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CN-121991115-A - Benzo-silicon heterocyclic compound, and preparation method and application thereof

CN121991115ACN 121991115 ACN121991115 ACN 121991115ACN-121991115-A

Abstract

The invention discloses a benzo-silicon heterocycle compound and a preparation method and application thereof. The structural formula of the benzosilacycle compound is as follows: Wherein R 1 is selected from phenyl, 4-methylphenyl, 4-chlorophenyl or R 2 is selected from-H, methyl or-Cl, and R 3 is selected from-H or phenyl. The benzosilacycle compound can be used as a raw material for synthesizing medicines or electrical insulation materials, and the preparation method has the advantages of low-cost and easily-obtained raw materials, simplicity, convenience, high efficiency, mild reaction conditions, high atom economy, easy purification of products, green economy and the like, and is suitable for large-scale industrial production and application.

Inventors

  • ZENG WEI
  • ZHANG ZILU
  • HUANG FANGSHENG

Assignees

  • 华南理工大学
  • 广东良仕工业材料有限公司

Dates

Publication Date
20260508
Application Date
20260126

Claims (10)

  1. 1. The benzosilacycle compound is characterized by having the following structural formula: Wherein R 1 is selected from phenyl, 4-methylphenyl, 4-chlorophenyl or R 2 is selected from-H, methyl or-Cl, and R 3 is selected from-H or phenyl.
  2. 2. A process for preparing a benzosilacycle compound as claimed in claim 1, comprising the step of dispersing an orthoalkynylarylalkenyl silane compound, phenylhydrosilane, a cobalt catalyst, an organic ligand, an additive and a reducing agent in an organic solvent to effect a hydrosilicon cyclization reaction, wherein the orthoalkynylarylalkenyl silane compound is Phenylhydrosilane is Obtaining the benzosilacycle compound.
  3. 3. The method of claim 2, wherein the molar ratio of the o-alkynylarylalkenyl silane compound to the phenylhydrosilane is 1:1-3.
  4. 4. The method of claim 2, wherein the molar ratio of the ortho-alkynyl arylalkenyl silane compound, the cobalt catalyst, the organic ligand, the additive and the reducing agent is 1:0.05-0.20:0.05-0.30:0.1-0.5.
  5. 5. The method according to claim 2 to 4, wherein the cobalt catalyst is at least one of cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) acetate and cobalt (III) pentamethylcyclopentadienyl carbonyl diiodo-compound.
  6. 6. The method according to claim 2 to 4, wherein the organic ligand is at least one of 1, 3-bis (diphenylphosphine) propane, 1, 3-bis (diphenylphosphine) ethane, 2' -bipyridine, 1, 10-phenanthroline, 2':6',2' ' -tripyridine.
  7. 7. The method according to claim 2 to 4, wherein the additive is at least one of zinc iodide, zinc bis (trifluoromethanesulfonyl) imide, zinc acetate, sodium iodide, and silver hexafluoroantimonate.
  8. 8. The method for preparing the zinc powder/manganese powder composite material according to any one of claims 2 to 4, wherein the reducing agent is at least one of zinc powder and manganese powder.
  9. 9. The method of claim 2 to 4, wherein the hydrosilicon cyclization is carried out at a temperature of 0 ℃ to 100 ℃ for 6 hours to 24 hours.
  10. 10. Use of a benzosilacycle compound as claimed in claim 1 in the preparation of a medicament or an electrical insulating material.

Description

Benzo-silicon heterocyclic compound, and preparation method and application thereof Technical Field The invention relates to the technical field of organic synthesis, in particular to a benzo-silicon heterocycle compound and a preparation method and application thereof. Background The silicon heterocyclic compound has unique biological activity and photoelectric property, and has great application potential in the fields of biochemistry, medicinal chemistry, material science and the like. However, doping a silicon atom in a cyclic molecular skeleton is not easy, so how to economically and efficiently construct a heterocyclic molecular skeleton is of great interest. Currently, the construction of the backbone of a silicon heterocyclic molecule mainly includes two strategies: 1) Construction of silicon heterocyclic Compounds by means of a ring-tensioning strategy, typically Cyclobutylsilane (SCB), by use of Small Ring-tensioning Release, e.g., a) construction of silicon heterocyclic molecular skeleton by a) use of alpha, beta unsaturated aldehydes/ketones and their derivatives as coupling reagents （Hirano, K., Yorimitsu, H., Oshima, K. Palladium-catalyzed formal cycloaddition of silacyclobutanes with enones: Synthesis of eight-membered cyclic silyl enolates[J]. Org. Lett., 10(11), 2199-2201.）;b） and other small ring compounds as coupling reagents （Qin, Y., Han, J.-L., Ju, C.-W., Zhao, D. Ring Expansion to 6-, 7-, and 8-Membered Benzosilacycles through Strain-Release Silicon-Based Cross-Coupling[J]. Angew. Chem., 2020, 132(22), 8559-8563;Wang, X.-C., Wang, H.-R., Xu, X., Zhao, D. Ring Expansion to 8-Membered Silacycles through Formal Cross-Dimerization of 5-Membered Palladacycles with Silacyclobutanes[J]. Eur. J. Org. Chem., 2021, 2021(21), 3039-3042;Qin, Y., Li, L., Liang, J.-Y., Li, K., Zhao, D. Silacyclization through palladium-catalyzed intermolecular silicon-based C(sp2)-C(sp3) crosscoupling[J]. Chem. Sci., 2021, 12(42), 14224-14229.）; 2) Construction of silicon-heterocyclic compounds using acyclic tonicity strategies, e.g. transition metal-catalyzed C-H/Si-H coupling reactions and hydrosilylation reactions of unsaturated hydrocarbons （Fang, H., Hou, W., Liu, G., and Huang, Z. Ruthenium-catalyzed site-selective intramolecular silylation of primary C-H bonds for synthesis of sila-heterocycles. J. Am. Chem. Soc., 2017, 139(33), 11601-11609;Tang, R.-H., Xu, Z., Nie, Y.-X., Xiao, X.-Q., Yang, K.-F., Xie, J.-L., Guo, B., Yin, G.-W., Yang, X.-M., Xu, L.-W. Catalytic asymmetric trans-selective hydrosilylation of bisalkynes to access AIE and CPL-active silicon-stereogenic benzosiloles[J]. iScience, 2020, 23(7), 101268;Huang, Y.-H., Wu, Y., Zhu, Z., Zheng, S., Ye, Z., Peng, Q., Wang, P. Enantioselective synthesis of silicon-stereogenic monohydrosilanes by rhodiumcatalyzed intramolecular hydrosilylation[J]. Angew. Chem. Int. Ed., 61(1), e202113052.）. However, the substrates adopted by the above method are generally not easy to synthesize (part of the substrates even need to be modified by groups), and noble transition metal catalysts such as Pd (II), rh (II) and the like are often needed to catalyze the reaction, so that the practical application of the substrates is limited greatly. Therefore, the development of the preparation method of the silicon heterocyclic compound has the advantages of cheap and easily obtained raw materials, simplicity, convenience, high efficiency, mild reaction conditions, high atom economy, easy purification of products, green and economy, and has very important significance in preparing various benzo silicon heterocyclic compounds. Disclosure of Invention The invention aims to provide a benzo-silicon heterocycle compound, and a preparation method and application thereof. The technical scheme adopted by the invention is as follows: A benzosilacycle compound has the following structural formula: Wherein R 1 is selected from phenyl, 4-methylphenyl, 4-chlorophenyl or (2-Thienyl), R 2 is selected from-H, methyl or-Cl, and R 3 is selected from-H or phenyl. The preparation method of the benzo-silicon heterocycle compound comprises the following steps: Dispersing an o-alkynyl aryl alkenyl silane compound, phenyl hydrosilane, a cobalt catalyst, an organic ligand, an additive and a reducing agent in an organic solvent to perform hydrosilicon cyclization reaction, wherein the o-alkynyl aryl alkenyl silane compound is Phenylhydrosilane isObtaining the benzosilacycle compound. Preferably, the molar ratio of the o-alkynyl aryl alkenyl silane compound to the phenyl hydrogen silane is 1:1-3. Preferably, the molar ratio of the ortho-alkynyl aryl alkenyl silane compound, the cobalt catalyst, the organic ligand, the additive and the reducing agent is 1:0.05-0.20:0.05-0.30:0.1-0.5. Preferably, the cobalt catalyst is at least one of cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) acetate and cobalt (III) pentamethylcyclopentadienyl carbonyl diiodo-compound. Further preferably, the co