全文获取类型
收费全文 | 580篇 |
免费 | 26篇 |
专业分类
化学 | 490篇 |
晶体学 | 1篇 |
力学 | 12篇 |
数学 | 32篇 |
物理学 | 71篇 |
出版年
2023年 | 2篇 |
2022年 | 9篇 |
2021年 | 10篇 |
2020年 | 12篇 |
2019年 | 9篇 |
2018年 | 5篇 |
2017年 | 9篇 |
2016年 | 14篇 |
2015年 | 15篇 |
2014年 | 17篇 |
2013年 | 28篇 |
2012年 | 47篇 |
2011年 | 45篇 |
2010年 | 32篇 |
2009年 | 15篇 |
2008年 | 30篇 |
2007年 | 32篇 |
2006年 | 25篇 |
2005年 | 24篇 |
2004年 | 28篇 |
2003年 | 25篇 |
2002年 | 17篇 |
2001年 | 8篇 |
2000年 | 11篇 |
1999年 | 9篇 |
1998年 | 5篇 |
1997年 | 5篇 |
1996年 | 20篇 |
1995年 | 7篇 |
1994年 | 8篇 |
1993年 | 9篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 12篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 8篇 |
1986年 | 11篇 |
1985年 | 3篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1961年 | 1篇 |
1959年 | 1篇 |
1891年 | 1篇 |
1882年 | 1篇 |
排序方式: 共有606条查询结果,搜索用时 31 毫秒
1.
2.
Uwe Bhme Ines C. Foehn 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):o613-o616
TBPY‐5‐34‐(Butane‐1,4‐diyl)(2‐{[1‐(2‐oxidophenyl)ethylidene‐κO]amino‐κN}ethanolato‐κO)silicon, C14H19NO2Si, crystallizes in two modifications. The monoclinic form, (IIm), was obtained by crystallization over a period of 2 d at room temperature; the orthorhombic form, (IIo), crystallized overnight at 248 K. The main difference between the two molecular structures involves the angles in the equatorial plane of the trigonal bipyramid around silicon. Form (IIm) has an O—Si—O angle of ca 121° and O—Si—C angles of ca 121 and 116°. In form (IIo), the corresponding angles are ∼123, 124 and 111°. There are also significant differences in the packing: (IIm) shows π stacking, whereas (IIo) does not. 相似文献
3.
4.
5.
Alessandro D' Aprano Dorina Ines Donato Antonio Carrubba Doctor in Chemistry thesis of A. Carrubba 《Journal of solution chemistry》1983,12(3):209-220
Conductance measurements are reported for LiPi, NaPi, KPi, RbPi, CsPi, Bu4NPi, Bu4NBr, Bu4NClO4, Bu4NNO3, and Bu4NBBu4 at 25°C in -butyrolactone-sulfolane mixtures. In these mixtures of solvents that are practically homomorphous, isodielectic and with comparable dipole moments, the ion pair association and ionic mobilities of large ions conform to the expectations of the primitive model. Electrolytes containing lithium or sodium ions show anomalies indicating that other factors besides shape, dipole moment, and polarizability of the solvent molecules are involved in the association and transport processes of these ions. 相似文献
6.
7.
Treatment of the bis(allylsulfoximine)titanium complexes derived from the beta-methyl-substituted acyclic allylic sulfoximines 13a and 13b with aldehydes gave with high selectivities the corresponding sulfoximine-substituted homoallylic alcohols which were isolated as the silyl ethers 15a-h. Methylation of sulfoximines 15a-h afforded the aminosulfoxonium salts 5a-h which upon treatment with LiN(H)tBu gave in high yields the enantio- and diastereomerically pure silyl-substituted 2,3-dihydrofurans 4a-h. Treatment of the titanium complexes derived from the cyclic allylic sulfoximines 17a, 17b, and ent-17c with p-MeOC(6)H(4)CHO delivered with high selectivities the corresponding sulfoximine-substituted cyclic homoallylic alcohols which were isolated as the silyl ethers 18a, 18b, and ent-18c, respectively. Methylation of sulfoximines 18a, 18b, and ent-18c furnished the aminosulfoxonium salts 8a, 8b, and ent-8c, respectively, whose treatment with LiN(H)t-Bu gave the enantio- and diastereomerically pure fused bicyclic 2,3-dihydrofurans 6a, 6b, and ent-6c, respectively, in good yields. It is proposed that the 1-alkenyl aminosulfoxonium salts 5a-h, 8a, 8b, and ent-8c react with the base under alpha-elimination and formation of the acyclic and cyclic beta-silyloxy alkylidene carbenes 2a-h, 7a, 7b, and ent-7c, respectively, which then undergo a 1,5-O,Si-bond insertion and 1,2-silyl migration. The cyclic aminosulfoxonium salts 8a, 8b, and ent-8c upon treatment with 1,8-diazabicyclo[5.4.0]-7-undecene did not undergo an alpha-elimination but suffered a novel migratory cyclization with formation of the enantio- and diastereomerically pure bicyclic tetrahydrofurans 9a, 9b, and ent-9c, respectively. It is proposed that the 1-alkenyl sulfoxonium salts 8a, 8b, and ent-8c are isomerized to the allylic aminosulfoxonium salts 10a, 10b, and ent-10c, respectively, which then suffer an intramolecular substitution of the (dimethylamino)sulfoxonium group by the silyloxy group followed by a desilylation. The syntheses of the 2,3-dihydrofurans 4a-h, 6a, and 6b and of the tetrahydrofurans 9a and 9b are accompanied by the formation of sulfinamide 16 of >or=98% ee, which can be converted via sulfoxide 28 of >or=98% to the starting sulfoximine 11 of >or=98% ee. 相似文献
8.
Bolm C Verrucci M Simic O Cozzi PG Raabe G Okamura H 《Chemical communications (Cambridge, England)》2003,(22):2826-2827
Quinoline-based C1-symmetric sulfoximines have been used as chiral ligands in copper-catalyzed asymmetric hetero Diels-Alder reactions leading to cycloadducts with up to 96% ee. 相似文献
9.
Hans‐Jürgen Holdt Holger Müller Alexandra Kelling Hans‐Joachim Drexler Thomas Müller Thomas Schwarze Uwe Schilde Ines Starke 《无机化学与普通化学杂志》2006,632(1):114-122
Mercury(II) Chloride and Iodide Complexes of Dithia‐ and Tetrathiacrown Ethers The complexes [(HgCl2)2((ch)230S4O6)] ( 1 ), [HgCl2(mn21S2O5)] ( 2 ), [HgCl2(ch18S2O4)] ( 3 ) and [HgI(meb12S2O2)]2[Hg2I6] ( 4 ) have been synthesized, characterized and their crystal structures were determined. In [(HgCl2)2((ch)230S4O6)] two HgCl2 units are discretely bonded within the ligand cavity of the 30‐membered dichinoxaline‐tetrathia‐30‐crown‐10 ((ch)230S4O6) forming a binuclear complex. HgCl2 forms 1 : 1 “in‐cavity” complexes with the 21‐membered maleonitrile‐dithia‐21‐crown‐7 (mn21S2O5) ligand and the 18‐membered chinoxaline‐dithia‐18‐crown‐6 (ch18S2O4) ligand, respectively. The 12‐membered 4‐methyl‐benzo‐dithia‐12‐crown‐4 (meb12S2O2) ligand gave with two equivalents HgI2 the compound [HgI(meb12S2O2)]2[Hg2I6]. In the cation [HgI(meb12S2O2)]+ meb12S2O2 forms with the cation HgI+ a half‐sandwich complex. 相似文献
10.
Reaction of 2,3,7,8,12,13,17,18-octaethylporphyrin with LiR reagents containing functional groups readily yields meso substituted derivatives suitable for further transformations with residues such as -p-C6H5Br, -p-C6H5-CCH, -p-C6H5-NH2 or -(CH2)3-CHCH2. Similar reactions of tetrabenzoporphyrin with alkyllithium reagents afforded the first entry into meso mono- and dialkylsubstituted tetrabenzoporphyrins while reaction of bicyclo[2.2.2]oct-type masked isoindole precursors with LiR followed by in situ retro-Diels-Alder reaction also afforded the 5-phenyl and 5,10-diphenyltetrabenzoporphyrins in high purity. 相似文献