全文获取类型
收费全文 | 2023篇 |
免费 | 115篇 |
国内免费 | 94篇 |
专业分类
化学 | 2154篇 |
晶体学 | 12篇 |
力学 | 2篇 |
综合类 | 6篇 |
物理学 | 58篇 |
出版年
2023年 | 16篇 |
2022年 | 35篇 |
2021年 | 31篇 |
2020年 | 51篇 |
2019年 | 56篇 |
2018年 | 54篇 |
2017年 | 64篇 |
2016年 | 57篇 |
2015年 | 67篇 |
2014年 | 97篇 |
2013年 | 228篇 |
2012年 | 89篇 |
2011年 | 79篇 |
2010年 | 74篇 |
2009年 | 92篇 |
2008年 | 82篇 |
2007年 | 101篇 |
2006年 | 103篇 |
2005年 | 99篇 |
2004年 | 110篇 |
2003年 | 93篇 |
2002年 | 156篇 |
2001年 | 41篇 |
2000年 | 31篇 |
1999年 | 30篇 |
1998年 | 28篇 |
1997年 | 31篇 |
1996年 | 20篇 |
1995年 | 20篇 |
1994年 | 36篇 |
1993年 | 27篇 |
1992年 | 31篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1989年 | 10篇 |
1988年 | 11篇 |
1987年 | 9篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 12篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1981年 | 2篇 |
1980年 | 6篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1972年 | 1篇 |
1969年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有2232条查询结果,搜索用时 15 毫秒
81.
Dr. Christopher R. Emerson Dr. Lev N. Zakharov Prof. Dr. Paul R. Blakemore 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16342-16356
Four putative functionalized α‐chloroakyllithiums RCH2CHLiCl, where R=CHCH2 ( 18 a ), CCH ( 18 b ), CH2OBn ( 18 c ), and CH[O(CH2)2O] ( 18 d ), were generated in situ by sulfoxide–lithium exchange from α‐chlorosulfoxides, and investigated for the stereospecific reagent‐controlled homologation (StReCH) of phenethyl and 2‐chloropyrid‐5‐yl ( 17 ) pinacol boronic esters. Deuterium labeling experiments revealed that α‐chloroalkyllithiums are quenched by proton transfer from their α‐chlorosulfoxide precursors and it was established that this effect compromises the yield of StReCH reactions. Use of α‐deuterated α‐chlorosulfoxides was discovered to ameliorate the problem by retarding the rate of acid‐base chemistry between the carbenoid and its precursor. Carbenoids 18 a and 18 b showed poor StReCH efficacy, particularly the propargyl group bearing carbenoid 18 b , the instability of which was attributed to a facile 1,2‐hydride shift. By contrast, 18 d , a carbenoid that benefits from a stabilizing interaction between O and Li atoms gave good StReCH yields. Boronate 17 was chain extended by carbenoids 18 a , 18 b , and 18 d in 16, 0, and 68 % yield, respectively; α‐deuterated isotopomers D ‐ 18 a and D ‐ 18 d gave yields of 33 and 79 % for the same reaction. Double StReCH of 17 was pursued to target contiguous stereodiads appropriate for the total synthesis of (?)‐epibatidine ( 15 ). One‐pot double StReCH of boronate 17 by two exposures to (S)‐D ‐ 18 a (≤66 % ee), followed by work‐up with KOOH, gave the expected stereodiad product in 16 % yield (d.r.~67:33). The comparable reaction using two exposures to (S)‐D ‐ 18 d (≤90 % ee) delivered the expected bisacetal containing stereodiad (R,R)‐DD ‐ 48 in 40 % yield (≥98 % ee, d.r.=85:15). Double StReCH of 17 using (S)‐D ‐ 18 d (≤90 % ee) followed by (R)‐D ‐ 18 d (≤90 % ee) likewise gave (R,S)‐DD ‐ 48 in 49 % yield (≥97 % ee, d.r.=79:21). (R,S)‐DD ‐ 48 was converted to a dideuterated isotopomer of a synthetic intermediate in Corey’s synthesis of 15 . 相似文献
82.
Minami Odagi Kota Furukori Tatsuya Watanabe Prof. Dr. Kazuo Nagasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16740-16745
Highly enantioselective catalytic oxidation of 1‐tetralone‐derived β‐keto esters was achieved by using a guanidine–urea bifunctional organocatalyst in the presence of cumene hydroperoxide (CHP), a safe, commercially available oxidant. The α‐hydroxylation products were obtained in 99 % yield with up to 95 % enantiomeric excess (ee). The present oxidation was successfully applied to synthesize a key intermediate of the anti‐cancer agent daunorubicin ( 2 ). 相似文献
83.
Triflic acid-mediated stereoselective direct lactonization of a variety of α-amino γ,δ-unsaturated carboxylic acid esters and the construction of new γ-butyrolactone structural motifs are reported. Several α-amino γ,δ-unsaturated carboxylic acid esters underwent stereo- and regioselective 1,5-cyclization and afforded a variety of highly substituted homoserine lactone scaffolds having contiguous stereocenters. The direct lactonization of the chiral α-amino γ,δ-unsaturated carboxylic acid esters with triflic acid led to the enantioselective synthesis of the novel homoserine lactones. A plausible mechanism for the direct lactonization of α-amino γ,δ-unsaturated carboxylic acid esters is presented. The stereochemistry of major isomers 3f, 7a, 7b, and 7d was unambiguously established from the X-ray structure analysis. 相似文献
84.
The synthesis of 3-(4-alkyl-4,5-dihydropyrrolo[1,2-a]quinoxalin-4-yl)-2H-chromen-2-one derivatives by a three-component reaction of salicylaldehyde, β-keto esters, and 1-(2-aminophenyl)pyrrole using piperidine–iodine as a dual system catalyst is reported. Good yields, mild reaction conditions, and ease of handling are the main aspects of the method. The structural assignments are supported by 1H NMR, 13C NMR, and X-ray crystallography data. 相似文献
85.
Rapid analysis of phthalic acid esters in environmental water using fast elution gas chromatography with mass spectrometry and adaptive library spectra 下载免费PDF全文
A method for the fast determination of the components in a complex sample by using gas chromatography with mass spectrometry was developed and used for the quantitative analysis of phthalic acid esters in environmental water. In the method, the adaptively corrected mass spectra were used to compensate for the differences between the library spectra and the measured ones in the experiment. The correction was obtained by the iterative transformation of the library spectra using iterative target transformation factor analysis, and the resolution was performed by non‐negative immune algorithm using the corrected spectra. Rapid analysis of 16 phthalic acid esters in water samples was achieved using fast elution gas chromatography with mass spectrometry measurements. The results show that the mass spectra and chromatographic profiles of the phthalic acid esters can be obtained from the overlapping signal of 13 min elution, and accurate quantitative analysis can be obtained. The recoveries of the phthalic acid esters obtained by standard addition are between 90.3 and 107.4%, and the relative standard deviations obtained in repeated measurements are less than 9%. 相似文献
86.
Zinc‐Catalyzed Borylation of Primary,Secondary and Tertiary Alkyl Halides with Alkoxy Diboron Reagents at Room Temperature 下载免费PDF全文
Dr. Shubhankar Kumar Bose Dr. Katharina Fucke Prof. Dr. Lei Liu Prof. Dr. Patrick G. Steel Prof. Dr. Todd B. Marder 《Angewandte Chemie (International ed. in English)》2014,53(7):1799-1803
A new catalytic system based on a ZnII NHC precursor has been developed for the cross‐coupling reaction of alkyl halides with diboron reagents, which represents a novel use of a Group XII catalyst for C? X borylation. This approach gives borylations of unactivated primary, secondary, and tertiary alkyl halides at room temperature to furnish alkyl boronates, with good functional‐group compatibility, under mild conditions. Preliminary mechanistic investigations demonstrated that this borylation reaction seems to involve one‐electron processes. 相似文献
87.
Dehydrogenative Meyer–Schuster‐Like Rearrangement: A Gold‐Catalyzed Reaction Generating an Alkyne 下载免费PDF全文
M. Sc. Yang Yu M. Sc. Weibo Yang M. Sc. Daniel Pflästerer Prof. Dr. A. Stephen K. Hashmi 《Angewandte Chemie (International ed. in English)》2014,53(4):1144-1147
Easily accessible propargylic esters are converted to the inverted alkynyl ketones in an oxidative gold‐catalyzed reaction. Gagosz’s catalyst in combination with PhI(OAc)2 is the best system for this conversion and 18 examples with yields up to 80 % are reported. The results indicate that the triple bond in the product is formed by elimination from a vinylgold intermediate. In a formal sense the new conversion overall is a dehydrogenative Meyer–Schuster rearrangement. 相似文献
88.
Kinetic Resolution of Racemic Mandelic Acid Esters by N,N′‐Dioxide–Scandium‐Complex‐Catalyzed Enantiomer‐Selective Acylation 下载免费PDF全文
Yuheng Zhang Prof. Dr. Xiaohua Liu Lin Zhou Wangbin Wu Tianyu Huang Yuting Liao Lili Lin Prof. Dr. Xiaoming Feng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(48):15884-15890
A simple and efficient acylative kinetic resolution of racemic mandelic acid esters was accomplished with a chiral N,N’‐dioxide–scandium(III) complex under mild and base‐free reaction conditions. A variety of mandelic acid esters performed well in the reaction, obtaining both acylated products (up to 49% yield, 97% ee) and recovered substrates (up to 49% yield, 95% ee) in high enantioselectivities with perfect selectivity factors (up to 247). The enantioselective recognition and catalytic models were also proposed for the catalytic KR reaction. 相似文献
89.
90.
Biodegradable poly(lactic acid) is regarded as one of the most promising biopolymers with large market potential, but its applications are limited by the poor mechanical properties, since PLA is rigid and brittle. To enhance its mechanical, thermal and processability properties, at this study the authors use small molecules maleic acid (MA) and its propyl ester derivatives monopropyl maleate (MPM) and dipropyl maleate (DPM) as alternative plasticizers. The morphological, thermal, and mechanical properties of plasticized PLA were evaluated by DSC, FTIR, 1H NMR, DMA, PLOM and SEM into two controlled environment desiccators: SiO2 and water-saturated atmosphere. The results show that the increase in the substitution of MA increasing PLA plasticization ability, decreasing the PLA Tg from 48 °C to 5 °C and increasing percentage strain, while the presence of carboxyl groups from MA and MPM entails in water absorption to the bulk of the films which leads to a hydrolysis of MPM to MA. FTIR and 1H NMR confirmed these results and show that the hydrolysis and plasticizer evaporation occurs as a function of time. SEM images of fractured films analyzed after conditioned during a one-month present porous surface for PLA/MPM. In conclusion, maleate propyl esters have excellent PLA plasticizing properties and could improve the (using, market employment of this polymer. 相似文献