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排序方式: 共有450条查询结果,搜索用时 15 毫秒
141.
The attempted O-tosylation of tetracyclo[3.2.0.02,7.04,6]heptan-3-one (quadricyclanone) oxime with p-toluenesulfonyl chloride in dichloromethane in the presence of triethylamine/DMAP or pyridine resulted in the Beckmann fragmentation to give a mixture of 4-exo-/4-endo-tosyloxy- and 4-exo-/4-endo-chlorobicyclo[3.1.0]hex-2-ene-6-endo-carbonitriles in 90% overall yield. Solvolysis of all four products in 2,2,2-trifluoroethanol afforded the corresponding 4-exo-trifluoroethoxy derivative as the sole product. Quadricyclanone itself undergoes the fragmentation reaction with hydroxylamine-O-sulfonic acid, selectively affording the 4-exo-hydroxy-6-endo-nitrile in 90% isolated yield. 相似文献
142.
An efficient two-step synthetic pathway toward the preparation of diversely substituted 5-aroyl-3,4-dihydropyrimidin-2-ones is realized. The protocol involves an initial trimethylsilyl chloride-mediated Biginelli multicomponent reaction involving S-ethyl acetothioacetate, aromatic aldehydes, and ureas as building blocks to generate a set of 3,4-dihydropyrimidine-5-carboxylic acid thiol esters. These thiol esters serve as starting materials for a subsequent Pd-catalyzed Cu-mediated Liebeskind-Srogl cross-coupling reaction with boronic acids to provide the desired 5-aroyl-3,4-dihydropyrimidin-2-one derivatives. Both steps were performed using microwave heating in sealed vessels, either in an automated sequential or parallel format using dedicated microwave reactor instrumentation. A diverse library of 30 5-aroyl-3,4-dihydropyrimidin-2-ones was prepared with commercially available aldehyde, urea, and boronic acid building blocks as starting materials. 相似文献
143.
Vespalec R Langauf A Laromaine A Viñas C Horáková H 《Journal of separation science》2007,30(16):2733-2741
ACN is a better solvent than methanol for both [NMe(4)] [7-(2'-pyridyl)-nido-7,8-C(2)B(9)H(11)] and its protonated anion. The investigated laboratory preparations of the salt and of its protonated anion are electrophoretically pure solids stable for 2 months at 4 degrees C. At a longer storage, the solid salt is more stable than the solid protonated anion. In the 40:60 v/v water-methanol solvent, decomposition products of the salt anion are detectable after one-week storage of the salt solution at 4 degrees C. The protonated anion does not decompose for almost 1 year in water-organic solutions at 4 degrees C. The exchange of the proton between the protonated anion and the solution is reversible and fast at room temperature. The pH dependence of the mobility of the [7-(2(-pyridyl)-nido-7,8-C(2)B(9)H(11)](-) anion reveals that the basicity of the nitrogen atom in the pyridine ring is not significantly affected by the bonding of the pyridyl group to the nido-7,8-C(2)B(9)H(11) cluster in position 7 and that the proton from the solution is accepted by the nitrogen atom in the 2-pyridyl ring. The UV-spectra of the salt and of its protonated anion indicate that the accepted proton is probably slightly shifted to the open face of the nido-7,8-C(2)B(9)H(11) cluster. The [1](-) is chiral. 相似文献
144.
Dr. Veronika Novakova Miroslava Lásková Hana Vavřičková Dr. Petr Zimcik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(41):14382-14392
Tetrapyrazinoporphyrazines (TPyzPzs) bearing one, two, four or eight 3,5‐di(tert‐butyl)‐4‐hydroxyphenol moieties were synthesized as zinc(II) complexes and metal‐free derivatives. The deprotonation of the phenol using tetrabutylammonium hydroxide induced the formation of a strong donor for intramolecular charge transfer that switched OFF the red fluorescence (λF~660 nm) of the parent zinc TPyzPzs. The changes were fully reversible for TPyzPzs with one to four phenolic moieties, and an irreversible modification was observed for TPyzPzs substituted with eight phenols. The sensors were anchored to lipophilic particles in water, and a pKa approximately 12.5–12.7 was determined for the phenolic hydroxyl based on fluorescence changes in different buffers. In addition, a novel concept for fluorescence OFF‐ON‐OFF switching in metal‐free TPyzPzs bearing phenolic moieties upon addition of specific amounts of base was demonstrated. 相似文献
145.
Klára Drobíková Lucia Rozumová Hana Otoupalíková Jana Seidlerová 《Chemical Papers》2015,69(9):1193-1201
Landfill represents the least environmentally-friendly method of waste disposal because of possible pollution to the environment. Dangerous wastes pose the greatest problems and are often disposed of by combustion. This process reduces their volume but entails the formation of new types of dangerous waste. The present study focuses on the possibilities of the removal of the hazardous properties of waste originating from hazardous waste incinerators (three types of bottom ash and charcoal from flue gas cleaning) by bioleaching. Toxic pollutants originating from waste could be removed by bioleaching with Acidithiobacillus ferrooxidans. The effectiveness of bioleaching was evaluated on the basis of the pollutant content in the aqueous leachates. For studying the relation between the efficiency of bioleaching and the binding of pollutants in the waste, Tessier’s sequential extraction was used. A comparison of bioleaching efficiency and the results of sequential extraction shows that bioleaching can be used to remove elements which are in an exchangeable form or are bound to carbonates, meaning that they are bound in bio-available forms. Bacterial activity was also shown to change the bonds of pollutants in wastes, leading to increased solubility of the pollutant. 相似文献
146.
Prof. Jana Kasparkova Dr. Hana Kostrhunova Dr. Olga Novakova Dr. Radka Křikavová Dr. Ján Vančo Prof. Zdeněk Trávníček Prof. Viktor Brabec 《Angewandte Chemie (International ed. in English)》2015,54(48):14478-14482
We report toxic effects of a photoactivatable platinum(IV) complex conjugated with suberoyl‐bis‐hydroxamic acid in tumor cells. The conjugate exerts, after photoactivation, two functions: activity as both a platinum(II) anticancer drug and histone deacetylase (HDAC) inhibitor in cancer cells. This approach relies on the use of a PtIV pro‐drug, acting by two independent mechanisms of biological action in a cooperative manner, which can be selectively photoactivated to a cytotoxic species in and around a tumor, thereby increasing selectivity towards cancer cells. These results suggest that this strategy is a valuable route to design new platinum agents with higher efficacy for photodynamic anticancer chemotherapy. 相似文献
147.
Ten 2-(4-acetamidophenylimino)-5-arylidenethiazolidin-4-one derivatives 6a-k were synthesized and evaluated for their anticancer activity against MCF-7 cell line (breast adenocarcinoma). The synthetic approach involves cyclocondensation of N,N′-bis(4-acetamidophenyl)-thiourea (3) with ethyl bromoacetate in ethanol and sodium acetate to furnish the 2-(4-acetamidophenylimino)-4-thiazolidinone derivative 4 , which underwent Knoevenagel condensation reaction with some substituted aldehydes to afford the targeted 2-(4-acetamidophenylimino)-5-arylidenethiazolidin-4-ones 6a - k . The 4-chlorobenzylidene-thiazolidin-4-one compound 6h exhibited strong inhibitory effect on the growth of breast cancer cell with IC50 (58.33 ± 1.74μM), very close to that of the reference drug doxorubicin (IC50 48.06 ± 0.36μM). 相似文献
148.
The asymmetric aza-Henry reaction of α-substituted nitroacetates and N-Boc imines was achieved with a new-type thioureaguanidine bifunctional organocatalyst.The novel transformations exhibited high diastereoselectivities,and the adducts bearing adjacent quaternary and tertiary chiral centers were generally obtained in moderate to good enantioselectivities(up to 88%ee). 相似文献
149.
A new method for benzocaine determination employing FIA and HPLC with electrochemical detection on a carbon paste electrode was developed. The optimum conditions for the determination were found. Carrier solution for FIA consisted of B–R buffer pH 4 (80 % methanol, v/v) and used flow rate was 1.0 mL min?1. Mobile phase for HPLC consisted of B–R buffer pH 4 (75 % methanol, v/v) with flow rate 0.4 mL min?1. Working potential of +1.2 V was employed. Practical applicability of the methods was tested on the determination of benzocaine in selected pharmaceuticals. The results were in agreement with results obtained using spectrophotometric detection and with one exception also with the content declared by the manufacturer. 相似文献
150.
Kundrat O Dvorakova H Böhm S Eigner V Lhotak P 《The Journal of organic chemistry》2012,77(5):2272-2278
S-alkylation of all four thiacalix[4]arene conformations was accomplished using alkyl triflates. The corresponding sulfonium salts are formed in a highly regio- and stereoselective manner depending on the conformation used. Interestingly, only mono- or disubstituted sulfonium salts can be prepared. Although many regio- and stereoisomers are theoretically possible, only one dialkylated cone and 1,2-alternate derivatives were formed, while only a single isomer of monoalkylated partial cone and 1,3-alternate were isolated. The combination of experimental results with the quantum-chemical approach using the B3LYP/6-311G(d,p) method resulted in the elucidation of the rules governing the regio- and stereochemical outcomes of the alkylation reactions. All S-alkylated compounds represent a novel type of substitution pattern in calixarene chemistry showing the wide-ranging possibility of thiacalixarene skeleton modifications. 相似文献