420-32-6Relevant articles and documents
CO2 LASER-INDUCED INTERACTION BETWEEN SULFUR HEXAFLUORIDE AND CARBON DISULFIDE
Pola, J.,Horak, M.,Engst, P.
, p. 37 - 44 (1981)
Interaction between carbon disulfide and sulfur hexafluoride is excited by cw CO2 laser radiation and has been investigated for different ratiosover a pressure range from 3.1 to 34.6 kPa.The reaction yields sulfur tetrafluoride, sulfur, carbon, thiocarbonyl fluoride, tetrafluoromethane and hexafluoroethane, the ratio of these latter products is dependent on the partial pressure of sulfur hexafluoride in the initial CS2-SF6 mixture.Interaction is considered to include both the SF6-sensitized decomposition of carbon disulfide and reaction between sulfur hexafluoride and carbon disulfide.
A selected ion flow tube study of the reactions of gas-phase cations with PSCl3
Critchley, Andrew D.J.,Howle, Chris R.,Mayhew, Chris A.,Tuckett, Richard P.
, p. 235 - 241 (2008/10/09)
A selected ion flow tube was used to investigate the positive ion chemistry of thiophosphoryl chloride, PSCl3. Rate coefficients and ion product branching ratios have been determined at room temperature for reactions with 19 cations; H3O+, CF3+, CF +, NO+, NO2+, SF2 +, SF+, CF2+, O2 +, H2O+, N2O+, O +, CO2+, CO+, N+, N 2+, Ar+, F+ and Ne+ (in order of increasing recombination energy). Complementary data described in the previous paper have been obtained for this molecule via the observation of threshold photoelectron photoion coincidences. For ions whose recombination energies are in the range 10-22 eV, comparisons are made between the product ion branching rations of PSCl3 from photoionisation and from ion-molecule reactions. In most instances, the data from the two experiments are well correlated, suggesting that long-range charge transfer is the dominant mechanism for these ion-molecule reactions; the agreement is particularly good for the atomic ions Ar+, F+ and Ne+. Some reactions (e.g. O2++PSCl3), however, exhibit significant differences; short-range charge transfer must then be occurring following the formation of an ion-molecule complex. For ions whose recombination energies are less than 10 eV (i.e. H3O+, CF 3+, CF+ and NO+), reactions can only occur via a chemical process in which bonds are broken and formed, because the recombination energy of the cation is less than the ionisation energy of PSCl3.
Unusual reaction of Grignard reagents with bis(trifluoromethyl)disulfide
Munavalli, S.,Rossman, D. I.,Rohrbaugh, D. K.,Ferguson, C. P.
, p. 147 - 153 (2007/10/02)
Simultaneous scission of the C-S and S-S bonds of bis(trifluoromethyl)disulfide occurs on treatment with Grignard reagents at -78 deg C and gives rise to unsymmetrical disulfides and sulfides as well as alkyl sulfides.Under similar experimental conditions, alkyl disulfides are recovered unreacted.Probable mechanisms of the cleavage reactions are presented.
Simultaneous scission of C-S and S-S bonds of bis(trifluoromethyl)trisulfide by Grignard reagents
Munavalli, Shekar,Rossman, David I.,Rohrbaugh, Dennis K.,Ferguson, C. Parker,Szafraniec, Leonard J.
, p. 91 - 99 (2007/10/02)
Trifluoromethyl mono-, di- and tri-sulfides, and alkyl sulfides and disulfides, as well as dimerized products, are formed as a result of the simultaneous cleavage of the C-S and S-S bonds of bis(trifluoromethyl)trisulfide by Grignard reagents at -78 deg C.The formation of various products has been rationalized on the basis of the involvement of free radicals.
TRANSFORMATION OF ORGANOPHOSPHORUS S-TRIFLUOROMETHYLTHIOATES RR'P(O)SCF3 INTO FLUORIDES RR'P(O)F. STEREOCHEMICAL ASPECTS OF THIOCARBONYL FLUORIDE EXTRUSION
Lopusinski, Andrezej
, p. 383 - 390 (2007/10/02)
The stereochemical course of the thermal or by nucleophiles catalyzed extrusion reaction of thiocarbonyl fluoride from two diastereomeric (6) and optically active (10) organophosphorus S-trifluoromethylthioates has been investigated.To explain the observed retention of configuration at phosphorus in fluoridates 7 formed in the thermal reactions, a four center transition state for such reactions has been proposed.The lack of the stereoselectivity in the catalyzed reactions of 6, and the observed racemization of the final product 11 are briefly discussed.
Thiocarbonyl Fluoride in the Solvent System Hydrogen Fluoride: Preparation and Reactions of Halogenated Thiocarbenium Ions
Haas, Alois,Wanzke, Wolfgang
, p. 429 - 434 (2007/10/02)
Solvolysis of thiocarbonyl fluorides 1b, c in HF/SbF5 or FSO3H/SbF5 yields dithietane-2-ylium ions 2b, c, respectively.Reactions of 2b, c with the base F in the solvent system HF give the dithietanes 3b, c.The acidity dependance of the formation of 2b, c is demonstrated by gradation of the acidic strength with NbF5 and F(1-).The existence of thioacylium ions 5b, c in solutions of extremely high acidity is concluded from NMR spectroscopic data.The results of the solvolysis reactions are confirmed by thioacylation of the aromatic compounds 6a-d in the HF system leading to trifluoromethyl dithiobenzoates 7a-d.Among the corresponding carbonyl fluorides only 4 exhibits comparable basic properties in superacids.
Characterisierung und Photochemie von (Dihalogenmethylen)sulfoxiden, XYC=S=O
Sander, Wolfram,Henn, Rolf,Sundermeyer, Wolfgang
, p. 1281 - 1288 (2007/10/02)
Dihalogenomethylene sulfoxides (dihalogenosulfines) 2a-c were generated by flash vacuum pyrolysis of 2,2,4,4-tetrahalogeno-1,3-dithietane 1,3-dioxides 1a-c and trapping the pyrolysis products in argon at 10 K.At room temperature unstable difluorosulfine (2a) and chlorofluorosulfine (2b) were identified by i.r.spectroscopy, and the photochemistry of the sulfines was investigated.Chlorofluorosulfine (2b) exists in two geometrical isomers.Photolysis of 2a leads to fragmentation to give CF2 and SO, photolysis of the chlorine containing sulfines 2b and 2c to rearrangement to give sulfenyl chlorides 6 and 8.This is explained by different migratory tendencies of fluorine and chlorine and the stability of C-F bond.
Synthesis and Properties of New Perhalogenated 1,3-Dithietane S-Oxides
Eschwey, Manfred,Sundermeyer, Wolfgang,Stephenson, David S.
, p. 1623 - 1630 (2007/10/02)
New perchlorinated and perfluorinated 1,3-dithietanes (4, 6, 7, 12, 14, 15), which are partially oxidized at the sulfur atoms, are described.Pyrolysis of the 1,3-dioxides 7 and 15 leads to the sulfoxides 8 and 16, X2C=S=O (X=Cl, F), respectively.Two new oxidizing agents are used: trifluoromethane- and nonafluorobutanepersulfonic acid.
A COMPARATIVE STUDY OF THE SF6-SENSITIZED INTERACTION OF A CW-CO2 LASER RADIATION WITH METHYLTRICHLORO DERIVATIVES OF CARBON, SILICON AND GERMANIUM
Pola, Josef,Bellama, John M.,Chvalovsky, Vaclav
, p. 3088 - 3096 (2007/10/02)
A comparative study of the gas-phase interaction of methyltrichloro derivatives of carbon, silicon and germanium (CH3MCl3 where M=C, Si and Ge) with sulphur hexafluoride either excited by a cw-CO2 laser radiation or under conventional static pyrolytic conditions is reported. 1,1,1-Trichloroethane and methyltrichlorogermane do not react with SF6 under laser irradiation and undergo their decomposition leading to the same products as afforded by heating: CH3CCl3 yields Cl2C=CH2 and HCl, and CH3GeCl3 gives HGeCl3 along with CH4 and C2H2.Mixtures of methyltrichlorosilane and SF6 afford under both conditions product of the CH3SiCl3 decomposition - CH4, C2H2, HCl and SiCl4 and products of the CH3SiCl3-SF6 reaction - SiF4, SCF2, and CS2.Possible reasons for the different reactivity of CH3MCl3 compounds toward SF6 are briefly discussed.The decompositions of CH3GeCl3 to HGeCl3 offers new way for the preparation of the latter compound.
