非贵金属催化含硝基和芳香环双官能团的硝基芳香烃一步全加氢制备脂环胺的控制策略研究

Alicyclic amines are very important organic chemicals and fine chemical intermediates. Traditionally, the synthesis of alicyclic amines from nitro-aromatics is carried out by way of a ‘two-step’ catalytic reaction process. This project will break the restriction of traditional reactive mode, so that nitro and aromatic rings of nitro-aromatic hydrocarbons can “step” catalytic hydrogenation to prepare cycloaliphatic amine instead of the two-step hydrogenation method. This project will focus on the catalytic hydrogenation under easily controllable mild conditions, aided by ultrasonic, microwave and modify the catalyst preparation process innovation, involving non-noble metal catalysts to realize highly selective one-step hydrogenation of nitro-aromatics to alicyclic amines. The ideal catalysts include non-noble transition metal Ni, or non-noble bi-metallic catalysts containing Ni, or non-noble multi-metallic active centers containing Ni, which are supported on solid supporters, and directly used in one-step catalytic hydrogenation of nitro-aromatic hydrocarbons. Extensively physical and chemical characterizations, as well as deep investigations of reaction mechanism, will be carried out to reveal the actual hydrogenation process of double functional groups inclusive of nitro- groups and aromatic rings, i.e. the hydrogenation reaction is sequential or mutually synergic or how do the two-step hydrogenation synergy? Also,many physicochemical problems relevent to the reaction mechanism of one-step hydrogenation of dual-functional groups will be carefully investigated. Hopefully, the investigations of the present project will provide theoretical and experimental basis on the future implementation of one-step hydrogenation of other dual-functional groups, inclusive of aromatic ring and carbonyl group, aromatic ring and ester group or carboxyl group etc.

脂环胺是重要的有机化工和精细化工中间体,传统工业上通常采用“两步法”反应才能实现脂环胺的催化合成。本项目突破传统反应模式，使传统两步加氢从硝基芳香烃制脂环胺的反应能通过硝基和芳香环仅“一步”协同加氢实施。本项目拟在易操控的温和条件下，发展高效催化剂控制策略，以超声波和微波为辅助手段并改性处理催化剂的创新制备过程，制备仅以非贵过渡金属Ni、或者其它非贵金属与Ni掺杂的双金属或多金属为主要催化活性中心的负载型固体催化剂，并直接应用于催化硝基芳香烃类化合物“一步”全加氢制备脂环胺化合物的反应过程中；通过系统的深入研究，揭示硝基、芳香环加氢还原的实际过程（如先后顺序氢化、或是相互协同氢化、两步氢化如何协同作用等？），以及与双官能团“一步”加氢反应机理相关的一系列物理化学问题，并希望为将来实施其它双官能团（芳香环与羰基、酯基或羧基）的“一步”催化加氢提供理论和实验依据。

有机胺一般是指有机烃类与氨发生化学反应生成的有机类物质，分为脂肪胺类、醇胺类、酰胺类、脂环胺类、芳香胺类和其它胺类等。脂环胺是重要的有机化工和精细化工中间体，传统工业上通常采用“两步法”反应才能实现脂环胺的催化合成。. （1）通过特别的浸渍方法将活性组分镍等金属，浸渍负载到经过改性处理的氧化物或炭材料载体上，浸渍过程中分别采用了普通搅拌和微波两种辅助方式，以微波为辅助手段并改性处理催化剂的创新制备过程，制备了一系列具有高催化活性的负载非贵金属的固体催化剂，设计和构建了高活性的非贵过渡金属催化体系。. （2）在易操控的温和条件下，以氢气为加氢试剂，以负载非贵过渡金属的固体催化剂催化硝基苯、取代硝基苯、硝基萘、二硝基萘等含硝基、芳香环双官能团的硝基芳香烃仅“一步”全加氢制备脂环胺。进一步研究催化剂的制备技术及反应过程的选择性控制。研究了普通浸渍法和微波辅助加热方法对催化加氢的活性差异，并探讨相关作用机制。. （3）通过对硝基芳香烃类化合物催化加氢还原反应的机理深入研究，揭示了硝基、芳香环加氢还原的实际过程，通过调变因硝基和芳香环加氢活化能的差异而将两者的全加氢过程有机的结合了起来，实现高转化率、高选择性硝基芳香烃类化合物双官能团一步氢化转化的目标。