Helge Kjøsen

Acetylenic thiophenes from the roots of Echinops ellenbeckii from Ethiopia

The hexane fraction from the roots of Echinops ellenbeckii O. Hoffm. from Ethiopia yielded seven acetylenic thiophenes of which five compounds (1, 3, 4, 6, 7) are reported for the first time in this species: the monothiophenes 5-(penta-1,3-diynyl)-2-(but-3-en-1-ynyl)-thiophene (1), 5-(penta-1,3-diynyl)-2-(4-acetoxy-but-1-ynyl)-thiophene (2), 5-(penta-1,3-diynyl)-2-(3-hydroxy-4-acetoxy-but-1-ynyl)-thiophene (3), 5-(penta-1,3-diynyl)-2-(3,4-diacetoxy-but-1-ynyl)-thiophene (4), 5-(penta-1,3-diynyl)-2-(3-chloro-4-acetoxy-but-1-ynyl)-thiophene (5), 5-(penta-1,3-diynyl)-2-(3,4-epoxy-but-1-ynyl)-thiophene (6) and the dithiophene 5-[(5-acetoxymethyl-2-thienyl)-2-(but-3-en-1-ynyl)]-thiophene (7). Additionally, four fatty acids (C14, C15, C16 and C18), seven fatty acid esters and three long-chain hydrocarbons could be identified. All the structures were elucidated on the basis of spectral data by GC-MS, HRMS and the NMR techniques.

Syntheses of Octa(2-heteroaryl) Azaphthalocyanines

Magnesium, copper(II) and nickel(II) complexes of octasubstituted azaphthalocyanines 3 — 5 have been prepared from di-fur-2-yl, di-thien-2-yl and di-pyrid-2-yl pyrazine-2,3-dicarbonitriles 2. Compounds 2 were prepared in good yields from condensations of diaminomaleonitrile and the diketones 2,2′-furil, 2,2′-thenil and 2,2′-pyridil. AzaPcs 3—5 give green pyridine solutions with Q-bands at 650—670 nm and e-values of 60 000—190 000.

Syntheses of octa(dialkylamino)azaphthalocyanines

Nickel(II) octa(4-morpholinyl)- (11a) and copper(II) octa(1-pyrrolidinyl)- (11b) azaphthalocyanines have been prepared from the corresponding pyrazine diiminoimides (10). The precursor pyrazine dicarbonitriles (2) gave 6-cyanopyrazine-5-alkyl carboximidates (3-9) as stable intermediates when reacted with ammonia and catalytic amounts of sodium alkoxide in alcohols. Compounds 3-9 were converted to the diiminoimides 10 upon reflux in propanol or butanol for several hours. This unusual reaction pattern was observed for pyrazine-2,3-dicarbonitriles 2 substituted in the 5- and 6-positions with morpholine, thiomorpholine, piperidine or pyrrolidine.

Zn(quinoline)2Cl2: an efficient reagent for synthesis of zinc azaphthalocyanines with thiomorpholine- or pyrazole substituents

The Zn(quinoline)2Cl2 complex is found to be a convenient reagent for the direct synthesis of amino-substituted, zinc azaphthalocyanines. Octa(4-thiomorpholinyl)- and octa(1-pyrazolyl)- substituted zinc azaphthalocyanines were synthesized from pyrazines, 5,6-bis(4-thiomorpholinyl)pyrazine-2,3-dicarbonitrile and 5,6-bis(1-pyrazolyl)pyrazine-2,3-dicarbonitrile, respectively and dry Zn(quinoline)2Cl2. Two zinc azaphthalocyanines, both mixtures of four constitutional isomers, were synthesized by the same method, from 6-(2-thienyl)-5-(4-thiomorpholinyl)pyrazine-2,3-dicarbonitrile and from 6-(2-thienyl)-5-(1-pyrazolyl)pyrazine-2,3-dicarbonitrile respectively. The octa(4-thiomorpholinyl)- and octa(1-pyrazolyl)-substituted zinc azaphthalocyanines and the zinc azaphthalocyanines with mixed substituents were characterized by elemental analyses, TOF-SIMS, 1H and 13C NMR, and UV-vis spectroscopic methods. Q-bands for octa(4-thiomorpholinyl)- and octa(1-pyrazolyl)-substituted zinc azaphthalocyanines and the zinc azaph...

Synthesis and properties of novel components for organic metals : dihydrotellurophene derivatives

Two series of dihydrotellurophenes have been synthesized: derivatives of 4,6-dihydro-1H,3,H-telluropheno[3,4-c ]tellurophene (1) and derivatives of 1,3,6,8-tetrahydrobenzo[1,2-c;3,4-c′]ditellurophene (2). X-Ray structure determinations confirm the tetraiodo structures of 1a and 2a. The tetraiodo derivatives are reduced by sodium borohydride to the corresponding dihydrotellurophenes, 1b and 2b, which undergo the characteristic divalent tellurium reaction with iodomethane to form telluronium methiodides. Both dihydrotellurophenes 1b and 2b are moderate electron donors and react with 7,7,8,8-tetracyanoqiunodimethane TCNQ affording blue semiconductive solids.

Matrix-assisted laser desorption/ionization and Fourier transform ion cyclotron resonance mass spectrometry of metalloporphyrazines and metallophthalocyanines

High-resolution matrix-assisted laser desorption/ionization (MALDI) mass spectra of the title compounds were obtained using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The results show that this technique is well suited for obtaining molecule ions of the title compounds. The main peaks in the spectra are due to the molecular ion, M+• and/or the protonated molecule, MH+. Little fragmentation is observed. Isotopic masses were measured for one of the compounds with an estimated accuracy of ± 5 ppm. In addition, experiments were performed with the neat compounds, without a matrix. This direct laser desorption method is useful in some cases, but is generally not applicable for these types of compounds, even when great care is exercised in controlling the laser pulse energy.

(22S)-6-O-Acetyl-21bH-hopane-3b,6b,22,29-tetrol from Oakmoss (Evernia prunastri)

A novel hopanoid triterpene, (22S)-6-O-acetyl-21βH-hopane-3β,6β,22,29-tetraol, was isolated from oakmoss (Evernia prunastri (L.) Ach.), as identified from 1H, 13C, DEPT, COSY, NOESY, HSQC and HMBC NMR, MS and IR spectroscopy. During recrystallisation a new compound, 30-nor-6-O-acetyl-3β,6β-dihydroxy-21αH-hopan-22-one, was formed by a formal loss of methanol from the dihydroxypropyl moiety. No biological activity was found for the naturally occurring compound upon testing against a series of fish and human pathogenic bacteria.