新型苯乙酰脒类化合物的合成及其感光性能

Synthesis and Photosensitivities of Novel Phenylacetyl Amidines

以氢化铝锂为还原剂,甲基叔丁基醚为溶剂,1,5-二氮杂双环[4.3.0]-5-壬烯(1)于55℃反应9 h制得1,5-二氮杂双环[4.3.0]壬烷(2),收率87.9%,纯度>95.0%。2分别与溴代苯乙酮(3a),对甲氧基溴代苯乙酮(3b)和对溴基溴代苯乙酮(3c)进行消除反应合成了3个新型的苯乙酰基潜双环脒类化合物(4a^4c),其结构经1H NMR和LC-MS表征。采用正交实验对合成4a^4c的反应条件进行了优化。在最佳反应条件[以甲苯为溶剂,3a 25.2 mmol,n(3a)∶n(K2CO3)∶n(2)=1.0∶2.0∶1.4,于15℃反应24 h]下,1,5-二氮杂双环[4.3.0]-5-苯乙酰基壬烷(4a)收率89.0%,纯度87.9%。感光性能研究结果表明,1,5-二氮杂双环[4.3.0]-5-(4-甲氧基)苯乙酰基壬烷(4b)经紫外曝光400 mJ·cm-1,其引发性能最强,分解转化近45%;曝光2 000 mJ·cm-1,4b分解转化近90%。

1,5-Diazabicyclo [4.3.0] nonane （2） in yield of 87.9 % with 95 % purity was prepared by reduction of 1,5-diazabicyclo[4.3.0]nonene using LiAlH4 as the reductant and methyl tert-butyl ether as the solvent at 55 ℃ for 9 h.Three novel amidine photobase generators（4a ～4c） were synthesized by elimination reaction of 2 with bromoacetophenene（3a）,p-hydroxy-bromoacetophenene（3b） and p-bromoyl-bromoacetophenene （3c）,respectively.Reaction conditions of synthesizing 4a ～ 4c were optimized by L9（33）.The yield and purity of 1,5-diazabicyclo[4.3.0]-5-phenylacetyl-nonane （4a） were 89.0% and 87.9% under optimum reaction conditions[toluene was the solvent,3a 25.2 mmol,n（3a） ∶n（K2CO3） ∶n（2） was 1.0∶2.0 ∶ 1.4,at 15 ℃ for24 h].The structure and photosensitivity were characterized by 1 H NMR,LC-MS and TG.The results showed that conversion of 5-（4-methoxyphenylacetyl）-1,5-diazabicyclo [4.3.0] nonane （4b） at exposure 400 mJ · cm-1 was 45%.Conversion of 4b was 90% at exposure 2 000 mJ · cm-1.