Poly-sulfur-nitrogen heterocycles via sulfur chlorides and nitrogen reagents

Abstract

Nitrogen and sulfur organic aromatic heterocycles are formally derived from aromatic carbon cycles by a heteroatom taking the place of a ring carbon atom or a complete CH=CH group. The presence of heteroatoms results in significant changes in the cyclic molecular structure due to the availability of unshared pairs of electrons and the difference in electronegativity between heteroatoms and carbon. Therefore, nitrogen and sulfur heterocyclic compounds display physicochemical characteristics and reactivity far from the parent aromatic hydrocarbons. On the other hand, the presence of many nitrogen and sulfur atoms in a ring is normally associated with instability and difficulties in the synthesis but, in fact, surprisingly stable heterocycles with unusual properties can be frequently obtained from simple or- Poly-Sulfur-Nitrogen Heterocycles via Sulfur Chlorides and Nitrogen ReagentsTomás Torroba* Burgos/Spain, Departamento de Química, Facultad de Ciencias, Universidad Received October 28th, 1998, respectively January 4th, 1999Keywords: Conducting materials, Nitrogen heterocycles, Phosphorus heterocycles, Selenium, Sulfur heterocycles Abstract: The family of poly-sulfur-nitrogen heterocycles includes highly stable aromatic compounds that display physicochemical properties with relevance in the design of new materials, especially those relating to molecular conductors and magnets. The interesting characteristics found in many of these heterocycles have led to the development of modern synthetic methods that are the subject of this review. Heterocycles such as 1,2,3-and 1,2,5-thiadiazoles, 1,2,3-and 1,3,2-dithiazoles, 1,2,3,5-dithiadiazoles, thiatriazines, trithiadiganic substrates and the appropriate inorganic reagent. This paper reviews the most common synthetic methods to obtain poly-sulfur-nitrogen heterocyclic systems that lie in the middle way between organic and inorganic chemistry. Carbon atoms confer high stability to such rings, according to the aromaticity and antiaromaticity rules, and the nitrogen-sulfur core gives unusual properties to the compounds, in accordance with their electron rich π-excessive nature. The physicochemical properties of this family of compounds have relevance in the design of new materials, specially concerning organic conductors. In contrast with the number and variety of such heterocycles, the number of synthetic methods to afford them is, in practice, restricted to the availability of the appropriate sulfur reagent. The classification of synthetic methods follows the applications of the most common sulfur reagents to the synthesis of heteroaromatic carbon-nitrogen-sulfur rings and sometimes extends to selenium or phosphorus related heterocycles. Binary inorganic sulfur-nitrogen cycles are covered by some reports from Chivers and Oakley [1]. Some binary S-N rings, as B-F in figure 1, constitute the models and sometimes precursors of the organic members of the series.azines, dithia(and trithia)diazepines, trithiatriazepines, dithia(and trithia)tetrazozines, and fused systems are mo...

One-pot synthesis of sulfur heterocycles from simple organic substrates

“…Thus, the parent ring, having a hydrogen on the nitrogen, is a planar compound in the solid state. This compound 9 is obtained by debenzylation of the N-benzyl substituted bis [1,2]dithiolo [1,4]thiazine derivative (Equation 2).…”

“…The N-(2-chloroethyl)diisopropylamine 10 constitutes a very special case. Its reaction with sulfur monochloride, whether or not in the presence of formic acid, gives the tricyclic bis [1,2]dithiolo [1,4]thiazine derivatives. The course of the reaction is completely changed by addition of phosphorus pentasulfide at the last stage of the reaction.…”

“…The course of the reaction is completely changed by addition of phosphorus pentasulfide at the last stage of the reaction. In this case, the chlorine atom is replaced by sulfur both in the lateral chain or in the intermediate salt, thus giving a new [1,2]ditiolo [1,4]thiazine ring system. 15 This new compound 11 has shown a notable antitumor activity against breast cancer cells at low concentration (10 -4 M).…”

“…2,3 Also sulfur monochloride can be considered as a reactive electrophile 4,5 and oxidant (see examples in review [1]). But the sulfurating ability of sulfur monochloride is more important.…”

Synthesis and Characterization of Novel N-(Benzo[d]Thiazol-2-yl)-2-(2-(6-Chloroquinolin-4-yl)Hydrazinyl)Acetamide Derivatives Containing Quinoline Linkage as Potent Antibacterial Agents

“…The grounds of this interest were their biological activities and unique structures that led to several applications in different areas of pharmaceutical and agrochemical research or, more recently, in material sciences. [2] Benzothiazole is one of the infrequently obtainable heterocyclic compound, which found in alkaloids. It derived from terrestrial and marine natural products.…”