ThioformaldehydeS-sulfide (Thiosulfine)

Mlostoń, Grzegorz; Romański, Jarosław; Reisenauer, Hans Peter; Maier, Günther

doi:10.1002/1521-3773(20010119)40:2<393::aid-anie393>3.0.co;2-j

Cited by 44 publications

(25 citation statements)

References 21 publications

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“…As the intermediacy of thiocarbonyl S-sul®des and their isomeric dithiiranes has frequently been proposed to explain the formation of polysulfur heterocycles El-Essawy et al, 1998;Fabian & Senning, 1998;Hegab et al, 1999;Hawata et al, 2000), many attempts have been undertaken to synthesize those compounds. Within the last few years, several stable dithiiranes have been prepared (Ishii et al, 1994;Ishii & Nakayama, 1999Shimada et al, 1999), and the parent compound has been generated photolytically and isolated in a matrix at 10 K (Mloston et al, 2001).…”

Section: Commentmentioning

confidence: 99%

Four bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)oligosulfanes

et al. 2002

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The four oligosulfanes, bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)disulfane, C(16)H(24)Cl(2)O(2)S(2), (III), 1,3-bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)trisulfane, C(16)H(24)Cl(2)O(2)S(3), (V), 1,4-bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)tetrasulfane, C(16)H(24)Cl(2)O(2)S(4), (VII), and 1,6-bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)hexasulfane, C(16)H(24)Cl(2)O(2)S(6), (VIII), all have similar geometric parameters, with the C-C bond lengths involving the chloro-substituted cyclobutanyl C atom being elongated to about 1.59 A. There are two molecules in the asymmetric units of the tri- and tetrasulfanes, and the molecules in the latter compound have local C(2) symmetry. The molecule of the hexasulfane has crystallographic C(2) symmetry. Most of the cyclobutanyl rings are not perfectly planar and have slight but varying degrees of distortion towards a flattened tetrahedron. The polysulfane chain in each structure has a helical conformation, with each additional S atom in the chain adding approximately one quarter of a turn to the helix.

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Section: Commentmentioning

confidence: 99%

Four bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)oligosulfanes

et al. 2002

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“…Our recent studies employed matrix isolation techniques for the spectroscopic characterization of products formed after gas‐phase flash‐vacuum pyrolysis (FVP) of the parent 1,2,4‐trithiolane ( 11 )8a and its 3,3,5,5‐tetramethyl derivative 15 8b (Scheme ). Subsequently, we studied the reactivity of the matrix‐isolated products by irradiation with UV light or by annealing of the matrix.…”

Section: Introductionmentioning

confidence: 99%

“…In the case of 11 , we observed the formation of comparable amounts of both thioformaldehyde S ‐sulfide ( 12 ) and isomeric dithiirane ( 13 ). Upon irradiation with λ = 570 nm light, parent thiosulfine 12 isomerized to 13 and further into dithioformic acid ( 14 ) 8a. Gas‐phase thermolysis of 15 led to the formation of the product resulting from a [1,4] H‐shift, identified as vinyldisulfane 18 (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Generation and Rearrangement of Some Spirocycloaliphatic Thiosulfines and Dithiiranes

et al. 2008

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The flash‐vacuum pyrolysis of selected dispirodicycloaliphatic 1,2,4‐trithiolanes was studied by using matrix isolation techniques. The formation of thiosulfines and dithiiranes along with the corresponding thioketones was detected spectroscopically and confirmed by comparison with computed spectra. In the case of tetramethylcyclobutanone 1,2,4‐trithiolane, the thermal formation of the dithiolactone was observed. Pyrolysis of the (dichloro)tetramethylcyclobutane derivative resulted only in the formation of a mixture of the thiosulfine and dithiirane. In this case, conversion into the corresponding dithiolactone could be achieved photochemically. The dispirodiadamantane derivative gave a mixture of the respective thiosulfine and dithiirane but no dithiolactone could be detected in the mixture. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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“…Bereits vor 20 Jahren wurde postuliert, daû Thiosulfine im Gleichgewicht mit ihren cyclischen Valenzisomeren, den Dithiiranen R 2 C±S±S, vorliegen und sich irreversibel in die entsprechenden Dithiocarbonsa È ure-Derivate umwandeln sollen [3]. Ku È rzlich konnte durch Vakuumblitzpyrolyse von 1,2,4-Trithiolan I das Thiosulfin H 2 C=S + ±S ± erzeugt und durch Photolyse bei 10 K zuna È chst in das Dithiiran H 2 C±S±S und anschlieûend in die Dithioameisensa È ure u È berfu È hrt werden [4]. Ku È rzlich konnte durch Vakuumblitzpyrolyse von 1,2,4-Trithiolan I das Thiosulfin H 2 C=S + ±S ± erzeugt und durch Photolyse bei 10 K zuna È chst in das Dithiiran H 2 C±S±S und anschlieûend in die Dithioameisensa È ure u È berfu È hrt werden [4].…”

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Herstellung von 1,2,4-Trithiolan-, 1,2,4,5-Tetrathian- sowie 1,2,3,5,6-Pentathiepan-S-oxiden und deren Reaktionen mit (Ph3P)2Pt(η2-C2H4). Kristallstrukturanalyse von 3,3,5,5-Tetraphenyl-1,2,4-trithiolan-1-oxid

Weigand

Wünsch²,

Polborn

et al. 2001

Z. anorg. allg. Chem.

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Bei der Oxidation von 3,3,5,5‐Tetraphenyl‐1,2,4‐trithiolan (1) mit m‐Chlorperbenzoesäure entsteht selektiv das 3,3,5,5‐Tetraphenyl‐1,2,4‐trithiolan‐1‐oxid (2). Die Molekülstruktur von 2 wurde durch Röntgenstrukturanalyse bestimmt. Die Oxidation von Octamethyltetrathiadispiro[3.2.3.2]dodecan‐2,9‐dion (3) mit Trifluorperessigsäure bei –50 °C liefert das 5‐Oxid 4. Das Octamethylpentathiadispiro[3.3.3.2]tridecan‐2,9‐dion (5) wird mit m‐Chlorperbenzoesäure bei 0 °C zum 12‐Oxid 6 oxidiert. Das 1‐Oxid 2 reagiert mit zwei Äquivalenten (Ph3P)2Pt(η2‐C2H4) (7) zu einem 1 : 1 Gemisch von (Ph3P)2PtSCPh2S (8) und (Ph3P)2Pt(η2‐Ph2C=S=O) (9).

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ThioformaldehydeS-sulfide (Thiosulfine)

Abstract: Matrix isolation spectroscopy allows the direct identification of ylide 1 and its cyclic isomer 2. They were obtained by pyrolysis of 1,2,4‐trithiolane under high vacuum; the cyclic compound forms from 1 by thermal ring closure in a kinetically controlled reaction.

Cited by 44 publications

References 21 publications

Four bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)oligosulfanes

Four bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)oligosulfanes

Generation and Rearrangement of Some Spirocycloaliphatic Thiosulfines and Dithiiranes

Herstellung von 1,2,4-Trithiolan-, 1,2,4,5-Tetrathian- sowie 1,2,3,5,6-Pentathiepan-S-oxiden und deren Reaktionen mit (Ph3P)2Pt(η2-C2H4). Kristallstrukturanalyse von 3,3,5,5-Tetraphenyl-1,2,4-trithiolan-1-oxid

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