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

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.

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

References and Notes

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For recent works on acid-catalyzed dehydrative etherification, esterification, and acetalization reactions with metal catalysts, see for example:

13a Sharma GVM. Mahalingam AK. J. Org. Chem.  1999,  64:  8943 

13b Sharma GVM. Prasad TR. Mahalingam AK. Tetrahedron Lett.  2001,  42:  759 

13c Saburi H. Tanaka S. Kitamura M. Angew. Chem. Int. Ed.  2005,  44:  1730 

13d Shibata T. Fujiwara R. Ueno Y. Synlett  2005,  152 

With solid-acid catalysis:

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In supercritical fluids:

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In ionic liquids:

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13l Davis JH. inventors; WO  03086605.  ; Chem. Abstr. 2003, 139, 325782

In water:

13m Manabe K. Iimura S. Sun X.-M. Kobayashi S. J. Am. Chem. Soc.  2002,  124:  11971 

14a Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   3rd ed.:  Wiley; New York: 1999.  Chap. 2. p.17-245  

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15a Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   3rd ed.:  Wiley; New York: 1999.  Chap. 5. p.369-453  

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16a Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   3rd ed.:  Wiley; New York: 1999.  Chap. 4. p.293-368  

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16d Shimizu K.-I. Hayashi E. Hatamachi T. Kodama T. Kitayama Y. Tetrahedron Lett.  2004,  45:  5135 

16e Kumar R. Kumar D. Chakraborti AK. Synthesis  2007,  299 

17

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).

18

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).

19a

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).

19b Katritzky AR. Odens HH. Voronkov MV. J. Org. Chem.  2000,  65:  1886 

20

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).

21 Matsuda I. Wakamatsu S. Komori K.-I. Makino T. Itoh K. Tetrahedron Lett.  2002,  43:  1043 

For compound 6a, see:

22a Sharghi H. Sarvari MH. Eskandari R. J. Chem. Res., Synop.  2005,  488 

22b Vijayakumar B. Iyengar P. Nagendrappa G. Prakash BSJ. J. Indian Chem. Soc.  2005,  82:  922 

22c Banerjee A. Sengupta S. Adak MM. Banerjee GC. J. Org. Chem.  1983,  48:  3106 

22d For compounds 6a and 6b, see: Gumaste VK. Deshmukh ARAS. Bhawal BM. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  1996,  35:  1174 

For compounds 8a and 8b, see:

23a Shimizu K.-I. Hayashi E. Hatamachi T. Kodama T. Kitayama Y. Tetrahedron Lett.  2004,  45:  5135 

For compound 8d, see:

23b Azzena U. Dettori G. Sforazzini G. Yus M. Foubelo F. Tetrahedron  2006,  62:  1557 

23c Shimizu K.-I. Hayashi E. Hatamachi T. Kodama T. Higuchi T. Satsuma A. Kitayama Y. J. Catal.  2005,  231:  131 

23d Huerta FF. Gomez C. Yus M. Tetrahedron  1999,  55:  4043