New method of synthesis of 1,5‐benzodiazepin‐2‐ones from 4‐hydroxycoumarin

Hamdi, Maâmar; Grech, Odile; Sakellariou, R.; Spézale, Vincent

doi:10.1002/jhet.5570310242

Cited by 32 publications

(22 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The structure of compound 5 was confirmed by the 1 H NMR spectra, which show singlets for the me thylene groups at δ 3.6-3.7, multiplets for aromatic pro tons, and singlets at δ 10.75 and 13.7-14.2, which disap pear after deuterium exchange. In addition, the spectro scopic and physicochemical characteristics of diazepinone 5a are consistent with the data from the study, 9 where this compound was synthesized from 4 hydroxycoumarin and o PDA.…”

supporting

confidence: 81%

Aroyl[bis(4-hydroxycoumarin-3-yl)]methanes in reactions with 1,2-diaminobenzenes

et al. 2007

View full text Add to dashboard Cite

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

show abstract

supporting

confidence: 81%

Aroyl[bis(4-hydroxycoumarin-3-yl)]methanes in reactions with 1,2-diaminobenzenes

et al. 2007

View full text Add to dashboard Cite

show abstract

“…4-Hydroxycoumarin with anticoagulant activity 1 is widely used to prepare pharmaceutical and some of biologically important compounds, such as warfarin 2 diazepins, 3 pyranocoumarins and coumarinopyrano pyrimidines, 4 antiplatelet compounds, 5 benzopyranopyrano quinolines 6 and fercoprolones, 7 analogues of novobicin 8 and coumestans. 9,10 It has also been identified as an intermediate in many processes.…”

Section: Introductionmentioning

confidence: 99%

Electrooxidation of Iodide in the Presence of 4-Hydroxycoumarin: Application to a Simple Coulometric Titration of 4-Hydroxycoumarin

2003

View full text Add to dashboard Cite

The electrochemical oxidation of iodide ion in the presence of 4-hydroxycoumarin (1) was studied using cyclic voltammetry and controlled-potential coulometry. The result indicates that the resulting iodine takes part in a halogenation reaction and reacts with 4-hydroxycoumarin (1). According to the obtained results, a new and simple coulometric titration method with potentiometric end-point detection for the determination of 4-hydroxycoumarin (1) is presented. In the presented method, 2 -200 µmol of 4-hydroxycoumarin (1) was successfully determined.

show abstract

“…The structure of the obtained products 9-11 was determined by reference to the ring substituents and are a consequence of the starting 1,2-phenylenediamines 7b-d. When an electron-donating group is present (CH 3 , Cl), the 1-NH 2 reacts first, whereas for an electron-withdrawing substituent (NO 2 ), the 2-NH 2 group reacts first, giving products 9-11 after a cyclocondensation reaction [24][25][26]. The 13 C NMR spectrum of 9 confirms a 4-hydroxy-2-pyrone ring whereas in compounds 10 and 11, the presence of the methine group of a b-ketoester system is amply confirmed using HSQC and HMBC correlations (H-3!C-3 and C-2 0 ; H-3 0 !C-3 and C-10; NH!C-5 0 ).…”

Section: Resultsmentioning

confidence: 99%

New synthesis and reactivity of 3‐bromoacetyl‐4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one with binucleophilic amines

Hikem-Oukacha

Hamdi

Silva

et al. 2010

Journal of Heterocyclic Chem

View full text Add to dashboard Cite

3‐(Bromoacetyl)‐4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one was synthesized by the reaction of dehydroacetic acid (DHAA) with bromine in glacial acetic acid. Novel heterocyclic products were synthesized from the reaction of bromo‐DHAA with alkanediamines, phenylhydrazines, ortho‐phenylenediamines, and ortho‐aminobenzenethiol. The obtained new products 3‐(2‐N‐substituted‐acetyl)‐4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐ones, 4‐hydroxy‐3‐[1‐hydroxy‐2‐(2‐phenylhydrazinyl)vinyl]‐6‐methyl‐2H‐pyran‐2‐one, 1‐(2,4‐dinitrophenyl)‐7‐methyl‐2,3‐dihydro‐1H‐pyrano[4,3‐c]pyridazine‐4,5‐dione, 3‐(3,4‐dihydroquinoxalin‐2‐yl)‐4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one/3‐(3,4‐dihydroquinoxalin‐2‐yl)‐6‐methyl‐2H‐pyran‐2,4(3H)‐dione, 6‐methyl‐3‐(3,4‐dihydroquinoxalin‐2‐yl)‐2H‐pyran‐2,4(3H)‐dione, and (E)‐3‐(2H‐benzo[b][1,4]thiazin‐3(4H)‐ylidene)‐6‐methyl‐2H‐pyran‐2,4(3H)‐dione were fully characterized by IR, 1H and 13C NMR, and mass spectra. J. Heterocyclic Chem., 2011.

show abstract

New method of synthesis of 1,5‐benzodiazepin‐2‐ones from 4‐hydroxycoumarin

Abstract: A new method of synthesis of 1,5‐benzodiazepine‐2‐ones, from 4‐hydroxycoumarin and substituted 1,2‐phenylenediamines by heating in xylene or acetic acid‐ethanol, is reported.

Cited by 32 publications

References 11 publications

Aroyl[bis(4-hydroxycoumarin-3-yl)]methanes in reactions with 1,2-diaminobenzenes

Aroyl[bis(4-hydroxycoumarin-3-yl)]methanes in reactions with 1,2-diaminobenzenes

Electrooxidation of Iodide in the Presence of 4-Hydroxycoumarin: Application to a Simple Coulometric Titration of 4-Hydroxycoumarin

New synthesis and reactivity of 3‐bromoacetyl‐4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one with binucleophilic amines

Contact Info

Product

Resources

About