Wet and Dry Processes for the Selective Transformation of Phosphonates to Phosphonic Acids Catalyzed by Brønsted Acids
| Autor: | Li-Biao Han, Shu Kobayashi, Kazuhiko Sato, Chunya Li, Yuta Saga, Norihisa Fukaya, Shun-ya Onozawa |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Trifluoromethyl 010405 organic chemistry Organic Chemistry Sulfonic acid Alkylation 010402 general chemistry 01 natural sciences Phosphonate Medicinal chemistry 0104 chemical sciences Catalysis chemistry.chemical_compound Hydrolysis chemistry Brønsted–Lowry acid–base theory Alkyl |
| Zdroj: | The Journal of organic chemistry. 85(22) |
| ISSN: | 1520-6904 |
| Popis: | A "wet" process and two "dry" processes for converting phosphonate esters to phosphonic acids catalyzed by a Bronsted 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. |
| Databáze: | OpenAIRE |
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