超临界二氧化碳介质中钯催化炔烃羰基化反应

研究了以超临界二氧化碳为反应介质实现改善钯催化炔烃羰基化反应绿色性的方法 .研究结果表明 :醇的用量、二氧化碳压力和反应温度等因素均对钯催化炔烃羰基化反应的化学选择性均有影响 ,即存在炔烃的羰基化反应与氧化偶合反应的竞争     

钯催化α-炔醇立体专一合成α-（Z）-氯亚甲基-β-内酯

首次在一氧化碳存在下，以仲丁醇和苯为混合反应溶剂，氯化钯和氯化铜为催 化体系催化α-炔醇羰基化，立体专一合成α-（Z）-氯亚甲基-β-内酯环。     

Protolytic reactions of 3,3'-dimethylnaphthidine and 3,3'-dimethoxybenzidine

The dissociation constants of diprotonated 3,3'-dimethylnaphthidine (DMN) and 3,3'-dimethoxybenzidine (DMB) have been determined spectrophotometrically. They are: pK(a1) = 2.62 +/- 0.03, pK(a2) = 3.33 +/- 0.09 for DMN: pK(a1) = 2.83 +/- 0.07, pK(a2) = 4.05 +/- 0.12 for DMB. The molar absorptivities (l.mole(-1).cm(-1)) of all forms of the indicators have been also determined: epsilon(B) = 1.68 x 10(4), epsilon(BH(+)) = 9.34 x 10(3), epsilon(BH(2+)(2)) = 1.80 x 10(3) at 300 nm for DMB; epsilon(B) = 7.33 x 10(3), epsilon(BH(+)) = 3.73 x 10(3), epsilon(BH(2+)(2)) = 0 at 330 nm for DMN.     

Potentiometric determination of dialysate urea nitrogen

An enzymatically modified ammonium ion-selective electrode has been applied for the determination of urea in spent dialysate. The biosensor has been used in a simple flow-injection analysis (FIA) system. The system enables one to perform over 25 dialysate urea nitrogen (DUN) determinations per hour. The interferences from other components of posthemodialysis fluid were eliminated by simultaneous measurements with non-modified enzymatically ion-selective electrode. It is possible to use both the sensors in a simplified differential potentiometric system. The results of DUN determination using the biosensor/FIA system and a conventional method of urea determination were comparable. The presented analytical system can potentially find wider biomedical application in the monitoring of hemodialysis progress.     

Spectroscopic Study of the Interaction between New Fluorescent Dyes with Nucleic Acids

Considerableefforthasbeencofltinuingtofocusonthedevelopmentofnewfluorescentdyestorecognizenucleicacids'-'.Althoughdansylisawell-knownsensitivehydrophobicprobewhichhasbeenwidelyutilizedasafluorescentprobeforthestudyofproteins,yetlittleefforthasbeenfocusedontheexploringdansylamidederivativeswhichmayhavespecificeffectsonnucleicacids.Sincethebindingaffinityofsuchfluorophorestopolynucleotideswasgreatlyaffectedbytheirsidechainsubstitutions,inthisworkseveralnewdansylderivativeswithspecificbindingtonu…     

氟化银促进烯炔分子内串联反应研究

以烯炔为反应原料,在碱性条件下,顺利地发生分子内串联反应合成了芳基萘类木脂素.研究发现,加入氟化银可以高效地促进反应进行.实验结果表明,以CH2C1CH2C1作溶剂,在AgF和K2CO3存在下,烯炔可以顺利发生分子内串联反应,高产率得到芳基萘类木脂素.     

Diiodination of Alkynes in supercritical Carbon dioxide

A general,green and efficient method for the synthesis of transdiiodoalkenes in CO2(sc) has been developed.Trans-diiodoalkenes were obtained stereospecifically in quantitative yields via diiodination of both electron-rich and electron-deficient alkynes in the presence of KI,Ce(SO4)2 and water in supercritical carbon dioxide [CO2(sc)]at 40℃.     

在催化体系可回收和无配体条件下溴化四丁基铵中钯催化卤代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应

我们发展一种在催化体系可回收和无配体条件下溴化四丁基铵（TBAB）中钯催化卤代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应方法。我们发现水的量对反应有很大的影响。当水的用量为1 %（质量比）时,反应的结果最好。在3 mol%的醋酸钯和1.5 g的TBAB（含1%的水）,一系列卤代芳烃与芳基硼酸的顺利地发生Suzuki-Miyaura交叉偶联反应,得到中等及良好的产率。而且在溴代芳烃和活泼的氯代芳烃的交叉反应中,Pd(OAc)2/TBAB催化体系可以回收重复使用多次,并且催化活性基本不变。     

Potentiometric study of end-point detection in the coulometric determination of carbon dioxide

The coulometric determination of carbon dioxide is based on the alkalimetric titration of the product of absorption of carbon dioxide in an organic solution of monoethanolamine. The processes occurring in various solvents have been investigated and optimized for analytical application. The protolytic reactions of 2-hydroxyethylcarbamic acid have been investigated in 2-propanol + 2, 5 and 10% water, dimethylformamide + 2% water, dimethylsulphoxide +5, 10 and 20% water. In coulometric generation of the base, 0.1M solutions of tetraethylammonium bromide in these solvents were used. The course of the titration was followed potentiometrically with glass and antimony indicator electrodes. From the titration curves the autoprotolysis constants of the mixed solvents and protonation constants of monoethanolamine in them were calculated. These constants and the concentration of monoethanolamine influence the size of the end-point break for the titrations. On this basis, optimal conditions for analysis have been selected and the total carbon content in samples of natural waters has been determined.     

Ammonium Chloride Promoted Palladium-Catalyzed UIImann Coupling of Aryl Bromide

In water, ammonium chloride was found to promote palladium-catalyzed Ullmann coupling reactions of aryl bromides. In the presence of Pd/C, zinc, NH4Cl, and water, coupling of various aryl bromides was carried out smoothly to afford the corresponding homocoupling products in moderate yields.