聚(N-丙烯酰基-氨基四唑)合成及表征

在浓碱溶液条件下丙烯酰氯和5-氨基四唑反应,合成了新型高含氮聚合物聚(N-丙烯酰基-氨基四唑)。其主要创新点是将高氮化合物5-氨基四唑引入到了高分子链上。测定了此聚合物在选定溶剂中的溶解度,用二甲基亚砜溶解聚合物测定特性黏度,并测定了聚合物的吸湿率等性能。结果表明,此聚合物相对分子质量适中,吸湿率较低,可以用作发射药的高分子消焰剂。     

氨基四唑含能化合物研究进展

氨基四唑是有机物中含氮量最高的一类化合物,具有高的正生成焓和良好的热力学稳定性,在高能钝感炸药、气体发生剂、无烟烟火剂、固体推进剂等领域有着广泛的应用前景。氨基四唑主要包括分子化合物、离子化合物和配合物3种。本文综述了5-氨基四唑和1,5-二氨基四唑类含能化合物的合成及性能。在此基础上,分析了氨基四唑类含能化合物的未来发展趋势。     

2-甲基-5-乙烯基四唑的合成与表征

由3-羟基丙腈与叠氮化铵采用超声波辐射技术经1,3-偶极环化加成获得母体化合物5-羟乙基四唑;母体化合物与硫酸二甲酯经取代反应得到中间体甲基-5-羟乙基四唑,然后甲基-5-羟乙基四唑再与氯化亚砜经卤代反应得到中间体2-甲基-5-氯乙基四唑,收率为68%;2-甲基-5-氯乙基四唑在碱性条件下经消除反应生成2-甲基-5-乙烯基四唑,收率为75%。采用红外光谱、核磁共振、元素分析等对2-甲基-5-氯乙基四唑、2-甲基-5-乙烯基四唑进行了结构表征。该法具有反应收率较高且稳定、易操作等优点。     

四唑结构在生物活性小分子设计中的研究进展

四唑环在生物活性小分子设计合成方面的应用日益广泛。四唑化合物不仅具有广泛的生物活性,同时四唑结构也是多种化学结构的电子等排体,通过基团替换获得结构多样性的四唑衍生物以改善小分子化合物的生物活性。对四唑结构在生物活性小分子的设计方面的进展情况进行了综述。     

5-乙烯基四唑的合成及表征

3-羟基丙腈与叠氮化铵(叠氮化钠与氯化铵反应获得)经1,3-偶极环化加成获得5-羟乙基四唑,在该合成过程中应用超声波技术,使收率提高至90.5%.5-羟乙基四唑与氯化亚砜经卤代反应得到5-氯乙基四唑,收率为77%;5-氯乙基四唑在碱性条件下经消除反应生成目标化合物5-乙烯基四唑,收率为70%.采用红外光谱、核磁共振、元素分析等对5-氯乙基四唑、5-乙烯基四唑进行结构表征.结果表明,所得产物为目标化合物.该法具有反应收率较高且稳定、易操作等优点.     

3,4-双(5-氢-1-四唑基)呋咱的合成及理论计算

以3-氨基-4-硝基呋咱(ANF)为原料,与原甲酸三乙酯、叠氮化钠反应,得到3-硝基-4-(5-氢-1-四唑基)呋咱(化合物1),然后低温下经氨水胺化得到3-氨基-4-(5-氢-1-四唑基)呋咱(化合物2),化合物2与原甲酸三乙酯、叠氮化钠反应,最终得到3,4-双(5-氢-1-四唑基)呋咱(化合物3)。采用IR、~1 H NMR、~(13) C NMR及元素分析对3种化合物的结构进行了表征;采用密度泛函理论B3LYP/6-311+G**方法预估了化合物1~3的标准生成焓、密度、爆速、爆压。结果表明,通过控制反应条件,确定了制备化合物2的最佳工艺条件为:化合物1与氨水摩尔比为1∶2,反应时间3h,反应温度-10℃。化合物2的收率为70%。四唑环的引入使化合物1~3都具有较高的正生成焓,其中化合物3最高,达到1 090.07kJ/mol。化合物1的爆速、爆压与RDX相当。除化合物2密度略低于TNT外,化合物1~3各性能均优于TNT。与化合物2和3综合比较,化合物1的性能最佳,密度为1.76g/cm~3,爆速为8 590m/s,爆压为32.3GPa。     

四唑基聚合物的研究进展

综述了四唑基聚合物的合成方法,包括环加成反应、自由基聚合反应、官能团反应。介绍了四唑基聚合物在含能材料和质子交换膜材料方面的应用,四唑基聚合物用于制备含能材料具有能量高、感度低的优点,而作为质子交换膜材料,不但具有基本的导电性能,还能在高温及无水情况下的应用。     

含二茂铁基及取代四唑的酰腙化合物合成

本文用甲酰基二茂铁和乙酰基二茂铁分别与取代四唑类酰肼化合物在乙醇介质中反应，合成了八个未见报道的二茂铁基取代四唑杂环酰腙化合物。所有化合物都通过了元素分析，红外光谱，以及核磁共振氢谱的确证，并对这些化合物的酸催化合成方法进行了讨论。     

2-噁唑啉化合物的合成及其在聚合物中的应用

综述了近年来2-噁唑啉化合物在合成领域的研究进展,主要介绍了β-氨基醇与羧酸或羧酸酯反应,酰胺环化反应,以腈类化合物为原料反应等合成方法。总结了2-噁唑啉化合物在聚合物改性方面的应用进展,并预测了2-噁唑啉化合物的合成与应用发展趋势。     

新型塑料助剂——2—噁唑啉化合物的合成与应用

本文介绍了一种新型塑料助剂2-噁唑啉化合物的合成方法及应用领域。该类化合物由于有活性基团,能在混炼时与缩聚系聚合物反应可以起扩链效果,增加塑料的相容性,改善塑料的机械性能,具有广泛的应用前景。     

Polymers and copolymers based on vinyl tetrazoles, 1. Synthesis of poly(5-vinyl tetrazole) by polymer-analogous conversion of polyacrylonitrile

Interaction of polyacrylonitrile with sodium azide and ammonium chloride leading to the formation of poly(5-vinyl tetrazole) has been studied in detail. The reaction is found to proceed to high conversion extents (up to 94–94.5%) and allows to obtain polymeric products with a wide range of poly(5-vinyl-tetrazole) content. Comparative studies of the structures and properties of the obtained polymers and 5-vinyl tetrazole homopolymer as well as copolymers of 5-vinyl tetrazole with acrylonitrile have been carried out using IR, ¹³C NMR and complex thermal analysis data.     

Thermoanalytical Screening of Nitrogen-Rich Substances

The thermal decomposition behaviour of approx. 60 nitrogen-rich substances on the basis of tetrazole and tetrazine structures was investigated by thermoanalytical methods. Decomposition mechanisms initiated by ring opening of the heterocycles could be established. Substituent effects on the exothermic decomposition characteristics of nitrogen-rich compounds are demonstrated.     

Designing Multitarget Anti-inflammatory Agents: Chemical Modulation of the Lumiracoxib Structure toward Dual Thromboxane Antagonists-COX-2 Inhibitors

A series of lumiracoxib derivatives were designed to explore the influence of isosteric substitution on balancing COX-2 inhibition and thromboxane A(2) prostanoid (TP) receptor antagonism. The compounds were synthesized through a copper-catalyzed coupling procedure and characterized for their pK(a) values. TP receptor antagonism was assessed on human platelets; COX-2 inhibition was determined on human isolated monocytes and human whole blood. TPα receptor binding of the most promising compounds was evaluated through radioligand binding assays. Some of the isosteric substitutions at the carboxylic acid group afforded compounds with improved TP receptor antagonism; of these, a tetrazole derivative retained good COX-2 inhibitory activity and selectivity. The identification of this tetrazole acting as a balanced dual-acting compound in human whole blood, along with SAR analysis of the synthesized lumiracoxib derivatives, might contribute to the rational design of a new class of cardioprotective anti-inflammatory agents.     

Theoretical Study on Tetrazole and its Derivatives: 4. Ab Initio Study on Hydroxyl Derivatives of Tetrazole

Ab initio MO calculations at MP2/6-31G* level were performed on hydroxyl derivatives of tetrazole and their anions. Their fully optimized geometries, electronic structures, IR spectra and thermodynamic functions are reported. The calculation results show that all the titled compounds are practically planar and aromatic. The N4 atom on the ring is most negatively charged. The N-hydroxytetrazoles are more stable than the C-hydroxytetrazoles. The thermodynamic properties of the titled compounds are similar.     

唑类含能离子化合物的合成研究进展

综述了以咪唑、三唑、四唑以及五唑等唑类化合物为母体的一些含能盐的合成,系统总结了这类新型含能材料的熔点、密度、生成焓等理化性能以及爆轰性能,并分析了分子结构及取代基对含能盐性能的影响。对唑类含能盐在火炸药和推进剂等方面的应用进行了展望。附36篇参考文献。     

Polyacrylonitrile‐based proton conducting membranes containing sulfonic acid and tetrazole moieties

Proton conducting membranes based on polymers containing sulfonic acid and tetrazole moieties were developed. Successful syntheses of poly(acrylonitrile‐co ‐styrene sulfonic acid) (PAN‐co ‐PSSA), poly(acrylonitrile‐co ‐5‐vinyl tetrazole) (PAN‐co ‐PVTz), and poly(acrylonitrile‐co ‐5‐vinyl tetrazole‐co ‐styrene sulfonic acid) (PAN‐co ‐PVTz‐co ‐PSSA) were confirmed by ¹H‐nuclear magnetic resonance spectroscopy, elemental analysis, and Fourier transform infrared spectroscopy. Two approaches were performed to study the effects of molar ratio of sulfonic acid to tetrazole and tetrazole content on membrane properties. In the first approach, PAN‐co ‐PSSA was blended with PAN‐co ‐PVTz at three molar ratios. The second approach focused on PAN‐co ‐PVTz‐co ‐PSSA membranes with various tetrazole contents. PAN‐co ‐PSSA membrane was also prepared. All solution‐cast membranes were hydrolytically stable, except for PAN‐co ‐PVTz‐co ‐PSSA with 71% tetrazole. Surface morphologies of blend membranes were studied using scanning electron microscopy, and no phase separation was observed. Water uptake was shown to increase with increasing tetrazole. All membranes exhibited high thermal stability (up to 250 °C) and high storage moduli. Proton conductivity was found to depend significantly on relative humidity. The influences of sulfonic acid to tetrazole ratio and tetrazole content on proton conduction were observed and discussed. A maximum proton conductivity of 7.1 × 10^?3 S/cm at 26 °C was obtained from PAN‐co ‐PSSA membrane. In addition, all tested membranes showed relatively good oxidative stability after treatment in Fenton's reagent. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45411.     

Co-Precipitation Studies on Lead Azide with Tetrazole Derivatives-a search for lead azide substitute

Co-precipitation of lead azide with various tetrazole and nitrophenol derivatives is discussed. Thermal behaviour of lead azide before and after co-precipitation is studied suing DSC. Thermal study indicated that the co-precipitation of lead azide with other flame sensitive compounds produced an intimate mixture of lead azide and lead salts of tetrazole and nitrophenyl derivatives but not a single compounds. Explosive properties evaluation indicated that the co-precipitation process not only improves the flame sensitivity of lead azide but also eliminates the hazardous process of physical mixing of lead azide with flame sensitive materials. A good correlation between thermal sensitivity and flame sensitivity is noticed. Both thermal and flame sensitivity decreases.     

杂环类植物抗病毒剂的研究进展

介绍了近年来杂环类植物抗病毒剂的研究进展及开发情况，杂环类植物抗病毒剂化合物主要包括生物碱，吡啶衍生物，吡唑衍生物，咪唑衍一物，三唑衍生物，四唑衍生物，噻唑衍生物，噻二唑衍生物，吡唑衍生物，三嗪衍生物及喹啉肟醚等十一类。     

叠代化钠下游产品开发现状与应用

叠氮化钠是一种有亲核性的叠氮化物,主要用于叠氮化物的制造,在医药、农药等领域有广泛用途。综述了近年来叠氮化钠在有机合成中的应用,主要包括四唑类化合物的合成、三唑类化合物的制备等一系列的制备方法。以期发现新的合成方法。     

Polymers and copolymers based on vinyl tetrazoles, 2. Alkylation of poly(5-vinyl tetrazole)

Alkylation of poly(5-vinyl tetrazole) with dimethyl sulfate and tert-butyl alcohol as well as with alkyl halides RHal (R?CH₃, C₂H₅, CH₂? CH?CH₂, n-C₄H₉, t-C₄H₉) has been studied under various conditions in order to develop a new method of synthesis of tetrazole-containing polymers having a complex of valuable properties. The kinetic study of the process and comparison of isomeric compositions and spectroscopic characteristics (IR, ¹H NMR and ¹³C NMR) of poly(N-alkyl-5-vinyl tetrazole)s synthesized by alkylation of poly(5-vinyl tetrazole) and of those prepared by (co)polymerization of the corresponding vinyl tetrazoles have been carried out. The alkylation is found to proceed to high conversion extents (up to 99.8%) and enables to obtain a wide variety of polymeric products having the composition, structure and properties very similar to those of homo- and copolymers.