Studies on indian medicinal plants-XLIV: Solanoforthine,a new steroidal alkaloid from solanum seaforthianum. a note on the mass spectrum of solanocapsine

The structure of solanoforthine, m.p. 208–10°, [α]_D- 26.6°, a new steroidal alkaloid isolated from Solanum seaforthianum Andr., has been established as 3β-amino-22,26-epimino-16α,23-epoxy-22αH,25βH-cholest- 5- en -23β - ol 3, based on chemical and spectroscopic evidence and by its reduction to solanocapsine 2, another steroidal alkaloid encountered in the same species. The mass spectra of2 and 3 are discussed.     

Synthesis,crystal structure,and magnetic properties of an alkoxo-hydroxo-bridged octanuclear copper(II) complex showing chemically significant hydrogen-bonding interactions involving a metallamacrocyclic core

A novel 16-member metallamacrocyclic octanuclear copper(II) complex of formulation [Cu8L4(OH)4] (1) has been prepared from a reaction of [Cu2L(O2CMe)] and NaOH in methanol, where L is a pentadentate trianionic Schiff base ligand N,N'-(2-hydroxypropane-1,3-diyl)bis(salicylaldimine). The complex has been characterized by analytical, structural, and spectral methods. It crystallizes in the monoclinic space group C2/c with the following unit cell dimensions: a = 30.365(3) A; b = 14.320(2) A; c = 19.019(2) A; beta = 125.33(2) degrees; V = 6746.7(13) A3; Z = 4. A total of 4589 unique data with l > 2 sigma (l) were used to refine the structure to R1(F0) = 0.0525 and wR2 = 0.1156. The structure consists of four binuclear [Cu2L]+ units linked covalently by four hydroxide ligands to form an octanuclear core which is stabilized by strong hydrogen-bonding interactions involving the hydroxide ligands. Each binuclear unit has a pentadentate ligand L showing N2O3 coordination with an endogenous alkoxide bridging atom. The magnetic susceptibility data of 1, obtained in the temperature range 14-306 K, show the presence of antiferromagnetic exchange interactions between adjacent spin-1/2 Cu(II) ions. The mu eff values are 1.54 and 0.26 microB (per copper) at 295 and 15 K, respectively. The magnetic data have been theoretically fitted using a Heisenberg spin-1/2 Hamiltonian with nearest-neighbor antiferromagnetic interactions. The spin coupling in the metallamacrocyclic ring has been modeled using four different coupling constants (J) on the basis of the structural parameters of the octanuclear core. The coupling constants obtained are J1 = -318.8, J2 = -293.3, J3 = -111.6, and J4 = -63.8 cm-1. The theoretical modeling of the susceptibility data gives a higher magnitude of the antiferromagnetic interaction within the binuclear [Cu2L]+ unit compared to those involving adjacent dimeric units.     

Condensed cyclic and bridged-ring systems. VII. Acid-catalysed cyclisation of methyl substituted benzylcyclohexanols. Factors influencing the nature of cyclisation products

The gross structures of the cyclised products from the acid-catalysed cyclisations of 2-benzyl-1, 3-dimethylcyclohexanol (6) and 1-benzyl-3, 5-dimethylcyclohexanol (11) revealing the influence of the structure of the benzylcyclohexanol derivative, and of the cyclisation reagent, have been evaluated. Polyphosphoric acid and aluminium chloride catalysed cyclisations of (6) result in the formation of predominantly 1, 4a-dimethyl-1, 2, 3, 4, 4a, 9a-hexahydrofluorene (7) and 4, 9-dimethyl-7, 8-benzobicyclo [3.3.1] non-7-ene (9) respectively. Under the same conditions, (11) produced cyclised products consisting mostly the benzobicyclo [3.3.1] non-7-ene derivative (12), characterised through 1,3-dimethyl-7,8-benzobicyclo [3.3.1] non-6-oxo-7-ene (14) by oxidation with chromium trioxide. Phosphorus pentoxide induced cyclisation of (6), followed by oxidation gave a mixture of the bridged-ring ketone (10) and the 9-oxohydrofluorene (8) in a ratio ofca. 3 : 2, whereas 2-benzyl-5-methylcyclohexanol (19) resulted in mostly 2-methyl-7,8-benzobicyclo [3.3.1] non-6-oxo-7-ene (19).     

Synthesis, characterization and electron transfer properties of some picolinate complexes of ruthenium

In aqueous solution ruthenium trichloride reacted with picolinic acid (Hpic) in the presence of a base to afford [Ru(pic)₃]. In solution it shows intense ligand-to-metal charge transfer transitions near 310 and 370 nm, together with a low-intensity absorption near 2000 nm. [Ru(pic)₃] is one-electron paramagnetic and shows a rhombic ESR spectrum in 1:1 dimethylsulphoxide-methanol solution at 77 K. The distortions from octahedral symmetry have been calculated by ESR data analysis. The axial distortion is larger than the rhombic one. In acetonitrile solution it shows a reversible ruthenium(III)-ruthenium(II) reduction at −0.09 V vs. SCE and a reversible ruthenium(III)-ruthenium(IV) oxidation at 1.52 V vs. SCE. Chemical or electrochemical reduction of [Ru^III(pic)₃] gives [Ru^II(pic)₃]⁻, which in solution shows intense MLCT transitions near 360, 410 and 490 nm, and is converted back to [Ru(pic)₃] by exposure to air. Reaction of [Ru(pic)₃] with 8-quinolinol (HQ) in dimethylsulphoxide solution affords [RuQ₃]. [Ru(bpy)(pic)₂] (bpy = 2,2′-bipyridine) has been prepared by the reaction of Hpic with [Ru(bpy)(acac)₂]Cl (acac = acetylacetonate ion) in ethyleneglycol. It is diamagnetic and in solution shows intense MLCT transitions near 370, 410 and 530 nm. In acetonitrile solution it shows a reversible ruthenium(II)-ruthernium(III) oxidation at 0.44 V vs. SCE and a reversible one-electron reduction of bpy at − 1.64V vs. SCE.     

Kinetics and mechanisms of the reactions of thiosulphato-amine complexes of cobalt(III). Part I. Isomerization and base hydrolysis ofcis andtrans isomers of dithiosulphatobis(ethylenediamine) cobalt(III) ion in aqueous solution

Summary Investigations were carried out on the isomerization and base hydrolysis ofcis andtrans forms of dithiosulphatobis-(ethylenediamine)cobalt(III) ions. Thecis form isomerizes to thetrans form in neutral aqueous medium, rates being 1.15, 2.30 and 4.0×10^–5s^–1, respectively at 42, 50 and 58 °C. Thetrans complex isomerizes to thecis form in basic solution only, the rate varying with pH in a sigmoid pattern. In presence of OH^–, an acid-base equilibrium of the complex ion sets in, but only the basic form takes part in the isomerization reaction. Hydrolysis of thecis isomer proceeds through a base-dependent path only, but that of thetrans isomer proceeds both through base-dependent and base-independent paths. The mechanisms are associative in nature. Thetrans form reacts faster thancis in all cases.     

Intramolecular nucleophilic activation promoting efficient hydrolytic cleavage of DNA by (aqua)bis(dipyridoquinoxaline)copper(II) complex

The axial aqua bound copper(II) complex [Cu(dpq)2(H2O)](ClO4)2, having a planar NN-donor heterocyclic base dipyridoquinoxaline (dpq) as the DNA minor groove binder, shows efficient hydrolytic cleavage of supercoiled DNA in the dark and in the absence of any external reagents, as evidenced from T4 ligase experiments, with a rate of 5.58 +/- 0.4 h(-1) and a rate enhancement of 1.55 x 10(8).     

Preparation of Aryl‐Substituted E‐Homoallylic Bromides from Cyclopropylcarbinol and PBr3

An expeditious synthesis of aryl substituted E‐homoallylic bromides has been accomplished by the cleavage of cyclopropylcarbinols with phosphorus tribromide.     

Dioxane Dibromide–Mediated Solvent‐Free Synthesis of Vicinal Dibromides

Structurally varied vicinal dibromides have been synthesized in high yield and good purity through highly stereoselective anti‐addition of bromine across the olefinic linkages using dioxane dibromide (DD) under solvent‐free conditions.