磷酸钾中和法邻甲酚羧化反应的绿色合成

doi:10.11944/j.issn.1000-0518.2015.06.140342

摘要/Abstract

摘要：

以邻甲酚和二氧化碳为原料,以磷酸钾为中和剂一步羧化合成邻甲基水杨酸及相关产物。探讨了反应条件对产率的影响。实验结果表明,当磷酸钾与邻甲酚物料比为2.5:1,反应温度150 ℃,反应压力3.0 MPa时,羧化反应产物总收率达到95.4%,同时邻甲基水杨酸收率也达到最大。与传统碳酸钾中和法相比,磷酸钾中和法产物在后处理过程中无二氧化碳放出,后处理过程中的磷酸根可制备为磷酸钾使用,新工艺是一条绿色化工路线。

关键词: 二氧化碳, 磷酸钾, 邻甲基水杨酸, 绿色合成, 邻甲酚

Abstract:

A green process of the carboxylation reaction of o-cresol with CO₂ using K₃PO₄ as a base was studied for the synthesis of 2-hydroxy-3-methylbenzoic acid (o-MSA) and related carboxylated products. Various reaction parameters such as temperature, pressure, and the ratio of the base to substrate had been tested. The results show that 95.4% total yield of all carboxylated products in this Koble-Schmitt reaction is obtained using K₃PO₄ as a base under 3.0 MPa CO₂ and 150 ℃. Additionally, no CO₂ is released during the neutralization process following the Koble-Schmitt reaction and the K₃PO₄ can be recovered and recycled by neutralization of KH₂PO₄ with KOH. Therefore, this process allows a green fixation of CO₂.

Key words: carbon dioxide, potassium phosphate, hydroxy-methylbenzoic acid, green synthesis, o-cersol

中图分类号:

伍琳娟, 朱大建, 肖瑟, 雷以柱, 郭园园, 张盼盼, 李光兴. 磷酸钾中和法邻甲酚羧化反应的绿色合成[J]. 应用化学, 2015, 32(6): 647-651.

WU Linjuan, ZHU Dajian, XIAO Se, LEI Yizhu, GUO Yuanyuan, ZHANG Panpan, LI Guangxing. Green Process for o-Cersol Carboxylation Using Potassium Phosphate Base[J]. Chinese Journal of Applied Chemistry, 2015, 32(6): 647-651.

参考文献

[1]	Peters M,Köhler B,Kuckshinrichs W,et al.Chemical Technologies for Exploiting and Recycling Carbon Dioxide into the Value Chain[J]. ChemSusChem,2011,4(9):1216-1240.
[2]	Sakakura T,Choi J C,Yasuda H. Transformation of Carbon Dioxide[J]. Chem Rev,2007,107(6):2365-2387.
[3]	Huang K,Sun C L,Shi Z J. Transition-metal-catalyzed C—C Bond Formation Through the Fixation of Carbon Dioxide[J]. Chem Soc Rev,2011,40(5):2435-2452.
[4]	Patil Y P,Tambade P J,Jagtap S R,et al.Carbon Dioxide:A Renewable Feedstock for the Synthesis of Fine and Bulk Chemicals[J]. Front Chem Eng China,2010,4(2):213-235.
[5]	CHEN Xinzhi,CHEN Han'geng,QIAN Chao. CPreparation of Salicylic Acid:CN,101613270A[P],2009-12-30(in Chinese). 陈新志,陈汉庚,钱超. 一种水杨酸的制备方法:中国专利,CN101613270A[P],2009-12-30.
[6]	ZHENG Yiwu. Studies on Supercritical Fluid Chemistry Reaction to Synthesis p-Hydroxybenzoic Acid[D]. Guangzhou:Ji'nan University,2000(in Chinese). 郑轶武. 超临界化学反应合成对羟基苯甲酸的研究[D]. 广州:暨南大学,2000.
[7]	Marković Z, Marković S, Durović I. Kolbe-Schmitt Reaction of Sodium 2-Naphthoxide[J]. Monatsh Chem, 2008,139(4):329-335.
[8]	Lindsey A S,Jeskey H. The Koble-Schmitt Reations[J]. Chem Rev,1957,57(4):583-620.
[9]	WANG Yihua,ZHANG Dexiang. The Synthesis of Hydroxyl Aromatic Acid[J]. Zhejiang Chem Ind,1989,20(2):19-23(in Chinese). 王煜华,章德祥. 芳香族羟基羧酸的合成评述[J]. 浙江化工,1989,20(2):19-23.
[10]	ZHANG Dexiang,WANG Yihua,WU Jinlin,et al.The Synthesis of 3-Methyl Salicylic Acid[J]. Dyest Color,1988,4:004(in Chinese). 章德祥,王煜华,吴金林,等. 固相法合成邻甲基水杨酸[J]. 染料与染色,1988,4: 004.
[11]	Cameron D O N,Jeskey H,Baine O. The Koble-Schmitt Reation. I. Varitions in the Carbonation of p-Cresol[J]. J Org Chem,1950,15(2):233-236.
[12]	Marković Z, Marković S,Begović N. Influence of Alkali Metal Cations upon the Kolbe-Schmitt Reaction Mechanism[J]. Chem Inf Model,2006,46(5):1957-1964.
[13]	Wessely F,Benedikt K,Benger H,et al.Zur Kenntnis der Carboxylierung yon Phenolen[J]. Monatsh Chem,1950,81(7):1071-1091.
[14]	Lee K S,Kim I W. New Phase Transition at 155 K and Thermal Stability in KHCO3[J]. J Phys Soc Jpn,2001,70(12):3581-3584.

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