Trichloromethanesulfenyl Chloride Research Articles

A facile, catalyst- and additive-free, and scalable approach to the photochemical preparation of disulfides from organosulfenyl chlorides.

A novel, clean and efficient protocol for the preparation of disulfides has been developed through the photochemical radical homo- and cross-coupling reaction of sulfenyl chlorides under LED irradiation and without the use of any catalyst and additive. The representative photochemical homo-coupling of trichloromethyl sulfenyl chloride has been successfully conducted on kilogram-scale in a continuous flow mode. The solvent and the main byproduct can be recovered in high yields, which makes the approach be highly atom economical.

Trichlates, an unattended class of compounds Characterization of Cl3CSO2Cl, and (H5O2)[Cl3CSO3

Chlorination of CS2 leads to trichloromethanesulfenyl chloride, Cl3CSCl, in moderate yields. The oxidation of Cl3CSCl with H2O2 gives Cl3CSO2Cl, the chloride of trichloromethanesulfonic acid. Cl3CSO2Cl is the crucial product for the preparation of trichloromethanesulfonates ("trichlates") and has been characterized by IR spectroscopy, differential scanning calorimetry (DSC) and X-ray diffraction measurements (P-1, a = 609.99(5) pm, b = 727.45(6) pm, c = 782.49(7) pm, α = 80.644(3)°, β = 85.175(3)°, γ = 88.311(3)°. The acid Cl3CSO3H can be gained in form of the hydrate (H5O2)[Cl3CSO3] in two different modifications (I: monoclinic, P21/n, Z = 8, a = 1292.47(7) pm, b = 605.89(2) pm, c = 2661.1(1) pm, β = 98.708(4)°, V = 1672.8(1) Å3; II: monoclinic, Cc, Z = 4, a = 699.80(5) pm, b = 1054.72(8) pm, c = 1139.88(8) pm, β = 95.303(3)°, V = 837.7(1) Å3. Both modifications have been investigated by IR spectroscopy, thermal analyses and theoretical calculations.

Synthesis of Trifluoromethyl Tetrafluoro‐λ6‐sulfanyl‐Substituted Alkenes, Ketones, and Acids: Polar Hydrophobic Building Blocks

The trifluoromethyl tetrafluoro‐λ6‐sulfanyl (CF3SF4) group is both extraordinarily lipophilic and profoundly electron withdrawing, properties associated with polar hydrophobicity. Utilization of the CF3SF4 group to prepare novel materials or biologically active agents will not be possible without new methods for the synthesis of aliphatic CF3SF4‐substituted building blocks. To advance those studies, trichloromethanesulfenyl chloride was conveniently converted to trans‐trifluoromethyl tetrafluoro‐λ6‐sulfanyl chloride (CF3SF4Cl) by oxidative chlorofluorination. Triethylborane‐promoted addition reactions of trans‐CF3SF4Cl to substituted olefins and alkynes yielded a variety of new materials. Those addition products were subsequently transformed to CF3SF4‐substituted carboxylic acids, CF3SF4‐substituted ketones, and a CF3SF4‐substituted aldehyde.

Vibrationally resolved emission of thiophosgene dimer

During a study of thiophosgene electronic spectra, Fujiwara and co-workers observed a broad electronic transition peaked at 37 000 cm −1, attributed to thiophosgene dimer. Our dispersed fluorescence spectra of a thiophosgene molecular beam excited at 36 000 cm −1 reveal several vibrational modes too low in frequency for thiophosgene. We assign them to modes of thiophosgene dimer or their combination bands. MP2 calculations support the vibrational assignment. TD-DFT, CASSCF, and coupled cluster calculations suggest that the bright electronic state of thiophosgene dimer is the B 2u symmetry fifth excited singlet state. Two additional transitions are assigned to a thiophosgene synthesis impurity, trichloromethanesulfenyl chloride.

Perchloromethyl Mercaptan, CCl3SCl, Excited with Synchrotron Radiation in the Proximity of the Sulfur and Chlorine 2p Edges: Dissociative Photoionization of Highly Halogenated Species

We have investigated the dissociative photoionization of shallow-core excited CCl3SCl by using multicoincidence time-of-flight mass spectrometry and synchrotron radiation in the S 2p and Cl 2p edges. The relative abundances of the ionic fragments and their kinetic energy release values were obtained from both PEPICO (photoelectron photoion coincidence) and PEPIPICO (photoelectron photoion photoion coincidence) spectra. The dynamic of the ionic fragmentation of S and Cl 2p excited CCl3SCl has been studied and compared with those of CCl4. Features determined in the present study seem to be relevant aspects for explaining the dissociation of highly chlorinated species under the action of VUV irradiation. The fragmentation pattern shows that chlorine ion (Cl+) is prominently formed upon both S and Cl 2p excitations.

HeI Photoelectron Spectroscopy and Theoretical Study of Trichloromethanesulfenyl Acetate, CCl3SOC(O)CH3, and Trichloromethanesulfenyl Trifluoroacetate, CCl3SOC(O)CF3

Two novel species, trichloromethanesulfenyl acetate, CCl(3)SOC(O)CH(3), and trichloromethanesulfenyl trifluoroacetate, CCl(3)SOC(O)CF(3), have been generated in situ by the heterogeneous reactions between trichloromethanesulfenyl chloride, CCl(3)SCl, and corresponding silver salts, silver acetate (AgOC(O)CH(3)) and silver trifluoroacetate (AgOC(O)CF(3)), respectively. Photoelectron spectroscopy and quantum chemical calculations are performed to investigate these two molecules, together with their precursor, CCl(3)SCl. Both of these two compounds may exist in the gas phase as a mixture of gauche and trans conformations. As for the dihedral angles delta(RSOR') of the gauche conformers, 107.0 degrees and 108.5 degrees are derived by theoretical calculations (at the B3LYP/6-311+G(3df) level) for CCl(3)SOC(O)CH(3) and CCl(3)SOC(O)CF(3), respectively. The first vertical ionization energies of CCl(3)SOC(O)CH(3) and CCl(3)SOC(O)CF(3), which have been determined by photoelectron spectroscopy, are 9.67 and 10.34 eV, respectively. According to the experimental results and theoretical analysis, the first ionization energy of these two molecules both come from the ionization of the lone pair electron of S atom.

CHLOROSULFONATION OF SOME CRISSCROSS CYCLOADDUCTS FROM ISOCYANATES AND DIARYL AZINES

Reaction of chlorosulfonyl isocyanate (1) with arylaldehyde azines (7) gave the 2:1 crisscross adducts (8);attempts to prepare a disulphonamide of 8a gave only a mixture of the monosulfamide 9 and the diureide 10. The latter with trichloromethanesulfenyl chloride afforded the derivative 12a. and with chlorosulfonic acid hydrazinodicarbonamide (11). The azine 7a with benzoyl isocyanate (2) gave the expected crisscross adduct 13. With thiobenzoyl isocyanate (3) however, both 7a and 7d gave the 1: 1 adducts (14). whereas 7c gave a different 2: 1 adduct (15). Treatment of 14a with 1 gave the ureide 16. With both methyl isocyanate (4) and phenyl isocyanate (S), 7a gave the expected crisscross adducts (17a and b), and 7c with 5 similarly gave 17c. When 7a was treated with 1 followed by aqueous potassium iodide, the diureide (10) was formed; concentrated nitric acid converted 10 into the triazolenone (18). Treatment of 18 with chlorosulfonic acid-thionyl chloride gave the sulfonyl chloride (19) which was characterised as the sulfonamides (20 a-d). Diarylsulfamoyl azines (21 a-f) with 1 and potassium iodide, gave the diureides 22 a-f. 4-Methoxy-3-sulfamoylbenzaldehydeazines (23 a-c) reacted with 3 to give the 1: I adducts 24 a-c, while 4-chlorosulfonylphenyl isocyanate (6) with benzaldehyde azine (7a) gave the bis-chlorosulfonyl adduct (25a). characterised as the diethylsulfonamide 25b. Attempted chlorosulfonation of the tetraphenyl cycloadduct 17b did not give the tetrasulfonyl chloride (although the reaction was successful with the more reactive rnethoxy adduct 17c); the tetrasulfonyl chloride (26a) was converted into 3 sulfonamides (26 b-d). The unsymmetrically-substituted diaryl azines (27) reacted with 1 and potassium iodide to yield the diureides 28 a-f. Analogous cycloadditions of 1 with several keto azines were unsuccessful. Selected compounds will be screened for medicinal and pesticidal activity; compounds 9,10 and 12a showed fungicidal activity against barley powdery mildew.

Synthesis of Conjugated Diallenes by Double [2,3]-Sigmatropic Rearrangement of Conjugated Diyne Trichloromethanesulfenates

The preparation of several 2,4-diyne-l,6-diols and their esterification with trichloromethanesulfenyl chloride is described. The thus generated bis-propargylic trichloromethanesulfenates undergo spontaneous double [2,3]-sigmatropic rearrangement which leads to the formation of conjugated diallenic trichloromethyl sulfoxides in good to excellent yields.

Industrial Scale Synthesis of Thiophosgene and Its Derivatives

Thiophosgene is manufactured on a mulittonne scale, using the continuous chlorination of carbon disulfide under aqueous conditions to prepare the key intermediate perchloromethyl mercaptan. The development of this process is described, and the uses of thiophosgene in the manufacture of chlorothioformates and isothiocyanates are reviewed.

ChemInform Abstract: Synthesis of 3H‐1,2,4‐Thiadiazolo(3,4‐b)benzothiazoles.

AbstractThe reaction between 2‐aminobenzothiazole (I) and trichloromethanesulfenyl chloride (II), which is run according to a literature procedure, affords the product (III).

Conversion of some azaheterocyclic-acetic esters and -acetonitriles into fused heterocycles

Various heterocyclic acetic esters and nitriles of the pyridine, thiazole, and imidazole series react with 3-methylthio-4-phenyl-1,2-dithiolium perchlorate to form fused pyridinethiones or dithiolylidene esters. These esters or nitriles also react with trichloromethanesulfenyl chloride to form fused isothiazoles.

N‐ and C‐sulfenylation of 1‐(1,2‐oxazol‐3 (and 5)‐yl)‐3‐alkylureas with organic sulfenyl chlorides

AbstractCondensation of chlorocarbonylsulfenyl chloride 1 with 1‐(5‐(1,1‐dimethylethyl)‐1,2‐oxazol‐3‐yl)‐3‐methylurea 4a has been found to give isomeric 2,4‐disubstituted‐1,2,4‐thiazolidine‐3,5‐diones 5 and 6. Assignments are confirmed by the X‐ray structure data of 6. Sulfenylation with alkoxycarbonylsulfenyl chlorides 7 and trichloromethylsulfenyl chloride 10 of 4 occurs exclusively on N‐1 rather than N‐3 of the urea moiety. With the isomeric 1‐[3‐(1,1‐dimethylethyl)‐1,2‐oxazol‐5‐yl]‐3‐methylurea 14 and ethoxycarbonylsulfenyl chloride 7b, C‐sulfenylated derivatives 15 and 16 are formed in low yield.

ChemInform Abstract: The Chemistry of Thiophosgene

Abstract The physical and chemical properties of thiophosgene with spefial reference to its use in organic syntheses are reviewed. Thiophosgene is best prepared by reductive dechlorination of trichloromethanesulfenyl chloride. Besides its use in classical preparations of isothiocyanates, thioureas, thiocarbamates, and thiocarbonates, it has been extensively used to synthesize a wide variety of thioxo substituted heterocycles of pharmaceutical importance by cyclisation of amines, phenols, alcohols, and thiols. Thiophosgene is also used to prepare various inorganic complexes and in the conversion of phenols, thioureas, and thioamides to thiophenols, ureas, and amides, respectively. Reaction of thiophosgene with dienes and alkenes gives bridged compounds and different reactive synthons. The review also discusses the chemistry of the thiophosgene dimer.

THE CHEMISTRY OF THIOPHOSGENE

Abstract The physical and chemical properties of thiophosgene with spefial reference to its use in organic syntheses are reviewed. Thiophosgene is best prepared by reductive dechlorination of trichloromethanesulfenyl chloride. Besides its use in classical preparations of isothiocyanates, thioureas, thiocarbamates, and thiocarbonates, it has been extensively used to synthesize a wide variety of thioxo substituted heterocycles of pharmaceutical importance by cyclisation of amines, phenols, alcohols, and thiols. Thiophosgene is also used to prepare various inorganic complexes and in the conversion of phenols, thioureas, and thioamides to thiophenols, ureas, and amides, respectively. Reaction of thiophosgene with dienes and alkenes gives bridged compounds and different reactive synthons. The review also discusses the chemistry of the thiophosgene dimer.

ChemInform Abstract: Some Reactions of Trichloromethanesulfenyl Chloride with Alcohols and Thiols.

AbstractDie aus Trichlormethansulfenylchlorid (II) erhaltenen Verbindungen wirken möglicherweise als Pestizide.

The Chemistry of Thiophosgene

The physical and chemical properties of thiophosgene with special reference to its use in organic syntheses are reviewed. Thiophosgene is best prepared by reductive dechlorination of trichloromethane-sulfenyl chloride. Besides its use in classical preparations of isothiocyanates, thioureas, thiocarbamates, and thiocarbonates, it has been extensively used to synthesize a wide variety of thioxo substituted heterocycles of pharmaceutical importance by cyclisation of amines, phenols, alcohols, and thiols. Thiophosgene is also used to prepare various inorganic complexes and in the conversion of phenols, thioureas, and thioamides to thiophenols, ureas, and amides, respectively. Reaction of thiophosgene with dienes and alkenes gives bridged compounds and different reactive synthons. The review also discusses the chemistry of the thiophosgene dimer.

Some reactions of trichloromethanesulfenyl chloride with alcohols and thiols

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSome reactions of trichloromethanesulfenyl chloride with alcohols and thiolsNafisa B. Islam, Harold Kwart, and S. KhanCite this: J. Chem. Eng. Data 1985, 30, 4, 509–512Publication Date (Print):October 1, 1985Publication History Published online1 May 2002Published inissue 1 October 1985https://doi.org/10.1021/je00042a046RIGHTS & PERMISSIONSArticle Views280Altmetric-Citations11LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (333 KB) Get e-Alerts Get e-Alerts

Interesting Errors in Sulfur Chemistry, 3

Abstract 3,6-DICHLORO-l,4,2,5-DITHIADIAZINE In 1963 it was found that trichloromethanesulfenyl chloride and ammonia could be made to react with elimination of hydrogen chloride according to (l):1 N CCI3SCI + n NH3 ← (CCINS)n + 3 n HCI

Interesting Errors in Sulfur Chemistry, 1

Abstract In 1959 Kober1 described the reaction of trichloromethanesulfenyl chloride 1 with mercury(II) fluoride and identified the reaction product as trichloromethanesulfenyl fluoride 2:

45] Methoxycarbonyl-CoA disulfide: An active site=directed sulfhydryl reagent

Publisher Summary This chapter discusses the preparation and effects of methoxycarbonyl-CoA disulfide. The relative ease with which protein sulfhydryl groups reacted with a variety of compounds has led to the preparation of a large number of sulfhydryl reagents. These reagents have been classified according to the groups that are delivered, including blocking and labeling groups, reporter groups, cross-linking groups, and afffinity-abeling groups. Methoxycarbonyl-CoA disulfide is prepared by the reaction of free CoA with methoxycarbonylsulfenyi chloride. The latter compound is prepared in a two-step synthesis starting with trichloromethanesulfenyl chloride. Trichloromethanesulfenyl chloride is added to 211 g of concentrated sulfuric acid and 18 g of water. The mixture is stirred at 45–50° in a well-vented hood until hydrogen chloride evolution ceases. The methyl group of methoxycarbonyl-CoA disulfide can be replaced with a variety of alkyl groups by substituting different alcohols for methanol in the reaction with chlorocarbonylsulfenyl chloride. Radiolabeled reagent can be prepared by using 3 H-labeled CoA. The reaction of methoxycarbonyl-CoA disulfide with choline acetyltransferase is also discussed.