Uses
2,4,6-Trichlorophenyl forMate is a highly active and readily available carbon monoxide (CO) substitute, primarily used in palladium-catalyzed carbonylation reactions, especially as an intermediate in the synthesis of chemicals such as pesticides, insecticides, and herbicides.
Synthesis
1. In a dry reaction flask, formic acid (57.3 mL, 1519 mmol) and acetic anhydride (115 mL, 1216 mmol) were added, stirred and heated to 60 °C, and the reaction was maintained at this temperature for 1.5 hours.
2. Upon completion of the reaction, the reaction mixture was cooled to room temperature.
3. The cooled reaction solution was slowly poured into a flask containing 2,4,6-trichlorophenol (30 g, 152 mmol) and sodium acetate (12.46 g, 152 mmol).
4. The mixture was stirred and reacted at room temperature for 3.5 hours.
5. At the end of the reaction, the reaction mixture was diluted with toluene (300 mL) followed by washing the organic phase with deionized water (2 x 200 mL).
6. The organic phase was separated, dried over anhydrous sodium sulfate and filtered to remove the desiccant.
7. The filtrate was concentrated to dryness under reduced pressure to give white needle-like crystals of 2,4,6-trichlorophenyl formate (32.45 g). 8. The product was analyzed by liquid chromatography.
8. The product was analyzed and confirmed by liquid chromatography-mass spectrometry (LCMS) using 2 mM formic acid as the mobile phase with a retention time (Rt) of 1.15 min. The [M + Na]+ peak was observed by mass spectrometry at m/z of 249.8.
References
[1] Organic Letters, 2012, vol. 14, # 20, p. 5370 - 5373,4
[2] ChemCatChem, 2016, vol. 8, # 10, p. 1788 - 1791
[3] Recueil des Travaux Chimiques des Pays-Bas, 1965, vol. 84, p. 1247 - 1252
[4] Patent: WO2017/37116, 2017, A1. Location in patent: Page/Page column 76
[5] Patent: WO2017/50714, 2017, A1. Location in patent: Page/Page column 53
