Chemistry of acetylenic ethers 81: synthesis of β‐alkoxy‐β‐chloroacrylic chlorides by addition of phosgene to 1‐alkynyl ethers

Abstract 1‐Alkynyl ethers of the type R‐C≡C‐OR′ (R = H or alkyl and R′ = alkyl) were converted by addition of phosgene into β‐alkoxy‐β‐chloroethene carbonic chlorides RO‐CCl = CR‐CO‐Cl (II). From the adducts some amides were prepared. Hexachloroacetone and chloral reacted with ethoxyethyne without a catalyst to (CCl3)2CCH‐COOC2H5 (I) and CCl3CHCHCOOC2H5 respectively. Sulfur dichloride already adds on to ethoxyethyne at a low temperature, forming bis(2‐ethoxy‐2‐chlorovinyl) sulfide (VIII), which upon alcoholysis yields bis(ethoxycarbonylmethyl) sulfide (IX).