Mapping the chemistry of phosphorus-containing analogues of urea. From fundamental chemistry to high-performance compounds and materials.

绘制尿素含磷类似物的化学图谱。

基本信息

批准号：
EP/M027732/1
负责人：
Jose Goicoechea
金额：
$ 46.45万
依托单位：
University of Oxford
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2015
资助国家：
英国
起止时间：
2015 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FM027732%2F1
关键词：
Mapping chemistry phosphorus containing analogues

项目摘要

The isolobal analogy is frequently invoked to draw comparisons between the fundamental chemistry of small inorganic molecules and more established organic species. For example, the diagonal relationship between a methine fragment (C-H) and phosphorous has led to the latter being nicknamed a "carbon-copy". This has resulted in extensive chemistry aimed at developing phosphorus-containing analogues of organic molecules such as phospha-alkenes (RP=PR) and -alkynes (PCR), amongst many other examples. However, an isolobal relationship does not imply that phosphorus-containing congeners of specific organic molecules can be readily synthesized. In fact, the synthesis of relatively simple molecules where a C-H unit, or even an isoelectronic element such as nitrogen, has been replaced by a phosphorus atom still represents a significant technical and intellectual challenge. In this regard synthetic inorganic chemistry lags far behind organic synthesis.As a case in point, while urea was first synthetically isolated in 1829, it was not until late 2013 that our research group succeeded in the isolation of a phosphorus analogue, phosphinecarboxamide. Considering the importance of urea as a chemical feedstock, we propose to utilize this heavier analogue (and other related species) for the synthesis of novel molecules and solids. This is a completely new approach to organophosphorus compounds which, while inherently risky, has the potential to generate fascinating new species that are related to those derived from urea, but that have fundamentally different chemical and physical properties. Current methods for the synthesis of phosphorus-containing chemicals (employed, for example, in pharmaceuticals and specialty chemicals such as photo-initiators) require the use of phosphorus (III) chloride as a feedstock. While such processes currently represent the industrial state-of-the-art, the use of alternative non-toxic precursors remains a highly desirable objective. Alternative strategies to organophosphorus compounds based on the chemical activation of white phosphorus are possible (and well-documented in the literature), however such transformations are often marred by low selectivities or require multiple subsequent manipulations to be competitive with industrial processes. Moreover, white phosphorus is itself highly pyrophoric and dangerous to manipulate. The risks associated with these precursors make the identification of novel phosphorus-atom feedstocks highly desirable.We propose to develop the chemistry of a new class of phosphorus-containing small molecules that are accessible using red phosphorus, a non-pyrophoric allotrope of the element. Ultimately, this will allow us to reduce the safety risks typically encountered when manipulating conventional precursors for the synthesis of specialty chemicals. Building on recent breakthroughs in our laboratory, we will explore the chemistry of the 2-phosphaethynolate anion and phosphinecarboxamide, two novel phosphorus-containing analogues of otherwise ubiquitous chemicals (the cyanate ion and urea, respectively). Our ultimate goal is to access novel molecular, supramolecular and polymeric species with potential applications in catalysis, chemical sensing and materials chemistry. This proposal represents an entirely novel approach to the development of phosphorus-containing molecules and solids of enormous potential societal and economic impact.

经常调用隔离的类比，以在小型无机分子的基本化学和更具成熟的有机物种之间进行比较。例如，甲基碎片（C-H）和磷之间的对角线关系导致后者被昵称为“碳拷贝”。这导致了广泛的化学作用，旨在开发有机分子的含磷的类似物，例如磷酸 - 烷烃（RP = PR）和-alkynes（PCR），以及许多其他例子。但是，孤立关系并不意味着可以很容易地合成特定有机分子的含磷的同源物。实际上，相对简单的分子的合成，其中C-H单元，甚至是氮等异元素元素，已被磷原子所取代，仍然代表着一项重大的技术和智力挑战。在这方面，合成无机化学远远落后于有机合成的情况。在一个很好的例子中，尿素在1829年首次合成分离，直到2013年下半年，我们的研究小组才成功地隔离了磷类模拟磷酸酰胺。考虑到尿素作为化学原料的重要性，我们建议利用这种较重的类似物（及其他相关物种）来合成新的分子和固体。这是一种全新的有机磷化合物的方法，尽管固有的风险，但具有与尿素衍生的新物种相关的引人入胜的新物种，但具有根本不同的化学和物理性能。当前合成含磷化学物质的方法（例如，在药物和特种化学物质（例如光寄生体）中使用）需要使用磷（III）氯化物作为原料。尽管此类过程目前代表了工业的最新工艺，但使用替代性无毒前体仍然是一个非常理想的目标。基于白磷化学激活的有机磷化合物的替代策略是可能的（文献中有充分记录的），但是这种转化通常会因低选择性而破坏，或者需要多次随后的操纵才能与工业过程具有竞争力。此外，白磷本身是高度热的，并且可以操纵危险。与这些前体相关的风险使新型的磷 - 原子原料非常需要。我们建议开发一种新的含磷的小分子的化学，这些分子使用红色磷，该元素的非磷磷可访问。最终，这将使我们能够降低操纵常规前体合成特种化学品时通常遇到的安全风险。在我们实验室最近突破的基础上，我们将探索2-磷酸乙醇酸酯阴离子和磷酸二羧酰胺的化学，这是两个新型含磷的新型化学物质（分别为cyanate Ion和尿素）。我们的最终目标是获取具有潜在应用于催化，化学感应和材料化学的新型分子，超分子和聚合物物种。该提案代表了一种完全新颖的方法，用于开发含磷的分子以及巨大潜在的社会和经济影响的固体。

项目成果

期刊论文数量（9）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Phosphinecarboxamide as an unexpected phosphorus precursor in the chemical vapour deposition of zinc phosphide thin films.

DOI：
10.1039/c8dt00544c
发表时间：
2018-07
期刊：
Dalton transactions
影响因子：
4
作者：
Samuel V F Beddoe;Samuel D. Cosham;A. Kulak;A. Jupp;J. Goicoechea;G. Hyett
通讯作者：
Samuel V F Beddoe;Samuel D. Cosham;A. Kulak;A. Jupp;J. Goicoechea;G. Hyett

Amino acid functionalisation using the 2-phosphaethynolate anion. A facile route to (phosphanyl)carbonyl-amino acids.