应用阴离子交换树脂有效合成3—芳氨基—4—氰基—5—氨基吡唑

研究了不活泼芳胺（杂环胺）与α，α－二氰基二硫缩醛的加成－消除反应，报道了一种应用阴离子交换树脂有效合成３－芳氨基－４－氰基－５－氨基吡唑的一锅煮方法。     

β—芳氧基丙酸衍生物的合成及生物活性

合成了β－芳氧基丙酸芳酯及β－芳氧基丙酰芳胺等１７种化合物，经ＩＲ，ＵＶ，ＨＮＭＲ和元素分析确定了它们的结构，并对它们的生物活性进行了初步考察。     

1—芳酰基—3—（4—苯磺酰胺）硫脲类化合物的合成

以无水丙酮作溶剂，由芳酰基异硫氰酸酯与左侧胺反应合成了一系列新的１－芳酰基－３－（４－苯磺酰胺）硫脲。     

3—芳基—5—巯基—1,2,4—均三唑的双—Mannich反应研究

研究了在氯化氢－乙醇溶液中，３－芳基－５－巯基－１，２，４－均三唑与甲醛和伯胺（芳胺或脂肪胺）的双Ｍａｎｎｉｃｈ反应，合成了１３的的稠杂环化合物３，５－二取代０四氢均三唑并「３，４－ｂ」「１，３，５」噻二嗪，经元素分析、Ｉ手ＭＳ确定了结构，初步测定了该类化合物的生物活性。     

2,4—二羟基—3—芳氨基甲基苯乙酮和8—乙酰基—3—芳基—3,4—二…

研究了在氯化氢－乙醇溶液或乙醇溶液中，２，４－二羟基苯乙酮与甲醛和芳胺的Ｍａｎｎｉｃｈ反应，分别得到了５个２，４－二羟基－３－芳氨基甲基苯乙酮和５个８－乙酰基－３－芳基－３，４－二氧－５－羟基－２Ｈ－１，３－苯并恶嗪新化合物，用元素分析，ＩＲ，ＨＮＭＲ，ＭＳ，ＵＶ确定了它们的结构，并成功地实现了２，４－二羟基－３－芳氨基甲基苯乙酮和８－乙酰基－３－芳基－３，４－二氢－５羟基－２Ｈ，１，３－苯并恶嗪     

N—（1—氧代—1—磷杂—2,6,7—三氧杂双环[2.2.2]—辛烷—4—羰…

首次合成了酰基异硫氰酸酯４，并将其与各种芳胺、脂肪胺和肼衍生物加成，得到了２２种未见文献报道的含双环笼状磷酸酯结构的酰基硫脲化合物（５ａ－５ｘ）。４与丁胺反应未得到预期的加成产物，而得到相应的取代产物６。研究了５的结构。     

3—芳胺甲烯基—6—烷基（芳基）_5,6—二氢—2H—吡喃—2,4—二 …

以５,６－二氢－６－烷基（芳基）－２Ｈ－吡喃－２,４－二酮（１）、芳胺（２）和原甲酸三乙酸进行缩合反应、合成了２０个３－芳胺甲烯基－６－烷基（芳基）－５,６－二 喃－２,４－二酮（３）,由于分子内氢键的合成,化合物３由一对构象异构体４和５组成,生物活性初步测定结果表明,这些化合物均有一定的杀菌活性。     

β－芳氧基丙酸衍生物的合成及生物活性

合成了β－芳氧基丙酸芳酯及β－芳氧基丙酰芳胺等１７种化合物，经ＩＲ、ＵＶ、１ＨＮＭＲ和元素分析确定了它们的结构，并对它们的生物活性进行了初步考察。     

相转移催化法合成N—2—苯基—1,2,3—三唑—4—甲酰基—N′—芳基硫脲

报道了２－苯基－１，２，３－三唑－４－甲酰氯和硫氰酸铵在ＰＥＧ－４００固液相转移催化下与芳胺反应，制得一系列新的含２－苯基－１，２，３－三唑环的硫脲衍生物，并经ＩＲ，＾１ＨＮＭＲ和元素进行了结构确证。     

相转移催化法合成N,N‘—二芳基—1,4—苯二氧基二乙酰胺

于液－液相转移催化条件下，以ＰＥＧ－４００为催化剂，通过１，４－苯二氧基二乙酰氯与芳胺反应，合成了相应的酰胺３ａ～３ｏ。     

Determination of aromatic amines from azo dyes reduction by liquid‐phase sorbent trapping and thermal desorption‐gas chromatography‐mass spectrometry

A novel method based on thermal desorption was developed for the trapping of aromatic amines from azo dyes reduction in liquid phase. Combining GC‐MS, the detection limits for 21 kinds of aromatic amines ranged from 0.1 to 3 mg/kg. The recoveries of most aromatic amines were ?70% with RSDs ?10%. This method also offers low sample and organic solvent requirements, effective preconcentration and convenient procedure. It has been applied to determine aromatic amines from the real samples of textile and yielded good results.     

离子液体作高效液相色谱流动相添加剂分离测定芳香胺

建立了以离子液体作反相高效液相色谱流动相添加剂分离测定邻苯二胺、苯胺和对甲苯胺3种芳香胺的方法。实验以C18反相色谱柱为分离柱,采用紫外检测方法,考察了检测波长、甲醇含量、咪唑离子液体烷基链长度、离子液体溶液浓度等条件对分离和测定的影响,并与其它分离测定芳香胺的方法进行了比较。优化的色谱条件为:以甲醇/1-丁基-3-甲基咪唑四氟硼酸盐水溶液(3.0mmol/L,乙酸调节pH 3.5)=30/70(V/V)为流动相;检测波长254 nm;流速1.0mL/min;柱温30℃。在此条件下,3种芳香胺达到基线分离,在6.5 min之内分离完全;在1～40 mg/L范围内,线性回归方程的相关系数达到0.99以上;检出限为0.07～0.41 mg/L。将本方法应用于废水的测定,加标回收率在92.3%～96.7%之间,相对标准偏差小于3.5%。     

Thermometric titrations of amines with nitrosyl perchlorate in acetonitrile solvent

Thirteen aliphatic and four aromatic amines, namely diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-butylamine, isopropylamine, di-isopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, aniline, N,N-dimethylaniline, 2-nitroaniline and 4-nitroaniline were titrated thermometrically with nitrosyl perchlorate in acetonitrile solvent. All the aliphatic amines gave very well-shaped thermometric titration curves. The calculated recovery values of the amines were very good. In comparison, the aromatic amines, aniline and N,N-dimethylaniline gave rather well-shaped titration curves, but the recovery values were fairly low. 2-Nitro- and 4-nitro anilines gave no thermometric response at all. The heats of reaction of the amines with nitrosyl perchlorate are rather high. However, the average heat of reaction of the aromatic amines is approximately two-thirds that of the average heat of the aliphatic amines. To support this method all the amines were also titrated potentiometrically and very similar results to those obtained with the thermometric method are seen. The nitrosyl ion is a Lewis acid, strong enough to titrate quantitatively aliphatic amines in acetonitrile solvent, but not strong enough to titrate aromatic amines at the required level in the same solvent.     

快速溶剂萃取-在线净化-GCMS联用分析纺织品中10种芳香胺

利用在线净化-快速溶剂萃取结合气相色谱-质谱联用技术,建立了一种快速、高效的多种致癌芳香胺类成分的样品前处理及分析方法。纺织样品中的偶氮染料在萃取池内高温和高压条件下进行氧化-还原裂解反应,裂解芳香胺产物萃取后,经池内硅藻土填料实现在线净化。10种芳香胺类物质在0.5~90 mg/L的范围内与峰面积呈线性,检测限在1.2~4.6 mg/kg之间,快速溶剂萃取处理所得10种致癌芳香胺成分的回收率在82.6%~96.3%之间,RSD范围在1.8%~4.7%之间。     

Analysis of aromatic amines as N-propoxycarbonyl derivatives by gas chromatography with nitrogen-phosphorus selective detection

A selective and sensitive method for the analysis of aromatic amines by GC was developed. Aromatic amines were converted to their N-n-propoxycarbonyl derivatives and measured by GC with nitrogen-phosphorus selective detection (NPD) using an HP-5 fused-silica capillary column. The derivatives of the 20 aromatic amines provided excellent NPD responses, and were resolved both quantitatively and reproducibly within 15 min. The calibration curves for aromatic amines in the range 20-500 ng were linear and the detection limits at an S/N of 3 were ca. 19-139 pg injected. This method was applied successfully to combustion smoke and human urine samples, and analyzed without any interference from coexisting substances.     

液液萃取-分散液液微萃取-气相色谱-质谱联用测定纺织废水中痕量禁用偶氮染料

建立了液液萃取-分散液液微萃取-气相色谱-质谱联用技术测定纺织废水中痕量偶氮染料的方法。废水中的偶氮染料在碱性条件下经连二亚硫酸钠还原成芳香胺后,先用叔丁基甲醚液液萃取、盐酸反萃进行预浓缩及净化;再以乙腈-氯苯体系进行分散液液微萃取,气相色谱-质谱测定。对前处理条件进行了优化,考察了酸碱度及盐效应对芳香胺萃取效率的影响,结果表明：液液萃取过程中加入30 g NaCl,分散液液微萃取过程中加入1 mL 5 mol/L的NaOH调节体系至碱性才能达到较好的萃取效率。在优化的实验条件下,21种目标物均呈现良好的线性关系,其中13种芳香胺的线性范围为0.05~10 μg/L,7种芳香胺的线性范围为0.05~5 μg/L,2,4-二氨基苯甲醚的线性范围为20~100 μg/L,相关系数为0.996~0.999。20种芳香胺的检出限可达0.05 μg/L,2,4-二氨基苯甲醚检出限为20 μg/L。印染、机织、印花等实际废水加标试验表明,方法的回收率为75.6%~115.1%。该方法富集倍数高,检出限低,适用于纺织废水中痕量禁用偶氮染料的检测。     

分散液相微萃取-气相色谱法测定水样中六种芳香胺

建立了分散液相微萃取-气相色谱同时测定环境水样中氟苯胺等6种芳香胺的方法.确定了色谱条件,在4 min内实现了对6种芳香胺的分离与测定;对萃取剂种类及用量、分散剂种类及用量;水样pH值、NaCl加入量等前处理条件进行了优化,使得水样中6种芳香胺得到了同时提取和富集.在最佳实验条件下,建立了6种物质的工作曲线,其相关系数...     

固相萃取-气相色谱／质谱同时测定卷烟滤嘴中的四种芳香胺

采用固相萃取-气相色谱/质谱(SPE-GC/MS)法同时测定了卷烟抽吸后滤嘴中截留的1-氨基萘、2-氨基萘、3-氨基联苯和4-氨基联苯四种芳香胺.该法采用5%的盐酸超声振荡提取滤嘴中的芳香胺,提取液经液液萃取后进行衍生化和固相萃取,浓缩后进行GC/MS分析.1-氨基萘、2-氨基萘、3-氨基联苯和4-氨基联苯的检出限分别为0.51、0.42、0.18、0.18 ng/mL,相对标准偏差在0.94%～3.02%之间,回收率在92.67%～97.20%之间.该方法用于卷烟滤嘴中四种芳香胺的测定,结果发现不同材料的滤嘴对四种芳香胺有不同的截留作用.     

Simultaneous determination of aliphatic and aromatic amines in water and sediment samples by ion-pair extraction and gas chromatography-mass spectrometry

A gas chromatography-mass spectrometry (GC-MS) method has been proposed for the determination of aliphatic and aromatic amines in a variety of environmental samples including wastewater, river water, sea water and sediment samples. The method includes ion-pair extraction with bis-2-ethylhexylphosphate (BEHPA), derivatisation of compounds with isobutyl chloroformate (IBCF) and their GC-MS analysis. Aliphatic and aromatic amines were isolated from aqueous samples using BEHPA as ion-pair reagent and derivatised with IBCF for their chromatographic analysis. Solid-liquid extraction of aliphatic and aromatic amines in sediment samples were performed in Soxhlet apparatus with acidic MeOH and ion-pair extraction with BEHPA were carried out for the isolation of amines followed by derivatisation with IBCF. Aliphatic and aromatic amines were then analysed with GC-MS in both electron impact (EI) and positive and negative ion chemical ionisation (PNICI) mode as their isobutyloxycarbonyl (isoBOC) derivatives. The obtained recoveries ranged from 81.0 to 98.0% and the precision of this method, as indicated by the relative standard deviations (RSDs) was within the range of 0.5 and 4.3%. The detection limits obtained from calculations by using GC-MS results based on S/N = 3 were within the range from 0.07 to 0.50 ng/l.     

Development of a new open-tubular capillary electrochromatography method for in vitro monitoring of toxic aromatic amines distribution in rat blood

Exposure to aromatic amines from different industrial and agricultural activities entails a substantial risk of deleterious somatic effects, genetic damage and cancer development. Thus, a new and simple method for separation and analysis of aromatic amines has been developed by open-tubular capillary electrochromatography with a novel amphipathic block copolymer (poly(tert-butyl acrylate)(127)-block-poly(glycidyl methacrylate)(86)) coating based on its self-assembled property. Key factors affecting the separation efficiency of the test analytes, such as pH, buffer concentration and selective solvent, were studied in detail. Meanwhile, method validation was well evaluated by linearity (≥0.998), detection limit and recovery. Application of this developed protocol on in vitro monitoring of the target aromatic amines distribution in rat blood demonstrated its potential usage for separation and determination of aromatic amines in biological samples. Additionally, for assimilating more polymeric materials into analysis of aromatic amines, the effect of morphology changes of the amphipathic block copolymer coating on open-tubular capillary electrochromatography separation was also studied, and the result revealed that the block copolymer coating could play the same role as surfactant.