对甲苯磺酰胺和1.4—丁炔二醇在汞电极上的共吸附

用电毛细曲线、微分电容曲线、Ｓｔｕａｒｔ模型和自洽场分子轨道法（ＣＮＤＯ／２）研究对甲苯磺酰胺和１．４－丁炔二醇在汞电极上的共吸附特性。此共吸附本质上是一种物理吸附。在其最大的吸附电位附近，二者分别以侧卧方式吸附于表面，并在共吸附层表现出静电斥力作用作用。当两者的浓度相等时，１．４－丁炔二醇的吸附占优势。     

紫外光谱法和高效液相色谱法测定邻、对甲苯磺酰胺

本文采用紫外光谱法(UV)和高效液相色谱法(HPLC),分别成功地测定了邻、对位甲苯磺酰胺的异构体分布。UV法采用邻、对位异构体在异吸收点的紫外吸收比例来计算。HPLC法采用ZORBAX C_8柱,25cm×4.6mmi·d,流动相乙腈/水的比例为15/85,在UV268nm下检测。两种方法的相对标准偏差小于3.4％。     

对甲苯磺酰胺电还原过程的电化学-ESR研究

对一些含硫的镀镍光亮剂电还原反应曾提出过两种反应机理，一种是生成硫酸的机理，一种是脱磺酸（酞）基团的机理．Brook和Crossleyu］认为这类反应是按后一种机理进行的自由基反应，但未对中间产物作出检测．因此目前对反应机理尚无定论．为了阐明还原中间产物与反应本性，本文利用自旅捕集技术与UV光谱研究了对甲基磺欧胺在汞电机上的电还原过程．1实验1．1仪器HDVI－xFD｛－x－Y仅组装CV图测量系统；日本JE巳FElxG波谱仪；xJP七ZI新极谱仪阳春应化所）2751G紫外分光光度计．1．2主要试剂苯亚甲基叔丁基氮氧化物（PBN，由中科…     

(S)-N-苯亚甲基对甲苯亚磺酰胺与1°RMgBr选择性加成反应的研究

(S) N 苯亚甲基对甲苯亚磺酰胺与 1°RMgBr通常发生 1,2 加成反应。在催化量CuI存在下 1,4 加成产物明显增加 ,采用烷基铜溴化镁 ,反应具有高的区域选择性和立体选择性。当用 3 丁烯基铜溴化镁时 1,4 加成产物收率达 80 % ,1,4 加成异构体 (SS,S)和 (SS,R)的摩尔比为 1∶6     

钴－5－（4－硝基苯偶氮）－8－（4－甲苯磺酰氨基）－喹啉配合物的极谱波研究

钴（Ⅱ）在ＨＡｃ－ＮａＮＯ＿２－吐温－８０－ＮＰＴＳＱ体系中有一灵敏的阴极极化导数波，其峰电位－１．００Ｖ（ｖｓ．ＳＣＥ），钴浓度在４．０×１０￣（－９）～３．０×１０￣（－７）ｇ／ｍＬ范围内与峰电流有良好的线性关系。本文讨论了测定钴（Ⅱ）的最佳实验条件，对极谱波的性质进行了初步探讨，并作了维生素Ｂ＿（１２）中钴的测定，测定结果的相对标准偏差为３．７４％，回收率为９６～１０８％。     

l—对甲苯磺酰乳酸乙酯合成中产率分析方法的研究

报道了实验室可行、工业生产实用的l－对甲苯磺酸乳酸乙酯产率的分析方法,采用K2CrO4-K2Cr2O7混合指示剂,其最佳配比为K2CrO4:K2Cr2O7=6:1（质量比）,体系的最佳pH为5．8,测得l-乳酸乙酯与对甲苯碘酰氯反应制备和的l-对甲苯磺酰乳酸乙酯的产率为94．0％。     

单取代对甲苯磺酰环糊精在树脂上的吸附分离特性

单取代对甲苯磺酰环糊精在树脂上的吸附分离特性;对甲苯磺酰-β-环糊精;树脂;吸附;分离     

对甲苯磺酰氟/双氧水/碱体系和烯烃环氧化反应的研究

研究了对甲苯磺酰氟和双氧水在碱性条件下原位生成对甲苯过氧磺酸和烯烃尤其是富电子烯烃的环氧化反应的情况. 该氧化体系能将位阻较小的富电子烯烃环氧化, 并以良好的得率给出环氧化产物; 对位阻较大的富电子烯烃, 只以中等得率生成了环氧化产物. 它也能将α,β-不饱和酮环氧化. 实验结果进一步拓展了磺酰氟试剂在有机合成化学中的应用.     

Synthesis of Dopamine,Rotigotin, Ladostigil,Rasagiline Analogues 2-Amino-4,5,6-trimethoxyindane, 1-Amino-5,6,7-trimethoxyindane,and Their Sulfamide Derivatives

Dopamine, rotigotin, ladostigil, and rasagiline analogues 2-amino-4,5,6-trimethoxyindane and 1-amino-5,6,7-trimethoxyindane were synthesized starting from 5,6,7-trimethoxyindan-1-one for the first time with 34% and 45% total yields. α-Carboxylation of indanone, reduction of ketone group with Et₃SiH, basic hydrolysis of ester, Curtius reaction of the acid, and addition of BnOH afforded the corresponding carbamate. Pd-C-catalyzed hydrogenolysis of carbamate and deprotonation of amine hydrochloride with NaOH gave the dopamine and rotigotin analogue 2-aminoindane. Reduction of 5,6,7-trimethoxyindan-1-one with NaBH₄ afforded the alcohol, which was then converted to the azide derivative via Mitsunobu reaction with diphenylphosphoryl azide; Pd-C catalyzed hydrogenation of the azide to the amine hydrochloride and then deprotonation of the amine hydrochloride with NaOH furnished the ladostigil and rasagiline analogue 1-aminoindane. These amines and BnOH were reacted with CSI to produce sulfamoyl carbamates, which were converted to sulfamides via Pd-C-catalyzed hydrogenolysis reaction with 20% and 25% total yields.     

硫脲与多种阴离子共吸附行为的拉曼光谱研究

在电化学的研究与应用中，因硫豚（1’川可用作电镀添加剂、金属的缓蚀剂和一些电极反应的催化剂［‘］而受到人们的广泛重视．早在三十年代初就开展了有关水溶液和非水溶液体系中硫豚在不同金属电极表面的吸附行为的研究【’，’］、随着光谱电化学技术的建立、发展和不断完善     

Coadsorption of Tetraalkylammonium Cations and Halide Anions on the Uncharged Surface of Mercury Electrode

The data on coadsorption of tetraethylammonium (Et₄N⁺), tetrapropylammonium (Pr₄N⁺), and tetrabutylammonium (Bu₄N⁺) cations with Cl^–, Br^–, and I^– anions on an uncharged mercury electrode are compared with the models of coadsorption in a common monolayer and two parallel layers. The second model is shown to be in best agreement with experimental isotherms. However, the least discrepancy between calculations and experimental results is obtained when coadsorption of mentioned cations and anions is described by the Frumkin isotherm for neutral molecules with certain effective adsorption parameters.     

Rh2CO2/Al2O3上H2吸附及CO和H2共吸附

CO加氢反应机理一直是许多化学工作者感兴趣的课题．Rh催化剂因其优良的性能而被用于 CO加氢机理研     

负载Ni催化剂上1,4-丁炔二醇加氢反应的载体效应研究

制备了Ni负载量为15%的3种催化剂Ni/Al_2O_3、Ni/SiO_2、Ni/ZrO_2,考察了其在1,4-丁炔二醇加氢反应中的催化性能,结合XRD、H_2-TPR、H_2-TPD、N_2物理吸附等表征,研究了载体性质对催化剂1,4-丁炔二醇加氢性能的影响.结果表明,Ni/SiO_2催化剂上,由于Ni与SiO_2间弱的相互作用,Ni物种主要以大晶粒形式存在,产生大量弱吸附H_2物种,有利于低温下1,4-丁炔二醇加氢,在温度50℃,氢气压力1 MPa时,反应2 h可实现1,4-丁炔二醇的完全转化,1,4-丁烯二醇和1,4-丁二醇选择性分别达到68.1%与18.2%.Ni/Al_2O_3中Ni与载体间具有强相互作用,主要存在Ni-Al_2O_3界面或溢流到Al_2O_3载体表面的强吸附H_2物种,而Ni表面的弱吸附H_2物种较少,催化加氢活性明显降低.Ni/ZrO_2中由于还原过程中ZrO_2的迁移包裹作用,Ni表面低温吸附H_2物种最少,活性最低,1,4-丁炔二醇转化率仅为8.1%,主产物为1,4-丁烯二醇.     

Silver Cation Reduction on a Mercury Electrode: Effect of Two-Dimensional Condensed Layer of 1-AdOH during Individual Adsorption and Coadsorption with Tetraalkyl Cations

Effect of a condensed layer (CL) of 1-adamantanol (1-AdOH) during individual adsorption and coadsorption with tetraalkyl cations on the kinetics of the electroreduction (ER) of cation Ag⁺ at a mercury electrode is studied with the aim of revealing the link between the rate of electrode processes and the structure of two-dimensional CL. It is shown that ER of Ag⁺ occurs by means of penetration of the depolarizer particles through the adsorption layer. Polarization curves are calculated under the assumption that the potential barrier for ER of Ag⁺ in the presence of CL of 1-AdOH is defined by the work for overcoming two-dimensional pressure in the layer. Satisfactory agreement between experimental and calculated dependences in the region of ascending branches of polarization curves is demonstrated. It is established that the degree of the inhibiting action of mixed adsorption layers (as compared with individual CL of 1-AdOH) on ER of Ag⁺ depends on the 1-AdOH activity in solution and the nature of the organic cation. It is assumed that the latter effect is caused by the surface activity of cations studied.     

FeTPP和CoTPP电化学氧化还原的量子化学研究

用限制性的CNDO/2方法研究了FeTPP和CoTPP不同还原阶段的电子结构,结果表明,在FeTPP还原反应中第一个还原电子和Fe的d轨道相作用,第二个还原电子与卟啉环的4个氮原子及同它相连的8个碳原子的p轨道相作用,而CoTPP的2个还原电子与Co的d轨道相互作用,这与紫外原位光谱的实验结果完全一致。     

Molecular orbital treatments of hydrogen bonded systems. 2. Dimers of water and HCN

Calculations were performed to investigate the reliabilities of the CNDO/2, PRDDO, and MNDO approximate molecular orbital methods. Systems selected for study included the linear, cyclic, and bifurcated dimers of water as well as the linear and cyclic dimers of HCN. The PRDDO method was found to provide the most consistently accurate reproduction of ab initio and experimental data. CNDO/2 performed fairly well in a number of cases but yielded extremely poor results for the cyclic dimers of both H₂O and HCN. Hydrogen bond strengths were consistently underestimated by MNDO which also furnished erroneously large intermolecular separations. In addition, MNDO calculations indicate the bifurcated water dimer to be most stable in contrast to other quantum mechanical and experimental information.See Ref. [1] for Paper 1 of this series.     

Voltammetry of Potassium Octyl Xanthate at Mercury Electrode

Abstract

Electrochemical studies of potassium octyl xanthate at the mercury electrode reveal that the product of the anodic reaction is strongly adsorbed at the mercury surface as indicated by a prewave. The adsorbed film greatly affects the characteristics of the anodic wave of xanthate in aqueous medium. The current of total wave is proportional to the concentration of xanthate from 0.32 to 1.6 mM.     

汞膜电极上N-乙酰-L-半胱氨酸的电化学行为

研究了汞膜电极上N 乙酰 L 半胱氨酸 (C5H8O3 SH ,NAC)的电化学行为和测定方法。在 0 .1mol LHAc NaAc缓冲溶液 (pH =4 .5 )介质中 ,方波伏安扫描于～ -0 .2 5V(vs.Ag AgCl)处出现一灵敏的阴极还原峰 ,用循环伏安法、线性扫描极谱法和脉冲极谱法等手段研究了体系的电化学行为及其反应机理。实验表明 :该峰具有明显吸附性 ,吸附分子为Hg2 (C5H8O3 S) 2 ,电子转移系数α为 0 .82 ,电子转移数为 1。NAC的浓度在1 2×1 0 - 8～ 5 .0× 1 0 - 6 mol L范围与其方波伏安峰高有良好的线性关系。方法的检出限为 5 .0× 1 0 - 9mol L ,用于富露施颗粒剂中NAC含量的测定 ,结果满意