In the title solvate, C29H21ClN2O2·C3H6O, a prop-2-en-1-one bridge links two quinolinyl residues; the latter are almost perpendicular [dihedral angle = 78.27 (6)°]. The dihedral angle between the quinonyl ring system and its pendant phenyl group is 59.78 (8)°. A small twist in the bridging prop-2-en-1-one group is noted [O=C—C=C torsion angle = −10.6 (3)°]. In the crystal, a three-dimensional architecture arises as a result of C—H⋯O and π–π stacking [centroid–centroid distances = 3.5504 (12)–3.6623 (12) Å].
In the title compound, C29H21ClN2O, there is a twist in the bridging prop-2-en-1-one group [C=C—C=O torsion angle = 22.7 (2)°]. The quinolinyl residues form a dihedral angle of 86.92 (4)°, indicating an almost perpendicular relationship. In the crystal, supramolecular layers in the bc plane are stabilized by C—H⋯π and π–π interactions [centroid–centroid distance = 3.4947 (7) Å].
The molecule of the title compound, C24H19ClN2O2, is bent, with the dihedral angle between the terminal quinoline ring systems being 63.30 (5)°. The quinolinyl residues are connected by an almost planar prop-2-en-1-one bridge (r.m.s. deviation = 0.022 Å), with the dihedral angles between this plane and the appended quinolinyl residues being 75.86 (7) and 38.54 (7)°. The C atom of the methoxy group is close to coplanar with its attached ring [deviation = 0.116 (2) Å]. In the crystal, a three-dimensional architecture is constructed by methyl–carbonyl C—H⋯O interactions and π–π interactions between centrosymmetrically related quinolinyl residues [centroid-to-centroid separations 3.5341 (10) and 3.8719 (9) Å].
In the molecule of the title compound, C24H19ClN2O, the terminal quinolinyl residues are close to perpendicular to each other [dihedral angle 83.72 (4)°]. The quinolinyl residues are connected by and inclined to the prop-2-en-1-one bridge, with the Car—Car—C—C (ar = aromatic) torsion angles being 71.01 (17) and 20.6 (2)°. The crystal structure features phenyl–carbonyl C—H⋯O interactions and π–π interactions between centrosymmetrically related quinolinyl residues [3.5341 (10) and 3.8719 (9) Å], which together lead to a three-dimensional architecture.
Pyrazolones are traditionally synthesized by the reaction of β-keto esters with hydrazine and its derivatives. There are methods to synthesize β-keto esters from esters and aldehydes, but these methods have main limitation in varying the substituents. Often, there are a number of methods such as acylation of enolates in which a chelating effect has been employed to lock the enolate anion using lithium and magnesium salts; however, these methods suffer from inconsistent yields in the case of aliphatic acylation. There are methods to synthesize β-keto esters from ketones like caboxylation of ketone enolates using carbon dioxide and carbon monoxide sources in the presence of palladium or transition metal catalysts. Currently, the most general and simple method to synthesize β-keto ester is the reaction of dimethyl or ethyl carbonate with ketone in the presence of strong bases which also requires long reaction time, use of excessive amount of reagent and inconsistent yield. These factors lead us to develop a simple method to synthesize β-keto esters by changing the base and reagent.
A series of β-keto esters were synthesized from ketones and ethyl chloroformate in the presence of base which in turn are converted to pyrazolones and then subjected to cytotoxicity studies towards various cancer cell lines and antimicrobial activity studies towards various bacterial and fungal strains.
The β-keto esters from ethyl chloroformate was successfully attempted, and the developed method is simple, fast and applicable to the ketones having the alkyl halogens, protecting groups like Boc and Cbz that were tolerated and proved to be useful in the synthesis of fused bicyclic and tricyclic pyrazolones efficiently using cyclic ketones. Since this method is successful for different ketones, it can be useful for the synthesis of pharmaceutically important pyrazolones also. The synthesized pyrazolones were subjected to antimicrobial, docking and cytotoxicity assay against ACHN (human renal cell carcinoma), Panc-1 (human pancreatic adenocarcinoma) and HCT-116 (human colon cancer) cell line, and lead molecules have been identified. Some of the compounds are found to have promising activity against different bacterial and fungal strains tested.
β-keto esters; Ethyl chloroformate; Pyrazolones; Efficient synthesis; Anti-bacterial activity; Fungicidal activity; Cytotoxicity studies
In the title compound, C20H22O5, the tetrahydropyran, cyclohexene and cyclohexane rings of the xanthene ring system adopt half-chair, half-boat and chair conformations, respectively. The mean plane of the four roughly planar atoms of the tetrahydropyran ring (r.m.s. deviation = 0.111 Å) forms a dihedral angle of 82.91 (4)° with the methoxybenzene group. In the crystal, molecules are linked via O—H⋯O and C—H⋯O hydrogen bonds into sheets lying parallel to the ac plane. The crystal is further consolidated by weak C—H⋯π interactions.
In the title compound, C19H20F6N2O8, the ethoxy and ethyl groups are disordered over two sets of sites, with occupancy ratios of 0.212 (18):0.788 (18) and 0.746 (6):0.254 (6), respectively. The piperidine ring adopts a chair conformation. In the molecule, intramolecular O—H⋯O hydrogen bonds form two S(6) ring motifs. In the crystal, molecules are linked via O—H⋯O and C—H⋯O hydrogen bonds, forming dimers.
The asymmetric unit of the title compound, C25H35NO6, contains two independent molecules. In each molecule, the 1,4-dihydropyridine ring adopts a flattened boat conformation. The dihedral angles between the 1,4-dihydropyridine and benzene rings are 87.55 (7) and 87.23 (7)°. In one of these molecules, one of the isobutyl groups is disordered over two sets of sites, with an occupancy ratio of 0.890 (2):0.110 (2). In the crystal, molecules are linked through N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds forming two-dimensional networks parallel to the ab plane. The crystal structure is further stabilized by weak C—H⋯π interactions.
The title compound, C6H10N2O, is a zwitterionic pyrazole derivative. The crystal packing is predominantly governed by a three-center iminium–amine N+—H⋯O−⋯H—N interaction, leading to an undulating sheet-like structure lying parallel to (100).
In the title compound, C23H26O4, the two cyclohexene rings adopt envelope conformations whereas the pyran ring adopts a boat conformation. In the crystal, pairs of intermolecular O—H⋯O hydrogen bonds link the molecules into inversion dimers.
The asymmetric unit of the title compound, C23H23ClFN5O2, contains two crystallographically independent molecules. In one molecule, the pyrazole ring makes dihedral angles of 43.93 (7) and 35.82 (7)°, respectively, with the fluoro- and chloro-substituted benzene rings, while the corresponding angles in the other molecule are 52.26 (8) and 36.85 (7)°. The piperazine rings adopt chair conformations. In the crystal, adjacent molecules are connected via intermolecular N—H⋯O, C—H⋯F, C—H⋯N and C—H⋯O hydrogen bonds, forming a two-dimensional network parallel to the bc plane. The crystal structure is further stabilized by a weak π–π interaction with a centroid–centroid distance of 3.6610 (8) Å and by C—H⋯π interactions.
In the title compound, C27H24N2O·0.7H2O, the quinoline ring system is approximately planar, with a maximum deviation of 0.011 (1) Å, and forms dihedral angles of 74.70 (4) and 80.14 (4)° with the phenyl and benzene rings, respectively. In the crystal, the molecules are linked to the water molecules via intermolecular O—H⋯N hydrogen bonds and further stabilized by C—H⋯π interactions involving the centroid of the benzene ring of the quinoline group. This benzene ring is observed to form a π–π interaction with an adjacent pyridine ring [centroid–centroid distance = 3.7120 (6) Å].
In the title compound, C25H19NO, the quinoline ring system is approximately planar, with a maximum deviation of 0.32 (1) Å, and forms dihedral angles of 80.74 (3) and 81.71 (4)° with the two phenyl rings. In the crystal. molecules are stacked along the b axis by way of a C—H⋯π interaction and a weak π–π interaction between the pyridine and phenyl rings with a centroid–centroid distance of 3.6924 (5) Å.
In the title compound, C11H12N2OS, the pyrazole ring makes a dihedral angle of 85.40 (8)° with the phenyl ring. In the crystal, intermolecular N—H⋯O and C—H⋯O hydrogen bonds link molecules into a two-dimensional network parallel to the bc plane.
Two independent molecules comprise the asymmetric unit of the title chalcone, C25H17Cl2NO, and while each has an E configuration about the ethylene double bond, they differ in the relative orientations of the carbonyl and ethylene double bonds within the prop-2-en-1-one residues, i.e. anti and syn. For each molecule, the benzene [dihedral angles = 71.04 (9) and 73.34 (12)°] and prop-2-en-1-one [C—C—C—O = 91.2 (2) and −119.1 (3)°] substituents are twisted out of the plane of the quinoline moiety to which they are attached. The crystal structure is stabilized by C—H⋯π and π–π [Cg(quinoline)⋯Cg(quinoline) = 3.7809 (12) and 3.8446 (11) Å] interactions.
In the title compound, C11H10O3, the benzodioxole ring adopts a flattened [puckering parameters: q
2 = 0.107 (2) Å, ϕ2 = 160 (1)°] envelope conformation with the methylene C atom as the flap. The crystal packing features chains, parallel to the c axis, composed of dimers connected by weak C—H–O hydrogen bonds and extending in layers in the bc plane.
The asymmetric unit of the title compound, C13H16N2OS, contains two independent molecules (A and B). The pyrazole ring [maximum deviations = 0.0049 (17) Å in molecule A and 0.0112 (19) Å in molecule B] makes a dihedral angle of 70.23 (11) and 73.18 (12)° with the phenyl ring in molecules A and B, respectively. The isobutyl group in molecule B is disordered over two sets of sites with a ratio of refined occupancies of 0.858 (5):0.142 (5). In the crystal, molecules A and B are linked via a pair of intermolecular N—H⋯O hydrogen bonds, generating an R
2(8) ring motif. These ring motifs are further linked into two-dimensional arrays parallel to the bc plane by intermolecular N—H⋯O and weak C—H⋯S hydrogen bonds. The crystal is further stablized by weak π–π interactions [centroid–centroid distances = 3.5698 (13) and 3.5287 (12) Å].
The asymmetric unit of the title compound, C10H10N2O, contains two crystallographically independent molecules with similar geometries, which exist in the keto form. The C=O bond lengths are 1.2878 (12) Å in molecule A and 1.2890 (12) Å in molecule B, indicating that the compound undergoes enol-to-keto tautomerism during the crystallization process. In molecule A, the pyrazole ring is approximately planar [maximum deviation = 0.007 (1) Å] and forms a dihedral angle of 36.67 (6)° with the attached phenyl ring. In molecule B, the dihedral angle formed between the pyrazole ring [maximum deviation = 0.017 (1) Å] and the phenyl ring is 41.19 (6)°. In the crystal, intermolecular N—H⋯O hydrogen bonds link neighbouring molecules into dimers generating R
2(8) ring motifs. These dimers are linked into ribbons along  via intermolecular N—H⋯O hydrogen bonds, forming R
2(10) ring motifs.
In the title compound, C20H22O5, an S(6) ring motif is formed by an intramolecular C—H⋯O hydrogen bond, which contributes to the stabilization of the molecule. In the xanthene system, the cyclohexane ring adopts a chair conformation, the cyclohexene ring adopts a half-boat conformation and the tetrahydropyran ring adopts a half-chair conformation. The mean plane of the four essentially planar atoms of the tetrahydropyran ring [r.m.s deviation = 0.092 (1) Å] forms a dihedral angle of 64.13 (6)° with the mean plane of the methoxyphenyl group. In the crystal, intermolecular O—H⋯O and weak C—H⋯O hydrogen bonds link molecules into chains along the a axis, which are further stabilized by C—H⋯π interactions.
The title hydrate, C27H23NO2·H2O, features an almost planar quinoline residue (r.m.s. deviation = 0.015 Å) with the benzene [dihedral angle = 63.80 (7) °] and chalcone [C—C—C—O torsion angle = −103.38 (18)°] substituents twisted significantly out of its plane. The configuration about the C=C bond [1.340 (2) Å] is E. In the crystal, molecules related by the 21 symmetry operation are linked along the b axis via water molecules that form O—H⋯Oc and O—H⋯Nq hydrogen bonds (c = carbonyl and q = quinoline). A C—H⋯O interaction also occurs.
Corrigendum to Acta Cryst. (2010), E66, o3020–o3021.
The address of three of the authors in the paper by Shahani et al. [Acta Cryst. (2010), E66, o3020–o3021] is corrected.
In the title 1:1 adduct, C6H12N2O2·C9H10N2O2, the maximum deviations from the 1H-pyrazole-5-ol and furan rings are 0.014 (1) and 0.003 (1) Å, respectively. The dihedral angle formed between the 1H-pyrazol-5-ol and 2,5-dimethylfuran rings is 21.07 (5)°. In the crystal, pairs of intermolecular O—H⋯N hydrogen bonds form inversion dimers of the 3-(2,5-dimethylfuran-3-yl)-1H-pyrazol-5-ol species, generating R
2(8) ring motifs. Molecules are further linked by intermolecular N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds to form ribbons along the  direction containing bifurcated R
2(5) and R
1(7) ring motifs. Further stablization of the packing is provided by weak π–π [centroid–centroid distance = 3.5686 (15) Å] and C—H⋯π interactions.
The title compound, C9H14N2O, exists in the zwitterionic form in the crystal. The cyclooctane ring adopts a twisted boat-chair conformation. In the crystal, intermolecular N—H⋯O hydrogen bonds link the molecules into sheets lying parallel to bc. The structure is also stabilized by π–π interactions, with a centroid-to-centroid distance of 3.5684 (8) Å.
In the title compound, C22H17ClFN3O2S, the pyrazole ring is approximately planar with a maximum deviation of 0.001 (4) Å and makes dihedral angles of 4.95 (19), 35.78 (18) and 54.73 (18)° with the thiazole, fluorobenzene and chlorobenzene rings, respectively. In the crystal, intermolecular C—H⋯O hydrogen bonds link the molecules into chains along the a axis.
Each of the cyclohexenone rings in the title compound, C23H27NO6, adopts a half-chair (envelope) conformation with the C atom carrying the methyl groups lying out of the plane defined by the five remaining C atoms; the O atoms lie to the same side of the molecule as the respective >C(CH3)2 atoms. The hydroxy and carbonyl O atoms face each other and are orientated to allow for the formation of two intramolecular O—H⋯O hydrogen bonds. In the crystal, the presence of C—H⋯O contacts leads to the formation of supramolecular chains along the b axis. These aggregate into layers that stack along c.