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本文总结光化学中又一种氧化单元反应,即羟基直链化合物通过光照氧化,高选择性地生成1-羟基-2-酮化合物。将1,2-丁二醇用溴酸钾作氧化剂,在溴氢酸催化作用下,常温或较高的温度,分别用自然或人造光源照射,以较高的转化率得到1-羟基-2-丁酮。并且,本光氧化反应对于邻羟基脂肪族化合物或芳香族侧链邻羟基化合物中仲羟基选择性氧化有一定的意义[10],是一种简单的α-羟基-β-酮基化合物制备方法。 1-羟基-2-丁酮(1-Hydroxyl-2-Butylene)是合成抗结核药乙胺丁醇的重要中间体[1-3]。关于1-羟基-2-丁酮的制备报导很少。BASF公司来华访问时声称,该公司以1-羟基-2-丁酮路线合成乙胺丁醇[4]。该公司曾以专利[5]报导,将1,2-丁二醇在C_2CO_3加2％CrO_3和1％NiCo_3作催化剂条件下,200℃高温在固定床反应器内得1-羟基-2-丁酮,收率为40％。即使改变条件,采用CuO作催化剂,在1800℃反应温度下,也只能以45％收率得到1-羟基-2-丁酮。本文主要总结光化领域中氧化单元反应,即将邻羟基直链化合物经氧化剂溴酸钾在溴氢酸催化作用下,在室温及较短的反应时间内,用自然光源和人造光源照射,高选择性氧化,以1,2-丁二醇为例,其转化率大于90％。
This article summarizes yet another oxidation unit reaction in photochemistry, in which hydroxyl linear compounds are oxidized by light to generate 1-hydroxy-2-ketone compounds with high selectivity. The 1,2-butanediol with potassium bromate as oxidant, under the catalysis of bromine hydrogen acid, at room temperature or higher temperature, respectively, with natural or artificial light irradiation, with a higher conversion of 1-hydroxy-2-butyl ketone. In addition, the present photooxidation reaction is of certain significance for the selective oxidation of the secondary hydroxyl groups in o-hydroxy aliphatic compounds or aromatic side-chain o-hydroxy compounds [10], which is a simple method for preparing α-hydroxy-β-keto compounds . 1-Hydroxy-2-butanone (1-Hydroxyl-2-Butylene) is an important intermediate for synthesizing ethambutol [1-3]. Preparation of 1-hydroxy-2-butanone reported little. BASF’s visit to China claimed that the company synthesized 1-hydroxy-2-butanone ethambutol [4]. The company once reported in the patent [5] that 1,2-butanediol can react with 1-hydroxy-2-butanediol in a fixed bed reactor under the conditions of C 2 CO 3 and 2% CrO 3 and 1% NiCo 3 as catalysts Ketone, yield 40%. Even if the conditions are changed, with CuO as a catalyst, 1-hydroxy-2-butanone can only be obtained in 45% yield at a reaction temperature of 1800 ° C. In this paper, we mainly summarize the oxidation unit reaction in the field of photochemistry, that is, the ortho-hydroxy linear compounds are oxidized by the oxidant potassium bromate under the catalysis of bromine hydrogen acid, at room temperature and short reaction time, irradiated with natural light source and artificial light source, , 1,2-butanediol, for example, the conversion rate is greater than 90%.