合成(R)-(+)-N,N-二甲基-1-二茂铁基乙胺的方法改进

二茂铁与乙酰氯经傅-克反应制得乙酰基二茂铁(1);1在Ru(Ⅱ)-(R,R)-TsDPEN催化下完成不对称氢转移制得手性仲醇(3);3酯化后再与二甲胺通过亲核取代反应合成了光学活性的(R)-(+)-N,N-二甲基-1-二茂铁基乙胺,总产率54.5%,其结构经1H NMR和IR确证。     

新型6-(4-氨基苯基)-4,5-二氢-3(2H)-哒嗪酮α-氨基膦酸酯衍生物的合成

以乙酰苯胺与丁二酸酐为原料,经Friedel-Crafts酰化反应、水解脱乙酰基和水合肼缩合制得中间体6-(4-氨基苯基)-4,5-二氢-3(2H)-哒嗪酮(3);3与芳醛和亚磷酸二乙酯经类Mannich-type反应合成了5个新型的6-(4-氨基苯基)-4,5-二氢-3(2H)-哒嗪酮α-氨基膦酸酯衍生物,其结构经1H NMR,~(13)C NMR,31P NMR,IR和ESI-MS表征。     

轴向取代邻苯二氧-四-α-(戊氧基)钛酞菁配合物的合成

以1-氯萘为溶剂,3-戊氧基邻苯二甲腈与TICl4经高温缩合反应制备四-α-(戊氧基)钛氧酞菁(2);2与邻苯二酚反应合成了新型轴向取代邻苯二氧-四-α-(戊氧基)钛酞菁配合物,其结构经荧光光谱,UV-Vis,1H NMR,IR,MS和元素分析表征.     

2-乙酰基-6-三甲基硅基苯基三氟甲磺酸酯的合成

以2-三甲基硅基苯酚为原料,经甲酰化、酯化、亲核加成和氧化反应首次合成了3-乙酰基苯炔的前体——2-乙酰基-6-三甲基硅基苯基三氟甲磺酸酯,总收率35%,其结构经1H NMR和13C NMR确证。     

合成β-甘油磷酸的新方法

报道了一种合成β-甘油磷酸(β-3)的新方法。在相转移催化剂的作用下,环氧氯丙烷与苄醇反应制得1,3-二苄氧-2-丙醇(1);1与五氧化二磷缩合后经氢化脱苄合成了β-3,纯度98%,总产率62%,其结构经31P NMR确证。并解释了脱苄反应过程中磷原子的邻位迁移现象。     

新型2-甲基吲哚衍生物的合成

2-甲基吲哚在草酰氯的存在下与DMF或DMA通过Vilsmeier-Haack反应制得2-甲基-3-甲酰基吲哚(1)或2-甲基-3-乙酰基吲哚(2);1或2与烷基化试剂通过N-烷基化反应合成了一系列新型的2-甲基吲哚类衍生物,其结构经1HNMR,13C NMR,IR和MS表征。     

N-(ω-三丁基锡甲氧基聚乙氧基)邻苯甲酰磺酰亚胺的合成及其光化学反应

烷基二醇与三丁基锡碘甲烷反应得到三丁基锡甲氧基烷基醇(2);2与邻苯甲酰磺酰亚胺反应得到N-(ω-三丁基锡甲氧基聚乙氧基)邻苯甲酰磺酰亚胺(3);3在光诱导下发生单电子转移,经分子间自由基偶合合成了新化合物1,4-二(2-邻苯甲酰磺酰亚胺基乙氧基)丁烷(7).2,3和7的结构经1H NMR,13C NMR及MS表征.     

新型1,1-双二茂铁基丁烷衍生物的合成

1,1-双二茂铁基丁烷和乙酸酐经Friedel-Crafts酰基化反应得6-乙酰基-1,1-双二茂铁基丁烷(2);2经LiAlH4还原得6-α-羟乙基-1,1-双二茂铁基丁烷(3);3经消除反应合成了6-乙烯基-1,1-双二茂铁基丁烷(4)。2~4为新化合物,其结构经1H NMR,IR,MS和元素分析表征。     

新型含1,2,3-三氮唑的染料木素糖缀合物的合成

以染料木素为起始原料,经两步反应制得中间体7-O-炔丙基染料木素(3);以CuI为催化剂,3与叠氮乙酰基糖经Click反应合成了7-O-［1-(2,3,4,6-四-O-乙酰基-β-D-糖苷)1H-1,2,3-三氮唑-4-甲基］-染料木素(5a~5c); 5a~5c经去乙酰基制得三种含1,2,3-三氮唑的氮苷染料木素糖缀合物(6a~6c)。3, 5和6均为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS表征。     

2-乙氧基-N-(4-甲基-2-丙基-1H-咪唑基-1)-苯甲酰胺的合成

2-乙氧基苯甲酸甲酯与水合肼发生肼解反应生成2-甲氧基苯甲酰肼(1);1与丁亚氨酸乙酯盐酸盐进行二次肼解反应制得2-乙氧基-N'-(1-亚胺丁基)苯甲酰肼盐酸盐(3);3与氯丙酮环化合成了2-乙氧基-N-(4-甲基-2-丙基-1H-咪唑基-1-)苯甲酰胺(合成伐地那非的关键中间体),总收率48%,其结构经1H NMR和MS确证.     

3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸的合成

以2,3-二氯吡啶为起始原料,通过水合肼亲核取代、马来酸二乙酯环合制得2-(3-氯-2-吡啶基)-5-氧-3-吡唑烷甲酸乙酯(5);5经苯磺酰氯酯化、溴化氢溴化制得3-溴-1-(3-氯-2-吡啶基)-4,5-二氢-1H-吡唑-5-甲酸乙酯(7);7经脱氢、水解合成了用于制备氯虫酰胺的关键中间体--3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸,总收率39.5%,其结构经~1H NMR和MS确证.     

合成E-10-羟基-2-癸烯酸的新方法

以1,8-辛二醇（1）为起始原料,经4步反应合成了（E）-10-羟基-2-癸烯酸,其结构经¹H NMR, ¹³C NMR和MS确证。考察了乙酰氯、缚酸剂种类及其用量［r=n（1）: n（乙酰氯）: n（缚酸剂）］对8-乙酰氧基-1-辛醇（2）收率的影响以及反应温度、三乙胺滴加温度、低温停留时间对8-乙酰氧基辛醛（3）收率的影响。结果表明：以三乙胺为缚酸剂,r=1.0 : 1.1 : 2.0时,2产率达78%;反应温度为-65 ℃、三乙胺滴加温度低于-50 ℃、低温反应3 h, 3产率达97%。     

含2-苯基-1，2，3-三唑基的单环β-内酰胺及噻唑啉酮衍生物的合成

以2-苯基-4-甲酰基-1，2，3-三唑为原料和芳胺缩合成一系列Schiff碱3， Schifft碱3与氯乙酰氯或苯氧乙酰氯在三乙胺条件下发生[2+2]环加成得到单环β- 内酰胺衍生物4a～4f或5a～5f，噻唑啉酮衍生物6是由Schifft碱3与巯基乙酸缩环 得到，化合物4a～4f, 5a～5f和6a～6f的组成及结构经元素分析，IR，~1H NMR和 MS确证。     

2-(4-咔唑-1-基-苯基)-1H-苯并咪唑的合成及其光学性质

以邻苯二胺与4-(咔唑-1-基)苯甲醛为原料,合成了一种新型苯并咪唑衍生物--2-(4-咔唑-1-基-苯基)-1H-苯并咪唑(2),其结构经¹H NMR, ¹³C NMR, MS（ESI), IR和元素分析表征。通过理论计算,结合UV-Vis和单光子荧光光谱研究了其光学性质,结果表明：2在二氯甲烷,乙酸乙酯,乙醇,乙腈和DMF中的λ_max均位于292 nm和330 nm 附近, λ_em分别为389 nm, 379 nm, 395 nm, 400 nm和390 nm。     

取代肉桂酰甘氨酸酯的合成

在N-甲基吡咯烷酮(NMP)促进下,取代肉桂酸(1a^1g)与二氯亚砜(SOCl2)在20℃酰氯化反应0.5 h,再加入甘氨酸乙酯盐酸盐,在40℃下酰胺化反应4 h,n(取代肉桂酸)/n(SOCl2)/n(甘氨酸乙酯盐酸盐)=1.0/1.2/1.4,合成了一系列取代肉桂酰甘氨酸乙酯(2a^2g),其结构经1H NMR、13C NMR、IR和MS(EI)确证。并探讨了NMP促进取代肉桂酰甘氨酸乙酯反应可能的机理。     

Azines and Azoles: CXX. Synthesis of Acyclic Analogs of N1-Ribosides of Barbituric Acid and Its 5-ylidene Derivatives

The reaction of 2,4,6-tris(trimethylsiloxy)pyrimidine with 2-oxabutane-1,4-diyl diacetate in methylene chloride in methylene chloride in the presence of SnCl₄ proceeds regioselectively to form 1-[(2-acetoxyethoxy)methyl]barbituric acid. The latter is readily deacetylated to a free acyclic analog of N-ribosides of barbituric acid. 1-[(2-Acetoxy- and 2-hydroxyethoxy)methyl]barbituric acids easily react with aromatic and heterocyclic aldehydes in water and organic solvents, forming 5-ylidenebarbituric acids. The structure of the products was proved by ¹H NMR and UV spectroscopy. Certain of the products exhibit a moderate antimicrobial and antiviral activity.     

2-羟基-4-(1′-甲庚氧基)苯烷酮肟的合成

具有邻位羟基的酮肟化合物(1)作为过渡金属螯合剂已在铜的萃取-电积工艺中得到广泛应用,如:LIX 64N(1a),LIX84(1b)及LIX 860(1c)。从萃取动力学行为来衡     

1-烷基-3-甲基咪唑氯化物焓变的热重分析

The structures of ionic liquids (ILs) based on 1-alkyl-3-methylimidazolium chloride [C_nmim]Cl (n = 2, 4, 6), (1-ethyl-3-methylimidazolium chloride [C₂mim]Cl, 1-butyl-3-methylimidazolium chloride [C₄mim]Cl, and 1-hexyl-3-methylimidazolium chloride [C₆mim]Cl) were elucidated by ¹H NMR and ¹³C NMR experiments. The vaporization characteristics of these ILs were studied by thermogravimetric analysis. Dynamic and isothermal thermogravimetric experiments were conducted in this study. The purpose of the dynamic experiments was to determine the initial decomposition temperature of the experimental sample and the temperature range for the isothermal thermogravimetric experiments. The purpose of the isothermal experiments was to record the mass dependence of the sample on time in the experimental temperature range. The Langmuir equation and Clausius-Clapeyron equation were used to fit the experimental data and obtain the vaporization enthalpies of these ILs at the average temperature within the experimental temperature range. However, in order to expand the applicability of the estimated values and to compare them with the literature data, the vaporization enthalpy ΔH_vap(T_av) measured at the average temperature was converted into vaporization enthalpy ΔH_vap(298) at ambient temperature. The difference between the heat capacities of the ILs in the gaseous and liquid states at constant pressure, Δ_l^gC_pm^ө proposed by Verevkin, was used in this conversion process. The experimental data for substance density and surface tension at other temperatures were obtained by referring to the literature. In addition, the data for density and surface tension at T = 298.15 K were obtained by applying the extrapolation method to the literature values for other temperatures. The vaporization enthalpy of the 1-octyl-3-methylimidazolium chloride IL [C₈mim]Cl was estimated by using the new vaporization model we had proposed in our previous work and compared with the reference value. The estimated value for [C₈mim]Cl was on the same order of magnitude as the reference value. We compared the vaporization enthalpies in the present study with those for the carboxylic acid imidazolium and amino acid imidazolium ILs ([C_nmim]Pro (n = 2-6) and [C_nmim]Thr (n = 2-6), respectively in our previous work. The results revealed that a change in the anion type affects the vaporization enthalpy of the ILs in the order amino acid imidazolium > carboxylic acid imidazolium > halogen imidazolium, when the cation is the same. Considering the structural differences between the three kinds of ILs, the abovementioned order may be related to the intermolecular hydrogen bonds. There were no intermolecular hydrogen bonds in the [C_nmim]Cl (n = 2, 4, 6) ILs studied here. Therefore, the vaporization enthalpy of [C_nmim]Cl (n = 2, 4, 6) was the lowest among the three kinds of ILs considered.     

磷酰化氨基酸酯的合成、波谱表征及生物活性

磷酰化氨基酸及其酯属于磷酰胺类, 它们作为天然氨基酸的含磷类似物, 具有良好的生物活性, 它的合成与性质的研究引起人们的浓厚兴趣. 本工作用亚硫酰氯先合成磷酰化酰氯, 再由其与氨基酸甲酯反应合成了一系列磷酰化氨基酸酯, 产物经红外光谱, 核磁共振氢谱、碳谱、磷谱, 质谱及元素分析鉴定, 并初步研究这些化合物的抗菌与抗肿瘤的生物活性.     

A functionalised ionic liquid: 1-(3-chloro-2-hydroxypropyl)-3-methyl imidazolium chloride

An ionic liquid (IL) containing an appended 3-chloro-2-hydroxypropyl functionality group 1-(3-chloro-2-hydroxypropyl)-3-methyl imidazolium chloride was synthesised by the reaction of N-methyl imidazole, hydrochloric acid and epichlorohydrin. The ionic liquid showed reasonably high conductivity and heat stability up to 230°C. Its structures were characterised by FT-IR, ¹H NMR and ¹³C NMR spectra. The physical characteristics of the ionic liquid, such as conductivity and solvation abilities have been investigated. Due to its high polarity, the IL is able to dissolve many inorganic salts, and due to hydroxyl-rich microenvironment, it is able to dissolve cellulose go up to 10 (wt%). The ILs can be used for synthesising other ILs or polyelectrolyte.