Dioxycarbene chemistry

二氧卡宾化学

• 批准号: 1110-2007
• 负责人: Warkentin, John
• 金额: $ 2.4万
• 依托单位: McMaster University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2007
• 资助国家: 加拿大
• 起止时间: 2007-01-01 至 2008-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=363724
• 关键词: Dioxycarbene; chemistry

Organic reactions often proceed through reactiveintermediates. Some of these can be observed by means of spectroscopy, but many are too short-lived to accumulate to a detectable level.Carbenes (divalent carbon intermediates)are of the latter type. With only two bonds to carbon, rather than the usual four, they react with a large variety of organic compounds, forming cyclopropanes by addition to a double bond, for example, and/ or products of rearrangement. They also react with themselves or with the products formed in a primary reaction.We propose to study dioxycarbenes, generated by a reaction that we have discovered. Dioxycarbenes, although quite short-lived, are less reactive than dialkylcarbene analogs and are therefore more discriminating in their reactions. We will study their chemistry toward small molecules such as carbon dioxide and carbon disulfide (heterocumulenes), as well as their reactions with compounds having small bond angles (strained compounds).

有机反应经常通过活性中间体进行。其中一些可以通过光谱法观察到，但许多都是短暂的积累到可检测的水平。卡宾（二价碳中间体）属于后一种类型。由于只有两个碳键，而不是通常的四个，它们与各种有机化合物反应，例如通过添加到双键和/或重排产物形成环丙烷。它们也与自身或与初级反应中形成的产物反应。我们建议研究由我们发现的反应生成的二氧卡宾。二氧卡宾虽然寿命很短，但其反应活性低于二烷基卡宾类似物，因此其反应更具区别性。我们将研究它们对小分子如二氧化碳和二硫化碳的化学反应，以及它们与具有小键角的化合物（应变化合物）的反应。