全文获取类型
| 收费全文 | 248篇 |
| 免费 | 0篇 |
| 国内免费 | 2篇 |
专业分类
| 化学 | 157篇 |
| 晶体学 | 1篇 |
| 力学 | 11篇 |
| 数学 | 28篇 |
| 物理学 | 53篇 |
出版年
| 2022年 | 6篇 |
| 2021年 | 7篇 |
| 2020年 | 1篇 |
| 2019年 | 3篇 |
| 2018年 | 1篇 |
| 2017年 | 2篇 |
| 2016年 | 1篇 |
| 2015年 | 4篇 |
| 2014年 | 4篇 |
| 2013年 | 8篇 |
| 2012年 | 11篇 |
| 2011年 | 19篇 |
| 2010年 | 17篇 |
| 2009年 | 9篇 |
| 2008年 | 13篇 |
| 2007年 | 16篇 |
| 2006年 | 17篇 |
| 2005年 | 12篇 |
| 2004年 | 8篇 |
| 2003年 | 4篇 |
| 2002年 | 9篇 |
| 2001年 | 5篇 |
| 2000年 | 6篇 |
| 1999年 | 4篇 |
| 1998年 | 3篇 |
| 1997年 | 6篇 |
| 1996年 | 5篇 |
| 1995年 | 1篇 |
| 1994年 | 6篇 |
| 1993年 | 2篇 |
| 1992年 | 5篇 |
| 1991年 | 2篇 |
| 1990年 | 1篇 |
| 1989年 | 3篇 |
| 1988年 | 4篇 |
| 1987年 | 3篇 |
| 1986年 | 5篇 |
| 1985年 | 1篇 |
| 1984年 | 1篇 |
| 1983年 | 1篇 |
| 1980年 | 2篇 |
| 1979年 | 4篇 |
| 1978年 | 3篇 |
| 1977年 | 1篇 |
| 1976年 | 1篇 |
| 1975年 | 1篇 |
| 1974年 | 1篇 |
| 1969年 | 1篇 |
排序方式： 共有250条查询结果，搜索用时 15 毫秒
181.
Kuo-Liang Chiou 《Journal of Differential Equations》1978,28(1):104-123
The study of stability behavior of the canonical system is closely linked to the geometrical properties of indefinite J-spaces. Using results from the theory of indefinite J-spaces and studying the locus of the spectrum of the monodromy operator of (1) we provide several new sufficient conditions for stability behavior of (1) and its special forms. Moreover, we extend M. G. Neǐgauz and V. B. Lidskiǐ's criterion to the infinite-dimensional case. To study stability criteria for the system , under suitable conditions we transform (7) into a Hamiltonian system and then use stability criteria for Hamiltonian systems to obtain several new stability criteria. These new stability criteria generalize or are related to R. W. Brockett's criterion. We also give some relationships between system (7) and Hamiltonian systems. Moreover, via classical methods we obtain several new stability criteria for (7) which are related to the Nyquist criterion and circle criteria (Brockett). 相似文献
182.
183.
Multisubstituted pyrroles are important fragments that appear in many bioactive small molecule scaffolds. Efficient synthesis of multisubstituted pyrroles with different substituents from easily accessible starting materials is challenging. Herein, we describe a metal-free method for the preparation of pentasubstituted pyrroles and hexasubstituted pyrrolines with different substituents and a free amino group by a base-promoted cascade addition–cyclization of propargylamides or allenamides with trimethylsilyl cyanide. This method would complement previous methods and support expansion of the toolbox for the synthesis of valuable, but previously inaccessible, highly substituted pyrroles and pyrrolines. Mechanistic studies to elucidate the reaction pathway have been conducted.This method is a toolbox for the synthesis of valuable, but previously inaccessible, highly substituted pyrroles and pyrrolines.Pyrroles are molecules of great interest in a variety of compounds including pharmaceuticals, natural products and other materials. Pyrrole fragments for example are key motifs in bioactive natural molecules, forming the subunit of heme, chlorophyll and bile pigments, and are also found in many clinical drugs, including those in Fig. 1a.1 Although many classical methods of pyrrole synthesis, including the Paal–Knorr condensation,2 the Knorr reaction,3 the Hantzsch reaction,4 transition metal-catalyzed reactions,5 and multicomponent coupling reactions,6 have been developed over many years, the efficient synthesis of multisubstituted pyrroles is still challenging. In condensation syntheses of pyrroles, the major problems lie in the extended syntheses of complex precursors and limited substitution patterns that are allowed. Multicomponent reactions are superior when building pyrrole core structures with more substituents. Among these, the [2+2+1] cycloaddition reaction of alkynes and primary amines is attractive because of the readily available alkyne and amine substrates and the ability to construct fully substituted pyrroles.7 However, with the exception of some rare examples,8 most [2+2+1] cycloaddition reactions afford pyrroles with two or more identical substituents. The synthesis of multisubstituted pyrroles with all different substituents from simple starting materials therefore remains a major challenge.Open in a separate windowFig. 1Previous reports and this work on propargylamides transformation.Easily accessible propargylamides are classical, privileged building blocks broadly utilized for the synthesis of a large variety of heterocyclic molecules such as pyrroles, pyridines, thiazoles, oxazoles and other relevant organic frameworks.9 For example, Looper10et al. reported the synthesis of 2-aminoimidazoles from propargyl cyanamides and Eycken11 reported a method starting from propargyl guanidines which undergo a 5-exo-dig heterocyclization as shown in Fig. 1b. Subsequently, Wan12et al. revealed the cyclization of N-alkenyl propargyl sulfonamides into pyrroles via sulfonyl migration. Inspired by these transformations and multi-substituted pyrrole synthesis, we report herein a direct synthesis of pentasubstituted pyrroles and hexasubstituted pyrrolines with all different substituents from propargyl sulfonylamides and allenamides.Previously, Zhu,13 Ji14 and Qiu13b,15 reported efficient syntheses of 2-aminopyrroles from isocyanides. Ye16 and Huang17 independently developed gold-catalyzed syntheses of 2-amino-pentasubstituted pyrroles with ynamides. Despite the many advantages of these methods, they all afford protected amines, rather than free amines. The deprotection of these amines may cause problems in further transformations of the products. Our method delivers pyrroles with an unprotected free amino group and are often complementary to the previously well-developed classical methods.Initially, the cyclization reaction of N-(1,3-diphenylprop-2-yn-1-yl)-N-ethylbenzenesulfonamide (1a) with trimethylsilyl cyanide (TMSCN) was carried out with Ni(PPh3)2Cl2 as a catalyst, a base (Cs2CO3) and DMF as a solvent. Different metal catalysts, such as Ni(PPh3)2Cl2, Pd(OAc)2, Cu(OAc)2, and Co(OAc)2 provided the desired product with similar yields (Table 1, entries 1–4), suggesting that this reaction probably does not benefit from a metal catalyst. The reaction without any metal catalyst was conducted and as suspected, the same yield of 2a was obtained (Table 1, entry 5). In order to further optimize the reaction conditions, different bases, such as KF, K3PO4, K2CO3, KOH, KOtBu, and Et3N were investigated but failed to deliver a better result (Table 1, entries 6–11). Screening of solvents indicated that DMF is optimal for this transformation (Table 1, entries 12–16).Optimization of the reaction conditionsa
Open in a separate windowaReaction conditions: 1a (0.1 mmol, 1 equiv.), TMSCN (0.3 mmol, 3 equiv.), cat. (0 or 10 mol%), base (0.3 mmol, 3 equiv.) and solvent (1 mL), at 80 °C for 10 h; isolated yield.With the optimal reaction conditions in hand, we investigated the scope of this reaction. As shown in Fig. 2, the transformation tolerates a broad variety of substituted propargylamides (1). The R1 group could be an aryl group containing either electron-donating groups or electron-withdrawing groups, and the corresponding products (2b–2h) were obtained in yields of 62–80%. The substituent R1 could also be an alkyl group such as 1-hexyl in which case the reaction provided the corresponding pyrrole (2i) in 53% yield. Exploration of the R2 substituent was also conducted. Electron-rich and electron-deficient substituents in the aromatic ring of R2 gave the desired products (2j–2o) with yields of 70–81%. The product bearing a furyl group (2p) can be produced in 61% yield. However, when R2 group is an aliphatic group, the reaction failed to provide the desired product. Substituent groups R3, such as benzyl (2q) or 3,4-dimethoxyphenylethyl (2r) were also compatible in the reaction, providing the corresponding products in moderate yields. Significantly, this method has the potential to produce core structures (for example 2s) similar to that in Atorvastatin. Interestingly, when alkynyl substituted isoquinolines (1t–1v) were used as the substrates, the reactions smoothly afforded fused pyrrolo[2,1-α]isoquinoline derivatives (2t–2v), members of a class of compounds that are found widely in marine alkaloids and exhibit anticancer and antiviral activity.18Open in a separate windowFig. 2Substrate scope of propargylamides. Reaction conditions: 1 (0.20 mmol, 1 equiv.), TMSCN (0.60 mmol, 3 equiv.), Cs2CO3 (0.60 mmol, 3 equiv.) and DMF (2 mL), at 80 °C for 10 h; isolated yield.Allenes are key intermediates in the synthesis of many complex molecules.19 As a subtype of allenes, allenamines are also useful as reaction intermediates.20 Although the transformation of allenamides to multisubstituted pyrroles has not been previously recorded, this reaction probably goes through the allenamide intermediates which can be derived from propargyl sulfonamides under basic conditions. To verify this hypothesis, the trisubstituted allenamide (3) was synthesized and subjected to the standard reaction conditions. A pyrrole (2a) was isolated in 82% yield from this reaction (Fig. 3). This result confirmed our assumption and raised a new question: is it possible to build hexasubstituted pyrrolines from tetrasubstituted allenamides? A range of tetrasubstituted allenamides21 was tested under the standard reaction conditions, and the hexasubstituted pyrrolines were obtained as is shown in Fig. 4. The R1 group could be an aryl substituent or an alkyl chain, and the corresponding products (5a–5e) were obtained with good yields. Various aryl groups with either electron-donating groups or electron-withdrawing groups in the aromatic ring of R2 provided the desired products (5f–5k) in 62–83% yields. In addition, the difluoromethyl group can also be replaced by a phenyl group, and the reaction provided the corresponding product 5l in 82% yield. It is worth noting that these pyrroline products are not easily accessible from other methods.Open in a separate windowFig. 3Synthesis of substituted pyrroles from allenes.Open in a separate windowFig. 4Substrate scope of tetrasubstituted allenamides. Reaction conditions: 4 (0.10 mmol, 1 equiv.), TMSCN (0.30 mmol, 3 equiv.), K2CO3 (0.30 mmol, 3 equiv.) and DMF (1 mL), at 80 °C for 10 h, isolated yield.Some synthetic applications of this method are shown in Fig. 5. The amide is a naturally occurring and ubiquitous functional group. When using benzoyl chloride to protect the free amino group of the fully-substituted pyrrole (2a), a bis-dibenzoyl amide (6) was obtained in the presence of a base, triethylamine while the monobenzoyl protected amide (7) was obtained in the presence of pyridine as the base (Fig. 5a). This method also provides a straightforward approach to pyrrole fused lactam structures (Fig. 5b). For examples, a five-membered lactam and a six-membered lactam were generated separately in a one pot reaction, directly from, (8 and 10), respectively. Taking advantage of this method, an analogue of the drug Atorvastatin was synthesized in 5 steps (Fig. 5c), demonstrating the synthetic value of the reaction.Open in a separate windowFig. 5Synthetic applications.Mechanistic experiments were performed (Fig. 6) to explore the mechanism of the reaction. When 3 equivalents of TEMPO were added, the reaction was not inhibited and the desired product (2a) was formed in 62% yield (Fig. 6a). This result suggested that the reaction might not involve a radical process. To probe the reaction further, a kinetic study was conducted (Fig. 6b). According to this study, the propargylamide (1a) was completely converted to an allenamide (3a) in 10 min under the standard conditions. The multi-substituted pyrrole (2a) was then gradually produced from the intermediate allenamide and no other reaction intermediates were observed or identified. On the other hand, DFT calculations of substrates 3b and 4a were carried out at the B3LYP-D3(SMD)/Def2-TZVP//B3LYP-D3/Def2-SVP level of theory to identify the natural bond orbital (NBO) charges on the carbons of the allene moieties. NBO charges on the internal carbon in both 3b and 4a are 0.11 and 0.18, respectively (Fig. 6c) indicating that the nucleophilic addition of cyanide anion onto the internal carbon should be reasonable as opposed to its addition onto the terminal carbon. Pathways of the cyano addition to 3b were also calculated (Fig. 6d). The transition state of cyano addition on the internal carbon (TS1), is indeed much lower than addition on the terminal carbon (TS2). The intermediate of internal carbon addition int1, is more stable than int2, implying that the internal carbon addition pathway is not only kinetically but also thermodynamically favoured.Open in a separate windowFig. 6Mechanistic studies and proposed mechanism.Based on the results of these mechanistic studies, a plausible reaction mechanism for the synthesis of pentasubstituted pyrroles and hexasubstituted pyrrolines is proposed and is shown in Fig. 6e. First, under basic conditions, the propargylamide isomerizes to an intermediate allenamide (A), which can be attacked nucleophilically by the cyanide anion to afford an intermediate imine (B) with release of the sulfonyl group. Then, the second cyanide anion attacks the imine to form an intermediate (C), which can undergo cyclization and protonation to afford the fully substituted pyrrole (2). Similarly, the hexasubstituted pyrroline product (5) can be obtained from double nucleophilic attack of the intermediate (A) by the cyanide ion. 相似文献
| Entry | Cat. | Base | Solvent | Yield |
|---|---|---|---|---|
| 1 | Ni(PPh3)2Cl2 | Cs2CO3 | DMF | 67% |
| 2 | Pd(OAc)2 | Cs2CO3 | DMF | 65% |
| 3 | Cu(OAc)2 | Cs2CO3 | DMF | 65% |
| 4 | Co(OAc)2 | Cs2CO3 | DMF | 63% |
| 5 | Cs2CO3 | DMF | 65% | |
| 6 | KF | DMF | Trace | |
| 7 | K3PO4 | DMF | Trace | |
| 8 | K2CO3 | DMF | 48% | |
| 9 | KOH | DMF | 52% | |
| 10 | KOtBu | DMF | 46% | |
| 11 | Et3N | DMF | Trace | |
| 12 | Cs2CO3 | CH3CN | 18% | |
| 13 | Cs2CO3 | DME | 23% | |
| 14 | Cs2CO3 | Toluene | Trace | |
| 15 | Cs2CO3 | DCE | Trace | |
| 16 | Cs2CO3 | Dioxane | Trace |
184.
Elemental selenium and tellurium, and gaseous inorganic forms of Se(IV), Se(VI), Te(IV) and Te(VI) have been determined after their adsorption on gold-coated beads. After leaching, with water and dilute hydrochloric and nitric acids, the different chemical species in each acid fraction were separated with an anion-exchange resin (Bio-Rad AG-1X8) and a cation-exchange resin (Amberlite IR-120 Plus) by varying the acidity of the leaching agent. Subsequent analysis was by graphite-fumace atomic-absorption spectrometry. The lower detection limit for Se and Te was 0.03 ng/M(3) with a precision of +/- 5%. The average amounts of selenium in interior and exterior air samples were about 4.73 and 1.93 ng/m(3) respectively. For tellurium the corresponding values were about 0.78 and 0.24 ng/m(3). 相似文献
185.
The synthesis, absorption and emission spectra, fluorescence quantum yields, and fluorescence lifetimes of three compound series of trans-4,4'-disubstituted aminostilbenes (1-3) are reported. The chromo-/fluoroionophoric behavior of the monoaza-15-crown-5- (A15C5) and monoaza-18-crown-6 (A18C6)-derived species (1A(5)()-3A(5)() and 1A(6)()-3A(6)()) in acetonitrile and dichloromethane are also investigated. Great similarities in electronic spectroscopic properties (chemical shifts, wavelength, intensity, and lifetime) between the metal ion-complexed supermolecules and the corresponding chloro-substituted molecules have been observed: namely, 1A(5)()/Ca(2+)-3A(5)()/Ca(2+) approximately 1A(6)()/Ba(2+)-3A(6)()/Ba(2+) approximately 1C-3C in acetonitrile and 1A(5)()/Na(+)-2A(5)()/Na(+) approximately 1A(6)()/K(+)-2A(6)()/K(+) approximately 1C-2C in dichloromethane. Such spectroscopic correlations allow us to define the metal ion-modulated electronic character of the azacrown nitrogen atom in the ground and excited states and, in turn, to gain insights into the observed fluoroionophoric behavior of these probes in terms of the size and direction of fluorescence shifts and intensity variations. 相似文献
186.
A one-step conversion of l-tryptophan and activated aldehydes (1,2-dicarbonyl compounds) directly to 1-substituted β-carbolines without formation of the tetrahydro derivatives under modified Pictet-Spengler conditions was described. Moreover, a practical application for the synthesis of a natural 1-substituted β-carboline, luzongerine A, isolated from Illigera luzonensis was also successfully carried out utilizing this protocol. The effects of synthetic compounds 11 and 11a on nitric oxide (NO) production in LPS/IFN-γ stimulated RAW 264.7 macrophage cells were evaluated in vitro. They displayed significant dose-dependent inhibition of inducible nitric oxide synthase (iNOS). 相似文献
187.
The unprecedented nickel(III) thiolate [Ni (III)(OR)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) [R = Ph ( 1), Me ( 3)] containing the terminal Ni (III)-OR bond, characterized by UV-vis, electron paramagnetic resonance, cyclic voltammetry, and single-crystal X-ray diffraction, were isolated from the reaction of [Ni (III)(Cl)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) with 3 equiv of [Na][OPh] in tetrahydrofuran (THF)-CH 3CN and the reaction of complex 1 with 1 equiv of [Bu 4N][OMe] in THF-CH 3OH, respectively. Interestingly, the addition of complex 1 into the THF-CH 3OH solution of [Me 4N][OH] also yielded complex 3. In contrast to the inertness of complex [Ni (III)(Cl)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) toward 1 equiv of [Na][OPh], the addition of 1 equiv of [Na][OMe] into a THF-CH 3CN solution of [Ni (III)(Cl)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) yielded the known [Ni (III)(CH 2CN)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) ( 4). At 77 K, complexes 1 and 3 exhibit a rhombic signal with g values of 2.31, 2.09, and 2.00 and of 2.28, 2.04, and 2.00, respectively, the characteristic g values of the known trigonal-bipyramidal Ni (III) [Ni (III)(L)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) (L = SePh, SEt, Cl) complexes. Compared to complexes [Ni (III)(EPh)(P(C 6H 3-3-SiMe 3-2-S) 3)] (-) [E = S ( 2), Se] dominated by one intense absorption band at 592 and 590 nm, respectively, the electronic spectrum of complex 1 coordinated by the less electron-donating phenoxide ligand displays a red shift to 603 nm. In a comparison of the Ni (III)-OMe bond length of 1.885(2) A found in complex 3, the longer Ni (III)-OPh bond distance of 1.910(3) A found in complex 1 may be attributed to the absence of sigma and pi donation from the [OPh]-coordinated ligand to the Ni (III) center. 相似文献
188.
R. B. Prime G. Y. Chiou R. J. Twieg 《Journal of Thermal Analysis and Calorimetry》1996,46(3-4):1133-1150
Optical data storage is poised to benefit from a new class of advanced polymeric materials engineered to exhibit photorefractivity. Likewise, the transmission and processing of data will also benefit from a related class of materials with electro-optic activity. Organic chromophores are critical constituents of these materials which function due to a change of index of refraction in response to an electric field. However, a number of materials and processing problems remain to be solved before devices incorporating these optically nonlinear chromophores are practical. For example, for electrooptical applications the NLO waveguide should be able to withstand short duration processing temperatures in excess of 300°C and long duration use temperatures of at least 80°C. The requirement for thermochemical stability follows from the need to implement highT
g matrices to provide stability of the orientational or polar order required for long-term device performance and reliability. As a result, the thermal stability of chromophores is now more closely evaluated in addition to their transparency and optical nonlinearity properties. Some chromophore classes, such as the azo dyes studied here, have attractive properties for these applications but further enhancements in overall properties are needed. Identification of the fundamental chemical processes in thermal decomposition of these dyes should lead to introduction of structural changes which provide better stability. Here thermogravimetric analysis (TGA) coupled with mass spectrometry (TGA/MS) is used to provide an assay of thermochemical stability with an added benefit that insight into the mechanisms of thermal decomposition may by identified. In this initial study diaryl substitution of the amine in derivatives of 4-amino-4-nitroazobenzene was observed to greatly enhance thermal stability relative to dialkyl substitution. Substitution of phenyl for alkyl eliminates structural features involved in the most facile degradation mechanism available to the alkyl derivative.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThe authors acknowledge contributions by colleagues at IBM including H. Truong and R. Siemens for the thermal analysis. This work was supported by the Air Force Office of Scientific Research and the National Institute of Science and Technology Advanced Technology Program. 相似文献
189.
190.
The configurations of several 1,4- (= 2,5-) disubstituted adamantanes have been determined by means of X-ray diffraction. Since these compounds have rigid skeletons and since there is almost no difference in stability or steric requirements between the geometric isomers, these epimers are expected to be very useful for stereochemical studies. 相似文献