首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   342篇
  免费   37篇
  国内免费   8篇
化学   384篇
晶体学   2篇
物理学   1篇
  2023年   6篇
  2022年   6篇
  2021年   7篇
  2020年   11篇
  2019年   12篇
  2018年   9篇
  2017年   10篇
  2016年   8篇
  2015年   14篇
  2014年   19篇
  2013年   58篇
  2012年   8篇
  2011年   16篇
  2010年   10篇
  2009年   8篇
  2008年   21篇
  2007年   17篇
  2006年   14篇
  2005年   14篇
  2004年   7篇
  2003年   21篇
  2002年   45篇
  2001年   13篇
  2000年   5篇
  1999年   4篇
  1998年   3篇
  1997年   2篇
  1996年   2篇
  1995年   5篇
  1994年   2篇
  1993年   3篇
  1992年   2篇
  1991年   3篇
  1988年   1篇
  1982年   1篇
排序方式: 共有387条查询结果,搜索用时 15 毫秒
61.
A novel synthetic protocol of ozonolytic cleavage of 18α-oleanane triterpenoid with the five-membered α,β-alkenenitrile moiety dissolved in dichloromethane to selectively synthesize a 1,3-secotriterpene derivative with 78% yield was developed. Spontaneous condensations of the synthesized 19β,28-epoxy-1,3-seco-2-nor-18α-olean-3-al-1-oic acid followed by formation of unsubstituted 1,3- and 1,4-lactones were registered in reactions with sodium borohydride as a reducing reagent or oxalyl chloride as an activating agent, respectively. α-Methoxy- and α-ethoxy-substituted 1,3-lactones were obtained when the polar protic solvents methanol or ethanol were used for the ozonolysis of the alkenenitrile. Experiments on ozonolysis were carried out in combination with reduction with dimethyl sulfide. Ozonolysis of alkenenitrile in dichloromethane without reductive treatment was found out to have resulted in stable triterpene ozonide.  相似文献   
62.
[Zn(SO2)2][AsF6]2 (1) has been prepared from zinc metal and AsF5 in liquid sulfur dioxide, and crystallized from sulfur dioxide giving crystals of [Zn(SO2)4(AsF6)2] (1a). The compound 1 forms the homoleptic complexes [Zn(NCR)6](AsF6)2 (R: CH3 (2a), C6H5 (3a), C6F5 (3b)) with the corresponding nitriles. In these complexes, the metal center is octahedrally surrounded by six ligands (average Zn–N 2.13 ?). Reaction of 1 with the weaker ligand F3CCN results in dicoordination at the metal center complemented by a two-dimensional polymeric network (2b) containing bridging AsF6 anions. [Zn(SO2)4(AsF6)2] (1a): monoclinic, P21/c, a=8.5176(8) ?, b=13.5787(14) ?, c=14.7661(15) ?, β=99.296(2)°; [Zn(NCCH3)6][AsF6]2 (2a): rhombohedral, R-3, a=11.2225(8) ?, b=11.2225(8) ?, c=16.9393(14) ?; [Zn (NCCF3)2][μ-FAsF5)2( (2b): monoclinic, P21/c, a=11.226(3) ?, b=6.6147(19) ?, c=10.460(3) ?, β=104.028(5)°; [Zn(NCC6H5)6][AsF6]2 (3a): monoclinic, P21/n, a=13.7968(10) ?, b=19.8861(15) ?, c=16.1692(12) ?, β=91.563(2)°; [Zn(NCC6F5)6][AsF6]2·2SO2 (3b): monoclinic, P21/n, a=10.8448(9) ?, b=154456(13) ?, c=17.5206(15) ?, β=104.158(1)°.  相似文献   
63.
64.
A new one-pot neat synthesis of some 5-aryl-2,4-dihydro-3H-1,2,4-triazol-3-ones through cyclocondensation of ethyl carbazate with aryl nitriles catalyzed by DMAP as an efficient and basic nucleophilic catalyst is described.  相似文献   
65.
The synthesis, structure, and dynamic behavior of bistable C- and N-bound isomers of transition-metal cyanocarbanions are described. A series of C-bound cyclopentadienyl (Cp) ruthenium phosphane complexes, [Ru{CH(CN)SO2Ph}(Cp)L1L2] (3), and their N-bound isomers, [Ru+(Cp)(NCCH(-)SO2Ph)L1L2] (4), were prepared by treating [RuCl(Cp)(PR3)2] with the sodium salt of phenylsulfonylacetonitrile and performing ligand-exchange reactions with the resulting compounds. Structural characterization by X-ray diffraction indicates that the cyanocarbanion moiety of 3 has an alpha-metalated structure, whereas that of 4 has a zwitterionic, end-on structure. Heating these complexes in aprotic solvents gives rise to irreversible linkage isomerization between C- and N-bound isomers, in which the relative thermal stabilities vary greatly depending on the steric and electronic nature of the ligands. Mechanistic studies of N-to-C isomerization revealed that the reaction proceeds irreversibly in a unimolecular manner without the formation of coordinatively unsaturated species. A metal-sliding process, which occurs over the -C-C triple chemical bond N pi-conjugated surface of the cyanocarbanion moiety, was suggested by results from kinetic studies and density functional theory (DFT) calculations. C-to-N isomerizations proceed by the above-mentioned intramolecular process, with a temperature-dependent contribution from the formation and cleavage of mu2-C,N coordination dimers [{Ru{CH(CN)SO2Ph}(Cp)(PPh3)}2] (15 and 16).  相似文献   
66.
67.
68.
69.
70.
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号