伯胺N1923萃淋树脂吸萃钯的研究

伯胺Ｎ_（１９２３）萃淋树脂吸萃钯的研究程德平，夏式均（杭州大学化学系杭州３１０００８）关键词钯，萃淋树脂，吸附伯胺萃取剂Ｎ（１９２３）用以萃取金属离子有不少研究［１－３］，但以Ｎ（１９２３）萃淋树脂作固定相的萃取色层研究未见报道。本文研究了此树脂在?..     

用N—苯基—N′—（氨基对苯磺酸钠）硫脲光度法测定微量钯（Ⅱ）

１引言 硫脲类化合物作为显色剂测钯已有报道,氨基硫脲及其衍生物分子中,含有的氮、硫两种原子均可作为电子的给予体,提供电子对与多种金属离子生成金属资合物,因而广泛应用于金属离子的定性、定量分析。本实验室合成的系列氨基硫脲类化合物已成功应用于钯的定量分析。本文研究了新的水溶性试剂Ｎ－苯基－Ｎ’－（氨基对苯磷酸钠）硫脲（ＰＰＴ）与钯（Ⅱ）的显色反应,通过寻找适宜的反应条件,建立了测定微量把（Ⅱ）的新方法。该法灵敏度高、操作简便,且测定结果准确可靠。将该法用于废催化剂中把的测定,所得结果令人满意。２实验…     

新显色剂2－（5－硝基－2－吡啶偶氮）－5－二甲氨基苯胺与钯显色反应的研究及其应用

用新合成的偶氮试剂２－（５－硝基－２－吡啶偶氮）－５－二甲氨基苯胺（５－ＮＯ＿２－ＰＡＤＭＡ）研究了光度法测定他的反应条件。结果表明，在０．４５～１．２ｍｏｌ／Ｌ盐酸介质中，钯与试剂形成稳定的蓝色配合物，其最大吸收波长位于６２１ｎｍ处，表观摩尔吸收系数为９．４×１０￣４Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），配合成的组成为Ｐｄ：５－ＮＯ＿２－ＰＡＤＭＡ＝１：２，钯浓度在０～１０μｇ／１０ｍＬ范围内符合比尔定律。本方法是目前测定钯的高灵敏度和高选择性体系之一。用于含钯分子筛及二次合金管理样－８８中微量钯的测定，结果满意。     

甘氨酸—N,N—双亚甲基膦酸锆—钯催化剂的催化加氢性能

甘氨酸┐Ｎ，Ｎ┐双亚甲基膦酸锆┐钯催化剂的催化加氢性能傅相锴＊马学兵刘昌华何佑秋（西南师范大学化学化工学院重庆６３０７１５）关键词甘氨酸－Ｎ，Ｎ－双亚甲基膦酸锆，钯催化剂，催化加氢，催化活性１９９６－０３－２５收稿，１９９６－０６－１９修回国家自然科...     

新显色剂N-对甲苯基-N′-(氨基对苯磺酸钠)硫脲的合成及与钯(Ⅱ)的显色反应

合成了新试剂Ｎ－对甲苯基－Ｎ′－（氨基对苯磺酸钠）硫脲（ＰＭＰＴ）。经红外、紫外、核磁共振和元素分析等方法测试,确定了其组成和结构,并研究了新试剂与钯（Ⅱ）的显色反应,建立了光度法测定微量钯（Ⅱ）的新方法。在ｐＨ３．６～５．８的ＨＡｃ－ＮａＡｃ缓冲体系中,该试剂和钯（Ⅱ）形成一种稳定的组成比（摩尔比）为１∶２的水溶性配合物,其最大吸收峰位于３１８．６ｎｍ处,表观摩尔吸光系数为２．６６×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。钯（Ⅱ）在８．０～４２４μｇ／Ｌ服从比尔定律,相关系数ｒ＝０．９９９７。将该法应用于阳极泥和矿石样品中微量钯的测定,获得满意的结果。     

新试剂二溴对硝基苯基重氮氨基—4—苯基—2—噻唑的合成及其与钯显色反应的研

报道了新试剂二溴对硝基苯基重氮氨基－４－苯基－２－噻唑的合成方法，并研究了在表面活性剂ＣＰＣ存在下，该试剂与钯（Ⅱ）的显色反应，结果表明，在ｐＨ６．４～７．８范围内，钯（Ⅱ）与该试剂可形成１：２灰紫色的配合物，其最大吸收波长位于６５０ｎｍ，表观摩尔吸光系数为７．０２×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１钯量在０～２２μｇ／２５ｍＬ，范围内符合比尔定律，该方法已用于Ｐｄ－Ｃ催化 微是钯的测定，结果满     

新试剂N—庚基—N‘—（对氨基苯磺酸钠）硫脲光度法测定数量钯（Ⅱ）的研究

研究了Ｎ－庚基－Ｎ’－（对氨基苯磺酸钠）硫脲与钯的反应条件。结果表明：在ｐＨ４．８－５．８的ＨＡｃ－ＮａＡｃ介质中，并有溴化十六烷基三甲胺存在下，试剂ＨＰＴ与钯形成稳定的黄色配合物，其最大吸收波长为２９５．２ｎｍ，表观摩尔吸光系数为２．９８×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１。     

新显色剂2—（5—硝基—2—吡啶偶氮）—5—二甲所苯胺与钯显色反应的研究及其…

用新合成的偶氮试剂２－（５－硝基－２－吡啶偶氮）－５－二甲氨基苯胺研究了光度法测定钯的反应条件。结果表明，在０．４５－１．２ｍｏｌ／Ｌ盐酸介质中，钯与试剂形成稳定的蓝色配合物，其最大吸收波长位于６２１ｎｍ处，表观摩尔吸收系数为９．４×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，配合成的组成为Ｐｄ：５－ＮＯ２－ＰＡＤＭＡ＝１：２，钯浓度在０－１０μｇ／１０ｍＬ范围内符合比尔定律。本方法是目前测定钯的高灵敏     

2—羟基—5—仲辛基—二苯甲酮肟与P204对钯的协同萃取

２┐羟基┐５┐仲辛基┐二苯甲酮肟与Ｐ２０４对钯的协同萃取董彦杰刘建宁（庆阳师范高等专科学校西峰７４５０００）Ｐ２０４单独萃取金属离子研究较多［１～３］，Ｐ２０４与螯合萃取剂Ｎ５１０的协萃体系报道较少，只研究过金属离子ＣＯ２＋、Ｎｉ２＋［５］等，而用Ｐ...     

显色剂N—烯丙基—N‘—（氨基对苯磺酸钠）硫脲与钯（Ⅱ）显色反应的研究和…

本报道了极易溶于水的显色剂Ｎ－烯丙基－Ｎ＇－（氨基对苯磺酸钠）硫脲光度法测定钯的条件，：在ＰＨ４．０－５．５缓冲介质中，ＡＳＡＴｕ与钯生成易溶于水的、稳定的黄色络合物，组成比为：Ｐｄ（Ⅲ）：ＡＳＡＴｕ＝１：４；络合物的最大吸收波长为２９６．０ｎｍ表观摩尔吸光系数ε２９６＝１．３３×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１；钯（Ⅱ）在０－２０嗳μｇ／２５ｍＬ呈线性，相关系数γ＝０．９９９５。该法灵敏度     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.