水杨醛苯腙与铜荧光反应的研究及其应用

水杨醛苯腙与铜荧光反应的研究及其应用江崇球，唐波，傅红燕，曹红，张晓刚（山东师范大学化学系，济南，２５００１４）关键词铜，水杨醛苯腙，荧光分析胺类试剂是一类理想的荧光分析试剂［１］，用其测定Ａｌ３＋［２］、Ｇａ３＋［３］、Ｚｎ２＋［４］已显示出其灵敏...     

二氧化硅-聚硅氧烷负载富勒烯铂配合物的合成及其催化硅氢化性能

富勒烯及其衍生物的催化性能的研究是当前的一个热点,并显示出良好的工业应用前景［１］．研究表明,富勒烯及其衍生物的金属配合物对氢化［２,３］,不对称偶联［４］,烯烃的聚合［５］等都有优异的催化性能．我们也发现Ｃ６０Ｐｔ（ＰＰｈ３）２和Ｃ６０Ｐｔｎ是高效...     

芳香硝基物CO选择还原—环境友好芳胺合成新路线

含有羰基、氯、氰基和双键的芳胺类化合物是染料、颜料、医药和农药等领域的重要中间体［1］.然而,它们难以从相应的芳香硝基物与金属氢化物试剂的催化加氢直接制得,因为在这些还原条件下,羰基、氯、氰基和双键也能发生还原反应［2］ .目前,工业上通常还只能用经典的铁粉还原法或硫化碱还原法生产这些芳胺衍生物,但用铁粉还原法,产生的大量铁泥严重污染环境;硫化碱还原法,则存在合成路线复杂、成本高、收率低和废液量大等不足之处［3］ .近年来,一种以CO为还原剂还原芳香硝基物的反应,以其对硝基的高选择性而日益引起人们的兴趣,因而有望成为合成含有羰基、氯和氰基的芳香胺类衍生物的一条环境友好新途径［4］.     

Co(Ⅱ)、Mn(Ⅱ)Schiff碱配合物的合成及其对超氧离子的抑制作用

Ｓｃｈｉｆｆ碱及其金属配合物具有抗菌、抗癌等生物活性［１］,尤其是钴（Ⅱ）Ｓｃｈｉｆｆ碱配合物具有催化及可逆载氧等特殊性能［２］,引起人们极大的研究兴趣。本文合成了四种新型的未见文献报道的Ｃｏ（Ⅱ）、Ｍｎ（Ⅱ）Ｓｃｈｉｆｆ碱配合物。研究表明这类配合物结构稳定、生物活性高,可作超氧化物歧化酶的模拟物,对超氧离子Ｏ２-自由基有良好的催化歧化作用。１实验部分１１配体（５氯水杨醛缩盐酸氨基脲ＨＬ）的合成将等摩尔的自制５氯水杨醛［３］（３１３ｇ）的乙醇液滴加于盐酸氨基脲（２２３ｇ）的中性水溶液中,在８６℃的恒…     

氯化钇与水杨醛类杂环息夫碱配合物的合成与表征

由水杨醛制得的息夫碱及其配合物具有显著的抗癌活性［１］。近年来,过渡金属离子与此类配合物的研究已有文献报道［２］。为了研究钇与此类息夫碱的配位能力,我们在无水乙醇体系中合成了氯化钇与水杨醛类杂环息夫碱的三种新的固体配合物,并对其组成和配位方式进行了研...     

N-二茂铁甲酰基-芳基羟胺及其铜(Ⅱ)螯合物的合成与表征

二茂铁甲酰羟胺衍生物分子中含有N-羟基和α-羰基,可与过渡金属形成螯合物.我们试图将该类螯合物用作复合固体推进剂的燃速调节剂,为此,研究了该类化合物的合成方法及其性质,并使它们与铜(Ⅱ)螯合制成铜螯合物.     

脱氯化氢法合成聚(2,5-二乙氧基对苯乙炔)

聚对苯乙炔（ＰＰＶ）及其衍生物具有独特的光电性能，经强氧化剂掺杂后是一类重要的导电材料［１］，而且具有良好的非线性光学（ＮＬＯ）性质［２］，也是目前为止性能最好的电致发光材料［３］，因而ＰＰＶ及其衍生物的合成成为电致发光领域研究的热点之一。目前国内外...     

二苄基一氯化锡二硫代氨基甲酸酯的合成

二烃基氯化锡及其衍生物具有较强的抗癌活性，日益受到人们的重视。关于含有Ｓｎ—Ｏ键的二烃基锡衍生物的合成研究已有大量报道［１］。但含Ｓｎ—Ｓ键二烃基锡衍生物的合成研究则较少［２］，而二烃基一氯化锡二硫代氨基甲酸酯的合成研究尚未见报道。为了寻找具有抗癌活...     

双穴二氧四胺Cu(Ⅱ)和Ni(Ⅱ)配合物的合成和性质

本文合成了二种新配体，Ｎ，Ｎ＇－双［水杨醛缩（２－氨乙基）］乙二酰胺（ｄｓａｅ）和Ｎ，Ｎ＇－双［水杨醛缩（２－氨乙基）］丙二酰胺（ｄｓａｐ）及其Ｃｕ、Ｎｉ的配合物，并用元素分析、红外、摩尔电导、磁化率表征，测定了ＣｕＨ－２ｄｓａｐ配合物的稳定常数，结果表明Ｃｕ、Ｎｉ与ｄｓａｅ生成双核配合物，Ｃｕ与ｄｓａｐ生成单核配合物，并对其原因进行了讨论。     

棉杆纤维素的改性(Ⅲ)——多乙撑多胺纤维素醚的制备及其吸附性能

化学改性制备纤维素衍生物对金属离子的富集分离［１～３］,膜分离［４,５］等方面的研究已有不少报道．我们近期研究［６,７］表明,由农业废弃物棉杆纤维制得的含氮纤维素醚衍生物对有毒的金属离子,尤其是对Ｈｇ２＋、Ｃｄ２＋、Ｃｒ３＋、Ｐｂ２＋离子有较好的吸附...     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.