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241.
Bis‐hydrazonoyl chloride 1 reacts regioselectively with 3‐mercapto‐1,2,4‐triazole 2a , 2,3‐dihydro‐3‐thioxo‐1,2,4‐triazin‐5(4H)‐one 2b and 2‐mercaptobenzimidazole 2c to give the hitherto unknown annelated 2,3‐bis‐(phenylhydrazono)thiazoles 6a‐c , respectively. Reactions of 1 with the methylthio derivatives of such heterocycles afforded the annelated 3,3′‐bis‐(1,2,4‐triazoles) 11a‐c , respectively. Similar reaction of 1 with 2‐phenylamino‐4(3H)‐pyrimidinones 4 gave 2,3‐bis(phenylhydrazono)imidazo[1,2‐a]pyrimidin‐5(1H)‐ones 16 . Oxidation of 6c yielded the corresponding bis(phenylazo) derivative 15 . The regiochemistry of the studied reactions is discussed. 相似文献
242.
243.
Manfred T. Reetz 《Angewandte Chemie (International ed. in English)》1984,23(8):556-569
The addition of C-nucleophiles such as Grignard reagents or enolates to chiral α- or β-alkoxy aldehydes or ketones creates a new center of chirality and is therefore diastereogenic. In order to control stereoselectivity, two strategies have been developed: (1) Use of Lewisacidic reagents which form intermediate chelates, these being attacked stereoselectively from the less hindered side (chelation control); (2) use of reagents incapable of chelation, stereoselective attack being governed by electronic and/or steric factors (non-chelation control). Generally, the two methods lead to the opposite sense of diastereoselectivity. It is possible to predict the outcome by careful choice of organometallic reagents containing elements such as Li, Mg, B, Si, Sn, Cu, Zn, or Ti. For corrigendum see DOI: 10.1002/anie.198407461 相似文献
244.
Paul Caubre 《Angewandte Chemie (International ed. in English)》1983,22(8):599-613
Why do we hardly use the simplest and, at the same time, inexpensive reducing agent sodium hydride in organic chemistry? To this question the answer is invariably: “It is too basic”. In this progress report we describe work we have performed aimed at controlling the basicity of NaH using sodium alcoholates and metal salts. The complex reducing agents (CRA's) developed (symbolized NaH-RONa-MXn) allow organic halides, alkenes, alkynes and ketones to be reduced selectively. Highly regioselective 1,4- and 1,2-reductions of α,β-unsaturated ketones are easily performed using appropriate metal salts. Modified CRA's have proved to be excellent hydrosilylating reagents for carbonyl groups, non-pyrophoric heterogeneous hydrogenation catalysts, coupling reagents for aryl and vinyl halides, and reagents for the carbonylation of organic halides under very mild conditions. The study of these reactions opened up the field to phase-transfer-catalyzed photostimulated carbonylations as well as to SRN1 reactions of metalates.–Thus, starting from the simple sodium hydride a large number of useful reagents have become accessible. 相似文献
245.
S. Podzimek 《Chromatographia》1992,33(7-8):377-384
Summary The article gives a brief survey of the use of liquid chromatography in characterizing different kinds of synthetic resins and presents several examples of the application of this technique for analysis of such materials. 相似文献
246.
E. Kühle B. Anders E. Klauke H. Tarnow G. Zumach 《Angewandte Chemie (International ed. in English)》1969,8(1):20-34
The readily obtainable isocyanide dichlorides can be used as starting materials for the preparation of many types of substances. Exchange reactions yield numerous derivatives of formic and carbonic acids, while heterocyclic products have been obtained by reaction with bifunctional partners. The present article deals not only with reactions that are known from the literature but also with the author's own work, some of which has not been published before. 相似文献
247.
FTIR analysis and monitoring of synthetic aviation engine oils 总被引:2,自引:0,他引:2
Synthetic turbine oils from military aircraft engines were analysed for antioxidant content and total acid number using infrared (IR) spectroscopy. Two-dimensional IR correlation analysis was employed to investigate and interpret observed trends in the spectra, as acid was formed and antioxidant species were depleted in the oils, as a function of aging and engine wear. Principal components and partial least squares algorithms were used and compared for the development of calibration and prediction models. Transmission IR spectrometry is demonstrated to be effective for the analysis and monitoring of synthetic aviation turbine engine oils and shown to provide rapid and accurate information as compared with traditional analytical techniques and methods. 相似文献
248.
Horst Kunz 《Angewandte Chemie (International ed. in English)》1987,26(4):294-308
Glycopeptides are partial structures of the connecting regions of glycoproteins and, like these, always contain glycosidic bonds between the carbohydrate and peptide parts. Glycoproteins are not only widely distributed but are also decisive factors in post-translational biological selectivity, especially in biological recognition. Targeted syntheses of glycopeptides require stereoselective formation of the glycosidic bonds between the carbohydrate and the peptide parts and protective group methods that enable selective deblocking of only one functional group in these polyfunctional molecules. These heavy demands have been met by the well-established use of benzylic protective groups, which can be removed by hydrogenolysis, combined with the use of base-labile 2-phosphonioethoxycarbonyl (Peoc) or 9-fluorenylmethoxycarbonyl (Fmoc) protective groups or of bromoethyl esters, which can be removed under neutral conditions. The acidolysis of tert-butyloxycarbonyl (Boc) groups and of tert-butyl esters has also been successfully used, although, under acidic conditions, anomerization or rupture of the glycosidic bonds may occur, especially when nucleophiles are present. The stable, two-stage 2-(pyridyl)ethoxycarbonyl (Pyoc) protective groups allow a more reliable synthesis of complex glycopeptides since they can be removed, after modifications, under mild conditions. Particularly suitable for the synthesis of sensitive glycopeptides are the stable allyl protective groups. They can be removed from the complex glycopeptides in a highly selective and effective manner by means of noble-metal catalysts under practically neutral conditions. These methods have been employed to synthesize glycopeptides corresponding to partial structures of interesting glycoproteins. Deprotected glyopeptides representing tumor-associated antigen structures can be coupled to bovine serum albumin, which serves as a biological carrier molecule, without the necessity of using an artificial coupling component (spacer). 相似文献
249.
In 1963, it was found that sterically unhindered esters of cyanic acid, which had previously been considered unobtainable, could be easily prepared from phenols and cyanogen halides. Another synthesis, involving the thermolysis of thiatriazole derivatives, was discovered in 1964. The aryl cyanates in particular have since been found to have many uses as starting materials for the preparation of numerous new classes of compounds [e.g. derivatives of esters of imidocarbonic acid (esters, amides, imides, hydrazides, hydroxylamides, sulfamides, sulfhydrazides, semicarbazides); esters of imidocarboxylic acids; s-triazines, pyrimidines, tetrazoles, triazoles, triazolones, oxadiazoles, thiadiazoles, benzoxazinones, etc.], mainly by addition of nucleophilic or 1,3-dipolar reactants, or as aids e.g. in the elimination of H2O or H2S or in the transfer of CN groups. 相似文献
250.
An efficient metal-free procedure for the synthesis of tertiary amines by the reductive amination of carbonyl compounds is reported, which allows a convergent access to sterically hindered amines of the general formulas NR(R′)2 and NRR′R″. The mild and operationally simple protocol uses the Hantzsch ester for transfer hydrogenation and catalytic amounts of thiourea for imine activation. 相似文献