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CN-122011050-A - 2N-type cobalt complex, preparation method thereof and hydrosilylating reaction of hydrosilane and alcohol

CN122011050ACN 122011050 ACN122011050 ACN 122011050ACN-122011050-A

Abstract

The invention relates to a 2N-type cobalt complex, a preparation method thereof and a silicon-based reaction of hydrogen-containing silane and alcohol. The 2N-type cobalt complex is one of Co 1-Co 6. The 2N-type cobalt complex and the preparation method thereof, and the silicon-based reaction of hydrogen-containing silane and alcohol can be used for catalyzing the silicon-based reaction of hydrogen-containing silane and alcohol to synthesize triphenylsilyl ether, and have the advantages of mild condition, simple synthesis steps, low cost, high catalytic activity, good substrate universality, no need of using active auxiliary agent and the like, and provide a new method for constructing a silicon-oxygen bond.

Inventors

  • YANG SHENGCHAO
  • ZHANG ZHANDONG
  • SHU LONGSHENG
  • WANG XIAOHUI
  • ZENG XINGWANG
  • WANG HAIYI
  • JIANG SIWEI
  • BU QINGQING
  • ZHANG PENG
  • CAO SONG
  • ZHOU JIAN
  • LIU ZHICHAO
  • HAO HAN
  • GUO YUAN

Assignees

  • 石河子大学
  • 新疆西部合盛硅业有限公司
  • 新疆合盛硅业新材料有限公司

Dates

Publication Date
20260512
Application Date
20260126

Claims (10)

  1. 1. The 2N-type cobalt complex is characterized in that the 2N-type cobalt complex is one of Co 1-Co 6; The structural formula of the Co 1-Co 6 is shown as follows: 。
  2. 2. the preparation method of the 2N-type cobalt complex according to claim 1, which is characterized in that the preparation method comprises the steps of dissolving a ligand and cobalt acetylacetonate in tetrahydrofuran solution, and reacting for 10-14 hours at 60-70 ℃ to obtain the 2N-type cobalt complex; The ligand is one of 2- (1H-pyrazol-1-yl) pyridine, 2- (3-methyl-1H-pyrazol-1-yl) pyridine, phenanthroline, bipyridine or 4,4 '-dimethyl-2, 2' -bipyridine and 4,4 '-di-tert-butyl-2, 2' -bipyridine.
  3. 3. The method according to claim 2, wherein, The molar ratio of the ligand to the cobalt acetylacetonate is 1:0.5-0.7.
  4. 4. The method according to claim 2, wherein, The synthesis method of the 2- (1H-pyrazol-1-yl) pyridine comprises the steps of adding 2-bromo-pyridine, pyrazole, potassium carbonate and cuprous iodide into dimethyl sulfoxide solution, and reacting for 20-28H at 110-130 ℃; The synthesis method of the 2- (3-methyl-1H-pyrazol-1-yl) pyridine comprises the steps of adding 2-bromo-pyridine, 3-methylpyrazole, potassium carbonate and cuprous iodide into a dimethyl sulfoxide solution, and reacting for 20-28H at 110-130 ℃.
  5. 5. The silylation reaction of hydrogen-containing silane and alcohol is characterized in that the silylation reaction is carried out by uniformly mixing hydrogen-containing silane, alcohol, catalyst and organic solvent, and then carrying out the silylation reaction in inert gas atmosphere to obtain dehydrogenation coupling product, namely triphenyl silyl ether; the catalyst is the 2N-type cobalt complex as claimed in claim 1.
  6. 6. A silylation reaction according to claim 5, characterized in that, The hydrogen-containing silane is triphenylsilane; The chemical structural formula of the alcohol used is: wherein R is a benzene ring substituent or an aliphatic chain group.
  7. 7. A silylation reaction according to claim 6, characterized in that, The alcohol is at least one of benzyl alcohol, 4-methylbenzyl alcohol, 3-methylbenzyl alcohol, 2-methylbenzyl alcohol, 4-methoxybenzyl alcohol, 4-isopropylbenzyl alcohol, 2,4, 6-trimethylbenzyl alcohol, p-ethylbenzyl alcohol, 2- (methylthio) ethanol, cyclohexanol, 4-chlorobenzyl alcohol, 4-trifluoromethyl benzyl alcohol, 3-nitrobenzyl alcohol and 2-phenethyl alcohol.
  8. 8. A silylation reaction according to claim 5, characterized in that, The organic solvent is tetrahydrofuran.
  9. 9. A silylation reaction according to claim 5, characterized in that, The molar ratio of the hydrogen-containing silane to the alcohol to the catalyst is 1:0.5-2:0.005-0.02; the temperature of the silicon-based reaction is 40-80 ℃ and the time is 8-20 h.
  10. 10. A silylation reaction according to claim 4, characterized in that, The molar ratio of the hydrogen-containing silane to the alcohol to the catalyst is 1:2:0.02; The temperature of the silicon-based reaction is 70 ℃ and the time is 12h.

Description

2N-type cobalt complex, preparation method thereof and hydrosilylating reaction of hydrosilane and alcohol Technical Field The invention belongs to the technical field of organic chemistry catalysis, and particularly relates to a 2N type cobalt complex, a preparation method thereof and a silicon-based reaction of hydrogen-containing silane and alcohol. Background Organosilicon ether compounds (si—o bonds) play a vital role in the chemical industry as a class of important chemicals, since they find application in the production of adhesives, adhesion promoters, lubricants, waterproofing agents, etc., and furthermore, the dehydrocoupling of hydrosilanes with alcohols generates hydrogen as a by-product, which also leads to an increasing interest in the use of hydrosilanes as hydrogen storage materials. The traditional synthesis method of the silyl ether is through the alcoholysis reaction of chlorosilane, but a large amount of alkali is needed to neutralize HCl gas generated by the reaction, so a more environment-friendly and sustainable scheme is needed. The hydrosilanes thus replace traditional chlorosilanes, the dehydrogenation coupling is the most attractive route from an atomic economy point of view, forming H 2 as the only by-product, generating the silyl ether, which avoids the production of unnecessary acids, these reactions being driven mainly by the formation of stable si—o bonds, which is a chemically favourable but kinetically slow process designed for the synthesis of organosilanes, which requires to a large extent the development of an effective catalyst capable of operating under mild conditions, but almost all processes for the dehydrogenation coupling reaction to give the silyl ether require the use of noble metal catalysts or strong base catalysis. More importantly, for tertiary silanes such as triphenylsilanes, which have a large steric hindrance, low reactivity profile, direct dehydrogenative coupling with alcohols remains a challenge. The existing few non-noble metal catalytic systems (such as certain iron catalysts) have one or more defects of high catalyst load (5 mol%), poor economy, narrow substrate universality, particularly rapid reduction of catalytic efficiency on secondary alcohols, tertiary alcohols or long-chain fatty alcohols with larger steric hindrance, severe reaction conditions, high temperature (150 ℃) or strong base additives, poor chemical selectivity, easiness in causing side reactions such as self dehydrogenation polymerization of triphenylsilane, and low yield of target silyl ether. Therefore, the development of a metal catalyst with low price, high catalytic efficiency and good substrate universality is necessary for the dehydrogenation coupling reaction of silane. In view of the above, the invention provides a 2N-type cobalt complex, a preparation method thereof, and a catalytic hydrosilylation reaction for preparing triphenylsilyl ether by using hydrosilane and alcohol, wherein the 2N-type cobalt complex is low in cost, has the advantages of high reaction activity and good substrate universality in the dehydrogenation coupling reaction of triphenylsilane and alcohol, and does not need to add an activating agent in the silylation reaction. Disclosure of Invention The invention aims to provide a 2N type cobalt complex which can catalyze the silylation reaction of triphenylsilane and alcohol to prepare triphenylsilyl ether under the condition of no additive. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a 2N-type cobalt complex, wherein the 2N-type cobalt complex is one of Co 1-Co 6; The structural formula of the Co 1-Co 6 is shown as follows: the invention also aims to provide a preparation method of the 2N-type cobalt complex, which is simple and convenient, and raw materials are cheap and easy to obtain. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: The preparation method of the 2N-type cobalt complex comprises the steps of dissolving a ligand and cobalt acetylacetonate in tetrahydrofuran solution, and reacting for 10-14 hours at 60-70 ℃ to obtain the 2N-type cobalt complex; The ligand is one of 2- (1H-pyrazol-1-yl) pyridine, 2- (3-methyl-1H-pyrazol-1-yl) pyridine, phenanthroline, bipyridine or 4,4 '-dimethyl-2, 2' -bipyridine and 4,4 '-di-tert-butyl-2, 2' -bipyridine. Further, the molar ratio of the ligand to the cobalt acetylacetonate is 1:0.5-0.7. The synthesis method of the 2- (1H-pyrazol-1-yl) pyridine comprises the steps of adding 2-bromo-pyridine, pyrazole, potassium carbonate and cuprous iodide into dimethyl sulfoxide solution, and reacting for 20-28H at 110-130 ℃. The synthesis method of the 2- (3-methyl-1H-pyrazol-1-yl) pyridine comprises the steps of adding 2-bromo-pyridine, 3-methylpyrazole, potassium carbonate and cuprous iodide into a dimethyl sulfoxide solution, and reacting for 20-28H at 110-130 ℃. The invention also aims to provide a preparat