阳、阴、非离子表面活性剂胶束对酯碱性水解的影响

应用紫外分光光度法和热动力学方法研究了芳香酸酯和正脂肪酸酯在表面活性剂ＤＴＡＢ、ＴＴＡＢ、ＣＴＡＢ、ＳＤＳ、Ｂｒｉｊ３５、ＴｒｉｔｏｎＸ－１００胶束中的碱性水解反应。阳、阴、非离子表面活性剂胶束对酯的碱性水解均有禁阻作用。讨论了胶束对酯碱性水解禁阻作用的原因。     

相转移催化合成增塑剂BBP和水杨醛的研究

相转移催化合成增塑剂ＢＢＰ和水杨醛的研究郭锡坤，高文华，曾东宇（汕头大学化学系，汕头５１５０６３）关键词相转移催化，季铵盐，聚乙二醇，邻苯二甲酸丁苄酯，水杨醛，增塑剂邻苯二甲酸丁苄酯（增塑剂ＢＢＰ）是一种优良的增塑剂．邻羟基苯甲醛（水杨醛）不仅是重要...     

Comparison of polydimethyl siloxane stationary phases with 5% and 50% phenyl substitution for the separation of organophosphorus and organonitrogen pesticides under optimized gas chromatographic conditions

The CGC analysis of 25 organophosphorus and organonitrogen pesticides was optimized on two different stationary phases, namely a 5% diphenyl dimethyl silicone (SE-54 type) and a 50% diphenyl dimethyl silicone (OV-17 type) by selecting the best temperature program conditions, using computer simulation.     

Studies on the thermotropic liquid crystalline polymer. XII. Synthesis and properties of crosslinkable thermotropic liquid crystalline homo- and copoly(ether-ester)s

A series of crosslinkable thermotropic liquid crystalline poly(ether-ester)s and copoly(ether-ester)s was prepared. All of the polymers were crosslinked by thermal treatment or photo-irradiation upon heating. The thermal stability and thermal crosslinking reaction of these polymers were investigated. These polymers also could be crosslinked by copolymerization with vinyl monomers, such as styrene or methyl methacrylate. The crosslinked polymers exhibited thermotropic liquid crystalline behavior after softening by heating. The phase behavior of linear polymers and crosslinked polymers was studied by differential scanning calorimetry (DSC) and an optical polarizing microscope equipped with a heating stage. © 1995 John Wiley & Sons, Inc.     

A new method for the synthesis of 2-cyclopenten-1-one-5-carboxylic ester derivatives via Rh2(OAc)4-mediated intramolecular C-H insertion reaction of 4Z-β-vinyl-α-diazo β-ketoesters

2-Cyclopenten-1-one-5-carboxylic ester derivatives 14 are synthesized in a four-step-reaction sequence starting from alkynyl aldehydes 9 via 4Z-β-vinyl-α-diazo β-ketoesters intermediate 8. The synthetic method for 8 is described. When the δ substituent is an alkyl group, Rh(II)-mediated decomposition of the diazo compounds 8 led to an intramolecular C-H insertion to afford 2-cyclopenten-1-one-5-carboxylic ester derivatives 14 in high yields. When the δ substituent is an aryl group, 2-hydroxynaphthoate 15 is obtained exclusively. In both cases, no Wolff rearrangement product was observed.     

A stannylene strategy for regioselective acylation and phosphorylation of 1,2-cyclohexylidene-myo-inositol. Its convenient resolution and phosphatidylinositol synthesis

The bis(dibutylstannylene) derivative of 1,2-cyclohexylidene-myo-inositol reacted with (S)-O-acetylmandeloyl chloride and diphosphate tetraesters to give 3,6-dimandelate and 3-phosphate, respectively. Using the stannylene methodology for the optical resolution and regioselective phosphorylation of the ketal, a concise synthesis of phosphatidylinositol with the natural configuration was accomplished.     

A novel method for asymmetric synthesis of both enantiomers of α-substituted carboxylic acid derivatives from optically active 1-chlorovinyl p-tolyl sulfoxides and lithium ester enolates with 1,4-chiral induction from the sulfur chiral center

Treatment of optically active 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from symmetrical ketones and (R)-(−)-chloromethyl p-tolyl sulfoxide in three steps, with lithium enolate of carboxylic acid tert-butyl esters gave optically active adducts having a substituent at the α-position with high 1,4-chiral induction from the sulfur chiral center in high yields. The adducts were converted to optically active esters and carboxylic acids having a chiral center at the α-position. When this addition reaction was carried out with the ester enolate generated from excess carboxylic acid tert-butyl ester with LDA in the presence of HMPA, the diastereomer of the adduct was obtained. By using the two reaction conditions for the generation of the ester enolates, a new method for asymmetric synthesis of both enantiomers of carboxylic acid derivatives having a substituent at the α-position from the one chiral source, (R)-(−)-chloromethyl p-tolyl sulfoxide, was realized.     

The first total synthesis of a bioactive metabolite, a spirobenzofuran isolated from the fungi Acremonium sp. HKI 0230

The first total synthesis of a bioactive metabolite, isolated from the fungi Acremonium sp. HKI 0230, containing a cyclopentaspirobenzofuran carbon framework, employing an Ireland ester Claisen rearrangement and RCM reaction based strategy has been accomplished.     

Ionic Association and Mobility IV. Ionophores in Dimethylsulfoxide at 25°C

The results of conductance measurements on pyridinium picrate, tetraphenylo-sonium picrate, potassium picrate, tetraphenylantimony picrate, tetrapropylam-monium, tetrafluoroborate, tetramethylammonium hexafluorophosphate ion association noncoulombic interaction in dimethyl sulfoxide (DMSO) at 25°C in the concentration range 1–15×10^–4 M are reported. The data were analyzed by the Justice modification of the Fuoss–Hsia equation. Except for pyridinium picrate all salts studied were found to be associated.Application of the Justice Barthel–Bjerrum model of ion association permitted calculation of the noncoulombic portion of the potential of mean force, W _±. Ionic limiting conductances were calculated for six ions using known values of previously determined transport numbers. A table of most current limiting ionic conductances for a variety of ions in DMSO at 25°C has been established.     

逐步法合成杯[4]芳烃关环反应的改进

对位带有3种或4种不同取代基的杯「4］芳烃一般通过逐步合成法合成．50年代后期,wS和Hllfl比rI'·'a就用［1十1十1十工］的逐步法9步合成出了杯［4］芳烃,总产率相当低·1979年B6hmer等［'·'报道用对位取代酚的线型三聚体与2,6一双溪甲基对取代酚在乙酸中进行关环反应合成杯［4」芳烃,这种［3＋l」的逐步法只需3步连续反应就能合成带有3种不同取代基的杯卜」芳烃,但最后。步关环产率仍然很低（2％、15％）［"．后来＊dhmeTD'等将关环反应改进为在TICI。／二氧六环体系中进行,产率有所提高,这种逐步法曾用于不对称杯［4」芳烃的…