Synthesis of Carbosilane and Carbosilane-Siloxane Dendrons Based on Limonene

Abstract

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.

Keywords: carbosilane dendrimers; hydrosilylation; limonene; siloxanes.

Figure 1

Typical scheme for the synthesis of carbosilane dendrons using the starting chloropropyl triallyl silane as an example (top); scheme for the synthesis of carbosilane dendrons based on limonene (bottom).

Figure 2

Library of obtained dendrons based on limonene with allyl functionality on the periphery and blocked with heptamethyltrisiloxane.