NonclassicalPschorr andSandmeyer Reactions in Pyrazole Series

The diazonium salt derived from 4-amino-N,1,3-trimethyl-N-(3-methyl-1-phenyl-1H-pyrazol-5-yl)-1H-pyrazole-5-carboxamide (14) was reacted with a mixture of CuSO4 and NaCl, with ascorbic acid as an initiator to afford the planar derivative 4,6-dihydro-1,4,6,8-tetramethyl-3-phenyldipyrazolo[3,4-b:4′,3′-d]pyridin-5(3H)-one (16) and its unexpected isomer 4,6-dihydro-3,4,6,8-tetramethyl-1-phenyldipyrazolo[4,3-b:4′,3′-d]pyridin-5(1H)-one (17), as well as the epimers (3S,4S)- (or (3S,4R)-) and (3S,4R)- (or (3S,4S)-) 4-chloro-2,4-dihydro-1′,3′,5,5′-tetramethyl-2-phenylspiro[pyrazole-3,4′(1′H)-pyrrolo[3,4-c]pyrazol]-6′(5′H)-one (18a and b, respectively). Epimers 18a and b were converted under basic c…

The influence of the cation on the conformation of the anion μ-hydridobis[pentacarbonylchromium(0)]: crystal and molecular structure of [(phenH)2Cl][Cr2(CO)10(μ-H)] and [K(phen)2][Cr2(CO)10(μ-H)]

Abstract The crystal and molecular structures of [(phenH)2Cl][Cr2(CO)10(μ-H)] (1) and [K(phen)2][Cr2(CO)10(μ-H)] (2) have been determined by single crystal X-ray diffraction. The availability of the potassium cation for the carbonyl oxygens coordination influences the conformation of the anion in 2 as demonstrated by the comparison with the non-coordinating [(phenH)2Cl] cation in 1 and with literature data.

One-step synthesis, crystallographic studies and antimicrobial activity of new 4-diazopyrazole derivatives

Summary A number of new 4-diazopyrazole derivatives were prepared by the reaction of 1- R -3-methyl-5(R 1 -substituted)benzamidopyrazoles with a sevenfold excess of nitrous acid in acetic medium. The compounds were tested for activity against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Staphylococcus epidermidis, Streptococcus faecalis, Listeria monocytogenes, Candida albicans, Candida tropicalis and Paecilomyces varioti . The highest microbial susceptibility was shown by Gram-positive bacteria, with minimum inhibitory concentrations (MIC) in the range 0.5–12.5 μg/mL. For S aureus the R 1 substituents were screened utilizing the Topliss operational scheme. The 4-nitro g…

The yttrium chloride-1,10-phenanthroline interaction: Synthesis and X-ray crystal structure of the complex [Y(OH)(H2O)2(phen)2]2Cl4·2(phen)·MeOH

Abstract Investigations on the reaction between YCl3·H2O and phen (1,10-phenanthroline) led to the isolation of the title compound. The synthesis, IR and X-ray structural characterization are described. The crystal contains centrosymmetric binuclear dications [Y2(phen)4(μ-OH)2(H2O)4]4+, uncoordinated chloride anions, two clathrated phen molecules and a disordered methanol molecule. The yttrium ions are eight-coordinated with square antiprismatic geometry to the nitrogen atoms of two phen molecules, to bridging hydroxyl groups and to two water molecules. The Y ⋯ YI separation in the dimer is 3.651(2)A˚.

Synthesis and biological evaluation of new indazole derivatives

New N-methyl and N-ethyl substitutions in the indazole nucleus are reported by reacting 3-(2-aminobenzamido)indazole and the appropriate trimethyl/triethyl orthobenzoate. Single crystal X-ray analysis confirms the N-ethylation position for the 3-(1-ethyl-1H-indazol-3-yl)-2-phenylquinazolin-4(3H)-one derivative 3f. Compounds 11a-d and 3a-d were tested to evaluate their antimicrobial, their antiproliferative activity and their COX inhibitory activities showing scarce or moderately antiproliferative activity and some inhibitory activity against COX-1 and COX-2.

Comparative studies of the Pschorr reaction in the pyrazole series. Access to the new dibenzo[e,g]pyrazolo[1,5-a][1,3]diazocine system of pharmaceutical interest

The diazonium tetrafluoroborate 11 obtained from 2-amino-N-methyl-N-(1-phenyl-3- methylpyrazol-5-yl)benzamide was transformed in dry acetonitrile via an ionic or radical pathway. Differences were observed with respect to ionic or radical transformations in aqueous media of the analogous diazonium hydrogen sulfate 1 derived from the same amine. In acetonitrile solution, the ionic pathway was characterized by an increased yield of 1,4-dimethyl- 3-phenyl-pyrazolo(3,4-c)isoquinolin-5-one 4 and by the formation of its isomer, the new derivative 7,9-dimethyldibenzo(e,g)pyrazolo(1,5-a)(1,3)diazocin-10(9H)-one 12. When the reaction followed a radical pathway, the pyrazolo(3,4-c)isoquinoline derivat…

Synthesis and antiproliferative activity of 3-amino-N-phenyl-1H-indazole-1-carboxamides

Abstract A series of new 3-amino-N-phenyl-1H-indazole-1-carboxamides 10 have been prepared from commercially available phenyl isocyanate precursors 8 and 3-aminoindazole 9. Some of the synthesized compounds were evaluated for their in vitro antineoplastic activity against 60 human cell lines derived from seven clinically isolated cancer types (lung, colon, melanoma, renal, ovarian, brain, and leukemia) according to the NCI standard protocol. The test results indicated that 3-amino-1H-indazole-1-carboxamides 10 were endowed with an interesting antiproliferative activity. The most active compounds of this series, 10d,e, were able to inhibit cell growth of many neoplastic cell lines at concent…

Comparative Structural Studies of 4-Diazopyrazole Derivatives by X-Ray Diffraction and Theoretical Investigation

The X-Ray crystal and molecular structures of the 4-pyrazol derivatives 3-methyl-4-diazo-5-benzamido-1H-pyrazole (4) and 3-benzamido-5-methyl-1H-pyrazole (3) have been determined. A dimeric structure has been found for the first and polymeric for the second. A comparison of 4 with 1,3-dimethyl-4-diazo-5-benzamido-lH-pyrazole (2) shows differences in the geometrical parameters of the pyrazole ring due to electron delocalization in 2 consequent to the nitrogen negative charge in the latter. Theoretical investigation at the density functional theory (DFT) level shows difference in the molecular electronic distribution of 2 and 4, in agreement with the structural parameters and the IR stretchin…

ChemInform Abstract: One-Step Synthesis, Crystallographic Studies and Antimicrobial Activity of New 4-Diazopyrazole Derivatives.

Summary A number of new 4-diazopyrazole derivatives were prepared by the reaction of 1- R -3-methyl-5(R 1 -substituted)benzamidopyrazoles with a sevenfold excess of nitrous acid in acetic medium. The compounds were tested for activity against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Staphylococcus epidermidis, Streptococcus faecalis, Listeria monocytogenes, Candida albicans, Candida tropicalis and Paecilomyces varioti . The highest microbial susceptibility was shown by Gram-positive bacteria, with minimum inhibitory concentrations (MIC) in the range 0.5–12.5 μg/mL. For S aureus the R 1 substituents were screened utilizing the Topliss operational scheme. The 4-nitro g…

1,4-Dimethyl-3-phenyl-3H-pyrazolo[3,4-c]isoquinolin-5(4H)-one

The title compound, C18H15N3O, is the product of the thermal decomposition of the diazonium salt derived from 2-amino-N-methyl-N-(3-methyl-1-phenyl-1H-pyrazol-5-yl)benzamide. It is characterized by a trans orientation of the methyl groups with respect to the tricyclic ring system. The molecule has a nearly planar phenylpyrazolo[3,4-c]isoquinolin-5-one system, the largest deviation from the mean plane being 0.066 (2) angstrom for the O atom. The dihedral angle between the phenyl substituent and the heterotricycle is 67 (1)degrees. The packing is stabilized by C-H center dot center dot center dot N hydrogen-bond interactions, with the formation of molecular chains along the c axis.

Structural studies on 2-pyridyl complexes of the platinum triad metals. The crystal and molecular structure of the 2-pyridylium derivative trans-[PdCl(C5H5NC2)(PMe2Ph)2]ClO4

Abstract In solution, the complex trans -[PdCl(C 5 H 4 N C 2 )(PMe 2 Ph) 2 ] ( 1 ) is in equilibrium with a small amount of the binuclear species [{PdCl(μ-C 5 H 4 N C 2 , N )(PMe 2 Ph)} 2 ] ( 2 ), which can be isolated upon recrystallization. The compound 1 is easily N-protonated by HClO 4 to the 2-pyridylium product trans -[PdCl(C 5 H 5 N C 2 )(PMe 2 Ph) 2 ]ClO 4 ( 3 ), which crystallizes in the orthorhombic space group P2 1 2 1 2 1 , with cell parameters a =15.761(3), b =14.369(2), c =11.132(2) A and Z =4. The X-ray crystal structure analysis of 3 , using 3744 observed reflections in the refinement and resulting in a final R value of 0.0298, shows that the coordination around palladium…

Tetramethylammonium chlorodiphenylthiocyanatoantimonate(III)

The crystal structure of the title compound, (C4H12N)[Sb(C6H5)2Cl(NCS)], contains two cations and two anions in the asymmetric unit. The Sb atom exhibits a distorted pseudo-trigonal–bipyramidal coordination, with the phenyl groups and the lone pair of electrons in equatorial positions and N-bonded thio­cyanate and Cl− ligands in axial positions.

ChemInform Abstract: Synthesis, Crystallographic Studies and Biological Evaluation of Some 2-Substituted 3-Indazolyl-4(3H)-quinazolinones and 3-Indazolyl-4(3H)- benzotriazinones.

The influence of aromatic cations on the geometries of the Bi(III) halide polyhedra. Synthesis and crystal structures of quinolinium, isoquinolinium and 8-hydroxyquinolinium polychlorobismuthate(III) derivatives

Abstract The compounds [quinolinium]4[Bi2Cl10] (1), [isoquinolinium]4[Bi2Cl10].2H2O (2) and [8-hydroxyquinolinium]4[BiCl6]·Cl·2H2O (3) have been obtained by reacting bismuthate oxide and the appropriate base in HCl acid medium. The crystal structures of 1 and 2 consist of quinolinium and isoquinolinium cations, respectively, interacting through hydrogen bonding with [Bi2Cl10]4− dimers. The different degree of interactions in the two derivatives causes significant differences in the bond distances of the anions. The crystal structure of 3 is made of [BiCl6]3− and Cl− anions and 8-hydroxyquinolinium cations. Hydrogen bond interactions including the N-bonded and O-bonded H atoms together with …

Synthesis and X-ray crystal structure of cationic polynuclear hydroxide acetylacetonate lanthanide(III) clusters with homodinuclear or heterodinuclear decacarbonyl hydrides: [HMo2(CO)10]− and [HCrW(CO)10]−

The synthesis and characterization of new polynuclear lanthanide(III) ionic clusters of general formula [Ln 9 (acac) 16 (OH) 10 ] + [Mo 2 (CO) 10 (μ-H)]- (Ln = Sm, Eu, Gd, Dy, Yb) and [Sm 9 (acac) 16 OH) 10 ] + [CrW(CO) 10 (μ-H)] - is reported. The polynuclear complexes, prepared under pure nitrogen atmosphere by interaction of the hydridic metal carbonyls with the β-dichetonate Ln(acac) 3 ·3H 2 O (Ln=Sm, Eu, Gd, Dy, Yb). The new clusters were characterized by elemental analysis, complexometric titration for Ln, atomic absorption for Cr, W and Mo, gas-volumetric analysis for CO, FTIR spectroscopy and single crystal X-ray structure determination of [Sm 9 (acac) 16 (OH) 10 ][Mo 2 (CO) 10 (μ-H…

Synthesis, crystallographic studies and biological evaluation of some 2-substituted 3-indazolyl-4(3H)-quinazolinones and 3-indazolyl-4(3H)-benzotriazinones

Synthesis, infrared and M�ssbauer characterization and X-ray crystal structure of 1,10-phenanthrolinium tetrachloromethoxy phenylantimonate(V)

The compound has been characterized by X-ray crystal structure determination, Mossbauer and i.r. spectroscopy. It crystallizes in the monoclinic space groupP21/c (No. 14) witha=24.228(4),b=8.335(2),c=23.975(4) A,β=117.83(3)° andZ=8. Least-squares refinement on 3749 observed reflections gave finalR=0.034 (Rw=0.037). The compound is constituted by [(C6H5)SbCl4OMe]− anions andphenH+cations. The coordination polyhedron about Sb is an octahedron (Sb-Cl 2.416(3), Sb-O 1.962(7) and Sb-C 2.138(9) A). The whole structure is characterized by two short contacts (O(1)⋯N(2) 2.76(1) O(2)⋯N(4) 2.75(1) A) involving the methoxy oxygens of the two independent anionic units [(C6H5)SbCl4OMe]− and two nitrogens…

Synthesis and Chemical physical characterization of a new series of hydroxil, acetylacetonate lanthanide (III) – ditungsten decacarbonyl hydride complexes

A novel series of the heterometallic lanthanide(III) ionic cluster complexes of general formula Ln 9 (acac) 16 (OH) 10 [W 2 (CO) 10 (μ-H)] with Ln = Sm (la), Eu (1b), Gd (1c), Dy (1d), and Yb (le) was prepared and characterized by FTIR, 1 H NMR spectroscopy and single crystal X-ray analysis. The cluster series was obtained by reaction in ethanol solution of the 2,4-pentanedionate hydrate of lanthanide(III), Ln(acac) 3 .3H 2 O, with the hydridic ditungsten decacarbonyl, [W 2 (CO) 10 (μ-H)] - . X-ray analysis showed that the complexes la-le are isostructural. The complete structural characterization of the Eu derivative (1b) shows, similarly to their chromium derivative analogues, a square an…