全文获取类型
收费全文 | 2777篇 |
免费 | 386篇 |
国内免费 | 210篇 |
专业分类
化学 | 3264篇 |
晶体学 | 4篇 |
综合类 | 6篇 |
物理学 | 19篇 |
综合类 | 80篇 |
出版年
2024年 | 2篇 |
2023年 | 44篇 |
2022年 | 48篇 |
2021年 | 75篇 |
2020年 | 117篇 |
2019年 | 98篇 |
2018年 | 98篇 |
2017年 | 74篇 |
2016年 | 129篇 |
2015年 | 119篇 |
2014年 | 241篇 |
2013年 | 326篇 |
2012年 | 139篇 |
2011年 | 194篇 |
2010年 | 151篇 |
2009年 | 159篇 |
2008年 | 184篇 |
2007年 | 180篇 |
2006年 | 157篇 |
2005年 | 134篇 |
2004年 | 158篇 |
2003年 | 166篇 |
2002年 | 67篇 |
2001年 | 44篇 |
2000年 | 49篇 |
1999年 | 30篇 |
1998年 | 27篇 |
1997年 | 30篇 |
1996年 | 19篇 |
1995年 | 20篇 |
1994年 | 18篇 |
1993年 | 17篇 |
1992年 | 18篇 |
1991年 | 8篇 |
1990年 | 10篇 |
1989年 | 4篇 |
1988年 | 6篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有3373条查询结果,搜索用时 62 毫秒
31.
P. M. Kochergin I. A. Mazur G. K. Rogul'chenko E. V. Aleksandrova B. E. Mandrichenko 《Chemistry of Heterocyclic Compounds》2001,37(2):224-226
Two novel preparative methods have been developed for the synthesis of 2,3-dihydroimidazo[1,2-a]pyrimidine from 2-aminopyrimidine. These are the reaction with 1,2-dibromoethane and also the reaction with ethylene chloro(bromo)hydrin, subsequent treatment of 1--hydroxyethyl-2-imino-1,2-dihydropyrimidine with thionyl chloride, and cyclization of the intermediate 1--chloroethyl-2-imino-1,2-dihydropyrimidine in the presence of sodium hydroxide. 相似文献
32.
Sixteen compounds containing the bicyclic moiety (3,8,10-trisubstituted 2,9-dioxo-5-thia-1,8-diazabicyclo[4.4.0]decane) were produced via solid-phase synthesis. Differing substitution at the 3- and 10-positions was used. These were analyzed using 2-D NMR techniques (ROESY) to determine the stereoselectivity of ring formation in the core heterocycle. Conformational analysis of the proposed transition state structure using Sybyl 6.8® was used to rationalize the stereochemical outcome of ring formation. 相似文献
33.
Tomoyuki Yoshimura 《Tetrahedron letters》2004,45(50):9241-9244
Diastereoselective construction of the 19-epi-C18-C25 segment of (−)-lasonolide A was achieved using a 5-exo-trigonal mode of radical cyclization for the creation of the contiguous quaternary and tertiary stereogenic centers at C22 and C23 as the key reaction step. During the dehydration stage, it was found that an unusual inversion of configuration took place. 相似文献
34.
氯铝酸室温离子液体介质中正碳十二烯选择环化反应 总被引:3,自引:0,他引:3
在氯化1-丙基-3-甲基咪唑(PMImCl)、氯化1-丁基-3-甲\r\n基咪唑(BMImCl)、氯化1-丁基吡啶(BPCl)和溴化1-乙基吡啶(E\r\nPBr)季铵盐与AlCl3构成的室温离子液体介质中,首次发现正十二碳烯\r\n(简称十二烯)可以高选择性地发生环化反应生成环十二烷.依次在反\r\n应管中加入氯铝酸室温离子液体、乙醇和十二烯,其中AlCl3的量为0.\r\n01mol,AlCl3与季铵盐的摩尔比为2,乙醇为10ml,十二烯为2ml(9.\r\n3mmol).当反应体系中不添加乙醇时,十二烯转化率和环十二烷选择\r\n性仅分别为4.2%和73.1%.这是由于十二烯和氯铝酸离子液体形成\r\n两相体系而不易充分接触,故十二烯转化率和环十二烷选择性较低.当\r\n反应体系中加入乙醇时,十二烯和氯铝酸离子液体体系变为单相,使得\r\n十二烯和氯铝酸离子液体可以充分接触,十二烯转化率和环十二烷选择\r\n性可分别达到12.4%和82.9%.压力对提高十二烯转化率和环十二烷\r\n选择性有很大的影响.p(N2)=3.0~6.0MPa下反应12h,十二烯转\r\n化率和环十二烷选择性可分别达到27.2%和93.8%.反应结束后加热\r\n除去乙醇,产物自动与离子液体分层,便于分离,且离子液体介质可重\r\n复使用. 相似文献
35.
A. A. Avetissian G. G. Tokmajian L. V. Karapetian 《Chemistry of Heterocyclic Compounds》2005,41(7):841-844
The reaction of 3-acetyl-4,6,6-trimethyl-5,6-dihydro-2-pyrone with the hydrazides of a series of carboxylic acids led to the
synthesis of 5-alkyl(cyanomethyl)carbonyl-3,5a,7,7-tetramethylpyrazolino-4,5-c]tetrahydro-2-pyrones, which are the products
from cyclization of the intermediately formed alkyl(cyanomethyl)hydrazones of 3-acetyl-4,6,6-trimethyl-5,6-dihydro-2-pyran.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 998–1001, July, 2005. 相似文献
36.
L. G. Shagun L. V. Klyba I. A. Dorofeev E. R. Zhanchipova I. A. Mikhailova M. G. Voronkov 《Chemistry of Heterocyclic Compounds》2007,43(2):166-168
2,5-Dimercapto-2,5-dimethyltetrahyrothiophene was synthesized by the reaction of 1-iodopropan-2-one with hydrogen sulfide
in an ether solution of hydrogen chloride at-70°C. Its structure was established by mass spectrometry, 1H and 13C NMR spectroscopy.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, 216–219, February, 2007. 相似文献
37.
The reaction of various α-silyl-α-keto esters with thiosemicarbazide at 50 °C in ethyl acetate was found to give α-silyl-substituted thiosemicarbazone-acetic acid esters in good yield. These may then be converted to their corresponding silyl-substituted 1,2,4-triazin-5-ones by cyclization under basic conditions. 相似文献
38.
39.
40.
Intramolecular cyclization reactions of 3,4-bis(indol-3-yl)maleimides 1, 3-(indol-1-yl)-4-(indol-3-yl)maleimides 2, and 3,4-bis(indol-1-yl)maleimides 3 under the action of protic acids were studied in order to estimate the parameters of the interaction between protonated and
unprotonated indole moieties. Geometric parameters, charge distributions, energy characteristics, and information concerning
the frontier orbitals of bisindolylmaleimides 1–3 were obtained from density functional B3LYP/6-31G(d) quantum chemical calculations. Alternative pathways of protonation of
bisindolylmaleimides with differently bonded indole and maleimide moieties were studied and pathways of cyclization of corresponding
conjugated acids leading to polyannelated compounds were analyzed. All the key intermediates of the cyclization reactions
correspond to stationary points on the potential energy surfaces (minima and transition states). Analysis of the potential
energy surfaces revealed almost linear dependences of the activation energies of the cyclization reactions under study on
the distances between the reaction centers, on the angle of approach of intramolecular electrophile, and on the energy gap
(energy difference between frontier orbitals). The key role in the cyclization reactions is played by structural similarity
between the starting indoleninium cations and the activated complexes of the reactions under study.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 754–760, May, 2006. 相似文献