共查询到20条相似文献,搜索用时 62 毫秒
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离子液体的酸性测定及其催化的二苯醚/十二烯烷基化反应 总被引:20,自引:0,他引:20
采用乙腈探针红外光谱法测定了[bmim]Cl/AlCl3类离子液体的酸性.结果表明,乙腈可以区分离子液体的酸类型(Bronsted酸或Lewis酸),同时可以指示离子液体的Lewis酸强度.使用[bmim]Cl/AlCl3类离子液体催化二苯醚与十二烯的烷基化反应,研究了离子液体的酸强度、反应温度和醚烯比对反应的影响,并与AlCl3催化体系进行对比.结果发现,该离子液体对二苯醚与十二烯烷基化反应的催化活性明显高于AlCl3.使用离子液体作催化剂显著提高了烷基化反应的产率,简化了产物的分离与提纯,且对环境友好.当控制反应温度为80℃,原料醚烯摩尔比为7,并采用酸强度适中的离子液体时,目标产物单十二烷基二苯醚的产率接近90%. 相似文献
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王华 《影像科学与光化学》2017,35(5)
本文综述了近年来噻吩螺烯的化学与光化学合成方面的重要进展。在螺烯的化学合成方面,阐明了单螺烯的常见合成手法,即以并三噻吩为构筑模块,合成螺烯前驱体联并三噻吩,其后通过硫代关环手法制备噻吩单螺烯。由于前驱体的两个并噻吩片段可能存在分子内的相互作用,造成无法无限制增长螺烯分子的尺寸。通过增加助溶基团的合成策略可以将螺烯的分子结构由单螺烯引入到双螺烯。在螺烯的光化学合成方面,光化学氧化关环的实例表明了光化学是构筑单螺烯与双螺烯的有效手法。由于存在前驱体双键在光照条件下可以打开产生双自由基的光化学反应机理,在其后关环步骤可有效产生外消旋体与内消旋体这样有趣的双螺烯产物。此外,本文针对噻吩螺烯领域的前景,提出了3个方面的观点:1)通过设计末端噻吩环上硫原子的位置异构,形成新的螺烯同分异构体;2)通过合成设计,可以制备新结构的双螺烯与多螺烯;3)通过手性拆分,可将螺烯旋光体应用于手性催化、手性组装等应用领域。 相似文献
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手性联烯是一类具有丙二烯结构的轴手性化合物,不仅广泛存在于众多天然产物[1]、药理活性分子及功能材料中[2],还是有机化学中非常重要的合成砌块[3].其中,含有一个中心手性和轴手性的2,3-联烯醇结构是类胡萝卜、素类、萜类以及溴代联烯天然产物的核心片段,表现出广泛的生理活性,并且由于同时含有联烯和醇羟基官能团,也具有多样的反应化学.因此,2,3-联烯醇的不对称合成具有重要的研究意义. 相似文献
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通过单-2-对甲苯磺酰基-β-环糊精(1)与马来二腈基二硫烯钠盐的取代反应制得单-2-马来二腈基二硫烯-β-环糊精(2),并经红外光谱、紫外光谱、热重分析、1H和13C NMR等手段对产物进行了表征.虽然化合物2的异构体--单-6-马来二腈基二硫烯9-β-环糊精在溶液中因为相互包合作用而在圆二色性光谱中产生分裂的Cot... 相似文献
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1,3-偶极环加成法合成异噁唑啉新化合物及其生物活性的研究 总被引:1,自引:0,他引:1
以N-甲羟胺硫酸盐和芳香族羰基化合物为主要原料合成了一系列不同的1,3-偶极化合物, 并合成了四种不同的单取代苯乙烯. 以该系列1,3-偶极化合物和单取代苯乙烯为主要中间体, 采用1,3-偶极环加成反应合成了一系列异噁唑啉类新化合物. 同时研究了1,3-偶极化合物与单取代烯发生的1,3-偶极环加成反应, 该合成过程为理想的绿色反应, 合成产物是5位取代异噁唑啉. 通过质谱和核磁共振等表征了化合物的化学结构. 同时对系列异噁唑啉类新化合物进行了实验室内植物生物活性的测试, 发现了对植物灰霉病有效的新化合物. 相似文献
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Abstract— In dimethylsulfoxide the emission spectrum of luminol chemiluminescence is red-shifted by 300 cm-1 from the photoexcited fluorescence of the product 3-aminophthalate dianion, while in aqueous solvent the two spectra are identical. The spectral properties of the product dianion have been measured in aqueous solvent and in a number of aprotic solvents, both at room temperature and at 77°K. The ground states and the excited states from which emissions are observed are characterized. Two alternatives are presented to explain the aprotic emission spectra. 相似文献
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WielA. G. BrulsJoop A. J. Faber†Jan C. van der Leun 《Photochemistry and photobiology》1982,36(5):531-535
The minimal erythema dose (MED) is often used as a quantity by which the influence of certain treatments of the skin can be measured. Differential measurements are performed by assessing the difference of the MED on the skin treated in some way and the untreated skin.
As the MED-measuring scale is discrete, the question is sometimes raised whether it is possible to measure differences smaller than one scale unit. In the present paper it is shown that this is indeed possible; in principle the discreteness of the scale does not impose any restriction on the smallest value of the difference that can be measured. The discreteness of the scale introduces an extra random variation into the measurement. This variation is estimated theoretically. It is automatically included in the usual error analysis.
The discreteness variance is small when compared to other variance components, which are computed from an analysis of variance of actual experiments. Reducing the discreteness variance, by reducing the dose decrement of the MED-measuring scale, therefore, does not enhance the overall accuracy considerably. Finally, it is found that the assessments of the MED by the various observers do not differ significantly from each other, and that multiple assessments do increase the accuracy, especially for small effects. 相似文献
As the MED-measuring scale is discrete, the question is sometimes raised whether it is possible to measure differences smaller than one scale unit. In the present paper it is shown that this is indeed possible; in principle the discreteness of the scale does not impose any restriction on the smallest value of the difference that can be measured. The discreteness of the scale introduces an extra random variation into the measurement. This variation is estimated theoretically. It is automatically included in the usual error analysis.
The discreteness variance is small when compared to other variance components, which are computed from an analysis of variance of actual experiments. Reducing the discreteness variance, by reducing the dose decrement of the MED-measuring scale, therefore, does not enhance the overall accuracy considerably. Finally, it is found that the assessments of the MED by the various observers do not differ significantly from each other, and that multiple assessments do increase the accuracy, especially for small effects. 相似文献
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分光光度法低浓度区不成线性关系的探讨 总被引:3,自引:0,他引:3
本文研究分光光度法低浓度区不成线性的有关因素及其克服方法,以铝-二甲酚橙体系为例,通过对体系不同条件下吸收光谱及其等色点的研究,发现当体系pH渐变时(铝,二甲酚橙浓度固定不变),曲线簇现两个等色点.从对等色点的分析,证明体系形成络合物须按一个反应式进行才能出现等色点,而与反应式是否涉及到两个或三个有色化合物无关.若同时按两个反应式进行,则不能得到等色点,测定时也无线性关系.所以用这个体系进行铝的测定,铝浓度的变化范围只能限于存在等色点的区间才有线性关系. 为了克服常法测定铝时不符线性的现象,本文采用的方法是在二甲酚橙中预先加适量的铝作为显色剂,使反应严格按一个反应式进行,所得结果为一直线. 相似文献
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对苯二胺衍生物的光催化氧化 总被引:1,自引:0,他引:1
以TiO2作为催化剂,利用波长>330nm的光辐照研究了N-取代的对苯-二胺衍生物的光催化氧化。研究表明,氧分子与光生电子 反应生成羟基自由基,羟基自由基氧化PPDs,生成醌二亚胺,后者在羟基的进攻下脱氨生成苯醌,苯醌继续光解无机化。PPDs光催化氧化近似遵循一级反应动力学,醇类和硫酸根离子可抑制PPDs的光催化氧化。催化剂表面荷影响电子转移速率,从而控制光催化氧化的反应速率。 相似文献
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The kinetics of the decomposition of cyclohexyl hydroperoxide(CHHP) in benzene catalyzed by vanadyl dibenzoylmethane[V0(DBM).,] has been studied.It was found that the products of decomposition of CHHP were cyclohexanol and cyclohexanone,which are produced in about equimolar amount,and the product cyclohexanol obviously inhibited the decomposition of CHHP.The kinetics data can be satisfactorily described by the following equation (with [CHHP]0>>[VO(DBM)2]0)R0=kK[CHHP]0[VO(DBM)2]0/(1+k[CHHP]0)This is the kinetic evidence for the formation of a catalyst-hydro-peroxide intermediate.In the equation K is the stability constant of the catalyst-hydroperoxide intermediate complex;k is the rate constant for the decomposition of the complex.The rate constant K at 500℃ may be expressed as follows:k=1.9×108exp(-53.7×103/RT)S-1 with the activation energy Ea=53.7kJ mol-1 相似文献