A kind of synthetic method of 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine

A technology of nitromethylene and chloromethylpyridine, which is applied in the field of organic synthesis and can solve problems such as unfavorable industrial production, low atom economy, and poor operability

Active Publication Date: 2020-10-23
SHANGHAI SHENGNONG PESTICIDE
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Problems solved by technology

[0004] In the prior art, the synthesis method of 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine has complex process, poor operability, high cost, and is unfavorable for industrialized production
Such as the synthesis method reported in the patent CN103524489A, after the imidazolidine potassium salt is prepared through a multi-step reaction, the target product——2-chloro-5-((2-(nitromethylene)imidazolin-1-yl) is synthesized methyl)pyridine; yet, each step reaction of this method not only yield is low, and all needs to feed feeding after separating and purifying, thereby causes complicated operation
Another example is the report of the patent PCT2007101369 and the document Bioorg.Med.Chem., 2008, 18, 6513-6516: after preparing chloropyridine ethylenediamine with chloropyridine and ethylenediamine, and then reacting with dithiomethylnitroethylene, Removal of methyl mercaptan to synthesize 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine; The methyl mercaptan released by the reaction has a bad smell and seriously pollutes the air. It can be seen that it is difficult to realize industrial production

Method used

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  • A kind of synthetic method of 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine
  • A kind of synthetic method of 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine
  • A kind of synthetic method of 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine

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preparation example Construction

[0028] And, the synthetic method of described 2-chloro-5-((2-(nitromethylene) imidazolin-1-yl) methyl) pyridine comprises the following steps:

[0029] Step 1. Add 2-chloro-5-chloromethylpyridine (2) and a solvent as starting materials into the container, add a phase transfer catalyst and a base, and add ethylenediamine at a temperature of -20°C to 50°C; Then, a substitution reaction was carried out at a temperature of -20°C to 50°C for 3-5 hours to obtain chloropyridine ethylenediamine (3);

[0030] Step ②Heat up to 0°C-35°C, then add 1,1-dimethoxy-2-nitroethylene, heat to reflux, and stir the reaction until the reaction is complete; after-treatment, the target product 2-chloro- 5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine.

[0031] In a preferred embodiment, in the above synthesis method, the solvent is selected from any one of the following: water, methanol, ethanol, sec-butanol, tert-butanol, ethylene glycol, acetonitrile, N,N-dimethyl Formamide, dimethyl sulfox...

Embodiment 1

[0041] Add 2-chloro-5-chloromethylpyridine (0.2mol) and toluene 60mL into a 250ml three-necked flask, add tetrabutylammonium bromide (5mmol) and potassium carbonate solid (0.4mol), cool to -20°C, Then add ethylenediamine (1.0mol); then react at -20°C for 5h, and a substitution reaction occurs to obtain chloropyridine ethylenediamine; heat up to 20°C, and then add 1,1-dimethoxy-2-nitroethylene (0.18mol), heated to reflux, and stirred at reflux for 4h. After the reaction is complete, cool to room temperature, filter with suction, recrystallize the filter cake with absolute ethanol, and then dry the resulting crystalline substance to obtain the target product 2-chloro-5-((2-(nitromethylene) Imidazolin-1-yl)methyl)pyridine with a purity of 98.5% and a yield of 76% (based on 2-chloro-5-chloromethylpyridine).

Embodiment 2

[0043] Add 2-chloro-5-chloromethylpyridine (0.2mol) and toluene 60mL in a 250ml three-necked flask, and add dodecyltrimethylammonium chloride (5mmol), add potassium hydroxide solid (0.4mol), Cool down to -15°C, then add ethylenediamine (1.0mol); then react at -15°C for 5 hours, a substitution reaction occurs to obtain chloropyridine ethylenediamine; heat up to 20°C, then add 1,1-dimethoxy -2-Nitroethylene (0.18mol), heated to reflux, and stirred at reflux for 5h. After the reaction is complete, cool to normal temperature, filter with suction, recrystallize the filter cake with absolute ethanol, and then dry the resulting crystalline substance to obtain the target product 2-chloro-5-((2-(nitromethylene) Imidazolin-1-yl)methyl)pyridine with a purity of 98.8% and a yield of 91% (based on 2-chloro-5-chloromethylpyridine).

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Abstract

The invention provides a synthetic method of 2-chlorine-5-((2-(nitromethylene)imidazoline-1-yl)methyl)pyridine. The method comprises the steps of taking 2-chlorine-5-nitrapyrin as a starting material, enabling the starting material to be subjected to a substitution reaction with ethylenediamine in the presence of a phase transfer catalyst and alkali to generate chloropyridine ethylenediamine, adding 1,1-dimethoxy-2-nitroethylene into the same reaction vessel, performing a reflux reaction, performing after-treatment to prepare a target product, i.e., the 2-chlorine-5-((2-(nitromethylene)imidazoline-1-yl)methyl)pyridine is synthesized by a one-pot method. By adopting the synthetic method, the target product of high content can be obtained, an intermediate of the first-step reaction does not need separation and purification, the two-step synthesis unit operation is completed in the same reaction vessel, the equipment utilization rate is high, the after-treatment is simple in process, the operation conditions are mild, thus a prospect of industrial production is achieved.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for synthesizing 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine. Background technique [0002] 2-Chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine is an important fine chemical intermediate, which is often used as insecticide imidacloprid, It is the main raw material for the synthesis of pyridine and cyclopyrid. The molecular formula of 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine is: C 5 h 6 Cl 2 O, the English name is: 2-chloro-5-[[2-(nitromethylene)-1-imidazolidinyl]methyl]pyridine; the CAS number is: 101336-63-4; its structural formula is as follows: [0003] [0004] In the prior art, the synthesis method of 2-chloro-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine has complicated process, poor operability and high cost, which is unfavorable for industrialized production . Such as the synthesis method report...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D401/06
CPCC07D401/06
Inventor 叶振君王曼方燕董建生吴清阳张芝平韩海平顾浩桦徐海燕
Owner SHANGHAI SHENGNONG PESTICIDE
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