Structure of 2,3-dihydro-5-nitro-6-phenyl-1,4-dithiin

Ferguson, George; Kaitner, Branko; Brewer, A. D.

doi:10.1107/s0108270189010541

Cited by 3 publications

(3 citation statements)

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“…1,4-Dithiin compounds (a class of heterocyclic compounds with a C 2 S 2 C 2 ring) have attracted renewed interest since the discovery that plants of the sunflower family contain dimethipin, a commercial plant growth regulant. These 1,4-dithiin derivatives have been reported to exhibit a wide range of biological activity , (Chart a). The substitution on the 1,4-dithiin ring plays an important role in governing the chemical reactivity and biological activity of these compounds.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Boron-Fused 1,4-Dithiin via Cobalt-Mediated Disulfuration of Alkyne at the o-Carborane-9,12-dithiolate Unit

2014

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We present the first synthesis and characterization of a series of boron-fused 1,4-dithiin compounds through the reactions of newly established boron-substituted 16e half-sandwich complex Cp*Co(9,12-S 2 C 2 B 10 H 10 ) with alkynes. The generated C 2 S 2 B 2 ring in these 1,4-dithiin species is a stable structural motif with electron-negative sulfur atoms, as evidenced by theoretical calculation and its solid-state self-assembly. Single-crystal X-ray analysis indicates that C carb −H•••S hydrogen bonding is involved in the self-assemblies of these compounds, which serves as a compatible interaction with stronger C carb −HAll new compounds are characterized by NMR, mass spectroscopy, and X-ray structural analysis.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Boron-Fused 1,4-Dithiin via Cobalt-Mediated Disulfuration of Alkyne at the o-Carborane-9,12-dithiolate Unit

2014

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“…The factors governing the selectivity of these compounds have not been investigated and thus remain unknown. In addition, although dimethipin has been proposed to exert herbicidal and PGR activities by inhibiting protein synthesis, 1,10,11 the mechanism of action for the other dithiins of our previous studies [2][3][4][5][6][7][8][9] remains to be elucidated.…”

Section: Introductionmentioning

confidence: 99%

“…1 We have previously observed that, depending on the type and number of substitutions on the ␣,␤-unsaturated bond in the ring, tetraoxide I may exhibit either herbicidal and PGR activities [2][3][4][5][6] or microbicidal activity. 3,[7][8][9] In particular, dithiin tetraoxides containing an ␣,␤-unsaturated system doubly substituted with alkyl groups (e.g., structures 1−3) show plant growth control activities, but those with an unsubstituted, singly substituted, or electron-withdrawing groups substituted ␣,␤-unsaturated system (e.g., structures 4-6 and 8) exhibit microbicidal activity instead. The factors governing the selectivity of these compounds have not been investigated and thus remain unknown.…”

Section: Introductionmentioning

confidence: 99%

Chemical reactivity and biological activity of dihydro-1,4-dithiin tetraoxides

et al. 2013

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Certain dihydro-1,4-dithiin tetraoxides such as dimethipin, a commercial plant growth regulant, have been reported to exhibit highly selective biological activities depending on the type and number of substitutions on the ␣,␤-unsaturated bond in the dithiin ring. Despite the abundant reports on this class of compounds, the study of chemical reactivity of the ␣,␤-unsaturated bond in the dithiin ring has not been reported and the factors governing the biological selectivity of these compounds are still unknown. In this study, the reactivity of eight dithiin compounds substituted in varying degrees at the ␣,␤-unsaturated bond towards biologically important nucleophilic groups at pH 7.4 were investigated using UV-vis, fluorescence, and 1 H NMR spectroscopies. Their reactivity towards glutathione correlated strongly with their cell growth inhibitory activity and inhibition of DNA topoisomerase II, an enzyme containing critical sulfhydryl groups. On this basis, the mechanism by which these dithiins achieve the biological selectivity previously reported was proposed. Excellent correlations between glutathione reactivity and Taft's polar substituent constants or electrostatic atomic charges of the dithiins were also demonstrated, suggesting that these descriptors might be useful for predicting the reactivity of other dithiins towards sulfhydryl nucleophiles.Key words: dithiins, dimethipin, herbicides, plant growth regulants, microbicides, sulfhydryl binding, reactivity, topoisomerase II, cell growth inhibition, QSAR.Résumé : On a signalé que certains tétraoxydes de dihydro-1,4-dithiine, dont la diméthipine, un régulateur de croissance végétale du commerce, présentent une activité biologique hautement sélective qui dépend du type et du nombre de substitutions sur la liaison ␣,␤-non saturée dans le noyau dithiine. Malgré les nombreux rapports ayant trait à cette classe de composés, aucune étude de la réactivité chimique de la liaison ␣,␤-non saturée dans le noyau dithiine n'a été décrite et les facteurs qui régissent la sélectivité biologique de ces composés demeurent inconnus. Dans la présente étude, on explore la réactivité de huit composés de la dithiine substitués à divers degrés sur la liaison ␣,␤-non saturée vis à vis de groupes nucléophiles importants du point de vue biologique à pH 7,4 par spectrométrie UV vis, de fluorescence et RMN de 1 H. Leur réactivité vis à vis du glutathion était fortement corrélée à leur activité d'inhibition de la croissance cellulaire et à l'inhibition de la topoisomérase II de l'ADN, un enzyme contenant des groupements sulfhydryles critiques. Ces constatations ont permis de proposer le mécanisme grâce auquel ces dithiines manifestent la sélectivité biologique signalée antérieurement. On a aussi montré l'existence d'excellentes corré-lations entre la réactivité du glutathion et les constantes polaires de Taft ou les charges électrostatiques atomiques des dithiines, ce qui donnent à penser que ces descripteurs pourraient être utiles pour prédire la réactivité d'autres dithiines ...

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