Zum Mechanismus der Chemilumineszenz cyclischer Diacylhydrazide Konstitution und Chemilumineszenz, IV¹⁾ Chemilumineszenz von Diazachinonen

Abstract

Die Diazachinone [I .4-Dihydrophthalazindione-( I .4)] 3 und 4 werden aus den Mononatriumsalzen der entsprechenden Hydrazide dargestellt, welche bei 430 nm stark chemilumineszieren. Ebenso verhalten sich 3 und 4 beim Mischen ihrer acetonischen Losungen mit waBriger Natronlauge und Wasserstoffperoxid oder Luft. Ein EinfluR von Hamin oder Diimin auf diese Chemilumineszenz wird nicht beobachtet. Der EinfluB der Wasserstoffperoxid-und Natriumhydroxid-Konzentration auf die Quantenausbeute ist vereinbar mit der Bildung eines cyclischen Peroxids (vgl. S . 152) als wesentlicher Zwischenstufe der Luminol-Chemilumineszenz. Das relativ stabile Diazachinon 4 wird auch bei der chemilumineszenten Oxydation waBrig-alkalischer Losungen von Anthracen-dicarbonsaure-(2.3)-hydrazid (10) mit tert.-Butylhypochlorit gebildet. Constitution and Chemiluminescerrce. I V ' 1. Chemiluminescence of Diazaquinones. Mechanism for the Chemiluminescent Reaction of Cyclic Diacylic HydrazidesThe diazaquinones (phthalazine-l,4-diones) 3 and 4 are synthetized from the mono sodium salts of the corresponding hydrazides which chemiluminesce strongly near 430 nm. So do 3 and 4 on mixing their acetone solutions with aqueous sodium hydroxide and hydrogen peroxide or air. No influence of hemin or diimine on this chemiluminescence is observed. The effect of hydrogen peroxide and of sodium hydroxide concentration on the quantum yield of 4 chemiluminescence is compatible with the formation of a cyclic peroxide (p. 152) as the key intermediate of luminol chemiluminescence. The relatively stable diazaquinonr 4 is also formed duringthe chemiluminescent oxidation of aqueous alkaline solutions of anthracene-2,3-dicarboxylic acid hydrazide by tert. butyl hypochlorite.

Synthesis of 2,3-Anthracenedicarboxylic-acid-derived Fluorophore and Chemiluminophore Incorporating Dipicolylaminomethyl Receptors, and Their Luminescence Responses to Metal Ions

“…After the CL reaction, the original absorption band of cyclic-hydrazide 2 (around 440 nm) vanished and a new absorption band evolved in a shorter wavelength region (360-430 nm, Figure 5a, solid lines). These results indicate that the cyclic-hydrazide 2 was consumed through the CL reaction to form a product (presumably the corresponding dicarboxylate) 19,20 which might display the blue-shifted absorption band compared to the cyclic-hydrazide 2.…”

“…It would, thus, be of interest to construct a chemiluminophore incorporating dipicolylaminomethyl host moiety and to reveal whether natures of the chemically generated luminescent state can be manipulated by PET switching. Since anthracene-2,3-dicarbohydrazide has been known to be chemiluminenscent, 19,20 we attempted to modify the chemiluminophore with dipicolylaminomethyl host functionality to construct a novel luminescent probe.…”