N,N,N',N'-四丁基丙二酰胺萃取硝酸铥(Ⅲ)

N;N;N';N'-四丁基丙二酰胺萃取硝酸铥(Ⅲ)     

N,N,N',N'-四丁基丙二酰胺萃取铀(VI)的机理

研究了N,N,N',N'-四丁基丙二酰胺(TBMA)以甲苯为稀释剂,从硝酸介质中萃取硝酸和铀(Ⅵ)的机理。在该萃取体系中,TBMA和HNO₃形成TBMA·HNO₃,和U(Ⅵ)形成为UO₂(NO₃)₂·3TNMA.借助红外光谱分析,确定了在萃合物中NO₃^-不参与UO₂²⁺的直接配位,并对萃合物中配体的配位方式进行     

N,N,N',N'-四丁基丙二酰胺萃取铀(VI)的机理

研究了Ｎ,Ｎ,Ｎ’,Ｎ’－四丁基丙二酰胺（ＴＢＭＡ）以甲苯为稀释剂,从硝酸介质中萃取硝酸和铀（Ⅵ）的机理。在该萃取体系中,ＴＢＭＡ和 ＨＮＯ_３形成 ＴＢＭＡ· ＨＮＯ_３,和 Ｕ（Ⅵ）形成为 ＵＯ_２（ＮＯ_３）_２· ３ＴＮＭＡ。借助红外光谱分析,确定了在萃合物中ＮＯ_３~－不参与ＵＯ_２~（２＋）的直接配位,并对萃合物中配体的配位方式进行了讨论。     

N,N,N',N'-四丁基丙二酰胺从硝酸盐介质中萃取铈(Ⅲ)

核燃料后处理的一个目标是利用中子放射将半衰期很长的锕系元素转变为半衰期短的同位素.由于镧系元素能有效地吸收中子,从而阻止可嬗变的锕系元素捕获中子,所以必须利用溶剂萃取的方法将高放废液中三价的锕系元素与三价的镧系元素分离开来.     

碘·(N,N'联吡啶)·(三苯基膦)合铜(I)的合成和晶体结构

铜（Ｉ）配合物的研究在金属酶的化学模拟和配合物结构及反应性能等研究方面具有重要的理论和实际意义［１］。但由于铜（Ｉ）配合物不稳定,且在多数有机溶剂中的溶解度较小,铜（Ｉ）配合物的合成比较困难。我们在铜（Ｉ）配合物的合成方面积累了一些经验,合成了一系列含有三苯基膦和氮杂环配体的铜（Ｉ）配合物［ＣｕＸ（ＰＰｈ３）Ｌ］ｎ［２～４］（ｎ＝１,Ｘ＝Ｉ,Ｌ＝１,１０ｐｈｅｎ;ｎ＝２,Ｘ＝Ｂｒ,Ｉ,Ｌ＝Ｃ９Ｈ７Ｎ）,并对它们的结构进行了研究。本文报道一个类似的新配合物［ＣｕＩ（ＰＰｈ３）（ｂｐｙ）］（Ｉ）的合成…     

二硝酸(N,N,N',N'-四正丁基丁二酰胺)合铀(Ⅱ)酰配合物的合成和结构

合成的配合UO~2[Bu~2NCO(CH~2)~2CONBu~2](NO~3)~2的晶体属四方晶系,a=b=3.3207(8),c=1.0711(4)nm,α=β=γ=90.00(0)°,V=11.811(7)nm^3,D~c=1.65g.cm^-3,Z=16,空间群为14~1/\α.配合物分子中铀酰离子由六个氧原子配位,其中四个来自两个硝酸根,另外两个来自有机配体的两个羰基,两个硝酸根被七原子环排斥而挤在一边,以铀原子为中心的六方双锥结构受到扭曲.     

富勒烯(C60/C70)与N,N,N',N'一四-(对甲苯基)-4,4'-二胺-1,1'-二苯硒醚(TPDASe)间光诱导电子转移过程的激光光解研究

富勒烯(C60/Z70)与N,N,N',N'-四-(对甲苯基)-4,4'-二胺-1,1'-二苯硒醚(TPDASe)间在激光光诱导条件下,发生了分子间的电子转移过程.在可见-近红外区(600～1200mm),观测到了TPDASe阳离子自由基、富勒烯(C60/C70)激发三线态和阴离子自由基,在苯腈溶液中,观测瞬态谱测定了电子从TPDASe转移到富勒烯(C60/C70)激发三线态的量子转化产率(ΦT et)和电子转移常数(Ket).     

N,N,N',N'-四[(二苯基膦)甲基]乙二胺钯配合物催化Heck反应研究

以乙二胺为骨架的含氮四膦配体N’NN,N',N'-四[(二苯基膦)甲基]乙二胺和钯组成的催化体系用于丙烯酸酯和芳卤的Heck反应,该催化体系对许多卤代芳烃,尤其含吸电基的溴代芳烃显示了良好的催化活性.对活化底物对溴苯甲醛,即使底物与催化剂的物质的量比达到1000000,其转化率也能达到96％;催化非活化溴代芳烃对溴苯甲醚以及难以反应的氯代芳烃,在Pd含量为0.1 mol％时同样表现出优良催化性能.     

Ring Closure of N,N′:N,N′-bis(decamethylene)-1, 4-diamino-2,5-bis(10-cyanodecyloxy)benzene (IV)

Recently, β-chloro-α,β-unsaturated carbonyl compounds have become increasingly useful as intermediates in organic synthesis. For example, reactions involving a number of different cyclic β-chloro-α,β-unsaturated ketones with a variety of reagents (a malonate anion², the anion of the dithiolane derivative of ethyl glyoxalate³, zinc-silver couple in methanol⁴, dimethylsulfoxonium methylide^5,6) have produced a series of structurally diverse and potentially fruitful synthetic intermediates. The second-mentioned reagent has also been successfully reacted with a β-chloro-α,β-unsaturated ester³.     

N,N,N',N'-四丁基丙二酰胺萃取镧系元素的性能及机理

研究新型萃取剂从硝酸盐介质中萃取分离稀土元素对于后处理工艺具有重要意义.本文报道以甲苯为稀释剂,N,N,N',N'-四丁基丙二酰胺(TBMA)从硝酸盐介质中萃取铈(Ⅲ)、镝(Ⅲ)、铒(Ⅲ)、镨(Ⅲ)、钐(Ⅲ)、铽(Ⅲ)、铥(Ⅲ)、镱(Ⅲ)的机理.考察了硝酸浓度、TBMA浓度、盐析剂浓度以及温度对上述三价镧系离子分配比的影响.得出萃合物的组成主要是三配体配合物M(NO3)3·3TBMA;计算出萃取反应的条件平衡常数、萃取平衡常数.温度效应研究表明萃取反应主要是焓驱动的.对萃取分离系数以及TBMA萃取三价镧系离子的规律进行了初步研究.     

Conjugate Addition of Alkyllithium Reagents to α,β-Unsaturated N,N',N'-Trimethylhydrazides

The site of nucleophilic attack by an alkyllithium reagent upon an α,β-unsaturated carbonyl compound is governed by, among other factors, the nature of the group attached to the carbonyl.¹ Thus the amount of carbonyl addition decreases in favor of conjugate addition for the α,β-unsaturated series: aldehyde, ketone, ester, amide. We wish to report that α,β-unsaturated carboxylic acid trimethylhydrazides, which have an exceptionally unreactive carbonyl group², undergo exclusive conjugate addition with simple alkyllithium reagents.³ Furthermore, the derived hydrazide lithium enolates can be transformed in convenient and useful ways.     

N,N′-Bis(trimethylsilyl)dicyandiamide

N,N-Bis(trimethylsilyl)dicyandiamide was prepared for the first time by the reaction of dicyandiamide with hexamethyldisilazane in boiling tetrahydrofuran. Thermal transformations of this compound were studied by DTA. The novel compound may be used in the synthesis of bis(trimethylsilyl)carbodiimide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 498–500, March, 1994.     

Kristallstruktur von N,N,N′,N′-Tetraisopropyl-p-phenylen-diammonium-dichlorid und-bis(tetrachloroaluminat)

Summary Protonation of the sterically overcrowded N,N,N,N-tetraisopropyl-p-phenylenediamine leads to a significant shortening of the C-N bond lengths of 7 pm as well as to a widening of the phenyl ipso-angle to 122°. All structural changes can be attributed to the twisted diisopropylammonium substituents and their electron acceptor properties.

     

N,N,N',N'-四[4-(4'-羧基)联苯基)]-9,10-蒽二胺的合成及荧光性质

以9,10-二溴蒽,二苯胺等为原料经Buchwald-Hartwig芳胺化、溴化、Suzuki偶联和水解等反应合成一个新的芳香四元羧酸N,N,N',N'-四[4-(4'-羧基)联苯基)]-9,10-蒽二胺。其结构经~1H NMR,~(13)C NMR和高分辨质谱表征。初步荧光研究表明,该化合物钠盐水溶液具有发绿光的性质,最大发射波长为497 nm,同时也有较好的荧光量子效率。循环伏安法测试得到其钠盐的HOMO和LUMO分别为-5. 2 eV和-4. 4 eV。     

N,N',N″-三-(2-羟基丙基)-1,4,7-三氮杂环癸烷钴(Ⅱ)配合物的合成及其结构表征

合成了侧臂带有醇羟基的十元环大环三胺衍生物配体N,N',N″-三-(2-羟基丙基)-1,4,7-三氮杂环癸烷(L)及它的过渡金属配合物[CoL][ClO_4]_2,利用元素分析、红外光谱以及热重分析等技术手段对其结构进行了表征,并测定了配合物的晶体结构。解析结果表明,配合物属于Monoclinic晶系,P2(1)/n空间群,中心的Co(Ⅱ)原子为六配位,处于一个畸变的三棱柱配位环境。其中6个配位原子分别来自配体的3个N原子和3个O原子。平均的Co—N键长和Co—O键长分别为:0.2114(6)和0.2097(6)nm。高氯酸根中的3个氧原子分别与邻近的配合物阳离子中的3个O原子通过氢键O…H—O连接起来,形成了一个具有规则结构的超分子网络结构。     

N,N′-Bis(silylmethyl)azodicarboxamides

Russian Journal of General Chemistry - The first representatives of silicon-containing azocarboxamides, N,N′-bis(silylmethyl) azodicarboxamides, were synthesized by the reaction of...     

Synthesis, Crystal Structure, Antibacterial Activity and Interaction with BSA of Copper( Ⅱ ) Complex with Ligand N, N' -Bis ( 4-chlorobenzyl ) propane-1, 2-diamine

合成了N,N'-双(4-氯苄基)-1,2-丙二胺铜(Ⅱ)配合物[ CuCl( C17 H20C12N2)2]·(NH4)·Cl2,通过元素分析和IR光谱对其进行了表征,并通过X射线单晶衍射确定了其晶体结构.晶体结构分析表明,该晶体属于三斜晶系,P1空间群,晶胞参数a=1.35222(16) nm,b=1.37899(17) nm,c=1.39806(19) nm;α=60.954(1)°,β=87.502(2)°,γ=65.970(1)°,V=2.0424(4) nm3,Dc=1.357 g/cm3,Z=2,F(000)=862,R1=0.0925,wR2=0.2668[ Ⅰ＞2σ(Ⅰ)],S=1.001.配合物的金属中心与来自2个配体的4个氮原子和1个末端氯原子配位,形成了轻微扭曲的四方锥几何构型,扭曲指数τ=0.04(1).抗菌实验结果显示,配合物对大肠杆菌、枯草杆菌和金色葡萄球菌均表现出良好的抑菌作用.采用荧光光谱研究了不同温度下配合物与牛血清白蛋白( BSA)的相瓦作用,结果表明,配合物对BSA的荧光猝灭属于静态猝灭.计算了不同温度下配合物与BSA间的结合常数(Ka)、结合位点(n≈1)及相关热力学参数(△H＞0,△S＞0,△G＜0),结果表明,二者主要靠疏水作用力结合.依据F(o)ster的非辐射能量转移理论,求得给体(BSA)与受体(配合物)间的距离r=2.56 nm,说明配合物与BSA之间可能发生了非辐射能量转移.     

Five coordinate complexes of N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamide with copper Crystal and molecular structures of dichloro(N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamido)copper(II) and chloro(perchlorato)(N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamido)copper(II)

The title compound N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamide (DEAP) forms a 1:1 complex with anhydrous CuCl₂, [Cu(DEAP)Cl₂], (1) which was crystallized from EtOH solution in the monoclinic space group P2_{1/ n} with cell constant, a = 10.024(1); b = 13.122(1); c = 14.404(1) Å β = 101.31(1)° V = 1857.8(3) ų and Z = 4. The chloro-perchlorato complex, [Cu(DEAP)Cl(ClO₄)], (2) obtained in near quantitative yield by reacting (1) with an excess of NaClO₄ in EtOH, crystallized in the monoclinic space group P2_{1/ n} with cell constants, a = 7.965(1); b = 25.827(2); c = 10.046(1) Å β = 98.81(1)° V = 2042.2(4) ų and Z = 4. Both (1) and (2) contain 5-coordinated copper linked to DEAP through O～N～O donor set of atoms with covalently bonded chlorine atoms in (1) and chlorine and perchlorate groups in (2). The coordination geometry is intermediate between square pyramidal and trigonal bipyramidal, and is probably best described as a trigonally distorted rectangular pyramid.     

过硫酸盐-N,N,N',N'-四甲基乙二胺体系引发丙烯腈水溶液聚合

过硫酸盐与三乙醇胺或二乙醇胺组成的引发体系,能引发丙烯腈(AN)水溶液聚合。最近 Gupta等报道过硫酸盐-N,N,N′,N′-四甲基乙二胺(TMEDA)体系能在室温引发丙烯酰胺水溶液聚合。