Chemistry of acetylenic ethers 97: Claisen‐rearrangement of 1‐alkynyl allenyl sulfides synthesis of acetylenic thioamides and derivatives of thiophene
- 1 January 1972
- journal article
- research article
- Published by Wiley in Recueil des Travaux Chimiques des Pays-Bas
- Vol. 91 (5) , 578-582
- https://doi.org/10.1002/recl.19720910509
Abstract
1‐Alkynyl allenyl sulfides H2C=C=CHSC≡ CR1 (R1 = CH3, C2H5), prepared from alkynethiolates LiSC≡CR1 and propargyl bromide in liquid ammonia, rearrange at room temperature to thioketenes HC≡CCH2C(R1)=C=S. These can be trapped by amines R22NH (R2 = C2H5, C3H7) to give the acetylenic thioamides H≡CCH2CH(R1)C(=S)NR22 in fair to good yields. Potassium tert‐butoxide in liquid ammonia causes cyclization of the thioamides to 2‐dialkylamino‐3,5‐dialkylthiophenes. The same thiophenes are obtained by simply heating the thioamides in hexamethylphosphoric triamide.Keywords
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