Convenient and Eco-Friendly Method for the Conversion of Benzylic Alcohols into Aldehydes, Ketones, and Carboxylic Acids Using NaOCl without any Additives in 1,2-Dimethoxyethane

Abstract

Oxidation of benzylic alcohols to aldehydes, ketones, and carboxylic acids using NaOCl in 1,2-dimethoxyethane without any additives has been developed. 4-Methylbenzyl alcohol and diphenyl methanol were converted into the corresponding aldehyde and ketone in 97% and 92% yield, respectively. Furthermore, 4-­nitrobenzyl alcohol was directly converted into the corresponding carboxylic acid in 99% yield.

Key words

NaOCl - 1,2-dimethoxyethane - oxidation - alcohol - carbonyl compound

• References and Notes

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• 21 General Procedure A mixture of 1a (10 g, 54.3 mmol) and DME (100 mL) was stirring at 20–30 °C, and 10% (w/w) NaOCl (72.7 g, 97.7 mmol; Wako Pure Chemical Industries, Ltd.) was gradually added to the mixture at 20–25 °C. The reaction was continued for 4 h while keeping the temperature at 20–25 °C. After the reaction was completed, 5% aq Na₂S₂O₃ (50 mL) and toluene (50 mL) were added to the reaction mixture, and the mixture was stirred for 20 min. The organic layer was collected, washed with 1 N NaOH (50 mL) followed by H₂O (50 mL), and concentrated. To the concentrate was added i-PrOH (50 mL), and the mixture was heated to 35–45 °C. H₂O (25 mL) and seed crystals of 2a (10 mg) were added to the mixture to initiate crystallization. Additional H₂O (125 mL) was added dropwise for over 1 h, and then the mixture was stirred at 35–45 °C, 20–25 °C, and 0–10 °C, for over 1 h at each. The resultant crystals were collected by filtration, washed with H₂O (50 mL), and dried under reduced pressure at 50 °C to provide 2a as white crystals (8.93 g, 90.3%). ¹H NMR (500 MHz, CDCl₃): δ = 7.35–7.50 (m, 3 H), 7.58–7.64 (m, 2 H), 7.69–7.75 (m, 2 H), 7.88–7.95 (m, 2 H), 10.03 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 127.4, 127.7, 128.5, 129.0, 130.3, 135.3, 139.7, 147.2, 191.9.
• 22 Conditions: 2.3 or 2.4 equiv of NaOCl were used for these reactions because the oxidations of some substrates with 1.8 equiv of NaOCl required longer reaction time.
• 23 The Procedure for Oxidation to Carboxylic Acid To a solution of 1f (1.00 g, 6.53 mmol) in DME (20 mL) was added 10% aq NaOCl (11.67 g, 15.67 mmol) at r.t. The mixture was stirred at r.t. for 4 h before adding 10% Na₂SO₃ (10 mL). The mixture was adjusted to pH 3.5 with 6 M HCl and extracted with EtOAc (20 mL). The aqueous layer was extracted again with EtOAc (10 mL), and the combined organic extract was washed with H₂O (10 mL) before being concentrated under reduced pressure. EtOAc (4 mL) and n-heptane (4 mL) were added at r.t., then the solids were collected by filtration and washed with n-heptane (3 mL) to afford 3f (1.01 g, 93%). ¹H NMR (500 MHz, DMSO-d ₆): δ = 8.18 (d, J = 8.8 Hz, 2 H), 8.33 (d, J = 8.8 Hz, 2 H), 13.68 (br s, 1 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 123.6, 130.6, 136.4, 150.0, 165.7.
• 24 The Procedure for Oxidation of 1o A mixture of 1o (500 mg, 2.74 mmol) and DME (10 mL) was stirred at r.t. and then 10% aq NaOCl (4.90 g, 6.59 mmol) was gradually added to the mixture. Stirring of the mixture was continued at r.t. for 4 h. Then 10% aq Na₂SO₃ (5 mL) was added to the mixture, and stirring was continued for 5 min. EtOAc (20 mL) and H₂O (10 mL) were added to the mixture. Quantitative analysis of the organic layer by HPLC showed the yield of 2o to be 100%, and then the organic layer was concentrated, and the residue was purified by column chromatography on silica gel using n-hexane–EtOAc (10:1) as eluent to provide the desired ketone 2o (492 mg, 99%). ¹H NMR (500 MHz, CDCl₃): δ = 7.17–7.27 (m, 2 H), 7.35–7.47 (m, 4 H), 7.54–7.63 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 120.3, 124.2, 129.0, 134.1, 134.6, 144.3, 193.7.