全文获取类型
收费全文 | 1137篇 |
免费 | 30篇 |
国内免费 | 231篇 |
专业分类
化学 | 1331篇 |
晶体学 | 4篇 |
综合类 | 11篇 |
物理学 | 52篇 |
出版年
2024年 | 1篇 |
2023年 | 11篇 |
2022年 | 14篇 |
2021年 | 23篇 |
2020年 | 19篇 |
2019年 | 30篇 |
2018年 | 20篇 |
2017年 | 30篇 |
2016年 | 24篇 |
2015年 | 20篇 |
2014年 | 63篇 |
2013年 | 135篇 |
2012年 | 58篇 |
2011年 | 69篇 |
2010年 | 33篇 |
2009年 | 52篇 |
2008年 | 84篇 |
2007年 | 61篇 |
2006年 | 72篇 |
2005年 | 75篇 |
2004年 | 77篇 |
2003年 | 68篇 |
2002年 | 36篇 |
2001年 | 20篇 |
2000年 | 28篇 |
1999年 | 27篇 |
1998年 | 25篇 |
1997年 | 22篇 |
1996年 | 20篇 |
1995年 | 22篇 |
1994年 | 21篇 |
1993年 | 24篇 |
1992年 | 20篇 |
1991年 | 15篇 |
1990年 | 16篇 |
1989年 | 17篇 |
1988年 | 21篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有1398条查询结果,搜索用时 15 毫秒
991.
The development of manganese-catalyzed carbomagnesation of alkynes is reviewed. Manganese salts mediate the efficient addition of a variety of Grignard reagents to alkynes. Allyl, aryl, and alkyl Grignard reagents participate in these reactions. In many cases, a hetero atom such as oxygen or nitrogen in substrates facilitates the addition reaction. Stoichiometric carbometalation reactions with manganese ate complexes are also discussed, as is cyclization of 1,6-diynes and 1,6-enynes via carbometalation with triallylmanganate. 相似文献
992.
Anirban KarNarshinha P Argade 《Tetrahedron》2003,59(17):2991-2998
A facile new route to the potential building blocks 2-bromomethyl-3-alkylmaleic anhydrides 15a/b for the synthesis of natural and unnatural dialkylsubstituted maleic anhydrides has been demonstrated, starting from dimethyl citraconate (9) via NBS-bromination, SN2′ Grignard coupling reactions, hydrolysis, molecular bromine addition and dehydrative ring closure reactions pathway with 49-51% overall yield in 5-steps. Chemoselective allylic substitution of bromoatom in 15a/b with Grignard reagents has been described to obtain the unsymmetrical maleic anhydride 16 and symmetrically dialkylsubstituted maleic anhydrides 25a/b in 55% yield. The naturally occurring 2-carboxymethyl-3-hexylmaleic anhydride (1) has been synthesized from 16 via esterification, ozonolysis and an oxidation route. The synthesis of two naturally occurring 2-(β-carboxyethyl)-3-alkylmaleic anhydrides 2a/b have been completed via a chemoselective diethylmalonate coupling reaction followed by acid induced hydrolysis. In our hands the SN2 or SN2′ coupling of Grignard reagent with 21 to obtain 1 and Reformatsky reaction with 15a/b to obtain 2c/d met with failure. 相似文献
993.
Hydromagnesiation of alkylarylacetylenes 1 in diethyl ether gave (E)-α-arylvinyl Grignard reagents 2, which reacted with trialkylstannyl chlorides 3 in diethyl ether to afford stereoselectively (E)-1,2-disubstituted vinylstannanes 4 in high yields. 相似文献
994.
995.
用反相离子对色谱分离和检测水溶性维生素——十二烷基磺酸钠作离子对试剂 总被引:4,自引:0,他引:4
本文使用十二烷基磺酸钠(SDS)作离子对试剂,研究了用反相离子对色谱法对混合水溶性维生素的检测和分离,确定了最佳实验条件,包括SDS浓度,pH值,甲醇与水的配比,三乙胺浓度及柱温等。用本方法对九种混合水溶性维生素〔B_1,B_2,B_5(烟酰胺和烟酸),B_6(吡哆醛和吡哆醇),B_(11),B_(12)和C〕的标样和西瓜汁的分离表明,在所选定的实验条件下,可于10min内一次分离。 相似文献
996.
A facile preparation of Tebbe reagent (1) by reacting AlMe3 solution with Cp1TiCl2 is reported. After complete removal of solvent and excess of AlMe3, the crude Tebbe reagent could be used without purification to react with ketones in a Wittig-type manner. 相似文献
997.
998.
Nina M. Ivanova 《International journal of quantum chemistry》2005,101(1):90-96
The structures of coordination complexes of methylmagnesium chloride with 1‐halogen‐3‐methoxy‐1‐propynes have been studied by means of ab initio methods (RHF/3‐21G*, RHF/6‐31G* and RHF/6‐31G**), taking into account the electron correlation by Møller‐Plesset perturbation theory (MP2). Two pathways of the nucleophilic halogen substitution reaction between the reagents have been considered. The calculations predict the addition–elimination mechanism as advantageous for the reaction. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
999.
Three 3,4-dihydroxy-2,5-bis-(2′-(4′-substituted-oxazolinyl)) furans were synthesized at 90%–94% yields from reaction of 3,4-dihydroxyfuran-2,5-dicar-boxylic
acid or its dimethyl ester with chiral β-amino alcohol via a one-step process. Their chemical structures were determined by 1H NMR, IR, MS, and elemental analysis. With these chiral bisoxazoline ligands, the asymmetric reductive reaction of β-acetonaphthalene
with KBH4 or NaBH4 was preliminarily studied. The enantiomeric excess of the reduction product was up to 83.2% with cyclohexane as the solvent,
the molar ratio of ligand: reductive agent: β-acetonaphthalene is 0.04:1.6:1, and 72-hours reaction time at 0°C. Furancontaining
bisoxazoline with 4-benzyl on oxazoline rings exhibited higher enatioselectivity than congeneric bisoxazolines with 4-ethyl
on oxazoline rings.
__________
Translated from Chinese Journal of Applied Chemistry, 2005, 22(12) (in Chinese) 相似文献
1000.