Rearranged Products from the Reaction of Benzenesulfonic Acids with Caustic

Synthesis of 1,3,5-tris[4-(diarylamino)phenyl]benzene and 1,3,5-tris(diarylamino)benzene derivatives

“…The reaction bears resemblance to the formation of phenols by the fusion of sulfonic acids with alkali. 18 Treatment of the aniline 9 with sodium amide generates the sodium anilinide 11 and gives off ammonia. An excess of the anilinide salt is used so that the sulfonic acid is deprotonated.…”

Thermal decomposition of o- and p-benzenedisulfonyl azides in benzene, cyclohexane, cyclohexene, and tetracyclone

“…Addition of anhydrous ether (ca. 15 ml) caused a white, crystalline solid to separate. This was quickly filtered in a drybox and identified as N,N'-di-(l-cyclohexenyl)-o-benzenedisulfonamide (0.64 g, 65%): mp 162-164°; ir (KBr) 3280 (N-H), 1575 (C=C), 1325 (S02), and 1175 cm"1 (S02); NMR (CDCI3) 8.10 (d of d, H3 and He, J3,4 = 6.0, J3,s = 3.0 Hz), 7.66 (d of d, H4 and H5), 7.23 (N-H, 2 H, D20 exchange), 5.50 (m, 2 vinyl ), 2.04-1.82 (m, 8 allylic H), and 1.54-1.32 (m, 8 aliphatic H); MS (70 eV) m/e 396 (M-+, 3), 172 (16), 99 (24), 98 (100), 97 (64).…”

“…Benzene-ether (1:1 v/v, 250 ml) and ether (350 ml) eluted a white, powdery solid (0.99 g, 84%), mp 240-245°. Two recrystallizations from acetonitrile gave granular crystals of a mixture of p-benzenedisulfonyltoluidides: mp 248-257°; ir (KBr) 3270-3220 (N-H), 1340 (S02), and 1165 cm-1 (S02); NMR (DMSO-dg) 10.39, 9.93, and 9.86 (NH, 2 H, D20 exchange), 7.89 (s, 4 H), 7.25-6.9 (m, 8 H), 2.24 (s), 2.03 (s), and 1.87 (s) (6 H); MS (70 eV) m/e 416 (M-+, 8), 107 (15), 106 (100), 79 (11), 78 (6), 77 (15).…”