全文获取类型
收费全文 | 120篇 |
免费 | 5篇 |
专业分类
化学 | 106篇 |
晶体学 | 1篇 |
力学 | 1篇 |
数学 | 3篇 |
物理学 | 14篇 |
出版年
2023年 | 1篇 |
2021年 | 2篇 |
2019年 | 1篇 |
2018年 | 1篇 |
2016年 | 4篇 |
2015年 | 3篇 |
2014年 | 1篇 |
2013年 | 3篇 |
2012年 | 1篇 |
2011年 | 4篇 |
2010年 | 4篇 |
2009年 | 3篇 |
2008年 | 10篇 |
2007年 | 10篇 |
2006年 | 8篇 |
2005年 | 11篇 |
2004年 | 9篇 |
2003年 | 13篇 |
2002年 | 9篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1999年 | 1篇 |
1998年 | 2篇 |
1996年 | 2篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1989年 | 2篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有125条查询结果,搜索用时 15 毫秒
1.
2.
The separation of diastereomeric esters derived from (±)-pyridylethanols and 3β-acetoxyetienic acid were achieved by an extraction technique using diethyl ether and aqueous hydrochloric acid. A formal total synthesis of PNU-142721 was effectively carried out to prepare the chiral, non-racemic synthon 1-furo[2,3-c]pyridin-5-yl-ethanol (1) by means of this technique. The structure optimized using MOPAC calculations on each diastereomer suggested the presence of intramolecular CH/π interaction in only the (S)-isomer of the diastereomers. 相似文献
3.
Paterno-Buchi coupling, photochemical [2 + 2] cycloaddition, of carbonyl compounds 2a-f with 2-siloxyfurans 1a-d has been investigated in detail. The stereoselective formations of exo-oxetanes 3 and 4 were observed in high yields. The regioselectivity (double-bond selection, 3 vs 4) was found to be largely dependent upon the carbonyls, the substituents at the furan ring, and the excited state of the carbonyls (singlet vs triplet). The photoreaction of aldehydes 2a-c gave bicyclic exo-oxetanes 3 and 4 at regio-random, independent upon their excited states and the substituents at furan ring. However, the photoreaction of the triplet state of ketones 2d-f was found to give regioselectively exo-oxetanes 4, except for the 4-methyl-2-siloxyfurane 1d case. The singlet-excited state of acetone 2f gave both oxetanes 3 and 4 at regio-random. For the singlet-state photochemistry, the approach direction of the electrophilic oxygen of the excited carbonyls to the furan ring is proposed to be an important factor for the exo-stereoselection. The Griesbeck model can rationalize the regio- and exo-selective formation of oxetanes in the triplet-state photoreaction. 相似文献
4.
5.
Generation of singlet and triplet 2-silylcyclopentane-1,3-diyls and their reactivity have been investigated in the thermal and photochemical denitrogenation of 2,3-diaza-7-silylbicyclo[2.2.1]hept-2-ene. 5-Silylcyclopentene (silyl migration product) is quantitatively obtained, while 5-silylbicyclo[2.1.0]pentane (intramolecular ring-closure product) is not detected in the denitrogenation reactions. Deuterium labeling studies clarify that 5-silylcyclopentene is formed by a suprafacial [1,2] silyl migration in singlet 2-silylcyclopentane-1,3-diyl. UDFT calculations closely reproduce the observed reactivity of the singlet diradical: The enthalpic barriers of the intramolecular ring-closure are calculated to be DeltaH++exo468 = 5.8 kcal/mol and DeltaH++endo468 = 6.7 kcal/mol, which are much higher than the energy barrier for the [1,2] silyl migration, DeltaH++468 = 2.7 kcal/mol. The notable effect of the silyl group on raising the energy barrier of the intramolecular cyclization is rationalized by an electronic configuration of the lowest singlet state of 2-silylcyclopentane-1,3-diyls. 相似文献
6.
Abe M Adam W Hara M Hattori M Majima T Nojima M Tachibana K Tojo S 《Journal of the American Chemical Society》2002,124(23):6540-6541
Photodenitrogenation of the diazenes 4 affords exclusively the housanes 5 through intramolecular cyclization of the spectrally detected and characterized singlet diradicals 3. The lifetime of singlet diradical 3, determined by transient absorption measurements, depends on the Y and Z substituents at the para position of the phenyl ring and has the following order: Y, Z = OMe, OMe > OMe, CN > CN, CN > OMe, H > Cl, Cl approximately CN, H approximately Me, Me > H, H. This unprecedented substituent effect reveals stabilization of the singlet 2,2-dimethoxycyclopentane-1,3-diyl diradicals 3 through radical, zwitterionic, pi-bonding, and hyperconjugative structures. 相似文献
7.
Shoichi Kutsumizu Koushi Morita Tatsuya Ichikawa Shinichi Yano Shuichi Nojima Takanari Yamaguchi 《Liquid crystals》2013,40(11):1447-1458
The structure of the thermotropic cubic phases of 4′- n -alkoxy-3′-nitrobiphenyl-4-carboxylic acids (ANBC- n , where n indicates the number of carbon atoms in the alkoxy group) was studied by X-ray diffraction. For the homologues with n = 15, 16, 17, and 18, the cubic phase was of an Ia 3 d type, whereas the homologues with n = 19, 20, and 21 exhibited an Im 3 m cubic structure; for these seven homologues the same type of cubic structure was observed both on heating and cooling. Further lengthening of the alkoxy chain to n = 22 and 26, however, gave two types of cubic structure in the cubic phase region on heating, one with Im 3 m symmetry in the low temperature region and the other with Ia 3 d symmetry in the high temperature region. On cooling, the two homologues exhibited the Ia 3 d cubic structure only. This is the first example in the cubic phase region of a series of homologues containing two types of structure, dependent on temperature and n . Such a complicated phase diagram in the cubic region is clearly understood qualitatively in terms of Gibbs free energy-temperature diagrams. The dependence of structural parameters such as the cubic lattice constant on the alkoxy chain length n are also presented and discussed. 相似文献
8.
The phase behaviour of the binary systems 4′- n -tetradecyloxy-3′-nitrobiphenyl-4-carboxylic acid (ANBC-14)- n -alkane ( n -tetradecane or n -hexadecane) was investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. The phase behaviour was a function of temperature ( T ) and the effective carbon number of the system ( n*), where n* involves carbon atoms both from the alkoxy group of ANBC-14 and from the n -alkane added. ANBC-14 shows no cubic phase, but the addition of n -alkane induced cubic phases when n*≧c. 15. An interesting point is that the type of cubic phase is Ia 3 d for 15≦n*≦17, while an Im 3 m type is formed for 18≦n*≦20. Furthermore, for n* = 22, two types of cubic phase, one with Im 3 m symmetry in the low temperature region and the other with Ia 3 d in the high temperature region, were observed both on heating and cooling. The phase diagram with respect to T and n* is very similar to that of pure one-component ANBC- n , which is a function of T and the number of carbon atoms in the alkoxy group n . 相似文献
9.
The spin-state-dependent reactivity, singlet versus triplet, of the 2-spiroepoxy-1,3-cyclopentane-1,3-diyl DR2 has been assessed through alcohol-trapping reactions for which the effect of solvent acidity on the product distribution of the alcohol trapping products 2 versus 3 + 4 and stereochemical deuterium-labeling studies have been performed. The proposed mechanism for the solvent effect on the product ratio (2/3 + 4) reveals the importance of the hydrogen-bonded intermediates I1 and I2 in the trapping reactions; the stereochemical deuterium-labeling results clarify the dipole structure trapped by the alcohol. The dipoles DP1 and DP2, in which the configuration between the epoxide oxygen and the deuterium atoms is retained, are inferred for the direct photodenitrogenation reactions (singlet state), whereas for the benzophenone-sensitized photoreactions (triplet state), after ISC, the ring-opened dipole DP3 is implied as the intermediate that is trapped by the alcohol. 相似文献
10.
Yusaku Iwasawa Tetsuroh Shirasawa Takehiro Nojima Toshio Takahashi Masuaki Matsumoto Koichi Akimoto Hiroshi Sugiyama 《Applied Surface Science》2008,254(23):7803-7806
The structure of buried Si(1 1 1)-5 × 2-Au capped with amorphous Si was investigated using surface X-ray diffraction. It was found that the 5 × 2 structural periodicity is kept under the amorphous Si from the in-plane measurement. Furthermore, the intensity variation along the fractional-order rod indicates that Au atoms are located almost on the same plane. 相似文献