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Preparation method of allylboronic acid pinacol ester

A technology of pinacol ester and alkenyl boronic acid, which is applied in the general preparation field of alkenyl boronic acid pinacol ester, and can solve problems such as potential safety hazards in the production process

Inactive Publication Date: 2019-03-19
DALIAN RES & DESIGN INST OF CHEM IND
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0013] Although this route has a short process, it uses highly flammable n-butyllithium, and there are great safety hazards in the production process.

Method used

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  • Preparation method of allylboronic acid pinacol ester
  • Preparation method of allylboronic acid pinacol ester
  • Preparation method of allylboronic acid pinacol ester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] [Example 1] Preparation of cyclohexene-1-boronic acid pinacol ester

[0019]

[0020] After mixing cyclohexanone (20g, 0.2mol), pyridine p-toluenesulfonate (5g, 0.02mol), p-toluenesulfonyl hydrazide (38g, 0.2mol), and acetonitrile (200mL), the temperature was raised to reflux, and after the reaction , acetonitrile was distilled off under reduced pressure, 49 g of sulfonylhydrazone compound was obtained after adding isopropanol for recrystallization, and the yield was 90%;

[0021] Mix sulfonylhydrazone compound (49g, 0.18mol), isopropylmagnesium chloride solution (370mL, 1.0M) and tetramethylethylenediamine (23g, 0.2mol) and react at 40°C for 3h. After the reaction is complete, drop Add methylboronic acid pinacol ester (26.5g, 0.19mol), react for 2h, then heat up to reflux for 1h. After the reaction was completed, after the solvent was evaporated, the product cyclohexene-1-boronic acid pinacol ester was continuously evaporated at about 100° C. to obtain 27.5 g, with...

Embodiment 2

[0022] [Example 2] Preparation of 1-ethyl-1,2,3,6-tetrahydropyridine-4-boronic acid pinacol ester

[0023]

[0024] After mixing N-ethyl-4-piperidone (25g, 0.2mol), pyridine p-toluenesulfonate (5g, 0.02mol), p-toluenesulfonyl hydrazide (40g, 0.21mol) and ethanol (250mL), The temperature was raised to reflux, and after the reaction was completed, the solvent was evaporated, and 50 g of the sulfonyl hydrazone compound recrystallized from isopropanol was added, with a yield of 86%;

[0025] Mix the compound hydrazone (50g, 0.17mol), isopropylmagnesium chloride solution (430mL, 1.0M), and tetramethylethylenediamine (22g, 0.19mol) and react under reflux for 3h. After the reaction is complete, add methyl Boric acid pinacol ester; (24g, 0.17mol), react for 2h, then heat up to reflux for 1h. After the reaction was completed, after the solvent was evaporated, the product 1-ethyl-1,2,3,6-tetrahydropyridine-4-boronic acid pinacol ester was continuously evaporated to obtain 25.5 g, wi...

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PUM

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Abstract

The invention provides a common preparation method of allylboronic acid pinacol ester. The common preparation method takes aliphatic ketone as a raw material and comprises the following steps: takingaliphatic ketone and p-toluenesulfonohydrazide as raw materials to react to generate p-toluenesulfonylhydrazone; taking the p-toluenesulfonylhydrazone and a Grignard reagent to react, so as to generate an intermediate allylmagnesium chloride; and taking the allylmagnesium chloride and methoxyboronic acid pinacol ester (isopropoxyboronic acid pinacol ester) to react, so as to prepare the allylboronic acid pinacol ester. A synthesis route has moderate reaction conditions, high yield and good commonality.

Description

technical field [0001] The invention relates to a general preparation method of alkenylboronic acid pinacol ester, which belongs to the technical field of organic synthesis. Background technique [0002] Alkenyl boronic acid pinacol ester compounds are widely used in the synthesis of anti-cancer and anti-HIV drugs. The existing preparation methods mainly include the following: [0003] Route 1: first prepare alkenyllithium compound from aliphatic ketone, then react alkenyllithium with alkoxyboronic acid pinacol ester to generate alkenylboronic acid pinacol ester, such as: [0004] [0005] The yield of this synthetic route is generally not high, and the elemental lithium is too active. At the same time, phosphorus pentachloride is relatively toxic and absorbs water to generate a large amount of irritating acid gas. There is a large safety hazard in the industrial use of this method. [0006] Route 2: First prepare alkenyllithium compound from aliphatic ketone, then react...

Claims

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Application Information

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IPC IPC(8): C07F5/02
CPCC07F5/025
Inventor 王可为赵文武唐培昆蔡小川
Owner DALIAN RES & DESIGN INST OF CHEM IND
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