Sulfur Dichloride Research Articles

Reaction of Sulfur Chlorides with Metal β-Diketonates

Metal β-diketonates react with sulfur dichloride to form sulfenyl chlorides irrespective of β-substituent. Bulky phenyl and tert-butyl groups do not prevent formation of fully substituted complexes. The possibility of preparing sulfenyl chloride derivatives of rhodium, ruthenium, and vanadium β-diketonates was demonstrated. A new procedure was suggested for preparing chlorosulfenyl-substituted β-diketonates. Disulfur dichloride reacts with metal chelates with the substitution of both chlorine atoms and formation of polynuclear complexes in which the diketonate groups are linked by disulfide bridges.

The synthesis of thiobisphenols from 3-alkylphenols derived from natural phenolic lipids

3-Alkylphenols derived from renewable natural resources have been used to synthesise thiobisphenols by reaction with sulfur dichloride. In contrast to previous work, we have found that 3-alkylphenols give isomeric products, the major symmetrical, the 4,4′-thiobis compound, the minor symmetrical, 2,2′-thiobisphenol, and some of the believed unsymmetrical isomer. The role of the solvent and catalyst have been studied in the reaction of 3-pentadecylphenol with sulfur dichloride. Evidence for the structures of the 2,2′ and 4,4′ isomers has been obtained from related reactions of 4-bromo-3-methylphenol, 2-bromo-5-methylphenol and their chloro analogues.

Straightforward synthesis of sulfur bridged oligopyrrolic macrocycles

Di- and trisulfide linked oligopyrrolic macrocycles are obtained when appropriate alpha,alpha'-free pyrrolic precursors are reacted with sulfur dichloride; these systems represent the first examples of what might be a general new class of porphyrin analogues.

Montmollironite K10-Promoted Synthesis of 1,4-Dithiane Derivatives from β,β′-Dichloro Sulfides and Hydrogen Sulfide

The reaction of β,β′-dichloro sulfides, prepared by the addition of sulfur dichloride to olefins, with hydrogen sulfide was promoted by montmollironite K10 to afford 1,4-dithiane derivatives in good to excellent yields.

10‐Thia‐mesobilirubin‐XIIIα

AbstractFor Abstract see ChemInform Abstract in Full Text.

10‐Thia‐mesobilirubin‐xiiiα

AbstractThe 10‐thia analog of mesobilirubin‐XIIIα, with the central C(10) CH2 group replaced by sulfur (1a) was synthesized by condensation of neoxanthobilirubic acid (3) with sulfur dichloride. Thia‐rubin 1a is a brilliant yellow solid, forming bright yellow solutions with uv‐visible absorption maximum from 425–440 nm.

Optimization of the Synthesis of Symmetric Aromatic Tri‐ and Tetrasulfides.

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Induced Alkene Reactions with Sulfur Dichloride. System Sulfur Dichloride—Dimethyl Sulfide as a Reagent for Polysulfonation and Conjugate Chlorination of Alkenes.

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Optimization of the synthesis of symmetric aromatic tri- and tetrasulfides.

The reaction of aromatic thiols with sulfur dichloride and sulfur monochloride to form the corresponding aromatic trisulfides, 2a-d, and tetrasulfides, 3a-d, has been optimized with respect to yield and purity. The use of pyridine as an amine base and the use of freshly distilled sulfur monochloride (S(2)Cl(2)) serve as important alterations to the synthetic method. Their physical properties have been characterized, revealing some discrepancies with the literature.

Synthesis of Oxathiacrown Compounds by the Reactions of Sulfur Dichloride with Unsaturated Compounds and Their Extraction Characteristics

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Generation of Sulfenylnitrenes by N‐Sulfenylation of Triphenyl‐λ6‐sulfanenitrile.

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Practical Synthesis of Thiirene 1‐Oxides that Possess Two Bulky Alkyl Substituents.

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Generation of sulfenylnitrenes by N-sulfenylation of triphenyl-λ 6-sulfanenitrile

The sulfenylation of triphenyl-λ 6-sulfanenitrile ( 1 ) with 2,4-dinitrobenzenesulfenyl chloride in the presence of alkenes affords aziridines together with triphenylsulfonium salt. The reaction of 1 with sulfur dichloride also generates ClSN which is trapped by 2,5-diphenylfuran to give 5-benzoylisothiazole.

Highly sulfurated heterocycles via dithiiranes and trithietanes as key intermediates.

2,2,4,4-Tetramethyl-3-thioxocyclobutanone (8b) easily reacts with gaseous chlorine to yield the stable alpha-chloro sulfenyl chloride 10. The same product was obtained when 8b was treated either with phosphorus pentachloride (PCl(5)) or sulfuryl chloride (SO(2)Cl(2)) in CCl(4) solution. Sulfur dichloride (SCl(2)) reacts with 8b to give the alpha-chloro thiosulfenyl chloride 12 along with an almost equimolar amount of the trisulfide 13b. The less reactive disulfur dichloride (S(2)Cl(2)) was shown to react slowly with 8b and the symmetrical tetrasulfide 15 was found as the exclusive product. The pure thiosulfenyl chloride 12 added to adamantanethione (8c) yielded the unsymmetrical trisulfide 13c. When 12 was treated with thioacetic acid, the acetylated trisulfide 17 was formed in high yield. "Unzipping" reactions with the acetylated disulfide 16 and trisulfide 17 with morpholine in THF at -40 degrees C led to the formation of mixtures of two sulfur-rich heterocycles identified as the pentathiepane 6b and the hexathiepane 7b. A mixture of analogous products was obtained when alpha-chloro sulfenyl chloride 10 was treated with sodium sulfide in anhydrous THF at -40 degrees C. The formation of 6b and 7b is believed to occur via the intermediate dithiirane 1b and/or the isomeric thiosulfine 2b. In the case of 17 the reaction starts probably with the formation of a nonisolable tetrathiane 18b as presented in Scheme 5.

Induced Alkene Reactions with Sulfur Dichloride. System Sulfur Dichloride-Dimethyl Sulfide as a Reagent for Polysulfonation and Conjugate Chlorination of Alkenes

In reaction of unsaturated compounds with sulfur dichloride in the presence of dimethyl sulfide radically new induced directions are realized: the reagent is involved as dimer or trimer (formation of di- and trisulfides). Alongside this process a conjugate chlorination occurred with participation of external nucleophiles, dimethyl sulfide and acetonitrile, furnishing sulfonium chlorides and N-substituted acetamides respectively. The relative importance of these alternative reactions depends on solvent, alkene structure, and order of reagents addition.

Practical synthesis of thiirene 1‐oxides that possess two bulky alkyl substituents

AbstractAcetylenes that possess two bulky alkyl substituents reacted with sulfur dichloride to furnish the corresponding 2,3‐dialkyl‐2,3‐dichlorothiiranes (5) nearly quantitatively. The alkaline hydrolysis of 5 afforded 2,3‐dialkylthiirene 1‐oxides (10) in high yields. These two reactions could be successively carried out in one flask, and 2,3‐di‐tert‐butyl‐, 2,3‐di‐(1‐adamantyl)‐, and 2‐(1‐adamantyl)‐3‐tert‐butylthiirene 1‐oxides (10a–c) were obtained in 70, 80, and 90% yields, respectively, based on the starting acetylenes, thus providing the most convenient synthesis of thiirene 1‐oxides. Disulfur dichloride also reacted with acetylenes to give 5 in good yields with the elimination of one sulfur atom. Although the alkaline hydrolysis of 5 provided 10 exclusively, acid hydrolysis gave a mixture of α‐oxothioketone 9 and thiirene 1‐oxide 10 in modest yields. All thiirene 1‐oxides 10a–c isomerized to produce α‐oxothioketones 9 in high yields when heated in boiling toluene. Reactions of a bis‐acetylene (18) with disulfur dichloride and with sulfur dichloride gave a dihydropentathiepin (19) in high yields. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:424–430, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10070

Synthesis of Oxathiacrown Compounds by the Reactions of Sulfur Dichloride with Unsaturated Compounds and Their Extraction Characteristics. (Review)

Published data of the last 10-15 years on the use of the reactions of sulfur dichloride with various unsaturated compounds for the synthesis of oxathia- and thiacrown compounds and study of their extraction characteristics toward various transition and heavy metals are reviewed. Some previously unpublished results and associated experimental data are also included.

A convenient synthesis of thiirene 1-oxides

Acetylenes ( 1 ), carrying two bulky alkyl substituents, reacted with sulfur dichloride (ClSCl) to give 2,3-dialkyl-2,3-dichlorothiiranes ( 2 ) nearly quantitatively. The alkaline hydrolysis of crude 2 resulted in the formation of thiirene 1-oxides ( 3 ) in 68–90% yields based on 1 , thus providing a convenient synthesis of 3 .

2,6-Dichloro-9-thiabicyclo[3.3.1]nonane: a privileged, bivalent scaffold for the display of nucleophilic components.

The title compound, the condensation product of sulfur dichloride and 1,5-cyclooctadiene, is a reliable acceptor of a wide variety of heteroatom nucleophiles, sometimes in reversible fashion. Optical resolution of the core structure has been achieved and preserved in succeeding transformations. The high reactivity and reliable stereochemical control afforded by this system illustrates the power of neighboring-group participation by the sulfur center.

Synthesis and metabolism of the first thia-bilirubin.

A symmetrical C(10)-thiabilirubin analogue, 8,12-bis(2-carboxyethyl)-2,3,17,18-tetraethyl-7,13-dimethyl-10-thia-(21H,23H,24H)-bilin-1,19-dione (1), was synthesized from 8-(2-carboxyethyl)-2,3-diethyl-7-methyl-10H-dipyrrin-1-one in one step by reaction with sulfur dichloride. The thia-rubin exhibited the expected IR, UV-vis, and NMR spectroscopic properties, which are rather similar to those of mesobilirubin-XIIIalpha. Like bilirubin and mesobilirubin, 1 adopts an intramolecularly hydrogen-bonded conformation, shaped like a ridge-tile but with a steeper pitch. The longer C-S bond lengths and smaller bond angles at C-S-C, as compared to C-CH(2)-C, lead to an interplanar angle between the two dipyrrinones of only 74 degrees -or considerably less than that of bilirubin (approximately 100 degrees). On normal- and reversed-phase chromatography, 1 is substantially less polar than bilirubin. Despite this conformational distortion, 1 is metabolized in normal rats to acyl glucuronides, which are secreted into bile. In mutant (Gunn) rats lacking bilirubin glucuronosyl transferase, 1 (like bilirubin) was not excreted in bile.