用离子抑制色谱法分析二（2,2,6,6—四甲基—4—哌啶基）马来酸酯合？…

建立了用离子抑制色谱法分析二（２,２,６,６－四甲基－４－哌啶基）马来酸酯合成反应液的方法。平均回收率为９８．８％,相对标准偏差为０．５６％,测量的平均相对偏差不大于５．０％,方法简单,快速,可用于工艺条件的选择和质量检测。     

N,N''''-二(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺合成研究

采用超声波辐射使2,2,6,6-四甲基-4-哌啶酮(俗称三丙酮胺)和己二胺在室温条件下发生亲核加成反应,加成产物经减压蒸馏脱除水分子生成西佛碱,收率达75%;然后,在55～80℃、1.9～2.0 MPa条件下,以W-7型或-4型骨架镍作催化剂,对该西佛碱氢化,得到N,N'-二(2,2,6,6-四甲基-4-哌啶基)-1,6己二胺.     

二(2,2,6,6-四甲基-4-哌啶基)马来酸酯的合成新工艺

受阻胺类高分子合成材料光稳定剂(简称HALS)具有高效、耐热、耐抽提、无毒等优异特性,且与酚类抗氧剂有协同作用,广泛用于聚丙烯、聚乙烯、聚氯乙烯、聚碳酸酯、聚苯乙烯、聚氨酯、丙烯酸树脂、环氧树脂等高分子材料合成中,是当前世界受人注目、发展较快的一类光稳定剂[1...     

温度对4-甲基丙烯酸2,2,6,6-四甲基哌啶醇酯与苯乙烯自由基共聚活性的影响

本文研究了4-甲基丙烯酸2,2,6,6-四甲基哌啶醇酯和苯乙烯在不同温度下的自由基共聚合反应。发现在石油醚、苯和二甲基甲酰胺等溶剂中,反应温度对共聚活性的影响不同。用NMR法测定了单体与溶剂的络合常数;计算了单体与溶剂相互作用的活化能和活化熵,依此对共聚活性与温度之间的关系进行了讨论。     

2,2,6,6-四甲基哌啶氧化物催化的高选择性羟基氧化反应

次氯酸钠在2,2,6,6-四甲基哌啶氧化物(TEMPO)的催化下,可在温和的条件下选择性氧化胆酸类化合物的C3位羟基.该方法提供了与常规的氧化剂相反的区域选择性,为胆酸类化合物的结构改造提供了简洁的路线.     

薄层色谱法分离分析N,N-双(2,2,6,6-四甲基-4-哌啶)己二胺产物

研究了用薄层色谱法分离分析N,N 双(2,2,6,6 四甲基 4 哌啶)己二胺(简称哌啶胺)。该方法使用环己烷∶氨水∶甲醇∶乙醇∶异丙醇=2∶3∶4∶7∶8(V/V)为流动相(展开剂)、硅胶G为固定相、碘为显色剂,对哌啶胺的产物进行分离、分析,测定结果最小的ΔRf>0.06。该方法较高效液相色谱法方便、简单,且费用低,试样不用作任何处理,分析结果可用来指导哌啶胺的合成研究和工业化生产。     

反应型受阻胺-4-丙烯酰胺基-2,2,6,6-四甲基哌啶(AATP)熔融本体光聚合反应动力学研究

合成了反应型受阻胺4-丙烯酰胺基-2,2,6,6-四甲基哌啶(AATP),用FTIR、¹H-NMR和元素分析对其结构和组成进行了综合表征.以AATP为聚合单体,利用光-DSC技术研究了AATP熔融本体光聚合反应动力学.结果表明:AATP光聚合的诱导时间随引发剂浓度和辐照光强增加而缩短,光聚合速率随温度的升高而减小;在聚合初期,AATP光聚合速率分别与引发剂浓度和辐照光强的平方根呈较好的线性增长关系.并用稳态和非稳态相结合的光-DSC方法测定了AATP光聚合过程的动力学参数:链增长速率常数k_p=2.22-7.96×10²L/mol·s、链终止速率常数k_t=0.08-2.67×10⁴L/mol·s、表观活化能为E_p-E_t/2=-7.70-13.36kJ/mol、指前因子A_p/A_t^0.5=0.076-0.333(L/mol·s)0.5,k_p和k_t在聚合初期均随单体转化率的提高而增大,但kt增加的幅度远大于k_p.     

4-(4-吗啉)哌啶盐酸盐的合成

4-甲酸乙酯哌啶与溴苄反应,再经酰胺化和氨化反应制得关键中间体4-氨基-1-苄基哌啶(5);5与2,2-二溴二乙醚经环化反应制得N-苄基-4-(4-吗啉)哌啶,再经成盐,加氢合成了4-(4-吗啉)哌啶盐酸盐(1,总收率24.9%),1的结构经1HNMR,IR和GC-MS确认。     

3,4-二氢-1-(4-哌啶基)-2(1H)-喹啉酮的合成

以苄胺为原料,经6步反应得到新型抗高血压药OPC-21268的中间体3,4-二氢-1-(4-哌啶基)-2(1H)-喹啉酮,总收率13．9％．     

方酸衍生物的光敏性与结构关系的理论研究

量子化学方法早已成功地运用于探索药物分子的定量构效关系（QSAR）[1，2]，然而通过查阅近十几年的CA，发现用该方法进行有机光导材料（OPC）的QSAR研究工作甚少［3，4］．据推测，造成这种情况的原因是，影响OPC的光导性能的因素太多．例如，化合物的纯度、电行产生层（CGL）厚度、电行产生材料（CGM）与高分子粘结剂的配比、颗粒大小、结晶度、堆积方式、从CGL到电荷传输层（CTL）的空穴注人效率等．这么多的影响因素无疑是量子化学方法研究OPC的难点．随着大量OPCat合成出来及OPC研究的逐步深入，采用量子化学方法探讨化…     

离子抑制色谱法化学镀液中4种有机酸的含量及形态分析

离子抑制色谱法化学镀液中4种有机酸的含量及形态分析;离子抑制色谱;化学镀液;有机酸;形态分析     

离子色谱法分析衣康酸成品中的Cl~-,NO_3~-和SO_4~(2-)

采用离子色谱法分析衣康酸成品中的Cl-,NO-3和SO2-4。通过改变淋洗液碳酸盐的总浓度和CO2-3与HCO-3的比例,比较衣康酸与Cl-,NO-3,SO2-4在AS14阴离子交换柱上的保留行为。结果表明,衣康酸和SO2-4的保留行为相似,二价离子受影响程度较一价离子大;另外,选择AS11阴离子交换柱进行比较,两柱均适合衣康酸成品中痕量Cl-,NO-3,SO2-4的分析,但溶质的出峰顺序有所不同。在AS14分析柱上,Cl-,NO-3和SO2-4的检出限分别为20,40和50μg/L,在0 5～200mg/L内其浓度与峰面积均有良好的线性关系。     

Use of 1,4-bis(2,2,6,6-tetramethyl-1-oxyl-4-piperidyl)butane as a probe for studying acid sites

ESR spectroscopy was applied to study paramagnetic complexes of the nitroxyl biradical of 1,4-bis(2,2,6,6-tetramethyl-1-oxyl-4-piperidyl)butane formed with AlCl₃ in a toluene solution and resulted from the interaction with the acid sites on the SiO₂ and γ-Al₂O₃ surface. This biradical in solution forms a complex with two AlCl₃ molecules, and a complex with two hydroxyl groups is formed on the SiO₂ surface. When the biradical is adsorbed on the γ-Al₂O₃ surface, complex formation is complicated because of steric hindrance preventing bidentate coordination. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 165–167, January, 2007.     

Efficient Synthesis of Bis(4-Dimethaminophenyl)arylmethanes and Bis(4-Diamethaminophenyl)alkanes Using Iodine Reagent

A novel synthetic utility of NaICl₂ for the preparation of bis(4-dimethaminophenyl)arylmethanes and bis(4-dimethaminophenyl)alkanes is described. In the presence of an aqueous solution of NaICl₂, the reaction of arenes with aromatic aldehydes gives corresponding triarylmethane derivatives regioselectively in moderate to good yields. The method is also useful for the preparation of diarylalkane derivatives by using aliphatic aldehydes.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications ^® to view the free supplemental file.     

有机锡修饰的双吡唑甲烷及其与W(CO)5THF的反应

通过双吡唑甲基锂(LiCHPz₂)与有机锡卤化物(R₃SnX)的反应合成了一系列有机锡修饰的双吡唑甲烷配体(R₃SnCHPz₂).由于锡上取代基的不同,这些配体与W(CO)₅THF反应时表现出了不同的反应方式.三芳基锡修饰的双吡唑甲烷与W(CO)₅THF反应发生Sn-C(sp₃)键对W(0)中心的氧化加成;而三苄基锡修饰的双吡唑甲烷与其反应时仅给出羰基取代产物[Bz₃SnCHPz₂W(CO)₄].另外,二苯基苄基锡以及三(2-苯基-2-甲基丙基)锡修饰的双吡唑甲烷配体类似的反应导致配体的分解,产生单吡唑配体取代的羰基钨衍生物[W(CO)₅PzH]以及脱有机锡的双吡唑甲烷四羰基钨衍生物[CH₂Pz₂W(CO)₄].     

方酸衍生物的光敏性与结构关系的理论研究

The geometries of bis(4-dimethylaminophenyl)squaraine and its N and C-2 derivatives have been obtained by AMl and Gaussian 92.The relationship between their photosensitivties and geometries has been studied respectively. The linear relationships between oxidation Potential (EOX) of compounds 1-6 and their HOMO energy (EH), between the Photosensitivity (lgE0.5) of compound 1-5 and ΔET-GOX (the difference of the oxidation potential of charge-transporting material (CTM) and charge-generating material (CGM)), between lgE0.5 and ΔET-G (the difference of the HOMO energy of CGM and CTM) have been studied respectively by the least square fitting method. The result indicates that Eox and EH exhibit certain linearity (r=0.883), the correlation coefficient of lgE0.5 and ΔET-G (r=0.980) is greater than that of lgE0.5 and ET-GOX (r=0.883). It is concluded that the method of calculating the HOMO energy is better than that of detecting the oxidation potential during the study of QSAR of bis(4-dimethylaminophenyl)and its C-2 derivatives. According to the linear relationship obtained by AM1,bis(4-dimethylamino-2,6-fluorophenyl)squaraine has good photosensitivty.     

Synthesis and Analytical Application of Bis（2-diazoaminobenzothiazoyl）-benzidine to Determination of Mercury Ion by Fluorimetry

A new fluorescent reagent bis(2-diazoaminobenzothiazoyl)-benzidine(BDABTB) was synthesized by combining benzothiazole with benzidine and triazene reagent. The product was confirmed by elemental analysis, 1H NMR and FTIR. The excitation and emission wavelengths of BDABTB were 214 and 338 nm in a basic medium, respectively. The fluorescence was quenched by Hg2+ selectively and sensitively. The linear range of Hg2+ was 1.0×10-8―1.0×10-5 mol/L with a detection limit of 5.0×10-10 mol/L. It has been used to deter...     

双（1—乙酰基—4—取代苯甲酰基氨基硫脲）及其衍生物的合成

由丁二酰肼Ⅰ与取代苯甲酰基异硫氰酯在无水CaCl_2处理过的乙腈溶剂中亲核加成,制得一系列未知的双(1-乙酰基-4-取代苯甲酰基氨基硫脲)衍生物Ⅱ,Ⅱ在碱性条件下环化为未知的双(3-亚甲基-4-取代苯甲酰基-1,2,4-三唑啉-5-硫酮)Ⅲ ,所有化合物结构均经鉴定,部分化合物对枯草芽孢杆菌和大肠杆菌有抑制作用。