Investigation on the thio-Claisen rearrangement of 2-[(4-aryloxy-2- butynyl)sulfanyl]thiophene

Debabrata Singha; Anwesha Bhattacharya; Nilasish Pal

doi:10.52756/ijerr.2022.v27.006

Debabrata Singha Barashimul High School (H.S), Jangipur, Murshidabad-742213, West Bengal, India https://orcid.org/0000-0001-8958-2016
Anwesha Bhattacharya Department of Chemistry, Seth Anandram Jaipuria College, Kolkata-700005, West Bengal, India https://orcid.org/0000-0002-0110-4640
Nilasish Pal Department of Chemistry, Seth Anandram Jaipuria College, Kolkata-700005, West Bengal, India https://orcid.org/0000-0002-7206-5407

DOI: https://doi.org/10.52756/ijerr.2022.v27.006

Keywords: 2H-thiopyrano[3,2- c]coumarins, [3,3] sigmatropic rearrangement, thio Claisen rearrange-ment

Abstract

2H-thiopyrano[3,2-c]coumarins have been regioselectively produced in 55-78% yield by the thermal [3,3] sigmatropic rearrangement led us to conduct research on the thio Claisen rearrangement of 2-[(4-aryloxy-2-butynyl)sulfanyl]thiophene. Six different cases using various 4-chlorobut-2-ynes were subjected to [3,3] sigmatropic rearrangement. The first cyclization in every cases were successful. The products formed contain allyl aryl ether moiety and as such there was scope for the second Claisen rearrangement with the products. The first Claisen product with Ar = 3,5-Me₂C₆H₃ has been successfully undergone double Claisen rearrangement. As double Claisen rearrangement requires higher activation energy, the selection of solvent and catalyst was very important. In this case, anhydrous AlCl₃, BF₃-etherate was successfully chosen to get the reaction completed within one hour with enhanced yield.

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