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

Figures(11)

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
1. [1]
  (a) Deming, T. J. Nature 1997, 390, 386; (b) Liang, J.; Zhi, X.; Zhou, Q.; Yang, J. Polymer 2019, 165, 830; (c) Nie, Y.; Zhi, X.; Du, H.; Yang, J. Molecules 2018, 23, 760; (d) Lu, H.; Cheng, J. J. Am. Chem. Soc. 2007, 129, 14114; (e) Aliferis, T.; Iatrou, H.; Hadjichristidis, N. Biomacromolecules 2004, 5, 1653.
2. [2]
  (a) Deming, T. J. Adv. Polym. Sci. 2006, 202, 1; (b) Cheng, R. P.; Fisher, S. L.; Imperiali, B. J. Am. Chem. Soc. 1996, 118, 11349.
3. [3]
  Maji, S. K.; Banerjee, R.; Velmurugan, D.; Razak, A.; Fun, H. K.; Banerjee, A. J. Org. Chem. 2002, 67, 633. doi: 10.1021/jo010314k
4. [4]
  Frank, A. O.; Vangamudi, B.; Feldkamp, M. D. J. Med. Chem. 2014, 57, 2455. doi: 10.1021/jm401730y
5. [5]
  (a) Cha, J. N.; Stucky, G. D.; Morse, D. E.; Deming, T. J. Nature 2000, 403, 289; (b) Deming, T. J. Adv. Drug. Delive. Rev. 2002, 54, 1145; (c) Dos Santos, S.; Chandravarkar, A.; Mandal, B.; Mimna, R.; Murat, K.; Saucede, L.; Tella, P.; Tuchscherer, G.; Mutter, M. S. J. Am. Chem. Soc. 2005, 127, 11888; (d) Deng, C.; Wu, J.; Cheng, R.; Meng, F.; Klok, H.; Zhong, Z. Prog. Polym. Sci. 2014, 39, 330; (e) Lu, H.; Wang, J.; Song, Z.; Yin, L.; Zhang, Y.; Tang, H.; Tu, C.; Lin, Y.; Cheng, J. Chem. Commun. 2014, 50, 139.
6. [6]
  Leuchs, H. J. Ber. Dtsch. Chem. Ges. 1906, 39, 857. doi: 10.1002/cber.190603901133
7. [7]
  (a) Kricheldorf, H. R.; Lossow, C. V.; Schwarz, G. Macromol. Chem. Phys. 2005, 206, 282; (b) Ohkawa, K.; Nagai, T.; Nishida, A.; Yamomoto, H. J. Adhes. 2009, 85, 770.
8. [8]
  (a) Vayaboury, W.; Giani, O.; Collet, H.; Commeyras, A.; Schué, F. Amino Acids 2004, 27, 161; (b) Collet, H.; Bied, C.; Mion, L.; Taillades, J.; Commeyras, A. Tetrahedron Lett. 1996, 37, 9043.
9. [9]
  (a) Tundo, P.; Selva, M. J. Acc. Chem. Res. 2002, 35, 706; (b) Tundo, P.; Musolino, M.; Aricò, F. Green Chem. 2018, 20, 28; (c) Anastas, P. T.; Lankey, R. L. Green Chem. 2000, 2, 289; (d) Li, Z.; Cheng, B.; Su, K.; Gu, Y.; Xi, P.; Guo, M. J. Mol. Catal. A 2008, 289, 100.
10. [10]
  Zhang, Z.; Su, K.; Li, Z. Org. Lett. 2019, 21, 749. doi: 10.1021/acs.orglett.8b03984
11. [11]
  Nenoff, T. M.; Harrison, W. T. A.; Gier, T. E.; Stucky, G. S. J. Am. Chem. Soc. 1991, 113, 378. doi: 10.1021/ja00001a065
12. [12]
  Tundo, P.; Arico, P.; Rosamilia, A. E.; Rigo, M.; Maranzana, A.; Tonachini, G. Pure Appl. Chem. 2009, 81, 1971. doi: 10.1351/PAC-CON-08-12-02
13. [13]
  Wang, J. X. M.S. Thesis, North University of China, Taiyuan, 2005 (in Chinese).
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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