生色冠醚研究：Ⅵ.荧光性Schiff碱型苯并冠醚的合成和性质

用４－甲基－７－羟基－８－甲酰基香豆素与三种４’－氨基苯并冠醚和４’，４”－二氨基二苯并－１８－冠－６反应，合成了四个新的Ｓｃｈｉｆｆ碱型苯并冠醚，它们都是有色化合物，具有强荧光性质，在这些Ｓｃｈｉｆｆ碱型苯并冠醚溶液中加入过渡金属盐时，不同程度地发生荧光猝灭现象，生成的配合也是荧光化合物，而加入碱金属和碱土金属盐时，则荧光性质几乎不受影响。     

生色冠醚研究

用４－甲基－７－羟基－８－甲酰基香豆素与三种４′－氨基苯并冠醚和４′，４″－二氨基二苯并－１８－冠－６反应，合成了四个新的Ｓｃｈｉｆ碱型苯并冠醚。它们都是有色化合物，具有强荧光性质。在这些Ｓｃｈｉｆ碱型苯并冠醚溶液中加入过渡金属盐时，不同程度地发生荧光猝灭现象，生成的配合物也是荧光化合物；而加入碱金属和碱土金属盐时，则荧光性质几乎不受影响     

冠醚增敏稀土配合物荧光增强效应的研究及其应用

本文详细研究了二苯并－１８冠－６对Ｓｍ－ＴＴＡ荧光体系的增敏作用和稀土离子Ｄｙ＾３＋对Ｓｍ－ＴＴＡ－冠醚体系的荧光增强效应，在冠醚存在下，Ｓｍ－ＴＴＡ二元配合物荧光体系的荧光强度增加了２８０倍，Ｓｍ－ＴＴＡ－二苯并－１８－冠－６体系中引入适量的Ｄｙ＾３＋后，使体系的荧光强度提高２６倍，对Ｓｍ－ＴＴＡ－冠醚和Ｓｍ－Ｄｙ－ＴＴＡ－冠醚体系，Ｓｍ的浓度分别在２．０×１０＾－７～１．０×１０＾－５ｍｏｌ／     

1,4—双（取代苯乙炔基）苯及反,反—1,4—双（β—取代苯乙…

测定了１，４－双（取代苯乙炔基）苯（Ⅰ）和反，反－１，４－双（β－取代苯乙烯基）苯（Ⅱ）的紫外光谱、荧光光谱。用ＣＮＤＯ／Ｓ－ＣＩ和ＨＭＯ方法对苯乙炔、二苯乙炔和（Ⅰ）及苯乙烯、１，２－二苯乙烯和（Ⅱ）的激发能进行了计算和研究。讨论了化合物结构对光谱的影响。     

2－（4－联苯基）苯并噁唑衍生物的合成及其光学性能

合成了７种２－（４－联苯基）苯并　唑衍生物，其中５种为未知物．经元素分析、ＩＲ、ＵＶ、１ＨＮＭＲ和ＭＳ表征，并测定了上述化合物的荧光发射光谱、荧光量子产率和激光转换效率，结果发现５，７－二异丙基－２－（４－联苯基）苯并　唑的激光转换效率高，具有应用价值．     

6,7—取代—1H—苯并（de）异喹啉—1,3（2H）二酮的合成

从二氢苊出发合成了６－溴－７－氨基２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮，６－甲氧基－７－氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮和６，７－二氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮，测定了它们的荧光量子产率，讨论了分子内重原子溴和给电子基对化合物荧光性质的影响。     

吖啶类衍生物的荧光性质

用比较法测得23种啶类衍生物的荧光量子效率（Φf)，以评估这些化合物的荧光性质，结果表明，N－烃基吖啶酮类化合物的荧光量子效率要比9－取代苯基吖啶类和9－取代苯亚甲基－10－甲基－9，10－二氢吖啶类化合物的荧光量子效率大，在非极性溶剂中，9－聚代苯亚甲基－9，10二氢吖啶分子内的强吸电子基NO2增强荧光量子效率，强推电子基OCH3降低荧光量子效率，这些测量结果与取代基的电子作用经验规律不相符，这种现象可以用分子内电荷转移理论进行解释。     

新荧光试剂3—对甲苯基—5—（2‘—羧基苯偶氮）绕丹宁的合成及荧光光度…

本文报道了新荧光试剂３－对甲苯基－５－（２＇－羧基苯偶氮）绕丹宁的合成。用元素分析、红外光谱、核磁共振氢谱和质谱确证了其结构，研究了其荧光性质。在ＰＨ５．６时，该试剂与Ｃｕ＾２＋形成稳定的荧光螯合物，且在λｅｘ／λｅｍ＝３０５ｎｍ／４０５ｎｍ产生强烈荧光。     

5—（4—甲氧基苯偶氮）—8—（苯磺酰氨基）喹啉的合成及其与钴荧光反应的研究

本文报告了５－（４－甲氧基苯偶氮）－８－（苯磺酰氨基）喹啉（ＭＯＰＢＳＱ）的合成及结构鉴定，建立了ＭＯＰＢＳＱ－吐温８０测钴的新荧光分析方法。方法的检测限为０．５ｎｇ／ｍＬ，线性范围为０～４０μｇ／Ｌ螯合物在λｅｘ／λｅｍ＝３４１ｎｍ／４０５ｎｍ和产生经烈荧光。不经分离可直接用于维生素Ｂ１２及蔬菜中痕量钴的测定。     

杂多核配位荧光增敏法测定痕量铍

研究了新荧光试剂２－「５－羧基－２－胂酸基苯偶氮」－１,８－二羟基－３,６－萘二碘酸与铍络合的荧光性能。铍与试剂形成荧光络全物,在硼砂介质啼生增敏效应,据此建立了测定痕量铍的新方法。Ｂｅ（Ⅱ）浓度在０－０．１２ｍｇ／Ｌ范围内一荧光哟度呈良好线性关系,方法检测限为０．０７６μｇ／ＬＢｅ（Ⅱ）,用于水及铜基合金样中的痕量铍的测定,结果满意。     

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.     

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.     

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.     

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.     

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.     

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.     

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.