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Journal of Chemistry Volume 2018 ,2018-04-18
Full N,N-Methylation of 4,4′-Methylenedianiline with Dimethyl Carbonate: A Feasible Access to 4,4′-Methylene bis(N,N-Dimethylaniline)
Research Article
Zegang Qiu 1 Kunjie Wang 2 Zhiqin Li 1 Tao Li 1 Jinhao Bai 1 Chanjuan Yin 1 Xiushen Ye 3 Haining Liu 3
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DOI:10.1155/2018/4627903
Received 2017-12-25, accepted for publication 2018-02-14, Published 2018-02-14
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摘要

The full N,N-methylation of 4,4′-methylenedianiline (MDA) with dimethyl carbonate (DMC) was investigated. The yield of the major product 4,4′-methylene bis(N,N-dimethylaniline) (MBDMA) reached as high as 97% over NaY catalyst at 190°C for 6 h. The catalyst could be used for two more times with acceptable MBDMA yields higher than 90%. The main by-products were identified as three N-methylated derivatives. Surprisingly, the formation of the N-methoxycarbonylation product was extremely restrained, which could be produced in high yields of 98% on zinc acetate catalyst. Furthermore, the reaction pathway to the major product MBDMA was proposed. Finally, a feasible synthetic route of 4,4′-methylene bis(N,N-dimethylaniline) (MBDMA) was established, featuring a high yield, mild reaction conditions, and simple operations.

授权许可

Copyright © 2018 Zegang Qiu et al. 2018
This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

图表

Two possible N-methylation reaction pathways of MDA with DMC.

The liquid chromatogram of the filtrate obtained after the reaction of MDA with DMC.

MS spectra of the by-products 1, 2, and 3. Subfigures (a), (b), and (c) present the MS spectra of the pseudomolecular ions of compounds 1, 2, and 3, respectively. 4 stands for the ion with an m/z value of 106.

MS spectra of the by-products 1, 2, and 3. Subfigures (a), (b), and (c) present the MS spectra of the pseudomolecular ions of compounds 1, 2, and 3, respectively. 4 stands for the ion with an m/z value of 106.

MS spectra of the by-products 1, 2, and 3. Subfigures (a), (b), and (c) present the MS spectra of the pseudomolecular ions of compounds 1, 2, and 3, respectively. 4 stands for the ion with an m/z value of 106.

Liquid chromatograms obtained after the reaction between MDA and DMC under different temperatures. Reaction conditions: DMC 27.0 g (0.30 mol), MDA 1.98 g (0.01 mol), NaY 1.98 g, and reaction time 6 h. m(NaY)/m(DMC) (g/g) = 0.07/1.

Liquid chromatograms obtained after the reaction between MDA and DMC under different reaction times. Reaction conditions: DMC 27.0 g (0.30 mol), MDA 1.98 g (0.01 mol), NaY 1.98 g, and reaction temperature 190°C. m(NaY)/m(DMC) (g/g) = 0.07/1.

XRD spectra of fresh and reused NaY catalysts. (a) Fresh NaY; (b) NaY after used for the first time; (c) NaY after used for the second time.

IR spectra of fresh and reused NaY catalysts. (a) Fresh NaY; (b) NaY after used for the first time; (c) NaY after used for the second time.

NH3-TPD profiles of fresh and reused NaY catalysts. (a) Fresh NaY; (b) NaY after used for the first time; (c) NaY after used for the second time.

Two possible pathways of the N-methylation process of MDA with DMC in the presence of NaY.

通讯作者

Zhiqin Li.College of Chemistry and Chemical Engineering, Xi’an Shiyou University, Xi’an 710065, China, xsyu.edu.cn.lizhiqin@xsyu.edu.cn

推荐引用方式

Zegang Qiu,Kunjie Wang,Zhiqin Li,Tao Li,Jinhao Bai,Chanjuan Yin,Xiushen Ye,Haining Liu. Full N,N-Methylation of 4,4′-Methylenedianiline with Dimethyl Carbonate: A Feasible Access to 4,4′-Methylene bis(N,N-Dimethylaniline). Journal of Chemistry ,Vol.2018(2018)

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