The hitherto unknown 5‐(2‐aryl‐2‐oxoethyl)‐4‐oxo‐1,3‐thiazolidines 1a‐l have been synthesized viacycloaddition process between thiourea and/or its derivatives with 3‐aroylpropenoic acids. 1H NMR spectra revealed the presence of 1a‐c as a tautmeric mixture. The presence of the thiazoline tautmers (1a‐c) ′ was confirmed by methylating the tautmeric mixture, to the respective methylated derivatives 2‐N‐methylanilino‐5‐(2‐aryl‐2‐oxoethyl)‐4‐oxo‐1,3‐thiazolines 2a‐c and 1g‐i . Acidic treatment of 1 provided the respective 2‐oxo homologues 3a‐i . When 1a‐d , k were refluxed with DMF, molecular rearrangement was achieved, providing the 4‐oxo‐2‐thioxoimidazolidine isomers 4a‐d , k . Bromination of 4a and 4d in hot acetic acid afforded the respective (E,Z)‐5‐benzoylmethylene derivatives 5a,d which were prepared authentically. Thiation of 1a‐c and 4a‐c gave 5‐aryl‐2,3‐dihydro‐2‐phenyliminothieno[2,3‐d]thiazoles 6a‐c and 1‐phenyl‐5‐aryl‐2,3‐dihydro‐2‐thioxothieno[2,3‐d]imidazoles 7a‐c , respectively. The proposed structures have been confirmed by elemental analysis and spectroscopic data. The selected products showed different antimicrobial effect. 相似文献
Talatisamine ( 1 ) is a member of the C19‐diterpenoid alkaloid family, and exhibits K+ channel inhibitory and antiarrhythmic activities. The formidable synthetic challenge that 1 presents is due to its highly oxidized and intricately fused hexacyclic 6/7/5/6/6/5‐membered‐ring structure (ABCDEF‐ring) with 12 contiguous stereocenters. Here we report an efficient synthetic route to 1 by the assembly of two structurally simple fragments, chiral 6/6‐membered AE‐ring 7 and aromatic 6‐membered D‐ring 6 . AE‐ring 7 was constructed from 2‐cyclohexenone ( 8 ) through fusing an N‐ethylpiperidine ring by a double Mannich reaction. After coupling 6 with 7 , an oxidative dearomatization/Diels–Alder reaction sequence generated fused pentacycle 4 b . The newly formed 6/6‐membered ring system was then stereospecifically reorganized into the 7/5‐membered BC‐ring of 3 via a Wagner–Meerwein rearrangement. Finally, Hg(OAc)2 induced an oxidative aza‐Prins cyclization of 2 , thereby forging the remaining 5‐membered F‐ring. The total synthesis of 1 was thus accomplished by optimizing and orchestrating 33 transformations from 8 . 相似文献
The performance of a blue polymer light‐emitting diodes (PLED) was significantly improved by doping a controlled amount (<1%) of a hole transport molecule N,N′‐bis‐(1‐naphthyl)‐N,N′‐diphenyl‐1,1′‐biphenyl‐4,4″‐diamine (NPB) into the emitting layer. Hole carrier mobility of the blue emitting polymer, BP105 (trade name of The Dow Chemicals Co.), increased from 5.27 × 10‐7 cm‐2/Vs of the pristine BP105 to 1.80 × 10‐6 cm‐2/Vs with the addition of 1% NPB in BP105. The enhanced carrier mobility greatly promoted performance of a blue PLED device with a device structure of ITO/PEDOT:PSS/BP105+x% NPB/LiF/Ca/Al. Luminance increased from 573 cd/m2 to 2,720 cd/m2 at 6V and efficiency increased from 1.1 lm/W to 1.6 lm/W at 1,000 cd/m2 with 1% NPB in BP105. The most important improvement was an increase in the lifetime of the blue device from 80 to 120 hours at an initial luminance of 400 cd/m2. We found that by choosing the appropriate dopant with good energy alignment and controlled dopant concentration, the performance of a blue PLED device could be greatly improved. 相似文献
The synthesis and structural properties of two kinds of thiosemicarbazide derivatives ( 2a‐c and 3a‐c ) and one kind of semicarbazide derivatives ( 4a, 4b ) have been described. These compounds were synthesized by treating 2‐(4‐amino‐3‐alkyl‐5‐oxo‐4,5‐dihydro‐1H‐1,2,4‐triazol‐1‐yl)acetohydrazides ( 1a‐c ) with benzyl isothiocyanate, 3‐florophenyl isothiocyanate and benzylisocyanate, respectively. The synthesis of 4‐amino‐3‐alkyl‐1‐[(4‐alkyl‐5‐mercapto(or 5‐oxo)‐4H‐1,2,4‐triazol‐3‐yl)methyl]‐4,5‐dihydro‐1H‐1,2,4‐triazol‐5‐ones ( 5a‐c, 6a‐c and 7 ) have been performed from the reaction with sodium hydroxide. On the other hand, the acidic treatment of compounds 2b, 3b and 4b has afforded 4‐amino‐3‐(4‐chlorobenzyl)‐1‐[(5‐alkylamino‐1,3,4‐thidazol(or 1,3,4‐oxazol)‐2‐yl)methyl]‐4,5‐dihydro‐1H‐1,2,4‐triazol‐5‐ones ( 8, 9 and 10 ). The condensation of thiosemi(or semi)carbazide derivatives ( 2a‐c, 3c and 4b ) with 4‐chlorophenacylbromide have resulted in the formation of 2‐[4‐amino‐3‐alkyl‐5‐oxo‐4,5‐dihydro‐1H‐1,2,4‐triazol‐1‐yl]‐N′‐(3,4‐dialkyl‐1,3‐thiazol(or oxazol)‐2(3H)‐yliden]acetohydrazides ( 11a‐c, 12, 13 ), while their condensation with chloroacetic acid has produced 2‐[4‐amino‐3‐alkyl‐5‐oxo‐4,5‐dihydro‐1H‐1,2,4‐triazol‐1‐yl]‐N′‐[3‐(3‐alkyl)]‐4‐oxo‐1,3‐thiazolidin(or oxazolidin)‐2‐yliden}acetohydrazides ( 14, 15 and 16 ). The spectral data and elemental analyses have support the proposed structures. 相似文献
The 1,3‐dipolar cycloaddition of an azomethine ylide generated by a decarboxylative route from sarcosine and isatin to 1‐benzyl‐3,5‐diarylmethylidene‐piperidin‐4‐ones afforded novel di‐spiro‐indolo/pyrrolidino/piperidines in moderate yields. Further cycloaddition of these di‐spiro compounds to nitrile oxide afforded tri‐spiro‐indolo/pyrrolidino/piperadino/isoxazolines in moderate yields with high regio‐ and stereoselectivity. 相似文献
We report a novel composite electrode made of chitosan‐SiO2‐multiwall carbon nanotube (CHIT‐SiO2‐MWNT) composite coated on the indium‐tin oxide (ITO) glass substrate. Cholesterol oxidase (ChOx) was covalently immobilized on the CHIT‐SiO2‐MWNT/ITO electrode that resulted in a ChOx/CHIT‐SiO2‐MWNT/ITO cholesterolactive bioelectrode. The CHIT‐SiO2‐MWNT/ITO and ChOx/CHIT‐SiO2‐MWNT/ITO electrodes were characterized with Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The influence of various parameters was investigated, including the applied potential, pH of the medium, and the concentration of the enzyme on the performance of the biosensor. The cholesterol bioelectrode exhibited a sensitivity of 3.4 nA/ mgdL?1 with a response time of five seconds. The biosensor using ChOx/CHIT‐SiO2‐MWNT/ITO as the working electrode retained its original response after being stored for six months. The biosensor using ChOx/CHIT‐SiO2‐MWNT/ITO as the working electrode showed a linear current response to the cholesterol concentration in the range of 50–650 mg/dL. 相似文献
A series of novel methylene‐bis‐pyrimidinyl‐spiro‐4‐thiazolidinones 6a‐h have been synthesized by cyclocondensation of thioglycolic acid with methylene‐bis‐(N‐cyclohexylidene‐N‐pyrimidine) 5a‐h , which in turn have been prepared by the reaction of cyclohexanone with methylene‐bis‐2‐aminopyrimidines 4a‐h , which are prepared by the reaction of guanidine hydrochloride with methylene‐bis‐chalcones 3a‐h . The compounds 3a‐h have been synthesized by the reaction of 5‐(3‐formyl‐4‐hydroxybenzyl)‐2‐hydroxybenzaldehyde 2 with various acetophenones in presence of KOH. The compound 2 is prepared by the reported method. The structures of the compounds synthesized have been confirmed by their elemental analysis and spectral data. Their antibacterial and antifungal activities have also been evaluated. 相似文献
Four series of substituted furan and pyrrole have been synthesized. The first series was prepared by cyclization of the key intermediates ethyl 5‐[(4‐substituted thiosemicarbazido)methyl]‐2‐methylfuran‐3‐carboxylates 2a‐2d and 1‐[(4‐acetyl‐5‐methyl‐1H‐pyrrol‐2‐yl)methylene]‐4‐substituted thiosemicarbazides 8a‐8d with chloroacetic acid or (ethyl bromoacetate) to afford the corresponding 4‐oxo‐3‐substituted thiazolidin‐2‐ylidene 3a‐3d or 3‐substituted thiazolidin‐4‐one 9a‐9d . On the other hand, heating of the intermediates 2a‐2d or 8a‐8d with acetic anhydride afforded the corresponding (N‐substituted acetylamino)‐2,3‐dihydro‐[1,3,4]thiadiazol‐2‐yl derivatives 4a‐4d and [1,3,4]thiadiazol‐2‐yl‐N‐substituted acetamide 10a‐10d respectively, while cyclization with p‐bromophenacyl bromide gave rise to the corresponding 3‐substituted thiazol‐2‐yl‐ylidene 5a‐5d and 11a‐11d respectively. Furthermore, 4‐oxo‐3‐substituted thioureido‐thiazolidin‐2‐yl 6a‐6d or 4‐oxo‐thiazolidin‐3‐yl‐3‐substituted thiourea 12a‐12d were obtained by reaction of the intermediates 2a‐2d or 8a‐8d with thioglycolic acid. Some of the synthesized compounds showed promising antimicrobial activities. 相似文献
Summary: The MADIX/RAFT mechanism, employing a xanthate as the reversible chain‐transfer agent, has been shown to facilitate the living radical polymerization of vinyl acetate in miniemulsion. Methyl (ethoxycarbonothioyl)sulfanyl acetate (MESA) successfully mediated the polymerization which was initiated with either of the water‐soluble initiators 2,2′‐azobis{2‐[1‐(2‐hydroxyethyl)‐2‐imidazolin‐2‐yl]propane} dihydrochloride (VA‐060) or 2,2′‐azobis[2‐(2‐dimidazolin‐2‐yl)propane] dihydrochloride (VA‐044). The polymerizations exhibit living characteristics, demonstrated by the evolution of molecular weight distributions. The formulation of the miniemulsion produced stable latexes with no coagulum.
The number‐average molecular weight and PDI as a function of monomer conversion for the RAFT miniemulsion polymerization of vinyl acetate. 相似文献