Reagents for new heteroannelation reactions III. 2-(Methylthio)-2-thiazoline

Summary A variety of partly novel tri- and tetracyclic hetero systems were obtained by reaction of heteroaromatic 2-aminoesters with 2-(methylthio)-2-thiazoline, yielding double-annelation of a thiazolo[2,3-b]pyrimido moiety in a one-pot process.On leave from University of Chittagong, Bangladesh     

Surfactant effect on enhancing (S)-naproxen prodrug production from racemic naproxen by lipase

In the enantioselective esterification of racemic naproxen with 4(2-hydroxyethyl) morpholine by Lipase MY in organic solvents, a productivity improvement of the desired (S)-naproxen ester from 0.42 to 0.72 mM at the reaction time of 130 h was observed, when the surfactantbis (2-ethylhexyl) sodium sulfosuccinate (AOT) was added in the reaction mixture. The presence of a small amount of exogenously added water dramatically activated the enzyme in AOT/cyclohexane-reversed micelles. Desorption of the surfactant molecule from the enzyme mass and solubilization of the enzyme into reversed micelles were used to elucidate an existing maximum of the initial rate of (S)-naproxen synthesis with the water content. Moreover, the effects of alcohol and surfactant concentration on the enzyme activity are reported.     

Syntheses and structural characterizations of Fe_4S_4 cubane-like cluster compounds containing cycloalkylthiolate ligands

In a reaction system consisting of FeCl2,tetrathiometallate and cycloalkylthiolate,two Fe4S4 cubane-like cluster compounds were obtained with the following crystallographic data:(PhCH2NMe32[Fe4S4 (SC5H9)4](Ⅰ),monoclinic space group P21/c,a=1.6327(4),6=1.1229(3),c=2.802 5( 10) nm,β=94.63(2)°,Z=4,and R=0.074; (Et4N)2[Fe4S4(SC6H11)4](Ⅱ),tetragonal space group I42m,a=1.16705(9),b=1.167 06(2),c=2.063 26(5) nm,Z=2,Dabs=1.28 g/cm3,and R=0.078 The participation of cy-cloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure.Meanwhile,the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.     

Alternating iteration and elliptic variational inequalities

Summary Free boundary value problems, too complicated for formulation as a variational inequality, are broken up into two problems on overlapping regions. On one region the problem is treated as an ordinary boundary value problem; on the second region, the free boundary part of the problem is reduced to a variational inequality. By solving the two problems successively it is shown that under certain conditions the successive solutions converge to a single function that gives a solution of the original problem. Application to a filtration problem is given.     

聚对苯二甲酸乙二酯非晶态膜片单轴热——拉伸中的结晶与松弛

用动态力学损耗温度谱作为测试手段,研究了非晶态PET膜片在78—112℃温度范围内的单轴拉伸。实验结果说明,在较低温度下所得结晶的拉伸试样,完全由于应变诱发结晶,发生在应力-应变曲线的屈服后应力开始上升的阶段。在较高温度下(90℃或更高)拉伸可得非晶态而且光学各向同性的试样,是由于分子链的小尺度取向在拉伸过程中已完全热松弛所致,而分子链的大尺度取向要通过高弹态流动而松弛,其速率较慢,用拉伸后试样两端固定时的应力松弛进行了观察。在较低温度下应力松弛后仍为非晶态,在较高温度下应力松弛到起始应力的1O％下才开始结晶。FTIR研究表明在这种状态下的结晶有一结晶诱导期,其时间尺度与应力松弛阶段相当。     

Microkinetics of H2S Removal by Zinc Oxide in the Presence of Moist Gas Atmosphere

The microkinetics os H2S removeal by ZnO desulfurization in H2O-CO2-N2,H2O-CO-N2 and H2O-O2-N2 gas mixtures was studied by thermogravimetric andlysis.Experiments were carried out with 100-120 mesh ZnO powder at temperatures from 473K to 563K.The results show that the kinetic behaviors of desulfurization could all be described by an improved shrinking-core model.The activation energies of the reaction and the diffusion in different gas atmospheres were estimated.     

The regioselectivity of the formation of 2-pyrazolylthiazoles and their precursors from the reaction of 2-hydrazinothiazoles with 4,4,4-trifluoro-1-hetaryl-1,3-butanediones

Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c.     

联苯甲酰双缩氨基脲硫氰酸根硝酸根混合阴离子配位钕(Ⅲ)配合物的合成与结构

合成了联苯甲酰双缩氨基脲硫氰酸根、硝酸根混合配位的钕(Ⅲ)配合物。在此配合物中只有1个链状配体,另有2个硫氰酸根、1个硝酸根和1个水分子参与配位。总配位数是9。晶体结构分析表明,该配合物晶体属三斜晶系,P空间群。晶胞参数a=10。866(2),b=13.687(3),c=15.433(3),α=98.75(4)°,β=107.64(5)°,γ=112.14(5)°。最终偏差因子R=0.075。用INDO方法计算结果表明:NCS对Nd(Ⅲ)的配位比=C基对Nd(Ⅲ)的配位强。     

以硫醚为主链的螯合树脂研究Ⅰ.4-氨基安替吡啉树脂和乙基原磺酸基树脂的合成及吸附性能

聚环硫氯丙烷或环硫氯丙烷与环氧氯丙烷共聚物，在少量二乙烯三胺存在下制得交联预聚物，将交联预聚物与4－氨基安替吡啉（4AAP）或乙基原磺酸钾（PEA）反应，制得四种侧链带氨基安替吡啉，乙基原碘酸基的新型螯合树脂。它们对贵金属具有优良的吸附性能和高的吸附选择性。并通过X－射线光电子能谱初步探讨了树脂对金属离子的螯合作用。     

Phase Transition and Crystal Structure of the Monomeric Europium(II) Thiolate Eu(SC36H49)2

Single crystal X‐ray diffraction of Eu(SC₃₆H₄₉)₂ has revealed a first order phase transition at a temperature of 119 K, that involves a reduction of the specific volume by 1 %. The transition corresponds to a doubling of the unit cell, as it is the result from reorientations of isopropyl groups that appear at peripheral sites of the organic ligands. It is argued that a denser packing is achieved at the expense of a less favourable conformation of one of the two crystallographically‐independent complexes in the low‐temperature phase. The Bond‐Valence method is used to show that interactions of equal strengths are present between europium and both sulphur atoms and both coordinating phenyl rings.