Synthesis of Siloxane Derivatives of Phenylboronic Acids of Different Structures.

The synthesis of a storage-stable organosilicon modifier with a dioxaborolane-protecting group is described. Its high reactivity and selective anti-Markovnikov addition in hydrosilylation reactions to afford siloxanes of various structures are shown. The possibility of deprotection of both the initial modifier and its siloxane derivatives under mild conditions using water in yields up to 96% is demonstrated. The existence of an equilibrium between the organosilicon derivatives of phenylboronic acids and their cyclic six-membered boroxines was confirmed by 1H NMR spectroscopy and X-ray diffraction analysis data. The use of siloxane derivatives of phenylboronic acids in Suzuki-Miyaura and Chan-Lam cross-coupling reactions was studied. All synthesized compounds were characterized by NMR (1H, 11B, 13C, and 29Si), IR spectroscopy, and high-resolution mass spectrometry.

Polyborosiloxanes (PBS): Evolution of Approaches to the Synthesis and the Prospects of Their Application.

The mini-review deals with borosiloxanes as a class of organoelement compounds that comprise Si-O-B bonds, including individual compounds and polymeric structures. The borosiloxanes first synthesized in the 1950s using simple methods demonstrated very unusual properties but were hydrolytically unstable. However, in recent times, synthetic methods have changed significantly, which made it possible to synthesize borosiloxanes that are resistant to external factors, including atmospheric moisture. Borosiloxanes became important due to their unique properties. For example, borosiloxane liquids acquire a thixotropic behavior due to donor-acceptor interchain interactions. In addition, borosiloxanes are used to produce flame-retardant ceramics. An analysis of the literature sources shows that no review has yet been completed on the topic of borosiloxanes. Therefore, we decided that even a brief outlook of this area would be useful for researchers in this and related fields. Thus, the review shows the evolution of the synthesis methods and covers the studies on the properties of these unique molecules, the latest achievements in this field, and the prospects for their application.

Synthesis of Carbosilane and Carbosilane-Siloxane Dendrons Based on Limonene.

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.

Chemical Structural Coherence Principle on Polymers for Better Adhesion.

Composite materials are the most variative type of materials employed in almost every task imaginable. In the present study, a synthesis of a novel perfluoroalkyltriethoxysilane is reported to be used in creating composites with polyhexafluoropropylene-one of the most indifferent and adhesion-lacking polymers existing. The mechanism of adhesion of hexafluoropropylene is proved to be due to chemical structural coherence of perfluoroalkyltriethoxysilane to a link of polyhexafluoropropylene chain. The ability of perfluoroalkyltriethoxysilane to attach to surfaces was studied by FT-IR spectroscopy of modified glass microspheres. Although the perfluoroalkyltriethoxysilane surface modifier allowed partial adhesion of polyhexafluoropropylene, some detachment took place; therefore, the surface nanostructuring was used to increase its specific area by aluminum foil anodizing. An anodized aluminum surface was studied by scanning electron microscopy. The resulting composite consisting of anodized aluminum, perfluoroalkyl surface modifier, and polyhexafluoropropylene layer was proved to be stable, showed no signs of detachment, and is a promising material for usage in harsh environments.

Organoboron Derivatives of Stereoregular Phenylcyclosilsesquioxanes.

This study presents the synthesis of organoboron derivatives of stereoregular 4-, 6-, and 12-unit phenylcyclosilsesquioxanes. All compounds obtained were isolated in good yields (70-80 %) and were fully characterized by 1 H, 13 C, 29 Si, 11 B NMR, IR spectroscopy, HRMS ESI, and elemental microanalysis. The structure of the key modifier, obtained for the first time, 4-(tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) dimethylvinylsilane, was also confirmed by single-crystal XRD.