绿色的Curtius重排及其新应用的研究

Curtius重排是众多重排反应中较为绿色的重排反应。它易反应,几乎无污染,产率高,因此其应用相当广泛,前景也很诱人。近年来,Curtius重排在精细有机合成中又有了令人注目的新应用。     

1，2，4-三唑类衍生物的研究进展

三唑类杂环衍生物不仅具有广谱、高效的杀菌活性,而且具有良好的杀虫、除草及植物生长调节活性。综述了1,2,4-三唑类衍生物的生物活性和合成方法,同时指出了该类衍生物具有广阔的开发前景。     

新型巯基三唑化合物对HCl介质中碳钢的缓蚀作用研究

合成了两种新型巯基三唑化合物，分别采用腐蚀失重法、动电位扫描极化曲线和交流阻抗法研究了其在1．0mol／L HCl介质中对Q235钢的缓蚀作用，分析了缓蚀作用机理．结果表明：对碳钢在1．0mol／L HCl溶液中，合成的巯基三唑化合物是性能优异的缓蚀剂．     

新型聚三唑酯和聚三唑醚树脂的合成及性能

合成了三种含酯基和三种含醚键的炔单体,通过核磁共振氢谱(¹H NMR)、红外光谱(FT-IR)、质谱(MS)、液相色谱(LC)对其结构进行了表征。用这六种炔单体与叠氮单体反应制备了一系列新型聚三唑酯树脂(PTAE)和聚三唑醚树脂(PTAO)。利用差示扫描量热分析(DSC)、FT-IR、动态力学热分析(DMA)、力学试验机和热失重分析(TGA)表征了树脂的固化行为、固化树脂的力学性能、耐热性和热稳定性。结果表明PTAE和PTAO树脂易溶于有机溶剂,可低温(60℃)固化,固化树脂的弯曲强度超过了100 MPa,可达158 MPa,玻璃化转变温度(T _g)超过180℃,高者达251℃,热分解温度可达360℃。     

A P/N-containing flame retardant constructed by phosphaphenanthrene,phosphonate, and triazole and its flame retardant mechanism in reducing fire hazards of epoxy resin

A P/N-containing flame retardant (PPT) constructed by phosphaphenanthrene, phosphonate, and triazole groups was successfully synthesized and used as a reactive co-curing agent for epoxy resin (EP). The curing behavior, thermal property, combustion behavior, and flame retardant mechanism of EP thermosets were comprehensively investigated. According to the analysis of DSC and TGA, PPT accelerated the crosslinking reaction and enhanced the charring ability for EP thermosets at high temperature. The results of combustion test indicated that PPT endowed epoxy thermoset with outstanding flame retardancy. When the phosphorus content was 0.71 wt%, EP/DDS/PPT-2 achieved a LOI value of 33.2% and passed V-0 rating in UL-94 test, and its peak heat release rate and total heat release were decreased by 63.7 and 30.5%, respectively, relative to EP/DDS. Moreover, the FIGRA of EP/DDS/PPT-2 was reduced from 9.7 to 3.5 kW m⁻² s⁻¹, manifesting the significantly improved fire safety of EP thermoset. The flame retardant mechanism was summarized as two parts: (a) the barrier effect of continuous phosphorus-rich char layers in condensed phase, (b) the quenching effect of phosphorous radicals and diluting effect of nonflammable gases in gaseous phase.     

5-氨基-3-硝基-1,2,4-三唑(ANTA)的合成工艺改进

以3,5-二氨基-1,2,4-三唑为原料,经重氮化、盐化合成中间体3,5-二硝基-1,2,4-三唑的铵盐(ADNT),用水合肼还原,得到目标产物5-氨基-3-硝基-1,2,4-三唑(ANTA)。采用红外光谱、核磁共振、质谱及元素分析鉴定了ANTA的结构;同时,探索了反应温度对反应收率及纯度的影响,改进了ADNT的萃取及精制方法,提高了产品的纯度(98%以上),反应总收率达64%。     

Synthesis and Immunological Evaluation of Mannosylated Desmuramyl Dipeptides Modified by Lipophilic Triazole Substituents

Muramyl dipeptide (N-acetylmuramyl-L-alanyl-D-isoglutamine, MDP) is the smallest peptidoglycan fragment able to trigger an immune response by activating the NOD2 receptor. Structural modification of MDP can lead to analogues with improved immunostimulating properties. The aim of this work was to prepare mannosylated desmuramyl peptides (ManDMP) containing lipophilic triazole substituents to study their immunomodulating activities in vivo. The adjuvant activity of the prepared compounds was evaluated in the mouse model using ovalbumin as an antigen and compared to the MDP and referent adjuvant ManDMPTAd. The obtained results confirm that the α-position of D-isoGln is the best position for the attachment of lipophilic substituents, especially adamantylethyl triazole. Compound 6c exhibited the strongest adjuvant activity, comparable to the MDP and better than referent ManDMPTAd.     

2-取代-7-苄氧基-4，5-二氢-[1，2,4]-氮唑[4，3-a]喹啉-1（2H）-酮的合成及其抗癫痫活性研究

为了寻找具有更好抗惊厥活性及低神经毒性的化合物,文章以6-羟基-3,4-二氢-2（1忉-喹啉酮为起始原料合成了4个2-取代-7-苄氧基-4,5-二氢-[1,2,4】三氮唑[4,3-a】喹啉-1（2H）-酮衍生物,对目标化合物,采用小鼠最大电惊厥实验（MES）,皮下戊四唑实验（sc-PTZ）测定了其抗惊厥活性,采尉旋转法测定了神经毒性。药理实验结果显示目标化合物表现出了较强的抗惊厥活性,该结论证明喹啉并三氮唑化合物具有被开发为新型癫痫治疗药的优良品质。     

1,2,3-三氮唑-马来酰亚胺类化合物的合成及抑菌活性研究

通过Click反应,将1,2,3-三氮唑和马来酰亚胺结合在一个分子中,合成了一系列新化合物,并通过IR,NMR及HR-MS对其结构进行了确证。对目标化合物体外抑菌活性进行了初步测定。结果表明,部分化合物对细菌金黄色葡萄球菌和大肠杆菌有较强的抑制作用,对真菌葡萄炭疽病原菌有中等抑制作用。