摘要
前手性酮类化合物不对称还原制备相应的手性醇化合物,成为近年来不对称还原的前沿领域,此方面的研究迅速发展,并已取得了显著的成绩。本实验以Ni-B非晶态合金为催化剂,催化樟脑加氢制得合成龙脑,研究表明Ni-B非晶态合金为催化剂在显示了很好的催化活性和选择性,樟脑转化率和异龙脑产率均较高,分别达到91.2%和85.67%,证明了以Ni-B非晶态合金为催化剂,常压下催化樟脑不对称加氢制备异龙脑的实验方法可行性和优越性。该实验研究的主要内容如下:
(1)通过查阅大量文献和理论分析,得出Ni-B非晶态合金催化剂对饱和环酮的羰基具有较好的催化活性,初步确定实验方案以Ni-B非晶态合金为催化剂,常压下催化樟脑不对称加氢合成龙脑。
(2)对Ni-B非晶态合金催化剂催化樟脑加氢的各个影响因素进行了考察,确定了催化剂的最佳制备条件,樟脑的最高转化率可到91. 2%。在最佳条件下制备催化剂,对该反应的工艺条件进行了优化,得出反应温度为40℃,反应时间为8h为最佳工艺条件,该条件下樟脑的最高转化率大91.2%。
(3)考察了添加Co、Cu、Mo、Zn、Sn等金属助剂的Ni-B对樟脑催化加氢性能的影响,结果发现Co、Cu、Mo在不同程度上降低了催化剂的催化活性,Zn和Sn的加入可大大提高催化剂活性。考察了加入不同含量Sn(w(Sn)/w(Ni-B)不同)对催化剂活性的影响,得出当w(Sn)/w(Ni-B)为8%催化剂活性最高。
(4)以γ-Al_2O_3为催化剂载体,分别考察了制备方法、pH值、镍负载量、n(KBH_4)/(Ni) (摩尔比)、催化剂的焙烧温度等因素对催化剂性能的影响,研究表明Ni-B催化剂的γ-Al_2O_3改性可以较大程度的提高催化剂的催化活性。pH值为12、n(KBH_4)/(Ni)为3.5、镍负载含量为12%时的催化剂活性最高,进一步优化了制备条件和工艺条件。
(5)采用超声波清洗器处理催化剂,考察超声波处理时间对催化剂活性的影响作用。发现随着处理时间的延长,催化剂活性先逐渐升高,20min后又呈现下降趋势。
Asymmetric synthesis of chiral alcohol from former chiral ketone compounds has become the frontier filed of asymmetric synthesis research in resent years. This research has been developed rapidly and some progress has been made. In this paper, Ni-B amorphous alloy catalysts showed high catalytic activity and the conversation of camphor and the yield of isoborn -eol has been showed high, which proved that this experiment method was feasible. The main contents of this experimental study are as follows:
(1) Through consulting a large number of documents, we concluded that Ni-B amorphous alloy catalyst showed high catalytic activity when applied in saturate ring ketone catalysis hydrogenation. The preliminarily experiment program that camphor asymmetric catalysis hydrogenation producing borneol at normal pressure with Ni-B as catalyst was decided.
(2) The influencing factors of Ni-B cataliyst catalytic camphor hydrogenation were investigated and the best preparation conditions were decided. The production process was optimized and the conversation of camphor achieves to 91.2% at the conditions of reaction time 8h and reaction temperature 40℃.
(3) The influence of a small amount of Co, Cu, Mo, Zn and Sn as peomoter were investigated respectively in camphor hydrogenation. It was found that Co, Cu and Mo decreased the acivity of the catalyst to a certain degree and the addition of Zn and Sn can improve the activity of Ni-B catalyst. The activity of catalyst is highest when w(Sn)/w(Ni-B)=8% .
(4) The influencing factors, such as different preparation, pH value, Ni/KBH_4, load content, roasting temperature, of Ni-B whitγ-Al_2O_3 as suppors were investigated.We can draw a conclusion that the activity of Ni-B withγ-Al_2O_3 as suppors was dramatically improved. The preparation conditions and process conditions were further optimized in this chapter.
(5) It was investigated the effect on ultrasonic processing time. We can conclude that the catalytic activity gradually increase with the extension of processing time, and after 20min, the catalytic activity decline.
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