3-亚甲基异吲哚酮的合成新方法

亚甲基异吲哚酮衍生物2是一类重要的药物合成中间体, 近来又被用作新型有机金属染料合成的配体。文献报道化合物2的主要合成方法是采用苯基锂衍生物的分子内反应, 或以有机钛为主要原料合成目标产物, 但以上方法原料难得, 反应条件苛刻, 产率不理想, 难以大规模合成。我们首次发现以苯基环缩醛为原料一步法合成亚甲基异吲哚酮2的新方法, 原料易得, 条件温和, 操作简便, 产率良好, 为苯甲醛作起始原料合成化合物2提供了一条新途径。     

3-亚甲基异吲哚酮的合成新方法(英文)

亚甲基异吲哚酮衍生物2是一类重要的药物合成中间体,近来又被用作新型有机金属染料合成的配体。文献报道化合物2的主要合成方法是采用苯基锂衍生物的分子内反应,或以有机钛为主要原料合成目标产物,但以上方法原料难得,反应条件苛刻,产率不理想,难以大规模合成。我们首次发现以苯基环缩醛为原料一步法合成亚甲基异吲哚酮2的新方法,原料易得,条件温和,操作简便,产率良好,为本甲醛作起始原料合成化合物2提供了一条新途径。     

三芳基咪唑类化合物的合成及其双光子吸收性能研究

双光子吸收是指物质分子或原子在强激光激发下同时吸收两个光子,从基态跃迁到两倍光子能量激发态的过程。目前,双光子吸收材料已广泛地应用到双光子激发显微[1]、频率上转换激射[2-3]、光学限幅、三维光信息存储[4]以及光生物学等领域。但在已报道的双光子诱导上转换荧光的有机     

Cu（Ⅱ）—Mn（Ⅱ）—Cu（Ⅱ）异三核配合物合成与磁性研究

分子磁体化合物的设计合成是近年来迅速发展的一个新兴前沿领域[1 ,2 ] ,它涉及化学、物理、材料等诸多领域 ,多核配合物体系是分子磁体化合物中研究最为广泛和深入的一类体系。在多核金属配合物中 ,异多核体系的分子磁性研究尤为引人注目。有关草胺酸类、草酰胺类、草酸根类、二肟类和氰根类多原子桥异多核配合物分子磁体的设计合成已有综述报道[3] 。硫氰酸根可以将多个顺磁性金属离子桥联成一维、二维或三维分子 ,但有关硫氰酸根桥异多核配合物磁性研究的报道比较少[4,5] ,本文报道二个硫氰酸根桥联异三核配合物的合成与磁性研究。1　实…     

新型三维H0.5CoP0.5O2.5的水热合成与结构表征

分子筛在催化、吸附和离子交换等方面具有广泛的应用 ,一直是重要的工业材料 .自 1 982年Wilsion首次合成磷酸铝以来 [1] ,人们发现磷酸盐具有类似于分子筛的结构特征 [2～ 4 ] ,随着研究的不断深入 ,近来具有空旷结构的磷酸盐分子筛由于在催化、光学、磁学等领域具有潜在的应用前景日益受到人们的关注 .具有微孔结构的过渡金属磷酸盐因可作为分子反应器而使许多新的过渡金属磷酸盐被合成出来[5～ 9] .文献 [1 0 ,1 1 ]报道 Co PO4 具有层状、多孔、高聚合度的结构 ,这些分子多数经过有机模板剂或其它分子的修饰 ,形成混合配体的配合物 .…     

手性高效液相色谱拆分3-取代异吲哚-1-酮的研究

从伏牛花类植物中提取的生物碱Lennoxam ine^[1]、Nuevam ine和Chilenine,新研发的抗焦虑药Paz-inaclone^[2]和Pagoclone^[3]以及利尿、抗高血压药Chlortalidone^[4]等均含有光活性3-取代异吲哚-1-酮(2,3-二氢-1H -异吲哚-1-酮).这类化合物还是一类新型的不对称合成手性辅助基^[5].因此,光学纯的3-取代异吲哚-1-酮化合物在药物研发和不对称合成等领域具有应用前景.但有关它们的色谱拆分少见报道^[6,7].本文对15个外消旋3-取代异吲哚-1-酮样品进行高效液相色谱拆分研究,通过建立的手性色谱方法,不仅准确测定了相关产物的光学纯度,而且确认了N -取代邻苯二甲酰亚胺上手性辅助基在不对称合成过程^[8]中未发生消旋化.同时探讨了样品中3-位取代基对手性拆分的影响.     

芳环取代的俘精酸酐的合成及光致变色反应研究

本文报道四个芳环取代的俘精酸酐:2-亚异丙基-3-[1-(4-甲氧苯基)-亚乙基]-丁二酸酐(BF1);2-亚异丁基-3-1[1-(4-甲氧苯基)-亚乙基]-丁二酸酐(BF2);2-亚异丙基-3-[1-(α-萘基)-亚乙基]-丁二酸酐(NF1);2-亚异丙基-3-[1-(β-萘基)-亚乙基]-丁二酸酐(NF2)的合成及其光致变色性质.测定了它们在不同溶剂中光致变色前后的吸收光谱.利用纳秒级激光闪光光解技术研究了它们的光致变色过程,并讨论了其光致变色机理.结果表明,这类芳环取代的俘精酸酐的光致环合反应是经过激发单重态进行的快速过程.     

超分子化合物｛[8-hydroxyquinolineH]_4~(4+)·[SiW_(12)O_(40)]~(4-)·2H_2O｝的水热合成、晶体结构及热稳定性

近些年来,合成和研究开发新型结构的有机鄄无机配合功能性材料日益成为人们关注的热点[1￣3]。金属杂多酸盐以其独特的分子结构及理化性质,已经成为构造新型分子功能材料的重要无机构筑块,作为电子受体的金属杂多酸盐可以与有机π电子给体如TTF、ET和有机金属茂合物结合,形成有机鄄无机复合物。该类化合物在光、电、磁、催化和超导领域有潜在的应用前景[4￣6],它们的结构不同,性质各异,其中一些具有超分子结构[7]。本研究通过水热合成法,合成了一种未见报道的Keggin结构硅钨酸盐超分子化合物｛[8鄄hydroxyquinolineH]44·+[SiW12O40]4·…     

共轭多烯异核双金属配合物的合成及性质

分子电子器件是近年来的一个热门课题,共轭有机分子是形成分子导线、分子开关等分子电子器件的模型化合物之一,其中一些已经得到应用.过去几年中,以sp碳为骨架的共轭桥联双金属配合物备受关注,长度为20个碳原子的此类双金属配合物已合成,大多数此类配合物金属端基之间有电子相互作用,具有良好的光电性质.由于合成的困难,以sp2碳为骨架的共轭多烯双金属配合物,近年来才有报道[1,2],且都是同核双金属配合物.共轭多烯异核双金属配合物的报道很少,由于分子的不对称,它们具有非线性光学性质.本文选用一取代二茂铁的三苯基磷盐与醛发生Wittig反应,生成的多烯单炔金属配合物与金属氢化物RuHCl(CO)(PPh3)3发生插入反应,合成了一系列长度为6个碳的稳定的共轭多烯异核双金属配合物(Scheme 1).     

钒氧酞菁的合成及其薄膜结构与光电性能的研究

自从60年前^[1]金属酞菁被发现以来,就引起人们的广泛兴趣,其原因主要在于它们在染料颜料、光化学、催化、和成像中的应用. 和许多其它酞菁衍生物一样,钒氧酞菁具有光导和半导体特性,这使得它在光电子学、电子成像、化学传感器、甚至于微电子器件中有潜在的十分光明的应用前景^[2]. 例如, 钒氧酞菁在电子成像体系中已成为有用的感光材料. 近年来,金属酞菁等有机材料的结晶薄膜开始不断地吸引人们的注意力. 人们考察了不同的金属酞菁如: 酞菁铜、酞菁铅、酞菁镍、和酞菁锡 等的光电导和光电压^[3]. 通常酞菁以几种不同的多晶异构体、即以不同的晶体排列结构方式存在. 因此,其光电特性不仅取决于分子中心的金属原子、而且取决于它们的晶体结构. 总之,值得我们研究钒氧酞菁薄膜的光电特性以及它与吸收光谱和薄膜晶体结构的关系.     

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.     

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.     

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.     

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%).     

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.     

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.