氮杂环脒类光产碱剂的合成及性能研究

The Synthesis and performance of the nitrogen heterocyclic Amidines as Photobase Generators

摘要:

1 ,5-二氮杂双环[4,3,0]-5-壬烯(DBN)是20世纪60年代开发的强碱性有机试剂,因其碱性较强，亲和性较弱，在有机反应中常作为催化试剂, 本文以DBN为起始原料，采用氢化铝锂为还原剂，在55℃条件下反应9h，生成1, 5-二氮杂双环[4,3,0]壬烷(1a)，最高收率可达87.9﹪，纯度大于95.0﹪。再将1a分别与四种氯甲基吡啶类化合物反应，合成了系列新型含氮杂环脒类光产碱剂，实验中通过对其工艺条件的考察和优化，得到合成此类光产碱剂最高收率达84.7﹪，纯度大于95.7﹪。并对合成的系列新型光产碱剂进行最大紫外吸收、感光性、热稳定性等性能测试，分析该系列光产碱剂的构效关系。产品及中间体经高效气相色谱(HPGC)、高效液相色谱(HPLC)、液相色谱-质谱联用仪（LC-MS）、核磁共振氢谱(1H-NMR)对其进行了定量和定性分析,为此类光产碱剂的进一步研究奠定理论基础。

Abstract:

1, 5 - diaza-bicyclo [4.3.0]-5-nonene (DBN), which usually plays an important role as a catalyts in organic synthesis due to its strongly basic, is developed in the 1960s. In this paper, 1, 5-diazabicyclo[4,3,0]nonane was prepared by reduction of 1,5-diazabicyclo[4,3,0]nonene(DBN) with LiAlH4 in methyl tert-butyl ether at 55℃ for 9h. The yield and purity of the product can reach 87.9% and 95%, respectively. This series of amidine photobase generators was synthesized through the reaction of 1, 5-diazabicyclo[4,3,0]nonane with corresponding chloro-methyl-pyridine compounds and the yield and purity was even up to 84.7% and 95.7%, respectively. The structure-activity relationship of the photobase- generators was investigated by UV absorbance, thermal stability and photo-sensitivity and so on. HPLC, LC-MS and 1H-NMR were also applied to monitor and characterize the intermediates and products.