Theoretical Study of Hydration Effects on the Selectivity of 18-Crown-6 Between K~＋ and Na~＋

A combination of molecular dynamics （MD） and density functional theory （DFT） calculations were used to study the hydration structures of K＋ and Na＋ ions under the confinement of 18-crown-6 in order to identify the role of water in the selectivity of 18-crown-6 towards K＋.The radial distribution functions,coordination num-bers,orientation structures and interaction energies were analyzed to investigate the hydration of K＋ and Na＋ in 18-crown-6/cation complexes.All calculations of K＋ and Na＋ in bulk water were also conducted for comparison.The simulation results show that the orientation distributions of the water molecules in the first coordination shell of K＋ are more sensitive to the confinement of 18-crown-6 than those of Na＋.It is more favorable to confine a K＋ in 18-crown-6 than a Na＋ in terms of interaction energy.Good agreement is obtained between MD results and DFT results.

Lanthanum(Ⅲ) sorption studies on poly[dibenzo-18-crown-6] and its separation from uranium(Ⅵ) and thorium(Ⅳ) in L-valine medium

The sorption study of La(Ⅲ) was carried out on poly[dibenzo-18-crown-6] and L-valine medium. The quantitative adsorption of La(Ⅲ) was found at 1×10-2 to 1×10-5 mol/L L-valine. The various eluting agents were found efficient eluents for La(Ⅲ). The capacity of crown polymer for La(Ⅲ) was found to be 0.43 ±0.01 mmol/g. The tolerance limit of various cations and anions for La(Ⅲ) was determined. La(Ⅲ) was quantitatively separated from other metal ions in binary as well as multicomponent mixtures. The study was extended to sequential separation of La(Ⅲ), U(VI) and Th(IV). The good separation yields were obtained and had good reproducibility (±2%). The method incorporated the determination of La(Ⅲ) in real sample. The method was simple, rapid and selective.

Synthesis and Crystal Structure of 3,3'-Dimethyl-dibenzo-18-crown-6

3,3′-Dimethyl-dibenzo-18-crown-6 was synthesized and characterized by elemental analysis, FT-IR, ^1H NMR, UV, MS spectra and X-ray single-crystal diffraction. It belongs to orthorhombic, space group Pna21 with a = 8.0790（18）, b = 16.780（4）, c = 15.222（3） .A, Z= 4, V= 2063.6（8） A3 Dc = 1.250 g/cm^3,μ = 0.090 mm^-1, F（000） = 832, R = 0.0474 and wR = 0.1103. According to structural analysis, the title compound possesses a boat-like configuration.

Synergistic Effect in Mixed Capillary Gas Chromatographic Stationap Phases Containing Heptakis(2,3,6-tri-o-pentyl)-β-cyclodextrin and Dibenzo-18-crown-6

used－silical capillary columns containing heptakis（2、3、6－tri－o－pentyl）-β-cyclodextrinand dibenzo-18-crown-6 were prepared．By studying the selectivity of mixed stationary phases forsome solute pairs.as well as comparing with the heptakis（2．3、6-tri-O-pentyl）-β-cyclodextrin and thedibenzo-18-crown-6 used as individual stationary phase、the synergistic effects were observed.These effects were affected by the column temperature．mixed ratio and linear velocity of carrier gas．

Fluorescence-quenching of Tryptophan Ion-18-crown-6 Complex——A Different Observation from Its Neutral Counterpart

It is well-known that primary amines form inclusive complexes with crown ethers. This kind of noncovalently inclusive complexes, exemplified tryptophan complex with 18-crown-6, was studied by combination of two experimental methods, fluorimetry and mass spectrometry, with theoretical calculation. Fluorescence intensity of tryptophan in the absence and the presence of 18-crown-6 in aqueous HAc-NaAc buffer solution at pH=3.73 has been studied by fluorometry. The fuorescence intensity decreases significantly with increasing the concentration of 18-crown-6. The association constant K for the 1：1 complex of tryptophan ion-18-crown-6 was determined by means of fuorimetry. Mass spectrometric study of the complex gives direct evidence of the complex in the gas phase whose structure and binding energy are properly predicted by ab initio calculation.

Synthesis and Crystal Structure of a Sandwiched Trinuclear Complex [Tl_2(18-Crown-6)_2Pt(CN)_4]·2H_2O

The trinuclear complex bis（18-crown-6）thallium tetracyanoplatinate [Tl2（1 8-crown- 6）2Pt（CN）4]·2H2O was prepared and its structure was determined by X-ray diffraction analysis. The compound （C28H52N4O14PtTl2, Mr = 1272.57） crystallizes in monoclinic, space group P21/n with a = 10.5180（10）, b = 8.6162（8）, c = 21.118（2） A, β= 92.577（2）°, V= 1911.9（3） A^3, Z = 2, Dc = 2.211 g/cm^3, F（000） = 1200,μ= 12.123 mm^-1, R = 0.0181 and wR = 0.0427. The linearly arranged three metals are sandwiched by two 18-crown-6 molecules.

{[K.18-Crown-6]Br_3}_n:A tribromide catalyst for the catalytic protection of amines and alcohols

{[K.18-Crown-6]Br3}n,a unique tribromide-type catalyst,was utilized for the N-boc protection of amines and trimethylsilylation(TMS)and tetrahydropyranylation(THP)of alcohols.The method is general for the preparation of N-boc derivatives of aliphatic(acyclic and cyclic)and aromatic,and primary and secondary amines and also various TMS-ethers and THP-ethers.The simple separation of the catalyst from the product is one of the many advantages of this method.

Bibracchial Lariat Ethers(Ⅰ)——The Synthesis and Crystal Structure of the N,N'-bis(2-Methoxy-1-Naphthylmethyl)-4,13-Diaza-18-Crown-6 Sodium Iodide Complex

Diaza Crown ethers are versatile complexing reagents, their complexing abilities are dramatically modified by the electron donating atoms on substituents attached to the nitrogen if they can give a three-dimensional cavity as in cryptates. Hence the synthesis and characterization of bibracchial lariat ethers (BIBLES) have received much attention. In the preparation of new BIBLES, a complex Ⅱ was unexpectedly obtained.

REGIOSELECTIVE OXIDATION OF KETONE BY AN OXIDATIVE REAGENT SYSTEM KH/O_2/18-CROWN-6/THF:APPLICATION TO SYNTHESIS OF VARIOUS LACTONES

the regioselectivity in the oxidation of different types of ketone compounds 1--6 with an oxidative reagent system,KH/O_2/18- Crown-6/THF is described.From these oxidative products,the various lactones have been prepared.

Chromatographic separation of Be（Ⅱ） from Mg（Ⅱ）, Ca（Ⅱ）, Sr（Ⅱ） and Ba（Ⅱ） using poly[dibenzo-18-crown-6] and L-arginine

A simple and selective method for the separation of Be（Ⅱ） was developed using poly[dibenzo-18-crown-6] as a stationary phase in column chromatography. The study was carried out in L-arginine medium. 1.0-8.0 M HCl and CH3COOH, 0.5-8.0 M HBr, HClO4 and H2SO4, 0.2-1.0 M EDTA and 0.02-0.12 M ammonium oxalate were found to be an efficient eluents for Be（Ⅱ）. The capacity of polymer was 0.554-0.01 mmol/g of crown polymer. The tolerance limit of various cations and anions were reported. Be（Ⅱ） was quantitatively separated from Mg（Ⅱ）, Ca（Ⅱ）, Sr（Ⅱ） and Ba（Ⅱ）. The selective separation of Be（Ⅱ） was possible from multicomponent mixtures. The method was extended to determine Be（Ⅱ） from geological samples. Method was simple, rapid and selective having good reproducibility （approximately4-2%）.

CdI₂Extraction with 18-Crown-6 Ether into Various Diluents: Classification of Extracted Cd(II) Complex Ions Based on the HSAB Principle

CdI2 in water was extracted with 18-crown-6 ether (L) into 10 diluents at 298 K. The following equilibrium constants were determined or evaluated: some extraction constants (Kex/mol-3·dm9 & Kex,ip/mol-2·dm6 for CdLI2, Kex±/mol-2·dm6 for CdLI+ with I-, & Kex2±/mol-1·dm3 for CdL2+ with 2I-), conditional distribution constants (KD,I for I-, KD,CdLI for CdLI+, & KD,CdL for CdL2+) between the two phases, and an ion-pair formation constant (K1,org/mol-1·dm3) for CdLI+ and that (K2,org/mol-1·dm3) for CdLI2 in the organic (org) phases. Using the K1,org and K2,org values, acidities of the complex ions, CdL2+ and CdLA+ (A- = I-, Br-, & Cl-), in the 11 diluents were classified by applying the HSAB rule. Especially, the CdLA+ ions were classified as the soft acids in 9 diluents. Also, molar volumes (Vj/cm3·mol-1) of j = CdLI2 and CdL2+ were determined with the regular-solution-theory plot of logKex,ip vs. logKD,L and its pseudo-plot of logKD,CdL, respectively. Here, KD,L denotes the distribution constant of L between the two phases. So, sizes among CdLA2 and CdL2+ were compared by using the Vj values. Additionally, some distribution equilibrium potentials (dep/V) between the water and org bulk phases were topically calculated from an equation of KD,I with KSD,I, where the symbol KSD,I shows a standard distribution constant of I- at dep = 0 V for a given diluent.

One-dimensional Chain Crown Ether Complexes Synthesis and Crystal Structure of ([K(DB18-crown-6)]_(2)(CH_(3)CN))[Pt(SCN)_(4)]

The complexe{[K(DB18-crown-6)]_(2)(CH_(3)CN)}[Pt(SCN)_(4)]was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complexe belongs to monoclinic,space group c2/c with cell dimensions,a=2.5904(8),6=1.3653(4),c-1.84706(6)nm,β=123.811(4)°,V=5-339(3)nm^(3),Z=4,.Dcalcd=l.577 g/cm^(3),F(000)=2552,R_(1)=0.051 l,wR_(2)=0.1411.The complexe shows one-dimensional chain of{[K(DB18-crown-6)]+complex cation and[Pt(SCN),i]2-complex anion bridged by N atom of CHaCN moleculer between two[K(DB18-crown-6)]_(2)[Pt(SCN)_(4)]groups respectively.

二环己基-18-冠-6对锶的萃取

为了解二环己基-18-冠-6(DCH18C6)在酸性介质中对锶的萃取行为,考察了DCH18C6的浓度、不同酸介质、不同稀释剂、硝酸浓度对锶分配比的影响。结果表明,该萃取体系在硝酸介质中能够有效的萃取锶,当DCH18C6浓度为0.1 mol/L时,萃取率高于92%,用去离子水反萃时,反萃率可达100%。采用双对数斜率法确定了DCH18C6萃取锶的萃合物组成,当c(DCH18C6)<8 mmol/L时,DCH18C6同锶萃合物的组成为1:2应占主要份额。当c(DCH18C6)≥8 mmol/L时,此时DCH18C6同锶萃合物的组成为1:1应占主要份额。

冠醚萃取法从高放废液中去除锶Ⅲ．二环己基18冠6－辛醇－［2］对锶的萃取

研究了在硝酸介质中二环已基１８冠６－辛醇－［２］对锶的萃取。结果表明，这种萃取体系对锶具有良好的萃取性能。同时还研究了水相硝酸浓度、平衡时间及锶浓度对萃取的影响。该萃取体系具有较快的反应动力学，锶浓度对萃取没有很大的影响。体系具有良好的反萃性能，可用去离子水作为反萃剂。从模拟高放废液中对锶和其它主要阳离子的萃取分离表明，该体系不仅对锶具有很好的萃取性能，而且对其它阳离子也具有很好的分离性能。

硝酸介质中二环己基18-冠-6对锶的萃取

利用冠醚二环己基-18-冠-6(DCH18C6)作为萃取剂在硝酸介质中对锶的萃取性能进行了系统研究,考察了稀释剂、硝酸浓度、振荡时间、温度对锶萃取的影响,结果表明,该萃取体系与硝酸的浓度有关,当萃取剂浓度为0.01mol/L,以1,1,2,2-四氯乙烷为稀释剂,硝酸浓度为1mol/L时,锶的萃取率可高达92%左右,利用纯水作为反萃剂,反萃率可达(99.56±1.7)%左右。该萃取反应动力学比较快,可在10min达到平衡,热力学实验表明该萃取反应是一个放热反应。同时选择性萃取实验结果表明,冠醚二环己基-18-冠-6能有效地从多种离子共存的体系中选择性地萃取锶。

二环己基并-18-冠-6合成工艺的改进

报道了改进的二环己基并-18-冠-6（DCH-18-C-6）合成方法，并用该法实现了DCH-18-C-6的工业规模合成。对由二苯并-18-冠-6加氢合成DCH-18-C-6的反应中使用的Picher-钌催化剂进行了改性，用pH3—5条件下新制备的Picher-钌催化剂，将反应温度提高并控制在130—140℃之间，可使氢化产率由文献报道的最高65％提高到85％以上，还显著提高了产物中DCH-18-C-6的立体异构体A（cis-syn-cis）含量。建立了用气相色谱法测定DCH-18-C-6异构体含量的方法，并用正庚烷进行结晶以实现A（cis-syn-cis）的提纯。

二环己基并18冠6的制备方法

For hydrogenation of dibenzo 18 crown 6 the catlalyst RuO 2 on alumina was used instead of reported Pichler ruthenium. The separation and purification processes of the targ et product also have been improved. The method is much simple, economic and time saving.

硝酸介质中DCH_(18)C_6对Sr^(2+)的萃取行为研究

文章研究了硝酸介质中二环己基-18-冠醚-6(DCH18C6)对锶的萃取行为。通过考察稀释剂、相比(O/A)、萃取剂浓度及硝酸浓度对萃取过程中分配比和萃取率的影响,得出了DCH18C6在硝酸介质中对Sr2+的萃取规律。实验结果表明,该萃取体系在硝酸介质中能够有效地萃取锶,在萃取相比为1∶4,DCH18C6的浓度为0.1 mol/L,硝酸浓度为1.0 mol/L时,一次萃取率高于90%,用去离子水反萃四次,反萃率可达100%。

二环己基-18冠-6加速锶离子在微米管支撑的水/1,2-二氯乙烷界面上的转移反应

采用玻璃微米管支撑的液/液界面通过循环伏安法(CV)研究了二环己基-18冠6(DCH18C6)加速Sr2+在水/1,2-二氯乙烷(W/DCE)界面上的转移反应,考察了DCH18C6加速Sr2+在W/DCE界面转移的影响因素,如DCH18C6和Sr2+浓度等,并求算其络合物的稳定常数。实验结果表明,Sr2+与DCH18C6发生的是一个1:1的扩散控制的界面络合转移过程,其络合常数β为5.31×1023。本研究可为理解溶剂萃取Sr2+行为提供基础理论数据。

18-冠-6/ADN含能共晶氧化剂对BAMO-THF推进剂能量特性的影响

采用X射线单晶衍射表征了新型18-冠-6/二硝酰胺铵含能共晶(18-Crown-6/ADN)氧化剂晶体的结构;采用氧弹式量热计测定了其燃烧热并获得其标准摩尔生成焓(Δ_fH_m~θ);采用最小自由能法计算了18-Crown-6/ADN对3,3-二叠氮甲基氧丁环与四氢呋喃共聚醚(BAMO-THF)推进剂能量性能的影响。结果表明,18-Crown-6/ADN晶体属于单斜晶系,C2/c空间群,晶胞参数:a=2.393 5nm、b=0.863 27nm、c=2.032 4nm;α=90°、β=112.874°、γ=90°;18-Crown-6/AND的Δ_fH_m~θ为-(833.57±4.89)kJ/mol,其取代配方中的AP、HMX、ADN或CL-20后推进剂的理论比冲(I_(sp))最低;含18-Crown-6/ADN的BAMO-THF推进剂中加入部分高能组分(如CL-20、HMX)可提高其能量性能;能量计算表明,BAMO-THF/A3、Al、AP、(18-Crown-6/ADN)/CL-20/HMX的质量分数分别为25%、18%、15%、42%,18-Crown-6/ADN、CL-20和HMX的质量比约3∶4∶3时,配方的I_(sp)约2 550N·s/kg,燃烧室温度约2 900K,燃气平均相对分子质量约24.50,特征速度约1 540m/s。