An economical and safe procedure to synthesize 2-hydroxy-4-pentynoic acid: A precursor towards 'clickable' biodegradable polylactide

Quanxuan Zhang, Hong Ren, Gregory L. Baker

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

2-Hydroxy-4-pentynoic acid (1) is a key intermediate towards 'clickable' polylactide which allows for efficient introduction of a broad range of pendant functional groups onto polymers from a single monomer via convenient 'click' chemistry with organic azides. The incorporation of various pendant functional groups could effectively tailor the physicochemical properties of polylactide. The reported synthesis of 1 started from propargyl bromide and ethyl glyoxylate. However, both of starting materials are expensive and unstable; especially, propargyl bromide is shock-sensitive and subjected to thermal explosive decomposition, which makes the preparation of 1 impractical with high cost and high risk of explosion. Herein, we report a simple, economical and safe synthetic route to prepare 1 using cheap and commercially available diethyl 2-acetamidomalonate (4) and propargyl alcohol. The desired product 1 was obtained via alkylation of malonate 4 with propargyl tosylate followed by a one-pot four-step sequence of hydrolysis, decarboxylation, diazotization and hydroxylation of propargylic malonate 5 without work-up of any intermediate.

Original languageEnglish (US)
Pages (from-to)1365-1371
Number of pages7
JournalBeilstein Journal of Organic Chemistry
Volume10
DOIs
StatePublished - Jun 17 2014

Keywords

  • 'Click' chemistry
  • 'Clickable' polylactide
  • 2-hydroxy-4-pentynoic acid
  • Alkylation
  • Decomposition
  • Diethyl 2-acetamidomalonate
  • One-pot
  • Optimization
  • Propargyl bromide
  • Propargyl tosylate
  • Safe and economical

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