ChemInform Abstract: SULFENSAEUREN 1. MITT. SYNTH. VON ARENSULFONSAEURECHLORIDEN UND ‐AMIDEN

Abstract

Die Oxidation der Thiophenole (I) mit Chlor in Tetrachlormethan bei ‐15 bis +5°C liefert die Sulfenylchloride (I) (Ausbeute 78‐89%).

Nitrogen-centered free radicals. IX. The ease of formation of thionitroxide radicals

“…The smaller difference in reactivity between 8 and 9 could plausibly reflect subtle steric and/or electronic differences between these two compounds. However, as was shown above, the S-S bond dissociation energy of 8 is [30][31][32][33][34][35][36][37][38][39][40] kcal/mol less than that of 9. The small ratio of k$/kg indicates that there is little or no breaking of the S-S bond in the transition states of these Sh2 reactions.…”

Rearrangements in Lewis acid catalyzed Diels-Alder reactions. Route to substituted bicyclo[2.2.1]heptanones

“…Distillation gave 1.614 g (69%) of pale yellow liquid, bp 112.5-116.5 °C (0.40 mm), which was shown by NMR to contain ca. 15% of the less abundant aldehyde isomer (186) and 85% of the rearrangement product 19: IR (neat) 1737 cm-1 (C=0); NMR (CC14) 0.6-2.6 (broad multiplet, 24 H, aliphatic CH, including a small CH3 singlet at 0.92 due to unreacted 18 and a large CH3 singlet at 1.00 due to 19), 917 (s, -0.15 H, CHO of unreacted 18); MS m/e (rel intensity) 232 (M+,22), 203 (17), 189 (14), 174 (31), 161 (27), 150 (100), 135 (23), 119 (20), 105 (39), 93 (43), 91 (76), 81 (42), 79 (76), 77 (49), 67 (67), 55 (70), 42 (71), 41 (96), 39 (52).…”

“…1.2-3.2 (m. 6 H, aliphatic CH), 6.97 (m, 10 H, ArH), 9.52 (s, 1 H. CHO); MS m/e (rel intensity) 276 (M+, 32), 248 (M -CO, 23), 247 (M -CHO, 20), 205 (15), 172 (26). 129 (37), 115 (40), 104 (40), 91 (100), 77 (30), 43 (23).…”

“…The resulting yellow solution was stirred for an additional 15 min with ice bath cooling and then allowed to warm to room temperature and stirred for another 5 h. The clear dark brown solution was then poured into ice water, and the organic phase was separated and washed successively with portions of 5% HC1, saturated NaHC03, and brine. Drying and concentration gave a golden yellow liquid which was distilled to separate 8.770 g (58%) of ketone 2 as a water-white liquid: bp 54.5-55 °C (5.2 mm); IR (neat) 1740 (C=0), 2970, 2880,1460,1380,967 cm"1; NMR (90 MHz, CC14) 0.97 (d, J = 7 Hz, 3 H, CH3CHC=0), 1.10 (s, 3 H, CH3), 1.19 (s, 3 H, CH3), 1.2-2.0 (m, 7 H, aliphatic CH, including a partially overlapped quartet at 1.83, J = 7 Hz, due to CHC=0); MS m/e (rel intensity) 152 (M+, 17), 137 (M -CH3, 3), 123 (1), 109 (14), 95 (100), 94 (34), 82 (18), 81 (23). 69 (21), 67 (26), 55 (16).…”