全文获取类型
收费全文 | 162篇 |
免费 | 0篇 |
国内免费 | 17篇 |
专业分类
化学 | 177篇 |
力学 | 1篇 |
物理学 | 1篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 2篇 |
2020年 | 1篇 |
2019年 | 6篇 |
2017年 | 5篇 |
2016年 | 1篇 |
2015年 | 2篇 |
2014年 | 8篇 |
2013年 | 13篇 |
2012年 | 4篇 |
2011年 | 12篇 |
2010年 | 10篇 |
2009年 | 10篇 |
2008年 | 16篇 |
2007年 | 11篇 |
2006年 | 15篇 |
2005年 | 19篇 |
2004年 | 6篇 |
2003年 | 5篇 |
2002年 | 2篇 |
2001年 | 4篇 |
1999年 | 4篇 |
1998年 | 2篇 |
1997年 | 5篇 |
1996年 | 4篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1985年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有179条查询结果,搜索用时 0 毫秒
51.
The reaction of diphenyl diselenides with aldehydes in the presence of In-TMSCl has been investigated. Aliphatic aldehydes provide the corresponding selenoacetals, whereas aromatic aldehydes lead predominantly to alkyl phenyl selenides under the same reaction conditions. This constitutes a new approach for the synthesis of selenoacetals and selenides from aldehydes. 相似文献
52.
A combination of triphenylphosphine (PPh3) and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) provides a safe and easily available mixed reagent system for the conversion of 1° and 2° alcohols, thiols, trimethylsilyl-, and tetrahydropyranyl ethers to their corresponding thiocyanates and the 3° ones to isothiocyanates in good to high yields. 相似文献
53.
N-Trimethylsilyloxy-N-benzyl-1-alkyl-2-acetoxy-3-buten-1-amines 13, obtained in good yields and moderate diastereoselectivities by TMSOTf promoted α-acetoxyallylation of nitrones using metallic zinc and 3-bromo-propenyl acetate 11, are exploited in a stereospecific 5-exo-trig iodocyclization reaction to afford 4,5-cis-3-alkyl-4-acetoxy-5-iodomethyl isoxazolidines 14, promising starting materials for the synthesis of pyrrolidine azasugars. 相似文献
54.
Tris(trimethylsilyl)silyllithium ( 3 ) reacted with aldehydes and ketones (molar ratio 2 : 1) according to a modified Peterson mechanism under formation of transient silenes, which were immediately trapped by excess 3 to give the organolithium derivatives (Me3Si)3SiSi(SiMe3)2C(Li)R1R2 ( 7 ). Hydrolysis of 7 afforded the alkylpolysilanes (Me3Si)3SiSi(SiMe3)2CHR1R2 ( 8 ). Depending on the substituents R1 and R2, 7 proved to be rather unstable in THF solution and underwent a rapid rearrangement, involving a 1,3‐Si,C‐trimethylsilyl migration, resulting in the formation of the lithium silanides (Me3Si)2Si(Li)Si(SiMe3)2C(SiMe3)R1R2 ( 9 ), which were hydrolized during the aqueous workup to give the H‐silanes (Me3Si)2Si(H)Si(SiMe3)2C(SiMe3)R1R2 ( 10 ). Reaction of 9 with chlorotrimethylsilane produced the 1‐trimethylsilylalkylpolysilanes (Me3Si)3SiSi(SiMe3)2C(SiMe3)R1R2 ( 11 ). The structures of the products described were elucidated by comprehensive spectral analyses. The results of X‐ray crystal structure analyses, performed for 8 l (R1 = H, R2 = 2,4,6‐(MeO)3C6H2), 10 d (R1 = H, R2 = Mes) and 11 d (R1 = H, R2 = Mes) are discussed and confirm the expected extreme sterical congestion of the molecules. 相似文献
55.
研究了三氟甲基磺酸三甲基硅酯/三氯化锑((CH3)3SiOSO2CF3/SbCl3)复合引发体系对1,3 戊二烯的聚合行为.在(CH3)3SiOSO2CF3引发剂中加入SbCl3后,使聚合反应速率提高了24倍,产率从(CH3)3SiOSO2CF3引发的55%提高到80%以上,分子量提高17倍.在聚合体系中加入酮类后,产率和分子量相对于(CH3)3SiOSO2CF3/SbCl3配比为02:1时引发所得聚合物均呈下降趋势;但对不同的酮来说,随着酮的位阻的增大,聚合物的产率和分子量均增大.聚合物的1H NMR图和红外谱图数据均证明该聚合反应是通过(CH3)3SiOSO2CF3与体系中残存的水水解所形成的质子酸HOSO2CF3与SbCl3反应所形成的复合体系引发进行的. 相似文献
56.
研究了三甲基硅化合物 ,主要是三甲基硅酯和三甲基硅氯化物 (TMSCI)与路易斯酸所形成的复合引发体系引发聚合 ,1,3 戊二烯 (PD)的聚合反应行为 ,考察了引发体系引发PD聚合所得聚合物的产率 ,分子量及分子量分布 ,聚合反应速率和聚合反应机理等 ;研究了多种给电体———醚、酮对聚合反应的影响 相似文献
57.
Aminoflavonoids are unique antioxidants comparing to other abundant flavonoids in nature. Their syntheses and biological activities were scarcely reported. An effectively copper-mediated amination of the corresponding bromoflavonoids to synthesize a series of new aminoflavonoids is described. 相似文献
58.
Yuliya V. Rassukana Oleg V. Stanko Ivanna P. Yelenich Petro P. Onysko 《Tetrahedron letters》2017,58(35):3449-3452
A convenient synthetic approach towards previously unknown N- and N,O-silylated α-iminophosphonates bearing fluoroalkyl groups at the imine C atom was developed. The synthetic potential of the compounds was demonstrated by their easy functionalization and the straightforward preparation of biorelevant aminophosphonates and free aminophosphonic acids with heterocyclic residues in the α-position. 相似文献
59.
《合成通讯》2013,43(21):3653-3660
Abstract Silica chloride (SiO2-Cl), as a heterogeneous reagent, has been used for the efficient dehydration of tertiary alcohols under mild reaction conditions. For comparison, we have also used trimethylsilyl chloride (TMSCl) as a homogeneous reagent for this purpose. We have found that silica chloride is a more efficient reagnet than trimethylsilyl chloride for this purpose. Handling of SiO2-Cl is much safer and easier than TMSCl, especially for large-scale operation. The selectivity of the method is also demonstrated by several competitive reactions. Ether formation, rearranged products, and polymerization have not been observed in the reactions. 相似文献
60.
《Journal of carbohydrate chemistry》2013,32(6):453-470
Glycosylation of 2-(trimethylsilyl)ethanol with various ethyl 1-thioglycosides, which were activated with N-iodosuccinimide and silver triflate, was studied. The starting thioglycosides, some prepared for the first time, were obtained conventionally from the corresponding α-1-acetates. When β-1-acetates were more readily available, these were converted to the α-anomers by anomerization, prior to the glycosylation. Using ethyl 1-thioglycosides as glycosyl donors, especially those bearing a pivaloyl or a nonparticipating group at O-2, the corresponding 2-(trimethylsilyl)ethyl α-d-mannopyranosides were obtained in excellent yields. 相似文献