Citation: WU Jianhong, CHEN Dongyin, LI Fei. Synthesis of tert-Butyl Ethers and tert-Butyl Esters Catalyzed by Acid-treated Montmorillonite Supported Zinc Chloride[J]. Chinese Journal of Applied Chemistry, ;2016, 33(5): 565-570. doi: 10.11944/j.issn.1000-0518.2016.05.150318 shu

Synthesis of tert-Butyl Ethers and tert-Butyl Esters Catalyzed by Acid-treated Montmorillonite Supported Zinc Chloride

1.
School of Pharmacy, Nanjing Medical University, Nanjing 211166, China

Corresponding author: LI Fei,
Received Date: 31 August 2015
Available Online: 10 December 2015
Fund Project:

With acid-treated montmorillonite supported zinc chloride(H-mont/ZnCl₂) as the catalyst, phenols, alcohols, and carboxylic acid were reacted with di-tert-butyl dicarbonate to give tert-butyl ether and tert-butyl ester derivatives at 120 ℃ in sealed tube with yields ranging from 61% to 75%, which is simple and environmentally friendly. All the compounds synthesized were confirmed by ¹H NMR and ESI-MS. The effect of solvent, temperature, metal ion and some other factors to the reaction were investigated. A possible mechanism for this reaction was proposed. Provided a new method for this type of synthesis in the future.
- acid-treated montmorillonite,
- zinc chloride,
- tert-butyl ethers,
- tert-butyl esters,
- organic synthesis
1. [1]
  [1] SONG Wen. The Production and Development of Methyl Tert Butyl Ether[J]. Fine Chem Ind Raw Mater Intermed,2011,2(2):33-38.(in Chinese).松文. 甲基叔丁基醚生产与发展趋势[J]. 精细化工原料及中间体,2011,2(2):33-38.
2. [2]
  [2] YANG Xianjian,TANG Ji,FEI Zhaoyang,et al. The Dynamics of Synthesis Tert Butyl Acrylate by Using Acrylic Acid and Isobutene Catalyzed[J]. Chem React Eng Technol,2015,31(1):63-68.(in Chinese).杨仙健,汤吉,费兆阳,等. 丙烯酸与异丁烯酯化合成丙烯酸叔丁酯动力学[J]. 化学反应工程与工艺,2015,31(1):63-68.
3. [3]
  [3] LIN Ruan,ZHEN Gengxiu,TIAN Zhongzhen,et al. Bromoacetic Acid and Isobutene Synthesis of Tert Butyl 2-Bromoacetate[J]. J Univ Jinan(Sci Technol),2013,2(2):173-176.(in Chinese).林沅,郑庚修,田忠贞,等. 溴乙酸和异丁烯合成溴乙酸叔丁酯[J]. 济南大学学报(自然科学版),2013,2(2):173-176.
4. [4]
  [4] YAN Yinmei,SUN Binbin. Progress in Synthesis of Gasoline Antiknock Additives Methyl tert-Butyl Ether[J]. Appl Chem Eng,2011,9(40):1645-1647(in Chinese).闫银梅,孙宾宾. 汽油抗爆剂甲基叔丁基醚合成研究进展[J]. 应用化工,2011,9(40):1645-1647.
5. [5]
  [5] LI Chunjing,SHEN Jian. Synthesis of Ethyl tert-Butyl Ether by Niobic Acid[J]. Chem Ind Eng,2009,26(1):32-35(in Chinese).李春晶,沈健. 酸处理的铌酸催化合成乙基叔丁基醚[J]. 化学工业与工程,2009,26(1):32-35.
6. [6]
  [6] LIN Yingming,LIU Suyun. Synthesis of t-Butyl 4'-Bromomethylbiphenyl-2-carboxylate[J]. Chinese J Pharm Ind,2006,37(5):304-305(in Chinese).林迎明,刘素云. 4'-溴甲基-2-联苯甲酸叔丁酯的合成[J]. 中国医药工业杂志,2006,37(5):304-305.
7. [7]
  [7] HAO Yongbing,ZHU Zhenfu,HU Xianming. Simple Synthesis of Glycine tert-Butyl Ester[J]. Guangdong Chem Ind,2010,37(3):134-134(in Chinese).郝永兵,祝振福,胡先明. 甘氨酸叔丁酯的简便合成[J]. 广东化工,2010,37(3):134-134.
8. [8]
  [8] Kaneda K. Cation-exchanged Montmorillonites as Solid Acid Catalysts for Organic Synthesis[J]. Synlett,2007,38(28):999-1015.
9. [9]
  [9] Motokura K,Fujita N,Mori K,et al. Brønsted Acid Mediated Heterogeneous Addition Reaction of 1,3-Dicarbonyl Compounds to Alkenes and Alcohols[J]. Angew Chem Int Ed,2006,45(16):2605-2609.
10. [10]
  [10] Harrane A,Meghabar R,Belbachir M. Kinetics of the Ring Opening Polymerization of ε-Caprolactone Catalysed by a Proton Exchanged Montmorillonite Clay[J]. React Funct Polym,2006,66(12):1696-1702.
11. [11]
  [11] Motokura K,Nakagiri N,Mizugaki T,et al. Nucleophilic Substitution Reactions of Alcohols with Use of Montmorillonite Catalysts as Solid Brønsted Acids[J]. J Org Chem,2007,72(16):6006-6015.
12. [12]
  [12] Chen D Y,Xu C,Deng J,et al. Proton-exchanged Montmorillonite-mediated Reactions of p-Methoxybenzyl Esters and Ethers[J]. Tetrahedron,2014,70(11):1975-1983.
13. [13]
  [13] Ken Motokura,Toshihide Baba. An Atom-efficient Synthetic Method: Carbosilylations of Alkenes, Alkynes, and Cyclic Acetals Using Lewis and Br nsted Acid Catalysts[J]. Green Chem,2012,14(3):565-579.
1. [1]
  Fengxiao Wang , Zhiwei Miao , Yaofeng Yuan . 有机磷化学与化学教学. University Chemistry, 2025, 40(8): 158-168. doi: 10.12461/PKU.DXHX202410077
2. [2]
  Yongjian Zhang , Fangling Gao , Hong Yan , Keyin Ye . Electrochemical Transformation of Organosulfur Compounds. University Chemistry, 2025, 40(5): 311-317. doi: 10.12461/PKU.DXHX202407035
3. [3]
  Aidang Lu , Yunting Liu , Yanjun Jiang . Comprehensive Organic Chemistry Experiment: Synthesis and Characterization of Triazolopyrimidine Compounds. University Chemistry, 2024, 39(8): 241-246. doi: 10.3866/PKU.DXHX202401029
4. [4]
  Shuhui Li , Rongxiuyuan Huang , Yingming Pan . Electrochemical Synthesis of 2,5-Diphenyl-1,3,4-Oxadiazole: A Recommended Comprehensive Organic Chemistry Experiment. University Chemistry, 2025, 40(5): 357-365. doi: 10.12461/PKU.DXHX202407028
5. [5]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, 2024, 39(10): 408-415. doi: 10.12461/PKU.DXHX202403024
6. [6]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003
7. [7]
  Jinghua Wang , Yanxin Yu , Yanbiao Ren , Yesheng Wang . Integration of Science and Education: Investigation of Tributyl Citrate Synthesis under the Promotion of Hydrate Molten Salts for Research and Innovation Training. University Chemistry, 2024, 39(11): 232-240. doi: 10.3866/PKU.DXHX202402057
8. [8]
  Jiaojiao Yu , Bo Sun , Na Li , Cong Wen , Wei Li . Improvement of Classical Organic Experiment Based on the “Reverse-Step Optimization Method”: Taking Synthesis of Ethyl Acetate as an Example. University Chemistry, 2025, 40(3): 333-341. doi: 10.12461/PKU.DXHX202405177
9. [9]
  Shengbiao Zheng , Liang Li , Nini Zhang , Ruimin Bao , Ruizhang Hu , Jing Tang . Metal-Organic Framework-Derived Materials Modified Electrode for Electrochemical Sensing of Tert-Butylhydroquinone: A Recommended Comprehensive Chemistry Experiment for Translating Research Results. University Chemistry, 2024, 39(7): 345-353. doi: 10.3866/PKU.DXHX202310096
10. [10]
  Hong CAI , Jiewen WU , Jingyun LI , Lixian CHEN , Siqi XIAO , Dan LI . Synthesis of a zinc-cobalt bimetallic adenine metal-organic framework for the recognition of sulfur-containing amino acids. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 114-122. doi: 10.11862/CJIC.20240382
11. [11]
  Aiyi Xin , Jiawei Li , Xinyang Ran , Chuanjiang Fu , Zhiguo Wang . Collaborative Science and Education Based Experimental Design in Organic Chemistry: A Case Study of the Nucleophilic Substitution Reaction of 2-Hydroxymethyl-4,6-Di-Tert-Butylphenol. University Chemistry, 2025, 40(5): 366-375. doi: 10.12461/PKU.DXHX202407031
12. [12]
  Ping Song , Nan Zhang , Jie Wang , Rui Yan , Zhiqiang Wang , Yingxue Jin . Experimental Teaching Design on Synthesis and Antitumor Activity Study of Cu-Pyropheophorbide-a Methyl Ester. University Chemistry, 2024, 39(6): 278-286. doi: 10.3866/PKU.DXHX202310087
13. [13]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
14. [14]
  Qiuyang LUO , Xiaoning TANG , Shu XIA , Junnan LIU , Xingfu YANG , Jie LEI . Application of a densely hydrophobic copper metal layer in-situ prepared with organic solvents for protecting zinc anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1243-1253. doi: 10.11862/CJIC.20240110
15. [15]
  Feng Sha , Xinyan Wu , Ping Hu , Wenqing Zhang , Xiaoyang Luan , Yunfei Ma . Design of Course Ideology and Politics for the Comprehensive Organic Synthesis Experiment of Benzocaine. University Chemistry, 2024, 39(2): 110-115. doi: 10.3866/PKU.DXHX202307082
16. [16]
  Xinyu Zhu , Meili Pang . Application of Functional Group Addition Strategy in Organic Synthesis. University Chemistry, 2024, 39(3): 218-230. doi: 10.3866/PKU.DXHX202308106
17. [17]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
18. [18]
  Lewang Yuan , Yaoyao Peng , Zong-Jie Guan , Yu Fang . Insights into the development of 2D covalent organic frameworks as photocatalysts in organic synthesis. Acta Physico-Chimica Sinica, 2025, 41(8): 100086-0. doi: 10.1016/j.actphy.2025.100086
19. [19]
  Hui-Ying Chen , Hao-Lin Zhu , Pei-Qin Liao , Xiao-Ming Chen . Integration of Ru(Ⅱ)-Bipyridyl and Zinc(Ⅱ)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2306046-0. doi: 10.3866/PKU.WHXB202306046
20. [20]
  Liang TANG , Jingfei NI , Kang XIAO , Xiangmei LIU . Synthesis and X-ray imaging application of lanthanide-organic complex-based scintillators. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1892-1902. doi: 10.11862/CJIC.20240139

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(579)
HTML views(42)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142