磷酸三丁酯—钛—钽试剂第三相的形成与应用

本文研究了强酸性介质中，磷酸三丁酯萃取体系（ＴＢＰ．ＨＡ）第三相的形成条件；探讨了ＴＢＰ．ＨＡ对钛的萃取行为；建立了ＨＣｌＯ４－Ｈ２ＳＯ４介质中，利用ＴＢＰ．ＨＡ第三相萃取，然后用ＩＣＰ－ＡＥＳ温室痕量钛的方法。结果表明，由于第三相体积小，对钛有较高的富集倍数，降低了分析的检出限，用ＩＣＰ－ＡＥＳ检测，可以消除基体及其他大部分元素对测定的干扰，测定钛的回收率在９７％－１０１％。利用本法对钢样标准物     

1－苯基－3－甲基－4－（a－呋喃甲酰基）－5－吡唑酮与中性萃取剂协同萃取镱的研究

研究了１－苯基３－甲基－４－（呋喃甲酰基）－５－吡唑酮（ＨＡ）萃取镱及其分别与丁基辛基亚砜（ＢＯＳＯ）、戊基已基亚砜（ＰＨＳＯ）、乙基十二烷基亚砜（ＥＤＳＯ）、二苯亚砜（ＤＰＳＯ）和ＴＢＰ协同萃取镱的行为。协萃配合物的组成为ＹｂＡ＿３·Ｂ，ＨＡ的萃取平衡常数为—５．６４±０．０４，中性萃取剂的协萃能力比单独萃取时高３～４个数量级，协萃效果明显。     

Ga^3＋的新萃取体系的界面特性和胶团化作用研究

研究了Ｇａ~（３＋）协萃体系（Ｇａ~（３＋）－Ｄ_２ＥＨＰＡ－Ｈ_２ＭＰＡ－正十二烷－Ｈ_２ＳＯ_４）的界面吸附和胶团形成热力学，发现该萃取体系中［Ｈ_２ＭＰＡ］影响Ｄ_２ＥＨＰＡ和Ｈ_２ＭＰＡ的界面吸附性质。在中、高［Ｈ_２ＭＰＡ］范围内Ｄ_２ＥＨＰＡ与Ｈ_２ＭＰＡ的界面吸附行为相反，Ｄ_２ＥＨＰＡ的存在也影响Ｈ_２ＭＰＡ的界面吸附行为。研究了界面张力与各因素关系的数学模型，并获得某些胶团形成和界面吸附特性的物化参数。     

皂化酸性磷酸酯萃取稀土离子过程中有机相的FTIR光谱表征

研究了不同浓碱皂化的Ｄ２ＥＨＰＡ－正庚烷体系萃取－系列稀土离子（Ｌａ＾３＋－Ｌｕ＾３＋）放射性的Ｐｍ除外）过程中有机相的ＦＴＩＲ光谱变化规律，结果说明，Ｄ２ＥＨＰＡ萃取稀土离子后，Ｐ－Ｏ基团５的红外吸收频率降低，吸收强度升高，说明Ｐ－Ｏ基团与稀土离子发生配位；红外光谱研究研究结果表明：不同稀土离子与Ｐ－Ｏ配位能力有差别，从Ｌａ＾３＋－Ｓｍ＾３＋ｓｇｎ ｗｕｇ ｃｅｌｔｗｙｅ ｕｑｗ ｆｕｌｊｅ ｓ     

二（2,4,4—三甲基戊基）膦酸从盐酸介质中萃取钍（Ⅳ）的机理

研究了二（２，４，４－三甲基戊基）膦酸的正辛烷溶液从盐酸介质中萃取钍的机理。在未控制离子强度下，萃取平衡反应为：Ｔｈ＾４＋＋Ｃｌ＾－＋３（ＨＡ）２（ｏ）→ＴｈＣｌＡ３（ＨＡ）３（ｏ）＋３Ｈ＾＋。在控制离子强度为１．０ｍｏｌ／Ｌ时，萃取反应为Ｔｈ＾４＋＋２Ｃｌ＾－＋３（ＨＡ）２（Ｏ）→ＴｈＣｌ２Ａ２．（ＨＡ）４（Ｐ）＋２Ｈ＾＋。用饮和法确定的萃合物组成为ＴｈＣｌＡ３．计算了萃取反应的平衡常数及热力学     

BTMPPA与HPMBP协同萃取稀土元素（Ⅲ）的研究

研究了二（２，４，４－三甲基戊基）膦酸（ＢＴＭＰＰＡ，ＨＬ）和１－苯基－３－甲基－４－苯甲酰基吡唑酮－５（ＨＰＭＢＰ，ＨＡ）的苯溶液在不同矿物酸介质中，对稀土元素（Ⅲ）的ＡＡ类协同革取。以Ｎｄ￣（３＋）、Ｙｂ￣（３＋）为例，研究了ＢＴＭＰＰＡ－ＨＰＭＢＰ苯溶液从ＨＮＯ＿３介质中协同萃取稀土元素（Ⅲ）的机理。用斜率法确定了协萃配合物组成为Ｎｄ（ＨＬ＿２）Ａ＿２、Ｙｂ（ＨＬ）２）＿２·Ａ·ＨＡ，计算了协萃平衡常数。     

铁钴镍铜锌镉铝在聚乙二醇—硫酸铵—茜素S体系中萃取分离

本文用茜素Ｓ作萃取剂，研究了Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｃｄ，Ａｌ在聚乙二醇－硫酸铵－茜素Ｓ体系中的非有机溶剂萃取行为。实验结果表明，在ｐＨ５的ＨＡｃ－ＮａＡｃ缓冲溶液中，Ｆｅ，Ａｌ与茜素Ｓ的络合物可被ＰＥＧ相几乎完全萃取，Ｃｕ，Ｎｉ部分被萃取，而Ｃｏ，Ｚｎ，Ｃｄ则不被萃取，从而实现了Ｆｅ与Ｃｏ，Ｚｎ，Ｃｄ及Ａｌ与Ｃｏ，Ｚｎ，Ｃｄ混合离子间的定量分离。     

1,10—双（1′—苯基—3′—甲基—5′—氧代吡唑—4′—基）癸二酮—（1,10）？…

研究了１，１０－双（１′－苯基－３′－甲基－５′－氧代吡唑－４－基）癸二酮－（１，１０）（ＢＰＭＰＤＤ，Ｈ２Ａ）与三苯基氧化膦（ＴＰＰＯ，Ｂ）的氯仿溶液从硝酸介质中对Ｓｎ（Ⅲ）的协同萃取行为，计算了体系的酸性协萃系数ＲＡ和协萃系数Ｒ，用斜率法测得协萃合物的组成为ＳｍＡ．ＨＡ．Ｂ，计算了协萃平衡常数，用萃取法制得了固态协萃合物，并对其组成ＩＲ及ＴＧ－ＤＴＡ进行了研究。     

1,9—双（1′—苯基—3′—甲基—5′—氧代吡唑—4′—基）壬二酮—（1,9）与三？…

研究了１，９－双（１′－苯基－３′－甲基－５′－氧代吡唑－４′－基）壬二酮－（１，９）（ＢＰＭＰＮＤ，Ｈ２Ａ）与三辛基氧膦（ＴＯＰＯ，Ｂ）的氯仿溶液，从硝酸介质中对Ｌａ（Ⅲ），Ｄｙ（Ⅲ）的协同萃取，计算了体系的酸性协萃系数ＲＡ和协萃系数Ｒ，用斜率法测得协萃合物的组成ＬａＡ．ＨＡ．Ｂ和ＤｙＡ．ＨＡ．Ｂ计算了协萃取平衡常数，研究了温度对协萃反应的影响，用萃取法制得了固态协萃合物，并对其组成，ＩＲ及ＴＧ     

N，N’－双［（1－苯基－3－甲基－5－氧－4－吡唑啉基）亚苄基］乙二亚胺萃取钯的机理及钯－铂体系中钯的选择性萃取

本文首次报道了标题试剂Ｈ２Ａ对钯的萃取行为，确定了萃取物的组成，讨论了萃取机理，算出了萃取平衡常数．通过化学分析、红外及拉曼光谱、紫外光谱，研究得出了萃合物的结构，并且实现了Ｈ２Ａ从钯－铂混合溶液中选择性萃取钯．     

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.     

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.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.