1-氯甲基萘催化羰化合成α-萘乙酸的研究

A Study on Catalytic Carbonylation Synthesis of α-naphthylacetic Acid from the 1-naphthylmethyl Chloride

论文导师 朱康玲,论文学位 硕士,论文专业 物理化学

论文单位 华中科技大学,点击次数 12,论文页数 60页File Size1148K

carbonylation；Sol-gel；α-naphthylacetic acid；potassium pyridine-2-carboxylate；1-chloromethyl naphthalene

α-萘乙酸(NAA)是一种重要的精细化工产品,是农业及园艺上使用最广泛的人工合成生长素之一,是广谱型植物生长调节剂。精制的NAA还是重要的医药合成中间体。 对α-萘乙酸合成方法的研究很多,本文针对传统的合成方法存在收率低、反应时间长、环境污染严重等一系列问题,研究了氯化钴/吡啶-2-羧酸钾均相催化体系对1-氯甲基萘催化合成α-萘乙酸的新方法,探讨了催化剂配比,溶剂,CO压强以及反应时间等条件对反应的影响。同时还初步研究了该催化体系固载化的方法。

主要研究内容为:

(1)研究了用氯化钴/吡啶-2-羧酸钾均相催化1-氯甲基萘合成α-萘乙酸的新方法。探讨了合成过程中的主要因素对反应的影响,实验确定最佳反应条件为:氯化钴8.3×10~(-4)mol/l,吡啶-2-羧酸钾3.3×10~(-3) mol/l,n(氢氧化钠)/n(1-氯甲基萘)=1.5,V(1,4-二氧六环)/V(水)=5,反应温度333K,一氧化碳压力1.8MPa,反应时间6小时,对应的α-萘乙酸产率为53.2%。同时对该催化体系的反应机理进行了初步探讨。
(2)研究了不同配体与氯化钴组成的催化体系对1-氯甲基萘羰化反应的催化性能。实验结果表明,不同配体对产品的产率和反应的选择性都有很大的影响。

(3)初步探索了将氯化钴/吡啶-2-羧酸钾催化体系固载化的方法,得到的凝胶催化剂具有良好的催化活性,α-萘乙酸产率达到51.6%,催化剂循环使用8次后仍具有一定的催化活性。

(4)对产物的化学结构进行了鉴定。

α-Naphthylacetic acid is one of the most important fine chemicals. It is a modifying agent which is widely used to adjust plant’s growing. The chemically pureα-naphthylacetic acid is an import intermediate in medicinal synthesis. The traditional methods of synthesizingα-naphthylacetic acid have some shortages such as low yield, long time for reaction, pollution to the environment, and so on. Aiming at these, a novel method for preparingα-naphthylacetic acid from the carbonylation of 1-naphthylmethyl chloride has been researched. The effects of the reaction conditions, such as the n(CoCl2)/n(Kpyca), CO pressure, solvents and the reaction time have been studied. The carbonylation mechanism about this reaction is discussed. At the same time, it has been groped that CoCl_2/Kpyca supported on the functional silicon. The main research contents are followed: (1) Synthesis ofα-naphthylacetic acid from carbonylation of 1-naphthylmethyl chloride by CoCl_2/KPyca catalyze system is studied. Optimal reaction conditions are established through experiments. Under the conditions of c(CoCl_2)=8.3×10~(-4)mol/l, c(KPyca)=3.3×10~(-3) mol/l, n(NaOH)/n(1-naphthylmethyl chloride)=1.5, V(DO)/V(H_2O)=5,θ=333K, p=1.8Mpa, and t=6h, the yield ofα-naphthylacetic acid is 53.2%. The mechanism of the catalytic reaction has all been discussed. (2) The catalysis performance of the catalysis systems which are composed of the other ligands and cobaltous chloride in the carbonylation of 1-naphthylmethyl chloride is studied .When the ligand differs, the yield and selectivity for NAA are differents. (3) The grafting method CoCl_2/potassium pyridine-2-carboxylate to the functional silicon has been researched initially. Using this catalyst, the yield of NAA is 51.6%, and it has still catalytic activity when it was recovered for 8 times. (4) Chemical structures of the products has been characterized.