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

被引：2

作者：

Barany, George ^{[1
]}

Britton, Doyle ^{[1
]}

Chen, Lin ^{[1
]}

Hammer, Robert P. ^{[1
]}

Henley, Matthew J. ^{[1
]}

Schrader, Alex M. ^{[1
]}

Young, Victor G., Jr. ^{[1
]}

机构：

[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2015年 / 80卷 / 22期

基金：

美国国家卫生研究院; 美国国家科学基金会;

关键词：

N-ALPHA-DITHIASUCCINOYL; PHASE PEPTIDE-SYNTHESIS; AMINO PROTECTING GROUP; MILD CONDITIONS; EFFICIENT SYNTHESIS; ACIDS; DERIVATIVES; ISOCYANATE; CHEMISTRY; BIS(CHLOROCARBONYL)DISULFANE;

D O I：

10.1021/acs.joc.5b01826

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The Zumach-Weiss-Kuhle (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-ethoxycarbonylcarbamoy1)(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.

引用

页码：11313 / 11321

页数：9