RU-2861463-C1 - METHOD FOR PRODUCING 1-(3-(METHYL(DIMETHOXY)SILYL)PROPYL)-1H-AZOLES

RU2861463C1RU 2861463 C1RU2861463 C1RU 2861463C1RU-2861463-C1

Abstract

FIELD: chemistry. SUBSTANCE: invention relates to methods for producing carbofunctional dialkoxy(organo)silanes. A method is proposed for producing 1-(3-(methyl(dimethoxy)silyl)propyl)-1H-1,2,4-triazole and 1-(3-(methyl(dimethoxy)silyl)propyl)-1H-benzimidazole by obtaining the sodium salt of the azole from equimolar amounts of 1,2,4-triazole or benzimidazole and sodium hydroxide while heating with water removal in a toluene medium, followed by alkylation with methyl(dimethoxy)(3-chloropropyl)silane while boiling the reaction mass for 6 hours, distilling off, before introducing the alkylating reagent, half of the initially taken toluene and adding an equal amount of dimethylformamide. EFFECT: expansion of the arsenal of methods for producing 1-(3-(methyl(dimethoxy)silyl)propyl)-1H-azoles using available starting reagents and a solvent that provides a good yield of the target products, amounting to 70-71%. 1 cl, 2 ex

Inventors

Konshin Valerii Viktorovich
Spesivaia Ekaterina Sergeevna
Dzhamilia Naibovna Konshina

Dates

Publication Date: 20260505
Application Date: 20250811

Claims (1)

A method for obtaining 1-(3-(methyl(dimethoxy)silyl)propyl)-1H-1,2,4-triazole and 1-(3-(methyl(dimethoxy)silyl)propyl)-1H-benzimidazole by alkylation with methyl(dimethoxy)(3-chloropropyl)silane of the sodium salt of azole, which is obtained from equimolar quantities of 1,2,4-triazole or benzimidazole and sodium hydroxide by heating with water separation in a toluene medium, and the alkylation is carried out with methyl(dimethoxy)(3-chloropropyl)silane by boiling the reaction mass for 6 hours, distilling off, before introducing the alkylating reagent, half of the initially taken toluene and adding an equal amount of dimethylformamide.

Description

The invention relates to organoelement chemistry, and more specifically to methods for producing carbofunctional dialkoxy(organo)silanes. 1-(3-(Alkyl(dialkoxy)silyl)propyl)-1H-azoles are used, for example, to obtain polysiloxane biocides (Mizerska, U., Fortuniak, W., Chojnowski, J., Hałasa, R., Konopacka, A., Werel, W. Polysiloxane cationic biocides with imidazolium salt (ImS) groups, synthesis and antibacterial properties. European Polymer Journal, 2009, 45(3), 779–787. doi: 10.1016/j.eurpolymj.2008.11.045), as coupling agents to improve the compatibility of silica dispersion with rubber used to produce wear-resistant tires (patent JP2010189613), to obtain a polysiloxane palladium catalyst for the reaction Suzuki-Miyaura (T. Borkowski, W. Zawartka, P. Pospiech, U. Mizerska, A. M. Trzeciak, M. Cypryk, W. Tylus. Reusable functionalized polysiloxane-supported palladium catalyst for Suzuki–Miyaura cross-coupling. Journal of Catalysis, 2011, Vol. 282, Iss. 2, P. 270-277. DOI: 10.1016/j.jcat.2011.06.023). A two-stage process for the preparation of 1-(3-(methyl(diethoxy)silyl)propyl)-1H-imidazole 5 is known. In the first stage, sodium imidazole salt 3 is obtained by fusing imidazole 1 with sodium hydroxide 2 at 91 °C and a molar ratio of reactants of 1.2:1, followed by washing the resulting reaction product with tetrahydrofuran and drying. The yield of 3 is 82.2%. In the second stage, the obtained sodium salt of imidazole 3 is alkylated with (3-iodopropyl)methyl(diethoxy)silane 4 in a tetrahydrofuran medium at 70 °C for 48 hours. The yield of the target compound is 47.8% or 39.3% based on the amount of imidazole taken. The resulting compound was used to obtain polysiloxane polar phases for gas chromatography. (Xiaojie Zhao, Kaifeng Tan, Jun Xing. A flexible and convenient strategy for synthesis of ionic liquid bonded polysiloxane stationary phases. Journal of Chromatography A Volume 1587, 22 February 2019, Pages 197-208.) A one-stage method for obtaining 1-(3-methyl(diethoxy)silyl)propyl-1H-imidazole 5 is known: hydrosilylation of N-allylimidazole 6 with methyldiethoxysilane 7 is carried out in a toluene medium at 90 °C for three days in the presence of Karstedt's catalyst. (Mizerska, U., Fortuniak, W., Chojnowski, J., Hałasa, R., Konopacka, A., Werel, W. Polysiloxane cationic biocides with imidazolium salt (ImS) groups, synthesis and antibacterial properties. European Polymer Journal, 2009, 45(3), 779–787. doi: 10.1016/j.eurpolymj.2008.11.045) The objective of the present invention is to expand the range of methods for producing 1-(3-(methyl(dimethoxy)silyl)propyl)-1H-azoles using available starting reagents and solvents, ensuring a high yield of the target product. The technical result of the invention is the implementation of the claimed method for producing 1-(3-(methyl(dimethoxy)silyl)propyl)-1H-azoles. The technical result is achieved by carrying out a one-reactor two-stage process, including the production of sodium salt of azole 10, 11 by heating in a toluene medium with the separation of equimolar quantities of azole 8, 9 and sodium hydroxide 2 . In the second stage, alkylation of methyl(dimethoxy)(3-chloropropyl)silane 12 is carried out by boiling the reaction mixture for 6 hours, distilling off, before introducing the alkylating reagent, half of the initially taken toluene and adding an equal amount of dimethylformamide: The yield of target compounds is 70-71%. The structure and purity of the obtained compounds were confirmed by NMR spectroscopy and chromatograph mass spectrometry. Thus, a one-pot, two-stage process for the preparation of 1-(3-(methyl(dimethoxy)silyl)propyl)-1H-azoles is proposed, which uses readily available, inexpensive starting compounds. An example of obtaining 1-(3-(methyl(dimethoxy)silyl)propyl)-1H-1,2,4-triazole. In a flask equipped with a magnetic stirring element and a Dean-Stark trap with a reflux condenser, 100 ml of toluene, 9.67 g (0.14 mol) of 1,2,4-triazole and 5.6 g (0.14 mol) of sodium hydroxide are placed. The reaction mass is heated with vigorous stirring and boiling until the separation of water in the trap is complete. After this, 50 ml of toluene is distilled off. 50 ml of dimethylformamide are added to the residue, then 25 ml (25.58 g, 0.14 mol) of methyl (dimethoxy) (3-chloropropyl) silane and the reaction mass is vigorously boiled for 6 hours. The resulting sodium chloride precipitate is filtered off on a Schott filter and washed with toluene. The filtrate is evaporated on a rotary evaporator, and the residue is subjected to fractional distillation under vacuum, collecting the 113°C/0.7 Torr fraction. Yield 70%. The product is a viscous, colorless liquid with a specific odor. 1H NMR spectrum (399.78 MHz, CDCl3 ) δ, ppm: 0.07 s (3H, CH3 ), 0.47-0.52 m (2H, CH2 ), 1.88 – 1.95 m (2H, CH2 ), 3.45 s (6H, CH3 ), 4.11 t ( J = 6.8 Hz, 2H, CH2 ), 7.89 br s (1H, CH), 8.02 br s (1H, CH). 13 C NMR spectrum (100.5 MHz, CDCl 3 , δ, ppm): -6.0 (CH 3 ), 9.9 (CH 2 ), 23.4 (CH 2