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Current Organic Chemistry


ISSN (Print): 1385-2728
ISSN (Online): 1875-5348

Research Article

The Synthesis of α-Hydroxy- and α-Chlorophosphonic Acid Derivatives Starting from Benzaldehydes and Phosphorous Acid or Dimethyl Phosphite

Author(s): Alajos Grün*, István Greiner and György Keglevich*

Volume 23, Issue 8, 2019

Page: [968 - 973] Pages: 6

DOI: 10.2174/1385272823666190611103102

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The addition of phosphorous acid on the C=O group of substituted benzaldehydes in the presence of hydrochloric acid in water affords a mixture of the corresponding α - chlorophosphonic acid and α-hydroxyphosphonic acid. The selectivity towards the α-chloro derivatives may be increased to 92% by the excess of HCl applying forcing conditions. α- Hydroxyphosphonic acids may be synthesized better in yields of 83-92% by the hydrolysis of the corresponding dimethyl α-hydroxyphosphonates. α-Chlorophosphonic acids may also be obtained in yields of 66-79% from α -hydroxyphosphonic esters by reaction with thionyl chloride followed by hydrolysis. The α -chlorophosphonic acids and esters are useful intermediates for other phosphonic derivatives.

Keywords: Phosphorous acid, dimethyl phosphite, substituted benzaldehydes, α-chlorophosphonic acid, α -hydroxyphosphonic acid, organophosphorus compounds.

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Graphical Abstract
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