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21.
Anton Dmitrienko Prof. Melanie Pilkington Prof. Georgii I. Nikonov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(18):5730-5736
The AlI compound NacNacAl ( 1 , NacNac = [ArNC(Me)CHC(Me)NAr]−, Ar = 2,6-iPr2C6H3) serves as a template for the chemoselective coupling between carbonyls (benzophenone, fenchone, isophorone, p-tolyl benzoate, N,N-dimethylbenzamide, (1-phenylethylidene)aniline) and pyridine. With the CH-acidic ketone (1R)-(+) camphor, the reaction affords a hydrido alkoxide compound of Al, formed as the result of enolization, whereas an enolizable imine, (1-phenylethylidene)aniline, and the bulky ketone isophorone, still chemoselectively couple with pyridine. In contrast, reaction with the ester p-tolyl benzoate results in cleavage of the ester bond together with replacement of the alkoxy group by a hydrogen atom of the pyridine moiety. This study demonstrates that for carbonyl substrates featuring phenyl substituents, the reaction proceeds via intermediate formation of η2(C,X)-coordinated (X = O, N) carbonyl adducts, whereas the reaction of 1 with (R)-(−)-fenchone in the absence of pyridine leads to CH activation in the pendant isopropyl group of the Ar substituent of the NacNac ligand. 相似文献
22.
Dr. Eduard Baal Marius Klein Dr. Klaus Harms Prof. Dr. Jörg Sundermeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(49):12610-12618
The synthesis of 2,9-diaza-1,3,8,10-tetratriflato-dibenzoperylene (DDP 3 a ) and corresponding 2,9-dimethyl-1,3,8,10-tetratriflato-dibenzoperylene (DBP 3 b ) has been developed at multigram scale via reduction of one of the industrially most important high-performance dyes, perylene-3,4,9,10-tetracarboxylic diimide (PTCDI), and of the corresponding dihydroxy peropyrenequinone precursor. The focus of this paper is on the reactivity pattern of 3 a as key intermediate towards highly functionalized 2,9-diazadibenzopyrelenes (DDPs) obtained via catalytic substitution of four triflate by aryl, heteroaryl, alkynyl, aminyl, and O-phosphanyl substituents. The influence of electron-donating substituents (OSiMe3, OPt-Bu2, N-piperidinyl), electron-withdrawing (OTf, 3,5-bis-trifluoromethyl-phenyl), and of electron-rich π-conjugated (2-thienyl, 4-tert-butylphenyl, trimethylsilyl-ethynyl) substituents on optoelectronic and structural properties of these functionalized DDPs has been investigated via XRD analyses, UV/Vis, PL spectroscopy, and by electroanalytical CV. These results were correlated to results of DFT and TD-DFT calculations. Thus, functionalized DPPs with easily tunable HOMO and LUMO energies and gap became available via a new and reliable synthetic strategy starting from readily available PTCDI. 相似文献
23.
Dr. Ze-Jie Lv Wei Liu Miaomiao Zhu Zhengqi Chai Junnian Wei Prof. Wen-Xiong Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(66):16498-16504
Although the reaction chemistry of transition metallacyclopropenes has been well-established in the last decades, the reactivity of rare-earth metallacyclopropenes remains elusive. Herein, we report the reaction of lutetacyclopropene 1 toward a series of unsaturated molecules. The reaction of 1 with one equiv. of PhCOMe, Ar1CHO (Ar1=2,6-Me2C6H3), W(CO)6, and PhCH=NPh provided oxalutetacyclopentenes, metallacyclic lutetoxycarbene, and azalutetacyclopentene via 1,2-insertion of C=O, C≡O, or C=N bonds into Lu−Csp2 bond, respectively. However, the reaction between 1 and Ar2N=C=NAr2 (Ar2=4-MeC6H4) gave an acyclic lutetium complex with a diamidinate ligand by the coupling of one molecule of 1 with two carbodiimides, irrespective of the amount of carbodiimide employed. More interestingly, when 1 was treated with two equiv. of Ar1CHO, the reductive coupling of two C=O bonds was discovered to give a lutetium pinacolate complex along with the release of tolan. Remarkably, the reactivity of 1 is significantly different from that of scandacyclopropenes; these metallacycles derived from 1 all represent the first cases in rare-earth organometallic chemistry. 相似文献
24.
A practical and scalable synthesis of ethyl (R)-piperidine-3-acetate was achieved from commercially available 3-pyridylacetic acid in 76% overall yield. The practical synthesis was demonstrated on 100-g scale. One-pot reductive N-ethylation of the pyridinium salt with acetonitrile gave an N-ethyl piperidine derivative. 相似文献
25.
Dr. Marc Presset Dr. Jérôme Paul Ghania Nait Cherif Nisanthan Ratnam Nicolas Laloi Prof. Eric Léonel Dr. Corinne Gosmini Prof. Erwan Le Gall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(17):4491-4495
The reductive Barbier coupling of aromatic halides and electrophiles has been achieved using a CoBr2/1,10-phenanthroline catalytic system and over stoichiometric amounts of zinc. The reaction displayed a broad scope of substrates, including (hetero)aryl chlorides as pro-nucleophiles and aldehydes or imines as electrophiles, leading to diarylmethanols and diarylmethylamines in moderate to excellent yields, respectively. 相似文献
26.
An efficient synthesis of diversely substituted N,N-dimethyl-4-oxo-2-(E)-alkenamides is reported. These derivatives were obtained in three steps from I,4benzodioxin with fair to good yields 相似文献
27.
The activity of the [Pd{C6H4(CH2N(CH2Ph)2)}(µ-Br)]2 complex was investigated in the synthesis of symmetrical biaryls under both conventional and microwave irradiation conditions, and their results were compared. This complex is efficient, stable, and not sensitive to air or moisture and is a catalyst for the homo-coupling reaction of aryl iodides, bromides, and even chlorides. The products were produced in excellent yields in short reaction times using a catalytic amount of [Pd{C6H4(CH2N(CH2Ph)2)(µ-Br)]2 complex in N-methylpyrolidine (NMP) at 130 °C. In comparison to conventional heating conditions, the reactions under microwave irradiation gave better yields in shorter reaction times. 相似文献
28.
A simple Ni(dppe)Cl2/Ag2O combination has been established as an efficient catalyst system for the homo-coupling of aromatic terminal alkynes. This reaction proceeds under mild conditions and can be applied to alkynone substrates. Various aromatic 1,3-diynes were obtained in good to excellent yields. 相似文献
29.
Pinacol-type coupling reaction products presenting a high meso-diastereoselectivity (the ratio dl/meso was 4/96 up to 1/99) were obtained in fair to good yields (24–69%) using several aromatic aldehydes as starting materials and aluminium powder/copper sulfate as catalysts, in water, under reflux conditions. 相似文献
30.
Synthesis of 7-bromo-1,2,3,4-tetrahydroisoquinoline and 6-methoxy-1,2,3,4-tetrahydro-[2,7]-naphthyridine via lithiation of 2-methylarylidene-tert-butylamines, followed by formylation, reductive amination in one-pot, and removal of the tert-butyl group from the nitrogen, is described. 相似文献