Efficient synthesis of 1,6-hexamethylene diurethane through coupling transesterification and methoxycarbonylation with methyl phenyl carbonate as intermediate

doi:10.1016/j.cjche.2014.11.033

Chinese Journal of Chemical Engineering ›› 2015, Vol. 23 ›› Issue (7): 1147-1152.DOI: 10.1016/j.cjche.2014.11.033

• 催化、动力学与反应工程 • 上一篇下一篇

Efficient synthesis of 1,6-hexamethylene diurethane through coupling transesterification and methoxycarbonylation with methyl phenyl carbonate as intermediate

Yong Yang^1,3, Jihai Tang¹, Xian Chen¹, Zhaoyang Fei^1,2, Mifen Cui¹, Xu Qiao^1,2

1 College of Chemistry and Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
2 State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
3 College of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaiyin 223003, China

收稿日期:2014-06-26 修回日期:2014-11-04 出版日期:2015-07-28 发布日期:2015-08-21
通讯作者: Xian Chen, Xu Qiao
基金资助:
Supported by the National Natural Science Foundation of China (21276126, 21306089) and the Jiangsu Province Higher Education Natural Science Foundation (09KJA530004, 13KJB530006).

Efficient synthesis of 1,6-hexamethylene diurethane through coupling transesterification and methoxycarbonylation with methyl phenyl carbonate as intermediate

Yong Yang^1,3, Jihai Tang¹, Xian Chen¹, Zhaoyang Fei^1,2, Mifen Cui¹, Xu Qiao^1,2

1 College of Chemistry and Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
2 State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
3 College of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaiyin 223003, China

Received:2014-06-26 Revised:2014-11-04 Online:2015-07-28 Published:2015-08-21
Contact: Xian Chen, Xu Qiao
Supported by:
Supported by the National Natural Science Foundation of China (21276126, 21306089) and the Jiangsu Province Higher Education Natural Science Foundation (09KJA530004, 13KJB530006).

摘要/Abstract

摘要： A reaction coupling system of transesterification and methoxycarbonylation with methyl phenyl carbonate (MPC) as intermediate was established to efficiently prepare 1,6-hexamethylene diurethane (HDU) from 1,6-hexamethylene diamine (HDA). The feasibility of the system was explored using the thermodynamics analysis, the reaction mechanism and the experiment results. The optimal reaction was carried out to get higher HDU yield. The thermodynamic analysis showed that the methoxycarbonylation of HDA with MPC, the Gibbs free energy of which was negative, was a spontaneous process. Furthermore, the equilibrium constant of the methoxycarbonylation of HDA with MPC was much greater than that of the transesterification of dimethyl carbonate (DMC) with phenol, so the reaction coupling could be realized under mild conditions. The reaction mechanismanalysis indicated that phenoxy anion was the key species for reaction coupling. HigherMPC concentration was detected when sodium phenoxide was used as transesterification reactant with DMC, since the phenoxy anion of sodium phenoxide could be dissociated more easily. Sodium phenoxide was more suitable to prepare HDU through reaction coupling. A yield of HDU as high as 98.3% could be reached under the optimal conditions of m_PhONa/m_DMC = 0.027 and n_DMC/n_HDA = 8/1 at 90 ℃ in 2 h.

关键词: Methyl phenyl carbonate, 1, 6-Hexamethylene diurethane, Transesterification, Methoxyl carbonate, Reaction coupling

Abstract: A reaction coupling system of transesterification and methoxycarbonylation with methyl phenyl carbonate (MPC) as intermediate was established to efficiently prepare 1,6-hexamethylene diurethane (HDU) from 1,6-hexamethylene diamine (HDA). The feasibility of the system was explored using the thermodynamics analysis, the reaction mechanism and the experiment results. The optimal reaction was carried out to get higher HDU yield. The thermodynamic analysis showed that the methoxycarbonylation of HDA with MPC, the Gibbs free energy of which was negative, was a spontaneous process. Furthermore, the equilibrium constant of the methoxycarbonylation of HDA with MPC was much greater than that of the transesterification of dimethyl carbonate (DMC) with phenol, so the reaction coupling could be realized under mild conditions. The reaction mechanismanalysis indicated that phenoxy anion was the key species for reaction coupling. HigherMPC concentration was detected when sodium phenoxide was used as transesterification reactant with DMC, since the phenoxy anion of sodium phenoxide could be dissociated more easily. Sodium phenoxide was more suitable to prepare HDU through reaction coupling. A yield of HDU as high as 98.3% could be reached under the optimal conditions of m_PhONa/m_DMC = 0.027 and n_DMC/n_HDA = 8/1 at 90 ℃ in 2 h.

Key words: Methyl phenyl carbonate, 1,6-Hexamethylene diurethane, Transesterification, Methoxyl carbonate, Reaction coupling

Yong Yang, Jihai Tang, Xian Chen, Zhaoyang Fei, Mifen Cui, Xu Qiao. Efficient synthesis of 1,6-hexamethylene diurethane through coupling transesterification and methoxycarbonylation with methyl phenyl carbonate as intermediate[J]. Chinese Journal of Chemical Engineering, 2015, 23(7): 1147-1152.

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Efficient synthesis of 1,6-hexamethylene diurethane through coupling transesterification and methoxycarbonylation with methyl phenyl carbonate as intermediate

Efficient synthesis of 1,6-hexamethylene diurethane through coupling transesterification and methoxycarbonylation with methyl phenyl carbonate as intermediate

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