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Preparation method of 4-(E3-ethoxyl-3-oxo-1-propylene-1-yl) borophenylic acid

A technology of phenylboronic acid and formylphenylboronic acid, which is applied in the field of pharmaceutical intermediates, can solve the problems of complex processing procedures, pollution, harsh conditions, etc., and achieve the effect of simple post-treatment process, high atom economy and mild reaction conditions

Inactive Publication Date: 2017-05-17
GUIZHOU UNIV
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AI Technical Summary

Problems solved by technology

[0003] At present, the synthetic routes for 4-(E-3-ethoxyl-3-oxo-1-propen-1-yl)phenylboronic acid mainly contain: (1) take the coordination compound of phenylboronic acid as raw material through 3 ~4-step reaction to prepare 4-(E-3-ethoxy-3-oxo-1-propen-1-yl)phenylboronic acid; in this synthetic route, the coordination compound of phenylboronic acid used is difficult to buy , and needs to be reacted at -78°C, the conditions are harsh, and there are many steps in the preparation process, the yield of the product is low, and the by-products are difficult to separate
(2) 4-(E-3-ethoxyl-3-oxo-1-propylene-1 -yl) phenylboronic acid; in this synthetic route, the atom economy of ethoxyformyl methylene triphenylphosphine is not high, and the pollution is more serious, and its product separation difficulty is bigger, needs to adopt column chromatography to carry out purification, handles The process is complicated, the product yield is low, and the cost is high

Method used

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  • Preparation method of 4-(E3-ethoxyl-3-oxo-1-propylene-1-yl) borophenylic acid
  • Preparation method of 4-(E3-ethoxyl-3-oxo-1-propylene-1-yl) borophenylic acid

Examples

Experimental program
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Effect test

Embodiment 1

[0017] In a 250mL three-neck flask, dissolve lithium chloride (4.2g, 100.0mmol) and DBU (15.2g, 100.0mmol) in acetonitrile (50mL), and add triethylphosphonoacetic acid at 0°C under N2 protection The ester (22.4g, 100.0mmol) was stirred for 10min, raised to room temperature and stirred for 30min, then added 4-formylphenylboronic acid (5.0g, 33.3mmol), and reacted at room temperature for 5h. After the reaction is complete, pour the reaction solution into water, extract with ethyl acetate (50mL×3), combine the organic layers, dry over anhydrous sodium sulfate, concentrate under reduced pressure, add concentrated hydrochloric acid (2mL) and a solid is precipitated, suction filtered, and the filter cake Slurry with a small amount of n-hexane (5 mL) and dry to obtain 5.8 g of 4-(E-3-ethoxy-3-oxo-1-propen-1-yl)phenylboronic acid with a yield of 78.8%.

[0018] 1 H NMR (400MHz, DMSO) δ7.82(d, J=8.2Hz, 2H), 7.67(d, J=7.4Hz, 2H), 7.62(s, 1H), 6.66(d, J=16.1Hz, 1H ), 4.20 (q, J=7.1Hz, ...

Embodiment 2

[0020] In a 250mL three-neck flask, dissolve lithium chloride (7.1g, 166.7mmol) and DBU (25.4g, 166.7mmol) in acetonitrile (50mL), and add triethylphosphonoacetic acid at 0°C under N2 protection The ester (37.4g, 166.7mmol) was stirred for 10min, raised to room temperature and stirred for 30min, then added 4-formylphenylboronic acid (5.0g, 33.3mmol), and reacted at room temperature for 3h. After the reaction is complete, pour the reaction solution into water, extract with ethyl acetate (50mL×3), combine the organic layers, dry over anhydrous sodium sulfate, concentrate under reduced pressure, add concentrated hydrochloric acid (2mL) and a solid is precipitated, suction filtered, and the filter cake Slurry with a small amount of n-hexane (5 mL) and dry to obtain 5.9 g of 4-(E-3-ethoxy-3-oxo-1-propen-1-yl)phenylboronic acid with a yield of 80.3%.

[0021] 1 H NMR (400MHz, DMSO) δ7.82(d, J=8.2Hz, 2H), 7.67(d, J=7.4Hz, 2H), 7.62(s, 1H), 6.66(d, J=16.1Hz, 1H ), 4.20 (q, J=7.1Hz, ...

Embodiment 3

[0023] In a 250mL three-neck flask, dissolve lithium chloride (1.4g, 33.3mmol) and DBU (5.1g, 33.3mmol) in acetonitrile (50mL), and add triethylphosphonoacetic acid at 0°C under N2 protection The ester (7.5g, 33.3mmol) was stirred for 10min, warmed up to room temperature and stirred for 30min, 4-formylphenylboronic acid (5.0g, 33.3mmol) was added, and reacted at room temperature for 8h. After the reaction is complete, pour the reaction solution into water, extract with ethyl acetate (50mL×3), combine the organic layers, dry over anhydrous sodium sulfate, concentrate under reduced pressure, add concentrated hydrochloric acid (2mL) and a solid is precipitated, suction filtered, and the filter cake Slurry with a small amount of n-hexane (5 mL) and dry to obtain 5.0 g of 4-(E-3-ethoxy-3-oxo-1-propen-1-yl)phenylboronic acid with a yield of 67.9%.

[0024] 1 H NMR (400MHz, DMSO) δ7.82(d, J=8.2Hz, 2H), 7.67(d, J=7.4Hz, 2H), 7.62(s, 1H), 6.66(d, J=16.1Hz, 1H ), 4.20 (q, J=7.1Hz, 2H)...

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Abstract

The invention relates the technical field of medical intermediates, and in particular relates to a preparation method of 4-(E3-ethoxyl-3-oxo-1-propylene-1-yl) borophenylic acid. By taking 4-formylphenylboronic acid as a raw material, a Wittig-Horner reaction is performed to obtain a target product, namely 4-(E3-ethoxyl-3-oxo-1-propylene-1-yl) borophenylic acid. The yield of the 4-(E3-ethoxyl-3-oxo-1-propylene-1-yl) borophenylic acid can reach about 80%. Moreover, lithium chloride and a DBU organic reagent which are low in price and are easily available are adopted, so that a low-temperature operation is avoided; and the preparation method is mild in reaction condition, simple in post-treatment process and suitable for industrial application.

Description

technical field [0001] The invention relates to the technical field of pharmaceutical intermediates, in particular to a method for preparing 4-(E-3-ethoxy-3-oxo-1-propen-1-yl)phenylboronic acid. Background technique [0002] 4-(E-3-ethoxy-3-oxo-1-propen-1-yl)phenylboronic acid is an important intermediate, which is widely used in fine chemicals, medicine, pesticides, fuels, functional materials and other chemical Chemical and pharmaceutical fields. In recent years, 4-(E-3-ethoxy-3-oxo-1-propen-1-yl)phenylboronic acid has been used in the synthesis of monocyclic or polycyclic estrogen receptor degradation and regulators in the treatment of breast cancer, etc. Aspects are used as intermediates. [0003] At present, the synthetic routes for 4-(E-3-ethoxyl-3-oxo-1-propen-1-yl)phenylboronic acid mainly contain: (1) take the coordination compound of phenylboronic acid as raw material through 3 ~4-step reaction to prepare 4-(E-3-ethoxy-3-oxo-1-propen-1-yl)phenylboronic acid; in ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02
CPCC07F5/025
Inventor 黄筑艳赵庆平闫沛沛乐意
Owner GUIZHOU UNIV
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