0000000000535235
AUTHOR
Frank Kosteyn
4,4′‐Distyrylazobenzol als Mesogen
4,4′-Distyrylazobenzene as Mesogen From 3,4-dihydroxybenzaldehyde (1) the tetraalkoxy-substituted 4,4′-distyrylazobenzenes (E,E,E)-5a – c are synthesized. A similar reaction sequence leads from ethyl 3,4,5-trihydroxy-benzoate (6) to the hexaalkoxy-substituted 4,4′-distyrylazobenzenes (E,E,E)-11 b, c. With the exception of 5a all products show thermotropic LC properties. Smectic phases have been characterized by polarizing microscopy and by differential scanning calorimetry.
4,4′‐Distyrylazobenzol als Chromophor
4,4′-Distyrylazobenzene as Chromophore 4,4′-Distyrylazobenzenes are prepared from 4,4′-dimethylazobenzene. Whereas the Siegrist method furnishes stereoselectively the (E,E,E) configuration, a Wittig olefination leads to a mixture of (Z,E,Z), (Z,E,E) and (E,E,E) isomers which can be easily separated. Irradiation of the intense absorption at λ ≈ 400 nm causes a selective (E) (Z) isomerization of the N = N bond of all three isomers. The reverse reaction takes part in the photochemical equilibration, moreover, it is a thermal process with a relatively low activation barrier.
Photochemie elektronenreicher 1,3‐Distyrylbenzole
Die 1,3-Distyrylbenzole 3 mit bis zu sieben Alkoxygruppen werden der oxidativen Photocyclisierung unterworfen. Bei der Bildung der Produkte 6, 7 und 8 konnen als Konkurrenz- bzw. Folgeprozesse die Abspaltung von Methanol (3bb 7bb, 3bf 7bf) und die Chinonoxidation (3cf 8) auftreten. Die eigensensiblisierte Erzeugung von Singulettsauerstoff kann bei 6bf zur Endoperoxidbildung fuhren (6bf 11). Photochemistry of Electron-Rich 1,3-Distyrylbenzenes The 1,3-distyrylbenzenes 3, containing up to seven alkoxy groups, are subjected to the oxidative photocyclization. Elimination of methanol (3bb 7bb, 3bf 7bf) and quinone oxidation can occur as competitive or consecutive reactons in the formation of the…