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Mannich and O‐Alkylation Reactions of Tetraalkoxyresorcin[4]arenes – The Use of Some Products in Ligand‐Assisted Reactions

“…Many reactions of resorcinarenes have been carried out with mild electrophiles 3. Mannich reactions are such reactions and have been studied widely; they include the use of secondary amines,4 including aza‐crown secondary amines,4ewhich have been used under mild classical conditions with aqueous formaldehyde at an early stage4a–4d and can lead to tetra(dialkylaminomethyl) derivatives 4k–4n. Oxazolidines derived from secondary β‐amino alcohols4f and aminal bis(dimethylamino)methane4g have been used as the equivalents of secondary amines and formaldehyde in Mannich reactions.…”

Synthesis of 3,5-di-tert-butyl-4-hydroxyphenylsulfanylmethyl-substituted tetramethylcalix[4]resorcinarenes

“…According to [9], molecules of calix [4]resorcinarene Ia in crystal are linked to dimers where dimethylaminomethyl groups of neighboring molecules enter the macroring cavity in each other; therefore, these groups become spatially inaccessible for nucleophilic attack. Such associates are likely to dissociate by the action of solvent, whereas prolonged drying favors the 1 10 11 NUGUMANOVA et al…”

“…By contrast, the reaction of benzenethiol II with calixarene Ia preliminarily stored for 3 months gave a mixture of products of partial replacement of the dimethylamino groups (according to the 1 H NMR data) even after heating for 66 h. The reactivity of calix[4]resorcinarene Ia can be restored after prolonged storage by washing with dimethyl sulfoxide and then with water, followed by drying in air. Presumably, the reactivity of aminomethyl calixarene derivatives Ia and Ib depends on their supramolecular organization.According to [9], molecules of calix[4]resorcinarene Ia in crystal are linked to dimers where dimethylaminomethyl groups of neighboring molecules enter the macroring cavity in each other; therefore, these groups become spatially inaccessible for nucleophilic attack. Such associates are likely to dissociate by the action of solvent, whereas prolonged drying favors the R = Me (a), Et (b).…”

Mannich and O‐Alkylation Reactions of Tetraalkoxyresorcin[4]arenes – The Use of Some Products in Ligand‐Assisted Reactions

“…The organic layer was washed with water (2 x 250 CHCl 3 ); C 104 H 108 N 4 O8 : calcd. C, 80.80; H, 7.30; N, 3.62; found: C, 80.86; H, 6.90; N, 3.56; ν max (CH 2 Cl 2 ) /cm-1 3054, 2986, 1421, 1265, 896, 740; δ H (400 MHz, CDCl 3 ) 1.39(12 H, d, J 6.4 Hz),m), 2.69(8 H, t, J 7.6 Hz), 3.21 (12 H, s), 3.81 (4 H, q, J 6.4 Hz),3.87 (4 H, d, J 16.8 Hz), 4.19 (4 H, d, J 16.8 Hz), 4.53 (4 H, t, J 7.6 Hz), 4.57(4 H, d, J 10…”

“…733; δ H (400 MHz, CDCl 3 ) 0.81 (18 H, t, J 7.2 Hz), 0.88 (18 H, t, J 7.2 Hz), 1.46 (36 H, t, J 6.2 Hz), 2.03 (12 H, m), 2.26 (12 H, m), 3.91(6 H, d, J 17.3 Hz), 3.95(6 H, d, J 17.3 Hz), 3.98 (12 H,m), 4.08(6 H, d, J …”