二茂铁甲酸(2-丙烯酰氧乙基)酯的合成及优化

doi:10.11944/j.issn.1000-0518.2015.07.140400

摘要/Abstract

摘要：

二茂铁类燃速催化剂在使用过程中存在的主要问题是在推进剂贮存过程中易产生迁移和挥发问题。针对这些不足,对二茂铁衍生物进行改性,在二茂铁的茂环上引入极性基团以增大分子极性。以二茂铁甲酸(FCA)和2-羟乙基丙烯酸酯(HEA)为反应物,以二环己基碳二亚胺(DCC)为脱水剂,以对二甲氨基吡啶(DMAP)为催化剂,在二氯甲烷(DCM)中合成二茂铁甲酸(2-丙烯酰氧乙基)酯(AEFC),优化各反应条件,确定最佳投料摩尔比为n(FCA):n(HEA):n(DMAP):n(DCC)=20:28:20:24,反应温度为0 ℃,DCC溶液滴加时间为60~75 min,反应时间为15 h,搅拌速率为1000 r/min,在此条件下得到的AEFC的产率为75.1%,纯度为98%。

关键词: 酯化反应, 二茂铁衍生物, 二环己基碳二亚胺/对二甲氨基吡啶法

Abstract:

The main problems in the use and storage of ferrocene derivatives as burning rate catalysts are the migration and volatility of catalysts. A solution for the problems is to introduce polar groups on ferrocene. This paper reported the synthesis of 2-acryloyloxyethyl ferrocenecarboxylate (AEFC) from ferrocenecarboxylic acid (FCA) and 2-hydroxyethyl acrylate (HEA) with N,N'-dicyclohexylcarbodiimide (DCC) as the dehydration agent in the presence of 4-dimethylaminopyridine (DMAP). Under optimized reaction conditions, the synthesis was conducted with FCA, HEA, DMAP, and DCC in a molar ratio of 20:28:20:24 at 0 ℃ and addition of DCC solution in 60~75 min to give AEFC in 75.1% yield and 98% purity.

Key words: esterification reaction, ferrocene derivatives, N, N'-dicyclohexylcarbodiimide/dimethylaminopyridine

中图分类号:

李科, 张教强, 康拴艳, 石绘敏, 周宏玉, 豆荣荣. 二茂铁甲酸(2-丙烯酰氧乙基)酯的合成及优化[J]. 应用化学, 2015, 32(7): 765-770.

LI Ke, ZHANG Jiaoqiang, KANG Shuanyan, SHI Huimin, ZHOU Hongyu, DOU Rongrong. 2-Acryloyloxyethyl Ferrocene Carboxylate:Synthesis and Optimization[J]. Chinese Journal of Applied Chemistry, 2015, 32(7): 765-770.

参考文献

[1]	CAI Yuping,ZHANG Tonglai. Advances on Burning Rate Catalyzer of Composite Solid Propellant at Home and Abroad[J]. J Solid Rocket Technol,2007,30(1):44-47(in Chinese). 柴玉萍,张同来. 国内外复合固体推进剂燃速催化剂研究进展[J]. 固体火箭技术,2007,30(1):44-47.
[2]	Zhong D Y,Blomker T,Wedeking K,et al.Surface-Mounted Molecular Rotors with Variable Functional Groups and Rotation Radii[J]. Nano Lett,2009,9(12):4387-4391.
[3]	Liu L L,He G Q,Wang Y H. RDX/HMX Effects on Combustion Performance of Boron-based Fuel-rich Propellant[J]. Chinese J Energy Mater,2013,21(2):278-283.
[4]	GUO Jiying. Preparation and Applieation Research of New Burning Rate Catalyst[D]. Xi'an:Northwestern Polytechnical University,2006(in Chinese). 国际英. 新燃速催化剂的制备与应用研究[D]. ,西安:西北工业大学,2006.
[5]	Gao J M,Wang L,Yu H J,et al.Recent Research Progress in Burning Rate Catalysts[J]. Propell Explos Pyrot,2011,36(12):404-409.
[6]	GAO Yong,KE Chengfeng,LI Hengdong,et al.Synthesis of Ferrocenyl Dihydropyrazole Derivatives and Their Catalysis on Thermal Decomposition of AP[J]. Chinese J Energy Mater,2011,19(1):19-22(in Chinese). 高勇,柯成锋,李恒东,等. 二茂铁氮杂环衍生物的合成及对高氯酸铵热分解的催化作用[J]. 含能材料,2011,19(1):19-22.
[7]	Zhao H Y,Guo L,Chen S F,et al.Synthesis, Complexation of 1,2,3-(NH)-Triazolylferrocene Derivatives and Their Catalytic Effect on Thermal Decomposition of Ammonium Perchlorate[J]. RSC Adv,2013,33(3):19929-19932.
[8]	GUO Jiying,ZHANG Jiaoqiang,Su Lihong,et al.Improving Synthesis of Hydroxymethyl-Bisferrocene-Propane[J]. J Northwestern Polytech Univ,2006,24(3):350-353(in Chinese). 国际英,张教强,苏力宏,等. 一元羟甲基-双(二茂铁)丙烷的合成与应用研究[J]. 西北工业大学学报,2006,24(3):350-353.
[9]	Tolvanen P,Kilpio T,Maki-Arvela P,et al.Esterification of Fatty Acids and Short-Chain Carboxylic Acids with Stearyl Alcohol and Sterols[J]. ACS Sus Chem Eng,2014,35(2):537-545.
[10]	Guan Q Y, Li C H, Schmidt E J. Preparation and Characterization of Cholic Acid-Derived Antimicrobial Agents with Controlled Stabilitie[J]. Org Lett,2000,2(18):2837-2840.
[11]	DENG Libo. Synthesis of Novel Ferroeene-based Compounds and Their Applications in Anion Recognition[D]. Hangzhou:Zhejiang University,2007(in Chinese). 邓立波. 新型二茂铁基化合物的合成及其在阴离子识别中的应用 [D]. 杭州:浙江大学,2007.
[12]	LIAO Lianan,LI Zhengming,FANG Hongyun,et al.Synthesis and Bioactivity of 5-Ivermectin B1a Esters[J]. Acta Chim Sin,2002,60(3):468-474(in Chinese). 廖联安,李正名,方红云,等. 5-依维菌素B1a酯的合成和生物活性[J]. 化学学报,2002,60(3):468-474.
[13]	LI Qianrong,GU Chengzhi,YIN Hao,et al.Synthesis of Menthyl Esters of N-Benzoxycarbonylaminoacid Using DCC/DMAP[J]. Chinese J Org Chem,2005,25(11):1416-1419(in Chinese). 李前荣,顾承志,尹浩,等. 用DCC/DMAP合成N-苄氧羰基氨基酸薄荷酯[J]. 有机化学,2005,25(11):1416-1419.
[14]	XIAO Anguo. Study on Preparation, Characterization and Properties of Novel Hyperbranched Polyofins[D]. Hangzhou:Zhejiang University,2009(in Chinese). 肖安国. 新型超支化聚烯烃的制备、表征及性能研究[D]. 杭州:浙江大学,2009.
[15]	Vargun E, Usanmaz A. Polymerization of 2-hydroxyethyl Acrylate in Bulk and Solution by Chemical Initiator and by ATRP Method[J]. J Polym Sci Part A:Polym Chem,2005,43(17):3957-3965.
[16]	DU Ping. Supramolecular Hybrid Hydrogels and Macromolecular Self-Assembly Based on Eleetrochemical Sensitive Inclusion Complexation Interactions[D]. Shanghai:Fudan University,2011(in Chinese). 杜萍. 基于具有电化学响应性的包结络合作用的超分子杂化水凝胶及大分子自组装 [D]. 上海:复旦大学,2011.
[17]	Zhai S J,Sahng J,Yang D,et al.Successive SET-LRP and ATRP Synthesis of Ferrocene-Based PPEGMEA-g-PAEFC Well-defined Amphiphilic Graft Copolymer[J]. J Polym Sci Part A:Polym Chem,2012,50(6):811-820.
[18]	Emanuel B,Contreras C,Dake G R. DMAP Promoted Tandem Addition Reactions Forming Substituted Tetrahydroxanthones[J]. Org Lett,2014,16(7):1642-1645.