AHMT分光光度法测定废水中微量甲醛

甲醛与4-氨基-3-联氨-5-巯基-1,2,4-三氮杂茂(简称AHMT)溶液在碱性条件下缩合,然后经高碘酸钾氧化成6-巯基-5-三氮杂茂(4,3-b)-S-四氮杂苯紫红色化合物,其颜色的深浅与甲醛含量成正比。方法的最大吸收波长为554nm,甲醛含量在0~12μg·10mL-1范围内具有良好的线性关系,相关系数为0.9959,用于测定有机实验废水中微量甲醛的含量,相对标准偏差为3.45%,加标回收率在95.4%~110.5%之间。     

AHMT分光光度法测定乙二醛中微量甲醛

在氢氧化钾溶液介质中,甲醛与4-氨基-3-联氨-5-巯基-1,2,4-三氮杂茂(简称AHMT)起缩合反应,高碘酸钾将缩合反应产物氧化成6-巯基-5-三氮杂茂﹝4,3-b﹞-S-四氮杂苯紫红色化合物,据此建立了分光光度法测定乙二醛中微量甲醛的新方法。最大吸收波长为554nm,吸光度变化值与甲醛浓度在0~1.4μg·m L-1范围内呈良好的线性关系,相关系数为0.9956,相对标准偏差为2.57%(n=6),加标回收率在95.8%~108.7%之间。     

7-氮杂吲哚及其衍生物5-溴-7-氮杂吲哚的合成

7-氮杂吲哚是一种重要的杂环化合物,是合成维罗非尼、ABT-199等抗肿瘤药物的重要中间体,具有较高的生物医药价值。优化了合成7-氮杂吲哚的方法,以廉价易得的2-氨基-3-甲基吡啶为起始原料,经过两步反应,以48%的总收率得到7-氮杂吲哚。并在此合成方法的基础上进一步合成了5-溴-7-氮杂吲哚,经过三步反应,总收率达到43%。该合成方法具有原料易得、操作简便、路线简短、收率较高等优点。产物的结构经过核磁共振和高分辨质谱得到确认。     

2,8,9-三氧杂-5-氮杂-1-硅双环[3,3,3]-十一碳烷-3-酮类化合物的合成

具有五配位键的有机硅化合物—杂氮硅三环(silatrane),由于具有独特的生物活性和分子结构,正日益引起人们的兴趣。对一般杂氮硅三环的合成方法及其物理化学性质的报导甚多,但对环上带有羰基的另一类杂氮硅三环(2,8,9-三氧杂-5-氮杂-1-硅双环[3,3,3]十一碳烷-3-酮)的合成的报导直到目前只见到一篇。这类化合物的结构如下:     

5-溴-7-氮杂吲哚的合成工艺研究

以7-氮杂吲哚为原料,经氢化还原、溴化和脱氢等三步反应,制备了5-溴-7-氮杂吲哚;研究了氢化还原和溴化反应的工艺条件。较佳工艺条件:1氢化还原,反应压力为4 MPa,反应温度为95℃,反应时间12 h,溴化,7-氮杂吲哚啉和溴素的摩尔比为1∶1.15,总收率74.7%。     

二氮杂芴-9-酮的高效液相色谱分析

采用KromasilC18柱为分离柱 ,甲醇 -水 (体积比 6 0∶4 0 )为流动相 ,检测波长为 2 5 4nm ,苯乙酮做内标 ,对二氮杂芴 9 酮的含量进行了液相色谱定量检测。在 8～ 180 μg/mL峰面积 (y ,Ai/As)对标准溶液的质量浓度 (x ,μg/mL)线性关系良好 (r =0 99996 ) ,该法快速、准确     

氮-氨基-3-氮杂双环[3.3.0]辛烷盐酸盐合成工艺研究

以3-氮杂双环[3.3.0]辛烷盐酸盐为原料,采用亚硝化和金属还原两步法与氯胺法制备氮-氨基-3-氮杂双环[3.3.0]辛烷盐酸盐,利用正交实验研究了工艺条件对产品收率的影响。实验说明,亚硝化和金属还原两步法适合工业化,亚硝化温度85℃,溶液pH值1.5,还原温度30℃,N-亚硝基-氮杂双环[3.3.0]辛烷被锌粉还原,氮-氨基-3-氮杂双环[3.3.0]辛烷盐酸盐的总收率大于90%。     

硫代十二烷基-二巯基-1,3,4-硫二氮茂的合成

<正> 2,5-二巯基-1,3,4-硫二氮茂(DMTD)的烷基或二烷基衍生物是优良的霉菌抑制剂,避免显影液变暗和产生沉淀的添加剂;润滑油抗腐蚀添加剂;以及输油管路中防腐蚀的保护剂。文献[1]报道过DMTD的合成法。为了促进该产品的工业化和降低成本,我们用水代替乙醇精制。 DMTD的卤代烷衍生物种类繁多,其基本方法是DMTD的碱金属盐与Rx(R=烷基,x=Cl,Br等)在回流温度下反应生成烷基或二烷基衍生物。我们合成的硫代十二烷基-二巯基1,3,4-硫二氮茂(Ⅰ)。     

(6R,7R)-苯甲酰氨基-3-(1-甲基-5-四氮唑)-硫甲基-7-甲氧基-8-氧代-5-氧杂-1-氮杂二环[4.2.0]辛-2-烯-2-羧酸二苯甲酯的合成

以氧头孢烯为起始原料,通过甲氧基化得到甲氧基氧头孢烯,再在磺酰氯和三乙胺催化作用下与1-甲基-5-巯基四氮唑反应,得到(6R,7R)-苯甲酰氨基-3-(1-甲基-5-四氮唑)-硫甲基-7-甲氧基-8-氧代-5-氧杂-1-氮杂二环[4.2.0]辛-2-烯-2-羧酸二苯甲酯,总收率约78%,产物结构经核磁,质谱数据表征确认。     

3,5-二硝基-1-氧杂-3,5-二氮杂环己烷的分离、热分解及硝解机理分析

为掌握乌洛托品的硝解机理,研究了直接法硝解乌洛托品制备黑索今(RDX)的废水。实验通过乙酸乙酯萃取富集废水中的副产物,水洗至中性,浓缩,用薄层色谱法分析,展开系统为:丙酮/二氯甲烷/冰乙酸=1/6/0.1。采用硅胶柱柱层析法分离,丙酮/二氯甲烷梯度洗脱,分离得到两种物质,一种物质通过熔点、红外、核磁比对确认为1,3,5-三硝基-1,3,5-三氮杂环己烷(RDX);另一种物质采用红外光谱、核磁、质谱、元素分析及单晶衍射等分析方法进行结构表征,认定其为3,5-二硝基-1-氧杂-3,5-二氮杂环己烷。用DSC-TG技术研究了3,5-二硝基-1-氧杂-3,5-二氮杂环己烷热行为,结果表明该化合物是一种熔点低、热稳定性好的化合物,对主要副产物的分离和结构鉴定为直接法硝解反应机理提供了可靠的实验依据。     

COMPARATIVE METABOLISM OF PHENANTHRO[3,4-B]THIOPHENE,PHENANTHRO[4,3-B]THIOPHENE AND THEIR CARBON ANALOG BENZO[C]PHENANTHRENE BY RAT LIVER MICROSOMES

Phenanthro[3,4-b]thiophene (P[3,4-b]T) and phenanthro[4,3-b]thiophene (P[4,3-b]T) are thiasters of weakly mutagenic benzo[c]phenanthrene (B[c]P). These polycyclic sulfur heterocycles (thia-PAHs) represent a group of chemicals which have been identified in cigarette smoke. P[3,4-b]T is a potent mutagen in Salmonella typhimurium strain TA100 in the presence of rat liver S9, whereas its isosteric isomer P[4,3-b]T is a nonmutagenic compound. In order to understand the mechanism underlying the differences in the mutagenic activity of P[3,4-b]T and P[4,3-b]T, we have investigated the metabolism of P[3,4-b]T, P[4,3-b]T, and their carbon analogue B[c]P by rat liver microsomes. The liver microsomes from rats treated with Aroclor 1254 metabolized P[3,4-b]T, P[3,4-b]T, and B[c]P at a rate nearly 7- to 9-fold greater than of the control liver microsomes. High-performance liquid chromatography (HPLC) analysis of the metabolites formed showed that B[c]P was metabolized almost exclusively to its dihydrodiols which comprised predominantly K-region diol as noted in the previous studies. Our preliminary studies on the metabolism of P[3,4-b]T, P[4,3-b]T and B[c]P by liver microsomes from control and Aroclor 1254-treated rats have shown a significant reduction in the formation of 6,7-diol (K-region diol) and 8,9-diol (diol with a bay-region double bond) of the two thia-PAHs compared to the formation of analogous 5,6-diol (K-region diol) and 3,4-diol (diol with a bay-region double bond) from B[c]P. Both P[3,4-b]T and P[4,3b]T produced a major, relatively nonpolar metabolite(s) (80–96% of total metabolites). These studies indicate that the highly mutagenic P[3,4-b]T is not metabolized to dihydrodiol with a bay-region double bond to any greater extent than the weakly or nonmutagenic B[c]P or P[4,3-b]T, suggesting that the metabolite(s) other than P[3,4-b]T8,9-diol is likely to be involved in the mutagenicity of P[3,4-b]T.     

Synthesis of new Thiopyranopyridines

The synthesis of 5H-thiopyrano[4,3-b]pyridines, 8H-thiopyrano[3,4-b]pyridines, 1H-thiopyrano[3,4-c]pyridines and 1H-thiopyrano[4,3-c]pyridines from methyl pyridine esters 5–8 and nitriles 17–20 by simple photobromination, followed by reaction of the intermediate bromomethyl derivative with methyl thioglycolate and subsequent base induced cyclisation of the latter are reported.     

1,2,4-三唑并[3,4-b]-1,3,4-噻二唑的合成、结构及生物活性

为了筛选出新的高活性化合物,以二氨基硫脲与有机羧酸为原料,回流反应生成中间体4-氨基-5-取代-1,2,4-三唑硫酮,再与羧酸在POCl3的催化下合成了3,6-双取代1,2,4-三唑并[3,4-b]-1,3,4-噻二唑新化合物。目标化合物通过IR、元素分析和1H NMR对其结构进行了表征。并初步测定了该化合物对5种植物病原菌(烟草赤星病、马铃薯干腐病、小麦赤霉病、番茄早疫病、西瓜枯萎病)的杀菌活性,结果表明此类化合物对所测菌种具有良好的杀菌、抑菌作用。     

Fatty acid triazoles: Novel corrosion inhibitors for oil well steel (N-80) and mild steel

Three fatty acid triazoles, namely, 3-undecane-4-aryl-5-mercapto-1,2,4-triazole (triazole 1), 3(heptadeca-8-ene)-4-aryl-5-mercapto-1,2,4-triazole (triazole 2), and 3(deca-9-ene)-4-aryl-5-mercapto-1,2-4-triazole (triazole 3) were synthesized and their corrosion-inhibiting action in 15% hydrochloric acid was evaluated by weight-loss method and electrochemical techniques. Electrochemical polarization studies at room temperature indicated that all the triazoles are mixed-type inhibitors, i.e., they inhibit both anodic and cathodic reactions. The adsorption of these compounds onto mild steel from 15% HCl followed Temkin's adsorption isotherm.     

Green chemistry preparation of MgO nanopowders: efficient catalyst for the synthesis of thiochromeno[4,3-b]pyran and thiopyrano[4,3-b]pyran derivatives

A mild and efficient method for the synthesis of thiochro meno[4,3-b]pyran and thiopyrano[4,3-b]pyran derivatives using MgO nanopowders as a catalyst is described. The MgO nanopowders were prepared via a green biosynthesis method using an extract of Rosmarinus officinalis leaves and were characterized by Field Emission Scanning Electron Microscopy and X-ray diffraction analyses.     

5,7-二甲基-N-芳基-1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺的合成

以5-氨基-3-巯基-1,2,4-三唑为原料,经氧氯化后分别与6个芳胺反应,得到5氨基-N-芳基1,2,4-三唑-3-磺酰胺,继而和乙酰丙酮于乙酸中环合,制得6个取代的1,2,4-三唑[1,5-a]嘧啶-2-磺酰胺衍生物,同时讨论了胺解反应和环合反应的影响因素。所有目标产物的结构均经IR和1HNMR谱验证。     

三唑并嘧啶磺酰胺类化合物的合成及除草活性

以5-氨基-3-巯基-1,2,4-三唑为起始原料,经氧氯化、胺解和环合,制得了9个1,2,4-三唑[1,5-a]嘧啶磺酰胺类化合物,产物结构经IR和1H NMR验证,并测定了它们的除草活性。     

紫外分光光度法测定阔草清合成原料三唑的含量

建立了紫外分光光度法测定阔草清合成原料5-氨基-3-巯基-1，2，4-三唑的含量．方法为：用0．01M NaOH溶液溶解样品，在240nm处测定样品的吸光度，确定组分含量：该方法设备简单、操作迅速、方法准确。适于推广。     

2,3-Heterokondensierte Thiophene aus substituiertem 2-Aminothiophen-3-thiol

2,3-Heterocondensed Thiophenes from Substituted 2-Aminothiophen-3-thiole Ethyl 5-amino-4-mercapto-3-methyl-thiophen-2-carboxylate ( 2 ), obtainable from the appropriate thienylthiocyanate 1 by reduction, undergoes reactions in analogy to the 2-aminobenzenthiole. Thus, with formic acid or trimethylorthoacetat the thieno [2,3-d]thiazoles 4 and 5 are formed. Aromatic aldehydes yield the thieno[2,3-d]thiazolines ( 6 ) which can be dehydrogenated by sulphur to form 9 . From carbon disulfide and 2 the thieno[2,3-d]thiazol-2-thione ( 7 ) is formed. With phenacylbromide or ethyl bromoacetate 2 can be converted into the thieno[3,2-b] thiazine derivatives 11 or 12 . Diazotation of 2 yields the thieno[2,3-d]1,2,3-thiadiazole derivative ( 14 ).     

2,6-双-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑吡啶类衍生物的合成及抗菌活性

芳香羧酸酯化、肼解、成盐、环化成3-芳基-4-氨基-5-巯基-1,2,4-三唑与2,6-吡啶二甲酸在相转移催化剂四丁基碘化铵和POCl3作用下,高产率制得8种标题化合物,并利用IR、1HNMR、MS和元素分析对目标化合物的结构进行了表征.初步的抗菌实验表明,部分目标化合物表现出较好的抑菌活性.