Regioselectivity of the reaction of 4H-1,2,4-triazole-3-thiol derivatives with chloroethynylphosphonates and structure of the products

Erkhitueva, E. B.; Догадина, А. В.; Khramchikhin, A. V.; Ионин, Б. И.

doi:10.1134/s1070428013040155

Cited by 9 publications

(2 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Only an attempt to crystallize chloride 1a from a mixture of methyl and isopropyl alcohols resulted in the isolation of crystalline zwitterionic product 1j, which was formed via the elimination of methyl chloride from chloride 1a. 10,11 The structure of phosphonate 1j was determined by X ray diffraction (Fig. 1).…”

Section: R = Ph 2 Thienylmentioning

confidence: 99%

Chloroacetylenephosphonates in reactions with tetrazolethiones

2014

Self Cite

View full text Add to dashboard Cite

Chloroacetylenephosphonates react with 1 substituted tetrazole 5 thiones in anhydrous acetonitrile to form fused heterocycles, viz., 3 substituted 6 (dialkoxyphosphoryl) 3H thiazolo [3,2 d]tetrazol 7 ium chlorides, along with a small amount of compounds having a linear structure, viz., Z dialkyl {1,2 bis[(1 methyl(phenyl) 1H tetrazol 5 yl)sulfanyl]ethenyl} phosphonates.Chloroacetylenephosphonates were synthesized for the first time in 1965. 1 These compounds came to the atten tion of chemists due to the presence of several highly reac tive centers in their structure: an acetylenic bond, a labile halogen atom, and an electron withdrawing phosphonate group. Various possible applications of these compounds for the synthesis of phosphorus containing carbo and het erocycles, addition products at the triple bond, and vari ous compounds with retention of the triple bond were described in the literature. 2,3In the present study, we consider a new area of the use of chloroacetylenephosphonates in the synthesis of phos phorylated fused heterocycles. Five membered heterocy cles with two or three heteroatoms, such as imidazoles, thiazoles, triazoles, and so on, serve as key structural blocks for many pharmacological agents. 4-8 The conventional method for the synthesis of these compounds is based on reactions of binucleophiles (diamines, diols, thioleamines containing nucleophilic groups at adjacent carbon atoms) with carbonyl compounds and carboxylates. In the past decades, acetylenes and haloacetylenes have found increas ing use for the design of heterocyclic structures. The reac tivity of haloacetylenes increases in the presence of an electron withdrawing activating group, such as a carbon yl, carboxyl, or phosphoryl group, at the triple bond. One of advantages of the use of haloacetylenes for the heterocyclization is that their reactions, as opposed to reactions with carbonyl (carboxyl) reagents, do not pro duce a water molecule, which can have an effect on the course of the reaction.The reactions of haloacetylenephosphonates with bi nucleophiles usually proceed with high regioselectivity via the attack of both nucleophilic centers on the haloacetyl ene carbon atom. Thus, the reactions of chloroacetylene phosphonates with o phenylenediamine, o aminophenol, 1,2 alkanediols, and 1,2 ethanolamines afford (dialk oxyphosphorylmethyl)benzimidazoles, benzoxazoles, 1,3 oxolanes, and 4,5 dihydrooxazoles, respectively. 3 This reaction of 2 acyl 1 bromoacetylenes with 4 ami no 5 phenyl 3 thio 1,2,4 triazole proceeds through the same pathway. 9 In this study, it was shown that the reac tion produces fused aromatic systems due to the involve ment of two nucleophilic centers (sulfur and the NH 2 group of thiotriazole) and one electrophilic center (the haloacetylene carbon atom). 2 Acylmethylene 5 phenyl 3H 1,3,4 thiadiazolo[2,3 c] 1H(2H) 1,2,4 triazolium bromides were synthesized in 65-69% yields (Scheme 1). Scheme 1 R = Ph, 2 thienylIn a continuation of our studies of the reactivity and synthetic potential of chloroacetylenephosphona...

show abstract

Section: R = Ph 2 Thienylmentioning

confidence: 99%

Chloroacetylenephosphonates in reactions with tetrazolethiones

2014

Self Cite

View full text Add to dashboard Cite

show abstract

“…Synthesis of condensed 1,2,4‐triazoles from 4‐amino‐3‐mercapro‐1,2,4‐triazole have been reported in literature widely . Preparation of structurally related condensed 1,2,3‐triazoles from 1‐amino‐5‐mercapto‐1,2,3‐triazoles was observed only for few examples .…”

Section: Introductionmentioning

confidence: 99%

Transformation of 1,2,3‐Thiadiazolyl Hydrazones as Method for Preparation of 1,2,3‐Triazolo[5,1‐b][1,3,4]thiadiazines

Калинина

Bystrykh

Глухарева

et al. 2015

Journal of Heterocyclic Chem

View full text Add to dashboard Cite

The transformation of 1,2,3‐thiadiazolyl hydrazones of aldehydes and ketones including Dimroth rearrangement giving 1‐alkylidenamino‐5‐mercapto‐1,2,3‐triazoles, alkylation of mercapto group of these heterocyclic compounds by α‐bromoacetophenones and cyclization giving 6,7‐dihydro‐5H‐[1,2,3]triazolo[5,1‐b][1,3,4]thiadizines have been investigated. It was shown that the reaction for hydrazones of acetophenones and benzoaldehydes is diastereoselective. Triazolothiadiazine spiro derivatives were prepared with transformation of hydrazones of cyclic ketones.

show abstract

Addition Reactions: Polar Addition

Kočovský¹

2016

Organic Reaction Mechanisms · 2013

View full text Add to dashboard Cite

Regioselectivity of the reaction of 4H-1,2,4-triazole-3-thiol derivatives with chloroethynylphosphonates and structure of the products

Cited by 9 publications

References 5 publications

Chloroacetylenephosphonates in reactions with tetrazolethiones

Chloroacetylenephosphonates in reactions with tetrazolethiones

Transformation of 1,2,3‐Thiadiazolyl Hydrazones as Method for Preparation of 1,2,3‐Triazolo[5,1‐b][1,3,4]thiadiazines

Addition Reactions: Polar Addition

Contact Info

Product

Resources

About