19617-44-8Relevant articles and documents
Reaction of Ethyl Chlorosodiocarbamate with Organic Azides
Gibson, Harry H.,Macha, Matthew R.,Farrow, Sherry J.,Ketchersid, Terry L.
, p. 2062 - 2065 (1983)
Ethyl chlorosodiocarbamate (3) is reactive as a nucleophile toward ethyl azidoformate (4) and tosyl azide but not toward alkyl or aryl azides.Diethyl iminodiformate (5), nitrogen gas, and sodium chloride are the principal products from the reaction of 3 with 4.Mechanistic studies support a reaction scheme involving attack of 3 at the carbonyl group of azide 4, instead of attack at the terminal azido nitrogen.The results of this study are correlated with hard and soft acid and base theory.
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
Barany, George,Britton, Doyle,Chen, Lin,Hammer, Robert P.,Henley, Matthew J.,Schrader, Alex M.,Young, Victor G.
, p. 11313 - 11321 (2015/12/01)
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.
Synthesis of 1-Oxo-1H-pyrazolotriazol-4-ium-3-olates. - A Ring-Chain Tautomerism in the Series of Bicyclic Dipolar Heterocycles
Boettcher, Andreas,Debaerdemaeker, Tony,Radziszewski, Juliusz G.,Friedrichsen, Willy
, p. 895 - 908 (2007/10/02)
1-(Trimethylsilyl)pyrazole (12) reacts with chlorocarbonyl isocyanate to give a compound, which - dependent on the state of aggregation - may exist both as a bicyclic dipolar heterocycle (7) and as monocyclic 1-pyrazolyl carbonyl isocyanate (8).Methyl-substituted derivatives (19a, b) show a similar behaviour.MNDO calculations for the parent systems (7, 8) are in accord with these experimental observations.The structure of 5,6,7-trimethyl-1-oxo-1H-pyrazolotriazol-4-ium-3-olate (19b) has been clarified by X-ray analysis.
THE ELECTROCHEMICAL REDUCTION OF N-FLUOROETHANS IN ACETONITRILE. THE GENERATION OF CARBETHOXYNITRENE
Lessard, Jean,Berube, Denis
, p. 768 - 777 (2007/10/02)
The electrochemical reduction of N-fluoro-N-methylurethan (1a) and N-fluorourethan (2a) in acetonitrile generates the amide anion and fluoride ion.Both the fluoride and the amide react with the starting N-fluoroamide either as bases or as nucleophiles.Many products are formed and the coulometric results are low (0.5 to 0.7 F/mol).In the case of NFU (2a), abstraction of the proton on nitrogen both by the urethan anion and the fluoride anion generates the conjugate base EtOCOF (7) which immediately undergoes α-elimination of the fluoride ion to give carbethoxynitrene (11).This nitrene was generated also by treating NFU (2a) with a base such as triethylamine of lithium hydride.The α-elimination of F1- from EtOCOF is much easier than α-elimination of Cl1- from EtOCOCl.