N,N'-二乙基-N,N'-二(丙氧基苯基)-2,6-吡啶二酰胺对铀酰离子的选择性络合萃取

研究了新型萃取剂N,N'-二乙基-N,N'-二(丙氧基苯基)-2,6-吡啶二酰胺(1a~1c)对铀酰离子(UO2+2)的络合萃取.结果表明,当不加硝酸或硝酸浓度为6 mol/L时,化合物1a对UO2+2的萃取率分别高达99%和94%.在6 mol/L HNO3的高酸度条件下,化合物1a能实现UO2+2和镧系元素(La,Eu及Yb)的选择性分离[分离比SFU(Ⅵ)/Ln(Ⅲ)20];而化合物1b和1c则可以实现UO2+2和轻镧系元素(La,Eu)之间的分离.双对数图(lg-lg plot)实验结果表明,化合物1a~1c与UO2+2的萃合比在1~2之间,表明同时存在2∶1和1∶1两种比例的萃合物.核磁共振波谱和红外光谱数据证明吡啶氮和羰基氧参与了对UO2+2的配位.     

Spectkophotometric determination of the dissociation constants of n,n'-bis(3-hydroxypropyl)dithiooxamide and n,n'-bis(2-hydroxypropyl)dithiooxamide

The dissociation constants of N,N'-bis(3-hydroxypropyl)dithiooxamide and N,N'-bis(2-hydroxypropyl)dithiooxamide were determined by a spectrophotometric method using a weighted least squares technique for the calculations. For N,N'-bis(3-hydroxypropyl) dithiooxamide a thermodynamic constant pK₁^T of 11.37 was found. At ionic strength μ = 1, pK₁ = 11.27 and pK₂ = 14.29. For N,N'-bis-(2-hydroxypropyl) dithiooxamide, these values were respectively: pK₁^T = 11.11; pK₁ = 10.99 and pK₂ = 13.75.     

反应型无卤阻燃剂N,N’-双(2-羟乙基)磷酸二乙酯的合成及应用

本文以亚磷酸二乙酯和二乙醇胺为原料合成了一种新型反应型无卤阻燃剂N,N’-双(2-羟乙基)磷酸二乙酯(DEHPA),采用红外光谱、核磁氢谱、核磁碳谱以及核磁磷谱表征了其化学结构。利用DEHPA制备了本质阻燃硬质聚氨酯泡沫材料,通过氧指数(LOI)、水平燃烧测试研究了材料的阻燃性能。同时利用热重分析表征了阻燃剂以及泡沫材料的热稳定性。测试结果表明,当DEHPA以30份替代聚醚多元醇时,聚氨酯硬泡LOI值从19.5%提高到23.6%,通过水平燃烧HB级,继续提高阻燃剂添加量,材料阻燃性能进一步提高。热重分析的结果表明DEHPA可以促进聚氨酯硬泡提前分解并具有优良成炭性能。     

Dissociation constants of n,n'-bis(2-carboxyethyl)dithiooxamide

The dissociation constants of N,N'-bis(2-carboxyethyl)dithiooxamide have been determined by potentiometric and spectrophotometric methods. They were calculated by a modified Ricci formula and by a weighted least-squares treatment. The thermodynamic constant pK₃^T is 12.32. At ionic strength 1.00, pK₁=3.76, pK₂=4.74, pK₃=11.41 and pK₄=14.19.     

水诱导N,N′,N″-三(4-吡啶基)-均三苯甲酰胺形成超分子凝胶研究

以均三苯甲酸为母体分子,用4-氨基吡啶对其进行化学修饰,合成了N,N′,N″-三(4-吡啶基)-均三苯甲酰胺(4-btapa)并考察其在不同溶剂及酸碱度中的胶凝性能.实验结果表明,4-btapa不溶于水,但可溶于一些极性溶剂中.室温条件下,在4-btapa的DMSO溶液中加入适量的水,可直接形成稳定凝胶.而在DMF,THF等溶剂形成的溶液中室温条件下加入适量的水得到只能得到粘度较大具有流动性的混浊液,但将得到的混浊液加热溶解后室温冷却均能形成稳定凝胶.扫描电子显微镜观察到4-btapa在不同含水有机溶剂中都能形成纤维状自组装聚集体,而4-btapa在p H=3.0的水-乙醇体系中呈明显的纤维团簇结构,与p H=7.0时的规则的纤维结构相比存在较大的差异,说明p H值会影响凝胶因子聚集形貌.核磁共振和红外光谱结果表明凝胶中存在N—H…Py的分子间氢键和芳香环的π-π堆积作用.根据FT-IR,1H NMR结果并比对干凝胶与晶体XRD曲线得到了凝胶因子4-btapa在凝胶(p H=7.0)中的自组装排列方式.     

Bola型表面活性剂N,N′-二苯丙氨酸酰基-1,8-辛二胺的合成及性质研究

以L-苯丙氨酸为亲水部分和1,8-辛二胺为疏水部分,通过酯化生成酰胺和HCl脱去BOC保护基两步反应,合成一种新型Bola型表面活性剂N,N′-二苯丙氨酸酰基-1,8-辛二胺(DAOPh),采用IR、质谱和~1H NMR对其结构进行了表征.应用酸碱滴定法测得其pKa,采用电导率法、表面张力和芘荧光探针法测定了DAOPh水溶液的临界胶束浓度(CMC),进而预测其在水溶液中的聚集行为,探讨其作为药物载体的潜在优势.     

A potentiometric study of the water-soluble silver(I) complexes of n,n'-bis(2-hydroxyethyl)dithiooxamide : Part III. Determination of the different species

Silver(I) and N,N'-bis(2-hydroxyethyl)dithiooxamide (H₂X) in acidic solutions, form a series of water-soluble polynuclear complexes. These complexes can be represented by two general formulae: H_2qAg_pX_q and H_2q-1Ag_pX_q with q=1,2,3 and p=q, q-1.     

N,N′-bis(2-Vinyloxyethyl)carbodiimide

Previously unreported N,N-bis(2-vlnyloxyethyl)carbodiimide was synthesized by the reaction of N,N -bis(2-vinyloxyethyl)thiourea with yellow mercuric oxide in CH₂Cl₂ at room temperature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1897–1898, August, 1990.     

Amidines-XVIII: Tautomeric equilibria and pka values of N,N'-disubstituted amidines. Substituent effects

The influence of substitution of amidine group on tautomeric equilibria constants and basicities is discussed. Equations based on correlation analysis methods are derived enabling predictions of both, microscopic pK_a, values of individual tautomers, measured macroscopic pK_a values of the tautomeric mixture, as well as the tautomeric equilibrium constant (as pK_T). It is shown that pK_arn values of unsymmetrically N,N'-disubstituted amidines should obey a non-linear relation with σ° constants, and only for symmetrically N,N'-disubstituted amidines obey the linear Hammett equation. Tautomeric equilibrium constants of N,N'-disubstituted amidines correlate withσ° substituent constants. The methods of prediction of pK_a value of both tautomers and pK_T value are proposed.Derived relations are applied to the series of N,N'-diphenylacetamidines and benzamidines.     

对称-3,3'-二(取代苯基氨基)-4,4'-二(氨基)-5,5'-(1,4-丁二基)-1,2,4-三唑的合成

以己二酸为原料,经酯化、肼解后与异硫氰酸苯酯(或对氯异硫氰酸苯酯)反应合成了两个新化合物——对称-N1,N1'-(1,4-丁二基)二(甲酰胺基)-N4,N4'-二(取代苯基)硫脲(3a和3b);3a和3b分别经肼解合环合成了两个新化合物——对称-3,3'-二(取代苯基氨基)-4,4'-二(氨基)-5,5'-(1,4-丁二基)-1,2,4-三唑,其结构经1H NMR,IR和元素分析表征。     

A FOUR-NUCLEAR Ag(I) COMPLEX SUPPORTED BY A N,N′,N″,P-LIGAND: SYNTHESIS,CRYSTAL AND ELECTRONIC STRUCTURE

Journal of Structural Chemistry - A four-nuclear complex [Ag4(Lut3P)2(MeCN)2](BF4)4 is synthesized by treating tris[(6-methylpyridin-2-yl)methyl]phosphine (Lut3P) with AgBF4 in a MeCN solution. The...     

(S)-5,5'-二氨基-2,2'-双二苯基膦基-1,1'-联萘的绿色合成

以2,2'-双二苯基磷基-1,1'-联萘[(S)-1]为原料,与H2O2经氧化反应制得(S)-2,2'-双二苯基磷氧基-1,1'-联萘[(S)-2];(S)-2经酸性树脂催化硝化制得(S)-5,5'-二硝基-2,2'-双二苯基磷氧基-1,1'-联萘[(S)-3)];(S)-3经Pd/C催化硝基氢化还原制得(S)-5,5'-二氨基-2,2'-双二苯基磷氧基-1,1'-联萘[(S)-4];(S)-4经HSi Cl3/PPh3还原制得(S)-5,5'-二氨基-2,2'-双二苯基膦基-1,1'-联萘,总产率65.6%,其结构经1H NMR,31P NMR和IR确证。     

EFFECTS OF L-PHENYLALANINE ON THE RADIATION SYNTHESIS OF POLY （N,N＇-METHYLENEBIS A CR YLAMIDE-co-4-VINYLPYRID INE） （MICRO）GELS

The effects of L-phenylalanine （L-Phe） on the synthesis ofpoly（N,N＇-methylenebisacrylamide-co-4-vinylpyridine） （poly（Bis-co-4-VP）） （micro）gels by γ-ray irradiation were studied. The addition of L-Phe could not only decrease the gelation dose （Dg） of the synthesis obviously, but also transform the morphology of copolymer from microgel to gel. In addition, the swelling ability of the （micro）gels was also affected in the presence of L-Phe. The decrease of Dg was ascribed to the effect of pH, while the transformation of the morphology was ascribed to the effect of L-Phe on the stability of the poly（Bis-co-4-VP） microgel. Such an effect was confirmed further as compared with the effects of L-alanine, L-glutamic acid, L-arginine, sulfuric acid and aqueous ammonia.