STEREOELECTRONIC EFFECTS ON HETEROATOMIC CHEMISTRY

异原子化学的立体电子效应

• 批准号: 3277207
• 负责人: STEPHEN F. NELSEN
• 金额: $ 5.39万
• 依托单位: UNIVERSITY OF WISCONSIN-MADISON
• 依托单位国家: 美国
• 财政年份: 1982
• 资助国家: 美国
• 起止时间: 1982-07-01 至 1989-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3277207
• 关键词: amines; drug design /synthesis /production; drug screening /evaluation; hydrazines; hydrazones; hydrogen transport; nitrogen compounds; triazines

Employing bicyclic and polycyclic structures, it is possible to control bond rotations to enforce low nitrogen lone pair, lone pair interactions in chains of saturated nitrogens, and also to slow down proton transfer reactions in bond-cleaved intermediates. Using the principles, we will try to synthesize the first long-lived examples (of R2NN(R)Cl, R2NN(R)NR2, R2NN(R)N(R)NR2, RON(R)N(R)OR, and RSN(R)N(R)SR, as well as to study decomposition reactions of cations of these compounds and R2NOR-prime and R2NSR-prime. This work will make available new compounds with unprecidented functional groups which are easily oxidized; they may well prove biologically active. Tricyclic hexaalkylhydrazine dications of special structures chosen to make the neutral NN cleaved compounds exist in structures with large through-space NN interactions, yet have room for reagents to approach the nitrogen lone pairs will be prepared, and their redox chemistry studied. We are hoping to develop systems in which both the neutral and NN-cleaved dicationic forms with an NN bond will give the same 3e-sigma bonded intermediate. The neutral forms of these compounds will have strong through-space lone pair, lone pair interaction, which is destabilizing, and also will allow reagents to approach the lone pairs. We will study complexation of electrophiles such as protons and metal atoms by these compounds, looking for special selectivities in complexation. Electron-transfer of cyclic hydrazine cation radicals with the neutral hydrazine appears to generate unstable forms of certain hydrazines, which are not available by other methods. Study of the reactivity of these electronically and sterically destabilized conformational isomers will be pursued.

采用双环和多环结构，可以控制 键旋转，以加强低氮孤对，孤对相互作用， 饱和氮的链，并且还减慢质子转移 键裂中间体中的反应。 利用这些原则，我们将尝试 为了合成第一个长寿命的实例（R2 NN（R）Cl，R2 NN（R）NR 2， R2 NN（R）N（R）NR 2、罗恩（R）N（R）OR和RSN（R）N（R）SR，以及研究 这些化合物的阳离子和R2 NOR-素数的分解反应， R2NSR-prime。 这项工作将提供新的化合物， 容易氧化的未沉淀官能团;它们可以很好地 证明具有生物活性。 三环六烷基肼双阳离子 选择使中性NN裂解化合物存在的特殊结构 具有大的通过空间NN相互作用的结构，但有空间 将制备接近氮孤对的试剂，并且它们的 氧化还原化学研究。 我们希望开发出一种系统， 具有NN键的中性和NN-裂解的双阳离子形式将得到 相同的3e-sigma键合中间体。 这些化合物的中性形式 会有很强的穿越空间的孤对电子相互作用， 不稳定，也将允许试剂接近孤对电子。 我们 将研究亲电体如质子和金属原子的络合作用， 这些化合物，寻找特殊的选择性络合。 环肼阳离子自由基与中性分子的电子转移 肼似乎产生某些肼的不稳定形式， 是其他方法所不能提供的。 研究这些反应性 电子和空间不稳定的构象异构体将是 追求。