Wet and Dry Processes for the Selective Transformation of Phosphonates to Phosphonic Acids Catalyzed by Brønsted Acids

• Published in: Journal of organic chemistry Vol. 85; no. 22; pp. 14411 - 14419
• Main Authors: Li, Chunya, Saga, Yuta, Onozawa, Shun-ya, Kobayashi, Shu, Sato, Kazuhiko, Fukaya, Norihisa, Han, Li-Biao
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 20.11.2020; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; INHIBITION; REAGENTS; ESTERS; HYDROLYSIS; DEALKYLATION; EFFICIENT; ACCESS
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.0c00550

A “wet” process and two “dry” processes for converting phosphonate esters to phosphonic acids catalyzed by a Brønsted acid have been developed. Thus, in the presence of water, a range of alkyl-, alkenyl-, and aryl-substituted phosphonates can be generally hydrolyzed to the corresponding phosphonic acids in good yields catalyzed by trifluoromethyl sulfonic acid (TfOH) at 140 °C (the wet process). On the other hand, with specific substituents of the phosphonate esters, the conversion to the corresponding phosphonic acids can be achieved under milder conditions in the absence of water (the dry process). Thus, the conversion of dibenzyl phosphonates to the corresponding phosphonic acids took place smoothly at 80 °C in toluene or benzene in high yields. Moreover, selective conversion of benzyl phosphonates RP­(O)­(OR′)­(OBn) to the corresponding mono phosphonic acids RP­(O)­(OR′)­(OH) can also be achieved under the reaction conditions. The dealkylation via the generation of isobutene of di-tert-butyl phosphonate, and the related catalysis by TfOH took place even at room temperature to give the corresponding phosphonic acids in good to high yields. Nafion also shows high catalytic activity for these reactions. By using Nafion as the catalyst, phosphonic acids could be easily prepared on a large scale via a simple process.