The formation and stabillity of spiro-compounds. Part I. Spiro-compounds from cyclo-hexane.
The formation and stabillity of spiro-compounds. Part I. Spiro-compounds from cyclo-hexane.
复制标题
DOI：
10.1039/ct9150701080
复制
发表时间：
1915-01-01
期刊：
影响因子：
--
通讯作者：
Thorpe, JF
中科院分区：
文献类型：
--
作者：
Beesley, RM;Ingold, CK;Thorpe, JF
在本通讯为第一部分的一系列研究中，旨在确定由于改变四面体角度而导致的011环构型的变化对第二个环的形成和稳定性的影响，该第二个环由两个共同的四元碳原子连接。根据Baeyer的应变假说，为了产生环己烷环，必须改变四面体的法线角度，而产生环结构所需的变化量通常取决于形成的环的性质。因此，两个侧链连接到环己烷环的任何一个碳原子上形成的角度可能会随着参与环形成的那些价态之间的角度的任何变化而成比例地改变。换句话说，与环己烷衍生物的同一碳原子发出的两个侧链上的基团相比，连接到两个侧链上的基团将比具有开链结构的相应化合物中的基团更紧密。这可以通过图(A)粗略地说明，在图(A)中，假设参与环的两个价态向外弯曲，导致另外两个价态在剩余空间中均匀分布。那么角度将不再是109O28/，而是10928‘-2x(假设a)。另一方面，如果参与环结构的碳原子的两个剩余价态保持四面体角度(图3)。B)，则剩余的空间必须在
IN the series of investigations of which this coinmunicatioii is Part I, it is intended to ascertain thel effect which is produced by the alteration of the tetrahedral angle, consequent 011 ring-f orina-tion, on the formatdon and stability of a second ring joined to the existing ring by a quaternary carbon atom common to both. In accordance with Baeyer’s strain hypothesis, the normal angle of the tetrahedron has to be altered in order to produce the cyclo-hexane ring, and the amount of change necessary to produce ringstructure, generally, is dependent on the character of the ring formed. It is possible, therefore, that the angle formed by two sidechains attached to any one carbon atom of, for example, the cyclohexane ring, will be altered in proportion to any change in the angle between those valencies which participate in the ringformation. In other words, the groups attached to two side-chains emanating from the same carbon atom of a cyclohexane derivative will be closer together than in a corresponding compound having an open-chain structure.This can be illustrated, roughly, by means of Fig.(a), in which it is assumed that the bending outwards of the two valencies, participating in the ring, causes the other two to distribute themselves equally in the remaining space. The angles will then no longer be 109O28/, but 109 28’-2x (hypothesis a). On the other hand, if the two remaining valencies of the carbon atom participating in the ring-structure retain the tetrahedral angle (Fig. b), the space remaining would have to be distributed equally between the