| Autor: |
Goncharova IK; Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences , 28 Vavilova Street , Moscow 119991 , Russian Federation., Silaeva KP; Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences , 28 Vavilova Street , Moscow 119991 , Russian Federation.; Mendeleev University of Chemical Technology of Russia , 9 Miusskaya Sq. , Moscow 125047 , Russian Federation., Arzumanyan AV; Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences , 28 Vavilova Street , Moscow 119991 , Russian Federation., Anisimov AA; Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences , 28 Vavilova Street , Moscow 119991 , Russian Federation., Milenin SA; Enikolopov Institute of Synthetic Polymeric Materials , Russian Academy of Sciences , 70 Profsoyuznaya Street , Moscow 117393 , Russian Federation., Novikov RA; Engelhardt Institute of Molecular Biology , Russian Academy of Sciences , 32 Vavilova Street , Moscow 119991 , Russian Federation.; Zelinsky Institute of Organic Chemistry , Russian Academy of Sciences , 47 Leninsky Pr. , Moscow 119991 , Russian Federation., Solyev PN; Engelhardt Institute of Molecular Biology , Russian Academy of Sciences , 32 Vavilova Street , Moscow 119991 , Russian Federation., Tkachev YV; Engelhardt Institute of Molecular Biology , Russian Academy of Sciences , 32 Vavilova Street , Moscow 119991 , Russian Federation., Volodin AD; Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences , 28 Vavilova Street , Moscow 119991 , Russian Federation., Korlyukov AA; Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences , 28 Vavilova Street , Moscow 119991 , Russian Federation.; Pirogov Russian National Research Medical University , 1 Ostrovityanov Street , Moscow 117997 , Russian Federation., Muzafarov AM; Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences , 28 Vavilova Street , Moscow 119991 , Russian Federation.; Enikolopov Institute of Synthetic Polymeric Materials , Russian Academy of Sciences , 70 Profsoyuznaya Street , Moscow 117393 , Russian Federation. |
| Abstrakt: |
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, O 2 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-CH 3 , Ar-CH 2 -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. |
