全文获取类型
收费全文 | 1635篇 |
免费 | 68篇 |
国内免费 | 2篇 |
专业分类
化学 | 1331篇 |
晶体学 | 16篇 |
力学 | 19篇 |
数学 | 45篇 |
物理学 | 294篇 |
出版年
2023年 | 13篇 |
2022年 | 15篇 |
2021年 | 25篇 |
2020年 | 30篇 |
2019年 | 41篇 |
2018年 | 30篇 |
2017年 | 15篇 |
2016年 | 41篇 |
2015年 | 36篇 |
2014年 | 40篇 |
2013年 | 70篇 |
2012年 | 120篇 |
2011年 | 115篇 |
2010年 | 61篇 |
2009年 | 65篇 |
2008年 | 83篇 |
2007年 | 77篇 |
2006年 | 109篇 |
2005年 | 82篇 |
2004年 | 75篇 |
2003年 | 51篇 |
2002年 | 53篇 |
2001年 | 30篇 |
2000年 | 34篇 |
1999年 | 24篇 |
1998年 | 11篇 |
1997年 | 9篇 |
1996年 | 20篇 |
1995年 | 12篇 |
1994年 | 15篇 |
1993年 | 8篇 |
1992年 | 18篇 |
1991年 | 17篇 |
1990年 | 20篇 |
1989年 | 8篇 |
1988年 | 13篇 |
1987年 | 9篇 |
1986年 | 9篇 |
1985年 | 11篇 |
1984年 | 17篇 |
1982年 | 11篇 |
1981年 | 10篇 |
1980年 | 10篇 |
1979年 | 15篇 |
1978年 | 14篇 |
1977年 | 10篇 |
1975年 | 9篇 |
1974年 | 17篇 |
1973年 | 20篇 |
1970年 | 8篇 |
排序方式: 共有1705条查询结果,搜索用时 15 毫秒
41.
Oxetanes were reacted with lithium enolates generated from esters or amides in the presence of boron trifluoride etherate to give δ-hydroxyesters or amides in high yield, which were hydrolyzed and converted to δ-lactones. 相似文献
42.
Majima K Takita R Okada A Ohshima T Shibasaki M 《Journal of the American Chemical Society》2003,125(51):15837-15845
We describe the development of a general catalytic asymmetric Michael reaction of acyclic beta-keto esters to cyclic enones, in which asymmetric induction occurs at the beta-position of the acceptors. Among the various asymmetric catalyst systems examined, the newly developed La-NR-linked-BINOL complexes (R = H or Me) afforded the best results in terms of reactivity and selectivity. In general, the NMe ligand 2 was suitable for the combination of small enones and small beta-keto esters, and the NH ligand 1 was suitable for bulkier substrates (steric tuning of the catalyst). Using the La-NMe-linked-BINOL complex, the Michael reaction of methyl acetoacetate (8a) to 2-cyclohexen-1-one (7b) gave the corresponding Michael adduct 9ba in 82% yield and 92% ee. The linker heteroatom in linked-BINOL is crucial for achieving high reactivity and selectivity in the Michael reaction of beta-keto esters. The amine moiety in the NR-linked-BINOL can also tune the Lewis acidity of the central metal (electronic tuning of the catalyst), which was supported by density functional studies and experimental results. Another advantage of the NR-linked-BINOL ligand as compared with O-linked-BINOL is the ease of modifying a substituent on the amine moiety, making it possible to synthesize a variety of NR-linked-BINOL ligands for further improvement or development of new asymmetric catalyses by introducing additional functionality on the linker with the amine moiety. The efficiency of the present asymmetric catalysis was demonstrated by the synthesis of the key intermediate of (-)-tubifolidine and (-)-19,20-dihydroakuammicine in only five steps compared to the nine steps required by the original process from the Michael product of malonate. This strategy is much more atom economical. On the basis of the results of mechanistic studies, we propose that a beta-keto ester serves as a ligand as well as a substrate and at least one beta-keto ester should be included in the active catalyst complex. Further improvement of the reaction by maintaining an appropriate ratio of the La-NMe-linked-BINOL complex and beta-keto esters is also described. 相似文献
43.
Hiroshi Tanaka Toru Masuko Keisuke Homma Saburo Okajima 《Journal of polymer science. Part A, Polymer chemistry》1969,7(7):1997-2006
Polypropylene films of various isotacticities and crystallinities were stretched biaxially in one step in air at 140–152°C or polyaxially in poly(ethylene glycol) at 130–160°C, and the morphological changes were studied by electron microscopy (replica). In the initial stage of stretching, with vA = 1.4, the spherulites of one of the films used for the experiment were broken both from the centers and boundaries, and those of another film were broken mainly from the center. This difference in the deformation behavior seems to be characteristic of the film properties and independent of the method of stretching, although the factors involved are still unknown. On further stretching (vA = 22), well annealed spherulites were broken into many small blocklike fragments with unfolded fibrils running among them, particularly at the low stretching temperature (140°C), and fibrillation proceeded at the expense of the residual fragments. In the case of quenched or slightly crystallized material, the fragments were dendritic and divided into finer and finer fibrils on stretching. At elevated temperature, however, even for well annealed spherulites, the deformation behavior resembles that of the quenched material, and at a high degree of stretching the spherulites take on the fibrillar net structure in every case. In films containing a high amount of atactic fraction, radial, tangential, and boundary cracking occurred more easily, and broad fibrils were observed across the cracks. 相似文献
44.
Keisuke Kato Chie Matsuba Hiroyuki Takayama Tomoyuki Mochida Tat'yana A. Peganova Oleg V. Gusev 《Tetrahedron》2006,62(42):9988-9999
The oxidative cyclization-carbonylation of meso-2-alkyl-2-propargylcyclohexane-1,3-diols mediated by Pd(II) with chiral bisoxazoline (box ligand) afforded bicyclic-β-alkoxyacrylates. Based on a ligand screening, 2,2′-isopropylidenebis[(4S,5R)-4,5-di(2-naphthyl)-2-oxazoline] ligand has been developed. The products with a chiral quaternary carbon were obtained in 71-100% yields with 85-95% ee. 相似文献
45.
Tatsuya Oshima Kaoru Oishi Keisuke Ohto Katsutoshi Inoue 《Journal of inclusion phenomena and macrocyclic chemistry》2006,55(1-2):79-85
Extraction behaviors of catecholamines with a series of calixarene carboxylic acid derivatives were investigated. Relatively large calix[6]arene and calix[8]arene extract catecholamines into the organic solution, while smaller calix[4]arene and the monomer analog do not. The calix[6]arene, which has a cavity that fits a protonated amino group well, selectively extracts a primary amino compound dopamine over other catecholamines. Slope analysis and Job’s method confirmed formation of a 1:1 complex between the calix[6]arene and dopamine. On the other hand, the calix[8]arene extracts both dopamine and adrenaline, due to the large cavity for induced-fit recognition. Dopamine extracted with the calixarene is quantitatively stripped by contacting the organic solution with a fresh acidic solution. 相似文献
46.
Akai S Kawashita N Satoh H Wada Y Kakiguchi K Kuriwaki I Kita Y 《Organic letters》2004,6(21):3793-3796
[reaction: see text] The reactions of (phenylsulfinyl)furans or -thiophenes with carbon nucleophiles in the presence of trifluoroacetic anhydride allowed the nucleophilic installation of carbon functional groups on the furan and thiophene nuclei with complete regioselectivity. 相似文献
47.
Shunichi Manabe Kazumasa Wakamatsu Yoshimasa Hirata Kiyoyuki Yamada 《Tetrahedron》1979,35(16):1925-1929
13C NMR spectra are reported for derivatives of toxic sesquiterpenes, anisatin (I) and neoanisatin (II). Chemical shifts for each compound have been assigned on the basis of off-resonance decoupling experiments, known chemical shift rules, and comparison of the spectra among the compounds examined. Toxic anisatin (I) is known to isomerize under mild conditions to a non-toxic compound, anisatinic acid. The structure of anisatinic acid has been determined unambiguously to be IIIa by the 13C NMR spectral analysis of a derivative 8 of anisatinic acid. Some aspects of the substituent effects on the 13C chemical shifts obtained in the present investigation are described. 相似文献
48.
Masaaki Fujimatsu Tadao Natsuume Hirotaka Hirata Yasuhiko Shirota Shigekazu Kusabayashi Hiroshi Mikawa 《Journal of polymer science. Part A, Polymer chemistry》1970,8(11):3349-3357
Copolymerizations of N-vinylcarbazole with both isobutyl vinyl ether and N-vinyl-pyrrolidone initiated by some organic electron acceptors have been investigated for the purpose of elucidating the propagation mechanism in the charge-transfer polymerization. Copolymerizations of the same system catalyzed by authentic cationic catalysts have also been made for comparison. The results indicate that the propagation mechanism of the charge-transfer polymerization studied is catio ie. 相似文献
49.
Y Naito T Goto F Akahoshi S Ono H Yoshitomi T Okano N Sugiyama S Abe S Hanada M Hirata 《Chemical & pharmaceutical bulletin》1991,39(9):2323-2332
A series of 2-[4-(thiazol-2-yl)phenyl]propionic acids substituted at various positions were prepared by the reaction of diethyl 2-methyl-2-(4-thiocarbamoylphenyl)malonates with alpha-bromoaldehyde diethyl acetals or alpha-haloketones followed by hydrolysis of esters. The inhibition of prostaglandin H synthetase (cyclooxygenase) was assayed by use of an enzyme preparation from guinea pig polymorphonuclear leukocytes. Examination of the structure-activity relationship of these compounds indicated that the substitution pattern with halogens at position 3 (R1) of the benzene ring and a methyl group in position 4 (R2) and/or 5 (R3) of the thiazole ring were favorable for inhibitory activity. The compounds bearing bulky alkyl or polar functional groups at the R2 position were weak inhibitors. The potent inhibitors of cyclooxygenase were tested for their ability to reduce carrageenin-induced inflammation of rat paws. These derivatives had strong anti-inflammatory activity based on their strong inhibition of cyclooxygenase, with some exceptions, including those with a thiomethyl group at R1. 相似文献
50.