2,7-二溴螺[芴-9,9′-(2′,7′-二羟基-1′,8′-二磺酸基氧杂蒽)]的合成与表征

以芴为原料,经Br2/Fe溴代、CrO3/Ac2O氧化、间苯二酚/ZnCl2催化缩合得到2,7-二溴螺[芴-9,9′-(2′,7′-二羟基氧杂蒽)](Ⅲ),化合物Ⅲ经浓硫酸磺化合成目标产物2,7-二溴螺[芴-9,9′-(2′,7′-二羟基-1′,8′-二磺酸基氧杂蒽)](Ⅳ).考察了反应温度、反应物配比、反应时间等对磺化产物Ⅳ收率的影响,并通过傅里叶红外光谱、氢核磁共振谱、紫外?可见光谱等手段对化合物Ⅳ的结构进行了表征.确定了磺化反应的最佳条件,即反应温度70℃、每1g化合物Ⅲ对应加入浓硫酸3mL、反应时间2 h,该条件下磺化产物(化合物Ⅳ)收率达86.5%.

Synthesis and Characterization of 2,7-Dibromospiro [Fluorene-9,9'-(2',7'-Dihydroxy-1',8'-Disulfonic-Xanthene)]

The synthesis of 2,7-dibromospiro[fluorene-9,9’-(2’,7’-dihydroxy-1’,8’-disulfonic-xanthene)] (4) was studied systematically. 2,7-dibromospiro[fluorene-9,9’-(2’,7’-dihydroxy -xanthene)] (3) was obtained from 2,7-dibromo- fluorenone (2) and resoreinol in the presence of zinc chloride by melting reaction with a yield of 61.8%, where 2 was prepared by two steps of Br2/Fe and CrO3/Ac2O oxidation reactions, fluorene as starting material. Sulfonation of 3 with concentrated sulfuric acid gave 4 with a yield of 86.5% under optimal reaction conditions (70oC, 1/5.6 mass ratio of 3/H2SO4, 2h). The structure of 4 was characterized by IR, 1H NMR and UV-vis measurements.