Sulfur Dichloride Research Articles

ChemInform Abstract: Regioselective Addition of Sulfur Dichloride and Selenium Tetrachloride to Diallyldimethylsilane as the Method of Preparation of Eight‐Membered Heterocycles Containing Silicon and Chalcogens.

AbstractThe electrophilic addition of SCl2 or SeCl4 to diallylsilane (I) proceeds strictly according to the Markovnikoff rule furnishing previously unknown thiasilacyclooctane (II) or selenasilaoctane (III), respectively.

New Bridges in [2.2]Paracyclophanes: The Interaction of Chalcogenide Halides with Pseudo-Geminal Triple Bonds

Novel heteroatom containing bridges have been introduced in [2.2]paracyclophanes by the interaction of chalcogenide halides with pseudo-geminal triple bonds. The anti-addition with Markovnikov orientation of selenium halides to 4,15-bisethynyl[2.2]paracyclophane leads to the corresponding E-adducts. The interaction of pseudo-geminally substituted bispropargylic alcohols with disulfur dichloride and sulfur dichloride leads to a mixture of cyclic ethers. These compounds are formed under mild acidic conditions provided by the organic ammonium chlorides or silica gel. The corresponding dipropargyloxy sulfides have been identified as reaction intermediates. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

Novel and Efficient Synthesis of Unsymmetrical Trisulfides

We have developed a convenient method for the synthesis of unsymmetricaltrisulfides under mild conditions in very good yields. The designedmethod is based on the straightforward preparation of 1-[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)trisulfanyl]dodecanefrom readily available 5,5-dimethyl-2-sulfanyl-2-thioxo-1,3,2-dioxaphosphorinane,sulfur dichloride (SCl 2 ) and dodecane-1-thiol. The unsymmetricaltrisulfides can be obtained from aliphatic, aromatic thiols and L-cysteine derivatives as well.

Regioselective addition of sulfur dichloride and selenium tetrachloride to diallyldimethylsilane as the method of preparation of eight-membered heterocycles containing silicon and chalcogens

The electrophilic additiob of sulfur dichloride and selenium tetrachloride to diallyldimethylsilane proceeds strictly according Markownikoff rule and results in the formation of previously unknown saturated siliconcontaining heterocycles, 5,5-dimethyl-3,7-dichloro-1,5-thiasilacyclooctane and 5,5-dimethyl-1,1,3,7-tetrachloro-1,5-selena(IV)silacyclooctane. The structure of heterocycles obtained was confi rmed by 1H, 13C NMR spectra, in the case of selenium-containing heterocycle, by 77Se NMR spectrum, among them the 2D HMBC spectrum.

ChemInform Abstract: Formation of 2,3-Dihydro-3-chloromethylnaphtho(1,2-b)(1,4)dithiin (II) by Reaction of Allyl 1-Naphthyl Sulfide with Sulfur Dichloride.

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: Novel Synthesis of Thianonanam Using Sulfur Dichloride as a Sulfur Transfer Reagent.

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: Poly-Sulfur-Nitrogen Heterocycles via Sulfur Chlorides and Nitrogen Reagents

The family of poly-sulfur-nitrogen heterocycles includes highly stable aromatic compounds that display physicochemical properties with relevance in the design of new materials, especially those relating to molecular conductors and magnets. The interesting characteristics found in many of these heterocycles have led to the development of modern synthetic methods that are the subject of this review. Heterocycles such as 1,2,3- and 1,2,5-thiadiazoles, 1,2,3- and 1,3,2-dithiazoles, 1,2,3,5-dithiadiazoles, thiatriazines, trithiadiazines, dithia(and trithia)diazepines, trithiatriazepines, di-thia(and trithia)tetrazozines, and fused systems are most commonly synthesized from tetrasulfur tetranitride and organic substrates (alkynes, diazomethanes), and from sulfenyl chlorides, sulfur or disulfur dichlorides and nitrogen containing reagents such as bis(trimethylsilyl)sulfurdiimide, trimethylsilyl azide, trisilylated amidines, N-imidoylamidines, hydrazones, oximes, and amines.

Enhanced Elemental Mercury Removal from Coal-Fired Flue Gas by Sulfur−Chlorine Compounds

Oxidation of Hg(0) with any oxidant or converting itto a particle-bound form can facilitate its removal. Two sulfur-chlorine compounds, sulfur dichloride (SCl2) and sulfur monochloride (S2Cl2), were investigated as oxidants for Hg(0) by gas-phase reaction and by surface-involved reactions in the presence of flyash or activated carbon. The gas-phase reaction between Hg(0) and SCl2 is shown to be more rapid than the gas-phase reaction with chlorine, and the second order rate constant was 9.1 (+/- 0.5) x 10(-18) mL-molecules(-1) x s(-1) at 373 K. The presence of flyash or powdered activated carbon in flue gas can substantially accelerate the reaction. The predicted Hg(0) removal is about 90% with 5 ppm SCl2 or S2Cl2 and 40 g/m3 of flyash in flue gas. The combination of activated carbon and sulfur-chlorine compounds is an effective alternative. We estimate that coinjection of 3-5 ppm of SCl2 (or S2Cl2) with 2-3 Lb/MMacf of untreated Darco-KB is comparable in efficiency to the injection of 2-3 Lb/MMacf Darco-Hg-LH. Extrapolation of kinetic results also indicates that 90% of Hg(0) can be removed if 3 Lb/MMacf of Darco-KB pretreated with 3% of SCl2 or S2Cl2 is used. Mercuric sulfide was identified as one of the principal products of the Hg(0)/SCl2 or Hg(0)/S2Cl2 reactions. Additionally, about 8% of SCl2 or S2Cl2 in aqueous solutions is converted to sulfide ions, which would precipitate mercuric ion from FGD solution.

(1,1-Dichloro-2,2,2-trifluoroethylimino)sulfur dichloride, CF 3CCl 2N [dbnd]SCl 2: Vibrational spectra and quantum chemical calculations

The vibrational spectra of (1,1-dichloro-2,2,2-trifluoroethylimino)sulfur dichloride, CF 3CCl 2N SCl 2, were recorded in the gas phase with IR spectroscopy and in the liquid state with Raman spectroscopy. Quantum chemical calculations at the HF, B3LYP (6-311+G(d) and 6-311+G(2df) basis sets) and MP2 levels of theory (6-31+G(d) and 6-311+G(df) basis sets) were performed. According to all calculations the lowest energy conformer possesses C 1 symmetry with syn orientation of the SCl 2 group relative to the N C bond and near-trans orientation of the CF 3 group relative to the N S bond. Calculations predict the presence of a second stable conformer with anticlinal orientation of the SCl 2 group which, however, possesses considerably higher energy and is therefore not observed in the analysis of the experimental vibrational spectra. The vibrational spectra were assigned for a single conformer in accordance with these calculations.

Design, Synthesis, and Insecticidal Activities of New N-Benzoyl-N′-phenyl-N′-sulfenylureas

A series of new N'-alkylaminothio, N'-arylaminothio (or dithio), and N',N'-thio (or dithio) derivatives of N-benzoyl-N'-phenylureas were designed and synthesized as insect-growth regulators with sulfur dichloride or disulfur dichloride as the original reactant. The new compounds were identified by (1)H nuclear magnetic resonancee (NMR) spectroscopy, elemental analysis [or high-resolution mass spectrometry (HRMS)], and single-crystal X-ray diffraction analysis. The X-ray results demonstrated that there exist N-S-N or N-S-S-N bonds in these new compounds. In comparison to the parent N-benzoyl-N'-phenylureas, these derivatives displayed better solubility. The insecticidal activities of the target compounds were evaluated. The results of bioassays showed that compounds 1-24 retained the larvicidal activities of the corresponding benzoylphenylureas (BPUs) and some compounds exhibited better larvicidal activities against oriental armyworm and mosquitoes than the parent BPUs. The larvicidal activities of the selected target compounds 1 and 24 against diamondback moth were better than that of the corresponding parent compounds E and triflumuron.

Reactions of hexamethylphosphoramide with sulfur dichloride with the ambivalent participation of methylene chloride

Reactions of hexamethylphosphoramide with sulfur dichloride with the ambivalent participation of methylene chloride

Synthesis and Insecticidal Evaluation of N‐tert‐Butyl‐N′‐thio [O‐(1‐methylthioethylimino)‐N′′‐methylcarbamate]‐N,N′‐diacylhydrazines.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Synthesis and insecticidal evaluation of N‐tert‐butyl‐N′‐thio[O‐(1‐methylthioethylimino)‐N″‐methylcarbamate]‐N,N′‐diacylhydrazines

AbstractA series of novel N‐tert‐butyl‐N′‐thio[O‐(1‐methylthioethylimino)‐N″‐methylcarbamate]‐N,N′‐diacylhydrazines were synthesized by the reaction of chlorosulfenyl[O‐(1‐methylthioethylimino)‐N‐methylcarbamate] with N‐tert‐butyl‐N,N′‐diacylhydrazine in the presence of sodium hydride. The reaction of sulfur dichloride with O‐(1‐methylthioethylimino)‐N‐methylcarbamate (Methomyl) in the presence of pyridine to yield chlorosulfenyl[O‐(1‐methylthioethylimino)‐N‐methylcarbamate] was reported for the first time. X‐ray single crystal diffraction of N‐tert‐butyl‐N′‐thio[O‐(1‐methylthioethylimino)‐N″‐methylcarbamate]‐N,N′‐dibenzoylhydrazine demonstrated that the parent compounds N‐tert‐butyl‐N,N′‐dibenzoylhydrazine and O‐(1‐methylthioethylimino)‐N‐methylcarbamate were combined by NSN band to give the product. Their larvicidal activities against Oriental armyworm and Aphis laburni were evaluated. All of them exhibited excellent larvicidal activities against Oriental armyworm, with some of them showing higher larvicidal activities than the parent diacylhydrazines. Toxicity assays indicated that the products show knockdown activity for O‐(1‐methylthioethylimino)‐N‐methylcarbamate at higher concentration and insect growth regulators' activities of diacylhydrazines at lower concentrations. At the same time, the products possess insecticidal activities against the aphids. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:631–636, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20360

Synthesis and Antioxidancy of Some n‐Alkyl, t‐Alkyl, Homologous and Isomeric Lipidic Alkylthiobisphenols

AbstractTo study the relationship between structure and properties of members of the lipidic thiobis phenol series, as extreme pressure additives in lubricants, a series of homologous compounds has been synthesised by the reaction of alkylphenols with sulphur dichloride. The isomeric n‐nonylphenols have been reacted to form the C9 isomeric 2,2′‐and 4,4′‐thiobisphenols. Longer alkyl side‐chains resulted mainly in the formation of 4,4′‐thiobisphenols and some of the 2,2′ isomer. With short alkyl, particularly t‐alkyl side‐chains, steric hindrance resulted in the 2,2′‐compound. Additive studies have indicated that the longer chain 4,4′ compounds possessed antioxidant properties comparable and superior to former commercial branched chain 2,2′ compounds produced from petrochemical intermediates.

Soluble and thermally stable polyamides bearing 1,1′-thiobis(2-naphthoxy) groups

A new-type of sulfide containing diacid (1,1′-thiobis(2-naphthoxy acetic acid)) was synthesized from 2-naphthol in three steps. Reaction of 2-naphthol with sulfur dichloride afforded 1,1′-thiobis(2-naphthol) ( TBN). 1,1′-Thiobis(2-naphthoxy acetic ester) ( TBNAE) was successfully synthesized by refluxing the TBN with methylcholoroacetate in the presence of potassium carbonate. The related diacid was synthesized by basic solution reduction of TBNAE. The obtained diacid was fully characterized and used to prepare novel thermally stable poly(sulfide ether amide)s via polyphosphorylation reaction with different aromatic diamines. The properties of these new polyamides were investigated and compared with similar polyamides. These polyamides showed inherent viscosities in the range of 0.39–0.87 dL g −1 in N, N-dimethylacetamide (DMAc) at 30 °C and at a concentration of 0.5 g dL −1. All the polyamides were readily soluble in a variety of polar solvents such as DMAc and tetrahydrofuran (THF). These polyamides showed glass transition temperature ( T g) between 241–268 °C. Thermogravimetric analysis measurement revealed the decomposition temperature at 10% weight loss ( T 10) ranging from 441– 479 °C in argon atmosphere.

Gas‐Phase Spectroscopy of the Unstable Sulfur Diisocyanate Molecule S(NCO)2

Sulfur diisocyanate is generated from a heterogeneous reaction of gaseous sulfur dichloride with silver cyanate and studied for the first time in the gas phase. Combined with quantum chemical calculations, the electronic structure is characterized by photoelectron spectroscopy (PES). Simultaneously, an investigation of the possible ionization and dissociation processes for the molecular cation is presented based on experimental soft ionization mass spectrometry. From the calculated bond-dissociation energies, the dissociation pathway is determined. S(NCO)2+ undergoes 1,3-sigmatropic rearrangement with a smaller barrier height (9.9 kcal mol(-1)) than the neutral counterpart. Thus, the 1,3-sigmatropic rearrangement is preferred for the molecular cation, and OCNCO+ and NS+ is produced by subsequent dissociation of the rearrangement product. The analysis agrees very well with the experimental mass spectrum.

Heterocyclic Chemistry of Sulfur Chlorides — Fast Ways to Complex Heterocycles.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

2,6-Dichloro-9-thiabicyclo[3.3.1]nonane: Multigram Display of Azide and Cyanide Components on a Versatile Scaffold

2,6-Dichloro-9-thiabicyclo[3.3.1]nonane, easily available by an improved condensation of sulfur dichloride, sulfuryl chloride, and 1,5-cyclooctadiene, is a well- behaved scaffold for the nucleophilic substitution of azides and cyanides via neighboring- group participation by the sulfur atom. The products are isolated in high yields with purity >95% by simple extraction and washing protocols.

Heterocyclic Chemistry of Sulfur Chlorides – Fast Ways to Complex Heterocycles

AbstractThis microreview highlights the most important advances in the synthetic applications of sulfur dichloride and disulfur dichloride for the preparation of heterocycles. Sulfur chlorides can be considered some of the best sulfur‐transfer reagents for the synthesis of heterocyclic systems. Their high reactivity towards nucleophilic organic compounds such as alkenes, alkynes, amines, nitriles, oximes, and their both chlorinating and sulfurating character explain the extensive use of these reagents. In many cases, the initial reactions give rise to reactive intermediates that can be trapped by nucleophiles in a tandem fashion, expanding the possibilities of the reactions. In this way, several new heterocyclic systems can be obtained by a careful selection of the appropriate combination of reagents. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Silica gel-promoted synthesis of 3,4,5-triaryltetrahydro-1,4-thiazine derivatives from β,β′-dichloro sulfides and aromatic amines

A novel and efficient synthesis of 3,4,5-triaryltetrahydro-1,4-thiazine derivatives by treatment of β,β′-dichloro sulfides, 2:1 adducts of alkenes and sulfur dichloride, with aromatic amines in the presence of silica gel is described. The silica gel can be easily recovered and reused in up to four consecutive reactions without any significant decrease in product yield.