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.

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

References and Notes

1 Barbero M. Bazzi S. Cadamuro S. Dughera S. Piccinini C. Synthesis  2010,  315 ; and references cited therein

2a Hollemann AF. Recl. Trav. Chim. Pays-Bas  1921,  40:  446 

2b Hurtley WR. Smiles S. J. Chem. Soc.  1926,  1821 

2c Hendrickson JB. Okano S. Bloom RK. J. Org. Chem.  1969,  34:  3434 

2d Blaschette A. Jones PG. Hamann T. Näveke M. Z. Anorg. Allg. Chem.  1993,  619:  912 

2e Davis FA. Sundarababu G. Qi H. Org. Prep. Proced. Int.  1998,  30:  107 

2f Barbero M. Degani I. Fochi R. Regondi V. Gazz. Chim. Ital.  1986,  116:  165 

2g Sørbye K. Tautermann C. Carlsen P. Fiksdahl A. Tetrahedron: Asymmetry  1998,  9:  681 

2h Karino H, Goda H, Sakamoto J.-I, Yoshida K, and Nishiguchi H. inventors;  WO96/33167.  ; Chem. Abstr. 1997, 126, 18657

3a Garcia-Garcia P. Lay F. Garcia-Garcia P. Rabalakos C. List B. Angew. Chem. Int. Ed.  2009,  48:  4363 

3b Treskow M. Neudörfl J. Giernoth R. Eur. J. Org. Chem.  2009,  3693 

4a Hoyle J. In The Chemistry of Sulphonic Acids, Esters and their Derivatives   Patai S. Rappoport Z. Wiley; New York: 1991.  p.379-386  

4b Nishiguchi A. Maeda K. Miki S. Synthesis  2006,  4131 

5a Barbero M, Cadamuro S, Degani I, Fochi R, and Regondi V. inventors; EP  234249.  ; Chem. Abstr. 1988, 108, 23697

5b Barbero M. Cadamuro S. Degani I. Fochi R. Regondi V. Synthesis  1989,  957 

5c Barbero M, Cadamuro S, Degani I, and Fochi R. inventors; IT  0001245596. 

6 Romagnoli R. Baraldi PG. Carrion MD. Cara CL. Preti D. Fruttarolo F. Pavani MG. Tabrizi MA. Tolomeo M. Grimaudo S. Di Cristina A. Balzarini J. Hadfield JA. Brancale A. Hamel E. J. Med. Chem.  2007,  50:  2273 

7 Damschroder RE. Peterson WD. Org. Synth., Coll. Vol. III  1955,  106 

8a Leuckart R. J. Prakt. Chem.  1890,  41:  179 

For reviews, see:

8b Baguley PA. Walton JC. Angew. Chem. Int. Ed.  1998,  37:  3072 

8c Studer A. Synthesis  2003,  835 

9a Barbero M, Degani I, Fochi R, and Perracino P. inventors; WO  98/39312.  ; Chem. Abstr. 1998, 129, 244942

9b Barbero M. Crisma M. Degani I. Fochi R. Perracino P. Synthesis  1998,  1171 

10a Wang C. Hamilton C. Meister P. Menning C. Org. Process Res. Dev.  2007,  11:  52 

10b Percec V. Bera TK. De B B. Sanai Y. Smith J. Holerca MN. Barboiu B. J. Org. Chem.  2001,  66:  2104 

11 Barbero M. Degani I. Dughera S. Fochi R. Perracino P. Synthesis  1999,  90 

12 Farrar WV. J. Chem. Soc.  1960,  3063 

13 Limpricht H. Liebigs Ann. Chem.  1891,  261:  310 

14 Barber HJ. Smiles S. J. Chem. Soc.  1928,  1141 

15a Armarego WLF. Turner EE. J. Chem. Soc.  1956,  1665 

15b Armarego WLF. Turner EE. J. Chem. Soc.  1957,  13 

16 Aikawa K. Mikami K. Chem. Commun.  2005,  5799 

17 Robinson MK. Kochurina VS. Hanna JM. Tetrahedron Lett.  2007,  48:  7687 

18 Darses S. Jeffery T. Genet J.-P. Tetrahedron Lett.  1996,  37:  3857 

19 Barbero M. Degani I. Dughera S. Fochi R. J. Org. Chem.  1999,  64:  3448 

20 Bhar D. Chandrasekaran S. Synthesis  1994,  785 

21 Fabbri D. Delogu G. De Lucchi O. J. Org. Chem.  1993,  58:  1748 

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).

23 Chau MM. Kice JL. J. Org. Chem.  1977,  42:  3265