四丁基溴化铵-KI-水体系浮选分离钯(Ⅱ)的研究

研究了四丁基溴化铵-KI体系分离钯的行为及与其他金属离子分离的条件。实验结果表明,在水溶液中,Pd(Ⅱ)与四丁基溴化铵和KI形成不溶于水的三元缔合物[PdI4][TBAB]2,此三元缔合物沉淀浮于盐水相上层形成界面清晰的液-固两相。当四丁基溴化铵和KI的浓度分别为7.0×10-4mol/L和2.0×10-3mol/L时,Pd(Ⅱ)的浮选率达到99.5%以上。而Ce(Ⅲ),Fe(Ⅱ),Sn(Ⅳ),Co(Ⅱ),Mn(Ⅱ),Rh(Ⅲ),Zn(Ⅱ),Ga(Ⅲ),Cr(Ⅲ),Mo(Ⅵ),W(Ⅵ),Ni(Ⅱ),Al(Ⅲ)和V(Ⅴ)离子在该体系中不被浮选,实现了Pd(Ⅱ)与这些金属离子的定量分离。对合成水样中Pd(Ⅱ)的分离和测定,结果满意。该方法在微量钯的分离和富集分析中有一定的实用价值。     

氯化钠-硫氰酸铵-溴化十六烷基三甲基铵体系浮选分离锌

研究观察到,在水溶液中Zn(Ⅱ）与硫氰酸铵、溴化十六烷基三甲基铵形成不溶于水的三元缔合物,在少量氯化钠存在下此三元合物沉淀浮于水相上层并与水分成界面清晰的两相,分相过程中Zn(Ⅱ）被定量浮选。实现了Zn(Ⅱ）与Fe(Ⅲ）、Al(Ⅲ）、Co(Ⅱ）、Ni(Ⅱ）、Mn(Ⅱ）等离子的分离,是一种无毒且更为简便、经济、快速的分离方法。     

十六烷基三甲基溴化铵-硫氰酸铵-氯化钠体系浮选分离钌(Ⅲ)

在水溶液中,Ru(Ⅲ)与硫氰酸铵、十六烷基三甲基溴化铵形成不溶于水的三元缔合物.在少量NaCl存在下,此三元缔合物沉淀浮于盐水相上层形成界面清晰的液-固两相,当溶液中硫氰酸铵、十六铵基三甲基溴化铵和氯化钠的浓度分别为0.20 mol/L、1×10-3 mol/L,0.1 g/mL, pH=5.0时, Ru(Ⅲ)被定量浮选.Cr(Ⅲ)、Mn(Ⅱ)、Al(Ⅲ)、Ni(Ⅱ)、Co(Ⅱ)、Fe(Ⅱ)、Au(Ⅲ)离子在该体系中不被浮选,从而使Ru(Ⅲ)与这些离子定量分离,对合成水样进行的定量浮选分离测定,结果满意.     

溴化钾-四丁基溴化铵体系浮选分离钯(Ⅱ)

在pH 2的水溶液中,钯(Ⅱ)与溴化钾和四丁基溴化铵(TBAB)形成不溶于水的三元离子缔合物,此三元配合物浮于盐水相上层形成界面清晰的液-固两相,当溶液中溴化钾和四丁基溴化铵的浓度分别为1.5×10-2,2.0×10-3mol·L-1,酸度为pH 2.0时,钯(Ⅱ)被定量浮选.汞(Ⅱ)、铅(Ⅱ)、钨(Ⅵ)和钒(Ⅴ)离子在该体系中不被浮选,实现了钯(Ⅱ)与这些离子的定量分离.对合成水样中100μg钯(Ⅱ)进行了定量浮选分离和测定,结果表明此方法的浮选率达99.7%.     

氯化钠-碘化钾-甲基紫-水液-固体系浮选分离汞(Ⅱ)的研究

研究了NaCl-KI-甲基紫-水液-固体系浮选分离汞(Ⅱ)的行为及其与常见离子分离的条件。结果表明,在0.5~1.0 g NaCl存在下,当0.1 mol/L KI溶液和1.0×10-3mol/L甲基紫(MV)溶液的用量分别为0.5,0.4 mL时,体系中形成的不溶于水的KI-MV-Hg三元缔合物可浮于盐水相上形成界面清晰的液-固两相,从而使Hg(Ⅱ)被定量浮选,而Cd(Ⅱ),Co(Ⅱ),Mn(Ⅱ),Ni(Ⅱ),Zn(Ⅱ),Al(Ⅲ)等在此条件下不被浮选,实现了Hg(Ⅱ)与这些离子之间的定量分离,对合成水样中微量汞(Ⅱ)进行的定量分离测定,结果满意。     

结晶紫-硫氰酸铵体系浮选分离钌(Ⅲ)

在水溶液中Ru(Ⅲ)与硫氰酸铵、结晶紫形成不溶于水的三元缔合物,在少量氯化钠存在下,此三元缔合物沉淀浮于盐水相上层形成界面清晰的液-固两相.当溶液中氯化钠、硫氰酸铵、结晶紫的质量浓度分别为50 g·L-1、0.04 mol·L-1、2.5×10-4mol·L-1,pH 4.0时,Ru(Ⅲ)被定量浮选.Rh(Ⅲ)、Mn(Ⅱ)、Al(Ⅲ)、Ni(Ⅱ)、Cr(Ⅲ)、Cd(Ⅱ)、V(Ⅴ)、Fe(Ⅱ)离子在该体系中不被浮选,实现了Ru(Ⅲ)与这些离子的定量分离,对合成水样和纯镍中钌进行定量浮选分离测定.     

丙醇-硫酸铵双水相体系萃取金(Ⅲ)-氯化物-罗丹明B

水溶性聚合物如聚乙二醇 (ＰＥＧ )、吐温(Ｔｗｅｅｎ) 80的水溶液在电解质存在下萃取分离贵金属离子已有报道[1] ;小分子的有机物如乙醇、丙醇在硫酸铵、氯化钠等电解质存在下也能分为两相形成双水相体系 ,可应用于金属离子的分离[2 ] ;该类体系也可以用于萃取分离贵金属络阴离子[3,4] 。我们发现金 (Ⅲ )与氯离子在碱性染料罗丹明Ｂ(ＲｈＢ)参与下所形成的三元缔合物 ,可被丙醇 硫酸铵双水相体系定量萃取而与大量常见贱金属分离 ,体系同时具有溶剂萃取法及溶剂浮选法的优点 :既可以分离简单贵金属络阴离子[3,4] ,又可以分离贵金属三元缔…     

溴化钾-溴化十六烷基吡啶-水体系浮选分离金(Ⅲ)的研究

研究了溴化十六烷基吡啶和KBr分离金(Ⅲ)的行为及与一些金属离子分离的条件。在水溶液中,Au(Ⅲ)与溴化十六烷基吡啶和KBr形成不溶于水的三元缔合物AuBr4-.CPB+,此三元缔合物沉淀浮于水相上层形成界面清晰的液-固两相。当溶液中溴化十六烷基吡啶和KBr的浓度分别为5.0×10-4mol/L和7.0×10-3mol/L时,Au(Ⅲ)可与Ce(Ⅳ),Ni(Ⅱ),Ru(Ⅲ),Cr(Ⅲ),Ga(Ⅲ),Rh(Ⅲ),Co(Ⅱ),Fe(Ⅲ),Zn(Ⅱ),Cu(Ⅱ),Al(Ⅲ),Sn(Ⅳ)和V(Ⅴ)进行分离,对合成水样中的Au(Ⅲ)进行了分离和测定,Au(Ⅲ)的浮选率达到99.8%以上,其他金属离子的浮选率都在3.3%以下。     

硫氰酸铵-罗丹明 B-H2O的液-固体系浮选分离铜(Ⅱ)的研究

研究了硫酸铵存在下硫氰酸铵-罗丹明B-H2O的液-固体系浮选分离铜(Ⅱ)的行为及其与常见离子分离的条件.结果表明,当(NH4)2SO4用量为1.0 g,0.1 mol·L-1硫氰酸铵溶液1.5 mL和0.001 mol·L-1罗丹明B溶液2.0 mL时,铜(Ⅱ)以不溶于水的三元离子缔合物(RhB)2[Cu(SCN)4]形式在液-固两相界面定量浮选析出,而Cdd2、Mn2+、Co2+、Ni2+、Al3+等离子在此条件下不被浮选,实现了铜(Ⅱ)与这些离子的定量分离,对合成水样中微量铜(Ⅱ)进行的定量浮选分离测定,浮选富集的平均回收率达101.4%.     

氯化钠-硫氰酸铵-氯化十四烷基吡啶体系浮选分离铜

在水溶液中Ｃｕ(Ⅱ )与硫氰酸铵、氯化十四烷基吡啶形成不溶于水的三元缔合物 ,在少量氯化钠存在下此三元缔合物沉淀浮于水相上层并与水分成界面清晰的两相 ,分相过程中Ｃｕ(Ⅱ )被定量浮选。而Ｆｅ(Ⅲ )、Ｃｏ(Ⅱ )、Ｎｉ(Ⅱ )、Ｍｎ(Ⅱ )、Ｃｄ(Ⅱ )等离子在该体系中不能被浮选 ,借此可实现Ｃｕ(Ⅱ )与这些离子的分离。1　实验部分1 1　仪器与试剂氯化钠 (Ａ .Ｒ .,洛阳市化学试剂厂 ) ;1 .0×1 0 - 2 ｍｏｌ·Ｌ- 1 氯化十四烷基吡啶溶液 (ＴＢＰＣ)(ｐａｃｋｅｄｉｎＳｗｉｔｚｅｒｌａｎｄ) ;0 .2ｍｏｌ·Ｌ- 1 硫氰酸铵标准溶液按文…     

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%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.