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Brominated Trihalomethylenones as Versatile Precursors to 3-Ethoxy, -Formyl, -Azidomethyl, -Triazolyl, and 3-Aminomethyl Pyrazoles

  作者 MARTINS MARCOS A P; SINHORIN ADILSON P; FRIZZO CLARISSA P; BURIOL LILIAN; SCAPIN ELISANDRA; ZANATTA NILO; BONACORSO HELIO G  
  选自 期刊  Journal of Heterocyclic Chemistry;  卷期  2013年50-1;  页码  71-77  
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[摘要]5-Bromo[5,5-dibromo]-1,1,1-trihalo-4-methoxy-3-penten[hexen]-2-ones are explored as precursors to the synthesis of 3-ethoxymethyl-5-trifluoromethyl-1H-pyrazoles from a cyclocondensation reaction with hydrazine monohydrate in ethanol. 3-Ethoxymethyl-carboxyethyl ester pyrazoles were formed as a result of a substitution reaction of bromine and chlorine by ethanol. The dibrominated precursor furnished 3-acetal-pyrazole that was easily hydrolyzed to formyl group. In addition, brominated precursors were used in a nucleophilic substitution reaction with sodium azide to synthesize the 3-azidomethyl-5-ethoxycarbonyl-1H-pyrazole from the reaction with hydrazine monohydrate. These products were submitted to a cycloaddition reaction with phenyl acetylene furnishing the 3-[4(5)-phenyl-1,2,3-triazolyl]5- ethoxycarbonyl-1H-pyrazoles and to reduction conditions resulting in 3-aminomethyl-1H-pyrazole-5-carboxyethyl ester. The products were obtained by a simple methodology and in moderate to good yields.

 
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