2,2′,7,7′-四溴-9,9′-螺二芴的合成

以2-溴联苯的Grignard试剂和9-芴酮反应制备9-(2-联苯基)-9-芴醇,经关环反应制备了9,9′-螺二芴(SBF),并以溴化钠为溴源、过氧化氢为氧化剂、1,2-二氯乙烷为溶剂,通过SBF的氧化溴化反应制备了2,2′,7,7′-四溴-9,9′-螺二芴(TBSBF)。采用质谱、核磁共振对SBF和TBSBF的结构进行了表征,并用高效液相色谱仪测定了SBF和TBSBF的含量;考察了反应物配比、反应时间、反应温度和溶剂种类对氧化溴化合成TBSBF反应的影响。确定了较佳的工艺条件为:n(SBF)∶n(溴化钠)∶n(过氧化氢)∶n(硫酸)=1∶8∶6∶6,溶剂为1,2-二氯乙烷,反应温度20℃,反应时间48h。在此条件下,TBSBF的选择性达到95.1%,产物TBSBF纯度大于98%,收率约为80%。

Synthesis of 2,2'''',7,7'''' - Tetrabromo - 9,9'''' - Spirobifluorene

9,9′-spirobifluorene(SBF) was synthesized from 9-fluorenone and 2-biphenylmagnesium bromide through 9-(2-biphenyl)-9-fluorenol. The obtained SBF then reacted by oxy-bromation at room temperature with sodium bromide as bromo source, H2O2 as oxidant and 1,2-dichloroethane as solvent to produce 2,2′,7,7′-tetrabromo-9,9′-spirobifluorene (TBSBF). The obtained TBSBF and SBF were characterized by means of mass spectrometry, 1H NMR and 13C NMR. Purities of TBSBF and SBF was measured by means of HPLC. Effects of ratio between reactants, reaction time and temperature, and solvents on oxy-bromation were investigated. Under optimal reaction conditions: n(SBF) ∶n (sodium bromide) ∶n(H2O2) ∶n(H2SO4) 1 ∶8 ∶6 ∶6, 1,2-dichloroethane as solvent, reaction temperature 20 ℃ and reaction time 48 h, selectivity to TBSBF and its yield can reach 95.1% and about 80%, respectively. Purity of product TBSBF is more than 98%.