STEREOELECTRONIC EFFECTS ON HETEROATOMIC CHEMISTRY

异原子化学的立体电子效应

• 批准号: 3277203
• 负责人: STEPHEN F. NELSEN
• 金额: $ 6.64万
• 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 1988-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3277203
• 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.

利用双环和多环结构，可以控制 键旋转，以加强低氮孤对，孤对相互作用 饱和氮素链，并减缓质子转移 键断裂中间体中的反应。利用这些原则，我们将尝试 为了合成第一个长寿命的例子(R2NN(R)Cl，R2NN(R)NR2， R2NN(R)N(R)NR2、RON(R)N(R)OR和RSN(R)N(R)SR，以及研究 这些化合物的阳离子与R2NOR-素数和的分解反应 R2NSR-素数。这项工作将提供新的化合物和 易被氧化的稀有官能团；它们很可能 证明它具有生物活性。三环六烷基肼类药物 选择特殊的结构使中性的NN裂解化合物存在于 具有大的贯通空间NN相互作用的结构，但仍有空间 将准备接近氮孤子对的试剂，并将其 研究了氧化还原化学。我们希望开发出这样的系统，其中既有 中性和带有NN键的NN裂解形式将给出 相同的3e-sigma键合中间体。这些化合物的中性形式 将具有强大的跨空间独行对、独行对交互，这是 不稳定，也会使试剂接近孤立的对。我们 将研究亲电性物质，如质子和金属原子的络合作用 这些化合物，在络合中寻找特殊的选择性。 环肼阳离子自由基与中性基团的电子转移 联氨似乎会产生不稳定形式的某些联氨，这 通过其他方法是不可用的。这些化合物的反应性研究 电子和空间不稳定的构象异构体将是 被追捕。