An Improved Synthesis of Hydroxy Aryl Ketones by Fries Rearrangement with Methanesulfonic Acid/Methanesulfonic Anhydride

Ingyu Jeon; Ian K. Mangion

doi:10.1055/s-0032-1316568

Synlett, Table of Contents

Synlett 2012; 23(13): 1927-1930
DOI: 10.1055/s-0032-1316568

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An Improved Synthesis of Hydroxy Aryl Ketones by Fries Rearrangement with Methanesulfonic Acid/Methanesulfonic Anhydride

Authors

Ingyu Jeon*

Department of Process Research, Merck and Co., Inc., PO Box 2000, Rahway, NJ 07065, USA, Fax: +1(732)5941499 Email: Ingyu.jeon@merck.com
Ian K. Mangion

Department of Process Research, Merck and Co., Inc., PO Box 2000, Rahway, NJ 07065, USA, Fax: +1(732)5941499 Email: Ingyu.jeon@merck.com

Abstract

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Abstract

Methanesulfonic acid treated with methanesulfonic anhydride effectively mediates the Fries rearrangement of aryl esters to give hydroxy aryl ketones with high yields.

Key words

rearrangement - ketones - esters - methanesulfonic acid - methanesulfonic anhydride

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References

References and Notes
1 Martin R. Org. Prep. Proced. Int. 1992; 24: 369
2 Gerecs A. The Fries Reaction in Friedel–Crafts and Related Reactions . Olah GA. Interscience; New York: 1964. Part 1, Vol. 3

For HF-mediated reactions, see:

3a Davenport KG. EP 251552, 1988
3b Yanagawa T. JP 63132 855, 1988
3c Patton JR. EP 228172, 1987
3d Fukuoka S. JP 62114927, 1987

4 For HF-, AlCl₃-, and BF₃-mediated reactions, see: Hocking MB. J. Chem. Technol. Biotechnol. 1980; 30: 626
5 For TiCl₄- and SnCl₄-mediated reactions, see: Ramesh BB. IN 171970, 1993
6 For BF₃-mediated reaction, see: Boyer JL. J. Org. Chem. 2000; 65: 4712
7 Mouhtady O, Iloughmane HG, Roques N, Roux CL. Tetrahedron Lett. 2003; 44: 6379
8 Commarieu A, Hoelderich W, Laffitte JA, Dupont MP. J. Mol. Catal. A.: Chem. 2002; 182: 137

9a Staniland PA. EP 57503, 1982
9b Kusuda M. JP 62234041, 1987
9c Behr A. DE 19736905, 1998

10 Sharghi H. J. Chem. Res., Synop. 1998; 10: 628
11 Kaboudin B. Tetrahedron 1999; 55: 12865
12 Springbor Laboratories, Inc., An acute oral toxicity study in rats with methanesulfonic acid, SLI Study No. 3255.11, November 7, 1997.
13 Typical Procedure for the Fries Rearrangement with MSA/Methanesulfonic Anhydride The methanesulfonic anhydride (59.1 mmol) was added to a MSA (384 mL) at 90 °C. The reaction mixture was stirred for 1 h, at this time KF (%) was measured. To MSA/methane-sulfonic anhydride solution, 139.43 g of 3-bromophenyl 2-(2,5-dibromophenyl)acetate (295 mmol, Table 3, entry 9) was added under nitrogen atmosphere at 65 °C. The resulting solution was stirred for 22–24 h, at this time TLC indicated completion. After reaction was completed, batch was cooled to r.t. followed by addition of 2-PrOH–H₂O (3:1, 1115 mL) while maintaining batch temperature at below 65 °C. Batch was then stirred for 20 min, filtered, and dried to afford 108 g (81% yield) of the desired product as a crystalline solid (Table 3, entry 9). ¹H NMR (500 MHz, DMSO-d ₆): δ = 11.60 (s, 1 H), 7.87 (d, J = 8.5 Hz, 1 H), 7.67 (d, J = 2.4 Hz, 1 H), 7.59 (d, J = 8.7 Hz, 1 H), 7.45 (dd, J = 8.7, 2.4 Hz, 1 H), 7.26 (d, J = 1.9 Hz, 1 H), 7.20 (dd, J = 8.4, 1.8 Hz, 1 H), 4.59 (s, 2 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 199.5, 160.7, 138.4, 135.5, 134.5, 132.6, 132.1, 129.2, 124.5, 123.0, 121.5, 120.9, 120.8, 47.9.