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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%.
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