Crystal structure of<i>O</i>-ethyl<i>N</i>-(ethoxycarbonyl)thiocarbamate

Henley, Matthew J.; Schrader, Alex M.; Bárány, George

doi:10.1107/s2056989015016989

Cited by 2 publications

(1 citation statement)

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“…The four structures described in the current work can be compared to previously reported structures for the starting thiocarbamate 2e, 38 for several other compounds 39 that model (chlorocarbonyl)(carbamoyl)disulfanes by replacement of the acid chloride with a trichloromethyl moiety, for a cyclized intermediate (11) 9 that has not yet lost ethyl chloride (created by ZWK chemistry with R = H), and for several Dts-amines (1). 9,40−42 Taken together, these should provide the basis for a complete structural analysis of all of the participants and possible intermediates of the ZWK reaction.…”

Section: The Journal Of Organic Chemistrymentioning

confidence: 99%

Unexpectedly Stable (Chlorocarbonyl)(N-ethoxycarbonylcarbamoyl)disulfane, and Related Compounds That Model the Zumach–Weiss–Kühle (ZWK) Reaction for Synthesis of 1,2,4-Dithiazolidine-3,5-diones

et al. 2015

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The Zumach-Weiss-Kühle (ZWK) reaction provides 1,2,4-dithiazolidine-3,5-diones [dithiasuccinoyl (Dts)-amines] by the rapid reaction of O-ethyl thiocarbamates plus (chlorocarbonyl)sulfenyl chloride, with ethyl chloride and hydrogen chloride being formed as coproducts, and carbamoyl chlorides or isocyanates generated as yield-diminishing byproducts. However, when the ZWK reaction is applied with (N-ethoxythiocarbonyl)urethane as the starting material, heterocyclization to the putative "Dts-urethane" does not occur. Instead, the reaction directly provides (chlorocarbonyl)(N-ethoxycarbonylcarbamoyl)disulfane, a reasonably stable crystalline compound; modified conditions stop at the (chlorocarbonyl)[1-ethoxy-(N-ethoxycarbonyl)formimidoyl]disulfane intermediate. The title (chlorocarbonyl)(carbamoyl)disulfane cannot be converted to the elusive Dts derivative, but rather gives (N-ethoxycarbonyl)carbamoyl chloride upon thermolysis, or (N-ethoxycarbonyl)isocyanate upon treatment with tertiary amines. Additional transformations of these compounds have been discovered, providing entries to both known and novel species. X-ray crystallographic structures are reported for the title (chlorocarbonyl)(carbamoyl)disulfane; for (methoxycarbonyl)(N-ethoxycarbonylcarbamoyl)disulfane, which is the corresponding adduct after quenching in methanol; for [1-ethoxy-(N-ethoxycarbonyl)formimidoyl](N'-methyl-N'-phenylcarbamoyl)disulfane, which is obtained by trapping the title intermediate with N-methylaniline; and for (N-ethoxycarbonylcarbamoyl)(N'-methyl-N'-phenylcarbamoyl)disulfane, which is a short-lived intermediate in the reaction of the title (chlorocarbonyl)(carbamoyl)disulfane with excess N-methylaniline. The new chemistry and structural information reported herein is expected to contribute to accurate modeling of the ZWK reaction trajectory.

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Section: The Journal Of Organic Chemistrymentioning

confidence: 99%