稀土与含硫有机配体配合物的研究(Ⅷ)——甘氨酸二硫代甲酸镍与稀土醋酸盐多核配合物的合成与性质

在乙醇—水溶液中,用稀土醋酸盐与氨基乙酸二硫代甲酸镍[H_2Ni(Gc)_2]反应,制备出14种稀土元素的多核配合物,通过元素分析确定了配合物的组成为RENi(Gc)_2·AC·H_2O(RE=La—Gd,除Ce、Pm外)和RE_2[Ni(Gc)_2]_3·xH_2O(RE=Tb—Lu,Y;x=4,8,10),研究了配合物的溶解性、红外光谱、X射线光电子能谱和核磁共振氢谱。     

稀土高氯酸盐与1,10—二氮杂菲—1—氧化物的配合物研究

本研究合成出十三种稀土高氯酸盐与phenNO的配合物。元素分析确定配合物的组成为RE(phenNO)_4(ClO_4)_3·H_2O(RE=La、Pr、Nd,Sm～Lu)。对该系列配合物的红外光谱、紫外光谱、荧光光谱、热谱、摩尔电导等性质进行了研究。     

稀土与含硫有机配体配合物的研究 Ⅴ.哌啶荒酸重稀土配合物的制备与性质

在干燥的氮气氛中制备了重稀土与哌啶荒酸形成的7个固体配合物,确定其组成为C_5H_(10)NH_2[RE(S_2CNC_5H_(10)_4]·xH_2O(RE=Y,Tb～Er;x=2,6)和RE(S_2CNC_5H_(10))Cl_2·2H_2O(RE=Tm、Yb)。通过红外光谱、摩尔电导、差热-热重分析等对配合物进行了鉴定。结果表明,在该类配合物中配体通过硫原子以二齿形式与稀土离子配位。     

硼合多羟基醇希土配合物的合成与性质及其配位作用的研究

本文合成了硼合甘油希土和硼合葡萄糖希土二类共八个配合物。用化学分析、红外光谱、紫外光谱及热谱确定其组成为:RE(BO_2·C_3H_8O_3)_3·nCH_3OH和RE(BO_2·C_6H_(12)O_6)_3·3H_2O(RE=Nd、Gd、Y、Yb)。摩尔电导测定表明这两类化合物均为中性配合物。红外光谱显示出硼与多羟基醇之间以硼氧四面体形式结合。本文还通过电位滴定法讨论了希土与硼合多羟基醇之间的配位作用。     

具有生物活性的金属配合物的研究——Ⅵ.3,6-二(二甲氨基)-二苯并碘六环镧反式-1,2-环己烷二胺四乙酸配合物的合成、性质及抗肿瘤活性

反式-1,2-环己烷二胺四乙酸(H_4DCTA)可作为体内锰中毒的解毒剂,它在溶液中与稀土离子的配合行为及体内载体效应和代谢机制均曾被研究。但H_4DCTA的稀土配合物作为抗癌药物的筛选以及其配阴离子[RE(DCTA)]-的抗衡离子是大体积有机阳离子的配合物的合成则未见报道。为此我们在完成了[C_(17)H_(20)N_2I][RE(EDTA)]·nH_2O[C_(17)H_(20)N_2I]_3[RE(Cit)_2]·nH_2O及[C_(17)H_(20)N_2I]_3[RE(NTA)_2]·nH_2O等多种配合物的     

希土配合物的研究——Ⅷ.1,4-双(1’-苯基-3’-甲基-5’-氧代吡唑酮基-4’)代-1,4-丁二酮(BPMPBD)与希土元素配合物的合成及表征

在乙醇-水溶液中,当pH=5-6时,用希土硝酸盐与BPMPBD反应,合成了15种希土元素(除Sc、Pm外)的二元配合物.通过化学分析和元素分析确定了配合物的组成为REL_2·nH_2O(RE=La,n=5,RE=Y,n=4,RE=Pr、Nd、Sm、Eu、Gd,n=3),RE_2L_3·5H_2O(RE=Tb、Dy、Ho、Er、Tm、Yb、Lu)及CeL_2·4H_2O.研究了这些配合物的一些性质及红外光谱、紫外光谱、核磁共振、荧光光谱和差热分析,认为重希土配合物具有双核结构。     

希土冠醚类配合物的研究--Ⅹ.轻希土硝酸盐与二苯并-24-冠-8固态配合物的合成及性质

在乙腈介质中制得了2:1型固态配合物[Ln(NO_3)_3]_2·DB24C8.2H_2O(Ln=La、Pr)和3:2型固态配合物[Ln(NO_3)_3]_3(DB24C8)_2·3H_2O(Ln=Nd,Sm,Eu)。研究了冠醚及其配合物的红外光谱、紫外光谱、热稳定性及X—射线粉末衍射等性质,观察了它们在常见有机溶剂中的溶解情况,在乙腈中的电导测定结果表明这些配合物均为非电解质。     

芳香胺及其氮氧化物合希土配合物的研究 V.2, 2''—联喹啉—N, N''—二氧化物合硝酸希土固体配合物的合成及其性质

在无水乙醇和氯仿混合溶剂中使重希土硝酸盐与2,2′—联喹啉—N,N′—二氧化物(BiqO_2)作用,制得了固体配合物Ln(BiqO_2)(NO_3)_3·2H_2O(Ln=Tm,Yb,Lu,Y)。通过元素分析、X光粉末衍射物相分析、差热—热重分析、红外光谱、紫外光谱、溶解性及摩尔电导测定,研究了配合物的组成及其有关性质。     

希土与甘氨酸及2, 2''—联吡啶氮氧化物多元固体配合物研究

在非水介质中合成出希土氯化物、硝酸盐与甘氨酸及2,2 ′—联吡啶氮氧化物的多元固体配合物LnGly(BipyO_2)_2Cl_3·H_2O和LnGly(BipyO_2)_2(NO_3)_3·H_2O(Ln=La,Ce,Pr,Nd,Sm,Eu)通过元素分析、红外光谱、荧光光谱、DSC—TGA分析、溶解性及摩尔电导测定,研究了配合物的组成和性质.     

具有生物活性的金属配合物的研究 Ⅲ.3-6-二(二甲氨基)-二苯并碘六环稀土二柠檬酸配合物的合成、性质及抗肿瘤活性

合成了十五种新的3,6-二(二甲氨基)-二苯并碘六环稀土二柠檬酸配合物,其化学式为:[C_(17)H_(20)N_2I]_3[RE(C_6H_5O_7)_2]·xH_2O(RE=La-Nd,x=5;Sm-Tb,x=4;Dy-Lu,Y,x=3)。利用X射线粉末衍射、热重-差热,红外光谱、紫外光谱、摩尔电导等对这些配合物进行了表征。试验表明,镧配合物对L_(7712)癌细胞DNA合成的抑制率(97.3％)明显高于其前体(C_(17)H_(20)N_2I~+·HCOO~-,72.5％;Na_3[La(C_6H_5O_7)_2],-16.5％)。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.