The reaction of aroyl[bis(4 hydroxycoumarin 3 yl)]methanes with 1,2 phenylenediamines in Pr i OH is accompanied by the recyclization to 8 R or 7 R 4 (2 hydroxyphenyl) 1,5 benzodiazepin 2 ones, whereas the reaction with o phenylenediamine and its 4 methyl sub stituted derivatives in MeOH produces organic ionic salts of the bis coumarin anion with monoprotonated o phenylenediamine as the cation.Key words: aroyl[bis(4 hydroxycoumarin 3 yl)]methanes, 4 R 1,2 diaminobenzenes, 8 R (7 R) 4 (2 hydroxyphenyl) 1,5 benzodiazepin 2 ones, recyclization, ionic salts, X ray diffraction study.Various 4 hydroxycoumarin derivatives have found use as drugs. 1-5 Among these is neodicoumarin (ethyl di(4 hydroxycoumarin 3 yl)acetate), which is used in medicine as an anticoagulant. 6 These bis adducts based on heterocyclic CH acids and active carbonyl compounds (aldehydes or glyoxals) have attracted interest because their molecules contain several electrophilic centers, thus giving promise that various heterocyclization path ways are possible in the reactions with binucleophilic re agents.Earlier, 7 we have demonstrated that the reaction of aryl(aroyl)[bis(5,5 dimethyl 1,3 dioxocyclohexan 2 yl)]methanes with o phenylenediamine (o PDA) produces hexahydrobenzo[b,e] 1,4 diazepin 1 one derivatives 1A or 9 aryl(aroyl) 10 (2 aminophenyl)decahydroacridine 1,8 dione derivatives 2 depending on the electronic char acter of the substituent in the aryl or aroyl fragments. Electron withdrawing substituents in the aromatic moi ety facilitate the formation of the diazepine ring, whereas the formation of acridones is typical of the starting polyketones containing electron releasing substituents in the benzene ring.In the present study, we investigated the reaction of 4 R benzoyl[bis(4 hydroxycoumarin 3 yl)]methanes 3a-c with o PDA (4a) and its substituted derivatives 4b-d with the aim of synthesizing diazepines 1B, which are structurally similar to diazepines 1A and in which the diazepine fragment is annulated with the coumarin ring. The starting ketones 3a-c were synthesized in good yields by heating 4 hydroxycoumarin with p substituted aryl glyoxals in AcOH for a short period of time. Their struc tures were confirmed by 1 H NMR spectra, which show singlets for the methine protons at δ 6.2-6.4 and multi R = Ar, COAr

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Multi-membered N-heterocycles R 0690Aroyl[bis(4-hydroxycoumarin-3-yl)]methanes in Reactions with 1,2-Diaminobenzenes. -The reaction affords benzodiazepinone derivatives (V) or organic salts of bis(coumarin) anion (VI) depending on the conditions. -(KOLOS*, N. N.; GOZALISHVILI, L. L.; YAREMENKO, F. G.; SHISHKIN, O. V.; SHISHKINA, S. V.; KONOVALOVA, I. S.; Russ.

Benzopyran derivatives R 0350Reaction of 4-Hydroxycoumarin with Arylglyoxals and Ureas. -One-pot condensation reactions of 4-hydroxycoumarin (I) with various arylglyoxals and ureas afford imidazolylchromene derivatives (IV) (12 examples) instead of the expected benzopyrano[4,3-d]pyrimidine derivatives. -(KOLOS*, N. N.; GOZALISHVILI, L. L.; SIVOKON, E. N.; KNYAZEVA, I. V.; Russ.