No abstract

Trisalkylpyridiniurn porphyrins substituted by one glycosyl (glucosyl, maltosyl, and lactosyl) moiety have been prepared in acceptable yields. These glycosylated cationic porphyrins have been synthesized from pyrrole condensed with 4-pyridinecarboxaldehyde, and suitable ortho-orpara peracetylglycosyloxybenzaldehyde derivatives in refluxing propionic acid -Ac20 followed by action of alkyliodide in DMF. Deprotection of the glycosylated moieties led to a new class of representative glycosylated porphyrins.Key words: porphyrins, cationic, glycosylated; phototherapy, cancer.RCsumk : On a prCparC des tris(alky1pyridiniurn)porphyrines substituCes par une portion glycosyle (glucosyle, maltosyle et lactosyle) avec des rendements acceptables. On a synthttist ces porphyrines cationiques glycosylCes a partir de pyrrole condens6 avec un pyridine-4-carboxyaldChyde et des derives ortho-ou para-peracCtylglycosyloxybenzaldChydes approprits, par reflux dans de l'acide propanoi'que -Ac20, suivi par l'action d'un iodure d'alkyle dans le DMF. La dkprotection des portions glycosylCes conduit a une nouvelle classe de porphyrines glycosyltes representatives.

Mixed 2-(trimethylsilyl)ethyl sulfides were synthesized and used in the von Braun cyanogen bromide reaction for preparing selectively thiocyanates in high yield. We show here that this cleavage reaction is highly selective in methanol in comparison with the reaction of the corresponding non-silyl sulfide analogues. This reaction was applied to the synthesis of nucleosidic thiocyanates such as the new nucleosides 14 and 18 in the search for mechanism-based inhibitors of ribonucleoside diphosphate reductase and bioactive molecules. The selective cleavage is possible for sulfides bearing hydroxyl functions and aromatic rings. The reactions of cyanogen bromide as cyanating and brominating agent were observed for the first time under the same conditions with the naphthoxyhexyl 2-trimethylsilylethyl sulfide 7, which, treated with cyanogen bromide in dichloromethane, led selectively to the p-bromonaphthoxyhexyl thiocyanate 10 in 89% yield. Another reaction induced by cyanogen bromide was observed in dichloromethane with the 2-(trimethylsilylethyl)thio nucleoside 13, which gives the corresponding symmetrical disulfide 21 in good yield.

A series of 3‐carboxylic derivatives of disubstituted 1,5‐benzodiazepines (5–9) was synthesized by hetero‐cyclisation from 1,2‐diaminobenzene (1) with dibenzoylmethane (2) followed by bromination on position 3 and by introduction of the carboxylic group or introduction of the malonic moiety. Reduction of the hetero‐cycle gave the perhydro derivative diethyl (2,4‐diphenyl‐1,2,4,5‐tetrahydro‐3H‐1,5‐benzodiazepin‐3‐yl)malonate (9).