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Cheap and efficient preparation method of benzene triimide and derivative thereof

A technology of phenyl and compound, applied in the field of cheap and efficient preparation, can solve the problems of harsh reaction conditions, expensive raw materials, lack of synthesis methods, etc., and achieves the effects of stable separation and purification, mild reaction conditions, and easy separation and purification

Active Publication Date: 2020-04-17
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Trisimide (BTI) and its derivatives have a similar skeleton structure to NDI, so they also have great potential in the fields of organic optoelectronics, molecular recognition, and sensing. However, due to the lack of mature synthesis methods, Restricted the development of trimesimide (BTI) and its derivatives in related fields
[0003] So far, there are few reports about the synthesis of trimellitic imide (BTI) and its derivatives. The main synthetic method is to start from pyromellitic acid, form a salt by reacting with the corresponding primary amine, and further pass high temperature thermal (McMenimen, K.A.; Hamilton, D.G.J.Am.Chem.Soc.2001, 123, 6453; Hamilton, D.G.J.Org.Chem.2008, 73, 3950; Minami, T and Mamada, M.Chem.Commun.2017, 53 , 63.)
However, existing synthetic methods have problems such as expensive raw materials, harsh reaction conditions, and low overall yield, and lack cheap and efficient methods for the synthesis of trimellitamide (BTI) and derivatives thereof. Therefore, the development of new trimellitamides Synthetic methods for imines (BTI) and their derivatives are necessary

Method used

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  • Cheap and efficient preparation method of benzene triimide and derivative thereof
  • Cheap and efficient preparation method of benzene triimide and derivative thereof
  • Cheap and efficient preparation method of benzene triimide and derivative thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] Example 1. Preparation of Trimellimides Compounds Shown in Formula Ia (wherein R is hydrogen)

[0053] according to figure 1 The shown reaction equation prepares the trimellitic imide compound shown in formula Ia.

[0054] The specific preparation method is:

[0055]Add magnetons and maleimide derivatives shown in IIa (445mg, 3.0mmol) to a clean round bottom bottle, and add 15mL of a mixed solvent of acetic acid and water (v / v, 4 / 1). Then put the reaction solution in an oil bath, heat and reflux for 3 hours, insoluble matter is formed in the reaction solution, after the reaction is completed, the reaction solution is cooled, filtered with suction, the solid is washed with a large amount of acetic acid and acetone, and dried to obtain the structure shown in formula Ia Compound 183mg, yield 60%.

[0056] 1 H NMR (400MHz, DMSO-d 6 ,ppm):δ12.06(s,3H);

[0057] HRMS(ESI):m / z calcd:283.9944[M-H] - ;Found: 283.9944[M-H] - .

[0058] It can be seen from the above that ...

Embodiment 2

[0066] Embodiment 2, the trimellitic imide compound (R is a methyl group) shown in the preparation formula Ib

[0067] The specific preparation method is:

[0068] Add magnetons and maleimide derivatives (720 mg, 5.1 mmol) shown in IIb to a clean round bottom bottle, and add 20 mL of a mixed solvent of acetic acid and water (v / v, 4 / 1). Then the reaction solution was put into an oil bath, heated and refluxed for 3 hours, after the reaction was completed, the reaction solution was cooled, a large amount of solids were precipitated in the reaction solution, filtered by suction, the solids were washed with a large amount of acetic acid and acetonitrile, and dried to obtain the compound shown in the structure of formula IIa Compound 240 mg, yield 44%.

[0069] the product is a solid;

[0070] 1 H-NMR (300MHz, DMSO-d 6 ,ppm):δ3.12(s,12H);

[0071] 13 C-NMR (75MHz, DMSO-d 6 , ppm): δ163.5, 133.1, 25.0;

[0072] HRMS(ESI):m / z calcd:328.0570[M+H] + ;Found:328.0559[M+H] + .

...

Embodiment 3

[0080] Example 3, the preparation of the trimesimide compound represented by formula Ic (R is ethyl)

[0081] according to Figure 5 The shown reaction equation prepares trimellitamide compounds shown in Formula Ic.

[0082] The specific preparation method is:

[0083] Add magneton and maleimide derivative shown in IIc (312mg, 1.86mmol) to a clean round bottom bottle, and add 10mL of a mixed solvent of acetic acid and water (v / v, 4 / 1). Then the reaction solution was put into an oil bath, and heated to reflux for 3 hours. After the reaction was completed, the solvent was removed by rotary evaporation, followed by 100-200 mesh silica gel column chromatography, and rinsed with a mixed solvent of petroleum ether and ethyl acetate (1:1). 78 mg of the compound represented by the structure of formula Ic was isolated with a yield of 34%.

[0084] 1 H-NMR (400MHz, CDCl 3 , ppm): δ3.92(q, J=7.2Hz, 6H), 3.92(t, J=7.2Hz, 6H);

[0085] HRMS(ESI):m / z calcd:392.0859[M+Na] + ;Found:392...

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Abstract

The invention discloses a preparation method of benzene triimide (BTI) and a derivative thereof, wherein the structural general formula of the compound is represented by a formula I. The preparation method comprises the following steps: under the condition of refluxing in a mixed solution of acetic acid and water, carrying out an intermolecular aromatic ring construction reaction on a maleimide derivative represented by a formula II to obtain the benzene triimide (BTI) and the derivative I thereof. According to the invention, the cheap and easily available raw materials maleic anhydride and maleimide and the cheap and easily available primary amine compound are selected and subjected to simple addition, elimination and amination to rapidly prepare a large amount of maleimide derivatives, and further the maleimide derivatives are subjected to an intermolecular cyclization reaction to rapidly prepare the benzene triimide (BTI) and the derivative thereof in one step, so that the reactionconditions are mild, and the obtained product is stable in air and easy to separate and purify, and has good application prospect.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a cheap and efficient preparation method of trimellitamide (BTI) and derivatives thereof. Background technique [0002] 1,4,5,8-Naphthalene tetracarbodiimide (NDI) and its derivatives have been widely used in organic optoelectronics, transmembrane transport, molecular recognition, and transmission due to their rigid conjugated skeleton and electron-deficient properties. Sensitivity, catalysis and other fields play an important role (Matile, S.J.Am.Chem.Soc.2006, 128, 14788; Guha, S.; Saha, S.J.Am.Chem.Soc. 2010, 132, 17674; Matile, S.Angew . Chem. Int. Ed. 2013, 52, 9940; Stoddart, J.F.et.al., Angew. Chem. Int. Ed. 2013, 52, 13100.). Trisimide (BTI) and its derivatives have a similar skeleton structure to NDI, so they also have great potential in the fields of organic optoelectronics, molecular recognition, and sensing. However, due to the lack of mature synthesis methods, This...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D487/14G01N27/48G01N21/78
CPCC07D487/14G01N21/78G01N27/48
Inventor 王德先敖宇飞王其强庹德辉何清
Owner INST OF CHEM CHINESE ACAD OF SCI