Synthesis method of aromatic borate compounds

The technology of an aromatic boronate ester and a synthesis method is applied in the field of using ultraviolet light to induce the synthesis of aromatic boronate ester compounds, which can solve the problems such as no literature report, and achieve the effects of high yield, economical raw materials and easy operation.

Active Publication Date: 2016-08-17
丽水遂智科技咨询有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

So far, there have been no literature reports

Method used

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  • Synthesis method of aromatic borate compounds
  • Synthesis method of aromatic borate compounds
  • Synthesis method of aromatic borate compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] Embodiment 1: the synthesis of phenylboronic acid ester

[0015]

[0016] Add 2mL of acetonitrile, benzenesulfonyl chloride (52.8mg, 0.3mmol), pinacol diborate (114.3mg, 0.45mmol), dipotassium hydrogen phosphate (104.4mg, 2.0eq.) into a 25mL reaction tube, and use a UV lamp The reaction tube was irradiated and the reaction was stirred magnetically at room temperature for 24 hours. After the reaction was completed, most of the solvent was evaporated under reduced pressure, and the remaining mixed solution was separated and purified by column chromatography with petroleum ether / ethyl acetate (30:1) as the eluent to obtain the desired product as a white solid , 39.8mg, yield 65%.

[0017] Its NMR data are as follows:

[0018] 1 H NMR (300MHz, CDCl 3 )δ=7.94~7.90(m,1H),7.84(d,J=6.0Hz,1H),7.64(d,J=6.0Hz,1H),7.50~7.28(m,2H),1.37(s,12H ). 13 C NMR (75MHz, CDCl 3 )δ=137.6, 134.7, 131.2, 127.7, 127.1, 83.8, 24.9.

Embodiment 2

[0019] Embodiment 2: the synthesis of 4-methylphenyl borate

[0020]

[0021] Add acetonitrile 2mL, 4-methylbenzenesulfonyl chloride (57.0mg, 0.3mmol), diboronic acid pinacol ester (114.3mg, 0.45mmol), dipotassium hydrogen phosphate (104.4mg, 2.0eq.) into a 25mL reaction tube , the reaction tube was irradiated with ultraviolet light, and the reaction was stirred by magnetic force at room temperature for 24 hours. After the reaction was completed, most of the solvent was evaporated under reduced pressure, and the remaining mixed solution was separated and purified by column chromatography with petroleum ether / ethyl acetate (30:1) as the eluent to obtain the desired product as a white solid , 44.5 mg, yield 68%.

[0022] Its NMR data are as follows:

[0023] 1 H NMR (300MHz, CDCl 3 )δ=7.81(d, J=9.0Hz, 2H), 7.27(d, J=9.0Hz, 2H), 2.44(s, 3H), 1.41(s, 12H). 13 C NMR (75MHz, CDCl 3 )δ=141.4, 134.9, 128.6, 83.6, 24.9, 21.8.

Embodiment 3

[0024] Embodiment 3: the synthesis of 4-methoxyphenyl borate

[0025]

[0026] Add acetonitrile 2mL, 4-methylbenzenesulfonyl chloride (61.8mg, 0.3mmol), diboronic acid pinacol ester (114.3mg, 0.45mmol), dipotassium hydrogen phosphate (104.4mg, 2.0eq.) into a 25mL reaction tube , the reaction tube was irradiated with ultraviolet light, and the reaction was stirred by magnetic force at room temperature for 24 hours. After the reaction was completed, most of the solvent was evaporated under reduced pressure, and the remaining mixed solution was separated and purified by column chromatography with petroleum ether / ethyl acetate (20:1) as the eluent to obtain the desired product as a white solid , 49.2 mg, yield 70%.

[0027] Its NMR data are as follows:

[0028] 1 H NMR (300MHz, CDCl 3 )δ=7.81(d, J=9.0Hz, 2H), 6.92(d, J=9.0Hz, 2H), 3.83(s, 3H), 1.36(s, 12H). 13 C NMR (75MHz, CDCl 3 )δ=162.2, 136.5, 113.3, 83.5, 55.0, 24.9.

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Abstract

The invention discloses a synthesis method of aromatic borate compounds, belonging to the technical field of chemical synthesis of intermediates. The method particularly comprises the following steps: (1) adding acetonitrile, aryl sulfonyl chloride, pinacone biborate and dipotassium hydrogen phosphate into a reaction tube, tightening the plug of the reaction tube, and carrying out reaction at room temperature in the reaction tube under the irradiation of an ultraviolet lamp for 24 hours while magnetically stirring; and (2) after the reaction finishes, evaporating under reduced pressure to remove most of the solvent, carrying out separation purification on the residual mixed solution by column chromatography by using an eluent composed of petroleum ether and ethyl acetate in a volume ratio of 10:1-30:1, thereby obtaining the product. The method has wide applicability in the fields of organic synthesis, materials, medicine, pesticides and the like. The method has the advantages of low cost, high yield and the like, is simple to operate, and thus, has favorable application prospects.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis intermediates, and in particular relates to a method for synthesizing aromatic borate compounds induced by ultraviolet light. Background technique [0002] Aromatic borate ester compounds are very important intermediates in organic synthesis and are widely used in cross-coupling reactions such as suzuki. The traditional preparation method of aryl borates is to react Grignard reagents or organolithium reagents with trialkyl borates, then hydrolyze and then esterify. However, this method has certain limitations, requiring low temperature and strict anhydrous and oxygen-free conditions, and poor functional group tolerance. [0003] In recent years, there are many synthetic methods of aromatic borate ester compounds reported in the literature. The transition metal-catalyzed coupling reaction of aryl halides with pinacol diboronate is the most classic method for the synthesis of these compo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02
CPCC07F5/025
Inventor 严国兵于健
Owner 丽水遂智科技咨询有限公司
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