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41.
Recent advances in organocatalytic asymmetric synthesis of polysubstituted pyrrolidines 总被引:1,自引:0,他引:1
Chiral substituted pyrrolidines are important N-heterocyclic structural motifs, existing in many natural products, drug candidates, ligands and organocatalysts. We summarise herein the recent (between January 2010 and July 2013) developments on synthesising the chiral polysubstituted pyrrolidines through asymmetric organocatalysis. The organocatalytic strategies for constructing the pyrrolidine scaffolds can be divided into one-step and sequential approaches, respectively. The straightforward one-step approach is mainly the [3+2] cycloaddition based on the iminium activation, chiral Brønsted acid catalysis, bifunctional organocatalysis and SOMO activation. In the sequential approach (multi-step or one-pot reactions), the primary construction of chiral linear precursors is followed by the sequential cyclisation. Other important strategies, such as the organocatalytic bromoaminocyclisation were also described. These organocatalytic strategies have enriched the synthetic chemistry of chiral pyrrolidines, especially towards the target-, diversity- and application-oriented synthesis. New organocatalytic approaches are thus expected for the facile construction of polysubstituted pyrrolidines with well-controlled stereochemistry and for the practical synthesis of pyrrolidine-related natural alkaloids, drug candidates and functional proline derivatives. 相似文献
42.
Keng Yoon Yeong Mohamed Ashraf Ali Chee Wei Ang Soo Choon Tan Hasnah Osman 《Tetrahedron letters》2014
A facile method to synthesize various 1,2-disubstituted benzimidazoles is developed. It is suggested that formation of a Meisenheimer adduct between the substrate, amine, and solvent aids the N-arylation process. The generality of the protocol is demonstrated by the efficient reactions involving numerous substituents ranging from electron-withdrawing groups to electron-donating groups. 相似文献
43.
《Tetrahedron letters》2014,55(51):7039-7042
N-Methyl-2-phenylimidazole (Ph-NMI) and 2-phenylimidazo[2,1-b]benzothiazoles (Ph-IBT) catalyzed selective acylation of primary alcohols using acid anhydrides. The Ph-NMI- or Ph-IBT-catalyzed reaction using (PhCO)2O as an acylating agent could particularly acylate the primary hydroxy group of 1,n-diols (n ⩾ 3) with a high, synthetically useful selectivity. 相似文献
44.
A mild,effective,and selective procedure is reported for the mono N-benzylation and N,N-dibenzylation of primary amines as well as mono N-benzylation of secondary amines using silicasupported copper(I) oxide in water.The silica-supported Cu2O was generated in situ by the reaction of Fehling solution and glucose at 100 °C onto activated silica.The catalyst was filtered,washed with water,and oven-dried,and was characterized by Fourier transform infrared spectroscopy,thermogravimetric analysis,scanning electron microscopy,transmission electron microscopy,and atomic absorption spectroscopy.The prepared Cu2O-SiO2 was found to be thermally stable up to 325 °C.The copper was uniformly distributed onto the surface of the silica,and the mean particle diameter was 7 nm.The catalyst served as a selective heterogenous catalyst for the N-benzylation of primary and secondary amines.The catalyst is recyclable and was used effectively upto fifth run without a significant loss of catalytic activity.Various reaction solvents including water,acetonitrile,and toluene were screened for N-benzylation of amines,and the success of the aqueous system highlights the low environmental impact of the procedure. 相似文献
45.
Siphamandla B. Simelane Monisola I. Ikhile Xavier Y. Mbianda 《Phosphorus, sulfur, and silicon and the related elements》2020,195(7):556-561
AbstractA series of 2-substituted vinylidene-1,1-bisphosphonate esters and their acids were synthesized and tested in vitro for activity against Plasmodium falciparum and Trypanosoma brucei. For each compound, % parasite viability in treated wells was calculated relative to untreated controls for both P. falciparum and T. brucei. Fifty percentage inhibitory concentration (IC50) was also determined for the compounds. Chloroquine and pentamidine were used as positive control drug standards for activity against P. falciparum and T. brucei, respectively. The esters had better antiparasitic activity compared to their corresponding acids. Some of the compounds reduced % parasite viability to as low as 24.3% for P. falciparum and down to 0.602% for T. brucei. Tetraethyl-2-(o-tolyl)-ethene-1,1-bisphosphonate (3b) recorded the best IC50 against T. brucei which was 0.0345?µmol/mL. 相似文献
46.
Two acetylene polymers containing cyanobiphenyl-based mesogens,poly { 10-[ ((4'- cyano-4-biphenylyl ) oxy ) carbonyl] - 1 -decyne } (PA8CN ), which has a relativelyfiexible polyalkyne backbone, and poly {[4-(((12-((4'-cyano-4-biphenylyl)oxy)dodecyl)oxy)carbonyl) phenyl]-acetylene} (PB12CN), which has a fairly rigid poly (phenylacetylene )backbone, were synthesized using respectively WCl_6 and [Rh(nbd)Cl]_2 as the catalysts.PA8CN exhibits enantiotropic interdigitated smectic A phase (S_(Ad)) over a temperaturerange as wide as ca. 100℃, whereas PB12CN is non-mesomorphic, demonstrating thatthe backbone rigidity plays an important role in determining the liquid crystallinity of thepolyacetylenes. 相似文献
47.
以1,2-二苯基菲并咪唑(PPI)为模型化合物, 通过改变N1苯环上取代基结构制备了2类PPI衍生物, 并采用核磁共振谱对其化学结构进行了确认. 通过对PPI及其衍生物的单分子荧光光谱精细结构的分析, 比较了取代基位置和结构的变化对菲并咪唑类化合物荧光过程中发射主峰精细振动结构及所占比例的影响. 其中, N1链接苯环中R4位的取代基效应最显著, 当引入推电子或弱的吸电子取代基时, 菲并咪唑类衍生物的低能级发射比例降低, 荧光色纯度提高; 当引入强吸电子取代基时, 低能级发射比例增加, 光谱半峰宽加大. 本文结果为菲并咪唑基“蓝光”材料的设计提供了一定数据的支持与科学依据. 相似文献
48.
通过2-甲基苯并噁唑或2-甲基-5-叔丁基苯并噁唑在KOH/DMF介质中与苯甲醛或取代苯甲醛反应,合成了22个标题化合物,其中13个未见报道。测定了它们的结构和紫外光谱、荧光光谱、荧光量子产率,并对母体化合物的溶剂效应进行了研究。 相似文献
49.
A substituted polyacetylene bearing a furan ring, poly(2-propynyl 2-furoate) (PPF), was synthesized for the first time with palladium acetylide complex catalysts in CHCl3 at 60℃ to give a soluble and stable polymer with a yield of ca.75%. Some features for polymerization of 2-propynyl 2-furoate are described and discussed. The resulting polymer was characterized by IR, GPC and ^1H-NMR analysis. 相似文献
50.
以单硅酯 (2-(环戊基-1,3-二烯基) 乙基) 三乙氧基硅烷 (TEECp) 和含有亚乙基桥键的硅酯 1,2-二 (三乙氧基硅基) 乙烷为硅源, 以三嵌段共聚物 P123 为模板剂, 通过调节 TEECp 预水解时间, 采用共聚法合成了环戊二烯掺杂乙烷桥联材料 (Cp-PMO), 并采用小角 X 射线衍射、N2 物理吸附、透射电镜、红外光谱和热重等技术对样品进行了表征. 结果表明, 环戊二烯基被成功引入到乙烷桥联材料中, 所得 Cp-PMO 样品具有高度有序的二维六方介孔孔道, 热稳定性较高; 随着材料中环戊二烯含量的增加, 其有序性降低, 孔径、比表面积和孔体积均有所减小, 孔壁逐渐增厚. 在乙酸乙酯与正丁醇的酯交换反应中, Cp-PMO 样品表现出较高的催化活性. 当该样品中环戊二烯含量为 30% 时, 乙酸乙酯转化率和乙酸丁酯收率分别可达 19.3% 和 10.6%. 相似文献