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31.39.1.1.2.4 Variation 4: The Phospho-Fries Rearrangement

DOI: 10.1055/sos-SD-031-02217

Gorrell, I. B.; Kee, T. P.Science of Synthesis, (2007311953.

The base-induced rearrangement of dialkyl aryl phosphates into the corresponding (2-hydroxyaryl)phosphonates is analogous to the well-known Fries rearrangement in which a phenolic ester is converted into an acyl phenol. Both mono and bis(phosphonic acids) have been prepared by this method (Table 1).[‌80‌,‌81‌] For example, diethyl phenyl phosphate is converted into (2-hydroxyphenyl)phosphonic acid by treatment with lithium diisopropylamide followed by hydrolysis of the resulting phosphonate, with the product isolated as its anilinium salt (Table 1, entry 1).[‌80‌] The preparation of (2-hydroxyphenyl)phosphonic acid can be modified so as to avoid the need to isolate the anilinium salt, by using the di-tert-butyl phosphate and carrying out the hydrolysis with trifluoroacetic acid in benzene (Table 1, entry 2).[‌82‌] The use of tert-butyl phosphates has been found to have limitations[‌83‌] but this is still the best method for preparing (2-hydroxyphenyl)phosphonic acid. The method employing trifluoroacetic acid hydrolysis conditions has also been used to prepare (2-hydroxy-5-methoxyphenyl)phosphonic acid in 73% yield,[‌82‌] and a similar methodology has been used to prepare (2-hydroxy-6-methoxyphenyl)phosphonic acid and (2-hydroxy-4,6-dimethoxyphenyl)phosphonic acid.[‌84‌] The preparation of (2-sulfanylphenyl)phosphonic acid (17) by the same method has also been reported (Scheme 14).[‌66‌]

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References


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