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A kind of preparation method of ethylene glycol aryl borate

The technology of ethylene glycol aryl borate and ethylene glycol is applied in the field of simple preparation of ethylene glycol aryl borate, which can solve the problem of high consumption of organic solvent and waste silica gel, harsh requirements for crystallization solvent, and insoluble borate. water and other problems, to achieve the effect of improving environmental friendliness, reducing the use of organic solvents, and low cost

Inactive Publication Date: 2016-01-06
NANJING UNIV OF POSTS & TELECOMM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The acid precipitation method increases many purification steps, produces a large amount of acid waste liquid, increases the production cost, and when the hydrocarbyl group in the boric acid is large, the borate is not easy to dissolve in water, and is not suitable for acid precipitation; The requirements are relatively strict, and solvent selection is not easy; chromatography will consume a large amount of organic solvents and waste silica gel, and there are major problems in terms of cost and environmental friendliness
These separation and purification methods all have their limitations, which cause certain difficulties for industrial production.
[0004] In addition, the currently reported aryl borates are mainly propylene glycol aryl borate and pinacol aryl borate. These two types of aryl borate have good solubility in organic solvents, and the products are separated and purified. The method is mainly column chromatography separation, which needs to consume a large amount of organic solvents; if the method of recrystallization is used for separation, the loss of the product is relatively large, so it is still necessary to develop a simple synthesis and separation method for aryl boronate, so that it can be used on a large scale. To adapt to the rapid development of the field of organic semiconductors and the wide application of Suzuki reaction in the construction of carbon-carbon bonds

Method used

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  • A kind of preparation method of ethylene glycol aryl borate
  • A kind of preparation method of ethylene glycol aryl borate
  • A kind of preparation method of ethylene glycol aryl borate

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0025] Example 1: Preparation of ethylene glycol 2-spirobifluorene borate.

[0026]

[0027] Under nitrogen protection and dry ice-ethanol bath conditions, 1.6mol / L n-butyllithium / hexane solution (15mL, 0.024mol, 1.2eq) was added dropwise to 2-bromospirobifluorene (7.9g, 0.02mol, 1eq ) in tetrahydrofuran (50mL) solution, maintain the reaction at low temperature for 1h; tri-n-butyl borate (9.2g, 0.04mol, 2eq) and maintain low temperature for 0.5h, then remove the low temperature bath, react at room temperature for 4h; add 2mol / L of hydrochloric acid (100mL), the reaction was completed after 2h. Extract with dichloromethane, combine the organic phases and dry with anhydrous magnesium sulfate, concentrate by distillation, dissolve in toluene (20mL), add ethylene glycol (1.24g, 0.02mol, 1eq), react at 110°C for 2h, stop the reaction and static Placed and cooled, a white solid was precipitated, and 5.3 g of the product was obtained by suction filtration, with a yield of 68.8%....

example 2

[0028] Example 2: Preparation of 2,7-spirobifluorene bisboronic acid ethylene glycol ester.

[0029]

[0030] Under nitrogen protection and dry ice-acetone bath conditions, 1.6mol / L n-butyllithium / hexane solution (29mL, 0.046mol, 2.2eq) was added dropwise to 2,7-dibromospirobifluorene (10g, 0.021mol , 1eq) in tetrahydrofuran (200mL) solution, maintain the reaction at low temperature for 2h; tri-n-butyl borate (14.5g, 0.063mol, 3eq) and maintain low temperature for 0.5h, then remove the low temperature bath, and react at room temperature for 10h; 2mol / L hydrochloric acid (150mL) was added, and the reaction was terminated after 2h of reaction. Extract with dichloromethane, combine the organic phases and dry with anhydrous magnesium sulfate, concentrate by distillation, dissolve in toluene (30mL), add ethylene glycol (2.73g, 0.044mol, 2.1eq), react at 110°C for 5h, stop the reaction and After standing and cooling, a white solid was precipitated, and 7.7 g of the product was o...

example 3

[0031] Example 3: Preparation of ethylene glycol 2-spirofluorene xanthene borate.

[0032] Under nitrogen protection and dry ice-ethanol bath conditions, 1.6mol / L n-butyllithium / hexane solution (15mL, 0.024mol, 1.2eq) was added dropwise to 2-bromospirofluorene xanthene (8.2g, 0.02mol , 1eq) in tetrahydrofuran (50mL) solution, maintain the reaction at low temperature for 1h; tri-n-butyl borate (9.2g, 0.04mol, 2eq) and maintain low temperature for 0.5h, then remove the low temperature bath, and react at room temperature for 4h; 2mol / L hydrochloric acid (100mL) was added, and the reaction was terminated after 2h of reaction. Extract with dichloromethane, combine the organic phases and dry with anhydrous magnesium sulfate, distill and concentrate, dissolve in toluene (25mL), add ethylene glycol (1.24g, 0.02mol, 1eq), react at room temperature for 4h, stop the reaction and static Placed, a white solid was precipitated, and 6.0 g of the product was obtained by suction filtration, ...

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Abstract

The invention discloses a preparation method of gylcol ester arylboronate, belonging to the field of fine organic synthesis and preparation of organic semiconductor materials. The preparation method comprises the following steps: by taking aryl halide as an initial raw material and tetrahydrofuran as a solvent, carrying out a metallization reaction to obtain corresponding aryl metal salt; then, adding tributyl borate for reaction, wherein the molar ratio of tributyl borate to aryl halide is 1:(1.5-6), and hydrolyzing by hydrochloric acid to obtain corresponding arylboronic acid; and then, carrying out reaction on ethylene glycol as an esterifying agent in arene liquor, wherein the molar ratio of ethylene glycol to aryl halide is 1:(1.0-4), standing, separating out a product from the reaction system to obtain a corresponding gylcol ester arylboronate intermediate. The preparation method is simple to operate, low in cost, good in repeatability, high in yield, high in product quality, applicable to batch production and has a broad application prospect, and the reaction is easy to control.

Description

technical field [0001] The invention belongs to the fields of fine organic synthesis and preparation of organic semiconductor materials, and in particular relates to a simple preparation method of a class of arylboronic acid ethylene glycol esters Background technique [0002] The Suzuki reaction is palladium-catalyzed to construct sp from aryl boronic acid or boronic acid ester and halogenated aromatic 2 carbon-sp 2 Or sp carbon coupling has extremely wide applications in modern organic synthesis, especially in the field of organic semiconductor material preparation and pharmaceuticals. Aryl boronic acid or boric acid ester is the key synthetic component of Suzuki reaction. At present, there are generally two main ways to prepare (references: J.Org.Chem.1995,60,7508-7510; J.Org.Chem. 2002, 67, 1041-1044; Adv. Mater. 2000, 12, 828-831). One is to prepare the corresponding aryl borate by coupling reaction of aryl halide or aryl sulfonate with biboronic acid pinacol ester u...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/02
Inventor 黄维解令海欧昌金孙辰孙明礼韩业龙
Owner NANJING UNIV OF POSTS & TELECOMM