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Synthesis and application of novel vinyl boronizing reagent

A technology of vinyl boron and reagents, applied in the field of boron chemical synthesis, can solve the problems of high price and high price of metal ruthenium reagents

Active Publication Date: 2014-12-17
CANGZHOU PURUI DONGFANG SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage of this method is that dibromoborane is only available in reagent grade and is expensive
The disadvantage of this method is that the metal ruthenium reagent is expensive and uses an excessive amount of pinacol borane

Method used

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  • Synthesis and application of novel vinyl boronizing reagent
  • Synthesis and application of novel vinyl boronizing reagent
  • Synthesis and application of novel vinyl boronizing reagent

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Synthesis of trans-bromovinyl potassium trifluoroborate (1): under the protection of argon, in a 5L three-neck flask equipped with ventilation and airtight buffer system, first add boron tribromide (250 grams, 1.0 mole) and anhydrous 1500 ml of dichloromethane, stirred evenly, cooled to -10°C. Start to feed acetylene gas slowly, and keep the gas bubbling from below the liquid surface during the feeding. At this time, there will be obvious heat generation, and keep the system temperature not exceeding 0°C and continue feeding. The entire aeration process is completed within 4-8 hours. If the aeration is too fast, the cooling should be accelerated or the aeration should be stopped to avoid excessive pressure in the system. When there is no longer gas absorption, about 1.4 moles (36.5 grams) of acetylene are passed into. At this time, the reaction solution is carefully sampled. The reaction solution is added to the previously cooled pinacol and methanol mixed solution, and...

Embodiment 2

[0033] Synthesis of trans-bromovinyl potassium trifluoroborate (1): under the protection of argon, in a 10L glass kettle equipped with ventilation and a closed buffer system, first add boron tribromide (500 grams, 2.0 moles) and anhydrous 2500 ml of dichloromethane, after stirring evenly, cooled to -10°C. Start to feed acetylene gas slowly, and keep the gas bubbling from under the liquid surface when feeding. At this time, there will be obvious heat release, and keep the system temperature not exceeding 0°C and continue feeding. The entire aeration process is completed within 6-10 hours. If the aeration is too fast, the cooling should be accelerated or the aeration should be stopped to avoid excessive pressure in the system. When there is no longer gas absorption, about 3.0 moles (78.1 grams) of acetylene are passed into, and the reaction solution is carefully sampled at this time, and the reaction solution is added to the previously cooled pinacol and methanol mixed solution,...

Embodiment 3

[0036]Synthesis of trans-1-propenyl potassium trifluoroborate (3, R=Me): In a fully dried 250 ml three-necked flask, 0.05 mole of boronating reagent 1 (10.6 g), methyl boric acid (0.06 mole, 3.6 grams) and 150 milliliters of toluene were added, and after stirring evenly, the trachea was inserted until the solution was below the liquid level, and nitrogen was bubbled to remove oxygen for about 10-20 minutes. Subsequently, anhydrous potassium fluoride (0.125 mol, 7.26 g) and PdCl2 (dppf) (1.1 g, 3% mol) were added under nitrogen protection, and reacted at 45° C. overnight. After the detection reaction is finished, filter with diatomaceous earth and wash with 30 ml of toluene. After the combined filtrates were spin-dried under reduced pressure, 160 ml of acetone was added, the insoluble solids were filtered off, the filtrate was spin-dried again, 110 ml of diethyl ether was added for beating, and 4.59 g of off-white flaky solids were obtained with a yield of 62%. H NMR (400MHz, ...

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Abstract

The invention relates to synthesis and application of a novel vinyl boronizing reagent, the reagent can be coupled with other organic boric acid to obtain trans potassium alkenyltrifluoroborate in various forms. The synthesis method is as below: slowly introducing propyne into a dichloromethane solution of boron tribromide at -10 to 0 DEG C; directly adding potassium fluoride aqueous solution or quenching under acidic conditions to obtain boric acid; then directly addingg potassium hydrogen fluoride to obtain a target boronizing reagent trans-bromoethenyl trifluoro borane potassium (1), which is a white flake solid, wherein the yield in the step is 71-82%. The boronizing reagents can be subjected to Suzuki coupling to be effectively applied in synthesis of trans potassium alkenyltrifluoroborate (3) in different forms. The invention has the advantages of high stereoselectivity and strong stability of the product, suitability for long time storage, and simple, fast and high yield synthesis method.

Description

Technical field: [0001] The invention belongs to the technical field of boron chemical synthesis. Background technique: [0002] In recent years, the application of alkenyl boronic acids / esters in organic synthesis has gradually increased. However, due to the instability of alkenyl boronic acids / esters and the characteristics of easy polymerization, they either need to be stored at low temperature, or they can only be synthesized without separation. However, it directly limits the application in the scale-up of drug synthesis. At the same time, there are very few methods for the synthesis of pure trans-alkenyl boronic acids / esters, and most of them do not have the feasibility of scale-up operations. [0003] Regarding trans-alkenyl boronic acid, the existing methods in the literature are as follows: starting from a trans-substituted alkenyl bromide compound, preparing a Grignard reagent, then reacting with a boron reagent, and post-processing to obtain trans-alkenyl boronic...

Claims

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Application Information

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IPC IPC(8): C07F5/02
Inventor 冷延国桂迁张进余锦华
Owner CANGZHOU PURUI DONGFANG SCI & TECH
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