The synthesis of α-hydroxy-and α-chlorophosphonic acid derivatives starting from benzaldehydes and phosphorous acid or dimethyl phosphite

A. Grün, István Greiner, G. Keglevich

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish
Pages (from-to)968-973
Number of pages6
JournalCurrent Organic Chemistry
Volume23
Issue number8
DOIs
Publication statusPublished - Jan 1 2019

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Benzaldehydes
Hydroxy Acids
Derivatives
Acids
Hydrolysis
Esters
Hydrochloric Acid
dimethyl hydrogen phosphite
phosphonic acid
Water

Keywords

  • Dimethyl phosphite
  • Organophosphorus compounds
  • Phosphorous acid
  • Substituted benzaldehydes
  • α-chlorophosphonic acid
  • α-hydroxyphosphonic acid

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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abstract = "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.",
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T1 - The synthesis of α-hydroxy-and α-chlorophosphonic acid derivatives starting from benzaldehydes and phosphorous acid or dimethyl phosphite

AU - Grün, A.

AU - Greiner, István

AU - Keglevich, G.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - 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.

AB - 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.

KW - Dimethyl phosphite

KW - Organophosphorus compounds

KW - Phosphorous acid

KW - Substituted benzaldehydes

KW - α-chlorophosphonic acid

KW - α-hydroxyphosphonic acid

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