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12-crown ether-4 lithium salt complex and its preparation method and application

A technology of complexes and crown ethers, applied in the preparation of sulfonates, organic chemistry, etc., can solve the problems of high risk of raw materials, low product purity, low product yield, etc., and achieve high reaction selectivity and high product purity , the effect of reducing production costs

Active Publication Date: 2021-10-19
SUZHOU BAILINGWEI HYPERFINE MATERIAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0012] In view of the problems existing in the above-mentioned prior art, the present invention provides 12-crown ether-4 lithium salt complex and its preparation method and application, which are used to solve the preparation work of 12-crown ether-4 in the prior art There are problems such as poor safety, high risk of raw materials, low product purity and low product yield

Method used

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  • 12-crown ether-4 lithium salt complex and its preparation method and application
  • 12-crown ether-4 lithium salt complex and its preparation method and application
  • 12-crown ether-4 lithium salt complex and its preparation method and application

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Experimental program
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Effect test

Embodiment 1

[0033] The synthetic route is as follows:

[0034]

[0035] Step (1): Preparation of formula 3 compound 12-crown-4 p-nitrobenzenesulfonate lithium complex

[0036] Maintain a slight positive pressure of nitrogen, and add 60 L of toluene, 6.31 kg of formula 2 compound lithium p-nitrobenzenesulfonate, 5.29 kg of formula 1 compound triethylene glycol monovinyl ether, and stir well in the 100L reactor; 5 L of 2M lithium tert-butoxide tetrahydrofuran solution was added to the reaction solution, and stirred at room temperature for 1 hour. The temperature of the reaction solution was raised to 70° C. for 6 hours, and the reaction was completed.

[0037] The reaction solution was naturally cooled to room temperature, and a large amount of light yellow solid was precipitated. Filtrate, recover the filtrate for mechanical application, and dry the filter cake to obtain 11.32 kg of product. Product HPLC purity 99.1%, yield 97.84%, 1H NMR (400MHz, d6-DMSO): δ8.43 (d, 2H), 8.02 (d, 2H...

Embodiment 2

[0044] The synthetic route is as follows:

[0045]

[0046] Step (1): Preparation of 12-crown-4 (2,4-dinitrobenzenesulfonate lithium) complex compound of formula 3

[0047] Maintain a slight positive pressure of nitrogen, add 50 L tetrahydrofuran, 8.05 kg formula 2 compound 2,4-dinitrobenzene sulfonate lithium, 5.29 kg formula 1 compound triethylene glycol monovinyl ether, and stir and then add 300 g of sodium ethylate in three batches to the reaction solution, and stir at room temperature for 1 hour. The temperature of the reaction solution was raised to 40° C. for 7 hours, and the reaction was completed.

[0048] The reaction solution was naturally cooled to room temperature, and a large amount of light yellow solid was precipitated. Filtrate, recover the filtrate for mechanical application, and dry the filter cake to obtain 12.01kg of product. Product HPLC purity 98.2%, yield 93%, 1H NMR (400MHz, d6-DMSO): δ9.07(s, 1H), 8.91(d, 1H), 8.34 (d, 1H), 3.77(s, 16H) .

[0...

Embodiment 3

[0055] The synthetic route is as follows:

[0056]

[0057] Step (1): Preparation of Formula 3 Compound 12-Crown Ether-4 o-Nitrobenzenesulfonate Lithium Complex

[0058] Maintaining a slight positive pressure of nitrogen, add 45 L of xylene, 7.31 kg of formula 2 compound o-nitrobenzene sulfonate lithium, 5.29 kg of formula 1 compound triethylene glycol monovinyl ether, and stir well; Add 200 g of sodium methoxide in four batches to the reaction solution, and stir at room temperature for 1 hour. The temperature of the reaction solution was raised to 45° C. for 5 hours, and the reaction was completed.

[0059] Most of the solvent was recovered by rotary evaporation of the reaction solution, and an appropriate amount of tert-butyl methyl ether was added to the residue, cooled in an ice-water bath to precipitate a large amount of light yellow solid. Filtrate, recover the filtrate and apply mechanically, and dry the filter cake to obtain 10.64kg of product. Product HPLC purit...

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Abstract

The invention discloses a 12-crown ether-4 lithium salt complex and a preparation method thereof, as well as a method for preparing 12-crown ether-4 by using the complex. The preparation method of the described 12-crown ether-4 takes the compound of formula 1 triethylene glycol monovinyl ether as a raw material, and the compound of formula 2 contains substituent lithium alkoxide under the condition of isolated air, in the first reaction solvent , adding a basic substance to catalyze the reaction, and after the reaction is complete, the compound 12-crown-4 lithium salt complex of formula 3 is obtained; then the compound 12-crown-4 lithium salt complex of formula 3 and the acidic substance are added to the second reaction In a solvent, react at a reaction temperature of -20 to 100°C. After the reaction is complete, the compound 12-crown ether-4 of formula 4 is obtained. The design route of the invention is reasonable, the raw materials are safe and easy to obtain, the process safety is high, the reaction selectivity is high, the product purity is high, the operator is friendly, the production cost is greatly reduced, and the demand for industrial production of products can be fully met.

Description

technical field [0001] The invention relates to the technical field of synthesis of crown ether compounds, in particular to a 12-crown ether-4 lithium salt complex and a preparation method thereof, and a method for preparing 12-crown ether-4 using the complex. Background technique [0002] 12-Crown-4, also known as 1,4,7,10-tetraoxacyclododecane or lithium ionophore V, is a chemical formula C 8 h 16 o 4 of crown ethers. It is a cyclic tetramer of ethylene glycol, and its internal hole size perfectly matches the diameter of lithium ions, so it has a very good selective binding ability for lithium ions. According to the report published by Li Ning et al. in "Journal of the American Chemical Society" in 2020 (Ning Li, Feng Chen, et al. J. Am. Chem. Soc., 2020, 142, 21082–21090), 12-crown ether- 4 The ion transmembrane transporter formed with fullerene has a selectivity of lithium ions that is 47.5 times that of other alkali metal ions (sodium ions, potassium ions, and cesiu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D323/00C07C309/40C07C303/32
CPCC07C303/32C07C309/40C07D323/00
Inventor 龙韬张军陈丕证邹增龙
Owner SUZHOU BAILINGWEI HYPERFINE MATERIAL
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