2,2′,7,7′-四溴-9,9′-螺二芴的合成

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

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%。

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 ℃ 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%.