Conversion of a thiohydantoin to the corresponding hydantoin via a ring-opening/ring closure mechanism

Goubet, F.; Teutsch, G.

doi:10.1016/0040-4039(96)01735-2

Cited by 6 publications

(2 citation statements)

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“…Existing methods for desulfurization of 2-thiohydantoins use dimethyl formamide (DMF)/H 2 O 2 /CH 3 COOH, 13 H 2 O 2 /NaHCO 3 /CH 3 CN-H 2 O, 14 NaOMe/MeI/DMF, 15 and S-alkylation of 2-thiohydantoin followed by treatment with ethanolic HCl, 16 bromoacetyl benzene, and Hg(OAc) 2 with a microwave. 17 All of these methods suffer from no or poor selectivity and the use of hazardous chemicals, oxidizing agents (H 2 O 2 ), or strong acids.…”

Section: Introductionmentioning

confidence: 99%

SnCl₂·2H₂O: An Efficient Reagent for Selective and Direct Oxidative Desulfurization of Phenylmethylene-2-thiohydantoins to Corresponding Hydantoins

Kumar

Pandey

Khan

et al. 2011

Phosphorus, Sulfur, and Silicon and the Related Elements

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GRAPHICAL ABSTRACTNH HN O S R NH HN O O R NH HN O S R NH HN O O R NR 1 HN O S R NR 1 H N O O R SnCl 2 .2H 2 O, EtOH, reflux × × Abstract A new and efficient protocol is presented for selective and direct oxidative conversion of phenylmethylene-2-thiohydantoins to corresponding hydantoins. It involves the use of SnCl 2 .2H 2 O, which oxidatively desulfurizes the phenylmethylene-2-thiohydantoins to their corresponding hydantoin analogues in good to excellent yields while all other 2-thiohydantoins remain unaffected.

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Section: Introductionmentioning

confidence: 99%

SnCl₂·2H₂O: An Efficient Reagent for Selective and Direct Oxidative Desulfurization of Phenylmethylene-2-thiohydantoins to Corresponding Hydantoins

Kumar

Pandey

Khan

et al. 2011

Phosphorus, Sulfur, and Silicon and the Related Elements

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“…2 The known preparative methods are based on catalytic asymmetric aza-Henry reactions 3 or rearrangement of thiohydantoins by the ANRORC mechanism. 4 The closest known homologues of 2-thioxoimidazolidine-4,5dicarboxylates, the 2-oxoimidazolidine-4,5-dicarboxylic acids and esters, have found numerous applications. The synthetic utility of the 2-oxoimidazolidine-4,5-dicarboxylic derivatives can be seen in their uses in the synthesis of d-biotin 5 and in the preparation of a streptolidine lactam, which is the core structure of streptothricin antibiotics.…”

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confidence: 99%

A Simple Synthesis of New 2-Thioxoimidazolidine-4,5-dicarboxylates from Vicinal Diisothiocyanatocarboxylates

Cież¹,

Kalinowska‐Tłuścik²,

Peyrat³

et al. 2008

Synthesis

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A simple synthesis of novel symmetrical and unsymmetrical 2-thioxoimidazolidine-4,5-dicarboxylates is described. The symmetrical 2-thioxoimidazolidine-4,5-dicarboxylates were obtained through partial hydrolysis of vicinal 2,3-diisothiocyanatocarboxylates. The unsymmetrical 2-thioxoimidazolidine-4,5-dicarboxylates were prepared by addition of a stoichiometric amount of primary and secondary amines to vicinal 2,3-diisothiocyanatocarboxylates. The resulting imidazolidine derivatives were found to be convenient reactants for the construction of a new bicyclic imidazo[2,1-b]thiazole system. The addition of a twofold excess of amine to vicinal 2,3-diisothiocyanatocarboxylates gave rise to competitive condensations yielding bi-imidazolidine and bi-1,2,4-triazine derivatives.Numerous 2-thioxoimidazolidine derivatives attract attention as compounds of medical use, for example, as octopaminergic agonists, 1a,b and because they exhibit antimicrobial activity. 1c They also have industrial applications as vulcanization accelerators. 1d However, there have so far been no reports regarding the synthesis of 2-thioxoimidazolidine-4,5-dicarboxylates and only several examples of 2-thioxoimidazolidines mono-substituted by an ester group. 2 The known preparative methods are based on catalytic asymmetric aza-Henry reactions 3 or rearrangement of thiohydantoins by the ANRORC mechanism. 4 The closest known homologues of 2-thioxoimidazolidine-4,5-dicarboxylates, the 2-oxoimidazolidine-4,5-dicarboxylic acids and esters, have found numerous applications. The synthetic utility of the 2-oxoimidazolidine-4,5-dicarboxylic derivatives can be seen in their uses in the synthesis of d-biotin 5 and in the preparation of a streptolidine lactam, which is the core structure of streptothricin antibiotics. 6 Some methods for the synthesis of imidazolidine-4,5-dicarboxylic acids from aspartates 7 and glycinate Schiff bases 8 have been reported but all the mentioned protocols consist of multistep reactions.Our investigations on titanium(IV) mediated oxidative coupling reactions of 2-isothiocyanatocarboxylic esters 1 resulted in a novel method for diastereoselectively preparing vicinal diisothiocyanatocarboxylates 2. 9 We have found that the prepared new vicinal dl-diisothiocyanatocarboxylates 2 were useful in the direct synthesis of symmetrical and unsymmetrical dl-2-thioxoimidazolidine-4,5-dicarboxylates. Following the general procedure of acidic transformations of isothiocyanates into amines, 10 we hydrolyzed the obtained vicinal diisothiocyanates 2a and 2b in 50% perchloric acid. After addition of a stoichiometric amount of sodium hydroxide, we isolated crystalline products 3a and 3b with good yields (Scheme 1). Their structures were determined by spectroscopic methods and confirmed by an X-ray diffraction analysis of compound 3a (Figure 1). Scheme 1 Reagents and conditions: (a) See Cież; 9 (b) (i) 50% HClO 4 , dioxane, 60°C, 24 h; (ii) aq NaOH.The asymmetric unit of compound 3a contains only half of the molecule; the remainder can be rebuilt by rotati...

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Methods for substitution of the thioxo group with the oxo group in imidazolidine-2-thione derivatives

et al. 2022

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Conversion of a thiohydantoin to the corresponding hydantoin via a ring-opening/ring closure mechanism

Cited by 6 publications

References 10 publications

SnCl₂·2H₂O: An Efficient Reagent for Selective and Direct Oxidative Desulfurization of Phenylmethylene-2-thiohydantoins to Corresponding Hydantoins

SnCl₂·2H₂O: An Efficient Reagent for Selective and Direct Oxidative Desulfurization of Phenylmethylene-2-thiohydantoins to Corresponding Hydantoins

A Simple Synthesis of New 2-Thioxoimidazolidine-4,5-dicarboxylates from Vicinal Diisothiocyanatocarboxylates

Methods for substitution of the thioxo group with the oxo group in imidazolidine-2-thione derivatives

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Conversion of a thiohydantoin to the corresponding hydantoin via a ring-opening/ring closure mechanism

Cited by 6 publications

References 10 publications

SnCl2·2H2O: An Efficient Reagent for Selective and Direct Oxidative Desulfurization of Phenylmethylene-2-thiohydantoins to Corresponding Hydantoins

SnCl2·2H2O: An Efficient Reagent for Selective and Direct Oxidative Desulfurization of Phenylmethylene-2-thiohydantoins to Corresponding Hydantoins

A Simple Synthesis of New 2-Thioxoimidazolidine-4,5-dicarboxylates from Vicinal Diisothiocyanatocarboxylates

Methods for substitution of the thioxo group with the oxo group in imidazolidine-2-thione derivatives

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SnCl₂·2H₂O: An Efficient Reagent for Selective and Direct Oxidative Desulfurization of Phenylmethylene-2-thiohydantoins to Corresponding Hydantoins

SnCl₂·2H₂O: An Efficient Reagent for Selective and Direct Oxidative Desulfurization of Phenylmethylene-2-thiohydantoins to Corresponding Hydantoins