Reactions of Cookson’s diketone with potassium halides in the polyphosphoric acid medium

Authors

  • Oleksandr V. Gaidai National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine https://orcid.org/0000-0003-1325-1928
  • Yevheniia Yu. Zhyhadlo National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine https://orcid.org/0000-0001-9369-3800
  • Igor A. Levandovskiy National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine https://orcid.org/0000-0002-2237-0403
  • Olena G. Sidorenko National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine
  • Oleg V. Shishkin State Scientific Institution “Institute for Single Crystals” of the National Academy of Sciences of Ukraine, Ukraine
  • Svitlana V. Shishkina State Scientific Institution “Institute for Single Crystals” of the National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0002-3946-1061
  • Yuliya V. Rassukana Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0003-2344-9153

DOI:

https://doi.org/10.24959/ophcj.20.186967

Keywords:

Cookson’s diketone, polyphosphoric acid, ring opening, CS-trishomocubane, reduction

Abstract

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: 12.12.2019
Revised: 10.01.2020
Accepted: 27.02.2020

Supporting Agency

  • The budget theme of the Ministry of Education and Science of Ukraine No. 0111U003972

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Published

2020-03-05

How to Cite

(1)
Gaidai, O. V.; Zhyhadlo, Y. Y.; Levandovskiy, I. A.; Sidorenko, O. G.; Shishkin, O. V.; Shishkina, S. V.; Rassukana, Y. V. Reactions of Cookson’s Diketone With Potassium Halides in the Polyphosphoric Acid Medium. J. Org. Pharm. Chem. 2020, 18, 34-38.

Issue

Vol. 18 No. 1(69) (2020)

Section

Original Researches

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