双碳醇水溶液的~1H NMR实验与理论分析（英文）

采用核磁共振氢谱(~1H NMR)和量子化学(QC)方法研究不同温度下乙醇水溶液和乙二醇水溶液中醇与水之间的相互作用。观察实验结果发现两种醇水溶液中水质子的化学位移呈现两种不同的变化趋势。随着含水量的增加,乙醇(ET)水溶液中水质子化学位移急剧降低,而乙二醇(EG)水溶液中水质子的化学位移缓慢增加。两种醇水溶液中的羟基质子随着浓度的增加,其共振峰移向低场。不同温度下随着浓度的增加两种醇水溶液的烷基质子共振峰单调的移向低场。几何结构优化结果表明醇羟基质子与水质子之间氢键的形成弱化了醇中O—H键,从而导致其键长增加。值得注意的是在相同的极化作用和扩散作用下采用密度泛函理论(DFT)(B3LYP)计算得到的ET和EG的C-H键,C-C键和O-H键的键长值大于采用HF理论计算得到的结果。与此相反的是采用HF理论得到的ET和EG的O-H…O键强度大于采用DFT(B3LYP)理论得到的结果。几何构型优化结果与实验结果相吻合。在NMR化学位移的计算中,就文中所提到的理论水平而言,DFT要优于HF。而对于同一理论,其基组越大,计算值越接近实验值。     

二化螟性信息素组分(Z）-13-十八碳烯醛的合成

利用炔化物路线合成二化螟性信息素-（Z）-13-十八碳烯醛（1）。以1,12-十二烷二醇为原料,经单边溴化,羟基保护,偶联反应,选择性还原,去保护,氧化得到目标产物。反应共6步,总产率可达45%,各产物结构经¹H NMR确认。      

2-羟基-1-萘醛缩2-氨基-4-硝基苯酚亚胺的合成及其阴离子识别性能

以2-羟基-1-萘醛和2-氨基-4-硝基苯酚为原料,通过缩合反应合成了阴离子识别受体2-羟基-1-萘醛缩2-氨基-4-硝基苯酚亚胺（R）,其结构经¹H NMR, ¹³C NMR和IR表征。采用UV-Vis和¹H NMR等研究了受体R对阴离子的识别性能。结果表明：受体R在乙腈中对F^-、 H₂PO₄^-和AcO^-表现出良好的UV0Vis识别能力,且对上述阴离子表现出裸眼识别性能。通过核磁滴定、紫外滴定、络合常数及Job曲线等对受体R的识别机理进行了研究。结果表明：受体R与阴离子通过分子间氢键结合形成主客体配合物,对F^-具有更好的结合能力（络合常数为2.503 × 10⁴ L/mol）,与阴离子以比例1/1相互结合。     

绿色农药中间体羟基取代苯并吡喃的合成及自降解

自降解绿色农药对环境保护有重要意义。以苯硼酸为催化剂,1,4-苯二酚和-α,β-不饱和醛为原料,在质子酸作用下首次合成了绿色农药中间体--羟基取代苯并吡喃化合物（HBPR）,其结构经¹H NMR, ¹³C NMR, MS(ESI)和元素分析表征。并研究了目标化合物的自降解性能。结果表明：化合物在自然光照射下显示出与早熟素类似的自降解特性。     

FeCl3催化4-羟基香豆素烷基化衍生物的合成

以4-羟基香豆素、查尔醇（或苄醇）为原料,FeCl₃作催化剂,1,2-二氯乙烷作溶剂,在室温下实现了4-羟基香豆素的烷基化反应,高效合成了10个4-羟基香豆素的烷基化衍生物（3a~3e, 5a~5e）,收率70%~91%和67%~78%。在此基础上,利用FeCl₃/DDQ催化体系的一锅法串联环化反应合成了一系列2,4-二芳基-2H,5H-吡喃并[3,2-c]苯并吡喃-5-酮衍生物（6a~6d）,收率52%~85%。其中3b, 3d, 3e, 6b, 6c, 6d为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS（ESI）表征。     

新型3-氨基氮杂环丁烷衍生物的合成

以3-羟基氮杂环丁烷盐酸盐为原料,与4-氟苯乙酮反应制得1-（4-乙酰苯基）-3-羟基氮杂环丁烷（1）; 1经甲磺酰化反应、取代反应、还原反应及酰化反应,合成了6个新型的3-氨基氮杂环丁烷衍生物,其结构经¹H NMR和¹³C NMR表征。     

6-羟基染料木素和6,8-二羟基染料木素的简便合成

以鹰嘴豆芽素A为原料,通过溴代、甲氧基化和去甲基化三步反应合成了6-羟基染料木素（2b）和6,8-二羟基染料木素（3b）,总产率分别为20%和40%,其结构经¹H NMR, ¹³C NMR, HR-MS（ESI）和IR表征。      

合成(R)-2-异戊氧基丙醇的新方法

以(R)-1,2-丙二醇为原料,经伯醇羟基保护、仲醇O-异戊基取代、脱羟基保护三步反应合成了手性醇(R)-2-异戊氧基丙醇,其结构经NMR和MS确证.     

N,N-二[二(3-甲氧基丙基)膦基乙基]-2-乙氧基乙胺盐酸盐的合成

以2-乙氧基乙胺和3-氯-1-丙醇等为起始原料, 经7步反应, 制备了N,N-二[二(3-甲氧基丙基)膦基乙基]-2-乙氧基乙胺(PNP5)盐酸盐, 其中关键步骤是后两步. PNP5盐酸盐的结构和组成通过IR, ¹H NMR, ¹³C NMR, ³¹P NMR, MS和元素分析等方法确认.     

十二烷基硫醇催化合成2-芳基苯并呋喃

以邻羟基二芳基乙烯为底物,十二烷基硫醇为催化剂,在氧气氛围、无溶剂条件下构建了一种合成2-芳基苯并呋喃类化合物的新方法,产率28%~91%,其结构经¹ H NMR, ¹³ C NMR, HR-MS（ESI）和LR-MS（APCI）确证。      

Kinetic Studies on the Urethane Reaction of Propanediol with Isocyanate in Nitrogenous Solvents

The urethane reactions of 1,2-propanediol, 1,3-propanediol, and n-propanol with phenyl isocyanate were respectively carried out in nitrogenous solvents. In situ FT-IR was used to monitor the reactions, and rate constants were determined. It was shown that the reaction rate of 1,2-propanediol was fastest, followed by the reaction rates of 1,3-propanediol and n-propanol. After that, activation energy (E_a), activation enthalpy (ΔH), and activation entropy (ΔS) were calculated. It was found that these thermodynamic parameters for 1,2-propanediol and 1,3-propanediol are very similar, but they were very different from those of n-propanol, which is very useful to understand the urethane reaction mechanism.     

Solubility of carbon dioxide in aqueous solutions of 2-amino-2-ethyl-1,3-propanediol

The solubilities of carbon dioxide in aqueous solutions of 2-amino-2-ethyl-1,3-propanediol (AEPD) were measured at 313.15, 323.15, and 333.15 K over the partial pressure range of carbon dioxide from 1 to 3000 kPa. The concentrations of aqueous AEPD solutions were 10 and 30 mass%. The solubilities of carbon dioxide in aqueous 10 mass% AEPD solutions at 313.15 K and 30 mass% at 333.15 K were compared with those in aqueous solutions of various amines such as monoethanolamine (MEA), 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-methyl-1-propanol (AMP), and N-methyldiethanolamine (MDEA).     

Ionization constants for very weak organic acids in aqueous solution and apparent ionization constants for water in aqueous organic mixtures

A potentiometric method using a glass electrode has been applied to determination of apparent ionization constants for water in binary mixtures of water with tetrahydrofuran, methanol, 1,3-propanediol, glycerol, sucrose, and glucose at 25°C. Further calculations with these apparent ionization constants, which are now based explicitly on the previously implicit assumption that ionization of the organic component is negligible compared to ionization of water, permit evaluation of ionization constants for several very weak acids in purely aqueous solvent. Resulting pK values derived from this work and from our earlier work are as follows: glucose (12.38), sucrose (12.75 and 12.80), glycerol (14.05 and 14.07), ethylene glycol (14.44 and 14.52), methanol (15.2), 1,3-propanediol (14.8 and 15.0), 1-propanol (15.1), 2-propanol (15.7), and 2-methyl-2-propanol (15.0).     

Biocompatible microemulsions based on limonene: formulation, structure, and applications

The preparation of biocompatible (w/o) microemulsions based on R-(+)-limonene, water, and a mixture of lecithin and either 1-propanol or 1,2-propanediol as emulsifiers was considered. The choice of the compositions of the microemulsions used was based on the pseudo-ternary phase diagrams of the four-component system determined at 30 degrees C for different weight ratios of the components. When 1-propanol was considered as co-surfactant, the area of the microemulsion zone was remarkably increased. Interfacial properties and the dynamic structure of the emulsifier's monolayer were studied by electron paramagnetic resonance (EPR) spectroscopy using the spin-labeling technique. The rigidity and polarity of the interface were affected by the nature of the alcohol used as co-surfactant. When 1-propanol was used, the emulsifier's interface was much more flexible, indicating a less tight packing of lecithin molecules than in the case of 1,2-propanediol. In addition, the membrane's polarity was decreased when the diol was added as co-surfactant in the microemulsion system. To evaluate the size of the dispersed aqueous domains as a function of water content and other additives concentration, dynamic light scattering (DLS) measurements were carried out. Radii in the range from 60 to 180 nm were observed when 1-propanol was used as co-surfactant, and the water content varied from 0 to 12% w/w. Electrical conductivity measurements of R-(+)-limonene/lecithin/1-propanol/water microemulsions with increasing weight fractions of water indicated the appearance of a percolation threshold at water content above 4% w/w. Lipase from Rhizomucor miehei was solubilized in the aqueous domains of the biocompatible microemulsions, and the esterification of octanoic, dodecanoic, and hexadecanoic acids with the short-chained alcohols used as co-surfactants for the formulation of microemulsions was studied. The enzyme efficiency was affected by the chain length of the carboxylic acids and the nature of the alcohol. In the case of 1-propanol, a preference for the long-chain carboxylic acids was observed. On the contrary, when 1,2-propanediol was used formulation of the corresponding esters was not observed. This behavior could be possibly attributed to either the specificity of the lipase toward the alcohol employed for the esterification of the acids or the structural changes induced in the system when 1-propanol was replaced by 1,2-propanediol.     

GC-MS法分析S-环氧氯丙烷制备过程副产物的组成

利用GC-MS法对Salen催化水解拆分法制备S-环氧氯丙烷过程中所得副产物的组成进行了分析，结果表明，副产物有1，3-二氯-2-丙醇、3-氯-1，2-丙二醇，缩水甘油、1-羟基-2-丙酮、2，3-二氯-1-丙醇及2，3-二氯-1-丙醇乙酸酯等化合物，其中主要的水解副产物为1，3-二氯-2-丙醇和3-氯-1，2-丙二醇。     

Determination of halogenated mono-alcohols and diols in water by gas chromatography with electron-capture detection

We have developed an analytical method for the detection of halogenated alcohols in water with particular focus on 3-chloro-1,2-propanediol and 3-bromo-1,2-propanediol. In this method the target analytes are extracted from water, derivatized with heptafluorobutyric anhydride, and then analyzed with gas chromatography with electron-capture detection. The effects of water, pH and seawater constituents on the method were investigated. Method detection limits for a 5 ml aqueous sample ranged from 0.14 microg l(-1) for 2-bromo-1,3-propanediol to 1.7 microg l(-1) for 1,3-dichloro-2-propanol (1,3DCP).     

Protonation and silver(I) complex-formation equilibria of some amino-alcohols

Formation constants of the silver(I) complexes with some amino-alcohols have been determined at 25 degrees C in 0.5 M KNO(3) by means of two independent potentiometric measurements employing glass and silver electrode. The ligands considered are: sec-butylamine, 2-amino-1-propanol, 2-amino-1-methoxy-propane, 2-amino-2-methyl-1-propanol, 2-amino-1-butanol, 2-amino-1-pentanol, 2-amino-1-hexanol, 2-amino-1,3-propanediol, 2-amino-1,3-hexandiol, 2-amino-2-methyl-1,3-propanediol and Tris(hydroxymethyl)-aminomethane. Protonation constants of the selected ligands have also been determined. Calculations were made using HYPERQUAD computer program. The influence exerted by the introduction of hydroxy groups and by the presence of alkyl residuals in the ligand structure on the formation equilibria, is discussed.     

Enthalpies of proton transfer of hydroxy amines and maltol in methanol-water mixtures by direct calorimetry

Enthalpies of proton transfer in methanol-water mixtures (0–90 wt. % methanol) have been measured by direct calorimetry for the bases 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol and 2,2-bis(hydroxymethyl)-2,2,2-nitrilotriethanol at 25°C. Also reported are the data for 3-hydroxy-2-methyl-4-pyrone. The results are discussed in terms of an adaptation of classical electrostatic formula.     

A New Perspective of Enthalpies of Proton Transfer of Aliphatic Amines, Hydroxyamines, and Aminoalkylsulfonic Acids in Methanol–Water Mixtures by Direct Calorimetry

The enthalpies of proton transfer in methanol–water mixtures (0–90 wt.% methanol) of the aliphatic amines: triethylamine (Et₃N), t-butylamine, and quinuclidine (Q); the hydroxyamines:2-amino-2-methyl-1-propanol (Amp), 2-amino-2-methyl-1,3-propanediol (Bis), tris(hydroxymethyl)-aminomethane (Tris), and 2,2-bis(hydroxymethyl)-2,2′,2′′-nitrilotriethanol (Bis-Tris); and the aminoalkylsulfonic acids: 3-(N-morpholino)-propanesulfonic acid (MOPS), N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (Bes), and N-(2-hydroxyethyl)piperazine-N′-2-ethanesulfonic acid (HEPES), have been measured by direct calorimetry at 25°C. The results of the protonation reactions have been reported. All the salient features are now examined together with a view to assessing the success of interpretations using classical electrostatic formulation and three-dimensional structures in methanol–water mixtures. The objective is to find answers to the complex phenomena of solvation.     

Derived Properties of Binary Mixtures Containing (Acetone or Methanol) + Hydroxil Compounds

Abstract

This work reports values of the density, refractive index and speed of sound of the binary mixtures acetone or methanol with (2-methyl, 1-propanol, 3-methyl, 1-butanol, 1,2-ethanediol, 1,2-propanediol and 1,3-propanediol) at 298.15 K and atmosphere, as a function of the mole fraction. From the experimental values, the corresponding excess and derived magnitudes were computed (excess molar volumes, changes of refractive index on mixing and changes of isentropic compressibility on mixing), variable-degree polynomials being fitted to the results. Only expansive trend was observed for those mixtures enclosing branched alcohols. The influence of the hydroxil group in the nonideal behaviour of these mixtures were analyzed in terms of the partial molar excess volumes.