Mg/K2S2O8-promoted direct carboxylation of saturated hydrocarbons with CO

✍ Scribed by Mohammad Asadullah; Tsugio Kitamura; Yuzo Fujiwara

• Book ID: 101274430
• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 93 KB
• Volume: 13
• Category: Article
• ISSN: 0268-2605
• DOI: 10.1002/(sici)1099-0739(199907)13:7<539::aid-aoc883>3.0.co;2-2

✦ Synopsis

Saturated hydrocarbons react with carbon monoxide in the presence of magnesium powder and potassium peroxodisulfate in trifluoroacetic acid (TFA) to afford the corresponding carboxylic acids as major products and alkyl trifluoroacetates as minor products in high yields. The use of equimolar amounts of magnesium (5 mmol) and K 2 S 2 O 8 (5 mmol) is best for this reaction. Cyclohexane is carboxylated most effectively at 80 °C for 30 h using 50 atm CO, 3 ml of TFA and 1 mmol of cyclohexane, giving 80% conversion (95% conversion yield) based on cyclohexane. The reactivity of various saturated hydrocarbons has been determined by competitive reactions of equimolar amounts of cyclohexane (5 mmol) and another hydrocarbon (5 mmol). The order of decreasing reactivity obtained is cycloheptane b cyclohexane b cyclopentane b n-propane b methane.