Alkanedisulfamic acid-functionalized silica-coated magnetic nanoparticles (ADSA-MNPs) were prepared by a simple method and evaluated as efficient catalysts for the preparation of mono-, bis-, and tris[bis(4-hydroxycoumarinyl)methanes] through condensation of 4-hydroxy-2H-coumarin-2-one with mono-, di-, or trialdehydes, respectively. The heterogeneous nanocatalyst was readily recovered from the reaction mixture by using external magnet and was reused five times without significant loss of catalytic activity.Acid-functionalized silica-coated magnetic nanoparticles have recently emerged as attractive supports for immobilization of homogeneous catalysts. Various acid-functionalized silica-coated magnetic nanoparticles have been prepared and used as efficient catalysts for a range of organic transformations, such as deprotection of benzaldehyde dimethylacetals 1 and the synthesis of α-amino nitriles; 2 mono-, bis-, and tris[bis(6-aminopyrimidinyl)methanes]; 3 quinolines; 4 benzo[a]xanthenone derivatives; 5 and aminoimidazopyridine skeletons. 6 Coumarin derivatives have received considerable attention because of their useful pharmacological activities. 4-Hydroxycoumarin derivatives have attracted particular attention because of their useful biological and pharmacological properties, such as anticoagulant, 7 spasmolytic, 8 and rodenticidal activities. 9 Coumarins in general, and biscoumarins in particular, exhibit antifungal, anti-HIV, anticancer, antithrombotic, antimicrobial, antioxidant 10,11 urease-inhibitory, 12 cytotoxic, and enzyme inhibitory activities. 13 As a result, the synthesis of this class of compounds is very important. The reaction of 4-hydroxycoumarin with aldehydes affords the corresponding bis(4-hydroxycoumarinyl)methanes, a useful class of organic compounds. This reaction is catalyzed by ruthenium(III) chloride hydrate, 14 piperidine, 12 sulfated titania, 15 iodine, 16 or a poly(4-vinylpyridinium butylsulfonate)-supported catalyst. 17 Although the known procedures for the synthesis of corresponding bis(4-hydroxycoumarinyl)methanes have their merits, they also suffer from some drawbacks, such as low yields, prolonged reaction times, the use of costly reagents or catalysts, or the use of toxic organic solvents. The recovery of the catalyst can also be a problem. Although the reaction of 4-hydroxycoumarin with monoaldehydes has been investigated, [11][12][13][14][15][16][17][18][19] there have been no reports on reactions of 4-hydroxycoumarin with di-or trialdehydes for the synthesis of bis-and tris[bis(4-hydroxycoumarinyl)methanes], respectively. As a continuation of our research on the preparation and catalytic investigation of new acid-functionalized magnetic nanoparticles, 3,20 we synthesized new alkanedisulfamic acid magnetic nanoparticles (ADSA-MNPs) by direct reaction of chlorosulfonic acid with diaminoalkylsilicacoated magnetic nanoparticles (Scheme 1), and we used these nanoparticles as a catalyst system for the synthesis of mono-, bis-, and tris[bis(4-hydroxycoumarinyl)methanes] by condensa...