Reaction Of Disulfide Research Articles

Rhodium-catalyzed interconversion between acid fluorides and thioesters controlled using heteroatom acceptors

A rhodium complex catalyzed the equilibrium acyl transfer reaction between acid fluorides and thioesters. In the presence of fluoride or thiolate acceptors, the reaction could be shifted to either product. RhH(PPh 3) 4-dppe catalyzed the reaction of acid fluorides and diorgano disulfides in the presence of triphenylphosphine giving thioesters, which was accompanied by triphenylphosphine difluoride. The same complex catalyzed the reaction of aryl thioesters and hexafluorobenzene giving acid fluorides, which was accompanied by 1,4-di(arylthio)-2,3,5,6-tetrafluorobenzenes.

An expedient synthesis of N-p-tosyl macrocycles containing two thiourea moieties from trisulfonamide and bisdithiocarbamate salts at room temperature in aqueous media

The nucleophilic reaction of diamines and carbon disulfide in aqueous NaOH afforded a series of bis-dithiocarbamate salts. Activation of these with aqueous ClCH2COOK and subsequent nucleophilic substitution reaction with trisulfonamide aqueous KOH at room temperature provided N-tosyl-macrocycles containing two thiourea units. This strategy has the advantages of simple operation, mild reaction condition, easy product-isolation and environmental friendliness.

ChemInform Abstract: Formation of 1,3-Oxathiole-2-thione and 1,2,4-Trithiolane Derivatives by the Catalytic Reaction of α-Diazocarbonyl Compounds with Carbon Disulfide.

The rhodium(II) acetate-catalyzed decomposition of α-diazocarbonyl compounds such as substituted α-diazoacetophenones, cyclic diazoketones, cyclic diazodiketones, and α-diazo-β-ketoesters in carbon disulfide gave 1,3-oxathiole-2-thione derivatives in good yields. Diazomalonates also gave alkyl 5-alkoxy-2-thioxo-1,3-oxathiole-4-carboxylates together with 3,5-bis[bis(alkoxycarbonyl)methylene]-1,2,4-trithiolanes. The formation of 1,3-oxathiole-2-thiones can be explained by the intermediacy of zwitterionic intermediate containing rhodium(II) acetate formed by the reaction of carbon disulfide with ketocarbenoids generated in the catalytic decomposition of the diazocarbonyl compounds.

ChemInform Abstract: Gold Thiolate Complexes with Short Intermolecular Au-Au Distances from Reactions of Organic Disulfides with Gold(I) Complexes. Syntheses and Crystal Structures of (Au(I)2(PPh3)2(μ-SCH2Ph))(NO3) and Au(III) 2Cl4(μ-SPh)2.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Thiadiazines with Adjacent Sulfur and Nitrogen Ring Atoms

Publisher Summary This chapter presents the syntheses; the chemical and physical properties; and the applications of 1,2,3-thiadiazines, 1,2,4-thiadiazines, 1,2,5-thiadiazines, and 1,2,6-thiadiazines. Cyclization using hydrazine or hydrazones by the formation of the N–S bond is frequently used for synthesizing 1,2,3-benzothiadiazines. 2H-1,2,3-benzothiadiazine can be methylated at N-2. Acetylation also takes place at the N-2 position. Hydrogenation of 1,2,3-benzothiadiazine 1,1-dioxides gives 3,4-dihydro-derivatives. Monocyclic 1,2,4-thiadiazines can be synthesized by the treatment of thiamine hydrochloride and related thiazolium compounds with hydroxylamine in strong alkali. 1,2,4-thiadiazines exhibit an intense end-absorption in their UV spectra, but otherwise, neither they nor their monoanions give rise to any distinctive UV absorption. The reaction of carbon disulfide with N,N’-dialkylethylenediamines, RNHCH2CH2NHR, gives γ-alkylaminodithiocarbamic acids, the zwitterions of which can be oxidized with iodine/potassium iodide in alkali to yield 1,2,5-thiadiazines. 1,2,6-thiadiazine-6-thione is the main product of the benzoylation of 5-hydroxyaminothiazolidine-2-thione, and the other products are benzamide and benzoic anhydride. The application of X-ray crystallography in determining the structure of 1,2,6-thiadiazine 1,1-dioxides confirms that the ring is not aromatic. In general, the ring is nonplanar and either exists in an envelope form with the sulfur atom at the flap or in a boat form with one of the oxygen atoms attached to the ring sulfur atom situated close to the C4 hydrogen atom.

ChemInform Abstract: Lewis Acid-Catalyzed Addition Reaction of Disulfides to 3-Carene.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Reaction of 2,2′-Biphenoxyborane in Tetrahydrofuran with Selected Organic Compounds Containing Representative Functional Groups.

The approximate rates and stoichiometry of the reaction of excess 1,3,2-biphenyldioxaborepin [2,2'-biphenoxyborane (BPB)] with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, hydride to compound being 4 : 1, room temperature) was examined in order to define the characteristics of the reagent for selective reductions and compare its reducing power with those of other substituted boranes. The results indicate that BPB is unique and the reducing power is much stronger than that of other dialkoxyboranes, such as catecholborane and di-s-butoxyborane. BPB reduces aldehydes, ketones, quinones, lactones, tertiary amides, and sulfoxides readily. Carboxylic acids, anhydrides, esters, and nitriles are also reduced slowly. However, the reactions of acid chlorides, epoxides, primary amides, nitro compounds, and disulfides with this reagent proceed only sluggishly.

ChemInform Abstract: Free-Radical Reactions of Benzenethiol and Diphenyl Disulfide with Alkynes. Chemical Reactivity of Intermediate 2-(Phenylthio)vinyl Radicals.

ChemInform Abstract: Free-Radical Reactions of Benzenethiol and Diphenyl Disulfide with Alkynes. Chemical Reactivity of Intermediate 2-(Phenylthio)vinyl Radicals.

ChemInform Abstract: A Novel Synthesis of Diaryl Sulfides.

Abstract Reaction of diphenyl disulfide and aryl iodides or diiodides at high temperature affords phenyl aryl sulfides or bis(phenylthio)arenes in good yields. Thermolysis of dialkyl disulfide with aryl iodides yields only diaryl sulfides.

ChemInform Abstract: Facile Formation of Lanthanoid(III) Thiolates from Benzophenone- Catalyzed Reaction of Lanthanoid Metals and Disulfides, and Their Use as Sulfenylating Reagents.

Abstract Lanthanoid metal reacts with diaryl and -alkyl disulfides in the presence of a catalytic amount of benzophenone to generate lanthanoid (III) thiolates. Lanthanoid thiolates thus formed in situ, react with enones to give Michael adducts in good yields.

ChemInform Abstract: The Reaction of Carbon Disulfide with 2-Aminoprop-1-ene-1,1,3- tricarbonitrile: One-Pot Synthesis of Thiophenes and Their Condensed Derivatives.

ChemInform Abstract: The Reaction of Carbon Disulfide with 2-Aminoprop-1-ene-1,1,3- tricarbonitrile: One-Pot Synthesis of Thiophenes and Their Condensed Derivatives.

Synthesis of acylphosphine sulfides by rhodium-catalyzed reaction of acid fluorides and diphosphine disulfides

A rhodium complex catalyzed the reaction of acid fluorides and tetraethyldiphosphine disulfide giving acylphosphine sulfides. Aromatic acid fluorides with electron donating p-groups reacted smoothly giving the products in high yields. Aliphatic acid fluorides with secondary and tertiary α-carbons were also converted to alkanoylphosphine sulfides, whereas the reaction of a substrate with an α-methylene carbon was accompanied by enol ester formation.

A facile synthesis of novel nanorod-assembling hollow nanowires of cadmium sulfide/DBTU nanocomposite

Novel nanorod-assembling hollow nanowires of cadmium sulfide/DBTU (N,N'-dibutylthiourea) nanocomposite were synthesized by reacting CdCl{sub 2} with in situ produced H{sub 2}S from reaction of butylamine and carbon disulfide at molar ratio 3:3 of CS{sub 2}:BuNH{sub 2} at 50 {sup o}C. This product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SEAD), energy dispersive X-ray spectroscopy (EDAX), thermogravimetric (TG), Fourier transform infrared (FTIR) and UV-vis absorption spectra. A plausible mechanism that the extending DBTU molecules in solvent of CS{sub 2} induce the formation of CdS/DBTU nanorods by coordinating with the formed CdS particles, and construct these nanorods to hollow nanowires via molecular interactions is proposed and discussed on the basis of experimental results. Photoluminescence (PL) of CdS/DBTU nanocomposite exhibits increasing emission intensity largely.

ChemInform Abstract: Preparation of Functionalized Unsymmetrical Disulfides by a Base-Induced Crossed Reaction of Symmetrical Disulfides.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Radical Addition to Isonitriles: A Route to Polyfunctionalized Alkenes Through a Novel Three-Component Radical Cascade Reaction.

The reaction of aromatic disulfides, alkynes, and isonitriles under photolytic conditions affords polyfunctionalized alkenesβ-arylthio-substituted acrylamides or acrylonitrilesin fair yields through a novel three-component radical cascade reaction. The procedure entails addition of a sulfanyl radical to the alkyne followed by attack of the resulting vinyl radical to the isonitrile. A fast reaction, e.g., scavenging by a nitro derivative or β-fragmentation, is necessary in order to trap the final imidoyl radical, since addition of vinyl radicals to isonitriles seems to be a reversible process. The stereochemistry of the reaction is discussed, particularly with respect to the stereochemical outcome of related hydrogen abstraction reactions by the same vinyl radicals. The lower or even inverted preference for either geometrical isomer observed in our cases with respect to that encountered in hydrogen abstraction reactions is explained in terms of transition-state interactions and/or isomerization of the fina...

Water-Mediated Multicomponent Reaction: A Facile and Efficient Synthesis of Multisubstituted Thiazolidine-2-thiones

A facile, efficient, and green method for the synthesis of multisubstituted thiazolidine-2-thione derivatives via a three-component reaction of amine, carbon disulfide, and α-bromoketone is described. By using water as the reaction medium, the reaction proceeds smoothly to give corresponding products in good to excellent yields.

Toward a practical and waste-free synthesis of thioureas in water

An operationally simple and entirely green protocol for the synthesis of thiourea derivatives by the reaction of carbon disulfide with primary amines in pure water is developed. This reaction is a highly atom-economic process for production of highly pure, hindered thioureas without any catalyst and tedious work-up.

ChemInform Abstract: Unexpected Reaction of Dibenzyl Disulfide with Hydrazine.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Dithiothreitol revisited in red cells: A new head for an old hat

In the present article the authors make an approach over the applications of dithiothreitol (DTT) in its different clinical-laboratory, potential and up-to-date sources. Dithiothreitol is a chemical reagent with a wide actuation spectrum not only from a laboratorial view but also from a therapeutic standpoint, more clinical and practical. DTT (i) is frequently used in a variety of experiences that involve proteins or peptides, protecting sulfhydryl groups from oxidation and reducing disulfide bonds between cysteines; (ii) is also used in the study of disulfide exchange reactions of protein disulfides; (iii) is able to keep glutathione in the reduced state; (iv) acts as an "antidote" enabling the activity of detoxification systems; (v) participates in cellular mechanisms such as vesiculation, cell morphology, signal transduction pathways (hormone-'like' role), etc.; (vi) can be used in the treatment approach of diseases like cystinosis or medical conditions resulting from ion or metal toxicity. In erythrocytes, there's literature pointing that DTT may trigger changes on the normal discoid shape following metabolic depletion, and additionally modulate the exovesiculation kinetics as demonstrated by us. The present article dissects in detail recent findings in our Unit concerning the DTT influence on human erythrocytes.

Rhodium-Catalyzed Organothio Exchange Reaction of .ALPHA.-Organothioketones with Disulfides

RhH(PPh(3))(4) and 1,2-bis(diphenylphosphino)ethane (dppe) catalyzed the organothio exchange reaction of α-organothioketones and organic disulfides. The reaction was affected by the structure of the substrate: α-phenylthio and α-alkylthio aryl ketones reacted effectively with diaryl and dialkyl disulfides; α-phenylthio dialkyl ketones reacted with diaryl disulfides but not with dialkyl disulfides; diaryl disulfides with electron-donating p-substituents were more reactive than those with electron-withdrawing p-substituents.