Preparation method and application of 1,4-diboric acid ester-2-butyne

A technology of diboronic acid ester and butyne, which is applied in the field of organic compound synthesis and application, and achieves the effect of easy operation

Active Publication Date: 2017-04-19
湖北航聚科技股份有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The synthesis of 1,4-diboronate-2-butyne has not yet been reported in the literature, and it will be possible to obtain 1,3-butadiene- 2,3-disecondary alcohol products

Method used

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  • Preparation method and application of 1,4-diboric acid ester-2-butyne
  • Preparation method and application of 1,4-diboric acid ester-2-butyne
  • Preparation method and application of 1,4-diboric acid ester-2-butyne

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preparation example Construction

[0017] The preparation method of 1,4-diboronic acid ester-2-butyne, its step is: in N 2 , Under the condition of -78°C, use n-butyllithium as the base, add trichlorethylene dropwise to the flask; after the dropwise addition, raise the temperature of the mixed solution to 30°C for 12 hours, and then cool to -78°C; then Add iodomethyleneboronic acid pinacol ester dropwise to the mixed solution, continue to react for 2 hours after the dropwise addition, and then raise the temperature to 30°C for 48 hours; after the reaction is completed, add water to quench, separate and purify to obtain the product 1,4-di Borate-2-butyne, the general reaction formula is as follows:

[0018]

[0019] The application of synthesizing 1,3-butadiene-2,3-disecondary alcohol with 1,4-diboronic acid ester-2-butyne as raw material, the steps are: in N 2 Atmosphere, 30°C or 50°C or 80°C, aromatic aldehydes (benzaldehyde, 4-methylbenzaldehyde, 4-bromobenzaldehyde), 1,4-diboronate-2-butyne, toluene or ...

Embodiment 1

[0023] Preparation of 1,4-diboronate-2-butyne.

[0024]

[0025] Under nitrogen atmosphere, add 45mL THF / Et into a 250mL two-necked flask 2 A mixed solvent of O (volume ratio 1:1) and 17.5 mL of diethyl ether solution (2.5 M, 43.7 mmol) of n-butyllithium were stirred and cooled to -78 °C. Dissolve 1.3mL of trichlorethylene (14.6mmol) in 10mL of anhydrous ether, slowly drop it into the above mixed solution, raise the temperature to 30°C and stir for 12 hours to obtain a white turbid solution. Under a nitrogen atmosphere, an anhydrous ether solution (50 mL) of iodomethyleneboronic acid pinacol ester (7.8 g) was cooled to -78° C., and the above white turbid liquid was slowly added dropwise into the cooled solution with a syringe. After the dropwise addition, the reaction was continued at -78°C for 2 hours, and then the temperature was slowly raised to 30°C for 48h. After the reaction was completed, 30 mL of water was added to quench the reaction and the liquids were separate...

Embodiment 2

[0027] Preparation of 1,3-butadiene-2,3-disecondary alcohol compound

[0028]

[0029] Under nitrogen atmosphere, add benzaldehyde (10.6mg, 0.1mmol), 1,4-diboronate-2-butyne (15.3mg, 0.05mmol), 2-nitrobenzoic acid (1.0mg, 10mol%) and anhydrous toluene (0.25mL), stirred and reacted at 30°C for 48 hours, and then directly separated by column chromatography to obtain the target product 1,3-butadiene-2,3-disecondary alcohol compound. Yield 51%, dr=3.8:1.

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Abstract

The invention relates to a preparation method and application of 1,4-diboric acid ester-2-butyne. The preparation method comprises the steps of performing pinacol ester reaction of trichloro ethylene and iodine methylene boric acid by regarding n-butyllithium as alkali, and obtaining a product 1,4-diboric acid ester-2-butyne through separation and purification; performing tandem propargyl / guildline alkenyl reaction on 1,4-diboric acid ester-2-butyne and aromatic aldehyde to prepare a 1,3-butadiene-2,3-di-secondary alcohol compound. The preparation method is simple and convenient to operate; the used reagents are nontoxic, green and environment-friendly; the prepared 1,3-butadiene-2,3-di-secondary alcohol compound can be further subjected to derivatization through Diels-Alder or Shapless epoxidation reaction, and is an important organic synthon.

Description

technical field [0001] The invention belongs to the technical field of synthesis and application of organic compounds, and relates to a preparation method of 1,4-diboronate-2-butyne and the synthesis of 1,3-butadiene-2,3-disecondary alcohols using it as a raw material Compound application. Background technique [0002] Organoboron compounds have important properties such as non-toxicity, good stability, and adjustable reactivity, and are an important class of organic synthesis reagents [Kennedy, J.W.J.; Hall, D.G.Angew.Chem., Int.Ed. 4739; Denmark, S.E.; Fu, J. Chem. Rev. 2003, 103, 2763; Huo, H.-X.; Duvall, J.R.; Huang, M.-Y.; 2014, 1, 303.]. Cascade reactions between unsaturated bisboronic esters and carbonyl-containing compounds have attracted attention for the construction of complex and useful products. [0003] In 2013, the Morken group started from 1,3-butadiene through an asymmetric borylation reaction to obtain a chiral unsaturated ortho bis-boronate, followed by...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02C07C33/28C07C33/48C07C29/42
CPCC07C29/42C07F5/025C07C33/28C07C33/486
Inventor 黄毅勇杨星蔡亚鹏江文钞
Owner 湖北航聚科技股份有限公司
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