Key Intermediates: A Simple and Highly Selective Synthesis of 5-<i>Amino</i>-1-<i>aryl</i>-1<i>H</i>-<i>pyrazole</i>-4-<i>carbonitriles</i> for Applications in the Crop Protection — Oak Academic Publishing
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Key Intermediates: A Simple and Highly Selective Synthesis of 5-<i>Amino</i>-1-<i>aryl</i>-1<i>H</i>-<i>pyrazole</i>-4-<i>carbonitriles</i> for Applications in the Crop Protection
Laboratorio de Química Aplicada (LAQUIMAP), Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral (UNL), Santa Fe, Argentina
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Laboratorio de Química Aplicada (LAQUIMAP), Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral (UNL), Santa Fe, Argentina
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Laboratorio de Química Aplicada (LAQUIMAP), Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral (UNL), Santa Fe, Argentina
1 Laboratorio de Química Aplicada (LAQUIMAP), Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral (UNL), Santa Fe, Argentina
2 Laboratorio de Química Aplicada (LAQUIMAP), Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral (UNL), Santa Fe, Argentina
3 Laboratorio de Química Aplicada (LAQUIMAP), Facultad de Bioquímica y Ciencias Biológicas, Universidad Nacional del Litoral (UNL), Santa Fe, Argentina
A series of six pyrazoles was synthesized by Michael-type addition reaction. The molecules 5- amino -1- aryl -1H- pyrazole -4- carbonitrile (3a-f) were synthesized from (ethoxymethylene)malo-nonitrile (1) and fluorinated and non-fluorinated aryl hydrazines (2a-f) using ethanol and fluorinated ethanol as solvents at reflux. An excellent regio-selectivity was found when pyrazole derivatives were formed as an exclusive product. No other regioisomer or uncyclised hydrazide was observed. Their structures were confirmed by spectroscopy data ( 1 H, 13 C, 19 F, COSY (correlation spectroscopy), HSQC (heteronuclear single-quantum correlation spectroscopy) and HMBC (heteronuclear multiple-bond correlation spectroscopy); MS (mass-spectrometry). The yields ranged from good to excellent (47% - 93%) under mild reaction conditions. It would indicate a high selectivity in the one-step work procedure. These products (3a-f) and derivatives have a potential academic and industrial use as key intermediates, in special, for application in crop protection.
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