全文获取类型
收费全文 | 1620篇 |
免费 | 77篇 |
国内免费 | 16篇 |
专业分类
化学 | 1045篇 |
晶体学 | 4篇 |
力学 | 55篇 |
数学 | 338篇 |
物理学 | 271篇 |
出版年
2024年 | 3篇 |
2023年 | 19篇 |
2022年 | 42篇 |
2021年 | 53篇 |
2020年 | 36篇 |
2019年 | 42篇 |
2018年 | 34篇 |
2017年 | 30篇 |
2016年 | 46篇 |
2015年 | 47篇 |
2014年 | 70篇 |
2013年 | 84篇 |
2012年 | 138篇 |
2011年 | 150篇 |
2010年 | 94篇 |
2009年 | 82篇 |
2008年 | 99篇 |
2007年 | 105篇 |
2006年 | 85篇 |
2005年 | 67篇 |
2004年 | 75篇 |
2003年 | 80篇 |
2002年 | 66篇 |
2001年 | 31篇 |
2000年 | 11篇 |
1999年 | 12篇 |
1998年 | 15篇 |
1997年 | 14篇 |
1996年 | 6篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 5篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1975年 | 3篇 |
1969年 | 1篇 |
1938年 | 1篇 |
1930年 | 1篇 |
排序方式: 共有1713条查询结果,搜索用时 15 毫秒
11.
Emmanuel A. Adegoke Babajide I. Alo Oluwole B. Familoni 《Journal of heterocyclic chemistry》1987,24(1):107-110
Regiospecific synthesis of 4H-3,3a-dihydrothiazolo[4,3-b]quinazolines and 7-methyl-4H-3,3a-dihydrothiazolo[4,3-b]quinazolines IVa and IVb is described. The N-substituted thiazolidinecarboxylic acids Ia and Ib were converted to the corresponding acid chlorides, IIa and IIb but neither reacted with silver trifluoromethanesulphonate. The carboxylic acids Ic and Id were however, decarboxylated to the corresponding iminium ions using phosphorus oxychloride and these afforded the nitroamines IIIa and IIIb. Reductive cyclisation led to the quinazolines IVa and IVb. 相似文献
12.
Bonvin Y Callens E Larrosa I Henderson DA Oldham J Burton AJ Barrett AG 《Organic letters》2005,7(21):4549-4552
[reaction: see text] Oxidation of alkyl and cycloalkyl arenes with tert-butyl hydroperoxide catalyzed by bismuth and picolinic acid in pyridine and acetic acid gave the corresponding benzylic ketones (48-99%). Alternatively, oxidation of methyl arenes gave the corresponding substituted benzoic acids (50-95%). Preliminary mechanistic studies were consistent with a radical mechanism rather than a bismuth(III)-bismuth(V) cycle. 相似文献
13.
A methodology allowing the construction of spiropiperidine scaffolds similar to those found in naturally occurring alkaloids has been developed. This approach begins with the well-established CN(R,S) strategy, the spiro-center being built by way of an intramolecular attack of a nitrile function by an organolithium species obtained by a halogen/lithium exchange reaction mediated by either t-BuLi or lithium naphthalenide. 相似文献
14.
Emmanuel Burgos 《Tetrahedron letters》2004,45(17):3465-3469
4-deoxy-4-Phosphonomethyl-d-erythronate, an isosteric and hydrolytically stable analogue of the known ribose-5-phosphate isomerase inhibitor 4-deoxy-4-phospho-d-erythronate, was obtained by a 14-step synthesis from d-arabinose through an highly improved synthesis of the precursor 5-deoxy-5-phosphonomethyl-d-arabinose. The title compound appears as the first stable and potent competitive inhibitor of the enzyme catalyzed isomerization of ribose-5-phosphate to d-ribulose-5-phosphate (Ki=74 μM, Km/Ki=100), exhibiting only a 3-fold weaker inhibitory activity than its phosphate analogue. 相似文献
15.
Wender PA Baryza JL Bennett CE Bi FC Brenner SE Clarke MO Horan JC Kan C Lacôte E Lippa B Nell PG Turner TM 《Journal of the American Chemical Society》2002,124(46):13648-13649
Macrocycle 1 is a new highly potent analogue of bryostatin 1, a promising anti-cancer agent currently in human clinical trials. In vitro, 1 displays picomolar affinity for PKC and exhibits over 100-fold greater potency than bryostatin 1 when tested against various human cancer cell lines. Macrocycle 1 can be generated in clinically required amounts by chemical synthesis in only 19 steps (LLS) and represents a new clinical lead for the treatment of cancer. 相似文献
16.
A recently introduced technique, simultaneous multiple sample light scattering (SMSLS), was used to monitor parallel polymerization reactions in situ. SMSLS is designed for real-time, high-throughput screening and provides a time-dependent light scattering signature for each reaction, which contains both qualitative and semiquantitative information. Qualitatively, the signature immediately indicates whether the reaction occurs or not, whether there is an initial lag period, and how long the reaction takes until it stops. The signature also provides estimates of the reaction rate and weight average molecular mass M(w), and its shape can help identify mechanistic aspects, for example, controlled versus free radical polymerization, presence of impurities, etc. The method is inherently adapted to small sample volumes and requires no special sample preparation or postpolymerization characterization. The demonstration here involved the free radical polymerization of acrylamide under varying conditions and should be readily applicable to a wide variety of other reactions. Results were cross-checked with multi-detector gel permeation chromatography. 相似文献
17.
Jean BourguignonUlf Bremberg Georges DupasKristina Hallman Lars HagbergLaurent Hortala Vincent LevacherSerghey Lutsenko Emmanuel MacedoChristina Moberg Guy QuéguinerFredrik Rahm 《Tetrahedron》2003,59(48):9583-9589
Chiral pyridinooxazoline, quinolinooxazoline, bis(oxazolino)pyridine (pybox), and bisoxazoline (box) derivatives containing crown ether residues were prepared. Some of the ligands were assessed in substrate binding studies and in palladium catalyzed allylic alkylations. 相似文献
18.
A short and efficient synthesis of 2'-O-methoxyethylguanosine (8) is described. Central to this strategy is the development of a novel silicon-based protecting group (MDPSCl(2), 2) used to protect the 3',5'-hydroxyl groups of the ribose. Silylation of guanosine with 2 proceeded with excellent regioselectivity and in 79% yield. Alkylation of the 2'-hydroxyl group of 6 proceeded with methoxyethyl bromide and NaHMDS and afforded compound 7 in 85% yield, without any noticeable cleavage of the silyl protecting group and without the need to protect the guanine base moiety. Finally, deprotection of 7 was achieved using TBAF and produced 8 in 97% yield. 相似文献
19.
Gas chromatography-mass spectrometry with the mass spectrometer operated in the tandem mode at a constant accelerating voltage was used to analyse for triterpanes in Arabian crude oils. Specific molecular parent-daughter ion pairs were selected for quantitative measurements owing to their metastable transitions in the first field-free region. More accurate relative distribution ratios of hydrocarbon biomarkers were determined by this sequential gating technique than by the conventional diagnostic daughter ion mass fragmentogram in common GC-MS. The data and spectra obtained from MS-MS operation may serve as unique “fingerprints” for these regional crudes 相似文献
20.
The bicyclic keto lactone 26 was synthesized for the purpose of developing a viable route to marine diterpenes of the crenulatan type. Following the efficient conversion of (S)-citronellol ( 5 ) to the allylated alcohol 9a (Scheme 2), the αβ-unsaturated lactone 12 was efficiently accessed in preparation for stereocontrolled conjugate addition. The hydroxymethyl equivalent most suited to this task was (i-PrO)Me2SiCH2MgCl, which gave 13 predominantly in the presence of CuI and Me3SiCl. Once the OH group was deprotected (→ 14 ), it proved an easy matter to implement acid-catalyzed isomerization to lactone 15 , oxidation of which gave the pivotal aldehyde 16 . Condensation of 16 with PhSeCH2Li led via 21 to 22 (Scheme 3). Once the OH group was protected (→ 22b ), it proved possible to effect aldolization with crotonaldehyde (→ 23 ). Exposure of 23 to acid gave the sub-target compound 25 . Its subsequent oxidation and thermal activation resulted in sequential selenoxide elimination with Claisen rearrangement (→ 26 ). The structural features of 26 require that a chair-like transition state be adopted during the [3.3]sigmatropic event. With the clarification of these issues, a highly serviceable and more advanced assault on the crenulatans should prove capable of being mounted. 相似文献