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Sulphonic Acid-induced Fragmentation of Dialkyl Acylphosphonates, Formation of Alkyl Carboxylates and Alkyl Sulphonates

DOI: 10.1039/P29880002029

Source and publish data:

Journal of the Chemical Society. Perkin transactions II p. 2029 - 2034 (1988)

Update date:2022-08-10

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Authors:

Breuer, EliBreuer, Eli

Karaman, RafikKaraman, Rafik

Goldblum, AmiramGoldblum, Amiram

Leader, HaimLeader, Haim

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Article abstract of DOI:10.1039/P29880002029

Heating of dialkyl acylphosphonates with sulphonic acids under anhydrous conditions leads to the formation of alkyl sulphonates and alkyl carboxylates. 31P N.m.r. spectroscopy revealed that the reaction of equimolar amounts of dimethyl benzoylphosphonate (1) and toluene-p-sulphonic acid at room temperature gives dimethyl phosphonate (6) in 50percent yield.It is proposed that the by-product of this reaction, benzoic toluene-p-sulphonic anhydride (8), reacts with the excess of toluene-p-sulphonic acid, to yield toluene-p-sulphonic anhydride (9) and benzoic acid.Heating of these two compounds with dimethyl phosphonate was shown to yield methyl toluene-p-sulphonate and methyl benzoate, respectively.A postulated by-product of these reactions is phosphenous acid (HPO2).Quantum mechanical calculations by the MNDO/H method carried out on dimethyl benzoylphosphonate and its protonation products show that the preferred site of protonation of dimethyl benzoylphosphonate is the P=O oxygen, and that protonation at this site is followed by C-P bond breaking, with zero energy of activation, leading to dimethyl phosphite and benzoylium cation.

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