Iodine(III)-mediated bicyclic diazenium salt formation

The hypervalent iodine(III) reagent PhI(OTf)₂ has been shown to be an effective oxidant for the conversion of linear aryl-hydrazones bearing a pendant alkene into bicyclic diazenium salts. This oxidative cyclization presumably occurs by the iodine(III) mediated formation of a 1-aza-2-azoniaallene salt intermediate that undergoes a subsequent intramolecular 1,3-dipolar cycloaddition with the pendant alkene.     

A new efficient method for the synthesis of 3,4-dihydro-2H-1,4-benzoxazines via iodocyclization

An efficient approach for the synthesis of 3,4-dihydro-2H-1,4-benzoxazine derivatives is described by molecular iodine- mediated cyclization. The reaction condition is very simple, offers easy isolation, and affords good to excellent yields of the products.     

New chiral hypervalent iodine(V) compounds as stoichiometric oxidants

The synthesis and application of some new hypervalent iodine compounds bearing chiral and achiral ester motives derived from easily accessible starting materials is presented. The oxidation is carried out using dimethyldioxirane as an oxidant providing the desired compounds in moderate to high yields. A crystal structure analysis for one iodine(V) derivative is investigated. The λ⁵-iodanes are applied as stoichiometric reagents in the oxidation of thioanisole to phenylmethyl sulfoxide, benzyl alcohol to benzaldehyde, and meso-hydrobenzoine to benzaldehyde, benzyl, and benzoin.     

Das erste Alkalimetall‐Lanthanoid(III)‐Iodid‐Oxotellurat(IV): Na2Lu3I3[TeO3]4

Colorless platelets of Na₂Lu₃I₃[TeO₃]₄ were obtained within five days at 775 °C by the reaction of Lu₂O₃ and TeO₂ in a 3:8 molar ratio with NaI added in excess as both fluxing agent and reactant in evacuated silica ampoules. It crystallizes in the monoclinic space group P2/c with the lattice parameters a = 921.69(5), b = 552.71(3), c = 1664.37(9) pm, β = 90.218(4)° and Z = 2. The crystal structure of Na₂Lu₃I₃[TeO₃]₄ exhibits two crystallographically different Lu³⁺ cations, both coordinated by eight O^2– anions as square antiprisms. These polyhedra are interconnected through four common edges to build up {}^2_∞ {[LuO{}^e_8/2 ]^5–} layers (e = edge‐linking) parallel to (100). Furthermore, the crystal structure includes a crystallographically unique Na⁺ cation surrounded by four O^2– and four I^– anions also in the shape of a square antiprism. These polyhedra connect via common (I2)^–···(I2)^– edges in generating {}^1_∞ {[Na₂O₈I{}^e_4 ]^18–} double‐strands that are further linked by (I1)^– vertices to result in the formation of {}^2_∞ {[Na₂O₈I₃{}^e,v_3 ]^17–} layers (v = vertex‐linking) spreading out parallel to (100) as well. Thus, the crystal structure contains two crystallographically distinct I^– anions, of which (I1)^– is coordinated nearly linear (? (Na–I1–Na) = 179.6°) by two Na⁺ cations, whereas (I2)^– has contact to three of them displaying a distance of 114 pm from the triangular (Na⁺)₃ plane. The crystal structure of Na₂Lu₃I₃[TeO₃]₄ is completed by two crystallographically independent Te⁴⁺ cations that show stereochemically active non‐bonding electron pairs (“lone pairs”) and are located above and below the {}^2_∞ {[LuO{}^e_8/2 ]^5–} layers forming isolated ψ¹‐tetrahedral [TeO₃]^2– anions (d(Te–O) = 188–190 pm) with all oxygen atoms.     

酸性介质中碘离子在铂电极上的电化学氧化行为

采用循环伏安法研究了酸性介质中碘离子在铂电极上不同电位区间, 不同酸度下的电化学反应行为. 结果表明, 当极化电位较低(小于0.6 V(vs Hg/Hg2SO4))时, 碘离子在铂电极上发生2I--2e→I2电氧化反应, 反应产物通过I2+I-=I-3被进一步溶解, 整个反应属于E-C(electrochemical-chemical)模式. 电氧化过程中可以形成碘膜, 其也可以被碘离子溶解. 当极化电位升高至0.6 V(vs Hg/Hg2SO4)或以上时, 碘离子会直接电氧化为高价态碘化合物, I-+3H2O→IO-3+6H++6e, 而析出的碘膜并不发生再氧化反应; 在电化学还原过程中, 出现了两个还原峰, 分别对应于I2、I-3的还原反应; 在无碘膜时, 碘离子电氧化过程受溶液中碘离子的液相扩散步骤控制; 碘膜形成后, 主要受碘膜中碘离子的固相扩散控制; 酸度对于碘离子的电化学氧化过程有很大的影响, 其线性极化曲线的起峰电位及电流峰值电位均随酸浓度升高而负移.     

碘、碘离子和碘三离子的紫外吸收光谱

研究了碘I₂、碘离子I- 和碘三离子I-₃ 水溶液的紫外吸收光谱,测定了三种型体的摩尔吸光系数。I₂水溶液在203 nm呈现一吸收峰,摩尔吸光系数为1.96×104 L·mol-1·cm-1;I- 水溶液在193和226 nm呈现双吸收峰,摩尔吸光系数分别为1.42×104和1.34×104 L·mol-1·cm-1;当I₂水溶液与KI溶液混合时,在288和350 nm出现两个吸收峰,表明I-₃的形成。利用饱和法测得I-₃在288和350 nm处的摩尔吸光系数分别为3.52×104和2.32×104 L·mol-1·cm-1。     

酸性络蓝K褪色光度法测定食盐中微量碘

在硫酸介质中 ,碘酸根对酸性络蓝 K具有褪色作用 ,且褪色的程度与碘酸根存在量有关 ,从而建立了光度法测定碘的新方法。方法最大吸收波长为 52 4 nm,表观摩尔吸光系数为 2 .1 9×1 0 4 L·mol-1·cm-1,碘的浓度在 0～ 60 μg/2 5ml范围内符合比耳定律。方法简单、快速、准确、选择性好、灵敏度高 ,用于测定碘食盐中的碘含量 ,结果满意     

二甲酚橙褪色光度法测定微量碘的研究

研究了在硫酸介质中,溴化钾催化下,碘酸根氧化二甲酚橙褪色的最佳条件。其最大吸收波长λmax为430nm,表观摩尔吸光系数为1．3×104L·mol-1·cm-1,碘浓度在0-30μg／25ml范围内呈线性关系。方法用于测定加碘食盐中碘,回收率可达98．0％-101．3％,结果满意。     

末端硫醇化的甲氧基聚乙二醇分子自组装膜电极对碘离子的电化学分析研究

碘离子的测量方法有化学法和电化学方法等多种,电化学方法有离子选择性电极、阴极溶出伏安法等［１,２］,但以上方法易受共存离子的干扰．自组装膜修饰电极具有分子识别功能,因而可用于特定物质的检测［３］．末端硫醇化的聚乙二醇分子在金电极表面形成自组装膜后具有分子识别特性［４］,碘离子和聚乙二醇膜有较好的相容性,可以进入膜内进而到达电极表面进行反应,而其它干扰离子较难进入．因而,该膜电极能用于碘离子测定,检测下限低,并具有较强的抗干扰能力．１　实验部分１．１　试剂及仪器　甲氧基聚乙二醇（ＭＷ＝５０００）等…     

用碘释放法研究双束超声辐照的脉冲空化峰

本文使用双束同频脉冲超声水平正交辐照,通过磺释放法检测,发现双束同频水平正交辐照亦可观察到明显的空化峰现象及声化学产额增长。