Behavior of PQQ Glucose Dehydrogenase on Prussian Blue‐Modified Carbon Electrode

Glucose sensitive biosensor containing pyrroloquinoline quinone (PQQ)‐dependent glucose dehydrogenase immobilized on Prussian blue (PB)‐modified graphite electrode was designed. Properties of the biosensor were investigated in the cathodic and anodic response detection regions. It was shown, that anodic response of the biosensor is sum of two signals: direct electron transport from reduced PQQ to the electrode and by formation of the PQQ‐oxygen‐PB‐carbon ternary complex. Cathodic response of the biosensor is based on the oxidation of the reduced PQQ by PB‐oxygen‐PB complex. Electrochemical regeneration of the enzyme does not produce free hydrogen peroxide.     

Regioselective conversion of 3-cyano-6-hydroxy-2-pyridones into 3-cyano-6-amino-2-pyridones

The reaction of a tautomeric mixture of 1-butyl-1,2-dihydro-6-hydroxy-4-methyl-2-oxopyridine-3-carbonitrile and its 2-hydroxy-6-oxo analog with phosphorus oxychloride gave 1-butyl-6-chloro-1,2-dihydro-4-methyl-2-oxopyridine-3-carbonitrile (68%) and 1-butyl-2-chloro-1,6-dihydro-4-methyl-6-pyridine-3-car-bonitrile (3%). Both chloropyridones were converted to their corresponding aminopyridones by reaction with liquid ammonia. Strong support for the molecular structure of 6-amino-1-butyl-1,2-dihydro-4-methyl-2-oxopyridine-3-carbonitrile was obtained on the basis of nmr techniques.     

Chemistry of α-(benzotriazol-l-yl)alkylpyridines. Unusual nucleophilic attack at c-3a of the benzotriazolyl ring

Lithiation of 2-, 3- and 4-[α-(benzotriazol-l-yl)methyl]pyridines with butyllithium followed by reactions with electrophiles (alkyl halides, aldehydes, ethyl benzoate and diphenyl disulfide) gave the corresponding α-sub-stituted derivatives in good yields. Repetition of the reaction sequence allowed substitution of the second α-proton by an electrophile. 2-[α-(Benzotriazol-l-yl)-α-(phenylthio)pentyl]pyridine thus obtained gave an unusual attack of the Grignard reagents at C-3a of the benzotriazole system on treatment with arylmagnesium bromides.