The Oxidation of Trlthlocyanurlc Acid and Of Its N-and S-Esters

Tripolt, Robert; Nachbaur, E.

doi:10.1080/10426509208055346

Cited by 5 publications

(8 citation statements)

References 6 publications

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“…Trimerization of Isothiocyanate. Our efforts to prepare the dppe analogues of 3 and 5 by reacting Cp(dppe)RuC⋮CPh ( 1 ‘) with PhNCS led to isolation of a cocrystallization product of 1 ‘ and 1,3,5-triphenyl-1,3,5-triazinane-2,4,6-trithione (PhNCS) 3 ( 8 ), a trimerization product of isothiocyanate. In the reaction, the [2 + 2] cycloaddition ( 9a ) ( 10a ) were also isolated and identified.…”

Section: Resultsmentioning

confidence: 99%

Reactions of Ruthenium Acetylide Complexes with Isothiocyanate

et al. 1998

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Treatment of Cp(PPh 3 )[P(OMe) 3 ]RuCtCPh (2; Cp ) η 5 -C 5 H 5 ) with PhNdCdS at room temperature affords the [2 + 2] cycloaddition product Cp(PPh 3 )[P(OMe) 3 ]RuCdC(Ph)C-(dNPh)S (3a), containing a four-membered ring, and the neutral vinylidene phosphonate complex Cp(PPh 3 )[P(dO)(OMe) 2 ]RudCdC(Ph)C(SH)dNPh (4a) in a 9:1 ratio. Formation of 4a results from an Arbuzov-like dealkylation reaction possibly after addition of PhNdCdS.The same reaction at 40 °C affords a higher yield of 4a and Cp(PPh 3 )[P(OMe) 3 ]RuCdC-(Ph)C(dS)N(R)C(dNR)S (5a; R ) Ph) which results from addition of a second isothiocyanate to the four-membered ring of 3a. The reaction of 2 with PhCH 2 NdCdS at room temperature directly affords the six-membered-ring product 5b (R ) CH 2 Ph). Trimerization of phenyl isothiocyanate is catalyzed by Cp(dppe)RuCtCPh (1′; dppe ) Ph 2 PCH 2 CH 2 PPh 2 ) in refluxing CH 2 Cl 2 . This catalytic reaction proceeds through a pathway in which the first two steps are the same as those observed in the reaction of 2a. An attempt to purify the precursor of the trimerization product gave the cocrystallization of 1′ and (PhNCS) 3 (8). The structures of 3a, 4a, 5b, and the cocrystallization product of 1′ and 8 have been determined by singlecrystal X-ray diffraction analysis.

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Section: Resultsmentioning

confidence: 99%

Reactions of Ruthenium Acetylide Complexes with Isothiocyanate

et al. 1998

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“…2,4,6-Trimethyl-1,3,5-benzenetrimethanethiol (5). Trithiol 5 was prepared according to Whitesides protocol . To commercially available 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene (5.0 g, 12.53 mmol) suspended in EtOH (55 mL), thiourea (2.8 g, 36.78 mmol) was added, and the reaction mixture was maintained under stirring at rt overnight.…”

Section: Methodsmentioning

confidence: 99%

“…In this paper we describe the three-step generation of transient diarenesulfenic acids and di- and triarylmethanesulfenic acids, starting from the corresponding thiols, and the results of their additions onto the triple bonds of di- and triethynyl benzenes. The presence of elements of symmetry, such as C 2 and C 3 axes, in some of the aromatic polysulfenic acids and acceptors, the formation of stereogenic sulfoxide sulfur atoms, the partner choice in the addition sulfenic acid/triple bond, and the nature and conditions of the syn -addition allowed the preparation of π-electron-rich molecules, such as the predicted thiaCP S-oxides, together with open-chain polysulfinyl and polysulfinylmethyl benzenes, quite promising in the field of organic materials.…”

Section: Introductionmentioning

confidence: 99%

“…This reaction and its applications in organic synthesis have been widely studied by us, showing that (i) it is possible to generate sulfenic acids in three steps starting from the suitable thiols; in the thermolysis, that represents the last step, with the sulfenic acid generated in the presence of the unsaturated acceptor leading to sulfoxide formation; 6 (ii) it is possible to generate enantiopure sulfenic acids by synthesizing their precursors with an enantiopure alkyl or aryl residue; 7 and (iii) the generation of sulfenic acids carrying an aminoacidic or a glycosidic residue corresponds to a direct strategy for the stereocontrolled preparation of sulfinyl molecules possessing biological active residues. 8 In this paper we describe the three-step generation of transient diarenesulfenic acids and di-and triarylmethanesulfenic acids, 9 starting from the corresponding thiols, and the results of their additions onto the triple bonds of di-and triethynyl benzenes. The presence of elements of symmetry, such as C 2 and C 3 axes, in some of the aromatic polysulfenic acids and acceptors, the formation of stereogenic sulfoxide sulfur atoms, the partner choice in the addition sulfenic acid/triple bond, and the nature and conditions of the syn-addition allowed the preparation of π-electron-rich molecules, such as the predicted thiaCP S-oxides, together with open-chain polysulfinyl and polysulfinylmethyl benzenes, quite promising in the field of organic materials.…”

Section: Introductionmentioning

confidence: 99%

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Thiacyclophane Cages and Related Bi- and Tripodal Molecules via Transient Polysulfenic Acids

et al. 2007

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A series of bis- and tris-bridged thiacyclophane S-oxides, as racemates or meso products, have been synthesized with a new procedure. Starting from the corresponding thiols, in three steps, transient polyarene- and polyarylmethane-sulfenic acids were generated in the presence of di- and triethynylbenzenes. The thermal syn-addition of these sulfenic acids onto the triple bonds of the unsaturated acceptors was conducted in CH2Cl2 at 40 degrees C. The concentration of sulfoxide precursors of sulfenic acid and the sulfoxide/acceptor molar ratio addressed the syn-addition toward open-chain benzene sulfoxides or thiacyclophane S-oxides. Complete stereochemical control was observed in some reactions between polysulfenic acids and ethynylbenzenes, where the meso dithiacyclophane S,S'-dioxides were obtained exclusively, whereas 1:1 mixtures of meso/rac dithiacyclophanes S,S'-dioxides were isolated as products of other reactions. In almost all the cases, the obtained compounds were separated by column chromatography. The structure assignment of the new heterophanes was done on the basis of their diagnostic NMR spectra and X-ray crystallographic analysis of some of them. Open-chain polysulfinyl and polysulfinylmethyl benzenes, obtained as meso/rac mixtures, were separated and the products were fully characterized. Both synthesized cages, including trithia[3(3)](1,3,5)cyclophane S,S',S' '-trioxides, and bi- and tripodal benzene sulfoxides, appear promising in the field of coordination and material chemistry.

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“…The oxidation of trithiocyanuric acid (1,3,5-triazine-2,4,6-trithiol) with 2-benzenesulfonyl-3-phenyloxaziridine gives the unstable 1,3,5-triazine-2,4,6-trisulfenic acid [9], trapped in solution by diazomethane to give the corresponding trimethyl ester. This oxidative method (by 8) is utilized by the same research group [10] for the synthesis of stable 4,6-dimethoxy-1,3,5-triazine-2-sulfenic acid (10) from 4,6dimethoxy-1,3,5-triazine-2(1H)-thione (9) (Scheme 4).…”

Section: Stable Sulfenic Acidsmentioning

confidence: 99%

Recent Advances and Perspectives in the Chemistry of Sulfenic Acids

Aversa¹,

Barattucci²,

Bonaccorsi³

et al. 2007

COC

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This review provides a comprehensive survey of the literature on sulfenic acid chemistry from 1990 through June 2006, focusing the attention on salient aspects of their structures and involvement in organic processes. Even if the majority of known sulfenic acids cannot be isolated, some stable ones have been obtained, and their study helped dramatically the comprehension of chemical and physical properties of all sulfenic acids and indirectly of the role that Cys-SOHs play in protein biochemistry. Many papers have been published in the last fifteen years about the sulfenic acid intermediacy in organic chemistry. Once generated, they can be involved in intra-and intermolecular additions to unsaturated molecules. Few examples of sulfenic acid addition to double bonds have been recently described and most of them are intramolecular processes, whereas the addition of enantiopure sulfenic acids onto carbon-carbon triple bonds has been widely exploited in the synthesis of vinyl sulfoxides to be used in many stereoselective transformations. The thermicelimination from sulfinyl precursors is a way to generate sulfenic acids but it has been also used for removing the sulfinyl moiety from organic molecules and forming double bonds with controlled stereochemistry. Some significant applications of extrusion processes are also described in the present review.

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The Oxidation of Trlthlocyanurlc Acid and Of Its N-and S-Esters

Cited by 5 publications

References 6 publications

Reactions of Ruthenium Acetylide Complexes with Isothiocyanate

Reactions of Ruthenium Acetylide Complexes with Isothiocyanate

Thiacyclophane Cages and Related Bi- and Tripodal Molecules via Transient Polysulfenic Acids

Recent Advances and Perspectives in the Chemistry of Sulfenic Acids

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