Synthesis and Spectral Characterization of Novel Spiroindan-1,3-Dione: A Diels Alder Adduct

N D Zargar,K Z Khan

doi:10.1155/2013/415639

Abstract

DMSO/Ac2O reagent converts 1,3-indandione (1) to an unusual dimer 1H,1′H-2,2′-biindene-1,1′,3,3′(2H,2′H) tetrone and a dimeric condensation product along with an ylide (1a) at room temperature. This reagent also brings about oxidation of secondary alcohols to corresponding ketones, methyl thiomethylation, and N-hydroxymethylation in phthalimide and converts 4-hydroxycoumarins and dicoumarol to different oxidative and degradation products under varying conditions. However, when 1,3-indandione was refluxed with DMSO/Ac2O reagent at 150°C, it afforded a novel compound, 2-spiroindan 1,3-dione (2), a Diels Alder Adduct, analogous to (3) obtained upon treatment of 1,3-indandione with formaldehyde in presence of primary amines.

Highlights

Dimethyl sulphoxide, a polar aprotic liquid, has been used in combination with a number of activators but the most important and extensively used was acetic anhydride
Keeping in view it was thought better to interact 1,3indandione with DMSO-acetic anhydride reagent at elevated temperature (∼150∘C) as the former contains active hydrogens which can protonate the oxygen of DMSO and set the reaction in motion
Workup of the reaction mixture and chromatography of the material resulted in only one pure compound m.p. 244–246∘C and was found to be devoid of sulphur

Summary

Introduction

A polar aprotic liquid, has been used in combination with a number of activators but the most important and extensively used was acetic anhydride. DMSO-acetic anhydride reagent has been a subject of monographs It brings about oxidative rearrangements [1], oxidative degradation, oxidation of secondary alcohols [2], and methyl thiomethylates –OH group in different sugar units [3]. Interaction of this reagent with 4-hydroxy coumarins and 3-substituted 4hydroxy coumarins results in a wide range of products under varying conditions both of mechanistic and pharmacological interests [4]. Its interaction with 5-bromo furfural in ethanol gives 5-bromo furfuryl diindandionyl-methane [5] It reacts with cyclic ketones such as cyclopentanone and cyclohexanone to give the corresponding 2-cycloalkylidene1,3-indandione [6]. Keeping in view it was thought better to interact 1,3indandione with DMSO-acetic anhydride reagent at elevated temperature (∼150∘C) as the former contains active hydrogens which can protonate the oxygen of DMSO and set the reaction in motion

Experimental

Results and Discussion

Conclusion