Reaction of chloroacetylenephosphonates with 5-thiotetrazoles

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

doi:10.1016/j.tetlet.2013.07.032

Cited by 19 publications

(4 citation statements)

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“…Another trend was observed in this reaction when reacting 2-chloroethynylphosphonate with 1-substituted NH-thiotetrazole-5-ones: Under a basic catalysis in a protic solvent the reaction led to the formation of vicinally disubstituted alkenylphosphonates in 80-90% yields [4]. Some of the obtained Z-1,2-bis[(1H-1,2,3,4-tetrazol-5-yl)sulfanyl]ethenylphosphonates showed high antifungal activity comparable with the activity of fluconazole widely used in medical practice for the treatment of various fungal infections (Scheme 2).…”

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confidence: 81%

Phosphorylation of 5-substituted NH-tetrazoles with dimethyl chloroacetylenephosphonate

2015

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confidence: 81%

Phosphorylation of 5-substituted NH-tetrazoles with dimethyl chloroacetylenephosphonate

2015

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“…From 5-thiotetrazole 42, new fused heterocycles can be formed after reaction with 1chloroacetylene-2-phosphonate 41 in acetonitrile (Scheme 18). (26,27) This chemo-and regioselective reaction can be explained by the attack of the sulfur atom of thiotetrazole to the carbon bearing the halogen of 1-chloroacetylene-2-phosphonate, forming a sulfenium cation 43. The proton-containing nitrogen atom attacks the acetylenephosphonate carbon atom bonded to the phosphorus atom.…”

Section: Scheme 17mentioning

confidence: 99%

Bicyclic 5-5 Systems With One Bridgehead (Ring Junction) Nitrogen Atom: Four Extra Heteroatoms 3:1

Norsikian

2022

Comprehensive Heterocyclic Chemistry IV

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“…This reaction pathway was observed also for 1 substi tuted tetrazole 5 thiones. 12 In this case, 3 substituted 6 (dialkoxyphosphoryl) 3H thiazolo[3,2 d]tetrazol 7 ium chlorides are produced along with a small amount of alk ene compounds (Scheme 3). We failed to convincingly prove the thione structure of the starting tetrazole 5 thiones based on 15 N NMR spectra recorded with proton decoupling and coupling due apparently to high mobility of the tetrazole proton.…”

Section: R = Ph 2 Thienylmentioning

confidence: 99%

Chloroacetylenephosphonates in reactions with tetrazolethiones

2014

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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...

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Reaction of chloroacetylenephosphonates with 5-thiotetrazoles

Cited by 19 publications

References 3 publications

Phosphorylation of 5-substituted NH-tetrazoles with dimethyl chloroacetylenephosphonate

Phosphorylation of 5-substituted NH-tetrazoles with dimethyl chloroacetylenephosphonate

Bicyclic 5-5 Systems With One Bridgehead (Ring Junction) Nitrogen Atom: Four Extra Heteroatoms 3:1

Chloroacetylenephosphonates in reactions with tetrazolethiones

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