Trapping of a Thiocarbonyl Ylide with Imidazolethiones, Pyrimidinethione, and Thioamides

Mlostoń, Grzegorz; Gendek, Tomasz; Linden, Anthony; Heimgartner, Heinz

doi:10.1002/(sici)1522-2675(19990210)82:2<290::aid-hlca290>3.0.co;2-p

Cited by 8 publications

(6 citation statements)

References 7 publications

(8 reference statements)

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“…The CÐC bond lengths involving the chloro-substituted cyclobutanyl C atom are longer than normal CÐC single bonds, in the range 1.585 (2)± 1.601 (2) A Ê . However, they are consistent with those previously found in a similar environment (Mloston et al, 1999). This is evidently due to the electron-withdrawing properties of the S and Cl substituents.…”

Section: Crystal Structure Communicationssupporting

confidence: 92%

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: Crystal Structure Communicationssupporting

confidence: 92%

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

et al. 2002

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“…This chemoselectivity corresponds with that observed in the reactions of 6 with phenylisocyanate. 21 Neither products of the nucleophilic attack onto the C=S group nor products of the insertion into the S-H bond could be detected.…”

Section: Discussionmentioning

confidence: 99%

“…21 The results showed that, depending on the reagent, the reactions occurred selectively either at the S-(with dimethyl acetylenedicarboxylate) or N-atom (with phenylisocyanate). For the present study, selected imidazole-2(3H)-thiones of type 6 were used in reactions with 1a.…”

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confidence: 99%

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Unexpected Insertion Reaction of Dimethoxycarbene with Imidazole-2(3H)-thiones

Mlostoń

Heimgartner

2010

Phosphorus, Sulfur, and Silicon and the Related Elements

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“…Thiophenol and enolizable heterocyclic thiones are also efficient trapping reagents for thiocarbonyl S-methylides [2,19]. Therefore, thiophenol, benzo-1,3-thiazole-2-thione, and 1-cyclohexyl-4,5-dimethylimidazole-2-thione were applied to capture the reactive dipolar intermediates in reactions with 15a.…”

Section: Methodsmentioning

confidence: 99%

Addition of Diazomethane to Phosphonodithioformates and Reactions of Phosphonylated Thiocarbonyl S‐Methylides.

et al. 2005

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The reaction of phosphonodithioformates 14 with diazomethane at -60°C yielded 2,5-dihydro-1,3,4-thiadiazoles 15 as unstable intermediates. Their structure was evidenced by the base-catalyzed elimination of methylsulfane leading to 1,3,4-thiadiazole-2-phosphonates. At ca. -35°C, thermal decomposition of 15 by N2-elimination led to reactive thiocarbonyl S-methylides 17. In the absence of trapping reagents, these 1,3-dipoles undergo a head-to-head dimerization leading to 1,4-dithianes 18. An intermediate zwitterionic dimer 19 was detected by 31P NMR spectroscopy. The initially formed thiocarbonyl S-methylide 17 as well as an open-chain zwitterionic dimer 20 was intercepted by methanol. Stable interception products were also obtained with S-and N-nucleophiles.

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Trapping of a Thiocarbonyl Ylide with Imidazolethiones, Pyrimidinethione, and Thioamides

Cited by 8 publications

References 7 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

Unexpected Insertion Reaction of Dimethoxycarbene with Imidazole-2(3H)-thiones

Addition of Diazomethane to Phosphonodithioformates and Reactions of Phosphonylated Thiocarbonyl S‐Methylides.

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