Reaction of β-alkoxyvinyl halomethyl ketones with cyanoacetohydrazide (original) (raw)

Reaction of β-alkoxyvinyl halomethyl ketones with cyanoacetohydrazide

Journal of The Brazilian Chemical Society, 2008

The synthesis of thirteen 1-cyanoacetyl-5-hydroxy-5-halomethyl-1H-4,5-dihydropyrazoles from the reaction of 4-alkoxy-3-alken-2-ones [R3C(O)C(R2)=C(R1)(OR), where R3 = CF3, CCl3, CHCl2, CO2Et; R2 = H, Me; R1 = H, Me, Et, Pr, Pentyl, c-Hexyl, Ph, and R = Me, Et] with cyanoacetohydrazide is reported. In order to show the versatility of using the 1-cyanoacetyl-substituted pyrazoles as important building blocks in organic synthesis, some attempts to obtain pyrazole derivatives also are described.

Synthesis of Some Pyrazole Derivatives from 5-Chloro-and 5-Azido-1,3-diphenyl-1H-pyrazole-4-carbaldehydes

N-[(5-Azido-1,3-diphenyl-1H-pyrazole-4-yl)methylene]-N-arylamines (4a-c) and N-[(5-Substituted-1,3-diphenyl-1H-pyrazole-4-yl)methylene]hydrazides (5a-e) were prepared from 5-azido-1,3-diphenyl-1H-pyrazole-4-carbaldehyde (3) and 5-chloro-1,3diphenyl-1H-pyrazole-4-carbaldehyde (2), respectively. Thermolysis of (4a-c) and (5d-e) afforded 5-arylamino-1,3-diphenyl-1H-pyrazol-4-carbonitriles (8a-c) and N-(4-cyano-1,3diphenyl-1H-pyrazol-5-yl)hydrazides (13a,b), respectively. N-[2-(5-Chloro-1,3-diphenyl-1H-pyrazol-4-yl)-4-oxo-thiazolidin-3-yl]amides (14a,b) and 3-acetyl-2-(5-chloro-1,3diphenyl-1H-pyrazol-4-yl)-5-aryl-2,3-dihydro-1,3,4-oxadiazoles (15a,b) were obtained from N-[(5-chloro-1,3-diphenyl-1H-pyrazole-4-yl)methylene]hydrazides (5a,b). 5-Azido-1,3-diphenyl-1H-pyrazol-4-carbaldehyde (3) gave unexpectedly 1-(1,3-diphenyl-1,6dihydropyrrolo-2,3-c]pyrazol-5-yl)ethan-1-one (17).

Solvent-free one-pot cyclization and acetylation of chalcones: Synthesis of some 1-acetyl pyrazoles and spectral correlations of 1-(3-(3,4-dimethylphenyl)-5-(substituted phenyl)-4,5-dihydro-1H-pyrazole-1-yl) ethanones

2014

One-pot synthesis of some 1 N-acetyl pyrazoles including 1-(3-(3,4-dimethylphenyl)-5-(substituted phenyl)-4,5-dihydro-1 H-pyrazole-1-yl) ethanones has been achieved via solvent-free microwave irradiation using substituted chalcones, hydrazine hydrate and acetic anhydride in the presence of catalytic amount of fly-ash: PTS catalyst. The yield of these 1 N-acetyl pyrazole derivatives is more than 75%. The synthesized 1 N-acetyl pyrazoline derivatives were characterized by their physical constants and spectral data. The infrared spectral mC‚N and C‚O (cm À1) frequencies, NMR chemical shifts (d, ppm) of H a , H b , H c , CH 3 protons, C‚N, C‚O and CH 3 carbons of 1-(3-(3,4-dimethylphenyl)-5-(substituted phenyl)-4,5-dihydro-1 H-pyrazole-1-yl) ethanones have been assigned and correlated with Hammett substituent constants and Swain-Lupton's parameters using single and multi-regression analysis. From the results of statistical analyses, the effect of substituents on the above group frequencies and chemical shifts of the acetylated pyrazoles were discussed.

Use of transesterified 1,3-diketoesters in the synthesis of trisubstituted pyrazoles and their biological screening

Bulletin of the Chemical Society of Ethiopia, 2012

Starting from 2-acetylbenzofuran derivatives 1a-d, methyl/ethyl 4-substituted/unsubstituted benzofuran-2-yl)-2,4-dioxobutanoate 2a-d and 3a-d have been synthesized by Claisen's condensation reaction with diethyloxalate. The transesterified product, 1,3-diketoester 2a-d on condensation with phenyl hydrazine undergo cyclization to afford the corresponding methyl 5-(substituted/unsubstituted benzofuran-2-yl)-1-phenyl-1H-pyrazole-3-carboxylate 4a-d, which upon further condensation with hydrazine hydrate yielded 5-(substituted/unsubstituted benzofuran-2-yl)-1-phenyl-1H-pyrazole-3-carbohydrazide 5a-d. The structures of the newly synthesized compounds 2a-d, 3a-d, 4a-d and 5a-d were characterized by their elemental analysis and spectral studies such as IR, 1 H NMR, 13 C NMR and MS. All the synthesized compounds were screened for their antimicrobial activity. Most of the synthesized compounds showed high sensitivity against the selected bacteria and fungi at various concentrations.