Citation: Jia Xiaoyan, Li Zhenhuan. Synthesis of N-Carboxy Alanine Anhydride from Alanine and Dimethyl Carbonate over NaZnPO₄ in One-pot[J]. Acta Chimica Sinica, ;2020, 78(6): 540-546. doi: 10.6023/A20020024 shu

Synthesis of N-Carboxy Alanine Anhydride from Alanine and Dimethyl Carbonate over NaZnPO₄ in One-pot

Jia Xiaoyan ,
Li Zhenhuan ^,

School of Materials Science and Engineering, Tiangong University, Tianjin 300387

Corresponding author: Li Zhenhuan, lizhenhuan@tiangong.edu.cn
Received Date: 7 February 2020
Available Online: 13 May 2020
Fund Project: the National Natural Science Foundation of China 21376177Project supported by the National Natural Science Foundation of China (Nos. 21676202, 21376177)the National Natural Science Foundation of China 21676202

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In this paper, the environmentally friendly synthesis of N-carboxy alanine anhydride (Ala-NCA) from alanine and dimethyl carbonate (DMC) over NaZnPO₄ was carried out in one-pot, and the NaZnPO₄ catalyst with the acid-base double active sites was prepared by the solid phase synthesis method. The X-ray diffraction spectrometer (XRD) was used to characterize the structure of NaZnPO₄, and the reaction products were analyzed by the high performance liquid chromatography (HPLC) with evaporative light scattering detector (ELSD). The GC-MS characterized result of obtained Ala-NCA was extremely consistent with that of the standard sample, which indicated that Ala-NCA was synthesized successfully. When the reaction was carried out at 150℃ for 8 h, the maximum 46.84% yield of Ala-NCA can be obtained in DMF solvent. As the reaction temperature increased to 160℃, Ala-NCA yield significantly declined because of the instability of Ala-NCA at higher temperature. However, there was no Ala-NCA formation without catalyst existence because DMC is not easy to undergo carboxymethylation with amino acids. NaZnPO₄ could be recycled, but Ala-NCA yield declined to 38.62% after the fifth cycle. The reasons for that were attributed to the catalyst surface area reduction and the active site loss of Na-O and Zn²⁺. The reaction between DMC and amino acids over NaZnPO₄ were characterized by TG-MS-IR, and the possible catalytic mechanism was provided. Namely, Zn²⁺ and Na-O in NaZnPO₄ perform an effective acid-base synergistic catalysis, on the one hand the basic Na-O active sites play an key role on amino group deprotonation, which promotes the carboxymethylation of amino acids with DMC, on the other hand the acid active sites of Zn²⁺ can well catalyze the cyclization of intermediate into Ala-NCA. In this cyclization process, NaZnPO₄ also can transfer the trapped protons to carboxymethylation intermediate to facile the formation of target compounds.
- N-carboxy alanine anhydride,
- dimethyl carbonate,
- carboxymethylation,
- acid-base coordination catalysis,
- cyclization
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Synthesis of N-Carboxy Alanine Anhydride from Alanine and Dimethyl Carbonate over NaZnPO4 in One-pot

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Synthesis of N-Carboxy Alanine Anhydride from Alanine and Dimethyl Carbonate over NaZnPO₄ in One-pot