全文获取类型
收费全文 | 647篇 |
免费 | 36篇 |
国内免费 | 45篇 |
专业分类
化学 | 688篇 |
晶体学 | 2篇 |
力学 | 1篇 |
综合类 | 2篇 |
物理学 | 35篇 |
出版年
2024年 | 2篇 |
2023年 | 4篇 |
2022年 | 7篇 |
2021年 | 9篇 |
2020年 | 15篇 |
2019年 | 15篇 |
2018年 | 14篇 |
2017年 | 21篇 |
2016年 | 23篇 |
2015年 | 11篇 |
2014年 | 15篇 |
2013年 | 92篇 |
2012年 | 25篇 |
2011年 | 22篇 |
2010年 | 18篇 |
2009年 | 33篇 |
2008年 | 31篇 |
2007年 | 32篇 |
2006年 | 35篇 |
2005年 | 37篇 |
2004年 | 40篇 |
2003年 | 38篇 |
2002年 | 27篇 |
2001年 | 24篇 |
2000年 | 16篇 |
1999年 | 5篇 |
1998年 | 16篇 |
1997年 | 12篇 |
1996年 | 8篇 |
1995年 | 6篇 |
1994年 | 8篇 |
1993年 | 15篇 |
1992年 | 8篇 |
1991年 | 6篇 |
1990年 | 5篇 |
1989年 | 7篇 |
1988年 | 7篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1983年 | 4篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1976年 | 2篇 |
1969年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有728条查询结果,搜索用时 62 毫秒
21.
Gerhard Hamprecht Karl-Heinz Knig Gerd Stubenrauch 《Angewandte Chemie (International ed. in English)》1981,20(2):151-164
Due to their bifunctional character, alkylsulfamoyl chlorides are versatile units for the synthesis of heterocycles, polar sulfamates, and sulfonamides. In the last decade, synthetic methods of general preparative use have been developed, by means of which amine hydrochlorides, isocyanates, aziridines or tertiary alcohols can be reacted with suitable sulfuric acid derivatives to give novel, variously substituted alkylsulfamoyl chlorides. These compounds can subsequently be converted either to previously unobtainable N-alkoxyalkyl-N-alkylsulfamoyl chlorides or to novel heterocycles of the type 1H-2,1,3-benzothiadiazin-4-one-2,2-dioxide, 2H-1,2,6-thiadia-zin-3-one-1,1-dioxide and 2H-1,2,4,6-thiatriazin-5-one-1,1-dioxide; these compounds are examples of interesting models which illustrate the relation between the structure and the action of the compound, and in some cases lead to highly selective, ecologically unobjectionable herbicides. On the other hand, the alkylsulfamoyl chlorides themselves can be N-acylated to give further 3- to 5-atom bifunctional synthesis units, with which novel heterocyclic syntheses can be carried out. Further uses of the alkylsulfamoyl chlorides include the preparation of biologically active sulfamates, and cycloaddition reactions of N-sulfonylamines prepared in situ. 相似文献
22.
IntroductionAcetolactatesynthase(ALS)isthefirstcommonenzymeinthebiosyntheticpathwayforthebranched-chainaminoacidsvaline,leucineandisoleucine.Itisaveryeffectivetargetsiteforherbicidalaction,whichistheselectedmodeofactionasitisspecificforplantsanddoesnotaffectmammals.Sulfonylureaherbicidesareanewclassofherbicidesdiscoveredinthemid-l97O'sl.ItsmodeofactionhasbeenestablishedtobeinhibitorytowardALS2.Muchattentionhasbeenfocusedonthiskindofcompounds,sincetheyhaveexcellentactivity,ahighdegreeofseIe… 相似文献
23.
四氟乙烯和全氟4-甲基-3,6-二氧杂-△~7辛基磺酰氟在溶剂氟里昂-113(F-113)中进行自由基引发聚合反应时,共聚物(T-O)是否有链转移,可以通过测定所得共聚物中的含氯量来得以证实。我们首次应用质子X萤光分析法(PIXE)进行分析。结果表明,共聚物中含氯量小于1ppm,F-113溶剂并未发生链转移。同时,我们测定了已证明有F-113参与链转移反应的F_(40)试样,含氯量高达700ppm。 相似文献
24.
Photochemical reactions of benzyl, heteroaromaticmethyl and allylcobaloximes with aryldisulfonyl chlorides yield symmetrical disulfones. Allyl cobaloximes yield allyldisulfones as the major product whereas bibenzyl is the major product in benzylcobaloximes. A time dependent 1H NMR studies show that bibenzyl is formed from O-benzyldimethylglyoxime - a predominant product in the initial stage of the reaction. 相似文献
25.
The standard potentialss
E
o of M/M+ (M=Li, Na, K, Rb, and Cs) electrodes in aqueous urea solutions containing 12, 20, 30 and 37% by weight of urea have been determined at 25°C from emf measurements on the cell M(Hg)/MCl (m), solvent/AgCl–Ag, from the activities of metals in amalgams by use of a similar type of cell in water, and from the values ofs
E
o of the Ag/AgCl electrode determined earlier. The standard free energies of transfer of MCl, G
t
o
(MCl), from water to the mixed solvents, computed by use of these values and those for the Ag–AgCl electrode, rise sharply from Li+ to Na+ but fall from Na+ to K+ and rather sharply from K+ to Cs+ with a maximum at Na+ in all the solvent compositions. This has been attributed to the superimposition of soft-soft interactions on the electrostatic interactions between the ions and the negative charge centers of the possible hydrogen-bonded solvent complexes in the mixed solvents. Comparison of G
t
o
(i) values for individual ions, obtained by a simultaneous extrapolation procedure, with those in aqueous mixtures of methanol,t-butanol, and dimethyl sulfoxide leads to the conclusion that the solvation of these ions in all these solvents is chiefly dictated by the acid-base type of ion-solvent interactions. 相似文献
26.
3-Arylsydnone-4-carbonitrile oxides may undergo 1,3-dipolar cycloadditions with alkenes to produce the corresponding 3-aryl-4-(5-substituted-isoxazolin-3-yl)sydnones. The direct reaction of 3-arylsydone-4-carbohydroximic acid chlorides with alkenes may also give the same products, and with higher yield. 相似文献
27.
Simple catalytic systems for cross-coupling reactions of acyl chlorides with arylboronic acids under microwave conditions were tested. Microwave irradiation facilitated the reaction course. Mild reaction conditions afford the symmetrical and unsymmetrical aryl ketones in reasonable to high yields within a short time. A wide range of substrates bearing an electron-donating or an electron-withdrawing substituent on aryl ring of acid chloride as well as on boronic acid were examined and high yields of ketones were produced. 相似文献
28.
A study on the free radical cyclization reaction of substituted 1,6-dienes mediated by p-toluenesulfonyl chloride is described. 相似文献
29.
A. N. Chekhlov 《Journal of Structural Chemistry》2007,48(6):1160-1163
The second crystal modification (II) of 1,10-diazonia-18-crown-6 dichloride [H2DA18C6]2+·2Cl?, where [H2DA18C6]2+ is the 1,10-diaza-18-crown-6 dication (DA18C6) with two protonated nitrogen atoms, was investigated by XRD. The monoclinic modification (II) (space group P21/n, a = 9.600 Å, b = 5.689 Å, c = 15.749 Å, β = 91.03°, Z = 2) was solved by direct methods and refined by full-matrix least squares analysis in an anisotropic approximation to R = 0.032 for all 2494 independent reflections collected (CAD-4 automatic diffractometer, λMoK α). In modification II, the conformation of the DA18C6 dication and the ion packing differ from those in triclinic modification I investigated previously. 相似文献
30.
The molar enthalpies of the solid–solid and solid–liquid phase transitions were determined by differential scanning calorimetry
for pure TbCl3 and KTb2Cl7, RbTb2Cl7, CsTb2Cl7, K3TbCl6, Rb3TbCl6 and Cs3TbCl6 compounds. Both types of compounds, i.e. M3TbCl6 and MTb2Cl7 (M=K, Rb, Cs) melt congruently and show additionally a solid–solid phase transition with a corresponding enthalpy Δtrs
H
0 of 6.1, 7.6 and 7.0 kJ mol–1 for potassium, rubidium and caesium M3TbCl6 compounds andΔtrs
H
0 of 17.1 (rubidium) and of 12.1 and 10.9 kJ mol–1 (caesium) for MTb2Cl7 compounds, respectively. The enthalpies of fusion were measured for all the above compounds with the exception of Rb3TbCl6 and Cs3TbCl6. The heat capacities of the solid and liquid compounds have been determined by differential scanning calorimetry (DSC) in
the temperature range 300–1100 K. The experimental heat capacity strongly increases in the vicinity of a phase transition,
but varies smoothly in the temperature ranges excluding these transformations. C
p data were fitted by an equation, which provided a satisfactory representation up to the temperatures of C
p discontinuity. The measured heat capacities were checked for consistency by calculating the enthalpy of formation of the
liquid phase, which had been previously measured. The results obtained agreed satisfactorily with these experimental data.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献