丁基罗丹明B-碲钼杂多酸缔合显色反应的研究

本文研究了在聚乙烯醇(PVA)存在下,丁基罗丹明B(BRB)与碲钼杂多酸的离子缔合显色反应,碲钼杂多酸在0.025～0.075 mol/L硫酸溶液中形成丁基罗丹明B-碲钼杂多酸离子缔合物。形成酸度为1.26～2.16 mol/L硫酸,钼酸铵、丁基罗丹明B及PVA的适宜条件分别4.6×10~(-3)mol/,5.3×10~(-5) mol/L和0.16％。缔合物最大吸收波长为570 nm,表观摩尔吸光系数ε值为3.2×10~5 L·mol~(-1)·cm~(-1),符合比耳定律范围0～16μg Te/25ml。探讨了反应机理,用平衡移动法确定缔合物的摩尔比为Te:Mo:BRB=1:7:2,缔合物的可能化学式为(BRB)_2[TeMo_7O_(24)]。方法已用于烟尘中碲的测定,结果满意。     

亚甲基蓝光度法测定西地那非的含量

在pH3.0～6.0的条件下,亚甲基蓝(MB)与西地那非(SD)反应,生成蓝色离子缔合物,最大吸收波长位于600nm,SD浓度在0～1.6×10-5mol/L范围服从比耳定律,由此建立了测定西地那非含量的分光光度法。缔合物的表观摩尔吸光系数(ε)为3.0×104L·mol-1·cm-1。该方法用于市售药物中西地那非含量的测定,结果满意。     

痕量碘离子的铬(Ⅵ)-碱性呫吨染料体系分光光度法测定

在过量溴化物存在下的稀磷酸介质中 ,I-被Cr(Ⅵ )氧化成I2 后与Br-结合形成[I2Br] -配阴离子 ,该配阴离子能进一步与罗丹明6G、罗丹明B、吖啶红等碱性吨染料阳离子形成离子缔合配合物。在聚乙烯醇存在下 ,缔合物体系稳定且溶液颜色有明显的变化 ,可用于I-离子的光度测定。方法具有高灵敏度 ,不同体系的摩尔吸光系数在4 .96×104 ～1 .1×105 L·mol-1·cm-1 之间 ,以罗丹明6G和罗丹明B体系灵敏度较高。碘离子质量浓度分别在0～0.8mg/L(罗丹明B和罗丹明6G体系)、0～1.0mg/L(吖啶红体系 )之间遵守比尔定律。方法具有良好的选择性 ,用于海带、黄豆和含碘药片的测定结果令人满意     

甲基蓝与庆大霉素、妥布霉素的褪色反应及其应用

在酸性条件下,硫酸庆大霉素(GEN)、硫酸妥布霉素(TOB)与甲基蓝(MB)反应,生成离子缔合物,使甲基蓝褪色,其最大褪色波长位于606nm(GEN)和610nm(TOB),表观摩尔吸光系数(ε)为1.80×104(GEN)和2.93×104(TOB)L·mol-1·cm-1;庆大霉素、妥布霉素浓度在0～1 2×10-5mol·L-1范围内遵从比耳定律。该法用于市售药物及人体尿液中庆大霉素及妥布霉素含量的测定,结果满意。     

铑(Ⅲ)-钼酸盐-丁基罗丹明B缔合显色反应的研究

在聚乙烯醇(PVA)存在下,铑与钼酸盐和丁基罗丹明B(BRB)形成寓于缔合物,缔合物的最大吸收峰位于570nm,摩尔吸光系数ε值为3.22×10~5L·mol~(-1)·cm~(-1),服从比耳定律范围0～8μgRh/25ml,摩尔比Rh:BRB1:4:,缔合物至少稳定240h。测定铑的适宜条件为C_(HCIO_4)=1.5mol/L,C_(MoO_4~(8-)),3.3×10~(-8)mol/L,C_(BRA)=3.8×10~(-5)mol/L,PVA0.08％。考察了41种共存离子的影响,常见元素不干扰。本法已用于催化剂和回收液中铑的测定,结果满意。本文还探讨了反应机理。     

碱性染料杂多酸多元配合物显色反应的研究——Ⅵ.丁基罗丹明B-砷钼杂多酸-聚乙烯醇-124体系

本文研究了丁基罗丹明B-砷钼杂多酸-PVA-124体系,由于形成高取代氢原子的杂多酸而使反应灵敏度大增,ε值高达6.9×10~5 L·mol~(-1)·cm~(-1)。缔合物的组成比As(V):BRB=1:7。红外光谱研究证明,染料和杂多酸形成了离子对缔合物。本法可成功地用于水样和试剂中痕量砷的测定。测定下限分别为2.0ppb(水样)和2×10~(-6)％(试剂)。     

银与碘化物和罗丹明B在水溶液中显色反应的研究

基于(AgIs)~2-络阴离子在聚乙烯醇存在下的水溶液中,与罗丹明 B 产生的离子缔合反应,提出了一个高灵敏度分光光度法测定银的方法.形成离子缔合物的适宜酸度范围是0～0.04N 硝酸(pH7～1.4).以连续变化法和平衡移动法确定离子缔合物的组成是[RB]_2[AgI_s].离子缔合物溶液的最大吸收位=j=600nm处,摩尔吸光系数为1.65×10~5·mol·~(-1)cm~(-1).方法有较好的选择性.在某些掩蔽剂存在下可用于钢中微量银的测定.     

水溶苯胺蓝褪色光度法测定庆大霉素及妥布霉素的研究

在酸性条件下,水溶苯胺蓝(ABWS)与硫酸庆大霉素(GEN)或硫酸妥布霉素(TOB)反应,生成离子缔合物,使水溶苯胺蓝溶液褪色,其最大褪色波长分别位于606nm(GEN)和608nm(TOB);在0～1.2×10-5mol·L-1(GEN)和0～1.5×10-5mol·L-1(TOB)的浓度范围内遵从比耳定律;表观摩尔吸光系数(ε)分别为2.21×104L·mol-1·cm-1(GEN)和3.10×104(TOB)L·mol-1·cm-1。本法已用于市售药物及人体尿液中庆大霉素及妥布霉素含量的测定,结果满意。     

盐酸氯丙嗪-卤代荧光素体系的光度法测定

在NaAc HCl缓冲介质中,盐酸氯丙嗪可与曙红Y、赤藓红、乙基署红等卤代荧光素染料反应,形成离子缔合物,溶液颜色发生明显改变,可用光度法测定。盐酸氯丙嗪的浓度在0～1.6×10-5mol·L-1(曙红Y)、0～1.3×10-5mol·L-1(赤鲜红)、0～1.5×10-5mol·L-1(乙基曙红)范围内遵守比耳定律,其表观摩尔吸光系数分别为4.63×104L·mol-1·cm-1、2.50×104L·mol-1·cm-1、为4.32×104L·mol-1·cm-1。方法用于片剂和针剂中盐酸氯丙嗪的测定,结果满意。     

铕-伊文思蓝分光光度法测定新霉素及妥布霉素

在酸性条件下,铕(Ⅲ) 伊文思蓝(EB)与硫酸新霉素(NEO)或硫酸妥布霉素(TOB)反应生成三元蓝色离子缔合物。最大吸收波长位于668nm(NEO)和670nm(TOB);线性范围分别为0～15.5μg·mL-1(NEO)和0～15.0μg·mL-1(TOB);摩尔吸收光系数(ε)为1.19×105(NEO)和9.05×104(TOB)L·mol-1·cm-1;最大负吸收波长位于608nm,线性范围分别为0～16.5μg·mL-1(NEO)和0～16.0μg·mL-1(TOB),摩尔吸收光系数(ε)为1.54×105(NEO)和1.08×105(TOB)L·mol-1·cm-1。当用双波长叠加时,ε值为2.73×105(NEO)和2.00×105(TOB)L·mol-1·cm-1。该法已用于市售药物及尿液中新霉素和妥布霉素含量的测定,分析结果满意。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.