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New method for cracking and hydrogenating carbon-boron bond of green organic boron reagent

An organic boron, a new method of technology, applied in the preparation of organic compounds, organic chemistry, hydrocarbons and other directions, can solve problems such as unreported

Active Publication Date: 2017-09-22
TAIZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2013, Cheon’s research group developed a hydroxyl-directed DMSO-promoted deborylation reaction of ortho- and p-arylboronic acids. This method does not require the use of any catalyst, but the substrates are limited to 2- or 4-substituted phenol derivatives. matter, very limited (J.Org.Chem., 2013, 78, 12154)
[0004] Compared with the traditional or expensive metal-catalyzed deborylation of organoboron reagents with poor atom economy, the cheap and easy-to-obtain potassium methoxide catalyzed method obviously has the advantages of convenient operation, low production cost, and high industrial application value. However, this Class methods have not been reported at home and abroad

Method used

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  • New method for cracking and hydrogenating carbon-boron bond of green organic boron reagent

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Add 4-biphenylboronic acid (1mmol), potassium methoxide (0.05mmol), 2mL methanol or ethanol to a sealed tube of 10mL sequentially, heat and stir in an oil bath at 120°C for 12 hours, and when the reaction is complete, add an equivalent amount of homogenate to the crude product Trimethylbenzene was used as an internal standard to determine the exact yield of product by GC. According to GC, when methanol or ethanol is used as the reaction solvent, the yields are 87% and 80% respectively; according to the column chromatography separation result, the product yield is 82%. 1 H NMR (400MHz, CDCl 3 ) δ7.62 (d, J=8.0Hz, 4H), 7.46 (t, J=8.0Hz, 4H), 7.37 (t, J=8.0Hz, 2H).

Embodiment 2

[0021] Add 4-biphenyl borate (1mmol), potassium methoxide (0.05mmol), 2mL methanol or ethanol to a 10mL sealed tube in sequence, heat and stir in an oil bath at 120°C for 12 hours, and when the reaction is complete, add an equivalent amount of Mesitylene was used as an internal standard to determine the exact yield of the product by GC. According to GC, when methanol or ethanol is used as the reaction solvent, the yields are 83% and 77% respectively; according to the column chromatography separation result, the product yield is 75%. 1 H NMR (400MHz, CDCl 3 ) δ 7.62 (d, J=8.0Hz, 4H), 7.46 (t, J=8.0Hz, 4H), 7.37 (t, J=8.0Hz, 2H).

Embodiment 3

[0023] Add 4-tert-butylboronic acid (1mmol), potassium methoxide (0.05mmol), 2mL methanol or ethanol to a sealed tube of 10mL sequentially, heat and stir in an oil bath at 120°C for 12 hours, and when the reaction is complete, add an equivalent amount of Mesitylene was used as an internal standard to determine the exact yield of product by GC. According to GC, when methanol or ethanol was used as the reaction solvent, the yields were 79%, 66%, respectively.

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Abstract

The invention relates to a new method for efficiently cracking and hydrogenating a carbon-boron bond of an environment-friendly organic boron reagent. The new method is characterized in that inorganic base which is cheap and easy to obtain is used as a catalyst, and common organic alcohol is used as a reaction solvent and a hydrogen source, organic boric acid or borate can be conveniently catalyzed under an atmosphere environment, so as to carry out carbon-boron bond cracking and hydrogenating reaction, the universality of reaction substrates is wide, and the compatibility of functional groups is excellent. Carbon-boron bond breaking reaction caused by catalyzing all kinds of boric acid and borate by non-metal is systematically realized, the limit that a traditional method requires boron removing and hydrogenating by using excessive organic base, organic fluoric acid which is large in environment hazard or a complicated metal catalyst is also overcome, and a bran-new strategy is provided for boron removing and hydrogenating reaction for preparing the organic boron reagent in a lab and industrially producing the organic boron reagent.

Description

technical field [0001] The invention relates to a new green and high-efficiency method for cracking and hydrogenating the carbon-boron bond of an organic boron reagent. Background technique [0002] Organic boronic acid and boric acid ester are cheap, easy to obtain, low toxicity, and unique chemical properties, so they are widely used as organic chemical intermediates in organic synthesis. The dehydroboration reaction, as a by-product of metal-catalyzed coupling reactions of organoboron reagents, has attracted little attention from chemists. As early as 1930, Ainley et al first reported the equivalent metal salt (CuSO 4 , ZnCl 3 etc.) to promote the dehydroboration reaction of aryl boronic acid (J.Chem.Soc.,1930,2171). Subsequently, many reports and very important progress have been made on the dehydrogenation reactions of organoboron reagents. In 2013, Cheon’s research group developed a hydroxyl-directed DMSO-promoted deborylation reaction of ortho- and p-arylboronic a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C1/32C07C15/14C07C15/02C07C15/06C07C15/24C07C15/28C07C15/30C07C17/354C07C25/02C07C22/08C07C25/13C07D213/06C07D213/127C07C67/317C07C69/78
CPCC07C1/321C07C17/354C07C67/317C07C2531/02C07D213/06C07D213/127C07C15/14C07C15/02C07C15/06C07C15/24C07C15/28C07C15/30C07C25/02C07C22/08C07C25/13C07C69/78
Inventor 姚武冰
Owner TAIZHOU UNIV