66870-89-1Relevant academic research and scientific papers
Construction of siloxane structures with P-Tolyl substituents at the silicon atom
Ardabevskaia, Sofia N.,Korlyukov, Alexander A.,Milenin, Sergey A.,Muzafarov, Aziz M.,Novikov, Roman A.,Solyev, Pavel N.,Tkachev, Yaroslav V.,Volodin, Alexander D.
, (2020/09/11)
In this work, general approaches for preparing p-tolylsilanes as promising precursors for the synthesis of functionalized organosilicon compounds are discussed. Various synthetic techniques, including new and specially developed ones, were used to obtaine
Aerobic Co-/ N-Hydroxysuccinimide-Catalyzed Oxidation of p-Tolylsiloxanes to p-Carboxyphenylsiloxanes: Synthesis of Functionalized Siloxanes as Promising Building Blocks for Siloxane-Based Materials
Goncharova, Irina K.,Silaeva, Kseniia P.,Arzumanyan, Ashot V.,Anisimov, Anton A.,Milenin, Sergey A.,Novikov, Roman A.,Solyev, Pavel N.,Tkachev, Yaroslav V.,Volodin, Alexander D.,Korlyukov, Alexander A.,Muzafarov, Aziz M.
supporting information, p. 2143 - 2151 (2019/02/05)
Synthesis of organosilicon products with a "polar" functional group within organic substituents is one of the most fundamentally and practically important challenges in today's chemistry of silicones. In our study, we suggest a solution to this problem, viz., a high-efficiency preparative method based on aerobic Co-/N-hydroxysuccinimide (NHSI) catalyzed oxidation of p-tolylsiloxanes to p-carboxyphenylsiloxanes. This approach is based on "green", commercially available, simple, and inexpensive reagents and employs mild reaction conditions: Co(OAc)2/NHSI catalytic system, O2 as the oxidant, process temperature from 40 to 60 °C, atmospheric pressure. This reaction is general and allows for synthesizing both mono- and di-, tri-, and poly(p-carboxyphenyl)siloxanes with p-carboxyphenyl groups at 1,1-, 1,3-, 1,5-, and 1,1,1-positions. All the products were obtained and isolated in gram amounts (up to 5 g) and in high yields (80-96%) and characterized by NMR, ESI-HRMS, GPC, IR, and X-ray data: p-carboxyphenylsiloxanes in crystalline state form HOF-like structures. Furthermore, it was shown that the suggested method is applicable for the oxidation of organic alkylarene derivatives (Ar-CH3, Ar-CH2-R) to the corresponding acids and ketones (Ar-C(O)OH and Ar-C(O)-R), as well as hydride silanes ([Si]-H) to silanols ([Si]-OH). The possibility of synthesizing monomeric (methyl) and polymeric (siloxane-containing PET analogue, Sila-PET) esters based on 1,3-bis(p-carboxyphenyl)disiloxane was studied. These processes occur with retention of the organosiloxane frame and allow to obtain the corresponding products in 90 and 99% yields.
Use of MnCl2/tBuOOH oxidizing system for conversion of p-tolyldisiloxanes to p-carboxyphenyldisiloxanes
Goncharova, Irina K.,Arzumanyan, Ashot V.,Milenin, Sergey A.,Muzafarov, Aziz M.
supporting information, p. 28 - 30 (2018/05/03)
The possibility of Mn-catalyzed oxidation of p-tolyldisiloxanes 1a-b to the corresponding p-carboxyphenyldisiloxanes 2a-b was studied using a commercially available and inexpensive system based on MnCl2/tBuOOH. Products 2a and 2b were isolated in 51% and 32% yields, respectively.
New achiral phenylacetylene monomers having an oligosiloxanyl group most suitable for helix-sense-selective polymerization and for obtaining good optical resolution membrane materials
Liu, Lijia,Zang, Yu,Hadano, Shingo,Aoki, Toshiki,Teraguchi, Masahiro,Kaneko, Takashi,Namikoshi, Takeshi
, p. 9268 - 9276 (2011/11/14)
To develop new phenylacetylene monomers more suitable for helix-sense-selective polymerization (HSSP) we reported previously and to improve the efficiency of the HSSP and membrane performance of the resulting polymers, novel phenylacetylenes having a flexible oligosiloxanyl group (SnBDHPA)together with the other related three series of monomers were synthesized and polymerized by using a chiral catalytic system and enantioselectivity in permeation of the membranes from the resulting chiral polymers were examined. SnBDHPA was the most suitable for the HSSP and the CD absorptions (G values) of poly- (SnBDHPA) were stronger and more stable than those of the corresponding polymers having rigid alkyl groups. The polymers could be fabricated to flexible self-supporting membranes by using solvent-casting method. In addition, enantioselectivity in permeation of one of poly(SnBDHPA) membranes was much higher than that of a poly(phenylacetylene) membrane having alkyl groups. This was because the polymers having oligosiloxane groups had high regularity of structures, i.e., chemical structures of the macromolecules such as one handedness and high order structures such as columnar contents in the membranes, and the membranes were flexible and had almost no defects. These good properties as optical resolution membrane materials were caused by flexibility, hydrophobicity, and bulkiness of the oligosiloxane chains. S3BDHPA having a trisiloxanyl group was found to be the best monomer for the HSSP and for obtaining good optical resolution membrane materials.
