无溶剂固相合成3,3,6,6-四甲基-9-芳基-1,8-二氧代-1,2,3,4,5,6,7,8-八氢化氧杂蒽

以芳香醛和5,5-二甲基-1,3-环己二酮为原料,以磷磺酸作为催化剂固相合成了6个氧杂蒽二酮类衍生物。结果表明,在催化剂用量为5%,反应温度为120℃,反应时间为45 min时该方法产物产率可达89%~94%。方法具有产率高、操作简单、反应时间短和绿色环保等优点。     

无溶剂固相合成3,3,6,6-四甲基-9-芳基-1,8-二氧代-1,2,3,4,5,6,7,8-八氢化氧杂蒽

以芳香醛和5,5-二甲基-1,3-环己二酮为原料,以磷磺酸作为催化剂固相合成了6个氧杂蒽二酮类衍生物。结果表明,在催化剂用量为5%,反应温度为120℃,反应时间为45 min时该方法产物产率可达89%⁹4%。方法具有产率高、操作简单、反应时间短和绿色环保等优点。     

室温下碘催化合成3,3,6,6-四甲基-9-芳基-1,8-二氧代-1,2,3,4,5,6,7,8-八氢化氧杂蒽

以碘单质为催化剂,在冰醋酸介质中,由芳香醛与5,5-二甲基-1,3-环己二酮衍生物制备标题化合物,该反应在室温下反应2 h,产率达86%～92%.该法具有反应时间短、产率高、操作简便和环境友好等优点.     

酸性离子液体催化合成9-芳基-2,3,4,5,6,7-六氢-2H-氧杂蒽-1,8-二酮

报道了酸性离子液体1-(3-磺酸)-丙基-3-甲基咪唑磷酸二氢盐([HSO3(CH2)3mim]H2PO4)能有效促进1,3-环己二酮和芳香醛的缩合反应,生成标题化合物.反应具有环境友好、操作简单、速度快、产率高、离子液体可回收使用等优点,反应中酸性离子液体能同时起到催化剂和溶剂的双重作用.     

茚二酮、1,8-二氮杂-9-芴酮和茚三酮在手印序列显现中的应用

为了提高纸张上汗潜手印的显出率,选用茚三酮、1,8-二氮杂-9-芴酮(DFO)和茚二酮3种氨基酸检测试剂,对复印纸上连续按捺5次的手印进行序列显现,探究这3种试剂联合使用时显出率较高的序列。研究结果表明单独使用1种试剂时灵敏度排序是茚二酮>DFO>茚三酮;2种试剂联用序列显出率高的是DFO→茚三酮和茚二酮→DFO;3种试剂联用序列显出率最高的是茚二酮→DFO→茚三酮。因此,在进行手印序列显现时,先使用茚二酮,再用DFO,最后用茚三酮能达到最佳显现效果。     

Ullmann法合成氧杂蒽酮的研究

以2-氯苯甲酸和苯酚为原料,先经过Ullmann缩合反应制得2-苯氧基苯甲酸,再在三氯氧磷作用下脱水环合得到氧杂蒽酮。合成中间体产物的最佳条件是:n(2-氯苯甲酸)∶n(苯酚)∶n(碳酸钾)∶n(氧化铜)为1∶6∶1.5∶0.06。该方法具有操作简便、条件温和、环境友好等优点,氧杂蒽酮总产率有63.84%。     

SiO_2-SO_3H异相催化一步合成9-芳基-3,4,5,6,7,9-六氢-1H-氧杂蒽-1,8(2H)-二酮

以硅胶磺酸(SiO2-SO3H)为催化剂,4-芳硫基芳醛和1,3-环己二酮为原料,于乙醇中合成了标题化合物。该方法具有处理方便、反应时间短、产率高、催化剂价廉易得、可回收重复使用等优点。     

光引发剂硫杂蒽酮的合成工艺研究

硫杂蒽酮作为一类非常重要的光引发剂,是紫外固化涂料的重要组成部分。本文通过合成工艺改进,采用邻氯苯甲酸、对异丙基苯硫酚、氢氧化钠为原料,反应生成了2-异丙基硫杂蒽酮(ITX)。并通过一系列实验确定最佳参数,总收率达到85.5%。     

3-芳基-2,5-二甲基吡嗪类化合物的合成

利用Suzuki偶联反应以2,5-二甲基-3-氯吡嗪及取代苯硼酸为起始原料,合成了吡嗪衍生物,其结构经1H NMR、IR、EI-MS分析表征。结果表明:在氮气保护条件下,碱性二氧六环中,使用Pd(PPh3)4催化剂,除邻氰基苯硼酸因位阻效应收率较低外,其他产物的收率可达56%~94%。     

光引发剂1-氯-4-丙氧基硫杂蒽酮的合成

1 氯 4 丙氧基硫杂蒽酮(1 chloro 4 propoxythioxanthone,CPTX)是一种重要的紫外光固化材料光引发剂。以邻巯基苯甲酸为原料,与对氯苯酚在浓硫酸中环合,得到中间体1 氯 4 羟基硫杂蒽酮,收率为97 1%。1 氯 4 羟基硫杂蒽酮、溴丙烷和碳酸钾在丁酮中回流,得到CPTX,收率为87 5%。综合两步反应,收率由文献的52 6%提高到84 9%。     

SiO2-SO3H异相催化一步合成9-芳基-3,4,6,7,9,10-六氢吖啶-1,8(2H,5H)-二酮

以硅胶磺酸(SiO2-SO3H)为催化剂,4-芳硫基芳醛、1,3-环己二酮及醋酸铵为原料,于乙醇中合成了标题化合物.该方法具有处理方便、反应时间短、产率高、催化剂价廉易得、可回收重复使用等优点.     

Synthesis and pH‐induced phase transition behavior of PAA/PVA nanogels in aqueous media

Polyacrylic acid (PAA) and polyvinyl alcohol (PVA) are well‐known FDA‐approved biocompatible polymers. A novel method for preparing PAA/PVA complex nanoneedles in PVA aqueous solution is presented in this article. The PAA/PVA complex nanogels are obtained via polymerization of acrylic acid monomer after PVA nanoparticles formed in water/acetone cosolvent. The results of TEM images showed that the PVA chains were aggregated to form gel particles with some erose nanoparticles. As AA monomers polymerized around PVA nanoparticles, PAA/PVA complex nanogels formed. The PAA/PVA nanogels had an average diameter of 300–100 nm with AA concentration of 0.5–2 g/100 mL. As acetone concentration varied, TEM images demonstrated that the morphologies of resulting nanogels are different. Without acetone in PVA aqueous solution, however, PAA/PVA complexes aggregated to form earthnut‐like particles. These results show that the shape and size of PVA/PAA nanogels can be tailored as a template or core for the formation of PAA/PVA nanogels. These PAA/PVA nanogels exhibited pH‐induced phase transition due to protonation of PAA chains. The novel PVA/PAA nanogels promise to be developed into pH‐controlled drug delivery system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

可聚合乳化剂的合成及其在水性复膜胶中的应用

报道了马来酸酐单酯羧酸钠的合成,从理论上分析马来酸酐单酯羧酸钠作为水性复膜胶乳化剂的可行性,并与工业上可聚合乳化剂SVS、HPMAS、HAPS及常规的复合乳化剂K-12和OP-10进行比较,得出马来酸酐单酯羧酸钠A/B可用于水性复膜胶的制备,且性能优于SVS、HPMAS、HAPS、K-12和OP-10。     

冠醚催化氧化法合成对硝基苯甲酸

研究了冠醚作为相转移催化剂催化KMnO4氧化对硝基甲苯合成对硝基苯甲酸的反应,对影响反应的各种因素进行了分析讨论,如相转移催化剂用量、反应温度、反应时间、KMnO4用量等,优化了工艺条件.得出较优工艺条件为：n（KMnO4）∶n（对硝基甲苯）=3∶1,冠醚用量为反应底物的4％（摩尔分数）,反应温度为25℃,反应时间为6h,产物收率达74.8％.实验表明,冠醚对于KMnO4氧化对硝基甲苯合成对硝基苯甲酸的反应是一种优良的相转移催化剂.     

Partitioning behaviour of cephalexin and 7‐aminodeacetoxicephalosporanic acid in PEG/ammonium sulfate aqueous two‐phase systems

In order to develop an aqueous two‐phase system (ATPS) for cephalexin synthesis with extractive bioconversion, the partitioning behaviour of cephalexin and 7‐aminodeacetoxicephalosporanic acid (7‐ADCA) in poly(ethylene glycol) (PEG)/salt ATPS were examined. Parameters such as PEG size, salt type and tie line length were investigated to find a primary extraction system. In PEG400/ammonium sulfate and PEG400/magnesium sulfate systems, the partition coefficient of cephalexin (K_C) was larger than 1 while that of 7‐ADCA (K_A) deviated about 1.5. Addition of neutral salts, surfactants and water‐miscible solvents were also investigated in the primary ATPS in order to improve the separation efficiency. K_C greatly increased when neutral salts and surfactants were added to the PEG400/ammonium sulfate primary systems whereas K_A was only slightly higher than that of the additive‐free ATPS. In an improved ATPS for extractive bioconversion, consisting of PEG400 (20% w/w), ammonium sulfate (17.5% w/w), methanol (5% w/w) and NaCl (3% w/w), a K_C value of up to 15.2 was achieved; K_A was 1.8; K_P (partition coefficient of phenylglycine methyl ester) was 1.2 and the recovery yield of cephalexin was 94.2%. The results obtained from the extractive bioconversion of cephalexin in the improved ATPS showed that it is feasible to perform such an enzymatic process in an ATPS and the system offers the potential as a model for enzymatic synthesis of some water soluble products. © 2001 Society of Chemical Industry     

Immobilized Sulfuric Acid on Silica Gel as Highly Efficient and Heterogeneous Catalyst for the One-Pot Synthesis of Novel α-Acyloxycarboxamides in Aqueous Media

The application of immobilized sulfuric acid on silica gel (H₂SO₄-SiO₂) as an efficient and easily reusable solid catalyst was explored in the synthesis of novel α-acyloxycarboxamide derivatives via a Passerini reaction of benzoic acid, aldehyde/ketone, and isocyanides. The Passerini adducts were obtained in high to excellent yields within 10 min in aqueous media under catalytic conditions. The key advantages of the process include a short reaction time, high yields, the catalyst’s low cost, and the catalyst’s reusability.     

4-(9-蒽基)-6-辛氧基-1,3,5-三嗪-2-胺的合成及其在酸性介质中的光谱行为研究

以2,4-二氯-6-辛氧基-1,3,5-三嗪为原料,经Kumada偶联及胺化两步反应合成了三嗪胺衍生物:4-(9-蒽基)-6-辛氧基-1,3,5-三嗪-2-胺(AOOTA),总产率为38%.通过紫外-可见吸收光谱及荧光光谱研究了氯仿溶液中AOOTA在乙酸(HOAc)及三氟乙酸(TFA)作用下的光谱行为.研究发现AOOTA与HOAc在基态及激发态下均不能发生双氢键作用,而AOOTA与TFA相互作用基态下形成双氢键复合物,激发态下由于分子中蒽基及辛氧基与三嗪环间的C—C单键以及C—O单键的自由旋转,从而使得AOOTA与TFA分子间不能形成有效的氢键相互作用.