香料1,5-二硫杂螺[5,5]十一烷的合成

以环己酮和1,3-丙二硫醇为原料,TiSiW12O40/TiO2作催化剂,合成了一种新型香料化合物1,5-二硫杂螺[5,5]十一烷,并用元素分析、IR、1HNMR对其结构进行表征。结果表明,n(环己酮)∶n(1,3-丙二硫醇)=1.0∶1.2,催化剂用量约为环己酮质量的4%,反应3 h,目标产物的收率为86.5%。催化剂无需处理可直接重复使用8次以上。     

除草剂解毒剂N-二氯乙酰基-2-甲基-1-氧杂-4-氮杂-螺[4.4]壬烷的合成

以33%的氢氧化钠水溶液为缚酸剂,异丙醇胺、环戊酮和二氯乙酰氯为原料,采用“一锅法”合成了N-二氯乙酰基-2-甲基-1-氧杂-4-氮杂-螺[4.4]壬烷,采用正交实验法得到最佳反应条件：反应原料摩尔比为1∶1∶1.2,苯作溶剂,反应的温度为-15℃～-10℃,搅拌时间为3h,产率达到50.0%。并采用UV、IR、1HNMR和MS对该化合物的结构进行了表征。     

螺[3.4]辛-6-酮的合成研究

在二聚醋酸铑的催化作用下,5-环丁基-2-重氮-3-氧代戊酸甲酯经C-H插入反应得到6-氧代螺[3.4]辛烷-5-羧酸甲酯,再在酸性条件下经脱羧反应得到目标化合物螺[3.4]辛-6-酮;通过~1HNMR和ESI-MS对中间体及目标化合物的结构进行了确证,并对合成工艺进行了考察。确定C-H插入反应的最佳条件如下:二聚醋酸铑与5-环丁基-2-重氮-3-氧代戊酸甲酯物质的量比为0.05∶1、反应溶剂为二氯甲烷、反应温度为25℃、反应时间为2 h;脱羧反应的最佳条件如下:反应温度为70℃、反应时间为8 h。在上述条件下,反应总收率达到60.6%。该方法操作简单、收率高,为螺[3.4]辛-6-酮衍生物的合成提供了一种简便有效的途径。     

9-Boc-1-氧-4,9-二氮杂螺[5,5]十一烷的合成

以N-Boc-4-哌啶酮为原料,经亲核加成、氢化还原、氯乙酰化、环化及还原等反应合成目标产物9-Boc-1-氧-4,9-二氮杂螺[5,5]十一烷,并对其中影响收率的关键步骤进行优化,得到了反应条件温和、操作简便、收率高的合成路线,总收率达50%。     

1,4-二氧杂螺[4.5]癸烷-8-酮的回收与提纯

在生产液晶中间体4-羟基-4-(2,3-二氟-4-正丁氧基)苯基环己酮的废液中含有10%~30%的1,4-二氧杂螺[4.5]癸烷-8-酮,采用亚硫酸氢钠盐析法得到磺酸盐与有机物分离,然后还原得到1,4-二氧杂螺[4.5]癸烷-8-酮粗品,再经过重结晶得到合格的目的产品,GC含量>99.5%,回收率>80%。并对产品进行了GC-MSS,DCS,IR,1H NMR的确认。     

8-氧杂双环[3.2.1]辛-3-胺盐酸盐的合成研究

报道了一种8-氧杂双环[3.2.1]辛-3-胺盐酸盐的简便制备方法。以8-氧杂双环[3.2.1]辛-3-酮为原料,通过刘卡特反应,再与氯化氢二氧六环溶液成盐得到目标化合物。产物结构经1H NMR和ESI-MS确证。最佳反应条件为:反应温度室温,反应溶剂甲醇/水,甲酸铵用量5当量,Pd/C催化剂用量为原料质量的10%,反应时间16 h,收率为67.0%。     

4-溴螺环[芴-9,9'-氧杂蒽]的合成与表征

以二苯醚为原料,惰性气体保护下,与仲丁基锂反应,加入4-溴-9-芴酮,在冰乙酸溶剂中闭环合成4-溴螺环[芴-9,9'-氧杂蒽]。其结构经~1H NMR等表征确证。优化反应条件为:n(二苯醚)∶n(仲丁基锂)=1∶1,锂化温度-75℃。总收率86%。     

甘油与环己酮缩合反应催化剂的研究

通过比较Lewis酸、质子酸、无机酸酐、分子筛、酸化蒙脱土在催化甘油与环己酮缩合反应中的活性,研究了催化剂结构和性质对环己酮转化率和反应选择性的影响。结果表明,Lewis酸有较高的催化活性和稳定性,而且表现为L酸和B酸两种酸的催化形式。催化剂结构对环己酮转化率和反应选择性的影响为:(1)Lewis酸的构成:对相同阴离子的Lewis酸而言,其阳离子的L酸酸强度越强或水解程度越大,催化活性和2-羟甲基-1,4-二氧杂螺环[4,5]癸烷(产物a)的选择性越高;对相同阳离子的Lewis酸而言,其盐酸盐型的催化活性和产物a的选择性要高于硫酸盐型的;(2)水合硫酸盐的催化活性与其煅烧温度有关。催化活性和产物a的选择性最好的Lewis酸为AlCl3。当n(AlCl3)∶n(环己酮)∶n(甘油)=1∶10 000∶15 000,带水剂环己烷加入量为反应物总体积的47%,92℃回流反应2 h,环己酮转化率为97.9%;最终产物中产物a的选择性为97.8%。     

3-溴螺环[芴-9,9'-氧杂蒽]的合成工艺研究

螺[芴-9,9'-氧杂蒽]衍生物作为蓝光材料或掺杂材料,被广泛应用于有机发光半导体(OLED)器件.本文以二苯醚为起始原料,经仲丁基锂锂化后,与3-溴-9H-芴酮反应得到中间体化合物,在二氯甲烷溶剂中,经对甲基苯磺酸催化闭环反应,合成了3-溴螺环[芴-9,9'-氧杂蒽].研究表明,当锂化反应温度为-45℃,原料n(二苯...     

11,12-二氢-11-苯基-吲哚并[2,3-a]咔唑的合成研究

以1-氨基-N-苯基咔唑为起始原料,经选择性溴化反应、Suzuki偶联反应和Buchwald偶联反应合成了11,12-二氢-11-苯基-吲哚并[2,3-a]咔唑,通过NMR对化合物结构进行了表征。研究了反应温度、催化剂用量、反应时间等因素对目标化合物收率的影响,得出最佳反应条件:反应温度为90℃,反应时间为26h,催化剂醋酸钯用量为1-氨基-N-苯基咔唑摩尔量的4%。     

Spray-dried hydroxyapatite-5-Fluorouracil granules as a chemotherapeutic delivery system

This study describes the preparation and characterization of hydroxyapatite-5-Fluorouracil (5FU) granules, which are intended to be used as chemotherapeutic delivery matrices and bone regeneration templates. Suspensions of hydroxyapatite (Hap) nanoparticles in 5FU solution are spray dried as micro sized granules having donut type shape. Several spray drying temperatures are studied 80 °C being the optimized condition for obtaining granules composed by Hap and 5FU without secondary phases. The produced granules at 80 °C reveal a fast releasing rate of 5FU when soaked in buffer phosphate solution maintained at physiological temperature (37 °C), thereby indicating the potential application of the produced Hap matrices for drug delivery systems (DDSs).     

Two-component,one-pot synthesis of pyrimido[1,2-b] [1,2,4,5]tetrazines

Derivatives containing the cyclohepta4′,5′thieno[2′,3′:4,5]pyrimido[1,2-b][1,2,4,5]-tetrazin-6-one system were prepared from the reaction of 3-amino-2-thioxo-1,2,3,5,6,7,8,9-octahydro-4H-cyclohepta[4,5]thieno[2,3-d]pyrimidin-4-one (5) or its 2-methylthio derivative 6 with hydrazonoyl chlorides 9. The mechanism of the studied reactions has been discussed and the biological activity of the isolated products has been evaluated.     

室温离子液体的制备及物化性能研究

合成了[bm im]B r和[bm im]BF4室温离子液体,考察了其在不同溶剂中的溶解性能及导电性能,同时对离子液体在不同溶剂中的紫外吸收进行了测定。结果表明,离子液体在水、乙醇、乙酸、丙酮中可以较好的溶解,而在乙醚、苯、正己烷中不溶解;离子液体的电导率随浓度的增大和温度的升高而增大,在不同的溶剂中的电导率K不同,而且相差很大,其顺序为K(水作溶剂)>K(乙醇作溶剂)>K(乙酸作溶剂)。溶剂的极性对离子液体的紫外吸收影响较大,最大吸收波长的顺序为:λm ax(水为溶剂)<λm ax(乙醇为溶剂)<λm ax(乙酸为溶剂)。     

离子液体中间体1-丁基-3-甲基咪唑溴盐的合成

以N-甲基咪唑和1-溴代正定烷为原料合成1-丁基-3-甲基咪唑溴盐[Bmim]Br,研究了反应时间、反应温度、及N-甲基咪唑与1-溴代正丁烷的摩尔比(原料比)和溶剂对[Bmim]Br收率的影响,产物结构经过1H NMR及FT-IR确认.实验结果表明,反应温度在60℃,反应时间为24h,N-甲基咪唑与1-溴代正丁烷的摩尔比(原料比)为1:1.2时,收率为93.13%.     

离子液体N-甲基咪唑对甲苯磺酸盐催化剂的制备及应用

采用一步法制备Brφnsted酸性离子液体N-甲基咪唑对甲苯磺酸盐催化剂（[Hmjm]TsO）,并对其进行了红外光谱、拉曼光谱等表征。将其应用于醋酸和正丁醇的酯化反应,详细考察了离子液体用量、反应时间、醇酸物料比、反应温度等因素对酯化反应的影响,并确定了较佳反应条件为：温度95～98℃,n（丁醇）：n（醋酸）：1．2：1,离子液体用量为反应物总质量的20．O％,反应时间6h,酯化率可达到85．0％。同时,[Hmim]TsO离子液体循环使用6次后,酯化率仍可达到78．2％。     

Synthetic strategies for thiazoloquinoxalines and their applications

The current review article represents a survey of the literature covering the synthetic strategies leading to thiazoloquinoxalines for the first time. The review is divided into four parts discussing four groups of thiazoloquinoxalines classified based on the type of fusion between the thiazole and quinoxaline nuclei.     

四氮杂杯[2]芳烃[2]三嗪的合成及其叠氮化研究

研究了四氮杂杯[2]芳烃[2]三嗪的合成及其叠氮化。以三聚氯氰和间苯二胺(摩尔比>2∶1)为原料,碳酸钾为缚酸剂,四氢呋喃为溶剂,在冰浴条件下合成中间体N,N’-二(4,6-二氯-1,3,5-均三嗪-2-基)-1,3-苯二胺,产率为85.8%;该中间体和间苯二胺(摩尔比为1∶1)丙酮为溶剂,在室温条件下反应,生成四氮杂杯[2]芳烃[2]三嗪,产率为45.5%;四氮杂杯[2]芳烃[2]三嗪和叠氮钠在40~50℃条件下反应生成四氮杂杯[2]-1,5-芳烃[2]-2-叠氮基-1,3,5-三嗪产率为90.0%。产物通过元素分析、红外光谱和氢谱的表征,其结构得到了确定。     

Chemistry of 2-cyanomethylene-4-thiazolidinone

This article is a brief review about the synthesis and chemistry of 2-cyanomethylene-4-thiazolidinone 1. The most significant applications of 4-thiazolidinone 1 in heterocyclic synthesis are due to its two reactive methylenes. The endo-cyclic methylene protons are activated by the neighboring carbonyl moiety and the exo-cyclic methylene protons by the adjacent cyano group. Different types of reactions, such as alkylation, coupling, and Knoevenagel condensation, as well as cyclization reactions are illustrated for the synthesis of different classes of biologically important heterocyclic skeletons from this novel precursor.     

Algebraic Structure Count of Cyclobutadienyl Bridged Polyacenes

Abstract

By substitution of the benzene rings in [n]phenylenes with polyacene units (all being of the same length) a new class of compounds is obtained. By analogy we call this class [n]acenylenes. Beside linear (X_n), we also examine angularly linked acenylenes which might be realized in two extreme ways: by connecting the polyacene units in a strictly spiral way (Y_n) or in the so called zig-zag manner (Z_n).

The recursion formulae for the algebraic structure count (ASC) of X_n, Y_n and Z_n are derived here, and they read as:

ASC(X_n) = (h + 1). ASC(X_n-1)—ASC(X_n-2)

ASC(Y_n) = h. ASC(Y_n-1) + ASC(Y_n-2)

ASC(Z_n) = h. ASC(Z_n-1) + ASC(Z_n-2)

where n denotes the number of polyacene units and h the number of hexagons in each polyacene unit.

It is proved that Y_n and Z_n have equal ASCs.     

Imidazobenzothiazoles: synthesis and application

This review article focuses on the synthesis of various types of imidazobenzothiazoles, which are potentially useful for the development of biologically active heterocycles. The synthetic methods are simple and practical and are conceivably applicable to analogous heterocyclic systems possessing nitrogen and sulfur. Also, some commercial applications of these compounds are reported as well.