Heterocyclization of Bis(2-chloroprop-2-en-1-yl)sulfide in Hydrazine Hydrate–KOH: Synthesis of Thiophene and Pyrrole Derivatives

Abstract

The article is devoted to heterocyclization of bis(2-chloroprop-2-en-1-yl)sulfide which proceeds in hydrazine hydrate–alkali medium and leads to formation of thiophene and pyrrole derivatives: previously described 4,5,9,10-tetrahydrocycloocta[1,2-c;5,8-c’]dithiophene, as well as unknown hydrazone of 5-methylidene-3-methyldihydrothiophen-2-one and 1-amino-2-(propynylsulfanylpropenylsulfanyl)-3,5-dimethylpyrrole. Tentative mechanisms for the formation of the heterocyclic products are discussed. Obtained hydrazone of 5-methylidene-3-methyldihydrothiophen-2-one was used for the synthesis of a range of azine derivatives and in oxidation process with SeO2. The found reactions open up expedient approaches to the formation of various hardly accessible thiophene and pyrrole compounds from 2,3-dichloropropene and elemental sulfur as starting reagents.

Reactivity of bis(2‐chloroprop‐2‐enyl)sulfide in the system hydrazine hydrate/alkali: A quantum chemical insight

“…In this section, the possible formation of the thiiranium and thiirenium cations, proposed earlier as hypothetical intermediates, 20 in the system bis(2‐chloroprop‐2‐enyl)sulfide/hydrazine hydrate/alkali, was evaluated. The thiiranium cation 26 can be formed directly from bis(2‐chloroprop‐2‐enyl)sulfide 1 by the substitution of the chloride ion with sulfur atom (Figure 7).…”

“…It was previously shown that the hard-to-reach representatives of thiophene series and other can be synthesized from sulfide 1. [18][19][20] The present work is a preliminary study necessary to further investigation the mechanism of the reaction described in Rozentsveig et al 20 The formation of product I (Scheme 4) in the KOH/MeCN system has already been studied by spectral and quantum-chemical methods. 18 The mechanism of product II formation excites a special interest and seems to be rather intriguing.…”

“…The present work is a preliminary study necessary to further investigation the mechanism of the reaction described in Rozentsveig et al 20 The formation of product I (Scheme 4) in the KOH/MeCN system has already been studied by spectral and quantum‐chemical methods 18 …”

“…It was previously shown that the hard‐to‐reach representatives of thiophene series and other can be synthesized from sulfide 1 . 18–20 …”

The Use of Polysaccharide Matrices as a Basis for the Formation of Tellurium Nanoparticles with Different Morphologies

“…The “hydrazine hydrate-NaOH” base-reducing system which was used for the synthesis of Te 0 NPs was previously actively used not only for the activation of elemental chalcogenes to obtain various functionalized chalcogenorganic compounds [ 67 , 68 ], but also for the synthesis of nanoparticles of elemental chalcogenes—S and Se, including those stabilized by natural polysaccharides [ 33 ]. In addition, this system was used to generate highly reactive chalcogenide anions involved in the synthesis of nanoparticles of metal chalcogenides (Ag 2 Se, Bi 2 Se 3 , Bi 2 Te 3 , ZnTe, etc.)…”