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.
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.
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出乎意料地稳定的（氯羰基）（N-乙氧基羰基氨基甲酰基）二硫烷以及模拟 Zumach-Weiss-Kühle (ZWK) 反应以合成 1,2,4-二噻唑烷-3,5-二酮的相关化合物。
DOI：
10.1021/acs.joc.5b01826
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发表时间：
2015
期刊：
影响因子：
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通讯作者：
YoungJr,VictorG
中科院分区：
文献类型：
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作者：
Barany,George;Britton,Doyle;Chen,Lin;Hammer,RobertP;Henley,MadeleineJ;Schrader,AlexM;YoungJr,VictorG
Zumach-Weiss-Ku Bohle（ZWK）反应通过O-乙基硫代氨基甲酸酯与（氯羰基）次磺酰氯的快速反应提供1，2，4-二噻唑烷-3，5-二酮[二硫代琥珀酰基（Dts）-胺]，其中氯乙烷和氯化氢作为副产物形成，而氨基甲酰氯或异氰酸酯作为产率降低的副产物产生。然而，当使用（N-乙氧基硫代羰基）氨基甲酸酯作为起始材料应用ZWK反应时，不发生杂环化成推定的“Dts-氨基甲酸酯“。相反，该反应直接提供（氯羰基）（N-乙氧基羰基氨基甲酰基）二硫烷，一种相当稳定的结晶化合物;改性的条件在（氯羰基）[1-乙氧基-（N-乙氧基羰基）甲亚胺基]二硫烷中间体处停止。标题（氯羰基）（氨基甲酰基）二硫烷不能转化为难以得到的Dts衍生物，但在热处理时得到（N-乙氧羰基）氨基甲酰氯，或在用叔胺处理时得到（N-乙氧羰基）异氰酸酯。已经发现了这些化合物的其他转化，为已知和新物种提供了条目。报道了标题化合物的X射线晶体结构（氯羰基）（氨基甲酰基）二硫烷;用于（甲氧羰基）（N-乙氧基羰基氨基甲酰基）二硫烷，其是在甲醇中淬灭后的相应加合物;对于[1-乙氧基-（N-乙氧羰基）甲亚胺基]（N′-甲基-N ′-苯基氨基甲酰基）二硫烷，用N-甲基苯胺捕集得到;（N-乙氧羰基氨基甲酰基）（N′-甲基-N ′-苯基氨基甲酰基）二硫烷，它是标题（氯羰基）（氨基甲酰基）二硫烷与过量N-甲基苯胺反应的短寿命中间体。本文报道的新的化学和结构信息预计将有助于ZWK反应轨迹的准确建模。
The Zumach–Weiss–Kühle (ZWK) reaction provides 1,2,4-dithiazolidine-3,5-diones [dithiasuccinoyl (Dts)-amines] by the rapid reaction ofO-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)disulfanecannotbe 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 withN-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 excessN-methylaniline. The new chemistry and structural information reported herein is expected to contribute to accurate modeling of the ZWK reaction trajectory.