Synthesis of biscoumarin derivatives as biological compounds using cellulose sulfonic acid

Abstract

Cellulose sulfonic acid efficiently catalyzes the one-pot reaction of 4hydroxycoumarin and aryl aldehydes under mild reaction conditions to yield biscoumarin derivatives in high yields. This method is of great value because of its easy processing, short reaction time and high yields. We anticipate the present method will receive the attention of medicinal chemists and be used for elaborate synthesis and pharmaceutical screening of biscoumarin based molecules.

Recent Advances in the Synthesis of Biscoumarin Derivatives

“…Cellulose sulfonic acid as solid catalyst was prepared from the reaction of cellulose and chlorosulfonic acid at 100 °C, and efficiently catalyzed the synthesis of biscoumarins (Table , entry 22) …”

“…Also, 4-(bis(4-hydroxy-2oxo-2H-chromen-3-yl)methyl)benzaldehyde was prepared in moderate yield (76%) from the reaction of 1 equiv of terephthaldehyde and 4 equiv of 4hydroxycoumarin in the presence of nano SiO 2 Cl within 7 h ( Nano-TiO 2 @KSF was prepared from the reaction of montmorillonite KSF and titanium (IV) isopropoxide in AcOH at room temperature, and 20 mg of this catalyst was used in the synthesis of bis(4-hydroxycoumarin) derivatives under optimized condition of the reaction, including solvent-free, at 100 C. Also, the efficiency of nanoTiO 2 @KSF changed only slightly (from 95% to 88%) even after three cycles (Table 1, entry 21) 36 Cellulose sulfonic acid as solid catalyst was prepared from the reaction of cellulose and chlorosulfonic acid at 100 C, and efficiently catalyzed the synthesis of biscoumarins ( Table 1, entry 22). 37 o-Benzenedisulfonimide (OBS) (32) is an organocatalyst and highly soluble in both organic solvents and water: also, it is a safe, nonvolatile, noncorrosive catalyst ( Figure 4). OBS as a very strong acidic catalyst (pK a = −4.1 at 20 C) was used in the preparation of biscoumarins at 50 mol% in H 2 O under reflux condition.…”

Sustainable and Eco‐Friendly Method for the Synthesis of Some Bioactive Derivatives of Biscoumarin and Pyrano[3,2‐c]Chromene‐3‐Carbonitrile Using Taurine, as the Catalyst

“…The main method for the preparation of biscomarin derivatives is the Knoevenagel‐Michael reaction. Because of the importance of biscoumarins essentially bis(4‐hydroxycoumarin) in the mentioned fields, many catalysts in various conditions have been introduced for the preparation of them such as [bmim]BF 4 , SDS, [PSebim][OTf], propane‐1,2,3‐triyl tris(hydrogen sulfate), [pyridine–SO 3 H]Cl, phospho sulfonic acid, cellulose sulfonic, W‐doped ZnO nanocomposite, Bi(NO 3 ) 3 ⋅5H 2 O, choline hydroxide, o ‐benzenedisulfonimide, P 4 VPy–CuO‐NPs, sulfonated rice husk ash, silica‐Bonded N ‐propylpiperazine sodium n ‐propionate, boron‐sulfuric acid Nanoparticles, P 4 VPy‐BuSO 3 H−X(AlCl 3 ), 4‐(dimethylamino)pyridine, and piperidine …”

Magnetite-Containing Sulfonated Polyacrylamide as a Nanocatalyst for the Preparation of Biscoumarins

“…Several types of catalysts were introduced previously for this reaction, such as piperidine, 17 tetrabutylammonium bromide, 18 I 2 , 19 sodium dodecyl sulfate, 20 1buthyl-3-methylimidazolium tetrafluoroborate, 21 1-ethyl-3-(3-sulfopropyl)-benzimidazolium trifluoromethanesulfonate, 22 para-dodecylbenzenesulfonic acid/piperidine, 23 3-methyl-1-(4-sulfonic acid)butylimidazolium hydrogen sulfate, 24 B(HSO 4 ) 3 , 25 polyvinylpyrrolidone-supported nickel nanoparticles, 26 poly(4-vinylpyridine)-supported ionic liquids, 27,28 and cellulose sulfonic acid. 29 Also, biscoumarin derivatives have been prepared by the condensation of 1,2-diols and 4-hydroxycoumarin using Pb(OAc) 4 . 30 However, many of these methods have some drawbacks, such as a requirement for either a long reaction time or harsh reaction conditions, provide low yields, include laborious work-up procedures, inefficiency of method when aliphatic aldehydes are used in the reaction, and the use of unrecyclable, hazardous or difficult to handle catalysts.…”