全文获取类型
收费全文 | 383篇 |
免费 | 4篇 |
国内免费 | 4篇 |
专业分类
化学 | 270篇 |
晶体学 | 8篇 |
力学 | 7篇 |
数学 | 77篇 |
物理学 | 29篇 |
出版年
2021年 | 6篇 |
2018年 | 2篇 |
2017年 | 4篇 |
2016年 | 4篇 |
2015年 | 3篇 |
2014年 | 13篇 |
2013年 | 16篇 |
2012年 | 15篇 |
2011年 | 8篇 |
2010年 | 10篇 |
2009年 | 10篇 |
2008年 | 14篇 |
2007年 | 15篇 |
2006年 | 20篇 |
2005年 | 12篇 |
2004年 | 11篇 |
2003年 | 8篇 |
2002年 | 9篇 |
2001年 | 7篇 |
2000年 | 4篇 |
1999年 | 12篇 |
1998年 | 29篇 |
1997年 | 26篇 |
1996年 | 13篇 |
1995年 | 12篇 |
1994年 | 7篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 4篇 |
1970年 | 2篇 |
1969年 | 2篇 |
1968年 | 2篇 |
1964年 | 4篇 |
1963年 | 3篇 |
1962年 | 2篇 |
1954年 | 2篇 |
排序方式: 共有391条查询结果,搜索用时 31 毫秒
91.
Mario Merslavič Branko Stanovnik Miha Tišler 《Monatshefte für Chemie / Chemical Monthly》1985,116(12):1447-1458
New syntheses of oxazolo[4,5—d]pyridazine derivatives7 and11 were achieved by the cyclization of substituted N-pyridazin-5-ylformamide oximes6 and10. Under mild reaction conditions the transformations of the substituted amino group at position 2 of the oxazolo[4,5—d]pyridazine system7 occured to produce the compounds11, 14, and15, while under more drastic reaction conditions the nucleophilic attack at carbon at position 2 followed by the ring opening of the oxazole part of the molecule was observed to give the compounds13, 16, 17 and18.
Transformationen von N-Heteroarylformamidinen und N-Heteroarylformamidinoximen. Neue Synthesen und Transformationen von Oxazolo[4,5—d]pyridazinen
Zusammenfassung Mittels Cyclisierung substituierter N-Pyridazin-5-ylformamidoxime6 und10 wurden neue Synthesemöglichkeiten von Oxazolo[4,5—d]pyridazinderivaten erschlossen. Bei milden Reaktionsbedingungen trat Transformation der substituierten Aminogruppe an Position 2 des Oxazolo[4,5—d]pyridazin-Systems unter Bildung der Verbindungen11, 14 und15 ein, währenddessen unter drastischeren Reaktionsbedingungen ein nucleophiler Angriff am Kohlenstoff-2, gefolgt von einer Ringöffnung unter Bildung der Verbindungen13, 16, 17 und18 eintrat.相似文献
92.
Jurij Svete Branko Stanovnik Miha Tiler Ljubo Goli
Ivan Leban 《Journal of heterocyclic chemistry》1989,26(1):145-153
From heteroarylaminomethyleneoxazolones 4 , obtained from N-heteroarylformamidines 2 and 2-phenyl-5-oxo-4,5-dihydro-1,3-oxazole ( 3 ), the following β-heteroarylamino-α,β-dehydro-α-amino acid derivatives were prepared: methyl 8 and ethyl esters 9 , amides 10 and 11 , hydrazides 12 , and azides 15 . By catalytic hydrogenation the compounds 4 were converted into β-heteroarylamino substituted amides 18 and β-heteroarylamino-α-amino acids 20 . 相似文献
93.
Branko Kozuilić Ivančica Leuštek Branka Pavlović Pavao Mildner Slobodan Barbarić 《Applied biochemistry and biotechnology》1987,15(3):265-278
Each of the three high-mannose type glycoproteins studied, acid phosphatase, invertase, and glucose oxidase, could be specifically
cross-linked through its carbohydrate chains. The procedure involves periodate oxidation of carbohydrate residues followed
by reaction of the generated aldehyde groups with adipic acid dihydrazide as a cross-linker. The amount and size as well as
solubility of the formed polymers could be efficiently controlled by varying the reaction conditions, i.e., the oxidation
degree and the concentrations of glycoproteins, cross-linker, and hydrogen ions during the cross-linking reaction. It was
found that the quantity and size of polymers increased with oxidation degree and protein concentration and by lowering the
pH. When the protein concentration was above and pH below certain values, depending on the glycoenzyme, insoluble polymers
formed. The soluble cross-linked polymers retained a high level of original activity, and the minor decrease in specific activity
noticed was shown to occur during the periodate oxidation step. The cross-linked glycoenzymes are much more resistant to denaturation
by high temperature and by changes in pH, demonstrating the usefulness of this method in preparation of the stabilized glycoprotein
derivatives. 相似文献
94.
2-Alkoxy-4-heteroarylaminomethylene-5(4H)-thiazolones 4 were converted with various nucleophiles into β-heteroarylamino-α,β-dehydro-α-amino acid derivatives 11, 14, 15, 16, 17, 18 , and 19 . Reduction of 4 with sodium borohydride in ethanol saturated with gaseous ammonia afforded the corresponding β-heteroaryl-amino substituted alanyl amides 20 . Thiazoledione derivative 7a was transformed with sodium methoxide in methanol into 1-(4,6-dimethylpyrimidinyl-2)-4-mercaptocarbonylimidazol-2(3H)-one ( 8a ). 相似文献
95.
In the search for potential immunomodulators methyl L-(—)-thiazolidine-4-carboxylate (2), 2-amino-2-thiazoline (12), and 2-aminothiazole (19) were transformed into derivatives of various bicyclic systems. Thus, from compound 2 derivatives of perhydrothiazolo[3,4-a]pyrazine 4 and 5, perhydrothiazolo[4,3-c]-[1,4]oxazine 7, and perhydroimidazo[1,5-c]thiazole 9a,b, from compound 12 derivatives of 2,3-dihydro-thiazolo[2,3-b]pyrimidine 13a,b , and from compound 19 derivatives of imidazo[2,1-b]thiazole 21, 22, 24, and 25 were prepared. 6-(p-Sulfamoylphenyl)-7-oxoperhydroimidazo[1,5-c]thiazole-5-thione (9a) was found to exhibit immunorestoration activity. 相似文献
96.
The transformation of 2-acetyl-5-substituted-tetrazoles into the corresponding 1,3,4-oxadiazoles was studied with the
semiempirical and
ab initio methods. Two mechanisms, one with two transition states and the other with three, were elucidated by
. The first mechanism supported by PM3 and MNDO has a two-step, almost concerted, mechanism for the elimination of a nitrogen molecule from the tetrazole ring and formation of the oxadiazole product from an open-chain intermediate through carbon C5 and acetyl oxygen bond formation. The second mechanism supported by AM1 and MINDO/3 breaks the elimination of the nitrogen molecule into two steps: first breaking the N4-C5 and then the N2-N3 bonds. Even when the AM1 and MINDO/3 transition state structures were optimized by PM3 and MNDO, the obtained transition states present only one bond breaking. The HF/STO-3G and HF/3-21G ab initio methods agree with the first mechanism where two bonds are breaking almost simultaneously. Despite the disagreement in the mechanism of the nitrogen elimination, the transition state that presents the product formation from open-chain intermediates is quite similar for all methods studied. The semiempirical calculation of this transition state is possible only if it is assumed that it has biradical character. The activation energies calculated by PM3 seem to be insensitive to the nature of the substituents. 相似文献
97.
Branko S. Brčić Marko Bulc Jože Šiftar Anton Urbanc 《Monatshefte für Chemie / Chemical Monthly》1964,95(1):248-256
Zusammenfassung Der zeitliche Verlauf der Oxydation von granuliertem Blei ist unregelmäßig, weil sich dessen Oberfläche während der Reaktion nicht konstant vermindert. Die Reaktion verläuft an der Luft mit und ohne CO2 mit gleicher Geschwindigkeit, weil auch an der Luft nur eine Mischung von Bleioxyd und Hydroxydcarbonat entsteht. Auf die geometrische Oberfläche bezogen, hat die Oxydationsgeschwindigkeit unter den beschriebenen Bedingungen eine Größenordnung von 0,6 g/dm2h. Auch die Abhängigkeit der oxydierten Bleimenge vom Partialdruck des Sauerstoffes (0,00–0,21) wurde bestimmt. Die Bleikonzentration hat in breitem Intervall praktisch keinen Einfluß. Der Lichteinfluß ist positiv, auf die Reaktion in der Dunkelheit bezogen, ist die oxydierte Bleimenge 1,2mal höher. Die Bedingungen für die Herstellung von tetragonalem Bleioxyd, dessen Bildung über das rhombische Bleioxyd verläuft, werden wiedergegeben.Mit 3 Abbildungen 相似文献
98.
Methyl 2-benzoylamino-3-oxobutanoate ( 3 ) was prepared from hippuric acid (1) which was converted with N,N-dimethylacetamide and phosphorus oxychloride into 4-(1-dimethylaminoethylidene)-2-phenyl-5(4H)-oxazolone ( 2 ) followed by hydrolysis with hydrochloric acid in methanol. Compound 3 was treated with hydrazines 4 to give 4-benzoylamino-3-methyl-1H-pyrazol-5(2H)-one ( 6a ) and its 1-substituted derivatives 6b-j . The corresponding hydrazones 5f, i, j were isolated as intermediates. 相似文献
99.
David Bevk Uro Groelj Anton Meden Jurij Svete Branko Stanovnik 《Helvetica chimica acta》2006,89(11):2774-2782
A simple and efficient synthesis of novel 2‐heteroaryl‐substituted 1H‐indole‐2‐carboxylates and γ‐carbolines, compounds 1 – 3 , from methyl 2‐(2‐methoxy‐2‐oxoethyl)‐1‐methyl‐1H‐indole‐3‐carboxylate ( 4 ) by the enaminone methodology is presented. 相似文献
100.
A novel simple synthesis of 5-substituted-1,2,4-oxadiazole-3-carboxylates 5 from N-acylglycines 1 , which are transformed with DMF in the presence of phosphorus oxychloride into 2-substituted-4-dimethyl-aminomethyleneoxazol-5(4H)-ones 2 , followed by opening into 2-aroylamino-3-dimethylamino-propenoates 3 , and nitrosation to give the oximes 4 as intermediates, which cyclize spontaneously into 5-substituted-1,2,4-oxadiazole-3-carboxylates 5 . The compounds 2 can be transformed into 5 without isolation of 3 and 4 . 相似文献