2-甲基-4-羟基-6-苯基嘧啶和2-甲基-4-羟基-5-溴-6-苯基嘧啶的高效液相色谱法分离测定

采用ODS-C18色谱柱和紫外检测器,对2-甲基-4-羟基-6-苯基嘧啶和2-甲基-4-羟基-5-溴-6-苯基嘧啶的含量进行HPLC分离测定.以甲醇水=4555为流动相,紫外检测波长为237 nm,样品线性范围为0.001～0.1 mg/mL.2-甲基-4-羟基-6-苯基嘧啶的RSD为0.5%;2-甲基-4-羟基-5-溴-6-苯基嘧啶的RSD为1.0%.     

3-甲基-1-戊烯-4-炔-3-醇的合成

以甲基乙烯酮为原料,用乙炔基格氏试剂对其加成,然后水解得到目标物3-甲基-1-戊烯-4-炔-3-醇。研究了温度对反应的影响,发现在25℃的反应温度下,目标化合物的气相色谱产率为50%,减压蒸馏纯化后收率为30%。目标产物用1HNMR、IR进行了表征。     

6-叔丁基-3-氯甲基-2,4-二甲基苯酚的合成

以2,4-二甲基-6-叔丁基苯酚、多聚甲醛和三氯氧磷为原料,在四氯化碳溶剂中合成了6-叔丁基-3-氯甲基-2,4-二甲基苯酚并确定较佳的工艺条件,分别考察了物料配比、反应温度、反应时间和相转移催化剂用量对反应收率的影响。确定较佳工艺为:在四氯化碳溶剂中,反应温度为40℃,2,4-二甲基-6-叔丁基苯酚用量为60 g,多聚甲醛12 g,浓盐酸30 g,相转移催化剂4 g,三氯氧磷40 g。在上述条件下,6-叔丁基-3-氯甲基-2,4-二甲基苯酚的收率为95%,纯度>99%(HPLC面积归一化法),产品结构经IR、MS和~1H-NMR表征。     

2-甲氧基-3-氟-4-碘吡啶的合成

2-甲氧基-3-氟-4-碘吡啶是一个重要的医药化工中间体,其合成路线未见文献报道。以2-甲氧基-3-氟-5-氯吡啶为起始原料,经氢解和碘代两步反应合成标题化合物,总收率62.8%,其结构经¹H NMR, ¹³C NMR和MS确证。     

(±)-12-乙基-13-甲氧基-8,11,13-罗汉松三烯-7-酮和(±)-12-乙基-13-甲氧基-8,11,13-罗汉松三烯的全合成

以α-环柠檬醛(1)为A环合成子,以季盐(2)为C环合成子,经缩合及分子内环化反应得到关键中间体(5).为引入乙基,进行了Friedel-Crafts反应和脱氧反应等,共经7步反应得到了(±)-12-乙基-13-甲氧基-8,11,13-罗汉松三烯-7-酮[(±)-nimbonone](9)及(±)-12-乙基-13-甲氧基-8,11,13-罗汉松三烯(10).     

6-甲基-5-硝基-3-吡啶硼酸频哪酯合成工艺的改进

以2-氯-3-硝基-5-溴吡啶为起始原料,经取代反应、水解反应、Suzuki偶联反应得到6-甲基-5-硝基-3-吡啶硼酸频哪酯。反应总收率为51%,中间体及目标产物结构由IR和1H-NMR表征。     

稳定烯醇结构3-氯-2-羟基-4-羰基-4-对甲苯基-2-丁烯酸乙酯的合成

以甲苯为起始原料,通过傅克-酰基化、Aldol反应合成了具有稳定烯醇结构的3-氯-2-羟基-4-羰基-4-对甲苯基-2-丁烯酸乙酯,反应过程生成了中间体3,3-二氯-2-羟基-4-羰基-4-对甲苯基丁酸乙酯,采用红外、核磁共振谱、HRMS产品进行了测定和结构表征。对反应机理进行了初步探讨。     

水溶剂中反-2,3-环氧-1-苯基-3-(2′-硝基-5′-氯苯基)-1-丙酮的合成及产物的晶体结构

用 2-硝基-5-氯苯甲醛、氯代苯乙酮和氢氧化钠以三乙基苄基氯化铵作催化剂在水溶剂中反应可合成反-2,3-环氧-1-苯基-3-(2′-硝基-5′-氯苯基)-1-丙酮(C15H10ClNO4)。产物的结构通过单晶 X-射线衍射法确定,其晶体属于单斜晶系。空间群 P21/c, a = 9.942(1), b = 15.774(3), c =8.756(1) ?, β = 96.39(1)°, Mr = 303.69, Z = 4,V = 1364.6(3) ?3, Dc = 1.478 g/cm3, μ(MoKα) =0.295 mm–1, F(000) = 624, 最终的偏离因子为 R = 0.0336, wR = 0.0745。X-衍射分析表明, 该产物为反式异构体。     

2-氨基-4-甲氧基氯代苯甲酸的合成研究

以2-氨基-4-甲氧基苯甲酸甲酯为原料,通过氯代反应,再分别通过酯水解反应得到化合物2-氨基-5-氯-4-甲氧基苯甲酸和2-氨基-3-氯-4-甲氧基苯甲酸。其中间体及产物结构经~1H NMR、~(13)C NMR和ESI-MS确证,并考察了最佳氯代反应条件。结果表明:物料配比为n(2-氨基-4-甲氧基苯甲酸甲酯)∶n(NCS)=1∶1. 2,反应溶剂为N,N-二甲基甲酰胺,反应时间为16 h,两种氯代产物2-氨基-5-氯-4-甲氧基苯甲酸甲酯和2-氨基-3-氯-4-甲氧基苯甲酸甲酯收率分别为47%和39%。     

合成3-羟基-2-(4-吡啶基)-1H-茚-1-酮的工艺改进

以邻苯二甲酸酐和4-甲基吡啶为起始原料,正十二烷为溶剂,氯化锌为催化剂,于190℃反应24 h合成了抗癌药物瓦他拉尼的关键中间体——3-羟基-2-(4-吡啶基)-1H-茚-1-酮,收率90.6%,其结构经1H NMR,IR和MS确证。     

Aluminosilicate and aluminosilicate based polymer composites: Present status,applications and future trends

Aluminosilicates have traditionally been important materials for applications related to adsorbents, water softeners, catalysis and mechanical and thermal reinforcement due to their high surface area, excellent thermal/hydrothermal stability, high shape-selectivity and superior ion-exchange ability. Recently, their use as polymer fillers has allowed to increasingly extending their application range to innovative areas such as medical and biological fields as well as in sensors, filtration membranes, energy storage and novel catalysis routes. Further, the large versatility and tailoring possibilities of both filler and matrix indicates this area as one of the enabling key technologies of the near future.This work summarizes the main developments up to date in this increasingly interesting field, focuses on the main applications already developed as well as on the key challenges for the near future.     

Benzothiazoles from Condensation of o-Aminothiophenoles with Carboxylic Acids and Their Derivatives: A Review

Nowadays, organic chemists are interested in the field of heterocyclic chemistry due to its use in the synthesis of a great variety of biologically active compounds. Heterocyclic compounds are widely found in nature and are essential for life. Among these, some natural nitrogen containing heterocyclic compounds have been used as chemotherapeutic agents. Their attachment to sugar molecules either as thioglycosides or as nucleosides analogues plays an important role in vital biological processes as well as in synthetic organic chemistry. Molecules containing benzothiazole (BT) nuclei are of this interesting class of compounds because some of them have been found to have a wide variety of biological activities. In this sense, we selected this topic to review and to then summarize the procedures related to the condensation reactions of o-aminothiophenoles (ATPs) as well as their disulfides with carboxylic acids, esters, orthoesters, acyl chlorides, amides, and nitriles. The condensation reactions with carbon dioxide (CO₂) are included. Conventional methods with the use of acid and metal catalysts as well as recent green techniques, such as microwave irradiation, the use of ionic liquids, and ultrasound (US) chemistry, which have proven to have many advantages, were found in the review.     

和医学相关有机化合物绿色鉴别实验的设计*

为了将医用化学实验中“有机化合物的鉴别”实验更加密切地与医学相关专业结合,并提高实验操作的安全性,降低化学试剂的毒性与刺激性,甄选出一系列与医学密切相关的有机化合物作为待鉴别试剂,同时设计绿色环保、安全低毒、现象明显、操作简便、成本低廉的鉴别方法,为学生实验方案的设计提供指导。以期提高医学生学习的积极性与主动性,促进学生灵活运用知识分析问题、解决问题,为相关教学工作的改进提供借鉴意义。     

Reaction of Oximes of α-Diketones with Diphosphorous Tetraiodide for Preparation of Oxadiazoles and Nitriles

The utility of diphosphorous tetraiodide as a new, mild, condensing agent for synthesis of oxadiazole is described. These data indicate the simple dehydration of oximes to 1,2,5-oxadiazole as well as the rearrangements of oximes to normal Beckmann product 1,2,4-oxadiazole. However, mono-oxime of benzil undergoes abnormal Beckman rearrangement to benzaldehyde as major product. The described method is simple and important for the synthesis of the oxadiazoles as well as for nitriles.     

Nitraza-/Oxa-Propylene- and Hydrazonemethylene-Bridged 1,2,4-Nitraminotriazoles and Selected Salts

Two new bridged nitraminotriazoles with bridging oxapropylene and nitrazapropylene moieties were synthesized, and converted into several salts, as well as from the hydrazonemethylene bridged nitraminotriazole. All compounds were fully characterized by NMR and IR spectroscopy, elemental analysis as well as differential thermal analysis. The sensitivity towards friction and impact were determined according to BAM standard technics and the energetic properties were calculated by using the EXPLO5 computer code. The neutral compounds as well as the various salts were examined in terms of their physicochemical properties and detonation performance to each other and compared to the commonly used secondary explosive RDX.     

片状纳米CuO用于苯乙烯氧化反应的研究

苯甲醛又称安息香醛,是医药、染料、香料工业的一种重要的中间体,主要用于制造品绿、月桂醛、月桂酸等;也有时用作有机溶剂,测定臭氧及位于羰基旁边的亚甲基及检定酚和生物碱的试剂.传统的工业生产方法是以石油化工中的甲苯为原料,经氯化生成二氯化苄,再经酸性或碱性水解、真空     

Enzyme-based biocatalysis for the treatment of organic pollutants and bioenergy production

Enzyme-based biocatalysis is emerging as an advanced technique to develop green processes that help to maintain the sustainability of the environment. The bioremediation of toxic organic pollutants and waste to bioenergy production using enzymes as biocatalysts is rapidly growing due to its eco-friendly and sustainable nature. Additionally, a range of microbial species that typically grow on organic wastes can be used to produce these enzymes in an efficient manner. This is seen as a potential strategy for the development of cost-effective manufacturing for a number of biotechnological applications. The present study discusses biocatalysis as a promising and sustainable method toward the bioremediation of hazardous organic pollutants as well as for bioenergy production, based on the immense potential of enzymes as biocatalysts. Emphasis has been placed on evaluating the critical elements that can enhance the production of enzymes used as biocatalysts, as well as their functional effectiveness and stability.     

Application of Carrageenan extract from red seaweed (Rhodophyta) in cosmetic products: A review

Cosmetic industries have expanded globally and will continue to increase as there are consumers. Nowadays, the interest starts to incline towards cosmetics formulated using plant-based ingredients. Marine plants such as seaweed possess numerous natural polysaccharides. Carrageenan is one of the compounds that can be extracted from red seaweed (Rhodophyta). This natural polysaccharide is widely known to act as a thickener, stabilizer, and water-binding agent as well as have diverse biological activities that make it a suitable active ingredient in cosmetic products. The review paper is organized by starting with discussing the significant aspects related to carrageenan which are the source, structure, as well as general and biological properties of carrageenan that make it appropriate to be applied in cosmetics. This paper also highlighted the applications of carrageenan in cosmetics, followed by the extraction method and instrument used.     

Colloidal chemistry as a guide to design intended dispersions of carbon nanomaterials

In this review, some established concepts from Colloidal Science and their application to graphene and carbon nanotubes dispersions in organic or aqueous media are highlighted to rationalize alternatives for some issues in terms of colloidal properties. Recent applications for carbon-based dispersions are presented, as well as van der Waals interactions in carbon materials and strategies to overcome these interactions, such as increasing electrostatic repulsion between dispersed particles, surface functionalization, or adsorption of passivation agents such as macromolecules, which are the basis of many dispersion and exfoliation procedures. The demonstration of how knowledge and fine control of colloidal interactions have been used to overcome several limitations, such as the preparation of stable and concentrated dispersions of carbon materials and keeping appreciable electrical conductivity, is presented. It is also showed that the same knowledge can help the development of more environmentally friendly carbon-based colloids as well as the improvement of similar systems as dispersions of two-dimensional materials.     

Two-mode Fluorescent Detection of Cyanide by a Simple AIE-based Chemosensor with Red Emission

TPE-TCF, a simple TPE-derivative with red-emission was used to detect cyanide in the condition of single dispersion as well as under aggregate state. It could be found that TPE-TCF exhibited excellent fluorescent response to cyanide in both situations, and the mechanism was supposed to be the reaction between cyanide and the double bond in TPE-TCF as well as the aggregation induced emission property of the reacted TPE-TCF molecules. What's more, TPE-TCF could distinguish cyanide with other species, such as common anions and biotiol well, which indicated it as a potential indicator for cyanide with good selectivity and specificity.