A New Effective Synthesis of Arene Mono- and Disulfonyl Chlorides

Abstract

Arene mono- and disulfonyl chlorides have been easily synthesized starting from the corresponding anilines via aqueous oxidative chlorination of S-aryl O-ethyl dithiocarbonates intermediates, aryl methyl sulfides, or from arenethiols.

Key words

arenesulfonyl chlorides - disulfonyl chlorides - oxidative chlorination - arenediazonium salts - aryl dithiocarbonates

References and Notes

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22

Diazotization of Amines 2 - General Procedure To a stirred solution of amines 2 (1.0 mmol) and HBF₄ (54% in Et₂O. 1.2 mmol. 1.90 g) in HCOOH (15 mL), at 5-10 ˚C, 3-methylbutyl nitrite (1.29 g, 1.1 mmol) was slowly added at such a rate that the temperature did not exceed 10 ˚C. Then the reaction mixture was stirred for 10 min in an ice bath, and at r.t. for 5 min. Finally, after cooling at 0-5 ˚C, anhyd Et₂O was added to precipitate salts 3, gathered by filtration on a Büchner funnel, and washed several times with Et₂O. After drying under vacuum, pure salts 3 were obtained and immediately reacted (physical and ^¹H NMR and ^¹³C NMR spectral data identical to literature).
Conversion of Crude Salts 3 to O -Ethyl S -Aryl Dithiocarbonates 4 and Oxidative Chlorination of Crudes 4 to Arenesulfonyl Chlorides 5 - General Procedures Crude salts 3 (1.0 mmol) were carefully added under stirring to a solution of potassium O-ethyl dithiocarbonate (1.0 mmol, 1.60 g) and Na₂CO₃ (1.0 mmol, 1.06 g) in H₂O (40 mL), heated to 35-40 ˚C. Then the reaction mixture was stirred at 60 ˚C for 20 min. After cooling to r.t., the resultant mixture was poured into Et₂O-H₂O (40 mL, 2:1). The aqueous layer was separated and extracted with Et₂O (2 × 20 mL). The combined organic extracts were washed with H₂O (20 mL), dried over Na₂SO₄, and evaporated. The crude residues were directly reacted to give arenesulfonyl chlorides 5. A small stream of Cl₂ was bubbled through a well-stirred ice-cooled emulsion of crudes 4 in H₂O (20 mL) or HCOOH-H₂O (40 mL, 9:1; for crude 4f), at such a rate that the temperature did not rise to 10 ˚C. The reaction was stopped when Cl₂ was no longer absorbed and TLC analysis (PE-Et₂O, 8:2) showed the presence of only one persistent spot. After removing chlorine excess, the reaction mixture was extracted with CH₂Cl₂ (3 × 20 mL); organic extracts were neutralized with 10% aq NaHCO₃, dried, and evaporated under reduced pressure. Crude residues chromatographed on a short column (PE-Et₂O, 9:1) provided pure arenesulfonylchlorides 5 (comparison with literature data or commercially pure samples).
Benzene-1,2-disulfonyl Chloride (5f) ^²g After completion of oxidative chlorination (TLC analysis and appearance of a fine dispersed white solid), chlorine excess was removed under vacuum; crude virtually pure 5f was filtered on a Büchner funnel and washed with cold H₂O. Mp 143-144 ˚C (CCl₄; lit. 143-144 ˚C).^{²f ¹}H NMR (200 MHz, CDCl₃): δ = 8.04-8.11 (m, 2 H), 8.45-8.53 (m, 2 H). ^¹³C NMR (50 MHz, CDCl₃): δ = 132.6 (2 C), 136.4 (2 C), 141.4 (2 C). MS (EI): m/z (%) = 274 (20) [M⁺].
Biphenyl-2,2′-disulfonyl Chloride (7) Mp 143-144 ˚C (CHCl₃-PE; lit. 144-145 ˚C).^²³ Prepared by suspending crude 17 in CH₂Cl₂/H₂O (10 mL, 10:1) and reacting with excess chlorine at 0-10 ˚C for 30 min; then HCOOH (10 mL) was added, and chlorination was continued until only two persisting spots were present on TLC analysis. By column chromatography (CH₂Cl₂-MeOH, 99:1), disulfonyl chloride 7 was eluted as first product (R _f = 0.8); the second eluted product was 13 (R _f = 0.3); mp 143-144 ˚C (CHCl₃-PE; lit.^²³ 144-145 ˚C). ^¹H NMR (200 MHz, CDCl₃): δ = 7.49 (dd,, J = 1.8, 7.2 Hz, 1 H), 7.67 (td, J = 1.8, 7.6 Hz, 1 H), 7.75 (td, J = 1.6, 7.6 Hz, 1 H), 8.20 (dd, J = 1.6, 8.0 Hz, 1 H). ^¹³C NMR (50 MHz, CDCl₃): δ = 129.0 (2 C), 129.8 (2 C),132.0 (2 C), 134.3 (2 C), 135.7 (2 C), 142.6
(2 C).
( R )-Binaphthyl-2,2′-disulfonyl Chloride (8)
Colorless needles; mp 241.2-242.2 ˚C (CHCl₃-PE; lit. 244.3 ˚C).^{³b ¹}H NMR (200 MHz, CDCl₃): δ = 7.09 (d, J = 8.6 Hz, 2 H), 7.38 (ddd, J = 1.4, 7.0, 8.6 Hz, 2 H), 7.65 (ddd, J = 1.2, 7.0, 8.2 Hz, 2 H), 8.00 (d, J = 8.4 Hz), 8.20 (d, J = 9.0 Hz, 2 H), 8.27 (d, J = 9.0 Hz, 2 H). ^¹³C NMR (50 MHz, CDCl₃): δ = 123.2 (2 C), 127.9 (2 C), 128.4 (2 C), 128.5 (2 C), 130.1 (2 C), 131.0 (2 C), 131.8 (2 C), 133.6
(2 C), 135.3 (2 C), 140.7 (2 C).