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12-crown ether-4 lithium salt complex as well as preparation method and application thereof

A complex, crown ether technology, applied in sulfonate preparation, organic chemistry and other directions, can solve the problems of high raw material risk, low product yield, low product purity, etc., and achieve high reaction selectivity and high product purity. , the effect of high process safety

Active Publication Date: 2021-08-13
SUZHOU BAILINGWEI HYPERFINE MATERIAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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 as well as preparation method and application thereof
  • 12-crown ether-4 lithium salt complex as well as preparation method and application thereof
  • 12-crown ether-4 lithium salt complex as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
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, and a method for preparing 12-crown ether-4 by adopting the complex. The preparation method of the 12-crown ether-4 comprises the following steps: by taking a compound triethylene glycol monovinyl ether in a formula 1 as a raw material, adding an alkaline substance into a first reaction solvent for catalytic reaction with a compound lithium alkoxide containing a substituent group in a formula 2 under the condition of air isolation, and obtaining a compound 12-crown ether-4 lithium salt complex in a formula 3 after the reaction is completed; and then adding a compound 12-crown ether-4 lithium salt complex as shown in a formula 3 and an acidic material into a second reaction solvent, reacting at the reaction temperature of-20 to 100 DEG C, and after the reaction is completed, obtaining a compound 12-crown ether-4 as shown in a formula 4. The design route is reasonable in design, 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 method is friendly to operators, the production cost is greatly reduced, and the requirements of 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 Applications(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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