Ryzhkov Aleksei I, Drozdov Fedor V, Cherkaev Georgij V, Muzafarov Aziz M
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991 Moscow, Russia.
Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Sciences, 117393 Moscow, Russia.
Polymers (Basel). 2022 Aug 12;14(16):3279. doi: 10.3390/polym14163279.
In this work, carbosilane dendrons of the first, second, and third generations were obtained on the basis of a natural terpenoid, limonene. Previously, we have shown the possibility of selective hydrosilylation and hydrothiolation of limonene. It is proved that during hydrosilylation, only the isoprenyl double bond reacts, while the cyclohexene double bond does not undergo into the hydrosilylation reaction. However, the cyclohexene double bond reacts by hydrothiolation. This selectivity makes it possible to use limonene as a dendron growth center, while maintaining a useful function-a double bond at the focal point. Thus, the sequence of hydrosilylation and Grignard reactions based on limonene formed carbosilane dendrons. After that, the end groups were blocked by heptamethyltrisiloxane or butyllithium. The obtained substances were characterized using NMR spectroscopy, elemental analysis and GPC. Thus, the proposed methodology for the synthesis of carbosilane dendrons based on the natural terpenoid limonene opens up wide possibilities for obtaining various macromolecules: dendrimers, Janus dendrimers, dendronized polymers, and macroinitiators.
在这项工作中，基于天然萜类化合物柠檬烯制备了第一代、第二代和第三代碳硅烷树枝状分子。此前，我们已证明柠檬烯进行选择性硅氢化和氢硫基化反应的可能性。事实证明，在硅氢化过程中，只有异戊二烯双键发生反应，而环己烯双键不参与硅氢化反应。然而，环己烯双键会通过氢硫基化反应发生反应。这种选择性使得可以将柠檬烯用作树枝状分子的生长中心，同时在焦点处保留一个有用的官能团——双键。因此，基于柠檬烯的硅氢化反应和格氏反应序列形成了碳硅烷树枝状分子。之后，端基用七甲基三硅氧烷或丁基锂进行封端。使用核磁共振光谱、元素分析和凝胶渗透色谱对所得物质进行了表征。因此，所提出的基于天然萜类化合物柠檬烯合成碳硅烷树枝状分子的方法为获得各种大分子：树枝状聚合物、Janus树枝状聚合物、树枝状化聚合物和大分子引发剂开辟了广阔的可能性。
