Selective Sulfonylation of Arenes and Benzoylation of Alcohols Using Lithium Perchlorate as a Catalyst Under Neutral Conditions

Abstract

Sulfonylation of aromatics with p-toluenesulfonyl chloride and benzoylation of alcohols with benzoyl chloride using lithium perchlorate as a catalyst is described. The remarkable selectivity under neutral conditions is an attractive feature of this method

Key words

sulfonylation - benzoylation - lithium perchlorate - catalyst - neutral conditions

References

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12

A Typical Procedure for Sulfonylation of Arenes: A mixture of anisole (10 mL), p-toluene sulfonyl chloride (2 mmol) and lithium perchlorate (0.4 mmol) was refluxed for 2.5 h. On completion of the reaction, the mixture was cooled and excess anisole was removed under reduced pressure. To the residue chloroform (10 mL) and water (10 mL) was added. The aq layer was washed with chloroform (3 × 5mL). The combined organic layer was dried with anhyd Na₂SO₄ and removal of the solvent under vacuum furnished crude product, which was further purified by column chromatography.
Yield = 90%; mp = 149 °C; IR (KBr): 683, 834, 1007, 1360, 1599, 2910, 3300 cm^-1; ¹H NMR (300 MHz, CDCl₃): δ = 2.36 (s, 3 H, CH₃), 3.81 (s, 3 H, OCH₃), 6.95 (d, 2 H, J = 8.3 Hz, Ar-H), 7.31 (d, 2 H, J = 7.4 Hz, Ar-H), 7.85 (d, 2 H, J = 8.3 Hz, Ar-H), 7.90 (d, 2 H, J = 7.4 Hz, Ar-H).

19

Typical Procedure for Benzoylation: A mixture of benzyl alcohol (5 mmol), benzoyl chloride (5 mmol) and LiClO₄ (1 mmol) was stirred for 7 h at 25 °C (Table [3] , entry 3). After completion of the reaction (TLC), the solvent was removed under reduced pressure and the product was purified by column chromatography on silica gel. Yield = 80%; IR(neat): 712, 1065, 1107, 1272, 1450, 1716 cm^-1; ¹H NMR (CDCl₃): δ = 4.4 (s, 2 H), 7.3-7.4 (m, 5 H), 8.1-8.15 (m, 5 H); ¹³C NMR: δ = 70.2, 125.8, 127.77, 128.42, 128.61, 129.74, 130.55, 133.02, 141.78, 145.81, 175.9.