Isomerisation of 1-methylene-2-methyl-2-(2-oxopropyl)-cyclohexanes to 2-methylene-1-methyl-1-(2-oxopropyl)-cyclohexanes by ene and retro-ene reaction

Thermal activation of the normal Claisen products, the enones 4 7 and 14 in the presence of a catalytic amount of propionic acid generated the isomeric enones 6 9 and 15 via the sequential intramolecular ene-reaction of the enol tautomer followed by 1,5-hydrogen transfer (or retro ene-reaction) of the resultant acetyl cyclopropane intermediate. conversion of the enones 9 and 15 into the corresponding cyclohexenones 10 and 16 established the structures of the rearrangement products.

A comparison of the DNMR behaviour of methyl 5,6-bis(2-methoxyphenyl)-1,4-dimethyl-7-oxobicyclo[2.2.1]hept-5-en-2-endo-carboxylate and its 7-oxa analogue

Methyl 5,6-Bis(2-methoxyphenyt)-1,4-dimethyl-7-oxobicyclo[2.2.1]hept-5-en-2-endo-carboxylate, a moderately crowded norbornenone ester, exhibits complex VT-DNMR behaviour. A similar behaviour is not seen in its 7-oxa analogue, showing that conformational transmission from position 7 has a crucial influence on the distance parameters that govern the dynamic processes involving the substituents on the bicycloheptene framework.

Synthesis and Antileukemic Activity of Novel 2-(4-(2,4-dimethoxybenzoyl)phenoxy)-1-(4-(3-(piperidin-4-yl)propyl)piper idin-1-yl)ethanone Derivatives

A series of novel 2-(4-(2,4-dimethoxybenzoyl)phenoxy)-1-(4-(3-(piperidin-4-yl)propyl) piperidin-1-yl)ethanone derivatives 9(ae) and 10(ag) were synthesized and characterized by 1H NMR, IR, mass spectral, and elemental analysis. These novel compounds were evaluated for their antileukemic activity against two human leukemic cell lines (K562 and CEM) by using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide assay. Some of the tested compounds showed good antiproliferative activity with IC50 values ranging from 1.6 to 8.0 mu m. Compound 9c, 9e, and 10f with an electron-withdrawing halogen substituent at the para position on the phenyl ring showed excellent in vitro potency against tested human leukemia cells (K562 and CEM).

Propyl-2-(8-(3,4-Difluorobenzyl)-2 `,5 `-Dioxo-8-AzaspiroBicyclo3.2.1] Octane-3,4 `-Imidazolidine]-1 `-yl) Acetate Induces Apoptosis in Human Leukemia Cells through Mitochondrial Pathway following Cell Cycle Arrest

Background: Due to the functional defects in apoptosis signaling molecules or deficient activation of apoptosis pathways, leukemia has become an aggressive disease with poor prognosis. Although the majority of leukemia patients initially respond to chemotherapy, relapse is still the leading cause of death. Hence targeting apoptosis pathway would be a promising strategy for the improved treatment of leukemia. Hydantoin derivatives possess a wide range of important biological and pharmacological properties including anticancer properties. Here we investigated the antileukemic activity and mechanism of action of one of the potent azaspiro hydantoin derivative, (ASHD). Materials and Methods: To investigate the antileukemic efficacy of ASHD, we have used MTT assay, cell cycle analysis by FACS, tritiated thymidine incorporation assay, Annexin V staining, JC1 staining and western blot analysis. Results: Results showed that ASHD was approximately 3-fold more potent than the parent compounds in inducing cytotoxicity. Tritiated thymidine assay in conjunction with cell cycle analysis suggests that ASHD inhibited the growth of leukemic cells. The limited effect of ASHD on cell viability of normal cells indicated that it may be specifically directed to cancer cells. Translocation of phosphatidyl serine, activation of caspase 3, caspase 9, PARP, alteration in the ratio of BCL2/BAD protein expression as well as the loss of mitochondrial membrane potential suggests activation of the intrinsic pathway of apoptosis. Conclusion: These results could facilitate the future development of novel hydantoin derivatives as chemotherapeutic agents for leukemia.

以1-苯基-3-甲基-4-苯甲酰基代吡唑酮[5]萃取稀土和钍铀钛锆及其在分析化学中的某些应用

本文研究了以PMBP-苯萃取稀土和钍、铀、钛、锆的萃取行为。测定了La、Ce、Pr、Nd、Sm、Gd、Dy、Yb、Y、U(Ⅵ)、Ti、Th和Zr的pH_(1/2)值,计算了它们的萃取平衡常数。并介绍了近十年来作者将此萃取剂应用于铀、钍、稀土、鋰、钢铁合金及岩石中痕量稀土、钍和钙的分离和测定方面的工作。实践证明,PMOP合成简便、价格低廉、萃取能力较强,是比TTA更为优越的萃取剂。

用1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮萃取~(46)Sc的研究

用1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮(PMBP)做萃取剂,氯仿和环己烷为稀释剂,观察了在HCl溶液46Sc的溶剂萃取行为。实验结果表明,从10-3~10-2mol/L的HCl溶液中用PMBP-氯仿(或环己烷)能有效地萃取46Sc,萃取率可达95%以上。另外,对PMBP从HCl溶液中萃取46Sc和234Th的结果也做了比较,结果表明,通过控制水溶液中HCl的浓度,能实现234Th与46Sc的分离。

1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮和磷酸三丁脂协同萃取镭的研究

用1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮(PMBP)为萃取剂,苯为稀释剂,从pH5的水相中萃取船224Ra,发现224Ra的萃取效率非常低。若往PMBP中加入少量的磷酸三丁脂(TBP),则会极大地提高镭的萃取效率,这说明TBP对PMBP萃取镭有显著的协同萃取效应。完成了萃取时间和反萃时间对224Ra萃取效率的影响以及224Ra萃取效率与TBP量之间的依赖关系等条件实验。

用1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮从硝酸介质中萃取钪

用1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮(PMBP)做萃取剂研究了从HNO_3介质中痕量钪的溶剂萃取行为。发现在很低的酸度下,PMBP几乎可以定量地萃取痕量的钪。同时,也讨论了用PMBP从~(18)O离子辐照过的铀靶溶液中萃取分离钍时钪的沾污。

1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮(PMBP)萃取钍流程的改进

在用PMBP(1 苯基 3 甲基 4 苯甲酰基 5 吡唑啉酮 )从 14MeV中子照射过的天然U靶溶液中萃取Th流程的基础上 ,将萃取介质改为HNO3溶液 ,并将单次萃取 反萃改为两次萃取 反萃 ;在反萃溶液中加入I- 载体和NaNO2溶液 ,在Fe(OH) 3沉淀溶液中加入Br- 载体。用改进后的流程从 6 0MeV/u18O离子轰击天然U的HNO3溶液中分离Th ,从制得的Th样品的γ射线谱可以看出 ,该流程能去除绝大部分产物元素 ,特别是能完全去除溴和碘

用1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮从硝酸中萃取痕量钍

用1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮(PMBP)为萃取剂,~(234)Th作示踪剂,完成了在硝酸介质中痕量钍溶剂萃取行为的研究。在~(234)Th萃取效率与酸度、萃取剂浓度、平衡时间等依赖关系的条件实验的基础上,获得了萃取钍的最佳条件。使用改进的PMBP萃取钍的流程,从~(18)O离子辐照过的铀靶中分离钍,钍样品的γ射线单谱显示绝大部分反应产物和大量铀的去除是满意的。

1-苯基-3-甲基-4-苯甲酰基-吡唑酮-5与中性磷(膦)萃取剂协同萃取镧B

研究了 1 苯基 3 甲基 4 苯甲酰基 -吡唑酮 5 (HPMBP)和中性有机磷 (膦 )类萃取剂Cyanex 4 71X(TIBPS ,B)在硝酸介质中对稀土元素La 的萃取 ,用斜率法和恒摩尔法探讨了萃取机理 ,确定了萃合物的组成为La(NO3 ) 2 ·PMBP·B ,计算了萃取平衡常数。比较了HPMBP与Cyanex 4 71X、Cyanex 92 1、Cyanex 92 3、Cyanex 92 5、DEH/EHP、P35 0及TBP的单独及混合体系萃取La 的性能 ,结果表明 :所有混合体系对La 均有协同效应 ,其中HPMBP与Cyanex 92 3、Cyanex 92 1、Cyanex 92 5的混合体系是萃取La 的有效体系。

Synthesis of 2-benzylthio-5-phenyl-3,4-disubstituted thiophenes by intramolecular condensation of alpha-oxo ketene dibenzylthioacetals

A facile route to 2-benzylthio-5-phenyl-3,4-disubstituted thiophenes was described. Catalyzed by sodium hydroxide, the title compounds were synthesized in moderate to good yields simply from the intramolecular aldol type condensation of alpha-oxo ketene dibenzylthioacetals. The chemical selectivity for this annulation reaction was studied and discussed.

Resolution of 3,3 '-dioxo-1,1 '(3H,3 ' H)spirobi[isobenzofuran]-5,6,5 ' 6 '-tetracarboxylic acid and Optically active Polyimides thereof

3,3'-Dioxo-1.1'(3H.3'H)spirobi[isobenzofuran]-5,6,5',6 acid 1 was resolved successfully and the corresponding optically active polyimides PI were synthesized. The properties of the optically active PI and the racemic one were investigated. The results showed that the specific rotation of(-)-PI was about two times to that of the: (+)-PI, and the regularity of the optically active PI was higher than that of the racemic one.