不同酸促进的 4-(4-硫代氨基甲酰基)丁-2-酮腙环氧化聚合模式：14 元环与 28 元聚氮大环的形成。

Different Modes of Acid-Promoted Cyclooligomerization of 4-(4-Thiosemicarbazido)butan-2-one Hydrazone: 14-Membered versus 28-Membered Polyazamacrocycle Formation.

机构信息

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Avenue, 119991 Moscow, Russian Federation.

Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Avenue, Bldg 4, 119071 Moscow, Russian Federation.

出版信息

J Org Chem. 2022 Dec 2;87(23):15722-15731. doi: 10.1021/acs.joc.2c01199. Epub 2022 Nov 16.

DOI:10.1021/acs.joc.2c01199

PMID:36383744

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9724087/

Abstract

Unprecedented self-assembly of a novel 14-membered cyclic bis-thiosemicarbazone or/and a 28-membered cyclic tetrakis-thiosemicarbazone upon acid-promoted cyclooligomerization of 4-(4-thiosemicarbazido)butan-2-one hydrazone has been discovered. A thorough study of the influence of various factors on the direction of macrocyclization provided the optimal conditions for the highly selective formation of each of the macrocycles in excellent yields. Plausible pathways for macrocyclizations have been discussed. The macrocycle precursor was prepared by the reaction of readily available 4-isothiocyanatobutan-2-one with an excess of hydrazine.

摘要

在酸促进的 4-(4-硫代氨基甲酰基)丁-2-酮腙的环齐聚反应中，发现了一种新型的 14 元环双硫代缩氨基脲和/或 28 元环四硫代缩氨基脲的前所未有的自组装。对各种因素对大环化方向的影响进行了深入研究，为每种大环化合物的高产率高选择性形成提供了最佳条件。讨论了大环化的可能途径。大环前体通过与过量的肼反应由易得的 4-异硫氰酸丁-2-酮制备。