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多元曲线分辨结合在线红外用于3-氨基-4-氨基肟基呋咱的合成反应机理

刘瑜1,张天龙1,王伯周2,葛忠学2,李华1*   

  1. (1.西北大学化学与材料科学学院 西安 710069;2.西安近代化学研究所 西安 710065)
  • 收稿日期:2011-10-27 修回日期:2012-02-27 出版日期:2012-09-10 发布日期:2012-09-10
  • 通讯作者: 李华，教授; Tel:029-88302635; Fax:029-88303527; E-mail:huali@nwu.edu.cn; 研究方向：化学计量学与过程分析化学
  • 基金资助:
    国家自然科学基金(21175106)资助项目

Mechanistic Synthesis of 3-Amino-4-amino-oxime Furazan Using Multivariate Curve Resolution Combined with On-line Infrared Spectroscopy

LIU Yu1, ZHANG Tianlong1, WANG Bozhou2, GE Zhongxue2, LI Hua1*   

  1. (1.Institute of Chemical and Material Science,Northwest University,Xi′an 710069,China;
    2.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)
  • Received:2011-10-27 Revised:2012-02-27 Published:2012-09-10 Online:2012-09-10

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摘要： 利用红外光谱在线监测丙二睛、亚硝酸钠和盐酸羟胺合成3-氨基-4-氨基肟基呋咱的反应过程，采用多元曲线分辨-交替最小二乘法（MCR-ALS）、直观推导式演进特征投影法(HELP)等化学计量学方法对反应过程所获得的实时红外光谱数据矩阵进行解析，得到了各组分纯物质的浓度变化曲线和对应的红外光谱，并将多元曲线分辨交替最小二乘法与直观推导式演进特征投影法的分析结果进行比较，得出可相互验证的一致结论，据此推出该反应合理的反应机理。 2种方法得到的反应物与生成物的光谱与原光谱的相似度近似于1，说明该解析方法具有准确性和可靠性。 结果表明，化学计量学结合红外光谱可有效的应用于3-氨基-4-氨基肟基呋咱合成过程的机理推断。

关键词: 在线红外光谱, 多元曲线分辨-交替最小二乘, 直观推导式演进特征投影, 反应机理

Abstract: On-line infrared spectroscopy was used to monitor the reaction process for synthesizing 3-amino-4-amino oxime furazan from malononitrile, sodium nitrite and hydroxylamine hydrochloride catalyzed by acetic acid. The concentration profiles and spectra of the reactant, intermediates and product were obtained by analyzing the real-time infrared spectroscopy(IR) data using chemometric methods such as multiple curve resolution-alternating least squares(MCR-ALS), heuristic evolving latent projections(HELP) and etc. A reasonable mechanism was induced by the conclusion acquired from comparing MCR-ALS with HELP. Spectral similarity between the original and the obtained spectra of the reactants and the product was close to one, which showed that the methods used in this article were accurate and reliable. The experimental results showed that the chemometric resolution combined with IR spectroscopy could effectively be applied to mechanistic study on the formation of 3-amino-4-amino oxime furazan. It would provide significant insights into the reaction mechanism.

Key words: infrared spectroscopy, multivariate curve resolution - alternating least squares, heuristic evolving latent projection(HELP), reaction mechanism

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