两个新型氮氧自由基及其配合物的合成、晶体结构和磁性

合成并表征了两种新的含有酰氨基取代的氮氧自由基配体L1和L2。将L1和L2与六氟乙酰丙酮盐(Co(II), Ni(II),Mn(II))配位得到五个新的单核金属配合物L1Co(hfac)2, L1Ni(hfac)2, L2Co(hfac)2,L2Ni(hfac)2和L2Mn(hfac)2。对L1和L2及其配合物的结构和磁性进行了表征,在配合物中氮氧自由基的氧和取代基羰基氧均和金属离子配位,自由基和金属离子之间存在着强的反铁磁相互作用。     

氟脲嘧啶自旋标记衍生物的合成与抗肿瘤活性（Ⅲ）

合成了９个新的５－氟脲嘧啶自旋标记衍生物２、５ａ－ｃ和７ａ－ｃ，经元素分析、ＩＲ、ＵＶ、ＭＳ和ＥＳＲ确定了其组成和结构，对化合物２和５ａ－ｃ进行了抗小艾氏腹水肉瘤Ｓ１８０的体内筛选，初步试验结果表明：化合物５ｃ对两种瘤株均显示较强的抑制作用，其抗肿瘤活性与５－氟脲嘧啶相似，而５ｃ（ＬＤ５０＝９４４．８ｍｇ／ｋｇ）的急性毒性比５－氟脲嘧啶（ＬＤ５０＝１１７．２ｍｇ／ｋｇ）降低约８倍。     

氮氧自由基的应用研究进展

氮氧自由基化合物是指含碳、氮、氧、氢等元素以及自旋单电子的有机化合物,因其自身的特殊性质被广泛应用于很多领域。本文结合氮氧自由基的特点,对其在生物学、磁性、有机催化和阻聚等方面的应用研究进行了总结,并对氮氧自由基化合物的发展趋势进行了展望。     

氮氧自由基单核钬配合物的合成与结构

A novel mononuclear Ho(Ⅲ) nitronyl nitroxide complex [Ho(hfac)₃(NITPhDma)₂], (NITPhDma=2-(4-dimethylamino-phenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, hfac=hexafluoroacetylacetonate), was synth-esized and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P2₁/n with a=1.274 5(1) nm, b=1.753 1(2) nm, c=2.482 8(2) nm, β=93.753(2)°. The Ho(Ⅲ) ion is eight-coordinated with a distorted dodecahedron environment. Each NITPhDma radical acts as monodentate ligand towards Ho(Ⅲ) ion through the NO group, and the complex molecules are well isolated. CCDC: 775839.     

氮氧自由基——Ⅶ.双多氟和全氟烷基氮氧自由基与烷烃攫氢反应的顺磁共振研

本文报道将先前合成的双多氟和全氟烷基氮氧自由基1与多氟和合氟亚硝基烷烃2混合溶液的技术应用于烷烃、芳烃3自由基攫氢反应的研究，氮氧自由基1由烷烃，芳烃迅速攫氢转变为羟胺，生成的烷基自由基中间体立即被2截捕得到稳定的自旋加合物4和5.由自施加合物ESR参数，可以确定自由基结构并由引来研究攫氢反应机理，本文也提供了一个产生大量含氟烷基氮氧自由基并研究其结构的有效而简单的方法。     

4-取代硫脲基-2,2,6,6-四甲基哌啶氮氧自由基化合物的合成

本文报道了五种新型的4-取代硫脲基-2,2,6,6-四甲基哌啶氮氧自由基化合物6(a～e)。并经元素分析、红外光谱及电子自旋共振波谱确证了它们的结构。药理实验表明,化合物6(a～c)对 L7712白血病细胞具有一定的抑制作用。     

氮氧自由基与氨基酸偶联物的设计合成与结构表征

将对甲酰基苯甲酸分别与氨基乙酸甲酯和4-氨基丁酸甲酯生成酰胺后,再分别与2,3-二甲基-2,3-二羟氨基丁烷进行缩合反应,最后经高碘酸钠氧化得到两种氮氧自由基与氨基酸偶联物,并通过IR、EPR、EI-MS和元素分析对目标化合物的结构进行了表征.     

氯球键合氮氧自由基的合成及在醇氧化中的应用

本文以氯甲基化聚苯乙烯珠体（简称氯球）为原料,和４－羟基－２．２．２．２－四甲基哌啶氮氧自由基反应,合成出氯球键合氮氧自由基。通过基对醇的氧化反应,考察了负载氮氧自由基的氧化性能。     

氮氧自由基自旋标记川芎嗪的合成及抗辐射性能评价

设计合成氮氧自由基自旋标记川芎嗪（NTMP）,研究其抗辐射性能。通过川芎嗪甲醛与四甲基羟胺反应合成了4,4,5,5-四甲基-2-（3,5,6-三甲基吡嗪）咪唑烷-1,3-二醇,利用高碘酸钠氧化制备得到了NTMP。通过红外光谱、核磁、质谱表征证实NTMP成功合成。评价了NTMP的对小鼠胸腺上皮细胞（MTEC1）的细胞的毒性,辐射前和辐射后分别给药的抗辐射性能,以及100 mg·kg^-1的NTMP的小鼠生存率。NTMP对MTEC1细胞在0.1～10μg·mL^-1的浓度范围内没有明显的细胞毒性。辐射前和辐射后给药对MTEC1细胞均有较好的辐射损伤保护作用。小鼠生存率实验表明NTMP在照射后给药（存活率60%）的抗辐射性能优于辐射前给药（存活率43%）。NTMP在体内外具有较好的辐射保护性能。     

一种长链结构稳态氮氧自由基的合成

从提高光稳定剂与聚合物的相容性及光稳定效能的目的出发,以受阻胺为原料,H2O2为氧化剂,合成了具有高分子长链结构的新型稳态氮氧自由基,其结构经IR,ESR,GPC及元素分析表征。     

A Kinetic Evidence for the Nitroxyl Radicals Recycling Mechanism in the Photostabilizing Process of HALS

The photoinduced bulk polymerization of a reactive-hindered amine fight stabilizers(r-HALS), 4-acryloyl-2, 2, 6, 6-tetramethylpiperidinyl (ATMP), was performed at 80℃ by using a DPC technique. An unique periodic exponential attenuation-type oscillating curve was found when the polymerization was carried out in air, but this phenomenon was not found in nitrogen.It is supposed that this unique kinetic performance may be attributed to nitroxyl radicals that are produced in situ from the oxidation of ATMP. ATMP polymer with narrow polydispersity (d =1.03) can be obtained by photoinduced solution polymerization of ATMP. The signal detected in ESR may be assigned to the nitroxyl radicals in the matrix of ATMP polymer. Since this kind of recycling of nitroxyl radicals is well documented for the photostabilizing mechanism of HALS, the present results may serve as a kinetic evidence for this mechanism.     

Stable nitroxyl radicals with a hydrogen atom at α-carbon atom of nitroxyl group

Nitroxyl radicals containing the diphenylmethyl group as one of the substituents at the nitroxyl group are stable compounds that can be isolated in an individual state.N-(2-Hydroxy-3-methyl-2-phenylcyclohexyl)-N-diphenylmethylnitroxyl was characterized by X-ray diffraction analysis for the first time.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 400–408, February, 1996.     

Synthesis,Reactions and Applications of Phosphorus Containing Carbon Centered Radicals

A general method for synthesis of C_n-C (n=1, 2...) phosphonate bonds involving a reaction of 1-diethoxy-phosphorylalkan-1-, -2-and -3-yl radicals 1,3,6 with alkenes 4, a new example of functional group interconversion in 1-heterosubstituted phosphonates and synthesis of useful phosphoroorganic compounds and methylenomycin B are described.     

Solid-phase mechanochemical incorporation of a spin label into cellulose

Samples of cellulose labeled with stable nitroxyl radicals were prepared by mechanochemical synthesis. The samples were studied by IR and EPR spectroscopies, X-ray phase analysis, and electron microscopy. The EPR spectral patterns indicate a uniform distribution of “grafted” paramagnetic centers over the cellulose macromolecular chains. X-Ray diffraction patterns obtained and the results of crystallinity index calculations for the samples showed that strong bonding of spin labels causes changes in the cellulose structure up to nearly complete amorphization of the material. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1127–1130, May, 2005.     

Stable vinylnitroxyl radicals, pyrroline derivatives

The first representatives of stable vinyl nitroxides,viz., radicals of the pyrroline series, were synthesized. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 103–111, January, 2000.     

Stable vinylnitroxyl radicals, pyrroline derivatives

The first representatives of stable vinyl nitroxides,viz., radicals of the pyrroline series, were synthesized. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 103–111, January, 2000.     

Reaction of dihydropyrazine-1,4-dioxides with organolithium compounds. Synthesis of nitroxyl radicals — derivatives of tetrahydropyrazine oxide

Reaction of dihydropyrazine-1,4-dioxides with organoiithium compounds followed by oxidation with MnO₂ gives stable nitroxides of the pyrazine series. The reaction of a pyrazine containing methylnitrone groupings with ethylbenzoate in the presence of NaH or PhLi leads to mono- or diphenacyl derivatives, which have been shown to exist in solution as a mixture of tautomers. On treatment with hydroxylamine and subsequent oxidation the monophenacyl nitrone derivative yields a stable nitroxyl radical derived from spiroisoxazolopyrazine.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 927–931, May, 1993.     

Synthesis,structure, and antitumor properties of platinum(iv) complexes with aminonitroxyl radicals

The platinum(iv) complexes cis,trans,cis-Pt^IV(RNH₂)(NH₃)(OH)₂Cl₂, where R is 2,2,6,6-tetramethyl-1-oxyl-4-piperidinyl (1) or 2,2,5,5-tetramethyl-1-oxyl-3-pyrrolidinyl (2), were prepared by oxidation of the corresponding cis-Pt^II(RNH₂)(NH₃)Cl₂ complexes with hydrogen peroxide. The reactions are catalyzed by tungstate salts, which makes it possible to carry out oxidation under mild conditions. The resulting complexes were characterized by elemental analysis, HPLC, and IR, UV, and ESR spectroscopy. The structure of complex 1 was established by X-ray diffraction analysis. Complex 1 exhibits the highest antitumor activity in an experimental tumor, viz., in P388 leukemia. The resistance of the tumor to this complex developed much slower than that to Cisplatin.     

哌啶氮氧自由基与环糊精作用的电化学研究

采用循环伏安法测量水溶液中β-环糊精(β-CD)/哌啶氮氧自由基(以2,2,6,6-四甲基哌啶-1-氧化物(TEMPO)为例)体系氧化还原电位及峰值电流,并基于此探讨TEMPO与β-CD之间的包结反应。电化学测量表明,在pH=7.4的磷酸盐缓冲溶液中,以玻碳电极为工作电极,随β-CD浓度增大,β-CD/TEMPO体系的峰电位不断增大,峰电流不断减小。通过电位法测得TEMPO与β-CD的包络比为1∶1,包络常数KS为154L/mol,与电流法测得的包络常数基本吻合。