Synthesis of some novel α-cyanoketene-n, s-acetals derived from secondary aliphatic amines and their use in pyrazole synthesis

New α-cyanoketene-N,S-acetals 2(a–g) and β-dialkylamine-α-cyanoacrylates 3(g–i) were synthesized in good to excellent yields by the reaction of ethyl 2-cyano-3,3-bis(methylthio)acrylate 1 with secondary aliphatic amines (i.e., N-methylalkyl- and N-ethylalkylamines), and pyrrolidine, in the presence of triethylamine, under reflux in ethanol, for 1–16 h, depending on the amine used. Five N-methylalkyl amines and pyrrolidine yielded exclusively mono-substituted N,S-acetals 2(a–f) in good yields. On the other hand, N-ethylbenzylamine gave a mixture of monosubstituted products including N,S-acetal 2g in 35% yield and the unexpected product ethyl 3-[benzyl(ethyl)amino]-2-cyanoacrylate 3g in 50% yield. N-Ethylcyclohexylamine and N-ethylbutylamine did not produce N,S-acetals and gave only the unexpected products ethyl 2-cyano-3-[cyclohexyl(ethyl)amino]acrylate 3h and ethyl 3-[butyl(ethyl)amino]-2-cyanoacrylate 3i in good yields. The α-cyanoketene-N,S-acetals 2(a–f), 2j, and 2k underwent cyclization with the binucleophile hydrazine in ethanol under reflux to afford substituted pyrazoles 4(a–f), 4j, and 4k in good yields

Synthesis and Antibacterial Activity of Thiophenes

2-[Bis(methylthio)methylene]propanedinitrile 1a reacted in one-pot successively with piperidine, sodium sulfide, chloroacetonitrile, and potassium carbonate to afford 3-amino-5-(1-piperidinyl)-2,4-thiophenedicarbonitrile 2a. Similar reaction using the last three reagents with ethyl 2-cyano-3,3-bis(methylthio)acrylate 1b produced ethyl 4-amino-5-cyano-2-(methylthio)thiophene-3-carboxylate 2b. The synthesized compounds were characterized by using FT-IR, 1H-NMR, 13C-NMR, and mass spectral data. Antibacterial activities of the synthesized compounds are also reported

3-Amino-5-(piperidin-1-yl)thio­phene-2,4-dicarbonitrile

In the title compound, C11H12N4S, the thio­phene ring is roughly planar, with a maximum deviation of 0.012 (1) Å for the S atom, and makes a dihedral angle of 7.89 (8)° with the mean plane of the piperidine ring, which is in a chair conformation. The crystal packing is stabilized by pairs of centrosymmetric inter­molecular N—H⋯N hydrogen bonds, which results in the formation of a step-wise chain parallel to [10]

Synthesis, antibacterial activity and cytotoxicity of new fused pyrazolo[1,5-a]pyrimidine and pyrazolo[5,1-c][1,2,4]triazine derivatives from new 5-aminopyrazoles

New 5-aminopyrazoles 2a–c were prepared in high yields from the reaction of known α,α-dicyanoketene-N,S-acetals 1a–c with hydrazine hydrate under reflux in ethanol. These compounds were utilized as intermediates to synthesize pyrazolo[1,5-a]-pyrimidines 3a–c, 4a–d, 5a–c, and 6a–c, as well as pyrazolo[5,1-c][1,2,4]triazines 7a–c and 8a–c, by the reaction of 2-[bis(methylthio)methylene]malononitrile, α,α-dicyanoketene-N,S-acetals 1a–b, acetylacetone, acetoacetanilide as well as acetylacetone, and malononitrile, respectively. Furthermore, cyclization of 2a–c with pentan-2,5-dione yielded the corresponding 5-pyrrolylpyrazoles 9a–c. Moreover, fusion of 2a–c with acetic anhydride resulted in the corresponding 1-acetyl-1H-pyrazoles 10a–c. The antibacterial activity and cytotoxicity against Vero cells of several selected compounds are also reported

3-Oxo-5-(piperidin-1-yl)-2,3-dihydro-1H-pyrazole-4-carbonitrile

In the title compound, C9H12N4O, the piperidine ring adopts a chair conformation and makes a dihedral angle of 42.49 (11)° with the approximately planar pyrazole moiety [maximum deviation = 0.038 (2) Å]. In the crystal, N—H⋯O and N—H⋯N hydrogen bonds and a weak C—H⋯O inter­action link the mol­ecules into sheets lying parallel to (110)