A Novel and Efficient Synthesis of δ-Sultones

Abstract

A class of sulfonic ionic liquids, with the supremacy of methylsulfonylimidazolium triflate hydrochloride, was found to be efficient for catalyzing the self-condensation of acetophenone derivatives and sulfonating the resulting condensates in a one-pot rapid reaction leading to the synthesis of 4,6-diaryl-1,2-oxathiine-2,2-dioxides (diaryl-δ-sultones).

Key words

δ-sultone - ionic liquid - sulfonation - domino reaction - oxathiine-2,2-dioxide

• References and Notes

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• 7 General Method for the Synthesis of 1,2-Oxathiine-2,2-dioxides 2a–f: An acetophenone derivative (1 mmol in each case) was mixed with the ionic liquid 1-methyl-3-sulfonyl-imidazolium triflate hydrochloride (0.2 mL) in a glass vial containing a stirring bar. The mixture was stirred for appropriate time until disappearance of acetophenone at r.t. (see Table 2). Progress of the reaction was monitored by TLC using silica gel coated sheets and EtOAc–petroleum ether (1:4) as eluents. After completion of the reaction (usually less than 5 min), cold distilled H₂O (10 °C, 10 mL) was added to the reaction mixture and the precipitated solids were filtered, dried in air and recrystallized from EtOH (95%). Selected Data for 4,6-Di(4-fluorophenyl)-[1,2]-oxathiine-2,2-dioxide (2b): mp 220 °C. IR (KBr): 3100, 1622, 1350, 1160, 780, 840 cm^–1. ¹H NMR (400.2 MHz, CDCl₃): δ = 7.84 (dd, ³ J _HH = 8.6 Hz, ⁴ J _FH = 4.8 Hz, 2 H), 7.60 (dd, ³ J _HH = 8.6 Hz, ⁴ J _FH= 5.2 Hz, 2 H), 7.23 (t, J = 8.6 Hz, 2 H), 7.22 (t, J = 8.6 Hz, 2 H), 6.72 (s, 1 H), 6.66 (s, 1 H). ¹³C NMR (100.63 MHz, CDCl₃): δ = 164.7 (d, J = 254 Hz), 164.3 (d, J = 253 Hz), 155.8, 146.7, 131.6 (d, J = 4 Hz), 128.9 (d, J = 9 Hz), 128.3 (d, J = 9 Hz), 127.1 (d, J = 3 Hz), 116.6 (d, J = 22 Hz), 116.4 (d, J = 22 Hz), 113.0, 101.9. MS (70 eV): m/z (%) = 320 (52) [M⁺], 256 (83) [M⁺ – SO₂], 227 (100) [M⁺ – CHSO₃], 207 (19), 149 (22), 133 (40), 123 (45), 95 (62). Anal. Calcd for C₁₆H₁₀F₂O₃S (320.31): C, 60.00; H, 3.15. Found: C, 60.13; H, 3.21. Selected Data for 4,6-Di(4-bromophenyl)-[1,2]-oxathiine-2,2-dioxide (2c): mp 216 °C. IR (KBr): 3095, 1620, 1355‌, 1165, 770, 820 cm^–1. ¹H NMR (400.2 MHz, CDCl₃): δ = 7.70 (d, J = 9.2 Hz, 2 H), 7.68 (d, J = 9.2 Hz, 2 H), 7.66 (d, J = 8.8 Hz, 2 H), 7.45 (d, J = 8.4 Hz, 2 H), 6.77 (d, J = 1 Hz, 1 H), 6.70 (d, J = 1 Hz, 1 H). ¹³C NMR (100.63 MHz, CDCl₃): δ = 155.9, 146.5, 134.3, 129.7, 126.4, 125.6, 132.7, 132.4, 128.4, 127.3, 113.7, 102.1. MS (70 eV): m/z (%) = 444 (12) [M⁺, ⁸¹Br ⁸¹Br], 442 (22) [M⁺, ⁸¹Br ⁷⁹Br], 440 (12) [M⁺, ⁷⁹Br ⁷⁹Br], 380 (42) [M⁺ – SO₂, ⁸¹Br ⁸¹Br], 378 (53) [M⁺ – SO₂, ⁸¹Br ⁷⁹Br], 376 (22) [M⁺ – SO₂, ⁷⁹Br ⁷⁹Br], 359 (37), 351 (5) [M⁺ – CHSO₃, ⁸¹Br ⁸¹Br], 349 (10) [M⁺ – CHSO₃, ⁸¹Br ⁷⁹Br], 347 (6) [M⁺ – CHSO₃, ⁷⁹Br ⁷⁹Br], 301 (60), 299 (62), 271 (32) [M⁺ – BrC₆H₄O, ⁸¹Br], 269 (33) [M⁺ – BrC₆H₄O, ⁷⁹Br], 220 (66), 189 (81), 157 (50), 155 (52), 115 (100). Anal. Calcd for C₁₆H₁₀Br₂O₃S (442.12): C, 43.47; H, 2.28. Found: C, 43.41; H, 2.33.
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• 17 Typical Procedure for Synthesis of 1-Methyl-3-sulfonylimidazolium Triflate Hydrochloride: To a flask, kept in an ice-cooled bath and equipped with a magnetic stirring bar, was added a solution of 1-methylimidazole, (0.8 mL, 10 mmol), in anhyd CH₂Cl₂ (15 mL). To this continuously stirred solution was added dropwise chlorosulfonic acid, (0.66 mL, 10 mmol), whereupon white suspended solids were produced. After an hour of additional stirring at r.t., trifluoromethanesulfonic acid (0.88 mL, 10 mmol) was added slowly over a period of 15 min to the flask. Within this time, the suspended white salt inside the flask was completely dissolved. Stirring of this solution was continued for about 30 min at r.t., and then the solvent was removed under reduced pressure. According to this procedure, the ionic liquid [MSIm]OTf·HCl was obtained as a viscous yellow oil. Treatment of aqueous solution of the ionic liquid with AgNO₃ (aq) resulted in the formation and precipitation of AgCl solids. Anal. Calcd for [MSIm]OTf·HCl: C, 17.22; H, 2.31; N, 8.03. Found: C, 17.33; H, 2.43; N, 7.87. NMR Data for [MSIm]OTf·HCl: ¹H NMR (400.13 MHz, CDCl₃): δ (minor component) = 12.62 (s, 1 H), 12.52 (s, 1 H), 8.75 (s, 1 H, CH), 7.60 (s, 1 H, CH), 7.31 (s, 1 H, CH), 4.00 (s, 3 H, Me). ¹H NMR (400.13 MHz, CDCl₃): δ (major component) = 12.62 (s, 1 H), 11.49 (s, 1 H, NH), 8.44 (s, 1 H, CH), 7.36 (s, 1 H, CH), 7.31 (s, 1 H, CH), 3.90 (s, 3 H, Me). ¹³C NMR (100.6 MHz, CDCl₃): δ (minor component) = 135.15 (CH), 123.90 (CH), 12.30 (CH), 118.93 (q, ¹ J _C–F = 317 Hz, CF₃), 36.29 (Me). ¹³C NMR (100.6 MHz, CDCl₃): δ (major component) = 134.77 (CH), 123.19 (CH), 119.90 (CH), 118.93 (q, ¹ J _C–F = 317 Hz, CF₃), 35.84 (Me).
• 18 For quantitative measurement of chloride ion by Mohr’s method, see: Skoog DA, West DM, Holler FJ. Fundamentals of Analytical Chemistry. 7th ed Thomson Learning Inc; Stamford (CT, USA): 1996