手性甲基脂肪烃类昆虫信息素的合成研究进展

手性甲基脂肪烃类昆虫信息素包括单手性甲基、双手性甲基和多手性甲基脂肪烃类昆虫信息素,在棘翅夜蛾、南部云杉天牛、桃潜叶蛾等多种农林害虫的绿色防控领域具有极具发展的前景.按手性甲基的构建方法,分类阐述了单手性甲基昆虫信息素的合成方法;根据手性甲基片段的连接策略对双手性甲基与多手性甲基脂肪烃类昆虫信息素的合成方法进行了详细介绍;并对各种合成方法的优势与不足进行简单讨论,以及对手性甲基脂肪烃类昆虫信息素的合成研究进行了展望.     

聚合物保护基团在有机合成中的应用

本文论述了聚合物保护基团在对称双功能基单保护合成不对称化合物,作为助剂合成手性化合物和作为载体合成昆虫性信息素和不对称卟啉,酞菁类化合物方面的应用。     

聚合物支持的三苯基氯硅烷在昆虫性信息素固相合成中的应用

1%二乙烯基苯交联的聚苯乙烯树脂在N,N,N',N'-四甲基乙二胺的存在下用丁基锂进行锂化后与二苯基二氯硅烷反应制得聚苯乙烯支持的三苯基氯硅烷(2).这种聚合物用于一些鳞翅目(lepidoptera)昆虫的性信息素的固相合成.2与1,9-壬二醇,1,10-癸二醇和1,12-十二碳二醇反应分别生成聚合物支持的二醇单硅醚(4a,4b,4c),游离的醇基用Swern试剂(DMSO和草酸酰氯)氧化成聚合物支持的醛(5a,5b,5c),经Wittig缩合反应和用氟离子裂解后分别得到9-十四碳烯醇-1(8a),10-十四碳烯醇-1(8b)和12-十四碳烯醇-1(8c).化合物8经乙酰化后分别得到9-十四碳烯醇-1乙酸酯(9a),其顺式异构体是秋灰夜蛾(S.frugiperda,Smith)的性信息素;10-十四碳烯醇-1乙酸酯(9b),其顺式异构体是橡卷叶蛾(A.semiferamus,Walker)的性信息素;和12-十四碳烯醇-1乙酸酯(9C).9C与四氯化碲反应,硫化钠还原后转化成E-和Z-异构体比例为54:46的亚洲玉米螟(Ostriniafurnicalis)的性信息素.     

昆虫信息素结构鉴定和合成的研究ⅩⅩⅤ.用三乙胺作烯铜锂试剂配位体合成棉铃虫和午毒蛾性信息素

烯铜锂试剂对合成含有顺式双键的昆虫信息素极为有效,可以缩短合成步骤,产率高,而且顺式产物纯度非常高。我们曾用这种试剂合成了棉铃虫性信息素,因为烯铜锂试剂配位体亚膦酸三乙酯的毒性较大,且气味难闻,操作不方便。本文报道以三乙胺代替亚膦酸三乙酯,合成了棉铃虫性信息素顺-7-十六碳烯醛(1)和顺-11-十六碳烯醛(2)以及消旋的午毒蛾性信息素顺-7,8-环氧-2-甲基十八烷(3)。     

印迹分子聚合物结合低共熔溶剂用于山楂中咖啡酸的固相萃取（英文）

在相同的实验条件下,分别合成了以咖啡酸为模板的印迹分子聚合物和无模板分子聚合物。使用场发射扫描电镜法和吸附实验表征这两种聚合物材料的孔状结构和选择性吸附性能。然后利用印迹分子聚合物、无模板分子聚合物、C18萃取小柱这3种材料结合固相萃取法纯化山楂提取物中的咖啡酸,提取率分别为3.46、1.01、1.17μg/g。为了优化固相萃取过程,实验研究了不同洗脱剂的影响。分别利用用氯化胆碱和甘油、氯化胆碱和尿素(摩尔比均为1∶2)合成出两种低共熔溶剂。甲醇与这两种低共熔溶剂分别以不同的体积比混合作为洗脱剂,用于优化咖啡酸的固相萃取过程。实验结果表明,印迹分子聚合物是一种良好的固相萃取材料;当甲醇和甘油基低共熔溶剂在体积比为3∶1混合时,表现出最好的洗脱能力,得到咖啡酸的回收率为82.32%。     

粉蠹虫性信息素的不对称合成新方法

昆虫性信息素;粉蠹虫性信息素的不对称合成新方法     

顺,顺,顺-3,6,9-二十碳三烯及顺,顺,顺-3,6-9-二十一碳三烯的合成

由于昆虫信息素研究的需要,我们曾于1979年合成了顺、顺、顺-3,6,9-二十碳三烯(1)和顺、顺、顺-3,6,9-二十一碳三烯(2),最近Conner等报道,1和2为鳞翅目昆虫信息素组分,并发表了以亚麻油酸及亚麻油醇为原料的合成路线。本文报道我们的合成路线,以丙炔醇为原料,经2-戊炔醇-[1](3),1-溴-2-戊炔     

加替沙星分子印迹聚合物的制备及其应用

以加替沙星为模板分子,采用溶胶-凝胶分子印迹技术,合成具有分子识别作用的新型有机-无机杂化分子印迹聚合物,对其进行吸附性能研究证明了印迹聚合物对加替沙星的专一吸附性能。以该印迹聚合物为固相萃取材料填充固相萃取柱,优化固相萃取条件,结合超高效液相色谱法,对牛奶样品进行检测。建立了分子印迹固相萃取方法,分离富集并检测牛奶中的加替沙星,其回收率为79.87%,富集倍数为38,高于市售C18柱,具有一定的实际应用价值。     

德国小蠊性信息素类似物的设计与合成

德国小蠊是世界上最难治理的卫生害虫之一.昆虫性信息素可作为一种安全有效的引诱剂用于害虫的综合治理.德国小蠊性信息素(blattellaquinone)因其结构不稳定而妨碍了它的实际应用.为了发现结构新颖且稳定的性信息素类似物,对blattellaquinone的结构中苯醌(A)、酯基(B)和脂肪链(C)部分进行了改造,设计并合成了一系列类似物,结构均通过1H NMR,IR和HRMS分析确证.     

己烯雌酚印迹分子聚合物合成及其在残留分析中的应用

以己烯雌酚（Diethylstilbestrol,DES）为模板分子,α-甲基丙烯酸为功能单体,二甲基丙烯酸乙二醇酯为交联剂,合成己烯雌酚分子印迹聚合物;以该聚合物为填料制成固相萃取小柱,应用于己烯雌酚残留分析的样品前处理,并比较了该固相萃取小柱与C18固相萃取小柱对DES保留行为的差异。通过选择不同浓度的甲醇水溶液,己烯雌酚达到理想的分离纯化效果;对加标鸡肉样进行了含量测定,回收率可达95％以上。     

Synthesis of polymer-supported phosphonium salts and their use as phase transfer catalysts

Spacer-modified polymer supports have been synthesized through the polymeric Grignard reagent method. Phosphonium-active sites were then introduced into these supports and the polymer-supported phosphonium salts were used as phase transfer catalysts for the nucleophilic substitution reactions. Influences of organic solvent, properties of the spacer and temperature on the catalytic activity have been investigated. Based on the experimental results, it was assumed that there might exist a dissolubility equilibrium of the catalytic site between the organic phase and the aqueous phase. With this idea, the results have been reasonably elucidated.     

A novel and selective oxidation of benzylic alcohols with polymer-supported periodic acid under mild aprotic conditions

A new polymeric oxidizing reagent was prepared by supporting periodic acid on poly（1,4-phenylene-2,5-pyridine dicarboxyamide）. This polymeric reagent was used for the selective oxidation of primary benzylic alcohols to the corresponding benzaldehydes in CH₃CN at reflux conditions.Excellent selectivity was observed between primary benzyl alcohols and secondary ones as well as non-benzylic alcohols in the oxidation reactions.Allylic alcohols were also converted to the corresponding aldehydes with good yields.     

昆虫性信息素的研究 Ⅱ.顺-11-十六碳烯醛的合成

顺-11-十六碳烯醛(10)是鳞翅目昆虫信息素的主要组份之一,它的合成在文献上已有一些报道。本文则报道从顺-5-癸烯醇-1(3)     

合成抗病毒母体三羟基核苷的新方法

三羟基核苷因其具有良好的抗病毒性能及作为核酸代谢作用的抑制剂而受到人们的关注．文献报道的合成方法［１～３］因反应需避光，温度控制要求严格，中间体二醛不稳定［４］，给操作带来困难．产物不易纯化，一般局限于使用离子交换色谱法［５］，而按此方法得到的无环核...     

聚合物硼氢阴离子还原剂的制备及其对酯的还原研究

氯型季我安盐型强碱性阴离子交换树脂７１１＾＃与硼氢化钾反应制得聚合物硼氢阴离子还原剂，树脂容量３．２ｍｍｏｌ ＢＨ４／ｇ。用于不同酯化合物的还原，操作简便，树脂可再生重复使用。     

Liquid crystal stationary phases for gas chromatography and supercritical fluid chromatography

Novel monomeric and polymeric liquid crystalline compounds were synthesized as stationary phases for gas chromatography (GC) and supercritical fluid chromatography (SFC). Monomeric liquid crystalline compounds were used in packed column gas chromatography for the separation of isomeric aromatic compounds and insect sex pheromones. Liquid crystalline polymers possess long nematic ranges and a uniform coating was easily achieved in glass and fused silica capillaries, which could stand temperatures up to 250°C in GC and pressures of 200 MPa at 160°C in SFC. The columns provide excellent selectivity and resolution for fused ring aromatic compounds such as the isomers anthracene and phenanthrene or triphenylene and chrysene.     

Acylation of linalool in the presence of polymeric pyrrolidinopyridines

The effects of a number of factors on the efficiency of polymers containing immobilized pyrrolidinopyridine groups as polymeric activating reagents for the acylation of weakly reactive sterically hindered alcohols was studied. The conditions of the acylation of linalool with acetic anhydride in the presence of polymeric pyrrolidinopyridines were selected in such a way that the activity of polymeric systems under study was close to that of their low-molecular-weight analog, pyrrolidinopyridine (in a homogeneous medium).Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No 5, pp. 1287–1290, May, 1996.     

Novel immonium type peptide coupling reagent: 5‐(1H‐benzotriazol‐1‐yloxy)‐3,4‐dihydro‐1‐methyl 2H‐pyrrolium hexachloroantimonate (BDMP® )

A novel immonium type coupling reagent, 5‐(1H‐benzotriazol‐1‐yloxy)‐3,4‐dihydro‐1‐methyl 2H‐pyrrolium hexachloroantimonate (BDMP) has been designed, synthesized and utilized to synthesize oligopeptides and biologically active peptide both in solution and solid phase with satisfactory yield, low racemization and fast reaction rate. The estimation of racemization and the influence of several reaction parameters were studied by HPLC method using the model reaction: Z‐Gly‐Phe‐OH + Val‐OMe·HCl·Z‐Gly‐D/L‐Phe‐Val‐OMe. It was shown that the reactivity of BDMP was much higher and the racemization was much lower than those of HOBt‐based ‘onium’ reagents, even though its analogues BOMI. To further verified me effectiveness of BDMP, Leu‐enkephalin was synthesized both in solution and solid phase using BDMP as coupling reagent. The proposed mechanism was also speculated.     

长链单不饱和脂肪醇乙酸酯的红外和拉曼光谱研究

本文研究了鳞翅目昆虫性外激素——长链单不饱和脂肪醇乙酸脂系列化合物的红外和拉曼光谱。对主要谱带进行了归属。探讨了十一种系列化合物在室温液态和低温固态的光谱差异,得到了某些特征带与链结构的关系。结合其它物理性质,它们可用于估计同系物的双键位置和链长。