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CN-116903551-B - Nitrogen-containing heterocyclic compound and process for producing alkali metal salt of nitrogen-containing heterocyclic compound

CN116903551BCN 116903551 BCN116903551 BCN 116903551BCN-116903551-B

Abstract

The invention discloses a preparation method of a nitrogen-containing heterocyclic compound and an alkali metal salt of the nitrogen-containing heterocyclic compound, wherein the preparation method comprises the steps of (1) uniformly mixing cyanuric acid with a first solvent, introducing sulfuryl fluoride gas or adding alkenyl sulfonyl fluoride for reaction, and obtaining a crude product through crude treatment after the reaction is finished; Wherein R 1 、R 2 、R 3 is independently selected from-H, -SO 2 F or-CH 2 -(CH 2 ) n -SO 2 F, n is selected from an integer of 1-10, and R 1 、R 2 、R 3 is not H at the same time. The nitrogen-containing heterocyclic compound and the preparation method of the alkali metal salt of the nitrogen-containing heterocyclic compound can be used for applying cyanuric acid in lithium battery electrolyte in a large amount, and the preparation method has the advantages of easily available raw materials, simple operation, high yield, mild condition, low requirement on equipment and suitability for industrial production.

Inventors

  • ZENG YIAN
  • HAN HUI
  • MAO CHONG
  • WANG PIPI
  • FENG HUITAO
  • MO DEHUAN
  • Pan Dongyou
  • XIE JINXIN
  • DAI XIAOBING
  • FENG PAN

Assignees

  • 合肥市赛纬电子材料有限公司
  • 珠海市赛纬电子材料股份有限公司
  • 淮南市赛纬电子材料有限公司

Dates

Publication Date
20260512
Application Date
20230713

Claims (8)

  1. 1. A method for preparing a nitrogen-containing heterocyclic compound, comprising the steps of: (1) Uniformly mixing cyanuric acid with a first solvent, introducing sulfuryl fluoride gas or adding alkenyl sulfonyl fluoride for reaction, and performing coarse treatment after the reaction is finished to obtain a coarse product, wherein the reaction time is 2-3 hours, the reaction temperature is-20-40 ℃, the molar ratio of cyanuric acid to the sulfuryl fluoride is 1:1-3.2, the molar ratio of cyanuric acid to the alkenyl sulfonyl fluoride is 1:1-3.2, and the boiling point of the first solvent is less than 100 ℃; (2) Purifying the crude product to obtain a nitrogen-containing heterocyclic compound shown in a structural formula 1; Wherein R 1 、R 2 、R 3 is independently selected from-H, -SO 2 F or-CH 2 -(CH 2 ) n -SO 2 F, n is selected from an integer of 1-10, and R 1 、R 2 、R 3 is not H at the same time.
  2. 2. The method for producing a nitrogen-containing heterocyclic compound according to claim 1, wherein step (1) comprises uniformly mixing the cyanuric acid, the organic base and the first solvent, introducing sulfuryl fluoride gas for reaction, evaporating and spin-drying after the reaction is completed to obtain an intermediate, and subjecting the intermediate to a first pretreatment to obtain a crude product.
  3. 3. The method for producing a nitrogen-containing heterocyclic compound according to claim 1, wherein step (1) comprises uniformly mixing the cyanuric acid with a first solvent, adding an alkenyl sulfonyl fluoride for reaction, evaporating and spin-drying after the reaction is completed to obtain a first intermediate, quenching the first intermediate to obtain a second intermediate, and pretreating the second intermediate for the first time to obtain a crude product.
  4. 4. The method for preparing a nitrogen-containing heterocyclic compound according to any one of claims 2 to 3, wherein the first pretreatment comprises dissolving the intermediate or the second intermediate with a second solvent, taking an organic phase, and then washing, dehydrating, drying, filtering, and concentrating in sequence.
  5. 5. The method for producing a nitrogen-containing heterocyclic compound according to claim 1, wherein step (2) comprises subjecting the crude product to a second pretreatment comprising cooling crystallization or column separation, and vacuum drying to obtain the nitrogen-containing heterocyclic compound represented by structural formula 1.
  6. 6. A process for preparing an alkali metal salt of a nitrogen-containing heterocyclic compound, comprising the steps of: (1) Uniformly mixing a cyanuric acid compound and a third solvent, adding an alkali metal compound, and adjusting the pH value to react, wherein the cyanuric acid compound is a nitrogen-containing heterocyclic compound prepared by adopting the preparation method of the nitrogen-containing heterocyclic compound according to any one of claims 1-5, and the preparation method of the cyanuric acid compound is the preparation method of the nitrogen-containing heterocyclic compound according to any one of claims 1-5; (2) Purifying the product after the reaction of the step (1) to obtain an alkali metal salt of the nitrogen-containing heterocyclic compound shown in the structural formula 2; Wherein R 4 、R 5 、R 6 is independently selected from-SO 2 F or-CH 2 -(CH 2 ) n -SO 2 F or alkali metal, n is selected from an integer of 1-10, and at least one of R 4 、R 5 、R 6 is alkali metal.
  7. 7. The method for producing an alkali metal salt of a nitrogen-containing heterocyclic compound according to claim 6, wherein the pH in the step (1) is 7 to 8, the reaction temperature is 40 to 60℃and the reaction time is 1 to 5 hours.
  8. 8. The process for producing an alkali metal salt of a nitrogen-containing heterocyclic compound as described in claim 6, wherein the purification in the step (2) comprises concentration, crystallization at a temperature lower than that, filtration and drying in this order.

Description

Nitrogen-containing heterocyclic compound and process for producing alkali metal salt of nitrogen-containing heterocyclic compound Technical Field The invention belongs to the technical field of compound synthesis, and particularly relates to a nitrogen-containing heterocyclic compound and a preparation method of an alkali metal salt of the nitrogen-containing heterocyclic compound. Background The lithium battery electrolyte mainly comprises electrolyte salt (lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate and the like), carbonate solvent (DMC, EMC, EC, PC and the like) and functional additives (VC, PS, DTD, TMSP and the like), the electrolyte is a non-aqueous system, the water content is a very important technical index, water in the electrolyte can react with the lithium hexafluorophosphate to generate hydrofluoric acid with very strong corrosiveness, and the electrolyte is in direct contact with an anode, a cathode and a diaphragm, so that the first charge and discharge capacity, the internal resistance, the battery cycle life and the battery volume of the battery can be influenced to different degrees, and the molecular structure of the electrolyte additives generally requires that the electrolyte additives do not contain active hydrogen protons. Cyanuric acid is a heavy metal ion remover with good performance, and the sodium salt hydrate (TMT-3 Na9H 2 O) is reported by US4849517A at the earliest, and the action mechanism is mainly that the cyanuric acid anions form stable complex precipitates with metal ions such as Ni +、Pb2+、Cu2+、Ag+、Zn2+、Cd2+、Hg2+ in solution, so that the purpose of removing the heavy metal ions is achieved. However, since cyanuric acid contains active hydrogen protons, the use of cyanuric acid as an electrolyte additive has been recently reported. Therefore, there is a need for a nitrogen-containing heterocyclic compound and a method for preparing an alkali metal salt of the nitrogen-containing heterocyclic compound, so that cyanuric acid can be applied to lithium battery electrolyte in a large amount. Disclosure of Invention The invention aims to provide a preparation method of a nitrogen-containing heterocyclic compound, which is simple to operate, high in yield and mild in condition, and can replace active proton hydrogen of cyanuric acid with sulfonyl fluoride or alkenyl sulfonyl fluoride functional groups. The invention also aims to provide a preparation method of the alkali metal salt of the nitrogen-containing heterocyclic compound, which is simple to operate, high in yield, free from high temperature and mild in condition, and can replace active proton hydrogen of cyanuric acid with alkali metal. In order to achieve the above object, the present invention provides a method for preparing a nitrogen-containing heterocyclic compound, comprising the steps of: (1) Uniformly mixing cyanuric acid with a first solvent, introducing sulfuryl fluoride gas or adding alkenyl sulfonyl fluoride for reaction, and performing crude treatment after the reaction is finished to obtain a crude product; (2) Purifying the crude product to obtain a nitrogen-containing heterocyclic compound shown in a structural formula 1; Wherein R 1、R2、R3 is independently selected from-H, -SO 2 F or-CH 2-(CH2)n-SO2 F, n is selected from an integer of 1-10, and R 1、R2、R3 is not H at the same time. Compared with the prior art, the preparation method of the nitrogen-containing heterocyclic compound adopts sulfuryl fluoride or alkenyl sulfonyl fluoride to modify and synthesize the cyanuric acid molecule to prepare the nitrogen-containing heterocyclic compound without active hydrogen, and at the same time, the cyanuric acid ion in the nitrogen-containing heterocyclic compound has high-efficiency complexing effect on metal ions, so that the nitrogen-containing heterocyclic compound can be used as an electrolyte additive or used as a coating agent of the anode, thereby improving the problem of Mn 2+ ion dissolution in the anode of the LFP battery, and having guiding significance for improving the first efficiency of the battery, reducing the internal resistance of the battery, forming a more stable SEI film and improving the cycle life of the battery. The preparation method of the nitrogen-containing heterocyclic compound has the advantages of easily available raw materials, simple operation, high yield, mild conditions, low requirements on equipment and suitability for large-scale industrial production. Preferably, the structural formula of the alkenyl sulfonyl fluoride is CH 2＝CH-(CH2)n-1-SO2 F, and n is selected from integers from 1 to 10. Preferably, the reaction time in the step (1) is 2-3 hours, the reaction temperature is 0-40 ℃, the reaction temperature is low, the energy consumption can be effectively reduced, more particularly, the end point of the reaction can be monitored through LC/MS or GC/MS, and the reaction is stopped after detecting the peak without raw materials after 2-3 hou