New "green" approaches to the synthesis of pyrazole derivatives.
A novel approach to the synthesis of pyrazole derivatives from tosylhydrazones of alpha,beta-unsaturated carbonyl compounds possessing a beta-hydrogen is proposed, exploiting microwave (MW) activation coupled with solvent free reaction conditions. The cycloaddition was studied on three ketones (trans-4-phenyl-3-buten-2-one, beta-ionone and trans-chalcone). The corresponding 3,5-disubstituted-1H-pyrazoles were obtained in high yields and after short reaction times. In order to simplify and point out the green chemistry features of the method, a further improvement was achieved under the same catalytic conditions with a "one pot" synthesis of these heterocyclic compounds, starting directly from their carbonyl precursors via tosylhydrazones generated in situ. For an exhaustive study, the dielectric properties of the solid reaction mixtures were also measured, in order to obtain input data for the numerical simulation of their heating behaviour in the single mode MW cavity which was used for experimental work. In order to supply a valid methodology and tool for measuring the environmental impact, a comparative study between the synthetic route proposed and the classical synthetic route has been carried out.
Corradi
Anna
A
Dipartimento di Ingegneria dei Materiali e dell'Ambiente, Università degli Studi di Modena e Reggio Emilia, Via Vignolese, 905, 41100 Modena, Italy. anna@unimore.it <anna@unimore.it>
Leonelli
Cristina
C
Rizzuti
Antonino
A
Rosa
Roberto
R
Veronesi
Paolo
P
Grandi
Romano
R
Baldassari
Sara
S
Villa
Carla
C
D002384:Catalysis; D006835:Hydrazones / Q000737:chemistry; D008872:Microwaves; D008956:Models, Chemical; D011720:Pyrazoles / Q000138:chemical synthesis* / Q000737:chemistry; D012997:Solvents / Q000737:chemistry; D013329:Structure-Activity Relationship; D013696:Temperature; D013997:Time Factors
D006835:Hydrazones; D011720:Pyrazoles; D012997:Solvents; C031280:pyrazole