Sulfur Monochloride Research Articles

Reactions of sulfur monochloride with some aromatic aldehyde semicarbazones and thiosemicarbazones: New syntheses of substituted 2,4‐dihydro‐1,2,4‐triazol‐3‐ones, 2,4‐dihydro‐1,2,4‐triazole‐3‐thiones and 2‐amino‐1,3,4‐oxadiazoles

AbstractTreatment of various substituted semicarbazones of aromatic aldehydes with sulfur monochloride yields the corresponding substituted 2,4‐dihydro‐1,2,4‐triazol‐3‐ones. With thiosemicarbazones, the products are derivatives either of the 2‐amino‐1,3,4 thiadiazole or of the 2,4‐dihydro‐1,2,4‐triazole‐3‐thione depending on the experimental conditions.

The microwave spectrum of the pyramidal isomer of disulfur difluoride: SSF2

Abstract The pyramidal isomer of disulfur difluoride, SSF2, has been prepared by passing gaseous disulfur dichloride through heated potassium fluoride. The microwave spectra of three isotopic species of SSF2 have been measured in the 26- to 76-GHz frequency region. For the most abundant isotopic species transitions with J values up to 79 have been observed. These data have been combined with previous measurements of low-J lines by R. L. Kuczkowski [J. Amer. Chem. Soc. 86, 3617–3621 (1964)] and fit to obtain values for the rotational constants and centrifugal distortion constants. The quartic centrifugal distortion constants have been used together with existing vibrational data to determine an harmonic force field for the molecule. Finally, ground state average and equilibrium structures have been calculated for SSF2.

ChemInform Abstract: Reaction of Aldehyde‐N,N‐tetramethylenehydrazones with Disulphurdichloride: Synthesis of 1,2‐Dithiol Derivatives.

ChemInform Abstract: Reaction of Aldehyde‐N,N‐tetramethylenehydrazones with Disulphurdichloride: Synthesis of 1,2‐Dithiol Derivatives.

Study of reaction of sulfur halides with unsaturated. Compounds. 24. Reaction of sulfur monochloride with adamantylidene-adamantane

In the reaction of adamantylideneadamantane with S2Cl2 at an equimolar ratio of the reagents, 2,2′-epithio-2-(2′-adamantyl)adamantane and 4-chloro-2,2′-epithio-2-(2′-adamantyl)-adamantane are formed, while with an excess of S2Cl2, the products are 4e-chloro- and 4e,4′e-dichloroadamantylideneadamantane.

Synthesis and identification of [ 76As]arsenic trichloride

Radiosynthesis of arsenic trichloride (AsCl 3) was achieved using 76As as the radionuclide of choice for preliminary investigations. The synthesis required neutron activation of arsenic trioxide (As 2O 3) followed by reaction with sulfur monochloride (S 2Cl 2) under a dry inert atmosphere. The synthesized 76AsCl 3 was purified by distillation or partially purified by treatment with dry acetonitrile followed by filtration. Identification was accomplished by thin layer chromatography (TLC) and reversed phase high performance liquid chromatography (HPLC). 76AsCl 3 was used for synthesis of a dihydrophenarsazine derivative.

Reaction of sulfur monochloride with hexafluoropropylene in the presence of fluorosulfonic and chlorosulfonic acids

In the reaction of sulfur chlorides with hexafluoropropylene in the presence of halosulfonic acids products of conjugated electrophilic addition are produced. Bis[(β-halosulfonyloxy)hexafluoroisopropyl] trisulfides are formed as a result of the reaction of 2-(chlorodithio)hexafluoropropyl halosulfates with halosulfonic acids.

Bis-(2-chloropolyfluoroalkyl)disulfides. Synthesis and properties

Thermal reactions of polyfluoralkenes with disulfur dichloride lead to bis-(2-chloropolyfluoroalkyl)disulfides (I), which proved to be effective precursors of diverse fluorosulfurorganic compounds. By present preparative syntheses of disulfides were developed out of trifluoromethylethylene, trifluoro-, tetrafluoro- and trifluorochloroethylenes, perfluoromethylvinyl ether, 2-hydropentafluoropropilene. Regularities of these reactions were revealed, the effects of different factors on addition regioselectivity were studied. Some disulfides (I) are converted into 2-chloropolyfluoralkylsulfonylchlorides out of which polyfluoralkenylsulfonyl halogenides are obtained (II). Under certain conditions disulfides (I) are converted into 2-chlopolyfluoroalkanesulfonyl chlorides that proved to be good precursors of fluorcontaining unsaturated sulfides (III), sulfoxides (IV) and sulfones (V). On the basis of unsaturated compounds (II)–(V) various polyfluoralkylsubstituted alicyclic, acyclic and hetero- cyclic sulfurorganic compounds were synthesized. Highlyelectrophilic perfluorated unsaturated compounds such as hexafluorodimethylketene and oktafluoroisobutilene do not interact with disulfur dichloride in thermal processes. It was possible to perform these reactions under mild conditions using the effects of specific solvatation of reagents. Products of these reactions (disulfides and thiosulfenyl chlorides) also proved to be effective precursors of different fluorosulfurorganic compounds.

ChemInform Abstract: SYNTHESIS AND PROPERTIES OF TRIFLUOROMETHYLTHIIRANE

1. A method for synthesis of trifluoromethylthiirane has been found which is based on the reaction of H2S with 1,1,1-trifluoro-3-chloropropane-2-sulfenyl chloride in N-methylpyrrolidone. 2. Reactions of trifluoromethylthiirane with electrophilic (Cl2, HCl, CH3COCl) and nucleophilic (LiAlH4, Me2NH) reagents have been investigated, leading to 1,1,1-trifluoro-3-chloropropane-2-sulfenyl chloride, 1,1,1-trifluoro-3-chloro-2-propanethiol, 1-(trifluoromethyl)-2-chloroethyl thioacetate, 1,1,1-trifluoro-2-propanethiol, and 1,1,1-trifluoro-3-(N,N-dimethylamino)-2-propanethiol, respectively. 3. The order of addition of sulfur monochloride to 1,1,1-trifluoropropene with the formation of bis-[1-(trifluoromethyl)-2-chloroethyl] disulfide has been established.

Organoxytitanium and Organotin Derivatives of Dibasic Tetradentate Chelating Disulphides

Abstract The reaction between sulphur monochloride and salicylaldehyde has been found to give preferentially para-substituted bis(salicylaldehyde)disulphide, [C6H3(OH) (CHO)]2S2, A similar reaction has been observed in the case of ketonic phenols (2-hydroxyacetophenone, 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone). β-Diketones (acetylacetone, benzoylacetone, dibenzoylmethane, acetoacetanilide) give predominantly the enolised disulphide moiety. However, bis(dibenzoylmethane)-disulphide has been found to exist in the ketonic form probably due to steric demand. Coordination compounds of these disulphides with organotitanium(IV) and organotin(IV) have been synthesised and characterised; they are thermally stable polymeric substances. The disulphides themselves are monomeric in boiling benzene.

Discovery and crystal structure of a novel chlorocarbon host: perchlorofluorene-9-spirocyclohexa-2′,5′-diene

Chlorination of triphenylene (1a) employing a mixture of aluminium trichloride and sulphur monochloride in sulphuryl chloride leads to rearrangement with formation of the title chlorocarbon (2), a new host, as main product. X-ray crystal structure analyses of the unsolvated spirocycle (2) as well as of its inclusion compounds with guests benzene and cyclohexa-1,4-diene are described.

Recent Advances in Thermally and Photochemically Initiated Cationic Polymerization

Several new classes of triarylsulfonium salts have been discovered which possess enhanced efficiency as photoinitiators of cationic polymerization. One of these compounds was identified among the components of the Friedel Crafts reaction of benzene with sulfur monochloride and chlorine. Specific new syntheses were developed and are described for the synthesis of these compounds in high yields. The development of several new thermal initiator systems for cationic polymerization based on dialkyl-4-hydroxyphenylsulfonium and dialkylphenacylsulfonium salts is also discussed.

Synthesis and properties of trifluoromethylthiirane

1. A method for synthesis of trifluoromethylthiirane has been found which is based on the reaction of H2S with 1,1,1-trifluoro-3-chloropropane-2-sulfenyl chloride in N-methylpyrrolidone. 2. Reactions of trifluoromethylthiirane with electrophilic (Cl2, HCl, CH3COCl) and nucleophilic (LiAlH4, Me2NH) reagents have been investigated, leading to 1,1,1-trifluoro-3-chloropropane-2-sulfenyl chloride, 1,1,1-trifluoro-3-chloro-2-propanethiol, 1-(trifluoromethyl)-2-chloroethyl thioacetate, 1,1,1-trifluoro-2-propanethiol, and 1,1,1-trifluoro-3-(N,N-dimethylamino)-2-propanethiol, respectively. 3. The order of addition of sulfur monochloride to 1,1,1-trifluoropropene with the formation of bis-[1-(trifluoromethyl)-2-chloroethyl] disulfide has been established.

A novel photoinitiator of cationic polymerization: Preparation and characterization of bis [4‐(diphenylsulfonio)phenyl]sulfide–bis‐hexafluorophosphate

AbstractEfforts to prepare triphenylsulfonium hexafluorophosphate by metathesis between commercially available “triphenylsulfonium chloride” and potassium hexafluorophosphate failed to yield the expected product but gave, instead, in approximately 50% yield, a crystalline substance with well‐defined properties readily distinguishable from triphenylsulfonium hexafluorophosphate. The unexpected substance is identified as bis‐[4(diphenylsulfonio)phenyl]sulfide–bis‐hexafluorophosphate, for which no previous reference has been found in the literature. Its identification is based on elemental analysis, NMR, mass spectrometry, and infrared analysis. Bis‐[4‐(diphenylsulfonio)phenyl]sulfide–bis‐hexafluorophosphate was also prepared by the reaction of benzene with sulfur monochloride in the presence of aluminum chloride and chlorine, followed by addition of potassium hexafluorophosphate. The product is an effective photonitiator for the crosslinking of epoxide resins.

Structural studies of technetium complexes. V. The preparation and crystal structure of Dichlorobis(diethyldithiocarbamato)thionitrosyltechnetium(III)

Dichlorobis(diethyldithiocarbamato)thionitrosyltechnetium(III), [Tc(S2CNEt2)2Cl2(NS)], has been prepared by the reaction of [Tc(S2CNEt2)2N] with either disulfur dichloride or thionyl chloride. The crystal structure of [TC(S2CNEt2)2Cl2(NS)] has been determined by single-crystal X-ray diffraction methods at 15�C. Crystals are orthorhombic, space group Pcmn, with a 8.936(1), b 15.681(1), c 28.445(7) �, and Z 8. Automatic diffractometry has provided significant Bragg intensities for 2078 independent reflections, and the structure has been refined by full-matrix least-squares methods to R 0.078. The crystal lattice is disordered across a non-crystallographic mirror plane, the degree of disorder being 4.0(2)% for the crystal described above, and 21.9(7)% for another crystal initially used to obtain an intensity data set. There are two independent molecules of [Tc(S2CNEt2)2Cl2(NS)] in the asymmetric unit, and in each the technetium atom is seven-coordinate with a pentagonal-bipyramidal coordination environment. The Tc=N=S bonding is linear with Tc=N c. 1.75 and N=S c. 1.52 �, which indicates that the thionitrosyl group is a three-electron donor with a formal positive charge. This is only the third crystal structure of a complex containing the thionitrosyl group to be determined, and the first for technetium.

The Use of S 2Cl2 for Doping Poly ‐ GaAs Films Grown by the Organometallic Process

This work reports on the use of sulfur monochloride, , as a dopant for n+‐layers in gallium arsenide. This compound was chosen for its ready availability, convenient vapor pressure, and rapid breakdown at growth temperatures. Our results indicate that its use is beneficial for both high doping and good morphology in polycrystalline gallium arsenide solar cells, made on foreign (molybdenum) substrates.

Reaction of octafluoroisobutylene with sulfur monochloride

In contrast to tetrafluoroethylene [l], octafluoroisobutylene does not react with S=C12 in the absence of solvents or in solutions in CC14 on heating to 200~ It has been impossible, also, to carry out nucleophilic addition under the conditions of the reactions of highly electrophilic polyfluoroalkenes with alkyland arylsulfenyl chlorides [2]. It has been possible to obtain products of the addition of $2C12 to octafluoroisobutylene only in acetonitrile or benzonitrile in the presence of triethylamine. Under these conditions the first step of the reaction -the formation of chlorooctafluoro-tert-butylthiosulfenyl chloride (I) -takes place exothermically at 20~ (5-6 h); for the formation of bis(chlorooctafluoro-tert-butyl) disulfide (II) under the same conditions the mixture of reactants must be kept for not less than 2 days.

ChemInform Abstract: REACTIONS OF KETONE HYDRAZONES AND β‐KETO ENAMINES WITH DISULFUR DICHLORIDE. NEW SYNTHESIS OF THIOKETONES AND 5H‐1,2,3‐DITHIAZOLES

AbstractDie Ketohydrazone (I) reagieren mit 82C], in Gegenwart von Et3N zu den Thioketonen (II) (Bildungsmechanismus mit Zwischenstufen wird erörtert).

ChemInform Abstract: PHOTOIONIZATION MASS SPECTRA OF SULFUR DICHLORIDE (SCL2), DISULFUR DICHLORIDE (S2CL2) AND DISULFUR DIBROMIDE (S2BR2)

Chemischer InformationsdienstVolume 13, Issue 6 Physical Inorganic Chemistry ChemInform Abstract: PHOTOIONIZATION MASS SPECTRA OF SULFUR DICHLORIDE (SCL2), DISULFUR DICHLORIDE (S2CL2) AND DISULFUR DIBROMIDE (S2BR2) R. KAUFEL, Search for more papers by this authorG. VAHL, Search for more papers by this authorR. MINKWITZ, Search for more papers by this authorH. + BAUMGAERTEL, Search for more papers by this author R. KAUFEL, Search for more papers by this authorG. VAHL, Search for more papers by this authorR. MINKWITZ, Search for more papers by this authorH. + BAUMGAERTEL, Search for more papers by this author First published: February 9, 1982 https://doi.org/10.1002/chin.198206004Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume13, Issue6February 9, 1982 RelatedInformation

Synthesis of 2,4,6-tri-t-butylthiobenzaldehyde, the first stable thiobenzaldehyde

The title compound, an extremely stable thiobenzaldehyde, was prepared by the reaction of 2,4,6-tri-t-butylphenyl-lithium with O-ethyl thioformate or the reaction of 2,4,6-tri-t-butylbenzaldehyde hydrazone with disulphur dichloride.

Reactions of Ketone Hydrazones and β-Keto Enamines with Disulfur Dichloride. New Synthesis of Thioketones and 5H-1,2,3-Dithiazoles

Abstract Ketone hydrazones react with disulfur dichloride in the presence of triethylamine to afford thioketones in good yields. The reaction mechanism involving N-thiosulfinylamine (R2C=N–N=S=S) and S-thioxothioketone (R2C=S=S) is proposed. The formation of t-butyl and di-1-adamantyl thioketones even at low temperatures has been interpreted as steric congestion alone being not enough to stabilize the corresponding S-thioxothioketones. The reaction of β-ketoenamines with disulfur dichloride gives 5H-1,2,3-dithiazoles via intramolecular cyclization of intermediary N-thiosulfinylamines.