High resolution electrospray and electrospray tandem mass spectra of rotenone and its isoxazoline cycloadducts

An evaluation of the gas-phase ion chemistry of rotenone (1) by electrospray ionisation (ESI) mass spectrometry (MS) and tandem mass spectrometry (MS2) is presented, aiming at providing tools for its determination in natural and biological matrices. The behaviour of its cycloadducts with benzonitrile-N-oxide (2) and 2,4,6-trimethylbenzonitrile-N-oxide (3) was also evaluated and the MS data thus obtained have provided evidence into the mechanism of formation of the key product ion at m/z 192 which can be considered a marker in the MS and MS2 spectra of rotenone and its derivatives.     

Amide-water interactions in cosolvent systems. I. Solubilities and apparent molar volumes of methyl paraben

Solubility and apparent molar volume data are used to demonstrate effects of amide alkylation on amide-water interactions at 25° C. Precise measurements were made of the apparent molar volumes of the amides in binary amide-water mixtures using a dilatometric technique. The results show that the apparent molar volumes of alkyl-substituted amides in water pass through a minimum at an amide concentration which varies inversely with the degree of alkylation. Further studies showed that the solubilities of methyl paraben (methyl-p-hydroxybenzoate) and naphthalene in various amide-water solvent systems increased in characteristic fashion with amide alkylation.     

Novel heterocycle-based two-photon absorbing dyes

[structure: see text]. The synthesis and nonlinear optical characterization of two novel heteroaromatic-based chromophores is described. The new dyes present an A-pi-D-pi-A general framework, where A is a pi-deficient heteroaromatic ring (pyridine, quinoline, benzothiazole) and D a pi-excessive pyrrolyl moiety. Both systems exhibit large two-photon absorption (TPA) values in the femtoseconds regime (TPA cross section as high as 150 x 10(-50) cm(4) s photon(-1) molecule(-1) with 150 fs laser pulses). Their TPA-based optical limiting activity is also shown.     

Di­chloro­bis(1‐propyl­imidazolidine‐2‐thione‐κS)­cobalt(II)

The crystal structure of the title compound, [CoCl₂(C₆H₁₂N₂S)₂], consists of monomer units of a Co^II atom coordinated to two 1‐propyl­imidazolidine‐2‐thione ligands and to two chloride ions. The heterocyclic thione ligand is monodentate and coordinated to the metal through the thione S atom. The environment around the Co^II atom is a slightly distorted tetrahedron. The Co—S bond lengths are 2.341 (2) and 2.330 (2) Å, and the Co—Cl bond lengths are 2.234 (2) and 2.238 (2) Å. The most important point of distortion is the S—Co—S bond angle of only 97.83 (8)°. Intramolecular classical hydrogen bonds are found between the chloride ions and the N—H groups. Additionally, intra‐ and intermolecular non‐classical hydrogen bonds are found.     

Structural control of dithiazolyl radicals: Case studies on 3′- and 4′-cyano-benzo-1,3,2-dithiazolyl, NCC6H3S2N

Dithiazolyl radicals with π-stacking motifs have attracted particular interest because of their ability to exhibit spin-switching between diamagnetic distorted π-stacks and paramagnetic regular π-stacked structures through a solid state phase transition. Previous studies indicate that inclusion of electronegative heteroatoms into the backbone favours lamellar structures. This methodology has been extended to the synthesis and characterisation of the title compound, 4′-cyanobenzo-1,3,2-dithiazolyl (4-NCBDTA). Its electronic structure is probed through DFT calculations, cyclic voltammetry and EPR spectroscopy and its crystal structure determined by X-ray powder diffraction at room temperature. Variable temperature SQUID magnetometry reveals that 4-NCBDTA undergoes two phase transitions, each exhibiting bistability; a high temperature phase transition occurs at room temperature (T_C↓ = 291 K, T_C↑ = 304 K, ΔT = 13 K); whilst the low temperature phase transition occurs below liquid nitrogen temperatures (T_C↓ = 37 K, T_C↑ = 28 K;ΔT = 9 K).     

Convenient synthesis of nucleoside and isonucleoside analogues

[reaction: see text]. A very simple methodology to stereoselectively achieve tricyclic isonucleosides (nucleobase = thymine, uracil, and 5-fluoruracil) and 3'-C-branched nucleosides (nucleobase = theophylline) was performed by means of a DBU-mediated addition process using a readily available 2-bromo sugar. The mechanism for these transformations implies the loss of both substituents at C-2 and C-3 on the sugar moiety, and although it seems that DBU is probably involved, its involvement has not yet been ascertained. Cytosine did not react under these conditions.     

Synthesis of fused purinoquinazolines. Three new heterocyclic ring systems

The Ullmann reaction of 8-aminotheophylline or 8-aminocaffeine with 2-chlorobenzoic acid and of 8-bromotheophylline with ethyl-2-aminobenzoate afforded derivatives of three new heterocyclic systems: purino[7,8-α]quinazoline-5,9,11(6H,8H,10H)-trione, purino[8,9-b]quinazoline-2,4,11(1H,3H,5H)-trione and purino[8,7-b]quinazoline-2,4,6(1H,3H,11H)-trione, respectively.     

Assignment of the relative configuration of spiro[4.5]decanes by 13C, 15N and 17O NMR

The relative configuration of 11 1,4-diazaspiro[4.5]decanes (1a-1j and 1m), 15 1,4-oxazaspiro[4.5]decanes (2a-2o) and 10 1,4-dioxaspiro[4.5]decanes (3a-3n) substituted at the 2-, 6-, 7- or 8-position by a methyl group or using the tert-butyl group as a model for the ananchomeric structure is reported. The relative stereochemistry was analyzed by 1H, 13C, 15N and 17O NMR and all isomers present were characterized spectroscopically. Compounds with a methyl group in the six-membered ring show a chair conformation preference with the methyl group in the equatorial position. Compounds with one or two nitrogens exhibit a tautomeric equilibrium between the imine-diazolidine forms, as demonstrated by IR and 13C NMR.     

A pyrimidine thiolate Rh(I) complex: structure, bonding and one-dimensional interactions in solid and in solution

The reaction of [Rh(micro-Cl)(COD)]2 with 4,6-dimethyl-pyrimidinethiolate (Me2-pymt) and subsequent substitution of COD by CO yields [Rh(Me2-pymt)(CO)2]. The stacking pattern found in this compound is in contradiction with previously studied comparable square-planar complexes of type d8-[M(chelate)(monodentate)2] in which each ligand has different pi-acidic character. A theoretical study of the intermolecular interactions and conformation of the title compound has been carried out, combining semi-empirical band calculations on the real chains and ab initio(MP2 level) calculations on a model dimer. The combination of electronic and steric effects determines the rotation of the successive monomers and the deviation from linearity of the one-dimensional stacks. Its behaviour in solution is also special, developing a blue colour and forming micelles, when adding water to acetone solutions.     

Synthesis and antifungal activity against strains of candida albicans of 6‐fluoro‐4(5 or 7)‐chloro‐2‐(difluorobenzoyl)aminobenzothiazoles

A series of 6‐fluoro‐4‐(5 or 7)‐chloro‐2‐(difluorobenzoyl)aminobenzothiazoles 3a‐r were prepared to investigate their potential biological activity. In this work, the results of their in vitro antifungal activity against some strains of Candida albicans are reported. It was found that some derivatives displayed antifungal activity higher than that for 3k [1a] compound already described in literature.