phenazine‐like structure. The probable mechanism of their formation is suggested. Copyright © 2011 Society of Chemical Industry     

Cu/SiO_2催化剂上苯胺与正丙醇气相合成N-丙基苯胺

采用等体积浸渍法制备了一系列铜系催化剂,考察了载体、Cu物种、Cu担载量、催化剂焙烧温度及焙烧时间等因素对苯胺与正丙醇气相合成N-丙基苯胺的影响。实验结果表明,Cu/SiO2催化剂具有很好的活性和选择性,在铜担载量为0.70 mmol/g SiO2、催化剂前体500℃焙烧4 h的最佳制备条件下,正丙醇转化率为100%,N-丙基苯胺的选择性高达92%;150 h的连续使用表明,Cu/SiO2催化剂具有良好的稳定性。催化剂的X射线衍射结果表明,具有一定铜结晶度的Cu/SiO2催化剂能够获得高收率的N-丙基苯胺,铜的结晶度过大或过小都会使副产物增加,N-丙基苯胺的选择性降低。     

Co-N-C催化剂的制备及“一锅法”合成N-亚苄基苯胺

以甲酰胺为氮源和碳源,乙酸钴为钴源,采用预先缩合/高温焙烧两步法制备了一系列Co-N-C催化剂,利用XRD、TEM、N₂吸附-脱附以及XPS等表征了催化剂结构,考察了催化剂用于硝基苯与苯甲醇"一锅法"合成N-亚苄基苯胺的催化性能及其稳定性。结果表明,焙烧温度和掺杂氮元素对Co-N-C催化剂性能影响显著,催化剂Co-N-C/800具有最好的催化性能,0.6 MPa氮气气氛下,温度140℃,反应12 h,硝基苯转化率达99%,N-亚苄基苯胺选择性达99%,催化剂重复使用5次,其活性无明显下降。