全文获取类型
收费全文 | 2520篇 |
免费 | 249篇 |
国内免费 | 239篇 |
专业分类
化学 | 2431篇 |
晶体学 | 35篇 |
力学 | 8篇 |
综合类 | 15篇 |
数学 | 139篇 |
物理学 | 263篇 |
无线电 | 117篇 |
出版年
2024年 | 3篇 |
2023年 | 26篇 |
2022年 | 56篇 |
2021年 | 65篇 |
2020年 | 81篇 |
2019年 | 77篇 |
2018年 | 71篇 |
2017年 | 85篇 |
2016年 | 97篇 |
2015年 | 84篇 |
2014年 | 110篇 |
2013年 | 198篇 |
2012年 | 117篇 |
2011年 | 158篇 |
2010年 | 143篇 |
2009年 | 148篇 |
2008年 | 164篇 |
2007年 | 155篇 |
2006年 | 156篇 |
2005年 | 142篇 |
2004年 | 158篇 |
2003年 | 140篇 |
2002年 | 135篇 |
2001年 | 55篇 |
2000年 | 60篇 |
1999年 | 41篇 |
1998年 | 30篇 |
1997年 | 36篇 |
1996年 | 38篇 |
1995年 | 30篇 |
1994年 | 26篇 |
1993年 | 23篇 |
1992年 | 22篇 |
1991年 | 9篇 |
1990年 | 12篇 |
1989年 | 13篇 |
1988年 | 10篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1982年 | 8篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有3008条查询结果,搜索用时 379 毫秒
61.
Effects of double substitution on the thermodynamic stabilities of nitrogen radicals 总被引:1,自引:0,他引:1
Studiesonkineticsofradicalreactions[1]andonCHbonddissociationenergies(BDE)[2]haveshownthatcarbonradicalsarestabilizedbyeitheranelectrondonatinggroup(EDG)oranelectronwithdrawinggroup(EWG),andthatifacarbonradicalissubstitutedwithbothanEDGandanEWGatthesamecen… 相似文献
62.
Hong Xin SHI * Hui LIN Gérard MANDVILLE Zhejiang Key Lab. of Green-chemical Synthetic Technology Zhejiang University of Technology Hangzhou .Department of Chemistry Institute of Science Zhejiang University Hangzhou Université de Paris-Sud ICMO Orsay Cédex France 《中国化学快报》2004,15(3):288-291
The reaction of aromatic carboxylic acid with oxalyl chloride gives rise to the corresponding acid chloride which without purification is treated with the sodium salt of mercaptopyridine oxide in the presence of 2,2-azo-bisisobutyronitrile (AIBN), radical initiator to give a brominated aromatic compound. After etherification and oxidation, 5-iodovaniline was converted to trisubstituted benzene carboxylic acid which give 1-bromo-3-methoxy-4-propoxy-5-iodobenzene by this new brominating process with a yield of 74%. 相似文献
63.
Rybachenko V. I. Schroeder G. Chotii K. Yu. Lenska B. Kovalenko V. V. Red'ko A. N. 《Theoretical and Experimental Chemistry》2003,39(6):359-363
We have studied the rate of 15 reactions of acyl transfer from O-acyl salts of 4-dimethylaminostyryl-4-pyridine N-oxide to 4-morpholinopyridine and 4-dimethylaminopyridine N-oxides in acetonitrile solutions. Analysis of the results based on the Shaik – Pross approach and the Marcus equation shows that if the structure of the acyl group is varied, then the reactivity is determined by such parameters as the resonance interaction in the transition state (B) or the internal barrier (G
0) of the reaction. 相似文献
64.
Kazuyuki MiyashitaHidenobu Murafuji Hiroshi IwakiEito Yoshioka Takeshi Imanishi 《Tetrahedron》2003,59(26):4873-4879
As a second-generation pyridoxal model compound for cystathionine β-synthase, we designed a novel model compound having an ionophore function and an imidazole function, application of which to the β-replacement reaction with various thiols smoothly took place to give S-substituted cysteines. Peptides having a serine-O-carbonate residue at the N-terminal position were also converted to the corresponding peptides having an S-substituted cysteine residue under the catalytic conditions of the novel pyridoxal model compound. 相似文献
65.
A novel convergent approach to dendritic macromolecules is described in which 4,6-dichloro-2-(4-methoxyphenyl)-pyrimidine is used as the building block. The nucleophilic aromatic substitution reaction at this AB2-monomer was used as the key step in the propagation of the dendrons. Different core reagents were used to form the dendrimers, including a 5,15-bis(pyrimidyl)porphyrin core. Fourth-generation dendrons and third-generation dendrimers could be synthesized. The presented dendrimers are promising candidates to be used in applications where a more rigid structure and a larger resistance towards the applied conditions is required. 相似文献
66.
A new entry for the synthesis of 3-alkyl substituted 5-vinyloxazolidin-2-one derivatives 2 from cis-2-butenylene-1,4-dicarbonate 1 and primary amines mediated by palladium-phosphine catalysts is described. The scope and limitation, a plausible mechanism, and an asymmetric version of the reaction are also discussed. 相似文献
67.
在B3LYP/6-311 G(2df,p)的水平上,对反应X- CH3SCl(X=F,Cl,Br,I)进行了理论研究.计算结果表明:X-(X=Cl,Br,I)与CH3SCl作用时,实际发生的是在硫原子上而不是在碳原子上的亲核取代反应,而且属于加成-消去机理.但是F-与CH3SCl作用则容易发生脱质子反应. 相似文献
68.
I. G. Abramov A. V. Smirnov L. S. Kalandadze N. P. Gerasimova N. A. Nozhnin V. N. Sakharov 《Chemistry of Heterocyclic Compounds》2005,41(2):238-240
New 3-aryl-substituted [1,2,4]triazolo][3,4-b][1,3]benzothiazole-6,7-dicarbonitriles have been synthesized by successive interaction of 5-aryl-4H-triazole-2-thiols with 4-bromo-5-nitrophthalonitrile in the presence of K2CO3 initially at the bromine atoms and then at the nitro group.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, 270–272, February, 2005. 相似文献
69.
Kinetic studies of the aminolysis of [methyl(thiomethyl)carbene]pentacarbonyl chromium(0),(CO)5CrC(CH3)(SCH3) (1-Cr(S)) and [methyl(thiomethyl)carbene]pentacarbonyltungsten(0), (CO)5WC(CH3)(SCH3) (1-W(S)), with morpholine, a secondary amine, in 50% acetonitrile-50% H2O (v/v at 25 °C) is reported. The second-order rate constant (kA in m−1 s−1) increases with amine concentration, giving a linear dependence with an intercept on the rate axis and a tendency towards leveling off at higher amine concentration. The reaction was found to undergo general base catalysis. The mechanism proposed is very similar to those for ester reactions, involving a nucleophilic addition of amine to the substrate to yield a zwitterionic tetrahedral intermediate in the first step, followed by deprotonation to form in the second step, which, in the third step, converted to product by H2O and/or conjugate acid of the base (BH+), assisted MeS− expulsion. The reactivity (k1) of 1-W(S) was found to be higher than that of 1-Cr(S), whereas, comparable , water catalyzed and , BH+ catalyzed, leaving group departure were found for both the carbenes complexes. All these observations have been explained successfully. 相似文献
70.
T. M. Zubareva T. M. Prokop’eva I. V. Kapitanov I. A. Belousova N. G. Razumova A. F. Popov 《Theoretical and Experimental Chemistry》2007,43(4):247-254
Neutral forms of hydroxylamine, N-methylhydroxylamine, and N,N-dimethylhydroxylamine are typical α-nucleophiles in water.
In comparison with aryl anions of similar basicity their rate of reaction in the decomposition of 4-nitrophenyl diethylphosphonate
is increased by about 102 times. Decomposition of the substrate is accelerated in cetyltrimethylammonium bromide micelles (about 4 to 30 fold). Hydroxylamine
and its N-alkyl derivatives are the most effective low basicity nucleophiles. The sole factor responsible for the micellar
effects is the concentration of the reagent in the surfactant micelles.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 4, pp. 231–236, July–August, 2007. 相似文献