3－乙酰乙酰基－4－羟基香豆素希土配合物的合成和性质

本文报道了稀土与３－乙酰乙酰基－４－羟基香豆素配合物的合成，其化学组成为Ｌｎ（Ｈａａｃ）３．ｎＨ２Ｏ（Ｌｎ为Ｌａ，Ｐｒ，Ｎｄ，Ｇｄ，Ｄｙ，Ｅｒ，ｎ为１或２），基于Ｈ－ＮＭＲ，ＩＲ的结果，提出了稀土离子与配位体４位羟基氧与邻近羰基双齿配位结构，对Ｎｄ＾３＋及Ｅｒ＾３＋配合物的超灵敏吸收带的形状和吸收强度等也作了讨论。     

稀土离子与牛血Cu（Zn）—SOD的作用

采用ＥＳＲ、ＣＤ谱和荧光光谱研究了ｐＨ＝６．３时六次甲基四胺－ＨＣｌ缓冲溶液中ＬａＣｌ３和ＴｂＣｌ３与Ｃｕ（Ｚｎ）－ＳＯＤ的配位作用和结构。Ｃｕ（Ｚｎ）－ＳＯＤ可增强Ｔｂ＾３＋的荧光发射，Ｔｂ＾３＋与Ｃｕ（Ｚｎ）－ＳＯＤ有多个配位位置，其中有２个强结合位点，Ｌａ＾３＋可Ｔｂ＾３＋可竞争Ｃｕ（Ｚｎ）…ＳＯＤ上相同结合位点，７７Ｋ下Ｌａ＾３＋与Ｔｂ＾３＋使Ｃｕ（Ｚｎ）－ＳＯＤ的Ｃｕ＾２＋活性中心的配位     

用于分离稀土的螯合纤维的制备及性能的研究（Ⅰ）

用反应性纤维ＰＰ（ＰＶＡ，ＰＡ６）－ｇ－ＰＧＭＡ与二乙氧基亚膦酸钠反应可制得含二乙氧基亚膦酸酯的螯合纤维。研究表明，反频性纤维以接枝率１２００％的ＰＰ－ｇ－ＰＧＭＡ较子，在１４０℃下和ＮａＰＯ（ＯＥｔ）２反应１２小时，增重率可达７４％。螯合纤维ＰＰ－ｇ－ＰＧＭＡ－ＰＯ（ＯＥｔ）２对稀土离子的吸附量差异较大，其顺序为ＨＯ＾３＾＋＞Ｙｂ＾３＾＋＞Ｎｄ＾３＾＋＞Ｔｂ＾３＾＋＞Ｓｍ＾３＾＋＞Ｄｙ＾３＾＋     

壳聚糖镍和壳聚糖镧配位聚合物的配位数研究

从ＩＲ、ＥＳＲ和ＸＰＳ的测试结果可知,Ｎｉ＾２＋或Ｌａ＾３＋与壳聚糖（ＣＳ）键节单元上的氨基Ｎ和仲羟基Ｏ发生配位反应,形成ＣＳ－Ｎｉ＾２＋或ＣＳ－Ｌａ＾３＋配位聚合物膜。通过电导率研究其配位数,发现Ｎｉ＾２＋或Ｌａ＾３＋可与壳聚糖的３个或５个键节单元配位。根据以上的实验可推定中心离子Ｎｉ＾２＋与壳聚糖３个键节单元上的氨基Ｎ和仲羟基Ｏ结合,形成六配位的ＣＳ－Ｎｉ配位聚合物Ｌａ＾３＋与壳聚糖５个键节单     

镧系元素Dawson结构钨钒磷四元杂多配合物的合成,表征以…

合成了通式为Ｋ１５Ｈ３〔Ｃｅ（Ｐ２Ｗ１６ＶＯ６１）２〕．６１Ｈ２Ｏ、Ｋ１５Ｈ４〔Ｌｎ（Ｐ２Ｗ１６ＶＯ６１）２〕．ｘＨ２Ｏ（Ｌｎ＝Ｌａ＾３＋，Ｐｒ＾３＋，Ｎｄ＾３＋，Ｓｍ＾３＋，Ｅｕ＾３＋，Ｇｄ＾３＋，Ｄｙ＾３＋，Ｙｂ＾３＋）的９种镧系元素Ｄａｗｓｏｎ结构的钨钒磷四元杂多配合物，并用ＩＲ、ＵＶ、ＮＭＲ、ＥＳＲ、ＸＲＤ、ＴＧ－ＤＴＡ等对其结构和性质进行子研究。该类配合物具有与Ｋ１６〔Ｃｅ（Ｐ２Ｗ１７Ｏ     

Ga^3＋的新萃取体系的界面特性和胶团化作用研究

研究了Ｇａ~（３＋）协萃体系（Ｇａ~（３＋）－Ｄ_２ＥＨＰＡ－Ｈ_２ＭＰＡ－正十二烷－Ｈ_２ＳＯ_４）的界面吸附和胶团形成热力学，发现该萃取体系中［Ｈ_２ＭＰＡ］影响Ｄ_２ＥＨＰＡ和Ｈ_２ＭＰＡ的界面吸附性质。在中、高［Ｈ_２ＭＰＡ］范围内Ｄ_２ＥＨＰＡ与Ｈ_２ＭＰＡ的界面吸附行为相反，Ｄ_２ＥＨＰＡ的存在也影响Ｈ_２ＭＰＡ的界面吸附行为。研究了界面张力与各因素关系的数学模型，并获得某些胶团形成和界面吸附特性的物化参数。     

β—型过渡元素三取代钨锗杂多配合物的合成,表征和催化活性

报道Ａ－β－Ｍ＇ｘＨｙ－［ＧｅＷＯＭ３（Ｈ２Ｏ）３Ｏ３７］．ｎＨ２Ｏ（Ｍ＝Ｃｒ＾３＾＋，Ｃｏ＾２＾＋，Ｎｉ＾２＾＋，Ｃｕ＾２＾＋；Ｍ＇＝Ｂｕ４Ｎ＾＋，Ｋ＾＋）的立体有择合成法制备及红外和远红外光谱，紫外和可见光谱和循环伏安，磁化率和磁矩，ＸＰＳ，ＥＳＲ以及催化活性等研究结果。     

硝酸镧与N,N—双（苯并三唑甲）—[2,2]及N—三唑甲基—[2,2]配合物…

合成了Ｌａ（ＮＯ３）３与Ｎ，Ｎ－双（苯半三唑甲基）－［２，］［Ｌ（Ｉ）］及Ｎ－三唑甲基－［２，２］（Ｌ（Ⅲ）的配合物单晶，测定了结构，并进行了元素分析，红外光谱及热分析表征。Ｌａ＾３＋离子均与［２，２］环中六个杂原子及三个ＮＯ＾３－离子配位，稍偏离环平面，三个ＮＯ＾３－离子分别位于环平面的两侧，初步讨论了［２，２］环所连接支链对配合的结构及其稳定性的影响。     

呋喃甲酰基吡唑啉酮双席夫碱稀土配合物的合成、表征及生物活性

合成了１１种新的稀土与Ｎ,Ｎ’－双「（１－苯基－３－甲基－５－氧－４－吡唑啉基）α－呋喃次甲基」乙二亚胺（ＨＰＭαＦＰ）２ｅｎ配合物。元素分析及摩尔电导值表明配合物的组成为「ＲＥ（ＨＰＭαＦＰ）２ｅｎ（ＮＯ３）２」ＮＯ３」ＮＯ３（ＲＥ＝Ｌａ,Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｔｂ,Ｄｙ,Ｈｏ,Ｅｒ,Ｙｂ,Ｙ）。用红外学谱、紫外学谱、磁共振谱和荧光光谱对配合物进行了表征,证实席夫碱配体以四齿形式配位,ＲＥ＾３     

镧系元素的中性络合固-液萃取分离研究(Ⅱ)--TOPO-NaClO4-石蜡体系

本文以正三辛基氧膦为萃取剂,以熔融石蜡为稀释剂,研究了ＨＣｌＯ４－ＮａＣｌＯ４介质中Ｌａ＾３＋、Ｎｄ＾３＋、Ｓｍ＾３＋、Ｄｙ＾３＋Ｙｂ＾３＋的固－－液萃取行为及萃取反应热力学性能。斜率比法给出萃合物组成为Ｌｎ（ＴＯＰＯ）２（ＯＨ）（ＣｌＯ４）２。测定了萃取反应势力学参数、平衡常数及半萃取ｐＨ值。     

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.     

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.     

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.     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.