Home

Citation: XU Haiyun, FENG Cuilan. Improved Synthesis of 2-Ethoxycarbonyl-3-trifluoromethyl-4-methyl-pyrrole Based on Barton-Zard Reaction and Its Porphyrin Derivative[J]. Chinese Journal of Applied Chemistry, ;2011, 28(7): 739-746. doi: 10.3724/SP.J.1095.2011.00641 shu

Improved Synthesis of 2-Ethoxycarbonyl-3-trifluoromethyl-4-methyl-pyrrole Based on Barton-Zard Reaction and Its Porphyrin Derivative

XU Haiyun ^, ,
FENG Cuilan

1.
Department of Chemistry, Shangqiu Normal College, Shangqiu 476000

Corresponding author: XU Haiyun,
Received Date: 10 November 2010
Available Online: 14 January 2011

In the synthesis of pyrrole 2-ethoxycarbonyl-3-trifluoromethyl-4-methylpyrrole(1) from 2-acetoxy-3-nitro-1,1,1-trifluorobutane(1b) and ethyl isocyanoacetate according to the Barton-Zard reaction,the organic base 1,8-diazabicyclo undec-7-ene(DBU) and the solvent tetrahydrofuran(THF) were replaced with K₂CO₃ and ethanol,respectively.The improved Barton-Zard procedure had advantages such as less expensive and safe reagents,higher yield and more convenient operation procedures than original Barton-Zard method.Moreover,the preparation of the intermediate 1b from compound 1a by acetylation reaction was carried out by employing acetyl chloride in boiling toluene solution instead of acetic anhydride and the catalyst concentrated sulfuric acid.Its optimum reaction conditions were that the molar ratio of acetyl chloride to compound 1a and reaction time were set as 1.2:1 and 3~3.5 h,respectively.After treatment of compound 1 with excess LiAlH₄ at low temperature,it affords the crude product α-(hydroxymethyl)-3-trifluoromethyl-4-methylpyrrole(1c),which immediately reacted via a tetramerization in the presence of the catalyst BF₃·OEt₂ and in CHCl₃,followed by oxidation of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone(DDQ) to provide the corresponding trifluoromethylated porphyrin derivative 2.The results indicate that using boron trifluoride diethyl etherate(BF₃·OEt₂) as catalyst instead of p-toluenesulphonic acid(p-TsOH) in the synthesis of compound 2 from compound 1c can significantly increases the yield of product 2 up to 50% from 14%.
1. [1]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
2. [2]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
3. [3]
  Fengmiao Yu , Yang Sheng , Chanyue Li , Bao Li . The Three Lives of Aspirin. University Chemistry, 2024, 39(9): 115-121. doi: 10.12461/PKU.DXHX202402033
4. [4]
  Jiaqi AN , Yunle LIU , Jianxuan SHANG , Yan GUO , Ce LIU , Fanlong ZENG , Anyang LI , Wenyuan WANG . Reactivity of extremely bulky silylaminogermylene chloride and bonding analysis of a cubic tetragermylene. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1511-1518. doi: 10.11862/CJIC.20240072
5. [5]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191
6. [6]
  Jinfeng Chu , Yicheng Wang , Ji Qi , Yulin Liu , Yan Li , Lan Jin , Lei He , Yufei Song . Comprehensive Chemical Experiment Design: Convenient Preparation and Characterization of an Oxygen-Bridged Trinuclear Iron(III) Complex. University Chemistry, 2024, 39(7): 299-306. doi: 10.3866/PKU.DXHX202310105
7. [7]
  Hailang JIA , Hongcheng LI , Pengcheng JI , Yang TENG , Mingyun GUAN . Preparation and performance of N-doped carbon nanotubes composite Co₃O₄ as oxygen reduction reaction electrocatalysts. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 693-700. doi: 10.11862/CJIC.20230402
8. [8]
  Tingting Yu , Si Chen , Lianglong Sun , Tongtong Shi , Kai Sun , Xin Wang . Comprehensive Experimental Design for the Photochemical Synthesis, Analysis, and Characterization of Difluoropyrroles. University Chemistry, 2024, 39(11): 196-203. doi: 10.3866/PKU.DXHX202401022
9. [9]
  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
10. [10]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响. Acta Physico-Chimica Sinica, 2025, 41(1): 2309002-. doi: 10.3866/PKU.WHXB202309002
11. [11]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
12. [12]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
13. [13]
  Yang WANG , Xiaoqin ZHENG , Yang LIU , Kai ZHANG , Jiahui KOU , Linbing SUN . Mn single-atom catalysts based on confined space: Fabrication and the electrocatalytic oxygen evolution reaction performance. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2175-2185. doi: 10.11862/CJIC.20240165
14. [14]
  Yuanyin Cui , Jinfeng Zhang , Hailiang Chu , Lixian Sun , Kai Dai . Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2405016-. doi: 10.3866/PKU.WHXB202405016
15. [15]
  Dan Li , Hui Xin , Xiaofeng Yi . Comprehensive Experimental Design on Ni-based Catalyst for Biofuel Production. University Chemistry, 2024, 39(8): 204-211. doi: 10.3866/PKU.DXHX202312046
16. [16]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
17. [17]
  Qilu DU , Li ZHAO , Peng NIE , Bo XU . Synthesis and characterization of osmium-germyl complexes stabilized by triphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1088-1094. doi: 10.11862/CJIC.20240006
18. [18]
  Hongwei Ma , Hui Li . Three Methods for Structure Determination from Powder Diffraction Data. University Chemistry, 2024, 39(3): 94-102. doi: 10.3866/PKU.DXHX202310035
19. [19]
  Liangyu Gong , Jie Wang , Fengyu Du , Lubin Xu , Chuanli Ma , Shihai Yan , Zhuwei Song , Fuheng Liu , Xiuzhong Wang . Construction and Practice of “One-Point, Two-Lines and Three-Sides” Innovative Experimental Platform. University Chemistry, 2024, 39(4): 26-32. doi: 10.3866/PKU.DXHX202308023
20. [20]
  Jin Yan , Chengxia Tong , Yajie Li , Yue Gu , Xuejian Qu , Shigang Wei , Wanchun Zhu , Yupeng Guo . Construction of a “Dual Support, Triple Integration” Chemical Safety Practical Education System. University Chemistry, 2024, 39(7): 69-75. doi: 10.12461/PKU.DXHX202405008

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(404)
HTML views(45)

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

Address：Zhongguancun North First Street 2,100190 Beijing, PR China Tel: +86-010-82449177-888

DownLoad: Full-Size Img PowerPoint

Return