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Efficient production of high value added materials via selective hydroformylation of difficult substrates like internal alkenes and butadiene.

通过对内烯烃和丁二烯等困难底物进行选择性加氢甲酰化，高效生产高附加值材料。

基本信息

批准号：
EP/E022154/1
负责人：
Paul Kamer
金额：
$ 40.66万
依托单位：
University of St Andrews
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2007
资助国家：
英国
起止时间：
2007 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FE022154%2F1
关键词：
Efficient production value added materials

项目摘要

Aldehydes are important intermediates for the preparation of a large variety of fine- and bulk-chemicals. Applications of these compounds are found in the pharmaceutical industry, aroma and flavour industry, and in the production of agrochemicals and detergents. Many of these products are currently prepared via stoichiometric reactions which often results in large amounts of chemical waste. There is an increasing demand for new production methods based on mild and selective reactions with a very high atom efficiency , thus reducing the chemical waste problem. The rhodium catalysed hydroformylation of alkenes is an example of such a mild and clean process for the production of high-quality aldehydes, using only CO and H2 as reagents and therefore producing no waste products at all.In this project we will develop a new generally applicable catalyst system capable of converting both internal alkenes and conjugated dienes into high value-added aldehydes and / or esters. Atom economic and clean hydroformylation technology of butadiene to the intermediate 1,6-hexanedial would create a major contribution to the sustainable production of polyamides. Many industries and academic researchers, however, have studied the rhodium-catalyzed hydroformylation of butadiene, but generally the reported selectivity for the desired product 1,6-hexanedial is very low. This is caused by the formation of deleterious Rh allyl and enolate complexes, which can be suppressed by simultaneous activation of both alkene functions using properly designed bimetallic catalysts.Therefore, we will develop well-defined tetraphosphine ligand systems for the formation of bimetallic complexes capable of activating otherwise unreactive substrates by mutual interactions with functional groups by both metals. Starting point will be a successful class of bidentate ligands, already developed by the PI, which will be modified in such a way that they can be bridged straightforwardly by condensation with diacids. The resulting tetraphosphines will provide novel bimetallic complexes that will be applied in the hydroformylation of conjugated dienes. In a later stage the novel ligands systems will be explored in different reactions like palladium catalyzed alkoxycarbonylation of dienes. The exact ligand structures can be optimized by subtle changes in steric, electronic and bite-angle properties. In another approach we will aim at coupling of two different ligand backbones which opens the possibility of the formation of heterobimetallic complexes. Differences in the structure of the ligand backbone will have impact on the complexation constants of different transition metals. It is anticipated that this can be employed to influence the preferential coordination of one transition metal over another. It will be investigated if this will lead to the selective formation of heterobimetallic complexes based on rhodium and palladium without interference of homometallic binuclear compounds. We will explore the use of these rhodium palladium heterobimetallic complexes as catalyst for one-pot hydroformylation / methoxycarbonylation of dienes. The formation of these alpha,omega-aldehyde esters via a two-step process has been investigated intensively by DSM/DuPont.The design of the new chiral catalysts will be supported by fundamental spectroscopic (including kinetic) studies of the catalytic species present under actual reaction conditions. HP-NMR will be used to study the structure of the bimetallic complexes under static conditions. The effect of the metal-metal distance on the interaction with bifunctional substrates will be investigated. HP-IR will be used to study these complexes under actual catalytic conditions.

醛是制备各种精细化学品和大宗化学品的重要中间体。这些化合物在制药工业、香料和香料工业以及农用化学品和洗涤剂的生产中都有应用。目前，这些产品中有许多是通过化学计量反应制备的，这往往会产生大量的化学废物。人们对基于温和和选择性反应的新的生产方法的需求越来越大，原子效率非常高，从而减少了化学废物问题。催化烯烃氢甲酰化反应是一种温和、清洁的生产高质量醛的工艺，只用CO和H2作为试剂，因此不会产生任何废物。在这个项目中，我们将开发一种新的通用催化剂体系，能够将内部烯烃和共轭双烯转化为高附加值的醛和/或酯。原子经济、清洁的丁二烯氢甲酰化合成中间体1，6-己二醛技术将为聚酰胺的可持续生产做出重大贡献。然而，许多行业和学术研究人员已经研究了铑催化的丁二烯氢甲酰化反应，但通常报道的目标产物1，6-己二醛的选择性很低。这是由于有害的Rh烯丙基和烯醇络合物的形成，这可以通过使用适当设计的双金属催化剂同时激活两个烯烃功能来抑制。因此，我们将开发定义明确的四膦配体系统来形成双金属络合物，能够通过两种金属与官能团相互作用来激活原本不反应的底物。起点将是一类成功的双齿配体，已经由PI开发，它将进行修饰，使它们可以通过与二元酸的缩合直接连接起来。由此得到的四膦类化合物将提供新型的双金属配合物，用于共轭双烯的氢甲酰化反应。在以后的阶段中，我们将在不同的反应中探索新的配体体系，如钯催化的二烯烃的烷氧羰化反应。精确的配体结构可以通过空间、电子和咬角性质的细微变化来优化。在另一种方法中，我们将针对两个不同的配体骨架的偶联，这为形成异双金属络合物打开了可能性。配体主链结构的不同会对不同过渡金属的络合常数产生影响。预计这可以被用来影响一种过渡金属相对于另一种过渡金属的优先配位。将研究这是否会导致在没有同金属双核化合物干扰的情况下选择性地形成基于Rh和Pd的异双金属配合物。我们将探索将这些钯钯异双金属络合物作为催化剂用于双烯的一锅氢甲酰化/甲氧羰化反应。DSM/DuPont二步法研究了这些α，omega-醛酯的两步生成过程，通过对实际反应条件下存在的催化物种的基础光谱(包括动力学)研究，将支持新型手性催化剂的设计。在静态条件下，用核磁共振波谱研究了双金属配合物的结构。研究了金属-金属距离对双功能基片相互作用的影响。在实际催化条件下，用HP-IR对这些配合物进行了研究。