Реакції дикетону Куксона з галогенідами калію в середовищі поліфосфорної кислоти

• Main Authors: Gaidai, Oleksandr V., Zhyhadlo, Yevheniia Yu., Levandovskiy, Igor A., Sidorenko, Olena G., Shishkin, Oleg V., Shishkina, Svitlana V., Rassukana, Yuliya V.
• Format: Article
• Language: English
• Published: National University of Pharmacy 2020
• Subjects: Cookson’s diketone; polyphosphoric acid; ring opening; CS-trishomocubane; reduction; UDC 547-316 54.057; дикетон Куксона; поліфосфорна кислота; розкриття циклу; CS-трисгомокубан; відновлення; УДК 547-316 54.057; полифосфорная кислота; раскрытие цикла; восстановление
• Online Access: https://ophcj.nuph.edu.ua/article/view/ophcj.20.186967

Aim. To study the rearrangement of Cookson’s diketone by the action of potassium halides under conditions of polyphosphoric acid catalysis.Results and discussion. Chemical behaviour of Cookson’s diketone (CS-trishomocubane-8,11-dione) in the reactions with potassium halides (KCl, KBr, KI) in the polyphosphoric acid (PPA) medium have been studied. When treated with the KI/PPA mixture Cookson’s diketone undergoes reduction leading to tetracyclo[6.3.0.0.4,11.05,9]undecane-2,7-dione. The use of KBr instead of KI leads to formal addition of HBr to the cyclobutane ring of CS-trishomocubane-8,11-dione and gives 3-bromotetracyclo[6.3.0.04,11.05,9]undecane-2,7-dione. The general scheme of the cycle opening mechanism has been proposed. In the case of using the KCl/PPA mixture the reaction does not occur.Experimental part. The structure and composition of compounds were proved by the methods of 1H and 13C NMR-spectroscopy, and also X-ray diffraction analysis. Elemental analysis was performed for the compounds obtained.Conclusions. It has been shown that hydrohalic acids generated in situ under the reaction conditions do not induce the rearrangement of Cookson’s diketone to the D3-trishomocubane system. The cyclobutane ring opening and reduction take place instead. Received: 12.12.2019Revised: 10.01.2020Accepted: 27.02.2020