o-Benzenedisulfonimide: A Novel and Reusable Catalyst for Acid-Catalyzed Organic Reactions

Margherita Barbero; Silvano Cadamuro; Stefano Dughera; Paolo Venturello

doi:10.1055/s-2007-985559

LETTER

o-Benzenedisulfonimide: A Novel and Reusable Catalyst for Acid-Catalyzed Organic Reactions

Margherita Barbero*, Silvano Cadamuro, Stefano Dughera, Paolo Venturello
Dipartimento di Chimica Generale ed Organica Applicata dell’Università, Via Pietro Giuria, 7, 10125 Torino, Italy
Fax: +39(011)6707642; e-Mail: margherita.barbero@unito.it;

Abstract

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Abstract

The o-benzenedisulfonimide is used as Brønsted acid in catalytic amounts in various acid-catalyzed organic reactions, such as etherification, esterification, and acetalization; the conditions required are mild and in the considered examples the results are always good. A useful aspect of the use of this catalyst is its easy recovery in high yield from the reaction mixture and its reuse in other reactions, with economic and ecological advantages.

Key words

o-Benzenedisulfonimide - Brønsted acid - acid-catalyzed organic reactions - reusable catalyst - dehydrative reactions

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References

References and Notes

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Typical Procedure for o -Benzenedisulfonimide-Catalyzed Etherification (Entry 1, Table 1) To a solution of 1,3-diphenylprop-2-en-1-ol (3; 0.42 g, 2.0 mmol) in abs. EtOH (10 mL) was added o-benzenedisulfon-imide (1; 5 mol%; 0.02 g, 0.1 mmol); the reaction mixture was stirred at r.t. The reaction was monitored by TLC (PE-Et₂O, 6:4), GC, and GC-MS analyses until complete disappearance of the starting material. Then the reaction mixture was evaporated under reduced pressure and the residue was poured into Et₂O-H₂O (40 mL, 1:1). The aqueous layer was separated. The organic extract was washed with H₂O (20 mL), dried over Na₂SO₄, and evaporated under reduced pressure. The crude residue was chromatographed on a short column (PE-Et₂O, 6:4) to provide pure (E)-1,3-diphenyl-3-ethoxyprop-1-ene (4a; GC, GC-MS, TLC, ¹H NMR) in 77% yield (0.37 g); colorless oil. ¹H NMR: δ = 1.33 (t, J = 7.0 Hz, 3 H), 3.60 (superimposed q, J = 7.0 Hz, 2 H diastereotopic), 4.98 (d, J = 6.8 Hz, 1 H), 6.38 (dd, J = 16.0, 6.8 Hz, 1 H), 6.68 (d, J = 16.0 Hz, 1 H), 7.25-7.50 (m, 10 H). ¹³C NMR: δ = 15.72, 64.33, 82.86, 126.93 (2 C), 127.17 (2 C), 127.94, 128.00, 128.84 (4 C), 131.00, 131.45, 136.97, 141.86. MS (EI, 70 eV): m/z (%) 238 (70) [M⁺], 105 (100).

Typical Procedure for o -Benzenedisulfonimide-Catalyzed Esterification (Entry 5, Table 1) To a solution of phenylacetic acid (5; 0.27 g, 2.0 mmol) and butan-1-ol (0.16 g, 2.2 mmol) in toluene (10 mL) was added o-benzenedisulfonimide (1; 25 mol%; 0.11 g, 0.5 mmol) and the reaction mixture was stirred at 90 °C for 30 min. After the usual workup, the crude residue was chromatographed on a short column (PE-Et₂O, 8:2) to provide pure butyl phenylacetate (6a; GC, GC-MS, TLC, ¹H NMR) in 90% yield (0.38 g); colorless oil with spectral data identical to those reported. [22d] ¹H NMR: δ = 0.85 (t, J = 7.0 Hz, 3 H), 1.23-1.34 (m, 2 H), 1.48-1.58 (m, 2 H), 3.56 (s, 2 H), 4.04 (t, J = 6.6 Hz, 2 H), 7.15-7.28 (m, 5 H). ¹³C NMR: δ = 13.86, 19.27, 30.80, 41.66, 64.94, 127.21, 128.72 (2 C), 129.43 (2 C), 134.40, 171.88; MS (EI, 70 eV): m/z (%) = 192 (5) [M⁺], 91 (100).

Typical Procedure for o -Benzenedisulfonimide-Catalyzed Acetalization (Entry 10, Table 1) To a solution of 4-chlorobenzaldehyde (7a; 0.28 g, 2 mmol) and ethane-1,2-diol (9; 0.37 g, 6 mmol) in toluene (5 mL) was added o-benzenedisulfonimide (1; 1 mol%; 0.0044 g, 0.02 mmol) and the reaction mixture was stirred at 90 °C for 60 min. The reaction mixture was treated with solid NaHCO₃, evaporated under reduced pressure, and the residue was poured into Et₂O-H₂O (40 mL, 1:1). The aqueous layer was separated. The organic extract was dried over Na₂SO₄, and evaporated under reduced pressure; the crude residue was chromatographed on a short column (PE-Et₂O, 9.5:0.5) to provide pure 4-chlorobenzaldehyde ethlylene acetal in 87% yield (8d; 0.32 g); colorless oil with spectral data identical to those reported. [19b] ¹H NMR: δ = 3.92-3.99 (m, 2 H), 4.02-4.09 (m, 2 H), 5.72 (s, 1 H), 7.29 (d, J = 8.8 Hz, 2 H), 7.36 (d, J = 8.6 Hz, 2 H). ¹³C NMR: δ = 65.51 (2 C), 103.21, 128.10 (2 C), 128.75 (2 C), 135.20, 136.69. MS (EI, 70 eV): m/z (%) = 184 (35) [M⁺], 183 (100).

<A NAME="RG18207ST-19B">19b</A> Katritzky AR. Odens HH. Voronkov MV. J. Org. Chem. 2000, 65: 1886

The aqueous layer and aqueous washing from the various reactions were collected and evaporated under reduced pressure. The residue was passed through a column of Dowex 50X8 ion-exchange resin (1.6 g for 1 g of product), eluting with H₂O (about 35 mL). After removal of H₂O under reduced pressure, virtually pure (¹H NMR) o-benzenedisulfonimide(1) was recovered; mp 192-194 °C, from toluene (lit. 3: mp 192-194 °C).

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For compound 8d, see:

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