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Synthesis process of 2-chlorin-5-((2-(nitryl methylene) imidazoline-1-yl) methyl) pyridine

A technology of nitromethylene imidazolidine and nitromethylene is applied in the field of organic compound synthesis, and can solve the problems of poor photostability hindering commercialization, large feed ratio, low yield and the like

Active Publication Date: 2014-01-22
EAST CHINA UNIV OF SCI & TECH +1
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Problems solved by technology

[0002] 2-Chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine was developed by Bayer Corporation of Japan in the early 1980s with the compound of formula A (Nithiazine) as the guide Synthesized, although its biological activity has been significantly improved compared with the lead compound, but its poor photostability hinders its commercialization
[0008] (1) When 2-chloro-5-chloromethylpyridine and ethylenediamine react, ethylenediamine not only participates in the reactant, but also acts as an acid-binding agent. The ratio of feed to material is large, and the consumption of raw materials is large, resulting in an increase in cost
[0009] (2) When the route uses the more expensive 2-chloro-5-chloromethylpyridine as a raw material, the target compound will be generated in two steps, and the cost is higher
[0014] (1) When the route uses the more expensive 2-chloro-5-chloromethylpyridine as a raw material, the target compound is generated in two steps, and the cost is higher
[0015] (2) When 2-chloro-5-chloromethylpyridine and ethylenediamine react, ethylenediamine not only participates in the reactant, but also acts as an acid-binding agent. The ratio of feed to material is large, and the consumption of raw materials is large, resulting in an increase in cost
[0016] (3) Dichloronitroethylene is active and reacts with 2-chloro-5-(methylenediamine)pyridine, and the yield is not high
Tetrafluoroethane needs to be prepared under the condition of hydrochloric acid to produce trichloronitroethylene, and the equipment corrosion is relatively serious
[0021] (2) This route uses the more expensive 2-chloro-5-chloromethylpyridine as the starting material, and the target compound is generated in three steps of reaction, and the cost is relatively high
[0022] (3) When 2-chloro-5-chloromethylpyridine and ethylenediamine react, ethylenediamine not only participates in the reactant, but also acts as an acid-binding agent. The ratio of feed to material is large, and the consumption of raw materials is large, resulting in an increase in cost

Method used

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  • Synthesis process of 2-chlorin-5-((2-(nitryl methylene) imidazoline-1-yl) methyl) pyridine
  • Synthesis process of 2-chlorin-5-((2-(nitryl methylene) imidazoline-1-yl) methyl) pyridine
  • Synthesis process of 2-chlorin-5-((2-(nitryl methylene) imidazoline-1-yl) methyl) pyridine

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preparation example Construction

[0110] A preferred method for preparing the intermediate 2-nitromethylene imidazolidine potassium salt, comprising the steps of: (a) using vinylidene chloride as a raw material, and adding vinylidene chloride dropwise to the mixed acid of nitric acid and other acids , to prepare 1,1-dichloro-2-nitroethylene; (b) adding ethylenediamine dropwise to 1,1-dichloro-2-nitroethylene solution to synthesize 2-nitromethylene Imidazolidine; (c) 2-nitromethylene imidazolidine and potassium hydroxide generate 2-nitromethylene imidazolidine potassium salt.

[0111] Generally, the time for dropwise addition of ethylenediamine is 0.5 to 10h, preferably 0.5 to 5h; the holding time after the dropwise addition is 0.5 to 10h, preferably 0.5 to 5h; 2-nitromethyleneimidazolidine The molar ratio to potassium hydroxide is 1:1 to 1:10, preferably 1:5.

[0112] Synthesis of 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine (Process A)

[0113] A synthetic method for synthesizing 2-chloro-...

Embodiment 1

[0181] Embodiment 1. Compound 1, the synthesis of 1-dichloro-2-nitroethylene

[0182]

[0183] A mixture of 41.7g (417mmol) of 36.5% hydrochloric acid and 39.8g (411mmol) of 65% of nitric acid was added dropwise to the reaction solution, and the reaction temperature was controlled at 20~ Between 25°C, add dropwise for 3 hours, keep stirring for 1 hour, wash with water, extract and separate the organic phase with chloroform. Under the condition of stirring in an ice bath, 4% sodium hydroxide solution was added to the chloroform layer to neutralize to pH=7~8, then added chloroform for extraction, combined the extracts, dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 24.6g Yellow-green liquid with a yield of 54.5%.

[0184] GC-MS (m / s): 141(37), 95(85), 83(78), 60(100).

Embodiment 2

[0185] Embodiment 2. The synthesis of compound 2-nitromethylene imidazolidine

[0186]

[0187] 1.175 g (5 mmol) of 1,1-dichloro-2-nitroethylene was dissolved in 10 mL of ethanol and cooled to 0°C. 0.75 g (12.5 mmol) of ethylenediamine dissolved in 10 mL of ethanol was slowly added dropwise to the reaction liquid, the dropping temperature was controlled at 0° C., and the dropping time was 1 h. After the dropwise addition was completed, it was incubated at 0° C. for 1 h. Suction filtration to obtain an orange liquid, wash the filter cake 3 to 4 times with ethanol, combine the filtrates, and concentrate. Recrystallization with ethanol gave 0.37 g of a light brown solid with a yield of 57.1%.

[0188] 1 H NMR (400MHz, DMSO-d6): δ 8.32 (s, 2H), 6.33 (s, 1H), 3.57 (s, 4H) ppm.

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Abstract

The invention provides a synthesis process of 2-chlorin-5-((2-(nitryl methylene) imidazoline-1-yl) methyl) pyridine. Particularly, the method comprises the following steps: preparing 2-nitryl methylene imidazolidine from vinylidene chloride serving as a raw material; and reacting the 2-nitryl methylene imidazolidine with a 2-chlorin-5-chloromethyl pyridine compound so as to form 2-chlorin-5-((2-(nitryl methylene) imidazoline-1-yl) methyl) pyridine. The synthesis process has the advantages that raw materials are easily available, production cost is low, conditions are mild, and the operation is simple and convenient; moreover, synthesis process is environmentally-friendly and suitable for industrial production.

Description

technical field [0001] The invention relates to the field of organic compound synthesis, in particular, the invention relates to a synthesis process of 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine. Background technique [0002] 2-Chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine was developed by Bayer Corporation of Japan in the early 1980s with the compound of formula A (Nithiazine) as the guide Although the biological activity of the synthesized compound has been significantly improved compared with the lead compound, its poor photostability hinders its commercialization. Although the compound has not been commercialized, the structural optimization and derivation of the compound have been in progress. Until now, 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine has become an important intermediate in the synthesis of some medicines and pesticides, and is widely used in the synthesis of cis-nitrorene Neonicotinoid pesticides. ...

Claims

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Application Information

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IPC IPC(8): C07D401/06C07D233/20C07C205/28C07C201/12
CPCC07C201/12C07C205/28C07D233/20C07D401/06
Inventor 李忠董建生徐晓勇施顺发范叶峰于广郭梦菲王正荣张芝平
Owner EAST CHINA UNIV OF SCI & TECH
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