硒代吗啉的曼尼希反应

用硒代吗啉与不同的酸组分、醛组分反应得到七个曼尼希反应的产物。     

稀土元素及其显色效应的研究 VI:镧-偶氮氯膦III——-钇混合多核配合物的生成

The interference of lanthanum in the spectrophotometric determination of yttrium in the form of β-type complex with chlorophosphonazo III (CPA III) is proved to be a cocoloration effect. It is due to the formation of a mixed polynuclear complex between CPA III and lanthahum-yttrium with a cyclic structure. The composition of the complex has been established to be La:CPA III:Y = 1:2:1 by the method of molar ratio. The optimal conditions for the formation of polynuclear complex and influence factors have also been studied. A "replacement type" reaction is proposed to account for the cocoloration effect.     

由热重数据计算动力学参数

热重法(TG)是一种动态测量技术,可在程序升温或降温情况下对给定物质或体系提供一个连续的,以温度或时间为函数的重量变化曲线,所以由它跟踪反应能给出反应动力学的有关信息。这种非等温法与早期使用的等温法相比,有快速、连续和需要较少实验数据等优点,近年来在动力学研究方面得到广泛应用,但还只限于研究下列几种类型的简单     

双硫碳阴离子与溴乙酸烷基酯的反应

双硫碳阴离子1是一个极为有用的合成原(Synthon),它在合成化学中已得到广泛应用。1通常与单官能团亲电试剂反应能产生满意的结果~([3a]),我们用此法从环氧乙烷成功地合成了化合物2a~([3b])。1与双官能团化合物的反应,例如与N,N-二乙基溴乙酰胺~([1b])或β-溴丙酸乙酯~([4])的反应均能得到溴被取代的产物,得率分别为50%和74%。这可能是由于酰氨羰基的不活泼性(前者)和β-溴丙酸酯的烯醇化使溴原子处于活泼的烯丙位(后者),从而有利于1进攻与溴相连的碳原子。本文报道1与滇乙酸烷基酯的反应以制备溴被取代的产物2b。1与溴乙酸叔丁酯反应,主要得到溴被取代的2-(3′-硫杂戊基)-2-叔丁氧甲酰甲基-1,3-二硫杂环己烷(3),得率70%;若与溴乙酸甲酯或乙酯反     

生化模型化合物的热化学研究 I.L(+)-天氡氨酸和L(+)-谷氨酸在水中的低浓度溶解焓

It has been found that an ordinary reaction calorimeter can be used for the determination of small heat effects (10^-^3 to 10^-^4 C temperature change) by correctly evaluating the Newton's cooling constant K through a reference temperature technique. This technique was applied to the determination of the integral enthalpies of solution of L(+)-aspartic acid and L(+)-glutamic acid in water in the concentration range of 10^-^3 to 10^-^4 mol/kg which were found equal to 25.8+/-0.6 and 25.7+/-0.4kJ/mol respectively (twice standard deviation). No CH2 increment effect has been revealed in the solution enthalpies of these two amino-acids.     

全氟和多氟烷基磺酸的研究 IX. 5-卤-3-氧杂-全氟戊磺酰氟的化学转化

5-Halo-3-oxa-perfluoropentanesulfonic acids 2,4 were obtained in high yields by treating the corresponding sulfonyl fluorides successively with KOH and concentrated H2SO4: Treatment of the acids with P2O5 gave corresponding anhydrides 3, 5. 3 reacted with various alcohols in the presence of pyridine to yield sulfonates 6. 5-Iodo-3-oxa-perfluoropentanesulfonyl fluoride (1) was converted to the acyl fluoride 9 by fuming sulfuric acid. Depending on the reaction temperature 9 can be hydrolyzed to fluorosulfonyl perfluoroalkanoic acid 10 and/or mixed dibasic acid 11. A similar phenomenon was also observed in the case of hydrolysis of fluorocarbonyl-perfluoromethanesulfonyl fluoride(13). Alcohol reacted readily with the acyl fluoride group but not with the sulfonyl group in 9 giving carboxylic esters, which can be further transformed to the corresponding sulfonates. Perfluoroalkoxide ion -O(CF2)2O(CF2)2SO2F prepared from 9 and F- reacted with active alkyl halides yielding the corresponding ethers. The interaction of 5-halo-3-oxa-perfluoroalkane-sulfonyl fluoride with AlCl3 was investigated. Friedel-crafts acylation of aromatic compounds with 9 in the presence of anhydrous AlCl3 is also reported. The yields of the desired ketones can be improved by using CCl4 as a solvent and changing the order of addition of reactants.     

有机磷化合物的研究 X:五价膦(磷)酸酯与卤代烷在卤化钠存在下的酯烷基交换反应

A detailed study on the ester alkyl exchange reaction of various types of quinique-valent phosphorus esters with alkyl halide in the presence of sodium bromides was reported. This ester alkyl exchange reaction was evidently influenced by the structure of phosphorus esters and alkyl halides as well as by the nature of the halides of metal ions. In contrast with the reaction without sodium hadlide, the alkyl phosphinmate is more reactive than phosphonate and phosphate by treatment with alkyl halide in the presence of sodium halide. This is consistent with the high nucleophilicity of >P(CO)O- as leaving group. The reactivity of butyl halides was decreased in the following order: n-BuBr>i-BuBr=s-BuBr>t-BuBr. Alkyl iodide was proved to be more reactive than the corresponding bromide and chloride. However, the use of iodioe is limited by the formation of alkene resulted from the elimination of HI. These structural effects show the general characteristics of a nucleophilic substitution reaction. A reaction mechanism involving the formation of sodium salt intermecutiate was proposed based on the concept of HSAB principle. This reaction may, however, be used as a convenient method for the preparation of mixed esters of quinque-valent phosphorus acids.     

SULFATION OF PACHYMAN WITH CHLOROSULFONIC ACID USING THE IMPROVED WOLFROM METHOD

High purity polysaccharide of pachyman was isolated from the powder of Poria cocos sclerotium with an yield of 77.8%. The intrinsic viscosity of polysaccharide was found to be 78.95 mL/g in DMSO solution at 25℃. The isolated polysaccharide was reacted with chlorosulfonic acid to obtain pachyman sulfate using the improved Wolfrom method. The results of the orthogonality experiment on the sulfation reaction identified that the effectiveness of the reaction conditions on the degree of sulfation and the value of intrinsic viscosity is in the following order: molar ratio of chlorosulfonic acid to glucoside (3-5) ＞ reaction temperature (60-80℃) ＞ reaction time (1-2 h). The kinetic studies of the pachyman sulfationindicated that the hydrolysis is accompanied with the sulfation process. The decrease in intrinsic viscosity of the sulfated pachyman is proportional to the increase in the degree of sulfation under the mild reaction conditions of ＜ 80℃,chlorosulfonic acid/glucoside mole ratio ＜ 5, and reaction time ＜ 2 h. Beyond the above reaction conditions, excessive loss of -OH group occurs during hydrolysis. The NMR results indicated a complete sulfation on C-6 and a partial sulfation on the C-2 and C-4 of glucoside.     

一缩二乙醇二甲基丙烯酸酯对真丝接枝的反应性

研究了一缩二乙二醇二甲基丙烯酸酯在空气存在下,用过硫酸钾(KPS)在水液 中对真丝的接枝。对接枝的条件,如单体、引发剂、甲酸(FA)和乳化剂OP的浓度以 及温度和时间对接枝率的影响进行了测试。发现了较佳的接枝条件是：温度 = 80 ℃,时间 = 30 min,[KPS] = 1.85% (owm),[OP] = 1% (owf),[FA] = 0.2%。 接枝率的大小可以用单体浓度来调节,接枝活化能是86.94 kJ/mol。     

超声波辐射下固-液相转移催化法合成N-(α -萘乙酰基)-N'- 芳基硫脲化合物

利用超声波辐射固－液相转移催化法合成了十三种未见文献报道的N(α-萘乙酰基)-N'-芳基硫脲新化合物,并经IR,1^HNMR,13^CNMR和元素分析确定了它们的结构。初步考查它们对玉米生长的促进作用,初步生物活性实验结果表明所有合成的化合物在(0.1～10)×10^-6的浓度内对玉米的根部生长具有显著的促进作用,部分化合物对玉米的幼苗具有促生长作用。