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41.
42.
Palladium‐Catalyzed Carbonylations of Aryl Bromides using Paraformaldehyde: Synthesis of Aldehydes and Esters 下载免费PDF全文
Dr. Kishore Natte Dr. Andreas Dumrath Dr. Helfried Neumann Prof. Dr. Matthias Beller 《Angewandte Chemie (International ed. in English)》2014,53(38):10090-10094
Carbonylation reactions represent useful tools for organic synthesis. However, the necessity to use gaseous carbon monoxide is a disadvantage for most organic chemists. To solve this problem, novel protocols have been developed for conducting palladium‐catalyzed reductive carbonylations of aryl bromides and alkoxycarbonylations using paraformaldehyde as an external CO source (CO gas free). Hence, aromatic aldehydes and esters were synthesized in moderate to good yields. 相似文献
43.
V. V. Yanilkin E. L. Stranskaya F. F. Ngmadzyanov B. M. Garifullin 《Russian Chemical Bulletin》1996,45(3):620-622
Direct and indirect electrochemical reductive carbonylation of 2,2-dibromo 1-carbomethoxy-l-methylcyclopropane involving NiII ions and CO was studied in an McCN-benzene (3 : 1) mixture in the presence of n-PrOH and Et2NH. 2-Bromo 1-carbomethoxy-l-methylcyclopropane with cis-configuration of substituents is formed upon-direct carbonylation in the case of n-propanol, while ester or amide of I-carbomethoxy 1-methylcyclopropanecarboxylic acid are obtained in the other cases. In the presence of amine, the direct electrochemical carbonylation occurs under milder conditions and results in a different ratio of stereoisomeric products.Translated fromIzvestiya Akademii Sauk. Seriya Khimicheskaya, No. 3, pp. 659–662, March, 1996. 相似文献
44.
This article reviews recent discovery and progress of copolymerization of CO with cyclic monomers such as methylenecyclopropanes and propylene oxide promoted by transition metal complexes. 2-Aryl-1-methylenecyclopropanes react with CO in the presence of the Pd catalyst under mild conditions (1 atm, room temperature) to afford the polyketones. The reaction involves alternating insertion of the two monomers and opening of the three-membered ring of the cyclic monomers. Mechanistic study of the polymer growth revealed that 2-aryl-1-methylenecyclopropane undergoes 1,2-insertion into the Pd–acyl bond and subsequent -alkyl elimination of the cyclopropylmethylpalladium group. A bicyclic methylenecyclopropane, 7-methylenebicyclo[4.1.0]heptane, also reacts with CO in the presence of the Pd complexes with diimine ligands to afford the polyketone with six-membered rings in the repeating unit. The NMR spectra of the polyketone indicate the regulated tacticity of the monomer units. Co complexes and a mixture of Co and Ru complexes with carbonyl ligands promote the copolymerization of CO with propylene oxide in the presence of amine additives under CO pressure at 50 atm. Structures of the produced polyesters vary depending on the reaction conditions. 相似文献
45.
CuNaY分子筛的制备及其催化甲醇氧化羰基化 《燃料化学学报》2013,41(11):1361-1366
采用多种铜盐溶液与NaY分子筛离子交换制备了CuNaY催化剂,通过加入氨水提高溶液pH值以及高温活化,显著提高了该催化剂对甲醇氧化羰基化合成碳酸二甲酯的反应活性。不同的铜盐水溶液交换制备的CuNaY催化剂催化活性不同,添加氨水将溶液pH值调节为11后,离子交换制备的CuNaY催化剂的催化活性和DMC选择性明显升高且趋于一致。经元素分析、XRD、XPS和H2-TPR表征可知,加入氨水可促进Cu2+离子交换的进行,提高CuNaY催化剂中Cu的交换量,催化剂中约75%的Cu2+定位于分子筛的超笼中。 相似文献
46.
Yao Yun Hu Jing Mei Yin Da Bin Gao Ying Ping Jia Guang Yun Zhou Ying Na Cui Shen Min Li 《中国化学快报》2008,19(5):529-532
Photopromoted carbonylation of 1-bromo-6-chlorohexane with CO catalyzed by CuBr2 and CdI2 has been carried out under ambient conditions. The results indicate that the carbonylation proceeds with the major product of chloroester ClCH2(CH2)5COOCH3 under catalysis of CuBr2. Furthermore, the activity of the carbonylation can be improved by addition of basic additives (NaOAc, Na3PO4 or (n-C4H9)3N). Among these additives, (n-C4H9)3N is the most efficient in terms of the yield of ClCH2(CH2)5COOCH3. However, the methoxycarbonyl substituting chlorine product of BrCH2(CH2)5COOCH3 is not obtained in the presence of CdI2. This is quite different from the carbonylation of monochloroalkane. 相似文献
47.
Iwao Omae 《应用有机金属化学》2009,23(3):91-107
Group 9 metal compounds in organic synthesis have two characteristic reactions. The first occurs because the group 9 metals have a high affinity to carbon–carbon or carbon–nitrogen π‐bonds. The first type of characteristic reactions in these group 9 metal compounds includes Pauson–Khand reactions, the Pauson–Khand‐type reactions ([2 + 2 + 1] cyclization), the other cyclizations and coupling reactions. The second occurs because the group 9 metals have a high affinity to carbonyl groups. The second type of characteristic reactions includes carbonylations such as hydroformylations, the carbonylations of methanol, amidocarbonylations and other carbonylations. The first characteristic reactions are applied for the synthesis of fine chemicals such as pharmaceuticals and agrochemicals. However, the second characteristic reactions are utilized not only for fine chemicals but also for important bulk commodity chemicals such as aldehydes, carboxylic acids and alcohols. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
48.
Luigino Troisi Catia Granito Francesca Rosato Valeria Videtta 《Tetrahedron letters》2010,51(2):371-206
Amides can be prepared from allyl or benzyl halides and primary or secondary amines, using Pd(0) catalyst under CO pressure, in a one-pot synthesis. The reaction proceeds through the acyl palladium halide formation which undergoes an acylic nucleophilic substitution from the amine. 相似文献
49.
Satoshi Motodate Takuya Kobayashi Mikio Fujii Prof. Tomoyuki Mochida Dr. Taichi Kusakabe Shigeki Katoh Prof. Hiroyuki Akita Prof. Keisuke Kato 《化学:亚洲杂志》2010,5(10):2221-2230
Bis(oxazoline)‐palladium(II) catalyzed carbonylation of homopropargyl alcohols afforded acyclic methoxyacrylate 2 and 6‐membered lactone 3a , 3b , 3d , 3e , 3f , 3g , 3h , 3i , 3j , 3k in good combined yield. In the case of propargyl alcohols, 5‐membered lactones 3p , 3q , 16 were obtained in moderate yields. The one‐pot synthesis of kawa lactones 3a , 3r , 3s and formal synthesis of dihydroxycystothiazole A and dihydroxycystothiazole C are presented. To elucidate the stereochemistry of (+)‐annularin G and (?)‐annularin H, the first asymmetric syntheses of these natural products were achieved. 相似文献
50.
在微波辐射条件下, 将 CuCl 快速分散到载体表面制得 CuCl/SiO2-TiO2 催化剂, 利用 X 射线衍射、透射电镜、N2 吸附-脱附、热重、H2 程序升温还原和 CO 程序升温脱附对催化剂进行了表征. 结果表明, 微波辐射制备的催化剂中 CuCl 和载体发生了强相互作用, 比传统加热制备的催化剂中形成更多的易还原铜物种, 吸附 CO 的能力更强. 在甲醇液相氧化羰基化反应中, 微波辐射制备的催化剂上甲醇转化率为 11.7%, 碳酸二甲酯选择性达 96.5%, 高于相同条件下传统加热制备催化剂的活性. 相似文献