Chemistry of acetylenic ethers XVII: The reactions of some ethoxyethynylcarbinols with mercaptans and thio‐acids
- 1 January 1956
- journal article
- research article
- Published by Wiley in Recueil des Travaux Chimiques des Pays-Bas
- Vol. 75 (12) , 1358-1368
- https://doi.org/10.1002/recl.19560751202
Abstract
The addition of ethyl mercaptan to 1‐ethoxy‐3‐methylbut‐1‐yn‐3‐ol (V) under the influence of peroxides yielded 1‐ethoxy‐2‐ethylmercaptobut‐1‐ene‐3‐ol (VI) in high yield (reaction scheme A). This substance could be rearranged to 2‐ethylmercapto‐3‐methylcrotonaldehyde (VII) (reaction scheme B). The same reaction took place with other mercaptans.The addition of ethyl mercaptan to 1‐(1‐hydroxycyclohexyl)‐2‐ethoxyethyne (XV) and 1‐(1‐hydroxycyclopentyl)‐2‐ethoxyethyne (XVI) under the same conditions yielded 2‐cyclohexylidene‐2‐ethylmercaptoacetaldehyde (XVIII) and 2‐cyclopentylidene‐2‐ethylmercaptoacetaldehyde (XXII) after rearrangement (reaction scheme D).Other thioenol ether compounds were prepared (reaction schemes C and D) starting from the aldehydes VII, XVIII and XXII.Addition of thiobenzoic acid to 1‐ethoxy‐3‐methylbut‐1‐yn‐3‐ol (V) proceeded by a different (probably ionic) mechanism and yielded ‐ after rearrangement and saponification ‐ β,β‐dimethylacrylic acid (reaction scheme E).Keywords
This publication has 3 references indexed in Scilit:
- 390. Studies in the polyene series. Part XXIX. Ethoxyacetylenic carbinols and their conversion into αβ-unsaturated aldehydes and acidsJournal of the Chemical Society, 1949
- 132. Researches on acetylenic compounds. Part XVIII. The addition of thiolacetic acid to acetylenic hydrocarbons. The conversion of monosubstituted acetylenes into aldehydes and 1 : 2-dithiolsJournal of the Chemical Society, 1949
- Cycloalkeneacetic Acids in the Perkin Reaction1Journal of the American Chemical Society, 1945