The characterization of 3,4-dimethylmethcathinone (3,4-DMMC).

Analogs and derivatives of traditional illicit drugs are ever increasing in variety and creativity. Staying abreast of the new developments is a constant challenge for every forensic laboratory. Recently, a seizure from Australian Customs Service presented our laboratory with the designer cathinone 3,4-dimethylmethcathinone (3,4-DMMC). Gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS), nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and ultraviolet (UV) spectrophotometry were employed to analyze the spectroscopic characteristics of this cathinone. As an analog, 3,4-DMMC exhibits similar if not identical IR and UV profiles to mephedrone (4-MMC) and methcathinone; however, the retention time from GC is unique as expected, and the electron impact fragmentation pattern is consistent with the fragmentation pattern of other cathinones. The chemical shifts of the carbons and hydrogens were assigned by both one- and two-dimensional NMR techniques, while the molecular weight was confirmed by LC/MS.

Homo- and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins: preparation, x-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations.

Homo- and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M(2)10 (M(2) =H(2)/Ni, Ni(2), Ni/Zn, H(4), H(2)Zn, Zn(2)) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H(2), Ni, and ZnTriPP on the other (M(2)11), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, (1)H NMR spectra, and for the Ni(2) bis(TriPP) complex Ni(2)10, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni(II) porphyrins, and the (E)-C(2)H(2) bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H(4)10 and H(2)Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni(2)10 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV.

The Heck reaction for porphyrin functionalisation: synthesis of meso-alkenyl monoporphyrins and palladium-catalysed formation of unprecedented meso-beta ethene-linked diporphyrins.

Palladium-catalysed coupling of the vinyl derivatives methyl acrylate, styrene and acrylonitrile with 5-bromo-10,15,20-triphenylporphyrin (MTriPPBr; M = 2H, Ni, Zn) and 5,15-dibromo-10,20-bis(3,5-di-tert-butylphenyl)porphyrin (MDAPBr(2)) produced a series of mono- and disubstituted alkenylporphyrins, thus demonstrating the applicability of meso-haloporphyrins in Heck-type reactions. The same technique was also applied to meso-ethenylporphyrins and simple aryl halides, with mixed results. Only meso-vinyl nickel(ii) porphyrins showed any reactivity under our conditions. A mixture of 1,1- and 1,2-disubstitution across the alkene was observed for 5-vinyl-10,15,20-triphenylporphyrinatonickel(ii) (meso-vinylNiTriPP), whereas 5-vinyl-10,20-bis(3,5-di-t-butylphenyl)porphyrinatonickel(ii) (meso-vinylNiDAP) produced a mixture of meso-1,1-, meso-1,2- and, surprisingly, beta-1,2-disubstituted Heck products. Coupling meso-vinylNiDAP with MTriPPBr under similar Heck conditions led unexpectedly to transbeta-meso-NiDAP-ethene-MTriPP dyads, affording the first members of a new class of alkenyl-linked diporphyrins. A mechanism for the unusual meso to beta rearrangement is discussed. The electronic absorption spectra of the dyads have a red-shifted shoulder on the Soret (B) band, which is evidence of a moderate degree of electronic interaction between the porphyrins via the ethenyl bridge.