Microwave-assisted esterification of phosphinic acids

G. Keglevich, Erika Bálint, Nóra Zs Kiss, Erzsébet Jablonkai, L. Hegedûs, A. Grün, István Greiner

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

The usual synthesis of phosphinates involving the reaction of phosphinic chlorides with alcohols or phenols in the presence of a tertiary amine in an apolar solvent cannot be regarded as "green" and requires expensive P-reagents. We have found that in certain cases phosphinic acids can be esterified by simple alcohols under microwave (MW) conditions. Hence, cyclic phosphinic acids, such as 1-hydroxy-3- and 2-phospholene 1-oxide derivatives (A), 1-hydroxyphospholane 1-oxides (B) and 1-hydroxy-1,2,3,4,5,6- hexahydrophosphinine 1-oxide (C) could be converted to the corresponding esters by reaction with alcohols. Using a 15-fold excess of the alcohol at around 200 °C, the preparative yields of the phosphinates amounted to 45-60%. The novel reaction is the consequence of the beneficial specific MW effect that was proved by comparative thermal experiments. Phosphinates may also be prepared by the alkylating esterification of phosphinic acids with alkyl halides. Under solventless and MW conditions in the presence of a phase transfer (PT) catalyst and K2CO3, cyclic phosphinic acids A, B and C mentioned above were converted to the corresponding phosphinates in 85-95% yields. It was found that the simultaneous use of the MW and PT catalytic techniques is beneficial when alkyl halides of normal or decreased reactivity are applied. Both methods described can be regarded as environmentally friendly and offer advantages over the traditional esterifications of phosphinic acids.

Original languageEnglish
Pages (from-to)1802-1810
Number of pages9
JournalCurrent Organic Chemistry
Volume15
Issue number11
Publication statusPublished - Jun 2011

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Phosphinic Acids
Esterification
Microwaves
Alcohols
Oxides
Phenols
Amines
Chlorides
Esters
Derivatives
Catalysts

Keywords

  • Esterification
  • Green chemistry
  • Microwave
  • Phosphinates
  • Phosphinic acids

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Keglevich, G., Bálint, E., Kiss, N. Z., Jablonkai, E., Hegedûs, L., Grün, A., & Greiner, I. (2011). Microwave-assisted esterification of phosphinic acids. Current Organic Chemistry, 15(11), 1802-1810.

Microwave-assisted esterification of phosphinic acids. / Keglevich, G.; Bálint, Erika; Kiss, Nóra Zs; Jablonkai, Erzsébet; Hegedûs, L.; Grün, A.; Greiner, István.

In: Current Organic Chemistry, Vol. 15, No. 11, 06.2011, p. 1802-1810.

Research output: Contribution to journalArticle

Keglevich, G, Bálint, E, Kiss, NZ, Jablonkai, E, Hegedûs, L, Grün, A & Greiner, I 2011, 'Microwave-assisted esterification of phosphinic acids', Current Organic Chemistry, vol. 15, no. 11, pp. 1802-1810.
Keglevich, G. ; Bálint, Erika ; Kiss, Nóra Zs ; Jablonkai, Erzsébet ; Hegedûs, L. ; Grün, A. ; Greiner, István. / Microwave-assisted esterification of phosphinic acids. In: Current Organic Chemistry. 2011 ; Vol. 15, No. 11. pp. 1802-1810.
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