以无水乙醇为溶剂,1-硝基环己烯与异氰基乙酸乙酯在K2CO3催化下经Barton-Zard反应制得2-乙氧羰基-3,4-四亚甲基吡咯(3);用过量氢化铝锂高温还原3得2-甲基-3,4-四亚甲基吡咯(4);通过“一瓶三步骤”合成法,4与4-羟基-3-硝基苯甲醛在三氟乙酸催化下经缩合反应后,用2,3-二氯-5,6-二氰基-1,4-苯醌氧化并依次用NEt3和BF3·OEt2处理合成了一种新型的含稠合外环的中位取代4-羟基-3-硝基苯基亚单元的BDP类染料衍生物(7),其结构经1H NMR和元素分析表征.光学性质研究结果表明,7在氯仿中的最大吸收峰位于525 nm,496 nm和390 nm;7的吸收光谱特征与溶液pH无关,但其发射光谱在强极性溶剂中表现出较强的碱性依赖性,可作为碱性条件下的pH荧光探针;7与OH-以1∶1结合的结合常数Ks为1 579 L·tmol-1,酸度常数pKa约为10.80.
2-Ethoxycarbonyl-3,4-tetramethylene pyrrole(3) was synthesized by Barton-Zardon reaction of 1-nitrocyclohexene with ethyl isocyanoacetate using K2CO3 as the catalyst and dry ethanol as the solvent.2-Methyl-3,4-tetramethylene pyrrole(4) was obtained after treating 3 with excess LiAlH4 at high temperature.A novel kind of BDP derivative (7) substituted with 4-hydroxy-3-nitro phenyl subunit at meso was synthesized by "one-pot-three-step" reaction of 4 with 4-hydroxy-3-nitrobenzaldehyde using TFA as the catalyst,then oxidized with DDQ,followed by treating with NEt3 and BF3 · Et2O.The structure was characterized by 1H NMR and elemental analysis.Absorption and emission spectroscopic proerties of 7 were investigated by UV-Vis and FL spectra.The results showed that λmaxof 7 was 525 nm,496 nm and 390 nm.7 was sensitive to pH value in the basic CH3OH/H2O(1/1,V/V) solution and 7 can be applied as a fluorescent probe for pH sensing in the alkaline region under exciting with visible light.Ks =1 579 L · mol-1and pKa =10.80 with n(7) ∶ n(OH-) =1 ∶ 1.