FeCl_3·6H_2O/C催化水合肼还原制备2,2-二(4-羟基-3-氨基)苯基丙烷

Synthesis of 2.2-Bis(4-hydroxy-3-amido-phenyl)-propane Catalyzed by the FeCl_3·6H_2O/C Catalyst with Hydrazine Hydration

以ω(Fe)=5%的FeCl3·6H2O/C为催化剂,用ω(NH2NH2)=80%的水合肼,在乙醇溶剂中将2,2-二(4-羟基-3-硝基)苯基丙烷还原成为阻燃剂的中间体2,2-二(4-羟基-3-氨基)苯基丙烷.实验条件:用0.3g的催化剂(每10mmol反应物),反应物与水合肼的摩尔比为1∶4.5,控制反应温度为70℃,反应时间为3.5h,目标产物的产率为93.0%,纯度为98.5%,考察9种金属离子对催化活性的影响.结果表明:Pb2+会引起催化剂中毒;Mg2+、Cu2+和Zn2+钝化了催化剂的催化活性;Ba2+和Cr3+对反应几乎不影响;只有Al3+、Ni2+、Ti4+3种离子能活化催化剂,从而使反应速度加快,但这3种金属离子单独作为催化剂时都没有催化活性.

Catalyzed by the FeCl_3·6H_2O/C catalyst [w(Fe)=5%] with hydrazine hydration [w(NH_2NH_2)=80%], 2.2-Bis(4-hydroxy-3-nitro-phenyl)-propane was reduced in the alcohol solvent to 2.2-Bis(4-hydroxy-3-amido-phenyl)-propane which is an intermediate of fire-retardants. The results show that the best condition of the reduction is that the catalyst is 0.3 g (10 mmol reactant), the mole scale of reactant and hydrazine hydration is 1∶4.5, the temperature should be 70℃, the test hour is 3.5 h , the yield is 93.0% and the purity is 98.5%. We have even made a study of the nine kinds of metal ions to learn what influence they could make on catalyst activity. The results show that Pb^(2+) can cause the catalyst to be poisoned; that Mg^(2+), Cu^(2+) and Zn^(2+) blunt the activity of catalyst; that Ba^(2+) and Cr^(3+) can hardly affect the activity of catalyst; and that Ni^(2+), Al^(3+) and Ti^(4+) can activate the activity of catalyst and quicken the reaction rapidly. But none of Ni^(2+), Al^(3+) and Ti^(4+) has any catalytic activity to the reaction when they are used as catalyst alone.