Unimolecular isomerization of chemically activated thiirane to vinylthiol

Sherwood, A. G.; Safarik, I.; Verkoczy, Bela; Almadi, G.; Wiebe, H. A.; Strausz, O. P.

doi:10.1021/ja00505a029

Cited by 20 publications

(32 citation statements)

References 2 publications

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“…The high vacuum apparatus and procedures employed were similar to those described in previous reports from this laboratory (4).…”

Section: Methodsmentioning

confidence: 99%

“…Recently, the photolysis of trithiocarbonates has been shown to be a superior source of thiirene (19) and the isolation and esr identification of a thioketocarbene, namely, the To state thiobenzoylphenylmethylene, has also been accomplished (21). The To state of the thioketocarbene, formed in [4], is nearly isoenergetic with the S, state; both are double open shell species and are better represented by the 1,3-diradical structure as indicated above.…”

Section: S('d)+ Hc=ch -Hc=ch-s ( S I ) Ah--46 Kcal/mol [3] S('d) + mentioning

confidence: 99%

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Thiirene formation in the reactions of sulfur atoms with alkynes

Verkoczy¹,

Sherwood²,

Safarik³

et al. 1983

Can. J. Chem.

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The gas phase reactions of S(1D2) and S(3PJ) atoms with alkynes have been studied by photolyzing COS in the presence of CH≡CH, CF3C≡CH, and CF3C≡CCF3. In the reactions with CH≡CH, CS2, benzene, and thiophene were formed; with CF3C≡CH, eight products were found with disubstituted thiophenes and trisubstituted benzenes as the major products. In the case of CF3C≡CCF3, only perfluorotetramethylthiophene was detected at low conversion but at long photolysis several new products were observed. Many of the reaction products characterized here have not been reported before.The formation and distribution of the reaction products could be rationalized by an overall mechanism in which the formation of the highly reactive primary adducts, thiirene and thioformylmethylene, is followed by bimolecular reactions yielding the principal end products. The formation of minor products could be explained by secondary photoisomerizations, secondary photolysis, and by secondary decompositions and the secondary reactions of sulfur atoms with primary products.

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“…The high vacuum apparatus and procedures employed were similar to those described in previous reports from this laboratory (4).…”

Section: Methodsmentioning

confidence: 99%

Section: S('d)+ Hc=ch -Hc=ch-s ( S I ) Ah--46 Kcal/mol [3] S('d) + mentioning

confidence: 99%

Thiirene formation in the reactions of sulfur atoms with alkynes

Verkoczy¹,

Sherwood²,

Safarik³

et al. 1983

Can. J. Chem.

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“…[17] ), ethenethiol and thiirane are produced by reactions of S( 1 D) and S( 3 P) atoms with ethene, [18][19][20] hydrogen sulfide is formed by reaction of S atoms with H 2 (whose presence in the irradiated system is proven by the occurrence of ethyne, butadiyne and butenyne), and thiophene is produced by reaction of S atoms with ethyne. [21] While the S-containing products prove the transient occurrence of S atoms, their low quantities (not more than 10 percent of the depleted CS 2 ) indicate that the extent of CS 2 fragmentation into CS and S is rather low.…”

Section: Gas-phase Photolysis and Volatile Productsmentioning

confidence: 99%

UV Laser Chemical Vapor Deposition of Nano‐Chained Copolymer from Carbon Disulfide and Ethene

Bastl¹,

Pola²

2004

Macro Chemistry & Physics

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Summary: Laser irradiation at 193 nm of gaseous mixtures of carbon disulfide and ethene induces copolymerization of both compounds and affords chemical vapor deposition of conjugated nano‐chained C/S/H polymer, with contributions from C2H4 and CS2 almost unaffected by very different initial ratio of both educts. The polymer structure is interpreted on the basis of X‐ray photoelectron and FTIR spectra as consisting of >CS, >CC<, CH2CH2, (CC)SnC4−n, C(CS)S, S(CS)S and CSSC configurations, whose extent is dependent on the irradiation conditions.Typical TEM image of the solid copolymer obtained by laser‐induced copolymerization of carbon disulfide and ethene.magnified imageTypical TEM image of the solid copolymer obtained by laser‐induced copolymerization of carbon disulfide and ethene.

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“…It may, however, be formed either from a "hot" thiirane-thiol rearrangement involving thiirane 1 or via an enethiol-thioketeneenethiol tautomerization of 1,2-butadiene-3-thiol 6 formed in step [5e], Scheme 1. The occurrence of a hot thiirane-thiol rearrangement 1-2 is, however, unlikely since in chemically activated methylthiirane, which has fewer degrees of freedom than the C4H6S adduct, this process is of very minor importance even at low pressures (2). On the other hand, the existence of enethiol-thioketone rearrangements is well documented (18) and moreover, of the three species involved in the tautomerization of 6, the most stable, by virtue of carbon-carbon (Table 4), the total product recovery is estimated to be 81 % at zero time, of which the thiiranes comprise 94%.'…”

Section: H3c /C=c-ch2 H /C=c=ch2 Hs /C=c=ch2mentioning

confidence: 99%

“…Thus, the low yields (or absence) of insertion products in these systems may also be a consequence of the fact that most of the S('D) atoms generated in step [ l ] had been deactivated to the ground ('P) state prior to reaction. It should be noted, however, that the branching ratio for step [ l ] and the abstraction/deactivation rate constant ratio for step [2] are indirect estimates only, and a more quantitative assessment of the relative concentrations of (ID) and (") atoms awaits our studies on direct rate measurements of these reactions.…”

Section: H3c /C=c-ch2 H /C=c=ch2 Hs /C=c=ch2mentioning

confidence: 99%

The reactions of sulfur atoms with propadiene and 1,2-butadiene

Green¹,

Verkoczy²,

Lown³

et al. 1985

Can. J. Chem.

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The gas phase reactions of both S('D) and S(?P) atoms with propadiene afford methylenethiirane in nearly quantitative yields at high pressure. With 1,2-butadiene the three novel unsaturated isomeric thiirane products, resulting from addition to the 2,3 double bond and cis-and trans-addition to the 1,2 double bond, have been characterized. The yields are pressure and exposure-time dependent and, at zero conversion and high pressures, comprise -94% of the C4H,S adducts, the remainder being two thiol insertion products. The ratio of 2,3-addition to 1,2-addition is -1.3 for S('D) atoms and -2.1 for S(?P) atoms.Rate parameters for the S(") + 1.2-butadiene reaction were determined in competition with the S(?P) + I-C,H, reaction and found to be A = 6.4 + I. l X 10"' M -' s-' and E, = 1.4 + 0.2 kcal mol-'. The E,,'s associated with 1.

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Unimolecular isomerization of chemically activated thiirane to vinylthiol

Cited by 20 publications

References 2 publications

Thiirene formation in the reactions of sulfur atoms with alkynes

Thiirene formation in the reactions of sulfur atoms with alkynes

UV Laser Chemical Vapor Deposition of Nano‐Chained Copolymer from Carbon Disulfide and Ethene

The reactions of sulfur atoms with propadiene and 1,2-butadiene

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