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11.
A robust, practical synthesis of (20S)‐10‐(3‐aminopropyloxy)‐7‐ethylcamptothecin (T‐2513, 5 ), which is a water‐soluble analogue of camptothecin, has been developed. The key step in this synthesis is a highly diastereoselective ethylation at the C20 position by using N‐arylsulfonyl‐(R)‐1,2,3,4‐tetrahydroisoquinoline‐3‐carboxylic acid ester as a chiral auxiliary, which affords the key intermediate ethyl‐(S)‐2‐acyloxy‐2‐(6‐cyano‐5‐oxo‐1,2,3,5‐tetrahydroindolizin‐7‐yl)butanoate ( 8 k ) in 93 % yield and 87 % de. Optically pure compound 8 k was obtained by a single recrystallization from acetone and its further elaboration through Friedlander condensation afforded compound 5 . This synthesis does not require any chromatographic purification steps and can provide compound 5 on a multi‐gram scale in 6.3 % overall yield (16 steps). 相似文献
12.
Machiko Shigemi Takahiro Takekiyo Hiroshi Abe Nozomu Hamaya Yukihiro Yoshimura 《Journal of solution chemistry》2014,43(9-10):1614-1624
We have used Raman spectroscopy to investigate the high-pressure phase behavior of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), a representative ionic liquid, at pressures up to ~7.5 GPa. We have also studied how increasing pressure leads to conformational changes in the [bmim]+ cation. We have found that liquid [bmim][BF4] undergoes pressure-induced solidification (freezing) into a superpressed (metastable) state at 2.5 GPa; another structural change probably occurs at ~6 GPa. Remarkably, conformational changes in the [bmim]+ cation between trans and gauche conformers are concordant with the metastable structural changes of [bmim][BF4]. As the pressure is increased from ambient, the fraction of gauche conformers increases, but the gauche fraction decreases above the solidification pressure (2.5 GPa), and slope of the gauche/trans ratio changes again above 6 GPa. We interpret these results in terms of the fragility of the ionic liquid. 相似文献
13.
Susumu Tajima Yukiyoshi Nagai Osamu Sekiguchi Masao Fujishige Nozomu Uchida 《Journal of the American Society for Mass Spectrometry》1995,6(3):202-206
The spontaneous unimolecular dissociation reaction of methyl lactate (1) ionized by electron impact was investigated by a combination of mass-analyzed ion kinetic energy spectrometry and deuterium labeling. The metastable ions 1+· decompose in a variety of ways: four fragment peaks are observed at m/z 89, 76, 61, and 45, which correspond to the losses of ?H3, CO, CH3?O, and ?OOCH3, respectively. Double hydrogen atom transfer occurs in the third reaction. The source-generated m/z 61 ions decompose into oxygen-protonated methanols at m/z 33 ([CH3OH 2 + ]) by the loss of CO with double hydrogen atom migration. Both hydroxyl and methyne hydrogen atoms in 1 +· are present in the resultant protonated methanols. 相似文献
14.
Arunabhiram Chutia Riadh SahnounRamesh C. Deka Zhigang ZhuHideyuki Tsuboi Hiromitsu TakabaAkira Miyamoto 《Physica B: Condensed Matter》2011,406(9):1665-1672
Based on experimental findings models of amorphous graphene related carbon materials were generated using graphene nano flakes. On the optimized structures detailed local electronic properties were investigated using density functional theory. The electrical conductivities of all these models were also estimated using an in-house program based on tight-binding method. The calculated electrical conductivity values of all the models agreed well with the trend of calculated energy gap and graphitic character. 相似文献
15.
Md. Khorshed Alam Ryuji Miura Hideyuki Tsuboi Akira Endou Momoji Kubo 《Applied Surface Science》2010,257(5):1383-1389
Ceria plays an important role in catalysis, due to its ability to store and release oxygen depending on the condition present in the catalyst environment. To analyze the role of ceria in catalytic reactions, it is necessary to know the details of the interaction of ceria surface with environmentally sensitive molecules. This study was conducted using ultra accelerated quantum chemical molecular dynamics. Its purpose was to investigate the reduction process of the (1 1 1) and (1 1 0) surfaces of ceria with atomic hydrogen as well as water desorption mechanisms from the surfaces. This simulation demonstrated that when a high-energy colliding hydrogen atoms are adsorbed on the ceria, it pulls up an O atom from the ceria surfaces and results in the formation of a H2O molecule. This is the first dynamics simulation related to such reduction processes based on quantum chemistry. 相似文献
16.
Silviu Polosan Tahsin J. Chow Taiju Tsuboi 《Journal of Physical Organic Chemistry》2008,21(4):315-320
Electronic states and their energies are calculated for a mixed‐ligand Ir(III) compound, (5‐chloro‐8‐hydroxyquinoline) bis(2‐phenylpyridyl) iridium (called IrQ(ppy)2‐5Cl) using time‐dependent density functional theory (TDDFT) calculations and are compared with the experimental result. A good agreement is obtained between the calculated and measured absorption spectra. The d‐πQ* molecular orbital transition gives the lowest‐energy triplet state absorption band. Its energy is estimated as 1.84 eV (671 nm), which is close to the absorption band position of 1.86 eV (666 nm) observed for IrQ(ppy)2‐5Cl doped in 4,4′‐N,N′‐dicarbazole‐biphenyl (CBP) host and of 1.88 eV (660 nm) observed for IrQ(ppy)2‐5Cl doped in polystyrene (PS). The second triplet state absorption band is caused by d‐πppy transition. Its position is calculated as 2.51 eV (494 nm). The dipole moment is estimated as 3.45 D, which is lower than the dipole moment of fac‐Ir(ppy)3. This is understood by a reduced charge transfer between Ir(III) and quinoline ligand. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
17.
Ken-Ichi Okamoto Nozomu Tanihara Hitoshi Watanabe Kazuhiro Tanaka Hidetoshi Kita Asumaru Nakamura Yoshihiro Kusuki Kanji Nakagawa 《Journal of Polymer Science.Polymer Physics》1992,30(11):1223-1231
Sorption and diffusion of water vapor are investigated gravimetrically for polyimide films. The activity dependence of the solubility and diffusion coefficients, S and D, respectively, is classified under four types: (1) constant S and D type, (2) dual-mode sorption and transport type, (3) dual-mode type followed by a deviation due to a plasticization effect at high vapor activity, and (4) constant S and D type followed by a deviation due to water cluster formation at high activity. For the dual-mode type, the Henry's law component is much larger than the Langmuir component except at low activity, and therefore deviation in behavior from the first type is small. S is larger for polyimides with higher content of polar groups such as carbonyl, carboxyl, and sulfonyl. D is larger for polyimides with a higher fraction of free space, with some exceptions. The polyimide from 3,3′,4,4′-biphenyltetracarboxylic dianhydride and dimethyl-3,7-diaminodibenzothiophene-5, 5-dioxide belongs to the third type and displays both large S and large D. The polyimide from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 4,4′-oxydianiline belongs to the fourth type, and has the largest D but rather small S because of the hydrophobic C(CF3)2 groups. © 1992 John Wiley & Sons, Inc. 相似文献
18.
19.
Takahiko Ishiguro Ei-ichiro Suzuki Akiko Y. Hirakawa Masamichi Tsuboi 《Journal of Molecular Spectroscopy》1980,83(2):360-372
Raman spectra of thiourea have been observed in H2O and D2O solutions with the exciting laser beams of 514.5, 488.0, 457.9, 363.8, 325.0, and 257.3 nm. The resonance Raman excitation profile of the 729-cm?1 line has been examined in the region of the 237-nm absorption band () by use of a solvent shift of the absorption band instead of by changing the wavelength of the exciting beam. The depolarization degree of this line was measured and its overtone Raman line was also observed. On the basis of the results of these experiments, it has been concluded that the 729-cm?1 Raman line, assignable to the CS stretching vibration, derives its intensity solely from the 237-nm band when it is excited at 257.3 or 325.0 nm. On exciting in the region 363.8–514.5 nm, however, contributions of the higher-frequency bands are predominant rather than the contribution from the 237-nm band. The Raman line at 1520 cm?1 of thiourea-d4 is assignable to the NCN antisymmetric stretching vibration. From its excitation profile, its intensity has been considered to come from a vibronic coupling between the excited electronic states of the 220-nm () and the 197-nm () bands. 相似文献
20.