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101.
A simple and efficient method for the solid-phase synthesis of benzimidazole libraries is described. Monoalkylation of various o-phenylenediamines on resin-bound bromoacetamide proceeded smoothly to give the monoalkyl resin-bound o-phenylenediamines in high yields. Subsequent cyclization of the diamines with various aldehydes afforded solid-supported benzimidazoles. Cleavage from the resin gave benzimidazoles in good yields. The present method enabled the introduction of the diversity on the benzene ring of imidazoles. Azabenzimidazoles, such as 4-azabenzimidazoles, 5-azabenzimidazoles, and purines, were also synthesized in good yields with high purities by the same procedure. 相似文献
102.
Adachi K Sugiyama Y Yoneda K Yamada K Nozaki K Fuyuhiro A Kawata S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6616-6628
Novel triply hydrogen bonded suprastructures based on [M(tdpd)2(L)2]2- (H2tdpd=1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile, L=solvent) and melamine-analogous cations have been synthesized and characterized. The use of anions containing two AAA sets from [M(tdpd)2(L)2]2- together with cations containing one DDD set (A=hydrogen-bond acceptor, D=hydrogen-bond donor) leads to the formation of complementary triply hydrogen bonded modules in the solid state. In all cases, the building module is further extended via additional hydrogen-bonding interactions to produce a tape, and tapes are assembled into sheets. These results show that a hydrogen-bonded module consisting of different kinds of building blocks, one of which is a metal complex that includes hydrogen-bond acceptor sites and the other is a hydrogen-bond donor molecule, will be attractive for constructing metal-containing supramolecular systems by the self-assembly technique. 相似文献
103.
We used a combination of theoretical and experimental methods to derive the spectroscopic properties of imidazolium-based ionic liquids. Vibrational frequencies, NMR chemical shifts, and quadrupole coupling constants react in comparable manner to changes in the chemical environment. This suggests that both the IR and the NMR spectroscopic properties reflect a similar type of electronic perturbation caused by hydrogen bonding. These relationships of the spectroscopic properties provide detailed information about structural complexes and may thus serve as good indicators of ion-pair formation. They also help to decide which spectroscopic tool is the most sensitive for investigating molecular interactions. The measurement of only one spectroscopic property allows the prediction of other properties that cannot be so easily measured. In some cases, this is the only way to obtain reliable coupling constants for deriving molecular correlation times from macroscopic NMR relaxation times, thus opening a new path for studying structure-dynamics relations in ionic liquids. 相似文献
104.
Ogata Atsushi Mizuno Koichi Kushiyama Satoshi Yamamoto Toshiaki 《Plasma Chemistry and Plasma Processing》1998,18(3):363-373
The behavior of lattice oxygen species of the ferroelectric material during methane oxidation was investigated using a nonthermal plasma reactor packed with BaTiO
3
pellets. Lattice oxygen species in BaTiO
3
play an important role in the formation of N
2
O and the oxidation of CH
4
. The oxidation products such as CO and CO
2
were formed from independent reaction pathways. Lattice oxygen species were able to preferentially oxidize the carbon species deposited on the pellet surface into CO. Also, N
2
O and NO
x
were independently formed in the N
2–O
2
reaction, suggesting that different oxygen species give N
2
O and NO
x. N
2
O was produced by the oxidation of molecular nitrogen with lattice oxygen species. 相似文献
105.
Ishiguro R Yokoyama Y Maeda H Shimamura A Kameyama K Hiramatsu K 《Journal of colloid and interface science》2005,290(1):91-101
Infrared spectra of hen egg white lysozyme and bovine serum albumin (BSA) adsorbed on a solid poly tris(trimethylsiloxy)silylstyrene (pTSS) surface in D2O solution were measured using attenuated total reflection (ATR) Fourier transform infrared spectroscopy. From the area and shape of the amide I' band of each spectrum, the adsorption amount and the secondary structure were determined simultaneously, as a function of adsorption time. We could show that the average conformation for all the adsorbed lysozyme molecules was solely determined by the adsorption time, and independent of the bulk concentration, while the adsorption amount increased with the bulk concentration as well as the adsorption time. These results suggest that lysozyme molecules form discrete assemblies on the surface, and that the surface assemblies grow over several hours to have a definite architecture independent of the adsorption amount. As for BSA, the extent of the conformational change was solely determined by the adsorption amount, regardless of the bulk concentration and the adsorption time. These differences in the adsorption properties of lysozyme and BSA may reflect differences in their conformational stabilities. 相似文献
106.
Heng-dao Quan Hui-e Yang Masanori Tamura Akira Sekiya 《Journal of fluorine chemistry》2004,125(7):1169-1172
A novel fluorination reagent and catalyst, SbF5/PAF (porous aluminum fluoride), was prepared by impregnating SbCl5 into PAF and then treating with anhydrous hydrogen fluoride. The prepared reagent had an excellent catalytic activity in halogen-exchange, and also improved the properties of SbF5, such as hydroscopicity, corrosion, and toxicity. SbF5/PAF was successfully used in organic synthesis as a fluorinating reagent, and a fixed bed catalyst for F/Cl exchange. 相似文献
107.
Simons electrochemical fluorination (ECF) of 1,4-dimethyl-1,4-homopiperazine, methyl 4-ethylhomopiperazin-1-ylacetate and 1,4-bis(methoxycarbonylmethyl)-1,4-homopiperazine was studied. For comparison, ECF of three piperazines with a N-(methoxycarbonylmethyl) group(s) was also studied. ECF of 1,4-dimethyl-1,4-homopiperazine gave a low yield of corresponding perfluoro(1,4-dimethyl-1,4-homopiperazine) together with perfluoro(2,6-diaza-2,6-dimethylheptane) as the major product. Corresponding perfluoro(homopiperazines) with mono- and/or di-(fluorocarbonyldifluoromethyl) groups [CF2C(O)F] at the 1- and/or 4-position were formed in low yields from methyl 4-ethylhomopiperazin-1-ylacetate and 1,4-bis(methoxycarbonylmethyl)-1,4-homopiperazine, respectively. These new seven-membered perfluoro(1,4-dialkyl-1,4-homopiperazines) were accompanied by the formation of mono- and/or di-basic linear perfluoroacid fluorides resulting from the CC bond scission at the 2- and 3-positions of the ring. From mono- and/or di-N-(methoxycarbonylmethyl)-substituted piperazines, corresponding perfluoropeperazines having the acid fluoride group(s) were formed in low yields. 相似文献
108.
Lee K Kim H Miura T Kiyota K Kusama H Kim S Iwasawa N Lee PH 《Journal of the American Chemical Society》2003,125(32):9682-9688
3-tert-Butyldimethylsilyloxyalk-2-enylsulfonium salts, generated in situ from the reaction of alpha,beta-enones with dimethyl sulfide in the presence of TBSOTf, underwent a novel nucleophilic substitution with allylindiums to give silyl enol ethers of delta,epsilon-alkenyl ketones in good yields, which correspond to formal Michael addition products. In a similar manner, 1,4-propargylation of propargylindiums onto the sulfonium salts produced the corresponding silyl enol ethers of delta,epsilon-alkynyl ketones in good yields. Organoindium reagents derived from gamma-substituted propargyl bromide and indium afforded the corresponding silyl enol ethers of beta-allenyl ketones in good yields. The reaction proceeds via an addition-substitution mechanism involving the formation of allylic sulfonium salts. The presence of the intermediate sulfonium salt was confirmed by observation of the low-temperature (1)H NMR spectra. 相似文献
109.
Evaluating the acute toxic effects of drugs or toxins is based mainly on studies which require the use of light microscopy. Recently, the effects of such substances on biological membranes, such as the nasal membrane, has been studied using the traditional Ussing chambers, which make it possible to study the transepithelial flux of drugs across membranes and to measure some bioelectrical parameters. A model is described, with which the changes in the membrane permeability, for sodium, potassium and chlorine, can be calculated directly, based on values obtained from the Ussing chamber system. Also, an experiment is described for evaluating the toxic effects of the cholera toxin B subunit, by measuring these changes in isolated rabbit nasal mucosa. 相似文献
110.
A simple method for the rapid and simultaneous analysis of dichlorvos (DDVP), malathion, carbaryl, and 2,4-dichlorophenoxy acetic acid (2,4-D) in citrus fruit, which uses flow-injection ion spray ionization tandem mass spectrometry, has been developed for the first time. The method involves the combined use of stable isotopically labeled internal standards (DDVP-d6, malathion-d10, carbaryl-d7, and 2,4-D-d5) and a multiple reaction monitoring technique. The average recoveries for the pesticides at the same concentrations as their tolerance levels (DDVP: 0.1-0.2 μg g−1; malathion: 0.5-4.0 μg g−1; carbaryl: 1.0 μg g−1; 2,4-D: 1.0-2.0 μg g−1) ranged from 90 to 119% with the relative standard deviation (R.S.D.) ranging from 1.0 to 13.1% (n = 5). Analysis time, including sample preparation and determination, was only 15 min. The present method is effective for screening DDVP, malathion, carbaryl, and 2,4-D in citrus fruit. 相似文献