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Synthesis method for 4, 4'-dibromo-2, 2'-dipyridyl

A synthetic method, bipyridine technology, applied in the direction of organic chemistry, can solve problems such as inappropriateness, achieve the effects of increased yield, simplified process, and reduced adverse effects

Inactive Publication Date: 2013-06-05
JIANGSU ZHONGDAN PHARMA RES +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0015] (3) In the existing literature, the use of acetyl bromide (2.5-39.8 molar equivalents) and phosphorus tribromide (11-36.7 molar equivalents), especially phosphorus tribromide, is greatly excessive, and there are HSE (health, safety, environment) problems, not suitable for application in modern industrial production

Method used

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  • Synthesis method for 4, 4'-dibromo-2, 2'-dipyridyl
  • Synthesis method for 4, 4'-dibromo-2, 2'-dipyridyl
  • Synthesis method for 4, 4'-dibromo-2, 2'-dipyridyl

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045]Add 50ml of water to a 100ml four-necked flask, then add 7.5g (48mmol) 2,2'-dipyridine, add 1.6g (0.0048mmol) sodium tungstate and 2.2g (0.0048mmol) trioctyl ammonium methyl hydrogen sulfate, Raise the temperature to 60°C, slowly add 18.75ml (182.4mmol) of 30% hydrogen peroxide dropwise, react for 5h, no raw materials were detected by HPLC, filter, wash with water three times, and dry to obtain 7.2g of 2,2'-bipyridine nitrogen oxide, the yield 80%, purity 99.4% (HPLC). 1H-NMR(DMSO-d6) of 2,2'-bipyridine nitrogen oxide: 8.31-8.33 (d, J=6.3Hz, 2H) 7.39-7.62 (m, 6H), such as figure 1 shown.

[0046] Add 35ml (657mmol) of concentrated sulfuric acid and 40ml of 30% oleum into a 250ml four-neck flask, add 25g (133mmol) of 2,2'-bipyridine nitrogen oxide in batches, raise the temperature to 110°C, add dropwise 80ml (1942mmol) of fuming Nitric acid, reacted for 5h after the dropwise addition, and monitored by HPLC. The reaction solution was poured into ice water, filtered, rec...

Embodiment 2

[0049] Add 50ml of water to a 100ml four-necked flask, then add 7.5g (48mmol) 2,2'-dipyridine, add 0.8g (0.0024mmol) sodium tungstate and 1.1g (0.0024mmol) trioctylmethyl ammonium bisulfate, The temperature was raised to 70°C. Slowly add 18.75ml (182.4mmol) 30% hydrogen peroxide dropwise, react for 8 hours, no raw materials are detected by HPLC, filter, wash with water three times, and dry to obtain 7.0g of 2,2'-bipyridine nitrogen oxide, yield 77%, purity 99.6 % (HPLC).

[0050] Add 35ml (657mmol) of concentrated sulfuric acid and 40ml of 30% oleum into a 250ml four-neck flask, add 25g (133mmol) of 2,2'-bipyridine nitrogen oxide in batches, raise the temperature to 120°C, add dropwise 80ml (1942mmol) of fuming Nitric acid, reacted for 5h after the dropwise addition, and monitored by HPLC. The reaction solution was poured into ice water, filtered, recrystallized, and dried to obtain 18.4 g of a yellow solid with a yield of 50.0% and a purity of 99.3%.

[0051] In a 250ml fo...

Embodiment 3

[0053] Add 50ml of water to a 100ml four-neck flask, add 7.5g (48mmol) of 2,2'-bipyridine, add 0.82g of sodium molybdate and 1.35g of trioctylmethylammonium chloride, and heat up to 65°C. Slowly add 18.75ml (182.4mmol) of 30% hydrogen peroxide dropwise, react for 5 hours, no raw material is detected by HPLC, filter, wash with water three times, and dry to obtain 7.1g of 2,2'-bipyridine nitrogen oxide, with a yield of 78.1% and a purity of 99.5 % (HPLC).

[0054] Add 35ml (657mmol) of concentrated sulfuric acid and 40ml of 30% oleum into a 250ml four-neck flask, add 25g (133mmol) of 2,2'-bipyridyl nitrogen oxide in batches, raise the temperature to 110~120°C, and add 80ml (1942mmol) dropwise Fuming nitric acid, react for 5 hours after the dropwise addition, and monitor by HPLC. The reaction solution was poured into ice water, filtered, recrystallized, and dried to obtain 18.4 g of a yellow solid with a yield of 50% and a purity of 99.3%.

[0055] In a 250ml four-necked flask,...

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Abstract

The invention discloses a synthesis method for 4, 4'-dibromo-2, 2'-dipyridyl and belongs to the field of organic synthesis. The synthesis method includes the following steps: (A) oxidizing reaction: 2, 2'-dipyridyl reacts with 30% of hydrogen under the action of a metal catalyst and a phase transfer catalyst in the medium of water, and 2, 2'-dipyridyl nitrogen oxide is obtained; (B) nitration reaction: the 2, 2'-dipyridyl nitrogen oxide and fuming sulphuric acid are heated and react with fuming nitric acid in the medium of concentrated sulfuric acid, and 4, 4'-dinitro-2, 2'-dipyridyl nitrogen oxide is obtained; and (C) bromination reaction and deoxygenation reaction: the 4, 4'-dinitro-2, 2'-dipyridyl nitrogen oxide is added into acetic acid and heated till backflow, an acetyl bromide acetic acid solution is added, reaction is finished, a reducing agent is added, and the 4, 4'-dibromo-2, 2'-dipyridyl is obtained. According to the synthesis method for the 4, 4'-dibromo-2, 2'-dipyridyl, the solvent-free environment-friendly oxidizing reaction is adopted, the dosage of acetyl bromide is reduced, other reducing agents are used to replace phosphorus tribromide for the deoxygenation reaction, the bromination and reduction are changed into a one-pot method, harmful effects in the aspects of HSE (health, safety, environment) are reduced, and the synthesis method is environment-friendly and suitable for industrial production.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and specifically relates to a synthesis method of 4,4'-dibromo-2,2'-bipyridine. Background technique [0002] Energy is the primary issue of the world's economic development. In order to solve the problems caused by the depletion of conventional energy sources, countries around the world are making great efforts to develop new energy sources. Solar energy is the most active field in the development and utilization of new energy sources. Dye-Sensitized solar cells (Dye-Sensitized Solar Cells, DSSCs) belong to the third generation of solar cells. Due to the characteristics of lower raw material and manufacturing costs and a wide range of applications, they have great development potential and broad prospects, and may become the mainstream of solar cells in the future. Photosensitive dyes are applied to the photoanode of solar cells, and their function is to absorb solar energy and generate photoele...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/61
Inventor 毛永生贺鹰吉海峰韩澜吴雅霜董泽军
Owner JIANGSU ZHONGDAN PHARMA RES
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