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

論文導師 朱康玲,論文學位 碩士,論文專業 物理化學

論文單位 華中科技大學,點擊次數 12,論文頁數 60頁File Size1148K

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

     α-萘乙酸(NAA)是一種重要的精細化工產品,是農業及園藝上使用最廣泛的人工合成生長素之一,是廣譜型植物生長調節劑。精制的NAA還是重要的醫藥合成中間體。 對α-萘乙酸合成方法的研究很多,本文針對傳統的合成方法存在收率低、反應時間長、環境污染嚴重等一系列問題,研究了氯化鈷/吡啶-2-羧酸鉀均相催化體系對1-氯甲基萘催化合成α-萘乙酸的新方法,探討了催化劑配比,溶劑,CO壓強以及反應時間等條件對反應的影響。同時還初步研究了該催化體系固載化的方法。

主要研究內容為:

(1)研究了用氯化鈷/吡啶-2-羧酸鉀均相催化1-氯甲基萘合成α-萘乙酸的新方法。探討了合成過程中的主要因素對反應的影響,實驗確定最佳反應條件為:氯化鈷8.3×10~(-4)mol/l,吡啶-2-羧酸鉀3.3×10~(-3) mol/l,n(氫氧化鈉)/n(1-氯甲基萘)=1.5,V(1,4-二氧六環)/V(水)=5,反應溫度333K,一氧化碳壓力1.8MPa,反應時間6小時,對應的α-萘乙酸產率為53.2%。同時對該催化體系的反應機理進行了初步探討。
(2)研究了不同配體與氯化鈷組成的催化體系對1-氯甲基萘羰化反應的催化性能。實驗結果表明,不同配體對產品的產率和反應的選擇性都有很大的影響。

(3)初步探索了將氯化鈷/吡啶-2-羧酸鉀催化體系固載化的方法,得到的凝膠催化劑具有良好的催化活性,α-萘乙酸產率達到51.6%,催化劑循環使用8次后仍具有一定的催化活性。

(4)對產物的化學結構進行了鑒定。

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.