Chemistry of acetylenic ethers XL: Rearrangement during the conversion of ethoxyethyne with butynedioic acid

✍ Scribed by J. Cley; J. F. Arens

• Publisher: Elsevier Science
• Year: 2010
• Tongue: English
• Weight: 253 KB
• Volume: 78
• Category: Article
• ISSN: 0165-0513
• DOI: 10.1002/recl.19590781114

✦ Synopsis

Abstract

Ethoxyethyne I readily reacted with an ethereal solution of butynedioic acid V affording a product, C~12~H~16~O~7~, obviously formed from 1 mole of butynedioic acid, two moles of ethoxyethyne and one mole of water. Further investigations revealed that it had the anhydride structure IX. By performing the conversion in alcohol, tetraethyl DL‐butane‐1,2,3,4‐tetra‐carboxylate X, was obtained.

The reactions probably involved a rearrangement as pictured in the scheme on page 931 and thus proceeded via the bis‐ketene VIII.

From phenylpropiolic acid and ethoxyethyne the anhydride XI of 1‐phenylnaphthalene‐2,3‐dicarboxylic acid was obtained in low yield. Tetrolic acid was converted into its anhydride in high yield.