The charge delocalised beta,beta-carotene dication--preparation, structure elucidation by NMR and reactions with nucleophiles.
The reaction between beta,beta-carotene and BF3-etherates has been investigated, leading to structural elucidation of the blue product, formed in appropriate organic solvents, as a symmetrical charge delocalised dication (lambda(max) 985 nm at room temperature in CHCl3) with considerable stability. The reaction, monitored by EPR studies at -25 degrees C, occurred via free radical intermediates. A C40H56BF3 intermediate was captured by EIMS. The detailed structure of the dication was established by COSY, HSQC, HMBC and 1D and 2D ROESY NMR techniques (600 MHz, CDCl3, -20 degrees C) leading to complete assignments of 1H and 13C chemical shifts and 3J(H,H) coupling constants. The effects of the two delocalised charges on chemical shift (charge distribution) and bond distance (3J(H,H)) were considered. The results are consistent with charge delocalisation mainly in the C-5-C-9 and C-5'-C-9' regions and with bond inversion to retro shifted double bonds in the central C-13-C-13' region. A convention for denoting the charge delocalisation and bond types is presented. The experimental results are discussed relative to previous theoretical calculations of the beta,beta-carotene dication structure. (All-E) and (15-Z)-beta,beta-carotene provided the same dication. The NIR spectra and stability of dications prepared in the same manner from the related carotenes 20,20'-dinor-beta,beta-carotene, heptapreno-beta,beta-carotene and nonapreno-beta,beta-carotene were examined for comparison. Reactions of the beta,beta-carotene dication with selected nucleophiles provided products including isocryptoxanthin, isocarotene and mutatochrome with H2O as nucleophile, and isocryptoxanthin methyl ether, 8-methoxy-7,8-dihydro-beta,beta-carotene and isocarotene with CH3ONa as nucleophile. The formation of these products is rationalised from the structure assigned to the dication.
Lutnaes
Bjart Frode
BF
Department of Chemistry, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway.
Bruås
Liv
L
Kildahl-Andersen
Geir
G
Krane
Jostein
J
Liaaen-Jensen
Synnøve
S
D002338:Carotenoids / Q000737:chemistry; D065366:Cryptoxanthins; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008738:Methyl Ethers / Q000737:chemistry; D008956:Models, Chemical; D013696:Temperature; D013997:Time Factors; D014466:Ultraviolet Rays; D024341:Xanthophylls; D019207:beta Carotene / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry*
D065366:Cryptoxanthins; D005609:Free Radicals; D008738:Methyl Ethers; D024341:Xanthophylls; D019207:beta Carotene; D002338:Carotenoids