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Preparation method of 1-fluoro-2-bromo-iodobenzene

A technology of iodobenzene and iodized salt, applied in the chemical field, can solve the problems of high risk, harsh conditions, and low utilization rate, and achieve the effects of low equipment requirements, mild conditions, and easy operation

Active Publication Date: 2018-05-08
KINGCHEM LIAONING CHEMICAL CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the tert-butyllithium or n-butyllithium used in these methods are highly flammable, dangerous, and have high requirements for operation; tert-butyllithium or n-butyllithium and 1,2-dibromotetrafluoroethane are expensive , the cost is soaring; the reaction temperature is -75°C or -78°C, the conditions are harsh, and the requirements for equipment are also high; the iodine element is lost during the reaction, and the utilization rate is low

Method used

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  • Preparation method of 1-fluoro-2-bromo-iodobenzene
  • Preparation method of 1-fluoro-2-bromo-iodobenzene

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Example 1 Preparation of 1-fluoro-2-bromo-3-iodobenzene

[0046] The synthetic route is as follows:

[0047]

[0048] 1. Preparation of 1-fluoro-2-bromo-3-nitrobenzene

[0049] Under mechanical stirring, 94.0 g of water, 102.2 g of concentrated sulfuric acid, 19.5 g of acetic acid, 19.5 g of 1-fluoro-2-amino-3-nitrobenzene, 63.2 g of concentrated hydrobromic acid (bromo 48% aqueous solution of hydrogen hydride) and cuprous bromide 9.0g. A solution made of 11.2 g of sodium nitrite and 22.4 g of water was added dropwise at room temperature, and the dripping was completed in about 5 hours, and stirring was continued for 2 hours at room temperature. It was diluted with 130.8 g of water and extracted with 39.0 g of dichloromethane. The oily layer was washed with 39.0 g of water and the solvent was concentrated to obtain 23.4 g of 1-fluoro-2-bromo-3-nitrobenzene with a yield of 85%.

[0050] 2. Preparation of 1-fluoro-2-bromo-3-aminobenzene

[0051] Into a 500 mL stain...

Embodiment 2

[0054] Example 2 Preparation of 1-fluoro-2-bromo-3-iodobenzene

[0055] The synthetic route is as follows:

[0056]

[0057] 1. Preparation of 1-fluoro-2-bromo-3-nitrobenzene

[0058] Under mechanical stirring, 76.6 g of water, 127.7 g of concentrated sulfuric acid, 19.5 g of 1-fluoro-2-amino-3-nitrobenzene, 42.1 g of concentrated hydrobromic acid (48 % aqueous solution) and cuprous bromide 9.0g. A solution made of 8.6 g of sodium nitrite and 17.2 g of water was added dropwise at room temperature, and the drop was completed in about 5 hours, and stirring was continued for 2 hours at room temperature. 130.8 g of water was added for dilution, and extracted with 39.0 g of dichloromethane. The oil layer was washed with 39.0 g of water and the solvent was concentrated to obtain 22.5 g of 1-fluoro-2-bromo-3-nitrobenzene with a yield of 82%.

[0059] 2. Preparation of 1-fluoro-2-bromo-3-aminobenzene

[0060] Into a 500 mL stainless steel autoclave, 22.0 g of 1-fluoro-2-bromo-3...

Embodiment 3

[0063] Example 3 Preparation of 1-fluoro-2-bromo-3-iodobenzene

[0064] The synthetic route is as follows:

[0065]

[0066] 1. Preparation of 1-fluoro-2-bromo-3-nitrobenzene

[0067] Under mechanical stirring, slowly add 19.5 g of acetic acid, 19.5 g of 1-fluoro-2-amino-3-nitrobenzene, 210.7 g of concentrated hydrobromic acid (48% aqueous solution of hydrogen bromide) and bromine Cuprous chloride 18.0g. A solution made of 12.9 g of sodium nitrite and 25.8 g of water was added dropwise at room temperature, and the drop was completed in about 5 hours, and stirring was continued for 2 hours at room temperature. It was diluted with 130.8 g of water and extracted with 39.0 g of dichloromethane. The oil layer was washed with 39.0 g of water and the solvent was concentrated to obtain 23.1 g of 1-fluoro-2-bromo-3-nitrobenzene, yield 84%.

[0068] 2. Preparation of 1-fluoro-2-bromo-3-aminobenzene

[0069] 22.0 g of 1-fluoro-2-bromo-3-nitrobenzene, 220.0 g of isopropanol and 3.3...

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Abstract

The invention provides a preparation method of 1-fluoro-2-bromo-iodobenzene. The method comprises the steps that 1-fluorine-2-amidogen-3-nitrobenzene is used as a raw material, 1-fluorine-2-bromine-3-nitrobenzene is obtained through a diazotization and bromination reaction, 1-fluoro-2-bromo-aminobenzene is obtained through a following reduction reaction, and then 1-fluoro-2-bromo-iodobenzene is obtained through a diazotization and iodination reaction. According to the preparation method, under the acidic condition, 1-fluoro-2-bromo-aminobenzene and sodium nitrite react in a solvent, hydrogen iodide or iodate is added to the mixed solution, and 1-fluoro-2-bromo-iodobenzene is obtained through a reaction. The preparation method of 1-fluoro-2-bromo-iodobenzene is high in safety, mild in reaction condition, low in cost, easy to operate and industrialize and high in utilization rate of iodine.

Description

technical field [0001] The invention relates to the field of chemistry, in particular to a method for preparing 1-fluoro-2-bromo-3-iodobenzene by using 1-fluoro-2-amino-3-nitrobenzene as a raw material. Background technique [0002] Iodobenzene derivatives are highly active compounds that are widely used in the synthesis of materials and drugs as chemical reagents, fine chemicals, pharmaceutical intermediates, and material intermediates. The synthetic method of 1-fluoro-2-bromo-3-iodobenzene still needs to be improved. [0003] Patent WO2011100502A1 and document Palladium-Catalyzed Aryl Amination-HeckCyclization Reaction Cascade: A One-Flask Approach to 3-Substituted Indoles (Angewandte Chemie, International Edition, 47 (5), 888-890; 2008 (Supporting Information)) all disclose the use of N-Boc-2-fluoroaniline and tert-butyllithium carry out lithiation reaction, add iodine and carry out iodination reaction, obtain N-Boc-2-fluoro-6-iodoaniline, yield 65~79%; Will obtain N-Bo...

Claims

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Application Information

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IPC IPC(8): C07C17/093C07C25/13
CPCC07C17/093C07C201/12C07C209/36C07C25/13C07C211/52C07C205/12
Inventor 李振威赵阳李德刚刘述宽姜志鹏刘海盛王栋赵宏阳宋桐集
Owner KINGCHEM LIAONING CHEMICAL CO LTD
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